Cu掺杂ZnSe高效量子点的合成及其光学特性研究

doi:10.3724/SP.J.1077.2013.12184

无机材料学报 ›› 2013, Vol. 28 ›› Issue (2): 159-164.DOI: 10.3724/SP.J.1077.2013.12184

Cu掺杂ZnSe高效量子点的合成及其光学特性研究

郑金桔^1,2, 曹盛², 高凤梅², 尉国栋², 贾龙¹, 杨为佑²

(宁波工程学院1. 机械工程学院; 2. 材料工程研究所, 宁波 315016)

收稿日期:2012-03-22 修回日期:2012-06-01 出版日期:2013-02-10 网络出版日期:2013-01-23
作者简介:郑金桔(1980?), 女, 博士, 讲师. E-mail: zhengzhao2007@163.com
基金资助:
国家自然科学基金(61106066);浙江省杰出青年基金(R4100242);宁波市自然科学基金(2011A610094) National Natural Science Foundation of China (61106066);Zhejiang Provincial Science Foundation for Distinguished Young Scholars (R4100242);Ningbo Municipal Natural Science Foundation of China (2011A610094)

Synthesis of Effective and Qualified Cu-doped ZnSe Quantum Dots and Their Optical Properties

ZHENG Jin-Ju^1,2, CAO Sheng², GAO Feng-Mei², WEI Guo-Dong², JIA Long¹, YANG Wei-You²

(1. School of Mechanical Engineering, Ningbo University of Technology, Ningbo 315016, China; 2. Institute of Materials, Ningbo University of Technology, Ningbo 315016, China)

Received:2012-03-22 Revised:2012-06-01 Published:2013-02-10 Online:2013-01-23
About author:ZHENG Jin-Ju. E-mail: zhengzhao2007@163.com

摘要/Abstract

摘要：

采用生长掺杂方式制备了Cu掺杂ZnSe高效量子点, 探索了不同Zn、Se前驱体配比对ZnSe晶核以及ZnSe:Cu量子点质量的影响, 并研究了Cu离子掺杂过程中的光谱特征。研究表明, 进一步通过在表面掺杂的ZnSe:Cu量子点上同质包覆ZnSe壳层, 能够实现其发光效率和稳定性的有效提高; 采用配体交换能够实现ZnSe:Cu量子点由油溶性到水溶性的转变。这种新型的掺杂量子点有望替代传统含Cd量子点应用于环境友好型固体发光器件和生物标记。

关键词: ZnSe, 量子点, 生长掺杂, 光学特性

Abstract:

Effective Cu-doped ZnSe quantum dots (ZnSe:Cu d-dots) with high qualities were synthesized by a growth-doping strategy. The effect of the ratios of Zn to Se precursor within the raw materials on the quality of the ZnSe cores and ZnSe:Cu d-dots was studied. The photoluminescence (PL) properties of ZnSe:Cu d-dots in Cu doping process were investigated systematically. The results suggested that the optical performance and stability of the d-dots could be remarkably improved by further coated with a homogeneous ZnSe shell on the fabricated surface-doped ZnSe:Cu d-dots. In addition, the obtained ZnSe:Cu d-dots could be changed to be water-soluble by ligand exchange. It implied that these novel d-dots could be a promising candidate to substitute for the conventional quantum dots containing Cd elements, suggesting their potentially environment-friendly applications in the fields of solid state lighting and diagnostics.

Key words: ZnSe, quantum dots, growth-doping strategy, photoluminescence

中图分类号:

TM23

郑金桔, 曹盛, 高凤梅, 尉国栋, 贾龙, 杨为佑. Cu掺杂ZnSe高效量子点的合成及其光学特性研究[J]. 无机材料学报, 2013, 28(2): 159-164.

ZHENG Jin-Ju, CAO Sheng, GAO Feng-Mei, WEI Guo-Dong, JIA Long, YANG Wei-You. Synthesis of Effective and Qualified Cu-doped ZnSe Quantum Dots and Their Optical Properties[J]. Journal of Inorganic Materials, 2013, 28(2): 159-164.

