JPH02260637A - Photochemical reaction and device therefor - Google Patents

Abstract

PURPOSE:To prevent the cloud of a window and to perform a uniform film formation by a method wherein two kinds or more of gases for producing active species are separately supplied in a reaction space through the blow-off nozzles of porous plates made of a sintered body consisting of heat-resistant particles, the gas, with which a solid matter is not generated, is supplied to the side of the light-transmitting window and the gas, with which a solid matter is generated, is supplied to the side of a substrate. CONSTITUTION:Porous plates 5a and 5b obtainable by sintering a metal consisting of fine particles of a particle diameter of 0.2 to 500mum are made on the side surface of a reaction chamber. Each reaction gas obtainable by diluting respectively O2 and monosilane with N2 or the like is supplied in a reaction space keeping their respective linear speeds V in a range of 0.01<=V<=8 (N.cm/s). In the reaction space, the ratio Rv of the linear speed of the O2- containing gas to the linear speed or the monosilane-containing gas is selected in 0.7<=Rv<=1.2, the total pressure Pt is selected in 0.3Torr or higher, the molar fraction of the monosilane- containing gas is selected in 0.001 or higher and tn 0.2 or lower and the molar fraction of the O2-containing gas is selected in the quantum theory ratio or higher of the monosilane- containing gas. The number Rv of rotations of a substrate is selected in 0.01<=Rv<=20 and active species are produced by the light of light sources 4 through a window 22. According to this constitution, the cloud of the window is prevented and a uniform thin film can be formed on the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photochemical reaction method and apparatus, and more particularly to a photochemical reaction method and apparatus suitable for preventing fogging of a light-transmitting window and achieving uniform film formation.

[Conventional technology]

A photochemical reaction promotes a chemical reaction by irradiating a reactive gas with light having a wavelength corresponding to the absorption wavelength of the gas. It is possible to selectively advance the reaction by combining the irradiated light and the reaction gas. Furthermore, photochemical reactions do not require high temperatures like thermochemical reactions, so they are effective in lowering the process temperature, and unlike plasma reactions, they are not affected by charged particles, so there is no damage to deposited films or etched underlying films. Therefore, it is considered to be effective in forming a silicon oxide film.

However, in thin film manufacturing equipment using photochemical reactions,
Since a reaction gas is supplied into the reaction vessel and a thin film is deposited on the substrate, reaction products adhere to the surface of the light-transmitting window, reducing the intensity of light inside the reaction vessel. There is a problem with particle generation due to falling.

[Problem to be solved by the invention]

In a photochemical reaction device, for example, Si is deposited on a substrate in a reaction chamber.
At the same time that nO is precipitated, S i Ot is also precipitated on the light transmitting window surface. The temperature of the light transmitting window surface is lower than the temperature of the substrate surface, and StO! precipitates on the light transmitting window surface. is less dense,
Since it absorbs and scatters ultraviolet light, it is a factor that reduces the intensity of transmitted light in the light transmission window.

In general, in the photochemical reaction method, under conditions where the substrate temperature, reaction gas composition ratio, and pressure are kept constant, the deposition rate of the thin film on the substrate increases in proportion to the light irradiation intensity. Are known. Therefore, Sin,
The precipitation not only reduces the deposition rate of the thin film over time, but also makes it difficult to uniformly deposit the film.

An object of the present invention is to provide a photochemical reaction method and apparatus that solves the problems of the prior art described above, prevents fogging of the light-transmitting window due to precipitates, and enables uniform film formation.

[Means to solve the problem]

In order to achieve the above-mentioned object, the method of the present invention generates active species by photoexcitation from a gas outlet formed of a porous plate made of a sintered body having a large number of fine communication holes made by sintering heat-resistant particles. More than one type of gas is separately supplied to the reaction space, with the light-transmitting window side being a reactive gas that does not produce solid matter, and the substrate side being a gas that reacts with this reactive gas to produce solid matter.

