JPH07307297A - Method of chemical vapor deposition - Google Patents

Abstract

PURPOSE:To manufacture a film, into which oxygen or carbon is not mixed, by forming the silicon film having concentration, in which oxygen or carbon reaches a specified value or less by measurement by a secondary ion analytic method, onto a surface to be formed by an exhaust means. CONSTITUTION:In an exhaust system 52 using a continuous exhaust system TP, carbon concentration has 1X10<17>-5X10<18>cm<-3> in the measurement of a secondary ion analytic method, and carbon is contained only in 1X10<18> or less generally. Oxygen is also contained in 5X10<18>cm<-3> or less, preferably 1X10<18>cm<-3> or less. A pressure regulating valve 72 is closed, pressure in a reaction vessel 101 is brought to 0.01-10Torr, preferably 0.05-1Torr, the lower sections of the valve are brought to 1X10<-2>Torr or less, generally 1X10<-4>-10<-7>Torr, and the degree of the vacuum is attained by rotating a TP 87. The inverse diffusion of the polymerized oil of a VP 36 and the back flow of atmospheric air for exhaust impregnated into oil, particularly oxygen can be prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and method for producing a vapor phase reaction coating.

[0002]

2. Description of the Related Art Conventionally, in a CVD apparatus such as a PCVD apparatus, since the pressure of the reaction system is as high as 0.05 to 10 torr, only VP is used for the exhaust system and the like, and TP etc. that generate a higher vacuum degree It was completely impossible to provide.
However, the present inventor has found that in such a PCVD device, the exhaust system has a VP
With this alone, this VP makes a discontinuous rotational motion, so the atmosphere (especially oxygen) from the exhaust system at atmospheric pressure that is in contact with air flows backward, and a part of this atmosphere mixes in the oil. From the above, it was found that re-vaporization causes backflow into the reaction vessel.

Therefore, due to this backflow, oxygen is mixed into the film formed, and for example, when a silicon film is produced, oxygen is mixed into the film at a concentration of 3 × 10 ¹⁹ to 2 × 10 ²⁰ cm ^-3. I got it. For this reason, hydrogen or fluorine is added to such a coating so that what should be a silicon semiconductor may be called lower silicon oxide.

[0004]

The present invention aims to prevent such drawbacks.

[0005]

The present invention relates to the production of a non-oxide coating when a coating is produced using a reactive gas, in which a gas phase reaction (hereinafter By performing CVD)
This is a method for producing a gas phase reaction coating in which the amount of oxygen mixed in the coating is set to a concentration of 1 × 10 ¹⁹ cm ⁻³ or less.

In order to prevent the backflow of the atmosphere from the exhaust system in the production of a non-oxygen type coating, the present invention uses a discontinuous rotation type vacuum such as an oil rotation type rotary pump and a mechanical booster pump. Pump (hereinafter simply vacuum pump or VP
Not only) but a continuous exhaust type
A feature of the present invention is that a bo molecular pump (hereinafter simply referred to as a turbo molecular pump or TP) is interposed between the reaction container and the vacuum pump to prevent backflow of the atmosphere from the exhaust system. Therefore a non-oxide film such as non-single-crystal silicon, a reactive gas silane in forming using _{(Si n H 2n + 2 n} > 1), oxygen in an amount of 5 × 10 ¹⁸ cm of that in the coating ^{- 3} or less, preferably 1 × 10 ¹⁸ cm ⁻³ or less.

According to the present invention, the exhaust system is provided between the reaction chamber and VP via a valve for adjusting the pressure during the reaction, so that the plasma gas phase in the reaction chamber is in the pressure range of 0.05 to 10 torr. A film is formed by using a reaction (referred to as PCVD), a photo CVD (referred to as Photo CVD), or a method in which these are used together (hereinafter simply referred to as a CVD method), and under a pressure adjusting valve, 1 × 10 ^-2 torr or less ( Generally 10 ^-4 to 10 ^-6 tor
The pressure of the reaction system is higher than that of this exhaust system (1 × 10 ^-2 torr or more, that is, 0.
05 to 10 torr) to form a film.

