Ultrashort Time Scales Research Articles

Sub-20-fs UV-XUV beamline for ultrafast molecular spectroscopy

We present an ultraviolet (UV) - extreme-ultraviolet (XUV) pump-probe beamline with applications in ultrafast time-resolved photoelectron spectroscopy. The UV pump pulses, tuneable between 255 and 285 nm and with µJ-level energy, are generated by frequency up-conversion between ultrashort visible/infrared pulses and visible narrow-band pulses. Few-femtosecond XUV probe pulses are produced by a high-order harmonic generation source equipped with a state-of-the-art time-delay compensated monochromator. Two-colour UV-XUV sidebands are used for a complete in situ temporal characterization of the pulses, demonstrating a temporal resolution of better than 20 fs. We validate the performances of the beamline through a UV-XUV pump-probe measurement on 1,3-cyclohexadiene, resolving the ultrashort dynamics of the first conical intersection. This instrument opens exciting possibilities for investigating ultrafast UV-induced dynamics of organic molecules in ultrashort time scales.

Carrier-envelope phase effects on the reflectance of diamond films irradiated by ultrashort single-cycle light pulses: A comparison study in attosecond and femtosecond regimes

Diamond films irradiated with few-cycle laser pulses are emerging as a all-optical information processing device with high-speed and low-power-consumption. The possibility to steer, control or switch such few-cycle laser pulses with diamond films is expected to pave the way towards ultrafast all-optical switching. Here, we show theoretically the effect of the carrier-envelope phase (CEP) of the ultrashort single-cycle light pulses on the reflectance of diamond films within the framework of multi-scale theory. We observe clear variations in the reflectance behavior of femtosecond pulses and attosecond pulses. Our most important finding is that the reflectivity difference of attosecond pulses with different waveforms and the same spectrum on diamond films exhibits a perfect quadratic relationship with the CEP. This observation suggests that the nonlinearity of attosecond pulses is different from that of femtosecond pulses. Analysis of these results allows us to gain new insights in the interaction between attosecond light pulses and matter. This opens fascinating avenues for all-optical information processing over ultrashort lengths and timescales.

Ultrafast Yttrium Hydride Chemistry at High Pressures via Non-equilibrium States Induced by an X-ray Free Electron Laser.

Controlling the formation and stoichiometric content of the desired phases of materials has become of central interest for a variety of fields. The possibility of accessing metastable states by initiating reactions by X-ray-triggered mechanisms over ultrashort time scales has been enabled by the development of X-ray free electron lasers (XFELs). Utilizing the exceptionally high-brilliance X-ray pulses from the EuXFEL, we report the synthesis of a previously unobserved yttrium hydride under high pressure, along with nonstoichiometric changes in hydrogen content as probed at a repetition rate of 4.5 MHz using time-resolved X-ray diffraction. Exploiting non-equilibrium pathways, we synthesize and characterize a hydride in a Weaire-Phelan structure type at pressures as low as 125 GPa, predicted using a crystal structure search, with a hydrogen content of 4.0-5.75 hydrogens per cation, that is enthalpically metastable on the convex hull.

Atomic-scale imaging of laser-driven electron dynamics in solids

Resolving laser-driven electron dynamics on their natural time and length scales is essential for understanding and controlling light-induced phenomena. Capabilities to reveal these dynamics are limited by challenges in interpreting wave mixing of a driving and a probe pulse, low energy resolution at ultrashort time scales and a lack of atomic-scale resolution by standard spectroscopic techniques. Here, we demonstrate how ultrafast x-ray diffraction can access fundamental information on laser-driven electronic motion in solids. We propose a method based on subcycle-resolved x-ray-optical wave mixing that allows for a straightforward reconstruction of key properties of strong-field-induced electron dynamics with atomic spatial resolution. Namely, this technique provides both phases and amplitudes of the spatial Fourier transform of optically-induced charge distributions, their temporal behavior, and the direction of the instantaneous microscopic optically-induced electron current flow. It captures the rich microscopic structures and symmetry features of laser-driven electronic charge and current density distributions.

How quickly does FLASH need to be delivered? A theoretical study of radiolytic oxygen depletion kinetics in tissues

Purpose. Radiation delivered over ultra-short timescales (‘FLASH’ radiotherapy) leads to a reduction in normal tissue toxicities for a range of tissues in the preclinical setting. Experiments have shown this reduction occurs for total delivery times less than a ‘critical’ time that varies by two orders of magnitude between brain (∼0.3 s) and skin (⪆10 s), and three orders of magnitude across different bowel experiments, from ∼0.01 to ⪆(1–10) s. Understanding the factors responsible for this broad variation may be important for translation of FLASH into the clinic and understanding the mechanisms behind FLASH. Methods. Assuming radiolytic oxygen depletion (ROD) to be the primary driver of FLASH effects, oxygen diffusion, consumption, and ROD were evaluated numerically for simulated tissues with pseudorandom vasculatures for a range of radiation delivery times, capillary densities, and oxygen consumption rates (OCR’s). The resulting time-dependent oxygen partial pressure distribution histograms were used to estimate cell survival in these tissues using the linear quadratic model, modified to incorporate oxygen-enhancement ratio effects. Results. Independent of the capillary density, there was a substantial increase in predicted cell survival when the total delivery time was less than the capillary oxygen tension (mmHg) divided by the OCR (expressed in units of mmHg/s), setting the critical delivery time for FLASH in simulated tissues. Using literature OCR values for different normal tissues, the predicted range of critical delivery times agreed well with experimental values for skin and brain and, modifying our model to allow for fluctuating perfusion, bowel. Conclusions. The broad three-orders-of-magnitude variation in critical irradiation delivery times observed in in vivo preclinical experiments can be accounted for by the ROD hypothesis and differences in the OCR amongst simulated normal tissues. Characterization of these may help guide future experiments and open the door to optimized tissue-specific clinical protocols.

Time-varying materials for analog optical computing

Subject of study. In this study, a new class of artificial electromagnetic media, known as time-varying materials, is explored. These materials are characterized by a rapid modulation of their optical parameters on ultrashort timescales that are comparable to or shorter than the wave period. Aim of study. The aim of this study was to develop a new platform for implementing analog optical computers. Specifically, we investigated the dependence of the amplitudes and frequencies of waves, formed through interaction with a time-varying medium, on the permittivity switching time and magnitude of spectral dispersion. Method. The amplitudes of reflected and refracted electromagnetic waves were calculated using the time-domain finite-element method. A Lorentz model with a time-dependent plasma frequency was employed to analyze the time-varying medium with spectral dispersion. The optical response of the medium, which exhibited noninstantaneous switching, was studied by considering a sigmoidal switching profile. Main results. Our findings show that a dispersive time-varying medium can generate several spectral components that are shifted from the frequency of the incident light. By controlling the speed and depth of permittivity switching, the amplitudes and frequencies of the time-reflected/refracted waves can be adjusted. To observe the reflected wave, the duration of switching should be comparable to or less than the period of the incident wave. Practical significance. The results of this study are valuable for developing next-generation optical devices. The ability to flexibly control the amplitude and frequency of light waves through the temporal modulation of homogeneous media offers new opportunities for the realization of analog optical computers.

Mean-field equation for phase-modulated optical parametric oscillator

The widely established techniques for the generation of ultrashort optical pulses rely on passive mode locking of lasers, with the output pulse duration and emission spectrum determined by the intrinsic lifetime of laser transition in the gain medium. Due to the instantaneous nature of nonlinear gain, optical parametric oscillators (OPOs) are capable of generating optical radiation in all timescales from continuous-wave (cw) to ultrashort femtosecond regime, if driven by laser pump sources in the corresponding time domain. In the ultrashort timescale, operation of OPOs conventionally relies on mode-locked pump lasers, with the concomitant disadvantages of large footprint and high cost. At the same time, the lack of gain storage mandates the use of synchronous pumping, resulting in increased complexity. In this paper, we present the concept of phase-modulated OPO driven by cw pump laser. The approach overcomes the traditional drawbacks of ultrafast OPOs, enabling femtosecond pulse generation without the need for synchronous pumping, resulting in a simplified, compact, and cost-effective architecture using cw input pump lasers. We derive a mean-field equation for a degenerate χ(2) OPO driven by a cw laser with intracavity electro-optic modulator (EOM), and also including dispersion compensation. The equation predicts the formation of stable femtosecond pulses (<200fs), in both normal and anomalous dispersion regimes, with a controllable repetition rate determined by the frequency of the EOM. The remarkable functionality of the proposed scheme paves the way for the development of an alternative class of widely tunable coherent femtosecond light sources in both bulk and integrated format based on χ(2) OPOs using cw pump lasers. Published by the American Physical Society 2024

Ultrafast orbital Hall effect in metallic nanoribbons

The orbital Hall effect can generate currents of angular momentum more efficiently than the spin Hall effect in most metals. However, so far, it has only been understood as a steady-state phenomenon. In this theoretical study, the orbital Hall effect is extended into the time domain. We investigate the orbital angular momenta and their currents induced by a femtosecond laser pulse in a Cu nanoribbon. Our numerical simulations provide detailed insights into the laser-driven electron dynamics on ultrashort timescales with atomic resolution. The ultrafast orbital Hall effect described in this paper is consistent with the familiar pictorial representation of the static orbital Hall effect, but we also find pronounced differences between physical quantities that carry orbital angular momentum and those that carry charge. For example, there are deviations in the time series of the respective currents. This paper lays the foundations for investigating ultrafast Hall effects in confined metallic systems. Published by the American Physical Society 2024

Exploring viscosity influence mechanisms on coating removal: Insights from single cavitation bubble behaviours in low-frequency ultrasonic settings

The role of acoustic cavitation in various surface cleaning disciplines is important. However, the physical mechanisms underlying acoustic cavitation-induced surface cleansing are poorly understood. This is due to the combination of microscopic and ultrashort timescales associated with the dynamics of acoustic cavitation bubbles. Here, we have precisely controlled single-bubble cavitation in both space and time. Ultrasonic excitation leads to the cavitation of generated single bubbles. A synchronous ultrafast photomicrographic system simultaneously records the dynamics of single acoustic cavitation bubbles (SACBs) and the cleaning process of the nearby surface in liquids with varying viscosities. Finally, we analysed the correlation between bubble dynamics and surface cleaning situations. The differences in the typical dynamic characteristics of the bubbles during collapse in liquids with varying viscosities reveal two main mechanisms underlying surface cleaning by acoustic cavitation, which are respective the Laplace pressure during the bubble’s movement and liquid jets during bubble collapse. Our study provides a better physical understanding of the ultrasonic cleaning process based on acoustic cavitation, and will help to optimize and facilitate the applications of surface cleaning, especially for the cleaning of substrates with tightly attached dirt.

Rebuilding the vibrational wavepacket in TRAS using attosecond X-ray pulses

Time-resolved X-ray photoelectron spectroscopy (TXPS) is a well-established technique to probe coherent nuclear wavepacket dynamics using both table-top and free-electron-based ultrafast X-ray lasers. Energy resolution, however, becomes compromised for a very short pulse duration in the sub-femtosecond range. By resonantly tuning the X-ray pulse to core-excited states undergoing Auger decay, this drawback of TXPS can be mitigated. While resonant Auger-electron spectroscopy (RAS) can recover the vibrational structures not hidden by broadband excitation, the full reconstruction of the wavepacket is a standing challenge. Here, we theoretically demonstrate how the complete information of a nuclear wavepacket, i.e., the populations and relative phases of the vibrational states constituting the wavepacket, can be retrieved from time-resolved RAS (TRAS) measurements. Thus, TRAS offers key insights into coupled nuclear and electronic dynamics in complex systems on ultrashort timescales, providing an alternative to leverage femtosecond and attosecond X-ray probe pulses.

O,S-Chelated bis(pentafluorophenyl)boron and diphenylboron-β-thioketonates: synthesis, photophysical, electrochemical and NLO properties.

Boron-β-diketonates are classical emissive materials that have been utilized in various fields, however, boron monothio-β-thioketonates, where one oxygen atom is exchanged for a sulphur atom, have not been explored in detail. To gain a better understanding of this class of materials, we synthesised various aryl substituted monothio-β-diketonate boron complexes with two different aryl substitutions on the boron center and studied their structural, optical and electrochemical properties. Single crystal X-ray analysis revealed that there is considerable deviation in B-O and B-S bond lengths for bis(pentafluorophenyl)boron complexes against diphenyl boron complexes. The bis(pentafluorophenyl)boron complexes have a relatively high absorption coefficient over diphenyl boron complexes. More importantly, a striking difference was observed for the emission behaviour of these compounds. The bis(pentafluorophenyl)boron complexes exhibit weak emission in the solution as well as in the solid state, whereas diphenyl boron complexes do not show any emission in either solution or the solid state. Further, the electrochemical study reveals that diphenyl boron complexes show a reduction potential that is more negative compared to the bis(pentafluorophenyl)boron complexes. The high absorption coefficient of the compounds pointed towards the possibility of high first order hyperpolarizability upon optical excitation, which motivated us to ascertain the nonlinear optical coefficients in the near infrared range, towards applicability of such compounds in optical limiting and switching. The open aperture Z-scan measurements at ultrashort time scales elucidated a few critical features of such compounds towards optical limiting applications.

Ultrafast Laser-Induced Dynamics of Non-Equilibrium Electron Spill-Out in Nanoplasmonic Bilayers.

Contemporary quantum plasmonics capture subtle corrections to the properties of plasmonic nano-objects in equilibrium. Here, we demonstrate non-equilibrium spill-out redistribution of the electronic density at the ultrafast time scale. As revealed by time-resolved 2D spectroscopy of nanoplasmonic Fe/Au bilayers, an injection of the laser-excited non-thermal electrons induces transient electron spill-out thus changing the plasma frequency. The response of the local electronic density switches the electronic density behavior from spill-in to strong (an order of magnitude larger) spill-out at the femtosecond time scale. The superdiffusive transport of hot electrons and the lack of a direct laser heating indicate significantly non-thermal origin of the underlying physics. Our results demonstrate an ultrafast and non-thermal way to control surface plasmon dispersion through transient variations of the spatial electron distribution at the nanoscale. These findings expand quantum plasmonics into previously unexplored directions by introducing ultrashort time scales in the non-equilibrium electronic systems.

Exploring fs-laser irradiation damage subthreshold behavior of dielectric mirrors via electrical measurements

Abstract With ultrafast laser systems reaching presently 10 PW peak power or operating at high repetition rates, research towards ensuring the long-term, trouble-free performance of all laser-exposed optical components is critical. Our work is focused on providing insight into the optical material behavior at fluences below the standardized laser-induced damage threshold (LIDT) value by implementing a simultaneous dual analysis of surface emitted particles using a Langmuir probe (LP) and the target current (TC). ${\mathrm{HfO}}_2$ and ${\mathrm{ZrO}}_2$ thin films deposited on fused silica substrates by pulsed laser deposition at various ${\mathrm{O}}_2$ pressures for defect and stoichiometry control were irradiated by Gaussian, ultrashort laser pulses (800 nm, 10 Hz, 70 fs) in a wide range of fluences. Both TC and LP collected signals were in good agreement with the existing theoretical description of laser–matter interaction at an ultrashort time scale. Our approach for an in situ LIDT monitoring system provides measurable signals for below-threshold irradiation conditions that indicate the endurance limit of the optical surfaces in the single-shot energy scanning mode. The LIDT value extracted from the LP-TC system is in line with the multipulse statistical analysis done with ISO 21254-2:2011(E). The implementation of the LP and TC as on-shot diagnostic tools for optical components will have a significant impact on the reliability of next-generation ultrafast and high-power laser systems.

A coherent phonon-induced hidden quadrupolar ordered state in Ca2RuO4

Ultrafast laser excitation provides a means to transiently realize long-range ordered electronic states of matter that are hidden in thermal equilibrium. Recently, this approach has unveiled a variety of thermally inaccessible ordered states in strongly correlated materials, including charge density wave, ferroelectric, magnetic, and intertwined charge-orbital ordered states. However, more exotic hidden states exhibiting higher multipolar ordering remain elusive owing to the challenge of directly manipulating and detecting them with light. Here we demonstrate a method to induce a dynamical transition from a thermally allowed to a thermally forbidden spin-orbit entangled quadrupolar ordered state in Ca2RuO4 by coherently exciting a phonon that is strongly coupled to the order parameter. Combining probe photon energy-resolved coherent phonon spectroscopy measurements with model Hamiltonian calculations, we show that the dynamical transition is manifested through anomalies in the temperature, pump excitation fluence, and probe photon energy dependence of the strongly coupled phonon. With this procedure, we introduce a general pathway to uncover hidden multipolar ordered states and to control their re-orientation on ultrashort timescales.

Discrete heat conduction equation: Dispersion analysis and continuous limits

The dispersion relation in ω-k space has been derived and analyzed for discrete heat conduction equation (DE). The DE is inherently nonlocal both in time and space and can be used to describe non-Fourier heat transport occurring on ultrashort time and length scales. An important distinction between the DE and the continuum description is that the frequencies and wave numbers available to the discrete system are limited, whereas in the continuum description there are no such limitations. Analytical expressions for the attenuation distance, group and phase velocities have been obtained and analyzed as functions of frequency. In the continuum limit, depending on the basic invariant of the continualization procedure, the dispersion relation for the DE reduces to either dispersion relation for the classical Fourier parabolic equation (PE) or to dispersion relation for the hyperbolic heat equation (HE). However, at the moderate and high frequencies the spectrum of the DE differs significantly from the spectra of the PE and HE. This implies that the continuum-based approaches, including both the PE and HE, unable to describe high-frequency and short-wavelength processes and the DE is preferable. This work provides a relatively simple analytical tool to interpret the transient wave-like behavior of heat transport on ultrashort space and time scales.

The Ultra-short-, Short- and Short-medium- Term Impact of Covid-19 Pandemic on Bitcoin Prices

The global outbreak of the COVID-19 pandemic has led to significant disruptions in financial markets, including the virtual currency market. This study examines the impact of the pandemic on Bitcoin prices across ultra-short, short, and short-medium time scales. Using ARIMA modeling, this paper analyze the dynamic behavior of Bitcoin prices in response to the effects of the pandemic. This findings illustrate distinct patterns of behavior in different time frames. First of all, from the ultra-short term perspective, after the local outbreak of the epidemic in China, compared with the control group constructed by the model, the price of Bitcoin has a relatively obvious upward trend during this period. In the short term, the outbreak of the global epidemic has led to a setback in investor confidence in all kinds of financial assets, and Bitcoin is no exception, and it is also facing a sharp decline. In the short to medium term, Bitcoin has acted as a safe haven asset in the context of the global pandemic of Covid-19. Understanding these intricate dynamics provides valuable insights into Bitcoin's multifaceted role during times of global uncertainty.

