Experimental Phonon Research Articles

Temperature-dependent lattice dynamics in iridium

The characterization of simple elemental systems is key to benchmarking first-principles modeling of electronic and vibrational behaviors of materials. A large body of literature has been built for most elemental systems in the periodic table. However, surprisingly little neutron work has been performed to probe the vibrational properties of iridium, likely due to its large neutron absorption cross section. Nonetheless, iridium is of significant scientific and technological interest due to large relativistic electron effects and electron-phonon coupling, particularly in strongly correlated iridate compounds. Here, we report temperature-dependent inelastic neutron scattering measurements of the vibrational properties of iridium, from which we extract key thermodynamic properties. To overcome the challenge of the large neutron absorption of iridium, we developed a simple postprocessing correction procedure. The measured densities of phonon states compare well with quasiharmonic density functional theory calculations, although the obtained experimental phonon Gr\uneisen parameters are much larger than expected, reaching as high as $\ensuremath{\gamma}=4.5$, indicating substantial anharmonicity.

Phononic bandgap and phonon anomalies in HfN and HfN/ScN metal/semiconductor superlattices measured with inelastic x-ray scattering

Epitaxial metal/semiconductor superlattice heterostructures with lattice-matched abrupt interfaces and suitable Schottky barrier heights are attractive for thermionic energy conversion, hot electron-based solar energy conversion, and optical hyperbolic metamaterials. HfN/ScN is one of the earliest demonstrations of epitaxial single-crystalline metal/semiconductor heterostructures and has attracted significant interest in recent years to harness its excellent properties in device applications. Although the understanding of the mechanism of thermal transport in HfN/ScN superlattices is extremely important for their practical applications, not much attention has been devoted to measuring their phonon dispersion and related properties. In this Letter, we employ non-resonant meV-resolution inelastic x-ray scattering to determine the momentum-dependent phonon modes in epitaxial metallic HfN and lattice-matched HfN/ScN metal/semiconductor superlattices. HfN exhibits a large phononic bandgap (∼40 meV) and Kohn anomaly in the longitudinal and transverse acoustic phonon modes at q ∼ 0.73 along the [100] and [110] directions of the Brillouin zone due to the nesting of the Fermi surface by the wave vector (q). The in-plane [100] acoustic phonon dispersion of the HfN/ScN superlattices is found to be dominated by the HfN phonons, while the optical phonons exhibit both ScN and HfN characteristics. First-principles density functional perturbation theory modeling is performed to explain the experimental phonon spectra, and temperature-dependent thermal conductivity is measured using a pump-probe spectroscopic technique. These results will help understand the phonons in HfN and HfN/ScN metal/semiconductor superlattices for thermionic energy conversion.

Impact of structural complexity and disorder on lattice dynamics and thermal conductivity in the o- Al13Co4 phase

Combining inelastic neutron and x-ray scattering with atomic scale simulation, we report on a comprehensive study of the lattice dynamics and its relationship with the low thermal conductivity of the o-${\mathrm{Al}}_{13}{\mathrm{Co}}_{4}$ phase, a periodic approximant (about 100 atoms per cell) to a decagonal quasicrystal. The obtained experimental data, phonon lifetimes, and temperature-independent lattice thermal conductivity can only be fully described by molecular dynamics simulations, using oscillating pair potential, when the disorder of 12 Al sites is properly taken into account. Our results pave the way for a detailed understanding of materials where structural complexity and local disorder are at play.

Structural and Lattice-Dynamical Properties of Tb2O3 under Compression: A Comparative Study with Rare Earth and Related Sesquioxides.

