Phonon Research Articles

Impact of the acoustic phonon bandwidth on three-phonon and four-phonon scattering in half-Heusler materials

Impact of the acoustic phonon bandwidth on three-phonon and four-phonon scattering in half-Heusler materials

Effect of 10 MeV electron irradiation on structural and magnetic properties of Ti- and Al- substituted strontium hexaferrite SrFe11.3Ti0.4Al0.3O19

The irradiation stability of Ti- and Al-substituted SrFe11.3Ti0.4Al0.3O19 strontium hexaferrite to 10 MeV electron irradiation with the fluences of 1014 and 2·1017 cm−2 was investigated using various characterization techniques such as scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectrum microanalysis, atomic force microscopy, Raman spectroscopy, vibrating sample magnetometry and magnetic force microscopy. Notable changes in lattice vibrations, magnetic domain microstructure and magnetization behavior were obtained after the electron irradiation with the fluence of 2·1017 cm−2. Phonon hardening observed by Raman spectroscopy confirms the increasing disorder in crystalline structure and the presence of spin-phonon coupling in the samples after electron irradiation with the fluence 2·1017 cm−2. It was found that the strongest spin-phonon interactions correspond to A1g vibration modes at trigonal bipyramidal 2b, 2a octahedral, 4f1 tetrahedral sites and E1g mode at 4f2 octahedral site in electron-irradiated SrFe11.3Ti0.4Al0.3O19 hexaferrite, while the most radiation-resistant phonon mode is A1g vibration of the Fe–O bonds at the 4f2 octahedral site. No significant change was observed in magnetic saturation magnitude after electron irradiation. The increase in coercivity and significant decrease of magnitude of the dM/dH derivative of magnetization curves with increasing radiation fluence is attributed to the increase in uniaxial magnetic-crystalline anisotropy. It is found that the fractal dimension of hierarchical magnetic domain structure in SrFe11.3Ti0.4Al0.3O19 continuously decreases with increasing fluence of 10 MeV electron irradiation, which can be caused by the distortion in uniaxial magnetocrystalline anisotropy and irradiation-induced defects.

Growth of anthracene microcrystals by the micro-space sublimation method and their photophysical properties

Anthracene and its derivatives are widely utilized in optoelectronic devices due to their unique properties. Generally, single-crystal structures can avoid non-radiative recombination, enhance carrier mobility, and ultimately improve device performance. In this work, anthracene microcrystals were prepared using the micro-space sublimation method. Through real-time in-situ observation, the crystallization dynamics of anthracene molecules were revealed. Unlike traditional vacuum evaporation deposition technique, the close proximity of the substrate to the source facilitates the self-assembly of anthracene molecules into an ordered crystal structure. Six peaks can be observed in the photoluminescence spectrum, corresponding to various lowest excited state decay processes. The fluorescence intensity at the peak of 423 nm decreases significantly with increasing temperature. The reason for this is the relatively high exciton binding energy, which makes excitons more stable and easier to form. The lattice vibrations induced by increased temperature were found to affect the transport and separation of excitons. Time-resolved fluorescence spectroscopy imaging revealed that a relatively uniform distribution of fluorescence lifetimes in the anthracene microcrystals, indicating high crystallization quality. This work provides valuable insights for controlling the morphology and investigating the photophysical properties of organic semiconductors.

Anomalous Raman Response in 2D Magnetic FeTe Under Uniaxial Strain: Tetragonal and Hexagonal Polymorphs.

2D Fe-chalcogenides emerge with rich structures, magnetisms, and superconductivities, which spark the growing research interests in the torturous transition mechanism and tunable properties for their potential applications in nanoelectronics. Uniaxial strain can produce a lattice distortion to study symmetry breaking induced exotic properties in 2D magnets. Herein, the anomalous Raman spectrum of 2D tetragonal (t-) and hexagonal (h-) FeTe is systematically investigated via uniaxial strain engineering strategy. It is found that both t- and h-FeTe keep the structural stability under different uniaxial tensile or compressive strain up to ± 0.4%. Intriguingly, the lattice vibrations along both in-plane and out-of-plane directions exceptionally harden (softened) under tensile (compressive) strain, distinguished from the behaviors of many conventional 2D systems. Further, the difference in thickness-dependent strain effect can be well explained by their structural discrepancy between two polymorphs of FeTe. These results can supply a unique platform to explore the vibrational properties of many novel 2D materials.

Layer stacking effect on structural, vibrational, and electronic properties of Janus-Ga2SeTe crystals

The van der Waals stacking of Janus Ga2SeTe quadruple-atomic layers leads to the formation of polytype bulk crystals, where the stacking order plays a critical yet elusive role in their fundamental properties. Here, we perform first-principles density functional theory calculations to investigate the stacking-dependent structural, electronic, and vibrational properties of four Ga2SeTe polytypes. Our results indicate that the γ polytype has two sub-phases of γ [ABC] and γ [ACB]. Lattice vibration studies manifest that symmetry operations depend on the stacking orders, in which the irreducible representations of optically active modes at Γ for the β, ε, γ, and δ phases are Γ = 3A1 + 4B1 + 4E2 + 3E1, Γ = 7E+7A1, Γ = 11A1 + 11E, and Γ = 8E2 + 7E1 + 8B1 + 7A1, respectively. Moreover, taking spin–orbit coupling into account, the estimated indirect bandgaps are 0.967, 0.926, 0.879, 0.925, and 0.950 eV for β, ε, γ [ABC], γ [ACB], and δ polytypes, respectively, in which the bandgap differences between indirect and direct transitions are within 10 meV. The Bader charge analysis indicates that the stacking order modulates the charge distribution among the compositional layers. These findings provide valuable insights for the development of optoelectronic devices based on Janus structures.

Praseodymium doped ceria: A new sight on coupled thermo-mechanical properties and oxygen vacancy diffusion via statistical moment approach

Applications of praseodymium doped ceria (PDC) in solid oxide fuel cells require a deep insight into the thermal expansion, stresses, and ionic conduction. Nonetheless, the investigation of thermo-mechanical properties and oxygen vacancy diffusion remains incomplete. Based on free Helmholtz energy, we formulate analytical expressions to directly connect thermal expansion coefficient, elastic moduli, oxygen vacancy–dopant binding and oxygen vacancy migration energies by employing statistical moment method (SMM). The SMM calculations capture the full anharmonicity of lattice thermal vibrations. Our analyses report the significant influences of temperature and dopant content on the thermal expansion coefficient, bulk and Young’s moduli, oxygen vacancy–dopant binding and oxygen vacancy migration energies, and ionic conductivity. The role of Pr dopant on the oxygen vacancy diffusion is fully described by combining the symmetric energy profiles related to blocking effect and asymmetric energy profiles generated from trapping effect. By switching van der Waals (vdW) forces on and off in the SMM calculations, we first show that the vdW forces cause a positive effect on the mechanical properties but reduce the thermal expansion and resist the oxygen vacancy diffusion. Our findings are discussed concerning the results from other calculations and experiments in the literature. The insights on the thermo-mechanical properties and oxygen vacancy diffusion for PDC crystal can be generalized and applied to other ceramic materials that are essential for solid state batteries.

Phonons in stringlet-land and the boson peak

Solid materials that deviate from the harmonic crystal paradigm exhibit characteristic anomalies in the specific heat and vibrational density of states (VDOS) with respect to Debye's theory predictions. The boson peak (BP), a low-frequency excess in the VDOS over Debye lawg(ω)∝ω2, is certainly the most famous among them; nevertheless, its origin is still subject of fierce debate. Recent simulation works provided strong evidence that localized one-dimensional string-like excitations (stringlets) might be the microscopic origin of the BP. In this work, we study the dynamics of acoustic phonons interacting with a bath of vibrating 1D stringlets with exponentially distributed size, as observed in simulations. We show that stringlets strongly renormalize the phonon propagator and naturally induce a BP anomaly in the VDOS, corresponding to the emergence of a dispersionless BP flat mode. Additionally, phonon-stringlet interactions produce a strong enhancement of sound attenuation and a dip in the speed of sound near the BP frequency, consistent with experimental and simulation data. The qualitative trends of the BP frequency and intensity are predicted within the model and shown to be in good agreement with previous observations. In summary, our results substantiate with a simple theoretical model the recent simulation results by Hu and Tanaka claiming the origin of the BP from stringlet dynamics.

Raman spectroscopic insights into the pressure-induced phase transition in natural elbaite

Tourmaline [XY₃Z₆(T₆O₁₈)(BO₃)₃V₃W] is a potential carrier for water and boron cycles in the Earth's interior. Its high-pressure structural behavior has been extensively investigated by single-crystal or powder X-ray diffraction. Here, we collected Raman spectroscopy data of natural elbaite with two different compositions (Fe-poor elbaite and Fe-rich elbaite) up to 35.1 GPa to complementarily characterize the structural modifications proposed by previous studies. Our results reveal two clear discontinuous changes in high-pressure Raman spectra of both samples. The first change occurred at around 15 GPa, characterized by changes in Raman peak intensity, and the pressure dependence of the frequencies of several lattice vibration modes and hydroxyl stretching vibrations. The second change emerged at around 26 GPa and was marked by the systematic appearance of new Raman peaks. Based on previous X-ray diffraction studies, the change at around 26 GPa is likely caused by a phase transition from rhombohedral R3m to rhombohedral R3, whereas the change at around 15 GPa is likely caused by a change in compression mechanism. Furthermore, the WOH stretching vibrations at 3691 cm−1 in Fe-rich elbaite exhibited a negative pressure coefficient, contrasting with the positive pressure coefficient observed in Fe-poor elbaite, suggesting a significant influence of chemical composition on the evolution of stretching vibration in WOH groups under high pressure. After release of pressure, the spectra return to their initial state, indicating the reversibility of all observed changes.

Analytical study of the thermoelectric properties in silicene

Theoretically, we investigate the thermoelectric (TE) properties namely, electrical conductivity (σ), diffusion thermopower (S d), power factor (PF), electronic thermal conductivity (κ e) and thermoelectric figure of merit (ZT) for silicene on Al2O3 substrate. TE coefficients are obtained by solving the Boltzmann transport equation taking account of the electron scattering by all the relevant scattering mechanisms in silicene, namely charged impurity (CI), short-range disorder (SD), intra- and inter-valley acoustic (APs) and optical (OPs) phonons, and surface optical phonons (SOPs). The TE properties are numerically studied as a function of temperature T (2–400K) and electron concentration n s(0.1–10 × 1012 cm−2). The calculated σ and S dare found to be governed by CIs at low temperatures (T< ∼ 10 K), similar to that in graphene. At higher T, they are found to be mainly dominated by the intra- and inter-valley APs. The resultant σ (S d) is found to decrease (increase) with increasing T, whereas PF remains nearly constant for T> ∼ 100 K. On the other hand, n s dependence shows that σ (S d) increases (decreases) with increasing n s; with PF relatively constant at lower n s and then decreases with increasing n s. At room temperature, the calculated σ (S d) in silicene is closer to that in graphene and about an order of magnitude greater (less) than that in monolayer (ML) MoS2. The κ e is found to be weakly depending on T and Wiedemann–Franz law is shown to be violated. We have predicted a maximum PF ∼3.5 mW m−1 K−2, at 300 K for n s = 0.1 × 1012 cm−2 from which the estimated ZT = 0.11, taking a theoretically predicted lattice thermal conductivity κ l = 9.4 Wm−1 K−1, is a maximum. This ZT is much greater than that of graphene and ML MoS2. The ZT is found to decrease with the increasing n s. The ZT values for other values of n s in silicene, at 300 K, also show much superiority over graphene, thus making silicene a preferred thermoelectric material because of its relatively large σ and very small κ l.

Chemochromism and Tunable Acoustic Phonons in Intercalated MoO3: Ag-, Bi-, In-, Mo-, Os-, Pd-, Pt-, Rh-, Ru-, Sb-, and W-MoO3.

Intercalation of several elements (Ag, Bi, In, Mo, Os, Pd, Pt, Rh, Ru, Sb, and W) is used to chemically alter a wide range of properties of two-dimensional layered α-MoO3. Intercalation modifies acoustic phonons and elastic constants, as measured with Brillouin scattering. Intercalation alters electronic bandgaps, color, structure, Raman shifts, and electron binding energies. Optical chemochromism is demonstrated with intercalants changing the color of MoO3 from transparent to brilliant blue (In, Mo, Os, and Ru) and orange (Ag). Correlations are investigated among material properties. There is evidence that in-plane longitudinal stiffness c11 correlates with changes in the bandgap, while various Raman modes appear to be connected to a variety of properties, including shear modulus c55, Mo binding energies, lattice constants, and the preferred crystal structure of the intercalant. The results indicate a surprising degree of complexity, suggesting competition among multiple distinct mechanisms and interactions involving specific intercalant species.

Controlled Phonon Transport via Chemical Bond Stretching and Defect Engineering: The Case Study of Filled β-Mn-Type Phases.

