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Self-Healing and Light-Soaking in MAPbI3: The Effect of H2O
Advanced Materials ( IF 27.4 ) Pub Date : 2022-06-22 , DOI: 10.1002/adma.202110239 Davide Raffaele Ceratti 1, 2 , Ron Tenne 3 , Andrea Bartezzaghi 4 , Llorenç Cremonesi 5 , Lior Segev 6 , Vyacheslav Kalchenko 1 , Dan Oron 3 , Marco Alberto Carlo Potenza 5 , Gary Hodes 1 , David Cahen 1
Advanced Materials ( IF 27.4 ) Pub Date : 2022-06-22 , DOI: 10.1002/adma.202110239 Davide Raffaele Ceratti 1, 2 , Ron Tenne 3 , Andrea Bartezzaghi 4 , Llorenç Cremonesi 5 , Lior Segev 6 , Vyacheslav Kalchenko 1 , Dan Oron 3 , Marco Alberto Carlo Potenza 5 , Gary Hodes 1 , David Cahen 1
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The future of halide perovskites (HaPs) is beclouded by limited understanding of their long-term stability. While HaPs can be altered by radiation that induces multiple processes, they can also return to their original state by “self-healing.” Here two-photon (2P) absorption is used to effect light-induced modifications within MAPbI3 single crystals. Then the changes in the photodamaged region are followed by measuring the photoluminescence, from 2P absorption with 2.5 orders of magnitude lower intensity than that used for photodamaging the MAPbI3. After photodamage, two brightening and one darkening process are found, all of which recover but on different timescales. The first two are attributed to trap-filling (the fastest) and to proton-amine-related chemistry (the slowest), while photodamage is attributed to the lead-iodide sublattice. Surprisingly, while after 2P-irradiation of crystals that are stored in dry, inert ambient, photobrightening (or “light-soaking”) occurs, mostly photodarkening is seen after photodamage in humid ambient, showing an important connection between the self-healing of a HaP and the presence of H2O, for long-term steady-state illumination, practically no difference remains between samples kept in dry or humid environments. This result suggests that photobrightening requires a chemical-reservoir that is sensitive to the presence of H2O, or possibly other proton-related, particularly amine, chemistry.
中文翻译：
MAPbI3 中的自愈和光浸泡：H2O 的影响
卤化物钙钛矿（HaPs）的未来因对其长期稳定性的有限了解而蒙上阴影。虽然 HaP 可以通过诱导多个过程的辐射来改变，但它们也可以通过“自我修复”恢复到原来的状态。这里使用双光子 (2P) 吸收来影响 MAPbI 3单晶内的光诱导修饰。然后在光损伤区域的变化之后测量光致发光，从 2P 吸收，强度比用于光损伤 MAPbI 3的强度低 2.5 个数量级. 在光损伤后，发现了两个变亮和一个变暗过程，所有这些过程都恢复了，但在不同的时间尺度上。前两个归因于陷阱填充（最快）和与质子胺相关的化学（最慢），而光损伤归因于碘化铅亚晶格。令人惊讶的是，在对储存在干燥、惰性环境中的晶体进行 2P 辐照后，会发生光亮（或“光浸泡”），而大多数光暗化是在潮湿环境中的光损伤后看到的，这表明了晶体的自我修复与HaP 和 H 2的存在O，对于长期稳态照明，在干燥或潮湿环境中保存的样品之间几乎没有差异。该结果表明，光亮化需要一个对 H 2 O 或其他可能与质子相关的化学物质，特别是胺化学物质的存在敏感的化学物质储存器。
更新日期：2022-06-22
中文翻译：
MAPbI3 中的自愈和光浸泡：H2O 的影响
卤化物钙钛矿（HaPs）的未来因对其长期稳定性的有限了解而蒙上阴影。虽然 HaP 可以通过诱导多个过程的辐射来改变，但它们也可以通过“自我修复”恢复到原来的状态。这里使用双光子 (2P) 吸收来影响 MAPbI 3单晶内的光诱导修饰。然后在光损伤区域的变化之后测量光致发光，从 2P 吸收，强度比用于光损伤 MAPbI 3的强度低 2.5 个数量级. 在光损伤后，发现了两个变亮和一个变暗过程，所有这些过程都恢复了，但在不同的时间尺度上。前两个归因于陷阱填充（最快）和与质子胺相关的化学（最慢），而光损伤归因于碘化铅亚晶格。令人惊讶的是，在对储存在干燥、惰性环境中的晶体进行 2P 辐照后，会发生光亮（或“光浸泡”），而大多数光暗化是在潮湿环境中的光损伤后看到的，这表明了晶体的自我修复与HaP 和 H 2的存在O，对于长期稳态照明，在干燥或潮湿环境中保存的样品之间几乎没有差异。该结果表明，光亮化需要一个对 H 2 O 或其他可能与质子相关的化学物质，特别是胺化学物质的存在敏感的化学物质储存器。
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