Hot Electron Dynamics Research Articles

Formation of hot-electron ensembles quasiequilibrated in momentum space by ultrafast momentum scattering of highly excited hot electrons photoinjected into the Γ valley of GaAs

We study ultrafast scattering dynamics of hot electrons photoinjected with high excess energies in the \ensuremath{\Gamma} valley of the conduction band of GaAs, using time- and angle-resolved photoemission spectroscopy and ab initio calculations. At ultrafast rates of the order of 10 fs, the packets in the \ensuremath{\Gamma} valley are transformed into hot-electron ensembles (HEEs) quasiequilibrated in momentum space but not in energy space. The energy relaxation of the HEEs takes place as a whole on a longer time scale with rates dependent only on the excess energy, irrespective of the momenta of hot electrons. Both momentum scattering and energy relaxation are ruled by the electron-phonon interaction.

Hot electron and hole dynamics in thiol-capped CdSe quantum dots revealed by 2D electronic spectroscopy.

Colloidal quantum dots (QDs) have attracted interest as materials for opto-electronic applications, wherein their efficient energy use requires the understanding of carrier relaxation. In QDs capped by bifunctional thiols, used to attach the QDs to a surface, the relaxation is complicated by carrier traps. Using 2D spectroscopy at 77 K, we follow excitations in thiol-capped CdSe QDs with state specificity and high time resolution. We unambiguously identify the lowest state as an optically allowed hole trap, and identify an electron trap with excited-state absorption. The presence of traps changes the initial dynamics entirely by offering a different relaxation channel. 2D electronic spectroscopy enables us to pinpoint correlations between states and to easily separate relaxation from different starting states. We observe the direct rapid trapping of 1S3/2, 2S3/2, and 1S1/2 holes, and several competing electron relaxation processes from the 1Pe state.

First Terahertz-range Experiments on Pump – Probe Setup at Novosibirsk free Electron Laser

A single-color pump-probe system has been commissioned at the Novosibirsk free electron laser. The laser emits a tunable monochromatic terahertz radiation. To prove the proper system operation, we investigated the time-resolved absorption of a sample of n-type germanium doped with antimony, which was previously investigated at the FELBE facility, in the temperature range from 5 to 40 K. The measured relaxation time amounted to about 1.7 ns, which agreed with the results obtained at the FELBE. The results of pump-probe measurements of non-equilibrium dynamics of hot electrons in the germanium crystal at cryogenic temperatures are presented for wavelengths of 105, 141 and 150 μm.

Study of Surface Plasmon Induced Hot Electron Relaxation Process and Third-Order Optical Nonlinearity in Gold Nanostructures

The relaxation dynamics of hot electrons and the third-order optical nonlinearity in gold nanorods (GNRs) with different aspect ratios were investigated with the help of femtosecond optical Kerr (OKE) technique. Relaxation process on the time scale of picosecond (ps) was obtained at the longitudinal surface plasmon resonant (SPR) wavelength. As the aspect ratio (AR) of the GNRs varied from 4.2 ± 0.3 to 3.3 ± 0.3, the SPR wavelength changed accordingly from 808 to 750 nm, but the corresponding relaxation time and the third-order optical susceptibility did not change much. However, as the pump power increased from 150 mW to 400 mW, the relaxation time of the nanorod with AR = 4.2 ± 0.3 increased by 50% from 1.20 ± 0.01 ps to 1.84 ± 0.04 ps, indicating that the pump power is an important factor that affects the response time of the nanostructures. Comparative studies between Au nanorods, Au nanobipyramids, and Au triangular prisms measured under the same setup demonstrated that excitation conditions (excitation wavelength or pump power) and structure shapes were key factors to modulate the relaxation time of hot electrons. These results are important for the control and modulation of the response time in metallic nanostructures, which is essential for their applications in photovoltaic, photocatalytic, and ultrafast optic devices.

Atomically resolved real-space imaging of hot electron dynamics.

