Member for semiconductor light emitting device and method of manufacturing the same, and semiconductor light emitting device using the same

0001The present invention relates to a novel member for a semiconductor light emitting device, a method for manufacturing the same, and a semiconductor light emitting device using the same. More specifically, the present invention relates to a member for a semiconductor light emitting device having high durability against ultraviolet rays and heat and excellent transparency, a method for manufacturing the same, and a semiconductor light emitting device using the same.

0002In semiconductor light emitting devices such as light emitting diodes (hereinafter abbreviated as "LED" as appropriate) and semiconductor lasers, the semiconductor light emitting element is sealed with a member such as a transparent resin (member for semiconductor light emitting device). Is common.

0003For example, an epoxy resin is used as the member for the semiconductor light emitting device. Further, there are known ones that convert the emission wavelength from a semiconductor light emitting element by containing a pigment such as a phosphor in this sealing resin.

0004However, since epoxy resin has high hygroscopicity, there are problems such as cracks due to heat from the semiconductor light emitting element generated when the semiconductor light emitting device is used for a long time, and deterioration of the phosphor and the light emitting element due to the infiltration of moisture. was there.

0005Further, in recent years, since the epoxy resin deteriorates and is colored as the emission wavelength is shortened, there is also a problem that the brightness of the semiconductor light emitting device is remarkably lowered in long-time lighting and use at high output.

0006In response to these problems, silicone resins having excellent heat resistance and ultraviolet light resistance have come to be used as alternatives to epoxy resins. However, the silicone resin is still insufficient in adhesion, transparency, and weather resistance. On the other hand, as a material having excellent heat resistance and ultraviolet light resistance, an inorganic encapsulant and a semiconductor light emitting device using the same have been proposed (see, for example, Patent Documents 1 to 5).

<p num="0007"><patcit num="1"><text>Japanese Patent No. 3275308</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 2003-197976</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2004-231947</text></patcit><patcit num="4"><text>JP-A-2002-33517</text></patcit><patcit num="5"><text>JP-A-2002-203989</text></patcit></p>

<p num="0008"> However, inorganic materials such as molten glass have not been industrially realized because the handling temperature is as high as 350 ° C. or higher and damages the light emitting element. Further, in the glass produced by the sol-gel method, there is a problem of crack generation and peeling due to curing shrinkage when molding as a member for a semiconductor light emitting device, and a glass that is stable in a thick film state for a long period of time has not yet been obtained. It was.</p><p num="0009"> Furthermore, since these inorganic encapsulants are extremely hard and brittle, they cannot follow the thermal expansion and contraction of each member with a different coefficient of thermal expansion used in semiconductor light emitting devices, and peeling, cracking, and disconnection occur frequently during use. There are some problems to be solved, and those having excellent reflow resistance and temperature cycle resistance have not yet been obtained. Here, reflow refers to a soldering method in which a solder paste is printed on a substrate, and parts are mounted on the substrate to be heated and joined. Reflow resistance refers to the property of being able to withstand thermal shock at a maximum temperature of 260 ° C for 10 seconds.</p><p num="0010"> For example, Patent Document 1 and Patent Document 2 describe a technique for forming a glass material using a tetrafunctional alkoxysilane. However, regarding the inorganic material obtained by the techniques described in Patent Document 1 and Patent Document 2, a hydrolyzed solution of tetrafunctional alkoxysilane is applied to the semiconductor light emitting device, and the performance of the semiconductor light emitting device is not impaired at 150 ° C. When cured at a moderate curing temperature for several hours, the obtained glass material was usually an incomplete glass body containing silanol in an amount of more than 10% by weight. Therefore, from the techniques described in Patent Document 1 and Patent Document 2, it was not possible to obtain a glass body consisting only of siloxane bonds, unlike the molten glass.</p><p num="0011"> This is because, unlike general organic resins, the inorganic materials used in Patent Document 1 and Patent Document 2 have a large number of cross-linking points, so that the structure is largely bound and the reactive end can be isolated and condensed. It is presumed that there is no such thing. Such a glass body is not dense, and its surface is in a state of being extremely hydrophilic like silica gel, so that it does not have a sufficient sealing ability.</p><p num="0012"> In general, heating at 250 ° C or higher causes a slight decrease in such silanol, which is difficult to react, and the amount of silanol is positively increased by firing at a high temperature of 350 ° C or higher, preferably 400 ° C or higher. Can be reduced. However, even if an attempt is made to remove silanol from the inorganic materials described in Patent Document 1 and Patent Document 2 by utilizing this, it is difficult to realize because the heat resistant temperature of the semiconductor light emitting device is usually 260 ° C. or less. ..</p><p num="0013"> Furthermore, since the tetrafunctional alkoxysilane has a large amount of components desorbed during dehydration / dealcohol condensation, the shrinkage rate during curing is essentially large. Moreover, since the tetrafunctional alkoxysilane has a high degree of cross-linking, curing starts from the surface portion where a part of the diluting solvent evaporates in the drying step, and after forming a hard gel body containing the solvent, the internal solvent is used. Since there is a tendency to release silane, the amount of shrinkage due to solvent evaporation also increases. Therefore, in the inorganic materials described in Patent Document 1 and Patent Document 2, a large internal stress is generated due to shrinkage as a result, and cracks frequently occur. Therefore, it has been difficult to obtain a large bulk body or thick film useful as a member for a semiconductor light emitting device using only tetrafunctional alkoxysilane as a raw material.</p><p num="0014"> Further, for example, Patent Document 3 describes a technique for producing a three-dimensional phosphor layer with high dimensional accuracy by a sol-gel method using a silane compound containing an organic group as a raw material. However, Patent Document 3 does not have a detailed description of the degree of cross-linking, and in order to obtain the inorganic material described in Patent Document 3, high-concentration phosphor particles are indispensable, and this substantially acts as an aggregate 3 When the inorganic material did not contain a phosphor in order to maintain the three-dimensional shape, it was not possible to obtain a transparent, crack-free, thick-film glass-like coating.</p><p num="0015"> Further, in the technique described in Patent Document 3, acetic acid is used as a catalyst, but since acetic acid is not removed from the obtained inorganic material, acetic acid adversely affects the semiconductor light emitting device. Further, when the inorganic material described in Patent Document 3 is formed, it requires a high temperature of 400 ° C. for curing, so that it is practically impossible to heat it together with the semiconductor light emitting device, and the inorganic material is formed by unreasonable condensation at a high temperature. The structure is distorted and cracks are not suppressed.</p><p num="0016"> Further, for example, Patent Document 4 describes a technique for obtaining a member for a semiconductor light emitting device by applying an inorganic coating agent obtained by mixing an inorganic light scattering agent with an inorganic sol having silica or siloxane as a skeleton. .. However, an inorganic light scattering agent is indispensable for the inorganic material described in Patent Document 4, and further, there is no detailed description of the raw material and the manufacturing method in Patent Document 4, and it is impossible to accurately reproduce the technique. ..</p><p num="0017"> Further, for example, Patent Document 5 describes a technique of applying a sol-gel process glass to obtain a member for a semiconductor light emitting device. However, as in Patent Document 3, a phosphor is indispensable for obtaining the inorganic material described in Patent Document 5. Further, this phosphor acts as an aggregate, and the obtained inorganic material has a thick film, but the film thickness does not exceed 100 μm. Further, Patent Document 5 does not describe a raw material or a manufacturing method, and it is difficult to stably reproduce the technique by using a general alkoxysilane.</p><p num="0018"> From the above background, the curing conditions are mild, the semiconductor light emitting device is excellent in transparency, light resistance, and heat resistance, and the semiconductor light emitting device can be sealed and the phosphor can be retained without causing cracks or peeling even after long-term use. A member for a semiconductor light emitting device has been required.</p><p num="0019"> The present invention has been made in view of the above-mentioned problems. That is, an object of the present invention is to have excellent transparency, light resistance, heat resistance, reflow resistance and temperature cycle resistance, and to seal a semiconductor light emitting device without causing cracks or peeling even after long-term use, and to fluoresce. It is an object of the present invention to provide a new member for a semiconductor light emitting device capable of holding a body.</p>

<p num="0020"> As a result of diligent studies to achieve the above object, the present inventors have a specific peak in the solid Si-nuclear magnetic resonance (hereinafter, appropriately referred to as "NMR") spectrum and contain silicon. A polymer whose rate is equal to or higher than a specific value, whose silanol content is within a predetermined range, and whose hardness measurement value by durometer type A is within a predetermined range can be thickened when used as a member for a semiconductor light emitting device. The present invention has been completed by finding that the occurrence of cracks is suppressed even in a thick film portion and the adhesion, heat resistance, transparency, reflow resistance and temperature cycle resistance are excellent.</p><p num="0021"> That is, the gist of the present invention is a light emitting device having a light emitting element and a sealing portion for sealing the light emitting element, and the sealing portion is (1) in a solid Si-nuclear magnetic resonance spectrum. i) The peak top position is in the region of chemical shift -40ppm or more and 0ppm or less, and the peak half price range is 0.3ppm or more and 3.0ppm or less, and (ii) the peak top position is chemical shift-80ppm or more. It has at least one peak selected from the group consisting of peaks in the region of less than -40ppm and whose half-price range is 0.3ppm or more and 5.0ppm or less, and (2) has a silicon content of 20% by weight or more. , (3) The silanol content is 0.1% by weight or more and 10% by weight or less, and (4) The hardness measurement value (shore A) by durometer type A is 5 or more and 90 or less.<u style="single">Is transparent</u>A semiconductor light emitting device, characterized in that it contains a member for a semiconductor light emitting device (claim 1). At this time,<u style="single">The semiconductor light emitting device member may have a light transmittance of 80% or more at a wavelength of 405 nm at a film thickness of 0.5 mm (claim 2).</u><u style="single"> Also,</u>The light emitting device further has an insulating substrate, and the insulating substrate is provided with a recess for accommodating the light emitting element on one surface thereof, and the light emitting element is mounted on the bottom of the recess, and the inside of the recess is provided. May be provided with the sealing portion (claim).<u style="single">3</u>). Further, in the semiconductor light emitting device, the light emitting element is a gallium nitride based LED chip, and the printed wiring formed on the insulating substrate is extended to the bottom of the recess, and the light emitting element is connected via a conductive wire. It may be electrically connected to the light emitting layer portion (claim).<u style="single">4</u>). Another gist of the present invention is a light emitting device having a light emitting element surface-mounted on an insulating substrate and a sealing portion for sealing the light emitting element, and the sealing portion seals the light emitting element. It is composed of a conical stand-shaped sealing function part that stops and a lens-shaped lens function part that functions as a lens at the front end of the sealing part, and the sealing part is (1) solid Si-nuclear magnetic resonance. In the spectrum, (i) the peak top position is in the chemical shift-40ppm or more and 0ppm or less region, the peak half-price range is 0.3ppm or more and 3.0ppm or less, and (ii) the peak top position is the chemical. The shift has at least one peak selected from the group consisting of peaks in the region of -80ppm or more and less than -40ppm, and the half-price range of the peak is 0.3ppm or more and 5.0ppm or less, and (2) the silicon content is 20% by weight. % Or more, (3) Syranol content is 0.1% by weight or more and 10% by weight or less, and (4) Hardness measurement value (shore A) by durometer type A is 5 or more and 90 or less.<u style="single">Is transparent</u>A semiconductor light emitting device, characterized in that it contains a member for a semiconductor light emitting device (claim).<u style="single">5</u>)。<u style="single"> At this time, the semiconductor light emitting device member may have a light transmittance of 80% or more at a wavelength of 405 nm at a film thickness of 0.5 mm (claim 6).</u><u style="single">Also,</u>In the above semiconductor light emitting device, the sealing portion is a phosphor portion containing a phosphor and having a wavelength conversion function, and further, ultrafine silica may be contained as inorganic oxide fine particles (claim).<u style="single">7</u>). Yet another gist of the present invention is a light emitting device having a light emitting element, an insulating substrate, and a sealing portion for sealing the light emitting element, and the insulating substrate accommodates the light emitting element on one surface thereof. A recess is provided, and the light emitting element is flip-chip mounted on the insulating substrate, the sealing portion is provided in the recess, and the light emitting layer of the light emitting element is located closest to the insulating substrate. A part is arranged, and a phosphor part containing a phosphor and a member for a semiconductor light emitting device is formed on the upper surface of the light emitting layer part, and the member for a semiconductor light emitting device is (1) solid Si-nuclear magnetism. In the resonance spectrum, (i) the peak top position is in the region of chemical shift -40ppm or more and 0ppm or less, and the peak half-price range is 0.3ppm or more and 3.0ppm or less, and (ii) the peak top position is. Chemical shift has at least one peak selected from the group consisting of peaks in the region of -80ppm or more and less than -40ppm, and the half-price range of the peak is 0.3ppm or more and 5.0ppm or less, and (2) the silicon content is 20. Weight% or more, (3) Silanol content is 0.1% by weight or more, 10% by weight or less, and (4) Durometer type A hardness measurement value (shore A) is 5 or more and 90 or less.<u style="single">Is transparent</u>It exists in the semiconductor light emitting device, characterized in that (claim).<u style="single">8</u>). At this time,<u style="single">The semiconductor light emitting device member may have a light transmittance of 80% or more at a wavelength of 405 nm at a film thickness of 0.5 mm (claim 9).</u><u style="single"> Also,</u>In the semiconductor light emitting device, the sealing portion is (1) in the solid Si-nuclear magnetic resonance spectrum, (i) the position of the peak top is in the region of chemical shift -40ppm or more and 0ppm or less, and the half price width of the peak is 0.3. A group consisting of peaks of ppm or more and 3.0 ppm or less, and (ii) peaks whose top position is in the chemical shift range of -80 ppm or more and less than -40 ppm, and whose half-price range is 0.3 ppm or more and 5.0 ppm or less. It has at least one peak selected from the above, (2) silicon content is 20% by weight or more, (3) silanol content is 0.1% by weight or more and 10% by weight or less, and (4) durometer type. A member for a semiconductor light emitting device having a hardness measurement value (shore A) according to A of 5 or more and 90 or less may be contained (claim).<u style="single">10</u>)。 </p>

<p num="0035"> The member for a semiconductor light emitting device of the present invention can be coated with a thick film as compared with a conventional member for an inorganic semiconductor light emitting device, and the semiconductor light emitting device can be easily sealed only by coating and drying on the semiconductor light emitting device. It can be stopped and retain the phosphor. In addition, it is excellent in transparency, light resistance, heat resistance, reflow resistance and temperature cycle resistance, and does not cause cracks or peeling even after long-term use.</p>

0036<figref num="1">It is schematic sectional drawing which shows Embodiment A-1.</figref><figref num="2">It is schematic sectional drawing which shows Embodiment A-2.</figref><figref num="3">Embodiment B-1 is shown, (a) is a schematic cross-sectional view, and (b) is an enlarged view of a main part of (a).</figref><figref num="4">It is a schematic sectional drawing which shows Embodiment B-2.</figref><figref num="5">It is schematic sectional drawing which shows Embodiment B-3.</figref><figref num="6">It is schematic sectional drawing which shows Embodiment B-4.</figref><figref num="7">It is schematic sectional drawing which shows Embodiment B-5.</figref><figref num="8">It is schematic sectional drawing which shows Embodiment B-6.</figref><figref num="9">It is schematic sectional drawing which shows Embodiment B-7.</figref><figref num="10">It is schematic sectional drawing which shows Embodiment B-8.</figref><figref num="11">It is schematic sectional drawing which shows Embodiment B-9.</figref><figref num="12">It is a schematic sectional drawing which shows Embodiment B-10.</figref><figref num="13">It is schematic sectional drawing which shows Embodiment B-11.</figref><figref num="14">It is a schematic sectional drawing which shows Embodiment B-12.</figref><figref num="15">It is schematic sectional drawing which shows Embodiment B-13.</figref><figref num="16">It is schematic sectional drawing which shows Embodiment B-14.</figref><figref num="17">It is a schematic sectional drawing which shows Embodiment B-15.</figref><figref num="18">It is schematic sectional drawing which shows Embodiment B-16.</figref><figref num="19">It is a schematic sectional drawing which shows embodiment B-17.</figref><figref num="20">It is a schematic sectional drawing which shows Embodiment B-18.</figref><figref num="21">It is schematic sectional drawing which shows Embodiment B-19.</figref><figref num="22">It is schematic sectional drawing which shows Embodiment B-20.</figref><figref num="23">It is a schematic sectional drawing which shows Embodiment B-21.</figref><figref num="24">It is sectional drawing of the main part which shows embodiment B-21.</figref><figref num="25">It is schematic sectional drawing which shows Embodiment B-22.</figref><figref num="26">It is sectional drawing of the main part which shows Embodiment B-22.</figref><figref num="27">It is schematic sectional drawing which shows Embodiment B-23.</figref><figref num="28">It is a main part perspective view which shows the embodiment B-23.</figref><figref num="29">It is the schematic sectional drawing which shows the embodiment B-24.</figref><figref num="30">It is sectional drawing of the main part which shows the Embodiment B-24.</figref><figref num="31">It is a main part perspective view which shows the Embodiment B-24.</figref><figref num="32">It is a schematic sectional drawing which shows Embodiment B-25.</figref><figref num="33">It is schematic cross-sectional view which shows embodiment B-26.</figref><figref num="34">It is schematic sectional drawing which shows Embodiment B-27.</figref><figref num="35">It is a schematic sectional drawing which shows Embodiment B-28.</figref><figref num="36">It is a schematic sectional drawing which shows Embodiment B-29.</figref><figref num="37">Embodiment B-30 is shown, (a) is a schematic cross-sectional view, and (b) is an enlarged view of a main part of (a).</figref><figref num="38">It is schematic sectional drawing which shows Embodiment B-31.</figref><figref num="39">It is schematic cross-sectional view which shows embodiment B-32.</figref><figref num="40">It is the schematic sectional drawing which shows Embodiment B-33.</figref><figref num="41">It is a schematic sectional drawing which shows Embodiment B-34.</figref><figref num="42">It is schematic cross-sectional view which shows embodiment B-35.</figref><figref num="43">It is sectional drawing which shows the embodiment B-36.</figref><figref num="44">It is schematic sectional drawing which shows Embodiment B-37.</figref><figref num="45">It is schematic sectional drawing which shows Embodiment B-38.</figref><figref num="46">It is schematic sectional drawing which shows Embodiment B-39.</figref><figref num="47">It is a schematic sectional drawing which shows Embodiment B-40.</figref><figref num="48">It is explanatory drawing of the other structural example of the main part of each embodiment.</figref><figref num="49">Both (a) and (b) are explanatory diagrams of the basic concept of each embodiment.</figref><figref num="50">It is an individual Si-NMR spectrum measured in Example 1 of this invention.</figref><figref num="51">It is an individual Si-NMR spectrum measured in Comparative Example 2.</figref>

0037Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

0038[I. Parts for semiconductor light emitting devices] The member for a semiconductor light emitting device of the present invention has the following features (1) to (4). (1) In the solid Si-NMR spectrum (i) The position of the peak top is in the region of chemical shift -40ppm or more and 0ppm or less, and the half width of the peak is 0.3ppm or more and 3.0ppm or less. (ii) The peak position is in the region of chemical shift -80ppm or more and less than -40ppm, and the half width of the peak is 0.3ppm or more and 5.0ppm or less. It has at least one peak selected from the group consisting of. (2) The silicon content is 20% by weight or more. (3) The silanol content is 0.1% by weight or more and 10% by weight or less. (4) The hardness measurement value (shore A) by durometer type A is 5 or more and 90 or less. Hereinafter, these features (1) to (4) will be described first.

0039[I-1. Solid Si-NMR spectrum] Silicon-based compounds are SiO₂ NH₂It is represented by the rational formula of O, but structurally, oxygen atom O is bonded to each vertex of the tetrahedron of silicon atom Si, and silicon atom Si is further bonded to these oxygen atom O to form a net. It has an expanded structure. The schematic diagram shown below shows the net structure of Si-O, ignoring the above tetrahedral structure. However, in the repeating unit of Si-O-Si-O-, one of the oxygen atoms O The department is another member (eg -H, -CH₃When focusing on one silicon atom Si, it is replaced with silicon atom Si (Q) having four -OSi as shown in (A) of the schematic diagram.⁴), Silicon atom Si with 3 -OSi as shown in (B) of the schematic diagram (Q)³) Etc. exist. Then, in the solid-state Si-NMR measurement, the peaks based on each of the above silicon atom Sis are sequentially Q.⁴Peak, Q³It is called the peak.

0040<chemistry num="3"><img id="000002" he="69" wi="159" file="JP5694875B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0041Silicon atoms with four of these oxygen atoms bonded together are generally collectively referred to as Q sites. In the present invention, Q derived from the Q site⁰~ Q⁴Q each peak ofⁿWe will call it the peak group. Q of silica film containing no organic substituentⁿThe peak group is usually observed as a continuous multimodal peak in the chemical shift range of -80 to -130 ppm.

0042On the other hand, a silicon atom in which three oxygen atoms are bonded and one other atom (usually carbon) is bonded is generally called a T site. The peak derived from the T site is T as in the case of the Q site.⁰~ T³It is observed as each peak of. In the present invention, each peak derived from the T site is T.ⁿWe will call it the peak group. TⁿPeaks are generally QⁿIt is observed as a continuous multimodal peak in the region on the higher magnetic field side (usually chemical shift -80 to -40ppm) than the peak group.

