JPH08241869A - Plasma treatment method - Google Patents

Abstract

PURPOSE: To clean the inside of a reaction furnace by a method wherein impurities existing in a reaction chamber are removed by forming a plasma consisting of hydrogen and hydrogen chloride or chlorine in the reaction furnace forming a film on a substrate surface. CONSTITUTION: A pair of electrodes 9, 10 is arranged outside a reaction furnace 25 arranging a substrate 1 inside. As a pretreatment step for forming a film on a substrate 1, a reaction furnace 25 is evacuated and a hydrogen plasma is formed by electromagnetic energy from the electrodes 9, 10 to perform plasma cleaning, and absorbed moisture and oxygen on a surface of the substrate 1 are removed. Further, after removing hydrogen, helium is made plasma and further hydrogen on a surface of the substrate 1 is removed. For this hydrogen plasma generation, hydrogen chloride or chlorine is added to hydrogen (for example, 1 to 5%), chlorine radical is simultaneously generated and this radical sucks an alkali metal like sodium in a quartz holder, and also chlorine which is left and sucked on a wall surface is removed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor device having good reproducibility and characteristics by a plasma vapor phase method.

[0002]

2. Description of the Related Art In the present invention, after a first semiconductor device having P-type and N-type semiconductor layers is formed on a substrate provided in a reaction furnace by a plasma vapor phase method, the N-type semiconductor device is formed.
Alternatively, P-type impurities may be re-emitted from the inner wall of the reactor or the holder of the substrate into the P- or N-type semiconductor layer to be formed next, and this may be mixed in at a concentration of 10 ¹⁵ -10 ¹⁸ cm ^-3. In order to prevent this, a step of forming a coating film for the intrinsic or substantially intrinsic (hereinafter referred to as I layer) coating on the semiconductor layer previously produced during each step (in this case, the step of forming at the beginning of the next step). The coating may be coated) to substantially remove the past history.

Further, it is necessary to provide a step of removing the previously deposited semiconductor layers adhered to the inner wall of the reaction apparatus, the surface of the substrate holder and the like by converting reactive gas such as CF into plasma. To aim.

By doing so, the RUN-T can be reproduced with good reproducibility.
The characteristics of O-RUN can be reduced and the obtained characteristics can be made very excellent.

Further, according to the present invention, in a semiconductor device having at least one junction, especially PIN, PI, NI or PN junction on a substrate provided in a reaction furnace, inner walls of the reaction furnace, particularly plasma atoms or reactive gas collide. In order to prevent the release of impurities, particularly oxygen and alkali metal atoms, from the inner wall, it is intended to form an intrinsic or substantially intrinsic semiconductor layer such as non-single-crystal silicon in advance on the surface of these.

In order to prevent re-emission with the coating for substantially removing them, the present invention causes the semiconductor layer to output the electromagnetic energy Po necessary for manufacturing a semiconductor device, eg, Po.
~ 100W, temperature To, for example, 200 ~ 320 ℃,
Po-10W (provided that the minimum is 5W) to Po + 30W, and To-50 ° C to To + 50 ° C are particularly preferably prepared under the same or substantially the same conditions as Po and To, and 0.
It is characterized in that it is formed to a thickness of 2-1 μm.

In the conventional plasma CVD method, a semiconductor device having a PIN junction or the like has been manufactured in one reaction furnace. However, if this bonding is repeated, it suffers from completely indefinite deterioration and variation, and only the reliability as a semiconductor device is unsuitable.

As a result of one of the causes, the most significant cause is that oxygen and alkali metals adhering to the inside of the reaction furnace are mixed in the semiconductor layer, resulting in a decrease in electric conductivity. Even if 1PPM is mixed, the dark conductivity of 10 ^-6 (Ωcm) ^-1 is 10 ^-8 (Ωcm) ^-1 and 1/100.
Had been lowered to.

