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At least 829 records · Page 46

Self-compensation induced vacancies for significant phonon scattering in InSb

Here, phonon scattering by point defects via mass differences and strain fluctuations could effectively reduce the lattice thermal conductivity. The atomic mass difference can be maximized by introducing the vacancies thus leading to a significant phonon scattering. Usually, the vacancies are introduced by tuning the stoichiometry or forming solid solution with certain compound that contains intrinsically high concentration of vacancies. In this work, we demonstrate that vacancies can be effectively induced by the self-compensation effect via chemical doping. Indium (In) vacancies in InSb were induced by Te-doping and a substantial reduction in thermal conductivity was observed. Room temperature lattice thermal conductivity of the melted and then hot-pressed InSb (without In vacancies) is ~ 14.5 W m –1 K –1 but only ~ 3.8 W m –1 K –1 for InSb 0.96 Te 0.04 (with In vacancies), a reduction of ~ 74%. The advantage of using this strategy for phonon engineering lies in the fact that a substantial reduction in thermal conductivity can be achieved even when the dopant concentration is rather low. Since the self-compensation effect is widely observed in different compounds, it indicates that the vacancy engineering strategy used here is also applicable to a variety of other materials to effectively reduce the lattice thermal conductivity.

36 MATERIALS SCIENCE↗

Phonon lifetimes and mode softening in cubic Cs 2 AgBiBr 6

Metal halide perovskites (MHPs) have emerged as noteworthy candidates for photovoltaic applications in recent years. Their high power-conversion efficiency is largely attributed to the structure-function relationship, which is not well understood. In this study, we examine the low-frequency phonons of the double perovskite Cs 2 AgBiBr 6 using neutron inelastic scattering. We find that the acoustic phonon lifetimes decrease from 16 to 3 ps along Γ to X, which is indicative of significant anharmonicity that contributes to the ultralow thermal conductivity. Additionally, we observe a linear temperature dependence of the square of the zone-center soft optical phonon energy, which is consistent with a weakly first-order displacive cubic-tetragonal structural phase transition. These results provide a deeper understanding of the lattice dynamics and phase transitions in MHPs as well as the effects of anharmonicity by comparison with prototypical hybrid organic-inorganic MHPs, (CH 3 NH 3 ) PbX 3 (X = Br, I).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a large-mass, low-threshold detector system with simultaneous measurements of athermal phonons and scintillation light

For this work, we have combined two low-threshold detector technologies to develop a large-mass, low-threshold detector system that simultaneously measures the athermal phonons in a sapphire detector while an adjacent silicon high-voltage detector detects the scintillation light from the sapphire detector. This detector system could provide event-by-event discrimination between electron and nuclear events due to the difference in their scintillation light yield. While such systems with simultaneous phonon and light detection have been demonstrated earlier with smaller detectors, our system is designed to provide a large detector mass with high amplification for the limited scintillation light. Future work will focus on at least an order of magnitude improvement in the light collection efficiency by having a highly reflective detector housing and custom phonon mask design to maximize light collection by the silicon high-voltage detector.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Surface phonons in the topological insulators Bi 2 Se 3 and Bi 2 Te 3

Raman scattering, inelastic helium scattering and photoemission experiments on the topological insulators Bi 2 Se 3 and Bi 2 Te 3 show features in the range ~ 50–160 cm -1 , which have been assigned alternatively to Raman-forbidden, bulk infrared modes arising from symmetry breaking at the surface or to surface phonons, which couple to the topologically protected electronic states. We present temperature- and wavelength- dependent Raman studies showing additional modes we ascribe to surface phonons in both Bi 2 Se 3 and Bi 2 Te 3 . Our assignment is supported by density functional theory calculations revealing surface phonons at frequencies close to those of the extra peaks in the Raman data. The theoretical results also indicate that these modes are not a consequence of spin-orbit coupling and, thus, that their occurrence is unrelated to the topological properties of these materials.

