Ultrafast Hole Dynamics Research Articles

Photoinduced dynamics of organic molecules using nonequilibrium Green's functions with second-Born, GW, T -matrix, and three-particle correlations

The ultrafast hole dynamics triggered by the photoexcitation of molecular targets is a highly correlated process even for those systems, like organic molecules, having a weakly correlated ground state. We here provide a unifying framework and a numerically efficient matrix formulation of state-of-the-art non-equilibrium Green's function (NEGF) methods like second-Born as well as $GW$ and $T$-matrix without and {\em with} exchange diagrams. Numerical simulations are presented for a paradigmatic, exactly solvable molecular system and the shortcomings of the established NEGF methods are highlighted. We then develop a NEGF scheme based on the Faddeev treatment of three-particle correlations; the exceptional improvement over established methods is explained and demonstrated. The Faddeev NEGF scheme scales linearly with the maximum propagation time, thereby opening prospects for femtosecond simulations of large molecules.

Analysis of a measurement scheme for ultrafast hole dynamics by few femtosecond resolution X-ray pump-probe Auger spectroscopy.

Ultrafast hole dynamics created in molecular systems as a result of sudden ionisation is the focus of much attention in the field of attosecond science. Using the molecule glycine we show through ab initio simulations that the dynamics of a hole, arising from ionisation in the inner valence region, evolves with a timescale appropriate to be measured using X-ray pulses from the current generation of SASE free electron lasers. The examined pump-probe scheme uses X-rays with photon energy below the K edge of carbon (275-280 eV) that will ionise from the inner valence region. A second probe X-ray at the same energy can excite an electron from the core to fill the vacancy in the inner-valence region. The dynamics of the inner valence hole can be tracked by measuring the Auger electrons produced by the subsequent refilling of the core hole as a function of pump-probe delay. We consider the feasibility of the experiment and include numerical simulation to support this analysis. We discuss the potential for all X-ray pump-X-ray probe Auger spectroscopy measurements for tracking hole migration.

Access to hole dynamics in graphite by femtosecond luminescence and photoemission spectroscopy

Ultrafast dynamics of holes in a solid is usually hard to observe directly because the optical transition includes both electron and hole dynamics. In this paper we show an approach combining femtosecond luminescence and photoemission spectroscopy, successfully applied to graphite. Ultrafast infrared luminescence is observed in graphite and ascribed to recombination luminescence, though graphite is a semimetal. The dynamics of holes is deduced by taking a ratio between the time-resolved luminescence and photoemission data recorded on the same sample, and shown to be very close to that of electrons.

Ultrafast hole dynamics in two-photon photoemission from metal surfaces

We investigate the effects of photoexcited-hole decay on time-resolved two-photon photoemission spectra of metal surfaces by non-equilibrium Green function method. We show that it is necessary for calculating the photoelectron intensity to introduce a Green function depending on the observation time of the photoelectron. The photoexcited-hole decay causes the loss of coherence of the system and hence accounts for acceleration of the decay of the photoexcited-electron density. Then the effective lifetimes estimated from the photoelectron intensity as a function of the pump–probe delay time can be the lifetimes of the photoexcited ‘(non-excitonic) electron–hole pairs’ even when direct interactions between photoexcited electrons and holes are negligible while it is usually considered that the effective lifetimes correspond to the electron lifetimes.

Ultrafast intersubband scattering of holes in p-type modulation-doped Si 1− xGe x/Si multiple quantum wells

We report on an experimental and theoretical study of intersubband relaxation of holes in p-type modulation-doped Si 1− x Ge x /Si multiple quantum wells. The ultrafast hole dynamics is studied in pump–probe experiments with 150 fs mid-infrared pulses. For 4.4 nm wide wells ( x=0.5) the lifetime of holes in the second heavy hole subband is only 250 fs due to rapid emission of optical phonons via the deformation potential interaction. Model calculations of hole–phonon scattering give an almost identical value and point to the crucial role of cascaded scattering via an intermediate subband with light-hole-split-off symmetry.

Ultrafast dynamics of intersubband excitations in a quasi-two-dimensional hole gas.

We present the first study of ultrafast hole dynamics after resonant intersubband excitation in a quasi-two-dimensional semiconductor. p-type Si0.5Ge 0.5/Si multiple quantum wells are studied in pump-probe experiments with 150 fs midinfrared pulses. Intersubband scattering from the second heavy-hole back to the first heavy-hole subband occurs with a time constant of 250 fs, followed by intrasubband carrier heating within 1 ps. Such processes give rise to a strong reshaping of the intersubband absorption line, which is accounted for by calculations of the subband structure, optical spectra, and hole-phonon scattering rates.

Electron and hole relaxation pathways in semiconductor quantum dots

Femtosecond (fs) broad-band transient absorption (TA) is used to study the intraband relaxation and depopulation dynamics of electron and hole quantized states in CdSe nanocrystals (NC's) with a range of surface properties. Instead of the drastic reduction in the energy relaxation rate expected due to a ``phonon bottleneck,'' we observe a fast subpicosecond $1P$-to-$1S$ electron relaxation, with the rate exceeding that due to phonon emission in bulk semiconductors. The energy relaxation is enhanced with reducing the NC's radius, and does not show any dependence on the NC surface properties (quality of the surface passivation). These data indicate that electron energy relaxation occurs by neither multiphonon emission nor by coupling to surface defects, but is likely meditated by Auger-type electron-hole energy transfer. We use fs infrared TA to probe electron and hole intraband transitions, which allows us to distinguish between electron and hole relaxation pathways leading to the depopulation of NC quantized states. In contrast to the electron relaxation, which is controlled by NC surface passivation, the depopulation of hole quantized states is extremely fast (sub-ps-to-ps time scales) in all types of samples, independent of NC surface treatment (including NC's overcoated with a ZnS layer). Our results indicate that ultrafast hole dynamics are not due to trapping at localized surface defects such as a vacancy, but rather arise from relaxation into intrinsic NC states or intrinsically unpassivated interface states.

Ultrafast dynamics of inter- and intraband transitions in semiconductor nanocrystals: Implications for quantum-dot lasers

Application of femtosecond transient absorption in the visible and near-IR spectral ranges and time-resolved photoluminescence allows us to separate electron and hole relaxation paths and to map the structure of interband and intraband optical transitions in CdSe and CdS nanocrystals (NC's) with a wide range of surface properties. In contrast to electron relaxation, which is controlled by NC surface passivation, depopulation of hole quantized states is extremely fast (sub-ps-to-ps time scales) in all types samples, independent of NC surface treatment (including NC's overcoated with a ZnS layer). Our results suggest that ultrafast hole dynamics are not due to trapping at localized surface defects such as a vacancy, but rather arise from relaxation into intrinsic NC states or intrinsically unpassivated interface states.

Ultrafast dynamics of holes in GaAs probed by two-color femtosecond spectroscopy

Ultrafast relaxation dynamics of light and heavy holes in GaAs following femtosecond valence-to-conduction-band excitation are measured by probing the light- and heavy-to-split-off hole transitions at different midinfrared wavelengths using the recently developed broadly tunable femtosecond optical parametric oscillator. The initial relaxation times are less than 75 fs, and a spectral hole-burning effect is seen. The results suggest that carrier–carrier and optical-phonon scattering, in particular, polar optical-phonon scattering, are the primary processes leading to the initial redistribution of heavy and light holes.

Broadly Tunable Femtosecond Sources in the Mid-Infrared and Two-Wavelength Ultrafast Spectroscopy of Holes in GaAs

The recent development of periodically poled lithium niobate (PPLN) has led to a variety of highly efficient and compact all-solid-state nonlinear optical devices. Of particular interest are the optical parametric oscillators. We have most recently demonstrated for the first time a highly efficient broadly tunable femtosecond optical parametric oscillator (fs OPO) using PPLN. The threshold for oscillation of the PPLN fs OPO is remarkably low, on the order of 50 mW. As a result, it is now possible to use a diode-pumped and frequency-doubled Nd:YVO 4 laser, rather than an Ar-ion laser, as the pump source for the mode-locked Ti:sapphire laser for pumping the fs OPO. Such an OPO can operate from approximately 1 μm to 5.4 μm. Femtosecond sources have been used in a variety of experiments to study the dynamics of hot carriers in semiconductors. Because of the limited available wavelength range of earlier femtosecond sources, most such studies have been limited to electron dynamics in the conduction band of III–V compounds such as GaAs. With the extended tuning range of the recently developed fs OPO's, it is now possible to study a much wider variety of materials and transitions. We have recently obtained preliminary results on the ultrafast dynamics of holes in GaAs using two-wavelength tunable femtosecond spectroscopy, by pumping the valence-to-conduction band transition at approximately 800 nm and simultaneously probing the transitions between the split-off band and the perturbed heavy-hole band at approximately 3 μm. These recent results are summarized and discussed briefly.

Electron and Hole Relaxation Pathways in II-VI Semiconductor Nanocrystals

AbstractFemtosecond (fs) broad-band transient absorption (TA) is used to study the intra-band relaxation and depopulation dynamics of electron and hole quantized states in CdSe nanocrystals (NC's) with a range of surface properties. Instead of the drastic reduction in the energy relaxation rate expected due to a 'phonon bottleneck', we observe a fast sub-picosecond 1P-to-1S relaxation, with the rate enhanced in NC's of smaller radius. We use fs IR TA to probe electron and hole intraband transitions, which allows us to distinguish between electron and hole pathways leading to the depopulation of NC quantized states. In contrast to electron relaxation, which is controlled by NC surface passivation, depopulation of hole quantized states is extremely fast (sub-ps-to-ps time scales) in all types samples, independent of NC surface treatment (including NC's overcoated with a ZnS layer). Our results indicate that ultrafast hole dynamics are not due to trapping at surface defects, but rather arise from relaxation into intrinsic NC states.