表面In掺杂TiO<sub>2</sub>的N719/TiO<sub>2</sub>-Inx%/FTO薄膜电极的光电转换效率

引用本文: 程辉, 姚江宏, 曹亚安. 表面In掺杂TiO₂的N719/TiO₂-Inx%/FTO薄膜电极的光电转换效率[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201207301 shu

Citation: CHENG Hui, YAO Jiang-Hong, CAO Ya-An. Photoelectric Conversion Efficiency of N719/TiO₂-Inx%/FTO Film Electrodes Incorporating In Doped at the TiO₂ Surface[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201207301 shu

表面In掺杂TiO₂的N719/TiO₂-Inx%/FTO薄膜电极的光电转换效率

基金项目:
国家自然科学基金(50872056, 51072082, 21173121)资助项目 (50872056, 51072082, 21173121)

摘要:

采用溶胶-凝胶法制备出In 表面修饰的TiO₂ (TiO₂-Inx%)纳米粒子, x%代表在In 掺杂的TiO₂样品中In³⁺与In³⁺和Ti⁴⁺离子摩尔百分含量. 利用二(四丁基铵)顺式-双(异硫氰基)双(2,2'-联吡啶-4,4'-二羧酸)钌(II)(N719)作为敏化剂, 制备出N719/TiO₂/FTO (氟掺杂锡氧化物)和N719/TiO₂-Inx%/FTO染料敏化薄膜电极. 光电转换效率实验表明, 在薄膜电极+0.5 mol·L^-1 LiI+0.05 mol·L^-1 I₂的三甲氧基丙腈(MPN)溶液+Pt 光电池体系中,N719/TiO₂-Inx%/FTO薄膜电极的光电转换效率均高于N719/TiO₂/FTO, 其中N719/TiO₂-In0.1%/FTO的光电转换效率比N719/TiO₂/FTO提高了20%. 利用X 射线衍射(XRD)、X 射线光电子能谱(XPS)、漫反射吸收光谱(DRS)、荧光(PL)光谱和表面光电流作用谱确定了TiO₂-Inx%样品中In3+离子的存在方式和能带结构; 利用表面光电流作用谱研究了N719/TiO₂-Inx%/FTO薄膜电极的光致界面电荷转移过程. 结果表明, In3+离子在TiO₂表面形成O-In-Cl_n (n=1, 2)物种, 该物种的表面态能级位于导带下0.3 eV处; 在光电流产生过程中, O-In-Cl_n (n=1, 2)表面态能级有效地抑制了光生载流子在TiO₂-Inx%层的复合, 促进了阳极光电流的增加, 从而导致N719/TiO₂-Inx%/FTO薄膜电极的光电转化效率高于N719/TiO₂/FTO, 并进一步讨论了光致界面电荷转移的机理.

关键词:

English

Photoelectric Conversion Efficiency of N719/TiO₂-Inx%/FTO Film Electrodes Incorporating In Doped at the TiO₂ Surface

1.
1. College of Physics, Nankai University, Tianjin 300071, P. R. China;
2. The Key Laboratory of Weak Light Nonlinear Photonics, Ministry of Education, Teda Applied Physics School, Nankai University, Tianjin 300457, P. R. China
Received Date: 07 June 2012
Available Online: 17 October 2012
Fund Project:
国家自然科学基金(50872056, 51072082, 21173121)资助项目

Abstract:

Nanoparticles of TiO₂ with surface modification by In doping were prepared using a sol-gel technique. These materials had the general formula TiO₂-Inx%, where x represents the mole percent of In3+ ions in the combined In³⁺ and Ti⁴⁺ metal ion content. N719/TiO₂/FTO (fluorine doped tin oxide) and N719/ TiO₂-Inx%/FTO film electrodes were prepared, using N719 dye as a sensitizing agent. These thin film electrodes were incorporated into solar cells composed of 0.5 mol·L^-1 LiI, 0.05 mol·L^-1 I₂, methoxypropionitrile (MPN) and Pt. It was determined that the photoelectric conversion efficiencies of the N719/TiO₂-Inx%/FTO film electrodes were higher than that of N719/TiO₂/FTO. In particular, the conversion efficiency of N719/TiO₂-In0.1%/FTO was 20% greater than that of N719/TiO₂/FTO. The band structure and In³⁺ ion content of TiO₂-Inx% samples were analyzed using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and optical diffuse-reflection spectroscopy (DRS), as well as by examination of photoluminescence (PL) and surface photocurrent action spectra. The photo-induced charge transfer processes of the N719/TiO₂-Inx%/FTO film electrodes were also elucidated using surface photocurrent action spectra. The results showed that O-In-Cl_n (where n=1 or 2) species were formed at the TiO₂ surface, with surface state energy levels 0.3 eV below the conduction band of TiO₂. The surface state energy levels of these species effectively inhibit the recombination of photo-generated carriers during the photocurrent generation process, and also serve to increase the anodic photocurrent and significantly improve the photoelectric conversion efficiency of N719/TiO₂-Inx%/FTO thin film electrodes. This work also discusses the interfacial light-induced charge transfer mechanisms in these materials.

