Light emitting element
Abstract
Problem to be solved.To provide a light emitting element having an improved degree of deterioration with respect to a driving time and a light emitting element whose emission color can be easily adjusted.
Solution.The layer has a first electrode, a second electrode, and a layer containing an organic compound located between the first electrode and the second electrode, and the layer containing the organic compound is the second. The first layer has at least a light emitting layer in which a first layer, a second layer, and a third layer are laminated from the electrode side of the above, and a hole transporting layer provided in contact with the third layer. It contains a first organic compound and a second organic compound, a second layer contains a third organic compound and a fourth organic compound, and a third layer contains a first organic compound and a fifth organic compound. To provide a light emitting element including. [Selection diagram] Fig. 1
Term
9.1 yearsto projected expiry
Projected expiry 22 October 2035, counted from filing; an application has no term until it is granted.
- Priority
- Filed
- Published
- Today
- Projected expiry
1 claim: 1 independent, 0 dependent
- 1陽極と、 陰極と、 前記陽極と前記陰極との間に、第1の発光層と、第2の発光層と、第3の発光層と、を有し、 前記第3の発光層は、前記陽極と前記第2の発光層との間に位置し、 前記第1の発光層は、前記陰極と前記第2の発光層との間に位置し、 前記第3の発光層は、正孔を輸送することができる機能を有する第5の有機化合物と、発光性の第1の有機化合物と、を有し、 前記第2の発光層は、正孔を輸送することができる機能を有する第4の有機化合物と、発光性の第3の有機化合物と、を有し、 前記第1の発光層は、電子を輸送することができる機能を有する第2の有機化合物と、発光性の前記第1の有機化合物と、を有し、 前記第1の有機化合物の発することができる色と、前記第3の有機化合物の発することができる色とは、互いに補色の関係にあり、 前記第1の有機化合物は、アミノ基とカルバゾリル基を有するアントラセン誘導体であることを特徴とする発光素子。
101 paragraphs, as filed
0001The present invention relates to a light emitting device using an organic compound at least in part. In addition, the luminescent element Regarding lighting devices, light emitting devices, and electronic devices equipped with children.
0002A layer containing an organic compound is provided between a pair of electrodes, and light is obtained by passing an electric current between the electrodes. Development of a light emitting device using a light emitting element capable of generating light is underway. Such a light emitting device Can be made thinner and lighter than the display devices currently called thin display devices. To. In addition, since it is self-luminous, it has good visibility and a fast response speed. Therefore, next-generation display equipment It has been actively developed as a device, and is currently being put into practical use, although it is a part of it.
0003Such a light emitting device depends on the material that becomes the light emitting center contained in the layer containing the organic compound. Various emission colors can be provided. In addition, a layer containing a light emitting center material exhibiting a different light emitting color. By stacking, the light emission is overlapped, and more light emission color variations are obtained. You can also do it. In particular, red, green, and blue lights are superimposed, and emission colors that complement each other are superimposed. The white light obtained by matching is used not only for displays, but also for bucklers. It is suitable for lighting and lighting, and is regarded as important.
0004One of the major reasons why such a light emitting device with many advantages is limited to practical use is There is a problem of deterioration of the optical element. Even if the light emitting element carries the same amount of current, it stores the drive time. As the product accumulates, its brightness decreases, causing deterioration. The degree of this deterioration is acceptable as an actual product It is not necessary to obtain a light emitting element that can be used in order for the light emitting device to be widely used. It is indispensable, and research has been done from many aspects such as drive circuit surface, sealing surface, element structure surface and material surface. (See, for example, Patent Document 1 and Patent Document 2).
0005However, there are various causes for the decrease in brightness due to the accumulation of drive time, and the current countermeasures have not been taken. It is also true that it is insufficient.
<p num="0006"><patcit num="1"><text>Japanese Unexamined Patent Publication No. 2006-114796</text></patcit><patcit num="2"><text>JP-A-2007-220593</text></patcit></p>
<p num="0007"> Therefore, in the present invention, a light emitting element or a lighting device in which the degree of deterioration with respect to the driving time is improved. The challenge is to provide.</p><p num="0008"> Further, the present invention provides a highly reliable light emitting device or electronic device in the display unit. Make it an issue.</p><p num="0009"> Another object of the present invention is to provide a light emitting element or a lighting device whose emission color can be easily adjusted. To do.</p><p num="0010"> Another object of the present invention is to provide a light emitting device or an electronic device having high display quality.</p>
<p num="0011"> One of the present invention is located between the first electrode, the second electrode, the first electrode and the second electrode. The layer containing the organic compound has a layer containing the organic compound, and the layer containing the organic compound is the first layer from the second electrode side. , A light emitting layer in which a second layer and a third layer are laminated, and a hole transport layer provided in contact with the third layer. The first layer contains the first organic compound and the second organic compound, and the second layer It contains a third organic compound and a fourth organic compound, and the third layer is the first organic compound and the fifth organic. Containing compounds, the second organic compound in the first layer is more by weight than the first organic compound In the second layer, the fourth organic compound contains more than the third organic compound in terms of weight. Rarely, in the third layer, the fifth organic compound is contained more than the first organic compound in terms of weight. It is a light emitting element. The light emitting device of the present invention having such a configuration accompanies the accumulation of driving time. It is possible to obtain a light emitting element having less decrease in brightness and improved reliability. Also, adjust the emission color It can be an easy light emitting element.</p><p num="0012"> Further, one of the present inventions is between the first electrode, the second electrode, the first electrode and the second electrode. It has a layer containing an organic compound located, and the layer containing an organic compound is the first layer from the second electrode side. A layer, a second layer, a layer responsible for light emission in which a third layer is laminated, and a layer provided in contact with the third layer. It has at least a hole transport layer, and the first layer contains a first organic compound and a second organic compound. , The second layer contains the third organic compound and the fourth organic compound, and the third layer is the first organic compound. And the fifth organic compound, the proportion of the first organic compound in the first layer is 0.1 wt% or more The top is less than 50 wt% and the proportion of the third organic compound in the second layer is more than 0.1 wt% Less than 50 wt% and the proportion of the first organic compound in the third layer is 0.1 wt% or more 5 It is a light emitting device having less than 0 wt%. The light emitting element of the present invention having such a configuration is driven. It is possible to obtain a light emitting element having improved reliability with less decrease in brightness due to accumulation of time. Ma In addition, it can be a light emitting element whose emission color can be easily adjusted.</p><p num="0013"> Further, one of the present inventions includes a first electrode, a second electrode, the first electrode, and the second electrode. It has a layer containing an organic compound located between the poles, and is the layer containing the organic compound on the second electrode side? The first layer, the second layer, and the third layer are laminated and provided in contact with the layer responsible for light emission and the third layer. It has at least a hole transporting layer, and the first layer contains a first organic compound and a second organic compound. Containing, the second layer contains the third organic compound and the fourth organic compound, the third layer is the first organicization The ratio of the first organic compound in the first layer is 0.1 wt, including the mixture and the fifth organic compound. % Or more and less than 50 wt%, and the proportion of the third organic compound in the second layer is 0.1 wt% More than 50 wt% and the proportion of the first organic compound in the third layer is 0.1 wt% or more Above 50 wt%, between the first electrode and the second electrode, the first electrode has a higher potential When a voltage is applied so as to be, light emission is obtained from the first organic compound and the third organic compound. It is a light emitting element. The light emitting device of the present invention having such a configuration accompanies the accumulation of driving time. It is possible to obtain a light emitting element having less decrease in brightness and improved reliability. Also, adjust the emission color It can be an easy light emitting element.</p><p num="0014"> Further, one of the present inventions includes a first electrode, a second electrode, the first electrode, and the second electrode. It has a layer containing an organic compound located between the poles, and is the layer containing the organic compound on the second electrode side? The first layer, the second layer, and the third layer are laminated and provided in contact with the layer responsible for light emission and the third layer. It has at least a hole transporting layer, and the first layer contains a first organic compound and a second organic compound. Containing, the second layer contains the third organic compound and the fourth organic compound, the third layer is the first organicization The ratio of the first organic compound in the first layer is 0.1 wt, including the mixture and the fifth organic compound. % Or more and less than 50 wt%, and the proportion of the third organic compound in the second layer is 0.1 wt% More than 50 wt% and the proportion of the first organic compound in the third layer is 0.1 wt% or more Above 50 wt%, the first organic compound is the luminescent center in the first and third layers It is a substance, and the third organic compound is a light emitting device which is a light emitting center material in the second layer. .. The light emitting element of the present invention having such a configuration has less decrease in brightness due to accumulation of driving time. , The light emitting element with improved reliability can be obtained. In addition, a light emitting element whose emission color can be easily adjusted. Can be.</p><p num="0015"> Further, in one of the present inventions, in the above configuration, the fourth organic compound and the fifth organic compound are positive. It is a pore-transporting material, and the second organic compound is a light-emitting device which is an electron-transporting material. This The light emitting element of the present invention having such a configuration has less decrease in brightness due to accumulation of driving time. , The light emitting element with improved reliability can be obtained. In addition, light emission with easy adjustment of emission color It can be an element.</p><p num="0016"> Further, in one of the present inventions, in the above configuration, the fourth organic compound is a condensed polycyclic substance. A light emitting element characterized by this. The light emitting device of the present invention having such a configuration has a band gap. Do not use a condensed polycyclic substance that is widely suitable as a host material as a host for the luminescent center material. However, it is possible to use a light emitting element with improved reliability with less decrease in brightness due to accumulation of drive time. it can. Further, the light emitting element can be easily adjusted in the light emitting color.</p><p num="0017"> Further, in one of the present inventions, in the above configuration, the fourth organic compound is condensed with 3 to 6 rings. A light emitting device characterized by being a polycyclic aromatic compound. The origin of the present invention having such a configuration The optical element has a wide bandgap and is suitable as a host material. Condensed polycyclics with 3 to 6 rings. While using an aromatic compound as a host for the luminescent center material, the brightness decreases as the driving time accumulates. It is possible to obtain a light emitting element with less reliability and improved reliability. In addition, it is easy to adjust the emission color. It can be an optical element.</p><p num="0018"> Further, in one of the present inventions, in the above configuration, the fourth organic compound is an anthracene derivative. A light emitting element characterized by the fact that. The light emitting device of the present invention having such a configuration is a band gear. Anthracene derivative, which is widely used as a host material, is used as a host for the luminescent center material. However, it should be a light emitting element with improved reliability with less decrease in brightness due to accumulation of drive time. Can be done. Further, the light emitting element can be easily adjusted in the light emitting color.</p><p num="0019"> Further, in one of the present inventions, the fourth organic compound and the fifth organic compound are the same in the above configuration. It is a light emitting element that is a substance. The light emitting device of the present invention having such a configuration is characterized by the above configuration. Further, it is possible to obtain a light emitting element having a simplified manufacturing process.</p><p num="0020"> Further, in one of the present inventions, in the above configuration, the peak wavelength of the light emitted by the first organic compound is It is a light emitting device having a wavelength shorter than the peak wavelength of light emitted by the third organic compound. like this The light-emitting element of the present invention having such a configuration has the characteristics of the light-emitting element having the above configuration, and further The light emitting element can be easily adjusted in the light emitting color.</p><p num="0021"> Further, one of the present inventions is the color of light emitted by the first organic compound and the third in the above configuration. It is a light emitting device in which the color of light emitted by an organic compound has a complementary color relationship with each other. Such a configuration The light emitting device of the present invention having the above-mentioned structure has the characteristics of the light emitting device having the above configuration, and is further white. You can get luminescence. The light emitting element of the present invention whose emission color can be easily adjusted is suitable for a white light emitting element. Can be applied to.</p><p num="0022"> Further, in one of the present inventions, in the above configuration, the first organic compound emits blue light, and the third An organic compound is a light emitting device that emits yellow light. Luminescent element of the present invention having such a configuration The child can obtain white light emission while having the characteristics of the light emitting element having the above configuration. .. The light emitting device of the present invention whose emission color can be easily adjusted can be suitably applied to a white light emitting device. ..</p><p num="0023"> Further, in one of the present inventions, in the above configuration, the peak wavelength of the light emitted by the first organic compound is It is in the range of 400 nm to 480 nm, and the peak wavelength of the light emitted by the third organic compound is 5. It is a light emitting device in the range of 40 nm to 600 nm. The present invention having such a configuration The light emitting element can obtain white light emission while having the characteristics of the light emitting element having the above configuration. it can. The light emitting device of the present invention whose emission color can be easily adjusted can be suitably applied to a white light emitting device. it can.</p><p num="0024"> Further, in one of the present inventions, in the above configuration, the first organic compound emits blue-green light, and the third The organic compound is a light emitting device that emits red light. Emission of the present invention having such a configuration While the element has the characteristics of the light emitting element having the above configuration, it is possible to further obtain white light emission. To. The light emitting device of the present invention whose emission color can be easily adjusted can be suitably applied to a white light emitting device. To.</p><p num="0025"> Further, in one of the present inventions, in the above configuration, the peak wavelength of the light emitted by the first organic compound is It is in the range of 480 nm to 520 nm, and the peak wavelength of the light emitted by the third organic compound is 6. It is a light emitting device in the range of 00 nm to 700 nm. The present invention having such a configuration The light emitting element can obtain white light emission while having the characteristics of the light emitting element having the above configuration. it can. The light emitting device of the present invention whose emission color can be easily adjusted can be suitably applied to a white light emitting device. it can.</p><p num="0026"> Further, one of the present inventions is a lighting device using the light emitting element described above. Such a configuration The lighting device having a long life is a lighting device having a small decrease in brightness due to the accumulation of driving time. Can be In addition, since it is easy to adjust the emission color, it is possible to output according to the application of the lighting device. The light color can be easily provided.</p><p num="0027"> Further, one of the present inventions includes the above-described light emitting element and means for controlling light emission of the light emitting element. It is a light emitting device. A light emitting device having such a configuration has a decrease in brightness due to accumulation of driving time. It can be a light emitting device having a short life and a long life. Also, because it is easy to adjust the emission color. It can be a light emitting device with high display quality.</p><p num="0028"> Further, one of the present inventions is an electronic device in which the above-described light emitting device is mounted on a display unit. this An electronic device having such a configuration can be an electronic device having a long display life. Also Since it is easy to adjust the emission color, it is possible to use an electronic device that has a display unit with high display quality. Wear.</p>
<p num="0029"> A light emitting device in which the degree of deterioration with respect to the driving time is improved by carrying out the present invention. Can be provided.</p><p num="0030"> Further, it is possible to provide a lighting device in which the degree of deterioration with respect to the driving time is improved.</p><p num="0031"> Further, it is possible to provide a highly reliable light emitting device or electronic device in the display unit.</p><p num="0032"> Further, it is possible to provide a light emitting element or a lighting device whose emission color can be easily adjusted.</p><p num="0033"> Further, it is possible to provide a light emitting device or an electronic device having high display quality.</p>
0034<figref num="1">The conceptual diagram of the light emitting element of this invention.</figref><figref num="2">Conceptual diagram of a conventional light emitting element.</figref><figref num="3">Top view and sectional view of the light emitting device of the present invention.</figref><figref num="4">A perspective view and a cross-sectional view of the light emitting device of the present invention.</figref><figref num="5">The figure which shows the electronic device of this invention.</figref><figref num="6">The figure which shows the electronic device of this invention.</figref><figref num="7">The figure which shows the electronic device of this invention.</figref><figref num="8">The figure which shows the electronic device of this invention.</figref><figref num="9">The figure which shows the current density-luminance characteristic of a light emitting element 1.</figref><figref num="10">The figure which shows the luminance-current efficiency characteristic of a light emitting element 1.</figref><figref num="11">The figure which shows the voltage-luminance characteristic of a light emitting element 1.</figref><figref num="12">The figure which shows the voltage-current characteristic of a light emitting element 1.</figref><figref num="13">The figure which shows the emission spectrum of a light emitting element 1.</figref><figref num="14">The figure which shows the current density-luminance characteristic of a light emitting element 2.</figref><figref num="15">The figure which shows the luminance-current efficiency characteristic of a light emitting element 2.</figref><figref num="16">The figure which shows the voltage-luminance characteristic of a light emitting element 2.</figref><figref num="17">The figure which shows the voltage-current characteristic of a light emitting element 2.</figref><figref num="18">The figure which shows the emission spectrum of a light emitting element 2.</figref><figref num="19">The figure which shows the emission spectrum of a light emitting element 3.</figref><figref num="20">The figure which shows the normalized luminance time change of a light emitting element 1 and a light emitting element 3.</figref><figref num="21">The figure which shows the current density-luminance characteristic of a light emitting element 4.</figref><figref num="22">The figure which shows the luminance-current efficiency characteristic of a light emitting element 4.</figref><figref num="23">The figure which shows the voltage-luminance characteristic of a light emitting element 4.</figref><figref num="24">The figure which shows the voltage-current characteristic of a light emitting element 4.</figref><figref num="25">The figure which shows the emission spectrum of a light emitting element 4.</figref><figref num="26">The figure which shows the current density-luminance characteristic of a light emitting element 5.</figref><figref num="27">The figure which shows the luminance-current efficiency characteristic of a light emitting element 5.</figref><figref num="28">The figure which shows the voltage-luminance characteristic of a light emitting element 5.</figref><figref num="29">The figure which shows the voltage-current characteristic of a light emitting element 5.</figref><figref num="30">The figure which shows the emission spectrum of a light emitting element 5.</figref><figref num="31">The figure which shows the emission spectrum of a light emitting element 6.</figref><figref num="32">The figure which shows the normalized luminance time change of a light emitting element 4 and a light emitting element 6.</figref><figref num="33">The figure which shows the current density-luminance characteristic of a light emitting element 7.</figref><figref num="34">The figure which shows the luminance-current efficiency characteristic of a light emitting element 7.</figref><figref num="35">The figure which shows the voltage-luminance characteristic of a light emitting element 7.</figref><figref num="36">The figure which shows the voltage-current characteristic of a light emitting element 7.</figref><figref num="37">The figure which shows the emission spectrum of a light emitting element 7.</figref><figref num="38">The figure which shows the current density-luminance characteristic of a light emitting element 8.</figref><figref num="39">The figure which shows the luminance-current efficiency characteristic of a light emitting element 8.</figref><figref num="40">The figure which shows the voltage-luminance characteristic of a light emitting element 8.</figref><figref num="41">The figure which shows the voltage-current characteristic of a light emitting element 8.</figref><figref num="42">The figure which shows the emission spectrum of a light emitting element 8.</figref>
0035Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, many of the present inventions It is possible to carry out in different aspects of the present invention, and deviates from the gist of the present invention and its scope. It is easily understood by those skilled in the art that the form and details can be changed in various ways. Obey Therefore, the interpretation is not limited to the description of the present embodiment.
0036(Embodiment 1) FIG. 2 shows a conceptual diagram of the conventional light emitting device 115 for the present invention. The light emitting element 115 is the first A layer 116 containing an organic compound is provided between the electrode 111 and the second electrode 110. It has become. Among the layers 116 containing the organic compound, the second layer 113 and the first layer 112 are the first. The hole transport layer 114 is provided in contact with the second layer 113, which is laminated from the electrode 111 side of the above. To. The first organic compound, which is the center of light emission, and the first organic compound are dispersed in the first layer 112. A second organic compound as a host material is contained, and the second layer 113 contains a second light emitting center. Includes a fourth organic compound as a host material that disperses the third organic compound and the third organic compound It is rare. The second organic compound is a material having electron transportability, and the fourth organic compound is a hole transporter. It is made of a material with properties. In addition, in this specification, "having electron transportability" means , At least the electron transportability is higher than the hole transportability, and "has hole transportability". At least means that the transportability of holes is higher than the transportability of electrons. Hole transport layer 114 is a substance having hole transporting property, which is provided to increase the distance between the electrode and the light emitting layer. It is configured.
0037In the light emitting element 115, the potential of the first electrode 111 is higher than the potential of the second electrode 110. When a voltage is applied between the first electrode 111 and the second electrode 110 to pass an electric current, the second electrode Electrons from 110 and holes from the first electrode 111 are on the layer 116 containing organic compounds. Infused. The injected carriers are located near the interface between the first layer 112 and the second layer 113. Most of them are recombined and the first organic compound and the third organic compound emit light, so that these 2 It is possible to obtain an emission in which the spectra of two emissions are overlapped. In addition, organic compounds In the containing layer 116, between the second electrode 110 and the first layer 112 and the first electrode 111 A layer may or may not be appropriately provided between the hole transport layer 114 and the hole transport layer 114.
0038In such a light emitting device 115, the present inventors have a second layer 113 and a hole transport layer 11. The first organic compound, which is the luminescent center substance contained in the first layer 112, is contained between the four and the first layer. A third layer containing the organic compound of 5 as a host material for dispersing the first organic compound is provided. It was found that the degree of deterioration of the light emitting element with respect to the driving time is improved by the above. Ta.
0039FIG. 1 shows a conceptual diagram of the light emitting element 106 according to the present embodiment. 1st electrode 101 and 2nd The third layer 104, the second layer 103, and the first layer 102 are the first electrodes between the electrodes 100 and the electrodes 100. It is stacked from the 101 side. Further, a hole transport layer 105 is provided in contact with the third layer 104. It has been. The first layer 102 separates the first organic compound and the first organic compound, which are the luminescence centers. The second organic compound as a host material to disperse is in the second layer 103, and the third is the emission center. The fourth organic compound as a host material for dispersing the organic compound and the third organic compound is the first. The host that disperses the first organic compound and the first organic compound, which are the luminescence centers, in the third layer 104. Each contains a fifth organic compound as a material. Here, in the first layer 102 The first organic compound and the first organic compound contained in the third layer 104 are the same substance. No. The second organic compound is a material having electron transportability, and the fourth organic compound is a material having hole transportability. Formed with.
0040Similarly to the light emitting element 115, the light emitting element 106 also has the potential of the first electrode 101 as the second electrode 1. When a voltage is applied between both electrodes so that the potential is higher than 00, the first organic compound and the third It is possible to obtain light emission from the organic compound of the above, but by providing the third layer 104, The light emitting element can have an improved degree of deterioration with respect to the moving time.
0041The reason why the degree of deterioration is improved is that in the light emitting element 115, the first layer 112 Electrons that did not contribute to recombination at the interface with the second layer 113 penetrated the second layer 113. Where deterioration occurred by reaching the hole transport layer 114, in the light emitting element 106, The provision of the third layer 104 reduced the number of electrons reaching the hole transport layer 105. It is thought that this is due to the fact.
0042A fifth organic substance contained as a host material for dispersing the luminescent center substance in the third layer 104. If the compound is a hole-transporting substance, the number of electrons reaching the hole-transporting layer 105 is further increased. This is a preferable configuration because it can be reduced. In addition, the fourth organic compound and the fifth possession The machine compound may be composed of the same material. In this case, the second layer 103 and the third layer 104 are formed. It is not necessary to replace the host material at the time of production, and the production process can be slightly simplified. When such a configuration is adopted, it is necessary to distinguish between the second layer 103 and the third layer 104. Depending on the type of luminescent center substance (third organic compound or first organic compound) Eggplant.
0043By the way, anthracene is a suitable substance as a host material for dispersing the luminescent center substance. There are condensed polycyclic materials such as condensed polycyclic aromatic compounds typified by derivatives. These materials Since the band gap is wide, the excitation energy is transferred from the luminescent center material. It is difficult to cause a decrease in luminous efficiency and a deterioration in color purity. Also, depending on the substituent, electron transport It has both properties and hole transport properties, and can be applied to light emitting devices having various configurations. However, there are many condensations Since the skeleton of the ring-based material itself has electron-transporting properties, it has hole-transporting properties due to substituents. Even if it is a high-quality material, it retains the ability to transport electrons to some extent, and it penetrates electrons. Depending on the conditions, the effect of deterioration due to injury may be large. In such a case In addition, when the configuration of the light emitting element 106 in the present embodiment is used, deterioration can be effectively suppressed. Can be done. The condensed polycyclic material used as the host material is 3 to 6 rings. Condensed polycyclic aromatic compounds of are particularly useful.
0044The first organic compound and the third organic compound, which are the luminescence center substances, have different emission colors. The substance to be presented may be used. As a result, the light emitting element emits light in which these two lights overlap. 106 can be exhibited and various emission colors can be obtained. Origin in this embodiment By using the configuration of the optical element 106, a desired emission color is exhibited and with respect to the driving time. A light emitting element having an improved degree of deterioration can be obtained.
0045Here, the light emitting device 106 of the present embodiment has a recombination region of electrons and holes as described above. Since the region is the interface between the first layer 102 and the second layer 103, there is a person who emits light with a shorter wavelength. Energy transfer has occurred from the machine compound to the organic compound that emits light with a longer wavelength. May occur. In such a case, why is the light emitted from an organic compound that emits light with a long wavelength? Also became stronger, and it was sometimes difficult to balance depending on the color combination. .. Therefore, in particular, as the first organic compound, the emission wavelength of the third organic compound is the emission of the third organic compound. In the third layer 104, the configuration using a substance exhibiting light emission shorter than the wavelength of the second layer 1 The first presence, albeit slightly, due to the recombination of the electrons and holes that penetrated from 03. Since the light emitted from the machine compound can be obtained, it is easy to balance the light emitting color of the light emitting element. To. This makes it possible to easily obtain a light emitting element having a desired light emitting color.
0046The configuration of the light emitting element 106 in the present embodiment as described above is white. It is also very useful in obtaining luminescence. Using the configuration of the light emitting element 106 in this embodiment By doing so, the desired white balance is achieved, and the degree of deterioration with respect to the driving time is achieved. Can be an improved white light emitting element. Further, the light emitting element 106 has the first presence. As a machine compound, its emission wavelength is shorter than the emission wavelength of the third organic compound. When a material-based configuration is applied, the desired white balance is achieved and the drive time is increased. It is possible to more easily obtain a light emitting element having an improved degree of deterioration.
0047When a white light emitting element is manufactured using the configuration of the light emitting element 106 in the present embodiment, the first The combination of emission colors emitted by the organic compound 1 and the organic compound 3 is red, blue-green, and yellow. A combination of colors that are complementary colors such as blue and blue may be used. In particular, the first organic matter A combination of substances that emit blue as a compound and yellow as a third organic compound, and the first A combination of substances that emit blue-green as an organic compound and red as a third organic compound. As a first organic compound, a substance that emits light having a wavelength shorter than the emission color of the third organic compound. Is preferable because it is easy to balance the emission color of the light emitting element. Is.
0048Further, a place where a white light emitting element is manufactured using the configuration of the light emitting element 106 in the present embodiment. Then, as another example of the combination of the emission colors emitted by the first organic compound and the third organic compound, , Light with peak wavelength in the range of 600nm to 700nm and peak wavelength of 480nm to 5 Light combinations within the 20 nm range and peak wavelengths within the 540 nm to 600 nm range There is a combination of some light and light with a peak wavelength in the range of 400 nm to 480 nm. Also Of course, in this case as well, the wavelength of the first organic compound is shorter than the emission color of the third organic compound. It is preferable to use a substance that emits light because it is easy to balance the emission color of the light emitting element. It will be a good composition.
0049Subsequently, the above-mentioned light emitting element will be described more specifically with reference to the manufacturing method. In addition, it should be noted The element configurations and manufacturing methods described here are merely examples, and are examples that do not impair the gist of the present invention. Other known configurations, materials and fabrication methods can be applied in the enclosure.
0050FIG. 1 schematically shows an example of the element configuration of the light emitting device in the present invention. Luminescent element shown in Fig. 1 The child has a layer 107 containing an organic compound between the second electrode 100 and the first electrode 101. It is composed. The layer 107 containing the organic compound is at least the first light emitting central substance. A third layer 104 containing the organic compound of the above and a fifth organic compound which is a host material, and a light emitting center. A second layer containing a third organic compound that is a substance and a fourth organic compound that is a host material 103 And the first layer 102 containing the first organic compound and the second organic compound which is the host material. Light emitting layer (here, light emission in the third layer) composed of laminated bodies laminated in order from the electrode 101 side of Can be obtained or not), and the hole transfer provided in contact with the third layer 104. It has a feed layer 105. An electron injection layer or an electron transport layer is located between the light emitting layer and the second electrode 100. A layer such as a hole injection layer is appropriately provided between the hole transport layer 105 and the first electrode 101. It may be. Either of the first electrode 101 and the second electrode 100 is an anode, The other is the cathode, but in this embodiment, the first electrode 101 is the anode and the second electrode 100 is the cathode. The case where is a cathode will be described. The anode in the present invention is a hole in a layer containing a light emitting material. The cathode is an electrode that injects electrons into a layer containing a light emitting material. Shown.
0051First, an anode is formed on the insulating surface. As an anode, it has a large work function (specifically, 4). .0eV and above) It is preferable to use metals, alloys, conductive compounds, and mixtures thereof. Good. Specifically, indium tin oxide (hereinafter referred to as ITO), silicon, or Indium tin oxide containing silicon oxide, indium oxide containing zinc oxide (ZnO), acid Examples thereof include indium oxide (IWZO) containing tungsten oxide and zinc oxide. This These conductive metal oxide films are usually formed by sputtering, but sol-gel methods are used. You may make it by using. For example, indium oxide containing zinc oxide (ZnO) is oxidized. Sputtering using a target with 1-20 wt% zinc oxide added to indium It can be formed by law. In addition, oxide a containing tungsten oxide and zinc oxide Indium (IWZO) contains 0.5 to 5 wt% of tungsten oxide with respect to indium oxide. Formed by sputtering using a target containing 0.1 to 1 wt% zinc oxide Can be In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (C) u), palladium (Pd), or a nitride of metallic material (eg titanium nitride) is used. It is also possible.
0052Subsequently, a layer containing an organic compound is formed. The layer 107 containing an organic compound is a low molecular weight material. Either a material or a polymer-based material can be used. Layer 107 containing an organic compound The materials that make up the above are not only those that consist only of organic compound materials, but also some inorganic compounds. The including configuration shall also be included. In addition, the layer 107 containing the organic compound is usually a hole injection layer, Hole transport layer, hole blocking layer (hole blocking layer), light emitting layer, electron transport layer, electron injection layer, etc. , It is configured by appropriately combining functional layers having each function. Functions of each layer A layer including a layer having two or more at the same time may be formed, and the above-mentioned waste It is not necessary that either layer is formed. Of course, a layer other than the above-mentioned functional layer is provided. You may stay. In the present embodiment, holes are injected in order from the anode side as the layer 107 containing the organic compound. It consists of an entry layer, a hole transport layer, and a light emitting layer (third layer 104, second layer 103, and first layer 102. A light emitting device having a laminated structure of an electron transport layer and an electron injection layer will be illustrated and described. I will do it.
0053When a hole injection layer is used, as a material that functions as the hole injection layer, vanadium oxide or Examples thereof include metal oxides such as molybdenum oxide, ruthenium oxide, and aluminum oxide. Alternatively, if it is an organic compound, a porphyrin-based compound is effective, and phthalocyanine ( Abbreviation: H<sub>2</sub>Pc), copper phthalocyanine (abbreviation: CuPc) and the like can be used. Also , Polymer compounds (oligomers, dendrimers, polymers, etc.) are used as the hole injection layer. You can also. For example, poly (N-vinylcarbazole) (abbreviation: PVK), poly (4) -Vinyltriphenylamine) (abbreviation: PVTPA), poly [N- (4- {N'-[4- (4-Diphenylamino) Phenyl] Phenyl-N'-Phenylamino} Phenyl) Meta Crillamide] (abbreviation: PTPDMA) Poly [N, N'-bis (4-butylphenyl)- Polymerization of N, N'-bis (phenyl) benzidine] (abbreviation: Poly-TPD) Things can be mentioned. Also, poly (3,4-ethylenedioxythiophene) / poly (styrene) Sulfonic Acid) (PEDOT / PSS), Polyaniline / Poly (Styrene Sulfonic Acid) (P An acid-added polymer compound such as Ani / PSS) can be used. The hole injection layer is positive Formed in contact with the poles, the use of hole injection layers reduces the injection barrier of carriers. Carriers are efficiently injected into the light emitting element, and as a result, the drive voltage can be reduced. ..
0054Further, as a hole injection layer, a material containing an acceptor substance in a substance having a high hole transport property. A material (hereinafter referred to as a composite material) can be used. It should be noted that substances with high hole transport properties By using a substance containing a scepter substance, ohm contact with the electrode becomes possible. , The material that forms the electrode can be selected regardless of the work function. In other words, work as an anode Not only a large number of materials but also a material having a small work function can be used. Acceptor As a sex substance, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquino Dimethane (abbreviation: F)<sub>4</sub>-TCNQ), chloranil, etc. can be mentioned. Also, transition money Genus oxides can be mentioned. In addition, metals belonging to Group 4 to Group 8 in the Periodic Table of the Elements Oxides can be mentioned. Specifically, vanadium oxide, niobium oxide, tanta oxide Le, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, rhenium oxide are electric It is preferable because it has high child receptivity. Above all, molybdenum oxide is stable in the atmosphere and absorbs It is preferable because it has low wettability and is easy to handle.
0055In addition, in this specification, a composite means not only mixing two materials but also a plurality of materials. By mixing the materials of, it is said that the charge can be transferred between the materials. ..
0056Aromatic amine compounds and carbazole are examples of substances with high hole transport properties used in composite materials. Derivatives, aromatic hydrocarbons, polymer compounds (oligomers, dendrimers, polymers, etc.), etc. , Various compounds can be used. In addition, with substances with high hole transport properties used in composite materials Then 10<sup>-6</sup>cm<sup>2</sup>It is preferable that the substance has a hole mobility of / Vs or more. However However, any substance other than these may be used as long as it is a substance having a higher hole transport property than electrons. After Below, organic compounds that can be used as substances with high hole transport properties in composite materials are listed. List specifically.
0057For example, 4,4'-bis is an aromatic amine compound that can be used in composite materials. [N- (1-naphthyl) -N-Phenylamino] Biphenyl (abbreviation: NPB or α-N) PD), N, N'-bis (4-methylphenyl) -N, N'-diphenyl-p-phenyle Ndiamine (abbreviation: DTDPPA), 4,4'-bis [N- (4-diphenylaminofe) Nyl) -N-Phenylamino] Biphenyl (abbreviation: DPAB), N, N'-bis [4- [ Bis (3-Methylphenyl) Amino] Phenyl] -N, N'-Diphenyl- [1,1'- Biphenyl] -4,4'-diamine (abbreviation: DNTPD), 1,3,5-tris [N-(abbreviation: DNTPD) 4-Diphenylaminophenyl) -N-Phenylamino] Benzene (abbreviation: DPA3B) And so on.
0058Specific examples of the carbazole derivative that can be used in the composite material include 3-[N-. (9-Phenylcarbazole-3-yl) -N-Phenylamino] -9-Phenylcarba Zol (abbreviation: PCzPCA1), 3,6-bis [N- (9-phenylcarbazole-3) -Il) -N-Phenylamino] -9-Phenylcarbazole (abbreviation: PCzPCA2) , 3- [N- (1-naphthyl) -N- (9-phenylcarbazole-3-yl) amino] -9-Phenylcarbazole (abbreviation: PCzPCN1) and the like can be mentioned.
