Secondary Mass Spectrometry Research Articles

IN SITU STABLE ISOTOPE MEASUREMENTS IN FORAMINIFERAL TESTS BY SIMS

ABSTRACT Fossilized tests of foraminifera are arguably the most important archives of past climate, and many of the longest paleoclimate records have been compiled by the measurement of the oxygen and carbon isotope composition of foraminiferal tests collected from seafloor sediments. Since the analytical methodology was established in the late 1940s, multiple tests are pooled and analyzed, resulting in a single oxygen and carbon isotope value representing their mean composition. These records compiled by multi-test analysis provide, in most scenarios, a faithful picture of the Earth’s past climate. However, foraminiferal tests feature isotopic heterogeneity on micrometer scales and thus record a wealth of additional information that can be assessed by secondary ion mass spectrometry (SIMS) using spots of 10 µm or less. This paper provides a history of in situ stable isotope measurements in foraminifer tests by SIMS, discusses landmark studies, and offers an outlook on future research.

Formation of n-type polycrystalline silicon with controlled doping concentration by flash lamp annealing of catalytic CVD amorphous silicon films

We investigated the properties of polycrystalline silicon (poly-Si) films formed by the flash lamp annealing (FLA) of hydrogenated amorphous Si (a-Si:H) films. Phosphorus- (P-) doped a-Si:H films with a thickness of several micrometers deposited by catalytic chemical vapor deposition (Cat-CVD) on a silicon nitride- (SiN x -) coated textured glass substrate are crystallized by FLA. P doping was achieved by flowing phosphine (PH3) during Cat-CVD, and the P concentration was controlled within a range of 1016–1021 cm−3, which was measured by secondary ion mass spectrometry. We also fabricated simple back-contact Si heterojunction solar cells to estimate a potential of flash-lamp-crystallized poly-Si as an absorption layer. The current-density–voltage (J–V) characteristics of the cells measured under 1 Sun light irradiation show an open-circuit voltage (V OC) of >0.4 V.

Low-pressure oxidation for improving interface properties and voltage instability of SiO2/4H-SiC MOS capacitor

The impact of high-temperature sub-atmospheric oxidation pressure on the interface properties of n-type 4H-SiC metal–oxide–semiconductor capacitors has been systematically investigated in this report. The bias temperature instability measurement was used to calculate the mobile ions and near-interface trap density that led to device instability at high temperatures. The density of near interface traps decreased from 88.3 × 1011 cm−2 to 10.2 × 1011 cm−2 when the growth pressure of SiO2 was reduced from 1 atm to 0.1 atm, while the mobile ions density decreased from 83.5 × 1011 to 4.18 × 1011 cm−2. The results show that SiO2 growing under lower oxidation pressure has better interfacial quality. The underlying mechanism was explored by secondary ion mass spectrometry (SIMS) and x-ray photoelectron spectroscopy (XPS). It is speculated that the SiO2/SiC interface was reconstructed under low-pressure oxidation: the excess Si-related defects near the interface, such as SiOxCy, were released while O atoms were accumulated to promote a complete oxidation reaction, thereby effectively reducing the number of defects in the SiO2 film and improving device performance.

Enhanced imaging of developed fingerprints and its contaminated substance using ToF-SIMS

Fingerprint is a common form of evidence utilized in crime cases, providing crucial information for suspect identification and the proof of key facts. However, traditional development methods are often ineffective for challenging fingerprints due to variations in information and surface characteristics, potentially causing damage to the fingerprint substance. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) offers a non-destructive approach that combines spatial imaging with mass spectrometry capabilities. This study employed ToF-SIMS to enhance natural fingerprints that showed poor visualization when treated with 1,2-indandione and ninhydrin on porous surfaces such as printing paper, kraft paper, newspaper, and thermal paper, especially on challenging textiles. We also imaged fingerprints on nonporous surfaces that were deposited over 30 days ago using ToF-SIMS, like aluminum foil, express packaging bags, and slides. We then extended the age of fingerprint detection to 3 months to explore the relationship between the aging of fingerprints and the morphological characteristics of sweat pores. Furthermore, the study examined the detection capabilities of ToF-SIMS on fingerprints contaminated with compound econazole nitrate cream after being interfered with by development agents, illustrating its effectiveness in extracting comprehensive fingerprint information.

