David Keen

Abstract:

Material functionality can be strongly determined by structure extending only over nanoscale distances. The pair distribution function presents an opportunity for structural studies beyond idealized crystal models and to investigate structure over varying length scales. Applying this method with ultrafast time resolution has the potential to similarly disrupt the study of structural dynamics and phase transitions. Here we demonstrate such a measurement of CuIr₂S₄ optically pumped from its low-temperature Ir-dimerized phase. Dimers are optically suppressed without spatial correlation, generating a structure whose level of disorder strongly depends on the length scale. The redevelopment of structural ordering over tens of picoseconds is directly tracked over both space and time as a transient state is approached. This measurement demonstrates the crucial role of local structure and disorder in non-equilibrium processes as well as the feasibility of accessing this information with state-of-the-art XFEL facilities.

Abstract:

Here we describe the synthesis of a compositional series of metal-organic framework crystalline-inorganic glass composites (MOF-CIGCs) containing ZIF-8 and an inorganic phosphate glass, 20Na₂O-10NaCl-70P₂O₅, to expand the library of host matrices for metal-organic frameworks. By careful selection of the inorganic glass component, a relatively high loading of ZIF-8 (70 wt%) was achieved, which is the active component of the composite. A Zn⋯O-P interfacial bond, previously identified in similar composites/hybrid blends, was suggested by analysis of the total scattering pair distribution function data. Additionally, CO₂ and N₂ sorption and variable-temperature PXRD experiments were performed to assess the composites' properties.

Abstract:

We use a combination of X-ray pair distribution function (PDF) measurements, lattice dynamical calculations, and ab initio density functional theory (DFT) calculations to study the local structure and dynamics in various MPt­(CN)6 Prussian blue analogues. In order to link directly the local distortions captured by the PDF with the lattice dynamics of this family, we develop and apply a new “interaction-space” PDF refinement approach. This approach yields effective harmonic force constants, from which the (experiment-derived) low-energy phonon dispersion relations can be approximated. Calculation of the corresponding Grüneisen parameters allows us to identify the key modes responsible for negative thermal expansion (NTE) as arising from correlated tilts of coordination octahedra. We compare our results against the phonon dispersion relations determined using DFT calculations, which identify the same NTE mechanism.

Abstract:

Hybrid organic-inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs. In this work, we describe the first mechanochemically-induced crystal-glass transformation of HOIPs as a rapid, green and efficient approach for producing glasses. The amorphous phase was formed from the crystalline phase within 10 minutes of ball-milling, and exhibited glass transition behaviour as evidenced by thermal analysis techniques. Time-resolved in situ ball-milling with synchrotron powder diffraction was employed to study the microstructural evolution of amorphisation, which showed that the crystallite size reaches a comminution limit before the amorphisation process is complete, indicating that energy may be further accumulated as crystal defects. Total scattering experiments revealed the limited short-range order of amorphous HOIPs, and their optical properties were studied by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy.