Femtosecond Pump-probe Experiments Research Articles

Effect of photoexcitation on high-harmonic generation in semiconductors

Solid-state high-harmonic generation is intrinsically sensitive to band structure, carrier population, and carrier scattering. As such, solid-state high-harmonic generation is increasingly used as a probe for femtosecond time-resolved pump-probe experiments. So far, most experimental pump-probe studies have reported photoexcitation-induced amplitude suppression of high-harmonic generation in solid-state media, yet the origins of this phenomenon remain elusive. Through simulations based on the semiconductor Bloch equations, we identify the dephasing of the coherent carrier population as the primary mechanism driving this suppression. Furthermore, we find band gap renormalization to be a source for phase shifts of high harmonics. We introduce an analytical model, based on a semi-classical action, that supports our numerical outcomes.

Ab initio-simulated optical response of hot electrons in gold and ruthenium

Optical femtosecond pump-probe experiments allow to measure the dynamics of ultrafast heating of metals with high accuracy. However, the theoretical analysis of such experiments is often complicated because of the indirect connection of the measured signal and the desired temperature transients. Establishing such a connection requires an accurate model of the optical constants of a metal, depending on both the electron temperature T e and the lattice temperature T l . In this paper, we present first-principles simulations of the two-temperature scenario with T e ≫ T l , showing the optical response of hot electrons to laser irradiation in gold and ruthenium. Comparing our simulations with the Kubo-Greenwood approach, we discuss the influence of electron-phonon and electron-electron scattering on the intraband contribution to optical constants. Applying the simulated optical constants to the analysis of ultrafast heating of ruthenium thin films we highlight the importance of the latter scattering channel to understand the measured heating dynamics.

Cooling times in femtosecond pump-probe experiments of phase transitions with latent heat

Cooling times in femtosecond pump-probe experiments of phase transitions with latent heat

Protective action of graphene oxide against singlet oxygen generation by cosmetic dye methylene blue

Nanohybrid methylene blue/graphene oxide (MB/GO) was prepared via non-covalent functionalization with the focus on spectroscopic characterization of MB molecules adsorbed on GO. Fluorescence was not detected for the MB/GO hybrid which indicates that other competitive fast singlet excited state deactivation process must take place. It was demonstrated by measuring singlet oxygen (1O2) phosphorescence at 1270 nm that MB functionalized with GO does not generate 1O2. Nanosecond transient absorption spectroscopy experiments pointed to a lack of population of triplet state by MB/GO hybrid material. Femtosecond pump–probe experiments revealed much faster dynamics of the singlet excited state of MB/GO in comparison to free MB, which was attributed to the photoinduced electron transfer from MB to GO. Suppressing of the singlet oxygen quantum efficiency by MB upon functionalization to GO might be useful for designing graphene-based dye additives to color cosmetics with a reduced risk of the 1O2 generation on the skin.

Single-Color and Two-Color Femtosecond Pump–Probe Experiments on Graphitic Carbon Nitrides Revealing Their Charge Carrier Kinetics

Graphitic carbon nitride related materials have been one type of the most promising photocatalysts. Comprehensive understanding of their genuine charge carrier kinetic aspects will strengthen their photocatalytic applications. Herein, we synthesized two samples with different termination/functionalization groups, CN and NCN, and performed both single-color and two-color femtosecond pump–probe experiments on them. We found that both the recovery kinetics obtained from single-color femtosecond pump–probe experiments (SCFPPE) and the decay kinetics obtained from two-color femtosecond pump–probe experiments (TCFPPE) for CN and NCN display stronger pump fluence dependences, indicating that their genuine charge carrier kinetics should be measured under very low pump fluence. The charge carrier kinetics obtained under higher pump fluence would introduce a dramatically short picosecond component due to carrier–carrier interactions. With the obtained pump fluence-dependent charge carrier kinetics, for the first time, we derived the absorption cross section of CN and NCN at pump wavelength. The derived absorption cross section of CN at ∼398 nm is ∼5.2 × 10–15 cm2, and the derived absorption cross section of NCN at ∼398 nm is ∼8.3 × 10–15 cm2. Under very low pump fluence, we also found that the recovery kinetics of CN and NCN obtained from SCFPPE is obviously faster than their decay kinetics obtained from TCFPPE, suggesting that an additional fast decay photophysical process of CN and NCN might not be detected in TCFPPE. On the base of those femtosecond studies, we proposed a model for CN and NCN to understand how the pump fluence affect their charge carrier kinetics. We also discussed how the introduced termination/functionalization group in CN and NCN affects their genuine charge carrier kinetics so as to modify their photocatalytic hydrogen production activities. FTIR, XPS, XRD, and SEM EDX of CN and NCN were also measured for characterizing their chemical compositions and structures.