Exploring the Optimal Binder Content in Composite Electrodes for Sulfide-Based All-Solid-State Lithium-Ion Batteries

All-solid-state batteries (ASSBs) are promising next-generation batteries owing to their improved safety compared with lithium-ion batteries using flammable liquid electrolytes. Among various solid electrolytes, sulfide-based electrolytes exhibit high ionic conductivities, and their ductile properties allow them to be easily processed without high-temperature sintering. In sulfide-based ASSBs, a polymer binder is essential for achieving a good cycling performance by maintaining strong interfacial contacts in the composite electrodes during cycling. In this study, we prepared a composite Si-C anode and a LiNi0.82Co0.1Mn0.08O2 cathode using a nitrile-butadiene rubber binder for ASSB applications, and investigated the effect of the binder content on the mechanical properties and electrochemical performance. The binder content significantly influenced the physical and electrochemical characteristics of the composite electrodes, and the ASSB prepared with 1.5 wt% binder showed the best cycling performance considering capacity retention and rate capability. Furthermore, we investigated how the excess binder adversely affected the cycling performance through time-of-flight secondary ion mass spectrometry analysis.

Variable Clinical Spectrum of Inborn Errors of Bile Acid Synthesis: A Report of 10 Cases.

Inborn errors of bile acid synthesis are rare genetic disorders that usually present as neonatal cholestasis and liver disease in older children and adults. The symptomatology of inborn errors of bile acid synthesis can markedly vary among individuals, ranging from mild to severe conditions. Diagnosis is based on genetic tests and/or urine liquid secondary ionization mass spectrometry. Here, we have described characteristics of patients who were diagnosed with inborn errors of bile acid synthesis in our department. We retrospectively evaluated data from patients diagnosed with inborn errors of bile acid synthesis by urine bile acid analysis and/or genetic tests between 2013 and 2023. Ten patients (8 boys, 2 girls) born to consanguineous parents were diagnosed with inborn errors of bile acid synthesis during the study period. Six patients were diagnosed with 3β-hydroxy-Δ5-C27-steroid dehydrogenase deficiency, 2 patients with peroxisomal acyl-CoA oxidase 2 deficiency, and 2 patients with peroxisome biogenesis disorder. In patients with 3β-hydroxy-Δ5-C27-steroid dehydrogenase deficiency, 3 patients were monitored with cholic acid treatment, 2 underwent liver transplant due to liver failure, and 1 patient died from liver failure. Ursodeoxycholic acid treatment was given to patients with acyl-CoA oxidase 2 deficiency. Cholic acid was given to patients with peroxisome biogenesis disorder. Inborn errors of bile acid synthesis can cause a variety of liver diseases, from asymptomatic liver enzyme elevation to cirrhosis. Clinical findings may include neurological symptoms and fat and fat-soluble vitamin malabsorption complications. Deficiency of 3β-hydroxy-Δ5-C27-steroid dehydrogenase is the most common bile acid synthetic defect presenting in cholestasis in infancy and childhood. Cholic acid is effective for most patients with inborn errors of bile acid synthesis. If patients do not receive an early diagnosis, progressive liver disease or other serious complications may develop.

POLYETHYLENE TEREPHTHALATE (PET) COATED WITH CHITOSAN AND CYCLOSPORINE A LAYERS AS A POTENTIAL STENT MATERIAL AND DRUG-DELIVERY SYSTEM

The aim of this paper was to design, prepare and characterise chitosan (Ch) and cyclosporine A (CsA) mixed films deposited on a plasma-activated polyethylene terephthalate (PET) polymer surface to be used as a cover for implantable blood vessel stents. The PET polymer coated with Ch and CsA layers was immersed in simulated body fluid (SBF) to examine how the obtained layers can behave in the environment of human body fluids. Time-of-flight secondary ion mass spectrometry was employed to determine the chemical composition of the deposited films and to analyse the spatial distribution of molecules on the PET surface. The results showed the controlled release of CsA from the chitosan matrix. It can be concluded that the modification of the PET polymer with layers of chitosan and CsA has great application potential in the tissue engineering as a biocompatible stent of blood vessels with therapeutic properties.

