We employ a combined experimental-theoretical study of the first- and second-order Raman modes of monoclinic $β$-Ga$_{2}$O$_{3}$. The investigated materials is of particular interest due to its deep-UV bandgap paired with a high critical field strength, offering promising applications in power-electronics. A crucial prerequisite for the future development of Ga$_{2}$O$_{3}$-based devices is a detailed understanding of the lattice dynamics as they are important for the elasticity (through acoustic phonons), thermal conductivity (through the heat transferred by phonons), the temperature-dependence of the bandgap (impacted by electron-phonon coupling) or the free carrier transport (via phonon scattering). Polarized micro-Raman spectroscopy measurements on the (010) and ($\bar{2}01$) planes enable the determination of the phonon frequencies of all 15 first-order and more than 40 second-order Raman modes. The experimental results are correlated with calculations of the mode frequencies, phonon dispersion relation and phonon density of states using density functional perturbation theory (DFPT). By applying a group-theoretical analysis, we are able to distinguish between overtones and combinational modes and identify the high symmetry points in the Brillouin zone which contribute to the observed second order modes. Based on these information, we demonstrate the simultaneous determination of Raman-, IR-, and acoustic phonons in $β$-Ga$_{2}$O$_{3}$ by second-order Raman spectroscopy.
We have studied electric-field-induced symmetry lowering in the tetragonal (001)-oriented heteroepitaxial (Ba$_{0.8}$Sr$_{0.2}$)TiO$_3$ thin film deposited on (001)MgO substrate. Polarized micro-Raman spectra were recorded from the film area in between two planar electrodes deposited on the film surface. Presence of \textit{c}-domains with polarization normal to the substrate was confirmed from polarized Raman study under zero field, while splitting and hardening of the \textit{E}(TO) soft mode and polarization changes in the Raman spectra suggest monoclinic symmetry under external electric fi…
Octahedral tilting is most common distortion process observed in centrosymmetric perovskite compounds (ABO$_{3}$). Indeed, crucial physical properties of this oxide stem from the tilts of BO$_{6}$ rigid octahedra. In microwave ceramics with perovskite-type structure, there is a close relation between the temperature coefficient of resonant frequency and tilt system of the perovskite structure. However, in many cases, limited access facilities are needed to assign correctly the space group, including neutron scattering and transmission electron microscopy. Here, we combine the Raman scattering …
Raman spectra of PbZr1-xTixO3 ceramics with titanium concentration varying between 0.40 and 0.60 were measured at 7 K. By observing the concentration-frequency dependence of vibrational modes, we identified the boundaries among rhombohedral, monoclinic, and tetragonal ferroelectric phases. The analysis of the spectra was made in the view of theory group analysis making possible the assignment of some modes for the monoclinic phase.
High-pressure synchrotron based angle dispersive x-ray diffraction (ADXRD) studies were carried out on SmGdO3 (SGO) up to 25.7GPa at room temperature. ADXRD results indicated a reversible pressure-induced phase transition from ambient monoclinic to hexagonal phase at about 8.9 GPa. The observed pressure-volume data were fitted into the third order Birch-Murnaghan equation of state yielding zero pressure bulk moduli B0 = 132(22) and 177(22) GPa for monoclinic and hexagonal phases, respectively. Pressure dependent micro-Raman spectroscopy further confirmed the phase transition. The mode Gruneise…
A nanometric Sb2Te3 rhombohedral phase was produced from Sb and Te by mechanical alloying for 3 hours and its structural stability was studied by synchrotron X-ray diffraction (XRD) and Raman spectroscopy (RS) measurements as a function of pressure. A phase transformation from the ambient pressure rhombohedral phase into a β-Sb2Te3 monoclinic structure between 9.8 and 13.2 GPa is observed by XRD. This phase transformation is confirmed by the Raman spectroscopy measurements. The pressure dependence of the volume fited to a Birch-Murnaghan equation of state gives a bulk modulus B0 = 40.6 +- 1.5 …
