K,Na掺杂Cu-S纳米晶的水热合成及对结构、性能的影响

万步勇; 苑进社; 冯庆; 王奥

doi:10.7498/aps.62.178102

摘要

利用水热合成技术, 分别以CuCl22H2O, 硫粉为铜源和硫源, 以KOH或NaOH为矿化剂, 成功合成了Cu2S纳米晶体和碱金属离子掺杂的KCu7S4纳米线和NaCu5S3 微纳米球. 通过X射线衍射(XRD)、电子能谱(EDS)、扫描电镜(SEM)、透射电镜(TEM)和高分辨率透射电镜 (HRTEM) 对产物的结构和形貌进行了表征和分析. 结果显示: KOH含量低于1g或NaOH低于2g时, 产物为斜方辉铜矿Cu2S; 高碱含量 (不低于3g) 时, K或Na离子成功掺入产物结构中, K掺杂产物为纯净的四方相KCu7S4, 单晶结构, 尺寸均匀, 长度可达几十微米的纳米线; Na掺杂未改变产物的形貌, 形成六方晶系结构的NaCu5S3. 产物的形成和生长与反应温度、反应时间和矿化剂密切相关. 并讨论了Cu2S纳米晶及其掺杂纳米晶的形成机理及掺杂机理. 最后研究了碱金属离子掺杂对产物的光学性能的影响, 漫反射光谱显示Cu2S, KCu7S4和NaCu5S3纳米晶的光学带隙分别为1.21eV, 0.49eV和0.42eV, K+和Na+的掺杂, 极大的改变了产物的光学特性.

关键词:

KCu7S4 /
NaCu5S3 /
水热法 /
掺杂

Abstract

Cuprous sulfide (Cu2S) nanocrystals and K or Na doped KCu7S4 nanowires and NaCu5S3 micro-nanospheres have been synthesized successfully by using a simple hydrothermal method, using KOH or NaOH as mineralizing agent, CuCl22H2O and S powders as copper and Sulfur sources, respectively. The structure and morphology are characterized and analyzed by X-ray diffraction (XRD), energy dispersive X-ray spectrum (EDS), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The results reveal that under conditions that the amount of KOH is below 1g or the amount of NaOH below 2 g, the product is of the orthorhombic chalcocite Cu2S, while with high alkali amount (no less than 3 g), K+ or Na+ is successfully incorporated into the Cu-S structure; KCu7S4 has the pure tetragonal single crystal structure, and its uniform nanowires can be up to several tens of micrometers in length. Na doping has no effect on the morphology of the product, which forms the hexagonal NaCu5S3. The formation and growth of the product are closely related to the reaction temperature, reaction time and mineralizing agent. And, the formation and doping mechanisms are discussed. Finally, the influence of the alkali metal ion doping on the optical properties of the product is investigated. The diffuse reflectance spectra demonstrate that the optical band gaps of Cu2S, NaCu5S3 and KCu7S4 nanocrystallines is 1.21, 0.49, 0.42 eV, respectively. And K+ or Na+ doping greatly affects the optical characteristics.

Keywords:

KCu7S4 /
NaCu5S3 /
hydrothermal method /
doping

作者及机构信息

1.
重庆师范大学物理与电子工程学院, 重庆 400047;

2.
重庆市光电功能材料重点实验室, 重庆 400047

基金项目: 国家自然科学基金(批准号: 61106129, 61274128);重庆市自然科学基金(批准号: cstc2012jjA50024)和重庆市教委科技项目(批准号: KJ130603)资助的课题.

Authors and contacts

1.
College of Physics and Electronic Engineering, Chongqing Normal University, Chongqing 400047, China;

2.
Key Laboratory of Optoelectronic Functional Materials of Chongqing, Chongqing 400047, China

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 61106129, 61274128), the Natural Science Foundation of Chongqing, China (Grant No. cstc2012jjA50024), and the Science and Technology Research Project of Chongqing Municipal Education Commission of China (Grant No. KJ130603).

