Strong Electron-Vibration Signals in Weakly Coupled Molecular Junctions: Activation of Spin-Crossover.

Manipulating individual molecular spin states with electronic current has the potential to revolutionize quantum information devices. However, it is still unclear how a current can cause a spin transition in single-molecule devices. Here, we propose a spin-crossover (SCO) mechanism induced by electron-phonon coupling in an iron(II) phthalocyanine molecule situated on a graphene-decoupled Ir(111) substrate. We performed simulations of both elastic and inelastic electron tunneling spectroscopy (IETS), which reveal current-induced Fe-N vibrations and an underestimation of established electron-vibration signals. Going beyond standard perturbation theory, we examined molecules in various charge and spin states using the Franck-Condon framework. The increased probability of spin switching suggests that notable IETS signals indicate SCO triggered by the inelastic vibrational excitation associated with Fe-N stretching.

Ultralow Thermal Conductivity in Vacancy-Ordered Halide Perovskite Cs3Bi2Br9 with Strong Anharmonicity and Wave-Like Tunneling of Low-Energy Phonons.

Halide perovskites are of great interest due to their exceptional optical and optoelectronic properties. However, thermal conductivity of many halide perovskites remains unexplored. In this study, an ultralow lattice thermal conductivity κL (0.24 W m-1 K-1 at 300 K) is reported and its weak temperature dependence (≈T-0.27) in an all-inorganic vacancy-ordered halide perovskite, Cs3Bi2Br9. The intrinsically ultralow κL can be attributed to the soft low-lying phonon modes with strong anharmonicity, which have been revealed by combining experimental heat capacity and Raman spectroscopy measurements, and first-principles calculations. It is shown that the highly anharmonic phonons originate from the Bi 6s2 lone pair expression with antibonding states of Bi 6s and Br 4p orbitals driven by the dynamic BiBr6 octahedral distortion. Theoretical calculations reveal that these low-energy phonons are mostly contributed by large Br motions induced dynamic distortion of BiBr6 octahedra and large Cs rattling motions, verified by the synchrotron X-ray pair distribution function analysis. In addition, the weak temperature dependence of κL can be traced to the wave-like tunneling of phonons, induced by the low-lying phonon modes. This work reveals the strong anharmonicity and wave-like tunneling of low-energy phonons for designing efficient vacancy-ordered halide perovskites with intrinsically low κL.

Effect of Nanoscale Surface Roughness and Electron-Phonon Interaction on Vibrational Modes of Cadmium Telluride Using Resonant Raman Spectroscopy.

This study investigates the combined effects of nanoscale surface roughness and electron-phonon interaction on the vibrational modes of cadmium telluride (CdTe) using resonant Raman spectroscopy. Raman spectra simulations aided in identifying the active phonon modes and their dependence on roughness. Our results reveal that increasing surface roughness leads to an asymmetric line shape in the first-order longitudinal optical (1LO) phonon mode, attributed to an increase in the electron-phonon interaction. This asymmetry broadens the entire Raman spectrum. Conversely, the overtone (second-order longitudinal optical [2LO]) mode exhibits a symmetrical line shape that intensifies with roughness. Additionally, we identify and discuss the contributions of surface optical phonon mode and multiphonon modes to the Raman spectra, highlighting their dependence on roughness. This work offers a deeper understanding of how surface roughness and electron-phonon scattering influence the line shape of CdTe resonant Raman spectra, providing valuable insights into its vibrational properties.

Giant Enhancement of Hole Mobility for 4H-Silicon Carbide through Suppressing Interband Electron-Phonon Scattering.

4H-silicon carbide (4H-SiC) possesses a high Baliga figure of merit, making it a promising material for power electronics. However, its applications are limited by low hole mobility. Herein, we found that the hole mobility of 4H-SiC is mainly limited by the strong interband electron-phonon scattering using mode-level first-principles calculations. Our research indicates that applying compressive strain can reverse the sign of crystal-field splitting and change the ordering of electron bands close to the valence band maximum. Therefore, the interband electron-phonon scattering is severely suppressed and the electron group velocity is significantly increased. The out-of-plane hole mobility of 4H-SiC can be greatly enhanced by ∼200% with 2% uniaxial compressive strain applied. This work provides new insights into the electron transport mechanisms in semiconductors and suggests a strategy to improve hole mobility that could be applied to other semiconductors with hexagonal crystalline geometries.

