CN106784038B - 一种组分可调光电薄膜的制备方法 - Google Patents
一种组分可调光电薄膜的制备方法 Download PDFInfo
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- 230000005693 optoelectronics Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- SIPWKRLRRXRIIX-UHFFFAOYSA-N [S].[Bi].[Sb].[Cu] Chemical compound [S].[Bi].[Sb].[Cu] SIPWKRLRRXRIIX-UHFFFAOYSA-N 0.000 claims abstract description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010408 film Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 238000004528 spin coating Methods 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000004073 vulcanization Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 239000005864 Sulphur Substances 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- JWVUFVZEYBYBAL-UHFFFAOYSA-N [Bi]=S.[Sb] Chemical compound [Bi]=S.[Sb] JWVUFVZEYBYBAL-UHFFFAOYSA-N 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- QYJPSWYYEKYVEJ-FDGPNNRMSA-L copper;(z)-4-oxopent-2-en-2-olate Chemical compound [Cu+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O QYJPSWYYEKYVEJ-FDGPNNRMSA-L 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 2
- 229950004394 ditiocarb Drugs 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- PORFVJURJXKREL-UHFFFAOYSA-N trimethylstibine Chemical compound C[Sb](C)C PORFVJURJXKREL-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 11
- 239000011259 mixed solution Substances 0.000 abstract description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 10
- 230000005622 photoelectricity Effects 0.000 description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 6
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 4
- CHRUUJJXTYHZCK-UHFFFAOYSA-N antimony;sulfanylidenecopper Chemical compound [Sb].[Cu]=S CHRUUJJXTYHZCK-UHFFFAOYSA-N 0.000 description 4
- KFSLRIDSBUUESB-UHFFFAOYSA-N bismuth;sulfanylidenecopper Chemical compound [Bi].[Cu]=S KFSLRIDSBUUESB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052969 tetrahedrite Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
- C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
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Abstract
本发明一种组分可调的光电薄膜的制备方法，按照摩尔比称取Cu、Sb、Bi对应的化合物以及硫源，将上述的化合物溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末；将前驱体粉末溶解在二甲基甲酰胺、聚乙烯吡咯烷酮和聚乙二醇组成的混合溶液中制得前驱物溶液，在FTO衬底上旋涂；将获得的产品在200‑500℃退火，得到铜锑铋硫预制薄膜；将预制薄膜在300‑700℃硫化退火获得光电薄膜。
