Coherent light control of a metastable hidden state.

Metastable phases present a promising route to expand the functionality of complex materials. Of particular interest are light-induced metastable phases that are inaccessible under equilibrium conditions, as they often host new, emergent properties switchable on ultrafast timescales. However, the processes governing the trajectories to such hidden phases remain largely unexplored. Here, using time- and angle-resolved photoemission spectroscopy, we investigate the ultrafast dynamics of the formation of a hidden quantum state in the layered dichalcogenide 1T-TaS2 upon photoexcitation. Our results reveal the nonthermal character of the transition governed by a collective charge-density-wave excitation. Using a double-pulse excitation of the structural mode, we show vibrational coherent control of the phase-transition efficiency. Our demonstration of exceptional control, switching speed, and stability of the hidden state are key for device applications at the nexus of electronics and photonics.

Observation of ultrafast interfacial Meitner-Auger energy transfer in a Van der Waals heterostructure.

Atomically thin layered van der Waals heterostructures feature exotic and emergent optoelectronic properties. With growing interest in these novel quantum materials, the microscopic understanding of fundamental interfacial coupling mechanisms is of capital importance. Here, using multidimensional photoemission spectroscopy, we provide a layer- and momentum-resolved view on ultrafast interlayer electron and energy transfer in a monolayer-WSe2/graphene heterostructure. Depending on the nature of the optically prepared state, we find the different dominating transfer mechanisms: while electron injection from graphene to WSe2 is observed after photoexcitation of quasi-free hot carriers in the graphene layer, we establish an interfacial Meitner-Auger energy transfer process following the excitation of excitons in WSe2. By analysing the time-energy-momentum distributions of excited-state carriers with a rate-equation model, we distinguish these two types of interfacial dynamics and identify the ultrafast conversion of excitons in WSe2 to valence band transitions in graphene. Microscopic calculations find interfacial dipole-monopole coupling underlying the Meitner-Auger energy transfer to dominate over conventional Förster- and Dexter-type interactions, in agreement with the experimental observations. The energy transfer mechanism revealed here might enable new hot-carrier-based device concepts with van der Waals heterostructures.

Orbital-resolved observation of singlet fission.

Singlet fission1-13 may boost photovoltaic efficiency14-16 by transforming a singlet exciton into two triplet excitons and thereby doubling the number of excited charge carriers. The primary step of singlet fission is the ultrafast creation of the correlated triplet pair17. Whereas several mechanisms have been proposed to explain this step, none has emerged as a consensus. The challenge lies in tracking the transient excitonic states. Here we use time- and angle-resolved photoemission spectroscopy to observe the primary step of singlet fission in crystalline pentacene. Our results indicate a charge-transfer mediated mechanism with a hybridization of Frenkel and charge-transfer states in the lowest bright singlet exciton. We gained intimate knowledge about the localization and the orbital character of the exciton wave functions recorded in momentum maps. This allowed us to directly compare the localization of singlet and bitriplet excitons and decompose energetically overlapping states on the basis of their orbital character. Orbital- and localization-resolved many-body dynamics promise deep insights into the mechanics governing molecular systems18-20 and topological materials21-23.

Direct Observation of Ultrafast Lattice Distortions during Exciton-Polaron Formation in Lead Halide Perovskite Nanocrystals.

The microscopic origin of slow hot-carrier cooling in lead halide perovskites remains debated and has direct implications for applications. Slow hot-carrier cooling of several picoseconds has been attributed to either polaron formation or a hot-phonon bottleneck effect at high excited carrier densities (>1018 cm-3). These effects cannot be unambiguously disentangled with optical experiments alone. However, they can be distinguished by direct observations of ultrafast lattice dynamics, as these effects are expected to create qualitatively distinct fingerprints. To this end, we employ femtosecond electron diffraction and directly measure the sub-picosecond lattice dynamics of weakly confined CsPbBr3 nanocrystals following above-gap photoexcitation. While we do not observe signatures of a hot-phonon bottleneck lasting several picoseconds, the data reveal a light-induced structural distortion appearing on a time scale varying between 380 and 1200 fs depending on the excitation fluence. We attribute these dynamics to the effect of exciton-polarons on the lattice and the slower dynamics at high fluences to slower sub-picosecond hot-carrier cooling, which slows down the establishment of the exciton-polaron population. Further analysis and simulations show that the distortion is consistent with motions of the [PbBr3]- octahedral ionic cage, and closest agreement with the data is obtained for Pb-Br bond lengthening. Our work demonstrates how direct studies of lattice dynamics on the sub-picosecond time scale can discriminate between competing scenarios proposed in the literature to explain the origin of slow hot-carrier cooling in lead halide perovskites.

