49 research outputs found
Does the bonding rule break down in AsSe glass?
The local coordination numbers of AsSe glass were determined by a
combination of anomalous x-ray scattering experiments, reverse Monte Carlo
calculations, and {\it ab initio} molecular dynamics simulations. The
well-known `8- bonding rule' proposed by Mott breaks down around the As
atoms, exceeding the rule by 7--26%. An experimental prediction based on
mean-field theory agrees with the present experimental and theoretical results.
The fourfold coordinated As atoms likely form As-As wrong bond chains rather
than ethan-like configurations, which is identified as the origin for the
breakdown of the `8- bonding rule'.Comment: 6 pages, 6figures, 1table, submitted to Europhysics Letter
Total scattering descriptions of local and cooperative distortions in the oxide spinel (Mg,Cu)Cr2O4 with dilute Jahn-Teller ions
The normal spinel oxide MgCr2O4 is cubic at room temperature while the normal
spinel CuCr2O4 is tetragonal as a consequence of the Jahn-Teller nature of Cu2+
on the tetrahedral sites. Despite different end-member structures, complete
solid solutions of Mg_{1-x}Cu_xCr2O4 can be prepared that display a first-order
structural transition with composition x = 0.43 at room temperature. Reverse
Monte Carlo analysis of total neutron scattering on data acquired between 300 K
and 15 K on samples with x = 0.10, 0.20, and 0.43 provides unbiased local and
average structure descriptions of the samples, including an understanding of
the transition from local Jahn-Teller distortions in the cubic phase to
cooperative distortions that result in a tetragonal structure. Distributions of
continuous symmetry measures help to understand and distinguish distorted and
undistorted coordination around the tetrahedral site in the solid solutions.
Magnetic exchange bias is observed in field-cooled hysteresis loops of samples
with dilute Cu2+ concentration and in samples with tetragonal--cubic phase
coexistence around 300 K.Comment: 10 pages, 14 figure
Exchange biasing of single-domain Ni nanoparticles spontaneously grown in an antiferromagnetic MnO matrix
Exchange biased composites of ferromagnetic single-domain Ni nanoparticles
embedded within large grains of MnO have been prepared by reduction of
NiMnO phases in flowing hydrogen. The Ni precipitates are 15-30
nm in extent, and the majority are completely encased within the MnO matrix.
The manner in which the Ni nanoparticles are spontaneously formed imparts a
high ferromagnetic- antiferromagnetic interface/volume ratio, which results in
substantial exchange bias effects. Exchange bias fields of up to 100 Oe are
observed, in cases where the starting Ni content in the precursor
NiMnO phase is small. For particles of approximately the same
size, the exchange bias leads to significant hardening of the magnetization,
with the coercive field scaling nearly linearly with the exchange bias field.Comment: 6 pages PDFLaTeX with 9 figure
Phase relations in K_xFe_{2-y}Se_2 and the structure of superconducting K_xFe_2Se_2 via high-resolution synchrotron diffraction
Superconductivity in iron selenides has experienced a rapid growth, but not
without major inconsistencies in the reported properties. For
alkali-intercalated iron selenides, even the structure of the superconducting
phase is a subject of debate, in part because the onset of superconductivity is
affected much more delicately by stoichiometry and preparation than in cuprate
or pnictide superconductors. If high-quality, pure, superconducting
intercalated iron selenides are ever to be made, the intertwined physics and
chemistry must be explained by systematic studies of how these materials form
and by and identifying the many coexisting phases. To that end, we prepared
pure K_2Fe_4Se_5 powder and superconductors in the K_xFe_{2-y}Se_2 system, and
examined differences in their structures by high-resolution synchrotron and
single-crystal x-ray diffraction. We found four distinct phases: semiconducting
K_2Fe_4Se_5, a metallic superconducting phase K_xFe_2Se_2 with x ranging from
0.38 to 0.58, an insulator KFe_{1.6}Se_2 with no vacancy ordering, and an
oxidized phase K_{0.51(5)}Fe_{0.70(2)}Se that forms the PbClF structure upon
exposure to moisture. We find that the vacancy-ordered phase K_2Fe_4Se_5 does
not become superconducting by doping, but the distinct iron-rich minority phase
K_xFe_2Se_2 precipitates from single crystals upon cooling from above the
vacancy ordering temperature. This coexistence of metallic and semiconducting
phases explains a broad maximum in resistivity around 100 K. Further studies to
understand the solubility of excess Fe in the K_xFe_{2-y}Se_2 structure will
shed light on the maximum fraction of superconducting K_xFe_2Se_2 that can be
obtained by solid state synthesis.Comment: 12 pages, 16 figures, supplemental materia
Magnetodielectric coupling in Mn3O4
We have investigated the dielectric anomalies associated with spin ordering
transitions in the tetragonal spinel MnO, using thermodynamic,
magnetic, and dielectric measurements. We find that two of the three magnetic
ordering transitions in MnO lead to decreases in the temperature
dependent dielectric constant at zero applied field. Applying a magnetic field
to the polycrystalline sample leaves these two dielectric anomalies practically
unchanged, but leads to an increase in the dielectric constant at the
intermediate spin-ordering transition. We discuss possible origins for this
magnetodielectric behavior in terms of spin-phonon coupling. Band structure
calculations suggest that in its ferrimagnetic state, MnO corresponds
to a semiconductor with no orbital degeneracy due to strong Jahn-Teller
distortion.Comment: 6 pages, 7 figure
Dilute ferrimagnetic semiconductors in Fe-substituted spinel ZnGaO
Solid solutions of nominal composition
[ZnGaO][FeO], of the semiconducting spinel
ZnGaO with the ferrimagnetic spinel FeO have been prepared with
= 0.05, 0.10, and 0.15. All samples show evidence for long-range magnetic
ordering with ferromagnetic hysteresis at low temperatures. Magnetization as a
function of field for the = 0.15 sample is S-shaped at temperatures as high
as 200 K. M\"ossbauer spectroscopy on the = 0.15 sample confirms the
presence of Fe, and spontaneous magnetization at 4.2 K. The magnetic
behavior is obtained without greatly affecting the semiconducting properties of
the host; diffuse reflectance optical spectroscopy indicates that Fe
substitution up to = 0.15 does not affect the position of the band edge
absorption. These promising results motivate the possibility of dilute
ferrimagnetic semiconductors which do not require carrier mediation of the
magnetic moment.Comment: 9 pages and 6 figure
Electronic structure, magnetism, and disorder in the Heusler compound CoTiSn
Polycrystalline samples of the half-metallic ferromagnet Heusler compound
CoTiSn have been prepared and studied using bulk techniques (X-ray
diffraction and magnetization) as well as local probes (Sn M\"ossbauer
spectroscopy and Co nuclear magnetic resonance spectroscopy) in order to
determine how disorder affects half-metallic behavior and also, to establish
the joint use of M\"ossbauer and NMR spectroscopies as a quantitative probe of
local ion ordering in these compounds. Additionally, density functional
electronic structure calculations on ordered and partially disordered
CoTiSn compounds have been carried out at a number of different levels of
theory in order to simultaneously understand how the particular choice of DFT
scheme as well as disorder affect the computed magnetization. Our studies
suggest that a sample which seems well-ordered by X-ray diffraction and
magnetization measurements can possess up to 10% of antisite (Co/Ti)
disordering. Computations similarly suggest that even 12.5% antisite Co/Ti
disorder does not destroy the half-metallic character of this material.
However, the use of an appropriate level of non-local DFT is crucial.Comment: 11 pages and 5 figure