Femtosecond Transient Absorption Microscopy Research Articles

Direct Visualization of Dark Interlayer Exciton Transport in Moiré Superlattices.

Moiré superlattices have emerged as an unprecedented manipulation tool for engineering correlated quantum phenomena in van der Waals heterostructures. With moiré potentials as a naturally configurable solid-state that sustains high exciton density, interlayer excitons in transition metal dichalcogenide heterostructures are expected to achieve high-temperature exciton condensation. However, the exciton degeneracy state is usually optically inactive due to the finite momentum of interlayer excitons. Experimental observation of dark interlayer excitons in moiré potentials remains challenging. Here we directly visualize the dark interlayer exciton transport in WS2/h-BN/WSe2 heterostructures using femtosecond transient absorption microscopy. We observe a transition from classical free exciton gas to quantum degeneracy by imaging temperature-dependent exciton transport. Below a critical degeneracy temperature, exciton diffusion rates exhibit an accelerating downward trend, which can be explained well by a nonlinear quantum diffusion model. These results open the door to quantum information processing and high-precision metrology in moiré superlattices.

The anisotropic nature of singlet fission in single crystalline organic semiconductors

The escalating global energy predicament implores for a revolutionary resolution—one that converts sunlight into electricity—holding the key to supreme conversion efficiency. This comprehensive review embarks on the exploration of the principle of generating multiple excitons per absorbed photon, a captivating concept that possesses the potential to redefine the fundamental confines of conversion efficiency, albeit its application remains limited in photovoltaic devices. At the nucleus of this phenomenon are two principal processes: multiple exciton generation (MEG) within quantum-confined environments, and singlet fission (SF) inside molecular crystals. The process of SF, characterized by the cleavage of a single photogenerated singlet exciton into two triplet excitons, holds promise to potentially amplify photon-to-electron conversion efficiency twofold, thereby laying the groundwork to challenge the detailed balance limit of solar cell efficiency. Our discourse primarily dissects the complex nature of SF in crystalline organic semiconductors, laying special emphasis on the anisotropic behavior of SF and the diffusion of the subsequent triplet excitons in single-crystalline polyacene organic semiconductors. We initiate this journey of discovery by elucidating the principles of MEG and SF, tracing their historical genesis, and scrutinizing the anisotropy of SF and the impact of quantum decoherence within the purview of functional mode electron transfer theory. We present an overview of prominent techniques deployed in investigating anisotropic SF in organic semiconductors, including femtosecond transient absorption microscopy and imaging as well as stimulated Raman scattering microscopies, and highlight recent breakthroughs linked with the anisotropic dimensions of Davydov splitting, Herzberg–Teller effects, SF, and triplet transport operations in single-crystalline polyacenes. Through this comprehensive analysis, our objective is to interweave the fundamental principles of anisotropic SF and triplet transport with the current frontiers of scientific discovery, providing inspiration and facilitating future ventures to harness the anisotropic attributes of organic semiconductor crystals in the design of pioneering photovoltaic and photonic devices.

Observation of energy transfer dynamics in a phycocyanin protein crystal by utilizing femtosecond transient absorption microscopy

Energy transfer reactions are important in photosynthetic systems as natural systems and solar cells as artificial systems. Especially in the biological system, the energy transfer reaction from the phycobilisome to the photoreaction system is the essence. Femtosecond transient absorption microscopy was utilized for the phycocyanin protein in crystals. The energy transfer reactions among pigments were observed with the changes in spectral shape. The time constants of energy transfer to the respective electronic states of 760 fs, 17 ps, and 62 ps were obtained. Transient absorption microscopy is a powerful nanotool for measuring the carrier dynamics in a microcrystal.

Observation of carrier dynamics in MoS2 thin layer by femtosecond transient absorption microscopy

Since the Nobel Prize was awarded in 2010 to Andre Geim and Konstantin Novoselov for their work on graphene, research in two-dimensional materials has attracted much attention. Transition metal dichalcogenides, which consist of transition metal atoms and chalcogen atoms other than oxygen, have potential applications in various electronics fields. However, there have been few observations of the transition processes of these electronic states, and the mechanisms of their functions are still unclear. In this study, the carrier dynamics of mechanically exfoliated MoS2 film were observed using femtosecond transient absorption microscopy. The time constant of carrier relaxation at the thin region was shorter than those of the thick. Electronic state differences and carrier trapping on the surface state regulate the lifetime of carriers in MoS2.

Observation of electronic spectra modulation in a CH3NH3PbBr3 crystal by utilizing transient absorption microscopy

Organic–inorganic lead halide perovskite materials have attractive properties not only for solar cells but also for LED because of their high performance and wavelength tunability. Such an efficient light-emitting and lasing nature are indispensable for their applications, and the essential needs are miniaturization and low lasing threshold. One material that satisfies these requirements is lead halide perovskite. To understand the time evolution of the interaction between light and matter in a perovskite crystal system, it is necessary to reveal the carrier dynamics in each crystal. In this study, the transient absorption spectra of CH3NH3PbBr3 crystals were measured using a femtosecond transient absorption microscopy. Surprisingly, strong spectra modulation has been observed and these results indicate the charge separation on the surface of the crystal. Amplified spontaneous emission dynamics were also observed in the transient absorption spectra.

Ultrafast transient absorption measurements of photocarrier dynamics in PdSe2.

We investigate the photocarrier dynamics in bulk PdSe2, a layered transition metal dichalcogenide with a novel pentagonal structure and unique electronic and optical properties. Using femtosecond transient absorption microscopy, we study the behavior of photocarriers in mechanically exfoliated bulk PdSe2 flakes at room temperature. By employing a 400 nm ultrafast laser pulse, electron-hole pairs are generated, and their dynamics are probed using an 800 nm detection pulse. Our findings reveal that the lifetime of photocarriers in bulk PdSe2 is approximately 210 ps. Furthermore, by spatially resolving the differential reflection signal, we determine a photocarrier diffusion coefficient of about 7.3 cm2 s-1. Based on these results, we estimate a diffusion length of around 400 nm and a photocarrier mobility of approximately 300 cm2 V-1 s-1. These results shed light on the ultrafast optoelectronic properties of PdSe2, offer valuable insights into photocarriers in this emerging material, and enable design of high-performance optoelectronic devices based on PdSe2.

Visualizing Ultrafast Defect-Controlled Interlayer Electron-Phonon Coupling in Van der Waals Heterostructures.

Engineering ultrafast interlayer coupling provides access to new quantum phenomena and novel device functionalities in atomically thin van der Waals heterostructures. However, due to all the atoms of a monolayer material being exposed at the interfaces, the interlayer coupling is extremely susceptible to defects, resulting in high energy dissipation through heat and low device performance. The study of how defects affect the interlayer coupling at ultrafast and atomic scales remains a challenge. Here, using femtosecond transient absorption microscopy, a new defect-induced ultrafast interlayer electron-phonon coupling pathway is identified in a WS2 /graphene heterostructure, involving a three-body collision between electrons in WS2 and both acoustic phonons and defects in graphene. This interaction manifests as the reduced defect-related Raman resonant activity and the accelerated electron-phonon scattering time from 7.1 to 2.4ps. Furthermore, the ultrafast interlayer coupling process is directly imaged. These insights will advance the fundamental knowledge of heat dissipation in nanoscale devices, and enable new ways to dynamically manipulate electrons and phonons via defects in van der Waals heterostructures.

Tuning the Coherent Propagation of Organic Exciton-Polaritons through Dark State Delocalization.

While there have been numerous reports of long‐range polariton transport at room‐temperature in organic cavities, the spatiotemporal evolution of the propagation is scarcely reported, particularly in the initial coherent sub‐ps regime, where photon and exciton wavefunctions are inextricably mixed. Hence the detailed process of coherent organic exciton‐polariton transport and, in particular, the role of dark states has remained poorly understood. Here, femtosecond transient absorption microscopy is used to directly image coherent polariton motion in microcavities of varying quality factor. The transport is found to be well‐described by a model of band‐like propagation of an initially Gaussian distribution of exciton‐polaritons in real space. The velocity of the polaritons reaches values of ≈ 0.65 × 106 m s−1, substantially lower than expected from the polariton dispersion. Further, it is found that the velocity is proportional to the quality factor of the microcavity. This unexpected link between the quality‐factor and polariton velocity is suggested to be a result of varying admixing between delocalized dark and polariton states.

Nonequilibrium Carrier Transport in Quantum Dot Heterostructures.

Understanding carrier dynamics and transport in quantum dot based heterostructures is crucial for unlocking their full potential for optoelectronic applications. Here we report the direct visualization of carrier propagation in PbS CQD solids and quantum-dot-in-perovskite heterostructures using femtosecond transient absorption microscopy. We reveal three distinct transport regimes: an initial superdiffusive transport persisting over hundreds of femtoseconds, an Auger-assisted subdiffusive transport before thermal equilibrium is achieved, and a final hopping regime. We demonstrate that the superdiffusive transport lengths correlate strongly with the degree of energetic disorder and carrier delocalization. By tailoring the perovskite content in heterostructures, we obtained a superdiffusive transport length exceeding 90 nm at room temperature and an equivalent diffusivity of up to 106 cm2 s-1, which is 4 orders of magnitude higher than the steady-state values. These findings introduce promising strategies to harness nonequilibrium transport phenomena for more efficient optoelectronic devices.

Singlet Fission in Terrylenediimide Single Crystals: Competition between Biexciton Annihilation and Free Triplet Exciton Formation

Understanding singlet fission (SF) is an important strategy for extending the power conversion efficiency of next-generation solar cells beyond the Shockley–Queisser limit. Thus far, most studies of SF have focused on polycrystalline films, whose heterogeneity often makes it difficult to probe the electronic states involved in the formation of the correlated triplet biexciton state, 1(T1T1), and its decorrelation into free triplet excitons. Polarization-resolved, femtosecond transient absorption microscopy of a 1,6,9,14-tetraphenylterrylene-3,4:11,13-bis(dicarboximide) (Ph4TDI) single crystal reveals the formation of transient spectra in <200 fs having features characteristic of 1(T1T1), 1(S1S0), and Ph4TDI•+-Ph4TDI•– charge-transfer (CT) states. This indicates that either an ultrafast equilibrium between these states occurs or that the initially formed biexciton state is a mixture of these states. This spectrum evolves in time to give the Tn ← T1 spectrum of the free triplet excitons. We show further that this initially formed state has its optical transition polarized nearly perpendicular to that of the Tn ← T1 transition in the free triplet excitons. This indicates that the observed free triplet excitons have migrated from the π-stacked Ph4TDI columns where the 1(T1T1) state is produced to neighboring, nearly orthogonal π-stacked Ph4TDI columns, resulting in a weaker electronic interaction between the free triplet excitons essential to extending their lifetimes. However, the mobility of the 1(T1T1) state in the Ph4TDI π-stacking direction results in significant annihilation of biexciton pairs limiting the yield of free triplet excitons to about 60%.

Dichroic Photoelasticity in Black Phosphorus Revealed by Ultrafast Coherent Phonon Dynamics.

Coherent longitudinal lattice vibrations of black phosphorus provide unique access to the out-of-plane strain coupled in-plane optical properties. In this work, polarization-resolved femtosecond transient absorption microscopy is applied to study the anisotropic coherent phonon responses. Multiorder phonon harmonics were observed with thickness dependence well explained by the linear chain model, allowing rapid optical mapping of phonon frequency distributions. More interestingly, exotic coherent phonon oscillations occourred with a π-phase jump between the armchair and zigzag polarizations, which reveals opposite signs of photoelasticity under the longitudinal strain. Specifically, compressive strain reduces the imaginary refractive index in the armchair polarization but increases the real refractive index in the zigzag polarization, as confirmed by the ab initio calculations and thin film model. These fundamental properties of black phosphorus hold potential for applications in ultrafast and polarization-sensitive photoacoustic/photoelastic modulators.

Angle-tunable intersubband photoabsorption and enhanced photobleaching in twisted bilayer graphene

Van der Waals heterostructures obtained by artificially stacking two-dimensional crystals represent the frontier of material engineering, demonstrating properties superior to those of the starting materials. Fine control of the interlayer twist angle has opened new possibilities for tailoring the optoelectronic properties of these heterostructures. Twisted bilayer graphene with a strong interlayer coupling is a prototype of twisted heterostructure inheriting the intriguing electronic properties of graphene. Understanding the effects of the twist angle on its out-of-equilibrium optical properties is crucial for devising optoelectronic applications. With this aim, we here combine excitation-resolved hot photoluminescence with femtosecond transient absorption microscopy. The hot charge carrier distribution induced by photo-excitation results in peaked absorption bleaching and photo-induced absorption bands, both with pronounced twist angle dependence. Theoretical simulations of the electronic band structure and of the joint density of states enable to assign these bands to the blocking of interband transitions at the van Hove singularities and to photo-activated intersubband transitions. The tens of picoseconds relaxation dynamics of the observed bands is attributed to the angle-dependence of electron and phonon heat capacities of twisted bilayer graphene.

Ultrafast photo-driven charge transfer exciton dynamics in mixed-stack pyrene-perylenediimide single co-crystals

Femtosecond transient absorption microscopy of organic donor–acceptor single co-crystals shows that photo-initiated charge transfer exciton diffusion as well as charge recombination rates depend critically on crystal morphology.

Enhanced Ballistic Transport of Charge Carriers in Alloyed and K-Passivated Alloyed Perovskite Thin Films.

Hybrid organic–inorganic perovskites show remarkable charge transport properties despite their deposition via low-temperature solution phase methods. It has recently been shown that this includes the ballistic transport of charges following photoexcitation, with ballistic transport lengths as large as 150 nm measured in MAPI3 films, which is almost twice the value reported for GaAs. Here we explore the ballistic transport regime in high-performance triple-cation and K-passivated triple-cation perovskite films, using femtosecond transient absorption microscopy, which allows us to image carrier motion with 10 fs temporal resolution and 10 nm spatial precision. We observe ballistic transport lengths of 160 and 220 nm in triple-cation and K-passivated triple-cation perovskite films, respectively. We propose that the ballistic transport is limited by nanoscale trap clusters at grain boundaries and interfaces, which can be passivated via chemical treatments to enhance the ballistic transport length, which implies that further enhancements are possible as passivation methods are improved.

Connecting Femtosecond Transient Absorption Microscopy with Spatially Coregistered Time Averaged Optical Imaging Modalities.

Multimodal all-optical imaging involving coregistered femtosecond transient absorption microscopy (TAM), time-integrated photoluminescence (PL), and steady-state modalities such as confocal reflectance and transmission offers an appealing approach to gain a comprehensive understanding of complex electronic excited-state phenomena in spatially heterogeneous systems. A unique combination of these modalities allows us to unravel not only the competing electronic excited-state dynamical processes but also the underlying morphological information with simultaneous high temporal and spatial resolution. However, correlating the various images obtained from time-resolved and time-independent modalities is generally nontrivial and particularly challenging when the electronic dynamics under study evolve in both time and space. Here, we demonstrate a new approach for rationally correlating time-resolved microscopy with coregistered time-integrated or steady-state modalities. Specifically, our approach involves an extended global lifetime analysis of the time-resolved microscopic data set to separate distinct dynamical processes taking place on commensurate time scales, and the resulting decay-associated amplitude maps (DAAMs) were applied to explore correlations with the images acquired using time-independent modalities. The feasibility of our approach was validated through analyzing a multimodal data set acquired from a thin film of chloride-containing mixed lead halide perovskites (CH3NH3PbI3-xClx) using femtosecond transient absorption, time-integrated PL, and confocal reflectance microscopies. Analysis of the results obtained enable us to gain new insight into the complex ultrafast relaxation dynamics in this highly heterogeneous system.

Femtosecond Transient Absorption Microscopy of Singlet Exciton Motion in Side-Chain Engineered Perylene-Diimide Thin Films.

We present a statistical analysis of femtosecond transient absorption microscopy applied to four different organic semiconductor thin films based on perylene-diimide (PDI). By achieving a temporal resolution of 12 fs with simultaneous sub-10 nm spatial precision, we directly probe the underlying exciton transport characteristics within 3 ps after photoexcitation free of model assumptions. Our study reveals sub-picosecond coherent exciton transport (12–45 cm2 s–1) followed by a diffusive phase of exciton transport (3–17 cm2 s–1). A comparison between the different films suggests that the exciton transport in the studied materials is intricately linked to their nanoscale morphology, with PDI films that form large crystalline domains exhibiting the largest diffusion coefficients and transport lengths. Our study demonstrates the advantages of directly studying ultrafast transport properties at the nanometer length scale and highlights the need to examine nanoscale morphology when investigating exciton transport in organic as well as inorganic semiconductors.

Visualizing the impact of chloride addition on the microscopic carrier dynamics of MAPbI3 thin films using femtosecond transient absorption microscopy.

The spatial heterogeneity of carrier dynamics in mixed halide perovskite CH3NH3PbI3-xClx thin films with a range of different chloride additions is mapped using femtosecond transient absorption microscopy (TAM). The comparison of TAM images of fibrous and granular polycrystalline CH3NH3PbI3-xClx films indicates that the impact of chloride addition on the local heterogeneity of carrier dynamics is highly dependent on the film preparation method and the resulting morphology. In addition to signals of pristine CH3NH3PbI3, CH3NH3PbI3-xClx films with a fibrous structure show long-lived excited state absorption (ESA) signals in localized, microscopic regions. The ESA signal exhibits transient absorption with a rise time of about 5 ps after the excitation pulse, indicating that these distinct micrograins have preferential carrier trapping properties. The chemical composition of these micrograins does not differ detectably from their surroundings. In contrast, in CH3NH3PbI3-xClx films with a granular structure, Cl addition does not seem to affect the charge carrier dynamics. These results provide insight into the localized effects of halide mixing and on the resulting photophysical properties of mixed halide perovskite materials on the micrometer length scale.

Long-range ballistic propagation of carriers in methylammonium lead iodide perovskite thin films

The performance of semiconductor devices is fundamentally governed by charge-carrier dynamics within the active materials1–6. Although advances have been made towards understanding these dynamics under steady-state conditions, the importance of non-equilibrium phenomena and their effect on device performances remains elusive7,8. In fact, the ballistic propagation of carriers is generally considered to not contribute to the mechanism of photovoltaics (PVs) and light-emitting diodes, as scattering rapidly disrupts such processes after carrier generation via photon absorption or electric injection9. Here we characterize the spatiotemporal dynamics of carriers immediately after photon absorption in methylammonium lead iodide perovskite films using femtosecond transient absorption microscopy (fs-TAM) with a 10 fs temporal resolution and 10 nm spatial precision. We found that non-equilibrium carriers propagate ballistically over 150 nm within 20 fs of photon absorption. Our results suggest that in a typical perovskite PV device operating under standard conditions, a large fraction of carriers can reach the charge collection layers ballistically. The ballistic transport distance appears to be limited by energetic disorder within the materials, probably due to disorder-induced scattering. This provides a direct route towards optimization of the ballistic transport distance via improvements in materials and by minimizing the energetic disorder. Our observations reveal an unexplored regime of carrier transport in perovskites, which could have important consequences for device performance. Charge-carrier dynamics are fundamental to the operation and performance of semiconductor devices. In methylammonium lead iodide perovskites, carriers in the non-equilibrium regime after excitation propagate ballistically over 150 nm within 20 fs.

Inhomogeneous photocarrier dynamics and transport in monolayer MoS2 by ultrafast microscopy

Monolayer MoS2 as a member of two-dimensional transition metal dichalcogenides (TMDs) has attracted considerable attention due to its superior optoelectronic properties. Understanding the photocarrier dynamics and transport in these two dimensional systems is beneficial for applications from photovoltaics to sensing. However, various structural defects strongly impact the dynamics and transport of photocarriers. Especially there lacks a precise measuring and understanding of photocarrier transport in TMDs. Here, femtosecond transient absorption spectroscopy and microscopy were employed to study the photocarrier dynamics and transport in monolayer MoS2. Defect correlated photocarrier dynamics are observed across the monolayer MoS2 where exciton formation and nonradiative recombination are the two dominant decay processes. To the best of our knowledge, we report two distinct photocarrier transport regimes in MoS2 for the first time with diffusion coefficients of cm2 s−1 and cm2 s−1, by taking advantages of ultrafast microscopy with ∼20 nm spatial precision and ∼200 fs temporal resolution. These two regimes are ascribed to fast hot photocarrier diffusion and slow phonon-limited thermal diffusion, respectively. The results indicate that the initial fast photocarrier transport is less dependent on structural defects compared to photocarrier relaxation dynamics which may be useful for hot photocarrier extraction applications.

On the origin of spatially dependent electronic excited-state dynamics in mixed hybrid perovskite thin films

The fundamental photophysics underlying the remarkable performance of organic-inorganic hybrid perovskites in optoelectronic device applications has been increasingly studied using complementary spectroscopic techniques. However, the spatially heterogeneous polycrystalline morphology of the solution-processed thin films is often overlooked in conventional ensemble measurements and therefore the reported results are averaged over hundreds or even thousands of nano- and micro-crystalline grains. Here, we apply femtosecond transient absorption microscopy to spatially and temporally probe ultrafast electronic excited-state dynamics in chloride containing mixed lead halide perovskite (CH3NH3PbI3–xClx) thin films. We found that the electronic excited-state relaxation kinetics are extremely sensitive to the spatial location probed, which was manifested by position-dependent transient absorption signal amplitude and decay behaviour, along with an obvious rise component at some positions. The analysis of transient absorption kinetics acquired at several distinct spatial positions enabled us to identify Auger recombination as the dominant mechanism underlying the initial portions of the spatially dependent dynamics with variable rate constants. The different rates observed suggest occurrence of distinct local electronic structures and variable contributions from impurities/defects and phonons in this nonlinear dynamical process.