CN105489673A - Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method - Google Patents

Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method Download PDF

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CN105489673A
CN105489673A CN201510943184.XA CN201510943184A CN105489673A CN 105489673 A CN105489673 A CN 105489673A CN 201510943184 A CN201510943184 A CN 201510943184A CN 105489673 A CN105489673 A CN 105489673A
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刘科高
李静
刘慧�
徐勇
石磊
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山东建筑大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and 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 peculiar to the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322Inorganic 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

Abstract

The invention discloses a method for preparing a copper-indium sulfide photoelectric thin film by a chloride system through a two-step method, and belongs to the preparation technical field of a thin film for a solar cell. The preparation method comprises the following steps of cleaning a stannic oxide conductive glass substrate; putting C6H5Na3O7.2H2O, CuCl2.2H2O, InCl3, and Na2S2O3.5H2O into distilled water; obtaining a precursor thin film by adopting an electrodeposition method on the conductive glass substrate; naturally drying, and putting into a tube furnace added with hydrazine hydrate to enable the precursor thin film product not to be in contact with hydrazine hydrate, wherein hydrazine hydrate is added with sublimed sulfur powder; heating in the sealed tube furnace to enable the precursor thin film to be vulcanized, and finally taking out the sample and drying the sample to obtain the copper-indium sulfide photoelectric thin film. The preparation method does not require a high vacuum condition, and is low in instrument equipment requirement, low in production cost, high in production efficiency and easy to operate; the obtained copper-indium sulfide photoelectric thin film is relatively high in continuity and uniformity; the main phase adopts a CuInS2 phase, so that the low-cost and large-scale industrial production can be realized.

Description

一种氯化物体系两步法制备铜铟硫光电薄膜的方法 Preparation of a thin film copper indium sulfur photovoltaic system two-step process one chloride method

技术领域 FIELD

[0001]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硫光电薄膜的方法。 [0001] The present invention pertains to thin-film photovoltaic solar cell preparation techniques, and more particularly relates to a two-step Method of Copper Indium a sulfur chloride film photovoltaic system.

背景技术 Background technique

[0002]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。 [0002] With the social and economic development, energy shortages and pollution caused by energy consumption has become a prominent issue in the domestic social development, coal, oil and other non-renewable resources, development and utilization of clean and renewable energy to protect the environment, ensure sustainable economic development and building a harmonious society has important significance. 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。 Photovoltaic power generation is safe and reliable, no noise, no pollution, less constrained, low failure rate, easy maintenance, etc., can use solar energy this clean, safe and environmentally friendly renewable energy, so in recent decades of research and development of solar cells and more attention.

[0003]铜铟硫基薄膜太阳能电池目前可以认为是最有发展前景的薄膜电池之一,这是因为其吸收层材料CuInS2具有一系列的优点:(1) CuInS2是直接带隙半导体。 [0003] thio copper indium thin film solar cell is currently considered one of the most promising thin-film batteries, because CuInS2 layer material that absorbs a series of advantages: (1) CuInS2 are direct band gap semiconductors. (2)在室温下CuInS2的禁带宽度为1.50eV,是太阳能电池中要求的最佳能隙,这方面优于CuInSe2(1.04^)。 (2) at room temperature, the band gap of 1.50 eV CuInS2, best bandgap solar cell requirements, which is superior CuInSe2 (1.04 ^). (3)0111^2不含任何有毒成分。 (3) ^ 2 0111 does not contain any toxic components. (4) CuInS2光吸收系数很大,转换效率高,性能稳定,薄膜厚度小,约2μπι,且硫的价格较低。 (4) CuInS2 large optical absorption coefficient, high efficiency, stable performance, a small film thickness, about 2μπι, sulfur and low price. (5)在CuInS2基础上掺杂其它元素,如使Ga或A1部分取代In原子,用Se部分取代S,即制备成Cu( Im—xGax)Se2,Cu(Im—xGax) (Se2-ySy),Cu(Im-xAlx)(Se2—XSX),其晶体结构仍然是黄铜矿。 (5) doped with other elements on the basis of CuInS2, such as partial substitution of Ga or In atoms A1, S substituted with Se portion, i.e., to prepare a Cu (Im-xGax) Se2, Cu (Im-xGax) (Se2-ySy) , Cu (Im-xAlx) (Se2-xSX), which is still chalcopyrite crystal structure. 改变其中Ga/(Ga+In)等的原子比,可以使其禁带宽度在1.04〜1.72 eV之间变化,包含高效率吸收太阳光的带隙范围1.4〜1.6^。 Wherein changing the Ga / (Ga + In) atomic ratio or the like, so that the band gap can be varied between 1.04~1.72 eV, comprising a high-efficiency solar absorption band gap range 1.4~1.6 ^. (6)抗辐射能力强,没有光致衰减效应,因而使用寿命长。 (6) strong anti-radiation, light-induced attenuation no effect, so long service life. (7) P型CIGS材料的晶格结构与电子亲和力都能跟普通的N型窗口材料(如CdS、ZnO)匹配。 Lattice structure and electron affinity (7) P-type CIGS material can be matched with the common N-type material window (e.g., CdS, ZnO).

