Electron Dynamics Research Articles

Multiphotonic Ablation and Electro-Capacitive Effects Exhibited by Candida albicans Biofilms.

This work reports the modification in the homogeneity of ablation effects with the assistance of nonlinear optical phenomena exhibited by C. albicans ATCC 10231, forming a biofilm. Equivalent optical energies with different levels of intensity were irradiated in comparative samples, and significant changes were observed. Nanosecond pulses provided by an Nd:YAG laser system at a 532 nm wavelength in a single-beam experiment were employed to explore the photodamage and the nonlinear optical transmittance. A nonlinear optical absorption coefficient -2 × 10-6 cm/W was measured in the samples studied. It is reported that multiphotonic interactions can promote more symmetric optical damage derived by faster changes in the evolution of fractional photoenergy transference. The electrochemical response of the sample was studied to further investigate the electronic dynamics dependent on electrical frequency, and an electro-capacitive behavior in the sample was identified. Fractional differential calculations were proposed to describe the thermal transport induced by nanosecond pulses in the fungi media. These results highlight the nonlinear optical effects to be considered as a base for developing photothermally activated phototechnology and high-precision photodamage in biological systems.

Nonadiabatic Charge Transfer within Photoexcited Nickel Porphyrins.

Metalloporphyrins with open d-shell ions can drive biochemical energy cycles. However, their utilization in photoconversion is hampered by rapid deactivation. Mapping the relaxation pathways is essential for elaborating strategies that can favorably alter the charge dynamics through chemical design and photoexcitation conditions. Here, we combine transient optical absorption spectroscopy and transient X-ray emission spectroscopy with femtosecond resolution to probe directly the coupled electronic and spin dynamics within a photoexcited nickel porphyrin in solution. Measurements and calculations reveal that a state with charge-transfer character mediates the formation of the thermalized excited state, thereby advancing the description of the photocycle for this important representative molecule. More generally, establishing that intramolecular charge-transfer steps play a role in the photoinduced dynamics of metalloporphyrins with open d-shell sets a conceptual ground for their development as building blocks capable of boosting nonadiabatic photoconversion in functional architectures through "hot" charge transfer down to the attosecond time scale.

Coherent phonon and unconventional carriers in the magnetic kagome metal Fe3Sn2

Temperature- and fluence-dependent carrier dynamics of the magnetic kagome metal Fe3Sn2 were studied using the ultrafast optical pump-probe technique. Two carrier relaxation processes and a laser-induced coherent optical phonon were observed. We ascribe the shorter relaxation (~1 ps) to hot electrons transferring their energy to the crystal lattice via electron–phonon scattering. The second relaxation (~30 ps), on the other hand, cannot be explained as a conventional process, and we attributed it to the unconventional (localized) carriers in the material. The observed coherent oscillation is assigned to be a totally symmetric A1g optical phonon dominated by Sn displacements out of the kagome planes and possesses a prominently large amplitude, on the order of 10−3, comparable to the maximum of the reflectivity change (ΔR/R). This amplitude is similar to what has been observed for coherent phonons in charge-density-wave (CDW) systems, although no signs of such instability were hitherto reported in Fe3Sn2. Our results suggest an unexpected connection between Fe3Sn2 and kagome metals with CDW instabilities and a strong interplay between phonon and electron dynamics in this compound.

Statistical Properties of Pc4‐5 ULF Waves in Plasmaspheric Plumes

AbstractUltra‐low‐frequency (ULF) waves emerge as pivotal factors in elucidating the mechanisms that drive the intricate dynamics of radiation belt electrons within the plasmasphere and plasmaspheric plumes. Utilizing THEMIS data from September 2012 to September 2017, we conducted a comprehensive statistical analysis of Pc4‐5 ULF waves within and outside the plasmaspheric plume. Our findings reveal a distinctive dawn‐dusk asymmetry in occurrence rate and wave power of poloidal mode waves in the absence of the plume, resembling the toroidal mode asymmetry observed. Poloidal mode waves exhibit a higher likelihood of formation within the plume, while the toroidal mode waves show the opposite trend, contributing to the elevated dusk‐side occurrence rate of poloidal mode waves. Moreover, both wave modes within the plume demonstrate lower peak frequencies compared to waves outside the plume. The global distribution of wave power within the plume suggests higher power at noon than on the dusk side.

Two-Dimensional Molybdenum Boride (MBene) Mo4/3B2Tx with Broadband and Termination-Dependent Ultrafast Nonlinear Optical Response.

Two-dimensional molybdenum borides (MBenes) comprise a new class of 2D transition metal borides that exhibit potential photonics applications. Recently, the synthesis of individual single-layer Mo4/3B2Tx (T = O, F, OH) MBene sheets has been realized, which attracted considerable attention in optoelectronics. However, there is still a lack of understanding and regulation of the photophysical processes of Mo4/3B2Tx MBene. Here, we demonstrate that Mo4/3B2Tx MBene exhibits a surface termination-dependent electronic structure, carrier dynamics, and nonlinear optical response over a wide wavelength range (500-1550 nm). As prepared 2D Mo4/3B2F2 MBene possesses a semimetal material property that exhibits a shorter intraband scattering process (<100 ps) and a considerable nonlinear optical response at a broadband cover optical communication C band at 1550 nm. These thrilling results are confirmed theoretically and experimentally. The analysis of these results adds to the regulating and understanding of the basic photophysical processes, which is anticipated to be beneficial for the further design of MBene-based photonics and nanoelectronics devices.

UV-induced resonant excitations of electrons near the Brillouin zone boundary in solid high harmonic generation

Abstract We propose a novel mechanism to manipulate the electron dynamics at the boundary of the Brillouin zone (BZ) through resonant excitation induced by ultraviolet (UV) laser pulses in solid high harmonic generation (HHG). When adding weak UV pulses to a stronger mid-infrared (MIR) driving field, we show that UV pulses with specific wavelengths generate a resonant excitation zone around the Γ point in k − space, which facilitates the interband transition of electrons in the BZ boundary region. The scheme is not only significant for achieving higher harmonic yield, but also exhibits strong robustness at a relatively low MIR driving intensity due to the inherent manipulation of UV pulses for interband dynamics of BZ boundary electrons. The semiclassical four-step model is adopted to elucidate underlying physics.

Unraveling Electron Dynamics in p-type Indium Phosphide (100): A Time-Resolved Two-Photon Photoemission Study.

Renewable ("green") hydrogen production through direct photoelectrochemical (PEC) water splitting is a potential key contributor to the sustainable energy mix of the future. We investigate the potential of indium phosphide (InP) as a reference material among III-V semiconductors for PEC and photovoltaic (PV) applications. The p(2 × 2)/c(4 × 2)-reconstructed phosphorus-terminated p-doped InP(100) (P-rich p-InP) surface is the focus of our investigation. We employ time-resolved two-photon photoemission (tr-2PPE) spectroscopy to study electronic states near the band gap with an emphasis on normally unoccupied conduction band states that are inaccessible through conventional single-photon emission methods. The study shows the complexity of the p-InP electronic band structure and reveals the presence of at least nine distinct states between the valence band edge and vacuum energy, including a valence band state, a surface defect state pinning the Fermi level, six unoccupied surface resonances within the conduction band, as well as a cluster of states about 1.6 eV above the CBM, identified as a bulk-to-surface transition. Furthermore, we determined the decay constants of five of the conduction band states, enabling us to track electron relaxation through the bulk and surface conduction bands. This comprehensive understanding of the electron dynamics in p-InP(100) lays the foundation for further exploration and surface engineering to enhance the properties and applications of p-InP-based III-V-compounds for, e.g., efficient and cost-effective PEC hydrogen production and highly efficient PV cells.

