基于聚合物多齿配体的高性能CdTe量子点的微波水相合成

doi:10.3866/PKU.WHXB201403131

物理化学学报 >> 2014, Vol. 30 >> Issue (5): 994-1000.doi: 10.3866/PKU.WHXB201403131

材料物理化学上一篇

基于聚合物多齿配体的高性能CdTe量子点的微波水相合成

宇文力辉, 薛冰, 汪联辉

南京邮电大学信息材料与纳米技术研究院, 南京210023

收稿日期:2013-12-20 修回日期:2014-03-12 发布日期:2014-04-25
通讯作者: 汪联辉 E-mail:iamlhwang@njupt.edu.cn
基金资助:
国家重大科学研究计划（2012CB933301），国家自然科学基金（21204038，81273409），教育部长江学者和创新团队发展计划（IRT1148），教育部博士点基金（20123223110007），江苏省自然科学基金（BK20130862），江苏省高校自然科学基金（13KJB150029），东南大学生物电子学国家重点实验室和南京大学配位化学重点实验室开放研究基金资助

Synthesis of High Quality CdTe Quantum Dots in Aqueous Solution Using Multidentate Polymer Ligands under Microwave Irradiation

YUWEN Li-Hui, XUE Bing, WANG Lian-Hui

Institute of Advanced Materials, Nanjing University of Posts and Telecommunications, Nanjing 210023, P. R. China

Received:2013-12-20 Revised:2014-03-12 Published:2014-04-25
Contact: WANG Lian-Hui E-mail:iamlhwang@njupt.edu.cn
Supported by:
The project was supported by the Major Research Plan of China (2012CB933301), National Natural Science Foundation of China (21204038, 81273409), PCSIRT of the Ministry of Education of China (IRT1148), Ph.D. Programs Foundation of Ministry of Education of China (20123223110007), Natural Science Foundation of Jiangsu Province, China (BK20130862), Natural Science Foundation of Universities from Jiangsu Province, China (13KJB150029), Open Research Fund of State Key Laboratory of Bioelectronics, Southeast University, China and Open Research Fund of State Key Laboratory of Coordination Chemistry, Nanjing University, China.

摘要/Abstract

摘要：

针对当前水相合成的量子点（QDs）光性能与稳定性等方面存在的不足，发展了基于聚合物多齿配体的水相制备策略. 利用巯基修饰的聚丙烯酸（PAA-SH）作为多齿配体代替常用的巯基丙酸等单齿配体，结合微波辅助加热制备了CdTe 量子点，研究了多齿配体对量子点的生长机制与荧光性能的影响. 以PAA-SH为配体制备的CdTe量子点荧光性能优异（荧光量子效率（PLQY）可达75%），流体力学直径较小（~10 nm），稳定性也有明显提高. 基于聚合物多齿配体的量子点制备技术有助于实现生物医学研究中急需的兼具高亮度、高稳定性、小尺寸等特征的高性能量子点生物探针的制备.

关键词: 多齿配体, 高性能, 量子点, 微波水相合成

Abstract:

Quantum dots (QDs) have recently attracted considerable attention due to their unique optical properties and potential applications in biomedicine and optoelectronics. Although the organic synthesis of QDs is popular, aqueous synthesis is also very attractive not only for its low cost, low toxicity, and low reaction temperature, but also because the as-prepared QDs can be used directly for bio-related applications without the requirement for complicated surface modification processes. However, the monodentate ligands typically used for aqueous synthesis have limited binding ability, which can lead to weak colloidal stability and low photoluminescence. To solve these problems, we explored the use of multidentate thiol-containing polymer (PAASH) as a ligand to synthesize CdTe QDs and studied the influence of the ligand on the growth mechanism and photoluminescent properties of the QDs. PAA-SH was synthesized by conjugating cysteamine to poly(acrylic acid) (PAA) in the presence of dicyclohexylcarbodiimide. CdTe QDs of different sizes were prepared in aqueous solutions using PAA-SH as a ligand under microwave irradiation. The resulting PAA-SH-capped CdTe QDs show high photoluminescence quantum yield (PLQY) (up to 75%) without CdS shell coating, which is much better than the CdTe QDs synthesized using monodentate ligands. Furthermore, the hydrodynamic diameter of the PAA-SH-coated CdTe QDs is about 10 nm, and therefore much smaller than the polymer or SiO₂ encapsulated QDs. In contrast, benefitting from cooperative binding effect of the multiple thiol groups and the high free energy for the ligand detachment from the QDs surface, PAA-SH-CdTe QDs show high storage stability.

Key words: Multidentate ligand, High quality, Quantum dots, Microwave aqueous synthesis

MSC2000:

O649

宇文力辉, 薛冰, 汪联辉. 基于聚合物多齿配体的高性能CdTe量子点的微波水相合成[J]. 物理化学学报, 2014, 30(5): 994-1000.