[0004]目前CuInS2的制备方法主要有溶剂热法、喷射热解法、电化学沉积法、化学沉积法、化学气相沉积、分子束外延、反应溅射法、真空蒸发法、溅射合金层后硫化法等。 [0004] The method of the present CuInS2 prepared mainly solvothermal method, a spray pyrolysis method, electrochemical deposition, chemical deposition, chemical vapor deposition, molecular beam epitaxy, reactive sputtering method, a vacuum evaporation method, a sputtering alloy layer vulcanization method. 其中,蒸发法和溅射法技术比较成熟,光电转换效率高,已实现产业化操作。 Wherein the evaporation and sputtering technology is relatively mature, high photoelectric conversion efficiency, the industry has achieved operation. 但是,这两种方法均需要真空设备,制备成本比较高,而且不能沉积大面积的太阳能薄膜,原材料的利用率较低。 However, both methods require a vacuum apparatus, the production cost is relatively high, but can not be deposited in a large area thin film solar, low utilization of raw materials. 电沉积成本低,易实现大面积沉积薄膜,同时也存在一些问题,比如Cu、In、S三种元素电位值相差较大,很难实现共沉积,并且发现在制备CuInS2时薄膜质量较差,孔洞多,硫元素较难进入薄膜,化学成分难以控制等问题,很难直接得到纯相。 Electrodeposition low cost, easy to achieve a large area thin film deposition, there are also some problems, such as Cu, In, S value potential difference between the larger three elements, difficult to achieve co-deposition, and found that the film quality is poor preparation CuInS2, multiple holes, into the film difficult to elemental sulfur, chemical composition and other issues is difficult to control, difficult to directly obtain pure phase. 因此选择合适的电沉积工艺制备均一致密的纯相CuInS2薄膜成为具有创新性的重要课题。 Thus selecting suitable electrical deposition process for preparing a homogeneous dense pure phase CuInS2 thin film is an important problem innovative.

[0005]如前面所述方法一样,其它方法也有不同的缺陷。 [0005] The method as previously described, other methods have different drawbacks. 与本发明相关的还有如下文献: Related to the present invention there are the following documents:

[1] S.Lugo, 1.Lopez, Y.Pena, M.Calixto, T.Hernandez, S.Messina, D.Avellaneda, Characterizat1n of CuInS2 thin films prepared by chemical bathdeposit1n and their implementat1n in a solar cell, Thin Solid Films 569(2014) 76-80.主要描述了用化学沉积法分别制备In2S3和CuS薄膜,后热处理得到CuInS2薄膜,并对其性能进行了表征。 [1] S.Lugo, 1.Lopez, Y.Pena, M.Calixto, T.Hernandez, S.Messina, D.Avellaneda, Characterizat1n of CuInS2 thin films prepared by chemical bathdeposit1n and their implementat1n in a solar cell, Thin Solid films 569 (2014) 76-80. describes the In2S3 and CuS films were prepared by a chemical deposition method, CuInS2 films obtained after the heat treatment, and its properties were characterized.

[0006] [2] Zhaomin Hao, Yong Cui, Gang Wang, Colloidal synthesis of wurtziteCuInS2 nanocrystals and their photovoltaic applicat1n, Materials Letters 146(2015) 77-80.主要描述了用胶体合成法制备纤锌矿CuInS2纳米晶体,对其晶体结构和光电性能进行了研究。 [0006] [2] Zhaomin Hao, Yong Cui, Gang Wang, Colloidal synthesis of wurtziteCuInS2 nanocrystals and their photovoltaic applicat1n, Materials Letters 146 (2015) 77-80. Describes the preparation fibers with colloidal nanocrystals synthesis zinc CuInS2, We studied its crystal structure and optical properties.