We report a joint experimental and theoretical investigation of the high pressure structural and vibrational properties of terbium sesquioxide (Tb2O3). Powder X-ray diffraction and Raman scattering measurements show that cubic Ia3̅ (C-type) Tb2O3 undergoes two phase transitions up to 25 GPa. We observe a first irreversible reconstructive transition to the monoclinic C2/m (B-type) phase at ∼7 GPa and a subsequent reversible displacive transition from the monoclinic to the trigonal P3̅m1 (A-type) phase at ∼12 GPa. Thus, Tb2O3 is found to follow the well-known C → B → A phase transition sequence found in other cubic rare earth sesquioxides with cations of larger atomic mass than Tb. Our ab initio theoretical calculations predict phase transition pressures and bulk moduli for the three phases in rather good agreement with experimental results. Moreover, Raman-active modes of the three phases have been monitored as a function of pressure, while lattice-dynamics calculations have allowed us to confirm the assignment of the experimental phonon modes in the C- and A-type phases as well as to make a tentative assignment of the symmetry of most vibrational modes in the B-type phase. Finally, we extract the bulk moduli and the Raman-active mode frequencies together with their pressure coefficients for the three phases of Tb2O3. These results are thoroughly compared and discussed in relation to those reported for rare earth and other related sesquioxides as well as with new calculations for selected sesquioxides. It is concluded that the evolution of the volume and bulk modulus of all the three phases of these technologically relevant compounds exhibit a nearly linear trend with respect to the third power of the ionic radii of the cations and that the values of the bulk moduli for the three phases depend on the filling of the f orbitals.

Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161 Dy Nuclear Resonance Vibrational Spectroscopy.

Synchrotron‐based nuclear resonance vibrational spectroscopy (NRVS) using the Mössbauer isotope 161Dy has been employed for the first time to study the vibrational properties of a single‐molecule magnet (SMM) incorporating DyIII, namely [Dy(Cy3PO)2(H2O)5]Br3⋅2 (Cy3PO)⋅2 H2O ⋅2 EtOH. The experimental partial phonon density of states (pDOS), which includes all vibrational modes involving a displacement of the DyIII ion, was reproduced by means of simulations using density functional theory (DFT), enabling the assignment of all intramolecular vibrational modes. This study proves that 161Dy NRVS is a powerful experimental tool with significant potential to help to clarify the role of phonons in SMMs.

Evaluating Computational Shortcuts in Supercell-Based Phonon Calculations of Molecular Crystals: The Instructive Case of Naphthalene.

Phonons crucially impact a variety of properties of organic semiconductor materials. For instance, charge- and heat transport depend on low-frequency phonons, while for other properties, such as the free energy, especially high-frequency phonons count. For all these quantities one needs to know the entire phonon band structure, whose simulation becomes exceedingly expensive for more complex systems when using methods like dispersion-corrected density functional theory (DFT). Therefore, in the present contribution we evaluate the performance of more approximate methodologies, including density functional tight binding (DFTB) and a pool of force fields (FF) of varying complexity and sophistication. Beyond merely comparing phonon band structures, we also critically evaluate to what extent derived quantities, like temperature-dependent heat capacities, mean squared thermal displacements, and temperature-dependent free energies are impacted by shortcomings in the description of the phonon bands. As a benchmark system, we choose (deuterated) naphthalene, as the only organic semiconductor material for which to date experimental phonon band structures are available in the literature. Overall, the best performance among the approximate methodologies is observed for a system-specifically parametrized second-generation force field. Interestingly, in the low-frequency regime also force fields with a rather simplistic model for the bonding interactions (like the General Amber Force Field) perform rather well. As far as the tested DFTB parametrization is concerned, we obtain a significant underestimation of the unit-cell volume resulting in a pronounced overestimation of the phonon energies in the low-frequency region. This cannot be mended by relying on the DFT-calculated unit cell, since with this unit cell the DFTB phonon frequencies significantly underestimate the experiments.

Lattice dynamics in FeSe via inelastic x-ray scattering and first-principles calculations

We report an inelastic x-ray scattering investigation of phonons in FeSe superconductor. Comparing the experimental phonon dispersion with density functional theory (DFT) calculations in the non-magnetic state, we found a significant disagreement between them. Improved overall agreement was obtained by allowing for spin-polarization in the DFT calculations, despite the absence of magnetic order in the experiment. This calculation gives a realistic approximation, at DFT level, of the disordered paramagnetic state of FeSe, in which strong spin fluctuations are present.

Measurement of the double-differential neutron cross section of UO2 from room temperature to hot full power conditions

Experimental phonon densities of states of UO2 have been deduced from double-differential neutron scattering data measured at 300 K, 600 K and 900 K using the IN6 time-of-flight spectrometer of the Institute Laue-langevin (ILL). The comparison with ab intio phonon spectra obtained at the North Caroline South University from first-principle calculations confirms that harmonic vibrations of the atoms cannot accurately reproduce the phonon broadening related to the oxygen atoms.

