WO2011125878A1 - 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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WO2011125878A1
WO2011125878A1 PCT/JP2011/058289 JP2011058289W WO2011125878A1 WO 2011125878 A1 WO2011125878 A1 WO 2011125878A1 JP 2011058289 W JP2011058289 W JP 2011058289W WO 2011125878 A1 WO2011125878 A1 WO 2011125878A1
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photoelectric conversion
layer
semiconductor layer
conversion unit
type semiconductor
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Japanese (ja)
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宏紀 茶谷
伸 浅利
征典 橋本
伸一 朝比奈
健一 今北
祥二 佐見津
忠正 小林
雅文 若井
喜信 植
貞次 若松
一也 斎藤
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株式会社アルバック
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Priority to JP2012509593A priority Critical patent/JPWO2011125878A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
    • H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0368—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors
    • H01L31/03682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors including only elements of Group IV of the Periodic Table
    • H01L31/03685—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors including only elements of Group IV of the Periodic Table including microcrystalline silicon, uc-Si
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0376—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
    • H01L31/03762—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors including only elements of Group IV of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H01L31/076—Multiple junction or tandem solar cells
    • H—ELECTRICITY
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/545—Microcrystalline silicon PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion device and a method for manufacturing the photoelectric conversion device.
  • This application claims priority based on Japanese Patent Application No. 2010-086181 filed in Japan on April 2, 2010, the contents of which are incorporated herein by reference.
  • 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 as a structure for improving the conversion efficiency of the photoelectric conversion device.
  • a tandem photoelectric conversion device 200 as shown in FIG. 7 is known.
  • an insulating transparent substrate 201 provided with a transparent conductive film 202 is used.
  • a pin-type first photoelectric conversion unit 203 obtained by sequentially stacking a p-type semiconductor layer 231, an i-type silicon layer (amorphous silicon layer) 232, and an n-type semiconductor layer 233 on the transparent conductive film 202. Is formed.
  • a pin-type second photoelectric conversion unit obtained by sequentially stacking a p-type semiconductor layer 241, an i-type silicon layer (crystalline silicon layer) 242, and an n-type semiconductor layer 243 on the first photoelectric conversion unit 203. 204 is formed. Further, a back electrode 205 is formed on the second photoelectric conversion unit 204.
  • a manufacturing method disclosed in Patent Document 1 is known.
  • the pin type first photoelectric conversion unit made of an amorphous silicon thin film and the pin type second photoelectric conversion unit made of a crystalline silicon thin film have the wavelength and The relationship with power generation efficiency is shown in FIG. As shown in FIG. 8, the pin-type second photoelectric conversion unit made of a crystalline silicon-based thin film has low power generation efficiency in the long wavelength region, and it is difficult to improve the photoelectric conversion efficiency of the entire device. It was.
  • the present invention has been made in view of the above circumstances, and in a tandem photoelectric conversion device, the power generation efficiency in the long wavelength region of a pin-type second photoelectric conversion unit made of a crystalline silicon-based thin film is improved.
  • a first object is to provide a tandem photoelectric conversion device with improved efficiency.
  • a second object of the present invention is to provide a method for manufacturing a photoelectric conversion device capable of manufacturing a photoelectric conversion device having a tandem structure with improved photoelectric conversion efficiency by a simple method.
  • the present invention also relates to 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.
  • a third object is to provide a device. Furthermore, this invention makes it the 4th objective to provide the manufacturing method of the photoelectric conversion apparatus which can manufacture the photoelectric conversion apparatus of the single structure which improved the photoelectric conversion efficiency by a simple method.
  • the photoelectric conversion device includes: a substrate on which a transparent conductive film is formed; a first p-type semiconductor layer made of an amorphous silicon-based thin film on the transparent conductive film; A pin-type first photoelectric conversion unit formed by sequentially stacking a substantially intrinsic i-type semiconductor layer and a first n-type semiconductor layer; and a crystalline material on the first photoelectric conversion unit; A second p-type semiconductor layer made of a silicon-based thin film, a second substantially intrinsic i-type semiconductor layer, and a second n-type semiconductor layer made of an amorphous silicon-based thin film were sequentially stacked. a pin-type second photoelectric conversion unit; and a back electrode formed on the second photoelectric conversion unit.
  • the thickness of the second n-type semiconductor layer is preferably 20 to 400 mm.
  • the manufacturing method of the photoelectric conversion device according to the second aspect of the present invention is the first p, which is composed of an amorphous silicon thin film on the transparent conductive film formed on the substrate and constitutes the pin type first photoelectric conversion unit.
  • a photoelectric conversion device includes: a substrate on which a transparent conductive film is formed; a third p-type semiconductor layer made of a crystalline silicon-based thin film on the transparent conductive film; A pin-type third photoelectric conversion unit formed by sequentially laminating an intrinsic i-type semiconductor layer and a third n-type semiconductor layer made of an amorphous silicon-based thin film; A back electrode formed thereon.
  • the thickness of the third n-type semiconductor layer is preferably 20 to 400 mm.
