Phonon Origin Research Articles

Phononic origin of the infrared dielectric properties of RE2O3 (RE = Y, Gd, Ho, Lu) compounds

Understanding the phononic origin of the infrared (IR) dielectric properties of yttria (Y2O3) and other rare-earth sesquioxides (RE2O3) is a fundamental task in the search of appropriate RE2O3 materials that serve particular IR optical applications. We herein investigate the IR dielectric properties of RE2O3 (RE = Y, Gd, Ho, Lu) using density functional theory-based phonon calculations and Lorentz oscillator model. The abundant IR-active optical phonon modes that are available for effective absorption of photons result in high reflectance of RE2O3, among which four IR-active modes originated from large distortions of REO6 octahedra are found to contribute dominantly to the phonon dielectric constants. Particularly, the present calculation method by considering one-phonon absorption process is demonstrated with good reliability in predicting the IR dielectric parameters of RE2O3 at the far-IR as well as the vicinity of mid-IR region, and the potential cutoff frequency/wavelength of its applicability is disclosed as characterized by the maximum frequency of IR-active longitudinal phonon modes. The results deepen the understanding on IR dielectric properties of RE2O3, and aid the computational design of materials with appropriate IR properties.

Metavalent Bonding-Mediated Dual 6s2 Lone Pair Expression Leads to Intrinsic Lattice Shearing in n-Type TlBiSe2.

Metavalent bonding has attracted immense interest owing to its capacity to impart a distinct property portfolio to materials for advanced functionality. Coupling metavalent bonding to lone pair expression can be an innovative way to propagate lattice anharmonicity from lone pair-induced local symmetry-breaking via the soft p-bonding electrons to achieve long-range phonon dampening in crystalline solids. Motivated by the shared chemical design pool for topological quantum materials and thermoelectrics, we based our studies on a three-dimensional (3D) topological insulator TlBiSe2 that held prospects for 6s2 dual-cation lone pair expression and metavalent bonding to investigate if the proposed hypothesis can deliver a novel thermoelectric material. Herein, we trace the inherent phononic origin of low thermal conductivity in n-type TlBiSe2 to dual 6s2 lone pair-induced intrinsic lattice shearing that strongly suppresses the lattice thermal conductivity to a low value of 1.1-0.4 Wm-1 K-1 between 300 and 715 K. Through synchrotron X-ray pair distribution function and first-principles studies, we have established that TlBiSe2 exists not in a monomorphous R-3m structure but as a distribution of distorted configurations. Via a cooperative movement of the constituent atoms akin to a transverse shearing mode facilitated by metavalent bonding in TlBiSe2, the structure shuttles between various energetically accessible low-symmetry structures. The orbital interactions and ensuing multicentric bonding visualized through Wannier functions augment the long-range transmission of atomic displacement effects in TlBiSe2. With additional point-defect scattering, a κlatt of 0.3 Wm-1 K-1 was achieved in TlBiSeS with a maximum n-type thermoelectric figure of merit (zT) of ∼0.8 at 715 K.

Phononic origin of strain-controlled friction force

Employing fast Fourier transform (FFT) of instantaneous friction and interfacial phonon spectrum, phononic origin of friction between graphene layers, in which one layer suffering different biaxial strain, is disclosed. FFT spectrum indicates washboard frequencies make major contribution to friction. Peak value in FFT spectrum decreases with increase of strain, leading to drop of friction. Density of states for interface atoms proves energy exchange between tip and substrate is conditional on coupling of interfacial vibration frequencies. There is unified phonon spectrum on relative sliding surfaces at zero strain, which can establish effective energy dissipation channels. Once a strain is applied, unified phonon modes are no longer formed, which destroys conditions for establishment of energy dissipation channels and thus hinders energy dissipation.

Phononic origin of structural lubrication

Atomistic mechanisms of frictional energy dissipation have attracted significant attention. However, the dynamics of phonon excitation and dissipation remain elusive for many friction processes. Through systematic fast Fourier transform analyses of the frictional signals as a silicon tip sliding over a graphite surface at different angles and velocities, we experimentally demonstrate that friction mainly excites non-equilibrium phonons at the washboard frequency and its harmonics. Using molecular dynamics simulations, we further disclose the phononic origin of structural lubrication, i.e., the drastic reduction of friction force as the contact angle between two commensurate surfaces changes. In commensurate contacting states, friction excites a large amount of phonons at the washboard frequency and many orders of its harmonics that perfectly match each other in the sliding tip and substrate, while for incommensurate cases, only limited phonons are generated at mismatched washboard frequencies and few low order harmonics in the tip and substrate.

