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WO2010146846A1 - Dispositif de conversion photoélectrique et procédé de production d'un dispositif de conversion photoélectrique - Google Patents

Dispositif de conversion photoélectrique et procédé de production d'un dispositif de conversion photoélectrique Download PDF

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WO2010146846A1
WO2010146846A1 PCT/JP2010/003997 JP2010003997W WO2010146846A1 WO 2010146846 A1 WO2010146846 A1 WO 2010146846A1 JP 2010003997 W JP2010003997 W JP 2010003997W WO 2010146846 A1 WO2010146846 A1 WO 2010146846A1
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layer
photoelectric conversion
type semiconductor
semiconductor layer
conversion unit
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Japanese (ja)
Inventor
今北健一
内田寛人
浅利伸
橋本征典
藤長徹志
小林忠正
若井雅文
朝比奈伸一
植喜信
中村久三
斎藤一也
清水康男
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Ulvac Inc
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Ulvac Inc
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/545—Microcrystalline silicon PV cells
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion device using a thin film and a method for manufacturing the photoelectric conversion device.
  • the present application claims priority based on Japanese Patent Application No. 2009-145691 filed on June 18, 2009 and Japanese Patent Application No. 2009-229881 filed on October 1, 2009, the contents of which are incorporated herein by reference. To do.
  • a photoelectric conversion device using single crystal silicon is excellent in energy conversion efficiency per unit area.
  • 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.
  • 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.
  • a tandem structure in which two photoelectric conversion units are stacked has been proposed.
  • a tandem photoelectric conversion device 200 as shown in FIG. 17 is known (see, for example, Patent Document 1).
  • an insulating transparent substrate 201 provided with a transparent conductive film 202 is used.
  • a p-type semiconductor layer 231 (p layer), an i-type silicon layer 232 (amorphous silicon layer, i layer), and an n-type semiconductor layer 233 (n layer) are sequentially stacked on the transparent conductive film 202.
  • a pin-type first photoelectric conversion unit 203 is formed.
  • a p-type semiconductor layer 241 (p layer), an i-type silicon layer 242 (crystalline silicon layer, i layer), and an n-type semiconductor layer 243 (n layer) are sequentially stacked on the first photoelectric conversion unit 203.
  • the obtained pin type second photoelectric conversion unit 204 is formed. Further, a back electrode 205 is formed on the second photoelectric conversion unit 204.
  • FIG. 18 shows the relationship between the wavelength and the power generation efficiency in the photoelectric conversion device having such a conventional tandem structure.
  • the relationship between the wavelength and the power generation efficiency of each of the pin-type first photoelectric conversion unit made of an amorphous silicon-based thin film and the pin-type second photoelectric conversion unit made of a crystalline silicon-based thin film is shown. It is shown.
  • the pin-type second photoelectric conversion unit made of a crystalline silicon thin film has low power generation efficiency in the long wavelength region. For this reason, it was difficult to improve the photoelectric conversion efficiency in the whole photoelectric conversion apparatus including the first photoelectric conversion unit and the second photoelectric conversion unit.
  • the present invention has been made to solve the above-described problem, and in a photoelectric conversion device having a tandem structure, power generation in a long wavelength region in a pin-type second photoelectric conversion unit made of a crystalline silicon-based thin film.
  • the primary purpose is to improve efficiency and improve photoelectric conversion efficiency.
  • this invention makes it the 2nd objective to provide the manufacturing method of the photoelectric conversion apparatus which can manufacture the photoelectric conversion apparatus which has a tandem structure with improved photoelectric conversion efficiency by a simple method.
  • the present invention provides a photoelectric conversion device having a single structure including a pin-type photoelectric conversion unit made of a crystalline silicon-based thin film, improving power generation efficiency in a long wavelength region and improving photoelectric conversion efficiency.
  • Third purpose Moreover, this invention makes it the 4th objective to provide the manufacturing method of the photoelectric conversion apparatus which can manufacture the photoelectric conversion apparatus which has a single structure with improved photoelectric conversion efficiency by a simple method.
  • the photoelectric conversion device includes a substrate, a transparent conductive film formed on the substrate, a first p-type semiconductor layer, a first i-type semiconductor layer, and a first n-type semiconductor layer.
  • the thickness of the barrier layer is preferably in the range of 10 to 200 mm, where “1 mm” is “0.1 nm”.
  • a photoelectric conversion device manufacturing method comprising: preparing a substrate on which a transparent conductive film is formed; and forming a first p-type semiconductor layer constituting a first photoelectric conversion unit on the transparent conductive film, A first p-type semiconductor layer, which is a crystalline silicon-based thin film that forms a second photoelectric conversion unit on the first n-type semiconductor layer by sequentially forming an i-type semiconductor layer and a first n-type semiconductor layer. , A second i-type semiconductor layer is formed in order, a barrier layer that is an i-type semiconductor layer of an amorphous silicon thin film is formed on the second i-type semiconductor layer, and the second photoelectric conversion is formed on the barrier layer. A second n-type semiconductor layer, which is a crystalline silicon-based thin film constituting the unit, is formed.
  • a photoelectric conversion device includes a substrate, a transparent conductive film formed on the substrate, a third p-type semiconductor layer, a third i-type semiconductor layer that are crystalline silicon-based thin films, and A third n-type semiconductor layer; and a barrier layer that is an i-type semiconductor layer of an amorphous silicon thin film provided between the third i-type semiconductor layer and the third n-type semiconductor layer, and the transparent conductive film A third photoelectric conversion unit formed above.
  • the manufacturing method of the photoelectric conversion device is a crystalline silicon-based thin film that prepares a substrate on which a transparent conductive film is formed and constitutes a third photoelectric conversion unit on the transparent conductive film.
  • a third p-type semiconductor layer and a third i-type semiconductor layer are formed in order, a barrier layer that is an i-type semiconductor layer of an amorphous silicon thin film is formed on the third i-type semiconductor layer, and the barrier layer is formed on the barrier layer.
  • a third n-type semiconductor layer which is a crystalline silicon-based thin film constituting the third photoelectric conversion unit is formed.
  • a photoelectric conversion device includes a substrate, a transparent conductive film formed on the substrate, a fourth p-type semiconductor layer, a fourth i-type semiconductor layer, and a fourth n-type semiconductor layer.
  • a fourth photoelectric conversion unit formed on the transparent conductive film, a fifth p-type semiconductor layer, a fifth i-type semiconductor layer, and a fifth n-type semiconductor layer, and formed on the fourth photoelectric conversion unit.
  • the fifth i-type semiconductor layer is an amorphous silicon germanium-based thin film.
  • the sixth i-type semiconductor layer is preferably a microcrystalline silicon germanium-based thin film.
  • the thickness of the barrier layer is preferably in the range of 10 to 200 mm.
  • a method for manufacturing a photoelectric conversion device comprising: preparing a substrate on which a transparent conductive film is formed; and forming a fourth p-type semiconductor layer constituting a fourth photoelectric conversion unit on the transparent conductive film; A fourth i-type semiconductor layer and a fourth n-type semiconductor layer are formed in order, and a fifth p-type semiconductor layer, a fifth i-type semiconductor layer constituting a fifth photoelectric conversion unit are formed on the fourth n-type semiconductor layer; And a fifth n-type semiconductor layer, and a sixth p-type semiconductor layer and a sixth i-type semiconductor which are crystalline silicon-based thin films constituting the sixth photoelectric conversion unit on the fifth n-type semiconductor layer.
  • a barrier layer which is an i-type semiconductor layer of an amorphous silicon thin film is formed on the sixth i-type semiconductor layer, and the crystalline material constituting the sixth photoelectric conversion unit is formed on the barrier layer
  • first photoelectric conversion device In the photoelectric conversion device according to the first aspect of the present invention (hereinafter, also referred to as “first photoelectric conversion device”), between the second i-type semiconductor layer and the second n-type semiconductor layer made of a crystalline silicon-based thin film.
  • an i-type semiconductor layer made of an amorphous silicon-based thin film is disposed as a barrier layer. For this reason, the holes (holes) flowing back toward the second n-type semiconductor layer are reflected by the barrier layer toward the second p-type semiconductor layer, thereby improving the short-circuit current (Jsc) (hereinafter, Also referred to as “barrier layer function 1”).
  • the barrier layer increases the band gap of the microcrystalline cell and improves the open-circuit voltage (Voc) (hereinafter also referred to as “barrier layer function 2”). Therefore, in the photoelectric conversion device according to the first aspect of the present invention, a barrier layer is provided between an appropriate interlayer, that is, a second i-type semiconductor layer and a second n-type semiconductor layer made of a crystalline silicon-based thin film. Therefore, both Voc and Jsc described above are improved. Therefore, the power generation efficiency in the second photoelectric conversion unit can be improved. As a result, according to the present invention, a photoelectric conversion device having a tandem structure with improved photoelectric conversion efficiency can be provided.
  • the second p-type semiconductor layer made of a crystalline silicon-based thin film and the second i-type semiconductor layers are sequentially formed (first step), an i-type semiconductor layer (barrier layer) made of an amorphous silicon thin film is formed on the second i-type semiconductor layer (second step), and crystals are formed on the barrier layer.
  • a second n-type semiconductor layer made of a high-quality silicon thin film is formed (third step). The first step, the second step, and the third step are performed in order.
  • both Voc and Jsc can be increased by functions 1 and 2 of the barrier layer, and the power generation efficiency in the second photoelectric conversion unit is improved.
  • the photoelectric conversion device In the photoelectric conversion device according to the third aspect of the present invention (hereinafter, also referred to as “second photoelectric conversion device”), between the third i-type semiconductor layer and the third n-type semiconductor layer made of a crystalline silicon-based thin film.
