Polar and magnetic order in GaV4Se8

In the present work, we provide results from specific heat, magnetic susceptibility, dielectric constant, ac conductivity, and electrical polarization measurements performed on the lacunar spinel GaV4Se8. With decreasing temperature, we observe a transition from the paraelectric and paramagnetic cubic state into a polar, probably ferroelectric state at 42 K followed by magnetic ordering at 18 K. The polar transition is likely driven by the Jahn-Teller effect due to the degeneracy of the V4 cluster orbitals. The excess polarization arising in the magnetic phase indicates considerable magnetoelectric coupling. Overall, the behavior of GaV4Se8 in many respects is similar to that of the skyrmion host GaV4S8, exhibiting a complex interplay of orbital, spin, lattice, and polar degrees of freedom. However, its dielectric behavior at the polar transition markedly differs from that of the Jahn-Teller driven ferroelectric GeV4S8, which can be ascribed to the dissimilar electronic structure of the Ge compound.Comment: 7 pages, 6 figures. Revised version according to suggestions of referee

Structural, magnetic, electric, dielectric, and thermodynamic properties of multiferroic GeV4S8

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.Comment: 15 pages, 9 figure

Polar Dynamics at the Jahn-Teller Transition in Ferroelectric GaV4S8

We present a dielectric spectroscopy study of the polar dynamics linked to the orbitally driven ferroelectric transition in the skyrmion host GaV4S8. By combining THz and MHz-GHz spectroscopy techniques, we succeed in detecting the relaxational dynamics arising from coupled orbital and polar fluctuations in this material and traced its temperature dependence in the paraelectric as well as in the ferroelectric phase. The relaxation time significantly increases when approaching the critical temperature from both sides of the transition. It is natural to assume that these polar fluctuations map the orbital dynamics at the Jahn-Teller transition. Due to the first-order character of the orbital-ordering transition, the relaxation time shows an enormous jump of about five orders of magnitude at the polar and structural phase transition.Comment: 5 pages, 4 figure

Interplay of Spin and Lattice Degrees of Freedom in the Frustrated Antiferromagnet CdCr_2O_4: High-field and Temperature Induced Anomalies of the Elastic Constants

Temperature and magnetic field studies of the elastic constants of the chromium spinel CdCr_2O_4 show pronounced anomalies related to strong spin-phonon coupling in this frustrated antiferromagnet. A detailed comparison of the longitudinal acoustic mode propagating along the [111] direction with theory based on an exchange-striction mechanism leads to an estimate of the strength of the magneto-elastic interaction. The derived spin-phonon coupling constant is in good agreement with previous determinations based on infrared absorption. Further insight is gained from intermediate and high magnetic field experiments in the field regime of the magnetization plateau. The role of the antisymmetric Dzyaloshinskii-Moriya interaction discussed and we compare the spin-phonon coupling in CdCr_2O_4 in both the ordered and disordered states.Comment: 12 pages, 8 figures; Appendix added,To appear in Phys Rev.

Relaxation dynamics and colossal magnetocapacitive effect in CdCr2S4

A thorough investigation of the relaxational dynamics in the recently discovered multiferroic CdCr2S4 showing a colossal magnetocapacitive effect has been performed. Broadband dielectric measurements without and with external magnetic fields up to 10 T provide clear evidence that the observed magnetocapacitive effect stems from enormous changes of the relaxation dynamics induced by the development of magnetic order.Comment: 4 pages, 4 figure

Nanoscale layering of antiferromagnetic and superconducting phases in Rb2Fe4Se5

We studied phase separation in a single-crystalline antiferromagnetic superconductor Rb2Fe4Se5 (RFS) using a combination of scattering-type scanning near-field optical microscopy (s-SNOM) and low-energy muon spin rotation (LE-\mu SR). We demonstrate that the antiferromagnetic and superconducting phases segregate into nanometer-thick layers perpendicular to the iron-selenide planes, while the characteristic in-plane size of the metallic domains reaches 10 \mu m. By means of LE-\mu SR we further show that in a 40-nm thick surface layer the ordered antiferromagnetic moment is drastically reduced, while the volume fraction of the paramagnetic phase is significantly enhanced over its bulk value. Self-organization into a quasiregular heterostructure indicates an intimate connection between the modulated superconducting and antiferromagnetic phases.Comment: 5 pages, 2 figures. Updated version published in Phys. Rev. Lett. on 5 July 201