参考文献

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施引文献

[1]	Liu J, Zhou W C, Zhang J F 2012 Acta Phys. Sin. 61 206101 (in Chinese) [刘军, 周伟昌, 张建福 2012 61 206101]
[2]	Yang Y P, Feng S, Feng H, Pan X C, Wang Y Q, Wang W Z 2011 Acta Phys. Sin. 60 027802 (in Chinese) [杨玉平, 冯帅, 冯辉, 潘学聪, 王义全, 王文忠 2011 60 027802]
[3]	Xin M, Cao W H 2010 Acta Phys. Sin. 59 5833 (in Chinese) [新梅, 曹望和 2010 59 5833]
[4]	Kim H S, Sung T K, Jang S Y, Myung Y, Cho Y J, Lee C W, Park J, Ahn J P, Kim J G, Kim Y 2011 Cryst. Eng. Comm. 13 2091
[5]	Peng M, Ma L L, Zhang Y G, Tan M, Wang J B, Yu Y 2009 Mater. Res. Bull. 44 1834
[6]	Zhao F, Chen X, Xu N, Lu P 2006 J. Phys. Chem. Solids 67 1786
[7]	Shi J Fu, Fan Y X, Xue Q, Xu G, Chen L H 2012 Acta Phys. Chim．Sin. 28 857 (in Chinese) [史继富, 樊晔, 徐雪青, 徐刚, 陈丽华 2012 物理化学学报 28 857]
[8]	Tang A W, Qu S C, Li K, Hou Y B, Teng F, Cao J, Wang Y S, Wang Z G 2010 Nanotechnology 21 285602
[9]	Nayak A, Ohno T, Tsuruoka T, Terabe K, Hasegawa T, Gimzewski J K, Aono M 2012 Adv. Funct. Mater. 22 3606
[10]	Boller H 2007 J. Alloys Compd. 442 3
[11]	Kuo Y K, Skove M J, Verebelyi D T, Li H, Mackay R, Hwu S J, Whangbo M H, Brill J W 1997 Phys. Rev. B 57 3315
[12]	Brown D B, Zubieta J A, Vella P A, Wrobleski J T, Watt T, Hatfield W E, Day P 1980 Inorg. Chem. 19 1945
[13]	Whangbo M H, Canadell E 1992 Solid State Commun. 81 895
[14]	Noren L, Berger R, Lidin S, Eriksson L, Huster J 1998 J. Alloys Compd. 281 186
[15]	Hwu S J, Li H, Mackay R, Kuo Y K, Skove M J, Mahapatro M, Bucher C K, Halladay J P, Hayes M W 1998 Chem. Mater. 10 6
[16]	Huang L, Liu J, Zuo Z, Liu H, Liu D, Wang J, Boughton R I 2010 J. Alloys Compd. 507 429
[17]	Effenberger H, Pertlik F 1985 Monatsh. Chem. 116 921
[18]	Liu B, Zeng H C 2005 Small 1 566
[19]	Purdy A P 1998 Chem. Mater. 10 692
[20]	Peng M, Ma L L, Zhang Y G, Tan M, Wang J B, Yu Y 2009 Mater. Res. Bull. 44 1834
[21]	Yuan M, Mitzi D B 2009 J. Chem. Soc. Dalton Trans. 31 6078
[22]	Ohtani T, Ogura J, Sakai M, Sano Y 1991 Solid State Commun. 78 913
[23]	Effenberger H, Pertlik F 1985 Monatshefte fr Chemie 116 921
[24]	Li J, Chen Z, Wang X X, Proserpio D M 1997 J. Alloys Compd. 262-263 28
[25]	Yang M, Yang X, Huai L, Liu W 2008 Appl. Surf. Sci. 255 1750
[26]	Bekenstein Y, Vinokurov K, Banin U, Millo O 2012 Nanotechnology 23 505710
[27]	Sun D M, Wu Q S, Ding Y P 2004 J. Inorg. Mater. 19 487 (in Chinese) [孙冬梅, 吴庆生, 丁亚平 2004 无机材料学报 19 487]

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