Ion beam analyses were completed on single crystal LiD (lithium hydride with deuterium on the hydrogen sites) to determine products of hydrolysis with decarbonated H2O (with protium-hydrogen) in an inert gas. Rutherford backscattering spectrometry showed movement of oxygen into the bulk of LiD samples. Hydrolysis rates for the single crystal LiD showed relatively slow initial growth of an oxygen-containing layer. Final growth rates varied widely with H2O level, from 1010 to 1015 (atoms/cm2)/min. at 5.6 and 28 mmol/min. H2O respectively. Simulations of spectra show the hydrolysis product to be LiOH. Elastic recoil detection identifies the hydrogen in the hydroxide layer upon dosing with H2O (with natural, protiated hydrogen) as primarily protium. Micrographs showed island growth occurring initially, with convergence to a full-coverage hydrolysis layer.

Multi-MeV proton beams can be generated by irradiating thin solid foils with ultra-intense (>1018 W/cm2) short laser pulses. Several of their characteristics, such as high bunch charge and short pulse duration, make them a complementary alternative to conventional radio frequency-based accelerators. A potential material science application is the chemical analysis of cultural heritage (CH) artifacts. The complete chemistry of the bulk material (ceramics, metals) can be retrieved through sophisticated nuclear techniques such as particle-induced X-ray emission (PIXE). Recently, the use of laser-generated proton beams was introduced as diagnostics in material science (laser-PIXE or laser-driven PIXE): Coupling laser-generated proton sources to conventional beam steering devices successfully enhances the capture and transport of the laser-accelerated beam. This leads to a reduction of the high divergence and broad energy spread at the source. The design of our hybrid beamline is composed of an energy selector, followed by permanent quadrupole magnets aiming for better control and manipulation of the final proton beam parameters. This allows tailoring both, mean proton energy and spot sizes, yet keeping the system compact. We performed a theoretical study optimizing a beamline for laser-PIXE applications. Our design enables monochromatizing the beam and shaping its final spot size. We obtain spot sizes ranging between a fraction of mm up to cm scale at a fraction of nC proton charge per shot. These results pave the way for a versatile and tunable laser-PIXE at a multi-Hz repetition rate using modern commercially available laser systems.

Liquid phase analysis dominates the field of blood diagnostics and requires drawing blood volumes of several ml for each test. To achieve acceptable accuracy, each single liquid blood test requires ∼7 mL per blood sample, and repeated blood tests are often needed. Frequent testing ca result in Hospital Acquired Anemia for infants, chronically ill, and critically ill patients. Blood testing methods that can be utilized with small amounts of blood are a critical need to save lives. Theranos claimed to have developed novel methods requiring only a few nL of blood. However, Theranos’ techniques led to errors that exceeded beyond the medically acceptable threshold of 10%. This work investigates solid state blood analysis using low volumes of several µL. The most common blood tests used as first line for diagnostics and monitoring patients’ status, always include blood electrolytes, iron, and in some cases, heavy metals.

The present work investigates the formation of rapidly solidified Homogeneous Thin Solid Films (HTSFs) formed from blood drops, in order to make them suitable for solid state analysis in vacuo and in air. The solidification of ∼5 micro-liter (µL)-sized blood droplets into HTSFs is studied with two goals: achieve reproducible HTSFs optimized for producing accurate analysis, and successfully measure the potential accuracy of measurements made on HTSFs for blood electrolytes Na, K, Mg, Ca, and Cl and heavy metals such as Fe.

The blood volumes selected for this work are in the µL range, one thousandth volumes drawn for current liquid phase analysis. Balanced Saline Solution (BSS) is used as an initial liquid for testing solidification uniformity and a potential calibration material. Next, canine and human blood are studied on two types of HemaDropTM coatings for solidification: super-hydrophilic and hyper-hydrophilic. HTSF formation from BSS and blood drops are compared on both coated and uncoated surfaces.

Three solid state analytical methods are investigated in parallel to probe composition at different depths and test each for reproducibility and accuracy: Ion Beam Analysis (IBA), X-ray Fluorescence (XRF), and X-ray Photoelectron Spectroscopy (XPS). The results show that using solid films of blood yields composition, which can be reproducibly measured by IBA, XPS and XRF to varying degrees. XPS’s depth of analysis, limited to ∼5 nm, probes a small fraction of the HTSF, but provides insights into the range of thickness for homogeneous compositions in HTSFs. Statistical and error analysis help establish whether measurements taken in sets of three typically used in lab fall below the medically accepted error threshold (<10%) for each technique and element detected. Measurements are repeated and taken at various locations and on different HTSFs to establish reproducibility. XRF is of particular interest, because it is fast, accurate, portable and can be conducted in air, making it ideal for areas with limited resources.

