CN107364836B - Tin-germanium-sulfur selenide thin film, preparation method thereof and photoelectric conversion device - Google Patents
Tin-germanium-sulfur selenide thin film, preparation method thereof and photoelectric conversion device Download PDFInfo
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- CN107364836B CN107364836B CN201710637683.5A CN201710637683A CN107364836B CN 107364836 B CN107364836 B CN 107364836B CN 201710637683 A CN201710637683 A CN 201710637683A CN 107364836 B CN107364836 B CN 107364836B
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- 239000010409 thin film Substances 0.000 title claims abstract description 25
- PDSAEKSMVWIHLR-UHFFFAOYSA-N S=[Se].[Ge].[Sn] Chemical compound S=[Se].[Ge].[Sn] PDSAEKSMVWIHLR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 title description 15
- 239000010408 film Substances 0.000 claims abstract description 108
- -1 tin germanium sulfide selenide Chemical compound 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011669 selenium Substances 0.000 claims abstract description 30
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 21
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 82
- 229910052717 sulfur Inorganic materials 0.000 claims description 71
- 239000011593 sulfur Substances 0.000 claims description 71
- 239000002243 precursor Substances 0.000 claims description 62
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 238000004528 spin coating Methods 0.000 claims description 25
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052711 selenium Inorganic materials 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- JLSJZFDZYLKROZ-UHFFFAOYSA-N [Ge]=[Se].[Sn] Chemical compound [Ge]=[Se].[Sn] JLSJZFDZYLKROZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000005987 sulfurization reaction Methods 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 229910000058 selane Inorganic materials 0.000 claims description 6
- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 claims description 6
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 6
- CUDGTZJYMWAJFV-UHFFFAOYSA-N tetraiodogermane Chemical compound I[Ge](I)(I)I CUDGTZJYMWAJFV-UHFFFAOYSA-N 0.000 claims description 6
- QIHHYQWNYKOHEV-UHFFFAOYSA-N 4-tert-butyl-3-nitrobenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1[N+]([O-])=O QIHHYQWNYKOHEV-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- JHMNLYGCJCJLEZ-UHFFFAOYSA-N S(=O)(=O)(O)[Se]S(=O)(=O)O.[Ge] Chemical compound S(=O)(=O)(O)[Se]S(=O)(=O)O.[Ge] JHMNLYGCJCJLEZ-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003842 bromide salts Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BLZMPOWLJVICEN-UHFFFAOYSA-N [Ge](=S)=[Se] Chemical compound [Ge](=S)=[Se] BLZMPOWLJVICEN-UHFFFAOYSA-N 0.000 claims 2
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001868 water Inorganic materials 0.000 abstract description 11
- 238000006303 photolysis reaction Methods 0.000 abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 4
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 21
- 238000001878 scanning electron micrograph Methods 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 11
- 239000010453 quartz Substances 0.000 description 10
- 239000012159 carrier gas Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- IAGYEMVJHPEPGE-UHFFFAOYSA-N diiodogermanium Chemical compound I[Ge]I IAGYEMVJHPEPGE-UHFFFAOYSA-N 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- BKQMNPVDJIHLPD-UHFFFAOYSA-N OS(=O)(=O)[Se]S(O)(=O)=O Chemical class OS(=O)(=O)[Se]S(O)(=O)=O BKQMNPVDJIHLPD-UHFFFAOYSA-N 0.000 description 1
- JQFIHKBKTGUSSS-UHFFFAOYSA-N S(=O)(=O)(O)[Se]S(=O)(=O)O.[Ge].[Sn] Chemical compound S(=O)(=O)(O)[Se]S(=O)(=O)O.[Ge].[Sn] JQFIHKBKTGUSSS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- PNEOBFGPZMCETM-UHFFFAOYSA-N [S].[Ge].[Sn].[Zn].[Cu] Chemical compound [S].[Ge].[Sn].[Zn].[Cu] PNEOBFGPZMCETM-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 230000005516 deep trap Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- JNMWHTHYDQTDQZ-UHFFFAOYSA-N selenium sulfide Chemical compound S=[Se]=S JNMWHTHYDQTDQZ-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 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
- 239000011592 zinc chloride Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- 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
- H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention prepares the high-quality tin-germanium-sulfur selenide film by simultaneously increasing the Ge content and the sulfur-selenium partial pressure, wherein the Ge content is tin-germanium-sulfur selenide (M1)x1M2x2Sn1‑xGexS1‑ySey) (M1 is one or two of Cu and Ag mixed at any ratio, M2 is one or two of Zn and Cd mixed at any ratio, x is more than or equal to 01≤1，0≤x2≤1，0<x is less than or equal to 1, y is less than or equal to 0 and less than or equal to 1), the relative proportion of Ge and Sn (Ge/(Ge + Sn)), and the sulfur-selenium partial pressure is simple substance S steam, simple substance Se steam and H in the sulfur-selenization treatment process2S gas or H2Partial pressure of Se gas. The photoelectric performance of the tin germanium sulfide selenide thin film is greatly improved by simultaneously increasing the Ge content and the sulfur selenium partial pressure, the method is simple to operate and has universality, and the prepared high-quality tin germanium sulfide selenide thin film can be applied to photoelectric devices such as solar cells, photolysis water cells, photoelectric detectors and the like.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a tin-germanium-sulfur selenide film, a preparation method thereof and a photoelectric conversion device.
