arXiv subjects

P. W. Stephens

Publications and source records attributed to P. W. Stephens.

15 recordsLinked to original sources

arXiv2015

Magnetism in a family of $S = 1$ square lattice antiferromagnets Ni$X_2$(pyz)$_2$ ($X = $ Cl, Br, I, NCS; pyz = pyrazine)

The crystal structures of Ni$X_2$(pyz)$_2$ ($X$ = Cl (\textbf{1}), Br (\textbf{2}), I (\textbf{3}) and NCS (\textbf{4})) were determined at 298~K by synchrotron X-ray powder diffraction. All four compounds consist of two-dimensional (2D) square arrays self-assembled from octahedral NiN$_4$$X_2$ units that are bridged by pyz ligands. The 2D layered motifs displayed by \textbf{1}-\textbf{4} are relevant to bifluoride-bridged [Ni(HF$_2$)(pyz)$_2$]$Z$F$_6$ ($Z$ = P, Sb) which also possess the same 2D layers. In contrast, terminal $X$ ligands occupy axial positions in \textbf{1}-\textbf{4} and cause a staggering of adjacent layers. Long-range antiferromagnetic order occurs below 1.5 (Cl), 1.9 (Br and NCS) and 2.5~K (I) as determined by heat capacity and muon-spin relaxation. The single-ion anisotropy and $g$ factor of \textbf{2}, \textbf{3} and \textbf{4} are measured by electron spin resonance where no zero--field splitting was found. The magnetism of \textbf{1}-\textbf{4} crosses a spectrum from quasi-two-dimensional to three-dimensional antiferromagnetism. An excellent agreement was found between the pulsed-field magnetization, magnetic susceptibility and $T_\textrm{N}$ of \textbf{2} and \textbf{4}. Magnetization curves for \textbf{2} and \textbf{4} calculated by quantum Monte Carlo simulation also show excellent agreement with the pulsed-field data. \textbf{3} is characterized as a three-dimensional antiferromagnet with the interlayer interaction ($J_\perp$) slightly stronger than the interaction within the two-dimensional [Ni(pyz)$_2$]$^{2+}$ square planes ($J_\textrm{pyz}$).

cond-mat.str-el↗

arXiv2014

Crystallography and Physical Properties of BaCo2As2, Ba{0.94}K{0.06}Co2As2 and Ba{0.78}K{0.22}Co2As2

The crystallographic and physical properties of polycrystalline and single crystal samples of BaCo2As2 and K-doped Ba{1-x}K{x}Co2As2 (x = 0.06, 0.22) are investigated by x-ray and neutron powder diffraction, magnetic susceptibility chi, magnetization, heat capacity Cp, {75}As NMR and electrical resistivity rho measurements versus temperature T. The crystals were grown using both Sn flux and CoAs self-flux, where the Sn-grown crystals contain 1.6-2.0 mol% Sn. All samples crystallize in the tetragonal ThCr2Si2-type structure (space group I4/mmm). For BaCo2As2, powder neutron diffraction data show that the c-axis lattice parameter exhibits anomalous negative thermal expansion from 10 to 300 K, whereas the a-axis lattice parameter and the unit cell volume show normal positive thermal expansion over this T range. No transitions in BaCo2As2 were found in this T range from any of the measurements. Below 40-50 K, we find rho ~ T^2 indicating a Fermi liquid ground state. A large density of states at the Fermi energy D(EF) ~ 18 states/(eV f.u.) for both spin directions is found from low-T Cp(T) measurements, whereas the band structure calculations give D(EF) = 8.23 states/(eV f.u.). The {75}As NMR shift data versus T have the same T dependence as the chi(T) data, demonstrating that the derived chi(T) data are intrinsic. The observed {75}As nuclear spin dynamics are consistent with the presence of ferromagnetic and/or stripe-type antiferromagnetic spin fluctuations. The crystals of Ba{0.78}K{0.22}Co2As2 were grown in Sn flux and show properties very similar to those of undoped BaCo2As2. On the other hand, the crystals from two batches of Ba{0.94}K{0.06}Co2As2 grown in CoAs self-flux show evidence of weak ferromagnetism at T < 10 K with small ordered moments at 1.8 K of 0.007 and 0.03 muB per formula unit, respectively.

