Time-of-flight Secondary Ion Mass Spectrometry Data Research Articles

Peak-Based Machine Learning for Plastic Type Classification in Time-of-Flight Secondary Ion Mass Spectrometry.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurement data and machine learning were used in this work to classify six different types of plastics. In order to take into account the characteristics of the measurement data, the local maxima of the measurement data were first examined in a preprocessing step. Several machine learning methods were then implemented to create a model that could successfully classify the plastics. To visualize the data distribution, we applied a dimensionality reduction method, namely, principal component analysis. Finally, to distinguish between the six types of plastics, we conducted an ensemble analysis using four tree-based algorithms: decision tree, random forest, gradient boosting, and LIGHTGBM. This approach can identify the feature importance of plastic samples and allow the inference of the chemical properties of each plastic type. In this way, ToF-SIMS data could be utilized to successfully classify plastics and enhance explainability.

Identification of Lithium Compounds on Surfaces of Lithium Metal Anode with Machine-Learning-Assisted Analysis of ToF-SIMS Spectra.

Detailed knowledge about contamination and passivation compounds on the surface of lithium metal anodes (LMAs) is essential to enable their use in all-solid-state batteries (ASSBs). Time-of-flight secondary ion mass spectrometry (ToF-SIMS), a highly surface-sensitive technique, can be used to reliably characterize the surface status of LMAs. However, as ToF-SIMS data are usually highly complex, manual data analysis can be difficult and time-consuming. In this study, machine learning techniques, especially logistic regression (LR), are used to identify the characteristic secondary ions of 5 different pure lithium compounds. Furthermore, these models are applied to the mixture and LMA samples to enable identification of their compositions based on the measured ToF-SIMS spectra. This machine-learning-based analysis approach shows good performance in identifying characteristic ions of the analyzed compounds that fit well with their chemical nature. Moreover, satisfying accuracy in identifying the compositions of unseen new samples is achieved. In addition, the scope and limitations of such a strategy in practical applications are discussed. This work presents a robust analytical method that can assist researchers in simplifying the analysis of the studied lithium compound samples, offering the potential for broader applications in other material systems.

Interfacial Chemistry Investigation of Initial Fouling Conditions in Isocyanate Production: The Antifouling Performance of AISI 316L Stainless Steel.

The fouling of AISI 316L stainless steel during themanufacture of polymeric methylene diphenyl diisocyanate (pMDI) has been investigated. Studies have been carried out using a laboratory-based rig that simulates the process chemistry of the production plant. A variety of solution concentrations and treatment times have been employed to represent different stages in the production process. Following exposure, steel coupons have been removed and studied by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The thickness of the fouling layer, determined by XPS, is found to vary inversely with exposure time and solution concentration. This is a result of the solubility of the different pMDI derivatives that have been formed at different stages, and a reaction scheme is developed to explain these inverse relationships. ToF-SIMS indicates the formation of metal chlorides as a result of the initial treatment of the steel in the reaction vessel with hydrogen chloride. Fragment ions characteristic of reacted and unreacted pMDI (at m/z = 106 and 132 au, respectively) were used as an indicator of the degree of reacted isocyanate groups within the fouling layer and show a decrease with increasing exposure time, as a result of the formation of intermediates such as amines, ureas, carbodiimides, and uretonimines. The ToF-SIMS data was also processed by principal component analysis (PCA). This generally reinforced the conclusions reached by XPS and ToF-SIMS but, in addition, gave confidence in the repeatability of the analyses with the repeat data (of four analyses) clustering very tightly in the PCA score plots.

High-throughput nitride and interstitial nitrogen analysis in ferritic/martensitic steels via time-of-flight secondary ion mass spectrometry

The following work focuses on characterizing nitrogen in several modified alloys of the precipitation strengthened ferritic/martensitic steel HT9 (12Cr-1MoWV (wt%)). Alloy HT9 is a candidate material for fuel rod cladding and ductwork in the core of the Versatile Test Reactor and other next-generation nuclear fast reactors. Nitrogen content has been shown to have a significant effect on irradiated properties in alloy HT9. To explore that theory, a more comprehensive assessment of the location of nitrogen must be performed; however, locating nano-precipitates, such as nitrides and light interstitial elements like nitrogen in steel, has proven difficult. To begin answering questions surrounding the location of nitrogen, Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) was employed as a primary analysis technique, together with extensive transmission electron microscopy, internal friction testing, and thermodynamic simulations, providing verification and context to trends found in the ToF-SIMS data. For the first time, ToF-SIMS was demonstrated to reliably measure relative differences in the vanadium carbonitride precipitate volume fraction across several chemistries and heat treatments of ferritic/martensitic steels. Additionally, associating matrix elements (iron and chromium) to nitrogen-containing ion clusters significantly reduced the ‘matrix effect that biases nitrogen detection towards nitride precipitates, providing a potential, high-throughput method for the measurement of relative interstitial nitrogen content in steels with ToF-SIMS. • ToF-SIMS provided a new high-throughput analysis method for microalloy precipitate and microstructure design. • ToF-SIMS was employed for semi-quantitative, bulk detection and measurement of nitrides and interstitial nitrogen in steel. • S/TEM provided a quantitative comparison of nitride content, while internal friction testing provided a semi-quantitative comparison of interstitial N.

Investigating matrix effects of different combinations of lipids and peptides on TOF-SIMS data.

Matrix effects, which cause a change in ion intensity, occur in mass spectrometry methods including time-of-flight secondary ion mass spectrometry (TOF-SIMS). Matrix effects often cause large issues in quantitative analysis because secondary ions related to a particular molecule could be dramatically enhanced or suppressed regardless of the concentration. To investigate matrix effects in biological samples, the authors evaluated mixed lipid {POPC [1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine, molecular weight (MW) 759.6]}, peptide [leu-enkephalin, neo-leu-enkephalin (amino acid sequence: YAGFL, MW 569.3), and neo-angiotensin II (amino acid sequence: DRVYIHAF, MW 1019.5)] samples. Matrix effect features were investigated by analyzing the concentration dependence of secondary ions in lipid-peptide mixed samples to develop a method that enables quantitative analysis using TOF-SIMS. Matrix effects depended on the lipid-peptide combination. Interestingly, some secondary ions possessed an intensity that was highly dependent on concentration.

Exploiting the Semidestructive Nature of Gas Cluster Ion Beam Time-of-Flight Secondary Ion Mass Spectrometry Imaging for Simultaneous Localization and Confident Lipid Annotations.

Lipids have been recognized as key players in cell signaling and disease. Information on their location and distribution within a biological system, under varying conditions, is necessary to understand the contributions of different lipid species to an altered phenotype. Imaging mass spectrometry techniques, such as time-of-flight secondary ion mass spectrometry (ToF-SIMS) and matrix-assisted laser desorption/ionization (MALDI), are capable of revealing global lipid distributions in tissues in an untargeted fashion. However, to confidently identify the species present in a sample, orthogonal analyses like tandem MS (MS/MS) are often required. This can be accomplished by bulk sample analysis with liquid chromatography (LC)-MS/MS, which can provide confident lipid identifications, at the expense of losing location-specific information. Here, using planarian flatworms as a model system, we demonstrate that imaging gas cluster ion beam (GCIB)-ToF-SIMS has the unique capability to simultaneously detect, identify, and image lipid species with subcellular resolution in tissue sections. The parallel detection of both, intact lipids and their respective fragments, allows for unique identification of some species without the need of performing an additional orthogonal MS/MS analysis. This was accomplished by correlating intact lipid and associated fragment SIMS images. The lipid assignments, respective fragment identities, and locations gathered from ToF-SIMS data were confirmed via LC-MS/MS on lipid extracts and ultrahigh mass resolution MALDI-MS imaging. Together, these data show that the semidestructive nature of ToF-SIMS can be utilized advantageously to enable both confident molecular annotations and to determine the locations of species within a biological sample.

