Ligand-Mediated Control of Dopant Oxidation State and X-ray Excited Optical Luminescence in Eu-Doped LaOCl.

The development of an expanded palette of X-ray phosphors is a critical imperative for applications in medical imaging, radiation detection, and scientific instrumentation. The rational design of X-ray phosphors has been stymied by the absence of fundamental understanding of activation channels, sensitization mechanisms, and recombination pathways induced upon high-energy excitation of luminescent centers. In this article, we describe the preparation of Eu-doped LaOCl nanocrystals based on the condensation of molecular precursors. The synthetic route allows for control of the oxidation state of the incorporated Eu-atoms based on ligand-induced oxidation or reduction of the Eu-precursors. Nanocrystals exhibiting blue and red X-ray excited optical luminescence are developed by tuning the oxidation state of europium ions incorporated within the LaOCl nanocrystal matrix. Pronounced modulation of the intensity of the optical luminescence is evidenced at and near the giant resonance absorption of the host matrix as a result of distinctly divergent recombination channels. Resonant excitation results in recombination via Auger electron ionization and relaxation of a single electron-hole pair, whereas excitation away from the giant resonance results in thermalization of "hot" electron-hole pairs, while launching cascades of energy transfer, excitation, and radiative recombination events at the Eu-luminescent centers. Mechanistic elucidation and the development of a generalizable synthetic route starting from molecular precursors paves the way to an expanded palette of X-ray phosphors.

Elucidating the Crystallite Size Dependence of the Thermochromic Properties of Nanocomposite VO2 Thin Films.

Fenestration elements that enable spectrally selective dynamic modulation of the near-infrared region of the electromagnetic spectrum are of great interest as a means of decreasing the energy consumption of buildings by adjusting solar heat gain in response to external temperature. The binary vanadium oxide VO2 exhibits a near-room-temperature insulator-metal electronic transition accompanied by a dramatic modulation of the near-infrared transmittance. The low-temperature insulating phase is infrared transparent but blocks infrared transmission upon metallization. There is considerable interest in harnessing the thermochromic modulation afforded by VO2 in nanocomposite thin films. However, to prepare a viable thermochromic film, the visible-light transmittance must be maintained as high as possible while maximizing thermochromic modulation in the near-infrared region of the electromagnetic spectrum, which necessitates the development of high-crystalline-quality VO2 nanocrystals of the optimal particle size embedded within the appropriate host matrix and refractive index matched to the host medium. Here, we demonstrate the preparation of acrylate-based nanocomposite thin films with varying sizes of embedded VO2 nanoparticles. The observed strong size dependence of visible-light transmittance and near-infrared modulation is explicable on the basis of optical simulations. In this article, we elucidate multiple scattering and absorption mechanisms, including Mie scattering, temperature-/phase-variant refractive-index mismatch between VO2 nanocrystals and the encapsulating matrix, and the appearance of a surface plasmon resonance using temperature-variant absorptance and diffuse transmittance spectroscopy measurements performed as a function of particle loading for the different sizes of VO2 nanocrystals. Nanocrystals with dimensions of 44 ± 30 nm show up to >32% near-infrared energy modulation across the near-infrared region of the electromagnetic spectrum while maintaining high visible-light transmission. The results presented here, providing mechanistic elucidation of the size dependence of the different scattering mechanisms, underscore the importance of nanocrystallite dimensions, refractive-index matching, and individualized dispersion of particles within the host matrix for the preparation of viable thermochromic thin films mitigating Mie scattering and differential refractive-index scattering.

Mapping polaronic states and lithiation gradients in individual V2O5 nanowires.

The rapid insertion and extraction of Li ions from a cathode material is imperative for the functioning of a Li-ion battery. In many cathode materials such as LiCoO2, lithiation proceeds through solid-solution formation, whereas in other materials such as LiFePO4 lithiation/delithiation is accompanied by a phase transition between Li-rich and Li-poor phases. We demonstrate using scanning transmission X-ray microscopy (STXM) that in individual nanowires of layered V2O5, lithiation gradients observed on Li-ion intercalation arise from electron localization and local structural polarization. Electrons localized on the V2O5 framework couple to local structural distortions, giving rise to small polarons that serves as a bottleneck for further Li-ion insertion. The stabilization of this polaron impedes equilibration of charge density across the nanowire and gives rise to distinctive domains. The enhancement in charge/discharge rates for this material on nanostructuring can be attributed to circumventing challenges with charge transport from polaron formation.

