Prof Henry Snaith FRS

Abstract:

Extensive transient absorption studies on hybrid organic-inorganic lead halide perovskites have elucidated many optical properties important for their device performance. Despite the enormous progress, the derivative shaped photoinduced absorption feature in transient spectra that is above the bandgap has many explanations, including the photoinduced Stark effect, where the bandgap is blue shifted due to a local electric field generated by charges. In this work, we employ broad band transient absorption and two-dimensional electronic spectroscopy (2DES) to examine the early transient events after photoexcitation of [CH(NH₂)₂]_0.83Cs_0.17PbBr₃ (FA_0.83Cs_0.17PbBr₃). 2DES resolves a photomodulation feature at the excitation energy of the exciton, suggesting the presence of a dipole field created by a polaron pair shifting the exciton transition to higher energies. As this polaron pair dissociates over 200 fs, the exciton transition shifts to higher energies over the same time scale, evidenced by the 2DES diagonal energy spectra. Given that the observations are well explained in terms of the Stark effect, our work provides extra grounds to support the Stark effect assignment of the above-gap photoinduced absorption. Furthermore, our study reports on the time scale of charge generation, contributing to the fundamental understanding of mixed-cation lead bromide perovskite photophysics.

Abstract:

All‐inorganic perovskite materials are attractive alternatives to organic‐inorganic perovskites because of their potential for higher thermal stability. While CsPbI3 is compositionally stable under elevated temperatures, the cubic perovskite α‐phase is thermodynamically stable only at >330°C and the low‐temperature perovskite γ−phase is metastable and highly susceptible to non‐perovskite δ‐phase conversion in moisture. Many methods have been reported which show that incorporation of acid (aqueous HI) or “HPbI3” – recently shown to be dimethylammonium lead iodide (DMAPbI3) – lower the annealing temperature required to produce the black, perovskite phase of CsPbI3. The optical and crystallographic data presented here show that DMA can successfully incorporate as an A‐site cation to replace Cs in the CsPbI3 perovskite material. This describes the stabilization and lower phase transition temperature reported in the literature when HI or HPbI3 are used as precursors for CsPbI3. The Cs‐DMA alloy only forms a pure‐phase material up to ∽25% DMA; at higher concentrations the CsPbI3 and DMAPbI3 begin to phase segregate. These alloyed materials are more stable to moisture than neat CsPbI3, but do not represent a fully inorganic perovskite material.

Abstract:

Despite their impressive performance as a solar absorber, much remains unknown on the fundamental properties of metal halide perovskites (MHPs). Their polar nature in particular is an intense area of study, and the relative permittivity (ε_r) is a parameter widely used to quantify polarization over a range of different time scales. In this report, we have exploited frequency-dependent time-resolved microwave conductivity (TRMC) to study how ε_r values of a range of MHPs change as a function of time, upon optical illumination. Further characterization of charge carriers and polarizability are conducted by femtosecond transient absorption and stimulated Raman spectroscopy. We find that changes in ε_r are roughly proportional to photogenerated carrier density but decay with a shorter time constant than conductance, suggesting that the presence of charge carriers alone does not determine polarization.

Abstract:

Hybrid organic-inorganic perovskites are exciting materials for solar-energy applications whose microscopic properties are still not well understood. Atomic-resolution (scanning) transmission electron microscopy, (S)TEM, has provided invaluable insights for many crystalline solar-cell materials, and is used here to successfully image CH(NH2)2PbI3 thin films with low electron-radiation dose. Such images reveal a highly ordered atomic arrangement of sharp grain boundaries and coherent perovskite/PbI2 interfaces, with a striking absence of long-range disorder in the crystal. We demonstrate that beaminduced degradation of the perovskite leads to an initial loss of CH(NH2)2 + ions, leaving behind a partially unoccupied perovskite lattice, which explains the unusual regenerative properties of these materials. We further observe aligned point defects and climbdissociated dislocations. Our findings thus provide an atomic-level understanding of technologically important lead-halide perovskites.