CN105932114A - Method for preparing solar cell absorbing layer film based on water bath and post-selenization - Google Patents
Method for preparing solar cell absorbing layer film based on water bath and post-selenization Download PDFInfo
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- CN105932114A CN105932114A CN201610567679.1A CN201610567679A CN105932114A CN 105932114 A CN105932114 A CN 105932114A CN 201610567679 A CN201610567679 A CN 201610567679A CN 105932114 A CN105932114 A CN 105932114A
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- 238000000034 method Methods 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011669 selenium Substances 0.000 claims abstract description 70
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 58
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 229910052959 stibnite Inorganic materials 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000010409 thin film Substances 0.000 claims description 54
- 239000010408 film Substances 0.000 claims description 45
- 229910052717 sulfur Inorganic materials 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011435 rock Substances 0.000 claims description 5
- 238000000427 thin-film deposition Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000005361 soda-lime glass Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 3
- 229910000058 selane Inorganic materials 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 2
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical group [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229940007424 antimony trisulfide Drugs 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000008946 yang xin Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical group [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a method for preparing solar cell absorbing layer film based on water bath and post-selenization, characterized in that inorganic salt of antimony is dissolved in a solution to obtain solution A; a sulfurous compound is dissolved in deionized water to obtain solution B; the solution B is added into the solution A and mixed well to form Sb2S3 precursor deposition; the Sb2S3 precursor deposition is deposited on a clean substrate under water bath to form Sb2S3 precursor film, and the film is blow-dried with nitrogen and stored in vacuum; the Sb2S3 precursor film is selenized and thermally treated in selenium atmosphere to finally obtain Sb2(S,S3)3 film described herein. The method synthesizing the Sb2S3 precursor film using chemical water bath and thermally treating in the selenium atmosphere is used in the invention and has the advantages such as process simplicity, safety and zero toxicity, low material cost, availability for large-scale production, and easiness in controlling film composition and thickness.
Description
Technical field
The present invention relates to solar cell material and device arts, be specifically related to a kind of water-bath and rear selenizing is prepared too
The method of sun energy battery obsorbing layer film.
Background technology
Along with socioeconomic fast development, traditional fossil energy consumes growing, thus causes the mankind to be badly in need of solving
Two matters of utmost importance: energy crisis and environmental pollution.Verify the conventional energy resource reserves such as coal, oil, natural gas at present limited,
And too much use fossil energy, will result in the negative effects such as greenhouse effects, acid rain, haze, environmental pollution.Therefore, in order to
Solving energy shortage problem and the relation of environmental harmony, searching one cleaning, the reproducible energy are extremely urgent.Solar radiation provides
Source is clearly a good selection solving energy crisis, and photovoltaic cell is the principal mode utilizing solar energy.
Current solar cell is broadly divided into first generation crystal silicon solar batteries, second generation thin-film solar cells and the
Three generations's organic solar batteries.Wherein, thin-film solar cells has that material materials are few, efficiency is high, can be flexible etc. feature, be one
Class has the solar cell of good application prospect.And antimony base Sb2(S, Se)3It it is copper-zinc-tin-sulfur (CZTS) the thin film solar electricity that continues
The class novel thin film solar cell grown up behind pond, it has abundant raw materials, lower-price characteristic and advantage.With
Time, quaternary compound material this kind of with CZTS is except that Sb2(S, Se)3The chemical constituent of film is the most single, can keep away
Exempt from the generation of other dephasign.And compare and be all the cadmium telluride CdTe that component is single, Sb2(S, Se)3Included in element more