Dynamical Bond Formation in KNi2Se2

AbstractEmphanisis, or the appearance out of nothing, has been used to describe the phenomena of spontaneous atom off‐centering and dipole formation at elevated temperatures in lead chalcogenides. Here, we provide spectroscopic evidence of spontaneous formation of metal‐metal bonds above T∼50 K in the layered metal KNi2Se2. These bonds form zig‐zag chains that lower the local symmetry from tetragonal to monoclinic. Energy‐resolved pair distribution function measurements exclude a pure phonon origin of our observations, and instead imply the existence of extra, slowly fluctuating, Ni−Ni bonds above T=50 K. Density functional theory calculations support this lower symmetry configuration as an instability of tetragonal KNi2Se2. We thus demonstrate that the phenomena of emphansis is not limited to local electric dipole formation, but can also be driven by the formation of metal‐metal bonds.

Titanium Nitride as a Plasmonic Material from Near-Ultraviolet to Very-Long-Wavelength Infrared Range.

Titanium nitride is a well-known conductive ceramic material that has recently experienced resumed attention because of its plasmonic properties comparable to metallic gold and silver. Thus, TiN is an attractive alternative for modern and future photonic applications that require compatibility with the Complementary Metal-Oxide-Semiconductor (CMOS) technology or improved resistance to temperatures or radiation. This work demonstrates that polycrystalline TiNx films sputtered on silicon at room temperature can exhibit plasmonic properties continuously from 400 nm up to 30 μm. The films’ composition, expressed as nitrogen to titanium ratio x and determined in the Secondary Ion Mass Spectroscopy (SIMS) experiment to be in the range of 0.84 to 1.21, is essential for optimizing the plasmonic properties. In the visible range, the dielectric function renders the interband optical transitions. For wavelengths longer than 800 nm, the optical properties of TiNx are well described by the Drude model modified by an additional Lorentz term, which has to be included for part of the samples. The ab initio calculations support the experimental results both in the visible and infra-red ranges; particularly, the existence of a very low energy optical transition is predicted. Some other minor features in the dielectric function observed for the longest wavelengths are suspected to be of phonon origin.

High-quality, temperature-dependent terahertz spectroscopy of single crystalline L-alanine: Experiment and density-functional theory.

For the first time, the terahertz transmittance spectra of l-alanine have been measured using a single crystal. Measurements were obtained over a large temperature range (12-300K) and revealed 18 absorptions between 20 and 250 cm-1. These modes were sharp and symmetric, a feature of single crystals and low temperatures. The spectra were directly compared to those of a powdered pellet sample. Raman spectroscopy and x-ray diffraction were used to confirm the sample's structure and purity. With increasing temperature, all modes exhibit spectral redshift, well described by a Bose-Einstein model, indicating the phonon origin of the absorptions. The exceptions are the 91 and 128 cm-1 modes. The former blueshifts. The latter initially blueshifts but transitions to redshifting. Both behaviors are anomalous. Density-functional theory modeling helped assign all the observed modes.

Phononic soft mode behavior and a strong electronic background across the structural phase transition in the excitonic insulator Ta2NiSe5

Ta$_2$NiSe$_5$ became one of the most investigated candidate materials for hosting an excitonic insulator ground state. Many studies describe the corresponding phase transition as a condensation of excitons breaking a continuous symmetry. This view got challenged recently pointing out the importance of the loss of two mirror symmetries at a structural phase transition that occurs together with the semiconductor-excitonic insulator transition. For such a scenario an unstable optical zone-center phonon at low energy is proposed to drive the transition. Here we report on the experimental observation of such a soft mode behavior using Raman spectroscopy. In addition we find a novel spectral feature, likely of electronic or joint electronic and phononic origin, that is clearly distinct from the lattice dynamics and that becomes dominant at Tc. This suggests a picture of joint structural and electronic order driving the phase transition.

Phonon origin and lattice evolution in charge density wave states.

Metallic transition metal dichalcogenides, such as tantalum diselenide (TaSe2), display quantum correlated phenomena of superconductivity and charge density waves (CDW) at low temperatures. Here, the photophysics of 2H-TaSe2 during CDW transitions is revealed by combining temperature-dependent, low-frequency Raman spectroscopy and density functional theory (DFT). The spectra contain amplitude, phase, and zone-folded modes that are assigned to specific phonons and lattice restructuring predicted by DFT calculations with superb agreement. The non-invasive and efficient optical methodology detailed here demonstrates an essential link between atomic-scale and microscopic quantum phenomena.