Further, according to the present invention, a plurality of reaction chambers are connected to the plasma CVD apparatus, and a P-type non-single crystal semiconductor, an I-type non-single crystal semiconductor and an N-type non-single crystal semiconductor are placed on a substrate in each reaction chamber. It can also be applied to a method for manufacturing a semiconductor device in which a PIN junction is formed by stacking layers.

[0009]

EXAMPLES As an example of the present invention, a vapor phase reactive coating forming apparatus (an apparatus whose outline is shown in FIGS. 1 and 2) for realizing the vapor phase reactive coating forming method of the present invention will be described, and thereafter, A method for manufacturing a semiconductor device that forms a PIN junction using the device will be described. This drawing (Fig. 1, Fig. 2) shows PIN junction, PI
P-junction, NIN-junction or PINPIN ... PIN-junction semiconductors on the substrate are semiconductor layers of different conductivity types, but with different main components or different stoichiometry. This is an apparatus for automatically and continuously forming a multi-layer for stacking without being influenced (mixed) by the semiconductor layer formed in the previous step.

As shown in FIG. 1, this vapor phase reactive film forming apparatus has a doping system (50) for introducing a reactive gas, a reaction vessel (51), and an exhaust system (52). A semiconductor layer is formed as a double reaction vessel type having a reaction space having an inner surface formed of an insulator inside the reaction vessel, and additionally, a P-type semiconductor (system A in the drawing) and an I-type semiconductor (system C in the drawing) A multi-chamber type PCVD apparatus in which respective reaction vessels are connected via a separating part (system B in the drawing) when a junction is formed on a substrate by laminating with and an N-type semiconductor.

The buffer chamber (7) of the separation unit (system B in the drawing) in this PCVD apparatus is used. In this embodiment, a non-single crystal semiconductor layer to which hydrogen or a halogen element is added is formed to form a semiconductor layer having P, I and N type conductivity types with a small recombination center density, and the PIN is formed at the stack boundary. While forming the junction, each semiconductor layer is prevented from being mixed with impurities from other adjacent semiconductor layers and deteriorating the junction characteristics, and the atmosphere, particularly oxygen is exposed during the process of forming each semiconductor layer. Thus, continuous production is performed so that an interlayer insulating material is not formed due to the oxidation of a part of the semiconductor. Further, the present embodiment is a so-called mass production method in which a large number of substrates are simultaneously increased in film growth rate in a multi-chamber plasma reaction method in which a large number of such reaction vessels are connected independently in each reaction. This example is 10 cm
X 10 cm or 10 to 50 cm in the electrode direction, for example 40 cm, with a width of 15 to 120 cm, for example 60 cm substrate (40 cm x 60 cm
Alternatively, 20 sheets of 20 cm × 60 cm were arranged in one batch).

In FIG. 1 and FIG. 2, a reactive gas introducing means and an exhausting means are provided, and these supply nozzles and exhausting nozzles are provided so as to face the inside of the insulator formed inside the reaction chamber. A pair of electrodes (61), (61 ') or (62), (62')
The reactive gas supply nozzles (17), (18) and the exhaust nozzles (17 '), (18') were arranged. That is, a structure (39) (39 ') is formed in which the outside of the electrode is wrapped with the hood insulator. Furthermore, in order to confine the reaction space between the hoods, the outer periphery is insulated.
Surrounded by (38) and (38 '). Further, FIG. 2 shows a drawing showing a cross section of FIG. 1. Opening and closing doors are provided in front of the reaction vessel (left side of the drawing) and after (right side of the drawing), and heating means (13) such as a halogen lamp is provided on the inner surface of the door. , (13 ') are provided.

