CN103943721A - Copper-zinc-tin-sulfur (CZTS) thin film and preparation method and purposes thereof - Google Patents
Copper-zinc-tin-sulfur (CZTS) thin film and preparation method and purposes thereof Download PDFInfo
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- CN103943721A CN103943721A CN201410120345.0A CN201410120345A CN103943721A CN 103943721 A CN103943721 A CN 103943721A CN 201410120345 A CN201410120345 A CN 201410120345A CN 103943721 A CN103943721 A CN 103943721A
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- zinc
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- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000010409 thin film Substances 0.000 title abstract 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000126 substance Substances 0.000 claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 30
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 18
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000001119 stannous chloride Substances 0.000 claims abstract description 18
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 18
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 18
- 239000011592 zinc chloride Substances 0.000 claims abstract description 18
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 113
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 83
- 239000007864 aqueous solution Substances 0.000 claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 35
- 229910052719 titanium Inorganic materials 0.000 claims description 35
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 29
- 239000005864 Sulphur Substances 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 238000004528 spin coating Methods 0.000 claims description 29
- 229910052793 cadmium Inorganic materials 0.000 claims description 28
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 14
- 238000011010 flushing procedure Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000003643 water by type Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229940075417 cadmium iodide Drugs 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000002120 nanofilm Substances 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 32
- 239000004408 titanium dioxide Substances 0.000 description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 238000000151 deposition Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 12
- 230000002000 scavenging effect Effects 0.000 description 12
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 230000005518 electrochemistry Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000005693 optoelectronics Effects 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—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
- 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
- H01L21/02425—Conductive materials, e.g. metallic silicides
-
- 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
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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
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
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- 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
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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- 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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Abstract
The invention discloses a preparation method of a copper-zinc-tin-sulfur (CZTS) thin film. The preparation method includes the first step of preparing a precursor solution, dissolving copper chloride, zinc chloride, stannous chloride and thiourea jointly into methyl alcohol or ethyl alcohol and stirring the solution to be clear and transparent, the second step of carrying out ultrasonic cleaning on a substrate FTO in acetone, ethanol and deionized water respectively and sequentially, the third step of coating the precursor solution on the surface of the substrate FTO and then drying the substrate FTO, and the fourth step of placing a sample obtained in the third step into nitrogen or argon for calcining to obtain the CZTS thin film. The preparation method of the CZTS thin film is simple, easy to implement and suitable for mass production; the prepared CZTS thin film is smooth in surface, free of cracks, excellent in performance, good in photoelectrochemical performance, high in chemical stability and capable of being widely applied to the field of production of semiconductor nano-films and photoelectrocatalysis.
Description
Technical field
The present invention relates to a kind of film and its production and use, relate in particular to a kind of copper-zinc-tin-sulfur film and its production and use.
Background technology
The energy and environmental problem are increasingly sharpened in recent years, and the research that solar energy is directly transformed to chemical energy more and more receives publicity, such as through Optical Electro-Chemistry process, solar energy are changed into hydrogen and/or oxygen.Copper-zinc-tin-sulfur (CZTS is made in abbreviation) has lot of advantages, such as: the absorption coefficient of light exceedes 10
4cm
-1, band gap is approximately 1.5eV, copper, zinc, tin, element sulphur enrich at nature reserves, free from environmental pollution.The efficiency that at present it is applied to solar cell has reached 12%, and is also receiving successively concern aspect optoelectronic pole material.For the preparation of copper-zinc-tin-sulfur film, conventionally adopt electrochemical process, continuous ionic layer absorption reaction, hydro thermal method etc.But the copper-zinc-tin-sulfur film that these methods are prepared all will be through over cure (having severe toxicity) in further crystallization.In addition, in Optical Electro-Chemistry application process, there will be larger dark current, this be due to film not the photoetch of densification or sulfide cause.In addition, chemical stability when copper-zinc-tin-sulfur is as optoelectronic pole material is also a very large challenge.
Consider for these, those skilled in the art wish to adopt simple, nontoxic synthetic method.Meanwhile, explore the use field of copper-zinc-tin-sulfur film actively.
