No Arabic abstract
The lacunar spinel GeV4S8 undergoes orbital and ferroelectric ordering at the Jahn-Teller transition around 30 K and exhibits antiferromagnetic order below about 14 K. In addition to this orbitally driven ferroelectricity, lacunar spinels are an interesting material class, as the vanadium ions form V4 clusters representing stable molecular entities with a common electron distribution and a well-defined level scheme of molecular states resulting in a unique spin state per V4 molecule. Here we report detailed x-ray, magnetic susceptibility, electrical resistivity, heat capacity, thermal expansion, and dielectric results to characterize the structural, electric, dielectric, magnetic, and thermodynamic properties of this interesting material, which also exhibits strong electronic correlations. From the magnetic susceptibility, we determine a negative Curie-Weiss temperature, indicative for antiferromagnetic exchange and a paramagnetic moment close to a spin S = 1 of the V4 molecular clusters. The low-temperature heat capacity provides experimental evidence for gapped magnon excitations. From the entropy release, we conclude about strong correlations between magnetic order and lattice distortions. In addition, the observed anomalies at the phase transitions also indicate strong coupling between structural and electronic degrees of freedom. Utilizing dielectric spectroscopy, we find the onset of significant dispersion effects at the polar Jahn-Teller transition. The dispersion becomes fully suppressed again with the onset of spin order. In addition, the temperature dependencies of dielectric constant and specific heat possibly indicate a sequential appearance of orbital and polar order.
The magnetic and dielectric properties under high magnetic fields are studied in the single crystal of Cu3Mo2O9. This multiferroic compound has distorted tetrahedral spin chains. The effects of the quasi-one dimensionality and the geometrical spin frustration are expected to appear simultaneously. We measure the magnetoelectric current and the differential magnetization under the pulsed magnetic field up to 74 T. We also measure the electric polarization versus the electric field curve/loop under the static field up to 23 T. Dielectric properties change at the magnetic fields where the magnetization jumps are observed in the magnetization curve. Moreover, the magnetization plateaus are found at high magnetic fields.
The mixed-valent multiferroic compound CaMn7O12 is studied for its magnetic and electric properties. The compound undergoes magnetic ordering below 90 K with a helimagnetic structure followed by a low temperature magnetic anomaly observed around 43 K. The present study shows that the magnetic anomaly at 43 K is associated with thermal hysteresis indicating first order nature of the transition. The compound also shows field-cooled magnetic memory and relaxation below 43 K, although no zero-field-cooled memory is present. Clear magnetic hysteresis loop is present in the magnetization versus field measurements signifying the presence of some ferromagnetic clusters in the system. We doped trivalent La at the cite of divalent Ca expecting to enhance the fraction of Mn$^{3+}$ ions. The La doped samples show reduced magnetization, although the temperatures associated with the magnetic anomalies remain almost unaltered. Interestingly, the spontaneous electrical polarization below 90 K increases drastically on La substitution. We propose that the ground state of the pure as well as the La doped compositions contain isolated superparamagnetic like clusters, which can give rise to metastability in the form of field-cooled memory and relaxation. The ground state is not certainly spin glass type as it is evident from the absence of zero-field-cooled memory and frequency shift in the ac suceptibility measurements.
We report on a systematic optical investigation of wustite. In addition, the sample under consideration, Fe0.93O, has been characterized in detail by electrical transport, dielectric, magnetic and thermodynamic measurements. From infrared reflectivity experiments, phonon properties, Drude-like conductivity contributions and electronic transitions have been systematically investigated. The phonon modes reveal a clear splitting below the antiferromagnetic ordering temperature, similar to observations in other transition-metal monoxides and in spinel compounds which have been explained in terms of a spin-driven Jahn-Teller effect. The electronic transitions can best be described assuming a crystal-field parameter Dq = 750 cm-1 and a spin-orbit coupling constant lambda = 95 cm-1. A well defined crystal field excitation at low temperatures reveals significant broadening on increasing temperature with an overall transfer of optical weight into dc conductivity contributions. This fact seems to indicate a melting of the on-site excitation into a Drude behavior of delocalized charge carriers. The optical band gap in wustite is close to 1.0 eV at room temperature. With decreasing temperatures and passing the magnetic phase transition we have detected a strong blue shift of the correlation-induced band edge, which amounts more than 15% and has been rarely observed in antiferromagnets.
LiCu2O2 is the first multiferroic cuprate to be reported and its ferroelectricity is induced by complex magnetic ordering in ground state, which is still in controversy today. Herein, we have grown nearly untwinned LiCu2O2 single crystals of high quality and systematically investigated their dielectric and ferroelectric behaviours in external magnetic fields. The highly anisotropic response observed in different magnetic fields apparently contradicts the prevalent bc- or ab- plane cycloidal spin model. Our observations give strong evidence supporting a new helimagnetic picture in which the normal of the spin helix plane is along the diagonal of CuO4 squares which form the quasi-1D spin chains by edge-sharing. Further analysis suggests that the spin helix in the ground state is elliptical and in the intermediate state the present c-axis collinear SDW model is applicable with some appropriate modifications. In addition, our studies show that the dielectric and ferroelectric measurements could be used as probes for the characterization of the complex spin structures in multiferroic materials due to the close tie between their magnetic and electric orderings.
We present an extensive study of the structural, magnetic and thermodynamic properties of high-quality monocrystals of the two heterometallic oxyborates from the ludwigite family: Cu$_2$GaBO$_5$ and Cu$_2$AlBO$_5$ in the temperature range above 2 K. The distinctive feature of the investigated structures is the selective distribution of Cu and Ga/Al cations. The unit cell of Cu$_2$GaBO$_5$ and Cu$_2$AlBO$_5$ contains four nonequivalent crystallographic sites of metal ions. Two sites in the structure from four nonequivalent crystallographic sites of metal ions of Cu$_2$GaBO$_5$ are fully occupied by Cu atoms which form the quasi one-dimensional chains along the a-axis. For Cu$_2$AlBO$_5$ all sites are partially occupied by Al and Cu atoms. The joint analysis of low-temperature data on magnetic susceptibility and magnetic contribution to the specific heat showed that Cu$_2$AlBO$_5$ and Cu$_2$GaBO$_5$ exhibit an antiferromagnetic transition at $T_{rm N} approx 3$ and 4 K, respectively. The magnetic contributions to the specific heat for both compounds were obtained after subtracting the phonon contribution. It is shown that the external magnetic field above 2.5 T leads to a broadening of the magnetic phase transition indicating suppression of the long-range antiferromagnetic order.