  • an i-type semiconductor layer made of an amorphous silicon-based thin film is disposed as a barrier layer. For this reason, the holes that flow backward toward the third n-type semiconductor layer are reflected by the barrier layer toward the third p-type semiconductor layer, and Jsc can be improved (Function 1 of the barrier layer).
  • the barrier layer increases the band gap of the microcrystalline cell and improves Voc (barrier layer function 2).
  • the barrier layer is provided, both Voc and Jsc described above are improved. Therefore, power generation efficiency can be improved. As a result, according to the present invention, a photoelectric conversion device having a single structure with improved photoelectric conversion efficiency can be provided.
  • the third p-type semiconductor layer and the third p-type semiconductor layer made of a crystalline silicon-based thin film are used.
  • i-type semiconductor layers are sequentially formed (first step)
  • an i-type semiconductor layer (barrier layer) made of an amorphous silicon thin film is formed on the third i-type semiconductor layer (second step)
  • crystals are formed on the barrier layer.
  • Forming a third n-type semiconductor layer made of a high-quality silicon-based thin film (third step); The first step, the second step, and the third step are performed in order.
  • both Voc and Jsc can be increased by the functions 1 and 2 of the barrier layer, and the power generation efficiency is improved.
  • the photoelectric conversion device in the photoelectric conversion device according to the fifth aspect of the present invention (hereinafter also referred to as “third photoelectric conversion device”), between the sixth i-type semiconductor layer and the sixth n-type semiconductor layer made of a crystalline silicon-based thin film.
  • an i-type semiconductor layer made of an amorphous silicon-based thin film is disposed as a barrier layer. Therefore, holes that have flowed back toward the sixth n-type semiconductor layer are reflected by the barrier layer toward the sixth p-type semiconductor layer, and the short-circuit current (Jsc) can be improved (barrier layer). Function 1).
  • the barrier layer increases the band gap of the microcrystalline cell and improves the open circuit voltage (Voc) (barrier layer function 2).
  • a barrier layer is provided between an appropriate interlayer, that is, a sixth i-type semiconductor layer and a sixth n-type semiconductor layer made of a crystalline silicon-based thin film. Therefore, both Voc and Jsc described above are improved. Therefore, the power generation efficiency in the sixth photoelectric conversion unit can be improved. As a result, according to the present invention, a photoelectric conversion device having a triple structure with improved photoelectric conversion efficiency can be provided.
  • a sixth p-type semiconductor layer and a sixth p-type semiconductor layer made of a crystalline silicon-based thin film are used.
  • i-type semiconductor layers are sequentially formed (first step)
  • an i-type semiconductor layer (barrier layer) made of an amorphous silicon thin film is formed on the sixth i-type semiconductor layer (second step)
  • crystals are formed on the barrier layer.
  • a sixth n-type semiconductor layer made of a high-quality silicon-based thin film is formed (third step). The first step, the second step, and the third step are performed in order.
  • both Voc and Jsc can be increased by the functions 1 and 2 of the barrier layer, and the power generation efficiency in the sixth photoelectric conversion unit is improved.
  • FIG. 1 It is the schematic which shows the manufacturing system which manufactures the photoelectric conversion apparatus (3rd photoelectric conversion apparatus) which concerns on 3rd embodiment of this invention. It is a figure which shows a discharge curve about the photoelectric conversion apparatus produced in Example 1 and Comparative Example 1.
  • FIG. It is a figure which shows the relationship between a wavelength and electric power generation efficiency about the photoelectric conversion apparatus produced in Example 1 and Comparative Example 1.
  • FIG. It is a figure which shows the relationship between the thickness of a barrier layer, and photoelectric conversion efficiency (eta) about the photoelectric conversion apparatus produced in Example 2-7 and Comparative Example 2.
  • FIG. It is a figure which shows the relationship between the thickness of a barrier layer, and the short circuit current Jsc about the photoelectric conversion apparatus produced in Example 2-7 and Comparative Example 2.
  • FIG. 2-7 It is a figure which shows the relationship between the thickness of a barrier layer, and the open circuit voltage Voc about the photoelectric conversion apparatus produced in Example 2-7 and the comparative example 2.
  • FIG. It is a figure which shows the relationship between Ic / Ia and Jsc about the photoelectric conversion apparatus produced in Example 2-7 and Comparative Example 2.
  • FIG. It is a figure which shows the relationship between a wavelength and power generation efficiency about the photoelectric conversion apparatus of Example 8. It is a figure which shows the relationship between a wavelength and power generation efficiency about the photoelectric conversion apparatus of Example 9.
  • FIG. It is a figure which shows the relationship between a wavelength and power generation efficiency about the photoelectric conversion apparatus of Example 8 and Comparative Example 3.
  • FIG. 1 is a cross-sectional view showing the layer configuration of the photoelectric conversion device according to the first embodiment of the present invention.
  • the photoelectric conversion device 10A (10) of the first embodiment of the present invention the substrate 1 on which a transparent conductive film is formed is used, and the transparent conductive film 2 is formed on the first surface 1a of the substrate 1.
  • the transparent conductive film 2 is formed on the first surface 1a of the substrate 1.
  • the 1st photoelectric conversion unit 3 and the 2nd photoelectric conversion unit 4 are piled up in order.
  • the first photoelectric conversion unit 3 and the second photoelectric conversion unit 4 have a pin-type semiconductor stacked structure in which a p-type semiconductor layer, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer are stacked.
  • a back electrode 5 is formed on the second photoelectric conversion unit 4.
  • the substrate 1 is an insulating substrate having a light transmission property, and is made of, for example, an insulating material made of glass, transparent resin, etc., having excellent sunlight transmission properties and durability.
  • the substrate 1 includes a transparent conductive film 2.
  • a transparent conductive film 2 As a material of the transparent conductive film 2, for example, a light transmissive metal oxide such as ITO (indium tin oxide), SnO 2 , ZnO or the like is employed.
  • the transparent conductive film 2 is formed on the substrate 1 by vacuum deposition or sputtering.
  • this photoelectric conversion device 10 ⁇ / b> A (10) the sunlight S is incident on the second surface 1 b of the substrate 1 as indicated by the arrow in FIG. 1.
  • the first photoelectric conversion unit 3 includes a p-type semiconductor layer 31 (p layer, first p-type semiconductor layer), a substantially intrinsic i-type semiconductor layer 32 (i layer, amorphous silicon layer, first i Type semiconductor layer) and an n-type semiconductor layer 33 (n layer, first n-type semiconductor layer) are 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, for example, an amorphous (amorphous) silicon-based material.
  • the thickness of the p layer 31 is, for example, 80 mm
  • the thickness of the i layer 32 is, for example, 1800 mm
  • the thickness of the n layer 33 is, for example, 100 mm.
  • the p layer 31, i layer 32, and n layer 33 of the first photoelectric conversion unit 3 are formed in a plurality of plasma CVD reaction chambers. That is, in each of a plurality of different plasma CVD reaction chambers, one layer constituting the first photoelectric conversion unit 103 is formed.
  • the second photoelectric conversion unit 4 includes a p-type semiconductor layer 41 (p layer, second p-type semiconductor layer), a substantially intrinsic i-type semiconductor layer 42 (i layer, crystalline silicon layer, second i-type semiconductor layer). ), And an n-type semiconductor layer 43 (n-layer, second n-type semiconductor layer) are stacked. That is, the second photoelectric conversion unit 4 is formed by stacking 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.
  • the thickness of the p layer 41 is 150 mm
  • the thickness of the i layer 42 is 15000 mm, for example
  • the thickness of the n layer 43 is 300 mm, for example.
  • an i-type semiconductor layer made of an amorphous silicon thin film is interposed between the i layer 42 and the n layer 43. Is arranged as. For this reason, by the function of the barrier layer 45, the holes (holes) flowing back toward the n layer 43 are reflected toward the p layer 41, and the short circuit current (Jsc) can be improved. Further, the band gap of the microcrystalline cell is increased by the action of the barrier layer 45, and the open circuit voltage (Voc) can be improved.
  • both Voc and Jsc can be improved, and the power generation efficiency of the second photoelectric conversion unit 4 can be improved. it can.
  • it is possible to improve the photoelectric conversion efficiency in the entire photoelectric conversion device including the first photoelectric conversion unit and the second photoelectric conversion unit.
  • the thickness of the barrier layer 45 is preferably in the range of 10 to 200 mm, for example, 50 mm. It has been confirmed that the photoelectric conversion efficiency increases when the thickness of the barrier layer 45 is in the range of 0 to 200 mm. When the thickness of the barrier layer 45 is 50 mm or more, Jsc decreases, while Voc and fill factor (FF) increase. Thereby, the photoelectric conversion efficiency in the whole photoelectric conversion device having a tandem structure is improved.
  • the crystallization rate in the barrier layer 45 constituting 10A (10) is less than 1.0.
  • the crystallization rate means a value obtained by dividing Ic by Ia (hereinafter referred to as Ic / Ia), and is a value obtained by quantifying the mixing ratio of crystalline and amorphous.
  • the crystallization rate of the barrier layer 45 can be independently controlled regardless of the crystallization rate (Ic / Ia) of the i layer 42 of the microcrystalline cell. That is, by adopting such a layer structure, Jsc can be improved in the photoelectric conversion device 10 of the first embodiment.
  • the power generation efficiency in the long wavelength region is improved by the layer structure of the first embodiment, and the photoelectric conversion efficiency in the microcrystalline tandem thin film solar cell can be improved by about 1%.
  • the back electrode 5 is made of, for example, a conductive light reflecting film such as Ag (silver) or Al (aluminum).
  • the back electrode 5 is formed using, for example, a sputtering method or a vapor deposition method.
  • a laminated structure in which a layer made of a conductive oxide such as ITO, SnO 2 , or ZnO is formed between the n layer 43 of the second photoelectric conversion unit 4 and the back electrode 5. Can also be used.