Engineering a superamphiphilic surface for enhanced interfacial bonding in metal-polymer hybrid structure

Insufficient wetting of polymer due to its poor compatibility with metals leads to non-intimate interfacial mutual contact during the thermal-direct bonding process, thus hindering the establishment of effective mechanical interlocking and substantial chemical bonding at the interface, resulting in deficient performance of metal-polymer hybrid structures. To achieve high-quality bonding between non-polar ultra-high molecular weight polyethylene (UHMWPE) and Ti6Al4V titanium alloy (TC4) for the application of artificial joint prostheses, this study innovatively engineered a superamphiphilic (simultaneously superhydrophilic and superlipophilic) TC4 surface, which was achieved through a morphology-chemistry dual regulation strategy. This pretreatment strategy aimed at improving the interfacial compatibility between in-situ oxidized UHMWPE and TC4 and ensuring intimate contact between these two materials during thermal-direct bonding, thus facilitating chemical reactions and mechanical interlocking at the interface. Defect-free and ultra-high-performance TC4-UHMWPE hybrid joints were successfully obtained via friction spot joining (FSpJ) with the lap shear strength reaching 18.05 MPa (higher than all those similar hybrid joints reported in existing literature) and the fracture was confined to the UHMWPE matrix, effectively avoiding interfacial failure. The formation of chemical bonds in the form of COTi at TC4/UHMWPE interface was solidly confirmed based on X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses. This research presents a compelling strategy for improving interfacial compatibility between polymer and metal for thermal-direct bonding, to overcome the general difficulties in achieving effective interfacial bonding between these two categories of materials with significantly different physiochemical properties.

Trace element analysis and luminescence behavior of quartz in pegmatites of the Tørdal Region, Norway

This publication presents a study on the mineral chemistry and luminescence properties of quartz samples from pegmatites of the Tørdal region in Norway. A total of 12 samples were analyzed using Secondary Ion Mass Spectrometry (SIMS), Electron Paramagnetic Resonance Spectroscopy (EPR), and Cathodoluminescence (CL) to gain insights into their trace element concentration and distribution as well as their luminescence behavior. The samples are characterized by different Cl emissions at 450 nm, 500 nm 650 nm and an additional shoulder at 390 nm, which is only partially visible due to the absorption of the glass optics. Of these luminescence bands, the 500 nm band is the most dominant in most samples and it is characterized by an initial blue-green luminescence, which is not stable under electron irradiation. Moreover, it is characterized by a heterogeneous distribution within the samples. This luminescence can be mostly assigned to [AlO4/M+]0 defects, with charge compensation mostly achieved by Li+. Analyses by EPR spectroscopy prove the dominance of structurally bound Al, Li, and Ti ions in the investigated samples. Further analyses using SIMS mapping demonstrate that Na and K are mainly bound to micro fractures or inclusions, suggesting a limited role in the compensation of the luminescence centers. Additionally, the SIMS mappings show that some samples contain Al-rich clusters of 10 to 20 μm in diameter, whereas other trace elements are characterized by a homogeneous distribution. These clusters correspond to bright luminescence areas in size and shape and could potentially indicate H+ compensated [AlO4/M+]0 defects.

Time-of-Flight Secondary Ion Mass Spectrometry Revealing the Organocatalyst Distribution in Functionalized Silica Monoliths.

Hierarchically porous monolithic silica shows promise as a carrier material for immobilized organocatalysts. Conventional analysis usually includes physisorption, infrared spectroscopy and elemental analysis, among others, to elucidate the pore space and degree of functionalization of the material. However, these methods do not yield information about the spatial distribution of the organic species inside the monolithic reactor. In this work, time-of-flight secondary ion mass spectrometry has been applied to characterize the surface of organically functionalized silica monoliths. Cross sections of a silica monolith functionalized with 4-dimethylaminopyridine were analyzed and the results were compared with physisorption and elemental analysis experiments of the same material. This way, insight into the radial distribution of the catalyst could be achieved, which might assist in interpreting the performance of such reactors in heterogeneous flow catalysis.

