JP2003188400A - Crystalline silicon carbide film and manufacturing method thereof, and solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a crystalline SiC film that has a wide band gap without losing conductivity, to provide the crystalline SiC film, and to provide a solar cell having a p-type crystalline SiC film. <P>SOLUTION: By the method, a crystalline SiC film used for a power generation section in a thin-film silicon-based solar cell is manufactured. In the method, a substrate is allowed to face a discharge electrode for accommodating into a container, the inside of the container is subjected to vacuum exhaust, a feed gas that at least contains organic silane, a dilute gas, and a dopant-containing gas and sets C/Si supply ratio to 1/5 to 3.0 is introduced into the container that is subjected to vacuum exhaust, high-frequency power having a frequency of 60 to 200 MHz is applied to the discharge electrode for generating plasma between the discharge electrode and substrate, a radical in the plasma is allowed to react on the surface of the substrate, and the crystalline SiC film where microcrystalline SiC and amorphous SiC are mixed is deposited on the substrate. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for manufacturing a crystalline SiC film, a crystalline SiC film, and the crystalline SiC film.
The present invention relates to a thin film silicon solar cell using a film as a conductive semiconductor layer and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a thin film silicon solar cell is manufactured as follows using a plasma CVD apparatus. First,
After forming the transparent electrode on the transparent insulating substrate, Si
A p-type silicon layer (p layer) is formed using H ₄ as a main gas, H ₂ as a diluent gas, and B ₂ H ₆ as a doping gas. Then p
An i-type silicon layer (i layer) is formed on the layer by using SiH ₄ as a main gas and H ₂ as a diluent gas. Further, SiH ₄ is used as a main gas, H ₂ is used as a diluent gas, and PH ₃ is used as a doping gas.
After forming the mold type silicon layer (n layer), a back electrode made of a metal such as aluminum is formed, and this serves as a solar cell.

In order to improve power generation efficiency, the p-layer of the power generation section has a wide bandgap to reduce light absorption as a window material, and has high conductivity to reduce resistance loss. Is desirable. That is, when the p layer has a wide bandgap, the open circuit voltage rises, and accordingly, the generated voltage at the time of light irradiation rises to increase the output.

[0004]

However, in the conventional silicon-based solar cell, even if the p-layer has a wide bandgap, the conductivity of the p-layer is greatly impaired and the short-circuit current is reduced. As a result, power generation efficiency is reduced.

Therefore, the present inventors have made various attempts to widen the band gap of the p layer without impairing the conductivity of the p layer. In addition, as another attempt, a SiC film, which is expected to have a wide bandgap and a high conductivity, is used in “Applied Surface Science 33/34”.
(1988) p. 1276; Hattori et al. (Hereinafter referred to as Reference 1) "using a microwave plasma CVD method.
It is synthesized at a high temperature of ℃ or higher and its characteristics are evaluated. However, the SiC film manufactured using the method of Document 1 has the following two problems.

First, in a low temperature range such as room temperature, it is difficult for carbon (C) to bond with silicon (Si) and carbon (C) is easily lost, so that high conductivity cannot be obtained.

Secondly, if carbon (C) is supplied in excess,
Since carbon (C) remains in the film as dangling bonds, it is difficult to crystallize as a SiC compound.
Therefore, the conductivity of the obtained SiC film is small.

The present invention has been made to solve the above problems, and is a method for producing a crystalline SiC film having a wide band gap and a crystalline SiC film at a low temperature without impairing the conductivity, and p. An object of the present invention is to provide a solar cell having a type crystalline SiC film.

[0009]

Means for Solving the Problems Crystalline Si according to the present invention
The method for producing a C film is as follows. A raw material gas having a supply ratio in the range of 1.5 to 3.0 is introduced into the vacuum-evacuated container, and (c) a high frequency power having a frequency of 60 to 200 MHz is applied to the discharge electrode to form the discharge electrode. Plasma is generated between the substrate and the radicals in the plasma to react on the surface of the substrate to deposit a crystalline SiC film in which microcrystalline SiC and amorphous SiC are mixed on the substrate. And

This is because if the frequency of the high frequency power is less than 60 MHz, the electron temperature in plasma is high and the number of film defects increases, so that it becomes difficult to generate SiC crystals. On the other hand, if the frequency of the high frequency power exceeds 200 MHz, it becomes difficult to secure the uniformity of the plasma generation density.

