Polar Phonon Research Articles

Ultrafast phonon diffuse scattering as a tool for observing chiral phonons in monolayer hexagonal lattices

At the 2D limit, hexagonal systems such as monolayer transition metal dichalcogenides (TMDs) and graphene exhibit unique coupled spin and momentum-valley physics (valley pseudospin) owing to broken spatial inversion symmetry and strong spin-orbit coupling. Circularly polarized light provides the means for pseudospin-selective excitation of excitons (or electrons and holes) and can yield momentum-valley polarized populations of carriers that are the subject of proposed valleytronic applications. The chirality of these excited carriers has important consequences for the available relaxation/scattering pathways, which must conserve (pseudo)angular momentum as well as energy. One available relaxation channel that satisfies these constraints is coupling to chiral phonons. Here, we show that chiral carrier-phonon coupling following valley-polarized photoexcitation is expected to lead to a strongly valley-polarized chiral phonon distribution when this relaxation mechanism is dominant. This momentum valley phonon polarization is directly measurable using ultrafast phonon diffuse scattering techniques. Using ab initio calculations, we show how the dynamic phonon occupations and valley anisotropy determined by nonequilibrium observations can provide a new window on the physical processes that drive carrier valley depolarization in monolayer TMDs.

The role of shear waves in electron-phonon relaxation and electrical resistivity of noble metals

• Shear waves make a main contribution to the resistivity of noble metals • At low temperatures, it is 95, 91, and 95% for crystals Au, Ag, and Cu, respectively • Results is aligns well with experiment in the temperature range from 10 to 1000 K The influence of elastic energy anisotropy on electron-phonon relaxation and electrical resistivity of noble metals has been studied within the Bloch-Grüneisen theory. Accounting for the influence of elastic anisotropy on spectrum, phonon polarization vectors, and electron relaxation by quasi-transverse modes makes it possible to quantitatively put in agreement the outcomes of calculating the temperature dependence of the electrical resistivity of noble metals with experimental data in the temperature range from 10 to 1000 K. A constant characterizing the interaction of electrons with shear waves in noble metals has been determined. The role of shear waves in electrical resistivity has been analyzed. It has been shown that the relaxation of electrons by shear waves, which was not previously taken into account, makes a dominant contribution to the electrical resistivity of noble metals in the entire temperature range from 10 to 1000 K. At temperatures well below the Debye temperature, this contribution is 95%, 91%, and 95% of the electrical resistivity for crystals Au, Ag, and Cu, respectively, and at T = 1000 K it decreases to 73%, 44%, and 68%.

Infrared and terahertz studies of phase transitions in the CH3NH3PbBr3 perovskite

We investigated the influence of two structural phase transitions in methylammonium lead tri-bromide ${\mathrm{CH}}_{3}{\mathrm{NH}}_{3}{\mathrm{PbBr}}_{3}$ $({\mathrm{MAPbBr}}_{3})$ single crystals on the activity of polar phonons using time-domain THz transmission and far infrared (IR) reflectance spectra. The fitting using the Lorentz model of damped harmonic oscillators also enables us to determine all the polar phonon parameters, IR response functions, and their temperature dependence. The fit of the far IR spectra provides a nearly perfect quantitative description of the measured reflectance at room temperature using three phonons. On cooling, three IR active phonons of the cubic and tetragonal structures split into 15 separate bands, signaling the transformation to the orthorhombic phase below 150 K. This result is compared with the factor group analysis of the polar phonons in all three crystallographic phases. The absence of a soft optical phonon supports the previously published order-disorder character of the structural phase transitions.

