Search for: All records

For the prototypical two-dimensional hybrid organic–inorganic perovskites (2D HOIPs) (AE4T)PbX4 (X = Cl, Br, and I), we demonstrate that the Frenkel–Holstein Hamiltonian (FHH) can be applied to describe the absorption spectrum arising from the organic component. We first model the spectra using only the four nearest neighbor couplings between translationally inequivalent molecules in the organic herringbone lattice as fitting parameters in the FHH. We next use linear-response time-dependent density functional theory (LR-TDDFT) to calculate molecular transition densities, from which extended excitonic couplings are evaluated based on the atomic positions within the 2D HOIPs. We find that both approaches reproduce the experimentally observed spectra, including changes in their shape and peak positions. The spectral changes are correlated with a decrease in excitonic coupling from X = Cl to X = I. Importantly, the LR-TDDFT-based approach with extended excitonic couplings not only gives better agreement with the experimental absorption line shape than the approach using a restricted set of fitted parameters but also allows us to relate the changes in excitonic coupling to the underlying geometry. We accordingly find that the decrease in excitonic coupling from X = Cl to Br to I is due to an increase in molecular separation, which in turn can be related to the increasing Pb–X bond length from Cl to I. Our research opens up a potential pathway to predicting optoelectronic properties of new 2D HOIPs from ab initio calculations and to gain insight into structural relations from 2D HOIP absorption spectra. 

Abstract Translation of chirality and asymmetry across structural motifs and length scales plays a fundamental role in nature, enabling unique functionalities in contexts ranging from biological systems to synthetic materials. Here, we introduce a structural chirality transfer across the organic–inorganic interface in two-dimensional hybrid perovskites using appropriate chiral organic cations. The preferred molecular configuration of the chiral spacer cations,R-(+)- orS-(−)-1-(1-naphthyl)ethylammonium and their asymmetric hydrogen-bonding interactions with lead bromide-based layers cause symmetry-breaking helical distortions in the inorganic layers, otherwise absent when employing a racemic mixture of organic spacers. First-principles modeling predicts a substantial bulk Rashba-Dresselhaus spin-splitting in the inorganic-derived conduction band with opposite spin textures betweenR- andS-hybrids due to the broken inversion symmetry and strong spin-orbit coupling. The ability to break symmetry using chirality transfer from one structural unit to another provides a synthetic design paradigm for emergent properties, including Rashba-Dresselhaus spin-polarization for hybrid perovskite spintronics and related applications. 

Abstract Electron–phonon interactions play an essential role in charge transport and transfer processes in semiconductors. For most structures, tailoring electron–phonon interactions for specific functionality remains elusive. Here, it is shown that, in hybrid perovskites, coherent phonon modes can be used to manipulate charge transfer. In the 2D double perovskite, (AE2T)₂AgBiI₈(AE2T: 5,5“‐diylbis(amino‐ethyl)‐(2,2”‐(2)thiophene)), the valence band maximum derived from the [Ag_0.5Bi_0.5I₄]^2–framework lies in close proximity to the AE2T‐derived HOMO level, thereby forming a type‐II heterostructure. During transient absorption spectroscopy, pulsed excitation creates sustained coherent phonon modes, which periodically modulate the associated electronic levels. Thus, the energy offset at the organic–inorganic interface also oscillates periodically, providing a unique opportunity for modulation of interfacial charge transfer. Density‐functional theory corroborates the mechanism and identifies specific phonon modes as likely drivers of the coherent charge transfer. These observations are a striking example of how electron–phonon interactions can be used to manipulate fundamentally important charge and energy transfer processes in hybrid perovskites.