Further, even in the case of alkali metal, the incorporation of 5PPM causes a decrease in the conductivity of P-type and I-type and a decrease in the conductivity of the transparent conductive film.

In order to prevent these contaminations, a semiconductor layer having a thickness of 0.2 to 2 μm is previously formed on the inner wall of the reaction furnace or the portion of the substrate holder (also referred to as a boat) which is sputtered by the reactive gas due to the plasma. It was extremely important to form and coat it. Further, with respect to deterioration of reproducibility characteristics, an attempt was made to form an N or P type semiconductor layer in the last step and to form a P or N type semiconductor layer in the next first step in the production of one semiconductor device. At this time, the first impurities such as phosphorus are mixed in the P-type semiconductor at a concentration of 10 ¹⁵ to 10 ¹⁸ cm ^-3 . Therefore, P
For example, even if a p-type layer is formed by adding boron to a concentration of 10 ¹⁸ to 10 ²¹ cm ⁻³ , the electric conductivity of the p-type semiconductor layer is extremely poor because the recombination centers increase due to the incorporation of phosphorus.
When there is no mixture, 10 ^-2 to 10 ⁺¹ (Ωcm) ^-1 against 10
Only ^-6 to 10 ^-4 (Ωcm) ^-1 and 1/100 to 1/1000 were obtained.

Therefore, in the PIN photoelectric conversion device, an efficiency of 2 to 4% was obtained only with a variation of ± 200% for each run, which was not preferable. However, according to the method of the present invention, it has become possible to obtain a high conversion efficiency of about 3 to 5 times, which is 8 to 10%.

In order to reduce the effect of the impurity oxygen doping, a patent application for semiconductor device fabrication method filed by the inventor of the present invention is 56-55608 (original display 53-1528).
87 filed on Dec. 10, 1978) is known. For example, when making a PIN semiconductor device, each P
Layers, I layers, and N layers are made into independent reactors, and the substrate is moved between the layers. This method can have the same measures as those of the present invention, and can obtain extremely preferable electric characteristics. However, in that case, the apparatus is three times as much as the one-chamber system, and the manufacturing cost is 2.5 to 3 times more expensive. Further, it has a defect that it is not suitable for mass production.

The present invention is particularly effective in such a reactor, especially in a horizontal reactor. In addition, it is particularly effective when trying to make a large number of semiconductor devices on a substrate, and has a major feature that the manufacturing cost including depreciation of each semiconductor device can be reduced to 1/100 of that of a vertical reactor. are doing. That is, the present invention is directed to such a horizontally arranged reaction furnace or reaction tube (10 to 30 cmφ,
A method using a length of 1 to 5 m) will be mainly described.

An electrode for supplying electromagnetic energy for converting a pair of reactive gases into plasma is provided outside the reaction tube, and a heating device is provided outside the electrode so as to surround the reaction tube and the electrode. A reactive gas is caused to flow in the direction of the furnace, and the substrate is arranged along the flow of this gas.

Further, substrates are arranged in the apparatus in a direction perpendicular or parallel to an electromagnetic field generated by a pair of electrodes, and the substrates are arranged in a plurality of stages or a plurality of rows to form a substrate of 2 to 20 cm □, for example, 20 stages of 10 cm □ substrates. It is mainly described that a film, in particular, a silicon, carbon silicon carbide or silicon germanium, germanium film, that is, a semiconductor film mainly composed of a tetravalent element is formed on one surface of 400 sheets of 20 rows in total.

The present invention relates to a reactive gas composed of a hydride or a halide (carbide silicide gas) having a carbon-silicon bond, a silicide gas such as silane (Si _n H _{2n + 1} n ≧ l) or acetylene. A non-single crystal silicon carbide, silicon or carbon-based coating film is formed on the surface to be formed using hydrocarbons at a reactor pressure of 0.05 to 1 torr at a pressure of 100 to 40
The present invention relates to a plasma vapor phase method for forming at a temperature of 0 ° C.