Unveiling heterogeneity of hysteresis in perovskite thin films

The phenomenon of current–voltage hysteresis observed in perovskite-based optoelectronic devices is a critical issue that complicates the accurate assessment of device parameters, thereby impacting performance and applicability. Despite extensive research efforts aimed at deciphering the origins of hysteresis, its underlying causes remain a subject of considerable debate. By employing nanoscale investigations to elucidate the relationship between hysteresis and morphological characteristics, this study offers a detailed exploration of photocurrent–voltage hysteresis at the nanoscale within perovskite optoelectronic devices. Through the meticulous analysis of localized I–V curve arrays, our research identifies two principal hysteresis descriptors, uncovering a predominantly inverted hysteresis pattern in 87% of the locations examined. This pattern is primarily attributed to the energetic barrier encountered at the interface between the probe and the perovskite material. Our findings underscore the pronounced heterogeneity and grain-dependent variability inherent in hysteresis behavior, evidenced by an average Hysteresis Index value of 0.24. The investigation suggests that the localized hysteresis phenomena cannot be exclusively attributed to either photocharge collection processes or organic cation migration at grain boundaries. Instead, it appears significantly influenced by localized surface trap states, which play a pivotal role in modulating electron and hole current dynamics. By identifying the key factors contributing to hysteresis, such as localized surface trap states and their influence on electron and hole current dynamics, our findings pave the way for targeted strategies to mitigate these effects. This includes the development of novel materials and device architectures designed to minimize energy barriers and enhance charge carrier mobility, thereby improving device performance and longevity. This breakthrough in understanding the microscale mechanisms of hysteresis underscores the critical importance of surface/interface defect trap passivation in mitigating hysteretic effects, offering new pathways for enhancing the performance of perovskite solar cells.

Phototransformation of achiral metasurfaces into handedness-selectable transient chiral media

Chirality is a geometric property describing the lack of mirror symmetry. This unique feature enables photonic spin-selectivity in light-matter interaction, which is of great significance in stereochemistry, drug development, quantum optics, and optical polarization control. The versatile control of optical geometry renders optical metamaterials as an effective platform for engineered chiral properties at prescribed spectral regimes. Unfortunately, geometry-imposed restrictions only allow one circular polarization state of photons to effectively interact with chiral meta-structures. This limitation motivates the idea of discovering alternative techniques for dynamically reconfiguring the chiroptical responses of metamaterials in a fast and facile manner. Here, we demonstrate an approach that enables optical, sub-picosecond conversion of achiral meta-structures to transient chiral media in the visible regime with desired handedness upon the inhomogeneous generation of plasmonic hot electrons. As a proof of concept, we utilize linearly polarized laser pulse to demonstrate near-complete conversion of spin sensitivity in an achiral meta-platform-a functionality yet achieved in a non-mechanical fashion. Owing to the generation, diffusion, and relaxation dynamics of hot electrons, the demonstrated technique for all-optical creation of chirality is inherently fast, opening new avenues for ultrafast spectro-temporal construction of chiral platforms with on-demand spin-selectivity.

Determining Quasi-Equilibrium Electron and Hole Distributions of Plasmonic Photocatalysts Using Photomodulated X-ray Absorption Spectroscopy.

Most photocatalytic and photovoltaic devices operate under broadband, constant illumination. Electron and hole dynamics in these devices, however, are usually measured by using ultrafast pulsed lasers in a narrow wavelength range. In this work, we use excited-state X-ray theory originally developed for transient X-ray experiments to study steady-state photomodulated X-ray spectra. We use this method to attempt to extract electron and hole distributions from spectra collected at a nontime-resolved synchrotron beamline. A set of plasmonic metal core-shell nanoparticles is designed as the control experiment because they can systematically isolate photothermal, hot electron, and thermalized electron-hole pairs in a TiO2 shell. Steady-state changes in the Ti L2,3 edge are measured with and without continuous-wave illumination of the nanoparticle's localized surface plasmon resonance. The results suggest that within error the quasi-equilibrium carrier distribution can be determined even from relatively noisy data with mixed excited-state phenomena. Just as importantly, the theoretical analysis of noisy data is used to provide guidelines for the beamline development of photomodulated steady-state spectroscopy.

In-Operando Spatiotemporal Imaging of Coupled Film-Substrate Elastodynamics During an Insulator-to-Metal Transition.

The drive toward non-von Neumann device architectures has led to an intense focus on insulator-to-metal (IMT) and the converse metal-to-insulator (MIT) transitions. Studies of electric field-driven IMT in the prototypical VO2 thin-film channel devices are largely focused on the electrical and elastic responses of the films, but the response of the corresponding TiO2 substrate is often overlooked, since it is nominally expected to be electrically passive and elastically rigid. Here, in-operando spatiotemporal imaging of the coupled elastodynamics using X-ray diffraction microscopy of a VO2 film channel device on TiO2 substrate reveals two new surprises. First, the film channel bulges during the IMT, the opposite of the expected shrinking in the film undergoing IMT. Second, a microns thick proximal layer in the substrate also coherently bulges accompanying the IMT in the film, which is completely unexpected. Phase-field simulations of coupled IMT, oxygen vacancy electronic dynamics, and electronic carrier diffusion incorporating thermal and strain effects suggest that the observed elastodynamics can be explained by the known naturally occurring oxygen vacancies that rapidly ionize (and deionize) in concert with the IMT (MIT). Fast electrical-triggering of the IMT via ionizing defects and an active "IMT-like" substrate layer are critical aspects to consider in device applications.

Stability of long-sustained oscillations induced by electron tunneling

Self-oscillations are the result of an efficient mechanism generating periodic motion from a constant power source. In quantum devices, these oscillations may arise due to the interaction between single electron dynamics and mechanical motion. We show that, due to the complexity of this mechanism, these self-oscillations may irrupt, vanish, or exhibit a bistable behavior causing hysteresis cycles. We observe these hysteresis cycles and characterize the stability of different regimes in both single- and double-quantum-dot configurations. In particular cases, we find these oscillations stable for over 20 s, many orders of magnitude above electronic and mechanical characteristic timescales, revealing the robustness of the mechanism at play. Published by the American Physical Society 2024

Robust Isolated Attosecond Pulse Generation with Self-Compressed Subcycle Drivers from Hollow Capillary Fibers.

High-order harmonic generation (HHG) arising from the nonperturbative interaction of intense light fields with matter constitutes a well-established tabletop source of coherent extreme-ultraviolet and soft X-ray radiation, which is typically emitted as attosecond pulse trains. However, ultrafast applications increasingly demand isolated attosecond pulses (IAPs), which offer great promise for advancing precision control of electron dynamics. Yet, the direct generation of IAPs typically requires the synthesis of near-single-cycle intense driving fields, which is technologically challenging. In this work, we theoretically demonstrate a novel scheme for the straightforward and compact generation of IAPs from multicycle infrared drivers using hollow capillary fibers (HCFs). Starting from a standard, intense multicycle infrared pulse, a light transient is generated by extreme soliton self-compression in a HCF with decreasing pressure and is subsequently used to drive HHG in a gas target. Owing to the subcycle confinement of the HHG process, high-contrast IAPs are continuously emitted almost independently of the carrier-envelope phase (CEP) of the optimally self-compressed drivers. This results in a CEP-robust scheme which is also stable under macroscopic propagation of the high harmonics in a gas target. Our results open the way to a new generation of integrated all-fiber IAP sources, overcoming the efficiency limitations of usual gating techniques for multicycle drivers.

Three-dimensional ultrafast charge-density-wave dynamics in CuTe

Charge density waves (CDWs) involved with electronic and phononic subsystems simultaneously are a common quantum state in solid-state physics, especially in low-dimensional materials. However, CDW phase dynamics in various dimensions are yet to be studied, and their phase transition mechanism is currently moot. Here we show that using the distinct temperature evolution of orientation-dependent ultrafast electron and phonon dynamics, different dimensional CDW phases are verified in CuTe. When the temperature decreases, the shrinking of c-axis length accompanied with the appearance of interchain and interlayer interactions causes the quantum fluctuations (QF) of the CDW phase until 220 K. At T < 220 K, the CDWs on the different ab-planes are finally locked with each other in anti-phase to form a CDW phase along the c-axis. This study shows the dimension evolution of CDW phases in one CDW system and their stabilized mechanisms in different temperature regimes.

