CN103779438B - A kind of electrochemical deposition prepares the method for CIGS preformed layer - Google Patents
A kind of electrochemical deposition prepares the method for CIGS preformed layer Download PDFInfo
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- CN103779438B CN103779438B CN201210405257.6A CN201210405257A CN103779438B CN 103779438 B CN103779438 B CN 103779438B CN 201210405257 A CN201210405257 A CN 201210405257A CN 103779438 B CN103779438 B CN 103779438B
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000000151 deposition Methods 0.000 claims abstract description 52
- 239000011669 selenium Substances 0.000 claims abstract description 49
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 37
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- 229910052738 indium Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 9
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 235000013877 carbamide Nutrition 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 229960003178 choline chloride Drugs 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229910001449 indium ion Inorganic materials 0.000 claims description 3
- 229940045136 urea Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 239000010409 thin film Substances 0.000 description 36
- 230000008859 change Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 150000004673 fluoride salts Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003891 oxalate salts Chemical class 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- OHUHAKQCZVMIOF-UHFFFAOYSA-N OS(O)(=O)=O.[SeH2] Chemical compound OS(O)(=O)=O.[SeH2] OHUHAKQCZVMIOF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000013084 building-integrated photovoltaic technology Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011800 void material Substances 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Photovoltaic Devices (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention belongs to technical field of solar batteries, be specifically related to a kind of method that electrochemical deposition prepares CIGS preformed layer.The electrochemical deposition of the present invention prepares the method for CIGS preformed layer, it is included in electric depositing solution, use current impulse or potential pulse to obtain CIGS preformed layer at cathode substrate substrates, described current impulse or potential pulse include electric current and voltage deposition surface be all direct impulse period of negative value and electric current and voltage deposition surface be all on the occasion of reverse impulse period.The present invention employs the method for reverse impulse in electrodeposition process, formed while CIGS preformed layer, part selenium element strip is returned in electroplate liquid, it is to avoid the generation of selenium ball, thus forming component uniformly, the mutually stable CIGS preformed layer of thing.
Description
Technical field
The invention belongs to area of solar cell, specifically, relate to a kind of electrochemical deposition and prepare CIGS preformed layer
Method.
Background technology
Along with being continuously increased of mankind's energy resource consumption, exhausting of the non-renewable energy such as Fossil fuel is urgently to be resolved hurrily
Problem.Will there is flex point in about the year two thousand thirty in fossil energy total amount consumed, and the proportion of regenerative resource will constantly rise, its
In, solar energy proportion in future source of energy structure is by increasing, and this proportion of conservative estimation can exceed in 2100
60%.Solar energy is the energy the abundantest in numerous regenerative resource, and the whole world sunlight energy of a hour is equivalent to
The earth energy consumption of a year, significantly larger than wind energy, underground heat, water power, ocean energy, bioenergy equal energy source.
The bottleneck that restriction solar energy generates electricity on a large scale is mainly the low transformation efficiency of photovoltaic device and high production cost,
The key element of core is the cost of photovoltaic generating system, including photovoltaic panel and other system component such as inverter, electric switch device,
Cable and support etc..Generating to realize " par online ", and cost of electricity-generating to reach often to spend RMB 0.6 yuan, photovoltaic panel cost
It is down to every watt of RMB 3-4 unit, price every watt RMB 5-7 unit.Owing to existing market polysilicon photovoltaic panel price connects
The cost price of nearly enterprise, polysilicon photovoltaic panel manufacturing technology relative maturity the most, lower limited space, with polysilicon photovoltaic
Plate realizes " par online " and is not easy to.
