Semiconductor device, apparatus and method for manufacturing the same

The present invention relates to a semiconductor device manufacturing apparatus, and in particular, manufactures a silicon nitride film (SiN film) for ICs formed at a low temperature, and a semiconductor device used for forming a passivation SiN film for a glass substrate used for liquid crystal or organic EL. Regarding the device.

The present invention also relates to a semiconductor device manufacturing apparatus used for photolithography that produces a finer pattern from a fine resist pattern.

Conventionally, aminosilane (H₃SiNH₂) A method of forming a silicon nitride film (SiN film) by thermochemical vapor deposition in the range of 0.1 Torr to 760 Torr, 500 ° C to 1000 ° C using gas as a raw material has been proposed (Patent Document 1). ..

<patcit num="1"><text>Patent No. 2890698</text></patcit>

<p> However, the method disclosed in Patent Document 1 requires high-temperature processing such as "500 ° C to 1000 ° C", which makes it difficult to miniaturize various ICs including DRAM and logic ICs. .. In order to prevent this, it is necessary to perform a low temperature treatment such that the temperature at which the sidewall SiN film is formed on the gate electrode on the wafer is suppressed to 450 ° C. or less.</p><p> For example, in a device with a design rule of 32 nm or less, the distance between the source region and the drain region is very narrow, so when processing exceeding 500 ° C is performed, the source region and the drain region physically come into contact with each other. It is possible that the device will not work.</p><p> Further, when forming a SiN film as a passivation film for a liquid crystal device or a flexible device, a low temperature treatment such as suppressing the temperature to 200 ° C. or less is required.</p><p> On the other hand, even if the high temperature treatment is simply replaced with the low temperature treatment, the carbon (C) component, the chlorine (Cl) component, or the hydrogen (H) component will be contained in the SiN film, so that the particles are contained in the SiN film. Will occur, and adverse effects such as inferior semiconductor characteristics will occur.</p><p> Therefore, in view of the above circumstances, it is an object of the present invention to devise manufacturing conditions so that a desired SiN film with less plasma damage can be manufactured by low-temperature treatment.</p>

<p> In order to solve the above problems, the semiconductor device manufacturing apparatus of the present invention is used. A means of supplying a silicon-based gas containing a hydrogen component to the object to be treated, A means for supplying the nitrogen-based gas to the processing target after supplying the silicon-based gas is provided. In order to solve the above problems, the semiconductor device manufacturing apparatus of the present invention includes means for supplying a silicon-based gas containing a hydrogen component or a halogen component to a processing target, and the processing target after supplying the silicon-based gas. A means for supplying a nitrogen-based gas to the lamp is provided.</p><p> The silicon-based gas containing a hydrogen component or a halogen component (hereinafter, may be simply referred to as silicon-based gas) according to the present invention has a hydrogen atom or a halogen atom in its molecular structure, and is hydrogen. The atom or halogen atom does not have to be directly bonded to the silicon atom. Aminosilane (H) has a hydrogen component.₃SiNH₂) Gas, diaminosilane (H)₂Si (NH₂)₂) Gas, triaminosilane (HSi (NH)₂)₃), Tetraaminosilane (Si (NH)₂)₄) Gases and other aminosilane gases; dimethylaminosilane (H)₃SiN (CH₃)₂) Gas, bis (dimethylamino) silane (H)₂Si [N (CH)₃)₂]₂) Gas, tris (dimethylamino) silane (HSi [N (CH)₃)₂]₃) Gas, tetrakis (dimethylamino) silane (Si [N (CH)₃)₂]₄) Gas, diethylaminosilane (H)₃SiN (C₂H₅)₂) Gas, bis (diethylamino) silane (H)₂Si [N (C)₂H₅)₂]₂) Gas, tris (diethylamino) silane (HSi [N (C)₂H₅)₂]₃) Gas, tetrakis (diethylamino) silane (Si [N (C)₂H₅)₂]₄) Gas, diisopropylaminosilane (H)₃SiN (iC₃H₇)₂) Gas, bis (diisopropylamino) silane (H)₂Si [N (iC₃H₇)₂]₂) Gas, tris (diisopropylamino) silane (HSi [N (iC)₃H₇)₂]₃) Gas, tetrakis (diisopropylamino) silane (Si [N (iC)₃H₇)₂]₄) Alkylaminosilanes such as gas; tetraaminodisilazane (H (NH)₂)₂Si-NH-Si (NH₂)₂H) gas, tetramethyldisilazane (H (CH)₃)₂Si-NH-Si (CH₃)₂H) Disilazans such as gas, monosilane (SiH)₄) Gas, disilane (Si₂H₆), And examples of the silicon-based gas containing a halogen component include tetrachlorosilane (SiCl).₄) Gas, tetrabromosilane (SiBr)₄) Gas, tetraiodosilane (SiI)₄) Gas, hexachlorodisilane (Cl₃Si-SiCl₃) Gas, hexabromodisilane (Br)₃Si-SiBr₃) Silane halides such as gas can be mentioned.</p><p> Further, the silicon-based gas according to the present invention may contain both hydrogen atoms of a hydrogen component and a halogen component. For example, chlorosilane (H₃SiCl) gas, dichlorosilane (H)₂SiCl₂) Gas, trichlorosilane (HSiCl)₃) Gas, dichlorodisilane (H)₂ClSi-SiClH₂) Gas, tetrachlorodisilane (HCl)₂Si-SiCl₂H) Partially halogen-substituted silanes such as gas; dimethylaminotrichlorosilane (Cl)₃SiN (CH₃)₂) Gas, bis [dimethylamino] dichlorosilane (Cl₂Si [N (CH)₃)₂]₂) Gas, Tris [dimethylamino] chlorosilane (ClSi [N (CH)₃)₂]₃) Gas, diethylaminotrichlorosilane (Cl₃SiN (C₂H₅)₂) Gas, bis [diethylamino] dichlorosilane (Cl₂Si [N (C)₂H₅)₂]₂) Gas, Tris [diethylamino] chlorosilane (ClSi [N (C)₂H₅)₂]₃) Gas, dimethylaminochlorosilane (H)₂ClSi [N (CH)₃)₂]) Gas, diethylaminochlorosilane (H₂ClSi [N (C)₂H₅)₂]) Gas, dipropylaminochlorosilane (H₂ClSi [N (C)₃H₇)₂]) Alkylaminosilane halides such as gas can be mentioned.</p><p> The silicon-based gas is adhered to a substrate, a wafer, or the like to be treated to form a silicon-based compound film, or is decomposed or reacted to form a precursor deposition film (hereinafter, a silicon-based compound film and a precursor deposition film, for example. , Si-H membrane, Si-NH membrane, SiO-NH membrane, etc., which may be described using reactive sites remaining in the membrane.)</p><p> The nitrogen-based gas according to the present invention is a gas containing a nitrogen atom, and is nitrogen (N).₂) Gas, ammonia (NH₃) Gas, diazine gas (N₂H₂), Hydrazine gas (N₂H₄), Alkyl hydrazine gas (RNHNH₂, R₂NNH₂; R represents methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl, etc.), etc., which may be used alone or in admixture of two or more. You may.</p><p> According to the semiconductor device manufacturing apparatus of the present invention, if a nitrogen-based gas is supplied with a silicon-based gas adhered to a processing target, a SiN film can be formed at a temperature of, for example, 450 ° C. or less. .. This SiN film can also be formed as a passivation film on a glass substrate. Further, according to the present invention, an etching pattern finer than the resist pattern can be formed, and a finer pattern exceeding the limit of photolithography can be formed. Further, excitation or decomposition of the nitrogen-based gas or silicon-based gas, including excitation treatment (decompression pulse CVD method or decompression pulse plasma method (including remote plasma method), etc.), ultraviolet light irradiation treatment, or heating treatment. It is good to have means. The nitrogen-based gas or silicon-based gas is either excited to the plasma state by the plasma excitation process or decomposed through the plasma state, and is excited or decomposed through the excited state by the irradiation treatment of ultraviolet light. It is thermally decomposed by heating. Further, the heating treatment may be provided to assist the excitation treatment. When only heating treatment is used as the decomposition means, hydrazine gas, alkyl hydrazine (RNHNH)₂, R₂NNH₂Etc.) It is advisable to select a nitrogen-based gas that decomposes at 450 ° C or less, such as gas and ammonia gas.</p><p> As the excitation or decomposition means of the semiconductor manufacturing apparatus of the present invention, when it is necessary to eliminate the concern about deformation or alteration of the processing target due to heating or plasma damage, ultraviolet light irradiation treatment is selected. For example, by selecting the ultraviolet light irradiation treatment, it is possible to avoid damage to the gate oxide film due to plasma and to avoid electrical short circuits due to contact between the source and drain of low-concentration impurity regions due to temperatures exceeding 450 ° C. , It is possible to manufacture semiconductors with a design rule of 32 nm or less. In particular, it is suitable for the deposition of the sidewall film type of SiN film necessary for forming the source and drain, which are high-concentration impurity regions with respect to the gate electrode on the wafer. Further, a heating means may be used in combination to assist the effect of the ultraviolet light irradiation treatment, but the temperature shall be 450 ° C. or less. The combined use of heating treatment has the effect of promoting the SiN film formation reaction and densifying the SiN film.</p><p> The silicon-based gas and the nitrogen-based gas may be supplied alternately or together. Further, after supplying the silicon-based gas, it is preferable to provide a means for performing a plasma excitation treatment or an ultraviolet light irradiation treatment on the nitrogen-based gas. Further, after supplying each gas, it is preferable to irradiate the processing target with visible light, ultraviolet light or infrared light.</p><p> Further, when the ultraviolet light irradiation treatment is provided, a means for supplying an inert gas to the ultraviolet light irradiation means can be provided. By supplying the inert gas to the light source of ultraviolet light from here, it is possible to prevent the adhesion of dirt due to the silicon-based gas and / or the nitrogen gas, and it is possible to reduce the labor and frequency of equipment maintenance. Unless otherwise specified, the inert gas in the present invention includes rare gases such as helium (He) gas, neon (Ne) gas, and argon (Ar) gas, and nitrogen (N).₂) A gas that does not directly contribute to the film formation reaction in semiconductor manufacturing such as gas. The inert gas is mainly used as a carrier gas, a diluting gas, and a purge gas. In the present invention, nitrogen may be used as a nitrogen-based gas or as an inert gas.</p><p> Further, the method for manufacturing a semiconductor device of the present invention includes a step of supplying a silicon-based gas containing a hydrogen component or a halogen component to the processing target, and a nitrogen-based gas to the processing target after supplying the silicon-based gas. One or both of the silicon-based gas and the nitrogen-based gas are excited or decomposed by at least one means selected from a heating treatment, a plasma excitation treatment, or an ultraviolet light irradiation treatment. , Is supplied to the processing target. In the case of excitation or decomposition, if the treatment is performed only on the nitrogen-based gas, it is possible to prevent the film from adhering to the substrate other than the substrate containing the treatment target, and thereby a good manufacturing method in which particles are suppressed can be realized. .. Further, further effects can be expected by performing the plasma treatment and the irradiation treatment of ultraviolet light only when the gas to be treated is introduced.</p><p> When the silicon-based gas is adsorbed or adhered to the treatment target to form a silicon-based compound film, the temperature of the treatment target is set to the lowest possible temperature so that the silicon-based compound does not desorb or volatilize from the treatment target. The temperature is preferably room temperature to 300 ° C.</p><p> Excitation or decomposition treatment is also applied to the bonding group of the silicon-based compound film adsorbed or adhered to the treatment target to improve the membrane properties obtained. When the nitrogen-based gas is supplied, the excitation or decomposition treatment is performed, and at the same time as the nitrogen-based gas, the bonding group of the silicon-based compound film is also excited or decomposed to efficiently form a good film.</p><p> Further, the semiconductor device of the present invention includes a processing target processed by being supplied with a silicon-based gas and then being supplied with a nitrogen-based gas. Specifically, the semiconductor device of the present invention is a device having a design rule of 32 nm or less, and the source region and the drain region are not in physical contact with each other. This semiconductor device can be manufactured by using the above-mentioned manufacturing apparatus.</p>

<figref num="1">It is a schematic block diagram of the manufacturing apparatus of the semiconductor device of Embodiment 1 of this invention.</figref><figref num="2">It is a schematic block diagram of the first chamber 5 of FIG.</figref><figref num="3">It is a schematic block diagram of the second chamber 6 of FIG.</figref><figref num="4">It is a schematic cross-sectional view of the wafer 41 manufactured by the semiconductor device manufacturing apparatus shown in FIG.</figref><figref num="5">It is a schematic partial cross-sectional view of the non-volatile memory including the semiconductor device manufactured by using the apparatus shown in FIG.</figref><figref num="6">It is a schematic partial cross-sectional view of a DRAM capacitor including a semiconductor device manufactured by using the manufacturing apparatus shown in FIG.</figref><figref num="7">It is a schematic block diagram of the 1st chamber 5 which concerns on Embodiment 5 of this invention.</figref><figref num="8">It is a schematic block diagram of the decompression CVD apparatus which concerns on Embodiments 6 and 7 of this invention.</figref>

1 cassette 2 Wafer alignment 3 Load lock chamber 4 Transfer chamber 5 First chamber 6 Second chamber

Embodiment of the invention

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each figure, the same parts are designated by the same reference numerals. (Embodiment 1) FIG. 1 is a schematic configuration diagram of a semiconductor device manufacturing apparatus according to the first embodiment of the present invention. FIG. 1 shows a cassette 1 in which a wafer is housed, a wafer alignment 2 for positioning a wafer taken out from the cassette 1, a load lock chamber 3 having a load lock mechanism, and an insulator for forming an insulator on the wafer. Between the first chamber 5, the second chamber 6 in which the wafer on which the insulator is formed in the first chamber 5 is subjected to ultraviolet light annealing treatment, and the load lock chamber 3, the first chamber 5, and the second chamber 6 are mutually connected. A transfer chamber 4 having a robot arm for transporting wafers is shown.

FIG. 2 is a schematic configuration diagram of the first chamber 5 of FIG. FIG. 2 shows aminosilane (H) for forming SiN film 603 (FIG. 4).₃SiNH₂) Gas, diaminosilane (H)₂Si (NH₂)₂) Gas, triaminosilane (HSi (NH)₂)₃) Gas, tetraaminosilane (Si (NH)₂)₄) Gas, or dimethylaminosilane (H)₃SiN (CH₃)₂) Gas, bis (dimethylamino) silane (H)₂Si (N (CH)₃)₂)₂) Gas, tris (dimethylamino) silane (HSi (N (CH)₃)₂)₃) Gas, tetrakis (dimethylamino) silane (Si (N (CH))₃)₂)₄) Gas, disilane (Si₂H₆) Gas supply pipe 71 and tetraaminodisilazane (H (NH)), which is an alternative gas such as triaminosilane gas.₂)₂Si-NH-Si (NH₂)₂H) gas or tetramethyldisilazane (H (CH)₃)₂Si-NH-Si (CH₃)₂H) Gas supply pipe 72, steam supply pipe 73, and N₂H₄Gas supply pipe 74 and helium gas, N₂It shows the supply pipe 75 for gas and the like. The supply pipes 71 and 72 are for supplying the silicon-based gas to the first chamber 5. The supply pipe 74 is for supplying the nitrogen-based gas to the first chamber 5. The supply pipe 75 is for supplying the inert gas to the first chamber 5. The above description has been described as a representative of a system using a silicon-based gas system containing a hydrogen component, but when a silicon-based gas containing a halogen component is used, it may be supplied through a supply pipe 71 or 72. Another supply pipe may be newly installed.

Each of the supply pipes 71 and the like is connected to the collective pipe 13 via the valve 16 and the mass flow controller 15, respectively. A valve 14 for switching various gases passing through the collecting pipe 13 is attached to the collecting pipe 13. An alumina pipe 12 is provided downstream of the valve 14.

Further, in the first chamber 5, a gas shower for spraying the gas passing through the collecting pipe 13 onto the wafer 41 is provided. The gas shower is provided with a gas dispersion plate 31 for supplying the gas to the first chamber 5 at a uniform concentration, and a shower plate 32 provided downstream of the gas dispersion plate 31 and having a plurality of openings 33 formed therein. Has been done.

