硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

引用本文: 汤子龙, 李冬梅, 程经纬, 蒋洁如. 硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性[J]. 物理化学学报, 2013, 29(03): 653-659. doi: 10.3866/PKU.WHXB201212272 shu

Citation: TANG Zi-Long, LI Dong-Mei, CHENG Jing-Wei, JIANG Jie-Ru. Preparation and Fluorescence Properties of Aqueous Soluble Thiourea Modified ZnSe:Cu Quantum Dots[J]. Acta Physico-Chimica Sinica, 2013, 29(03): 653-659. doi: 10.3866/PKU.WHXB201212272 shu

硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

摘要:

以3-巯基丙酸为稳定剂在水相中合成了Cu掺杂的ZnSe量子点(QDs), 并利用硫脲(CH₄N₂S)对其进行表面修饰, 制备出核壳结构的ZnSe:Cu/ZnS 量子点. 制得的量子点呈闪锌矿结构, 尺寸约为5 nm, 有较好的分散性, 其荧光发射峰在460 nm左右. 经CH₄N₂S修饰后, 量子点表面形成了宽禁带的ZnS包覆层, 将电子和空穴限域在了ZnSe:Cu 核内, 减少了表面发生非辐射复合的载流子, 显著提高了量子点的荧光强度. 与Na₂S、硫代乙酰胺(TAA)等常用硫源相比, 以CH₄N₂S为硫源制得的ZnSe:Cu/ZnS 量子点壳层厚度可控, 表面钝化效果更好, 显示出更佳的荧光效率和稳定性. ZnSe:Cu/ZnS 量子点经过紫外线照射后消除了表面的悬空键, 进一步提高了其量子产率, 最终获到了具有较好荧光性质的ZnSe:Cu/ZnS量子点.

关键词:

English

Preparation and Fluorescence Properties of Aqueous Soluble Thiourea Modified ZnSe:Cu Quantum Dots

1.
College of Materials Science and Engineering, Shanghai University, Shanghai 200072, P.R. China
Received Date: 01 November 2012
Available Online: 25 February 2013

Abstract:

Aqueous phase Cu doped ZnSe (ZnSe:Cu) quantum dots (QDs) stabilized with mercaptopropionic acid were prepared, and thiourea was used as a surface modifier to obtain core-shell ZnSe:Cu/ZnS QDs. QDs had a sphalerite structure, were uniformly dispersed, had an average particle size of approximately 5 nm and an emission peak at around 460 nm. After thiourea modification, a wide band-gap ZnS shell was coated on the QDs to passivate the surface, reduce surface states, and significantly improve fluorescence intensity. Thiourea modified ZnSe:Cu/ZnS QDs exhibit better surface passivation, fluorescence efficiency, and stability than those of other surface modifiers like Na₂S and thioacetamide. Quantum yields were further improved after UV irradiation eliminated surface dangling bonds.

Key words:

1. [1]
  
