Fabrication of Specimens for Atom Probe Tomography Using a Combined Gallium and Neon Focused Ion Beam Milling Approach.

We demonstrate a new focused ion beam sample preparation method for atom probe tomography. The key aspect of the new method is that we use a neon ion beam for the final tip-shaping after conventional annulus milling using gallium ions. This dual-ion approach combines the benefits of the faster milling capability of the higher current gallium ion beam with the chemically inert and higher precision milling capability of the noble gas neon ion beam. Using a titanium-aluminum alloy and a layered aluminum/aluminum-oxide tunnel junction sample as test cases, we show that atom probe tips prepared using the combined gallium and neon ion approach are free from the gallium contamination that typically frustrates composition analysis of these materials due to implantation, diffusion, and embrittlement effects. We propose that by using a focused ion beam from a noble gas species, such as the neon ions demonstrated here, atom probe tomography can be more reliably performed on a larger range of materials than is currently possible using conventional 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

Crystallographic polarity measurements in two-terminal GaN nanowire devices by lateral piezoresponse force microscopy.

Lateral piezoresponse force microscopy (L-PFM) is demonstrated as a reliable method for determining the crystallographic polarity of individual, dispersed GaN nanowires that were functional components in electrical test structures. In contrast to PFM measurements of vertically oriented (as-grown) nanowires, where a biased probe tip couples to out-of-plane deformations through the d33 piezoelectic coefficient, the L-PFM measurements in this study were implemented on horizontally oriented nanowires that coupled to shear deformations through the d15 coefficient. L-PFM phase-polarity relationships were determined experimentally using a bulk m-plane GaN sample with a known [0001] direction and further indicated that the sign of the d15 piezoelectric coefficient was negative. L-PFM phase images successfully revealed the in-plane [0001] orientation of self-assembed GaN nanowires as part of a growth polarity study and results were validated against scanning transmission electron microscopy lattice images. Combined characterization of electrical properties and crystallographic polarity was also implemented for two-terminal GaN/Al0.1Ga0.9N/GaN nanowires devices, demonstrating L-PFM measurements as a viable tool for assessing correlations between device rectification and polarization-induced band bending.

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.

Microwave near-field imaging of two-dimensional semiconductors.

Optimizing new generations of two-dimensional devices based on van der Waals materials will require techniques capable of measuring variations in electronic properties in situ and with nanometer spatial resolution. We perform scanning microwave microscopy (SMM) imaging of single layers of MoS2 and n- and p-doped WSe2. By controlling the sample charge carrier concentration through the applied tip bias, we are able to reversibly control and optimize the SMM contrast to image variations in electronic structure and the localized effects of surface contaminants. By further performing tip bias-dependent point spectroscopy together with finite element simulations, we distinguish the effects of the quantum capacitance and determine the local dominant charge carrier species and dopant concentration. These results underscore the capability of SMM for the study of 2D materials to image, identify, and study electronic defects.

GaN nanowire coated with atomic layer deposition of tungsten: a probe for near-field scanning microwave microscopy.

GaN nanowires were coated with tungsten by means of atomic layer deposition. These structures were then adapted as probe tips for near-field scanning microwave microscopy. These probes displayed a capacitive resolution of ~0.03 fF, which surpasses that of a commercial Pt tip. Upon imaging of MoS2 sheets with both the Pt and GaN nanowire tips, we found that the nanowire tips were comparatively immune to surface contamination and far more durable than their Pt counterparts.

On-chip optical interconnects made with gallium nitride nanowires.

In this Letter we report on the fabrication, device characteristics, and optical coupling of a two-nanowire device comprising GaN nanowires with light-emitting and photoconductive capabilities. Axial p-n junction GaN nanowires were grown by molecular beam epitaxy, transferred to a non-native substrate, and selectively contacted to form discrete optical source or detector nanowire components. The optical coupling demonstrated for this device may provide new opportunities for integration of optical interconnects between on-chip electrical subsystems.

Noncontact measurement of charge carrier lifetime and mobility in GaN nanowires.

The first noncontact photoconductivity measurements of gallium nitride nanowires (NWs) are presented, revealing a high crystallographic and optoelectronic quality achieved by use of catalyst-free molecular beam epitaxy. In comparison with bulk material, the NWs exhibit a long conductivity lifetime (>2 ns) and a high mobility (820 ± 120 cm(2)/(V s)). This is due to the weak influence of surface traps with respect to other III-V semiconducting NWs and to the favorable crystalline structure of the NWs achieved via strain-relieved growth.

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).

Microstructure evolution and development of annealed Ni/Au contacts to GaN nanowires.

The development of Ni/Au contacts to Mg-doped GaN nanowires (NWs) is examined. Unlike Ni/Au contacts to planar GaN, current-voltage (I-V) measurements of Mg-doped nanowire devices frequently exhibit a strong degradation after annealing in N(2)/O(2). This degradation originates from the poor wetting behavior of Ni and Au on SiO(2) and the excessive void formation that occurs at the metal/NW and metal/oxide interfaces. The void formation can cause cracking and delamination of the metal film as well as reduce the contact area at the metal/NW interface, which increases the resistance. The morphology and composition of the annealed Ni/Au contacts on SiO(2) and the p-GaN films were investigated by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) measurements. Adhesion experiments were performed in order to determine the degree of adhesion of the Ni/Au films to the SiO(2) as well as observe and analyze the morphology of the film's underside by SEM. Device degradation from annealing was prevented through the use of a specific adhesion layer of Ti/Al/Ni deposited prior to the nanowire dispersal and Ni/Au deposition. I-V measurements of NW devices fabricated using this adhesion layer showed a decrease in resistance after annealing, whereas all others showed an increase in resistance. Transmission electron microscopy (TEM) on a cross-section of a NW with Ni/Au contacts and a Ti/Al/Ni adhesion layer showed a lack of void formation at the contact/NW interface. Results of the XRD and TEM analysis of the NW contact structure using a Ti/Al/Ni adhesion layer suggests Al alloying of the Ni/Au contact increases the adhesion and stability of the metal film as well as prevents excessive void formation at the contact/NW interface.

Methanol, ethanol and hydrogen sensing using metal oxide and metal (TiO(2)-Pt) composite nanoclusters on GaN nanowires: a new route towards tailoring the selectivity of nanowire/nanocluster chemical sensors.

We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO(2)) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO(2)-Pt) nanowire-nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO(2) sensors. The GaN/TiO(2) NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO(2) sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO(2)-Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol(-1) (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 µmol mol(-1) (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential for tailoring the selectivity of the hybrid nanosensors for a multitude of environmental and industrial sensing applications.

Effect of growth orientation and diameter on the elasticity of GaN nanowires. A combined in situ TEM and atomistic modeling investigation.

We characterized the elastic properties of GaN nanowires grown along different crystallographic orientations. In situ transmission electron microscopy tensile tests were conducted using a MEMS-based nanoscale testing system. Complementary atomistic simulations were performed using density functional theory and molecular dynamics. Our work establishes that elasticity size dependence is limited to nanowires with diameters smaller than 20 nm. For larger diameters, the elastic modulus converges to the bulk values of 300 GPa for c-axis and 267 GPa for a- and m-axis.

Learning Atom Probe Tomography time-of-flight peaks for mass-to-charge ratio spectrometry.

In laser-assisted atom probe tomography, an important goal is to reconstruct the mass-to-charge ratio, (m/z), spectrum due to various ion species. In general, the probability mass function (pmf) associated with the time-of-flight (TOF) spectrum produced by each ion species is unknown and varies from species-to-species. Moreover, measuring pmfs for distinct ion species in calibration experiments is not practical. Here, we present a mixture model method to determine TOF pmfs that can vary from peak-to-peak. In this approach, we determine weights of candidate pmfs with a maximum likelihood method. In a proof-of-principle study, we apply our method to a TOF spectrum acquired from a silicon sample and determine intensity estimates of singly charged isotopes of silicon.

Highly selective GaN-nanowire/TiO2-nanocluster hybrid sensors for detection of benzene and related environment pollutants.

Nanowire-nanocluster hybrid chemical sensors were realized by functionalizing gallium nitride (GaN) nanowires (NWs) with titanium dioxide (TiO(2)) nanoclusters for selectively sensing benzene and other related aromatic compounds. Hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) nanoclusters using RF magnetron sputtering. The sensor fabrication process employed standard microfabrication techniques. X-ray diffraction and high-resolution analytical transmission electron microscopy using energy-dispersive x-ray and electron energy-loss spectroscopies confirmed the presence of the anatase phase in TiO(2) clusters after post-deposition anneal at 700 °C. A change of current was observed for these hybrid sensors when exposed to the vapors of aromatic compounds (benzene, toluene, ethylbenzene, xylene and chlorobenzene mixed with air) under UV excitation, while they had no response to non-aromatic organic compounds such as methanol, ethanol, isopropanol, chloroform, acetone and 1,3-hexadiene. The sensitivity range for the noted aromatic compounds except chlorobenzene were from 1% down to 50 parts per billion (ppb) at room temperature. By combining the enhanced catalytic properties of the TiO(2) nanoclusters with the sensitive transduction capability of the nanowires, an ultra-sensitive and selective chemical sensing architecture is demonstrated. We have proposed a mechanism that could qualitatively explain the observed sensing behavior.

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.

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-Field Control and Imaging of Free Charge Carrier Variations in GaN Nanowires.

Despite their uniform crystallinity, the shape and faceting of semiconducting nanowires (NWs) can give rise to variations in structure and associated electronic properties. Here we develop a hybrid scanning probe-based methodology to investigate local variations in electronic structure across individual n-doped GaN NWs integrated into a transistor device. We perform scanning microwave microscopy (SMM), which we combine with scanning gate microscopy (SGM) to determine the free-carrier SMM signal contribution and image local charge carrier density variations. In particular, we find significant variations in free carriers across NWs, with a higher carrier density at the wire facets. By increasing the local carrier density through tip-gating, we find that the tip injects current into the NW with strongly localized current when positioned over the wire vertices. These results suggest that the strong variations in electronic properties observed within NWs have significant implications for device design and may lead to new paths to optimization.

Passively mode-locked glass waveguide laser with 14-fs timing jitter.

Ultralow jitter pulse trains are produced from a passively mode-locked, erbium/ytterbium co-doped, planar waveguide laser by use of high-bandwidth feedback control acting on the physical cavity length and optical pump power. Synchronization of a 750-MHz, fundamentally mode-locked laser to an external clock signal yields an ultralow, root-mean-square relative timing jitter of 14.4 fs integrated from 10 Hz to the Nyquist frequency of 375 MHz.