Influence of RE2O3 (Dy2O3, Yb2O3, and Lu2O3) buffer layers on the structural and ferroelectric characteristics of BiFeO3 thin films

This study investigates the impact of RE2O3 (Dy2O3, Yb2O3, and Lu2O3) buffer layers on the structural and ferroelectric properties of BiFeO3 thin films grown using a spin-coating method. BiFeO3 thin films with various RE2O3 buffer layers were analyzed using x-ray diffraction, atomic force microscopy, secondary ion mass spectrometry, and x-ray photoelectron spectroscopy to determine their crystalline structures, surface topographies, depth profiles, and chemical compositions, respectively. The RE2O3-buffered BiFeO3 film showed better electrical properties compared to the control BiFeO3 film. The buffer layer composed of Yb2O3 showed the lowest leakage current of 6.82 × 10−6 A cm−2, highest remnant polarization of 44.1 μC cm−2, and smallest coercive field of 189 kV cm−1 because of the incorporation of Yb3+ ions into the BiFeO3 film, high degree of (110) preferred orientation, high Fe3+ content, low surface roughness, reduction of Fe3+ valence fluctuation to Fe2+ ions, and decrease in oxygen vacancies. Such BiFeO3 thin films with various RE2O3 buffer layers using spin-coating method pave a pathway toward practical applications of spintronic, sensor and memory.

Beyond Artists' Colors: A Spectral Reference Database for the Identification of β-Naphthol and Triarylcarbonium Colorants by MeVSIMS.

β-Naphthol and triarylcarbonium colorants were often used by modern and contemporary artists in materials such as inks and paints. Their poor stability and ability to fade upon exposure to light make their identification in artworks crucial for planning exhibitions and preventive conservation. Secondary ion mass spectrometry with MeV primary ions (MeV SIMS) is necessary when analyzing synthetic organic colorants (SOCs) with similar molecular structures due to its advantages in high sensitivity and soft ionization, which causes a low fragmentation of organic molecules. In this work, we applied MeV SIMS with 5 MeV Si4+ to identify selected β-naphthol and triarylcarbonium colorants from the 19th/20th century Materials Collection kept at the Academy of Fine Arts Vienna. The collection contains SOCs from renowned companies, such as I.G. Farben and I.C.I., and serves as a unique source of reference materials in the analysis of artworks. Previous research on these colorants with X-ray fluorescence analysis (XRF), micro-Raman, and Fourier transform infrared (FTIR) spectroscopies failed in the case of colorant mixtures. Similar spectral features of the SOCs within one chemical class and their low concentrations in mixtures did not lead to their identification using these techniques. MeV SIMS detected molecular ions or protonated molecules in the positive-ion mode. In the negative-ion mode, the functional groups (NO2 - and SO3 -) of β-naphthol lakes/pigments and heteropolyacid species (WO3 - and MoO3 -) characteristic of triarylcarbonium toners were determined. The results demonstrate that MeV SIMS is highly effective for identifying β-naphthol and triarylcarbonium colorants in mixtures and distinguishing between pigments, toners, lakes, and dyes.

High–precision determination of carbon stable isotope in silicate glasses by secondary ion mass spectrometry: Evaluation of international reference materials

Secondary ion mass spectrometry (SIMS) has been used for isotope analysis of volatile components dissolved in silicate melts for decades. However, carbon in situ stable isotope analysis in natural silicate glasses has remained particularly challenging, with the few published attempts yielding high uncertainties. In this context, we characterized 31 reference silicate glasses of basaltic and basanitic compositions, which we then used as reference materials to calibrate δ13C − value analyses in silicate glasses by SIMS. This set of reference materials covers a wide range of CO2 concentrations (380 ppm – 12,000 ppm) and δ13C values (−28.1 ± 0.2 to −1.1 ± 0.2 ‰, ±1σ). The sets of reference materials were analyzed using large−geometry SIMS at two ion microprobe facilities to test reproducibility across different instrumental setups. The instrumental mass fractionation (IMF) varied widely with two different large−geometry SIMS instruments as well as with different analytical parameters such as field aperture size and primary beam intensity. We found that a precision better than ±1.1 ‰ (both average internal and external precision, ±1σ) for CO2 content higher than 1800 ppm could be achieved using a primary beam intensity of less than 5 nA, resulting in a final spot size of 10–20 μm, allowing precise analysis of δ13C in mineral−hosted melt inclusions. This level of precision was achieved at CO2 concentrations as low as 1800 ppm. This advance opens a wide range of new possibilities for the study of δ13C − value in mafic melts and their mantle sources. The reference materials are now available at the CNRS–CRPG ion microprobe facility in Nancy, France and will be deposited at the Smithsonian National Museum of Natural History, Washington, USA where they will be freely available on loan to any researcher.

