Cooperative dynamics in doped manganite films: phonon anomalies in the ferromagnetic state

We present optical measurements of phononic excitations in La$_{2/3}$Ca$_{1/3}$MnO$_{3}$ (LCMO) and La$_{2/3}$Sr$_{1/3}$MnO$_{3}$ (LSMO) thin films covering the full temperature range from the metallic ferromagnetic to the insulating paramagnetic phase. All eight phonons expected for the R$\bar{3}$c symmetry in LSMO and 17 out of the expected 25 phonons for the Pnma symmetry in LCMO have been determined. Close to the ferromagnetic-to-paramagnetic transition both compounds reveal an anomalous behavior but with different characteristics. Anomalies in the phononic spectra are a manifestation of the coupling of lattice degrees of freedom (DOF) to electronic DOF. Specifically, the low-frequency external group proves to be an indicator for lattice modifications induced by electronic correlations. The enhanced electron-phonon coupling in LCMO is responsible for Fano-like interference effects of distinct phonon modes with electronic continuum excitations: we observe asymmetric phonon line shapes, mode splitting and spectral weight transfer between modes.Comment: 10 pages, 10 figure

Large and Small Polaron Excitations in La2/3(Sr/Ca)1/3MnO3 Films

We present detailed optical measurements of the mid-infrared (MIR) excitations in thin films of La2/3Sr1/3MnO3 (LSMO) and La2/3Ca1/3MnO3 (LCMO) across the magnetic transition. The shape of the excitation at about 0.2 eV in both samples is analyzed in terms of polaron models. We propose to identify the MIR resonance in LSMO as the excitation of large polarons and that in LCMO as a small polaron excitation. A scaling behavior for the low-energy side of the polaronic MIR resonance in LSMO is established

Spin-phonon coupling in antiferromagnetic chromium spinels

The temperature dependence of eigenfrequencies and intensities of the IR active modes has been investigated for the antiferromagnetic chromium spinel compounds CdCr2O4, ZnCr2O4, ZnCr2S4, ZnCr2Se4, and HgCr2S4 by IR spectroscopy for temperatures from 5 K to 300 K. At the transition into the magnetically ordered phases, and driven by spin-phonon coupling, most compounds reveal significant splittings of the phonon modes. This is true for geometrically frustrated CdCr2O4, and ZnCr2O4, for bond frustrated ZnCr2S4 and for ZnCr2Se4, which also is bond frustrated, but dominated by ferromagnetic exchange. The pattern of splitting is different for the different compounds and crucially depends on the nature of frustration and of the resulting spin order. HgCr2S4, which is almost ferromagnetic, exhibits no splitting of the eigenfrequencies, but shows significant shifts due to ferromagnetic spin fluctuations.Comment: 15 pages, 6 figure

Magnetic-field induced multiferroicity in a quantum critical frustrated spin liquid

Dielectric spectroscopy is used to check for the onset of polar order in the quasi one-dimensional quantum spin system Sul-Cu2Cl4 when passing from the spin-liquid state into the ordered spiral phase in an external magnetic field. We find clear evidence for multiferroicity in this material and treat in detail its H-T phase diagram close to the quantum-critical regime.Comment: 5 pages, 4 figures. Revised according to suggestions of referee

Electronic and phonon excitations in {\alpha}-RuCl3_3

We report on THz, infrared reflectivity and transmission experiments for wave numbers from 10 to 8000 cm$^{-1}$ ($\sim$ 1 meV - 1 eV) and for temperatures from 5 to 295 K on the Kitaev candidate material {\alpha}-RuCl$_3$. As reported earlier, the compound under investigation passes through a first-order structural phase transition, from a monoclinic high-temperature to a rhombohedral low-temperature phase. The phase transition shows an extreme and unusual hysteretic behavior, which extends from 60 to 166 K. In passing this phase transition, in the complete frequency range investigated we found a significant reflectance change, which amounts almost a factor of two. We provide a broadband spectrum of dielectric constant, dielectric loss and optical conductivity from the THz to the mid infrared regime and study in detail the phonon response and the low-lying electronic density of states. We provide evidence for the onset of an optical energy gap, which is of order 200 meV, in good agreement with the gap derived from measurements of the DC electrical resistivity. Remarkably, the onset of the gap exhibits a strong blue shift on increasing temperatures.Comment: 18 pages, 7 figure

