Pump-probe Measurements Research Articles

Ultrafast measurement of photoacoustic parameters with mid-infrared frequency comb transients.

The photoacoustic (PA) effect has been widely used in various applications, including highly sensitive spectroscopy and label-free, non-invasive imaging. In this work, we demonstrate a fast and precise measurement of PA parameters for light-absorbing liquids using mid-infrared asynchronous sampling pump-probe measurements. To simulate the observed PA oscillation signals and extract various PA parameters as a function of pump power, we derived analytical solutions of the PA wave equation driven by a train of ultrashort Gaussian pump pulses. By fitting the analytical solution to the measured PA signals using a nonlinear curve fitting method, we could measure the PA parameters, including damping rate, viscosity, and natural frequency. Furthermore, the dynamic response of thermophysical properties of the chloroform solution is also investigated by measuring the variation of the Grüneisen parameter with pump power. We anticipate that this work will open new possibilities for precise in situ measurements of the thermal properties of light-absorbing liquids.

Ultrafast energy quenching mechanism of LHCSR3-dependent photoprotection in Chlamydomonas

Photosynthetic organisms have evolved an essential energy-dependent quenching (qE) mechanism to avoid any lethal damages caused by high light. While the triggering mechanism of qE has been well addressed, candidates for quenchers are often debated. This lack of understanding is because of the tremendous difficulty in measuring intact cells using transient absorption techniques. Here, we have conducted femtosecond pump-probe measurements to characterize this photophysical reaction using micro-sized cell fractions of the green alga Chlamydomonas reinhardtii that retain physiological qE function. Combined with kinetic modeling, we have demonstrated the presence of an ultrafast excitation energy transfer (EET) pathway from Chlorophyll a (Chl a) Qy to a carotenoid (car) S1 state, therefore proposing that this carotenoid, likely lutein1, is the quencher. This work has provided an easy-to-prepare qE active thylakoid membrane system for advanced spectroscopic studies and demonstrated that the energy dissipation pathway of qE is evolutionarily conserved from green algae to land plants.

High-output ∼3 μ m MIR pulsed laser enabled by surface state regulation in PtTe2 optical switch

Mid-infrared (MIR) pulsed lasers operating in the ∼3 μm region play a crucial role in various applications, including molecular spectroscopy, ultrafast molecular imaging, and laser-assisted surgery. Despite recent advancements in MIR gain platforms, a notable technological challenge remains in the absence of an effective optical Q-switch. Here, a remarkable optical Q-switch in the 3 μm region based on a Dirac semimetal PtTe2 saturable absorber is realized. By modulating the surface state of PtTe2, the pulsed laser exhibited an increase in average power, escalating from 521 to 588 mW, accompanied by a significant decrease in pulse width from 368 to 187 ns. Nondegenerate pump–probe measurements showed that the recombination rate of the photocarrier in thinner PtTe2 nanoplates was effectively accelerated, primarily attributed to the substantial increase in surface state density, leading to better saturable absorption performance. As the thickness of the PtTe2 nanoplates decreases, the nonsaturable loss decreases from 12% to 3%, while the modulation depth increases from 6% to 12%. The enhanced ultrafast nonlinear absorption enables flexible modulation of saturation absorption parameters, which endows high-performance MIR pulsed laser generation.

Ultrafast nanometric resolution spatiotemporal measurement of ambipolar diffusivity and carrier-phonon coupling in doped and undoped silicon

Understanding and determination of the ambipolar diffusivity of a semiconductor is fundamental for predicting device behavior and optimizing its performance. Ultrafast pump-probe measurements allow for the determination of energy carrier dynamics with sub-picosecond resolution. Due to the inherent diffusive nature of carriers, measurements with a high spatial resolution are needed, in addition to the traditional pump-probe system, to determine not only the carrier dynamics but also the spatial extent caused by carrier diffusion as well. In this work, a spatiotemporal measurement system with ultrafast temporal and nanometric spatial resolution, together with a comprehensive transport model, is used to determine the ambipolar diffusivity and carrier-phonon energy coupling time in both undoped and doped silicon. The results show that as the carrier density increases, the measured ambipolar diffusivity decreases with minimal variation in the carrier-phonon energy coupling time. In general, this work demonstrates an optical-based method for determining ambipolar diffusivity in a semiconductor material.

