Thermodynamics and the Intrinsic Stability of Lead Halide Perovskites CH3NH3PbX3

The role of thermodynamics in assessing the intrinsic instability of the CH3NH3PbX3 perovskites (X = Cl,Br,I) is outlined on the basis of the available experimental information. Possible decomposition/degradation pathways driven by the inherent instability of the material are considered. The decomposition to precursors CH3NH3X(s) and PbX2(s) is first analyzed, pointing out the importance of both the enthalpic and the entropic factor, the latter playing a stabilizing role making the stability higher than often asserted. For CH3NH3PbI3, the disagreement between the available calorimetric results makes the stability prediction uncertain. Subsequently, the gas-releasing decomposition paths are discussed, with emphasis on the discrepant results presently available, probably reflecting the predominance of thermodynamic or kinetic control. The competition between the formation of NH3(g) + CH3X­(g), CH3NH2(g) + HX­(g) or CH3NH3X­(g) is analyzed, in comparison with the thermal decomposition of methylammonium halides. In view of the scarce and inconclusive thermodynamic studies to-date available, the need for further experimental data is emphasized.