Self-Organizing Maps for Secondary Ion Mass Spectrometry.

Secondary ion mass spectrometry (SIMS) is a powerful analytical technique for characterizing the molecular and elemental composition of surfaces. Individual mass spectra can provide information about the mean surface composition, while spatial mapping can elucidate the spatial distributions of molecular species in 2D and 3D with no prior labeling of molecular targets. The data sets produced by SIMS techniques are large and inherently complex, often containing subtle relationships between spatial and molecular features. Machine learning algorithms are well suited to exploring this complexity, making them ideal for data analysis, interpretation, and visualization of SIMS data sets. One such algorithm, the self-organizing map (SOM), is particularly well suited to clustering similar samples and reducing the dimensionality of hyperspectral data sets. Here, we present an introduction to the SOM, a concise mathematical description, and recent examples of its use in SIMS and other related mass spectrometry techniques. These examples demonstrate how SOMs may be used to interpret high volumes of individual mass spectra, imaging, or depth profiling data sets. This review will be useful for specialists in SIMS and other mass spectral techniques seeking to explore self-organizing maps for data analysis.

Complex Diagnostics of Silicon-on-Insulator Layers after Ion Implantation and Annealing

A technology was developed for activating ion-implanted dopants in silicon-on-insulator layers at a low annealing temperature (600°C) using the pre-amorphization technique of a silicon device layer. In the case of phosphorus implantation, silicon was amorphized directly by dopant ions. In the case of boron implantation for pre-amorphization, the layers were preliminary irradiated with argon or fluorine ions. Complex diagnostics of the implanted layers was carried out using secondary ion mass spectrometry, X-ray diffractometry and small-angle X-ray reflectometry. The combination of methods made it possible to characterize the impurity distribution, the degree of silicon crystallinity, the layer thicknesses, and the interface widths in structures. The results of diagnostics of the structure and composition correlate well with calculations in the SRIM software package and the electrophysical characteristics of the layers after annealing. It was shown that the use of argon for pre-amorphization of silicon interfered with the recrystallization process and did not make it possible to achieve acceptable electrical characteristics of the doped layer. Amorphization with phosphorus and pre-amorphization with fluorine during boron implantation allowed obtaining the required values of the resistance of the doped layers after annealing at a temperature of 600°C. The use of a complex approach made it possible to optimize the modes of amorphization, ion doping, and annealing of silicon-on-insulator structures at low temperatures, necessary for the creation of light-emitting device structures based on silicon-germanium nanoislands.

Effect of О<sub>2</sub><sup>+</sup> Ion Implantation on the Elemental and Chemical Composition of the Si(111) Surface

Using the methods of secondary ion mass spectrometry, elastic peak electron spectroscopy and Auger electron spectroscopy, the elemental and chemical composition of the surface, concentration profiles of the distribution of atoms over the depth of silicon implanted with O2+ ions with energy E0 = 1 keV at a dose of D = 6 × 1016 cm–2 were studied. It was found that oxides and suboxides of Si (SiO2, Si2O and SiO0.5) were formed in the ion-doped layer, and it also contained unbound O and Si atoms. Post-implantation annealing at 850–900 K led to the formation of a stoichiometric SiO2 layer ~25–30 Å thick.

Insight into the origins of mobility deterioration in indium phosphide-based epitaxial layer

Ultra-high mobility speciality is a critical figure of merit for ultrapure materials and high-speed optoelectronic devices. However, unintentional doping-inducing various scattering frequently deteriorates mobility capacity. Therefore, how to elucidate the origin of mobility deterioration is still an open and technically challenging issue. Here we report that unintentional-doping silicon ion would be propagated into the indium phosphide (InP)’s epitaxial layer via analysis of time-of-flight and dynamic secondary ion mass spectrometry. The unintentional silicon ion in the InP wafer surface is responsible for the subsequent InGaAs epitaxial layer's mobility attenuation. The first-principles calculations and Boltzmann transport theory prove that polar optical phonon scattering (Fröhlich scattering) in non-doping InGaAs is the dominant scattering mechanism at high temperatures over 100 K. In contrast, the low-temperature scattering process is dominated by ionized impurities scattering. The unintentional silicon ion improves the Fröhlich scattering-dominated critical temperature. Our findings provide insight into the mobility degeneration originating from unintentional pollution and underlying scattering mechanisms, which lay a solid foundation for developing high-grade, super-speed, and low-power photoelectronic devices.