Photoinduced carrier transfer dynamics in a monolayer MoS2/PbS quantum dots heterostructure

Two-dimensional molybdenum disulfide (MoS2) has been proven to be a candidate in photodetectors, and MoS2/lead sulfide (PbS) quantum dots (QDs) heterostructure has been used to expand the optical response wavelength of MoS2. Time-resolved pump-probe transient absorption measurements are performed to clarify the carrier transfer dynamics in the MoS2/PbS heterostructure. By comparing the carrier dynamics in MoS2 and MoS2/PbS under different pump wavelengths, we found that the excited electrons in PbS QDs can transfer rapidly (<100 fs) to MoS2, inducing its optical response in the near-infrared region, although the pump light energy is lower than the bandgap of MoS2. Besides, interfacial excitons can be formed in the heterostructure, prolonging the lifetime of the excited carriers, which could be beneficial for the extraction of the carriers in devices.

Single-shot pump-probe technique by the combination of an echelon and a grating with a time window of 109 ps

In this study, using only a single pulse, pump-probe measurement with a large time window of more than 100 ps is implemented. A commercial grating is used to encode a time window of ∼56 ps in a single pulse; therefore, there is no need for machining customization. In addition, in this technique, the grating surface is accurately imaged, eliminating the image blur problem caused by phase differences in previous echelon-based techniques. Moreover, to make full use of the grating surface and obtain a larger time window, a simple reflection echelon is combined that matches the grating in the time window. This combination encoding strategy results in a total time window of ∼109 ps and maintains accurate imaging of the grating surface. This time window is an order of magnitude greater than the maximum reported values of the echelon encoding strategy and the angle beam encoding strategy. To demonstrate this single-shot pump-probe technique, the two-photon absorption process of ZnSe and the excited-state absorption process of a symmetrical phenoxazinium bromine salt were studied. The possibility of further improving the experimental setup is also discussed.

Transient reflectance of silicon carbide during laser-induced phase separation

Laser irradiation can induce local modulations of functional material properties, such as a decreased resistivity or a variation in reflectance. Recent studies investigated the laser-induced phase separation of 4 H-SiC into carbon and silicon on top of regrown SiC to customize its electrical conductivity for the application in electronic devices. To understand the physical processes leading to the laser-induced phase separation, time-resolved pump-probe measurements represent a suitable tool. This study advances the state of the art by characterizing the transient reflectance changes in 4 H-SiC upon irradiation by spatially resolved pump-probe reflectometry. Since the laser heating alters the reflectance of the sample, the spatially resolved measurement enables to observe the heat conduction from the irradiated to the non-irradiated areas, which sustains for several milliseconds. Numerical simulations of the temperature evolution reveal a restricted one-dimensional heat conduction into depth due to the broad lateral extent of the irradiated area. The associated sustained increased temperature within the irradiated area most certainly abets the feasibility of the phase separation. These findings offer practical insights for optimizing the applied laser parameters to tailor the material properties via phase separation.

Generation of High-Lying Vibrational States in Carbon Dioxide through Coherent Ladder Climbing.

Mid-infrared laser excitation of molecules into high-lying vibrational states offers a novel route to realize controlled ground-state chemistry. Here we successfully demonstrate vibrational ladder climbing in the antisymmetric stretch of CO2 in the condensed phase by using intense down-chirped mid-infrared pulses. Spectrally resolved pump-probe measurements directly observe excited-state absorptions attributed to vibrational populations up to the v = 9 state, whose corresponding energy of 2.5 eV is 46% of the dissociation energy. By the use of global fitting analysis, important spectroscopic parameters in the high-lying vibrational states, such as transition frequencies and relaxation times, are quantitatively characterized. Remarkably, our analysis shows that 40% of the molecules are excited above the typical activation barriers in the metal-catalyzed CO2 conversions. These results not only demonstrate the promising ability of infrared excitation to produce elevated vibrational states but also represent a significant step toward accelerating CO2 conversions and other chemical processes via mode-specific vibrational excitation.

Coherent acoustic vibrations of Au nanoblocks and their modulation by Al2O3 layer deposition.

Coherent acoustic phonons induced in metallic nanostructures have attracted tremendous attention owing to their unique optomechanical characteristics. The frequency of the acoustic phonon vibration is highly sensitive to the material adsorption on metallic nanostructures and, therefore, the acoustic phonon offers a promising platform for ultrasensitive mass sensors. However, the physical origin of acoustic frequency modulation by material adsorption has been partially unexplored so far. In this study, we prepared Al2O3-deposited Au nanoblocks and measured their acoustic phonon frequencies using time-resolved pump-probe measurements. By precisely controlling the thickness of the Al2O3 layer, we systematically investigated the relation between the acoustic phonon frequency and the deposited Al2O3 amounts. The time-resolved measurements revealed that the acoustic breathing modes were predominantly excited in the Au nanoblocks, and their frequencies increased with the increment of the Al2O3 thickness. From the relationship between the acoustic phonon frequency and the Al2O3 thickness, we revealed that the acoustic phonon frequency modulation is attributed to the density change of the whole sample. Our results would provide fruitful information for developing quantitative mass sensing devices based on metallic nanostructures.

Thermal bridging effect enhancing heat transport across graphene interfaces with pinhole defects

Interfacial thermal conductance (G) is of critical significance to the efficient thermal management of two-dimensional (2D) material devices. Despite the importance of defects engineering in tuning G, the mechanisms of heat transport across defective graphene interfaces remain unclear. In this study, we have identified and demonstrated the origins of the enhanced heat transport across pinhole defective graphene through our ultrafast pump-probe measurements and molecular dynamics (MD) simulations. In prior work, the enhanced G across defective graphene interfaces was commonly attributed to the improved overlap of phonon density of states (DOS) or interfacial coupling strength. We, however, observe a remarkable 2.5-fold increase in heat conduction and a distinctly different temperature dependence of G for defective graphene with the same superstrate and substrate material, compared to pristine graphene. In contrast, interfaces with different superstrate and substrate materials show only minor changes (<15%) in thermal conductance after introducing defects in the graphene layer. Through careful analysis of our MD simulations for various defective graphene interfaces, we conclude that, contradictory to common beliefs, it is the formation of direct contact thermal bridge, instead of the improvement in the phonon DOS overlap or interfacial coupling strength, that has a decisive effect and promotes heat transport across defective graphene interfaces. The differing impacts of the thermal bridge on G of defective graphene sandwiched by layers of the same and different materials are primarily attributed to the varying coupling strength between the substrate and superstrate. Our work provides important insights and physical understandings of the mechanisms of heat conduction across defective graphene interfaces.

2D Time-Domain Spectroscopy for Determination of Energy and Momentum Relaxation Rates of Hydrogen-Like Donor States in Germanium.

We present measurements of the coherence times of excited states of hydrogen-like arsenic impurities in germanium (Ge:As) using a table-top two-dimensional time-domain spectroscopy (2D-TDS) system. We show that this laboratory system is capable of resolving the coherence lifetimes of atomic-like excited levels of impurity centers in semiconductors, such as those used in solid-state quantum information technologies, on a subpicosecond time scale. By fitting the coherent nonlinear response of the system with the known intracenter transition frequencies, we are able to monitor coherent population transfer and decay of the transitions from the 2p0 and 2p± states for different low excitation pulse fields. Furthermore, by examining the off-diagonal resonances in the 2D frequency-domain map, we are able to identify coherences between excited electronic states that are not visible via conventional single-frequency pump-probe or Hahn-echo measurements.

Transient pump-probe analysis of pump-induced lensing in laser amplifiers.

Understanding of pump-induced lensing in laser amplifiers is essential for the optimized design of high-power lasers with high spatial quality, but there is usually incomplete knowledge of the interplay between thermal and population induced lensing mechanisms, lensing under lasing and non-lasing conditions, and transient lensing effects under pulsed operation. This paper provides quantitative insight of pump-induced lensing effects by using experimental transient pump-probe measurements in an alexandrite laser amplifier end-pumped by a short pulse pump beam with Gaussian spatial intensity distribution. Lensing results are presented showing a large difference in lensing under both non-lasing and lasing conditions and distinction of the population lens and thermal lens contributions from their different response time. Different pump beam sizes are used to show the variation of the relative strength of the lensing mechanisms. Comparison of experimental results with the analytical transient theory developed in this paper for the Gaussian pump beam gives excellent agreement and quantitative information on the thermal and population contributions to the amplifier lens. This paper provides a methodology for quantitative investigation of pump-induced lensing in general laser amplifier systems, and potentially other classes of optical materials with residual optical absorption.

Ultrafast Spectroscopy under Vibrational Strong Coupling in Diphenylphosphoryl Azide.

Strong coupling of cavity photons and molecular vibrations creates vibrational polaritons that have been shown to modify chemical reactivity and alter material properties. While ultrafast spectroscopy of vibrational polaritons has been performed intensively in metal complexes, ultrafast dynamics in vibrationally strongly coupled organic molecules remain unexplored. Here, we report ultrafast pump-probe measurement and two-dimensional infrared spectroscopy in diphenylphosphoryl azide under vibrational strong coupling. Early time oscillatory structures indicate coherent energy exchange between the two polariton modes, which decays in ∼2 ps. We observe a large transient absorptive feature around the lower polariton, which can be explained by the overlapped excited-state absorption and derivative-shaped structures around the lower and upper polaritons. The latter feature is explained by the Rabi splitting contraction, which is ascribed to a reduced population in the ground state. These results reassure the previously reported spectroscopic theory to describe nonlinear spectroscopy of vibrational polaritons. We have also noticed the influence of the complicated layer structure of the cavity mirrors. The penetration of the electric field distribution into the layered structure of the dielectric-mirror cavities can significantly affect the Rabi splitting and the decay time constant of polaritonic systems.

Implementation of a laser-neutron pump-probe capability for inelastic neutron scattering.

Knowledge about nonequilibrium dynamics in spin systems is of great importance to both fundamental science and technological applications. Inelastic neutron scattering (INS) is an indispensable tool to study spin excitations in complex magnetic materials. However, conventional INS spectrometers currently only perform steady-state measurements and probe averaged properties over many collision events between spin excitations in thermodynamic equilibrium, while the exact picture of re-equilibration of these excitations remains unknown. In this paper, we report on the design and implementation of a time-resolved laser-neutron pump-probe capability at hybrid spectrometer (beamline 14-B) at the Spallation Neutron Source (SNS) at Oak Ridge National Laboratory. This capability allows us to excite out-of-equilibrium magnons with a nanosecond pulsed laser source and probe the resulting dynamics using INS. Here, we discussed technical aspects to implement such a capability in a neutron beamline, including choices of suitable neutron instrumentation and material systems, laser excitation scheme, experimental configurations, and relevant firmware and software development to allow for time-synchronized pump-probe measurements. We demonstrated that the laser-induced nonequilibrium structure factor is able to be resolved by INS in a quantum magnet. The method developed in this work will provide SNS with advanced capabilities for performing out-of-equilibrium measurements, opening up an entirely new research direction to study out-of-equilibrium phenomena using neutrons.

High-energy-resolution off-resonant spectroscopy with self-seeded x-ray free-electron laser pulses.

This paper presents the implementation of high-energy-resolution off-resonant spectroscopy (HEROS) measurements using self-seeded x-ray free-electron laser (XFEL) pulses. This study systematically investigated XFEL conditions, including photon energy and accumulated shot numbers, to optimize the measurement efficiency for copper foil samples near the K-edge. The x-ray absorption spectra reconstructed using HEROS were compared with those derived from fluorescence-yield measurements. The HEROS-based spectra exhibited consistent line shapes independent of the sample thickness. The potential application of HEROS to high-temperature copper was also explored. HEROS offers distinct advantages including scan-free measurement of x-ray absorption spectra with reduced core-hole lifetime broadening and self-absorption effects. Using self-seeded XFEL pulses, HEROS facilitates single-shot-based pump-probe measurements to investigate the ultrafast dynamics in various materials and diverse conditions.

Photodissociation Dynamics of the Highly Stable ortho-Nitroaniline Cation.