  • the manufacturing method of the photoelectric conversion device 10A (10) having the above configuration includes a step of sequentially forming the p layer 31, the i layer 32, and the n layer 33 constituting the first photoelectric conversion unit 3, and the n layer 33 of the first photoelectric conversion unit 3.
  • the open circuit voltage (Voc) and the short circuit current (Jsc) can be improved by the function of the barrier layer described above.
  • the power generation efficiency of the two photoelectric conversion units 4 is improved, and the photoelectric conversion efficiency in the entire photoelectric conversion device including the first photoelectric conversion unit 3 and the second photoelectric conversion unit 4 is improved.
  • the manufacturing method of the first embodiment it is possible to easily manufacture the photoelectric conversion device 10 with improved photoelectric conversion efficiency.
  • a method for manufacturing a photoelectric conversion device having a tandem structure will be described in order.
  • an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared.
  • the p layer 31, the i layer 32, the n layer 33, and the p layer 41 are formed on the transparent conductive film 2.
  • a plurality of plasma CVD reaction chambers in which the p layer 31, the i layer 32, the n layer 33, and the p layer 41 are formed are different from each other.
  • one layer of the p layer 31, the i layer 32, the n layer 33, and the p layer 41 is formed, and the p layer 31 is formed by a plurality of plasma CVD reaction chambers connected in a row.
  • the i layer 32, the n layer 33, and the p layer 41 are sequentially formed. That is, the first intermediate product 10a of the photoelectric conversion device in which the p layer 41 constituting the second photoelectric conversion unit 4 is provided on the n layer 33 of the first photoelectric conversion unit 3 is obtained.
  • the p layer 31 is formed using plasma CVD in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 70 to 120 Pa
  • monosilane (SiH 4 ) is 300 sccm
  • diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 180 sccm
  • methane (CH 4 ) is set to 500 sccm.
  • a p-layer made of amorphous silicon (a-Si) 31 can be formed.
  • the i layer 32 is formed using plasma CVD in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 70 to 120 Pa
  • monosilane (SiH 4 ) is set to 1200 sccm as the reaction gas flow rate.
  • the i layer 32 made of amorphous silicon can be formed.
  • the n layer 33 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 70 to 120 Pa
  • the reaction gas flow rate is phosphine (PH Under the condition that 3 / H 2 ) is set to 200 sccm, the n layer 33 made of amorphous silicon can be formed.
  • the p layer 41 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is set to 100 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate.
  • diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 50 sccm
  • the p-layer 41 of microcrystalline silicon ( ⁇ c-Si) can be formed. .
  • the substrate 1 on which the p layer 31, i layer 32, n layer 33, and p layer 41 are formed as described above is taken out of the reaction chamber, and the p layer 41 is exposed to the atmosphere.
  • the i layer 42, the barrier layer 45, and the n layer 43 constituting the second photoelectric conversion unit 4 are formed on the p layer 41 exposed to the atmosphere in a single plasma CVD reaction chamber. It is formed. That is, 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 obtained.
  • the photoelectric conversion apparatus 10A (10) shown in FIG. 1 is obtained by forming the back surface electrode 5 on the n layer 43 of the second photoelectric conversion unit 4.
  • the i layer 42 is formed using a plasma CVD method in the same reaction chamber as that in which the n layer 43 is formed.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is 180 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate.
  • the i-layer 42 of microcrystalline silicon can be formed.
  • the barrier layer 45 is formed using a plasma CVD method in the same reaction chamber as the reaction chamber in which the i layer 42 is formed.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 70 to 120 Pa
  • monosilane (SiH 4 ) is set to 1200 sccm as the reaction gas flow rate.
  • the barrier layer 45 i-type semiconductor layer made of amorphous silicon can be formed.
  • the n layer 43 is formed using a plasma CVD method in the same reaction chamber as that in which the i layer 42 is formed.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is 180 sccm
  • phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas is set to 200 sccm, and the n-layer 43 of microcrystalline silicon can be formed.
  • the manufacturing system of the photoelectric conversion apparatus 10 in the first embodiment includes a so-called in-line type first film forming apparatus 60, an exposure apparatus 80 that exposes the p layer 41 to the atmosphere, and a so-called batch type second film forming apparatus 70.
  • the inline-type first film forming apparatus 60 has a configuration in which a plurality of film forming reaction chambers called chambers are linearly connected.
  • the p layer 31, the i layer 32, the n layer 33 of the first photoelectric conversion unit 3, and the p layer 41 of the second photoelectric conversion unit 4 are formed separately.
  • the exposure apparatus 80 exposes the substrate processed in the first film forming apparatus 60 to the atmosphere, and then moves the substrate to the second film forming apparatus 70.
  • the i layer 42, the barrier layer 45, and the n layer 43 of the second photoelectric conversion unit 4 are stacked in this order in the same film forming reaction chamber.
  • a plurality of substrates are collectively conveyed, and an i layer 42, a barrier layer 45, and an n layer 43 are sequentially formed in each of the plurality of substrates in the film formation reaction chamber. (Batch processing).
  • a load chamber 61 (L: Lord) to which a substrate is first loaded and a vacuum pump for reducing the internal pressure is connected is disposed.
  • a heating chamber that heats the substrate so that the substrate temperature reaches a certain temperature may be provided in the subsequent stage of the load chamber 61 according to the film forming process.
  • Connected to the load chamber 61 is a P layer deposition reaction chamber 62 for forming the p layer 31.
  • An I layer deposition reaction chamber 63 for forming the i layer 32 is connected to the P layer deposition reaction chamber 62.
  • An N layer deposition reaction chamber 64 for forming the n layer 33 is connected to the I layer deposition reaction chamber 63.
  • a P layer deposition reaction chamber 65 for forming the p layer 41 is connected to the N layer deposition reaction chamber 64.
  • an unload chamber 66 (UL: United) that returns the internal pressure from reduced pressure to atmospheric pressure and carries the substrate out of the first film deposition apparatus 60.
  • the plurality of reaction chambers 62, 63, 64, 65 described above are continuously arranged in a straight line.
  • the substrate is sequentially transferred to the reaction chambers 62, 63, 64, and 65, and a film forming process is performed in each reaction chamber.
  • an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared as shown in FIG. 2A.
  • the p layer 31, i layer 32, n layer 33, and second photoelectric conversion unit 4 of the first photoelectric conversion unit 3 are formed on the transparent conductive film 2 as shown in FIG. 2B.
  • the first intermediate product 10a of the photoelectric conversion device 10 provided with the p layer 41 is formed.
  • the second film forming apparatus 70 in the manufacturing system includes a load / unload chamber 71 (L / UL) and an IIN layer film formation reaction chamber 72 connected to the load / unload chamber 71.
  • the load / unload chamber 71 carries the first intermediate product 10 a of the photoelectric conversion apparatus processed in the first film formation apparatus 60 into the IIN layer film formation reaction chamber 72.
  • the load / unload chamber 71 reduces the internal pressure after the substrate is loaded into the load / unload chamber 71, or returns the internal pressure from the reduced pressure to the atmospheric pressure when the substrate is unloaded from the load / unload chamber 71.
  • the i layer 42, the barrier layer 45, and the n layer 43 of the second photoelectric conversion unit 4 are stacked in this order in the same deposition reaction chamber. Further, in such a film formation reaction chamber, a plurality of substrates are collectively conveyed, and an i layer 42, a barrier layer 45, and an n layer 43 are sequentially formed in each of the plurality of substrates in the film formation reaction chamber. (Batch processing). Therefore, the film formation process in the IIN layer film formation reaction chamber 72 is performed simultaneously on a plurality of substrates.
  • the second intermediate product 10 b of the photoelectric conversion device 10 in which the second photoelectric conversion unit 4 is provided is disposed on the first photoelectric conversion unit 3.
  • the I-layer film formation reaction chamber 63 includes four reaction chambers 63a, 63b, 63c, and 63d.
  • film forming processes are simultaneously performed on six substrates.
  • the p layer of the second photoelectric conversion unit 4 which is a crystalline photoelectric conversion device is formed on the n layer 33 of the first photoelectric conversion unit 3 which is an amorphous photoelectric conversion device.
  • 41 is formed in advance, and the i layer 42, the barrier layer 45, and the n layer 43 of the second photoelectric conversion unit 4 are formed on the p layer 41.
  • the barrier layer 45 is formed between the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 in the same film formation chamber (IIN layer film formation reaction chamber 72). Therefore, the photoelectric conversion device 10 having good characteristics can be obtained.
  • the i layer 42, the barrier layer 45, and the n layer 43 constituting the second photoelectric conversion unit 4 are formed on the p layer 41 exposed to the atmosphere.
  • OH radical plasma treatment OH radical plasma treatment
  • hydrogen plasma treatment it is desirable to expose the p layer 41 exposed in the atmosphere to plasma in an atmosphere containing hydrogen gas (hydrogen plasma treatment).
  • the OH radical plasma treatment there is a method in which an OH 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. Adopted. Further, after the OH radical plasma treatment, the i layer 42, the barrier layer 45, and the n layer 43 constituting the second photoelectric conversion unit 4 are formed in a reaction chamber different from the OH radical plasma treatment chamber. On the other hand, as the OH radical plasma treatment, the OH radical plasma treatment and the treatment for forming the i layer 42, the barrier layer 45, and the n layer 43 constituting the second photoelectric conversion unit 4 are continuously performed in the same reaction chamber. May be.
  • the respective layers are formed.
  • the impurity gas PH 3 remaining in the reaction chamber can be decomposed and removed. Therefore, even when the film formation process of the i layer 42, the barrier layer 45, and the n layer 43 of the second photoelectric conversion unit 4 is repeatedly performed in the same processing chamber, a good impurity profile is obtained and a good condition is obtained.
  • a photoelectric conversion device 10 made of a laminated thin film having power generation efficiency can be obtained.
  • CO 2 , CH 2 O 2, or a mixed gas composed of H 2 O and H 2 is used as a process gas.
  • a process gas desirable. That is, in order to generate OH radical-containing plasma, (CO 2 + H 2 ), (CH 2 O 2 + H 2 ), or (H 2 O + H 2 ) is allowed to flow between the electrodes in the processing chamber while flowing into the processing chamber. For example, it can be effectively generated by applying a high frequency such as 13.5 MHz, 27 MHz, or 40 MHz.
  • alcohols such as (HCOOCH 3 + H 2 ) and (CH 3 OH + H 2 ), and hydrocarbons containing oxygen such as formate esters may be used.
  • hydrocarbons containing oxygen such as formate esters
  • the n layer 33 in which the microcrystalline phase formed on the p layer 31 and the i layer 32 of the first photoelectric conversion unit 3 is dispersed in the amorphous crystalline phase is obtained without damaging the lower layer.
  • an effect of activating the surface of the p layer 41 formed on the n layer 33 is obtained. Therefore, the surface of the p layer 41 of the second photoelectric conversion unit 4 can be activated, and the crystals of the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 stacked on the p layer 41 are effective. Can be generated.
  • the second photoelectric conversion unit 4 is formed on a large-area substrate, a uniform crystallization rate distribution can be obtained. Even if the hydrogen plasma treatment is performed instead of the OH radical plasma treatment, the same effect as the OH radical plasma treatment can be obtained.
  • a layer in which microcrystalline silicon is dispersed in an amorphous silicon layer may be employed.
  • a layer in which microcrystalline silicon is dispersed in an amorphous silicon oxide layer may be employed.
  • a-SiO amorphous silicon oxide layer
  • the refractive index can be adjusted to be lower than that of an amorphous silicon semiconductor layer. . It is possible to improve 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 this light, in the layer in which microcrystalline silicon is dispersed in the amorphous silicon oxide layer (a-SiO), the second photoelectric conversion unit 4 is subjected to OH radical plasma treatment. Crystal growth nuclei of the i layer 42 and the n layer 43 are effectively generated. Therefore, a uniform crystallization rate distribution can be obtained even on a large-area substrate.
  • a crystalline silicon-based thin film may be formed as the n layer 33 constituting the first photoelectric conversion unit 3. That is, the crystalline n layer 33 and the p layer 41 of the crystalline second photoelectric conversion unit 4 are formed on the p layer 31 and the i layer 32 of the amorphous first photoelectric conversion unit 3. At this time, the crystalline n layer 33 formed on the p layer 31 and the i layer 32 and the p layer 41 of the second photoelectric conversion unit 4 are formed in the atmosphere after the p layer 31 and the i layer 32 are formed. It is desirable to form continuously without exposing.
  • the first photoelectric conversion unit 3 is exposed to the air atmosphere, and then the second photoelectric conversion unit 4 of the reaction chamber is exposed.
  • a method of forming the p layer 41, the i layer 42, and the n layer 43 is known. In this method, the i-layer 32 of the first photoelectric conversion unit 3 deteriorates due to the time, temperature, atmosphere, etc., the substrate is exposed to the air atmosphere, and the device performance is degraded.
  • the crystalline n layer 33 and the second photoelectric conversion unit 4 are not exposed to the air atmosphere.
  • the p layer 41 is continuously formed.
  • the surface of the p layer 41 is activated by performing an OH radical plasma treatment in a separate reaction chamber on the substrate on which the crystalline n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 are formed. As a result, crystal nuclei are generated. Subsequently, the i-layer 42 of the crystalline second photoelectric conversion unit 4 is laminated on the p-layer 41, thereby comprising a laminated thin film having a uniform crystallization rate distribution over a large area and good power generation efficiency. A photoelectric conversion device 10A (10) can be obtained. Such OH radical plasma treatment may be performed in the same reaction chamber as the reaction chamber in which the i layer 42 is formed.
  • FIG. 4 is a cross-sectional view showing a layer configuration of the photoelectric conversion device 10 manufactured by the manufacturing method according to the second embodiment.
  • the photoelectric conversion device having a tandem structure has been described.
  • the present invention is not limited to the tandem structure, and can also be applied to a photoelectric conversion device having a single structure.
  • a substrate 1 on which a transparent conductive film is formed is used, and the transparent conductive film 2 is the first surface of the substrate 1. It is formed on 1a.
  • a pin-type third photoelectric conversion unit 8 is formed on the transparent conductive film 2.
  • a p-type semiconductor layer 81 (p layer, third p-type semiconductor layer), a substantially intrinsic i-type semiconductor layer 82 (i layer, third i-type semiconductor layer), n-type Semiconductor layers 83 (n layer and third n-type semiconductor layer) are sequentially stacked.
  • the p layer 81, the i layer 82, and the n layer 83 constituting the third photoelectric conversion unit 8 are made of a crystalline silicon-based thin film. Further, an i layer made of an amorphous silicon thin film is disposed as a barrier layer 85 between the i layer 82 and the n layer 83.
  • the barrier layer 85 is provided as described above, holes that have flowed back toward the n layer 83 are directed toward the p layer 81 by the barrier layer 85. Reflected and the short circuit current (Jsc) can be improved.
  • the barrier layer 85 is provided, the band gap of the microcrystalline cell can be increased and the open circuit voltage (Voc) can be improved.
  • the manufacturing method of the photoelectric conversion device 10 ⁇ / b> B (10) includes a step of sequentially forming a p layer 81 and an i layer 82 constituting the third photoelectric conversion unit 8, and a barrier on the i layer 82 constituting the third photoelectric conversion unit 8. Forming a layer 85, and forming an n layer 83 constituting the third photoelectric conversion unit 8 on the barrier layer 85.
  • the method of forming each of the p layer 81, the i layer 82, the barrier layer 85, and the n layer 83 constituting the third photoelectric conversion unit 8 is the p constituting the second photoelectric conversion unit 4 in the first embodiment described above.
  • FIG. 5 is a cross-sectional view showing a layer configuration of a photoelectric conversion device 10C (10) manufactured by the manufacturing method according to the third embodiment.
  • the photoelectric conversion device 10 having a tandem structure or a single structure has been described.
  • the present invention is not limited to these structures, and is also applicable to a photoelectric conversion device having a triple structure. Is possible.
  • the photoelectric conversion device 10 ⁇ / b> C (10) uses a substrate 1 on which a transparent conductive film is formed.
  • the transparent conductive film 2 is formed on the first surface 1 a of the substrate 1. ing.
  • a fourth photoelectric conversion unit 110, a fifth photoelectric conversion unit 120, and a sixth photoelectric conversion unit 130 are sequentially stacked.
  • the fourth photoelectric conversion unit 110, the fifth photoelectric conversion unit 120, and the sixth photoelectric conversion unit 130 are a pin type in which a p-type semiconductor layer, a substantially intrinsic i-type semiconductor layer, and an n-type semiconductor layer are stacked. It has a semiconductor laminated structure.
  • the fourth photoelectric conversion unit 110 includes a p-type semiconductor layer 111 (p layer, fourth p-type semiconductor layer), a substantially intrinsic i-type semiconductor layer 112 (i layer, amorphous silicon layer, fourth i-type semiconductor). Layer) and an n-type semiconductor layer 113 (n-layer, fourth n-type semiconductor layer) are stacked. That is, the fourth photoelectric conversion unit 110 is formed by stacking the p layer 111, the i layer 112, and the n layer 113 in this order.
  • the fourth photoelectric conversion unit 110 is made of, for example, an amorphous (amorphous) silicon-based material.
  • the thickness of the p layer 111 is, for example, 80 mm
  • the thickness of the i layer 112 is, for example, 1000 mm
  • the thickness of the n layer 113 is, for example, 300 mm.
  • the p layer 111, the i layer 112, and the n layer 113 constituting the fourth photoelectric conversion unit 110 are formed in a plurality of plasma CVD reaction chambers. That is, in each of a plurality of plasma CVD reaction chambers different from each other, one layer constituting the fourth photoelectric conversion unit 110 is formed.
  • the fifth photoelectric conversion unit 120 includes a p-type semiconductor layer 121 (p layer, fifth p-type semiconductor layer), a substantially intrinsic i-type semiconductor layer 122 (i layer, crystalline silicon layer, fifth i-type semiconductor layer). ), An n-type semiconductor layer 123 (n layer, fifth n-type semiconductor layer) is stacked. That is, the fifth photoelectric conversion unit 120 is formed by stacking the p layer 121, the i layer 122, and the n layer 123 in this order.
  • the fifth photoelectric conversion unit 120 is made of a silicon-based material containing a crystalline material.
  • the i layer 122 of the fifth photoelectric conversion unit 120 is preferably made of an amorphous silicon germanium-based thin film.
  • the thickness of the p layer 121 is 200 mm
  • the thickness of the i layer 122 is 12000 mm, for example
  • the thickness of the n layer 123 is 300 mm, for example.
  • the sixth photoelectric conversion unit 130 includes a p-type semiconductor layer 131 (p layer, sixth p-type semiconductor layer), a substantially intrinsic i-type semiconductor layer 132 (i layer, crystalline silicon layer, sixth i-type semiconductor layer). ) And an n-type semiconductor layer 133 (n-layer, sixth n-type semiconductor layer) are stacked. That is, the sixth photoelectric conversion unit 130 is formed by stacking the p layer 131, the i layer 132, and the n layer 133 in this order.
  • the sixth photoelectric conversion unit 130 is made of a silicon-based material containing a crystalline material.
