ZnSe/ZnS/L-Cys核壳结构量子点光声与表面光伏特性

林莹莹; 李葵英; 单青松; 尹华; 朱瑞苹

doi:10.7498/aps.65.038101

摘要

ZnSe量子点光电子特性的研究对于其微观电子结构探测和应用领域的扩展具有重要的意义. 本文结合表面光伏与光声技术以及激光Raman研究了不同回流温度下制备L-半胱氨酸(L-Cys)为配体核壳结构ZnSe量子点的微结构和光声与表面光伏特性. 结果发现, 具有n-型光伏特性的ZnSe 量子点在近紫外到可见光范围内展示出优良的表面光伏性质. 尤其在波长为350550 nm范围内光子能量绝大部分用于产生表面光伏效应, 而不是用于无辐射跃迁导致的晶格热振动, 同时证实了光声与表面光伏效应之间的能量互补关系. 实验指认ZnSe量子点在300350 nm短波区域出现的光声信号和在1120, 1340和1455 cm-1高频区域出现的Raman峰与配体L-Cys 的多声子振动模式密切相关. 实验结果表明, 随着回流温度的降低, ZnSe量子点的平均粒径有减小趋势, 这在改善样品的表面效应和小尺寸效应的同时, 有利于提高核壳结构ZnSe 量子点的光伏转换效率.

关键词:

Abstract

The study on photoelectronic characteristics of ZnSe quantum dots (QDs) is of significance for investigating its microelectronic structure and expanding its potential applications because ZnSe QD has low biologic toxicity. In the present paper, the surface photovoltaic and photoacoustic technologies, and laser Raman, X-ray diffraction, transmission electron microscopy and Foureier transform infrared spectroscopy spectrum are jointly used to probe the microstructures, the photoacoustic and surface photovoltaic characteristics of L-Cysteine-capped ZnSe QDs prepared by water-phase synthesis at different reflux temperatures. The results indicate that the ZnSe QDs with a mean grain size of about 3 nm has a core-shell ZnSe/ZnS/L-Cys structure, in which the sulfhydryl groups in ligand prefer reacting with Zn atom at the (220) face to form the ZnS shell layer between the core-ZnSe and ligand L-Cys. The results show that the QDs with n-type photovoltaic property display a wide range of surface photovoltaic response and weak photoacoustic signal upon the illumination of near ultraviolet to visible light as compared with others QDs with similar core-shell structures in II-VI group. Especially, the strong SPV response and the weak PA signal in a wavelength region of 350-550 nm imply that the photon energies in the range are almost all used to produce the surface photovoltaic (SPV) phenomenon instead of the thermal lattice vibration caused by non-radiative de-excitation process. This reveals the energy complementary relationship between the photoacoustic and the surface photovoltaic phenomena of the QDs. The PA signals appearing in a short wavelength range of 300-350 nm and the Raman peaks located in a high frequency ranges of 1120 cm-1, 1340 cm-1 and 1455 cm-1 are identified as relating closely to the multi-phonon vibration modes of ligand L-Cys. At low reflux temperature, the photoelectric threshold of the SPV response that relates to the core-ZnSe displays a red shift to a certain extent as compared with the bulk ZnSe. The narrowed bandgap may be attributed to quantum confinement effect of the QDs. In addition, the intensity of the SPV response that relates to the core-ZnSe gradually increases with the decrease of the reflux temperature. The results show that the above improved surface photovoltaic characteristics of the QDs may benefit from the reduced average grain size of the ZnSe QDs, thus causing its surface and small-size effects.

Keywords:

作者及机构信息

1.
燕山大学, 亚稳材料制备技术与科学国家重点实验室, 秦皇岛 066004

通信作者: 李葵英, kuiyingli@ysu.edu.cn

基金项目: 河北省自然科学基金(批准号: E2013203296)和河北省教育厅科研计划重点项目基金(批准号: ZH200814)资助的课题.