Key words:

1. [1]
  
  (1) O'Regan, B.; Grätzel, M. Nature 1991, 353, 737. doi: 10.1038/353737a0
  (1) O'Regan, B.; Grätzel, M. Nature 1991, 353, 737. doi: 10.1038/353737a0
2. [2]
  (2) Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.;Muller, E.; Liska, P.;Vlachopoulos, N.; Grätzel, M. J. Am. Chem. Soc. 1993, 115, 6382. doi: 10.1021/ja00067a063(2) Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.;Muller, E.; Liska, P.;Vlachopoulos, N.; Grätzel, M. J. Am. Chem. Soc. 1993, 115, 6382. doi: 10.1021/ja00067a063
3. [3]
  (3) Grätzel, M. J. Photochem. Photobiol. C 2003, 4, 145. doi: 10.1016/S1389-5567(03)00026-1(3) Grätzel, M. J. Photochem. Photobiol. C 2003, 4, 145. doi: 10.1016/S1389-5567(03)00026-1
4. [4]
  (4) Dloczik, L.; Ileperuma, O.; Lauermann, I. Peter, L. M.;Ponomarev, E. A.; Redmond, G.; Shaw, N. J.; Uhlendorf, I.J. Phys. Chem. B 1997, 101, 10281. doi: 10.1021/jp972466i(4) Dloczik, L.; Ileperuma, O.; Lauermann, I. Peter, L. M.;Ponomarev, E. A.; Redmond, G.; Shaw, N. J.; Uhlendorf, I.J. Phys. Chem. B 1997, 101, 10281. doi: 10.1021/jp972466i
5. [5]
  (5) Snaith, H. J.; Schmidt-Mende, L. Adv. Mater. 2007, 19, 3187.doi: 10.1002/adma.200602903(5) Snaith, H. J.; Schmidt-Mende, L. Adv. Mater. 2007, 19, 3187.doi: 10.1002/adma.200602903
6. [6]
  (6) Ito, S.; Zakeeruddin, S. M.; Humphry-Baker, R.; Liska, P.;Charvet, R.; Comte, P.; Nazeeruddin, M. K.; Péchy, P.; Takata,M.; Miura, H.; Uchida, S.; and Grätzel, M. Adv. Mater. 2006, 18,1202. doi: 10.1002/(ISSN)1521-4095(6) Ito, S.; Zakeeruddin, S. M.; Humphry-Baker, R.; Liska, P.;Charvet, R.; Comte, P.; Nazeeruddin, M. K.; Péchy, P.; Takata,M.; Miura, H.; Uchida, S.; and Grätzel, M. Adv. Mater. 2006, 18,1202. doi: 10.1002/(ISSN)1521-4095
7. [7]
  (7) Adachi, M.; Murata, Y.; Takao, J. J. Am. Chem. Soc. 2004, 126,14943. doi: 10.1021/ja048068s(7) Adachi, M.; Murata, Y.; Takao, J. J. Am. Chem. Soc. 2004, 126,14943. doi: 10.1021/ja048068s
8. [8]
  (8) Palomares, E.; Clifford, J. N.; Haque, S. A. J. Am. Chem. Soc.2003, 125, 475. doi: 10.1021/ja027945w(8) Palomares, E.; Clifford, J. N.; Haque, S. A. J. Am. Chem. Soc.2003, 125, 475. doi: 10.1021/ja027945w
9. [9]
  (9) Chiba, Y.; Islam, A.;Watanabe, Y.; Komiya, R.; Koide, N.; Han,L. Jpn. J. Appl. Phys. 2006, 45, L638.(9) Chiba, Y.; Islam, A.;Watanabe, Y.; Komiya, R.; Koide, N.; Han,L. Jpn. J. Appl. Phys. 2006, 45, L638.
10. [10]
  (10) Gao, F.;Wang, Y.; Shi, D.; Zhang, J.;Wang, M.; Jing, X.;Humphry-Baker, R.;Wang, P.; Zakeeruddin, S. M.; Grätzel, M.J. Am. Chem. Soc. 2008, 130, 10720. doi: 10.1021/ja801942j(10) Gao, F.;Wang, Y.; Shi, D.; Zhang, J.;Wang, M.; Jing, X.;Humphry-Baker, R.;Wang, P.; Zakeeruddin, S. M.; Grätzel, M.J. Am. Chem. Soc. 2008, 130, 10720. doi: 10.1021/ja801942j
