Carrier Relaxation Dynamics Research Articles

Enhancing the Hot-Phonon Bottleneck Effect in a Metal Halide Perovskite by Terahertz Phonon Excitation.

We investigate the impact of phonon excitations on the photoexcited carrier dynamics in a lead-halide perovskite CH_{3}NH_{3}PbI_{3}, which hosts unique low-energy phonons that can be directly excited by terahertz pulses. Our time-resolved photoluminescence measurements reveal that strong terahertz excitation prolongs the cooling time of hot carriers, providing direct evidence for the hot-phonon bottleneck effect. In contrast to the previous studies where phonons are treated as a passive heat bath, our results demonstrate that phonon excitation can significantly perturb the carrier relaxation dynamics in halide perovskites through the coupling between transverse- and longitudinal-optical phonons.

Optical study of relaxation dynamics of photo-induced absorption of Cr-doped Bi12SiO20 crystals

The charge carriers tunneling produced in the forbidden band of the Cr doped Bi12SiO20 has been studied using photo-induced absorption (PIA) spectroscopy. These are excited by a green nanosecond neodymium-doped Yttrium Aluminum Garnet; Nd: Y3Al5O12 (ND: YAG) laser at a wavelength of 532 nm. The relaxation dynamics of these charge carriers in this crystal are characterized by a stretched exponential decay with a highly correlated constant of a streched life time τ and a stretched coeffcient α. The charge transport processes of these charge carriers in the forbidden band in this crystal shows nearly temperature independent behavior from the Arrhenius plot. This corresponds to a very weak dependence of the PIA of the charge carriers' dynamics within the forbidden band. The electo-optical descriptions are explained in the framework of the fast and slow time decays of the charge carriers tunneling within the localized states.

Monte Carlo Solution of High Electric Field Hole Transport Processes in Avalanche Amorphous Selenium.

Amorphous selenium lacks the structural long-range order present in crystalline solids. However, the stark similarity in the short-range order that exists across its allotropic forms, augmented with a shift to non-activated extended-state transport at high electric fields beyond the onset of impact ionization, allowed us to perform this theoretical study, which describes the high-field extended-state hole transport processes in amorphous selenium by modeling the band-transport lattice theory of its crystalline counterpart trigonal selenium. An in-house bulk Monte Carlo algorithm is employed to solve the semiclassical Boltzmann transport equation, providing microscopic insight to carrier trajectories and relaxation dynamics of these non-equilibrium “hot” holes in extended states. The extended-state hole–phonon interaction and the lack of long-range order in the amorphous phase is modeled as individual scattering processes, namely acoustic, polar and non-polar optical phonons, disorder and dipole scattering, and impact ionization gain, which is modeled using a power law Keldysh fit. We have used a non-parabolic approximation to the density functional theory calculated valence band density of states. To validate our transport model, we calculate and compare our time of flight mobility, impact ionization gain, ensemble energy and velocity, and high field hole energy distributions with experimental findings. We reached the conclusion that hot holes drift around in the direction perpendicular to the applied electric field and are subject to frequent acceleration/deceleration caused by the presence of high phonon, disorder, and impurity scattering. This leads to a certain determinism in the otherwise stochastic impact ionization phenomenon, as usually seen in elemental crystalline solids.

Ultrafast dynamics of photoconductivity in lead sulfide nanocrystals in terahertz region

The dynamics of carrier relaxation and charge transport of photoinduced carriers in Lead Sulfide nanocrystals with quantum confinement, synthesized by chemical bath deposition method, have been simultaneously determined using time-resolved terahertz spectroscopy with sub-picosecond time resolution. We use both Drude-Smith and Drude Lorenz model to successfully reproduce the photoconductivity spectra, which manifest that localized free-carriers not bounded excitons are responsible to the THz transport in PbS nanocrystals. The pump fluence dependence of carrier dynamics reveals the process of Auger recombination through the interaction between free carriers and excitons.

