Carrier Relaxation Dynamics Research Articles

Modulating hot carrier relaxation and trapping dynamics in lead halide perovskite nanoplatelets by surface passivation.

Two-dimensional (2D) lead halide perovskite (LHP) nanoplatelets (NPLs) have recently emerged as promising materials for solar cells and light-emitting devices. The reduction of LHP dimensions introduces an abundance of surface defects, which can strongly influence the photophysical properties of these materials. However, an insightful understanding of the effect of surface defects on hot carrier (HC) relaxation, one of the important properties of LHP NPLs, is still inadequate. Herein, the HC relaxation and trapping dynamics in pristine and surface passivated two-layer (2L) CsPbBr3 NPLs have been investigated by using time-resolved spectroscopy. The results reveal that surface defects can trap HCs directly before they relax to the band edge, which accounts for the absence of the hot-phonon bottleneck (HPB) effect in LHP NPLs. After healing surface defects with a passivation agent, the relaxation time of HCs is extended from ∼73 to ∼130 fs in 2L CsPbBr3 NPLs, indicating that the channel of HCs trapped by the surface defects can be effectively blocked. Accordingly, the HPB effect is activated in surface-passivated CsPbBr3 NPLs. The finding of surface defect-related HC relaxation dynamics is important for guiding the development of high-performance LHP NPL devices related to HCs through surface defect engineering.

Quantifying relaxation time constants in MoS2xSe2(1-x) alloys: Impact of Stoichiometry and Si/SiO2 interference

Despite a decade of extensive research on two-dimensional transition metal dichalcogenides, there are still some gaps in our understanding of their remarkable properties, limiting their potential applications. One such gap relates to the properties of these alloys, which offer tunable band gaps and can serve as the basis for various optoelectronic and nonlinear optical devices. A comprehensive understanding of the ultrafast charge carrier excitation and relaxation dynamics as well as their characteristic relaxation time constants, is crucial for the further use of these materials in specific applications. In this work, we experimentally investigate the dynamics of ultrafast relaxation processes in monolayer MoS2xSe2(1-x) alloys on a Si/SiO2 substrate using time-resolved spectroscopy. We determine the characteristic relaxation time constants for structures with different stoichiometric compositions and refine these constants by accounting for interference effects arising from the substrate.

A room-temperature ultrafast carrier dynamical study and thickness-dependent investigation of WTe2 thin films on a flexible PET substrate

In the current era of increasing demand for optoelectronic-based devices with ultra-rapid response, it is important to understand the processes associated with the relaxation dynamics of hot carriers and transient electrical properties of WTe2 material under photoexcitation of charge carriers. In this work, using femtosecond laser pump–probe spectroscopy at room temperature we performed the transient absorption measurement on sputtered deposited WTe2 thin films having four different thicknesses to study dynamics associated with the relaxation of their hot carriers. The relaxation dynamics of photoexcited charge carriers undergo three exponential decay components associated with electron–phonon thermalization in the conduction band and phonon-assisted electron–hole recombination between the electron and hole pocket. The thickness-dependent investigation of WTe2 thin films reveals that the electron–hole recombination process is more prominent in thicker films than in thinner films, supporting previously published theoretical and experimental conclusions. The Ultrafast study of WTe2 thin films suggests that it is a suitable material for future ultrafast optoelectronic-based device applications.

Hot Electron Cooling in n-Doped Colloidal Nanoplatelets Following Near-Infrared Intersubband Excitation.

Intersubband transition was recently discovered in colloidal nanoplatelets, but the associated intersubband carrier relaxation dynamics remains poorly understood. In particular, it is crucial to selectively excite the intersubband transition and to follow the hot electron dynamics in the absence of valence-band holes. This is achieved herein by exciting the predoped electrons in CdSe/ZnS nanoplatelets using near-infrared femtosecond pulses and monitoring nonequilibrium electron dynamics using broad-band visible pulses. We find that the n = 2 electrons relax to the n = 1 subband and establish a Fermi-Dirac distribution within 200 fs, and finally reach an equilibrium with the lattice within a few ps. The cooling dynamics depend mainly on the excitation fluence but weakly on the doping density and the lattice temperature. These characteristics are well captured by our numerical simulation that explicitly accounts for the state occupation effect and optical phonon scattering.

Introducing Ag Dopants into CdSe Nanoplatelets (NPLs) Leads to Effective Charge Separation for Better Photodetector Performance.

Solution-processed colloidal cadmium chalcogenide nanoplatelets (NPLs)-based photodetectors (PD) are promising materials for next-generation optoelectronic devices due to their excellent optical properties. Here, we report on ultrafast carrier relaxation dynamics of four monolayer (4 ML) Ag-doped CdSe (Ag: CdSe) NPLs using ultrafast transient absorption spectroscopy and their photodetectors applications. A broad dopant emission is observed at around 650 nm with a large FWHM of ~431 meV and band edge emission at 515 nm. The intragap dopant state acts as a hole acceptor, which leads to better charge separation. The ultrafast transient absorption spectroscopy study shows faster carrier recombination dynamics with a hole transfer time scale of ~10 ps in Ag-doped CdSe NPLs. This supports the excited hole capture phenomenon at the dopant state. Ag-doped CdSe NPLs-based PD performed better than undoped CdSe NPLs with detectivity and responsivity values of 1.3×1010 Jones and 2.4 mA/W, respectively.

Unraveling the cation dependent carrier cooling and transient mobility in lead-free A3Sb2I9 perovskites.

Lead halide perovskites (LHPs) have gained prominence for their exceptional photophysical properties, holding promise for applications in high-end optoelectronic devices. However, the presence of lead is one of the major obstacles to the commercialization of LHPs in the field of photovoltaics. To address this, researchers have explored environment friendly lead-free perovskite solar cells by investigating non-toxic perovskite materials. This study explores the enhancement of photophysical properties through chemical engineering, specifically cation exchange, focusing on the crucial photophysical process of hot carrier cooling. Employing femtosecond transient absorption spectroscopy and optical pump terahertz probe spectroscopy, we have probed the carrier relaxation dynamics in A3Sb2I9 with cesium and rubidium cations. This study unravels that the carrier relaxation is found to be slower in Rb3Sb2I9; along with this, the transient mobility decay is found to be retarded. Overall, this study suggests that an antimony-based Rb3Sb2I9 perovskite could be a substantial lead-free perovskite in photovoltaics. These findings provide valuable insights into cation engineering strategies, aiming to improve the overall performance of lead-free-based photovoltaic devices.

Providing a Review of Hot Carrier (HC) Relaxation Dynamics and Strategies of HC Extraction in Perovskites Nanocrystals

AbstractMetal halide perovskite (MHPs) nanocrystals (NCs) have recently emerged as promising materials for optoelectronic applications due to their exceptional photophysical properties. A comprehensive understanding of the underlying principles and key challenges associated with controlling the hot carrier (HC) cooling dynamics in MHPs is pivotal for the design of efficient perovskite‐based optoelectronic applications. This review highlights the general carrier cooling mechanism and identifies influencing crucial controlling parameters for carrier dynamics. The discussion includes strategies for manipulating HC cooling dynamics through carrier‐phonon and carrier‐carrier interactions. Notably, recent advancements in HC extraction with suitable acceptors are explored, as efficient HC extraction is imperative for the advancement of optoelectronic applications. The objective of this review is to outline potential pathways for strategically modifying carrier cooling processes to align with specific optoelectronic applications. A profound comprehension of charge carrier dynamics in MHPs NCs will pave the way for the development of highly efficient optoelectronic applications.

Ultrafast relaxation dynamics of excited carriers in metals: Simplifying the intertwined dependencies upon scattering strengths, phonon temperature, photon energy, and excitation level

Ultrafast relaxation dynamics of excited carriers in metals: Simplifying the intertwined dependencies upon scattering strengths, phonon temperature, photon energy, and excitation level

Unveiling the Potential of Halide Perovskites for Seasonally Adaptive CO2 Photoreduction under Low Light Conditions

AbstractThe viability of double perovskite Cs2AgBiBr6 in low‐light environments is studied for CO2 photoreduction. It is observed that light intensity significantly influences product formation with I0.56 depending on the overall product formation rate. The photodetection measurement reveals that photocurrent as a function of incident power follows a power law ∝ I0α with α = 0.80, which is attributed to the carrier trapping at higher light power. Furthermore, power‐dependent transient absorption spectroscopy is studied and observed that at higher fluence, carrier scattering can be dominating. Interestingly, it is found that at higher power, hot carrier relaxation dynamics are altered, and electron‐phonon coupling is enhanced, resulting in a lower carrier concentration participating in the photocatalytic reaction, which can limit charge carrier extraction and CO2 reduction. This study highlights the potential of perovskite semiconductors as promising candidates for photocatalytic reactions in low‐light conditions, broadening their applicability in real‐world scenarios.

Exploring hot carrier relaxation dynamics in MoSi2N4 monolayer for photocatalytic applications: Insights into electron-phonon coupling mechanisms

The relaxation process of hot carriers in MoSi2N4 monolayer remains unclear due to the need to sample electron–phonon interaction at different momenta. Utilizing density functional theory (DFT) combined with nonadiabatic molecular dynamics (NAMD), we determined that the material possesses an indirect bandgap of approximately 2.33 eV, primarily originating from the d orbitals of inner Mo atoms. NAMD simulations unveil rapid relaxation of hot electrons and holes, exhibiting lifetimes of approximately 166 fs and 146 fs, respectively. The rapid relaxation of hot carriers couples with the vibrations of outer Si and N atoms, with no inter-valley scattering observed between the K and K′ valleys. Notably, the coupling between the d orbitals of inner Mo atoms and the vibrations of outer Si and N atoms plays a pivotal role in determining the relaxation dynamics of hot carriers, shedding light on the intricate interplay between electronic and vibrational modes in this material. Our research reveals the potential application value of MoSi2N4 monolayer material as a photocatalyst and elucidates a relaxation mechanism governing the dynamics of excited carriers.

Hot carrier relaxation dynamics of an aza-covalent organic framework during photoexcitation: An insight from abinitio quantum dynamics.

In order to develop an efficient metal-free solar energy harvester, we herein performed the electronic structure calculation, followed by the hot carrier relaxation dynamics of two dimensional (2D) aza-covalent organic framework by time domain density functional calculations in conjunction with non-adiabatic molecular dynamics (NAMD) simulation. The electronic structure calculation shows that the aza-covalent organic framework (COF) is a direct bandgap semiconductor with acute charge separation and effective optical absorption in the UV-visible region. Our study of non-adiabatic molecular dynamics simulation predicts the sufficiently prolonged electron-hole recombination process (6.8 nanoseconds) and the comparatively faster electron (22.48ps) and hole relaxation (0.51ps) dynamics in this two-dimensional aza-COF. According to our theoretical analysis, strong electron-phonon coupling is responsible for the rapid charge relaxation, whereas the electron-hole recombination process is slowed down by relatively weak electron-phonon coupling, relatively lower non-adiabatic coupling, and quick decoherence time. We do hope that our results of NAMD simulation on exciton relaxation dynamics will be helpful for designing photovoltaic devices based on this two dimensional aza-COF.

Phonon-mediated ultrafast energy- and momentum-resolved hole dynamics in monolayer black phosphorus.

The electron-phonon scattering plays a crucial role in determining the electronic, transport, optical, and thermal properties of materials. Here, we employ a non-Markovian stochastic Schrödinger equation (NMSSE) in momentum space, together with abinitio calculations for energy bands and electron-phonon interactions, to reveal the phonon-mediated ultrafast hole relaxation dynamics in the valence bands of monolayer black phosphorus. Our numerical simulations show that the hole can initially remain in the high-energy valence bands for more than 100fs due to the weak interband scatterings, and its energy relaxation follows single-exponential decay toward the valence band maximum after scattering into low-energy valence bands. The total relaxation time of holes is much longer than that of electrons in the conduction band. This suggests that harnessing the excess energy of holes may be more effective than that of electrons. Compared to the semiclassical Boltzmann equation based on a hopping model, the NMSSE highlights the persistence of quantum coherence for a long time, which significantly impacts the relaxation dynamics. These findings complement the understanding of hot carrier relaxation dynamics in two-dimensional materials and may offer novel insights into harnessing hole energy in photocatalysis.

Exciton-carrier coupling in a metal halide perovskite nanocrystal assembly probed by two-dimensional coherent spectroscopy

The surface chemistry and inter-connectivity within perovskite nanocrystals play a critical role in determining the electronic interactions. They manifest in the Coulomb screening of electron–hole correlations and the carrier relaxation dynamics, among other many-body processes. Here, we characterize the coupling between the exciton and free carrier states close to the band-edge in a ligand-free formamidinium lead bromide nanocrystal assembly via two-dimensional coherent spectroscopy. The optical signatures observed in this work show: (i) a nonlinear spectral lineshape reminiscent of Fano-like interference that evidences the coupling between discrete electronic states and a continuum, (ii) symmetric excited state absorption cross-peaks that suggest the existence of a coupled exciton-carrier excited state, and (iii) ultrafast carrier thermalization and exciton formation. Our results highlight the presence of coherent coupling between exciton and free carriers, particularly in the sub-100 femtosecond timescales.

Orbital ordering and ultrafast carrier dynamics anisotropies in orientation-engineered orthorhombic YMnO3 films

The rich physical properties unveiled in a plethora of transition and rare-earth metal oxides have been attributed to the intricate interplays between the orbital, charge, and spin degrees of freedom. Among them, rare-earth manganites (RMnO3) have been attracting tremendous attention owing to the ionic size-induced lattice distortion dictated by the Goldschmidt tolerance factor and the substantial Jahn–Teller distortion unique to Mn3+ ions, which evidently have resulted in a variety of emergent characteristics in electronic, magnetic, and orbital ordering. In this work, we deliberately engineered the orientation of a series of orthorhombic YMnO3 (o-YMO) films grown on SrTiO3(100) [STO(100)] and SrTiO3(110) [STO(110)] substrates by means of pulsed laser deposition. The x-ray diffraction (XRD) and reciprocal space mapping revealed that o-YMO/STO(100) is c-axis-oriented and o-YMO/STO(110) is a-axis-oriented, respectively. The XRD ϕ-scans further indicate that both films have excellent in-plane crystallinity, allowing the exploration of anisotropies along the respective crystallographic orientations. Indeed, the x-ray absorption linear dichroism spectroscopy taken along the respective crystallographic orientations evidently exhibited substantial anisotropy. Theoretical fitting with configuration interaction cluster calculations suggests that the d3z2−r2 orbitals are parallel to YMO[001]/(100), leading to stronger electron scattering along the c-axis. Independent polarization-dependent Δ R/R spectra obtained using the femtosecond pump–probe method exhibited substantial anisotropic behaviors in carrier relaxation dynamics when probing along different crystallographic orientations, presumably due to orbital ordering anisotropies.

Anisotropic carrier dynamics and laser-fabricated luminescent patterns on oriented single-crystal perovskite wafers

Perovskite materials and their applications in optoelectronics have attracted intensive attentions in recent years. However, in-depth understanding about their anisotropic behavior in ultrafast carrier dynamics is still lacking. Here we explore the ultrafast dynamical evolution of photo-excited carriers and photoluminescence based on differently-oriented MAPbBr3 wafers. The distinct in-plane polarization of carrier relaxation dynamics of the (100), (110) and (111) wafers and their out-of-plane anisotropy in a picosecond time scale were found by femtosecond time- and polarization-resolved transient transmission measurements, indicating the relaxation process dominated by optical/acoustic phonon interaction is related to photoinduced transient structure rearrangements. Femtosecond laser two-photon fabricated patterns exhibit three orders of magnitude enhancement of emission due to the formation of tentacle-like microstructures. Such a ultrafast dynamic study carried on differently-oriented crystal wafers is believed to provide a deep insight about the photophysical process of perovskites and to be helpful for developing polarization-sensitive and ultrafast-response optoelectronic devices.

Carrier relaxation and exciton dynamics in chemical-vapor-deposited two-dimensional hybrid halide perovskites

Transient absorption spectroscopy from chemical vapor deposited 2D perovskites shows differences in carrier dynamics depending on the organic cations. The decay reveals a strong contribution from the Auger recombination process at early times.

Point defect-mediated hot carrier relaxation dynamics of lead-free FASnI3 perovskites.

In search of a promising optoelectronic performance, we herein investigated the hot carrier relaxation dynamics of a lead-free cubic phased bulk formamidinium tin triiodide (FASnI3) perovskite. To gain detailed theoretical insights, we should estimate the carrier relaxation dynamics of this pristine perovskite. To control the dynamics, point defects like central tin (Sn), iodine(I) anions, and formamidinium (FA) cations were introduced. With the iodine vacancy in the FASnI3 perovskite, the system seems to be unstable at room temperature, whereas the other three types of FASnI3 perovskites (pristine, Sn vacancy, and FA vacancy) are significantly stable at 300 K having semiconducting nature and excellent optical absorption in the UV-visible range. The computed electron-hole recombination time for the pristine system is 3.9 nanoseconds, which is in good agreement with the experimental investigation. The exciton relaxation processes in Sn and FA vacancy perovskites require 2.8 and 4.8 nanoseconds, respectively. These variations in the hot carrier relaxation dynamics processes are caused by the generation of significant changes in non-adiabatic coupling between energy levels, electron-phonon coupling, and quantum decoherence in different point defect analogous systems. The results presented here offer deeper insight into the temperature-dependent carrier relaxation dynamics of FASnI3 perovskites and thus open up opportunities for future exploration of their optoelectronic properties.

Organic cation dependent hot carrier relaxation dynamics in two-dimensional perovskites

Organic cation dependent hot carrier relaxation dynamics in two-dimensional perovskites

Ultrafast magneto-optical dynamics in nickel (111) single crystal studied by the integration of ultrafast reflectivity and polarimetry probes

With the integration of ultrafast reflectivity and polarimetry probes, we observed carrier relaxation and spin dynamics induced by ultrafast laser excitation of Ni (111) single crystals. The carrier relaxation time within the linear excitation range reveals that electron–phonon coupling and dissipation of photon energy into the bulk of the crystal take tens of picoseconds. On the other hand, the observed spin dynamics indicate a longer time of about 120 ps. To further understand how the lattice degree of freedom is coupled with these dynamics may require the integration of an ultrafast diffraction probe.

Colossal permittivity, impedance analysis and electric properties in AlGaN/GaN HEMTs

The electric and dielectric processes of AlGaN/GaN/Si HEMTs produced by molecular beam epitaxy were examined utilizing direct current-voltage, impedance spectroscopy, and DLTS measurements. Using current-voltage measurements, the DC electrical characteristics of AlGaN/GaN/Si HEMTs revealed the self-heating effect. The relaxation dynamics of charge carriers appear to be studied by the conductance mechanism and electric modulus formalisms. Behavior that is frequency dependent has been observed in impedance spectroscopy. Last but not least, DLTS data have demonstrated the existence of electron traps. The prevalence of parasitic effects and conduction mechanisms are remarkably correlated with deep levels.