Multi-scale time-resolved electron diffraction: A case study in moiré materials.

Ultrafast-optical-pump - structural-probe measurements, including ultrafast electron and x-ray scattering, provide direct experimental access to the fundamental timescales of atomic motion, and are thus foundational techniques for studying matter out of equilibrium. High-performance detectors are needed in scattering experiments to obtain maximum scientific value from every probe particle. We deploy a hybrid pixel array direct electron detector to perform ultrafast electron diffraction experiments on a WSe2/MoSe2 2D heterobilayer, resolving the weak features of diffuse scattering and moiré superlattice structure without saturating the zero order peak. Enabled by the detector's high frame rate, we show that a chopping technique provides diffraction difference images with signal-to-noise at the shot noise limit. Finally, we demonstrate that a fast detector frame rate coupled with a high repetition rate probe can provide continuous time resolution from femtoseconds to seconds, enabling us to perform a scanning ultrafast electron diffraction experiment that maps thermal transport in WSe2/MoSe2 and resolves distinct diffusion mechanisms in space and time.

Observation of photo-induced plasmon-phonon coupling in PbTe via ultrafast x-ray scattering.

We report the observation of photo-induced plasmon-phonon coupled modes in the group IV-VI semiconductor PbTe using ultrafast x-ray diffuse scattering at the Linac Coherent Light Source. We measure the near-zone-center excited-state dispersion of the heavily screened longitudinal optical (LO) phonon branch as extracted from differential changes in x-ray diffuse scattering intensity following above bandgap photoexcitation. We suggest that upon photoexcitation, the LO phonon-plasmon coupled (LOPC) modes themselves become coupled to longitudinal acoustic modes that drive electron band shifts via acoustic deformation potentials and possibly to low-energy single-particle excitations within the plasma and that these couplings give rise to displacement-correlations that oscillate in time with a period given effectively by the heavily screened LOPC frequency.

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics.

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈10^{11} K/s) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO_{3} occurring on few picosecond time scales. We explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on a ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO_{3} and BaTiO_{3}. Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.

Engineering the Structural and Electronic Phases of MoTe2 through W Substitution.

MoTe2 is an exfoliable transition metal dichalcogenide (TMD) that crystallizes in three symmetries: the semiconducting trigonal-prismatic 2H- or α-phase, the semimetallic and monoclinic 1T'- or ß-phase, and the semimetallic orthorhombic γ-structure. The 2H-phase displays a band gap of ∼1 eV making it appealing for flexible and transparent optoelectronics. The γ-phase is predicted to possess unique topological properties that might lead to topologically protected nondissipative transport channels. Recently, it was argued that it is possible to locally induce phase-transformations in TMDs, through chemical doping, local heating, or electric-field to achieve ohmic contacts or to induce useful functionalities such as electronic phase-change memory elements. The combination of semiconducting and topological elements based upon the same compound might produce a new generation of high performance, low dissipation optoelectronic elements. Here, we show that it is possible to engineer the phases of MoTe2 through W substitution by unveiling the phase-diagram of the Mo1-xWxTe2 solid solution, which displays a semiconducting to semimetallic transition as a function of x. We find that a small critical W concentration xc ∼ 8% stabilizes the γ-phase at room temperature. This suggests that crystals with x close to xc might be particularly susceptible to phase transformations induced by an external perturbation, for example, an electric field. Photoemission spectroscopy, indicates that the γ-phase possesses a Fermi surface akin to that of WTe2.

The origin of incipient ferroelectricity in lead telluride.

The interactions between electrons and lattice vibrations are fundamental to materials behaviour. In the case of group IV-VI, V and related materials, these interactions are strong, and the materials exist near electronic and structural phase transitions. The prototypical example is PbTe whose incipient ferroelectric behaviour has been recently associated with large phonon anharmonicity and thermoelectricity. Here we show that it is primarily electron-phonon coupling involving electron states near the band edges that leads to the ferroelectric instability in PbTe. Using a combination of nonequilibrium lattice dynamics measurements and first principles calculations, we find that photoexcitation reduces the Peierls-like electronic instability and reinforces the paraelectric state. This weakens the long-range forces along the cubic direction tied to resonant bonding and low lattice thermal conductivity. Our results demonstrate how free-electron-laser-based ultrafast X-ray scattering can be utilized to shed light on the microscopic mechanisms that determine materials properties.

Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory.