Electrochemical, ToF-SIMS and computational studies of 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol as a novel corrosion inhibitor for copper in 3.5% NaCl

In the present work, 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol (AMTT) was synthesized and characterized using FTIR and 1H NMR. The triazole was for the first time investigated as a novel corrosion inhibitor for copper in 3.5% NaCl solution employing the electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. The AMTT showed a corrosion inhibition efficiency of >94% at a concentration of 0.5 mmol L−1 and behaved as a mixed type inhibitor with cathodic predominance. The influence of AMTT on the kinetics of the oxidation-reduction behaviour of copper in 3.5% NaCl was studied using cyclic voltammetry. The protective film of AMTT on the copper surface was studied in detail using time of flight-secondary ion mass spectrometry (ToF-SIMS), AFM and FTIR-ATR. The results of surface analysis suggested chemical adsorption of AMTT over copper surface. The inhibitor AMTT is found to interact with the copper surface via the sulphur atom of the thiol group and the nitrogen atoms of the amino group and the triazole ring. ToF-SIMS data also suggest that the inhibitor may bind to two copper surface atoms. The results of theoretical studies via pKa analysis and the quantum chemical calculations support the experimental observations.

Investigation of composition of boron carbide thin films by resonant soft x-ray reflectivity

Boron carbide thin films of different thicknesses deposited by ion beam sputtering were studied. The deposited films were characterized by grazing incidence hard x-ray reflectivity (GIXR), resonant soft x-ray reflectivity (RSXR), x-ray photo electron spectroscopy (XPS), resonant Rutherford backscattering spectrometry (RRBS), and time of flight secondary ion mass spectrometry (TOF-SIMS). Depth profile of the chemical elements constitute the films is reconstructed based on analysis of reflectivity curves measured in the vicinity of B K-edge. The composition of films is closely dependent on film thickness. Boron to Carbon (B/C) ratio reaches to ~4 as the thickness of deposited films increases. The B/C ratio estimated from RSXR measurements are in agreement with the RRBS measurements. TOF-SIMS data also suggested that decrease in boron content with decrease in film thickness. XPS measurements confirm the presence of little amount of B atoms on the surface of low thickness film.

Imaging mass spectrometry for novel insights into contact allergy-a proof-of-concept study on nickel.

In spite of extensive regulation to limit exposure, nickel remains the main cause of contact allergy in the general population. More detailed knowledge on the skin uptake of haptens is required. So far, no method exists for the visualization of this clinically relevant hapten and its distribution in the skin. To show, in terms of a proof of concept, that imaging mass spectrometry [time of flight secondary ion mass spectrometry (ToF-SIMS)] can be applied for investigation of the penetration and distribution of nickel in human skin. Full-thickness human skin obtained from breast reduction surgery was exposed to nickel sulfate (5% in deionized water) for 24 h in Franz-type diffusion cells. Biopsies were obtained from nickel-treated samples and control (deionized water). The tissue was sliced, and analysed with ToF-SIMS, generating high-resolution images of ion distribution in the epidermis and upper dermis. The skin layers could be discerned from the ToF-SIMS data, particularly on the basis of the collagen signal. Nickel ions were localized to the stratum corneum and upper epidermis. This is the first time that ToF-SIMS has been applied to trace the distribution of a hapten in human skin. Proof of principle was shown for nickel, and the technique can, in the future, be expanded for investigation of the skin distribution of clinically relevant sensitizers in general.

Development and characterization of a stable adhesive bond between a poly(dimethylsiloxane) catheter material and a bacterial biofilm resistant acrylate polymer coating.

Catheter associated urinary tract infections are the most common health related infections worldwide, contributing significantly to patient morbidity and mortality and increased health care costs. To reduce the incidence of these infections, new materials that resist bacterial biofilm formation are needed. A composite catheter material, consisting of bulk poly(dimethylsiloxane) (PDMS) coated with a novel bacterial biofilm resistant polyacrylate [ethylene glycol dicyclopentenyl ether acrylate (EGDPEA)-co-di(ethyleneglycol) methyl ether methacrylate (DEGMA)], has been proposed. The coated material shows excellent bacterial resistance when compared to commercial catheter materials, but delamination of the EGDPEA-co-DEGMA coatings under mechanical stress presents a challenge. In this work, the use of oxygen plasma treatment to improve the wettability and reactivity of the PDMS catheter material and improve adhesion with the EGDPEA-co-DEGMA coating has been investigated. Argon cluster three dimensional-imaging time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to probe the buried adhesive interface between the EGDPEA-co-DEGMA coating and the treated PDMS. ToF-SIMS analysis was performed in both dry and frozen-hydrated states, and the results were compared to mechanical tests. From the ToF-SIMS data, the authors have been able to observe the presence of PDMS, silicates, salt particles, cracks, and water at the adhesive interface. In the dry catheters, low molecular weight PDMS oligomers at the interface were associated with poor adhesion. When hydrated, the hydrophilic silicates attracted water to the interface and led to easy delamination of the coating. The best adhesion results, under hydrated conditions, were obtained using a combination of 5 min O2 plasma treatment and silane primers. Cryo-ToF-SIMS analysis of the hydrated catheter material showed that the bond between the primed PDMS catheter and the EGDPEA-co-DEGMA coating was stable in the presence of water. The resulting catheter material resisted Escherichia coli and Proteus mirabilis biofilm colonization by up to 95% compared with uncoated PDMS after 10 days of continuous bacterial exposure and had the mechanical properties necessary for use as a urinary catheter.

A comparative ToF-SIMS and GC–MS analysis of phototrophic communities collected from an alkaline silica-depositing hot spring

One of few techniques that is able to spatially resolve chemical data, including organic molecules, to morphological features in modern and ancient geological samples, is time-of-flight secondary ion mass spectrometry (ToF-SIMS). The ability to connect chemical data to morphology is key for interpreting the biogenicity of preserved remains in ancient samples. However, due to the lack of reference data for geologically relevant samples and the ease with which samples can be contaminated, ToF-SIMS data may be difficult to interpret. In this project, we aimed to build a ToF-SIMS spectral database by performing parallel ToF-SIMS and gas chromatography–mass spectrometry (GC–MS) analyses of extant photosynthetic microbial communities collected from an alkaline silica-depositing hot spring in Yellowstone National Park, USA. We built the library by analyzing samples of increasing complexity: pure lipid standards commonly found in thermophilic phototrophs, solvent extracts of specific lipid fractions, total lipid extracts, pure cultures of dominant phototrophic community members, and unsilicified phototrophic streamer communities.The results showed that important lipids and pigments originating from phototrophs were detected by ToF-SIMS (e.g., wax esters, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, sufloquinovosyldiaglycerol, alkanes, etc.) in the streamer lipid extracts. Many of the lipids were also detected in situ in the unsilicified streamer, and could even be spatially resolved to individual cells within the streamer community. Together with the ToF-SIMS database, this mapping ability will be used to further explore other microbial mats and their fossilized counterparts in the geological record. This is likely to expand the geochemical understanding of these types of samples.

ToF-SIMS and Principal Component Analysis Investigation of Denatured, Surface-Adsorbed Antibodies.

Antibody denaturation at solid-liquid interfaces plays an important role in the sensitivity of protein assays such as enzyme-linked immunosorbent assays (ELISAs). Surface immobilized antibodies must maintain their native state, with their antigen binding (Fab) region intact, to capture antigens from biological samples and permit disease detection. In this work, two identical sample sets were prepared with whole antibody IgG, F(ab')2 and Fc fragments, immobilized to either a silicon wafer or a diethylene glycol dimethyl ether plasma polymer surface. Analysis was conducted on one sample set at day 0, and the second sample set after 14 days in vacuum, with time-of-flight secondary ion mass spectrometry (ToF-SIMS) for molecular species representative of denaturation. A 1003 mass fragment peak list was compiled from ToF-SIMS data and compared to a 35 amino acid mass fragment peak list using principal component analysis. Several ToF-SIMS secondary ions, pertaining to disulfide and thiol species, were identified in the 14 day (presumably denatured) samples. A substrate and primary ion independent marker for denaturation (aging) was then produced using a ratio of mass peak intensities according to denaturation ratio: [I61.9534 + I62.9846 + I122.9547 + I84.9609 + I120.9461]/[I30.9979 + I42.9991 + I73.0660 + I147.0780]. The ratio successfully identifies denaturation on both the silicon and plasma polymer substrates and for spectra generated with Mn+, Bi+, and Bi3+ primary ions. We believe this ratio could be employed to as a marker of denaturation of antibodies on a plethora of substrates.

Differential surface activation of the A1 domain of von Willebrand factor.

The clotting protein von Willebrand factor (VWF) binds to platelet receptor glycoprotein Ibα (GPIbα) when VWF is activated by chemicals, high shear stress, or immobilization onto surfaces. Activation of VWF by surface immobilization is an important problem in the failure of cardiovascular implants, but is poorly understood. Here, the authors investigate whether some or all surfaces can activate VWF at least in part by affecting the orientation or conformation of the immobilized GPIbα-binding A1 domain of VWF. Platelets binding to A1 adsorbed onto polystyrene surfaces translocated rapidly at moderate and high flow, but detached at low flow, while platelets binding to A1 adsorbed onto glass or tissue-culture treated polystyrene surfaces translocated slowly, and detached only at high flow. Both x-ray photoelectron spectroscopy and conformation independent antibodies reported comparable A1 amounts on all surfaces. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and near-edge x-ray absorption fine structure spectra suggested differences in orientation on the three surfaces, but none that could explain the biological data. Instead, ToF-SIMS data and binding of conformation-dependent antibodies were consistent with the stabilization of an alternative more activated conformation of A1 by tissue culture polystyrene and especially glass. These studies demonstrate that different material surfaces differentially affect the conformation of adsorbed A1 domain and its biological activity. This is important when interpreting or designing in vitro experiments with surface-adsorbed A1 domain, and is also of likely relevance for blood-contacting biomaterials.

Stability of La0.6Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O2 cathodes during sintering and solid oxide fuel cell operation

Degradation phenomena of La0.58Sr0.4Co0.2Fe0.8O3/Ce0.9Gd0.1O2 (LSCF/CGO) cathodes were investigated via post-mortem analyses of an experimental solid oxide fuel cell (SOFC) stack tested at 700 °C for 2000 h using advanced electron microscopy (SEM-EDS, HR-TEM-EDS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). Similar studies were carried out on non-tested reference cells for comparison. The analysis focused on the LSCF/CGO cathode and the CGO barrier layer, as the cathode degradation can be a major contributor to the overall degradation in this type of SOFC. SEM-EDS and TOF-SIMS were used to investigate inter-diffusion across the barrier layer—electrolyte interface and the barrier layer—cathode interface. In addition, TOF-SIMS data were employed to investigate impurity distribution before and after testing. HR-TEM-EDS was used to investigate possible phase segregation in the LSCF and to look for reaction between the phases. The results show that phase separation and inter-diffusion across the cathode–barrier layer interface and the barrier layer–electrolyte interface happened mainly during sintering and cathode firing, and to a very little degree during the test period.

Multivariate Calibration of ToF-SIMS and XPS Data from Plasma-Treated Polypropylene Thin Films

The multivariate analysis techniques of principal components analysis (PCA), principal component regression (PCR), and partial least squares regression (PLSR) were used to calibrate time-of-flight secondaryion massspectrometry (ToF-SIMS)dataagainstX-rayphotoelectronspectroscopy (XPS) data obtained from plasma-treated polypropylene. This establishes correlations between quantitative information obtained from XPS with the molecular information indicated by ToF-SIMS, allowing the relative concentration of CO functional groups and C:O atomic concentration ratio on the surfaces of plasma-treated polypropylene to be predicted from ToF-SIMS data alone. A fourfactor prediction model was constructed, and was deemed as adequate to predict the concentrations of the surface CO functional groups, and of the C:O atomic ratio with root mean square error of prediction (RMSEP) values of 0.445 and 0.671at%,

ToF-SIMS evaluation of calcium-containing silica/γ-PGA hybrid systems for bone regeneration

Abstract Inorganic/organic hybrids have great potential for the production of bioactive scaffolds which have tailored mechanical properties and degradation rates suitable for tissue engineering. For bone regeneration, calcium incorporation into hybrids at low temperatures is important due to its ability to stimulate new bone formation. As a consequence, understanding the homogeneity of the critical inorganic and organic components will be the key to the development of such hybrids. The aim of this interdisciplinary study was to use time-of-flight secondary ion mass spectrometry (ToF-SIMS) to determine the homogeneity of these critical components. We evaluated various sol–gel silica/γ-polyglutamic acid (γ-PGA) hybrid systems produced using different routes to introduce the calcium, thereby tailoring and optimizing hybrid syntheses and processing routes. Dimethyl carbonate (DMC) was used to improve the inorganic/organic coupling and its influence on the homogeneity of the hybrid structures was also examined. The results revealed that the calcium salt form of γ-PGA was promising for calcium incorporation since homogeneous products could be obtained. The ToF-SIMS data also indicated that the reaction time of hybrid synthesis and the timing of the addition of DMC can affect the homogeneity of hybrids.

