WO2007086521A1 - 太陽電池およびその製造方法 - Google Patents
太陽電池およびその製造方法 Download PDFInfo
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- WO2007086521A1 WO2007086521A1 PCT/JP2007/051302 JP2007051302W WO2007086521A1 WO 2007086521 A1 WO2007086521 A1 WO 2007086521A1 JP 2007051302 W JP2007051302 W JP 2007051302W WO 2007086521 A1 WO2007086521 A1 WO 2007086521A1
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- Prior art keywords
- light absorption
- layer
- absorption layer
- solar cell
- contact electrode
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- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 230000031700 light absorption Effects 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 26
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 21
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 18
- 239000010409 thin film Substances 0.000 abstract description 17
- 239000004065 semiconductor Substances 0.000 abstract description 12
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 229910052738 indium Inorganic materials 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011669 selenium Substances 0.000 abstract description 7
- 229910052733 gallium Inorganic materials 0.000 abstract description 6
- 229910052711 selenium Inorganic materials 0.000 abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- -1 chalcopyrite compound Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 241000652704 Balta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000002329 Inga feuillei Species 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01L31/04—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 at least one potential-jump barrier or surface barrier
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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
- H01L31/02—Details
- H01L31/0236—Special surface textures
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- H—ELECTRICITY
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- 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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- 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
- H01L31/0392—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 thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- 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
- H01L31/0392—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 thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
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- 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
- H01L31/0392—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 thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03925—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 thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
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- 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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
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- 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
- H01L31/04—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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
- H01L31/046—PV modules composed of a plurality of thin film solar cells deposited on the same substrate
- H01L31/0463—PV modules composed of a plurality of thin film solar cells deposited on the same substrate characterised by special patterning methods to connect the PV cells in a module, e.g. laser cutting of the conductive or active layers
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- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
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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 chalcopyrite solar cell that is a compound-based solar cell and a method for manufacturing the same, and in particular, a point using a substrate with irregularities on the surface and unit cells of the solar cell are connected in series.
- the present invention relates to a solar cell having a feature in a contact electrode portion and a manufacturing method thereof.
- Solar cells that receive light and convert it into electrical energy are classified into a Balta system and a thin film system depending on the thickness of the semiconductor.
- thin-film solar cells have several semiconductor layers! ⁇ Several; solar cells with thickness less than or equal to zm, classified into Si thin film type and compound thin film type.
- compound thin film systems such as II-VI group compounds and chalcopyrite systems.
- chalcopyrite solar cells belonging to the chalcopyrite system are also known as CIGS (Cu (InGa) Se) thin film solar cells, CIGS solar cells, or I III VI group materials, depending on the materials used. It is called.
- a chalcopyrite solar cell is a solar cell formed using a chalcopyrite compound as a light-absorbing layer, and has high efficiency, no light degradation (aging), excellent radiation resistance, and light absorption. It has features such as a wide wavelength range and a high light absorption coefficient, and is currently being studied for mass production.
- Fig. 1 shows a cross-sectional structure of a general chalcopyrite solar cell.
- a chalcopyrite solar cell has a lower electrode layer (Mo electrode layer) formed on a glass substrate (substrate) and a light absorption layer (CIGS) containing copper'indium.gallium.selenium. Light absorption layer), a high-resistance buffer layer thin film formed of InS, ZnS, CdS, etc. on the light absorption layer thin film, and an upper electrode thin film (TCO) formed of ZnOAl, etc.
- an alkali control layer mainly composed of SiO or the like is used to control the amount of alkali metal component (Na) leached into the light absorption layer.
- FIG. 2 shows a process for manufacturing a chalcopyrite solar cell.
- a Mo (molybdenum) electrode serving as a lower electrode is formed on a glass substrate such as soda lime glass by sputtering.
- the Mo electrode is divided by removing it by laser irradiation or the like (first scribe).
