We discuss the first infrared reflectivity measurement on a BiFeO3 single crystal between 5 K and room temperature. The 9 predicted ab-plane E phonon modes are fully and unambiguously determined. The frequencies of the 4 A1 c-axis phonons are found. These results settle issues between theory and data on ceramics. Our findings show that the softening of the lowest frequency E mode is responsible for the temperature dependence of the dielectric constant, indicating that the ferroelectric transition in BiFeO3 is soft-mode driven.
We present neutron inelastic scattering measurements of the low-energy phonons in single crystal BiFeO3. The dispersions of the three acoustic phonon modes (LA along [100], TA1 along [010] and TA2 along [110]) and two low energy optic phonon modes (LO and TO1) have been mapped out between 300 K and 700 K. Elastic constants are extracted from the phonon measurements. The energy linewidths of both TA phonons at the zone boundary clearly broaden when the system is warmed toward the magnetic ordering temperature TN = 640 K. This suggests that the magnetic and low-energy lattice dynamics in this mu…
We report the direct observation of a "resonance" mode in the lowest-energy optic phonon very near the zone center around (111) in the multiferroic BiFeO$_3$ using neutron scattering methods. The phonon scattering intensity is enhanced when antiferromagnetic (AFM) order sets in at T$_N = 640$~K, and it increases on cooling. This "resonance" is confined to a very narrow region in energy-momentum space where no spin-wave excitation intensity is expected, and it can be modified by an external magnetic field. Our results suggest the existence of a novel coupling between the lattice and spin fluctu…
In this paper we investigated the influence of the rare-earth ionic radii on the spin-phonon coupling in RE2NiMnO6 double perovskites by Raman spectroscopy. Spin-phonon in dense Nd2NiMnO6 and Gd2NiMnO6 ceramics were investigated by Raman spectroscopy at low temperatures. The magnitude of the coupling observed in comparison with other isostructural compounds shows that it is not influenced by the rare-earth ionic radius, as well as the deviation of the position of the stretching phonon in the ferromagnetic phase with relation to the anharmonic contributions follows a power law.
We report on bifurcations effect mediated by the electron-phonon coupling in a concentrated rare-earth-containing antiferromagnet, observed in the spectra of coupled $4f$-electron-phonon modes under the influence of an external magnetic field. The effect was observed in the low-temperature far-infrared (terahertz) reflection spectra of a multiferroic easy-axis antiferromagnet $PrFe_3(BO_3)_4$ in magnetic fields $\textbf{B}_{ext}||c$. Both paramagnetic and magnetically ordered phases (including a spin-flop one) were studied in magnetic fields up to 30 T. We show that the field behavior of the c…
Spin-Phonon Coupling, High Pressure Phase Transitions and Thermal Expansion of Multiferroic GaFeO3: A Combined First Principles and Inelastic Neutron Scattering Study
The present work reports the preparation of polycrystalline multiferroic $GdFeO_3$ (GdFO) and characterization with x-ray diffraction (XRD), magnetization, temperature dependent Raman spectroscopy, temperature and magnetic field dependent $^{57}Fe$ M$\ddot{o}$ssbauer spectroscopy measurements. The sample is found to be phase pure from Rietveld refinement of XRD pattern. The M$\ddot{o}$ssbauer spectra measured in the presence of external magnetic field show the signatures of field induced spin reorientation transition, which are corroborated by magnetization measurements. From the temperature d…