When the C / Si supply ratio is less than 1.5, carbon (C) is deficient, so that there is no difference in conductivity depending on the presence or absence of organic silane as shown in FIG. 2, and as shown in FIG. This is because the band gap becomes narrower. On the other hand, C / S
If the i supply ratio exceeds 3.0, carbon (C) is excessive,
This is because the conductivity decreases again as shown in FIG.

As the organic silane, monomethylsilane (C
H ₃ SiH _3), dimethylsilane ((CH _{3) 2} Si
H ₂ ), trimethylsilane ((CH ₃ ) ₃ SiH), and tetramethylsilane ((CH ₃ ) ₄ Si) are preferably used as a gas selected from the group consisting of one or more gases.

Depending on the type of organosilane, C /
In order to adjust the Si supply ratio, a silicon-containing gas or a carbon-containing gas is used, and silane (Si
H ₄₎ or disilane (Si ₂ H _6), using ethylene (C ₂ H ₄₎ or acetylene (C ₂ H ₂₎ as a carbon source.

Hydrogen gas (100%) is used as a diluent gas.
H ₂ ) or a mixed gas of hydrogen and argon (10% or less A
r-containing) is used. In this case, the dilution ratio ((H ₂ + Ar
(Gas) number of molecules / (number of Si + C) atoms) is preferably in the range of 50 to 300. If the dilution ratio is less than 50, the crystallinity of the film is lowered and SiC crystals are not formed. On the other hand, if the dilution ratio exceeds 300, the film-forming rate will be remarkably reduced, and the industrial productivity will be remarkably reduced.

The crystalline SiC film according to the present invention is a crystalline SiC film used as a wide band cap semiconductor in LSIs, photosensors, photocatalysts, solar cells, etc., and is a conductive semiconductor of a thin film silicon solar cell. When used in layers, it has a great effect. A raw material gas containing at least an organic silane, a diluent gas, and a dopant-containing gas and having a C / Si supply ratio in the range of 1.5 to 3.0 is introduced into the vacuum-evacuated container, and a frequency of 60 to 60 is supplied to the discharge electrode. 20
A high frequency power of 0 MHz is applied to generate plasma between the discharge electrode and the substrate, and radicals in the plasma react on the surface of the substrate to form plasma on the substrate. Characteristic SiC is mixed.

When a p-type crystalline SiC film is formed by doping boron (B), the B doping amount is 10 ^18.
It is preferably set to 10 ²¹ atoms / cm ³ . B doping amount is insufficient 10 ¹⁸ below atoms / cm ³ when the film conductivity of, whereas excess dopant when B doping amount exceeds 10 ^{2 1} atoms / cm ³ is generated a disadvantage that the defect.

In this case, p-type crystalline SiC for solar cells
It is preferable that the film thickness is 10 to 200 nm. If the film thickness is less than 10 nm, the inconvenience of lowering the generated voltage occurs. On the other hand, if the film thickness exceeds 200 nm, the amount of light reaching the substantially intrinsic i-layer, which is the photoelectric conversion layer, decreases because of large light absorption.

The solar cell according to the present invention comprises a light-transmissive substrate, a transparent electrode film formed on the substrate, and a transparent electrode film formed on the transparent electrode film, containing at least an organic silane, a diluent gas and a doping gas. Including C / Si supply ratio is 1.5 ~
A raw material gas having a range of 3.0 is introduced into the vacuum-evacuated container, and a frequency of 60 to 200 MHz is applied to the discharge electrode.
Is applied to the substrate to generate plasma between the discharge electrode and the substrate, and radicals in the plasma react on the surface of the substrate to form microcrystal SiC and amorphous SiC. P-type crystalline Si mixed with high quality SiC
C film, substantially intrinsic i-type silicon film formed on the p-type crystalline SiC film, n-type silicon film formed on the i-type silicon film, and n-type silicon film And a back electrode film formed on the above.

