Photoexcited Electron Dynamics Research Articles

Revealing Optical Transitions and Carrier Recombination Dynamics within the Bulk Band Structure of Bi2Se3.

Bismuth selenide (Bi2Se3) is a prototypical 3D topological insulator whose Dirac surface states have been extensively studied theoretically and experimentally. Surprisingly little, however, is known about the energetics and dynamics of electrons and holes within the bulk band structure of the semiconductor. We use mid-infrared femtosecond transient reflectance measurements on a single nanoflake to study the ultrafast thermalization and recombination dynamics of photoexcited electrons and holes within the extended bulk band structure over a wide energy range (0.3 to 1.2 eV). Theoretical modeling of the reflectivity spectral line shapes at 10 K demonstrates that the electrons and holes are photoexcited within a dense and cold electron gas with a Fermi level positioned well above the bottom of the lowest conduction band. Direct optical transitions from the first and the second spin-orbit split valence bands to the Fermi level above the lowest conduction band minimum are identified. The photoexcited carriers thermalize rapidly to the lattice temperature within a couple of picoseconds due to optical phonon emission and scattering with the cold electron gas. The minority carrier holes recombine with the dense electron gas within 150 ps at 10 K and 50 ps at 300 K. Such knowledge of interaction of electrons and holes within the bulk band structure provides a foundation for understanding how such states interact dynamically with the topologically protected Dirac surface states.

Trap-Door-Like Irreversible Photoinduced Charge Transfer in a Donor-Acceptor Complex.

For efficient conversion of light into useful energy sources, it is very important to study and describe the first steps of primary charge-transfer process in natural structures and artificial devices. The time scale of these processes in artificial photosynthetic and photovoltaic devices is on the order of femto- to picoseconds and involves vibronic coupling of electrons and nuclei and also nuclear alleviation to enhance charge separation. Here we present an atomistic description of the photoexcited electron dynamics in a noncovalently bonded system formed by an hydrogenated nanodiamond as donor and a perylene diimide as an acceptor. The complex shows extremely fast charge transfer, separation, and stabilization within 90 fs. This stabilization is purely electronic in nature. To the best of our knowledge, these results show for the first time that it is possible to stabilize charge without polaron formation or nuclear relaxation, reaching a steady state enhanced by a pure electronic reorganization.

Dynamics of out-of-equilibrium electron and hole pockets in the type-II Weyl semimetal candidate WTe2

We present a time- and angular-resolved photoemission (TR-ARPES) study of the transition- metal dichalcogenide WTe2, a candidate type II Weyl semimetal exhibiting extremely large magne- toresistence. Using femtosecond light pulses, we characterize the unoccupied states of the electron pockets above the Fermi level. We track the relaxation dynamics of photoexcited electrons along the unoccupied band structure and into a bulk hole pocket. Following the ultrafast carrier relaxation, we report remarkably similar decay dynamics for electrons and holes. Our results corroborate the hypothesis that carrier compensation is a key factor in the exceptional magnetotransport properties of WTe2.

Impact of Element Doping on Photoexcited Electron Dynamics in CdS Nanocrystals.

Element doping plays a key role in achieving desired properties of semiconductor nanocrystals. In the energy-state landscape the doping-induced localized impurity states (LIS) can bring on significant modification of photoelectrochemical effects. It is difficult to retrieve information regarding the doping-induced LIS. Here we report on such information gleaned on a prototypical system of CdS nanocrystals slightly doped with In3+, through joint observations from photoluminescence (PL) and ultrafast transient absorption (TA) spectroscopy. The nonradiative nature of the In-doping induced LIS is revealed by PL. The TA observations, with a set of control experiments, enable us to capture a picture of the photoexcited electron dynamics and unravel the photoexcited electron reservoir (PEER) effect associated with the In-doping induced band gap LIS. This work establishes a fundamental, mechanistic understanding of the significant impact of element doping on the photoexcited electron dynamics in this model system, offering useful inputs for relevant material design and applications.

