Ultrafast electron dynamics of solids after an absorption of femtosecond laser pulse is governed by electron-electron, electron-phonon, phonon-electron, and phonon-phonon collisions. It is of importance to construct a framework for interpreting experimental observations correctly. In this paper we review recent developments of modeling the relaxation dynamics of solids. We discuss the ultrafast relaxation in respect to the effective temperature dynamics and the excess energy dynamics.
Bi possesses intriguing properties due to its large spin-orbit coupling, e.g. as a constituent of topological insulators. While its electronic structure and the dynamics of electron-phonon coupling have been studied in the past, photo-induced charge carriers have not been observed in the early phases of their respective relaxation pathways. Using two-photon photoemission (2PPE) we follow the de-excitation pathway of electrons along the unoccupied band structure and into a bulk hole pocket. Two decay channels are found, one of which involves an Auger process. In the hole pocket, the electrons u…
We report ultrafast surface pump and interface probe experiments on photoexcited carrier transport across single crystal bismuth films on sapphire. The film thickness is sufficient to separate carrier dynamics from lattice heating and strain, allowing us to investigate the time-scales of momentum relaxation, heat transfer to the lattice and electron-hole recombination. The measured electron-hole ($e-h$) recombination time is 12--26 ps and ambipolar diffusivity is 18--40 cm$^{2}$/s for carrier excitation up to $\sim 10^{19} \text{cm}^{-3}$. By comparing the heating of the front and back sides o…
For most optoelectronic applications of graphene a thorough understanding of the processes that govern energy relaxation of photoexcited carriers is essential. The ultrafast energy relaxation in graphene occurs through two competing pathways: carrier-carrier scattering -- creating an elevated carrier temperature -- and optical phonon emission. At present, it is not clear what determines the dominating relaxation pathway. Here we reach a unifying picture of the ultrafast energy relaxation by investigating the terahertz photoconductivity, while varying the Fermi energy, photon energy, and fluenc…
We demonstrate that in confined plasmonic metal structures subject to ultra-fast laser excitation electron thermal diffusion can provide relaxation faster than the energy transfer to the lattice. This relaxation occurs due to excitation of nanometer-sized hot spots in the confined structure and the sensitivity of its optical parameters to the perturbation in these regions. Both factors become essential when the plasmonic resonance condition is met for both excitation and detection. A pump-probe experiment on plasmonic gold lattices shows sub-picosecond relaxation with the characteristic times …
We theoretically study the dynamic time evolution following laser pulse pumping in an antiferromagnetic insulator Cr$_{2}$O$_{3}$. From the photoexcited high-spin quartet states to the long-lived low-spin doublet states, the ultrafast demagnetization processes are investigated by solving the dissipative Schrödinger equation. We find that the demagnetization times are of the order of hundreds of femtosecond, in good agreement with recent experiments. The switching times could be strongly reduced by properly tuning the energy gaps between the multiplet energy levels of Cr$^{3+}$. Furthermore, th…
Phase change alloys have seen widespread use from rewritable optical discs to the present day interest in their use in emerging neuromorphic computing architectures. In spite of this enormous commercial interest, the physics of carriers in these materials is still not fully understood. Here, we describe the time and space dependence of the coupling between photoexcited carriers and the lattice in both the amorphous and crystalline states of one phase change material, GeTe. We study this using a time-resolved optical technique called picosecond acoustic method to investigate the \textit{in situ…
We investigate the dynamical formation of excitons from photoexcited electron-hole plasma and its subsequent decay dynamics in monolayer MoS2 grown by chemical vapor deposition using ultrafast pump and terahertz probe spectroscopy. Different photoexcited electron-hole states are resolved based on their distinct responses to THz photon and decay lifetime. The observed transient THz transmission can be fit with two decay components: a fast component with decay lifetime of 20 ps, which is attributed to exciton life time including the exciton formation and subsequent intraexciton relaxation; a slo…