CIGS (CuInxGaySez, it is possible to include sulfur, be abbreviated as CIGS) thin film photovoltaic panel is with its conversion efficiency
The advantages such as height, long-time stability are good, capability of resistance to radiation is strong become the study hotspot of photovoltaic circle, are expected to become follow-on honest and clean
Valency photovoltaic panel.It has a following advantage:
1) high photoelectric transformation efficiency, current glass substrate CIGS thin film photovoltaic panel Laboratory efficiencies alreadys more than 20%,
World record close to conventional crystalline silicon photovoltaic panel.The conversion efficiency of large area CIGS thin film photovoltaic panel assembly also has more than 14%
Product, be the highest in all thin film photovoltaic panels；
2) low light level performance is good, non-solar directly according to time also can produce electricity, from the experience of photovoltaic generation field actual motion, cloudy
The more electric energy of arch can be carried at it and at dusk in the morning；
3) temperature coefficient is low, includes that when temperature height local temperature is high or temperature is high, CIGS photovoltaic panel because sunlight irradiates
Higher conversion efficiency can be kept.Therefore, under identical efficiency, CIGS photovoltaic panel produces electricity more than conventional crystalline silicon photovoltaic panel
Many；
4) low cost, material consumption are few；
5) long-time stability are good, and outdoor application is unattenuated；
6) energy payback period is short；
7) it is suitable for developing multiduty flexible photovoltaic assembly.These advantages make CIGS thin-film photovoltaic panel at civil area
And military domain has broad application prospects, such as BIPV, large-scale low-cost electric station, solar energy
Lighting source, space and proximity space system etc..
CIGS thin-film photovoltaic panel is multi-layer film structure, generally includes: substrate, back electrode, CIGS absorbed layer, buffering
Layer, transparency conducting layer etc., wherein CIGS absorbed layer is the ingredient of solar energy photovoltaic panel most critical, and its preparation method is certainly
Quality and the cost of photovoltaic panel are determined.
The production technology of the compound semiconductor being commercially widely used in photoelectric device at present is nearly all to use fine vacuum
Technology is such as deposited with or sputters, particularly in CIGS field.But above-mentioned vacuum technique is at early investment and running
In be both needed to expend substantial amounts of cost.Additionally, the vacuum-chamber dimensions of instrument and equipment also can limit the yield of thin film, further shadow
Ring production efficiency.The development of antivacuum method is conducive to CIGS large-scale production.
Nanosolar company takes the lead in have employed ink printed and prepares the technology of CIGS thin film and (see .Pichler, United States Patent (USP)
Numbers 7,122,398 and quote document).Its preparation flow is: first passes through chemical method and prepares CIGS nano-particle,
Then the dispersion of these nano-particle is formed colloid solution (being generally termed CIGS nanometer ink), add suitable surface and live
Property agent, to prevent nanoparticle agglomerates, is in addition additionally added other chemical addition agents needed for print procedure.CIGS nanometer
Ink, after printing formation thin film, needs heat treatment to remove the solvent being previously joined, surfactant and other chemistry and adds
Add agent, then could sinter the homogeneous thin film of formation.
Many conductive materials can be prepared on a large scale by the electrochemical method of low cost, prepares with electrodeposition process
CIGS thin film becomes and reduces one of cost, the main direction of studying obtaining large area CIGS thin film.And at present by electrification
There are some problems for the suitable CIGS of stoichiometric proportion in length of schooling, in CIGS thin film, the mol ratio of each element is: Cu:
(In+Ga): during Se ≈ 1:1:2, conversion efficiency is higher, the content of Ga is
When 0.3, conversion efficiency is the highest.Such as: electro-deposition CIGS needs each unit of Cu, In, Ga, Se in strict control solution
The amount of element, and accurately control electrochemical reduction current potential, and controlling solution, not produce other in electrochemical deposition process secondary
Reaction.Even so, there is the pertinent literature of several research group to claim in aqueous phase, electroplate out CIGS thin film.Example
As: Y.P.Fuetal. (Journal of the Electro chemical Society, 2009,156,9 E133-E138) reports
Road prepares CIGS thin film in aqueous with LiCl for conducting salt.Water based electrolyte is due to the sedimentation potential of In and Ga
Low, use relatively negative sedimentation potential, negative electrode easily releases hydrogen, and making thin film is cellular (evolving hydrogen reaction).Additionally,
They do not prepare the suitable thin film of stoichiometric proportion, and in thin film, the content of Ga is on the low side.Add the change of more Ga
Compound can not increase the Ga content in CIGS thin film in aqueous.Fu et al. points out to add in aqueous the change of Ga
Compound causes the reduction potential of Ga more negative, and Ga3+ is difficult to be reduced out at negative electrode.