  • a method for producing a photoelectric conversion device comprising: a third photoelectric conversion unit comprising a crystalline silicon-based thin film on a transparent conductive film formed on a substrate; a p-type semiconductor layer and a third substantially intrinsic i-type semiconductor layer are sequentially formed; and the third photoelectric conversion unit is formed of an amorphous silicon-based thin film on the third i-type semiconductor layer. Forming a third n-type semiconductor layer; forming a back electrode on the third n-type semiconductor layer;
  • the p layer and the i layer constituting the second photoelectric conversion unit are made of a crystalline silicon-based thin film, and the second photoelectric conversion unit is constituted.
  • the n layer, which is disposed between the i layer and the back electrode and constitutes the second photoelectric conversion unit, is made of an amorphous silicon thin film.
  • the function of the i layer made of a crystalline silicon-based thin film can be effectively utilized in the first photoelectric conversion unit, and lattice matching at the interface between the i layer and the back electrode can be obtained, and the second photoelectric conversion unit can be used.
  • the open circuit voltage (Voc) on the conversion unit side can be improved.
  • the power generation efficiency of a 2nd photoelectric conversion unit can be improved, and the photoelectric conversion efficiency as the whole apparatus can be improved.
  • method for manufacturing device A a step of sequentially forming a p layer, an i layer, and an n layer of the first photoelectric conversion unit, A step of forming a p layer and an i layer constituting the second photoelectric conversion unit on the n layer of the conversion unit in order, and an n constituting the second photoelectric conversion unit on the i layer of the second photoelectric conversion unit A step of forming a layer, and a step of forming the back electrode on the n layer constituting the second photoelectric conversion unit, at least in order, so that the obtained photoelectric conversion device is provided on the second photoelectric conversion unit side.
  • the open circuit voltage (Voc) can be improved. For this reason, the power generation efficiency of a 2nd photoelectric conversion unit can be improved, and the photoelectric conversion efficiency as the whole apparatus can be improved. As a result, according to the present invention, it is possible to provide a method of manufacturing a photoelectric conversion device that can easily manufacture a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • the p layer and i layer constituting the third photoelectric conversion unit are made of a crystalline silicon-based thin film, and the third photoelectric conversion unit
  • the n layer constituting the third photoelectric conversion unit is made of an amorphous silicon-based thin film.
  • the present invention it is possible to provide a photoelectric conversion device having a single structure with improved photoelectric conversion efficiency.
  • the step of sequentially forming the p layer and the i layer of the third photoelectric conversion unit, a step of forming an n layer, and a step of forming the back electrode on the n layer constituting the third photoelectric conversion unit improves.
  • an open circuit voltage (Voc) improves.
  • Sectional drawing which shows an example of the laminated constitution of the photoelectric conversion apparatus (apparatus A) which concerns on this invention.
  • Explanatory drawing which shows the process example of the manufacturing method of the photoelectric conversion apparatus shown in FIG.
  • Explanatory drawing which shows the process example of the manufacturing method of the photoelectric conversion apparatus shown in FIG.
  • Explanatory drawing which shows the process example of the manufacturing method of the photoelectric conversion apparatus shown in FIG.
  • Schematic which shows an example of the manufacturing system which manufactures the photoelectric conversion apparatus which concerns on this invention.
  • Sectional drawing which shows an example of the laminated constitution of the photoelectric conversion apparatus (apparatus B) which concerns on this invention.
  • FIG. 1 is a cross-sectional view illustrating the layer structure of the photoelectric conversion device of the present invention.
  • a p-type semiconductor layer (p layer), a substantially intrinsic i-type semiconductor layer (i layer), and n are formed on the first surface 1a of the substrate with a transparent conductive film.
  • a pin-type first photoelectric conversion unit 3 and a second photoelectric conversion unit 4 each having a stacked type semiconductor layer (n layer) are sequentially stacked on the transparent conductive film 2. Further, a back electrode 5 is formed on the second photoelectric conversion unit 4 so as to overlap.
  • the substrate 1 is made of an insulating material that is excellent in sunlight transmittance and durable, such as glass and transparent resin.
  • the substrate 1 includes a transparent conductive film 2.
  • the transparent conductive film 2 include light-transmitting metal oxides such as ITO (indium tin oxide), SnO 2 , and ZnO.
  • the transparent conductive film 2 is formed on the substrate 1 by vacuum deposition or sputtering.
  • this photoelectric conversion device 10 ⁇ / b> A (10) sunlight S is incident on the second surface 1 b of the substrate 1 as indicated by a white arrow in FIG. 1.
  • the first photoelectric conversion unit 3 includes a p-type semiconductor layer (p layer, first p-type semiconductor layer) 31 and a substantially intrinsic i-type semiconductor layer (i layer, first i-type semiconductor layer) 32. , An n-type semiconductor layer (n layer, first n-type semiconductor layer) 33 is stacked. That is, the first photoelectric conversion unit 3 is formed by stacking the p layer 31, the i layer 32, and the n layer 33 in this order.
  • the first photoelectric conversion unit 3 is made of an amorphous silicon material.
