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Ferroelectric materials have technological applications in information storage and electronic devices. The ferroelectric polar phase can be controlled with external fields, chemical substitution and size-effects in bulk and ultrathin film form, providing a platform for future technologies and for exploratory research. In this work, we integrate spin-polarized density functional theory (DFT) calculations, crystal structure databases, symmetry tools, workflow software, and a custom analysis toolkit to build a library of known, previously-proposed, and newly-proposed ferroelectric materials. With our automated workflow, we screen over 67,000 candidate materials from the Materials Project database to generate a dataset of 255 ferroelectric candidates, and propose 126 new ferroelectric materials. We benchmark our results against experimental data and previous first-principles results. The data provided includes atomic structures, output files, and DFT values of band gaps, energies, and the spontaneous polarization for each ferroelectric candidate. We contribute our workflow and analysis code to the open-source python packages atomate and pymatgen so others can conduct analogous symmetry driven searches for ferroelectrics and related phenomena.

The path to realizing low-cost, stable, and earth-abundant photoelectrodes can be enabled through a detailed understanding of the optoelectronic properties of these materials by combining theory and experimental techniques. Of the limited set of oxide photocathode materials currently available, CuFeO2 has emerged as a promising candidate warranting detailed attention. In this work, highly compact thin films of rhombohedral (3R) CuFeO2 were prepared via reactive co-sputtering. Despite its 1.43 eV indirect band gap, a cathodic photocurrent of 0.85 mA/cm2 was obtained at 0.4 V versus reversible hydrogen electrode in the presence of a sacrificial electron acceptor. This unexpected performance was related to inefficient bulk charge separation because of the ultrafast (

Transient absorption (TA) spectroscopy is uniquely suited for understanding kinetic processes initiated by light over vast ranges of time. In combination with white light probes, the recorded differential absorption spectra can contain spectroscopic signatures characteristic of specific charge carrier population densities. However, disentangling the often-complex and convoluted spectra is made challenging without robust analysis methods relating the underlying physical mechanisms to the spectral components. In this work, we address the origin of the transient spectra of a model system of emerging solar energy harvesting materials using a monoclinic BiVO4 thin film. Using ground-state optical properties of the semiconductor, we find the main derivative-like spectral response to be related to shifting and broadening of oscillators, rather than specific carrier-related transitions. However, by using the Drude optical model of free carriers, we also identify the transient response related to free-hole density. Importantly, sample heating from the optical pumping, which begins at â10 ps and plateaus by â200 ps, dominates the overall spectral response at longer times. On the basis of a physical model of the spectral response, a kinetic model is developed that describes the pump power dependence of the free-hole density, as well as the temporal evolution of the spectral changes associated with shifting and broadening of oscillators. First-principles density functional theory calculations are used to rationalize experimental measurements. This comprehensive approach to analyzing and modeling the TA spectra offers a generalizable basis for understanding the complex pump-probe data, reveals thermal heating artifacts that are frequently erroneously assigned to long-lived photocarriers, and offers a path to eliminating ambiguity in analysis of photocarrier dynamics in solid-state systems.

Improving the efficiency of solar-powered oxygen evolution is both critical for development of solar fuels technologies and challenging due to the broad set of properties required of a solar fuels photoanode. Bismuth vanadate, in particular the monoclinic clinobisvanite phase, has received substantial attention and has exhibited the highest radiative efficiency among metal oxides with a band gap in the visible range. Efforts to further improve its photoelectrochemical performance have included alloying one or more metals onto the Bi and/or V sites, with progress on this frontier stymied by the difficulty in computational modelling of substitutional alloys and the high dimensionality of co-alloying composition spaces. Since substitutional alloying concurrently changes multiple materials properties, understanding the underlying cause for performance improvements is also challenging, motivating our application of combinatorial materials science techniques to map photoelectrochemical performance of 948 unique bismuth vanadate alloy compositions comprising 0 to 8% alloys of P, Ca, Mo, Eu, Gd, and W along with a variety of compositions from each pairwise combination of these elements. Upon identification of substantial improvements in the (Mo,Gd) co-alloying space, structural mapping was performed to reveal a remarkable correlation between performance enhancement and a lowered monoclinic distortion. First-principles density functional theory calculations indicate that the improvements are due to a lowered hole effective mass and hole polaron formation energy, and collectively, our results identify the monoclinic distortion as a critical parameter in the optimization and understanding of bismuth vanadate-based photoanodes.