11. [11]
  (11) Yu, Q.;Wang, Y.; Yi, Z.; Zu, N.; Zhang, J.; Zhang, M.;Wang, P.ACS Nano 2010, 4, 6032. doi: 10.1021/nn101384e(11) Yu, Q.;Wang, Y.; Yi, Z.; Zu, N.; Zhang, J.; Zhang, M.;Wang, P.ACS Nano 2010, 4, 6032. doi: 10.1021/nn101384e
12. [12]
  (12) Wang, K. P.; Teng, H. Phys. Chem. Chem. Phys. 2009, 11, 9489.(12) Wang, K. P.; Teng, H. Phys. Chem. Chem. Phys. 2009, 11, 9489.
13. [13]
  (13) Lu, X.; Mou, X.;Wu, J.; Zhang, D.; Zhang, L.; Huang, F.; Xu,F.; Huang, S. Adv. Funct. Mater. 2010, 20, 509. doi: 10.1002/adfm.v20:3(13) Lu, X.; Mou, X.;Wu, J.; Zhang, D.; Zhang, L.; Huang, F.; Xu,F.; Huang, S. Adv. Funct. Mater. 2010, 20, 509. doi: 10.1002/adfm.v20:3
14. [14]
  (14) Imahori, H.; Hayashi, S.; Umeyama, T.; Eu, S.; Oguro, A.;Kang, S.; Matano, Y.; Shishido, T.; Ngamsinlapasathian, S.;Yoshikawa, S. Langmuir 2006, 22, 11405. doi: 10.1021/la061527d(14) Imahori, H.; Hayashi, S.; Umeyama, T.; Eu, S.; Oguro, A.;Kang, S.; Matano, Y.; Shishido, T.; Ngamsinlapasathian, S.;Yoshikawa, S. Langmuir 2006, 22, 11405. doi: 10.1021/la061527d
15. [15]
  (15) Okuya, M.; Nakade, K.; Kaneko, S. Sol. Energy Mater. Sol. Cells 2002, 70, 425. doi: 10.1016/S0927-0248(01)00033-2(15) Okuya, M.; Nakade, K.; Kaneko, S. Sol. Energy Mater. Sol. Cells 2002, 70, 425. doi: 10.1016/S0927-0248(01)00033-2
16. [16]
  (16) Ko, K. H.; Lee, Y. C.; Jung, Y. J. J. Colloid Interface Sci. 2005,283, 482. doi: 10.1016/j.jcis.2004.09.009(16) Ko, K. H.; Lee, Y. C.; Jung, Y. J. J. Colloid Interface Sci. 2005,283, 482. doi: 10.1016/j.jcis.2004.09.009
17. [17]
  (17) Chandiran, A. K.; Sauvage, F.; Casas-Cabanas, M.; Comte, P.;Zakeeruddin, S. M.; Grätzel, M. J. Phys. Chem. C 2010, 114,15849. doi: 10.1021/jp106058c(17) Chandiran, A. K.; Sauvage, F.; Casas-Cabanas, M.; Comte, P.;Zakeeruddin, S. M.; Grätzel, M. J. Phys. Chem. C 2010, 114,15849. doi: 10.1021/jp106058c
18. [18]
  (18) Iwamoto, S.; Sazanami, Y.; Inoue, M.; Inoue, T.; Hoshi, T.;Shigaki, K.; Kaneko, M.; Maenosono, A. ChemSusChem 2008,1, 401. doi: 10.1002/(ISSN)1864-564X(18) Iwamoto, S.; Sazanami, Y.; Inoue, M.; Inoue, T.; Hoshi, T.;Shigaki, K.; Kaneko, M.; Maenosono, A. ChemSusChem 2008,1, 401. doi: 10.1002/(ISSN)1864-564X
19. [19]
  (19) Jing, L. Q.; Sun, X. J.; Xin, B. F.;Wang, B. Q.; Cai,W. M.; Fu,H. G. J. Solid State Chem. 2004, 177, 3375. doi: 10.1016/j.jssc.2004.05.064(19) Jing, L. Q.; Sun, X. J.; Xin, B. F.;Wang, B. Q.; Cai,W. M.; Fu,H. G. J. Solid State Chem. 2004, 177, 3375. doi: 10.1016/j.jssc.2004.05.064
20. [20]
  (20) Ma, T.; Akiyama, M.; Abe, E.; Imai, I. Nano Lett. 2005, 5, 2543.doi: 10.1021/nl051885l(20) Ma, T.; Akiyama, M.; Abe, E.; Imai, I. Nano Lett. 2005, 5, 2543.doi: 10.1021/nl051885l
21. [21]
