Abstract：Low cost and environment friendly Cu2ZnSnS4 (CZTS) is the best candidate to replace CuInxGa1-xSe2 (CIGS) which owns noble and toxic metal for thin film solar cells. Electrodeposition technique is a low cost method where vacuum equipment and target materials are not required. A simpler fabrication method is co-electrodeposition of Cu-Zn-Sn (CZT) alloy on fluorine-doped tin oxide (FTO) in aqueous solution. In this paper, CZTS thin films were successfully prepared by sulfurization of electrodeposited CZT alloy precursors at 550oC in protective argon gas. The CZT precursors were electrodeposited on FTO via a three-electrode system in which FTO is used as working electrode, platinum (Pt) mesh and Ag/AgCl as counter and reference electrodes. The electrolyte contains CuSO4, ZnSO4, SnSO4, complexing agent-Triethanolamine (TEA) and sodium citrate. The precursors were sulfurized by sulfur vapor at 550 ℃ in protective argon gas and then CZTS films were obtained. The structural, morphological, compositionaland optical properties of CZTS films have been characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), UV-vis spectroscopy and photoelectrochemical measurement (PEC). XRD and Raman spectroscopy have confirmed the kesterite structure of CZTS films sulfurized at 550 ℃. One major peak at 342 cm-1 and two second strong peaks at 289 and 370 cm-1 are observed in the Raman spectra, which agree with those reported from kesterite CZTS. SEM shows chemical composition of optimum CZTS film is near that of stoichiometric CZTS. The ratios of Cu/(Zn+Sn) and S/(Zn+Sn+Cu) in CZTS film are 0.52 and 1.01, respectively, which indicates that the content of S in “copper poor” CZTS film is very suitable. The photocurrent of the “copper-poor” CZTS film was measured by PEC. PEC results confirm that light current is produced by FTO/CZTS under front/back irradiation, and the photocurrent flows in the same direction in both cases. The band gap of CZTS is 1.45 eV. It is shown that high-quality CZTS thin films have been prepared via above analysis.
基金资助: the National High Technology Research and Development Program of China (863 program) (2015AA034201)
通讯作者:
王学进
E-mail: xjwang@cau.edu.cn
作者简介: SONG Si-yue，(1994—)，master, College of Science, China Agricultural University e-mail:
yue2605@163.com
引用本文:
宋思悦，刘旭炜，林鸿霄，王学进，何志巍. 电镀法在氧化铟锡上制备铜锌锡硫薄膜的光谱特征[J]. 光谱学与光谱分析, 2019, 39(09): 2940-2945.
SONG Si-yue, LIU Xu-wei, LIN Hong-xiao, WANG Xue-jin，HE Zhi-wei. Spectral Characterization of Electrodeposited Cu2ZnSnS4 Thin Films on Fluorine-Doped Tin Oxide. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2019, 39(09): 2940-2945.
[1] Jackson P, Hariskos D, Wuerz R, et al. Phys Status Solidi-R, 2014, 8: 219.
[2] Jackson P, Wuerz R, Hariskos D, et al. Phys Status Solidi-R，2016，10：583.
[3] Song X B, Ji X, Li M, Lin W D, et al. Int. J. Photoenergy, 2014.
[4] Katagiri H, Sasaguchi N, Hando S, et al. Sol. Energ. Mat. Sol. C, 1997, 49: 407.
[5] Clauwaert K, Binnemans K, Matthijs E, et al. Electrochimica Acta，2016，188：344.
[6] Li Y, Yuan T F, Jiang L X, et al. J. Mater. Sci-Mater. El., 2015, 26: 204.
[7] Chan C P, Lam H, Surya C. Sol. Energ. Mat. Sol. C, 2010, 94: 207.
[8] Katagiri H, Jimbo K, Maw W S, et al. Thin Solid Films, 200, 517: 2455.
[9] Shin B, Gunawan O, Zhu Y, et al. Prog Photovoltaics, 2013, 21: 72.
[10] Repins I, Beall C, Vora N, et al. Sol. Energ. Mat. Sol. C, 2012, 101: 154.
[11] Todorov T K, Reuter K B, Mitzi D B. Adv. Mater., 2010, 22: E156.
[12] Wang W, Winkler M T, Gunawan O, et al. Adv. Energy Mater, 2014, 4.
[13] Xu Dongmei, Pan Kun, Liu Xuwei, et al. Spectroscopy and Spectral Analysis，2016，36(10)：3197.
[14] Qu J Y, Guo Z F, Pan K, et al. Rare Metals，2017，36：729.
[15] Qu J Y, Guo Z F, Pan K, et al. Journal of Zhejiang University-Science A，2018，19：399.
[16] Guo L, Zhu Y, Gunawan O, et al. Prog Photovoltaics，2014，22：58.
[17] Tlemcani T S, El Moursli F C, Taibi M, et al. One Step Electrodeposited CZTS Thin Films: Preparation and Characterization, 2014.
[18] Ge J, Jiang J C, Yang P X, Peng C, et al. Sol. Energ. Mat. Sol. C, 2014, 125: 20.
[19] Araki H, Kubo Y, Jimbo K, et al. in: Sadewasser S, AbouRas D, Lake B, et al(Eds.). Physica Status Solidi C-Current Topics in Solid State Physics, 2009，6(5)：1266.
[20] Sarswat P K, Free M L. J. Electron. Mater. 2012, 41: 2210.
[21] Kondrotas R, JuKkenas R, Naujokaitis A, et al. Sol. Energ. Mat. Sol. C, 2015, 132: 21.
[22] Gougaud C, Rai D, Delbos S, et al. Journal of the Electrochemical Society, 2013, 160: D485.
[23] Guerrero-Lemus R, Vega R, Kim T, et al. Renewable and Sustainable Energy Reviews，2016，60：1533.
[24] Ge J, Chu J, Jiang J, et al. ACS Applied Materials & Interfaces, 2014, 6: 21118.
[25] Tapley A, Vaccarello D, Hedges J, Jia F, et al. Physical Chemistry Chemical Physics: PCCP，2013，15：1431.
[26] Fernandes P A, Salomé P M P, da Cunha A F. Thin Solid Films, 2009, 517: 2519.
[27] He J, Sun L, Chen S, et al. Journal of Alloys and Compounds，2012，511：129.
[28] Ozaki S, Hoshina K, Usami Y. Physica Status Solidi (C), 2015, 12: 717.
[29] Guc M, Levcenko S, Bodnar I V, et al. Scientific Reports，2016，6：19414.