When the p layer is made of crystalline SiC to have a wide bandgap, light absorption in the p layer is reduced, so that the amount of light reaching the next i layer is increased, and as a result, the short-circuit current is increased.

The substantially intrinsic i-type silicon film formed on the p-type crystalline SiC film is amorphous silicon (a-Si), microcrystalline silicon (μc-Si), polycrystalline silicon, monocrystalline silicon, or monocrystalline silicon. It may be any of crystalline silicon and a mixed structure of amorphous silicon and microcrystalline silicon. Similarly, the n-type silicon film may have any of amorphous silicon (a-Si), microcrystalline silicon (μc-Si), polycrystalline silicon, single crystal silicon, and a mixed structure of amorphous silicon and microcrystalline silicon. Good.

Plasma C using tetramethylsilane ((CH ₃ ) ₄ Si) having a Si--C bond as a source gas.
A microcrystalline SiC film was synthesized by the VD method. Here, the “microcrystalline SiC film” contains crystalline SiC, and was identified by having a peak in the vicinity of 750 cm ⁻¹ in the Raman spectroscopic analysis spectrum. In addition to the crystalline SiC, the SiC film of the present invention includes amorphous SiC (a
-SiC), crystalline silicon and amorphous silicon (a-Si) are also mixed.

[0022]

Various preferred embodiments of the present invention will be described below with reference to the accompanying drawings.

Example 1 The production of the crystalline SiC film of Example 1 was carried out by the following procedure using the plasma CVD apparatus shown in FIG.

(1) A colorless and transparent soda lime glass (blue plate glass) is set as the substrate 2 so as to be in close contact with the heater 3 of the plasma CVD apparatus, and then the internal pressure of the reaction vessel 4 is set to 5 × 10 ⁻ by the vacuum pump 5. ^It was evacuated to ⁷ Torr. The heater 3 was energized to heat the substrate 2 to a predetermined temperature to sufficiently stabilize the temperature. The heating temperature of the substrate 2 is not limited and can be changed in the range of 100 to 300 ° C.

(2) Next, as shown in Table 1, crystalline Si
Sila as a raw material gas for forming a C-conductivity type semiconductor layer
(SiH_Four), Tetramethylsilane ((CH₃)_FourS
i), hydrogen (H₂) And diborane (B₂H₆) The reaction vessel
Introduced in 4. The flow rate of each component gas is SiH_Four0.
6sccm, (CH₃)_FourSi; 1 sccm, H₂300sccm,
B ₂H₆; 0.01 sccm. The source gas is a component
It may be introduced into the reaction vessel 4 separately for each
Pre-mix it outside the vessel 4 and put it all together in the reaction vessel 4.
May be introduced. Silane (SiH_Four) And tetramethyl
The composition ratio of orchid is not limited to 0.6: 1 but C / Si
The ratio is preferably in the range of 2-3.

(3) After introducing the raw material gas, the internal pressure of the reaction vessel 4 was controlled to 1.0 Torr by a pressure control device (not shown).
Here, the control pressure in the reaction vessel 1 is not limited to 1.0 Torr, but can be adjusted to 0.
Various changes can be made within the range of 2 to 2.0 Torr. After sufficiently stabilizing the temperature of the substrate 2 and the pressure in the reaction container 4, high frequency power is supplied from the high frequency power source 11 to the discharge electrode 9 through an impedance matching device (not shown) to generate plasma, p-type crystalline SiC film 22
Was formed into a film.

