JP2006140339A - Silicon-based thin film photoelectric conversion device and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amorphous silicon-based thin film photoelectric conversion device and its manufacturing method, having excellent performance after its optical deterioration when forming a photoelectric conversion layer using a plasma CVD process. <P>SOLUTION: The silicon-based thin film photoelectric conversion apparatus is an amorphous silicon-based photoelectric conversion device composed of, in order from a light incidence side, a transparent conductive oxide layer, a p-type semiconductor layer, a photoelectric conversion initial layer, a photoelectric conversion layer, and an n-type semiconductor layer. Contents of hydrogen atoms in the p-type semiconductor layer, the photoelectric conversion initial layer, and the photoelectric conversion layer are increased in order. The apparatus is manufactured under the conditions that source gas is diluted with dilution gas to a degree where the photoelectric conversion initial layer is prevented from being crystallized. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an amorphous silicon-based thin film photoelectric conversion device and a method for manufacturing the same, and more particularly to improvement in performance of a silicon-based thin film photoelectric conversion device including an amorphous silicon-based photoelectric conversion layer. Note that the terms “crystalline” and “microcrystal” in the present specification include those that partially contain amorphous material.

  In recent years, in order to achieve both cost reduction and high efficiency of a photoelectric conversion device, a thin film photoelectric conversion device that has almost no problem in terms of resources has attracted attention and has been vigorously developed. Thin film photoelectric conversion devices are expected to be applied to various applications such as solar cells, optical sensors, and displays. An amorphous silicon photoelectric conversion device, which is one of thin film photoelectric conversion devices, can be formed on a large-area glass substrate or stainless steel substrate at a low temperature, so that cost reduction can be expected.

  An amorphous silicon-based photoelectric conversion device generally includes a first electrode of a transparent conductive oxide layer, one or more semiconductor thin film photoelectric conversion units, and a second electrode from the light incident side. One thin film photoelectric conversion unit includes an i-type photoelectric conversion layer sandwiched between a p-type semiconductor layer and an n-type semiconductor layer. Here, the photoelectric conversion unit or the thin film solar cell has an amorphous i-type photoelectric conversion layer that occupies the main part regardless of whether the p-type and n-type semiconductor layers contained therein are amorphous or crystalline. Are called amorphous photoelectric conversion units or amorphous thin-film solar cells.

  The p-type semiconductor layer and the n-type semiconductor layer play a role of generating a diffusion potential in the photoelectric conversion unit, and the value of the open end voltage, which is an important characteristic of the photoelectric conversion device, is influenced by the magnitude of the diffusion potential. . In an amorphous silicon-based photoelectric conversion device, p-type layer formation using a high-frequency plasma CVD method is performed to reduce the optical absorption loss in the p-type layer by expanding the optical forbidden band width of the p-type semiconductor layer. In general, amorphous silicon carbide is obtained by using a hydrocarbon gas such as methane or ethylene together with a doping gas such as silane gas, hydrogen gas, and diborane as a raw material gas. Further, a buffer layer is generally inserted between the p-type semiconductor layer and the photoelectric conversion layer in order to alleviate mismatch in the optical forbidden band width of the two layers. Then, substantially intrinsic amorphous silicon carbide is widely used for the buffer layer after the p-type semiconductor layer is formed, and the flow rate of the source gas is adjusted in the same reaction chamber after the p-type semiconductor layer is formed. It is formed by doing.

  In an amorphous silicon-based thin film solar cell using i-type amorphous silicon as a photoelectric conversion layer, a photodegradation phenomenon called the Stebleronsky effect occurs in which the photoelectric conversion efficiency of the solar cell is reduced by light irradiation. The cause of the occurrence of the Stebleronsky effect has not yet been clarified, but this photodegradation phenomenon is greatly affected by the characteristics of the p-type semiconductor layer and the photoelectric conversion layer near the junction interface in addition to the film characteristics of the i-type photoelectric conversion layer. I know that For this reason, various attempts are made to improve the interface characteristics between the p-type semiconductor layer and the photoelectric conversion layer by devising the initial layer of the photoelectric conversion layer and the closest layer in contact with the photoelectric conversion layer among the p-type semiconductor layers. Consideration has been made.

