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Tin-based perovskite solar cell

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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 corresponding perovskite solar cells (PSCs) with lead have reached a certified power conversion efficiency (PCE) of 25.2%. However, the toxic lead in perovskites has caused extensive concerns regarding to the real-life applications of PSCs.[1] There are environmental concerns with using lead-based perovskite solar cells in large-scale applications;[2][3] 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.[4][5] Therefore, the development of eco-friendly lead-free PSCs is highly desired and one promising strategy is to replace lead with tin. Several tin-based perovskites such as CsSnI3, MASnI3 ,and FASnI3 have been reported for fabricating lead-free PSCs.[6]

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,[7] 5.73% for CH3NH3SnIBr2,[8] 3% for CsSnI3 (5.03% in quantum dots), and above 10% for various compositions based on formamidinium tin triiodide.[9][10] 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.[11]

Enhance stability

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Solar cell stability is critical to practical applications especially for outdoor photovoltaic modules that are expected to be used for tens of years. The stability of Sn-based PSCs is greatly dependent on the fabrication pro-cess and perovskite composition.[12] Tin-based perovskites have the potential to outperform the PCE and stability of lead-based perovskite solar cells.[13] There are lots of ways to enhance the stability. Several experimental and simulation studies have predicted that the addition of the cesium Cs + can enhance the thermodynamic structural stability of FASnI3, prevent Sn2+ oxidation, and increase geometric symmetry.[14] Research from Marshall et al. has improved the stability and efficiency of PSCs without a hole-selective interfacial layer.[15] Next, by alloying Ge (II) in CsSnI3 to develop a CsSn0.5Ge0.5I3 composition perovskite, thin films of CsSnI3-based PSCs can become very stable and air tolerant.[16] Qiu et al. also suggested creating high-quality B-γ CsSnI3 thin films with a two-step sequential deposition process.[17] Furthermore, to overcome the difficulty of large-scale manufacturing, several researchers have focused on refining deposition techniques and enhancing perovskite nano crystals or perovskite ink.[18] The solvent SnI2 is also one of the additives commonly used in Sn-based alloys to reduce the impurity of the Sn source.[19] The charge transport in the 2D perovskite caused the efficiency to decrease, so a 3D precursor was introduced to develop 2D/3D mixed Sn-based perovskites to obtain far better performance and stability than pure quasi2D perovskites.[20]

Self-doping

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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+.[21] In solar cell research, this process is called self-doping,[22] 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.[23] In general, reducing tin vacancies is still ideal, because they impede charge carrier motion and lower efficiency.[24]

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.[25] Alternatively, increasing the size of the organic component is believed to geometrically bar diffusion of oxygen.[26] 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.[27]

Another option is adding reducing agents as sacrificial anodes: these may be as varied as maltol, gallic acid, or hydrazine.[28][29] Tin-based reductants, such as the pure element or stannous halides, also act as a tin source, filling in Sn vacancies.[29]

Annealing perovskite films during deposition also reduces self-doping.[30]

Morphology of thin films

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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[31] and hot antisolvent methods.[31] Other studies suggest that the addition of methylammonium chloride into the precursor solution improves the morphology of the tin perovskite thin films.[32] SnF2 is a key additive for tin-based PSCs because it can increase the energy of formation of tin vacancies, leading to decreased concentrations of defects of this kind. A similar result was reported with SnCl 2 as additive in tin perovskite.[33] An addition ofSnF2 can also improve the film morphology because the additive can act as heterogeneous nucleation sites, not only facilitating the formation of more tin perovskite nuclei but also enabling more homogeneous crystal growth with full surface coverage.[34]

References

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  2. ^ Espinosa, Nieves; Serrano-Luján, Lucía; Urbina, Antonio; Krebs, Frederik C. (June 2015). "Solution and vapour deposited lead perovskite solar cells: Ecotoxicity from a life cycle assessment perspective". Solar Energy Materials and Solar Cells. 137: 303–310. Bibcode:2015SEMSC.137..303E. doi:10.1016/j.solmat.2015.02.013.
  3. ^ Zhang, Jingyi; Gao, Xianfeng; Deng, Yelin; Li, Bingbing; Yuan, Chris (November 2015). "Life Cycle Assessment of Titania Perovskite Solar Cell Technology for Sustainable Design and Manufacturing". ChemSusChem. 8 (22): 3882–3891. Bibcode:2015ChSCh...8.3882Z. doi:10.1002/cssc.201500848. PMID 26489525.
  4. ^ Benmessaoud, Iness R.; Mahul-Mellier, Anne-Laure; Horváth, Endre; Maco, Bohumil; Spina, Massimo; Lashuel, Hilal A.; Forró, Làszló (2016). "Health hazards of methylammonium lead iodide based perovskites: cytotoxicity studies". Toxicology Research. 5 (2): 407–419. doi:10.1039/c5tx00303b. PMC 6062200. PMID 30090356.
  5. ^ Babayigit, Aslihan; Duy Thanh, Dinh; Ethirajan, Anitha; Manca, Jean; Muller, Marc; Boyen, Hans-Gerd; Conings, Bert (13 January 2016). "Assessing the toxicity of Pb- and Sn-based perovskite solar cells in model organism Danio rerio". Scientific Reports. 6 (1): 18721. Bibcode:2016NatSR...618721B. doi:10.1038/srep18721. PMC 4725943. PMID 26759068.
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