Further, the apparatus of the present invention is provided with a gas supply section on the side surface of the reaction chamber, which is equipped with a gas outlet formed of a perforated plate made of a sintered body having a large number of fine communication holes made by sintering heat-resistant particles. A gas exhaust section with a gas exhaust port is provided on the side of the reaction chamber opposite to the reaction space at the mouth, and the gas outlet is divided into two or more stages vertically, so that the depth of the gas exhaust section is approximately the same as that of the gas outlet. It was formed to the size of . - In the photochemical reaction method of the present invention, the gas outlet for supplying the reaction gas to the reaction space is formed of a porous plate made of a sintered body having a large number of fine communication holes formed by sintering heat-resistant particles. As the heat-resistant particles, especially Oo-1p~1
A sintered body of metal particles or ceramic particles having an average particle size of 0.2 μm to 500 μm is desirable.

Two or more types of gases that generate active species by photoexcitation are each separately supplied to the reaction space from the gas outlet as described above. Here, the gas that generates active species upon photoexcitation is arbitrarily selected depending on the components of the thin film to be deposited on the substrate.

For example, a gas containing an element of group 111B or group IVB of the periodic table, a gas containing Ta, or a gas containing an element of group VIA and group IVB of the periodic table can be used in the reaction space on the substrate side. Therefore, each of the above elements is used in the form of a gasifiable compound such as a chloride or a hydride depending on the element.

A gas containing Ol or NH's is used in the reaction space on the light transmission window side, depending on the oxide or nitride of the above element to be deposited on the substrate. The gas supplied to the substrate side and the gas supplied to the light transmission window side are each diluted with an inert gas as necessary, and the dilution gas is preferably a Group 0 rare gas, particularly N8 gas.

When depositing Sin on a substrate, monosilane (S i H4) and disilane (Siz
Higher order silanes such as H-), )disilane (SisHs), dimethylsilane [S i Ht(CHs)ol.

Tetraethoxysilane [S (OCg Hs) 4
] is preferably used, and Ot diluted with (18 or N2) is supplied to the reaction space of the light transmission window example.Also, when depositing a silicon nitride film on the substrate, A gas made of the above silane compound is supplied to the reaction space on the substrate side, and a gas containing NH is supplied to the reaction space on the light transmission window side.

In particular, when forming a silicon oxide film, a first reaction gas (18 diluted with N2) is supplied to the reaction space on the light transmission window side, and a first reaction gas (18 diluted with Nx) is supplied to the reaction space on the substrate side. It is desirable that the two reaction gases be supplied from gas outlets each made of a perforated plate so as not to generate jets.

In the present invention, as a light source, a deuterium lamp, excimer laser, etc. can also be used in addition to a low-pressure mercury lamp.

When the above-mentioned reaction gas is supplied to the reaction space, the characteristics of the gas introduced into the reaction space in a rectified state can be maintained depending on the operating conditions, and uniform film formation can be achieved. These operating conditions include the linear velocity of the reaction gas, the linear velocity ratio of the reaction gas in the light transmission window example and the reaction gas on the substrate side, the total pressure in the reaction space, the molar fraction of the reaction gas, and the rotation of the substrate in the reaction space. For example, the linear velocity of the reaction gas is 0.01≦
V≦8 (N-cm/s), the ratio of the linear velocity of the reaction gas on the light transmission window side/the linear velocity of the reaction gas on the substrate side is 0.7≦Rv≦
1.2. The total pressure of the reaction space is Pt≧0.3 Torr, and the gas (for example, 5iHa) containing an organic silane compound is introduced into the reaction space on the substrate side.

The mole fraction is 0.001≦m5iH,≦0.2, the 0□ mole fraction introduced into the reaction space on the light transmission window side is more than the stoichiometric ratio of 5tH4, and the rotation speed of the substrate placed in the reaction space is 0. .0
It is desirable that 1≦Rr≦20 (rpm).

As described above, depending on the operating conditions, the light transmittance of the light transmitting window can be maintained at approximately 95% or more, and the film thickness can be made uniform.

[Effect]

The reaction gas introduced into the reaction space through a porous plate made of a sintered body with fine communication holes is excited and decomposed by the light energy transmitted from the light source through the light transmission window, and predetermined reaction products are deposited on the substrate. . At this time, the reaction gas flows through the reaction space in a rectified state, separated into a light-transmitting window side and a substrate side, with a small number of gas blow-off ports made of a porous plate (both partitioned into two stages).

When the above operating conditions are set, mixing and entrainment of the gas flow on the light transmission window side, the gas flow on the substrate side, and the gas flow on the substrate side are prevented, the light transmittance of the light transmission window is maintained at a high level, and a uniform film thickness is achieved. Guaranteed.

〔Example〕

Embodiments of the present invention will be described below based on the drawings.

FIG. 1 is a longitudinal sectional view showing one embodiment of the photochemical reaction device of the present invention, and FIG. 2 is a detailed view of the gas supply section and gas exhaust section in FIG. 1.

As shown in FIG. 1, this photochemical reaction device mainly consists of a reaction chamber 1 and a preliminary chamber 2.
The gate mechanism 3 is connected to the gate mechanism 3 so as to be freely openable and closable. The reaction chamber 1 has multiple low-pressure mercury lamps 4 installed in the upper part of the chamber.
A plurality of heaters 7 are arranged in parallel at the bottom of the reaction chamber 1, in which a gas supply section 5 and a gas exhaust section 6 are arranged in the middle part of the chamber. A substrate rotating/elevating mechanism 9 having a susceptor 8 on the upper end surface is provided.

The preliminary chamber 2 is provided with a substrate transfer mechanism 12 including a transfer arm 10 and a transfer arm 11, and a substrate temporary storage table 13 provided adjacent to the substrate transfer mechanism 12 is equipped with an air cylinder 14.
It can be raised and lowered by the operation of the bellows 15, and has a sealing structure with bellows 15. Further, an exhaust port 16 for evacuating the interior of the preliminary chamber 2 and a gate mechanism 17 for opening and closing the substrate transfer port by the transfer arm 11 are provided.

As shown in FIG. 2, the gas supply section 5 provided in the reaction chamber 1 includes a box-shaped gas supply section 5c whose gas blowing surface is formed of a perforated plate 5a, and a box-shaped gas supply section whose gas blowing surface is formed of a perforated plate 5b. It has a structure in which gas supply sections 5d are stacked.

The depth of the gas exhaust section 6 is approximately the same area as the gas blowing surface made up of the perforated plates 5a and 5b, and is provided with an exhaust port extending downward.

The porous plates 5a and 5b are made of a porous material having fine communicating holes, and the porous material has an average particle size of, for example, 0.1 um to 1 μm, preferably 0.2 μm to 500 μm.
Although it can be formed from a sintered body of metal particles or ceramics, or a heat-resistant resin such as Teflon, a sintered body of metal particles is particularly desirable.

In the area between the low-pressure mercury lamp 4, the gas supply section 5, and the gas exhaust section 6, four rods 18 perpendicular to the wall surface of each reaction chamber are provided with seals, as shown in FIGS. 1 and 2. An actuator 20 connected through a portion 19 allows each rod 18 to rotate about its axis at an angle of 90°.

And the support plate 21 fixed on each rod 1 is
8, it can swing from a horizontal plane to a vertical plane as shown in FIG. 2 using the rod 18 as a fulcrum.

Furthermore, when the support plate 21 is placed on a horizontal plane, a circular space is formed at the center of the reaction space. Note that 24 indicates a plate.

In this photochemical reaction device, when the transfer arm 10 is rotated in a horizontal plane, the axis intersection angle of the transfer arm with respect to the transfer arm IO changes, and the transfer arm 11 is moved between the outside of the preliminary chamber above the gate mechanism 17 and the inside of the preliminary chamber 21 and the reaction chamber 1. The substrate 23 is transported through the light transmitting window 22 by moving the light transmitting window 22 .

Then, the light transmitting window 22 is supported by the support plate 21 via the elevating and rotating mechanism 9, while the susceptor 8 installed at the upper end of the elevating and rotating mechanism 9 is placed at the position shown in FIG.

Then, the reaction chamber 1 is evacuated to the order of 10-' Torr.
The substrate 23 on the susceptor 8 is heated to a predetermined temperature by the heater 7 inside.