Assessment of nanostructure, optical, dielectric and modulus response by Bi substitution in La1−xBixNi0.5Ti0.5O3 (x = 0.0–0.2) system

Perovskite-type oxides La1-xBixNi0.5Ti0.5O3 (x = 0.0, 0.2) were prepared by the sol–gel method employing the citric acid route and sintered at 820° C. The structural behavior analyzed by X-ray diffraction proved that all the samples have the same crystallographic structure (space group Pnma). The volume of the elemental lattice decreases with the rate of Bismuth substitution. Transmission electron microscopy (TEM) verified the nanosized grains. The FTIR spectra confirmed the formation of the orthorhombic perovskite structure. UV–Visible spectroscopy and photoluminescence were also applied to study the samples. The parameters of real and imaginary part of dielectric function (e′ and e″) and dielectric loss tangent (tg(δ)) show a strong frequency dependence. Those dependences explain a dispersive behavior at low frequencies and are outlined on the basis of the Maxwell–Wagner model and Koop theory. The compounds have very high dielectric constant values (e′ ≈ 103) that are useful in electronic devices. Electric modulus formalism was employed to investigate the relaxation dynamics of charge carriers. Moreover, a non-Debye type of relaxation was verified in our samples. The activation energy is specified from the analysis of the imaginary part of the electric modulus.

Efficient quantum-dot light-emitting diodes featuring the interfacial carrier relaxation and exciton recycling

Tremendous achievements of colloidal quantum-dot (QD) light-emitting diodes (QLEDs) in both efficiency and lifetime have been witnessed in the past decade. However, multiple interfacial losses such as defect-induced exciton quenching and multicarrier Auger recombination can severely suppress the device performance of QLEDs. Here, we present the efficient QLEDs by adopting the new liquid-solid-solution processed magnesium-doped zinc oxide nanocrystals (ZMO-LSS) as an electron-transport layer. A magic carrier relaxation dynamics is demonstrated at the QD emitter/ZMO-LSS interface for abnormal exciton recycling and enhanced radiative recombination, which arises from the subtle intragap band coupling of surface trap states as directly clarified by the prolonged electroluminescence decays of devices. Red-emitting QLEDs on rigid glass achieve a maximum external quantum efficiency (EQE) of 22.3% with virtual droop-free over a wide range of brightness from 10,000 to 200,000 cd m−2. By further combining a silver nanowires-based composited electrode on a plastic substrate, a substantial boost in EQE up to 24.0% is realized for flexible devices. The present results provide an in-depth study on interfacial recombination and convey a clear picture of constructing ZMO-LSS for efficient QLEDs and related optoelectronic devices.

Carrier Dynamics in Thin Germanium–Tin Epilayers

The Si-based mid-infrared photonics is an emerging technology in which group-IV germanium–tin (Ge1–xSnx) binary alloys can play a fundamental role in the development of a Si-compatible photonic components including monolithically integrated coherent light sources and detectors, on the same Si or SOI substrate. Although the Ge1–xSnx-on-Si lasers, at low temperatures, have already been demonstrated, the knowledge of the material properties necessary for such device optimization and real-life usage is very limited. In particular, carrier relaxation kinetics, relaxation pathways, and accompanied physical mechanisms, important for the laser’s dynamics, have not been subjected to in-depth research and understanding. In this work, we present detailed spectroscopic studies on photoinjected carrier dynamics in Ge1–xSnx epilayers, as a function of Sn content (6–12%) and temperature (20–300 K), by utilizing time-resolved differential reflectivity and photoluminescence. The latter technique allowed us to track separated electron and hole dynamics with a femtosecond time resolution, while the former experiment exploited a joined electron–hole recombination. This experimental approach allowed us to identify (i) two initial electron relaxation processes after photoexcitation; (ii) radiative electron–hole recombination on below-band gap states; (iii) nonradiative carrier recombination involving the Shockley–Read–Hall mechanism; and (iv) nonradiative recombination through the surface states. The research results significantly expand the knowledge on the initial carrier relaxation dynamics in the Ge1–xSnx epitaxial material. It provides unknown up-to-date kinetic parameters of the initial stage of electron relaxation and further carrier recombination dynamics, unveils the critical role of band gap inhomogeneity for the relaxation dynamics, and highlights the role of below-band gap states that can participate in the light generation process in Ge1–xSnx epilayers.