Background
With the continuous improvement of the industrialization level of the human society, the total energy demand of the society is continuously increased. The average energy consumption power around the world is about 14TW, based on data provided by the U.S. department of energy 2017 annual energy reports. Among them, the consumption of fossil energy such as oil, natural gas and coal accounts for about 85% of the total consumption of energy in human society. In the short term, the main problem facing human society is not the shortage of fossil energy reserves, but the greenhouse effect caused by the large consumption of fossil energy. Research has shown that the carbon dioxide content in the earth's atmosphere and oceans reaches values that were prior to the earth's early human presence, provided that all fossil energy resources on the earth have been consumed. In order to prevent the harm caused by the greenhouse effect, the development and utilization of abundant solar energy resources on the earth are a very urgent task. Although solar energy has the advantages of abundant total amount, reproducibility, cleanness and the like, the disadvantages of low energy density and discontinuous energy transmission limit large-scale practical application. Therefore, how to conveniently and economically capture and store solar energy remains a difficult problem for large-scale utilization of solar energy.
Thin-film solar photovoltaic cells and water-splitting cells are two technologies which can utilize solar energy on a large scale and have application prospects. Multi-sulfur selenides, e.g. Cu2ZnSn(SSe)4(CZTSSe) having a suitable band gap and a high light absorption coefficient (>104cm-1) And the like, and the light absorbing material has attracted much attention as a light absorbing material in the fields of solar photovoltaic cells, water-splitting cells and the like. However, CZTSSe (copper zinc tin sulfur selenium compound) contains deep level defects related to tin (ii) and limits the increase of photovoltage.
Disclosure of Invention
In the conventional process of preparing CZTSSe by adopting a solution-spin coating-sulfurization method, the Ge content is usually 0, and the partial pressure of sulfur and selenium (namely the vapor pressure of elemental sulfur or hydrogen sulfide, elemental selenium or hydrogen selenide above a film sample in the sulfur selenization process) is 0.03 atmospheric pressure or even lower during sulfur selenization treatment (including sulfurization, selenization or sulfur selenization). The invention aims to provide a method for improving the solar energy conversion efficiency of a tin germanium selenide sulfide solar cell or a photolysis water cell, namely, in the preparation process of a solution-spin coating-sulfuration method, a tin germanium selenide sulfide film with large grain size and pure phase is obtained by a method of simultaneously increasing germanium content and sulfur selenium partial pressure, so that the solar energy conversion efficiency of a photoelectric conversion device using the film as a light absorption material is greatly improved
The invention discloses a tin germanium sulfide selenide film, which has a chemical general formula of M1x1M2x2Sn1-xGexS1-ySeyWherein M1 is one or a mixture of two of metal elements Cu and Ag in any proportion, M2 is one or a mixture of two of metal elements Zn and Cd in any proportion, and x is more than or equal to 01≤1，0≤x2≤1，0<x is less than or equal to 1, y is less than or equal to 1 and is greater than or equal to 0, the tin-germanium-sulfur selenide film is prepared by a solution-spin coating-vulcanization method, and the following requirements are met during sulfur selenization treatment: if 0<x<0.1, the sulfur selenium partial pressure is 0.05-2 atmospheric pressures; if x is more than or equal to 0.1 and less than or equal to 0.4, the partial pressure of sulfur and selenium is 0.2-5 atmospheric pressures; if 0.40<x is less than or equal to 1, and the sulfur selenium partial pressure is 0.5-5 atmospheric pressures.
As a preferred embodiment, the sulfur selenium partial pressure is 0.05-1 atm if 0< x < 0.1; if x is more than or equal to 0.1 and less than or equal to 0.4, the partial pressure of sulfur and selenium is 0.2-2 atmospheric pressures; if x is more than 0.40 and less than or equal to 1, the partial pressure of sulfur and selenium is 1-3 atmospheric pressures.
The invention also discloses a tin germanium sulfide selenide film, and the chemical general formula of the tin germanium sulfide selenide film is M1x1M2x2Sn1-xGexS1-ySeyWherein M1 is one or a mixture of two of metal elements Cu and Ag in any proportion, M2 is one or a mixture of two of metal elements Zn and Cd in any proportion, and x is more than or equal to 01≤1，0≤x2X is not less than 1, x is not less than 0.1 and not more than 0.4, y is not less than 0 and not more than 1, the tin-germanium-sulfur selenide thin film is prepared by a solution-spin coating-vulcanization method, and the partial pressure of sulfur and selenium is 0.2-2 atmospheric pressure during sulfur selenization treatment.
The invention also discloses a photoelectric conversion device which adopts the tin-germanium-sulfur selenide film with the characteristics disclosed by the scheme as a light absorption material.