The present invention further includes an impurity gas containing trivalent impurities such as B, Al, Ga and In, such as diborane (B ₂ H ₆ ), and an impurity gas containing pentavalent impurities such as phosphine (PH). ₃ ) or arsine (A
sH ₃ ) is gradually added so that the P-type layer, the I-type layer and the N-type layer are further laminated in the order of PIN in close contact with the substrate having the surface to be formed, and this is repeated and stably manufactured. Is intended. Further, the present invention uses a semiconductor having an amorphous structure (referred to as AS), a semi-amorphous (semi-amorphous, hereinafter referred to as SAS) having a crystallinity of 5 to 100 Å, or 5 to 200 Å by the power of electromagnetic energy to generate plasma. A non-single-crystal semiconductor film such as a semiconductor having a micro-polycrystal (micro-polycrystal, hereinafter referred to as PC) structure having a size of 1 is produced. When stronger electromagnetic energy is applied, the substrate surface is apt to have an amorphous structure sputtered with defects. In order to eliminate such a defect structure, the substrates are separated from each other by 10 to 40 mm, typically 20 to 25 mm, and even when high energy of 200 to 500 W is required for the plasma reaction, this spice is formed on the surface to be formed. It is characterized in that it has characteristics equivalent to those obtained by controlling the distance for obtaining substantial plasma energy by the distance between the substrates and forming a film with a weak power of substantially 2 to 20 W.

Therefore, in the present invention, silicon carbide (SixC _1-x 0 <x <
When trying to make 1), a material having a carbon-silicon bond was used. That is, a hydride or a halide having a carbon-silicon bond such as tetramethylsilane (Si (CH
₃ ) ₄ ) (simply called TMS), tetraethylsilane (Si
(C ₂ H ₅ ) ₄ ), (Si (CH ₃ ) xCl _4-x (1 ≦ x ≦ 3)
A reactive gas such as Si (CH ₃ ) xH _4-x (1 ≦ x ≦ 3) is used to easily obtain a Si—C bond in the reaction product.

When a film containing silicon as the main component is to be obtained, Si _n H _{2n + 2} (n ≧ 1) silane, SiF ₄ or a mixed gas thereof is used. When trying to obtain carbon, acetylene (C ₂ H ₂ ) or ethylene (C
₂ H ₄ ) was mainly used. By doing so, silicon (Si), silicon carbide (SixC _1-x 0 <x <1) or carbon (C) (when these are combined, SixC _1-x (0 ≦ x
Since it can be expressed as ≦ 1), hereinafter, when referring to silicon carbide, SixC _1-x (meaning 0 ≦ x ≦ 1) is produced).

Further, trivalent or pentavalent impurities are added here to form a P type, an I type (intrinsic or substantially intrinsic without artificially adding impurities including autodoping) and an N type from the surface to be formed. A half body or a half insulator was produced.

Further, when such a reactive gas is used, the electromagnetic energy of 50 W or less at a pressure of 1 atm or less, particularly 0.01 to 10 torr, typically 0.3 to 0.6 torr, is applied to the reactor, for example. 0.01-100MHz
In particular, it is possible to form a coating at 500 KHz or 13.56 MHz. That is, a low energy plasma CVD apparatus could be obtained.

When a high-energy plasma atmosphere of 50 to 500 W is further applied, the formed silicon carbide is crystallized, and as a result, 0.1 to 5% of boron or phosphorus in the P-type or N-type (here, (BH or PH) / (carbide gas or silicon carbide gas + silicide gas ratio) is added, the electrical conductivity was 10 ^-9 to 10 ^-3 (Ωcm) ^-1 at low energy. Is 10 ^-6
We were able to increase it to about 10 times ⁺² (Ωcm) ^-1 .

