WO2010023948A1

WO2010023948A1 - Photoelectric conversion device manufacturing method, photoelectric conversion device, and photoelectric conversion device manufacturing system

Info

Publication number: WO2010023948A1
Application number: PCT/JP2009/004232
Authority: WO
Inventors: 朝比奈伸一; 内田寛人; 浅利伸; 橋本征典; 藤長徹志; 小林忠正; 若井雅文; 今北健一; 植喜信; 斎藤一也; 中村久三
Original assignee: 株式会社アルバック
Priority date: 2008-08-29
Filing date: 2009-08-28
Publication date: 2010-03-04

Abstract

Disclosed is a photoelectric conversion device manufacturing method whereby a first p-type semiconductor layer (31), a first i-type semiconductor layer (32) and a first n-type semiconductor layer (33) which configure a first photoelectric conversion unit (3), and a second p-type semiconductor layer (41) which configures a second photoelectric conversion unit (4) are respectively formed consecutively in a different reduced-pressure chamber; the second p-type semiconductor layer (41) is exposed to the atmosphere; and a second i-type semiconductor layer (42) and a second n-type semiconductor layer (43) which configure the second photoelectric conversion unit are formed in the same reduced-pressure chamber on the p-type semiconductor layer (41) of the second photoelectric conversion unit (4) which has been exposed to the atmosphere.

Description

Photoelectric conversion device manufacturing method, photoelectric conversion device, and photoelectric conversion device manufacturing system

The present invention relates to a method for manufacturing a photoelectric conversion device, a photoelectric conversion device, and a system for manufacturing a photoelectric conversion device. More specifically, the performance of a tandem photoelectric conversion device in which two photoelectric conversion units are stacked is improved. It is related to the technology.
This application claims priority based on Japanese Patent Application No. 2008-222818 filed on August 29, 2008 and PCT / JP2009 / 057976 filed on April 22, 2009, the contents of which are incorporated herein by reference. Incorporate.

In recent years, photoelectric conversion devices are generally used for solar cells, optical sensors, and the like, and in particular, solar cells have begun to spread widely from the viewpoint of efficient use of energy. In particular, a photoelectric conversion device using single crystal silicon is excellent in energy conversion efficiency per unit area.
However, on the other hand, since a photoelectric conversion device using single crystal silicon uses a silicon wafer obtained by slicing a single crystal silicon ingot, a large amount of energy is consumed for manufacturing the ingot and the manufacturing cost is high.
For example, if a large-area photoelectric conversion device installed outdoors or the like is manufactured using a silicon single crystal, it is considerably expensive at present.
Thus, a photoelectric conversion device using an amorphous (amorphous) silicon thin film (hereinafter also referred to as “a-Si thin film”) that can be manufactured at a lower cost is widely used as a low-cost photoelectric conversion device.

However, the conversion efficiency of a photoelectric conversion device using this amorphous (amorphous) silicon thin film is lower than the conversion efficiency of a crystalline photoelectric conversion device using single crystal silicon or polycrystalline silicon.
Therefore, as a structure for improving the conversion efficiency of the photoelectric conversion device, a tandem structure in which two photoelectric conversion units are stacked has been proposed.
For example, a tandem photoelectric conversion device 100 as shown in FIG. 15 is known.
In this photoelectric conversion device 100, an insulating transparent substrate 101 provided with a transparent conductive film 102 is used.
A pin-type first photoelectric conversion unit obtained by sequentially stacking a p-type semiconductor layer 131, an i-type silicon layer (amorphous silicon layer) 132, and an n-type semiconductor layer 133 on the transparent conductive film 102. 103 is formed.
On the first photoelectric conversion unit 103, a p-type semiconductor layer 141, an i-type silicon layer (a crystalline silicon layer including microcrystals, hereinafter referred to as a crystalline silicon layer) 142, and an n-type semiconductor layer 143 are sequentially stacked. A pin-type second photoelectric conversion unit 104 obtained in this manner is formed.
Further, a back electrode 105 is formed on the second photoelectric conversion unit 104.

As a method for manufacturing such a tandem photoelectric conversion device, for example, a manufacturing method disclosed in Patent Document 1 is known.
In this manufacturing method, a p-type semiconductor layer, an i-type amorphous silicon-based photoelectric conversion layer, and an n-type semiconductor layer that form an amorphous photoelectric conversion unit (first photoelectric conversion unit) are formed. Each plasma CVD reaction chamber is different.
Moreover, in this manufacturing method, the p-type semiconductor layer, the i-type crystalline silicon-based photoelectric conversion layer, and the n-type semiconductor layer constituting the crystalline photoelectric conversion unit (second photoelectric conversion unit) are the same. It is formed in a plasma CVD reaction chamber.

In the tandem photoelectric conversion device 100, as shown in FIG. 16A, first, an insulating transparent substrate 101 on which a transparent conductive film 102 is formed is prepared.
Next, as shown in FIG. 16B, a p-type semiconductor layer 131, an i-type silicon layer (amorphous silicon layer) 132, and an n-type are formed on the transparent conductive film 102 formed on the insulating transparent substrate 101. The plasma CVD reaction chamber in which the semiconductor layer 133 is formed is different.
As a result, the pin-type first photoelectric conversion units 103 sequentially stacked are formed on the insulating transparent substrate 101.
Subsequently, after the n-type semiconductor layer 133 of the first photoelectric conversion unit 103 is exposed to the atmosphere and moved to the plasma CVD reaction chamber, as shown in FIG. 16C, the first photoelectric conversion unit 103 exposed to the atmosphere is exposed. A p-type semiconductor layer 141, an i-type silicon layer (crystalline silicon layer) 142, and an n-type semiconductor layer 143 are formed over the n-type semiconductor layer 133 in the same plasma CVD reaction chamber.
As a result, pin-type second photoelectric conversion units 104 that are sequentially stacked are formed.
Then, by forming the back electrode 105 on the n-type semiconductor layer 143 of the second photoelectric conversion unit 104, the photoelectric conversion device 100 as shown in FIG. 15 is obtained.

The tandem photoelectric conversion device 100 having the above configuration can be broadly manufactured by the following two manufacturing systems.
First, in the first manufacturing system, first, the first photoelectric conversion is performed by using a so-called in-line type first film forming apparatus in which a plurality of film forming reaction chambers called chambers are arranged linearly (linearly). Unit 103 is formed.
Each layer constituting the first photoelectric conversion unit 103 is formed in a different film formation reaction chamber in the first film formation apparatus.
After the first photoelectric conversion unit 103 is formed, the second photoelectric conversion unit 104 is formed using a so-called batch-type second film forming apparatus.
Each layer constituting the second photoelectric conversion unit 104 is formed in one film forming reaction chamber in the second film forming apparatus.
Specifically, for example, as shown in FIG. 17, the first manufacturing system includes a load chamber (L) 161, a p-layer deposition reaction chamber 162, an i-layer deposition reaction chamber 163, and an n-layer deposition reaction. A first deposition apparatus in which a chamber 164 and an unload chamber (UL) 166 are continuously arranged in a straight line, a load / unload chamber (L / UL) 171 and a pin layer deposition reaction chamber 172. And a second film forming apparatus arranged.
In this first manufacturing system, first, a substrate is carried into and placed in a load chamber (L: Lord) 161, and the internal pressure is reduced.
Subsequently, while maintaining the reduced pressure atmosphere, the p-type semiconductor layer 131 of the first photoelectric conversion unit 103 is formed in the p-layer film formation reaction chamber 162, and the i-type silicon layer (amorphous) in the i-layer film formation reaction chamber 163. Silicon layer) 132 is formed, and an n-type semiconductor layer 133 is formed in the n-layer deposition reaction chamber 164.
The substrate on which the first photoelectric conversion unit 103 is formed is carried out to an unload chamber (UL) 166. In the unload chamber (UL) 166, the reduced-pressure atmosphere is returned to the air atmosphere, and the substrate is unloaded from the unload chamber (UL).
Thus, the substrate processed in the first film forming apparatus is exposed to the atmosphere and transferred to the second film forming apparatus.
The substrate on which the first photoelectric conversion unit 103 is formed is loaded into and placed in a load / unload chamber (L / UL) 171 and the pressure inside thereof is reduced.
The load / unload chamber (L / UL) 171 reduces the internal pressure after the substrate is loaded, or returns the reduced pressure atmosphere to the air atmosphere when the substrate is unloaded.
The substrate is carried into the pin layer film formation reaction chamber 172 via the load / unload chamber (L / UL) 171. On the n-type semiconductor layer 133 of the first photoelectric conversion unit 103, the p-type semiconductor layer 141, the i-type silicon layer (crystalline silicon layer) 142, and the n-type semiconductor layer 143 of the second photoelectric conversion unit 104 have the same reaction. The layers are sequentially formed in the chamber, that is, in the pin layer deposition reaction chamber 172.

At point G shown in FIG. 17 of the first manufacturing system, an insulating transparent substrate 101 on which a transparent conductive film 102 is formed is prepared as shown in FIG. 16A.
In addition, at the point H shown in FIG. 17, as shown in FIG. 16B, the photoelectric conversion device in which the first photoelectric conversion unit 103 is provided on the transparent conductive film 102 formed on the insulating transparent substrate 101. The first intermediate product 100a is formed.
Then, at the point I shown in FIG. 17, as shown in FIG. 16C, the second intermediate product 100 b of the photoelectric conversion device provided with the second photoelectric conversion unit 104 is formed on the first photoelectric conversion unit 103.
In FIG. 17, the in-line type first film forming apparatus is configured to process two substrates simultaneously. The i-layer film formation reaction chamber 163 includes four reaction chambers 163a to 163d.
In FIG. 17, the batch-type second film forming apparatus is configured to process six substrates simultaneously.

