Nonequilibrium Phonon Dynamics Research Articles

Non-thermal phonon dynamics and a quenched exciton condensate probed by surface-sensitive electron diffraction

Interactions among and between electrons and phonons steer the energy flow in photo-excited materials and govern the emergence of correlated phases. The strength of electron–phonon interactions, decay channels of strongly coupled modes and the evolution of three-dimensional order are revealed by electron or X-ray pulses tracking non-equilibrium structural dynamics. Despite such capabilities, the growing relevance of inherently anisotropic two-dimensional materials and functional heterostructures still calls for techniques with monolayer sensitivity and, specifically, access to out-of-plane phonon polarizations. Here, we resolve non-equilibrium phonon dynamics and quantify the excitonic contribution to the structural order parameter in 1T-TiSe2. To this end, we introduce ultrafast low-energy electron diffuse scattering and trace strongly momentum- and fluence-dependent phonon populations. Mediated by phonon–phonon scattering, a few-picosecond build-up near the zone boundary precedes a far slower generation of zone-centre acoustic modes. These weakly coupled phonons are shown to substantially delay overall equilibration in layered materials. Moreover, we record the surface structural response to a quench of the material’s widely investigated exciton condensate, identifying an approximate 30:70 ratio of excitonic versus Peierls contributions to the total lattice distortion in the charge density wave phase. The surface-sensitive approach complements the ultrafast structural toolbox and may further elucidate the impact of phonon scattering in numerous other phenomena within two-dimensional materials, such as the formation of interlayer excitons in twisted bilayers.

Direct observation of strong momentum-dependent electron-phonon coupling in a metal.

Phonon scattering in metals is one of the most fundamental processes in materials science. However, understanding such processes has remained challenging and requires detailed information on interactions between phonons and electrons. We use an ultrafast electron diffuse scattering technique to resolve the nonequilibrium phonon dynamics in femtosecond-laser-excited tungsten in both time and momentum. We determine transient populations of phonon modes which show strong momentum dependence initiated by electron-phonon coupling. For phonons near Brillouin zone border, we observe a transient rise in their population on a timescale of approximately 1 picosecond driven by the strong electron-phonon coupling, followed by a slow decay on a timescale of approximately 8 picosecond governed by the weaker phonon-phonon relaxation process. We find that the exceptional harmonicity of tungsten is needed for isolating the two processes, resulting in long-lived nonequilibrium phonons in a pure metal. Our finding highlights that electron-phonon scattering can be the determinant factor in the phonon thermal transport of metals.

Hidden phonon highways promote photoinduced interlayer energy transfer in twisted transition metal dichalcogenide heterostructures.

Vertically stacked van der Waals (vdW) heterostructures exhibit unique electronic, optical, and thermal properties that can be manipulated by twist-angle engineering. However, the weak phononic coupling at a bilayer interface imposes a fundamental thermal bottleneck for future two-dimensional devices. Using ultrafast electron diffraction, we directly investigated photoinduced nonequilibrium phonon dynamics in MoS2/WS2 at 4° twist angle and WSe2/MoSe2 heterobilayers with twist angles of 7°, 16°, and 25°. We identified an interlayer heat transfer channel with a characteristic timescale of ~20 picoseconds, about one order of magnitude faster than molecular dynamics simulations assuming initial intralayer thermalization. Atomistic calculations involving phonon-phonon scattering suggest that this process originates from the nonthermal phonon population following the initial interlayer charge transfer and scattering. Our findings present an avenue for thermal management in vdW heterostructures by tailoring nonequilibrium phonon populations.

Nonequilibrium Phonon Dynamics and Its Impact on the Thermal Conductivity of the Benchmark Thermoelectric Material SnSe.

Thermoelectric materials play a vital role in the pursuit of a sustainable energy system by allowing the conversion of waste heat to electric energy. Low thermal conductivity is essential to achieving high-efficiency conversion. The conductivity depends on an interplay between the phononic and electronic properties of the nonequilibrium state. Therefore, obtaining a comprehensive understanding of nonequilibrium dynamics of the electronic and phononic subsystems as well as their interactions is key for unlocking the microscopic mechanisms that ultimately govern thermal conductivity. A benchmark material that exhibits ultralow thermal conductivity is SnSe. We study the nonequilibrium phonon dynamics induced by an excited electron population using a framework combining ultrafast electron diffuse scattering and nonequilibrium kinetic theory. This in-depth approach provides a fundamental understanding of energy transfer in the spatiotemporal domain. Our analysis explains the dynamics leading to the observed low thermal conductivity, which we attribute to a mode-dependent tendency to nonconservative phonon scattering. The results offer a penetrating perspective on energy transport in condensed matter with far-reaching implications for rational design of advanced materials with tailored thermal properties.

Nanoscale imaging of phonon dynamics by electron microscopy

Spatially resolved vibrational mapping of nanostructures is indispensable to the development and understanding of thermal nanodevices1, modulation of thermal transport2 and novel nanostructured thermoelectric materials3–5. Through the engineering of complex structures, such as alloys, nanostructures and superlattice interfaces, one can significantly alter the propagation of phonons and suppress material thermal conductivity while maintaining electrical conductivity2. There have been no correlative experiments that spatially track the modulation of phonon properties in and around nanostructures due to spatial resolution limitations of conventional optical phonon detection techniques. Here we demonstrate two-dimensional spatial mapping of phonons in a single silicon–germanium (SiGe) quantum dot (QD) using monochromated electron energy loss spectroscopy in the transmission electron microscope. Tracking the variation of the Si optical mode in and around the QD, we observe the nanoscale modification of the composition-induced red shift. We observe non-equilibrium phonons that only exist near the interface and, furthermore, develop a novel technique to differentially map phonon momenta, providing direct evidence that the interplay between diffuse and specular reflection largely depends on the detailed atomistic structure: a major advancement in the field. Our work unveils the non-equilibrium phonon dynamics at nanoscale interfaces and can be used to study actual nanodevices and aid in the understanding of heat dissipation near nanoscale hotspots, which is crucial for future high-performance nanoelectronics.

Transport and relaxation of current-generated nonequilibrium phonons from nonlocal electronic measurements

We study phonons generated by current in a Pt nanowire, by measuring resistance of another nanowire separated from the first one by an insulating spacer. For thin spacers, the resistance varies almost linearly with current at cryogenic temperatures, while an additional quadratic contribution emerges for thicker spacers. These observations suggest a non-thermal distribution of current-generated phonons that relax via strongly nonlinear dynamical processes rather than few-phonon scattering. Our results provide insight into the nonequilibrium phonon dynamics at nanoscale, which may facilitate efficient heat management in electronic nanodevices.

Optical Control of Non-Equilibrium Phonon Dynamics.

The light-induced selective population of short-lived far-from-equilibrium vibration modes is a promising approach for controlling ultrafast and irreversible structural changes in functional nanomaterials. However, this requires a detailed understanding of the dynamics and evolution of these phonon modes and their coupling to the excited-state electronic structure. Here, we combine femtosecond mega-electronvolt electron diffraction experiments on a prototypical layered material, MoTe2, with non-adiabatic quantum molecular dynamics simulations and ab initio electronic structure calculations to show how non-radiative energy relaxation pathways for excited electrons can be tuned by controlling the optical excitation energy. We show how the dominant intravalley and intervalley scattering mechanisms for hot and band-edge electrons leads to markedly different transient phonon populations evident in electron diffraction patterns. This understanding of how tuning optical excitations affect phonon populations and atomic motion is critical for efficiently controlling light-induced structural transitions of optoelectronic devices.

Mapping momentum-dependent electron-phonon coupling and nonequilibrium phonon dynamics with ultrafast electron diffuse scattering

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 the relative EPC and PPC strength through their profound sensitivity to photoinduced changes in phonon populations. We measure strong EPC to the $K$-point transverse optical phonon of $A_1'$ symmetry ($K-A_1'$) and along the entire longitudinal optical branch between $\Gamma-K$, not only to the $\Gamma-E_{2g}$ phonon as previously emphasized. We also determine that the subsequent phonon relaxation pathway involves three stages; decay via several identifiable channels to transverse acoustic (TA) and longitudinal acoustic (LA) phonons (1-2 ps), intraband thermalization of the non-equilibrium TA/LA phonon populations (30-40 ps) and interband relaxation of the LA/TA modes (115 ps). Combining UEDS with ultrafast angle-resolved photoelectron spectroscopy will yield a complete picture of the dynamics within and between electron and phonon subsystems, helping to unravel complex phases in which the intertwined nature of these systems have a strong influence on emergent properties.