Summary of the invention
Because the above-mentioned defect of prior art, technical problem to be solved by this invention is to provide a kind of method of simple synthetic copper-zinc-tin-sulfur film.Meanwhile, in order to improve Optical Electro-Chemistry and the chemical stability of copper-zinc-tin-sulfur film as optoelectronic pole, the present invention modifies copper-zinc-tin-sulfur film surface with cadmium sulfide and titanium dioxide, make copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film optoelectronic pole.
For achieving the above object, the invention provides a kind of preparation method of copper-zinc-tin-sulfur film, comprise the following steps:
(1) preparation precursor liquid: copper chloride, zinc chloride, stannous chloride and thiocarbamide are dissolved in methyl alcohol or ethanol jointly, stir until solution clear;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water;
(3) precursor liquid is spun to the surface of substrate FTO, is then dried;
(4) sample step (3) being obtained is placed in nitrogen or argon gas is calcined, and obtains copper-zinc-tin-sulfur film.
Further, in step (1), in mole, copper chloride: zinc chloride: stannous chloride: thiocarbamide=0.5～2:1:0.5～1:4～20; Preferably, copper chloride: zinc chloride: stannous chloride: thiocarbamide=0.5:1:0.5:5.
Further, in step (2), the time of ultrasonic cleaning is 5～30 minutes.The effect that does not thoroughly affect very much film forming is cleaned in substrate.
Further, in step (3), the speed of spin coating is 300～3500 revs/min, and the time of spin coating is 5～120 seconds; Preferably, dry temperature is 100-200 DEG C, and the dry time is 5～30 points; Preferably, step (3) repeats more than twice.
Dry is the solution remaining in film in order to remove, and it is residual to reduce carbon in film.This process can repeatedly repeat, to obtain required film thickness.
Further, in step (4), the temperature of calcining is 200-600 DEG C, and the time of calcining is 1 hour.
The present invention also provides on a kind of basis of the copper-zinc-tin-sulfur film obtaining with said method, prepares the method for copper-zinc-tin-sulfur/cadmium sulfide/carbon dioxide film, and concrete steps are as follows:
(1) with cadmium iodide, caddy or cadmium acetate as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor is as complexing agent, and adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide;
(2) copper-zinc-tin-sulfur film is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 60～90 DEG C, be incubated and after 5～35 minutes, copper-zinc-tin-sulfur film taken out, with enough deionized waters and alcohol flushing and dry up, at 100～300 DEG C, calcine 30 minutes, obtain copper-zinc-tin-sulfur/cadmium sulphide membrane;
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane obtaining in step (2) is put into atomic layer deposition apparatus, at 100～250 DEG C, be incubated 30～300 minutes, obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Preferably, in step (2), in mole, cadmium source: sulphur source=1:1～10, the chemical bath aqueous solution of cadmium sulfide is alkalescence.
The invention has the beneficial effects as follows:
(1) preparation method of copper-zinc-tin-sulfur film is simple, is applicable to large-scale production;
(2) the copper-zinc-tin-sulfur film compactness that uses the preparation method of copper-zinc-tin-sulfur film of the present invention to make is good, and surfacing evenly and flawless;
(3) photoelectrochemical behaviour of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film is good, and chemical stability is high;
(4) prepared copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film can be widely used in production and the photoelectrocatalysis field of semiconductor nano film.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the copper-zinc-tin-sulfur film that makes of embodiment 1;
Fig. 2 is the Raman collection of illustrative plates of the copper-zinc-tin-sulfur film that makes of embodiment 1;
Fig. 3 is the surface scan photo of the copper-zinc-tin-sulfur film that makes of embodiment 1 under 5000 times of amplifications;
Fig. 4 is the surface scan photo of the copper-zinc-tin-sulfur film that makes of embodiment 1 under 25000 times of amplifications;
Fig. 5 is the surface scan photo of the copper-zinc-tin-sulfur film that makes of embodiment 1 under 50000 times of amplifications;
Fig. 6 is the surface scan photo of the copper-zinc-tin-sulfur film that makes of embodiment 1 under 100000 times of amplifications;
Fig. 7 is the uv-visible absorption spectra figure of the copper-zinc-tin-sulfur film that makes of embodiment 1, and the upper right corner is photon energy and (α h ν)
2relation curve;
Fig. 8 is the chopped photocurrent of copper-zinc-tin-sulfur film in sodium sulphate electrolyte and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes;
Fig. 9 is the chopped photocurrent of copper-zinc-tin-sulfur/cadmium sulphide membrane in sodium sulphate electrolyte and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes;
Figure 10 is the chopped photocurrent of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film in sodium sulphate electrolyte and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes;
Figure 11 is that the copper-zinc-tin-sulfur that makes of embodiment 1 and copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film are at 0V
rHEthe electricity conversion of (with respect to standard hydrogen electrode);
Figure 12 is chopper current-time (I-t) curve of the copper-zinc-tin-sulfur film that makes of embodiment 1;
Figure 13 is chopper current-time (I-t) curve of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film of making of embodiment 1.
