Picosecond Time-resolved X-ray Research Articles

Versatile tabletop setup for picosecond time-resolved resonant soft x-ray scattering and spectroscopy

Versatile tabletop setup for picosecond time-resolved resonant soft x-ray scattering and spectroscopy

(Invited) Discovering Bottlenecks and Opportunities in Hybrid Solar Light Harvesting Systems By Ultrafast X-Ray Spectroscopy

A prerequisite for advancing hybrid solar light harvesting systems is a comprehensive understanding of photoinduced electronic dynamics across a wide range of spatial and temporal scales. Time-resolved spectroscopy techniques in the optical domain have proven instrumental in identifying critical timescales of fundamental processes, such as interfacial charge transfer, charge migration, and carrier lifetimes, which are intimately linked to a system's performance. New light source and instrument developments open opportunities to extend such studies into the X-ray regime. Due to their inherent elemental specificity and sensitivity to local electronic environments, time-domain X-ray spectroscopy techniques are uniquely suited to gain a microscopic picture of dynamics from well-defined reporter sites within often complex nanoscale light harvesting architectures. We will present new insights into fundamental photoinduced dynamics in several archetypical heterostructures based on femtosecond and picosecond time-resolved X-ray photoemission spectroscopy (TRXPS).The photoinduced transient charge redistribution in the model hybrid system of nanoporous zinc oxide (ZnO) sensitized by ruthenium bipyridyl chromophores is probed independently from the viewpoints of the molecular electron donor and the semiconductor acceptor.[1] Charge injection from the chromophore into the semiconductor is found to proceed via a transiently populated interfacial charge transfer (ICT) complex on an overall timescale of ~300 ps. Our results show that, even after release from the ICT states into the ZnO conduction band, the injected electrons remain localized within less than 6 nm from the interface, due to enhanced downward band-bending by the photo-injected charge carriers. This spatial confinement suggests that light-induced charge generation and transport in nanoscale ZnO photocatalytic devices proceeds predominantly within the defect-rich surface region, which may lead to enhanced surface recombination and explain their lower performance compared to titanium dioxide (TiO2)-based systems. The quantitative nature and surface sensitivity of TRXPS also provides direct access to the spatial separation of the holes remaining on the bipyridyl chromophores after charge injection from the semiconductor surface with sub-nm precision.Complementary femtosecond and picosecond TRXPS studies of photoinduced dynamics in copper-phthalocyanine(CuPc)-C60 heterojunctions provide a deeper understanding of both exciton migration pathways toward the interface as well as the absolute efficiency by which ICT states dissociate into separate charges.[2] The measurements reveal surprisingly efficient charge generation from triplet excitons and from the lowest lying ICT states, both of which were previously believed to be inactive during light-to-charge conversion.Photoinduced charge transfer dynamics between spherical gold nanoparticles (AuNPs) and a nanoporous film of TiO2 is monitored by picosecond TRXPS, providing direct access to the absolute photon-to-charge conversion efficiency and subsequent electron-hole recombination dynamics.[3] Preliminary results will be presented for the extension of the measurements into the ambient pressure regime, taking a first step toward the study of photoinduced interfacial chemistry by TRXPS in this model system for nanoplasmonic light harvesting applications.[1] S. Neppl et al., “Nanoscale Confinement of Photo-Injected Electrons at Hybrid Interfaces”, J. Phys. Chem. Lett. 12, 11951 (2021).[2] F. Roth et al., “Direct observation of charge separation in an organic light harvesting system by femtosecond time-resolved XPS”, Nat. Commun. 12, 1196 (2021).[3] M. Borgwardt et al., “Photoinduced Charge Carrier Dynamics and Electron Injection Efficiencies in Au Nanoparticle-Sensitized TiO2 Determined with Picosecond Time-Resolved X-ray Photoelectron Spectroscopy”, J. Phys. Chem. Lett. 11, 5476 (2020). Figure 1

Picosecond time-resolved X-ray ferromagnetic resonance measurements at Shanghai synchrotron radiation facility

An experimental picosecond time-resolved X-ray ferromagnetic resonance (TR-XFMR) apparatus with a time resolution of 13 ps (RMS) or 31 ps (FWHM) was constructed and demonstrated in the 07U and 08U1A soft X-ray beamlines at the Shanghai Synchrotron Radiation Facility (SSRF) using pump-probe detection and X-ray magnetic circular dichroism (XMCD) spectroscopy. Element and time-resolved ferromagnetic resonance was excited by continuous microwave phase-locking of the bunch clock within the photon beam during synchrotron radiation and was characterized by detecting the magnetic circular dichroism signals of the elements of interest in the magnetic films. Using this equipment, we measured the amplitude of the element-specific moment precession during ferromagnetic resonance (FMR) at 2 GHz in a single Ni81Fe19 layer.