  • 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 plasma CVD reaction chambers for forming the p layer 31, i layer 32, and n layer 43 of the first photoelectric conversion unit 3 are different from each other.
  • the second photoelectric conversion unit 4 includes a p-type semiconductor layer (p layer, second p-type semiconductor layer) 41, a substantially intrinsic i-type semiconductor layer (i layer, second i-type semiconductor layer) 42, n And a pin structure in which a p-type semiconductor layer (n-layer, second n-type semiconductor layer) 43 is stacked. That is, the second photoelectric conversion unit 4 is formed by laminating the p layer 41, the i layer 42, and the n layer 43 in this order.
  • the p-type semiconductor layer (p layer) 41 and the i-type semiconductor layer (i layer) 42 constituting the second photoelectric conversion unit 4 are made of a crystalline silicon-based thin film.
  • the n-type semiconductor layer (n layer) 43 constituting the second photoelectric conversion unit 4 is amorphous by being formed between the i layer 42 constituting the second photoelectric conversion unit 4 and the back electrode 5.
  • the silicon-based thin film is used.
  • n layer 43 constituting the second photoelectric conversion unit 4 disposed between the i layer constituting the second photoelectric conversion unit 4 and the back electrode By forming the n layer 43 constituting the second photoelectric conversion unit 4 disposed between the i layer constituting the second photoelectric conversion unit 4 and the back electrode by an amorphous silicon-based thin film, The mismatch at the interface between the i layer 42 made of a crystalline silicon-based thin film and the back electrode 5 can be alleviated. Thereby, in the second photoelectric conversion unit 4, the function of the i layer 42 made of a crystalline silicon thin film can be effectively utilized, and lattice matching at the interface between the i layer 42 and the back electrode 5 can be obtained. The open circuit voltage (Voc) on the second photoelectric conversion unit 4 side can be improved.
  • Voc open circuit voltage
  • the power generation efficiency of the 2nd photoelectric conversion unit 4 can be improved, and the photoelectric conversion efficiency as the whole apparatus can be improved.
  • the present invention it is possible to provide a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • the n-layer 43 made of an amorphous silicon-based thin film is similar to the amorphous n-layer 43 observed with a laser Raman microscope.
  • the intensity (ic) of Raman scattered light caused by the crystalline silicon-based thin film is a peak near 520 nm. Is not observed.
  • the n layer 43 has a conductivity of, for example, 1.0 ⁇ 10 ⁇ 4 to 1.0 ⁇ 10 ⁇ 2 S / cm.
  • the thickness of the p-type semiconductor layer (p layer) 41 is 150 mm, for example, and the thickness of the i-type semiconductor layer (i layer) 42 is 15000 mm, for example.
  • the thickness of the n-type semiconductor layer (n layer) 43 is preferably in the range of 20 to 400 mm, for example, and can be 50 mm, for example.
  • the fill factor (FF) and the open circuit voltage (Voc) increase, and the effect of increasing the photoelectric conversion efficiency is recognized.
  • the thickness of the n layer 43 is 400 mm or more, Jsc and Voc are lowered. This is presumably because the n-layer 43 absorbed light and the Jsc on the i-layer 42 side made of a crystalline silicon-based thin film was lowered.
  • the back electrode 5 should just be comprised by electroconductive light reflection films, such as Ag (silver) and Al (aluminum).
  • the back electrode 5 can be formed, for example, by sputtering or vapor deposition.
  • a layer made of a conductive oxide such as ITO, SnO 2 , or ZnO is formed between the n-type semiconductor layer (n layer) 43 of the second photoelectric conversion unit 4 and the back electrode 5.
  • a laminated structure may be employed.
  • the manufacturing method of the photoelectric conversion device of the present invention includes a step of sequentially forming the p layer 31, the i layer 32, and the n layer 33 of the first photoelectric conversion unit 3, on the n layer 33 of the first photoelectric conversion unit 3, A step of sequentially forming a p layer 41 and an i layer 42 constituting the second photoelectric conversion unit 4, and an n layer 43 constituting the second photoelectric conversion unit 4 on the i layer 42 of the second photoelectric conversion unit 4. And the step of forming the back electrode 5 on the n layer 43 constituting the second photoelectric conversion unit 4 at least in order.
  • the open circuit voltage (Voc) on the unit 4 side can be improved.
  • the power generation efficiency of the 2nd photoelectric conversion unit 4 can be improved, and the photoelectric conversion efficiency as the whole apparatus can be improved.
  • the present invention it is possible to easily manufacture a tandem photoelectric conversion device with improved photoelectric conversion efficiency.
  • it demonstrates in order of a process.
  • an insulating transparent substrate 1 on which a transparent conductive film 2 is formed is prepared.
  • the p-type semiconductor layer 31 and the i-type silicon layer (amorphous silicon layer) of the first photoelectric conversion unit 3 are formed on the transparent conductive film 2 formed on the insulating transparent substrate 1.
  • Layer) 32, the n-type semiconductor layer 33, and the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 are formed.
