高质量Cu（In，Ga）Se_2薄膜的低成本制备工艺研究
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摘要
随着人类社会的发展,人们对能源的需求越来越大,然而,目前人们普遍使用的能源如煤炭、石油等都不是可再生能源,这些能源正在枯竭。因此,寻找可再生、获取方便、价格低廉的替代能源己成为目前人类面临的迫切问题。太阳能作为一种清洁、安全可靠并且无处不在的可再生能源而受到人们的普遍亲睐,已经在各个领域得到了广泛应用。在太阳能电池中,CuInSe2(CIS)以其吸收系数高、价格低廉、高稳定性而受到人们的广泛关注,被认为是第三代太阳能电池的主要材料。
本文首先以InCl、SeO2、CuCl2、络合剂柠檬酸和稳定剂KCl的水溶液为电解液,并以HCl溶液调节其PH值,在镀Mo的钠钙玻璃衬底上采用恒电位沉积的方法制备出太阳能电池吸收层CIS,并对所制备的薄膜进行热处理和后硒化工艺以提高薄膜的结晶性能和改善薄膜的化学计量比。其次用射频磁控溅射的方法以单一Cu(In,Ga)Se2 (CIGS)靶材在在镀Mo的钠钙玻璃衬底上溅射制备了Cu(In,Ga)Se2,同样对所制备薄膜进行了热处理和后硒化。最后用二者结合的方法,即先在镀Mo的钠钙玻璃衬底上用恒电位沉积的方法电化学沉积一层CIS,然后再在其上面射频磁控溅射生长一层CIGS。对所制备的薄膜进行了热处理和后硒化。实验中通过X射线衍射(XRD)、扫描电镜((SEM)、能谱仪(EDS)以及拉曼散射等方法对制备的CIS/CIGS薄膜的各种性能进行了表征。
实验结果表明：利用电化学沉积和磁控溅射沉积二者结合的方法,既有效利用电化学沉积生长速度快,沉积方法简单易行,生产成本低等优点弥补了磁控溅射沉积在生长速度和生长成本方面的不足,又利用磁控溅射沉积成膜结晶性好,表面质量高等优点改善了电化学沉积所制备的薄膜。结果显示,二者结合所制备出来的薄膜结合良好,具有比电化学沉积生长薄膜明显好得多的表面平整度和均匀性,结晶性也有所提高,而且制备同等厚度的薄膜比只用磁控溅射沉积所用时间大大减少,降低了制备成本。本文利用恒电位电化学沉积和射频磁控溅射结合的方法探索出了一条高质量低成本CIS的制备之路。
With the development of human society, people growing demand for energy. However, the current widespread use of is not renewable but depleted energy, such as coal, oil and so on. So, to search the energy which renewable, convenient, affordable for alternative has become urgent problems faced by humanity. As a clean, safe, and renewable energy, solar energy can be get everywhere, so it was widely courted and has been used in many fields. With its high absorption coefficient, low cost and high stability, CuInSe2 (CIS) solar cells were wide attention by the people. It is considered the main materials for third-generation solar cell.
First of all, this article make electrolyte potassium chloride with InCl3, SeO2, CuCl2, complexing agent sodium citrate and stabilizer KCl, use HCl to adjust the PH value. At Mo coated soda lime glass prepared thin film solar cell absorber CIS by the potentiostatic deposition method, and the films were during heat treatment and selenium process to improve crystallinity and stoichiometry. Second, use RF magnetron sputtering method prepared Cu (In, Ga) Se2 thin film on Mo coated soda lime glass substrate by a single Cu (In, Ga) Se2 (CIGS) targets sputtering, equally the films have heat treatment and selenium. Finally, a combination of both methods, on the Mo coated soda lime glass substrate deposit a layer CIS with a constant potential electrochemical deposition method first, and then RF magnetron sputtering growth of CIGS layer on the top, and always heat treatment and selenium the films. X-ray diffraction (XRD), scanning electron microscopy ((SEM), energy dispersive spectroscopy (EDS), Raman scattering and other methods were use to characterized the various properties of CIS/CIGS films in the experiment.
The results show that:the method that combining of electrochemical deposition and magnetron sputtering use the character of electrochemical like high growth speed, deposition simple and low cost to make up for the shortage of magnetron sputtering at speed and cost first, and also improving the quality of the films that prepared by electrochemical deposition by use the sputtering deposition film's high quality crystalline and good surface morphology. The results showed that the film prepared by the two stage method have a good combination and much better surface smoothness and uniformity than the only electrochemical deposition films, the crystalline also increased. And the time that prepared the same thickness of the film was greatly reduced to compare with magnetron sputtering only, reduce the production cost. Use the combining of potentiostatic electrochemical deposition and RF magnetron sputtering method, we have explored a low cost processing for preparation high quality CIS in this paper.