The invention also discloses a preparation method of the tin-germanium-sulfur selenide film, which is characterized by comprising the following stepsThe chemical general formula of the tin germanium selenide sulfide film is M1x1M2x2Sn1-xGexS1-ySeyWherein M1 is one or a mixture of two of metal elements Cu and Ag in any proportion, M2 is one or a mixture of two of metal elements Zn and Cd in any proportion, and x is more than or equal to 01≤1，0≤x2≤1，0<x is less than or equal to 1, y is less than or equal to 1 and is more than or equal to 0, and the tin germanium selenide film is prepared by a solution-spin coating-sulfuration method, which comprises the following steps:
step one, preparing a precursor solution: respectively adding one or a mixture of more than two of nitrate, acetate, chloride salt, bromide salt or iodide salt containing M1 and M2 metal ions, a tin source, a germanium source and sulfoselenourea into one or a mixed solvent of more than two of ethylene glycol monomethyl ether, dimethyl sulfoxide, methanol, ethanol or ethylene glycol in any proportion, and stirring and mixing to obtain a clear precursor solution;
step two, spin coating and calcining: aging the clarified precursor solution prepared in the step one; spin-coating the aged precursor solution on a conductive substrate and calcining to obtain a precursor sample film; repeating the spin coating and calcining processes to obtain a precursor sample film with a required thickness;
step three, selenizing sulfur: carrying out sulfur selenization treatment on the precursor sample film obtained in the second step, and obtaining a target tin-germanium-sulfur selenide film after the treatment is finished;
controlling the germanium content, namely the value of x, by adjusting the relative proportion of the tin source and the germanium source during the preparation of the precursor solution; satisfies the following conditions in the sulfur selenization treatment: if x is more than 0 and less than 0.1, the partial pressure of sulfur and selenium is 0.05-2 atmospheric pressures; if x is more than or equal to 0.1 and less than or equal to 0.4, the partial pressure of sulfur and selenium is 0.2-5 atmospheric pressures; if x is more than 0.40 and less than or equal to 1, the partial pressure of sulfur and selenium is 0.5-5 atmospheric pressures.
As a preferred embodiment, the sulfur selenium partial pressure is 0.05-1 atm if 0< x < 0.1; if x is more than or equal to 0.1 and less than or equal to 0.4, the partial pressure of sulfur and selenium is 0.2-2 atmospheric pressures; if x is more than 0.40 and less than or equal to 1, the partial pressure of sulfur and selenium is 1-3 atmospheric pressures.
As a preferable scheme, x is more than or equal to 0.1 and less than or equal to 0.4, and the partial pressure of sulfur and selenium is 0.2-2 atmospheric pressures during sulfur selenization treatment.
Preferably, in the first step, the tin source is Sn-containing2+And Sn4+One or a mixture of more than two of acetate, chloride, bromide or iodide of ions in any proportion; the germanium source is one or a mixture of more than two of germanium chloride, germanium bromide or germanium iodide in any proportion; the solvent is one or a mixture of more than two of ethylene glycol methyl ether, dimethyl sulfoxide, methanol, ethanol and glycol in any proportion.
As a preferable scheme, in the third step, the precursor sample film obtained in the second step is placed in one or a combination of elemental sulfur vapor, elemental selenium vapor, hydrogen sulfide gas and hydrogen selenide gas to be subjected to sulfur selenization.
As a preferable scheme, in the third step, the precursor sample thin film obtained in the second step and the germanium sulfoselenide are subjected to sulfoselenization treatment, and the germanium content is controlled by adjusting the quality of the germanium sulfoselenide. The sulfoselenides of germanium are: one or a mixture of more than two of germanium sulfide, germanium selenide and germanium selenide in any proportion.
As a preferable scheme, in the second step, aging is carried out for 0-200 hours in an environment with relative humidity of 5% -95%, and calcination is carried out for 1-60 minutes in air at 200-550 ℃; in the third step, the sulfur selenization is carried out at the temperature of 450-600 ℃, and the sulfur selenization time is 20-120 minutes.
As a preferable scheme, the thickness of the tin germanium selenide sulfide film obtained after the sulfur selenization is finished is 0.05-5 microns. Such as 0.05-3 microns.
Preferably, the device for performing the sulfur selenization treatment on the precursor sample thin film in the step three is an open type, the open type device is a quartz tube which is ventilated at two ends and heated by a tube furnace, when the sulfur selenization is performed, the flow rate of carrier gas in the quartz tube is adjusted within the range of 10m L/min-1000m L/min, and the heating temperature is adjusted within the range of 400 ℃ to 700 ℃.
As a preferable scheme, the device for performing the sulfur selenization treatment on the precursor sample thin film in the third step is a sealed device, the sealed device is a quartz tube which is provided with valves at two ends and is heated by a tube furnace, when performing the sulfur selenization, the valves at two ends of the quartz tube are closed, the inert gas and the sulfur selenium source are sealed in the quartz tube, and the heating temperature is adjusted within 400-700 ℃.