36 MATERIALS SCIENCE↗

Role of Electron Correlation beyond the Active Space in Achieving Quantitative Predictions of Spin-Phonon Relaxation

Single-molecule magnets (SMMs) are promising candidates for molecular-scale data storage and processing due to their strong magnetic anisotropy and long spin relaxation times. However, as temperature rises, interactions between electronic states and lattice vibrations accelerate spin relaxation, significantly limiting their practical applications. Recently, ab initio simulations have made it possible to advance our understanding of phonon-induced magnetic relaxation, but significant deviations from experiments have often been observed. The description of molecules’ electronic structure has been mostly based on complete active space self-consistent field (CASSCF) calculations, and the impact of electron correlation beyond the active space remains largely unexplored. In this study, we provide the first systematic investigation of spin-phonon relaxation in SMMs with post-CASSCF multiconfigurational methods, specifically CAS followed by second-order perturbation theory and multiconfiguration pair-density functional theory. Taking Co(II)- and Dy(III)-based SMMs as case studies, we analyze how electron correlation influences spin-phonon relaxation rates across a range of temperatures, comparing theoretical predictions with experimental observations. Our findings demonstrate that post-CASSCF treatments make it possible to achieve quantitative predictions for Co(II)-based SMMs. For Dy(III)-based systems, however, accurate predictions require consideration of additional effects, underscoring the urgent necessity of further advancing the study of the effects of electronic correlation in these complex systems.

Energy↗

Phonons in Copper Diphosphide (CuP 2 ): Raman Spectroscopy and Lattice Dynamics Calculations

Copper diphosphide (CuP 2 ) is an emerging binary semiconductor with promising properties for energy conversion and storage applications. While functionality and possible applications of CuP 2 have been studied, there is a curious gap in the investigation of its vibrational properties. In this work, we provide a reference Raman spectrum of CuP 2 , with a complete analysis of all Raman active modes from both experimental and theoretical perspectives. Raman measurements have been performed on polycrystalline CuP 2 thin films with close to stoichiometric composition. Detailed deconvolution of the Raman spectrum with Lorentzian curves has allowed identification of all theoretically predicted Raman active modes (9A g and 9B g ), including their positions and symmetry assignment. Furthermore, calculations of the phonon density of states (PDOS), as well as the phonon dispersions, provide a microscopic understanding of the experimentally observed phonon lines, in addition to the assignment to the specific lattice eigenmodes. We further provide the theoretically predicted positions of the infrared (IR) active modes, along with the simulated IR spectrum from density functional theory (DFT). Overall good agreement is found between the experimental and DFT-calculated Raman spectra of CuP 2 , providing a reference platform for future investigations on this material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical Investigations of Anharmonic Effects and Phonon Transport in the Cubic Phase of Crystalline Perovskite CsPbCl 3

The role of anharmonic effects on lattice dynamics and thermal transport has been investigated in the cubic phase of the CsPbCl 3 perovskite. Limitations of the harmonic approximation, which lead to phonon instabilities in the Brillouin zone, were addressed based on self-consistent phonon theory in combination with first-principles calculations and by incorporation of frequency renormalization effects from bubble and loop diagrams. This theoretical approach demonstrates significant improvements compared to results obtained using a self-consistent phonon dynamic matrix. Both the cubic-to-tetragonal phase transition temperature as well as the predicted lattice thermal conductivity values show good agreement with selected sets of available experimental data. In conclusion, the accuracy of the predicted thermal conductivity data is also tested against systems significantly larger than those allowed by quantum calculations, by using molecular dynamic simulations with machine-learning force fields.

Lattices↗

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 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 length and corner sharpness 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 edge length and truncation of the corners. Furthermore, quality factor values ranging from 10 to 15 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 the specific optically-relevant phonon modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extreme In-Plane Thermal Conductivity Anisotropy in Titanium Trisulfide Caused by Heat-Carrying Optical Phonons

High in-plane anisotropies arise in layered materials with large structural difference along different in-plane directions. Here, we report an extreme case in layered TiS 3 , which features tightly bonded atomic chains along the b-axis direction, held together by weaker, interchain bonding along the a-axis direction. Experiments show thermal conductivity along the chain twice as high as between the chain, an in-plane anisotropy higher than any other layered materials measured to date. We found that in contrast to most other materials, optical phonons in TiS 3 conduct an unusually high portion of heat (up to 66% along the b-axis direction). The large dispersiveness of optical phonons along the chains, contrasted to many fewer dispersive optical phonons perpendicular to the chains, is the primary reason for the observed high anisotropy in thermal conductivity. The finding discovers materials with unusual thermal conduction mechanism, as well as provides new material platforms for potential heat-routing or heat-managing devices.

36 MATERIALS SCIENCE↗

Exciton–Phonon Coupling Induces a New Pathway for Ultrafast Intralayer-to-Interlayer Exciton Transition and Interlayer Charge Transfer in WS 2 –MoS 2 Heterostructure: A First-Principles Study

Despite the weak, van der Waals interlayer coupling, photoinduced charge transfer vertically across atomically thin interfaces can occur within surprisingly fast, sub-50 fs time scales. An early theoretical understanding of charge transfer is based on a noninteracting picture, neglecting excitonic effects that dominate optical properties of such materials. We employ an ab initio many-body perturbation theory approach, which explicitly accounts for the excitons and phonons in the heterostructure. Our large-scale first-principles calculations directly probe the role of exciton-phonon coupling in the charge dynamics of the WS 2 /MoS 2 heterobilayer. We find that the exciton-phonon interaction induced relaxation time of photoexcited excitons at the K valley of MoS 2 and WS 2 is 67 and 15 fs at 300 K, respectively, which sets a lower bound to the intralayer-to-interlayer exciton transfer time and is consistent with experiment reports. We further show that electron-hole correlations facilitate novel transfer pathways that are otherwise inaccessible to noninteracting electrons and holes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Raman and Terahertz Spectroscopy of Low-Frequency Chiral Phonons in Amino Acids

Chiral phonons are mirror-symmetric vibrations with nonzero angular momenta that correspond to twisting and rotational motions of multiple atoms. In chiral crystals, these include low-energy terahertz (THz)-range vibrations of the molecular segments involving dozens of atoms with energies sensitive to molecular chirality. Here, we present spectral signatures of chiral phonons in circularly polarized Raman optical activity (ROA) spectra from enantiomers of amino acid crystals. Along with complementary THz circular dichroism (TCD) measurements, our ROA data reveal several vibrational bands in enantiomers of valine, alanine, tyrosine, and proline between 30 and 150 cm –1 (∼1–4.5 THz) that exhibit opposite intensities. Density functional theory calculations confirm their assignment to twisting and shearing molecular motions. The simultaneous registration of chiral phonon modes by ROA and TCD demonstrates the necessity of these complementary techniques to identify complex mirror-asymmetric vibrational modes and offers new insights into their interactions with circularly polarized light.

36 MATERIALS SCIENCE↗

Revealing the Phonon Bottleneck Limit in Negatively Charged CdS Quantum Dots

The capture of photoexcited hot electrons in semiconductors before they lose their excess energy to cooling is a long-standing goal in photon energy conversion. Semiconductor nanocrystals have large electron energy spacings that are expected to slow down electron relaxation by phonon emission, but hot electrons in photoexcited nanocrystals, nevertheless, cool rapidly by energy transfer to holes. This makes the intrinsic phonon-bottleneck-limited hot electron lifetime in nanocrystals elusive. For this work, we used a combination of theory and experiments to probe the hot-electron dynamics of negatively charged cadmium sulfide (CdS) colloidal quantum dots (QDs) in the absence of holes. Experiments found that these hot electrons cooled on a 100 ps time scale. Theoretical simulations predicted that pure phonon-bottleneck-limited hot electron cooling occurs on a similar time scale. This similarity suggests that the experimental measurements reflect the upper limit on the hot-electron lifetimes in these CdS QDs and the lower limit on the rates of processes that can harvest those hot electrons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Watching Polarons Dance: Coherent Carrier–Phonon Coupling in Hematite Revealed by Transient Absorption Spectroscopy

Hematite remains a prominent photoanode candidate for the oxygen evolution reaction in solar water splitting, despite efficiency limitations from rapid trapping of photoexcited electrons and holes. While the formation of polarons, quasiparticles formed by electron–hole interactions with lattice vibrations, is a proposed trapping mechanism, direct evidence of such states has been elusive. Here, we use potential-dependent transient absorption spectroscopy to identify the coherent phonon mode and strong exciton–phonon coupling responsible for exciton–polaron formation after band gap excitation in α-hematite and identify the three underlying d–d transitions that are strongly modulated by this phonon. The equilibrium geometry of exciton–polarons in α-hematite is displaced from the ground state geometry along the vibrational coordinate of an A 1g symmetric Fe–O stretching motion at 225 ± 7 cm –1 , resulting in vibrational coherence with a lifetime of 1.9 ± 0.1 ps. Our comparative ex situ and in situ experiments reveal that the energy and dephasing time of the A 1g mode are remarkably resilient to applied potential and the addition of an Al 2 O 3 overlayer; however, the dephasing time is sensitive to substrate identity. Furthermore, this potential-dependent transient absorption approach establishes a powerful platform for directly probing polaron dynamics in photoelectrochemical systems, opening new pathways to rationally design modified hematite and other transition metal oxide electrodes with enhanced charge transport properties for more efficient solar water splitting.

