Two-color Pump-probe Experiments Research Articles

Determining the Orbital Angular Momentum of a Vortex Beam Using Strong Field Ionization

While interferometric methods exist for classifying vortex states of light, these techniques usually require destroying the beam of interest to determine the light’s OAM. A recent two-color pump-probe experiment employed strong field ionization and beam sculpting to classify vortex beams. Here, we propose an alternative strong-field method for distinguishing OAM states of light which does not require beam sculpting and instead utilizes a noncollinear terahertz standing wave to probe ionized electrons. We then use classical trajectory Monte Carlo (CTMC) methods to simulate strong-field ionization of helium under this configuration with the terahertz field both on and off. We find that the resulting electron momenta distributions can be used to extract the OAM of the beam, as long as the vortex beam spot size does not exceed 1/4 the terahertz pulse’s wavelength.

Cavity-dumping a single infrared pulse from a free-electron laser for two-color pump-probe experiments.

Electromagnetic radiation in the mid- to far-infrared spectral range represents an indispensable tool for the study of numerous types of collective excitations in solids and molecules. Short and intense pulses in this terahertz spectral range are, however, difficult to obtain. While wide wavelength-tunability is easily provided by free-electron lasers, the energies of individual pulses are relatively moderate, on the order of microjoules. Here, we demonstrate a setup that uses cavity-dumping of a free-electron laser to provide single, picosecond-long pulses in the mid- to far-infrared frequency range. The duration of the Fourier-limited pulses can be varied by cavity detuning, and their energy was shown to exceed 100 µJ. Using the aforementioned infrared pulse as a pump, we have realized a two-color pump-probe setup facilitating single-shot time-resolved imaging of magnetization dynamics. We demonstrate the capabilities of the setup first on thermally induced demagnetization and magnetic switching of a GdFeCo thin film and second by showing a single-shot time-resolved detection of resonant phononic switching of the magnetization in a magnetic garnet.

Synchronized beamline at FLASH2 based on high-order harmonic generation for two-color dynamics studies.

We present the design, integration, and operation of the novel vacuum ultraviolet (VUV) beamline installed at the free-electron laser (FEL) FLASH. The VUV source is based on high-order harmonic generation (HHG) in gas and is driven by an optical laser system synchronized with the timing structure of the FEL. Ultrashort pulses in the spectral range from 10 to 40eV are coupled with the FEL in the beamline FL26, which features a reaction microscope (REMI) permanent endstation for time-resolved studies of ultrafast dynamics in atomic and molecular targets. The connection of the high-pressure gas HHG source to the ultra-high vacuum FEL beamline requires a compact and reliable system, able to encounter the challenging vacuum requirements and coupling conditions. First commissioning results show the successful operation of the beamline, reaching a VUV focused beam size of about 20 µm at the REMI endstation. Proof-of-principle photo-electron momentum measurements in argon indicate the source capabilities for future two-color pump-probe experiments.

Asymmetric Rydberg blockade of giant excitons in Cuprous Oxide

The ability to generate and control strong long-range interactions via highly excited electronic states has been the foundation for recent breakthroughs in a host of areas, from atomic and molecular physics to quantum optics and technology. Rydberg excitons provide a promising solid-state realization of such highly excited states, for which record-breaking orbital sizes of up to a micrometer have indeed been observed in cuprous oxide semiconductors. Here, we demonstrate the generation and control of strong exciton interactions in this material by optically producing two distinct quantum states of Rydberg excitons. This is made possible by two-color pump-probe experiments that allow for a detailed probing of the interactions. Our experiments reveal the emergence of strong spatial correlations and an inter-state Rydberg blockade that extends over remarkably large distances of several micrometers. The generated many-body states of semiconductor excitons exhibit universal properties that only depend on the shape of the interaction potential and yield clear evidence for its vastly extended-range and power-law character.