Relaxation of the photoexcited electrons in chevron-type graphene nanoribbons: Many-body theory and nonadiabatic molecular dynamics modeling

The dynamics of photoexcited electrons associated with the absorption processes of the dominant peaks in pristine and nitrogen-doped chevron-type graphene nanoribbons (CGNRs and NCGNRs) have been investigated via nonadiabatic molecular dynamics simulations. The results show that the decay time in NCGNR is shorter than in CGNR. The results rationalized by the large energy difference between LUMO and LUMO+3 in CGNR (0.61 eV) and in NCGNR (0.37 eV), the comparable coherence timescales (22 fs and 21 fs) and nonadiabatic couplings (2.97 meV and 2.48 meV) of these two systems. Furthermore, phonon influence spectra show that the modes participate in the relaxation of the photoexcited electron in CGNR reside around in 101 cm−1 while in NCGNR they are in a broad range of frequencies between 210 cm−1 to 2304 cm−1, which means there exist more additional channels for accelerating the transfer in NCGNR, rationalizing why the photoexcited electrons decay faster in NCGNR.

Dynamics of phonons in Sr3Ir4Sn13: an experimental study by ultrafast spectroscopy measurements

We report a study of ultrafast dynamics of photoexcited electrons and phonons in Sr3Ir4Sn13 using dual-color transient reflectivity change () measurements. Time resolved optical spectroscopy of collective excitations reveal the marked features near its structural phase transition temperature K. Two distinctive oscillatory timescales in have been clearly resolved. The rapid THz-range oscillations are attributed to the dynamics of the optical phonons which strongly correlate to the structural phase transition. The slow GHz-range oscillatory phenomenon which only occurs below about 150 K is associated with the dynamic response of the longitudinal-acoustic phonons. These low-energy phonons show a softening feature on approaching the transition temperature, also indicating a strong relevance to the structural phase transition. The information that we demonstrated would provide a deeper understanding of the structural phase transition in Sr3Ir4Sn13.

Optical pump-terahertz probe analysis of long-lived d-electrons and relaxation to self-trapped exciton states in MnO

The dynamics of photoexcited electrons in various excited d-states was investigated in a transition metal oxide MnO by tunable optical pump-terahertz probe measurements. Photoexcited electrons in the lowest excited d-state showed the longest relaxation time among the three excited d-states that are accessible in MnO at room temperature. The relaxation rate in the lowest excited d-state showed a drastic increase below the Neel temperature TN = 120 K in MnO. We conclude that this increase is caused by the appearance of a decay channel related to magnetic-excitation-assisted photoluminescence from self-trapped exciton (STE) states. The opening of relaxation channels to the STE states in an antiferromagnetic phase suggests that it may be possible to control photocarrier lifetime by magnetic order in transition metal oxides.

Photoinduced phase transitions in narrow-gap Mott insulators: The case ofVO2

We study the nonequilibrium dynamics of photoexcited electrons in the narrow-gap Mott insulator VO$_2$. The initial stages of relaxation are treated using a quantum Boltzmann equation methodology, which reveals a rapid ($\sim$ femtosecond time scale) relaxation to a pseudothermal state characterized by a few parameters that vary slowly in time. The long-time limit is then studied by a Hartree-Fock methodology, which reveals the possibility of nonequilibrium excitation to a new metastable $M_1$ metal phase that is qualitatively consistent with a recent experiment. The general physical picture of photoexcitation driving a correlated electron system to a new state that is not accessible in equilibrium may be applicable in similar materials.