A method of manufacturing a semiconductor device forming a PIN junction, which is an embodiment of the present invention, will be described below with reference to FIGS. The drawing shows some of the multiple reaction systems that make up the PIN junction. That is, two of the three reaction systems formed by stacking P, I and N type semiconductor layers (A,
An apparatus example of a multi-chamber type plasma vapor phase reaction apparatus having C), a first preliminary chamber, and a transfer buffer chamber (system B) is shown.

The systems A, B and C in the drawings have two reaction vessels (101), (103) and a buffer chamber (102), and a gate valve (44), (45), (4
It has 6) and (47). Independently, the reactive gas supply nozzles (17), (18) and the exhaust nozzles (17 '), (18')
And the reactive gas is provided as a laminar flow from the supply system to the exhaust system. This device has a first spare room on the entrance side.
(100) is installed. First, from the door (42) to the board holder (2) 2
Two substrates (1) having two surfaces to be formed on one surface were attached. In addition, attach this holder (3) to the outer frame jig (outer periphery only (3
8) and (38 ') are provided at a predetermined equidistant distance from each other. In other words, the substrate having this formation surface contacts the substrate holder (2) with the back surface on which no coating is formed, and the two substrates and the substrate holder are regarded as one holder (3), and 6 cm ± 0.5 c
It was made to stand in an outer frame jig of an insulator with a gap of m 3. As a result, 20 substrates of 40 cm × 60 cm could be simultaneously coated. Thus, the reaction space (6) (8) with a height of 55 cm, a depth of 80 cm and a width of 80 cm is surrounded by insulators (39) (39 ') on the upper and lower sides, and the outer periphery is insulated by an outer frame jig (38) (38). Surrounded by ').

First, the first auxiliary chamber (100) is provided with a pressure adjusting valve.
(71) was fully opened, and a vacuum pump (35) was used to evacuate through TP (86). After that, the pressure control valve (72) is fully opened, and the gate valve (44) for separation from the reaction vessel (101) which has been evacuated to 3 × 10 ⁻⁸ torr or less by TP is opened, The substrate held by the outer frame jig (38) was transferred. For example, the substrate is moved from the preliminary chamber (100) to the first reaction container (101) and then the gate valve (44) is closed to move the substrate to the first reaction container (101). At this time, the substrate (1) and the like held in the first reaction vessel (101) are held in the buffer chamber (102) in advance or at the same time, and the jig and the substrate (2) held in the buffer chamber (102). Is the second reaction vessel (1
03), and the substrate held in the second reaction container (103) is in the second buffer chamber (104). It is possible to open and move the gate valves (45), (46) and (47) to the second auxiliary chamber on the side. After this, the gate valves (44), (45), (46),
I closed (47).

That is, the movement of the gate valve is such that when the door (42) is opened at atmospheric pressure, the gate valves (44), (45), (46), (4
7) is closed, and plasma gas phase reaction is performed in each chamber. On the contrary, when the door (42) is closed and the auxiliary chamber (100) is sufficiently evacuated, the gate valve (44),
(45), (46), (47) are opened, the substrate and jig of each chamber have a mechanism to move to the adjacent chamber, and the outside air is
01) and the buffer chamber (102) are not mixed. The case where the P-type semiconductor layer is formed by the PCVD method in the first reaction container (101) in the system A is shown below. Reaction system A
0.01 to 10 torr (including the reaction vessel (101)), preferably 0.
01 to 1 torr For example, 0.08 torr.

That is, with the pressure regulating valve closed, the pressure in the reaction vessel (101) is 0.05 to 1 torr, and below this valve is 1 × 10 ⁻² torr or less, generally 1 × 10 ⁻⁴ to 1 × 10 5. ^-7
It becomes torr, and this vacuum degree is fulfilled by rotating TP (87). In addition, since the TP of this continuous exhaust system is operated, it was possible for the first time to prevent the reverse diffusion of the polymerized oil of VP (36) and the reverse flow of the exhaust atmosphere, especially oxygen, impregnated in the oil. . Reactive gas is a doping system of system A (50)
More supplied. That is, as the silicide gas (24), silane (Si _n H
_{2n + 2} n> 1, especially SiH ₄ or Si ₂ H ₆ ), silicon fluoride (SiF ₂
Or SiF ₄ ) was used. Here, ultra-high-purity silane (purity 99.99%, but 0.1PPM for water and oxygenates is easy to handle.
The following) was used.

