Dual Functionality of BODIPY Chromophore in Porphyrin-Sensitized Nanocrystalline Solar Cells

View Author Information
Center for Advanced Photovoltaics, and Department of Chemistry and Biochemistry, South Dakota State University, Brookings, South Dakota 57007, United States
§ Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, Hsinchu 30010, Taiwan
Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, United States
Department of Applied Chemistry, National Chi Nan University, Puli, Nantou Hsien 54561, Taiwan
*Tel.: (605) 688-6962. Fax: (605) 688-4401. E-mail: [email protected]
Cite this: J. Phys. Chem. C 2012, 116, 19, 10451–10460
Publication Date (Web):April 23, 2012
Copyright © 2012 American Chemical Society
Article Views
Read OnlinePDF (3 MB)
Supporting Info (1)»


A new organic dye (BET) was synthesized and coadsorbed on TiO2 nanoparticles to make mixed BET/porphyrin-sensitized solar cells (DSCs). The BET is a boron dipyrromethene compound with one benzoic acid group attached to the meso position for its binding to the TiO2 nanoparticles and two ethyl groups in the 3 and 3′ positions of pyrrolic units to broaden its absorption. Two ethyl groups are in the cis position, as revealed by its single-crystal X-ray diffraction analysis. The BET exhibits strong absorption in the green light region with an absorption maximum at 528 nm in CH2Cl2, which is complementary to the absorption spectrum of porphyrin dyes. When the BET coadsorbs on the TiO2 nanoparticles with porphyrin dyes (TMPZn and LD12), the power conversion efficiencies increase from 1.09% to 2.90% for TMPZn-sensitized solar cells and from 6.65% to 7.60% for LD12-sensitized solar cells, respectively. The IPCE of the devices in the green light region increases dramatically due to the cosensitizing effect of BET. The fluorescence of BET in solution is partially quenched and that of porphyrin is enhanced in the presence of BET dye, indicating an intermolecular energy transfer from BET to the porphyrin dyes. The direct electron injection from BET to the TiO2 conduction band was rather poor; only negligible photocurrent was observed. Comparative studies of absorption spectra on the TiO2 nanoparticle films and electrochemical impedance at the dye/TiO2 interface also indicate that the BET is an excellent coadsorber to prevent the aggregation of porphyrin dyes. An intermolecular energy transfer model is proposed to account for the observed photovoltaic enhancement of the cosensitization system.

Supporting Information

Jump To

Complete author lists of refs 8, 29, 30, 38, and 76. This material is available free of charge via the Internet at http://pubs.acs.org.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Cited By

This article is cited by 50 publications.

  1. Emmanouil Nikoloudakis, Palas Baran Pati, Georgios Charalambidis, Darya S. Budkina, Stéphane Diring, Aurélien Planchat, Denis Jacquemin, Eric Vauthey, Athanassios G. Coutsolelos, Fabrice Odobel. Dye-Sensitized Photoelectrosynthesis Cells for Benzyl Alcohol Oxidation Using a Zinc Porphyrin Sensitizer and TEMPO Catalyst. ACS Catalysis 2021, 11 (19) , 12075-12086. https://doi.org/10.1021/acscatal.1c02609