Also shown in FIG. 2 is nitrogen trifluoride (NF) for cleaning the first chamber 5.₃) Gas supply pipe 81, oxygen (O₂) Gas supply pipe 82, argon (Ar) gas supply pipe 83, and NH for forming SiN film 603.₃Gas supply pipe 84 and NH₃N, which is an alternative gas to gas₂H₄The gas supply pipe 85 is shown. The supply pipes 84 and 85 are for supplying nitrogen-based gas to the first chamber 5.

Each supply pipe 81 or the like is connected to a remote plasma device 21 that turns into plasma prior to supplying various gases passing through each supply pipe 81 or the like to the first chamber 5 via a valve 16 and a mass flow controller 15, respectively. It is connected. An RF oscillator 11 that supplies a high frequency required for plasma conversion of the reaction gas is attached in the vicinity of the remote plasma device 21.

Further, in the first chamber 5, a heater 51 made of an insulator (AlN or Al) for heating the wafer 41, a lift pin 52 for receiving the wafer 41 conveyed by the transfer chamber 4, and a lift pin 52 for raising and lowering the lift pin 52. The drive mechanism 53, the exhaust valve 62 for exhausting the gas in the first chamber 5, and the exhaust pump 61 connected to the exhaust valve 62 are connected.

FIG. 3 is a schematic configuration diagram of the second chamber 6 of FIG. In Fig. 3, a plurality of (for example, four) lamps 101 such as a low-pressure mercury lamp, an Xe excimer lamp, and a metal halide lamp that irradiate ultraviolet light, and each lamp 101 are protected from the stress applied during depressurization, and each lamp 101 is supplied. , A quartz pipe 102 that prevents contact with oxygen, silicon gas, and nitrogen gas, and an inert gas 103 such as helium gas, argon gas, and nitrogen gas supplied in the quartz pipe 102, continuously, regularly, and It indicates a light receiving sensor 104 attached to the inside or outside of the quartz pipe 102 or the second chamber 6 that intermittently measures the illuminance of the irradiation light from the lamp 101.

Further, FIG. 3 shows a gas pipe 75 for supplying nitrogen gas into the second chamber 6 and an oxygen gas or ozone gas for cleaning the inside of the second chamber 6 after processing the wafer 41. N for reacting with the supply pipe 76 and the Si-H-based, Si-NH-based, and SiO-NH-based films adsorbed or deposited on the substrate in the second chamber 6 as well.₂H₄A supply pipe 77 for supplying a nitrogen-based gas such as a gas is shown. If necessary, an inert gas instead of nitrogen gas may be supplied into the second chamber 6. Further, one chamber which also serves as the first chamber 5 and the second chamber 6 may be prepared. Specifically, it can be realized by providing a lamp 101 or the like in the first chamber 5.

FIG. 4 is a schematic cross-sectional view of the wafer 41 manufactured by the semiconductor device manufacturing apparatus shown in FIG. FIG. 4A shows a state in which the SiN film 603 is formed on the wafer 41 provided with the gate electrode 602. If the SiN film 603 is subjected to the required etching by a known method in an etching chamber (not shown) from the state shown in FIG. 4 (a), the gate electrode 602 has a sidewall 604 as shown in FIG. 4 (b). Will be formed.

Next, the processing procedure by the semiconductor device manufacturing apparatus shown in FIG. 1 will be described. In the present embodiment, first, the wafer 41 provided with the gate electrode 602 is conveyed from a cleaning device in a clean room (not shown) in a state of being housed in the hoop 1. After that, the wafer 41 is taken out from the hoop 1 and conveyed to the wafer alignment 2 side.

In wafer alignment 2, the wafer 41 is positioned. The wafer 41 is then transferred to the load lock chamber 3 prior to being transferred to the first chamber 5.

Next, the pressure inside the load lock chamber 3 is reduced. Then, when the pressure inside the load lock chamber 3 reaches a desired pressure, the gate valve that separates the load lock chamber 3 and the transfer chamber 4 is opened.

After that, the wafer 41 is transferred into the transfer chamber 4. Subsequently, the wafer 41 is conveyed from the load lock chamber 3 into the first chamber 5 by the robot arm in the transfer chamber 4.

In the first chamber 5, the heater 51 is set under the condition that the surface temperature of the wafer 41 is in the range of 200 ° C to 450 ° C (for example, 300 ° C). Next, the wafer 41 is placed on the lift pin 52 located above the fixed heater 51 in advance, and then the lift pin 52 is lowered by the drive mechanism 53 to place the wafer 41 on the heater 51. Place it.

Alternatively, the movable heater 51 may be lowered in advance, the wafer 41 may be placed on the lift pin 52, and then the heater 51 may be raised to place the wafer 41 on the heater 51. In the first chamber, the exhaust pump 61 is already turned on, the exhaust valve 62 is opened, and the inside of the first chamber 5 is exhausted.

Next, the valve 16 is opened under the control of the mass flow controller 15 related to the supply pipe 71, and triaminosilane gas or the like is flowed at a flow rate of 50 cc / min to 100 cc / min (for example, 75 cc / min) for 1 minute to 5 minutes (for example, 3 minutes). ), Supply to the first chamber 5.

At this time, the exhaust valve 62 is opened under the condition that the pressure in the first chamber 5 is 133 to 1330 Pa (for example, 399 Pa). The triaminosilane gas or the like supplied to the first chamber 5 reaches the wafer 41 through the openings 33 of the gas dispersion plate 31 and the shower plate 32.

Then, after setting the pressure in the first chamber 5 to 13.3 Pa to 133 Pa (for example, 67 Pa), the valve 16 related to the supply pipe 71 is closed and the valve 16 related to the supply pipe 74 is opened, and then N₂H₄After flowing gas at a flow rate of 400cc / min to 800cc / min (for example, 600cc / min) and setting the pressure in the first chamber 5 to 133Pa to 1330Pa (for example, 399Pa), for 1 to 5 minutes (for example, 3 minutes), N in the first chamber 5₂H₄Supply gas.

After that, N from the supply of triaminosilane gas etc.₂H₄The cycle up to gas supply is repeated 10 to 20 times (for example, 15 times) in total. As a result, a SiN film 603 having a thickness of about 30 nm is formed on the gate electrode 602 of the wafer 41. Wafer 41 was taken out from the first chamber 5, and the refractive index of SiN film 603 was measured. The refractive index of the SiN film 603 was measured for a plurality of wafers 41, and all of them were about 2.0 or less, and the average value was about 1.95. Further, when the source-drain impurity profile of the wafer 41 was measured, the impurities were not diffused in the channel region because the low temperature treatment was performed in this embodiment, and there was no source-drain short circuit.

Instead of supplying the triaminosilane gas or the like through the supply pipe 71, the tetraaminodisilazane gas or the like through the supply pipe 72 may be supplied at the same flow rate and the same time as, for example, the triaminosilane. In this case as well, the pressure in the first chamber 5 is N with tetraaminodisilazane gas or the like.₂H₄Both when supplied with gas, it may be about 133Pa to 1330Pa (for example, 399Pa), the number of cycles is 5 to 15 times (for example, 10 times), and the average refractive index is as described above under other conditions. Is about 1.96, and a SiN film 603 with a thickness of about 30 nm can be formed.

Then, the wafer 41 is subjected to an ultraviolet light annealing treatment having a wavelength of 254 nm or more in the second chamber 6. The ultraviolet light annealing treatment has the advantage that the extinction coefficient (corresponding to the absorption coefficient) increases and the SiN film 603 becomes dense. When the ultraviolet light annealing treatment is performed, the wafer 41 is transferred from the first chamber 5 to the second chamber 6 by the robot arm in the transfer chamber 4.

In the second chamber 6, the heater 51 is set under the condition that the surface temperature of the wafer 41 is in the range of 300 to 450 ° C (for example, 400 ° C). Here, the temperature may be set higher than that of the heater 51 of the first chamber 5. Next, the wafer 41 is placed on the heater 51. In the second chamber 6, the exhaust pump 61 is already turned on, the exhaust valve 62 is opened, and N₂The gas is supplied from 100 cc / min to 300 cc / min (for example, 200 cc / min) and exhausted under the condition that the pressure in the second chamber 6 is 13.3 Pa to 399 Pa (for example, 133 Pa).

