Hydrothermal synthesis of K, Na doped Cu-S nanocrystalline and effect of doping on crystal structure and performance

Wan Bu-Yong; Yuan Jin-She; Feng Qing; Wang Ao

doi:10.7498/aps.62.178102

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:

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).

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[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
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Cited By

[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 物理学报 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 物理学报 60 027802]
[3]	Xin M, Cao W H 2010 Acta Phys. Sin. 59 5833 (in Chinese) [新梅, 曹望和 2010 物理学报 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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Vol. 62, Issue 17 - 2013-09-05

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