Pulsed Laser-Bleaching Semiconductor and Photodetector.

Pulsed lasers alter the optical properties of semiconductors and affect the photoelectric function of the photodetectors significantly, resulting in transient changes known as bleaching. Bleaching has a profound impact on the control and interference of photodetector applications. Experiments using pump-probe techniques have made significant contributions to understanding ultrafast carrier dynamics. However, there are few theoretical studies to the best of our knowledge. Here, carrier dynamic models for semiconductors and photodetectors are established, respectively, employing the rectified carrier drift-diffusion model. The pulsed laser bleaching effect on seven types of semiconductors and photodetectors from visible to long-wave infrared is demonstrated. Additionally, a continuous bleaching method is provided, and the finite-difference time-domain (FDTD) method is used to solve carrier dynamic theory models. Laser parameters for continuous bleaching of semiconductors and photodetectors are calculated. The proposed bleaching model and achieved laser parameters for continuous bleaching are essential for several applications using semiconductor devices, such as infrared detection, biological imaging, and sensing.

Momentum-Space Observation of Optically Excited Nonthermal Electrons in Graphene with Persistent Pseudospin Polarization.

The unique optical properties of graphene, with broadband absorption and ultrafast response, make it a critical component of optoelectronic and spintronic devices. Using time-resolved momentum microscopy with high data rate and high dynamic range, we report momentum-space measurements of electrons promoted to the graphene conduction band with visible light and their subsequent relaxation. We observe a pronounced nonthermal distribution of nascent photoexcited electrons with lattice pseudospin polarization in remarkable agreement with results of simple tight-binding theory. By varying the excitation fluence, we vary the relative importance of electron-electron vs electron-phonon scattering in the relaxation of the initial distribution. Increasing the excitation fluence results in increased noncollinear electron-electron scattering and reduced pseudospin polarization, although up-scattered electrons retain a degree of polarization. These detailed momentum-resolved electron dynamics in graphene demonstrate the capabilities of high-performance time-resolved momentum microscopy in the study of 2D materials and can inform the design of graphene devices.

Observation of a Picosecond Light-Induced Spin Transition in Polymeric Nanorods.

Spin transition (ST) materials are attractive for developing photoswitchable devices, but their slow material transformations limit device applications. Size reduction could enable faster switching, but the photoinduced dynamics at the nanoscale remains poorly understood. Here, we report a femtosecond optical pump multimodal X-ray probe study of polymeric nanorods. Simultaneously tracking the ST order parameter with X-ray emission spectroscopy and structure with X-ray diffraction, we observe photodoping of the low-spin-lattice within ∼150 fs. Above a ∼16% photodoping threshold, the transition to the high-spin phase occurs following an incubation period assigned to vibrational energy redistribution within the nanorods activating the molecular spin switching. Above ∼60% photodoping, the incubation period disappears, and the transition completes within ∼50 ps, preceded by the elastic nanorod expansion in response to the photodoping. These results support the feasibility of ST material-based GHz optical switching applications.

Terahertz wave radiation simulation in the Fe thin film.

Femtosecond laser (FL) induced terahertz (THz) source is a new type of THz source based on injecting FL beams into ferromagnetic thin films by nonlinear effects to generate THz wave. It has a wider bandwidth compared to the traditional THz source, which provides higher flexibility and tunability in the application. In this paper, the three-temperature model and the stochastic Landau Lifshitz Gilbert equation at the atomic level are applied to simulate THz wave generation in Fe thin film induced by FL. Simulation results show that under a FL irradiance of 2 J m-2, the maximum demagnetization of the Fe thin film reaches 8.7%. The electromagnetic waves generated completely cover the THz band (0.1-10 THz), which fully satisfied the application requirements of the THz technology, verifying the feasibility of FL inducing the Fe thin film as a THz source. However, when the Fe thin film is overheated, it will be difficult for FL to excite valuable THz waves. Therefore, additional cooling devices are needed to keep the THz source in a workable temperature state, or to use ferromagnetic materials with magnetic moments that can quickly recover to saturation.

A Photoswitchable Metallocycle Based on Azobenzene: Synthesis, Characterization, and Ultrafast Dynamics.

The novel photoswitchable ligand 3,3'-Azobenz(metPA)2 (1) is used to prepare a [Cu2(1)2](BF4)2 metallocycle (2), whose photoisomerization was characterized using static and time-resolved spectroscopic methods. Optical studies demonstrate the highly quantitative and reproducible photoinduced cyclic E/Z switching without decay of the complex. Accordingly and best to our knowledge, [Cu2(1)2](BF4)2 constitutes the first reversibly photoswitchable (3d)-metallocycle based on azobenzene. The photoinduced multiexponential dynamics in the sub-picosecond to few picosecond time domain of 1 and 2 have been assessed. These ultrafast dynamics as well as the yield of the respective photostationary state (PSSZ = 65 %) resemble the behavior of archetypical azobenzene. Also, the innovative pump-probe laser technique of gas phase transient photodissociation (τ-PD) in a mass spectrometric ion trap was used to determine the intrinsic relaxation dynamics for the isolated complex. These results are consistent with the results from femtosecond UV/Vis transient absorption (fs-TA) in solution, emphasizing the azobenzene-like dynamics of 2. This unique combination of fs-TA and τ-PD enables valuable insights into the prevailing interplay of dynamics and solvation. Both analyses (in solution and gas phase) and quantum chemical calculations reveal a negligible effect of the metal coordination on the switching mechanism and electronic pathway, which suggests a non-cooperative isomerization process.

Room Temperature Phosphorescence in Crystalline Iodinated Eumelanin Monomer.

We report the room temperature phosphorescence upon iodination on a crystalline eumelanin monomer with shielded hydroxyl moieties, ethyl 5,6-dimethoxyindole-2-carboxylate (DMICE). Ultrafast intersystem crossing (ISC) is observed in the iodinated (IDMICE) as well as brominated (BDMICE) analogues of the eumelanin monomer derivative in solution. The triplet quantum yields (φT) and intersystem crossing rates (kISC) of the halogenated eumelanin derivatives are φ T B D M I C E ${{\phi{} }_{T}^{BDMICE}}$ =25.4±1.1 %; k I S C B D M I C E ${{k}_{ISC}^{BDMICE}}$ =1.95×109 s-1 and φ T I D M I C E ${{\phi{} }_{T}^{IDMICE}}$ =59.1±1.6 %; k I S C I D M I C E = ${{k}_{ISC}^{IDMICE}=}$ 1.36×1010 s-1, as monitored using transient absorption spectroscopy. Theoretical calculations based on nuclear ensemble method reveal that computed kISC and spin-orbit coupling matrix elements for eumelanin derivatives are larger for IDMICE relative to BDMICE. The halogen and π-π interactions, with distinct excitonic coupling and higher ISC rate promote phosphorescence in IDMICE molecular crystals. Accessing triplet excited states and resultant photoluminescence through structural modification of eumelanin scaffolds paves way for exploring the versatility of eumelanin-inspired molecules as bio-functional materials.

Development of the multiplex imaging chamber at PAL-XFEL.

Various X-ray techniques are employed to investigate specimens in diverse fields. Generally, scattering and absorption/emission processes occur due to the interaction of X-rays with matter. The output signals from these processes contain structural information and the electronic structure of specimens, respectively. The combination of complementary X-ray techniques improves the understanding of complex systems holistically. In this context, we introduce a multiplex imaging instrument that can collect small-/wide-angle X-ray diffraction and X-ray emission spectra simultaneously to investigate morphological information with nanoscale resolution, crystal arrangement at the atomic scale and the electronic structure of specimens.

Ultrafast Exciton Dynamics in the Atomically Thin van der Waals Magnet CrSBr.

Among atomically thin semiconductors, CrSBr stands out as both its bulk and monolayer forms host tightly bound, quasi-one-dimensional excitons in a magnetic environment. Despite its pivotal importance for solid-state research, the exciton lifetime has remained unknown. While terahertz polarization probing can directly trace all excitons, independently of interband selection rules, the corresponding large far-field foci substantially exceed the lateral sample dimensions. Here, we combine terahertz polarization spectroscopy with near-field microscopy to reveal a femtosecond decay of paramagnetic excitons in a monolayer of CrSBr, which is 30 times shorter than the bulk lifetime. We unveil low-energy fingerprints of bound and unbound electron-hole pairs in bulk CrSBr and extract the nonequilibrium dielectric function of the monolayer in a model-free manner. Our results demonstrate the first direct access to the ultrafast dielectric response of quasi-one-dimensional excitons in CrSBr, potentially advancing the development of quantum devices based on ultrathin van der Waals magnets.

Probing the Molecular Structure and Dynamics of Membrane-Bound Proteins during Misfolding Processes by Sum-Frequency Generation Vibrational Spectroscopy.

Protein misfolding and amyloid formation are implicated in the protein dysfunction, but the underlying mechanism remains to be clarified due to the lack of effective tools for detecting the transient intermediates. Sum frequency generation vibrational spectroscopy (SFG-VS) has emerged as a powerful tool for identifying the structure and dynamics of proteins at the interfaces. In this review, we summarize recent SFG-VS studies on the structure and dynamics of membrane-bound proteins during misfolding processes. This paper first introduces the methods for determining the secondary structure of interfacial proteins: combining chiral and achiral spectra of amide A and amide I bands and combining amide I, amide II, and amide III spectral features. To demonstrate the ability of SFG-VS in investigating the interfacial protein misfolding and amyloid formation, studies on the interactions between different peptides/proteins (islet amyloid polypeptide, amyloid ß, prion protein, fused in sarcoma protein, hen egg-white lysozyme, fusing fusion peptide, class I hydrophobin SC3 and class II hydrophobin HFBI) and surfaces such as lipid membranes are discussed. These molecular-level studies revealed that SFG-VS can provide a unique understanding of the mechanism of interfacial protein misfolding and amyloid formation in real time, in situ and without any exogenous labeling.

Near-IR Capturing N-Methylbenzene Sulfonamide-Phenothiazine Incorporating Strong Electron Acceptor Push-Pull Systems: Photochemical Ultrafast Carrier Dynamics.

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low-lying broad absorption band extended towards the near-infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry-optimized structures further support accessing donor-acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.

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.

Anomalous Hall Transport by Optically Injected Isospin Degree of Freedom in Dirac Semimetal Thin Film.

Chirality of massless fermions emerging in condensed matter is a key to understand their characteristic behavior as well as to exploit their functionality. However, the chiral nature of massless fermions in Dirac semimetals has remained elusive, due to equivalent occupation of carriers with the opposite chirality in thermal equilibrium. Here, we show that the isospin degree of freedom, which labels the chirality of massless carriers from a crystallographic point of view, can be injected by circularly polarized light. Terahertz Faraday rotation spectroscopy successfully detects the anomalous Hall conductivity by a light-induced isospin polarization in a three-dimensional Dirac semimetal, Cd3As2. Spectral analysis of the Hall conductivity reveals a long scattering time and a long decay time, which are characteristic of the isospin. The long-lived, robust, and reversible character of the isospin promises a potential application of Dirac semimetals in future information technology.

Imaging Ultrafast Dynamics of Pressure-Driven Phase Transitions in Black Phosphorus and Anomalous Coherent Phonon Softening.

Applying high pressure to effectively modulate the electronic and lattice structures of materials could unravel various physical properties associated with phase transitions. In this work, high-pressure-compatible femtosecond pump-probe microscopy was constructed to study the pressure-dependent ultrafast dynamics in black phosphorus (BP) thin films. We observed pressure-driven evolution of the electronic topological transition and three structural phases as the pressure reached ∼22 GPa, which could be clearly differentiated in the transient absorption images containing spatially resolved ultrafast carrier and coherent phonon dynamics. Surprisingly, an anomalous coherent acoustic phonon mode with pressure softening behavior was observed within the range of ∼3-8 GPa, showing distinct laser power and time dependences. Density functional theory calculations show that this mode, identified as the shear mode along the armchair orientation, gains significant electron-phonon coupling strength from out-of-plane compression that leads to decreased phonon frequency. Our results provide insights into the structure evolution of BP with pressure and hold potential for applications in microelectromechanical devices.

Transient Non-Collinear Magnetic State for All-Optical Magnetization Switching.

Resonant absorption of a photon by bound electrons in a solid can promote an electron to another orbital state or transfer it to a neighboring atomic site. Such a transition in a magnetically ordered material could affect the magnetic order. While this process is an obvious road map for optical control of magnetization, experimental demonstration of such a process remains challenging. Exciting a significant fraction of magnetic ions requires a very intense incoming light beam, as orbital resonances are often weak compared to above-band-gap excitations. In the latter case, a sizeable reduction of the magnetization occurs as the absorbed energy increases the spin temperature, masking the non-thermal optical effects. Here, using ultrafast X-ray spectroscopy, this work is able to resolve changes in the magnetization state induced by resonant absorption of infrared photons in Co-doped yttrium iron garnet, with negligible thermal effects. This work finds that the optical excitation of the Co ions affects the two distinct magnetic Fe sublattices differently, resulting in a transient non-collinear magnetic state. The present results indicate that the all-optical magnetization switching (AOS) most likely occurs due to the creation of a transient, non-collinear magnetic state followed by coherent spin rotations of the Fe moments.

Circular dichroism in Floquet Chern insulator via high-order harmonics spectroscopy.

High-order harmonics (HOHs) spectroscopy is attracting the attention of the condensed matter community, mostly because the HOHs spectrum encode the material property. Topological materials are of interest for both basic research and advanced technologies because of their robust properties against dissipation and perturbations. Floquet engineering technique have been demonstrated to be a unique tool to manipulate topological phase. In this paper, we apply HOH spectroscopy to characterize the Floquet state via the circular dichroism (CD). We find that the CD of the co-rotating harmonics is sensitive to Floquet topological states.

Unraveling the Ultrafast Coherent Dynamics of Exciton Polariton Propagation at Room Temperature.