Solar-driven oxygen evolution is a critical technology for renewably synthesizing hydrogen- and carbon-containing fuels in solar fuel generators. New photoanode materials are needed to meet efficiency and stability requirements, motivating materials explorations for semiconductors with (i) band-gap energy in the visible spectrum and (ii) stable operation in aqueous electrolyte at the electrochemical potential needed to evolve oxygen from water. Motivated by the oxygen evolution competency of many Mn-based oxides, the existence of several Bi-containing ternary oxide photoanode materials, and the variety of known oxide materials combining these elements with Sm, we explore the Bi-Mn-Sm oxide system for new photoanodes. Through the use of a ferri/ferrocyanide redox couple in high-throughput screening, BiMn2O5 and its alloy with Sm are identified as photoanode materials with a near-ideal optical band gap of 1.8 eV. Using density functional theory-based calculations of the mullite Bi3+Mn3+Mn4+O5 phase, we identify electronic analogues to the well-known BiVO4 photoanode and demonstrate excellent Pourbaix stability above the oxygen evolution Nernstian potential from pH 4.5 to 15. Our suite of experimental and computational characterization indicates that BiMn2O5 is a complex oxide with the necessary optical and chemical properties to be an efficient, stable solar fuel photoanode.

Antiferroelectric PbZrO3 is being considered for a wide range of applications where the competition between centrosymmetric and noncentrosymmetric phases is important to the response. Here, we focus on the epitaxial growth of PbZrO3 thin films and understanding the chemistry-structure coupling in Pb1+δZrO3 (δ = 0, 0.1, 0.2). High-quality, single-phase Pb1+δZrO3 films are synthesized via pulsed-laser deposition. Although no significant lattice parameter change is observed in X-ray studies, electrical characterization reveals that while the PbZrO3 and Pb1.1ZrO3 heterostructures remain intrinsically antiferroelectric, the Pb1.2ZrO3 heterostructures exhibit a hysteresis loop indicative of ferroelectric response. Further X-ray scattering studies reveal strong quarter-order diffraction peaks in PbZrO3 and Pb1.1ZrO3 heterostructures indicative of antiferroelectricity, while no such peaks are observed for Pb1.2ZrO3 heterostructures. Density functional theory calculations suggest the large cation nonstoichiometry is accommodated by incorporation of antisite PbZr defects, which drive the Pb1.2ZrO3 heterostructures to a ferroelectric phase with R3c symmetry. In the end, stabilization of metastable phases in materials via chemical nonstoichiometry and defect engineering enables a novel route to manipulate the energy of the ground state of materials and the corresponding material properties.

Photovoltaic devices based on hybrid perovskite materials have exceeded 22% efficiency due to high charge-carrier mobilities and lifetimes. Properties such as photocurrent generation and open-circuit voltage are influenced by the microscopic structure and orientation of the perovskite crystals, but are difficult to quantify on the intra-grain length scale and are often treated as homogeneous within the active layer. Here, we map the local short-circuit photocurrent, open-circuit photovoltage, and dark drift current in state-of-the-art methylammonium lead iodide solar cells using photoconductive atomic force microscopy. We find, within individual grains, spatially correlated heterogeneity in short-circuit current and open-circuit voltage up to 0.6 V. These variations are related to different crystal facets and have a direct impact on the macroscopic power conversion efficiency. We attribute this heterogeneity to a facet-dependent density of trap states. These results imply that controlling crystal grain and facet orientation will enable a systematic optimization of polycrystalline and single-crystal devices for photovoltaic and lighting applications.

