High-intensity THz laser pulses enable the light-mediated control of lattice vibrations by resonantly driving selected phonon modes. On ultrafast timescales, memory effects influence the phonon dynamics and must be accounted for to describe the heat production associated with energy dissipation. Here, we establish a microscopic framework for non-Markovian phonon dynamics by deriving the noise and dissipation kernels governing a driven phonon mode. Using large-scale molecular dynamics simulations, we reconstruct these kernels directly from the many-body lattice dynamics and determine the corresponding heat production rate. Our results provide a quantitative picture of the crossover between Markovian and non-Markovian dynamics on picosecond timescales and show how the finite bandwidth of the driving field limits the dynamically relevant bath spectrum. Furthermore, we demonstrate that thermodynamic quantities such as heat production can be inferred directly from the dynamics of an individual phonon mode, enabling their experimental measurement using time-resolved spectroscopy.
We analyze the effect of electron-phonon coupling on photoemission properties and ultrafast response of doped monolayer MoS2. The analysis is based on combined DFT and many-body (Eliashberg theory) approaches. In particular, we have calculated the electronic and phonon spectra, the electron-phonon coupling and the electronic spectral function of the system at different values of doping. We have also analyzed the emissive properties and the response of the system to femtosecond (fs) laser pulses. It is shown that position of the emission peak of undoped system is in agreement with the experimen…
We synthesize sub-THz longitudinal quasi-monochromatic acoustic phonons in a SrTiO$_3$ single crystal using a SrRuO$_3$/SrTiO$_3$ superlattice as an optical-acoustic transducer. The generated acoustic phonon spectrum is determined using ultrafast X-ray diffraction. The analysis of the generated phonon spectrum in the time domain reveals a k-vector dependent phonon lifetime. It is observed that even at sub-THz frequencies the phonon lifetime agrees with the 1/$ω^2$ power law known from Akhiezer's model for hyper sound attenuation. The observed shift of the synthesized spectrum to the higher $q$…
This study investigates the ultrafast dynamics of coherent phonons and phonon-polaritons in lithium niobate (LiNbO$_{3}$) crystals using reflective pump-probe spectroscopy with 25-fs time resolution. In addition to several coherent optical phonon modes, the electro-optic sampling measurements explored the coexistence of phonon-polariton E-modes near 3.8 and 14.9 THz, which agrees considerably with the theoretical phonon-polariton dispersion curves. We also discovered that a time lag ($Δ$t $\approx$ 0.2 ps) between the coherent optical phonon and phonon-polariton originates from the coupling ti…
Perturbo is a software package for first-principles calculations of charge transport and ultrafast carrier dynamics in materials. The current version focuses on electron-phonon interactions and can compute phonon-limited transport properties such as the conductivity, carrier mobility and Seebeck coefficient. It can also simulate the ultrafast nonequilibrium electron dynamics in the presence of electron-phonon scattering. Perturbo uses results from density functional theory and density functional perturbation theory calculations as input, and employs Wannier interpolation to reduce the computat…
We report a novel phenomenon in carbon nanotube (CNT) based devices, the transphonon effects, which resemble the transonic effects in aerodynamics. It is caused by dissipative resonance of nanotube phonons similar to the radial breathing mode, and subsequent drastic surge of the dragging force on the sliding tube, and multiple phonon barriers are encountered as the intertube sliding velocity reaches critical values. It is found that the transphonon effects can be tuned by applying geometric constraints or varying chirality combinations of the nanotubes.
