Phonon Modes Research Articles

Enhanced hypersensitive (5D0→7F2) transition characteristics of Eu3+ doped β-Ga2O3 microrods

Exploring and realizing the luminescence characteristics of rare earth metal (RE) ions doped gallium oxide (Ga2O3) is crucial for developing optoelectronic device applications. The current research used the solid-state reaction approach to synthesize Ga2O3 microrods doped with various europium (Eu3+) concentrations (0.1, 0.2, 0.3, 0.5, 0.75, and 1 mol). X-ray diffraction (XRD) and Raman spectral analyses confirm the monoclinic structure of β-Ga2O3. The intensity of the Raman phonon modes decreased and a peak shift was observed for Eu:β-Ga2O3. The electron microscopy (SEM, TEM) images depicted a nearly uniform distribution of microrods for undoped and Eu:β-Ga2O3 samples. The interplanar distance (d = 0.290 nm, 0.561 nm, and 0.433 nm), from HR-TEM images, corresponding to (0 0 4), (1 0 0), and (1 0 2) crystallographic orientations confirm the monoclinic structure of β-Ga2O3. The elemental mapping images showed a nearly homogeneous Ga, O, and Eu distribution. The UV–visible diffuse reflectance spectroscopy (UV-DRS) showed a notable reduction in the bandgap as the Eu3+ concentration increased. The emission spectra of Eu: β-Ga2O3 microrods showed a narrow red emission at 612 nm (5D0 → 7F2), which relates to the 5D0 → 7Fj (j = 0, 1, 2, 3) energy level arising from an intra-4f transition of Eu3+ ions upon 394 and 465 nm excitation. The red emission was found to increase with Eu content up to 0.5 mol.%. A quenching of emission due to the multipole–multipole interactions was obtained beyond 0.5 mol.% of Eu. The absolute quantum yield (η) calculated for Eu: β-Ga2O3 (0.5 mol.%) was 3.82 %. The luminescence decay curve using the bi-exponential fit and the average lifetime (τ) of the Eu: β-Ga2O3 (0.5 mol.%) was found to be ∼0.172 ms. CIE chromaticity and correlated color temperature analyses of Eu:β-Ga2O3 microrods yielded a red emission with a superior color purity (93 %). The obtained results suggest that Eu:β-Ga2O3 (0.5 wt.%) microrods could be one of the potential candidates for red light sources.

Janus Monolayer of 1T-TaSSe: A Computational Study.

Materials exhibiting charge density waves are attracting increasing attention owing to their complex physics and potential for applications. In this paper, we present a computational, first principles-based study of the Janus monolayer of 1T-TaSSe transition metal dichalcogenide. We extensively compare the results with those obtained for parent compounds, TaS2 and TaSe2 monolayers, with confirmed presence of 13×13 charge density waves. The structural and electronic properties of the normal (undistorted) phase and distorted phase with 13×13 periodic lattice distortion are discussed. In particular, for a normal phase, the emergence of dipolar moment due to symmetry breaking is demonstrated, and its sensitivity to an external electric field perpendicular to the monolayer is investigated. Moreover, the appearance of imaginary energy phonon modes suggesting structural instability is shown. For the distorted phase, we predict the presence of a flat, weakly dispersive band related to the appearance of charge density waves, similar to the one observed in parent compounds. The results suggest a novel platform for studying charge density waves in two-dimensional transition metal dichalcogenides.

The Rattler-Induced Flat Phonon Modes in KCaBi Driven Lower Thermal Conductivity Compared to KCaSb

The Rattler-Induced Flat Phonon Modes in KCaBi Driven Lower Thermal Conductivity Compared to KCaSb

Optical properties of 4H-SiC and 6H-SiC from infrared to vacuum ultraviolet spectral range ellipsometry (0.05–8.5 eV)

Complex dielectric function (ɛ = ɛ1 + iɛ2) spectra are obtained from reflection mode spectroscopic ellipsometry and unpolarized transmittance measurements for 4H and 6H stacking sequence silicon carbide (SiC) nitrogen-doped single crystals from the infrared (IR) to vacuum ultraviolet (VUV) spectral range. A single parametric model describing ɛ predominately for the ordinary directions is developed over the 0.05–8.5 eV spectral range from analysis of (0001)-oriented back side roughened 4H-SiC and 6H-SiC single crystals with some contribution from the extraordinary direction of 6H-SiC in the IR region. Indirect bandgaps for 4H-SiC and 6H-SiC are found to be 3.30 and 3.03 eV, respectively, and the corresponding direct optical gaps are at 4.46 and 4.42 eV. A model describing the optical response in the IR spectral range is created using a Drude expression and either transverse optical (TO) and longitudinal optical (LO) (TOLO) or Lorentz oscillator models. Free carrier concentration (N) is optically measured to be 3.7 × 1018 and 3.3 × 1018 cm−3 using TOLO and Lorentz oscillator models, respectively, and the corresponding carrier mobility (μ) is 34 and 39 cm2/V s for 4H-SiC. Under the same assumption for 6H-SiC, N is measured to 8 × 1018 cm−3 using either TOLO or Lorentz oscillator models and μ is 9 and 10 cm2/V s using the TOLO and Lorentz oscillator models, respectively, in the ordinary direction and 5 cm2/V s in the extraordinary direction using either model. For 4H-SiC, using the TOLO oscillator model, TO and LO phonon modes are measured at 797.7 and 992.1 cm−1, respectively, and corresponding modes are found at same locations using the Lorentz oscillator model. In 6H-SiC, using the TOLO model, TO modes in ordinary and extraordinary directions are found at 797.7 and 789.7 cm−1, and corresponding modes are at 796.9 and 788.9 cm−1 using the Lorentz oscillator model. The LO modes using the TOLO model are found at 992 and 984 cm−1 in the ordinary and extraordinary directions, respectively, and the same modes in the corresponding direction using the Lorentz oscillator model are located at 975.9 and 967.9 cm−1.

Modulating phononic landscapes: The role of silicon ion bombardment in tailoring Si/Si+Ge and SiO2/SiO2+Ge superlattices for advanced neutron superreflector applications

This study investigates the effects of silicon ion bombardment on the phononic properties of Si/Si+Ge and SiO2/SiO2+Ge superlattices to enhance neutron superreflector technology. Through precise ion implantation and Fourier Transform Infrared Spectroscopy (FTIR), we observed significant alterations in transverse and longitudinal optical phonon modes. The Si/Si+Ge system exhibited notable blueshifts and intensity changes, while SiO2/SiO2+Ge showed increased lattice disorder and peak broadening. These findings highlight ion bombardment's potential to optimize phononic landscapes for improved nuclear reactor safety and efficiency via advanced phonon engineering.

Ultralow Lattice Thermal Conductivity and Large Glass-Like Contribution in Cs3Bi2I6Cl3: Rattling Atoms and p-Band Electrons Driven Dynamic Rotation.

Understanding the origin of ultralow lattice thermal conductivity κL of halide perovskites is of great significance in the energy conversion field. The soft phonon modes and the large anharmonicity corresponding to the dynamic rotation of halogen atoms play an important role in limiting the thermal transport of halide perovskites. The dynamic rotation has long been thought to originate from the electrostatic repulsion of lone pairs around halogen atoms. Here, by studying the layered perovskite Cs3Bi2I6Cl3, it is found that the interaction between the lone pairs contributed by the s bands of halogen atoms is short-range, and the dynamic rotation is really driven by the occupied p-band electrons. It dominates Cs3Bi2I6Cl3 with ultralow κL, < 0.2 W mK-1 at 300 K. Moreover, soft optical phonons are presented ≈1 and 2.2 THz that constitute relatively flat and dense bands due to the rattling Cs and Cl atoms, contributing a large glass-like component to the κL. The results have important implications for understanding the origin of the ultralow κL in halide perovskites and for designing novel perovskites to serve the energy conversionfield.

Coherent Phonon Dynamics in Plasmonic Gold Tetrahedral Nanoparticle Ensembles.

Coherent phonon modes supported by plasmonic nanoparticles offer prospective applications in chemical and biological sensing. Whereas the characterization of these phonon modes often requires single-particle measurements, synthetic routes to narrow size distributions of nanoparticles permit ensemble investigations. Recently, the synthesis of highly monodisperse gold tetrahedral nanoparticles with tunable edge lengths and corner sharpnesses has been developed. Herein, we characterize a size series of these nanoparticles in colloidal dispersion via transient absorption spectroscopy to examine their mechanical and plasmonic responses upon photoexcitation. Oscillations of transient absorption signals are observed in the plasmon resonance and correspond to the lowest-order radial breathing modes of the nanoparticles, the frequencies of which are affected by the edge length and truncation of the corners. Homogeneous quality factor values ranging from 24 to 34 are observed for the oscillations that convey potential utility in mass-sensing and plasmon-exciton-coupling photonics schemes. Finite-difference time domain and finite element analysis calculations establish specific optically relevant phonon modes.

Tailoring thermal transport and confinement effect of GaN/Si3N4 nanowires utilizing core–shell architecture

The thermal transport properties of nanowires (NWs) can be significantly influenced by the implementation of a core-shell structure, which introduces interface scattering and phonon localization effects, opening avenues for novel applications. In this paper, we use the method of non-equilibrium molecular dynamics to simulate the effects of system temperature, cross-sectional width, and nanopillar interface on the thermal transport of GaN/Si3N4core-shell NWs. The thermal transport process of phonons in core-shell NWs is studied by calculating the vibrational density of states, phonon participation rate, and dispersion curve. The results show that the core-shell NWs characterized by smooth interfaces exhibit a 17.4% decrease in thermal conductivity (TC) at room temperature when contrasted with pristine GaN NWs. Furthermore, the TC of GaN/Si3N4core-shell NWs can be further reduced by adding nanopillars at the interface. Due to resonance effect, thus effectively regulating the thermal transport. The presence of nanopillars increases phonon-surface scattering intensity at low-frequency and modifies phonon dispersion to decrease the group velocity. In addition, the hybridization of phonon modes between those of the nanopillars and the Si3N4shell gives rise to numerous dispersionless resonance phonon modes that span the entire phonon spectrum. This research delves into the effects of nanopillars and interfaces on thermal transport, providing important guidance for understanding confinement effects and establishing a robust theoretical basis for the regulation of thermal transport.

Superconductivity in Monolayer Carbon Allotropes with High Thermal Stability.

Intrinsic superconductivity is rarely discovered in sp2-hybridized monolayer carbon allotropes. Here we design a carbon monolayer configured of pentagon, heptagon, and hexagon rings with p2 plane group symmetry. Full-sp2 hybridization is proposed to favor thermal metastability on a low Gibbs free energy. The extremely small thermal expansion coefficient is predicted to the turn negative value to positive with elevating temperature. Carbon polygon structures remain intact at a high thermal temperature of 3,000 K. The high specific surface area is found to approach 2,700 m2/g, with O2-adsorption being advantageous over pristine graphene. We reveal electronic Fermi surfaces mediated by phonon modes of carbon out-of-plane vibrations. By calculating the Eliashberg equation, we evaluate intrinsic superconductivity with a large electron-phonon coupling coefficient. The superconducting transition temperature is estimated to reach 20 K under a high logarithmic average frequency. These first-principles calculations shall stimulate experimentalists' interest in exploring low-dimensional carbon superconductors with gas sensitivity.

Effects of thickness, temperature and substrate on phonon anisotropy in layered Ta2NiSe5

Anisotropy in crystal structure has provided a new degree of freedom to tune the physical and photoelectric properties of low-symmetrical materials, enabling the anisotropic band structure and polarization-resolved applications. Thus, the identification and control on the anisotropy is of great importance for the development of polarization-integrated devices. In this work, we introduce a promising two-dimensional (2D) dimetal chalcogenide Ta2NiSe5 with strong in-plane anisotropic structure and explore the effects of thickness, temperature and substrate on its in-plane anisotropy via an angle-resolved polarized Raman spectra. It is shown that the Raman mode softens with increasing temperature, revealing the anharmonic phonon properties of the Ta2NiSe5 flakes. We found that the anisotropy of phonon vibration is strongly related with the thickness, temperature and used substrate, which is more obvious at thinner samples, higher temperature and opaque silicon substrate compared to sapphire and suspended conditions. This work first reveals the influence factor on the anisotropy of phonon mode, which will guide the fundamental research of anisotropic physics and experimental design for the angle-resolved electronics.