On the other hand, in the second manufacturing system, the first photoelectric conversion unit 103 is formed using the same first film forming apparatus shown in FIG.
After the first photoelectric conversion unit 103 is formed, a second photoelectric conversion unit 104 is formed using a plurality of dedicated film formation reaction chambers for forming each layer of the second photoelectric conversion unit 104. The second photoelectric conversion unit 104 is formed using the second film forming apparatus.
Specifically, for example, as shown in FIG. 18, the second manufacturing system includes a first film forming apparatus having the same configuration as that in FIG. 17, a load / unload chamber (L / UL) 173, and a p-layer formation. A film deposition chamber 174, an i-layer deposition reaction chamber 175, an n-layer deposition reaction chamber 176, and a second deposition apparatus in which an intermediate chamber 177 is disposed.
In the second manufacturing system, as described above, the first photoelectric conversion unit 103 is formed on the substrate by the first film forming apparatus as in the first manufacturing system, and the substrate is unloaded from the unload chamber (UL). : Unknown) 166.
Thus, the substrate processed in the first film forming apparatus is exposed to the atmosphere and transferred to the second film forming apparatus.
The substrate on which the first photoelectric conversion unit 103 is formed is carried into and placed in a load / unload chamber (L / UL) 173, and the internal pressure is reduced.
The load / unload chamber (L / UL) 173 reduces the internal pressure after the substrate is loaded, or returns the reduced pressure atmosphere to the air atmosphere when the substrate is unloaded.
The substrate is carried into the intermediate chamber 177 through the load / unload chamber (L / UL) 173. Further, the intermediate chamber 177 and the p-layer deposition reaction chamber 174 are transported, the intermediate chamber 177 and the i-layer deposition reaction chamber 175, and the intermediate chamber 177 and the n-layer deposition reaction chamber 176. .
In the p-layer deposition reaction chamber 174, the p-type semiconductor layer 141 of the second photoelectric conversion unit 104 is formed on the n-type semiconductor layer 133 of the first photoelectric conversion unit 103.
In the i-layer deposition reaction chamber 175, an i-type silicon layer (crystalline silicon layer) 142 is formed.
In the n-layer deposition reaction chamber 176, an n-type semiconductor layer 143 is formed.
Thus, in each of the

reaction chambers

174, 175, and 176, one of the p-type semiconductor layer 141, the i-type silicon layer 142, and the n-type semiconductor layer 143 is formed on one substrate.
In addition, a transfer device (not shown) provided in the intermediate chamber 177 is provided for each of the

reaction chambers

174, 175, and 176 in order to stack the p-type semiconductor layer 141, the i-type silicon layer 142, and the n-type semiconductor layer 143. The substrate is transported to the substrate, and the substrate is unloaded from each of the

reaction chambers

174, 175, and 176.

At a point J shown in FIG. 18 of the second manufacturing system, an insulating transparent substrate 101 on which a transparent conductive film 102 is formed is prepared as shown in FIG. 16A.
Further, at the point K shown in FIG. 18, as shown in FIG. 16B, the photoelectric conversion device in which the first photoelectric conversion unit 103 is provided on the transparent conductive film 102 formed on the insulating transparent substrate 101. The first intermediate product 100a is formed.
Then, at the point L shown in FIG. 18, as shown in FIG. 16C, the second intermediate product 100 b of the photoelectric conversion device provided with the second photoelectric conversion unit 104 is formed on the first photoelectric conversion unit 103.
In FIG. 18, the in-line type first film forming apparatus is configured to simultaneously process two substrates in each reaction chamber. The i-layer film formation reaction chamber 163 includes four reaction chambers 163a to 163d.
In FIG. 18, the i-layer film formation reaction chamber 175 in the single-wafer-type second film formation apparatus includes five reaction chambers 175a to 175e. Therefore, the second film forming apparatus shortens the tact time by simultaneously forming i layers having a long film forming time on five substrates.
FIG. 18 shows an example in which each of the p layer, the i layer, and the n layer is formed in the individual chambers 173 to 176. However, in each of the individual chambers 173 to 176, the p layer, You may employ | adopt the system which forms into a film the i layer and n layer continuously.
In the single wafer type film forming apparatus, the installation area becomes large, and the number of i-layer film forming reaction chambers may not be increased. In this case, the number of i-layer deposition reaction chambers can be substantially increased by depositing the p, i, and n layers in each reaction chamber.

In such a manufacturing method, the i layer, which is an amorphous photoelectric conversion layer, has a film thickness of 2000 to 3000 mm and can be produced in a dedicated reaction chamber. In addition, since a dedicated reaction chamber is used for each of the p, i, and n layers, diffusion of the p layer impurities into the i layer or residual impurities are prevented from being disturbed due to contamination of the p and n layers. A good impurity profile can be obtained in the pin junction structure.
On the other hand, the i-layer, which is a crystalline photoelectric conversion layer, has a thickness of 15000 to 25000 mm, which is one digit larger than that of an amorphous photoelectric conversion layer. Alternatively, it is advantageous to process a plurality of substrates side by side in a single-wafer reaction chamber.

However, when the p, i, n layers of the crystalline photoelectric conversion layer are formed in the same reaction chamber, the p-type impurities are diffused into the i-layer or the residual impurity p is processed in the same reaction chamber. The problem is that the disorder of the junction is caused by mixing into the n layer.
The entry of residual impurities into the p and n layers means that both impurities in the p layer (dopant) gas and n layer impurity (dopant) gas are used in the same chamber. This means that the impurity (dopant) gas component is mixed into the other layer.
For example, when an n layer is formed on a substrate and then a p layer is formed on the next substrate in the same chamber, impurities in the n layer may remain and be mixed into the p layer of the next substrate.

Japanese Patent No. 3589581

The present invention has been made in view of the above circumstances, and a pin-type first photoelectric conversion unit and a second photoelectric conversion unit are sequentially laminated on an insulating transparent substrate with a transparent conductive film, and at least a second photoelectric conversion unit is provided. In a photoelectric conversion device in which an i layer includes a crystalline silicon-based thin film, diffusion of an n layer impurity into the p layer constituting the second photoelectric conversion unit, excessive diffusion of the p layer impurity into the i layer, second Manufacture of a photoelectric conversion device having good power generation performance without any disturbance of junction caused by diffusion of n-layer impurities into the i-layer constituting the photoelectric conversion unit or mixing of n-layer residual impurities into the pi junction surface The primary purpose is to provide a method.
Moreover, this invention makes it the 2nd objective to provide the photoelectric conversion apparatus which has favorable electric power generation performance.
Furthermore, diffusion of n layer impurities into the p layer constituting the second photoelectric conversion unit, excessive diffusion of p layer impurities into the i layer, diffusion of n layer impurities into the i layer constituting the second photoelectric conversion unit, Alternatively, a third object is to provide a manufacturing system capable of producing a photoelectric conversion device having good power generation performance without causing disorder of the junction due to mixing of n-layer residual impurities into the pi junction surface.

The manufacturing method of the photoelectric conversion device according to the first aspect of the present invention includes a first p-type semiconductor layer, a first i-type semiconductor layer, and a first n-type semiconductor layer constituting the first photoelectric conversion unit, The second p-type semiconductor layer constituting the two-photoelectric conversion unit is continuously formed in different decompression chambers, and the second p-type semiconductor layer is exposed to an air atmosphere (air atmosphere). A second i-type semiconductor layer and a second n-type semiconductor layer constituting the second photoelectric conversion unit are formed in the same decompression chamber on the exposed second p-type semiconductor layer.

In the method for manufacturing a photoelectric conversion device according to the first aspect of the present invention, before forming the second i-type semiconductor layer, the second p-type semiconductor layer exposed to the air atmosphere contains hydrogen radicals. Exposure to plasma is preferred.

In the method for manufacturing a photoelectric conversion device according to the first aspect of the present invention, it is preferable to use hydrogen gas when the second p-type semiconductor layer is exposed to the plasma containing the hydrogen radicals.

In the method for manufacturing a photoelectric conversion device according to the first aspect of the present invention, before forming the second i-type semiconductor layer, in an atmosphere in which a dopant gas mixed into the second p-type semiconductor layer is present, It is preferable to expose the second p-type semiconductor layer to plasma containing hydrogen radicals.

In the method for manufacturing a photoelectric conversion device according to the first aspect of the present invention, it is preferable to form a crystalline silicon-based thin film as the first n-type semiconductor layer.

In the method for manufacturing a photoelectric conversion device according to the first aspect of the present invention, the third p-type semiconductor layer may be formed after the second i-type semiconductor layer and the second n-type semiconductor layer are formed. preferable.

The photoelectric conversion device according to the second aspect of the present invention is formed by the above-described method for manufacturing a photoelectric conversion device.

The manufacturing system of the photoelectric conversion device according to the third aspect of the present invention includes a first p-type semiconductor layer, a first i-type semiconductor layer, a first n-type semiconductor layer, and a first photoelectric conversion unit. A first film forming apparatus including a plurality of plasma CVD reaction chambers formed to form a second p-type semiconductor layer constituting each of the two photoelectric conversion units and connected to maintain a reduced pressure atmosphere; An unloading device for unloading the substrate on which the semiconductor layer is formed into an air atmosphere (air atmosphere); and a second i-type that houses the substrate unloaded in the air atmosphere and constitutes the second photoelectric conversion unit And a second film forming apparatus including a plasma CVD reaction chamber for forming the semiconductor layer and the second n-type semiconductor layer in a reduced pressure atmosphere.

