WO2013081114A1 - 薄膜太陽電池 - Google Patents
薄膜太陽電池 Download PDFInfo
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- WO2013081114A1 WO2013081114A1 PCT/JP2012/081105 JP2012081105W WO2013081114A1 WO 2013081114 A1 WO2013081114 A1 WO 2013081114A1 JP 2012081105 W JP2012081105 W JP 2012081105W WO 2013081114 A1 WO2013081114 A1 WO 2013081114A1
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- layer
- buffer layer
- light absorption
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- solar cell
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- 239000010409 thin film Substances 0.000 title claims abstract description 40
- 239000000872 buffer Substances 0.000 claims abstract description 77
- 230000031700 light absorption Effects 0.000 claims abstract description 54
- 239000010408 film Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000004020 conductor Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000004771 selenides Chemical class 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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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
-
- 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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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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
- H01L31/0248—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
- H01L31/0256—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 the material
- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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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
- H01L31/04—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
- H01L31/072—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 PN heterojunction type
- H01L31/0749—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 PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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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
- 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
- Y02E10/541—CuInSe2 material PV cells
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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
- 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 thin film solar cell, and more particularly to a thin film solar cell capable of achieving high photoelectric conversion efficiency.
- thin-film solar cells using an I-III-VI group 2 compound semiconductor or an I 2- (II-IV) -VI group 4 compound semiconductor have attracted attention as p-type light absorption layers.
- those using a chalcopyrite-structured I-III-VI 2 group compound semiconductor containing Cu, In, Ga, Se, and S are called CIS-based thin film solar cells.
- a p-type absorber layer using a chalcogenide-based I 2- (II-IV) -VI 4 group compound semiconductor containing Cu, Zn, Sn, S or Se is called a CZTS-based thin film solar cell.
- Typical examples include Cu 2 ZnSnS 4 , Cu 2 ZnSnSe 4 , and Cu 2 ZnSn (S, Se) 4 .
- These thin-film solar cells use materials that are relatively inexpensive and easy to obtain, are relatively easy to manufacture, and have a large absorption coefficient in the visible to near-infrared wavelength range, so high photoelectric conversion efficiency is expected. Therefore, it is regarded as a leading candidate for next-generation solar cells.
- the present invention has been made to solve the above-mentioned problems in CIS-based thin-film solar cells or CZTS-based thin-film solar cells, and provides a new manufacturing method capable of increasing the photoelectric conversion efficiency thereof. Is an issue.
- the thin-film solar cell of the present invention includes a metal back electrode layer formed on a substrate, a p-type light absorption layer formed on the metal back electrode layer, and a surface of the p-type light absorption layer.
- the InS buffer layer is formed as an n-type high resistance buffer layer on the oxidized p-type light absorption layer, and an n-type transparent conductive film is formed on the InS buffer layer. It is manufactured by doing.
- the surface of the p-type light absorption layer may be oxidized by annealing in the atmosphere.
- the InS buffer layer may be formed by a solution growth method (CBD method).
- the p-type light absorption layer may be formed of a CZTS semiconductor. Furthermore, the p-type light absorption layer may be formed of a CIS or CIGS semiconductor.
- the p-type light absorption layer is annealed in the atmosphere, for example, to form an oxide film on the surface, and then an InS buffer layer is formed by, for example, the solution growth method, the p-type light absorption layer is formed during the solution growth method.
- Oxygen from the upper oxide film diffuses into the formed InS buffer layer, and an In oxide film is formed at the junction with the p-type absorber layer. Since the oxide of In has a wider band gap than the sulfide of In, the amount of conductor band discontinuity associated with the heterojunction with the p-type light absorption layer is increased at the junction. As a result, leakage current is suppressed and the fill factor and open circuit voltage of the solar cell are improved.
- the buffer layer a material having a wide band gap is preferable from the viewpoint of light transmittance.
- a material having a wide band gap is preferable from the viewpoint of light transmittance.
- an In oxide layer having a wider band gap than In sulfide is formed at the junction, light transmission is improved and short-circuit current density is increased. By improving the fill factor, open circuit voltage, and short circuit current density, the photoelectric conversion efficiency is greatly improved.
- a thin film solar cell using a conventional CdS-based or ZnS-based buffer layer if an oxide film is present on the p-type light absorption layer, the discontinuous amount of the conductor band is reduced and the leakage current is increased.
- the presence was taboo, and after removal by etching, a buffer layer formation step was performed.
- the solar cell characteristics are rather improved by the presence of the oxide film, so that the etching process is unnecessary and the manufacturing process is simplified.
- Sectional drawing which shows the general schematic structure of a CZTS type thin film solar cell.
- FIG. 4 is a diagram showing a step after the step shown in FIG.
- FIG. 1 is a cross-sectional view showing a general schematic structure of a CZTS thin film solar cell 10.
- 1 is a glass substrate
- 2 is a metal back electrode layer made of a metal such as Mo
- 3 is a p-type CZTS-based light absorption layer (hereinafter referred to as p-type light absorption layer)
- 4 is an n-type high resistance buffer layer.
- Reference numeral 5 denotes an n-type transparent conductive film.
- the p-type light absorption layer 3 is formed by, for example, sequentially stacking Cu, Zn, and Sn on the metal back electrode layer 2 by electron beam vapor deposition or the like to form a metal precursor film, and sulfiding or selenizing it.
- the n-type high resistance buffer layer 4 is generally a thin film (thickness of about 3 nm to 50 nm) of a compound containing Cd, Zn, and In, and representative materials include CdS, ZnS, and In 2 S 3 .
- these buffer layers are formed by a solution growth method (CBD method).
- CBD method a thin film is deposited on a base material by immersing the base material in a solution containing a chemical species serving as a precursor and causing a heterogeneous reaction to proceed between the solution and the surface of the base material. Therefore, the n-type high resistance buffer layer 4 after film formation does not purely contain CdS, ZnS, and In 2 S 3 but contains O and OH.
- Such a buffer layer is referred to as a CdS buffer layer, a ZnS buffer layer, or an InS buffer layer.
- the InS buffer layer has a higher discontinuity of the conductor band due to the heterojunction with the p-type light absorption layer than the CdS buffer layer or the ZnS buffer layer. Therefore, there is a problem that the leakage current is large and the leakage current is large. For this reason, a CdS buffer layer or a ZnS buffer layer is generally used as the n-type high resistance buffer layer 4.
- the n-type high resistance buffer layer 4 can be formed not only by the CBD method but also by a metal organic chemical vapor deposition method (MOCVD method) or an atomic layer deposition method (ALD method) as a dry process.
- MOCVD method metal organic chemical vapor deposition method
- ALD method atomic layer deposition method
- the n-type transparent conductive film 5 is formed with a film thickness of 0.05 to 2.5 ⁇ m using a material having n-type conductivity, a wide band gap, a transparent and low resistance. Typically, there is a zinc oxide thin film (ZnO) or an ITO thin film. In the case of a ZnO film, a low resistance film is formed by adding a group III element (for example, Al, Ga, B) as a dopant.
- the n-type transparent conductive film 5 can also be formed by sputtering (DC, RF) or the like other than MOCVD.
- the surface of the p-type light absorption layer 3 is etched using an etching gas such as ammonia, and then, for example, A CdS buffer layer or a ZnS buffer layer is grown by a solution growth method or the like. This is because the oxide film formed on the surface of the p-type light absorption layer 3 is removed before the buffer layer is formed.
- an etching gas such as ammonia
- CdO is formed at the junction in the case of the CdS buffer layer
- ZnO is formed at the junction in the case of the ZnS buffer layer. This is because oxygen in the oxide film diffuses into the buffer layer and bonds with Cd or Zn.
- the band gap of CdS is 2.4 eV
- ZnS is 3.6 eV
- ZnS is 3.4 eV.
- the oxide has a narrower band gap than the sulfide.
- n-type high resistance buffer layer 4 is formed with the oxide film remaining on the p-type light absorption layer 3, a layer with a narrow band gap is formed at the junction, and the conductor band discontinuity associated with the heterojunction is reduced. It becomes small and causes inconveniences such as an increase in leakage current.
- FIG. 2 shows an energy band diagram in the vicinity of the junction between the p-type light absorption layer 3 and the n-type high resistance buffer layer 4 of the CZTS-based thin film solar cell.
- the preferred solar cell is designed such that a certain amount of conductor band discontinuity T is secured at the heterojunction between the p-type light absorption layer 3 and the n-type high-resistance buffer layer 4.
- the discontinuity amount T is small, a failure such as an increase in leakage current occurs.
- the CdS buffer layer 4 is provided in the p-type light absorption layer 3, the discontinuous amount T is 0.2 to 0.3 eV, which is a sufficient value for obtaining a preferable solar cell. Even in the case of a ZnS buffer layer, a sufficient discontinuous amount T can be secured.