Optical-vibration properties and pressure-induced phase transition in (In,Sc)2Ge2O7 pyrogermanates

Thortveitite-type (T-type) scandium and indium pyrogermanates were obtained through a solid-state reaction route. The crystal structures, morphologies, and chemical compositions of these compounds were investigated by X-ray diffraction and transmission electron microscopy techniques. The optical-vibration properties were evaluated by Raman scattering and infrared spectroscopy. Reflectivity far-infrared data were obtained for sintered Sc2Ge2O7 samples, which exhibited good surfaces after polishing, allowing the determination of the infrared optical functions, the complete polar phonon characteristics, the intrinsic dielectric constant and the unloaded quality factor. Because of the poor surface reflectivity of In2Ge2O7 samples, only mid-infrared absorbance data could be collected by using loose powders in an attenuated total reflectance accessory. By using polarized Raman spectroscopy on both ceramic materials, at room temperature and ambient pressure, all the 15 active Raman modes predicted by group theory for the monoclinic C2/m T-type structure were identified and assigned. Further, the phase stabilities of In2Ge2O7 and Sc2Ge2O7 were studied by high-pressure Raman spectroscopy. In the limit of pressures studied here (up to 10 GPa), a reversible structural phase transition (SPT) for In2Ge2O7 and Sc2Ge2O7 was induced by pressures of 4.2 GPa and 2.4 GPa, respectively. These would correspond to the reported C2/m (#12) ↔ P21/c (#14) SPT. Representative Raman spectra of the high-pressure phase for both materials were fitted and 24 first-order Raman modes were depicted for each material, a number greater than compatible with a proposed distorted and oxygen-deficient fluorite-like structure, but explained by an analysis of the gtroup-subgroup constraints of this SPT.

Modifying the magnetoelectric coupling in TbMnO3 by low-level Fe3+ substitution

We report a comprehensive study of the low-level substitution of ${\mathrm{Mn}}^{3+}$ by ${\mathrm{Fe}}^{3+}$ effect on the static and dynamic magnetoelectric coupling in $\mathrm{Tb}{\mathrm{Mn}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{x}{\mathrm{O}}_{3}$ ($x=0$, 0.02, and 0.04). The cationic substitution has a large impact on the balance between competitive magnetic interactions and, as a result, on the stabilization of the magnetic structures and ferroelectric phase at low temperatures. Low-lying electromagnon excitation is activated in the cycloidal modulated antiferromagnetic and ferroelectric phase in $\mathrm{TbMn}{\mathrm{O}}_{3}$, while it is observed up to ${T}_{N}$ in the Fe-substituted compounds, pointing at different mechanisms for static and dynamic magnetoelectric coupling. A second electrically active excitation near 40 $\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$ is explained by means of ${\mathrm{Tb}}^{3+}$ crystal-field effects. This excitation is observed up to room temperature, and exhibits a remarkable $15\phantom{\rule{4pt}{0ex}}\text{c}{\mathrm{m}}^{\ensuremath{-}1}$ downshift on cooling in Fe-substituted compounds. Both electromagnon and crystal-field excitations are found to be coupled to the polar phonons with frequencies up to 250 $\mathrm{c}{\mathrm{m}}^{\ensuremath{-}1}$. Raman spectroscopy reveals a spin-phonon coupling below ${T}_{N}$ in pure $\mathrm{TbMn}{\mathrm{O}}_{3}$, but the temperature where the coupling starts to be relevant increases with Fe concentration and reaches 100 K in $\mathrm{Tb}{\mathrm{Mn}}_{0.96}{\mathrm{Fe}}_{0.04}{\mathrm{O}}_{3}$. The anomalies in the $T$ dependence of magnetic susceptibility above ${T}_{N}$ are well accounted for by spin-phonon coupling and crystal-field excitation, coupled to oxygen motions.

Terahertz pulse induced second harmonic generation and Kerr effect in the quantum paraelectric KTaO3

We present a joint experimental and computational study of second harmonic generation and Kerr effect induced by intense terahertz electric fields in the quantum paraelectric material ${\mathrm{KTaO}}_{3}$. The single-cycle terahertz (THz) electric pulses induce the free induction decay of the polar soft phonon mode and a ferroelectric polarization response that lasts for several picoseconds in both experiment and computation. We observe a much longer-lasting (43-ps) transient Kerr effect that follows the THz excitation. We explain the disparity in the relaxation times between the THz-induced second harmonic generation and the Kerr effect by the presence of the polar nanoregions intrinsic to ${\mathrm{KTaO}}_{3}$. The origin of the slow THz Kerr effect dynamics is not presently understood. We speculate that it may be associated with the rotational motion of polar nanoregions due to the material's proximity to the ferroelectric phase transition.