0059Moreover, as a carbazole derivative that can be used for a composite material, 4,4'-di (N) -Carbazole) Biphenyl (abbreviation: CBP), 1,3,5-Tris [4- (N-carba) Zoryl) Phenyl] Benzene (abbreviation: TCPB), 9- [4- (10-Phenyl-9-a) Toril) Phenyl] -9H-carbazole (abbreviation: CzPA), 1,4-bis [4- ( N-carbazolyl) phenyl] -2,3,5,6-Tetraphenylbenzene, etc. should be used. Can be done.
0060In addition, aromatic carbonization that can be used for composite materials 2-tert. -Butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA), 2- tert-Butyl-9,10-di (1-naphthyl) anthracene, 9,10-bis (3, 5-diphenylphenyl) anthracene (abbreviation: DPPA), 2-tert-butyl-9 , 10-bis (4-phenylphenyl) anthracene (abbreviation: t-BuDBA), 9,1 0-di (2-naphthyl) anthracene (abbreviation: DNA), 9,10-diphenyl anthracene Sen (abbreviation: DPAnth), 2-tert-butylanthracene (abbreviation: t-BuAn) th), 9,10-bis (4-methyl-1-naphthyl) anthracene (abbreviation: DMNA) , 9,10-Bis [2- (1-naphthyl) phenyl] -2-tert-butyl-anthra Sen, 9,10-bis [2- (1-naphthyl) phenyl] anthracene, 2,3,6,7 -Tetramethyl-9,10-di (1-naphthyl) anthracene, 2,3,6,7-tetra Methyl-9,10-di (2-naphthyl) anthracene, 9,9'-bianthracene, 10, 10'-diphenyl-9,9'-bianthril, 10,10'-bis (2-phenylfe) Nil)-9,9'-Biantril, 10,10'-Bis [(2,3,4,5,6-Penta) Phenyl) Phenyl]-9,9'-bianthracene, anthracene, tetracene, rubrene , Perylene, 2,5,8,11-tetra (tert-butyl) perylene and the like. In addition, pentacene, coronene and the like can also be used. Thus, 1x10<sup>-</sup><sup>6</sup>cm<sup>2</sup>Uses aromatic hydrocarbons with hole mobility of / Vs or higher and 14 to 42 carbon atoms Is more preferable.
0061The aromatic hydrocarbon that can be used for the composite material may have a vinyl skeleton. I. Examples of aromatic hydrocarbons having a vinyl group include 4,4'-bis (2,2-). Diphenylvinyl) Biphenyl (abbreviation: DPVBi), 9,10-bis [4- (2,2-) Diphenylvinyl) Phenyl] Anthracene (abbreviation: DPVPA) and the like.
0062In addition, polymer compounds such as PVK, PVTPA, PTPDMA, and Poly-TPD described above A composite material is formed from the material and the acceptor material described above, and used as a hole injection layer. May be good.
0063When such a composite material is used as a hole injection layer, the anode is affected by the magnitude of the work function. Instead, various metals, alloys, electrically conductive compounds, and mixtures thereof can be used. it can. Therefore, as the anode, in addition to the materials described above, for example, aluminum (Al) and silver (Ag), an alloy containing aluminum (AlSi), or the like can be used. Also, work relations Elements belonging to Group 1 or Group 2 of the Periodic Table of the Elements, which is a small number of materials, that is, Lithium Alkali metals such as lithium (Li) and cesium (Cs), and magnesium (Mg) and calcium. Alkaline earth metals such as um (Ca) and strontium (Sr), and alloys containing them. Rare earth gold such as (MgAg, AlLi), Europium (Eu), Ytterbium (Yb) Genus and alloys containing these can also be used. Alkaline metal, alkaline earth metal, A film of an alloy containing these can be formed by using a vacuum deposition method. Also, alkaline gold Alloy films containing genus or alkaline earth metals can also be formed by sputtering. Is. It is also possible to form a film of silver paste or the like by an inkjet method or the like. ..
0064The hole transport layer is N, N'-bis (spiro-9,9'-bifluoren-2-yl) -N, N'-diphenylbenzidine (abbreviation: BSPB), 4,4'-bis [N- (1-naphthyl) )-N-Phenylamino] Biphenyl (abbreviation: NPB or α-NPD), 4,4'-bi Su [N- (3-Methylphenyl) -N-Phenylamino] Biphenyl (abbreviation: TPD), 4,4', 4''-Tris (N, N-diphenylamino) Triphenylamine (abbreviation: T) DATA), 4,4', 4''-Tris [N- (3-Methylphenyl) -N-Phenyla Mino] Triphenylamine (abbreviation: MTDATA), N, N'-bis [4- [bis (3-] Methylphenyl) amino] phenyl] -N, N'-diphenyl- [1,1'-biphenyl ] -4,4'-Diamine (abbreviation: DNTPD), 1,3,5-Tris [N, N-di (m-) Trill) Amino] Benzene (abbreviation: m-MTDAB), 4,4', 4''-Tris (N- Carbazole) Triphenylamine (abbreviation: TCTA), phthalocyanine (abbreviation: H)<sub>2</sub>P c), Copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc) ) And other suitable materials can be used. 10 as a hole transport layer<sup>-6</sup>cm<sup>2</sup>/ Vs and above It is preferable to use a substance having the hole mobility of, but a substance having a higher hole transport property than an electron. If so, it can be used as a hole transport layer. Also, the hole transport layer is only a single layer structure. Rather, it has a multi-layer structure in which two or more layers of substances that meet the above conditions are combined. It may be a layer. The hole transport layer can be formed by using a vacuum vapor deposition method or the like.
0065In addition, as hole transport layers, PVK, PVTPA, PTPDMA, Poly-TPD, etc. It is also possible to use the polymer compound of. In this case, the inkjet method or spin coating A solution process can be used.
0066The hole transport layer in contact with the light emitting layer has a first substance, which is the light emitting center substance of the third layer 104. It is preferable to use a substance having an excitation energy larger than the excitation energy of the machine compound. I'm sorry. With such a configuration, energy transfer from the light emitting layer to the hole transport layer is suppressed. It can be controlled and high luminous efficiency can be realized.
0067As for the light emitting layer, is the third layer 104, the second layer 103, or the first layer 102 on the side of the first electrode 101? Are laminated. In the first layer 102, the first organic compound which is the center of emission and the first A second organic compound as a host material for dispersing the organic compound emits light in the second layer 103. The fourth possession as a host material for dispersing the central third organic compound and the third organic compound The machine compound has the first organic compound and the first organic compound, which are the emission centers, in the third layer 104. Each contains a fifth organic compound as a host material to disperse. Here, the first The first organic compound in the layer 102 and the first organic compound contained in the third layer 104 are the same. It is a substance. The second organic compound is a material having electron transportability, the fourth organic compound and the fifth. The organic compound is made of a material having a hole transporting property. The host material is the light emitting center. Since it has the function of dispersing the substance, it is more than the substance that is the center of light emission in each layer. It will be included a lot. In addition, the ratio of the substance that becomes the center of light emission in each layer is 0.1. It may be wt% or more and less than 50 wt%. The light emitting layer can be made using the vacuum deposition method. It can be produced by a co-deposited method in which different materials are vapor-deposited at the same time.
0068The first organic compound and the third organic compound are substances that are the center of light emission, and each has a different wavelength. Select a substance that emits light. The following substances can be mentioned as substances that are the center of light emission. However, of course, it is not limited to this. Exhibits blue emission (emission wavelength 400nm ~ 480nm) N, N'-bis [4- (9H-carbazole-9-yl) pheni Le] -N, N'-diphenylstilbene-4,4'-diamine (abbreviation: YGA2S), 4 -(9H-carbazole-9-yl) -4'-(10-phenyl-9-anthril) tri Phenylamine (abbreviation: YGAPA), 4- (9H-carbazole-9-yl) -4'- (9,10-Diphenyl-2-anthril) Triphenylamine (abbreviation: 2YGAPPA) ), N, 9-Diphenyl-N- [4- (10-Phenyl-9-Anthryl) Phenyl]- 9H-carbazole-3-amine (abbreviation: PCAPA), 4- (10-phenyl-9-a) Toril) -4'-(9-Phenyl-9H-carbazole-3-yl) Triphenylami (Abbreviation: PCBAPA), perylene, 2,5,8,11-tetra-tert-butylpe Examples include riren (abbreviation: TBP). Also, bis [2- (4', 6'-difluoro Phenyl) pyridinato-N, C<sup>2’</sup>] Iridium (III) Tetrakis (1-Pyrazolyl ) Borato (abbreviation: FIr6), bis [2- (4', 6'-difluorophenyl) pyridi Nato-N, C<sup>2’</sup>] Like iridium (III) picolinate (abbreviation: F Irpic) Materials that emit phosphorescence can also be used. Blue-green emission (emission wavelength 480nm ~ 520n Examples of substances exhibiting m) are N, N''-(2-tert-butylanthracene-9). , 10-Diyldi-4,1-phenylene) Bis [N, N', N'-triphenyl-1,4 -Phenylene diamine] (abbreviation: DPABPA), N, 9-diphenyl-N- [4- (9) , 10-Diphenyl-2-anthryl) Phenyl] -9H-carbazole-3-amine ( Abbreviation: 2PCAPPA), N- [4- (9,10-diphenyl-2-anthril) pheni Le] -N, N', N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAP) PA), N, N, N', N', N'', N'', N''', N'''-octaphenyldi Benzo [g, p] Chrysene-2,7,10,15-Tetraamine (abbreviation: DBC1), Marine 30 and the like. Also, bis [2- (3', 5'-bistrifluoromethyl Phenyl) pyridinato-N, C<sup>2’</sup>] Iridium (III) picolinate (abbreviation: Ir (abbreviation: Ir) CF<sub>3</sub>ppy)<sub>2</sub>(pic)), bis [2- (4', 6'-difluorophenyl) pyridi Nato-N, C<sup>2’</sup>] Iridium (III) Acetylacetoneate (abbreviation: FIracac) A material that emits phosphorescence such as) can also be used. Yellow emission (emission wavelength 540nm ~ Examples of substances exhibiting (600 nm) are rubrene, 5,12-bis (1,1'-buffet). Nyl-4-yl) -6,11-diphenyltetracene (abbreviation: BPT), 2- (2- {2 -[4- (Dimethylamino) phenyl] ethenyl} -6-methyl-4H-pyran-4-i LIDEN) Propanedinitrile (abbreviation: DCM1), 2- {2-methyl-6- [2- (2,, 3,6,7-Tetrahydro-1H, 5H-benzo [ij] quinolizidine-9-yl) eteni Le] -4H-pyran-4-iriden} propandinitrile (abbreviation: DCM2), etc. Be done. Also, bis (benzo [h] quinolinato) iridium (III) acetylacetona (Abbreviation: Ir (bzq)<sub>2</sub>(acac)), bis (2,4-diphenyl-1,3-o) Kisazorat-N, C<sup>2’</sup>) Iridium (III) Acetylacetoneate (abbreviation: Ir (d) po)<sub>2</sub>(acac)), bis [2- (4'-perfluorophenylphenyl) pyridina G] Iridium (III) Acetylacetoneate (abbreviation: Ir (p-PF-ph))<sub>2</sub>(a cac))), bis (2-phenylbenzothiazolato-N, C<sup>2’</sup>) Iridium (III) Acetylacetone (abbreviation: Ir (bt))<sub>2</sub>(acac))) phosphorescent material Can also be used. Of a substance that emits red light (emission wavelength 600 nm to 700 nm) For example, N, N, N', N'-Tetrakis (4-methylphenyl) Tetracene-5, 11-diamine (abbreviation: p-mPhTD), 7,13-diphenyl-N, N, N', N' -Tetrakis (4-Methylphenyl) Asenaft [1,2-a] Fluoranthene-3,1 0-diamine (abbreviation: p-mPhAFD), {2-isopropyl-6- [2- (1,1,1) 7,7-Tetramethyl-2,3,6,7-Tetrahydro-1H, 5H-Benzodiazepine [ij] Nolysine-9-yl) ethenyl] -4H-pyran-4-iriden} propandinitrile ( Abbreviation: DCJTI), {2-tert-butyl-6- [2- (1,1,7,7-tetrame) Chill-2,3,6,7-Tetrahydro-1H, 5H-Benzodiazepine [ij] Quinolizidine-9-a Le) Ethenyl] -4H-pyran-4-iriden} propandinitrile (abbreviation: DCJTB) ), 4- (Dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4 H-Pyran (abbreviation: BisDCM), {2,6-bis [2- (8-methoxy-1,1,7) , 7-Tetramethyl-2,3,6,7-Tetrahydro-1H, 5H-Benzo [ij] Kino Lysine-9-yl) ethenyl] -4H-pyran-4-iriden} propandinitrile (abbreviation) Name: BisDCJTM) and so on. Also, the screw [2- (2'-benzo [4,5- α] thienyl) pyridinat-N, C<sup>3’</sup>] Iridium (III) Acetylacetoneate ( Abbreviation: Ir (btp)<sub>2</sub>(acac)), Bis (1-Phenylisoquinolinato-N, C<sup>2</sup><sup>’</sup>) Iridium (III) Acetylacetoneate (abbreviation: Ir (piq))<sub>2</sub>(acac) ), (Acetylacetonato) bis [2,3-bis (4-fluorophenyl) quinoxalina G] Iridium (III) (abbreviation: Ir (Fdpq)<sub>2</sub>(acac)), 2,3,7,8 , 12,13,17,18-Octaethyl-21H, 23H-Porphyrin Shirokane (II) (Abbreviation: PtOEP), Tris (1,3-diphenyl-1,3-propanedionat) (mo Nophenanthroline) Europium (III) (abbreviation: Eu (DBM)<sub>3</sub>(Phen)) , Tris [1- (2-tenoyl) -3,3,3-trifluoroacetonato] (monophena) Phosphorescent materials such as entroline) europium (III) can also be used. The materials are not listed in the range of 520nm to 540nm, but of course this Luminescent materials with emission wavelengths in the range (including materials that emit phosphorescence) can also be used. .. A substance having a different emission wavelength from these can be obtained from a light emitting element in a desired emission color. Each can be selected and used as described above. As an example of the combination, for example, the first When 2YGAPPA is used as the organic compound and rubrene is used as the third organic compound, the white color becomes white. can get. Also, for example, 2PCAPPA as the first organic compound and the third organic compound. White color can also be obtained by using BisDCM. Further, for example, 2Y as the first organic compound GAPPA, if BisDCM is used as the third organic compound, a neutral color such as purple can be obtained. Be done.
0069Further, the electron-hole recombination region is near the interface between the first layer 102 and the second layer 103. Therefore, from the organic compound that emits light with a short wavelength, the organic compound that emits light with a long wavelength Energy transfer may occur. In such a case, it emits light with a long wavelength. The luminescence from the organic compounds is inevitably strong, and it varies depending on the color combination. Sometimes it's difficult to get rid of. At this time, the substance that emits light with a short wavelength is the first organic substance. When a substance that emits light with a long wavelength is used as the third organic compound, the third is used. In the layer 104, the electrons and holes that penetrated from the second layer 103 are recombined. Therefore, although it is slight, the emission color of the light emitting element can be obtained because the emission from the first organic compound can be obtained. It becomes easy to balance. As a result, the desired emission color is exhibited and the driving time is increased. A light emitting element having an improved degree of deterioration can be easily obtained. This is especially white It is useful for adjusting the white balance of the light emitting element.