- the InS buffer layer is less utilized as a buffer layer for CIS or CZTS thin film solar cells because the discontinuity T is small and the leakage current is large compared to the CdS buffer layer and the ZnS buffer layer. Absent. However, as described above, the band gap of In 2 O 3 is 3.6 eV, which is considerably wider than the band gap of In 2 S 3 of 2.7 eV. In view of this, the inventors of the present invention, when the In 2 O 3 layer is positively interposed between the p-type light absorption layer 3 and the InS-based buffer layer, eliminates the conductor band caused by the heterojunction with the light absorption layer. It was thought that the continuous amount T could be increased and the leakage current could be suppressed. In that case, high photoelectric conversion efficiency can be expected by using the InS buffer layer as an n-type high resistance buffer layer of a CIS or CZTS thin film solar cell.
- the inventors of the present invention on the contrary to the conventional manufacturing method, positively form an oxide layer on the p-type light absorption layer 3 and then in the process of forming the InS buffer layer, In 2 O 3 We thought about promoting the formation of the film.
- the discontinuous amount T of the conductor band accompanying the heterojunction with the light absorption layer is increased and the leakage current is suppressed, so that the fill factor (FF) and the open circuit voltage (Voc) are reduced. This is because improvement can be expected.
- the buffer layer is preferably made of a material having a wide band gap from the viewpoint of light transmittance.
- the introduction of an In 2 O 3 film increases the band gap of the buffer layer, resulting in a short-circuit current density. An improvement in Jsc is expected.
- FIG. 3 (A) and 3 (B) schematically illustrate a manufacturing method according to an embodiment of the present invention.
- the p-type light absorption layer 3 is formed on the metal back electrode layer 2, this is annealed in the atmosphere, and an oxide film (see FIG. 3) is formed on the surface of the p-type light absorption layer 3. (Not shown).
- the CBD method is performed as usual to form the InS-based buffer layer 40.
- In ions which are precursor species react with the oxide film to form In 2 O 3 at the initial stage of the CBD treatment.
- the In 2 O 3 rich layer 4a is easily formed.
- In 2 S 3 is easily formed, and the In 2 S 3 rich layer 4b is formed.
- an n-type transparent conductive film 5 (see FIG. 1) is formed on the InS buffer layer 40. To do.
- Table 1 below shows the results of experiments conducted to verify the effects of the manufacturing method shown in FIG.
- Sample 1 of this experiment is a CZTS thin film solar cell in which an InS buffer layer is formed by directly performing CBD treatment without performing atmospheric annealing on the p-type light absorption layer, and sample 2 is subjected to atmospheric annealing. Then, a CZTS thin film solar cell in which an InS buffer layer is formed by performing CBD treatment. For these samples, photoelectric conversion efficiency (Eff), open circuit voltage Voc, short circuit current density Jsc, and fill factor (FF) values were measured.
- Eff photoelectric conversion efficiency
- Voc open circuit voltage
- Jsc short circuit current density Jsc
- FF fill factor
- Sample 2 that was subjected to atmospheric annealing before the CBD treatment was greatly improved in open-circuit voltage Voc and fill factor FF, and high photoelectric conversion efficiency Eff was obtained, compared with sample 1 that was not.
- Table 2 below shows the results of experiments conducted to verify the effect of the temperature of the annealing before CBD treatment.
- the temperature of atmospheric annealing is set to 130 ° C.
- the sample 4 is set to 180 ° C.
- the sample 5 is set to 250 ° C. for the experiment.
- the annealing time for each sample is 30 minutes.
- each sample formed an InS buffer layer by CBD treatment.
- Table 3 summarizes the composition of each part of the thin film solar cells of Samples 1 to 5 and the film forming method. Note that the atmospheric annealing process for the p-type light absorption layer has already been described with reference to Tables 1, 2 and 3, and is omitted in Table 3.
- Samples 1 to 5 have the p-type light absorption layer 3 having a composition of Cu 2 ZnSnS 4 , but the present invention is not limited to this example, and Cu 2 ZnSnSe 4 or Cu 2 ZnSn (S, Se It is clear that the same effect can be obtained even with 4 .
- the metal precursor film for forming the p-type light absorption layer 3 may also use Zn instead of ZnS shown in Table 3, or SnS instead of Sn.