  (21) Tian, H.; Hu, L.; Li,W.; Sheng, J.; Xu, S.; Dai, S. J. Mater. Chem. 2011, 21, 7074. doi: 10.1039/c1jm10853k(21) Tian, H.; Hu, L.; Li,W.; Sheng, J.; Xu, S.; Dai, S. J. Mater. Chem. 2011, 21, 7074. doi: 10.1039/c1jm10853k
22. [22]
  (22) Wang, E. J.; Yang,W. S.; Cao, Y. A. J. Phys. Chem. C 2009,113, 20912. doi: 10.1021/jp9041793(22) Wang, E. J.; Yang,W. S.; Cao, Y. A. J. Phys. Chem. C 2009,113, 20912. doi: 10.1021/jp9041793
23. [23]
  (23) Du1rr, M.; Rosselli, S.; Yasuda, A. J. Phys. Chem. B 2006, 110,21899. doi: 10.1021/jp063857c(23) Du1rr, M.; Rosselli, S.; Yasuda, A. J. Phys. Chem. B 2006, 110,21899. doi: 10.1021/jp063857c
24. [24]
  (24) Lee, J. C.; Kim, T. G.; Lee,W.; Han, S. H.; Sung, Y. M. Crystal. Growth. Design 2009, 9, 4519. doi: 10.1021/cg9005373(24) Lee, J. C.; Kim, T. G.; Lee,W.; Han, S. H.; Sung, Y. M. Crystal. Growth. Design 2009, 9, 4519. doi: 10.1021/cg9005373
25. [25]
  (25) Zhai, X. H.; Zhao, J. Y.; Chao, H.; Cao, Y. A. Acta Phys. -Chim. Sin. 2010, 26, 1617. [翟晓辉, 赵俊岩, 巢晖, 曹亚安. 物理化学学报, 2010, 26, 1617.] doi: 10.3866/PKU.WHXB20100635(25) Zhai, X. H.; Zhao, J. Y.; Chao, H.; Cao, Y. A. Acta Phys. -Chim. Sin. 2010, 26, 1617. [翟晓辉, 赵俊岩, 巢晖, 曹亚安. 物理化学学报, 2010, 26, 1617.] doi: 10.3866/PKU.WHXB20100635
26. [26]
  (26) Dong, J. Z.; Zhao, J. Y.; Chao, H.; Cao, Y. A. Acta Chim. Sin.2011, 69, 2781. [董江舟, 赵峻岩, 巢晖, 曹亚安. 化学学报.2011, 69, 2781.](26) Dong, J. Z.; Zhao, J. Y.; Chao, H.; Cao, Y. A. Acta Chim. Sin.2011, 69, 2781. [董江舟, 赵峻岩, 巢晖, 曹亚安. 化学学报.2011, 69, 2781.]
27. [27]
  (27) Gao, B.; Ma, Y.; Cao, Y.; Yang,W.; Yao, J. J. Phys. Chem. B2006, 110, 14391. doi: 10.1021/jp0624606(27) Gao, B.; Ma, Y.; Cao, Y.; Yang,W.; Yao, J. J. Phys. Chem. B2006, 110, 14391. doi: 10.1021/jp0624606
28. [28]
  (28) Surolia, P. K.; Tayade, R. J.; Jasra, R. V. Ind. Eng. Chem. Res.2007, 46, 6196. doi: 10.1021/ie0702678(28) Surolia, P. K.; Tayade, R. J.; Jasra, R. V. Ind. Eng. Chem. Res.2007, 46, 6196. doi: 10.1021/ie0702678
29. [29]
  (29) Cao, Y.; Yang,W.; Zhang,W.; Liu, G.; Yue, P. New J. Chem.2004, 28, 218. doi: 10.1039/b306845e(29) Cao, Y.; Yang,W.; Zhang,W.; Liu, G.; Yue, P. New J. Chem.2004, 28, 218. doi: 10.1039/b306845e
30. [30]
  (30) Okushita, H.; Shimidzu, T. Bull. Chem. Soc. Jpn. 1990, 63, 920.doi: 10.1246/bcsj.63.920(30) Okushita, H.; Shimidzu, T. Bull. Chem. Soc. Jpn. 1990, 63, 920.doi: 10.1246/bcsj.63.920
31. [31]
  (31) Reddya, B. M.; Chowdhury, B.; Smirniotis, P. G. Applied Catalysis A 2001, 219, 53. doi: 10.1016/S0926-860X(01)00658-5(31) Reddya, B. M.; Chowdhury, B.; Smirniotis, P. G. Applied Catalysis A 2001, 219, 53. doi: 10.1016/S0926-860X(01)00658-5
32. [32]
