Computational Condensed Matter Physics Group

Abstract:

Understanding competing charge density wave (CDW) orders in the bilayer kagome metal ScV₆Sn₆ remains challenging. Experimentally, upon cooling, short-range order with wave vector q 2 = ( 1 3 , 1 3 , 1 2 ) forms, which is subsequently suppressed by the condensation of long-range q 3 = ( 1 3 , 1 3 , 1 3 ) CDW order at lower temperature. Theoretically, however, the q₂ CDW is predicted as the ground state, leaving the CDW mechanism elusive. Here, using anharmonic phonon-phonon calculations combined with density functional theory, we predict a temperature-driven structural phase transitions from the high-temperature pristine phase to the q₂ CDW, followed by the low-temperature q₃ CDW, explaining experimental observations. We demonstrate that semi-core electron states stabilize the q₃ CDW over the q₂ CDW. Furthermore, we find that the out-of-plane lattice parameter controls the competing CDWs, motivating us to propose compressive bi-axial strain as an experimental protocol to stabilize the q₂ CDW. Finally, we suggest Ge or Pb doping at the Sn site as another potential avenue to control CDW instabilities. Our work provides a full theory of CDWs in ScV₆Sn₆, rationalizing experimental observations and resolving earlier discrepancies between theory and experiment.

Abstract:

Halide double perovskites are a chemically diverse and growing class of compound semiconductors that are promising for optoelectronic applications. However, the prediction of their fundamental gaps and optical properties with density functional theory (DFT) and ab initio many-body perturbation theory has been a significant challenge. Recently, a nonempirical Wannier-localized optimally tuned screened range-separated hybrid (WOT-SRSH) functional has been shown to accurately produce the fundamental band gaps of a wide set of semiconductors and insulators, including lead halide perovskites. Here, we apply the WOT-SRSH functional to five halide double perovskites and compare the results with those obtained from other known functionals and previous GW calculations. We also use the approach as a starting point for GW calculations and we compute the band structures and optical absorption spectrum for Cs2AgBiBr6, using both time-dependent DFT and the GW-Bethe-Salpeter equation approach. We show that the WOT-SRSH functional leads to accurate fundamental and optical band gaps, as well as optical absorption spectra, consistent with spectroscopic measurements, thereby establishing WOT-SRSH as a viable method for the accurate prediction of optoelectronic properties of halide double perovskites.

Abstract:

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfill ambitions for net-zero carbon dioxide equivalent (CO2eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the PVs community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.

Abstract:

We incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS (+NH3(CH2)2Se-), which occupies both the X- and A+ sites in the prototypical ABX3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX2 (X = Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77Se and 207Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable bandgap decrease. Optical absorbance measurements indeed show bandgaps of 2.07 and 1.86 eV for (SeCYS)PbX2 with X = Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the bandgap from 1.86 to 2.31 eV-straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the bandgap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.