In the system for manufacturing a photoelectric conversion device according to the third aspect of the present invention, the second film-forming device may be configured such that the second p exposed to the air atmosphere before forming the second i-type semiconductor layer. It is preferable to expose the type semiconductor layer to plasma containing hydrogen radicals.

In the photoelectric conversion device manufacturing system according to the third aspect of the present invention, the second film forming apparatus has a gas introduction part for introducing hydrogen gas, and uses the hydrogen gas introduced by the gas introduction part. The second p-type semiconductor layer is preferably exposed to the plasma containing the hydrogen radical.

In the system for manufacturing a photoelectric conversion device according to the third aspect of the present invention, the second p-type semiconductor is formed in the plasma CVD reaction chamber for forming the second i-type semiconductor layer and the second n-type semiconductor layer. The layer is preferably exposed to the plasma containing the hydrogen radicals.

In the manufacturing system of the photoelectric conversion device of the third aspect of the present invention, before forming the second i-type semiconductor layer, in an atmosphere in which a dopant gas mixed into the second p-type semiconductor layer is present, It is preferable to expose the second p-type semiconductor layer to plasma containing hydrogen radicals.

In the photoelectric conversion device manufacturing system according to the third aspect of the present invention, the first film forming device preferably forms a crystalline silicon-based thin film as the first n-type semiconductor layer.

In the photoelectric conversion device manufacturing system according to the third aspect of the present invention, the third p-type semiconductor layer may be formed after the second i-type semiconductor layer and the second n-type semiconductor layer are formed. preferable.

According to the method for manufacturing a photoelectric conversion device of the present invention, the first p-type semiconductor layer, the first i-type semiconductor layer, the first n-type semiconductor layer, or the second photoelectric conversion unit of the first photoelectric conversion unit. Since the plasma CVD reaction chamber in which the second i-type semiconductor layer is formed is different from the plasma CVD reaction chamber in which the second p-type semiconductor layer of the second photoelectric conversion unit is formed, the second photoelectric conversion unit is configured. The diffusion of the n-type impurity into the second p-type semiconductor layer and the excessive diffusion of the p-type impurity into the second i-type semiconductor layer can be suppressed. Further, since the second i-type semiconductor layer is not formed immediately after the second p-type semiconductor layer is formed, the pi junction can be easily controlled.
Further, when the p-type semiconductor layer of the second photoelectric conversion unit is exposed to the air atmosphere, OH is attached to the surface of the p-type semiconductor layer, or a part of the surface of the p-layer is oxidized, so that crystal nuclei are formed. This increases the crystallization rate of the i-type semiconductor layer of the second photoelectric conversion unit made of a crystalline silicon-based thin film.

Further, according to the photoelectric conversion device of the present invention, since it is formed by the method for manufacturing the photoelectric conversion device, a good impurity profile can be obtained in the pin junction structure. Accordingly, there is no disorder in bonding, and good performance as a thin film photoelectric conversion device can be obtained.

Further, according to the photoelectric conversion device manufacturing system of the present invention, the first p-type semiconductor layer, the first i-type semiconductor layer, the first n-type semiconductor layer, and the second photoelectric conversion unit of the first photoelectric conversion unit. The second p-type semiconductor layer of the conversion unit is formed by the first film formation apparatus, and the second i-type semiconductor layer and the second n-type semiconductor layer of the second photoelectric conversion unit are the second component. The film is formed by a film apparatus. Thereby, it is possible to suppress the diffusion of the n-type impurity into the second p-type semiconductor layer constituting the second photoelectric conversion unit and the excessive diffusion of the p-type impurity into the second i-type semiconductor layer. Further, since the second i-type semiconductor layer is not formed immediately after the second p-type semiconductor layer is formed, the pi junction can be easily controlled. Accordingly, a photoelectric conversion device having good performance can be manufactured.

Sectional drawing explaining the manufacturing method of the photoelectric conversion apparatus which concerns on this invention. Sectional drawing explaining the manufacturing method of the photoelectric conversion apparatus which concerns on this invention. Sectional drawing explaining the manufacturing method of the photoelectric conversion apparatus which concerns on this invention. Sectional drawing which shows an example of the laminated constitution of the photoelectric conversion apparatus which concerns on this invention. Schematic which shows the 1st manufacturing system which manufactures the photoelectric conversion apparatus which concerns on this invention. Schematic which shows the 2nd manufacturing system which manufactures the photoelectric conversion apparatus which concerns on this invention. The figure which shows the relationship between a current density and a voltage about the photoelectric conversion apparatus of Experimental example 1-Experimental example 6. FIG. The figure which shows the relationship between the atmospheric exposure time of a p layer, and photoelectric conversion efficiency about the photoelectric conversion apparatus of Experimental example 1-Experimental example 6. FIG. The figure which shows the relationship between the atmospheric exposure time of p layer, and a short circuit current about the photoelectric conversion apparatus of Experimental example 1-Experimental example 6. FIG. The figure which shows the relationship between the atmospheric exposure time of p layer, and the open circuit voltage about the photoelectric conversion apparatus of Experimental example 1-Experimental example 6. FIG. The figure which shows the relationship between the atmospheric exposure time of a p layer, and a curve factor about the photoelectric conversion apparatus of Experimental example 1-Experimental example 6. FIG. FIG. 10 is a graph showing the relationship between current density and voltage for the photoelectric conversion devices of Experimental Examples 7 to 11. The figure which shows the relationship between the atmospheric exposure time of a p layer, and photoelectric conversion efficiency about the photoelectric conversion apparatus of Experimental example 7-Experimental example 11. FIG. The figure which shows the relationship between the atmospheric exposure time of p layer, and a short circuit current about the photoelectric conversion apparatus of Experimental example 7-Experimental example 11. FIG. The figure which shows the relationship between the atmospheric exposure time of p layer, and the open circuit voltage about the photoelectric conversion apparatus of Experimental example 7-Experimental example 11. FIG. The figure which shows the relationship between the atmospheric exposure time of a p layer, and a curve factor about the photoelectric conversion apparatus of Experimental example 7-Experimental example 11. FIG. Sectional drawing which shows an example of the conventional photoelectric conversion apparatus. Sectional drawing explaining the manufacturing method of the conventional photoelectric conversion apparatus. Sectional drawing explaining the manufacturing method of the conventional photoelectric conversion apparatus. Sectional drawing explaining the manufacturing method of the conventional photoelectric conversion apparatus. Schematic which shows an example of the manufacturing system which manufactures the conventional photoelectric conversion apparatus. Schematic which shows an example of the manufacturing system which manufactures the conventional photoelectric conversion apparatus.

Below, embodiment of the manufacturing method of the photoelectric conversion apparatus which concerns on this invention is described based on drawing.
In the following embodiments, a tandem photoelectric device is formed by stacking a first photoelectric conversion unit that is an amorphous silicon photoelectric conversion device and a second photoelectric conversion unit that is a microcrystalline silicon photoelectric conversion device. The conversion device will be described.
1A to 1C are cross-sectional views illustrating a method for manufacturing a photoelectric conversion device according to the present invention, and FIG. 2 is a cross-sectional view illustrating a layer configuration of the photoelectric conversion device.

First, as shown in FIG. 2, in the photoelectric conversion device 10 manufactured by the manufacturing method of the present invention, a pin type first electrode is formed on the first surface 1 a (front surface) of the insulating substrate 1 having optical transparency. One photoelectric conversion unit 3 and a second photoelectric conversion unit 4 are formed to overlap in this order, and a back electrode 5 is formed on the second photoelectric conversion unit 4.

The substrate 1 is made of an insulating material that is excellent in sunlight transmittance and durable, such as glass and transparent resin.
The substrate 1 includes a transparent conductive film 2.
Examples of the material of the transparent conductive film 2 include metal oxides having optical transparency such as ITO (Indium Tin Oxide), SnO ₂ , and ZnO. The transparent conductive film 2 is formed on the substrate 1 by vacuum deposition or sputtering.
In this photoelectric conversion device 10, sunlight S is incident on the second surface 1 b of the substrate 1 as indicated by a white arrow in FIG. 2.

The first photoelectric conversion unit 3 includes a p-type semiconductor layer (p layer, first p-type semiconductor layer) 31 and a substantially intrinsic i-type semiconductor layer (i layer, first i-type semiconductor layer) 32. , An n-type semiconductor layer (n layer, first n-type semiconductor layer) 33 is stacked.
That is, the first photoelectric conversion unit 3 is formed by stacking the p layer 31, the i layer 32, and the n layer 33 in this order.
The first photoelectric conversion unit 3 is made of an amorphous silicon material.
In the first photoelectric conversion unit 3, the thickness of the p layer 31 is, for example, 90 mm, the thickness of the i layer 32, for example, 2500 mm, and the thickness of the n layer 33, for example, 300 mm.
The plasma CVD reaction chambers for forming the p layer 31, i layer 32, and n layer 33 of the first photoelectric conversion unit 3 are different from each other.
In the first photoelectric conversion unit 3, the p layer 31 and the i layer 32 can be formed of amorphous silicon, and the n layer 33 can be formed of amorphous silicon containing a crystalline material (so-called microcrystal silicon).