Understanding structure–properties relationships of porphyrin linked to graphene oxide through π–π-stacking or covalent amide bonds

Two graphene oxide nanoassemblies using 5-(4-(aminophenyl)-10,15,20-triphenylporphyrin (TPPNH2) were fabricated by two synthetic methods: covalent (GO-CONHTPP) and noncovalent bonding. GO-CONHTPP was achieved through amide formation at the periphery of GO sheets and the hybrid material was fully characterized by FTIR, XPS, Raman spectroscopy, and SEM. Spectroscopic measurements together with theoretical calculations demonstrated that assembling TPPNH2 on the GO surface in DMF-H2O (1:2, v/v) via non-covalent interactions causes changes in the absorption spectra of porphyrin, as well as efficient quenching of its emission. Interestingly, covalent binding to GO does not affect notably neither the porphyrin absorption nor its fluorescence. Theoretical calculations indicates that close proximity and π–π-stacking of the porphyrin molecule with the GO sheet is possible only for the non-covalent functionalization. Femtosecond pump–probe experiments revealed that only the non-covalent assembly of TPPNH2 and GO enhances the efficiency of the photoinduced electron transfer from porphyrin to GO. In contrast to the non-covalent hybrid, the covalent GO-CONHTPP material can generate singlet oxygen with quantum yields efficiency (ΦΔ = 0.20) comparable to that of free TPPNH2 (ΦΔ = 0.26), indicating the possible use of covalent hybrid materials in photodynamic/photothermal therapy. The spectroscopic studies combined with detailed quantum-chemical analysis provide invaluable information that can guide the fabrication of hybrid materials with desired properties for specific applications.

Ultrafast resonant exciton-plasmon coupling for enhanced emission in lead halide perovskite with metallic Ag nanostructures.

Integrating metal halide perovskites onto plasmonic nanostructures has recently become a trending method of enabling superior emissive performance of perovskite nanophotonic devices. In this work, we present an in-depth study on the spontaneous emission properties of hybrid systems comprising CsPbBr3 nanocrystals and silver nanostructures. Specifically, a 5.7-fold increment of the photoluminescence (PL) intensity and a 1.65-fold enhancement of the PL relaxation rate is attained when the transition energy of CsPbBr3 is spectrally resonant with the oscillational frequency of Ag nanodisks (NDs), which is attributed to the intense exciton-plasmon coupling-induced Purcell effect. Furthermore, a 540-fs ultrafast energy transfer from the CsPbBr3 excitons to Ag plasmons is revealed by femtosecond pump-probe experiments, suggesting the key mechanism responsible for the Purcell-enhanced radiative emission. Our finding offers a unique understanding of the enhanced emissive behavior in the plasmon-coupled perovskite system and paves the way for further applications.

Spin-Valley Depolarization in van der Waals Heterostructures.

The appearance of van der Waals heterostructures offers a new solution to valleytronics. Here, we observe the spin-valley depolarization process of electrons and holes in type-II MoS2-WSe2 heterostructures simultaneously for the first time by valley-resolved broad-band femtosecond pump-probe experiments. The different depolarization paths between electrons and holes make them have different spin-valley polarization lifetimes. The spin-valley depolarization pathway of holes is mainly dominated by a phonon-assisted intervalley scattering process, while intra- and intervalley coupling can trigger additional depolarization pathways for electrons. The hole polarization lifetime can be further prolonged to more than three times in trilayer heterostructure 2MoS2-WSe2. For MoS2-WS2 that has strong orbital hybridization of Mo and W atoms, both electrons and holes lose the spin-valley polarization extremely soon after charge separation, behaving similarly to intraexcitons in a monolayer. Our work advances the basic understanding of spin-valley depolarization of van der Waals heterostructures and facilitates the effort toward longer lifetime valleytronic devices for information transfer and storage applications.

Electron-phonon scattering in β -Ga2O3 studied by ultrafast transmission spectroscopy

Femtosecond pump-probe experiments in a transmission geometry were performed on Sn-doped n-type β-Ga2O3. With the pump and probe wavelengths below the bandgap, the differential transmission signal was determined by the free electron dynamics. Differential transmission decay times and their spectral dependence were used to evaluate electron-phonon scattering for polar optical (PO) and intervalley phonons. The obtained average electron-PO phonon scattering time is 4.5 ± 0.4 fs, while the electron scattering to and from the side valley is 80 ± 5 fs. The energy between the absolute and second lowest conduction band minima is estimated to be 2.6 ± 0.1 eV.

Through bonds or contacts? Mapping protein vibrational energy transfer using non-canonical amino acids

Vibrational energy transfer (VET) is essential for protein function. It is responsible for efficient energy dissipation in reaction sites, and has been linked to pathways of allosteric communication. While it is understood that VET occurs via backbone as well as via non-covalent contacts, little is known about the competition of these two transport channels, which determines the VET pathways. To tackle this problem, we equipped the β-hairpin fold of a tryptophan zipper with pairs of non-canonical amino acids, one serving as a VET injector and one as a VET sensor in a femtosecond pump probe experiment. Accompanying extensive non-equilibrium molecular dynamics simulations combined with a master equation analysis unravel the VET pathways. Our joint experimental/computational endeavor reveals the efficiency of backbone vs. contact transport, showing that even if cutting short backbone stretches of only 3 to 4 amino acids in a protein, hydrogen bonds are the dominant VET pathway.

Time-Resolved Observation of the Solvation Dynamics of a Rydberg Excited Molecule Deposited on an Argon Cluster. II. DABCO☆ at Long Time Delays.

The real-time dynamics of DABCO-argon clusters is investigated in a femtosecond pump-probe experiment where the pump excites DABCO to the S1 state within the argon cluster. The probe operates by photoionization and documents the energy and angular distributions of the resulting photoelectrons. The present work complements a previous work from our group [Awali Phys. Chem. Chem. Phys., 2014, 16, 516-526] where this dynamics was probed at short time, up to 4 ps after the pump pulse. Here, the dynamics is followed up to 500 ps. A multiscale dynamics is observed. It includes a jump between two solvation sites (time scale 0.27 ps) followed by the relaxation of the solvation cage excess vibrational energy (time scale 14 ps) and then by that of DABCO (time scale >150 ps). Polarization anisotropy, double polarization, and angular anisotropy effects are reported also. They are interpreted (quantitatively for the former effect) in terms of decoherence of rotational alignment, driven by the overall rotation of the DABCO-argon clusters. A tomographic view of the DABCO excited orbital, provided by the double anisotropy effect, is discussed on a qualitative basis.

Reexamination of electron-phonon coupling constant in continuum model by comparison with Boltzmann transport theory

The electron-phonon (e-ph) coupling process in ultrafast dynamics involves non-equilibrium effects including non-thermalized electrons and temporal non-equilibrium between different phonon branches. During such process, the two-temperature model (TTM) is employed to extract the relevant e-ph coupling constant though experiments themselves have demonstrated the invalidity of TTM. In this work, through fitting the results of Boltzmann transport theory by that of TTM, we quantitatively investigate the influence of the non-equilibrium effects on extraction of the e-ph coupling constant in TTM. The extracted e-ph coupling constant will be indeed underestimated yet not significantly by about 7% under the influence of non-equilibrium between different phonon branches for Au, Ag. Additionally, when the excitation pulse width is comparable to the e-ph relaxation time of electrons, non-thermalized electrons exists after excitation and thus the extracted e-ph coupling constant in TTM shows over 20% deviation. Therefore, the excitation pulse width is required to be larger than 300 fs and 500 fs for Au, Ag, respectively at room temperature if the error is controlled within 10%. This work will provide insightful indication for the measurement of the e-ph coupling constant in femtosecond pump-probe experiments.