Bosonic excitations and electron pairing in an electron-doped cuprate superconductor

Superconductivity originates from the coupling between charge carriers and bosonic excitations of either phononic or electronic origin. Identifying the most relevant pairing glue is a key step towards a clear understanding of the unconventional superconductivity. Here, by applying the ultrafast optical spectroscopy on the electron-doped cuprates La$_{1.9}$Ce$_{0.1}$CuO$_{4\pm\delta}$, we discern a bosonic mode of electronic origin that has the strongest coupling with the charge carriers near $T_c$. We argue that this mode is associated with the two-dimensional antiferromagnetic spin fluctuations, and can fully account for the superconducting pairing. Our work may help to establish a quantitative relation between bosonic excitations and superconducting pairing in electron-doped cuprates, and pave the way for systematic exploration of superconductivity and other collective phenomena in all correlated materials.

Landau Phonon-Roton Theory Revisited for Superfluid ^{4}He and Fermi Gases.

Liquid helium and spin-1/2 cold-atom Fermi gases both exhibit in their superfluid phase two distinct types of excitations, gapless phonons and gapped rotons or fermionic pair-breaking excitations. In the long wavelength limit, revising and extending the theory of Landau and Khalatnikov initially developed for helium [Zh. Exp. Teor. Fiz. 19, 637 (1949)], we obtain universal expressions for three- and four-body couplings among these two types of excitations. We calculate the corresponding phonon damping rates at low temperature and compare them to those of a pure phononic origin in high-pressure liquid helium and in strongly interacting Fermi gases, paving the way to experimental observations.

Thermal Hall Effect of Spin Excitations in a Kagome Magnet.

At low temperatures, the thermal conductivity of spin excitations in a magnetic insulator can exceed that of phonons. However, because they are charge neutral, the spin waves are not expected to display a thermal Hall effect. However, in the kagome lattice, theory predicts that the Berry curvature leads to a thermal Hall conductivity κ(xy). Here we report observation of a large κ(xy) in the kagome magnet Cu(1-3, bdc) which orders magnetically at 1.8 K. The observed κ(xy) undergoes a remarkable sign reversal with changes in temperature or magnetic field, associated with sign alternation of the Chern flux between magnon bands. The close correlation between κ(xy) and κ(xx) firmly precludes a phonon origin for the thermal Hall effect.

Phonon self-energy and origin of anomalous neutron scattering spectra in SnTe and PbTe thermoelectrics.

The anharmonic lattice dynamics of rock-salt thermoelectric compounds SnTe and PbTe are investigated with inelastic neutron scattering (INS) and first-principles calculations. The experiments show that, surprisingly, although SnTe is closer to the ferroelectric instability, phonon spectra in PbTe exhibit a more anharmonic character. This behavior is reproduced in first-principles calculations of the temperature-dependent phonon self-energy. Our simulations reveal how the nesting of phonon dispersions induces prominent features in the self-energy, which account for the measured INS spectra and their temperature dependence. We establish that the phase space for three-phonon scattering processes, combined with the proximity to the lattice instability, is the mechanism determining the complex spectrum of the transverse-optic ferroelectric mode.

Anomalies of transport properties in antiferromagnetic compound

The low-temperature transport properties (resistivity, thermal conductivity, thermoelectric power) are experimentally investigated for the compound YbMn2Sb2. Large Seebeck coefficient and nearly linear temperature dependence of resistivity are obtained. The thermal conductivity is large and has mainly phonon origin. Appreciable anomalies of transport characteristics near the antiferromagnetic transition point are found. Possible influence of pseudo-Kondo scattering is discussed.

Dynamical phenomena in fast sliding nanotube models

The experimentally known fact that coaxial carbon nanotubes can be forced to slide one inside the other stimulated in the past much detailed modelling of the dynamical sliding process. Molecular dynamics simulations of sliding coaxial nanotubes showed the existence of strong frictional peaks when, at large speed, one tube excites the other with a ‘washboard’ frequency that happens to resonate with some intrinsic vibration frequency. At some of these special speeds we discover a striking example of dynamical symmetry breaking taking place at the nanoscale. Even when both nanotubes are perfectly left–right symmetric and nonchiral, precisely in correspondence with the large peaks of sliding friction occurring at a series of critical sliding velocities, a nonzero angular momentum spontaneously appears. A detailed analysis shows that this internal angular momentum is of phonon origin, in particular arising from preferential excitation of a right polarized (or, with equal probability, of a left polarized) outer-tube ‘pseudorotation’ mode, thus spontaneously breaking their exact twofold right–left degeneracy. We present and discuss a detailed analysis of nonlinear continuum equations governing this phenomenon, showing the close similarity of this phenomenon with the well-known rotational instability of a forced string, which takes place under sufficiently strong periodic forcing of the string. We also point out new elements appearing in the present problem which are ‘nano’, in particular the involvement of Umklapp processes and the role of sliding nanofriction.

