Strain relaxation dynamics of multiferroic orthorhombic manganites.

Resonant ultrasound spectroscopy has been used to characterise strain coupling and relaxation behavior associated with magnetic/magnetoelectric phase transitions in GdMnO3, TbMnO3and TbMn0.98Fe0.02O3through their influence on elastic/anelastic properties. Acoustic attenuation ahead of the paramagnetic to colinear-sinusoidal incommensurate antiferromagnetic transition at ∼41 K correlates with anomalies in dielectric properties and is interpreted in terms of Debye-like freezing processes. A loss peak at ∼150 K is related to a steep increase in electrical conductivity with a polaron mechanism. The activation energy,Ea, of ≳0.04 eV from a loss peak at ∼80 K is consistent with the existence of a well-defined temperature interval in which the paramagnetic structure is stabilised by local, dynamic correlations of electric and magnetic polarisation that couple with strain and have relaxation times in the vicinity of ∼10-6s. Comparison with previously published data for Sm0.6Y0.4MnO3confirms that this pattern may be typical for multiferroic orthorhombicRMnO3perovskites (R= Gd, Tb, Dy). A frequency-dependent loss peak near 10 K observed for TbMnO3and TbMn0.98Fe0.02O3, but not for GdMnO3, yieldedEa⩾ ∼0.002 eV and is interpreted as freezing of some magnetoelastic component of the cycloid structure. Small anomalies in elastic properties associated with the incommensurate and cycloidal magnetic transitions confirm results from thermal expansion data that the magnetic order parameters have weak but significant coupling with strain. Even at strain magnitudes of ∼0.1-1‰, polaron-like strain effects are clearly important in defining the development and evolution of magnetoelectric properties in these materials. Strains associated with the cubic-orthorhombic transition due to the combined Jahn-Teller/octahedral tilting transition in the vicinity of 1500 K are 2-3 orders of magnitude greater. It is inevitable that ferroelastic twin walls due to this transition would have significantly different magnetoelectric properties from homogeneous domains due to magnetoelastic coupling with steep strain gradients.

Raman and infrared study of 4f electron-phonon coupling in HoVO3.

First-order Raman scattering and multiphonons are studied in RVO3 (R = Ho and Y) as a function of temperature in the orthorhombic and monoclinic phases. Raman spectra of HoVO3 and YVO3 unveil similar features since both compounds have nearly identical R-radii. However, the most important difference lies in the transition temperature involving the V(3+) orbitals, the V(3+) magnetic moments as well as the crystallographic structure. Particularly, the magnetic and orbital reorientations occur at T N2 = 40 K for HoVO3 instead T N2 =77 K in the case of YVO3. For both systems, anomalous phonon shifts which are related to spin-phonon coupling are observed below the V(3+) magnetic ordering temperature (T N1 ≈ 110 K) while additional phonon anomalies are exclusively observed in HoVO3 around T (*) ≈ 15 K. On the other hand, infrared (IR) transmittance measurements as a function of temperature reveal Ho(3+5)I8 → (5)I7 excitations and additional excitations assigned as vibronics. These latter combined with drastic changes in Ho(3+5)I8 → (5)I7 excitations at T N2, are indicative of a strong coupling between the Ho(3+) ions and the ligand field. This could explain the large magnetocaloric capacity shown by HoVO3.

Elastic anomalies associated with structural and magnetic phase transitions in single crystal hexagonal YMnO3.

Resonant ultrasound spectroscopy has been used to measure the elastic and anelastic behaviour through known structural and magnetic phase transitions in single crystal hexagonal YMnO3. Anomalous elastic behaviour is observed at the high temperature structural transition at ∼1260 K, with a discontinuity in the elastic constants and nonlinear recovery below Tc, consistent with [Formula: see text] coupling. There is no change in dissipation associated with this high temperature transition, and no evidence in the elastic or anelastic behaviour for any secondary transition at ∼920 K, thus supporting the thesis of a single high temperature transformation. Elastic stiffening is observed on cooling through TN, in accordance with previous studies, and the excess elastic constant appears to scale with the square of the magnetic order parameter. The strains incurred at TN are a factor of ∼20 smaller than those at the structural transition, implying very weak [Formula: see text] coupling and a dominant contribution to the variation in the elastic constants from [Formula: see text]. The increased acoustic dissipation above TN is consistent with an order-disorder process.

Thermochromic effects in a Jahn-Teller active CuCl(4-)6 layered hybrid system.