  Non-Patent Document 1 discloses a so-called pin-type photoelectric conversion, which is a photoelectric conversion device formed in the order of p, i, and n-type semiconductor layers on a transparent substrate such as a glass substrate on which a photoelectric conversion layer is formed by chemical vapor deposition. In the manufacturing method of the device, when forming the photoelectric conversion layer, after forming the photoelectric conversion layer under a condition where the growth rate is low in the initial film forming region near the interface located on the interface side with the p-type semiconductor layer, the growth rate A method of forming a photoelectric conversion layer by switching to a fast condition is described. According to this method, since the generation of defects in the photoelectric conversion layer in the region in contact with the p-type semiconductor layer can be suppressed, the photoelectric conversion characteristics are improved. However, the photoelectric conversion efficiency after light irradiation is 100 mW / cm 2 and remains at a value of 8% or less after 20 hours of light irradiation.

Patent Document 1 discloses a method for manufacturing a photoelectric conversion device in which a photoelectric conversion layer is formed by chemical vapor deposition, and a base semiconductor layer on which a photoelectric conversion layer is formed (in a pin type photoelectric conversion device, a p-type semiconductor layer is formed). A method of forming a photoelectric conversion layer after forming the hydrogen concentration in the film near the interface with the photoelectric conversion layer to be relatively lower than the hydrogen concentration in the bulk of the base semiconductor layer. Is described. According to this technique, a high concentration of hydrogen contained in the initial layer of the photoelectric conversion layer caused by the initial discharge of plasma CVD diffuses into the underlying semiconductor layer near the interface with a low hydrogen amount, thereby causing a certain amount of hydrogen. A density profile can be formed. That is, the manufacturing method described in Patent Document 1 is a technique based on the premise that the amount of hydrogen in the p-layer is larger than that of the photoelectric conversion layer, and the formation temperature of the p-layer described in the same document is 120. The amount of hydrogen in the film is as high as 21 atomic%. The p layer manufactured under such conditions has a low activation rate of boron, which is usually a dopant, and affects the output characteristics of the photoelectric conversion device. Therefore, the p-layer formation temperature is usually about 170 ° C. or higher in many cases. At such a formation temperature, the amount of hydrogen in the p layer is equal to or less than that of the photoelectric conversion layer.
REI Schropp, Solar Energy Materials and Solar Cells, Vol.34, pp455-463, 1994. JP 2002-270872 A

  In view of the problems as described above, the present invention provides a method for manufacturing an amorphous silicon thin film photoelectric conversion device having good performance after photodegradation when a photoelectric conversion layer is formed using a plasma CVD method. The purpose is that.

  The amorphous silicon-based photoelectric conversion device of the present invention includes a transparent conductive oxide layer, a p-type semiconductor layer, a photoelectric conversion initial layer, a photoelectric conversion layer, and an n-type semiconductor layer in order from the light incident side. An amorphous silicon photoelectric conversion device characterized in that a hydrogen atom content in a p-type semiconductor layer, the photoelectric conversion initial layer, and the photoelectric conversion layer satisfies the following relationship (formula 1): The layer is formed so that the dopant is sufficiently activated, and as a result, even when the amount of hydrogen in the p layer is equal to or less than that of the photoelectric conversion layer, photodegradation is suppressed.

Moreover, the manufacturing method of the amorphous silicon-type photoelectric conversion device of the present invention includes a transparent conductive oxide layer, a p-type semiconductor layer, a photoelectric conversion initial layer, a photoelectric conversion layer, and an n-type semiconductor layer in order from the light incident side. A method for manufacturing an amorphous silicon photoelectric conversion device formed, wherein the p-type semiconductor layer is formed in a reaction chamber different from the photoelectric conversion initial layer and the photoelectric conversion layer, and the photoelectric conversion initial stage And at least part of the photoelectric conversion layer is formed in the same reaction chamber, and the photoelectric conversion initial layer is formed under the condition that the silicon-based source gas is diluted with a diluent gas to such an extent that it does not crystallize. This is a method for manufacturing an amorphous silicon photoelectric conversion device. The light stability of the formed photoelectric conversion initial layer is improved by increasing the flow ratio of the diluent gas such as hydrogen to the silane-based gas at the time of preparing the photoelectric conversion initial layer. When the photoelectric conversion initial layer is crystallized, the optical band gap becomes smaller than the optical band gap of the p-type semiconductor layer and the photoelectric conversion layer, so that optical reflection loss and band gap mismatch occur. For this reason, it is necessary that the photoelectric conversion initial layer is not crystallized. Furthermore, the photoelectric conversion initial layer is formed in the same reaction chamber as that of at least a part of the photoelectric conversion layer, and a reaction chamber different from the reaction chamber for forming the p-type semiconductor layer is used. It is possible to suppress the amount of impurities such as doping elements that hinder the properties.

