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.

Solid systems with strong correlations and interactions under light illumination have the potential for exhibiting interesting bulk photovoltaic behavior in the non-perturbative regime, which has remained largely unexplored in the 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 orders of magnitude higher than other known ferroelectric oxides such as BiFeO$_3$. 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.

Improving the stability of semiconductor materials is one of the major challenges for sustainable and economic photoelectrochemical water splitting. N-terminated GaN nanostructures have emerged as a practical protective layer for conventional high efficiency but unstable Si and III-V photoelectrodes due to their near-perfect conduction band-alignment, which enables efficient extraction of photo-generated electrons, and N-terminated surfaces, which protects against chemical and photo-corrosion. Here, we demonstrate that Pt-decorated GaN nanostructures on an n+-p Si photocathode can exhibit an ultrahigh stability of 3000 h (i.e., over 500 days for usable sunlight ∼5.5 h per day) at a large photocurrent density (>35 mA cm-2) in three-electrode configuration under AM 1.5G one-sun illumination. The measured applied bias photon-to-current efficiency of 11.9%, with an excellent onset potential of ∼0.56 V vs. RHE, is one of the highest values reported for a Si photocathode under AM 1.5G one-sun illumination. This study provides a paradigm shift for the design and development of semiconductor photoelectrodes for PEC water splitting: stability is no longer limited by the light absorber, but rather by co-catalyst particles.

We present INQ, a new implementation of density functional theory (DFT) and time-dependent DFT (TDDFT) written from scratch to work on graphical processing units (GPUs). Besides GPU support, INQ makes use of modern code design features and takes advantage of newly available hardware. By designing the code around algorithms, rather than against specific implementations and numerical libraries, we aim to provide a concise and modular code. The result is a fairly complete DFT/TDDFT implementation in roughly 12,000 lines of open-source C++ code representing a modular platform for community-driven application development on emerging high-performance computing architectures for the simulation of materials.

We present inq, a new implementation of density functional theory (DFT) and time-dependent DFT (TDDFT) written from scratch to work on graphic processing units (GPUs). Besides GPU support, inq makes use of modern code design features and takes advantage of newly available hardware. By designing the code around algorithms, rather than against specific implementations and numerical libraries, we aim to provide a concise and modular code. The result is a fairly complete DFT/TDDFT implementation in roughly 12 000 lines of open-source C++ code representing a modular platform for community-driven application development on emerging high-performance computing architectures.

Development of an efficient yet durable photoelectrode is of paramount importance for deployment of solar-fuel production. Here, we report the photoelectrochemically self-improving behaviour of a silicon/gallium nitride photocathode active for hydrogen production with a Faradaic efficiency approaching ~100%. By using a correlative approach based on different spectroscopic and microscopic techniques, as well as density functional theory calculations, we provide a mechanistic understanding of the chemical transformation that is the origin of the self-improving behaviour. A thin layer of gallium oxynitride forms on the side walls of the gallium nitride grains, via a partial oxygen substitution at nitrogen sites, and displays a higher density of catalytic sites for the hydrogen-evolving reaction. This work demonstrates that the chemical transformation of gallium nitride into gallium oxynitride leads to sustained operation and enhanced catalytic activity, thus showing promise for oxynitride layers as protective catalytic coatings for hydrogen evolution.

We report on the electrical properties of 2.0 eV bandgap (EG) CuInGaS2 (CIGS) solar absorbers integrated on SnO2:F (FTO) substrates and interfaced with CdS buffer layers for multijunction solar cells and photoelectrochemical water splitting devices. The averaged short-circuit photocurrent density measured on nine ITO/ZnO/CdS/CIGS/FTO cells was 10.0 mA cm-2, a value corresponding to 70% of the optical limit for a 2.0 eV-bandgap absorber. However, the averaged power conversion efficiency was low (avg.: 2.4%) and for the most part limited by modest open circuit voltage values (avg.: 587 mV). Solid-state analyses performed at low temperatures revealed poor energetic alignment at the CdS/CIGS top interface. An activation energy (1.1 eV) for the dominant recombination mechanism significantly lower than the CIGS bandgap was measured, implying that recombination takes place near the CdS/CIGS interface. This finding is supported by the large difference found between the quasi Fermi level splitting of the bare absorber (1.17 eV) and the open circuit voltage of the device. Complementary theoretical calculations identified Fermi level pinning as a possible cause for the poor interface energetics through Cd incorporation on both the Cu and the group-III sites, resulting in a large conduction band offset (∼0.9 eV) at the CdS/CIGS interface. This work underlines the need for new EG-tunable buffers coupled with optimized CIGS surface energetics (e.g. ordered vacancy compounds) for future chalcopyrite-based multijunction solar cells and photoelectrochemical water splitting devices. This journal is

The oxygen-evolution reaction (OER) is pivotal in many energy-conversion technologies as it is an important counter reaction to others that convert stable chemicals to higher-value products using electrochemistry. The local microenvironment and pH for the anode OER can vary from acidic to neutral to alkaline depending on the system being explored, making definitive mechanistic insights difficult. In this paper, we couple experiments, first-principles calculations based on density functional theory, microkinetics, and transport modeling to explore the entire pH range of the OER. At low current densities, neutral pH values unexpectedly perform better than the acidic and alkaline conditions, and this trend is reversed at higher current densities (> 20 mA cm−2). Using multiscale modeling, this switch is rationalized by a change from a dual-reaction mechanism to a single rate-determining step. The model also shows how the alkaline reaction rates dominate in the middle to high pH range. Furthermore, we explore that the local pH for near-neutral conditions is much different (e.g., 2.4 at the reaction surface vs. 9 in the bulk) than the pH extremes, demonstrating the criticality that transport phenomena plays in kinetic activity.