Ultrafast atomic-scale visualization of acoustic phonons generated by optically excited quantum dots

Understanding the dynamics of atomic vibrations confined in quasi-zero dimensional systems is crucial from both a fundamental point-of-view and a technological perspective. Using ultrafast electron diffraction, we monitored the lattice dynamics of GaAs quantum dots—grown by Droplet Epitaxy on AlGaAs—with sub-picosecond and sub-picometer resolutions. An ultrafast laser pulse nearly resonantly excites a confined exciton, which efficiently couples to high-energy acoustic phonons through the deformation potential mechanism. The transient behavior of the measured diffraction pattern reveals the nonequilibrium phonon dynamics both within the dots and in the region surrounding them. The experimental results are interpreted within the theoretical framework of a non-Markovian decoherence, according to which the optical excitation creates a localized polaron within the dot and a travelling phonon wavepacket that leaves the dot at the speed of sound. These findings indicate that integration of a phononic emitter in opto-electronic devices based on quantum dots for controlled communication processes can be fundamentally feasible.

Optimization of phonon dynamics protocols in ion traps

We develop a theory to address the non equilibrium dynamics of phonons in a one-dimensional finite size trapped ion system for non linear ramp and periodic protocols. Our analysis, which is based on our earlier proposal of dynamics-induced cooling and entanglement generation between phonons in these systems when subjected to a linear ramp protocol [], identifies the optimal protocol within the above-mentioned classes, which minimizes both the cooling and entanglement generation time. We also introduce single-/two-site addressing to achieve cooling/entanglement, which is expected to lead to simpler implementation of these protocols. Finally, we discuss the effect of noise due to the fluctuation of the intensity of the laser used to generate the trap on entanglement generation. We also discuss realistic experimental setups that may serve as test beds for our theory.

Nonequilibrium phonon effects in midinfrared quantum cascade lasers

We investigate the effects of nonequilibrium phonon dynamics on the operation of a GaAs-based midinfrared quantum cascade laser over a range of temperatures (77–300 K) via a coupled ensemble Monte Carlo simulation of electron and optical-phonon systems. Nonequilibrium phonon effects are shown to be important below 200 K. At low temperatures, nonequilibrium phonons enhance injection selectivity and efficiency by drastically increasing the rate of interstage electron scattering from the lowest injector state to the next-stage upper lasing level via optical-phonon absorption. As a result, the current density and modal gain at a given field are higher and the threshold current density lower and considerably closer to experiment than results obtained with thermal phonons. By amplifying phonon absorption, nonequilibrium phonons also hinder electron energy relaxation and lead to elevated electronic temperatures.

Nonequilibrium phonon dynamics in trapped-ion systems

We propose a concrete experiment to probe the nonequilibrium local dynamics of the one-dimensional Bose-Hubbard model using a trapped ion system consisting of a linear chain of few ions prepared in a state of transverse motional mode which corresponds to a fixed number of phonons per ion. These phonons are well known to be described by an effective Bose-Hubbard model. We propose a protocol which leads to a sudden local sign reversal of the on-site interaction strength of this Hubbard model at one of the sites and demonstrate that the subsequent nonequilibrium dynamics of the model can be experimentally probed by measuring the time-dependent phonon number in a specific motional state of the ions. We back our experimental proposal with exact numerical calculation of the dynamics of a Bose-Hubbard model subsequent to a local quench.

Imaging single electrons to enable the generation of ultrashort beams for single-shot femtosecond relativistic electron diffraction

The generation and control of relativistic electron beams well suited for ultrafast electron diffraction application has rapidly advanced, greatly benefiting from the overlap in techniques and expertise with the accelerator community. However, imaging the diffracted MeV electrons with high detection efficiency has remained an under-explored area. In this paper, we report on a quantitative study of the imaging of MeV electrons using a detection system consisting of a phosphor screen, a lens-coupling optics, and a charge-coupled device camera. It is shown that every MeV electron in the beam yields a signal well above the camera noise. With this detection efficiency, only ∼105 electrons per pulse are needed to obtain a high quality single-shot diffraction pattern from a crystalline sample. We measured that such a low charge beam can be as short as 30 fs rms. Further, we discuss the possibility of compressing these electron beams to sub-5 fs rms bunch length by velocity bunching using a short high gradient rf accelerating structure scheduled to be installed next year at the UCLA Pegasus Laboratory. This opens the possibility of single-shot determinations of structural changes in many ultrafast physical processes like nonequilibrium phonon dynamics or relaxation pathways in systems with strong electron-phonon coupling.

