Primary Ion Beam Research Articles

Comparison of quantitative elemental depth distribution analyses of Ni and Ti in co-sputtered Ni-Ti alloy thin films using MCs+ and M+ secondary ions

Compositional uniformity in Ni-Ti thin alloy films, both at the surface and in the depth, significantly enhances their performance in various engineering applications. Quantitative depth distributions of Ni and Ti in magnetron co-sputtered Ni-Ti thin alloy films of various composition and thickness, were determined through an effective depth profiling technique. Secondary ion mass spectrometry (SIMS) was utilized to determine the qualitative elemental depth distribution of Ni and Ti in the films using MCs+-SIMS (Cs+ primary ion beam; MCs+ secondary ions, 'M' is the element of interest) and M+-SIMS (O2+ primary ion beam) approaches. The qualitative depth profiles were converted to quantitative depth profiles using the relative sensitivity factor values determined from the elemental concentrations obtained through energy dispersive x-ray spectroscopy analysis of one of the Ni-Ti thin film taken as reference. Thickness of the deposited films determined by x-ray reflectivity was used for depth scale calibration of SIMS raw profile. A comparison of the analytical capabilities of MCs+-SIMS and M+-SIMS approaches for determining the mean concentration and quantitative depth distribution of elements Ni and Ti in deposited Ni-Ti thin films has been presented.

Sensitivity enhancement using chemically reactive gas cluster ion beams in secondary ion mass spectrometry (SIMS)

We report for the first time on significant molecular secondary ion yield increases by modifying the chemistry of a water cluster primary ion beam. This was demonstrated using 70‐keV ion beams of 0.15 eV/amu. For the neutral drug Bezafibrate, secondary ion yield enhancements ×5–10 were observed when replacing the Ar carrier gas in a water gas cluster ion beam (GCIB) source with a mixture containing 12% CO2 and 2% O2 in Ar. For the cationic drug Ranitidine, the ion yield enhancements using the CO2‐containing carrier gas were up to ×20–50 in positive mode and ×2–4 in negative mode. The extent of molecular fragmentation was very similar from both cluster beams. We conclude that additional chemically reactive species are present in the impact zone using the (H2O/CO2)n projectile, which promote the formation of secondary ions of both polarity through projectile impact‐induced chemical reactions. This methodology can be applied to further extend the capabilities of high‐resolution 3‐dimensional mass spectral imaging using reactive GCIB‐SIMS.

Study of the critical angle of channeling of active metal ions through thin aluminum films

The spatial distributions of ions (K+, Na+) passed through thin polycrystalline and single-crystalline Al films with the thickness from 180 to 600 Angstrem and critical channeling angles have been studied. The ion energies have been varied within the range E0=10-30 keV. It has been shown that an increase in the energy of the primary ion beam leads to a decrease in the width of the maxima of the angular distribution, which is associated with a decrease in the critical channeling angle psicr. It has been found that the value psicr does not exceed 4-50 for axial channeling and 9-100 for planar channeling Keywords: critical angle, passage of ions, angular distribution, channeling, spatial distribution.

Improved Uranium Particle Analysis by SIMS using O3 - Primary Ions.

We have investigated the use of negative molecular oxygen primary ion beams (i.e., O2 - and O3 -) to determine the benefits of using such beams for uranium particle SIMS analyses. Typically, O- is the most practical negative primary ion species from the conventional duoplasmatron ion source for both age dating and uranium isotopic analysis of particles. Newer RF plasma ion sources make it possible to use O2 - and O3 - due to higher brightness and primary ion fluence, and the increased abundance of molecular species in the plasma relative to the duoplasmatron. We have determined that by using an O3 - beam, the ionization yield can be increased by a factor of approximately two over an O- beam, up to 4.7%, a substantial improvement that positively impacts measurement precision and detection limits. We also investigated the effect of the molecular oxygen beams on uranium isotope mass fractionation and the Th/U relative sensitivity factor for SIMS analyses in comparison to O- beams. We found that O3 - reduced instrumental mass fractionation and matrix/substrate effects relative to the other negative ion beams. Particle measurements using O3 - were improved compared to conventional O- beam analyses due to higher yields, smaller corrections, and reduced substrate effects.

Sputtering, Cluster Primary Ions and Static SIMS

Sputtering using cluster primary ion beams is very important for the future development of static SIMS and the SIMS depth profiling of organic layers. However, different results from different laboratories may be confusing. Analytical models have an important function for enabling the prediction of behaviour for practical analysis. Sigmund's model for sputtering, often used in surface analysis, is helpful and accurate in the linear cascade regime. However, for cluster sputtering this is no longer the case and spike effects need evaluation. Evidence will be presented of the spike model validity for clusters of up to more than 10 atoms over 3 orders of magnitude in sputtering yield. Using data from one primary ion, extremely good descriptions of measurements reported with other primary ions can then be achieved. This theory is then used to evaluate the molecular ion yield behaviour of interest in the static SIMS of organics. This leads to universal dependencies for the de-protonated molecular ion yields, relating all primary ions, both single atom and cluster, which are illustrated by experimental data over 5 decades of emission intensity. This formulation permits the prediction of the (M-H)- secondary ion yield for different, or new, primary ion sources. It is shown how further gains are predicted. For analysing materials, raising the molecular secondary ion yield is extremely helpful but it is the ratio of this yield to the disappearance cross-section (the efficiency) that is critical. The relation of the damage and disappearance cross sections is formulated. Data are evaluated and a description is given to show how these cross sections are related and to provide a further universal relation for the efficiency/yield dependence of all cluster ions.

Microanalysis using secondary ion emission By Raimond Castaing and Georges Slodzian

Secondary ion mass spectrometry (SIMS) is an analytical technique used to probe the composition of solids through the sputtering of the sample with a focussed primary ion beam and analyzing the emitted secondary ions generated under impact. These secondary ions ranging from elementals to low molecular weight organics offer precious information on the molecular composition and spatial organization within samples. Today, the combination of modern SIMS methodologies and instrumentation offers the most sensitive surface analysis approach, with elemental detection limits ranging from parts per million to parts per billion. In this month’s special feature article, we retrace the steps taken by Raimond Castaing and Georges Slodzian who in the early 1960’s developed a SIMS instrument based on a magnetic double focusing sector field mass spectrometer and using argon for the primary ion beam. This seminal work was first published in 1962, in French, in the Journal de Microscopie, which limited access to the scientific community at large. This article is now available in English and is beautifully prefaced by Georges Slodzian who revisits his steps as a young graduate student in the Castaing laboratory and discusses the scientific legacy of this article in the development of modern SIMS instrumentation.

A convolution approach to calculating the m/z-dependent mass analyzer response in orthogonal acceleration time-of-flight mass spectrometers

A novel computational method is developed to calculate the mass bias of orthogonal acceleration time-of-flight mass spectrometers (OA-TOFMS) by evaluating the m/z-dependent transmission efficiency with which ions strike the surface of the detector and the m/z-dependent ion sampling efficiency with which ions are selected for mass analysis. The theory considers the initial ion energy distribution of the primary ion beam and utilizes mathematical convolution to establish the subsequent trajectory of all ions extracted into the OA-TOFMS. By considering the energy-dependent transmission of ions and the ion sampling efficiency together, the resultant mass bias is estimated. The mathematical description is developed for OA-TOFMS using different ionization sources and ion energy distributions, and several examples covering possible time-of-flight conditions and aspects of their application are considered.

Characteristics of a mixed-gas cluster ion beam for time-of-flight secondary ion mass spectrometry

The gas cluster ion beam (GCIB) is a valuable tool for surface analysis, providing new 3D mass analysis equipment possibilities. The main feature of the GCIB is that many particles are involved during the collision of the cluster ion beam with a sample surface. Studying the characteristics of the GCIB is essential for improving the performance of the analysis equipment. We evaluated the efficiency of the GCIB using a mixed-gas of Ar and CO2 as a primary ion beam for time-of-flight secondary ion mass spectrometry. We measured the characteristic factors and composition of the cluster ion beam depending on the mole fraction ratio of CO2/Ar. We measured that the CO2 composition of the output cluster ion beam rapidly increases to over 95% when the mole fraction ratio of CO2 increases by more than 10% in the injected mixed gas. Nevertheless, the optimal ratio of the CO2/Ar mole fraction (%) to increase the secondary ion efficiency was 96% CO2, which more than doubled the secondary ion efficiency over that of pure Ar clusters. The beam spot size began rapidly decreasing from 95% CO2, and it was reduced by up to 0.67 times at 100% CO2. According to the mixed-gas ratio, the sputtering yield of the Si wafer was 8 times lower than that of pure Ar clusters.