We report two new cyanido-bridged Fe(II)-Ag(I) coordination polymers using different acetylpyridine isomers, {Fe(4acpy) 2 [Ag(CN) 2 ] 2 } 1 and {Fe(3acpy)[Ag(CN) 2 ] 2 } 2 (4acpy = 4-acetylpyridine; 3acpy = 3-acetylpyridine) displaying thermally and photoinduced spin crossover (SCO). In both cases, the acetylpyridine ligand directs the coordination polymer structure and the SCO of the materials. Using 4-acetylpyridine, a two-dimensional (2D) structure is observed in 1 made of layers stacked on each other by silver-ketone interactions leading to a complete SCO and reversible thermally and photoswitching of the magnetic and optical properties. Changing the acetyl group to a 3-position, a completely different structure is obtained for 2 . The unexpected coordination of the carbonyl group to the Fe(II) centers induces a three-dimensional (3D) structure, leading to statistical disorder around the Fe(II) with three different coordination spheres, [N 6 ], [N 4 O 2 ], and [N 5 O]. This disorder gives rise to an incomplete thermally induced SCO with a poor photoswitchability. These results demonstrate that the choice of the acetyl position on the pyridine dictates the structural characteristics of the compounds with a direct impact on the SCO behavior. Remarkably, this work opens interesting perspectives for the future design of Fe-Ag cyanido coordination polymers with judiciously substituted pyridine ligands to tune the thermally and photoinduced SCO properties.

In this study, we explore the effect of a single flat band in the electronic properties of a ferromagnetic two-dimensional Lieb lattice using the multiband Hubbard model with polarized carriers, spin-up and spin-down. We employ the self-consistent dynamical mean field theory and a Green functions cumulant expansion around the atomic limit to obtain the correlated densities of states while varying the intra- and interband interactions. Our findings demonstrate a renormalization of the correlated density of states in both the spin-up and spin-down carriers as we varied the intra- and interband interactions. We conclude that the presence of a flat band enables the system to maintain a metal state with itinerant ferromagnetism in the spin-up carrier., (© 2024 IOP Publishing Ltd.)

Ruddlesden-Popper halide perovskites are highly versatile quasi-two-dimensional energy materials with a wide range of tunable optoelectronic properties. Here we use the all-inorganic Csn+1Pb n X3n+1Ruddlesden-Popper perovskites with X = I, Br, and Cl to systematically model the effect of octahedral tilting distortions on the energy landscape, band gaps, macroscopic polarization, and the emergence of Rashba-/Dresselhaus splitting in these materials. We construct all unique n  = 1 and n  = 2 structures following from octahedral tilts and use first-principles density functional theory to calculate total energies, polarizations and band structures, backed up by band gap calculations using the GW approach. Our results provide design rules for tailoring structural distortions and band-structure properties in all-inorganic Ruddlesden-Popper perovskites through the interplay of the amplitude, direction, and chemical character of the antiferrodistortive distortion modes contributing to each octahedral tilt pattern. Our work emphasizes that, in contrast to three-dimensional perovskites, polar structures may arise from a combination of octahedral tilts, and Rashba-/Dresselhaus splitting in this class of materials is determined by the direction and Pb-I orbital contribution of the polar distortion mode., (Creative Commons Attribution license.)

Electronic synergy between metal ions and organic linkers is a key to engineering molecule-based materials with a high electrical conductivity and, ultimately, metallicity. To enhance conductivity in metal-organic solids, chemists aim to bring the electrochemical potentials of the constituent metal ions and bridging organic ligands closer in a quest to obtain metal-d and ligand-π admixed frontier bands. Herein, we demonstrate the critical role of the metal ion in tuning the electronic ground state of such materials. While VCl 2 (pyrazine) 2 is an electrical insulator, TiCl 2 (pyrazine) 2 displays the highest room-temperature electronic conductivity (5.3 S cm -1 ) for any metal-organic solid involving octahedrally coordinated metal ions. Notably, TiCl 2 (pyrazine) 2 exhibits Pauli paramagnetism consistent with the specific heat, supporting the existence of a Fermi liquid state (i.e., a correlated metal). This result widens perspectives for designing molecule-based systems with strong metal-ligand covalency and electronic correlations., (© 2022. The Author(s).)