Next, for example 0. or O! diluted with N! is introduced into the reaction space through the sintered porous plate 5a as a rectified flow, and on the other hand,
SiH, or N! 5iHa diluted with sintered porous body 5
It is rectified through b and introduced into the reaction space.

In this case, the flow rate of gas or fluid from the nozzle is generally proportional to the 1/2 power of the pressure difference before and after the nozzle. Therefore, the pressure loss before and after the sintered porous bodies 5a and 5b that form the blowout ports is large. Therefore, the gas pressure inside the nozzle remains at a nearly constant value, and the gas blowout ports formed by the sintered porous bodies 5a and 5b The flow rate of the gas blown out is constant on the perforated plate surface, and no drift occurs.Furthermore, since the perforated plate surface has many holes, the flow rate of the gas blown out from those holes is extremely small, and each hole is very close to each other. As a result, the dead space existing between each hole is relatively small, and gas turbulence is less likely to occur.As a result, the sintered porous bodies 5a, 5b
The gas blown out is not turbulent or biased, and is rectified.

Therefore, the gas from the perforated plate 5a forms a rectified upper gas flow, and the gas from the perforated plate 5b forms a rectified lower gas flow.

Moreover, the gas flow on the lower stage side gradually rises toward the light transmission window 22 side as it approaches the gas exhaust section 6 due to the concentration diffusion phenomenon. For this reason, the vertical distance on the perforated plate 5a side is set to the perforated plate 5b.
(preferably 0) For example, the upper gas contains 02, and the lower gas contains 5iHa.
When using a gas containing gas, it is desirable that the ratio of the vertical distance of the perforated plate 5a/the vertical distance of the perforated plate 5b be about 3.

Further, the gas flow path of the reaction space is connected to the side wall of the chamber and the plate 24. Formed by a susceptor 13 and a light transmission window 22,
The cross section of the flow path has the same area as the depth of the gas outlet and gas exhaust section of the gas supply section 25, and since there is no uneven shape in the gas flow path of the reaction space, it is easy to maintain gas rectification. .

In addition, in the gas exhaust section 6 shown in FIG. 2, a structure in which the relationship of 0.1 ≦ W/H ≦ 1 holds, where the internal height of the gas exhaust section 6 is H and the width of the exhaust port is W, is the gas exhaust section 6. W/H-115 is particularly desirable from the viewpoint of rectification.

Furthermore, FIG. 3 shows an embodiment in which a light transmission window 22 is placed on the upper end surface of the gas supply section 5 and the gas exhaust section 6. In this case, the structure of the gas exhaust section 6 is the same as described above, and the gas supply section 5 is is Δt≦0.015L,”/L.

This is desirable from the viewpoint of rectifying the gas and preventing fogging of the light transmission window 22.

Next, the relationship between various operating conditions in the photochemical reaction method, ultraviolet light transmittance of the light transmitting window, film thickness uniformity with respect to the substrate, film formation rate, etc. will be explained.

Figure 4 is a relationship diagram between the linear velocity of gas introduced into the reaction space and window transmittance, and Figure 5 is a relationship diagram between the linear velocity of gas introduced into the reaction space and film thickness uniformity with respect to the substrate. Yes. 4th
The figure shows that the gas linear velocity is 0.01≦V≦8 (N-Cal/S
), the window transmittance shows a high value of approximately 95% or more, and Figure 5 shows that when the linear velocity exceeds 8, powder is generated, and when the linear velocity is less than 0.01, the film uniformity decreases. It shows that it is rapidly decreasing.

The reason for this is that when V<0.01 (N-cm/s), 5iHa reaches the light transmission window due to the concentration diffusion of the reactant gas.
The window transmittance decreases, and photochemical reactions proceed near the gas outlet due to the concentration diffusion of the reactant gas, resulting in a decrease in film thickness uniformity. However, if the substrate is small, this level of film thickness distribution can be ignored.

In addition, at V > 8 (N-cm/s), slight irregularities in the reaction space cause gas turbulence, and the mixing action between the gas flow on the upper stage and the gas flow on the lower stage is accelerated, so the window is closed. As the transmittance decreases, powder is generated without forming a film.