DMS (dimethylsilane (SiH ₂ (CH ₃ ) ₂ purity 99.99%)) was used as the carbide gas (25) to form the Si _X C _1-X (0 <x <1) of this example. . Silicon carbide (Si
_{For X} C _1-X 0 <x <1, boron was supplied as a P-type impurity into the above-mentioned monosilane at a concentration of 0.5% at the same time (24) and supplied together with silane. If necessary, hydrogen (purity 7N or higher) or nitrogen (purity 7N or higher) was supplied from the time (23) when the reaction chamber was brought to atmospheric pressure. These reactive gases pass through their respective flow meters (33) and valves (32),
The reactive gas was supplied from the supply nozzle (17) to the reaction space (6) through the negative electrode (61) of the high frequency power supply (14).

The reactive gas was supplied into the cylindrical space (6) surrounded by the holder (38), and a film was formed on the substrate (1) constituting this space. Further, electric energy, for example, high frequency energy (13.56 MHz) (14) was applied between the negative electrode (61) and the positive electrode (61 ') to cause plasma reaction, and a reaction product was formed on the substrate. The substrate was heated to 100 to 400 ° C., for example 200 ° C., by the same means as the infrared heaters arranged before and after the reaction vessel (103) shown in FIG.

As the infrared heater, a near infrared halogen lamp (emission wavelength of 1 to 3 μ) or a far infrared ceramic heater (emission wavelength of 8 to 25 μ) is used, and a cylindrical space surrounded by a holder in the reaction container. To 200 ±
It was installed at 10 ° C, preferably within ± 5 ° C. After this, as described above, the reactive gas described above was introduced into this container, and
A high frequency energy (14) was supplied to 10 to 500 W, for example 100 W, to cause a plasma reaction. Thus, the P-type semiconductor layer is B ₂ H ₆
/ SiH ₄ = 0.5%, DMS / (SiH ₄ + DMS) = 10%,
This reaction system A was formed as a thin film having an average film thickness of 30 to 300Å, for example, about 100Å. Eg = 2.05eV, σ = 1
It was from × 10 ^{-6 to} 3 × 10 ^-5 (Ωcm) ^-1 .

The substrate is a conductor substrate (stainless steel, titanium, aluminum or other metal), a semiconductor (silicon, germanium), an insulator (glass, organic thin film) or a composite substrate (glass or transparent organic resin on which light is transmitted). Conductive conductive film such as tin oxide to which fluorine is added, ITO is a single conductive film, or a two-layered film in which SnO ₂ is formed on ITO)
Was used. These are collectively referred to as a substrate not only in this embodiment but also in all of the present invention. Of course, this substrate may be flexible or a rigid plate.

Thus, the plasma vapor phase reaction was carried out for 1 to 5 minutes to form a silicon carbide film to which boron was added as a P-type impurity in a thickness of about 100 Å. Further, the substrate on which the first semiconductor layer was formed was moved to the buffer chamber (102) by opening the gate (45) and following the above-mentioned operation sequence, and the gate (45) was closed. The buffer chamber (102) is evacuated in advance to less than 10 ^-8 torr, for example, 4 × 10 ^-10 torr by a turbo molecular pump (TP) (88). This substrate is also gated by TP (89) to a reaction vessel held at 1 × 10 ^-7 torr or less as in system C.
It was relocated after opening and closing (46). That is, in the reaction system C in FIG. 1, ultrahigh-purity monosilane or disilane is used as the reactive gas of the semiconductor (water or silicon oxide, the concentration of the oxide gas is 0.1 PPM or less) (28), and 10 ¹⁷ cm ^-3 Since the following boron is added, it is possible to add 0.5 to 0.5 by hydrogen, silane, etc.
B ₂ H ₆ diluted to 30 PPM was supplied from (27), and a carrier gas was supplied from (26) as needed. Reactive gas substrate (1)
It flows from the upper side to the lower side along the formation surface of TP and reaches TP (89). FIG. 2 shows a vertical sectional view of the system C as seen from the outlet side.

