CN105489673A - Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method - Google Patents
Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method Download PDFInfo
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- CN105489673A CN105489673A CN201510943184.XA CN201510943184A CN105489673A CN 105489673 A CN105489673 A CN 105489673A CN 201510943184 A CN201510943184 A CN 201510943184A CN 105489673 A CN105489673 A CN 105489673A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000010409 thin film Substances 0.000 title claims abstract description 25
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 24
- 230000005693 optoelectronics Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000000429 assembly Methods 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000000873 masking effect Effects 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 abstract 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910000238 buergerite Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 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
-
- 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
Abstract
The invention discloses a method for preparing a copper-indium sulfide photoelectric thin film by a chloride system through a two-step method, and belongs to the preparation technical field of a thin film for a solar cell. The preparation method comprises the following steps of cleaning a stannic oxide conductive glass substrate; putting C6H5Na3O7.2H2O, CuCl2.2H2O, InCl3, and Na2S2O3.5H2O into distilled water; obtaining a precursor thin film by adopting an electrodeposition method on the conductive glass substrate; naturally drying, and putting into a tube furnace added with hydrazine hydrate to enable the precursor thin film product not to be in contact with hydrazine hydrate, wherein hydrazine hydrate is added with sublimed sulfur powder; heating in the sealed tube furnace to enable the precursor thin film to be vulcanized, and finally taking out the sample and drying the sample to obtain the copper-indium sulfide photoelectric thin film. The preparation method does not require a high vacuum condition, and is low in instrument equipment requirement, low in production cost, high in production efficiency and easy to operate; the obtained copper-indium sulfide photoelectric thin film is relatively high in continuity and uniformity; the main phase adopts a CuInS2 phase, so that the low-cost and large-scale industrial production can be realized.
Description
Technical field
The invention belongs to optoelectronic film preparing technical field used for solar batteries, particularly relate to a kind of method that chloride system two-step method prepares copper indium sulphur optoelectronic film.
Background technology
Along with society and expanding economy; the pollution that energy scarcity and consuming energy bring has become the outstanding problem in domestic social development; coal, oil etc. are non-renewable resources, therefore develop clean reproducible energy to protection of the environment, ensure sustainable economic development and construct harmonious society have important meaning.Photovoltaic generation have safe and reliable, noiseless, pollution-free, restriction less, the advantage such as failure rate is low, easy maintenance, can utilize the regenerative resource of this clean, safety of solar energy and environmental protection, therefore the research and development of solar cell comes into one's own day by day in recent decades.
Copper indium sulfenyl thin-film solar cells can think one of the most promising hull cell at present, this is because its absorbed layer material C uInS
2there is a series of advantage: (1) CuInS
2it is direct gap semiconductor.(2) at room temperature CuInS
2energy gap be 1.50eV, be the best energy gap required in solar cell, this respect is better than CuInSe
2(1.04eV).(3) CuInS
2not containing any toxic component.(4) CuInS
2the absorption coefficient of light is very large, and conversion efficiency is high, stable performance, and film thickness is little, about 2 μm, and the price of sulphur is lower.(5) at CuInS
2adulterate in basis other element, as made Ga or Al part replace In atom, replacing S, be namely prepared into Cu (In by Se part
1-xga
x) Se
2, Cu (In
1-xga
x) (Se
2-ys
y), Cu (In
1-xal
x) (Se
2-xs
x), its crystal structure remains chalcopyrite.Change the atomic ratio of wherein Ga/ (Ga+In) etc., its energy gap can be made to change between 1.04 ~ 1.72eV, comprise bandgap range 1.4 ~ 1.6eV that high efficiency absorbs sunlight.(6) capability of resistance to radiation is strong, does not have photo attenuation effect, thus long service life.(7) lattice structure of P type CIGS material can be mated with common N-type window material (as CdS, ZnO) with electron affinity.