0rtho-Nitroaniline (ONA) is a model for the insensitive high explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) that shares strong hydrogen bonding character between adjacent nitro and amino groups. This work reports femtosecond time-resolved mass spectrometry (FTRMS) measurements and theoretical calculations that explain the high stability of the ONA cation compared with related nitroaromatic molecules. Ab initio calculations found that the lowest-lying electronic excited state of the ONA cation, D1, lies more than 2 eV above the ground state, and the energetic barriers to rearrangement and dissociation reactions exceed this D1 energy. These theoretical results were confirmed by FTRMS pump-probe measurements showing that (1) fragment ions represented less than 30% of the total ion yield when a 1014 W cm-2, 1300 nm, 20 fs pump pulse was used to ionize ONA; and (2) 3.1 eV (400 nm) photons were required to induce dissociation of the ONA cation. Stronger coupling between the ground D0 and excited D4 states of the ONA cation at the geometry of neutral ONA resulted in a transient enhancement of fragment ion yields at <300 fs pump-probe delay times, prior to relaxation of the ONA cation to its optimal geometry.

Chirped pulse upconversion for femtosecond mid-infrared spectroscopy at 100 kHz.

We demonstrate that chirped pulse up-conversion (CPU), a method routinely used with systems based on 1-kHz Titanium:Sapphire lasers, can be extended to a repetition rate of 100 kHz with an Ytterbium diode-pumped femtosecond amplifier. Individual mid-infrared spectra can thus be measured directly in the near infrared using a fast CMOS linescan camera. After an appropriate Fourier processing, a spectral resolution of 1.1 cm-1 is reported, currently limited by our spectrometer. Additionally, we demonstrate the application of CPU to a pump-probe measurement of the vibrational relaxation in carboxy-hemoglobin, and we show that the combination of fast scanning and fast acquisition enables a straightforward removal of pump scattering interference.

Mechanisms Underlying a Quantum Superposition Microscope Based on THz-Driven Coherent Oscillations in a Two-Level Molecular Sensor.

We report pump-probe measurements of a hydrogen molecule (H_{2}) in the tunnel junction of a scanning tunneling microscope coupled to ultrashort terahertz (THz) pulses. The coherent oscillation of the THz-induced dc tunneling current at a frequency of ∼0.5 THz fingerprints the absorption by H_{2} as a two-level system (TLS). Two components of the oscillatory signal are observed and point to both photon and field aspects of the THz pulses. A few loosely bound states with similar energies for the upper state of the TLS are evidenced by the coherent revival of oscillatory signal. Furthermore, the comparison of spectroscopic features of H_{2} with different tips provides an understanding of the TLS for H_{2}.

Exploring the Early Time Behavior of the Excited States of an Archetype Thermally Activated Delayed Fluorescence Molecule.

Optical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter DMAC-TRZ. The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements. The photoinduced absorption signals are highly dependent on polarity, affecting the transition oscillator strength but not their relative energy positions. In methylcyclohexane, a strong and vibronically structured local triplet excited state absorption (3LE → 3LEn) is observed, which is quenched in higher polarity solvents as 3CT becomes the lowest triplet state. Furthermore, ultrafast transient absorption (fsTA) confirms the presence of two stable conformers of DMAC-TRZ: (1) quasi-axial (QA) interconverting within 20 ps into (2) quasi-equatorial (QE) in the excited state. Moreover, fsTA highlights how sensitive excited state couplings are to the environment and the molecular conformation.

Interactions and ultrafast dynamics of exciton complexes in a monolayer semiconductor with electron gas

Abstract We present femtosecond pump-probe measurements of neutral and charged exciton optical response in monolayer MoSe2 to resonant photoexcitation of a given exciton state in the presence of 2D electron gas. We show that creation of charged exciton (X−) population in a given K+, K− valley requires the capture of available free carriers in the opposite valley and reduces the interaction of neutral exciton (X) with the electron Fermi sea. We also observe spectral broadening of the X transition line with the increasing X− population caused by efficient scattering and excitation induced dephasing. From the valley-resolved analysis of the observed effects we are able to extract the spin-valley relaxation times of free carriers as a function of carrier density. Moreover, we analyze the oscillator strength and energy shift of X in the regime of interaction with electron Fermi sea under resonant excitation. From this we can observe the process of X decay by radiative recombination paired with trion formation. We demonstrate an increase of neutral exciton relaxation rate with the introduction of Fermi sea of electrons. We ascribe the observed effect to the increased efficiency of the trion formation, as well as the radiative decay caused by the screening of disorder by the free carriers.