Bruno E. Schmidt

Attosecond spectroscopy in condensed matter

Comprehensive knowledge of the dynamic behaviour of electrons in condensed-matter systems is pertinent to the development of many modern technologies, such as semiconductor and molecular electronics, optoelectronics, information processing and photovoltaics. Yet it remains challenging to probe electronic processes, many of which take place in the attosecond (1 as = 10-18 s) regime. In contrast, atomic motion occurs on the femtosecond (1 fs = 10-15 s) timescale and has been mapped in solids in real time using femtosecond X-ray sources. Here we extend the attosecond techniques previously used to study isolated atoms in the gas phase to observe electron motion in condensed-matter systems and on surfaces in real time. We demonstrate our ability to obtain direct time-domain access to charge dynamics with attosecond resolution by probing photoelectron emission from single-crystal tungsten. Our data reveal a delay of approximately 100 attoseconds between the emission of photoelectrons that originate from localized core states of the metal, and those that are freed from delocalized conduction-band states. These results illustrate that attosecond metrology constitutes a powerful tool for exploring not only gas-phase systems, but also fundamental electronic processes occurring on the attosecond timescale in condensed-matter systems and on surfaces.

Linking high harmonics from gases and solids

When intense light interacts with an atomic gas, recollision between an ionizing electron and its parent ion creates high-order harmonics of the fundamental laser frequency. This sub-cycle effect generates coherent soft X-rays and attosecond pulses, and provides a means to image molecular orbitals. Recently, high harmonics have been generated from bulk crystals, but what mechanism dominates the emission remains uncertain. To resolve this issue, we adapt measurement methods from gas-phase research to solid zinc oxide driven by mid-infrared laser fields of 0.25 volts per ångström. We find that when we alter the generation process with a second-harmonic beam, the modified harmonic spectrum bears the signature of a generalized recollision between an electron and its associated hole. In addition, we find that solid-state high harmonics are perturbed by fields so weak that they are present in conventional electronic circuits, thus opening a route to integrate electronics with attosecond and high-harmonic technology. Future experiments will permit the band structure of a solid to be tomographically reconstructed.

Compression of 1.8 μm laser pulses to sub two optical cycles with bulk material

We demonstrate a simple scheme to generate 0.4 mJ 11.5 fs laser pulses at 1.8 μm. Optical parametrically amplified pulses are spectrally broadened by nonlinear propagation in an argon-filled hollow-core fiber and subsequently compressed to 1.9 optical cycles by linear propagation through bulk material in the anomalous dispersion regime. This pulse compression scheme is confirmed through numerical simulations.

All-Optical Reconstruction of Crystal Band Structure

The band structure of matter determines its properties. In solids, it is typically mapped with angle-resolved photoemission spectroscopy, in which the momentum and the energy of incoherent electrons are independently measured. Sometimes, however, photoelectrons are difficult or impossible to detect. Here we demonstrate an all-optical technique to reconstruct momentum-dependent band gaps by exploiting the coherent motion of electron-hole pairs driven by intense midinfrared femtosecond laser pulses. Applying the method to experimental data for a semiconductor ZnO crystal, we identify the split-off valence band as making the greatest contribution to tunneling to the conduction band. Our new band structure measurement technique is intrinsically bulk sensitive, does not require a vacuum, and has high temporal resolution, making it suitable to study reactions at ambient conditions, matter under extreme pressures, and ultrafast transient modifications to band structures.

CEP stable 1.6 cycle laser pulses at 1.8 μm

We report sub-mJ carrier envelope phase (CEP) stable 1.6 cycle pulses at 1.8μm. With those pulses, we have obtained 160eV cut-off in argon at an intensity of 1.4×10¹⁴W/cm² using the process of high harmonic generation.

Generation of a beam of fast electrons by tightly focusing a radially polarized ultrashort laser pulse

The generation of an electron beam through longitudinal field acceleration from a tightly focused radially polarized (TM01) laser mode is reported. The longitudinal field is generated by focusing a TM01 few-cycle laser pulse (1.8 μm, 550 μJ, 15 fs) with a high numerical aperture parabola. The created longitudinal field in the focal region is intense enough to ionize atoms and accelerate electrons to 23 keV of energy from a low density oxygen gas. The characteristics of the electron beam are presented.

High harmonic generation with long-wavelength few-cycle laser pulses

We report the extension of hollow-core fibre pulse compression to longer wavelengths. High-energy multi-cycle infrared pulses are generated via optical parametric amplification and subsequently broadened in the fibre. 2.5-cycle pulses at the Signal wavelength (1.4 ?m) and 1.6-cycle pulses at the Idler wavelength (1.8 ?m) in the sub-millijoule regime have been generated. New compression schemes can be applied at 1.8 ?m and beyond. In this manner, 1.6-cycle carrier envelope phase stable pulses were generated by linear propagation in the anomalous dispersion regime of bulk glass which surprisingly enables compression below its third-order dispersion limit. Furthermore, a dispersion-free way of controlling the carrier envelope phase is demonstrated. Moreover, we experimentally confirm the increase in high-harmonic cut-off energy with driving laser wavelength and demonstrate the beneficial effect of few-cycle pulses which enable higher saturation intensities on target compared to multi-cycle pulses. It will be an ideal tool for future synthesis of isolated attosecond pulses in the sub-keV regime. With this laser source, we revealed for the first time multi-electron effects in high harmonic generation in xenon.

Three-photon-induced luminescence of gold nanoparticles embedded in and located on the surface of glassy nanolayers

We report on the multiphoton-induced luminescence of gold nanoparticles embedded in thin glassy silicate–titanate films. The glassy layers doped with gold(III) chloride are synthesized by a sol–gel coating process. Gold nanoparticles are generated by subsequent annealing of the thin films at 300 ◦ C. Intensive near-infrared femtosecond laser irradiation also initiates the formation of gold particles, providing the possibility of spatially resolved photoactivation of the film. The reduction of gold ions to gold nanoparticles is monitored by Au L3-edge x-ray absorption near edge spectroscopy (XANES), UV–vis absorption spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The particle sizes and shapes can be tuned by changing the metal concentration in the matrix. We demonstrate that the particles exhibit an efficient, long time stable, white luminescence during near-infrared Ti:sapphire femtosecond laser excitation. The laser power-emission intensity law indicates that the luminescence is induced by the absorption of three laser photons. Cross-sectional TEM images show that gold nanoparticles are both embedded in the glassy matrix and located on the film surface. Hence, the particles should be accessible for viable applications, for example as sensor materials, and could therefore become a powerful alternative to organic and semiconducting fluorophores in biological imaging. (Some figures in this article are in colour only in the electronic version)

Tabletop imaging of structural evolutions in chemical reactions demonstrated for the acetylene cation

The introduction of femto-chemistry has made it a primary goal to follow the nuclear and electronic evolution of a molecule in time and space as it undergoes a chemical reaction. Using Coulomb Explosion Imaging, we have shot the first high-resolution molecular movie of a to and fro isomerization process in the acetylene cation. So far, this kind of phenomenon could only be observed using vacuum ultraviolet light from a free-electron laser. Here we show that 266 nm ultrashort laser pulses are capable of initiating rich dynamics through multiphoton ionization. With our generally applicable tabletop approach that can be used for other small organic molecules, we have investigated two basic chemical reactions simultaneously: proton migration and C=C bond breaking, triggered by multiphoton ionization. The experimental results are in excellent agreement with the timescales and relaxation pathways predicted by new and quantitative ab initio trajectory simulations.

Multioctave infrared supercontinuum generation in large-core As2S3 fibers

We report on infrared supercontinuum (SC) generation through laser filamentation and subsequent nonlinear propagation in a step-index As2S3 fiber. The 100 μm core and high-purity As2S3 fiber used exhibit zero-dispersion wavelength around 4.5 μm, a mid-infrared background loss of 0.2  dB/m, and a maximum loss of only 0.55  dB/m at the S-H absorption peak around 4.05 μm. When pumping with ultrashort laser pulses slightly above the S-H absorption band, broadband infrared supercontinua were generated with a 20 dB spectral flatness spanning from 1.5 up to 7 μm. The efficiency and spectral shape of the SC produced by ultrashort pulses in large-core As2S3 fiber are mainly determined by its dispersion, the S-H contaminant absorption, and the mid-infrared nonlinear absorption.