三碘合锡(II)酸甲铵

三碘合锡(II)酸甲铵
英文名	Methylammonium tin triiodide; Methylamine triiodostannate(1-)
别名	MASnI3
识别
CAS号	67908-87-6
性质
化学式	CH3NH3SnI3
摩尔质量	531.488 g·mol⁻¹
外观	黑色晶体
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

三碘合锡(II)酸甲铵是一种有机钙钛矿材料，化学式为CH₃NH₃SnI₃，它作为含铅钙钛矿的替代品，在光电领域有着潜在应用。^[1]

制备[编辑]

将碘化亚锡（或氧化亚锡^[2]）溶解在氮气保护的氢碘酸和次磷酸混合溶液中并加热，得到亮黄色溶液，向溶液中加入甲胺氢碘酸盐固体，于120 °C蒸去一半溶剂，冷却后析出黑色的MASnI₃晶体。该化合物在空气中放置很快变质。^[3]碘化亚锡和甲胺氢碘酸盐在2-丙醇中反应，也可以得到MASnI₃。^[4]

在MASnI₃的制备反应中，用DMF作为溶剂时，结晶速率要比同构物MAPbI₃要快。而在DMSO中的反应则会产生黄色的SnI₂·3DMSO中间体，该中间体与同族的PbI₂·2DMSO晶体结构不同。N-甲基吡咯烷酮和γ-丁内酯作为溶剂的反应也有研究。^[5]

性质[编辑]

三碘合锡(II)酸甲铵的带隙是1.15 eV，比多晶或薄膜的样品要小，但在空气中放置一个月后，带隙升至1.46 eV，并伴随着分子中的二价锡氧化为四价锡。

三碘合锡(II)酸甲铵加热至200 °C分解，主要产生是碘化亚锡。^[2]

参考文献[编辑]

^ Aashir Waleed, Mohammad Mahdi Tavakoli, Leilei Gu, Ziyi Wang, Daquan Zhang, Arumugam Manikandan, Qianpeng Zhang, Rongjun Zhang, Yu-Lun Chueh, Zhiyong Fan. Lead-Free Perovskite Nanowire Array Photodetectors with Drastically Improved Stability in Nanoengineering Templates. Nano Letters. 2017-01-11, 17 (1): 523–530 [2019-01-12]. ISSN 1530-6984. doi:10.1021/acs.nanolett.6b04587.
^ ^2.0 ^2.1 Yangyang Dang, Yian Zhou, Xiaolong Liu, Dianxing Ju, Shengqing Xia, Haibing Xia, Xutang Tao. Formation of Hybrid Perovskite Tin Iodide Single Crystals by Top-Seeded Solution Growth. Angewandte Chemie International Edition. 2016, 55 (10): 3447–3450 [2019-01-12]. ISSN 1521-3773. doi:10.1002/anie.201511792 （英语）.
^ Constantinos C. Stoumpos, Christos D. Malliakas, Mercouri G. Kanatzidis. Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties. Inorganic Chemistry. 2013-08-05, 52 (15): 9019–9038 [2019-01-12]. ISSN 0020-1669. doi:10.1021/ic401215x. (Supporting Information (PDF) （页面存档备份，存于互联网档案馆）)
^ Kangning Liang, David B. Mitzi, Michael T. Prikas. Synthesis and Characterization of Organic−Inorganic Perovskite Thin Films Prepared Using a Versatile Two-Step Dipping Technique. Chemistry of Materials. 1998-01-19, 10 (1): 403–411 [2019-01-12]. ISSN 0897-4756. doi:10.1021/cm970568f.
^ Feng Hao, Constantinos C. Stoumpos, Peijun Guo, Nanjia Zhou, Tobin J. Marks, Robert P. H. Chang, Mercouri G. Kanatzidis. Solvent-Mediated Crystallization of CH3NH3SnI3 Films for Heterojunction Depleted Perovskite Solar Cells. Journal of the American Chemical Society. 2015-09-09, 137 (35): 11445–11452 [2019-01-12]. ISSN 0002-7863. doi:10.1021/jacs.5b06658.

[1] Aashir Waleed, Mohammad Mahdi Tavakoli, Leilei Gu, Ziyi Wang, Daquan Zhang, Arumugam Manikandan, Qianpeng Zhang, Rongjun Zhang, Yu-Lun Chueh, Zhiyong Fan. Lead-Free Perovskite Nanowire Array Photodetectors with Drastically Improved Stability in Nanoengineering Templates. Nano Letters. 2017-01-11, 17 (1): 523–530 [2019-01-12]. ISSN 1530-6984. doi:10.1021/acs.nanolett.6b04587.

[Dang-2] 2.0 ^2.1 Yangyang Dang, Yian Zhou, Xiaolong Liu, Dianxing Ju, Shengqing Xia, Haibing Xia, Xutang Tao. Formation of Hybrid Perovskite Tin Iodide Single Crystals by Top-Seeded Solution Growth. Angewandte Chemie International Edition. 2016, 55 (10): 3447–3450 [2019-01-12]. ISSN 1521-3773. doi:10.1002/anie.201511792 （英语）.

[3] Constantinos C. Stoumpos, Christos D. Malliakas, Mercouri G. Kanatzidis. Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties. Inorganic Chemistry. 2013-08-05, 52 (15): 9019–9038 [2019-01-12]. ISSN 0020-1669. doi:10.1021/ic401215x. (Supporting Information (PDF) （页面存档备份，存于互联网档案馆）)

[4] Kangning Liang, David B. Mitzi, Michael T. Prikas. Synthesis and Characterization of Organic−Inorganic Perovskite Thin Films Prepared Using a Versatile Two-Step Dipping Technique. Chemistry of Materials. 1998-01-19, 10 (1): 403–411 [2019-01-12]. ISSN 0897-4756. doi:10.1021/cm970568f.

[5] Feng Hao, Constantinos C. Stoumpos, Peijun Guo, Nanjia Zhou, Tobin J. Marks, Robert P. H. Chang, Mercouri G. Kanatzidis. Solvent-Mediated Crystallization of CH3NH3SnI3 Films for Heterojunction Depleted Perovskite Solar Cells. Journal of the American Chemical Society. 2015-09-09, 137 (35): 11445–11452 [2019-01-12]. ISSN 0002-7863. doi:10.1021/jacs.5b06658.

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