WO2006126598A1 - Cis系薄膜太陽電池の高抵抗バッファ層・窓層(透明導電膜)連続製膜方法及びその連続製膜方法を実施するための連続製膜装置 - Google Patents
Cis系薄膜太陽電池の高抵抗バッファ層・窓層(透明導電膜)連続製膜方法及びその連続製膜方法を実施するための連続製膜装置 Download PDFInfo
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- WO2006126598A1 WO2006126598A1 PCT/JP2006/310371 JP2006310371W WO2006126598A1 WO 2006126598 A1 WO2006126598 A1 WO 2006126598A1 JP 2006310371 W JP2006310371 W JP 2006310371W WO 2006126598 A1 WO2006126598 A1 WO 2006126598A1
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- Prior art keywords
- film
- layer
- buffer layer
- solar cell
- window layer
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 111
- 239000010408 film Substances 0.000 title claims description 198
- 239000010409 thin film Substances 0.000 title claims description 79
- 238000000151 deposition Methods 0.000 title abstract description 17
- 230000008021 deposition Effects 0.000 title abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 36
- 239000011701 zinc Substances 0.000 claims description 36
- 230000031700 light absorption Effects 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011265 semifinished product Substances 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000001307 helium Substances 0.000 claims description 15
- 229910052734 helium Inorganic materials 0.000 claims description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 15
- 150000002902 organometallic compounds Chemical class 0.000 claims description 12
- 239000012159 carrier gas Substances 0.000 claims description 11
- 239000004065 semiconductor Substances 0.000 claims description 10
- 238000009751 slip forming Methods 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002019 doping agent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 6
- 229940007718 zinc hydroxide Drugs 0.000 claims description 6
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- -1 zinc organometallic compound Chemical class 0.000 claims description 2
- 229910007541 Zn O Inorganic materials 0.000 claims 2
- 238000005137 deposition process Methods 0.000 claims 2
- 230000000717 retained effect Effects 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 241
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 240000002329 Inga feuillei Species 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011669 selenium Substances 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 7
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 6
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-O hydridodioxygen(1+) Chemical compound [OH+]=O MYMOFIZGZYHOMD-UHFFFAOYSA-O 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L31/042—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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
- C23C16/306—AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/54—Apparatus specially adapted for continuous coating
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- 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
-
- 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 continuous film forming method for continuously forming a high-resistance buffer layer and a window layer (transparent conductive film) of a CIS-based thin film solar cell by a MOCVD method, and the continuous film forming method.
- the present invention relates to a continuous film forming apparatus.
- Patent Document 1 discloses a high-resistance buffer layer on a light-absorbing layer made of a CuInSe thin film.
- the solution growth method for film formation involves immersing the CuInSe thin film light absorption layer in the solution.
- a high-quality heterojunction is formed with the CuInSe thin film light absorption layer by etching or selective cleaning effect on the surface of the thin film light absorption layer.
- Patent Document 2 a zinc mixed crystal compound containing oxygen, ion and hydroxyl group chemically grown on a p-type light absorption layer, that is, zinc (0, S, OH) x is also included.
- a manufacturing method is disclosed that can be used as a high-resistance buffer layer to obtain a thin-film solar cell with high conversion efficiency equivalent to that obtained when a CdS layer is used as a buffer layer.
- Patent Document 2 discloses a manufacturing method effective for eliminating the CdS buffer layer, which is understood to be essential for a manufacturing method of a thin film solar cell with high conversion efficiency.
- Patent Document 1 US Patent No. 4611091 (Class 136Z260, issued September 9, 1986)
- Patent Document 2 Japanese Patent No. 3249342 (JP-A-8-330614)
- the present invention is for solving the above-mentioned problems, and the object of the present invention is to achieve output characteristics (conversion efficiency) equivalent to that of a conventional film growth method using a solution growth method, by a film formation method using a MOCVD method. , Open circuit voltage, short circuit current density, fill factor), and simplify manufacturing method, reduce raw material cost and waste disposal cost, and greatly reduce manufacturing cost. Means for solving the problem
- the present invention includes a glass substrate, a metal back electrode layer, a p-type conductive CIS-based (CuInSe-based) chalcopyrite multicomponent compound semiconductor thin film, a transparent high-resistance sub-layer
- the buffer is formed on the light absorption layer of a semi-finished solar cell substrate in which a metal back electrode layer and a light absorption layer are formed in this order on the glass substrate.
