A metal-insulator transition and its intriguing properties were recently reported based on doping of the antiferromagnetic insulator LaFeO₃. Through doping at the B site by Mo to the insulating perovskite LaFeO₃ exhibits a coexistence of an antiferromagnetic ordering with room-temperature metallicity at higher doping levels, an unusual ground state for an oxide perovskite. Replacing Fe by Mo in the Fe-O₆ octahedra enhances the separation of the two 2 Fe-O bonds relative to the orthorhombic LaFeO₃, largely retaining the centrosymmetric character of the Fe sites, as confirmed through extended x-ray absorption fine structure. Mo ions appear to be homogeneously doped, with average valency of both metal sites monotonically decreasing with increasing Mo concentration. Resonant photoemission was recorded for both Fe and Mo to obtain element specific spectral information on the projected 3d and 4d partial density of states. The data shows gradual increase of spectral weight at the Fermi level that is attributed to Mo d states, while the Fe d states primarily reside at higher binding energy in the valence band, with significant hybridization with O 2p states. The RIXS spectra show strong electron correlation effects from d-d inelastic features and broad charge-transfer excitations for x = 0.2 where the compound becomes metallic. This is in contrast to the insulating parent LaFeO₃ compound and insulating samples with lower Mo content. The coexistence of both bound and continuum excitations observed in the RIXS spectra provides strong evidence for charge disproportionation with features that are linked to the disproportionate Fe sites.

Resonant x-ray spectroscopies were used to investigate the double perovskite Sr₂FeMoO₆ (SFMO) in order to identify the compounds valence electronic structure known for its half-metallicity and ferrimagnetism above room temperature. A comprehensive resonant photoelectron spectroscopy (RPES) and resonant inelastic x-ray scattering (RIXS) study was carried out to acquire a more detailed understanding and interpretation of the valence band electronic structure and hybridization between Fe and Mo d bands. The RPES spectrum clearly show enhancement of Mo d states at the Fermi level that are partly responsible for the metallic behavior. The RPES data at the Fe L₃ edge shows strong hybridization with O 2p states as well hybridization with Mo d states. At the same time, characteristic d-d excitations are observed in the RIXS spectra at the Fe L edge indicative of Fe d states of more localized character. Although there are many valid definitions to the valency of the Fe and Mo ions and magnetic moments, the total electronic structure represented through element-resolved x-ray spectroscopies studies distinctly identifies the electronic states that results in its established correlated behavior and half-metallicity.

We recently demonstrated the lowest bandgap bulk ferroelectric material, BaTi1-x(Mn1/2Nb1/2)xO3, a promising candidate material for visible light absorption in opto- electronic devices. Using a combination of x-ray spectroscopies and density functional theory (DFT) calculations, we here elucidate this compound’s electronic structure and the modifications induced by Mn doping. In particular, we are able to rationalize how this compound retains its ferroelectricity even through a significant reduction of the optical gap upon Mn doping. The local electronic structure and atomic coordination are investigated using x-ray absorption at the Ti K, Mn K, and O K edges, which suggests only small distortions to the parent tetragonal ferroelectric system, BaTiO3, thereby providing a clue to the substantial retention of ferroelectricity in spite of doping. Features at the Ti K edge, which are sensitive to local symmetry and an indication of Ti off-centering within the Ti-O6 octahedra, show modest changes with doping and strongly corroborates with our measured polarization values. Resonant photoelectron spectroscopy results suggest the origin of the reduction of the bandgap in terms of newly created Mn d bands that hybridize with O 2p states. X-ray absorption spectra at the O K-edge provide evidence for new states below the conduction band of the parent compound, illustrating additional contributions facilitating bandgap reduction.

BaTiO₃ thin films co-doped at the Ti site with Mn and Nb were grown on 0.5% Nb-doped (001) oriented SrTiO₃ substrates by pulsed laser deposition. The films show single-phase tetragonal structure, growing epitaxially with a smooth interface to the substrate. Using piezoforce microscopy, we find that both doped and undoped films exhibit good ferroelectric response. The piezoelectric domain switching in the films was confirmed by measuring local hysteresis of the polarization at several different areas across the thin films, demonstrating a switchable ferroelectric state for these films. The doping of the BaTiO3 also reduces the bandgap of the material from 3.18 eV for BaTiO₃ to nearly 2.7 eV for the 7.5% doped sample, potentially making the films effective light-harvesters in the visible spectrum. The results demonstrate co-doping as an effective strategy for bandgap engineering and a guide for the realization of visible-light applications of related thin film systems.

We report the significant role of synthetic routes and the importance of solvents in the synthesis of organic-inorganic lead iodide materials. Through one route, the intercalation of dimethylformamide in the crystal structure was observed leading to a one-dimensional (1D) [NH3(CH2)(4)NH3]Pb2I6 structure of the product. This product was compared with the two-dimensional (2D) [NH3(CH2)(4)NH3]PbI4 recovered from aqueous solvent based synthesis with the same precursors. UV-visible absorption spectroscopy showed a red-shift of 0.1 eV for the band gap of the 1D network in relation to the 2D system. This shift primarily originates from a shift in the valence band edge as determined from photoelectron-and X-ray spectroscopy results. These findings also suggest the iodide 5p orbital as the principal component in the density of states in the valence band edge. Single crystal data show a change in the local coordination around iodide, while in both materials, lead atoms are surrounded by iodide atoms in octahedral units. The conductivity of the one-dimensional material ([NH3(CH2)(4)NH3]Pb2I6) was 50% of the two-d(i)mensional material ([NH3(CH2)(4)NH3]PbI4). The fabricated solar cells reflect these changes in the chemical and electronic structure of both materials, although the total light conversion efficiencies of solar cells based on both products were similar.