Hematite↗

Phonon modulation of strongly coupled gold tetrahedral plasmonic nanoparticles and a carbocyanine J-aggregate

Coupling exciton and plasmon excitations to form polaritons are of great interest for manipulating energy transfer at the nanoscale via the formation of hybrid light–matter states. In this study, we successfully couple gold tetrahedral nanoparticles with the J-aggregate forming dye 5,5′,6,6′-tetrachloro-1,1′-diethyl-3,3′-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC) to form a strongly coupled colloidal polariton system with a Rabi splitting energy of ∼206 meV. These gold tetrahedra exhibit coherent phonon modes upon photoexcitation, which produce transient oscillations of the LSPR energy for isolated tetrahedra. Transient absorption measurements of the polariton system were performed and show how these coherent phonon modes influence the polariton states’ extinction. We found that the oscillation period increases by 0.5 ± 0.14 ps upon surface deposition of TDBC dye, demonstrating LSPR sensitivity to the refractive index environment. Shifts in the plasmon resonance due to the coherent phonon modes transiently alters LSPR alignment with the J-aggregate exciton peak, resulting in shifts of the hybrid polariton states’ oscillator strength.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Femtosecond laser-induced crystallization of amorphous Sb{sub 2}Te{sub 3} film and coherent phonon spectroscopy characterization and optical injection of electron spins

A femtosecond laser-irradiated crystallizing technique is tried to convert amorphous Sb{sub 2}Te{sub 3} film into crystalline film. Sensitive coherent phonon spectroscopy (CPS) is used to monitor the crystallization of amorphous Sb{sub 2}Te{sub 3} film at the original irradiation site. The CPS reveals that the vibration strength of two phonon modes that correspond to the characteristic phonon modes (A{sub 1g}{sup 1} and E{sub g}) of crystalline Sb{sub 2}Te{sub 3} enhances with increasing laser irradiation fluence (LIF), showing the rise of the degree of crystallization with LIF and that femtosecond laser irradiation is a good post-treatment technique. Time-resolved circularly polarized pump-probe spectroscopy is used to investigate electron spin relaxation dynamics of the laser-induced crystallized Sb{sub 2}Te{sub 3} film. Spin relaxation process indeed is observed, confirming the theoretical predictions on the validity of spin-dependent optical transition selection rule and the feasibility of transient spin-grating-based optical detection scheme of spin-plasmon collective modes in Sb{sub 2}Te{sub 3}-like topological insulators.

36 MATERIALS SCIENCE↗

Optical phonon lifetimes in sputtered AlN thin films

We study the vibrational properties of AlN thin films deposited on silicon (100) substrates by the reactive DC-pulsed magnetron sputtering. The frequencies and lifetimes of the E{sub 1}(TO) and A{sub 1}(LO) optical phonons are calculated from Fourier transform infrared spectra using the factorized model of a damped oscillator. We analyze the structural properties by the x-ray diffraction technique to correlate the elongation of phonon lifetimes with increasing film thickness. The lifetimes of the phonon modes in AlN thin films are compared to the values in a single crystal.

36 MATERIALS SCIENCE↗

Probing confined acoustic phonons in free standing small gold nanoparticles

Polarized and depolarized spectra from gold (Au) nanoparticles of different sizes are investigated in the small size range, between 3 and 7 nm, using low frequency Raman spectroscopy. Acoustic vibrations of the free-standing Au nanoparticles are demonstrated with frequencies ranging from 5 to 35 cm{sup -1}, opening the way to the development of the acoustic resonators. A blue shift in the phonon peaks along with the broadening is observed with a decrease in particle size. Comparison of the measured frequencies with vibrational dynamics calculation and an examination as from the transmission electron microscopy results ascertain that the low frequency phonon modes are due to acoustic phonon quantization. Our results show that the observed low frequency Raman scattering originates from the spherical (l = 0) and quadrupolar (l = 2) vibrations of the spheroidal mode due to plasmon mediated acoustic vibrations in Au nanoparticles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optical phonon modes in InGaN/GaN dot-in-a-wire heterostructures grown by molecular beam epitaxy

We report on the studies of optical phonon modes in nearly defect-free GaN nanowires embedded with intrinsic InGaN quantum dots by using oblique angle transmission infrared spectroscopy. These phonon modes are dependent on the nanowire fill-factor, doping densities of the nanowires, and the presence of InGaN dots. These factors can be applied for potential phonon based photodetectors whose spectral responses can be tailored by varying a combination of these three parameters. The optical anisotropy along the growth (c-) axis of the GaN nanowire contributes to the polarization agility of such potential photodetectors.

36 MATERIALS SCIENCE↗