- a high-resistance buffer layer / window layer transparent conductive film
- the present invention has a structure in which the buffer layer and the window layer have a structure in which a plurality of preheating steps and film forming steps are connected in-line by a metal organic chemical vapor deposition (MOC VD) method.
- MOC VD metal organic chemical vapor deposition
- the buffer layer and the window layer are adjacent to each other in the same MOCVD film forming apparatus, and are continuously formed by independent buffer layer forming process and window layer forming process.
- This is a method for continuously forming a high-resistance buffer layer / window layer (transparent conductive film) of the CIS-based thin-film solar cell described in (1) above.
- the film forming step of the buffer layer and the window layer uses a metal organic compound of zinc and pure water as a film forming raw material, and these are filled in a bubbler and the like, and helium, argon Inactivity High-resistance buffer layer and window layer (transparent conductive film) of CIS-based thin-film solar cell as described in (2) or (3) above. It is a continuous film forming method.
- the film forming step of the window layer includes an organometallic compound of zinc and pure water (H 2 O).
- the organometallic compound of zinc is dimethyl zinc or jetyl zinc, preferably jetyl zinc (DEZ), which is filled in a bubbler, and helium or argon.
- the CIS thin film solar cell according to (4) or (5) described above is supplied to the MOCVD film forming apparatus in the window layer forming process by bubbling and entraining an inert gas such as Resistance buffer layer / window layer (transparent conductive film) This is a continuous film forming method.
- the present invention relates to the dopant force described in the above (5) used for adjusting the resistivity, hydrogenated or gas produced as an organometallic compound, or volatile (or high vapor pressure).
- CIS-based thin films that are liquids, each diluted with an inert gas such as helium or argon, mixed with a carrier gas accompanied by manufacturing raw materials, and supplied into the MOCVD film forming apparatus in the film forming process of the window layer
- the buffer layer is in the pre-heating step before step a buffer layer forming step, in a vacuum of up to 10- 3 Torr, a temperature range of 100 to 200 ° C, preferably Heated to 120 to 160 ° C, and immediately after reaching that temperature, it is transported to the buffer layer forming step maintained in the temperature range of 120 to 160 ° C.
- a buffer layer forming step Using water as a film-forming raw material, a film thickness containing a small amount of zinc hydroxide at a molar ratio of 0.5 to 0.7 DEZ / HO 2
- the window layer is a preheating step before the window layer forming step, and the substrate is placed in a temperature range of 140 to 250 ° C. in a vacuum up to lO or r, preferably Is heated to 160-190 ° C, and immediately after reaching that temperature, it is transported to the window layer forming process maintained in the temperature range of 160-190 ° C.
- the sheet resistance is 10 ⁇ or less.
- a low-resistance ZnO-based transparent conductive film having a transmittance of 85% or more and a film thickness in the range of 0.5 to 2.5 m, preferably in the range of 1 to 1.5 m is formed (1
- the present invention includes a glass substrate, a metal back electrode layer, a p-type conductive CIS-based (CuInSe-based) chalcopyrite multicomponent compound semiconductor thin film, a transparent and high-resistance layer
- the buffer layer and the window layer are sequentially formed in a laminated structure by the MOCVD method.
- the substrate introduction part for introducing the solar cell semi-finished product substrate, the solar A preheating chamber for preheating the battery semi-finished substrate, a high resistance buffer layer deposition chamber for forming a high resistance buffer layer on the preheated solar cell semi-finished substrate, and the high resistance buffer layer are formed.
- Dry and spare solar cell substrate Vacuum drying chamber / preheating chamber for heating, window layer film forming chamber for forming a window layer on the dried and preheated semi-finished solar cell substrate, solar cell on which the buffer layer and the window layer are formed
- High-resistance buffer layer of CIS-based thin-film solar cell for carrying out the method 'window layer (transparent conductive film) continuous film forming device.
- the present invention provides the high-resistance buffer layer / window layer (transparent conductive film) continuous film-forming apparatus for the CIS-based thin film solar cell according to (10), wherein the high-resistance buffer layer is formed.
- the room is Jechil Zinc and pure water are used as raw materials for film formation. These are filled into a bubbler, etc., and an inert gas such as helium or argon is used as a carrier gas to pass through the bubbler and supplied onto a heated solar cell semi-finished product substrate.