[0007] [3] S.Mostafa Hosseinpour-Mashkani, Masoud Salavat1-Niasari, FatemehMohandes,K.Venkateswara-Rao,CuInS2 nanoparticles: Microwave-assistedsynthesis, characterizat1n, and photovoltaic measurements, Materials Sciencein Semiconductor Processing 16 (2013) 390-402.主要描述微波辅助法制备CuInS2纳米颗粒及其光电性能的研究。 [0007] [3] S.Mostafa Hosseinpour-Mashkani, Masoud Salavat1-Niasari, FatemehMohandes, K.Venkateswara-Rao, CuInS2 nanoparticles: Microwave-assistedsynthesis, characterizat1n, and photovoltaic measurements, Materials Sciencein Semiconductor Processing 16 (2013) 390-402 . describes microwave-assisted particle Preparation and Optical properties of CuInS2 nm.

[0008] [4] SMHosseinpour-Mashkani, M.Salavat1-Niasari, F.Mohandes,CuInS2 nanostructures: Synthesis, characterizat1n, format1n mechanism andsolar cell applicat1ns, Journal of Industrial and Engineering Chemistry 20(2014) 3800-3807.主要描述微波辅助法制备黄铜矿CuInS2纳米颗粒,并对其进行了性能表征和形成机理研究。 [0008] [4] SMHosseinpour-Mashkani, M.Salavat1-Niasari, F.Mohandes, CuInS2 nanostructures: Synthesis, characterizat1n, format1n mechanism andsolar cell applicat1ns, Journal of Industrial and Engineering Chemistry 20 (2014) 3800-3807 describes a microwave. Preparation auxiliary chalcopyrite CuInS2 nanoparticles, and its performance was characterized and studied the formation mechanism.

[0009] [5] Xiaofeng ffu, Yaohan Huang, Qiqi Bai,Qingfei Fan, Guangli Li,Ximei Fan, Chaoliang Zhang, Hong Liu, Investigat1n of CuInS2 thin filmsdeposited on FT0 by one-pot solvothermal synthesis, Materials Science inSemiconductor Processing 37 (2015) 250-258.主要描述了溶剂热合成法制备的CuInS2薄膜的性能。 [0009] [5] Xiaofeng ffu, Yaohan Huang, Qiqi Bai, Qingfei Fan, Guangli Li, Ximei Fan, Chaoliang Zhang, Hong Liu, Investigat1n of CuInS2 thin filmsdeposited on FT0 by one-pot solvothermal synthesis, Materials Science inSemiconductor Processing 37 ( 2015) 250-258. describes the performance of a thin film of CuInS2 prepared by solvothermal synthesis.

[0010] [6] A.Shanmugave 1 , K.Srinivasan,KRMur a 1 i , Pulseelectrodeposited copper indium sulpho selenide films and their properties,Materials Science in Semiconductor Processing 16 (2013) 1665-1671.主要描述了脉冲电沉积法制备CuIn(S,Se)2薄膜,并研究了不同硫含量时的结构和性會^差异。 [0010] [6] A.Shanmugave 1, K.Srinivasan, KRMur a 1 i, Pulseelectrodeposited copper indium sulpho selenide films and their properties, Materials Science in Semiconductor Processing 16 (2013) 1665-1671. Describes a pulsed electrodeposition preparation of CuIn (S, Se) 2 thin film, and will study the structure and properties of the different time difference ^ sulfur content.

[0011] [7] Hsiang Chen, Yih-Min Yeh,Chuan Hao Liao, Jian Zhi Chen, Chau-1eWang, Removal of CuS phases from electrodeposited CuInS2 films,CeramicsInternat1nal 40 (2014) 67-72.主要描述了采用两步热处理去除电沉积制备的CuInS2薄膜里的CuS相并进行了形貌及成分分析。 [0011] [7] Hsiang Chen, Yih-Min Yeh, Chuan Hao Liao, Jian Zhi Chen, Chau-1eWang, Removal of CuS phases from electrodeposited CuInS2 films, CeramicsInternat1nal 40 (2014) 67-72. Describes a two-step removing heat CuInS2 thin film is deposited in the preparation phase and CuS morphology and composition analysis.

[0012] [8] MAMajeed Khan, Sushi 1 Kumar, Mohamad S.AlSalhi,Synthesis andcharacteristics of spray deposited CuInS2 nanocrystals thin films forphotovoltaic applicat1ns, Materials Research Bulletin 48 (2013) 4277-4282.主要描述用溅射沉积法制备CuInS2薄膜并用FESEM,FETEM,HRTEM,AFM,XRD等进行了表征。 [0012] [8] MAMajeed Khan, Sushi 1 Kumar, Mohamad S.AlSalhi, Synthesis andcharacteristics of spray deposited CuInS2 nanocrystals thin films forphotovoltaic applicat1ns, Materials Research Bulletin 48 (2013) 4277-4282. Preparation of CuInS2 describes a sputtering deposition method and films were characterized by FESEM, FETEM, HRTEM, AFM, XRD like.

[0013] [9] D.Abdelkader, N.Khemiri, M.Kanzari, The effect of annealing onthe physical properties of thermally evaporated CuIn2n+iS3n+2 thin films (n=0,l,2 and 3), Materials Science in Semiconductor Processing 16 (2013) 1997-2004.主要描述了退火工艺对热蒸发法制备的CuIn2n+iS3n+2(n=0,l,2 and 3)薄膜性能的影响。 [0013] [9] D.Abdelkader, N.Khemiri, M.Kanzari, The effect of annealing onthe physical properties of thermally evaporated CuIn2n + iS3n + 2 thin films (n = 0, l, 2 and 3), Materials Science in Semiconductor Processing 16 (2013) 1997-2004. CuIn2n describes a thermal evaporation method prepared by annealing + iS3n + 2 (n = 0, l, 2 and 3) thin film properties.

[0014] [10]马剑平,高杨,Cu-1n预置层后硫化法制备CuInS2薄膜,太阳能学报0254-0096(2013) 06-1010-05.主要描述采用脉冲磁控溅射法制备Cu-1n金属预制层后硫化得到CuInS2薄膜。 [0014] [10] Preparation of CuInS2 thin film prepared by sulfidation after Majian Ping, Gao Yang, Cu-1n pre-layer, solar UNIVERSITY 0254-0096 (2013) 06-1010-05. Describes were prepared by pulsed magnetron sputtering Cu- after 1n metal sulfide obtained CuInS2 thin preform layer.

[0015] [0015]

发明内容 SUMMARY

[0016]本发明为了解决现有制备CuInS2薄膜存在的问题,发明了一种氯化物体系两步法制备铜铟硫光电薄膜的方法。 [0016] In order to solve the conventional problems prepared CuInS2 thin film, a method of the invention was prepared in two steps from Chloride photovoltaic thin film copper indium sulfur.

[0017]本发明采用电沉积后硫化法制备铜铟硫薄膜,采用二氧化锡导电玻璃为基片,以CuCl2.2H20,InCl3,Na2S203.5H20为原料,以C6H5Na307.2H20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,在水合联氨中加入升华硫粉保证硫气氛,在密闭管式炉内加热,使前驱体薄膜硫化并得到目标产物。 [0017] The present invention uses the electrodeposited film of Copper Indium sulfur vulcanization Method using conductive tin oxide glass substrate to CuCl2.2H20, InCl3, Na2S203.5H20 as raw materials C6H5Na307.2H20 complexing agent, to distilled water as a solvent, the molar ratio of fixed electrodepositing solution prepared, a transistor potentiostat first precursor thin film was prepared at an electric potential and time, hydrated hydrazine as a reducing agent, powdered sulfur was added to ensure sublimation of sulfur in the atmosphere in the hydrazine hydrate in a closed tube furnace heating the precursor thin film and vulcanizing to give the desired product.

[0018]本发明的具体制备方法包括如下顺序的步骤: [0018] The specific method of preparation of the present invention comprises the steps in the following order:

a.进行二氧化锡导电玻璃基片的清洗,将大小为20mmX 20mm的玻璃放入体积比丙酮: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°C下烘干供制膜用。 . A cleaning conductive tin oxide glass substrates, the glass 20mmX 20mm size into a volume ratio of acetone: distilled water = 5: 1 solution, ultrasonic cleaning for 30 min; then the substrate into ethanol in ultrasonic cleaning for 30 min; then with distilled water in a glass substrate using an ultrasonic oscillation for 30 min; the glass substrate obtained above was discharged into a glass dish in an oven at 100 ° C for drying the film for use.

