溶剂热法制备Cu2ZnSnS4粉末及其表征

doi:10.3724/SP.J.1077.20143.13418

无机材料学报 ›› 2014, Vol. 29 ›› Issue (5): 487-492.DOI: 10.3724/SP.J.1077.20143.13418

溶剂热法制备Cu₂ZnSnS₄粉末及其表征

周超, 冯清, 高延敏

(江苏科技大学材料科学与工程学院, 镇江212003)

收稿日期:2013-08-13 修回日期:2013-10-16 出版日期:2014-05-20 网络出版日期:2014-04-24
作者简介:周超(1988–), 男, 硕士研究生. E-mail: chaozhou0721@126.com
基金资助:
国家自然科学基金(51075197); 江苏科技大学研究生创新基金(YCX11S-24)

Synthesis and Characterization of Cu₂ZnSnS₄ (CZTS) Powders by Solvothermal Method

ZHOU Chao, FENG Qing, GAO Yan-Min

(School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China)

Received:2013-08-13 Revised:2013-10-16 Published:2014-05-20 Online:2014-04-24
About author:ZHOU Chao. E-mail: chaozhou0721@126.com
Supported by:
National Natural Science Foundation of China (51075197); Graduate Student Innovation Program of Jiangsu University of Science and Technology(YCX11S-24)

摘要/Abstract

摘要： 采用溶剂热法, 以CuCl₂·2H₂O、Zn(Ac)₂·2H₂O、SnCl₄·5H₂O作金属源, 硫脲作硫源, 乙二醇作溶剂, PVP作表面活性剂, 制备了Cu₂ZnSnS₄(CZTS)粉末。利用XRD、SEM、Raman、TEM、EDS、UV-Vis吸收光谱探讨了反应温度和反应时间对制备CZTS粉末的相结构、成分、形貌以及光学性能的影响。结果表明: 反应温度和反应时间对CZTS粉末的颗粒形貌和光学性能影响较大, 最佳合成温度为230℃, 反应时间24 h。该条件下生成的CZTS粉末相较为纯净、结晶完全, 形貌为表面嵌有薄片的微球, 各元素原子比接近化学计量比, 光学带隙为1.52 eV, 与太阳能电池所需的最佳带隙接近。并对其形成机理进行了初步探讨。

关键词: Cu₂ZnSnS₄, 溶剂热法, 反应时间, 反应温度

Abstract: Cu₂ZnSnS₄(CZTS) powderss were synthesized by a facile solvothermal method in ethylene glycol with the presense of polyvinylpyrrolidone(PVP), using CuCl₂·2H₂O, Zn(Ac)₂·2H₂O and SnCl₄·5H₂O as metal precursor, thiourea as sulfur source. The effects of reaction temperature and time on crystal structure, composition, morphology and absorption spectra of CZTS powders were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectroscope, transmission electron microscope (TEM), energy dispersive X-ray spectroscope (EDS) and UV-Vis spectroscope. The results reveal that the reaction temperature and reaction time have a certain influence on the morphology and optical properties of the as-synthesized CZTS powders. The optimum solvothermal reaction condition is 230℃, 24 h. Under this condition, crystallization of the synthesized CZTS powders is pure and complete, and the particles are uniform and monodispersed sheets-contanimg microspheres. Elements’ atomic ratio of CZTS powder is close to stoichiometric coefficient and band gap of the products is about 1.52 eV, which is close to the optimum value for solar photoelectric conversion. In addition, a possible reaction mechanism of CZTS particle preparation is also inferred.

Key words: Cu₂ZnSnS₄, solvothermal method, reaction time, reaction temperature

中图分类号:

TM651

周超, 冯清, 高延敏. 溶剂热法制备Cu₂ZnSnS₄粉末及其表征[J]. 无机材料学报, 2014, 29(5): 487-492.

ZHOU Chao, FENG Qing, GAO Yan-Min. Synthesis and Characterization of Cu₂ZnSnS₄ (CZTS) Powders by Solvothermal Method[J]. Journal of Inorganic Materials, 2014, 29(5): 487-492.

参考文献

[1] PHILIP J, DIMITRIOS H, ERWIN L, et al. New world record efficiency for Cu(In, Ga)Se2 thin-film solar cells beyond 20%. Prog. Photovolt: Res Appl., 2011, 19(7): 894–897.

[2] NITSCHE R, SARGENT D F, WILD P. Crystal growth of quaternary 122464 chalcogenides by iodine vapor transport. J. Cryst. Growth, 1967, 1(1): 52–53.

[3] ITO K, NAKAZAWA T. Electrical and optical properties of stannite-type quaternary semiconductor thin films. Jpn. J. Appl. Phys., 1988, 27: 2094–2097.

[4] KATAGIRI H, SASAGUCHI N, HANDO S, et al. Preparation and evaluation of Cu2ZnSnS4 thin films by sulfurization of E-B evaporation precursors. Sol. Energy Mat. Sol. C, 1997, 49(1–4): 407–414.

[5] KATAGIRI H, JIMBO K, MAW W S, et al. Development of CZTS-based thin film solar cells. Thin Solid Films, 2009, 517(7): 2455–2460.

[6] RAMASAMY K, MOHAMMAD A M, PAUL O. Routes to copper zinc tin sulfide Cu2ZnSnS4 a potential material for solar cells. Chem. Commun., 2012, 48: 5703–5714.