  • the i layer 132 of the sixth photoelectric conversion unit 130 is preferably made of a microcrystalline silicon germanium-based thin film ( ⁇ c-SiGe).
  • the thickness of the p layer 131 is 200 mm
  • the thickness of the i layer 132 is 15000 mm, for example
  • the thickness of the n layer 133 is 300 mm, for example.
  • the p layer 131, the i layer 132, and the n layer 133 are made of a crystalline silicon thin film, Between the n layer 133, an i-type semiconductor layer made of an amorphous silicon thin film is disposed as a barrier layer 135.
  • the barrier layer 135 is provided as described above, the holes that flow backward toward the n layer 133 are directed toward the p layer 131 by the barrier layer 135. Reflected and the short circuit current (Jsc) can be improved.
  • the barrier layer 135 is provided, the band gap of the microcrystalline cell can be increased and the open-circuit voltage (Voc) can be improved.
  • the thickness of the barrier layer 135 is preferably in the range of 10 to 200 mm, for example, 50 mm. It has been confirmed that the photoelectric conversion efficiency is increased when the thickness of the barrier layer 135 is in the range of 0 to 200 mm. When the thickness of the barrier layer 135 is 50 mm or more, Jsc decreases, while Voc and fill factor (FF) increase. Thereby, the photoelectric conversion efficiency in the whole photoelectric conversion device having a triple structure is improved.
  • the manufacturing method of the photoelectric conversion device 10C (10) of the third embodiment includes a step of sequentially forming the p layer 111, the i layer 112, and the n layer 113 constituting the fourth photoelectric conversion unit 110, and the fourth photoelectric conversion unit 110. Forming a p-layer 121, an i-layer 122, and an n-layer 123 constituting the fifth photoelectric conversion unit 120 in this order on the n-layer 113, and a sixth photoelectric conversion on the n-layer 123 of the fifth photoelectric conversion unit 120.
  • both Voc and Jsc can be increased by the function of the barrier layer described above, and the power generation in the sixth photoelectric conversion unit 130 is performed. Efficiency is improved.
  • a photoelectric conversion device having a triple structure with improved photoelectric conversion efficiency can be easily manufactured.
  • a method for manufacturing a photoelectric conversion device having a triple structure will be described in order.
  • an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared. Thereafter, the p layer 111, the i layer 112, and the n layer 113 are formed on the transparent conductive film 2.
  • a plurality of plasma CVD reaction chambers in which the p layer 111, the i layer 112, and the n layer 113 are formed are different from each other.
  • one layer of the p layer 111, the i layer 112, and the n layer 113 is formed in one plasma CVD reaction chamber, and the p layer 111, the i layer 112, And the n layer 113 are sequentially formed.
  • the p layer 111 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 70 to 120 Pa
  • monosilane (SiH 4 ) is 300 sccm
  • diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 180 sccm
  • methane (CH 4 ) is set to 500 sccm
  • the layer 111 can be formed.
  • the i layer 112 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 70 to 120 Pa
  • monosilane (SiH 4 ) is set to 1200 sccm as the reaction gas flow rate.
  • the i layer 112 made of amorphous silicon can be formed.
  • the n layer 113 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is 180 sccm
  • the phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas is set to 200 sccm
  • the n layer 113 made of microcrystalline silicon can be formed.
  • the p layer 121, the i layer 122, and the n layer 123 that constitute the fifth photoelectric conversion unit 120, and the p layer 131 that constitutes the sixth photoelectric conversion unit 130. are sequentially stacked.
  • a plurality of plasma CVD reaction chambers in which the p layer 121, the i layer 122, the n layer 123, and the p layer 131 are formed are different from each other.
  • one layer of the p layer 31, the i layer 32, the n layer 33, and the p layer 41 is formed, and a plurality of plasma CVD reaction chambers connected in a row form the p layer 121, An i layer 122, an n layer 123, and a p layer 131 are sequentially formed.
  • the p layer 121 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is set to 100 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate.
  • Is set to 25000 sccm
  • diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 50 sccm
  • the p-layer 121 made of microcrystalline silicon can be formed.
  • the i layer 122 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 80 Pa
  • monosilane (SiH 4 ) is 700 sccm
  • monogermane (GeH 4 ) as the reaction gas flow rate.
  • the i layer 122 made of microcrystalline silicon germanium ( ⁇ c-SiGe) can be formed under the condition that is set to 500 sccm.
  • the n layer 123 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is 180 sccm
  • phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas is set to 200 sccm, and the n-layer 123 of microcrystalline silicon can be formed.
  • the p layer 131 is formed using a plasma CVD method in a separate reaction chamber.
  • the substrate temperature is set to 180 to 200 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 500 to 900 Pa
  • monosilane (SiH 4 ) is set to 100 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate.
  • diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 50 sccm, and the p-layer 131 of microcrystalline silicon can be formed.
  • the substrate 1 on which the p layer 121, the i layer 122, the n layer 123, and the p layer 131 are formed as described above is taken out of the reaction chamber, and the p layer 131 is exposed to the atmosphere. Subsequently, the i layer 132, the barrier layer 135, and the n layer 133 constituting the sixth photoelectric conversion unit 130 are formed on the p layer 131 exposed in the atmosphere in a single plasma CVD reaction chamber.
  • the i layer 132 is formed using a plasma CVD method in the same reaction chamber as that in which the n layer 133 is formed.
  • the substrate temperature is set to 170 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 1600 Pa
  • the reaction gas flow rates are 1800 sccm for monosilane (SiH 4 ) and 18000 sccm for hydrogen (H 2 ).
  • the i layer 132 made of microcrystalline silicon can be formed.
  • the i layer 132 of the sixth photoelectric conversion unit 130 is formed of a microcrystalline silicon germanium ( ⁇ c-SiGe) -based thin film.
  • the i layer 132 is formed using a plasma CVD method in the same reaction chamber as that in which the n layer 133 is formed.
  • the substrate temperature is set to 170 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 1600 Pa
  • the reaction gas flow rate is 1500 sccm for monosilane (SiH 4 )
  • 300 sccm for monogermane
  • the i layer 132 made of microcrystalline silicon germanium ( ⁇ c-SiGe) can be formed under the condition that hydrogen (H 2 ) is set to 180000 sccm.
  • the barrier layer 135 is formed using a plasma CVD method in the same reaction chamber as that in which the i layer 132 is formed. For example, under the conditions where the substrate temperature is set to 170 to 190 ° C., the power supply frequency is set to 13.56 MHz, the pressure in the reaction chamber is set to 1200 Pa, and monosilane (SiH 4 ) is set to 4300 sccm as the reaction gas flow rate, A barrier layer 135 (i-type semiconductor layer) made of amorphous silicon can be formed.
  • the n layer 133 is formed by plasma CVD in the same reaction chamber as that in which the i layer 132 is formed.
  • the substrate temperature is set to 170 to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 1200 Pa
  • monosilane (SiH 4 ) is 720 sccm
  • hydrogen (H 2 ) is used as the reaction gas flow rate.
  • the n-layer 133 of microcrystalline silicon can be formed under the conditions of 108000 sccm and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 720 sccm.
  • the manufacturing system of the photoelectric conversion device 10 in the third embodiment is an exposure that exposes the so-called in-line third film forming device 160 and fourth film forming device 170 and the p layer 131 to the atmosphere.
  • An apparatus 190 and a so-called batch-type fifth film forming apparatus 180 are arranged in order.
  • the in-line type third film forming apparatus 160 has a configuration in which a plurality of film forming reaction chambers called chambers are linearly connected. In the third film forming apparatus 160, each of the p layer 111, the i layer 112, and the n layer 113 of the fourth photoelectric conversion unit 3 is formed separately.
  • the in-line type fourth film forming apparatus 170 has a configuration in which a plurality of film forming reaction chambers called chambers are linearly connected.
  • the p layer 121, the i layer 122, the n layer 123 of the fifth photoelectric conversion unit 3, and the p layer 131 of the sixth photoelectric conversion unit 130 are formed separately.
  • the exposure apparatus 190 exposes the substrate processed in the fourth film forming apparatus 170 to the atmosphere, and then moves the substrate to the fifth film forming apparatus 180.
  • the i layer 132, the barrier layer 135, and the n layer 133 in the sixth photoelectric conversion unit 130 are stacked in this order in the same film forming reaction chamber.
  • a plurality of substrates are collectively transferred into such a deposition reaction chamber, and an i layer 132, a barrier layer 135, and an n layer 133 are sequentially formed in each of the plurality of substrates in the deposition reaction chamber. (Batch processing).
  • a load chamber 161 (L: Lord) to which a substrate is first loaded and a vacuum pump for reducing the internal pressure is connected is disposed.
  • a heating chamber that heats the substrate so that the substrate temperature reaches a certain temperature may be provided in the subsequent stage of the load chamber 161 in accordance with the film forming process.
  • a P layer film formation reaction chamber 162 for forming the p layer 111 is connected to the load chamber 161.
  • An I layer deposition reaction chamber 163 for forming the i layer 112 is connected to the P layer deposition reaction chamber 162.
  • An N layer deposition reaction chamber 164 for forming the n layer 113 is connected to the I layer deposition reaction chamber 163.
  • the plurality of reaction chambers 162 and 163 described above are continuously arranged in a straight line.
  • the substrate is sequentially transferred to the reaction chambers 162, 163, 164, and 165, and film formation is performed in each reaction chamber.
  • an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared at a point A shown in FIG.
  • a photoelectric conversion device 10 ⁇ / b> C (a p-layer 111, an i-layer 112, and an n-layer 113 are sequentially provided on the transparent conductive film 2 formed on the insulating transparent substrate 1.
  • the first intermediate product 10) is arranged.
  • the P layer film formation reaction chamber 171 for forming the p layer 121 is connected to the N layer film formation reaction chamber 164.