Ultrafast spectroscopies can access the dynamics of electrons and nuclei at short timescales, shedding light on nonequilibrium phenomena in materials. However, development of accurate calculations to interpret these experiments has lagged behind as widely adopted simulation schemes are limited to sub-picosecond timescales or employ simplified interactions lacking quantitative accuracy. Here we show a precise approach to obtain the time-dependent populations of nonequilibrium electrons and atomic vibrations (phonons) up to tens of picoseconds, with a femtosecond time resolution. Combining first…
Using ultrafast optical pump-probe spectroscopy, we study the relaxation dynamics of hot optical phonons in few-layer and multi-layer graphene films grown by epitaxy on silicon carbide substrates and by chemical vapor deposition on nickel substrates. In the first few hundred femtoseconds after photoexcitation, the hot carriers lose most of their energy to the generation of hot optical phonons which then present the main bottleneck to subsequent carrier cooling. Optical phonon cooling on short time scales is found to be independent of the graphene growth technique, the number of layers, and the…
We report the ultrafast dynamics of the 47.4 THz coherent phonons of graphite interacting with a photoinduced non-equilibrium electron-hole plasma. Unlike conventional materials, upon photoexcitation the phonon frequency of graphite upshifts, and within a few picoseconds relaxes to the stationary value. Our first-principles density functional calculations demonstrate that the phonon stiffening stems from the light-induced decoupling of the non-adiabatic electron-phonon interaction by creating the non-equilibrium electron-hole plasma. Time-resolved vibrational spectroscopy provides a window on …
Fast carrier cooling is important for high power graphene based devices. Strongly Coupled Optical Phonons (SCOPs) play a major role in the relaxation of photoexcited carriers in graphene. Heterostructures of graphene and hexagonal boron nitride (hBN) have shown exceptional mobility and high saturation current, which makes them ideal for applications, but the effect of the hBN substrate on carrier cooling mechanisms is not understood. We track the cooling of hot photo-excited carriers in graphene-hBN heterostructures using ultrafast pump-probe spectroscopy. We find that the carriers cool down f…
Ultrafast time-resolved differential reflectivity of Bi2Se3 crystals is studied using optical pump-probe spectroscopy. Three distinct relaxation processes are found to contribute to the initial transient reflectivity changes. The deduced relaxation timescale and the sign of the reflectivity change suggest that electron-phonon interactions and defect-induced charge trapping are the underlying mechanisms for the three processes. After the crystal is exposed to air, the relative strength of these processes is altered and becomes strongly dependent on the excitation photon energy.
Time-domain femtosecond laser spectroscopic measurements of the ultrafast lattice dynamics in 2H-MoTe2 bulk crystals were carried out to understand the carrier-phonon interactions that govern electronic transport properties. An unusually long lifetime coherent A1g phonon mode was observed even in the presence of very large density of photo-excited carriers at room temperature. The decay rate was observed to decrease with increasing excitation laser fluence. Based on the laser fluence dependence including the inducement of significant phonon softening and a peculiar decrease in phonon decay rat…
Despite being the most studied nodal line semimetal, a clear understanding of the transient state relaxation dynamics and the underlying mechanism in ZrSiS is lacking. Using time and angle resolved photoemission spectroscopy, we study the ultrafast relaxation dynamics in ZrSiS and reveal a unique relaxation in the bulk nodal-line state which is well captured by a simple model based on optical and acoustic phonon cooling. We find linear decay processes for both optical and acoustic phonon relaxations with acoustic cooling suppressed at high temperatures. Our results reveal different decay mecha…
Ultrafast dynamics of graphite is investigated by time-resolved photoemission spectroscopy. We observe spectral features of direct photoexcitations, non-thermal electron distributions, and recovery dynamics occurring with two time scales having distinct pump-power dependences. Additionally, we find an anomalous increase of the spectral intensity around the Fermi level, and we attribute this to spectral broadenings due to coupled optical phonons in the transient. The fingerprints of the coupled optical phonons occur from the temporal region where the electronic temperature is still not definabl…
We describe an ultrafast coherent control of the transient structural distortion arising from nonlinear phononics in ErFeO$_3$. Using density functional theory, we calculate the structural properties as input to an anharmonic phonon model that describes the response of the system to a pulsed optical excitation. We find that the trilinear coupling of two orthogonal infrared-active phonons to a Raman-active phonon causes a transient distortion of the lattice. The direction of the distortion is determined by the polarization of the exciting light, suggesting a route to nonlinear phononic lattice …
The zone-center $E_{2g}$ modes play a crucial role in MgB$_2$, controlling the scattering mechanisms in the normal state as well the superconducting pairing. Here, we demonstrate via first-principles quantum-field theory calculations that, due to the anisotropic electron-phonon interaction, a $hot$-$phonon$ regime where the $E_{2g}$ phonons can achieve significantly larger effective populations than other modes, is triggered in MgB$_2$ by the interaction with an ultra-short laser pulse. Spectral signatures of this scenario in ultrafast pump-probe Raman spectroscopy are discussed in detail, rev…
The valley degree of freedom and the possibility of spin-valley coupling of solid materials have attracted growing interest, and the relaxation dynamics of spin- and valley-polarized states has become an important focus of recent studies. In spin-orbit-coupled inversion-asymmetric two-dimensional materials, such as MoS_{2} it has been found that the spin randomization is characteristically faster than the time scales for inter- and intra-valley scatterings. In this study, we examined the ultrafast non-collinear spin dynamics of an electron valley in monolayer MoS_{2} by using real-time propaga…
Identifying an efficient pathway to change the order parameter via a subtle excitation of the coupled high-frequency mode is the ultimate goal of the field of ultrafast phase transitions. This is an especially interesting research direction in magnetism, where the coupling between spin and lattice excitations is required for magnetization reversal. Despite several attempts however, the switching between magnetic states via resonant pumping of phonon modes has not yet been demonstrated. Here we show how an ultrafast resonant excitation of the longitudinal optical phonon modes in magnetic garnet…
We investigate ultrafast phonon dynamics in the Bi$_{1-x}$Sb$_{x}$ alloy system for various compositions $x$ using a reflective femtosecond pump-probe technique. The coherent optical phonons corresponding to the A$_{1g}$ local vibrational modes of Bi-Bi, Bi-Sb, and Sb-Sb are generated and observed in the time domain with a few picoseconds dephasing time. The frequencies of the coherent optical phonons were found to change as the Sb composition $x$ was varied, and more importantly, the relaxation time of those phonon modes was dramatically reduced for $x$ values in the range 0.5--0.8. We argue …
The magnetization response of bulk ferromagnets after excitation by an ultrashort optical pulse is calculated using a dynamical model of the Elliott-Yafet type that includes the effects of the spin-orbit interaction in the ab-initio ferromagnetic band structure, the electron-phonon interaction at the level of Boltzmann scattering integrals, and dynamical changes in the temperature of the phonon bath. Using realistic parameters for the ultrashort optical pulse, the computed maximum magnetization quenching achievable with electron-phonon scattering in a fixed band structure is much smaller than …
We report a computational theoretical investigation of electron spin-flip scattering induced by the electron-phonon interaction in the transition-metal ferromagnets bcc Fe, fcc Co and fcc Ni. The Elliott-Yafet electron-phonon spin-flip scattering is computed from first-principles, employing a generalized spin-flip Eliashberg function as well as ab initio computed phonon dispersions. Aiming at investigating the amount of electron-phonon mediated demagnetization in femtosecond laser-excited ferromagnets, the formalism is extended to treat laser-created thermalized as well as nonequilibrium, nont…
We present ultrafast x-ray diffraction experiments on thin films of metallic SrRuO$_3$ (SRO) after their excitation with ultrashort intense laser pulses. Depending on the layer thickness, the data exhibit a transient splitting of the (002) SRO Bragg peak evidencing the generation and propagation of sharp acoustic strain waves. These distinct structural dynamics are due to the exceptionally fast electron-phonon relaxation that gives rise to a quasi-instantaneous thermal stress in SRO. The interpretation is corroborated by numerical simulations which show excellent agreement with the experimenta…