- a vapor deposition source in which two or three of Zn, Sn, and Cu are pre-alloyed, and a vapor deposition source composed of these selenides and / or sulfides. May be used.
- simultaneous vapor deposition or sputtering may be used in addition to EB vapor deposition.
- the substrate 1, the metal back electrode layer 2, the n-type high resistance buffer layer 4 and the n-type transparent conductive film 5 are not limited to the examples shown in Table 3.
- a metal substrate such as a stainless plate, a polyimide resin substrate, or the like can be used.
- a method for forming the metal back electrode layer 2 there are an electron beam evaporation method, an electron layer deposition method (ALD method) and the like in addition to the DC sputtering method described in Table 2.
- ALD method electron layer deposition method
- a high corrosion resistance and high melting point metal such as chromium (Cr), titanium (Ti), or the like may be used.
- the same effect can be expected when the light absorption layer is formed of a CIS semiconductor or CIGS semiconductor instead of the CZTS semiconductor.
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Abstract
InS系バッファ層を用いた薄膜太陽電池は、基板上に金属裏面電極層を形成し、前記金属裏面電極層上にp型光吸収層を形成し、前記p型光吸収層表面を酸化し、酸化された前記p型光吸収層上にn型高抵抗バッファ層としてInS系バッファ層を形成し、前記InS系バッファ層上にn型透明導電膜を形成することによって、製造される。
Description
本発明は、薄膜太陽電池に関し、特に、高い光電変換効率を達成することが可能な薄膜太陽電池に関する。
近年、p型光吸収層として、I-III-VI2族化合物半導体やI2-(II-IV)-VI4族化合物半導体を用いた薄膜太陽電池が注目されている。このうち、Cu、In、Ga、Se、Sを含むカルコパイライト構造のI-III-VI2族化合物半導体を用いたものは、CIS系薄膜太陽電池と呼ばれ、代表的な材料として、Cu(In、Ga)Se2、Cu(In、Ga)(Se、S)2、CuInS2などがある。
また、p型光吸収層として、Cu,Zn,Sn,SまたはSeを含むカルコゲナイド系のI2-(II-IV)-VI4族化合物半導体を用いたものは、CZTS系薄膜太陽電池と呼ばれ、代表的なものとして、Cu2ZnSnS4、Cu2ZnSnSe4、Cu2ZnSn(S,Se)4等がある。
これらの薄膜太陽電池は、比較的安価で手に入れやすい材料を使用し、製造方法が比較的容易で、しかも可視から近赤外の波長範囲に大きな吸収係数を有するので高い光電変換効率が期待されることから、次世代型太陽電池の有力候補とみなされている。
しかしながら、これらの薄膜太陽電池で現在実現されている光電変換効率は、理論値よりもかなり低く、従って、その製造方法に大きく改善の余地がある。特に、CZTS系薄膜太陽電池では、実用に耐え得る高い光電変換効率を有する製品は得られておらず、製造技術の一層の進歩が求められている。なお、CIS系薄膜太陽電池の一般的な構造および製造方法は特許文献1にその開示があり、CZTS系薄膜太陽電池については、特許文献2に開示がある。
本発明は、CIS系薄膜太陽電池またはCZTS系薄膜太陽電池における上記の問題点を解決するためになされたものであり、その光電変換効率を増大することが可能な新たな製造方法を提供することを課題とする。
