CN105489672A - 一种氯化物体系两步法制备铜铟硒光电薄膜的方法 - Google Patents
一种氯化物体系两步法制备铜铟硒光电薄膜的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000010409 thin film Substances 0.000 title claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 9
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title abstract 4
- 239000011521 glass Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 24
- 239000011669 selenium Substances 0.000 claims description 20
- 230000005693 optoelectronics Effects 0.000 claims description 12
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000000429 assembly Methods 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000000873 masking effect Effects 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 abstract 2
- 229910018162 SeO2 Inorganic materials 0.000 abstract 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 abstract 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 238000005922 selenation reaction Methods 0.000 abstract 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 13
- 238000000151 deposition Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
一种氯化物体系两步法制备铜铟硒光电薄膜的方法，属于太阳能电池用光电薄膜制备技术领域，本发明通过如下步骤得到，首先清洗二氧化锡导电玻璃基片，然后将C6H5Na3O7·2H2O、CuCl2·2H2O、InCl3、SeO2放入蒸馏水中，用电沉积法在导电玻璃片上得到前驱体薄膜，自然干燥，放入加有水合联氨的管式炉中，使前驱体薄膜样品不与水合联氨接触，其中水合联氨中加有硒粉，在密闭管式炉内加热，使前驱体薄膜硒化，最后取出样品进行干燥，得到铜铟硒光电薄膜。本发明不需要高真空条件，对仪器设备要求低，生产成本低，生产效率高，易于操作。所得铜铟硒光电薄膜有较好的连续性和均匀性，主相为CuInSe2相，可以实现低成本大规模的工业化生产。
Description
技术领域
本发明属于太阳能电池用光电薄膜制备技术领域，尤其涉及一种氯化物体系两步法制备铜铟硒光电薄膜的方法。
背景技术
随着社会和经济的发展，能源紧缺及消费能源带来的污染已成为国内社会发展中的突出问题，煤炭、石油等为不可再生资源，因此开发利用清洁可再生能源对保护环境、保证经济可持续发展和构筑和谐社会都有重要的意义。光伏发电具有安全可靠、无噪声、无污染、制约少、故障率低、维护简便等优点，可以利用太阳能这种清洁、安全和环保的可再生能源，因此近几十年来太阳能电池的研究和开发日益受到重视。
铜铟硒薄膜太阳电池目前可以认为是最有发展前景的薄膜电池，这是因为其吸收层材料CuInSe2具有一系列的优点：(1)在CuInSe2基础上掺杂其它元素，如使Ga或Al部分取代In原子，用S部分取代Se即制备成Cu(In1-xGax)Se2，Cu(In1-xGax)(Se2-ySy)，Cu(In1-xAlx)(Se2-xSx)，其晶体结构仍然是黄铜矿。改变其中Ga/(Ga+In)等的原子比，可以使其禁带宽度在1.04~1.72eV之间变化，包含高效率吸收太阳光的带隙范围1.4~1.6eV；(2)CuInSe2、Cu(In1-xGax)Se2是直接带隙的半导体材料，对太阳光谱响应特性非常大，它的吸收系数很高，光吸收率高达1~6×105cm-1，因而电池中所需CuInSe2、Cu(In1-xGax)Se2薄膜厚度很小，约2μm，最适于太阳电池薄膜化；(3)化学计量比CuInSe2的光量子效率高；(4)高的光电转换效率；(5)在较宽成分范围内电阻率都较小；(6)抗辐射能力强，没有光致衰减效应，因而使用寿命长；(7)Cu(In1-xGax)Se2系电池容易做成多结系统。在4个结电池中，从光线入射方向按禁带宽度由大到小顺序排列，这时的理论转换效率极限可以超过50％。(8)P型CIGS材料的晶格结构与电子亲和力都能跟普通N型窗口材料(如CdS、ZnO)匹配。
目前处于先进水平的Cu(In1-xGax)Se2光伏吸收材料都是在真空条件下沉积制备的，主要有真空蒸镀法和(铜铟合金膜)溅射—硒化法。CuInSe2基吸收层的生产需要采用沉积合金层的昂贵的真空技术。真空技术中操作复杂难度大，所得薄膜也不均匀。另外含有硒化的工艺中薄膜也不均匀，难以控制各组分的化学计量比，其中H2Se和Se的毒气污染环境和危害操作人员。
与前面所述方法一样，其它方法也有不同的缺陷。与本发明相关的还有如下文献：
[1]M.Valdés,M.Vázquez,A.Goossens,ElectrodepositionofCuInSe2andIn2Se3onflatandnanoporousTiO2substrates,ElectrochimicaActa54(2008)524–529.
主要描述了用电沉积法分别制备In2Se3和CuInSe2薄膜，并对其性能进行了表征。
[2]AmolC.Badgujar,SanjayR.Dhage,ShrikantV.Joshi,Processparameterimpactonpropertiesofsputteredlarge-areaMobilayersforCIGSthinfilmsolarcellapplications,ThinSolidFilms589(2015)79–84.