[0019] b.将C6H5Na307.2H20、CuC12.2H20、InCl3、Na2S203.5H20放入蒸馏水中,获得均匀稳定的电沉积溶液。 [0019] b. The C6H5Na307.2H20, CuC12.2H20, InCl3, Na2S203.5H20 into distilled water to obtain a homogeneous and stable electrodeposition solution. 具体地说,可以将1.0〜2.0份C6H5Na307.2H20、4.5〜9.0份CuCl2.2Η20、6.0〜12.0份InCl3、65.0〜130.0份Na2S203.5H20放入2700.0〜5400.0份的蒸馏水中,使溶液中的物质溶解。 Specifically, 1.0~2.0 parts C6H5Na307.2H20,4.5~9.0 CuCl2.2Η20,6.0~12.0 parts parts parts Na2S203.5H20 InCl3,65.0~130.0 2700.0~5400.0 can be placed parts of distilled water, and the solution of the substance dissolved.

[0020] 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-1.0V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。 [0020] c. Said step b electrodeposition solution was poured into a three-electrode device to a saturated calomel electrode as the reference electrode, a platinum electrode as the auxiliary electrode, conductive tin oxide glass working electrode, a transistor potentiostat in the deposition potential of -1.0V to room temperature the deposited film, deposition time of 30min, and dried to give a natural precursor film sample.

[0021 ] d.将步骤c所得前驱体薄膜样品置于支架上,在水合联氨中加入升华硫粉,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。 [0021] d. The precursor thin film obtained in step c was placed on the sample holder, sublimation of sulfur powder was added, the precursor is not in contact with the film sample in hydrazine hydrate hydrazine hydrate, the precursor thin film into the tube and hydrazine hydrate furnace. 水合联氨放入为40.0〜50.0份,升华硫粉为1.0〜2.0份。 Add hydrazine hydrate to 40.0~50.0 parts, 1.0~2.0 parts by sublimation of sulfur powder. 将管式炉加热至250〜400°C之间,保温时间3〜9h,然后冷却到室温取出。 The tube furnace was heated to between 250~400 ° C, holding time 3~9h, taken out and then cooled to room temperature.

[0022] e.将步骤d所得物,使其常温自然干燥后,即得到铜铟硫光电薄膜。 [0022] e. The resultant product of step d, so that at room temperature after natural drying, to obtain copper indium thin film photovoltaic sulfur.

[0023]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。 [0023] The present invention does not require high vacuum equipment requirements for low, low production costs, high production efficiency, easy to operate. 所得铜铟硫光电薄膜有较好的连续性和均匀性,主相为CuInS2相,可以实现低成本大规模的工业化生产。 The resulting thin film copper indium sulfur photoelectric better continuity and uniformity, CuInS2 phase as the main phase, can be achieved at low cost large-scale industrial production.

[0024] [0024]

[0025] [0025]

具体实施方式 Detailed ways

[0026] 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20mmX20mm ο [0026] Example 1 a tin oxide conductive glass substrate cleaning: cleaning a glass substrate as described above, the substrate size 20mmX20mm ο

[0027] b.将1.0份C6H5Na307.2H20、4.5份CuCl2.2H20、6.0份InCl3、65.0份Na2S203.5H20放入2700.0份的蒸馏水中,使溶液中的物质溶解。 [0027] b. CuCl2.2H20,6.0 1.0 parts C6H5Na307.2H20,4.5 parts parts parts Na2S203.5H20 InCl3,65.0 2700.0 parts of distilled water into the solution of the material was dissolved.

[0028] 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-1.0V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。 [0028] c electrodeposition solution was poured into the above three-electrode device to a saturated calomel electrode as the reference electrode, a platinum electrode as the auxiliary electrode, conductive tin oxide glass working electrode, a transistor potentiostat deposition potential -1.0V at room temperature thin film deposition, the deposition time was 30min, and dried to give a natural precursor film sample.