Controlling the elastic properties of the material could become a powerful tool for tuning the thermal transport in solids. Nevertheless, the impact of the crystal structure, chemical bonding, and elastic properties on the lattice thermal conductivity remains to be elucidated. This is a pivotal issue for the advancement of thermoelectric (TE) materials. In this context, the influence of cation substitution in tetrahedral voids on the structural, thermal, and TE properties of α- and β-PbyGa6-xInxTe10─filled β-Mn-type phases─is reported here. The investigated materials show semiconducting behavior and a change from p- to n-type conductivity, depending on the chemical composition and temperature. Our findings indicate that the electronic transport in β-Mn-type phases is largely influenced by the substantial distortion of the Te framework, which causes the low weighted mobility and strong scattering of charge carriers. The presence of a significant anharmonicity of lattice vibrations results in the ultralow lattice thermal conductivity of PbyGa6-xInxTe10 materials. With increasing x, κL decreases from 0.59 to an extremely low value of 0.36 W m-1 K-1 at 298 K due to the decrease of bonding energy, intensification of anharmonic thermal vibrations of atoms, and formation of point defects. This work demonstrates the efficacy of utilizing the crystal structure and elastic properties to regulate phonon transport in functional materials.

Weak ferromagnetic interactions of [formula omitted] induced by coupling of the crystal and related lattice vibrations

There is an increase in demand of the next-generation spintronic devices with stable structural and magnetic properties in varying temperatures. An orthoferrites structure of the Pnma space group has been successfully prepared using high temperature solid-state reaction. In the Sm2Fe2O5+δ (SFO) material, Fe3+ ions occupy edge-cantered and face-cantered positions forming the tilted FeO6 octahedrons with Glazer's notation tilt a−a−c+. The ordering of the rare-earth ions at compensation temperature (Tcomp=2.3K), spin-flip transition in the range of 9.4−45.6K, and a second-type spin-reorientation transition around the anisotropy barrier with lower and higher transitional temperatures, TL=465 and TH=480K respectively. The canting of spins along with disordered spins at the surface results in a non-zero Tcomp and unsaturated magnetization. It is inferred that thermal activation of particle's moment over the anisotropy barriers (known as Kneller's law) only occurs above room temperature.

Intercalating Architecture for the Design of Charge Density Wave in Metallic MA2Z4 Materials.

We present a novel approach to induce charge density waves (CDWs) in metallic MA2Z4 materials, resembling the behavior observed in transition metal dichalcogenides (TMDCs). This method leverages the intercalating architecture to maintain the same crystal field and Fermi surface topologies. Our investigation reveals that CDW instability in these materials arises from electron-phonon coupling (EPC) between the d band and longitudinal acoustic (LA) phonons, mirroring TMDC's behavior. By combining α-MA2Z4 with 1H-MX2 materials in a predictive CDW phase diagram using critical EPC constants, we demonstrate the feasibility of extending CDW across material families with comparable crystal fields and reveal the crucial role in CDW instability of the competition between ionic charge transfer and electron correlation. We further uncover a strain-induced Mott transition in β2-NbGe2N4 monolayer featuring star-of-David patterns. This work highlights the potential of intercalating architecture to engineer CDW materials, expanding our understanding of CDW instability and correlation physics.

Surface Vibration‐Mediated and Multiphonon Relaxation‐Assisted Antithermal‐Quenching Shortwave Infrared Emission in Ho‐Based Double Perovskite With Long Lifetime

AbstractThermal quenching generally predominates in Er3+ 1540 nm luminescence quenching at elevated temperatures, due to intensified lattice vibration and efficient overtone vibrational relaxation by O─H stretch. This issue impedes practical device applications of shortwave infrared Er‐doped phosphors. Herein, with the mediation of surface vibrational phonons, anti‐thermal quenching of Er3+ 1540 nm emission is reported in (220)‐dominated Er3+‐doped Cs2NaHoCl6 double perovskite. The downshifting emissions can be boosted with rising temperatures from 303 to 543 K, reaching 225%@483 K of the initial intensity at 303 K, accompanied with a long lifetime of 33.02 ms at 483 K. By combining temperature‐dependent in situ Raman and Fourier transform infrared spectroscopies with the excited‐state dynamics results, the coordination role of water molecules is verified, serving as promoters instead of quenchers on the (220) facet at high temperatures. Furthermore, efficient energy transfer from Ho3+ to Er3+ enables intense 1540 nm emission with a photoluminescence quantum yield of 78.1% under 450 nm excitation. Finally, a compact thermally stable phosphor‐converted light‐emitting diode (LED) is designed as a narrowband shortwave infrared light source with a blue LED chip. This work pushes the improved understanding of achieving thermal‐enhanced Er3+ luminescence for potential broad applications.