Further, the silicon carbide obtained by using this high energy method could have a so-called SAS structure having a microcrystalline structure with a size of 5 to 200 Å. In such a SAS, the ionization rate of the P or N type impurity serving as an acceptor or a donor was 97 to 100%, and all of the added impurities could be activated. The plasma vapor phase method of the present invention will be described below with reference to the drawings.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an outline of a plasma CVD apparatus using the present invention. A substrate having a surface to be formed in FIG. 1 (1)
Is held by a square quartz holder, and in the drawing, it has a structure of 7 rows and 2 columns in total. The substrate and the holder are installed in advance in a separate room (29) in front of the reaction furnace from an inlet (30), and a valve (32) and a rotary pump (33) perform vacuum squeezing. Further, the opening / closing door (34) is opened and introduced into the reaction furnace by an automatic feeder, and the mixing plate (35) for the mixer is also arranged at the same time. These were made in a vacuum state in both the reaction furnace and the separate chamber, and efforts were made to prevent any oxygen (air) from entering the reaction furnace. Further, by closing the opening / closing door (34), the substrate was placed between the electrodes (9) and (10) as shown in the drawing.

Each substrate is 10 to 40 mm, typically 20 to 2
The reactive gases from the holder are arranged at intervals of 5 mm, and a mixer (8) is provided in front of the reaction furnace (25) to form a laminar flow, and these reactive gases are evenly distributed in the space between the substrates. It is provided to be injected into. The formation surface is a bottom surface of the substrate or a side surface vertically arranged with the back surfaces of the substrates overlapped with each other.

Further, the drawing shows a structure in which the reaction system is seen from above, and the substrates (1) are arranged vertically with their back surfaces aligned with each other. As described above, it is extremely important to remove the flake to the lower part by utilizing gravity, considering the mass production yield. Further, in the reaction furnace (25) in which the substrate (1) is inserted, an electric field of electromagnetic energy is perpendicular to or parallel to the substrate (especially if it is parallel, it is easy to obtain the uniformity of the coating). (B) In particular, a pair of electrodes (9) and (10) are arranged vertically or horizontally so as to be added as shown in (B). An electric furnace (5) is provided outside this electrode, and the substrate (1) is 100 to 400.
C. Typically, it is heated to 300.degree.

As the reactive gas, hydrogen or helium carrier gas such as helium is added from (13), trivalent impurity of diborane (14), and pentavalent additive phosphine from (15) to tetravalent. Silane gas silane, which is a substance, was introduced from (16).

A reactive gas T having a carbon-silicon bond is also used.
When MS (20) is used, it is stored in the stainless steel container (21) because it is a liquid in the initial state. This container is controlled to a predetermined temperature by the electronic thermostatic layer (22).

This TMS has a boiling point of 25 ° C., the rotary pump (12) is evacuated through the valve (11),
The inside of the reaction furnace is 0.01 to 10 torr, particularly 0.02 to 0.
It was kept at 4 torr. By doing this, a pressure lower than 1 atm results in no TM
S can be vaporized. This vaporized TMS is 1
Introducing into the reaction furnace at a concentration of 00% via a flow meter enables the flow rate to be controlled more accurately than in the conventional method in which the container (21) is bubbled to release the reactive gas. , Technically important.

When the flow meter was clogged for practical use, a helium was introduced from (24) in the drawing. In addition, the reaction tube (2
5) or when removing the reaction product attached to the inner wall or surface of the holder (2), CF ₄ or CF ₄ + O ₂ (2 to 5%) is introduced from (17), and electromagnetic energy is applied to add fluorine radicals. Were generated and vapor-phase-etched to remove.

Further, in this plasma discharge, after the reactive gas is mixed into the mixing chamber (8), the excitation chamber (2
In 6), a spatial reaction in which decomposition or reaction was caused and a reaction product was formed on the substrate was mainly used. As the electromagnetic energy, DC or high frequency was mainly used from the power source (4).