Abundant, safety non-toxic.So Sb2(S, Se)3Thin-film solar cells is considered as the most potential novel thin film of class
Solar cell.Sb2(S, Se)3It is a kind of direct band-gap semicondictor and there is the band gap width more mated with solar spectrum
(1.15-1.75eV), absorption coefficient big (105cm-1), about 500nm ensures that bigger absorptivity to sunshine.2009
Year, Mexican Messina et al. has prepared Sb initially with directly employing chemical bath method (CBD)2SxSe3-x: Sb2O3Material
Material, and it has been prepared as the solar cell that photoelectric efficiency is 0.66%, but the selenium source used during due to annealing is chemical thought
Selenium film, during annealing, volatile selenium film can cause the problems such as crystalline property is poor, defect is more, limit its battery conversion
The raising of efficiency, therefore be not affected by paying attention to (Messina S, Nair M T S, Nair P K. Solar cells with
Sb2S3Absorber films [J]. Thin Solid Films, 2009,517 (7): 2503-2507.).2014,
The Choi of Korea S and Ngo seminar of Spain are respectively adopted thermal decomposition and electrodeposition process concept based on dye sensitization is prepared for selenium
Changing antimony material class battery, efficiency is 6.6% and 2.1%(Choi Y C, Mandal T N, Yang W S, et al. Sb2Se3-
Sensitized Inorganic-Organic Heterojunction Solar Cells Fabricated Using a
Single-Source Precursor [J]. Angewandte Chemie, 2014, 126(5): 1353-1357； Ngo
T T, Chavhan S, Kosta I, et al. Electro deposition of Antimony Selenide Thin
Films and Application in Semiconductor Sensitized Solar Cells [J]. ACS
Applied materials & interfaces, 2014,6 (4): 2836-2841.).But the mixing of this organic-inorganic
Solar cell remains stablizes the problems such as poor.Until 2014, antimony, selenium simple substance are dissolved in hydrazine by the talent such as Zhou, adopt
Prepare pure antimony selenide film by the mode of annealing, and achieve the Sb of 2.26% conversion efficiency2Se3Thin film solar electricity
Pond (Zhou Y, Leng M, Xia Z, et al. Solution-Processed Antimony Selenide
Heterojunction Solar Cells [J]. Advanced Energy Materials 4 (2014) 1301846.).
In the same year, Chen etc. uses thermal evaporation to be prepared for CdS/Sb2Se3The thin-film solar cells of type structure, efficiency is 2.1%(Chen
J, Luo M, Zhou Y, et al. Thermal Evaporation and Characterization of Sb2Se3 Thin
Film for Substrate Sb2Se3/CdS Solar Cells [J]. ACS Applied Materials and
Interface, 6 (2014) 10687-10695.).Zhou in 2015 et al. uses and introduces selenium steam on the basis of thermal evaporation
Anneal, be finally prepared as CdS/Sb2Se3The solar cell of type structure, efficiency brings up to 5.6%, and this is current high stable
Property full-inorganic Sb2Se3Peak efficiency (Zhou Y, Wang L, Chen S, the et al, Thin-of thin-film solar cells
film Sb2Se3 photovoltaics with oriented one-dimensional ribbons and benign
Grain boundaries, Nature Photonics 9 (2015) 409 415.).Through prior art literature patent is examined
Suo Faxian, at preparation Sb2(S, Se)3Inorganic solar cell is received in the method for layer, has had utilization sputtering antimony trisulfide preformed layer
The patent (application number 201510489479.4) of selenium antimony trisulfide semiconductor film material is prepared in rear selenizing, but magnetron sputtering plating
The equipment that method needs is costly.All there is certain problem in above-mentioned all kinds of method, as hydrazine solution is poisonous, sets needed for vacuum method
Standby expensive, production cost is high.In order to reduce solar cell preparation cost further, improve production security, explore one
Novel Sb2(S, Se)3Method for manufacturing thin film is imperative.Therefore this patent is absorbed in this problem, uses low cost, easy
Immersion method prepares Sb2S3After precursor thin-film, then by being heat-treated in selenium atmosphere, it is thus achieved that uniform large-area, the height of band-gap
Quality Sb2(S, Se)3Film.
Summary of the invention
The purpose of the present invention is to propose to a kind of low cost, easy chemical bath combine with rear selenized annealing and prepare the sun
Can battery obsorbing layer Sb2(S, Se)3The method of film.Of the present invention is that chemical bath synthesizes Sb in atmosphere2S3Before
Drive body thin film, the preparation method being heat-treated in selenium (Se) atmosphere, have that synthesis technique is simple, safety non-toxic, Preparation equipment
Uncomplicated, low raw-material cost, can realize large area produce, thin film composition and the advantage such as thickness is easily-controllable, it is adaptable to extensive
Industrial production.