主要描述了用溅射法制备溅射CIGS,并研究了溅射工艺参数对其性能的影响。
[3]Yin-HsienSu,Tsung-WeiChang,Wen-HsiLee,Bae-HengTseng,CharacterizationofCuInSe2thinfilmsgrownbyphoto-assistedelectrodeposition,ThinSolidFilms535(2013)343–347.
主要描述光辅助电沉积法制备CuInSe2及其光电性能的研究。
[4]ArminE.Zaghi,MarieBuffière,JaseokKoo,GuyBrammertz,MariaBatuk,ChristopheVerbist,JokeHadermann,WooKyoungKim,MarcMeuris,JefPoortmans,JefVleugels,EffectofseleniumcontentofCuInSexalloynanopowderprecursorsonrecrystallizationofprintedCuInSe2absorberlayersduringselenizationheattreatment,ThinSolidFilms582(2015)11–17.
主要描述硒化热处理再结晶对CuInSex中硒含量的影响，并对其进行了性能表征和形成机理研究。
[5]ChaehwanJeong,JinHyeokKim,FabricationofCuInSe2thinfilmsolarcellwithselenizationofdoublelayeredprecursorsfromCu2SeandIn2Se3binary,ThinSolidFilms550(2014)660–664.
主要描述了利用Cu2Se和In2Se3两元硒化法制备CuInSe2。
[6]MengxiWang,SudipK.Batabyal,HuiMinLim,ZhenggangLi,YengMingLam,FormationofCuIn(SxSe1-x)2microcrystalsfromCuInSe2nanoparticlesbytwostepsolvothermalmethod,JournalofAlloysandCompounds618(2015)522–526.
主要描述了两步溶剂热法制备CuInSe2薄膜，并研究了CuIn(SxSe1-x)2和CuInSe2的结构和性能差异。
[7]Jeng-ShinMa,SubrataDas,Che-YuanYang,Fuh-ShanChen,Chung-HsinLu,Hydrothermally-assistedselenizationofCuInSe2thinfilmsoncopperfoils,CeramicsInternational40(2014)7555–7560.
主要描述了采用水热辅助硒化法制备CuInSe2相并进行了形貌及成分分析。
[8]JaseokKoo,Chae-WoongKim,ChaehwanJeong,WooKyoungKim,RapidsynthesisofCuInSe2fromsputter-depositedbilayerIn2Se3/Cu2Seprecursors,ThinSolidFilms582(2015)79–84.
主要描述了用分别溅射法制备Cu2Se和In2Se3，然后两元硒化制备CuInSe2。
[9]A.Shanmugavel,K.Srinivasan,K.R.Murali,Pulseelectrodepositedcopperindiumsulphoselenidefilmsandtheirproperties,MaterialsScienceinSemiconductorProcessing16(2013)1665–1671.
主要描述了用脉冲电沉积法制备CuIn(S,Se)2，并对其性能进行了表征。
[10]F.Caballero-Briones,A.Palacios-Padrós,FaustoSanz,CuInSe2filmspreparedbythreesteppulsedelectrodeposition.Depositionmechanisms,opticalandphotoelectrochemicalstudies,ElectrochimicaActa56(2011)9556–9567.
主要描述用三步脉冲电沉积法制备CuInSe2，并对其结构形貌进行了表征。
发明内容
本发明为了解决现有制备CuInSe2薄膜存在的问题，发明了一种氯化物体系两步法制备铜铟硒光电薄膜的方法。
本发明采用电沉积后硒化法制备铜铟硒薄膜，采用二氧化锡导电玻璃为基片，以CuCl2·2H2O、InCl3、SeO2为原料，以C6H5Na3O7·2H2O为络合剂，以蒸馏水为溶剂，按固定摩尔比配制电沉积溶液，先采用晶体管恒电位仪在一定电位和时间下制备前驱体薄膜，以水合联氨为还原剂，在水合联氨中加入硒粉保证硒气氛，在密闭管式炉内加热，使前驱体薄膜硒化并得到目标产物。