  2. Yuya Takekuma, Haruki Nagakawa, Tomoyasu Noji, Keisuke Kawakami, Rei Furukawa, Mamoru Nango, Nobuo Kamiya, Morio Nagata. Enhancement of Photocurrent by Integration of an Artificial Light-Harvesting Antenna with a Photosystem I Photovoltaic Device. ACS Applied Energy Materials 2019, 2 (6) , 3986-3990. https://doi.org/10.1021/acsaem.9b00349
  3. Hafsah Klfout, Adam Stewart, Mahmoud Elkhalifa, and Hongshan He . BODIPYs for Dye-Sensitized Solar Cells. ACS Applied Materials & Interfaces 2017, 9 (46) , 39873-39889. https://doi.org/10.1021/acsami.7b07688
  4. Chin-Li Wang, Jia-Wei Shiu, Yen-Ni Hsiao, Pei-Shang Chao, Eric Wei-Guang Diau, and Ching-Yao Lin . Co-Sensitization of Zinc and Free-Base Porphyrins with an Organic Dye for Efficient Dye-Sensitized Solar Cells. The Journal of Physical Chemistry C 2014, 118 (48) , 27801-27807. https://doi.org/10.1021/jp510057b
  5. Viktoras Dryza and Evan J. Bieske . Suppressing Förster Resonance Energy Transfer between Organic Dyes on a Cosensitized Metal Oxide Surface. The Journal of Physical Chemistry C 2014, 118 (34) , 19646-19654. https://doi.org/10.1021/jp506392u
  6. Liping Si and Hongshan He . Porphyrin Dyes on TiO2 Surfaces with Different Orientations: A Photophysical, Photovoltaic, and Theoretical Investigation. The Journal of Physical Chemistry A 2014, 118 (19) , 3410-3418. https://doi.org/10.1021/jp412609k
  7. Jie Luo, Mingfei Xu, Renzhi Li, Kuo-Wei Huang, Changyun Jiang, Qingbiao Qi, Wangdong Zeng, Jie Zhang, Chunyan Chi, Peng Wang, and Jishan Wu . N-Annulated Perylene as An Efficient Electron Donor for Porphyrin-Based Dyes: Enhanced Light-Harvesting Ability and High-Efficiency Co(II/III)-Based Dye-Sensitized Solar Cells. Journal of the American Chemical Society 2014, 136 (1) , 265-272. https://doi.org/10.1021/ja409291g
  8. Guo Li, Mao Liang, Hui Wang, Zhe Sun, Lina Wang, Zhihui Wang, and Song Xue . Significant Enhancement of Open-Circuit Voltage in Indoline-Based Dye-Sensitized Solar Cells via Retarding Charge Recombination. Chemistry of Materials 2013, 25 (9) , 1713-1722. https://doi.org/10.1021/cm400196w
  9. Bogyu Lim, George Y. Margulis, Jun-Ho Yum, Eva L. Unger, Brian E. Hardin, Michael Grätzel, Michael D. McGehee, and Alan Sellinger . Silicon-Naphthalo/Phthalocyanine-Hybrid Sensitizer for Efficient Red Response in Dye-Sensitized Solar Cells. Organic Letters 2013, 15 (4) , 784-787. https://doi.org/10.1021/ol303436q
  10. Lihong Yu, Jingyu Xi, Hung Tat Chan, Tao Su, Lucy Jane Antrobus, Bin Tong, Yuping Dong, Wai Kin Chan, and David Lee Phillips . Novel Organic D-π-2A Sensitizer for Dye Sensitized Solar Cells and Its Electron Transfer Kinetics on TiO2 Surface. The Journal of Physical Chemistry C 2013, 117 (5) , 2041-2052. https://doi.org/10.1021/jp3113182
