Improper Ferroelectric Polarisation in a Perovskite driven by Inter-site Charge Transfer and Ordering

It is of great interest to design and make materials in which ferroelectric polarisation is coupled to other order parameters such as lattice, magnetic and electronic instabilities. Such materials will be invaluable in next-generation data storage devices. Recently, remarkable progress has been made in understanding improper ferroelectric coupling mechanisms that arise from lattice and magnetic instabilities. However, although theoretically predicted, a compact lattice coupling between electronic and ferroelectric (polar) instabilities has yet to be realised. Here we report detailed crystallographic studies of a novel perovskite Hg$^{\textbf{A}}$Mn$^{\textbf{A'}}_{3}$Mn$^{\textbf{B}}_{4}$O$_{12}$ that is found to exhibit a polar ground state on account of such couplings that arise from charge and orbital ordering on both the A' and B-sites, which are themselves driven by a highly unusual Mn$^{A'}$-Mn$^B$ inter-site charge transfer. The inherent coupling of polar, charge, orbital and hence magnetic degrees of freedom, make this a system of great fundamental interest, and demonstrating ferroelectric switching in this and a host of recently reported hybrid improper ferroelectrics remains a substantial challenge.Comment: 9 pages, 7 figure

Interplay between the magnetic and electric degrees-of-freedom in multiferroic Co3TeO6

Neutron diffraction, magnetic susceptibility, specific heat, and dielectric constant measurements of single crystal Co3TeO6 have been measured to study the interplay between the ferroelectricity and magnetic order. Long range incommensurate magnetic order develops below TM1=26 K, which is followed by three additional zero-field phase transitions at TM2=19.5 K, TM3=18 K, and TM4=16 K where the incommensurate order changes and commensurate order develops. In magnetic fields up to 14 T we find that the magnetic intensities and incommensurate wave vector are dramatically altered as ferroelectricity develops, with a fifth abrupt transition around 10 T. The overall behavior characterizes Co3TeO6 as a type-II multiferroic.Comment: Phys. Rev. B (in press

Magnetocapacitance effect and magnetoelectric coupling in type-II multiferroic HoFeWO6

We have investigated the multiferroicity and magnetoelectric (ME) coupling in HoFeWO6. With a noncentrosymmetric polar structure (space group Pna21) at room temperature, this compound shows an onset of electric polarization with an antiferromagnetic ordering at the Néel temperature (TN ) of 17.8 K. The magnetic properties of the polycrystalline samples were studied by DC and AC magnetization and heat capacity measurements. The metamagnetic behavior at low temperatures was found to be directly related to the dielectric properties of the compound. In particular, field-dependent measurements of capacitance show a magnetocapacitance (MC) effect with double-hysteresis loop behavior in direct correspondence with the magnetization. Our x-ray diffraction results show the Pna21 structure down to 8 K and suggest the absence of a structural phase transition across TN . Soft x-ray absorption spectroscopy and soft x-ray magnetic circular dichroism (XMCD) measurements at the Fe L2,3 and Ho M4,5 edges revealed the oxidation state of Fe and Ho cations to be 3+. Fe L2,3 XMCD further shows that Fe3+ cations are antiferromagnetically ordered in a noncollinear fashion with spins arranged 90◦ with respect to each other. Our findings show that HoFeWO6 is a type-II multiferroic exhibiting a MC effect. The observed MC effect and the change in polarization by the magnetic field, as well as their direct correspondence with magnetization, further support the strong ME coupling in this compound.The work at University of Houston (UH) is supported by U. S. Air Force Office of Scientific Research Grants FA9550-15-1-0236 and FA9550-20-1-0068, the T. L. L. Temple Foundation, the John J. and Rebecca Moores Endowment, and the State of Texas through the Texas Center for Superconductivity at the University of Houston. The XRD patterns were collected at the National Synchrotron Radiation Research Center at Taiwan. The synchrotron XAS/XMCD experiments were performed at the BOREAS beamline of the ALBA Synchrotron Light Facility in collaboration with ALBA staff. Computational resources were provided by the Extreme Science and Engineering Discovery Environment (XSEDE) [55] supported by the National Science Foundation (ACI-1548562) and the National Energy Research Scientific Computing (NERSC) Center, a DOE Office of Science User Facility supported by the Office of Science, U. S. Department of Energy, under Contract No. DE-AC02-05CH11231. Additional support for this work was provided through resources of the uHPC cluster managed by UH and acquired through NSF Award 1531814. The authors acknowledge the use of the Maxwell/Opuntia/Sabine Cluster and the advanced support from the Research Computing Data Core at UH. The work at National Sun Yat-Sen University was partially supported by the Ministry of Science and Technology of Taiwan under Grant No. MOST 109-2112-M-110-019.Peer reviewe