(4) Here, the frequency of the high frequency power source 11 is
The effects of the present invention can be obtained if the frequency is 60 MHz or more and 200 MHz or less. However, when the frequency is less than 60 MHz, the electron temperature in the plasma is high, so that the film defects increase and it becomes difficult to crystallize SiC. Therefore, the frequency is preferably 60 MHz or more. On the other hand, if the frequency exceeds 200 MHz, it becomes difficult to secure the uniformity of the plasma generation density. Therefore, the frequency is preferably 200 MHz or less. Subsequently, in this state, the p-type crystalline SiC film 22 was formed for a predetermined time so that the film thickness was 100 nm.

[0028]

[Table 1]

Comparative Example 1 As Comparative Example 1, silane (Si
H ₄ ), methane (CH ₄ ), hydrogen (H ₂ ) and diborane (B ₂ H ₆ ) were introduced into the reaction vessel, and SiC having a film thickness of 100 nm was formed on the glass substrate in the same manner as in Example 1. Filmed The film forming conditions of Comparative Example 1 are shown below. Regarding the gas flow rate, silane (Si
Film formation was also carried out by changing the flow rates of H ₄ ) and methane (CH ₄ ).

Pressure: 1.0 Torr Gas flow rate: SiH ₄ / CH ₄ / H ₂ / B ₂ H ₆ = 1.6 sccm
/ 4 sccm / 300 sccm / 0.01 sccm (Evaluation result) As a result of analyzing the p-layer 22 of Example 1 using Raman spectroscopy, it has a peak in the vicinity of 750 cm ^-1 , that is, a SiC crystal is formed. There was found.

FIG. 2 is a characteristic diagram of the C / Si supply ratio of the source gas and the electrical conductivity. In the figure, the characteristic line A connecting the white circle plots shows the result of Example 1, and the characteristic line B connecting the black circle plots shows the result of Comparative Example 1. As is clear from the figure, when the film was formed under the condition that the C / Si supply ratio was in the range of 2 to 3, microcrystalline SiC was generated, and 0.1 S / c
A high conductivity of m or more can be obtained.

FIG. 3 is a characteristic diagram of the C / Si supply ratio and the band gap. In the figure, the characteristic line C connecting the white circle plots shows the result of Example 1, and the characteristic line D connecting the black circle plots shows the result of Comparative Example 1. As is clear from the figure, when the film is formed under the condition that the C / Si supply ratio is in the range of 2 to 3, microcrystalline SiC is generated and a wide band gap of 2 eV or more is obtained.

In Example 1, a film having a high conductivity and a high band gap can be obtained when the C / Si supply ratio is in the range of 2 to 3.

Even when the doping gas (B ₂ H ₆ ) is not added, the SiC crystal can be synthesized as in the case where the doping gas is added.

(Example 2) In Example 2, the p-layer of Example 1 was applied to a thin film solar cell. The solar cell of Example 2 will be described with reference to FIG. The solar cell 20 includes a transparent electrode film 21 and a p-type crystalline SiC film 22 on the glass substrate 2.
(P layer), a substantially intrinsic i-type microcrystalline silicon film 23
(I layer), n-type microcrystalline silicon film 24 (n layer), back surface side transparent electrode film 25, and back surface electrode film 26 are laminated in this order to form a thin film silicon solar cell.

The transparent electrode film 21 is composed of tin oxide (SnO ₂ ) deposited on the glass substrate 2 via an intermediate layer such as silicon dioxide (SiO ₂ ) and zinc oxide (ZnO) deposited thereon. The upper layer of zinc oxide (ZnO) has a function of preventing the lower layer of tin oxide (SnO ₂ ) from being reduced when the p layer 22 is formed. Silicon dioxide (SiO ₂ )
The intermediate layer such as has a function of preventing impurities contained in the glass substrate 2 from entering the upper transparent electrode film. The lower tin oxide (SnO ₂ ) transparent electrode film is connected to a negative electrode of an external load (not shown).

The pin layers 22 to 24 are portions having a power generation function. Of these, the p layer 22 is a mixed film in which p-type microcrystalline SiC and amorphous SiC are mixed, and has a film thickness of, for example, 3
0 nm, boron (B) doping amount is, for example, 10 ¹⁹ atoms / c
m is ^3. The substantially intrinsic i layer 23 is a microcrystalline silicon film having a film thickness of, for example, 1500 nm.

The n layer 24 is an amorphous silicon film having a film thickness of, for example, 40 nm and a phosphorus (P) doping amount of, for example, 10 ¹⁹ atoms / cm ³ .

The transparent electrode film 25 on the back side is made of tin oxide (Sn).
O ₂ ), indium tin oxide (ITO) or zinc oxide (ZnO), and is connected to the positive electrode of the external load.

The back electrode film 26 is made of aluminum (Al) having a thickness of 0.3 μm formed by the vacuum evaporation method, and totally reflects the light incident from the substrate 2 side.

(Manufacturing Method) Next, a method of manufacturing the solar cell of Example 2 will be described. Solar cell 20 of Example 2
Was manufactured by the following procedure using the plasma CVD apparatus shown in FIG.

(1) As the transparent insulating substrate 2, a colorless transparent soda lime glass (blue plate glass) whose surface was strengthened by heat treatment after die cutting was used. On this glass substrate 2, a silicon dioxide (SiO ₂ ) intermediate layer by a thermal CVD method and a two-layer transparent electrode film 21 of tin oxide (SnO ₂ ) by a thermal CVD method and zinc oxide (ZnO) by a sputtering method are formed. did.

(2) Next, the substrate 2 is placed on the plasma CVD apparatus 1
After being set so as to be in close contact with the heater 3, the vacuum pump 5 evacuated the inner pressure of the reaction container 4 to 5 × 10 ⁻⁷ Torr. The heater 3 was energized to heat the substrate 2 to a predetermined temperature to sufficiently stabilize the temperature. The heating temperature of the substrate 2 is not limited and can be variously changed within the range of 100 to 300 ° C. according to the design conditions of the solar cell.

(3) Next, as shown in Table 1, silane (SiH ₄ ), tetramethylsilane ((CH ₃ ) ₄ Si), hydrogen (H ₂ ) are used as raw material gases for forming the p-layer 22. ) And diborane (B ₂ H ₆ ) were introduced into the reaction vessel 4. The flow rate of each component gas is SiH ₄ ; 0.6 sccm, (CH ₃ ) ₄ S
i; 1 sccm, H ₂ ; 300 sccm, B ₂ H ₆ ; 0.01 sccm
And The raw material gas may be introduced into the reaction container 4 separately for each component, or may be mixed in advance outside the reaction container 4 and then introduced into the reaction container 4 all at once.

(4) After introducing the raw material gas, the internal pressure of the reaction vessel 4 was controlled to 1.0 Torr by a pressure control device (not shown).
Here, the control pressure in the reaction vessel 1 is not limited to 1.0 Torr, but can be adjusted to 0.
Various changes can be made within the range of 2 to 2.0 Torr. After sufficiently stabilizing the temperature of the substrate 2 and the pressure in the reaction container 4, high frequency power is supplied from the high frequency power source 11 to the discharge electrode 9 through an impedance matching device (not shown) to generate plasma, p-type crystalline SiC film 22
Was formed into a film.

(5) Here, the frequency of the high frequency power source 11 is
The effects of the present invention can be obtained if the frequency is 60 MHz or more and 200 MHz or less. However, when the frequency is less than 60 MHz, the electron temperature in the plasma is high, so that the film defects increase and it becomes difficult to crystallize SiC. Therefore, the frequency is preferably 60 MHz or more. On the other hand, if the frequency exceeds 200 MHz, it becomes difficult to secure the uniformity of the plasma generation density. Therefore, the frequency is preferably 200 MHz or less. Subsequently, in this state, the p-type crystalline SiC film 22 was formed for 30 minutes so that the film thickness was 30 nm.

