5(6)羧基荧光素敏化TiO2纳米粒子的光致电子转移的荧光特性研究

蒋礼林; 宋云飞; 刘伟龙; 于国洋; 何兴; 王阳; 吴红琳; 杨延强

doi:10.7498/aps.61.090505

摘要

通过水解TiCl4制备了锐钛矿结构TiO2纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO2纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO2纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数(D*)与电荷分离态波函数(D+ +e-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO2纳米粒子体系时, 电子以两种不同方式注入TiO2纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO2)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为1=41 ps (74.4%) 和2=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO2纳米粒子体系的荧光分别以时间常数为1=44 ps (90.4%),2=478 ps (8.6%) 和3=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.

关键词:

Abstract

Anatased TiO2 nanoparticles were prepared by controlling hydrolysis of the TiCl4. Time-resolved fluorescence experiments were carried out to study the photo-induced electron transfer dynamics in the system of the 5(6)CFL dye-sensitized TiO2 nanoparticles. For the aboved system, the formation of the charge transfer complex is attributed to the coupling interaction between the wave functions of the excited electronic state of the dye ((D*)) and the charge separated state ((D++e-)). On excitation of 5(6)CFL dye-sensitized TiO2 nanoparticle system. The injection of electrons into the conduction band of TiO2 nanoparticles takes place in two different ways: through the excited state of the 5(6)CFL dye and through direct injection from the charge transfer complex. The time-resolved fluorescence experimental results indicate that the free 5(6)CFL dye in water has double-exponential decay with lifetimes1=41 ps (74.4%) and2=3.22 ns (25.6%). However, 5(6)CFL dye-sensitized TiO2 nanoparticles have triple-exponential decay with lifetimes of1=44 ps (90.4%),2=478 ps (8.6%) and3=2.41 ns (1.0%). Our research will provide a valuable reference for the mechanism of dye-sensitized solar cell.

Keywords:

作者及机构信息

1.
哈尔滨工业大学物理系, 凝聚态科学与技术研究中心, 哈尔滨 150001;

2.
贺州学院物理与电子信息工程系, 贺州 542800

基金项目: 国家自然科学基金(批准号: 20973050)资助的课题.

Authors and contacts

1.
Centre for the Condensed Matter Science and Technology, Department of Physics, Harbin Institute of Technology, Harbin 150001, China;

2.
Department of Physics and Electronics Information Engineering, Hezhou University, Hezhou 542800, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 20973050).

参考文献

[1]	West W, Gilman P B Jr 1977 The Theory of the Photographic Process (New York: Macmillan) p251
[2]	Nazeerudin M K, Kay A, Rodicio I, Humphrey-Baker R, Müller E, Liska P, Vlachopoulos N, Grätzel M 1993 J. Am. Chem. Soc. 115 6382
[3]	Duncan W R, Prezhdo O V 2007 Annu. Rev. Phys. Chem. 58 143
[4]	Anderson N A, Lian T Q 2005 Annu. Rev. Phys.Chem. 5 491
[5]	Zeng L Y, Dai S Y, Wang K J, Shi C W, Kong F T, Hu L H, Pan X 2005 Acta Pyhs. Sin. 54 0053 (in Chinese) [曾隆月, 戴松元, 王孔嘉, 史成武, 孔凡太, 胡林华, 潘旭 2005 物理学报 54 0053]
[6]	Xu W W, Dai S Y, Fang X Q, Hu L H, Kong F T, Pan X, Wang K J 2005 Acta Pyhs. Sin. 54 5943 (in Chinese) [徐炜炜, 戴松元, 方霞琴, 胡林华, 孔凡太, 潘旭, 王孔嘉 2005 物理学报 54 5943]
[7]	Liu W Q, Kou D X, Hu L H, Huang Y, Jiang N Q, Dai S Y 2010 Acta Pyhs. Sin. 59 5141 (in Chinese) [刘伟庆, 寇东星, 胡林华, 黄阳, 姜年权, 戴松元, 2010 物理学报 59 5141]
[8]	Siders P, Marcus R A 1981 J. Am. Chem. Soc. 103 748
[9]	Huber R, Moser J E, Grätzel M, Wachtveitl J 2002 J. Phys. Chem. B 106 6494
[10]	Adachi M, Murata Y, Takao J, Jiu J, Sakamoto M, Wang F 2004 J. Am. Chem. Soc. 126 14943
[11]	Ito S, Murakami T N, Comte P, Liska P, Grätzel C, Nazeeruddin M K, Grätzel M 2008 Thin Solid Films 516 4613
[12]	Ko S H, Lee D, Kang H W, Nam K H, Yeo J Y, Hong S J, Grigoropoulos C P, Sung H J 2011 Nano Lett. 11 666
[13]	Peng W Q, Yanagida M, Han L Y, Ahmed S 2011 Nanotechnology 22 275709
[14]	Hardin B E, Gaynor W, Ding I K, Rim S B, Peumans P, McGehee M D 2011 Organic Electronics 12 875
[15]	Gao F F, Wang Y, Shi D, Zhang J, Wang M K, Jing X Y, Humphry-Baker R, Wang P, Zakeeruddin S M, Grätzel M 2008 J. Am. Chem. Soc. 130 10720
[16]	Ito S, Zakeeruddin S M, Humphry-Baker R 2006 Adv. Mate. 18 1202
[17]	Ghosh H N, Asbury J B, Lian T Q 1998 J. Phys. Chem. B 102 6482
[18]	Ramakrishna G, Ghosh H N 2001 J. Phys. Chem. B 105 7000
[19]	Ghosh H N 1999 J. Phys. Chem. B 103 10382
[20]	Huber R, Spo1rlein S, Moser J E, Grä1tzel M, Wachtveitl J 2000 J. Phys. Chem. B 104 8995
[21]	Cherepy N J, Smestad G P, Grätzel M, Zhang J Z 1997 J. Phys. Chem. B 101 9342
[22]	Jayaweera P M, Kumarasinghe A R, Tennakone K 1999 J. Photochem.Photobiol. A 126 111
[23]	Ghosh H N, Asbury J B, Weng Y, Lian T Q 1998 J. Phys. Chem. B 102 10208
[24]	Lu H, Prieskorn J N, Hupp J T 1993 J. Am. Chem. Soc. 115 4927
[25]	Weng Y, Wang Y, Asbury J B, Ghosh H N, Lian T Q 2000 J. Phys. Chem. B 104 93
[26]	Mulliken R S, Person W B 1969 Molecular Complexes: a lecture and reprint volume (New York: Wiley)
[27]	Cohen-Tannoudji C 1977 Quantum Mechanics (New York: Wiley)