NaOH-reacted graphite oxide film was prepared by decomposing epoxy groups in graphite oxide into hydroxyl and -ONa groups with NaOH solution. Ultrafast carrier dynamics of the sample were studied by time-resolved transient differential reflection (\DeltaR/R). The data show two exponential relaxation processes. The slow relaxation process (\sim2ps) is ascribed to low energy acoustic phonon mediated scattering. The electron-phonon coupling and first-principles calculation results demonstrate that - OH and -ONa groups in the sample are strongly coupled. Thus, we attribute the fast relaxation proc…
Despite intense experimental effort, theoretical proposals and modeling approaches, a lack of consensus exists about the intrinsic mechanisms driving ultrafast magnetization dynamics in 3$d$ ferromagnets. In this work, we find evidence of electron-phonon mediated spin-flip as the driving mechanism for the ultrafast magnetization dynamics in all three 3$d$ ferromagnets; nickel, iron and cobalt. We use a microscopic three temperature model with parameters calculated from first-principles, which has been validated by direct comparison to the electron and lattice dynamics extracted from previous e…
We discuss phonon-induced non-Markovian and Markovian features in QD-based optics. We cover lineshapes in linear absorption experiments, phonon-induced incoherence in the Heitler regime, and memory correlations in two-photon coherences. To quantitatively and qualitatively understand the underlying physics, we present several theoretical models which model the non-Markovian properties of the electron-phonon interaction accurately in different regimes. Examples are the Heisenberg equation of motion approach, the polaron master equation, and Liouville-propagator techniques in the independent boso…
In order to determine the role of non-thermal transport of hot carriers which is decisive for the dissipation of energy in condensed matter we performed time-resolved broadband femtosecond transient reflectivity measurements on $7-197 \mathrm{nm}$ thick Bi(111) films epitaxially grown on Si(111). We monitored the behavior of the Fourier amplitude and the central frequency of the coherent $A_\mathrm{1g}$ phonon mode as function of the incident fluence, film thickness, and probe wavelength in the range of $580 -700 \mathrm{nm}$. The frequency redshift that follows photoexcitation was used as a r…
Despite their fundamental role in determining material properties, detailed momentum-dependent information on the strength of electron-phonon and phonon-phonon coupling (EPC and PPC, respectively) across the entire Brillouin zone (BZ) has proved difficult to obtain. Here we demonstrate that ultrafast electron diffuse scattering (UEDS) directly provides such information. By exploiting symmetry-based selection rules and time-resolution, scattering from different phonon branches can be distinguished even without energy resolution. Using graphite as a model system, we show that UEDS patterns map t…
We theoretically investigate spin-dependent carrier dynamics due to the electron-phonon interaction after ultrafast optical excitation in ferromagnetic metals. We calculate the electron-phonon matrix elements including the spin-orbit interaction in the electronic wave functions and the interaction potential. Using the matrix elements in Boltzmann scattering integrals, the momentum-resolved carrier distributions are obtained by solving their equation of motion numerically. We find that the optical excitation with realistic laser intensities alone leads to a negligible magnetization change, and …
We use theory and first-principles calculations to investigate how structural changes induced by ultrafast optical excitation of infrared-active phonons change with hydrostatic pressure in LaAlO$_3$. Our calculations show that the observed structural changes are sensitive to pressure, with the largest changes occurring at pressures near the boundary between the cubic perovskite and rhombohedral phases. We rationalize our findings by defining a figure of merit that depends only on intrinsic materials quantities, and show that the peak response near the phase boundary is dictated by different mi…
One central challenge in understanding phonon thermal transport is a lack of experimental tools to investigate mode-based transport information. Although recent advances in computation lead to mode-based information, it is hindered by unknown defects in bulk region and at interfaces. Here we present a framework that can reveal microscopic phonon transport information in heterostructures, integrating state-of-the-art ultrafast electron diffraction (UED) with advanced scientific machine learning. Taking advantage of the dual temporal and reciprocal-space resolution in UED, we are able to reliabl…