[7] BARKHOUSE D A R, GUNAWAN O, GOKMEN T, et al. Device characteristics of a 10.1% hydrazine-processed Cu2ZnSn(Se,S)4 solar cell. Prog. Photovolt., 2012, 20(1): 6–11.

[8] TODOROV T K,TANG J, BAG S, et al. Beyond 11% efficiency: characteristics of state-of-the-art Cu2ZnSn(S,Se)4 solar cells. Adv. Energy Mater., 2012, 3(1): 34–38.

[9] SHOCKLEY W, QUEISSER H J. Detailed balance limit of efficiency of p-n junction solar cells. J. Appl. Phys., 1961, 32(3): 510–519.

[10] SEOL J S, LEE S Y, LEE J C, et al. Electrical and optical properties of Cu2ZnSnS4 thin films prepared by rf magnetron sputtering process. Sol. Energy Mat. Sol. C, 2003, 75(1/2): 155–162.

[11] ZHOU Z H, WANG Y Y, XU D, et al. Fabrication of Cu2ZnSnS4 screen printed layers for solar cells. Sol. Energy Mat. Sol. C, 2010, 94(12): 2042–2045.

[12] SCRAGG J J, DALE P J, PETER L M. Towards sustainable materials for solar energy conversion:preparation and photoelectrochemical characterization of Cu2ZnSnS4. Electrochem. Commun., 2008, 10(4): 639–642.

[1]	孙顶, 丁彦妍, 孔令炜, 张玉红, 郭秀娟, 魏立明, 张力, 张立新. Mg掺杂Cu₂ZnSnS₄的第一性原理研究[J]. 无机材料学报, 2020, 35(11): 1290-1294.
[2]	陈传杰, 魏李庚, 吴月, 胡成沛, 胡元聪, 蒋久信. 醇钙法和醇-水二元溶剂法制备亚稳态球霰石相CaCO₃[J]. 无机材料学报, 2019, 34(7): 755-760.
[3]	柯剑煌, 谢凯, 韩喻, 孙巍巍, 罗世强, 刘锦锋. 基于不同共溶剂体系对于高电压正极材料LiCoPO₄的形貌控制[J]. 无机材料学报, 2019, 34(6): 618-624.
[4]	隋丽丽,王润,赵丹,申书昌,孙立,徐英明,程晓丽,霍丽华. 多级结构α-MoO₃空心微球的构筑及其对有机染料的吸附性能[J]. 无机材料学报, 2019, 34(2): 193-200.
[5]	张翊青, 刘梨, 张淑娟, 万正睿, 刘红英, 周立群. NH₂-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢[J]. 无机材料学报, 2019, 34(12): 1316-1324.
[6]	张鹏飞, 闫淑芳, 陈伟东, 李世江, 赵丽, 王宏兴. 铝酸盐体系下反应时间对ZrH_1.8表面阻氢膜层制备的影响[J]. 无机材料学报, 2018, 33(3): 284-288.
[7]	武萱蓉, 杨巧珍, 赵永祥, 路艳罗. ZnS微球的水热/溶剂热法合成及其光催化性能研究[J]. 无机材料学报, 2016, 31(5): 473-478.
[8]	李斌, 李英莲, 莫淑一, 陈明光, 王东生, 龙飞. In₂Se₃/CuSe核壳结构微纳粉的合成及其喷涂热处理制备CuInSe₂薄膜[J]. 无机材料学报, 2016, 31(10): 1135-1140.
[9]	卢青, 华罗光, 陈亦琳, 高碧芬, 林碧洲. 氧缺陷Bi₂WO_6-_x可见光催化剂的制备和性能[J]. 无机材料学报, 2015, 30(4): 413-419.
[10]	王琨, 康利涛, 陈石, 董丽, 梁伟, 高峰. 水热法制备(NH₄)_xWO_3-y和WO₃·1/3H₂O: 反应温度对产物物相、微结构和光学性能的影响[J]. 无机材料学报, 2014, 29(5): 550-556.
[11]	李跃军, 曹铁平, 邵长路, 王长华. γ-Bi₂O₃/TiO₂复合纤维的制备及光催化性能[J]. 无机材料学报, 2012, 27(7): 687-692.
[12]	朱振峰, 王小枫, 刘辉, 刘佃光. 准单分散SnO₂微球的微波溶剂热合成[J]. 无机材料学报, 2012, 27(3): 311-316.
[13]	罗鹏, 赵丽霞, 徐键. Cu₂ZnSnS₄纳米颗粒及其薄膜的制备与表征[J]. 无机材料学报, 2012, 27(1): 79-82.
[14]	李天保, 梁建, 许并社, 王进. 硼酸镁一维纳米材料的制备和表征[J]. 无机材料学报, 2010, 25(9): 947-951.
[15]	朱孔军, 苏礼奎, 季宏丽, 裘进浩, 柏林, 柳泽河道, 梶芳浩二. 水热-溶剂热法合成(K, Na)NbO₃无铅压电陶瓷及其性能测试[J]. 无机材料学报, 2010, 25(11): 1159-1163.

溶剂热法制备Cu₂ZnSnS₄粉末及其表征

Synthesis and Characterization of Cu₂ZnSnS₄ (CZTS) Powders by Solvothermal Method

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价