Nonthermal Bonding Origin of a Novel Photoexcited Lattice Instability in SnSe.

Lattice dynamics measurements are often crucial tools for understanding how materials transform between different structures. We report time-resolved x-ray scattering-based measurements of the nonequilibrium lattice dynamics in SnSe, a monochalcogenide reported to host a novel photoinduced lattice instability. By fitting interatomic force models to the fluence dependent excited-state dispersion, we determine the nonthermal origin of the lattice instability to be dominated by changes of interatomic interactions along a bilayer-connecting bond, rather than of an intralayer bonding network that is of primary importance to the lattice instability in thermal equilibrium.

Ultrafast X-Ray Scattering Reveals Composite Amplitude Collective Mode in the Weyl Charge Density Wave Material (TaSe_{4})_{2}I.

We report ultrafast x-ray scattering experiments of the quasi-1D charge density wave (CDW) material (TaSe_{4})_{2}I following ultrafast infrared photoexcitation. From the time-dependent diffraction signal at the CDW sidebands we identify a 0.11 THz amplitude mode derived primarily from a transverse acoustic mode of the high-symmetry structure. From our measurements we determine that this mode interacts with the valence charge indirectly through another collective mode, and that the CDW system in (TaSe_{4})_{2}I has a composite nature supporting multiple dynamically active structural degrees of freedom.

All-Optical Probe of Three-Dimensional Topological Insulators Based on High-Harmonic Generation by Circularly Polarized Laser Fields.

We report the observation of an anomalous nonlinear optical response of the prototypical three-dimensional topological insulator bismuth selenide through the process of high-order harmonic generation. We find that the generation efficiency increases as the laser polarization is changed from linear to elliptical, and it becomes maximum for circular polarization. With the aid of a microscopic theory and a detailed analysis of the measured spectra, we reveal that such anomalous enhancement encodes the characteristic topology of the band structure that originates from the interplay of strong spin-orbit coupling and time-reversal symmetry protection. The implications are in ultrafast probing of topological phase transitions, light-field driven dissipationless electronics, and quantum computation.

Femtosecond x-ray diffraction reveals a liquid-liquid phase transition in phase-change materials.

In phase-change memory devices, a material is cycled between glassy and crystalline states. The highly temperature-dependent kinetics of its crystallization process enables application in memory technology, but the transition has not been resolved on an atomic scale. Using femtosecond x-ray diffraction and ab initio computer simulations, we determined the time-dependent pair-correlation function of phase-change materials throughout the melt-quenching and crystallization process. We found a liquid-liquid phase transition in the phase-change materials Ag4In3Sb67Te26 and Ge15Sb85 at 660 and 610 kelvin, respectively. The transition is predominantly caused by the onset of Peierls distortions, the amplitude of which correlates with an increase of the apparent activation energy of diffusivity. This reveals a relationship between atomic structure and kinetics, enabling a systematic optimization of the memory-switching kinetics.

Characterization of high-harmonic emission from ZnO up to 11 eV pumped with a Cr:ZnS high-repetition-rate source.

We report the measurement of high-order harmonics from a ZnO crystal with photon energies up to 11 eV generated by a high-repetition-rate femtosecond Cr:ZnS laser operating in the mid-infrared at 2-3 µm, delivering few-cycle pulses with multi-watt average power and multi-megawatt peak power. High-focus intensity is achieved in a single pass through the crystal without a buildup cavity or nanostructued pattern for field enhancement. We measure in excess of 108 high-harmonic photons/second.

Ultrafast disordering of vanadium dimers in photoexcited VO2.

Many ultrafast solid phase transitions are treated as chemical reactions that transform the structures between two different unit cells along a reaction coordinate, but this neglects the role of disorder. Although ultrafast diffraction provides insights into atomic dynamics during such transformations, diffraction alone probes an averaged unit cell and is less sensitive to randomness in the transition pathway. Using total scattering of femtosecond x-ray pulses, we show that atomic disordering in photoexcited vanadium dioxide (VO2) is central to the transition mechanism and that, after photoexcitation, the system explores a large volume of phase space on a time scale comparable to that of a single phonon oscillation. These results overturn the current understanding of an archetypal ultrafast phase transition and provide new microscopic insights into rapid evolution toward equilibrium in photoexcited matter.

Direct Measurement of Anharmonic Decay Channels of a Coherent Phonon.

We report channel-resolved measurements of the anharmonic coupling of the coherent A_{1g} phonon in photoexcited bismuth to pairs of high wave vector acoustic phonons. The decay of a coherent phonon can be understood as a parametric resonance process whereby the atomic displacement periodically modulates the frequency of a broad continuum of modes. This coupling drives temporal oscillations in the phonon mean-square displacements at the A_{1g} frequency that are observed across the Brillouin zone by femtosecond x-ray diffuse scattering. We extract anharmonic coupling constants between the A_{1g} and several representative decay channels that are within an order of magnitude of density functional perturbation theory calculations.

Solid-state harmonics beyond the atomic limit.

Strong-field laser excitation of solids can produce extremely nonlinear electronic and optical behaviour. As recently demonstrated, this includes the generation of high harmonics extending into the vacuum-ultraviolet and extreme-ultraviolet regions of the electromagnetic spectrum. High harmonic generation is shown to occur fundamentally differently in solids and in dilute atomic gases. How the microscopic mechanisms in the solid and the gas differ remains a topic of intense debate. Here we report a direct comparison of high harmonic generation in the solid and gas phases of argon and krypton. Owing to the weak van der Waals interaction, rare (noble)-gas solids are a near-ideal medium in which to study the role of high density and periodicity in the generation process. We find that the high harmonic generation spectra from the rare-gas solids exhibit multiple plateaus extending well beyond the atomic limit of the corresponding gas-phase harmonics measured under similar conditions. The appearance of multiple plateaus indicates strong interband couplings involving multiple single-particle bands. We also compare the dependence of the solid and gas harmonic yield on laser ellipticity and find that they are similar, suggesting the importance of electron-hole recollision in these solids. This implies that gas-phase methods such as polarization gating for attosecond pulse generation and orbital tomography could be realized in solids.

Imaging transient melting of a nanocrystal using an X-ray laser.

There is a fundamental interest in studying photoinduced dynamics in nanoparticles and nanostructures as it provides insight into their mechanical and thermal properties out of equilibrium and during phase transitions. Nanoparticles can display significantly different properties from the bulk, which is due to the interplay between their size, morphology, crystallinity, defect concentration, and surface properties. Particularly interesting scenarios arise when nanoparticles undergo phase transitions, such as melting induced by an optical laser. Current theoretical evidence suggests that nanoparticles can undergo reversible nonhomogenous melting with the formation of a core-shell structure consisting of a liquid outer layer. To date, studies from ensembles of nanoparticles have tentatively suggested that such mechanisms are present. Here we demonstrate imaging transient melting and softening of the acoustic phonon modes of an individual gold nanocrystal, using an X-ray free electron laser. The results demonstrate that the transient melting is reversible and nonhomogenous, consistent with a core-shell model of melting. The results have implications for understanding transient processes in nanoparticles and determining their elastic properties as they undergo phase transitions.

Ultrafast photovoltaic response in ferroelectric nanolayers.

We show that light drives large-amplitude structural changes in thin films of the prototypical ferroelectric PbTiO3 via direct coupling to its intrinsic photovoltaic response. Using time-resolved x-ray scattering to visualize atomic displacements on femtosecond time scales, photoinduced changes in the unit-cell tetragonality are observed. These are driven by the motion of photogenerated free charges within the ferroelectric and can be simply explained by a model including both shift and screening currents, associated with the displacement of electrons first antiparallel to and then parallel to the ferroelectric polarization direction.

Redshift in the optical absorption of ZnO single crystals in the presence of an intense midinfrared laser field.

We report time-resolved electroabsorption of a weak probe in a 500 µm thick zinc-oxide crystal in the presence of a strong midinfrared pump in the tunneling limit. We observe a substantial redshift in the absorption edge that scales with the cube root of intensity up to 1 TW/cm(2) (0.38 eV cm(2/3) TW(-1/3)) after which it increases more slowly to 0.4 eV at a maximum applied intensity of 5 TW/cm(2). The maximum shift corresponds to more than 10% of the band gap. The change in scaling occurs in a regime of nonperturbative high-order harmonic generation where electrons undergo periodic Bragg scattering from the Brillouin zone boundaries. It also coincides with the limit where the electric field becomes comparable to the ratio of the band gap to the lattice spacing.

Pulsed-laser creation and characterization of giant plasma membrane vesicles from cells.

Femtosecond-pulsed laser irradiation was found to initiate giant plasma membrane vesicle (GPMV) formation on individual cells. Laser-induced GPMV formation resulted from intracellular cavitation and did not require the addition of chemical stressors to the cellular environment. The viscosity, structure, and contents of laser-induced GPMVs were measured with fluorescence microscopy and single-particle tracking. These GPMVs exhibit the following properties: (1) GPMVs grow fastest immediately after laser irradiation; (2) GPMVs contain barriers to free diffusion of incorporated fluorescent beads; (3) materials from both the cytoplasm and surrounding media flow into the growing GPMVs; (4) the GPMVs are surrounded by phospholipids, including phosphatidylserine; (5) F-actin is incorporated into the vesicles; and (6) caspase activity is not essential for GPMV formation. The effective viscosity of 65 nm polystyrene nanoparticles within GPMVs ranged from 32 to 434 cP. The nanoparticle diffusion was commonly affected by relatively large, macromolecular structures within the bleb.

Wideband detection of transient solid-state dynamics using ultrafast fiber lasers and asynchronous optical sampling.

We demonstrate optical time-domain spectroscopy from femtoseconds to nanoseconds using an ultrafast dual-fiber-laser system with kilohertz continuous scanning rates. Utilizing different wavelengths for the pump and probe beams, we exploit this system's broad range of timescales for quantitative studies of thermal transport and the detection of coherent spin and lattice excitations in epitaxial magnetic thin films. The extraordinary temporal dynamic range provides a way to connect the fast and slow timescales in the observation of dissipation and decoherence processes.

X-ray synchrotron studies of ultrafast crystalline dynamics.

Ultrafast X-ray experiments at synchrotron sources hold tremendous promise for measuring the atomistic dynamics of materials under a wide variety of transient conditions. In particular, the marriage of synchrotron radiation and ultrafast laser technology is opening up a new frontier of materials research. Structural changes initiated by femtosecond laser pulses can be tracked in real time using time-resolved X-ray diffraction on picosecond time scales or shorter. Here, research at the Advanced Photon Source is described, illustrating the opportunities for ultrafast diffraction with some recent work on the generation of impulsive strain, coherent phonon generation and supersonic diffusion of electron-hole plasmas. The flexibility of time-resolved Bragg and Laue diffraction geometries are both utilized to illuminate the strain generation and evolution process. Time-resolved X-ray science will become increasingly important with the construction of linac-based ultrafast X-ray sources.