  • the plasma CVD reaction chambers for forming the p layer 31, the i layer 32, the n layer 33, and the p layer 41 are different. That is, on the n-type semiconductor layer 33 of the first photoelectric conversion unit 3, the photoelectric conversion device first intermediate product 10a provided with the p-type semiconductor layer 41 constituting the second photoelectric conversion unit 4 is formed.
  • the p-type semiconductor layer 31 is formed by plasma CVD in an individual reaction chamber.
  • the substrate temperature is 180 to 200 ° C.
  • the power supply frequency is 13.56 MHz
  • the reaction chamber pressure is 70 to 120 Pa
  • the reaction gas flow rate is 300 sccm for monosilane (SiH 4 ), 2300 sccm for hydrogen (H 2 ), and hydrogen as a dilution gas
  • the p-layer 31 of amorphous silicon (a-Si) can be formed under the conditions of 180 sccm for diborane (B 2 H 6 / H 2 ) and 500 sccm for methane (CH 4 ).
  • the i-type silicon layer (amorphous silicon layer) 32 is formed by plasma CVD in a separate reaction chamber.
  • the substrate temperature is 180 to 200 ° C.
  • the power supply frequency is 13.56 MHz
  • the pressure in the reaction chamber is 70 to 120 Pa
  • the reaction gas flow rate is 1200 scc for monosilane (SiH 4 )
  • the amorphous silicon (a-Si) i Layer 32 can be deposited.
  • the n-type semiconductor layer 33 is formed by plasma CVD in a separate reaction chamber.
  • the substrate temperature is 180 to 200 ° C.
  • the power supply frequency is 13.56 MHz
  • the pressure in the reaction chamber is 70 to 120 Pa
  • the flow rate of the reaction gas is phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • a-Si amorphous silicon
  • the p-type semiconductor layer 41 is formed by plasma CVD in a separate reaction chamber.
  • the substrate temperature is 180 to 200 ° C.
  • the power supply frequency is 13.56 MHz
  • the reaction chamber pressure is 500 to 900 Pa
  • the reaction gas flow rate is 100 sccm for monosilane (SiH 4 ), 25000 sccm for hydrogen (H 2 ), and hydrogen as a dilution gas
  • the p-layer 41 of microcrystalline silicon ( ⁇ c-Si) can be formed under the condition that the diborane (B 2 H 6 / H 2 ) used as is 50 sccm.
  • the second photoelectric conversion unit 4 is formed on the p-type semiconductor layer 41 exposed to the atmosphere.
  • An i-type silicon layer (crystalline silicon layer) 42 and an n-type semiconductor layer (amorphous silicon layer) 43 are formed in the same plasma CVD reaction chamber. That is, the second intermediate product 10 b of the photoelectric conversion device in which the second photoelectric conversion unit 4 is provided is formed on the first photoelectric conversion unit 3.
  • the i-type silicon layer (crystalline silicon layer) 42 is formed by a plasma CVD method in the same reaction chamber as the reaction chamber in which the n-type semiconductor layer 43 is formed.
  • the substrate temperature is 180 to 200 ° C.
  • the power supply frequency is 13.56 MHz
  • the pressure in the reaction chamber is 500 to 900 Pa
  • the reaction gas flow rate is 180 sccm for monosilane (SiH 4 ) and 27000 sccm for hydrogen (H 2 )
  • An i-layer of microcrystalline silicon ( ⁇ c-Si) can be formed.
  • the n-type semiconductor layer 43 is formed by plasma CVD in the same reaction chamber as the reaction chamber in which the i-type silicon layer (crystalline silicon layer) 42 is formed.
  • the substrate temperature is 180 to 200 ° C.
  • the power supply frequency is 13.56 MHz
  • the pressure in the reaction chamber is 70 to 120 Pa
  • the flow rate of the reaction gas is phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas at 200 sccm.
  • a-Si amorphous silicon
  • the photoelectric conversion apparatus 10A (10) as shown in FIG. 1 is obtained by forming the back surface electrode 5 on the n-type semiconductor layer 43 of the second photoelectric conversion unit 4.
  • the back electrode 5 should just be comprised by electroconductive light reflection films, such as Ag (silver) or Al (aluminum).
  • the back electrode 5 can be formed, for example, by sputtering or vapor deposition.
  • the manufacturing system of the photoelectric conversion device 10 includes a so-called in-line type first film forming device, an exposure device that exposes the p-layer of the second photoelectric conversion unit 4 to the atmosphere, and a so-called batch type second component.
  • the membrane device is arranged in order.
  • the in-line type first film forming apparatus has a configuration in which a plurality of film forming reaction chambers called chambers are arranged in a straight line.
  • the p-type semiconductor layer 31, the i-type silicon layer (amorphous silicon layer) 32, the n-type semiconductor layer 33, and the second photoelectric conversion unit 4 in the first photoelectric conversion unit 3 are used.
  • Each layer of the type semiconductor layer 41 is formed separately.
  • each of the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer (amorphous silicon layer) 43 in the second photoelectric conversion unit 4 is simultaneously applied to a plurality of substrates. Are formed in the same film formation reaction chamber.