图/表 5

图1 n(Zn):n(Se)=1:15时, ZnSe晶核在不同时间的吸收光谱(a), 在不同n(Zn):n(Se)下, ZnSe晶核生成5 min后的吸收((b)左)和发光光谱((b)右) 表1 不同n(Zn):n(Se)时, ZnSe晶核在不同时间的吸收峰位

Fig. 1 Temporal evolution of UV-Visible spectra of ZnSe QDs with n(Zn):n(Se)=1:15 (a), UV-Visible (left in (b)) and PL (b) of ZnSe QDs with various precursor ratios from 1:15 to 1:5, in which the QDs were taken from the three-neck flask at 5 min after the Se precursor injected

Table 1 Temporal evolution of the peak positions in UV-Visible spectra of ZnSe QDs with different n(Zn):n(Se)

n(Zn):n(Se)	0.5 min	2 min	5 min	10 min	20 min
1:5	378	388	391	390	388
1:10	375	384	385	386	388
1:15	370	386	386	388	387

图2 在掺Cu及包覆ZnSe壳层的过程中, ZnSe Core、ZnSe:Cu 40 min、ZnSe:Cu 80 min、ZnSe:Cu/ZnSe-1、ZnSe:Cu/ZnSe-2和ZnSe:Cu/ZnSe-3的吸收(a)及发光(b)光谱, 以及ZnSe:Cu 80 min样品在不同波长的光激发下的激发光谱(c)

Fig. 2 UV-visible (a) and PL (b) spectra of ZnSe core, ZnSe:Cu 40 min, ZnSe:Cu 80 min, ZnSe:Cu/ZnSe-1, ZnSe:Cu/ZnSe-2, ZnSe:Cu/ZnSe-3, and the PL spectra (c) of ZnSe:Cu 80 min excited at 320 nm, 335 nm and 350 nm, respectively

图3 ZnSe:Cu/ZnSe-3量子点的XRD图谱(插图是对应的TEM照片)

Fig. 3 Typical XRD pattern of as-synthesized ZnSe:Cu/ZnSe-3 QDs. The inset is a representative TEM image of this sample

图4 ZnSe:Cu量子点在配体交换前后的发光光谱及其量子效率

Fig. 4 PL spectra and corresponding PL QY of ZnSe:Cu QDs before and after thiol ligand exchange