Nonequilibrium effects on the electron-phonon coupling constant in metals

Understanding of the energy exchange between electrons and phonons in metals is important for micro- and nano-manufacturing and system design. The electron-phonon (e-ph) coupling constant is to describe such exchange strength, yet its variation remains still unclear at micro- and nanoscale where the non-equilibrium effects are significant. In this work, an e-ph coupling model is proposed by transforming the full scattering terms into relaxation time approximation forms in the coupled electron and phonon Boltzmann transport equations. Consequently, the non-equilibrium effects are included in the calculation of e-ph coupling constant. The coupling model is verified by modeling the ultrafast dynamics in femtosecond pump-probe experiments on metal surface, which shows consistent results with the full integral treatment of scattering terms. The e-ph coupling constant is strongly reduced due to both the temporal non-equilibrium between different phonon branches and the spatial non-equilibrium of electrons in confined space. The present work will promote not only a fundamental understanding of the e-ph coupling constant but also the theoretical description of coupled electron and phonon transport at micro- and nanoscale.

Near-field imaging of femtosecond propagating surface plasmon and regulation of excitation efficiency

Near-field imaging and active control of excitation efficiency of femtosecond propagating surface plasmon (fs-PSP) are the prerequisites for its application. Here, we perform near-field imaging of fs-PSP excited at the trench etched on silver nano-film by using photoemission electron microscopy (PEEM). As an excellent near-field microscopy technique of in situ imaging with a high spatial resolution (< 20 nm), it needs neither molecular reporters nor scanning probes as required in nonlinear fluorescence microscopy in nonlinear fluorescence microscopy or scanning near-field optical microscopy, both of which may potentially bias PSP derived from such measurements. The period of the interference patterns induced by the incident femtosecond laser and the laser-induced fs-PSP and the wavelength of fs-PSP in a range of 720–900 nm of the incident laser wavelength are systematically measured. The fringe period of the interference pattern between fs-PSP and the incident laser is a range of 5.9–7.7 µm, and the wavelength of fs-PSP is in a range of 700–879 nm. The experimental results are consistent with the theoretical simulation results. Furthermore, we demonstrate that the excitation efficiency of fs-PSP can be actively controlled by adjusting the polarization direction of the incident laser in the femtosecond pump-probe experiments. Specifically, it is found that when the incident laser is polarized to 0° (p-polarization light), the excitation efficiency of PSP reaches a maximum value, and when the incident light is polarized to 90° (s-polarization light), the excitation efficiency of fs-PSP is the lowest. Unlike the simulation result by the finite difference time domain (FDTD) method, a plateau area of the intensity of the photoemission signal with the polarization direction of the incident laser appears in the femtosecond pump-probe experiment. This phenomenon is attributed to the background noise of the detection laser that masks the change of the fs-PSP excitation efficiency. In a word, this research realizes the experimental measurement of the basic parameters of fs-PSP and the manipulation of fs-PSP excitation efficiency by adjusting the polarization angle of the incident laser. This research lays a foundation for realizing the engineering manipulation of fs-PSP excitation efficiency and optimizing the performance of plasmonic devices.

Influence of coherent adiabatic excitation on femtosecond transient signals

Femtosecond laser pulses are the tools of choice for inducing and tracking the temporal evolution of electronic excitation in molecular systems. To obtain this information, a proper theoretical modeling of the observables monitored in these experiments is essential. Herein, we present a coherent approach to simulate the time-dependent signals that result from femtosecond pump-probe experiments with ionization detection. Thus, the transient signals derived from femtosecond pump-probe experiments are analyzed in terms of the coherent evolution of the energy levels perturbed by the excitation pulse. The model system is treated as the sum of independent two-level subsystems that evolve adiabatically or are permanently excited, depending on the detuning from the central wavelength of the excitation laser. This approach will allow us to explain numerically and analytically the convergence between the coherent and incoherent (rate equations) treatments for complex multi-level systems. It will be also shown that the parameter that determines the validity of the incoherent treatment is the distribution of states outside and inside the laser bandwidth, rather than the density of states as it is commonly accepted.

Excited State Dynamics of Isolated 6- and 8-Hydroxyquinoline Molecules.