0070Used as a host material for dispersing the first organic compound or the third organic compound, Examples of the second organic compound, the fourth organic compound and the fifth organic compound include tris (8). -Kinolinolato) Aluminum (abbreviation: Alq), Tris (4-Methyl-8-Kinolinora) G) Aluminum (abbreviation: Almq<sub>3</sub>), Bis (10-hydroxybenzo [h] quinolina G) Beryllium (abbreviation: BeBq<sub>2</sub>), Bis (2-methyl-8-quinolinolato) (4-F) Enilphenorato) Aluminum (abbreviation: BAlq), Bis (8-quinolinolato) Zinc ( II) (abbreviation: Znq), bis [2- (2-benzoxazolyl) phenolato] zinc (I) I) (abbreviation: ZnPBO), bis [2- (2-benzothiazolyl) phenolato] zinc (I) Metal complexes such as I) (abbreviation: ZnBTZ), 2- (4-biphenylyl) -5- (4-te rt-Butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bi Su [5- (p-tert-butylphenyl) -1,3,4-oxadiazole-2-yl ] Benzene (abbreviation: OXD-7), 3- (4-biphenylyl) -4-phenyl-5- (4) -tert-Butylphenyl) -1,2,4-triazole (abbreviation: TAZ), 2,2' , 2''-(1,3,5-benzenetriyl) Tris (1-phenyl-1H-benzoimi) Dazole) (abbreviation: TPBI), basophenanthroline (abbreviation: BPhen), basocu Proin (abbreviation: BCP), 9- [4- (5-phenyl-1,3,4-oxadiazole) -2-Il) Phenyl] -9H-Heterocyclic compounds such as carbazole (abbreviation: CO11), Aromatic amine compounds such as NPB (or α-NPD), TPD, BSPB can be mentioned. .. In addition, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, chrysene derivatives, Condensed polycyclic aromatic compounds such as dibenzo [g, p] chrysene derivatives can be mentioned, specifically. 9,10-Diphenylanthracene (abbreviation: DPAnth), N, N-diphenyl-9- [4- (10-Phenyl-9-anthryl) phenyl] -9H-carbazole-3-ami (Abbreviation: CzA1PA), 4- (10-Phenyl-9-Anthryl) Triphenylami (Abbreviation: DPhPA), 4- (9H-carbazole-9-yl) -4'-(10-fe) Nyl-9-anthril) Triphenylamine (abbreviation: YGAPA), N, 9-diphenyl -N- [4- (10-Phenyl-9-Anthryl) Phenyl] -9H-Carbazole-3 -Amine (abbreviation: PCAPA), N, 9-diphenyl-N- {4- [4- (10-Pheni) Le-9-anthryl) Phenyl] Phenyl} -9H-carbazole-3-amine (abbreviation: abbreviation: PCAPBA), N,9-diphenyl-N- (9,10-diphenyl-2-anthril) -9H-carbazole-3-amine (abbreviation: 2PCAPA), 9-phenyl-9'-[4 -(10-Phenyl-9-anthryl) phenyl] -3,3'-bi (9H-carbazole) ) (Abbreviation: PCCPA), 4- (10-Phenyl-9-Anthril) -4'-(9-Fe Nyl-9H-carbazole-3-yl) triphenylamine (abbreviation: PCBAPA), 6 , 12-dimethoxy-5,11-diphenylchrysene, N, N, N', N', N'', N '', N''', N'''-Octaphenyldibenzo [g, p] Chrysene-2,7,10 , 15-Tetraamine (abbreviation: DBC1), 9- [4- (10-Phenyl-9-Antri) Le) Phenyl] -9H-carbazole (abbreviation: CzPA), 3,6-diphenyl-9- [ 4- (10-Phenyl-9-anthryl) phenyl] -9H-carbazole (abbreviation: DP) CzPA), 9,10-bis (3,5-diphenylphenyl) anthracene (abbreviation: DP) PA), 9,10-di (2-naphthyl) anthracene (abbreviation: DNA), 2-tert- Butyl-9,10-di (2-naphthyl) anthracene (abbreviation: t-BuDNA), 9,9 '-Biantril (abbreviation: BANT), 9,9'-(Stilbene-3,3'-Jill) Ji Phenanthrene (abbreviation: DPNS), 9,9'-(Stilbene-4,4'-Zeil) Ziff Enantren (abbreviation: DPNS2), 3,3', 3''-(benzene-1,3,5-tri) Il) Tripylene (abbreviation: TPB3) can be mentioned. These and known substances Energy gap larger than the energy gap of the luminescent central material in which each is dispersed A substance having a sap may be selected. In addition, when the light emitting center substance emits phosphorescence, the host material As a material, the triplet energy of the luminescent center material (energy between the ground state and the triplet excited state) -A substance having a triplet energy larger than (difference) may be selected.
0071The fourth organic compound and the fifth organic compound are hole-transporting materials and a second organic compound. The material is preferably an electron transporting material. As the hole transporting material, the above-mentioned aromatics Amine compounds, and DPAnth, CzA1PA, DPhPA, YGAPA, PCAPA , PCAPBA, 2PCAPA, DBC1 and other condensed polycyclic aromatic compounds. Den Examples of the child-transporting material include the above-mentioned heterocyclic compounds, and CzPA, DPCzPA, and DPPA. , DNA, t-BuDNA, BANT, DPNS, DPNS2, TPB3, etc. Aromatic compounds can be mentioned.
0072Among the above, condensed polycyclic aromatic compounds have a wide bandgap and can be used as a luminescent center material. Although it can be suitably used as a host material for dispersion, it is a hole-transporting material. However, it also retains the ability to transport electrons to some extent, and the electrons penetrate to the hole transport layer. In some cases, the deterioration was increased. Therefore, as the fourth organic compound, hole transfer DPANth, CzA1PA, DPhPA, YGAP, which are condensate polycyclic aromatic compounds A, PCAPA, PCAPBA, 2PCAPA, DBC1, PCBAPA, PCCPA By using the configuration of the light emitting element as in the present embodiment, it is very present. Deterioration can be effectively suppressed.
0073When an electron transport layer is used, it is installed between the light emitting layer and the electron injection layer. As a suitable material Tris (8-quinolinolato) aluminum (abbreviation: Alq)<sub>3</sub>), Tris (4-Mech Le-8-Kinolinolato) Aluminum (abbreviation: Almq), Bis (10-Hydroxyben) Zo [h]-Kinorinato) Beryllium (abbreviation: BeBq)<sub>2</sub>), Bis (2-methyl-8-quino) Rinorat)-(4-Hydroxy-biphenylyl) -aluminum (abbreviation: BAlq) etc. , A metal complex having a quinoline skeleton or a benzoquinoline skeleton can be used. In addition to this, bis [2- (2-hydroxyphenyl) -benzoxazolate] zinc ( Abbreviation: Zn (BOX)<sub>2</sub>), Bis [2- (2-Hydroxyphenyl) -benzothiazolato ] Zinc (abbreviation: Zn (BTZ))<sub>2</sub>) And other oxazole-based and thiazole-based ligands A metal complex or the like can also be used. In addition to metal complexes, 2- (4-biphenyli Le) -5- (4-tert-Butylphenyl) -1,3,4-oxadiazole (abbreviation: abbreviation: PBD) and 1,3-bis [5- (p-tert-butylphenyl) -1,3,4-oki Saziazole-2-yl] Benzene (abbreviation: OXD-7), vasofenanthroline (abbreviation) : BPhen), basocuproin (abbreviation: BCP), etc. can also be used. Electronic transportation 10 as a feed layer<sup>-6</sup>cm<sup>2</sup>It is preferable to use a substance with electron mobility of / Vs or higher. However, any substance having a higher electron transport property than holes can be used as an electron transport layer. In addition, the electron transport layer is not limited to a single-layer structure, but is composed of substances that meet the above conditions. It may be a layer having a multi-layer structure in which two or more layers are combined. The electron transport layer is a vacuum deposition method, etc. Can be produced using.
0074Further, a polymer compound can also be used as the electron transport layer. For example, poly [(9, 9-Dihexyl Fluorene-2,7-Diyl) -co- (Pyridine-3,5-Diyl)] (Abbreviation: PF-Py), Poly [(9,9-Dioctylfluorene-2,7-Diyl) -c o- (2,2'-bipyridine-6,6'-diyl)] (abbreviation: PF-BPy) etc. Can be In this case, apply a solution process such as an inkjet method or spin coating. can do.
0075The electron transport layer in contact with the light emitting layer has a first light-emitting central substance of the first layer 102. It is preferable to use a substance having a larger excitation energy than the machine compound. like this With the configuration, energy transfer from the light emitting layer to the electron transport layer can be suppressed. , High luminous efficiency can be realized.
0076When an electron injection layer is used, the electron injection material constituting the electron injection layer is not particularly limited. No, specifically, calcium fluoride, lithium fluoride, lithium oxide, lithium chloride. Which alkali metal compound, alkaline earth metal compound, etc. are suitable. Or Tris (8-Kinolinolato) Aluminum (abbreviation: Alq) and Basocuproin (abbreviation: BCP) ), So-called electron-transporting materials, alkali metals such as lithium and magnesium, or A layer combining alkaline earth metals can also be used. The electron injection layer is formed in contact with the cathode and By using the electron injection layer, the injection barrier of the carrier is reduced and the carrier is efficiently emitted. It is injected into the optical element, and as a result, the drive voltage can be reduced. In addition, with the electron injection layer Then, a layer in which a substance having electron transport property and an alkali metal or an alkaline earth metal are combined is formed. It is more preferable to use it because electron injection from the cathode occurs efficiently. Electronic The injection layer can be produced by using a vacuum vapor deposition method or the like.
0077In addition to the above-mentioned production method, a vapor deposition method and an ink are used to form the layer 107 containing the organic compound. Use regardless of wet or dry method such as jet method, spin coating method, dip coating method, etc. Can be done.
0078In addition, by providing an electron injection layer between the cathode and the electron transport layer, the work function can be increased or decreased. Regardless, indium oxide containing Al, Ag, ITO, silicon or silicon oxide-oxidation Various conductive materials such as tin can be used.
0079After this, a cathode is formed to complete the light emitting element. As a cathode, the work function is small (concrete) Use 3.8 eV or less) Metals, alloys, conductive compounds, and mixtures thereof. Is preferable. Specifically, metals belonging to Group 1 or Group 2 of the Periodic Table of the Elements, that is, Lithi Alkali metals such as um (Li) and cesium (Cs), and magnesium (Mg) and cal Alkaline earth metals such as Sium (Ca) and Strontium (Sr), and combinations containing these. Rare gold (MgAg, AlLi, etc.), europium (Er), ytterbium (Yb), etc. Examples include earth metals and alloys containing these. Alkaline metal, alkaline earth metal, Alloy films containing them can be formed using vacuum deposition. Also, alkali metals Alternatively, alloys containing alkaline earth metals can also be formed by the sputtering method. .. It is also possible to form a film of silver paste or the like by an inkjet method or the like.
0080A conductive set containing a conductive polymer (also referred to as a conductive polymer) as an anode or a cathode. Adults can also be used. When the conductive composition is formed as an anode or a cathode, it is formed on a thin film. Sheet resistance is 10000Ω / or less, and light transmittance at wavelength 550nm is 70% or more. Is preferable. In addition, the resistivity of the contained conductive polymer is 0.1 Ω · cm or less. Is preferable.
0081As the conductive polymer, a so-called π-electron conjugated conductive polymer can be used. Example For example, polyaniline and / or its derivatives, polypyrrole and / or its derivatives, polyti Offen and / or derivatives thereof, copolymers of two or more of these, and the like can be mentioned.
0082Specific examples of the conjugated conductive polymer include polypyrrole, poly (3-methylpyrrole), and po. Li (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole) ), Poly (3,4-dimethylpyrrole), Poly (3,4-dibutylpyrrole), Poly (3) -Hydroxypyrrole), poly (3-methyl-4-hydroxypyrrole), poly (3-me Toxipyrrole), poly (3-ethoxypyrrole), poly (3-octoxypyrrole), Poly (3-carboxypyrrole), Poly (3-methyl-4-carboxypyrrole), Poly N-methylpyrrole, polythiophene, poly (3-methylthiophene), poly (3- Butylthiophene), poly (3-octylthiophene), poly (3-decylthiophene) , Poly (3-dodecylthiophene), Poly (3-methoxythiophene), Poly (3-Eto) Xythiophene), poly (3-octoxythiophene), poly (3-carboxylthiophene) En), poly (3-methyl-4-carboxythiophene), poly (3,4-ethylenedi) Oxythiophene), polyaniline, poly (2-methylaniline), poly (2-octyl) Aniline), poly (2-isobutylaniline), poly (3-isobutylaniline), poly Examples thereof include (2-aniline sulfonic acid) and poly (3-aniline sulfonic acid).
0083The above conductive polymer may be used alone for an anode or a cathode, or for adjusting the film characteristics. Can be used as a conductive composition by adding an organic resin to the mixture.
0084The organic resin is a thermosetting resin if it can be compatible with or mixed and dispersed with a conductive polymer. It may be a thermoplastic resin or a photocurable resin. For example, poly Ethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. Polyester resin, polyimide, polyimide resin such as polyamide-imide, polyamide 6, Polyamide 6,6, Polyamide 12, Polyamide resin such as Polyamide 11, Polyamide Vinylidene chloride, polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluo Loethylene copolymer, fluororesin such as polychlorotrifluoroethylene, polyvinyl alcohol Lucor, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride Vinyl resin such as le, epoxy resin, xylene resin, aramid resin, polyurethane resin, Polyurea resin, melamine resin, phenol resin, polyether, acrylic resin and so on And these copolymers and the like.
0085Further, in order to adjust the electrical conductivity of the conductive polymer or the conductive composition, the accept Conjugated conductivity of conjugated conductive polymers by doping with T or donor dopants The redox potential of the offspring may be changed.
0086Acceptable dopants include halogen compounds, Lewis acids, protonic acids, and organic shears. No compound, organometallic compound, etc. can be used. As a halogen compound, chlorine, Examples include bromine, iodine, iodine chloride, iodine bromide, iodine fluoride and the like. As Lewis acid Phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, boron trifluoride, boron trichloride, triodorization Boron and the like can be mentioned. Protonic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and hydrogen borofluoride. Inorganic acids such as acids, hydrofluoric acids and perchloric acids and organic acids such as organic carboxylic acids and organic sulfonic acids Can be mentioned. Organic carboxylic acids and organic sulfonic acids include carboxylic acid compounds. And sulfonic acid compounds can be used. As an organic cyano compound, for conjugated bonds Compounds containing two or more cyano groups can be used. For example, tetracyanoethylene, tetra Cyanethylene oxide, tetracyanobenzene, tetracyanoquinodimethane, tetra Examples thereof include cyanoazanaphthalene.
0087Donor-type dopants include alkali metals, alkaline earth metals, quaternary amine compounds, etc. Can be mentioned.
0088The above conductive polymer or conductive composition is used in water or an organic solvent (alcohol-based solvent, ketone). Dissolve in based solvent, ester solvent, hydrocarbon solvent, aromatic solvent, etc.) and use the wet method. A thin film that becomes an anode or a cathode can be formed.
0089The solvent for dissolving the conductive polymer or the conductive composition is not particularly limited. If a polymer resin compound such as the above-mentioned conductive polymer and organic resin is used, Good. For example, water, methanol, ethanol, propylene carbonate, N-methylpyro Lidone, dimethylformamide, dimethylacetamide, cyclohexanone, acetone, For single or mixed solvents such as methyl ethyl ketone, methyl isobutyl ketone, and toluene It should be dissolved.
0090After dissolving the conductive composition in a solvent as described above, the coating method, the coating method, and the droplets are formed. The film can be formed by using a wet method such as a discharge method (also called an inkjet method) or a printing method. .. The solvent may be dried by heat treatment or under reduced pressure. Also, the organic resin is hot In the case of curability, further heat treatment may be performed, and in the case of photocurability, light irradiation treatment may be performed.
0091By changing the types of the second electrode 100 and the first electrode 101, the present embodiment can be generated. Optical elements have various variations. By making the second electrode 100 light-transmitting, the second electrode 100 It is configured to emit light from the electrode 100 side of 2, and the second electrode 100 has a light-shielding property (especially). (Reflective), and by making the first electrode 101 light-transmitting, light is emitted from the side of the first electrode 101. It is configured to inject. Further, both the second electrode 100 and the first electrode 101 are light-transmitting. By doing so, it is possible to emit light to both the second electrode side and the first electrode side.
0092(Embodiment 2) In this embodiment, an example of a light emitting device manufactured by using the light emitting element shown in the first embodiment. Will be described. The light emitting device of the present invention is only a light emitting device having the configuration described below. In the first embodiment, the portion responsible for the display (pixel portion 602 in the present embodiment) is not limited to It shall include all those including the indicated light emitting elements.
0093In this embodiment, an example of a light emitting device manufactured by using the light emitting element shown in the first embodiment. Will be described with reference to FIG. Note that FIG. 3 (A) is a top view showing the light emitting device, and FIG. 3 (B). ) Is a cross-sectional view of FIG. 3 (A) cut by A-A'and B-B'. This light emitting device emits Drive circuit unit (source side drive circuit) shown by the dotted line to control the light emission of the optical element 6 01, pixel unit 602, drive circuit unit (gate side drive circuit) 603 are included. Also 60 4 is a sealing substrate, 605 is a sealing material, and the inside surrounded by the sealing material 605 is a space 607. It has become.
0094In addition, the routing wiring 608 enters the source side drive circuit 601 and the gate side drive circuit 603. FPC (Flexible Device) that is a wiring for transmitting a power signal and serves as an external input terminal. Lint circuit) 609 to video signal, clock signal, start signal, reset signal Etc. are received. In addition, although only FPC is shown here, it is printed on this FPC. A wiring board (PWB) may be attached. The light emitting device in the present specification refers to light emitting. It includes not only the main body of the device but also the state where FPC or PWB is attached to it. To do.
0095Next, the cross-sectional structure will be described with reference to FIG. 3 (B). Drive circuit on the element board 610 A part and a pixel part are formed, but here, the source side drive circuit 601 which is a drive circuit part is formed. , One pixel in the pixel unit 602 is shown.
0096The source side drive circuit 601 is an n-channel type TFT623 and a p-channel type TFT62. A CMOS circuit combined with 4 is formed. In addition, the drive circuit is a variety of CMOS circuits. , It may be formed by a MOSFET circuit or an NMOS circuit. Further, in the present embodiment, the substrate The driver integrated type with the drive circuit formed above is shown, but it is not always necessary, and the drive circuit is It can also be formed on the outside instead of on the substrate.
0097Further, the pixel unit 602 includes a switching TFT 611, a current control TFT 612, and the like. The first electrode 613 electrically connected to the drain of the first electrode and the first electrode 613, organic compound Formed by a plurality of pixels including a layer 616 containing an object and a light emitting element composed of a second electrode 617. Is done. An insulator 614 is formed so as to cover the end portion of the first electrode 613. here , Formed by using a positive photosensitive acrylic resin film.
0098In addition, in order to improve the covering property, the upper end or lower end of the insulator 614 has a curvature. Make sure that a curved surface is formed. For example, as a material for insulator 614, positive photosensitive a. When using krill, there is a radius of curvature (0.2 μm to 3 μm) only at the upper end of the insulator 614. It is preferable to have a curved surface. Also, as an insulator 614, it can be squeezed by irradiation with light. Negative type that becomes insoluble in chants, or becomes soluble in etchants by irradiation with light Any of the positive types can be used.