Figure 6 is a relationship diagram between the ratio of the linear velocity of the gas on the upper stage (light transmission window) side/the linear velocity of the gas on the lower stage (substrate) side (hereinafter simply referred to as linear velocity ratio) and the window transmittance. is a relationship diagram between linear velocity ratio and film thickness uniformity.

Figure 6 shows that the window transmittance is 95% or more in the linear velocity range of 0.7≦Rv≦1.2, and Figure 7 shows that the window transmittance is 95% or more in the range of linear velocity of 0.7≦Rv≦1.2.
The film thickness uniformity is 5±% or less within the range of . The reason for this is that the region where the linear velocity is high becomes negative pressure, which entrains the gas in the region where the linear velocity is low, especially when Rv <
In the case of 0.7, the light-transmitting window side gas (OS or N*+o*
) is drawn into the substrate side gas (SiH4 or N, +5iH4), and the reaction causes fogging on the downstream side of the light transmission window.

When Rv > 1.2, the substrate-side gas is involved in the light-transmitting window-side gas, so that the concentration diffusion of S i H is accelerated, and the light-transmitting window transmittance decreases. When gas entrainment occurs, the mixing of the gas flows is accelerated to produce powder.

Figure 8 shows the relationship between total pressure Pt and window transmittance, Figure 9 shows the relationship between total pressure Pt and film formation rate, and Figure 1O shows the relationship between total pressure Pt and film thickness uniformity. It shows. Figure 8 shows the total pressure 0.
The window transmittance shows 95% or more at around 3 Torr or higher, and Figure 9 shows that the film formation rate begins to improve at a total pressure of around 0.3 Torr or higher, and especially increases at a total pressure of 3 Torr or higher. It shows.

Further, FIG. 10 shows that the film thickness uniformity is relatively high at a total pressure of 0.3 Torr or more, and in particular, the film thickness uniformity is 50% or less in the range of a total pressure of I Torr to 6 Torr. The reason for this is that when the total pressure P t < 0.3 Torr, the gas flow approaches the molecular flow region and the amount of 5iHn diffusion increases, resulting in a decrease in window transmittance. Although the film thickness distribution decreases, there is no problem with the decrease in window transmittance due to fogging of the window, and the film formation rate is saturated.

FIG. 11, FIG. 12, and FIG. 13 are relationship diagrams of SiH, mole fraction, window transmittance, film formation rate, and film thickness uniformity, respectively. If the SiH mole fraction is less than 0.001, no film will be formed, and if the SiH4 mole fraction is greater than 0.2, a combustion reaction of SiH4 will occur and powder will be produced. . Therefore, window transmittance, film formation rate, film thickness uniformity -
Considering the properties, the SiH4 mole fraction is o,oot~0.
It is desirable to adjust within the range of 2.

FIG. 14, FIG. 15, and FIG. 16 each show a relationship between the 0□ mole fraction, window transmittance, film formation rate, and film thickness uniformity. (When the 18 mole fraction is 0.0 (15 (stoichiometric ratio or less), the amount of diffusion of SiH4 to the light transmission window side increases and the window transmittance increases. (18 mole fraction is o, oos or more) This shows that there is no adverse effect on the window transmittance, film formation rate, and film thickness uniformity.However, since the minimum value of the SiH mole fraction is 0.001, the O-poor mole fraction It is desirable that the allowable range is 0.001 or more.

FIGS. 17 and 18 respectively show relationships between the rotational speed of a substrate placed on a susceptor, window transmittance, and film thickness uniformity. Figure 17 shows that when the rotational speed Rr is larger than 2 Orpm, the window transmittance is about 90% or less, and Fig. 18 shows that when the rotational speed Rr is smaller than 0.01, the film thickness distribution decreases significantly, and A number Rr greater than 20 indicates that powder is generated. The reason for this is that the rotation speed Rr
If Rr is smaller than 0 or Ol, the irradiation intensity of ultraviolet light on the substrate becomes non-uniform, and if the rotation speed Rr is larger than 20, the flow of gas on the substrate side is disturbed by the rotation of the substrate and susceptor, and the gas on the substrate side becomes uneven. This is because the mixing of the gas on the light-transmitting window side is promoted and powder is generated, reducing the window transmittance.