In the drawings, rod-shaped halogen lamps are used as the lamp heaters 13 and 13 '. The reaction space was set to 100 to 400 ° C., for example 250 ° C., by a heater. The board (1) is held by the board holder (2) and is enclosed by the outer frame jigs (38) (38 '),
It constitutes the space (8). Next, on the substrate (1) on which the P-type semiconductor layer moved to the second reaction chamber is formed, the I-type semiconductor layer is formed to a thickness of 5000 Å, SiH ₄ 60 cc / min, and a film formation rate.
2.5 Å / sec, substrate (20 cm x 60 cm, 20 sheets, total area 24000
It was formed at a pressure of 0.1 torr in cm ² ). When Si ₂ H ₆ was used, the film formation rate was 28 Å / sec. Thus, the P-type semiconductor layer is formed in the first reaction chamber by the plasma vapor phase method, and then the I-type semiconductor layer is formed by the PCVD method.
The joint was made up.

After forming the I-type semiconductor layer to a thickness of about 7,000 Å in the system C, the substrate is transferred to the adjacent buffer chamber (104) according to the above-mentioned operation and further transferred to the adjacent reaction chamber. Then, an N-type semiconductor layer was formed by the same PCVD process. This N-type semiconductor layer is formed by removing Phoshin by using the PCVD method.
₃ / SiH ₄ = 1.0% silane and carrier gas hydrogen
SiH ₄ / H ₂ = 20%, and supply about 20% in the same manner as system A
A polycrystalline semiconductor layer having an N-type microcrystalline or fibrous structure is formed to a thickness of 0 Å, and silicon carbide is further formed on the upper surface thereof with DMS / (SiH ₄ + DMS) = 0.1 to form Si _X C _{1 -X} (0 <
It is formed by laminating N-type semiconductor layers represented by x <1) to a thickness of 10 to 200Å, for example, 50Å. Other reactors are the same as those in the system A. After this step, a 100 to 1500Å thick ITO film is formed on the substrate formed by PIN bonding outside the second auxiliary chamber, and a reflective or sublimable metal electrode such as an aluminum electrode is further formed thereon. It is made to a thickness of about 1μ by the vacuum deposition method, and (ITO + SnO ₂ ) front surface electrode ─ (PIN semiconductor) ─ (back surface electrode) on the glass substrate.
Was configured.

The characteristics of the semiconductor device having the PIN junction thus formed as a photoelectric conversion device are 7 to 9%,
AM1 (100mW / cm ² ) on a 10cm x 10cm substrate with an average of 8%
It has intrinsic efficiency characteristics under the conditions of, and even in a 40 cm × 60 cm glass substrate that is integrated into a hybrid type,
It was possible to obtain 5.5% with effective efficiency. As a result, the open-circuit voltage was 0.85-0.9V (0.87 ± 0.02V) with one element, but the short-circuit current was as large as 18 ± 2mA / cm ^2, and the FF also
It was as large as 0.60 to 0.70 and the variation was small in the panel and in the batch, and it was found that the method of the present invention is industrially extremely effective. FIG. 3 shows concentration distributions of oxygen and carbon impurities in a semiconductor in a PIN photoelectric conversion device manufactured by the present invention and the conventional method. The drawing shows the aluminum back electrode (94), N-type semiconductor (93), I-type semiconductor (9
2), P-type semiconductor (91), tin oxide translucent conductive film (9
0) is shown respectively.