0043Furthermore, a silicon atom in which two oxygen atoms are bonded and two other atoms (usually carbon) are bonded is generally referred to as a D site. The peaks derived from the D site are also the same as the peaks derived from the Q site and the T site.⁰~ DⁿEach peak of (DⁿObserved as a peak group), QⁿAnd TⁿIt is observed as a multimodal peak in the region on the high magnetic field side (usually in the region of 0 to -40 ppm of chemical shift) from the peak group of. These Dⁿ, Tⁿ, QⁿSince the ratio of the area of each peak group in is equal to the molar ratio of silicon atoms in the environment corresponding to each peak group, if the area of all peaks is the molar amount of all silicon atoms, DⁿPeak group and TⁿThe total area of the peak group usually corresponds to the molar amount of total silicon directly bonded to the carbon atom.

0044When the solid Si-NMR spectrum of the member for the semiconductor light emitting device of the present invention is measured, D derived from the silicon atom in which the carbon atom of the organic group is directly bonded is obtained.ⁿPeak group and TⁿQ derived from the peak group and the silicon atom that is not bonded to the carbon atom of the organic groupⁿPeak groups appear in different regions. Of these peaks, peaks below -80ppm are Q as described above.ⁿCorresponds to the peak, peaks above -80ppm are Dⁿ, TⁿCorresponds to the peak. In the member for the semiconductor light emitting device of the present invention, QⁿPeak is not required, but Dⁿ, TⁿAt least one, preferably multiple, peaks are observed in the peak region.

0045The chemical shift value of the semiconductor light emitting device member can be calculated based on the result of solid-state Si-NMR measurement performed by, for example, the following method. Further, the analysis of the measurement data (half-value width and silanol amount analysis) is performed by a method of dividing and extracting each peak by, for example, a waveform separation analysis using a Gaussian function or a Lorentz function.

0046[Solid Si-NMR spectrum measurement and calculation of silanol content] When solid-state Si-NMR spectrum is performed on a member for a semiconductor light emitting device, solid-state Si-NMR spectrum measurement and waveform separation analysis are performed under the following conditions. Further, from the obtained waveform data, the half width of each peak is obtained for the semiconductor light emitting device member. In addition, the ratio (%) of the silicon atom that is silanol in the total silicon atom is obtained from the ratio of the peak area derived from silanol to the total peak area, and the silanol content is calculated by comparing with the silicon content analyzed separately. Ask.

0047&lt;Device conditions&gt; Equipment: Chemagnetics Infinity CMX-400 Nuclear Magnetic Resonance Spectroscopy²⁹Si resonance frequency: 79.436MHz Probe: 7.5mmφ CP / MAS probe Measurement temperature: room temperature Sample rotation speed: 4kHz Measurement method: Single pulse method¹H decoupling frequency: 50kHz²⁹Si flip angle: 90 °²⁹Si90 ° pulse width: 5.0 μs Repeat time: 600s Accumulation number: 128 times Observation width: 30kHz Broadening factor: 20Hz

0048&lt;Data processing method&gt; For semiconductor light emitting device members, 512 points are taken in as measurement data, zero-filled to 8192 points, and Fourier transformed.

0049&lt;Waveform separation analysis method&gt; For each peak of the spectrum after Fourier transform, the optimization calculation is performed by the nonlinear least squares method with the center position, height, and half width of the peak shape created by the Lorentz waveform and Gauss waveform or a mixture of both as variable parameters.

0050For peak identification, refer to AIChE Journal, 44 (5), p.1141, 1998, etc.

0051[I-2. Silicon content] The member for a semiconductor light emitting device of the present invention must have a silicon content of 20% by weight or more (feature (2)). The basic skeleton of conventional semiconductor light emitting device members is an organic resin such as an epoxy resin having carbon-carbon and carbon-oxygen bonds as the basic skeleton. On the other hand, the basic skeleton of the member for the semiconductor light emitting device of the present invention is the same inorganic siloxane bond as glass (silicate glass). As is clear from the chemical bond comparison table in Table 1 below, this siloxane bond has the following characteristics that are excellent as a member for a semiconductor light emitting device.

0052(I) It has good light resistance because it has a large binding energy and is difficult to thermally or photodecompose. (II) It is electrically slightly polarized. (III) The chain structure has a large degree of freedom, a highly flexible structure is possible, and it can freely rotate around the center of the siloxane chain. (IV) The degree of oxidation is high and it is not oxidized any more. (V) Rich in electrical insulation.

0053<tables num="1"><img id="000003" he="31" wi="159" file="JP5694875B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>

0054Due to these characteristics, the silicone-based semiconductor light-emitting device member formed by the skeleton in which the siloxane bond is three-dimensionally bonded with a high degree of cross-linking is different from the conventional resin-based semiconductor light-emitting device member such as epoxy resin. Alternatively, it can be understood that the protective film is close to an inorganic substance such as rock and has high heat resistance and light resistance. In particular, a member for a silicone-based semiconductor light emitting device having a methyl group as a substituent does not have absorption in the ultraviolet region, so photodecomposition is unlikely to occur, and the member is excellent in light resistance.

0055The silicon content of the member for the semiconductor light emitting device of the present invention is 20% by weight or more as described above, and among them, 25% by weight or more is preferable, and 30% by weight or more is more preferable. On the other hand, the upper limit is SiO₂It is usually in the range of 47% by weight or less because the silicon content of the glass made of chisel is 47% by weight.

0056The silicon content of the semiconductor light emitting device member is determined by inductively coupled plasma spectroscopy (hereinafter abbreviated as "ICP" as appropriate) analysis using, for example, the following method, and based on the result. It can be calculated.

0057[Measurement of silicon content] A single cured product of a semiconductor light emitting device member is crushed to about 100 μm and fired in a platinum crucible in the air at 450 ° C for 1 hour, then at 750 ° C for 1 hour, and at 950 ° C for 1.5 hours. After removing the carbon component, add 10 times or more of sodium carbonate to a small amount of the obtained residue, heat it with a burner to melt it, cool it, add desalted water, and adjust the pH to about neutral with hydrochloric acid. While adjusting, adjust the volume to about several ppm as silicon, and perform ICP analysis.

0058[I-3. Silanol content] The member for a semiconductor light emitting device of the present invention has a silanol content of usually 0.1% by weight or more, preferably 0.3% by weight or more, and usually 10% by weight or less, preferably 8% by weight or less, more preferably 5% by weight or less. The range of (feature (3)).

0059Normally, a glass body obtained by the sol-gel method using alkoxysilane as a raw material does not completely polymerize to form an oxide under mild curing conditions of about 3 hours at 150 ° C., and a certain amount of silanol remains. The glass body obtained only from tetraalkoxysilane has high hardness and high light resistance, but the degree of freedom of the molecular chain is small due to the high degree of cross-linking, and the amount of residual silanol is large because complete condensation does not occur. Further, when the hydrolyzed / condensed solution is dried and cured, the thickening is quick because there are many cross-linking points, and the drying and curing proceed at the same time, so that the bulk body has a large strain. When such a member is used as a member for a semiconductor light emitting device, new internal stress is generated due to condensation of residual silanol during long-term use, and defects such as cracks, peeling, and disconnection are likely to occur. Further, the fracture surface of the member contains more silanol, and although the moisture permeability is low, the surface hygroscopicity is high and moisture is likely to enter. Although it is possible to reduce the silanol content by firing at a high temperature of 400 ° C or higher, most semiconductor light emitting devices have heat resistance of 260 ° C or lower, which is not realistic.

0060On the other hand, the member for a semiconductor light emitting device of the present invention has a low silanol content, so that it does not change with time, has excellent long-term performance stability, and has excellent performance with low hygroscopicity and moisture permeability. However, since the member containing no silanol is inferior in adhesion to the semiconductor light emitting device, the silanol content has an optimum range as described above in the present invention.

0061The silanol content of the semiconductor light emitting device member is determined by using the method described in [Measurement of solid Si-NMR spectrum and calculation of silanol content] of [I-1. Solid Si-NMR spectrum], for example. By performing NMR spectrum measurement and determining the ratio (%) of the silicon atom that is silanol in the total silicon atom from the ratio of the peak area derived from silanol to the total peak area, and comparing it with the silicon content analyzed separately. Can be calculated.

0062[I-4. Hardness measurement value] The member for a semiconductor light emitting device of the present invention is an elastomer-like member. Specifically, the hardness measurement value (shore A) by the durometer type A is usually 5 or more, preferably 7 or more, more preferably 10 or more, and usually 90 or less, preferably 80 or less, more preferably 70 or less. There is (feature (4)). By having the hardness measurement value in the above range, the member for the semiconductor light emitting device of the present invention can obtain the advantages that cracks are less likely to occur and the reflow resistance and the temperature cycle resistance are excellent.

0063The above hardness measurement value (shore A) can be measured by the method described in JIS K 6253. Specifically, the measurement can be performed using an A-type rubber hardness tester manufactured by Furusato Seiki Seisakusho.

0064[I-5. Reasons why the effects of the present invention can be obtained by the above features (1) to (4)] By providing the above-mentioned features (1) to (4), the member for a semiconductor light emitting device of the present invention is densely cured without cracking even in a thick film portion, has less internal stress, and adheres to a case. It is possible to obtain a cured product having excellent chip sealing characteristics and excellent durability against light and heat after curing. The reason for this is not clear, but it is presumed as follows.

0065There are two methods for obtaining a member for a semiconductor light emitting device made of inorganic glass: a melting method in which low melting point glass is melted and sealed, and a solution in which alkoxysilane or the like is hydrolyzed and polycondensed at a relatively low temperature and dried. There is a sol-gel method for curing. Of these, the members obtained from the melting method are mainly QⁿOnly peaks are observed, but melting requires a high temperature of at least 350 ° C or higher, which is not a realistic method because it thermally deteriorates the semiconductor light emitting device.

0066On the other hand, the hydrolysis / polycondensation product obtained from the tetrafunctional silane compound in the sol-gel method is a completely inorganic glass and has extremely excellent heat resistance and weather resistance, but the curing reaction is the condensation (dehydration / decondensation) of silanol. Since cross-linking proceeds by the (alcohol) reaction, weight loss and volume shrinkage are accompanied by the amount of dehydration. Therefore, QⁿIf the raw material is composed of only tetrafunctional silane having a peak, the degree of curing shrinkage becomes too large, cracks are likely to occur in the film, and the film cannot be thickened. In such a system, attempts have been made to increase the film thickness by adding inorganic particles as an aggregate or by recoating, but generally, the limit film thickness is about 10 μm. When sol-gel glass is used as a member for a semiconductor light emitting device, it is necessary to mold it on a wiring portion having a complicated shape, so that there is a problem that a film thickness of 500 to 1000 μm must be secured. Further, as described above, in order to sufficiently reduce residual silanol and obtain a completely inorganic glass, heating at a high temperature of 400 ° C. or higher is required, which is not realistic because the semiconductor device is thermally deteriorated.

0067On the other hand, in the member for a semiconductor light emitting device of the present invention, in order to adjust the crosslink density and give the film flexibility, TⁿTrifunctional silane with peaks and / or DⁿBy introducing a bifunctional silane with a peak and performing hydrolysis / polycondensation at the same time, the volume reduction due to dehydration condensation and the crosslink density are appropriately reduced within a range that does not interfere with the function, and the hydrolysis / condensation step and drying are performed. By controlling the process, it is possible to obtain a transparent elastomer-like member having a film thickness of 1000 μm. Therefore, in the present invention, T observed above -80ppmⁿPeak and / or DⁿThe presence of peaks is essential.

0068As a method for thickening a film using a bifunctional or trifunctional raw material as a main component, for example, a technique for a hard coat film such as eyeglasses is known, but the film thickness is several μm or less. Since these hard coat films have a thin film thickness, the solvent can be easily volatilized and can be cured uniformly, and the difference in adhesion to the substrate and the coefficient of linear expansion has been regarded as the main cause of cracks. On the other hand, in the member for a semiconductor light emitting device of the present invention, since the film thickness is as large as that of a paint, the film itself has a certain degree of strength, and a slight difference in linear expansion coefficient can be absorbed, but due to solvent drying. Due to the volume reduction, the generation of internal stress, which is different from that of the thin film, becomes a new issue. That is, when molding a deep container having a narrow opening area such as an LED cup, if heat curing is performed in a state where the film is not sufficiently dried, solvent volatilization occurs after cross-linking and the volume is reduced, resulting in a large crack. Or foaming. A large internal stress is applied to such a film, and it is detected when solid Si-NMR of this film is measured.ⁿ, Tⁿ, QⁿThe peak group is whiter than when the internal stress is small. Distribution occurs in the xan bond angles, each with a broader peak. This fact means that there is a large strain on the bond angles represented by the two -OSi for Si. That is, even if the film is made of the same raw material, the narrower the half width of these peaks, the less likely it is that cracks will occur, resulting in a high-quality film.

0069The phenomenon that the half width increases according to the strain is observed more sensitively as the degree of restraint of the molecular motion of the Si atom increases, and its susceptibility to appear is D.ⁿ&lt;Tⁿ&lt;QⁿWill be.

0070In the present invention, the half width of the peak observed in the region of -80 ppm or more is smaller (narrower) than the half width range of the semiconductor light emitting device member known by the sol-gel method.

0071Arranged by chemical shift, in the present invention, the peak top position is observed to be -80ppm or more and less than -40ppm.ⁿThe half width of the peak group is usually 5.0 ppm or less, preferably 4.0 ppm or less, and usually 0.3 ppm or more, preferably 0.4 ppm or more.

0072Similarly, the peak top position is observed at -40ppm or more and 0ppm or less.ⁿThe half width of the peak group is generally T due to the small constraint of molecular motion.ⁿIt is smaller than the peak group, usually in the range of 3.0 ppm or less, preferably 2.0 ppm or less, and usually in the range of 0.3 ppm or more.

0073If the half-value width of the peak observed in the above chemical shift region is larger than the above range, the molecular motion is largely constrained and the strain becomes large, cracks are likely to occur, and the member may be inferior in heat resistance and weather resistance. There is. For example, when a large amount of tetrafunctional silane is used, or when rapid drying is performed in the drying step and a large internal stress is accumulated, the half width range becomes larger than the above range.

0074If the half width of the peak is smaller than the above range, the Si atom in the environment is not involved in siloxane cross-linking, and the trifunctional silane is formed mainly by siloxane bonds, such as in the case where it remains in an uncross-linked state. There is a risk that the member will be inferior in heat resistance and weather resistance to materials.

0075Further, as described above, in the solid Si-nuclear magnetic resonance spectrum of the member for the semiconductor light emitting device of the present invention, Dⁿ, TⁿAt least one, preferably multiple, peaks are observed in the peak region. Therefore, the solid Si-nuclear magnetic resonance spectrum of the member for the semiconductor light emitting device of the present invention has a half width in the above range.ⁿPeak group and TⁿIt is desirable to have at least one, preferably two or more peaks selected from the group consisting of peak groups.

0076The composition of the member for a semiconductor light emitting device of the present invention is limited to the case where the cross-linking in the system is mainly formed by an inorganic component such as silica. That is, even if a peak in the above-mentioned half-value width range is observed at -80 ppm or more in a member for a semiconductor light emitting device containing a small amount of Si component in a large amount of organic component, the good heat resistance and light resistance specified in the present invention and light resistance and light resistance Coating performance cannot be obtained. The member for a semiconductor light emitting device having a silicon content of 20% by weight or more according to the provisions of the present invention is silica (SiO).₂) Converted to 43% by weight or more SiO₂Contains.

0077Further, the member for a semiconductor light emitting device of the present invention has a predetermined hardness measurement value (shore A). That is, the member for a semiconductor light emitting device of the present invention exhibits an elastomer-like shape in which the crosslink density is adjusted. A plurality of members having different coefficients of thermal expansion are used for the semiconductor light emitting device, but the member for the semiconductor light emitting device of the present invention relaxes the stress due to the expansion and contraction of each of the above components by exhibiting an elastomer shape as described above. can do. Therefore, it is possible to provide a semiconductor light emitting device which is less likely to cause peeling, cracking, disconnection, etc. during use and has excellent reflow resistance and temperature cycle resistance.

0078Further, since the member for a semiconductor light emitting device of the present invention contains an appropriate amount of silanol, silanol is hydrogen-bonded to a polar portion existing on the surface of the device, and adhesion is exhibited. Examples of the polar portion include a hydroxyl group, a metalloxane-bonded oxygen, and the like. Further, the member for a semiconductor light emitting device of the present invention forms a covalent bond by dehydration condensation with a hydroxyl group on the surface of the device by heating in the presence of an appropriate catalyst, and further exhibits strong adhesion. Can be done. On the other hand, if there is too much silanol, the inside of the system becomes thick and difficult to apply, or the activity becomes high and the light boiling content solidifies before volatilizing due to heating, resulting in foaming and an increase in internal stress. It may occur and induce cracks and the like.

0079[I-6. UV transmittance] The member for a semiconductor light emitting device of the present invention preferably has a light transmittance of usually 80% or more, particularly preferably 85% or more, more preferably 90% or more at the light emitting wavelength of the semiconductor light emitting device at a film thickness of 0.5 mm. The light extraction efficiency of semiconductor light emitting devices has been improved by various technologies, but if the transparency of the translucent member for sealing the chip or holding the phosphor is low, the semiconductor light emitting device using this Since the brightness is reduced, it becomes difficult to obtain a high-brightness semiconductor light emitting device product.

0080Here, the "emission wavelength of the semiconductor light emitting device" is a value different depending on the type of the semiconductor light emitting device, but is generally 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm. Refers to wavelengths in the following range. If the light transmittance at wavelengths in this range is low, the semiconductor light emitting device member absorbs light, the light extraction efficiency is lowered, and a high-luminance device cannot be obtained. Further, the energy corresponding to the decrease in the light extraction efficiency is converted into heat, which causes thermal deterioration of the device, which is not preferable.

0081Since the sealing member is susceptible to photodegradation in the ultraviolet to blue region (300 nm to 500 nm), the semiconductor light emitting device member of the present invention having excellent durability is used for the semiconductor light emitting device having an emission wavelength in this region. This is preferable because the effect is increased.

0082The light transmittance of the semiconductor light emitting device member can be measured by an ultraviolet spectrophotometer using, for example, a sample of a single cured product film having a smooth surface formed to a film thickness of 0.5 mm by the following method. ..

0083[Measurement of transparency] Using an ultraviolet spectrophotometer (UV-3100 manufactured by Shimadzu Corporation) using a single cured product film with a smooth surface of about 0.5 mm in thickness that is not scattered by scratches or irregularities of the member for semiconductor light emitting devices, the wavelength is 200 nm. Transparency is measured at ~ 800 nm.

0084However, there are various shapes of semiconductor devices, and most of them are used in a thick film state exceeding 0.1 mm, but a thin film phosphor layer (for example, nanofluorescent material) is located at a position away from the LED chip (light emitting element). There are also applications for using a thin film, such as when providing a layer having a thickness of several μm containing particles and fluorescent ions) or when providing a highly refracting light extraction film on a thin film directly above the LED chip. In such a case, it is preferable to show a transmittance of 80% or more at this film thickness. Even in such a thin film application form, the member for a semiconductor light emitting device of the present invention exhibits excellent light resistance and heat resistance, has excellent sealing performance, and can stably form a film without cracks or the like.

0085[I-7. Peak area ratio] The member for a semiconductor light emitting device of the present invention preferably satisfies the following condition (5). That is, the member for a semiconductor light emitting device of the present invention has (5) the total area of peaks of (chemical shift -40ppm or more and 0ppm or less) / (total area of peaks of chemical shift less than -40ppm) in the solid Si-nuclear magnetic resonance spectrum. ) (As appropriate, hereinafter referred to as "peak area ratio according to the present invention") is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually 200 or less, preferably 100 or less, more preferably 50. The following is preferable.

0086The fact that the peak area ratio according to the present invention is within the above range means that the member for the semiconductor light emitting device of the present invention uses bifunctional silane (D site), trifunctional silane (T site) and tetrafunctional silane (Q site). It means that it has more than bifunctional or higher silane such as. As described above, by having a large amount of bifunctional silane, the member for a semiconductor light emitting device of the present invention can satisfy the condition (4) (it exhibits an elastomeric state), and can relieve stress.

0087However, the member for a semiconductor light emitting device of the present invention may exhibit an elastomeric state even if the condition (5) is not satisfied. For example, this case corresponds to the case where the member for the semiconductor light emitting device of the present invention is manufactured by using a coupling agent such as an alkoxide of a metal other than silicon as a cross-linking agent. The method for satisfying the condition (4) for the semiconductor light emitting device member of the present invention is arbitrary, and is not limited to this condition (5).

0088[I-8. Others] The member for a semiconductor light emitting device of the present invention can be applied in a thick film shape, has excellent transparency, and is also excellent in sealing property, heat resistance, ultraviolet resistance, etc., and therefore, as a member for a semiconductor light emitting device having various shapes. Can be applied. In particular, it can be used as a useful member with little deterioration in a semiconductor light emitting device having a light emitting wavelength in the blue to ultraviolet region.

0089The member for a semiconductor light emitting device of the present invention is excellent in adhesion to a container, heat resistance, and UV resistance. Since it has such advantageous characteristics, any of the semiconductor light emitting device members of the present invention can be suitably used as a sealing agent or the like for a semiconductor light emitting device. Each will be described below.