cond-mat.supr-con↗

arXiv2013

Crystal and Magnetic Structure of CaCo{1.86}As2 Studied by X-ray and Neutron Diffraction

Neutron and x-ray diffraction measurements are presented for powders and single crystals of CaCo{1.86}As2. The crystal structure is a collapsed-tetragonal ThCr2Si2-type structure as previously reported, but with 7(1)% vacancies on the Co sites corresponding to the composition CaCo{1.86(2)}As2. The thermal expansion coefficients for both the a- and c-axes are positive from 10 to 300 K. Neutron diffraction measurements on single crystals demonstrate the onset of A-type collinear antiferromagnetic order below the Neel temperature TN = 52(1) K with the ordered moments directed along the tetragonal c-axis, aligned ferromagnetically in the ab-plane and antiferromagnetically stacked along the c-axis.

cond-mat.supr-con↗

arXiv2013

Synthesis and properties of charge-ordered thallium halide perovskites, CsTl1+0.5Tl3+0.5X3 (X = F, Cl)- theoretical precursors for superconductivity?

Recently CsTlCl3 and CsTlF3 perovskites were theoretically predicted to be potential superconductors if they are optimally doped. The synthesis of these two compounds, together with a complete characterization of the samples are reported. CsTlCl3 is obtained as orange crystals in two different polymorphs: a tetragonal (I4/m) and a cubic (Fm-3m) phase. CsTlF3 is formed as a light brown powder, also as a double cubic perovskite (Fm-3m). In all three CsTlX3 phases Tl1+ and Tl3+ were located in two different crystallographic positions that accommodate their different bond lengths. In CsTlCl3 some Tl vacancies are found in the Tl1+ position. The charge ordering between Tl1+ and Tl3+ was confirmed by x-ray absorption and Raman spectroscopy. The Raman spectroscopy of CsTlCl3 under high pressure (58 GPa) did not indicate any phase transition to a possible single Tl2+ state. However, the highly insulating material becomes less resistive with increasing high pressure, while undergoing a change in the optical properties, from transparent to deeply opaque red, indicative of a decrease of the band gap. The theoretical design and experimental validation of the existence of CsTlF3 and CsTlCl3 cubic perovskites is the necessary first step in confirming the theoretical prediction of superconductivity in these materials.

cond-mat.mtrl-sci↗

arXiv2013

Crystallographic, Electronic, Thermal and Magnetic Properties of Single-Crystal SrCo2As2

In tetragonal SrCo2As2 single crystals, inelastic neutron scattering measurements demonstrated that strong stripe-type antiferromagnetic (AFM) correlations occur at a temperature T = 5 K [W. Jayasekara et al., arXiv:1306.5174] that are the same as in the isostructural AFe2As2 (A = Ca, Sr, Ba) parent compounds of high-Tc superconductors. This surprising discovery suggests that SrCo2As2 may also be a good parent compound for high-Tc superconductivity. Here, structural and thermal expansion, electrical resistivity rho, angle-resolved photoemission spectroscopy (ARPES), heat capacity Cp, magnetic susceptibility chi, 75As NMR and neutron diffraction measurements of SrCo2As2 crystals are reported together with LDA band structure calculations that shed further light on this fascinating material. The c-axis thermal expansion coefficient alpha_c is negative from 7 to 300 K, whereas alpha_a is positive over this T range. The rho(T) shows metallic character. The ARPES measurements and band theory confirm the metallic character and in addition show the presence of a flat band near the Fermi energy E_F. The band calculations exhibit an extremely sharp peak in the density of states D(E_F) arising from a flat d_{x^2 - y^2} band. A comparison of the Sommerfeld coefficient of the electronic specific heat with chi(T = 0) suggests the presence of strong ferromagnetic itinerant spin correlations which on the basis of the Stoner criterion predicts that SrCo2As2 should be an itinerant ferromagnet, in conflict with the magnetization data. The chi(T) does have a large magnitude, but also exhibits a broad maximum at 115 K suggestive of dynamic short-range AFM spin correlations, in agreement with the neutron scattering data. The measurements show no evidence for any type of phase transition between 1.3 and 300 K and we propose that metallic SrCo2As2 has a gapless quantum spin-liquid ground state.