  • a manufacturing system of the photoelectric conversion device 10 is shown in FIG. As shown in FIG. 3, the manufacturing system exposes the first film forming apparatus 60, the second film forming apparatus 70, and the substrate processed by the first film forming apparatus 60 to the second film forming apparatus 70. And a moving exposure device 80.
  • the first film forming apparatus 60 in the manufacturing system is provided with a load chamber (L: Load) 61 in which the substrate is first carried and the internal pressure is reduced. Note that a heating chamber for heating the substrate temperature to a certain temperature may be provided in the subsequent stage of the load chamber (L: Load) 61 in accordance with the film forming process.
  • An n-layer film formation reaction chamber 64 for forming the layer 33 and a p-layer film formation reaction chamber 65 for forming the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 are continuously arranged in a straight line.
  • an unload chamber (UL: UnLoad, unloading device) 66 for returning the reduced-pressure atmosphere to the atmospheric atmosphere and unloading the substrate is connected to the p-layer film formation reaction chamber 65.
  • an insulating transparent substrate 1 on which the transparent conductive film 2 is formed is prepared.
  • the p-type semiconductor layer 31 of the first photoelectric conversion unit 3 is formed on the transparent conductive film 2 formed on the insulating transparent substrate 1, as shown in FIG. 2B.
  • the first intermediate product 10a of the photoelectric conversion device provided with the i-type silicon layer (amorphous silicon layer) 32, the n-type semiconductor layer 33, and the p-type semiconductor layer 41 of the second photoelectric conversion unit 4 is formed.
  • the second film forming apparatus 70 in the manufacturing system includes a load / unload chamber (L / UL) 71 and an in-layer film forming reaction chamber 72.
  • the load / unload chamber (L / UL) 71 carries in the first intermediate product 10a of the photoelectric conversion device processed by the first film forming device 60, and reduces the internal pressure after the substrate is carried in, The reduced-pressure atmosphere is returned to the air atmosphere when unloading.
  • the in-layer deposition reaction chamber 72 is connected to the load / unload chamber (L / UL) 71.
  • the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer (non-layer) of the second photoelectric conversion unit 4 are formed on the p-type semiconductor layer 41 of the second photoelectric conversion unit 4.
  • a crystalline silicon layer) 43 is sequentially formed in the same reaction chamber. Further, this film forming process is performed simultaneously on a plurality of substrates. At this time, the second intermediate product 10b of the photoelectric conversion device in which the second photoelectric conversion unit 4 is provided is formed on the first photoelectric conversion unit 3, as shown in FIG. .
  • the i-layer film forming reaction chamber 63 includes four reaction chambers 63a and 63b. , 63c, 63d.
  • the batch-type second film forming apparatus 70 is configured to process six substrates simultaneously.
  • the photoelectric conversion device is a crystalline photoelectric conversion device on the p layer 31, the i layer 32, and the n layer 33 of the first photoelectric conversion unit 3 that is an amorphous photoelectric conversion device.
  • the p layer 41 of the second photoelectric conversion unit 4 is formed.
  • the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 are formed. Thereby, it is possible to easily control the crystallization rate distribution of the i layer 42 of the second photoelectric conversion unit 4.
  • the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer 43 constituting the second photoelectric conversion unit 4 are formed on the p-type semiconductor layer 41 exposed in the atmosphere.
  • the p layer, i layer, and n of the first photoelectric conversion unit 3 are formed on the transparent metal oxide electrode of the glass substrate 1 with the transparent metal oxide electrode (transparent conductive film 2) in a separate film formation chamber.
  • the OH radical-containing plasma processing chamber is used. Thereafter, the i-type silicon layer (crystalline silicon layer) 42 and the n-type semiconductor layer 43 constituting the second photoelectric conversion unit 4 may be formed in separate film formation chambers or in the same processing chamber. The i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 may be laminated continuously with the radical-containing plasma treatment.
  • the film formation chamber is treated with the OH radical-containing plasma for each treatment. Apply. This enables decomposition and removal of the residual impurity gas PH 3. Therefore, even if the film formation of the i layer 42 and the n layer 43 of the second photoelectric conversion unit 4 is repeated in the same processing chamber, a good impurity profile can be obtained, and the laminated thin film photoelectric conversion device 10 with good power generation efficiency can be obtained. Can do.
  • CO 2 , CH 2 O 2 or a mixture of H 2 O and H 2 is used as a process gas. It is desirable to use gas. That is, for the generation of OH radical-containing plasma, (CO 2 + H 2 ), (CH 2 O 2 + H 2 ), or (H 2 O + H 2 ) is allowed to flow in the film formation chamber between the electrodes, for example, 13. It can be effectively generated by applying a high frequency such as 5 MHz, 27 MHz, or 40 MHz.
  • alcohols such as (HCOOCH 2 + H 2 ) and (CH 2 OH + H 2 ), and oxygen-containing hydrocarbons such as formate esters may be used.