  In addition, the flow rate ratio of the dilution gas to the silane-based source gas used in the photoelectric conversion initial layer of the present invention is desirably in the range of 30 times or more and 100 times or less. By making such a manufacturing condition, the light stability of the photoelectric conversion initial layer which greatly affects the light stability of the entire photoelectric conversion device is improved, and as a result, the light stability of the amorphous silicon-based thin film photoelectric conversion device thus manufactured is improved. Improved characterization characteristics.

  ADVANTAGE OF THE INVENTION According to this invention, the amorphous silicon type photoelectric conversion element excellent in the initial characteristic and the characteristic after photodegradation, and its manufacturing method are provided.

  The present inventors formed the p layer at a formation temperature of about 170 ° C. or higher so that the dopant is sufficiently activated, and as a result, the hydrogen content in the p layer is equal to or less than that of the photoelectric conversion layer. Even in this case, in order to obtain an amorphous silicon-based photoelectric conversion device in which photodegradation is suppressed, the main species of the preferable amount of hydrogen in each layer film was studied, and the present invention was achieved. In other words, as long as the method disclosed in Patent Document 1 described above is used, the initial performance of the photoelectric conversion device and the performance after photodegradation are further improved when the amount of hydrogen in the p layer is equal to or less than that of the photoelectric conversion layer. Since it does not lead to doing so, the present invention has been made from the recognition that another method is necessary.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In each drawing of the present application, dimensional relationships such as thickness and length are appropriately changed for clarity and simplification of the drawings, and do not represent actual dimensional relationships. Moreover, in each figure, the same referential mark represents the same part or an equivalent part.

  FIG. 1 is a cross-sectional view of a photoelectric conversion device according to an example of an embodiment of the present invention. On the transparent substrate 1, a transparent conductive oxide layer 2, a p-type semiconductor layer 31, a substantially intrinsic photoelectric conversion initial layer 32, a photoelectric conversion layer 33, an n-type semiconductor layer 34, and a back electrode layer 4 are sequentially arranged. ing.

  A plate-like member or a sheet-like member made of glass, transparent resin or the like is used for the transparent substrate 1 used in a photoelectric conversion device of a type in which light enters from the substrate side. The transparent conductive oxide layer 2 is made of a conductive metal oxide such as tin oxide, and is preferably formed using a method such as CVD, sputtering, or vapor deposition. The transparent conductive oxide layer 2 desirably has the effect of increasing the scattering of incident light by having fine irregularities with a height difference of about 0.05 to 0.3 μm on the surface.

  A value called a haze ratio is used as an index representing the degree of unevenness of the transparent conductor. This is calculated by measuring the degree of light scattering using a light source of a specified light source, usually a C light source containing visible light. Of the embodiments of the present invention, the transparent conductive oxide layer preferably has a haze value of 7% or more, more preferably 15% or more.

  As the p-type semiconductor layer 31, for example, a p-type amorphous silicon thin film doped with 0.01 atomic% or more of boron, which is a conductivity determining impurity atom, can be used. However, these conditions for the p-type semiconductor layer 31 are not limited, and the impurity atom may be, for example, aluminum, or a layer of an alloy material such as amorphous silicon carbide or amorphous silicon germanium is used. May be.

  Next, a substantially intrinsic photoelectric conversion initial layer 32 is formed on the p-type semiconductor layer 31, and this photoelectric conversion initial layer is formed by plasma CVD, and at least the substantially intrinsic photoelectric conversion initial layer 32 and The p-type semiconductor layer 31 is produced in a different reaction chamber, and the substantially intrinsic photoelectric conversion initial layer 32 is formed in the same reaction chamber as that for producing the photoelectric conversion layer. In addition, as a film forming condition of the intrinsic photoelectric conversion initial layer, it is desirable that the flow rate ratio of the dilution gas to the silane-based gas is in a range of 30 times or more and 100 times or less.