[0029] d.将前驱体薄膜样品置于支架上,在水合联氨中加入升华硫粉,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。 [0029] d. The precursor was placed on the film sample holder, sublimation sulfur powder was added, the precursor is not in contact with the film sample in hydrazine hydrate hydrazine hydrate, the precursor thin film hydrazine hydrate and placed in a tube furnace . 水合联氨放入为40.0份,升华硫粉为1.0份。 Hydrazine hydrate into 40.0 parts, 1.0 parts of sulfur powder sublimation. 将管式炉加热至350°C,保温时间6h,然后冷却到室温取出。 The tube furnace was heated to 350 ° C, holding time 6h, and then cooled to room temperature and taken out.

[0030] e.将步骤d所得物,进行常温自然干燥,得到铜铟硫光电薄膜。 [0030] e. The resultant product of step d, at room temperature for natural drying, to obtain copper indium thin film photovoltaic sulfur.

Claims (4)

1.一种氯化物体系两步法制备铜铟硫光电薄膜的方法,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C6H5Na307.2H20、4.5〜9.0份CuCl2.2Η20、6.0〜12.0份InCl3、65.0〜130.0份Na2S203.5H20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,在水合联氨中加入升华硫粉,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°C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,进行自然干燥,得到铜铟硫光电薄膜。 1. A method for two-step Preparation of copper indium sulfur chloride film photovoltaic system, comprising the sequential steps of: a conductive tin dioxide cleaning a glass substrate; b. The 1.0~2.0 parts C6H5Na307.2H20,4.5~. 9.0 parts CuCl2.2Η20,6.0~12.0 InCl3,65.0~130.0 parts parts parts 2700.0~5400.0 Na2S203.5H20 into distilled water, and the solution of the material was dissolved; C using the electrodeposition solution in step b said conductive. is deposited on the glass sheet to obtain a precursor film, natural drying, to obtain a precursor film sample; D precursor obtained in step C was placed on the film sample holder, sulfur powder in the hydrazine hydrate, the precursor film sample not added with hydrated sublimation. with ammonia, a precursor thin film and hydrazine hydrate into the tube furnace; tube furnace heated to between 250~400 ° C, holding time 3~9h, then cooled to room temperature and taken out; E obtained to step d. It was naturally dried, to give copper indium thin film photovoltaic sulfur.
2.如权利要求1所述的一种氯化物体系两步法制备铜铟硫光电薄膜的方法,其特征在于,步骤a所述清洗,是将导电玻璃基片大小为20mm X 20mm,放入体积比丙酮:蒸馈水=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°C下烘干供制膜用。 2. The two-step method of Preparation Chloride photovoltaic thin film copper indium sulfur according to claim 1, wherein said cleaning step a, is a conductive glass substrate a size of 20mm X 20mm, into volume ratio acetone: distilled water = feed 5: 1 in solution, ultrasonic cleaning 30min; then the substrate into ethanol, the ultrasonic cleaning 30min; 30min with ultrasonic vibration and then the glass substrate in the distilled water; the above-obtained glass in the glass substrate discharged into an oven dish, dried at 100 ° C for the film for use.
3.如权利要求1所述的一种氯化物体系两步法制备铜铟硫光电薄膜的方法,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-1.0V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。 3. The two-step process of the indium thin film photovoltaic sulfur 1. A Method of Copper Chloride claim, wherein said step c, is added to the solution in a three electrode arrangement, with a saturated calomel electrode reference electrode, a platinum electrode as the auxiliary electrode, conductive tin oxide glass working electrode, a transistor potentiostat -1.0V at room temperature in depositing a thin film deposition potential, for a deposition time of 30min, and dried to give a natural precursor film sample.
4.如权利要求1所述的一种氯化物体系两步法制备铜铟硫光电薄膜的方法,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、1.0〜2.0份升华硫粉。 4. The two-step method of Preparation Chloride photovoltaic thin film copper indium sulfur according to claim 1, wherein said step d into a tube furnace 40.0~50.0 parts hydrazine hydrate, 1.0~ 2.0 parts of sulfur powder sublimation.
CN201510943184.XA 2015-12-17 2015-12-17 Method for preparing copper-indium sulfide photoelectric thin film by chloride system through two-step method CN105489673A (en)

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US20080142072A1 (en) * 2004-02-19 2008-06-19 Dong Yu Solution-based fabrication of photovoltaic cell
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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080142072A1 (en) * 2004-02-19 2008-06-19 Dong Yu Solution-based fabrication of photovoltaic cell
CN102034898A (en) * 2010-10-20 2011-04-27 山东建筑大学 Preparation method of Cu-In-S photoelectric film material for solar cells

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