The second photoelectric conversion unit 4 includes a p-type semiconductor layer (p layer, second p-type semiconductor layer) 41, a substantially intrinsic i-type semiconductor layer (i layer, second i-type semiconductor layer) 42. , An n-type semiconductor layer (n layer, second n-type semiconductor layer) 43 is stacked.
That is, the second photoelectric conversion unit 4 is formed by laminating the p layer 41, the i layer 42, and the n layer 43 in this order.
The second photoelectric conversion unit 4 is made of a silicon-based material containing a crystalline material.
In the second photoelectric conversion unit 4, the thickness of the p layer 41 is 100 mm, the thickness of the i layer 42 is 15000 mm, for example, and the thickness of the n layer 43 is 150 mm, for example.
In the second photoelectric conversion unit 4, the plasma CVD reaction chamber for forming the p layer 41 is different from the plasma CVD reaction chamber for forming the i layer 42 and the n layer 43. The i layer 42 and the n layer 43 are formed in the same plasma CVD reaction chamber.

The back electrode 5 should just be comprised by electroconductive light reflection films, such as Ag (silver) and Al (aluminum).
The back electrode 5 can be formed, for example, by sputtering or vapor deposition.
Further, as the back electrode 5, a layer made of a conductive oxide such as ITO, SnO ₂ , or ZnO is formed between the n-type semiconductor layer (n layer) 43 of the second photoelectric conversion unit 4 and the back electrode 5. A laminated structure may be employed.

Next, a manufacturing method for manufacturing the photoelectric conversion device 10 having the above configuration will be described.
First, as shown in FIG. 1A, an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared.
Next, as shown in FIG. 1B, a p-type semiconductor layer 31, an i-type silicon layer (amorphous silicon layer) 32, and an n-type semiconductor are formed on the transparent conductive film 2 formed on the insulating transparent substrate 1. Layer 33 and p-type semiconductor layer 41 are formed.
Here, the plasma CVD reaction chambers for forming the p layer 31, the i layer 32, the n layer 33, and the p layer 41 are different.
That is, the first intermediate product 10a of the photoelectric conversion device in which the p-type semiconductor layer 41 constituting the second photoelectric conversion unit 4 is provided on the n-type semiconductor layer 33 of the first photoelectric conversion unit 3 is formed.

The p-type semiconductor layer 31 is formed by plasma CVD in an individual reaction chamber.
For example, the substrate temperature is 170 to 200 ° C., the power supply frequency is 13.56 MHz, the reaction chamber pressure is 70 to 120 Pa, the reaction gas flow rates are 300 sccm for monosilane (SiH ₄ ), 2300 sccm for hydrogen (H ₂ ), and hydrogen as a dilution gas The p-layer 31 of amorphous silicon (a-Si) can be formed under the conditions of 180 sccm for diborane (B ₂ H ₆ / H ₂ ) and 500 sccm for methane (CH ₄ ).
The i-type silicon layer (amorphous silicon layer) 32 is formed by plasma CVD in a separate reaction chamber.
For example, under the conditions that the substrate temperature is 170 to 200 ° C., the power supply frequency is 13.56 MHz, the pressure in the reaction chamber is 70 to 120 Pa, and the reaction gas flow rate is 1200 sccm of monosilane (SiH ₄ ), the amorphous silicon (a-Si) i Layers can be deposited.
Further, the n-type semiconductor layer 33 is formed by plasma CVD in a separate reaction chamber.
For example, the substrate temperature is 170 to 200 ° C., the power supply frequency is 13.56 MHz, the pressure in the reaction chamber is 70 to 120 Pa, and the flow rate of the reaction gas is phosphine (PH ₃ / H ₂ ) using hydrogen as a diluent gas. Thus, an n layer of amorphous silicon (a-Si) can be formed.
Further, the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 is formed by plasma CVD in an individual reaction chamber.
For example, the substrate temperature is 170 to 200 ° C., the power source frequency is 13.56 MHz, the pressure in the reaction chamber is 500 to 1200 Pa, the reaction gas flow rate is 100 sccm for monosilane (SiH ₄ ), 25000 sccm for hydrogen (H ₂ ), and hydrogen as a dilution gas A p-layer of microcrystalline silicon (μc-Si) can be formed under the condition that the diborane (B ₂ H ₆ / H ₂ ) used as is 50 sccm.

Subsequently, after the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 is exposed to the atmosphere, as shown in FIG. 1C, the second photoelectric conversion unit 4 is formed on the p-type semiconductor layer 41 exposed to the atmosphere. An i-type silicon layer (crystalline silicon layer) 42 and an n-type semiconductor layer 43 are formed in the same plasma CVD reaction chamber.
That is, the second intermediate product 10 b of the photoelectric conversion device in which the second photoelectric conversion unit 4 is provided is formed on the first photoelectric conversion unit 3.
And the photoelectric conversion apparatus 10 as shown in FIG. 2 is obtained by forming the back surface electrode 5 on the n-type semiconductor layer 43 of the second photoelectric conversion unit 4.

The i-type silicon layer (crystalline silicon layer) 42 is formed by a plasma CVD method in the same reaction chamber as the reaction chamber in which the n-type semiconductor layer 43 is formed.
For example, the substrate temperature is 170 to 200 ° C., the power supply frequency is 13.56 MHz, the reaction chamber pressure is 500 to 1200 Pa, the reaction gas flow rate is 180 sccm for monosilane (SiH ₄ ), and 27000 sccm for hydrogen (H ₂ ). An i-layer of microcrystalline silicon (μc-Si) can be formed.
The n-type semiconductor layer 43 is formed by plasma CVD in the same reaction chamber as the reaction chamber in which the i-type silicon layer (crystalline silicon layer) 42 is formed.
For example, the substrate temperature is 170 to 200 ° C., the power supply frequency is 13.56 MHz, the reaction chamber pressure is 500 to 1200 Pa, the reaction gas flow rate is 180 sccm for monosilane (SiH ₄ ), 27000 sccm for hydrogen (H ₂ ), and hydrogen as a dilution gas An n-layer of microcrystalline silicon (μc-Si) can be formed under the condition that the phosphine (PH ₃ / H ₂ ) used as is 200 sccm.

Next, a system for manufacturing the photoelectric conversion device 10 will be described with reference to the drawings.
The photoelectric conversion device manufacturing system according to the present invention can be divided into a first manufacturing system and a second manufacturing system.

The first manufacturing system includes a so-called in-line type first film forming apparatus, an exposure apparatus that exposes the p layer of the second photoelectric conversion unit to the atmosphere (in the air), and a so-called batch type second film forming apparatus. It has the structure arranged in order.
The in-line type first film forming apparatus has a configuration in which a plurality of film forming reaction chambers called chambers are linearly connected.
In the first film forming apparatus, the p-type semiconductor layer 31, the i-type silicon layer (amorphous silicon layer) 32, the n-type semiconductor layer 33, and the second photoelectric conversion unit 4 in the first photoelectric conversion unit 3 are used. Each layer of the type semiconductor layer 41 is formed separately.
In the second film forming apparatus, each of the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer 43 in the second photoelectric conversion unit 4 is simultaneously applied to a plurality of substrates in the same film formation reaction chamber. It is formed.

The second manufacturing system includes a so-called in-line type first film forming device, an exposure device that exposes the p layer of the second photoelectric conversion unit to the atmosphere (in the air), and a so-called single wafer type second film forming device. The apparatus is arranged in order.
The first film forming apparatus and the exposure apparatus in the second manufacturing system have the same configuration as the first film forming apparatus and the exposure apparatus in the first manufacturing system.
In the second film forming apparatus, the second photoelectric conversion unit 104 is formed using a plurality of dedicated film forming reaction chambers for forming the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer 43. .

(First production system)
First, a first manufacturing system of a photoelectric conversion device according to the present invention is shown in FIG.
As shown in FIG. 3, the first manufacturing system is configured such that the first film forming apparatus 60, the second film forming apparatus 70 </ b> A, and the substrate processed by the first film forming apparatus 60 are exposed to the atmosphere (air). The exposure apparatus 80A moves to the film forming apparatus 70A.
The first film forming apparatus 60 in the first manufacturing system is provided with a load chamber (L: Lord) 61 in which the substrate is first carried and the internal pressure is reduced.
Note that a heating chamber for heating the substrate temperature to a certain temperature may be provided in the subsequent stage of the load chamber (L: Lord) 61 in accordance with the film forming process.
Subsequently, a p-layer film formation reaction chamber (decompression chamber) 62 for forming the p-type semiconductor layer 31 of the first photoelectric conversion unit 3 and an i-layer film formation reaction chamber for forming an i-type silicon layer (amorphous silicon layer) 32 ( Decompression chamber) 63, n-layer film formation reaction chamber (decompression chamber) 64 for forming the n-type semiconductor layer 33, and p-layer film formation reaction chamber (decompression chamber) for forming the p-type semiconductor layer 41 of the second photoelectric conversion unit 4. 65 is continuously arranged in a straight line.
Finally, an unload chamber (UL: Unload, unloading device) 66 for returning the reduced-pressure atmosphere to the atmospheric atmosphere and carrying out the substrate is connected to the p-layer film formation reaction chamber 65.
Thus, a load chamber (L) 61, a p-layer deposition reaction chamber 62, an i-layer deposition reaction chamber 63, an n-layer deposition reaction chamber 64, a p-layer deposition reaction chamber 65, an unload chamber (UL: The substrate can be transported while maintaining a reduced pressure atmosphere.
At this time, as shown in FIG. 1A, an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared at a point A shown in FIG.
3, the p-type semiconductor layer 31 and the i-type silicon layer (amorphous silicon layer) 32 of the first photoelectric conversion unit 3 are formed on the transparent conductive film 2 as shown in FIG. 1B. The first intermediate product 10a of the photoelectric conversion device provided with the n-type semiconductor layer 33 and the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 is formed.