Characteristics of ferroelectric-ferroelastic domains in N{\'e}el-type skyrmion host GaV4_4S8_8

GaV$_4$S$_8$ is a multiferroic semiconductor hosting N{\'e}el-type magnetic skyrmions dressed with electric polarization. At T$_s$ = 42K, the compound undergoes a structural phase transition of weakly first-order, from a non-centrosymmetric cubic phase at high temperatures to a polar rhombohedral structure at low temperatures. Below T$_s$, ferroelectric domains are formed with the electric polarization pointing along any of the four $\left< 111 \right>$ axes. Although in this material the size and the shape of the ferroelectric-ferroelastic domains may act as important limiting factors in the formation of the N{\'e}el-type skyrmion lattice emerging below T$_C$=13\:K, the characteristics of polar domains in GaV$_4$S$_8$ have not been studied yet. Here, we report on the inspection of the local-scale ferroelectric domain distribution in rhombohedral GaV$_4$S$_8$ using low-temperature piezoresponse force microscopy. We observed mechanically and electrically compatible lamellar domain patterns, where the lamellae are aligned parallel to the (100)-type planes with a typical spacing between 100 nm-1.2 $\mu$m. We expect that the control of ferroelectric domain size in polar skyrmion hosts can be exploited for the spatial confinement and manupulation of N{\'e}el-type skyrmions

Evidence for local lattice distortions in giant magnetocapacitive CdCr2S4

Raman scattering experiments on CdCr2S4 single crystals show pronounced anomalies in intensity and frequency of optical phonon modes with an onset temperature T*=130 K that coincides with the regime of giant magnetocapacitive effects. A loss of inversion symmetry and Cr off-centering are deduced from the observation of longitudinal optical and formerly infrared active modes for T<T_c=84 K. The intensity anomalies are attributed to the enhanced electronic polarizability of displacements that modulate the Cr-S distance and respective hybridization. Photo doping leads to an annihilation of the symmetry reduction. Our scenario of multiferroic effects is based on the near degeneracy of polar and nonpolar modes and the additional low energy scale due to hybridization.Comment: 4 pages, 6 figure

Multiferroicity and skyrmions carrying electric polarization in GaV4S8

Skyrmions are whirl like topological spin objects with high potential for future magnetic data storage. It is a fundamental question, relevant for both basic research and application, if a ferroelectric (FE) polarization can be associated with their magnetic texture and if these objects can be manipulated by electric fields. Here, we study the interplay between magnetism and electric polarization in the lacunar spinel GaV4S8, which undergoes a structural transition associated with orbital ordering at 44 K and reveals a complex magnetic phase diagram below 13 K, including a ferromagnetic (FM), cycloidal, and N\'eel-type skyrmion lattice (SkL) phase. We found that the orbitally ordered phase of GaV4S8 is FE with a sizable polarization of ~1 {\mu}C/cm2. Moreover, we observed spin-driven excess polarizations in all magnetic phases and, hence, GaV4S8 hosts three different multiferroic phases with coexisting polar and magnetic order. These include the SkL phase where we predict a strong spatial modulation of the FE polarization close to the skyrmion cores. By taking into account the crystal symmetry and spin patterns of the magnetically ordered phases, we identify the exchange striction as the main microscopic mechanism behind the spin-driven FE polarization in each multiferroic phase. Since GaV4S8 is unique among the known SkL host materials due to its polar crystal structure and the observed strong magnetoelectric effect, this study is an important step towards the non-dissipative electric-field control of skyrmions.Comment: 17 pages, 7 figures + 2 pages, 4 figures in Supplementary Materials. Revised version as accepted for publication in Science Advance