Black phosphorus (BP) exhibits highly anisotropic properties and dynamical behavior that are unique even among two-dimensional and van der Waals (vdW) layered materials. Here, we show that an interlayer lattice contraction and concerted, symmetric intralayer vibrations take place concurrently within few picoseconds following the photoinjection and relaxation of carriers, using ultrafast electron diffraction in the reflection geometry to probe the out-of-plane motions. A strong coupling between the photocarriers and BP's puckered structure, with the alignment of the electronic band structure, i…
Chiral Phonons Enable Ultrafast Magnetization Switching via Magnetoelastic Coupling
Nanjing University of Aeronautics and Astronautics (NUAA)（南京航空航天大学）；Instituto de Ciencia de Materiales de Madrid (ICMM), CSIC（马德里材料科学研究所，西班牙国家科学研究委员会）；The University of Manchester（曼彻斯特大学）；University of York（约克大学）
We show that large amplitude, coherent acoustic phonon wavepackets can be generated and detected in In$_x$Ga$_{1-x}$N/GaN epilayers and heterostructures in femtosecond pump-probe differential reflectivity experiments. The amplitude of the coherent phonon increases with increasing Indium fraction $x$ and unlike other coherent phonon oscillations, both \textit{amplitude} and \textit{period} are strong functions of the laser probe energy. The amplitude of the oscillation is substantially and almost instantaneously reduced when the wavepacket reaches a GaN-sapphire interface below the surface indi…
The out-of-equilibrium dynamics of electrons and phonons upon laser excitation are often described by the two-temperature model, which assumes that both subsystems are separately in thermal equilibrium. However, recent experiments show that this description is not sufficient to describe the out-of-equilibrium dynamics on ultrashort timescales. Here, we extend and apply a parameter-free microscopic out-of-equilibrium model to describe the ultrafast laser-induced system dynamics of archetypical metallic systems such as gold, aluminum, iron, nickel, and cobalt. We report strong deviations from th…
We report the investigation of the generation and detection of GHz coherent acoustic phonons in plasmonic gold nanoparticles superlattices (NPS). The experiments have been performed from an optical femtosecond pump-probe scheme across the optical plasmon resonance of the superlattice. Our experiments allow to estimate the collective elastic response (sound velocity) of the NPS as well as an estimate of the nano-contact elastic stiffness. It appears that the light-induced coherent acoustic phonon pulse has a typical in-depth spatial extension of about 45 nm which is roughly 4 times the optical …
Ultrafast two-color pump-probe measurements, involving coherent acoustic phonon (CAP) waves, have provided information simultaneously on the mechanical properties and on the electronic structure of ferromagnetic GaMnAs. The elastic constant C11 of Ga1-xMnxAs (0.03<x<0.07) are observed to be systematically smaller than those of GaAs. Both C11 and Vs of GaMnAs are found to increase with temperature (78 K<T<295 K), again in contrast to the opposite behavior in GaAs. In addition, the fundamental bandgap (at E0 critical point) of Ga1-xMnxAs is found to shift slightly to higher energies with Mn conc…
The interaction between lattice and spins is at the heart of an extremely intriguing ultrafast dynamics in magnetic materials. In this work we formulate a general non-equilibrium theory that disentangles the complex interplay between them in a THz laser-excited antiferromagnetic insulator. The theory provides a quantitative description of the transient energy flow between the spin and lattice sub-systems, subject to magnon-phonon and phonon-phonon scatterings, giving rise to finite life-times of the quasiparticles and to the equilibration time of the system. We predict a novel kind of scatteri…
Ultrafast lattice dynamics of few quintuple layers of topological insulator (TI) Bi$_2$Te$_3$ is studied with time-resolved optical pump-probe spectroscopy. Both optical and acoustic phonons are photogenerated and detected. Here, in order to get new insights on the out-of-equilibrium electron-phonon coupling and phonons dynamics in confined TI, different nanostructures have been investigated (single or polycrystalline QLs assemblies and nano-crystallized islands). Contrary to previous literature claims, we show that even for nanostructures containing only 10 quintuple layers (QLs), the symmetr…