Phonon dispersion of Mo-stabilized γ-U measured using inelastic x-ray scattering.

We have measured the room-temperature phonon spectrum of Mo-stabilized γ-U. The dispersion curves show unusual softening near the H point, q = [1/2, 1/2, 1/2], which may derive from the metastability of the γ-U phase or from strong electron-phonon coupling. Near the zone center, the dispersion curves agree well with theory, though significant differences are observed away from the zone center. The experimental phonon density of states is shifted to higher energy compared to theory and high-temperature neutron scattering. The elastic constants of γ-UMo are similar to those of body-centered cubic elemental metals.

Possible mechanism for superconductivity in doped SrTiO3

The soft ferro-electric phonon in SrTiO3 observed with optical spectroscopy has an extraordinary strong spectral weight which is much stronger than expected in the limit of a perfectly ionic compound. The "charged phonon" in SrTiO3 is caused by the close-to-covalent character of the Ti-O ionic bond and implies a strong coupling between the soft ferro-electric phonon and the inter band transitions across the 3 eV gap of SrTiO3. We demonstrate that this coupling leads, in addition to the charged phonon effect, to a pairing interaction involving the exchange of two transverse optical phonons. This process owes its relevance to the strong electron-phonon coupling and to the fact that the interaction mediated by a single transverse optical phonon vanishes at low electron density. We use the experimental soft phonon spectral weight to calculate the strength of the bi-phonon mediated pairing interaction in the electron doped material and show that it is of the correct magnitude when compared to the experimental value of the superconducting critical temperature.

Toward a better thermal scattering law of (C5O2H8)n: Inelastic neutron scattering and oClimax + NJOY2016

With the advancements in technology (both experimental and computational) the determination of the“true” experimental phonon spectrum became more accessible. In this work a methodology for producing thermal scattering libraries from the experimental data (namely the DFT + oClimax method) for lucite (C5O2H8)n is discussed. Double differential scattering cross section (DDSCS) experiments were performed at the Spallation Neutron Source of Oak Ridge National Laboratory (SNS ORNL). New scattering kernel evaluations, based on the phonon spectrum for (C5O2H8)n,were created using oClimax and NJOY2016 codes. In order to compare and asses the performance of the newly created library, the experimental setup was simulated using MCNP6.1. Compared to the current ENDF/B-VIII.0, the resulting RPI (C5O2H8)n library improved the calculation of both double differential scattering and total scattering cross sections. A set of criticality benchmarks containing (C5O2H8)n from HEU-MET-THERM resulted in an overall improved calculation of Keff. The DFT + oClimax method is shown to be the most comprehensive method for analysis of moderator materials, due to the fact that it can be verified against all data measured at VISION, ARCS and SEQUOIA neutron spectrometers at SNS ORNL, and experimental total scattering cross section measurements. This method also provides a new technique for calculating any phonon spectrum-related quantities such as scattering law kernel, specific heat capacity, thermal conductivity, etc. for any solid state material.

Non-Markovian features in semiconductor quantum optics: quantifying the role of phonons in experiment and theory

AbstractWe discuss phonon-induced non-Markovian and Markovian features in QD-based quantum nanooptics. We cover lineshapes in linear absorption experiments, phonon-induced incoherence in the Heitler regime, and memory correlations in two-photon coherences. To qualitatively and quantitatively understand the underlying physics, we present several theoretical models that capture the non-Markovian properties of the electron–phonon interaction accurately in different regimes. Examples are the Heisenberg equation of motion approach, the polaron master equation, and Liouville propagator techniques in the independent boson limit and beyond via the path integral method. Phenomenological modeling overestimates typically the dephasing due to the finite memory kernel of phonons and we give instructive examples of phonon-mediated coherence such as phonon-dressed anticrossings in Mollow physics, robust quantum state preparation, cavity feeding, and the stabilization of the collapse and revival phenomenon in the strong coupling limit of cavity quantum electrodynamics.