Further, the exposure apparatus 80A in the first manufacturing system temporarily places or stores the first intermediate product 10a in which the surface of the p-type semiconductor layer 41 is exposed in an air atmosphere (air atmosphere). It is a shelf used for. Further, the exposure apparatus 80A may be a substrate storage cassette used for handling a plurality of first intermediate products 10a as one group. Further, the exposure apparatus 80A may include a transport mechanism (atmospheric transport mechanism) that transports the first intermediate product 10a from the first film forming apparatus 60 to the second film forming apparatus 70A. In addition, when the first manufacturing system is operating in a clean room, the exposure apparatus 80A allows the first intermediate product 10a to be used in an air atmosphere in the clean room in which the humidity, temperature, or the amount of particles per unit volume is controlled. It is exposed.

The second film forming apparatus 70 </ b> A in the first manufacturing system includes a load / unload chamber (L / UL) 71 and an in-layer film formation reaction chamber 72.
The load / unload chamber (L / UL) 71 carries in the first intermediate product 10a of the photoelectric conversion device processed by the first film forming device 60, and reduces the internal pressure after the substrate is carried in, The reduced-pressure atmosphere is returned to the air atmosphere when unloading.
The in-layer deposition reaction chamber 72 is connected to the load / unload chamber (L / UL) 71.
In the in-layer film formation reaction chamber 72, the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer 43 of the second photoelectric conversion unit 4 are formed on the p-type semiconductor layer 41 of the second photoelectric conversion unit 4. Sequentially formed in the same reaction chamber.
Further, this film forming process is performed simultaneously on a plurality of substrates.
At this time, the second intermediate product 10b of the photoelectric conversion device in which the second photoelectric conversion unit 4 is provided is formed on the first photoelectric conversion unit 3, as shown in FIG. .

Further, as shown in FIG. 3, in the in-line type first film forming apparatus 60, film forming processing is simultaneously performed on two substrates, and the i-layer film forming reaction chamber 63 includes four

reaction chambers

63a and 63b. , 63c, 63d.
In FIG. 3, the batch-type second film forming apparatus 70 </ b> A is configured to simultaneously process six substrates.

(Second manufacturing system)
Next, the second manufacturing system of the photoelectric conversion device according to the present invention is shown in FIG.
As shown in FIG. 4, the second manufacturing system is configured such that the first film forming apparatus 60, the second film forming apparatus 70 </ b> B, and the substrate processed by the first film forming apparatus 60 are exposed to the atmosphere (air). The exposure apparatus 80B moves to the film forming apparatus 70B.
Similar to the first film forming apparatus 60 in the first manufacturing system, the first film forming apparatus 60 in the second manufacturing system has a load chamber (L: Lord) 61 for reducing the internal pressure after the substrate is loaded.
Note that a heating chamber for heating the substrate temperature to a constant temperature may be provided in the subsequent stage of the load chamber (L) 61 depending on the process.
Subsequently, a p-layer film formation reaction chamber 62 for forming the p-type semiconductor layer 31 of the first photoelectric conversion unit 3, an i-layer film formation reaction chamber 63 for forming the i-type silicon layer (amorphous silicon layer) 32, and n An n-layer film formation reaction chamber 64 for forming the p-type semiconductor layer 33 and a p-layer film formation reaction chamber 65 for forming the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 are continuously arranged in a straight line.
Finally, an unload chamber (UL) 66 for returning the decompressed atmosphere to the atmospheric atmosphere and carrying out the substrate is connected to the p-layer deposition reaction chamber 65.
Thus, a load chamber (L) 61, a p-layer deposition reaction chamber 62, an i-layer deposition reaction chamber 63, an n-layer deposition reaction chamber 64, a p-layer deposition reaction chamber 65, an unload chamber (UL: The substrate can be transported while maintaining a reduced pressure atmosphere.
At this time, as shown in FIG. 1A, an insulating transparent substrate 1 having a transparent conductive film 2 formed thereon is prepared at a point D shown in FIG.
4, the p-type semiconductor layer 31, i-type silicon layer (amorphous silicon layer) 32 of the first photoelectric conversion unit 3 on the transparent conductive film 2, as shown in FIG. 1B. The first intermediate product 10a of the photoelectric conversion device provided with the n-type semiconductor layer 33 and the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 is formed.

Further, the configuration of the exposure apparatus 80B in the second manufacturing system is the same as that of the exposure apparatus 80A in the first manufacturing system. Further, the exposure apparatus 80B may have a transport mechanism (atmospheric transport mechanism) that transports the first intermediate product 10a from the first film forming apparatus 60 to the second film forming apparatus 70B in an air atmosphere.

The second film forming apparatus 70B in the second manufacturing system includes a load / unload chamber (L / UL) 73, an i-layer film forming reaction chamber 74, an n-layer film forming reaction chamber 75, and an intermediate structure. A chamber 77 is provided.
The load / unload chamber (L / UL) 73 is used for reducing the internal pressure after unloading the first intermediate product 10a of the photoelectric conversion apparatus processed by the first film forming apparatus 60 or unloading the substrate. Return the reduced-pressure atmosphere to the air atmosphere.
Subsequently, the substrate is carried into the intermediate chamber 77 through the load / unload chamber (L / UL) 73. Further, the intermediate chamber 77 and the p-layer film formation reaction chamber 74, the intermediate chamber 77 and the i-layer film formation reaction chamber 75, and the intermediate chamber 77 and the n-layer film formation reaction chamber 76 are transported. .
In the i layer deposition reaction chamber 74, the i type silicon layer (crystalline silicon layer) 42 of the second photoelectric conversion unit 4 is formed on the p type semiconductor layer 41 of the second photoelectric conversion unit 4.
In the n-layer deposition reaction chamber 75, an n-type semiconductor layer 43 is formed on the i-type silicon layer (crystalline silicon layer) 42.
In each of the i-layer deposition reaction chamber 74 and the n-layer deposition reaction chamber 75, one of the i-type silicon layer 42 and the n-type semiconductor layer 43 is formed on a single substrate.
In addition, a transfer device (not shown) provided in the intermediate chamber 77 transfers a substrate to each of the

reaction chambers

73 and 74 in order to stack the i-type silicon layer 42 and the n-type semiconductor layer 43, The substrate is unloaded from each of 174, 175, and 176.
Note that the second film forming apparatus 70B may have a heating chamber that heats the substrate temperature to a certain temperature in accordance with the film forming process.
At this time, as shown in FIG. 1C, the second intermediate product 10b of the photoelectric conversion device in which the second photoelectric conversion unit 4 is provided on the first photoelectric conversion unit 3 is formed at the point F shown in FIG.

In FIG. 4, in the in-line type first film forming apparatus 60, film formation processing is simultaneously performed on two substrates, and the i-layer film formation reaction chamber 63 includes four

reaction chambers

63 a, 63 b, 63 c, 63d.
In FIG. 4, in the single wafer type second film forming apparatus 70B, seven substrates are simultaneously processed in each reaction chamber.
In FIG. 4, the i-layer film formation reaction chamber 74 includes six

reaction chambers

74a, 74b, 74c, 74d, 74e, and 74f.
Since the i-type silicon layer 42 constituting the second photoelectric conversion unit 4 has a larger film thickness than the n-type semiconductor layer 43, the film formation time is longer than when the n-type semiconductor layer 43 is formed.
Therefore, the throughput for producing the photoelectric conversion device is determined depending on the number of reaction chambers in the i-layer film formation reaction chamber 74.
As described above, in the single wafer type second film forming apparatus 70B, the i layer film forming reaction chamber 74 has six reaction chambers, so that the i type silicon layer 42 can be simultaneously formed on a plurality of substrates. And throughput is improved.

According to the manufacturing method of the photoelectric conversion device as described above, crystalline photoelectric is formed on the p layer, i layer, and n layer of the first photoelectric conversion unit 3 that is an amorphous photoelectric conversion device in the first film forming device 60. The p layer of the 2nd photoelectric conversion unit 4 which is a converter is formed. Further, the i layer and the n layer of the second photoelectric conversion unit 4 are formed in the second

film forming apparatuses

70A and 70B. Thereby, the control of the crystallization rate distribution of the i layer of the second photoelectric conversion unit 4 can be facilitated.

In the present invention, the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer 43 constituting the second photoelectric conversion unit 4 are formed on the p-type semiconductor layer 41 exposed in the atmosphere. At this time, before forming the i layer 42, it is desirable to expose the p layer 41 of the second photoelectric conversion unit 4 exposed to the atmosphere to plasma containing hydrogen radicals (hydrogen radical plasma treatment).

As the hydrogen radical plasma treatment, there is a method in which a hydrogen radical plasma treatment chamber is prepared in advance, the substrate on which the p layer 41 of the second photoelectric conversion unit 4 is formed is transferred to the plasma treatment chamber, and the p layer 41 is exposed to plasma. It is done. In addition, after the hydrogen radical plasma treatment, an i-type silicon layer (crystalline silicon layer) 42 and an n-type semiconductor layer 43 constituting the second photoelectric conversion unit 4 are formed in separate reaction chambers.
On the other hand, as the hydrogen radical plasma treatment, the hydrogen radical plasma treatment and the treatment for forming the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 may be continuously performed in the same reaction chamber.

Here, when the process of forming the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 and the hydrogen radical plasma process are performed in the same processing chamber, the inner wall of the reaction chamber is formed before the i layer 42 is formed. Is exposed to plasma containing hydrogen radicals, it is possible to decompose and remove the residual impurity gas PH ₃ introduced when forming the previous n layer 43.
Therefore, even when the film formation process of the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 is repeatedly performed in the same processing chamber, a good impurity profile can be obtained, and a laminated thin film having good power generation efficiency. A photoelectric conversion device can be obtained.