- a ZnO thin film having a thickness of 2 to 50 nm is formed by MOCVD, and a CIS-based thin film solar cell for carrying out the continuous film forming method described in (4) and (8) above.
- High resistance buffer layer / window layer transparent conductive film
- the present invention relates to the high resistance buffer layer / window layer (transparent conductive film) continuous film forming apparatus of the CIS-based thin film solar cell according to (10), wherein the window layer film forming chamber includes
- the resistivity is adjusted by using an organometallic compound of zinc and pure water as a film-forming raw material, filling them into a bubbler, and using an inert gas such as helium or argon as a carrier gas through the bubbler. Therefore, a group III element in the periodic table, for example, any one of boron, aluminum, indium, and gallium or a combination thereof is used as a dopant in the method described in the above (7), and the MOCVD method is used.
- a ZnO-based transparent conductive film is formed, and a high-resistance buffer layer / window layer (transparent conductive film) of a CIS-based thin-film solar cell for carrying out the continuous film-forming method described in (5) above It is a membrane device.
- the film formation method by the MOCVD method of the present invention can obtain output characteristics (conversion efficiency, open-circuit voltage, short-circuit current density, fill factor) equivalent to those of the conventional film formation method by the solution growth method, High resistance buffer layer 1D and window layer (transparent conductive film) 1E are continuously formed by the MOCVD method, simplifying the manufacturing method and reducing raw material costs and waste disposal costs. Can be greatly reduced.
- the present invention relates to a method for continuously forming a high resistance buffer layer / window layer (transparent conductive film) of a CIS-based thin film solar cell and a continuous film forming apparatus for carrying out the continuous film forming method.
- the CIS thin film solar cell is composed of a glass substrate 1A (thickness 1 to 3 mm) and a metal back electrode layer 1B (thickness 1 to 2 / ⁇ ⁇ molybdenum). , Titanium, etc.), vertical CIS light absorption layer 1C, high resistance buffer layer 1D, n-type window layer (transparent conductive film) 1E This is a pn heterojunction device with a substrate structure stacked in this order.
- the light-absorbing layer has a p-type conductivity Cu-III VI group chalcopyrite structure with a thickness of 1 to 3 m.
- CuInSe Cu (InGa) Se
- Cu (InGa) (SSe) Cu (InGa) (SSe), etc.
- the p-type CIS light absorption layer 1C includes a selenium-containing CIS light absorption layer, a sulfide-based CIS light absorption layer, and a sulfur / selenium-containing CIS light absorption layer.
- the selenide-based CIS-based light absorption layer is made of CuInSe, Cu (InGa) Se, or CuGaSe, and
- the sulfide-based CIS-based light absorption layer is made of CuInS, Cu (InGa) S, CuGaS, and the sulfur
- Selenide-based CIS-based light absorption layers are Culn (SSe), Cu (InGa) (SSe), CuGa (SSe).
- the high-resistance buffer layer / window layer (transparent conductive film) continuous film forming method is a solar cell semi-finished product additional substrate A (hereinafter referred to as a metal back electrode layer 1B and a light absorption layer 1C) formed in this order on a glass substrate 1A.
- This is a method in which a high-resistance buffer layer 1D and a window layer (transparent conductive film) 1E are continuously formed on the substrate by MOCVD.
- the high-resistance buffer layer 1D is a transparent, high-resistance (10 4 ⁇ 'cm or more) and intrinsic acid-zinc thin film
- the window layer (transparent conductive film) 1E has a wide forbidden band with n-type conductivity. It is a semiconducting thin film that is transparent, has low resistance, and has a thickness of 0.5 to 2.5 m and has a strength of acid and zinc.
- a high-resistance buffer layer is formed by a solution growth method in which solution force is also chemically grown on the light absorption layer 1C of the substrate A. 1D is grown, and then a window layer (transparent conductive film) 1E is grown thereon in another process.
- the film formation method by the MOCVD method of the present invention uses the high resistance buffer layer 1D on the light absorption layer 1C of the substrate A by MOCVD method using jetyl zinc and pure water as raw materials.
- a low-resistance window layer (transparent conductive film) using the same raw material in the same MOCVD deposition apparatus and using diborane-powered boron as a dopant. Grow.