Carrier mobility and high-field velocity in 2D transition metal dichalcogenides: degeneracy and screening

The effect of degeneracy and the impact of free-carrier screening on a low-field mobility and a high-field drift velocity in MoS2 and WS2 are explored using an in-house ensemble Monte Carlo simulator. Electron low field mobility increases to for MoS2 and to for WS2 when temperature decreases to and carrier concentration is around . In the case of holes, best mobility values were and , reached at similar temperature and carrier concentration conditions while at room temperature these fall to and for MoS2 and WS2, respectively. The carrier screening effect plays a major role at low fields, and low and intermediate temperatures, where a combination of large occupancy of primary valleys and carrier–phonon interactions dominated by relatively low energy exchange processes results in an enhanced screening of intrinsic scattering. For electrons, degeneracy yields to transport in secondary valleys, which plays an important role in the decrease of the low field mobility at high concentrations and/or at room temperature. The high-field drift velocity is not much affected by carrier screening because of an increased carrier scattering with surface optical polar phonons, favouring larger phonon wavevector interactions with small dielectric function values.

ElecTra code: Full-band electronic transport properties of materials

This paper introduces ElecTra, an open-source code which solves the linearized Boltzmann transport equation in the relaxation time approximation for charge carriers in a full-band electronic structure of arbitrary complexity, including their energy, momentum, and band-index dependence. ElecTra stands for ‘ELECtronic TRAnsport’ and computes the electronic and thermoelectric transport coefficients electrical conductivity, Seebeck coefficient, electronic thermal conductivity, and mobility, for semiconductor materials, for both unipolar and bipolar (small bandgap) materials. The code uses computed full-bands and relevant scattering parameters as inputs and considers single crystal materials in 3D and 2D. The present version of the code (v1) considers: i) elastic scattering with acoustic phonons and inelastic scattering with non-polar optical phonons in the deformation potential approximation, ii) inelastic scattering with polar phonons, iii) scattering with ionized dopants, and iv) alloy scattering. The user is given the option of intra- and inter-band scattering considerations. The simulation output also includes relevant relaxation times and mean-free-paths. The transport quantities are computed as a function of Fermi level position, doping density, and temperature. ElecTra can interface with any DFT code which saves the electronic structure in the ‘.bxsf’ format. In this paper ElecTra is validated against ideal electronic transport situations of known analytical solutions, existing codes employing the constant relaxation time approximation, as well as experimentally well-assessed materials such as Si, Ge, SiGe, and GaAs. Program summaryProgram title: ElecTra – Electronic Transport simulation labCPC Library link to program files:https://doi.org/10.17632/ycgx2fjzb6.1Licensing provisions: GPLv3Programming Language: MATLAB®Nature of the problem: computing the electronic and thermoelectric charge transport coefficients of materials with arbitrary complex full-band electronic structures, considering the carrier energy-, momentum-, and band-dependence of the scattering rates.Solution method: Semiclassical Linearized Boltzmann transport equation, with electronic structures (DFT or analytical) as input, formed into constant-energy surfaces, with scattering rates evaluated using Fermi's Golden Rule.Additional comments including restrictions and unusual features:•Programming interface: any DFT code which saves data in the ‘.bxsf’ format.•RAM: a case study for a half-Heusler bandstructure on a 51×51×51k-mesh, 2 Gb per processor is needed•Running time: for the example above, depending on the number and complexity of the scattering mechanisms and the number of simulated Fermi levels and temperatures considered, the time needed varies from ∼ 1 hour on a desktop PC or laptop (light simulations), to 5-10 hours on an HPC with 30-45 cores (heavy simulations). Using the constant relaxation time and constant mean-free-path approximations on a desktop PC or laptop, the running time is of the order of minutes.

