Structural Evolution of Ultrathin SrFeO3-δ Films during Oxygen Evolution Reaction Revealed by In Situ Electrochemical Stress Measurements.

We report the electrochemical stress analysis of SrFeO3-δ (SFO) films deposited on Au substrates during oxygen evolution reactions (OERs). Our in situ analysis of Au reveals conversion reactions from Au to Au(OH)3, AuOOH, and AuOx during the OER. Au reactions cause a monotonic compressive stress on surfaces assigned to the formation of Au hydroxides and oxides. Electrochemical stress analysis of SrFeO3-δ/Au shows a dramatically different behavior during the OER, which we attribute to structural evolutions and conversion reactions, such as the conversion of SFO to iron (oxy)hydroxides. Interestingly, electrochemical stress analysis of SrFeO3-δ/Au shows a tensile trend, which evolves with cycling history. Electrochemical stress analysis of SFO films before the onset of the OER shows in situ changes, which cause tensile stresses when cycling to 1.2 V. We attribute these stresses to the formation of Fe2+δOδ(OH)2-δ (0 ≤ δ ≤ 1.5)-type materials where δ approaches 1.5 at higher potentials. At potentials higher than 1.2 V and during OER, surface stress response is rather stable, which we assign to the full conversion of SFO to iron (oxy)hydroxides. This analysis provides insight into the reaction mechanism and details of in situ structural changes of iron perovskites during the OER in alkaline environments.

Interfacial Topochemical Fluoridation of MAPbI3 by Fluoropolymers.

Herein it is demonstrated that, under conditions relevant to perovskite synthesis (>140 °C in air), fluoride can topochemically react across the interface between a halide perovskite and a fluoropolymer when in close contact, thereby creating a small quantity of strongly bonded lead fluoride species. The quantity increases with temperature and processing duration. Photoinduced charge carrier lifetime provides a metric for the resulting changes in electronic structure of the perovskite. Under short-duration and/or moderate temperature processing, fluoride transfer to the perovskite yields increased carrier lifetimes, up to 3-fold longer than control samples, which is attributed to passivation of surface defects. Under more forcing conditions, the trend reverses: excessive fluoridation leads to shortened carrier lifetimes, which is ascribed to substantial interfacial formation of PbF2. It is demonstrated that an interface with bulk crystalline PbF2 quenches perovskite photoluminescence, likely due to PbF2 serving as an electron acceptor for the conduction band of MAPbI3.

A multiscale ion diffusion framework sheds light on the diffusion-stability-hysteresis nexus in metal halide perovskites.

Stability and current-voltage hysteresis stand as major obstacles to the commercialization of metal halide perovskites. Both phenomena have been associated with ion migration, with anecdotal evidence that stable devices yield low hysteresis. However, the underlying mechanisms of the complex stability-hysteresis link remain elusive. Here we present a multiscale diffusion framework that describes vacancy-mediated halide diffusion in polycrystalline metal halide perovskites, differentiating fast grain boundary diffusivity from volume diffusivity that is two to four orders of magnitude slower. Our results reveal an inverse relationship between the activation energies of grain boundary and volume diffusions, such that stable metal halide perovskites exhibiting smaller volume diffusivities are associated with larger grain boundary diffusivities and reduced hysteresis. The elucidation of multiscale halide diffusion in metal halide perovskites reveals complex inner couplings between ion migration in the volume of grains versus grain boundaries, which in turn can predict the stability and hysteresis of metal halide perovskites, providing a clearer path to addressing the outstanding challenges of the field.

Synthesis and Characterization of SrFexMn1-x(O,F)3-δ Oxide (δ = 0 and 0.5) and Oxyfluoride Perovskite Films.

We report the synthesis and characterization of as-grown SrFexMn1-xO2.5 epitaxial films, which were also subjected to postgrowth oxidation and topotactic fluorination to obtain SrFexMn1-xO3 and SrFexMn1-xO2.5-δFγ films. We show how both the B-site cation and anion composition influence the structural, electronic, and optical properties of this family of perovskite materials. The Fe substitution of Mn in SrMnO2.5 gradually expands the c-axis parameter, as indicated by X-ray diffraction. With increasing x, the F content incorporated under identical fluorination conditions increases, reaching its maximum in SrFeO2.5-δFγ. In the compounds with mixed B-site occupation, the Fe 2p photoemission peaks are shifted upon fluorination, while the Mn 2p peaks are not, suggesting inductive effects lead to asymmetric responses in how F alters the Mn and Fe bonds. Electronic transport measurements reveal all compounds are insulators, with the exception of SrFeO3, and demonstrate that fluorination increases resistivity for all values of x. Optical absorption spectra in the SrFexMn1-xO2.5 and SrFexMn1-xO3 films evolve systematically as a function of x, consistent with a physical scenario in which optical changes with Fe substitution arise from a linear combination of Mn and Fe 3d bands within the electronic structure. In contrast, the F incorporation induces nonlinear changes to the optical response, suggesting a more complex impact on the electronic structure in materials with concurrent B-site and anion site substitution.