The chiral langasite Ba$\_3$NbFe$\_3$Si$\_2$O$\_{14}$ is a multiferroic compound. While its magnetic order below T$\_N$=27 K is now well characterised, its polar order is still controversial. We thus looked at the phonon spectrum and its temperature dependence to unravel possible crystal symmetry breaking. We combined optical measurements (both infrared and Raman spectroscopy) with ab initio calculations and show that signatures of a polar state are clearly present in the phonon spectrum even at room temperature. An additional symmetry lowering occurs below 120~K as seen from emergence of soft…
IR Phonon signatures of multiferroicity in TbMn$_{2}$O$_{5}$
研究了多铁性TbMn $_2$ O $_5$的红外（IR）激活声子随温度的变化.观察到了大部分沿\textit{a}和\textit{b}晶轴极化的对称性允许的红外模式，并且几个\textit{b}极化声子的行为与磁和铁电跃迁相关。顺电相只允许拉曼的高频\textit{b}极化声子在铁电相变时变为IR活性。该模式的IR强度与铁电体序参量的平方成比例，并且给出了降低铁电体相中晶格畸变的对称性的灵敏量度。
Spin and lattice dynamics of CaMn7O12 ceramics were investigated using infrared, THz and inelastic neutron scattering (INS) spectroscopies in the temperature range 2 to 590 K, and, at low temperatures, in applied magnetic fields of up to 12 T. On cooling, we observed phonon splitting accompanying the structural phase transition at Tc = 450K as well as the onset of the incommensurately modulated structure at 250 K. In the two antiferromagnetic phases below T_N1 = 90K and T_N2 = 48 K, several infrared-active excitations emerge in the meV range; their frequencies correspond to the maxima in the m…
We have carried out temperature-dependent inelastic neutron scattering measurements of YMnO3 over the temperature range 50 - 1303 K, covering both the antiferromagnetic to paramagnetic transition (70 K), as well as the ferroelectric to paraelectric transition (1258 K). Measurements are accompanied by first principles calculations of phonon spectra for the sake of interpretation and analysis of the measured phonon spectra in the room temperature ferroelectric (P63cm) and high temperature paraelectric (P63/mmc) hexagonal phases of YMnO3. The comparison of the experimental and first-principles ca…
Multiferroics possess two or more switchable states such as polarization, magnetization, etc. Phonon excitations in multiferroic phase are strongly modified by magnetoelectric coupling, spin-phonon coupling, and anharmonic phonon-phonon interactions. Here, we have investigated the correlation between phonons and multiferroic order parameters in hexagonal BaMO3: M = Ti1-x(Mn/Fe)x systems using powder x-ray diffraction (PXRD), Raman spectroscopic, and magnetic measurements. The structural transformation from a polar tetragonal to a non-polar 6H-type hexagonal phase is observed as a function of d…
Colossal magnon-phonon coupling in multiferroic Eu$_{0.75}$Y$_{0.25}$MnO$_3$
本文报道了Eu $_{0.75}$ Y $_{0.25}$ MnO $_3$的变温远红外光谱（10-250 cm $^{-1}$）的磁诱导电偶极吸收谱。这些光谱只发生在$e||a$极化中，由两个相对窄的电磁子特征和一个宽的吸收带组成，其中电磁子特征在$T_{FE}=30$ K开始，而吸收带在远高于$T_N=47$ K的温度下持续存在。所观察到的激发占步的静态介电常数在铁电相。观测到80 cm $^{-1}$处的电磁振子与附近的最低光学声子强耦合，该声子将其光谱重量的1/2以上转移到磁振子。我们把宽背景吸收的起因归结为声子的两个磁振子发射衰变过程。
We report on polarized infrared reflectivity measurements of multiferroic, monoclinic MnWO4 between 10K and 295K. The full dielectric tensor and the frequency dependence of the orientation of the principal axes have been determined in the frequency range of the phonons. All infrared-active phonon modes (7 A_u modes and 8 B_u modes) are unambiguously identified. In particular the strongest B_u modes have been overlooked in previous studies, in which the monoclinic symmetry was neglected in the analysis. Using a generalized Drude-Lorentz model, we determine the temperature dependence of the phon…
We studied the ultrafast third-order optical nonlinearity in a single crystal of multiferroic bismuth ferrite (BiFeO3) in the near-infrared range of 0.5-1.0 eV, where the material is fundamentally transparent,at room temperature. With pump pulses at 1.55 eV, which is off-resonant to the strong inter-band charge transfer (CT) transition, we observed instantaneous transient absorption with pencil-like temporal profile originating from the two-photon CT transition from the oxygen 2p to the iron 3p levels. In contrast, under pumping with 3.10-eV photons, the pencil-like absorption change was not o…