We present a theory of ultrafast photo-induced dynamics in a spin-charge coupled system, motivated by pump-probe experiments in perovskite manganites. A microscopic picture for multiple dynamics in spin and charge degrees is focused on. Real-time simulations are carried out by two complimentary methods. Our calculation demonstrates that electron motion governs a short-time scale where charge and spin dynamics are combined strongly, while, in a long-time scale controlled by spin relaxation, charge sector does not follow remarkable change in spin sector. Present results are in contrast to a conv…
We present a complementary experimental and theoretical investigation of relaxation dynamics in the charge-density-wave (CDW) system TbTe$_3$ after ultrafast optical excitation. Using time- and angle-resolved photoemission spectroscopy, we observe an unusual transient modulation of the relaxation rates of excited photocarriers. A detailed analysis of the electron self-energy based on a nonequilibrium Green's function formalism reveals that the phase space of electron-electron scattering is critically modulated by the photoinduced collective CDW excitation, providing an intuitive microscopic un…
We present a first-principles method for the calculation of the temperature-dependent relaxation of symmetry-breaking atomic driving forces in photoexcited systems. We calculate the phonon-assisted decay of the photoexcited force on the low-symmetry $E_g$ mode following absorption of an ultrafast pulse in the prototypical group-V semimetals, Bi, Sb and As. The force decay lifetimes for Bi and Sb are of the order of $10$ fs and in good agreement with recent experiments, demonstrating that electron-phonon scattering is the dominant mechanism relaxing the symmetry-breaking forces. Calculations fo…
We demonstrate an ultrafast reversible modulation of resonant terahertz (THz) response in strongly photoexcited metamaterials. The transient spectral-temporal response of the dipole transition ~1.6 THz exhibits a distinct non-monotonic variation as a function of pump fluence. The transition energy shift, strength, spectral width and density-dependent ultrafast relaxation manifest a remarkable re-emergence of the resonances after initial quenching. Our simulation, incorporating the first-order diffraction from the photoinduced transient grating, reproduces the salient features, providing a new …
The diffusion of electron-hole pairs, which are excited in an intrinsic graphene by the ultrashort focused laser pulse in mid-IR or visible spectral region, is described for the cases of peak-like or spread over the passive region distributions of carriers. The spatio-temporal transient optical response on a high-frequency probe beam appears to be strongly dependent on the regime of diffusion and can be used for verification of the elasic relaxation mechanism. Sign flip of the differential transmission coefficient takes place due to interplay of the carrier-induced contribution and weak dynami…
Transient X-ray spectroscopies have become ubiquitous in studying photoexcited dynamics in solar energy materials due to their sensitivity to carrier occupations and local chemical or structural dynamics. The interpretation of solid-state photoexcited dynamics, however, is complicated by the core-hole perturbation and the resulting many-body dynamics. Here, an ab initio, Bethe-Salpeter equation (BSE) approach is developed that can incorporate photoexcited state effects for solid-state materials. The extreme ultraviolet (XUV) absorption spectra for the ground, photoexcited, and thermally expand…
We report results from ultrafast two-color optical pump-probe spectroscopy on bulk $β$-Ga$_2$O$_3$. A two-photon absorption scheme is used to photoexcite carriers with the pump pulse and free-carrier absorption of the probe pulse is used to record the subsequent dynamics of the photoexcited carriers. Our results are consistent with carrier recombination via defect-assisted processes. We also observe transient polarization-selective optical absorption of the probe pulse by defect states under nonequilibrium conditions. A rate equation model for electron and hole capture by defects is proposed a…
We report ultrafast response of femtosecond photoexcited carriers in single layer reduced graphene oxide flakes suspended in water as well as few layer thick film deposited on indium tin oxide coated glass plate using pump-probe differential transmission spectroscopy at 790 nm. The carrier relaxation dynamics has three components: ~200 fs, 1 to 2 ps, and ~25 ps, all of them independent of pump fluence. It is seen that the second component (1 to 2 ps) assigned to the lifetime of hot optical phonons is larger for graphene in suspensions whereas other two time constants are the same for both the …