前記課題を解決するために、本発明の薄膜太陽電池は、基板上に金属裏面電極層を形成し、前記金属裏面電極層上にp型光吸収層を形成し、前記p型光吸収層表面を酸化し、酸化された前記p型光吸収層上にn型高抵抗バッファ層としてInS系バッファ層を形成し、前記InS系バッファ層上にn型透明導電膜を形成する、各ステップを実行することによって、製造される。
前記製造方法において、p型光吸収層表面の酸化を、大気中でのアニールによって行っても良い。また、前記InS系バッファ層の形成は溶液成長法(CBD法)によって行っても良い。
さらに、前記p型光吸収層を、CZTS系半導体で形成しても良い。またさらに、前記p型光吸収層を、CISまたはCIGS系半導体で形成しても良い。
p型光吸収層を、例えば大気中でアニールしてその表面に酸化膜を形成し、その後、例えば溶液成長法によってInS系バッファ層を形成すると、溶液成長法の過程で、p型光吸収層上の酸化膜からの酸素が形成されたInS系バッファ層中に拡散し、p型光吸収層との接合部分にInの酸化膜を形成する。Inの酸化物はInの硫化物よりも広いバンドギャップを有するので、接合部において、p型光吸収層とのヘテロ接合に伴う伝導体バンド不連続量を増加させる。この結果、リーク電流が抑制され、太陽電池のフィルファクタおよび開放電圧を向上させる。
さらに、バッファ層としては、光の透過性の観点からバンドギャップの広い材料が好ましい。本発明の製造方法では、接合部にIn硫化物よりバンドギャップの広いIn酸化物層が形成されるので、光の透過性が向上し、短絡電流密度が増大する。フィルファクタ、開放電圧および短絡電流密度の向上により、光電変換効率が大きく向上する。
なお、従来のCdS系或いはZnS系バッファ層を用いた薄膜太陽電池では、p型光吸収層上に酸化膜が存在すると伝導体バンド不連続量が低下しリーク電流が増大するので、酸化膜の存在はタブーとされ、エッチングにより除去した後、バッファ層の形成工程が実施されていた。本発明の方法では、酸化膜の存在によってむしろ太陽電池特性が向上するため、エッチング工程が不必要となり、製造工程が簡略化される。
以下に、本発明の種々の実施形態を図面を参照して説明する。なお、以下の図面において概略図と記載されたものは、理解を容易にするために各層の厚さを実際のものとは異なった関係で表している。また、各図面において、同一の符号は同一又は類似の構成要素を示す。さらに、以下では、本発明をCZTS系薄膜太陽電池を例にして説明しているが、本発明は、CZTS系薄膜太陽電池の製造方法にのみ限定されるものではなく、類似の組成を有するカルコゲナイド半導体である、CIS系薄膜太陽電池の製造方法にも適用されることは勿論である。
図1は、CZTS系薄膜太陽電池10の一般的な概略構造を示す断面図である。図において、1はガラス基板、2はMo等の金属を材料とする金属裏面電極層、3はp型CZTS系光吸収層(以下、p型光吸収層)、4はn型高抵抗バッファ層、5はn型透明導電膜である。p型光吸収層3は、例えば、Cu、Zn、Snを金属裏面電極層2上に順次電子ビーム蒸着等により積層して金属プリカーサー膜を形成し、これを硫化又はセレン化して形成される。
n型高抵抗バッファ層4は、一般には、Cd、Zn、Inを含む化合物の薄膜(膜厚3nm~50nm程度)であり、代表的な材料としてCdS、ZnS、およびIn2S3がある。なお、通常、これらのバッファ層は一般的には溶液成長法(CBD法)により製膜される。CBD法とは、プリカーサーとなる化学種を含む溶液に基材を浸し、溶液と基材表面との間で不均一反応を進行させることによって薄膜を基材上に析出させるものである。そのため、製膜後のn型高抵抗バッファ層4は純粋にCdS、ZnS、In2S3ではなく、O,OHを含んだものとなる。このようなバッファ層を、CdS系バッファ層、ZnS系バッファ層、InS系バッファ層と呼ぶ。
CIS系薄膜太陽電池、CZTS系薄膜太陽電池では、InS系バッファ層は、CdS系バッファ層やZnS系バッファ層と比較してp型光吸収層とのヘテロ接合に伴う伝導体バンド不連続の高さが低く、リーク電流が大きいという問題があり、そのため、一般には、n型高抵抗バッファ層4としてCdS系バッファ層やZnS系バッファ層が使用されている。
なお、n型高抵抗バッファ層4はCBD法だけではなく、ドライプロセスとして有機金属気相成長法(MOCVD法)、原子層堆積法(ALD法)によっても製膜することができる。
n型透明導電膜5としては、n型の導電性を有し、バンドギャップが広く、透明でかつ低抵抗の材料を用いて、膜厚0.05~2.5μmに形成される。代表的には酸化亜鉛系薄膜(ZnO)あるいはITO薄膜がある。ZnO膜の場合、III族元素(例えばAl、Ga、B)をドーパントとして添加することで低抵抗膜とする。n型透明導電膜5は、MOCVD法以外に、スパッタ法(DC、RF)等で形成することもできる。