The invention has the following beneficial effects:
(1) based on a conventional solution-spin coating-sulfuration method, the tin germanium selenide sulfide thin film with large grain size and pure phase is prepared by simultaneously increasing the solid solution content of germanium and the partial pressure of sulfur and selenium, so that the photoelectric property of the tin germanium selenide sulfide thin film is greatly improved, and the invention also provides a preferred embodiment with ten times of improvement.
(2) The tin germanium selenide sulfide film disclosed by the invention can be used as a light absorption material to be applied to solar energy conversion devices, such as photovoltaic cells, photolysis water cells, photoelectric detectors and the like, so as to improve the solar energy conversion efficiency of the tin germanium selenide sulfide solar cells or photolysis water cells.
(3) The method is improved based on the existing solution-spin coating-vulcanization method, is simple to operate, has low cost and is easy for large-scale production.
Drawings
FIG. 1 is surface and cross-sectional SEM images of CZTS film prepared in comparative example 1 and Ge-CZTS film prepared in example 1. (a) And (c) is a surface and cross-sectional SEM image of the CZTS film prepared in comparative example 1; (b) and (d) is the surface and cross-sectional SEM image of the Ge-CZTS film prepared in example 1.
FIG. 2 is XRD patterns of CZTS thin films prepared in comparative example 1 and Ge-CZTS thin films prepared in example 1 according to the present invention.
FIG. 3 is a Raman spectrum of a CZTS film prepared in comparative example 1 and a Ge-CZTS film prepared in example 1 according to the present invention. (a) Visible Raman spectrum and ultraviolet Raman spectrum.
FIG. 4 shows a CdS/In supported CZTS film prepared In comparative example 1 and a Ge-CZTS film prepared In example 1 according to the present invention2S3Photocurrent vs. potential after Pt.
FIG. 5 is surface and cross-sectional SEM images of CZTS thin films prepared in inventive comparative example 1 and Ge-CZTS thin films prepared in example 2. (a) And (c) is a surface and cross-sectional SEM image of the CZTS film prepared in comparative example 1; (b) and (d) is the surface and cross-sectional SEM image of the Ge-CZTS film prepared in example 2.
FIG. 6 is CZTS/CdS/In prepared In comparative example 1 of the invention2S3Pt photocathode and Ge-CZTS/CdS/In prepared In example 22S3Photocurrent-potential curves for Pt photocathodes.
Fig. 7 is surface and cross-sectional SEM images of CZTS thin films prepared in comparative example 1 and Ge-CZTS thin films prepared in example 3 of the invention. (a) And (c) is a surface and cross-sectional SEM image of the CZTS film prepared in comparative example 1; (b) and (d) is the surface and cross-sectional SEM image of the Ge-CZTS film prepared in example 2.
FIG. 8 is CZTS/CdS/In prepared In comparative example 1 of the invention2S3Pt photocathode and Ge-CZTS/CdS/In prepared In example 32S3Photocurrent-potential curves for Pt photocathodes.
Fig. 9 is surface and cross-sectional SEM images of CZTS thin films prepared in comparative example 1 and Ge-CZTS thin films prepared in example 4 of the invention. (a) And (c) is a surface and cross-sectional SEM image of the CZTS film prepared in comparative example 1; (b) and (d) is the surface and cross-sectional SEM image of the Ge-CZTS film prepared in example 2.
FIG. 10 shows CZTS/CdS/In prepared In comparative example 1 of the present invention2S3Pt photocathode and Ge-CZTS/CdS/In prepared In example 42S3Photocurrent-potential curves for Pt photocathodes.
Detailed Description
The tin germanium selenide sulfide film can be prepared by a solution-spin coating-sulfuration method, and comprises the following specific steps:
step one, preparing a precursor solution:
the multi-element sulfur selenide contains Sn in the mixture of one or more than two of nitrate, acetate, chloride, bromide or iodide of M1 and M2 metal ions in any proportion2+And Sn4+One or more than two of acetate, chloride, bromide or iodide of ion (i.e. tin source) in any proportion, and one or more than two of germanium chloride, germanium bromide or germanium iodide in any proportionThe proportional mixture (germanium source) and the sulfoselenourea are respectively added into the solvent to be stirred and mixed, and clear precursor solution is obtained. Wherein the solvent is selected from one or a mixture of more than two of ethylene glycol methyl ether, dimethyl sulfoxide, methanol, ethanol and ethylene glycol in any proportion.
Wherein the tin source in the precursor solution contains Sn2+And Sn4+One or a mixture of more than two of acetate, chloride, bromide or iodide of ions in any proportion; the germanium salt is one or a mixture of more than two of germanium chloride, germanium bromide or germanium iodide in any proportion; the solvent is one or a mixture of more than two of ethylene glycol methyl ether, dimethyl sulfoxide, methanol, ethanol and glycol in any proportion. The types of germanium sources in the precursor solution include: germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, germanium diiodide and germanium dioxide, wherein one or more of the germanium tetrachloride, the germanium tetrabromide, the germanium tetraiodide, the germanium diiodide and the germanium dioxide can be mixed in any proportion when preparing the solution. The Ge content in the tin germanium sulfoselenide can be adjusted by adjusting the relative proportions of the germanium source and the tin source in the precursor.