We discuss the photovoltaic effect at a p-n heterojunction, in which the illuminated side is a doped Mott insulator, using the simplest description of a Mott insulator within the Hubbard model. We find that the internal quantum efficiency of such a device, if we choose an appropriate narrow-gap Mott insulator, can be significantly enhanced due to impact ionization caused by the photoexcited ``hot'' electron/hole pairs. Namely, the photoexcited electron and/or hole can convert its excess energy beyond the Mott-Hubbard gap to additional electrical energy by creating multiple electron/hole pairs …
Tuning of Photoexcited Electron Dynamics at Monolayer h-BN/Metal Interfaces by Corrugation
Osaka Metropolitan University（大阪公立大学）；Institute for Molecular Science, National Institutes of Natural Sciences（国立自然科学院分子科学研究所）；Friedrich Schiller University Jena（耶拿弗里德里希·席勒大学）
Transient XUV spectroscopy is growing in popularity for the measurement of solar fuel and photovoltaic materials as it can separately measure electron and hole energies for multiple elements at once. However, interpretation of transient XUV measurements is complicated by changes in core-valence exciton and angular momentum effects after photoexcitation. Here, we report the photoexcited electron and hole dynamics for ZnTe, a promising material for CO2 reduction, following 400 nm excitation. We apply a newly developed, ab-initio theoretical approach based on density functional theory and the Bet…
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…
Two-dimensional (2D) crystals of semiconducting transition metal dichalcogenides (TMD) absorb a large fraction of incident photons in the visible frequencies despite being atomically thin. It has been suggested that the strong absorption is due to the parallel band or "band nesting" effect and corresponding divergence in the joint density of states. Here, we show using photoluminescence excitation spectroscopy that the band nesting in mono- and bilayer MX$_2$ (M = Mo, W and X = S, Se) results in excitation-dependent characteristic relaxation pathways of the photoexcited carriers. Our experimen…
We employ ultra-broadband terahertz-midinfrared probe pulses to characterize the optical response of photoinduced charge-carrier plasmas in high-resistivity silicon in a reflection geometry, over a wide range of excitation densities (10^{15}-10^{19} cm^{-3}) at room temperature. In contrast to conventional terahertz spectroscopy studies, this enables one to directly cover the frequency range encompassing the resultant plasma frequencies. The intensity reflection spectra of the thermalized plasma, measured using sum-frequency (up-conversion) detection of the probe pulses, can be modeled well by…
Photoexcited metals can produce highly-energetic hot carriers whose controlled generation and extraction is a promising avenue for technological applications. While hot carrier dynamics in Au-group metals have been widely investigated, a microscopic description of the dynamics of photoexcited carriers in the mid-infrared and near-infrared Pt-group metals range is still scarce. Since these materials are widely used in catalysis and, more recently, in plasmonic catalysis, their microscopic carrier dynamics characterization is crucial. We employ \emph{ab initio} many-body perturbation theory to i…
The element specificity of soft X-ray spectroscopy makes it an ideal tool for analyzing the microscopic origin of ultrafast dynamics induced by localized optical excitation in metal-insulator heterostructures. Using [Fe/MgO]$_n$ as a model system, we perform ultraviolet pump/soft X-ray probe experiments, which are sensitive to all constituents of these heterostructures, to probe both electronic and lattice excitations. Complementary ultrafast electron diffraction experiments independently analyze the lattice dynamics of the Fe constituent, and together with ab initio calculations yield compreh…
We report a comprehensive study of ultrafast carrier dynamics in single crystals of multiferroic BiFeO$_{3}$. Using femtosecond optical pump-probe spectroscopy, we find that the photoexcited electrons relax to the conduction band minimum through electron-phonon coupling with a $\sim$1 picosecond time constant that does not significantly change across the antiferromagnetic transition. Photoexcited electrons subsequently leave the conduction band and primarily decay via radiative recombination, which is supported by photoluminescence measurements. We find that despite the coexisting ferroelectri…
