Origin of Persisting Photoresponse of One-Year Aged Two-Dimensional Lead Halide Perovskites Stored in Air Under Dark Conditions

Abstract

Two-dimensional halide perovskites are promising for advanced photonic, optoelectronic and photovoltaic applications. However, their long-term stability is still a critical factor limiting their implementation into further commercial applications. Here, we present an environmental stability analysis of BA2(MA)n-1PbnI3n+1 (BA=C4H12N+, MA=CH6N+) two-dimensional perovskites with the lowest quantum well thicknesses of n=1 and n=2, after one year of aging under ambient humidity, oxygen content, and light conditions. We observed that both crystal phases (n=1, 2) degraded similarly, resulting in the removal of organic components and crystal decomposition into PbI2, Pb oxides and Pb hydroxides. However, we have found a significant difference between their aging under ambient light and dark conditions, affecting their degraded morphology and photoactivity. Both crystal phases exposed to ambient light aged into a morphology characteristic by the formation of several pinholes and voids, accompanied by photoluminescence degradation. Samples stored under dark conditions surprisingly preserved photoluminescence activity, which morphologically aged into microrod structures. We conclude that the observed loss of photoactivity of 2D perovskites aged under ambient light is attributed to photo-accelerated degradation processes causing faster crystal surface photo-oxidation accompanied with a creation of multiple I vacancies and hydration of the inner crystal. The retainment of photoactivity in 2D perovskites aged under dark conditions is attributed to slower surface oxidation processes into Pb salts, as confirmed by X-ray photoemission spectroscopy. The formed surface layer even allow for a layer-by-layer degradation and act as a protection barrier against further additional loss of I atoms and the consequent hydration of the inner part of samples. We demonstrate that light is the most critical external factor accelerating 2D perovskite degradation processes in ambient air and thus affecting their long-term stability. We conclude in this work that perovskitematerial structural engineering, together with their surface passivation or encapsulation strategical

Keywords: Two-dimensional perovskites, Stability, Degradation, Surface oxidation, Photoluminescence spectroscopy, Photoemission spectroscopy.