The conventional exhaust system is a rotary pump or a mechanism.
In the exhaust method using only the nical booster pump
Does not use a continuous exhaust type TP, so the carbon curve (9
5), oxygen contains high concentration of impurities shown in curve (96)
Was. Especially oxygen is 5 × 10¹⁹~ 2 x 10²⁰cm^-3Type I
Had in semiconductors (92). Drawing is 5 × 10¹⁹cm^-3of
This is the case when oxygen is included. In addition, oil from the oil rotary pump
5 × 10 carbon due to backflow of components²⁰~ 4 x 10²⁰cm^-3Have
Was there. Drawing is 1 × 10²⁰cm ^-3Is the case.

On the other hand, in the exhaust system as shown in the present invention, the carbon concentration is 1 × 10 ^{17 to} 5 × as shown by the curve (98).
It has 10 ¹⁸ cm ^-3 and generally contains no more than 1 x 10 ¹⁸ cm ^-3 . In addition, oxygen is also 5 × 10 ¹⁸ as shown by curve (97).
cm ⁻³ or less, preferably 1 × 10 ¹⁸ cm ⁻³ or less, and FIG. 3 shows the case of 2 × 10 ¹⁸ cm ⁻³ . In FIG. 3, the aluminum of the back electrode (94) has 3 to 6 × 10 ²⁰ cm ⁻³ of oxygen. Therefore, this oxygen becomes the background oxygen in the measurement of SIMS (secondary ion analysis method) (using Kameka Co. 3F type), and the oxygen in the N-type semiconductor (93) becomes
It is thought that it became 10 ¹⁸ to 10 ²⁰ cm ^-3 .

Further, there are impurities in the P-type semiconductor due to oxygen and water contained in DMS, and the starting material is purified from silane to obtain oxygen or oxide of 0.1 PPM or less, thereby further increasing the oxygen concentration. It is possible to estimate the possibility of lowering. Regarding the types of semiconductors to be formed, not only Si but also other group 4 Ge, SixC _1-X (0 <x <1), SixGe _1-X (0
<X <1), SixSn (0 <x <1), single-layer or multi-layer, or non-oxygenated compound semiconductor such as GaAs, GaAlAs, BP, CdS. Needless to say. The present invention has shown a PCVD method in a multi-chamber system using three reaction vessels. However, it is effective to use this as one reaction vessel and to form silicon nitride by the PCVD method by the PCVD reaction of silane (SiH ₄ or Si ₂ H ₆ ) and ammonia (NH ₃ ).

The non-single-crystal semiconductor film formed by the present invention is an N (source) I (channel forming region) N (drain) junction or an insulating gate type field effect semiconductor device.
It is also effective for PIP bonding. Furthermore, it is a PIN diode and its energy bandwidth is W-N-W (WIDE-NALLO
W-WIDE) or Si _X C _1-X ─Si─Si _X C _1-X (0 <x <
1) A PIN junction type visible light laser, a light emitting element or a photoelectric conversion device having the structure may be manufactured. In particular, so-called W (P or N type) -N (I type) (WIDE TO NALLOW) having a heterojunction structure in which the energy band width on the light incident light side is wide and not only the conductive type but also the product in each reaction chamber We believe that it is industrially extremely important because it is possible to produce different layers independently of each other and laminate them. In the present invention, the separating section is not limited to the gate valve, but is provided with two gate valves and one buffer chamber as the system 2
It was effective to further prevent the impurities of the type semiconductor from mixing into the I type semiconductor layer and improve the characteristics. In addition, the provision of a buffer chamber to prevent reaction gases from mixing in the reaction chambers is effective when a large number of semiconductor devices with PINPIN ... PIN junctions are produced using a multi-chamber CVD device. It is a means.