0090[Adhesion] The member for a semiconductor light emitting device of the present invention has a functional group capable of hydrogen bonding with a predetermined functional group (for example, a hydroxyl group, oxygen in a metalloxene bond, etc.) existing on the surface of a resin such as polyphthalacid, ceramic or metal. .. Containers for semiconductor light emitting devices (such as cups described below) are usually made of ceramic or metal. In addition, hydroxyl groups are usually present on the surface of ceramics and metals. On the other hand, the member for a semiconductor light emitting device of the present invention usually has a functional group capable of hydrogen bonding with the hydroxyl group. Therefore, due to the hydrogen bond, the semiconductor light emitting device member of the present invention has excellent adhesion to the container for the semiconductor light emitting device.

0091Examples of the functional group capable of hydrogen bonding with the hydroxyl group of the semiconductor light emitting device member of the present invention include silanol and an alkoxy group. The functional group may be one type or two or more types. Whether or not the member for a semiconductor light emitting device of the present invention has a functional group capable of hydrogen bonding with respect to a hydroxyl group is determined by solid-state Si-NMR and solid.¹It can be confirmed by spectroscopic methods such as H-NMR, infrared absorption spectrum (IR), and Raman spectrum.

0092[Heat-resistant] The member for a semiconductor light emitting device of the present invention has excellent heat resistance. That is, it has a property that the transmittance of light having a predetermined wavelength does not easily fluctuate even when left under high temperature conditions. Specifically, the member for a semiconductor light emitting device of the present invention has a retention rate of transmittance for light having a wavelength of 405 nm of usually 80% or more, preferably 90% or more, before and after being left at 200 ° C. for 500 hours. It is preferably 95% or more, and usually 110% or less, preferably 105% or less, and more preferably 100% or less. The fluctuation ratio can be measured in the same manner as in the above-mentioned [Measurement of transmittance] by measuring the transmittance with an ultraviolet / visible spectrophotometer.

0093[UV resistance] The member for a semiconductor light emitting device of the present invention has excellent light resistance. That is, even when irradiated with UV (ultraviolet light), the transmittance for light having a predetermined wavelength does not easily fluctuate. Specifically, the member for a semiconductor light emitting device of the present invention has a center wavelength of 380 nm and a radiant intensity of 0.4 kW / m.²The maintenance rate of the transmittance in light having a wavelength of 405 nm is usually 80% or more, preferably 90% or more, more preferably 95% or more, and usually 110% or less, preferably before and after irradiation with the light of Is 105% or less, more preferably 100% or less. The fluctuation ratio can be measured in the same manner as in the above-mentioned [Measurement of transmittance] by measuring the transmittance with an ultraviolet / visible spectrophotometer.

0094[II. Manufacturing method for semiconductor light emitting device members] Method of manufacturing a semiconductor light-emitting device member of the present invention is not particularly limited, for example, one described general formula (1) or the general compound represented by the formula (2) and / or hydrolysis and polycondensation oligomers thereof It can be obtained by drying the polycondensate (hydrolyzed / polycondensate). However, since it is preferable that the member for a semiconductor light emitting device of the present invention mainly contains a siloxane bond, it is desirable that the compound represented by the general formula (1) or an oligomer thereof is mainly used as a raw material. When the hydrolyzed / polycondensate contains a solvent, the solvent may be distilled off in advance before drying. Hereinafter, this manufacturing method (this is appropriately referred to as a method for manufacturing a member for a semiconductor light emitting device of the present invention) will be described in detail.

0095[II-1. Raw materials] As the raw material, a compound represented by the following general formula (1) (hereinafter, appropriately referred to as compound (1)) and / or an oligomer thereof is used.<chemistry num="4"><img id="000004" he="6" wi="159" file="JP5694875B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0096In the general formula (1), M is at least one element selected from the group consisting of silicon, aluminum, zirconium, and titanium. Of these, silicon is preferable.

0097In the general formula (1), m represents the valence of M and is an integer of 1 or more and 4 or less. Also, "m +" means that it is a positive valence. n represents the number of X groups and is an integer greater than or equal to 1 and less than or equal to 4. However, m n.

0098In the general formula (1), X is a hydrolyzable group that is hydrolyzed by water in a solution or water in the air to generate a highly reactive hydroxyl group, and conventionally known ones are arbitrarily used. can do. For example, C1 to C5 lower alkoxy groups, acetoxy groups, butanoxim groups, chlor groups and the like can be mentioned. Here, the notation Ci (i is a natural number) indicates that the number of carbon atoms is i. In addition, one of these hydrolyzable groups may be used alone, or two or more of these hydrolyzable groups may be used in any combination and ratio.

0099Of these, lower alkoxy groups of C1 to C5 are preferable because the component released after the reaction is neutral. In particular, a methoxy group or an ethoxy group is preferable because it is highly reactive and the solvent to be liberated is light boiling.

0100Furthermore, when X is an acetoxy group or a chlor group in the general formula (1), acetic acid and hydrochloric acid are liberated after the hydrolysis reaction, so that when used as a member for a semiconductor light emitting device that requires insulation. It is preferable to add a step of removing the acid component.

0101In general formula (1), Y¹Can be arbitrarily selected and used as a monovalent organic group of a so-called silane coupling agent. Above all, in the present invention, Y in the general formula (1)¹The organic groups that are particularly useful as are the following Y⁰It is selected from the group represented by (useful organic group group). Further, other organic groups may be appropriately selected in order to improve the affinity with other materials constituting the semiconductor light emitting device, improve the adhesion, adjust the refractive index of the semiconductor light emitting device member, and the like.

0102&lt;Useful organic group Y⁰&gt; Y⁰: A monovalent or higher organic group derived from an aliphatic compound, an alicyclic compound, an aromatic compound, or an aliphatic aromatic compound. Also, group Y⁰The number of carbon atoms of the organic group belonging to is usually 1 or more, and usually 1000 or less, preferably 500 or less, more preferably 100 or less, still more preferably 50 or less.

0103In addition, group Y⁰At least a part of the hydrogen atoms of the organic group belonging to the above may be substituted with an atom exemplified below and / or a substituent such as an organic functional group. At this time, group Y⁰A plurality of hydrogen atoms of the organic group belonging to the above may be substituted with the following substituents, and in this case, they are substituted with one or a combination of two or more selected from the substituents shown below. Is also good.

0104Group Y⁰Examples of substituents substitutable with hydrogen atoms of organic groups belonging to are F, Cl, Br, I and other atoms; vinyl group, methacryloxy group, acryloxy group, styryl group, mercapto group, epoxy group, epoxycyclohexyl group. , Glycydoxy group, amino group, cyano group, nitro group, sulfonic acid group, carboxy group, hydroxy group, acyl group, alkoxy group, imino group, phenyl group and other organic functional groups.

0105In all of the above cases, group Y⁰Of the substituents substitutable with the hydrogen atom of the organic group belonging to, at least a part of the hydrogen atom of the organic functional group is a halogen atom such as F, Cl, Br, I or the like. It may be replaced.

0106However, group Y⁰Among those exemplified as substituents substitutable with hydrogen of the organic group belonging to, the organic functional group is an example of one that can be easily introduced, and other organic functional groups having various physicochemical functions depending on the purpose of use. A group may be introduced. Also, group Y⁰The organic group belonging to the above may have various atoms or atomic groups such as O, N, or S as a linking group.

0107In general formula (1), Y¹Is the above useful organic group Y⁰Various groups can be selected from the organic groups belonging to the above, depending on the purpose, but it is preferable to mainly use a methyl group from the viewpoint of excellent ultraviolet resistance and heat resistance.

0108To give a specific example of the above-mentioned compound (1), examples of the compound in which M is silicon include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, and vinyltriethoxy. Silane, vinyl triacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxipropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltri Methoxysilane, β-cyanoethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxy Silane, tetrabutoxysilane, dimethyldichlorosilane, diphenyldichlorosilane, methylphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, methyltrichlorosilane, γ-asinopropyltriethoxysilane, 4-asinobutyltriethoxysilane, p-Aminophenyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, aminoethylaminomethylphenetyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3- Chloropropyltrimethoxysilane, 3-chloropropyltrichlorosilane, (p-chloromethyl) phenyltrimethoxysilane, 4-chlorophenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3 -Acryloxypropyltrimethoxysilane, styrylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrichlorosilane, vinyltris (2-methoxyethoxy) silane, trifluoropropyltrimethoxysilane and the like.

0109In addition, among the compound (1), examples of the compound in which M is aluminum include aluminum triisopropoxide, aluminum tri n-butoxide, aluminum tri t-butoshikide, and aluminum triethoxydo.

0110Among the compounds (1), examples of the compound in which M is zirconium include zirconium tetramethoxyde, zirconium tetraethoxydo, zirconium tetra n-propoxide, zirconium tetra i-propoxide, zirconium tetra n-butoxide, and the like. Examples thereof include zirconium tetra i-butoxide, zirconium tetra t-butoxide, zirconium dimethacrylate dibutoxide and the like.

0111Among the compounds (1), examples of the compound in which M is titanium include titanium tetraisopropoxide, titanium tetra n-butoxide, titanium tetra i-butoxide, titanium methacrylate triisopropoxide, and titanium tetramethoxypropoxide. , Titanium Tetra n-propoxide, Titanium Tetraethoxydo and the like.

0112However, the compounds specifically exemplified in these are some of the commercially available coupling agents that are easily available. For more details, for example, in Chapter 9 of "Coupling Agent Optimal Utilization Technology" published by the Institute of Science and Technology Research. It can be indicated by a list of coupling agents and related products. Also, of course, the coupling agents that can be used in the present invention are not limited by these examples.

0113In addition, the compound represented by the following general formula (2) (hereinafter, appropriately referred to as compound (2)) and / or its oligomer may be used in the same manner as the above compound (1) and / or its oligomer. You can.<chemistry num="5"><img id="000005" he="6" wi="159" file="JP5694875B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0114In general formula (2), M, X and Y¹Represents the same as the general formula (1) independently of each other. Especially Y¹As in the case of the general formula (1), the above-mentioned useful organic group Y⁰Various groups can be selected from the organic groups belonging to the above, depending on the purpose, but it is preferable to mainly use a methyl group from the viewpoint of excellent ultraviolet resistance and heat resistance. Further, in the general formula (2), s represents the valence of M and is an integer of 2 or more and 4 or less. Also, "s +" indicates that it is a positive integer. Furthermore, in the general formula (2), Y²Represents a u-valent organic group. However, u represents an integer of 2 or more. Therefore, in general formula (2), Y²Can be arbitrarily selected and used from those known as organic groups of so-called silane coupling agents having a valence of 2 or more. Further, in the general formula (2), t represents an integer of 1 or more and s-1 or less. However, t s.

0115Examples of the above compound (2) include those in which a plurality of hydrolyzable silyl groups are bonded as side chains to various organic polymers and oligomers, and those in which a hydrolyzable silyl group is bonded to a plurality of ends of a molecule. And so on.

0116Specific examples of the above compound (2) and their product names are listed below. Bis (triethoxysilylpropyl) tetrasulfide (Shin-Etsu Chemical, KBE-846) -2-Diethoxymethylethylsilyldimethyl-2-furanylsilane (Shin-Etsu Chemical, LS-7740) N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine (Made by Chisso, Sila Ace XS1003) -N-glycidyl-N, N-bis [3- (methyldimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8227) -N-glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8228) N, N-bis [(methyldimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8206) N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine (Made by Toshiba Silicone, TSL8212) N, N-bis [(methyldimethoxysilyl) propyl] methacrylamide (Made by Toshiba Silicone, TSL8213) N, N-bis [3- (trimethoxysilyl) propyl] amine (Toshiba Silicone, TSL8208) N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine (Made by Toshiba Silicone, TSL8214) N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide (Toshiba Silicone, TSL8215) N, N', N -tris [3- (trimethoxysilyl) propyl] isocyanurate (Hydras Chemical, 12267-1) 1,4-Bishydroxydimethylsilylbenzene (Shin-Etsu Chemical, LS-7325)

0117As a raw material, compound (1), compound (2), and / or oligomers thereof can be used. That is, in the method for producing a member for a semiconductor light emitting device of the present invention, the compound (1), the oligomer of the compound (1), the oligomer (2), the oligomer of the compound (2), and the compound (1) and the compound ( Any of the oligomers with 2) may be used. When the oligomer of compound (1) or the oligomer of compound (2) is used as a raw material, the molecular weight of the oligomer is arbitrary as long as the member for the semiconductor light emitting device of the present invention can be obtained, but is usually 400 or more. is there.

0118Here, if compound (2) and / or an oligomer thereof is used as a main raw material, the main chain structure in the system may become an organic bond and the durability may be deteriorated. For this reason, it is desirable to use the compound (2) in the minimum amount mainly for imparting functionality such as imparting adhesion, adjusting the refractive index, controlling reactivity, and imparting dispersibility of inorganic particles. When compound (1) and / or an oligomer thereof (component derived from compound (1)) and compound (2) and / or an oligomer thereof (component derived from compound (2)) are used at the same time, the compound in the total weight of the raw material (component) 2) It is desirable that the ratio of the amount of the derived component used is usually 30% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less.

0119Further, in the method for manufacturing a member for a semiconductor light emitting device of the present invention, when an oligomer of compound (1) or compound (2) is used as a raw material, the oligomer may be prepared in advance, but the manufacturing process The oligomer may be prepared in. That is, a monomer such as compound (1) or compound (2) may be used as a raw material, which may be once used as an oligomer during the production process, and the subsequent reaction may proceed from this oligomer.

0120Further, as the raw material, only one of these compounds (1), compound (2), and oligomers thereof may be used, but two or more of them may be mixed in any combination and composition. Further, compounds (1), compounds (2) and oligomers thereof that have been hydrolyzed in advance (that is, in the general formulas (1) and (2) in which -X is an OH group) may be used.

0121However, in the present invention, as a raw material, silicon is contained as M and the organic group Y¹Or organic group Y²It is necessary to use at least one compound (1), compound (2) and its oligomers (including hydrolyzed ones) having at least one of them. Further, since it is preferable that the cross-linking in the system is mainly formed by an inorganic component such as a siloxane bond, when the compound (1) and the compound (2) are used together, the compound (1) is mainly used. Is preferable.

0122Further, in order to obtain a member for a semiconductor light emitting device mainly composed of a siloxane bond, it is preferable to use compound (1) and / or an oligomer thereof as a main material. Further, it is more preferable that the oligomer of the compound (1) and / or the oligomer of the compound (2) is composed mainly of bifunctional composition. In particular, the oligomer of compound (1) and / or the bifunctional unit of the oligomer of compound (2) is preferably used as the bifunctional oligomer.

0123Further, when the oligomer of compound (1) and / or the oligomer of compound (2), which is bifunctional (hereinafter, appropriately referred to as "bifunctional component oligomer") is mainly used, the amount of these bifunctional component oligomers used is used. Is usually 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight, based on the total weight of the raw material (that is, the sum of the weights of compound (1), compound (2), and its oligomer). That is all. The upper limit of the amount used is usually 97% by weight. The use of the bifunctional component oligomer as the main material is one of the factors that make it possible to easily manufacture the semiconductor light emitting device member of the present invention by the method for manufacturing the semiconductor light emitting device member of the present invention. Because it is.

0124Hereinafter, the advantages of using the bifunctional component oligomer as the main material will be described in detail. For example, in a member for a semiconductor light emitting device manufactured by a conventional sol-gel method, a hydrolyzed / polycondensed product obtained by hydrolyzing and polycondensing the raw material (including one contained in a coating liquid (hydrolyzed liquid)). Had high reactive activity. Therefore, unless the hydrolyzed / polycondensate is diluted with a solvent such as alcohol, the polymerization in the system proceeds and the polycondensate is cured immediately, which makes molding and handling difficult. For example, conventionally, when not diluted with a solvent, it may be cured even if the temperature is about 40 ° C to 50 ° C. Therefore, in order to ensure the handleability of the hydrolyzed / polycondensate obtained after hydrolysis, it was essential to coexist the solvent with the hydrolyzed / polycondensate.

0125Further, when the hydrolysis / polycondensate is dried / cured while the solvent is coexisting with the hydrolysis / polycondensate, the shrinkage due to dehydration condensation (desolvent shrinkage) is added to the shrinkage due to dehydration condensation at the time of curing. Will be done. As a result, in the conventional semiconductor light emitting device, the internal stress of the cured product tends to be large, and cracks, peeling, disconnection, etc. due to this internal stress are likely to occur.

0126Further, when a large amount of bifunctional component monomer is used as a raw material for the purpose of softening the member for a semiconductor light emitting device in order to relax the internal stress, there is a possibility that the number of low boiling cyclic bodies in the polycondensate increases. Since the low boiling ring is volatilized at the time of curing, the weight yield is lowered when the amount of the low boiling ring is increased. The low boiling ring also volatilizes from the cured product, which may cause stress. Further, a member for a semiconductor light emitting device containing a large amount of low boiling annulus may have low heat resistance. For these reasons, conventionally, it has been difficult to obtain a member for a semiconductor light emitting device as an elastomeric cured product having good performance.

0127On the other hand, in the method for producing a member for a semiconductor light emitting device of the present invention, as a raw material, a bifunctional component is previously oligomerized in a separate system (that is, in a system not involved in the hydrolysis / polycondensation step), and the reactive terminal is used. The raw material is made by distilling off low boiling impurities that do not have. Therefore, even if a large amount of the bifunctional component (that is, the above-mentioned bifunctional component oligomer) is used, those low boiling impurities do not volatilize, the weight yield of the cured product can be improved, and the performance is good. An elastomeric cured product can be obtained.

0128Furthermore, by using the bifunctional component oligomer as the main raw material, the reaction activity of the hydrolyzed / polycondensate can be suppressed. It is presumed that this is due to the steric hindrance and electronic effect of the hydrolyzed / polycondensate, and the reduction in the amount of silanol terminals due to the use of the bifunctional oligomer. By suppressing the reaction activity, the hydrolyzed / polycondensate does not cure even if the solvent does not coexist. Therefore, the hydrolyzed / polycondensate can be made into a one-component type and solvent-free system. it can.

0129In addition, the reduced reaction activity of the hydrolyzed / polycondensate made it possible to raise the curing start temperature higher than before. Therefore, when a solvent having a temperature lower than the curing start temperature of the hydrolysis / polycondensate is allowed to coexist in the hydrolysis / polycondensate, the hydrolysis / polycondensate starts to cure when the hydrolysis / polycondensate is dried. The solvent will volatilize before it is done. This makes it possible to suppress the generation of internal stress due to desolvation shrinkage even when a solvent is used.

0130[II-2. Hydrolysis / polycondensation process] In the present invention, first, the above-mentioned compound (1), compound (2), and / or oligomers thereof are hydrolyzed / polycondensed (hydrolysis / polycondensation step). This hydrolysis / polycondensation reaction can be carried out by a known method. In the following, when compound (1), compound (2), and an oligomer thereof are referred to without distinction, they are referred to as "raw material compound".

0131The theoretical amount of water used to carry out the hydrolysis / polycondensation reaction of the raw material compound is a 1/2 molar ratio of the total amount of hydrolyzable groups in the system based on the reaction formula shown in the following formula (3). ..

0132<maths num="1"><img id="000006" he="7" wi="159" file="JP5694875B2_D0001.tif" img-format="tif" img-content="drawing" /></maths> The above equation (3) is expressed as an example when M in the general equations (1) and (2) is silicon. In addition, "Si" and "Si" are expressed by omitting three of the four bonds possessed by the silicon atom.

0133In the present specification, the theoretical amount of water required for this hydrolysis, that is, the amount of water corresponding to a 1/2 molar ratio of the total amount of hydrolyzable groups is used as a reference (hydrolysis rate 100%), and at the time of hydrolysis. The amount of water used is expressed as a percentage of this reference amount, or "hydrolysis rate".

0134In the present invention, the amount of water used to carry out the hydrolysis / polycondensation reaction is usually 80% or more, preferably 100% or more when expressed by the above-mentioned hydrolysis rate. If the hydrolysis rate is less than this range, the hydrolysis / polymerization is insufficient, so that the raw material may volatilize during curing or the strength of the cured product may be insufficient. On the other hand, when the hydrolysis rate exceeds 200%, free water always remains in the system during curing, causing deterioration due to moisture in the chips and phosphors, water absorption in the cup part, and foaming during curing. It may cause cracks and peeling. However, what is important in the hydrolysis reaction is that hydrolysis / polycondensation is performed with water of about 100% or more (for example, 80% or more), and if a step of removing free water is added before application, 200% is added. It is possible to apply a hydrolysis rate that exceeds. In this case, if too much water is used, the amount of water to be removed and the amount of the solvent used as the phase solvent increase, the concentration process becomes complicated, and the polycondensation proceeds too much, and the coating performance of the member deteriorates. Therefore, the upper limit of the hydrolysis rate is usually 500% or less, particularly preferably 300% or less, preferably 200% or less.

0135When the raw material compound is hydrolyzed / polycondensed, a known catalyst or the like may be allowed to coexist to promote the hydrolysis / polycondensation. In this case, as the catalyst to be used, an organic acid such as acetic acid, propionic acid or butyric acid, an inorganic acid such as nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, or an organic metal compound catalyst can be used. Of these, when the member is used for the portion in direct contact with the semiconductor light emitting device, an organometallic compound catalyst having less influence on the insulating characteristics is preferable.