The photoinduced dynamics of isolated n-hydroxyquinoline (nHQ) molecules (n=6,8) was investigated in femtosecond pump-probe experiments. A qualitative difference was found between 8HQ and 6HQ. After an initial rapid decay corresponding to the departure of the initial wavepacket out of the Franck-Condon region of the excitation, the 8HQ probe signal decays to zero in 0.37 ps whereas a much longer time constant of 10.4 ps is observed in 6HQ. This interrogates on the role played by the intramolecular H-bond N HO which is at play the 8HQ molecule. Ab-initio were performed at the MCSCF/aug-cc-pVDZ level on the 8HQ molecule to help the discussion. A complex energy landscape was found, which includes a conical intersection.

Observation of the femtosecond laser-induced ultrafast amorphization in Ge2Sb2Te5 films by dynamics spectrum

We demonstrate ultrafast amorphization in a Ge2Sb2Te5 (GST) film through a nonthermal process by femtosecond pump-probe experiments. A strong absorption peak in 532 nm is founded during the amorphization and the energy level corresponded is about 0.65~3.82 eV by calculations. First-Principles Calculations simulation experiments are used to prove the results of experiment and then explain the mechanism of amorphization of GST. Also, results of experiments show that the time to reach the absorption peak is decided by pulse width and wavelength but not the laser influence.

Nonlinear optical responses and ultrafast dynamics of three soluble ladder-conjugated molecules: A study on the terminal group effect

To study the structure-property relationship as well as the intramolecular charge transfer properties of typical ladder-conjugated molecules, three ladder-conjugated molecules named LT2, LT3 and BPTF-2 were systematically investigated by UV–vis absorption spectra and fluorescence spectra, the open-aperture Z-scan technique, two-photon excited fluorescence and femtosecond pump-probe experiments. These ladder-conjugated molecules employ the same fluorene group as the π-bridge and the central core, with substituent changes at the terminal position. These molecules exhibit a large two-photon absorption response and two molecules emit intense two-photon fluorescence at a wavelength of 800 nm, which is a commonly used wavelength in two-photon absorption/two-photon fluorescence applications. Our results indicate that the π-bridge and the terminal group play an important role in determining the two-photon absorption response. The dynamic results obtained from degenerated pump-probe experiments revealed that the evolution times of the intramolecular charge transfer state were >1000 ps, >1000 ps, and 40 ps for LT2, LT3 and BDTF-2, respectively. The results match those of the two-photon absorption responses and the fluorescence emission properties of these ladder-conjugated molecules. Our results also indicate that ladder-conjugated molecules have potential applications in two-photon absorption/two-photon fluorescence fields.

Coherent phonon dynamics in a c-plane sapphire crystal before and after intense femtosecond laser irradiation.

Femtosecond pump-probe experiments with a ∼6.4 fs time-resolution were performed to investigate the coherent phonon dynamics in a c-plane sapphire crystal before and after intense 800 nm femtosecond laser irradiation. The intense femtosecond laser induced defect/distortion and even re-crystallization of crystalline structures, which result in the appearance of new peaks and relative intensity change in coherent phonon and Raman spectra. The combination of these two spectra was found to be beneficial to evidence the variation of crystalline structure and further to differentiate the origins of new Raman peaks after irradiation. Further analysis of time-dependent differential absorbance with damped cosine function fitting and Fourier transfer calculation yields the vibrational parameters, including periods, damping times and initial phases, before and after irradiation. With these parameters, the defect-effects on damping time and the mechanism of coherent phonon generation were addressed.

Generation of exchange magnons in thin ferromagnetic films by ultrashort acoustic pulses

We investigate generation of exchange magnons by ultrashort, picosecond acoustic pulses propagating through ferromagnetic thin films. Using the Landau-Lifshitz-Gilbert equations we derive the dispersion relation for exchange magnons for an external magnetic field tilted with respect to the film normal. Decomposing the solution in a series of standing spin wave modes, we derive a system of ordinary differential equations and driven harmonic oscillator equations describing the dynamics of individual magnon mode. The external magnetoelastic driving force is given by the time-dependent spatial Fourier components of acoustic strain pulses inside the layer. Dependencies of the magnon excitation efficiencies on the duration of the acoustic pulses and the external magnetic field highlight the role of acoustic bandwidth and phonon-magnon phase matching. Our simulations for ferromagnetic nickel evidence the possibility of ultrafast magneto-acoustic excitation of exchange magnons within the bandwidth of acoustic pulses in thin samples under conditions readily obtained in femtosecond pump-probe experiments.