- the shore IJ waste is washed with water or the like, and copper (Cu), indium (In) and gallium (Ga) are deposited by sputtering or the like to form a precursor.
- This precursor is put into a furnace and annealed in an atmosphere of H Se gas, so that a chalcopyrite light absorption is achieved.
- This annealing process is usually referred to as gas phase selenization or simply selenization.
- an n-type buffer layer such as CdS, ZnO, or InS is laminated on the light absorption layer.
- the buffer layer is generally formed by a method such as sputtering or CBD (Chemical 'Bath' Deposition).
- CBD Chemical 'Bath' Deposition
- the buffer layer and the precursor are removed by laser irradiation, metal needles, or the like (second scribe).
- Figure 3 shows the scribing with a metal needle.
- a transparent electrode (TCO: Transparent Conducting Oxides) film such as ZnOAl is formed by sputtering or the like as the upper electrode.
- TCO transparent Conducting Oxides
- the upper electrode (TCO), buffer layer, and precursor are divided by laser irradiation, metal needles, etc. (third scribe: element separation), so that the CIGS thin film solar cell Complete
- the solar cell obtained here is called a cell in which each unit cell is monolithically connected in series.
- a single cell or a plurality of cells are packaged to form a module.
- a cell is configured by connecting a plurality of unit cells in series by each scribing process.
- the cell voltage can be set arbitrarily by changing the number of series cells (number of unit cells). The design can be changed to It becomes ability.
- Patent Document 1 discloses a technique in which a light-absorbing layer and a buffer layer are scraped off by moving a metal needle (needle) having a tapered tip at a predetermined pressure. ing.
- the light absorption layer is removed by irradiating the light absorption layer with a laser (Nd: YAG laser) oscillated by exciting a Nd: YAG crystal with a continuous discharge lamp such as an arc lamp.
- a laser Nd: YAG laser
- a glass substrate (texture substrate) having a concave and convex surface is used, electrodes are formed on the glass substrate, and silicon semiconductors are sequentially formed.
- a technology has been developed to improve the conversion efficiency by the light confinement effect by creating a solar cell by stacking layers.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2004-115356
- Patent Document 2 Japanese Patent Laid-Open No. 11 312815
- Patent Document 3 Japanese Patent Laid-Open No. 2-164077
- the conventional texture substrate disclosed in Patent Document 3 has a power that cannot be applied to a power rucopyrite type solar cell that is a compound solar cell. The reason is that if the substrate is concave and convex, the second scribe cannot be performed and a monolithic series-stage connection structure cannot be adopted.
- Fig. 4 (a) is a photo when a glass substrate with a smooth surface is used
- (b) is This is a photograph when a textured substrate with an uneven surface is used.
- FIG. 4 (b) when a second scribe is performed when a texture substrate is used, a scribe residue is clearly generated. This is because the diameter of the metal needle (two dollars) used for the mecha-cal scribing is wider than the unevenness of the texture substrate.
- the texture substrate used in the experiment in Fig. 4 has a concavo-convex period (horizontal distance from the maximum height to the minimum height) of 5.9 ⁇ m, whereas the needle tip diameter is about 35 ⁇ m. m and the tip of the needle has a diameter about 6 times larger.
- the light absorbing layer that has not been removed by one dollar remains between the transparent electrode and the lower electrode after the transparent electrode (TCO) is deposited.
- the light absorption layer has a resistivity of about 10 4 ⁇ cm, while the resistivity of molybdenum constituting the lower electrode is 5.4 X 10 _6 Q cm. If the part exists as a residue, the resistance value increases, and the light energy conversion efficiency (power generation efficiency) decreases.
- the intensity of the laser beam to remove only the light absorption layer where the thickness of the light absorption layer and the incident angle of the laser are not uniform.
- the laser beam to be irradiated is strong, after the light absorption layer is removed, one more laser beam is irradiated, resulting in damage to the lower electrode (Mo electrode).