And from the lamp 101, for example, wavelength 185 + 254 nm, power 10 mW / cm²The wafer 41 is subjected to ultraviolet annealing treatment by irradiating the wafer 41 with low-pressure mercury light for 1 to 5 minutes (for example, 2 minutes).

Further, the first chamber 5 is cleaned after performing the above-described processing on about 10 wafers 41. Specifically, the valve 16 is opened under the control of the mass flow controller 15, and the Ar gas with a flow rate of about 200 cc / min and the O with a flow rate of about 100 cc / min enter the first chamber 5 through the gas supply pipes 81 to 83.₂Gas and NF with a flow rate of about 400cc / min₃The mixed gas with the gas is output to the remote plasma device (or RF plasma device 11) 21.

Then, the remote plasma device 21 is turned on to turn each gas into plasma and supply it to the chamber 5. At this time, the inside of the first chamber 5 is exhausted by turning on the exhaust pump 61 and opening the exhaust valve 62. The pressure in the first chamber 5 at the time of exhaust may be about 67 to 399 Pa.

In the present embodiment, the case where the average value of the refractive index is about 1.96 and a SiN film 603 with a thickness of about 30 nm is formed has been described as an example. However, a semiconductor device having a SiN film 603 with a thickness of about 3 nm is formed. By manufacturing, it is also possible to realize a non-volatile memory having excellent memory characteristics, which incorporates silicon oxide (SONOS).

FIG. 5 is a schematic partial cross-sectional view of a non-volatile memory including a semiconductor device manufactured using the apparatus shown in FIG. In FIG. 5, the source region 801 and the drain region 802 formed in the wafer 41 and the SiO which is the tunnel insulating film formed on the wafer 41.₂SiO for floating gates formed on Membrane 803 and SiN Membrane 603₂Membrane 805 and SiO₂It shows a control gate 806 formed on the membrane 805.

The formation of the SiN film 603 can be realized by reducing the number of cycles described above to about 1 to 3 times. However, N₂H₄The gas flow rate is the same, and the triaminosilane flow rate may be as low as 50 cc / min.

However, when manufacturing this non-volatile memory, the wafer 41 transferred to the first chamber 5 has already been subjected to the source region 801 and the drain region 802 and SiO.₂Note that the membrane 803 needs to be formed.

Further, a small DRAM capacitor can be realized by manufacturing a semiconductor device in which a SiN film 603 having a thickness of about 20 nm is formed.

FIG. 6 is a schematic partial cross-sectional view of a DRAM capacitor including a semiconductor device manufactured by using the manufacturing apparatus shown in FIG. Figure 6 shows SiO₂A high-k insulating film 704 selectively formed on the film 803, a metal or polysilicon film 705 formed on the high-k insulating film 704, and a SiO formed on the metal or polysilicon film 705.₂Membrane 706 and SiO₂Sidewall SiO formed on the side wall of membrane 706₂The film 707, the capacitor lower electrode (polysilicon) 708 formed on the drain 802, and the capacitor upper electrode 710 formed via the SiN film 603 with respect to the capacitor lower electrode are shown.

The formation of SiN film 603 can be realized by reducing the number of cycles described above to about 5 to 10 times.

In the present embodiment, the case where the SiN film 603 is formed on the wafer 41 has been described as an example, but by changing the gas supplied to the first chamber 5, the silicon oxide film (SiO)₂A membrane) or a silicon oxynitride membrane (SiON membrane) can also be formed. Specifically, SiO₂When forming a film, water vapor is passed through the supply pipe 73, and N is passed through the supply pipe 75.₂The gas may be supplied at the same time at a flow rate of 100 cc / min to 300 cc / min (for example, 200 cc / min).

When forming a SiON film on the wafer 41, N₂H₄When supplying gas, water vapor may be supplied from 20 cc / min to 100 cc / min (for example, 50 cc / min) through the supply pipe 73 at a flow rate of 50 cc / min to 100 cc / min (for example, 75 cc / min). Since the depotation is improved by supplying water vapor, the number of cycles described above can be reduced to about half (5 to 10 times).

(Embodiment 2) In the embodiment of the present invention, a method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 using a gas different from the gas described in the first embodiment using the apparatus shown in FIG. 1 and the like will be described. To do. The production conditions are the same as in the case of the first embodiment except for the following points.

1. Use tetraaminodisilazane gas, etc. instead of triaminosilane gas, etc. Therefore, the valve 16 related to the supply pipe 72 is opened.

2.N₂H₄NH instead of gas₃Use gas. Therefore, the valve 16 related to the supply pipe 84 is opened. NH₃The gas flow rate shall be 400cc / min to 800cc / min (for example, 600cc / min).

3. After opening the valve 16 related to the supply pipe 84, turn on the remote plasma device 21 for 1 to 5 minutes (for example, 3 minutes). The remote plasma device 21 uses, for example, a high frequency of 13.56 MHz or 400 Hz, and has an output of 400 W to 1000 W (for example, 750 W), and is NH.₃Turn the gas into plasma. As a result, NH₃The gas is supplied to the first chamber 5 in a plasmaized state.

In addition to supplying each of the above gases to the first chamber 5 several times, tetraaminodisilazane gas and NH₃It is also possible to supply the gas not only alternately but also once together for 20 to 50 seconds (for example, 30 seconds). At this time, the "flow rate", "pressure", and "temperature" of the gas may be the same as in the cases 1 to 3 above.

As a result, a SiN film 603 having an average refractive index of about 1.97 and a thickness of about 50 nm can be formed on the wafer 41.

The wafer 41 of the present embodiment can also be incorporated into a non-volatile memory, a DRAM capacitor, or the like by appropriately selecting the thickness of the SiN film 603, as in the case of the first embodiment. The same applies to each embodiment described below.

(Embodiment 3) In the embodiment of the present invention, the SiN film 603 is formed on the glass substrate by using the manufacturing apparatus shown in FIG. 1 or the like and using a gas different from the gas described in the first embodiment. The production conditions are the same as in the case of the first embodiment except for the following points.

1. Wafer 41 is used as a glass substrate.

2.N₂H₄NH instead of gas₃Use gas. In addition, NH₃The gas flow rate and plasma conversion conditions may be the same as those in the second embodiment.

3. Not only supply each of the above gases to the first chamber 5 several times (in this case, the same conditions as in the second embodiment), but also triaminosilane gas and the like and NH.₃The gas may be supplied not only alternately but also once for 1 minute to 3 minutes (for example, 2 minutes).

4. When supplying each of the above gases, the pressure in the first chamber 5 shall be 13.3 Pa to 1330 Pa (for example, 399 Pa).

As a result, a SiN film 603 having an average refractive index of about 1.93 and a thickness of about 100 nm can be formed on the wafer 41.

After that, the wafer 41 is subjected to an ultraviolet light annealing treatment at 200 to 400 ° C (300 ° C) under the same conditions as in the first embodiment, for example. N-type amorphous silicon was formed on the glass substrate wafer 41 with a thickness of about 100 nm, and a SiN film was formed on the glass substrate wafer 41 by the method of the present embodiment at about 100 nm. Then, the SiN film was subjected to an ultraviolet annealing treatment. In addition, SiO on the SiN film₂The film was formed to a thickness of about 100 nm. Then, 100 nm of N-type amorphous silicon is formed on it, and patterning is performed. After applying a voltage of 200 V and a temperature of 300 ° C to the upper and lower amorphous silicon, V is measured by CV measurement._FBWhen the shift was examined, the fact that sodium and the like were diffused from the glass substrate wafer 41 was not found.

In addition, instead of triaminosilane gas or the like, tetraaminodisilazane gas or the like may be used. At this time, if it is not necessary to shorten the time required for forming the SiN film 603, first, tetraaminodisilazane gas or the like is applied at a flow rate of 50 cc / min to 100 cc / min (for example, 75 cc / min) for 1 minute to. It is supplied to the first chamber 5 under the condition of 133 to 1330 Pa (for example, 399 Pa) for 5 minutes (for example, 3 minutes).