本文首先以InCl、SeO2、CuCl2、络合剂柠檬酸和稳定剂KCl的水溶液为电解液,并以HCl溶液调节其PH值,在镀Mo的钠钙玻璃衬底上采用恒电位沉积的方法制备出太阳能电池吸收层CIS,并对所制备的薄膜进行热处理和后硒化工艺以提高薄膜的结晶性能和改善薄膜的化学计量比。其次用射频磁控溅射的方法以单一Cu(In,Ga)Se2 (CIGS)靶材在在镀Mo的钠钙玻璃衬底上溅射制备了Cu(In,Ga)Se2,同样对所制备薄膜进行了热处理和后硒化。最后用二者结合的方法,即先在镀Mo的钠钙玻璃衬底上用恒电位沉积的方法电化学沉积一层CIS,然后再在其上面射频磁控溅射生长一层CIGS。对所制备的薄膜进行了热处理和后硒化。实验中通过X射线衍射(XRD)、扫描电镜((SEM)、能谱仪(EDS)以及拉曼散射等方法对制备的CIS/CIGS薄膜的各种性能进行了表征。
实验结果表明：利用电化学沉积和磁控溅射沉积二者结合的方法,既有效利用电化学沉积生长速度快,沉积方法简单易行,生产成本低等优点弥补了磁控溅射沉积在生长速度和生长成本方面的不足,又利用磁控溅射沉积成膜结晶性好,表面质量高等优点改善了电化学沉积所制备的薄膜。结果显示,二者结合所制备出来的薄膜结合良好,具有比电化学沉积生长薄膜明显好得多的表面平整度和均匀性,结晶性也有所提高,而且制备同等厚度的薄膜比只用磁控溅射沉积所用时间大大减少,降低了制备成本。本文利用恒电位电化学沉积和射频磁控溅射结合的方法探索出了一条高质量低成本CIS的制备之路。
With the development of human society, people growing demand for energy. However, the current widespread use of is not renewable but depleted energy, such as coal, oil and so on. So, to search the energy which renewable, convenient, affordable for alternative has become urgent problems faced by humanity. As a clean, safe, and renewable energy, solar energy can be get everywhere, so it was widely courted and has been used in many fields. With its high absorption coefficient, low cost and high stability, CuInSe2 (CIS) solar cells were wide attention by the people. It is considered the main materials for third-generation solar cell.
First of all, this article make electrolyte potassium chloride with InCl3, SeO2, CuCl2, complexing agent sodium citrate and stabilizer KCl, use HCl to adjust the PH value. At Mo coated soda lime glass prepared thin film solar cell absorber CIS by the potentiostatic deposition method, and the films were during heat treatment and selenium process to improve crystallinity and stoichiometry. Second, use RF magnetron sputtering method prepared Cu (In, Ga) Se2 thin film on Mo coated soda lime glass substrate by a single Cu (In, Ga) Se2 (CIGS) targets sputtering, equally the films have heat treatment and selenium. Finally, a combination of both methods, on the Mo coated soda lime glass substrate deposit a layer CIS with a constant potential electrochemical deposition method first, and then RF magnetron sputtering growth of CIGS layer on the top, and always heat treatment and selenium the films. X-ray diffraction (XRD), scanning electron microscopy ((SEM), energy dispersive spectroscopy (EDS), Raman scattering and other methods were use to characterized the various properties of CIS/CIGS films in the experiment.
The results show that:the method that combining of electrochemical deposition and magnetron sputtering use the character of electrochemical like high growth speed, deposition simple and low cost to make up for the shortage of magnetron sputtering at speed and cost first, and also improving the quality of the films that prepared by electrochemical deposition by use the sputtering deposition film's high quality crystalline and good surface morphology. The results showed that the film prepared by the two stage method have a good combination and much better surface smoothness and uniformity than the only electrochemical deposition films, the crystalline also increased. And the time that prepared the same thickness of the film was greatly reduced to compare with magnetron sputtering only, reduce the production cost. Use the combining of potentiostatic electrochemical deposition and RF magnetron sputtering method, we have explored a low cost processing for preparation high quality CIS in this paper.
引文
[1]王正安.铜铟镓硒薄膜太阳能电池CIGS吸收层的研究与制备.华东师范大学,硕士学位论文：1-4.
[2]沈辉,舒碧芬,闻立时,中国储能电池与动力电池及其关键材料学术研讨会.2005.5,中国,长沙.
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[10]Goetzberger A, Knobloch J, Vob B, Crystalline silicon solar cell. Chichester: JohnWiley&Sons;1998.
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[16]Ingrid Repins, Miguel A. Contreras, Brian Egaas, Clay DeHart, John Scharf, Craig L. Perkins, Bobby To and Rommel Noufi,19.9%-efficient ZnO/CdS/CuInGaSe2 Solar Cell with 81.2% Fill Factor.Prog.Photovolt:Res. Appl.2008; 16:235-239
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[1]W E Devaney,R A Mickelsen, W S Chen, et al. Cadmium Sulfide/copper Ternary Hetero-junction Cell Research. Final Technical Progress Report for the period. July 1987,21-24.
[2]Ingrid Repins, Miguel A. Contreras, Brian Egaas, Clay DeHart, John Scharf, Craig L. Perkins, Bobby To and Rommel Noufi,19.9%-efficient ZnO/CdS/CuInGaSe2 Solar Cell with 81.2% Fill Factor.Prog.Photovolt:Res.Appl.2008; 16:235-239
[3]铜铟镓硒薄膜太阳能电池CIGS吸收层的研究与制备
[4]ULLAL H S,ZWEIBEL K,VON-ROEDERN B. Polycrystalline Thin Film Photovoltaics: Research, Development, and Technologies[R].New Orleans, Louisiana, The 29th IEEE PV Specialists Conference,2002.
[5]Jonas Hodstrom, Marika Bodegard, Dimitri Hariskoas, et al. ZnO/CdS/Cu(In,Ga)Se2 thin films solar cells with improved performance. Schwartz RJ. The 23rd IEEE Photovoltaic Specialists Conference, Louisville KY,1993 [C]. Louisville, KY:Electron Device Sociaty,1993:364-371.
[6]Stolt L, Hedstrom J, Kessler J, et al.ZnO/CdS/Cu(In,Ga)Se2 thin film solar cells with improved performance [J].Appl.Phys.Lett.,1993,62:597.
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