Microscopy provides a proxy for assessing the operation of perovskite solar cells, yet most works in the literature have focused on bare perovskite thin films, missing charge transport and recombination losses present in full devices. Here we demonstrate a multimodal operando microscopy toolkit to measure and spatially correlate nanoscale charge transport losses, recombination losses and chemical composition. By applying this toolkit to the same scan areas of state-of-the-art, alloyed perovskite cells before and after extended operation, we show that devices with the highest macroscopic performance have the lowest initial performance spatial heterogeneity—a crucial link that is missed in conventional microscopy. We show that engineering stable interfaces is critical to achieving robust devices. Once the interfaces are stabilized, we show that compositional engineering to homogenize charge extraction and to minimize variations in local power conversion efficiency is critical to improve performance and stability. We find that in our device space, perovskites can tolerate spatial disorder in chemistry, but not charge extraction.

显微镜为评估钙钛矿太阳能电池的运行提供了代理，但文献中的大多数工作都集中在裸露的钙钛矿薄膜、完整器件中存在的缺失电荷传输和复合损耗。在这里，我们展示了一个多模态原位显微镜工具包，用于测量纳米级电荷传输损耗、复合损耗和化学成分并在空间上关联。通过将该工具包应用于长时间运行前后最先进的合金钙钛矿电池的相同扫描区域，我们发现具有最高宏观性能的设备具有最低的初始性能空间异质性——这是传统显微镜中遗漏的关键环节。我们表明，设计稳定的接口对于实现稳健的设备至关重要。一旦界面稳定下来，我们表明，用于同质化电荷提取并最大限度地减少局部功率转换效率变化的成分工程对于提高性能和稳定性至关重要。我们发现，在我们的器件空间中，钙钛矿可以容忍化学中的空间无序，但不能容忍电荷提取。