Direct measurements of photoexcited carrier dynamics in nickel are made using few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy at the nickel M$_{2,3}$ edge. It is observed that the core-level absorption lineshape of photoexcited nickel can be described by a Gaussian broadening ($σ$) and a red shift ($ω_{s}$) of the ground state absorption spectrum. Theory predicts, and the experimental results verify that after initial rapid carrier thermalization, the electron temperature increase ($ΔT$) is linearly proportional to the Gaussian broadening factor $σ$, providing quant…
The spin relaxation time in solids is determined by several competing energy scales and processes and distinct methods are called for to analyze the various regimes. We present a stochastic model for the spin dynamics in solids which is equivalent to solving the spin Boltzmann equation and takes the relevant processes into account on equal footing. The calculations reveal yet unknown parts of the spin-relaxation phase diagram, where strong spin-dephasing occurs in addition to spin-relaxation. Spin-relaxation times are obtained for this regime by introducing the numerical Loschmidt echo. This a…
In hybrid lead halide perovskites, the coupling between photogenerated charges and the ionic degrees of freedom plays a crucial role in defining the intrinsic limit of carrier mobility and lifetime. However, direct investigation of this fundamental interaction remains challenging because its relevant dynamics occur on ultrashort spatial and ultrafast temporal scales. Here, we unveil the coupled electron-lattice dynamics of a CH3NH3PbI3 single crystal upon intense photoexcitation through a unique combination of ultrafast electron diffraction, time-resolved photoelectron spectroscopy, and time-d…
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…
We investigate adsorption of a gas on the flat surface of a solid deformable adsorbent taking into account thermal fluctuations and analyze in detail the effect of thermal fluctuations on the adsorbent deformation in adsorption. The condition for coexistence of two states of a bistable system of adsorbed particles is derived. We establish the specific properties of the adsorption-induced surface normal relaxation of an adsorbent caused by thermal fluctuations. The mean transition times between two stable states of the bistable system are derived in the parabolic approximation and in the genera…
We find that if solid xenon is formed from liquid xenon, denoted "ice", there is a 10% increase of $^{129}$Xe longitudinal relaxation $T_1$ time (taken at 77 K and 2 Tesla) over a trickle-freeze formation, denoted "snow". Forming xenon ice also gives unprecedented reproducibility of $^{129}$Xe $T_1$ measurements across a range of 77-150 K. This temperature dependence roughly follows the theory of spin-rotation mediated by Raman scattering of harmonic phonons (SRRS), though it results in a smaller-than-predicted spin-rotation coupling strength $c_{K0}/h$. Enriched ice $^{129}$Xe $T_1$ experimen…
Understanding how photoexcited electron dynamics depend on electron-electron (e-e) and electron-phonon (e-p) interaction strengths is important for many fields, e.g. ultrafast magnetism, photocatalysis, plasmonics, and others. Here, we report simple expressions that capture the interplay of e-e and e-p interactions on electron distribution relaxation times. We observe a dependence of the dynamics on e-e and e-p interaction strengths that is universal to most metals and is also counterintuitive. While only e-p interactions reduce the total energy stored by excited electrons, the time for energy…
Spin orientation of photoexcited carriers and their energy relaxation is investigated in bulk Ge by studying spin-polarized recombination across the direct band gap. The control over parameters such as doping and lattice temperature is shown to yield high polarization degree, namely larger than 40%, as well as a fine-tuning of the angular momentum of the emitted light with a complete reversal between right- and left-handed circular polarization. By combining the measurement of the optical polarization state of band-edge luminescence and Monte Carlo simulations of carrier dynamics, we show that…
Few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy, performed with optical 500-1000 nm supercontinuum and broadband XUV pulses (30-50 eV), simultaneously probes dynamics of photoexcited carriers in WS$_{2}$ at the W O$_3$ edge (37-45 eV) and carrier-induced modifications of core-exciton absorption at the W N$_{6,7}$ edge (32-37 eV). Access to continuous core-to-conduction band absorption features and discrete core-exciton transitions in the same XUV spectral region in a semiconductor provides a novel means to investigate the effect of carrier excitation on core-exciton…
Present paper reports, the structural, microstructural, electrical, dielectric properties and ion dynamics of a sodium based solid polymer electrolyte films comprising of PEO8-NaPF6+ x wt. % SN. The structural and surface morphology properties have been investigated by XRD and FESEM. Different microscopic interaction among the polymer, salt and SN have been analyzed through FTIR. The dielectric permittivity and loss tangent enable us to estimate the dc conductivity, dielectric strength, double layer capacitance, and relaxation time. The loss tangent relaxation peak shifts towards high-frequenc…
Nonlinear optical properties and carrier relaxation dynamics in graphene, suspended in three different solvents, are investigated using femtosecond (80 fs pulses) Z-scan and degenerate pumpprobe spectroscopy at 790 nm. The results demonstrate saturable absorption property of graphene with a nonlinear absorption coefficient, $beta$, of ~2 to 9x10^-8 cm/W. Two distinct time scales associated with the relaxation of photoexcited carriers, a fast one in the range of 130-330 fs (related to carrier-carrier scattering) followed by a slower one in 3.5-4.9 ps range (associated with carrier-phonon scatte…
We employ few-femtosecond extreme ultraviolet (XUV) transient absorption spectroscopy to reveal simultaneously the intra- and interband carrier relaxation and the light-induced structural dynamics in nanoscale thin films of layered 2H-MoTe$_{2}$ semiconductor. By interrogating the valence electronic structure via localized Te 4$\textit{d}$ (39-46 eV) and Mo 4$\textit{p}$ (35-38 eV) core levels, the relaxation of the photoexcited hole distribution is directly observed in real time. We obtain hole thermalization and cooling times of 15$\pm$5 fs and 380$\pm$90 fs, respectively, and an electron-ho…
Ultrafast light-matter interaction is a powerful tool for the study of solids. Upon laser excitation, carrier multiplication and lattice acceleration beyond thermal velocity can occur, as a result of far-from-equilibrium carrier relaxation. The roles of electron-electron and electron-phonon scatterings are identified by first-principles dynamic simulations, from which a unified phase diagram emerges. It not only explains the experimentally-observed "inertial" melting but also predicts abnormal damping by Pauli Exclusion Principle with a new perspective on ultrahigh-intensity laser applications…
Nanowires (NWs) with their quasi-one-dimensionality often present different structural and opto-electronic properties than their thin-film counterparts. The thinner they are the larger these differences are, in particular in the carrier-phonon scattering and thermal conductivity. In this work, we present femtosecond transient absorbance measurements on GaAs0.8P0.2 NWs of two different diameters, 36 and 51 nm. The results show that thinner NWs sustain the hot-carriers at a higher temperature for longer times than thicker NWs. We explain the observation suggesting that in thinner NWs, the build-…
Energetic disorder in disordered organic solids has been found to alter their physical parameters. Here, we have demonstrated, by means of Monte-Carlo simulation and experiments, that the electroluminescence (EL) spectrum is dependent on energetic disorder. This dependence has been attributed to the charge carrier relaxation during hopping process. The dependence of EL spectrum on energetic disorder makes it temperature dependent and temperature dependence has been found to vary with energetic disorder in a variety of materials. The simulation has been performed by taking the relaxation of cha…
Spin-phonon coupling is the main drive of spin relaxation and decoherence in solid-state semiconductors at finite temperature. Controlling this interaction is a central problem for many disciplines, ranging from magnetic resonance to quantum technologies. Spin relaxation theories have been developed for almost a century but often employ a phenomenological description of phonons and their coupling to spin, resulting in a non-predictive tool and hindering our detailed understanding of spin dynamics. Here we combine fourth-order time-local quantum master equations with advanced electronic structu…