Determining Quasiparticle Bandgap of Two-Dimensional Transition Metal Dichalcogenides by Observation of Hot Carrier Relaxation Dynamics.

Using excitation-energy-scanning ultrafast infrared microspectroscopy, the excess energy-dependent hot carrier relaxation dynamics in atomically thin two-dimensional transition metal dichalcogenides (2D TMDs) after femtosecond photoexcitation was directly monitored. A good linear relationship between the carrier relaxation time and the excitation wavelength is observed for all measured monolayer (ML) and bilayer (BL) TMD samples, which allows us to determine their quasiparticle bandgaps as well as corresponding exciton binding energies. A carrier-optical-phonon scattering-mediated cascading-relaxation model is proposed, which can perfectly describe all the measured dynamics. As a consequence, the quasiparticle bandgaps of ML MoSe2, ML MoS2, BL MoSe2, and BL WSe2 are determined to be 2.07, 2.11, 1.67, and 1.81 eV, respectively. Our work reveals a general picture for the hot carrier relaxation dynamics in atomically thin TMDs and offers an effective experimental approach in probing the bandgaps of TMDs under ambient conditions.

Temperature-Dependent Ultrafast Response and π-Plasmon Dynamics in Single-Walled Carbon Nanotubes.

Temperature-dependent femtosecond time-resolved carrier relaxation dynamics has been studied in thin films of single-walled carbon nanotubes. An early time evolution of the photoexcited relaxation shows evidence of superimposed transient bleaching and induced photo absorption of almost similar strengths, whereas at longer times it is governed by slow recovery of long-lived dark excitons. After about 3 ps, the signal is dictated by the slowest negative relaxation component attributed to the low-energy π-plasmons. An absorption trough near 500 fs in the ultrafast response evolves with the increasing sample temperature. This particular feature is masked by the reduced induced transmission at room temperature and above. We have estimated the electron-phonon coupling constant to be ∼0.86 from the linear temperature dependence of the slow relaxation time constant. More such studies can help advance the understanding of the intrinsic charge and energy loss mechanisms to improve the efficiency of the optoelectronic devices based on them.

Ultrafast Charge Delocalization Dynamics of Ambient Stable CsPbBr3 Nanocrystals Encapsulated in Polystyrene Fiber.

CsPbBr3 nanocrystals (NCs) encapsulated in a transparent polystyrene (PS) fiber matrix (CsPbBr3 @PS) have been synthesized to protect the NCs. The ultrafast charge delocalization dynamics of the embedded NCs have been demonstrated, and the results are compared with the pristine CsPbBr3 in toluene. The electrospinning method was employed for the preparation of CsPbBr3 @PS fibers by using a polystyrene solution doped with pre-synthesized CsPbBr3 and characterized by XRD, HRTEM, and X-ray photoelectron spectroscopy (XPS). Energy level diagrams of CsPbBr3 and PS suggest that CsPbBr3 @PS fibers make a type I core-shell structure. The carrier cooling for CsPbBr3 @PS fibers is found to be much slower than pure CsPbBr3 NCs. This observation suggests that photoexcited electrons from CsPbBr3 NCs get delocalized from the conduction band of the perovskite to lowest unoccupied molecular orbital (LUMO) of the PS fiber matrix. The CsPbBr3 @PS fibers possess remarkable stability under ambient conditions as well as in water over months. The clear understanding of charge carrier relaxation dynamics of CsPbBr3 confined in PS fibers could help to design robust optoelectronic devices.

Elucidating the Influence of Sulfur Vacancies on Nonradiative Recombination Dynamics in Cu2ZnSnS4 Solar Absorbers.

We report a time-domain ab initio simulation of charge carrier trapping and relaxation dynamics in pristine and defect-containing kesterite Cu2ZnSnS4 (CZTS) structures. Our simulations show that introduction of a neutral sulfur vacancy in the CZTS system leads to a decrease of the charge recombination rate by a factor of ∼4, and the doubly positively charged sulfur vacancy results in a minor decrease of carrier lifetime, as compared to the pristine CZTS system. The neutral sulfur vacancy weakens the nonadiabatic (NA) electron-phonon coupling by moderately localizing charge density and accelerates the pure dephasing process, extending charge carrier lifetime. Therefore, the neutral sulfur vacancy is electrically benign. The doubly positively charged sulfur vacancy introduces a subgap state which is hardly populated, and recombination of the electron and hole bypassing the trap state dominates. As a result, the recombination rate decreases in the doubly charged sulfur vacancy structure. The reported results identified the key role of the sulfur-related vacancy on charge carrier trapping and relaxation of CZTS materials, carrying important implications for further optimization of CZTS and other thin-film solar cell materials.

Ultrafast Carrier Relaxation Dynamics in Quantum Confined Non-Isotropic Silicon Nanostructures Synthesized by an Inductively Coupled Plasma Process.

To exploit the optoelectronic properties of silicon nanostructures (SiNS) in real devices, it is fundamental to study the ultrafast processes involving the photogenerated charges separation, migration and lifetime after the optical excitation. Ultrafast time-resolved optical measurements provide such information. In the present paper, we report on the relaxation dynamics of photogenerated charge-carriers in ultrafine SiNS synthesized by means of inductively-coupled-plasma process. The carriers’ transient regime was characterized in high fluence regime by using a tunable pump photon energy and a broadband probe pulse with a photon energy ranging from 1.2 eV to 2.8 eV while varying the energy of the pump photons and their polarization. The SiNS consist of Si nanospheres and nanowires (NW) with a crystalline core embedded in a SiOx outer-shell. The NW inner core presents different typologies: long silicon nanowires (SiNW) characterized by a continuous core (with diameters between 2 nm and 15 nm and up to a few microns long), NW with disconnected fragments of SiNW (each fragment with a length down to a few nanometers), NW with a “chaplet-like” core and NW with core consisting of disconnected spherical Si nanocrystals. Most of these SiNS are asymmetric in shape. Our results reveal a photoabsorption (PA) channel for pump and probe parallel polarizations with a maximum around 2.6 eV, which can be associated to non-isotropic ultra-small SiNS and ascribed either to (i) electron absorption driven by the probe from some intermediate mid-gap states toward some empty state above the bottom of the conduction band or (ii) the Drude-like free-carrier presence induced by the direct-gap transition in the their band structure. Moreover, we pointed up the existence of a broadband and long-living photobleaching (PB) in the 1.2–2.0 eV energy range with a maximum intensity around 1.35 eV which could be associated to some oxygen related defect states present at the Si/SiOx interface. On the other hand, this wide spectral energy PB can be also due to both silicon oxide band-tail recombination and small Si nanostructure excitonic transition.

Charge Carrier Relaxation in Colloidal FAPbI3 Nanostructures Using Global Analysis

We study the hot charge carrier relaxation process in weakly confined hybrid lead iodide perovskite colloidal nanostructures, FAPbI3 (FA = formaminidium), using femtosecond transient absorption (TA). We compare the conventional analysis method based on the extraction of the carrier temperature (Tc) by fitting the high-energy tail of the band-edge bleach with a global analysis method modeling the continuous evolution of the spectral lineshape in time using a simple sequential kinetic model. This practical approach results in a more accurate way to determine the charge carrier relaxation dynamics. At high excitation fluence (density of charge carriers above 1018 cm−3), the cooling time increases up to almost 1 ps in thick nanoplates (NPs) and cubic nanocrystals (NCs), indicating the hot phonon bottleneck effect. Furthermore, Auger heating resulting from the multi-charge carrier recombination process slows down the relaxation even further to tens and hundreds of picoseconds. These two processes could only be well disentangled by analyzing simultaneously the spectral lineshape and amplitude evolution.

