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).

Atom probe tomography.

Atom probe tomography (APT) provides three-dimensional compositional mapping with sub-nanometre resolution. The sensitivity of APT is in the range of parts per million for all elements, including light elements such as hydrogen, carbon or lithium, enabling unique insights into the composition of performance-enhancing or lifetime-limiting microstructural features and making APT ideally suited to complement electron-based or X-ray-based microscopies and spectroscopies. Here, we provide an introductory overview of APT ranging from its inception as an evolution of field ion microscopy to the most recent developments in specimen preparation, including for nanomaterials. We touch on data reconstruction, analysis and various applications, including in the geosciences and the burgeoning biological sciences. We review the underpinnings of APT performance and discuss both strengths and limitations of APT, including how the community can improve on current shortcomings. Finally, we look forwards to true atomic-scale tomography with the ability to measure the isotopic identity and spatial coordinates of every atom in an ever wider range of materials through new specimen preparation routes, novel laser pulsing and detector technologies, and full interoperability with complementary microscopy techniques.

Comparative Apex Electrostatics of Atom Probe Tomography Specimens.

Rigorous electrostatic modeling of the specimen-electrode environment is required to better understand the fundamental processes of atom probe tomography (APT) and guide the analysis of APT data. We have developed a simulation tool that self-consistently solves the nonlinear electrostatic Poisson equation along with the mobile charge carrier concentrations and provides a detailed picture of the electrostatic environment of APT specimen tips. We consider cases of metals, semiconductors, and dielectrics. Traditionally in APT, and regardless of specimen composition, the apex electric field Eapex has been approximated by the relation Eapex=SV/(kr), which was originally derived for sharp, metallic conductors; we refer to this equation as the "k-factor approximation". Here, SV is tip-electrode bias, r is the radius of curvature of the tip apex, and k is a dimensionless fitting parameter with 1.5

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.

Atomically thin layers of B-N-C-O with tunable composition.

In recent times, atomically thin alloys of boron, nitrogen, and carbon have generated significant excitement as a composition-tunable two-dimensional (2D) material that demonstrates rich physics as well as application potentials. The possibility of tunably incorporating oxygen, a group VI element, into the honeycomb sp(2)-type 2D-BNC lattice is an intriguing idea from both fundamental and applied perspectives. We present the first report on an atomically thin quaternary alloy of boron, nitrogen, carbon, and oxygen (2D-BNCO). Our experiments suggest, and density functional theory (DFT) calculations corroborate, stable configurations of a honeycomb 2D-BNCO lattice. We observe micrometer-scale 2D-BNCO domains within a graphene-rich 2D-BNC matrix, and are able to control the area coverage and relative composition of these domains by varying the oxygen content in the growth setup. Macroscopic samples comprising 2D-BNCO domains in a graphene-rich 2D-BNC matrix show graphene-like gate-modulated electronic transport with mobility exceeding 500 cm(2) V(-1) s(-1), and Arrhenius-like activated temperature dependence. Spin-polarized DFT calculations for nanoscale 2D-BNCO patches predict magnetic ground states originating from the B atoms closest to the O atoms and sizable (0.6 eV < E g < 0.8 eV) band gaps in their density of states. These results suggest that 2D-BNCO with novel electronic and magnetic properties have great potential for nanoelectronics and spintronic applications in an atomically thin platform.

Gold Nanoparticle Quantitation by Whole Cell Tomography.

Many proposed biomedical applications for engineered gold nanoparticles require their incorporation by mammalian cells in specific numbers and locations. Here, the number of gold nanoparticles inside of individual mammalian stem cells was characterized using fast focused ion beam-scanning electron microscopy based tomography. Enhanced optical microscopy was used to provide a multiscale map of the in vitro sample, which allows cells of interest to be identified within their local environment. Cells were then serially sectioned using a gallium ion beam and imaged using a scanning electron beam. To confirm the accuracy of single cross sections, nanoparticles in similar cross sections were imaged using transmission electron microscopy and scanning helium ion microscopy. Complete tomographic series were then used to count the nanoparticles inside of each cell and measure their spatial distribution. We investigated the influence of slice thickness on counting single particles and clusters as well as nanoparticle packing within clusters. For 60 nm citrate stabilized particles, the nanoparticle cluster packing volume is 2.15 ± 0.20 times the volume of the bare gold nanoparticles.