Imaging surfaces at the space–time limit: New perspectives of time-resolved scanning tunneling microscopy for ultrafast surface science

Many fundamental processes in nature occur on ultrashort time scales within picoseconds to attoseconds, and on intrinsic length scales from nanometers to picometers. The structure of crystalline solids is dictated by long range order and the periodic arrangement of atoms, but the elementary excitations that define its interaction with the environment may vary locally at the atomic scale. Multiple domains and phases can coexist on length scales down to a few nanometer, and impurities and defects can influence the collective many-body response of solids at the single-atom level. Ultrafast pump–probe techniques provide valuable information about fundamental many-body interactions in solids and at surfaces, but spatially average over macroscopic spot sizes such that the influence of local order or disorder at angstrom scales is not directly accessible. Therefore, real-space observation of ultrafast dynamics with atomic spatial resolution is highly desirable, and motivates the development of time-resolved ultrafast scanning tunneling microscopy (USTM) since the early 1990’s. Tremendous progress has been made in this field in the past decade, and a number of breakthrough achievements have significantly advanced our possibilities to add ultrafast time resolution to the angstrom spatial resolution of STM. This article reviews new technical approaches and developments in the field of USTM. A particular focus will be the classification of light-matter interaction in tunnel junctions, based on the criteria for adiabatic tunneling from Keldysh's theory of strong-field ionization and a tunneling time as defined by Büttiker and Landauer, and on Tucker's definition of quantum detection in a tunnel junction mixer. Moreover, various mechanisms to generate an ultrafast tunneling current in USTM are discussed and are to some extent related to those from other techniques such as optical spectroscopy or photoemission spectroscopy. The resulting new possibilities for imaging the ultrafast dynamics of electronic and vibrational excitations at surfaces with USTM will be highlighted. Finally, the article outlines possible future directions of USTM for studying ultrafast processes and light-induced phenomena at surfaces and in quantum materials.

Tomographic reconstruction of picosecond acoustic strain pulses using automated angle-scan probing with visible light

By means of an ultrafast optical technique, picosecond acoustic strain pulses in a transparent medium are tomographically visualized at GHz frequencies. The strain distribution in BK7 glass is reconstructed from time-domain reflectivity changes of 415-nm probe light as a function of the optical incidence angle with 1 ps temporal and 120 nm spatial resolutions, enabled by automated angle scanning. The latter resolution is achieved owing to the commensurate acoustic wavelength. Applications include imaging strain, carrier and temperature distributions on ultrashort timescales.

Determining hot-carrier transport dynamics from terahertz emission.

Understanding the ultrafast excitation and transport dynamics of plasmon-driven hot carriers is critical to the development of optoelectronics, photochemistry, and solar-energy harvesting. However, the ultrashort time and length scales associated with the behavior of these highly out-of-equilibrium carriers have impaired experimental verification of ab initio quantum theories. Here, we present an approach to studying plasmonic hot-carrier dynamics that analyzes the temporal waveform of coherent terahertz bursts radiated by photo-ejected hot carriers from designer nano-antennas with a broken symmetry. For ballistic carriers ejected from gold antennas, we find an ~11-femtosecond timescale composed of the plasmon lifetime and ballistic transport time. Polarization- and phase-sensitive detection of terahertz fields further grant direct access to their ballistic transport trajectory. Our approach opens explorations of ultrafast carrier dynamics in optically excited nanostructures.

High harmonic generation in monolayer MoS2 controlled by resonant and near-resonant pulses on ultrashort time scales

We report on experimental investigation of nonperturbative high harmonic generation (HHG) in monolayer MoS2 in the ultraviolet spectral region driven by mid-infrared light. We study how the HHG is influenced by pre-excitation of the monolayer using resonant and near-resonant pulses in a pump–probe-like scheme. The resonant light creates high density exciton population. Due to ultrafast dephasing caused by electron–electron scattering, the HHG is suppressed in the presence of pre-excited carriers. In the case of near-resonant excitation with photon energy below the exciton transition, the dynamics of the observed suppression of the HHG yield contains a fast component, which is a consequence of momentum scattering at carriers, which are excited by two-photon transition when the two pulses temporally overlap in the sample. This interpretation is supported by comparing the experimental data with theoretical calculations of the two-photon absorption spectrum of the MoS2 monolayer. This work demonstrates a possibility to control HHG in low-dimensional materials on ultrashort timescales by combining the driving strong-field pulse with a weak near-resonant light.