Attosecond electron microscopy of sub-cycle optical dynamics.

The primary step of almost any interaction between light and materials is the electrodynamic response of the electrons to the optical cycles of the impinging light wave on sub-wavelength and sub-cycle dimensions1. Understanding and controlling the electromagnetic responses of a material2-11 is therefore essential for modern optics and nanophotonics12-19. Although the small de Broglie wavelength of electron beams should allow access to attosecond and ångström dimensions20, the time resolution of ultrafast electron microscopy21 and diffraction22 has so far been limited to the femtosecond domain16-18, which is insufficient for recording fundamental material responses on the scale of the cycles of light1,2,10. Here we advance transmission electron microscopy to attosecond time resolution of optical responses within one cycle of excitation light23. We apply a continuous-wave laser24 to modulate the electron wave function into a rapid sequence of electron pulses, and use an energy filter to resolve electromagnetic near-fields in and around a material as a movie in space and time. Experiments on nanostructured needle tips, dielectric resonators and metamaterial antennas reveal a directional launch of chiral surface waves, a delay between dipole and quadrupole dynamics, a subluminal buried waveguide field and a symmetry-broken multi-antenna response. These results signify the value of combining electron microscopy and attosecond laser science to understand light-matter interactions in terms of their fundamental dimensions in space and time.

Single-Cycle Optical Control of Beam Electrons.

We report the single-cycle optical control of a freely propagating electron beam with an isolated cycle of midinfrared light. In particular, we produce and characterize a modulated electron current with peak-cycle-specific subfemtosecond structure in time. The direct effects of the carrier-envelope phase, amplitude, and dispersion of the optical waveform on the temporal composition, pulse durations, and chirp of the free-space electron wave function demonstrate the subcycle nature of our control. These results and concept may create novel opportunities in free-electron lasers, laser-driven particle accelerators, ultrafast electron microscopy, and wherever else high-energy electrons are needed with the temporal structure of single-cycle light.

Octave-spanning single-cycle middle-infrared generation through optical parametric amplification in LiGaS2.

We report the generation of extremely broadband and inherently phase-locked mid-infrared pulses covering the 5 to 11 µm region. The concept is based on two stages of optical parametric amplification starting from a 270-fs Yb:KGW laser source. A continuum seeded, second harmonic pumped pre-amplifier in ß-BaB2O4 (BBO) produces tailored broadband near-infrared pulses that are subsequently mixed with the fundamental pump pulses in LiGaS2 (LGS) for mid-infrared generation and amplification. The pulse bandwidth and chirp is managed entirely by selected optical filters and bulk material. We find an overall quantum efficiency of 1% and a mid-infrared spectrum smoothly covering 5-11 µm with a pulse energy of 220 nJ at 50 kHz repetition rate. Electro-optic sampling with 12-fs long white-light pulses directly from self-compression in a YAG crystal reveals near-single-cycle mid-infrared pulses (32 fs) with passively stable carrier-envelope phase. Such pulses will be ideal for producing attosecond electron pulses or for advancing molecular fingerprint spectroscopy.

Second-harmonic generation and self-phase modulation of few-cycle mid-infrared pulses.

Near-single-cycle mid-infrared pulses with a spectrum covering 5.4-11 µm are efficiently frequency-doubled in different GaSe crystals. The second-harmonic spectrum spans 3-4.3 µm at a power conversion efficiency of >20%. We measure an effective nonlinear coefficient of deff≈35 pm/V. We also report on self-phase modulation and spectral broadening of the mid-infrared pulses in various bulk materials and find an increase of 45% of spectral width for 5 mm of Ge. These results demonstrate that nonlinear optical conversions can efficiently be driven by few-cycle mid-infrared radiation.

Compression of picosecond pulses from a thin-disk laser to 30fs at 4W average power.

We investigate two approaches for the spectral broadening and compression of 1-ps long pulses of a thin-disk laser amplifier running at 50 kHz repetition rate at 1030 nm wavelength. We find that with a single, 2.66-m long stretched flexible hollow fiber filled with xenon gas, Fourier transform limited output pulse duration of 66 fs can be directly reached. For larger pulse shortening, we applied a hybrid cascaded approach involving a BBO-based pre-compressor and a long hollow fiber. We could achieve 33-times temporal shortening of 1-ps pulses down to a duration of 30 fs at an overall efficiency of ~29% with an output power level of 3.7 W. These results demonstrate the potential of stretched flexible fibers with their free length scalability for shortening laser pulses of moderate peak power.

