Focused Ion Beam Milling Technique Research Articles

Atomic-Scale Characterization of Microscale Battery Particles Enabled by a High-Throughput Focused Ion Beam Milling Technique.

The cathode materials in lithium-ion batteries (LIBs) require improvements to address issues such as surface degradation, short-circuiting, and the formation of dendrites. One such method for addressing these issues is using surface coatings. Coatings can be sought to improve the durability of cathode materials, but the characterization of the uniformity and stability of the coating is important to assess the performance and lifetime of these materials. For microscale particles, there are, however, challenges associated with characterizing their surface modifications by transmission electron microscopy (TEM) techniques due to the size of these particles. Often, techniques such as focused ion beam (FIB)-assisted lift-out can be used to prepare thin cross sections to enable TEM analysis, but these techniques are very time-consuming and have a relatively low throughput. The work outlined herein demonstrates a FIB technique with direct support of microscale cathode materials on a TEM grid that increases sample throughput and reduces the processing time by 60-80% (i.e., from >5 to ∼1.5 h). The demonstrated workflow incorporates an air-liquid particle assembly followed by direct particle transfer to a TEM grid, FIB milling, and subsequent TEM analysis, which was illustrated with lithium nickel cobalt aluminum oxide particles and lithium manganese nickel oxide particles. These TEM analyses included mapping the elemental composition of cross sections of the microscale particles using energy-dispersive X-ray spectroscopy. The methods developed in this study can be extended to high-throughput characterization of additional LIB cathode materials (e.g., new compositions, coating, end-of-life studies), as well as to other microparticles and their coatings as prepared for a variety of applications.

Plasmonic Nanocone Scanning Antenna: Fabrication and Optical Properties

Optical antennas are nanostructures that introduce unprecedented possibilities for light–matter interaction at the nanoscale. An appropriately tailored plasmonic antenna can enhance the total radiative decay rate and modify the angular radiation pattern of a single‐quantum emitter through controlled near‐field coupling. Despite their ability to surpass the fundamental diffraction limit and confine the electromagnetic field to a tiny mode volume, fabricating 3D sharp scanning nanoscale plasmonic structures with desired aspect ratio is yet an ambitious goal. The fabrication of nanocones by gold evaporation on commercial atomic force microscopy probes followed by a focused ion beam milling technique is presented. The method is versatile and allows the fabrication of nanocones with desired dimensions around 100 nm along with an aspect ratio of ≈1. Their optical properties are studied and it is shown how the variation in the refractive index of the dielectric substrate affects the localized surface plasmon resonance of the nanocones, the decay rate enhancement, and the quantum yield of an emitter relevant for fluorescence/Raman scanning experiments. Theoretical studies using finite‐difference time‐domain calculations have guided the fabrication process and are consistent with experimental results.

Pulsed electrophoretic deposition of hybrid coatings from aqueous suspensions as surface functionalization and sealing technique of anodized AA2024. Part I: Morphological characterization, analysis of the interfacial interactions, and evaluation of pore impregnation of the anodic layer

In this two-part series, pulsed direct current for cathodic electrophoretic deposition (pulsed-CEPD) was studied as sealing technique of anodized AA2024 by depositing hybrid sol-gel films from aqueous suspensions. The coating was obtained using tetraethyl orthosilicate and hexadecyltrimethoxysilane as precursors and two pulse widths were used: 10 microseconds and 100 milliseconds. For comparison, continuous direct current for cathodic electrophoretic deposition was also performed. In this first article, it was developed a low-cost automated apparatus capable of creating pulsed fields using a commercial power supply. This was necessary since the automation system provided by the power supply manufacturer did not have a short enough response time able to create pulse widths in the order of microseconds. Field emission scanning electron microscopy (FESEM) and focused ion beam milling techniques were utilized to evaluate the surface morphology and interaction mechanisms in the interface anodic layer/film. Low voltage scanning transmission electron microscopy (STEM)-in-FESEM, and transmission electron microscopy (TEM) were used to evaluate the pore impregnation provided by pulsed-CEPD. Results demonstrated that the developed apparatus successfully created pulsed fields. FESEM micrographs of the anodic layer sealed by pulsed-CEPD showed that the shortest pulse provided the best films, likely due to the greater control of hydrogen bubbles generation and the promotion of a more regular deposition. Also, they revealed two interfacial interactions between the anodic layer and the film. STEM-in-FESEM images showed that the shortest pulse width provided greater pore impregnation by particles. This observation was confirmed by TEM, which demonstrated an incomplete pore impregnation for the longest pulse. Discussion regarding result interpretations is presented based on the generation and dissipation of H2(g) (considering the current interruption); on an alternative to the colloidal stability theory due to the presence of a pulsed field; and on the electrokinetic effects at the electrodes during pulsed-CEPD, that discusses how electroosmotic flow influences the deposition.

Polarization-dependent photonic crystal fiber optical filters enabled by asymmetric metasurfaces

Abstract We demonstrate in-fiber polarization-dependent optical filter by nanopatterning an asymmetric metallic metasurface array on the end-facet of polarization-maintaining photonic-crystal fibers. The asymmetric cross-typed nanoslit metasurface arrays are fabricated on the core of the optical fiber using the focused ion beam milling technique. Highly polarization- and wavelength-dependent transmission with transmission efficiency of ∼70% in the telecommunication wavelength was observed by launching two orthogonal linear-polarization states of light into the fiber. Full-wave electromagnetic simulations are in good agreement with the experimental results. These advanced meta-structured optical fibers can potentially be used as novel ultracompact in-fiber filters, splitters, and polarization converters.

Accessing phase slip events in Nb meander wires

We report transport studies through Nb-based superconducting meander wires fabricated by focused ion beam milling technique. The effect of meandering on quantum transport has been probed experimentally by a direct comparison with the pristine thin-film device before meandering. The normal metal (NM) to superconductor (SC) phase transition becomes a wide and multi-step transition by meandering. Below the transition temperature (T c), the resistance-versus-temperature measurements reveal resistive tailing which is explained by the thermally activated phase slip (TAPS) mechanism. The TAPS fit indicates a selective region of the meander to be responsible for the resistive tailing. Besides, the phase slip (PS) mechanism in the meander is evident in its current–voltage characteristics that feature the stair-case type intermediate resistive steps (IRSs) during the SC–NM transition. The modulation of the IRSs is investigated with respect to temperature and external magnetic field. It is observed that the PS events are facilitated by magnetic fields up to about 250 mT. Further, the critical current varies strongly on the temperature and magnetic field for T < 0.5 T c and H ⩽ 100 mT where it fluctuates in an oscillatory manner. Finally, Nb based meander structures can be promising candidates for future PS based studies and applications.

Investigation into water-induced surface oxidization of GaN lamella structure

The interaction between gallium nitride (GaN) and H2O has been thoroughly investigated using a novel methodology involving the fabrication of a well-defined nanometer scale GaN lamella by means of a focused ion beam milling technique. Electrical characterization results show that the exposure of the GaN surface to water at room temperature causes the device resistivity to continuously increase, which makes the GaN lamella a stable polar liquid sensor. To explain the relationship between the reduced conductivity of GaN and water dissociation on the GaN surface, we utilize surface sensitive x-ray photoelectron spectroscopy and density-functional theory calculations to investigate surface oxidation of the dry and wet GaN surface. Our studies show that the water molecules are stably adsorbed on the GaN surface and are favorable to being dissociated into hydrogen atoms and hydroxyl groups on the GaN surface even if the surface is oxidized.

(Invited) Understanding the Corrosion of SS316L in Molten LiCl-Li2O-Li Using 3D Transmission X-Ray Microscopy and 3D XANES