従来のCZTS系薄膜太陽電池の製造方法では、n型高抵抗バッファ層4の製膜前に、アンモニア等のエッチングガスを使用して、p型光吸収層3の表面をエッチングし、その後、例えば溶液成長法等によってCdS系バッファ層あるいはZnS系バッファ層を成長させている。これは、バッファ層の製膜前に、p型光吸収層3表面に形成された酸化膜を除去するためである。
バッファ層を形成する表面に酸化膜が存在すると、CdS系バッファ層の場合はCdOが、ZnS系バッファ層の場合はZnOが、接合部に形成される。これは、酸化膜中の酸素がバッファ層中に拡散してCd或いはZnと結合するためである。CdS系バッファ層の場合、CdSのバンドギャップは2.4eVであるのに対し、CdOは2.1eV、ZnS系バッファ層の場合、ZnSが3.6eVであるのに対し、ZnOは3.4eVであり、何れの場合も酸化物の方が硫化物より狭いバンドギャップを有する。従って、p型光吸収層3上に酸化膜を残したままでn型高抵抗バッファ層4を形成すると、接合部にバンドギャップの狭い層が形成され、ヘテロ接合に伴う伝導体バンド不連続量が小さくなって、リーク電流を増加させるなどの不都合を生じる。
図2は、CZTS系薄膜太陽電池のp型光吸収層3とn型高抵抗バッファ層4との接合付近のエネルギーバンド図を示す。好ましい太陽電池では、p型光吸収層3とn型高抵抗バッファ層4とのヘテロ接合において、ある程度の伝導体バンド不連続量Tが確保されるように設計されている。この不連続量Tが小さいと、リーク電流の増大等の障害が発生する。p型光吸収層3にCdS系バッファ層4を設けた場合、この不連続量Tは0.2~0.3eVであり、好ましい太陽電池を得るためには充分な値である。ZnS系バッファ層の場合も、充分な不連続量Tが確保できる。
ところが、これらのバッファ層4とp型光吸収層3との界面に、硫化物よりバンドギャップの小さいCdOあるいはZnO等の酸化膜が形成されると、不連続量Tが低下し、障害を発生させる。従って、このような酸化膜の形成を排除するために、p型光吸収層3の表面に形成される酸化膜を予めエッチング等で除去する必要がある。
本発明者等は、望ましいn型高抵抗バッファ層材料の探索中、InS系バッファを用いた場合には状況が全く異なることに気がついた。InS系バッファの場合、In2S3のバンドギャップが2.7eVであるのに対し、In2O3のバンドギャップは3.6eVであり、酸化物の方が硫化物よりバンドギャップがかなり大きい。従って、この特性をうまく利用できれば、InS系バッファ層を用いて光電変換効率の高い太陽電池を実現できるのではないか、と考えた。
InS系バッファ層は、CdS系バッファ層およびZnS系バッファ層と比較して不連続量Tが小さく、リーク電流が大きいために、CIS系またはCZTS系薄膜太陽電池のバッファ層としては余り利用されていない。しかしながら、上述したように、In2O3のバンドギャップは3.6eVと、In2S3のバンドギャップ2.7eVと比較してかなり広い。そこで、本発明者等は、In2O3層をp型光吸収層3とInS系バッファ層との間に積極的に介在させると、光吸収層とのヘテロ接合に伴う伝導体バンドの不連続量Tが大きくなり、リーク電流を抑制することができるのではないかと考えた。その場合、InS系バッファ層を、CIS系またはCZTS系薄膜太陽電池のn型高抵抗バッファ層として使用して、高い光電変換効率を期待することができる。
従って、本発明者等は、従来の製造方法とは反対に、p型光吸収層3上に積極的に酸化層を形成して、その後のInS系バッファ層の製膜過程でIn2O3膜の生成を促すことを考えた。In2O3膜の生成によって、光吸収層とのヘテロ接合に伴う伝導体バンドの不連続量Tを大きくし、リーク電流を抑制することで、フィルファクタ(FF)および開放電圧(Voc)の向上が期待できるからである。
さらに、バッファ層としては光の透過性の観点からバンドギャップが広い材料が好ましいが、InS系バッファの場合、In2O3膜を導入することでバッファ層のバンドギャップが広くなり、短絡電流密度Jscの向上が期待される。
図3(A)および(B)は、本発明の一実施形態に係る製造方法を概略図示するものである。図3(A)に示すように、金属裏面電極層2上にp型光吸収層3が形成された後、これを大気中でアニールし、p型光吸収層3の表面に酸化膜(図示せず)を形成する。次に、図3(B)に示すように、通常通りにCBD法を実行してInS系バッファ層40を形成する。このとき、p型光吸収層3上には大気アニールによって酸化膜が形成されているため、CBD処理の初期では、プリカーサー種であるInイオンが酸化膜と反応してIn2O3を形成しやすく、In2O3リッチ層4aが形成される。CBD処理が進むと、In2S3が形成されやすくなり、In2S3リッチ層4bが形成される。
In2O3リッチ層4aとIn2S3リッチ層4bを含むInS系バッファ層40が形成されると、その上に、n型透明導電膜5(図1参照)を形成して太陽電池とする。