Superconductivity, magnetism, and charge density wave formation in ternary compounds with the Sc5Co4Si10-type structure

The variation of the superconducting transition temperature T(,c) with hydrostatic pressure up to 23.7 kbar is reported for eleven compounds with the Sc(,5)Co(,4)Si(,10)-type structure. Most of these compounds display a modest linear depression of T(,c) with pressure (dT(,c)/dp (TURN) 10('-5) K/bar), however, two materials, Lu(,5)Ir(,4)Si(,10) and Lu(,5)Rh(,4)Si(,10), undergo a discontinuous transformation above a critical pressure of about 20 kbar to a state with a significantly higher T(,c);The resistivity and magnetic susceptibility show an anomaly in Lu(,5)Ir(,4)Si(,10) and Lu(,5)Rh(,4)Si(,10) at T(,o) = 83 K and 155 K respectively. It is interpreted that this phase transformation may involve a charge density wave (CDW) formation that opens an energy gap over a portion of the Fermi surface. The P-T phase diagram for Lu(,5)Ir(,4)Si(,10), given to demonstrate the correlation between T(,o) and T(,c), provides the clear evidence that the pressure enhancement of T(,c) is due to a progressive removal of the charge density wave in the crystal;Combining the magnetic susceptibility and heat capacity data, we give a quantitative estimate of a 36% loss in the electronic density of states at the Fermi level due to this energy gap in Lu(,5)Ir(,4)Si(,10);The pseudoternary system (Lu(,1-x)Sc(,x))(,5)Ir(,4)Si(,10), 0 (LESSTHEQ) x (LESSTHEQ) 0.05, is used to study the doping (impurity) effect on the CDW and the competition between T(,o) and T(,c) in Lu(,5)Ir(,4)Si(,10). It is found that (dT(,o)/dx)(,x=0) = -18.5 K/at % and (dT(,c)/dx)(,x=0) = 0.5 K/at %, are comparable to another CDW system (Ta(,1-x)Nb(,x))S(,3);The electrical and magnetic properties for R(,5)Ir(,4)Si(,10) (R = Dy-Yb) are also reported. All of these compounds exhibit an anomaly in resistivity, which is considered to be due to the formation of a CDW, similar to the one observed in Lu(,5)Ir(,4)Si(,10). Two distinct magnetic transitions with different features, seen in the ac magnetic susceptibility and heat capacity at low temperature for Tm(,5)Ir(,4)Si(,10) indicate two different types of magnetic structure. Strong crystal field effects or valence fluctuations are suggested to occur in Yb(,5)Ir(,4)Si(,10);because of the noticeable deviation of the magnetic susceptibility from Curie-Weiss law below 70 K; *DOE Report IS-T-1281. This work was performed under contract No. W-7045-Eng-82 with the U.S. Department of Energy.</p

Complex magnetic incommensurability and electronic charge transfer through the ferroelectric transition in multiferroic Co3TeO6

Polarized and unpolarized neutron diffractions have been carried out to investigate the nature of the magnetic structures and transitions in monoclinic Co3TeO6. As the temperature is lowered below 26 K long range order develops, which is fully incommensurate (ICM) in all three crystallographic directions. Below 19.5 K additional commensurate magnetic peaks develop, consistent with the T-4 irreducible representation, along with a splitting of the ICM peaks along the h direction which indicates that there are two separate sets of magnetic modulation vectors. Below 18 K, this small additional magnetic incommensurability disappears, ferroelectricity develops, an additional commensurate magnetic structure consistent with T-3 irreducible representation appears, and the k component of the ICM wave vector disappears. Synchrotron x-ray diffraction measurements demonstrate that there is a significant shift of the electronic charge distribution from the Te ions at the crystallographic 8f sites to the neighboring Co and O ions. These results, together with the unusually small electric polarization, its strong magnetic field dependence, and the negative thermal expansion in all three lattice parameters, suggest this material is an antiferroelectric. Below15 K the k component of the ICM structure reappears, along with second-order ICM Bragg peaks, which polarized neutron data demonstrate are magnetic in origin