Lattice dynamics of Bi12GeO20 crystal: Polarized Raman scattering and first-principles analysis

Our paper presents a combined experimental and theoretical study of the lattice dynamics of Bi12GeO20 crystal. Polarized Raman spectra were measured in two x-ray oriented single crystals. In a crystal of cubic symmetry, phonon modes of A- and E-types are spectroscopically indistinguishable. Using a special experimental technique, we separated the phonon modes that transform according to A and E irreducible representations. Since the number of E-type lines observed in Raman scattering is higher than theoretically allowed by group theory, we performed a first-principles calculation of the Bi12GeO20 lattice dynamics to accurately identify the symmetry of phonon modes. All experimental lines observed in Raman scattering are classified according to irreducible representations of the cubic I23 group. Using samples of different thicknesses, 10 mm and 0.120 mm, we have demonstrated that the optical activity plays an insignificant role at Raman backscattering in Bi12GeO20 crystal.

Ab-Initio calculations on physical properties of Dirac semimetal AMgBi (A=K, Rb, Cs)

This study presents a comprehensive first-principles investigation of the structural, mechanical, vibrational, thermodynamic and electronic properties of AMgBi (A = K, Rb, Cs) compounds using Density Functional Theory. Also, the effect of substituting alkali atoms on the physical properties has been discussed. The tetragonal PbClF-type structure has been confirmed by the analysis and the results revealed good agreement between calculated and experimental lattice parameters for KMgBi. The mechanical properties have been investigated for the first time for RbMgBi and CsMgBi. The mechanical stability of the materials in the ground state has been confirmed through the use of obtained elastic constants. Furthermore, derived parameters from elastic constants such as bulk modulus, shear modulus, and Poisson's ratio indicated that the materials are brittle and exhibited anisotropic mechanical behavior due to their layered structure. This study conducts a detailed analysis of phonon modes, explores their connections to thermal and elastic properties, visualizes the movements of phonon modes at the gamma point, determines Born effective charges, and discusses LO/TO splitting, which is for the first time for RbMgBi and CsMgBi. Phonon dispersion calculations confirmed the dynamical stability of the compounds and revealed the presence of phonon band gaps, supporting their quasi-two-dimensional nature. Investigation of thermodynamic properties using the quasi-harmonic approximation has shown the temperature dependence of internal energy, Helmholtz free energy, specific heat, and entropy for the first time for all compounds. The materials exhibited relatively low thermal conductivity, following the order KMgBi > RbMgBi > CsMgBi. The calculated Grüneisen parameter values were found to be 1.42, 1.44, and 1.53 for KMgBi, RbMgBi, and CsMgBi, respectively, suggesting relatively weak anharmonicity within the materials.

Systematic investigation of physical properties of Mg3XO4 (X = Cr, Mn, Fe, Co, Ni); a computational approach

Material development is primarily dependent on their design and theoretical exploration. Density functional theory is a great tool to achieve this goal. Here, Mg3XO4 (X = Cr, Mn, Fe, Co, Ni) are considered in order to reveal their full characteristics using density functional theory. Mg3XO4 (X = Cr, Mn, Fe, Co, Ni) are investigated in terms of their structural, elastic, mechanical, thermodynamic, electronic, and dynamic properties. The formation energies for Mg3XO4 (X = Cr, Mn, Fe, Co, Ni) are found to be negative implying synthesisability and dynamic stability of these materials. The evolution of elastic constants of materials demonstrates that all materials satisfy the Born stability criterion, hence Mg3XO4 (X = Cr, Mn, Fe, Co, Ni) are mechanically stable. Several polycrystalline parameters are derived by using elastic constants and evaluated. All materials are found be brittle, hard (Vickers hardness) and magnetic. They exhibit some degree of anisotropy in Young/Shear modulus and Poisson’s ratio. The electronic band structures for Mg3CrO4, Mg3MnO4 and Mg3FeO4 indicated a semi-metallic nature whereas for Mg3CoO4 and Mg3NiO4 indicated metallic nature because both the majority and minority energy bands cut the Fermi level. The phonon modes are found to be in positive frequencies that confirms dynamical stability. The materials’ free energy, entropy, specific heat capacity, Debye and melting temperatures, minimum thermal conductivity and Grüneisen parameters are also obtained and discussed.