A Direct Mapping Approach to Understand Carrier Relaxation Dynamics in Varied Regions of a Polycrystalline Perovskite Film.

We developed a direct mapping approach to overlay the image of a polycrystalline perovskite film obtained from the transient absorption microscope (TAM) with that from the scanning electron microscope (SEM). By mapping these imaging data pixel by pixel, we are able to observe the relaxation dynamics of the photo-generated charge carriers on varied regions of the film. The carrier relaxation dynamics contain a dominated single-exponential decay component owing to the recombination of charge carriers. The lifetime distribution of charge recombination shows a bimodal feature, for which the rapid and slow distributions are assigned as free and trapped carriers, respectively. The charge recombination was slower in the grain boundary (GB) region than in the grain interior (GI) region. The small grains have longer lifetimes than the large grains for the crystal size smaller than 500 nm. Therefore, GB with retarded charge recombination might play a positive role in a perovskite solar cell.

A Direct Mapping Approach to Understand Carrier Relaxation Dynamics in Varied Regions of a Polycrystalline Perovskite Film

AbstractWe developed a direct mapping approach to overlay the image of a polycrystalline perovskite film obtained from the transient absorption microscope (TAM) with that from the scanning electron microscope (SEM). By mapping these imaging data pixel by pixel, we are able to observe the relaxation dynamics of the photo‐generated charge carriers on varied regions of the film. The carrier relaxation dynamics contain a dominated single‐exponential decay component owing to the recombination of charge carriers. The lifetime distribution of charge recombination shows a bimodal feature, for which the rapid and slow distributions are assigned as free and trapped carriers, respectively. The charge recombination was slower in the grain boundary (GB) region than in the grain interior (GI) region. The small grains have longer lifetimes than the large grains for the crystal size smaller than 500 nm. Therefore, GB with retarded charge recombination might play a positive role in a perovskite solar cell.

High refractive nonlinearity of PdO films under femtosecond 800 nm laser pulses

Nonlinear optical properties of thin polycrystalline PdO films are investigated using the Z-scan technique and a 800 nm 180 fs laser, whose wavelength is significantly longer than the absorption edge at 500 nm. Cubic nonlinear susceptibility Re χ(3) = +1.1 × 10−6 esu (n2 = 5.6 × 10−9 cm2/W) and nonlinear absorption coefficient β ≈ 5 × 10−5 cm/W are determined. The positive sign of Re χ(3) implies intraband carrier (predominantly holes) relaxation dynamics and the optical Kerr effect as underlying mechanisms. Relaxation time of refractive nonlinearity is estimated in the picosecond range. Linear absorption spectra in the interval of 1.5–6 eV, compared with the literature data, suggest that microcrystals in our films are predominantly oriented with the С axis orthogonal to the film.

Femtosecond Transient Absorption Spectra and Dynamics of Carrier Relaxation of Tin Perovskites in the Absence and Presence of Additives.

The effects of additives SnF2 (10%) and EDAI2 (1%) on the dynamics of carrier relaxation of formamidinium tin triiodide (FASnI3) perovskite were studied using femtosecond transient absorption spectra (TAS) with excitation at 600 and 870 nm. The TAS were analyzed according to a parallel sequential kinetic model with a global fit through singular-value decomposition. For excitation at 600 nm, two relaxation paths were found: one involved hot and cold carriers in the bulk state undergoing shallow bulk-defect-mediated charge recombination; the other involved trap carriers in the surface state undergoing deep surface-defect-mediated charge recombination. For excitation at 870 nm, only cold carriers were subjected to the bulk-state relaxation channel. Our spectral results indicate significant effects of the additives on retarding charge recombination in both bulk and surface states as well as decreasing the bandgap renormalization energy, the bandwidth of the photobleaching (PB) band, and the Stokes shift between the PB and photoluminescence bands, explaining how the device performance of FASnI3 solar cells became enhanced in the presence of SnF2 and EDAI2.

