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Atomic layer deposition (ALD) benefits from high process temperatures when the substrate is not temperature-sensitive because the films deposited at higher temperatures exhibit better electrical properties. In this study, we investigated the ALD process of silicon oxide films by alternating injections of tris(dimethylamino)silane (tris-DMAS) and O 3 /O 2 at temperatures ranging from 400 to 700 °C. The saturation dose of tris-DMAS was 1.5 × 106 L at 400 °C. Self-limiting growth with a growth rate of approximately 0.9 Å/cycle was observed up to 600 °C, allowing excellent step coverage. However, at 700 °C, the growth rate increased significantly to 4.6 Å/cycle, carbon and nitrogen impurities were detected by secondary ion mass spectrometry, and step coverage was poor, supporting the thermal decomposition of tris-DMAS at this temperature. Therefore, the optimum temperature for ALD SiO 2 using tris-DMAS is 600 °C for application as an insulating film on high aspect ratio patterns. At this temperature, the leakage current density was 0.58 nA/cm2, and the oxide-trapped charge density was 4.0 × 1010 cm−2. [ABSTRACT FROM AUTHOR]

Understanding crystal characteristics down to the atomistic level increasingly emerges as a crucial insight for creating solid state platforms for qubits with reproducible and homogeneous properties. Here, isotope concentration depth profiles in a SiGe/28Si/SiGe heterostructure are analyzed with atom probe tomography (APT) and time‐of‐flight secondary‐ion mass spectrometry down to their respective limits of isotope concentrations and depth resolution. Spin‐echo dephasing times T2echo=128μs$T_2^\mathbf {echo}=128 \,\umu\mathrm{s}$ and valley energy splittings EVS around 200μeV$200 \,\umu\mathrm{e\mathrm{V}}$ have been observed for single spin qubits in this quantum well (QW) heterostructure, pointing toward the suppression of qubit decoherence through hyperfine interaction with crystal host nuclear spins or via scattering between valley states. The concentration of nuclear spin‐carrying 29Si is 50 ± 20ppm in the 28Si QW. The resolution limits of APT allow to uncover that both the SiGe/28Si and the 28Si/SiGe interfaces of the QW are shaped by epitaxial growth front segregation signatures on a few monolayer scale. A subsequent thermal treatment, representative of the thermal budget experienced by the heterostructure during qubit device processing, broadens the top SiGe/28Si QW interface by about two monolayers, while the width of the bottom 28Si/SiGe interface remains unchanged. Using a tight‐binding model including SiGe alloy disorder, these experimental results suggest that the combination of the slightly thermally broadened top interface and of a minimal Ge concentration of 0.3$0.3$% in the QW, resulting from segregation, is instrumental for the observed large EVS=200μeV$E_\mathrm{VS}=200 \,\umu\mathrm{e\mathrm{V}}$. Minimal Ge additions <1%, which get more likely in thin QWs, will hence support high EVS without compromising coherence times. At the same time, taking thermal treatments during device processing as well as the occurrence of crystal growth characteristics into account seems important for the design of reproducible qubit properties. [ABSTRACT FROM AUTHOR]

The primary component of the lipid barrier on human hair, which is essential for defense against aging and environmental stresses, is 18-methyleicosanoic acid (18-MEA), which provides hydrophobic properties and protective benefits. Since 18-MEA cannot be regenerated once damaged, developing technology that can permanently bind alternative materials to hair is critical. Once 18-MEA was removed from hair via X-ray photoelectron spectroscopy (XPS), pentaerythritol tetraisoosterate (PTIS) was hydrolyzed and observed via gas chromatography/mass spectrometry (GC/MS) to confirm that it mimicked 18-MEA, and 16-methylheptadecanoic acid (16-MHA) was obtained at pH 4 or lower. 16-MHA was bioconjugated to damaged hair from which 18-MEA was removed via a carbodiimide reaction using polycarbodiimide. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) confirmed that 16-MHA remained on the surface of the bioconjugated hair even after washing. Observation of the endothermic reaction of moisture in hair via a differential scanning calorimetry (DSC) and evaluation of the moisture content confirmed that the physical properties of hair enriched with 16-MHA were similar to those of virgin hair. This biomimetic approach has been shown to restore both external structural integrity and internal moisture homeostasis. [ABSTRACT FROM AUTHOR]

Few aerobic hyperthermophilic microorganisms degrade polysaccharides. Here, we describe the genome-enabled enrichment and optical tweezer-based isolation of an aerobic polysaccharide-degrading hyperthermophile, Fervidibacter sacchari, previously ascribed to candidate phylum Fervidibacteria. F. sacchari uses polysaccharides and monosaccharides for growth at 65–87.5 °C and expresses 191 carbohydrate-active enzymes (CAZymes) according to RNA-Seq and proteomics, including 31 with unusual glycoside hydrolase domains (GH109, GH177, GH179). Fluorescence in-situ hybridization and nanoscale secondary ion mass spectrometry confirmed rapid assimilation of 13C-starch in spring sediments. Purified GHs were optimally active at 80–100 °C on ten different polysaccharides. Finally, we propose reassigning Fervidibacteria as a class within phylum Armatimonadota, along with 18 other species, and show that a high number and diversity of CAZymes is a hallmark of the phylum, in both aerobic and anaerobic lineages. Our study establishes Fervidibacteria as hyperthermophilic polysaccharide degraders in terrestrial geothermal springs and suggests a broad role for Armatimonadota in polysaccharide catabolism. Few aerobic hyperthermophilic microorganisms are known to degrade polysaccharides. Here, Nou et al. use genomic information to enrich and optical tweezers to isolate an aerobic hyperthermophilic bacterium that can grow at 65–87.5 °C using polysaccharides as sole carbon sources. [ABSTRACT FROM AUTHOR]

Doping silicon wafers without using highly toxic or corrosive chemical substances has become a critical issue for semiconductor device manufacturing. In this work, ultra‐thin films of hydroxyapatite (Ca5(PO4)3OH) are prepared by tethering by aggregation and growth (T‐BAG), and further processed by spike annealing. Via in situ infrared (IR), the decomposition of hydroxyapatite and intermixing with the native silicon oxide is observed already at temperatures as low as 200 °C. Phosphate transport through the native silicon oxide is driven by a phase transformation into a more stable thermal oxide. At 700 °C, diffusion of phosphorus into the sub‐surface region of oxide‐free silicon is observed. In situ IR combined with electrical impedance spectroscopy (EIS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), and X‐ray photoelectron spectroscopy (XPS) measurements allows to conclude that the phosphorus is: i) transported through the silicon oxide barrier, ii)) diffused inside the oxide‐free silicon, and iii) finally modified the electrical activity of the silicon wafer. To further explain the experimental findings, density‐functional theory (DFT) is used to demonstrate the extent of the effect of phosphorus doping on the electronic nature of silicon surfaces, showing that even small amounts of doping can have a measurable effect on the electrical performance of semiconductor wafers. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The advancement of solid-state hydrogen storage materials is critical for the realization of a sustainable hydrogen economy. This comprehensive review elucidates the state-of-the-art characterization techniques employed in solid-state hydrogen storage research, emphasizing their principles, advantages, limitations, and synergistic applications. We critically analyze conventional methods such as the Sieverts technique, gravimetric analysis, and secondary ion mass spectrometry (SIMS), alongside composite and structure approaches including Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). This review highlights the crucial role of in situ and operando characterization in unraveling the complex mechanisms of hydrogen sorption and desorption. We address the challenges associated with characterizing metal-based solid-state hydrogen storage materials discussing innovative strategies to overcome these obstacles. Furthermore, we explore the integration of advanced computational modeling and data-driven approaches with experimental techniques to enhance our understanding of hydrogen–material interactions at the atomic and molecular levels. This paper also provides a critical assessment of the practical considerations in characterization, including equipment accessibility, sample preparation protocols, and cost-effectiveness. By synthesizing recent advancements and identifying key research directions, this review aims to guide future efforts in the development and optimization of high-performance solid-state hydrogen storage materials, ultimately contributing to the broader goal of sustainable energy systems. [ABSTRACT FROM AUTHOR]

The application of hydrogen flooding was recently shown to be a simple and effective approach for improved layer differentiation and interface determination during secondary ion mass spectrometry (SIMS) depth profiling of thin films, as well as an approach with potential in the field of quantitative SIMS analyses. To study the effects of hydrogen further, flooding of H2 molecules was compared to reactions with atomic H on samples of pure metals and their alloys. H2 was introduced into the analytical chamber via a capillary, which was heated to approximately 2200 K to achieve dissociation. Dissociation of H2 up to 30% resulted in a significant increase in the intensity of the metal hydride cluster secondary ions originating from the metallic samples. Comparison of the time scales of possible processes provided insight into the mechanism of hydride cluster secondary ion formation. Cluster ions presumably form during the recombination of the atoms and molecules from the sample and atoms and molecules adsorbed from the gas. This process occurs on the surface or just above it during the sputtering process. These findings coincide with those of previous mechanistic and computational studies. [ABSTRACT FROM AUTHOR]

This study employs secondary ion mass spectrometry (SIMS) to investigate the diffusion behavior of hydrogen and carbon in a CdxZn1−xO:Eu multilayer at different annealing temperatures (500–900 °C). The SIMS results reveal a significant out-diffusion of these elements toward the surface and diffusion to the interface region. The diffusion flow rates are asymmetric and favor the interface direction. The depth profiles of diffused elements are fitted using the forward timecentered space (FTCS) iteration method. The activation energies are determined to be 0.35 ± 0.06 eV for hydrogen and 0.33 ± 0.09 eV for carbon, suggesting an interstitial mechanism in CdxZn1−xO. The results indicate that increasing the annealing temperatures leads to a significant decrease in impurity concentrations. [ABSTRACT FROM AUTHOR]