Figure 14 is the chopped photocurrent of copper-zinc-tin-sulfur film in the europium nitrate solution of 0.1M and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes;
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 0.5:1:0.5:5 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 5 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 2000 revs/min, and the time of spin coating is 30 seconds; Then at 150 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 350 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 60 DEG C, be incubated and after 20 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 200 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
The present invention prepares copper-zinc-tin-sulfur film by spin-coating method and under the condition that does not need to vulcanize, component ratio to reactant, the choose reasonable of temperature and time, obtain the fine and close flawless of surfacing, can be with as 1.5eV, and there is good Optical Electro-Chemistry and the copper-zinc-tin-sulfur film of chemical stability.The simple chemical bath deposition method of this external application and Atomic layer deposition method are modified copper-zinc-tin-sulfur film surface.
Fig. 1 is the X-ray diffractogram of the copper-zinc-tin-sulfur film that makes of embodiment 1.As can be seen from the figure be: the peak of CZTS and ZnS all exists, because they have similar structure, so need Raman collection of illustrative plates further to prove to the existence of CZTS pure phase.
Fig. 2 is the Raman collection of illustrative plates of the copper-zinc-tin-sulfur film that makes of embodiment 1.As can be seen from the figure: only have the characteristic peak of CZTS, there is no the characteristic peak of ZnS, illustrate and have pure phase CZTS.
Fig. 3, Fig. 4, Fig. 5 and Fig. 6 are the surface scan photo of the copper-zinc-tin-sulfur film that makes of embodiment 1, and multiplication factor is respectively 5000 times, 25000 times, 50000 times and 100000 times.As can be seen from the figure: copper-zinc-tin-sulfur film surface compact, smooth, there is no a crackle; The surface uniform diameter that distributing is the hole of 150-250nm.
Fig. 7 is the uv-visible absorption spectra figure of the copper-zinc-tin-sulfur film that makes of embodiment 1, and the upper right corner is photon energy and (α h ν)
2relation curve.As can be seen from the figure the band gap of copper-zinc-tin-sulfur film is in 1.5eV left and right.
Fig. 8 is the chopped photocurrent of copper-zinc-tin-sulfur film in sodium sulphate electrolyte and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes.As can be seen from the figure: in metabisulfite solution, copper-zinc-tin-sulfur demonstrates the semi-conductive feature of p-type clearly, has larger density of photocurrent.
Fig. 9 is the chopped photocurrent of copper-zinc-tin-sulfur/cadmium sulphide membrane in sodium sulphate electrolyte and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes.As can be seen from the figure: after cadmium sulfide is modified, copper-zinc-tin-sulfur film electrode still shows cathode photo current, and photoelectric current has increased.
Figure 10 is the chopped photocurrent of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film in sodium sulphate electrolyte and the relation curve of voltage (with respect to saturated calomel electrode) that embodiment 1 makes.As can be seen from the figure: cathode photo current further increases, and transient current significantly reduces.
Figure 11 is that the copper-zinc-tin-sulfur that makes of embodiment 1 and copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film are at 0V
rHEthe electricity conversion (IPCE) of (with respect to standard hydrogen electrode).This test completes in traditional three-electrode system, and calomel electrode is as reference electrode, and platinum filament is as to electrode, and electrolyte is the aqueous sodium persulfate solution of 0.2M, and as light source, (light intensity is 15mW/cm to xenon lamp
2), sweep speed is 0.01V/s.As can be seen from the figure: this semi-conducting material is p-type; Dark current is very little, so the hole of surface distributed does not have a negative impact to electrode performance; Copper-zinc-tin-sulfur film photoelectric current after the modification of cadmium sulfide and titanium dioxide constantly increases; Copper-zinc-tin-sulfur surface is after cadmium sulfide and titanium dioxide modification, at 0V
rHEunder (with respect to standard hydrogen electrode) condition, electricity conversion (IPCE) has improved 1.2 times.