施引文献

[1]	West W, Gilman P B Jr 1977 The Theory of the Photographic Process (New York: Macmillan) p251
[2]	Nazeerudin M K, Kay A, Rodicio I, Humphrey-Baker R, Müller E, Liska P, Vlachopoulos N, Grätzel M 1993 J. Am. Chem. Soc. 115 6382
[3]	Duncan W R, Prezhdo O V 2007 Annu. Rev. Phys. Chem. 58 143
[4]	Anderson N A, Lian T Q 2005 Annu. Rev. Phys.Chem. 5 491
[5]	Zeng L Y, Dai S Y, Wang K J, Shi C W, Kong F T, Hu L H, Pan X 2005 Acta Pyhs. Sin. 54 0053 (in Chinese) [曾隆月, 戴松元, 王孔嘉, 史成武, 孔凡太, 胡林华, 潘旭 2005 物理学报 54 0053]
[6]	Xu W W, Dai S Y, Fang X Q, Hu L H, Kong F T, Pan X, Wang K J 2005 Acta Pyhs. Sin. 54 5943 (in Chinese) [徐炜炜, 戴松元, 方霞琴, 胡林华, 孔凡太, 潘旭, 王孔嘉 2005 物理学报 54 5943]
[7]	Liu W Q, Kou D X, Hu L H, Huang Y, Jiang N Q, Dai S Y 2010 Acta Pyhs. Sin. 59 5141 (in Chinese) [刘伟庆, 寇东星, 胡林华, 黄阳, 姜年权, 戴松元, 2010 物理学报 59 5141]
[8]	Siders P, Marcus R A 1981 J. Am. Chem. Soc. 103 748
[9]	Huber R, Moser J E, Grätzel M, Wachtveitl J 2002 J. Phys. Chem. B 106 6494
[10]	Adachi M, Murata Y, Takao J, Jiu J, Sakamoto M, Wang F 2004 J. Am. Chem. Soc. 126 14943
[11]	Ito S, Murakami T N, Comte P, Liska P, Grätzel C, Nazeeruddin M K, Grätzel M 2008 Thin Solid Films 516 4613
[12]	Ko S H, Lee D, Kang H W, Nam K H, Yeo J Y, Hong S J, Grigoropoulos C P, Sung H J 2011 Nano Lett. 11 666
[13]	Peng W Q, Yanagida M, Han L Y, Ahmed S 2011 Nanotechnology 22 275709
[14]	Hardin B E, Gaynor W, Ding I K, Rim S B, Peumans P, McGehee M D 2011 Organic Electronics 12 875
[15]	Gao F F, Wang Y, Shi D, Zhang J, Wang M K, Jing X Y, Humphry-Baker R, Wang P, Zakeeruddin S M, Grätzel M 2008 J. Am. Chem. Soc. 130 10720
[16]	Ito S, Zakeeruddin S M, Humphry-Baker R 2006 Adv. Mate. 18 1202
[17]	Ghosh H N, Asbury J B, Lian T Q 1998 J. Phys. Chem. B 102 6482
[18]	Ramakrishna G, Ghosh H N 2001 J. Phys. Chem. B 105 7000
[19]	Ghosh H N 1999 J. Phys. Chem. B 103 10382
[20]	Huber R, Spo1rlein S, Moser J E, Grä1tzel M, Wachtveitl J 2000 J. Phys. Chem. B 104 8995
[21]	Cherepy N J, Smestad G P, Grätzel M, Zhang J Z 1997 J. Phys. Chem. B 101 9342
[22]	Jayaweera P M, Kumarasinghe A R, Tennakone K 1999 J. Photochem.Photobiol. A 126 111
[23]	Ghosh H N, Asbury J B, Weng Y, Lian T Q 1998 J. Phys. Chem. B 102 10208
[24]	Lu H, Prieskorn J N, Hupp J T 1993 J. Am. Chem. Soc. 115 4927
[25]	Weng Y, Wang Y, Asbury J B, Ghosh H N, Lian T Q 2000 J. Phys. Chem. B 104 93
[26]	Mulliken R S, Person W B 1969 Molecular Complexes: a lecture and reprint volume (New York: Wiley)
[27]	Cohen-Tannoudji C 1977 Quantum Mechanics (New York: Wiley)

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