Ultrahigh-resolution imaging of biogenic phosphorus and molybdenum in palaeoproterozoic gunflint microfossils

Phosphorus and molybdenum play important roles in the formation of microbial cell structures and specific enzymes crucial for metabolic processes. Nevertheless, questions remain about the preservation of these elements within ancient microfossils. Here, we present shape-accurate ion images capturing phosphorus and molybdenum on Palaeoproterozoic filamentous microfossils by pioneering a methodology using lateral high-resolution secondary ion mass spectrometry. Introducing electrically conductive glass for mounting isolated microfossils facilitated clearer observations with increased secondary ion yields. Phosphorus was detected along the contours of microfossils, providing direct evidence of phospholipid utilization in the cell membrane. Trace amounts of molybdenum were detected within microfossil bodies, suggesting potential remnants of molybdenum-bearing proteins, such as nitrogenase. These findings align with the hypothesized cyanobacterial origin of filamentous gunflint microfossils. Our methodology introduces a groundbreaking tool for obtaining crucial insights into the cellular evolution and metabolic pathways of microorganisms, allowing comparisons of their morphological characteristics.

Selective control of surface characteristics of magnesite and quartz by a novel silicophilic collector stearylamine acetate

Reverse flotation desiliconization from magnesite is significant for the exploitation of complex and barren magnesite resources. In this process, a critical issue is to find efficient and selective chemicals as flotation collectors. Herein, a cationic surfactant stearylamine acetate (SAA) was first used as a collector for the separation of magnesite and quartz. Micro-flotation experiments demonstrate that quartz can be separated from magnesite with a high Gaudin’s selectivity index of 6.51 at slurry pH 5.0 and 70 mg/L SAA. Measurements of zeta potential and contact angle show that SAA selectively increased the surface charge and hydrophobicity of quartz. Field emission scanning electron microscopy (FESEM/EDS) and atomic force microscope (AFM) imaging indicate greater adsorption density of SAA on quartz than magnesite, with significantly higher nitrogen element content and RMS surface roughness of quartz. We also used surface-sensitive time of flight secondary ion mass spectrometry (TOF-SIMS) and FTIR spectroscopy to characterize the selective adsorption of SAA on quartz from quartz-magnesite mixtures. Apart from electrostatic attraction, it is found that the selective adsorption was attributed to hydrogen bonding formed between the −N–H group of SAA and the oxygen atom of the O-Si-O group on quartz surface.

Analysis of lipid composition of cell-bound membrane vesicles (CBMVs) derived from endothelial cells

Cell-bound membrane vesicles (CBMVs), a novel type of membrane vesicles, have been identified through a series of characterization tools. However, the lipid composition of CBMVs has not yet been characterized. This study focuses on the differences in lipid composition between CBMVs and cell membranes. In order to determine the lipid composition of CBMVs and cell membranes of Human umbilical vein endothelial cells (HUVECs) and find out differential metabolites, this study was carried out by isolating CBMVs lipids and characterizing them using high-performance liquid chromatography tandem secondary mass spectrometry (LC-MS/MS). The results showed the presence of 213 up-regulated and 726 down-regulated lipids in CBMVs compared to cell membranes which produced CBMVs. There are lipids expressed in CBMVs and not in cell membranes: DGDG 18:0_8:0, DGDG O-8:0_16:1, DGDG O-26:7_26:7, DGDG O-16:3_26:7, TG 15:4_21:5_22:5; 4O, PC 49:11, PG 19:5_38:10, PI 60:14, PI 44:9, PI 25:2, PI 43:5, PI 50:10, PS 55:10. DGDG (digalactosyl diglyceride), MGDG (monogalactosyl diglyceride) belongs to galactosyl diglyceride, promotes fat catabolism, which also has antioxidant and anti-inflammatory effects, and unsaturated diacylglycerols are a class of antioxidant compounds, which enables CBMVs to have a therapeutic potential.