  • An I-layer deposition reaction chamber 172 for forming the i layer 122 is connected to the P-layer deposition reaction chamber 171.
  • An N layer deposition reaction chamber 173 for forming the n layer 123 is connected to the I layer deposition reaction chamber 172.
  • a P layer deposition reaction chamber 174 for forming the p layer 131 is connected to the N layer deposition reaction chamber 173.
  • an unload chamber 175 (UL: United) that returns the internal pressure from reduced pressure to atmospheric pressure and carries the substrate out of the fourth film deposition apparatus 170.
  • the plurality of reaction chambers 172, 173, 174, and 175 described above are continuously arranged in a straight line between the P layer deposition reaction chamber 171 and the unload chamber 175.
  • the substrate is sequentially transferred to the reaction chambers 171, 172, 173, 174, and 175, and film formation is performed in each reaction chamber.
  • the photoelectric conversion device 10 ⁇ / b> C in which the p layer 121, the i layer 122, the n layer 123, and the p layer 131 of the fifth photoelectric conversion unit 120 are sequentially provided on the n layer 113.
  • the second intermediate product 10) is arranged.
  • the fifth film forming apparatus 180 in the manufacturing system includes a load / unload chamber 181 (L / UL) and an IIN layer film formation reaction chamber 182 connected to the load / unload chamber 181.
  • the load / unload chamber 181 carries the second intermediate product of the photoelectric conversion device processed in the fourth film formation apparatus 170 into the IIN layer film formation reaction chamber 182.
  • the load / unload chamber 181 reduces the internal pressure after the substrate is loaded into the load / unload chamber 181 or returns the internal pressure from the reduced pressure to the atmospheric pressure when the substrate is unloaded from the load / unload chamber 181.
  • the i layer 132, the barrier layer 135, and the n layer 133 of the sixth photoelectric conversion unit 130 are stacked in this order in the same deposition reaction chamber.
  • a plurality of substrates are collectively transferred into such a deposition reaction chamber, and an i layer 132, a barrier layer 135, and an n layer 133 are sequentially formed in each of the plurality of substrates in the deposition reaction chamber. (Batch processing). Therefore, the film formation process in the IIN layer film formation reaction chamber 182 is performed simultaneously on a plurality of substrates.
  • the third intermediate product of the photoelectric conversion device 10 provided with the sixth photoelectric conversion unit 130 is disposed on the fifth photoelectric conversion unit 120.
  • the I-layer deposition reaction chamber 163 includes four reaction chambers 163a, 163b, 163c, and 163d.
  • the I-layer film formation reaction chamber 172 includes four reaction chambers 172a, 172b, 172c, and 172d.
  • film forming processes are simultaneously performed on six substrates.
  • the p layer of the sixth photoelectric conversion unit 130 which is a crystalline photoelectric conversion device is formed on the n layer 123 of the fifth photoelectric conversion unit 120 which is an amorphous photoelectric conversion device.
  • 131 is formed in advance, and the i layer 132, the barrier layer 135, and the n layer 133 of the sixth photoelectric conversion unit 130 are formed on the p layer 131.
  • the barrier layer 135 is formed between the i layer 132 and the n layer 133 of the sixth photoelectric conversion unit 130 in the same film formation chamber (IIN layer film formation reaction chamber 182). Therefore, the photoelectric conversion device 10C (10) having favorable characteristics can be obtained.
  • i layer 132 on p layer 131 exposed in the atmosphere it is desirable to perform hydrogen plasma treatment on p layer 131 exposed in the atmosphere.
  • An n layer 133 in which phases are dispersed in an amorphous crystal phase is obtained. As a result, an effect of activating the surface of the p layer 131 formed on the n layer 133 is obtained.
  • the surface of the p layer 131 of the sixth photoelectric conversion unit 130 can be activated, and the crystal of the i layer 132 of the sixth photoelectric conversion unit 130 stacked on the p layer 131 can be effectively generated. Can do. Therefore, even when the sixth photoelectric conversion unit 130 is formed on a large-area substrate, a uniform crystallization rate distribution can be obtained.
  • both Voc and Jsc can be improved by the function of the barrier layer 135, and the photoelectric conversion efficiency is improved.
  • the manufacturing method of the third embodiment it is possible to easily manufacture the photoelectric conversion device 10C (10) with improved photoelectric conversion efficiency.
  • the substrate processed by the third film forming device 160 is exposed to the atmosphere, and then the substrate is moved to the fourth film forming device 170.
  • a device (not shown) may be provided as necessary.
  • Example 1 and Comparative Example 1 a photoelectric conversion device having a tandem structure was manufactured.
  • Examples 2 to 7 and Comparative Example 2 photoelectric conversion devices having a single structure were manufactured.
  • Examples 8 to 9 and Comparative Examples 3 to 4 photoelectric conversion devices having a triple structure were manufactured.
  • a photoelectric conversion device was manufactured using a substrate having a size of 1100 mm ⁇ 1400 mm.
  • Example 1 a photoelectric conversion device having a structure in which a first photoelectric conversion unit was formed on a substrate and a second photoelectric conversion unit was formed on the first photoelectric conversion unit was produced. Specifically, in Example 1, a p-layer made of an amorphous amorphous silicon-based thin film constituting the first photoelectric conversion unit, a buffer layer, an i-layer made of an amorphous amorphous silicon-based thin film, and an i-layer An n layer containing microcrystalline silicon and a p layer containing microcrystalline silicon constituting the second photoelectric conversion unit were sequentially stacked on the substrate using a plurality of different deposition chambers.
  • the p layer of the second photoelectric conversion unit was exposed to the atmosphere.
  • hydrogen plasma treatment was performed on the p layer of the second photoelectric conversion unit using hydrogen (H 2 ) as a process gas.
  • an i layer made of microcrystalline silicon, an i layer (barrier layer) made of an amorphous amorphous silicon thin film, and an n layer made of microcrystalline silicon constituting the second photoelectric conversion unit were formed.
  • 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 using a plasma CVD method in individual reaction chambers.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 110 Pa
  • monosilane (SiH 4 ) is 300 sccm as a reaction gas flow rate.
  • the film is formed to a thickness of 80 mm under the conditions that hydrogen (H 2 ) is set to 2300 sccm, diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 180 sccm, and methane (CH 4 ) is set to 500 sccm. did.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 110 Pa
  • monosilane (SiH 4 ) is 300 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate. ) was set to 2300 sccm and methane (CH 4 ) was set to 100 sccm.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 80 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • the film was formed to a thickness of 1800 mm under the condition set to 1200 sccm.
  • the n layer of the first photoelectric conversion unit has a substrate temperature set to 180 ° C., a power supply frequency set to 13.56 MHz, a reaction chamber pressure set to 700 Pa, and monosilane (SiH 4 ) as a reaction gas flow rate.
  • the film was formed to a thickness of 100 ⁇ under the conditions of 180 sccm, hydrogen (H 2 ) of 27000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is set as the reaction gas flow rate.
  • the film was formed to a thickness of 150 mm under the conditions of 100 sccm, hydrogen (H 2 ) 25000 sccm, and diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas at 50 sccm.
  • the p layer of the second photoelectric conversion unit was exposed to the atmosphere here.
  • plasma treatment was performed under the conditions that the substrate temperature was set to 190 ° C., the power supply frequency was set to 13.56 MHz, the pressure in the reaction chamber was set to 700 Pa, and H 2 was set to 1000 sccm as the process gas. did. That is, H 2 gas in a plasma state was exposed to the p layer.
  • the substrate temperature is set to 170 ° C.
  • the applied RF power is set to 550 W
  • the pressure in the reaction chamber is set to 1200 Pa
  • monosilane (SiH 4 ) is 40 sccm as the reaction gas flow rate.
  • hydrogen (H 2 ) was set to 2800 sccm
  • a film having a thickness of 15000 mm was formed. At this time, the film formation rate was 262 Km / min.
  • the substrate temperature is set to 170 ° C.
  • the applied RF power is set to 40 W
  • the reaction chamber pressure is set to 40 Pa
  • monosilane (SiH 4 ) is 300 sccm as the reaction gas flow rate.
  • the film was formed to a film thickness of 50 mm under the conditions set as above. The film formation rate at this time was 141 ⁇ / min.
  • the substrate temperature is set to 170 ° C.
  • the applied RF power is set to 1000 W
  • the reaction chamber pressure is set to 800 Pa
  • monosilane (SiH 4 ) is 20 sccm as the reaction gas flow rate.
  • a film having a thickness of 300 mm was formed under the conditions where hydrogen (H 2 ) was set to 2000 sccm and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas was set to 15 sccm. At this time, the film formation rate was 174 ⁇ / min.
  • Comparative Example 1 a barrier layer was not formed between the i layer and the n layer of the second photoelectric conversion unit, and a photoelectric conversion device having a tandem structure was produced in the same manner as in Example 1. Specifically, the p layer, the buffer layer, the i layer, the n layer formed on the i layer, and the p layer constituting the second photoelectric conversion unit constituting the first photoelectric conversion unit are formed into a plurality of different films. The layers were sequentially stacked on the substrate using a chamber. Thereafter, the p layer of the second photoelectric conversion unit was exposed to the atmosphere. Next, hydrogen plasma treatment was performed on the p layer of the second photoelectric conversion unit. Then, i layer and n layer which comprise a 2nd photoelectric conversion unit were formed.
  • Example 2 the p layer containing microcrystalline silicon constituting the third photoelectric conversion unit on the substrate, the i layer made of microcrystalline silicon, the i layer made of an amorphous silicon thin film (barrier layer), A photoelectric conversion device having a structure in which an n layer made of microcrystalline silicon was formed was manufactured.
  • the p layer, i layer, barrier layer, and n layer of the third photoelectric conversion unit were formed using the plasma CVD method in the same film formation chamber.
