Radiative Thermal Annealing/in Situ X-ray Diffraction Study of Methylammonium Lead Triiodide: Effect of Antisolvent, Humidity, Annealing Temperature Profile, and Film Substrates

Organic-inorganic hybrid halide perovskites are one of the most promising emerging photovoltaic materials due to their high efficiency and potentially low processing cost. Here, we present a well-controlled, manufacturing relevant annealing method, radiative thermal annealing, for the methylammonium lead triiodide (MAPbI3) films formed by a solvent engineering process, with dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) as solvent and diethyl ether as the antisolvent. Radiative thermal annealing can produce high quality perovskite films, evidenced by high efficiency solar cell devices (~18% power conversion efficiency), in a shorter time than the widely used hot plate annealing. Using in situ X-ray diffraction during the radiative annealing, we show that the role of the antisolvent is not to form an important intermediate compound (a PbI2-MAI-DMSO complex) by washing of the main solvent (DMF), but to achieve a pinhole free, uniform film of MAPbI3 with minimal intermediate compound. Importantly, we show that having a PbI2-MAI-DMSO intermediate compound does not guarantee a high quality (pinhole free) perovskite film. We directly show that humidity induces MAPbI3 to decompose into PbI2 more rapidly and, as such, negatively impacts the reproducibility of the device performance. The study is extended to reveal the effect of annealing temperature profile and deposition substrate to demonstrate the complexity of perovskite processing parameters. This coupled experimental approach allows a better understanding of the effect of processing protocols, including antisolvent, humidity, and annealing profile, on MAPbI3 film quality and the resultant solar cell performance.