Also, NH₃Plasmaized NH using gas₃Gas is applied to the first chamber 5 at a flow rate of 400 cc / min to 800 cc / min (for example, 600 cc / min) for 1 minute to 5 minutes (for example, 2 minutes) under the condition of 13.3 Pa to 1330 Pa (for example, 399 Pa). Supply. In this case, supply of tetraaminodisilazane gas, etc. and NH₃The gas supply may be repeated alternately in a cycle of 15 to 25 times (for example, 20 times) in total.

Even when tetraaminodisilazane gas or the like is used, tetraaminodisilazane gas and N₂H₄When the gas is supplied at the same time, the supply time of each gas is shortened to 15 to 40 seconds (for example, 25 seconds), and even if the other conditions are the same as those of the present embodiment, the wafer 41 has a refractive index. A SiN film 603 with an average value of about 1.97 and a thickness of about 100 nm can be formed.

(Embodiment 4) In the embodiment of the present invention, a method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 by a method different from the method described in the first embodiment will be described using the manufacturing apparatus shown in FIG. 1 and the like. .. The production conditions are the same as in the case of the first embodiment except for the following points.

1. NH excited by triaminosilane gas etc. and plasma₃The SiN film 603 is formed by alternately supplying gas. Specifically, a Si-NH film is formed on the gate electrode 602 of the wafer 41 with a thickness of about 2 nm. The flow rate and pressure are the same as those in the third embodiment.

2. NH plasmalized by the remote plasma device 21 under the same conditions as in the second embodiment.₃The gas is supplied to the first chamber 5 having a pressure of 67 Pa to 399 Pa (for example, 133 Pa). NH₃The flow rate of the gas may be 400 cc / min to 800 cc / min (for example, 600 cc / min), and the supply time may be 1 minute to 5 minutes (for example, 3 minutes).

As a result, the previously formed Si-NH film is nitrided to obtain a SiN film 603 having a thickness of about 20 nm and an average refractive index of 1.99.

Further, after forming the SiN film 603, the SiN film 603 may be further strengthened by irradiating with ultraviolet rays having a wavelength equal to or higher than that of low-pressure mercury.

(Embodiment 5) In the embodiment of the present invention, a method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 by a method different from the method described in the first embodiment will be described using the manufacturing apparatus shown in FIG. 1 and the like. .. The production conditions are the same as in the case of the first embodiment except for the following points.

1. Triaminosilane gas, etc. and illuminance of 10 W / cm²NH excited by UV irradiation₃A Si-NH film is formed by alternately supplying gas. Specifically, a Si-NH film is formed on the gate electrode 602 of the wafer 41 with a thickness of about 2 nm. The flow rate and pressure of each gas are the same as those in the third embodiment.

2. NH excited by UV irradiation₃The gas is supplied to the first chamber 5 having a pressure of 67 Pa to 399 Pa (for example, 133 Pa). NH₃The flow rate of the gas may be 400 cc / min to 800 cc / min (for example, 600 cc / min), and the supply time may be 1 minute to 5 minutes (for example, 3 minutes).

As a result, NH excited by ultraviolet light₃At the same time as the gas, the Si-NH film in which the bonding groups in the film are excited or decomposed by ultraviolet light reacts more efficiently, and a SiN film 603 with a thickness of about 20 nm and an average refractive index of 1.99 is obtained. ..

By heating at 450 ° C or less, N₂H₄The gas may be decomposed. Further, after forming the SiN film 603, the SiN film 603 may be further strengthened by irradiating with ultraviolet light having a wavelength equal to or higher than that of low-pressure mercury light.

(Embodiment 6) In the embodiment of the present invention, a method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 by a method different from the method described in the first embodiment will be described using the manufacturing apparatus shown in FIG. 1 and the like. .. The production conditions are the same as in the case of the first embodiment except for the following points.

1. Instead of triaminosilane gas, disilane gas, etc., and illuminance of 10 W / cm²NH excited by UV irradiation₃The SiN film 603 is formed by alternately supplying gas. Specifically, a SiH film is formed on the gate electrode 602 of the wafer 41 with a thickness of about 2 nm. The flow rate and pressure of each gas are the same as those in the fourth embodiment.

2. NH decomposed by an ultraviolet light irradiation device₃The gas is supplied to the first chamber 5 having a pressure of 67 Pa to 399 Pa (for example, 133 Pa). NH₃The flow rate of the gas may be 400 cc / min to 800 cc / min (for example, 600 cc / min), and the supply time may be 1 minute to 5 minutes (for example, 3 minutes).

As a result, the previously formed Si-H film is nitrided to obtain a SiN film 603 having a thickness of about 20 nm and an average refractive index of 2.0.

By heating at 450 ° C or less, N₂H₄The gas may be decomposed. Further, after forming the SiN film 603, the SiN film 603 may be further strengthened by irradiating with ultraviolet light having a wavelength equal to or higher than that of low-pressure mercury light.

(Embodiment 7) FIG. 7 is a schematic configuration diagram of the first chamber 5 according to the seventh embodiment of the present invention. In short, the first chamber 5 shown in FIG. 7 has a changed arrangement of the remote plasma device 21, a lamp 101 is provided inside, and a quartz plate 111 and a quartz plate 112 having a plurality of openings. It is different from the one shown in Fig. 2 in that it is provided with.

A method of manufacturing a semiconductor wafer using the first chamber 5 shown in FIG. 7 will be described.

First, since the lamp 101 is used, the temperature of the heater 51 may be lower than that in the case of the first embodiment. Specifically, it may be in the range of 200 ° C to 400 ° C (for example, 300 ° C). The lamp 101 uses an Xe excimer lamp capable of irradiating light with a wavelength of 172 nm, and the illuminance is 10 mW / cm.²It should be about.

The gas supplied to the first chamber 5 is tetrakis (dimethylamino) silane gas or the like and NH.₃Gas or N₂H₄Can be gas. The flow rate of each gas may be about 50cc / min to 100cc / min (for example, 75cc / min) and 400cc / min to 800cc / min (for example, 600cc / min), respectively.

Also, NH₃Gas or N₂H₄In addition to gas, N to prevent products from adhering to the quartz tube 102 that protects the UV lamp₂Gas may be added. N₂The gas may be about 200cc / min to 600cc / min (for example, 400cc / min). Open the gas supply valve 16 and NH₃Gas or N₂H₄Gas and N₂Gas is supplied to chamber 5. Then, tetrakis (dimethylamino) silane gas is supplied between the quartz plate 111 and the quartz plate 112.

The supply time of each gas is 30 to 90 seconds (for example, 60 seconds), and the pressure in the first chamber 5 is 13.3 Pa to 399 Pa (for example, 67 Pa). And NH₃Gas or N₂H₄Turn on the Xe excimer lamp while the gas is flowing. As a result, a SiN film 603 having a thickness of 20 nm and an average refractive index of 2.0 is formed on the wafer 41.

Here, the manufacturing conditions suitable for the semiconductor wafer for the DRAM capacitor are illustrated, but it can be applied to various electronic devices by changing, for example, the gas supply method and the time according to the incorporating target of the semiconductor wafer. ..

As an example, when the non-volatile memory is manufactured using the first chamber 5 shown in FIG. 7, the temperature of the heater 51 is set to the surface temperature of the wafer 41 in the range of 150 ° C to 450 ° C (for example, 300 ° C). Set under the condition of ° C). The flow rate of tetrakis (dimethylamino) silane gas, etc. is set to 20 cc / min to 100 cc / min (for example, 50 cc / min), and N₂H₄The gas flow rate shall be 200cc / min to 800cc / min (for example, 400cc / min).

Xe excimer lamp is NH₃Gas or N₂H₄Turn on while gas is flowing. Tetrakis (dimethylamino) silane gas, etc. and N₂H₄Gases and the like are supplied alternately, and the supply time of each gas is 20 to 60 seconds (for example, 30 seconds). After supplying each gas, the pressure in the chamber is lowered to 1.33Pa to 133Pa. While each gas is being supplied, the pressure in the first chamber 5 is 13.3 to 399 Pa (for example, 67 Pa). By repeating the pulse cycle of each gas twice, a SiN film 603 having a thickness of 3 nm and an average refractive index of 1.97 is formed on the wafer 41.

