Photoinduced Ultrafast Symmetry Switch in SnSe.

Layered tin selenide (SnSe) has recently emerged as a high-performance thermoelectric material with the current record for the figure of merit (ZT) observed in the high-temperature Cmcm phase. So far, access to the Cmcm phase has been mainly obtained via thermal equilibrium methods based on sample heating or application of external pressure, thus restricting the current understanding only to ground-state conditions. Here, we investigate the ultrafast carrier and phononic dynamics in SnSe. Our results demonstrate that optical excitations can transiently switch the point-group symmetry of the crystal from Pnma to Cmcm at room temperature in a few hundreds of femtoseconds with an ultralow threshold for the excitation carrier density. This nonequilibrium Cmcm phase is found to be driven by the displacive excitation of coherent Ag phonons and, given the absence of low-energy thermal phonons, exists in SnSe with the status of 'cold lattice with hot carriers'. Our findings provide an important insight for understanding the nonequilibrium thermoelectric properties of SnSe.

Ultrafast atomic-scale visualization of acoustic phonons generated by optically excited quantum dots.

Understanding the dynamics of atomic vibrations confined in quasi-zero dimensional systems is crucial from both a fundamental point-of-view and a technological perspective. Using ultrafast electron diffraction, we monitored the lattice dynamics of GaAs quantum dots-grown by Droplet Epitaxy on AlGaAs-with sub-picosecond and sub-picometer resolutions. An ultrafast laser pulse nearly resonantly excites a confined exciton, which efficiently couples to high-energy acoustic phonons through the deformation potential mechanism. The transient behavior of the measured diffraction pattern reveals the nonequilibrium phonon dynamics both within the dots and in the region surrounding them. The experimental results are interpreted within the theoretical framework of a non-Markovian decoherence, according to which the optical excitation creates a localized polaron within the dot and a travelling phonon wavepacket that leaves the dot at the speed of sound. These findings indicate that integration of a phononic emitter in opto-electronic devices based on quantum dots for controlled communication processes can be fundamentally feasible.

Design and implementation of an optimal laser pulse front tilting scheme for ultrafast electron diffraction in reflection geometry with high temporal resolution.

Ultrafast electron diffraction is a powerful technique to investigate out-of-equilibrium atomic dynamics in solids with high temporal resolution. When diffraction is performed in reflection geometry, the main limitation is the mismatch in group velocity between the overlapping pump light and the electron probe pulses, which affects the overall temporal resolution of the experiment. A solution already available in the literature involved pulse front tilt of the pump beam at the sample, providing a sub-picosecond time resolution. However, in the reported optical scheme, the tilted pulse is characterized by a temporal chirp of about 1 ps at 1 mm away from the centre of the beam, which limits the investigation of surface dynamics in large crystals. In this paper, we propose an optimal tilting scheme designed for a radio-frequency-compressed ultrafast electron diffraction setup working in reflection geometry with 30 keV electron pulses containing up to 105 electrons/pulse. To characterize our scheme, we performed optical cross-correlation measurements, obtaining an average temporal width of the tilted pulse lower than 250 fs. The calibration of the electron-laser temporal overlap was obtained by monitoring the spatial profile of the electron beam when interacting with the plasma optically induced at the apex of a copper needle (plasma lensing effect). Finally, we report the first time-resolved results obtained on graphite, where the electron-phonon coupling dynamics is observed, showing an overall temporal resolution in the sub-500 fs regime. The successful implementation of this configuration opens the way to directly probe structural dynamics of low-dimensional systems in the sub-picosecond regime, with pulsed electrons.

Rippling ultrafast dynamics of suspended 2D monolayers, graphene.

Here, using ultrafast electron crystallography (UEC), we report the observation of rippling dynamics in suspended monolayer graphene, the prototypical and most-studied 2D material. The high scattering cross-section for electron/matter interaction, the atomic-scale spatial resolution, and the ultrafast temporal resolution of UEC represent the key elements that make this technique a unique tool for the dynamic investigation of 2D materials, and nanostructures in general. We find that, at early time after the ultrafast optical excitation, graphene undergoes a lattice expansion on a time scale of 5 ps, which is due to the excitation of short-wavelength in-plane acoustic phonon modes that stretch the graphene plane. On a longer time scale, a slower thermal contraction with a time constant of 50 ps is observed and associated with the excitation of out-of-plane phonon modes, which drive the lattice toward thermal equilibrium with the well-known negative thermal expansion coefficient of graphene. From our results and first-principles lattice dynamics and out-of-equilibrium relaxation calculations, we quantitatively elucidate the deformation dynamics of the graphene unit cell.

Transient Structures and Possible Limits of Data Recording in Phase-Change Materials.

Phase-change materials (PCMs) represent the leading candidates for universal data storage devices, which exploit the large difference in the physical properties of their transitional lattice structures. On a nanoscale, it is fundamental to determine their performance, which is ultimately controlled by the speed limit of transformation among the different structures involved. Here, we report observation with atomic-scale resolution of transient structures of nanofilms of crystalline germanium telluride, a prototypical PCM, using ultrafast electron crystallography. A nonthermal transformation from the initial rhombohedral phase to the cubic structure was found to occur in 12 ps. On a much longer time scale, hundreds of picoseconds, equilibrium heating of the nanofilm is reached, driving the system toward amorphization, provided that high excitation energy is invoked. These results elucidate the elementary steps defining the structural pathway in the transformation of crystalline-to-amorphous phase transitions and describe the essential atomic motions involved when driven by an ultrafast excitation. The establishment of the time scales of the different transient structures, as reported here, permits determination of the possible limit of performance, which is crucial for high-speed recording applications of PCMs.

Nanomechanics and intermolecular forces of amyloid revealed by four-dimensional electron microscopy.

The amyloid state of polypeptides is a stable, highly organized structural form consisting of laterally associated ß-sheet protofilaments that may be adopted as an alternative to the functional, native state. Identifying the balance of forces stabilizing amyloid is fundamental to understanding the wide accessibility of this state to peptides and proteins with unrelated primary sequences, various chain lengths, and widely differing native structures. Here, we use four-dimensional electron microscopy to demonstrate that the forces acting to stabilize amyloid at the atomic level are highly anisotropic, that an optimized interbackbone hydrogen-bonding network within ß-sheets confers 20 times more rigidity on the structure than sequence-specific sidechain interactions between sheets, and that electrostatic attraction of protofilaments is only slightly stronger than these weak amphiphilic interactions. The potential biological relevance of the deposition of such a highly anisotropic biomaterial in vivo is discussed.

Origin of axial and radial expansions in carbon nanotubes revealed by ultrafast diffraction and spectroscopy.

The coupling between electronic and nuclear degrees of freedom in low-dimensional, nanoscale systems plays a fundamental role in shaping many of their properties. Here, we report the disentanglement of axial and radial expansions of carbon nanotubes, and the direct role of electronic and vibrational excitations in determining such expansions. With subpicosecond and subpicometer resolutions, structural dynamics were explored by monitoring changes of the electron diffraction following an ultrafast optical excitation, whereas the transient behavior of the charge distribution was probed by time-resolved, electron-energy-loss spectroscopy. Our experimental results, and supporting density functional theory calculations, indicate that a population of the excited carriers in the antibonding orbitals of the nanotube walls drives a transient axial deformation in ∼1 ps; this deformation relaxes on a much longer time scale, 17 ps, by nonradiative decay. The electron-driven expansion is distinct from the phonon-driven dynamics observed along the radial direction, using the characteristic Bragg reflections; it occurs in 5 ps. These findings reveal the nonequilibrium distortion of the unit cell at early times and the role of the electron(phonon)-induced stress in the lattice dynamics of one-dimensional nanostructures.

Diffraction of quantum dots reveals nanoscale ultrafast energy localization.

Unlike in bulk materials, energy transport in low-dimensional and nanoscale systems may be governed by a coherent "ballistic" behavior of lattice vibrations, the phonons. If dominant, such behavior would determine the mechanism for transport and relaxation in various energy-conversion applications. In order to study this coherent limit, both the spatial and temporal resolutions must be sufficient for the length-time scales involved. Here, we report observation of the lattice dynamics in nanoscale quantum dots of gallium arsenide using ultrafast electron diffraction. By varying the dot size from h = 11 to 46 nm, the length scale effect was examined, together with the temporal change. When the dot size is smaller than the inelastic phonon mean-free path, the energy remains localized in high-energy acoustic modes that travel coherently within the dot. As the dot size increases, an energy dissipation toward low-energy phonons takes place, and the transport becomes diffusive. Because ultrafast diffraction provides the atomic-scale resolution and a sufficiently high time resolution, other nanostructured materials can be studied similarly to elucidate the nature of dynamical energy localization.

Observing (non)linear lattice dynamics in graphite by ultrafast Kikuchi diffraction.

In materials, the nature of the strain-stress relationship, which is fundamental to their properties, is determined by both the linear and nonlinear elastic responses. Whereas the linear response can be measured by various techniques, the nonlinear behavior is nontrivial to probe and to reveal its nature. Here, we report the methodology of time-resolved Kikuchi diffraction for mapping the (non)linear elastic response of nanoscale graphite following an ultrafast, impulsive strain excitation. It is found that the longitudinal wave propagating along the c-axis exhibits echoes with a frequency of 9.1 GHz, which indicates the reflections of strain between the two surfaces of the material with a speed of ∼4 km/s. Because Kikuchi diffraction enables the probing of strain in the transverse direction, we also observed a higher-frequency mode at 75.5 GHz, which has a relatively long lifetime, on the order of milliseconds. The fluence dependence and the polarization properties of this nonlinear mode are entirely different from those of the linear, longitudinal mode, and here we suggest a localized breather motion in the a-b plane as the origin of the nonlinear shear dynamics. The approach presented in this contribution has the potential for a wide range of applications because most crystalline materials exhibit Kikuchi diffraction.

4D cryo-electron microscopy of proteins.

Cryo-electron microscopy is a form of transmission electron microscopy that has been used to determine the 3D structure of biological specimens in the hydrated state and with high resolution. We report the development of 4D cryo-electron microscopy by integrating the fourth dimension, time, into this powerful technique. From time-resolved diffraction of amyloid fibrils in a thin layer of vitrified water at cryogenic temperatures, we were able to detect picometer movements of protein molecules on a nanosecond time scale. Potential future applications of 4D cryo-electron microscopy are numerous, and some are discussed here.

Homogeneity of Ge-rich nanostructures as characterized by chemical etching and transmission electron microscopy.

The extension of SiGe technology towards new electronic and optoelectronic applications on the Si platform requires that Ge-rich nanostructures be obtained in a well-controlled manner. Ge deposition on Si substrates usually creates SiGe nanostructures with relatively low and inhomogeneous Ge content. We have realized SiGe nanostructures with a very high (up to 90%) Ge content. Using substrate patterning, a regular array of nanostructures is obtained. We report that electron microscopy reveals an abrupt change in Ge content of about 20% between the filled pit and the island, which has not been observed in other Ge island systems. Dislocations are mainly found within the filled pit and only rarely in the island. Selective chemical etching and electron energy-loss spectroscopy reveal that the island itself is homogeneous. These Ge-rich islands are possible candidates for electronic applications requiring locally induced stress, and optoelectronic applications which exploit the Ge-like band structure of Ge-rich SiGe.