- the laser light is weak! If the light absorption layer cannot be completely removed, it remains as a high resistance layer as described above, so the upper transparent electrode (TCO) and the lower Mo electrode There is a problem that the contact resistance with is extremely bad.
- a solar cell according to the present invention includes a substrate having irregularities on a main surface, and a plurality of lower electrodes formed on the main surface side of the substrate and formed by dividing a conductive layer, A chalconeite-type light absorption layer formed on the plurality of lower electrodes and divided into a plurality of parts, a plurality of upper electrodes that are transparent conductive layers formed on the light absorption layer, and the lower electrode layer And a contact electrode portion having a conductivity higher than that of the light absorption layer in which a part of the light absorption layer is modified so that unit cells composed of the light absorption layer and the upper electrode are connected in series.
- the basic configuration of the solar cell according to the present invention is configured by laminating the lower electrode, the light absorption layer, and the upper electrode on the substrate, and these layers constitute the solar cell according to the present invention.
- the solar cell of the present invention also includes an indispensable constituent element that includes a nofer layer, an alkali passivation film, an antireflection film, and the like as required between the respective layers.
- the contact electrode portion is modified from a P-type semiconductor by functioning as a CuZln ratio force light absorption layer higher than the CuZln ratio ratio of the light absorption layer, and functions as an electrode. Further, when the lower electrode also has a molybdenum (Mo) force, it is modified to an alloy containing molybdenum.
- Mo molybdenum
- the method for manufacturing a solar cell according to the present invention includes a lower electrode forming step of forming a lower electrode layer on a main surface side of a substrate having an uneven surface, and the lower electrode layer is formed into a plurality of lower electrodes.
- the buffer layer forming step is provided after the light absorbing layer forming step, the laser beam is irradiated from above the buffer layer.
- the portion for connecting the unit cells as in the conventional case is thin. Therefore, resistance does not increase. Even if a textured substrate with an uneven surface is used as the substrate, the second scribe is not performed, so the lower electrode (Mo electrode) is damaged or a part of the light absorption layer cannot be removed and remains. And there is also a disadvantage.
- the electrode layer formed on the substrate is not peeled, and the light receiving area is further increased, so that the photoelectric conversion efficiency is improved.
- FIG. 1 is a cross-sectional view showing the structure of a conventional chalcopyrite solar cell
- FIG.2 Diagram showing a series of manufacturing processes for conventional chalcopyrite solar cells
- FIG.3 Diagram showing scribing with a metal needle
- FIG. 4 Photographs taken from the top surface of the substrate after mecha-calc scribing, (a) is a photograph using a glass substrate with a smooth surface, and (b) is a texture with uneven surfaces. Photo of using a board
- FIG. 5 is a cross-sectional view of the main part of a chalcopyrite solar cell according to the present invention.
- FIG. 6 is a diagram showing a method for manufacturing a chalcopyrite solar cell of the present invention
- FIG. 8 (a) is a graph showing the result of component analysis of the light absorption layer without the laser contact formation process, and (b) is a graph showing the component analysis result of the laser contact part after the laser contact formation process.
- FIG. 9 (a) is a graph showing the difference in carrier concentration in the light absorption layer depending on the CuZln ratio, and (b) is a graph showing the change in resistivity depending on the first uZln ratio.
- FIG. 10 SEM photograph of the surface of the solar cell where the contact electrode was formed by the laser contact formation process of the present invention.
- FIG. 5 shows a chalconeite solar cell according to the present invention.
- Figure 5 shows a solar cell
- a chalcopyrite solar cell comprises a lower electrode layer 2 (Mo electrode layer) formed on a substrate 1 (texture substrate) such as glass having an uneven surface, and copper 'indium' gallium.
- a light absorption layer 3 (CIGS light absorption layer) containing mu-selenium, a high resistance nofer layer thin film 4 formed of InS, ZnS, CdS, etc. on the light absorption layer 3, and ZnOAl, etc.