Alternatively, in order to form a SiN film 603 having a thickness of 20 nm and a refractive index of 1.97 on the wafer 41, for example, N₂Gas is supplied to chamber 5 at a flow rate of 100 cc / min to 500 cc / min (for example, 200 cc / min). Next, the pressure in the first chamber 5 is set to about 13.3 to 133 Pa (for example, 67 Pa), and N₂H₄Gas is continuously supplied at a flow rate of 200cc / min to 800cc / min (for example, 400cc / min). N₂H₄Turn on the Xe excimer lamp while the gas is being supplied.

Tetrakis (dimethylamino) silane gas or tris (dimethylamino) silane gas is surrounded by a perforated quartz plate 111 and a quartz plate 112, which are partition plates, installed in the first chamber 5 shown in FIG. The region is supplied with a flow rate of 20 cc / min to 100 cc / min (for example, 50 cc / min) for 10 seconds to 30 seconds (for example, 20 seconds). Repeat this operation 1 to 10 times (for example, 5 times). At this time, the pressure in the first chamber 5 is 13.3 Pa to 399 Pa (for example, 67 Pa).

Then, while tetrakis (dimethylamino) silane gas or tris (dimethylamino) silane gas is being supplied, and as the lamp 101, an Xe excimer lamp capable of irradiating light having a wavelength of 172 nm is used, and the illuminance is 10 mW / cm.²It should be about. In this way, a SiN film 603 having a thickness of about 20 nm is obtained.

Further, the hole of the lower quartz plate 102 may be enlarged or removed so as to eliminate the adhesion of the product to the quartz slope 102, and the Xe excimer lamp capable of irradiating light having a wavelength of 172 nm may be continuously irradiated. In this case, a low-pressure Hg lamp capable of continuously irradiating light having a wavelength of 254 nm may be used.

(Embodiment 8) FIG. 8 is a schematic configuration diagram of the decompression CVD apparatus according to the eighth embodiment of the present invention. The decompression CVD apparatus shown in FIG. 8 is not the so-called cluster type chamber described up to the seventh embodiment, but a batch type chamber. Using this type of chamber has the advantage that the SiN film 603 can be formed on a plurality of wafers 41 in a single process.

FIG. 8 shows the He gas supply pipe 200, the steam supply pipe 201, and NH.₃Gas supply pipe 202, N₂H₄Gas supply pipe 203 and triaminosilane (H-Si (NH)₂)₃) Gas supply pipe 204 and tris (dimethylamino) silane (H-Si (N (CH)), which is an alternative gas to triaminosilane gas.₃)₂)₃Gas or tetrakis (dimethylamino) silane gas supply pipe 205 and tetraaminodisilazane ((H (NH) NH), which is an alternative gas to triaminosilane gas.₂) Si-NH-Si ((NH₂) H) Gas supply pipe 206 and tetramethylaminodisilazan ((HN (CH)), which is an alternative gas to triaminosilane gas.₃)₂) Si-N-Si ((N (CH)₃)₂H) Gas supply pipe 207 and N₂The gas supply pipe 208 is shown. That is, the supply pipe 200 is an inert gas supply pipe, the supply pipe 202 is a nitrogen-based gas supply pipe, the supply pipes 203 to 207 are silicon-based gas supply pipes, and the supply pipe 208 is an inert gas. It is a supply pipe.

Further, in FIG. 8, an air valve 209 connected to each supply pipe 200 to 208, a mass flow controller 210 for controlling the flow rate of various gases, and an internal quartz having a plurality of holes through which various gases pass are formed. A tube 213, an outer quartz tube 212 that covers the periphery of the inner quartz tube 213 to form a decompression CVD processing chamber, a heater 211 that heats each quartz tube 212,213, and a wafer holder 214 that holds a plurality of wafers 41. The quartz buffer 216 on which the wafer holder 214 is placed is shown.

Further, FIG. 8 shows a nozzle 317 for injecting various gases toward the wafer 41, a nozzle hole 318 formed in the nozzle 317, a manifold 321 for collecting the supply pipes 200 to 208, and an internal quartz tube 213. And the measurement results of the quartz tube base 222 on which the external quartz tube 212 is placed, the exhaust valve 231 connected to the external quartz tube 212, the pressure gauge 232 provided in the vicinity of the exhaust valve 231 and the pressure gauge 232. A pressure adjusting valve 233 that adjusts the exhaust valve 231 according to the above, an exhaust pump 234 that exhausts the inside of the external quartz pipe 212 and the internal quartz pipe 213, a wafer transfer robot 241 that transfers the wafer 41 to the wafer holder 214, and N.₂It shows a shield box 242 filled with gas.

The processing of the wafer 41 itself in the decompression CVD apparatus shown in FIG. 8 is the same as the known method, but the condition that the surface temperature of the wafer 41 is 300 ° C to 450 ° C (for example, 400 ° C) in the heater 211. Set to N₂In a decompression CVD apparatus accommodating a wafer holder 214 in which the wafer 41 on which the gate electrode 602 is formed is held, with gas supplied and the pressure in the internal quartz tube 213 set to 67 Pa to 399 Pa (for example, 133 Pa). On the other hand, gas is supplied under the following conditions for about 10 to 30 minutes (for example, 20 minutes).

1. Aminosilane gas is supplied at a flow rate of about 100cc / min to 300cc / min (for example, 200cc / min).

2. N through supply pipe 203₂H₄Gas is supplied at a flow rate of about 400cc / min to 1000cc / min (for example, 800cc / min).

3. Water vapor is supplied from the nozzle 317 through the supply pipe 201 at a flow rate of about 30 cc / min to 70 cc / min (for example, 50 cc / min). The supply of water vapor promotes the decomposition of aminosilane gas.

4. He gas is supplied through the supply pipe 200 at a flow rate of about 100cc / min to 500cc / min (for example, 300cc / min).

As a result, a SiON film having a thickness of 50 nm and a refractive index of 1.85 can be obtained.

In addition to aminosilane gas, tetrakis (dimethylamino) silane gas, tetraaminodisilazane gas, tetramethylaminodisilazane gas, and tris (dimethylamino) silane gas described with reference to FIG. 2 and the like are used instead. You may use it. The gas supply time may be determined according to the gas used.

(Embodiment 9) A method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 using a gas different from the gas described in the eighth embodiment will be described using the apparatus shown in FIG. 8 and the like. The production conditions are the same as in the case of the sixth embodiment except for the following points.

1. Two types of gas are alternately supplied into the decompression CVD equipment. The surface temperature of the wafer 41 in the internal quartz tube 213 is set to be 200 ° C to 450 ° C (for example, 300 ° C).

2. The pressure inside the internal quartz tube 213 is 133Pa to 1330Pa (for example, 399Pa), and the flow rate of tetrakis (dimethylamino) silane gas is 100cc / min to 300cc / min (for example, 200cc / min) for 1 to 5 minutes (for example). Supply for about 3 minutes).

3. Next, stop the supply of tetrakis (dimethylamino) silane gas, set the pressure inside the internal quartz tube 213 to 1.33Pa to 133Pa (for example, 67Pa), and then from nozzle 317 to N.₂H₄Gas is applied at a flow rate of 400 cc / min to 1000 cc / min (for example, 800 cc / min), and the pressure inside the internal quartz tube 213 is again set to 133 Pa to 1330 Pa (for example, 399 Pa) for 1 minute to 5 minutes (for example, 3 minutes). Supply for a while.

The supply of each of the above gases is alternately repeated in a cycle of 10 to 20 times (for example, 15 times) in total.

As a result, a SiN film 603 having a thickness of 30 nm and an average refractive index of 1.95 is obtained.

In addition, N₂H₄NH instead of gas₃Use gas and NH₃If the gas is supplied in a state of being excited by a remote plasma device, the number of cycles can be reduced to about 2/3.

(Embodiment 10) A method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 using a gas different from the gas described in the eighth embodiment will be described using the apparatus shown in FIG. 8 and the like. The production conditions are the same as in the case of the sixth embodiment except for the following points.

Specifically, the supply pipe 205 in FIG. 8 is connected to tris (dimethylamino) silane (H-Si (N (CH)).₃)₂)₃Gas, disilane (Si₂H₆) Changed to a gas supply pipe.