0099A layer 616 containing an organic compound and a second electrode 617 are laminated on the first electrode 613. The light emitting element is configured. Here, it is used for the first electrode 613 that functions as an anode. Materials that have a large work function (specifically, 4.0 eV or more), metals, alloys, and conductive materials It is preferable to use a mixture or a mixture thereof. Specifically, indium tin oxide Indium tin oxide containing a compound (hereinafter referred to as ITO) or silicon or silicon oxide Contains indium oxide containing zinc oxide (ZnO), tungsten oxide and zinc oxide Indium oxide (IWZO), gold (Au), platinum (Pt), nickel (Ni), tongue Stainless steel (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), A single nitride (eg, titanium nitride) of copper (Cu), palladium (Pd), or a metallic material. In addition to layered films, laminated structures can also be applied. For example, titanium nitride films and aluminum-based films. , A three-layer structure of a titanium nitride film, a film containing aluminum as a main component, and a titanium nitride film, etc. Can be used. In addition, if it is a laminated structure, the resistance as wiring is low and it is good. Mick contact can be made and it can function as an anode.
0100The layer 616 containing the organic compound is the same as the layer 107 containing the organic compound described in the first embodiment. It has the same structure. In addition, as a material constituting the layer 616 containing an organic compound, the content is low. Whether using a child compound or a polymer compound (including oligomers and dendrimers) Good. The material used for the layer 616 containing the organic compound is not limited to the organic compound. Inorganic compounds may be used as a part thereof. A vapor deposition mask is used for the layer 616 containing the organic compound. It is formed by various methods such as a vapor deposition method, an inkjet method, and a spin coating method.
0101In addition, a second electrode 61 formed on layer 616 containing the organic compound and functions as a cathode. The material used for 7 is a material with a small work function (Al, Mg, Li, Ca, or this. Alloys and compounds, MgAg, MgIn, AlLi, LiF, CaF<sub>2</sub>Etc.) Is preferable. The light generated in the layer 616 containing the organic compound is transmitted through the second electrode 617. In this case, as the second electrode 617, a thin metal thin film and a transparent conductive film (ITO) , Indium oxide containing 2-20 wt% zinc oxide, silicon or acid containing silicon oxide Indium-tin oxide, zinc oxide (ZnO), etc.) should be laminated.
0102Here, it is generated by the first electrode 613, the layer 616 containing the organic compound, and the second electrode 617. Although the optical element is configured, the detailed structure and material of the light emitting element will be described in the first embodiment. Since the explanation has been given, a repetitive explanation will be omitted. See Embodiment 1. In addition, the book The first electrode 613, the layer 616 containing the organic compound, and the second electrode 617 in the embodiment are The first electrode 101, the layer 107 containing the organic compound, and the second electricity in the first embodiment, respectively. Corresponds to pole 100.
0103The element substrate 610 on which the drive circuit, the TFT of the pixel portion, and the light emitting element described above are formed, and By bonding the sealing substrate 604 with the sealing material 605, the element substrate 610, The space 607 surrounded by the sealing substrate 604 and the sealing material 605 is shown in the first embodiment. A light emitting device having a structure including the light emitting element 106 is provided. The space 607 is filled. In addition to the case where the material is filled and is filled with an inert gas (nitrogen, argon, etc.), the sealing material It may be filled with 605.
0104It is preferable to use an epoxy resin for the sealing material 605. Also, these materials Is desirable to be a material that does not allow oxygen to permeate as much as possible. Also used for the sealing substrate 604 In addition to glass substrate and quartz substrate, FRP (Fiberglass-Reinfo) rced Plastics), PVF (Polyvinyl Fluoride), Polyester or A plastic substrate made of acrylic or the like can be used.
0105As described above, the light emitting device of the present invention produced by using the light emitting device shown in the first embodiment. You can get a place.
0106The light emitting device of the present invention uses the light emitting element shown in the first embodiment, and the light emitting element is driven by the light emitting element. High reliability because it is a light emitting element whose degree of deterioration is reduced with respect to the accumulation of moving time. A light emitting device can be obtained. In addition, the light emitting element can easily realize the light emitting color intended by the designer. From the point of view, it can be a light emitting device with excellent display quality.
0107Further, does the light emitting element shown in the first embodiment have a suitable configuration as a white light emitting element? Therefore, it can be suitably used for lighting applications.
0108As described above, in the present embodiment, the drive of the light emitting element is controlled by the transistor. The active matrix type light emitting device has been described, but in addition to this, the passive matrix type light emitting device It may be a light emitting device. FIG. 4 shows a passive matrix type generated by applying the present invention. Indicates an optical device. Note that FIG. 4 (A) is a perspective view showing the light emitting device, and FIG. 4 (B) is FIG. 4 (A). It is a cross-sectional view cut by XY. In FIG. 4, electrodes 952 and electrodes 9 are placed on the substrate 951. A layer 955 containing an organic compound is provided between 56 and 56. The end of the electrode 952 is an insulating layer Covered with 953. A partition layer 954 is provided on the insulating layer 953. Separation The side wall of the wall layer 954 has a narrower distance between one side wall and the other side wall as it gets closer to the substrate surface. It has a gradual slope. That is, the cross section of the partition wall layer 954 in the short side direction is trapezoidal. Yes, the bottom side (the side in contact with the insulating layer 953) is more than the top side (the side not in contact with the insulating layer 953) short. By providing the partition wall layer 954 in this way, defects in the light emitting element due to static electricity or the like can be prevented. It can be prevented. The passive matrix type light emitting device is also shown in the first embodiment. A light emitting element is used, and the degree of deterioration of the light emitting element with respect to the accumulation of driving time is reduced. Since it is a light emitting element, a highly reliable light emitting device can be obtained. In addition, the light emission A light emitting device with excellent display quality because the element easily realizes the emission color intended by the designer. Can be.
0109(Embodiment 3) In the present embodiment, an electronic device including the light emitting device shown in the second embodiment as a part thereof will be described. I will reveal. These electronic devices have a display unit including the light emitting element shown in the first embodiment.
0110As the electronic device having the light emitting element shown in the first embodiment, a video camera and a digital camera Cameras such as la, goggles type display, navigation system, sound reproduction device (car) Audio, audio components, etc.), computers, game machines, personal digital assistants (mobile) Computers, mobile phones, handheld game consoles or e-books, etc.), images with recording media Playback device (specifically, Digital Versatile Disc (DVD), etc. A device equipped with a display device capable of reproducing a recording medium and displaying the image) and the like. this A specific example of these electronic devices is shown in Fig. 5.
0111FIG. 5A shows a television device according to the present invention, which includes a housing 9101, a support base 9102, and a display unit. Includes 9103, speaker section 9104, video input terminal 9105, etc. This TV device , The display unit 9103 uses the light emitting element shown in the first embodiment as a display element. Is made. In addition, the light emitting element having a reduced degree of deterioration with respect to the accumulation of driving time The television device manufactured by using the display unit 9103 has high reliability, and the display unit 9103 is used. The provided television device is a highly reliable television device. The light emitting element has low deterioration Since it is a reduced light emitting element, the deterioration compensation function circuit mounted on the TV device has been significantly reduced. It can be reduced or reduced.
0112FIG. 5B shows a computer according to the present invention, which includes a main body 9201, a housing 9202, and a display unit. 9203, keyboard 9204, external connection port 9205, pointing device 92 Including 06 etc. In this computer, the display unit 9203 is a light emitting element shown in the first embodiment. Is manufactured by using as a display element. Also, the deterioration due to the accumulation of driving time A computer manufactured using the light emitting element with a reduced degree is a display unit 9203. Highly reliable, the computer equipped with this display 9203 is a highly reliable computer. It has become. Since the light emitting element is a light emitting element with reduced deterioration, this computer The deterioration compensation function circuit mounted on the data can be significantly reduced or reduced, and the computer can be reduced. It is possible to reduce the size and weight of the data.
0113FIG. 5C shows a mobile phone according to the present invention, which includes a main body 9401, a housing 9402, and a display unit 94. 03, audio input unit 9404, audio output unit 9405, operation key 9406, external connection port 9 Includes 407, antenna 9408, etc. In this mobile phone, the display unit 9403 is the embodiment 1. It is manufactured by using the light emitting element shown in the above as a display element. Also, drive time In a mobile phone manufactured using the light emitting element in which the degree of deterioration with respect to the accumulation of , Display 9403 is highly reliable, and the mobile phone equipped with this display 9403 is reliable. It is an expensive mobile phone. Since the light emitting element is a light emitting element with reduced deterioration, The deterioration compensation function circuit installed in this mobile phone can be significantly reduced or reduced. It is possible to further reduce the size and weight of mobile phones. The mobile phone of the present invention that has been made smaller and lighter. Even if the phone has various added values, it can be kept in a size and weight suitable for carrying, and a book The mobile phone of the present invention has a configuration suitable as a high-performance mobile phone.
0114FIG. 5 (D) shows the camera according to the present invention, which includes a main body 9501, a display unit 9502, and a housing 950. 3, external connection port 9504, remote control receiver 9505, image receiver 9506, battery 9 Includes 507, voice input section 9508, operation key 9509, eyepiece section 9510, etc. This camera The display unit 9502 uses the light emitting element shown in the first embodiment as a display element. It is made. In addition, the light emission has a reduced degree of deterioration with respect to the accumulation of driving time. The display unit 9502 is highly reliable in cameras manufactured using elements, and this display unit 9502 The camera equipped with the above is a highly reliable camera. Deterioration of the light emitting element is reduced Since it is a light emitting element, the deterioration compensation function circuit installed in this camera can be significantly reduced. It can be reduced in size, and the size and weight of the camera can be reduced.
0115As described above, the applicable range of the light emitting device manufactured by using the light emitting element shown in the first embodiment is Very widely, this light emitting device can be applied to electronic devices in all fields. Also , A table prepared using the light emitting element in which the degree of deterioration with respect to the accumulation of driving time is reduced. The display unit is highly reliable, and the electronic device having the display unit can be a highly reliable electronic device. it can.
0116Further, as the light emitting device of the present invention, a lighting device can be mentioned. Shown in Embodiment 1 A mode of applying the light emitting element to the lighting device will be described with reference to FIG.
0117FIG. 6 shows a liquid crystal display device to which the light emitting element shown in the first embodiment is applied as a backlight. This is an example. The liquid crystal display device shown in FIG. 6 includes a housing 901, a liquid crystal layer 902, and a backlight unit. It has a knit 903 and a housing 904, and the liquid crystal layer 902 is connected to the driver IC 905. To. Further, the backlight unit 903 is formed by using the light emitting element shown in the first embodiment. The current is supplied by the terminal 906.
0118Here, the liquid crystal backlight unit 903 uses a color filter provided for each pixel. Light emission that provides optimum light when it is transmitted and is exposed to the eyes of the person who actually views the liquid crystal display device. It is desirable to have a color. That is, usually, as a color filter, each pixel is red. , A film that transmits blue or green light is provided, but the light transmittance depends on the material of the color filter. The backlights are red, blue, and green because humans have different luminosity factors depending on the color. It is desirable to have the desired brightness in each wavelength component. In this regard, embodiments The light emitting element shown in 1 has a liquid crystal back because it is easy to adjust the color balance. It can be very suitably used as a light unit 903.
0119The backlight unit 903 uses only one light emitting element shown in the first embodiment. Alternatively, a plurality of the light emitting elements may be used.
0120In this way, the light emitting element shown in the first embodiment is applied to the backlight of the liquid crystal display device. be able to. Since the backlight can be increased in area, the area of the liquid crystal display device can be increased. Will also be possible. Further, by using the light emitting element having a small degree of deterioration due to the accumulation of driving time. By manufacturing, a highly reliable backlight can be obtained. In addition, the backlight Because it is thin and the desired emission color can be easily obtained, the liquid crystal display device is made thinner and the image quality is higher. Quality can also be improved.
0121FIG. 7 shows an example in which the light emitting element shown in the first embodiment is used for a desk lamp which is a lighting device. is there. The desk lamp shown in FIG. 7 has a housing 2001 and a light source 2002, and has a light source 2002. As a result, the light emitting element shown in the first embodiment is formed. The light source 2002 is the light emitting element. It may be composed of one, or may be composed of a plurality of the light emitting elements. Ma Further, it may be composed of a plurality of types of light emitting elements exhibiting different light emitting colors. in this way , The light source 2002 can be manufactured by using the light emitting element shown in the first embodiment. When driving The light source 2002 manufactured by using the light emitting element having a small degree of deterioration due to accumulation during the period is Since the desk lamp is highly reliable, the desk lamp equipped with this should also be a desk lamp with high reliability. Can be done. Further, the color balance of the light emitting element shown in the first embodiment can be easily adjusted. Therefore, a desk lamp that has a luminescent color that matches the application, such as exhibiting a luminescent color that is easy on the eyes. Can be easily provided.