Sputtering of Oxides from LaNi5 Surface

The changes in chemical composition of the intermetallic alloy LaNi5 surface monolayers were studied using secondary ion mass spectrometry (SIMS) in the process of the alloy interaction with oxygen. The investigated samples were pellets made by pressing the fine-grained LaNi5 alloy. Ar+ ions having energies of 10-18 keV were used as primary ions. The primary beam current density was 9-17 μA·cm-2, which corresponds to the dynamic SIMS mode. The emission intensities of secondary ions were measured within the dynamic range of at least 6 orders of magnitude. Before the measurements, the samples were annealed in residual vacuum at a temperature of ~ 1000 K. After the annealing, the sample surface was cleaned using the primary ion beam until the mass-spectrum composition and secondary ion emission intensity stabilized completely. The gas phase composition was monitored using a gas mass spectrometer. The conducted studies showed that a complex chemical structure including oxygen, lanthanum, and nickel is formed on the surface and in the near-surface region of LaNi5 as a result of its exposure to oxygen. Oxygen forms strong chemical bonds in such a structure with both components of the alloy. This is evidenced by the presence of a large set of oxygen containing emissions of positive and negative secondary ions with lanthanum, with nickel, and oxygen containing lanthanum-nickel cluster secondary ions in mass spectra. The resulting oxide compounds have a bulk structure and occupy dozens of monolayers. In such a bulk oxide structure, the outer monolayers are characterized by the highest ratio of oxygen atom number to the number of matrix atoms. This ratio decreases along the transition from the surface to the underlying monolayers. This process occurs uniformly, without any phase transformation. The observed secondary ions are not a product of association between sputtered surface fragments and oxygen in the gas phase at the fly-off stage after sputter-ejection, but they are products of the oxide compounds being sputtered, hence they characterize the composition of surface and near-surface region.

Advanced focusing system for secondary electrons in a bunch shape monitor

Measurements of longitudinal beam profile in non-relativistic hadron accelerators are usually performed with Bunch Shape Monitors that utilize secondary electron emission to reproduce the shape of a primary ion beam. The existing devices, however, have poor electron collection efficiency from the wire and are limited to one dimensional measurements of the phase coordinate. In this paper we present the performance improvements for a bunch shape monitor for proton beams used in the Spallation Neutron Source accelerator. These improvements were achieved by adding focusing optics between the wire and the entrance slit, which will also allow measurements over a much higher dynamic range. Here we present the design, simulation and experimental test results of the developed new electron beam guidance system for the existing SNS bunch shape monitor that allowed significant improvement in the collection efficiency.

Neutral gas effect on the surface potential and charge compensation of an insulating sample

Surface charging of an insulating sample has been a significant issue in surface analysis. In time-of-flight secondary ion mass spectrometry, the charge also accumulates on the surface of an insulating sample by the primary ion beam, such as an argon gas cluster ion beam. Such charging can lead to not only degraded mass resolution but also low image resolution, and thus it is necessary to compensate for surface charging of insulating sample. Therefore, several efficient methods have been proposed for charge compensation, such as using a low-energy electron flood gun, applying a bias voltage to the sample stage, and using a gas flooding system. Here, we measured the surface potential of a polymer film to investigate the gas effect on the charge compensation using a Kelvin probe. During the measurements, the chamber pressure was gradually increased by injecting gases, such as He, Ne, Ar, N2, and O2. We found that the injection gas may reduce the surface charging of the sample, depending on the type of gas.

Imaging of Organic Samples with Megaelectron Volt Time-of-Flight Secondary Ion Mass Spectrometry Capillary Microprobe.

Time-of-flight Secondary Ion Mass Spectrometry (TOF SIMS) with MeV primary ions offers a fine balance between secondary ion yield for molecules in the mass range from 100 to 1000 Da and beam spot size, both of which are critical for imaging applications of organic samples. Using conically shaped glass capillaries with an exit diameter of a few micrometers, a high energy heavy primary beam can be collimated to less than 10 μm. In this work, imaging capabilities of such a setup are presented for some organic samples (leucine-evaporated mesh, fly wing section, ink deposited on paper). Lateral resolution measurement and molecular distributions of selected mass peaks are shown. The negative influence of the beam halo, an unavoidable characteristic of primary beam collimation with a conical capillary, is also discussed. A new start trigger for TOF measurements based on the detection of secondary electrons released by the primary ion is presented. This method is applicable for a continuous primary ion beam, and for thick targets that are not transparent to the primary ion beam. The solution preserves the good mass resolution of the thin target setup, where the detection of primary ions with a PIN diode is used for a start trigger, reduces the background, and enables a wide range of samples to be analyzed.

Deep depth profiling using gas cluster secondary ion mass spectrometry: Micrometer topography development and effects on depth resolution.

Secondary ion mass spectrometry using the argon cluster primary ion beam enables molecular compositional depth profiling of organic thin films with minimal loss of chemical information or changes in sputter rate. However, for depth profiles of thicker organic films (> 10 μm of sputtered depth) we have observed the rapid formation of micron-scale topography in the shape of pillars that significantly affect both the linearity of the sputter yield and depth resolution. To minimize distortions in the 3D reconstruction of the sample due to this topography, a step-wise, staggered sample rotation was employed. By using polymer spheres embedded in an organic film, it was possible to measure the depth resolution at the film-sphere interface as a function of sputtered depth and observe when possible distortions in the 3D image occurred. In this way, it was possible to quantitatively measure the effect of micron-scale topography and sample rotation on the quality of the depth profile.

(CO2)n+, (H2O)n+, and (H2O)n+ (CO2) gas cluster ion beam secondary ion mass spectrometry: analysis of lipid extracts, cells, and Alzheimer\u2019s model mouse brain tissue

This work assesses the potential of new water cluster-based ion beams for improving the capabilities of secondary ion mass spectrometry (SIMS) for in situ lipidomics. The effect of water clusters was compared to carbon dioxide clusters, along with the effect of using pure water clusters compared to mixed water and carbon dioxide clusters. A signal increase was found when using pure water clusters. However, when analyzing cells, a more substantial signal increase was found in positive ion mode when the water clusters also contained carbon dioxide, suggesting that additional reactions are in play. The effects of using a water primary ion beam on a more complex sample were investigated by analyzing brain tissue from an Alzheimer’s disease transgenic mouse model. The results indicate that the ToF-SIMS results are approaching those from MALDI as ToF-SIMS was able to image lyso-phosphocholine (LPC) lipids, a lipid class that for a long time has eluded detection during SIMS analyses. Gangliosides, sulfatides, and cholesterol were also imaged.Graphical abstract

EVALUATION OF NEUTRON AMBIENT DOSE EQUIVALENT IN INTENSITY-MODULATED COMPOSITE PARTICLE THERAPY.

Several studies have reported benefits derived from cancer treatment using various heavy-ion beams. Based on these reports, the National Institutes for Quantum and Radiological Science and Technology started developing intensity-modulated composite particle therapy (IMPACT) using He-, C-, O-, and Ne-ions. In ion beam therapy, nuclear interactions in the beamline devices or patient produce secondary neutrons. This study evaluated the characteristics of secondary neutrons in IMPACT. Neutron ambient dose equivalents were measured using WENDI-II. Measurements were performed under realistic case scenarios using He-, C-, O- and Ne-ion beams. Moreover, neutron ambient dose equivalents generated by He-, C-, O- and Ne-ion beams were compared with neutron ambient dose equivalents in proton therapy. No differences exist in the distance-dependence even when the primary ions are different. Neutrons generated by primary ion beams of high atomic numbers tend to emit forward. Moreover, in contrast with proton therapy, IMPACT can reduce neutron doses.

Изучение критического угла каналирования ионов активных металлов через тонкие пленки алюминия

The spatial distributions of ions (K+, Na+) passed through thin polycrystalline and single-crystalline Al films with the thickness from 180 to 600 Å and critical channeling angles have been studied. The ion energies have been varied within the range E0 = 10-30 keV. It has been shown that an increase in the energy of the primary ion beam leads to a decrease in the width of the maxima of the angular distribution, which is associated with a decrease in the critical channeling angle ψcr. It has been found that the value ψcr does not exceed 4-50 for axial channeling and 9-100 for planar channeling.

Development of methodology for determining the isotopic composition of boron in powder and solid nuclear materials using secondary ion mass spectrometer

A method has been developed to determine the isotopic composition of boron (10B/11B) in powder and solid nuclear materials using secondary ion mass spectrometry (SIMS). Isotopic composition of boron in standard sample matrices such as H3BO3, B2O3, B4C (powder) and TiB2 (solid alloy) were measured by the method and compared with the isotopic composition determined from thermal ionization mass spectrometer. Powder samples were ultrasonicated in Milli-Q water and the solutions/slurry obtained were deposited on cleaned silicon wafers, dried under halogen lamp and analysed by SIMS whereas solid alloy sample TiB2 was directly analysed after mechanical polishing and cleaning. Detailed analyses have been carried out using both oxygen and cesium primary ion beams under different analysis conditions. Various elemental and molecular secondary ions were monitored for determining the isotopic composition of boron present in the samples. Standard of boron, NIST-SRM-951 sample was utilized for determining the instrument bias correction factor for different primary beam analysis conditions. The determined instrument bias correction factor was then utilized to measure the isotopic composition of boron in other samples. Surface distribution analysis was also carried out to determine the isotopic distribution of boron deposited on Si wafers. Determination of boron isotopic ratio in refractory nuclear materials (B4C, TiB2) using this method requires minimal sample preparation and avoids commonly used complex dissolution process.

Interrogation of chemical changes on, and through, the bacterial envelope of Escherichia coli FabF mutant using time‐of‐flight secondary ion mass spectrometry

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) using a primary ion beam of (CO2)6k+ was used to analyse chemical changes in the bacterial envelope of a fabF knock‐out Escherichia coli strain. fabF is the gene coding for FabF, the enzyme involved in the elongation of FA(16:1) to FA(18:1) and has been associated with plasmid transfer that can lead to acquired multiantibiotic resistance. Comparison of the membrane composition between fabF mutant E. coli and wild type E. coli during the logarithmic and stationary growth phases at two culture temperatures (37°C and 30°C) revealed substantial depletion of FA(18:1) in the fabF mutant during logarithmic growth that resulted in a correlated reduction in FA(cp19:0) during stationary phase. While no clear temperature dependence on the effect of the fabF mutation was found, a reduction in cyclopropanation was observed at lower culture temperature in the wild type strain. Additionally, depth profile analysis revealed a ‘thickening’ of the lipid A layer on the surface of the bacteria during stationary phase and also the appearance of cyclic enterobacterial common antigen (ECACYC) below the surface of the bacteria upon the shift from logarithmic to stationary growth phase.

Anomalous enhancement of focused ion beam etching by single raster propagating toward ion beam at glancing incidence

Focused ion beam (FIB) sample preparation for electron microscopy often requires large volumes of materials to be removed. Prior efforts to increase the rate of bulk material removal were mainly focused on increasing the primary ion beam current. Enhanced yield of etching at glancing ion beam incidence is known but has not found widespread use in practical applications. In this study, etching at glancing ion beam incidence was explored for its advantages in increasing the rate of bulk material removal. Anomalous enhancement of material removal at glancing angles of ion beam incidence was observed with single-raster etching in along-the-slope direction with toward-FIB direction of raster propagation. Material removal was inhibited in an away-from-FIB direction of raster propagation. The effects of glancing angles and ion doses on depth of cut and volume of removed materials were also recorded. We demonstrated that the combination of single-raster FIB etching at glancing incidence in along-the-slope direction with toward-FIB raster propagation and a “staircase” type of etching strategy holds promise for reducing the processing time for bulk material removal in FIB sample preparation applications.

Dynamics of Molecules Observed at Crude-Oil-Gas Interfaces by Time-of-Flight Secondary Ion Mass Spectrometry Imaging.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging provides molecular speciation at the micrometer scale, while the penetration depth of the primary ion beam is limited to the top-layers of a sample. These combined properties make TOF-SIMS potentially an ideal technique to study oil–gas interfaces. TOF-SIMS spectra of three crude oils were evaluated, and only low-mass fragment ions could be assigned to molecular structures unambiguously. Films of crude oils were incubated under air, oil vapor, or water vapor for various times. TOF-SIMS images of a polar crude oil revealed feeble structures of ∼10 μm large round patches that grew to ∼30 μm large crystals when incubated under air and oil vapor, respectively. Principal component analysis of the images showed that the continuous phase had typical aromatic signatures, while the patches and crystals had alkane-like characteristics. No features showed up when the oil film was incubated under water vapor, which indicated that saturated water vapor prevented the accumulation of nonpolar alkane-like compounds at the oil–gas interface. These examples showed that crude oils do not behave as dead fluids but that their constituents accumulate at the oil–gas interfaces in a dynamic way.