In-Plane Overdamping and Out-Plane Localized Vibration Contribute to Ultralow Lattice Thermal Conductivity of Zintl Phase KCdSb.

Zintl phases typically exhibit low lattice thermal conductivity, which are extensively investigated as promising thermoelectric candidates. While the significance of Zintl anionic frameworks in electronic transport properties is widely recognized, their roles in thermal transport properties have often been overlooked. This study delves into KCdSb as a representative case, where the [CdSb4/4]- tetrahedrons not only impact charge transfer but also phonon transport. The phonon velocity and mean free path, are heavily influenced by the bonding distance and strength of the Zintl anions Cd and Sb, considering the three acoustic branches arising from their vibrations. Furthermore, the weakly bound Zintl cation K exhibits localized vibration behaviors, resulting in strong coupling between the high-lying acoustic branch and the low-lying optical branch, further impeding phonon diffusion. The calculations reveal that grain boundaries also contribute to the low lattice thermal conductivity of KCdSb through medium-frequency phonon scattering. These combined factors create a glass-like thermal transport behavior, which is advantageous for improving the thermoelectric merit of zT. Notably, a maximum zT of 0.6 is achieved for K0.84Na0.16CdSb at 712 K. The study offers both intrinsic and extrinsic strategies for developing high-efficiency thermoelectric Zintl materials with extremely low lattice thermal conductivity.

Anisotropic Electron-Phonon Interactions in 2D Lead-Halide Perovskites.

Two-dimensional (2D) hybrid organic-inorganic metal halide perovskites offer enhanced stability for perovskite-based applications. Their crystal structure's soft and ionic nature gives rise to strong interaction between charge carriers and ionic rearrangements. Here, we investigate the interaction of photogenerated electrons and ionic polarizations in single-crystal 2D perovskite butylammonium lead iodide (BAPI), varying the inorganic lamellae thickness in the 2D single crystals. We determine the directionality of the transition dipole moments (TDMs) of the relevant phonon modes (in the 0.3-3 THz range) by the angle- and polarization-dependent THz transmission measurements. We find a clear anisotropy of the in-plane photoconductivity, with a ∼10% reduction along the axis parallel with the transition dipole moment of the most strongly coupled phonon. Detailed calculations, based on Feynman polaron theory, indicate that the anisotropy originates from directional electron-phonon interactions.

Phonon excitations in Eu2Ir2O7probed by inelastic x-ray scattering.

The study of phonon dynamics and its interplay with magnetic ordering is crucial for understanding the unique quantum phases in the pyrochlore iridates. Here, through inelastic x-ray scattering on a single crystal sample of the pyrochlore iridate Eu2Ir2O7, we map out the phonon excitation spectra in Eu2Ir2O7and compare them with the theoretical phonon spectra calculated using the density functional theory. Possible phonon renormalization across the magnetic long-range order transition is observed in our experiments, which is consistent with the results of the previous Raman scattering experiments.

Ab-initio insights into the mechanical, phonon, bonding, electronic, optical and thermal properties of hexagonal W2N3 for prospective applications.

We thoroughly investigated the structural, mechanical, electronic, vibrational, optical, thermodynamic, and a number of thermophysical properties of W2N3 compound through first-principles calculations using the DFT based formalism. The calculated structural parameters show very good agreement with the available theoretical and experimental results. The mechanical and dynamical stabilities of this compound have been investigated theoretically from the elastic constants and phonon dispersion curves. The Pugh's and Poisson's ratios of W2N3 are located quite close to the brittle/ductile borderline. W2N3 is elastically anisotropic. The calculated electronic band structure and density of states reveal that W2N3 is conducting in nature. The Fermi surface topology has also been explored. The analysis of charge density distribution map shows that W atoms have comparatively high electron density around compared to the N atoms. Presence of covalent bondings between W-N, W-W, and N-N atoms are anticipated. High melting temperature and high phonon thermal conductivity of W2N3 imply that the compound has potential to be used as a heat sink system. The optical characteristics show anisotropy. The compound can be used in optoelectronic devices due to its high absorption coefficient and low reflectivity in the visible to ultraviolet spectrum. Furthermore, the quasi-harmonic Debye model is used to examine temperature and pressure dependent thermal characteristics of W2N3 for the first time.

Tailoring structural and optical properties of ZnO system through elemental Mn Doping through First-principles calculations.

In this study, band structure and optical properties of Manganese (Mn) doped ZnO are investigated adopting first-principles study calculations. It is observed that, by addition of Mn in ZnO crystal, the electrical properties like conductivity and dielectric function of material have been improved. The elastic constants for the elements are also calculated which shows that the element is stable after addition of dopant. The computational study is done on CASTEP and Material Studio. The ZnO system is simulated and atoms of Mn has been added replacing Zn atoms. The properties that studied are band structure and optics including conductivity, reflectivity, dielectric function, absorption and refractive index. Furthermore, this study also includes calculation of Elastic constants, XRD Spectra, Phonon dispersion and Temperature profile of doped ZnO systems. The computational study produced promising results and experimental approach can be adopted to reinforce the outcomes of this study.

Spin-Phonon Coupling and Magnetic Transition in an Organic Molecule Intercalated Cr2Ge2Te6.

The manipulation of spin-phonon coupling in both formations and explorations of magnetism in two-dimensional van der Waals ferromagnetic semiconductors facilitates unprecedented prospects for spintronic devices. The interlayer engineering with spin-phonon coupling promises controllable magnetism via organic cation intercalation. Here, spectroscopic evidence reveals the intercalation effect on the intrinsic magnetic and electronic transitions in quasi-two-dimensional Cr2Ge2Te6 using tetrabutyl ammonium (TBA+) as the intercalant. The temperature evolution of Raman modes, Eg3 and Ag1, along with the magnetization measurements, unambiguously captures the enhancement of the ferromagnetic Curie temperature in the intercalated heterostructure. Moreover, the Eg4 mode highlights the increased effect of spin-phonon interaction in magnetic-order-induced lattice distortion. Combined with the first-principle calculations, we observed a substantial number of electrons transferred from TBA+ to Cr through the interface. The interplay between spin-phonon coupling and magnetic ordering in van der Waals magnets appeals for further understanding of the manipulation of magnetism in layered heterostructures.

Unveiling Spatiotemporal Diffusion of Hot Carriers Influenced by Spatial Nonuniform Hot Phonon Bottleneck Effect in Monolayer MoS2.

The exceptional semiconducting properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) have made them highly promising for the development of future electronic and optoelectronic devices. Extensive studies of TMDs are partly associated with their ability to generate 2D-confined hot carriers above the conduction band edges, enabling potential applications that rely on such transient excited states. In this work, room-temperature spatiotemporal hot carrier dynamics in monolayer MoS2 is studied by transient absorption microscopy (TAM), featuring an initial ultrafast expansion followed by a rapid negative diffusion, and ultimately a slow long-term expansion of the band edge C-excitons. We provide direct experimental evidence to identify the abnormal negative diffusion process as a spatial contraction of the hot carriers resulting from spatial variation in the hot phonon bottleneck effect due to the Gaussian intensity distribution of the pump laser beam.

Detrimental Increase of Spin-Phonon Coupling in Molecular Qubits on Substrates.

Molecular qubits are a promising platform for quantum information systems. Although single molecule and ensemble studies have assessed the performance of S = 1/2 molecules, it is understood that to function in devices, regular arrays of addressable qubits supported by a substrate are needed. The substrate imposes mechanical and electronic boundary conditions on the molecule; however, the impact of these effects on spin-lattice relaxation times is not well understood. Here we perform electronic structure calculations to assess the effects of a graphene (Cgr) substrate on the molecular qubit copper phthalocyanine (CuPc). We use a progressive Hessian approach to efficiently calculate and separate the substrate contributions. We also use a simple thermal model to predict the impact of these changes on the spin-phonon coupling from 0 to 200 K. Further analysis of the individual vibrational modes with and without Cgr shows that an overall increase in SPC between the vibrations modes of CuPc with the surface reduces the spin-lattice relaxation time T1. We explain these changes by examining how the substrate lifts symmetries of CuPc in the absorbed configuration. Our work shows that a surface can have a large unintentional impact on SPC and that ways to reduce this coupling need to be found to fully exploit arrays of molecular qubits in device architectures.

Phonon screening and dissociation of excitons at finite temperatures from first principles.

The properties of excitons, or correlated electron-hole pairs, are of paramount importance to optoelectronic applications of materials. A central component of exciton physics is the electron-hole interaction, which is commonly treated as screened solely by electrons within a material. However, nuclear motion can screen this Coulomb interaction as well, with several recent studies developing model approaches for approximating the phonon screening of excitonic properties. While these model approaches tend to improve agreement with experiment, they rely on several approximations that restrict their applicability to a wide range of materials, and thus far they have neglected the effect of finite temperatures. Here, we develop a fully first-principles, parameter-free approach to compute the temperature-dependent effects of phonon screening within the ab initio [Formula: see text]-Bethe-Salpeter equation framework. We recover previously proposed models of phonon screening as well-defined limits of our general framework, and discuss their validity by comparing them against our first-principles results. We develop an efficient computational workflow and apply it to a diverse set of semiconductors, specifically AlN, CdS, GaN, MgO, and [Formula: see text]. We demonstrate under different physical scenarios how excitons may be screened by multiple polar optical or acoustic phonons, how their binding energies can exhibit strong temperature dependence, and the ultrafast timescales on which they dissociate into free electron-hole pairs.

Influence of Edges and Interlayer Electron-phonon Coupling in WS2/h-BN Heterostructure.

The semiconducting layered transition metal dichalcogenides (e.g., WS2) are excellent candidates for the realization of optoelectronic and nanophotonic applications on account of their band gap tunability, high binding energy and oscillator strength of the excitons, strong light-matter interaction, appreciable charge carrier mobility, and valleytronic properties. However, the photoluminescence (PL) emissions are reported to show a nonuniform spatial distribution, with the edges emitting features like defect-bound excitons and biexcitons at low temperatures in addition to the typical excitons and trions. The appearance of these additional PL features has been shown in the literature to have a strong dependence on the presence of S-vacancies and excess charge carriers. We demonstrate an enhancement of the defect-bound excitons and biexcitons by creating a heterostructure of WS2 with h-BN where the coupling between the charge carriers in WS2 with the polar phonons in h-BN governs the enhancement. Furthermore, we have performed a comprehensive resonant Raman study with varying polarization and magnetic field which not only confirms the presence of electron-phonon coupling in WS2/h-BN heterostructure, it further demonstrates a thermally induced differential resonance behavior with the excitonic level and the defect-induced midgap states (due to S-vacancies at the edge of WS2) exhibited by a dome-shaped behavior of the Raman intensities with temperature for the normal and defect-induced phonon modes. The defect-bound Raman modes exhibit maximum resonance at ∼240 K while normal Raman modes show at ∼280 K owing to a thermal variation of the electronic states.

Quantitative regulation of electron-phonon coupling.

Electron-phonon (e-p) coupling plays a crucial role in various physical phenomena, and regulation of e-p coupling is vital for the exploration and design of high-performance materials. However, the current research on this topic lacks accurate quantification, hindering further understanding of the underlying physical processes and its applications. In this work, we demonstrate quantitative regulation of e-p coupling, by pressure engineering andin-situspectroscopy. We successfully observe both a distinct vibrational mode and a strong Stokes shift in layered CrBr3, which are clear signatures of e-p coupling. This allows us to achieve precise quantification of the Huang-Rhys factorSat the actual sample temperature, thus accurately determining the e-p coupling strength. We further reveal that pressure efficiently regulates the e-p coupling in CrBr3, evidenced by a remarkable 40% increase inSvalue. Our results offer an approach for quantifying and modulating e-p coupling, which can be leveraged for exploring and designing functional materials with targeted e-p coupling strengths.

Inferior Interfacial Superconductivity in 1 UC FeSe/SrVO3/SrTiO3 with Screened Interfacial Electron-Phonon Coupling.

Single-unit cell (1 UC) FeSe interfaced with TiOx or FeOx exhibits significantly enhanced superconductivity compared to that of bulk FeSe, with interfacial electron-phonon coupling (EPC) playing a crucial role. However, the reduced dimensionality in 1 UC FeSe, which may drive superconducting fluctuations, complicates our understanding of the enhancement mechanisms. We construct a new superconducting interface, 1 UC FeSe/SrVO3/SrTiO3. Here, the itinerant electrons of highly metallic SrVO3 films can screen all high-energy Fuchs-Kliewer phonons, including those of SrTiO3, making it the first FeSe/oxide system with screened interfacial EPC while maintaining the 1 UC FeSe thickness. Despite comparable doping levels, the heavily electron-doped 1 UC FeSe/SrVO3 exhibits a pairing temperature (Tg ∼ 48 K) lower than those of FeSe/SrTiO3 and FeSe/LaFeO3. Our findings disentangle the contributions of interfacial EPC from dimensionality in terms of enhancing Tg in FeSe/oxide interfaces, underscoring the critical importance of interfacial EPC. This FeSe/VOx interface also provides a platform for studying interfacial superconductivity.