YUWEN Li-Hui, XUE Bing, WANG Lian-Hui. Synthesis of High Quality CdTe Quantum Dots in Aqueous Solution Using Multidentate Polymer Ligands under Microwave Irradiation[J]. Acta Phys. -Chim. Sin., 2014, 30(5): 994-1000.

参考文献

(1) Alivisatos, A. P. Science 1996, 271, 933. doi: 10.1126/science.271.5251.933
(2) Michalet, X.; Pinaud, F. F.; Bentolila, L. A.; Tsay, J. M.; Doose, S.; Li, J. J.; Sundaresan, G.; Wu, A. M.; Gambhir, S. S.; Weiss, S. Science 2005, 307, 538. doi: 10.1126/science.1104274
(3) Mattoussi, H.; Palui, G.; Na, H. B. Adv. Drug Delivery Rev. 2012, 64, 138.
(4) Medintz, I. L.; Uyeda, H. T.; Goldman, E. R.; Mattoussi, H. Nat. Mater. 2005, 4, 435. doi: 10.1038/nmat1390
(5) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. 1993, 115, 8706. doi: 10.1021/ja00072a025
(6) Qu, L. H.; Peng, X. G. J. Am. Chem. Soc. 2002, 124, 2049. doi: 10.1021/ja017002j
(7) Zrazhevskiy, P.; Sena, M.; Gao, X. H. Chem. Soc. Rev. 2010, 39, 4326. doi: 10.1039/b915139g
(8) Sapsford, K. E.; Algar, W. R.; Berti, L.; Gemmill, K. B.; Casey, B. J.; Oh, E.; Stewart, M. H.; Medintz, I. L. Chem. Rev. 2013, 113, 1904. doi: 10.1021/cr300143v
(9) Dubavik, A.; Sezgin, E.; Lesnyak, V.; Gaponik, N.; Schwille, P.; Eychmüller, A.ACS Nano 2012, 6, 2150.
(10) Uyeda, H. T.; Medintz, I. L.; Jaiswal, J. K.; Simon, S. M.; Mattoussi, H. J. Am. Chem. Soc. 2005, 127, 3870.
(11) Susumu, K.; Uyeda, H. T.; Medintz, I. L.; Pons, T.; Delehanty, J. B.; Mattoussi, H. J. Am. Chem. Soc. 2007, 129, 13987. doi: 10.1021/ja0749744
(12) Stewart, M. H.; Susumu, K.; Mei, B. C.; Medintz, I. L.; Delehanty, J. B.; Blanco-Canosa, J. B.; Dawson, P. E.; Mattoussi, H. J. Am. Chem. Soc. 2010, 132, 9804. doi: 10.1021/ja102898d
(13) Smith, A. M.; Nie, S. J. Am. Chem. Soc. 2008, 130, 11278. doi: 10.1021/ja804306c
(14) Liu, W. H.; Greytak, A. B.; Lee, J.; Wong, C. R.; Park, J.; Marshall, L. F.; Jiang, W.; Curtin, P. N.; Ting, A.Y.; Nocera, D. G.; Fukumura, D.; Jain, R. K.; Bawendi, M. G. J. Am. Chem. Soc. 2010, 132, 472. doi: 10.1021/ja908137d
(15) Rogach, A. L.; Franzl, T.; Klar, T. A.; Feldmann, J.; Gaponik, N.; Lesnyak, V.; Shavel, A.; Eychmuller, A.; Rakovich, Y. P.; Donegan, J. F. J. Phys. Chem. C 2007, 111, 14628. doi: 10.1021/jp072463y
(16) Gaponik, N.; Rogach, A. L. Phys. Chem. Chem. Phys. 2010, 12, 8685. doi: 10.1039/c000916d
(17) Zhang, H.; Wang, L.; Xiong, H.; Hu, L.; Yang, B.; Li, W. Adv. Mater. 2003, 15, 1712.
(18) Li, L.; Qian, H. F.; Ren, J. C. Chem. Commun. 2005, 528.
(19) He, Y.; Lu, H. T.; Sai, L. M.; Lai, W.Y.; Fan, Q. L.; Wang, L. H.; Huang, W. J. Phys. Chem. B 2006, 110, 13352. doi: 10.1021/jp061719h
(20) Yuwen, L.; Lu, H.; He, Y.; Chen, L.; Hu, M.; Bao, B.; Boey, F.; Zhang, H.; Wang, L. J. Mater. Chem. 2010, 20, 2788. doi: 10.1039/b924579k
(21) Liu, L.; Guo, X. H.; Li, Y.; Zhong, X. H. Inorg. Chem. 2010, 49, 3768. doi: 10.1021/ic902469d
(22) Jiang, W.; Mardyani, S.; Fischer, H.; Chan, W. C.W. Chem. Mater. 2006, 18, 872. doi: 10.1021/cm051393+
(23) He, Y.; Lu, H. T.; Sai, L. M.; Su, Y.Y.; Hu, M.; Fan, C. H.; Huang, W.; Wang, L. H. Adv. Mater. 2008, 20, 3416. doi: 10.1002/adma.200701166
(24) Brus, L. J. Phys. Chem. 1986, 90, 2555. doi: 10.1021/j100403a003
(25) Yin, Y.; Alivisatos, A. P. Nature 2005, 437, 664. doi: 10.1038/nature04165
(26) Kilina, S.; Ivanov, S.; Tretiak, S. J. Am. Chem. Soc. 2009, 131, 7717. doi: 10.1021/ja9005749
(27) Shavel, A.; Gaponik, N.; Eychmüller, A. J. Phys. Chem. B 2006, 110, 19280. doi: 10.1021/jp063351u
(28) Zou, L.; Gu, Z.; Zhang, N.; Zhang, Y.; Fang, Z.; Zhu, W.; Zhong, X. J. Mater. Chem. 2008, 18, 2807. doi: 10.1039/b801418c
(29) Niu, H. J.; Gao, M.Y. Angew. Chem. Int. Edit. 2006, 45, 6462.
(30) Guo, J.; Yang, W. L.; Wang, C. C. J. Phys. Chem. B 2005, 109, 17467. doi: 10.1021/jp044770z

