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.

Since O’Regan and Grätzel’s first report in 1991, dye-sensitized solar cells (DSSCs) appeared immediately as a promising low-cost photovoltaic technology. In fact, though being far less efficient than conventional silicon-based photovoltaics (being the maximum, lab scale prototype reported efficiency around 13%), the simple design of the device and the absence of the strict and expensive manufacturing processes needed for conventional photovoltaics make them attractive in small-power applications especially in low-light conditions, where they outperform their silicon counterparts. Nanomaterials are at the very heart of DSSC, as the success of its design is due to the use of nanostructures at both the anode and the cathode. In this review, we present the state of the art for bothn-type andp-type semiconductors used in the photoelectrodes of DSSCs, showing the evolution of the materials during the 25 years of history of this kind of devices. In the case ofp-type semiconductors, also some other energy conversion applications are touched upon.