The hybrid material copper (II) tetrachloro-bis(phenyl ethyl ammonium) (C6H5CH2CH2NH3)2CuCl4, or PEACuCl, has been investigated by temperature-dependent spectroscopic absorption experiments. The absorption bands observed in the near-infrared region (1.3-1.9 eV) generally exhibit redshifts with increasing temperature. The temperature-induced energy shifts of the spectral components are shown to be consistently related to temperature-induced Cu-Cl bond length changes. Additionally, the thermochromic color change is caused by a charge transfer band edge redshifting (in the visible region 2.0-2.8 eV) with increasing temperature. By comparison with similar Cu-based systems, it is suggested that this shift is caused by broadening and strengthening of the band.

Surface-enhanced charge-density-wave instability in underdoped Bi2Sr(2-x)La(x)CuO(6+δ).

Neutron and X-ray scattering experiments have provided mounting evidence for spin and charge ordering phenomena in underdoped cuprates. These range from early work on stripe correlations in Nd-LSCO to the latest discovery of charge-density-waves in YBa2Cu3O(6+x). Both phenomena are characterized by a pronounced dependence on doping, temperature and an externally applied magnetic field. Here, we show that these electron-lattice instabilities exhibit also a previously unrecognized bulk-surface dichotomy. Surface-sensitive electronic and structural probes uncover a temperature-dependent evolution of the CuO2 plane band dispersion and apparent Fermi pockets in underdoped Bi2 Sr(2-x) La(x) CuO(6+δ) (Bi2201), which is directly associated with an hitherto-undetected strong temperature dependence of the incommensurate superstructure periodicity below 130 K. In stark contrast, the structural modulation revealed by bulk-sensitive probes is temperature-independent. These findings point to a surface-enhanced incipient charge-density-wave instability, driven by Fermi surface nesting. This discovery is of critical importance in the interpretation of single-particle spectroscopy data, and establishes the surface of cuprates and other complex oxides as a rich playground for the study of electronically soft phases.

Dynamics of photo-excited electrons in magnetically ordered TbMnO3.

Time resolved optical spectroscopy is used to elucidate the dynamics of photodoped spin-aligned carriers in the presence of an underlying magnetic lattice in the multiferroic compound TbMnO(3). The transient responses while probing d-d intersite transitions show marked differences along different crystallographic directions, which are discussed in terms of the interplay between the processes of hopping of the photo-injected electrons and the magnetic order in the material.

Magnetodielectric coupling in frustrated spin systems: the spinels MCr2O4 (M = Mn, Co and Ni).

We have studied the magnetodieletric coupling of polycrystalline samples of the spinels MCr(2)O(4) (M = Mn, Co and Ni). Dielectric anomalies are clearly observed at the onset of the magnetic spiral structure (T(s)) and at the 'lock-in' transition (T(f)) in MnCr(2)O(4) and CoCr(2)O(4), and also at the onset of the canted structure (T(s)) in NiCr(2)O(4). The strength of the magnetodielectric coupling in this system can be explained by spin-orbit coupling. Moreover, the dielectric response in an applied magnetic field scales with the square of the magnetization for all three samples. Thus, the magnetodielectric coupling in this state appears to originate from the P(2)M(2) term in the free energy.

Magnetoelectric and multiferroic properties of ternary copper chalcogenides Cu(2)M(II)M(IV)S(4).

We investigate theoretically the ternary copper chalcogenides with the general formula Cu(2)M(II)M(IV)S(4). This family of compounds can crystallize in two different non-centrosymmetric structures, [Formula: see text] or Pnm 2(1). We show that all the reported members of Cu(2)M(II)M(IV)S(4) having the Pnm 2(1) symmetry exhibit a large spontaneous polarization. This result suggests that several of these materials are likely to be multiferroics since they order magnetically at low temperature. We discuss in detail in the framework of Landau theory the members Cu(2)MnSnS(4) and Cu(2)MnGeS(4) which should present both a linear magnetoelectric effect and multiferroic behavior.

Scaling behavior of the magnetocapacitance of YbMnO(3).

We observe a seemingly complex magnetic field dependence of the dielectric constant of hexagonal YbMnO(3) near the spin ordering temperature. After rescaling, the data taken at different temperatures and magnetic fields collapse on a single curve describing the sharp anomaly in nonlinear magnetoelectric response at the magnetic transition. We show that this anomaly is a result of the competition between two magnetic phases. The scaling and the shape of the anomaly are explained using the phenomenological Landau description of the competing phases in hexagonal manganites.