Ultrafast electronic response of Ag(111) and Cu(111) surfaces: From early excitonic transients to saturated image potential

We investigate the evolution of attosecond to femtosecond screening and emergent potentials that govern the dynamics and energetics of electrons and holes excited in the various stages of multiphoton photoemission processes and control the photoelectron yield in recently reported experiments [X. Cui, C. Wang, A. Argondizzo, S. Garrett-Roe, B. Gumhalter, and H. Petek, Nat. Phys. 10, 505 (2014)]. The study is focused on the dynamical screening of holes created in preexistent quasi-two-dimensional Shockley state bands on Ag(111) and Cu(111) surfaces and of electrons excited to the intermediate and emerging screened states. Using the formalism of self-consistent electronic response, we analyze first the effects of screening on the dynamics of photoexcited electrons and holes and then of the Coulomb correlated photoexcited pair. Special attention is paid to the correlated primary electron-hole states, which commence as transient surface excitons and develop in the course of screening into uncorrelated electrons and holes propagating in the image potential and surface state bands, respectively. The obtained results enable to establish a consistent picture of transient electron dynamics at Ag(111) and Cu(111) surfaces that are becoming accessible by the time-, energy-, and momentum-resolved pump-probe multiphoton photoelectron spectroscopies.

Carrier-carrier and carrier-phonon interactions in the dynamics of photoexcited electrons in graphene

In this work we use the Monte Carlo method to simulate the photoexcited carrier relaxation dynamics in suspended monolayer graphene to unveil the role of the different scattering mechanisms involved. The results show a strong activity of carrier-carrier and carrier-optical phonon interactions in the very early stages of the relaxation process driving the thermalization and cooling dynamics. The consideration of the coupling between the electron and phonon population reveals an intense damping in the cooling rates that is dependent on the pumped carrier concentration.

Visible-Light Photoexcited Electron Dynamics of Scandium Endohedral Metallofullerenes: The Cage Symmetry and Substituent Effects.

Endohedral metallofullerenes (EMFs) have become an important class of molecular materials for optoelectronic applications. The performance of EMFs is known to be dependent on their symmetries and characters of the substituents, but the underlying electron dynamics remain unclear. Here we report a systematic study on several scandium EMFs and representative derivatives to examine the cage symmetry and substituent effects on their photoexcited electron dynamics using ultrafast transient absorption spectroscopy. Our attention is focused on the visible-light (530 nm as a demonstration) photoexcited electron dynamics, which is of broad interest to visible-light solar energy harvesting but is considered to be quite complicated as the visible-light photons would promote the system to a high-lying energy region where dense manifolds of electronic states locate. Our ultrafast spectroscopy study enables a full mapping of the photoinduced deactivation channels involved and reveals that the long-lived triplet exciton plays a decisive role in controlling the photoexcited electron dynamics under certain conditions. More importantly, it is found that the opening of the triplet channels is highly correlated to the fullerene cage symmetry as well as the electronic character of the substituents.

Gigahertz longitudinal acoustic phonons originating from ultrafast ligand field transitions in hematite thin films

The creation and propagation of longitudinal acoustic phonons (LAPs) in high quality hematite thin films (α-Fe2O3) epitaxially grown on different substrates (BaTiO3, SrTiO3, and LaAlO3) are investigated using the femtosecond pump–probe technique. Transient reflection measurements (ΔR/R) indicate the photo-excited electron dynamics, and the initial decay less than 1 ps and the slow decay of ∼500 ps are attributed to the electron-LO phonon coupling and electron–hole nonradiative recombination, respectively. LAPs in α-Fe2O3 film can be created by ultrafast excitation of the ligand field state, such as the ligand field transitions under 800-nm excitation as well as the ligand to metal charge-transfer with 400-nm excitation. The strain modulations of the sound velocity and the out-of-plane elastic properties are demonstrated in α-Fe2O3 film on different substrates.

Twisted-light-induced intersubband transitions in quantum wells at normal incidence

We examine theoretically the intersubband transitions induced by laser beams of light with orbital angular momentum (twisted light) in semiconductor quantum wells at normal incidence. These transitions become possible in the absence of gratings thanks to the fact that collimated laser beams present a component of the light’s electric field in the propagation direction. We derive the matrix elements of the light–matter interaction for a Bessel type twisted light beam represented by its vector potential in the paraxial approximation. Then, we consider the dynamics of photoexcited electrons making intersubband transitions between the first and second subbands of a standard semiconductor quantum well. Finally, we analyze the light–matter matrix elements in order to evaluate which transitions are more favorable for a given orbital angular momentum of the light beam in the case of small semiconductor structures.

