Argon Ion Beam Milling Research Articles

Emergence of Amphiphilicity on Surfaces of Pure Cellulose Nanofibrils Directly Generated by Aqueous Counter Collision Process.

The present paper describes a downsizing mechanism of an aqueous counter collision (ACC) process that enables the rapid preparation of cellulose nanofibrils (CNFs) as an aqueous dispersion solely by impinging a pair of water jets containing the raw materials. Extensive studies have revealed that the resulting CNFs by ACC have amphiphilic fiber surfaces, in which two kinds of faces with different natures are present along the entire fiber axis. They therefore have superior adsorption to surfaces of various conventional polymer plastics. These characteristic adsorption behaviors, which are totally different from those for other CNFs prepared by other means, are attributable to their hydrophobic surfaces. In the present study, high-resolution microscopy, including atomic force microscopy, confocal laser scanning microscopy, and scanning electron microscopy with broad argon ion beam milling, was used to determine how the emergence of such hydrophobic characteristics in a nanofibril face occurs in relation to the ACC nanopulverization mechanism due to the collision of the pair of water jets.

Pore Distribution Characteristics of Different Lithofacies Shales: Evidence from Scanning Electron Microscopy

To disclose the pore distribution characteristics of different lithofacies lacustrine shales, ten samples collected from the Shahejie Formation, Dongying Sag, Bohai Bay Basin, China, were examined using argon ion beam milling–scanning electron microscopy (SEM). A quantitative method was adopted to characterize shale pore distributions based on the SEM images. Mercury intrusion capillary pressure was employed to determine the pore throat size distributions of the shales. The SEM images indicated that in shale reservoirs, interparticle pores at the edges of brittle particles and intraparticle pores in clay mineral aggregates primarily contribute to the reservoir spaces and that in calcite-rich shales, dissolution pores provide secondary reservoir space. Among the morphologies of dissolution, intraparticle, and interparticle pores, the morphology of the dissolution pores is the simplest, followed by those of intraparticle and interparticle pores in that order. Clay and felsic minerals primarily control the shale pore sizes and the larger the clay mineral content in the shales, the smaller their pore size; the felsic minerals demonstrate the opposite behavior. The image-based point counting data indicate that shale pore sizes are mostly between 20 nm and 2 μm. In contrast, most pore throats are less than 20 nm in diameter, implying that the pores in the nanometer to micrometer scales are connected by tiny throats. Among the four lithofacies shales, felsic-rich shales are favorable for shale oil accumulation and seepage because of their large pore sizes and throats their ability to form intercalated shale oil adjacent to organic-rich shales. Calcareous shales with a large number of dissolution pores and a large content of organic matter could produce self-generation and self-storage matrix shale oil and would typically develop fractures, thereby creating a seepage channel for shale oil. This study presents the micro-distributions of different lithofacies of shale pores, which would help in understanding the occurrence and seepage of oil in shale reservoirs.

A combination of scanning electron microscopy and broad argon ion beam milling provides intact structure of secondary tissues in woody plants

The secondary tissues of woody plants consist of fragile cells and rigid cell walls. However, the structures are easily damaged during mechanical cross-sectioning for electron microscopy analysis. Broad argon ion beam (BIB) milling is commonly employed for scanning electron microscopy (SEM) of hard materials to generate a large and distortion-free cross-section. However, BIB milling has rarely been used in plant science. In the present study, SEM combined with BIB milling was validated as an accurate tool for structural observation of secondary woody tissues of two samples, living pine (Pinus densiflora) and high-density oak wood (Quercus phillyraeoides), and compared with classical microtome cross-sectioning. The BIB milling method does not require epoxy resin embedding because of prior chemical fixation and critical point drying of the sample, thus producing a three-dimensional image. The results showed that xylem structures were well-preserved in their natural state in the BIB-milled cross-section compared with the microtome cross-section. The observations using SEM combined with BIB milling were useful for wide-area imaging of both hard and soft plant tissues, which are difficult to observe with transmitted electron microscopy because it is difficult to obtain sections of such tissues, particularly those of fragile reaction woods.

Sample preparation and microscopical investigation techniques for metal and ceramics containing graphite and graphene-like layered particles.

Scanning electron microscopy (SEM) techniques are widely used in microstructural investigations of materials since it can provide surface morphology, topography, and chemical information. However, it is important to use correct imaging and sample preparation techniques to reveal the microstructures of materials composed of components with different polishing characteristics such as grey cast iron, graphene platelets (GPLs)-added SiAlON composite, SiC and B4 C ceramics containing graphite or graphene-like layered particles. In this study, all microstructural details of gray cast iron were successfully revealed by using argon ion beam milling as an alternative to the standard sample preparation method for cast irons, that is, mechanical polishing followed by chemical etching. The in-lens secondary electron (I-L-SE) image was clearly displayed on the surface details of the graphites that could not be revealed by backscattered electron (BSE) and Everhart-Thornley secondary electron (E-T SE) images. Mechanical polishing leads to pull-out of GPLs from SiAlON surface, whereas argon ion beam milling preserved the GPLs and resulted in smooth surface. Grain and grain boundaries of polycrystalline SiC and B4 C were easily revealed by using I-L SE image in the SEM after only mechanical polishing without any etching process. While the BSE and E-T SE images did not clearly show the residual graphites in the microstructure, their distribution in the B4 C matrix was fully revealed in the I-L SE image.

Assessment of pitting corrosion in bare and passivated (wet scCO2‐induced patination and chemical passivation) hot‐dip galvanized steel samples with SVET, FTIR, and SEM (EDS)

AbstractIn this study, the local electrochemical activity of untreated and passivated (natural or chemical passivation) zinc specimens was observed during immersion in a 0.1‐M NaCl solution. The localized anodic activity during the exposure, measured with the scanning vibrating electrode technique, was linked to zinc dissolution by the pitting corrosion mechanism. It was correlated to specific corrosion products characterized by Fourier transmission infrared (FTIR) microscopy. FTIR molecule maps were produced from individual pitting corrosion sites (100–200 µm in width). With argon ion beam milling and latest energy‐dispersive X‐ray spectroscopy (EDS) technology, element maps with a high spatial resolution (≪100 nm) were recorded from abrasion‐ and beam‐sensitive corrosion products, showing a residual layer structure. This study demonstrates the capability of FTIR mapping, cross‐section polishing, and state‐of‐the‐art scanning electron microscopy imaging, and EDS element mapping to produce high‐resolution elemental, molecular, and visual information about pitting corrosion mechanisms on a hot‐dip galvanized steel sample.

An argon ion beam milling process for native AlOx layers enabling coherent superconducting contacts

We present an argon ion beam milling process to remove the native oxide layer forming on aluminum thin films due to their exposure to atmosphere in between lithographic steps. Our cleaning process is readily integrable with conventional fabrication of Josephson junction quantum circuits. From measurements of the internal quality factors of superconducting microwave resonators with and without contacts, we place an upper bound on the residual resistance of an ion beam milled contact of 50 mΩ μm2 at a frequency of 4.5 GHz. Resonators for which only 6% of the total foot-print was exposed to the ion beam milling, in areas of low electric and high magnetic fields, showed quality factors above 106 in the single photon regime, and no degradation compared to single layer samples. We believe these results will enable the development of increasingly complex superconducting circuits for quantum information processing.

Silica imprint templates with concave patterns from single-digit nanometers fabricated by electron beam lithography involving argon ion beam milling

To maintain the silica surface of imprint templates without a fluorine-containing passivation layer on sidewalls after dry etching, we investigated whether a physical dry etching process entailing exposure to Ar ion beam is useful for the fabrication of silica templates. An almost same etching rate of a positive-tone electron beam (EB) resist as silica in Ar ion beam milling allowed for the fabrication of bar-shaped patterns with micrometer lengths and widths for moiré alignment and of hole patterns with diameters of around 20 nm in silica templates. The EB resist layer of 40 nm thickness generated partially non-etched defects of 10-nm-diameter holes in silica templates because the Ar ion beam was completely unable to reach silica surfaces through resist sidewalls with a depth of 40 nm. The break-through etching of a hard mask sacrifice Cr layer with a thickness of 5 nm by Ar ion milling and the subsequent inductively coupled plasma etching of silica enabled the fabrication of silica hole templates with diameters of 7–20 nm and depths of 20–30 nm.

Effects of Thickness on the Metal-Insulator Transition in Free-Standing Vanadium Dioxide Nanocrystals.

Controlling solid state phase transitions via external stimuli offers rich physics along with possibilities of unparalleled applications in electronics and optics. The well-known metal-insulator transition (MIT) in vanadium dioxide (VO2) is one instance of such phase transitions emerging from strong electronic correlations. Inducing the MIT using electric field has been investigated extensively for the applications in electrical and ultrafast optical switching. However, as the Thomas-Fermi screening length is very short, for considerable alteration in the material's properties with electric field induced MIT, crystals below 10 nm are needed. So far, the only way to achieve thin crystals of VO2 has been via epitaxial growth techniques. Yet, stress due to lattice mismatch as well as interdiffusion with the substrate complicate the studies. Here, we show that free-standing vapor-phase grown crystals of VO2 can be milled down to the desired thickness using argon ion-beam milling without compromising their electronic and structural properties. Among our results, we show that even below 4 nm thickness the MIT persists and the transition temperature is lowered in two-terminal devices as the crystal gets thinner. The findings in this Letter can be applied to similar strongly correlated materials to study quantum confinement effects.

Pore structure characteristics of lower Silurian shales in the southern Sichuan Basin, China: Insights to pore development and gas storage mechanism

Silurian shale in Sichuan Basin is currently the most important target zone for shale gas exploration and development in China. Pore structure characteristics of Lower Silurian Longmaxi shales from southern Sichuan Basin were investigated. The combination of field emission scanning electron microscope (FE–SEM) and argon ion beam milling was utilized to describe the nanometer-to micrometer-scale (>1.2nm) pore systems. The shales were characterized by organic geochemical and mineralogical analyses. Total porosity, pore size distribution (PSD), specific surface area, and gas content were determined. Controls of organic matter richness, thermal maturity, and mineralogy on porosity were examined. The contribution of individual mineral components to total porosity was analyzed quantitatively. Total gas contents of the shales determined from canister desorption data were compared with theoretical (sorptive and volumetric) gas storage capacities.The total organic carbon (TOC) content of the shale samples ranges between 0.1 and 8.0 wt.% and helium porosity varies between 0.7 and 5.7%. Maturity in terms of equivalent vitrinite reflectance of bitumen (Reqv) ranges from 1.8 to 3.2%. TOC content is a strong control for the pore system of these shales, and shows a positive correlation with porosity. Porosity increases with increasing thermal maturity when Reqv is less than 2.5%, but decreases for higher thermal maturity samples. FE–SEM reveals four pore types related to the rock matrix that are classified as follows: organic matter (OM)–hosted pores, pores in clay minerals, pores of framework minerals, and intragranular pores in microfossils. Pores in clay minerals are always associated with the framework of clay flakes, and develop around rigid mineral grains because the pressure shadows of mineral grains prevent pores from collapsing. Pores of framework minerals are probably related to dissolution by acidic fluids, and the dissolution–related pores promote porosity of shales. A unimodal PSD exists in the micropore range of TOC–rich samples, while the PSD of carbonate–rich samples are bimodal. A PSD maximum in the micropore range is attributed by OM and another maximum in the range of mesopore–macropores is probably caused by the dissolution of carbonate minerals. Quantitative evaluation of the contribution of individual mineral components to porosity shows that the organic matter contributes approximately 62% to the total porosity. Framework minerals (quartz, feldspar, and carbonates, et al.) and clay minerals contribute 25% and 13%, respectively. The total gas content of these shales ranges from 0.4 to 6.2m3/t, and the total gas contents of selected samples determined from canister desorption tests agree with the theoretically estimated original gas-in-place (OGIP). OM-hosted pores are the main space for gas storage, and accounted for about 78% (55% adsorbed gas plus 23% free gas) of the OGIP, while pores in the inorganic matter accommodate 22% free gas of the OGIP.

Pore structure of Cambrian shales from the Sichuan Basin in China and implications to gas storage

The microstructure of black siliceous shale from the lower Cambrian Niutitang Formation, Sichuan Basin in China was investigated by the combination of field emission scanning electron microscope (FE-SEM) and argon ion beam milling. The nanometer-to micrometer-scale pore systems of shales are an important control on gas storage and fluid migration. In this paper, the organic porosity in shale samples within oil and gas window has been investigated, and the formation mechanism and diagenetic evolution of nanopores have been researched.FE-SEM reveals five pore types that are classified as follows: organic nanopores, pores in clay minerals, nanopores of framework minerals, intragranular pores in microfossils, and microfractures. Numerous organic nanopores are observed in shales in the gas window, whereas microfractures can be seen within the organic matter of shales in the oil window. Microfractures in oil window shales could be attributed to pressure buildup in the organic matter when incompressible liquid hydrocarbon are generated, and the orientation of microfractures is probably parallel to the bedding and strength anisotropy of the formation. Pores in clay minerals are always associated with the framework of clay flakes, and develop around rigid mineral grains because the pressure shadows of mineral grains protect pores from collapse, and the increasing of silt content would lead to an increase in pressure shadows and improve porosity. Nanopores of rock framework are probably related to dissolution by acidic fluids from hydrocarbon generation, and the dissolution-related pores promote permeability of shales. Porosity in the low-TOC, low-thermal-maturity shales contrast greatly with those of high-TOC, high-thermal-maturity shales. While the high-TOC shales contain abundant organic microporosity, the inorganic pores can contribute a lot to the porosity of the low-TOC shales.

Terahertz Waves Emission From Two <formula formulatype="inline"><tex Notation="TeX">$\hbox{Bi}_{2}\hbox{Sr}_{2} \hbox{CaCu }_{2} \hbox{O} _{8}$</tex></formula> Mesas in Series

The dependence of terahertz (THz) emission power on the thickness of series Bi <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> Sr <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> CaCu <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">8</sub> (BSCCO) mesas is studied in this letter. An intrinsic Josephson junction (IJJ) array with two BSCCO mesas in series is proposed. The current-voltage characteristics of the IJJs, the powers, and Fourier spectra of the THz emission are measured for different thicknesses of the mesas, which is gradually mounted by the argon ion beam milling. Experiment results indicate that the THz emission power grows as the thickness of the mesas is increasing. The power reaches a maximum value of about 0.502 μW at a frequency of 0.708 THz when the thickness is 1200 nm. However, the THz emission power decreases while the thickness of the mesas keeps increasing. This nonlinearity between the THz emission power and the thickness of the mesas is due to the cavity resonance of the mesas and the self-heating generated by the IJJs in the mesas. The structure of connecting two mesas in series can be extended to form an IJJ array of multiple series mesas, which could further improve the THz emission power.

Size-tuned ZnO nanocrucible arrays for magnetic nanodot synthesis via atomic layer deposition-assisted block polymer lithography.

Low-temperature atomic layer deposition of conformal ZnO on a self-assembled block polymer lithographic template comprising well-ordered, vertically aligned cylindrical pores within a poly(styrene) (PS) matrix was used to produce nanocrucible templates with pore diameters tunable via ZnO thickness. Starting from a PS template with a hexagonal array of 30 nm diameter pores on a 45 nm pitch, the ZnO thickness was progressively increased to narrow the pore diameter to as low as 14 nm. Upon removal of the PS by heat treatment in air at 500 °C to form an array of size-tunable ZnO nanocrucibles, permalloy (Ni80Fe20) was evaporated at normal incidence, filling the pores and creating an overlayer. Argon ion beam milling was then used to etch back the overlayer (a Damascene-type process), leaving a well-ordered array of isolated ZnO nanocrucibles filled with permalloy nanodots. Microscopy and temperature-dependent magnetometry verified the diameter reduction with increasing ZnO thickness. The largest diameter (30 nm) dots exhibit a ferromagnetic multidomain/vortex state at 300 K, with relatively weakly temperature-dependent coercivity. Reducing the diameter leads to a crossover to a single-domain state and eventually superparamagnetism at sufficiently high temperature, in quantitative agreement with expectations. We argue that this approach could render this form of block polymer lithography compatible with high-temperature processing (as required for technologically important high perpendicular anisotropy ordered alloys, for instance), in addition to enabling separation-dependent studies to probe interdot magnetostatic interactions.

Effect of feature size on dielectric nonlinearity of patterned PbZr0.52Ti0.48O3 films

Lead zirconate titanate, PZT (52/48), thin films with a PbTiO3 seed layer were patterned into features of different widths, including various sizes of squares and 100 μm, 50 μm, and 10 μm serpentine designs, using argon ion beam milling. Patterns with different surface area/perimeter ratios were used to study the relative importance of damage produced by the patterning. It was found that as the pattern dimensions decreased, the remanent polarization increased, presumably due to the fact that the dipoles near the feature perimeter are not as severely clamped to the substrate. This investigation is in agreement with a model in which clamping produces deep wells, which do not allow some fraction of the spontaneous polarization to switch at high field. The domain wall mobility at modest electric fields was investigated using the Rayleigh law. Both the reversible, εinit, and irreversible, α, Rayleigh coefficients increased with decreasing serpentine line width for de-aged samples. For measurements made immediately after annealing, εinit of 500 μm square patterns was 1510 ± 13; with decreasing serpentine line width, εinit rose from 1520 ± 10 for the 100 μm serpentine to 1568 ± 23 for the 10 μm serpentine. The irreversible parameter, α, for the square patterns was 39.4 ± 3.2 cm/kV and it increased to 44.1 ± 3.2 cm/kV as the lateral dimension is reduced. However, it was found that as the width of the serpentine features decreased, the aging rate rose. These observations are consistent with a model in which sidewall damage produces shallow wells that lower the Rayleigh constants of aged samples at small fields. These shallow wells can be overcome by the large fields used to measure the remanent polarization and the large unipolar electric fields typically used to drive thin film piezoelectric actuators.

Sensing properties of infrared nanostructured plasmonic crystals fabricated by electron beam lithography and argon ion milling

In this paper, the authors report on the fabrication, theory simulation, and optical characterization of X-shaped nanoscale plasmonic crystals (PCs) and their application in biosensors. X-shaped PCs with 30 nm feature line-widths and different intersection angles were fabricated by a combination of electron beam lithography and argon ion beam milling techniques. Both experimental measurement and finite-difference time-domain simulations were employed to study the transmission properties of PCs under two different incident light polarizations. With the reduction of the symmetry of the X-shaped PCs, the transmission spectra of PCs show a new peak at ∼900 nm in the near-infrared region, and the optical experimental results were consistent with the simulated results. Plasmonic crystal-based biosensors were then prepared by self-assembly of octadecanethiol to the PCs followed by biotinylation and immobilization of streptavidin to the biosensor. The sensing properties of the PC-based biosensors with a 30° intersection angle, which is enhanced by a localized surface plasmon resonance with the asymmetry of the PC, are superior to those with a larger intersection angle in biosensor application. The robust fabrication technique and the strategy for enhancing the sensitivity of the biosensor endow X-shaped PCs with a great competitive advantage over other candidates.

Anisotropic electrical resistivity of LaFeAsO: Evidence for electronic nematicity

Single crystals of LaFeAsO were successfully grown out of KI flux. Temperature dependent electrical resistivity was measured with current flow along the basal plane, \rho_perpend(T), as well as with current flow along the crystallographic c-axis, \rho_parallel(T), the latter one utilizing electron beam lithography and argon ion beam milling. The anisotropy ratio was found to lie between \rho_parallel/\rho_perpend = 20 - 200. The measurement of \rho_perpend(T) was performed with current flow along the tetragonal [1 0 0] direction and along the [1 1 0] direction and revealed a clear in-plane anisotropy already at T \leq 175 K. This is significantly above the orthorhombic distortion at T_0 = 147 K and indicates the formation of an electron nematic phase. Magnetic susceptibility and electrical resistivity give evidence for a change of the magnetic structure of the iron atoms from antiferromagnetic to ferromagnetic arrangement along the c-axis at T^\ast = 11 K.

New method for characterizing paper coating structures using argon ion beam milling and field emission scanning electron microscopy

We have developed a new method for characterizing microstructures of paper coating using argon ion beam milling technique and field emission scanning electron microscopy. The combination of these two techniques produces extremely high-quality images with very few artefacts, which are particularly suited for quantitative analyses of coating structures. A new evaluation method has been developed by using marker-controlled watershed segmentation technique of the secondary electron images. The high-quality secondary electron images with well-defined pores makes it possible to use this semi-automatic segmentation method. One advantage of using secondary electron images instead of backscattered electron images is being able to avoid possible overestimation of the porosity because of the signal depth. A comparison was made between the new method and the conventional method using greyscale histogram thresholding of backscattered electron images. The results showed that the conventional method overestimated the pore area by 20% and detected around 5% more pores than the new method. As examples of the application of the new method, we have investigated the distributions of coating binders, and the relationship between local coating porosity and base sheet structures. The technique revealed, for the first time with direct evidence, the long-suspected coating non-uniformity, i.e. binder migration, and the correlation between coating porosity versus base sheet mass density, in a straightforward way.

Cross-Section Preparation for Solder Joints and MEMS Device Using Argon Ion Beam Milling

<para xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> Mechanical cross-section polishing has traditionally been the method of choice for preparing samples to be examined by Scanning Electron Microscopy (SEM). Although mechanical polishing, allied to selective chemical etching can reveal the most important characteristics of solder joint microstructure, subtle details may be lost. A relatively new cross section polishing method has been developed using an Argon ion beam to prepare a flat surface with potentially less sample damage. In this study we compare these two methods of cross section polishing for solder-substrate couples, and for delicate MEMS type structures. Four solder samples were prepared, consisting of SAC (Sn-Ag-Cu) solder, SAC solder on copper substrate, SAC solder on nickel substrate and In-Sn solder on niobium substrate. SEM was used to examine the polished samples and it was found that features such as the internal structure of intermetallic compounds (IMCs) was more readily identified using the new technique. The ion beam milling technique was also found to be more suitable for simultaneous observation of multiple aspects of microstructure (e.g., identification of IMCs in relation to grain boundaries, substrate crystal structure or the eutectic solder structure). The MEMS device cross-sections could only be prepared by the ion beam method as mechanical polishing caused too much damage. </para>

Nd : Ta 2 O 5 rib waveguide lasers

Ta 2 O 5 waveguides offer great potential for high-density active photonic crystal circuits and their combination with rare-earth dopants for active devices is of interest for increasing their potential functionality. To this end, neodymium-doped Ta2O5 rib waveguide lasers have been fabricated on an oxidized silicon wafer by rf sputtering and argon ion-beam milling and laser action in this material has been demonstrated. Lasing was observed at wavelenghts between 1060 and 1080 nm and an absorbed pump power threshold of 87 mW was obtained.

P- to n-type conversion in GaSb by ion beam milling

Inversion in conductivity type of GaSb from p- to n- has been observed as a result of argon ion beam milling. Electron beam induced current (EBIC) measurements have been employed for detecting the type conversion. Enhancement in the luminescence intensity is seen after ion beam treatment. The type conversion is proposed to occur due to a combined effect of generation of native donors and gettering of native acceptors originally present in the as-grown samples.

Dissociated 60° dislocations in CdTe studied by high-resolution electron microscopy

Abstract High-resolution electron microscopy has been used to characterize disclocations in CdTe which were induced by argon ion-beam milling. The core structures of the 30° and 90° partial dislocations resulting from the dissociation of 60° dislocations have been analysed with assistance from multislice image simulations, and it is found that various structural models (glide set and shuffle set) can be differentiated. Chemical information (α or β form) about the dislocations can be deduced by first determining the Burgers vectors of the dislocations and the crystal polarity. Experimentally, for a 60° dislocation dissociated with an intrinsic stacking fault, the 30° partial is found to be the glide set, independent of its chemical nature; however, no shuffle set is found. For a 60° dislocation dissociated with an extrinsic stacking fault, the 90° partial is usually kinked and therefore much more difficult to recognize. In one particular example, however, it was found to be the glide set.