Magnetic field induced ferroelectric to relaxor crossover in Tb(1-x)Ca(x)MnO(3).

The influence of magnetic field on the electrical properties of Tb(1-x)Ca(x)MnO(3) has been investigated by means of dielectric, polarization and neutron diffraction measurements. A field of 6 T applied along the b-axis induces a crossover from ferroelectric to relaxor behavior for the x = 0.02 compound at temperatures close to the ferroelectric transition. The mechanism of this field induced crossover involves a decrease in the coherence length of the Mn-spin-spiral structure due to increasing electron hopping rates associated with double exchange. Moreover, a large negative magnetocapacitance is observed at the freezing temperature for x = 0.05, which originates from suppression of the relaxor state and thus represents a new mechanism of magnetocapacitance.

On the mechanism of charge transport in pentacene.

Terahertz transient conductivity measurements are performed on pentacene single crystals, which directly demonstrate a strong coupling of charge carriers to low frequency molecular motions with energies centered around 1.1 THz. We present evidence that the strong coupling to low frequency motions is the factor limiting the conductivity in these organic semiconductors. Our observations explain the apparent paradox of the "bandlike" temperature dependence of the conductivity beyond the validity limit of the band model.

Electronic band structure of tetracene-TCNQ and perylene-TCNQ compounds.

The relationship between the crystal structures, band structures, and electronic properties of acene-TCNQ complexes has been investigated. We focus on the newly synthesized crystals of the charge-transfer salt tetracene-TCNQ and similar to it perylene-TCNQ, potentially interesting for realization of ambipolar transport. The band structures were calculated from first principles using density-functional theory (DFT). Despite the similarity in the crystal structures of the acene-TCNQ complexes studied here, the band structures are very different. Hole and electron transport properties are predicted to be equally good in perylene-TCNQ, in contrast to the tetracene-TCNQ, which has good transport properties for electrons only. The estimated degree of charge transfer for tetracene-TCNQ is 0.13e and for perylene-TCNQ 0.46e.

Prediction for new magnetoelectric fluorides.

We use symmetry considerations in order to predict new magnetoelectric fluorides. In addition to these magnetoelectric properties, we discuss which among these fluorides are the ones susceptible to present multiferroic properties. We emphasize that several materials exhibit ferromagnetic properties. This ferromagnetism should enhance the interplay between the magnetic and dielectric properties in these materials.

Evidence for electronic phase separation between orbital orderings in SmVO3.

We report evidence for phase coexistence of orbital orderings of different symmetry in SmVO3 by high resolution x-ray powder diffraction. The phase coexistence is triggered by an antiferromagnetic ordering of the vanadium spins near 130 K, below an initial orbital ordering near 200 K. The phase coexistence is the result of the intermediate ionic size of samarium coupled to exchange striction at the vanadium spin ordering.

Evidence for differentiation in the iron-helicoidal chain in GdFe3(BO3)4.

A single-crystal X-ray structure study of gadolinium triiron tetraborate, GdFe3(BO3)4, at room temperature and at 90 K is reported. At room temperature GdFe3(BO3)4 crystallizes in a trigonal space group, R32 (No. 155), the same as found for other members of the iron borate family RFe3(BO3)4. At 90 K the structure of GdFe3(BO3)4 transforms to the space group P3(1)21 (No. 152). The low-temperature structure determination gives new insight into the weakly first-order structural phase transition at 156 K and into the related Raman phonon anomalies. The presence of two inequivalent iron chains in the low-temperature structure provides a new perspective on the interpretation of the low-temperature magnetic properties.

The effect of oxygen exposure on pentacene electronic structure.

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O(2) and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O(2) at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.

Spin-polarized transport across sharp antiferromagnetic boundaries.

We report spin-polarized transport experiments across antiphase domain boundaries which act as atomically sharp magnetic interfaces. The antiphase boundaries are prepared by growing Fe(3)O(4) epitaxially on MgO, the magnetic coupling over a large fraction of these boundaries being antiferromagnetic. Magnetoresistance measurements yield linear and quadratic field dependence up to the anisotropy field for fields applied parallel and perpendicular to the film plane, respectively. This behavior can be explained by a hopping model in which spin-polarized electrons traverse an antiferromagnetic interface between two ferromagnetic chains.