Nonequilibrium dynamics of photoexcited electrons in graphene: Collinear scattering, Auger processes, and the impact of screening

We present a combined analytical and numerical study of the early stages (sub-100-fs) of the nonequilibrium dynamics of photoexcited electrons in graphene. We employ the semiclassical Boltzmann equation with a collision integral that includes contributions from electron-electron (e-e) and electron--optical phonon interactions. Taking advantage of circular symmetry and employing the massless Dirac fermion (MDF) Hamiltonian, we are able to perform an essentially analytical study of the e-e contribution to the collision integral. This allows us to take particular care of subtle collinear scattering processes---processes in which incoming and outgoing momenta of the scattering particles lie on the same line---including carrier multiplication (CM) and Auger recombination (AR). These processes have a vanishing phase space for two-dimensional MDF bare bands. However, we argue that electron-lifetime effects, seen in experiments based on angle-resolved photoemission spectroscopy, provide a natural pathway to regularize this pathology, yielding a finite contribution due to CM and AR to the Coulomb collision integral. Finally, we discuss in detail the role of physics beyond the Fermi golden rule by including screening in the matrix element of the Coulomb interaction at the level of the random phase approximation (RPA), focusing in particular on the consequences of various approximations including static RPA screening, which maximizes the impact of CM and AR processes, and dynamical RPA screening, which completely suppresses them.

Dynamics of photo-excited electrons in magnetically ordered TbMnO3

Time resolved optical spectroscopy is used to elucidate the dynamics of photodoped spin-aligned carriers in the presence of an underlying magnetic lattice in the multiferroic compound TbMnO3. The transient responses while probing d–d intersite transitions show marked differences along different crystallographic directions, which are discussed in terms of the interplay between the processes of hopping of the photo-injected electrons and the magnetic order in the material.

Exciton Relaxation in PbSe Nanorods

Measurements of the picosecond-time-scale dynamics of photoexcited electrons in PbSe nanorods are reported. The intraband (1Π → 1Σ) relaxation occurs with a time constant of ~500 fs, which corresponds to a fast energy-relaxation rate of ~0.6 eV/ps. The biexciton lifetime in PbSe nanorods is significantly (3-4 times) longer than the lifetime of PbSe quantum dots with the same energy gap, roughly as expected considering the increased volume. The multiexciton lifetimes of PbSe nanorods scale as expected for a bimolecular recombination mechanism. Implications of the observed relaxations will be discussed.

Full characterization and optimization of a femtosecond ultraviolet laser source for time and angle-resolved photoemission on solid surfaces

A novel experimental apparatus for time and angle-resolved photoemission on solid surfaces is presented. A 6.28 eV laser source operating at 250 kHz repetition rate is obtained by frequency mixing in nonlinear beta barium borate crystals. This UV light source has a high photon flux of 10(13) photons/s with relatively low number of photons/pulse so that Fermi surface mapping over a wide region of the Brillouin zone is possible while mitigating space charge effects. The UV source has been fully characterized spatially, spectrally, and temporally. Its potential for time and angle-resolved photoemission is demonstrated through Fermi surface mapping and photoexcited electron dynamics in Bismuth. True femtosecond time resolution <65 fs is obtained while the energy resolution of 70 meV appears to be mainly limited by the laser bandwidth.