以下の表1は、図3に示した製造方法の効果を検証するために行った実験の結果を示す。この実験のサンプル1は、p型光吸収層に対して大気アニールを行わず、直接CBD処理を行ってInS系バッファ層を形成したCZTS系薄膜太陽電池であり、サンプル2は、大気アニールを実施した後、CBD処理を行ってInS系バッファ層を形成したCZTS系薄膜太陽電池である。これらのサンプルに対して、光電変換効率(Eff)、開放電圧Voc、短絡電流密度Jscおよびフィルファクタ(FF)の値を測定した。なお、サンプル2では、大気アニールを雰囲気温度130℃で、約30分間おこなった。
CBD処理前に大気アニールを行ったサンプル2は、行わなかったサンプル1に比べて、開放電圧VocおよびフィルファクタFFが大きく改善し、高い光電変換効率Effを得ることができた。これは、InS系バッファの場合、CBD処理前にp型光吸収層3上に酸化膜を形成しておくことによって、InS系バッファ層の光吸収層接合側がIn2O3リッチとなった効果であると推測される。
以下に示す表2は、CBD処理前アニールの温度の効果を検証するために行った実験結果を示す。サンプル3では大気アニールの温度を130℃とし、サンプル4では180℃とし、サンプル5では250℃として、実験を行っている。各サンプルともアニール時間は30分である。p型光吸収層3の大気アニール後、何れのサンプルもCBD処理によってInS系バッファ層を形成した。
180℃でCBD処理前アニールを行ったサンプル4と、250℃でアニールを行ったサンプル5は、130℃でアニールを行ったサンプル3に比べて高い光電変換効率Effを有している。このことから、比較的高いアニール温度で充分にp型光吸収層の酸化を行った方が、光電変換効率の改善に繋がるものと考えられる。
なお、サンプル2~サンプル5では、p型光吸収層3上に酸化膜を形成する方法として、大気中でのアニールを採用したが、本発明はこれに限定されることなく、酸素含有雰囲気中でのアニールであれば良い。
なお、サンプル1~5では、組成がCu2ZnSnS4のp型光吸収層3を有するが、本発明はこの事例に限定されるものではなく、Cu2ZnSnSe4又はCu2ZnSn(S,Se)4であっても、同様の効果が得られることは明らかである。さらに、p型光吸収層3を形成するための金属プリカーサー膜も、表3に示すZnSの代わりにZnを用いても良く、Snの代わりにSnSであっても良い。さらに、Zn、Sn、Cuを順次製膜する以外に、Zn、Sn、およびCuのうち2種あるいは3種を予め合金化した蒸着源や、これらのセレン化物及び/又は硫化物からなる蒸着源を用いても良い。製膜方法として、EB蒸着以外に同時蒸着法やスパッタ法を用いても良い。
さらに、基板1、金属裏面電極層2、n型高抵抗バッファ層4及びn型透明導電膜5も、表3に記載する事例に限定されない。例えば、基板1として、青板ガラス、低アルカリガラス等のガラス基板の他に、ステンレス板等の金属基板、ポリイミド樹脂基板等を用いることができる。金属裏面電極層2の形成方法としては、表2に記載するDCスパッタ法以外に、電子ビーム蒸着法、電子層堆積法(ALD法)等がある。金属裏面電極層2の材料としては、高耐蝕性でかつ高融点金属、例えばクロム(Cr)、チタン(Ti)等を用いても良い。
さらに、CZTS系半導体の代わりに、CIS系半導体或いはCIGS系半導体によって光吸収層を形成した場合も、同様の効果を期待することができることは勿論である。
上述の表1から表3に示した実験は、光吸収層としてp型CZTS系光吸収層を形成した太陽電池に対して行われたものである。しかしながら、CIS系(或いはCIGS系)薄膜太陽電池とCZTS系薄膜太陽電池は共に、類似の組成を有する硫化物半導体を光吸収層に用いているので、CIS系薄膜太陽電池の場合も、CZTS系薄膜太陽電池と同様に、InS系バッファ層の形成前の光吸収層の酸化が光電変換効率の改善に効果がある。
1 基板
2 金属裏面電極層
3 p型光吸収層
4 n型高抵抗バッファ層
4a In2O3リッチ層
4b In2S3リッチ層
5 n型透明導電膜
40 InS系バッファ層
2 金属裏面電極層
3 p型光吸収層
4 n型高抵抗バッファ層
4a In2O3リッチ層
4b In2S3リッチ層
5 n型透明導電膜
40 InS系バッファ層
Claims (5)
- 基板上に金属裏面電極層を形成し、
前記金属裏面電極層上にp型光吸収層を形成し、
前記p型光吸収層表面を酸化し、
酸化された前記p型光吸収層上にn型高抵抗バッファ層としてInS系バッファ層を形成し、
前記InS系バッファ層上にn型透明導電膜を形成する、
各ステップを備える、薄膜太陽電池の製造方法。 - 請求項1に記載の製造方法において、前記p型光吸収層表面の酸化は、前記p型光吸収層を大気中でアニールすることによって行われる、薄膜太陽電池の製造方法。
- 請求項1または2に記載の製造方法において、前記InS系バッファ層の形成は溶液成長法(CBD法)によって行われる、薄膜太陽電池の製造方法。
- 請求項1乃至3の何れか1項に記載の製造方法において、前記p型光吸収層は、CZTS系半導体で形成される、薄膜太陽電池の製造方法。