0122FIG. 8 shows an example in which the light emitting element shown in the first embodiment is applied to the indoor lighting device 3001. To. The lighting device 3001 may be composed of one light emitting element, or a plurality of the light emitting elements. It may be composed of children. In addition, it depends on multiple types of light emitting elements that exhibit different emission colors. It may be configured. As described above, the luminescent element described in the light emitting device shown in the first embodiment The lighting device 3001 can be manufactured using the child. Manufactured by applying the light emitting element Since the lighting device 3001 can be used as a large-area lighting device, it can be used as a large-area lighting device. it can. Further, the lighting device 3001 manufactured by using the light emitting element having good luminous efficiency It can be a thin and low power consumption lighting device. In addition, the degree of deterioration due to the accumulation of driving time The illuminating device 3001 manufactured by using the light emitting element having a small fit is a highly reliable illuminating device. Can be. Further, the light emitting element shown in the first embodiment can be adjusted in color balance. Because it is easy, it can easily provide light emission of various colors from warm colors to cold colors. It is possible to do. As a result, for example, warm colors for the living room, kitchen and die Easily provide lighting devices that have emission colors that match the application, such as colors with good color rendering properties for lighting. Can be
<p num="0123"> In this embodiment, the manufacturing method and element characteristics of the light emitting device described in the first embodiment will be described. The element configurations of the light emitting elements 1 to 6 are shown in Table 1, respectively.<tables num="1"><img id="000003" he="92" wi="170" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0124">(Light emitting element 1) First, indium tin oxide containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. The material was formed into a film by a sputtering method to form a first electrode (electrode area 2 mm × 2 mm).</p><p num="0125"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa 4,4'-Bis [N- (1-naphthyl) -N-Phenylamino] Biphenyl (abbreviation: NP) By co-depositing B) and molybdenum oxide (VI), an organic compound and an inorganic compound can be obtained. A layer containing the composite composite material was formed. Its film thickness is 50 nm, and NPB and moly oxide The ratio to Buden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted. The co-evaporation method is steaming in which vapor deposition is performed simultaneously from multiple evaporation sources in one processing chamber. It is a method of wearing.</p><p num="0126"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0127"> After this, 9,10-diphenylanthracene (abbreviation: DPAnth) and 4- (9H-ca) Rubazole-9-yl) -4'-(9,10-diphenyl-2-anthril) tripheni By co-depositing with luamine (abbreviation: 2YGAPPA), a third film thickness of 10 nm A layer was formed. Here, the weight ratio of DPAnth and 2YGAPPA is 1: 0.1 (= DP). Anth: 2YGAPPA) was adjusted.</p><p num="0128"> And 4- (9H-carbazole-9-yl) -4'-(10-phenyl-9-an) By co-depositing triphenylamine (abbreviation: YGAPA) and rubrene A second layer with a film thickness of 10 nm was formed. Here, the weight ratio of YGAPA and rubrene is 1. Adjusted to: 0.0025 (= YGAPA: rubrene).</p><p num="0129"> In addition, 9- [4- (10-Phenyl-9-Anthryl) Phenyl] -9H-Carbazo By co-depositing all (abbreviation: CzPA) and 2YGAPPA, the film thickness is 20 nm. Formed the first layer. Here, the weight ratio of CzPA and 2YGAPPA is 1: 0.05 (=) CzPA: 2YGAPPA) was adjusted.</p><p num="0130"> Then, using the vapor deposition method by resistance heating, tris (8-quinolinolato) aluminum ( Abbreviation: Alq) is deposited to a film thickness of 10 nm, and then vapor deposition by resistance heating is also performed. Using the method, basophenanthroline (abbreviation: BPhen) was formed to a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0131"> Then, using the same resistance-heated thin-film deposition method, lithium fluoride (LiF) was added to 1 nm. To some extent, form an electron injection layer, and finally aluminum to a film thickness of 200 nm. A second electrode was formed by forming a film, and a light emitting element 1 was manufactured.</p><p num="0132"> The light emitting element 1 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it is not exposed to the atmosphere, about the operating characteristics of this light emitting element Measurements were made. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0133"> The current density-luminance characteristics of the light emitting element 1 are shown in FIG. In addition, the brightness-current efficiency characteristics are shown in Fig. 10. Shown. The voltage-luminance characteristics are shown in FIG. The voltage-current characteristics are shown in Fig. 12. Ma The emission spectrum when a current of 1 mA is passed through the light emitting element 1 is shown in FIG.</p><p num="0134"> In the light emitting element 1, 2YGAPPA, which is the light emitting center substance of the first layer and the third layer, is blue. Rubrene, which is the central substance that emits color, is a substance that emits yellow light. That is, in FIG. 13, the emission having a peak near 462 nm is that of 2YGAPPA. The light emission having a peak near 549 nm is the light emission of rubrene, and in the light emitting element 1, The emission of 2YGAPPA on the short wavelength side and the emission of rubrene on the long wavelength side can be obtained with almost the same intensity. You can see that it is. In the conventional configuration, the long wavelength is affected by energy transfer and the like. It was difficult to balance the emission color because the emission on the side was strong, but the configuration of the present invention By using, as in the light emitting element 1 described above, the light emission intensity on the short wavelength side and the long wave It is also possible to make the emission intensity on the long side almost the same, and the balance of emission colors can be easily adjusted. You will be able to. The brightness of the light emitting element 1 is 900 cd / m.<sup>2</sup>CIE chromaticity coordinates It emitted white light at (x = 0.26, y = 0.35).</p><p num="0135">(Light emitting element 2) First, indium tin oxide containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. The material was formed into a film by a sputtering method to form a first electrode (electrode area 2 mm × 2 mm).</p><p num="0136"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa By co-depositing NPB and molybdenum oxide (VI), organic compounds and inorganic compounds A layer containing a composite material was formed. Its film thickness is 50 nm, and NPB and oxides are used. The ratio with ribden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted to. The co-evaporation method is to simultaneously evaporate from a plurality of evaporation sources in one processing chamber. It is a thin-film deposition method.</p><p num="0137"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0138"> After that, by co-depositing DPAnth and 2YGAPPA, the film thickness is 20 nm. A third layer was formed. Here, the weight ratio of DPAnth and 2YGAPPA is 1: 0.1 ( = DPAnth: 2YGAPPA).</p><p num="0139"> Then, by co-depositing YGAPA and rubrene, a second layer with a film thickness of 10 nm Was formed. Here, the weight ratio of YGAPA and rubrene is 1: 0.0025 (= YGAP). A: Rubrene) was adjusted.</p><p num="0140"> Furthermore, by co-depositing CzPA and 2YGAPPA, the first film thickness of 20 nm is achieved. Formed a layer of. Here, the weight ratio of CzPA and 2YGAPPA is 1: 0.05 (= Cz). PA: 2YGAPPA) was adjusted.</p><p num="0141"> After that, Alq was deposited to a film thickness of 10 nm using a vapor deposition method by resistance heating. Then, using the same resistance heating vapor deposition method, BPhen was made to have a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0142"> Then, using the same resistance-heated thin-film deposition method, lithium fluoride (LiF) was added to 1 nm. To some extent, form an electron injection layer, and finally aluminum to a film thickness of 200 nm. A second electrode was formed by forming a film, and a light emitting element 2 was manufactured.</p><p num="0143"> The light emitting element 2 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it is not exposed to the atmosphere, about the operating characteristics of this light emitting element Measurements were made. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0144"> The current density-luminance characteristics of the light emitting element 2 are shown in FIG. In addition, the brightness-current efficiency characteristics are shown in Fig. 15. Shown in. The voltage-luminance characteristics are shown in FIG. The voltage-current characteristics are shown in FIG. Further, FIG. 18 shows the emission spectrum when a current of 1 mA is passed through the light emitting element 2.</p><p num="0145"> In the light emitting element 2, 2YGAPPA, which is the light emitting center substance of the first layer and the third layer, is blue. Rubrene, which is the central substance that emits color, is a substance that emits yellow light. That is, in FIG. 18, the emission having a peak near 462 nm is that of 2YGAPPA. The light emission having a peak near 549 nm is the light emission of rubrene, and in the light emitting element 2, The emission of 2YGAPPA on the short wavelength side is obtained with a higher intensity than the emission of rubrene on the long wavelength side. You can see that. In the conventional configuration, the long wavelength side is affected by energy transfer and the like. It was difficult to balance the emission color due to the strong emission of the light emitted. By using it, as in the light emitting element 2 described above, the light emission intensity on the short wavelength side is changed to the long wavelength side. It is also possible to obtain stronger than the emission intensity of, and the balance of emission color can be easily adjusted. You will be able to. The brightness of the light emitting element 2 is 780 cd / m.<sup>2</sup>CIE chromaticity coordinates are (x = 0 It was white emission at .26, y = 0.34).</p><p num="0146">(Light emitting element 3) The light emitting element 3 is a light emitting element on which the third layer is not formed as a comparative example of the light emitting elements 1 and 2. A child, that is, a luminescent element having the configuration of the light emitting element 115 shown as a conventional example in the first embodiment. A child was produced. First, an inn containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. A dim tin oxide was formed by a sputtering method to form a first electrode (electrode area 2 mm ×). 2mm).</p><p num="0147"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa By co-depositing NPB and molybdenum oxide (VI), organic compounds and inorganic compounds A layer containing a composite material was formed. Its film thickness is 50 nm, and NPB and oxides are used. The ratio with ribden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted to. The co-evaporation method is to simultaneously evaporate from a plurality of evaporation sources in one processing chamber. It is a thin-film deposition method.</p><p num="0148"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0149"> Then, by co-depositing YGAPA and rubrene, a second layer with a film thickness of 10 nm Was formed. Here, the weight ratio of YGAPA and rubrene is 1: 0.0025 (= YGAP). A: Rubrene) was adjusted.</p><p num="0150"> Furthermore, by co-depositing CzPA and 2YGAPPA, the first film thickness of 20 nm is achieved. Formed a layer of. Here, the weight ratio of CzPA and 2YGAPPA is 1: 0.05 (= Cz). PA: 2YGAPPA) was adjusted.</p><p num="0151"> After that, Alq was deposited to a film thickness of 10 nm using a vapor deposition method by resistance heating. Then, using the same resistance heating vapor deposition method, BPhen was made to have a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0152"> Then, using the same resistance-heated thin-film deposition method, lithium fluoride (LiF) was added to 1 nm. To some extent, form an electron injection layer, and finally aluminum to a film thickness of 200 nm. A second electrode was formed by forming a film, and a light emitting element 3 was manufactured.</p><p num="0153"> The light emitting element 3 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it is not exposed to the atmosphere, about the operating characteristics of this light emitting element Measurements were made. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0154"> FIG. 19 shows the emission spectrum of the light emitting element 3. In the light emitting element 3, the light emission of the first layer 2YGAPPA, the central substance, emits blue light, and rubrene, the central substance of light emission in the second layer. Is a substance that emits yellow light. That is, in FIG. 19, the peak is near 465 nm. Emission with 2YGAPPA, luminescence with a peak near 549 nm is rubrene Although it is light, in the light emitting element 3, the emission of rubrene on the long wavelength side is 2YGA on the short wavelength side. It can be seen that the intensity is higher than that of PPA emission. Here, see the composition of the second layer In light, the second layer co-deposited YGAPA and rubrene at a ratio of 1: 0.0025. However, this is currently the lowest level of rubrene concentration that we can control. To. That is, even if the rubrene concentration is reduced as much as possible, the rubrene has an emission color on the long wavelength side. It turns out that it is difficult to control the emission color with the conventional configuration because the emission of Bren is strong. .. The brightness of the light emitting element 3 is 1740 cd / m.<sup>2</sup>CIE chromaticity coordinates are (x = 0.28, y = It was bluish white at 0.38).</p><p num="0155"> Next, the results of the evaluation regarding reliability are shown. FIG. 20 shows the light emitting element 1 and the light emitting element. 3 the initial brightness 1000 cd / m<sup>2</sup>At the time of standardized brightness when driven under constant current density conditions The figure showing the interim change is shown. In the figure, the thick line shows the result of the light emitting element 1, and the thin line shows the result of the light emitting element 3. It is a graph. From the figure, the brightness of the light emitting element 1 is lower than that of the light emitting element 3 which is a comparative example. Can be seen to be suppressed. The brightness of the light emitting element 3 drops to 53% in 590 hours. On the other hand, the light emitting element 1 maintains 54% brightness up to 1100 hours, which is about twice the life. I was able to get.</p><p num="0156">(Light emitting element 4) First, indium tin oxide containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. The material was formed into a film by a sputtering method to form a first electrode (electrode area 2 mm × 2 mm).</p><p num="0157"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa By co-depositing NPB and molybdenum oxide (VI), organic compounds and inorganic compounds A layer containing a composite material was formed. Its film thickness is 50 nm, and NPB and oxides are used. The ratio with ribden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted to. The co-evaporation method is to simultaneously evaporate from a plurality of evaporation sources in one processing chamber. It is a thin-film deposition method.</p><p num="0158"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0159"> After that, by co-depositing DPAnth and 2YGAPPA, the film thickness is 10 nm. A third layer was formed. Here, the weight ratio of DPAnth and 2YGAPPA is 1: 0.1 ( = DPAnth: 2YGAPPA).</p><p num="0160"> And 9-Phenyl-9'-[4- (10-Phenyl-9-Anthryl) Phenyl] Co-deposited -3,3'-bi (9H-carbazole) (abbreviation: PCCPA) and rubrene As a result, a second layer having a film thickness of 10 nm was formed. Here, with PCCPA and rubrene The weight ratio was adjusted to 1: 0.0025 (= PCCPA: rubrene).</p><p num="0161"> Furthermore, by co-depositing CzPA and 2YGAPPA, the first film thickness of 20 nm is achieved. Formed a layer of. Here, the weight ratio of CzPA and 2YGAPPA is 1: 0.05 (= Cz). PA: 2YGAPPA) was adjusted.</p><p num="0162"> After that, Alq was deposited to a film thickness of 10 nm using a vapor deposition method by resistance heating. Then, using the same resistance heating vapor deposition method, BPhen was made to have a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0163"> Then, similarly, using the thin-film deposition method by resistance heating, lithium fluoride is formed to about 1 nm. , An electron injection layer is formed, and finally aluminum is formed to a film thickness of 200 nm. A second electrode was formed by the above, and the light emitting element 4 was manufactured.</p><p num="0164"> The light emitting element 4 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it is not exposed to the atmosphere, about the operating characteristics of this light emitting element Measurements were made. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0165"> The current density-luminance characteristics of the light emitting element 4 are shown in FIG. In addition, the brightness-current efficiency characteristics are shown in Fig. 22. Shown in. The voltage-luminance characteristic is shown in FIG. The voltage-current characteristics are also shown in FIG. Further, FIG. 25 shows the emission spectrum when a current of 1 mA is passed through the light emitting element 4.</p><p num="0166"> In the light emitting element 4, 2YGAPPA, which is the light emitting center substance of the first layer and the third layer, is blue. Rubrene, which is the central substance that emits color, is a substance that emits yellow light. That is, in FIG. 25, the emission having a peak near 462 nm is 2YGAPPA, 5 The light emission having a peak near 49 nm is the light emission of rubrene, and in the light emitting element 4, it is short. The emission of 2YGAPPA on the wavelength side is obtained with a higher intensity than the emission of rubrene on the long wavelength side. You can see that there is. In the conventional configuration, the long wavelength side is affected by energy transfer and the like. It was difficult to balance the emission color because the emission was strong, but the configuration of the present invention was used. As a result, as in the light emitting element 4 described above, the light emission intensity on the short wavelength side is set on the long wavelength side. It is also possible to obtain stronger than the emission intensity, and the balance of emission colors can be easily adjusted. Become so. The brightness of the light emitting element 4 is 810 cd / m.<sup>2</sup>The CIE chromaticity coordinates of are (x = 0. At 25, y = 0.34), it emitted a bluish white luminescence.</p><p num="0167">(Light emitting element 5) First, indium tin oxide containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. The material was formed into a film by a sputtering method to form a first electrode (electrode area 2 mm × 2 mm).</p><p num="0168"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa By co-depositing NPB and molybdenum oxide (VI), organic compounds and inorganic compounds A layer containing a composite material was formed. Its film thickness is 50 nm, and NPB and oxides are used. The ratio with ribden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted to. The co-evaporation method is to simultaneously evaporate from a plurality of evaporation sources in one processing chamber. It is a thin-film deposition method.</p><p num="0169"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0170"> After that, by co-depositing DPAnth and 2YGAPPA, the film thickness is 20 nm. A third layer was formed. Here, the weight ratio of DPAnth and 2YGAPPA is 1: 0.1 ( = DPAnth: 2YGAPPA).</p><p num="0171"> Then, by co-depositing PCCPA and rubrene, a second layer with a film thickness of 10 nm Was formed. Here, the weight ratio of PCCPA and rubrene is 1: 0.0025 (= PCCP). A: Rubrene) was adjusted.</p><p num="0172"> Furthermore, by co-depositing CzPA and 2YGAPPA, the first film thickness of 20 nm is achieved. Formed a layer of. Here, the weight ratio of CzPA and 2YGAPPA is 1: 0.05 (= Cz). PA: 2YGAPPA) was adjusted.