[1]	吴进, 刘京, 夏雾, 任颖异, 王锋. 基于CdS和CdSe纳米半导体材料的可见光催化二氧化碳还原研究进展[J]. 物理化学学报, 2021, 37(5): 2008043 -0 .
[2]	郑超, 刘阿强, 毕成浩, 田建军. SCN掺杂提高CsPbI₃胶体量子点的稳定性和光探测性能[J]. 物理化学学报, 2021, 37(4): 2007084 -0 .
[3]	朱家瑶, 董玥, 张苏, 范壮军. 炭-/石墨烯量子点在超级电容器中的应用[J]. 物理化学学报, 2020, 36(2): 1903052 -0 .
[4]	黄彦捷, 连超, 周瑾艳, 黄梓宸, 康晓红, 黄振宇, 李小菁, 陈玲, 关妍. 由蚕砂制备的碳量子点在不同激发、pH、金属离子、温度及极性环境下的荧光性质研究[J]. 物理化学学报, 2019, 35(11): 1267 -1275 .
[5]	吴昊,严仲. 液相剥离法大规模制备锑烯量子点[J]. 物理化学学报, 2019, 35(10): 1052 -1057 .
[6]	李少海,翁波,卢康强,徐艺军. 聚胺界面修饰改善碳量子点可见光光敏化性能[J]. 物理化学学报, 2018, 34(6): 708 -718 .
[7]	贺平,袁方龙,王子飞,谭占鳌,范楼珍. 基于碳量子点的光电器件应用新进展[J]. 物理化学学报, 2018, 34(11): 1250 -1263 .
[8]	夏锐,王时茂,董伟伟,方晓东. 量子点敏化太阳能电池对电极研究进展[J]. 物理化学学报, 2017, 33(4): 670 -690 .
[9]	颜稔,赖璐,许子强,蒋风雷,刘义. 量子点与蛋白质相互作用热力学[J]. 物理化学学报, 2017, 33(12): 2377 -2387 .
[10]	陈军军,史成武,张正国,肖冠南,邵章朋,李楠楠. 4.81%光电转换效率的全固态致密PbS量子点薄膜敏化TiO₂纳米棒阵列太阳电池[J]. 物理化学学报, 2017, 33(10): 2029 -2034 .
[11]	王菡,王晓敏. 制备条件对PEI功能化石墨烯量子点荧光性能的影响[J]. 物理化学学报, 2016, 32(5): 1267 -1272 .
[12]	王丽娟,李琦,郝彦忠,申世刚,徐东升. CdS/CdSe/TiO₂多级空心微球光阳极中量子点覆盖度的提高[J]. 物理化学学报, 2016, 32(4): 983 -989 .
[13]	史继富,黄启章,万青翠,徐雪青,李春生,徐刚. 硫基离子液体电解质拓宽量子点敏化太阳能电池的应用温度范围[J]. 物理化学学报, 2016, 32(4): 822 -827 .
[14]	王云晶,刘迎秋,高秀秀,展艳珊,潘立洋,张文凯,房晓敏. 氨基功能化石墨烯量子点表面缺陷钝化及其发光增强[J]. 物理化学学报, 2016, 32(10): 2636 -2644 .
[15]	卫会云,王国帅,吴会觉,罗艳红,李冬梅,孟庆波. 量子点敏化太阳能电池研究进展[J]. 物理化学学报, 2016, 32(1): 201 -213 .

基于聚合物多齿配体的高性能CdTe量子点的微波水相合成

Synthesis of High Quality CdTe Quantum Dots in Aqueous Solution Using Multidentate Polymer Ligands under Microwave Irradiation

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

本文评价

推荐阅读 0