Sub-ps Time Scale Research Articles

4f electron temperature driven ultrafast electron localization

Valence transitions in strongly correlated electron systems are caused by orbital hybridization and Coulomb interactions between localized and delocalized electrons. The transition can be triggered by changes in the electronic structure and is sensitive to temperature variations, applications of magnetic fields, and physical or chemical pressure. Launching the transition by photoelectric fields can directly excite the electronic states and thus provides an ideal platform to study the correlation among electrons on ultrafast timescales. The EuNi2(Si0.21Ge0.79)2 mixed-valence metal is an ideal material to investigate the valence transition of the Eu ions via the amplified orbital hybridization by the photoelectric field on subpicosecond timescales. A direct view on the 4f electron occupancy of the Eu ions is required to understand the microscopic origin of the transition. Here we probe the 4f electron states of EuNi2(Si0.21Ge0.79)2 at the sub-ps timescale after photoexcitation by x-ray absorption spectroscopy across the Eu M5-absorption edge. The observed spectral changes due to the excitation indicate a population change of total angular momentum multiplet states J = 0, 1, 2, and 3 of Eu3+ and the Eu2+ J = 7/2 multiplet state caused by an increase in 4f electron temperature that results in a 4f localization process. This electronic temperature increases combined with fluence-dependent screening accounts for the strongly nonlinear effective valence change. The data allow us to extract a time-dependent determination of an effective temperature of the 4f shell, which is also of great relevance in the understanding of metallic systems' properties, such as the ultrafast demagnetization of ferromagnetic rare-earth intermetallic and their all-optical magnetization switching. In addition, our results elucidate the energetics of charge fluctuations in valence-mixed electronic systems, which provide enriched knowledge regarding the role of valence transitions and orbital hybridization for quantum critical phenomena. Published by the American Physical Society 2024

Iminothioindoxyl Donors with Exceptionally High Cross Section for Protein Vibrational Energy Transfer.

Various protein functions are related to vibrational energy transfer (VET) as an important mechanism. The underlying transfer pathways can be experimentally followed by ultrafast Vis-pump/IR-probe spectroscopy with a donor-sensor pair of non-canonical amino acids (ncAAs) incorporated in a protein. However, so far only one donor ncAA, azulenylalanine (AzAla), exists, which suffers from a comparably low Vis extinction coefficient. Here, we introduce two novel donor ncAAs based on an iminothioindoxyl (ITI) chromophore. The dimethylamino-ITI (DMA-ITI) and julolidine-ITI (J-ITI) moieties overcome the limitation of AzAla with a 50 times higher Vis extinction coefficient. While ITI moieties are known for ultrafast photoswitching, DMA-ITI and J-ITI exclusively form a hot ground state on the sub-ps timescale instead, which is essential for their usage as vibrational energy donor. In VET measurements of donor-sensor dipeptides we investigate the performance of the new donors. We observe 20 times larger signals compared to the established AzAla donor, which opens unprecedented possibilities for the study of VET in proteins.

Temperature dependent charge carrier dynamics in 2D ternary Cu2MoS4 nanoflakes: An effect of electron-phonon coupling.

Two-dimensional transition metal chalcogenides (2D TMCs) like MoS2, WS2 etc., have established significant dominance in the field of nanoscience and nanotechnology, owing to their unique properties like strong light-matter interaction, high carrier mobility, large photo-responsivity etc. Despite the widespread utilization of these binary TMCs, their potential in the advancement of the optoelectronic research is limited due to the constraints in band tuning and charge carrier lifetime. To overcome these limitations, ternary transition metal chalcogenides have emerged as promising alternatives. Although, the optical properties of these materials have never been explored properly. Herein, we have investigated one such promising member of this group, Cu2MoS4 (CMS) using both steady state and time-resolved spectroscopic techniques. The material exhibits a broad range of visible light absorption, peaking at 576nm. Photoluminescence spectroscopy confirmed the presence of both band gap emission and trap state-mediated emissions. Transient absorption spectroscopy unraveled the excited state charge carrier dynamics of CMS in sub-ps timescale, upon irradiation of visible light. We found significant influence of the trap mediated recombination, while Auger process being dominant at high charge density. We extended our study in a wide temperature range (5-300K), which reveals the impact of electron-phonon coupling strength on the band gap and charge carrier dynamics of this material. This detailed study would draw more attention toward the unexplored optical properties of ternary 2D chalcogenides and will open new avenues for the construction of 2D material-based optical devices.

Ultrafast Proton Transfer and Contact Ion-Pair Formation in Formic Acid Clusters.

The ultrafast proton transfer dynamics of homogeneous formic acid clusters (FA)n, n < 10, are investigated with femtosecond time-resolved mass spectrometry. We monitor the proton transfer pathway following Rydberg state electronic relaxation and find that successful ion pair formation increases logarithmically with cluster size. Ab initio calculations demonstrate similar excitation/relaxation behavior for each cluster, revealing a contact ion pair forms between two molecules composing the cluster before finally a formate anion (HCOO-) is dissociated by the probe pulse. The sub-ps time scale for rearrangement and proton transfer increases almost linearly with cluster size, requiring ∼67 fs per additional formic acid molecule and ranging from 213 ± 51 fs for the trimer to 667 ± 116 fs for FA9. The near-linear trends measured for both rearrangement lifetime and ion pair formation suggest that proton transfer is unlikely in the formic acid dimer but becomes prominent in small clusters.

Optical Pump Terahertz Probe (OPTP) and Time Resolved Terahertz Spectroscopy (TRTS) of emerging solar materials

Photoconductivity is the crucial benchmark to assess the potential of any emerging material for future solar applications. Many optical techniques, like transient absorption and photoluminescence, explore bound electron states and provide indirect access to photoconductivity. Direct current (DC) measurements under solar simulation determine the total performance of a novel solar device. While this technique has a clear appeal, it involves electrical contacts, causing contact resistance, which impacts the measured conductivity. Furthermore, DC measurements do not provide any insight into ultrafast effects and the photophysics defining a novel material. Terahertz (THz) spectroscopy presents a contact-free technique to measure photoconductivity on a sub-ps time scale. These measurements can be performed on as-synthesized sample materials, including powders. The ultrafast time resolution informs us of trapping dynamics and reveals what physical processes limit the carrier lifetime in a novel material. Additionally, complex conductivity can be measured at THz frequencies. THz-conductivity and photoconductivity shed light on scattering effects, providing a road map toward minimizing these effects. However, THz spectroscopy is less intuitive than widely used DC measurements, and the interpretation of THz-results is more challenging. This tutorial aims to familiarize the reader with the main THz techniques used to explore emerging materials. We will illustrate how carrier lifetimes can be extracted from optical pump THz probe measurements. We will guide the reader through the process of extracting accurate photoconductivities from time resolved THz spectroscopy measurements and present the most commonly used models to describe the underlying physics. We will then discuss the difference between sample and material parameters and highlight potential pitfalls. The tutorial concludes with a perspective view on the ever evolving field of optical pump-THz probe spectroscopy of emerging materials.

Non-Phenomenological Description of the Time-Resolved Emission in Solution with Quantum-Classical Vibronic Approaches-Application to Coumarin C153 in Methanol.

We report a joint experimental and theoretical work on the steady-state spectroscopy and time-resolved emission of the coumarin C153 dye in methanol. The lowest energy excited state of this molecule is characterized by an intramolecular charge transfer thus leading to remarkable shifts of the time-resolved emission spectra, dictated by the methanol reorganization dynamics. We selected this system as a prototypical test case for the first application of a novel computational protocol aimed at the prediction of transient emission spectral shapes, including both vibronic and solvent effects, without applying any phenomenological broadening. It combines a recently developed quantum-classical approach, the adiabatic molecular dynamics generalized vertical Hessian method (Ad-MD|gVH), with nonequilibrium molecular dynamics simulations. For the steady-state spectra we show that the Ad-MD|gVH approach is able to reproduce quite accurately the spectral shapes and the Stokes shift, while a ∼0.15 eV error is found on the prediction of the solvent shift going from gas phase to methanol. The spectral shape of the time-resolved emission signals is, overall, well reproduced, although the simulated spectra are slightly too broad and asymmetric at low energies with respect to experiments. As far as the spectral shift is concerned, the calculated spectra from 4 ps to 100 ps are in excellent agreement with experiments, correctly predicting the end of the solvent reorganization after about 20 ps. On the other hand, before 4 ps solvent dynamics is predicted to be too fast in the simulations and, in the sub-ps timescale, the uncertainty due to the experimental time resolution (300 fs) makes the comparison less straightforward. Finally, analysis of the reorganization of the first solvation shell surrounding the excited solute, based on atomic radial distribution functions and orientational correlations, indicates a fast solvent response (≈100 fs) characterized by the strengthening of the carbonyl-methanol hydrogen bond interactions, followed by the solvent reorientation, occurring on the ps timescale, to maximize local dipolar interactions.

Dynamics of the Femtosecond Mid-IR Laser Pulse Impact on a Bulk Silicon

In this study, we reconstructed the dynamics of the impact of mid-IR-range (4.6 μm) femtosecond laser pulses on bulk silicon under tight focusing conditions (NA = 0.5). Our experimental results show that under this impact, the deposited energy density (DED) reaches approximately 4 kJ/cm3 (at an energy slightly above the plasma-formation threshold). Initially, the femtosecond pulse energy is absorbed by the laser-induced plasma, with a lifetime of approximately 160–320 fs (depending on the laser pulse energy). The energy transfer from the plasma to the atomic subsystem occurs on a sub-ps timescale, which generates a shock wave and excites coherent phonons on a sub-ps scale. The shift of atoms in the lattice at the front of the shock wave results in a cascade of phase transitions (Si-X =&gt; Si-VII =&gt; Si-VI =&gt; Si-XI =&gt; Si-II), leading to a change in the phonon spectra of silicon.

Dual photoisomerization mechanism of azobenzene embedded in a lipid membrane.

The photoisomerization of chromophores embedded in biological environments is of high importance for biomedical applications, but it is still challenging to define the photoisomerization mechanism both experimentally and computationally. We present here a computational study of the azobenzene molecule embedded in a DPPC lipid membrane, and assess the photoisomerization mechanism by means of the quantum mechanics/molecular mechanics surface hopping (QM/MM-SH) method. We observe that while the trans-to-cis isomerization is a slow process governed by a torsional mechanism due to the strong interaction with the environment, the cis-to-trans mechanism is completed in sub-ps time scale and is governed by a pedal-like mechanism in which both weaker interactions with the environment and a different geometry of the potential energy surface play a key role.

Exciton dynamics in conjugated polymer systems

Exciton dynamics in π-conjugated polymers systems encompass multiple time and length scales. Ultrafast femtosecond processes are intrachain and involve a quantum mechanical correlation of the exciton and nuclear degrees of freedom. In contrast, post-picosecond processes involve the incoherent Förster transfer of excitons between polymer chains. Exciton dynamics is also strongly determined by the spatial and temporal disorder that is ubiquitous in conjugated polymers. Since excitons are delocalized over hundreds of atoms, a theoretical understanding of these processes is only realistically possible by employing suitably parametrized coarse-grained exciton-phonon models. Moreover, to correctly account for ultrafast processes, the exciton and phonon modes must be treated on the same quantum mechanical basis and the Ehrenfest approximation must be abandoned. This further implies that sophisticated numerical techniques must be employed to solve these models. This review describes our current theoretical understanding of exciton dynamics in conjugated polymer systems. We begin by describing the energetic and spatial distribution of excitons in disordered polymer systems, and define the crucial concept of a “chromophore” in conjugated polymers. We also discuss the role of exciton-nuclear coupling, emphasizing the distinction between “fast” and “slow” nuclear degrees of freedom in determining “self-trapping” and “self-localization” of exciton-polarons. Next, we discuss ultrafast intrachain exciton decoherence caused by exciton-phonon entanglement, which leads to fluorescence depolarization on the timescale of 10-fs. Interactions of the polymer with its environment causes the stochastic relaxation and localization of high-energy delocalized excitons onto chromophores. The coupling of excitons with torsional modes also leads to various dynamical processes. On sub-ps timescales it causes exciton-polaron formation (i.e., exciton localization and local polymer planarization). Conversely, on post-ps timescales stochastic torsional fluctuations cause exciton-polaron diffusion along the polymer chain and at higher temperatures to transient exciton delocalization via extended exciton states. We next describe a first-principles, Förster-type model of interchain exciton transfer and diffusion in the condensed phase, whose starting point is a realistic description of the donor and acceptor chromophores. Finally, we discuss condensed phase transient exciton delocalization in highly-ordered nanofibers. We survey experimental results and explain how they can be understood in terms of our theoretical description of exciton dynamics coupled to information on polymer multiscale structures. The review also contains a brief critique of computational methods to simulate exciton dynamics.

Probing laser-induced spin-current generation in synthetic ferrimagnets using spin waves

Several rare-earth transition-metal ferrimagnetic systems exhibit all-optical magnetization switching upon excitation with a femtosecond laser pulse. Although this phenomenon is very promising for future opto-magnetic data storage applications, the role of non-local spin transport in these systems is scarcely understood. Using Co/Gd and Co/Tb bilayers we isolate the contribution of the rare-earth materials to the generated spin currents by using the precessional dynamics they excite in an adjacent ferromagnetic layer as a probe. By measuring THz standing spin-waves as well as GHz homogeneous precessional modes, we probe both the high- and low-frequency components of these spin currents. The low-frequency homogeneous mode indicates a significant contribution of Gd to the spin current, but not from Tb, consistent with the difficulty in achieving all-optical switching in Tb-containing systems. Measurements on the THz frequency spin waves reveal the inability of the rare-earth generated spin currents to excite dynamics at the sub-ps timescale. We present modelling efforts using the $s$-$d$ model, which effectively reproduce our results and allow us to explain the behavior in terms of the temporal profile of the spin current.

Ultrafast Terahertz Self-Induced Absorption and Phase Modulation on a Graphene-Based Thin Film Absorber

Interaction of intense terahertz (THz) waves with graphene based modulation devices holds great potential for the optoelectronic applications of the future. Here, we present a thin film graphene-based THz perfect absorbing device whose absorption and phase characteristics can be modulated through THz self-actions in the subps time scale. The device consists of a single-layer graphene placed on an ionic liquid substrate, back-plated by a metallic back-reflector, with the graphene doping level mediated through electrostatic gating. We experimentally record an absorption modulation of more than 3 orders of magnitude from the initial perfect absorption state, when the device is illuminated with THz field strengths in the range of 102 to 654 kV/cm. Furthermore, an absolute phase modulation of 130° is recorded. Detailed theoretical analysis indicates that the origin of the THz nonlinear response is the THz-induced heating of the graphene’s carriers that leads to a reduction of its conductivity and, consequently, to reduced absorption of the THz radiation. Our analysis also maps the temporal dynamics of the THz-induced temperature elevation of the graphene’s carriers, illustrating the ultrafast, subps nature of the overall process. These results can find applications in future dynamically controlled flat optics and spatiotemporal shaping of intense THz electric fields.

Ultrafast Electron Transfer from CdSe Quantum Dots to an [FeFe]-Hydrogenase Mimic.

The combination of CdSe nanoparticles as photosensitizers with [FeFe]-hydrogenase mimics is known to result in efficient systems for light-driven hydrogen generation with reported turnover numbers in the order of 104-106. Nevertheless, little is known about the details of the light-induced charge-transfer processes. Here, we investigate the time scale of light-induced electron transfer kinetics for a simple model system consisting of CdSe quantum dots (QDs) of 2.0 nm diameter and a simple [FeFe]-hydrogenase mimic adsorbed to the QD surface under noncatalytic conditions. Our (time-resolved) spectroscopic investigation shows that both hot electron transfer on a sub-ps time scale and band-edge electron transfer on a sub-10 ps time scale from photoexcited QDs to adsorbed [FeFe]-hydrogenase mimics occur. Fast recombination via back electron transfer is observed in the absence of a sacrificial agent or protons which, under real catalytic conditions, would quench remaining holes or could stabilize the charge separation, respectively.

High-frequency magnon excitation due to femtosecond spin-transfer torques

Femtosecond laser pulses can induce ultrafast demagnetization as well as generate bursts of hot electron spin currents. In trilayer spin valves consisting of two metallic ferromagnetic layers separated by a nonmagnetic one, hot electron spin currents excited by an ultrashort laser pulse propagate from the first ferromagnetic layer through the spacer reaching the second magnetic layer. When the magnetizations of the two magnetic layers are noncollinear, this spin current exerts a torque on magnetic moments in the second ferromagnet. Since this torque is acting only within the sub-ps timescale, it excites coherent high-frequency magnons as recently demonstrated in experiments. Here, we calculate the temporal shape of the hot electron spin currents using the superdiffusive transport model and simulate the response of the magnetic system to the resulting ultrashort spin-transfer torque pulse by means of atomistic spin-dynamics simulations. Our results confirm that the acting spin-current pulse is short enough to excite magnons with frequencies beyond 1 THz, a frequency range out of reach for current induced spin-transfer torques. We demonstrate the formation of thickness dependent standing spin waves during the first picoseconds after laser excitation. In addition, we vary the penetration depth of the spin-transfer torque to reveal its influence on the excited magnons. Our simulations clearly show a suppression effect of magnons with short wavelengths already for penetration depths in the range of 1 nm confirming experimental findings reporting penetration depths below $2\, {\rm nm}$.

Real-time observation of the intravalley spin-flip process in single-layer WS2

We use helicity-resolved transient absorption spectroscopy to track intravalley scattering dynamics in monolayer WS2. We find that spin-polarized carriers scatter from upper to lower conduction band by reversing their spin orientation on a sub-ps timescale.

Intravalley Spin-Flip Relaxation Dynamics in Single-Layer WS2.

In monolayer (1L) transition metal dichalcogenides (TMDs) the valence and conduction bands are spin-split because of the strong spin-orbit interaction. In tungsten-based TMDs the spin-ordering of the conduction band is such that the so-called dark excitons, consisting of electrons and holes with opposite spin orientation, have lower energy than A excitons. The transition from bright to dark excitons involves the scattering of electrons from the upper to the lower conduction band at the K point of the Brillouin zone, with detrimental effects for the optoelectronic response of 1L-TMDs, since this reduces their light emission efficiency. Here, we exploit the valley selective optical selection rules and use two-color helicity-resolved pump-probe spectroscopy to directly measure the intravalley spin-flip relaxation dynamics in 1L-WS2. This occurs on a sub-ps time scale, and it is significantly dependent on temperature, indicative of phonon-assisted relaxation. Time-dependent ab initio calculations show that intravalley spin-flip scattering occurs on significantly longer time scales only at the K point, while the occupation of states away from the minimum of the conduction band significantly reduces the scattering time. Our results shed light on the scattering processes determining the light emission efficiency in optoelectronic and photonic devices based on 1L-TMDs.

Ultrafast interligand electron transfer in cis-[Ru(4,4'-dicarboxylate-2,2'-bipyridine)2(NCS)2]4- and implications for electron injection limitations in dye sensitized solar cells.

Interligand electron transfer (ILET) of the lowest metal-to-ligand charge transfer (MLCT) state of N712 (cis-[Ru(dcb)2(NCS)2]4-, where dcb = 4,4'-dicarboxylate-2,2'-bipyridine) in a deuterated acetonitrile solution has been studied by means of femtosecond transient absorption anisotropy in the mid-IR. Time-independent B3LYP density functional calculations were performed to assign vibrational bands and determine their respective transition dipole moments. The transient absorption spectral band at 1327 cm-1, assigned to a symmetric carboxylate stretch, showed significant anisotropy. A rapid anisotropy increase (τ 1 ≈ 2 ps) was tentatively assigned to vibrational and solvent relaxation, considering the excess energy available after the excited singlet-triplet conversion. Thereafter, the anisotropy decayed to zero with a time constant τ 2 ≈ 240 ps, which was assigned to the rotational correlation time of the complex in deuterated acetonitrile. No other distinctive changes to the anisotropy were observed and the amplitude of the slow component at time zero agrees well with that predicted for a random mixture of MLCT localization on either of the two dcb ligands. The results therefore suggest that MLCT randomization over the two dcb ligands occurs on the sub-ps time scale. This is much faster than proposed by previous reports on the related N3 complex [Benkö et al., J. Phys. Chem. B, 2004, 108, 2862, and Waterland et al., J. Phys. Chem. A, 2001, 105, 4019], but in agreement with that found by Wallin and co-workers [J. Phys. Chem. A, 2005, 109, 4697] for the [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) complex. This suggests that electron injection from the excited dye into TiO2 in dye-sensitized solar cells is not limited by ILET.

Excited state dynamics and time-resolved photoelectron spectroscopy of para-xylylene.

We investigated the excited-state dynamics of para-xylylene using a combination of field-induced surface hopping (FISH) simulations and time-resolved ionisation experiments. Our simulations predict an ultrafast decay of the initially excited bright state (S2/S3) to the S1 state on a sub-100 fs time scale, followed by return to the ground state within ∼1 ps. This is accompanied by a transient change of the biradical character of the molecule, as monitored by calculating natural orbital occupation numbers. Specifically, the initially low biradicality is increased by electronic excitation as well as by vibrational activation. Experimentally, para-xylylene was generated by pyrolysis from [2,2]paracyclophane and excited with 266 nm radiation into the S2/S3 bright state. The subsequent dynamics were followed using ionisation as the probe step, with both mass spectra and photoelectron spectra recorded as a function of pump-probe delay. The observed decay of photoelectron and photoion intensities closely matches the theoretical predictions and is consistent with the sequential mechanism found in the simulations. This mechanism exhibits characteristic signatures in both time-resolved mass and photoelectron spectra, in particular in the appearance of fragment ions that are exclusively generated from the S1 state. This allows for a separation of the S2 and S1 dynamics in the photoelectron and mass spectra. An excellent agreement between the observed and the simulated ion signal is observed.

High temperature limit of semiconductor nanowire lasers

Nanoscale light sources for intense laser emission based on CdS nanowires provide both an extremely localized emission and an ultrafast response even on sub-ps timescales. These fundamental mechanisms were investigated in the past, and practical device applications, such as on-chip laser driven applications working in different temperature ranges up to values far beyond room temperature, are becoming the focus of research. Here, we present a detailed study of the power dependent performance of CdS nanowire lasers which exhibit four distinct working regimes divided by certain threshold values. These regimes are spontaneous emission, amplified spontaneous emission, lasing, and a regime of vanishing laser oscillations due to active material degradation. The three threshold values bridging these four regimes are evaluated as a function of operating temperature, enabling the determination of an upper temperature limit for stable CdS nanowire lasing, at which the degradation threshold drops below the lasing threshold. Furthermore, the degradation mechanism of the CdS nanolasers will be proposed.

Terahertz dynamics of lattice vibrations in Au/CdTe plasmonic crystals: Photoinduced segregation of Te and enhancement of optical response

Excitation of coherent optical phonons in solids provides a pathway for ultrafast modulation of light on a sub-ps timescale. Here, we report on efficient 3.6 THz modulation of light reflected from hybrid metal/semiconductor plasmonic crystals caused by lattice vibrations in a few nm thick layer of elemental tellurium. We observe that surface plasmon polaritons contribute significantly to photoinduced formation of this thin layer at the interface between a telluride-based II-VI semiconductor, such as (Cd,Mg)Te or (Cd,Mn)Te, and a one-dimensional gold grating. The change in interface composition is monitored via the excitation and detection of coherent optical tellurium phonons of $A_1$ symmetry by femtosecond laser pulses in a pump-probe experiment. The patterning of a plasmonic grating onto the semiconductor enhances the transient signal which originates from the interface region. This allows monitoring the layer formation and observing the shift of the phonon frequency caused by confinement of the lattice vibrations in the nm-thick segregated layer. Efficient excitation and detection of coherent optical phonons by means of surface plasmon polaritons are evidenced by the dependence of the signal strength on polarization of pump and probe pulses and its spectral distribution.

Four-wave-mixing experiments with seeded free electron lasers.

The development of free electron laser (FEL) sources has provided an unprecedented bridge between the scientific communities working with ultrafast lasers and extreme ultraviolet (XUV) and X-ray radiation. Indeed, in recent years an increasing number of FEL-based applications have exploited methods and concepts typical of advanced optical approaches. In this context, we recently used a seeded FEL to demonstrate a four-wave-mixing (FWM) process stimulated by coherent XUV radiation, namely the XUV transient grating (X-TG). We hereby report on X-TG measurements carried out on a sample of silicon nitride (Si3N4). The recorded data bears evidence for two distinct signal decay mechanisms: one occurring on a sub-ps timescale and one following slower dynamics extending throughout and beyond the probed timescale range (100 ps). The latter is compatible with a slower relaxation (time decay > ns), that may be interpreted as the signature of thermal diffusion modes. From the peak intensity of the X-TG signal we could estimate a value of the effective third-order susceptibility which is substantially larger than that found in SiO2, so far the only sample with available X-TG data. Furthermore, the intensity of the time-coincidence peak shows a linear dependence on the intensity of the three input beams, indicating that the measurements were performed in the weak field regime. However, the timescale of the ultrafast relaxation exhibits a dependence on the intensity of the XUV radiation. We interpreted the observed behaviour as the generation of a population grating of free-electrons and holes that, on the sub-ps timescale, relaxes to generate lattice excitations. The background free detection inherent to the X-TG approach allowed the determination of FEL-induced electron dynamics with a sensitivity largely exceeding that of transient reflectivity and transmissivity measurements, usually employed for this purpose.