X-ray excited photoluminescence near the giant resonance in solid-solution Gd(1-x)Tb(x)OCl nanocrystals and their retention upon solvothermal topotactic transformation to Gd(1-x)Tb(x)F3.

Design rules for X-ray phosphors are much less established as compared to their optically stimulated counterparts owing to the absence of a detailed understanding of sensitization mechanisms, activation pathways and recombination channels upon high-energy excitation. Here, we demonstrate a pronounced modulation of the X-ray excited photoluminescence of Tb(3+) centers upon excitation in proximity to the giant resonance of the host Gd(3+) ions in solid-solution Gd1-xTbxOCl nanocrystals prepared by a non-hydrolytic cross-coupling method. The strong suppression of X-ray excited optical luminescence at the giant resonance suggests a change in mechanism from multiple exciton generation to single thermal exciton formation and Auger decay processes. The solid-solution Gd1-xTbxOCl nanocrystals are further topotactically transformed with retention of a nine-coordinated cation environment to solid-solution Gd1-xTbxF3 nanocrystals upon solvothermal treatment with XeF2. The metastable hexagonal phase of GdF3 can be stabilized at room temperature through this topotactic approach and is transformed subsequently to the orthorhombic phase. The fluoride nanocrystals indicate an analogous but blue-shifted modulation of the X-ray excited optical luminescence of the Tb(3+) centers upon X-ray excitation near the giant resonance of the host Gd(3+) ions.

Transformers: the changing phases of low-dimensional vanadium oxide bronzes.

In this feature article, we explore the electronic and structural phase transformations of ternary vanadium oxides with the composition MxV2O5 where M is an intercalated cation. The periodic arrays of intercalated cations ordered along quasi-1D tunnels or layered between 2D sheets of the V2O5 framework induce partial reduction of the framework vanadium atoms giving rise to charge ordering patterns that are specific to the metal M and stoichiometry x. This periodic charge ordering makes these materials remarkably versatile platforms for studying electron correlation and underpins the manifestation of phenomena such as colossal metal-insulator transitions, quantized charge corrals, and superconductivity. We describe current mechanistic understanding of these emergent phenomena with a particular emphasis on the benefits derived from scaling these materials to nanostructured dimensions wherein precise ordering of cations can be obtained and phase relationships can be derived that are entirely inaccessible in the bulk. In particular, structural transformations induced by intercalation are dramatically accelerated due to the shorter diffusion path lengths at nanometer-sized dimensions, which cause a dramatic reduction of kinetic barriers to phase transformations and facilitate interconversion between the different frameworks. We conclude by summarizing numerous technological applications that have become feasible due to recent advances in controlling the structural chemistry and both electronic and structural phase transitions in these versatile frameworks.

Emptying and filling a tunnel bronze.

The classical orthorhombic layered phase of V2O5 has long been regarded as the thermodynamic sink for binary vanadium oxides and has found great practical utility as a result of its open framework and easily accessible redox states. Herein, we exploit a cation-exchange mechanism to synthesize a new stable tunnel-structured polymorph of V2O5 (ζ-V2O5) and demonstrate the subsequent ability of this framework to accommodate Li and Mg ions. The facile extraction and insertion of cations and stabilization of the novel tunnel framework is facilitated by the nanometer-sized dimensions of the materials, which leads to accommodation of strain without amorphization. The topotactic approach demonstrated here indicates not just novel intercalation chemistry accessible at nanoscale dimensions but also suggests a facile synthetic route to ternary vanadium oxide bronzes (M x V2O5) exhibiting intriguing physical properties that range from electronic phase transitions to charge ordering and superconductivity.

Scalable hydrothermal synthesis of free-standing VO2 nanowires in the M1 phase.

VO2 nanostructures derived from solution-phase methods are often plagued by broadened and relatively diminished metal-insulator transitions and adventitious doping due to imperfect control of stoichiometry. Here, we demonstrate a stepwise scalable hydrothermal and annealing route for obtaining VO2 nanowires exhibiting almost 4 orders of magnitude abrupt (within 1 °C) metal-insulator transitions. The prepared nanowires have been characterized across their structural and electronic phase transitions using single-nanowire Raman microprobe analysis, ensemble differential scanning calorimetry, and single-nanowire electrical transport measurements. The electrical band gap is determined to be 600 meV and is consistent with the optical band gap of VO2, and the narrowness of differential scanning calorimetry profiles indicates homogeneity of stoichiometry. The preparation of high-quality free-standing nanowires exhibiting pronounced metal-insulator transitions by a solution-phase process allows for scalability, further solution-phase processing, incorporation within nanocomposites, and integration onto arbitrary substrates.