Crystalline materials with broken inversion symmetry can exhibit a spontaneous electric polarization, which originates from a microscopic electric dipole moment. Long-range polar or anti-polar order of such permanent dipoles gives rise to ferroelectricity or antiferroelectricity, respectively. However, the recently discovered antiferroelectrics of fluorite structure (HfO 2 and ZrO 2 ) are different: A non-polar phase transforms into a polar phase by spontaneous inversion symmetry breaking upon the application of an electric field. Here, we show that this structural transition in antiferroelectric ZrO 2 gives rise to a negative capacitance, which is promising for overcoming the fundamental limits of energy efficiency in electronics. Our findings provide insight into the thermodynamically forbidden region of the antiferroelectric transition in ZrO 2 and extend the concept of negative capacitance beyond ferroelectricity. This shows that negative capacitance is a more general phenomenon than previously thought and can be expected in a much broader range of materials exhibiting structural phase transitions., (© 2022. The Author(s).)

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi-modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo-BiVO 4 . By using scanning transmission X-ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X-ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V 2 O 5 at grain boundaries of Mo-BiVO 4 thin films, which is further supported by X-ray photoelectron spectroscopy and many-body density functional theory calculations. Theoretical calculations also enable to predict the X-ray absorption spectral fingerprint of polarons in Mo-BiVO 4 . After photo-electrochemical operation, the degraded Mo-BiVO 4 films show similar grain center and grain boundary spectra indicating V 2 O 5 dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl 2 (pyrazine) 2 , an air-stable layered solid, by reaction of CrCl 2 with pyrazine (pyz). This compound displays a ferrimagnetic order below ∼55 K, reflecting the presence of strong magnetic interactions. Electrical conductivity measurements demonstrate that CrCl 2 (pyz) 2 reaches a conductivity of 32 mS cm -1 at room temperature, which operates through a 2D hopping-based transport mechanism. These properties are induced by the redox-activity of the pyrazine ligand, which leads to a smearing of the Cr 3d and pyrazine π states. We suggest that the combination of redox-active ligands and reducing paramagnetic metal ions represents a general approach towards tuneable 2D materials that consist of charge-neutral layers and exhibit both long-range magnetic order and high electronic conductivity.

Conductive metal-organic frameworks are an emerging class of three-dimensional architectures with degrees of modularity, synthetic flexibility and structural predictability that are unprecedented in other porous materials. However, engendering long-range charge delocalization and establishing synthetic strategies that are broadly applicable to the diverse range of structures encountered for this class of materials remain challenging. Here, we report the synthesis of K x Fe 2 (BDP) 3 (0 ≤ x ≤ 2; BDP 2-  = 1,4-benzenedipyrazolate), which exhibits full charge delocalization within the parent framework and charge mobilities comparable to technologically relevant polymers and ceramics. Through a battery of spectroscopic methods, computational techniques and single-microcrystal field-effect transistor measurements, we demonstrate that fractional reduction of Fe 2 (BDP) 3 results in a metal-organic framework that displays a nearly 10,000-fold enhancement in conductivity along a single crystallographic axis. The attainment of such properties in a K x Fe 2 (BDP) 3 field-effect transistor represents the realization of a general synthetic strategy for the creation of new porous conductor-based devices.

Hybrid organic-inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb-I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm -1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I-Pb-I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI 6 4- geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.