Charge transfer enhanced magnetic correlations in type-II multiferroic Co3TeO6

Magnetic structure of the Co ions in monoclinic Co3TeO6 in the antiferroelectric state at 16 K has been determined by neutron powder together with single-crystal diffractions. The indices of the magnetic reflections that appear at the incommensurate positions were determined by diffractions from a single crystal, which allow to uniquely identify the magnetic modulation vector. There are two crystallographically distinct Co layers. Magnetic incommensurability appears in the Co spins in the layers comprising zig-zag chains, with a magnetic modulation vector of (0.357, 0.103, 0.121) at 3 K but changes to (0.4439, 0, 0.137) at 16 K, while the Co ions in the honeycomb webs form a collinear antiferromagnetic structure. Thermal reduction rate of the Co moments in the honeycomb webs was found to be much smaller than those in the zig-zag chains. Shifting of large amounts of electronic charge into the Co-O bonds in the honeycomb webs on warming is used to understand the behavior

Room-temperature skyrmion phase in bulk Cu2OSeO3 under high pressures

A skyrmion state in a noncentrosymmetric helimagnet displays topologically protected spin textures with profound technological implications for high-density information storage, ultrafast spintronics, and effective microwave devices. Usually, its equilibrium state in a bulk helimagnet occurs only over a very restricted magnetic field-temperature phase space and often in the low-temperature region near the magnetic transition temperature T-c. We have expanded and enhanced the skyrmion phase region from the small range of 55 to 58.5 K to 5 to 300 K in single-crystalline Cu2OSeO3 by pressures up to 42.1 GPa through a series of phase transitions from the cubic P2(1)3, through orthorhombic P2(1)2(1)2(1) and monoclinic P2(1), and finally to the triclinic P1 phase, using our newly developed ultrasensitive high-pressure magnetization technique. The results are in agreement with our Ginzburg-Landau free energy analyses, showing that pressures tend to stabilize the skyrmion states and at higher temperatures. The observations also indicate that the skyrmion state can be achieved at higher temperatures in various crystal symmetries, suggesting the insensitivity of skyrmions to the underlying crystal lattices and thus the possible more ubiquitous presence of skyrmions in helimagnets

Complex magnetic couplings in Co3TeO6

We report powder and single-crystal neutron diffractionmeasurements, combinedwith x-ray powder diffraction data, to unravel the complex magnetic phase diagram and exchange coupling in Co3TeO6. The magnetic structures of the various phases differ markedly from those proposed by Ivanov et al. [Mater. Res. Bull. 47, 63 (2012)] on the basis of only powder diffraction data. The dominant exchange interactions are identified by considering the geometrical arrangement of severely distorted CoO6 octahedra and CoO4 tetrahedra, which naturally divide into two different types of layers, one of which consists of zigzag chains. These zigzag chains are the first to develop magnetic order at T-M1 = 26 K, which is incommensurate in nature. The other separate layer of Co spins develops antiferromagnetic order of Gamma 4 symmetry at zero wave vector at T-M2 = 19.5 K. Our results are consistent with the previous findings of a spontaneous polarization below T-M3 = 18 K. Our neutron powder diffraction data indicate that the increase in the single-crystal (600) Bragg peak is due to a relief of extinction rather than to magnetic effects associated with the observed anomalous variation in the incommensurate wave vector at T-M4 = 16 K. The commensurate order parameter is shown to have a small dependence on the applied electric field, whereas no such effect is found for the incommensurate ordering. Below T-M3, the thermal expansion is negative, and it also exhibits anomalies at T-M2 and T-M4. A symmetry analysis and comprehensive phase diagram are given