Description
技术领域：
本发明属于材料学领域，涉及一种光伏电池材料，具体来说是一种组分可调的铜锑铋硫光电薄膜的制备方法。
背景技术:
随着人类社会的发展，如何同时解决能源问题与可持续发展的问题逐渐成为困扰人类社会进步的一大难题。将太阳能转换为电能的光伏技术是创造社会发展与能源需求的最佳能源形式。降低光伏器件成本，提高器件的转换效率一直是太阳电池材料与器件行业关注的焦点和主要的目标。
近年来，出现了三种主要的薄膜太阳电池半导体材料：砷化镓(GaAs)材料、铜铟镓硒(CIGS)材料和碲化镉(CdTe)材料。砷化镓(GaAs)材料转化效率虽高，但价格不菲，因而在很大程度上限制了砷化镓(GaAs)电池的普及。铜铟镓硒（CIGS）材料中铟和硒的稀缺、昂贵限制了这类电池的发展。碲化镉(CdTe)带隙为1.5 eV，与太阳光谱非常匹配，最适合于光电能量转化，但镉(Cd)元素的毒性和有限的蕴藏量限制了其发展。因此，寻找性能更优的吸收层半导体材料成为一种更具潜力的选择。铜基硫族化合物中Cu3BiS3、Cu3SbS4带隙分别为1.4eV、1.5eV，接近太阳能电池的最优带隙，并且其光吸收系数很高(＞105cm-1)，且具有较高的光电转换效率。Cu3BiS3还可以用来做光伏器件，例如太阳能电池等。Cu3SbS3也是一种重要的半导体材料，广泛地应用于光电、热电设备和光记录媒介等。
铜基硫族化合物半导体如：Cu-Bi-S(Cu3BiS3、Cu9BiS6、CuBiS2、Cu4Bi4S9)，Cu-Sb-S(Cu3SbS4、CuSbS2、Cu12Sb4S13)因其廉价、环保、自然储量丰富、良好的光电性能，越来越受到人们的关注。这些化合物广泛应用于太阳电池、晶体管、光探测器及热敏器件等领域。
发明内容：
针对现有技术中的上述技术问题，本发明提供了一种组分可调的铜锑铋硫光电薄膜的制备方法，所述的这种组分可调的铜锑铋硫光电薄膜的制备方法要解决现有技术中的薄膜太阳电池半导体材料成本高、工艺复杂的技术问题。
本发明提供了一种组分可调的光电薄膜的制备方法，包括如下步骤：
1)按照摩尔比称取Cu、Sb、Bi对应的化合物以及硫源；在各反应物前驱体中，Cu元素、Sb元素、Bi元素、S元素的摩尔比为3 : (1-x) : x : y，其中0≤ x ≤1 ; 6 ≤ y ≤ 18。
2)将上述的化合物溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末；
3)将铜锑铋硫前驱体粉末溶解在二甲基甲酰胺、聚乙烯吡咯烷酮和聚乙二醇组成的混合溶液中制得前驱物溶液，前驱体粉末和二甲基甲酰胺、聚乙烯吡咯烷酮和聚乙二醇之间的物料比为0.01-1 g：15-60 mL：0.30-1.30 g：5-20 mL，在FTO衬底上以转速1000-3000 r/min旋涂10-60 s；
4)将步骤3）获得的产品在200-500℃退火1-10 min，以上步骤重复2-10次，得到铜锑铋硫预制薄膜；
5)将预制薄膜在300-700 ℃硫化退火20-60 min获得铜锑铋硫光电薄膜，所述的铜锑铋硫光电薄膜的化学式为Cu3(Sb1-xBix)S3，其中0≤x≤1。
进一步的，所述铋对应的化合物为硝酸铋、三氯化铋、乙酰丙酮铋、氧化铋、氯化铋或碳酸铋中任意一种。
进一步的，所述铜对应的化合物为硝酸铜、醋酸铜、氯化铜、乙酰丙酮酸铜、或硫酸铜中任意一种。
进一步的，所述锑对应的化合物为氯化锑、醋酸锑、三甲基锑、或者三乙基锑中的任意一种。
进一步的，所述的硫源为二乙基二硫代氨基甲酸钠、硫代乙醇酸、或者硫脲。
本发明将Cu、Sb、Bi、S按照计量比共沉淀得到铜锑铋硫前驱体，然后将前驱体溶解在DMF中形成澄清的溶液，制成铜锑铋硫前驱物溶液。然后通过旋涂法，将铜锑铋硫前驱物溶液涂覆在FTO导电玻璃上，经过硫化退火处理，最终得到铜锑铋硫光电薄膜。本发明通过简单的旋涂法工艺制备铜基硫化物薄膜，有效减少太阳薄膜吸收层的制作成本和对真空等苛刻制备条件的依赖，提供了一种制造低价高效太阳电池器件的制备方法。
本发明和已有技术相比，其技术进步是显著的。本发明提供工艺简单，制备方便，成本低廉的一种铜锑铋硫光电薄膜的制备方法，制备的铜锑铋硫薄膜具有良好的光吸收及光热效果，在光伏领域具有潜在的应用价值。本发明的方法操作简单，反应温度低，元素化学计量比控制精确，所用前驱体材料成本低廉、无毒性，适合工业化生产与应用。
附图说明：
图1为实施例1制备的光电薄膜的扫描电镜图，从图中可以看出薄膜形貌致密、平整。
图2为实施例1合成的铜锑铋硫纳米晶的晶体结构图，可以看出其为正交晶系，晶胞中原子并没有占据在顶点上而是分布在晶胞内。
图3为实施例1合成的铜锑铋硫纳米晶的XRD衍射图谱，可以看出结晶性较好，且不含其它杂相。
具体实施方式
实施例1：
称取3 mmol CuCl2·2H2O、2 mmol Bi(NO3)3·5H2O、和9 mmol (C2H5)2NCSSNa·3H2O溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑硫前驱体粉末。将0.8 g的铜锑硫前驱体粉末溶解在60 mL DMF，0.30 g PVP和20 mL PEG中制得前驱物溶液，在FTO衬底上以转速1000 r/min旋涂10 s，然后在250℃退火20 min，以上步骤重复4次，得到铜锑硫预制薄膜，最后将预制薄膜在400℃硫化退火6 min获得铜锑硫光电薄膜。
