Hot Carrier Relaxation Research Articles

Influence of the rate of radiation energy on the charge-carrier kinetics application of all-inorganic CsPbBr3 perovskite nanocrystals.

In the field of optoelectronics, all-inorganic CsPbBr3 perovskite nanocrystals (PNCs) have gained significant interest on account of their superb processability and ultra-high stability among all the counterparts. In this study, we conducted an in-depth analysis of CsPbBr3 PNCs using joint transient optical spectroscopies (time-resolved photoluminescence and ultrafast transient absorption) in a very comprehensive manner. In order to understand the in-depth analysis of excited-state kinetics, the transient absorption spectroscopy has been performed. The structure of interest of CsPbBr3 PNCs was subjected to the rates of the radiation energy of 0.10 mW (κr/κnr = ∼0.62) and 0.30 mW (κr/κnr = ∼0.64). With the rate of radiation energy 0.30 mW, it was observed that there was a significant increase in hot carrier relaxation together with high radiative recombination, resulting in a decrease in charge trappings. Herein, we demonstrate that the tuning of the rate of radiation energies helps to understand the charge-carrier kinetics of CsPbBr3 PNCs, which would thus improve the manufacturing of efficient photovoltaic devices.

Hot carrier dynamics in a dispersionless plasmonic system

Hot carrier dynamics in a broadband, dispersionless, plasmonic structure are studied using pump-probe measurements with 45 fs time resolution. The results obtained by simultaneous measurement of differential transmittance and reflectance show the influence of pump generated carriers on the probe generated plasmons. The dependence of decay time on the pump fluence is linear for the interband and intraband carrier excitation near the L-symmetry point in gold. However, 1.908 eV pump excitation, which allows both interband transition at the X-symmetry point and intraband excitation at the L-symmetry point, shows quadratic dependence of decay time on the pump fluence. Degenerate pump-probe measurements at 1.55 eV, which allow L-valley intraband excitations, highlight the difference in surface (reflection) and the bulk (transmission) mechanisms. Hot carrier relaxation time is in the 1–3 ps range for different excitation energies. Rise time, governed by the plasmon to hot carrier conversion and electron-electron scattering processes, is about 200 ± 35 fs for the hot carrier and hot plasmon excitation cases that increased to about 485 ± 35 fs when the pump is resonant with the interband transition at the X-symmetry point. Results show that the hot carrier dynamics are governed by the bulk metal band structure. The dipole matrix element for each of the transitions is estimated by density matrix calculations.

Tuning Hot Carrier Cooling Dynamics by Dielectric Confinement in Two-Dimensional Hybrid Perovskite Crystals

Hot carrier (HC) cooling is a critical photophysical process that significantly influences the optoelectronic performance of hybrid perovskite-based devices. The hot carrier extraction at the device interface is very challenging because of its ultrashort lifetime. Here, ultrafast transient reflectance spectroscopy measurements and time-domain ab initio calculations show how the dielectric constant of the organic spacers can control and slow the HC cooling dynamics in single-crystal 2D Ruddlesden-Popper hybrid perovskites. We find that (EA)2PbI4 (EA = HOC2H4NH3+) that correspond to a high dielectric constant organic spacer has a longer HC cooling time compared to that of (AP)2PbI4 (AP = HOC3H6NH3+) and (PEA)2PbI4 (PEA = C6H5C2H4NH3+). The slow HC relaxation process in the former case can be ascribed to a stronger screening of the Coulomb interactions, a small nonradiative internal conversion within the conduction bands, as well as a weak electron-phonon coupling. Our findings provide a strategy to prolong the hot carrier cooling time in low-dimensional hybrid perovskite materials by using organic spacers with reduced dielectric confinement.

Infrared ultrafast spectroscopy of solution-grown thin film tellurium

Several materials studied intensively in their bulk forms several decades ago have re-emerged in recent years in their thin film and monolayer manifestations. Tellurium, like black phosphorus, is one such elemental two-dimensional material with promising semiconducting properties for electronic and optoelectronic applications. To study fundamental carrier properties such as hot carrier relaxation and recombination, we performed ultrafast femtosecond pump-probe spectroscopy on thin flakes of solution-grown tellurium. To access the low band gap of tellurium, we used infrared, near-band-gap and below-band-gap probes to monitor the relaxation processes. Sweeping the probing wavelengths across the band gap helps to shed light on the anisotropic band structure of the material. We find that relaxation in flakes of 60--160 nm thickness is on the order of 100 s of picoseconds. Thinner flakes (10--20 nm), on the other hand, exhibit fast relaxation times of sub-20 ps. Radiative recombination is identified as the relaxation mechanism in thick flakes, whereas midgap trap states arising from surface defects and impurities are responsible for the fast relaxation in thin flakes. A diffusion-recombination model accounting for the surface defect and radiative recombinations explains the experimental data well.

Layer-Dependent Coherent Acoustic Phonons in Two-Dimensional Ruddlesden-Popper Perovskite Crystals.

By combining femtosecond transient reflectance (TR) spectroscopy and density functional theory (DFT) calculations, we reveal the impact of the length of the organic linkers (HOC2H4NH3+ and C6H5C2H4NH3+) and the number of inorganic layers (n = 1-3) on the hot carrier relaxation dynamics and coherent acoustic phonons in 2D Ruddlesden-Popper (RP) perovskites. We find that the interplay between the hot carriers and the coherent longitudinal acoustic phonons (CLAPs) can extend the oscillation of the TR kinetics to nanoseconds, which could lead to the higher thermal conductivities of 2D RP perovskites. Moreover, we find that the frequency of the acoustic phonon oscillation and phonon velocity decreases with the increasing number of layers due to the increased mass of the inorganic layers and reduced electron-phonon coupling. This finding provides new physical insights into how the organic spacers and number of inorganic layers control the overall carrier dynamics of 2D perovskite materials.

Ultrafast Photoluminescence from Suspended Gold/Graphene Hybrid Structures

Gold is a classical metal with the Fermi level lying in the sp-band, while graphene is a zero-bandgap semiconductor with Dirac band structure. Thus, the photon emission from both gold and graphene can not be effectively achieved by electron–holes recombination as direct bandgap semiconductors. Alternatively, optical emission from hot carriers is possible in graphene and gold, but usually with very low efficiency. This is because the hot carrier relaxation time is much faster than the radiative lifetime in both graphene and gold. To solve this problem, here we show that in suspended graphene structures the photon emission intensity can be enhanced by increasing the hot carrier relaxation time, while in suspended gold/graphene hybrid structures, the photon emission intensity also increased with increasing holes sizes. Since nowadays most semiconductor light sources are based on bandgap design and also restricted by it, the study could help to develop materials with the emission wavelength not being limited ...

Monitoring Electron-Phonon Interactions in Lead Halide Perovskites Using Time-Resolved THz Spectroscopy.

Lead halide perovskite semiconductors have low-frequency phonon modes within the lead halide sublattice and thus are considered to be soft. The soft lattice is considered to be important in defining their interesting optoelectronic properties. Electron-phonon coupling governs hot-carrier relaxation, carrier mobilities, carrier lifetimes, among other important electronic characteristics. Directly observing the interplay between free charge carriers and phonons can provide details on how phonons impact these properties (e.g., exciton populations and other collective modes). Here, we observe a delicate interplay among carriers, phonons, and excitons in mixed-cation and mixed-halide perovskite films by simultaneously resolving the contribution of charge carriers and phonons in time-resolved terahertz photoconductivity spectra. We are able to observe directly the increase in phonon population during carrier cooling and discuss how thermal equilibrium populations of carriers and phonons modulate the carrier transport properties, as well as reduce the population of carriers within band tails. We are also able to observe directly the formation of free charge carriers when excitons interact with phonons and dissociate and to describe how free carriers and exciton populations exchange through phonon interactions. Finally, we also time-resolve how the carriers are screened via the Coulomb interaction at low and room temperatures. Our studies shed light on how charge carriers interact with the low-energy phonons and discuss implications.

The fast and the furious: Ultrafast hot electrons in plasmonic metastructures. Size and structure matter

Abstract This review focuses on the generation of energetic (hot) electrons in plasmonic metastructures and nanomaterials, and their characterization through time-resolved spectroscopy. Excitation of hot electrons under illumination occurs in any metal or conductor, but their number will vary for each type of nanostructure. While plasmonic resonances are well described classically, the excitation of hot electrons (HEs) is a quantum process and its description requires further elaboration. Some potential applications for HEs lie in the fields of photo-catalysis and optoelectronics, and their study constitutes a very active interdisciplinary research direction that involves chemistry, physics and device engineering. Here we focus on some particular developments enabling the use of hot carriers for these applications. Particularly, we discuss the approaches and structures required to create hot carriers, the temporal dynamics of hot carrier formation and relaxation, and relevant theoretical methods used to compute the HE dynamics. The observations presented here support the conclusion that the shape of the nanostructure matters. Although metastructures with infrared gap plasmons can exhibit spatially extended hot spots and anomalously large numbers of non-thermalized HEs, most excited carriers in a plasmonic nanostructure typically have small excitation energies. Here we discuss ways to strongly increase the number of high-energy electrons, highlighting the role of hot spots, system size, geometry and resonant frequencies. To generate HEs efficiently, we can take advantage of special geometries with hot spots, such as metamaterial absorbers with ultra-narrow gaps or nanostars. Furthermore, we discuss the applications in ultrafast electronics based on plasmon-enhanced photoemission and tunneling in the nonlinear regime. Considering the longer timescale phenomena, we also present studies on the coherent dynamics in a nanostructure after electron thermalization, showing acoustic breathing modes. In this paper, we review some key developments in the field of ultra-fast plasmonic dynamics and provide a perspective for its possible next steps.

Cooling, Scattering, and Recombination—The Role of the Material Quality for the Physics of Tin Halide Perovskites

AbstractTin‐based perovskites have long remained a side topic in current perovskite optoelectronic research. With the recent efficiency improvement in thin film solar cells and the observation of a long hot carrier cooling time in formamidinium tin iodide (FASnI3), a thorough understanding of the material's photophysics becomes a pressing matter. Since pronounced background doping can easily obscure the actual material properties, it is of paramount importance to understand how different processing conditions affect the observed behavior. Using photoluminescence spectroscopy, thin films of FASnI3 fabricated through different protocols are therefore investigated. It is shown that hot carrier relaxation occurs much faster in highly p‐doped films due to carrier–carrier scattering. From high quality thin films, the longitudinal optical phonon energy and the electron–phonon coupling constant are extracted, which are fundamental to understanding carrier cooling. Importantly, high quality films allow for the observation of a previously unreported state of microsecond lifetime at lower energy in FASnI3, that has important consequences for the discussion of long lived emission in the field of metal halide perovskites.

Nonadiabatic molecular dynamics with decoherence and detailed balance under a density matrix ensemble formalism

Author(s): Kang, J; Wang, LW | Abstract: The mixed quantum-classical nonadiabatic molecular dynamics (NAMD) is a powerful tool to study many phenomena, especially ultrafast carrier transport and cooling. Carrier decoherence and detailed balance are two major issues in NAMD. So far, there is no computationally inexpensive approach to incorporate both effects. While the decoherence effect can be easily included in the state density matrix formalism and the detailed balance can be included in surface hopping or the wave function collapse approach, it is difficult to include both of them in a unified formalism. In this work we introduce a state density matrix formalism (referred to as P-matrix) including both the decoherence and detailed balance effects for NAMD. This method is able to explicitly treat the decoherence between different pairs of adiabatic states. Moreover, the off-diagonal density matrix elements are divided into two parts, corresponding to energy-increasing and energy-decreasing transitions. The detailed balance is then enforced by a Boltzmann factor applied to the energy-increasing transition part. The P-matrix formalism is applied to study hot-hole cooling and transfer processes in Si quantum dot (QD) systems. The calculated hot-carrier relaxation time is consistent with experiments. In a QD-pair system, the hot-hole cooling time shows weak dependence on the QD spacing. However, the hot-carrier transfer rate from one QD to another is found to decrease exponentially with the QD-QD distance. When the QD spacing is small (∼1 nm), the hot-carrier transfer can be very efficient. It is also shown that the explicit treatment of decoherence time is important in order to treat this hot-carrier transfer correctly.

Ultrafast nonlinear absorption and carrier relaxation in ReS2 and ReSe2 films

As two important members of two-dimensional (2D) transition metal dichalcogenides, ReS2 and ReSe2 have gained interest for optoelectronic and photonic applications. The key to the application of the 2D materials to the optoelectronic devices is to understand the interaction between light and matter. Here, we report that the chemical vapor deposition-grown few-layer ReS2 and ReSe2 display saturable absorption under 400 nm pulse excitation, measured through intensity dependent transmission and confirmed by ΔT/T spectroscopy. ΔT/T spectroscopy substantiates the coexistence of saturable absorption and excited state absorption at 800 nm for both ReS2 and ReSe2. Two time constants are extracted from time-resolved spectroscopy; the short time constant of 10–20 ps is associated with the relaxation of hot carriers and exciton formation, and the long time constant of 70–100 ps is assigned to exciton lifetime. The polarization dependence of ΔT/T reveals that the initial distribution of photoexcited carriers centered at excitation state is anisotropic, and this initial anisotropy loses rapidly with carrier relaxation. The nonequilibrium carriers scattered far away from excitation state are fully isotropic in the entire relaxation process. These findings provide fundamental information for using the two materials in ultrafast optoelectronic and photonic devices.

Infrared Photodetector Based on the Photothermionic Effect of Graphene-Nanowall/Silicon Heterojunction.

Because of the slow relaxation process according to weak acoustic phonon interaction, the photothermionic effect in graphene could be much more obvious than in the metal film, so a graphene heterojunction photodetector based on the photothermionic effect is promising for infrared imaging applications. However, the 2.3% absorption rate of the graphene film presents a severe limitation. Here, in situ grown graphene nanowalls (GNWs) were integrated on the silicon substrate interfaced with Au nanoparticles. Because of the strong infrared absorption and hot-carrier relaxation process in GNWs, the as-prepared GNWs/Au/silicon heterojunction has a photo to dark ratio of 2 × 104, responsivity of 138 mA/W, and linear dynamic range of 89.7 dB, with a specific detectivity of 1.4 × 1010 and 1.6 × 109 cm Hz1/2/W based on calculated and measured noise, respectively, in 1550 nm at room temperature, and has the best performance among silicon-compatible infrared photodetectors without any complicated waveguide structures. Obvious photoresponses are also detected in the mid-infrared and terahertz band. The interface Au particle is found to reduce the barrier height and enhance absorption. The device structure in this report could be compatible with the semiconductor process, so that infrared photodetectors with high integration density and low cost could be potentially realized.

Controlling the Efficiency of Singlet Fission in TIPS-Pentacene/Polymer Composite Nanoparticles

Singlet fission (SF) is a process with the potential to increase the efficiency of solar cells by reducing losses from thermal relaxation of hot carriers. By generating two triplet excitons from one singlet exciton, the process effectively splits the energy of high-energy photons into two, providing a means to circumvent the Shockley–Queisser limit. Although the applications of SF are promising, questions remain about the mechanistic details and practicalities of implementation in photovoltaic devices that must be resolved to exploit its full potential. In this study, we present a way to investigate the effect of average intermolecular distance on SF by embedding 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pn) in an amorphous polymer matrix in the form of aqueous nanoparticle dispersions. By controlling the mass ratio of TIPS-Pn to the host polymer, we systematically tune the concentration of TIPS-Pn molecules in a nanoparticle and in turn, the average intermolecular separation, leading to a range of SF quantum yields. We study this system using both steady-state and ultrafast time-resolved spectroscopic techniques and fit the results to a kinetic model to decipher the observed behavior. The quantum yield of SF is shown to decrease with average intermolecular separation, which is explained by diffusion-limited SF and an increase in loss pathways through isolated sites. Additionally, we identify an intermediate species in the SF process and show that a significant proportion of this species decays nonradiatively without dissociating to form separated triplets, revealing a major loss pathway that has important implications for future research and applications.

Effect of Water on the Structural, Optical, and Hot-Carrier Cooling Properties of the Perovskite Material MASnI3

Understanding the stability, carrier transport, and relaxation of Sn-based hybrid perovskite CH3NH3SnI3 is of high interest to develop lead-free perovskite solar cells. In this study, we perform first-principles and nonadiabatic ab initio molecular dynamics simulations to address the electronic and optical properties as well as hot-carrier relaxation dynamics of pristine CH3NH3SnI3 and its monohydrated phase CH3NH3SnI3·H2O. Our results show that the water molecules interact strongly with the organic part [CH3NH3]+ of the material by forming hydrogen bonding. They also interact with the inorganic lattice (mostly with iodide ions). Our study also indicates a profound effect of water molecules on the optical properties of the perovskite materials. For example, the water molecules reduce the absorption of the system mostly in the visible range of the solar spectrum. The presence of water molecules also leads to faster hot-carrier cooling and enhanced polarization of the material.

Cation-Dependent Hot Carrier Cooling in Halide Perovskite Nanocrystals.

Lead halide perovskites (LHPs) nanocrystals (NCs), owing to their outstanding photophysical properties, have recently emerged as a promising material not only for solar cells but also for lighting and display applications. The photophysical properties of these materials can be further improved by chemical engineering such as cation exchange. Hot carrier (HC) cooling, as one of the key photophysical processes in LHPs, can strongly influence performance of LHPs NCs based devices. Here, we study HC relaxation dynamics in LHP NCs with cesium (Cs), methylammonium (MA, CH3NH3+), and formamidinium (FA, CH(NH2)2+) cations by using femtosecond transient absorption spectroscopy. The LHP NCs show excitation intensity and excitation energy-dependent HC cooling. We investigate the details of HC cooling in CsPbBr3, MAPbBr3, and FAPbBr3 at three different excitation energies with low excitation intensity. It takes longer time for the HCs at high energy to relax (cool) to the band edge, compared to the HCs generated by low excitation energy. At the same excitation energy (350 nm, 3.54 eV), all the three LHP NCs show fast HC relaxation (<0.4 ps) with the cooling time and rate in the following order: CsPbBr3 (0.39 ps, 2.9 meV/fs) > MAPbBr3 (0.27 ps, 4.6 meV/fs) > FAPbBr3 (0.21 ps, 5.8 meV/fs). The cation dependence can be explained by stronger interaction between the organic cations with the Pb-Br frameworks compared to the Cs. The revealed cation-dependent HC relaxation process is important for providing cation engineering strategies for developing high performance LHP devices.

Colloidal Synthesis and Charge-Carrier Dynamics of Cs2 AgSb1-y Biy X6 (X: Br, Cl; 0 ≤y ≤1) Double Perovskite Nanocrystals.

A series of lead-free double perovskite nanocrystals (NCs) Cs2 AgSb1-y Biy X6 (X: Br, Cl; 0≤y≤1) is synthesized. In particular, the Cs2 AgSbBr6 NCs is a new double perovskite material that has not been reported for the bulk form. Mixed Ag-Sb/Bi NCs exhibit enhanced stability in colloidal solution compared to Ag-Bi or Ag-Sb NCs. Femtosecond transient absorption studies indicate the presence of two prominent fast trapping processes in the charge-carrier relaxation. The two fast trapping processes are dominated by intrinsic self-trapping (ca. 1-2 ps) arising from giant exciton-phonon coupling and surface-defect trapping (ca. 50-100 ps). Slow hot-carrier relaxation is observed at high pump fluence, and the possible mechanisms for the slow hot-carrier relaxation are also discussed.