Step two, spin coating and calcining
And (3) aging the clarified precursor solution prepared in the first step for 0-200 hours in an environment with the relative humidity of 5% -95% to obtain an aged precursor solution.
And spin-coating the aged precursor solution on a conductive substrate, and calcining the conductive substrate in air at the temperature of 200-550 ℃ for 1-60 minutes to obtain a layer of precursor sample film.
And repeating the spin coating and calcining steps to obtain a precursor sample film with a certain thickness, wherein the thickness of the precursor sample film needs to be optimized according to the photoelectric property of the tin-germanium-sulfur selenide film.
Step three, sulfur selenization treatment
After the spin coating and the calcination are finished, the precursor sample film is subjected to sulfur selenization at the temperature of 450-600 ℃, the sulfur selenization time is 20-120 minutes, and the sulfur selenization can be carried out in elemental sulfur steam, elemental selenium steam or hydrogen sulfide, hydrogen selenide gas.
The types of germanium sulfoselenides in the sulfoselenization step include: germanium sulfide, germanium selenide. One or more of them may be used in the selenization step in any ratio.
In the method, the tin germanium selenide sulfide film with large grain size and pure phase can be obtained by simultaneously increasing the solid solution content of germanium and the sulfur partial pressure.
The gas pressure of the hydrogen selenide gas can control the partial pressure of the sulfur and the selenium by adjusting the quality of elemental sulfur and elemental selenium or hydrogen sulfide used in the sulfur selenizing process. After the selenization of sulfur is finished, the tin germanium selenide sulfide film with the thickness of about 0.05-5 microns is obtained, and the thickness of the film can be adjusted according to the requirements of corresponding photoelectric conversion devices, such as 0.05-3 microns. During the preparation process, the tin germanium selenide sulfide thin film with large grain size and pure phase is prepared by simultaneously increasing the germanium content and the sulfur selenium partial pressure in the sulfur selenization treatment process. The content of Ge can be adjusted by adjusting the relative proportion of the tin source and the germanium source in the precursor solution and adjusting the quality of the germanium sulfoselenide in the sulfoselenization step. In the method, devices for carrying out sulfur selenization treatment on tin-germanium-sulfur selenide are divided into an open type device and a sealed type device, the effect of the sealed type device is the same as that of the open type device, but the sealed type device can save the using amount of a sulfur-selenium source in the sulfur selenization process.
The open device is a quartz tube which is aerated at two ends and heated by a tube furnace, when the sulfur selenization is carried out, the flow rate of carrier gas in the quartz tube can be adjusted within the range of 10ml/min-1000ml/min, and the heating temperature can be adjusted within the range of 400 ℃ to 700 ℃.
The sealed device is a quartz tube which is heated by a tube furnace and provided with valves at two ends, when the sulfur selenization is carried out, the valves at two ends of the quartz tube are closed, the inert gas and the sulfur selenium source are sealed in the quartz tube, and the heating temperature can be adjusted within 400-700 ℃. The sealed device can also be replaced by a sealed quartz glass test tube filled with inert gas and containing a sulfur and selenium source and a sample, and when the sulfur selenization is carried out, the sealed quartz glass test tube is placed in a tube furnace to be heated.
For different types of sulfur selenization processing devices, the method for increasing the sulfur selenium partial pressure in the sulfur selenization step comprises the following steps: increasing the mass of S powder or Se powder used in an open sulfur selenization apparatus, H2S or H2Se gasThe flow rate of the body; the quality of S powder or Se powder used in the sealed sulfur selenization device is improved. In the open sulfur selenization processing device, the normal direction of the precursor sample film can be adjusted between 0-360 degrees in the open device relative to the direction of the carrier gas flow, so as to obtain different sulfur selenization effects. For example, for an open device, x may be selected as>At 0.25, mS>12/2600g/cm3(i.e. per 2600 cm)3The unit volume used 12g elemental sulfur).
The invention is further illustrated by the following specific examples:
comparative example 1:
And 2, aging the clear precursor solution in air with the temperature of 20 ℃ and the humidity of 70% for 3 hours to prepare the aged precursor solution. And preparing the precursor sample film on the molybdenum glass substrate by the aged precursor solution in a spin coating mode. The spin speed was 3000 rpm for 30 seconds. Each layer was spun on and calcined in air at 400 ℃ for 5 minutes. Spin coating was repeated 5 times in order to obtain the optimum film thickness.
And 3, after the spin coating is finished, vulcanizing for 60 minutes at 580 ℃ in a nitrogen atmosphere by adopting an open device and taking 0.5 g of sulfur powder as a sulfur source. The flow rate during vulcanization is 100ml min-1The nitrogen of (2) is a carrier gas. After completion of the vulcanization, a 1.2 μm-thick CZTS (copper zinc tin sulfide) film (one of tin germanium sulfide selenide films) was obtained.