Observation of Multi-Directional Energy Transfer in a Hybrid Plasmonic-Excitonic Nanostructure.

Hybrid plasmonic devices involve a nanostructured metal supporting localized surface plasmons to amplify light-matter interaction, and a non-plasmonic material to functionalize charge excitations. Application-relevant epitaxial heterostructures, however, give rise to ballistic ultrafast dynamics that challenge the conventional semiclassical understanding of unidirectional nanometal-to-substrate energy transfer. Epitaxial Au nanoislands are studied on WSe2 with time- and angle-resolved photoemission spectroscopy and femtosecond electron diffraction: this combination of techniques resolves material, energy, and momentum of charge-carriers and phonons excited in the heterostructure. A strong non-linear plasmon-exciton interaction that transfers the energy of sub-bandgap photons very efficiently to the semiconductor is observed, leaving the metal cold until non-radiative exciton recombination heats the nanoparticles on hundreds of femtoseconds timescales. The results resolve a multi-directional energy exchange on timescales shorter than the electronic thermalization of the nanometal. Electron-phonon coupling and diffusive charge-transfer determine the subsequent energy flow. This complex dynamics opens perspectives for optoelectronic and photocatalytic applications, while providing a constraining experimental testbed for state-of-the-art modelling.

A machine learning route between band mapping and band structure.

The electronic band structure and crystal structure are the two complementary identifiers of solid-state materials. Although convenient instruments and reconstruction algorithms have made large, empirical, crystal structure databases possible, extracting the quasiparticle dispersion (closely related to band structure) from photoemission band mapping data is currently limited by the available computational methods. To cope with the growing size and scale of photoemission data, here we develop a pipeline including probabilistic machine learning and the associated data processing, optimization and evaluation methods for band-structure reconstruction, leveraging theoretical calculations. The pipeline reconstructs all 14 valence bands of a semiconductor and shows excellent performance on benchmarks and other materials datasets. The reconstruction uncovers previously inaccessible momentum-space structural information on both global and local scales, while realizing a path towards integration with materials science databases. Our approach illustrates the potential of combining machine learning and domain knowledge for scalable feature extraction in multidimensional data.

Photoinduced Ultrafast Transition of the Local Correlated Structure in Chalcogenide Phase-Change Materials.

Revealing the bonding and time-evolving atomic dynamics in functional materials with complex lattice structures can update the fundamental knowledge on rich physics therein, and also help to manipulate the material properties as desired. As the most prototypical chalcogenide phase change material, Ge_{2}Sb_{2}Te_{5} has been widely used in optical data storage and nonvolatile electric memory due to the fast switching speed and the low energy consumption. However, the basic understanding of the structural dynamics on the atomic scale is still not clear. Using femtosecond electron diffraction, structure factor calculation, and time-dependent density-functional theory molecular dynamic simulation, we reveal the photoinduced ultrafast transition of the local correlated structure in the averaged rocksalt phase of Ge_{2}Sb_{2}Te_{5}. The randomly oriented Peierls distortion among unit cells in the averaged rocksalt phase of Ge_{2}Sb_{2}Te_{5} is termed as local correlated structures. The ultrafast suppression of the local Peierls distortions in the individual unit cell gives rise to a local structure change from the rhombohedral to the cubic geometry within ∼0.3 ps. In addition, the impact of the carrier relaxation and the large number of vacancies to the ultrafast structural response is quantified and discussed. Our Letter provides new microscopic insights into contributions of the local correlated structure to the transient structural and optical responses in phase change materials. Moreover, we stress the significance of femtosecond electron diffraction in revealing the local correlated structure in the subunit cell and the link between the local correlated structure and physical properties in functional materials with complex microstructures.

Field-induced ultrafast modulation of Rashba coupling at room temperature in ferroelectric α-GeTe(111).