Energy relaxation of hot carriers near the charge neutrality point in HgTe-based 2D topological insulators

We present experimental results of non-linear transport in HgTe-based 2D topological insulators, where the conductance is dominated by Dirac-like helical edge states when the Fermi level is pinned to the bulk insulating gap. We find that hot carrier's energy relaxation is faster close to the charge neutrality point (CNP) which can be attributed to localized nature and incompressibility of charge puddles resulting from inhomogeneous charge distribution near CNP. The tunnel-coupling of these puddles (quantum dots) to 1D edge channels can randomize phase memory leading to incoherent inelastic processes. Hot edge carriers, excited by the electric field, relax to equilibrium via thermalization in multiple puddles resulting in the emission of phonons in the puddles. At relatively low temperature (T ≤ 10 K), the energy relaxation time shows strong temperature dependence (τε ∝ (Te−5)), which is interpreted as small angle scattering, consistent with resistance saturation at low temperatures.

Anion-dependent Hot Carrier Dynamics in Chalcogenide Perovskites SrSnX3 (X = S, Se)

The hot carrier relaxation dynamics in inorganic perovskites SrSnS3 and SrSnSe3 has been investigated using nonadiabatic molecular dynamics simulation. The results indicate that the hot carrier relaxation dynamics strongly depends on the chalcogenide element. It is found that the hot electrons and hot holes have a fast relaxation time in SrSnS3 than SrSnSe3 with the similar excess energy due to the strong nonadiabatic couplings. Moreover, the hot holes hold a dramatic faster decay time than hot electrons for both of the two systems because of the large density of states and the smaller energy level differences in the valence band. Generally, our findings here show that the hot carrier relaxation time in chalcogenide perovskites SrSnS3 and SrSnSe3 is longer than the organic–inorganic perovskites, indicating the present chalcogenide perovskites are promising candidates for solar cell applications.

Impact of Organic Spacers on the Carrier Dynamics in 2D Hybrid Lead-Halide Perovskites

We have carried out nonadiabatic molecular dynamics simulations combined with time-dependent density functional theory calculations to compare the properties of the two-dimensional (2D) (BA)2(MA)Pb2I7 and three-dimensional (3D) MAPbI3 (where MA = methylammonium and BA = butylammonium) materials. We evaluate the different impacts that the 2D-confined spacer layer of butylammonium cations and the 3D-confined methylammonium cations have on the charge carrier dynamics in the two systems. Our results indicate that, while both the MA+ and BA+ cations play important roles in determining the carrier dynamics, the BA+ cations exhibit stronger nonadiabatic couplings with the 2D perovskite framework. The consequence is a faster hot-carrier decay rate in 2D (BA)2(MA)Pb2I7 than in 3D MAPbI3. Thus, tuning of the functional groups of the organic spacer cations in order to reduce the vibronic couplings between the cations and the Pb–I framework can offer the opportunity to slow down the hot-carrier relaxations and increa...

CsPbBr3 Nanocrystal/MO2 (M = Si, Ti, Sn) Composites: Insight into Charge-Carrier Dynamics and Photoelectrochemical Applications.

Though coating CsPbBr3 nanocrystal (NC) with an outer layer has been regarded as an effective strategy to address its instability issues, deep investigations into the electronic interaction between CsPbBr3 NC and coating layer have yet to be conducted. In this study, the dynamics of hot carrier and charge carrier of CsPbBr3 nanocrystal with various MO2 (M = Si, Ti, Sn) coating layers have been comprehensively studied. Combined transient optical characterizations (time-resolved photoluminescence and ultrafast transient absorption) and photoelectrochemical measurements reveal that coating with insulating SiO2 accelerates the hot carrier relaxation and enhances the radiative recombination by passivating surface traps, whereas efficient charge-carrier separation and extraction are observed after coating with SnO2 and TiO2. The electron injection from CsPbBr3 NC to SnO2 (1.14 × 108 s-1) is 2-fold faster than to TiO2 (5.4 × 107 s-1) owing to the lower conduction band edge and the higher electron mobility of SnO2. Particularly, the first time fabricated CsPbBr3 NC/SnO2 composite exhibits superior stability against UV light and moisture, as well as the best photocurrent response in this study. This work has implied that rational design of the coating layer for perovskite NC can not only improve the stability but also tailor the electronic and optoelectronic properties for various applications.