Multiphoton-pumped UV-Vis transient absorption spectroscopy of 2D materials: basic concepts and recent applications.

2D materials are considered a key element in the development of next-generation electronics (nanoelectronics) due to their extreme thickness in the nanometer range and unique physical properties. The ultrafast dynamics of photoexcited carriers in such materials are strongly influenced by their interfaces, since the thickness of 2D materials is much smaller than the typical depth of light penetration into their bulk counterparts and the mean free path of photoexcited carriers. The resulting collisions of photoexcited carriers with interfacial potential barriers of 2D materials in the presence of a strong laser field significantly alter the overall dynamics of photoexcitation, allowing laser light to be directly absorbed by carriers in the conduction/valence band through the inverse bremsstrahlung mechanism. The corresponding ultrafast carrier dynamics can be monitored using multiphoton-pumped UV-Vis transient absorption spectroscopy. In this review, we discuss the basic concepts and recent applications of this spectroscopy for a variety of 2D materials, including transition-metal dichalcogenide monolayers, topological insulators, and other 2D semiconductor structures.

Characterization of charge-carrier dynamics at the Bi2Se3/MgF2interface by multiphoton pumped UV-Vis transient absorption spectroscopy.

Separate relaxation dynamics of electrons and holes in experiments on optical pumping-probing of semiconductors is rarely observed due to their overlap. Here we report the separate relaxation dynamics of long-lived (∼200µs) holes observed at room temperature in a 10 nm thick film of the 3D topological insulator (TI) Bi2Se3coated with a 10 nm thick MgF2layer using transient absorption spectroscopy in the UV-Vis region. The ultraslow hole dynamics was observed by applying resonant pumping of massless Dirac fermions and bound valence electrons in Bi2Se3at a certain wavelength sufficient for their multiphoton photoemission and subsequent trapping at the Bi2Se3/MgF2interface. 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 splitting at the valence band maximum and the resulting intervalley scattering between the splitting components. The observed dynamics of long-lived holes is gradually suppressed with decreasing Bi2Se3film thickness for the 2D TI Bi2Se3(film thickness below 6 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.

Two-photon IR pumped UV-Vis transient absorption spectroscopy of Dirac fermions in the topological insulator Bi2Se3.

It is often taken for granted that in pump-probe experiments on the topological insulator (TI) Bi2Se3using 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-2range. Here, using UV-Vis transient absorption (TA) spectroscopy, we show that even at low-power Infrared (IR) pumping with absorbed fluences in theµJ cm-2range, the TA spectra of the TI Bi2Se3extend 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 and cause the appearance of three different relaxation dynamics. These two mechanisms were attributed to the filling of the phase-space in the Dirac SS and bulk states, followed by the corresponding Pauli blocking.

Coherent surface-to-bulk vibrational coupling in the 2D topologically trivial insulator Bi2Se3 monitored by ultrafast transient absorption spectroscopy.

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 (1.65-3.9 eV). The negative and positive contributions of TA spectra were attributed to absorption bleaching that mostly occurs in the bulk states and to the inverse bremsstrahlung type free carrier absorption in the gapped Dirac SS, 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.

Dynamic Opening of a Gap in Dirac Surface States of the Thin-Film 3D Topological Insulator Bi2Se3 Driven by the Dynamic Rashba Effect.

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 the 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.

Nonlinear optical observation of coherent acoustic Dirac plasmons in thin-film topological insulators.

Low-energy collective electronic excitations exhibiting sound-like linear dispersion have been intensively studied both experimentally and theoretically for a long time. However, coherent acoustic plasmon modes appearing in time-domain measurements are rarely observed due to Landau damping by the single-particle continua. Here we report on the observation of coherent acoustic Dirac plasmon (CADP) modes excited in indirectly (electrostatically) opposite-surface coupled films of the topological insulator Bi2Se3. Using transient second-harmonic generation, a technique capable of independently monitoring the in-plane and out-of-plane electron dynamics in the films, the GHz-range oscillations were observed without corresponding oscillations in the transient reflectivity. These oscillations were assigned to the transverse magnetic and transverse electric guided CADP modes induced by the evanescent guided Lamb acoustic waves and remained Landau undamped due to fermion tunnelling between the opposite-surface Dirac states.

Effect of Mn doping on ultrafast carrier dynamics in thin films of the topological insulator Bi2Se3.

Transient reflectivity (TR) measured at laser photon energy 1.51 eV from the indirectly intersurface-coupled topological insulator Bi2-x Mn x Se3 films (12 nm thick) revealed a strong dependence of the rise-time and initial decay-time constants on photoexcited carrier density and Mn content. In undoped samples (x = 0), these time constants are exclusively governed by electron-electron and electron-phonon scattering, respectively, whereas in films with x = 0.013-0.27 ultrafast carrier dynamics are completely controlled by photoexcited electron trapping by ionized Mn(2+) acceptors and their dimers. The shortest decay-time (~0.75 ps) measured for the film with x = 0.27 suggests a great potential of Mn-doped Bi2Se3 films for applications in high-speed optoelectronic devices. Using Raman spectroscopy exploiting similar laser photon energy (1.58 eV), we demonstrate that due to indirect intersurface coupling in the films, the photoexcited electron trapping in the bulk enhances the electron-phonon interaction strength in Dirac surface states.

Thickness tunable quantum interference between surface phonon and Dirac plasmon states in thin films of the topological insulator Bi2Se3.

We report on a >100-fold enhancement of Raman responses from Bi2Se3 thin films if laser photon energy switches from 2.33 eV (532 nm) to 1.58 eV (785 nm), which is due to direct optical coupling to Dirac surface states (SS) at the resonance energy of ∼1.5 eV (a thickness-independent enhancement) and due to nonlinearly excited Dirac plasmon (a thickness-dependent enhancement). Owing to the direct optical coupling, we observed an in-plane phonon mode of hexagonally arranged Se-atoms associated with a continuous network of Dirac SS. This mode revealed a Fano lineshape for films <15 nm thick, resulting from quantum interference between surface phonon and Dirac plasmon states.