Current CuInS
2preparation method mainly contain solvent-thermal method, spray pyrolysis method, electrochemical deposition method, chemical deposition, chemical vapour deposition (CVD), molecular beam epitaxy, reactive sputtering, vacuum vapor deposition method, sputtered alloy layers after cure method etc.Wherein, evaporation and sputtering method Technical comparing maturation, photoelectric conversion efficiency is high, has realized industrialization operation.But these two kinds of methods all need vacuum equipment, and preparation cost is higher, and can not the solar energy film of depositing large-area, raw-material utilance is lower.Electro-deposition cost is low, easily realizes large-area film deposition, also there are some problems simultaneously, and such as Cu, In, S tri-kinds of element potential value differences are comparatively large, are difficult to realize codeposition, and find at preparation CuInS
2time film quality poor, hole is many, element sulphur film more difficult to get access, and chemical composition is difficult to the problems such as control, be difficult to directly obtain pure phase.Therefore suitable electrodeposition technology is selected to prepare the pure phase CuInS of uniform compact
2film becomes the important topic with novelty.
Method is the same as previously described, and other method also has different defects.Related to the present invention also has as Publication about Document:
[1]S.Lugo,I.López,Y.Pe?a,M.Calixto,T.Hernández,S.Messina,D.Avellaneda,CharacterizationofCuInS
2thinfilmspreparedbychemicalbathdepositionandtheirimplementationinasolarcell,ThinSolidFilms569(2014)76–80.
Essentially describe and prepare In respectively with chemical deposition
2s
3with CuS film, after-baking obtains CuInS
2film, and its performance is characterized.
[2]ZhaominHao,YongCui,GangWang,ColloidalsynthesisofwurtziteCuInS
2nanocrystalsandtheirphotovoltaicapplication,MaterialsLetters146(2015)77–80.
Essentially describe and prepare buergerite CuInS by colloid synthetic method
2nanocrystal, is studied its crystal structure and photoelectric properties.
[3]S.MostafaHosseinpour-Mashkani,MasoudSalavati-Niasari,FatemehMohandes,K.Venkateswara-Rao,CuInS
2nanoparticles:Microwave-assistedsynthesis,characterization,andphotovoltaicmeasurements,MaterialsScienceinSemiconductorProcessing16(2013)390–402.
Main description microwave assisting method prepares CuInS
2the research of nano particle and photoelectric properties thereof.
[4]S.M.Hosseinpour-Mashkani,M.Salavati-Niasari,F.Mohandes,CuInS
2nanostructures:Synthesis,characterization,formationmechanismandsolarcellapplications,JournalofIndustrialandEngineeringChemistry20(2014)3800–3807.
Main description microwave assisting method prepares chalcopyrite CuInS
2nano particle, and performance characterization and formation mechanism study have been carried out to it.
[5]XiaofengWu,YaohanHuang,QiqiBai,QingfeiFan,GuangliLi,XimeiFan,ChaoliangZhang,HongLiu,InvestigationofCuInS
2thinfilmsdepositedonFTObyone-potsolvothermalsynthesis,MaterialsScienceinSemiconductorProcessing37(2015)250–258.
Essentially describe the CuInS that solvent-thermal process legal system is standby
2the performance of film.
[6]A.Shanmugavel,K.Srinivasan,K.R.Murali,Pulseelectrodepositedcopperindiumsulphoselenidefilmsandtheirproperties,MaterialsScienceinSemiconductorProcessing16(2013)1665–1671.
Essentially describe pulse electrodeposition legal system for CuIn (S, Se)
2film, and stuctures and properties difference when have studied different sulfur content.
[7]HsiangChen,Yih-MinYeh,ChuanHaoLiao,JianZhiChen,Chau-leWang,RemovalofCuSphasesfromelectrodepositedCuInS
2films,CeramicsInternational40(2014)67–72.
Essentially describe the CuInS adopting two-step thermal processing removal electro-deposition to prepare
2cuS phase in film has also carried out pattern and constituent analysis.
[8]M.A.MajeedKhan,SushilKumar,MohamadS.AlSalhi,SynthesisandcharacteristicsofspraydepositedCuInS
2nanocrystalsthinfilmsforphotovoltaicapplications,MaterialsResearchBulletin48(2013)4277–4282.
Main description sputtering method prepares CuInS
2film also characterizes with FESEM, FETEM, HRTEM, AFM, XRD etc.
[9]D.Abdelkader,N.Khemiri,M.Kanzari,TheeffectofannealingonthephysicalpropertiesofthermallyevaporatedCuIn
2n+1S
3n+2thinfilms(n=0,1,2and3),MaterialsScienceinSemiconductorProcessing16(2013)1997–2004.
Essentially describe the CuIn that annealing process is prepared thermal evaporation
2n+1s
3n+2the impact of (n=0,1,2and3) film performance.