The desire for low-power/voltage operation of devices is driving renewed interest in understanding scaling effects in ferroelectric thin films. As the dimensions of ferroelectrics are reduced, the properties can vary dramatically, including the robust scaling relationship between coercive field ( E c ) and thickness ( d), also referred to as the Janovec-Kay-Dunn (JKD) law, wherein E c ∝ d -2/3 . Here, we report that whereas (001)-oriented heterostructures follow JKD scaling across the thicknesses range of 20-330 nm, (111)-oriented heterostructures of the canonical tetragonal ferroelectric PbZr 0.2 Ti 0.8 O 3 exhibit a deviation from JKD scaling wherein a smaller scaling exponent for the evolution of E c is observed in films of thickness ≲ 165 nm. X-ray diffraction reveals that whereas (001)-oriented heterostructures remain tetragonal for all thicknesses, (111)-oriented heterostructures exhibit a transition from tetragonal-to-monoclinic symmetry in films of thickness ≲ 165 nm as a result of the compressive strain. First-principles calculations suggest that this symmetry change contributes to the deviation from the expected scaling, as the monoclinic phase has a lower energy barrier for switching. This structural evolution also gives rise to changes in the c/ a lattice parameter ratio, wherein this ratio increases and decreases in (001)- and (111)-oriented heterostructures, respectively, as the films are made thinner. In (111)-oriented heterostructures, this reduced tetragonality drives a reduction of the remanent polarization and, therefore, a reduction of the domain-wall energy and overall energy barrier to switching, which further exacerbates the deviation from the expected scaling. Overall, this work demonstrates a route toward reducing coercive fields in ferroelectric thin films and provides a possible mechanism to understand the deviation from JKD scaling.

Raman and photoluminescence (PL) spectroscopy are used to investigate dynamic structure-function relationships in methylammonium lead iodide (MAPbI 3 ) perovskite. The intensity of the 150 cm -1 methylammonium (MA) librational Raman mode is found to be correlated with PL intensities in microstructures of MAPbI 3 . Because of the strong hydrogen bond between hydrogens in MA and iodine in the PbI 6 perovskite octahedra, the Raman activity of MA is very sensitive to structural distortions of the inorganic framework. The structural distortions directly influence PL intensities, which in turn have been correlated with microstructure quality. Our measurements, supported with first-principles calculations, indicate how excited-state MA librational displacements mechanistically control PL efficiency and lifetime in MAPbI 3 -material parameters that are likely important for efficient photovoltaic devices.

This study demonstrates that antiferroelectricity can be stabilized in NaNbO(3) (NN) based ceramics by lowering the tolerance factor. Through consideration of the crystal chemistry via the Goldschmidt tolerance factor and polarizability, we show that simultaneous substitution of Zr(4+) and Ca(2+) ions in the Nb and Na sites, respectively, lowers the polarizability and tolerance factor of the (Na(1-x)Ca(x))(Nb(1-x)Zrx)O(3) (CZNN100x) solid solution, while maintaining charge neutrality. Structural investigations using both X-ray diffraction and transmission electron microscopy (TEM) indicated an enhancement of antiferroelectric (AFE) superlattice peaks with CaZrO(3) substitution. The TEM domain analysis revealed that only AFE domains existed in the CZNN4 and CZNN5 ceramics; in contrast, normal NN ceramics displayed coexistence of AFE and ferroelectric (FE) domains at room temperature. The CZNN100x (0.02 ≤x≤ 0.05) ceramics showed double polarization hysteresis loops, characteristic of reversible AFE↔FE phase transition switching. The field-induced polarization decreased drastically with increasing substitution, an effect of the decreases in tolerance factor. In addition, the AFE switching field was increased by the chemical substitution. First principles calculations are performed to obtain insights into the relative stability and coexistence of the AFE and FE phases in single domains. The large decrease of polarization in the CZNN system is explained by a modification of the relative stability of the relevant structures, which favours nonpolar-to-polar AFE transitions over polar-to-polar FE domain switching.