  11. Soumik Sarkar, Abhinandan Makhal, Tanujjal Bora, Karthik Lakhsman, Achintya Singha, Joydeep Dutta, and Samir Kumar Pal . Hematoporphyrin–ZnO Nanohybrids: Twin Applications in Efficient Visible-Light Photocatalysis and Dye-Sensitized Solar Cells. ACS Applied Materials & Interfaces 2012, 4 (12) , 7027-7035. https://doi.org/10.1021/am302288m
  12. Weijiang Ying, Fuling Guo, Jing Li, Qiong Zhang, Wenjun Wu, He Tian, and Jianli Hua . Series of New D-A-π-A Organic Broadly Absorbing Sensitizers Containing Isoindigo Unit for Highly Efficient Dye-Sensitized Solar Cells. ACS Applied Materials & Interfaces 2012, 4 (8) , 4215-4224. https://doi.org/10.1021/am300925e
  13. Samir Kumar Sarkar, Lauren J. Kang, Upendra Kumar Pandey, Christine K. Luscombe, Pakkirisamy Thilagar. Triarylborane-BODIPY conjugate: An efficient non-fullerene electron acceptor for bulk heterojunction organic solar cell. Solar Energy 2021, 230 , 242-249. https://doi.org/10.1016/j.solener.2021.10.048
  14. Diana Barraza-Jiménez, Azael Martínez-De la Cruz, Leticia Saucedo-Mendiola, Sandra Iliana Torres-Herrera, Adolfo Padilla Mendiola, Elva Marcela Coria Quiñones, Raúl Armando Olvera Corral, María Estela Frías-Zepeda, Manuel Alberto Flores-Hidalgo. Solvent Effects on Dye Sensitizers Derived from Anthocyanidins for Applications in Photocatalysis. 2020,,https://doi.org/10.5772/intechopen.87151
  15. Peng Zhang, Jingping Hu, Bingchuan Liu, Jiakuan Yang, Huijie Hou. Recent advances in metalloporphyrins for environmental and energy applications. Chemosphere 2019, 219 , 617-635. https://doi.org/10.1016/j.chemosphere.2018.12.024
  16. Gachumale Saritha, Sambandam Anandan, Muthupandian Ashokkumar. Cosensitization Strategies for Dye-Sensitized Solar Cells. 2018,,, 15-60. https://doi.org/10.1002/9781119437499.ch2
  17. Po‐Yu Ho, Michael F. Mark, Yi Wang, Sze‐Chun Yiu, Wai‐Hong Yu, Cheuk‐Lam Ho, David W. McCamant, Richard Eisenberg, Shuping Huang. Panchromatic Sensitization with Zn II Porphyrin‐Based Photosensitizers for Light‐Driven Hydrogen Production. ChemSusChem 2018, 11 (15) , 2517-2528. https://doi.org/10.1002/cssc.201801255
  18. Hu Lei, Paul-Ludovic Karsenti, Pierre D. Harvey. Azophenine as Central Core for Efficient Light Harvesting Devices. ChemPhysChem 2018, 19 (5) , 596-611. https://doi.org/10.1002/cphc.201701183
  19. Jamie C. Wang, Sean P. Hill, Tristan Dilbeck, Omotola O. Ogunsolu, Tanmay Banerjee, Kenneth Hanson. Multimolecular assemblies on high surface area metal oxides and their role in interfacial energy and electron transfer. Chemical Society Reviews 2018, 47 (1) , 104-148. https://doi.org/10.1039/C7CS00565B
  20. Narra Vamsi Krishna, Jonnadula Venkata Suman Krishna, Madoori Mrinalini, Seelam Prasanthkumar, Lingamallu Giribabu. Role of Co-Sensitizers in Dye-Sensitized Solar Cells. ChemSusChem 2017, 10 (23) , 4668-4689. https://doi.org/10.1002/cssc.201701224
  21. Lei Xu, Bin Wen, Gakhyun Kim, Taeyeon Kim, Fei Cheng, Mingbo Zhou, Ling Xu, Takayuki Tanaka, Bangshao Yin, Atsuhiro Osuka, Dongho Kim, Jianxin Song. Strategic Construction of Directly Linked Porphyrin-BODIPY Hybrids. Angewandte Chemie 2017, 129 (40) , 12490-12494. https://doi.org/10.1002/ange.201707237