Ultrafast light-induced shear strain probed by time-resolved x-ray diffraction: Multiferroic BiFeO3 as a case study

Enabling the light-control of complex systems on ultra-short timescales gives rise to rich physics with promising applications. While crucial, the quantitative determination of both the longitudinal and shear photo-induced strains still remains challenging. Here, by scrutinizing asymmetric Bragg peaks pairs $(\pm h01)$ using picosecond time-resolved X-ray diffraction experiments in BiFeO$_3$, we simultaneously determine the longitudinal and shear strains. The relative amplitude of those strains can be explained only if both thermal and non-thermal processes contribute to the acoustic phonon photogeneration process. Importantly, we also reveal a difference of the dynamical response of the longitudinal strain with respect to the shear one due to an interplay of quasi-longitudinal and quasi-transverse acoustic modes, well reproduced by our model.

(Invited) Ultrafast X-Ray Studies of Electron Dynamics Underlying Molecular and Nanoplasmonic Light Harvesting Architectures

Chemically engineered light harvesting architectures based on molecular and nanoplasmonic chromophores in contact with semiconducting electron acceptors provide exciting opportunities for novel photocatalytic and photovoltaic applications. Optimizing their performance, however, often hinges on a deeper understanding of the underlying fundamental electronic and chemical dynamics. Processes evolving on spatial and temporal scales spanning many orders of magnitude have to be connected in order to enable molecular, interfacial, and macroscopic charge and energy transport. We will discuss the application of ultrafast X-ray spectroscopy techniques to gain deep insight into photoinduced electronic dynamics in complex, heterogeneous light-harvesting systems based on organic heterojunctions as well as molecule-semiconductor and metal nanoparticle-semiconductor interfaces.Femtosecond and picosecond time-resolved X-ray photoelectron spectroscopy (TRXPS) is used to study photoinduced charge injection in N3 dye-sensitized films of ZnO nanoparticles. The elemental site-specificity and surface sensitivity of TRXPS provides a comprehensive real-time picture of the interfacial charge dynamics including the locations of intermittently trapped electrons, the emergence and decay of interfacial dipoles, as well as charge-injection induced band-bending dynamics in the semiconductor substrate. Potential consequences of the findings for the design of dye-sensitized nanoporous electrodes are discussed.TRXPS studies of photoinduced dynamics in copper-phthalocyanine(CuPc)-C60 heterojunctions provide a deeper understanding of the predominant energy transport and charge generation mechanisms. Ultrafast X-ray probing captures the actual moment of charge generation from interfacial charge-transfer (ICT) states and provides a quantitative measure of the exciton dissociation efficiency compared to photon energy loss by exciton recombination. The findings complement observations with ultrafast optical techniques, adding important aspects regarding the dynamic pathways and branching ratios that govern charge generation efficiencies in this canonical model system for organic light harvesting concepts.In a third showcase example, photoinduced charge transfer dynamics in a nanoporous film of TiO2 sensitized with gold nanoparticles (AuNPs) is monitored by TRXPS. Direct access to the absolute photon-to-charge conversion efficiency and subsequent electron-hole recombination dynamics is demonstrated with single-electron sensitivity. The results provide important boundary conditions for the design of AuNP-TiO2 based light harvesting systems. Opportunities for extending the measurements toward studies of photoinduced interfacial chemical transformations will be discussed.

Photoinduced Charge Carrier Dynamics and Electron Injection Efficiencies in Au Nanoparticle-Sensitized TiO2 Determined with Picosecond Time-Resolved X-ray Photoelectron Spectroscopy.