Phonon Origin of High T c in Superconducting Cuprates

Eliashberg theory (ET), generalized for the account of the peculiar properties of the finite zone width electron-phonon (EP) systems with the non-constant electron density of states, the electron-hole nonequivalence, chemical potential renormalization with doping and frequency, and electron correlations in the vertex function, is used for the study of T c in cuprates. The phonon contribution to the nodal anomalous electron Green function (GF) in cuprates is considered. The pairing on the full width of the electron zone was taken into account, not just on the Fermi surface. It is found that the finite zone width phenomenon in the newly derived Eliashberg equations for the finite zone width EP system together with the abrupt fall of the density of states above the Fermi surface are the crucial factors for the appearance of the high temperature superconductivity phenomenon. It is shown that near the optimal doping in the hole-doped cuprates high T c value is reproduced with the EP interaction constant obtained from tunnel experiments.

Gap modification of atomically thin boron nitride by phonon mediated interactions

A theory is presented for the modification of bandgaps in atomically thin boron nitride (BN) by attractive interactions mediated through phonons in a polarizable substrate, or in the BN plane. Gap equations are solved, and gap enhancements are found to range up to 70% for dimensionless electron-phonon coupling λ =1, indicating that a proportion of the measured BN bandgap may have a phonon origin.

Isotope effect on the superfluid density in conventional and high-temperature superconductors

We investigate the isotope effect on the London penetration depth of a superconductor which measures ${n}_{S}/{m}^{*}$, the ratio of superfluid density to effective mass. We use a simplified model of electrons weakly coupled to a single phonon frequency ${\ensuremath{\omega}}_{E}$, but assume that the energy gap $\ensuremath{\Delta}$ does not have any isotope effect. Nevertheless, we find an isotope effect for ${n}_{S}/{m}^{*}$ which is significant if $\ensuremath{\Delta}$ is sufficiently large that it becomes comparable to ${\ensuremath{\omega}}_{E}$, a regime of interest to high-${T}_{c}$ cuprate superconductors and possibly other families of unconventional superconductors with relatively high ${T}_{c}$. Our model is too simple to describe the cuprates and it gives the wrong sign of the isotope effect when compared with experiment, but it is a proof of principle that the isotope effect exists for ${n}_{S}/{m}^{*}$ in materials where the pairing gap and ${T}_{c}$ are not of phonon origin and have no isotope effect.

Elastic and magnetic effects on the infrared phonon spectra ofMnF2

We measured the temperature dependent infrared reflectivity spectra of MnF2 between 4 K and room temperature. We show that the phonon spectrum undergoes a strong renormalization at TN. The ab-initio calculation we performed on this compound accurately predict the magnitude and the direction of the phonon parameters changes across the antiferromagnetic transition, showing that they are mainly induced by the magnetic order. In this material, we found that the dielectric constant is mostly from phonon origin. The large change in the lattice parameters with temperature seen by X-ray diffraction as well as the A2u phonon softening below TN indicate that magnetic order induced distortions in MnF2 are compatible with the ferroelectric instabilities observed in TiO2, FeF2 and other rutile-type fluorides. This study also shows the anomalous temperature evolution of the lower energy Eu mode in the paramagnetic phase, which can be compared to that of the B1g one seen by Raman spectroscopy in many isostructural materials. This was interpreted as being a precursor of a phase transition from rutile to CaCl2 structure which was observed under pressure in ZnF2.

NaAlSi: Self-doped semimetallic superconductor with free electrons and covalent holes

The layered ternary $sp$ conductor NaAlSi, possessing the iron-pnictide ``111'' crystal structure, superconducts at 7 K. Using density-functional methods, we show that this compound is an intrinsic (self-doped) low-carrier-density semimetal with a number of unusual features. Covalent Al-Si valence bands provide the holes, and free-electronlike $\text{Al}\text{ }3s$ bands, which propagate in the channel between the neighboring Si layers, dip just below the Fermi level to create the electron carriers. The Fermi level (and therefore the superconducting carriers) lies in a narrow and sharp peak within a pseudogap in the density of states. The small peak arises from valence bands which are nearly of pure Si, quasi-two-dimensional, flat, and coupled to Al conduction bands. Isostructural NaAlGe, which is not superconducting above 1.6 K, has almost exactly the same band structure except for one missing piece of small Fermi surface. Certain deformation potentials induced by Si and Na displacements along the $c$ axis are calculated and discussed. It seems likely that the mechanism of pairing is related to that of several other lightly doped two-dimensional nonmagnetic semiconductors (TiNCl, ZrNCl, HfNCl), which is not well understood but apparently not of phonon origin.