Exciton polaritons are widely considered as promising platforms for developing room-temperature polaritonic devices, owing to the high-speed propagation and nonlinear interactions. However, it remains challenging to explore the dynamics of exciton polaritons specifically at room temperature, where the lifetime could be as small as a few picoseconds and the prevailing time-averaged measurement cannot give access to the true nature of it. Herein, by using the time-resolved photoluminescence, we have successfully traced the ultrafast coherent dynamics of a moving exciton polariton condensate in a one-dimensional perovskite microcavity. The propagation speed is directly measured to be ∼12.2 ± 0.8 µm/ps. Moreover, we have developed a time-resolved Michelson interferometry to quantify the time-dependent phase coherence, which reveals that the actual coherence time of exciton polaritons could be much longer (nearly 100%) than what was believed before. Our work sheds new light on the ultrafast coherent propagation of exciton polaritons at room temperature.

Ultrafast Switching of Interfacial Thermal Conductance.

Dynamical control of thermal transport at the nanoscale provides a time-domain strategy for optimizing thermal management in nanoelectronics, magnetic devices, and thermoelectric devices. However, the rate of change available for thermal switches and regulators is limited to millisecond time scales, calling for a faster modulation speed. Here, time-resolved X-ray diffraction measurements and thermal transport modeling reveal an ultrafast modulation of the interfacial thermal conductance of an FeRh/MgO heterostructure as a result of a structural phase transition driven by optical excitation. Within 90 ps after optical excitation, the interfacial thermal conductance is reduced by a factor of 5 and lasts for a few nanoseconds, in comparison to the value at the equilibrium FeRh/MgO interface. The experimental results combined with thermal transport calculations suggest that the reduced interfacial thermal conductance results from enhanced phonon scattering at the interface where the lattice experiences transient in-plane biaxial stress due to the structural phase transition of FeRh. Our results suggest that optically driven phase transitions can be utilized for ultrafast nanoscale thermal switches for device application.

Vibrational Dichroism of Chiral Valley Phonons.

Valley degrees of freedom in transition metal dichalcogenides thoroughly influence electron-phonon coupling and its nonequilibrium dynamics. We conducted a first-principles study of the quantum kinetics of chiral phonons following valley-selective carrier excitation with circularly polarized light. Our numerical investigations treat the ultrafast dynamics of electrons and phonons on equal footing within a parameter-free ab initio framework. We report the emergence of valley-polarized phonon populations in monolayer MoS2 that can be selectively excited at either the K or K' valleys depending on the light helicity. The resulting vibrational state is characterized by a distinctive chirality, which lifts time-reversal symmetry of the lattice on transient time scales. We show that chiral valley phonons can further lead to fingerprints of vibrational dichroism detectable by ultrafast diffuse scattering and persist beyond 10 ps. The valley polarization of nonequilibrium phonon populations could be exploited as an information carrier, thereby extending the paradigm of valleytronics to the domain of vibrational excitations.

Ultrafast Dynamics of Extraordinary Optical Transmission through Two-Slit Plasmonic Antenna.

We have theoretically investigated the spatial-temporal dynamics of extraordinary optical transmission (EOT) through a two-slit plasmonic antenna under femtosecond laser dual-beam irradiation. The dynamic interference of the crossed femtosecond laser dual-beam with the transiently excited surface plasmon polariton waves are proposed to characterize the particular spatial-temporal evolutions of EOT. It is revealed that the dynamic EOT can be flexibly switched with tunable symmetry through the respective slit of a two-slit plasmonic antenna by manipulating the phase correlation of the crossed femtosecond laser dual-beam. This is explained as tunable interference dynamics by phase control of surface plasmon polariton waves, allowing the dynamic modulation of EOT at optimized oblique incidences of dual-beams. Furthermore, we have obtained the unobserved traits of symmetry-broken transient spectra of EOT from the respective up- and down-slit of the antenna under crossed femtosecond laser dual-beam irradiation. This study can provide fundamental insights into the ultrafast dynamics of EOT in two-slit plasmonic antennas, which can be helpful to advance a wide range of applications, such as ultrafast plasmonic switch, ultrahigh resolution imaging, the transient amplification of non-linear effects, etc.

Microscopic investigation of intrinsic defects in CVD grown MoS2monolayers.

Defects in two-dimensional (2D) transition metal dichalcogenides (TMDs) greatly influence their electronic and optical properties by introducing localized in-gap states. Using different non-invasive techniques, we have investigated the spatial distribution of intrinsic defects in as-grown chemical vapor deposition (CVD) MoS2monolayers and correlated the results with the growth temperature of the sample. We have shown that by increasing the CVD growth temperature the concentration of defects decreases and their spatial distribution and type change, influencing the sample's electronic and optical properties.