[10] Ma Jianping, Gao Yang, Cu-In initialization layer after cure legal system is for CuInS
2film, solar energy journal 0254-0096 (2013) 06-1010-05.
Main description adopts pulsed magnetron sputtering legal system to obtain CuInS for the after cure of Cu-In metal preformed layer
2film.
Summary of the invention
The present invention is in order to solve existing preparation CuInS
2film Problems existing, has invented a kind of method that chloride system two-step method prepares copper indium sulphur optoelectronic film.
The present invention adopts electro-deposition after cure legal system for copper-indium-sulfur film, adopts tin dioxide conductive glass to be substrate, with CuCl
22H
2o, InCl
3, Na
2s
2o
35H
2o is raw material, with C
6h
5na
3o
72H
2o is complexing agent, take distilled water as solvent, by fixed molar ratio preparation electric depositing solution, transistor potentiostat is first adopted to prepare precursor thin-film under certain potentials and time, take hydrazine hydrate as reducing agent, in hydrazine hydrate, add sublimed sulfur powder ensure sulphur atmosphere, heat in airtight tube type stove, make precursor thin-film sulfuration and obtain target product.
Concrete preparation method of the present invention comprises the step of following order:
A. carrying out the cleaning of tin dioxide conductive glass substrate, is that volume ratio acetone put into by the glass of 20mm × 20mm by size: the solution of distilled water=5:1, Ultrasonic Cleaning 30min; Again substrate is put into ethanol, Ultrasonic Cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; Being emitted in glass dish by glass substrate obtained above sends in baking oven, dries for masking at 100 DEG C.
B. by C
6h
5na
3o
72H
2o, CuCl
22H
2o, InCl
3, Na
2s
2o
35H
2o puts into distilled water, obtains uniform and stable electric depositing solution.Specifically, can by 1.0 ~ 2.0 parts of C
6h
5na
3o
72H
2o, 4.5 ~ 9.0 parts of CuCl
22H
2o, 6.0 ~ 12.0 parts of InCl
3, 65.0 ~ 130.0 parts of Na
2s
2o
35H
2o puts into the distilled water of 2700.0 ~ 5400.0 parts, makes the substance dissolves in solution.
C. electric depositing solution described in step b is poured in three electrode assemblies, take saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-1.0V, sedimentation time is 30min, and natural drying obtains precursor thin-film sample.
D. be placed on support by step c gained precursor thin-film sample, in hydrazine hydrate, add sublimed sulfur powder, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace.It is 40.0 ~ 50.0 parts that hydrazine hydrate is put into, and sublimed sulfur powder is 1.0 ~ 2.0 parts.By between diamond heating to 250 ~ 400 DEG C, temperature retention time 3 ~ 9h, then cool to room temperature takes out.
E., by steps d gains, after making its normal temperature natural drying, copper indium sulphur optoelectronic film is namely obtained.
The present invention does not need high vacuum condition, and require low to instrument and equipment, production cost is low, and production efficiency is high, is easy to operation.Gained copper indium sulphur optoelectronic film has good continuity and uniformity, and principal phase is CuInS
2phase, can realize low cost large-scale industrial production.
Embodiment
Embodiment 1
A. the cleaning of tin dioxide conductive glass substrate: carry out cleaning glass substrate as previously mentioned, substrate size is 20mm × 20mm.
B. by 1.0 parts of C
6h
5na
3o
72H
2o, 4.5 parts of CuCl
22H
2o, 6.0 parts of InCl
3, 65.0 parts of Na
2s
2o
35H
2o puts into the distilled water of 2700.0 parts, makes the substance dissolves in solution.
C. above-mentioned electric depositing solution is poured in three electrode assemblies, take saturated calomel electrode as reference electrode, platinum electrode is auxiliary electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-1.0V, sedimentation time is 30min, and natural drying obtains precursor thin-film sample.
D. be placed on support by precursor thin-film sample, add sublimed sulfur powder in hydrazine hydrate, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace.It is 40.0 parts that hydrazine hydrate is put into, and sublimed sulfur powder is 1.0 parts.By diamond heating to 350 DEG C, temperature retention time 6h, then cool to room temperature takes out.