  (1) Cooper, J. K.; Franco, A. M.; Gul, S.; Corrado, C.; Zhang, J. Z.Langmuir 2011, 27 (13), 8486. doi: 10.1021/la201273x
  (1) Cooper, J. K.; Franco, A. M.; Gul, S.; Corrado, C.; Zhang, J. Z.Langmuir 2011, 27 (13), 8486. doi: 10.1021/la201273x
2. [2]
  (2) Derfus, A. M.; Chan, C.W.; Bhatia, S. N. Nano Lett. 2004, 4 (1), 11218.(2) Derfus, A. M.; Chan, C.W.; Bhatia, S. N. Nano Lett. 2004, 4 (1), 11218.
3. [3]
  (3) Cho, S. J.; Maysinger, D.; Manasi, J. M.; Roder, B.; Hackbarth,S.;Winnik, F. M. Langmuir 2007, 23 (4), 1974. doi: 10.1021/la060093j(3) Cho, S. J.; Maysinger, D.; Manasi, J. M.; Roder, B.; Hackbarth,S.;Winnik, F. M. Langmuir 2007, 23 (4), 1974. doi: 10.1021/la060093j
4. [4]
  (4) Chen, L. L.; Jiang, Y.;Wang, C.; Liu, X. M.; Chen, Y.; Jie, J. S.J. Exp. Nanosci. 2010, 5 (2), 106. doi: 10.1080/17458080903314022(4) Chen, L. L.; Jiang, Y.;Wang, C.; Liu, X. M.; Chen, Y.; Jie, J. S.J. Exp. Nanosci. 2010, 5 (2), 106. doi: 10.1080/17458080903314022
5. [5]
  (5) Pol, S. V.; Pol, V. G.; Calderon-Moreno, J. M.; Cheylan, S.;Gedanken, A. Langmuir 2008, 24 (18), 104622.(5) Pol, S. V.; Pol, V. G.; Calderon-Moreno, J. M.; Cheylan, S.;Gedanken, A. Langmuir 2008, 24 (18), 104622.
6. [6]
  (6) Qin, H. Y.; Jian,W. P.; Zhang, Y. N.; Kim, T.; Jiang, Z. H.;Jiang, D.; Sun, D. H. Mater. Lett. 2012, 67 (1), 28. doi: 10.1016/j.matlet.2011.09.033(6) Qin, H. Y.; Jian,W. P.; Zhang, Y. N.; Kim, T.; Jiang, Z. H.;Jiang, D.; Sun, D. H. Mater. Lett. 2012, 67 (1), 28. doi: 10.1016/j.matlet.2011.09.033
7. [7]
  (7) Cai, Z. X.; Shi, B. Q.; Zhao, L.; Ma, M. H. Spectrochim. ActaPart A: Mol. Biomol. Spectrosc. 2012, 97, 909.(7) Cai, Z. X.; Shi, B. Q.; Zhao, L.; Ma, M. H. Spectrochim. ActaPart A: Mol. Biomol. Spectrosc. 2012, 97, 909.
8. [8]
  (8) Huang, L.; Han, H. Y. Mater. Lett. 2010, 64 (9), 1099. doi: 10.1016/j.matlet.2010.02.026(8) Huang, L.; Han, H. Y. Mater. Lett. 2010, 64 (9), 1099. doi: 10.1016/j.matlet.2010.02.026
9. [9]
  (9) Bhargava, R. N.; Gallagher, D. Phys. Rev. Lett. 1994, 72 (3),416. doi: 10.1103/PhysRevLett.72.416(9) Bhargava, R. N.; Gallagher, D. Phys. Rev. Lett. 1994, 72 (3),416. doi: 10.1103/PhysRevLett.72.416
10. [10]
  (10) Zhu, D.; Chen, Y.; Jiang, L. P.; Geng, J.; Zhang, J. R.; Zhu, J. J.Analytical Chemistry 2011, 83 (23), 9076. doi: 10.1021/ac202101u(10) Zhu, D.; Chen, Y.; Jiang, L. P.; Geng, J.; Zhang, J. R.; Zhu, J. J.Analytical Chemistry 2011, 83 (23), 9076. doi: 10.1021/ac202101u
11. [11]
  (11) Aboulaich, A.; Balan, L.; Ghanbaja, J.; Medjahdi, G.; Merlin,C.; Schneider, R. Chem. Mater. 2011, 23 (16), 3706. doi: 10.1021/cm2012928(11) Aboulaich, A.; Balan, L.; Ghanbaja, J.; Medjahdi, G.; Merlin,C.; Schneider, R. Chem. Mater. 2011, 23 (16), 3706. doi: 10.1021/cm2012928
12. [12]
  (12) Pradhan, N.; orskey, D.; Thessing, J.; Peng, X. J. Am. Chem.Soc. 2005, 127, 17586. doi: 10.1021/ja055557z(12) Pradhan, N.; orskey, D.; Thessing, J.; Peng, X. J. Am. Chem.Soc. 2005, 127, 17586. doi: 10.1021/ja055557z
13. [13]
  (13) Viswanatha, R.; Brovelli, S.; Pandey, A.; Crooker, S. A.;Klimov, V. Nano Lett. 2011, 11 (11), 4753. doi: 10.1021/nl202572c(13) Viswanatha, R.; Brovelli, S.; Pandey, A.; Crooker, S. A.;Klimov, V. Nano Lett. 2011, 11 (11), 4753. doi: 10.1021/nl202572c
14. [14]
  (14) Xi, B. J.; Xu, D. C.; Xiong, S. L.;Wang, C. M.; Feng, X. M.;Zhou, H. Y.; Qian, Y. T. J. Phys. Chem. C 2008, 112 (14), 5333.(14) Xi, B. J.; Xu, D. C.; Xiong, S. L.;Wang, C. M.; Feng, X. M.;Zhou, H. Y.; Qian, Y. T. J. Phys. Chem. C 2008, 112 (14), 5333.
15. [15]
  (15) Han, J.; Zhang, H.; Tang, Y.; Liu, Y.; Yao, X.; Yang, B. J. Phys.Chem. C 2009, 113, 7503.(15) Han, J.; Zhang, H.; Tang, Y.; Liu, Y.; Yao, X.; Yang, B. J. Phys.Chem. C 2009, 113, 7503.