0136The hydrolyzed / polycondensate (polycondensate) of the above-mentioned raw material compound is preferably liquid. However, even a solid hydrolyzed / polycondensate product can be used as long as it becomes liquid by using a solvent.

0137If the inside of the system is separated and becomes non-uniform during the hydrolysis / polycondensation reaction, a solvent may be used. As the solvent, for example, lower alcohols C1 to C3, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl ethyl ketone, and other solvents that can be uniformly mixed with water can be arbitrarily used. Of these, those that do not show strong acidity or basicity are preferable because they do not adversely affect hydrolysis / polycondensation. One type of solvent may be used alone, or a plurality of types may be used in combination. The amount of the solvent used can be freely selected, but it is preferable to use the minimum necessary amount because the solvent is often removed when coating the semiconductor light emitting device. Further, in order to facilitate solvent removal, it is preferable to select a solvent having a boiling point of 100 ° C. or lower, more preferably 80 ° C. or lower. Since a solvent such as alcohol is generated by the hydrolysis reaction without adding a solvent from the outside, the solvent may be non-uniform at the beginning of the reaction but uniform during the reaction.

0138When the hydrolysis / polycondensation reaction of the above raw material compound is carried out at normal pressure, it is usually 15 ° C or higher, preferably 20 ° C or higher, more preferably 40 ° C or higher, and usually 140 ° C or lower, preferably 140 ° C or lower. The temperature is 135 ° C or lower, more preferably 130 ° C or lower. It is possible to carry out at a higher temperature by maintaining the liquid phase under pressure, but it is preferable that the temperature does not exceed 150 ° C.

0139The hydrolysis / polycondensation reaction time varies depending on the reaction temperature, but is usually 0.1 hour or more, preferably 1 hour or more, more preferably 3 hours or more, and usually 100 hours or less, preferably 20 hours or less, still more preferably 15 hours. It will be implemented within the following range.

0140If the time is too short or the temperature is too low under the above hydrolysis / polycondensation conditions, the raw material may volatilize during curing or the strength of the cured product may become insufficient due to insufficient hydrolysis / polymerization. is there. In addition, if the time is too long or the temperature is too high, the molecular weight of the polymer increases, the amount of silanol in the system decreases, poor adhesion occurs during coating, or curing is too fast, resulting in poor structure of the cured product. It becomes uniform and easily cracks. Based on the above tendency, it is desirable to appropriately select the conditions according to the desired physical property values.

0141After the above hydrolysis / polycondensation reaction is completed, the obtained hydrolysis / polycondensation product is stored at room temperature or lower until its use, but the polycondensation proceeds slowly even during this period, so that the thick film is particularly thick. When used as a member, it should be stored at room temperature within 60 days, preferably within 30 days, and more preferably within 15 days after the completion of the hydrolysis / polycondensation reaction by heating. Is preferable. If necessary, this period can be extended by storing at a low temperature within a range that does not freeze.

0142[II-3. Solvent distilling] When a solvent is used in the above hydrolysis / polycondensation step, it is usually preferable to distill off the solvent from the hydrolysis / polycondensation product before drying (solvent distillation step). As a result, a liquid hydrolyzed / polycondensate product containing no solvent can be obtained. As described above, conventionally, when the solvent is distilled off, the hydrolyzed / polycondensate is hardened, which makes it difficult to handle the hydrolyzed / polycondensate. However, in the method for producing a member for a semiconductor light emitting device of the present invention, the reactivity of the hydrolysis / polycondensate is suppressed when the bifunctional component oligomer is used, so that even if the solvent is distilled off before drying, the hydrolysis is performed. -The polycondensate does not cure and the solvent can be distilled off. By distilling off the solvent before drying, cracks, peeling, disconnection and the like due to desolvation shrinkage can be prevented.

0143Normally, when the solvent is distilled off, the water used for hydrolysis is also distilled off. The solvent to be distilled off also includes a solvent represented by XH or the like, which is produced by a hydrolysis / polycondensation reaction of the raw material compounds represented by the above general formulas (1) and (2).

0144The method of distilling off the solvent is arbitrary as long as the effects of the present invention are not significantly impaired. However, it is necessary to avoid distilling off the solvent at a temperature higher than the curing start temperature of the hydrolyzed / polycondensate. The specific range of temperature conditions when distilling off the solvent is usually 60 ° C or higher, preferably 80 ° C or higher, more preferably 100 ° C or higher, and usually 150 ° C or lower, preferably 150 ° C or lower. It is 130 ° C or less, more preferably 120 ° C or less. If it is below the lower limit of this range, the solvent may be insufficiently distilled, and if it exceeds the upper limit, the hydrolyzed / polycondensate may be gelled.

0145The pressure condition for distilling off the solvent is usually normal pressure. Further, if necessary, the pressure is reduced so that the boiling point of the reaction solution at the time of distilling off the solvent does not reach the curing start temperature (usually 120 ° C. or higher). The lower limit of the pressure is such that the main component of the hydrolyzed / polycondensate does not distill.

0146However, distilling off the solvent is not an essential operation. In particular, when a solvent having a boiling point equal to or lower than the curing temperature of the hydrolyzed / polycondensate is used, the solvent is used during drying of the hydrolyzed / polycondensate before the curing of the hydrolyzed / polycondensate is started. Is volatilized, so that the formation of cracks and the like due to desolvation shrinkage can be prevented even if the solvent distillation step is not particularly performed. However, since the volume of the hydrolyzed / polycondensate may change due to the volatilization of the solvent, it is preferable to distill off the solvent from the viewpoint of precisely controlling the dimensions and shape of the semiconductor light emitting device member.

0147[II-4. Drying] The member for a semiconductor light emitting device of the present invention can be obtained by drying the hydrolyzed / polycondensated product obtained by the above-mentioned hydrolysis / polycondensation reaction (drying step or curing step). As described above, this hydrolyzed / polycondensate is usually liquid, but the semiconductor light emitting device of the present invention having the desired shape can be obtained by drying the product in a mold having the desired shape. It becomes possible to form a member for use. Further, by drying the hydrolyzed / polycondensate in a state of being applied to a target site, it is possible to directly form the member for the semiconductor light emitting device of the present invention on the target site. In this specification, this liquid hydrolyzed / polycondensate product is appropriately referred to as "hydrolyzed / polycondensed liquid" or "member forming liquid for semiconductor light emitting device". Further, although the solvent is not necessarily vaporized in the drying step, the drying step is referred to here including the phenomenon that the hydrolyzed / polycondensate having fluidity loses its fluidity and hardens. Therefore, when the solvent is not vaporized, the above-mentioned "drying" may be read as "curing" and recognized.

0148In the drying step, the hydrolyzed / polycondensate is further polymerized to form a metalloxane bond, and the polymer is dried / cured to obtain the member for the semiconductor light emitting device of the present invention. At the time of drying, the hydrolyzed / polycondensate is heated to a predetermined curing temperature to be cured. The specific temperature range is arbitrary as long as the hydrolyzable / polycondensate can be dried, but since the metalloxane bond is usually efficiently formed at 100 ° C or higher, it is preferably 120 ° C or higher, more preferably 120 ° C or higher. Conducted above 150 ° C. However, when heated together with the semiconductor light emitting device, it is usually preferable to carry out drying at a temperature equal to or lower than the heat resistant temperature of the device component, preferably 200 ° C or lower.

0149The time (curing time) for keeping the hydrolyzed / polycondensate at the curing temperature to dry is not unconditionally determined depending on the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hours or more, preferably 0.5 hours or more. It is more preferably carried out for 1 hour or more, usually 10 hours or less, preferably 5 hours or less, still more preferably 3 hours or less.

0150The temperature rising conditions in the drying step are not particularly limited. That is, the temperature may be maintained at a constant temperature during the drying step, or the temperature may be changed continuously or intermittently. Further, the drying step may be further divided into a plurality of times. Further, in the drying step, the temperature may be changed stepwise. By changing the temperature stepwise, it is possible to obtain the advantage that foaming due to the residual solvent or dissolved steam can be prevented.

0151However, when the above-mentioned hydrolysis / polycondensation reaction is carried out in the presence of a solvent, the solvent may not be distilled off, or even if the solvent distillation step is performed, the solvent may be contained in the hydrolyzed / polycondensate. When is residual, the drying step is performed by a first drying step of substantially removing the solvent at a temperature equal to or lower than the boiling point of the solvent and a second drying step of drying at a temperature equal to or higher than the boiling point of the solvent. It is preferable to perform it separately from the drying step. The "solvent" referred to here also includes a solvent represented by XH or the like, which is produced by the hydrolysis / polycondensation reaction of the above-mentioned raw material compound. Further, "drying" in the present specification refers to a step in which the hydrolyzed / polycondensate of the above-mentioned raw material compound loses a solvent and is further polymerized / cured to form a metalloxane bond.

0152The first drying step is to substantially remove the contained solvent at a temperature equal to or lower than the boiling point of the solvent without actively proceeding with the hydrolysis of the raw material compound and further polymerization of the polycondensate. .. That is, the product obtained in this step is a product obtained by concentrating the hydrolyzed / polycondensate product before drying into a viscous liquid or a soft film by hydrogen bonding, or by removing the solvent and hydrolyzing. The polycondensate exists in a liquid state.

0153However, it is usually preferable to carry out the first drying step at a temperature lower than the boiling point of the solvent. When the first drying is performed at a temperature equal to or higher than the boiling point of the solvent, the obtained film is foamed by the vapor of the solvent, and it becomes difficult to obtain a homogeneous film without defects. This first drying step may be performed in a single step when the evaporation efficiency of the solvent is good, such as when a thin film member is formed, but when the evaporation efficiency is poor, such as when molded on a cup, a plurality of steps may be performed. The temperature may be raised in steps of. Further, in the case of a shape having extremely poor evaporation efficiency, it may be dried and concentrated in another efficient container in advance, applied in a state where fluidity remains, and further dried. When the evaporation efficiency is poor, it is preferable to devise a way to uniformly dry the entire member without taking measures such as ventilation drying with a large air volume to promote concentration only on the surface of the member.

0154In the second drying step, the hydrolyzed / polycondensate is heated at a temperature equal to or higher than the boiling point of the solvent in a state where the solvent of the hydrolyzed / polycondensate is substantially eliminated by the first drying step. By forming a metalloxane bond, a stable cured product is obtained. If a large amount of solvent remains in this step, the cross-linking reaction proceeds and the volume is reduced due to solvent evaporation, so that a large internal stress is generated, which causes peeling or cracking due to shrinkage. Since the metalloxane bond is usually efficiently formed at 100 ° C. or higher, the second drying step is preferably carried out at 100 ° C. or higher, more preferably 120 ° C. or higher. However, when heated together with the semiconductor light emitting device, it is usually preferable to carry out drying at a temperature equal to or lower than the heat resistant temperature of the device component, preferably 200 ° C or lower. The curing time in the second drying step is not unconditionally determined by the catalyst concentration, the thickness of the member, etc., but is usually 0.1 hour or more, preferably 0.5 hours or more, more preferably 1 hour or more, and usually 10 hours or less, preferably 10 hours or less. Is carried out within a range of 5 hours or less, more preferably 3 hours or less.

0155By clearly separating the solvent removing step (first drying step) and the curing step (second drying step) in this way, the physical characteristics of the present invention are obtained even when the solvent distilling step is not performed. It is possible to obtain a member for a semiconductor light emitting device having excellent light resistance and heat resistance without cracking or peeling. However, curing proceeds even during the first drying step.<u style="single">If</u>It is possible, and solvent removal may proceed during the second drying step. However, the curing during the first drying step and the removal of the solvent during the second drying step are usually small enough not to affect the effect of the present invention.

0156As long as the above-mentioned first drying step and second drying step are substantially realized, the temperature rising conditions in each step are not particularly limited. That is, it may be kept at a constant temperature during each drying step, or the temperature may be changed continuously or intermittently. Further, each drying step may be further divided into a plurality of times. Furthermore, even if the temperature temporarily exceeds the boiling point of the solvent during the first drying step, or the temperature becomes lower than the boiling point of the solvent during the second drying step, the temperature is substantially equal. As long as the solvent removing step (first drying step) and the curing step (second drying step) as described above are independently achieved, they are included in the scope of the present invention.

0157Further, when a solvent having a boiling point equal to or lower than the curing temperature of the hydrolyzed / polycondensate, preferably lower than the curing temperature is used, the solvent coexisting with the hydrolyzed / polycondensate has a particularly high temperature. Even if the hydrolyzed / polycondensate is heated to the curing temperature without adjustment, it will be distilled off from the hydrolyzed / polycondensate when the temperature reaches the boiling point in the middle of the drying process. .. That is, in this case, in the process of raising the temperature of the hydrolyzed / polycondensate to the curing temperature in the drying step, the solvent is substantially removed at a temperature equal to or lower than the boiling point of the solvent before the hydrolyzed / polycondensate is cured. The step (first drying step) is carried out. As a result, the hydrolyzed / polycondensate becomes a liquid hydrolyzed / polycondensate containing no solvent. Then, after that, the process of drying at a temperature equal to or higher than the boiling point of the solvent (that is, the curing temperature) and curing the hydrolyzed / polycondensate product (second drying step) proceeds. Therefore, if a solvent having a boiling point equal to or lower than the curing temperature is used as the solvent, the first drying step and the second drying step are performed even if they are not intended to be carried out. Therefore, if a solvent having a boiling point equal to or lower than the curing temperature of the hydrolyzed / polycondensate, preferably lower than the curing temperature is used, the hydrolyzed / polycondensate contains a solvent when the drying step is carried out. Even if it is, it can be said that it is preferable because it does not significantly affect the quality of the member for the semiconductor light emitting device.

0158[II-5. Others] After the above-mentioned drying step, various post-treatments may be applied to the obtained semiconductor light emitting device member, if necessary. Examples of the type of post-treatment include surface treatment for improving the adhesion to the mold portion, preparation of an antireflection film, preparation of a fine uneven surface for improving light extraction efficiency, and the like.

0159[III. Applications of semiconductor light emitting device members] The application of the member for a semiconductor light emitting device of the present invention is not particularly limited, and it can be used for various applications represented by a member (sealing agent) for sealing a semiconductor light emitting element or the like. Above all, by using the phosphor particles and / or the inorganic oxide particles described later in combination, it is possible to use them more preferably for a specific application. Hereinafter, the combined use of these phosphor particles and inorganic oxide particles will be described.

0160[III-1. Combined use of phosphor] The member for a semiconductor light emitting device of the present invention is, for example, a member in which a phosphor is dispersed in a member for a semiconductor light emitting device and molded in a cup of the semiconductor light emitting device, or coated in a thin layer on an appropriate transparent support. Therefore, it can be used as a wavelength conversion member. One type of phosphor may be used alone, or two or more types may be used in any combination and ratio.

0161[Fluorescent material] The composition of the phosphor is not particularly limited, but Y is the crystal base.₂O₃, Zn₂SiO₄Metal oxides such as Ca₅(PO₄)₃Phosphates represented by Cl, etc. and sulfides represented by ZnS, SrS, CaS, etc., and rare earths such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, etc. A combination of metal ions or metal ions such as Ag, Cu, Au, Al, Mn, and Sb as an activator or co-activator is preferable.

0162Preferred examples of the crystal matrix include, for example, (Zn, Cd) S, SrGa.₂S₄, SrS, ZnS and other sulfides, Y₂O₂Acid sulfides such as S, (Y, Gd)₃Al₅O₁₂, YAlO₃, BaMgAl₁₀O₁₇, (Ba, Sr) (Mg, Mn) Al₁₀O₁₇, (Ba, Sr, Ca) (Mg, Zn, Mn) Al₁₀O₁₇, BaAl₁₂O₁₉, CeMgAl₁₁O₁₉, (Ba, Sr, Mg) O Al₂O₃, BaAl₂Si₂O₈, SrAl₂O₄, Sr₄Al₁₄O₂₅, Y₃Al₅O₁₂Such as aluminate, Y₂SiO₅, Zn₂SiO₄Silicates such as SnO₂, Y₂O₃Oxides such as GdMgB₅O₁₀, (Y, Gd) BO₃Boric acid circle, Ca, etc.₁₀(PO₄)₆(F, Cl)₂, (Sr, Ca, Ba, Mg)₁₀(PO₄)₆Cl₂Harophosphate, etc., Sr₂P₂O₇, (La, Ce) PO₄Phosphates and the like can be mentioned.

0163However, the above-mentioned crystal matrix and activator or co-activator are not particularly limited in element composition and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near-ultraviolet to visible region. Anything that absorbs and emits visible light can be used.

0164Specifically, the following phosphors can be used, but these are merely examples, and the phosphors that can be used in the present invention are not limited to these. In the following examples, phosphors having only a part of the structure different are shown by omitting them as appropriate. For example, "Y₂SiO₅: Ce³⁺, "Y₂SiO₅: Tb³⁺And "Y₂SiO₅: Ce³⁺, Tb³⁺"Y"₂SiO₅: Ce³⁺, Tb³⁺"," La₂O₂S: Eu "," Y₂O₂S: Eu "and" (La, Y)₂O₂"S: Eu" to "(La, Y)₂O₂It is collectively shown as "S: Eu". Omitted parts are separated by commas (,).

0165Red phosphor: To exemplify a specific wavelength range of fluorescence emitted by a phosphor that emits red fluorescence (hereinafter, appropriately referred to as "red fluorescence"), the peak wavelength is usually 570 nm or more, preferably 580 nm or more, and usually 700 nm or less. , Preferably 680 nm or less.

0166Such a red phosphor is composed of, for example, broken particles having a red fracture surface and emits light in a red region (Mg, Ca, Sr, Ba).₂Si₅N₈: Active alkaline earth with europium represented by Eu Silicon nitride-based phosphor, composed of growth particles having a nearly spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) )₂O₂Examples thereof include live rare earth oxycalcogenide phosphors with europium represented by S: Eu.

0167Further, an oxynitride and / or an acid containing at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in JP-A-2004-300247. A phosphor containing a sulfide and containing an oxynitride having an alpha sialone structure in which a part or all of the Al element is replaced with a Ga element can also be used in the present embodiment. In addition, these are phosphors containing acid nitride and / or acid sulfide.

0168In addition, as a red phosphor, (La, Y)₂O₂S: Active acid sulfide phosphor with Eu such as Eu, Y (V, P) O₄: Eu, Y₂O₃: Active oxide phosphor with Eu such as Eu, (Ba, Sr, Ca, Mg)₂SiO₄: Eu, Mn, (Ba, Mg)₂SiO₄: Eu, Mn-activated silicate phosphors such as Eu, Mn, (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, YAlO₃: Eu active aluminate phosphor such as Eu, LiY₉(SiO₄)₆O₂: Eu, Ca₂Y₈(SiO₄)₆O₂: Eu, (Sr, Ba, Ca)₃SiO₅: Eu, Sr₂BaSiO₅: Active silicate phosphor with Eu such as Eu, (Y, Gd)₃Al₅O₁₂: Ce, (Tb, Gd)₃Al₅O₁₂: Ce-activated aluminate phosphor such as Ce, (Ca, Sr, Ba)₂Si₅N₈: Eu, (Mg, Ca, Sr, Ba) SiN₂: Eu, (Mg, Ca, Sr, Ba) AlSiN₃: Active nitride phosphor with Eu such as Eu, (Mg, Ca, Sr, Ba) AlSiN₃: Active nitride phosphor with Ce such as Ce, (Sr, Ca, Ba, Mg)₁₀(PO₄)₆Cl₂: Eu, Mn-activated halophosphate phosphors such as Eu, Mn, (Ba₃Mg) Si₂O₈: Eu, Mn, (Ba, Sr, Ca, Mg)₃(Zn, Mg) Si₂O₈: Eu, Mn active silicate phosphors such as Eu, Mn, 3.5MgO / 0.5MgF₂ GeO₂: Mn-activated germanate phosphors such as Mn, Eu-activated acid nitride phosphors such as Eu-activated α-sialon, (Gd, Y, Lu, La)₂O₃: Eu, Bi active oxide phosphors such as Eu, Bi, (Gd, Y, Lu, La)₂O₂S: Active acid sulfide phosphor with Eu, Bi such as Eu, Bi, (Gd, Y, Lu, La) VO₄: Eu, Bi active vanadate phosphors such as Eu, Bi, SrY₂S₄: Eu, Ce active sulfide phosphor such as Eu, Ce, CaLa₂S₄: Active sulfide phosphor with Ce such as Ce, (Ba, Sr, Ca) MgP₂O₇: Eu, Mn, (Sr, Ca, Ba, Mg, Zn)₂P₂O₇: Eu, Mn-activated phosphate phosphors such as Eu, Mn, (Y, Lu)₂WO₆: Eu, Mo active tungstate phosphors such as Eu, Mo, (Ba, Sr, Ca)_xSi_yN_zActive nitride phosphor with Eu, Ce, such as: Eu, Ce (where x, y, z are integers greater than or equal to 1), (Ca, Sr, Ba, Mg)₁₀(PO₄)₆(F, Cl, Br, OH): Eu, Mn-activated halophosphate phosphors such as Eu, Mn, ((Y, Lu, Gd, Tb)_1-xSc_xCe_y)₂(Ca, Mg)_1-r(Mg, Zn)_{2 + r}Si_zqGe_qO_{12 + δ}It is also possible to use a Ce-activated silicate phosphor or the like.