Authors and contacts

1.
State Key Laboratory of Metastable Materials Technology and Science, Yanshan University, Qinhuangdao 066004, China

Corresponding author: Li Kui-Ying, kuiyingli@ysu.edu.cn

Funds: Project supported by the Natural Science Foundation of Hebei Province, China (Grant No. E2013203296), and the Key Reserch Foundation of the Education Department of Hebei Province, China (Grant No. ZH200814).

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施引文献

[1]	Li K Y, Xue Z J 2014 Mater. Chem. Phys. 148 253
[2]	Feng B, Cao J, Yang J H, Yang S, Han D L 2014 Mater. Res. Bull. 60 794
[3]	Senthilkumar K, Kalaivani T, Kanagesan S, Balasubramanian V, Balakrishnan J 2013 J. Mater. Sci: Mater. Electron 24 692
[4]	Carbone L, Cozzoli P D 2010 Nano Today 5 449
[5]	Goswami B, Pal S, Ghosh C, Sarkar P 2009 J. Phys. Chem. C 113 6439
[6]	Colibaba G, Caraman M, Evtodiev I, Evtodiev S, Goncearenco E, Nedeoglo D, Nedeoglo N 2014 J. Lumin. 145 237
[7]	Zhang L, Yang H, Yu J, Shao F, Li L, Zhang F, Zhao H 2009 J. Phys. Chem. C 113 5434
[8]	Pardo-Gonzalez A P, Castro-Lora H G, Lpez-Carreo L D, Martnez H M, Salcedo N J T 2014 J. Phys. Chem. Solids 75 713
[9]	Archana J, Navaneethan M, Hayakawa Y, Ponnusamy S, Muthamizhchelvan C 2012 Mater. Res. Bull. 47 1892
[10]	Weaver A L, Gamelin D R 2012 J. Am. Chem. Soc. 134 6819
[11]	Wang X, Zhu J, Zhang Y, Jiang J, Wei S 2010 Appl. Phys. A 99 651
[12]	Zhu J, Koltypin Y, Gedanken A 2000 Chem. Mater. 12 73
[13]	Shakir M, Kushwaha S K, Maurya K K, Bhagavannarayana G 2009 Solid State Commun. 149 2047
[14]	Yang L, Xie R, Liu L, Xiao D, Zhu J 2011 J. Phys. Chem. C 115 19507
[15]	Yang Y J, Xiang B J 2005 J. Cryst. Growth 284 453
[16]	Peng X G, Manna L, Yang W D, Wickham J, Scher E, Kadavanich A, Allvisatos A P 2000 Nature 404 59
[17]	Bruchez M, Moronne M, Gin P, Weiss S, Alivisatos A P 1998 Science281 2013
[18]	An H Z, Zhao Q, Du W M 2004 Chin. Phys. B 13 1753
[19]	Zafar M, Ahmed S, Shakil M, Choudhary M A, Mahmood K 2015 Chin. Phys. B 24 0761061
[20]	Hines M A, Guyot-Sionnest P 1998 J. Phys. Chem. B 102 3655
[21]	Xiong S, Huang S, Tang A, Teng F 2007 Mater. Lett. 61 5091
[22]	Lu L W, Wang Z G 2002 Acta Phya. Sin. 51 310 (in Chinese) [卢励吾, 王占国 2002 物理学报 51 310]
[23]	Qu J R, Zhen J B, Wang C F, Wu G R, Hao J 2013 Acta Phys. Sin. 62 0788021 (in Chinese) [屈俊荣, 郑建邦, 王春锋, 吴广荣, 郝娟 2013 物理学报 62 0788021]
[24]	Xia M L, Liu C, Zhao Z Y, Ai B, Yin Q Y, Xie J, Han J J, Zhao X J 2015 J. Non-Cryst. Solids 429 79
[25]	Murase N, Gao M Y 2004 Mater. Lett. 58 3898