Be the technical scheme is that by realizing the purpose of the present invention
Step one: select substrate, is carried out substrate surface obtaining cleaning substrate；
Step 2: the inorganic salts of antimony are dissolved and obtains solution A in the solution；Sulfur-containing compound is dissolved and obtains in deionized water
Solution B；Solution B is added in solution A, rock and make it be sufficiently mixed, then deionized water is added in above-mentioned mixed solution, formed
Sb2S3Presoma deposition liquid；
Step 3: the Sb under water bath condition, step 2 obtained2S3Presoma deposition liquid is deposited on cleaning lining described in step one
, Sb is formed at the end2S3Precursor thin-film, and dry up with nitrogen, vacuum preserves；Sedimentation time 3～6h.
Step 4: Sb will be obtained in step 32S3Precursor thin-film, carries out selenizing heat treatment under selenium atmosphere, finally gives
Sb described in this method2(S, Se)3Film.
Substrate described in step one of the present invention is plating molybdenum film, electro-conductive glass, soda-lime glass, quartz glass and metal forming
In one.
Sb described in step 2 of the present invention2S3Precursor thin-film deposition liquid in, containing the antimony that concentration is 0.005～0.05M without
Machine salt, containing the sulfur-containing compound that concentration is 0.01～0.5M；
The inorganic salts of antimony of the present invention refer to the mixed of one or more arbitrary proportions in nitric acid antimony, antimony sulfate and trichloride antimony
Close；
Sulfur-containing compound of the present invention refers to that one or more in thioacetamide, sodium thiosulfate or thiocarbamide are any
The mixing of ratio；
Solvent of the present invention is the mixing of one or more arbitrary proportions in water, ethanol or acetone.
Water bath condition described in step 3 of the present invention refers to that temperature controls at 0～40 DEG C.
Sb of the present invention2S3The deposition of precursor thin-film, the time is 2 ~ 10h, its THICKNESS CONTROL 0.2～1 μm it
Between.
Selenizing described in step 4 of the present invention is heat-treated, and refers to Sb2S3Precursor thin-film and solid selenium source or selenizing hydrogen
Body is placed in confined space and carries out selenizing heat treatment, or by Sb2S3Precursor thin-film is in selenium steam or the hydrogen selenide of flowing
Gas carries out selenizing heat treatment；
Selenizing of the present invention is heat-treated and conventional tube stove can be used to anneal, annealing temperature 230～600 DEG C, and heat up speed
Rate controls at 1～40 DEG C/min, temperature retention time 1～60 min；Or using quick anneal oven (RTP) to anneal, heat up speed
Rate controls at 40～80 DEG C/s, annealing temperature 230～600 DEG C, temperature retention time 1～60 min.
When the selenizing in above-mentioned steps is heat-treated and uses solid selenium source, selenium powder and Sb2S3Precursor thin-film is placed in sealed tube
In formula stove, take out background vacuum to 10-2Pa, makes selenium powder and Sb2S3Precursor thin-film starts to warm up from room temperature simultaneously, or selenium powder one
End first heats up.40 DEG C/min of heating rate, holding solid selenium source temperature 230～600 DEG C, Sb2S3Precursor thin film temperature maintains
250～450 DEG C, temperature retention time 1～60 min, it is slowly cooled to room temperature subsequently.
The chemical reagent such as the inorganic salts of antimony involved in technique scheme, sulfur-containing compound, solvent all purchase in
Chemical reagents corporation of traditional Chinese medicines group, selenium powder is purchased in Aladdin Chemistry co.ltd, the plating molybdenum glass involved by substrate
Glass and soda-lime glass are purchased respectively in raw Yangxin material science and technology (Ningbo) Co., Ltd and Luoyang Long Yao Glass Co., Ltd..
The principle of the present invention is:
1) chemical bath is used to deposit the Sb containing antimony and sulphur on substrate2S3Precursor thin-film.
2) by above-mentioned Sb2S3Precursor thin-film is annealed under selenium atmosphere and is formed solar battery obsorbing layer Sb2(S, Se)3Thin
Film.
The present invention has beneficial effect highlighted below: the present invention proposes one and utilizes low cost, preparation process simple
The preparation of chemical bath method is containing antimony and the Sb of sulfur-bearing2S3Precursor thin-film, and utilize follow-up selenized annealing technique to obtain solar cell
Absorbed layer Sb2(S, Se)3Film.According to above pertinent literature and patent report, other high-quality Sb2(S, Se)3The system of film
For typically requiring high toxicity solvent, expensive vacuum equipment etc., preparation condition is the harshest.Therefore this patent have employed public affairs
The preparation method simple chemical bath method recognized successfully synthesizes the Sb containing antimony and sulphur2S3Precursor thin-film, imposes on middle high temperature simultaneously
Selenized annealing finally obtains solar battery obsorbing layer Sb2(S, Se)3Film.Concrete useful following some:
1) document report is had to use hydrazine to dissolve Sb2Se3After powder, it is coated on substrate, carries out selenized annealing process subsequently, but
Solvent for use hydrazine is high toxicity solvent, the chemical bath method that this patent uses, and preparation process is simple, solvent for use safety, low toxicity,
Deposition process can complete in atmospheric environment, solves large-scale production poor stability single-candidate problem.