Rashba materials have appeared as an ideal playground for spin-to-charge conversion in prototype spintronics devices. Among them, α-GeTe(111) is a non-centrosymmetric ferroelectric semiconductor for which a strong spin-orbit interaction gives rise to giant Rashba coupling. Its room temperature ferroelectricity was recently demonstrated as a route towards a new type of highly energy-efficient non-volatile memory device based on switchable polarization. Currently based on the application of an electric field, the writing and reading processes could be outperformed by the use of femtosecond light pulses requiring exploration of the possible control of ferroelectricity on this timescale. Here, we probe the room temperature transient dynamics of the electronic band structure of α-GeTe(111) using time and angle-resolved photoemission spectroscopy. Our experiments reveal an ultrafast modulation of the Rashba coupling mediated on the fs timescale by a surface photovoltage, namely an increase corresponding to a 13% enhancement of the lattice distortion. This opens the route for the control of the ferroelectric polarization in α-GeTe(111) and ferroelectric semiconducting materials in quantum heterostructures.

Traversing Double-Well Potential Energy Surfaces: Photoinduced Concurrent Intralayer and Interlayer Structural Transitions in XTe2 (X = Mo, W).

The microscopic arrangement of atoms and molecules is the determining factor in how materials behave and perform; i.e., the structure determines the property, a traditional paradigm in materials science. Photoexcitation-driven manipulation of the crystal structure and associated electronic properties in quantum materials provides opportunities for the exploration of exotic physics and practical applications; however, a generalized mechanism for such symmetry engineering is absent. Here, by ultrafast electron diffraction, structure factor calculation, and TDDFT-MD simulations, we report the photoinduced concurrent intralayer and interlayer structural transitions in the Td and 1T' phases of XTe2 (X = Mo, W). We discuss the modification of multiple quantum electronic states associated with the intralayer and interlayer structural transitions, such as the topological band inversion and the higher-order topological state. The twin structures and the stacking faults in XTe2 are also identified by ultrafast structural responses. The comprehensive study of the ultrafast structural response in XTe2 suggests the traversal of all double-well potential energy surfaces (DWPES) by laser excitation, which is expected to be an intrinsic mechanism in the field of photoexcitation-driven global/local symmetry engineering and also a critical ingredient inducing the exotic properties in the non-equilibrium state in a large number of material systems.

Ultrafast Momentum-Resolved Hot Electron Dynamics in the Two-Dimensional Topological Insulator Bismuthene.

Two-dimensional quantum spin Hall (QSH) insulators are a promising material class for spintronic applications based on topologically protected spin currents in their edges. Yet, they have not lived up to their technological potential, as experimental realizations are scarce and limited to cryogenic temperatures. These constraints have also severely restricted characterization of their dynamical properties. Here, we report on the electron dynamics of the novel room-temperature QSH candidate bismuthene after photoexcitation using time- and angle-resolved photoemission spectroscopy. We map the transiently occupied conduction band and track the full relaxation pathway of hot photocarriers. Intriguingly, we observe photocarrier lifetimes much shorter than those in conventional semiconductors. This is ascribed to the presence of topological in-gap states already established by local probes. Indeed, we find spectral signatures consistent with these earlier findings. Demonstration of the large band gap and the view into photoelectron dynamics mark a critical step toward optical control of QSH functionalities.

Efficient First-Principles Methodology for the Calculation of the All-Phonon Inelastic Scattering in Solids.

Inelastic scattering experiments are key methods for mapping the full dispersion of fundamental excitations of solids in the ground as well as nonequilibrium states. A quantitative analysis of inelastic scattering in terms of phonon excitations requires identifying the role of multiphonon processes. Here, we develop an efficient first-principles methodology for calculating the all-phonon quantum mechanical structure factor of solids. We demonstrate our method by obtaining excellent agreement between measurements and calculations of the diffuse scattering patterns of black phosphorus, showing that multiphonon processes play a substantial role. The present approach constitutes a step towards the interpretation of static and time-resolved electron, x-ray, and neutron inelastic scattering data.

Revealing momentum-dependent electron-phonon and phonon-phonon coupling in complex materials with ultrafast electron diffuse scattering.

ABSTRACT: Despite their fundamental role in determining many important properties of materials, detailed momentum-dependent information on the strength of electron-phonon and phonon-phonon coupling across the entire Brillouin zone has remained elusive. Ultrafast electron diffuse scattering (UEDS) is a recently developed technique that is making a significant contribution to these questions. Here, we describe both the UEDS methodology and the information content of ultrafast, photoinduced changes in phonon-diffuse scattering from single-crystal materials. We present results obtained from Ni, WSe2, and TiSe2, materials that are characterized by a complex interplay between electronic (charge, spin) and lattice degrees of freedom. We demonstrate the power of this technique by unraveling carrier-phonon and phonon-phonon interactions in both momentum and time and following nonequilibrium phonon dynamics in detail on ultrafast time scales. By combining ab initio calculations with ultrafast diffuse electron scattering, insights into electronic and magnetic dynamics that impact UEDS indirectly can also be obtained.

Ultrafast lattice dynamics and electron-phonon coupling in platinum extracted with a global fitting approach for time-resolved polycrystalline diffraction data.

Quantitative knowledge of electron-phonon coupling is important for many applications as well as for the fundamental understanding of nonequilibrium relaxation processes. Time-resolved diffraction provides direct access to this knowledge through its sensitivity to laser-induced lattice dynamics. Here, we present an approach for analyzing time-resolved polycrystalline diffraction data. A two-step routine is used to minimize the number of time-dependent fit parameters. The lattice dynamics are extracted by finding the best fit to the full transient diffraction pattern rather than by analyzing transient changes of individual Debye-Scherrer rings. We apply this approach to platinum, an important component of novel photocatalytic and spintronic applications, for which a large variation of literature values exists for the electron-phonon coupling parameter G ep . Based on the extracted evolution of the atomic mean squared displacement and using a two-temperature model, we obtain G ep = ( 3.9 ± 0.2 ) × 10 17 W m 3 K (statistical error). We find that at least up to an absorbed energy density of 124 J/cm3, G ep is not fluence-dependent. Our results for the lattice dynamics of platinum provide insights into electron-phonon coupling and phonon thermalization and constitute a basis for quantitative descriptions of platinum-based heterostructures in nonequilibrium conditions.

Accessing the Anisotropic Nonthermal Phonon Populations in Black Phosphorus.

We combine ultrafast electron diffuse scattering experiments and first-principles calculations of the coupled electron-phonon dynamics to provide a detailed momentum-resolved picture of lattice thermalization in black phosphorus. The measurements reveal the emergence of highly anisotropic nonthermal phonon populations persisting for several picoseconds after exciting the electrons with a light pulse. Ultrafast dynamics simulations based on the time-dependent Boltzmann formalism are supplemented by calculations of the structure factor, defining an approach to reproduce the experimental signatures of nonequilibrium structural dynamics. The combination of experiments and theory enables us to identify highly anisotropic electron-phonon scattering processes as the primary driving force of the nonequilibrium lattice dynamics in black phosphorus. Our approach paves the way toward unravelling and controlling microscopic energy flows in two-dimensional materials and van der Waals heterostructures, and may be extended to other nonequilibrium phenomena involving coupled electron-phonon dynamics such as superconductivity, phase transitions, or polaron physics.

Nuclear dynamics of singlet exciton fission in pentacene single crystals.

Singlet exciton fission (SEF) is a key process for developing efficient optoelectronic devices. An aspect rarely probed directly, yet with tremendous impact on SEF properties, is the nuclear structure and dynamics involved in this process. Here, we directly observe the nuclear dynamics accompanying the SEF process in single crystal pentacene using femtosecond electron diffraction. The data reveal coherent atomic motions at 1 THz, incoherent motions, and an anisotropic lattice distortion representing the polaronic character of the triplet excitons. Combining molecular dynamics simulations, time-dependent density-functional theory, and experimental structure factor analysis, the coherent motions are identified as collective sliding motions of the pentacene molecules along their long axis. Such motions modify the excitonic coupling between adjacent molecules. Our findings reveal that long-range motions play a decisive part in the electronic decoupling of the electronically correlated triplet pairs and shed light on why SEF occurs on ultrafast time scales.

Ultrafast dynamical Lifshitz transition.

Fermi surface is at the heart of our understanding of metals and strongly correlated many-body systems. An abrupt change in the Fermi surface topology, also called Lifshitz transition, can lead to the emergence of fascinating phenomena like colossal magnetoresistance and superconductivity. While Lifshitz transitions have been demonstrated for a broad range of materials by equilibrium tuning of macroscopic parameters such as strain, doping, pressure, and temperature, a nonequilibrium dynamical route toward ultrafast modification of the Fermi surface topology has not been experimentally demonstrated. Combining time-resolved multidimensional photoemission spectroscopy with state-of-the-art TDDFT+U simulations, we introduce a scheme for driving an ultrafast Lifshitz transition in the correlated type-II Weyl semimetal T d-MoTe2 We demonstrate that this nonequilibrium topological electronic transition finds its microscopic origin in the dynamical modification of the effective electronic correlations. These results shed light on a previously unexplored ultrafast scheme for controlling the Fermi surface topology in correlated quantum materials.

An open-source, end-to-end workflow for multidimensional photoemission spectroscopy.

Characterization of the electronic band structure of solid state materials is routinely performed using photoemission spectroscopy. Recent advancements in short-wavelength light sources and electron detectors give rise to multidimensional photoemission spectroscopy, allowing parallel measurements of the electron spectral function simultaneously in energy, two momentum components and additional physical parameters with single-event detection capability. Efficient processing of the photoelectron event streams at a rate of up to tens of megabytes per second will enable rapid band mapping for materials characterization. We describe an open-source workflow that allows user interaction with billion-count single-electron events in photoemission band mapping experiments, compatible with beamlines at 3rd and 4rd generation light sources and table-top laser-based setups. The workflow offers an end-to-end recipe from distributed operations on single-event data to structured formats for downstream scientific tasks and storage to materials science database integration. Both the workflow and processed data can be archived for reuse, providing the infrastructure for documenting the provenance and lineage of photoemission data for future high-throughput experiments.

Observation of an Excitonic Mott Transition through Ultrafast Core-cum-Conduction Photoemission Spectroscopy.

Time-resolved soft-x-ray photoemission spectroscopy is used to simultaneously measure the ultrafast dynamics of core-level spectral functions and excited states upon excitation of excitons in WSe_{2}. We present a many-body approximation for the Green's function, which excellently describes the transient core-hole spectral function. The relative dynamics of excited-state signal and core levels clearly show a delayed core-hole renormalization due to screening by excited quasifree carriers resulting from an excitonic Mott transition. These findings establish time-resolved core-level photoelectron spectroscopy as a sensitive probe of subtle electronic many-body interactions and ultrafast electronic phase transitions.

Anisotropic Nonequilibrium Lattice Dynamics of Black Phosphorus.

Black phosphorus has recently attracted significant attention for its highly anisotropic properties. A variety of ultrafast optical spectroscopies has been applied to probe the carrier response to photoexcitation, but the complementary lattice response has remained unaddressed. Here we employ femtosecond electron diffraction to explore how the structural anisotropy impacts the lattice dynamics after photoexcitation. We observe two time scales in the lattice response, which we attribute to electron-phonon and phonon-phonon thermalization. Pronounced differences between armchair and zigzag directions are observed, indicating a nonthermal state of the lattice lasting up to ∼60 ps. This nonthermal state is characterized by a modified anisotropy of the atomic vibrations compared to equilibrium. Our findings provide insights in both electron-phonon as well as phonon-phonon coupling and bear direct relevance for any application of black phosphorus in nonequilibrium conditions.

Symmetry-guided nonrigid registration: The case for distortion correction in multidimensional photoemission spectroscopy.

Image symmetrization is an effective strategy to correct symmetry distortion in experimental data for which symmetry is essential in the subsequent analysis. In the process, a coordinate transform, the symmetrization transform, is required to undo the distortion. The transform may be determined by image registration (i.e. alignment) with symmetry constraints imposed in the registration target and in the iterative parameter tuning, which we call symmetry-guided registration. An example use case of image symmetrization is found in electronic band structure mapping by multidimensional photoemission spectroscopy, which employs a 3D time-of-flight detector to measure electrons sorted into the momentum (kx, ky) and energy (E) coordinates. In reality, imperfect instrument design, sample geometry and experimental settings cause distortion of the photoelectron trajectories and, therefore, the symmetry in the measured band structure, which hinders the full understanding and use of the volumetric band mapping datasets. We demonstrate that symmetry-guided registration can correct the symmetry distortion in the momentum-resolved photoemission patterns. Using proposed symmetry metrics, we show quantitatively that the iterative approach to symmetrization outperforms its non-iterative counterpart in the restored symmetry of the outcome while preserving the average shape of the photoemission pattern. Our approach is generalizable to distortion corrections in different types of symmetries and should also find applications in other experimental methods that produce images with similar features.