Lai et al. (Electro chimica Acta2009,54,3004-3010) reports in water-Dimethylformamide
One step electro-deposition CIGS thin film.Even if in this system, due to Cu, In, Ga, Se tetra-reduction potential phase of element
Difference is very big, or is difficult to a step codeposition.In order to solve this problem, Lai etc. adds in water-Dimethylformamide
Enter chelating agent, in this article, their the most also evolving hydrogen reaction of above relating to of labor, but chelating agent
The addition of sodium citrate does not produce obvious Complex effect change the reduction electricity of In and Ga with In3+, Ga3+ ion
Position, it prepares corresponding under the current potential of-0.3V ,-0.4V ,-0.5V ,-0.6V ,-0.7V ,-0.8V ,-0.9V ,-1.0V
CuIn0.21Ga0.10Se1.75, CuIn0.40Ga0.14Se1.41, CuIn0.35Ga0.12Se1.21, CuIn0.42Ga0.17Se1.24,
CuIn0.43Ga0.18Se1.32, CuIn0.47Ga0.22Se1.22, CuIn0.62Ga0.22Se1.20, CuIn0.57Ga0.16Se1.52.These
It not the most the suitable CIGS of stoichiometric proportion, all rich Cu lean In, Ga.
In other method, Kois et al. (Thin Solid Films 2008,516,5948-5952) reports use sulfur cyanogen
Hydrochlorate composite electrolyte prepares CIGS thin film.They again underscores the necessity of selenizing heat treatment after plating.And they
Report shows that Ga content is not enough in the CIGS thin film that plating obtains too.
In another method, Long and he partner (Journal of Physics:Conference Series 2009,
152,012074) a step electro-deposition CIGS thin film in ethanol solution is reported.Equally, the CIGS obtained after plating is thin
Film needs to sinter 30 minutes in 550 DEG C, and in its CIGS thin film obtained, Cu content is not enough.
Peter etc. are reported in electro-deposition in nonaqueous phase and prepare CIGS (" Electro chemical Deposition of CIGS by
Means of Room Temperature Ionic Liquids ", Thin solid Films, 2007,515,5899-5903).This
Piece document describes preparation Cu-In-Ga and Cu-In-Ga-Se thin film in ionic liquid, at 500 DEG C of selenium after this thin film electroplating
Change and within 30 minutes, prepare the suitable CIS of stoichiometric proportion and CIGS thin film respectively.
The document of the studies above electro-deposition, is focused mainly on the impact on electrodeposition process of the electro-deposition liquid.
CN101079454A discloses a kind of method of pulse electrodeposit CIGS semiconductor film material, and the method uses the moon
Pole pulse potential sedimentation deposits the preformed layer containing CIGS in substrate, and described pulse potential waveform is square wave, triangle
Ripple or sine wave.CN101570871A discloses one and utilizes special burst power supply deposition CIGS or CIGS half
The method of conductor thin film material, this patent uses the square-wave pulse of bells regulation, prepares pre-at cathode substrate substrates
Preparative layer.Above two method uses impulse wave, although alleviate constant potential electro-deposition controllable parameter to a certain extent few, analysis
Hydrogen reaction is serious, the problem that thin film void rate is high；But, the method the most fundamentally solves the current potential because of CIGS
Gap and cause four elements can not synchronize codeposition, the deposition velocity of particularly Se is very fast, it is impossible to obtain stoichiometric proportion close
Suitable CIGS thin film, generates some pure selenium balls (spheroid as in accompanying drawing 1) in electrodeposition process.These selenium clubs
Affect CIGS crystal formation, also result in and have little cavity in CIGS layer after annealing.