  Further, the photoelectric conversion layer 33 is formed in the same reaction chamber as the CVD reaction chamber in which the substantially intrinsic photoelectric conversion initial layer 32 is formed. As the photoelectric conversion layer 33, a non-doped amorphous silicon thin film or a silicon-based thin film material having a weak p-type or weak n-type containing a minute impurity and sufficiently having photoelectric conversion efficiency can be used. The photoelectric conversion layer 33 is not limited to these materials, and a layer of an alloy material such as amorphous silicon carbide or amorphous silicon germanium may be used.

  As n-type semiconductor layer 34, for example, an n-type amorphous silicon thin film doped with 0.01 atomic% or more of phosphorus, which is a conductivity determining impurity atom, may be used. However, these conditions for the n-type semiconductor layer 34 are not limited, and a microcrystalline silicon thin film or a layer of an alloy material such as amorphous silicon carbide or amorphous silicon germanium may be used.

  As the back electrode layer 4, it is preferable to form at least one metal layer made of at least one material selected from Al, Ag, Au, Cu, Pt and Cr by sputtering or vapor deposition. Moreover, you may form the layer which consists of electroconductive oxides, such as ITO, SnO2, ZnO, between a photoelectric conversion unit and a back surface electrode (not shown).

  Hereinafter, amorphous silicon thin film solar cells as amorphous silicon thin film photoelectric conversion devices according to some embodiments of the present invention will be described together with solar cells according to comparative examples.

Example 1
Corresponding to the first embodiment described with reference to FIG. 1, an amorphous silicon solar cell as Example 1 was fabricated. Glass was used for the substrate 1, and SnO 2 formed by a thermal CVD method was used for the transparent conductive oxide layer 2. The film thickness of the transparent conductive oxide layer 2 at this time was 800 nm, the sheet resistance was 10 ohm / □, and the haze ratio was 15 to 20%. On top of this, plasma CVD is performed with a boron-doped p-type silicon carbide (SiC) layer 31 having a thickness of 10 nm, a non-doped amorphous silicon photoelectric conversion layer 33 having a thickness of 250 nm, and a phosphorus-doped n-type microcrystalline silicon layer 34 having a thickness of 20 nm. The film was formed by the method. Thereby, an amorphous silicon photoelectric conversion unit having a pin junction was formed. Further, as the back electrode layer 4, a ZnO film having a thickness of 80 nm and an Ag film having a thickness of 300 nm were formed by sputtering.

  The p-type silicon carbide layer 31 was deposited by a parallel plate type high-frequency plasma CVD method. Regarding the film forming conditions at that time, the plasma excitation frequency was 27.12 MHz, the substrate temperature was 190 ° C., and the pressure in the reaction chamber was 3 Torr. Silane, methane, diborane, and hydrogen are used as source gases introduced into the plasma CVD reaction chamber, and the flow ratio of these gases is 1.6 for methane and 0.01 for diborane relative to silane 1. , Hydrogen was set to 38. After depositing a 10 nm film under the above conditions, the gas supply of diborane and methane was stopped without turning off the discharge as it was, and a 10 nm film was continuously deposited by setting the gas flow rate ratio of hydrogen to silane to 80.

  Then, a substantially intrinsic photoelectric conversion initial layer 32 was formed on the p-type silicon carbide layer 31 by a parallel plate high-frequency plasma CVD method using a reaction chamber different from that of the p-type silicon carbide layer. The film-forming conditions at that time were such that the plasma excitation frequency was 27.12 MHz, the substrate temperature was 215 ° C., and the reaction chamber pressure was 3 Torr. Silane, which is a silicon-based source gas, and hydrogen, which is a diluent gas, are used as source gases introduced into the plasma CVD reaction chamber, and the flow rate ratio of these gases (diluted gas / silicon-based source gas) 50, that is, silane 1 Hydrogen was set to 80. After the intrinsic photoelectric conversion initial layer 32 is formed in this manner, the photoelectric conversion layer 33 is formed by plasma CVD using the same reaction chamber as the intrinsic photoelectric conversion initial layer 32 is formed. .