  22. Lei Xu, Bin Wen, Gakhyun Kim, Taeyeon Kim, Fei Cheng, Mingbo Zhou, Ling Xu, Takayuki Tanaka, Bangshao Yin, Atsuhiro Osuka, Dongho Kim, Jianxin Song. Strategic Construction of Directly Linked Porphyrin-BODIPY Hybrids. Angewandte Chemie International Edition 2017, 56 (40) , 12322-12326. https://doi.org/10.1002/anie.201707237
  23. Liang Gao, Cong Ge, Wenhui Li, Chuancheng Jia, Kai Zeng, Weicheng Pan, Haodi Wu, Yang Zhao, Yisu He, Jungang He, Zhixin Zhao, Guangda Niu, Xuefeng Guo, F. Pelayo Garcia de Arquer, Edward H. Sargent, Jiang Tang. Flexible Filter-Free Narrowband Photodetector with High Gain and Customized Responsive Spectrum. Advanced Functional Materials 2017, 27 (33) , 1702360. https://doi.org/10.1002/adfm.201702360
  24. Hongshan He, James D. Bosonetta, Kraig A. Wheeler, Stanley P. May. Sisters together: co-sensitization of near-infrared emission of ytterbium( iii ) by BODIPY and porphyrin dyes. Chemical Communications 2017, 53 (73) , 10120-10123. https://doi.org/10.1039/C7CC05437H
  25. Venkataiah Mallam, Sanjib Baral, Santosh Gyawali, Robert P. Oda, Hytham Elbohy, Jeevan Nepal, Qiquan Qiao, Mahdi Farrokh Baroughi, Brian A. Logue. Functionalized Carboxylate Deposition for rapid sensitization of dye-sensitized solar cells. Solar Energy 2016, 126 , 128-136. https://doi.org/10.1016/j.solener.2015.12.044
  26. Shengbo Zhu, Zhongwei An, Xiao Sun, Zhisheng Wu, Xinbing Chen, Pei Chen. Synthesis and evaluation of simple molecule as a co-adsorbent dye for highly efficient co-sensitized solar cells. Dyes and Pigments 2015, 120 , 85-92. https://doi.org/10.1016/j.dyepig.2015.04.003
  27. Bo Zheng, Randy P. Sabatini, Wen-Fu Fu, Min-Sik Eum, William W. Brennessel, Lidong Wang, David W. McCamant, Richard Eisenberg. Light-driven generation of hydrogen: New chromophore dyads for increased activity based on Bodipy dye and Pt(diimine)(dithiolate) complexes. Proceedings of the National Academy of Sciences 2015, 112 (30) , E3987-E3996. https://doi.org/10.1073/pnas.1509310112
  28. Weixue Gao, Mao Liang, Yulin Tan, Min Wang, Zhe Sun, Song Xue. New triarylamine sensitizers for high efficiency dye-sensitized solar cells: Recombination kinetics of cobalt(III) complexes at titania/dye interface. Journal of Power Sources 2015, 283 , 260-269. https://doi.org/10.1016/j.jpowsour.2015.02.121
  29. Sudhan Sigdel, Hytham Elbohy, Jiawei Gong, Nirmal Adhikari, Krishnan Sumathy, Hui Qiao, Qufu Wei, Muhammad Hassan Sayyad, Jiantao Zai, Xuefeng Qian, Qiquan Qiao. Dye-Sensitized Solar Cells Based on Porous Hollow Tin Oxide Nanofibers. IEEE Transactions on Electron Devices 2015, 62 (6) , 2027-2032. https://doi.org/10.1109/TED.2015.2421475
  30. Sandeep B. Mane, Liyang Luo, Hsin-Han Tsai, Chen-Hsiung Hung. Co-sensitization of free-base and zinc porphyrins: An effective approach to improve the photon-to-current conversion efficiency of dye-sensitized solar cells. Journal of Porphyrins and Phthalocyanines 2015, 19 (05) , 695-707. https://doi.org/10.1142/S1088424615500170