- 請求項1乃至3の何れか1項に記載の製造方法において、前記p型光吸収層は、CISまたはCIGS系半導体で形成される、薄膜太陽電池の製造方法。
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EP12853469.0A EP2787537B1 (en) | 2011-12-02 | 2012-11-30 | THIN FILM SOLAR CELL with indium sulfide buffer layer |
US14/362,065 US20140315348A1 (en) | 2011-12-02 | 2012-11-30 | Thin film solar cell |
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JP2011264652A JP5258951B2 (ja) | 2011-12-02 | 2011-12-02 | 薄膜太陽電池 |
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JP2006165386A (ja) | 2004-12-09 | 2006-06-22 | Showa Shell Sekiyu Kk | Cis系薄膜太陽電池及びその作製方法 |
JP2007317885A (ja) * | 2006-05-25 | 2007-12-06 | Honda Motor Co Ltd | 太陽電池およびその製造方法 |
WO2010023264A2 (en) * | 2008-08-29 | 2010-03-04 | Odersun Ag | Thin film solar cell and photovoltaic string assembly |
JP2010215497A (ja) | 2009-02-20 | 2010-09-30 | Toyota Central R&D Labs Inc | 硫化物及び光電素子 |
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JP4055053B2 (ja) * | 2002-03-26 | 2008-03-05 | 本田技研工業株式会社 | 化合物薄膜太陽電池およびその製造方法 |
US20100273287A1 (en) * | 2009-04-23 | 2010-10-28 | Reel Solar, Inc. | Methods for integrating quantum window structures into solar cells |
JP2011165900A (ja) * | 2010-02-10 | 2011-08-25 | Fujifilm Corp | 光電変換素子の製造方法 |
CN102782853A (zh) * | 2010-03-05 | 2012-11-14 | 第一太阳能有限公司 | 具有分级缓冲层的光伏器件 |
US20130037100A1 (en) * | 2010-04-09 | 2013-02-14 | Charlotte PLATZER BJÖRKMAN | Thin Film Photovoltaic Solar Cells |
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JP2006165386A (ja) | 2004-12-09 | 2006-06-22 | Showa Shell Sekiyu Kk | Cis系薄膜太陽電池及びその作製方法 |
JP2007317885A (ja) * | 2006-05-25 | 2007-12-06 | Honda Motor Co Ltd | 太陽電池およびその製造方法 |
WO2010023264A2 (en) * | 2008-08-29 | 2010-03-04 | Odersun Ag | Thin film solar cell and photovoltaic string assembly |
JP2010215497A (ja) | 2009-02-20 | 2010-09-30 | Toyota Central R&D Labs Inc | 硫化物及び光電素子 |
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US20140315348A1 (en) | 2014-10-23 |
JP5258951B2 (ja) | 2013-08-07 |
EP2787537A4 (en) | 2015-08-05 |
EP2787537B1 (en) | 2016-07-20 |
JP2013118265A (ja) | 2013-06-13 |
EP2787537A1 (en) | 2014-10-08 |
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