(6) Next, the supply of high frequency power and the raw material gas is stopped, the inside of the reaction vessel 4 is evacuated once, and then monosilane (SiH) is used as the raw material gas for the i layer 23 in the reaction vessel 4.
₄ ) and hydrogen (H ₂ ) were introduced to form a microcrystalline silicon i layer 23 having a film thickness of 1500 nm.

(7) Next, after stopping the supply of the high frequency power and the raw material gas and evacuating the inside of the reaction vessel 4 once, SiH ₄ , H ₂ and phosphine as the raw material gas of the n layer 24 are placed in the reaction vessel 4. (PH ₃ ) was introduced to form a microcrystalline silicon n layer 24 having a film thickness of 40 nm. The supply gas flow rates of the n layer 24 are SiH ₄ : 3 sccm, H ₂ : 300 sccm, PH
₃ : It was set to 0.02 sccm.

(8) Next, a transparent electrode film 25 made of indium tin oxide (ITO) was formed on the n layer 24 by a sputtering method. The thickness of the transparent electrode film 25 on the back surface side was 100 nm.

(9) Finally, aluminum (Al) was vacuum-deposited on the transparent electrode film 25 to form the back electrode 26 having a thickness of 0.3 μm. As a result, the solar cell 20 as a product
Got

Comparative Example 2 As Comparative Example 2, an example of manufacturing a solar cell in which a conventional amorphous SiC is applied to the p layer will be shown. The film forming conditions for the p layer are shown below. The cell structure and other layers are the same as in Example 2.

Pressure: 1.0 Torr Gas flow rate: SiH ₄ / CH ₄ / H ₂ / B ₂ H ₆ = 1.6 sccm
/ 2 sccm / 300 sccm / 0.01 sccm p-layer film thickness; 30 nm (Comparative Example 3) As Comparative Example 3, an example of producing a solar cell in which conventional microcrystalline silicon is applied to the p-layer is shown. The film forming conditions for the p layer are shown below. The cell configuration and other layer conditions are the same as in Example 2.

Pressure: 1.0 Torr Gas flow rate: SiH ₄ / H ₂ / B ₂ H ₆ = 4 sccm / 300 sccm
/0.01 sccm p layer film thickness; 30 nm (cell evaluation result) The solar cell 20 of the above-mentioned Example 2 was subjected to simulated sunlight (spectrum: AM1.5, irradiation intensity: 100 mW /
cm ² , irradiation temperature: room temperature) and the power generation characteristics were evaluated. In Example 2, the open circuit voltage and the power generation efficiency were 1.15 times and 1.50 times that of Comparative Example 2, and 1.
It was improved to 06 times and 1.09 times.

Also, when applied to an amorphous silicon solar cell, the open circuit voltage increases 1.05 times that of the conventional one,
The power generation efficiency is 1.08 times higher than the conventional one.

In addition, although the case where tetramethylsilane is used as the organic silane gas has been described in the above embodiment, the present invention is not limited to this, and other monomethylsilane, dimethylsilane, or trimethylsilane is used. Organosilane gas can also be used.

[0056]

According to the present invention, there is provided a method for producing a crystalline SiC film having a wide band gap without deteriorating the conductivity, a crystalline SiC film, and a solar cell having a p-type crystalline SiC film. .

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a plasma CVD apparatus.

FIG. 2 is a characteristic diagram showing a correlation between carbon / silicon supply ratio and conductivity.

FIG. 3 is a characteristic diagram showing a correlation between a carbon / silicon supply ratio and a band gap.

FIG. 4 is a schematic cross-sectional view showing a solar cell.

[Explanation of symbols]

1 ... Plasma CVD apparatus, 2 ... substrate, 3 ... heater, 4 ... container, 5 ... pump, 6 ... Exhaust pipe, 7 ... Gas supply pipe, 8 ... Film forming unit, 9 ... Electrode, 11 ... High frequency power supply, 20 ... Solar cells, 21, 25 ... Transparent electrode film, 22 ... p-type crystalline SiC film (p layer), 23 ... i-type Si film (i-layer), 24 ... n-type Si film (n layer), 26 ... Back electrode film (Al).