本发明的具体制备方法包括如下顺序的步骤：
a.进行二氧化锡导电玻璃基片的清洗，将大小为20mm×20mm的玻璃基片放入体积比丙酮：蒸馏水=5：1的溶液中，超声波清洗30min；再将基片放入乙醇中，超声波清洗30min；再在蒸馏水中将玻璃基片用超声振荡30min；将上述得到的玻璃基片排放在玻璃皿中送入烘箱中，在100℃下烘干供制膜用。
b.将C6H5Na3O7·2H2O、CuCl2·2H2O、InCl3、SeO2放入蒸馏水中，获得均匀稳定的电沉积溶液。具体地说，可以将1.0～2.0份C6H5Na3O7·2H2O、4.5～9.0份CuCl2·2H2O、6.0～12.0份InCl3、6.0～12.0份SeO2放入2700.0～5400.0份的蒸馏水中，使溶液中的物质溶解。
c.将步骤b所述电沉积溶液倒入三电极装置中，以饱和甘汞电极为参比电极，铂电极为辅助电极，二氧化锡导电玻璃为研究电极，采用晶体管恒电位仪在沉积电位为-0.5V下常温沉积薄膜，沉积时间为30min，自然干燥得到前驱体薄膜样品。
d.将步骤c所得前驱体薄膜样品置于支架上，在水合联氨中加入硒粉，前驱体薄膜样品不与水合联氨接触，将前驱体薄膜和水合联氨放入管式炉中。水合联氨放入为40.0～50.0份，硒粉为4.0～8.0份。将管式炉加热至250～400℃之间，保温时间3～9h，然后冷却到室温取出。
e.将步骤d所得物，使其常温自然干燥后，即得到铜铟硒光电薄膜。
本发明不需要高真空条件，对仪器设备要求低，生产成本低，生产效率高，易于操作。所得铜铟硒光电薄膜有较好的连续性和均匀性，主相为CuInSe2相，可以实现低成本大规模的工业化生产。
具体实施方式
实施例1
a.二氧化锡导电玻璃基片的清洗：如前所述进行清洗玻璃基片，基片大小为20mm×20mm。
b.将1.0份C6H5Na3O7·2H2O、4.5份CuCl2·2H2O、6.0份InCl3、6.0份SeO2放入2700.0份的蒸馏水中，使溶液中的物质溶解。
c.将上述电沉积溶液倒入三电极装置中，以饱和甘汞电极为参比电极，铂电极为辅助电极，二氧化锡导电玻璃为研究电极，采用晶体管恒电位仪在沉积电位为-0.5V下常温沉积薄膜，沉积时间为30min，自然干燥得到前驱体薄膜样品。
d.将前驱体薄膜样品置于支架上，在水合联氨中加入硒粉，前驱体薄膜样品不与水合联氨接触，将前驱体薄膜和水合联氨放入管式炉中。水合联氨放入为40.0份，硒粉为4.0份。将管式炉加热至350℃，保温时间6h，然后冷却到室温取出。
e.将步骤d所得物，进行常温自然干燥，得到铜铟硒光电薄膜。
Claims (4)
1.一种氯化物体系两步法制备铜铟硒光电薄膜的方法，包括如下顺序的步骤：
a.二氧化锡导电玻璃基片的清洗；
b.将1.0～2.0份C6H5Na3O7·2H2O、4.5～9.0份CuCl2·2H2O、6.0～12.0份InCl3、6.0～12.0份SeO2放入2700.0～5400.0份的蒸馏水中，使溶液中的物质溶解；
c.采用电沉积法将步骤b所述溶液在导电玻璃片上沉积得到前驱体薄膜，自然干燥，得到前驱体薄膜样品；
d.将步骤c所得前驱体薄膜样品置于支架上，在水合联氨中加入硒粉，前驱体薄膜样品不与水合联氨接触，将前驱体薄膜和水合联氨放入管式炉中；将管式炉加热至250～400℃之间，保温时间3～9h，然后冷却到室温取出；
e.将步骤d所得物，自然干燥，得到铜铟硒光电薄膜。
2.如权利要求1所述的一种氯化物体系两步法制备铜铟硒光电薄膜的方法，其特征在于，步骤a所述清洗，是将导电玻璃基片大小为20mm×20mm，放入体积比丙酮：蒸馏水=5：1的溶液中，超声波清洗30min；再将基片放入乙醇中，超声波清洗30min；再在蒸馏水中将玻璃基片用超声振荡30min；将上述得到的玻璃基片排放在玻璃皿中送入烘箱中，在100℃下烘干供制膜用。
3.如权利要求1所述的一种氯化物体系两步法制备铜铟硒光电薄膜的方法，其特征在于，步骤c所述，是将溶液加入三电极装置中，以饱和甘汞电极为参比电极，铂电极为辅助电极，二氧化锡导电玻璃为研究电极，采用晶体管恒电位仪在沉积电位为-0.5V下常温沉积薄膜，沉积时间为30min，自然干燥得到前驱体薄膜样品。
4.如权利要求1所述的一种氯化物体系两步法制备铜铟硒光电薄膜的方法，其特征在于，步骤d所述管式炉内放入40.0～50.0份水合联氨、4.0～8.0份硒粉。
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| CN108878557A (zh) * | 2018-07-01 | 2018-11-23 | 山东建筑大学 | 一种用氯化物制备铜铁硒光电薄膜的方法 |
| CN108878556A (zh) * | 2018-07-01 | 2018-11-23 | 山东建筑大学 | 一种用硒粉辅助制备铜铁硒光电薄膜的方法 |
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