Summary of the invention
It is an object of the invention to the CIGS thin film in the presence of overcoming above-mentioned electro-deposition to prepare CIGS thin-film technology is changed
Learn metering and form the deficiency of the almost selenium ball of pure selenium than in improper, coating, it is provided that the electrochemical deposition system of a kind of improvement
The method of standby CIGS preformed layer.The present invention utilizes reverse impulse electrochemical deposition to prepare the side of CIGS preformed layer
Method, while forming CIGS preformed layer, returns to part selenium element strip in electroplate liquid, can avoid coating
Interior formation selenium ball, thus the CIGS preformed layer that forming component is uniform, thing is mutually stable.
In order to realize foregoing invention purpose, the invention provides techniques below scheme: a kind of electrochemical deposition prepares copper and indium gallium
The method of selenium preformed layer, is included in electric depositing solution, uses electric current to control pulse or Control of Voltage pulse and serves as a contrast at negative electrode
End substrates obtains CIGS preformed layer, and wherein, described electric current controls pulse or Control of Voltage pulse includes electric current
And voltage deposition surface all reach direct impulse period of negative value and electric current and voltage deposition surface all reach on the occasion of anti-
To pulse period.Described electric depositing solution is ion liquid system.In electrodeposition process, use reverse impulse, permissible
By in the selenium element strip that deposits at relative low voltage to electric depositing solution, it is to avoid form selenium ball in coating.
Preferably, above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, the impulsive condition of described current impulse
For: the working time in direct impulse period is 3 milliseconds～1 second, electric current density-0.05ASD～-5.0ASD；Reverse impulse
The working time in period is 1 millisecond～0.5 second, and electric current density is 0.1ASD～20ASD；The pulse bar of described potential pulse
Part is: the working time in direct impulse period is 3 milliseconds～1 second, voltage-0.5V～-8.0V；The work in reverse impulse period
It is 1 millisecond～0.5 second as the time, voltage 0.1V～5.0V.Under above-mentioned impulsive condition, form CIGS in electro-deposition
While preformed layer, be conducive in segregation selenium element strip to electric depositing solution, and this strip have selectivity,
Other elements of strip hardly, can obtain the suitable CIGS thin film of stoichiometric proportion, it is to avoid form selenium ball in coating.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, copper, indium, gallium, plasma selenium in electric depositing solution
Concentration be respectively 0.1mM-50mM, 0.1mM-60mM, 0.1mM-80mM, 0.1mM-50mM.Described ion
Liquid system is made up of carbamide and choline chloride, and choline chloride is 1:0.5-5, preferably 1:2 with the weight ratio of carbamide.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and the copper ion in electric depositing solution carrys out self-contained copper
Sulfate, acetate, Bromide, fluoride salt, chlorate, iodized salt, nitridation salt, oxalates, citrate,
Phosphate, tungstates, hydrate or combinations thereof.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and the gallium ion in electric depositing solution carrys out self-contained gallium
Sulfate, acetate, Bromide, fluoride salt, chlorate, iodized salt, nitridation salt, oxalates, citrate,
Phosphate, tungstates, hydrate or combinations thereof.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and the indium ion in electric depositing solution carrys out self-contained indium
Sulfate, acetate, Bromide, fluoride salt, chlorate, iodized salt, nitridation salt, oxalates, citrate,
Phosphate, tungstates, hydrate or combinations thereof.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and the plasma selenium in electric depositing solution carrys out self-contained selenium
Sulfate, acetate, Bromide, fluoride salt, chlorate, iodized salt, nitridation salt, oxalates, citrate,
Phosphate, tungstates, hydrate or combinations thereof.Above-mentioned electrochemical deposition prepares the method for CIGS preformed layer
In, described substrate can be conducting polymer, the polymer covering metal, cover the polymer of transparency conducting layer, covering
The glass of ITO, the polymer of covering ITO, the covering pottery of conductive layer, metal, amorphous semiconductor material, crystal half
Any one or combinations thereof in conductor material, polycrystalline semiconductor material.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and in electric depositing solution, all or part of copper ion is
By entering electric depositing solution after anodic oxidation.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, all or part of gallium ion of electric depositing solution be by
Electric depositing solution is entered after anodic oxidation.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and in electric depositing solution, all or part of indium ion is
By entering electric depositing solution after anodic oxidation.
Above-mentioned electrochemical deposition is prepared in the method for CIGS preformed layer, and in electric depositing solution, all or part of plasma selenium is
By entering electric depositing solution after anodic oxidation.
Using CIGS preformed layer prepared by above-mentioned electrochemical deposition method, described reverse impulse participates in deposition preformed layer
Thickness is more than the 20% of integral prefabricated layer thickness.Inventor finds, in electrochemical deposition process, uses reverse impulse system
During for preformed layer is integral prefabricated layer thickness more than 20% obtained, can reduce at CIGS layer and metal level interface
It is formed about cavity.
Compared with prior art, beneficial effects of the present invention:
During electrochemical deposition prepares CIGS, owing to CIGS four element exists potential difference, each element electricity
The complexity solved is different, and four elements can not synchronize codeposition, and particularly Se deposits under relatively low voltage, thus difficult
To obtain the suitable CIGS thin film of stoichiometric proportion, electrodeposition process generates some selenium balls (such as the ball in accompanying drawing 1
Body).These selenium ball impact CIGSs are crystal formation, also result in and have little cavity in CIGS layer after annealing.This
The electrochemical deposition of invention is prepared in CIGS preformed layer method, during electrochemical deposition, have employed reverse arteries and veins
Rush ripple, while preparing CIGS preformed layer, the part selenium element strip that can will deposit at relative low voltage
To electroplating solution, it is to avoid form selenium ball in coating, thus the CIGS that forming component is uniform, thing is mutually stable is prefabricated
Layer.
Inventor finds, in electrochemical deposition process, the preformed layer using reverse impulse to prepare is integral prefabricated thickness
Degree more than 20% time, can reduce and be formed about cavity at CIGS layer and metal level interface.Further, invention
The impulsive condition of people is preferred reverse impulse, is carried out at the direct impulse that deposition surface is all negative value at electric current and voltage period
Electro-deposition, electric current and voltage deposition surface be all on the occasion of reverse impulse carry out strip period, at above-mentioned impulsive condition
Under effect, while electro-deposition forms CIGS preformed layer, be conducive to selenium element portions strip to electric depositing solution
In, other elements of strip hardly, the suitable CIGS thin film of stoichiometric proportion can be obtained, it is to avoid in coating, form selenium
Ball.
Accompanying drawing illustrates:
Fig. 1 is the electron-microscope scanning figure of CIGS preformed layer in prior art, and in figure, ball is selenium ball.Fig. 2 is embodiment
1 pulse current density and corresponding change in voltage figure.
Fig. 3 is the configuration of surface figure of the embodiment 1 that scanning electron microscope obtains.
Fig. 4 is embodiment 2 pulse voltage and corresponding current density change figure.
Fig. 5 is the configuration of surface figure of the embodiment 2 that scanning electron microscope obtains.
Fig. 6 is comparative example 1 constant current electric current density and corresponding change in voltage figure.
Fig. 7 is the configuration of surface figure of the comparative example 1 that scanning electron microscope obtains.
Fig. 8 is comparative example 2 constant voltage and corresponding current density change figure.