  • oxygen-containing hydrocarbons such as formate esters
  • H 2 When CO 2 is used as the plasma generation gas in the generation of this OH radical-containing plasma, the presence of H 2 is necessary in the system, but in addition to (CH 2 O 2 + H 2 ) and (H 2 O + H 2 ), When oxygen-containing hydrocarbons such as alcohols such as (HCOOCH 3 + H 2 ) and (CH 3 OH + H 2 ) and formate esters are used, the presence of H 2 is not necessarily required in the system.
  • the reaction is milder than that of the O radical and the lower layer is not damaged, and the p layer 31, i layer 32, and n layer 33 of the first photoelectric conversion unit 3 are not damaged.
  • This is effective for the surface activity of the p layer 41 of the formed second photoelectric conversion unit 4. Therefore, the surface activation of the p layer 41 of the second photoelectric conversion unit 4 becomes possible. It effectively works for crystal formation of the i layer 42 of the second photoelectric conversion unit 4 laminated thereon, and a uniform crystallization rate distribution can be obtained even on a large-area substrate. Even if the hydrogen plasma treatment is performed instead of the OH radical-containing plasma treatment, the same effect as the OH radical-containing plasma treatment can be obtained.
  • the p layer 41 of the second photoelectric conversion unit 4 formed on the amorphous p layer 31, i layer 32, and n layer 33 of the first photoelectric conversion unit 3 in an individual film formation chamber is amorphous.
  • amorphous amorphous oxidation is required. It is preferable to employ a film in which microcrystalline silicon ( ⁇ c-Si) is dispersed in the silicon (a-SiO) layer.
  • a film in which microcrystalline silicon ( ⁇ c-Si) is dispersed in an amorphous amorphous silicon oxide (a-SiO) layer has a lower refractive index than an amorphous silicon (a-Si) semiconductor layer. It is possible to adjust as follows. Therefore, it is possible to improve the conversion efficiency by making this layer function as a wavelength selective reflection film and confining short wavelength light on the top cell side. Regardless of the effect of confining light, a film in which microcrystalline silicon ( ⁇ c-Si) is dispersed in an amorphous amorphous silicon oxide (a-SiO) layer is subjected to OH radical-containing plasma treatment. It is effective for generating crystal growth nuclei of the i-layer 42 and the n-layer 43 of the two photoelectric conversion unit 4, and 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.
  • the substrate on which the n layer 33 and the p layer 41 of the second photoelectric conversion unit 4 are formed is subjected to OH radical-containing plasma treatment in an individual reaction chamber or the same film formation chamber, and the surface is activated to produce crystals.
  • a laminated thin film photoelectric conversion device 10A (10 having a uniform crystallization rate distribution over a large area and good power generation efficiency. ) Can be obtained.
  • FIG. 4 is a cross-sectional view illustrating a layer configuration of the photoelectric conversion device according to the present embodiment.
  • the tandem structure photoelectric conversion device has been described.
  • the present invention is not limited to the tandem structure, and can be applied to a single structure photoelectric conversion device.
  • this photoelectric conversion device 10B a substrate with a transparent conductive film is used, a p-type semiconductor layer (p layer, third p-type semiconductor layer) 81, a substantially intrinsic i-type semiconductor layer (i layer, A pin type third photoelectric conversion unit 8 in which a third i-type semiconductor layer) 82 and an n-type semiconductor layer (n-layer, third n-type semiconductor layer) 83 are stacked, and the back electrode 5 include the transparent conductive material.
  • the film 2 is formed on the film 2 in order.
  • the p layer 81 and the i layer 82 constituting the third photoelectric conversion unit 8 are formed of a crystalline silicon-based thin film, and the third photoelectric conversion unit 8 is configured.
  • the n layer 83 disposed between the i layer 82 and the back electrode 5 and constituting the third photoelectric conversion unit 8 is formed of an amorphous silicon-based thin film.
  • the p layer 81 and i layer 82 constituting the third photoelectric conversion unit 8 are formed of a crystalline silicon thin film, and the i layer 82 constituting the third photoelectric conversion unit 8.
  • an n-layer 83 disposed between the back electrode 5 and the third photoelectric conversion unit 8 is formed of an amorphous silicon-based thin film, thereby forming an i-layer 82 formed of a crystalline silicon-based thin film,
  • the mismatch at the interface of the back electrode 5 can be alleviated.
  • the function of the i layer 82 formed of a crystalline silicon-based thin film can be effectively utilized, and the open circuit voltage (Voc) is improved.
  • the photoelectric conversion efficiency of the photoelectric conversion device 10B (10) is improved.
  • the manufacturing method of the photoelectric conversion apparatus 10B (10) of this invention forms the p layer 81 and the i layer 82 of the 3rd photoelectric conversion unit 8 in order, and forms the n layer 83 of the 3rd photoelectric conversion unit 8.
  • the p layer 81, i layer 82, and n layer 83 constituting the third photoelectric conversion unit 8 are all the p layer 41, i layer 42, and the second photoelectric conversion unit 4 in the first embodiment described above.
  • the n layer 43 can be formed in the same manner.
  • the open circuit voltage (Voc) is improved, and the photoelectric conversion efficiency is improved.