Space- and time-resolved UV-to-NIR surface spectroscopy and 2D nanoscopy at 1 MHz repetition rate.

We describe a setup for time-resolved photoemission electron microscopy with aberration correction enabling 3 nm spatial resolution and sub-20 fs temporal resolution. The latter is realized by our development of a widely tunable (215-970 nm) noncollinear optical parametric amplifier (NOPA) at 1 MHz repetition rate. We discuss several exemplary applications. Efficient photoemission from plasmonic Au nanoresonators is investigated with phase-coherent pulse pairs from an actively stabilized interferometer. More complex excitation fields are created with a liquid-crystal-based pulse shaper enabling amplitude and phase shaping of NOPA pulses with spectral components from 600 to 800 nm. With this system we demonstrate spectroscopy within a single plasmonic nanoslit resonator by spectral amplitude shaping and investigate the local field dynamics with coherent two-dimensional (2D) spectroscopy at the nanometer length scale ("2D nanoscopy"). We show that the local response varies across a distance as small as 33 nm in our sample. Further, we report two-color pump-probe experiments using two independent NOPA beamlines. We extract local variations of the excited-state dynamics of a monolayered 2D material (WSe2) that we correlate with low-energy electron microscopy (LEEM) and reflectivity measurements. Finally, we demonstrate the in situ sample preparation capabilities for organic thin films and their characterization via spatially resolved electron diffraction and dark-field LEEM.

Physical mechanisms encoded in photoionization yield from IR+XUV setups

We theoretically examine how and to which extent physical processes can be retrieved from two-color pump-probe experiments of atomic and molecular gases driven by an attosecond XUV pulse train and an infrared (IR) pulse. The He atom, the N2 molecule and Na clusters are investigated with time-dependent density functional theory. Results are interpreted on the basis of a simple model system. We consider observables most commonly used in experiments: ionization yield, photo-electron spectra, and angular distributions. We find that the basic time-dependent signatures are dominated by the interplay of IR laser and continuum electrons. System information, contained in the signal, will in general require careful disentangling from the effects of photon-electron dynamics.Graphical abstract

Tracing charge transfer in argon dimers by XUV-pump IR-probe experiments at FLASH.

Charge transfer (CT) at avoided crossings of excited ionized states of argon dimers is observed using a two-color pump-probe experiment at the free-electron laser in Hamburg (FLASH). The process is initiated by the absorption of three 27-eV-photons from the pump pulse, which leads to the population of Ar2+*-Ar states. Due to nonadiabatic coupling between these one-site doubly ionized states and two-site doubly ionized states of the type Ar+*-Ar+, CT can take place leading to the population of the latter states. The onset of this process is probed by a delayed infrared (800 nm) laser pulse. The latter ionizes the dimers populating repulsive Ar2+ -Ar+ states, which then undergo a Coulomb explosion. From the delay-dependent yields of the obtained Ar2+ and Ar+ ions, the lifetime of the charge-transfer process is extracted. The obtained experimental value of (531 ± 136) fs agrees well with the theoretical value computed from Landau-Zener probabilities.

Delayed Relaxation of Highly Excited Cationic States in Naphthalene.

Rapid energy transfer from electronic to nuclear degrees of freedom underlies many biological processes and astrophysical observations. The efficiency of this energy transfer depends strongly on the complex interplay between electronic and nuclear motions. In this study, we report two-color pump-probe experiments that probe the relaxation dynamics of highly excited cationic states of naphthalene, a prototypical polycyclic aromatic hydrocarbon molecule, which are produced using wavelength-selected, ultrashort extreme ultraviolet pulses. Surprisingly, the relaxation lifetimes increase with the cationic excitation energy. We postulate that the observed effect is the result of a population trapping that leads to delayed relaxation.

Acoustic Far-Field Hypersonic Surface Wave Detection with Single Plasmonic Nanoantennas.

The optical properties of small metallic particles allow us to bridge the gap between the myriad of subdiffraction local phenomena and macroscopic optical elements. The optomechanical coupling between mechanical vibrations of Au nanoparticles and their optical response due to collective electronic oscillations leads to the emission and the detection of surface acoustic waves (SAWs) by single metallic nanoantennas. We take two Au nanoparticles, one acting as a source and the other as a receptor of SAWs and, even though these antennas are separated by distances orders of magnitude larger than the characteristic subnanometric displacements of vibrations, we probe the frequency content, wave speed, and amplitude decay of SAWs originating from the damping of coherent mechanical modes of the source. Two-color pump-probe experiments and numerical methods reveal the characteristic Rayleigh wave behavior of emitted SAWs, and show that the SAW-induced optical modulation of the receptor antenna allows us to accurately probe the frequency of the source, even when the eigenmodes of source and receptor are detuned.

Development of a hard X-ray split-and-delay line and performance simulations for two-color pump-probe experiments at the European XFEL.

A hard X-ray Split-and-Delay Line (SDL) under construction for the Materials Imaging and Dynamics station at the European X-Ray Free-Electron Laser (XFEL) is presented. This device aims at providing pairs of X-ray pulses with a variable time delay ranging from -10 ps to 800 ps in a photon energy range from 5 to 10 keV for photon correlation and X-ray pump-probe experiments. A custom designed mechanical motion system including active feedback control ensures that the high demands for stability and accuracy can be met and the design goals achieved. Using special radiation configurations of the European XFEL's SASE-2 undulator (SASE: Self-Amplified Spontaneous Emission), two-color hard x-ray pump-probe schemes with varying photon energy separations have been proposed. Simulations indicate that more than 109 photons on the sample per pulse-pair and up to about 10% photon energy separation can be achieved in the hard X-ray region using the SDL.

Ultrafast responses of two V-shaped compounds with a reverse conjugated structural configuration: an investigation of the reason for the enhanced two-photon absorption cross-section

To study the effect of the conjugated structural configuration on the two-photon absorption (TPA) properties of V-shaped compounds, two 1,3,5-triazine-based compounds with the same electron donor (D) and acceptor (A) connected in a reverse-conjugated structural configuration (T02: D- $$\pi$$ -A- $$\pi$$ -D; R02: A- $$\pi$$ -D- $$\pi$$ -A) were systematically investigated using steady-state and transient absorption spectroscopy, open-aperture Z-scan measurements, and two-photon fluorescence measurements. The TPA cross-section of compound R02 connected in a A- $$\pi$$ -D- $$\pi$$ -A-conjugated structural configuration with triphenylamine as the central core was 203 GM, which showed a 2.3-fold enhancement compared with compound T02 connected in a reverse D- $$\pi$$ -A- $$\pi$$ -D-conjugated structural configuration (90 GM, with 1,3,5-triazine as the central core). This result indicates that the conjugated structural configuration plays an important role in the TPA properties. A two-color pump–probe experiment was used to investigate the effect of the conjugated structural configuration on the excited state and intra-molecular charge transfer (ICT) properties of these V-shaped compounds. The formation and relaxation lifetimes of the ICT state were determined. The results indicate that the electron-donating/accepting strength of the central group, which serves as a communal group for two D- $$\pi$$ -A subunits, was confirmed to be a key role to the overall effect of the ICT for V-shaped compounds. These ultrafast dynamic results are in agreement with the TPA properties.

Ultrafast dynamics of a series multi-branched styryl derivatives with reverse conjugated structural configuration

To study the effect of conjugated structural configurations on the two-photon absorption properties, tri-branched compounds with the same electron-donating and electron-accepting groups connected in a reverse conjugated structural mode, are systematically investigated using steady-state and transient absorption spectroscopies, open-aperture Z-scan, and two-photon fluorescence measurements. The two-photon absorption cross-section of compound R03 with the strong electron donor triphenylamine as the central core of 766 GM is notably large and is approximately 1.7 times larger than that of the tri-branched compound T03-a with a reverse conjugated structural mode and with the 1,3,5-triazine electron acceptor as the central core. This finding indicates that the conjugated mode does have an important effect on the nonlinear optical properties. A two-color pump-probe experiment is used to investigate the ultrafast responses and intra-molecular charge transfer properties of these multi-branched compounds. The form...

Theory of multiexciton dynamics in molecular chains

Ultrafast and strong optical excitation of a molecular system is considered which is formed by a regular one-dimensional arrangement of identical molecules. As it is typical for zinc chlorine-type molecules the transition energy from the ground state to the first excited singlet state is assumed to be smaller than the energy difference between the first excited state and the following one. This enables the creation of many excitons without their immediate quenching due to exciton-exciton annihilation. As a first step into the field of dense Frenkel-exciton systems the present approach stays at a mean-field type of description and ignores vibrational contributions. The resulting nonlinear kinetic equations mix Rabi-type oscillations with those caused by energy transfer and suggest an excitation-dependent narrowing of the exciton band. The indication of this effect in the framework of a two-color pump-probe experiment and of the detection of photon emission is discussed.

Ultrafast vibrational energy flow in water monomers in acetonitrile

Vibrational relaxation of the OH stretching and bending modes of water monomers in acetonitrile is studied by two-color pump–probe experiments in a frequency range from 1400 to 3800cm−1. Measurements with resonant infrared excitation reveal vibrational lifetimes of 6.4±1.0ps of the OH stretching modes and 4.0±0.5ps of the OH bending mode. After OH stretching excitation, the OH bending mode shows an instantaneous response, a hallmark of the anharmonic coupling of stretching and bending modes, and a delayed population buildup by relaxation of the stretching via the bending mode. The relaxation steps are discussed within the framework of current theoretical pictures of water’s vibrational relaxation.

Theoretical Study of Ultrafast Electron Dynamics in Amino Acids

SynopsisPrompt ionization of large biological molecules may induce ultrafast charge migration along the molecular skeleton, preceding any nuclear rearrangement. This phenomenon has been recently observed in the amino acid phenylalanine in a two-color pump probe experiment, where the production of ionic fragments was measured as a function of the time delay between the two pulses and charge fluctuations manifested as sub-4.5 fs oscillations in the quantum yield of a specific doubly charged fragment. We present our latest results in glycine, and compare with previous findings in phenylalanine. We seek to perform a systematic study including larger aminoacids such as tryptophan.

Crossed excitons in a semiconductor nanostructure of mixed dimensionality

Semiconductor systems of reduced dimensionality, e.g., quantum dots or quantum wells, display a characteristic spectrum of confined excitons. Combining several of these systems may lead to the formation of “crossed” excitons, and thus new equilibrium states and scattering channels. We derive gain excitation spectra from two-color pump-probe experiments on an In(Ga)As based quantum dot semiconductor optical amplifier by analyzing the amplitudes of the traces. This grants access to the quantum dot response, even in the presence of strong absorption by the surroundings at the excitation energy. The gain excitation spectra yield evidence of crossed quantum dot-bulk states.

Ultrafast vibrational dynamics of BH4(-) ions in liquid and crystalline environments.

Ultrafast vibrational dynamics of BH4(-) ions, the key units in boron hydride materials for hydrogen storage, are studied in diluted polar liquid solution and in NaBH4 crystallites by femtosecond infrared spectroscopy. Two-color pump-probe experiments reveal v = 1 lifetimes of 3 ps for the asymmetric BH4(-) stretching mode ν3 and of 3.6 ps for the asymmetric bending mode ν4 in the solvent isopropylamine. We provide direct evidence for the BH4(-) stretching relaxation pathway via the asymmetric bending mode ν4 by probing the latter after femtosecond excitation of ν3. Pump-probe traces measured in the crystalline phase show signatures of radiative coupling between the densely packed BH4(-) oscillators, most clearly manifested in an accelerated subpicosecond depopulation of the v = 1 state of the ν4 mode. The radiative decay is followed by incoherent vibrational relaxation similar to the liquid phase. The excess energy released in the relaxation processes of the BH4(-) intramolecular modes is transferred into the environment with thermal pump-probe signals being much more pronounced in the dense solid than in the diluted solution.

Gain dynamics of quantum dot devices for dual-state operation

Ground state gain dynamics of In(Ga)As-quantum dot excited state lasers are investigated via single-color ultrafast pump-probe spectroscopy below and above lasing threshold. Two-color pump-probe experiments are used to localize lasing and non-lasing quantum dots within the inhomogeneously broadened ground state. Single-color results yield similar gain recovery rates of the ground state for lasing and non-lasing quantum dots decreasing from 6 ps to 2 ps with increasing injection current. We find that ground state gain dynamics are influenced solely by the injection current and unaffected by laser operation of the excited state. This independence is promising for dual-state operation schemes in quantum dot based optoelectronic devices.

Nonlinear spectroscopy in the near-field: time resolved spectroscopy and subwavelength resolution non-invasive imaging

AbstractThe combination of near-field microscopy along with nonlinear optical spectroscopic techniques is presented here. The scanning near-field imaging technique can be integrated with nonlinear spectroscopic techniques to improve spatial and axial resolution of the images. Additionally, ultrafast dynamics can be probed down to nano-scale dimension. The review shows some examples for this combination, which resulted in an exciton map and vibrational contrast images with sub-wavelength resolution. Results of two-color femtosecond time-resolved pump-probe experiments using scanning near-field optical microscopy (SNOM) on thin films of the organic semiconductor 3,4,9,10 Perylenetetracarboxylic dianhydride (PTCDA) are presented. While nonlinear Raman techniques have been used to obtain highly resolved images in combination with near-field microscopy, the use of femtosecond laser pulses in electronic resonance still constitutes a big challenge. Here, we present our first results on coherent anti-Stokes Raman scattering (fs-CARS) with femtosecond laser pulses detected in the near-field using SNOM. We demonstrate that highly spatially resolved images can be obtained from poly(3-hexylthiophene) (P3HT) nano-structures where the fs-CARS process was in resonance with the P3HT absorption and with characteristic P3HT vibrational modes without destruction of the samples. Sub-diffraction limited lateral resolution is achieved. Especially the height resolution clearly surpasses that obtained with standard microCARS. These results will be the basis for future investigations of mode-selective dynamics in the near-field.

Strong Terahertz Emission and Its Origin from Catalyst-Free InAs Nanowire Arrays

The unique features of nanowires (NW), such as the high aspect ratio and extensive surface area, are expected to play a key role in the development of very efficient semiconductor surface emitters in the terahertz (THz) spectral range. Here, we report on optically excited THz emission from catalyst-free grown arrays of intrinsically n-type InAs NWs using THz time-domain spectroscopy. Depending on the aspect ratio, the THz emission efficiency of the n-type InAs NWs is found to be up to ∼3 times stronger than that of bulk p-type InAs, known as currently the most efficient semiconductor-based THz surface emitter. Characteristic differences from bulk p-type InAs are particularly revealed from excitation wavelength-dependent measurements, showing monotonously increasing THz pulse amplitude in the NW arrays with increasing photon energy. Further polarization-dependent and two-color pump-probe experiments elucidate the physical mechanism of the THz emission: In contrast to bulk p-type InAs, where the anisotropic photoconductivity in the surface electric field is the dominant cause for THz pulse generation, the origin of the intrinsic THz emission in the NWs is based on the photo-Dember effect. The strong THz emission from high aspect ratio NW arrays further suggests an improved out-coupling of the radiation, while further enhancements in efficiency using core-shell NW geometries are discussed.