The coexisting magnetic and ferroelectric orders in multiferroic materials give rise to a handful of novel magnetoelectric phenomena, such as the absorption difference for the opposite propagation directions of light called the non-reciprocal directional dichroism (NDD). Usually these effects are restricted to low temperature, where the multiferroic phase develops. In this paper we report the observation of NDD in the paramagnetic phase of Sr2CoSi2O7 up to temperatures more than ten times higher than its Néel temperature (7 K) and in fields up to 30 T. The magnetically induced polarization and…
We have carried out a detailed experimental investigation on CuO using dielectric constant, ac resistance, Raman spectroscopy and X-ray diffraction measurements at high pressures and room temperature. Both dielectric constant and dielectric loss show an anomalous peak in the pressure range 3.4-4 GPa indicating a ferroelectric transition. Raman studies show anomalous behaviour of the Ag mode with a slope change in the mode frequency and a minimum in the mode FWHM at 3.4 GPa indicating a strong spin phonon coupling along [1 0 -1] direction. A step like behaviour in the intensity of the Ag mode i…
We have elucidated the spin, lattice, charge and orbital coupling mechanism underlying the multiferroic character in tensile strained EuTiO3 films. Symmetry determined by oxygen octahedral tilting shapes the hybridization between the Eu 4f and Ti 3d orbitals and this inhibits predicted Ti displacement proper ferroelectricity. Instead, phonon softening emerges at low temperatures within the pseudo-cube (110) plane, orthogonal to the anticipated ferroelectric polarization symmetry. Additionally, the magnetic anisotropy is determined by orbital distortion through hybridization between the Ti 3d a…
With infrared and terahertz ellipsometry we investigated the anisotropy of the infrared active phonon modes in SrTiO3 (110) single crystals in the tetragonal state below the so-called antiferrodistortive transition at T* = 105 K. In particular, we show that the anisotropy of the oscillator strength of the so-called R-mode, which becomes weakly infrared active below T*, is a valuable indicator for the orientation of the structural domains. Our results reveal that a mono-domain state with the tetragonal axis (c-axis) parallel to the [001] direction can be created by applying a moderate uniaxial …
Cavity control of multiferroic order in single-layer NiI$_2$
Max Planck Institute for the Structure and Dynamics of Matter（马普结构与动力学物质研究所）；RWTH Aachen University（亚琛工业大学）；Universidad del País Vasco UPV/EHU（巴斯克大学）；Columbia University（哥伦比亚大学）
In this work, we performed temperature-dependent Raman spectroscopy studies on three layered metal thiophosphates: CuInP2S6, CuCrP2S6, and CuInP2S6-In4/3P2S6 heterostructures. These materials are emerging multiferroics, with CuInP2S6 and CuInP2S6-In4/3P2S6 exhibiting room temperature ferrielectric polarization while CuCrP2S6 is both anti-ferroelectric and antiferromagnetic at low temperatures (<145 and <30 K, respectively). We studied two prominent peaks in the Raman spectra of these compounds, namely their P-P and P-S stretching modes. First order linear fits to the mode softening yielded coe…
Dimensionality provides a clear fingerprint on the dispersion of infrared-active, polar-optical phonons. For these phonons, the local dipoles parametrized by the Born effective charges drive the LO-TO splitting of bulk materials; this splitting actually breaks down in two-dimensional materials. Here, we extend the existing theory to the one-dimensional (1D) case. Combining an analytical model with the implementation of density-functional perturbation theory in 1D boundary conditions, we show that the dielectric splitting in the dispersion relations collapses logarithmically at the zone center.…