Progress in the development of plasmon-enabled light-harvesting technologies requires a better understanding of their fundamental operating principles and current limitations. Here, we employ picosecond time-resolved X-ray photoemission spectroscopy to investigate photoinduced electron transfer in a plasmonic model system composed of 20 nm sized gold nanoparticles (NPs) attached to a nanoporous film of TiO2. The measurement provides direct, quantitative access to transient local charge distributions from the perspectives of the electron donor (AuNP) and the electron acceptor (TiO2). On average, approximately two electrons are injected per NP, corresponding to an electron injection yield per absorbed photon of 0.1%. Back electron transfer from the perspective of the electron donor is dominated by a fast recombination channel proceeding on a time scale of 60 ± 10 ps and a minor contribution that is completed after ∼1 ns. The findings provide a detailed picture of photoinduced charge carrier generation in this NP-semiconductor junction, with important implications for understanding achievable overall photon-to-charge conversion efficiencies.

Direct observation of elastic softening immediately after femtosecond-laser excitation in a phase-change material

The generation and propagation of photoexcited elastic waves in crystalline $\mathrm{G}{\mathrm{e}}_{2}\mathrm{S}{\mathrm{b}}_{2}\mathrm{T}{\mathrm{e}}_{5}$ were analyzed by picosecond time-resolved x-ray diffraction using a femtosecond-laser pump and an x-ray free-electron laser probe technique. The crystalline lattice anisotropically expanded initially in approximately 20 ps after the excitation. This was followed by a periodic oscillation of the lattice strain. The elastic stiffness along the cubic $\ensuremath{\langle}111\ensuremath{\rangle}$ direction had significantly softened during the initial expansion, and the strain magnitude was the largest in the $\ensuremath{\langle}100\ensuremath{\rangle}$ and $\ensuremath{\langle}110\ensuremath{\rangle}$ directions. This indicates that femtosecond-laser excitation creates a shallower interlayer potential between the Te and Ge-Sb layers and eventually leads to softening of the elastic stiffness along the cubic $\ensuremath{\langle}111\ensuremath{\rangle}$ direction. Furthermore, this softened state increases the system's sensitivity to an external stress field. This residual internal stress in a thin film enhances the selective formation of a particular type of variant during the symmetry change from cubic to rhombohedra. This causes the subsequent anisotropic expansion. These phenomena are quite interesting and align with the ultrafast amorphization of this material.

Efficient charge generation from triplet excitons in metal-organic heterojunctions

The success of many emerging molecular electronics concepts hinges on an atomistic understanding of the underlying electronic dynamics. We employ picosecond time-resolved x-ray photoemission spectroscopy (tr-XPS) to elucidate the roles of singlet and triplet excitons for photoinduced charge generation at a copper-phthalocyanine--${\mathrm{C}}_{60}$ heterojunction. Contrary to common belief, fast intersystem crossing to triplet excitons after photoexcitation is not a loss channel but contributes to a significantly larger extent to the time-integrated interfacial charge generation than the initially excited singlet excitons. The tr-XPS data provide direct access to the diffusivity of the triplet excitons ${D}_{\mathrm{CuPc}}=(1.8\ifmmode\pm\else\textpm\fi{}1.2)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}5}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{2}/\mathrm{s}$ (where CuPc is copper-phthalocyanine) and their diffusion length ${L}_{\mathrm{diff}}=(8\ifmmode\pm\else\textpm\fi{}3)\phantom{\rule{0.16em}{0ex}}\mathrm{nm}$.

Real-time probing of charge-transfer induced interfacial fields in a dye-semiconductor system using time-resolved XPS

Photo-induced charge carrier dynamics and transient interfacial fields at the interface between N3 polypyridine complexes and films of nanocrystalline ZnO are probed by picosecond time-resolved X-ray photoelectron spectroscopy.

Energy transfer dynamics in strongly inhomogeneous hot-dense-matter systems.

Direct measurements of energy transfer across steep density and temperature gradients in a hot-dense-matter system are presented. Hot-dense-plasma conditions were generated by high-intensity laser irradiation of a thin-foil target containing a buried metal layer. Energy transfer to the layer was measured using picosecond time-resolved x-ray emission spectroscopy. The data show two x-ray flashes in time. Fully explicit, coupled particle-in-cell and collisional-radiative atomic kinetics model predictions reproduce these observations, connecting the two x-ray flashes with staged radial energy transfer within the target.

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH2S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Picosecond time-resolved measurements of dense plasma line shifts

Picosecond time-resolved x-ray spectroscopy is used to measure the spectral line shift of the 1s2p-1s^{2} transition in He-like Al ions as a function of the instantaneous plasma conditions. The plasma temperature and density are inferred from the Al He_{α} complex using a nonlocal-thermodynamic-equilibrium atomic physics model. The experimental spectra show a linearly increasing redshift for electron densities of 1-5×10^{23}cm^{-3}. The measured line shifts are broadly consistent with a generalized analytic line-shift model based on calculations of a self-consistent field ion-sphere model.

Development of picosecond time-resolved X-ray absorption spectroscopy by high-repetition-rate laser pump/X-ray probe at Beijing Synchrotron Radiation Facility.

A new setup and commissioning of transient X-ray absorption spectroscopy are described, based on the high-repetition-rate laser pump/X-ray probe method, at the 1W2B wiggler beamline at the Beijing Synchrotron Radiation Facility. A high-repetition-rate and high-power laser is incorporated into the setup with in-house-built avalanche photodiodes as detectors. A simple acquisition scheme was applied to obtain laser-on and laser-off signals simultaneously. The capability of picosecond transient X-ray absorption spectroscopy measurement was demonstrated for a photo-induced spin-crossover iron complex in 6 mM solution with 155 kHz repetition rate.

Cooperative protein structural dynamics of homodimeric hemoglobin linked to water cluster at subunit interface revealed by time-resolved X-ray solution scattering.

Homodimeric hemoglobin (HbI) consisting of two subunits is a good model system for investigating the allosteric structural transition as it exhibits cooperativity in ligand binding. In this work, as an effort to extend our previous study on wild-type and F97Y mutant HbI, we investigate structural dynamics of a mutant HbI in solution to examine the role of well-organized interfacial water cluster, which has been known to mediate intersubunit communication in HbI. In the T72V mutant of HbI, the interfacial water cluster in the T state is perturbed due to the lack of Thr72, resulting in two less interfacial water molecules than in wild-type HbI. By performing picosecond time-resolved X-ray solution scattering experiment and kinetic analysis on the T72V mutant, we identify three structurally distinct intermediates (I1, I2, and I3) and show that the kinetics of the T72V mutant are well described by the same kinetic model used for wild-type and F97Y HbI, which involves biphasic kinetics, geminate recombination, and bimolecular CO recombination. The optimized kinetic model shows that the R-T transition and bimolecular CO recombination are faster in the T72V mutant than in the wild type. From structural analysis using species-associated difference scattering curves for the intermediates, we find that the T-like deoxy I3 intermediate in solution has a different structure from deoxy HbI in crystal. In addition, we extract detailed structural parameters of the intermediates such as E-F distance, intersubunit rotation angle, and heme-heme distance. By comparing the structures of protein intermediates in wild-type HbI and the T72V mutant, we reveal how the perturbation in the interfacial water cluster affects the kinetics and structures of reaction intermediates of HbI.

X-ray characterization of a multichannel smart-pixel array detector.

The Voxtel VX-798 is a prototype X-ray pixel array detector (PAD) featuring a silicon sensor photodiode array of 48 × 48 pixels, each 130 µm × 130 µm × 520 µm thick, coupled to a CMOS readout application specific integrated circuit (ASIC). The first synchrotron X-ray characterization of this detector is presented, and its ability to selectively count individual X-rays within two independent arrival time windows, a programmable energy range, and localized to a single pixel is demonstrated. During our first trial run at Argonne National Laboratory's Advance Photon Source, the detector achieved a 60 ns gating time and 700 eV full width at half-maximum energy resolution in agreement with design parameters. Each pixel of the PAD holds two independent digital counters, and the discriminator for X-ray energy features both an upper and lower threshold to window the energy of interest discarding unwanted background. This smart-pixel technology allows energy and time resolution to be set and optimized in software. It is found that the detector linearity follows an isolated dead-time model, implying that megahertz count rates should be possible in each pixel. Measurement of the line and point spread functions showed negligible spatial blurring. When combined with the timing structure of the synchrotron storage ring, it is demonstrated that the area detector can perform both picosecond time-resolved X-ray diffraction and fluorescence spectroscopy measurements.

Towards efficient time-resolved X-ray absorption studies of electron dynamics at photocatalytic interfaces.

We present a picosecond time-resolved X-ray absorption spectroscopy (tr-XAS) setup designed for synchrotron-based studies of interfacial photochemical dynamics. The apparatus combines a high power, variable repetition rate picosecond laser system with a time-resolved X-ray fluorescence yield detection technique. Time-tagging of the detected fluorescence signals enables the parallel acquisition of X-ray absorption spectra at a variety of pump-probe delays employing the well-defined time structure of the X-ray pulse trains. The viability of the setup is demonstrated by resolving dynamic changes in the fine structure near the O1s X-ray absorption edge of cuprous oxide (Cu2O) after photo-excitation with a 355 nm laser pulse. Two distinct responses are detected. A pronounced, quasi-static, reversible change of the Cu2O O1s X-ray absorption spectrum by up to ∼30% compared to its static line shape corresponds to a redshift of the absorption edge by ∼1 eV. This value is small compared to the 2.2 eV band gap of Cu2O but in agreement with previously published results. The lifetime of this effect exceeds the laser pulse-to-pulse period of 8 μs, resulting in a quasi-static spectral change that persists as long as the sample is exposed to the laser light, and completely vanishes once the laser is blocked. Additionally, a short-lived response corresponding to a laser-induced shift of the main absorption line by ∼2 eV to lower energies appears within <200 ps and decays with a characteristic timescale of 43 ± 5 ns. Both the picosecond rise and nanosecond decay of this X-ray response are simultaneously captured by making use of a time-tagging approach - highlighting the prospects of the experimental setup for efficient probing of the electronic and structural dynamics in photocatalytic systems on multiple timescales.

News Article

News Article

Experimental station for laser-based picosecond time-resolved x-ray absorption near-edge spectroscopy.

We present an experimental station designed for time-resolved X-ray Absorption Near-Edge Spectroscopy (XANES). It is based on ultrashort laser-plasma x-ray pulses generated from a table-top 100 mJ-class laser at 10 Hz repetition rate. A high transmission (10%-20%) x-ray beam line transport using polycapillary optics allows us to set the sample in an independent vacuum chamber, providing high flexibility over a wide spectral range from 0.5 up to 4 keV. Some XANES spectra are presented, demonstrating 1% noise level in only ∼1 mn and ∼100 cumulated laser shots. Time-resolved measurements are reported, indicating that the time resolution of the entire experimental station is 3.3 ± 0.6 ps rms.

X-rays only when you want them: optimized pump-probe experiments using pseudo-single-bunch operation.

Laser pump-X-ray probe experiments require control over the X-ray pulse pattern and timing. Here, the first use of pseudo-single-bunch mode at the Advanced Light Source in picosecond time-resolved X-ray absorption experiments on solutions and solids is reported. In this mode the X-ray repetition rate is fully adjustable from single shot to 500 kHz, allowing it to be matched to typical laser excitation pulse rates. Suppressing undesired X-ray pulses considerably reduces detector noise and improves signal to noise in time-resolved experiments. In addition, dose-induced sample damage is considerably reduced, easing experimental setup and allowing the investigation of less robust samples. Single-shot X-ray exposures of a streak camera detector using a conventional non-gated charge-coupled device (CCD) camera are also demonstrated.

Site-specific probing of charge transfer dynamics in organic photovoltaics

We report the site-specific probing of charge-transfer dynamics in a prototype system for organic photovoltaics (OPVs) by picosecond time-resolved X-ray photoelectron spectroscopy. A layered system consisting of approximately two monolayers of C60 deposited on top of a thin film of Copper-Phthalocyanine (CuPC) is excited by an optical pump pulse and the induced electronic dynamics are probed with 590 eV X-ray pulses. Charge transfer from the electron donor (CuPC) to the acceptor (C60) and subsequent charge carrier dynamics are monitored by recording the time-dependent C 1s core level photoemission spectrum of the system. The arrival of electrons in the C60 layer is readily observed as a completely reversible, transient shift of the C60 associated C 1s core level, while the C 1s level of the CuPC remains unchanged. The capability to probe charge transfer and recombination dynamics in OPV assemblies directly in the time domain and from the perspective of well-defined domains is expected to open additional pathways to better understand and optimize the performance of this emerging technology.