Non-equilibrium phonon dynamics studied by grazing-incidence femtosecond X-ray crystallography

The timescales for structural changes in a single crystal of bismuth after excitation with an intense near-infrared laser pulse are studied with femtosecond pump-probe X-ray diffraction. Changes in the intensity and reciprocal-lattice vector of several reflections give quantitative information on the structure factor and lattice strain as a function of time, with a resolution of 200 fs. The results indicate that the majority of excess carrier energy that remains near the surface is transferred to vibrational modes on a timescale of about 10 ps, and that the resultant increase in the variance of the atomic positions at these times is consistent with the overall magnitude of lattice strain that develops.

Carrier heating in light-emitting quantum-dot heterostructures at low injection currents

We present microscopic calculations of the light emission and carrier dynamics in an electrically pumped quantum-dot emitter at low injection currents and room temperature. The modeled structure consists of a bulk semiconductor and self organized InGaAs/GaAs quantum-dot layers (embedded by a wetting layer). Carrier transport through the structure is driven by scattering with longitudinal optical phonons including the nonequilibrium phonon dynamics. Even though the phonon distribution remains at room temperature, a substantial carrier heating corresponding to more than 50 K above the phonon temperature occurs in the wetting layer. Surprisingly, this temperature difference is observed in particular at low pump currents. It can be attributed to a nonequilibrium in the sample due to energy level alignment and external pumping.

Observation of local heating in an ion track by measuring the ion-induced luminescence spectrum

The rise of the local temperature in an ion track was observed by utilizing fast exciton radiative recombination in the layered perovskite-type materials (C 3H 7NH 3) 2PbBr 4 and (C 4H 9NH 3) 2PbBr 4. In (C 3H 7NH 3) 2PbBr 4, the local temperature was an increasing function of the excitation density or linear energy transfer (LET). However, the same local temperature was obtained for different LETs in (C 4H 9NH 3) 2PbBr 4, which was attributed to local melting of the organic layers. Furthermore, the obtained value of the local “melting point” was much higher than that in the bulk analog of the organic and inorganic layers, which indicates that nonequilibrium phonon dynamics plays a crucial role in the thermal spike process.

Subpicosecond Time-Resolved Raman Studies of Non-Equilibrium Excitations in Wide Bandgap GaN

Non-equilibrium phonon dynamics in wurtzite GaN have been studied by subpicosecond time-resolved Raman spectroscopy. The population relaxation time of longitudinal optical phonons was directly measured to be τ ≅ (5 ± 1) ps at T = 25 K. The experimental results on the temperature dependence of the lifetime of longitudinal optical phonons suggest that the primary decay channels for these phonons are the decay into (i) one transverse optical phonon and one high energy, longitudinal or transverse acoustical phonons; and (ii) one transverse optical phonon and one E2 phonon.

Picosecond dynamics of nonequilibrium phonons in trans-polyacetylene studied by transient photoinduced resonance Raman scattering

The technique of picosecond transient resonant anti-Stokes (AS) Raman scattering has been applied to polyacetylene thin films for studying electronic photoexcitation and phonon dynamics. We observed a transient photoinduced increase in the AS scattering intensity for the CC stretching mode at 1088 cm −1. This enhancement is assigned to a nonequilibrium phonon population, which is generated by the formation, thermalization and geminate recombination of the photoexcited charged solitons. From the decay of the nonequilibrium CC stretching mode population, we determined its lifetime to be 5.5 ± 0.5 ps. We also found a much longer none-quilibrium phonon relaxation process, which does not exist in conventional semiconductors.

Nonequilibrium phonon dynamics and electron distribution functions in InP and InAs

We have used subpicosecond laser pulses to study the generation of nonequilibrium LO phonons in both InP and InAs. These two semiconductors provide a contrast in that the decaying of the Raman signal probes different relaxation mechanisms. In InP, for example, we find that the decay of the Raman signal is dominated by the lifetime of the LO phonons. On the contrary, in InAs, our studies show that the decay of the Raman signal is governed by the time required for electrons to return to the \ensuremath{\Gamma} valley from the L valleys of the conduction bands. In addition, nonequilibrium electron distributions were also studied in InP and InAs. We have found that the single-particle-scattering spectrum in InAs can only be observed with the use of a much longer laser pulse width than subpicosecond as a result of electron intervalley scattering and very small electron effective mass. \textcopyright{} 1996 The American Physical Society.

The investigation of nonequilibrium phonon dynamics using defect induced one phonon absorption

The combination of defect induced one phonon absorption and absorption vibronic sideband spectroscopy can be used to investigate the spectral, temporal and spatial dynamics of nonequilibrium phonon populations. The implementation of these techniques is described and the details of two experiments using these techniques are provided.