Tilted Electron Pulses.

We report the all-optical generation and characterization of tilted electron pulses by means of single-cycle terahertz radiation at an electron-transmitting mirror at slanted orientation. Femtosecond electron pulses with a chosen tilt angle are produced at an almost arbitrary target location. The experiments along with theory further reveal that the pulse front tilt in electron optics is directly connected to angular dispersion. Quantum mechanical considerations suggest that this relation is general for particle beams at any degree of coherence. These results indicate that ultrashort electron pulses can be shaped in space and time as versatilely as femtosecond laser pulses, but at 10^{5} times finer wavelength and subnanometer imaging resolution.

Kerr effect in multilayer dielectric coatings.

We report the utilization of the optical Kerr effect in multilayer dielectric coatings, previously discussed only theoretically. We present the design and realization of multilayer dielectric optical structures with layer-specific Kerr nonlinearities, which permit tailoring of the intensity-dependent effects. The modulation depth in reflectance reaches up to 6% for the demonstrated examples of dielectric nonlinear multilayer coatings. We show that the nonlinearity is based on the optical Kerr effect, with the recovery time faster than the laser pulse envelope of 1 ps. Due to high flexibility in design, the reported dielectric nonlinear multilayer coatings have the potential to open hitherto unprecedented possibilities in nonlinear optics and ultrafast laser applications.

Conversion of chirp in fiber compression.

Focusing positively chirped femtosecond pulses into nonlinear fibers provides significant spectral broadening and compression at higher pulse energies than achievable conventionally because self-focusing and damage are avoided. Here, we investigate the transfer of input to output chirp in such an arrangement. Our measurements show that the group delay dispersion of the output pulse, originating from the nonlinearities, is considerably reduced as compared to the initial value, by about a factor of 10. The mechanism of chirp reduction is understood by an interplay of self-phase modulation with initial chirp within the fiber. A simple model calculation based on this picture yields satisfactory agreement with the observations and predicts significant chirp reduction for input pulses up to the µJ regime. In practice, the reduction of chirp observed here allows for compressing the spectrally broadened intense pulses by ultrabroadband dispersive multilayer mirrors of quite moderate dispersion.

Femtosecond electron beam probe of ultrafast electronics.

The need for ever-faster information processing requires exceptionally small devices that operate at frequencies approaching the terahertz and petahertz regimes. For the diagnostics of such devices, researchers need a spatiotemporal tool that surpasses the device under test in speed and spatial resolution. Consequently, such a tool cannot be provided by electronics itself. Here we show how ultrafast electron beam probe with terahertz-compressed electron pulses can directly sense local electro-magnetic fields in electronic devices with femtosecond, micrometre and millivolt resolution under normal operation conditions. We analyse the dynamical response of a coplanar waveguide circuit and reveal the impulse response, signal reflections, attenuation and waveguide dispersion directly in the time domain. The demonstrated measurement bandwidth reaches 10 THz and the sensitivity to electric potentials is tens of millivolts or -20 dBm. Femtosecond time resolution and the capability to directly integrate our technique into existing electron-beam inspection devices in semiconductor industry makes our femtosecond electron beam probe a promising tool for research and development of next-generation electronics at unprecedented speed and size.

Structured electrons with chiral mass and charge.

Chirality is a phenomenon with widespread relevance in fundamental physics, material science, chemistry, optics, and spectroscopy. In this work, we show that a free electron can be converted by the field cycles of laser light into a right-handed or left-handed coil of mass and charge. In contrast to phase-vortex beams, our electrons maintained a flat de Broglie wave but obtained their chirality from the shape of their expectation value in space and time. Measurements of wave function densities by attosecond gating revealed the three-dimensional shape of coils and double coils with left-handed or right-handed pitch. Engineered elementary particles with such or related chiral geometries should be useful for applications in chiral sensing, free-electron quantum optics, particle physics or electron microscopy.

Terahertz control and timing correlations in a transmission electron microscope.

Ultrafast electron microscopy provides a movie-like access to structural dynamics of materials in space and time, but fundamental atomic motions or electron dynamics are, so far, too quick to be resolved. Here, we report the all-optical control, compression, and characterization of electron pulses in a transmission electron microscope by the single optical cycles of laser-generated terahertz light. This concept provides isolated electron pulses and merges the spatial resolution of a transmission electron microscope with the temporal resolution that is offered by a single cycle of laser light. We also report the all-optical control of multi-electron states and find a substantial two-electron and three-electron anticorrelation in the time domain. These results open up the possibility to visualize atomic and electronic motions together with their quantum correlations on fundamental dimensions in space and time.

Avoiding temporal distortions in tilted pulses.

Tilted femtosecond laser pulses, having an intensity front with an angle to the propagation direction, can be generated by a dispersive element and a lens or mirror for imaging. Here we show that conventional geometries, for example with a grating at Littrow's condition, produce significant temporal distortions over the beam profile. The aberrations are the result of a mismatch between the grating's surface and the object plane of the imaging system. This changes the chirp of the pulses over the beam profile and lengthens the pulses to picoseconds for millimeter-sized beams. The distortions can be avoided by choosing a geometry in which the propagation direction of the tilted pulses is perpendicular to the grating's surface.

Distinct in vitro binding properties of the anti-CD20 small modular immunopharmaceutical 2LM20-4 result in profound and sustained in vivo potency in cynomolgus monkeys.

OBJECTIVES: To characterize the in vitro binding and effector function properties of CD20-directed small modular immunopharmaceutical (SMIP) 2LM20-4, and to compare its in vivo B-cell depletion activity with the mutated 2LM20-4 P331S [no in vitro complement-dependent cytotoxicity (CDC)] and rituximab in cynomolgus monkeys. METHODS: Direct binding is examined in flow cytometry, confocal microscopy, scatchard and lipid raft assays. Effector function assays include CDC and Fc-mediated cellular toxicity. In the 6-month-long in vivo B-cell depletion study, single i.v. dosages of 1 or 10 mg/kg of anti-CD20 proteins were administered to monkeys and B-cell counts were monitored in peripheral blood, bone marrow and lymph nodes. RESULTS: 2LM20-4 has lower saturation binding to human primary B cells and recruits fewer CD20 molecules into lipid rafts compared with rituximab; however, it induces higher in vitro CDC. In competitive binding, 2LM20-4 only partially displaces rituximab, suggesting that it binds to a fraction of CD20 molecules within certain locations of the plasma membrane as compared with rituximab. In monkeys, 2LM20-4 had more sustained B-cell depletion activity than rituximab in peripheral blood and had significantly more profound and sustained activity than 2LM20-4 P331S and rituximab in the lymph nodes. CONCLUSIONS: SMIP 2LM20-4, which binds to a fraction of CD20 molecules as compared with rituximab, has more potent in vitro CDC, and more potent and sustained B-cell depletion activity in cynomolgus monkeys. Our work has considerable clinical relevance since it provides novel insights related to the emerging B-cell depletion therapies in autoimmune diseases.

Photo-Switchable Nanoripples in Ti3C2Tx MXene.

MXenes are two-dimensional materials with a rich set of chemical and electromagnetic properties, the latter including saturable absorption and intense surface plasmon resonances. To fully harness the functionality of MXenes for applications in optics, electronics, and sensing, it is important to understand the interaction of light with MXenes on atomic and femtosecond dimensions. Here, we use ultrafast electron diffraction and high-resolution electron microscopy to investigate the laser-induced structural dynamics of Ti3C2Tx nanosheets. We find an exceptionally fast lattice response with an electron-phonon coupling time of 230 fs. Repetitive femtosecond laser excitation transforms Ti3C2Tx through a structural transition into a metamaterial with deeply sub-wavelength nanoripples that are aligned with the laser polarization. By a further laser illumination, the material is reversibly photo-switchable between a flat and rippled morphology. The resulting nanostructured MXene metamaterial with directional nanoripples is expected to exhibit an anisotropic optical and electronic response as well as an enhanced chemical activity that can be switched on and off by light.

Attosecond electron pulses for 4D diffraction and microscopy.

In this contribution, we consider the advancement of ultrafast electron diffraction and microscopy to cover the attosecond time domain. The concept is centered on the compression of femtosecond electron packets to trains of 15-attosecond pulses by the use of the ponderomotive force in synthesized gratings of optical fields. Such attosecond electron pulses are significantly shorter than those achievable with extreme UV light sources near 25 nm ( approximately 50 eV) and have the potential for applications in the visualization of ultrafast electron dynamics, especially of atomic structures, clusters of atoms, and some materials.

Light-Triggered Boost of Activity of Catalytic Bola-Type Surfactants by a Plasmonic Metal-Support Interaction Effect.

The maximization of activity is a general aim in catalysis research. The possibility for light-triggered enhancement of a catalytic process, even if the process is not photochemical in nature, represents an intriguing concept. Here, we present a novel system for the exploration of the latter idea. A surfactant with a catalytically active head group, a protonated polyoxometalate (POM) cluster, is attached to the surface of a gold nanoparticle (Au NP) using thiol coupling chemistry. The distance of the catalytically active center to the gold surface could be adjusted precisely using surfactants containing hydrocarbon chains (C n) of different lengths ( n = 4-10). Radiation with VIS-light has no effect on the catalytic activity of micellar aggregates of the surfactant. The situation changes, as soon as the surfactants have been attached to the Au NPs. The catalytic activity could almost be doubled. It was proven that the effect is caused by coupling the surface plasmon resonance of the Au NPs with the properties of the POM head group. The improvement of activity could only be observed if the excitation wavelength matches the absorption band of the used Au NPs. Furthermore, the shorter the distance between the POM group and the surface of the NP, the stronger is the effect. This phenomenon was explained by lowering the activation energy of the transition state relevant to the catalytic process by the strong electric fields in the vicinity of the surfaces of plasmonic nanoparticles. Because the catalytic enhancement is wavelength-selective, one can imagine the creation of complex systems in the future, a system of differently sized NPs, each responsible for a different catalytic step and activated by light of different colors.

Electron energy analysis by phase-space shaping with THz field cycles.

Time-resolved electron energy analysis and loss spectroscopy can reveal a wealth of information about material properties and dynamical light-matter interactions. Here, we report an all-optical concept for measuring energy spectra of femtosecond electron pulses with sub-eV resolution. Laser-generated terahertz radiation is used to measure arrival time differences within electron pulses with few-femtosecond precision. Controlled dispersion and subsequent compression of the electron pulses provide almost any desired compromise of energy resolution, signal strength, and time resolution. A proof-of-concept experiment on aluminum reveals an energy resolution of <3.5 eV (rms) at 70-keV after a drift distance of only 0.5 m. Simulations of a two-stage scheme reveal that pre-stretched pulses can be used to achieve <10 meV resolution, independent of the source's initial energy spread and limited only by the achievable THz field strength and measuring time.

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.

A high-resolution time-of-flight energy analyzer for femtosecond electron pulses at 30 keV.

We report a time-of-flight spectrometer for electron pulses at up to 30 keV, which is a suitable energy for atomic-resolution femtosecond investigations via time-resolved electron diffraction, microscopy, and energy loss spectroscopy. For realistic femtosecond beams without apertures, the instrument's energy resolution is ∼0.5 eV (full width at half maximum) or 2 × 10(-5) at a throughput of 50%-90%. We demonstrate the analyzer's versatility by three first applications, namely, femtosecond electron pulse metrology via optical streaking, in situ drift correction in laser-microwave synchronization for electron pulse compression, and time-resolved electron energy loss spectroscopy of aluminum, showing the instrument's capability of tracking plasmonic loss peak positions with few-meV accuracy.

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide.

Time-resolved electron diffraction with atomic-scale spatial and temporal resolution was used to unravel the transformation pathway in the photoinduced structural phase transition of vanadium dioxide. Results from bulk crystals and single-crystalline thin-films reveal a common, stepwise mechanism: First, there is a femtosecond V-V bond dilation within 300 fs, second, an intracell adjustment in picoseconds and, third, a nanoscale shear motion within tens of picoseconds. Experiments at different ambient temperatures and pump laser fluences reveal a temperature-dependent excitation threshold required to trigger the transitional reaction path of the atomic motions.