cond-mat.supr-con↗

arXiv2012

Infrared phonon anomaly and magnetic excitations in single-crystal Cu$_{3}$Bi(SeO$_{3}$)$_{2}$O$_{2}$Cl

Infrared reflection and transmission as a function of temperature have been measured on single crystals of Cu$_{3}$Bi(SeO$_{3}$)$_{2}$O$_{2}$Cl. The complex dielectric function and optical properties along all three principal axes of the orthorhombic cell were obtained via Kramers-Kronig analysis and by fits to a Drude-Lorentz model. Below 115 K, 16 additional modes (8(E$\parallel\hat{a}$)+6(E$\parallel\hat{b}$)+2(E$\parallel\hat{c}$)) appear in the phonon spectra; however, powder x-ray diffraction measurements do not detect a new structure at 85 K. Potential explanations for the new phonon modes are discussed. Transmission in the far infrared as a function of temperature has revealed magnetic excitations originating below the magnetic ordering temperature ($T_{c}\sim$24 K). The origin of the excitations in the magnetically ordered state will be discussed in terms of their response to different polarizations of incident light, behavior in externally-applied magnetic fields, and the anisotropic magnetic properties of Cu$_{3}$Bi(SeO$_{3}$)$_{2}$O$_{2}$Cl as determined by d.c. susceptibility measurements.

cond-mat.mtrl-sci↗

arXiv2012

Engineering polarization rotation in a ferroelectric superlattice

A key property that drives research in ferroelectric perovskite oxides is their strong piezoelectric response in which an electric field is induced by an applied strain, and vice-versa for the converse piezoelectric effect. We have achieved an experimental enhancement of the piezoelectric response and dielectric tunability in artificially layered epitaxial PbTiO$_{3}$/CaTiO$_{3}$ superlattices through an engineered rotation of the polarization direction. As the relative layer thicknesses within the superlattice were changed from sample to sample we found evidence for polarization rotation in multiple x-ray diffraction measurements. Associated changes in functional properties were seen in electrical measurements and piezoforce microscopy. The results demonstrate a new approach to inducing polarization rotation under ambient conditions in an artificially layered thin film.

cond-mat.mtrl-sci↗

arXiv2012

Anomalous Nuclear Quantum Effects in Ice

One striking anomaly of water ice has been largely neglected and never explained. Replacing hydrogen ($^1$H) by deuterium ($^2$H) causes ice to expand, whereas the "normal" isotope effect is volume contraction with increased mass. Furthermore, the anomaly increases with temperature $T$, even though a normal isotope shift should decrease with $T$ and vanish when $T$ is high enough to use classical nuclear motions. In this study, we show that these effects are very well described by {\it ab initio} density functional theory. Our theoretical modeling explains these anomalies, and allows us to predict and to experimentally confirm a counter effect, namely that replacement of $^{16}$O by $^{18}$O causes a normal lattice contraction.

cond-mat.mtrl-sci↗

arXiv2011

NaIrO3 - A pentavalent post-perovskite

Sodium iridium(V) oxide, NaIrO3, was synthesized by a high pressure solid state method and recovered to ambient conditions. It is found to be isostructural with CaIrO3, the much-studied structural analogue of the high-pressure post-perovskite phase of MgSiO3. Among the oxide post-perovskites, NaIrO3 is the first example with a pentavalent cation. The structure consists of layers of corner- and edge-sharing IrO6 octahedra separated by layers of NaO8 bicapped trigonal prisms. NaIrO3 shows no magnetic ordering and resistivity measurements show non-metallic behavior. The crystal structure, electrical and magnetic properties are discussed and compared to known post-perovskites and pentavalent perovskite metal oxides.

cond-mat.mtrl-sci↗

arXiv2010

Magnetic phase transition in V2O3 nanocrystals

V2O3 nanocrystals can be synthesized through hydrothermal reduction of VO(OH)2 using hydrazine as a reducing agent. Addition of different ligands to the reaction produces nanoparticles, nanorods and nanoplatelets of different sizes. Small nanoparticles synthesized in this manner show suppression of the magnetic phase transition to lower temperatures. Using muon spin relaxation spectroscopy and synchrotron x-ray diffraction, it is determined that the volume fraction of the high-temperature phase, characterized by a rhombohedral structure and paramagnetism, gradually declines with decreasing temperature, in contrast to the sharp transition observed in bulk V2O3.

cond-mat.str-el↗

arXiv2009

Lattice collapse and the magnetic phase diagram of Sr$_{1-x}$Ca$_x$Co$_2$P$_2$

We report that the 122 type Sr$_{1-x}$Ca$_x$Co$_2$P$_2$ solid solution undergoes an anomalous structural transition from the uncollapsed to the collapsed ThCr$_2$Si$_2$ structure at a distinct onset composition near $x=0.5$. Correlated with the structural changes, the electronic system evolves from a nearly ferromagnetic Fermi liquid to an antiferromagnetic metal, through a complex crossover regime. The structural collapse, driven by P-P bonding across the (Sr,Ca) layers, is much more pronounced in this system than it is in the analogous Fe-based system, indicating a strong sensitivity of structure to total electron count in the transition metal pnictide 122 family.

cond-mat.str-el↗

arXiv2009

The Structural Phase Transition in FeSe (Fe1+dSe)

In this letter we show that superconducting Fe1.01Se undergoes a structural transition at 90 K from a tetragonal to an orthorhombic phase but that non-superconducting Fe1.03Se does not. Further, high resolution electron microscopy study at low temperatures reveals an unexpected additional modulation of the crystal structure of the superconducting phase involving displacements of the Fe atoms, and that the non-superconducting material shows a distinct, complex nanometer-scale structural modulation. Finally, we show that magnetism is not the driving force for the phase transition in the superconducting phase.

cond-mat.supr-con↗

arXiv2009

Suppression of the structural phase transition and lattice softening in slightly underdoped Ba(1-x)K(x)Fe2As2 with electronic phase separation

We present x-ray powder diffraction (XRPD) and neutron diffraction measurements on the slightly underdoped iron pnictide superconductor Ba(1-x)K(x)Fe2As2, Tc = 32K. Below the magnetic transition temperature Tm = 70K, both techniques show an additional broadening of the nuclear Bragg peaks, suggesting a weak structural phase transition. However, macroscopically the system does not break its tetragonal symmetry down to 15 K. Instead, XRPD patterns at low temperature reveal an increase of the anisotropic microstrain proportionally in all directions. We associate this effect with the electronic phase separation, previously observed in the same material, and with the effect of lattice softening below the magnetic phase transition. We employ density functional theory to evaluate the distribution of atomic positions in the presence of dopant atoms both in the normal and magnetic states, and to quantify the lattice softening, showing that it can account for a major part of the observed increase of the microstrain.

cond-mat.supr-con↗

arXiv2007

Crystalline electric fields and the magnetic ground state of the novel Heusler intermetallic YbRh$_{2}$Pb

We have synthesized a new intermetallic compound with a distorted Heusler structure, YbRh$_{2}$Pb. We present a study of the magnetic, thermal, and transport properties. Heat capacity measurements revealed that YbRh$_{2}$Pb orders magnetically below T$_{N}$=0.57 K from a paramagnetic state with substantial crystal electric field splitting. Magnetic field further splits the ground state, which leads to the suppression of magnetic order in YbRh$_{2}$Pb.

cond-mat.str-el↗

arXiv2001

Mixed lattice and electronic states in high-temperature superconductors

Inelastic neutron scattering measurements are presented which show the abrupt development of new oxygen lattice vibrations near the doping-induced metal-insulator transition in La(2-x)Sr(x)CuO(4). A direct correlation is established between these lattice modes and the electronic susceptibility (as measured by photoemission) inferring that such modes mix strongly with charge fluctuations. This electron-lattice coupling can be characterized as a localized one-dimensional response of the lattice to short-ranged metallic charge fluctuations.

cond-mat.supr-con↗