The processing of the wafer 41 itself in the reduced pressure CVD apparatus shown in FIG. 8 is the same as the known method, but the surface temperature of the wafer 41 is heated to 300 ° C to 450 ° C (for example, 400 ° C) by the heater 211. , N₂A decompression CVD apparatus accommodating a wafer holder 214 in which the wafer 41 on which the gate electrode 602 is formed is held while the gas is supplied and the pressure in the internal quartz tube 213 is set to 67 Pa to 399 Pa (for example, 133 Pa). On the other hand, gas is supplied under the following conditions for about 10 to 30 minutes (for example, 20 minutes).

1. Dissilane gas is supplied from nozzle 317 at a flow rate of about 100 cc / min to 300 cc / min (for example, 200 cc / min).

2. At the same time as the supply of disilane gas, N through the supply pipe 203₂H₄Gas is supplied at a flow rate of about 400cc / min to 1000cc / min (for example, 800cc / min).

3. He gas is supplied through the supply pipe 200 at a flow rate of about 100cc / min to 600cc / min (for example, 300cc / min).

As a result, a SiN film 603 having a thickness of 50 nm and a refractive index of 1.97 is obtained.

(Embodiment 11) A method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 using a gas different from the gas described in the eighth embodiment will be described using the apparatus shown in FIG. 8 and the like. The production conditions are the same as in the case of the sixth embodiment except for the following points.

Specifically, the supply pipe 205 in FIG. 8 is connected to trisdimethylaminosilane (H-Si (N (CH)).₃)₂)₃Gas, disilane (Si₂H₆) Changed to a gas supply pipe.

The processing of the wafer 41 itself in the reduced pressure CVD apparatus shown in FIG. 8 is the same as the known method, but the surface temperature of the wafer 41 is heated to 300 ° C to 450 ° C (for example, 400 ° C) by the heater 211. The difference is that disilane gas and hydrazine gas are alternately supplied into the internal quartz tube 213. Gas is supplied to the decompression CVD apparatus in which the wafer holder 214 on which the wafer 41 on which the gate electrode 602 is formed is held, under the following conditions for about 1 to 5 minutes (for example, 3 minutes).

1. Dissilane gas is supplied from nozzle 317 at a flow rate of about 100 cc / min to 300 cc / min (for example, 200 cc / min). The pressure is 133 Pa to 1330 Pa (for example, 399 Pa) and is supplied for 1 to 5 minutes (for example, 3 minutes). After that, the pressure is reduced to 1.33 Pa to 133 Pa (for example, 67 Pa).

2. Next, N through the supply pipe 203₂H₄Gas is supplied at a flow rate of about 400 cc / min to 1000 cc / min (for example, 800 cc / min) for 1 minute to 5 minutes (for example, 3 minutes). The pressure should be 133Pa to 1330Pa (for example, 399Pa). Also, N₂H₄He gas may be supplied together with the gas at a flow rate of about 100 cc / min to 500 cc / min (for example, 300 cc / min) through the supply pipe 200. After that, the pressure is reduced to 1.33 Pa to 133 Pa (for example, 67 Pa).

3. Repeat this operation from 1 to 10 times (for example, 2 times).

As a result, a SiN film 603 having a thickness of 3 nm and a refractive index of 2.0 is obtained.

(Embodiment 12) A method for forming a SiN film on the gate electrode of the wafer 41 will be described using the first chamber 5 shown in FIG. 7 and using a method different from the method described in the seventh embodiment. The production conditions are the same as in the case of the seventh embodiment except for the following points.

1. Set the temperature of the heater 51 to a condition where the surface temperature of the wafer 41 is equal to or lower than the boiling point of the silicon-based gas (under normal pressure).

2. Set the pressure in the first chamber 5 to 133Pa to 1330Pa (for example, 399Pa) and the temperature of the heater 51 to the condition that the surface temperature of the wafer 41 is 50 ° C to 180 ° C (for example, 140 ° C). , Tetrakis (dimethylamino) silane gas is supplied at a flow rate of 100 cc / min to 300 cc / min (for example, 200 cc / min) for about 1 minute to 5 minutes (for example, 3 minutes).

3. Next, stop the supply of tetrakis (dimethylamino) silane gas, set the pressure in the first chamber 5 to 1.33Pa to 133Pa (for example, 67Pa), and then N.₂H₄At a flow rate of 400cc / min to 1000cc / min (for example, 800cc / min) for gas, the pressure in the first chamber 5 is again set to 133Pa to 1330Pa (for example, 399Pa) for 1 to 5 minutes (for example, 3 minutes). Supply degree. At this time, as in the seventh embodiment, the lamp 101 irradiates ultraviolet rays. However, the "temperature" remains at 50 ° C to 180 ° C (eg 140 ° C).

The supply of each of the above gases is alternately repeated in a cycle of 5 to 10 times (for example, 7 times) in total.

As a result, a SiN film having a thickness of 30 nm and an average refractive index of 1.93 is obtained.

In addition, N₂H₄NH instead of gas₃Use gas and NH₃The gas may be supplied in a state of being excited by a remote plasma device.

Further, since the SiN film is formed at a relatively low temperature in the present embodiment, the wafer 41 in the first chamber 5 is then heated and annealed under the condition that the surface temperature is 450 ° C. or less. Alternatively, if the wafer 41 after forming SiN is transferred to another furnace or the like and an annealing treatment is performed in a state where the wafer 41 is heated to 450 ° C. or lower, the SiN film becomes dense.

Each embodiment of the present invention has been described above, but here, an outline of the contents of each embodiment will be summarized.

Table 1 is a table summarizing the types of semiconductor device manufacturing apparatus, the method of manufacturing semiconductor devices, the gas used, and the like in Embodiments 1 to 12. The gases used are (1) silicon-based gas, (2) nitrogen-based gas, and (3) selectively used gas.<tables num="1"><img file="JP2010103484A_D0001.tif" /></tables>

Tables 2 and 3 are tables summarizing the gas used, the flow rate of the gas, the pressure in the chamber, the gas supply time, the temperature in the chamber, etc. in the first to 12th embodiments. The numbers in parentheses in the table mean typical numbers.<tables num="2"><img file="JP2010103484A_D0002.tif" /></tables><tables num="3"><img file="JP2010103484A_D0003.tif" /></tables>

(Embodiment 13) A method of forming a SiN film on the gate electrode of the wafer 41 will be described using the first chamber 5 shown in FIG. 7 by a method different from the method described in the seventh embodiment. The production conditions are the same as in the case of the seventh embodiment except for the following points.

1. Set the temperature of the heater 51 to a condition where the surface temperature of the wafer 41 is 450 ° C or less.

2. Set the pressure in the first chamber 5 to 133Pa to 1330Pa (for example, 399Pa) and the temperature of the heater 51 to the condition that the surface temperature of the wafer 41 is 350 ° C to 450 ° C (for example, 400 ° C). , Hexachlorodisilane (Si₂Cl₆) Gas is supplied at a flow rate of 50cc / min to 100cc / min (for example, 75cc / min) for about 1 to 5 minutes (for example, 3 minutes).

3. Next, stop the supply of hexachlorodisilane gas, set the pressure in the first chamber 5 to 1.33Pa to 133Pa (for example, 67Pa), and then N.₂H₄At a flow rate of 400cc / min to 800cc / min (for example, 600cc / min) for gas, the pressure in the first chamber 5 is again set to 133Pa to 1330Pa (for example, 399Pa) for 1 to 5 minutes (for example, 3 minutes). Supply degree. At this time, as in the seventh embodiment, the lamp 101 irradiates ultraviolet rays. However, the "temperature" remains at 350 ° C to 450 ° C (eg 400 ° C).

The supply of each of the above gases is alternately repeated in a cycle of 5 to 10 times (for example, 7 times) in total.

As a result, a SiN film having a thickness of 30 nm and an average refractive index of 1.95 can be obtained.

In addition, N₂H₄NH instead of gas₃Use gas and NH₃The gas may be supplied in a state of being excited by a remote plasma device.

Further, since the SiN film is formed at a relatively low temperature in the present embodiment, the wafer 41 in the first chamber 5 is then heated and annealed under the condition that the surface temperature is 450 ° C. or less. Alternatively, if the wafer 41 after forming SiN is transferred to another furnace or the like and an annealing treatment is performed in a state where the wafer 41 is heated to 450 ° C. or lower, the SiN film becomes dense.