  • the p layer of the third photoelectric conversion unit has a substrate temperature set to 180 ° C., a power supply frequency set to 13.56 MHz, a reaction chamber pressure set to 700 Pa, and monosilane (SiH 4 ) as a reaction gas flow rate of 100 sccm,
  • the film was formed to a thickness of 150 mm under the conditions that hydrogen (H 2 ) was set to 25000 sccm and diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas was set to 50 sccm.
  • the substrate temperature is set to 170 ° C.
  • the applied RF power is set to 550 W
  • the reaction chamber pressure is set to 1200 Pa
  • monosilane (SiH 4 ) is 40 sccm as the reaction gas flow rate.
  • hydrogen (H 2 ) was set to 2800 sccm
  • a film having a thickness of 15000 mm was formed. At this time, the film formation rate was 262 Km / min.
  • the substrate temperature is set to 170 ° C.
  • the applied RF power is set to 40 W
  • the reaction chamber pressure is set to 40 Pa
  • monosilane (SiH 4 ) is 300 sccm as the reaction gas flow rate.
  • the film was formed to a thickness of 10 mm under the conditions set as above. The film formation rate at this time was 141 ⁇ / min.
  • the substrate temperature is set to 170 ° C.
  • the applied RF power is set to 1000 W
  • the reaction chamber pressure is set to 800 Pa
  • monosilane (SiH 4 ) is 20 sccm as the reaction gas flow rate.
  • a film having a thickness of 300 mm was formed under the conditions where hydrogen (H 2 ) was set to 2000 sccm and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas was set to 15 sccm. At this time, the film formation rate was 174 ⁇ / min.
  • the photoelectric conversion devices in Examples 3 to 7 are microcrystalline photoelectric conversion devices having a single structure that is the same as the structure of Example 2 except for the thickness of the barrier layer. Moreover, the thickness of the barrier layer in Example 3 is 20 mm. The thickness of the barrier layer in Example 4 is 50 mm. The thickness of the barrier layer in Example 5 is 100 mm. The thickness of the barrier layer in Example 6 is 150 mm. The thickness of the barrier layer in Example 7 is 200 mm.
  • Comparative Example 2 a barrier layer was not formed between the i layer and the n layer of the third photoelectric conversion unit, and a microcrystalline photoelectric conversion device having a single structure was produced in the same manner as in Example 2. did. That is, a p-layer containing microcrystalline silicon is formed on a substrate, and then an i layer made of microcrystalline silicon and an n layer made of microcrystalline silicon are sequentially formed to form the photoelectric conversion device of Comparative Example 2. Has been.
  • Example 8 the fourth photoelectric conversion unit is formed on the substrate, the fifth photoelectric conversion unit is formed on the fourth photoelectric conversion unit, and the sixth photoelectric conversion unit is formed on the fifth photoelectric conversion unit.
  • a photoelectric conversion device having the above structure was manufactured.
  • the fourth photoelectric conversion unit is composed of an amorphous amorphous silicon carbide (a-SiC) thin film, a p layer, a buffer layer, and an amorphous amorphous silicon thin film.
  • a-SiC amorphous amorphous silicon carbide
  • An i layer and an n layer containing microcrystalline silicon formed on the i layer were sequentially stacked on the substrate using a plurality of different deposition chambers. Thereafter, the n layer of the fourth photoelectric conversion unit was exposed to the atmosphere.
  • Example 8 the p layer, i layer, n layer of the fourth photoelectric conversion unit, the p layer, i layer, n layer of the fifth photoelectric conversion unit, and the p layer of the sixth photoelectric conversion unit are different from each other.
  • the layers were sequentially stacked on the substrate using a plasma CVD method in a film formation chamber.
  • the i layer of the sixth photoelectric conversion unit, the i layer (barrier layer) made of an amorphous amorphous silicon thin film, and the n layer were formed by plasma CVD in the same film formation chamber.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 110 Pa
  • monosilane (SiH 4 ) is 300 sccm as a reaction gas flow rate
  • the film is formed to a thickness of 80 mm under the conditions that hydrogen (H 2 ) is set to 2300 sccm, diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 180 sccm, and methane (CH 4 ) is set to 500 sccm. did.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 110 Pa
  • monosilane (SiH 4 ) is 300 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate. ) was set to 2300 sccm
  • methane (CH 4 ) was set to 100 sccm.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 80 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • the film was formed to a thickness of 1000 mm under the condition set to 1200 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film having a thickness of 300 mm was formed under the conditions of 180 sccm, hydrogen (H 2 ) of 27000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • the n layer of the fourth photoelectric conversion unit was exposed to the atmosphere here.
  • plasma treatment was performed under the conditions that the substrate temperature was set to 190 ° C., the power supply frequency was set to 13.56 MHz, the pressure in the reaction chamber was set to 700 Pa, and H 2 was set to 1000 sccm as the process gas. did.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • hydrogen (H 2) is 25000Sccm
  • diborane hydrogen is used as the diluent gas (B 2 H 6 / H 2 ) was set to 50 sccm, and formed into a film having a thickness of 200 ⁇ .
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 80 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • the film was formed to a thickness of 1200 mm under the conditions that 700 sccm and monogermane (GeH 4 ) were set to 500 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film having a thickness of 300 mm was formed under the conditions of 180 sccm, hydrogen (H 2 ) of 27000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • the reaction gas flow rate is monosilane (SiH 4 ).
  • hydrogen (H 2) is 25000Sccm
  • diborane hydrogen is used as the diluent gas (B 2 H 6 / H 2 ) was set to 50 sccm, and formed into a film having a thickness of 200 ⁇ .
  • the p layer of the sixth photoelectric conversion unit was exposed to the atmosphere here.
  • the reaction chamber pressure is 1200 Pa
  • H 2 as a process gas in the conditions set in the 4000 sccm
  • facilities plasma treatment did.
  • the substrate temperature is set to 170 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 1600 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • the film was formed to a thickness of 15000 mm under the conditions of 1800 sccm and hydrogen (H 2 ) of 180000 sccm.
  • the barrier layer of the sixth photoelectric conversion unit has a substrate temperature set at 170 ° C., a power supply frequency set at 13.56 MHz, a reaction chamber pressure set at 1200 Pa, and monosilane (SiH 4 ) as a reaction gas flow rate.
  • the film was formed to a thickness of 100 mm under the condition set to 4300 sccm.
  • the substrate temperature is set to 170 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 1200 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film was formed to a thickness of 300 mm under the conditions of 720 sccm, hydrogen (H 2 ) of 108000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 720 sccm.
  • Comparative Example 3 a barrier layer was not formed between the i layer and the n layer of the sixth photoelectric conversion unit, and a photoelectric conversion device having a triple structure was produced in the same manner as in Example 8. Specifically, a p layer, a buffer layer, an i layer, and an n layer formed on the i layer constituting the fourth photoelectric conversion unit are sequentially stacked on the substrate using a plurality of different film forming chambers. . Thereafter, the n layer of the fourth photoelectric conversion unit was exposed to the atmosphere. Next, hydrogen plasma treatment was performed on the n layer of the fourth photoelectric conversion unit.
  • the p-layer, i-layer, and n-layer constituting the fifth photoelectric conversion unit, and the p-layer constituting the sixth photoelectric conversion unit were sequentially stacked on the substrate using a plurality of different film formation chambers. . Thereafter, the p layer of the sixth photoelectric conversion unit was exposed to the atmosphere. Next, hydrogen plasma treatment was performed on the p layer of the sixth photoelectric conversion unit. Then, i layer and n layer which comprise a 6th photoelectric conversion unit were formed.
  • Example 9 the fourth photoelectric conversion unit is formed on the substrate, the fifth photoelectric conversion unit is formed on the fourth photoelectric conversion unit, and the sixth photoelectric conversion unit is formed on the fifth photoelectric conversion unit.
  • a photoelectric conversion device having the above structure was manufactured.
  • the fourth photoelectric conversion unit is composed of an amorphous amorphous silicon carbide (a-SiC) thin film, a p layer, a buffer layer, and an amorphous amorphous silicon thin film.
  • a-SiC amorphous amorphous silicon carbide
  • An i layer and an n layer containing microcrystalline silicon formed on the i layer were sequentially stacked on the substrate using a plurality of different deposition chambers. Thereafter, the n layer of the fourth photoelectric conversion unit was exposed to the atmosphere.
  • hydrogen plasma treatment was performed on the n layer of the fourth photoelectric conversion unit using hydrogen (H 2 ) as a process gas. Thereafter, an i layer composed of an amorphous silicon germanium (a-SiGe) thin film constituting the fifth photoelectric conversion unit, an n layer formed on the i layer and containing microcrystalline silicon, and a microcrystalline silicon constituting the sixth photoelectric conversion unit The p layer containing was sequentially laminated on the substrate using a plurality of different film formation chambers. Thereafter, the p layer of the sixth photoelectric conversion unit was exposed to the atmosphere. Next, hydrogen plasma treatment was performed on the p layer of the sixth photoelectric conversion unit using hydrogen (H 2 ) as a process gas.
  • hydrogen (H 2 ) hydrogen
  • Example 9 the p layer, i layer, n layer of the fourth photoelectric conversion unit, the p layer, i layer, n layer of the fifth photoelectric conversion unit, and the p layer of the sixth photoelectric conversion unit are different from each other.
  • the layers were sequentially stacked on the substrate using a plasma CVD method in a film formation chamber.