0169Examples of the red phosphor include a red organic phosphor composed of a rare earth element ion complex having an anion such as β-diketonate, β-diketone, aromatic carboxylic acid, or blended acid as a ligand, and a perylene pigment (for example, perylene pigment). Dibenzo {[f, f']-4,4',7,7'-tetraphenyl} diindeno [1,2,3-cd: 1', 2', 3'-lm] perylene), anthraquinone pigments, Lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindrin pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanslon pigments, indophenol pigments, It is also possible to use cyanine pigments and dioxazine pigments.

0170Further, among the red phosphors, those having a peak wavelength in the range of 580 nm or more, preferably 590 nm or more, and 620 nm or less, preferably 610 nm or less can be suitably used as the orange phosphor. An example of such an orange phosphor is (Sr, Ba).₃SiO₅: Eu, (Sr, Mg)₃(PO₄)₂: Sn²⁺, SrCaAlSiN₃: Eu etc. can be mentioned.

0171Green phosphor: To exemplify a specific wavelength range of fluorescence emitted by a fluorescent substance that emits green fluorescence (hereinafter, appropriately referred to as "green fluorescent substance"), the peak wavelength is usually 490 nm or more, preferably 500 nm or more, and usually 570 nm or less. , Preferably 550 nm or less.

0172As such a green phosphor, for example, it is composed of broken particles having a fracture surface and emits light in a green region (Mg, Ca, Sr, Ba) Si.₂O₂N₂: Active alkaline earth with europium represented by Eu Siliconoxynitride-based phosphor, composed of fractured particles with fracture surface, emits light in the green region (Ba, Ca, Sr, Mg)₂SiO₄: Examples include an active alkaline earth silicate-based phosphor with europium represented by Eu.

0173In addition, as a green phosphor, Sr₄Al₁₄O₂₅: Eu, (Ba, Sr, Ca) Al₂O₄: Eu-activated aluminate phosphor such as Eu, (Sr, Ba) Al₂Si₂O₈: Eu, (Ba, Mg)₂SiO₄: Eu, (Ba, Sr, Ca, Mg)₂SiO₄: Eu, (Ba, Sr, Ca)₂(Mg, Zn) Si₂O₇: Active silicate phosphor with Eu such as Eu, Y₂SiO₅: Ce, Tb-attached active silicate phosphor such as Ce, Tb, Sr₂P₂O₇-Sr₂B₂O₅: Active borate phosphate phosphor with Eu such as Eu, Sr₂Si₃O₈-2SrCl₂: Eu-activated halosilicate phosphors such as Eu, Zn₂SiO₄: Active silicate phosphor with Mn such as Mn, CeMgAl₁₁O₁₉: Tb, Y₃Al₅O₁₂: Tb-activated aluminate phosphor such as Tb, Ca₂Y₈(SiO₄)₆O₂: Tb, La₃Ga₅SiO₁₄: Active silicate phosphor with Tb such as Tb, (Sr, Ba, Ca) Ga₂S₄: Eu, Tb, Sm active thiogallate phosphors such as Eu, Tb, Sm, Y₃(Al, Ga)₅O₁₂: Ce, (Y, Ga, Tb, La, Sm, Pr, Lu)₃(Al, Ga)₅O₁₂: Ce-activated aluminate phosphor such as Ce, Ca₃Sc₂Si₃O₁₂: Ce, Ca₃(Sc, Mg, Na, Li)₂Si₃O₁₂: Ce active silicate phosphor such as Ce, CaSc₂O₄: Ce-attached active oxide phosphor such as Ce, SrSi₂O₂N₂: Eu, (Sr, Ba, Ca) Si₂O₂N₂: Eu-activated acid nitride phosphors such as Eu, Eu-activated β-sialon, Eu-activated α-sialon, BaMgAl₁₀O₁₇: Eu, Mn active aluminate phosphors such as Eu, Mn, SrAl₂O₄: Active aluminate phosphor with Eu such as Eu, (La, Gd, Y)₂O₂S: Active acid sulfide phosphor with Tb such as Tb, LaPO₄: Ce, Tb-activated phosphate phosphors such as Ce, Tb, ZnS: Cu, Al, ZnS: Cu, Au, Al and other sulfide phosphors, (Y, Ga, Lu, Sc, La) BO₃: Ce, Tb, Na₂Gd₂B₂O₇: Ce, Tb, (Ba, Sr)₂(Ca, Mg, Zn) B₂O₆: Active borate phosphor with Ce, Tb such as K, Ce, Tb, Ca₈Mg (SiO)₄)₄Cl₂: Eu, Mn-activated halosilicate phosphors such as Eu, Mn, (Sr, Ca, Ba) (Al, Ga, In)₂S₄: Eu-activated thioaluminate phosphors such as Eu and thiogallate phosphors, (Ca, Sr)₈(Mg, Zn) (SiO₄)₄Cl₂It is also possible to use an Eu, Mn-activated halosilicate phosphor such as: Eu, Mn.

0174Examples of the green phosphor include pyridine-phthalimide condensed derivatives, benzooxadinone-based, quinazolinone-based, coumarin-based, quinophthalone-based, naltaric acidimide-based fluorescent dyes, terbium complexes having hexylsalicylate as a ligand, and the like. It is also possible to use the organic phosphor of.

0175Blue phosphor: To exemplify a specific wavelength range of fluorescence emitted by a fluorescent substance that emits blue fluorescence (hereinafter, appropriately referred to as "blue phosphor"), the peak wavelength is usually 420 nm or more, preferably 440 nm or more, and usually 480 nm or less. , Preferably 470 nm or less.

0176Such a blue phosphor is composed of grown particles having a substantially hexagonal shape as a regular crystal growth shape, and emits light in the blue region.₁₀O₁₇: It is composed of an active barium magnesium aluminate-based phosphor with europium represented by Eu and grown particles having a nearly spherical shape as a regular crystal growth shape, and emits light in the blue region (Ca, Sr, Ba).₅(PO₄)₃It is composed of an active calcium halophosphate-based phosphor with europium represented by Cl: Eu and grown particles having a nearly cubic shape as a regular crystal growth shape, and emits light in the blue region (Ca, Sr, Ba).₂B₅O₉It is composed of an active alkaline earth chloroborate-based phosphor with europium represented by Cl: Eu and broken particles having a fracture surface, and emits light in a blue-green region (Sr, Ca, Ba) Al.₂O₄: Eu or (Sr, Ca, Ba)₄Al₁₄O₂₅: Active alkaline earth with europium represented by Eu Aluminate-based phosphors and the like can be mentioned.

0177In addition, as a blue phosphor, Sr₂P₂O₇: Sn active phosphate phosphors such as Sn, Sr₄Al₁₄O₂₅: Eu, BaMgAl₁₀O₁₇: Eu, BaAl₈O₁₃: Eu-activated aluminate phosphor such as Eu, SrGa₂S₄: Ce, CaGa₂S₄: Ce-activated thiogallate phosphor such as Ce, (Ba, Sr, Ca) MgAl₁₀O₁₇: Eu, BaMgAl₁₀O₁₇: Eu activated aluminate phosphors such as Eu, Tb, Sm, (Ba, Sr, Ca) MgAl₁₀O₁₇: Eu, Mn-activated aluminate phosphors such as Eu, Mn, (Sr, Ca, Ba, Mg)₁₀(PO₄)₆Cl₂: Eu, (Ba, Sr, Ca)₅(PO₄)₃(Cl, F, Br, OH): Eu-activated halophosphate phosphors such as Eu, Mn, Sb, BaAl₂Si₂O₈: Eu, (Sr, Ba)₃MgSi₂O₈: Active silicate phosphor with Eu such as Eu, Sr₂P₂O₇: Eu-activated phosphate phosphors such as Eu, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, Y₂SiO₅: Ce active silicate phosphor such as Ce, CaWO₄Tungstate phosphors such as (Ba, Sr, Ca) BPO₅: Eu, Mn, (Sr, Ca)₁₀(PO₄)₆ NB₂O₃: Eu, 2SrO 0.84P₂O₅ 0.16B₂O₃: Eu, active borate phosphate phosphor with Mn such as Eu, Sr₂Si₃O₈ 2SrCl₂It is also possible to use an Eu-activated halosilicate phosphor such as: Eu.

0178Further, as the blue phosphor, for example, an imide-based naphthalate, a benzoxazole-based, a styryl-based, a coumarin-based, a pyrarizone-based, a triazole-based compound fluorescent dye, an organic phosphor such as a turium complex, or the like can be used. .. One type of phosphor may be used alone, or two or more types may be used in any combination and ratio.

0179The median particle size of these phosphor particles is not particularly limited, but is usually 100 nm or more, preferably 2 μm or more, particularly preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less, particularly preferably 20 μm or less. Further, as long as the shape of the phosphor particles does not affect the formation of the semiconductor light emitting device member, for example, a phosphor part forming liquid (a liquid obtained by adding a phosphor to the above-mentioned semiconductor light emitting device member forming liquid). There is no particular limitation as long as it does not affect the liquidity of.

0180In the present invention, the method of adding the phosphor particles is not particularly limited. If the dispersed state of the phosphor particles is good, it is only necessary to post-mix the phosphor particles with the above-mentioned semiconductor light emitting device member forming liquid. When agglutination of the fluorescent particles is likely to occur, the fluorescent particles are mixed in advance with a reaction solution containing the raw material compound before hydrolysis (hereinafter, appropriately referred to as pre-hydrolysis solution), and in the presence of the phosphor particles. When hydrolysis / polycondensation is carried out in, the surface of the particles is partially subjected to silane coupling treatment, and the dispersed state of the phosphor particles is improved.

0181Although some fluorescent materials are hydrolyzable, the member for a semiconductor light emitting device of the present invention has a potential water content as a silanol body in a liquid state before coating (a member forming liquid for a semiconductor light emitting device). Since it is present in Silanol and there is almost no free water, even such a fluorescent substance can be used without being hydrolyzed. Further, if the member forming liquid for a semiconductor light emitting device after hydrolysis / polycondensation is dehydrated / dealcoholicized before use, there is an advantage that it can be easily used in combination with such a phosphor.

0182Further, the member for a semiconductor light emitting device of the present invention can be a fluorescent glass in which an ionic fluorescent substance or an organic / inorganic fluorescent component is uniformly and transparently dissolved / dispersed.

0183[III-2. Combined use of inorganic oxide particles] Further, the member for a semiconductor light emitting device of the present invention is further subjected to inorganic oxidation for the purpose of improving optical characteristics and workability, and for the purpose of obtaining any of the following effects &lt;1&gt; to &lt;5&gt;. It may contain physical particles.

0184&lt;1&gt; By mixing inorganic oxide particles as a light scattering substance into the semiconductor light emitting device member and scattering the light of the semiconductor light emitting device, the amount of light of the semiconductor light emitting element that hits the phosphor is increased and the wavelength conversion efficiency is improved. At the same time, the directivity angle of the light emitted from the semiconductor light emitting device to the outside is widened. &lt;2&gt; By blending inorganic oxide particles as a binder into the semiconductor light emitting device member, the occurrence of cracks is prevented. &lt;3&gt; The viscosity of the forming liquid is increased by adding inorganic oxide particles as a viscosity adjusting agent to the member forming liquid for a semiconductor light emitting device. &lt;4&gt; By blending inorganic oxide particles into the semiconductor light emitting device member, its shrinkage is reduced. &lt;5&gt; By blending inorganic oxide particles into the semiconductor light emitting device member, the refractive index thereof is adjusted to improve the light extraction efficiency.

0185In this case, an appropriate amount of inorganic oxide particles may be mixed with the semiconductor light emitting device member forming liquid together with the phosphor powder. In this case, the effect obtained depends on the type and amount of the inorganic oxide particles to be mixed.

0186For example, when the inorganic oxide particles are ultrafine silica (manufactured by Nippon Aerosil Co., Ltd., trade name: AEROSIL # 200) having a particle size of about 10 nm, the thixotropic property of the member forming liquid for a semiconductor light emitting device increases. The effect of &lt;3&gt; is great.

0187Further, when the inorganic oxide particles are crushed silica or spherical silica having a particle size of about several μm, there is almost no increase in thixotropic property, and the inorganic oxide particles mainly function as aggregates for semiconductor light emitting device members. The effects of 2&gt; and &lt;4&gt; are great.

0188Further, if inorganic oxide particles having a particle size of about 1 μm having a refractive index different from that of the semiconductor light emitting device member are used, light scattering at the interface between the semiconductor light emitting device member and the inorganic oxide particles becomes large. The effect of&gt; is great.

0189Further, when inorganic oxide particles having a particle size of 3 to 5 nm, which has a higher refractive index than the member for the semiconductor light emitting device, specifically, a particle size equal to or less than the emission wavelength, are used, the transparency of the member for the semiconductor light emitting device is maintained. Since the refractive index can be improved, the effect of &lt;5&gt; above is large.

0190Therefore, the type of inorganic oxide particles to be mixed may be selected according to the purpose. Further, the type may be single or a combination of a plurality of types. Further, the surface may be treated with a surface treatment agent such as a silane coupling agent in order to improve the dispersibility.

0191Examples of the type of inorganic oxide particles used include silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, and yttrium oxide, but other substances may be selected according to the purpose. It can also be, and is not limited to these.

0192The form of the inorganic oxide particles may be any form such as powder or slurry depending on the purpose, but when it is necessary to maintain transparency, the refractive index may be the same as that of the semiconductor light emitting device member of the present invention. It is preferable to add it as an aqueous / solvent-based transparent sol to the semiconductor light emitting device member forming liquid.

0193[IV. Semiconductor light emitting device] Hereinafter, a semiconductor light emitting device (semiconductor light emitting device of the present invention) using the semiconductor light emitting device member of the present invention will be described with reference to embodiments. In each of the following embodiments, the semiconductor light emitting device is appropriately abbreviated as "light emitting device". Further, which portion of the member for the semiconductor light emitting device of the present invention is used will be collectively described after the description of all the embodiments. However, these embodiments are used only for convenience of explanation, and examples of a light emitting device (semiconductor light emitting device) to which the member for a semiconductor light emitting device of the present invention is applied are limited to these embodiments. is not it.

0194[Basic concept] The semiconductor light emitting device using the semiconductor light emitting device member of the present invention has, for example, the following application examples of A) and B). In any of the application examples, the semiconductor light emitting device member of the present invention exhibits excellent light durability and thermal durability as compared with the conventional semiconductor light emitting device member, is less likely to crack or peel, and has a brightness. There is little decrease. Therefore, according to the member for a semiconductor light emitting device of the present invention, it is possible to provide a member with high reliability for a long period of time. A) A semiconductor light emitting device that uses the light emitting color of the light emitting element as it is. B) A semiconductor in which a phosphor portion is arranged in the vicinity of the light emitting element, the phosphor and the phosphor component in the phosphor portion are excited by the light from the light emitting element, and light of a desired wavelength is emitted using fluorescence. Luminous device.

0195In the application example of A), the high durability, transparency, and sealing agent performance of the semiconductor light emitting device member of the present invention are utilized, and the highly durable sealing agent, light extraction film, and various functional components are retained when used alone. It can be used as an agent. In particular, when the semiconductor light emitting device member of the present invention is used as a functional component preserving agent for holding the inorganic oxide particles and the like and the semiconductor light emitting device member of the present invention holds a transparent high refractive index component, the present invention By using the semiconductor light emitting device member of the present invention in close contact with the light emitting surface of the light emitting element and having a refractive index close to that of the light emitting element, reflection on the light emitting surface of the light emitting element is reduced and higher light extraction efficiency is achieved. Can be obtained.

0196Further, also in the application example of B), the member for the semiconductor light emitting device of the present invention can exhibit the same excellent performance as the application example of A) above, and retains the phosphor and the phosphor component. By doing so, it is possible to form a phosphor portion having high durability and high light extraction efficiency. Further, when the member for the semiconductor light emitting device of the present invention holds a transparent high refraction component in addition to the phosphor and the phosphor component, the refractive index of the member for the semiconductor light emitting device of the present invention is changed to the light emitting element and the phosphor. By setting it near the refractive index of, it is possible to reduce the interfacial reflection and obtain a higher light extraction efficiency.

0197Hereinafter, the basic concept of each embodiment to which the member for the semiconductor light emitting device of the present invention is applied will be described with reference to FIGS. 49 (a) and 49 (b). Note that FIG. 49 is an explanatory diagram of the basic concept of each embodiment, in which (a) corresponds to the application example of A) above, and (b) corresponds to the application example of B) above.

0198As shown in FIGS. 49 (a) and 49 (b), the light emitting devices (semiconductor light emitting devices) 1A and 1B of each embodiment are a light emitting element 2 composed of an LED chip and a book arranged in the vicinity of the light emitting element 2. It includes the semiconductor light emitting device members 3A and 3B of the present invention.

0199However, in the embodiment (Embodiments A-1, A-2) corresponding to the application example of A) as shown in FIG. 49 (a), the light emitting device 1A is a member 3A for a semiconductor light emitting device and is a phosphor. And does not contain fluorescent components. In this case, the semiconductor light emitting device member 3A exhibits various functions such as sealing of the light emitting element 2, a light extraction function, and retention of functional components. In the following description, the semiconductor device member 3A that does not contain a fluorescent substance or a fluorescent substance component is appropriately referred to as a transparent member.

0200On the other hand, in the embodiment (Embodiments B-1 to B-40) corresponding to the application example of B) as shown in FIG. 49B, the light emitting device 1B is a member 3B for a semiconductor light emitting device and is a phosphor. And phosphor components. In this case, the semiconductor device member 3B can also exhibit a wavelength conversion function in addition to the various functions that the semiconductor device member 3A of FIG. 49 (a) can exhibit. In the following description, the semiconductor device member 3B containing a phosphor or a phosphor component is appropriately referred to as a fluorescent portion. Further, the phosphor portion may be indicated by reference numerals 33, 34 and the like as appropriate depending on its shape and function.

0201The light emitting element 2 is composed of, for example, an LED chip that emits blue light or ultraviolet light, but may be an LED chip having a light emitting color other than these.

0202Further, the transparent member 3A exhibits functions such as a highly durable sealing agent for the light emitting element 2, a light extraction film, and various function addition films. The transparent member 3A may be used alone, but any additive may be contained except for the fluorescent substance and the fluorescent substance component as long as the effect of the present invention is not significantly impaired.

0203On the other hand, the phosphor portion 3B can exhibit functions such as a highly durable sealing agent for the light emitting element 2, a light extraction film, and various function addition films, and is excited by light from the light emitting element 2 to have a desired wavelength. It exhibits a wavelength conversion function that emits light. The phosphor portion 3B may contain at least a fluorescent substance that is excited by the light from the light emitting element 2 and emits light having a desired wavelength. Examples of such fluorescent substances include various fluorescent substances exemplified above. As the emission color of the phosphor portion 3B, not only the three primary colors of red (R), green (G), and blue (B), but also white like a fluorescent lamp and yellow like a light bulb are possible. In short, the phosphor unit 3B has a wavelength conversion function of emitting light having a desired wavelength different from the excitation light.

0204In the above-mentioned light emitting device 1A shown in FIG. 49 (a), the light 4 emitted from the light emitting element 2 passes through the transparent member 3A and is emitted to the outside of the light emitting device 1A. Therefore, in the light emitting device 1A, the light 4 emitted from the light emitting element 2 is used as it is in the emission color when it is emitted from the light emitting element 2.

0205On the other hand, in the light emitting device 1B shown in FIG. 49 (b), a part 4a of the light emitted from the light emitting element 2 passes through the phosphor portion 3B as it is and is radiated to the outside of the light emitting device 1B. Further, in the light emitting device 1B, the other part 4b of the light emitted from the light emitting element 2 is absorbed by the phosphor portion 3B to excite the phosphor portion 3B, and the phosphor particles contained in the phosphor portion 3B, Light 5 having a wavelength peculiar to a fluorescent component such as a fluorescent ion or a fluorescent dye is emitted to the outside of the light emitting device 1B.

0206Therefore, from the light emitting device 1B, the combined light 6 of the light 4a emitted by the light emitting element 2 and transmitted through the phosphor portion 3B and the light 5 emitted by the phosphor portion 3B is emitted as wavelength-converted light. Therefore, the emission color of the light emitting device 1B as a whole is determined by the emission color of the light emitting element 2 and the emission color of the phosphor unit 3B. The light 4a that is emitted by the light emitting element 2 and passes through the phosphor portion 3B is not always necessary.

0207[A. Embodiment not using fluorescence] [Embodiment A-1] In the light emitting device 1A of the present embodiment, as shown in FIG. 1, the light emitting element 2 is surface-mounted on the insulating substrate 16 on which the printed wiring board 17 is provided. In the light emitting element 2, the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to the printed wirings 17 and 17 via the conductive wires 15 and 15, respectively. Has been done. The conductive wires 15 and 15 having a small cross-sectional area are used so as not to interfere with the light emitted from the light emitting element 2.