参考文献 26

[1]	Acharya S, Pradhan N. Insertion/ejection of dopant ions in composition tunable semiconductor nanocrystals. J. Phys. Chem. C, 2011, 115(40): 19513-19519.
[2]	Erwin S C, Zu L, Haftel M I, et al. Doping semiconductor nanocrystals. Nature, 2005, 436(7047): 91-94.
[3]	Nag A, Chakraborty S, Sarma D. To dope Mn2+ in a semiconducting nanocrystal. J. Am. Chem. Soc, 2008, 130(32): 10605-10611.
[4]	Norris D, Yao N, harnock F, et al. High-quality manganese-doped ZnSe nanocrystals. Nano Lett., 2001, 1(1): 3-7.
[5]	Zheng J J, Yuan X Y, Ikezawa M Y, et al. Efficient photoluminescence of Mn2+ ions in MnS/ZnS Core/Shell quantum dots. J. Phys. Chem. C, 2009, 113(39): 16969-16974.
[6]	Zheng J, Ji W, Wang X.et al. Improved photoluminescence of MnS / ZnS core / shell nanocrystals by controlling diffusion of Mn ions into the ZnS shell. J. Phys. Chem. C, 2010, 114(36): 15331-15336.
[7]	Xie R G, Peng X G. Synthesis of Cu-doped InP nanocrystals (d-dots) with ZnSe diffusion barrier as efficient and color-tunable NIR emitters. J. Am. Chem. Soc., 2009, 131(30): 10645-10651.
[8]	Pradhan N, Battaglia D M, Liu Y, et al. Efficient, stable, small, and water-soluble doped ZnSe nanocrystal emitters as non-cadmium biomedical labels. Nano Lett., 2007, 7(2): 312-317.
[9]	Sarkar S, Bose R, Jana S, et al. Doped semiconductor nanocrystals and organic dyes: an efficient and greener FRET system. J. Phys. Chem. Lett., 2010, 1(3): 636-640.
[10]	Chen J, Zheng A, Gao Y, et al. Functionalized CdS quantum dots-based luminescence probe for detection of heavy and transition metal ions in aqueous solution. Spectrochim Acta Part A: Mol. Biomol. Spectrosc., 2008, 69(3): 1044-1052.
[11]	Pradhan N, Goorskey D, Thessing J, et al. An alternative of CdSe nanocrystal emitters: pure and tunable impurity emissions in ZnSe nanocrystals. J. Am. Chem. Soc., 2005, 127(50): 17586-17587.
[12]	Soo Y L, Ming Z H, Huang S W, et al. Local structures around Mn luminescent centers in Mn-doped nanocrystals of ZnS. Phys. Rev. B, 1994, 50(11): 7602-7607.
[13]	Nag A, Sapra S, Nagamani C, et al. A study of Mn2+ doping in CdS nanocrystals. Chem. Mater., 2007, 19(13): 3252-3259.
[14]	Pradhan N, Peng X. Efficient and color-tunable Mn-doped ZnSe nanocrystal emitters: control of optical performance via greener synthetic chemistry. J. Am. Chem. Soc., 2007, 129(11): 3339-3347.
[15]	Chang W L, Wei L, Zhen S M, et al. Posterior rotating rod reduction strategy for irreducible atlantoaxial subluxations with congenital odontoid aplasia. Spine, 2010, 35(23): 2064-2070.
[16]	Li Dan, Liu Junye, Meng Jiwu, et al. The PL decay of Cu2+ doped ZnS nanoparticle. Chin. J. Lumin. 1998, 19(1): 85-88.
[17]	Srivastava B B, Jana S, Pradhan N. Doping Cu in semiconductor nanocrystals: some old and some new physical insights. J. Am. Chem. Soc., 2011, 133(4): 1007-1015.
[18]	Quan Z W, Yang D M, Li C X, et al. Multicolor tuning of manganese- doped ZnS colloidal nanocrystals. Langmuir, 2009, 25(17): 1025-1026.
[19]	Cao L X, Zhang J H, Ren S L, et al. Luminescence enhancement of core-shell ZnS:Mn/ZnS nanoparticles. Appl. Phys. Lett., 2002, 80(23): 4300-4302.
[20]	Karar N, Chander H, Shivaprasad S M. Enhancement of luminescent properties of ZnS: Mn nanophosphors by controlled ZnO capping. Appl. Phys. Lett., 2004, 85(21): 5058-5060.
[21]	Yang H, Holloway P H. Efficient and photostable ZnS-passivated CdS:Mn luminescent nanocrystals. Adv. Funct. Mater., 2004, 14(2): 152-156.
[22]	Jana S, Srivastava B B, Acharya S, et al. Prevention of photooxidation in blue-green emitting Cu doped ZnSe nanocrystals. Chem. Comm., 2010, 46(16): 2853-2855.
[23]	Lippens P E, Lannoo M. Calculation of the band gap for small CdS and ZnS crystallites. Phys. Rev. B., 1989, 39(15): 10935-10942.
[24]	Suyver J, Beek, T, Wuister S.et al. Luminescence of nanocrystalline ZnSe:Cu. Appl. Phys. Lett., 2001, 79(25): 4222-4224.
[25]	Bruchez M, Moronne M, Gin, P, et al. Semiconductor nanocrystals as fluorescent biological labels. Science, 1998, 281(5385): 2013-2016.
[26]	Zheng J, Gao F, Wei G.et al. Enhanced photoluminescence of water- soluble Mn-doped ZnS quantum dots by thiol ligand exchange. Chem. Phys. Lett., 2012, 5(519/520): 73-77.

Cu掺杂ZnSe高效量子点的合成及其光学特性研究

Synthesis of Effective and Qualified Cu-doped ZnSe Quantum Dots and Their Optical Properties

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