In the hydrogen radical plasma processing is performed on the p layer 41 of the second photoelectric conversion unit 4, using a H ₂ gas (hydrogen gas) as the process gas when desired.
That is, in order to generate hydrogen radical plasma, plasma is effectively generated by applying a high frequency such as 13.5 MHz, 27 MHz, 40 MHz, or the like between the electrodes in the processing chamber with H ₂ flowing into the processing chamber. Can be generated.
Further, in the above-described second

film forming apparatuses

70A and 70B, a gas box (gas introduction unit) and a gas line (gas introduction unit) for supplying H ₂ gas used for hydrogen radical plasma processing into the processing chamber (reaction chamber). Is provided. In addition, a mass flow controller (gas introduction unit) is connected to the processing chamber, the flow rate of H ₂ gas supplied through the gas box and the gas line is controlled, and a gas having a controlled flow rate is supplied into the processing chamber. The

When the hydrogen radical plasma treatment is performed in this manner, a mild reaction occurs as compared with the O radical, and therefore, there is an effect of activating the surface of the p layer 41 of the second photoelectric conversion unit 4 without damaging the lower layer. .
Therefore, the surface of the p layer 41 of the second photoelectric conversion unit 4 can be activated, and crystals of the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 stacked thereon are effectively generated. be able to. Even when the second photoelectric conversion unit 4 is formed on a large-area substrate, a uniform crystallization rate distribution can be obtained.

Further, as the n layer 33 of the first photoelectric conversion unit 3 and the p layer 41 of the second photoelectric conversion unit 4, microcrystalline silicon (μc-Si) is dispersed in an amorphous silicon (a-Si) layer. Alternatively, a layer in which microcrystalline silicon (μc-Si) is dispersed in an amorphous silicon oxide (a-SiO) layer may be used.
However, in order to obtain a uniform crystallization distribution rate required when the area of the substrate is increased, that is, a uniform crystallization distribution rate by generation of crystal growth nuclei of the crystalline photoelectric conversion layer i layer and n layer. For this, it is preferable to employ a layer in which microcrystalline silicon (μc-Si) is dispersed in an amorphous amorphous silicon oxide (a-SiO) layer.

As described above, a layer in which microcrystalline silicon (μc-Si) is dispersed in an amorphous amorphous silicon oxide (a-SiO) layer has a lower refractive index than an amorphous silicon (a-Si) semiconductor layer. It is possible to adjust as follows.
Therefore, it is possible to improve the conversion efficiency by making this layer function as a wavelength selective reflection film and confining short wavelength light on the top cell side.
Regardless of the effect of confining light, a layer in which microcrystalline silicon (μc-Si) is dispersed in an amorphous amorphous silicon oxide (a-SiO) layer is formed by hydrogen radical plasma treatment. Generation of crystal growth nuclei of the i layer 42 and the n layer 43 of the photoelectric conversion unit 4 is effectively performed, and a uniform crystallization rate distribution can be obtained even on a large-area substrate.

In the present invention, a crystalline silicon-based thin film may be formed as the n layer 33 constituting the first photoelectric conversion unit 3.
That is, on the p layer 31 and the i layer 32 of the first photoelectric conversion unit 3 of amorphous silicon, the n layer 33 of microcrystal silicon and the p layer 41 of the second photoelectric conversion unit 4 of microcrystal silicon are formed.
At this time, the p layer 31 of the amorphous first photoelectric conversion unit 3, the amorphous i layer 32 formed on the p layer 31, and the crystalline n layer 33 formed on the i layer 32. It is desirable that the p layer 41 of the second photoelectric conversion unit 4 formed on the n layer 33 is continuously formed without being exposed to the atmosphere.

In particular, after forming the p layer 31, i layer 32, and n layer 33 of the first photoelectric conversion unit 3, the atmosphere is released and the p layer 41, i layer 42, n of the second photoelectric conversion unit 4 is opened in another reaction chamber. In the method of forming the layer 43, the i-layer 32 of the first photoelectric conversion unit 3 is deteriorated due to the time, temperature, atmosphere, etc. in which the substrate is left open to the atmosphere and the device performance is deteriorated.
Therefore, after the p layer 31 and the i layer 32 of the first photoelectric conversion unit 3 are formed, the crystalline n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 are continuously formed without opening to the atmosphere. .

In this way, the substrate on which the crystalline n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 are formed is subjected to hydrogen radical plasma treatment in an individual reaction chamber or the same reaction chamber to activate the surface. By producing crystal nuclei and subsequently laminating the i layer 42 and the n layer 43 of the crystalline second photoelectric conversion unit 4, a laminated thin film photoelectric conversion device with good power generation efficiency can be obtained.
FIG. 4 shows an example in which each of the i layer and the n layer of the second photoelectric conversion unit 4 is formed in the

individual chambers

74 and 75. However, in each of the

individual chambers

74 and 75, FIG. , I layer and n layer may be successively formed.

(Experimental example)
Next, the following experiment was conducted on the photoelectric conversion device manufactured by the method for manufacturing a photoelectric conversion device according to the present invention.
The photoelectric conversion device manufactured by each experimental example and its manufacturing conditions are as follows.
In any of the experimental examples described below, the photoelectric conversion device is manufactured using a substrate having a size of 1100 mm × 1400 mm.

(1) In the experimental examples shown below, the relationship between the time during which the p layer of the second photoelectric conversion unit was exposed to the air atmosphere and the photoelectric conversion characteristics was evaluated.
(Experimental example 1)
In Experimental Example 1, a p layer and an i layer made of an amorphous amorphous silicon (a-Si) thin film are formed as a first photoelectric conversion unit on a substrate, and microcrystalline silicon (μc−) is formed on the i layer. An n layer containing Si) was formed, and a p layer containing microcrystalline silicon (μc-Si) constituting the second photoelectric conversion unit was formed. These layers were continuously formed in a vacuum atmosphere, and the reaction chambers for forming these layers were made different from each other. Thereafter, the p layer of the second photoelectric conversion unit was exposed to the atmosphere, and the hydrogen radical plasma treatment was performed on the p layer of the second photoelectric conversion unit. Thereafter, an i layer and an n layer made of microcrystalline silicon (μc-Si) constituting the second photoelectric conversion unit were formed.

In Experimental Example 1, the p layer, i layer, n layer of the first photoelectric conversion unit, and the p layer of the second photoelectric conversion unit were formed by plasma CVD. The reaction chambers for forming the p layer, i layer, and n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were made different from each other. On the other hand, the i layer and the n layer of the second photoelectric conversion unit were formed by plasma CVD in the same reaction chamber.
The p layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., a power output of 40 W, a reaction chamber pressure of 80 Pa, an E / S (distance between the substrate and the counter electrode) of 20 mm, and a reaction gas flow rate of monosilane. A film thickness of 80 cm under conditions of (SiH ₄ ) 150 sccm, hydrogen (H ₂ ) 470 sccm, diborane (B ₂ H ₆ / H ₂ ) using hydrogen as a diluent gas, 45 sccm, and methane (CH ₄ ) 300 sccm. A film was formed.
Further, the buffer layer has a substrate temperature of 170 ° C., a power output of 40 W, a reaction chamber pressure of 60 Pa, an E / S of 17 mm, and a reaction gas flow rate of monosilane (SiH ₄ ) of 150 sccm, hydrogen (H ₂ ) of 1500 sccm, The film was formed to a thickness of 60 mm under the condition that methane (CH ₄ ) was changed from 200 sccm to 0 sccm.

In addition, the i layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., a power output of 40 W, a reaction chamber pressure of 40 Pa, an E / S of 14 mm, and a reaction gas flow rate of monosilane (SiH ₄ ) of 300 sccm. The film was formed to a thickness of 1800 mm.
Further, the n layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., a power output of 1000 W, a reaction chamber pressure of 800 Pa, an E / S of 14 mm, a reaction gas flow rate of monosilane (SiH ₄ ) of 20 sccm, hydrogen ( H ₂₎ is 2000 sccm, phosphine using hydrogen as the diluent gas _(PH 3 / _{H 2)} is in the condition of 15 sccm, was deposited to a thickness of 100 Å.

Next, the p layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., a power output of 750 W, a reaction chamber pressure of 1200 Pa, an E / S of 9 mm, a reactive gas flow rate of monosilane (SiH ₄ ) of 30 sccm, hydrogen A film was formed to a thickness of 150 mm under the conditions of 9000 sccm of (H ₂ ) and 12 sccm of diborane (B ₂ H ₆ / H ₂ ) using hydrogen as a diluent gas.

Here, the p layer of the second photoelectric conversion unit was exposed to the atmosphere for 5 minutes.
Subsequently, the i-layer of the second photoelectric conversion unit was formed with a substrate temperature of 170 ° C., a power output of 550 W, a reaction chamber pressure of 1200 Pa, an E / S of 9 mm, a reactive gas flow rate of 45 sccm of monosilane (SiH ₄ ), hydrogen ( A film having a thickness of 15000 mm was formed under the condition of H ₂ ) of 3150 sccm.
The n layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., a power output of 1000 W, a reaction chamber pressure of 800 Pa, an E / S of 14 mm, a reaction gas flow rate of monosilane (SiH ₄ ) of 20 sccm, hydrogen ( H ₂₎ is 2000 sccm, phosphine using hydrogen as the diluent gas _(PH 3 / _{H 2)} is in the condition of 15 sccm, was deposited to a thickness of 300 Å.

(Experimental example 2)
In this experimental example, in the same manner as in Experimental Example 1, after forming the p layer of the first photoelectric conversion unit, the i layer, the n layer, and the p layer of the second photoelectric conversion unit on the substrate, the second photoelectric conversion unit The p-layer of was exposed to the atmosphere for 5 minutes.
The p layer was subjected to hydrogen radical plasma treatment for 60 seconds under the conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.
Thereafter, in the same manner as in Experimental Example 1, an i layer and an n layer of the second photoelectric conversion unit were formed.