Investigation of phase stability and martensitic transformation of all-d-metal Heusler alloys Fe2VIr and Fe2TaIr in high pressure: A first-principles study

First-principles calculations are used to investigate the phase stability and martensitic transformation of two new all-d-metal Heusler alloys Fe2VIr and Fe2TaIr at 0–50 GPa. The difference in phase stability between Fe2VIr and Fe2TaIr is due to the effect of d-d orbital hybridisation between different atoms and the appearance of triply degenerate in the pressure-induced phonon optical modes. The softening behaviour of the transverse phonon mode along the high symmetry point X is responsible for the martensitic transformation of Fe2TaIr. We also observed the softening of the shear elastic constant C′ = (C11-C12)/2. Strong Fe-Fe magnetic coupling, softening of transverse acoustic phonon modes and anomalous softening of C′ awaken the martensitic transformation. Low-frequency phonon hybridisation of the heavy elements Ta and Ir is the driving force behind the softening. A surprising phenomenon is found during tetragonal deformation of the structure of Fe2TaIr at 45 GPa, whereby the structure break through the energy barrier of the leap and produced a tetragonal martensitic phase with a much lower energy. It may imply that pressure-induced Fe2TaIr produced a premartensitic phase. This work presents a detailed analysis of the anomalous softening behaviour of Fe2TaIr and the mechanism of the pressure-induced martensitic transformation. A new idea is proposed for an in-depth study of the martensitic phase transition precursor reaction.

Synthesis and physical characterization of novel Ag2S-CdS /Ag /GNP ternary nanocomposite

A new type of Ag2S-CdS/Ag/GNP nanocomposite material was successfully synthesized in the presented work. The structural and physical properties of compounds were studied separately and together. Ag2S-CdS/Ag/GNP nanocomposite materials were studied by Xray diffraction (XRD), Ultraviolet-Visible (UV-Vis), Fourier Transform Infrared (FTIR), Raman spectroscopy and Scanning Electron Microscopy (SEM). Based on the results, Ag nanowires (NWs) were successfully synthesized, and then it was determined that during the hybridization process, two phases of acanthite Ag2S and the cubic crystal system of Ag2O were formed. Then, Ag2S-CdS NWs were formed from mixed monoclinic Ag2S and hexagonal CdS. In the absorption spectrum of Ag NWs, the main absorbance peaks were observed at 357.3 nm and 380.2 nm. The energy gap (Eg) values of the Ag sample are 3.8 eV. The band gap value of Ag2S (2.5, 3.8, 4.6 eV) and Ag2S-CdS (2.5, 3.8, 4.8 eV) have a triple value due to the formation of a hybrid structure. The Raman spectrum of Ag2S-CdS belongs to longitudinal-optical (LO) phonon modes of zinc-blende phase CdS and for the 1, 2, and 3 times spin-coated samples on the surface of GNP/PVA have observed all characteristic Raman peaks, which belong to NWs at 485.13 cm-1, and 960.22 cm-1.

CO2 and NO2 formation on amorphous solid water

Context. The dynamics of molecule formation, relaxation, diffusion, and desorption on amorphous solid water (ASW) is studied in a quantitative fashion. Aims. The formation probability, stabilization, energy relaxation, and diffusion dynamics of CO2 and NO2 on cold ASW following atom+diatom recombination reactions are characterized quantitatively. Methods. Accurate machine-learned energy functions combined with fluctuating charge models were used to investigate the diffusion, interactions, and recombination dynamics of atomic oxygen with CO and NO on ASW. Energy relaxation to the ASW and into water internal degrees of freedom were determined from the analysis of the vibrational density of states. The surface diffusion and desorption energetics were investigated with extended and nonequilibrium MD simulations. Results. The reaction probability is determined quantitatively and it is demonstrated that surface diffusion of the reactants on the nanosecond time scale leads to recombination for initial separations of up to 20 Å. After recombination, both CO2 and NO2 stabilize by energy transfer to water internal and surface phonon modes on the picosecond timescale. The average diffusion barriers and desorption energies agree with those reported from experiments, which validates the energy functions. After recombination, the triatomic products diffuse easily, which contrasts with the equilibrium situation, in which both CO2 and NO2 are stationary on the multinanosecond timescale.