The dynamics of hot electrons are central to understanding the properties of many electronic devices. But their ultra-short lifetime, typically 100 fs or less, and correspondingly short transport length-scale in the nanometre range constrain real-space investigations. Here we report variable temperature and voltage measurements of the nonlocal manipulation of adsorbed molecules on the Si(111)-7 × 7 surface in the scanning tunnelling microscope. The range of the nonlocal effect increases with temperature and, at constant temperature, is invariant over a wide range of electron energies. The measurements probe, in real space, the underlying hot electron dynamics on the 10 nm scale and are well described by a two-dimensional diffusive model with a single decay channel, consistent with 2-photon photo-emission (2PPE) measurements of the real time dynamics.

Wannier interpolation of the electron-phonon matrix elements in polar semiconductors: Polar-optical coupling in GaAs

We generalize the Wannier interpolation of the electron-phonon matrix elements to the case of polar-optical coupling in polar semiconductors. We verify our methodological developments against experiments, by calculating the widths of the electronic bands due to electron-phonon scattering in GaAs, the prototype polar semiconductor. The calculated widths are then used to estimate the broadenings of excitons at critical points in GaAs and the electron-phonon relaxation times of hot electrons. Our findings are in good agreement with available experimental data. Finally, we demonstrate that while the Fr\"ohlich interaction is the dominant scattering process for electrons/holes close to the valley minima, in agreement with low-field transport results, at higher energies, the intervalley scattering dominates the relaxation dynamics of hot electrons or holes. The capability of interpolating the polar-optical coupling opens new perspectives in the calculation of optical absorption and transport properties in semiconductors and thermoelectrics.

Anomalous ultrafast dynamics of hot plasmonic electrons in nanostructures with hot spots.

The interaction of light and matter in metallic nanosystems is mediated by the collective oscillation of surface electrons, called plasmons. After excitation, plasmons are absorbed by the metal electrons through inter- and intraband transitions, creating a highly non-thermal distribution of electrons. The electron population then decays through electron-electron interactions, creating a hot electron distribution within a few hundred femtoseconds, followed by a further relaxation via electron-phonon scattering on the timescale of a few picoseconds. In the spectral domain, hot plasmonic electrons induce changes to the plasmonic resonance of the nanostructure by modifying the dielectric constant of the metal. Here, we report on the observation of anomalously strong changes to the ultrafast temporal and spectral responses of these excited hot plasmonic electrons in hybrid metal/oxide nanostructures as a result of varying the geometry and composition of the nanostructure and the excitation wavelength. In particular, we show a large ultrafast, pulsewidth-limited contribution to the excited electron decay signal in hybrid nanostructures containing hot spots. The intensity of this contribution correlates with the efficiency of the generation of highly excited surface electrons. Using theoretical models, we attribute this effect to the generation of hot plasmonic electrons from hot spots. We then develop general principles to enhance the generation of energetic electrons through specifically designed plasmonic nanostructures that could be used in applications where hot electron generation is beneficial, such as in solar photocatalysis, photodetectors and nonlinear devices.

Theoretical analysis of hot electron dynamics in nanorods.

Localised surface plasmons create a non-equilibrium high-energy electron gas in nanostructures that can be injected into other media in energy harvesting applications. Here, we derive the rate of this localised-surface-plasmon mediated generation of hot electrons in nanorods and the rate of injecting them into other media by considering quantum mechanical motion of the electron gas. Specifically, we use the single-electron wave function of a particle in a cylindrical potential well and the electric field enhancement factor of an elongated ellipsoid to derive the energy distribution of electrons after plasmon excitation. We compare the performance of nanorods with equivolume nanoparticles of other shapes such as nanospheres and nanopallets and report that nanorods exhibit significantly better performance over a broad spectrum. We present a comprehensive theoretical analysis of how different parameters contribute to efficiency of hot-electron harvesting in nanorods and reveal that increasing the aspect ratio can increase the hot-electron generation and injection, but the volume shows an inverse dependency when efficiency per unit volume is considered. Further, the electron thermalisation time shows much less influence on the injection rate. Our derivations and results provide the much needed theoretical insight for optimization of hot-electron harvesting process in highly adaptable metallic nanorods.

Ultrafast electron scattering from surface to bulk states at the InP(100) surface

We investigated the scattering dynamics of hot electrons at the atomically well-defined In-rich $(2\ifmmode\times\else\texttimes\fi{}4)$-reconstructed InP(100) surface in the presence of different surface states. Using energy- and time-resolved femtosecond two-photon photoemission spectroscopy, we determined the electron transfer between three-dimensional bulk states and the two-dimensional surface state C2, located high above the conduction band minimum (CBM) avoiding energetic overlap with relaxed bulk electrons. At excitation energies, where C2 was populated through hot bulk electrons, relaxing towards the CBM, we found evidence that the energy loss rate of the photoexcited electron distribution is mostly determined by inelastic electron-phonon scattering between bulk states. This was confirmed by measurements repeated after quenching the surface states with oxygen. For resonant photoexcitation, on the other hand, we measured a time constant of ${\ensuremath{\tau}}_{\mathrm{fast}}=20\phantom{\rule{0.28em}{0ex}}\mathrm{fs}$ for the depopulation of C2, showing that electron-phonon scattering between bulk and surface states might have direct consequence on ultrafast relaxation dynamics for materials with a high surface-to-bulk ratio.

Field emission at terahertz frequencies: AC-tunneling and ultrafast carrier dynamics

We demonstrate ultrafast terahertz (THz) field emission from a tungsten nanotip enabled by local field enhancement. Characteristic electron spectra which result from acceleration in the THz near-field are found. Employing a dual frequency pump–probe scheme, we temporally resolve different nonlinear photoemission processes induced by coupling near-infrared (NIR) and THz pulses. In the order of increasing THz field strength, we observe THz streaking, THz-induced barrier reduction (Schottky effect) and THz field emission. At intense NIR-excitation, the THz field emission is used as an ultrashort, local probe of hot electron dynamics in the apex. A first application of this scheme indicates a decreased carrier cooling rate in the confined tip geometry. Summarizing the results at various excitation conditions, we present a comprehensive picture of the distinct regimes in ultrafast photoemission in the near- and far-infrared.

State-resolved ultrafast dynamics of impact ionization in InSb.

Impact ionization (IMP) is a fundamental process in semiconductors, which results in carrier multiplication through the decay of a hot electron into a low-energy state while generating an electron-hole pair. IMP is essentially a state selective process, which is triggered by electron-electron interaction involving four electronic states specified precisely by energy and momentum conservations. However, important state-selective features remain undetermined due to methodological limitations in identifying the energy and momentum of the states involved, at sufficient temporal resolution, to reveal the fundamental dynamics. Here we report state-resolved ultrafast hot electron dynamics of IMP in InSb, a semiconductor with the lowest band-gap energy. The ultrafast decay of state-resolved hot-electron populations and the corresponding population increase at the conduction band minimum are directly captured, and the rate of IMP is unambiguously determined. Our analysis, based on the direct knowledge of state-resolved hot electrons, provides far deeper insight into the physics of ultrafast electron correlation in semiconductors.

Impact ionization and large room-temperature magnetoresistance in micron-sized high-mobility InAs channels

We report on hot electron induced impact ionization and large room-temperature magnetoresistance (MR) in micron-sized channels of $n$-type high-mobility InAs $(\ensuremath{\mu}=3.3{\mathrm{m}}^{2}{\mathrm{V}}^{\ensuremath{-}1}{\mathrm{s}}^{\ensuremath{-}1}$ at $T=300\mathrm{K})$: the MR reaches values of up to 450% in magnetic fields of 1 T and applied voltages of \ensuremath{\sim}1 V and is weakly dependent on temperature. We present Monte Carlo simulations of the hot electron dynamics to account for the large MR and its dependence on the sample geometry and applied electric and magnetic fields. Our work demonstrates that the impact ionization of electrons at room temperature, under small applied magnetic fields (1 T) and small voltages (1 V), can provide an extremely sensitive mechanism for controlling the electrical resistance of high-mobility semiconductors.

Prolonged hot electron dynamics in plasmonic-metal/semiconductor heterostructures with implications for solar photocatalysis.

Ideal solar-to-fuel photocatalysts must effectively harvest sunlight to generate significant quantities of long-lived charge carriers necessary for chemical reactions. Here we demonstrate the merits of augmenting traditional photoelectrochemical cells with plasmonic nanoparticles to satisfy these daunting photocatalytic requirements. Electrochemical techniques were employed to elucidate the mechanics of plasmon-mediated electron transfer within Au/TiO2 heterostructures under visible-light (λ>515 nm) irradiation in solution. Significantly, we discovered that these transferred electrons displayed excited-state lifetimes two orders of magnitude longer than those of electrons photogenerated directly within TiO2 via UV excitation. These long-lived electrons further enable visible-light-driven H2 evolution from water, heralding a new photocatalytic paradigm for solar energy conversion.

Prolonged Hot Electron Dynamics in Plasmonic‐Metal/Semiconductor Heterostructures with Implications for Solar Photocatalysis

AbstractIdeal solar‐to‐fuel photocatalysts must effectively harvest sunlight to generate significant quantities of long‐lived charge carriers necessary for chemical reactions. Here we demonstrate the merits of augmenting traditional photoelectrochemical cells with plasmonic nanoparticles to satisfy these daunting photocatalytic requirements. Electrochemical techniques were employed to elucidate the mechanics of plasmon‐mediated electron transfer within Au/TiO2 heterostructures under visible‐light (λ>515 nm) irradiation in solution. Significantly, we discovered that these transferred electrons displayed excited‐state lifetimes two orders of magnitude longer than those of electrons photogenerated directly within TiO2 via UV excitation. These long‐lived electrons further enable visible‐light‐driven H2 evolution from water, heralding a new photocatalytic paradigm for solar energy conversion.

Ultrafast terahertz dynamics of hot Dirac-electron surface scattering in the topological insulatorBi2Se3

Two-dimensional surface-scattering dynamics are central in the physics of topological insulators. Numerous electrical and optical measurements have evidenced that the origins of novel optoelectronic response can be traced back to Dirac surface-electron dynamics. Intrinsic surface dynamics, however, remain elusive because these experiments cannot access the frequencies of the surface-scattering rate. Time-resolved terahertz spectroscopy is the only apparatus for directly probing the collective response of low-energy electronic transitions. Here, by utilizing ultrafast optical-pump terahertz-probe spectroscopy, we discovered anomalous characteristics of the surface-scattering dynamics. Upon photoexcitation, the surface-scattering rate is increased and results in negative dynamic conductance at low temperature. Surprisingly, the differential changes of the surface-scattering rate are strongly reduced by photoexcited electrons at elevated temperature. We find that this nontrivial surface-electron dynamics is due to opening a carrier-relaxation channel from bulk to the surface state---one distinct characteristic of topological insulators. Our observations reveal unexpected surface dynamics of hot Dirac electrons, providing experimental a priori knowledge toward ultrafast optoelectronic operations.

Investigation of relativistic intensity laser generated hot electron dynamics via copper Kα imaging and proton acceleration

Simultaneous experimental measurements of copper Kα imaging and the maximum target normal sheath acceleration proton energies from the rear target surface are compared for various target thicknesses. For the T-cubed laser (≈4 J, 400 fs) at an intensity of ≈2 × 1019 W cm−2, the hot electron divergence is determined to be θHW HM≈22° using a Kα imaging diagnostic. The maximum proton energies are measured to follow the expected reduction with increasing target thickness. Numerical modeling produces copper Kα trends for both signal level and electron beam divergence that are in good agreement with the experiment. A geometric model describing the electron beam divergence reproduces the maximum proton energy trends observed from the experiment and the fast electron density and the peak electric field observed in the numerical modeling.

Ultrafast dynamics of hot electrons and phonons in chemical vapor deposited graphene

The relaxation dynamics of photoexcited carriers in a chemical vapor deposited graphene transferred on quartz substrate has been investigated by using ultrafast optical-pump terahertz (THz)-probe spectroscopy. Terahertz transmission through graphene sample is reduced by optical pumping. The change of transmission decays exponentially after the optical pulse. We find the relaxation time is insensitive to the substrate temperature from 10 K to 300 K but increases sublinearly with pump fluence. We model the relaxation process involving electron-phonon coupling together with a set of rate equations to describe the transient responses of quasi-particles and optical phonons. The increases of the extracted carrier temperature and the measured relaxation time with pump fluence are associated with the fact that high pump fluence significantly increases the carrier temperature and broadens the carrier distribution. As a result, it leads to the reduction of optical phonon emission efficiency and the decrease of cooling rate as well.

Ultrafast photodoping and effective Fermi-Dirac distribution of the Dirac particles in Bi2Se3

We exploit time- and angle-resolved photoemission spectroscopy to determine the evolution of the out-of-equilibrium electronic structure of the topological insulator ${\mathrm{Bi}}_{2}{\mathrm{Se}}_{3}$. The response of the Fermi-Dirac distribution to ultrashort IR laser pulses has been studied by modeling the dynamics of hot electrons after optical excitation. We disentangle a large increase in the effective temperature (${T}^{*}$) from a shift of the chemical potential (${\ensuremath{\mu}}^{*}$), which is consequence of the ultrafast photodoping of the conduction band. The relaxation dynamics of ${T}^{*}$ and ${\ensuremath{\mu}}^{*}$ are $k$ independent and these two quantities uniquely define the evolution of the excited charge population. We observe that the energy dependence of the nonequilibrium charge population is solely determined by the analytical form of the effective Fermi-Dirac distribution.

Nonplanar electron acoustic shock waves in a plasma with electrons featuring Tsallis distribution

The properties of cylindrical and spherical electron acoustic shock waves (EASWs) in an unmagnetized plasma consisting of cold electrons, immobile ions, and hot electrons featuring Tsallis statistics are investigated by employing the reductive perturbation technique. A Korteweg-de Vries Burgers (KdVB) equation is derived and its numerical solution is obtained. The effects of electron nonextensivity and electron kinematic viscosity on the basic features of EA shock waves are discussed in nonplanar geometry. It is found that nonextensive nonplanar EA shock waves behave quite differently from their planar counterpart. Deviations from a pure planar geometry are significant only for times shorter that the inverse of the cold electron plasma frequency. Given that the hot electron dynamics is the most interesting one, and that in many astrophysical scenarios the cold electrons can be significantly rarefied, this restriction is not too limiting for the applicability of our model.

ULTRAFAST ELECTRON DIFFRACTIVE VOLTAMMETRY: GENERAL FORMALISM AND APPLICATIONS

We present a general formalism of ultrafast diffractive voltammetry approach as a contact-free tool to investigate the ultrafast surface charge dynamics in nanostructured interfaces. As case studies, the photoinduced surface charging processes in oxidized silicon surface and the hot electron dynamics in nanoparticle-decorated interface are examined based on the diffractive voltammetry framework. We identify that the charge redistribution processes appear on the surface, sub-surface, and vacuum levels when driven by intense femtosecond laser pulses. To elucidate the voltammetry contribution from different sources, we perform controlled experiments using shadow imaging techniques and N-particle simulations to aid the investigation of the photovoltage dynamics in the presence of photoemission. We show that voltammetry contribution associated with photoemission has a long decay tail and plays a more significant role in the nanosecond timescale, whereas the ultrafast voltammetry are dominated by local charge transfer, such as surface charging and molecular charge transport at nanostructured interfaces. We also discuss the general applicability of the diffractive voltammetry as an integral part of quantitative ultrafast electron diffraction methodology in researching different types of interfaces having distinctive surface diffraction and boundary conditions.