2) there is patent report magnetron sputtering Sb2S3After precursor thin-film, carry out selenized annealing and obtained solar cell absorption
Layer Sb2(S, Se)3Film, equipment needed thereby costly, complicated, this patent uses chemical bath that Sb is synthesized2S3Presoma
Film, preparation process can complete in antivacuum, and process is simple, and the cycle is short, solves high the asking of large-scale production cost
Topic.
3) patent retrieval finds, this patent combines the chemical bath of low cost first and rear selenized annealing prepares solar energy
Battery obsorbing layer Sb2(S, Se)3Film；Chemical bath method prepares inorganic thin film has document report to have the benefit of two big aspects
Place: one, is that film thickness can be realized by control reaction temperature and time easily；Its two, be immersion method
Prepare precursor thin film and can accomplish that large-area deposition, applicable industrialization prepare requirement on a large scale.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings, the invention will be further described.
Fig. 1 is the Sb of embodiment 1 of the present invention preparation2S3Precursor thin-film surface is schemed with section SEM.
Fig. 2 is the solar battery obsorbing layer Sb of embodiment 1 of the present invention preparation2(S, Se)3Film XRD.
Fig. 3 is the solar battery obsorbing layer Sb of embodiment 1 of the present invention preparation2(S, Se)3Film surface and section
SEM schemes.
Detailed description of the invention
In order to present invention may be better understood, existing the present invention is described further by way of example.
Embodiment 1
1, first glass substrate is carried out: glass substrate is immersed successively washing agent, deionized water, ethanol, acetone soln
In, then deionized water is ultrasonic and rinses well, and nitrogen dries up；
2, by 0.13g trichloride antimony SbCl3It is dissolved in 500ul acetone soln, referred to as solution A.By the five hydration sulphur generations of 1.24g
Sodium sulphate (Na2S2O3•5H2O) dissolve in 5 ml of water, referred to as solution B.Solution B is added solution A, rocks and make it the most mixed
Close, then the deionized water of 14.5ml is added in above-mentioned mixed solution, form Sb2S3Presoma deposition liquid.
3, the cleaned glass substrate that step 1 obtains is put into the Sb that step 2 configures2S3Presoma deposition liquid, in water-bath temperature
Degree carries out thin film deposition under conditions of being 20 DEG C, form Sb2S3Precursor thin-film, sedimentation time 3h.
4, step 3 is obtained the Sb caused2S3Precursor thin-film uses deionized water rinsing 3 times after taking out, and dries up with nitrogen,
Vacuum keeps in Dark Place.Its surface and profile scanning Electronic Speculum result are as shown in Figure 1.
5, the Sb that step 4 obtains is utilized2S3Precursor thin-film is placed in selenium atmosphere heat treatment.Select airtight intensification tube furnace,
Use solid selenium powder is as selenium source, by 0.02g selenium powder and Sb2S3Film is placed in airtight tube type stove, is added on the one of tube furnace
End, takes out background vacuum to 10-2pa.Make selenium powder and Sb2S3Film starts to warm up from room temperature simultaneously, 40 DEG C/min of heating rate,
It is maintained at 400 DEG C eventually, is incubated 10min, after being slowly cooled to room temperature subsequently, obtains solar battery obsorbing layer Sb2(S, Se)3Thin
Film.
Utilize the solar battery obsorbing layer Sb that the present embodiment is prepared by X-ray diffraction2(S, Se)3Film is tested,
As in figure 2 it is shown, the solar battery obsorbing layer Sb prepared for the present embodiment2(S, Se)3The X ray diffracting spectrum of film, from Fig. 2
It can be seen that the XRD diffraction maximum of described annealing thin film and standard Sb2Se3XRD diffraction maximum coincide, binding constituents EDS analyze can
Knowing in annealing rear film and still contain a small amount of sulphur (S), obtained annealing thin film is Sb2(S, Se)3Phase.Fig. 3 is that this moves back
The scanning electron microscopic picture of fire film, it can be seen that this film compactness is good, crystallinity is strong, planarization is high.