0208Here, as the light emitting element 2, an element that emits light of any wavelength from the ultraviolet to the infrared region may be used, but here, it is assumed that a gallium nitride based LED chip is used. Further, in this light emitting element 2, an n-type semiconductor layer (not shown) is formed on the lower surface side in FIG. 1 and a p-type semiconductor layer (not shown) is formed on the upper surface side, and light is output from the p-type semiconductor layer side. Will be described with the upper part of FIG. 1 as the front.

0209Further, a frame-shaped frame material 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16, and a sealing portion 19 for sealing and protecting the light emitting element 2 is provided inside the frame material 18. The sealing portion 19 is formed of the transparent member 3A, which is a member for a semiconductor light emitting device of the present invention, and can be formed by potting with the above-mentioned liquid for forming a member for a semiconductor light emitting device.

0210Since the light emitting device 1A of the present embodiment includes the light emitting element 2 and the transparent member 3A, the light durability and thermal durability of the light emitting device 1A can be improved. Further, since cracks and peeling are unlikely to occur in the sealing portion 3A, the transparency of the sealing portion 3A can be improved.

0211Further, the light color unevenness and the light color variation can be reduced as compared with the conventional case, and the efficiency of extracting light to the outside can be improved. That is, since the sealing portion 3A can be made highly transparent without fogging or turbidity, the uniformity of the light color is excellent, there is almost no variation in the light color between the light emitting devices 1A, and the light of the light emitting element 2 The efficiency of taking out the light to the outside can be improved as compared with the conventional case. In addition, the weather resistance of the luminescent substance can be improved, and the life of the luminescent device 1A can be extended as compared with the conventional case.

0212[Embodiment A-2] In the light emitting device 1A of the present embodiment, as shown in FIG. 2, a transparent member 3A covers the front surface of the light emitting element 2, and a sealing portion 19 is made of a material different from the transparent member 3A on the transparent member. Is formed in the same manner as in the above-described embodiment A-1. Further, the transparent member 3A on the surface of the light emitting element 2 is a transparent thin film that functions as a light extraction film and a sealing film. For example, when the chip of the light emitting element 2 is formed, the above-mentioned member forming liquid for a semiconductor light emitting device is spin-coated. It can be formed by applying with. The same components as those of the embodiment A-1 are designated by the same reference numerals, and the description thereof will be omitted.

0213Therefore, since the light emitting device 1A of the present embodiment also includes the light emitting element 2 and the transparent member 3A as in the embodiment A-1, the light durability and thermal durability of the light emitting device 1A are improved. Since cracks and peeling are unlikely to occur in the sealing portion 3A, the transparency of the sealing portion 3A can be improved. Furthermore, it is possible to obtain the same advantages as in the A-1 embodiment.

0214[B. Embodiment using fluorescence] [Embodiment B-1] As shown in FIG. 3A, the light emitting device 1B of the present embodiment includes a light emitting element 2 made of an LED chip and a molded portion 11 formed of a transparent transparent material in a bullet shape. The mold portion 11 covers the light emitting element 2, and the light emitting element 2 is electrically connected to lead terminals 12 and 13 formed of a conductive material. The lead terminals 12 and 13 are formed by a lead frame.

0215The light emitting element 2 is a gallium nitride based LED chip, and has an n-type semiconductor layer (not shown) formed on the lower surface side and a p-type semiconductor layer (not shown) formed on the upper surface side in FIG. 3 (a). Since the light output is taken out from the p-type semiconductor layer side, the upper part of FIG. 3 will be described as the front. The rear surface of the light emitting element 2 is joined to the mirror (cup portion) 14 attached to the front end portion of the lead terminal 13 by a die bond. Further, in the light emitting element 2, conductive wires (for example, gold wires) 15, 15 are connected to each of the above-mentioned p-type semiconductor layer and n-type semiconductor layer by bonding, and the light emitting element 2 and the light emitting element 2 are connected via the conductive wires 15, 15. The lead terminals 12 and 13 are electrically connected. The conductive wires 15 and 15 have a small cross-sectional area so as not to interfere with the light emitted from the light emitting element 2.

0216The mirror 14 has a function of reflecting the light radiated from the side surface and the rear surface of the light emitting element 2 forward, and the light radiated from the LED chip and the light reflected forward by the mirror 14 are molded portions that function as lenses. It is radiated forward from the mold portion 11 through the front end portion of 11. The mold portion 11 covers the light emitting element 2 together with the mirror 14, the conductive wires 15, 15 and a part of the lead terminals 12, 13, and the characteristics deteriorate due to the light emitting element 2 reacting with moisture in the atmosphere. It is prevented. The rear ends of the lead terminals 12 and 13 project outward from the rear surface of the mold portion 11, respectively.

0217By the way, in the light emitting element 2, as shown in FIG. 3B, a light emitting layer portion 21 made of a gallium nitride based semiconductor is formed on the phosphor portion 3B by using a semiconductor process, and the phosphor portion 3B is formed. A reflective layer 23 is formed on the rear surface. The light emitted from the light emitting layer portion 21 is radiated in all directions, but some of the light absorbed by the phosphor portion 3B excites the phosphor portion 3B and emits light having a wavelength peculiar to the fluorescent component. .. The light emitted by the phosphor portion 3B is reflected by the reflection layer 3 and radiated forward. Therefore, the light emitting device 1B can obtain the combined light of the light radiated from the light emitting layer portion 21 and the light radiated from the phosphor unit 3B.

0218Thus, the light emitting device 1B of the present embodiment includes a light emitting element 2 and a phosphor unit 3B that is excited by the light from the light emitting element 2 and emits light having a desired wavelength. Here, if a phosphor portion 3B having excellent translucency is used, a part of the light emitted from the light emitting element 2 is emitted to the outside as it is, and other light emitted from the light emitting element 2 is emitted to the outside. Since the fluorescent component that is the center of light emission is excited by a part of the light and the light emitted by the light emitted unique to the fluorescent component is emitted to the outside, the light emitted from the light emitting element 2 and the light emitted from the fluorescent component of the phosphor portion 3B It is possible to obtain the combined light with the above, reduce the light color unevenness and the light color variation as compared with the conventional case, and improve the efficiency of extracting the light to the outside. That is, if a phosphor portion 3B having high transparency without fogging or turbidity is used, the uniformity of the light color is excellent, there is almost no variation in the light color between the light emitting devices 1B, and the light of the light emitting element 2 goes out of the light. The efficiency of taking out the light can be improved as compared with the conventional case. In addition, the weather resistance of the luminescent substance can be improved, and the life of the luminescent device 1B can be extended as compared with the conventional case.

0219Further, in the light emitting device 1B of the present embodiment, since the phosphor portion 3B is also used as the substrate forming the light emitting element 2, the fluorescence that becomes the center of light emission in the phosphor portion by a part of the light from the light emitting element 2. The body can be excited efficiently, and the brightness of light due to the emission peculiar to the fluorescent component can be increased.

0220[Embodiment B-2] In the light emitting device 1B of the present embodiment, as shown in FIG. 4, the light emitting element 2 is surface-mounted on the insulating substrate 16 on which the printed wiring board 17 is provided. Here, the light emitting element 2 has the same configuration as that of the embodiment B-1, and the light emitting layer portion 21 made of a gallium nitride based semiconductor is formed on the phosphor portion 3B, and the reflective layer is formed on the rear surface of the phosphor portion 3B. 23 is formed. Further, in the light emitting element 2, the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to the printed wirings 17 and 17 via the conductive wires 15 and 15, respectively. It is connected.

0221Further, a frame-shaped frame material 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16, and a sealing portion 19 for sealing and protecting the light emitting element 2 is provided inside the frame material 18.

0222Thus, also in the light emitting device 1B of the present embodiment, similarly to the embodiment B-1, the light emitting element 2 and the phosphor unit 3B which is excited by the light from the light emitting element 2 and emits light of a desired wavelength. Therefore, it is possible to obtain a combined light of the light from the light emitting element 2 and the light from the phosphor. Further, as in the case of the B-1, the light color unevenness and the light color variation can be reduced as compared with the conventional case, the efficiency of extracting light to the outside can be improved, and the life can be extended. It becomes.

0223[Embodiment B-3] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and the frame material 18 (see FIG. 4) described in the second embodiment is not used, as shown in FIG. In addition, the shape of the sealing portion 19 is different. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0224The sealing portion 19 in the present embodiment is composed of a truncated cone-shaped sealing function portion 19a for sealing the light emitting element 2 and a lens-shaped lens function portion 19b that functions as a lens at the front end portion of the sealing portion 19. ing.

0225Therefore, in the light emitting device 1B of the present embodiment, the number of parts can be reduced as compared with the embodiment B-2, and the size and weight can be reduced. Moreover, by providing the lens function portion 19b that functions as a lens in a part of the sealing portion 19, it is possible to obtain a light distribution having excellent directivity.

0226[Embodiment B-4] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 6, a recess for accommodating the light emitting element 2 on one surface (upper surface in FIG. 6) of the insulating substrate 16. The feature is that 16a is provided, the light emitting element 2 is mounted on the bottom of the recess 16a, and the sealing portion 19 is provided in the recess 16a. Here, the printed wirings 17 and 17 formed on the insulating substrate 16 are extended to the bottom of the recess 16a, and are electrically connected to the light emitting layer portion 21 made of the gallium nitride based semiconductor of the light emitting element 2 via the conductive wires 15 and 15. It is connected to the. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0227Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed by filling the recess 16a formed on the upper surface of the insulating substrate 16, the frame material 18 described in the embodiment B-2 is described. The sealing portion 19 can be formed without using (see FIG. 5) or the molding die described in the embodiment B-3, and the light emitting element 2 is sealed as compared with the embodiments B-2 and B-3. There is an advantage that the stopping process can be easily performed.

0228[Embodiment B-5] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and is characterized in that the light emitting element 2 is mounted on the insulating substrate 16 by a so-called flip chip as shown in FIG. .. That is, the light emitting element 2 is provided with bumps 24 and 24 made of a conductive material on the surface side of each of the p-type semiconductor layer (not shown) and the n-type semiconductor layer (not shown) of the light emitting layer portion 21. The light emitting layer portion 21 is electrically connected to the printed wirings 17 and 17 of the insulating substrate 16 via bumps 24 and 24 face-down. Therefore, in the light emitting element 2 of the present embodiment, the light emitting layer portion 21 is arranged on the side closest to the insulating substrate 16, the reflecting layer 23 is arranged on the side farthest from the insulating substrate 16, and the light emitting layer portion 21 and the light emitting element 2 are reflected. The phosphor portion 3B will be interposed between the layer 23 and the layer 23. The same components as those of the embodiment B-4 are designated by the same reference numerals, and the description thereof will be omitted.

0229In the light emitting device 1B of the present embodiment, the light reflected downward (rearward) in FIG. 7 by the reflective layer 23 is reflected by the inner peripheral surface of the recess 16a and radiated upward (forward) in FIG. Here, it is desirable to separately provide a reflective layer made of a material having high reflectance on the inner peripheral surface of the recess 16a other than the printed wirings 17 and 17.

0230Therefore, the light emitting device 1B of the present embodiment does not require the conductive wires 15 and 15 as in the embodiment B-4 in order to connect the printed wirings 17 and 17 provided on the insulating substrate 16 and the light emitting element 2. Therefore, it is possible to improve the mechanical strength and reliability as compared with the embodiment B-4.

0231[Embodiment B-6] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, except that the reflection layer 23 described in the embodiment B-5 is not provided as shown in FIG. In short, in the light emitting device 1B of the present embodiment, the light emitted by the light emitting layer portion 21 and the light emitted by the phosphor unit 3B pass through the sealing portion 19 and are radiated forward as they are. The same components as those of the embodiment B-5 are designated by the same reference numerals, and the description thereof will be omitted.

0232Therefore, the light emitting device 1B of the present embodiment can reduce the number of parts as compared with the embodiment B-5, and can be easily manufactured.

0233[Embodiment B-7] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the first embodiment B-1, and as shown in FIG. 9, a mold portion 11 for covering the light emitting element 2 is provided, and the mold portion 11 is a phosphor portion. It is characterized in that it is formed integrally with. The same components as those of the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0234In the production of the light emitting device 1B of the present embodiment, a work-in-process product without the mold portion 11 is immersed in a molding mold containing a phosphor portion-forming liquid, and the phosphor-forming liquid (polycondensate) is mixed. The mold portion 11 is formed by a method of curing or the like.

0235Therefore, in the present embodiment, since the mold portion 11 is integrally formed with the phosphor portion, the mold portion 11 is sealed by using the semiconductor light emitting device member of the present invention as the phosphor portion as described later. It is possible to improve the stopping property, transparency, light resistance, heat resistance, etc., and to suppress cracks and peeling due to long-term use.

0236[Embodiment B-8] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the first embodiment, and as shown in FIG. 10, a cup-shaped phosphor portion 3B having an open rear surface is mounted on the outer surface of the mold portion 11. The feature is that it is done. That is, in the present embodiment, instead of providing the phosphor portion 3B in the light emitting element 2 as in the embodiment B-1, the phosphor portion 3B having a shape along the outer circumference of the mold portion 11 is provided. The same components as those of the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0237The phosphor portion 3B in the present embodiment may be formed as a thin film by the method of curing the phosphor portion forming liquid (polycondensate) described in the embodiment B-7, or a solid phosphor portion may be formed in advance. A member molded into a cup shape may be attached to the mold portion 11.

0238Therefore, in the light emitting device 1B of the present embodiment, the amount of material used in the phosphor portion is larger than that in the case where the entire mold portion 11 is integrally formed with the phosphor portion as in the light emitting device 1B of the embodiment B-7. It is possible to reduce the cost and reduce the cost.

0239[Embodiment B-9] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 11, the light emitting element 2 is surrounded on one surface (upper surface of FIG. 11) of the insulating substrate 16. The frame-shaped frame material 18 arranged in the above is provided, and the sealing portion 19 inside the frame material 18 is formed by the same phosphor portion as the phosphor portion 3B described in the embodiment B-2. It is characterized by points. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0240Therefore, in the present embodiment, since the sealing portion 19 is formed by the phosphor portion, the molding portion 11 is sealed by using the semiconductor light emitting device member of the present invention as the phosphor portion as described later. It is possible to improve the properties, transparency, light resistance, heat resistance, etc., and to suppress cracks and peeling due to long-term use.

0241[Embodiment B-10] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 12, the light emitting element 2 is surrounded on one surface (upper surface of FIG. 12) of the insulating substrate 16. The frame-shaped frame material 18 arranged in the above is provided, and the sealing portion 19 inside the frame material 18 is formed by the same phosphor portion as the phosphor portion 3B described in the embodiment B-2. It is characterized by points. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0242Therefore, in the present embodiment, since the sealing portion 19 is formed by the phosphor portion, the molding portion 11 is sealed by using the semiconductor light emitting device member of the present invention as the phosphor portion as described later. It is possible to improve the properties, transparency, light resistance, heat resistance, etc., and to suppress cracks and peeling due to long-term use.

0243Further, in the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 covering the light emitting element 2 is formed by the phosphor portion. Since the phosphor portion is present in all directions of the light emitting layer portion 21, there is an advantage that the excitation and emission of the phosphor portion can be performed more efficiently as compared with the embodiment B-9.

0244[Embodiment B-11] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 13, a lens shape is formed in advance on the upper surface of the sealing portion 19 made of a translucent material. It is characterized in that the phosphor portion 33 is arranged. Here, the phosphor portion 33 is made of the same material as the phosphor portion 3B described in the embodiment B-2, is excited by the light from the light emitting element 2, and emits light having a desired wavelength. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0245Therefore, in the light emitting device 1B of the present embodiment, the phosphor unit 33 has not only a wavelength conversion function but also a function as a lens, and the directivity of light emission can be controlled by the lens effect.

0246[Embodiment B-12] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 14, the upper surface of the sealing portion 19 made of a translucent material is preliminarily formed into a lens shape. It is characterized in that the phosphor portion 33 is arranged. Here, the phosphor portion 33 is made of the same material as the phosphor portion 3B described in the embodiment B-2, is excited by the light from the light emitting element 2, and emits light having a desired wavelength. .. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0247Therefore, in the light emitting device 1B of the present embodiment, the phosphor unit 33 has not only a wavelength conversion function but also a function as a lens, and the directivity of light emission can be controlled by the lens effect. Further, in the present embodiment, since the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, the excitation and light emission of the phosphor portion are more efficiently performed than in the embodiment B-11. There is an advantage that it can be done.

0248[Embodiment B-13] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. 15, a sealing portion 19 for covering the light emitting element 2 is provided on the upper surface side of the insulating substrate 16. It is characterized in that the sealing portion 19 is formed by a phosphor portion. Here, the sealing portion 19 has a truncated cone-shaped sealing function portion 19a for sealing the light emitting element 2 and a lens-shaped sealing portion 19 that functions as a lens at the front end portion of the sealing portion 19, similarly to the embodiment B-3. It is composed of the lens function unit 19b. The same components as those of the embodiment B-3 are designated by the same reference numerals, and the description thereof will be omitted.

0249Therefore, in the light emitting device 1B of the present embodiment, not only the function of the sealing portion 19 to seal and protect the light emitting element 2 but also the wavelength conversion function of wavelength-converting the light from the light emitting element 2 and the directivity of light emission are provided. It will have a lens function to control. In addition, the weather resistance of the sealing portion 19 can be improved, and the life of the sealing portion 19 can be extended. Further, in the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 covering the light emitting element 2 is formed by the phosphor portion. Since the phosphor portion is present in all directions of the light emitting layer portion 21, there is an advantage that the excitation and emission of the phosphor portion can be performed more efficiently as compared with the embodiment B-12.

0250[Embodiment B-14] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. 16, the sealing that covers the light emitting element 2 on one surface (upper surface of FIG. 16) of the insulating substrate 16. It is characterized in that the portion 19 is provided and the sealing portion 19 is formed by the phosphor portion 3B. Here, the sealing portion 19 has a truncated cone-shaped sealing function portion 19a for sealing the light emitting element 2 and a lens-shaped sealing portion 19 that functions as a lens at the front end portion of the sealing portion 19, similarly to the embodiment B-3. It is composed of the lens function unit 19b. The same components as those of the embodiment B-3 are designated by the same reference numerals, and the description thereof will be omitted.

0251Therefore, in the light emitting device 1B of the present embodiment, not only the function of the sealing portion 19 to seal and protect the light emitting element 2 but also the wavelength conversion function of wavelength-converting the light from the light emitting element 2 and the directivity of light emission are provided. It will have a lens function to control. In addition, the weather resistance of the sealing portion 19 can be improved, and the life of the sealing portion 19 can be extended.

0252[Embodiment B-15] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. 17, a dome-shaped phosphor portion 34 covering the light emitting element 2 is provided on the upper surface side of the insulating substrate 16. It is characterized in that a sealing portion 19 made of a translucent resin is formed on the outer surface side of the phosphor portion 34. Here, the sealing portion 19 is a lens-shaped lens functioning portion 19a that seals the light emitting element 2 and functions as a lens at the front end portion of the sealing portion 19 as in the embodiment B-3. It is composed of and. The same components as those of the embodiment B-3 are designated by the same reference numerals, and the description thereof will be omitted.

0253Therefore, in the light emitting device 1B of the present embodiment, the amount of material used in the phosphor portion 34 can be reduced as compared with the embodiments B-13 and B-14. Further, in the present embodiment, since the dome-shaped phosphor portion 34 covering the light emitting element 2 is disposed, the semiconductor light emitting device member of the present invention can be used as the phosphor portion as described later from the outside. Deterioration of the light emitting element 2 due to moisture or the like can be prevented more reliably, and the life can be extended.

0254[Embodiment B-16] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. 18, a dome-shaped phosphor portion 34 covering the light emitting element 2 is provided on the upper surface side of the insulating substrate 16. It is characterized in that it is arranged and the sealing portion 19 is formed on the outer surface side of the phosphor portion 34. Here, the sealing portion 19 is a lens-shaped lens functioning portion 19a that seals the light emitting element 2 and functions as a lens at the front end portion of the sealing portion 19 as in the embodiment B-3. It is composed of and. The same components as those of the embodiment B-3 are designated by the same reference numerals, and the description thereof will be omitted.

0255Therefore, in the light emitting device 1B of the present embodiment, the amount of material used in the phosphor portion 34 can be reduced as compared with the embodiments B-13 and B-14. Further, in the present embodiment, since the dome-shaped phosphor portion 34 covering the light emitting element 2 is disposed, the semiconductor light emitting device member of the present invention can be used as the phosphor portion as described later from the outside. Deterioration of the light emitting element 2 due to moisture or the like can be prevented more reliably, and the life can be extended. Further, in the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 covering the light emitting element 2 is formed by the phosphor portion. Since the phosphor portion is present in all directions of the light emitting layer portion 21, there is an advantage that the excitation and emission of the phosphor portion can be performed more efficiently as compared with the embodiment B-15.

0256[Embodiment B-17] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 19, on the bottom of the recess 16a provided on one surface (upper surface in FIG. 19) of the insulating substrate 16. It is provided with a sealing portion 19 for sealing the arranged light emitting element 2, and is characterized in that the sealing portion 19 is formed by a phosphor portion. Here, the phosphor unit is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor unit 3B described in the embodiment B-1. The same components as those of the embodiment B-4 are designated by the same reference numerals, and the description thereof will be omitted.