In this way, a silicon carbide coating film was formed on the formation surface. For example, the substrate temperature was 300 ° C., the high-frequency energy output was 25 W, silane or TMS was 50 cc / min and He was 250 cc / min as a carrier gas. With (reactive gas / He) 5, a film growth rate of 160Å / min could be obtained.

Furthermore, for this film formation, a PIN junction, P
An N junction, a PI, an NI junction, a PINPIN junction, etc. were formed by gradually laminating reaction products required to have the required thickness on the substrate.

After the coating film has been formed on the surface to be formed in this way, after the reactive gas is sufficiently purged from the reaction tube, the opening / closing door (34) is opened and the mixer mixing plate (35). , The substrate on the jig (3) is placed in a separate chamber (29) by an automatic drawing tube, and the reaction cylinder and the separate chamber are both vacuumed (0.01
(below torr) and moved. Further, after closing the opening / closing door (34), the valve was opened from (31) in another room to fill the air with air to bring it to atmospheric pressure, and then the substrate on which the jig and the film were formed was taken out.

As is clear from the above examples, according to the present invention, the reactive gas is mixed in the mixer (8), and then the exhaust port (6) is randomly moved in a layered state (microscopically in a plasmaized state). The substrate is arranged in parallel with this flow, and a film is formed on the surface to be formed to a thickness of 0.1 to 3 μ with a variation of ± 5% or less. There is.

Further, at this time, the plasma is generated by utilizing the glow discharge method, and the feature thereof is that the electrode is arranged outside the reaction tube so that the plasma is uniformly generated on a large amount of the substrates.

Further, in forming the film, 7 steps 2 as shown in the drawing.
When the reaction cylinder is lengthened to 20 rows and 20 rows instead of a row, it is not 0.4 torr but 0.2, 0.1,
The lower pressure of 0.05 torr is important for obtaining the uniformity of the film quality, particularly the uniformity of the front row and the last row.

Further, in order to prevent mixing of uncontrollable oxide gas such as oxygen into the reaction cylinder, a separate chamber was provided, and it was combined with the work in the atmosphere through this separate chamber. Was very important to obtain reproducibility of.

FIG. 2 shows the relationship between the arrangement of the substrate (1) and the electrodes (9) and (10) as seen from the direction of the exhaust port (6) in the drawing of FIG. In the drawing, (A) shows the substrates arranged horizontally and the electromagnetic fields of the electrodes (9) and (10) arranged in the horizontal direction. In this case, the number of substrates that can be introduced at one time can be increased.

FIG. 2B shows an electromagnetic field generated by the electrodes (9) and (10) and the substrate (1) is vertically arranged, and the number of substrates arranged is twice that of (A).

FIG. 3 shows an operation procedure chart of the semiconductor device manufacturing method of the present invention. "0" in the drawing
(49) is 0.01 torr due to vacuuming of the reactor.
Retention below r is shown. Furthermore, the "1" (40) indicates the coating of silicon or silicon carbide on the reactor or reactor and the holder according to the invention. Details of this coating are shown in FIGS. 3 (B) and 3 (C). FIG. 3 (B)
Is less than 0.01 torr by vacuuming (49), 1
After holding for 0 to 30 minutes, hydrogen is 0 to 0 by electromagnetic energy.
Plasma cleaning was performed at an output of 30 to 50 W for 30 minutes to remove adsorption, moisture and oxygen. After further removing the hydrogen, the helium is simultaneously set to 3 by (51).
Plasma was generated for 10 to 30 minutes with an output of 0 to 50 W, and hydrogen on the surface was removed. This hydrogen plasma generation (5
Regarding 0), when HCl or Cl is added to hydrogen at a concentration of 1 to 5%, chlorine radicals are simultaneously generated, and the radicals are present inside a holder such as quartz such as a sodium. Has the effect of sucking out alkali metals. Therefore, the concentration of sodium, water, oxygen, etc. at the background level is 10 ^{14 in the} formed film.
It was a very important pretreatment step, as it could be less than cm ^-3 .

