Femtosecond transient absorption spectroscopy and microscopy were employed to study exciton dynamics in suspended and Si 3 N 4 substrate-supported monolayer and few-layer MoS 2 2D crystals. Exciton dynamics for the monolayer and few-layer structures were found to be remarkably different from those of thick crystals when probed at energies near that of the lowest energy direct exciton (A exciton). The intraband relaxation rate was enhanced by more than 40 fold in the monolayer in comparison to that observed in the thick crystals, which we attributed to defect assisted scattering. Faster electronÀhole recombination was found in monolayer and few-layer structures due to quantum confinement effects that lead to an indirectÀdirect band gap crossover. Nonradiative rather than radiative relaxation pathways dominate the dynamics in the monolayer and few-layer MoS 2 . Fast trapping of excitons by surface trap states was observed in monolayer and few-layer structures, pointing to the importance of controlling surface properties in atomically thin crystals such as MoS 2 along with controlling their dimensions.

The Shockley-Queisser limit for solar cell efficiency can be overcome if hot carriers can be harvested before they thermalize. Recently, carrier cooling time up to 100 picoseconds was observed in hybrid perovskites, but it is unclear whether these long-lived hot carriers can migrate long distance for efficient collection. We report direct visualization of hot-carrier migration in methylammonium lead iodide (CHNHPbI) thin films by ultrafast transient absorption microscopy, demonstrating three distinct transport regimes. Quasiballistic transport was observed to correlate with excess kinetic energy, resulting in up to 230 nanometers transport distance that could overcome grain boundaries. The nonequilibrium transport persisted over tens of picoseconds and ~600 nanometers before reaching the diffusive transport limit. These results suggest potential applications of hot-carrier devices based on hybrid perovskites.

We systematically investigate the exciton dynamics in monolayered, bilayered, and trilayered WS2 two-dimensional (2D) crystals by time-resolved photoluminescence (TRPL) spectroscopy. The exciton lifetime when free of exciton annihilation was determined to be 806 ± 37 ps, 401 ± 25 ps, and 332 ± 19 ps for WS2 monolayer, bilayer, and trilayer, respectively. By measuring the fluorescence quantum yields, we also establish the radiative and nonradiative lifetimes of the direct and indirect excitons. The exciton decay in monolayered WS2 exhibits a strong excitation density-dependence, which can be described using an exciton-exciton annihilation (two-particle Auger recombination) model. The exciton-exciton annihilation rate for monolayered, bilayered, and trilayered WS2 was determined to be 0.41 ± 0.02, (6.00 ± 1.09) × 10(-3) and (1.88 ± 0.47) × 10(-3) cm(2) s(-1), respectively. Notably, the exciton-exciton annihilation rate is two orders of magnitude faster in the monolayer than in the bilayer and trilayer. We attribute the much slower exciton-exciton annihilation rate in the bilayer and trilayer to reduced many-body interaction and phonon-assisted exciton-exciton annihilation of indirect excitons.

No abstract

Two-dimensional (2D) atomically thin perovskites with strongly bound excitons are highly promising for optoelectronic applications. However, the nature of nonradiative processes that limit the photoluminescence (PL) efficiency remains elusive. Here, we present time-resolved and temperature-dependent PL studies to systematically address the intrinsic exciton relaxation pathways in layered (CHNH)(CHNH)PbI (n = 1, 2, 3) structures. Our results show that scatterings via deformation potential by acoustic and homopolar optical phonons are the main scattering mechanisms for excitons in ultrathin single exfoliated flakes, exhibiting a T (γ = 1.3 to 1.9) temperature dependence for scattering rates. We attribute the absence of polar optical phonon and defect scattering to efficient screening of Coulomb potential, similar to what has been observed in 3D perovskites. These results establish an understanding of the origins of nonradiative pathways and provide guidelines for optimizing PL efficiencies of atomically thin 2D perovskites.

Charge carrier diffusion coefficient and length are important physical parameters for semiconducting materials. Long-range carrier diffusion in perovskite thin films has led to remarkable solar cell efficiencies; however, spatial and temporal mechanisms of charge transport remain unclear. Here we present a direct measurement of carrier transport in space and in time by mapping carrier density with simultaneous ultrafast time resolution and ∼50-nm spatial precision in perovskite thin films using transient absorption microscopy. These results directly visualize long-range carrier transport of ∼220 nm in 2 ns for solution-processed polycrystalline CH3NH3PbI3 thin films. Variations of the carrier diffusion coefficient at the μm length scale have been observed with values ranging between 0.05 and 0.08 cm2 s−1. The spatially and temporally resolved measurements reported here underscore the importance of the local morphology and establish an important first step towards discerning the underlying transport properties of perovskite materials.

Singlet fission presents an attractive solution to overcome the Shockley-Queisser limit by generating two triplet excitons from one singlet exciton. However, although triplet excitons are long-lived, their transport occurs through a Dexter transfer, making them slower than singlet excitons, which travel by means of a Förster mechanism. A thorough understanding of the interplay between singlet fission and exciton transport is therefore necessary to assess the potential and challenges of singlet-fission utilization. Here, we report a direct visualization of exciton transport in single tetracene crystals using transient absorption microscopy with 200 fs time resolution and 50 nm spatial precision. These measurements reveal a new singlet-mediated transport mechanism for triplets, which leads to an enhancement in effective triplet exciton diffusion of more than one order of magnitude on picosecond to nanosecond timescales. These results establish that there are optimal energetics of singlet and triplet excitons that benefit both singlet fission and exciton diffusion.

No abstract