0257Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed by the phosphor portion, it is sealed by using the semiconductor light emitting device member of the present invention as the phosphor portion as described later. It is possible to improve the sealing property, transparency, light resistance, heat resistance, etc. of the part 19 and suppress cracks and peeling due to long-term use. Further, in the present embodiment, the phosphor portion 3B is formed on the rear surface of the light emitting layer portion 21 of the light emitting element 2, and the sealing portion 19 covering the light emitting element 2 is formed by the phosphor portion 3B. Since the phosphor part is present in all directions of the light emitting layer part 21, there is an advantage that the excitation and light emission of the phosphor part can be performed more efficiently as compared with the embodiment B-15.

0258[Embodiment B-18] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 20, on the bottom of the recess 16a provided on one surface (upper surface in FIG. 20) of the insulating substrate 16. It is provided with a sealing portion 19 for sealing the arranged light emitting element 2, and is characterized in that the sealing portion 19 is formed by the phosphor portion 3B. Here, the phosphor portion 3B is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor portion 3B described in the embodiment B-1. The same components as those of the embodiment B-4 are designated by the same reference numerals, and the description thereof will be omitted.

0259Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed by the phosphor portion, it is sealed by using the semiconductor light emitting device member of the present invention as the phosphor portion 3B as described later. It is possible to improve the sealing property, transparency, light resistance, heat resistance, etc. of the stop portion 19 and suppress cracks and peeling due to long-term use.

0260[Embodiment B-19] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 21, a phosphor molded in advance into a lens shape on the upper surface (light extraction surface) of the sealing portion 19. The feature is that the portion 33 is arranged. Here, the phosphor unit 33 is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor unit 3B described in the embodiment B-1. The same components as those of the embodiment B-4 are designated by the same reference numerals, and the description thereof will be omitted.

0261Therefore, in the light emitting device 1B of the present embodiment, the phosphor unit 33 has not only a wavelength conversion function but also a function as a lens, and the directivity of light emission can be controlled by the lens effect.

0262[Embodiment B-20] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 22, a phosphor molded in advance into a lens shape on the upper surface (light extraction surface) of the sealing portion 19. The feature is that the portion 33 is arranged. Here, the phosphor unit 33 is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor unit 3B described in the embodiment B-1. The same components as those of the embodiment B-4 are designated by the same reference numerals, and the description thereof will be omitted.

0263Therefore, in the light emitting device 1B of the present embodiment, the phosphor unit 33 has not only a wavelength conversion function but also a function as a lens, and the directivity of light emission can be controlled by the lens effect. Further, in the present embodiment, since the phosphor portion 3B is also arranged on the rear surface of the light emitting layer portion 21 of the light emitting element 2, the excitation and light emission of the phosphor portion are more efficient than in the embodiment B-19. There is an advantage that it is done in a targeted manner.

0264[Embodiment B-21] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, and as shown in FIG. 23, at the bottom of the recess 16a provided on one surface (upper surface in FIG. 23) of the insulating substrate 16. It is provided with a sealing portion 19 for sealing the arranged light emitting element 2, and is characterized in that the sealing portion 19 is formed by the phosphor portion 3B. Here, as shown in FIG. 24, the sealing portion 19 has a recess 19c for accommodating the light emitting element 2 in a portion having an outer peripheral shape corresponding to the recess 16a and corresponding to the light emitting element 2. Since the material processed into the shape to have is mounted in the recess 16a of the insulating substrate 16 on which the light emitting element 2 is mounted, the sealing process can be simplified. Further, the phosphor portion 3B forming the sealing portion 19 is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor portion 3B described in the embodiment B-1. The same components as those of the embodiment B-5 are designated by the same reference numerals, and the description thereof will be omitted.

0265Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed by the phosphor portion, it is sealed by using the semiconductor light emitting device member of the present invention as the phosphor portion 3B as described later. It is possible to improve the sealing property, transparency, light resistance, heat resistance, etc. of the stop portion 19 and suppress cracks and peeling due to long-term use. Further, in the present embodiment, the light radiated forward from the light emitting layer portion 21 of the light emitting element 2 is once reflected by the reflection layer 23 toward the inner bottom surface side of the recess 16a, so that the inner bottom surface of the recess 16a is reflected. And if a reflective layer is provided on the inner peripheral surface, it is further reflected on the inner bottom surface and the inner peripheral surface of the recess 16a and radiated forward, so that the optical path length can be lengthened and the phosphor portion 3B is more efficient. Has the advantage of being able to excite and emit light.

0266[Embodiment B-22] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-5, and as shown in FIG. 25, at the bottom of the recess 16a provided on one surface (upper surface in FIG. 25) of the insulating substrate 16. It is provided with a sealing portion 19 for sealing the arranged light emitting element 2, and is characterized in that the sealing portion 19 is formed by the phosphor portion 3B. Here, as shown in FIG. 26, the sealing portion 19 has a recess 19c for accommodating the light emitting element 2 in a portion having an outer peripheral shape corresponding to the recess 16a and corresponding to the light emitting element 2. Since the material processed into the shape to have is mounted in the recess 16a of the insulating substrate 16 on which the light emitting element 2 is mounted, the sealing process can be simplified. Further, the phosphor portion 3B forming the sealing portion 19 is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor portion 3B described in the embodiment B-1. The same components as those of the embodiment B-5 are designated by the same reference numerals, and the description thereof will be omitted.

0267Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is formed by the phosphor portion 3B, the semiconductor light emitting device member of the present invention can be used as the phosphor portion 3B as described later. It is possible to improve the sealing property, transparency, light resistance, heat resistance, etc. of the sealing portion 19, and to suppress cracks and peeling due to long-term use.

0268[Embodiment B-23] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-6, and as shown in FIG. 27, a phosphor portion 3B processed into a rod shape in advance is arranged on the upper surface of the light emitting element 2. It is characterized by the fact that it does. Here, a sealing portion 19 made of a translucent material is formed around the light emitting element 2 and the phosphor portion 3B, and one end surface (lower end surface in FIG. 27) of the phosphor portion 3B is the light emitting element 2. The other end surface (upper end surface in FIG. 27) is exposed in close contact with the light emitting layer portion 21. The same components as those of the embodiment B-6 are designated by the same reference numerals, and the description thereof will be omitted.

0269Therefore, in the light emitting device 1B of the present embodiment, since the phosphor portion 3B whose one end surface is in close contact with the light emitting layer portion 21 of the light emitting element 2 is formed in a rod shape, the light emitted by the light emitting layer portion 21 is emitted. It can be efficiently taken into the phosphor part 3B through the one end surface of the phosphor part 3B, and the emission of the phosphor part 3B excited by the taken-in light can be efficiently taken out through the other end surface of the phosphor part 3B. Can be radiated. In this embodiment, the phosphor portion 3B is formed in a rod shape having a relatively large diameter and only one is used. However, as shown in FIG. 28, the phosphor portion 3B is formed in a fiber shape having a relatively small diameter. Then, a plurality of phosphor portions 3B may be arranged side by side. Further, the cross-sectional shape of the phosphor portion 3B is not limited to a circle, and may be formed into, for example, a quadrangular shape or any other shape.

0270[Embodiment B-24] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-23, and as shown in FIG. 29, a sealing portion 19 provided in the recess 16a of the insulating substrate 16 is provided and sealed. The feature is that the portion 19 is formed by the phosphor portion 3B. Here, as shown in FIG. 30, the sealing portion 19 has a through hole 19d for accommodating the light emitting element 2 in a portion having an outer peripheral shape corresponding to the recess 16a and corresponding to the light emitting element 2. Since the material processed into the shape having the above is mounted in the recess 16a of the insulating substrate 16 on which the light emitting element 2 is mounted, the sealing process can be simplified. Further, the phosphor portion 3B forming the sealing portion 19 is excited by the light from the light emitting element 2 and emits light having a desired wavelength, similarly to the phosphor portion 3B described in the embodiment B-1. The same components as those of the embodiment B-23 are designated by the same reference numerals, and the description thereof will be omitted.

0271Therefore, in the light emitting device 1B of the present embodiment, since the sealing portion 19 is also formed by the phosphor portion 3B, it is possible to extend the life and improve the efficiency of light emission. In this embodiment, the phosphor portion 3B is formed into a rod shape having a relatively large diameter and only one is used. However, as shown in FIG. 31, the phosphor portion 3B is formed into a fiber shape having a relatively small diameter. Then, a plurality of phosphor portions 3B may be arranged side by side. Further, the cross-sectional shape of the phosphor portion 3B is not limited to a circle, and may be formed into, for example, a quadrangular shape or any other shape.

0272[Embodiment B-25] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the second embodiment, and as shown in FIG. 32, the frame member 18 arranged on one surface (upper surface in FIG. 32) of the insulating substrate 16 is provided. The light emitting layer portion 21 of the light emitting element 2 is AlGaN-based and emits near-ultraviolet light, and a phosphor powder (for example, near-ultraviolet) is contained in the translucent material used as the sealing portion 19 inside the frame material 18. YAG: Ce that is excited by light and emits yellow light³⁺It is characterized by the fact that (fluorescent powder) is dispersed. Further, in the present embodiment, as the phosphor portion 3B, P is a fluorinated glass (for example, P that is excited by near-ultraviolet light and emits blue light.₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the second embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0273Therefore, in the light emitting device 1B of the present embodiment, since the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, the light emitted from the light emitting element 2 and the phosphor A light output consisting of a composite light of the light emitted from the part 3B and the light emitted from the phosphor powder can be obtained.

0274Therefore, if a material that emits near-ultraviolet light is selected as the material for the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 causes the phosphor portion 3B and the phosphor powder in the sealing portion 19 to be combined. Both of them are excited and each emits a unique emission, and the combined light is obtained. In the present embodiment, blue light is emitted from the phosphor portion 3B and yellow light is emitted from the phosphor powder, so that white light different from any emission color can be obtained.

0275In addition, the existing fluorescent powder and the fluorescent particles of the phosphor portion are limited in the materials capable of emitting light, and it may not be possible to obtain a desired light color with only one of them. In such a case, Is extremely effective in this embodiment. That is, when the desired light color characteristic cannot be obtained only by the phosphor portion 3B, the desired light color characteristic is complemented by using a phosphor powder having an appropriate light color characteristic lacking in the phosphor portion 3B in combination. A light emitting device 1B having light color characteristics can be realized. Further, in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the phosphor The light emission of the phosphor powder is superimposed on the light emission of the part 3B, the light output can be increased, and the light emission efficiency can be improved. Here, when the emission color of the phosphor portion 3B and the phosphor powder is substantially the same, for example, P that emits red light as the phosphor particles of the phosphor portion 3B.₂O₅ SrF₂ BaF₂:EU³⁺Y that emits red light as a phosphor powder₂O₂S: Eu³⁺Can be used to improve the efficiency of red light emission. Of course, this combination of the phosphor portion 3B and the phosphor powder is an example, and other combinations may be adopted.

0276[Embodiment B-26] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the third embodiment, and as shown in FIG. 33, the light emitting element 2 is sealed on one surface (upper surface of FIG. 33) of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 is AlGaN-based and emits near-ultraviolet light, and the phosphor powder (for example, near-ultraviolet light) is contained in the translucent material used as the sealing portion 19. YAG: Ce that is excited by and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-3 are designated by the same reference numerals, and the description thereof will be omitted.

0277Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0278[Embodiment B-27] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-4, and as shown in FIG. 34, the light emitting element 2 is filled in the recess 16a formed on the upper surface of the insulating substrate 16. A sealing portion 19 for sealing is provided, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and a phosphor powder (for example, for example) is contained in the translucent material used as the sealing portion 19. YAG: Ce that is excited by near-ultraviolet light and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-4 are designated by the same reference numerals, and the description thereof will be omitted.

0279Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0280[Embodiment B-28] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the fifth embodiment, and as shown in FIG. 35, the recess 16a formed on one surface (upper surface in FIG. 35) of the insulating substrate 16 is filled. A sealing portion 19 for sealing the light emitting element 2 is provided, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is contained in a translucent material used as the sealing portion 19. Fluorescent powder (for example, YAG: Ce that is excited by near-ultraviolet light and emits yellow light.³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-5 are designated by the same reference numerals, and the description thereof will be omitted.

0281Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0282[Embodiment B-29] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-6, and as shown in FIG. 36, the recess 16a formed on one surface (upper surface in FIG. 36) of the insulating substrate 16 is filled. A sealing portion 19 for sealing the light emitting element 2 is provided, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is contained in a translucent material used as the sealing portion 19. Fluorescent powder (for example, YAG: Ce that is excited by near-ultraviolet light and emits yellow light.³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-6 are designated by the same reference numerals, and the description thereof will be omitted.

0283Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0284[Embodiment B-30] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-1, and as shown in FIGS. 37 (a) and 37 (b), the light emitting element 2 is provided with a bullet-shaped mold portion 11. The light emitting layer portion 21 is an AlGaN-based material that emits near-ultraviolet light, and a phosphor powder (for example, excited by near-ultraviolet light to emit yellow light) is contained in the translucent material used as the mold portion 11. YAG: Ce³⁺The feature is that the (fluorescent powder) is dispersed and the mold portion 11 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.

0285Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the mold portion 11, so that the light emitting element 2 is used. An optical output consisting of a composite light of the emitted light, the light emitted from the phosphor unit 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the phosphor portion 3B and the mold are formed by the light emitted from the light emitting element 2. Both of the fluorescent substance powder in the part 11 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the light emission efficiency can be improved.

0286[Embodiment B-31] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-8, and as shown in FIG. 38, a bullet-shaped mold portion 11 is provided, and a light emitting layer portion 21 of the light emitting element 2 (FIG. 38). (The illustration is omitted) is an AlGaN-based device that emits near-ultraviolet light, and emits yellow light when excited by phosphor powder (for example, near-ultraviolet light) in the translucent material used as the mold portion 11. YAG: Ce³⁺The feature is that the (fluorescent powder) is dispersed and the mold portion 11 functions as the phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-8 are designated by the same reference numerals, and the description thereof will be omitted.

0287Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the mold portion 11, so that the light emitting element 2 is used. An optical output consisting of a composite light of the emitted light, the light emitted from the phosphor unit 3B, and the light emitted from the phosphor powder can be obtained. That is, in Embodiment B-25 Likewise as, by selecting material that emits near ultraviolet light as material of luminous layer part 21 in luminous element 2, due to the light emitted from the light emitting element 2 phosphor part 3B and And the phosphor powder in the mold portion 11 are both excited to exhibit their own luminescence, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0288[Embodiment B-32] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-11, and as shown in FIG. 39, the light emitting element 2 is sealed on one surface (upper surface of FIG. 39) of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 is AlGaN-based and emits near-ultraviolet light, and the phosphor powder (for example, near-ultraviolet light) is contained in the translucent material used as the sealing portion 19. YAG: Ce that is excited by and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-11 are designated by the same reference numerals, and the description thereof will be omitted.

0289Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0290[Embodiment B-33] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-15, and as shown in FIG. 40, the light emitting element 2 is sealed on one surface (upper surface of FIG. 40) of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 is AlGaN-based and emits near-ultraviolet light, and the phosphor powder (for example, near-ultraviolet light) is contained in the translucent material used as the sealing portion 19. YAG: Ce that is excited by and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-15 are designated by the same reference numerals, and the description thereof will be omitted.

0291Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0292[Embodiment B-34] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-19, and as shown in FIG. 41, the recess 16a formed on one surface (upper surface in FIG. 41) of the insulating substrate 16 is filled. A sealing portion 19 for sealing the light emitting element 2 is provided, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is contained in a translucent material used as the sealing portion 19. Fluorescent powder (for example, YAG: Ce that is excited by near-ultraviolet light and emits yellow light.³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-19 are designated by the same reference numerals, and the description thereof will be omitted.

0293Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0294[Embodiment B-35] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiments B-12 and B-22, and as shown in FIG. 42, a recess formed on one surface (upper surface in FIG. 42) of the insulating substrate 16. A sealing portion 19 is provided in the place 16a to seal the light emitting element 2, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is used as the sealing portion 19. Fluorescent powder in the sex material (eg, YAG: Ce that is excited by near-ultraviolet light and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiments B-12 and B-22 are designated by the same reference numerals, and the description thereof will be omitted.

0295Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0296[Embodiment B-36] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-12, and as shown in FIG. 43, a sealing portion 19 for sealing the light emitting element 2 is provided on the upper surface side of the insulating substrate 16. , The light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and a phosphor powder (for example, yellow light excited by near-ultraviolet light) is contained in the translucent material used as the sealing portion 19. YAG: Ce³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-12 are designated by the same reference numerals, and the description thereof will be omitted.

0297Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0298[Embodiment B-37] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-16, and as shown in FIG. 44, the light emitting element 2 is sealed on one surface (upper surface of FIG. 44) of the insulating substrate 16. The light emitting layer portion 21 of the light emitting element 2 is AlGaN-based and emits near-ultraviolet light, and the phosphor powder (for example, near-ultraviolet light) is contained in the translucent material used as the sealing portion 19. YAG: Ce that is excited by and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-16 are designated by the same reference numerals, and the description thereof will be omitted.

0299Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0300[Embodiment B-38] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiment B-20, and as shown in FIG. 45, the recess 16a formed on one surface (upper surface in FIG. 45) of the insulating substrate 16 is filled. A sealing portion 19 for sealing the light emitting element 2 is provided, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is contained in a translucent material used as the sealing portion 19. Fluorescent powder (for example, YAG: Ce that is excited by near-ultraviolet light and emits yellow light.³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiment B-20 are designated by the same reference numerals, and the description thereof will be omitted.

0301Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0302[Embodiment B-39] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiments B-5 and B-12, and as shown in FIG. 46, a recess formed on one surface (upper surface in FIG. 46) of the insulating substrate 16. A sealing portion 19 is provided in the place 16a to seal the light emitting element 2, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is used as the sealing portion 19. Fluorescent powder in the sex material (eg, YAG: Ce that is excited by near-ultraviolet light and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiments B-5 and B-12 are designated by the same reference numerals, and the description thereof will be omitted.

0303Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0304[Embodiment B-40] The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the embodiments B-20 and B-21, and as shown in FIG. 47, a recess formed on one surface (upper surface in FIG. 47) of the insulating substrate 16. A sealing portion 19 is provided in the place 16a to seal the light emitting element 2, and the light emitting layer portion 21 of the light emitting element 2 emits near-ultraviolet light in an AlGaN system, and is used as the sealing portion 19. Fluorescent powder in the sex material (eg, YAG: Ce that is excited by near-ultraviolet light and emits yellow light³⁺It is characterized in that the (fluorescent powder) is dispersed and the sealing portion 19 functions as a phosphor portion. Further, in the present embodiment, as the phosphor particles of the phosphor portion 3B, P phosphate-based glass (for example, P that is excited by near-ultraviolet light and emits blue light).₂O₅ AlF₃ MgF CaF₂ SrF₂ BaCl₂:EU²⁺) Is used. The same components as those of the embodiments B-20 and B-21 are designated by the same reference numerals, and the description thereof will be omitted.

0305Therefore, in the light emitting device 1B of the present embodiment, as in the embodiment B-25, the phosphor powder that is excited by the light from the light emitting element 2 and emits light is dispersed in the sealing portion 19, so that the light emitting element 2 An optical output consisting of a composite light of the light emitted from the light, the light emitted from the phosphor portion 3B, and the light emitted from the phosphor powder can be obtained. That is, similarly to the embodiment B-25, if a material that emits near-ultraviolet light is selected as the material of the light emitting layer portion 21 of the light emitting element 2, the light emitted from the light emitting element 2 seals the phosphor portion 3B. Both of the fluorescent substance powder in the stop portion 19 are excited, and each of them exhibits a unique emission, and the synthesized light is obtained. Further, also in the present embodiment, the emission color of the phosphor powder is different from the emission color of the phosphor portion 3B, but if the emission color of the phosphor powder is aligned with the emission color of the phosphor portion 3B, the fluorescence The light emission of the phosphor powder is superimposed on the light emission of the body part 3B, the light output can be increased, and the luminous efficiency can be improved.

0306By the way, in each of the above embodiments, the phosphor portion 3B is processed into a desired shape or formed by the solgel method, but as shown in FIG. 48, the diameter of the phosphor portion 3B is slightly larger than the visible wavelength. If a large number of phosphor portions 3B are formed in a large spherical shape and dispersed in a solid medium 35 made of a translucent material to be used in place of the phosphor portion in each of the above embodiments, fluorescence in the visible wavelength region can be obtained. It is possible to reduce the amount of material used in the phosphor part while maintaining the transparency of the body part, and it is possible to reduce the cost.

0307Further, although the light emitting device 1B of each of the above embodiments includes only one light emitting element 2, a plurality of light emitting elements 2 constitute one unit of a module, and at least a part of the module is a phosphor as a light emitting substance. Of course, the portions may be arranged in close proximity to each other. For example, in the case of a light emitting device including a bullet-shaped mold portion 11 as described in the embodiment B-1, a plurality of light emitting devices are mounted on the same printed circuit board to form one unit module. May be good. Further, for example, in the surface mount type light emitting device as described in the embodiment B-2, a plurality of light emitting elements 2 may be arranged on the same insulating substrate 16 to form one unit module. Good.