Multiple electron injection dynamics in linearly-linked two dye co-sensitized nanocrystalline metal oxide electrodes for dye-sensitized solar cells

Understanding the electron transfer dynamics at the interface between dye sensitizer and semiconductor nanoparticle is very important for both a fundamental study and development of dye-sensitized solar cells (DSCs), which are a potential candidate for next generation solar cells. In this study, we have characterized the ultrafast photoexcited electron dynamics in a newly produced linearly-linked two dye co-sensitized solar cell using both a transient absorption (TA) and an improved transient grating (TG) technique, in which tin(IV) 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (NcSn) and cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato)ruthenium(II) bis(tetrabutylammonium) (N719) are molecularly and linearly linked and are bonded to the surface of a nanocrystalline tin dioxide (SnO(2)) electrode by a metal-O-metal linkage (i.e. SnO(2)-NcSn-N719). By comparing the TA and TG kinetics of NcSn, N719, and hybrid NcSn-N719 molecules adsorbed onto both of the SnO(2) and zirconium dioxide (ZrO(2)) nanocrystalline films, the forward and backward electron transfer dynamics in SnO(2)-NcSn-N719 were clarified. We found that there are two pathways for electron injection from the linearly-linked two dye molecules (NcSn-N719) to SnO(2). The first is a stepwise electron injection, in which photoexcited electrons first transfer from N719 to NcSn with a transfer time of 0.95 ps and then transfer from NcSn to the conduction band (CB) of SnO(2) with two timescales of 1.6 ps and 4.2 ps. The second is direct photoexcited electron transfer from N719 to the CB of SnO(2) with a timescale of 20-30 ps. On the other hand, back electron transfer from SnO(2) to NcSn is on a timescale of about 2 ns, which is about three orders of magnitude slower compared to the forward electron transfer from NcSn to SnO(2). The back electron transfer from NcSn to N719 is on a timescale of about 40 ps, which is about one order slower compared to the forward electron transfer from N719 to NcSn. These results demonstrate that photoexcited electrons can be effectively injected into SnO(2) from both of the N719 and NcSn dyes.

Effect of Photoexcited Electron Dynamics on Photocatalytic Efficiency of Bismuth Tungstate

Photoexcited carrier dynamics of bismuth tungstate (Bi2WO6) photocatalysts was investigated by time-resolved infrared (IR) absorption spectroscopy. Monotonic absorption at the mid-IR region, which is attributable to absorption by photoexcited electrons, was monitored as a function of time delay from the microsecond to millisecond range after photoexcitation. Bi2WO6 particles with different crystalline content were prepared by hydrothermal reaction at several temperatures and used to elucidate the relation between density of photoexcited carriers and steady-state photocatalytic efficiency. Photocatalytic efficiency was tested using two reactions: oxidative decomposition of acetic acid in an aqueous solution (reaction 1) and oxidative decomposition of acetaldehyde in air (reaction 2). Crystallization of Bi2WO6 particles suppressed the fast recombination of photoexcited electrons and holes within 1 μs. In the case of crystallized particles, the density of the photoexcited electron increased with an increase in the crystalline content, and the photocatalytic efficiency for reaction 1 strongly depended on the crystalline content, indicating that photoexcited electrons remaining in the submillisecond time range significantly affect the reaction rate. On the other hand, photocatalytic efficiency for reaction 2 showed a proportional relation with specific surface area rather than crystalline content. The difference in a decisive factor depending on reaction condition is considered to be the slower rate of reaction of photoexcited electrons with molecular oxygen, which might occur within a time range between 200 μs and 3 ms over Bi2WO6.

Pump-probe reflectivity study of ultrafast dynamics of strongly correlated 5f electrons in UO2

5f electrons in the Mott insulator UO2 produce intriguing electronic states and dynamics, such as strong correlation and f-f excitations. We have performed femtosecond pump-probe reflectivity measurements on a single crystal UO2 at temperatures of 5-300 K to study the ultrafast dynamics of photoexcited 5f electrons. Laser pulses at 400 nm pump 5f electrons across the Mott gap, while those at 800 nm probe the pump-induced change of reflectivity. We find temperature-dependent excitation and relaxation processes and long-lived acoustic phonons, and extract picosecond risetimes and microsecond relaxation times at low temperatures. The observed slow relaxation is ascribed to the decay of Hubbard excitons formed by U3+-U5+ pairs.