Figure 12 is chopper current-time (I-t) curve of the copper-zinc-tin-sulfur film that makes of embodiment 1.As can be seen from the figure: in Optical Electro-Chemistry product hydrogen is tested for a long time, copper-zinc-tin-sulfur is after 4000s test, and defect appears in surface, and along with the time constantly extends, this trend is more and more obvious, and stability has weakened accordingly.
Figure 13 is chopper current-time (I-t) curve of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.As can be seen from the figure: after the Optical Electro-Chemistry test of 12000s, photoelectric current has still kept 80%, and curve flattening, illustrates that film has been subject to titanium dioxide and has well protected, and stability increases greatly.
Figure 14 is the chopped photocurrent of copper-zinc-tin-sulfur optoelectronic pole in the europium nitrate solution of 0.1M and the relation curve of voltage (with respect to saturated calomel electrode).This test completes in above-mentioned traditional three-electrode system, and electrolyte is the europium nitrate solution of 0.1M.As can be seen from Figure 14: what this kind of electrode presented is the semi-conductive feature of p-type, and large than in sodium sulphate of density of photocurrent, illustrate that redox reaction more easily occurs copper-zinc-tin-sulfur in europium nitrate.
Embodiment 2
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 0.5:1:0.5:4 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 5 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 300 revs/min, and the time of spin coating is 120 seconds; Then at 100 DEG C, be dried 30 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 200 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:10;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 60 DEG C, be incubated and after 35 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 100 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 100 DEG C, and the time is 300 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 3
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 2:1:1:20 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 30 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 3500 revs/min, and the time of spin coating is 5 seconds; Then at 200 DEG C, be dried 5 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 600 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with caddy as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:5;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 90 DEG C, be incubated and after 5 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 300 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 250 DEG C, and the time is 30 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 4
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 0.5:1:0.5:8 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 20 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 2000 revs/min, and the time of spin coating is 80 seconds; Then at 150 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 300 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium acetate as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 80 DEG C, be incubated and after 5 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 150 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 5
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 1.5:1:1:4 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 15 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 2000 revs/min, and the time of spin coating is 100 seconds; Then at 200 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 200 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:9;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 60 DEG C, be incubated and after 20 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 100 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 6
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 1.5:1:1:10 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 15 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 3000 revs/min, and the time of spin coating is 70 seconds; Then at 160 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 400 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium acetate as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 70 DEG C, be incubated and after 35 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 200 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 100 DEG C, and the time is 30 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 7
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 1.5:1:1:10 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 15 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 3000 revs/min, and the time of spin coating is 30 seconds; Then at 150 DEG C, be dried 5 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 600 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium acetate as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:10;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 80 DEG C, be incubated and after 20 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 200 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 8
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 1.5:1:1:10 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 30 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 3000 revs/min, and the time of spin coating is 60 seconds; Then at 200 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 350 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 80 DEG C, be incubated and after 30 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 300 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 9
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 2:1:1:20 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 25 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 3500 revs/min, and the time of spin coating is 30 seconds; Then at 170 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 300 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 60 DEG C, be incubated and after 20 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 300 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 300 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 10
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 2:1:1:20 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 25 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 3500 revs/min, and the time of spin coating is 5 seconds; Then at 150 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 350 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 70 DEG C, be incubated and after 20 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 200 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 250 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 11
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 2:1:1:20 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 15 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 2000 revs/min, and the time of spin coating is 30 seconds; Then at 150 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 350 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with caddy as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:10;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 90 DEG C, be incubated and after 20 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 200 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 60 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Embodiment 12
1, the preparation of copper-zinc-tin-sulfur film
(1) under room temperature by copper chloride, zinc chloride, stannous chloride and thiocarbamide taking molar ratio as 2:1:1:20 is dissolved in methyl alcohol or ethanol jointly, stir to clarify the transparent precursor liquid that makes;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water, scavenging period is 20 minutes;
(3) this precursor liquid is spun to substrate FTO above, the speed of spin coating is 2000 revs/min, and the time of spin coating is 30 seconds; Then at 150 DEG C, be dried 10 minutes.By this step repeatedly, until obtain required film thickness.