Example 1:
And 2, aging the clear precursor solution in air with the temperature of 20 ℃ and the humidity of 70% for 6 hours to prepare the aged precursor solution. And preparing the precursor sample film on the molybdenum glass substrate by the aged precursor solution in a spin coating mode. The spin speed was 1500 rpm for 30 seconds. Each layer was spun on and calcined in air at 400 ℃ for 5 minutes. Spin coating was repeated 11 times in order to obtain the optimum film thickness.
Step 3, after the spin coating is finished, an open device is adopted, 12g of sulfur powder is used as a sulfur source to control the sulfur bias pressure to be 0.5 atmosphere, (10 g of sulfur powder is added compared with the comparative example, the sulfur selenium partial pressure is increased), the vulcanization is carried out for 60 minutes under the nitrogen atmosphere at the temperature of 580 ℃, and the flow rate is 100m L min during the vulcanization-1The nitrogen of (2) is a carrier gas. After completion of the vulcanization, a 1.2 μm-thick Ge-CZTS (copper-zinc-tin-germanium-sulfur) film (one of tin-germanium-sulfur selenide film) was obtained.
Example 2:
And 2, aging the clear precursor solution in air with the temperature of 20 ℃ and the humidity of 70% for 4 hours to prepare the aged precursor solution. And preparing the precursor sample film on the molybdenum glass substrate by the aged precursor solution in a spin coating mode. The spin speed was 1500 rpm for 30 seconds. Each layer was spun on and calcined in air at 400 ℃ for 5 minutes. Spin coating was repeated 8 times in order to obtain the optimum film thickness.
Step 3, after the spin coating is finished, vulcanizing for 60 minutes at 580 ℃ in a nitrogen atmosphere by adopting an open device and taking 12g of sulfur powder as a sulfur source at the flow rate of 100m L min during vulcanization-1The nitrogen of (2) is a carrier gas. After completion of the vulcanization, a 1.2 μm thick Ge-CZTS film was obtained.
Example 3:
And 2, aging the clear precursor solution in air with the temperature of 20 ℃ and the humidity of 70% for 8 hours to prepare the aged precursor solution. And preparing the precursor sample film on the molybdenum glass substrate by the aged precursor solution in a spin coating mode. The spin speed was 1500 rpm for 30 seconds. Each layer was spun on and calcined in air at 400 ℃ for 5 minutes. Spin coating was repeated 14 times in order to obtain the optimum film thickness.
And 3, after the spin coating is finished, vulcanizing for 60 minutes at 580 ℃ in a nitrogen atmosphere by adopting an open device and taking 12g of sulfur powder as a sulfur source. The flow rate during vulcanization is 100ml min-1The nitrogen of (2) is a carrier gas. After completion of the vulcanization, a 1.2 μm thick Ge-CZTS film was obtained.
Example 4:
And 2, aging the clear precursor solution in air with the temperature of 20 ℃ and the humidity of 70% for 6 hours to prepare the aged precursor solution. And preparing the precursor sample film on the molybdenum glass substrate by the aged precursor solution in a spin coating mode. The spin speed was 1500 rpm for 30 seconds. Each layer was spun on and calcined in air at 400 ℃ for 5 minutes. Spin coating was repeated 11 times in order to obtain the optimum film thickness.
Step 3, after the spin coating is finished, an open device is adopted, 0.5 g of sulfur powder is used as a sulfur source, and the temperature is 580 ℃ in a nitrogen atmosphereVulcanizing for 60 minutes at a flow rate of 100m L min-1The nitrogen of (2) is a carrier gas. After completion of the vulcanization, a 1.2 μm thick Ge-CZTS film was obtained.
Before the photocurrent-potential curve test of the tin germanium selenide film samples of comparative example 1 and examples 1-3, the surface modification is carried out, and the steps are as follows:
firstly, 5ml of CdSO with the concentration of 0.015 mol/L46.5ml of concentrated ammonia (28-30%) is added into deionized water with the concentration of 36m L and stirred for 5 minutes, then thiourea aqueous solution with the concentration of 2.5m L and the concentration of 1.5 mol/L is added into the solution, the water bath heating of the reaction solution is started after the tin germanium selenide film is immersed into the solution, the reaction time is 5 minutes, and after the reaction is finished, the tin germanium selenide film is taken out of the reaction solution and is lightly washed by deionized water, and the precursor which is not completely reacted on the surface of the tin germanium selenide film is removed.
In after completion of the chemical bath deposition step of the CdS buffer layer2S3Buffer layers were also prepared by a similar procedure, 10m L concentration was 0.025 mol/L In (NO)3)3After the solution and 3ml of glacial acetic acid (30%) were added to 13m L of deionized water and stirred for 5 minutes, 25m L of a thioacetamide solution with a concentration of 1 mol/L was added to the solution, after the sample was immersed in the reaction solution, heating in a water bath was started at 70 ℃ for 14 minutes, after the reaction was completed, the sample was taken out and washed with deionized water.