Further, in the above-mentioned embodiments, thin film formation by photo-CVD method was explained, but it goes without saying that the present invention can be applied to photo-excited etching. Furthermore, phosphorus-added poly-Si
CI membrane! Etching can be performed by irradiating ultraviolet light from a low-pressure mercury lamp in a gas containing F (for example, C2 gas).

Operation example: N to the upper gas! A photochemical reaction method was carried out under the following conditions using 0□ diluted with N and S i Ha diluted with N as the lower stage gas.

Total pressure P t = 3 Torr Linear velocity V = 0.2N -cm/s (ato
'C, 1 atm) linear velocity ratio Rv = 1.0 molar fraction of S I Ha in the total feed gas mS i H,
= 0.0 (15 molar fraction of Ol in the total supply gas mO□1,000, (15 Substrate rotation speed Rr = 1 rpm) As a result, clouding of the light transmission window is prevented and the uniformity of the thickness of the rapidly deposited film is improved. was achieved.

〔Effect of the invention〕

As described above, according to the present invention, the gas supplied to the reaction space can be flowed in a laminar flow state to the light-transmitting window side and the substrate side, respectively, suppressing the concentration diffusion of the reaction gas, and causing the gas on the light-transmitting window side and the substrate side to flow in a laminar flow state. By preventing the mixing and entrainment of side gases, clouding of the light transmission window can be prevented, and a thin film with a uniform thickness can be produced on the substrate.

[Brief explanation of drawings]

FIG. 1 is a vertical cross-sectional view showing one embodiment of the photochemical reaction device of the present invention, FIG. 2 is an enlarged detailed view of the gas supply section and gas exhaust section in the device of FIG. 1, and FIG. 3 is the same as that of FIG. An enlarged detailed view showing a modified example, Figure 4 is a diagram showing the relationship between the linear velocity of the reaction gas introduced into the reaction space and the window transmittance, and Figure 5 is a diagram showing the relationship between the linear velocity of the reaction gas introduced into the reaction space and the substrate. Figure 6 is a diagram of the relationship between linear velocity ratio and window transmittance, Figure 7 is a diagram of the relationship between linear velocity ratio and film thickness uniformity, and Figure 8 is a diagram of the relationship between linear velocity ratio and window transmittance. Figure 9 is a diagram of the relationship between total pressure and film formation rate, Figure 10 is a diagram of the relationship between total pressure and film thickness uniformity, and Figure 11 is a diagram of the relationship between 5iHn mole fraction and window transmittance. The relationship diagram, Figure 12, is 3
Figure 13 shows the relationship between iH4 mole fraction and film formation rate.
Relationship diagram between H4 mole fraction and film thickness uniformity, Figure 14 is 0□
Figure 15 is a diagram showing the relationship between mole fraction and window transmittance. Figure 15 is a diagram showing the relationship between 0□ mole fraction and film formation rate. Figure 16 is a diagram showing the relationship between 0□ mole fraction and film thickness uniformity. Figure 17 is a diagram showing the relationship between the rotation speed of the substrate in the reaction space and window transmittance, and Figure 18 is a diagram showing the relationship between the rotation speed of the substrate in the reaction space and film thickness uniformity. 1...Reaction chamber, 2...Preliminary room, 3...
...Gate mechanism, 4...Low pressure mercury lamp,
5... Gas supply section, 6... Gas exhaust section, 7... Heater, 8... Susceptor, 9
・・・・・・Substrate rotation lifting mechanism, 10.11・・・・・・
・Transport arm, 12...Substrate transfer mechanism, 13.
...Temporary board storage stand, 14...Air cylinder, 15...Bello 16...Exhaust port, 1
7...Gate mechanism, 18...Rod,
19... Seal part, 20... Actuator, 21... Support plate, 22... Light transmission window, 23... Substrate, 24 ······plate. Agent Patent Attorney Masaru Nishimoto (2) Figure 3 ○○ゝO○○ ○○ 4 Figure 5 Linear speed (N-cm/s)

