We derive upper bounds on the magnitude of shift photocurrent generation of materials in two limiting cases: the flat-band limit of almost-isolated systems such as molecular crystals, and the wide-band limit of one-dimensional or quasi-one-dimensional materials such as ferroelectric polymers or other materials with chain-like motifs. These bounds relate the magnitudes of the shift current bulk photovoltaic effect to materials parameters. In both cases, we find that ratio of electron hopping amplitudes to the band gap plays a vital role in maximizing the amount of nonlinear response. Furthermore, by using the Wannier function formalism, we quantify the effect of long-range hopping amplitudes, showing how delocalization of electronic states gives rise to larger photocurrents. These results inform the design and selection of new materials for large shift current generation.

The stability of halide perovskites has been a long-standing issue for their real-world application. Approaches to improve stability include nanostructuring, dimensionality reduction, and strain engineering, where surfaces play an important role in the formation of a stable structure. To understand the mechanism we compute the lattice dynamics of the surface of CsPbI₃ using density functional theory. We demonstrate, for the first time, that CsPbI₃ crystals exhibit surface phonons that are localized on the outermost layers of the slabs, and we perform a complete symmetry characterization including an identification of the Raman/IR active modes. These surface phonons are present in the optically active cubic phase but are absent in the optically inactive "yellow" phase. Furthermore, we show that the surface suppresses bulk instabilities by hardening soft modes of the bulk cubic phase, resulting in phase stabilization and quenching of dynamical disorder. This study is fundamental for understanding the structural behavior of halide perovskite materials with high surface area-to-volume ratios, and for guiding stabilization strategies.

Despite a long history of research into nonlinear response theory, there has been no systematic investigation into the maximum amount of nonlinear optical response attainable in solid-state materials. In this work, we present an upper bound on the second-order response functions of materials, which controls the shift current response. We show that this bound depends on the band gap, bandwidth, and geometrical properties of the material in question. We find that delocalized systems generally have larger responses than more localized or isolated ones. As a proof of principle, we perform first-principles calculations of the response tensors of a wide variety of materials, finding that the materials in our database do not yet saturate the upper bound. This suggests that new large shift current materials will likely be discovered by future materials research guided by the factors mentioned in this work.

Two-dimensional (2D) organic-inorganic hybrid perovskites have been intensively explored in recent years due to their tunable band gaps and exciton binding energies and increased stability with respect to three-dimensional (3D) hybrid perovskites. Experimental observations suggest the existence of localized edge states in 2D hybrid perovskites which facilitate extremely efficient electron-hole dissociation and long carrier lifetimes, while multiple origins for their formation have been proposed. Using first-principles calculations, we demonstrate that layer edge states are stabilized by internal electric fields created by polarized molecular alignment of organic cations in 2D hybrid perovskites when they are two layers or thicker. Our study gives a simple physical explanation of the edge state formation, and facilitating the design and manipulation of layer edge states for optoelectronic applications.

Inorganic halide perovskites CsPbX₃ (X = Cl, Br, I) have been widely studied as colloidal quantum dots for their excellent optoelectronic properties. Not only is the long-term stability of these materials improved via nanostructuring, their optical bandgaps are also tunable by the nanocrystal (NC) size. However, theoretical understanding of the impact of the NC size on the phase stability and bandgap is still lacking. In this work, the relative phase stability of CsPbI₃ as a function of the crystal size and the chemical potential is investigated by density functional theory. The optically active phases (α- and γ-phase) are found to be thermodynamically stabilized against the yellow δ-phase by reducing the size of the NC below 5.6 nm in a CsI-rich environment. We developed a more accurate quantum confinement model to predict the change in bandgaps at the sub-10 nm regime by including a finite-well effect. These predictions have important implications for synthesizing ever more stable perovskite NCs and bandgap engineering.

