We study the mechanisms of CH3NH3PbI3 degradation and its transformation to PbI2 by means of X-ray diffraction and the density functional theory. The experimental analysis shows that the material can degrade in both air and vacuum conditions, with humidity and temperature-annealing strongly accelerating such process. Based on ab initio calculations, we argue that even in the absence of humidity, a decomposition of the perovskite structure can take place through the statistical formation of molecular defects with a non-ionic character, whose volatility at surfaces should break the thermodynamic defect equilibria. We finally discuss the strategies that can limit such phenomenon and subsequently prolong the lifetime of the material.

No abstract

No abstract

We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X-ray diffraction, spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2 . We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3 NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.

A nanoscale investigation on the capacitive behavior of graphene deposited on a SiO2/n(+) Si substrate (with SiO2 thickness of 300 or 100 nm) was carried out by scanning capacitance spectroscopy (SCS). A bias V(g) composed by an AC signal and a slow DC voltage ramp was applied to the macroscopic n(+) Si backgate of the graphene/SiO(2)/Si capacitor, while a nanoscale contact was obtained on graphene by the atomic force microscope tip. This study revealed that the capacitor effective area (A(eff)) responding to the AC bias is much smaller than the geometrical area of the graphene sheet. This area is related to the length scale on which the externally applied potential decays in graphene, that is, the screening length of the graphene 2DEG. The nonstationary charges (electrons/holes) induced by the AC potential spread within this area around the contact. A(eff) increases linearly with the bias and in a symmetric way for bias inversion. For each bias V(g), the value of A(eff) is related to the minimum area necessary to accommodate the not stationary charges, according to the graphene density of states (DOS) at V(g). Interestingly, by decreasing the SiO(2) thickness from 300 to 100 nm, the slope of the A(eff) versus bias curve strongly increases (by a factor of approximately 50). The local quantum capacitance C(q) in the contacted graphene region was calculated starting from the screening length, and the distribution of the values of C(q) for different tip positions was obtained. Finally the lateral variations of the DOS in graphene was determined.