Prediction of hot zone-center optical phonons in laser-irradiated molybdenum disulfide with a semiconductor multitemperature model

A previous multitemperature model (MTM) resolving phonon temperatures at the polarization level and measurements have uncovered remarkable nonequilibrium among different phonon polarizations in laser-irradiated graphene and metals. Here, we develop a semiconductor-specific MTM (SC-MTM) by including electron-hole pair generation, diffusion, and recombination, and show that a phonon polarization-level model does not yield observable polarization-based nonequilibrium in laser-irradiated molybdenum disulfide (${\mathrm{MoS}}_{2}$). In contrast, appreciable nonequilibrium is predicted between zone-center optical phonons and the other modes. The momentum-based nonequilibrium ratio is found to increase with decreasing laser spot size and interaction with a substrate. This finding is relevant to the understanding of the energy relaxation process in two-dimensional optoelectronic devices and Raman measurements of thermal transport.

Phonon polarization deformation in graphene induced by substrate coupling strengths

Displacement in the Raman shift of conventional Raman spectroscopy usually includes an increase in the number of material layers or a strain variation. To distinguish them, polarization-resolved Raman spectroscopy provides an additional degree of freedom to resolve it. In this work, strained graphene induced by different substrates on G band and 2D band phonon modes is studied by polarization-resolved Raman spectroscopy and verified by numerical analysis using Raman tensors and optical Jones calculus. For the strained graphene case, polarization properties of scattered light are obviously different from that in the case of unstrained graphene. Deformation of phonon polarization is seen to originate from different strengths of substrate coupling. This research provides an efficient quantitative method to explore any distortion of strain anisotropy in two-dimensional materials, which is important for the development of straintronics in the future.

Can the ferroelectric soft mode trigger an antiferromagnetic phase transition?

Type-II multiferroics, where spin interactions induce a ferroelectric polarization, are interesting for new device functionalities due to large magnetoelectric coupling. We report on a new type of multiferroicity in the quadruple-perovskite BiMn3Cr4O12, where an antiferromagnetic phase is induced by the structural change at the ferroelectric phase transition. The displacive nature of the ferroelectric phase transition at 125 K, with a crossover to an order-disorder mechanism, is evidenced by a polar soft phonon in the THz range and a central mode. Dielectric and pyroelectric studies show that the ferroelectric critical temperature corresponds to the previously reported Néel temperature of the Cr3+ spins. An increase in ferroelectric polarization is observed below 48 K, coinciding with the Néel temperature of the Mn3+ spins. This increase in polarization is attributed to an enhanced magnetoelectric coupling, as no change in the crystal symmetry below 48 K is detected from infrared and Raman spectra.

Hierarchical Superhydrophobic Poly(vinylidene fluoride-co-hexafluoropropylene) Membrane with a Bead (SiO2 Nanoparticles)-on-String (Nanofibers) Structure for All-Day Passive Radiative Cooling.

Passive all-day radiative cooling has been proposed as a promising pathway to cool objects by reflecting sunlight and dissipating heat to the cold outer space through atmospheric windows without any energy consumption. However, most of the existing radiative coolers are susceptible to contamination, which may decrease the optical property and gradually degrade the outdoor radiative cooling performance. Herein, we prepared a hierarchical superhydrophobic fluorinated-SiO2/PVDF-HFP nanofiber membrane by a facile and scalable technology of electrospinning and electrostatic spraying. Due to the synergistic effects of the efficient scattering of nanofibers/micropores and the phonon polarization resonance of SiO2 nanoparticles, the membrane achieves up to 97.8% average solar reflectance and 96.6% average atmospheric window emittance. The membrane displays sub-ambient temperature drop values of 11.5 and 4.1 °C in daytime and nighttime outdoor conditions, respectively, exhibiting remarkable radiative cooling performance. Importantly, the unique bead (SiO2 nanoparticles)-on-string (nanofibers) structure forms hierarchical roughness that endows the surface with a superior self-cleaning property. In addition, the obtained membrane exhibits remarkable flexibility and mechanical stability, which are of significant importance in cooling vehicles, buildings, and large-scale equipment.