We report evolution of the surface and wetting behavior of Barium fluoride (BaF2) thin films under the effect of swift heavy ion (SHI) irradiation at different fluences. The analogy of this study may be used may be used for the development of dust resistant fabric technology for rural area. The ion irradiation has been performed at normal incidence on the films with Au ions having 100 MeV energy. Further, the wettability of irradiated surfaces is studied through contact angle of water droplet. The value of contact angle of droplet changes with irradiation, it increases from 111° to 123° with the increase in fluence from 5×1011 to 1×1013 ions/cm2. The mechanism of wettability of BaF2 is explained on the basis of increase in contact area of water droplet with surface. SHI irradiation deposits a huge amount of energy in materials due to extreme electronic excitation and it causes a large increase in the temperature of material around the ion track. Ion beam irradiation leads to the large ejection of atoms from the surface which is one of the major factors in increasing the roughness of the surface and thus for the change in contact angle.

Analysis of the total surface energy γT and its three components as established by the van Oss-Chaudhury-Good Theory (vOCG) is conducted via Three Liquid Contact Angle Analysis (3LCAA). γT is correlated with the composition of the top monolayers (ML) obtained from High-Resolution Ion Beam Analysis (HR-IBA). Control of γT enables surface engineering for wafer bonding (Nano-BondingTM) and/or epitaxial growth. Native oxides on boron-doped p-Si(100) are found to average γT of 53 ± 1.4 mJ/m2) and are always hydrophilic. An HF in methanol or aqueous HF etch for 60 s always renders Si(100) hydrophobic. Its γT decreases by 20% to 44 ± 3 mJ/m2 in HF in methanol etch and by 10% to 48 ± 3 mJ/m2 in aqueous HF. On the contrary, GaAs(100) native oxides are found to always be hydrophobic. Tellurium n+-doped GaAs(100) yields an average of γT of 37 ± 2 mJ/m2, 96% of which is due to the Lifshitz-Van der Waals molecular interactions (γLW = 36 ± 1 mJ/m2). However, hydrophobic GaAs(100) can be made highly hydrophilic. After etching, γT increases by almost 50% to 66 ± 1.4 mJ/m2. 3LCAA shows that the γT increase is due to electron acceptor and donor interactions, while the Lifshitz-van der Waals energy γLW remains constant. IBA combining the 3.039 ± 0.01 MeV oxygen nuclear resonance with <111> channeling, shows that oxygen on Si(100) decreases by 10% after aqueous HF etching, from 13.3 ± 0.3 monolayers (ML) to 11.8 ± 0.4 ML 1 hour after etch.Te-doped GaAs(100) exhibits consistent oxygen coverage of 7.2 ± 1.4 ML, decreasing by 50% after etching to a highly hydrophilic surface with 3.6 ± 0.2 oxygen ML. IBA shows that etching does not modify the GaAs surface stoichiometry to within 1% . Combining 3LCAA with HR-IBA provides a quantitative metrology to measure how GaAs and Si surfaces can be altered to a different hydroaffinity and surface termination.

The effects of crystal orientation and doping on the surface energy, γT, of native oxides of Si(100) and Si(111) are measured via Three Liquid Contact Angle Analysis (3LCAA) to extract γT, while Ion Beam Analysis (IBA) is used to detect Oxygen. During 3LCAA, contact angles for three liquids are measured with photographs via the “Drop and Reflection Operative Program (DROP™). DROP™ removes subjectivity in image analysis, and yields reproducible contact angles within < ±1°. Unlike to the Sessile Drop Method, DROP can yield relative errors < 3% on sets of 20-30 drops. Native oxides on 5 x 1013 B/cm3 p- doped Si(100) wafers, as received in sealed, 25 wafer teflon boats continuously stored in Class 100/ISO 5 conditions at 24.5°C in 25% controlled humidity, are found to be hydrophilic. Their γT, 52.5 ± 1.5 mJ/m2, is reproducible between four boats from three sources, and 9% greater than γT of native oxides on n- doped Si(111), which averages 48.1 ± 1.6 mJ/m2 on four 4” Si(111) wafers. IBA combining 16O nuclear resonance with channeling detects 30% more oxygen on native oxides of Si(111) than Si(100). While γT should increase on thinner, more defective oxides, Lifshitz-Van der Waals interactions γLW on native oxides of Si(100) remain at 36 ± 0.4 mJ/m2, equal to γLW on Si(111), 36 ± 0.6 mJ/m2, since γLW arises from the same SiO2 molecules. Native oxides on 4.5 x 1018 B/cm3 p+ doped Si(100) yield a γT of 39 ± 1 mJ/m2, as they are thicker per IBA. In summary, 3LCAA and IBA can detect reproducibly and accurately, within a few %, changes in the surface energy of native oxides due to thickness and surface composition arising from doping or crystal structure, if conducted in well controlled clean room conditions for measurements and storage.

Helium ion microscopy (HIM), enabled by a gas field ion source (GFIS), is an emerging imaging and nanofabrication technique compatible with many applications in materials science. The scanning electron microscope (SEM) has become ubiquitous in materials science for high-resolution imaging of materials. However, due to the fundamental limitation in focusing of electron beams, ion-beam microscopy is now being developed (e.g., at 20 kV the SEM beam diameter ranges from 0.5 to 1 nm, whereas the HIM offers 0.35 nm). The key technological advantage of the HIM is in its multipurpose design that excels in a variety of disciplines. The HIM offers higher resolution than the best available SEMs as well as the traditional gallium liquid-metal ion source (LMISs) focused ion beams (FIBs), and is capable of imaging untreated biological or other insulating samples with unprecedented resolution, depth of field, materials contrast, and image quality. GFIS FIBs also offer a direct path to defect engineering via ion implantation, three-dimensional direct write using gaseous and liquid precursors, and chemical-imaging options with secondary ion mass spectrometry. HIM covers a wide range of tasks that otherwise would require multiple tools or specialized sample preparation. In this article, we describe the underlying technology, present materials, relevant applications, and offer an outlook for the potential of FIB technology in processing materials.

Accurate analysis of microliter blood samples can improve patient care during medical testing and forensics. Patients can suffer from anemia due to the larger volume required for blood tests, 7 milliliters per vial. Attempts at analysis of nanoliter blood samples by Theranos have systematic errors > 10%, higher than medically acceptable thresholds. Our research aims to analyze composition of microliters of blood. This research investigates accuracy of analyzing blood via HemaDrop™, a patented technique to create a Homogenous Thin Solid Film (HTSF) on super-hydrophilic and hyper-hydrophilic surfaces with 5 microliter droplets of blood. To investigate HemaDrop™’s accuracy, Ion Beam Analysis (IBA) is conducted on dried blood spots (DBS) and HTSFs from congealed blood drops on HemaDrop™-treated samples. HTSFs are observed via optical microscopy to compare uniformity, precipitation, and phase separation. DBSs and HTSFs are compared via optical microscopy for canine blood and human blood. After drying uncoated samples, canine and human blood DBSs exhibit cratering, phase separation, and lack of uniformity. Conversely, HTSFs are uniform, exhibiting no cratering and little phase separation. Next, IBA demonstrates that HTSFs of canine and human blood solidified on super-hydrophilic and hyper-hydrophilic coatings yield spectra where species and electrolytes can be identified, unlike on DBSs. The damage curve method enables extracting accurate blood composition for elements, accounting for IBA damage. Relative error in blood elemental composition is within the 10% medical threshold. While both produced films within the 10% threshold, hyper-hydrophilic coatings eliminated phase separation from serum observed in HTSFs on super-hydrophilic coatings. HemaDrop™ provides consistent measurements independent of sample, showing HTSFs from µL blood drops are uniform, reproducible, and free of phase separation. Thus, HemaDrop™ allows for analysis in vacuum from congealed blood drops and expands the range of techniques to identify elements and molecules.

Percolation of blood and of interstitial fluids into implantable continuous glucose sensors (CGS) for diabetics presently limits sensor lifetime between 3 and 7 days. Na+ mobile ions in body fluids damage Si-based CGS sensors electronics. The direct detection of Na percolation is investigated by Ion Beam Analysis (IBA) and Proton Induced X-ray Emission (PIXE) in previously used CGS. Based on these results, a new technology called HemaDropTM is then tested to prepare small volume (5-10 µL) of blood for IBA. A species’s detectability by IBA scales with the square of the ratio of element’s atomic number Z to that of the substrate. Because Na has a low atomic number (Z=11), Si signals from sensor substrates can prevent Na detection in Si by 2 mega electron volt (MeV) IBA.

Using 4.7 MeV 23Na (α, α)23Na nuclear resonance (NR) can increase the 23Na scattering cross section and thus its detectability in Si. The NR energy, width, and resonance factor, is calibrated via two well-known alpha (α) particle signals with narrow energy spreads: a 5.486 ± 0.007 MeV 241Am α-source (ΔΕ = 0.12%) and the 3.038 ± 0.003 MeV 16O(α, α)16O NR (ΔΕ = 0.1%). Next, the NR cross section is calibrated via 100 nm NaF thin films on Si(100) by scanning the beam energy. The23Na (α, α) NR energy is found to be 4.696 ± 0.180 MeV, and the NR/RBS cross section 141 ± 7%. This is statistically significant but small compared to the 4.265 MeV 12C NR (1700%) and 3.038 MeV 16O NR (210%), and insufficient to detect small amounts of 23Na in Si. Next, a new method of sample preparation HemaDropTM, is tested for detection of elements in blood, such Fe, Ca, Na, Cl, S, K, C, N, and O, as an alternative to track fluid percolation and Na diffusion in damaged sensors. Detecting more abundant, heavier elements in blood and interstitial fluids can better track fluid percolation and Na+ ions in sensors. Both Na detection and accuracy of measured blood composition by IBA is greatly improved by using HemaDropTM sample preparation to create Homogeneous Thin Solid Films (HTSFs) of blood from 5-10 µL on most substrates. HTSF can be used in vacuo such as 10-8 –10-6 Torr).

Knowledge of the composition of many cultural heritage objects is limited, resulting in many unanswered questions in regards to the provenance, composition, and production methods. In this paper, our objective is to show that dual beam scanning electron microscope (SEM) and focused ion beam (FIB) can be used rapidly and non-destructively to determine the surface and bulk metal compositions in small cultural heritage objects. We show, for the first time, that this novel FIB technique can be successfully applied non-destructively to cultural heritage objects by examining three representative silver plated objects (Candelabra, “Century” spoon, and New York World’s Fair spoon) from the Dallas Museum of Art’s unparalleled collection of modern American silver. In each case, we successfully reveal and characterize the bulk metal as well as the Ag-plating, up to ∼80 µm deep and show that there is no visual damage resulting from the milling process of the FIB. This novel characterization technique can be applied, due to its ease of availability and rapid use, to many other problems in addition to silver plated objects, making dual beam SEM/FIB a possible cornerstone technique in the study of cultural heritage objects.

Ion beams are now widely used to thin, shape, or cut materials on the submicrometer scale. This is possible because ions can sputter (i.e., physically remove) material from the target. Ions can also be used to image materials because the incident beam generates ion-induced secondary electrons (iSE). In both cases, the nature of the target material and the choice of the ion employed and its initial energy will determine not only how quickly the beam can thin a specimen, but also the resolution and contrast of the iSE image that is generated. Clearly, there is a need to be able to predict parameters, such as the nature, information content, and spatial resolution of the iSE image. These and other related questions have been investigated using Monte Carlo simulations. We show how the parameters defining quantities, such as depth of penetration and the energy deposited by the incident beam, or the signal yield and resolution of the iSE image, can be predicted using this approach and how these results make it possible to interpret data and optimize operating conditions.

Owing to the development of new ion source technology, users of focused ion beams (FIBs) have access to superior performance when compared with the industry standard Ga+ liquid metal ion source. FIBs equipped with an inductively coupled plasma (ICP) ion source are better able to carry out large volume milling applications by providing up to 2 µA of Xe+ ions focused into a sub-5 µm spot. However, ICP FIBs are presently limited to 25 nm imaging resolution at 1 pA.The gas field ionization source (GFIS) relies upon an ion source that is the size of a single atom and correspondingly gains high brightness through its very small source size. The high brightness allows the GFIS to produce a very small focused probe size (<0.35 nm for helium), but with comparatively small beam currents (less than 2 pA). The Cs+ low temperature ion source, still being developed, has a projected sub-nm focal spot size at 1 pA, a maximum current of several nanoamps, and has the potential to offer integrated secondary ion mass spectrometry capabilities.

The altarpiece dedicated to San Antonio de Padua was made of wood assembled and self-supporting structure attached to the wall. It is a straight plant altarpiece designed to withstand sculptures. This master piece belongs to the a set of Baroque altarpieces preserved in the state of Campeche and is located in San Roque Church in the City of San Francisco de Campeche, Mexico. This altarpiece was decorated following the traditional technique of the seventeenth century in Mexico, a technique derived from Spain. According to literature sources we know that the strata are the wood, the imprimatura, the pictorial strata and metal sheets that make the golden color and corladuras. The characterization of the constituent materials was of great importance for the interpretation of the constructions system and manufacture of the decoration. The present study shows the results of analysis techniques such as optical microscopy, Particle Induce X Ray Emission (PIXE), and X Ray Florescence Spectroscopy (XRF) and interpretation of the different layers constituting the altarpiece of San Antonio.

This work clearly demonstrates that the X Ray Reflectometry technique (XRR), extensively used to assess the quality of microelectronic devices can be a useful tool to study the first stages of ion beam mixing. This technique allows measuring the evolution of the Si concentration profile in irradiated Cr/Si layers. From the analysis of the XRR profiles, it clearly appears that the Si profile cannot be described by a simple error function.

In the past fifty years, experimental works based on TEM or grazing incidence X ray diffraction have clearly shown that alloys and ceramics exhibit a nano pattering under irradiation [1,2,3]. Many works were devoted to study the nano patterning induced by ion beam mixing in solids [17,18,19]. Understanding the nano patterning will provide scientific bases to tailor materials with well-defined microstructures at the nanometric scale. The slowing down of impinging particles in solids leads to a complex distribution of subcascades. Each subcascade will give rise to an athermal diffusion of atoms in the medium. In this work, we focused on this point. Based on the well-known Cahn Hilliard Cook (CHC) equation, we analytically calculate the structure factor describing the nano patterning within the mean field approximation. It has shown that this analytical structure factor mimics the structure factor extracted from direct numerical simulations of the time dependent CHC equation. It appears that this structure factor exhibits a universal feature under irradiation.

An experimental set up has been designed to suppress electron currents generated during energetic ion irradiation to obtain accurate current integration for Heavy Ion Rutherford Backscattering Spectroscopy (HIRBS) measurements of heavy element concentrations and target depth profiles. A combination of an electron trap to suppress any electrons ejected from beam collimators and slits, and a biased aluminum mesh to suppress any secondary electrons ejected from the target was used. Two samples that produce cleanly interpreted spectra have been used as targets to check the accuracy of the system for 3.0 and 4.5 MeV O+2 projectile ions. Details of the experimental set up and data are presented.

The interactions of fully stripped Argon-40 heavy ion beams with 140 MeV/nucleon with a series of increasingly polygonal carbon onions are investigated by high-resolution transmission electron microscopy and thermogravimetric analysis. The experimentally observed graphene layer linking is compared with expected results from the displacement and dislocation migration models. The results suggest that dislocation-driven mechanisms may play a significant role in graphene layer linking induced by heavy ion interactions with carbon onions.

Graphite electrode surface degradation mechanisms and formation of solid electrolyte layers (SEI) at the interface with the electrolyte were studied as a function of the applied voltage and voltage scan rates using in situ optical microscopy. Voltammetry tests were initiated from a peak voltage of 3.00 V during which the voltage was decreased to a constant base potential (0.02 V) using different scan rates of 0.05-5.00 mV/s. Cross-sectional FIB microscopy indicated that graphite surface and subsurface damage -- in the form of loss of material from graphite -- was reduced when dense and continuous deposits of SEI formed at low scan rates (e.g. 0.05 mV/s).Whereas, non-uniform and discontinuous SEI formed at high scan rates (∼ 5.00 mV/s) was unable to alleviate graphite surface damage.

During the excavations made at a burial of the post-Classic Mayan period (1220-1521 A.D.) in the pyramid number 2 of the pre-Hispanic site of Lagartero, Chiapas, Mexico, a set of four small metallic artifacts depicting reptile’s heads, were recovered. The objects were in poor conservation conditions and were taken to the Metal Conservation Laboratory of the National School of Conservation (ENCRyM- INAH) for suitable cleaning and conservation treatments.

Analyses allowed identifying important technological features such as gilding remains. The analytical techniques included optical microscopy followed by X-Ray Fluorescence Spectroscopy (XRF), and Scanning Electron Microscope-coupled with Energy Dispersive Spectrometer (MEB-EDS). For the elemental depth profile a combined Particle X-Ray Emission Spectroscopy and Rutherford Backscattering Spectrometry (PIXE–RBS) analysis was carried out.

The results indicate that the objects are made of a copper alloy, and then gilded probably using electrochemical replacement gilding (thickness has less than 1 μm). This technology has been observed in other metallic objects recovered from the Chichen-Itza Cenote in Yucatan, but it was not available in Mesoamerican areas so far. So, it could imply that these artifacts might have been imported from South American areas.

Over a long period (>10 years), the prediction of iron/mild steel corrosion in concrete requires the use of a mechanistic approach. For that purpose, a key point of the mechanisms involved is the localization of the oxygen reduction sites within the thick corrosion layers, which may greatly influence the nature of the rate-limiting step. In this context, iron rebars (originally covered with concrete) were sampled from a 50-year-old historical building and submitted to isotopic tracers methods (18O) combined with structural Raman microspectroscopy analyses on transverse sections. By this method, the authors demonstrate that the oxygen reduction sites are strongly impacted by the presence of a conductive phase (magnetite) in contact with the metallic substrate.