Fig. 9 is the configuration of surface figure of the comparative example 2 that scanning electron microscope obtains.
Detailed description of the invention
Below in conjunction with test example and detailed description of the invention, the present invention is described in further detail.But this should be interpreted as
The scope of the above-mentioned theme of the present invention is only limitted to below example, and all technology realized based on present invention belong to this
The scope of invention.
Embodiment 1
The electrochemical deposition that the present embodiment is enumerated prepares the method for CIGS preformed layer, is included in electric depositing solution, adopts
CIGS preformed layer is obtained at cathode substrate substrates with current impulse.Described cathode substrate is soda-lime glass, on it
Cover one layer with the conduction molybdenum layer formed after vacuum splashing and plating.Wherein, described current impulse includes that electric current and voltage are in deposition
Surface be all direct impulse period of negative value and electric current and voltage deposition surface be all on the occasion of reverse impulse period.Pulse
Electric current density and corresponding change in voltage are shown in Fig. 2, and electric current density and the working time of pulse are shown in Table 1.
In the present embodiment, electric depositing solution is ion liquid system, and ion liquid system is made up of carbamide and choline chloride,
Choline chloride is 1:0.5 with the weight ratio of carbamide；In ion liquid system, copper, indium, gallium, the content of plasma selenium and source are seen
Table 2.Electrochemical deposition arranges and includes the platinized platinum as anode, can provide reverse arteries and veins as the platinum filament of reference electrode and one
The power supply of punching.With electric current control during electrochemical deposition, measure simultaneously and note down the change of electric current and relevant voltage.
The CIGS preformed layer configuration of surface prepared according to the method for the present embodiment carries out electron microscope scanning, such as Fig. 3
Shown in, CIGS surface without chondritic, X-ray energy spectrum show the content of selenium 51.7%, overall composition meets copper and indium
The requirement of gallium selenium preformed layer.
Embodiment 2
The electrochemical deposition that the present embodiment is enumerated prepares the method for CIGS preformed layer, is included in electric depositing solution, adopts
CIGS preformed layer is obtained at cathode substrate substrates with potential pulse.Described cathode substrate is the glass of plating Mo and Cu
Glass substrate.Wherein, described potential pulse includes that electric current and voltage are at direct impulse period and the electricity that deposition surface is all negative value
Stream and voltage deposition surface be all on the occasion of reverse impulse period.Pulse voltage and corresponding current density change are shown in figure
4, voltage and the working time of reverse impulse ripple are shown in Table 1.
In the present embodiment, electric depositing solution is ion liquid system, and described ion liquid system is by carbamide and choline chloride
Composition, the weight ratio of choline chloride and carbamide is 1:1, copper, indium, gallium, the content of plasma selenium and come in ion liquid system
Source is shown in Table 2.Electrochemical deposition arranges and includes the platinized platinum as anode, can provide anti-as the platinum filament of reference electrode and one
To the power supply of pulse.With Control of Voltage during electrochemical deposition, measure simultaneously and note down voltage and the change of corresponding electric current density
Change.
The CIGS preformed layer configuration of surface prepared according to the method for the present embodiment carries out electron microscope scanning, such as Fig. 5
Shown in, CIGS surface without chondritic, Energy Dispersive X-ray power spectrum show the content of selenium 50.8%, overall composition
Meet the requirement of CIGS preformed layer.
Comparative example
Comparative example 1
The method preparing CIGS preformed layer according to embodiment 1 electrochemical deposition.It neutralizes embodiment 1 different is institute
Stating electrochemical deposition is constant current, and electric current density and the corresponding change in voltage of galvanostatic deposition are shown in Fig. 6, the electricity of constant current
Current density is shown in Table 1, and remaining condition is with embodiment 1.