  (32) Mousty-Desbuquoit, C.; Riga, J.; Verbist, J. J. J. Chem. Phys.1983, 79, 26. doi: 10.1063/1.445567(32) Mousty-Desbuquoit, C.; Riga, J.; Verbist, J. J. J. Chem. Phys.1983, 79, 26. doi: 10.1063/1.445567
33. [33]
  (33) Freeland, B. H.; Habeeb, J. J.; Tuck, D. G. Can. J. Chem. 1977,55, 1528.(33) Freeland, B. H.; Habeeb, J. J.; Tuck, D. G. Can. J. Chem. 1977,55, 1528.
34. [34]
  (34) Zhu, J.; Zheng,W.; He, B.; Zhang, J.; Anpo, M. J. Mol. Catal. A2004, 216, 35. doi: 10.1016/j.molcata.2004.01.008(34) Zhu, J.; Zheng,W.; He, B.; Zhang, J.; Anpo, M. J. Mol. Catal. A2004, 216, 35. doi: 10.1016/j.molcata.2004.01.008
35. [35]
  (35) Liang, C.; Li, F.; Liu, C.; Lu, J.;Wang, X. Dyes Pigm. 2008, 76,477. doi: 10.1016/j.dyepig.2006.10.006(35) Liang, C.; Li, F.; Liu, C.; Lu, J.;Wang, X. Dyes Pigm. 2008, 76,477. doi: 10.1016/j.dyepig.2006.10.006
36. [36]
  (36) Li, D.; Haneda, H.; Hishita, S.; Ohashi, N. Chem. Mater. 2005,17, 2596. doi: 10.1021/cm049099p(36) Li, D.; Haneda, H.; Hishita, S.; Ohashi, N. Chem. Mater. 2005,17, 2596. doi: 10.1021/cm049099p
37. [37]
  (37) Serpone, N.; Lawless, D.; Khairutdinov, R. J. Phys. Chem.1995, 99, 16655. doi: 10.1021/j100045a027(37) Serpone, N.; Lawless, D.; Khairutdinov, R. J. Phys. Chem.1995, 99, 16655. doi: 10.1021/j100045a027
38. [38]
  (38) Yu, J. C.; Ho,W.; Yu, J.; Hark, S. K.; Iu, K. Langmuir 2003, 19,3889. doi: 10.1021/la025775v(38) Yu, J. C.; Ho,W.; Yu, J.; Hark, S. K.; Iu, K. Langmuir 2003, 19,3889. doi: 10.1021/la025775v
39. [39]
  (39) Saraf, L. V.; Patil, S. I.; Ogale, S. B.; Sainkar, S. R.; Kshirsager,S. T. Int. J. Mod. Phys. B 1998, 12, 2635. doi: 10.1142/S0217979298001538(39) Saraf, L. V.; Patil, S. I.; Ogale, S. B.; Sainkar, S. R.; Kshirsager,S. T. Int. J. Mod. Phys. B 1998, 12, 2635. doi: 10.1142/S0217979298001538
40. [40]
  (40) Matar, F.; Ghaddar, T. H.; O'Regan, B. J. Mater. Chem. 2008,18, 4246. doi: 10.1039/b808255c
  (40) Matar, F.; Ghaddar, T. H.; O'Regan, B. J. Mater. Chem. 2008,18, 4246. doi: 10.1039/b808255c

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沈阳化工大学材料科学与工程学院沈阳 110142

表面In掺杂TiO₂的N719/TiO₂-Inx%/FTO薄膜电极的光电转换效率

English

Photoelectric Conversion Efficiency of N719/TiO₂-Inx%/FTO Film Electrodes Incorporating In Doped at the TiO₂ Surface

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

表面In掺杂TiO2的N719/TiO2-Inx%/FTO薄膜电极的光电转换效率

English

Photoelectric Conversion Efficiency of N719/TiO2-Inx%/FTO Film Electrodes Incorporating In Doped at the TiO2 Surface

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

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

表面In掺杂TiO₂的N719/TiO₂-Inx%/FTO薄膜电极的光电转换效率

Photoelectric Conversion Efficiency of N719/TiO₂-Inx%/FTO Film Electrodes Incorporating In Doped at the TiO₂ Surface

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs