Atom probe tomography using an extreme ultraviolet trigger pulse.

Atom probe tomography (APT) is a powerful materials characterization technique capable of measuring the isotopically resolved three-dimensional (3D) structure of nanoscale specimens with atomic resolution. Modern APT instrumentation most often uses an optical pulse to trigger field ion evaporation-most commonly, the second or third harmonic of a Nd laser is utilized (∼λ = 532 nm or λ = 355 nm). Herein, we describe an APT instrument that utilizes ultrafast extreme ultraviolet (EUV) optical pulses to trigger field ion emission. The EUV light is generated via a commercially available high harmonic generation system based on a noble-gas-filled capillary. The centroid of the EUV spectrum is tunable from around 25 eV (λ = 50 nm) to 45 eV (λ = 28 nm), dependent on the identity of the gas in the capillary (Xe, Kr, or Ar). EUV pulses are delivered to the APT analysis chamber via a vacuum beamline that was optimized to maximize photon flux at the APT specimen apex while minimizing complexity. We describe the design of the beamline in detail, including the various compromises involved. We characterize the spectrum of the EUV light and its evolution as it propagates through the various optical elements. The EUV focus spot size is measured at the APT specimen plane, and the effects of misalignment are simulated and discussed. The long-term stability of the EUV source has been demonstrated for more than a year. Finally, APT mass spectra are shown, demonstrating the instrument's ability to successfully trigger field ion emission from semiconductors (Si, GaN) and insulating materials (Al2O3).

An algorithm for correcting systematic energy deficits in the atom probe mass spectra of insulating samples.

Improvements in the mass resolution of a mass spectrometer directly correlate to improvements in peak identification and quantification. Here, we describe a post-processing technique developed to increase the quality of mass spectra of strongly insulating samples in laser-pulsed atom probe microscopy. The technique leverages the self-similarity of atom probe mass spectra collected at different times during an experimental run to correct for electrostatic artifacts that present as systematic energy deficits. We demonstrate the method on fused silica (SiO2) and neodymium-doped ceria (CeO2) samples which highlight the improvements that can be made to the mass spectrum of strongly insulating samples.

Field Ion Emission in an Atom Probe Microscope Triggered by Femtosecond-Pulsed Coherent Extreme Ultraviolet Light.

This paper describes initial experimental results from an extreme ultraviolet (EUV) radiation-pulsed atom probe microscope. Femtosecond-pulsed coherent EUV radiation of 29.6 nm wavelength (41.85 eV photon energy), obtained through high harmonic generation in an Ar-filled hollow capillary waveguide, successfully triggered controlled field ion emission from the apex of amorphous SiO2 specimens. The calculated composition is stoichiometric within the error of the measurement and effectively invariant of the specimen base temperature in the range of 25 K to 150 K. Photon energies available in the EUV band are significantly higher than those currently used in the state-of-the-art near-ultraviolet laser-pulsed atom probe, which enables the possibility of additional ionization and desorption pathways. Pulsed coherent EUV light is a new and potential alternative to near-ultraviolet radiation for atom probe tomography.

A Three-Dimensional Atom Probe Microscope Incorporating a Wavelength-Tuneable Femtosecond-Pulsed Coherent Extreme Ultraviolet Light Source.

Pulsed coherent extreme ultraviolet (EUV) radiation is a potential alternative to pulsed near-ultraviolet (NUV) wavelengths for atom probe tomography. EUV radiation has the benefit of high absorption within the first few nm of the sample surface for elements across the entire periodic table. In addition, EUV radiation may also offer athermal field ion emission pathways through direct photoionization or core-hole Auger decay processes, which are not possible with the (much lower) photon energies used in conventional NUV laser-pulsed atom probe. We report preliminary results from what we believe to be the world's first EUV radiation-pulsed atom probe microscope. The instrument consists of a femtosecond-pulsed, coherent EUV radiation source interfaced to a local electrode atom probe tomograph by means of a vacuum manifold beamline. EUV photon-assisted field ion emission (of substrate atoms) has been demonstrated on various insulating, semiconducting, and metallic specimens. Select examples are shown.

Near- and Extended-Edge X-Ray-Absorption Fine-Structure Spectroscopy Using Ultrafast Coherent High-Order Harmonic Supercontinua.

Recent advances in high-order harmonic generation have made it possible to use a tabletop-scale setup to produce spatially and temporally coherent beams of light with bandwidth spanning 12 octaves, from the ultraviolet up to x-ray photon energies >1.6 keV. Here we demonstrate the use of this light for x-ray-absorption spectroscopy at the K- and L-absorption edges of solids at photon energies near 1 keV. We also report x-ray-absorption spectroscopy in the water window spectral region (284-543 eV) using a high flux high-order harmonic generation x-ray supercontinuum with 10^{9} photons/s in 1% bandwidth, 3 orders of magnitude larger than has previously been possible using tabletop sources. Since this x-ray radiation emerges as a single attosecond-to-femtosecond pulse with peak brightness exceeding 10^{26} photons/s/mrad^{2}/mm^{2}/1% bandwidth, these novel coherent x-ray sources are ideal for probing the fastest molecular and materials processes on femtosecond-to-attosecond time scales and picometer length scales.

Beating Darwin-Bragg losses in lab-based ultrafast x-ray experiments.

The use of low temperature thermal detectors for avoiding Darwin-Bragg losses in lab-based ultrafast experiments has begun. An outline of the background of this new development is offered, showing the relevant history and initiative taken by this work.

Ultrafast Time-Resolved X-ray Absorption Spectroscopy of Ferrioxalate Photolysis with a Laser Plasma X-ray Source and Microcalorimeter Array.

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. These results are compared to previously published transient X-ray absorption measurements on the same reaction and found to be consistent with the results from Ogi et al. and inconsistent with the results of Chen et al. ( Ogi , Y. ; et al. Struct. Dyn. 2015 , 2 , 034901 ; Chen , J. ; Zhang , H. ; Tomov , I. V. ; Ding , X. ; Rentzepis , P. M. Chem. Phys. Lett. 2007 , 437 , 50 - 55 ). We provide quantitative limits on the Fe-O bond length change. Finally, we review potential improvements to our measurement technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.

Photoelectron spectroscopy of CdSe nanocrystals in the gas phase: a direct measure of the evanescent electron wave function of quantum dots.

We present the first photoelectron spectroscopy measurements of quantum dots (semiconductor nanocrystals) in the gas phase. By coupling a nanoparticle aerosol source to a femtosecond velocity map imaging photoelectron spectrometer, we apply robust gas-phase photoelectron spectroscopy techniques to colloidal quantum dots, which typically must be studied in a liquid solvent or while bound to a surface. Working with a flowing aerosol of quantum dots offers the additional advantages of providing fresh nanoparticles for each laser shot and removing perturbations from bonding with a surface or interactions with the solvent. In this work, we perform a two-photon photoionization experiment to show that the photoelectron yield per exciton depends on the physical size of the quantum dot, increasing for smaller dots. Next, using effective mass modeling we show that the extent to which the electron wave function of the exciton extends from the quantum dot, the so-called "evanescent electron wavefunction", increases as the size of the quantum dot decreases. We show that the photoelectron yield is dominated by the evanescent electron density due to quantum confinement effects, the difference in the density of states inside and outside of the quantum dots, and the angle-dependent transmission probability of electrons through the surface of the quantum dot. Therefore, the photoelectron yield directly reflects the fraction of evanescent electron wave function that extends outside of the quantum dot. This work shows that gas-phase photoelectron spectroscopy is a robust and general probe of the electronic structure of quantum dots, enabling the first direct measurements of the evanescent exciton wave function.

Observing the multiexciton state in singlet fission and ensuing ultrafast multielectron transfer.

Multiple exciton generation (MEG) refers to the creation of two or more electron-hole pairs from the absorption of one photon. Although MEG holds great promise, it has proven challenging to implement, and questions remain about the underlying photo-physical dynamics in nanocrystalline as well as molecular media. Using the model system of pentacene/fullerene bilayers and femtosecond nonlinear spectroscopies, we directly observed the multiexciton (ME) state ensuing from singlet fission (a molecular manifestation of MEG) in pentacene. The data suggest that the state exists in coherent superposition with the singlet populated by optical excitation. We also found that multiple electron transfer from the ME state to the fullerene occurs on a subpicosecond time scale, which is one order of magnitude faster than that from the triplet exciton state.

Communication: Momentum-resolved quantum interference in optically excited surface states.

Surface states play essential roles in condensed matter physics, e.g., as model two-dimensional (2D) electron gases and as the basis for topological insulators. Here, we demonstrate quantum interference in the optical excitation of 2D surface states using the model system of C(60)/Au(111). These surface states are transiently populated and probed in a femtosecond time- and angle-resolved two-photon photoemission experiment. We observe quantum interference within the excited populations of these surface states as a function of parallel momentum vector. Such quantum interference in momentum space may allow one to control 2D transport properties by optical fields.