- a unit cell (unit cell) is formed from the upper electrode layer 5 (transparent electrode layer: TCO), and the upper electrode layer 5 and the lower electrode layer 2 are formed for the purpose of connecting a plurality of unit cells in series.
- a contact electrode portion 6 is formed to connect the two.
- the contact electrode portion 6 is configured such that the Cu / In ratio is larger than the CuZln ratio of the light absorption layer 3, in other words, the In is configured to be less, and the light that is a p-type semiconductor Show p + (plus) type or conductor characteristics for absorbing layer 3! /
- the glass substrate as a material for the texture substrate has a resistance to heat of about 650 ° C, and it is only required to have resistance from the vapor phase selenization process.
- it may be a substrate including My power, polyimide, ceramic, stainless steel or carbon with an insulating covering, or the like.
- the texture substrate is provided with irregularities on the surface by a physical cutting process such as sandblasting or a chemical treatment process such as hydrofluoric acid on a substrate (glass) as a material.
- a physical cutting process such as sandblasting or a chemical treatment process such as hydrofluoric acid on a substrate (glass) as a material.
- the average height difference is 2 .: m and the average horizontal distance from the maximum height to the minimum height is 5.9 m.
- the adhesion between the substrate and molybdenum as the lower electrode is improved, and the contact area between the lower electrode and the light absorption layer is increased, resulting in a decrease in electrical resistance.
- the optical confinement effect can be obtained.
- the optical confinement effect is to increase the optical energy that stays at the pn junction for a long time (that is, confine light) by increasing the optical path length, and consequently promote more photoelectric conversion. .
- FIG. 6 shows a method for manufacturing a chalcopyrite solar cell of the present invention.
- a Mo (molybdenum) electrode to be a lower electrode is formed on the texture substrate by sputtering or the like.
- titanium or tungsten can be used for the lower electrode.
- the lower electrode (molybdenum Mo electrode) is divided by laser irradiation or the like. (First scribe)
- the laser is preferably an excimer laser with a wavelength of 256 nm or the third harmonic of a YAG laser with a wavelength of 355 nm.
- Cu copper
- In indium
- Ga gallium
- This precursor is put into the furnace, and the temperature is about 400 ° C to 600 ° C in the atmosphere of H Se gas.
- the light absorption layer thin film is obtained by annealing. This annealing process is usually called gas phase selenization or simply selenium.
- a buffer layer which is an n-type semiconductor such as CdS, ZnO, or InS, is stacked on the light absorption layer.
- the buffer layer is generally formed by a dry process such as sputtering or a wet process such as CBD (Chemical 'Bath Deposition).
- the nota layer can be omitted by improving the transparent electrode described later.
- the light absorption layer is modified to form a contact electrode portion.
- the laser is also applied to the buffer layer.
- the buffer layer itself is formed to be extremely thin compared to the light absorption layer, and no influence due to the presence or absence of the buffer layer is observed in the experiments of the present inventors.
- a transparent electrode (TCO) such as ZnOAl to be an upper electrode is formed by sputtering or the like on the notch layer and the contact electrode. Finally, the TCO, the noffer layer and the precursor are removed and divided by laser irradiation or metal needles. (Scribe for device isolation).
- FIG. 7 shows SEM photographs of the light absorption layer and the surface of the contact electrode after laser irradiation. As shown in Fig. 7, contact power is applied to the light-absorbing layer grown in the form of particles. It can be seen that the pole is melted and recrystallized by the energy of the laser.
- FIG. 8 is used to verify the contact electrode formed according to the present invention in comparison with the light absorption layer before laser irradiation.
- Fig. 8 (a) shows the component analysis results of the light absorption layer without the laser contact formation process, and (b) shows the component analysis results of the laser contact part with the laser contact formation process.
- EPMA Electro Probe Micro-Analysis
- EP MA detects constituent elements by analyzing the spectrum of characteristic X-rays generated by irradiating a substance with an accelerated electron beam and exciting the electron beam. Furthermore, the ratio (concentration) of each constituent element is determined. To analyze.