The CIGS preformed layer configuration of surface prepared according to this comparative example carries out electron microscope scanning, as it is shown in fig. 7,
CIGS surface is filled with a lot of chondritic, and the X-ray energy spectrum obtained on spherical shows that the content of selenium is 98%, ball
The content of the structure selenium on shape side is 44%, and other composition includes copper, indium and gallium.
Comparative example 2
The method preparing CIGS preformed layer according to embodiment 2 electrochemical deposition.It neutralizes embodiment 2 different is institute
Stating electrochemical deposition is constant voltage, and the voltage of constant voltage and corresponding current density change are shown in Fig. 8, the electricity of constant voltage deposition
Pressure is shown in Table 1, and remaining condition is with embodiment 2.
The CIGS preformed layer configuration of surface prepared according to this comparative example carries out electron microscope scanning, as it is shown in figure 9,
CIGS surface is filled with a lot of chondritic, and the X-ray energy spectrum obtained on spherical shows that the content of selenium is 86%, ball
The content of the structure selenium on shape side is 38%, and other composition includes copper, indium and gallium.
The impulse wave that table 1 embodiment and comparative example are used
Copper, indium, gallium, the content of selenium and source in table 2 electrochemical deposition liquid
Claims (9)
1. the method that an electrochemical deposition prepares CIGS preformed layer, it is included in electric depositing solution, use electric current to control pulse or Control of Voltage pulse and obtain CIGS preformed layer at cathode substrate substrates, it is characterised in that: described electric current controls pulse or Control of Voltage pulse include electric current and voltage deposition surface all reach direct impulse period of negative value and electric current and voltage deposition surface all reach on the occasion of reverse impulse period；
Described electric depositing solution is ion liquid system；
Described electric current controls the impulsive condition of pulse: the working time in direct impulse period is 3 milliseconds～1 second, electric current density-0.05ASD～-5ASD；The working time in reverse impulse period is 1 millisecond～0.5 second, and electric current density is 0.1ASD～20ASD；.
Electrochemical deposition the most according to claim 1 prepares the method for CIGS preformed layer, it is characterised in that in described electric depositing solution, copper, indium, gallium, the concentration of plasma selenium are respectively 0.1mM-50mM, 0.1mM-60mM, 0.1mM-80mM, 0.1mM-50mM.
Electrochemical deposition the most according to claim 1 prepares the method for CIGS preformed layer, it is characterised in that the solvent of described ion liquid system is made up of choline chloride and carbamide, and choline chloride is 1: 0.5-5 with the weight ratio of carbamide.
Electrochemical deposition the most according to claim 3 prepares the method for CIGS preformed layer, it is characterised in that choline chloride is 1:2 with the weight ratio of carbamide.
Electrochemical deposition the most according to claim 2 prepares the method for CIGS preformed layer, it is characterised in that in electric depositing solution, all or part of copper ion is by entering electric depositing solution after anodic oxidation.
Electrochemical deposition the most according to claim 2 prepares the method for CIGS preformed layer, it is characterised in that in electric depositing solution, all or part of gallium ion is by entering electric depositing solution after anodic oxidation.
Electrochemical deposition the most according to claim 2 prepares the method for CIGS preformed layer, it is characterised in that in electric depositing solution, all or part of indium ion is by entering electric depositing solution after anodic oxidation.
Electrochemical deposition the most according to claim 2 prepares the method for CIGS preformed layer, it is characterised in that in electric depositing solution, all or part of plasma selenium is by entering electric depositing solution after anodic oxidation.
9. prepare CIGS preformed layer prepared by the method for CIGS preformed layer according to the electrochemical deposition described in claim 1～8 any one, it is characterised in that: use described reverse impulse to participate in thickness is integral prefabricated layer thickness more than the 20% of deposition preformed layer.
