CN105551936A - 一种硝酸盐体系两步法制备铜铟硫光电薄膜的方法 - Google Patents
一种硝酸盐体系两步法制备铜铟硫光电薄膜的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- LCUOIYYHNRBAFS-UHFFFAOYSA-N copper;sulfanylideneindium Chemical compound [Cu].[In]=S LCUOIYYHNRBAFS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 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 18
- 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 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-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
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 25
- 239000010409 thin film Substances 0.000 claims description 17
- 230000005693 optoelectronics Effects 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 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
- 239000000126 substance Substances 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
- 230000000873 masking effect Effects 0.000 claims description 2
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- 230000008569 process Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 239000002105 nanoparticle Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910000238 buergerite Inorganic materials 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
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Abstract
一种硝酸盐体系两步法制备铜铟硫光电薄膜的方法,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、Cu(NO3)2·3H2O、In(NO3)3·4.5H2O、Na2S2O3·5H2O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升华硫粉,在密闭管式炉内加热,使前驱体薄膜硫化,最后取出样品进行干燥,得到铜铟硫光电薄膜。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。
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,尤其涉及一种硝酸盐体系两步法制备铜铟硫光电薄膜的方法。
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。(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(1.04eV)。(3)CuInS2不含任何有毒成分。(4) CuInS2光吸收系数很大,转换效率高,性能稳定,薄膜厚度小,约2μm,且硫的价格较低。(5)在CuInS2基础上掺杂其它元素,如使Ga或Al部分取代In原子,用Se部分取代S,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1.04~1.72 eV之间变化,包含高效率吸收太阳光的带隙范围1.4~1.6eV。(6) 抗辐射能力强,没有光致衰减效应,因而使用寿命长。(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。
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。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。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。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。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。
如前面所述方法一样,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] S. Lugo, I. López, Y. Peña, M. Calixto,
T. Hernández, S. Messina, D.
Avellaneda, Characterization of CuInS2 thin films prepared by
chemical bath deposition and their implementation 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。
[2] Zhaomin Hao, Yong Cui, Gang Wang, Colloidal synthesis of
wurtzite CuInS2 nanocrystals and their photovoltaic application,
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。
[3] S. Mostafa Hosseinpour-Mashkani, Masoud Salavati-Niasari,
Fatemeh Mohandes, K. Venkateswara-Rao, CuInS2 nanoparticles:
Microwave-assisted synthesis, characterization, and photovoltaic measurements,
Materials Science in 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。
[4] S.M. Hosseinpour-Mashkani, M. Salavati-Niasari, F.
Mohandes, CuInS2 nanostructures: Synthesis, characterization,
formation mechanism and solar cell applications, 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。
[5] Xiaofeng Wu, Yaohan Huang, Qiqi Bai, Qingfei Fan, Guangli
Li, Ximei Fan, Chaoliang Zhang, Hong Liu, Investigation of CuInS2
thin films deposited on FTO by one-pot solvothermal synthesis, Materials
Science in Semiconductor 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。
[6] A. Shanmugavel, K. Srinivasan, K.R. Murali, Pulse
electrodeposited 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能差异。
[7] Hsiang Chen, Yih-Min Yeh, Chuan Hao Liao, Jian Zhi Chen,
Chau-le Wang , Removal of CuS phases from electrodeposited CuInS2 films,
Ceramics International 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。
[8] M.A. Majeed Khan, Sushil Kumar, Mohamad S. AlSalhi,
Synthesis and characteristics of spray deposited CuInS2 nanocrystals
thin films for photovoltaic applications, 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。
[9] D. Abdelkader, N. Khemiri, M. Kanzari, The effect of
annealing on the physical properties of thermally evaporated CuIn2n+1S3n+2
thin films (n=0,1,2 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+1S3n+2(n=0,1,2
and 3)薄膜性能的影响。
[10] 马剑平, 高 杨, Cu-In 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-In金属预制层后硫化得到CuInS2薄膜。
发明内容
本发明为了解决现有制备铜铟硫光电薄膜存在的问题,发明了一种硝酸盐体系两步法制备铜铟硫光电薄膜的方法。
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Cu(NO3)2·3H2O,In(NO3)3·4.5H2O,Na2S2O3·5H2O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。
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、Cu(NO3)2·3H2O、In(NO3)3·4.5H2O、Na2S2O3·5H2O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、6.5~13.0份Cu(NO3)2·3H2O、10.0~20.0份In(NO3)3·4.5H2O、65.0~130.0份Na2S2O3·5H2O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-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。
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。水合联氨放入为40.0~50.0份,升华硫粉为1.0~2.0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,即得到铜铟硫光电薄膜。
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。
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、6.5份Cu(NO3)2·3H2O、10.0份In(NO3)3·4.5H2O、65.0份Na2S2O3·5H2O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-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。
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。水合联氨放入为40.0份,升华硫粉为1.0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,得到铜铟硫光电薄膜。
Claims (4)
1.一种硝酸盐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C6H5Na3O7·2H2O、6.5~13.0份Cu(NO3)2·3H2O、10.0~20.0份In(NO3)3·4.5H2O、65.0~130.0 Na2S2O3·5H2O份放入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℃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。
2.如权利要求1所述的一种硝酸盐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×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所述的一种硝酸盐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。
4.如权利要求1所述的一种硝酸盐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。
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CN107620103B (zh) * | 2017-09-11 | 2019-12-24 | 洛阳师范学院 | 一种一硫化锗薄膜的制备方法 |
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