Secondary Ion Mass Spectrometry Instrument Research Articles

Secondary Ion Mass Spectral Imaging of Metals and Alloys.

Secondary Ion Mass Spectrometry (SIMS) is an outstanding technique for Mass Spectral Imaging (MSI) due to its notable advantages, including high sensitivity, selectivity, and high dynamic range. As a result, SIMS has been employed across many domains of science. In this review, we provide an in-depth overview of the fundamental principles underlying SIMS, followed by an account of the recent development of SIMS instruments. The review encompasses various applications of specific SIMS instruments, notably static SIMS with time-of-flight SIMS (ToF-SIMS) as a widely used platform and dynamic SIMS with Nano SIMS and large geometry SIMS as successful instruments. We particularly focus on SIMS utility in microanalysis and imaging of metals and alloys as materials of interest. Additionally, we discuss the challenges in big SIMS data analysis and give examples of machine leaning (ML) and Artificial Intelligence (AI) for effective MSI data analysis. Finally, we recommend the outlook of SIMS development. It is anticipated that in situ and operando SIMS has the potential to significantly enhance the investigation of metals and alloys by enabling real-time examinations of material surfaces and interfaces during dynamic transformations.

The restriction of calcium influx in metaphase and post-metaphase stages of cell division revealed by imaging secondary ion mass spectrometry (SIMS).

A secondary ion mass spectrometry (SIMS)-based isotopic imaging technique of ion microscopy was used for observing calcium influx in single renal epithelial LLC-PK1 cells. The CAMECA IMS-3f SIMS instrument, used in the study, is capable of producing isotopic images of single cells at 500nm spatial resolution. Due to the high-vacuum requirements of the instrument the cells were prepared cryogenically with a freeze-fracture method and frozen freeze-dried cells were used for SIMS analysis. The influx of calcium was imaged directly by exposure of cells to 44 Ca stable isotope in the extracellular buffer for 10min. The 44 Ca influx was measured at mass 44 and the distribution of endogenous calcium at mass 40 (40 Ca) in the same cell. A direct comparison of interphase cells to cells undergoing division revealed that calcium influx is restricted in metaphase and post-metaphase stages of cell division. This restriction is lifted in late cytokinesis. The net influx of 44 Ca in 10min was approximately half under calcium influx restriction in comparison to interphase cells. Under calcium influx restriction the 44 Ca concentration was the same between the mitotic chromosome and the cytoplasm. These observations indicate that the endoplasmic reticulum (ER) calcium uptake is compromised under calcium influx restriction in cells undergoing division.

Label-free Chemical Characterization of Polarized Immune Cells in vitro and Host Response to Implanted Bio-instructive Polymers in vivo Using 3D OrbiSIMS.

The Three-dimensional OrbiTrap Secondary Ion Mass Spectrometry (3D OrbiSIMS) is a secondary ion mass spectrometry instrument, a combination of a Time of Flight (ToF) instrument with an Orbitrap analyzer. The 3D OrbiSIMS technique is a powerful tool for metabolic profiling in biological samples. This can be achieved at subcellular spatial resolution, high sensitivity, and high mass-resolving power coupled with MS/MS analysis. Characterizing the metabolic signature of macrophage subsets within tissue sections offers great potential to understand the response of the human immune system to implanted biomaterials. Here, we describe a protocol for direct analysis of individual cells after in vitro differentiation of naïve monocytes into M1 and M2 phenotypes using cytokines. As a first step in vivo, we investigate explanted silicon catheter sections as a medical device in a rodent model of foreign body response. Protocols are presented to allow the host response to different immune instructive materials to be compared. The first demonstration of this capability illustrates the great potential of direct cell and tissue section analysis for in situ metabolite profiling to probe functional phenotypes using molecular signatures. Details of the in vitro cell approach, materials, sample preparation, and explant handling are presented, in addition to the data acquisition approaches and the data analysis pipelines required to achieve useful interpretation of these complex spectra. This method is useful for in situ characterization of both in vitro single cells and ex vivo tissue sections. This will aid the understanding of the immune response to medical implants by informing the design of immune-instructive biomaterials with positive interactions. It can also be used to investigate a broad range of other clinically relevant therapeutics and immune dysregulations. Graphical overview.

Surface Analysis by Secondary Ion Mass Spectrometry (SIMS): Principles and Applications from Swiss laboratories

Secondary Ion Mass Spectrometry (SIMS) extracts chemical, elemental, or isotopic information about a localized area of a solid target by performing mass spectrometry on secondary ions sputtered from its surface by the impact of a beam of charged particles. This primary beam sputters ionized atoms and small molecules (as well as many neutral particles) from the upper few nanometers of the sample surface. The physical basis of SIMS has been applied to a large range of applications utilizing instruments optimized with different types of mass analyzer, either dynamic SIMS with a double focusing mass spectrometer or static SIMS with a Time of Flight (TOF) analyzer. Here, we present a short review of the principles and major applications of three different SIMS instruments located in Switzerland.

SIMS Analysis of Thin EUV Photoresist Films.

This study reports on the application of secondary ion mass spectrometry (SIMS) for examining thin (20-50 nm) chemically amplified resist films on silicon. SIMS depth profiling was carried out using a gas cluster ion beam to ensure minimal sputter-induced damage to the organic constituents of interest. Specific attention concerned the distribution of the photo acid generator (PAG) molecule within these films, along with the photo-induced fragmentation occurring on extreme ultra-violet photo exposure. Positive secondary ion spectra were collected using a traditional time of flight (ToF)-SIMS and the latest generation IONTOF Hybrid SIMS instrumentation equipped with an OrbitrapTM mass analyzer. Tandem mass spectrometry (MS/MS) capability within the OrbitrapTM secondary ion column was utilized to verify that the C19H17S+ secondary ion did indeed have the molecular structure consistent with the PAG structure. The superior mass resolving power of the OrbitrapTM mass analyzer (∼20× of the ToF mass analyzer) along with improved mass accuracy (a few ppm) proved pivotal in the mass spectral and depth profile analysis of these films. This was not the case for the ToF-SIMS experiments, as the mass spectra, as well as the associated depth profiles, exhibited severe molecular (isobaric) interferences.

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.

Instrumental mass fractionation during sulfur isotope analysis by secondary ion mass spectrometry in natural and synthetic glasses

Sulfur isotope ratios are among the most commonly studied isotope systems in geochemistry. While sulfur isotope ratio analyses of materials such as bulk rock samples, gases, and sulfide grains are routinely carried out, in-situ analyses of silicate glasses such as those formed in magmatic systems are relatively scarce in the literature. Despite a number of attempts in recent years to analyse sulfur isotope ratios in volcanic and experimental glasses by secondary ion mass spectrometry (SIMS), the effects of instrumental mass fractionation (IMF) during analysis remain poorly understood. In this study we use more than 600 sulfur isotope analyses of nine different glasses to characterise the matrix effects that arise during sulfur isotope analysis of glasses by SIMS. Samples were characterised for major element composition, sulfur content, and sulfur isotope ratios by independent methods. Our glasses contain between 500 and 3400 ppm sulfur and cover a wide compositional range, including low-silica basanite, rhyolite, and phonolite, allowing us to investigate composition-dependent IMF. We use SIMS in multi-collection mode with a Faraday cup/electron multiplier detector configuration to achieve uncertainty of 0.3‰ to 2‰ (2σ) on measured δ34S. At high sulfur content, the analytical error of our SIMS analyses is similar to that of bulk analytical methods, such as gas-source isotope ratio mass spectrometry. We find IMF causes an offset of −12‰ to +1‰ between bulk sulfur isotope ratios and those measured by SIMS. Instrumental mass fractionation correlates non-linearly with glass sulfur contents and with a multivariate regression model combining glass Al, Na, and K contents. Both ln(S) and Al-Na-K models are capable of predicting IMF with good accuracy: 84% (ln(S)) and 87% (Al-Na-K) of our analyses can be reproduced within 2σ combined analytical uncertainty after a correction for composition-dependent IMF is applied. The process driving IMF is challenging to identify. The non-linear correlation between glass S content and IMF in our dataset resembles previously documented correlation between glass H2O abundance and IMF during D/H ratio analyses by SIMS, and could be attributed to changes in 32S− and 34S− ion yields with changing S content and glass composition. However, a clear correlation between S ion yields and S content cannot be identified in our dataset. We speculate that accumulation of alkalis at the SIMS crater floor may be the principal driving force of composition-dependent IMF. Nonetheless, other currently unknown factors could also influence IMF observed during S isotope ratio analyses of glasses by SIMS. Our results demonstrate that the use of multiple, well-characterised standards with a wide compositional range is required to calibrate SIMS instruments prior to sulfur isotope analyses of unknown silicate glasses. Matrix effects related to glass Al-Na-K contents are of particular importance for felsic systems, where alkali and aluminium contents can vary considerably more than in mafic magmas.

Helium ion microscope - secondary ion mass spectrometry for geological materials.

The helium ion microscope (HIM) is a focussed ion beam instrument with unprecedented spatial resolution for secondary electron imaging but has traditionally lacked microanalytical capabilities. With the addition of the secondary ion mass spectrometry (SIMS) attachment, the capabilities of the instrument have expanded to microanalysis of isotopes from Li up to hundreds of atomic mass units, effectively opening up the analysis of all natural and geological systems. However, the instrument has thus far been underutilised by the geosciences community, due in no small part to a lack of a thorough understanding of the quantitative capabilities of the instrument. Li represents an ideal element for an exploration of the instrument as a tool for geological samples, due to its importance for economic geology and a green economy, and the difficult nature of observing Li with traditional microanalytical techniques. Also Li represents a “best-case” scenario for isotopic measurements. Here we present details of sample preparation, instrument sensitivity, theoretical, and measured detection limits for both elemental and isotopic analysis as well as practicalities for geological sample analyses of Li alongside a discussion of potential geological use cases of the HIM–SIMS instrument.

Cryo-OrbiSIMS for 3D Molecular Imaging of a Bacterial Biofilm in Its Native State.

Secondary ion mass spectrometry (SIMS) is gaining popularity for molecular imaging in the life sciences because it is label-free and allows imaging in two and three dimensions. The recent introduction of the OrbiSIMS has significantly improved the utility for biological imaging through combining subcellular spatial resolution with high-performance Orbitrap mass spectrometry. SIMS instruments operate in high-vacuum, and samples are typically analyzed in a freeze-dried state. Consequently, the molecular and structural information may not be well-preserved. We report a method for molecular imaging of biological materials, preserved in a native state, by using an OrbiSIMS instrument equipped with cryogenic sample handling and a high-pressure freezing protocol compatible with mass spectrometry. The performance is demonstrated by imaging a challenging sample (>90% water) of a mature Pseudomonas aeruginosa biofilm in its native state. The 3D distribution of quorum sensing signaling molecules, nucleobases, and bacterial membrane molecules is revealed with high spatial-resolution and high mass-resolution. We discover that analysis in the frozen-hydrated state yields a 10 000-fold increase in signal intensity for polar molecules such as amino acids, which has important implications for SIMS imaging of metabolites and pharmaceuticals.

Analysis of useful ion yield for the Mg dopant in GaN by quadrupole—SIMS

The authors present a quantitative secondary ion mass spectrometry (SIMS) analysis of the useful ion yield of magnesium dopant in a gallium nitride matrix. A quadrupole SIMS instrument was used to analyze an Mg-doped GaN sample grown by metal organic chemical vapor deposition. Oxygen (O2+) was used as the primary ion beam and its energy was varied in the range from 0.5 to 5 kV with and without oxygen flooding near the sample. The results of the analysis can be used to determine the primary beam energies for optimal magnesium sensitivity.

An overview of NRL's NAUTILUS: a combination SIMS-AMS for spatially resolved trace isotope analysis.

We present a description of the capabilities and performance of the NAval Ultra-Trace Isotope Laboratory's Universal Spectrometer (NAUTILUS) at the U.S. Naval Research Laboratory. The NAUTILUS combines secondary ion mass spectrometry (SIMS) and single-stage accelerator mass spectrometry (SSAMS) into a single unified instrument for spatially resolved trace element and isotope analysis. The NAUTILUS instrument is essentially a fully functional SIMS instrument with an additional molecule-filtering detector, the SSAMS. The combination of these two techniques mitigates the drawbacks of each and enables new measurement paradigms for SIMS-like microanalysis. Highlighted capabilities include molecule-free raster ion imaging for direct spatially resolved analysis of heterogeneous materials with or without perturbed isotopic compositions. The NAUTILUS' sensitivity to trace elements is at least 10× better than commercial SIMS instruments due to near-zero background conditions. We describe the design and construction of the NAUTILUS, and its performance applied to topics in nuclear materials analysis, cosmochemistry, and geochemistry.

High‐Mg# Olivine, Clinopyroxene and Orthopyroxene Reference Materials for In Situ Oxygen Isotope Determination

Secondary ion mass spectrometry (SIMS) requires matrix‐matched reference materials to calibrate mass fractionation during oxygen isotope measurement. Over one thousand SIMS oxygen isotope measurements were conducted on eleven natural mineral samples (five olivines, three clinopyroxenes and three orthopyroxenes) in nineteen sessions using CAMECA IMS 1280 SIMS instruments to evaluate their potential as SIMS reference materials. The obtained results reveal oxygen isotope homogeneity of these samples. No matrix effect was measured for the same variety of mineral samples with limited Mg‐number variations (89.6–94.2, 90–91.9 and 90.1–92.1 for olivine, clinopyroxene and orthopyroxene, respectively). The recommended oxygen isotope compositions of these samples were determined using laser fluorination. These samples are therefore suitable to be used as reference materials for in situ oxygen isotope microanalysis.

2019 Leonard Medal to Hisayoshi Yurimoto

2019 Leonard Medal to Hisayoshi Yurimoto

Secondary ion mass spectrometry depth profiling of ultrathick films using an argon gas cluster source: Crater shape implications on the analysis area as a function of depth

Argon cluster ions have enabled molecular depth profiling to unprecedented depths, with minimal loss of chemical information or changes in sputter rate. However, depth profiling of ultrathick films (>100 μm) using a commercial ion source oriented at 45° to the surface causes the crater bottom to shrink in size because of a combination of the crater wall angle, sputter rate differences along the trailing‐edge crater wall, and undercutting on the leading‐edge. The shrinking of the crater bottom has 2 immediate effects on dual‐beam depth profiling: first is that the centering of the analysis beam inside the sputter crater will no longer ensure the best quality depth profile because the location of the flat crater bottom progressively shifts toward the leading‐edge and second, the shifting of the crater bottom enforces a maximum thickness of the film that could be depth profiled. Experiments demonstrate that a time‐of‐flight secondary ion mass spectrometry instrument equipped with a 20 keV argon cluster source is limited to depth profiling a 180 μm‐thick film when a 500 μm sputter raster is used and a 100 μm square crater bottom is to be left for analysis. In addition, depth profiling of a multilayer film revealed that the depth resolution degrades on trailing‐edge side of the crater bottom presumably because of the redeposition of the sputtered flux from the crater wall onto the crater bottom.

ToF-SIMS analysis of an organic layer using toluene and its cluster ion beam projectiles generated by multiphoton ionization

Secondary ion mass spectrometry (SIMS) has become a powerful tool for a chemical imaging of surfaces. In particular, cluster ion beams have been widely implemented with SIMS using spatial distributions of molecules as an analysis and imaging method for a sample composed of organic molecules. In this study, we developed a home-built time-of-flight (ToF)-SIMS instrument and generated organic molecular cluster ion beams ionized by multiphoton ionization (MPI) as a primary ion beam. Further, the sample stage loaded with rhodamine 6G was bombarded with size-controlled toluene cluster ions to produce secondary ions. Mass spectra of rhodamine 6G were acquired as a function of the size of toluene cluster ions. We plotted the fragments-to-parent ion ratio against each size of cluster ion, and we found that an intact rhodamine 6G signal would be observed with less fragmentations using (Tol)n > 18+. We expect this combination of the organic molecular cluster ion beam generated by MPI and ToF-SIMS to greatly expand the field of surface analysis.

Determination of the ionization coefficient of carbon on an example of silicate glasses analysis by secondary ion mass spectrometry (SIMS)

A method is proposed for the quantitative estimation of the carbon ionization coefficient followed by the determination of its concentration in silicate glasses by secondary ion mass spectrometry (SIMS). The method is based on the calculation of the sputtering ratio of carbon from the surface of silicate glasses. The dependence of the ionization coefficient on the NBO/T parameter (ratio of the number of nonbridging oxygen atoms to the number tetrahedrally coordinated silicon and aluminum ions), corresponding to the structure and composition of the matrix, is shown. The dependences obtained are calibration graphs for the determination of the ionization coefficient and for the subsequent quantitative estimation of carbon in a silicate sample for a particular SIMS instrument and experimental conditions.

Experimental and simulation-based investigation of He, Ne and Ar irradiation of polymers for ion microscopy.