Machine learning assisted understanding of the layer-thickness dependent thermal conductivity in fluorinated graphene.

Manipulating thermal conductivity (κ) plays vital role in high-performance thermoelectric conversion, thermal insulation and thermal management devices. In this work, we using the machine learning-based interatomic potential and the phonon Boltzmann transport equation to systematically investigate layer thickness dependentκof fluorinated graphene (FG). We show that the latticeκof FG can be significantly decreased with Bernal bilayer stacking. Surprisingly, the further increasing of stacking layer can no longer affect theκ, however, theκis increased in the bulk configuration. The variation ofκcan be attributed to the crystal symmetry change from P-3m1 (164) at single layer to P3m1 (156) at multilayer. The decreasing crystal symmetry from single layer to bilayer resulting stronger phonon scattering and thus leading a lowerκ. Moreover, we also show that the contribution of acoustic mode toκdecreases with the increase of layers, while the contribution of optical mode toκis increased with increasing layers. These results provide a further understanding for the phonon scattering mechanism of layer thickness dependentκ.

Tailoring Phonon Dispersion of a Genetically Designed Nanophononic Metasurface.

Phonon engineering at the nanoscale holds immense promise for a myriad of applications. However, the design of phononic devices continues to rely on regular shapes chosen according to long-established simple rules. Here, we demonstrate an inverse design approach to create a two-dimensional phononic metasurface exhibiting a highly anisotropic phonon dispersion along the main axes of the Brillouin zone. A partial hypersonic bandgap of approximately 3.5 GHz is present along one axis, with gap closure along the orthogonal axis. Such a level of control is achieved through genetically optimized unit cells, with shapes exceeding conventional intuition. We experimentally validated our theoretical predictions using Brillouin light scattering, confirming the effectiveness of the inverse design method. Our approach unlocks the potential for automated engineering of phononic metasurfaces with on-demand functionalities, thus leading toward innovative phononic devices beyond the limitations of traditional design paradigms.

Quantum acoustics unravels Planckian resistivity.

Strange metals exhibit universal linear-in-temperature resistivity described by a Planckian scattering rate, the origin of which remains elusive. By employing an approach inspired by quantum optics, we arrive at the coherent state representation of lattice vibrations: quantum acoustics. Utilizing this nonperturbative framework, we demonstrate that lattice vibrations could serve as active drivers in the Planckian resistivity phenomenon, challenging prevailing theories. By treating charge carriers as quantum wave packets negotiating the dynamic acoustic field, we find that a competition ensues between localization and delocalization giving rise to the previously conjectured universal quantum bound of diffusion, [Formula: see text], independent of temperature or any other material parameters. This leads to the enigmatic T-linear resistivity over hundreds of degrees, except at very low temperatures. Quantum diffusion also explains why strange metals have much higher electrical resistivity than typical metals. Our work elucidates the critical role of phonons in Planckian resistivity from a unique perspective and reconsiders their significance in the transport properties of strange metals.

A new perspective on ductile high-Tcsuperconductors under ambient pressure: few-hydrogen metal-bonded hydrides.

Superconducting materials have garnered widespread attention due to their zero-resistance characteristic and complete diamagnetism. After more than 100 years of exploration, various high-temperature superconducting materials including cuprates, nickelates, iron-based compounds, and ultra-high pressure multi-hydrides have been discovered. However, the practical application of these materials is severely hindered by their poor ductility and/or the need for high-pressure conditions to maintain structural stability. To address these challenges, we first provide a new thought to build high-temperature superconducting materials based on few-hydrogen metal-bonded hydrides under ambient pressure. We then review the related research efforts in this article. Moreover, based on the bonding type of atoms, we classify the existing important superconducting materials and propose the new concepts of pseudo-metal and quasi-metal superconductivity, which are expected to be helpful for the design of new high-temperature superconducting materials in the future.