Particularly, when the reaction pressure during film formation in each reaction chamber is different, it is important that the substrate can be moved between the reaction chambers only by changing the pressure in the buffer chamber without changing the pressure in the reaction chamber. . This is because when a large number of semiconductor devices having PINPIN ... PIN junction or the like are produced using a multi-chamber CVD apparatus, conventionally, the reaction chambers involved in moving the substrates between the reaction chambers are set to a high vacuum,
After the substrate was moved, the original reaction pressure was adjusted again. However, in the case of using the method of moving the substrate through the buffer chamber according to the present invention, the pressure of each reaction chamber may remain unchanged and only the buffer chamber may be changed in pressure.
Moreover, it is also possible to prevent the reaction gases in the reaction chambers from being mixed with each other. The embodiment of the present invention is the multi-chamber system shown in FIG. 1, and the PCVD method is supplied to all the reaction vessels. However, if necessary, a part or all of the composite coating may be formed by using an optical CVD method that does not use plasma, an LT CVD method (also called a HOMO CVD method), or a low pressure CVD method.

[0031]

According to the present invention, in order to carry out the exhaust from the reaction vessel during the film formation by the exhaust means of the continuous exhaust system, the inside of the reaction vessel is adjusted by adjusting the valve provided between the exhaust means and the reaction vessel. Pressure of 0.01-10 torr
r, a step of forming a non-oxide coating on the substrate in which oxygen or carbon has a concentration of 5 × 10 ¹⁸ cm ⁻³ or less as measured by SIMS (secondary ion analysis method), and the valve is opened in the reaction chamber. And a step of supplying hydrogen or nitrogen to bring it to atmospheric pressure, it is possible to produce a coating film in which oxygen or carbon is not mixed.

[Brief description of drawings]

FIG. 1 shows an outline of an apparatus for producing a film for plasma vapor phase reaction for carrying out the present invention.

FIG. 2 shows an outline of an apparatus for producing a film for plasma vapor phase reaction for carrying out the present invention.

FIG. 3 shows the distribution of impurities in a semiconductor device made according to the present invention and a conventional method.

[Explanation of symbols]

 50 Doping System Introducing Reactive Gas 51 Reaction Vessel 52 Exhaust System 61, 61 ', 62, 62' Electrodes 17, 18 Reactive Gas Supply Nozzle 17 ', 18' Reactive Gas Exhaust Nozzle 14, 15 High Frequency Energy Source 38, 38 ', 39, 39' Insulator 13, 13 'Heating means such as halogen lamp 101, 103 Reaction vessel 102, 104 Buffer chamber vessel 44, 45, 46, 47 Gate valve 100 Preliminary chamber 42 Preliminary chamber door 5 Preliminary chamber space 2 Substrate holder 1 Substrate 6 Reaction space of the first reaction chamber 8 Reaction space of the second reaction chamber 7, 9 Buffer chamber space 71, 72, 73, 74 Pressure adjusting valve 86, 87, 88, 89 Turbo Molecular pump 34, 35, 36, 37 Vacuum pump

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C23C 16/54 H01L 31/04

Claims (2)

[Claims] 1. When forming a silicon film by reacting a reactive gas by a gas phase reaction method in a reaction container forming an I-type semiconductor layer of an insulating gate type field effect semiconductor device having a NIN or PIP junction, In order to carry out the exhaust from the reaction vessel during the film formation by the exhaust means of the continuous exhaust system, oxygen or carbon is converted to S by the exhaust means.
5 × 10 ¹⁸ c measured by IMS (secondary ion analysis)
A method for producing a vapor phase reaction coating, which comprises forming a silicon coating having a concentration of m ^-3 or less on a surface to be formed. 2. When forming the I-type semiconductor layer of an insulating gate type field effect semiconductor device having a NIN or PIP junction, a reactive gas is reacted by a gas phase reaction method in different reaction chambers to form a first layer. In the method for producing a semiconductor coating comprising a second layer and a third layer, at least one layer of which contains silicon, a reactive gas is introduced into a reaction chamber kept under reduced pressure when the semiconductor coating is formed, The second
The reaction chamber during formation of the layer is separated from other reaction chambers by a gate valve, and the reactive gas and reaction products from the reaction chamber during formation of the film are kept at a pressure of 0.01 in the reaction vessel by continuous evacuation means. A method for producing a gas phase reaction coating, which is characterized by setting the pressure to 10 torr.