When this chlorine was added, it was also effective to remove chlorine remaining adsorbed on the wall surface by sputtering with an inert gas (51).

Then, after vacuuming these systems, silane which is a silicide gas or TMS which is a silicon carbide is introduced and decomposed by plasma energy to obtain 0.1 to 2 μm.
Typically, it is formed to have a thickness of 0.2 to 0.5 μ. When these films were formed, it was particularly thick and easy to stick to a region to which high electromagnetic energy was applied, that is, a region where impurities were likely to be re-emitted, which gave doubly favorable results.

Even when the complicated pretreatment process of the present invention is not performed, after vacuuming as shown in FIG.
Silicon or silicon carbide in (52) is also 0.1 to
It was effective to prevent the re-release of oxygen and alkali metal from the reactor wall after forming 2 μm.

In FIG. 3A, for manufacturing a semiconductor device, substrate coating, system vacuuming (41), P or N-type semiconductor manufacturing (42), I-type semiconductor layer manufacturing (43). , Manufacturing an N-type semiconductor layer (44),
A first semiconductor device was produced (48). It goes without saying that this semiconductor device must be manufactured according to the device design specification having at least one junction such as PI, NI, PIN, PN.

Thereafter, for this system, the same semiconductor as the I-type semiconductor layer shown in (46) or the semiconductor layer shown in (42) for the reaction system in which only the reaction furnace or this reaction furnace and the holder are inserted is installed. The layer coating was such that the debris from step (44) used in the previous fabrication of the semiconductor device did not affect the next run. The details are shown in FIGS. 3 (B), (C), (D), and (E).

That is, as shown in FIG. 3B, the semiconductor layer is formed in the first step of vacuum drawing (49) hydrogen plasma discharge (50), helium plasma processing (51), and run of the semiconductor device as in the above-mentioned pretreatment. It has a step (52). However, these (50) and (51) are already (46) in (A)
Therefore, it is generally sufficient to form a semiconductor layer having a thickness of 0.1 to 2 μm in (52) of (C).

Further, in order to eliminate the history of the previous semiconductor device fabrication (40), that is, the previous run, (D), (E)
You may perform the plasma etching process shown in FIG. That is, in FIG. 3B, vacuum drawing (49) CF or CF + 0 (about 5%) was introduced from (17) in FIG. 1 and plasma etching (53) was performed for 20 to 1 hour. A vacuum is further applied, and then a hydrogen plasma treatment (50) is performed for 10 to 30 minutes to remove the C and F residues.
A semiconductor layer having a conductivity type and components similar to those of the semiconductor layer (42) of I-type of 5 to 0.5 μm or the first run in the next step was prepared. This method was the most thorough and guaranteed reproducibility.

A simple method is shown in (E) (49).
The steps of vacuum evacuation and plasma etching (53) and removal of residual adsorption gas (50) were performed.

By doing so, P or N type impurities are mutually () between the final step (44) of the fabrication (48) of the first semiconductor device and the first step (42) of the next step (48). It was possible to eliminate the possibility of contamination in 42). It was also possible to prevent the addition of additives such as carbon and germanium in (44) in (42).

FIG. 4 shows the result of evaluation of the effect by the method of the present invention.

FIG. 4 shows the result of a photoelectric conversion device manufactured using the method of the present invention. In this case, ITO is formed on a metal such as a stainless substrate or a glass which is a transparent substrate as a substrate.
Was used, and a substrate having a multi-layered electrode on which tin oxide or antimony oxide was formed to a thickness of 100 to 500Å was used. On top of this, P-type silicon carbide (SixC _1-x 0 ≦ x ≦ 1) (for example, x = 0.3 to
0.5) to a thickness of 100 to 300 Å and to this upper surface is added intrinsic or substantially intrinsic AS or SAS silicon.
N-type silicon carbide (SixC _1-x 0 ≦ x ≦ 1 such as x = 0.3 to 0.5) is formed on the upper surface to a thickness of 4 to 0.7 μm.
Was made to have a thickness of 100 to 300 Å. The specifications of the P, I, and N type semiconductors are shown in FIG.
(42), (43), (44),
(42) .....