  • the i layer of the sixth photoelectric conversion unit, the i layer (barrier layer) made of an amorphous amorphous silicon thin film, and the n layer were formed by plasma CVD in the same film formation chamber.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 110 Pa
  • monosilane (SiH 4 ) is 300 sccm as a reaction gas flow rate
  • the film is formed to a thickness of 80 mm under the conditions that hydrogen (H 2 ) is set to 2300 sccm, diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas is set to 180 sccm, and methane (CH 4 ) is set to 500 sccm. did.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the pressure in the reaction chamber is set to 110 Pa
  • monosilane (SiH 4 ) is 300 sccm
  • hydrogen (H 2 ) as the reaction gas flow rate. ) was set to 2300 sccm
  • methane (CH 4 ) was set to 100 sccm.
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 80 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • the film was formed to a thickness of 1000 mm under the condition set to 1200 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film having a thickness of 300 mm was formed under the conditions of 180 sccm, hydrogen (H 2 ) of 27000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • the n layer of the fourth photoelectric conversion unit was exposed to the atmosphere here.
  • plasma treatment was performed under the conditions that the substrate temperature was set to 190 ° C., the power supply frequency was set to 13.56 MHz, the pressure in the reaction chamber was set to 700 Pa, and H 2 was set to 1000 sccm as the process gas. did.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • hydrogen (H 2) is 25000Sccm
  • diborane hydrogen is used as the diluent gas (B 2 H 6 / H 2 ) was set to 50 sccm, and formed into a film having a thickness of 200 ⁇ .
  • the substrate temperature is set to 190 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 80 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • the film was formed to a thickness of 1200 mm under the conditions that 700 sccm and monogermane (GeH 4 ) were set to 500 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film having a thickness of 300 mm was formed under the conditions of 180 sccm, hydrogen (H 2 ) of 27000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 700 Pa
  • the reaction gas flow rate is monosilane (SiH 4 ).
  • hydrogen (H 2) is 25000Sccm
  • diborane hydrogen is used as the diluent gas (B 2 H 6 / H 2 ) was set to 50 sccm, and formed into a film having a thickness of 200 ⁇ .
  • the p layer of the sixth photoelectric conversion unit was exposed to the atmosphere here.
  • the reaction chamber pressure is 1200 Pa
  • H 2 as a process gas in the conditions set in the 4000 sccm
  • facilities plasma treatment did.
  • the substrate temperature is set to 170 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 1600 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film having a thickness of 9000 mm was formed under the conditions of 1500 sccm, monogermane (GeH 4 ) of 300 sccm, and hydrogen (H 2 ) of 180,000 sccm.
  • the barrier layer of the sixth photoelectric conversion unit has a substrate temperature set at 170 ° C., a power supply frequency set at 13.56 MHz, a reaction chamber pressure set at 1200 Pa, and monosilane (SiH 4 ) as a reaction gas flow rate.
  • the film was formed to a thickness of 100 mm under the condition set to 4300 sccm.
  • the substrate temperature is set to 180 ° C.
  • the power supply frequency is set to 13.56 MHz
  • the reaction chamber pressure is set to 1200 Pa
  • monosilane (SiH 4 ) is used as the reaction gas flow rate.
  • a film was formed to a thickness of 300 mm under the conditions of 720 sccm, hydrogen (H 2 ) of 108000 sccm, and phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 720 sccm.
  • a barrier layer was not formed between the i layer and the n layer of the sixth photoelectric conversion unit, and a photoelectric conversion device having a triple structure was produced in the same manner as in Example 9. Specifically, a p layer, a buffer layer, an i layer, and an n layer formed on the i layer constituting the fourth photoelectric conversion unit are sequentially stacked on the substrate using a plurality of different film forming chambers. . Thereafter, the n layer of the fourth photoelectric conversion unit was exposed to the atmosphere. Next, hydrogen plasma treatment was performed on the n layer of the fourth photoelectric conversion unit.
  • the p-layer, i-layer, and n-layer constituting the fifth photoelectric conversion unit, and the p-layer constituting the sixth photoelectric conversion unit were sequentially stacked on the substrate using a plurality of different film formation chambers. . Thereafter, the p layer of the sixth photoelectric conversion unit was exposed to the atmosphere. Next, hydrogen plasma treatment was performed on the p layer of the sixth photoelectric conversion unit. Then, i layer and n layer which comprise a 6th photoelectric conversion unit were formed.
  • Table 1 shows experimental results regarding a photoelectric conversion device having a tandem structure.
  • the photoelectric conversion devices of Example 1 and Comparative Example 1 were irradiated with AM 1.5 light at a light amount of 100 mW / cm 2 and output characteristics at 25 ° C. as photoelectric characteristics ( ⁇ ), short-circuit current (Jsc), open-circuit voltage (Voc) and fill factor (FF) were measured.
  • the results are shown in Table 1.
  • a discharge curve is shown in FIG. 7, and the relationship between a wavelength and electric power generation efficiency is shown in FIG.
  • FIGS. 9 to 11 are a graph in which ⁇ , Jsc, and Voc (vertical axis) are plotted with respect to the thickness of the barrier layer (horizontal axis).
  • the effect of increasing the photoelectric conversion efficiency ⁇ is confirmed when the thickness of the barrier layer is in the range of 10 to 200 mm.
  • the thickness of the barrier layer is 50 mm or more, Jsc decreases, but Voc and FF increase. This shows that ⁇ is improved.
  • the photoelectric conversion efficiency ⁇ is substantially constant when the thickness of the barrier layer is 200 mm or more, and it has not been confirmed that the photoelectric conversion efficiency ⁇ is further improved.
  • the thickness of the barrier layer may be 200 mm or more, but is preferably 200 mm or less in consideration of the film formation efficiency. If the photoelectric conversion device is evaluated based on Jsc, the thickness of the barrier layer is preferably 10 to 200 mm, and particularly preferably 20 to 100 mm.
  • the intensity of Raman scattered light observed with a laser Raman microscope will be described.
  • the intensity of Raman scattered light caused by the amorphous phase dispersed in the i layer made of microcrystals is represented by Ia
  • the intensity of Raman scattered light caused by the microcrystalline phase dispersed in the i layer made of microcrystals is expressed as Ia.
  • Ic the crystallization rate in the i layer composed of microcrystals constituting the photoelectric conversion device
  • Ic / Ia the crystallization ratio in the i layer composed of microcrystals constituting the photoelectric conversion device.
  • FIG. 12 shows the relationship between the crystallization ratio Ic / Ia and the Jsc of the photoelectric conversion device.
  • the solid line indicates the result in the photoelectric conversion device provided with the barrier layer of the present invention
  • the broken line indicates the result in the photoelectric conversion device not provided with the barrier layer of the present invention.
  • Jsc can be improved by the layer structure of the present invention in which a barrier layer is provided regardless of the crystallization rate (Ic / Ia) of the i-layer made of microcrystals. I understand. Therefore, Ic / Ia increases and Jsc increases as the microcrystalline layer manufacturing conditions are changed. However, Ic / Ia of the structure (microcrystalline layer) provided with the barrier layer and the barrier layer are provided.
  • the Jsc in the structure with the barrier layer can be increased. Even if Ic / Ia varies, Jsc in the structure provided with the barrier layer can be increased. That is, the effect obtained by the barrier layer (increase in Jsc) is not related to the increase in Ic / Ia.
  • the present invention is widely applicable to photoelectric conversion devices and methods for manufacturing photoelectric conversion devices.

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Abstract

Un dispositif de conversion photoélectrique (10) est composé de : un substrat (1) ; un film conducteur transparent (2) formé sur le substrat (1) ; une première unité de conversion photoélectrique (3) qui est composée d'une première couche semiconductrice de type p (31), d'une première couche semiconductrice de type i (32) et d'une première couche semiconductrice de type n (33) et qui est formée sur le film conducteur transparent (2) ; et une seconde unité de conversion photoélectrique (4) qui est composée d'une seconde couche semiconductrice de type p (41), c'est-à-dire un film mince de silicium cristallin, d'une seconde couche semiconductrice de type i (42), d'une seconde couche semiconductrice de type n (43) et d'une couche barrière (45), c'est-à-dire une couche semiconductrice de type i composée d'un film mince de silicium amorphe placé entre la seconde couche semiconductrice de type i (42) et la seconde couche semiconductrice de type n (43), et qui est formée sur la première unité de conversion photoélectrique (3).
PCT/JP2010/003997 2009-06-18 2010-06-16 Dispositif de conversion photoélectrique et procédé de production d'un dispositif de conversion photoélectrique Ceased WO2010146846A1 (fr)

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Cited By (1)

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WO2012057201A1 (fr) * 2010-10-28 2012-05-03 株式会社アルバック Dispositif de conversion photoélectrique et procédé de fabrication d'un dispositif de conversion photoélectrique

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JP2002198551A (ja) * 2000-12-27 2002-07-12 Mitsubishi Heavy Ind Ltd 光電変換素子とそれを用いた光電変換装置及び光電変換素子の製造方法
JP2002343991A (ja) * 2001-05-16 2002-11-29 Fuji Electric Co Ltd 非単結晶太陽電池
JP2003051604A (ja) * 2001-08-03 2003-02-21 Sanyo Electric Co Ltd 光起電力素子

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JPH1187742A (ja) * 1997-09-01 1999-03-30 Kanegafuchi Chem Ind Co Ltd シリコン系薄膜光電変換装置
JP2002198551A (ja) * 2000-12-27 2002-07-12 Mitsubishi Heavy Ind Ltd 光電変換素子とそれを用いた光電変換装置及び光電変換素子の製造方法
JP2002343991A (ja) * 2001-05-16 2002-11-29 Fuji Electric Co Ltd 非単結晶太陽電池
JP2003051604A (ja) * 2001-08-03 2003-02-21 Sanyo Electric Co Ltd 光起電力素子

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012057201A1 (fr) * 2010-10-28 2012-05-03 株式会社アルバック Dispositif de conversion photoélectrique et procédé de fabrication d'un dispositif de conversion photoélectrique

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