[26]	Liu B T, Yu H Y, Wang Y, Peng L G, Han T, Tian L L, Yan L T 2015 J. Alloy. Compd. 640 246
[27]	Xue Z J, Li K Y, Sun Z P 2013 Acta Phys. Sin. 62 066801 (in Chinese) [薛振杰, 李葵英, 孙振平 2013 物理学报 62 066801]
[28]	Li K Y, Shan Q S, Zhu R P, Yin H, Lin Y Y, Wang L Q 2015 Nanoscale 7 7906
[29]	Rosencwaig A, Gersho A 1976 J. Appl. Phys. 47 64
[30]	Yin Q R, Wang T, Qian M L 1999 Photoacoustic and Photo-Thermal Technology and Applications (Beijing: Science Press) pp18-34 (in Chinese) [殷庆瑞, 王通, 钱梦騄 1999 光声光热技术及其应用 (北京:科学出版社) 第1834页]
[31]	Rosencwaig A (translated by Wang Y J, Zhang S Y, Lu Z G) 1986 Photoacoustic and Photoacoustic Spectroscopy (Beijing: Science Press) pp94-105 (in Chinese) [罗森威格 A (王耀俊, 张淑仪, 卢宗桂译) 1986 光声学和光声谱学 (北京:科学出版社) 第94105页]
[32]	Reiss P, Carayon S, Bleuse J, Pron A 2003 Synthetic Met. 139 649
[33]	Kronik L, Shapira Y 1999 Surf. Sci. Rep. 37 1
[34]	Li K Y, Liu T, Zhou B J, Wei S L, Yang W Y 2010 Acta Phys. -Chim. Sin. 26 403 (in Chinese) [李葵英, 刘通, 周冰晶, 魏赛玲, 杨伟勇 2010 物理化学学报 26 403]
[35]	Li K Y, Zhang H, Yang W Y, Wei S L, Wang D Y 2010 Mater. Chem. Phys. 123 98
[36]	Li K Y, Ding Y Y, Guo J, Wang D Y 2008 Mater. Chem. Phys. 112 1001
[37]	Li K Y, Song G J, Zhang J, Wang C M, Guo B 2011 J. Photoch. Photobio. A 218 213
[38]	Feng B, Yang J H, Cao J, Yang L L, Gao M, Wei M B, Liu Y, Song H 2013 Mater. Res. Bull. 48 1040
[39]	Arivazhagan V, Manonmani P M, Rajesh S 2013 J. Alloy. Compd. 577 431
[40]	Zhou X, Zeng X H, Yan X Q, Xia W W, Zhou Y X, Shen X S 2014 Mater. Res. Bull. 59 25
[41]	Zeng X H, Zhang W, Cui J Y, Zhou M, Chen H T 2014 Mater. Res. Bull. 50 359
[42]	Trajić J, Kostić R, Romčević N, Romčević M, Mitrić M, Lazović V, Balaž P, Stojanović 2014 J. Alloy. Compd. 637 401
[43]	Daz-Reyes J, Castillo-Ojeda R S, Snchez-Espndola R, Galvn-Arellano M, Zaca-Morn O 2014 Curr. Appl. Phys. 15 103
[44]	Sotillo B, Fernndez P, Piqueras J 2013 J. Alloy. Compd. 563 113
[45]	Peng J J, Liu S P, Wang L, Liu Z W, He Y Q 2009 J. Colloid Interface Sci. 338 578
[46]	Xue X H, Pan J, Xie H M, Wang J H, Zhang S 2009 Talanta 77 1808
[47]	Lu G W, An H Z, Chen Y, Huang J H, Zhang H Z, Xiang B, Zhao Q, Yu D P, Du W M 2005 J. Cryst. Growth 274 530
[48]	Freitas-Neto E S, Silva A C A, Silva S W, Morais P C, Gmez J A, Baffa O, Dantas N O 2013 J. Raman Spectrosc. 44 1022
[49]	Kim K, Lee Y M, Lee H B, Park Y, Bae T Y, Jung Y M, Choi C H, Shin K S 2010 J. Raman Spectrosc. 41 187
[50]	Fu X G, An H Z, Du W M 2005 Mater. Lett. 59 1484
[51]	Lee H, Kim M S, Suh S W 1991 J. Raman Spectrosc. 22 91

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