(Experimental example 3)
In this experimental example, in the same manner as in Experimental Example 1, after forming the p layer of the first photoelectric conversion unit, the i layer, the n layer, and the p layer of the second photoelectric conversion unit on the substrate, the second photoelectric conversion unit The p-layer of was exposed to the atmosphere for 22 hours.
Thereafter, in the same manner as in Experimental Example 1, an i layer and an n layer of the second photoelectric conversion unit were formed.

(Experimental example 4)
In this experimental example, in the same manner as in Experimental Example 1, after forming the p layer of the first photoelectric conversion unit, the i layer, the n layer, and the p layer of the second photoelectric conversion unit on the substrate, the second photoelectric conversion unit The p-layer of was exposed to the atmosphere for 22 hours.
The p layer was subjected to hydrogen radical plasma treatment for 60 seconds under the conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.
Thereafter, in the same manner as in Experimental Example 1, an i layer and an n layer of the second photoelectric conversion unit were formed.

(Experimental example 5)
In this experimental example, in the same manner as in Experimental Example 1, after forming the p layer of the first photoelectric conversion unit, the i layer, the n layer, and the p layer of the second photoelectric conversion unit on the substrate, the second photoelectric conversion unit The p-layer was exposed to the atmosphere for 860 hours.
The p layer was subjected to hydrogen radical plasma treatment for 60 seconds under the conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.
Thereafter, in the same manner as in Experimental Example 1, an i layer and an n layer of the second photoelectric conversion unit were formed.

(Experimental example 6)
In this experiment example, the p layer, i layer, n layer of the first photoelectric conversion unit, and the p layer of the second photoelectric conversion unit were formed on the substrate in the same manner as in Experiment example 1.
In Experimental Example 6, the step of exposing the p layer to the air atmosphere and the hydrogen radical plasma treatment were not performed, and then the i layer and the n layer of the second photoelectric conversion unit were formed in the same manner as in Experimental Example 1.

Table 1 shows the film forming conditions of each layer in the photoelectric conversion devices manufactured in Experimental Examples 1 to 6.

The photoelectric conversion devices of Experimental Examples 1 to 6 manufactured as described above were irradiated with AM (air mass) 1.5 light at a light amount of 100 mW / cm ² and output characteristics were measured at 25 ° C. The conversion efficiency (η), short circuit current (Jsc), open circuit voltage (Voc), fill factor (FF), and Ic / Ia (spectrum intensity of crystals / spectrum intensity of amorphous by Raman spectroscopy) were evaluated. The results are shown in Table 2.
FIG. 5 shows the relationship between the current density and the voltage for the photoelectric conversion devices of Experimental Examples 1 to 6. FIG. 5 shows characteristic curves individually showing each experimental example and characteristic curves collectively showing experimental examples 1 to 6.
Further, the relationship between the exposure time of the p layer to the air atmosphere and the photoelectric conversion efficiency, Jsc, Voc, and FF are shown in FIGS. 6 to 9, respectively.

As is apparent from Table 2 and FIGS. 6 to 9, Experimental Example 1 and Experimental Example 3 in which the p layer of the second photoelectric conversion unit was exposed to the air atmosphere, and Experimental Example 6 in which the p layer was not exposed to the air atmosphere. When the p layer is exposed to the air atmosphere, it is confirmed that the characteristics are deteriorated, and it is understood that the degree of the deterioration is large as the exposure time is increased.
On the other hand, when Experimental Example 1 is compared with Experimental Example 2 and Experimental Example 3 is compared with Experimental Example 4, the decrease is suppressed in Experimental Example 2 and Experimental Example 4 that have been subjected to hydrogen radical plasma treatment. It can be seen that good characteristics almost equivalent to those of Experimental Example 6 in which the p layer is not exposed to the air atmosphere are obtained.
In particular, even when the p-layer is exposed for 860 hours as in Example 5, good characteristics almost equivalent to those of Experimental Example 6 in which the p-layer is not exposed to the air atmosphere are obtained by performing hydrogen radical plasma treatment. It has been.

Further, as can be seen from FIG. 5 showing the relationship between the current density and the voltage, a good curve closer to a square is obtained by performing the hydrogen radical plasma treatment.
From the above, by performing hydrogen radical plasma treatment on the p layer of the second photoelectric conversion unit, a photoelectric conversion device having excellent photoelectric conversion characteristics can be manufactured even if the p layer is exposed to the atmosphere for a long time. You can see that

(2) In the experimental examples shown below, the relationship between plasma processing time and photoelectric conversion characteristics was evaluated.
(Experimental example 7)
In Experimental Example 7, a p-layer and an i-layer made of an amorphous amorphous silicon (a-Si) -based thin film are formed as a first photoelectric conversion unit on a substrate, and microcrystalline silicon (μc−) is formed on the i-layer. An n layer containing Si) was formed, and a p layer containing microcrystalline silicon (μc-Si) constituting the second photoelectric conversion unit was formed. These layers were continuously formed in a vacuum atmosphere, and the reaction chambers for forming these layers were made different from each other. Thereafter, the p layer of the second photoelectric conversion unit was exposed to the atmosphere, and the hydrogen treatment-containing plasma treatment was performed on the p layer of the second photoelectric conversion unit. Thereafter, an i layer and an n layer made of microcrystalline silicon (μc-Si) constituting the second photoelectric conversion unit were formed.

In Experimental Example 7, the p layer, i layer, and n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were formed by plasma CVD. The reaction chambers for forming the p layer, i layer, and n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were made different from each other. On the other hand, the i layer and the n layer of the second photoelectric conversion unit were formed by plasma CVD in the same reaction chamber.
The p layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., a power supply output of 40 W, a reaction chamber pressure of 80 Pa, an E / S of 20 mm, a reaction gas flow rate of monosilane (SiH ₄ ) of 150 sccm, hydrogen (H ₂ ) Is 470 sccm, diborane (B ₂ H ₆ / H ₂ ) using hydrogen as a diluent gas is 45 sccm, and methane (CH ₄ ) is 300 sccm.
Further, the buffer layer has a substrate temperature of 170 ° C., a power output of 40 W, a reaction chamber pressure of 60 Pa, an E / S of 17 mm, and a reaction gas flow rate of monosilane (SiH ₄ ) of 150 sccm, hydrogen (H ₂ ) of 1500 sccm, A film of methane (CH ₄ ) was formed to a thickness of 60 mm under conditions of 200 sccm to 0 sccm.

Here, the p layer of the second photoelectric conversion unit was exposed to the atmosphere for 24 hours.
The p layer was subjected to hydrogen radical plasma treatment for 30 seconds under conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.

Subsequently, the i-layer of the second photoelectric conversion unit was formed with a substrate temperature of 170 ° C., a power output of 550 W, a reaction chamber pressure of 1200 Pa, an E / S of 9 mm, a reactive gas flow rate of 45 sccm of monosilane (SiH ₄ ), hydrogen ( The film was formed to a thickness of 15000 mm under the condition of H ₂ ) of 3150 sccm.
The n layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., a power output of 1000 W, a reaction chamber pressure of 800 Pa, an E / S of 14 mm, a reaction gas flow rate of monosilane (SiH ₄ ) of 20 sccm, hydrogen ( H ₂₎ is 2000 sccm, phosphine using hydrogen as the diluent gas _(PH 3 / _{H 2)} is in the condition of 15 sccm, was deposited to a thickness of 300 Å.

(Experimental example 8)
In this experimental example, in the same manner as in Experimental Example 6, after the p layer, i layer, n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were formed on the substrate, The p-layer was exposed to the atmosphere for 22 hours.
The p layer was subjected to hydrogen radical plasma treatment for 60 seconds under the conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.
Thereafter, the i layer and the n layer of the second photoelectric conversion unit were formed in the same manner as in Experimental Example 7.

(Experimental example 9)
In this experimental example, in the same manner as in Experimental Example 6, after the p layer, i layer, n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were formed on the substrate, The p-layer was exposed to the atmosphere for 24 hours.
The p layer was subjected to hydrogen radical plasma treatment for 120 seconds under the conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.
Thereafter, in the same manner as in Experimental Example 6, an i layer and an n layer of the second photoelectric conversion unit were formed.

(Experimental example 10)
In this experimental example, in the same manner as in Experimental Example 6, after the p layer, i layer, n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were formed on the substrate, The p-layer was exposed to the atmosphere for 24 hours.
The p layer was subjected to hydrogen radical plasma treatment for 300 seconds under conditions of a substrate temperature of 170 ° C., a power output of 500 W, a reaction chamber pressure of 400 Pa, and a process gas of H ₂ of 1000 sccm.
Thereafter, the i layer and the n layer of the second photoelectric conversion unit were formed in the same manner as in Experimental Example 7.

(Experimental example 11)
In this experiment example, the p layer, i layer, n layer of the first photoelectric conversion unit, and the p layer of the second photoelectric conversion unit were formed on the substrate in the same manner as in Experiment example 7.
In Experimental Example 11, the step of exposing the p layer to the air atmosphere and the hydrogen radical plasma treatment were not performed, and then the i layer and the n layer of the second photoelectric conversion unit were formed in the same manner as in Experimental Example 7.

Table 3 shows the film forming conditions of each layer of the photoelectric conversion devices manufactured in Experimental Example 7 to Experimental Example 11.