(4) sample step (3) being obtained is placed in argon gas or nitrogen, calcines 1 hour at 400 DEG C, obtains copper-zinc-tin-sulfur film.
2, the preparation of copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film
(1) with cadmium iodide as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor, as complexing agent, adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide, wherein, in mole, cadmium source: sulphur source=1:1;
(2) copper-zinc-tin-sulfur film making in 1 is immersed in the chemical bath aqueous solution of cadmium sulfide, oil bath is heated to 90 DEG C, be incubated and after 30 minutes, copper-zinc-tin-sulfur film taken out, fall the chemical bath aqueous solution of remaining cadmium sulfide and dry up with a large amount of deionized waters and alcohol flushing, gained sample is calcined 30 minutes at 200 DEG C, obtains copper-zinc-tin-sulfur/cadmium sulphide membrane after cooling with stove.
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane making in step (2) is put in atomic layer deposition apparatus and carried out titanium dioxide deposition, temperature setting is set to 200 DEG C, and the time is 100 minutes.Finally obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just can design according to the present invention make many modifications and variations without creative work.Therefore, all technical staff in the art, all should be in by the determined protection range of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a preparation method for copper-zinc-tin-sulfur film, is characterized in that, comprises the following steps:
(1) preparation precursor liquid: copper chloride, zinc chloride, stannous chloride and thiocarbamide are dissolved in methyl alcohol or ethanol jointly, stir until solution clear;
(2) substrate FTO is successively carried out respectively to ultrasonic cleaning in acetone, ethanol, deionized water;
(3) described precursor liquid is spun to the surface of described substrate FTO, is then dried;
(4) sample step (3) being obtained is placed in nitrogen or argon gas is calcined, and obtains copper-zinc-tin-sulfur film.
2. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, in described step (1), in mole, described copper chloride: zinc chloride: stannous chloride: thiocarbamide=0.5～2:1:0.5～1:4～20.
3. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, in described step (2), the time of described ultrasonic cleaning is 5～30 minutes.
4. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, in described step (3), the speed of described spin coating is 300～3500 revs/min, and the time of described spin coating is 5～120 seconds.
5. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, in described step (3), described dry temperature is 100-200 DEG C.
6. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 5, is characterized in that, in described step (3), the described dry time is 5～30 points.
7. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, described step (3) repeats more than twice.
8. the preparation method of copper-zinc-tin-sulfur film as claimed in claim 1, is characterized in that, in described step (4), the temperature of described calcining is 200-600 DEG C, and the time of described calcining is 1 hour.
9. the copper-zinc-tin-sulfur film making according to the preparation method described in claim 1-8, is characterized in that, described copper-zinc-tin-sulfur film compactness is good, surfacing even and flawless; Being with as 1.5eV of described copper-zinc-tin-sulfur film.
10. the copper-zinc-tin-sulfur film described in right to use requirement 9 is prepared a method for copper-zinc-tin-sulfur/cadmium sulfide/carbon dioxide film, it is characterized in that, comprises the following steps:
(1) with cadmium iodide, caddy or cadmium acetate as cadmium source, thiocarbamide is as sulphur source, ammoniacal liquor is as complexing agent, and adds appropriate buffer, is mixed with the chemical bath aqueous solution of cadmium sulfide;
(2) described copper-zinc-tin-sulfur film is immersed in the chemical bath aqueous solution of described cadmium sulfide, oil bath is heated to 60～90 DEG C, be incubated after 5～35 minutes described copper-zinc-tin-sulfur film is taken out, with enough deionized waters and alcohol flushing and dry up, at 100～300 DEG C, calcine 30 minutes, obtain copper-zinc-tin-sulfur/cadmium sulphide membrane;
(3) copper-zinc-tin-sulfur/cadmium sulphide membrane obtaining in step (2) is put into atomic layer deposition apparatus, at 100～250 DEG C, be incubated 30～300 minutes, obtain copper-zinc-tin-sulfur/cadmium sulfide/titanium deoxid film.
Wherein, in step (1), in mole, described cadmium source: sulphur source=1:1～10, the chemical bath aqueous solution of described cadmium sulfide is alkalescence.
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| CN105226131A (en) * | 2015-08-24 | 2016-01-06 | 中国工程物理研究院材料研究所 | A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film |
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