Further, after this, ITO is added in the range of 600 to
A photoelectric conversion device was made by forming an aluminum metal film with a thickness of 800Å by a vacuum deposition method. The conversion efficiency is shown in FIG.

With a cell size of 1 cm ² , AMl (100 m
Under the condition of W / cm ² ), 3% of the case (71) without the pretreatment (40) and the value (70) with the pretreatment were obtained. Furthermore, the efficiency (60) of the run (every production date) changes due to the addition of the intermediate step (46), and (61) is obtained without any addition.

The efficiency of (60) can be 11 to 9%, while 1 to 4 is obtained when the method of the present invention is not used.
There was only%.

Further, when the cell area was 100 cm ² , the efficiency of 7 to 9% could be obtained by using the method of the present invention, and it was 0 to 3% without using the method of the present invention. In particular, those having no diode characteristics had 30% or more and could not be manufactured.

FIG. 4B shows the electric conductivity value when an I-type silicon semiconductor is formed in the step of forming a P-type semiconductor in the surface step.

When a P-type semiconductor is produced in the previous step and the pretreatment of the intermediate treatment method of the present invention is not performed, the electric conductivity by light irradiation of AM1 is (65). The case opposite to the dark conductivity (64) was also observed, and the value was 10 ⁻⁶ to 10 ^−4, which was large and varied. On the other hand, when the pretreatment of the present invention was performed, photoconductivity (70) and dark conductivity (70 ') were obtained. Further, when the intermediate treatment was performed, photoconductivity (62) and dark conductivity (63) were obtained. These clearly show how important the prevention of the doping effect in the present invention is.

[0059]

As is apparent from the above description, the present invention is applicable to not only the photoelectric conversion device or the light emitting element but also various semiconductor devices such as a field effect semiconductor device and a photosensor array using the same reaction tube. It provides a very important manufacturing device and manufacturing method, and by this means, a single crystal of 100 to 500 substrates can be formed on 100 to 500 substrates in the same time as the production of four 10 cm □ by a conventional vertical plasma CVD device. A semiconductor film can be made, and it is suitable for mass production.
Further, by arranging the electrode structure or the substrate as in the present invention, the photoelectric conversion device having the PIN structure is
A conversion efficiency of 0% or more could be repeatedly and stably obtained, and the film quality was also excellent.

In the present invention, silicon carbide (SixC
_The description is centered on _1−x 0 ≦ x <1). However, if germane is used as the reactive gas, SixGe _1-x (0 ≦ x <
1) can be obtained, and it is also possible to obtain a so-called tandem structure, in which the first PIN structure is made of silicon and silicon carbide, and the second PIN structure is made of silicon and germanium silicide.

The present invention employs the horizontal plasma CVD shown in FIG.
The device is shown as the center. However, the method of making the electrode is a dielectric type, and plasma CV that uses arc discharge.
The present invention is effective even for the D device. The method of the present invention can be similarly applied to a vertical type and vertical type bell jar type plasma CVD apparatus.

[Brief description of drawings]

FIG. 1 is a plasma vapor phase apparatus of the present invention.

FIG. 2 shows a part of FIG.

FIG. 3 is a chart using the apparatus of FIG. 1 and a plasma vapor phase method of the method of the present invention.

4 (A) is the efficiency of the photoelectric conversion device obtained according to the chart of FIG. 3 and (B) is another material showing the doping prevention effect of the method of the present invention.

Claims (1)

[Claims] 1. A plasma processing method comprising removing hydrogen and hydrogen chloride or chlorine into plasma in a reaction furnace for forming a film to remove impurities existing in the reaction chamber.