CN105870001A - Method for preparing copper-indium-sulfur photo-electric film through copper nitrate - Google Patents
Method for preparing copper-indium-sulfur photo-electric film through copper nitrate Download PDFInfo
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- CN105870001A CN105870001A CN201610418927.6A CN201610418927A CN105870001A CN 105870001 A CN105870001 A CN 105870001A CN 201610418927 A CN201610418927 A CN 201610418927A CN 105870001 A CN105870001 A CN 105870001A
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- 238000000034 method Methods 0.000 title claims abstract description 27
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 title claims abstract description 9
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000011521 glass Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 21
- 239000010408 film Substances 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 14
- 230000005693 optoelectronics Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000873 masking effect Effects 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004528 spin coating Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229910017610 Cu(NO3) Inorganic materials 0.000 abstract 1
- 238000011068 loading method Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005118 spray pyrolysis Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000004913 activation Effects 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
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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-sulfur photo-electric film through copper nitrate, and belongs to the technical field of preparation of photo-electric films for solar batteries. The method comprises the following steps: firstly, cleaning a glass substrate; putting Cu(NO3)2.3H2O, In(NO3)3.4.5H2O and CH3CSNH2 into a solvent and uniformly mixing; preparing a precursor film on the glass substrate by using a spin-coating method, and drying; putting the dried precursor film into an enclosable container filled with hydrazine hydrate; preventing a precursor film sample from getting into contact with the hydrazine hydrate; loading the enclosed container loaded filled with the sample into a drying oven for heating, and preserving heat; finally, taking the sample out, soaking for 24 hours and drying to obtain the copper-indium-sulfur photo-electric film. The method has the advantages of no need of a high-temperature and high-vacuum condition, low instrument equipment, low production cost, high production efficiency, and easiness in operation; the copper-indium-sulfur photo-electric film has high continuity and uniformity; a CuInS2 phone is taken as a main phase; according to the novel process, components and structure of a target product can be controlled easily; and a production method which is low in cost and can be used for realizing industrialization is provided for preparation of a high-performance copper-indium-sulfur photo-electric film.
Description
Technical field
The invention belongs to solar cell optoelectronic film preparing technical field, particularly relate to a kind of method being prepared copper and indium sulfur optoelectronic film by copper nitrate.
Background technology
Along with society and expanding economy; the Fossil fuels such as coal, oil, natural gas are applied to produce and the various aspects of life; the continuous utilization of Fossil fuel; tellurian resource is constantly reduced; so seeking a kind of new energy to become the task of top priority of every country; on the other hand; the continuous utilization of Fossil fuel also brings the impact in terms of environment; particularly in terms of greenhouse effect, therefore develop clean reproducible energy and to protection environment, sustainable economic development and construct harmonious society and have important meaning.Photovoltaic generation have safe and reliable, noiseless, pollution-free, restriction less, the advantage such as failure rate is low, easy maintenance, this cleaning of solar energy, safety and the regenerative resource of environmental protection, the research and development of solar cell the most in recent decades can be utilized to be increasingly subject to pay attention to.
Copper and indium sulfenyl thin film solar cell may be considered one of the most promising hull cell at present, this is because its absorbed layer material C uInS2There is a series of advantage: (1) CuInS2Being direct band-gap semicondictor, this can reduce the requirement to minority carrier diffusion.(2) at room temperature CuInS2Energy gap be 1.50eV, be in solar cell require optimal energy gap, this respect is better than CuInSe2(1.04eV).(3)CuInS2Without any toxic component, and energy gap is bigger, it is possible to produce higher open-circuit voltage, so that hot coefficient is little, i.e. along with temperature raises, pressure drop reduces.(4) CuInS2Absorptance is very big, and conversion efficiency is high, and stable performance, film thickness is little, about 2 μm, and the price of sulfur is relatively low, and time prepared by large area, price is relatively low.(5) at CuInS2On the basis of adulterate other element, as made Ga or Al part replace In atom, replace S by Se part, be i.e. prepared as Cu (In1-xGax)Se2, Cu (In1-xGax)(Se2-ySy)
[10], Cu (In1-xAlx)(Se2-xSx), its crystal structure remains Chalkopyrite.Change the atomic ratio of wherein Ga/ (Ga+In) etc., its energy gap can be made to change between 1.04～1.72 eV, comprise high efficiency and absorb the bandgap range 1.4～1.6eV of sunlight；(6) the least in wider composition range internal resistance rate；(7) capability of resistance to radiation is strong, does not has photo attenuation effect, thus service life is long；(8) lattice structure of p-type CIGS material can be mated with common N-type window material (such as CdS, ZnO) with electron affinity.