We determine the frequency dependence of the four independent Cartesian tensor elements of the dielectric function for monoclinic symmetry Y$_2$SiO$_5$ using generalized spectroscopic ellipsometry from 40-1200 cm$^{-1}$. Three different crystal cuts, each perpendicular to a principle axis, are investigated. We apply our recently described augmentation of lattice anharmonicity onto the eigendielectric displacement vector summation approach [A. Mock et al., Phys. Rev. B 95, 165202 (2017)], and we present and demonstrate the application of an eigendielectric displacement loss vector summation app…
A detailed high pressure investigation is carried out on $Fe_4Nb_2O_9$ using angle resolved x-ray diffraction and Raman spectroscopy measurements. We find a structural transition from the ambient trigonal phase to a monoclinic phase above 8.8 GPa. The structural transition is assumed to be driven by a large distortion of $Nb-O_6$ octahedra as seen from x-ray diffraction analysis and a large pressure dependence of $Nb-O_6$ octahedra breathing Raman mode. Anomalous behaviour of Raman modes and increase in the phonon life time at the phase transition pressure indicate a trigonal paramagnetic phas…
The Raman spectrum and particularly the Raman scattering intensities of monoclinic $β\text{-Ga}_2\text{O}_3$ are investigated by experiment and theory. The low symmetry of $β\text{-Ga}_2\text{O}_3$ results in a complex dependence of the Raman intensity for the individual phonon modes on the scattering geometry which is additionally affected by birefringence. We measured the Raman spectra in dependence on the polarization direction for backscattering on three crystallographic planes of $β\text{-Ga}_2\text{O}_3$ and modeled these dependencies using a modified Raman tensor formalism which takes b…
The dielectric tensor of $β$-Ga$_2$O$_3$ was determined by generalized spectroscopic ellipsometry in a wide spectral range from $0.5\,\mathrm{eV}$ to $8.5\,\mathrm{eV}$ as well as by calculation including quasiparticle bands and excitonic effects. The dielectric tensors obtained by both methods are in excellent agreement with each other and the observed transitions in the dielectric function are assigned to the corresponding valence bands. It is shown that the off-diagonal element of the dielectric tensor reaches values up to $|\varepsilon_{xz} | \approx 0.30 $ and cannot be neglected. Even in…
A combined generalized spectroscopic ellipsometry measurement and density functional theory calculation analysis is performed to obtain the complete set of infrared active phonon modes in Lu$_{2}$SiO$_{5}$ with monoclinic crystal structure. Two different crystals, each cut perpendicular to a different crystal axis are investigated. Ellipsometry measurements from 40 - 1200 cm$^{-1}$ are used to determine the frequency dependent dielectric function tensor elements. The eigendielectric displacement vector summation approach and eigendielectric displacement loss vector summation approach both augm…
Recently discovered class of 2D materials based on transition metal phosphorous trichalcogenides exhibit antiferromagnetic ground state, with potential applications in spintronics. Amongst them, FePS$ _{3} $ is a Mott insulator with a band gap of $\sim$ 1.5 eV. This study using Raman spectroscopy along with first-principles density functional theoretical analysis examines the stability of its structure and electronic properties under pressure. Raman spectroscopy reveals two phase transitions at 4.6 GPa and 12 GPa marked by the changes in pressure coefficients of the mode frequencies and the nu…
We have carried out temperature-dependent x-ray diffraction and Raman scattering experiments on powder $Cs_3Bi_2Br_9$. Trigonal to monoclinic structural transition at around 95 K is discussed and shown to be driven by the softening of the soft mode. We propose a model to describe the dynamics of the incomplete soft-mode. Raman scattering experiments demonstrate the origin of the soft mode to the rocking motions of Br atoms that participate to form $BiBr_6$ octahedra, which correlates the reported theoretical calculations. Some of the Raman mode frequencies exhibit anomalous temperature depende…
A previous study of the growth conditions has shown that single-phase BiFeO3 thin films can only be obtained in a narrow pressure-temperature window and that these films display a weak magnetic moment. Here we study in more detail the structure and the magnetism of single-phase BiFeO3 films by means of reciprocal space mapping, Raman spectroscopy and neutron diffraction. X-ray and Raman data suggest that the BiFeO3 structure is tetragonal for 70 nm-thick films and changes to monoclinic for 240 nm-thick films, thus remaining different from that of the bulk (rhombohedral) structure. In the 240 n…