Photo-induced phase-transitions (PIPTs) driven by highly cooperative interactions are of fundamental interest as they offer a way to tune and control material properties on ultrafast timescales. Due to strong correlations and interactions, complex quantum materials host several fascinating PIPTs such as light-induced charge density waves and ferroelectricity and have become a desirable setting for studying these PIPTs. A central issue in this field is the proper understanding of the underlying mechanisms driving the PIPTs. As these PIPTs are highly nonlinear processes and often involve multiple time and length scales, different theoretical approaches are often needed to understand the underlying mechanisms. In this review, we present a brief overview of PIPTs realized in complex materials, followed by a discussion of the available theoretical methods with selected examples of recent progress in understanding of the nonequilibrium pathways of PIPTs.

We show that the carrier recombination rate of noncentrosymmetric materials can be strongly modified by spin-orbit coupling. Our proposed mechanism involves the separation of conduction and valence bands into their respective spin components, which changes the transition dipole moments between them. The change in the carrier recombination can be either positive or negative in sign, or vary depending on the location of carriers in the Brillouin zone. We have performed a large scale DFT screening study to identify candidate materials that display this effect. We have selected three materials, Pb4SeBr6, ReTe3Br5, and CsCu(BiS2)2, which span the range of behaviors, and discuss their electronic band structure in greater detail. We find transition dipole moment enhancement factors of up to three orders of magnitude, reflecting the physical impact of spin-orbit coupling on the carrier lifetime. Therefore, further explorations of the spin-orbit coupling and lattice symmetry could prove to be useful for manipulating the photophysics of materials.

Optically induced phase transitions of the manganite Pr1/3Ca2/3MnO3 have been simulated by using a model Hamiltonian that captures the dynamics of strongly correlated charge, orbital, lattice, and spin degrees of freedom. Its parameters have been extracted from first-principles calculations. Beyond a critical intensity of a femtosecond light pulse, the material undergoes an ultrafast and nonthermal magnetic phase transition from a noncollinear to collinear antiferromagnetic phase. The light-pulse excites selectively either a spin-nematic or a ferroelectric phase, depending on the light polarization. The behavior can be traced to an optically induced ferromagnetic coupling between Mn trimers, i.e., polarons which are delocalized over three Mn sites. The polarization guides the polymerization of the polaronic crystal into distinct patterns of ferromagnetic chains determining the target phase.

Halide perovskites are strongly influenced by large amplitude anharmonic lattice fluctuations at room temperature. We develop a tight binding model for dynamically disordered MAPbI$_3$ based on density functional theory (DFT) calculations to calculate electronic structure for finite temperature crystal structures at the length scale of thermal disorder and carrier localization. The model predicts individual Hamiltonian matrix elements and band structures with high accuracy, owing to the inclusion of additional matrix elements and descriptors for non-Coulombic interactions. We apply this model to electronic structure at length and time scales inaccessible to first principles methods, finding an increase in band gap, carrier mass, and the sub-picosecond fluctuations in these quantities with increasing temperature as well as the onset of carrier localization in large supercells induced by thermal disorder at 300 K. We identify the length scale $L^*= 5$ nm as the onset of localization in the electronic structure, associated with associated with decreasing band edge fluctuations, increasing carrier mass, and Rashba splitting approaching zero.

Solid systems with strong correlations and interactions under light illumination have the potential for exhibiting interesting bulk photovoltaic behavior in the nonperturbative regime, which has remained largely unexplored in past theoretical studies. We investigate the bulk photovoltaic response of a perovskite manganite with strongly coupled electron-spin-lattice dynamics using real-time simulations performed with a tight-binding model. The transient changes in the band structure and the photoinduced phase transitions, emerging from spin and phonon dynamics, result in a nonlinear current versus intensity behavior beyond the perturbative limit. The current rises sharply across a photoinduced magnetic phase transition, which later saturates at higher light intensities due to excited phonon and spin modes. The predicted peak photoresponsivity is an order of magnitude higher than another known transition metal ferroelectric oxide BiFeO3. We disentangle phonon-and spin-assisted components to the ballistic photocurrent, showing that they are comparable in magnitude. Our results illustrate a promising alternative way for controlling and optimizing the bulk photovoltaic response through the photoinduced phase transitions in strongly correlated systems.