实施例2：
称取5 mmol CuCl2·2H2O、0.8 mmol Sb(CH3COO)3、0.2 mmol Bi(NO3)3·5H2O和11mmol (C2H5)2NCSSNa·3H2O溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末。将0.1 g的铜锑铋硫前驱体粉末溶解在50 mL DMF，0.40 g PVP和17 mL PEG中制得前驱物溶液，在FTO衬底上以转速1500 r/min旋涂20 s，然后在260℃退火28 min，以上步骤重复2次，得到铜锑铋硫预制薄膜，最后将预制薄膜在450℃硫化退火20 min获得铜锑铋硫光电薄膜。
实施例3：
称取7 mmol CuCl2·2H2O、0.6 mmol Sb(CH3COO)3、0.4 mmol Bi(NO3)3·5H2O和18mmol (C2H5)2NCSSNa·3H2O溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末。将0.2 g的铜锑铋硫前驱体粉末溶解在40 mL DMF，0.70 g PVP和15 mL PEG中制得前驱物溶液，在FTO衬底上以转速2000 r/min旋涂30 s，然后在270℃退火5 min，以上步骤重复6次，得到铜锑铋硫预制薄膜，最后将预制薄膜在500℃硫化退火36 min获得铜锑铋硫光电薄膜。
实施例4：
称取9 mmol CuCl2·2H2O、0.4 mmol Sb(CH3COO)3、0.6 mmol Bi(NO3)3·5H2O和6mmol (C2H5)2NCSSNa·3H2O溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末。将0.4 g的铜锑铋硫前驱体粉末溶解在30 mL DMF，0.80 g PVP和12 mL PEG中制得前驱物溶液，在FTO衬底上以转速2500 r/min旋涂50 s，然后在280℃退火55 min，以上步骤重复8次，得到铜锑铋硫预制薄膜，最后将预制薄膜在550℃硫化退火40 min获得铜锑铋硫光电薄膜。
实施例5：
称取11 mmol CuCl2·2H2O、0.2 mmol Sb(CH3COO)3、0.8 mmol Bi(NO3)3·5H2O和16 mmol (C2H5)2NCSSNa·3H2O溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末。将0.01 g的铜锑铋硫前驱体粉末溶解在20 mL DMF，1.0 g PVP和7 mL PEG中制得前驱物溶液，在FTO衬底上以转速3000 r/min旋涂60 s，然后在290℃退火2 min，以上步骤重复10次，得到铜锑铋硫预制薄膜，最后将预制薄膜在600℃硫化退火60 min获得铜锑铋硫光电薄膜。
实施例6：
称取12 mmol CuCl2·2H2O、0.5 mmol Sb(CH3COO)3和12 mmol (C2H5)2NCSSNa·3H2O溶解在乙二醇中，经抽滤、洗涤、干燥制成铜铋硫前驱体粉末。将1 g的铜铋硫前驱体粉末溶解在15 mL DMF，1.3 g PVP和6 mL PEG中制得前驱物溶液，在FTO衬底上以转速2500r/min旋涂35 s，然后在300℃退火4 min，以上步骤重复15次，得到铜铋硫预制薄膜，最后将预制薄膜在500℃硫化退火30 min获得铜铋硫光电薄膜。
Claims (5)
1.一种组分可调的光电薄膜的制备方法，其特征在于包括如下步骤：
1）按照摩尔比称取Cu、Sb、Bi对应的化合物以及硫源；在各反应物前驱体中，Cu元素、Sb元素、Bi元素、S元素的摩尔比为3 : (1-x) : x : y，其中0≤ x ≤1 ; 6 ≤ y ≤ 18；
2）将上述的化合物以及硫源溶解在乙二醇中，经抽滤、洗涤、干燥制成铜锑铋硫前驱体粉末；
3）将铜锑铋硫前驱体粉末溶解在二甲基甲酰胺、聚乙烯吡咯烷酮和聚乙二醇组成的混合溶液中制得前驱物溶液，铜锑铋硫前驱体粉末和二甲基甲酰胺、聚乙烯吡咯烷酮和聚乙二醇之间的物料比为0.01-1 g：15-60 mL：0.30-1.30 g：5-20 mL；在FTO衬底上以转速1000-3000 r/min旋涂10-60 s；将获得的产品在200-500℃退火1-10 min；
4）将步骤3）重复2-10次，得到铜锑铋硫预制薄膜；
5）将铜锑铋硫预制薄膜在300-700 ℃硫化退火20-60 min获得铜锑铋硫光电薄膜，所述的铜锑铋硫光电薄膜的化学式为Cu3(Sb1-xBix)S3，其中0≤x≤1。
2.根据权利要求1所述的一种组分可调的光电薄膜的制备方法，其特征在于：所述铋对应的化合物为硝酸铋、三氯化铋、乙酰丙酮铋、氧化铋、氯化铋或碳酸铋中任意一种。
3.根据权利要求1所述的一种组分可调的光电薄膜的制备方法，其特征在于：所述铜对应的化合物为为硝酸铜、醋酸铜、氯化铜、乙酰丙酮酸铜、或硫酸铜中任意一种。
4.根据权利要求1所述的一种组分可调的光电薄膜的制备方法，其特征在于：所述锑对应的化合物为氯化锑、醋酸锑、三甲基锑、或者三乙基锑中的任意一种。
5.根据权利要求1所述的一种组分可调的光电薄膜的制备方法，其特征在于：所述的硫源为二乙基二硫代氨基甲酸钠、硫代乙醇酸、或者硫脲中的任意一种。
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