Dual Sensitization Strategy for High-Performance Core/Shell/Quasi-shell Quantum Dot Solar Cells

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Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur−741246, India
Cite this: Chem. Mater. 2015, 27, 13, 4848–4859
Publication Date (Web):June 11, 2015
Copyright © 2015 American Chemical Society
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The potential of quantum-dot sensitized solar cells (QDSCs), a promising candidate for third-generation photovoltaics, has not been fully realized with the corresponding power conversion efficiencies (PCE) still hovering below 9%. In this context, we demonstrate an optimized dual sensitization strategy that combines the linker-assisted self-assembly of QDs and successive ionic layer adsorption and reaction (SILAR) approach to assemble high-efficiency QDSCs. CdTe/CdS core/shell QDSC is chosen as the model system whose PCE, so far, has been reported at ∼3.8%. Our dual sensitization strategy comprises self-assembly of Type-II CdTe/CdS core/shell QDs on porous TiO2 followed by deposition of an additional CdS quasi-shell through SILAR. The highest QD surface coverage was optimized by systematic pH variation, whereby PCE improved from 2.04(1)% (pH 11) to 3.696(5)% (pH 13). It was observed that while the epitaxial shell passivates the core surface traps, the nonepitaxial quasi-shell passivates the TiO2 surface states. Thus, for core/shell, core/quasi-shell and core/shell/quasi-shell sensitized devices, PCE increased as 1.5(1)%, 3.6(4)%, and 5.69(2)%, respectively. The thickness of CdS shell and quasi-shell were optimized to achieve the PCE of CdTe/CdS/CdS core/shell/quasi-shell QDSCs as high as 6.32(9)% (6.41% for the champion cell), which notably is the highest for any aqueous processed QDSC.

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Tables of TrPL decay and photovoltaic parameters, OCVD data and discussion on integrated photocurrent density. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.5b01731.

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  3. Ganga Halder, Anima Ghosh, Sahanaz Parvin, Sayan Bhattacharyya. Cation Exchange in Zn–Ag–In–Se Core/Alloyed Shell Quantum Dots and Their Applications in Photovoltaics and Water Photolysis. Chemistry of Materials 2019, 31 (1) , 161-170. https://doi.org/10.1021/acs.chemmater.8b03743
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  11. Muhammad A. Abbas, Muhammad A. Basit, Seog Joon Yoon, Geun Jun Lee, Moo Dong Lee, Tae Joo Park, Prashant V. Kamat, and Jin Ho Bang . Revival of Solar Paint Concept: Air-Processable Solar Paints for the Fabrication of Quantum Dot-Sensitized Solar Cells. The Journal of Physical Chemistry C 2017, 121 (33) , 17658-17670. https://doi.org/10.1021/acs.jpcc.7b05207
  12. Partha Maity, Sourav Maiti, Tushar Debnath, Jayanta Dana, Saurav K. Guin, and Hirendra N. Ghosh . Intraband Electron Cooling Mediated Unprecedented Photocurrent Conversion Efficiency of CdSxSe1–x Alloy QDs: Direct Correlation between Electron Cooling and Efficiency. The Journal of Physical Chemistry C 2016, 120 (38) , 21309-21316. https://doi.org/10.1021/acs.jpcc.6b07876
  13. Metikoti Jagadeeswararao, Abhishek Swarnkar, Ganesh B. Markad, and Angshuman Nag . Defect-Mediated Electron–Hole Separation in Colloidal Ag2S–AgInS2 Hetero Dimer Nanocrystals Tailoring Luminescence and Solar Cell Properties. The Journal of Physical Chemistry C 2016, 120 (34) , 19461-19469. https://doi.org/10.1021/acs.jpcc.6b06394
  14. Jia-Yaw Chang, Chen-Hei Li, Ya-Han Chiang, Chia-Hung Chen, and Pei-Ni Li . Toward the Facile and Ecofriendly Fabrication of Quantum Dot-Sensitized Solar Cells via Thiol Coadsorbent Assistance. ACS Applied Materials & Interfaces 2016, 8 (29) , 18878-18890. https://doi.org/10.1021/acsami.6b05411
  15. Zhenwei Ren, Jin Wang, Zhenxiao Pan, Ke Zhao, Hua Zhang, Yan Li, Yixin Zhao, Ivan Mora-Sero, Juan Bisquert, and Xinhua Zhong . Amorphous TiO2 Buffer Layer Boosts Efficiency of Quantum Dot Sensitized Solar Cells to over 9%. Chemistry of Materials 2015, 27 (24) , 8398-8405. https://doi.org/10.1021/acs.chemmater.5b03864
  16. Ali Reza Amani-Ghadim, Ehsan Mohammad-Gholipour-Rezaei, Farzaneh Bayat, Samira Agbolaghi, Fatemeh Khodam. Enhancement in photovoltaic properties of exciplex quantum dot sensitized solar cells via gadolinium doping and formation of type II Core/Shell (Gd-doped [email protected]) structure. Solar Energy 2022, 231 , 402-413. https://doi.org/10.1016/j.solener.2021.11.055
  17. Sebastiano Bellani, Antonino Bartolotta, Antonio Agresti, Giuseppe Calogero, Giulia Grancini, Aldo Di Carlo, Emmanuel Kymakis, Francesco Bonaccorso. Solution-processed two-dimensional materials for next-generation photovoltaics. Chemical Society Reviews 2021, 50 (21) , 11870-11965. https://doi.org/10.1039/D1CS00106J
  18. Ru Zhou, Jun Xu, Paifeng Luo, Linhua Hu, Xu Pan, Jinzhang Xu, Yang Jiang, Lianzhou Wang. Near‐Infrared Photoactive Semiconductor Quantum Dots for Solar Cells. Advanced Energy Materials 2021, 11 (40) , 2101923. https://doi.org/10.1002/aenm.202101923
  19. S. Liu, R. Fan, Y. Zhao, M. Yu, Y. Fu, L. Li, Q. Li, B. Liang, W. Zhang. Assembly of Cu–In–Sn–Se quantum dot–sensitized TiO2 films for efficient quantum dot–sensitized solar cell application. Materials Today Energy 2021, 21 , 100798. https://doi.org/10.1016/j.mtener.2021.100798
  20. Han Song, Yu Lin, Mengsi Zhou, Huashang Rao, Zhenxiao Pan, Xinhua Zhong. Zn‐Cu‐In‐S‐Se Quinary “Green” Alloyed Quantum‐Dot‐Sensitized Solar Cells with a Certified Efficiency of 14.4 %. Angewandte Chemie 2021, 133 (11) , 6202-6209. https://doi.org/10.1002/ange.202014723
  21. Han Song, Yu Lin, Mengsi Zhou, Huashang Rao, Zhenxiao Pan, Xinhua Zhong. Zn‐Cu‐In‐S‐Se Quinary “Green” Alloyed Quantum‐Dot‐Sensitized Solar Cells with a Certified Efficiency of 14.4 %. Angewandte Chemie International Edition 2021, 60 (11) , 6137-6144. https://doi.org/10.1002/anie.202014723
  22. Wenhui Li, Xijia Yang, Liying Wang, Xueyu Zhang, Xuesong Li, Wei Lü. Improved performance of quantum dot-sensitized solar cells by full-spectrum utilization. Superlattices and Microstructures 2020, 148 , 106730. https://doi.org/10.1016/j.spmi.2020.106730
  23. Lingling Wen, Qian Chen, Liya Zhou, Meixin Huang, Jiangying Lu, Xiaoying Zhong, Hua Fan, Yingjun Ou. [email protected] composite material improved the photoelectric efficiency of cadmium-series QDSSCs. Optical Materials 2020, 108 , 110172. https://doi.org/10.1016/j.optmat.2020.110172
  24. Yifan Chen, Yinyin Li, Chunxia Wu, Dejun Wang, Yanhong Lin, Xintong Zhang, Xiaoxin Zou, Tengfeng Xie. In-situ preparation of ZnO/Cu2−xS on AZO conductive substrate and applied as counter electrode for quantum dot sensitized solar cells. Solar Energy 2020, 207 , 659-667. https://doi.org/10.1016/j.solener.2020.06.080
  25. Guoqiang Long, Wenhua Li, Wanyue Luo, Qianqiao Chen, Qin Zhong. Glucose-derived porous carbon as a highly efficient and low-cost counter electrode for quantum dot-sensitized solar cells. New Journal of Chemistry 2020, 44 (16) , 6362-6368. https://doi.org/10.1039/D0NJ00447B
  26. Vincent Tiing Tiong, Hongxia Wang. Photon-Responsive Nanomaterials for Solar Cells. 2020,,, 1-63. https://doi.org/10.1007/978-3-030-39994-8_1
  27. Yifan Chen, Dejun Wang, Yanhong Lin, Xiaoxin Zou, Tengfeng Xie. An in situ inward etching strategy for constructing a p-p heterojunction Cu2S/Cu2-xSe material based on brass as an effective counter electrode for quantum dot sensitized solar cells. Journal of Power Sources 2019, 442 , 227222. https://doi.org/10.1016/j.jpowsour.2019.227222
  28. Sourav Maiti, Pranav Anand, Farazuddin Azlan, Jayanta Dana, Hirendra N. Ghosh. Improving the Power‐Conversion Efficiency through Alloying in Common Anion CdZnX (X=S, Se) Nanocrystal Sensitized Solar Cells. ChemPhysChem 2019, 20 (20) , 2662-2667. https://doi.org/10.1002/cphc.201900379
  29. Yifan Chen, Dejun Wang, Yanhong Lin, Xiaoxin Zou, Tengfeng Xie. In situ fabrication of Cu2−xSe networks nanostructure counter electrode based on Ti substrate via sacrifice template method for quantum dot sensitized solar cells. Solar Energy 2019, 191 , 291-299. https://doi.org/10.1016/j.solener.2019.08.076
  30. Sourav Maiti, Farazuddin Azlan, Yogesh Jadhav, Jayanta Dana, Pranav Anand, Santosh K. Haram, G.R. Dey, Hirendra N. Ghosh. Efficient charge transport in surface engineered TiO2 nanoparticulate photoanodes leading to improved performance in quantum dot sensitized solar cells. Solar Energy 2019, 181 , 195-202. https://doi.org/10.1016/j.solener.2019.02.001
  31. Zhonglin Du, Mikhail Artemyev, Jin Wang, Jianguo Tang. Performance improvement strategies for quantum dot-sensitized solar cells: a review. Journal of Materials Chemistry A 2019, 7 (6) , 2464-2489. https://doi.org/10.1039/C8TA11483H
  32. Soosaimanickam Ananthakumar, Devakumar Balaji, Jeyagopal Ram Kumar, Sridharan Moorthy Babu. Role of co-sensitization in dye-sensitized and quantum dot-sensitized solar cells. SN Applied Sciences 2019, 1 (2) https://doi.org/10.1007/s42452-018-0054-3
  33. Sourav Maiti, Jayanta Dana, Hirendra N. Ghosh. Correlating Charge‐Carrier Dynamics with Efficiency in Quantum‐Dot Solar Cells: Can Excitonics Lead to Highly Efficient Devices?. Chemistry – A European Journal 2019, 25 (3) , 692-702. https://doi.org/10.1002/chem.201801853
  34. Ha Thanh Tung, Bui Van Thang, Nguyen Thu Thao, Nguyen Tan Phat, Huynh Thanh Dat, Lam Quang Vinh. A study of the degradation process of quantum dots sensitized solar cells. Advances in Natural Sciences: Nanoscience and Nanotechnology 2018, 9 (4) , 045008. https://doi.org/10.1088/2043-6254/aaeee4
  35. Zhenxiao Pan, Huashang Rao, Iván Mora-Seró, Juan Bisquert, Xinhua Zhong. Quantum dot-sensitized solar cells. Chemical Society Reviews 2018, 47 (20) , 7659-7702. https://doi.org/10.1039/C8CS00431E
  36. Rong Nie, Wenjie Ma, Yapeng Dong, Yanjie Xu, Jinyuan Wang, Jianguo Wang, Huanwang Jing. Artificial Photosynthesis of Methanol by Mn:CdS and CdSeTe Quantum Dot Cosensitized Titania Photocathode in Imine-Based Ionic Liquid Aqueous Solution. ChemCatChem 2018, 10 (15) , 3342-3350. https://doi.org/10.1002/cctc.201800190
  37. Anuraj S. Kshirsagar, Pawan. K. Khanna. Reaction Tailoring for Synthesis of Phase-Pure Nanocrystals of AgInSe 2 , Cu 3 SbSe 3 and CuSbSe 2. ChemistrySelect 2018, 3 (10) , 2854-2866. https://doi.org/10.1002/slct.201702986
  38. Xiaohui Song, Xingna Liu, Yong Yan, Jianping Deng, Yongyong Wang, Xiao Dong, Zhenkun Mo, Congxin Xia. One-pot hydrothermal synthesis of thioglycolic acid-capped CdSe quantum dots-sensitized mesoscopic TiO2 photoanodes for sensitized solar cells. Solar Energy Materials and Solar Cells 2018, 176 , 418-426. https://doi.org/10.1016/j.solmat.2017.10.032
  39. Chenguang Zhang, Shaowen Liu, Xingwei Liu, Fei Deng, Yan Xiong, Fang-Chang Tsai. Incorporation of Mn 2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells. Royal Society Open Science 2018, 5 (3) , 171712. https://doi.org/10.1098/rsos.171712
  40. Jayanta Dana, Sourav Maiti, Vaidehi S. Tripathi, Hirendra N. Ghosh. Direct Correlation of Excitonics with Efficiency in a Core-Shell Quantum Dot Solar Cell. Chemistry - A European Journal 2018, 24 (10) , 2418-2425. https://doi.org/10.1002/chem.201705127
  41. Md. Sariful Sheikh, Dibyendu Ghosh, Alo Dutta, Sayan Bhattacharyya, T.P. Sinha. Lead free double perovskite oxides Ln 2 NiMnO 6 (Ln = La, Eu, Dy, Lu), a new promising material for photovoltaic application. Materials Science and Engineering: B 2017, 226 , 10-17. https://doi.org/10.1016/j.mseb.2017.08.027
  42. Pei-Ni Li, Anil V. Ghule, Jia-Yaw Chang. Direct aqueous synthesis of quantum dots for high-performance AgInSe 2 quantum-dot-sensitized solar cell. Journal of Power Sources 2017, 354 , 100-107. https://doi.org/10.1016/j.jpowsour.2017.04.040
  43. Meidan Ye, Xiaoyue Gao, Xiaodan Hong, Qun Liu, Chunfeng He, Xiangyang Liu, Changjian Lin. Recent advances in quantum dot-sensitized solar cells: insights into photoanodes, sensitizers, electrolytes and counter electrodes. Sustainable Energy & Fuels 2017, 1 (6) , 1217-1231. https://doi.org/10.1039/C7SE00137A
  44. Ganga Halder, Sayan Bhattacharyya. Zinc-diffused silver indium selenide quantum dot sensitized solar cells with enhanced photoconversion efficiency. Journal of Materials Chemistry A 2017, 5 (23) , 11746-11755. https://doi.org/10.1039/C7TA00268H
  45. Xing Du, Xuan He, Lei Zhao, Hui Chen, Weixin Li, Wei Fang, Wanqiu Zhang, Junjie Wang, Huan Chen. TiO2 hierarchical porous film constructed by ultrastable foams as photoanode for quantum dot-sensitized solar cells. Journal of Power Sources 2016, 332 , 1-7. https://doi.org/10.1016/j.jpowsour.2016.09.103
  46. Tomah Sogabe, Qing Shen, Koichi Yamaguchi. Recent progress on quantum dot solar cells: a review. Journal of Photonics for Energy 2016, 6 (4) , 040901. https://doi.org/10.1117/1.JPE.6.040901
  47. Atharva Sahasrabudhe, Sutanu Kapri, Sayan Bhattacharyya. Graphitic porous carbon derived from human hair as ‘green’ counter electrode in quantum dot sensitized solar cells. Carbon 2016, 107 , 395-404. https://doi.org/10.1016/j.carbon.2016.06.015
  48. Jin Wang, Yan Li, Qing Shen, Takuya Izuishi, Zhenxiao Pan, Ke Zhao, Xinhua Zhong. Mn doped quantum dot sensitized solar cells with power conversion efficiency exceeding 9%. Journal of Materials Chemistry A 2016, 4 (3) , 877-886. https://doi.org/10.1039/C5TA09306F
  49. Dibyendu Ghosh, Ganga Halder, Atharva Sahasrabudhe, Sayan Bhattacharyya. A microwave synthesized Cu x S and graphene oxide nanoribbon composite as a highly efficient counter electrode for quantum dot sensitized solar cells. Nanoscale 2016, 8 (20) , 10632-10641. https://doi.org/10.1039/C6NR01161F
  50. Junwei Yang, Xinhua Zhong. CdTe based quantum dot sensitized solar cells with efficiency exceeding 7% fabricated from quantum dots prepared in aqueous media. Journal of Materials Chemistry A 2016, 4 (42) , 16553-16561. https://doi.org/10.1039/C6TA07399A
  51. Shuqin Zhou, Junyou Yang, Weixin Li, Qinghui Jiang, Yubo Luo, Dan Zhang, Zhiwei Zhou, Xin Li. Preparation and Photovoltaic Properties of Ternary AgBiS 2 Quantum Dots Sensitized TiO 2 Nanorods Photoanodes by Electrochemical Atomic Layer Deposition. Journal of The Electrochemical Society 2016, 163 (3) , D63-D67. https://doi.org/10.1149/2.0161603jes