CuInS at present2Preparation method mainly have solvent-thermal method, spray pyrolysis method (Spray Prolysis), electrojet method, electro-deposition, chemical deposition, the chemical vapor transportation method of closing, chemical gaseous phase deposition, molecular beam epitaxy, reactive sputtering, vacuum vapor deposition method, Metalorganic chemical vapor deposition method, sputtered alloy layers-sulfuration method etc..With CuInSe2Compare, CuInS2Without any toxic component, and energy gap is bigger, it is possible to produce higher open-circuit voltage, so that hot coefficient is little, i.e. along with temperature raises, pressure drop reduces.Due to CuInS2Cost of material is low, is therefore the most rising a kind of solar cell material, but existing process route is complicated, preparation cost high, thus needs also exist for exploring the preparation technology of low cost.
Method is the same as previously described, and other method also has different defects.Related to the present invention also has such as Publication about Document:
[1]R. Schurr, A. Hölzing, F. Hergert, R. Hock, M. Purwins, J.
Palma, The formation of the thin-lm solar cell
absorber CuInS2 by annealing of Cu–In–S stacked elemental layer precursors — A comparison of selenisation and sulfurisation.
Thin Solid Films 517 (2009) 2136–2139.
Essentially describe the CuInS sending out system with sputtering-sulfuration2Thin film, and selenizing method is prepared CuInSe2CuInS is prepared with sulfuration method2Do comparative study.
[2]Jicheng
Zhou, Shaowen Li, Xiaoliang
Gong, Yanlin Yang, Liang You, Rapid preparation of
CuInS2 microparticles via a
solution-chemical synthesis route and its characterization, Materials Letters
65 (2011) 3465–3467.
Article reports prepares CuInS with solution chemical method2, and have studied the impact on its performance of reaction temperature and time.
[3]M.S. Park, S.Y. Han, E.J. Bae, T.J. Lee,C.H. Chang,
Synthesis and characterization of polycrystalline CuInS2Thin lms for solar cell devices at low temperature processing
conditions, Current Applied Physics 10 (2010) S379–S382.
Essentially describe the solwution method by a kind of novelty and prepare CuInS at low temperatures2And the research of photoelectric properties.
[4]C. Mahendran,
N. Suriyanarayanan, Effect of temperature on
structural, optical and photoluminescence properties of polycrystalline CuInS2Thin lms prepared by spray pyrolysis,
Physica B 405 (2010) 2009–2013.
Mainly describe chemical spray-high-temperature decomposition and prepare CuInS2During thin film, temperature is on structure and the impact of performance.
[5] Xie Junye, Li Jian, Wang Yan are next, CuInS2The preparation of thin film and optical characteristics, functional material 42 (2011) 129 132.
Mainly report vacuum co-evaporation and prepare CuInS2Thin film, have studied different Cu, In, S element proportioning and the impact on membrane structure, stoichiometry when optical property of the heat treatment condition.
[6] Zhang Jidong, CuInS2The preparation of thin film and optical property research thereof, Zhengzhou teacher education 1 (2012) 25 29.
Article uses hydro-thermal method to prepare CuInS2Granule, then spin-coating prepares CuInS2Thin film, and study its optical property.
[7]R. Cayzac
, F. Boulc’h , M. Bendahan,M.
