Pump-probe Approach Research Articles

Optically Probing Unconventional Superconductivity in Atomically Thin Bi2Sr2Ca0.92Y0.08Cu2O8+δ.

Atomically thin cuprates exhibiting a superconducting phase transition temperature similar to that of the bulk have recently been realized, although the device fabrication remains a challenge and limits the potential for many novel studies and applications. Here, we use an optical pump-probe approach to noninvasively study the unconventional superconductivity in atomically thin Bi2Sr2Ca0.92Y0.08Cu2O8+δ (Y-Bi2212). Apart from finding an optical response due to the superconducting phase transition that is similar to that of bulk Y-Bi2212, we observe that the sign and amplitude of the pump-probe signal in atomically thin flakes vary significantly in different dielectric environments depending on the nature of the optical excitation. By exploiting the spatial resolution of the optical probe, we uncover the exceptional sensitivity of monolayer Y-Bi2212 to the environment. Our results provide the first optical evidence for the intralayer nature of the superconducting condensate in Bi2212 and highlight the role of double-sided encapsulation in preserving superconductivity in atomically thin cuprates.

A redox switch allows binding of Fe(II) and Fe(III) ions in the cyanobacterial iron-binding protein FutA from Prochlorococcus

The marine cyanobacterium Prochlorococcus is a main contributor to global photosynthesis, whilst being limited by iron availability. Cyanobacterial genomes generally encode two different types of FutA iron-binding proteins: periplasmic FutA2 ABC transporter subunits bind Fe(III), while cytosolic FutA1 binds Fe(II). Owing to their small size and their economized genome Prochlorococcus ecotypes typically possess a single futA gene. How the encoded FutA protein might bind different Fe oxidation states was previously unknown. Here, we use structural biology techniques at room temperature to probe the dynamic behavior of FutA. Neutron diffraction confirmed four negatively charged tyrosinates, that together with a neutral water molecule coordinate iron in trigonal bipyramidal geometry. Positioning of the positively charged Arg103 side chain in the second coordination shell yields an overall charge-neutral Fe(III) binding state in structures determined by neutron diffraction and serial femtosecond crystallography. Conventional rotation X-ray crystallography using a home source revealed X-ray-induced photoreduction of the iron center with observation of the Fe(II) binding state; here, an additional positioning of the Arg203 side chain in the second coordination shell maintained an overall charge neutral Fe(II) binding site. Dose series using serial synchrotron crystallography and an XFEL X-ray pump-probe approach capture the transition between Fe(III) and Fe(II) states, revealing how Arg203 operates as a switch to accommodate the different iron oxidation states. This switching ability of the Prochlorococcus FutA protein may reflect ecological adaptation by genome streamlining and loss of specialized FutA proteins.

S Hmax orientation in the Alpine region from observations of stress-induced anisotropy of nonlinear elasticity

SUMMARY The orientation of SHmax is commonly estimated from in situ borehole breakouts and earthquake focal mechanisms. Borehole measurements are expensive, and therefore sparse, and earthquake measurements can only be made in regions with many well-characterized earthquakes. Here, we derive the stress-field orientation using stress-induced anisotropy in nonlinear elasticity. In this method, we measure the strain derivative of velocity as a function of azimuth. We use a natural pump-probe (NPP) approach which consists of measuring elastic wave speed using empirical Green’s functions (probe) at different points of the earth tidal strain cycle (pump). The approach is validated using a larger data set in the Northern Alpine Foreland region where the orientation of maximum horizontal compressive stress is known from borehole breakouts and drilling-induced fractures. The technique resolves NNW-SSW to N-S directed SHmax which is in good agreement with conventional methods and the recent crustal stress model. We confirm that the NPP method can be applied to dense large-scale seismic arrays. The technique is then applied to the Southern Alps to understand the contemporary stress pattern associated with the ongoing deformation due to counterclockwise rotation of the Adriatic plate with respect to the European plate. Our results explain why the two major faults in Northeastern Italy, the Giudicarie Fault and the Periadriatic Line (Pustertal–Gailtal Fault) are currently inactive, while the currently acting stress field allows faults in Slovenia to deform actively. We have demonstrated that the pump-probe method has the potential to fill in the measurement gap left by conventional approaches, both in terms of regional coverage and in depth.

Broadband Two-Photon Absorption Spectroscopy with Stimulated Raman Scattering as an Internal Standard.

Two-photon absorption (2PA) spectroscopy provides valuable information about the nonlinear properties of molecules. In contrast with single-wavelength methods, broadband 2PA spectroscopy using a pump-probe approach gives a continuous 2PA spectrum across a wide range of transition energies without tuning the excitation laser. This contribution shows how stimulated Raman scattering from the solvent can be used as a convenient and robust internal standard for obtaining accurate absolute 2PA cross sections using the broadband approach. Stimulated Raman scattering has the same pump-probe overlap dependence as 2PA, thus eliminating the need to measure the intensity-dependent overlap of the pump and probe directly. Eliminating the overlap represents an important improvement because intensity profiles are typically the largest source of uncertainty in the measurement of absolute 2PA cross sections using any method. Raman scattering cross sections are a fundamental property of the solvent and therefore provide a universal standard that can be applied any time the 2PA and Raman signals are present within the same probe wavelength range. We demonstrate this approach using sample solutions of coumarin 153 in methanol, DMSO, and toluene, as well as fluorescein in water.

Free electron laser stochastic spectroscopy revealing silicon bond softening dynamics

Time-resolved x-ray emission/absorption spectroscopy (Tr-XES/XAS) is an informative experimental tool sensitive to electronic dynamics in materials, widely exploited in diverse research fields. Typically, Tr-XES/XAS requires x-ray pulses with both a narrow bandwidth and subpicosecond pulse duration, a combination that in principle finds its optimum with Fourier transform-limited pulses. In this work, we explore an alternative experimental approach, capable of simultaneously retrieving information about unoccupied (XAS) and occupied (XES) states from the stochastic fluctuations of broadband extreme ultraviolet pulses of a free electron laser. We used this method, in combination with singular-value decomposition and Tikhonov regularization procedures, to determine the XAS/XES response from a crystalline silicon sample at the ${L}_{2,3}$ edge, with an energy resolution of a few tens of meV. Finally, we combined this spectroscopic method with a pump-probe approach to measure structural and electronic dynamics of a silicon membrane. Tr-XAS/XES data obtained after photoexcitation with an optical laser pulse at 390 nm allowed us to observe perturbations of the band structure, which are compatible with the formation of the predicted precursor state of a nonthermal solid-liquid phase transition associated with a bond softening phenomenon.

Selective Detection in Impulsive Low-Frequency Raman Imaging Using Shaped Probe Pulses

Impulsive stimulated Raman scattering (ISRS) using a single short femtosecond pump pulse to excite molecular vibrations offers an elegant pump-probe approach to perform vibrational imaging below $200\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$. One shortcoming of ISRS is its inability to offer vibrational selectivity as all the vibrational bonds whose frequencies lie within the short pump-pulse bandwidth are excited. To date, several coherent control techniques have been explored to address this issue and selectively excite a specific molecular vibration by shaping the pump pulse. There has not been any systematic work that reports an analogous shaping of the probe pulse to implement preferential detection. In this work, we focus on vibrational imaging and report vibrational selective detection by shaping the probe pulse in time. We demonstrate numerically and experimentally two pulse-shaping strategies with one functioning as a vibrational notch filter and the other functioning as a vibrational low-pass filter. This enables fast ($25\phantom{\rule{0.2em}{0ex}}\text{\ensuremath{\mu}}\mathrm{s}/$pixel) and selective hyperspectral imaging in the low-frequency regime ($<200\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$).

Single-Shot Reconfigurable Femtosecond Imaging of Ultrafast Optical Dynamics.

Understanding ultrafast dynamics in the femtosecond timescale plays a pivotal role in fundamental research and technology innovation. Spatiotemporal observation of those events in real-time requires imaging speeds greater than 1012 frames per second (fps), far beyond the fundamental speed limits of the ubiquitous semiconductor sensor technologies. In addition, a majority of femtosecond events are non-repeatable or difficult-to-repeat since they either work in a highly unstable nonlinear regime or require extreme or rare conditions to initiate. Therefore, the traditional pump-probe imaging approach fails since it heavily depends on precise event repetition. Single-shot ultrafast imaging emerges as the only solution; however, existing techniques cannot reach more than 15×1012 fps, and they only record an insufficient number of frames. Compressed ultrafast spectral photography (CUSP) is proposed to overcome these limitations. Here, CUSP's full design space is explored by manipulating the ultrashort optical pulse in the active illumination. Via parameter optimization, an extraordinarily fast frame rate of 219×1012 fps is achieved. This implementation of CUSP is also highly flexible, allowing various combinations of imaging speeds and numbers of frames (several hundred up to 1000) to be readily deployed in diverse scientific studies, such as laser-induced transient birefringence, self-focusing, and filaments in dielectric media.

Understanding contact acoustic nonlinearity through coupled synchrotron x-ray imaging and dynamic acoustoelastic measurements under stress

Dynamic acoustoelastic testing (DAET) is a vibro-acoustic technique, which has been used to measure acoustic nonlinearity in disparate solid media. DAET is a pump-probe approach, where the strain pump-induced changes in the elastic properties of the medium are monitored by a pair of ultrasonic probes at frequencies much higher than that of the strain pump. In a fractured/cracked medium, the measured changes in the elastic properties are attributed to fracture breathing (opening/closing) or shearing caused by the low-frequency pumping. In a set of unprecedent experiments, we use time-lapse synchrotron x-ray imaging in tandem with quasi-static loading/unloading and DAET to visualize the fast dynamics mechanisms in four different materials systems under various stress levels. These include two samples with localized CAN: fractured Westerly granite and Berea sandstone and two samples of granular media with distributed CAN: glass beads and sand. The synchrotron x-ray images are analyzed to obtain true contact areas and changing strain fields under stress. The ultrasonic signals are analyzed in relation to the changes in contact areas during both the quasi-static and dynamic loading to examine the state-of-the-art understanding of ultrasonic transmission in fractured media as well as acoustoelasticity and dynamic acoustoelasticity.

Fast intersystem crossing in the tetracene dimers as a source of “dark” state

Tetracene (Tc) is a prototype material undergoing singlet fission (SF), the formation of a pair of triplet excitons from a singlet exciton. The tetracene dimer Tc2 is supposed to be a structural unit providing SF behavior. This work is devoted to the study of the mechanism of singlet exciton decay in van der Waals dimers of Tc2. A nanosecond pump-probe approach is used, tuning both pumping and probing wavelengths. It is shown that the photoexcitation of both the Tc monomer and dimer gives rise to a triplet Tc(T1) with very similar photoionization spectra, indicating an intersystem crossing (ISC) as the source of Tc(T1) in both cases. This finding, together with the very short lifetime of the singlet exciton in van der Waals Tc2 dimers as reported earlier in the literature, indicates that the ISC process is much faster in the dimer than in bare Tc. The factors that increase the rate of ISC in donor–acceptor complexes are the low-lying charge-transfer state in the Tc2 dimer and the proximity in the energy between the singlet S1 and triplet T2 states in tetracene. This fast ISC process is assigned to the temperature-independent process reported earlier in the literature, leading to a “dark” state in tetracene. The results obtained indicate that the dimer of tetracene can be considered to be a structural unit responsible for both fast ISC and SF processes.

Second-Order Photoinduced Reflectivity for Retrieval of the Dynamics in Plasmonic Nanostructures.

Measuring the change in reflectivity (ΔR) using the traditional pump–probe approach can monitor photoinduced ultrafast dynamics in matter, yet relating these dynamic to physical processes for complex systems is not unique. By applying a simple modification to the classical pump–probe technique, we simultaneously measure both the first and second order of ΔR. These additional data impose new constraints on the interpretation of the underlying ultrafast dynamics. In the first application of the approach, we probe the dynamics induced by a pump laser on the local-surface plasmon resonance (LSPR) in gold nanoantennas. Measurements of ΔR over several picoseconds and a wide range of probe wavelengths around the LSPR peak are followed by data fitting using the two-temperature model. The constraints, imposed by the second-order data, lead us to modify the model and force us to include the contribution of nonthermalized electrons in the early stages of the dynamics.

Element-selective analysis of ultrafast demagnetization in Co/Pt multilayers exhibiting large perpendicular magnetic anisotropy

We use time-resolved resonant magnetic scattering experiments to investigate the laser induced demagnetization of Co/Pt multilayers with large perpendicular magnetic anisotropy. Our pump-probe approach, which relies on extreme ultraviolet pulses obtained via high-harmonic generation, allows us to monitor the temporal evolution of the system in an element-selective fashion, thus to disentangle the contributions from permanent and proximity-induced magnetic moments. By analyzing the data gathered at the Co M2,3 and Pt O3 edges, we are able to show that after femtosecond laser irradiation, both components display a very similar loss of magnetic order, with almost identical demagnetization amplitudes and characteristic times, but a small delay (10–20 fs) of the Pt magnetization quenching with respect to Co. Comparing our experiments with literature results, therefore, suggests that in these 3d–5d multilayers and alloys, the different constituents remain strongly coupled after optical excitation; no matter whether the thin films possess a preferred in-plane or out-of-plane easy magnetization direction.

Nonlinear microscopy using impulsive stimulated Brillouin scattering for high-speed elastography.

The impulsive stimulated Brillouin microscopy promises fast, non-contact measurements of the elastic properties of biological samples. The used pump-probe approach employs an ultra-short pulse laser and a cw laser to generate Brillouin signals. Modeling of the microscopy technique has already been carried out partially, but not for biomedical applications. The nonlinear relationship between pulse energy and Brillouin signal amplitude is proven with both simulations and experiments. Tayloring of the excitation parameters on the biologically relevant polyacrylamide hydrogels outline sub-ms temporal resolutions at a relative precision of <1%. Brillouin microscopy using the impulsive stimulated scattering therefore exhibits high potential for the measurements of viscoelastic properties of cells and tissues.

Crystallographic Studies of Rhodopsins: Structure and Dynamics.

Crystal structures have provided detailed insight in the architecture of rhodopsin photoreceptors. Of particular interest are the protein-chromophore interactions that govern the light-induced retinal isomerization and ultimately induce the large structural changes important for the various biological functions of the family. The reaction intermediates occurring along the rhodopsin photocycle have vastly differing lifetimes, from hundreds of femtoseconds to milliseconds. Detailed insight at high spatial and temporal resolution can be obtained by time-resolved crystallography using pump-probe approaches at X-ray free-electron lasers. Alternatively, cryotrapping approaches can be used. Both the approaches are described, including illumination and sample delivery. The importance of appropriate photoexcitation avoiding multiphoton absorption is stressed.

Real-time observation of photoionization-induced water migration dynamics in 4-methylformanilide-water by picosecond time-resolved infrared spectroscopy and ab initio molecular dynamics simulations.

A novel time-resolved pump-probe spectroscopic approach that enables to keep high resolution in both the time and energy domain, nanosecond excitation-picosecond ionization-picosecond infrared probe (ns-ps-ps TRIR) spectroscopy, has been applied to the trans-4-methylformanilide-water (4MetFA-W) cluster. Water migration dynamics from the CO to the NH binding site in a peptide linkage triggered by photoionization of 4MetFA-W is directly monitored by the ps time evolution of IR spectra, and the presence of an intermediate state is revealed. The time evolution is analyzed by rate equations based on a four-state model of the migration dynamics. Time constants for the initial to the intermediate and hot product and to the final product are obtained. The acceleration of the dynamics by methyl substitution and the strong contribution of intracluster vibrational energy redistribution in the termination of the solvation dynamics is suggested. This picture is well confirmed by the ab initio on-the-fly molecular dynamics simulations. Vibrational assignments of 4MetFA and 4MetFA-W in the neutral (S0 and S1) and ionic (D0) electronic states measured by ns IR dip and electron-impact IR photodissociation spectroscopy are also discussed prior to the results of time-resolved spectroscopy.

Towards Understanding Excited-State Properties of Organic Molecules Using Time-Resolved Soft X-ray Absorption Spectroscopy.

The extension of the pump-probe approach known from UV/VIS spectroscopy to very short wavelengths together with advanced simulation techniques allows a detailed analysis of excited-state dynamics in organic molecules or biomolecular structures on a nanosecond to femtosecond time level. Optical pump soft X-ray probe spectroscopy is a relatively new approach to detect and characterize optically dark states in organic molecules, exciton dynamics or transient ligand-to-metal charge transfer states. In this paper, we describe two experimental setups for transient soft X-ray absorption spectroscopy based on an LPP emitting picosecond and sub-nanosecond soft X-ray pulses in the photon energy range between 50 and 1500 eV. We apply these setups for near-edge X-ray absorption fine structure (NEXAFS) investigations of thin films of a metal-free porphyrin, an aggregate forming carbocyanine and a nickel oxide molecule. NEXAFS investigations have been carried out at the carbon, nitrogen and oxygen K-edge as well as on the Ni L-edge. From time-resolved NEXAFS carbon, K-edge measurements of the metal-free porphyrin first insights into a long-lived trap state are gained. Our findings are discussed and compared with density functional theory calculations.

Thermal Characterization of Metal-Oxide Interfaces Using Time-Domain Thermoreflectance with Nanograting Transducers.

Metal-oxide thermal boundary conductance (TBC) strongly influences the temperature rise in nanostructured systems, such as dense interconnects, when its value is comparable to the thermal conductance of the amorphous dielectric oxide. However, the thermal characterization of metal-amorphous oxide TBC is often hampered by the measurement insensitivity of techniques such as time-domain thermoreflectance (TDTR). Here, we use metal nanograting structures as opto-thermal transducers in TDTR to measure the TBC of metal-oxide interfaces. Combined with an ultrafast pump-probe laser measurement approach, the nanopatterned structures amplify the contribution of the thermal boundary resistance (TBR), the inverse of TBC, over the thermal resistance of the adjacent material, thereby enhancing measurement sensitivity. For demonstration purposes, we report the TBC between Al and SiO2 films. We then compare the impact of Al grating dimensions on the measured TBC values, sensitivities, and uncertainties. The grating periods L used in this study range from 150 to 300 nm, and the bridge widths w range from 72 to 205 nm. With the narrowest grating transducers (72 nm), the TBC of Al-SiO2 interfaces is measured to be 159-48+61 MW m-2 K-1, with the experimental sensitivity being 5× higher than that of a blanket Al film. This improvement is attributed to the reduced contribution of the SiO2 film thermal resistance to the temperature signal from TDTR response. The nanograting measurement approach described here is promising for the thermal characterization of a variety of nanostructured metal-amorphous passivation systems and interfaces common in semiconductor technology.

Unraveling the nonlinear elastic response of materials with dynamic acousto-elastic testing

Compared to standard nonlinear ultrasonic techniques based on harmonic generation or resonance tests that provide an average nonlinearity level, Dynamic Acousto-Elastic Testing (DAET) is a pump-probe approach that allows one to track the nonlinear elastic response at each phase of the dynamic cycle, and to quantify additional features such as transient softening/weakening and hysteresis. These so-called nonlinear signatures can help us unravel the origins of the nonlinear response at the micro/mesoscopic scale. In this talk, we first review some of the DAET results obtained by our group and others in a wide range of materials from cracked metals to rocks and unconsolidated granular media. Next, we present some of our most recent results where we investigate the effect of relative humidity (RH) on the nonlinear elastic response of granular media. We use DAET on samples of glass beads under dry (∼10%), ambient (∼60%) and humid (∼100%) conditions. We find that all extracted nonlinear parameters in humid samples increases by an order of magnitude compared to those in dry samples. This is consistent with the idea that water adsorption on the grains makes the contact junctions weaker. This has great relevance when trying to quantify the nonlinearity of porous materials.

Label-Free Optical Microscope Based on a Phase-Modulated Femtosecond Pump–Probe Approach with Subdiffraction Resolution

A far-field optical microscope (OM) is a powerful noninvasive, nondestructive tool to study sub-micrometer structures and organisms, which has been used for decades to study the interactions betwee...

Secondary structure effects on internal proton transfer in poly-peptides.

A pump–probe approach was designed to determine the internal proton transfer (PT) rate in a series of poly-peptide radical cations containing both histidine and tryptophan. The proton transfer is driven by the gas-phase basicity difference between residues. The fragmentation scheme indicates that the gas-phase basicity of histidine is lower than that of radical tryptophan so that histidine is always pulling the proton away from tryptophan. However, the proton transfer requires the two basic sites to be in close proximity, which is rate limited by the peptide conformational dynamics. PT rate measurements were used to probe and explore the peptide conformational dynamics in several poly-glycines/prolines/alanines. For small and unstructured peptides, the PT rate decreases with the size, as expected from a statistical point of view in a flat conformational space. Conversely, if structured conformations are accessible, the structural flexibility of the peptide is decreased. This slows down the occurrence of conformations favorable to proton transfer. A dramatic decrease in the PT rates was observed for peptides HAnW, when n changes from 5 to 6. This is attributed to the onset of a stable helix for n = 6. No such discontinuity is observed for poly-glycines or poly-prolines. In HAnW, the gas-phase basicity and helix propensity compete for the position of the charge. Interestingly, in this competition between PT and helix formation in HA6W, the energy gain associated with helix formation is large enough to slow down the PT beyond experimental time but does not ultimately prevail over the proton preference for histidine.

Crystalline-like ordering of 8CB liquid crystals revealed by time-domain Brillouin scattering.

We demonstrate that time-domain Brillouin scattering (TDBS), a technique based on an ultrafast pump-probe approach, is sensitive to phase transitions and apply it to the study of structural changes in 8CB liquid crystals at different temperatures across the isotropic, nematic, smectic, and crystalline phases. We investigate the viscoelastic properties of 8CB squeezed in a narrow gap, from the nanometer to submicrometer thickness range, and conclude on the long-range molecular structuring of the smectic phase. These TDBS results reveal that confinement effects favor structuring of the smectic phase into a crystallinelike phase that can be observed at wide distances far beyond the molecular dimensions.