- the buffer layer 1D is formed on the light absorption layer 1C of the solar cell semi-finished product substrate A formed on the glass substrate 1A in the order of the metal back electrode layer 1B and the light absorption layer 1C.
- This is a continuous film forming method in which the film is continuously formed in a laminated structure in the order of the window layer 1E.
- the buffer layer 1D and the window layer 1E are manufactured by a metal organic chemical vapor deposition (MOCVD) method in which a plurality of preheating steps and film forming steps are connected in-line.
- MOCVD metal organic chemical vapor deposition
- the buffer layer 1D and the window layer 1E are successively formed in the same MOCVD film forming apparatus in an adjacent and independent buffer layer forming process and window layer forming process.
- an organometallic compound of zinc and pure water are used as film forming raw materials, and these are filled in a bubbler or the like, and an inert gas such as helium or argon is used. It is used as a carrier gas that passes through the bubbler and is deposited by MOCVD.
- the organometallic compound of zinc is dimethyl zinc or jetyl zinc, preferably jetyl zinc, which is filled in a bubbler, and an inert gas such as helium or argon is bubbled there and entrained.
- the buffer layer 1D and the window layer 1E are supplied to the film forming step (in the MOCVD film forming apparatus). Dimethyl zinc and jetyl zinc are liquids at room temperature.
- the buffer layer is a pre-heating step before step Roh Ffa layer forming step, 10- 3 Torr or in a vacuum at a temperature range of 100 to 200 ° C, preferably, 120 to 160 ° Heated to C, and immediately after reaching that temperature, it was transported to the buffer layer film forming process maintained in the temperature range of 120 to 160 ° C.
- jetyl zinc and pure water were used as film forming raw materials As a ZnO film with a DEZ / HO molar ratio of 0.5 to 0.9 and containing a small amount of zinc hydroxide in the range of 2 to 50 nm A thin film is formed.
- any one of a group III element of the periodic table for example, boron, aluminum, indium, gallium, or a combination thereof is used.
- dopants any one of a group III element of the periodic table, for example, boron, aluminum, indium, gallium, or a combination thereof is used.
- the dopant used to adjust the resistivity is a gas or a volatile (or high vapor pressure) liquid produced as a hydrogenated or organometallic compound, each of which is an inert gas such as helium or argon. It is diluted and mixed with a carrier gas accompanied by manufacturing raw materials and supplied to the window layer forming process (inside the MOCVD film forming apparatus).
- the window layer is a pre-heating step before steps window layer formation step, 10 3 up Torr in vacuum, the temperature range of 140 to 250 ° C the substrate, preferably, 160 to 190 ° Heated to C, and immediately after reaching that temperature, it was transported to a window layer film forming process maintained in a temperature range of 160 to 190 ° C.
- window layer film forming process jetyl zinc and pure water were used as film forming raw materials.
- the sheet resistance is 10 ⁇ or less and the transmittance is 85
- a low-resistance ZnO-based transparent conductive film having a thickness of at least% and a thickness in the range of 0.5 to 2.5 m, preferably in the range of 1 to 1.5 m is formed.
- each film forming method is as follows.
- MOCVD method After pattern 2 is formed, high resistance buffer layer is formed by MOCVD method Solution growth method 1: Pattern 2 is formed after high resistance buffer layer is formed by solution growth method Solution growth method 2: Solution growth is performed after pattern 2 is formed High resistance buffer layer is formed by the method [0031]
- Table 1 shows a CIS thin film solar cell using a high-resistance buffer layer ID formed by the MOCVD method of the present invention and a CIS using a high-resistance buffer layer ID formed by a conventional solution growth method.
- FIG. 6 is a comparison diagram of output characteristics with a thin-film solar cell. When a film is formed by the MOCVD method of the present invention, output characteristics equivalent to those obtained by a conventional solution growth method can be obtained.
- the window layer was formed by MOCVD under the same conditions.
- the film formation method by the MOCVD method of the present invention can obtain output characteristics (conversion efficiency, open-circuit voltage, short-circuit current density, fill factor) equivalent to those of the conventional film formation method by the solution growth method, and high performance.
- Resistive buffer layer 1D and window layer (transparent conductive film) 1E are continuously formed by the MOCVD method, which simplifies the manufacturing method and costs for raw materials used to form a high-resistance buffer layer by the conventional solution growth method In addition, since the waste disposal cost can be reduced, the manufacturing cost can be greatly reduced.