Secondary ion mass spectrometry (SIMS) on the helium ion microscope (HIM) promises higher lateral resolution than on classical SIMS instruments. However, full advantage of this new technique can only be obtained when the interaction of He+ or Ne+ primary ions with the sample is fully controlled. In this work we investigate how He+ and Ne+ bombardment influences roughness formation and preferential sputtering for polymer samples and how they compare to Ar+ primary ions used in classical SIMS by combining experimental techniques with Molecular Dynamics (MD) simulations and SD_TRIM_SP modelling. The results show that diffusion coefficients for He, Ne and Ar in polymers are sufficiently high to prevent any accumulation of rare gas atoms in the polymers which could lead to some swelling and bubble formation. Roughness formation was also not observed. Preferential sputtering is more of a problem, with enrichment of carbon up to surface concentrations above 80%. In general, the preferential sputtering is largely depending on the primary ion species and the impact energies. For He+ bombardment, it is more of an issue for low keV impact energies and for the heavier primary ion species the preferential sputtering is sample dependent. For He+ steady state conditions are reached for fluences much higher than 1018 ions/cm2. For Ne+ and Ar+, the transient regime extends up to fluences of 1017–1018 ions/cm2. Hence, preferential sputtering needs to be taken into account when interpreting images recorded under He+ or Ne+ bombardment on the HIM.

Mass bias corrections for U-Pb isotopic analysis by secondary ion mass spectrometry: Implications for U-Pb dating of uraninite.

Uranium (U)-lead (Pb) geochronology of uraninite is critical to the study of the genesis of U deposits throughout the world. Previous attempts at developing a technique to date uraninite using secondary ion mass spectrometry (SIMS) have, however, had limited success. Improper correction of mass bias results in incorrect reported U-Pb ratios. When these results are plotted on Concordia diagrams they produce erroneous ages, complicating the study of U deposits. Uranium and Pb isotope ratios were measured in three uraninite reference materials (RMs) with varying Pb content and three samples with unknown U-Pb isotope compositions using a CAMECA 7f SIMS instrument. Measurements were made using a primary beam of O(-) accelerated at 12.5 kV. A mass resolving power of 1300 and a 50-V offset were used to minimize interferences. The study demonstrates that the mass bias for U-Pb isotope ratio measurements in uraninite by SIMS varies as a function of Pb content. A three-point calibration curve was developed using uraninite RMs with low-, intermediate- and high-Pb contents. Corrected ratios for both concordant and discordant uraninite were plotted on a Concordia diagram to demonstrate the effect that different correction techniques have on the resulting age. Accurate determination of U-Pb ratios in uraninite using a SIMS instrument requires a suite of RMs with varying Pb content and the construction of a calibration curve, or a uraninite RM with a Pb content similar to that of the unknowns. Failure to standardize correctly will result in erroneous ages being calculated using Concordia diagrams. Copyright © 2016 John Wiley & Sons, Ltd.

SIMS Lab Potsdam: Secondary Ion Mass Spectrometry Laboratory Potsdam

Secondary Ion Mass Spectrometry (SIMS) is among the most powerful laboratory tools available to the analytical geochemist. Its strength lies in SIMS’ ability to produce high precision trace element and isotope ratio data on sample masses as small as 100 picograms. The Helmholtz-Centre Potsdam GFZ German Research Centre for Geosciences operates a fully equipped, large geometry SIMS instrument, which is supported by a comprehensive spectrum of peripheral instrumentation. This facility operates as an open user facility which supports the needs of the global geochemical community.

New sample preparation method using room-temperature direct bonding in backside SIMS analysis

Secondary ion mass spectrometry (SIMS) is one of the tools to investigate the dopant or impurity profiles of the semiconductor materials. In particular, the backside SIMS is a useful technique to examine the diffusion of dopant at the surface while minimizing knock-on effect. However, it is very difficult to prevent insulating samples from charging when O2+ source is used for positive secondary ion detection in magnetic sector SIMS. In order to overcome the problem, the authors have employed a new sample preparation method using a room-temperature direct bonding (RTDB). The authors investigated the depth profiling of insulating samples, which were stacked on a dielectric silicon dioxide films with silicon wafer as a magnetic sector SIMS instrument. The samples treated with and without RTDB were compared, and the results show that the depth profiles of RTDB-treated sample could be obtained no sign of charge-up in the backside SIMS analysis.