We use a combination of polarized Raman spectroscopy experiment and model magnetism-phonon coupling calculations to study the rich magneto-Raman effect in the two-dimensional (2D) magnet $\mathrm{CrI_3}$. We reveal a novel layered-magnetism-assisted phonon scattering mechanism below the magnetic onset temperature, whose Raman excitation breaks time-reversal symmetry, has an antisymmetric Raman tensor, and follows the magnetic phase transitions across critical magnetic fields, on top of the presence of the conventional phonon scattering with symmetric Raman tensors in $N$-layer $\mathrm{CrI_3}$…
Twisted van der Waals heterostructures unravel a new platform to study strongly correlated quantum phases. The interlayer coupling in these heterostructures is sensitive to twist angles ($θ$) and key to controllably tune several exotic properties. Here, we demonstrate a systematic evolution of the interlayer coupling strength with twist angle in bilayer $\mathrm{MoS_{2}}$ using a combination of Raman spectroscopy and classical simulations. At zero doping, we show a \textit{monotonic} increment of the separation between the $\mathrm{A_{1g}}$ and $\mathrm{E^{1}_{2g}}$ mode frequencies as $θ$ dec…
Complete Raman Tensor Determination in Birefringent $β$-Ga$_2$O$_3$ by Single-Stage Hyperspectral Analysis of Polarization Angle-Resolved Raman Spectra
Paul-Drude-Institut für Festkörperelektronik, Leibniz-Institut im Forschungsverbund Berlin e.V.（柏林莱布尼茨固体电子学保罗·德鲁德研究所）；Technische Universität Berlin（柏林工业大学）；Leibniz-Institut für Kristallzüchtung（莱布尼茨晶体生长研究所）；Institut de Ciència de Materials de Barcelona, ICMAB-CSIC（巴塞罗那材料科学研究所）
We report Raman signatures of electronic topological transition (ETT) at 3.6 GPa and rhombohedral (α-Bi2Te3) to monoclinic (β-Bi2Te3) structural transition at ~ 8 GPa. At the onset of ETT, a new Raman mode appears near 107 cm-1 which is dispersionless with pressure. The structural transition at ~ 8 GPa is marked by a change in pressure derivative of A1g and Eg mode frequencies as well as by appearance of new modes near 115 cm-1and 135 cm-1. The mode Grüneisen parameters are determined in both the α and β-phases.
(BiFeO3)(1-x)Λ/(LaFeO3)xΛ superlattices (SLs) with varying x have been grown by pulsed laser deposition on (111) oriented SrTiO3 substrates. In order to obtain good epitaxy and flat samples a conducting SrRuO3 buffer has been deposited prior to the superlattices to screen the polar mismatch for such (111) SrTiO3 orientation. X-ray diffraction reciprocal space mapping on different family of planes were collected and evidenced a room temperature structural change at x=0.5 from a rhombohedral/monoclinic structure for rich BiFeO3 to an orthorhombic symmetry for rich LaFeO3. This symmetry change ha…
The effect of pressure on the Raman spectrum of PbWO4 has been investigated up to 48 GPa in a diamond-anvil cell using neon as pressure-transmitting medium. Changes are detected in the Raman spectrum at 6.8 GPa as a consequence of a structural phase transition from the tetragonal scheelite structure to the monoclinic PbWO4-III structure. Two additional phase transitions are detected at 15.5 and 21.2 GPa to the previously unknown crystalline phases IV and V. The last one remains stable up to 43.3 GPa. At 47.7 GPa all Raman modes disappear, which could be caused by a pressure-induced amorphizati…
BiFeO$_3$ thin films can be epitaxially stabilized in a nearly-tetragonal phase under a high biaxial compressive strain. Here we investigate the polarized Raman spectra of constrained BiFeO$_3$ films with tetragonal-like (BFO-T), rhombohedral-like (BFO-R) and multiphase (BFO-T+R) structure. Based on analysis of the number and symmetry of the Raman lines, we provide strong experimental evidence that the nearly-tetragonal films are monoclinic ($Cc$ symmetry) and not tetragonal $(P4mm)$. Through the Raman mapping technique we show localized coexistence of BFO-T and BFO-R phases with the relative …
By means of in situ synchrotron X-ray diffraction and Raman spectroscopy under hydrostatic pressure, we investigate the structural stability of the quadruple perovskite LaMn7O12. At 34 GPa, the data unveil a first-order structural phase transition from monoclinic I2/m to cubic Im-3 symmetry characterized by a pronounced contraction of the unit cell and by a significant modifications in the Raman phonon modes. The phase transition is also marked by the suppression of Jahn-Teller distortion which is present in the ambient monoclinic phase. In addition, above 20 GPa pressure, a sudden and simulta…