Electron-phonon coupling dictates electron mean free paths and negative thermal diffusion in metals

The spatiotemporal dynamics of the fundamental energy carriers in metals underpin the efficiency of a wide array of technologies. Although much progress in our understanding of the temporal response of electronic relaxation processes following an external field perturbation has been achieved, the spatial relaxation dynamics of electrons after excitation remains unclear. Here, we employ a scanning ultrafast microscopy with high spatial resolution to directly measure the mean free paths of electrons in different metals. We show that the strength of electron-phonon coupling not only dictates the mean free paths, but also controls a peculiar spatial shrinking of the electronic temperature profile immediately after the electrons have thermalized with the ‘colder’ lattice. More specifically, from our experimental tracking of the spatial relaxation profiles, a clear observation of an effective negative thermal diffusion is apparent for metals with weaker electron-phonon coupling, while for metals with stronger electron-phonon coupling, the negative thermal diffusion effect is not observable. Our spatiotemporal modeling based on the two-temperature approach provides evidence that although negative diffusion occurs universally for materials with two different species that have varying diffusivities and are thermodynamically coupled, effective negative diffusion is masked for cases with stronger coupling between the species.

Using ‘designer’ coherences to control electron transfer in a model bis(hydrazine) radical cation: can we still distinguish between direct and superexchange mechanisms?

We have simulated two mechanisms, direct and superexchange, for the electron transfer in a model Bis(hydrazine) Radical Cation, which consists of two hydrazine moieties coupled by a benzene ring. The computations, that are inspired by the attochemistry approach, focus on the electron dynamics arising from a coherent superposition of four cationic states. The electron dynamics, originating from a solution of the time dependent Schrödinger equation within the Ehrenfest method, is coupled to the relaxation of the nuclei. Both direct (ca. 15 fs dynamics) and superexchange (ca. 2 fs dynamics) mechanisms are observed and turn out to lie on a continuum depending on the strength of the coupling of the benzene bridge electron dynamics with the hydrazine chromophore dynamics. This contrasts with the chemical pathway approach where the direct mechanism is completely non-adiabatic via a conical intersection, while the superexchange mechanism involves an intermediate radical with the unpaired electron localized on the benzene ring. Thus, with the attochemistry-inspired electron dynamics approach, one can distinguish direct from superexchange mechanisms depending on the strength of the coupling of two types of electron dynamics: the slow hydrazine dynamics (ca. 15 fs) and the fast benzene linker dynamics (ca. 2 fs). In this model bis(hydrazine) radical cation, only when the intermediate coupler is in an anti-quinoid state, does one see the coupling of the bridge and hydrazine chromophore dynamics.

Revealing the Hole and Electron Transport Dynamics in the Working Devices for Efficient Semitransparent Perovskite Solar Cells

AbstractThe performance and stability of perovskite solar cells (PSCs) are dominated by the electron and hole transport dynamics, which are highly desired to be characterized in the working devices. Nevertheless, for the opaque PSCs, the hole transport layer (HTL) in n–i–p devices or the electron transport layer (ETL) in p–i–n devices are typically buried beneath the metal electrode, which makes it difficult to simultaneously characterize the charge transport dynamics from both sides of the working devices. In this work, for the first time, the charge transport dynamics of the working devices from both the front and rear side of semitransparent PSCs (ST‐PSCs) is characterized via femtosecond transient reflection spectroscopy (FS‐TRS). A significant enhancement of the hole transport and negligible change of the electron transport is observed when the perovskite/HTL interface is treated by 2‐chloro‐phenethylammonium iodide (2‐Cl‐PEAI). A champion power conversion efficiency (PCE) of 23.3% (certified 22.3%) is achieved, which is the highest certified PCE for ST‐PSCs up to date. The ST‐PSCs maintained more than 90% of its initial efficiency after 2000 h of maximum power point tracking (MPPT). Additionally, the ST‐PSCs are implemented in 4‐terminal (4‐T) perovskite/passivated emitter rear silicon cell (PERC), reaching a simulated output power of 30.8 mW cm−2.