The output characteristics when such an amorphous silicon solar cell of Example 1 is irradiated with AM 1.5 light as incident light at a light illuminance of 100 mW / cm 2 have an open-circuit voltage of 0.905 V and a short-circuit current density of 15. 0.8 mA / cm2, the fill factor was 74.5%, and the conversion efficiency was 10.7%. In addition, after the solar cell produced in Example 1 was irradiated with light having an illuminance of 500 mW / cm ² at a solar cell temperature of 50 ° C. for 20 hours, the amorphous silicon solar cell was photodegraded. , output characteristics of light measured with light intensity of 100 mW / cm @ 2 of AM1.5 has an open end voltage is 0.866V, a short circuit current density of 15.0 mA / cm ^2, a fill factor is 64.2% and a conversion efficiency 8 34%.

When the hydrogen profile in the solar cell produced in Example 1 was measured at a plurality of locations by SIMS from the back electrode layer 4 side, the hydrogen amount was from the photoelectric conversion layer 33 to the p-type silicon carbide layer 31 side by the p-type silicon carbide layer 31 side. The measured value was slightly decreased toward 5.5, and the measured value was 5.5 × 10 ²¹ atoms cm ^{−3 to} 5.0 × 10 ²¹ atoms cm ⁻³ (corresponding to 11 to 10 atom%). Moreover, when the cross-section TEM of the solar cell produced in Example 1 was image | photographed, it was confirmed that the photoelectric conversion initial layer 32 is not crystallized, as shown in FIG.

(Comparative Example 1)
Similarly, an amorphous silicon solar cell having the configuration shown in FIG. 1 was produced. Only the formation of the substantially intrinsic photoelectric conversion initial layer 32 was omitted, and the other film forming conditions were the same as those in Example 1.

In the output characteristics when the amorphous silicon solar cell of Example 1 is irradiated with AM 1.5 light as incident light at a light illuminance of 100 mW / cm 2, the open-circuit voltage is 0.906 V, and the short-circuit current density is It was 15.8 mA / cm2, the fill factor was 74.5%, and the conversion efficiency was 10.7%. In addition, after the solar cell produced in Example 1 was irradiated with light having an illuminance of 500 mW / cm ² at a solar cell temperature of 50 ° C. for 20 hours, the amorphous silicon solar cell was photodegraded. The output characteristics of AM 1.5 light measured at 100 mW / cm 2 are as follows. The open circuit voltage is 0.868V, the short-circuit current density is 15.1 mA / cm ² , the fill factor is 62.3%, and the conversion efficiency is 8 15%.

(Comparative Example 2)
Similarly, an amorphous silicon solar cell having the configuration shown in FIG. 1 was produced. Except for the film forming conditions of the substantially intrinsic photoelectric conversion initial layer 32, it was exactly the same as Example 1.

  The film formation conditions of the substantially intrinsic photoelectric conversion initial layer 32 are as follows: the plasma excitation frequency is 27.12 MHz, the substrate temperature is 215 ° C., the distance between the substrate electrodes is 0.8 times that of Example 1, and the pressure in the reaction chamber is 3 Torr. Formed as. Silane and hydrogen were used as source gases introduced into the plasma CVD reaction chamber, and the flow rate ratio of these gases was set to 80 for silane 1 and hydrogen. By shortening the distance between the substrate electrodes, a part of the semiconductor layer manufactured under such conditions is crystallized into a microcrystalline state. After the intrinsic photoelectric conversion initial layer 32 is formed in this manner, the photoelectric conversion layer 33 is formed by plasma CVD using the same reaction chamber as the intrinsic photoelectric conversion initial layer 32 is formed. .

In the output characteristics when the amorphous silicon solar cell of Example 1 is irradiated with AM 1.5 light as incident light at a light illuminance of 100 mW / cm 2, the open-circuit voltage is 0.904 V and the short-circuit current density is It was 15.7 mA / cm2, the fill factor was 72.9%, and the conversion efficiency was 10.4%. In addition, after the solar cell produced in Example 1 was irradiated with light having an illuminance of 500 mW / cm ² at a solar cell temperature of 50 ° C. for 20 hours, the amorphous silicon solar cell was photodegraded. , output characteristics of light measured with light intensity of 100 mW / cm @ 2 of AM1.5 has an open end voltage is 0.864V, a short circuit current density of 14.6mA / cm ^2, a fill factor is 63.9% the conversion efficiency 8 0.08%, and the short-circuit current of the solar cell produced in comparison with the result of Example 1 was lowered particularly in the result after photodegradation, and the characteristics were deteriorated.