First principles computations of Raman intensities were performed for perovskite-family compound CaAl$_{1/2}$Nb$_{1/2}$O$_3$ (CAN). This compound features 1:1 (NaCl-type) ordering of Al and Nb superimposed onto the $b^-b^-c+$ octahedral tilting. Raman tensor for CAN was computed using the package for first-principles computations ABINIT (URL \underline {http://www.abinit.org}). Computations performed for both untilted cubic ($Fm\bar{3}m$) and tilted monoclinic ($P2_1/n$) CAN structures showed that the strongest Raman lines are associated with the ordering of Al and Nb. The computed spectrum ag…
An intrinsic antiferromagnetic topological insulator $\mathrm{MnBi_2Te_4}$ can be realized by intercalating Mn-Te bilayer chain in a topological insulator, $\mathrm{Bi_2Te_3}$. $\mathrm{MnBi_2Te_4}$ provides not only a stable platform to demonstrate exotic physical phenomena, but also easy tunability of the physical properties. For example, inserting more $\mathrm{Bi_2Te_3}$ layers in between two adjacent $\mathrm{MnBi_2Te_4}$ weakens the interlayer magnetic interactions between the $\mathrm{MnBi_2Te_4}$ layers. Here we present the first observations on the inter- and intra-layer phonon modes …
The monoclinic crystal structure of $β$-$\mathrm{Ga_2O_3}$ leads to significant anisotropy of the thermal properties. The 2$ω$-method is used to measure the thermal diffusivity $D$ in [010] and [001] direction respectively and to determine the thermal conductivity values $λ$ of the [100], [010] and [001] direction from the same insulating Mg doped $β$-$\mathrm{Ga_2O_3}$ single crystal. We detect a temperature independent anisotropy factor of both the thermal diffusivity and conductivity values of $D_{[010]}/D_{[001]}=λ_{[010]}/λ_{[001]}=1.4\pm 0.1$. The temperature-dependence is in accord with…
The vibrational properties of ferrimagnetic $\mathrm{Mn_3Si_{2}Te_6}$ single crystals are investigated using Raman spectroscopy and density functional theory calculations. Eighteen Raman-active modes are identified, fourteen of which are assigned according to with the trigonal symmetry. Four additional peaks, obeying the $A_{1g}$ selection rules, are attributed to the overtones. The unconventional temperature evolution of the $A_{1g}^5$ mode self-energy suggests a competition between different short-range magnetic correlations that significantly impact the spin-phonon interaction in $\mathrm{M…
Vanadium tetracyanoethylene (V[TCNE]$_{x}$, $x\approx 2$) is an organic-based ferrimagnet with a high magnetic ordering temperature $\mathrm{T_C>600 ~K}$, low magnetic damping, and growth compatibility with a wide variety of substrates. However, similar to other organic-based materials, it is sensitive to air. Although encapsulation of V[TCNE]$_{x}$ with glass and epoxy extends the film lifetime from an hour to a few weeks, what is limiting its lifetime remains poorly understood. Here we characterize encapsulated V[TCNE]$_{x}$ films using confocal microscopy, Raman spectroscopy, ferromagnetic …
Raman spectroscopy is a powerful tool for characterizing the local properties of graphene. Here, we introduce a method for evaluating unknown strain configurations and simultaneous doping. It relies on separating the effects of hydrostatic strain (peak shift) and shear strain (peak splitting) on the Raman spectrum of graphene. The peak shifts from hydrostatic strain and doping are separated with a correlation analysis of the 2D and G frequencies. This enables us to obtain the local hydrostatic strain, shear strain and doping without any assumption on the strain configuration prior to the analy…
We report high-pressure photoluminescence, Raman scattering, and x-ray diffraction measurements on a lead-free halide perovskite $Cs_3Sb_2Br_9$. At about 3 GPa, an electronic transition manifests itself through a broad minimum in linewidth, a maximum in the intensity of $E_g$, $A_{1g}$ Raman modes, and the unusual change in the $c/a$ ratio of the trigonal lattice. The large compressibility and observed Raman anomalies indicate to a soft material with strong electron-phonon coupling. The observed below bandgap broadband emission in the photoluminescence measurement indicates the recombination o…