The tin germanium selenide film prepared by the steps is put into a tube furnace, heated for 60 minutes at 200 ℃ under the protection of nitrogen, cooled and taken out, the tin germanium selenide film is used as a working electrode and immersed into a chloroplatinic acid solution with the concentration of 0.1 mmol/L, a 500W xenon lamp is used as a light source to irradiate the film, and the potential is set to-0.1V by utilizing the current-time test mode of an electrochemical workstationSCEAfter which electrodeposition is started. When the deposited electric quantity reaches 5mC/cm2Stopping deposition to obtain the tin germanium sulfide selenide photoelectrode.
We have performed various characterizations on the tin germanium sulfide selenide photoelectrode obtained through the above steps, and fig. 1 to 4 are the characterization results of the tin germanium sulfide selenide thin film photoelectrode. Wherein, the photocurrent-potential curve of the tin-germanium-sulfur selenide photoelectrode is tested by utilizing an electrochemical workstation of Shanghai Chenghua CHI633C model. The test adopts a three-electrode system, tin germanium selenide sulfide as a cathode, platinum as an anode and an SCE electrode as a reference electrode. AM 1.5G (100mW cm)-2) The solar simulator is used as a light source.
FIG. 1 is SEM images of the surface and cross-section of a CZTS film prepared without Ge and with a low sulfur selenium partial pressure (i.e., the CZTS film prepared in comparative example 1) and a Ge-CZTS film prepared with a Ge content of 0.25 and a high sulfur selenium partial pressure (i.e., the Ge-CZTS film prepared in example 1). From SEM images of the surface and the cross section, the Ge-CZTS film prepared by increasing the Ge content and the sulfur selenium partial pressure has obviously increased crystal grains and reduced number of crystal boundaries.
FIG. 2 is an XRD pattern of a CZTS film prepared without Ge and with a low sulfur selenium partial pressure and a Ge-CZTS film prepared with a Ge content of 0.25 and a high sulfur selenium partial pressure. As can be seen from FIG. 2, the peak position of the characteristic diffraction peak of the prepared Ge-CZTS film is shifted to a larger angle than that of the CZTS film, and the half-peak width of the Ge-CZTS diffraction peak is narrower, indicating that the Ge-CZTS film has higher crystallinity.
FIG. 3 is a graph of the visible (a) and ultraviolet (b) Raman spectra of a CZTS film prepared without Ge and with a low sulfur selenium partial pressure and a Ge-CZTS film prepared with a Ge content of 0.25 and a high sulfur selenium partial pressure. As can be seen from FIG. 3(a), all the oscillation peaks are classified as characteristic peaks of CZTS and Ge-CZTS. As can be seen from fig. 3(b), ZnS hetero-phase exists in the CZTS film prepared under the partial pressure of sulfur selenium without Ge and sulfur selenium, while the Ge-CZTS film prepared after increasing the partial pressure of sulfur selenium with Ge content does not contain ZnS hetero-phase.
FIG. 4 is a CZTS/CdS/In prepared at partial pressures of Ge-free and low sulfur selenium2S3Pt photocathode and Ge-CZTS/CdS/In prepared under the conditions that the Ge content is 0.25 and the high sulfur selenium partial pressure is high2S3Photocurrent-potential curves for Pt photocathodes. As can be seen from FIG. 4, the photocurrent of the Ge-CZTS photocathode prepared by increasing both Ge content and sulfur-selenium partial pressure was at 0VRHEApproximately ten times the lift is obtained.
FIG. 5 is SEM images of the surface and cross-section of a CZTS film prepared without Ge and with a low sulfur selenium partial pressure (i.e., the CZTS film prepared in comparative example 1) and a Ge-CZTS film prepared with a Ge content of 0.1 and a high sulfur selenium partial pressure (i.e., the Ge-CZTS film prepared in example 2). From SEM images of the surface and the cross section, the Ge-CZTS film prepared by increasing the Ge content and the sulfur selenium partial pressure has obviously increased crystal grains and reduced number of crystal boundaries.
FIG. 6 shows CZTS/CdS/In prepared under partial pressure without Ge and with low sulfur and selenium2S3Pt photocathode and Ge-CZTS/CdS/In prepared under high sulfur selenium partial pressure with Ge content of 0.12S3Photocurrent-potential curves for Pt photocathodes. As can be seen from FIG. 6, the photocurrent of the Ge-CZTS photocathode prepared by increasing both Ge content and sulfur-selenium partial pressure was at 0VRHEApproximately 7.6 times improvement is obtained.
FIG. 7 is SEM images of the surface and cross-section of a CZTS film prepared without Ge and with a low sulfur selenium partial pressure (i.e., the CZTS film prepared in comparative example 1) and a Ge-CZTS film prepared with a Ge content of 0.4 and a high sulfur selenium partial pressure (i.e., the Ge-CZTS film prepared in example 3). From SEM images of the surface and the cross section, the Ge-CZTS film prepared by increasing the Ge content and the sulfur selenium partial pressure has obviously increased crystal grains and reduced number of crystal boundaries.
FIG. 8 shows CZTS/CdS/In prepared under partial pressure without Ge and with low sulfur and selenium2S3Pt photocathode and Ge-CZTS/CdS/In prepared under the conditions that the Ge content is 0.4 and the high sulfur selenium partial pressure is high2S3Photocurrent-potential curves for Pt photocathodes. As can be seen from FIG. 8, the photocurrent of the Ge-CZTS photocathode prepared by increasing both Ge content and sulfur-selenium partial pressure was at 0VRHEApproximately 4 times improvement is obtained.
FIG. 9 is SEM images of the surface and cross-section of a CZTS film prepared without Ge and with a partial pressure of selenium lower than sulfur (i.e., the CZTS film prepared in comparative example 1) and a Ge-CZTS film prepared with a Ge content of 0.25 and a partial pressure of selenium lower than sulfur (i.e., the Ge-CZTS film prepared in example 4). From the SEM images of the surface and the cross section, the increase of the Ge content can obviously reduce the crystal grains of the Ge-CZTS film and increase the number of the crystal boundaries under the low sulfur selenium partial pressure.
FIG. 10 shows CZTS/CdS/In prepared at partial pressures without Ge and with low sulfur and selenium2S3Pt photocathode and Ge content of0.25 and Ge-CZTS/CdS/In prepared by low sulfur selenium partial pressure2S3Photocurrent-potential curves for Pt photocathodes. As can be seen from FIG. 10, the photocurrent of the Ge-CZTS photocathode with Ge content of 0.25 prepared under low sulfur-selenium partial pressure was at 0VRHEThe lower is reduced by a factor of two. Therefore, only the content of germanium is increased, and the partial pressure of sulfur and selenium is not increased, so that the photoelectric property of the obtained film cannot be improved, and the performance of the film is reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the tin germanium selenide sulfide film is characterized in that the chemical general formula of the tin germanium selenide sulfide film is M1x1M2x2Sn1-xGexS1-ySeyWherein M1 is one or a mixture of two of metal elements Cu and Ag in any proportion, M2 is one or a mixture of two of metal elements Zn and Cd in any proportion, 0<x1≤1，0<x2≤1，0.1≤x≤0.4，0<y<1, preparing the tin germanium selenide sulfide film by a solution-spin coating-sulfuration method, which comprises the following steps:
step one, preparing a precursor solution: respectively adding one or a mixture of more than two of nitrate, acetate, chloride salt, bromide salt or iodide salt containing M1 and M2 metal ions, a tin source, a germanium source and sulfoselenourea into one or a mixed solvent of more than two of ethylene glycol monomethyl ether, dimethyl sulfoxide, methanol, ethanol or ethylene glycol in any proportion, and stirring and mixing to obtain a clear precursor solution;
step two, spin coating and calcining: aging the clarified precursor solution prepared in the step one; spin-coating the aged precursor solution on a conductive substrate and calcining to obtain a precursor sample film; repeating the spin coating and calcining processes to obtain a precursor sample film with a required thickness;
step three, selenizing sulfur: carrying out sulfur selenization treatment on the precursor sample film obtained in the second step, and obtaining a target tin-germanium-sulfur selenide film after the treatment is finished;
controlling the germanium content, namely the value of x, by adjusting the relative proportion of the tin source and the germanium source during the preparation of the precursor solution;
satisfies the following conditions in the sulfur selenization treatment: the sulfur and selenium partial pressure is 0.2-5 atm.
2. The method of claim 1, wherein in step one, the Sn source is Sn-containing2+And Sn4+One or a mixture of more than two of acetate, chloride, bromide or iodide of ions in any proportion; the germanium source is one or a mixture of more than two of germanium chloride, germanium bromide or germanium iodide in any proportion; the solvent is one or a mixture of more than two of ethylene glycol methyl ether, dimethyl sulfoxide, methanol, ethanol and glycol in any proportion.
3. The method for preparing a tin-germanium-selenide sulfide thin film according to claim 1 or 2, wherein in the third step, the precursor sample thin film obtained in the second step is placed in one or a combination of elemental sulfur vapor, elemental selenium vapor, hydrogen sulfide gas and hydrogen selenide gas to be subjected to sulfur selenization.
4. The method for preparing a tin-germanium-selenide sulfide thin film according to claim 1 or 2, wherein in the third step, the precursor sample thin film obtained in the second step and the germanium-selenide sulfide are subjected to selenylation treatment, and the germanium content is controlled by adjusting the quality of the germanium-selenide sulfide.
5. The method of claim 4, wherein in step three, the germanium sulfoselenide is: one or a mixture of more than two of germanium sulfide, germanium selenide and germanium selenide in any proportion.
6. The method of claim 1 or 2, wherein in the second step, the tin germanium selenide film is aged for 0-200 hours in an environment with a relative humidity of 5-95%, and calcined in air at 200-550 ℃ for 1-60 minutes; in the third step, the sulfur selenization is carried out at the temperature of 450-600 ℃, the time of the sulfur selenization is 20-120 minutes, and the thickness of the tin-germanium-sulfur selenide film obtained after the sulfur selenization is finished is 0.05-5 microns.
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