</p><p num="0173"> After that, Alq was deposited to a film thickness of 10 nm using a vapor deposition method by resistance heating. Then, using the same resistance heating vapor deposition method, BPhen was made to have a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0174"> Then, similarly, using the thin-film deposition method by resistance heating, lithium fluoride is formed to about 1 nm. , An electron injection layer is formed, and finally aluminum is formed to a film thickness of 200 nm. A second electrode was formed by the above, and the light emitting element 5 was manufactured.</p><p num="0175"> The light emitting element 5 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it is not exposed to the atmosphere, about the operating characteristics of this light emitting element Measurements were made. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0176"> The current density-luminance characteristics of the light emitting element 5 are shown in FIG. In addition, the brightness-current efficiency characteristics are shown in Fig. 27. Shown in. The voltage-luminance characteristic is shown in FIG. The voltage-current characteristics are also shown in FIG. Further, FIG. 30 shows the emission spectrum when a current of 1 mA is passed through the light emitting element 5.</p><p num="0177"> In the light emitting element 5, 2YGAPPA, which is the light emitting center substance of the first layer and the third layer, is blue. Rubrene, which is the central substance that emits color, is a substance that emits yellow light. That is, in FIG. 30, the emission having a peak near 462 nm is that of 2YGAPPA. The light emission having a peak near 549 nm is the light emission of rubrene, and in the light emitting element 5, The emission of 2YGAPPA on the short wavelength side is obtained with a higher intensity than the emission of rubrene on the long wavelength side. You can see that. In the conventional configuration, the long wavelength side is affected by energy transfer and the like. It was difficult to balance the emission color due to the strong emission of the light emitted. By using it, as in the light emitting element 5 described above, the light emission intensity on the short wavelength side is changed to the long wavelength side. It is also possible to obtain stronger than the emission intensity of, and the balance of emission color can be easily adjusted. You will be able to. The brightness of the light emitting element 5 is 890 cd / m.<sup>2</sup>CIE chromaticity coordinates are (x = 0 At .25, y = 0.33), the emission was slightly bluish white.</p><p num="0178">(Light emitting element 6) The light emitting element 6 is a light emitting element on which the third layer is not formed as a comparative example of the light emitting elements 4 and 5. A child was produced. First, an inn containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. A dim tin oxide was formed by a sputtering method to form a first electrode (electrode area 2 mm ×). 2mm).</p><p num="0179"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa By co-depositing NPB and molybdenum oxide (VI), organic compounds and inorganic compounds A layer containing a composite material was formed. Its film thickness is 50 nm, and NPB and oxides are used. The ratio with ribden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted to. The co-evaporation method is to simultaneously evaporate from a plurality of evaporation sources in one processing chamber. It is a thin-film deposition method.</p><p num="0180"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0181"> Then, by co-depositing PCCPA and rubrene, a second layer with a film thickness of 10 nm Was formed. Here, the weight ratio of PCCPA and rubrene is 1: 0.0025 (= PCCP). A: Rubrene) was adjusted.</p><p num="0182"> Furthermore, by co-depositing CzPA and 2YGAPPA, the first film thickness of 20 nm is achieved. Formed a layer of. Here, the weight ratio of CzPA and 2YGAPPA is 1: 0.05 (= Cz). PA: 2YGAPPA) was adjusted.</p><p num="0183"> After that, Alq was deposited to a film thickness of 10 nm using a vapor deposition method by resistance heating. Then, using the same resistance heating vapor deposition method, BPhen was made to have a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0184"> Then, similarly, using the thin-film deposition method by resistance heating, lithium fluoride is formed to about 1 nm. , An electron injection layer is formed, and finally aluminum is formed to a film thickness of 200 nm. A second electrode was formed by the above, and a light emitting element 6 was manufactured.</p><p num="0185"> The light emitting element 6 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it is not exposed to the atmosphere, about the operating characteristics of this light emitting element Measurements were made. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0186"> FIG. 31 shows the emission spectrum of the light emitting element 6. In the light emitting element 6, the light emission of the first layer 2YGAPPA, the central substance, emits blue light, and rubrene, the central substance of light emission in the second layer. Is a substance that emits yellow light. That is, in FIG. 31, the peak is near 465 nm. Emission with 2YGAPPA, luminescence with a peak near 549 nm is rubrene Regarding light, in the light emitting element 6, the emission of rubrene on the long wavelength side is 2YGA on the short wavelength side. It can be seen that the intensity is higher than that of PPA emission. The brightness of the light emitting element 6 is 15. 20cd / m<sup>2</sup>The CIE chromaticity coordinates of are (x = 0.28, y = 0.36), which is slightly whiter than blue. It was luminescent.</p><p num="0187"> Next, the results of the evaluation regarding reliability are shown. FIG. 32 shows the light emitting element 4 and the light emitting element. 6 with initial brightness of 1000 cd / m<sup>2</sup>At the time of standardized brightness when driven under constant current density conditions The figure showing the interim change is shown. In the figure, the thick line shows the result of the light emitting element 4, and the thin line shows the result of the light emitting element 6. It is a graph. From the figure, the brightness of the light emitting element 4 is lower than that of the light emitting element 6 which is a comparative example. Can be seen to be suppressed. The brightness of the light emitting element 6 drops to 58% in 590 hours. On the other hand, the light emitting element 4 maintains 61% brightness up to 1100 hours, which is about twice the life. I was able to get.</p>
<p num="0188"> In this embodiment, the manufacturing method and element characteristics of the light emitting device described in the first embodiment will be described. The element configurations of the light emitting elements 7 and 8 are shown in Table 2, respectively.<tables num="2"><img id="000004" he="92" wi="170" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0189">(Light emitting element 7) First, indium tin oxide containing silicon or silicon oxide with a film thickness of 110 nm on a glass substrate. The material was formed into a film by a sputtering method to form a first electrode (electrode area 2 mm × 2 mm).</p><p num="0190"> Next, the substrate on which the first electrode is formed is placed so that the surface on which the first electrode is formed faces downward. Fixed to the substrate holder provided in the vacuum deposition apparatus, 10<sup>-4</sup>After decompressing to about Pa 4,4'-Bis [N- (1-naphthyl) -N-Phenylamino] Biphenyl (abbreviation: NP) By co-depositing B) and molybdenum oxide (VI), an organic compound and an inorganic compound can be obtained. A layer containing the composite composite material was formed. Its film thickness is 50 nm, and NPB and moly oxide The ratio to Buden (VI) should be 4: 1 (= NPB: molybdenum oxide) by weight. Adjusted. The co-evaporation method is steaming in which vapor deposition is performed simultaneously from multiple evaporation sources in one processing chamber. It is a method of wearing.</p><p num="0191"> Subsequently, NPB was deposited to a film thickness of 10 nm by a vapor deposition method using resistance heating. , A hole transport layer was formed.</p><p num="0192"> After this, 9-phenyl-9'-[4- (10-phenyl-9-anthril) phenyl] -3,3'-bi (9H-carbazole) (abbreviation: PCCPA) and 4- (10-phenyl- 9-Anthril) -4'-(9-Phenyl-9H-Carbazole-3-yl) Tripheni A third layer with a film thickness of 10 nm by co-depositing with ruamine (abbreviation: PCBAPA) Was formed. Here, the weight ratio of PCCPA and PCBAPA is 1: 0.1 (= PCCPA). : PCBAPA) was adjusted.</p><p num="0193"> And PCCPA and N,9-diphenyl-N- (9,10-diphenyl-2-ant) To co-deposit with -9H-carbazole-3-amine (abbreviation: 2PCAPA) A second layer with a film thickness of 10 nm was formed. Here, the weight of PCCPA and 2PCAPA The quantity ratio was adjusted to 1: 0.005 (= PCCPA: 2PCAPA).</p><p num="0194"> Furthermore, by co-depositing CzPA and PCBAPA, the first film thickness of 20 nm is achieved. A layer was formed. Here, the weight ratio of CzPA and PCBAPA is 1: 0.05 (= CzPA). : PCBAPA) was adjusted.</p><p num="0195"> Then, using the vapor deposition method by resistance heating, tris (8-quinolinolato) aluminum ( Abbreviation: Alq) is deposited to a film thickness of 10 nm, and then vapor deposition by resistance heating is also performed. Using the method, basophenanthroline (abbreviation: BPhen) was formed to a film thickness of 20 nm. A film was formed to form an electron transport layer.</p><p num="0196"> Then, using the same resistance-heated thin-film deposition method, lithium fluoride (LiF) was added to 1 nm. To some extent, form an electron injection layer, and finally aluminum to a film thickness of 200 nm. A second electrode was formed by forming a film, and a light emitting element 7 was manufactured.</p><p num="0197"> The light emitting element 7 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it would not be exposed to the atmosphere, the operating characteristics were measured. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0198"> The current density-luminance characteristics of the light emitting element 7 are shown in FIG. 33. In addition, the brightness-current efficiency characteristics are shown in Fig. 34. Shown in. The voltage-luminance characteristics are shown in Fig. 35. The voltage-current characteristics are also shown in FIG. Further, FIG. 37 shows the emission spectrum when a current of 1 mA is passed through the light emitting element 7.</p><p num="0199"> In the light emitting element 7, PCBAPA, which is the light emitting center substance of the first layer and the third layer, is blue. 2PCAPA, which is the central substance that emits light in the second layer, is a substance that emits green light. .. That is, in FIG. 37, the emission having a peak near 466 nm is that of PCBAPA. The light emission having a peak near 493 nm is the light emission of 2PCAPA, and in the light emitting element 7. The intensity of the emission of PCBAPA on the short wavelength side and the emission of 2PCAPA on the long wavelength side are almost the same. It can be seen that it is obtained in. In the conventional configuration, due to the influence of energy transfer etc. It was difficult to balance the emission color because the emission on the long wavelength side was strong, but the present invention By using the configuration of, as in the light emitting element 1 described above, the light emitting intensity on the short wavelength side It is also possible to make the emission intensity on the long wavelength side almost the same, and easily adjust the balance of emission colors. You will be able to knot. The brightness of the light emitting element 7 is 1100 cd / m.<sup>2</sup>CIE color The degree coordinates were (x = 0.18, y = 0.27) and it was a blue-green emission.</p><p num="0200">(Light emitting element 8) The light emitting element 8 was manufactured in the same manner as the light emitting element 7 until the third layer was formed.</p><p num="0201"> Subsequently, by co-depositing PCBAPA and 2PCAPA, a film thickness of 10 nm was obtained. Two layers were formed. Here, the weight ratio of PCBAPA and 2PCAPA is 1: 0.02 (=) PCBAPA: 2PCAPA) was adjusted.</p><p num="0202"> After that, from the first layer to the cathode was manufactured in the same manner as the light emitting element 7, and the light emitting element 8 was manufactured.</p><p num="0203"> The light emitting element 8 obtained as described above is placed in a glove box having a nitrogen atmosphere. After performing the work of sealing the child so that it would not be exposed to the atmosphere, the operating characteristics were measured. The measurement was performed at room temperature (atmosphere maintained at 25 ° C).</p><p num="0204"> The current density-luminance characteristics of the light emitting element 8 are shown in FIG. 38. In addition, the brightness-current efficiency characteristics are shown in Fig. 39. Shown in. The voltage-luminance characteristics are shown in FIG. The voltage-current characteristics are shown in FIG. Further, FIG. 42 shows the emission spectrum when a current of 1 mA is passed through the light emitting element 8.</p><p num="0205"> In the light emitting element 8, PCBAPA, which is the light emitting center substance of the first layer and the third layer, is blue. 2PCAPA, which is the central substance that emits light in the second layer, is a substance that emits green light. .. That is, in FIG. 42, the emission having a peak near 470 nm is that of PCBAPA. The emission with a peak near 500 nm is the emission of 2PCAPA. Thus, the present invention The light emitting element of the above can also strongly emit the light emission of the light emitting center substance on the long wavelength side, and the light emitting color of the light emitting element. It can be said that it is a light emitting element whose lance can be easily adjusted. The light emitting element 8 Brightness 1190 cd / m<sup>2</sup>CIE chromaticity coordinates are (x = 0.20, y = 0.33) and blue-green It was luminescent.</p><p num="0206"> In addition, a laminated structure (a laminated structure from a hole injection layer to an electron injection layer) that provides these blue-green light emission. A structure in which a laminated structure that provides light emission in red is laminated is provided as a layer containing an organic compound. By producing a light emitting element that emits white light, it is possible to provide a light emitting element that emits white light. Wear. At this time, between the laminated structure that provides blue-green light emission and the laminated structure that provides red light emission. Is provided with a charge generation layer. The charge generation layer is formed of the composite material described in the first embodiment. Can be done. Further, the charge generation layer has a laminated structure of a layer made of a composite material and a layer made of another material. In this case, as a layer made of other materials, an electron donating substance and an electron transfer material may be formed. A layer containing a highly feedable substance, a layer made of a transparent conductive film, or the like can be used. like this A light-emitting element having such a structure has energy even if red light emission is phosphorescence and blue-green light emission is fluorescence. Problems such as movement and quenching are unlikely to occur, and the range of material selection is widened, resulting in high luminous efficiency and long duration. It is easy to obtain a white light emitting element having a long life. In addition, the blue-green emission color can be adjusted. Since it is easy, there is also an advantage that it is easy to obtain white light emission of a desired color.</p><p num="0207">(Reference example) Since 2YGAPPA used in the light emitting devices 1 to 6 is not a known substance, the synthesis method thereof should be used. explain. 2YGAPPA is represented by the following structural formula (1).</p><p num="0208"><chemistry num="1"><img id="000005" he="47" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0209">[Step 1] Synthesis of 2-bromo-9,10-diphenylanthracene</p><p num="0210">(i) Synthesis of 2-bromo-9,10-anthraquinone The synthetic scheme of 2-bromo-9,10-anthraquinone is shown in (A-1).</p><p num="0211"><chemistry num="2"><img id="000006" he="35" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0212"> 46 g (0.20 mol) of copper (II) bromide, 500 mL of acetonitrile, 1 L I put it in Suko. In addition, 17 g (0.17 mol) of tert-butyl nitrite was added. this The mixture was heated to 65 ° C. To this mixture, 2-amino-9,10-anthraquinone 25 g (0.11 mol) was added, and the mixture was stirred at the same temperature for 6 hours. After the reaction, add 3 mol / of reaction solution Pour into 500 mL of L hydrochloric acid and stir this suspension for 3 hours to precipitate a solid. This The precipitate was collected by suction filtration and washed with water and ethanol while suction filtration. Filter Is dissolved in toluene and Florisil (Wako Pure Chemical Industries, Ltd., Catalog No .: 540-0) 0135 Same as below), Celite (Wako Pure Chemical Industries, Ltd., Catalog number: 531-168 The same applies to 55 and below), suction filtration was performed through alumina, and the obtained filtrate was concentrated to obtain a solid. This The solid of 2 was recrystallized from a mixed solvent of chloroform and hexane. A milky white powdery solid of bromo-9,10-anthraquinone was obtained in 18.6 g, yield 58%. ..</p><p num="0213">(ii) 2-Bromo-9,10-diphenyl-9,10-dihydroanthracene-9,1 Synthesis of 0-diol 2-Bromo-9,10-diphenyl-9,10-dihydroanthracene-9,10-dio The synthetic scheme of all is shown in (A-2).</p><p num="0214"><chemistry num="3"><img id="000007" he="35" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0215"> 2-Bromo-9,10-anthraquinone 4.9 g (17 mmol) in 300 mL Place in Lasco, replace the inside of the flask with nitrogen, and add 100 mL of tetrahydrofuran (THF). Well, it melted well. Then, into this solution, 18 mL (37 mmol) of phenyllithium Was added dropwise, and the mixture was stirred at room temperature for about 12 hours. After the reaction, the solution is washed with water, and the aqueous layer is acetic acid. Extracted with chill. The extract solution and the organic layer were combined and dried over magnesium sulfate. After drying The mixture is suction filtered and the filtrate is concentrated to give the desired 2-bromo-9,10-diphenyl. -9,10-dihydroanthracene-9,10-diol was obtained (about 7.6 g).</p><p num="0216">(iii) Synthesis of 2-bromo-9,10-diphenylanthracene The synthetic scheme of 2-bromo-9,10-diphenylanthracene is shown in (A-3).</p><p num="0217"><chemistry num="4"><img id="000008" he="41" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0218"> The resulting 2-bromo-9,10-diphenyl-9,10-dihydroanthracene-9, 10-diol about 7.6 g (17 mmol), potassium iodide 5.1 g (31 mmol) , Sodium phosphinate monohydrate 9.7 g (92 mmol), 500 mL glacial acetic acid It was placed in a mL three-necked flask and refluxed at 120 ° C for 2 hours. Then 50% phos to the reaction mixture 30 mL of finic acid was added, and the mixture was stirred at 120 ° C. for 1 hour. After the reaction, wash the solution with water and then the aqueous layer Was extracted with ethyl acetate. Combine the extract solution and the organic layer and dry with magnesium sulfate. Ta. After drying, the mixture was suction filtered and the obtained filtrate was concentrated to obtain a solid. This Was dissolved in toluene and then filtered through Celite, Florisil and Alumina. The solid obtained by concentrating the obtained filtrate was recrystallized from a mixed solvent of chloroform and hexane. A pale yellow powdery solid of 2-bromo-9,10-diphenylanthracene, which is the target product. I got 5.1g of body. The yield in the two steps (ii) and (iii) was 74%.</p><p num="0219">[Step 2] Synthesis of 2- (4-Bromophenyl) -9,10-diphenylanthracene</p><p num="0220">(i) Synthesis of 2-iodo-9,10-diphenylanthracene The synthetic scheme of 2-iodo-9,10-diphenylanthracene is shown in (A-4).