  • the manufacturing method of the present invention it is possible to easily manufacture the photoelectric conversion device 10B (10) with improved photoelectric conversion efficiency.
  • the photoelectric conversion device is manufactured using a substrate having a size of 1100 mm ⁇ 1400 mm.
  • the first photoelectric conversion unit is formed of a p-layer made of an amorphous amorphous silicon (a-Si) thin film, a buffer layer, and an amorphous amorphous silicon (a-Si) thin film on the substrate.
  • a-Si amorphous amorphous silicon
  • a buffer layer a buffer layer
  • a-Si amorphous amorphous silicon
  • An i layer, an n layer composed of an amorphous silicon (a-Si) thin film, and a p layer containing microcrystalline silicon ( ⁇ c-Si) constituting the second photoelectric conversion unit were formed. These layers are successively formed in separate film formation chambers.
  • the p layer of the second photoelectric conversion unit was exposed to the atmosphere, and hydrogen plasma treatment was performed on the p layer of the second photoelectric conversion unit using hydrogen (H 2 ) as a process gas. Thereafter, an i layer made of microcrystalline silicon ( ⁇ c-Si), an n layer made of an amorphous silicon (a-Si) thin film, and a back electrode constituting the second photoelectric conversion unit were formed.
  • ⁇ c-Si microcrystalline silicon
  • a-Si amorphous silicon
  • Example 1 the p layer, i layer, and n layer of the first photoelectric conversion unit and the p layer of the second photoelectric conversion unit were formed by plasma CVD in individual reaction chambers. On the other hand, the i layer and the n layer of the second photoelectric conversion unit were formed by plasma CVD in the same film formation chamber.
  • the p layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 80 Pa, and a reaction gas flow rate of 150 cc for monosilane (SiH 4 ), 470 sccm for hydrogen (H 2 ), hydrogen As a diluent gas, a film was formed to a thickness of 80 mm under conditions of 45 sccm for diborane (B 2 H 6 / H 2 ) and 300 sccm for methane (CH 4 ). The deposition rate at this time was 116 ⁇ / min.
  • the buffer layer has a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 60 Pa, a reaction gas flow rate of 150 sccm for monosilane (SiH 4 ), 1500 sccm for hydrogen (H 2 ), and methane (CH 4 ).
  • SiH 4 monosilane
  • SiH 2 1500 sccm for hydrogen
  • CH 4 methane
  • the i layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 40 W, a reaction chamber pressure of 40 Pa, and a reaction gas flow rate of 2000 ⁇ with monosilane (SiH 4 ) of 300 sccm. A film was formed. The film formation rate at this time was 131 kg / min. Furthermore, the n layer of the first photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 1000 W, a reaction chamber pressure of 800 Pa, and a reaction gas flow rate of 150 cc for monosilane (SiH 4 ) and 550 sccm for hydrogen (H 2 ).
  • the film was formed to a thickness of 20 mm under the condition of 60 sccm of phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas. At this time, the deposition rate was 158 ⁇ / min.
  • the substrate temperature is 170 ° C.
  • the applied RF power is 750 W
  • the reaction chamber pressure is 1200 Pa
  • the reaction gas flow rate is 30 sccm for monosilane (SiH 4 )
  • the reaction gas flow rate is 30 sccm for monosilane (SiH 4 )
  • the film was formed to a thickness of 150 mm under conditions of 9000 sccm and diborane (B 2 H 6 / H 2 ) using hydrogen as a diluent gas at 12 sccm.
  • the film formation rate at this time was 174 ⁇ / min.
  • the p layer of the second photoelectric conversion unit was exposed to the atmosphere.
  • the p layer was subjected to plasma treatment under the conditions of a substrate temperature of 190 ° C., a power supply frequency of 13.56 MHz, a reaction chamber pressure of 700 Pa, and H 2 as a process gas of 1000 sccm.
  • the i layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 550 W, a reaction chamber pressure of 1200 Pa, and a reaction gas flow rate of 45 sccm for monosilane (SiH 4 ) and 3150 sccm for hydrogen (H 2 ).
  • a film having a thickness of 15000 mm was formed. At this time, the film formation rate was 361 L / min.
  • the n layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 100 W, a reaction chamber pressure of 80 Pa, and a reaction gas flow rate of 150 sccm for monosilane (SiH 4 ) and 550 sccm for hydrogen (H 2 ).
  • the film was formed to a thickness of 20 mm under the condition of 60 sccm of phosphine (PH 3 / H 2 ) using hydrogen as a diluent gas. At this time, the deposition rate was 158 ⁇ / min.
  • zinc oxide (ZnO) was formed to a thickness of 800 mm on the n layer of the second photoelectric conversion unit by sputtering. Further, silver (Ag) was formed thereon to a film thickness of 2000 mm to form a back electrode.
  • Example 2 to Example 6 The thickness of the n layer constituting the second photoelectric conversion unit is changed to 20 mm, 50 mm (Example 2), 100 mm (Example 3), 150 mm (Example 4), 200 mm (Example 5), 400 mm (implemented)
  • a tandem photoelectric conversion device was produced in the same manner as in Example 1 except that Example 6) was used.