The photoelectric conversion devices of Experimental Examples 7 to 11 manufactured as described above were irradiated with AM1.5 light at a light amount of 100 mW / cm ² , output characteristics were measured at 25 ° C., and photoelectric conversion efficiency (η ), Short circuit current (Jsc), open circuit voltage (Voc), fill factor (FF), and Ic / Ia. The results are shown in Table 4.
FIG. 10 shows the relationship between the current density and the voltage for the photoelectric conversion devices of Experimental Examples 7 to 11. FIG. 10 shows characteristic curves individually showing each experimental example and characteristic curves collectively showing experimental examples 7 to 11.
Further, the relationship between the hydrogen radical plasma treatment time and the photoelectric conversion efficiency, Jsc, Voc, and FF is shown in FIGS. 11 to 14, respectively.

As is apparent from Table 4 and FIGS. 10 to 14, even if the p layer of the second photoelectric conversion unit is exposed to the air atmosphere, the characteristics are not deteriorated by performing the hydrogen radical plasma treatment, and the photoelectric conversion characteristics are good. In particular, it can be seen that the same effect is obtained regardless of the hydrogen radical plasma treatment time.

From the above, the p layer of the second photoelectric conversion unit is formed in succession to the p layer, i layer, and n layer of the first photoelectric conversion unit, and then the p layer of the second photoelectric conversion unit is exposed to the atmosphere. Then, when the i layer and the n layer of the second photoelectric conversion unit are formed, it is understood that a photoelectric conversion device having excellent photoelectric conversion characteristics can be manufactured.
It can also be seen that by performing hydrogen radical plasma treatment on the p layer of the second photoelectric conversion unit, it is possible to produce a photoelectric conversion device with better photoelectric conversion characteristics than when the p layer is exposed to the atmosphere. .
As described above, in the method for manufacturing a photoelectric conversion device of the present invention, the first exposed to the air atmosphere is formed before forming the i-type semiconductor layer (second i-type semiconductor layer) constituting the second photoelectric conversion unit. The p-type semiconductor layer (second p-type semiconductor layer) of the two photoelectric conversion unit is preferably exposed to plasma containing hydrogen radicals. Furthermore, it is preferable to form a p-type semiconductor layer (third p-type semiconductor layer) after forming an n-type semiconductor layer (second n-type semiconductor layer) of the second photoelectric conversion unit. Thus, when the substrate is unloaded, the reaction chamber becomes an atmosphere of the gas used to form the p-type semiconductor (B ₂ H ₆ (p-type dopant) atmosphere), and when the next substrate is loaded, the pH in the reaction chamber is increased. ₃ (n-type dopant) remains. Accordingly, when an i-type semiconductor layer (second i-type semiconductor layer) is formed on the next substrate, PH ₃ (n-type dopant) is mixed into the i-type semiconductor layer adjacent to the p-type semiconductor layer. Is suppressed, and deterioration of characteristics can be suppressed. Further, before carrying in the next substrate, or before forming the i-type semiconductor layer of the second photoelectric conversion unit on the next substrate, the reaction chamber is sufficiently purged with hydrogen so that the clean i-type can be obtained. This is preferable for forming a semiconductor layer.
Furthermore, before forming the i-type semiconductor layer, the reaction chamber is in an atmosphere of a gas used to form the p-type semiconductor (an atmosphere containing a B ₂ H ₆ (p-type dopant) gas). Then, hydrogen plasma treatment may be performed, and then an i-type semiconductor layer and an n-type semiconductor layer may be formed. The p-type atmosphere can be adjusted, the pi junction can be easily controlled, and a higher-performance photoelectric conversion device can be formed.

As described above in detail, in the photoelectric conversion device according to the present invention, junction disturbance caused by diffusion of p-layer impurities constituting the second photoelectric conversion unit into the i layer or mixing of residual impurities into the p and n layers. The present invention is useful for a method for manufacturing a photoelectric conversion device having good power generation performance, a photoelectric conversion device, and a system for manufacturing a photoelectric conversion device.

1 transparent substrate, 2 transparent conductive film, 3 first photoelectric conversion unit, 4 second photoelectric conversion unit, 5 back electrode, 10 photoelectric conversion device, 31 p-type semiconductor layer (first p-type semiconductor layer), 32 i-type Silicon layer (amorphous silicon layer, first i-type semiconductor layer), 33 n-type semiconductor layer (first n-type semiconductor layer), 41 p-type semiconductor layer (second p-type semiconductor layer), 42 i Type silicon layer (crystalline silicon layer, second i-type semiconductor layer), 43 n-type semiconductor layer (second n-type semiconductor layer), 60 first film forming device, 61 load chamber, 62 p layer film forming reaction Chamber (decompression chamber), 63 (63a, 63b, 63c, 63d), i layer deposition reaction chamber (decompression chamber), 64 n layer deposition reaction chamber (decompression chamber), 65 p layer deposition reaction chamber (decompression chamber) 66 unloading chamber, 70A, 70B second film forming apparatus, 71, 73 Load / unload chamber, 72 in-layer deposition reaction chamber, 74 (74a, 74b, 74c, 74d, 74e, 74f) i-layer deposition reaction chamber, 75 n-layer deposition reaction chamber, 77 intermediate chamber, 80A, 80B Exposure device.

Claims

A method for manufacturing a photoelectric conversion device, comprising:
A first p-type semiconductor layer, a first i-type semiconductor layer, and a first n-type semiconductor layer constituting the first photoelectric conversion unit; and a second p-type semiconductor layer constituting the second photoelectric conversion unit; Are continuously formed in different decompression chambers,
Exposing the second p-type semiconductor layer to an air atmosphere;
Forming a second i-type semiconductor layer and a second n-type semiconductor layer constituting the second photoelectric conversion unit in the same decompression chamber on the second p-type semiconductor layer exposed to the air atmosphere;
A method for manufacturing a photoelectric conversion device.
It is a manufacturing method of the photoelectric conversion device according to claim 1,
Before forming the second i-type semiconductor layer, the second p-type semiconductor layer exposed to the atmosphere is exposed to plasma containing hydrogen radicals;
A method for manufacturing a photoelectric conversion device.
It is a manufacturing method of a photoelectric conversion device according to claim 2,
When exposing the second p-type semiconductor layer to the plasma containing the hydrogen radicals, hydrogen gas is used.
A method for manufacturing a photoelectric conversion device.
It is a manufacturing method of the photoelectric conversion device according to claim 2,
Prior to forming the second i-type semiconductor layer, the second p-type semiconductor layer is exposed to plasma containing hydrogen radicals in an atmosphere in which a dopant gas mixed into the second p-type semiconductor layer is present. ,
A method for manufacturing a photoelectric conversion device.
It is a manufacturing method of the photoelectric conversion device according to any one of claims 1 to 4,
Forming a crystalline silicon-based thin film as the first n-type semiconductor layer;
A method for manufacturing a photoelectric conversion device.
It is a manufacturing method of the photoelectric conversion device according to any one of claims 1 to 5,
Forming a third p-type semiconductor layer after forming the second i-type semiconductor layer and the second n-type semiconductor layer;
A method for manufacturing a photoelectric conversion device.
A photoelectric conversion device,
A photoelectric conversion device formed by the method for manufacturing a photoelectric conversion device according to any one of claims 1 to 6.
A photoelectric conversion device manufacturing system,
A first p-type semiconductor layer, a first i-type semiconductor layer, and a first n-type semiconductor layer constituting the first photoelectric conversion unit; and a second p-type semiconductor layer constituting the second photoelectric conversion unit; A first film forming apparatus including a plurality of plasma CVD reaction chambers connected to maintain a reduced pressure atmosphere,
An unloading device for unloading the substrate on which the second p-type semiconductor layer is formed to an air atmosphere;
A second film forming apparatus including a plasma CVD reaction chamber that accommodates the substrate carried out in the air atmosphere and forms the second i-type semiconductor layer and the second n-type semiconductor layer in a reduced-pressure atmosphere;
A system for manufacturing a photoelectric conversion device comprising:
It is a manufacturing system of the photoelectric conversion device according to claim 8,
The second film forming apparatus exposes the second p-type semiconductor layer exposed to the air atmosphere to plasma containing hydrogen radicals before forming the second i-type semiconductor layer.
A manufacturing system for a photoelectric conversion device.
It is a manufacturing system of the photoelectric conversion device according to claim 8,
The second film forming apparatus has a gas introduction part for introducing hydrogen gas,
Using the hydrogen gas introduced by the gas introduction unit, the second p-type semiconductor layer is exposed to the plasma containing the hydrogen radicals.
A manufacturing system for a photoelectric conversion device.
It is a manufacturing system of the photoelectric conversion device according to claim 9,
In the plasma CVD reaction chamber forming the second i-type semiconductor layer and the second n-type semiconductor layer, the second p-type semiconductor layer is exposed to the plasma containing the hydrogen radicals;
A manufacturing system for a photoelectric conversion device.
It is a manufacturing system of the photoelectric conversion device according to claim 9,
Before forming the second i-type semiconductor layer, the second p-type semiconductor layer is exposed to plasma containing hydrogen radicals in an atmosphere in which a dopant gas mixed into the second p-type semiconductor layer is present. ,
A manufacturing system for a photoelectric conversion device.
It is a manufacturing system of the photoelectric conversion device according to any one of claims 8 to 12,
The first film forming apparatus forms a crystalline silicon-based thin film as the first n-type semiconductor layer.
A manufacturing system for a photoelectric conversion device.
It is a manufacturing system of the photoelectric conversion device according to any one of claims 8 to 13,
Forming a third p-type semiconductor layer after forming the second i-type semiconductor layer and the second n-type semiconductor layer;
A manufacturing system for a photoelectric conversion device.