- Fig. 3 shows the relationship between IIZVI group ratio and fill factor [FF] during the formation of a high-resistance buffer layer of a CIS-based thin-film solar cell using the high-resistance buffer layer 1D formed by the MOCVD method of the present invention
- the substrate temperature is 160 ° C and the film thickness is 5 nm.
- the fill factor [FF] needs to be 0.6 to 0.7, and therefore IIZVI during the formation of the high resistance buffer layer 1D.
- the group ratio eg, DEZ / HO molar ratio
- the film was formed by the MOCVD method under the same conditions.
- the element [FF] is required to be 0.6 to 0.7. Therefore, the substrate temperature when the high-resistance buffer layer 1D is formed is 100 ° C to 250 ° C, preferably 150 ° C. The range of C to 220 ° C proved to be optimal. In all cases, the window layer was formed by the MOCVD method under the same conditions.
- the film thickness [nm] of the high-resistance buffer layer 1D is optimally in the range of 2 nm to 50 nm.
- the window layer has the same conditions in all cases.
- a film was formed by MOCVD.
- FIG. 6 shows the relationship between the film thickness and the conversion efficiency when the high-resistance buffer layer 1D is formed using the high-resistance buffer layer 1D formed by the MOCVD method of the present invention (substrate temperature 190 ° C).
- the film thickness [nm] of the high-resistance buffer layer 1D is optimally in the range of 2 nm to 50 nm. In all cases, the window layer was formed by MOC VD under the same conditions.
- the metal back electrode layer It is necessary to provide a pattern formation step after film formation, after light absorption layer film formation, after high resistance buffer layer film formation, or after window layer (transparent conductive film) film formation.
- the high resistance buffer layer / window layer (transparent conductive film) continuous film forming apparatus 2 is a solar cell semi-finished product substrate (hereinafter referred to as a substrate) in which a metal back electrode layer 1B and a light absorption layer 1C are formed in this order on a glass substrate 1A.
- a substrate a solar cell semi-finished product substrate
- This is a device that continuously forms a high-resistance buffer layer and window layer (transparent conductive film) by the MOCVD method, as shown in Fig. 2.
- a preheating chamber 4 for preheating the solar cell semi-finished substrate 4 for preheating the solar cell semi-finished substrate 4, a high resistance buffer layer deposition chamber 5 for forming a high resistance buffer layer on the preheated solar cell semi-finished substrate 5, and the high resistance buffer Vacuum drying chamber / preheating chamber 6 for drying and pre-heating the solar cell semi-finished substrate with the layer formed thereon, window layer forming a window layer on the dried and pre-heated semi-finished solar cell substrate Film chamber 7, solar cell semi-finished product in which the buffer layer and window layer are formed Consisting substrate was taken out portion 9 for taking out a solar cell sub-product cooling chamber 8 and the buffer layer and the window layer is a film for cooling the plate.
- a solar cell semi-finished product substrate A (hereinafter referred to as substrate A) in which a metal back electrode layer 1B and a light absorption layer 1C were formed in this order on a glass substrate 1A was mounted on a hot plate HP.
- substrate A a solar cell semi-finished product substrate A
- the substrate A is carried into the preheating chamber 4 and preheated to a certain temperature by the heater H.
- the substrate A is a high resistance buffer layer. It is carried into the film forming chamber 5 and a high resistance buffer layer 1D is formed by MOCVD.
- the substrate A is carried into a vacuum drying chamber / preheating chamber 6 where vacuum drying and preheating are performed.
- the substrate A is carried into the window layer film forming chamber 7, and a window layer (transparent conductive film) 1E is formed to a predetermined film thickness by MOCVD.
- the substrate A is carried into the cooling chamber 8 and cooled.
- the substrate A is carried into the substrate take-out part 9, taken out from the hot plate HP, and on the glass substrate 1A, the metal back electrode layer 1B, the light absorption layer 1C, the high-resistance buffer layer 1D, and the window layer.
- Transparent conductive film A CIS-based thin film solar cell formed in the order of 1E is formed.
- the high-resistance buffer layer 1D is formed in the preheating chamber 4 in front of the buffer layer deposition chamber 5 by a vacuum pump P with a mechanical booster in a vacuum of 10 to 3 Torr. It is heated to a temperature range of 0 ° C, preferably 120 to 160 ° C, and immediately after reaching that temperature, it is transferred to the buffer layer deposition chamber 5 maintained in the temperature range of 120 to 160 ° C, where Then, using a small amount of zinc hydroxide of DEZZH 0 molar ratio 0.5 to 0.9, using jetyl zinc and pure water as film forming raw materials
- a ZnO thin film containing 2 to 50 nm in thickness is formed.
- deposition of the window layer 1E is a vacuum drying chamber and the preheating chamber 6 of the front chamber of the window layer formation chamber 7, the vacuum pump P with mechanical two local booster, a vacuum of up to 10- 3 Torr
- the substrate is heated to a temperature range of 140 to 250 ° C, preferably 160 to 190 ° C, and immediately after the temperature is reached, the temperature is maintained in the temperature range of 160 to 190 ° C.
- diborane gas diluted with an inert gas to a concentration of 1 to 5 Vol% is supplied into the raw material piping using the zinc zinc and pure water as the film-forming raw materials.
- the sheet resistance is 10 ⁇ / mouth or less, the transmittance is 85% or more, and the film thickness is in the range of 0.5 to 2.5 m, preferably 1 to 1.5 m.
- a ZnO-based transparent conductive film in the range is formed.
- Window layer (transparent conductive film) 1E is a semiconductor thin film having n-type conductivity, wide forbidden band width, low resistance, and 0.5 to 3 m thickness of zinc oxide.
- FIG. 1 is a schematic configuration diagram of a high resistance buffer layer'window layer (transparent conductive film) continuous film forming method of the present invention. is there.
- ⁇ 2 It is a schematic configuration diagram of a high resistance buffer layer'window layer (transparent conductive film) continuous film forming apparatus of the present invention.
- FIG. 3 Relationship between IIZVI group ratio and fill factor [FF] during CIS thin film solar cell high resistance buffer layer deposition using high resistance buffer layer 1D deposited by MOCVD method of the present invention (substrate temperature)
- FIG. 3 is a view showing a temperature of 160 ° C. and a film thickness of 5 nm.
- FIG. 5 CIS-based thin film using high resistance buffer layer 1D formed by MOCVD method of the present invention.
- Film thickness and fill factor [FF] high substrate temperature 160 ° C, when high resistance buffer layer of solar cell is formed
- II / VI group ratio for example, DEZ / HO molar ratio
- a Solar cell semi-finished product (multi-layer additional substrate)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP06746802.5A EP1898469A4 (en) | 2005-05-27 | 2006-05-24 | METHOD FOR CONTINUOUS STORAGE OF A BUFFER LAYER / WINDOW LAYER WITH A HIGH RESISTANCE (TRANSPARENT CONDUCTIVE FILM) OF A CIS-BASED THIN FILM SOLAR CELL AND DEVICES FOR REMOVING A CONTINUOUS FILM FOR CARRYING OUT THIS METHOD |
US11/915,423 US8093096B2 (en) | 2005-05-27 | 2006-05-24 | Method of successive high-resistance buffer layer/window layer (transparent conductive film) formation for CIS based thin-film solar cell and apparatus for successive film formation for practicing the method of successive film formation |
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JP2005155712A JP4841173B2 (ja) | 2005-05-27 | 2005-05-27 | Cis系薄膜太陽電池の高抵抗バッファ層・窓層連続製膜方法及び製膜装置 |
JP2005-155712 | 2005-05-27 |
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PCT/JP2006/310371 WO2006126598A1 (ja) | 2005-05-27 | 2006-05-24 | Cis系薄膜太陽電池の高抵抗バッファ層・窓層(透明導電膜)連続製膜方法及びその連続製膜方法を実施するための連続製膜装置 |
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US (1) | US8093096B2 (ja) |
EP (1) | EP1898469A4 (ja) |
JP (1) | JP4841173B2 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
EP1898469A1 (en) | 2008-03-12 |
CN101213674A (zh) | 2008-07-02 |
KR101274660B1 (ko) | 2013-06-14 |
KR20080033157A (ko) | 2008-04-16 |
CN100546051C (zh) | 2009-09-30 |
JP2006332440A (ja) | 2006-12-07 |
EP1898469A4 (en) | 2016-12-28 |
JP4841173B2 (ja) | 2011-12-21 |
US20090087940A1 (en) | 2009-04-02 |
US8093096B2 (en) | 2012-01-10 |
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