Prediction of novel layered indium halide superconductors

Abstract We design two new layered indium halide compounds LaOInF2 and LaOInCl2 by means of first-principles calculations and evolutionary crystal structure prediction. We find both compounds crystallize in a tetragonal structure with P4/nmm space group and have indirect band gaps of 2.58 eV and 3.21 eV, respectively. By substituting O with F, both of them become metallic and superconducting at low temperature. The F-doping leads to strong electron–phonon coupling in the low-energy acoustic phonon modes which is mainly responsible for the induced superconductivity. The total electron–phonon coupling strength are 1.86 and 1.48, while the superconducting transition temperature (T c) are about 7.2 K and 6.5 K with 10% and 5% F doping for LaOInF2 and LaOInCl2, respectively.

Chiral Twist Interface Modulation Enhances Thermoelectric Properties of Tellurium Crystal.

Manipulating the grain boundary and chiral structure of enantiomorphic inorganic thermoelectric materials facilitates a new degree of freedom for enhancing thermoelectric energy conversion. Chiral twist mechanisms evolve by the screw dislocation phenomenon in the nanostructures; however, contributions of such chiral transport have been neglected for bulk crystals. Tellurium (Te) has a chiral trigonal crystal structure, high band degeneracy, and lattice anharmonicity for high thermoelectric performance. Here, Sb-doped Te crystals are grown to minimize the severe grain boundary effects on carrier transport and investigate the interface of chiral Te matrix and embedded achiral Sb2Te3 precipitates, which induce unusual lattice twists. The low grain boundary scattering and conformational grain restructuring provide electrical-favorable semicoherent interfaces. This maintains high electrical conductivity leading to a twofold increase in power factor compared to polycrystal samples. The embedded Sb2Te3 precipitates concurrently enable moderate phonon scattering leading to a remarkable decrease in lattice thermal conductivity and a high dimensionless figure of merit(zT)of 1.1 at 623 K. The crystal growth and chiral atomic reorientation unravel the emerging benefits of interface engineering as a crucial contributor to effectively enhancing carrier transport and minimizing phonon propagation in thermoelectric materials.

Dynamics of Polar Vortex Crystallization.

Vortex crystals are commonly observed in ultrathin ferroelectrics. However, a clear physical picture of origin of this topological state is currently lacking. Here, we show that vortex crystallization in ultrathin Pb(Zr_{0.4},Ti_{0.6})O_{3} films stems from the softening of a phonon mode and can be described as a Z_{2}×SU(1) symmetry-breaking transition. This result sheds light on the topology of the polar vortex patterns and bridges polar vortices with smectic phases, spin spirals, and other modulated states. Finally, we predict a resonant switching of the vortex tube orientation driven by midinfrared laser light which could enable new technologies.

Synergistic effect of bonding heterogeneity and phonon localization in introducing excellent thermoelectric properties in layered heteroanionic NdZnSbO material

Layered rare-earth metal oxides, harnessing the dual properties of oxides and two-dimensional layered materials, exhibit remarkable thermal stability and quantum confinement effects. Therefore, this work adopts the first-principles calculation combined with the Boltzmann transport theory to predict the thermoelectric properties of NdZnSbO compound. The coexistence of weak interlayer van der Waals interactions, robust intralayer ionic bonding, and partial covalent bonding leads to remarkable bonding heterogeneity, which engenders pronounced phonon scattering and imposes constraints on thermal transport along the out-of-plane direction. The weakened chemical bonds induced by the antibonding states, together with the rattling-like behavior of the Zn atom, culminate in the profound anharmonicity in the layered NdZnSbO compound. The weakening bond and heavy element contribute to the softness of phonon modes, which significantly diminishes the phonon group velocity. The redistribution-dominated four-phonon scattering process spans a large optical gap, which effectively reduces the lattice thermal conductivity. The NdZnSbO compound exhibits direct semiconductor characteristic with a bandgap of 0.73 eV by adopting the Heyd-Scuseria-Ernzerhof (HSE06) functional in combination with spin–orbit coupling (SOC) effect. The multi-valley feature of NdZnSbO compound augur favorably for band degeneracy, thus amplifying the power factor. Consequently, an optimal figure-of-merit (ZT) of 3.40 at 900 K is achieved for the n-type NdZnSbO compound. The present study delves deeply insights into the origins for the low thermal conductivity of NdZnSbO compound and proposes an optimization scheme to enhance overall thermoelectric performance.