Experimental Phonon Dispersion and Lifetimes of Tetragonal CH3NH3PbI3 Perovskite Crystals.

Hybrid organic-inorganic perovskites were reported to have ultralow thermal conductivity in recent studies. In this Letter, we report the first experimental phonon dispersion and lifetimes of tetragonal CH3NH3PbI3 single crystals at both 200 and 300 K by high-energy resolution inelastic X-ray scattering, which enables a thorough understanding of the underlying mechanisms for the ultralow thermal conductivity. Notably, we observed unusual and significant phonon dips along the [100] and [110] directions at both temperatures. The ultralow thermal conductivity can be attributed to small group velocities due to ultrasoft acoustic modes and short phonon lifetimes originating from the strong acoustic-optical coupling. We further provided the structural origins for these peculiar phonon features. Moreover, our results and interpretation are consistent with the reported temperature-dependent trend for thermal conductivity of CH3NH3PbI3. Our work offers critical guidelines for accelerating the design and discovery of novel hybrid materials for energy applications including photovoltaics and thermoelectrics.

Recipe for Dirac Phonon States with a Quantized Valley Berry Phase in Two-Dimensional Hexagonal Lattices.

The topological quantum states in two-dimensional (2D) materials are fascinating subjects of research, which usually highlight electron-related systems. In this work, we present a recipe that leads to Dirac phonon states with a quantized valley Berry phase in 2D hexagonal lattices by first-principles calculations. We show that candidates possessing the 3-fold rotational symmetry at the corners of the hexagonal Brillouin zone host valley Dirac phonons, which are guaranteed to remain intact with respect to perturbations. We identify that such special topological features populated by Dirac phonons can be realized in various 2D materials. In particular, the monolayer CrI3, an attractive 2D magnetic semiconductor with exotic applications in spintronics, is an ideal platform to investigate nontrivial phonons in experiments. We further confirm that the phonon Berry phase is quantized to ± π at two inequivalent valleys. The phonon edge states terminated at the projection of phonon Dirac cones are clearly visible. This work demonstrates that 2D hexagonal lattices with attractive valley Dirac phonons will extend the knowledge of valley physics, providing wide applications of topological phonons.

Neutron Spectroscopy of the Atomic Dynamics of La2Zr2O7 at Fluorite–Pyrochlore Structural Transformations

The formation of the structural and dynamic properties of La2Zr2O7 in the process of crystallization at the isothermal annealing of initially amorphous precursors obtained by the coprecipitation of corresponding salts has been studied by neutron spectroscopy. The existence of vibrational states characteristic of hydrogen, which is in one or another of the possible chemical states and is incorporated into a solid matrix, has been detected in the spectra of amorphous and fluorite phases. The DFT calculation of the phonon density of states has been performed to analyze the energy structure of experimental phonon spectra for various phases of the La2Zr2O7 compound. The amount of hydrogen in the fluorite phase has been estimated.

Density Functional Theory Prediction of the Second Harmonic Generation and Linear Pockels Effect in Trigonal BaZnO2

Polycrystalline powder of trigonal BaZnO2 has been synthesized and characterized by X-ray diffraction, dielectric measurements, and vibrational spectroscopy (infrared and Raman). These properties have been also calculated using the density functional theory and compared with the experimental ones. The experimental phonon modes have been assigned, and we have revisited the previous theoretical assignment reported in the literature combining the calculated and the experimental data. The dielectric constant has been analyzed by decoupling it into three contributions (electronic, phonon, and strain). The second-order nonlinear susceptibility and the electro-optic response have been predicted as no theoretical or experimental investigations of these optical properties have been previously reported in the literature. The second-order nonlinear optical susceptibility and the electro-optic coefficients of BaZnO2 are predicted to be significantly higher than those reported in α-quartz or α-GeO2. Thus, considering ...

Toward a Reliable Description of the Lattice Vibrations in Organic Molecular Crystals: The Impact of van der Waals Interactions.