Pasquinelli, P. Knauth,
Preparation and optical absorption of electrodeposited or sputtered, dense or
porous nanocrystalline CuInS2Thin lms, C. R. Chimie 11 (2008) 1,016 1022.
Essentially describe sputtering method and electrodeposition process prepares nanocrystalline Cu InS2Thin film, and its optical absorption characteristics is compared research.
[8] Yang Yu, draws a bow, Zhuan great Ming, and cure time vulcanizes CuInS for solid-state2Film performance affects, vacuum science and Technology 30 (2010) 236 239.
Essentially describe employing Mid frequency alternative magnetron sputtering method deposition Cu-In prefabricated membrane, and use Solid-state sulfurization method to prepare CuInS2Thin film, have studied cure time for CuInS2Membrane structure, pattern and energy gap impact.
Summary of the invention
The present invention is to solve the deficiencies in the prior art, and invented a kind of diverse with the preparation method of prior art, the preparation technology of copper and indium sulfur solar energy thin-film material.
The present invention uses spin coating-chemistry co-reducing process to prepare copper-indium-sulfur film material, and employing soda-lime glass is substrate, with Cu (NO3)2·3H2O, In (NO3)3·4.5H2O, CH3CSNH2For raw material, with deionized water, the one or two kinds of of ethanol both solvents mixture as solvent, first prepare with spin-coating method that certain thickness (element metering ratio is as CuInS containing copper and indium sulfur2) precursor thin-film, with hydrazine hydrate as reducing agent, heat at a lower temperature in hermetic container, make precursor thin-film reduce concurrent GCMS computer reaction obtain target product.
The concrete preparation method of the present invention includes following steps in sequence:
A. carry out the cleaning of glass substrate, be to be 20mm × 20mm by glass substrate size, put into volume ratio concentrated sulphuric acid: in the solution of distilled water=1:20, boil 30 minutes；Then the above-mentioned back glass sheet that boils is put into water-bath 1 hour in 90 DEG C of water-baths；Again by glass substrate sonic oscillation 30 minutes in distilled water；Finally glass substrate obtained above is emitted in glass dish in feeding baking oven and dries for masking.
B. by Cu (NO3)2·3H2O、In(NO3)3·4.5H2O、CH3CSNH2Put in solvent, make the material in solution uniformly mix.Specifically, can be by 1.61 parts of Cu (NO3)2·3H2O, 2.55 parts of In (NO3)3·4.5H2O and 1.0 parts of CH3CSNH2Put in the solvent of 13.3 parts, make the material in solution uniformly mix, one or both mixed solution during wherein solvent is deionized water, ethanol.
C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample.Above-mentioned solution can be dripped on the glass substrate that is placed on sol evenning machine, start sol evenning machine and rotate certain time with 300～2500 revs/min, after making the solution on dripping be coated with uniformly, substrate is dried, dry again after again repeating to drip upper previous solu and spin coating, so repeat 3～5 times, obtained certain thickness precursor thin-film sample the most on a glass substrate.
D. step c gained precursor thin-film sample is placed on support, be placed with hydrazine hydrate can hermetic container, make precursor thin-film sample not contact with hydrazine hydrate.The hydrazine hydrate amount of putting into is 4.0 parts.The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated between 160～220 DEG C, temperature retention time 5～40 hours, is then cooled to room temperature and takes out.
E. step d gains are soaked 24 hours in deionized water, after carrying out room temperature natural drying, i.e. obtain copper and indium sulfur optoelectronic film.
The present invention need not high temperature high vacuum condition, requires low to instrument and equipment, and production cost is low, and production efficiency is high, it is easy to operation.Gained copper and indium sulfur optoelectronic film has preferable seriality and uniformity, and principal phase is CuInS2Phase, this new technology is easily controlled composition and the structure of target product, provides a kind of low cost for preparing high performance copper and indium sulfur optoelectronic film, can realize large-scale industrial production.