Ultrafast electron probes are powerful tools, complementary to x-ray free-electron lasers, used to study structural dynamics in material, chemical, and biological sciences. High brightness, relativistic electron beams with femtosecond pulse duration can resolve details of the dynamic processes on atomic time and length scales. SLAC National Accelerator Laboratory recently launched the Ultrafast Electron Diffraction (UED) and microscopy Initiative aiming at developing the next generation ultrafast electron scattering instruments. As the first stage of the Initiative, a mega-electron-volt (MeV) UED system has been constructed and commissioned to serve ultrafast science experiments and instrumentation development. The system operates at 120-Hz repetition rate with outstanding performance. In this paper, we report on the SLAC MeV UED system and its performance, including the reciprocal space resolution, temporal resolution, and machine stability.

Room-temperature stabilization of nanoscale superionic Ag2Se.

Superionic materials are multi-component solids in which one sub-lattice exhibits high ionic conductivity within a fixed crystalline structure. This is typically associated with a structural phase transition occurring significantly above room temperature. Here, through combined temperature-resolved x-ray diffraction and differential scanning calorimetry, we map out the nanoscale size-dependence of the Ag2Se tetragonal to superionic phase transition temperature and determine the threshold size for room-temperature stabilization of superionic Ag2Se. For the first time, clear experimental evidence for such stabilization of the highly ionic conducting phase at room temperature is obtained in ∼2 nm diameter spheres, which corresponds to a >100 °C suppression of the bulk phase transition temperature. This may enable technological applications of Ag2Se in devices where high ionic conductivity at room temperature is required.

Below gap optical absorption in GaAs driven by intense, single-cycle coherent transition radiation.

Single-cycle terahertz fields generated by coherent transition radiation from a relativistic electron beam are used to study the high field optical response of single crystal GaAs. Large amplitude changes in the sub-band-gap optical absorption are induced and probed dynamically by measuring the absorption of a broad-band optical beam generated by transition radiation from the same electron bunch, providing an absolutely synchronized pump and probe geometry. This modification of the optical properties is consistent with strong-field-induced electroabsorption. These processes are pertinent to a wide range of nonlinear terahertz-driven light-matter interactions anticipated at accelerator-based sources.

Measurement of transient atomic displacements in thin films with picosecond and femtometer resolution.

We report measurements of the transient structural response of weakly photo-excited thin films of BiFeO3, Pb(Zr,Ti)O3, and Bi and time-scales for interfacial thermal transport. Utilizing picosecond x-ray diffraction at a 1.28 MHz repetition rate with time resolution extending down to 15 ps, transient changes in the diffraction angle are recorded. These changes are associated with photo-induced lattice strains within nanolayer thin films, resolved at the part-per-million level, corresponding to a shift in the scattering angle three orders of magnitude smaller than the rocking curve width and changes in the interlayer lattice spacing of fractions of a femtometer. The combination of high brightness, repetition rate, and stability of the synchrotron, in conjunction with high time resolution, represents a novel means to probe atomic-scale, near-equilibrium dynamics.

The mechanism of ultrafast structural switching in superionic copper (I) sulphide nanocrystals.

Superionic materials are multi-component solids with simultaneous characteristics of both a solid and a liquid. Above a critical temperature associated with a structural phase transition, they exhibit liquid-like ionic conductivities and dynamic disorder within a rigid crystalline structure. Broad applications as electrochemical storage materials and resistive switching devices follow from this abrupt change in ionic mobility, but the microscopic pathways and speed limits associated with this switching process are largely unknown. Here we use ultrafast X-ray spectroscopy and scattering techniques to obtain an atomic-level, real-time view of the transition state in copper sulphide nanocrystals. We observe the transformation to occur on a twenty picosecond timescale and show that this is determined by the ionic hopping time.

X-ray diffuse scattering measurements of nucleation dynamics at femtosecond resolution.

Femtosecond time-resolved small and wide angle x-ray diffuse scattering techniques are applied to investigate the ultrafast nucleation processes that occur during the ablation process in semiconducting materials. Following intense optical excitation, a transient liquid state of high compressibility characterized by large-amplitude density fluctuations is observed and the buildup of these fluctuations is measured in real time. Small-angle scattering measurements reveal snapshots of the spontaneous nucleation of nanoscale voids within a metastable liquid and support theoretical predictions of the ablation process.

Large acoustic transients induced by nonthermal melting of InSb.

We have observed large-amplitude strain waves following a rapid change in density of InSb due to nonthermal melting. The strain has been measured in real time via time-resolved x-ray diffraction, with a temporal resolution better than 2 ps. The change from the solid to liquid density of the surface layer launches a high-amplitude strain wave into the crystalline material below. This induces an effective plane rotation in the asymmetrically cut crystal leading to deflection of the diffracted beam. The uniform strain in the layer below the molten layer is 2.0(+/-0.2)%. A strain of this magnitude develops within 5 ps of the incident pulse showing that the liquid has reached the equilibrium density within this time frame. Both the strain amplitude and the depth of the strained material in the solid can be explained by assuming a reduction in the speed of sound in the nonequilibrium liquid compared to measured equilibrium values.

Carrier-density-dependent lattice stability in InSb.

The ultrafast decay of the x-ray diffraction intensity following laser excitation of an InSb crystal has been utilized to observe carrier dependent changes in the potential energy surface. For the first time, an abrupt carrier dependent onset for potential energy surface softening and the appearance of accelerated atomic disordering for a very high average carrier density have been observed. Inertial dynamics dominate the early stages of crystal disordering for a wide range of carrier densities between the onset of crystal softening and the appearance of accelerated atomic disordering.

Ultrafast bond softening in bismuth: mapping a solid's interatomic potential with X-rays.

Intense femtosecond laser excitation can produce transient states of matter that would otherwise be inaccessible to laboratory investigation. At high excitation densities, the interatomic forces that bind solids and determine many of their properties can be substantially altered. Here, we present the detailed mapping of the carrier density-dependent interatomic potential of bismuth approaching a solid-solid phase transition. Our experiments combine stroboscopic techniques that use a high-brightness linear electron accelerator-based x-ray source with pulse-by-pulse timing reconstruction for femtosecond resolution, allowing quantitative characterization of the interatomic potential energy surface of the highly excited solid.

Observation of structural anisotropy and the onset of liquidlike motion during the nonthermal melting of InSb.

The melting dynamics of laser excited InSb have been studied with femtosecond x-ray diffraction. These measurements observe the delayed onset of diffusive atomic motion, signaling the appearance of liquidlike dynamics. They also demonstrate that the root-mean-squared displacement in the [111] direction increases faster than in the [110] direction after the first 500 fs. This structural anisotropy indicates that the initially generated fluid differs significantly from the equilibrium liquid.

Time-resolved measurements of the structure of water at constant density.

Dynamical changes in the structure factor of liquid water, S(Q,t), are measured using time-resolved x-ray diffraction techniques with 100 ps resolution. On short time scales following femtosecond optical excitation, we observe temperature-induced changes associated with rearrangements of the hydrogen-bonded structure at constant volume, before the system has had time to expand. We invert this data to extract transient changes in the pair correlation function associated with isochoric heating effects, and interpret these in terms of a decrease in the local tetrahedral ordering.

Clocking femtosecond X rays.

Linear-accelerator-based sources will revolutionize ultrafast x-ray science due to their unprecedented brightness and short pulse duration. However, time-resolved studies at the resolution of the x-ray pulse duration are hampered by the inability to precisely synchronize an external laser to the accelerator. At the Sub-Picosecond Pulse Source at the Stanford Linear-Accelerator Center we solved this problem by measuring the arrival time of each high energy electron bunch with electro-optic sampling. This measurement indirectly determined the arrival time of each x-ray pulse relative to an external pump laser pulse with a time resolution of better than 60 fs rms.

Atomic-scale visualization of inertial dynamics.

The motion of atoms on interatomic potential energy surfaces is fundamental to the dynamics of liquids and solids. An accelerator-based source of femtosecond x-ray pulses allowed us to follow directly atomic displacements on an optically modified energy landscape, leading eventually to the transition from crystalline solid to disordered liquid. We show that, to first order in time, the dynamics are inertial, and we place constraints on the shape and curvature of the transition-state potential energy surface. Our measurements point toward analogies between this nonequilibrium phase transition and the short-time dynamics intrinsic to equilibrium liquids.

Bonding in liquid carbon studied by time-resolved x-ray absorption spectroscopy.

Even the most basic properties of liquid carbon have long been debated due to the challenge of studying the material at the required high temperature and pressure. Liquid carbon is volatile and thus inherently transient in an unconstrained environment. In this paper we use a new technique of picosecond time-resolved x-ray absorption spectroscopy to study the bonding of liquid carbon at densities near that of the solid. As the density of the liquid increases, we see a change from predominantly sp-bonded atomic sites to a mixture of sp, sp2, and sp3 sites and compare these observations with molecular dynamics simulations.

Transient strain driven by a dense electron-hole plasma.

We measure transient strain in ultrafast laser-excited Ge by time-resolved x-ray anomalous transmission. The development of the coherent strain pulse is dominated by rapid ambipolar diffusion. This pulse extends considerably longer than the laser penetration depth because the plasma initially propagates faster than the acoustic modes. X-ray diffraction simulations are in agreement with the observed dynamics.