Interactions between the lattice and charge carriers can drive the formation of phases and ordering phenomena that give rise to conventional superconductivity, insulator-to-metal transitions, and charge-density waves. These couplings also play a determining role in properties that include electric and thermal conductivity. Ultrafast electron diffuse scattering (UEDS) has recently become a viable laboratory-scale tool to track energy flow into and within the lattice system across the entire Brillouin zone, and deconvolves interactions in the time domain. Here, we present a detailed quantitative…
Calculations combining first-principles electron-phonon ($e$-ph) interactions with the Boltzmann equation enable studies of ultrafast carrier and phonon dynamics. However, in materials with weak Coulomb screening, electrons and holes form bound excitons and their scattering processes become correlated, posing additional challenges for modeling nonequilibrium physics. Here we show calculations of ultrafast exciton dynamics and related time-domain spectroscopies using $ab~initio$ exciton-phonon (ex-ph) interactions together with an excitonic Boltzmann equation. Starting from the nonequilibrium e…
Femtosecond dynamics of coherent optical phonons in GeTe/Sb$_{2}$Te$_{3}$ superlattices (SLs), a new class of semiconductor SLs with three different states, have been investigated by using a reflection-type pump-probe technique at various lattice temperatures. The time-resolved transient reflectivity (TR) obtained in as-grown SLs exhibits the coherent A$_{1}$ optical modes at 5.10 THz and 3.78 THz, while only the single A$_{1}$ mode at 3.68 THz is observed in annealed SLs. The decay rate of the A$_{1}$ mode in annealed SLs is strongly temperature dependent, while that in as-grown SLs is not te…
The ultrafast dynamics of magnetic order in a ferromagnet are governed by the interplay between electronic, magnetic and lattice degrees of freedom. In order to obtain a microscopic understanding of ultrafast demagnetization, information on the response of all three subsystems is required. A consistent description of demagnetization and microscopic energy flow, however, is still missing. Here, we combine a femtosecond electron diffraction study of the ultrafast lattice response of nickel to laser excitation with ab initio calculations of the electron-phonon interaction and energy-conserving at…
Ultrafast optical excitation of gold-cobalt bilayers triggers the nontrivial interplay between the electronic, acoustic, and magnetic degrees of freedom. Laser-heated electrons generated at the gold-air interface diffuse through the layer of gold and strongly overheat the lattice in cobalt resulting in the emission of ultrashort acoustic pulses and generation of exchange-coupled magnons. Time-resolved optical measurements allow for extracting the thermal boundary (Kapitza) resistances at metal/metal interfaces and the hot electron diffusion length in ferromagnetic materials. Both the experimen…
While valleys (energy extrema) are present in all band structures of solids, their preeminent role in determining exciton resonances and dynamics in atomically thin transition metal dichalcogenides (TMDC) is unique. Using two-dimensional coherent electronic spectroscopy, we find that exciton decoherence occurs on a much faster time scale in MoSe$_2$ bilayers than that in the monolayers. We further identify two population relaxation channels in the bilayer, a coherent and an incoherent one. Our microscopic model reveals that phonon-emission processes facilitate scattering events from the $K$ va…
We report on the dynamics of coherent phonons in semimetal 1T'-MoTe2 using femtosecond pump-probe spectroscopy. On an ultrafast sub-picosecond time scale at room temperature, a low frequency and long-lifetime shear phonon mode was observed at 0.39 THz, which was previously reported in the form of a characteristic phonon only in the low temperature Td-MoTe2 phase. Unlike the other optical phonon modes, the shear phonon mode was found to strongly couple with photoexcited carriers. Moreover, the amplitude of the shear mode surprisingly decreased with increasing excitation density, a phenomenon wh…
The excitonic absorption spectrum for a disordered quantum well in presence of exciton-acoustic phonon interaction is treated beyond the Markov approximation. Realistic disorder exciton states are taken from a microscopic simulation, and the deformation potential interaction is implemented. The exciton Green's function is solved with a self energy in second order Born quality. The calculated spectra differ from a superposition of Lorentzian lineshapes by enhanced inter-peak absorption. This is a manifestation of pure dephasing which should be possible to measure in near-field experiments.