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| CN104141151A (en) * | 2014-08-06 | 2014-11-12 | 哈尔滨工业大学 | Method for forming metal simple substance through ionic liquid in electrolytic deposition mode |
| CN105633199B (en) * | 2014-11-06 | 2017-04-05 | 中物院成都科学技术发展中心 | Improve the electrochemical process for treating of copper-zinc-tin-sulfur film surface nature |
| CN105633205B (en) * | 2014-11-06 | 2017-03-29 | 中物院成都科学技术发展中心 | The electrochemical process for treating of modification copper-zinc-tin-sulfur film solar cell absorbed layer surface nature |
| CN105633200B (en) * | 2014-11-06 | 2017-04-05 | 中物院成都科学技术发展中心 | The electrochemical process for treating of CIGS thin-film surface etch |
| CN105633204B (en) * | 2014-11-06 | 2017-04-05 | 中物院成都科学技术发展中心 | Improve the electrochemical process for treating of CIGS thin-film surface nature |
| CN107507874A (en) * | 2017-08-07 | 2017-12-22 | 南开大学 | A kind of method that high quality indium film is prepared for the pulse electrodeposition of compound semiconductor film and solar cell |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101079454A (en) * | 2007-05-29 | 2007-11-28 | 中南大学 | A method for pulse electrodeposit CIGS semiconductor film material |
| CN101570871A (en) * | 2009-06-09 | 2009-11-04 | 河南大学 | Method for electrodepositing copper indium diselenide or copper indium gallium selenide film by special pulsing power source |
| CN102214735A (en) * | 2011-06-11 | 2011-10-12 | 蚌埠玻璃工业设计研究院 | Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell |
| CN102569508A (en) * | 2011-12-29 | 2012-07-11 | 中山大学 | Thin-film solar photovoltaic cell with nano wire array structure and preparation method for thin-film solar photovoltaic cell |
| CN102694068A (en) * | 2012-05-23 | 2012-09-26 | 中南大学 | Method for surface modification of copper indium gallium diselenide (Cu(In, Ga)Se2) film |
| CN102741458A (en) * | 2009-09-08 | 2012-10-17 | 西安大略大学 | Electrochemical method of producing copper indium gallium diselenide (cigs) solar cells |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120006687A1 (en) * | 2010-07-06 | 2012-01-12 | Chi-Woo Lee | Method of forming cigs thin film |
-
2012
- 2012-10-22 CN CN201210405257.6A patent/CN103779438B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101079454A (en) * | 2007-05-29 | 2007-11-28 | 中南大学 | A method for pulse electrodeposit CIGS semiconductor film material |
| CN101570871A (en) * | 2009-06-09 | 2009-11-04 | 河南大学 | Method for electrodepositing copper indium diselenide or copper indium gallium selenide film by special pulsing power source |
| CN102741458A (en) * | 2009-09-08 | 2012-10-17 | 西安大略大学 | Electrochemical method of producing copper indium gallium diselenide (cigs) solar cells |
| CN102214735A (en) * | 2011-06-11 | 2011-10-12 | 蚌埠玻璃工业设计研究院 | Method for preparing absorbed layer of CIGS (copper indium gallium selenide)/sulfur solar cell |
| CN102569508A (en) * | 2011-12-29 | 2012-07-11 | 中山大学 | Thin-film solar photovoltaic cell with nano wire array structure and preparation method for thin-film solar photovoltaic cell |
| CN102694068A (en) * | 2012-05-23 | 2012-09-26 | 中南大学 | Method for surface modification of copper indium gallium diselenide (Cu(In, Ga)Se2) film |
Non-Patent Citations (3)
| Title |
|---|
| − xGaxSe2 Absorber Layer Fabricated by Pulse-Reverse Electrodeposition Technique for Thin Films Solar Cell.《Journal of the Electrochemical Society》.2009,第156卷(第12期),第553-557页. * |
| Fu Y. P. 等.CuIn1  * |
| 周期换向脉冲电沉积-硒化法制备铜铟镓硒薄膜;曹洁 等;《功能材料与器件学报》;20110430;第17卷(第2期);第187-194页、图1-12 * |
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