Layered two-dimensional (2D) hybrid organic-inorganic perovskites (HOP) are promising materials for light-harvesting applications because of their chemical stability, wide flexibility in composition and dimensionality, and increases in photovoltaic power conversion efficiencies. Three 2D lead iodide perovskites were studied through various X-ray spectroscopic techniques to derive detailed electronic structures and band energetics profiles at a titania interface. Core-level and valence band photoelectron spectra of HOP were analyzed to resolve the electronic structure changes due to the reduced dimensionality of inorganic layers. The results show orbital narrowing when comparing the HOP, the layered precursor PbI2, and the conventional 3D (CH3NH3)PbI3 such that different localizations of band edge states and narrow band states are unambiguously due to the decrease in dimensionality of the layered HOPs. Support from density functional theory calculations provide further details on the interaction and band gap variations of the electronic structure. We observed an interlayer distance dependent dispersion in the near band edge electronic states. The results show how tuning the interlayer distance between the inorganic layers affects the electronic properties and provides important design principles for control of the interlayer charge transport properties, such as the change in effective charge masses as a function of the organic cation length. The results of these findings can be used to tune layered materials for optimal functionality and new applications.

Bismuth halide compounds as a non-toxic alternative are increasingly investigated because of their potential in optoelectronic devices and their rich structural chemistry. Hard X-ray spectroscopy was applied to the ternary bismuth halide Cs3Bi2I9 and its related precursors BiI3 and CsI to understand its electronic structure at an atomic level. We specifically investigated the core levels and valence band using X-ray photoemission spectroscopy (PES), high-resolution X-ray absorption (HERFD-XAS), and resonant inelastic X-ray scattering (RIXS) to get insight into the chemistry and the band edge properties of the two bismuth compounds. Using these element specific X-ray techniques, our experimental electronic structures show that the primary differences between the two bismuth samples are the position of the iodine states in the valence and conduction bands and the degree of hybridization with bismuth lone pair (6s(2)) states. The crystal structure of the two layered quasi-perovskite compounds plays a minor role in modifying the overall electronic structure, with variations in bismuth lone pair states and iodine band edge states. Density Functional Theory (DFT) calculations are used to compare with experimental data. The results demonstrate the effectiveness of hard X-ray spectroscopies to identify element specific bulk electronic structures and their use in optoelectronic devices.

We present a controlled, stepwise formation of methylammonium bismuth iodide (CH3NH3)(3)Bi2I9 perovskite films prepared via the vapour assisted solution process (VASP) by exposing BiI3 films to CH3NH3I (MAI) vapours for different reaction times, (CH3NH3)(3)Bi2I9 semiconductor films with tunable optoelectronic properties are obtained. Solar cells prepared on mesoporous TiO2 substrates yielded hysteresis-free efficiencies upto 3.17% with good reproducibility. The good performance is attributed mainly to the homogeneous surface coverage, improved stoichiometry, reduced metallic content in the bulk, and desired optoelectronic properties of the absorbing material. In addition, solar cells prepared using pure BiI3 films without MAI exposure achieved a power conversion efficiency of 0.34%. The non-encapsulated (CH3NH3)(3)Bi2I9 devices were found to be stable for as long as 60 days with only 0.1% drop in efficiency. This controlled formation of (CH3NH3)(3)Bi2I9 perovskite films highlights the benefit of the VASP technique to optimize material stoichiometry, morphology, solar cell performance, and long-term durability.

Solution-processed colloidal quantum dot (CQD) solar cells harvesting the infrared part of the solar spectrum are especially interesting for future use in semitransparent windows or multilayer solar cells. To improve the device power conversion efficiency (PCE) and stability of the solar cells, surface passivation of the quantum dots is vital in the research of CQD solar cells. Herein, inorganic CsPbI3 perovskite (CsPbI3-P) coating on PbS CQDs with a low-temperature, solution-processed approach is reported. The PbS CQD solar cell with CsPbI3-P coating gives a high PCE of 10.5% and exhibits remarkable stability both under long-term constant illumination and storage under ambient conditions. Detailed characterization and analysis reveal improved passivation of the PbS CQDs with the CsPbI3-P coating, and the results suggest that the lattice coherence between CsPbI3-P and PbS results in epitaxial induced growth of the CsPbI3-P coating. The improved passivation significantly diminishes the sub-bandgap trap-state assisted recombination, leading to improved charge collection and therefore higher photovoltaic performance. This work therefore provides important insight to improve the CQD passivation by coating with an inorganic perovskite ligand for photovoltaics or other optoelectronic applications.

Tailoring transport properties of strongly correlated electron systems in a controlled fashion counts among the dreams of materials scientists. In copper oxides, vary- ing the carrier concentration is a tool to obtain high- temperature superconducting phases. In manganites, dop- ing results in exotic physics such as insulator-metal tran- sitions (IMT), colossal magnetoresistance (CMR), orbital- or charge-ordered (CO) or charge-disproportionate (CD) states. In most oxides, antiferromagnetic order and CD phase is asssociated with insulating behavior. Here we re- port the realization of a unique physical state that can be induced by Mo doping in LaFeO3: the resulting metallic state is a site-selective Mott insulator where itinerant elec- trons evolving on low-energy Mo states coexist with local- ized carriers on the Fe sites. In addition, a local breathing- type lattice distortion induces charge disproportionation on the latter, without destroying the antiferromagnetic order. A state, combining antiferromangetism, metallic- ity and CD phenomena is rather rare in oxides and have utmost significance for future antiferromagnetic memory devices.