0308[Application of semiconductor light emitting device members] In the light emitting devices (semiconductor light emitting devices) 1A and 1B of the respective embodiments A-1, A-2, B-1 to B-40 described above, the place where the semiconductor light emitting device member of the present invention is applied is not particularly limited. In each of the above embodiments, an example in which the semiconductor light emitting device member of the present invention is applied as a member for forming the transparent member 3A, the phosphor portions 3B, 33, 34, etc. has been shown. It can be suitably used as a member for forming the mold portion 11, the frame material 18, the sealing portion 19, and the like. By using the semiconductor light emitting device member of the present invention as these members, various effects such as excellent sealing property, transparency, light resistance, heat resistance, and suppression of cracks and peeling due to long-term use can be obtained. It becomes possible.

0309Further, when the semiconductor light emitting device member of the present invention is applied, it is preferable to appropriately modify it according to the location to which the present invention is applied. For example, when the present invention is applied to the phosphor parts 3B, 33, 34, the above-mentioned fluorescent particles or fluorescent components such as fluorescent ion and fluorescent dye are mixed with the member for the semiconductor light emitting device of the present invention and used. Just do it. As a result, in addition to the various effects listed above, the effect of enhancing the retention of the phosphor can be obtained.

0310Further, since the member for a semiconductor light emitting device of the present invention has excellent durability, it is a sealing material having excellent light durability (ultraviolet durability) and thermal durability even when used alone without containing a phosphor. It is possible to seal a light emitting element (LED chip, etc.) as an inorganic adhesive application). Further, if the above-mentioned inorganic oxide particles are mixed with the member for the semiconductor light emitting device of the present invention and used, in addition to the various effects mentioned above, the above-mentioned effects can be obtained in the description of the combined use of the inorganic oxide particles. It becomes. In particular, a film adjusted to have a refractive index close to that of the light emitting element by using inorganic oxide particles in combination acts as a suitable light extraction film.

0311[Applications for semiconductor light emitting devices, etc.] The semiconductor light emitting device can be used, for example, in a light emitting device. When a semiconductor light emitting device is used as a light emitting device, the light emitting device may have a phosphor-containing layer containing a mixture of a red phosphor, a blue phosphor, and a green phosphor arranged on a light source. In this case, the red phosphor does not necessarily have to be mixed in the same layer as the blue phosphor and the green phosphor. For example, the red phosphor is placed on the layer containing the blue phosphor and the green phosphor. The containing layers may be laminated.

0312In the light emitting device, the phosphor-containing layer can be provided above the light source. The phosphor-containing layer can be provided as a contact layer between the light source and the sealing resin portion, as a coating layer on the outside of the sealing resin portion, or as a coating layer on the inside of the outer cap. It is also possible to take a form in which a phosphor is contained in the sealing resin.

0313As the sealing resin used, the member for a semiconductor light emitting device of the present invention can be used. In addition, other resins can also be used. Examples of such resins usually include thermoplastic resins, thermosetting resins, photocurable resins and the like. Specifically, for example, methacrylic resins such as methyl polymethacrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; polyvinyl alcohols; ethyl cellulose and cellulose acetate. , Cellulose-based resins such as cellulose acetate butyrate; epoxy resins; phenolic resins; silicone resins and the like. Further, an inorganic material such as a solution obtained by hydrolyzing and polymerizing a solution containing a metal alkoxide, a ceramic precursor polymer or a metal alkoxide by a sol-gel method, or an inorganic material obtained by solidifying a combination thereof, for example, a siloxane bond An inorganic material having can be used.

0314The amount of the phosphor used with respect to the binder resin is not particularly limited, but is usually 0.01 to 100 parts by weight, preferably 0.1 to 80 parts by weight, preferably 1 to 60 parts by weight with respect to 100 parts by weight of the binder resin. is there.

0315In addition, the sealing resin contains a dye for color tone correction, an antioxidant, a processing / oxidation and heat stabilizer such as a phosphorus-based processing stabilizer, a light resistance stabilizer such as an ultraviolet absorber, and a silane coupling agent. Can be made to.

0316The light source is not particularly limited as long as it emits light having a peak wavelength in the range of 350 nm to 500 nm, and specific examples thereof include a light emitting diode (LED) and a laser diode (LD). Among them, GaN-based LEDs and LDs using GaN-based compound semiconductors are preferable. This is because GaN-based LEDs and LDs have significantly higher emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, and when combined with the phosphor, they are extremely low in power and extremely bright. This is because light emission can be obtained. For example, a GaN-based LED or LD usually has a light emission intensity 100 times or more that of a SiC-based LED with a current load of 20 mA. For GaN-based LEDs and LDs, Al_XGa_YN light emitting layer, GaN light emitting layer, or In_XGa_YThose having an N light emitting layer are preferable. In GaN-based LEDs, among them, In_XGa_YThose having an N light emitting layer have a very strong light emitting intensity, and are particularly preferable. In GaN-based LD, In_XGa_YA multi-quantum well structure consisting of an N layer and a GaN layer is particularly preferable because it has a very strong emission intensity.

0317In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. Among GaN-based LEDs, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable in order to adjust the light emitting characteristics.

0318GaN-based LEDs have these light emitting layers, p layers, n layers, electrodes, and substrates as basic components, and the light emitting layers are n-type and p-type Al._XGa_YN layer, GaN layer, or In_XGa_YThose having a heterostructure sandwiched by an N layer or the like have high luminous efficiency and are preferable, and those having a heterostructure having a quantum well structure have higher luminous efficiency and are more preferable.

0319The light emitting device emits white light, and the luminous efficiency of the device is 20 lm / W or more, preferably 22 lm / W or more, more preferably 25 lm / W or more, particularly preferably 28 lm / W or more, and an average. The color rendering index Ra is 80 or more, preferably 85 or more, and more preferably 88 or more.

0320The light emitting device can be used alone or in combination of a plurality of light emitting devices, for example, as a lighting lamp, a backlight for a liquid crystal panel, various lighting devices such as ultra-thin lighting, and an image display device.

<p num="0321"> Hereinafter, the present invention will be described in more detail with reference to examples, but they are for the purpose of explaining the present invention and are not intended to limit the present invention to these aspects.</p><p num="0322">[Analysis method] The semiconductor light emitting device members of the Examples and Comparative Examples described later were analyzed by the following procedure.</p><p num="0323"> [Brightness improvement rate] The brightness at a wavelength of 405 nm before and after the formation of the semiconductor light emitting device member was compared for each of the semiconductor light emitting devices obtained in Examples and Comparative Examples.</p><p num="0324"> [Measurement of solid-state Si-NMR spectrum and calculation of silanol content] Solid Si-NMR spectrum measurement and waveform separation analysis were performed on the semiconductor light emitting device members of each Example and each Comparative Example under the following conditions. From the obtained waveform data, the half width of each peak was obtained for the semiconductor light emitting device member of each Example and each Comparative Example. In addition, the ratio (%) of the silicon atom that is silanol in the total silicon atom is obtained from the ratio of the peak area derived from silanol to the total peak area, and the silanol content is calculated by comparing with the silicon content analyzed separately. I asked.</p><p num="0325"> &lt;Device conditions&gt; Equipment: Chemagnetics Infinity CMX-400 Nuclear Magnetic Resonance Spectroscopy²⁹Si resonance frequency: 79.436MHz Probe: 7.5mmφ CP / MAS probe Measurement temperature: room temperature Sample rotation speed: 4kHz Measurement method: Single pulse method¹H decoupling frequency: 50kHz²⁹Si flip angle: 90 °²⁹Si90 ° pulse width: 5.0 μs Repeat time: 600s Accumulation number: 128 times Observation width: 30kHz Broadening factor: 20Hz</p><p num="0326"> &lt;Data processing method&gt; For the semiconductor light emitting device members of Example 1 and Comparative Examples 1, 3 and 4, 512 points were taken in as measurement data, zero-filled to 8192 points, and Fourier transformed. On the other hand, for the semiconductor light emitting device member of Comparative Example 2 made of silicone resin, the peak was very sharp, so 2048 points were taken in as measurement data, zero-filled to 8192 points, and Fourier transformed.</p><p num="0327"> &lt;Waveform separation analysis method&gt; For each peak of the spectrum after Fourier transform, the optimization calculation was performed by the nonlinear least squares method with the center position, height, and half width of the peak shape created by the Lorentz waveform and Gauss waveform or a mixture of both as variable parameters. For the identification of peaks, AIChE Journal, 44 (5), p.1141, 1998, etc. were referred to.</p><p num="0328"> [Hardness measurement] The hardness (shore A) of the semiconductor light emitting device members of Examples and Comparative Examples was measured in accordance with JIS K6253 using an A type (durometer type A) rubber hardness tester manufactured by Furusato Seiki Seisakusho.</p><p num="0329"> [Measurement of transmittance] An ultraviolet spectrophotometer (UV-3100 manufactured by Shimadzu Corporation) using a single cured product film with a smooth surface of about 0.5 mm in thickness that is not scattered by scratches or irregularities of the semiconductor light emitting device members of Examples and Comparative Examples. The transmittance was measured at a wavelength of 200 nm to 800 nm. Table 2 shows the transmittance at a wavelength of 405 nm.</p><p num="0330"> [Ultraviolet light resistance test] For the semiconductor light emitting device members of Examples and Comparative Examples, a sample having a diameter of 5 cm and a film thickness of about 0.5 mm prepared using a Teflon (registered trademark) petri dish was irradiated with ultraviolet light under the following conditions, and before and after irradiation. The appearance of the membranes was compared. Irradiation device: Acceleration light resistance tester manufactured by Suga Test Instruments Co., Ltd. Metering weather meter MV30 Irradiation wavelength: 255 nm or later. The main wavelength is 300 nm to 450 nm (there is a bright line at 480 nm to 580 nm) Irradiation time: 72 hours</p><p num="0331"> [Heat resistance test] For the semiconductor light emitting device members of Examples and Comparative Examples, a sample having a diameter of 5 cm and a film thickness of about 0.5 mm prepared using a Teflon (registered trademark) petri dish was held in a ventilation dryer at a temperature of 250 ° C. for 5 days. .. The change in transmittance of this sample at 405 nm was compared before and after the test.</p><p num="0332"> [Reflow resistance test] (1) 7 μL of the hydrolyzed / polycondensate liquid before curing of the semiconductor light emitting device members of Examples and Comparative Examples was dropped into a ceramic cup having an opening diameter of 4 mm and a recess depth of 1 mm, and was placed in an explosion-proof furnace in a slight wind down. , 50 ° C. for 30 minutes, then 120 ° C. for 1 hour, and then 150 ° C. for 3 hours to prepare a sample for measurement.</p><p num="0333">(2) The obtained measurement sample was absorbed in an atmosphere at a temperature of 85 ° C and a humidity of 95% for 6 hours. (3) The hygroscopic measurement sample was placed on an iron plate having a surface temperature of 280 ° C for 90 seconds. Under these conditions, the maximum temperature reached for the measurement sample was 260 ° C, and the holding time of the measurement sample at this temperature was 30 seconds. (4) Next, the measurement sample was placed on a cooling plate (room temperature, made of stainless steel with a thickness of 1 cm) and cooled for 30 seconds.</p><p num="0334">(5) The sample for measurement after cooling was grasped with tweezers, and the middle part of the tweezers was lightly struck against the corner (edge) of the cooling plate 60 times to give an indirect impact. (6) The above steps (1) to (5) were repeated 6 times, and it was confirmed whether or not the semiconductor light emitting device member was peeled off.</p><p num="0335"> [Continuous lighting test] The semiconductor light emitting devices obtained in Examples and Comparative Examples were energized with a drive current of 20 mA and continuously lit at a temperature of 85 ° C and a relative humidity of 85%. The brightness after 150 hours was measured and compared with the brightness before the lighting test.</p><p num="0336"> [Measurement of silicon content] The independently cured product of the semiconductor light emitting device member of each example and each comparative example was crushed to about 100 μm, and in a platinum crucible in the air at 450 ° C for 1 hour, then at 750 ° C for 1 hour, 950 ° C. After removing the carbon component, add 10 times or more of sodium carbonate to a small amount of the obtained residue, heat it with a burner to melt it, cool it, add desalted water, and then add hydrochloric acid. While adjusting the pH to a neutral level, the volume was adjusted to about several ppm as silicon, and ICP analysis was performed.</p><p num="0337">[Example 1] Stirring 698.3 g of both-terminal silanol dimethyl silicone oil XC96-723 (oligoform) manufactured by Toshiba Silicone, 69.8 g of phenyltrimethoxysilane, 153.4 g of 5 wt% aluminum acetylacetone methanol solution as a catalyst, and 18.3 g of water. It was weighed in a three-ported colben equipped with wings and a condenser, stirred at room temperature for 15 minutes under atmospheric pressure, subjected to initial hydrolysis, and then refluxed while stirring at about 75 ° C for 4 hours. After that, methanol and low silicon boiling components were distilled off until the internal temperature reached 100 ° C., and the mixture was further refluxed at 100 ° C. for 4 hours with stirring. The reaction solution was cooled to room temperature, and the hydrolyzed / polycondensed solution was prepared. The hydrolysis rate of this solution is 192% with respect to phenyltrimethoxysilane. The raw material XC96-723 is equivalent to a 200% hydrolyzed product.</p><p num="0338"> This hydrolyzed / polycondensed solution was divided into two parts using a micropipette and dropped onto a GaN-based semiconductor light emitting device having a total emission wavelength of 4.5 μL and 405 nm. Then, it was held at 50 ° C for 30 minutes for the first drying, then at 120 ° C for 1 hour, and then at 150 ° C for 3 hours for the second drying, and it was transparent without cracks. An elastomeric sealing member was formed. The obtained semiconductor light emitting device was energized with 20 mA, and the brightness was measured. As a result, the [luminance improvement rate] and the [continuous lighting test] were measured.</p><p num="0339"> In addition, 3 g of the above-mentioned hydrolyzed polycondensate solution is placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm and held in an explosion-proof furnace at 50 ° C for 30 minutes for first drying, and then 120 ° C. After holding for 1 hour at 150 ° C. for 3 hours and then performing the second drying, an independent circular transparent elastomeric film having a thickness of about 0.5 mm was obtained. Using this, [solid Si-NMR spectrum measurement and calculation of silanol content] [hardness measurement] [measurement of transmittance] [ultraviolet light resistance test] [heat resistance test] [measurement of silicon content] were performed. Further, a [reflow resistance test] was performed using the above-mentioned hydrolyzed polycondensate solution. The solid Si-NMR spectrum of this example is shown in FIG.</p><p num="0340">[Comparative example 1]</p><p num="0341"> 27.4 g of dimethyldimethoxysilane, 1.6 g of methyltrimethoxysilane, 5.8 g of 5% acetylacetone aluminum salt methanol solution as a catalyst, and 5.3 g of water are mixed in a sealable container, sealed tightly, and stirred with a stirrer at 50 ° C. After heating in a warm water bath for 8 hours, the temperature was returned to room temperature, and the hydrolyzed / polycondensed solution was prepared. The hydrolysis rate of this solution is 120%.</p><p num="0342"> This hydrolyzed / polycondensed solution was divided into 5 times using a micropipette, and dropped onto a GAN-based semiconductor light emitting device having a total emission wavelength of 20 μL and 405 nm. After each dropping, the mixture was left at room temperature for a while, and when the solvent was volatilized and the next one (about 2 μL) could be added, the next dropping was performed. Then, it was held at 35 ° C for 30 minutes, then at 50 ° C for 1 hour for the first drying, and then held at 150 ° C for 3 hours for the second drying. Much volatilized and the tip could be sealed but the wire was exposed. In addition, using this, the [luminance improvement rate] was measured. The [continuous lighting test] could not be measured.</p><p num="0343"> In addition, 8 g of the above-mentioned hydrolyzed polycondensate solution was placed in a Teflon (registered trademark) petri dish with a diameter of 5 cm and held in an explosion-proof furnace at 40 ° C for 4 hours, and then from 40 ° C to 65 ° C for 3 hours. After the temperature was raised over and the first drying was performed, the temperature was maintained at 150 ° C. for 3 hours and the second drying was performed. As a result, an independent circular transparent elastomer-like film having a thickness of about 0.2 mm was obtained. This film was very soft and sticky, and was torn when taken out, so it could not be used for [measurement of transmittance], [ultraviolet light resistance test], [heat resistance test], and [reflow resistance test]. However, using this, [measurement of solid Si-NMR spectrum and calculation of silanol content] [measurement of hardness] [measurement of silicon content] were performed.</p><p num="0344">[Comparative example 2] A commercially available silicone resin (JCR6101UP manufactured by Toray Dow Corning Co., Ltd.) used as a molding agent for semiconductor light emitting devices is dropped onto a GaN-based semiconductor light emitting device having an emission wavelength of 405 nm with a micropipette, and at 150 ° C. When it was heated and dried for 2 hours, it became an elastomer-like sealing member (member for semiconductor light emitting device: sample A). The obtained semiconductor light emitting device was energized at 20 mA, and the brightness was measured. As a result, the [luminance improvement rate] and the [continuous lighting test] were measured.</p><p num="0345"> In addition, the above-mentioned silicone resin is applied to a Teflon (registered trademark) plate with an applicator, vacuum degassed at 25 ° C for 1 hour, heated at 150 ° C for 2 hours to dry, and then dried. It was peeled off to obtain an elastomeric film having a thickness of about 0.5 mm. Using this, [solid Si-NMR spectrum measurement and calculation of silanol content] [hardness measurement] [measurement of transmittance] [ultraviolet light resistance test] [heat resistance test] [measurement of silicon content] were performed. Further, a [reflow resistance test] was performed using the above silicone resin. The solid Si-NMR spectrum of this comparative example is shown in FIG. 51.</p><p num="0346">[Comparative example 3] A commercially available two-component curable aromatic epoxy resin used as a molding agent for semiconductor light emitting devices is dropped onto a GaN-based semiconductor light emitting device having an emission wavelength of 405 nm using a micropipette, and the mixture is dropped at 120 ° C for 4 hours. When it was heated and dried, it became a hard transparent sealing member (member for semiconductor light emitting device). The obtained semiconductor light emitting device was energized at 20 mA, and the brightness was measured. As a result, the [luminance improvement rate] and the [continuous lighting test] were measured.</p><p num="0347"> In addition, the above-mentioned epoxy resin was placed in a Teflon (registered trademark) petri dish with a diameter of 5 cm, vacuum degassed at 25 ° C for 1 hour, and then heated at 120 ° C for 4 hours to dry. The thickness was approximately 1 mm. And 0.5 mm bluish circular transparent resin film was obtained as an independent film. Using this, [solid Si-NMR spectrum measurement and calculation of silanol content] [hardness measurement] [measurement of transmittance] [ultraviolet light resistance test] [heat resistance test] [measurement of silicon content] were performed. Further, a [reflow resistance test] was performed using the above epoxy resin.</p><p num="0348">[Comparative example 4] Methyl silicate (MKC silicate MS51 manufactured by Mitsubishi Chemical Co., Ltd.) 30.80 g, methanol 56.53 g, water 6.51 g, 5% acetylacetone aluminum salt methanol solution 6.16 g as a catalyst are mixed in a sealable container, sealed and stirred with a stirrer. After heating for 8 hours in a warm water bath at 50 ° C., the mixture was returned to room temperature and the hydrolyzed / polycondensed solution was prepared. The hydrolysis rate of this solution is 113%.</p><p num="0349"> This hydrolyzed / polycondensed solution is dropped onto a GaN-based semiconductor light emitting device having an emission wavelength of 405 nm with a micropipette, and held at 35 ° C for 30 minutes and then at 50 ° C for 1 hour for the first drying. After that, when it was held at 150 ° C. for 3 hours and then dried for the second time, a large amount of cracks were generated and it could not be used as a sealing member (member for semiconductor light emitting device).</p><p num="0350"> Further, when 10 ml of the above-mentioned hydrolysis / polycondensation solution was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm and dried under the same conditions as in Example 1, a glass film having a thickness of about 0.3 mm was obtained. A large amount of cracks were generated in the middle of drying and shattered, and it was not possible to take out as an independent circular transparent glass film. However, using this, [measurement of silicon content] was performed.</p><p num="0351">[result of analysis] Table 2 shows the analysis results of the samples produced in the above Examples and Comparative Examples.<tables num="2"><img id="000007" he="179" wi="159" file="JP5694875B2_D0001.tif" img-format="tif" img-content="drawing" /></tables></p>

0352The application of the member for a semiconductor light emitting device of the present invention is not particularly limited, and it can be suitably used for various applications represented by a member (sealing agent) for sealing a semiconductor light emitting element or the like. Above all, it is particularly preferably used as a sealant or light extraction film for blue LED or near-ultraviolet LED, and as a phosphor retainer for high-power white LED using a light emitting element such as blue LED or near-ultraviolet LED as a light source. can do.

03531,1A, 1B light emitting device (semiconductor light emitting device) 2 light emitting element 3A transparent member (member for semiconductor device) 3B phosphor part (member for semiconductor device) 4a, 4b Part of the light emitted from the light emitting element 5 Light with a wavelength peculiar to fluorescent components such as phosphor particles, fluorescent ions, and fluorescent dyes contained in the phosphor part. 11 Mold part 12,13 Lead terminal 14 Mirror (cup part) 15 Conductive wire 16 Insulated substrate 16a recess 17 Printed wiring 18 Frame material 19 Seal 19a Sealing function 19b Lens function 19c recess 19d through hole 21 Light emitting layer 23 Reflective layer 24 bumps 33,34 Fluorescent part 35 solid medium