Embodiment 2
1, first plating molybdenum substrate is carried out: plating molybdenum substrate is immersed washing agent, deionized water, ethanol, acetone soln successively
In, then deionized water is ultrasonic and rinses well, and nitrogen dries up；
2, by 0.52g trichloride antimony SbCl3It is dissolved in 4ml acetone soln, referred to as solution A.By the five hydration sulphur of 4.96g for sulphur
Acid sodium (Na2S2O3•5H2O) it is dissolved in 20ml water, referred to as solution B.Solution B is added solution A, rocks and make it the most mixed
Close, then the deionized water of 58ml is added in above-mentioned mixed solution, form Sb2S3Presoma deposition liquid.
3, clean plating molybdenum substrate step 1 obtained puts into the Sb that step 2 configures2S3Presoma deposition liquid, in water-bath temperature
Degree carries out thin film deposition, reaction time 6h under conditions of being 40 DEG C.
4, step 3 is obtained the Sb caused2S3Precursor thin-film uses deionized water rinsing 3 times after taking out, and dries up with nitrogen,
Vacuum keeps in Dark Place.
5, the Sb that step 4 obtains is utilized2S3Precursor thin-film is placed in selenium atmosphere heat treatment.Select the intensification pipe of open type
Formula stove, use solid selenium powder is as selenium source, by 0.1g selenium powder and Sb2S3Precursor thin-film is placed in open type tube furnace, takes out background
Vacuum is to 10-2High-purity argon gas (purity is 99.999%, and flow is 5sccm) it is passed through after pa.Make selenium powder and substrate open from room temperature simultaneously
Beginning to be warming up to 420 DEG C, heating rate is 40 DEG C/min, after reaction time 30min, is slowly cooled to room temperature, obtains solar energy
Battery obsorbing layer Sb2(S, Se)3Film.
Embodiment 3
1, first quartz substrate is carried out: quartz substrate is immersed successively washing agent, deionized water, ethanol, acetone soln
In, then deionized water is ultrasonic and rinses well, and nitrogen dries up；
2, by 0.26g trichloride antimony SbCl3It is dissolved in 4ml acetone soln, referred to as solution A.By the five hydration sulphur of 1.24g for sulphur
Acid sodium (Na2S2O3•5H2O) it is dissolved in 20ml water, referred to as solution B.Solution B is added solution A, rocks and make it the most mixed
Close, then the deionized water of 20ml is added in above-mentioned mixed solution, form Sb2S3Presoma deposition liquid.
3, clean quartz substrate step 1 obtained puts into the Sb that step 2 configures2S3Presoma deposition liquid, in water-bath temperature
Degree carries out thin film deposition, reaction time 5h under conditions of being 10 DEG C.
4, step 3 is obtained the Sb caused2S3Precursor thin-film uses deionized water rinsing 3 times after taking out, and dries up with nitrogen,
Vacuum keeps in Dark Place.
5, the Sb that step 4 obtains is utilized2S3Precursor thin-film is placed in selenium atmosphere heat treatment.Select airtight intensification tube furnace,
Use solid selenium powder is as selenium source, by 0.05g selenium powder and Sb2S3Precursor thin-film is placed in airtight tube type stove, is added on tube furnace
One end, take out background vacuum to 10-2pa.Make selenium powder start to warm up from 20 DEG C, after selenium source temperature is increased to 450 DEG C, immediately will
Sb2S3Precursor thin-film is warming up to 380 DEG C from 20 DEG C, and is incubated 20min.The heating rate of selenium source and film is 40 DEG C/min.
After reaction terminates, selenium source and underlayer temperature are slowly cooled to room temperature simultaneously, obtain solar battery obsorbing layer Sb2(S, Se)3Thin
Film.
In above three embodiment, the chemical reagent involved by preparation: trichloride antimony, sodium thiosulfate, absolute ethyl alcohol
Purchasing in chemical reagents corporation of traditional Chinese medicines group Deng all, selenium powder is purchased in Aladdin Chemistry co.ltd, involved by substrate
To plating molybdenum glass and soda-lime glass purchase respectively and have in raw Yangxin material science and technology (Ningbo) Co., Ltd and Luoyang dragon credit glass
Limit company.