(Examples 2 and 3 and Comparative Example 3)
Corresponding to the first embodiment described with reference to FIG. 1, the flow rate ratio of the dilution gas to the raw material gas is changed as the formation condition of the substantially intrinsic photoelectric conversion initial layer 32. An amorphous silicon solar cell was produced by the same method as in Example 1 or Comparative Example 2. As film forming conditions, the substrate temperature is 190 ° C., the pressure in the reaction chamber is 3 Torr, and the photoelectric conversion for each value of the flow rate ratio of the dilution gas to the source gas introduced into the reaction chamber when the substantially intrinsic photoelectric conversion initial layer 32 is formed. The results of comparing the characteristics are shown in Tables 1 and 2. The table also shows the results of Example 1 and Comparative Examples 1 and 2. Table 1 shows the output characteristics when the manufactured amorphous silicon solar cell was irradiated with AM1.5 light at a light illuminance of 100 mW / cm 2. Table 2 shows the output characteristics of this amorphous silicon solar cell. after allowed to photodegradation by the light of the solar cell temperature based at illuminance of 500 mW / cm ² in 50 ° C. irradiation 20 h, shows the output characteristic of the light of AM1.5 measured with light intensity of 100 mW / cm @ 2 .

From the above results, the film formation conditions for the substantially intrinsic semiconductor layer include an optimum flow ratio of the dilution gas to the source gas in order to improve the characteristics of the amorphous silicon solar cell after photodegradation. I understood.

(Examples 4 and 5 and Comparative Examples 4 and 5)
Moreover, what changed only the film thickness of the photoelectric converting layer 33 of the amorphous silicon solar cell of Example 1 from 250 nm to 300 nm and 330 nm is set to Examples 4 and 5, and the film thickness of the photoelectric converting layer 33 of the comparative example 1 is shown. Comparative Examples 4 and 5 were obtained by changing only the thickness from 250 nm to 300 nm and 330 nm. Tables 3 and 4 show the results of comparing the photoelectric conversion characteristics of the examples and comparative examples. Table 3 shows the output characteristics when the manufactured amorphous silicon solar cell is irradiated with AM 1.5 light at a light illuminance of 100 mW / cm 2. Table 4 shows the output characteristics of the amorphous silicon solar cell. after allowed to photodegradation by the light of the solar cell temperature based at illuminance of 500 mW / cm ² in 50 ° C. irradiation 20 h, shows the output characteristic of the light of AM1.5 measured with light intensity of 100 mW / cm @ 2 .

1 is a structural cross-sectional view of a photoelectric conversion device according to an embodiment of the present invention. The cross-sectional TEM image of the photoelectric conversion apparatus produced in Example 1 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Transparent conductive oxide layer 31 P-type semiconductor layer 32 Photoelectric conversion initial layer 33 Photoelectric conversion layer 34 n-type semiconductor layer 4 Back surface electrode layer

Claims (3)

An amorphous silicon photoelectric conversion device in which a transparent conductive oxide layer, a p-type semiconductor layer, a photoelectric conversion initial layer, a photoelectric conversion layer, and an n-type semiconductor layer are formed in order from the light incident side,
The hydrogen atom content in the p-type semiconductor layer, the photoelectric conversion initial layer, and the photoelectric conversion layer is
An amorphous silicon photoelectric conversion device satisfying the following relationship (Formula 1):
  A method for manufacturing an amorphous silicon photoelectric conversion device in which a transparent conductive oxide layer, a p-type semiconductor layer, a photoelectric conversion initial layer, a photoelectric conversion layer, and an n-type semiconductor layer are formed in order from the light incident side. The p-type semiconductor layer is formed in a reaction chamber different from the photoelectric conversion initial layer and the photoelectric conversion layer, and at least a part of the photoelectric conversion initial layer and the photoelectric conversion layer is formed in the same reaction chamber. 2. The manufacturing method of an amorphous silicon photoelectric conversion device according to claim 1, wherein the photoelectric conversion initial layer is formed under a condition in which a silicon source gas is diluted with a diluent gas so as not to be crystallized. Method.   3. The amorphous silicon photoelectric conversion according to claim 2, wherein a flow rate ratio of a dilution gas to a silicon source gas at the time of forming the photoelectric conversion initial layer is in a range of 30 times or more and 100 times or less. Device manufacturing method.