High-Harmonic Generation Spectroscopy of Gas-Phase Bromoform.

High-Harmonic Generation (HHG) spectra of randomly aligned bromoform (CHBr3) molecules have been experimentally measured and theoretically simulated at various laser pulse intensities. From the experiments, we obtained a significant number of harmonics that goes beyond the cutoff limit predicted by the three-step model (3SM) with ionization from HOMO. To interpret the experiment, we resorted to real-time time-dependent configuration interaction with single excitations. We found that electronic bound states provide an appreciable contribution to the harmonics. More in detail, we analyzed the electron dynamics by decomposing the HHG signal in terms of single molecular-orbital contributions, to explain the appearance of harmonics around 20-30 eV beyond the expected cutoff due to HOMO. HHG spectra can be therefore explained by considering the contribution at high energy of HOMO-6 and HOMO-9, thus indicating a complex multiple-orbital strong-field dynamics. However, even though the presence of the bromoform cation should be not enough to produce such a signal, we could not exclude a priori that the origin of harmonics in the H29-H45 to be due to the cation, which has more energetic ionization channels.

The dynamical behavior of the capacitively coupled argon plasma driven by very high frequency

The dynamical behavior of the capacitively coupled Ar plasma driven by four frequencies (54, 80, 94 and 100[Formula: see text]MHz) at fixed pressure are simulated by the particle-in-cell/Monte-Carlo collisions (PIC/MCC) model based on the electromagnetic field. The magnetic field is generated by plasma current itself. The results show that the electron density, charge density, and electron temperature increase with the frequency increase when radio frequency (RF) power is 40[Formula: see text]W. The electron heating rate and argon ion heating rate near the sheath increase with the frequency increase. The high-energy electron density ([Formula: see text] [Formula: see text]eV) varies nonlinearly with the frequency increase. The high-energy electron density is highest at 80[Formula: see text]MHz among the four frequencies. The electron density, charge density, and high-energy electron density increase with RF power (30, 45, 60, and 75[Formula: see text]W) increase at 80[Formula: see text]MHz. The electron temperature decreases with RF power increase at 80[Formula: see text]MHz. The electron heating rate and argon ion heating rate near the sheath have no change with RF power increase at 80[Formula: see text]MHz. The electron energy probability distributions (EEPF) show that the number of high-energy electrons ([Formula: see text] [Formula: see text]eV) is highest at 80[Formula: see text]MHz. The reason may be the electron resonant heating that occurs in the plasma when the electron cyclotron frequency equals source frequency at 80[Formula: see text]MHz. The electron dynamics of capacitively coupled plasma is important for microelectronics etching and membrane deposition.

Hydrated Electron Dynamics and Stimulated Raman Scattering in Water Induced by Ultrashort Laser Pulses.

For this study, we employed intense 400 nm, 100 fs pulses linearly propagated through a 50 cm water medium, initially self-stretching the excitation pulses to 2.50 ps. Subsequently, the self-stretched 2.50 ps pulses were focused into deionized water, and we conducted transient absorption experiments to measure and investigate the dynamics of hydrated electrons in water. The excess electrons generated were injected into the hydrogen bond network of the water cluster, leading to the observation of saturated hydrated electrons. Additionally, we observed the emergence of the forward stimulated Raman scattering (SRS) of water molecules. We report the experimental observation of a weak forward SRS emission at 463 nm (corresponding to 3400 cm-1), indicative of the ordinary OH stretching vibration in the liquid phase. Moreover, we observed an intense forward SRS emission at 460 nm in water, corresponding to two anomalous Raman shifts at 3260 cm-1 and 3355 cm-1. These anomalous Raman shifts resulted from changes in the hydrogen bond network structure. We determine that the formation of not fully hydrated and saturated hydrated electrons plays a crucial role in producing this phenomenon.