16. [16]
  (16) Gao, X.;Wang, C.; Niu, L.; Su, X. G. J. Luminescence 2011,131 (7), 1300.(16) Gao, X.;Wang, C.; Niu, L.; Su, X. G. J. Luminescence 2011,131 (7), 1300.
17. [17]
  (17) Jiang, L.W.; Zhou, J.; Yang, X. Z.; Peng, X. N.; Jiang, H.;Zhuo, D. Q.; Chen, L. D.; Yu, X. F. Chem. Phys. Lett. 2011, 510 (3), 135. doi: 10.1016/j.cplett.2011.05.040(17) Jiang, L.W.; Zhou, J.; Yang, X. Z.; Peng, X. N.; Jiang, H.;Zhuo, D. Q.; Chen, L. D.; Yu, X. F. Chem. Phys. Lett. 2011, 510 (3), 135. doi: 10.1016/j.cplett.2011.05.040
18. [18]
  (18) Liu, Y. F.; Yu, J. S. J. Colloid Interface Sci. 2010, 351 (1), 1.doi: 10.1016/j.jcis.2010.07.047(18) Liu, Y. F.; Yu, J. S. J. Colloid Interface Sci. 2010, 351 (1), 1.doi: 10.1016/j.jcis.2010.07.047
19. [19]
  (19) Rawalekar, S.; Kaniyankandy, S.; Verma, S.; Ghosh, H. N.J. Phys. Chem. C 2010, 114 (3), 1460. doi: 10.1021/jp909118c(19) Rawalekar, S.; Kaniyankandy, S.; Verma, S.; Ghosh, H. N.J. Phys. Chem. C 2010, 114 (3), 1460. doi: 10.1021/jp909118c
20. [20]
  (20) Park, C.; Yoon, T. H. Colloid Surf. B- Biointerfaces 2010, 75 (2), 472. doi: 10.1016/j.colsurfb.2009.09.021(20) Park, C.; Yoon, T. H. Colloid Surf. B- Biointerfaces 2010, 75 (2), 472. doi: 10.1016/j.colsurfb.2009.09.021
21. [21]
  (21) Wang, C. L.; Xu, S. H.;Wang, Z. Y.; Cui, Y. P. J. Phys. Chem. C2011, 115 (38), 18486. doi: 10.1021/jp206137f(21) Wang, C. L.; Xu, S. H.;Wang, Z. Y.; Cui, Y. P. J. Phys. Chem. C2011, 115 (38), 18486. doi: 10.1021/jp206137f
22. [22]
  (22) Lin, Z. H.;Wang, M. Q.;Wei, L. Z.; Song, X. H.; Xue, Y. H.;Yao, X. J. Alloy. Compd. 2011, 509 (33), 8356. doi: 10.1016/j.jallcom.2011.03.070(22) Lin, Z. H.;Wang, M. Q.;Wei, L. Z.; Song, X. H.; Xue, Y. H.;Yao, X. J. Alloy. Compd. 2011, 509 (33), 8356. doi: 10.1016/j.jallcom.2011.03.070
23. [23]
  (23) Chen, H. S.; Lo, B.; Hwang, J. Y.; Chang, G. Y.; Chen, C. M.;Tasi, S. J.;Wang, S. J. J. Phys. Chem. B 2004, 108 (44), 17119.(23) Chen, H. S.; Lo, B.; Hwang, J. Y.; Chang, G. Y.; Chen, C. M.;Tasi, S. J.;Wang, S. J. J. Phys. Chem. B 2004, 108 (44), 17119.
24. [24]
  (24) Chen, X. X.; Liu, F. T.; Jiang, Q. H.; Sun, L.;Wang, Q. J. Inorg.Organomet. Polym. Mater. 2012, 22 (1), 6. doi: 10.1007/s10904-011-9606-3(24) Chen, X. X.; Liu, F. T.; Jiang, Q. H.; Sun, L.;Wang, Q. J. Inorg.Organomet. Polym. Mater. 2012, 22 (1), 6. doi: 10.1007/s10904-011-9606-3
25. [25]
  (25) Xu, S. H.;Wang, C. L.;Wang, Z. Y.; Zhang, H. S.; Yang, J.; Xu,Q. Y.; Shao, H. B.; Li, R. Q.; Lei,W.; Cui, Y. P. Nanotechnology2011, 22 (27), 275605.(25) Xu, S. H.;Wang, C. L.;Wang, Z. Y.; Zhang, H. S.; Yang, J.; Xu,Q. Y.; Shao, H. B.; Li, R. Q.; Lei,W.; Cui, Y. P. Nanotechnology2011, 22 (27), 275605.
26. [26]
  (26) Deng, Z. T.; Lie, F. L.; Shen, S. Y.; Ghosh, I.; Mansuripur, M.;Muscat, A. J. Langmuir 2009, 25 (1), 434. doi: 10.1021/la802294e(26) Deng, Z. T.; Lie, F. L.; Shen, S. Y.; Ghosh, I.; Mansuripur, M.;Muscat, A. J. Langmuir 2009, 25 (1), 434. doi: 10.1021/la802294e
27. [27]
  (27) Qian, H. F.; Qiu, X.; Li, L.; Ren, J. C. J. Phys. Chem. B 2006,110 (18), 9034. doi: 10.1021/jp0539324
  (27) Qian, H. F.; Qiu, X.; Li, L.; Ren, J. C. J. Phys. Chem. B 2006,110 (18), 9034. doi: 10.1021/jp0539324

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

English

Preparation and Fluorescence Properties of Aqueous Soluble Thiourea Modified ZnSe:Cu Quantum Dots

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硫脲修饰ZnSe:Cu量子点的水相合成及荧光特性

English

Preparation and Fluorescence Properties of Aqueous Soluble Thiourea Modified ZnSe:Cu Quantum Dots

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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