Functionalization/passivation of porous graphitic carbon with di- tert-amylperoxide

Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di- tert-amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n-propyl benzene, n-butyl benzene, p-xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k, of these compounds decreased by about 5% and the number of theoretical plates ( N) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100 °C for 5 h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP additions are then increasingly thermodynamically favorable. Thus, this analysis suggests that the direct functionalization/passivation of PGC with DTAP is plausible. Chemometric analyses of the chromatographic and ToF-SIMS data are also presented.

Probing albumin adsorption onto calcium phosphates by x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry

In this study the binding and assembly of bovine serum albumin (BSA) onto three different calcium phosphate phases (hydroxyapatite, dibasic calcium phosphate dihydrate, and β-tricalcium phosphate) was investigated using a combination of X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). XPS was used to record adsorption isotherms and to quantify the amount of BSA adsorbed onto the different CaP surfaces. On all three surfaces a monolayer of adsorbed BSA was formed. ToF-SIMS was then used to investigate how the structure of BSA changes upon surface binding. ToF-SIMS data from BSA films on the three CaP surfaces showed intensity differences of secondary ions originating from both hydrophobic and hydrophilic amino acids. For a more quantitative examination of structural changes, we developed a ratio comparing the sum of intensities of secondary ions from hydrophobic and hydrophilic residues. A small, but statistically significant, increase in the value of this ratio (7%) was observed between a BSA film on hydroxyapatite versus dibasic calcium phosphate dihydrate. From this ratio we can make some initial hypotheses about what specific changes in BSA structure relate to these differences observed in the ToF-SIMS data.

Quantitative depth profiling of ultrathin high-k stacks with full spectrum time of flight–secondary ion mass spectrometry

Elemental concentration depth profiles of high-k material stacks for 32 nm node devices and below were acquired by high resolution backscattering spectrometry (HRBS), parallel angle resolved-x-ray photoelectron spectroscopy (pAR-XPS), and time of flight–secondary ion mass spectrometry (ToF-SIMS). ToF-SIMS data were analyzed using an original calibration method which the authors shall refer to as the full spectrum protocol. Three different samples were studied in this work, one ultrathin insulating layer (IL) alone and two nitridized high-k/IL samples with different nitridation conditions for the IL. Although HRBS and AR-XPS already proved their ability in this domain, SIMS or ToF-SIMS characterization of high-k material stacks is still hampered by various matrix effects. Comparison of the elemental profiles obtained by all three techniques allows the accuracy of the full spectrum ToF-SIMS protocol to be assessed, both in terms of chemical composition quantification and depth resolution. This study reveals the feasibility of quantitative and depth resolved ToF-SIMS profiling of ultrathin high-k material stacks.

Predicting the surface chemistry contribution to the flotation recovery of chalcopyrite by ToF-SIMS

In flotation, the surface chemistry of the minerals plays a crucial role in the selectivity and recovery of valuable minerals. Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) surface analysis is used in this study to investigate the impact of surface chemistry on the flotation of chalcopyrite with dithiophosphate collector. The ToF-SIMS data corresponding to concentrate and tail particles were statistically analysed employing a combination of multivariate statistical techniques – principal components analysis and discriminant analysis – to identify the surface species that are differential in the flotation of chalcopyrite. Two models were developed to predict the concentrate and tail deportment of particles, one targeting fine and intermediate particle sizes and the other for the coarse particle size. These models were tested using cross-validation and the results showed good prediction accuracy, 88% for fine and intermediate particles and 77% for coarse particles. The models were further tested on feed samples and the results show the developed models can be used as a predictive tool that estimates the maximum recovery expected based on the surface chemistry of particles, as evidenced by ToF-SIMS, under given hydrodynamic conditions.