Electric field control of electromagnon frequency in multiferroics

Electromagnons, which are coupled polar and magnetic excitations in magnetoelectric materials, are of large interest for electronic and computing technological devices. Using molecular dynamics simulations based on an ab initio effective Hamiltonian, we predict that the frequency of several electromagnons can be tuned by the application of electric fields in the model multiferroic ${\mathrm{BiFeO}}_{3}$, with this frequency either increasing or decreasing depending on the selected electromagnon. In particular, we show that the frequency of electromagnons localized at ferroelectric domain walls can be tuned over a 200 GHz range by realistic dc electric fields. We interpret the realized frequency increase (decrease) by local hardening (softening) of the associated polar phonons which couples to the applied electric field. The increase versus decrease in the electromagnon frequency is further found to be correlated with the real-space localization of such phonons.

Terahertz Magnetic and Lattice Excitations in van der Waals Ferromagnet VI3.

We use the synergy of infrared, terahertz, and Raman spectroscopies with DFT calculations to shed light on the magnetic and lattice properties of VI3. The structural transition at TS1 = 79 K is accompanied by a large splitting of polar phonon modes. Below TS1, strong ferromagnetic fluctuations are observed. The variations of phonon frequencies at 55 K induced by magnetoelastic coupling enhanced by spin-orbit interaction indicate the proximity of long-range ferromagnetic order. Below TC = 50 K, two Raman modes simultaneously appear and show dramatic softening in the narrow interval around the temperature TS2 of the second structural transition associated with the order-order magnetic phase transition. Below TS2, a magnon in the THz range appears in Raman spectra. The THz magnon observed in VI3 indicates the application potential of 2D van der Waals ferromagnets in ultrafast THz spintronics, which has previously been considered the exclusive domain of antiferromagnets.

Role of phonon mode in the enhancement of ferroelectric polarization in a perovskite-based eco-friendly functional material

We report here the role of component freezing of three-dimensional polar () phonon mode corresponding to the center of cubic Brillouin zone in tuning the structure-property correlations of a scientifically enriched and technologically important barium-titanate–based eco-friendly functional material (Ba0.92Ca0.08)(Zr0.05Ti0.95−x Sn x )O3; BCZTSnx synthesized via solid-state reaction method. The combined X-ray diffraction, Raman spectroscopic analysis, and temperature-dependent dielectric studies have revealed the presence of several crystallographic phase transitions with coexisting phases, viz., , as a function of Sn(x) content. These crystallographic phases, viz., P4mm, Amm2, and R3m results due to freezing of the component(s) of phonon mode (belonging to space group), with the respective order parameter directions (0,0,a), (a,a,0), and (a,a,a) leading to ferroelectric polarization along , and directions, respectively. The ceramic composition corresponding to exhibits a significant reduction in the coercive field (E c ) and an enhancement in ferroelectric polarization (P r ) in comparison to , inferred from PE loop measurements. The enhancement in ferroelectric polarization at has been attributed to the inter-ferroelectric three-phase coexistence around this composition and significantly enhanced amplitudes of ferroelectric phonon modes corresponding to orthorhombic and rhombohedral phases, calculated using the symmetry mode analysis technique. The existence of a high ferroelectric polarization and low coercive field may lead to composition as an eco-friendly candidate for ferroelectric memory devices.

Renormalization of excitonic properties by polar phonons.

We employ quasiparticle path integral molecular dynamics to study how the excitonic properties of model semiconductors are altered by electron-phonon coupling. We describe ways within a path integral representation of the system to evaluate the renormalized mass, binding energy, and radiative recombination rate of excitons in the presence of a fluctuating lattice. To illustrate this approach, we consider Fröhlich-type electron-phonon interactions and employ an imaginary time influence functional to incorporate phonon-induced effects nonperturbatively. The effective mass and binding energies are compared with perturbative and variational approaches, which provide qualitatively consistent trends. We evaluate electron-hole recombination rates as mediated through both trap-assisted and bimolecular processes, developing a consistent statistical mechanical approach valid in the reaction limited regime. These calculations demonstrate how phonons screen electron-hole interactions, generically reducing exciton binding energies and increasing their radiative lifetimes.