</p><p num="0221"><chemistry num="5"><img id="000009" he="41" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0222"> 500 mL of 2-bromo-9,10-diphenylanthracene 10 g (24 mmol) Place in a three-necked flask, replace the inside of the flask with nitrogen, and then 150 mL of tetrahydrofuran. Was added and dissolved. The solution was stirred at -78 ° C. 1.6 mmol / L n in this solution -Dripping 19 mL of butyllithium solution with a syringe and stirring at -78 ° C for 1 hour to react. When it was set, a white solid was precipitated. After the reaction, 12 g (49 mmol) of iodine was added to this reaction mixture. ) Was dissolved in 80 mL of tetrahydrofuran was added dropwise from a dropping funnel. After dripping The mixture was stirred at 78 ° C. for 1 hour and at room temperature for 12 hours. After the reaction, add thiosulfate to the reaction solution. An aqueous thorium solution was added, and the mixture was stirred at room temperature for 1 hour. Add ethyl acetate to this mixture and extract went. The aqueous layer and the organic layer are separated, and the organic layer is divided into sodium thiosulfate aqueous solution and saturated saline solution in this order. Washed. The aqueous layer and the organic layer were separated, and the organic layer was dried over magnesium sulfate. This mixture The material was suction filtered to remove magnesium sulfate. When the obtained filtrate was concentrated, a solid was formed. Obtained. When methanol was added to this solid and washed by irradiating with ultrasonic waves, the solid was precipitated. When this solid was collected by suction filtration, a pale yellow powdery solid was obtained in a yield of 9.9 g and a yield of 90. Obtained in%.</p><p num="0223">(ii) Synthesis of 2- (4-bromophenyl) -9,10-diphenylanthracene A synthetic scheme for 2- (4-bromophenyl) -9,10-diphenylanthracene (A) -5).</p><p num="0224"><chemistry num="6"><img id="000010" he="43" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0225"> 4-Bromophenylboronic acid 2.0 g (9.9 mmol), palladium acetate (0) 0. 02g (0.089 mmol), 2-iodine-9,10-diphenylanthracene 5.0 g (11 mmol), tris (o-trill) phosphine 0.30 g (0.99 mmol) ) Was placed in a 200 mL three-necked flask, and the inside of the flask was replaced with nitrogen. Toluene in this mixture 50 mL, 20 mL of potassium carbonate aqueous solution (2 mol / L), and 10 mL of ethanol were added. .. The mixture was heated and stirred at 100 ° C. for 8 hours to react. After the reaction, add to the reaction mixture Was added, and the suspension was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order. Organic layer And the aqueous layer are separated, and the organic layer is suction-filtered through Celite, Alumina, and Florisil, and the filtrate is filtered. Got The obtained filtrate was concentrated to give a solid. Methanol is added to this solid and it is super When washed by irradiating with sound waves, solids were precipitated. The place where this solid was recovered by suction filtration A pale yellow powdery solid was obtained in a yield of 4.6 g and a yield of 87%. By Nuclear Magnetic Resonance (NMR) So this compound is 2- (4-bromophenyl) -9,10-diphenylanthracene I confirmed that there was.</p><p num="0226"> 2- (4-Bromophenyl) -9,10-diphenylanthracene<sup>1</sup>1 NMR day The data is shown below.<sup>1</sup>1 H NMR (CDCl<sub>3</sub>, 300MHz): δ = 7.33-7.36 (m, 2H), 7.40 (d, J = 8.4Hz, 2H), 7.49-7.72 (m, 15) H), 7.78 (d, J = 9.3Hz, 1H), 7.85 (d, J = 1.5Hz, 1H) ..</p><p num="0227">[Step 3] A combination of 4- (carbazole-9-yl) diphenylamine (abbreviation: YGA) Naru</p><p num="0228">(i) Synthesis of N- (4-bromophenyl) carbazole The synthesis scheme of N- (4-bromophenyl) carbazole is shown in (A-6).</p><p num="0229"><chemistry num="7"><img id="000011" he="48" wi="148" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0230"> First, a method for synthesizing N- (4-bromophenyl) carbazole will be described. 300 56 g (0.24 mol) of 1,4-dibromobenzene in a mL three-necked flask, carba 31 g (0.18 mol) of sol, 4.6 g (0.024 mol) of copper iodide (I), 66g (0.48mol) of potassium carbonate, 2.1g of 18-crown-6-ether 0.008 mol), nitrogen substituted, 1,3-dimethyl-3,4,5,6-tetrahydro Add 8 mL of b-2 (1H) -pyrimidinone (abbreviation: DMPU) and stir at 180 ° C for 6 hours. did. After cooling the reaction mixture to room temperature, the precipitate was removed by suction filtration, and the obtained filter was obtained. The solution was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated brine in this order. Sulfuric acid in the organic layer The mixture was dried with magnesium, and after drying, the mixture was naturally filtered. Concentrate the obtained filtrate As a result, an oily substance was obtained. This oily substance is subjected to silica gel column chromatography (hex). Purification with sun: ethyl acetate = 9: 1), and the obtained solid is obtained with chloroform and hexane. When recrystallized from the mixed solvent of N- (4-bromophenyl) carbazo, which is the target product. 21 g of light brown plate crystals of allure were obtained in a yield of 35%. By Nuclear Magnetic Resonance (NMR) Therefore, it was confirmed that this compound was N- (4-bromophenyl) carbazole.</p><p num="0231"> Of this compound<sup>1</sup>The 1 H NMR data is shown below.<sup>1</sup>1 H NMR (300MHz, CDC l<sub>3</sub>); δ = 8.14 (d, J = 7.8Hz, 2H), 7.73 (d, J = 8.7Hz, 2H), 7.46 (d, J = 8.4Hz, 2H), 7.42-7.26 (m, 6H).</p><p num="0232">(ii) Synthesis of 4- (carbazole-9-yl) diphenylamine (abbreviation: YGA) 4- (Carbazole-9-yl) diphenylamine (abbreviation: YGA) synthesis scheme Shown in (A-7).</p><p num="0233"><chemistry num="8"><img id="000012" he="48" wi="148" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0234"> N- (4-bromophenyl) carbazo obtained in (i) above in a 200 mL three-necked flask. 5.4 g (17.0 mmol) of aniline, 1.8 mL (20.0 mmol) of aniline, Su (dibenzylideneacetone) palladium (0) 100 mg (0.17 mmol), na Thorium-tert-butoxide (abbreviation: tert-BuONa) 3.9g (40mm) ol) It was put in and the inside of the flask was replaced with nitrogen. To this mixture, tri (tert-butyl) phos 0.1 mL of fins (10 wt% hexane solution) and 50 mL of toluene were added. This mixture The material was stirred at 80 ° C. for 6 hours. After the reaction, the reaction mixture is mixed with Florisil, Celite, Aluminum. The filtrate was filtered through water and washed with water and saturated brine. Dry the organic layer with magnesium sulfate It was dried and the mixture was naturally filtered. Silica gel column chromatography on the oil obtained by concentrating the filtrate Purified by chromatography (hexane: ethyl acetate = 9: 1) is the desired product. 4.1 g of 4- (carbazole-9-yl) diphenylamine (abbreviation: YGA), yield 7 Obtained at 3%. By nuclear magnetic resonance (NMR), this compound is 4- (carbazole-9-). It was confirmed that it was diphenylamine (abbreviation: YGA).</p><p num="0235"> Of this compound<sup>1</sup>The 1 H NMR data is shown below.<sup>1</sup>1 H NMR (300MHz, DMS Od<sub>6</sub>); δ = 8.47 (s, 1H), 8.22 (d, J = 7.8Hz, 2H), 7. 44-7.16 (m, 14H), 6.92-6.87 (m, 1H).</p><p num="0236">[Step 4] 2YGAPPA synthesis method The synthesis scheme of 2YGAPPA is shown in (A-8).</p><p num="0237"><chemistry num="9"><img id="000013" he="97" wi="148" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0238"> 2- (4-Bromophenyl) -9,10-diphenylanthrace synthesized in step 2 0.51 g (1.1 mmol), tert-BuONa 0.20 g (2.1 mmol) , 4- (carbazole-9-yl) diphenylamine 0.35 g (1.1 mmol), bi 50 of Su (dibenzylideneacetone) palladium (0) 0.02 g (0.04 mmol) It was placed in a mL three-necked flask, and the inside of the flask was replaced with nitrogen. Toluene 10m in this mixture Add 0.02 mL of 10 wt% hexane solution of L, tri (tert-butyl) phosphine. Ta. The mixture was heated and stirred at 80 ° C. for 3 hours to react. After the reaction, add tor to the reaction mixture En was added and the suspension was suction filtered through Florisil, Celite and Alumina. Gain After washing the obtained filtrate with water and saturated brine, magnesium sulfate was added to the organic layer and dried. .. This mixture is suction filtered to remove magnesium sulfate, and the obtained filtrate is concentrated to make a solid. Obtained. The obtained solid was purified by silica gel column chromatography. Column black Matography first uses toluene: hexane = 10 as the developing solvent, then torr. This was done by using a mixed solvent of ene: hexane = 1: 5 as a developing solvent. Obtained The fraction was concentrated to give a solid. This solid is a mixed solvent of dichloromethane and methanol. When recrystallized in, a powdery yellow solid was obtained in a yield of 0.51 g and a yield of 65%. Nuclear magnetic resonance By the method (NMR), this compound was found to be 2- (4- {N- [4- (carbazole-9-a). Le) Phenyl] -N-Phenylamino} Phenyl) -9,10-Diphenylanthracene It was confirmed that it was (abbreviation: 2YGAPPA).</p><p num="0239">Sublimation purification of 1.4 g of the obtained yellow solid was carried out by the train sublimation method. Sublimation Purification is carried out under a reduced pressure of 7.0 Pa, with an argon flow rate of 3 mL / min at 333 ° C for 9 hours. It was. The yield was 1.2 g and the yield was 86%.</p><p num="0240"> Also, of the obtained compound<sup>1</sup>The 1 H NMR data is shown below. From this, the above-mentioned structural formula ( It was found that YGAPPA represented by 1) was obtained.</p><p num="0241"><sup>1</sup> NMR (CDCl<sub>3</sub>, 300MHz): δ = 7.06-7.15 (m, 1H), 7. 17-7.74 (m, 33H), 7.78 (d, J = 9.8Hz, 1H), 7.90 (s , 1H), 8.14 (d, J = 7.8Hz, 2H).</p><p num="0242"> As described above, 2YGAPPA can be synthesized.</p><p num="0243"> Next, since PCCPA used in the light emitting devices 4 to 6 is not a known substance, how to synthesize it. Explain the law. PCCPA is a substance having a structure represented by the structural formula (2).</p><p num="0244"><chemistry num="10"><img id="000014" he="39" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0245">[Step 1: 9-Phenyl-3,3'-bi (9H-carbazole) (abbreviation: PCC) Synthetic] 3-Bromocarbazole 2.5 g (10 mmol), N-Phenylcarbazole-3-bo Ronic acid 2.9 g (10 mmol), tri (ortho-tolyl) phosphine 152 mg (0. 50 mmol) was placed in a 200 mL three-necked flask. Replace the inside of the flask with nitrogen and mix this Dimethoxyethanol (DME) 50 mL, potassium carbonate aqueous solution (2 mol / L) 10 mL was added. This mixture is degassed by stirring while reducing the pressure, and after degassing, paraacetate is used. 50 mg (0.2 mmol) of dium was added. Place this mixture in a nitrogen stream at 80 ° C for 3 hours. Stirred. After stirring, add about 50 mL of toluene to this mixture, stir for about 30 minutes, and mix. The mixture was washed with water and saturated brine in that order. After washing, the organic layer is dried over magnesium sulfate. Ta. The mixture was naturally filtered, and the obtained filtrate was concentrated to obtain an oily substance. Obtained Dissolve the oily substance in toluene and pass this solution through Florisil, Alumina and Celite. When the obtained filtrate was concentrated, a white solid of the desired product was obtained in a 3.3 g yield of 80%. .. The synthesis scheme of step 1 is shown in (B-1) below.</p><p num="0246"><chemistry num="11"><img id="000015" he="72" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0247">The solid obtained in step 1 above<sup>1</sup>H NMR spectrum by nuclear magnetic resonance spectroscopy I measured it. The measurement data is shown below.</p><p num="0248"><sup>1</sup>H NMR (DMSO-d<sub>6</sub>, 300MHz): δ = 7.16-7.21 (m, 1H) , 7.29-7.60 (m, 8H), 7.67-7.74 (m, 4H), 7.81-7. 87 (m, 2H), 8.24 (d, J = 7.8Hz, 1H), 8.83 (d, J = 7.8) Hz, 1H), 8.54 (d, J = 1.5Hz, 1H), 8.65 (d, J = 1.5Hz , 1H), 11.30 (s, 1H)</p><p num="0249">[Step 2: PCCPA synthesis] 9-Phenyl-10- (4-Bromophenyl) anthracene 1.2 g (3.0 mmol) ), PCC 1.2g (3.0 mmol), tert-BuONa 1.0g (10mmo) l) was placed in a 100 mL three-necked flask. Replace the inside of the flask with nitrogen and add to this mixture. Ruen 20 mL, tri (tert-butyl) phosphine (10 wt% hexane solution) 0. 1 mL was added. The mixture was degassed by stirring while reducing the pressure. After degassing, this mixture To the mixture, bis (dibenzylideneacetone) palladium (0) 96 mg (0.17 mmol) ) Was added. The mixture was refluxed at 110 ° C for 8 hours under a nitrogen stream. After reflux, this mixture Add about 50 mL of toluene to the mixture, stir for about 30 minutes, and wash the mixture in the order of water and saturated saline. Purified. After washing, the organic layer was dried over magnesium sulfate. This mixture is naturally filtered and When the obtained filtrate was concentrated, an oily substance was obtained. The obtained oily substance is used as silica gel color. Purification was performed by muchromatography (developing solvent hexane: toluene = 1: 1). Obtained When the pale yellow solid is recrystallized from chloroform / hexane, the target PCCPA A pale yellow powdery solid was obtained in 1.2 g yield 54%. 2.4g of the obtained pale yellow powder solid It was sublimated and purified by the rain sublimation method. Sublimation purification conditions are pressure 8.7 Pa, al The PCCPA was heated at 350 ° C while flowing gongas at a flow rate of 3.0 mL / min. Noboru After Hana purification, a pale yellow solid of PCCPA was obtained in 2.2 g with a recovery rate of 94%. Also, in step 2 The synthesis scheme is shown in (B-2) below.</p><p num="0250"><chemistry num="12"><img id="000016" he="97" wi="147" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0251"> The solid obtained in step 2 above<sup>1</sup>1 H NMR was measured. The measurement data below Shown. From this, it was found that the PCCPA represented by the above structural formula (2) was obtained.</p><p num="0252"><sup>1</sup>1 H NMR (CDCl<sub>3</sub>, 300MHz): δ = 7.34-7.91 (m, 32H), 8.27 (d, J = 7.2Hz, 1H), 8.31 (d, J = 7.5Hz, 1H), 8. 52 (dd, J<sub>1</sub>= 1.5Hz, J<sub>2</sub>= 5.4Hz, 2H)</p><p num="0253"> Also, PCBAPA used in the light emitting devices 7 and 8 is not a known substance, so how to synthesize it. Explain the law. PCBAPA is a substance having a structure represented by the following structural formula (3).</p><p num="0254"><chemistry num="13"><img id="000017" he="58" wi="146" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0255">[Step 1: Synthesis of 9-Phenyl-9H-carbazole-3-boronic acid] 3-Bromo- 9-Phenyl-9H-carbazole 10 g (31 mmol) in a 500 mL three-necked flask The flask was placed in a flask and the inside of the flask was replaced with nitrogen. Frass 150 mL of tetrahydrofuran (THF) In addition to co, 3-bromo-9-phenyl-9H-carbazole was dissolved. This solution- Cooled to 80 ° C. To this solution n-butyllithium (1.58 mol / L hexane solution) 20 mL (32 mmol) was added dropwise with a syringe. After the dropping is completed, the solution is kept at the same temperature. The mixture was stirred at 1 hour. After stirring, add trimethyl borate 3.8 mL (34 mmol) to this solution. Was added, and the mixture was stirred for about 15 hours while returning to room temperature. After stirring, dilute hydrochloric acid (1.0 mo) is added to this solution. l / L) About 150 mL was added, and the mixture was stirred for 1 hour. After stirring, the aqueous layer of this mixture is acetylated. The extract was extracted with a solution, the extraction solution and the organic layer were combined, and the mixture was washed with saturated sodium hydrogen carbonate. Organic layer Was dried over magnesium sulfate, and after drying, the mixture was naturally filtered. Concentrate the obtained filtrate Upon shrinkage, a light brown oil was obtained. When this oil was dried under reduced pressure, the target product was light brown. A colored solid was obtained in 7.5 g yield 86%. The synthesis scheme of step 1 is shown in (C-1) below. ..</p><p num="0256"><chemistry num="14"><img id="000018" he="37" wi="146" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0257">[Step 2: 4- (9-Phenyl-9H-carbazole-3-yl) diphenylamine (Abbreviation: PCBA) synthesis] 4-Bromodiphenylamine 6.5g (26 mmol), 9-fe synthesized in step 1. Nyl-9H-carbazole-3-boronic acid 7.5 g (26 mmol), tri (o-tolyl) ) Put 400 mg (1.3 mmol) of phosphine into a 500 mL three-necked flask and put the flask. The inside was replaced with nitrogen. Toluene 100 mL, ethanol 50 mL, potassium carbonate to this mixture 14 mL of an aqueous solution (0.2 mol / L) was added. Stir this mixture under reduced pressure After degassing, 67 mg (30 mmol) of palladium (II) acetate was added. This mixture The material was refluxed at 100 ° C for 10 hours. After refluxing, the aqueous layer of this mixture is extracted with toluene and dissolved. The liquid and the organic layer were combined and washed with saturated brine. The organic layer is dried over magnesium sulfate and After drying, the mixture was naturally filtered, and the obtained filtrate was concentrated to obtain a light brown oily substance. .. This oil is subjected to silica gel column chromatography (developing solvent hexane: toluene = Purify by 4: 6), and the white solid obtained after purification is a mixture of dichloromethane and hexane. It was recrystallized from a medium to obtain a white solid of PCBA in a yield of 4.9 g and a yield of 45%. Step 2 synthesis The keem is shown in (C-2) below.</p><p num="0258"><chemistry num="15"><img id="000019" he="71" wi="148" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0259">[Step 3: Synthesis of PCBAPA] 9- (4-Bromophenyl) -10-Phenylanthracene 7.8 g (12 mmol), PCBA 4.8g (12 mmol), sodium tert-butoxide 5.2g (52) mmol) was placed in a 300 mL three-necked flask, and the inside of the flask was replaced with nitrogen. To this mixture , Toluene 60 mL, tri (tert-butyl) phosphine (10 wt% hexane solution) 0.30 mL was added. This mixture is degassed with stirring under reduced pressure, and after degassing, bis (di) Benzylideneacetone) palladium (0) 136 mg (0.24 mmol) was added. This The mixture was stirred at 100 ° C. for 3 hours. After stirring, add about 50 mL of toluene to this mixture. In addition, Celite (Wako Pure Chemical Industries, Ltd., Catalog No .: 531-16855), Aluminum Na, through Florisir ((Wako Pure Chemical Industries, Ltd., Catalog No .: 540-00135)) Then suction filtration was performed. The obtained filtrate was concentrated to obtain a yellow solid. Toluene and hex on this solid Recrystallized from a mixed solvent of sun, the target PCBAPA pale yellow solid 6.6 g, yield 75% Obtained. 3.0 g of the obtained pale yellow powder solid is sublimated and purified by the train sublimation method. did. Sublimation purification conditions are as follows: pressure 8.7 Pa, argon gas flow rate 3.0 mL / min While heating PCBAPA at 350 ° C. After sublimation purification, PCBAPA pale yellow solid Was obtained at 2.7 g and a recovery rate of 90%. In addition, the synthesis scheme of step 3 is changed to (C-3) below. Shown.</p><p num="0260"><chemistry num="16"><img id="000020" he="97" wi="148" file="JP2016012575A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry></p><p num="0261">The solid obtained in step 3 above<sup>1</sup>The 1 H NMR spectrum was measured. Measured below Show the data. From the measurement results, PCBAPA represented by the above structural formula (3) was obtained. I found out.</p><p num="0262"><sup>1</sup>1 H NMR (CDCl<sub>3</sub>, 300MHz): δ = 7.09-7.14 (m, 1H), 7 .28-7.72 (m, 33H), 7.88 (d, J = 8.4Hz, 2H), 8.19 ( d, J = 7.2Hz, 1H), 8.37 (d, J = 1.5Hz, 1H)</p>
0263100 Second electrode 101 First electrode 102 First layer 103 Second layer 104 Third layer 105 hole transport layer 106 Luminescent element 107 Layer containing organic compounds 110 Second electrode 111 First electrode 112 First layer 113 Second layer 114 Hole transport layer 115 light emitting element 116 Layer containing organic compounds 601 Drive circuit section (source side drive circuit) 602 pixel part 603 Drive circuit section (gate side drive circuit) 604 Encapsulation board 605 Sealing material 607 space 608 wiring 609 FPC (Flexible Print Circuit) 610 element board 611 TFT for switching 612 TFT for current control 613 1st electrode 614 insulation 616 Layer containing organic compounds 617 Second electrode 618 Light emitting element 623 n-channel TFT 624 p channel type TFT 901 housing 902 Liquid crystal layer 903 Backlight unit 904 chassis 905 driver IC 906 terminal 951 board 952 Electrode 953 Insulation layer 954 Bulkhead layer 955 Layer containing organic compounds 956 electrode 2001 chassis 2002 light source 3001 Lighting device 9101 chassis 9102 Support stand 9103 Display 9104 Speaker section 9105 Video input terminal 9201 body 9202 chassis 9203 Display 9204 keyboard 9205 External connection port 9206 Pointing device 9401 body 9402 chassis 9403 Display 9404 Voice input section 9405 Audio output section 9406 Operation key 9407 External connection port 9408 antenna 9501 body 9502 Display 9503 chassis 9504 External connection port 9505 Remote control receiver 9506 Image receiving part 9507 battery 9508 Voice input section 9509 Operation key 9510 Eyepiece
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Numbers
- Publication
- 2016012575
- Application
- 207666
Titles2
- Japanese
- 発光素子
- English
- Light emitting element
Classification
- CPC, 12
- H10K50/125
- H05B33/14
- H10K59/122
- H10K59/173
- H10K85/622
- H10K85/615
- H10K85/631
- H10K85/324
- H05B33/20
- H05B33/145
- H10K50/15
- H10K50/16
- IPC, 3
- H05B33 12
- H01L51 50
- H10K99 00