Mediating coherent acoustic phonon oscillation of a 2D semiconductor/3D dielectric heterostructure by interfacial engineering

Abstract Coherent acoustic phonon (CAP) oscillation of 2D layered semiconductor/3D dielectric heterostructure generated by femtosecond laser pulse excitation can realize ultrafast photoacoustic conversion, while the photoacoustic conversion efficiency suffers from interfacial phonon scatterings of simultaneously laser-induced lattice heat. Here, taking advantage of graphene’s high thermal conductivity and large acoustic impedance, we demonstrate that phonon scatterings can be markedly mediated in a MoS$_2$/graphene/glass heterostructure via femtosecond laser pump-probe measurements. Equilibrium temperatures of MoS$_2$ lattice have been cooled down by about 45 %. As a benefit, both lifetime of CAP oscillations and pump pulse-picosecond acoustic pulse energy conversion efficiency have been enhanced by a factor of about 2. Our results constitute insights into CAP manipulations via interfacial engineering, that are fundamentally important for ultrafast photoacoustics based on 2D layered semiconductors.

Two stage decoherence of optical phonons in long oligomers.

Molecular vibrations are generally responsible for chemical energy transport and dissipation in molecular systems. This transport is fast and efficient if energy is transferred by optical phonons in periodic oligomers, but its efficiency is limited by decoherence emerging due to anharmonic interactions with acoustic phonons. Using a general theoretical model, we show that in the most common case of the optical phonon band being narrower than the acoustic bands, decoherence takes place in two stages. The faster stage involves optical phonon multiple forward scattering due to absorption and emission of transverse acoustic phonons, i.e., collective bending modes with a quadratic spectrum; the transport remains ballistic and the speed can be altered. The subsequent slower stage involves phonon backscattering in multiphonon processes involving two or more acoustic phonons resulting in a switch to diffusive transport. If the initially excited optical phonon possesses a relatively small group velocity, then it is accelerated in the first stage due to its transitions to states propagating faster. This theoretical expectation is consistent with the recent measurements of optical phonon transport velocity in alkane chains, increasing with increasing the chain length.

Electron energy relaxation mechanism in n-type InxGa1-xAs1-yBiy alloys under electric and magnetic fields

We investigate the power loss per electron mechanism of hot electrons generated under electric and magnetic fields in n-type InxGa1-xAs1-yBiy epitaxial layers. Acoustic phonons are generated under various electric fields to determine the hot-electron energy relaxation mechanisms at low temperatures. The hot electron temperatures are determined by theoretical calculation of the amplitude of the magnetoresistance oscillation. The power loss per degenerate electron is analytically modeled with possible scattering mechanisms. The modeling of the experimental results reveals that power dissipation occurs by employing deformation potential energy scattering for all the samples. The deformation potential energy increases by ∼ 2.14 eV/Bi% when Bi atoms are introduced into ternary InGaAs alloy and the increase in the deformation potential energy is found to be independent of the electron density, which indicates that power dissipation occurs in the equipartition regime.

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.

Spatiotemporal determination of photoinduced strain in a Weyl semimetal.

The application of dynamic strain holds the potential to manipulate topological invariants in topological quantum materials. This study investigates dynamic structural deformation and strain modulation in the Weyl semimetal WTe2, focusing on the microscopic regions with static strain defects. The interplay of static strain fields, at local line defects, with dynamic strain induced from photo-excited coherent acoustic phonons results in the formation of local standing waves at the defect sites. The dynamic structural distortion is precisely determined utilizing ultrafast electron microscopy with nanometer spatial and gigahertz temporal resolutions. Numerical simulations are employed to interpret the experimental results and explain the mechanism for how the local strain fields are transiently modulated through light-matter interaction. This research provides the experimental foundation for investigating predicted phenomena such as the mixed axial-torsional anomaly, acoustogalvanic effect, and axial magnetoelectric effects in Weyl semimetals, and paves the road to manipulate quantum invariants through transient strain fields in quantum materials.

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.