Detailed description of the invention
Embodiment 1
A. the cleaning of glass substrate: be carried out glass substrate as previously mentioned, substrate size is 20mm × 20mm.
B. by 1.61 parts of Cu (NO3)2·3H2O, 2.55 parts of In (NO3)3·4.5H2O and 1.0 parts of CH3CSNH2Put in 13.3 parts of ethanol and uniformly mix, utilize ultrasonic activation more than 30 minutes, make the material in solution uniformly mix.
C. above-mentioned solution is dripped on the glass substrate that is placed on sol evenning machine, start sol evenning machine, sol evenning machine is rotated 5 seconds with 300 revs/min, rotate 15 seconds with 2150 revs/min, after making the solution on dripping be coated with uniformly, after substrate is dried, dry again after again repeating to drip upper previous solu and spin coating, so repeat 3～5 times, obtained certain thickness precursor thin-film sample the most on a glass substrate.
D. the precursor thin-film sample of above-mentioned technique gained is put into sealable container, and puts into 4.0 parts of hydrazine hydrates, presoma
Film sample is placed on support and makes it not contact with hydrazine hydrate.The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated between 160～200 DEG C, temperature retention time 20 hours, is then cooled to room temperature and takes out.
E. step d gains are soaked 24 hours in deionized water, carry out room temperature natural drying, obtain copper and indium sulfur optoelectronic film.
Claims (5)
1. the method being prepared copper and indium sulfur optoelectronic film by copper nitrate, including following steps in sequence:
A. the cleaning of glass substrate；
B. by 1.61 parts of Cu (NO3)2·3H2O, 2.55 parts of In (NO3)3·4.5H2O and 1.0 parts of CH3CSNH2Put in the solvent of 13.3 parts, make the material in solution uniformly mix；
C. make the substrate of solution described in outside uniform application step b, and dry, obtain precursor thin-film sample；
D. step c gained precursor thin-film sample is placed on support, be placed with hydrazine hydrate can hermetic container, make precursor thin-film sample not contact with hydrazine hydrate；The hermetic container that will be equipped with precursor thin film sample is put in baking oven, is heated between 160～220 DEG C, temperature retention time 5～40 hours, is then cooled to room temperature and takes out；
E. step d gains are soaked in deionized water 24 hours, then carry out room temperature natural drying, obtain copper and indium sulfur optoelectronic film.
A kind of method being prepared copper and indium sulfur optoelectronic film by copper nitrate, it is characterised in that clean described in step a, is to be 20mm × 20mm by glass substrate size, puts into volume ratio concentrated sulphuric acid: in the solution of distilled water=1:20, boil 30 minutes；Then the above-mentioned back glass sheet that boils is put into water-bath 1 hour in 90 DEG C of water-baths；Again by glass substrate sonic oscillation 30 minutes in distilled water；Finally glass substrate obtained above is emitted in glass dish in feeding baking oven and dries for masking.
A kind of method being prepared copper and indium sulfur optoelectronic film by copper nitrate, it is characterised in that the solvent described in step b is at least one in deionized water, ethanol.
A kind of method being prepared copper and indium sulfur optoelectronic film by copper nitrate, it is characterized in that, the substrate of uniform application described in step c, it is to be smeared by sol evenning machine, sol evenning machine is with 300～2500 revs/min of rotations, then, after substrate being dried, the most so repeat 3～5 times, obtained certain thickness precursor thin-film sample.
A kind of method being prepared copper and indium sulfur optoelectronic film by copper nitrate, it is characterised in that put into 4.0 parts of hydrazine hydrates in hermetic container described in step d.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610418927.6A CN105870001A (en) | 2016-06-15 | 2016-06-15 | Method for preparing copper-indium-sulfur photo-electric film through copper nitrate |
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| CN201610418927.6A CN105870001A (en) | 2016-06-15 | 2016-06-15 | Method for preparing copper-indium-sulfur photo-electric film through copper nitrate |
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| CN105870001A true CN105870001A (en) | 2016-08-17 |
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