In above-mentioned specific embodiment one, prepare gained Sb2S3Precursor thin-film SEM figure is as it is shown in figure 1, prepared Sb2
(S, Se)3Solar battery obsorbing layer film XRD, Raman and SEM test result respectively such as Fig. 2, shown in 3 and 4.Need to refer to
Going out, embodiment 2 and 3 test result is similar to Example 1.
Embodiment described above only have expressed two detailed description of the invention of the present invention, has been the present invention furtherly
Bright, describe more in detail and concrete, but can not be therefore understands that be the restriction to patent of the present invention.It should be pointed out that, not
On the premise of departing from present inventive concept, making some deformation and improvement, these broadly fall into protection scope of the present invention.Therefore, originally
The protection domain of patent of invention should be as the criterion with claims.
Claims (10)
1. the method preparing solar battery obsorbing layer film based on water-bath and rear selenizing, it is characterised in that:
Step one: select substrate, is carried out substrate surface obtaining cleaning substrate；
Step 2: the inorganic salts of antimony are dissolved and obtains solution A in the solution；Sulfur-containing compound is dissolved and obtains in deionized water
Solution B；Solution B is added in solution A, rock and make it be sufficiently mixed, then deionized water is added in above-mentioned mixed solution, formed
Sb2S3Presoma deposition liquid；
Step 3: the Sb under water bath condition, step 2 obtained2S3Presoma deposition liquid is deposited on cleaning substrate described in step one
On, form Sb2S3Precursor thin-film, and dry up with nitrogen, vacuum preserves；Sedimentation time 3～6h；
Step 4: thickness Sb between 0.2～1 μm will be obtained in step 32S3Precursor thin-film, carries out selenium under selenium atmosphere
Heat-transmission processes, and finally gives the Sb described in this method2(S, Se)3Film.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that the substrate described in step one of the present invention is plating molybdenum film, electro-conductive glass, soda-lime glass, quartz glass and metal
One in paper tinsel.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that the Sb described in step 22S3In precursor thin-film deposition liquid, inorganic containing the antimony that concentration is 0.005～0.05M
Salt, containing the sulfur-containing compound that concentration is 0.01～0.5M.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that the inorganic salts of described antimony refer to the mixed of one or more arbitrary proportions in nitric acid antimony, antimony sulfate and trichloride antimony
Close.
One the most according to claim 1 prepares solar battery obsorbing layer Sb based on water-bath and rear selenizing2(S, Se)3Thin
The method of film, it is characterised in that described sulfur-containing compound refers to the one in thioacetamide, sodium thiosulfate or thiocarbamide
Or the mixing of several arbitrary proportion.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that described solvent is the mixing of one or more arbitrary proportions in water, ethanol or acetone.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that the water bath condition described in step 3 refers to that bath temperature controls at 0～40 DEG C.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that selenizing described in step 4 is heat-treated, refer to Sb2S3Precursor thin-film is put with solid selenium source or hydrogen selenide gas
Selenizing heat treatment is carried out in confined space, or by Sb2S3Precursor thin-film is in selenium steam or the hydrogen selenide gas of flowing
In carry out selenizing heat treatment.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 1,
It is characterized in that selenizing of the present invention is heat-treated can use conventional tube stove to anneal, annealing temperature 230～600 DEG C,
Heating rate controls at 1～40 DEG C/min, temperature retention time 1～60 min；Or use quick anneal oven (RTP) to anneal,
Heating rate controls at 40～80 DEG C/s, annealing temperature 230～600 DEG C, temperature retention time 1～60 min.
A kind of method preparing solar battery obsorbing layer film based on water-bath and rear selenizing the most according to claim 9,
It is characterized in that when selenizing is heat-treated and uses solid selenium source, selenium powder and Sb2S3Precursor thin-film is placed in airtight tube type stove, takes out
Background vacuum is to 10-2Pa, makes selenium powder and Sb2S3Precursor thin-film starts to warm up from room temperature simultaneously, or first heats up in selenium powder one end,
40 DEG C/min of heating rate, holding solid selenium source temperature 230～600 DEG C, Sb2S3Precursor thin film temperature maintains 250～450 DEG C,
Temperature retention time 1～60 min, is slowly cooled to room temperature subsequently.
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