Band versus Polaron: Charge Transport in Antimony Chalcogenides.

Antimony sulfide (Sb2S3) and selenide (Sb2Se3) are emerging earth-abundant absorbers for photovoltaic applications. Solar cell performance depends strongly on charge-carrier transport properties, but these remain poorly understood in Sb2X3 (X = S, Se). Here we report band-like transport in Sb2X3, determined by investigating the electron–lattice interaction and theoretical limits of carrier mobility using first-principles density functional theory and Boltzmann transport calculations. We demonstrate that transport in Sb2X3 is governed by large polarons with moderate Fröhlich coupling constants (α ≈ 2), large polaron radii (extending over several unit cells), and high carrier mobility (an isotropic average of >10 cm2 V–1 s–1 for both electrons and holes). The room-temperature mobility is intrinsically limited by scattering from polar phonon modes and is further reduced in highly defective samples. Our study confirms that the performance of Sb2X3 solar cells is not limited by intrinsic self-trapping.

Systematic search of the rotation-compatible polar phases in perovskite oxides: A first-principles study

In many perovskite oxides, ferroelectricity is intimately related to octahedral rotation patterns, which can suppress or enhance polar distortions. Using first-principles density functional theory, we investigate the relation between octahedral rotation patterns and polar instability. Based on the rotation patterns commonly observed in perovskite oxides, we present a workflow that allows to systematically and efficiently search for the unstable polar phonon modes and identify metastable polar structures. We apply the workflow to investigate rotation-pattern-dependent polar phases of CaSnO3 and find metastable polar structures by changing rotation patterns. Further investigation of the polar R3c structures shows sizable polarization comparable to the conventional ferroelectrics. We discuss substrate materials having the potential to stabilize the polar structure. Our work provides an efficient way to identify new polar phases by changing the octahedral rotation patterns, which will be useful to design new functional materials in the thin-film/substrate configuration utilizing interfacial coupling.

Mutual spin-phonon driving effects and phonon eigenvector renormalization in nickel (II) oxide

The physics of mutual interaction of phonon quasiparticles with electronic spin degrees of freedom, leading to unusual transport phenomena of spin and heat, has been a subject of continuing interests for decades. Despite its pivotal role in transport processes, the effect of spin-phonon coupling on the phonon system, especially acoustic phonon properties, has so far been elusive. By means of inelastic neutron scattering and first-principles calculations, anomalous scattering spectral intensity from acoustic phonons was identified in the exemplary collinear antiferromagnetic nickel (II) oxide, unveiling strong spin-lattice correlations that renormalize the polarization of acoustic phonon. In particular, a clear magnetic scattering signature of the measured neutron scattering intensity from acoustic phonons is demonstrated by its momentum transfer and temperature dependences. The anomalous scattering intensity is successfully modeled with a modified magneto-vibrational scattering cross-section, suggesting the presence of spin precession driven by phonon. The renormalization of phonon eigenvector is indicated by the observed "geometry-forbidden" neutron scattering intensity from transverse acoustic phonon. Importantly, the eigenvector renormalization cannot be explained by magnetostriction but instead, it could result from the coupling between phonon and local magnetization of ions.

Inclusion of infrared dielectric screening in the GW method from polaron energies to charge mobilities

We introduce in the many-body GW scheme the modulation of the screened Coulomb interaction W arising from the macroscopic dielectric response in the infrared. We derive expressions for the polaron binding energies, the renormalization of the effective masses and for the electron and hole relaxation times. Electron and hole mobilities are then obtained from the incorporation of appropriate scattering rules. Zinc-blende GaN and orthorhombic MAPbI3 are used as test beds finding fair agreement with results from rigorous electron-phonon coupling approaches. Although limited to polar phonons, our method has a negligible computational cost.