Claims (1)

[Scope of Claims] (1) Gases are separately supplied to the reaction space from gas outlets formed of a perforated plate made of a sintered body having fine communication holes made by sintering heat-resistant particles, and the gases are The first reaction gas consists of a first reaction gas supplied to the reaction space on the light transmission window side and a second reaction gas supplied to the reaction space on the substrate side.
The reactive gas is a gas that generates active species but does not generate solid substances when excited by light, and the second reactive gas is a gas that generates solid substances by reaction with the first reactive gas. Characteristic photochemical reaction method. (2) The photochemical reaction method according to claim 1, wherein the sintered body is a metal or ceramic sintered body made of fine particles of 0.2 μm to 500 μm. (3) The photochemical reaction method according to claim (1), wherein the first reaction gas and the second reaction gas are each diluted with an inert gas. (4) Claim (3) characterized in that the inert gas is N_2 or a group O rare gas such as He or Ar.
Photochemical reaction method described. (5) The photochemical reaction method according to claim (1), wherein the first reaction gas is O_2 or NH_3. (6) The photochemical reaction method according to claim (1), wherein the second reaction gas is a gas containing an organic silane compound. (7) The photochemical reaction method according to claim (6), wherein the organic silane compound is selected from the group consisting of monosilane, disilane, trisilane, dimethylsilane, and tetraethoxysilane. (8) The first reaction gas and the second reaction gas are supplied to the reaction space at respective linear velocities V in the range of 0.01≦V≦8 (N cm/s). Claim (1
) Photochemical reaction method described. (9) The ratio (linear velocity ratio) of the gas velocity of the first reaction gas in the reaction space/the gas velocity of the second reaction gas in the reaction space is in the range of 0.7≦Rv≦1.2. The photochemical reaction force method according to claim (1), characterized in that: (10) The photochemical reaction method according to claim (1), characterized in that the total pressure Pt in the reaction space is 0.3 Torr or more. (11) The mole fraction of the second reaction gas containing the silane compound in the total gas supplied to the reaction space is 0.001.
Claim (1) characterized in that it is 0.2 or less.
Photochemical reaction method described. (12) The photochemical reaction method (13) according to claim (11), wherein the silane compound is monosilane.
The O_2 or N in the total gas supplied to the reaction space
Claim (1) characterized in that the mole fraction of the first reaction gas containing H_3 is greater than or equal to the stoichiometric ratio of the second reaction gas.
) Photochemical reaction method described. (14) Rotation speed R of the substrate placed in the reaction space
The photochemical reaction method according to claim 1, characterized in that r is 0.01≦Rr≦20 (rpm). (15) A gas supply section equipped with a gas outlet formed of a porous plate made of a sintered body having fine communication holes formed by sintering heat-resistant particles is provided on the side of the reaction chamber, and the reaction space at the gas outlet is A gas exhaust section with a gas exhaust port is provided on the opposite side of the reaction chamber, and the gas outlet is divided into at least two stages above and below, and the gas exhaust port has a size equal to or smaller than that of the gas outlet. A photochemical reaction device characterized by: (16) The photochemical reaction device according to claim 15, wherein the sintered body is a sintered body of metal or ceramics made of fine particles of 0.2 μm to 500 μm. (17) The photochemical reaction device according to claim (15), wherein the depth of the gas outlet and the gas exhaust section are approximately the same area as the cross section of the flow path of the reaction space. (18) The gas outlet is divided into two stages, and the distance in the vertical direction of the gas outlet on the light transmission window side is larger than the distance in the vertical direction of the gas outlet on the substrate side. photochemical reaction device. (19) The photochemical reaction apparatus according to claim (15), further comprising an elevating and rotating mechanism for elevating, lowering and rotating a susceptor on which a substrate is placed within the reaction chamber. (20) The photochemical reaction device according to claim (15), characterized in that when the susceptor is raised by the lifting/lowering rotation mechanism, the susceptor constitutes a bottom surface of the reaction space.