Real space investigation of structural changes at the metal-insulator transition in VO2

Synchrotron X-ray total scattering studies of structural changes in rutile VO2 at the metal-insulator transition temperature of 340 K reveal that monoclinic and tetragonal phases of VO2 coexist in equilibrium, as expected for a first-order phase transition. No evidence for any distinct intermediate phase is seen. Unbiased local structure studies of the changes in V--V distances through the phase transition, using reverse Monte Carlo methods, support the idea of phase coexistence and point to the high degree of correlation in the dimerized low-temperature structure. No evidence for short range V--V correlations that would be suggestive of local dimers is found in the metallic phase.Comment: 4 pages, 5 figure

Determining conductivity and mobility values of individual components in multiphase composite Cu_(1.97)Ag_(0.03)Se

The intense interest in phase segregation in thermoelectrics as a means to reduce the lattice thermal conductivity and to modify the electronic properties from nanoscale size effects has not been met with a method for separately measuring the properties of each phase assuming a classical mixture. Here, we apply effective medium theory for measurements of the in-line and Hall resistivity of a multiphase composite, in this case Cu_(1.97) Ag_(0.03)Se. The behavior of these properties with magnetic field as analyzed by effective medium theory allows us to separate the conductivity and charge carrier mobility of each phase. This powerful technique can be used to determine the matrix properties in the presence of an unwanted impurity phase, to control each phase in an engineered composite, and to determine the maximum carrier concentration change by a given dopant, making it the first step toward a full optimization of a multiphase thermoelectric material and distinguishing nanoscale effects from those of a classical mixture

Understanding complex magnetic order in disordered cobalt hydroxides through analysis of the local structure

In many ostensibly crystalline materials, unit-cell-based descriptions do not always capture the complete physics of the system due to disruption in long-range order. In the series of cobalt hydroxides studied here, Co(OH)$_{2-x}$(Cl)$_x$(H$_2$O)$_{n}$, magnetic Bragg diffraction reveals a fully compensated N\'eel state, yet the materials show significant and open magnetization loops. A detailed analysis of the local structure defines the aperiodic arrangement of cobalt coordination polyhedra. Representation of the structure as a combination of distinct polyhedral motifs explains the existence of locally uncompensated moments and provides a quantitative agreement with bulk magnetic measurements and magnetic Bragg diffraction

Tuning magnetic frustration on the diamond lattice of the A-site magnetic spinels CoAl2−x_{2-x}Gax_xO4_4: Lattice expansion and site disorder

The spinels CoB$_2$O$_4$ with magnetic Co$^{2+}$ ions on the diamond lattice A site can be frustrated because of competing near-neighbor ($J_1$) and next-near neighbor ($J_2$) interactions. Here we describe attempts to tune the relative strengths of these interactions by substitution on the non-magnetic B-site. The system we employ is CoAl$_{2-x}$Ga$_x$O$_4$, where Al is systematically replaced by the larger Ga, ostensibly on the B site. As expected, Ga substitution expands the lattice, resulting in Co atoms on the A-site being pushed further from one other and thereby weakening magnetic interactions. In addition, Ga distributes between the B and the A site in a concentration dependent manner displacing an increasing amount of Co from the A site with increasing $x$. This increased inversion, which is confirmed by neutron diffraction studies carried out at room temperature, affects magnetic ordering very significantly, and changes the nature of the ground state. Modeling of the magnetic coupling illustrates the complexity that arises from the cation site disorder.Comment: 9 pages, 10 figure

Influence of rotational distortions on Li⁺- and Na⁺- intercalation in anti-NASICON Fe₂(MoO₄)₃

Anti-NASICON Fe₂(MoO₄)₃ (<i>P</i>2₁/<i>c</i>) shows significant structural and electrochemical differences in the intercalation of Li⁺ and Na⁺ ions. To understand the origin of this behavior, we have used a combination of in situ X-ray and high-resolution neutron diffraction, total scattering, electrochemical measurements, density functional theory calculations, and symmetry-mode analysis. We find that for Li⁺-intercalation, which proceeds via a two-phase monoclinic-to-orthorhombic (<i>Pbcn</i>) phase transition, the host lattice undergoes a concerted rotation of rigid polyhedral subunits driven by strong interactions with the Li⁺ ions, leading to an ordered lithium arrangement. Na⁺-intercalation, which proceeds via a two-stage solid solution insertion into the monoclinic structure, similarly produces rotations of the lattice polyhedral subunits. However, using a combination of total neutron scattering data and density functional theory calculations, we find that while these rotational distortions upon Na⁺-intercalation are fundamentally the same as for Li⁺-intercalation, they result in a far less coherent final structure, with this difference attributed to the substantial difference between the ionic radii of the two alkali metals

Electronic structure and transport in thermoelectric compounds AZn_2Sb_2 (A = Sr, Ca, Yb, Eu)

The AZn_2Sb_2 (P¯3m1, A = Ca, Sr, Eu, Yb) class of Zintl compounds has shown high thermoelectric efficiency (zT ~ 1) and is an appealing system for the development of Zintl structure–property relationships. High temperature transport measurements have previously been conducted for all known compositions except for SrZn_2Sb_2; here we characterize polycrystalline SrZn_2Sb_2 to 723 K and review the transport behavior of the other compounds in this class. Consistent with the known AZn_2Sb_2 compounds, SrZn_2Sb_2 is found to be a hole-doped semiconductor with a thermal band gap ~ 0.27 eV. The Seebeck coefficients of the AZn2Sb2 compounds are found to be described by similar effective mass (m* ~ 0.6 m_e). Electronic structure calculations reveal similar m* is due to antimony p states at the valence band edge which are largely unaffected by the choice of A-site species. However, the choice of A-site element has a dramatic effect on the hole mobility, with the room temperature mobility of the rare earth-based compositions approximately double that found for Ca and Sr on the A site. This difference in mobility is examined in the context of electronic structure calculations