  31. Wenhui Li, Liping Si, Zonghao Liu, Huaizhi Wu, Zhixin Zhao, Yi-Bing Cheng, Hongshan He. Bis(9,9-dihexyl-9H-fluorene-7-yl)amine (BDFA) as a new donor for porphyrin-sensitized solar cells. Organic Electronics 2014, 15 (10) , 2448-2460. https://doi.org/10.1016/j.orgel.2014.07.006
  32. G.D. Sharma, G.E. Zervaki, P.A. Angaridis, A. Vatikioti, K.S.V. Gupta, T. Gayathri, P. Nagarjuna, Surya Prakash Singh, M. Chandrasekharam, Ajita Banthiya, K. Bhanuprakash, A. Petrou, A.G. Coutsolelos. Stepwise co-sensitization as a useful tool for enhancement of power conversion efficiency of dye-sensitized solar cells: The case of an unsymmetrical porphyrin dyad and a metal-free organic dye. Organic Electronics 2014, 15 (7) , 1324-1337. https://doi.org/10.1016/j.orgel.2014.03.033
  33. Simon Mathew, Aswani Yella, Peng Gao, Robin Humphry-Baker, Basile F. E. Curchod, Negar Ashari-Astani, Ivano Tavernelli, Ursula Rothlisberger, Md. Khaja Nazeeruddin, Michael Grätzel. Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nature Chemistry 2014, 6 (3) , 242-247. https://doi.org/10.1038/nchem.1861
  34. Swamy. P Chinna Ayya, Pakkirisamy Thilagar. Effect of substituent position on optical properties of boron-dipyrromethane isomers. Inorganica Chimica Acta 2014, 411 , 97-101. https://doi.org/10.1016/j.ica.2013.11.032
  35. Hai-Jun Xu, Antoine Bonnot, Paul-Ludovic Karsenti, Adam Langlois, Mohammed Abdelhameed, Jean-Michel Barbe, Claude P. Gros, Pierre D. Harvey. Antenna effects in truxene-bridged BODIPY triarylzinc( ii )porphyrin dyads: evidence for a dual Dexter–Förster mechanism. Dalton Trans. 2014, 43 (22) , 8219-8229. https://doi.org/10.1039/C3DT53630K
  36. Saumya Singh, Vijay Venugopalan, Kothandam Krishnamoorthy. Organic soluble and uniform film forming oligoethylene glycol substituted BODIPY small molecules with improved hole mobility. Phys. Chem. Chem. Phys. 2014, 16 (26) , 13376-13382. https://doi.org/10.1039/C4CP01098A
  37. Wenhui Li, Liping Si, Zonghao Liu, Zhixin Zhao, Hongshan He, Kai Zhu, Brian Moore, Yi-Bing Cheng. Fluorene functionalized porphyrins as broadband absorbers for TiO 2 nanocrystalline solar cells. Journal of Materials Chemistry A 2014, 2 (33) , 13667. https://doi.org/10.1039/C4TA01954G
  38. Chin-Li Wang, Jyun-Yu Hu, Cheng-Hua Wu, Hshin-Hui Kuo, Yu-Cheng Chang, Zih-Jian Lan, Hui-Ping Wu, Eric Wei-Guang Diau, Ching-Yao Lin. Highly efficient porphyrin-sensitized solar cells with enhanced light harvesting ability beyond 800 nm and efficiency exceeding 10%. Energy & Environmental Science 2014, 7 (4) , 1392. https://doi.org/10.1039/c3ee44168g
  39. Liping Si, Hongshan He, Kai Zhu. 8-Hydroxylquinoline-conjugated porphyrins as broadband light absorbers for dye-sensitized solar cells. New Journal of Chemistry 2014, 38 (4) , 1565. https://doi.org/10.1039/c3nj01643a
  40. Jolanda Spadavecchia, Christophe Méthivier, Jessem Landoulsi, Claire-Marie Pradier. Interaction of Zn II Porphyrin with TiO 2 Nanoparticles: From Mechanism to Synthesis of Hybrid Nanomaterials. ChemPhysChem 2013, 14 (11) , 2462-2469. https://doi.org/10.1002/cphc.201300193
  41. Abdolreza Rezaeifard, Vahideh Soltani, Maasoumeh Jafarpour. Nanoaggregates of Simple Mn Porphyrin Complexes as Catalysts for the Selective Oxidation of Hydrocarbons. European Journal of Inorganic Chemistry 2013, 2013 (14) , 2657-2664. https://doi.org/10.1002/ejic.201201437
  42. Christina Stangel, Kalliopi Ladomenou, Georgios Charalambidis, Manas K. Panda, Theodore Lazarides, Athanassios G. Coutsolelos. Synthesis, Characterization and Electronic Properties of trans ‐[4‐(Alkoxycarbonyl)phenyl]porphyrin‐[Ru II (bpy) 3 ] 2 Complexes or Boron–Dipyrrin Conjugates as Panchromatic Sensitizers for DSSCs. European Journal of Inorganic Chemistry 2013, 2013 (8) , 1275-1286. https://doi.org/10.1002/ejic.201201248
  43. Lu-Lin Li, Eric Wei-Guang Diau. Porphyrin-sensitized solar cells. Chem. Soc. Rev. 2013, 42 (1) , 291-304. https://doi.org/10.1039/C2CS35257E
  44. Samir Kumar Sarkar, Pakkirisamy Thilagar. A borane–bithiophene–BODIPY triad: intriguing tricolor emission and selective fluorescence response towards fluoride ions. Chemical Communications 2013, 49 (76) , 8558. https://doi.org/10.1039/c3cc42979b
  45. George Y. Margulis, Bogyu Lim, Brian E. Hardin, Eva L. Unger, Jun-Ho Yum, Johann M. Feckl, Dina Fattakhova-Rohlfing, Thomas Bein, Michael Grätzel, Alan Sellinger, Michael D. McGehee. Highly soluble energy relay dyes for dye-sensitized solar cells. Physical Chemistry Chemical Physics 2013, 15 (27) , 11306. https://doi.org/10.1039/c3cp51018b
  46. Yueqiang Wang, Xin Li, Bo Liu, Wenjun Wu, Weihong Zhu, Yongshu Xie. Porphyrins bearing long alkoxyl chains and carbazole for dye-sensitized solar cells: tuning cell performance through an ethynylene bridge. RSC Advances 2013, 3 (34) , 14780. https://doi.org/10.1039/c3ra40788h
  47. G. D. Sharma, D. Daphnomili, K. S. V. Gupta, T. Gayathri, S. P. Singh, P. A. Angaridis, T. N. Kitsopoulos, D. Tasis, A. G. Coutsolelos. Enhancement of power conversion efficiency of dye-sensitized solar cells by co-sensitization of zinc-porphyrin and thiocyanate-free ruthenium(ii)-terpyridine dyes and graphene modified TiO2 photoanode. RSC Advances 2013, 3 (44) , 22412. https://doi.org/10.1039/c3ra42537a
  48. Remya Narayanan, Melepurath Deepa, Avanish Kumar Srivastava. Förster resonance energy transfer and carbon dots enhance light harvesting in a solid-state quantum dot solar cell. Journal of Materials Chemistry A 2013, 1 (12) , 3907. https://doi.org/10.1039/c3ta01601c
  49. Chinna Ayya Swamy P, Sanjoy Mukherjee, Pakkirisamy Thilagar. Tuning the solid state emission of meso-Me3SiC6H4 BODIPYs by tuning their solid state structure. Journal of Materials Chemistry C 2013, 1 (31) , 4691. https://doi.org/10.1039/c3tc30632a
  50. Hongshan He, Ashim Gurung, Liping Si, Andrew G. Sykes. A simple acrylic acid functionalized zinc porphyrin for cost-effective dye-sensitized solar cells. Chemical Communications 2012, 48 (61) , 7619. https://doi.org/10.1039/c2cc33337f