This work assesses the reliability of different van der Waals (vdW) methods to describe lattice vibrations of molecular crystals in the framework of density functional theory (DFT). To accomplish this task, calculated and experimental lattice phonon Raman spectra of a pool of organic molecular crystals are compared. We show that the many-body dispersion (MBD@rsSCS) van der Waals method of Ambrosetti et al. and the pairwise method of Grimme et al. (D3-BJ) outperform the other tested approaches (i.e., the D2 method of Grimme, the TS method of Tkatchenko and Scheffler, and the nonlocal functional vdW-DF-optPBE of Klimeš et al.). For the worse-performing approaches the results could not even be fixed by the introduction of scaling parameters, as commonly used for high-energy intramolecular vibrations. Interestingly, when using the experimentally determined unit cell parameters, DFT calculations using the PBE functional without corrections for long-range vdW interactions provide spectra of similar accuracy as the MBD@rsSCS and D3-BJ simulations.

High-throughput density-functional perturbation theory phonons for inorganic materials

The knowledge of the vibrational properties of a material is of key importance to understand physical phenomena such as thermal conductivity, superconductivity, and ferroelectricity among others. However, detailed experimental phonon spectra are available only for a limited number of materials, which hinders the large-scale analysis of vibrational properties and their derived quantities. In this work, we perform ab initio calculations of the full phonon dispersion and vibrational density of states for 1521 semiconductor compounds in the harmonic approximation based on density functional perturbation theory. The data is collected along with derived dielectric and thermodynamic properties. We present the procedure used to obtain the results, the details of the provided database and a validation based on the comparison with experimental data.

Low-temperature heat capacities of Y2GaSbO7 and R2FeSbO7 (R = Y, Dy) pyrochlore compounds: Quasi-harmonic phonons calculation

Abstract Heat capacities at constant pressure, C°p,m, of three polycrystalline pyrochlore compounds, Y2GaSbO7, Y2FeSbO7 and Dy2FeSbO7, have been measured in the temperature range up to 300 K. Temperature variation of the Debye temperatures, θD(T), for Y2GaSbO7 is determined using a quasi-harmonic expression of Debye lattice heat capacity, which has been employed to estimate the phonon heat capacity, Cph, for the other two compounds, e.g., Y2FeSbO7 and Dy2FeSbO7. Theoretical analysis using phonon model shows that the acoustic and optic phonons contribute significantly to the thermodynamic properties. The effect of anharmonicity in the lattice vibrations at higher temperature (above 220 K) was also considered for Y2GaSbO7. The Cph of Y2FeSbO7, calculated using the experimental infra-red and Raman phonon spectra, are in good agreement with the measured heat capacity data and thus provides a good taste of understanding to the molecular dynamics in the pyrochlore structure. The Schottky heat capacity has been deduced from the crystal-field level scheme of Dy3+ ions and added to the Cph of Dy2FeSbO7 to estimate the total heat capacity, which is in reasonable agreement with the experimental heat capacity, C°p,m, of Dy2FeSbO7. From the integrated heat capacity data, the entropy and enthalpy relative to absolute zero have been generated for Y2GaSbO7 and Y2FeSbO7. The room-temperature thermal conductivity was estimated to be ∼2 W⋅m−1⋅K−1 for Y2GaSbO7 implying that Y2GaSbO7 could be a potential candidate for thermal barrier coating material.

Lattice dynamics of ultrathin FeSe films on SrTiO3

Charge transfer and electron-phonon coupling (EPC) are proposed to be two important constituents associated with enhanced superconductivity in the single unit cell FeSe films on oxide surfaces. Using high-resolution electron energy loss spectroscopy combined with first-principles calculations, we have explored the lattice dynamics of ultrathin FeSe films grown on SrTiO3. We show that, despite the significant effect from the substrate on the electronic structure and superconductivity of the system, the FeSe phonons in the films are unaffected. The energy dispersion and linewidth associated with the Fe- and Se-derived vibrational modes are thickness- and temperature-independent. Theoretical calculations indicate the crucial role of antiferromagnetic correlation in FeSe to reproduce the experimental phonon dispersion. Importantly, the only detectable change due to the growth of FeSe films is the broadening of the Fuchs-Kliewer (F-K) phonons associated with the lattice vibrations of SrTiO$_3$(001) substrate. If EPC plays any role in the enhancement of film superconductivity, it must be the interfacial coupling between the electrons in FeSe film and the F-K phonons from substrate rather than the phonons of FeSe.