E. by steps d gains, carry out normal temperature natural drying, obtain copper indium sulphur optoelectronic film.
Claims (4)
1. chloride system two-step method prepares a method for copper indium sulphur optoelectronic film, comprises the step of following order:
A. the cleaning of tin dioxide conductive glass substrate;
B. by 1.0 ~ 2.0 parts of C
6h
5na
3o
72H
2o, 4.5 ~ 9.0 parts of CuCl
22H
2o, 6.0 ~ 12.0 parts of InCl
3, 65.0 ~ 130.0 parts of Na
2s
2o
35H
2o puts into the distilled water of 2700.0 ~ 5400.0 parts, makes the substance dissolves in solution;
C. adopt electrodeposition process to be deposited on electro-conductive glass sheet by solution described in step b and obtain precursor thin-film, natural drying, obtain precursor thin-film sample;
D. be placed on support by step c gained precursor thin-film sample, in hydrazine hydrate, add sublimed sulfur powder, precursor thin-film sample does not contact with hydrazine hydrate, and precursor thin-film and hydrazine hydrate are put into tube furnace; By between diamond heating to 250 ~ 400 DEG C, temperature retention time 3 ~ 9h, then cool to room temperature takes out;
E. by steps d gains, carry out natural drying, obtain copper indium sulphur optoelectronic film.
2. a kind of chloride system two-step method as claimed in claim 1 prepares the method for copper indium sulphur optoelectronic film, it is characterized in that, clean described in step a, is be 20mm × 20mm by electro-conductive glass substrate size, put into volume ratio acetone: the solution of distilled water=5:1, Ultrasonic Cleaning 30min; Again substrate is put into ethanol, Ultrasonic Cleaning 30min; In distilled water, glass substrate is used sonic oscillation 30min again; Being emitted in glass dish by glass substrate obtained above sends in baking oven, dries for masking at 100 DEG C.
3. a kind of chloride system two-step method as claimed in claim 1 prepares the method for copper indium sulphur optoelectronic film, it is characterized in that, described in step c, being added by solution in three electrode assemblies, take saturated calomel electrode as reference electrode, and platinum electrode is auxiliary electrode, tin dioxide conductive glass is Electrode, adopt transistor potentiostat normal temperature deposit film under sedimentation potential is-1.0V, sedimentation time is 30min, and natural drying obtains precursor thin-film sample.
4. a kind of chloride system two-step method as claimed in claim 1 prepares the method for copper indium sulphur optoelectronic film, it is characterized in that, puts into 40.0 ~ 50.0 parts of hydrazine hydrates, 1.0 ~ 2.0 parts of sublimed sulfur powder in tube furnace described in steps d.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943184.XA CN105489673A (en) | 2015-12-17 | 2015-12-17 | Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510943184.XA CN105489673A (en) | 2015-12-17 | 2015-12-17 | Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method |
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| Publication Number | Publication Date |
|---|---|
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Family
ID=55676536
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807561A (en) * | 2018-07-01 | 2018-11-13 | 山东建筑大学 | A method of preparing copper and iron sulphur optoelectronic film with chloride |
| CN108807560A (en) * | 2018-07-01 | 2018-11-13 | 山东建筑大学 | A method of it is assisted preparing copper and iron sulphur optoelectronic film with sulphur powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080142072A1 (en) * | 2004-02-19 | 2008-06-19 | Dong Yu | Solution-based fabrication of photovoltaic cell |
| CN102034898A (en) * | 2010-10-20 | 2011-04-27 | 山东建筑大学 | Preparation method of Cu-In-S photoelectric film material for solar cells |
-
2015
- 2015-12-17 CN CN201510943184.XA patent/CN105489673A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080142072A1 (en) * | 2004-02-19 | 2008-06-19 | Dong Yu | Solution-based fabrication of photovoltaic cell |
| CN102034898A (en) * | 2010-10-20 | 2011-04-27 | 山东建筑大学 | Preparation method of Cu-In-S photoelectric film material for solar cells |
Non-Patent Citations (1)
| Title |
|---|
| 石璐丹: "电沉积制备硫族电池薄膜及其性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108807561A (en) * | 2018-07-01 | 2018-11-13 | 山东建筑大学 | A method of preparing copper and iron sulphur optoelectronic film with chloride |
| CN108807560A (en) * | 2018-07-01 | 2018-11-13 | 山东建筑大学 | A method of it is assisted preparing copper and iron sulphur optoelectronic film with sulphur powder |
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