  • n layer constituting the second photoelectric conversion unit was an n layer made of microcrystalline silicon ( ⁇ c-Si).
  • the n layer of the second photoelectric conversion unit has a substrate temperature of 170 ° C., an applied RF power of 1000 W, a reaction chamber pressure of 800 Pa, a reaction gas flow rate of 20 sccm for monosilane (SiH 4 ), 2000 sccm for hydrogen (H 2 ), hydrogen was used to form a film having a thickness of 100 mm under the condition of 15 sccm of phosphine (PH 3 / H 2 ) using as a diluent gas.
  • the film formation rate at this time was 174 ⁇ / min.
  • the conventional photoelectric conversion device (comparative example) Compared to the above, it showed good characteristics, and in particular, the photoelectric conversion efficiency could be improved by about 0.5% (contrast of Example 3 and Comparative Example).
  • FIGS. 5 and 6 show the photoelectric conversion efficiency ( ⁇ ) and the open-circuit voltage (Voc) obtained when the thickness of the n layer of the second photoelectric conversion unit was changed for the photoelectric conversion devices of Examples 1 to 6. ) Shows the measurement results. That is, FIGS. 5 and 6 are graphs in which ⁇ and Voc (vertical axis) are plotted with respect to the thickness (horizontal axis) of the n layer. As shown in Table 1, FIG. 5, and FIG. 6, when the thickness (film thickness) of the n layer is in the range of 20 to 400 mm, the open circuit voltage (Voc) increases and the photoelectric conversion efficiency ⁇ increases. It is done.
  • the film thickness of the n layer constituting the second light conversion unit is preferably in the range of 20 to 400 mm, and more preferably in the range of 100 to 200 mm.
  • the present invention is widely applicable to photoelectric conversion devices and methods for manufacturing photoelectric conversion devices.
  • first photoelectric conversion unit second photoelectric conversion unit 5 back electrode 10A, 10B (10) photoelectric conversion device 31 p-type semiconductor layer (first p-type semiconductor layer) 32 i-type silicon layer (amorphous silicon layer, first i-type semiconductor layer) 33 n-type semiconductor layer (first n-type semiconductor layer) 41 p-type semiconductor layer (second p-type semiconductor layer) 42 i-type silicon layer (crystalline silicon layer, second i-type semiconductor layer) 43 n-type semiconductor layer (second n-type semiconductor layer) 8 First photoelectric conversion unit 81 p-type semiconductor layer (third p-type semiconductor layer) 82 i-type silicon layer (crystalline silicon layer, third i-type semiconductor layer) 83 n-type semiconductor layer (third n-type semiconductor layer) 60 First film formation apparatus 61 Load chamber 62 P layer film formation reaction chamber 63 (63a, 63b, 63c, 63d) i layer film formation reaction chamber 64 n

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Abstract

L'invention concerne un dispositif de conversion photoélectrique comprenant : un substrat sur lequel un film conducteur transparent est formé ; une première unité de conversion photoélectrique de type pin qui comprend une première couche semi-conductrice de type p comprenant un film mince de silicium amorphe, une première couche semi-conductrice sensiblement intrinsèque, de type i, et une première couche semi-conductrice de type n, stratifiées dans cet ordre sur le film conducteur transparent ; une seconde unité de conversion photoélectrique de type pin qui comprend une seconde couche semi-conductrice de type p comprenant un film mince de silicium cristallin, une seconde couche semi-conductrice sensiblement intrinsèque, de type i, et une seconde couche semi-conductrice de type n, comprenant un film mince de silicium amorphe, stratifiées dans cet ordre sur la première unité de conversion photoélectrique ; et une électrode postérieure qui est formée sur la seconde unité de conversion photoélectrique.
PCT/JP2011/058289 2010-04-02 2011-03-31 Dispositif de conversion photoélectrique et procédé de production d'un dispositif de conversion photoélectrique WO2011125878A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04192373A (ja) * 1990-11-26 1992-07-10 Canon Inc 光起電力素子
JP2000068533A (ja) * 1998-08-25 2000-03-03 Sharp Corp 微結晶シリコン薄膜太陽電池及びその製造方法
JP2006120745A (ja) * 2004-10-20 2006-05-11 Mitsubishi Heavy Ind Ltd 薄膜シリコン積層型太陽電池
WO2009069544A1 (fr) * 2007-11-30 2009-06-04 Kaneka Corporation Dispositif de conversion photoélectrique à film mince de silicium

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04192373A (ja) * 1990-11-26 1992-07-10 Canon Inc 光起電力素子
JP2000068533A (ja) * 1998-08-25 2000-03-03 Sharp Corp 微結晶シリコン薄膜太陽電池及びその製造方法
JP2006120745A (ja) * 2004-10-20 2006-05-11 Mitsubishi Heavy Ind Ltd 薄膜シリコン積層型太陽電池
WO2009069544A1 (fr) * 2007-11-30 2009-06-04 Kaneka Corporation Dispositif de conversion photoélectrique à film mince de silicium

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