GB2370282A - Anodic process for producing chalcopyrite compounds - Google Patents
Anodic process for producing chalcopyrite compounds Download PDFInfo
- Publication number
- GB2370282A GB2370282A GB0030734A GB0030734A GB2370282A GB 2370282 A GB2370282 A GB 2370282A GB 0030734 A GB0030734 A GB 0030734A GB 0030734 A GB0030734 A GB 0030734A GB 2370282 A GB2370282 A GB 2370282A
- Authority
- GB
- United Kingdom
- Prior art keywords
- layers
- chalcopyrite
- alloy
- anodic
- metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical class [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 229910052951 chalcopyrite Inorganic materials 0.000 claims abstract description 12
- -1 chalcopyrite compound Chemical class 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract 7
- 230000008021 deposition Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims 6
- 150000002739 metals Chemical class 0.000 claims 6
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000002243 precursor Substances 0.000 abstract description 11
- 238000000151 deposition Methods 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 6
- 150000004763 sulfides Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 150000003346 selenoethers Chemical class 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000010409 thin film Substances 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 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
- 239000005864 Sulphur Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
A multiple step process to produce chalcopyrite compounds of the type, Cu(In<SB>x</SB> Ga<SB>1-x</SB>)( Sy Se<SB>1-y</SB>)<SB>2</SB>, (e.g. CuInS<SB>2</SB> or CuInSe<SB>2</SB>) involves depositing precursor layers of the metallic elements as stacked elemental layers or alloys of the elements followed by electrochemical conversion of the precursor layers into the chalcopyrite compound or alloy. The process involves the anodic sulphidisation or selenisation of the layers by passing an electric current through a solution of selenide/sulphide salts dissolved in an aqueous alkaline or neutral solution or an organic solvent. Annealing is used to complete the chemical reaction(s) to form the chalcopyrite compound and to improve the physical properties of the layers.
Description
Rapid Anodic Process for Producing ! Chalcopyrite Compounds This invention relates to a novel method for producing thin film chalcopyrite
semiconductors of the type Cu (InxGa l-x) (SySe i-y, e. g. CuInSe2 and Cuis2, which find k-y) 27 application in thin film solar cell devices.
Photovoltaic solar cells consist of a junction between a n-type and p-type semiconductor and use the phenomenon known as the photovoltaic effect for directly converting sunlight into electricity. The p-type semiconductor has an energy bandgap appropriate for absorbing incident solar radiation and it hence has an energy bandgap in the range 1. 0-1 7 eV ; it is referred to as the"absorber layer"in a solar cell. The n-type layer forms the p-n junction with the absorber layer and it must allow light to pass through it to the absorber layer; the wider energy bandgap, transmissive n-type layer is referred to as the"window layer"in a solar cell structure. In some devices a thin"buffer layer"is included between the n and p-type layers to improve the junction properties.
The most advanced methods to produce chalcopyrite thin films for use as"absorber layers"in thin film solar cells involve a two step process: 1. the formation of Cu/In/Ga precursor layers by co-evaporation, sputtering electrodeposition or electroless deposition or by annealing alternate Cu/In/Ga layers deposited using these methods, 2. annealing the precursor layers in a H2Se or selenium environment to form the chalcopyrite selenide or in a H2S or sulphur environment to form the chalcopyrite sulphide.
The latter annealing step involves heating the metallic precursors in environments containing highly toxic/corrosive gases.
This patent gives a novel process for producing chalcopyrite selenides and sulphides that is safer than the conventional method and also minimises the use of expensive vacuum technology.
The process is similar to the conventional method in that the first step is the formation of Cu/In/Ga precursor layers by co-evaporation, sputtering, electrodeposition or electroless deposition or by annealing alternate Cu/In/Ga layers deposited using these methods. The innovative step is the combination of this first step with anodic selenisation or sulphurisation to convert the layers into chalcopyrite selenides and sulphides.
The electrolyte used is a solution of a sulphide or selenide in an alkaline aqueous solvent, e. g. a solution of potassium or sodium hydroxide or an inorganic solvent such as ethylene glycol. Typical solutes are Na2S, Nits, Na2Se or NH4Se. The sodium salts are preferred because sodium ions play a role in passivating the grain boundaries in the synthesised layers. The precursor layers form the conducting anode. The other electrode (s) can be made from a wide range of materials, e. g. platinum.
The layers may then be annealed to complete the reaction between the precursor layer and the sulphur/selenium incorporated and to improve the grain size and other physical properties.
Typical Steps Taken to Fabricate a Chalcoovite-Based Thin Film Solar Cell, (Substrate Configuration).
Step 1 deposition of a back contact material onto a substrate, e. g. molydenum onto glass.
Step 2: deposition of the Cu/In/Ga precursor layers onto the molydenum coated glass substrates.
Step 3 selenisation/sulphurisation of the precursor layers using the anodic process given in this patent application.
Step 4: annealing.
Step 5: etching to remove binary sulphides using e. g. potassium cyanide.
Step 6: deposition of"buffer layer"., e. g. CdS, ZnS or ZnSe or alloys of these materials with (OH) groups.
Step 7: deposition of wide bandgap window layer, e. g. CdS, ZnO, ZnSe, SnO2 or indium tin oxide.
Step 8: deposition of a contact grid.
Step 9: anneal.
Tvoicai Steps Taken to Fabricate a Chalcopyrite -Based Thin Film Solar Cell.
(Superstrate Configuration) Step 1: deposit buffer layer onto tin oxide coated glass, e. g. ZnS.
Step 2: deposit precursor layers onto the buffer layer.
Step 3: anodically sulphidise/selenise.
Step 4: anneal.
Step 5: deposit back contact.