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 31/04 B W (72) Inventor Yoshimichi Yonekura 1-8 Sachiura, Kanazawa-ku, Yokohama, Kanagawa Mitsubishi Heavy Industries F-Terms in Basic Technology Research Institute Co., Ltd. (reference) 4G077 AA03 BE08 DB09 DB18 EA02 EA06 EB01 EC09 TB01 TC02 TC03 TC06 4K030 AA06 AA09 AA20 BA37 BB04 BB05 CA06 FA01 JA01 JA06 JA10 JA18 LA16 5F045 AA08 AB06 AC01 AC07 AC16 AC01 AD05 AD05 AD16 AD19 AD05 AD05 AD16 AD19 DP05 DQ10 EH14 5F051 AA04 AA05 CA02 CA07 CA08 CA09 CA16 CA37 CA40 DA04 DA15

Claims (14)

[Claims] 1. A method for producing a crystalline SiC film, comprising: (a) housing a substrate facing a discharge electrode in a container;
The inside of the container is evacuated, and (b) the source gas containing at least an organic silane, a diluent gas and a dopant-containing gas and having a C / Si supply ratio in the range of 1.5 to 3.0 is evacuated. (C) applying high frequency power of 60 to 200 MHz to the discharge electrode to generate plasma between the discharge electrode and the substrate, and reacting radicals in the plasma on the surface of the substrate, A method for producing a crystalline SiC film, which comprises depositing a film containing crystalline SiC on a substrate. 2. In the step (b), the organic silane is monomethylsilane (CH ₃ SiH ₃ ), dimethylsilane ((CH ₃ ) ₂ SiH ₂ ), trimethylsilane ((C
H ₃ ) ₃ SiH) and tetramethylsilane ((CH ₃ ) ₄ S
The method according to claim 1, which comprises one or more gases selected from the group i). 3. In the step (b), a pure hydrogen gas or a mixed gas of 30 mol% or less argon and hydrogen is used as a diluent gas, and a dilution ratio ((H ₂ + Ar gas) number of molecules /
2. The method according to claim 1, wherein (Si + C) number of atoms is in the range of 50 to 300. 4. The method according to claim 1, wherein in the step (c), the temperature of the substrate is controlled within a range of 100 to 300 ° C. 5. As a conductive semiconductor layer of a thin film silicon solar cell, p-type crystalline SiC is prepared by adding diborane (B ₂ H ₆ ) as a doping gas in the step (b).
The method of claim 1, wherein the film is deposited on a substrate. 6. The method according to claim 5, wherein the film thickness is controlled in the range of 10 to 200 nm. 7. A crystalline SiC film formed by the method of claim 1. 8. A crystalline SiC film formed by the method according to claim 2. 9. A crystalline SiC film formed by the method of claim 3. 10. A crystalline SiC film formed by the method of claim 4. 11. A crystalline SiC film used for a conductive semiconductor layer of a thin-film silicon solar cell, which is formed by the method according to claim 5. 12. The crystalline SiC film according to claim 11, which is doped with boron of 10 ¹⁸ to 10 ²¹ atoms / cm ³ . 13. A light-transmissive substrate, a transparent electrode film formed on the substrate, and a C / Si supply ratio formed on the transparent electrode film, containing at least organic silane, a diluent gas and a doping gas. To a range of 1.5 to 3.0 is introduced into the vacuum-evacuated container, and a frequency of 60 to 2 is applied to the discharge electrode.
A p-type crystalline SiC film formed on the substrate by applying a high frequency power of 00 MHz to generate plasma between the discharge electrode and the substrate and reacting radicals in the plasma on the surface of the substrate, Substantially intrinsic i-type silicon film formed on the p-type crystalline SiC film, n-type silicon film formed on the i-type silicon film, and formed on the n-type silicon film And a method of manufacturing the same. 14. At least one solar cell according to claim 13.
A tandem-type photoelectric conversion element characterized by including a set.