Pyrochemical reprocessing (pyroprocessing) of used nuclear fuel (UNF) is a promising pathway towards closing the nuclear fuel cycle and providing the means to generate durable wasteforms for portions of the UNF that are not able to be recycled. To incorporate commercial UNF (UO2) into the pyroprocessing scheme, the ceramic UNF must be converted to a metallic form at the head end of the process, which can be accomplished via electrolytic reduction of the UNF in LiCl-Li2O molten salt electrolyte. During the electrolytic reduction of UO2 at the cathode, metallic Li is inevitably co-reduced from the electrolyte due to the proximity of the reduction potential of the U4+ in UO2 and Li+ in the electrolyte. Metallic Li disperses into the LiCl electrolyte and can then interact with the process vessel and other apparatus in contact with the electrolyte, altering the rate and mechanism of the degradation of those materials.Our group has previously shown that the presence of metallic Li in the electrolyte creates a reducing condition where the surface oxide layer of SS316 is removed, and extensive intergranular corrosion takes place. To further the understanding of the mechanism and morphology of the intergranular corrosion, transmission X-ray microscopy (TXM) at Brookhaven National Laboratory’s National Synchrotron Light Source II (NSLSII) beamline 18-ID was used to examine ~20 μm diameter focused-ion beam (FIB) milled pillars of the cross-section of SS316L exposed to LiCl-Li2O-Li with 0 wt.%, 0.3 wt.%, 0.6 wt.% and 1 wt.% Li. Computed Tomographic (CT) images were obtained at X-ray energies above and below the absorption edges of alloying elements of interest, providing insight into the distribution of alloying elements after exposure to the molten salt. 3D X-ray absorption near edge spectroscopy (XANES) tomography at the Cr K-edge was also attempted. This analysis provided additional evidence of the formation of Cr-rich intermetallic phases and 3D CT images of the void structure of the exposed samples, strengthening the evidence that the sensitization of SS316L at process temperatures and the subsequent dissolution of the Cr carbide precipitates into the electrolyte is the primary driver of the deep intergranular corrosion of SS316L in LiCl-Li2O-Li. To our knowledge, this is the first application of this FIB milling technique and TXM imaging of the FIB-milled pillars to corrosion samples and lessons learned regarding the sample preparation and analysis will be presented.Acknowledgements: The authors thank Zachary Karmiol, research scientist at Materials Characterization Nevada, for technical assistance with the FIB sample preparation. This work was performed under the auspices of the Department of Energy (DOE) under contracts DE- NE0008236, and the US Nuclear Regulatory Commission (USNRC) under contract NRC-HQ-13-G-38-0027. Dr. Kenny Osborne and Ms. Nancy Hebron-Isreal serve as the program managers for the DOE and NRC awards, respectively. This research used beamline 18-ID of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This work was supported as part of the Molten Salts in Extreme Environments Energy Frontier Research Center, funded by the U.S. Department of Energy (US-DOE), Office of Science, Basic Energy Sciences, at Idaho National Laboratory under contract DE-AC07-05ID14517. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1447692. One of the authors, JM, acknowledges the Graduate Research Fellowship from the US National Science Foundation.

Amorphization and Plasticity of Olivine During Low‐Temperature Micropillar Deformation Experiments

AbstractExperimentally quantifying the viscoplastic rheology of olivine at the high stresses and low temperatures of the shallow lithosphere is challenging due to olivine's propensity to deform by brittle mechanisms at these conditions. In this study, we use microscale uniaxial compression tests to investigate the rheology of an olivine single crystal at room pressure and temperature. Pillars with nominal diameters of 1.25 μm were prepared using a focused ion beam milling technique and were subjected to sustained axial stresses of several gigapascal. The majority of the pillars failed after dwell times ranging from several seconds to a few hours. However, several pillars exhibited clear evidence of plastic deformation without failure after 4–8 hr under load. The corresponding creep strain rates are estimated to be on the order of 10−6 to 10−7 s−1. The uniaxial stresses required to achieve this deformation (4.1–4.4 GPa) are in excellent agreement with complementary data obtained using nanoindentation techniques. Scanning transmission electron microscopy observations indicate that deformation occurred along amorphous shear bands within the deformed pillars. Electron energy loss spectroscopy measurements revealed that the bands are enriched in Fe and depleted in Mg. We propose that inhomogeneities in the cation distribution in olivine concentrate stress and promote the amorphization of the Fe‐rich regions. The time dependence of catastrophic failure events suggests that the amorphous bands must grow to some critical length scale to generate an unstable defect, such as a shear crack.

Квантово-каскадные лазеры с распределенным брэгговским отражателем, сформированным методом ионно-лучевого травления

Single-frequency lasing of quantum-cascade lasers with a distributed Bragg reflector formed by the focused ion beam milling technique in the layers of the upper cladding of the waveguide is demonstrated. The active region In0.53Ga0.47As/Al0.48In0.52As is formed based on the scheme with two-phonon lower energy level depopulation in the cascade. Single-frequency lasing at a temperature of 280 K corresponded to a radiation wavelength of 7.74 μm; the side mode suppression ratio (SMSR) was 24 dB.

Creating electron phase holograms using femtosecond laser interference processing.

Recently, electron beams with structured phase fronts, such as electron vortex beams, have attracted considerable interest. Herein, we present a novel method of fabricating electron phase holograms using a femtosecond laser interference processing. A 35-nm-thick silicon membrane, corresponding to a phase shift of π for 200-keV electrons, was processed using single-shot laser irradiation, whereas processing such thin membranes with a focused ion beam milling technique would be very difficult. This rapid and efficient technique is expected to produce phase diffraction elements for practical applications in a wide range of electron optics fields.

Combining ECCI and FIB milling techniques to prepare site-specific TEM samples for crystal defect analysis of deformed minerals at high pressure

Dislocation microstructures in experimentally deformed single-crystal pyrope-rich garnet, (Mg,Fe)3(Al,Cr)3Si3O12, and polycrystalline forsterite, Mg2SiO4, were investigated by using electron channeling contrast imaging (ECCI) and transmission electron microscopy (TEM) combined with a focused ion beam (FIB)-microsampling. In the orientation-optimized ECCI method, we successfully observed individual dislocations across subgrain boundaries in a low-atomic-number mineral, pyrope-rich garnet (averaged Z-numbers, AZs∼10). Dislocations in a deformed forsterite (iron-free olivine) were also visible in the ECCI. In the ECCI on the single-crystal garnet, deformation bands consisting of dislocations, unusual contrasts in stripes and inhomogeneous distributions of sub-micrometer-sized pores were found. Further site-specific TEM observation on the deformation band revealed a high density of partial dislocations and stacking fault ribbons. The site-specific characterizations from ECCI to TEM, with assistance of FIB, can provide a new approach to investigate dislocation microstructures of deformed materials at high pressure and high temperature.

Mobilization and agglomeration of uraninite nanoparticles: A nano-mineralogical study of samples from the Matoush Uranium ore deposit

The occurrence of uraninite nanoparticles in the alteration zones of uranium ore deposits suggests potential mobilization of U(IV) under reducing conditions, which is important for understanding the mobility of uranium in contaminated sites and potential repositories for nuclear waste. This study investigates the occurrence of uraninite nanoparticles in the outer alteration zone of the Matoush uranium ore deposit, Quebec, Canada. Selected samples with finely disseminated uraninite from the outer alteration zone of the deposit are examined by X-ray fluorescence spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy on specimens prepared using the focused ion beam milling technique. Uraninite nanoparticles occur as single particles, in clusters, and in larger aggregates in close association with the Cr-rich phases chromceladonite (Cr-rich mica), ideally KMgCr3+(Si4O10)(OH)2, eskolaite, ideally Cr23+O3, bracewellite, Cr3+OOH, and an amorphous Cr-rich oxide matrix as well as with fluorapatite and galena. Nanoparticles on the surface and in the outer rim of single uraninite crystals indicate the growth of larger uraninite crystals via crystallization through particle attachment and Oswald ripening. The flow texture of the uraninite nanoparticles in the amorphous Cr-rich oxide matrix, their aggregation on the surface of nanocrystals of bracewellite, the absence of products of a redox reaction involving U(VI) and Fe(II), and the occurrence of amorphous Fe-depleted alteration layers between uraninite and eskolaite, and uraninite and Cr-rich mica indicate that the uraninite nanoparticles have been mobilized under reducing conditions (leaching of Fe2+ from the alteration layer) at low T (amorphous character of the alteration layer) after the main mineralization event from the center of the mineralization to the outer parts of the Matoush dike complex. These results indicate that fluids can mobilize U(IV) under reducing conditions in the form of uraninite nanoparticles albeit over limited distances. The potential mobilization of these nanoparticles may also explain the occurrence of proximal mineralized zones in U-ore deposits that lack common products resulting from the reduction of U(VI) by Fe2+ (e.g., hematite and other Fe3+-phases).

Fabrication and magnetic control of Y3Fe5O12 cantilevers

We have fabricated ferrite cantilevers in which their vibrational properties can be controlled by external magnetic fields. Submicron-scale cantilever structures were made from Y3Fe5O12 films by physical etching combined with the use of a focused ion beam milling technique. We found that the cantilevers exhibit two resonance modes which correspond to horizontal and vertical vibrations. Under external magnetic fields, the resonance frequency of the horizontal mode increases, while that of the vertical mode decreases, quantitatively consistent with our numerical simulation for magnetic forces. The changes in resonance frequencies with magnetic fields reach a few percent, showing that an efficient magnetic control of resonance frequencies was achieved.

Fabrication and convergent X-ray nanobeam diffraction characterization of submicron-thickness SrTiO3 crystalline sheets

The creation of thin SrTiO3 crystals from (001)-oriented SrTiO3 bulk single crystals using focused ion beam milling techniques yields sheets with submicron thickness and arbitrary orientation within the (001) plane. Synchrotron x-ray nanodiffraction rocking curve widths of these SrTiO3 sheets are less than 0.02°, less than a factor of two larger than bulk SrTiO3, making these crystals suitable substrates for epitaxial thin film growth. The change in the rocking curve width is sufficiently small that we deduce that dislocations are not introduced into the SrTiO3 sheets. Observed lattice distortions are consistent with a low concentration of point defects.

Extracting fundamental transverse mode operation in broad area quantum cascade lasers

Power scaling in broad area quantum cascade lasers results in the operation of high order transverse modes with a far-field profile consisting of two lobes propagating at large angles relative to the optical axis. We report a method of suppressing the high order transverse modes that can extract the fundamental mode and provide emission along the optical axis. By generating a lateral constriction in the waveguide in the form of short trenches defined by the focused ion beam milling technique, we report broad area devices in which most of the power is contained in a near diffraction-limited beam that provides high brightness.

Ga+ focused ion beam lithography as a viable alternative for multiple fin field effect transistor prototyping

A novel method for fast and flexible fin field effect transistor (FinFET) prototyping using a Ga+ focused ion beam is presented. The fin width and height control is explored, aiming for the successful fabrication of prototypes. This method results in fins with negligible Ga incorporation, when compared to traditional focused ion beam milling techniques. Our method for multiple fin FinFET prototyping enables advanced device fabrication and great flexibility regarding both the number of fins and fin width. Working FinFET prototypes have been fabricated using the proposed fin definition method, and the electrical characterization is discussed.

Light Emission Characteristics of Nonpolar &lt;inline-formula&gt; &lt;tex-math notation="LaTeX"&gt;$a$ &lt;/tex-math&gt; &lt;/inline-formula&gt;-Plane GaN-Based Photonic Crystal Defect Cavities

In this paper, the light emission performance from nonpolar $a$ -plane gallium nitride (GaN)-based photonic crystal (PC) slabs with line-type defect cavities has been investigated. Via the focused ion beam milling technique, thin membrane structures of the nonpolar GaN PC defect cavities were engineered, exhibiting one dominated resonant mode occurred at 419.3 nm with a high quality factor of $1.9\times 10^{3}$ in the photoluminescence emission characterizations. In the far-field region, light emission performance shows a high polarization degree of 50% with the beam direction perpendicular to the defect cavity. Compared with the PC defect cavity patterns fabricated on $c$ -axial oriented GaN materials, the $a$ -plane PC defect cavities display not only the linear light output–input power dependence, but also an invariant resonant mode of constant light emission behavior with increasing the injection carriers, therefore providing a new perspective for the future development of promising optoelectronic devices.

In Situ TEM Observations of Cu6Sn5 Polymorphic Transformations in Reaction Layers Between Sn-0.7Cu Solders and Cu Substrates

Direct evidence of the relationship between the polymorphic phase transformation from monoclinic Cu6Sn5 to hexagonal Cu6Sn5 and stress accumulation/release in Cu6Sn5, formed at the interface between Sn-0.7Cu lead-free solder and their Cu substrates, has been obtained. To explore this challenging phenomenon, we developed an in situ heating/isothermal observation technique in ultrahigh-voltage transmission electron microscopy that enables the observation of thick samples (around 0.5 μm) for solder joints, including Cu/Cu3Sn/Cu6Sn5/Sn-0.7Cu solder interfaces prepared by a focused ion beam milling technique. The results show evidence of stress creation and release events by imaging bend contours that may arise due to the polymorphic transformations of the Cu6Sn5 phase and the associated volumetric change.

Grain bridging locations of monolithic silicon carbide by means of focused ion beam milling technique

A slice and view approach using a focused ion beam (FIB) milling technique was employed to investigate grain bridging near the tip of cracks in four silicon carbide (SiC) based materials with different grain boundary chemistries and grain morphologies. Using traditional observations intergranular fracture behaviour and hence clear evidence of grain bridging was found for SiC based materials sintered with oxide additives. More surprisingly, in large grain materials, the FIB technique reveals evidence of grain bridging irrespective of the grain boundary chemistry, i.e. also in materials which macroscopically fail by transgranular failure. This helps to explain why the toughness of large grained materials is higher even if failure is transgranular.

Optical microfiber-based photonic crystal cavity

Using a focused ion beam milling technique, we fabricate broad stop band (∼10% wide) photonic crystal (PhC) cavities in adiabatically-tapered silica fibers. Abrupt structural design of PhC mirrors efficiently reduces radiation loss, increasing the cavity finesse to ∼7.5. Further experiments and simulations verify that the remaining loss is mainly due to Ga ion implantation. Such a microfiber PhC cavity probably has potentials in many light-matter interaction applications.