An ultrafast and low-power slow light tuning mechanism for compact aperture-coupled disk resonators**Project supported by the National Natural Science Foundation of China (Grant Nos. 11647122 and 61705064) and the Natural Science Foundation of Hubei Province, China (Grant Nos. 2018CFB672 and 2018CFB773).

An ultrafast and low-power slow light tuning mechanism based on plasmon-induced transparency (PIT) for two disk cavities aperture-coupled to a metal-dielectric-metal plasmonic waveguide system is investigated numerically and analytically. The optical Kerr effect is enhanced by the local electromagnetic field of surface plasmon polaritons, slow light, and graphene–Ag composite material structures with a large effective Kerr nonlinear coefficient. Through the dynamic adjustment of the frequency of the disk nanocavity, the group velocity is controlled between c/53.2 and c/15.1 with the pump light intensity increased from 0.41 MW/cm2 to 2.05 MW/cm2. Alternatively, through the dynamic adjustment of the propagation phase of the plasmonic waveguide, the group velocity is controlled between c/2.8 and c/14.8 with the pump light intensity increased from 5.88 MW/cm2 to 11.76 MW/cm2. The phase shift multiplication of the PIT effect is observed. Calculation results indicate that the entire structure is ultracompact and has a footprint of less than 0.8 μm2. An ultrafast responsive time in the order of 1 ps is reached due to the ultrafast carrier relaxation dynamics of graphene. All findings are comprehensively analyzed through finite-difference time-domain simulations and with a coupling-mode equation system. The results can serve as a reference for the design and fabrication of nanoscale integration photonic devices with low power consumption and ultrafast nonlinear responses.

Carrier dynamics and excitation of Eu3+ ions in GaN

The carrier mobility and dynamics of nonequilibrium carriers in Eu-doped GaN have been determined by above-band-gap, optically excited, time-resolved terahertz spectroscopy and compared with that of undoped GaN. The carrier mobility of GaN:Eu was an order of magnitude smaller than that of a similarly grown undoped GaN layer. Two time constants were observed in the carrier relaxation dynamics for GaN:Eu. A fast one (2.2 ps), which we related to an efficient nonradiative carrier trap, and a slower one (\ensuremath{\sim}85 ps) related to Eu-related traps. Ultrafast photoluminescence spectroscopy shows that Eu-related emission is observed within 100 ps after a pulsed excitation. These values set an upper value to the energy-transfer time from the Eu-related trap to $\mathrm{E}{\mathrm{u}}^{3+}$ ion and underlie the high efficiency of the excitation of $\mathrm{E}{\mathrm{u}}^{3+}$ ions in GaN.

Intraband Relaxation Dynamics of Charge Carriers within CdTe Quantum Wires.

The state-to-state intraband relaxation dynamics of charge carriers photogenerated within CdTe quantum wires (QWs) are characterized via transient absorption spectroscopy. Overlapping signals from the energetic-shifting of the quantum-confinement features and the occupancy of carriers in the states associated with these features are separated using the quantum-state renormalization model. Holes generated with an excitation energy of 2.75 eV reach the band edge within the instrument response of the measurement, ∼200 fs. This extremely short relaxation time is consistent with the low photoluminescence quantum yield of the QWs, ∼0.2%, and the presence of alternative relaxation pathways for the holes. The electrons relax through the different energetically available quantum-confinement states, likely via phonon coupling, with an overall rate of ∼0.6 eV ps-1.