Tin-based perovskite solar cell explained

A tin-based perovskite solar cell is a special type of perovskite solar cell, based on a tin perovskite structure (ASnX3, where 'A' is a monovalent cation, tin is in its Sn (II) oxidation state and 'X' is a monovalent halogen anion). As a technology, tin-based perovskite solar cells are still in the research phase, and are even less-studied than their counterpart, lead-based perovskite solar cells. The main advantages of tin-based perovskite solar cells are that they are lead-free. There are environmental concerns with using lead-based perovskite solar cells in large-scale applications;[1] [2] one such concern is that since the material is soluble in water, and lead is highly toxic, any contamination from damaged solar cells could cause major health and environmental problems.[3] [4]

The maximum solar cell efficiency reported and certified is 14.6% for a modified formamidinium tin triiodide-based (CH(NH2)2SnI3 or FAPbI3) composition with additional NH4SCN and PEABr content,[5] 5.73% for CH3NH3SnIBr2,[6] 3% for CsSnI3 (5.03% in quantum dots), and above 10% for various compositions based on formamidinium tin triiodide.[7] [8] FAPbI3 in particular may hold promise because, applied as a thin film, it appears to have the potential to exceed the Shockley–Queisser limit by allowing hot-electron capture, which could considerably raise the efficiency.[9]

Methylammonium tin triiodide (CH3NH3SnI3 or MASnI3) has a band gap range of 1.2–1.3 eV, while FASnI3 has a band gap of approximately 1.4 eV.

Self-doping

The main obstacle to viable tin perovskite solar cells is the instability of tin's oxidation state Sn2+, which is easily oxidized to the stabler Sn4+.[10] In solar cell research, this process is called self-doping,[11] because the Sn4+ acts as a p-dopant and reduces solar cell efficiency. The vacancy defects that promote this process are the subject of active research; folk wisdom holds that the process requires tin vacancies, but in CsSnI3, the primary hole contributors are instead Cs vacancies.[12] In general, reducing tin vacancies is still ideal, because they impede charge carrier motion and lower efficiency.[13]

Several techniques have been explored as a means of counteracting the self-doping of Sn-based perovskites. One method is the sealing of cells with polymers such as poly(methyl methacrylate) so that they are not exposed to oxygen.[14] Alternatively, increasing the size of the organic component is believed to geometrically bar diffusion of oxygen.[15] However, these techniques do not counteract Sn4+ ions formed during cell synthesis. Such ions can be with a chelating ligand, e.g. formamidinium chloride; the tin coordination complex can then be removed with gentle (<60 °C) heat. As long as the temperature to vaporize the complex is below that at which the perovskite loses mass, the perovskite film will remain intact after this processing step, save for the removed Sn(IV) ions.[16]

Another option is adding reducing agents as sacrificial anodes: these may be as varied as maltol, gallic acid, or hydrazine.[17] [18] Tin-based reductants, such as the pure element or stannous halides, also act as a tin source, filling in Sn vacancies.

Annealing perovskite films during deposition also reduces self-doping.[19]

Morphology of thin films

Another challenge of tin perovskite solar cells is to be found in the rapid crystallization of tin perovskite, often leading to poor morphology, high pinhole density and incomplete substrate coverage. The morphology of the tin perovskite thin films has been improved via vapor-assisted processing[20] and hot antisolvent methods. Other studies suggest that the addition of methylammonium chloride into the precursor solution improves the morphology of the tin perovskite thin films.[21]

Notes and References

  1. Espinosa . Nieves . Serrano-Luján . Lucía . Urbina . Antonio . Krebs . Frederik C. . Solution and vapour deposited lead perovskite solar cells: Ecotoxicity from a life cycle assessment perspective . Solar Energy Materials and Solar Cells . June 2015 . 137 . 303–310 . 10.1016/j.solmat.2015.02.013 . 2015SEMSC.137..303E .
  2. Zhang . Jingyi . Gao . Xianfeng . Deng . Yelin . Li . Bingbing . Yuan . Chris . Life Cycle Assessment of Titania Perovskite Solar Cell Technology for Sustainable Design and Manufacturing . ChemSusChem . November 2015 . 8 . 22 . 3882–3891 . 10.1002/cssc.201500848 . 26489525 . 2015ChSCh...8.3882Z .
  3. Benmessaoud . Iness R. . Mahul-Mellier . Anne-Laure . Horváth . Endre . Maco . Bohumil . Spina . Massimo . Lashuel . Hilal A. . Forró . Làszló . Health hazards of methylammonium lead iodide based perovskites: cytotoxicity studies . Toxicology Research . 2016 . 5 . 2 . 407–419 . 10.1039/c5tx00303b . 30090356 . 6062200 .
  4. Babayigit . Aslihan . Duy Thanh . Dinh . Ethirajan . Anitha . Manca . Jean . Muller . Marc . Boyen . Hans-Gerd . Conings . Bert . Assessing the toxicity of Pb- and Sn-based perovskite solar cells in model organism Danio rerio . Scientific Reports . 13 January 2016 . 6 . 1 . 18721 . 10.1038/srep18721 . 26759068 . 2016NatSR...618721B . 4725943 .
  5. Jiang . Xianyuan . Li . Hansheng . Zhou . Qilin . Wei . Qi . Wei . Mingyang . Jiang . Luozhen . Wang . Zhen . Peng . Zijian . Wang . Fei . Zang . Zihao . Xu . Kaimin . Hou . Yi . Teale . Sam . Zhou . Wenjia . Si . Rui . Gao . Xingyu . Sargent . Edward H. . Ning . Zhijun . One-Step Synthesis of SnI2·(DMSO)x Adducts for High-Performance Tin Perovskite Solar Cells . Journal of the American Chemical Society . 28 July 2021 . 143 . 29 . 10970–10976 . 10.1021/jacs.1c03032 . 34196528 .
  6. Hao . Feng . Stoumpos . Constantinos C. . Cao . Duyen Hanh . Chang . Robert P. H. . Kanatzidis . Mercouri G. . Lead-free solid-state organic–inorganic halide perovskite solar cells . Nature Photonics . June 2014 . 8 . 6 . 489–494 . 10.1038/nphoton.2014.82 . 2014NaPho...8..489H .
  7. Shuyan Shao, Jian Liu, Giuseppe Portale, Hong-Hua Fang, Graeme R. Blake, Gert H. ten Brink, L. Jan Anton Koster, Maria Antonietta Loi . 2018 . Highly Reproducible Sn-Based Hybrid Perovskite Solar Cells with 9% Efficiency . Advanced Energy Materials . 8 . 4 . 1702019 . 10.1002/aenm.201702019 . free. 2018AdEnM...802019S .
  8. Jokar . Efat . Chien . Cheng-Hsun . Tsai . Cheng-Min . Fathi . Amir . Diau . Eric Wei-Guang . Robust Tin-Based Perovskite Solar Cells with Hybrid Organic Cations to Attain Efficiency Approaching 10% . Advanced Materials . January 2019 . 31 . 2 . e1804835 . 10.1002/adma.201804835 . 30411826 . 2019AdM....3104835J .
  9. Fang . Hong-Hua . Adjokatse . Sampson . Shao . Shuyan . Even . Jacky . Loi . Maria Antonietta . January 16, 2018 . Long-lived hot-carrier light emission and large blue shift in formamidinium tin triiodide perovskites . . 9 . 243 . 2018NatCo...9..243F . 10.1038/s41467-017-02684-w . 5770436 . 29339814 . 243.
  10. Lee . Seon Joo . Shin . Seong Sik . Kim . Young Chan . Kim . Dasom . Ahn . Tae Kyu . Noh . Jun Hong . Seo . Jangwon . Seok . Sang Il . Fabrication of Efficient Formamidinium Tin Iodide Perovskite Solar Cells through SnF 2 –Pyrazine Complex . Journal of the American Chemical Society . 30 March 2016 . 138 . 12 . 3974–3977 . 10.1021/jacs.6b00142 . 26960020 .
  11. Takahashi . Yukari . Obara . Rena . Lin . Zheng-Zhong . Takahashi . Yukihiro . Naito . Toshio . Inabe . Tamotsu . Ishibashi . Shoji . Terakura . Kiyoyuki . Charge-transport in tin-iodide perovskite CH3NH3SnI3: origin of high conductivity . Dalton Transactions . 2011 . 40 . 20 . 5563–5568 . 10.1039/C0DT01601B . 21494720 . 2115/48597 . free .
  12. Zhang . Jiajia . Zhong . Yu . Origins of p-Doping and Nonradiative Recombination in CsSnI 3 . Angewandte Chemie . 2 November 2022 . 134 . 44 . 10.1002/ange.202212002 . 2022AngCh.13412002Z .
  13. Chang . Bohong . Li . Bo . Wang . Zhongxiao . Li . Hui . Wang . Lian . Pan . Lu . Li . Zihao . Yin . Longwei . Efficient Bulk Defect Suppression Strategy in FASnI 3 Perovskite for Photovoltaic Performance Enhancement . Advanced Functional Materials . March 2022 . 32 . 12 . 10.1002/adfm.202107710 .
  14. Yin . Yongqi . Wang . Mengqi . Malgras . Victor . Yamauchi . Yusuke . Stable and Efficient Tin-Based Perovskite Solar Cell via Semiconducting–Insulating Structure . ACS Applied Energy Materials . 23 November 2020 . 3 . 11 . 10447–10452 . 10.1021/acsaem.0c01422 .
  15. Lanzetta . Luis . Marin-Beloqui . Jose Manuel . Sanchez-Molina . Irene . Ding . Dong . Haque . Saif A. . Two-Dimensional Organic Tin Halide Perovskites with Tunable Visible Emission and Their Use in Light-Emitting Devices . ACS Energy Letters . 14 July 2017 . 2 . 7 . 1662–1668 . 10.1021/acsenergylett.7b00414 .
  16. Zhou . Jianheng . Hao . Mingwei . Zhang . Yu . Ma . Xue . Dong . Jianchao . Lu . Feifei . Wang . Jie . Wang . Ning . Zhou . Yuanyuan . Chemo-thermal surface dedoping for high-performance tin perovskite solar cells . Matter . February 2022 . 5 . 2 . 683–693 . 10.1016/j.matt.2021.12.013 .
  17. Hu . Shuaifeng . Truong . Minh Anh . Otsuka . Kento . Handa . Taketo . Yamada . Takumi . Nishikubo . Ryosuke . Iwasaki . Yasuko . Saeki . Akinori . Murdey . Richard . Kanemitsu . Yoshihiko . Wakamiya . Atsushi . Mixed lead–tin perovskite films with >7 μs charge carrier lifetimes realized by maltol post-treatment . Chemical Science . 2021 . 12 . 40 . 13513–13519 . 10.1039/D1SC04221A . 34777771 . 8528037 .
  18. Cao . Jiupeng . Yan . Feng . Recent progress in tin-based perovskite solar cells . Energy & Environmental Science . 2021 . 14 . 3 . 1286–1325 . 10.1039/D0EE04007J .
  19. Mu . Haichuan . Hu . Fan . Wang . Ruibin . Jia . Junlin . Effects of in-situ annealing on the electroluminescence performance of the Sn-based perovskite light-emitting diodes prepared by thermal evaporation . Journal of Luminescence . October 2020 . 226 . 117493 . 10.1016/j.jlumin.2020.117493 .
  20. Liu . Jiewei . Ozaki . Masashi . Yakumaru . Shinya . Handa . Taketo . Nishikubo . Ryosuke . Kanemitsu . Yoshihiko . Saeki . Akinori . Murata . Yasujiro . Murdey . Richard . Wakamiya . Atsushi . Lead-Free Solar Cells based on Tin Halide Perovskite Films with High Coverage and Improved Aggregation . Angewandte Chemie International Edition . October 2018 . 57 . 40 . 13221–13225 . 10.1002/anie.201808385 . 30110137 .
  21. Cuzzupè . Daniele T. . Öz . Seren Dilara . Ling . JinKiong . Illing . Elias . Seewald . Tobias . Jose . Rajan . Olthof . Selina . Fakharuddin . Azhar . Schmidt-Mende . Lukas . Understanding the Methylammonium Chloride-Assisted Crystallization for Improved Performance of Lead-Free Tin Perovskite Solar Cells . Solar RRL . December 2023 . 7 . 24 . 10.1002/solr.202300770 . free .

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