On the thermal and thermodynamic (In)stability of methylammonium lead halide perovskites

The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices.