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Individual relaxation dynamics of electrons and holes in optically pumped semiconductors is rarely observed due to their overlap. Here we report the individual dynamics of long-lived (~200 mks) holes observed at room temperature in a 10 nm thick film of the 3D topological insulator (TI) Bi2Se3 coated with a 10 nm thick MgF2 layer using transient absorption spectroscopy in the UV-Vis region. The ultraslow hole dynamics was observed by applying multiphoton resonant pumping of massless Dirac fermions and bound valence electrons in Bi2Se3 at a certain wavelength sufficient for their photoemission and subsequent trapping at the Bi2Se3/MgF2 interface. The emerging deficit of electrons in the film makes it impossible for the remaining holes to recombine, thus causing their ultraslow dynamics measured at a specific probing wavelength. We also found an extremely long rise time (~600 ps) for this ultraslow optical response, which is due to the large spin-orbit coupling (SOC) splitting at the valence band maximum and the resulting intervalley scattering between the splitting components. The ultraslow hole dynamics in Bi2Se3 due to the presence of the Bi2Se3/MgF2 interface is nevertheless much faster than the known ultraslow electron dynamics at the Si/SiO2 interface, also induced by multiphoton excitation in Si. The observed dynamics of long-lived holes is gradually suppressed with decreasing Bi2Se3 film thickness for the 2D TI Bi2Se3 (film thickness 5, 4, and 2 nm) due to the loss of resonance conditions for multiphoton photoemission caused by the gap opening at the Dirac surface state nodes. This behavior indicates that the dynamics of massive Dirac fermions predominantly determines the relaxation of photoexcited carriers for both the 2D topologically nontrivial and 2D topologically trivial insulator phases.

It is often taken for granted that in pump-probe experiments on the topological insulator (TI) Bi2Se3 using IR pumping with a commercial Ti:Sapphire laser [~800 nm (1.55 eV photon energy)], the electrons are excited in the one-photon absorption regime, even when pumped with absorbed fluences in the mJ cm-2 range. Here, using UV-Vis transient absorption (TA) spectroscopy, we show that even at low-power IR pumping with absorbed fluences in the mkJ cm-2 range, the TA spectra of the TI Bi2Se3 extend across a part of the UV and the entire visible region. This observation suggests unambiguously that the two-photon pumping regime accompanies the usual one-photon pumping regime even at low laser powers applied. We attribute the high efficiency of two-photon pumping to the giant nonlinearity of Dirac fermions in the Dirac surface states (SS). On the contrary, one-photon pumping is associated with the excitation of bound valence electrons in the bulk into the conduction band. Two mechanisms of absorption bleaching were also revealed since they manifest themselves in different spectral regions of probing. These two mechanisms were assigned to the filling of the phase-space in the Dirac SS and bulk states and the corresponding Pauli blocking.

Ultrafast carrier relaxation in the 2D topological insulator (TI) Bi2Se3 [gapped Dirac surface states (SS)] and how it inherits ultrafast relaxation in the 3D TI Bi2Se3 (gapless Dirac SS) remains a challenge for developing new optoelectronic devices based on these materials. Here ultrashort (100 fs) pumping pulses of ~340 nm wavelength (~3.65 eV photon energy) were applied to study ultrafast electron relaxation in the 2D TI Bi2Se3 films with a thickness of 2 and 5 quintuple layers (~2 and ~5 nm, respectively) using transient absorption (TA) spectroscopy in the ultraviolet-visible spectral region (1.65 - 3.85 eV). The negative and positive contributions of TA spectra were attributed to absorption bleaching that mostly occur in the bulk states and to the inverse bremsstrahlung type free carrier absorption in the surface states, respectively. Owing to this direct and selective access to the bulk and surface carrier dynamics, we were able to monitor coherent longitudinal optical (LO) phonon oscillations, which were successively launched in the bulk and surface states by the front of the relaxing electron population within the LO-phonon cascade emission. We have also recognized the coherent surface-to-bulk vibrational coupling that appears through the phase-dependent amplitude variations of coherent LO-phonon oscillations. This unique behavior manifests itself predominantly for the topologically trivial insulator phase of the 2D TI Bi2Se3 (2 nm thick film) in the photon energy range (~2.0 - 2.25 eV) where efficient energy exchange between the bulk and surface states occurs. We also found that the coherent surface-to-bulk vibrational coupling significantly weakens with increasing both the Bi2Se3 film thickness and pumping power.

Optical control of Dirac surface states (SS) in topological insulators (TI) remains one of the most challenging problems governing their potential applications in novel electronic and spintronic devices. Here, using visible-range transient absorption spectroscopy exploiting ~340 nm (~3.65 eV) pumping, we provide evidence for dynamic opening of a gap in Dirac SS of the thin-film 3D TI Bi2Se3, which has been induced by the dynamic Rashba effect occurring in the film bulk with increasing optical pumping power (photoexcited carrier density). The observed effect appears through the transient absorption band associated with inverse-bremsstrahlung-type free carrier absorption in the gapped Dirac SS. We have also recognized experimental signatures of the existence of the higher energy Dirac SS in the 3D TI Bi2Se3 (in addition to those known as SS1 and SS2) with energies of ~2.7 and ~3.9 eV (SS3 and SS4). It is evidenced that the dynamic gap opening has the same effect on the Dirac SS occurring at any energy.

Ultrafast carrier dynamics in the topological insulator Bi2Se3 have recently been intensively studied using a variety of techniques. However, we are not aware of any successful experiments exploiting transient absorption (TA) spectroscopy for these purposes. Here we demonstrate that if the ~730 nm wavelength pumping (~1.7 eV photon energy) is applied to ultrathin Bi2Se3 films, TA spectra cover the entire visible region, thus unambiguously pointing to two-photon excitation (~3.4 eV). The carrier relaxation dynamics is found to be governed by the polar optical phonon cascade emission occurring in both the bulk states and the Dirac surface states (SS), including SS-bulk-SS vertical electron transport and being also exclusively influenced by whether the Dirac point is presented between the Dirac cones of the higher energy (~1.5 eV) Dirac SS (known as SS2). We have recognized that SS2 act as a valve substantially slowing down the relaxation of electrons when the gap between Dirac cones exceeds the polar optical phonon and resonant defects energies. The resulting progressive accumulation of electrons in the gapped SS2 becomes detectable through the inverse bremsstrahlung type free carrier absorption.

The dynamical and static Rashba effects in hybrid methylammonium (MA) lead halide perovskites have recently been theoretically predicted. However, only the static effect was experimentally confirmed so far. Here we report on the dynamical Rashba effect observed using snapshot transient absorption spectral imaging with 400 nm pumping for a fully encapsulated film of 20-nm-sized 3D MAPbBr3 nanocrystals. The effect causes a 240 meV splitting of the lowest-energy absorption bleaching band, initially appearing over sub-ps timescale and progressively stabilizing to 60 meV during 500 ps. The integrated intensities of the split subbands demonstrate a photon-helicity-dependent asymmetry, thus proving the Rashba-type splitting and providing direct experimental evidence for the Rashba spin-split edge states in lead halide perovskite materials. The ultrafast dynamics is governed by the relaxation of two-photon-excited electrons in the Rashba spin-split system caused by a built-in electric field originating from dynamical charge separation in the entire MAPbBr3 nanocrystal., Comment: Under consideration at Nature Communications