Coupling of phonons and electromagnons in GdMnO_3

The infrared and Terahertz properties of GdMnO_3 have been investigated as function of temperature and magnetic field, with special emphasis on the phase boundary between the incommensurate and the canted antiferromagnetic structures. The heterogeneous incommensurate phase reveals strong magnetodielectric effects, characterized by significant magnetoelectric contributions to the static dielectric permittivity and by the existence of electrically excited magnons (electromagnons). In the commensurate canted antiferromagnetic phase the magnetoelectric contributions to the dielectric constant and electromagnons are suppressed. The corresponding spectral weight is transferred to the lowest lattice vibration demonstrating the strong coupling of phonons with electromagnons.Comment: 5 pages, 4 figure

Broadband dielectric response of CaCu3Ti4O12: From dc to the electronic transition regime

We report on phonon properties and electronic transitions in CaCu3Ti4O12, a material which reveals a colossal dielectric constant at room temperature without any ferroelectric transition. The results of far- and mid-infrared measurements are compared to those obtained by broadband dielectric and millimeter-wave spectroscopy on the same single crystal. The unusual temperature dependence of phonon eigenfrequencies, dampings and ionic plasma frequencies of low lying phonon modes are analyzed and discussed in detail. Electronic excitations below 4 eV are identified as transitions between full and empty hybridized oxygen-copper bands and between oxygen-copper and unoccupied Ti 3d bands. The unusually small band gap determined from the dc-conductivity (~200 meV) compares well with the optical results.Comment: 7 pages, 8 figure

Phonon anomalies and charge dynamics in Fe_{1-x}Cu_{x}Cr_{2}S_{4} single crystals

A detailed investigation of phonon excitations and charge carrier dynamics in single crystals of Fe_{1-x}Cu_{x}Cr_{2}S_{4} (x = 0, 0.2, 0.4, 0.5) has been performed by using infrared spectroscopy. In FeCr_{2}S_{4} the phonon eigenmodes are strongly affected by the onset of magnetic order. Despite enhanced screening effects, a continuous evolution of the phonon excitations can be observed in the doped compounds with x = 0.2 (metallic) and x = 0.4, 0.5 (bad metals), but the effect of magnetic ordering on the phonons is strongly reduced compared to x = 0. The Drude-like charge-carrier contribution to the optical conductivity in the doped samples indicates that the colossal magneto-resistance effect results from the suppression of spin-disorder scattering.Comment: 8 pages, 6 figure

Plastic-crystalline solid-state electrolytes: Ionic conductivity and orientational dynamics in nitrile mixtures

Many plastic crystals, molecular solids with long-range, center-of-mass crystalline order but dynamic disorder of the molecular orientations, are known to exhibit exceptionally high ionic conductivity. This makes them promising candidates for applications as solid-state electrolytes, e.g., in batteries. Interestingly, it was found that the mixing of two different plastic-crystalline materials can considerably enhance the ionic dc conductivity, an important benchmark quantity for electrochemical applications. An example is the admixture of different nitriles to succinonitrile, the latter being one of the most prominent plastic-crystalline ionic conductors. However, until now only few such mixtures were studied. In the present work, we investigate succinonitrile mixed with malononitrile, adiponitrile, and pimelonitrile, to which 1 mol% of Li ions were added. Using differential scanning calorimetry and dielectric spectroscopy, we examine the phase behavior and the dipolar and ionic dynamics of these systems. We especially address the mixing-induced enhancement of the ionic conductivity and the coupling of the translational ionic mobility to the molecular reorientational dynamics, probably arising via a "revolving-door" mechanism.Comment: 9 pages, 7 figures; revised version as accepted for publication in J. Chem. Phy