Step 6: anneal.
Claims (3)
- CLAIMS 1. The process of production of chalcopyrite selenide compounds and alloys, e. g.CuInSe2 or CuGaInSe2, by the multiple-step process, deposition of stacked elemental layers of the metals or an alloy of the metals followed by anodic selenisation to form the compound/alloy.
- 2. The process of production of chalcopyrite sulphide compounds and alloys, e. g.CuInS2 or CuGaInS2, by the multiple-step process, deposition of stacked elemental layers of the metals or an alloy of the metals followed by anodic sulphurisation to form the compound/alloy.
- 3. The process of production of chalcopyrite selenide/sulphide alloys, e. g.CuIn (Sel, S.) 2 by the multiple-step process, deposition of stacked elemental layers of the metals or an alloy of the metals followed by anodic selenisation/sulphurisation to form the compound/alloy.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0030734A GB2370282B (en) | 2000-12-16 | 2000-12-16 | Rapid anodic process for producing chalcopyrite compounds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0030734A GB2370282B (en) | 2000-12-16 | 2000-12-16 | Rapid anodic process for producing chalcopyrite compounds |
Publications (3)
Publication Number | Publication Date |
---|---|
GB0030734D0 GB0030734D0 (en) | 2001-01-31 |
GB2370282A true GB2370282A (en) | 2002-06-26 |
GB2370282B GB2370282B (en) | 2003-03-26 |
Family
ID=9905237
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB0030734A Expired - Fee Related GB2370282B (en) | 2000-12-16 | 2000-12-16 | Rapid anodic process for producing chalcopyrite compounds |
Country Status (1)
Country | Link |
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GB (1) | GB2370282B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011110763A1 (en) * | 2010-03-11 | 2011-09-15 | Electricite De France | Method for preparing an absorber thin film for photovoltaic cells |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2056609A1 (en) * | 1991-11-28 | 1993-05-29 | Ishiang Shih | Methods for fabrication of cuinse2 thin films and solar cells |
JPH09312409A (en) * | 1996-05-22 | 1997-12-02 | Matsushita Electric Ind Co Ltd | Manufacture of chalcopyrite structure semiconductor thin film and solar battery |
JPH10150212A (en) * | 1996-11-20 | 1998-06-02 | Matsushita Electric Ind Co Ltd | Precursor for semiconductor thin film formation use and manufacture of semiconductor thin film |
US5981868A (en) * | 1996-10-25 | 1999-11-09 | Showa Shell Sekiyu K.K. | Thin-film solar cell comprising thin-film light absorbing layer of chalcopyrite multi-element compound semiconductor |
US6023020A (en) * | 1996-10-15 | 2000-02-08 | Matsushita Electric Industrial Co., Ltd. | Solar cell and method for manufacturing the same |
US6048442A (en) * | 1996-10-25 | 2000-04-11 | Showa Shell Sekiyu K.K. | Method for producing thin-film solar cell and equipment for producing the same |
-
2000
- 2000-12-16 GB GB0030734A patent/GB2370282B/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2056609A1 (en) * | 1991-11-28 | 1993-05-29 | Ishiang Shih | Methods for fabrication of cuinse2 thin films and solar cells |
JPH09312409A (en) * | 1996-05-22 | 1997-12-02 | Matsushita Electric Ind Co Ltd | Manufacture of chalcopyrite structure semiconductor thin film and solar battery |
US6023020A (en) * | 1996-10-15 | 2000-02-08 | Matsushita Electric Industrial Co., Ltd. | Solar cell and method for manufacturing the same |
US5981868A (en) * | 1996-10-25 | 1999-11-09 | Showa Shell Sekiyu K.K. | Thin-film solar cell comprising thin-film light absorbing layer of chalcopyrite multi-element compound semiconductor |
US6048442A (en) * | 1996-10-25 | 2000-04-11 | Showa Shell Sekiyu K.K. | Method for producing thin-film solar cell and equipment for producing the same |
JPH10150212A (en) * | 1996-11-20 | 1998-06-02 | Matsushita Electric Ind Co Ltd | Precursor for semiconductor thin film formation use and manufacture of semiconductor thin film |
Non-Patent Citations (2)
Title |
---|
WPI Accession no 98-074148 & JP 09 312 409 A * |
WPI Accession no 98-373381 & JP 10 150 212 A * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011110763A1 (en) * | 2010-03-11 | 2011-09-15 | Electricite De France | Method for preparing an absorber thin film for photovoltaic cells |
FR2957365A1 (en) * | 2010-03-11 | 2011-09-16 | Electricite De France | PROCESS FOR PREPARING A THIN ABSORBER LAYER FOR PHOTOVOLTAIC CELLS |
CN103003475A (en) * | 2010-03-11 | 2013-03-27 | 法国电力公司 | Method for preparing an absorber thin film for photovoltaic cells |
AU2011225972B2 (en) * | 2010-03-11 | 2013-09-12 | Centre National De La Recherche Scientifique - Cnrs - | Method for preparing an absorber thin film for photovoltaic cells |
KR101426428B1 (en) * | 2010-03-11 | 2014-08-06 | 엘렉트리씨트 드 프랑스 | Method for preparing an absorber thin film for photovoltaic cells |
US8920624B2 (en) | 2010-03-11 | 2014-12-30 | Electricite De France | Method for preparing an absorber thin film for photovoltaic cells |
CN103003475B (en) * | 2010-03-11 | 2016-08-24 | 法国电力公司 | Preparation is applicable to the method for the absorbing membrane of photovoltaic cell |
Also Published As
Publication number | Publication date |
---|---|
GB0030734D0 (en) | 2001-01-31 |
GB2370282B (en) | 2003-03-26 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20041216 |