- FIG. 8 shows that indium (In) is significantly reduced in the contact electrode with respect to the light absorption layer.
- Mo molybdenum
- the surface temperature of the light absorption layer rises to about 6,000 ° C.
- the temperature is lower on the inside (lower) side of the light absorption layer, but the light absorption layer used in the examples is 1 ⁇ m, and it can be said that the temperature inside the light absorption layer is considerably high.
- the melting point of indium is 156 ° C
- the boiling point is 2,000 ° C
- the melting point of copper is 1,084 ° C and the boiling point is 2,595 ° C.
- indium has reached its boiling point deeper in the light absorption layer than copper.
- the melting point of molybdenum is 2,610 ° C, it is assumed that some molybdenum force existing in the lower electrode melts and is taken into the light absorption layer side.
- Figure 9 shows the change in characteristics due to the CuZln ratio.
- Fig. 9 (a) shows the difference in carrier concentration in the light absorption layer depending on the CuZln ratio
- Fig. 9 (b) shows the change in resistivity depending on the CuZln ratio. Yes.
- Molybdenum is a metal element belonging to Group 6 of the periodic table and has a specific resistance of 5.4 X 10 _6 Q cm. When the light absorption layer melts and recrystallizes in the form of molybdenum, the resistivity decreases.
- the contact electrode force (plus) type or metal changes to lower resistance than the light absorption layer.
- Figure 10 shows a SEM photo of the surface of the solar cell after TCO lamination.
- the light absorption layer remains on the texture substrate, so it was difficult to remove the light absorption layer without damaging the Mo electrode.
- a monolithic series connection structure is created by the contact electrode portion in which the light absorption layer is modified.
- a defect occurs in the transparent electrode.
- FIG. 11 shows a cross-sectional SEM photograph of the contact electrode portion and the light absorption layer in order to clarify that the contact electrode portion has no significant change compared to the thickness of the light absorption layer.
- the contact electrode shown in Fig. 11 was irradiated 5 times with a laser with a frequency of 20 kHz, an output of 467 mW, and a pulse width of 35 ns. The number of times was set to 5 in order to observe the decrease in the thickness of the contact electrode due to laser irradiation. As shown in FIG. 11, even if the laser is irradiated five times, the film thickness of the contact electrode part is likely to remain considerably.
- the light absorption layer was modified by adopting a contact electrode portion forming step of irradiating a laser instead of the second scribe when using a substrate material having irregularities on the surface.
- a contact electrode part can be obtained.
- the internal resistance in series connection can be reduced, and a chalcopyrite solar cell with high photoelectric conversion efficiency can be obtained.
Abstract
Description
Claims
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DE112007000269T DE112007000269T5 (de) | 2006-01-30 | 2007-01-26 | Solarzelle und Verfahren zur Herstellung derselben |
US12/162,727 US20090194150A1 (en) | 2006-01-30 | 2007-01-26 | Solar cell and method for fabricating the same |
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JP2006-019969 | 2006-01-30 | ||
JP2006019969A JP2007201304A (ja) | 2006-01-30 | 2006-01-30 | 太陽電池およびその製造方法 |
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US (1) | US20090194150A1 (ja) |
JP (1) | JP2007201304A (ja) |
CN (1) | CN101379622A (ja) |
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WO (1) | WO2007086521A1 (ja) |
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US8691619B2 (en) | 2007-11-30 | 2014-04-08 | Showa Shell Sekiyu, K.K. | Laminated structure for CIS based solar cell, and integrated structure and manufacturing method for CIS based thin-film solar cell |
US20110017289A1 (en) * | 2009-07-24 | 2011-01-27 | Electronics And Telecommunications Research Institute | Cigs solar cell and method of fabricating the same |
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DE112007000269T5 (de) | 2008-11-27 |
US20090194150A1 (en) | 2009-08-06 |
JP2007201304A (ja) | 2007-08-09 |
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