(Embodiment 14) A method of forming a SiN film on the gate electrode of the wafer 41 will be described using the first chamber 5 shown in FIG. 7 by a method different from the method described in the seventh embodiment. The production conditions are the same as in the case of the seventh embodiment except for the following points.

1. Set the temperature of the heater 51 to a condition where the surface temperature of the wafer 41 is equal to or lower than the boiling point of the silicon-based gas (under normal pressure).

2. Set the pressure in the first chamber 5 to 133Pa to 1330Pa (for example, 399Pa) and the temperature of the heater 51 to the condition that the surface temperature of the wafer 41 is 50 ° C to 145 ° C (for example, 140 ° C). , Hexachlorodisilane gas is supplied at a flow rate of 50 cc / min to 100 cc / min (for example, 75 cc / min) for about 1 minute to 5 minutes (for example, 3 minutes).

3. Next, stop the supply of hexachlorodisilane gas, set the pressure in the first chamber 5 to 1.33Pa to 133Pa (for example, 67Pa), and then N.₂H₄At a flow rate of 400cc / min to 800cc / min (for example, 600cc / min) for gas, the pressure in the first chamber 5 is again set to 133Pa to 1330Pa (for example, 399Pa) for 1 to 5 minutes (for example, 3 minutes). Supply degree. At this time, as in the seventh embodiment, the lamp 101 irradiates ultraviolet rays. However, the "temperature" remains at 50 ° C to 145 ° C (eg 140 ° C).

The supply of each of the above gases is alternately repeated in a cycle of 5 to 10 times (for example, 7 times) in total.

As a result, a SiN film having a thickness of 30 nm and an average refractive index of 1.93 is obtained.

In addition, N₂H₄NH instead of gas₃Use gas and NH₃The gas may be supplied in a state of being excited by a remote plasma device.

Further, since the SiN film is formed at a relatively low temperature in the present embodiment, the wafer 41 in the first chamber 5 is then heated and annealed under the condition that the surface temperature is 450 ° C. or less. Alternatively, if the wafer 41 after forming SiN is transferred to another furnace or the like and an annealing treatment is performed in a state where the wafer 41 is heated to 450 ° C. or lower, the SiN film becomes dense.

(Embodiment 15) A method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 with a gas different from the gas described in the eighth embodiment will be described using the apparatus shown in FIG. 8 and the like. The production conditions are the same as in the case of the sixth embodiment except for the following points.

Specifically, the supply pipe 205 in FIG. 8 is changed to a hexachlorodisilane gas supply pipe.

The processing of the wafer 41 itself in the reduced pressure CVD apparatus shown in FIG. 8 is the same as that of the known method, but the surface temperature of the wafer 41 is heated to 350 ° C to 450 ° C (for example, 400 ° C) by the heater 211. It is different that hexachlorodisilane gas and hydrazine gas are alternately supplied into the internal quartz tube 213. Gas is supplied to the decompression CVD apparatus in which the wafer holder 214 on which the wafer 41 on which the gate electrode 602 is formed is held, under the following conditions for about 1 to 5 minutes (for example, 3 minutes).

1. Hexachlorodisilane gas is supplied from nozzle 317 at a flow rate of about 100 cc / min to 300 cc / min (for example, 200 cc / min). The pressure is 133 Pa to 1330 Pa (for example, 399 Pa) and is supplied for 1 to 5 minutes (for example, 3 minutes). After that, the pressure is reduced to 1.33 Pa to 133 Pa (for example, 67 Pa).

2. Next, N through the supply pipe 203₂H₄Gas is supplied at a flow rate of about 400 cc / min to 1000 cc / min (for example, 800 cc / min) for 1 minute to 5 minutes (for example, 3 minutes). The pressure should be 133Pa to 1330Pa (for example, 399Pa). Also, N₂H₄He gas may be supplied together with the gas at a flow rate of about 100 cc / min to 500 cc / min (for example, 300 cc / min) through the supply pipe 200. After that, the pressure is reduced to 1.33 Pa to 133 Pa (for example, 67 Pa).

3. Repeat this operation from 1 to 10 times (for example, 2 times).

As a result, a SiN film 603 having a thickness of 3 nm and a refractive index of 2.0 is obtained.

Further, since the SiN film is formed at a relatively low temperature in the present embodiment, the wafer 41 in the first chamber 5 is then heated under the condition that the surface temperature is 450 ° C. or less to perform an ultraviolet annealing treatment. Alternatively, when the wafer 41 after forming SiN is transferred to another furnace or the like and heat-annealed while being heated to 450 ° C. or lower, the SiN film becomes dense.

(Embodiment 16) A method of forming the SiN film 603 on the gate electrode 602 of the wafer 41 with a gas different from the gas described in the eighth embodiment will be described using the apparatus shown in FIG. 8 and the like. The production conditions are the same as in the case of the sixth embodiment except for the following points.

Specifically, the supply pipe 205 in FIG. 8 is changed to a hexachlorodisilane gas supply pipe.

The processing of the wafer 41 itself in the reduced pressure CVD apparatus shown in FIG. 8 is the same as that of the known method, but the surface temperature of the wafer 41 is heated to 50 ° C to 145 ° C (for example, 140 ° C) by the heater 211. It is different that hexachlorodisilane gas and hydrazine gas are alternately supplied into the internal quartz tube 213. Gas is supplied to the decompression CVD apparatus in which the wafer holder 214 on which the wafer 41 on which the gate electrode 602 is formed is held, under the following conditions for about 1 to 5 minutes (for example, 3 minutes).

1. Hexachlorodisilane gas is supplied from nozzle 317 at a flow rate of about 100 cc / min to 300 cc / min (for example, 200 cc / min). The pressure is 133 Pa to 1330 Pa (for example, 399 Pa) and is supplied for 1 to 5 minutes (for example, 3 minutes) . After that, the pressure is reduced to 1.33 Pa to 133 Pa (for example, 67 Pa).

2. Next, N through the supply pipe 203₂H₄Gas is supplied at a flow rate of about 400 cc / min to 1000 cc / min (for example, 800 cc / min) for 1 minute to 5 minutes (for example, 3 minutes). The pressure should be 133Pa to 1330Pa (for example, 399Pa). Also, N₂H₄He gas may be supplied together with the gas at a flow rate of about 100 cc / min to 500 cc / min (for example, 300 cc / min) through the supply pipe 200. After that, the pressure is reduced to 1.33 Pa to 133 Pa (for example, 67 Pa).

3. Repeat this operation from 1 to 10 times (for example, 2 times).

As a result, a SiN film 603 having a thickness of 3 nm and a refractive index of 1.91 is obtained.

Further, since the SiN film is formed at a relatively low temperature in the present embodiment, the wafer 41 in the first chamber 5 is then heated under the condition that the surface temperature is 450 ° C. or less to perform an ultraviolet annealing treatment. Alternatively, when the wafer 41 after forming SiN is transferred to another furnace or the like and heat-annealed while being heated to 450 ° C. or lower, the SiN film becomes dense.

Table 4 is a table summarizing the types of semiconductor device manufacturing apparatus, the method of semiconductor device manufacturing method, the gas used, and the like in the 13th to 16th embodiments.<tables num="4"><img file="JP2010103484A_D0004.tif" /></tables>

Table 5 is a table summarizing the gas used, the flow rate of the gas, the pressure in the chamber and the like, the gas supply time, the temperature in the chamber and the like, etc. in the 13th to 16th embodiments. The numbers in parentheses in the table mean typical numbers.<tables num="5"><img file="JP2010103484A_D0005.tif" /></tables>

The semiconductor device manufactured by using the semiconductor manufacturing apparatus described in the first embodiment or the like can be suitably used for a display device such as a liquid crystal, plasma, or EL (electroluminescence). In addition, imaging devices such as digital cameras and digital still cameras, image forming devices such as facsimiles, printers and scanners, optical devices such as CLC elements and light emitting laser devices, communication devices such as mobile phones, personal computers, etc. Any device that uses a glass substrate for forming elements of electronic components, such as a memory built in or detachable from an information processing device, can be preferably used.