We have performed a first-principles study of the structural and vibrational properties of the three low-pressure (cubic, tetragonal, and especially monoclinic) phases of ZrO2, with special attention to the computation of the zone-center phonon modes and related dielectric properties. The calculations have been carried out within the local-density approximation using ultrasoft pseudopotentials and a plane-wave basis. The fully relaxed structural parameters are found to be in excellent agreement with experimental data and with previous theoretical work. The total-energy calculations correctly r…
Rare earth Manganite Nickelite double perovskites are prepared by solgel assisted combustion route, where, R varies from La, Pr, Nd, Sm, Gd, Tb, Dy, Y, and Ho. The samples have been systematically investigated using powder xray diffraction, Raman spectroscopy, ultraviolet visible spectroscopy, magnetization, and synchrotron based xray absorption spectroscopy measurements. All compounds in the family crystallize in the monoclinic structure and the monoclinic distortion enhances with decreasing trivalent rare earth radii. The magnetic ordering temperature, Tc, decreases from 270 K for La to 80 K…
We report the results of Raman spectroscopy high-pressure studies of alkali metal fluoroargentates (M2AgF4, where M=Na, K, Rb) associated with theoretical and x-ray diffraction studies for the K member of the series. Theoretical density functional calculations predict two structural phase transitions for K2AgF4: one from low pressure monoclinic P21/c (beta) phase to intermediate-pressure tetragonal I4!2d structure at 6 GPa, and another to high-pressure triclinic P1! phase at 58 GPa. However, Raman spectroscopy and X-ray diffraction data indicate that both polymorphic forms of K2AgF4 as well as…
We report non-resonant x-ray Raman scattering (XRS) measurements from hexagonal boron nitride for transferred momentum from 2 to 9 $\mathrmÅ^{-1}$ along directions both in and out of the basal plane. A symmetry-based argument, together with real-space full multiple scattering calculations of the projected density of states in the spherical harmonics basis, reveals that a strong pre-edge feature is a dominantly $Y_{10}$-type Frenkel exciton with no other \textit{s}-, \textit{p}-, or \textit{d}- components. This conclusion is supported by a second, independent calculation of the \textbf{q}-depen…
Absorption, luminescence and Raman spectra of interstitial bismuth atoms, $\mathrm{Bi}^{0}$, and negatively charged dimers, $\mathrm{Bi}^{2-}$, in alumosilicate, germanosilicate, phosphosilicate and phosphogermanate glasses networks are calculated by time-dependent density functional method. On grounds of this calculation an extension of our previously suggested model of broadband near-IR luminescence in bismuth-doped glasses is put forward.
Phonon-phonon anharmonic effects have a strong influence on the phonon spectrum; most prominent manifestation of these effects are the softening (shift in frequency) and broadening (change in FWHM) of the phonon modes at finite temperature. Using Raman spectroscopy, we studied the temperature dependence of the FWHM and Raman shift of $\mathrm{E_{2g}^1}$ and $\mathrm{A_{1g}}$ modes for single-layer and natural bilayer MoS$_2$ over a broad range of temperatures ($8 < $T$ < 300$ K). Both the Raman shift and FWHM of these modes show linear temperature dependence for $T>100$ K, whereas they become …
Vanadium Sesquioxide (V$_2$O$_3$) is an antiferromagnetic insulator below $T_{\mathrm N}\approx$ 155 K. The magnetic order is not of C- or G-type as one would infer from the bipartite character of the hexagonal basal plane in the high-temperature corundum structure. In fact, the Néel transition is accompanied by a monoclinic distortion that makes one bond of the honeycomb plane inequivalent from the other two, thus justifying a magnetic structure with one ferromagnetic bond and two antiferromagnetic ones. We show here that the magnetic ordering, the accompanying monoclinic structural distortio…
We investigate the electronic and magnetic properties as well as lattice dynamics and spin-phonon coupling of $β$-Na$_{0.33}$V$_2$O$_5$ using temperature-dependent Raman scattering, dc-magnetization and dc-resistivity, x-ray photoemission, and absorption spectroscopy. The Rietveld refinement of XRD pattern with space group C2/m confirms the monoclinic structure. The analysis of temperature-dependent Raman spectra in a temperature range of 13--673~K reveals an anharmonic dependence of the phonon frequency and full width at half maximum, which is accredited to the symmetric phonon decay. However…