Plasma etching is a crucial step in semiconductor manufacturing. High cleanliness and wafer‐to‐wafer reproducibility in the etching chamber are essential in order to successfully achieve nanometer‐sized integrated functions on the wafer. The trend toward the application of more aggressive plasma compositions leads to higher demands on the plasma resistance of the materials used in the etching chamber. Due to its excellent etch resistance, yttrium aluminum garnet Y3Al5O12 (YAG) is starting to replace established materials like SiO2 or Al2O3 in this kind of application. In this study, reactive spark plasma sintering (SPS) was used to manufacture highly dense YAG ceramics from the respective oxides. In addition, yttrium was replaced with heavier lanthanoids (Er, Lu), intending to investigate the role of the A‐site cation in the garnet type structure on the plasma erosion behavior. The produced materials were exposed to fluorine‐based etching plasmas mimicking the conditions in the semiconductor manufacturing apparatus and the erosion behavior was characterized by atomic force microscopy (AFM), secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM), and profilometry. The induced chemical gradient in the samples is limited to a few nanometers below the surface, which makes its characterization challenging. For advanced analysis, we developed a correlative characterization method combining SIMS and scanning TEM (STEM)–energy‐dispersive spectroscopy (EDS) enabling us to examine the structural and chemical changes in the reaction layer locally resolved. In the case of lanthanoid aluminates, an altered reaction layer and reduced fluorine penetration compared to YAG were found. However, a correlation between the characteristics of the induced chemical gradient and the determined physical erosion rates was not evident. [ABSTRACT FROM AUTHOR]

Samples of B‐type asteroid (101955) Bennu returned by the Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS‐REx) spacecraft will provide unique insight into the nature of carbonaceous asteroidal matter without the atmospheric entry heating or terrestrial weathering effects associated with meteoritic samples. Some of the Bennu samples will undergo characterization by X‐ray computed tomography (XCT). To protect the pristine nature of the samples, it is important to understand any adverse effects that could result from irradiation during XCT analysis. We analyzed acid‐insoluble residues produced from two powdered samples of the Murchison carbonaceous chondrite, one control and one XCT‐scanned, to assess the impact on insoluble organic matter (IOM) and presolar grains. Using a suite of in situ analytical techniques (field‐emission scanning electron microscopy, optical and ultraviolet fluorescence microscopy, microprobe two‐step laser mass spectrometry, and nanoscale secondary ion mass spectrometry), we found that the two residues had indistinguishable chemical, molecular, and isotopic signatures on the micron to submicron scale, indicating that an X‐ray dosage of 180 Gy (the maximum dose to be used during preliminary examination of Bennu materials) did not damage the IOM and presolar grains. To explore the use of acid‐insoluble residues to infer parent body processes in preparation for Bennu sample analysis, we also analyzed a residue produced from the Sutter's Mill carbonaceous chondrite. Multiple lines of evidence, including severely degraded UV fluorescence signatures and D‐rich hotspots, indicate that the parent body of Sutter's Mill was heated to >400°C. This heating event was likely short lived because the abundance of presolar SiC grains, which are destroyed by thermal metamorphism and prolonged oxidation, was consistent with those in Murchison and other unheated chondrites. The results of these in situ analyses of acid‐insoluble residues from Murchison and Sutter's Mill provide complementary detail to bulk analyses. [ABSTRACT FROM AUTHOR]

Accurately determining the timing of hydrothermal mineralization for sediment-hosted disseminated gold (SHDG) deposits is difficult because of a lack of both suitable chronometers and in situ techniques with the required spatial resolution and precision. The lack of precise age determinations on gold deposits has hindered understanding of their genesis and relation to the geodynamic setting. The Qiuling-Jinlongshan deposit is a typical SHDG deposit located in the eastern South Qinling Orogen (SQO), with 109 t Au at an average grade of 6.17 g/t. Devonian and Carboniferous metasedimentary rocks host structurally controlled gold mineralization, which is associated with silica-carbonate alteration. Pyrite, arsenopyrite, and arsenian pyrite are major gold carriers, and gold also occurs as native gold grains and invisible gold in the sulfides. In this study, the well-defined hydrothermal overgrowth rims (~2 μm) of single monazite grains, associated with disseminated auriferous arsenian pyrite and arsenopyrite in low-grade metasedimentary rocks, yield U-Pb ages of239 ± 13 Ma (2σ) by high spatial resolution secondary ion mass spectrometry (SIMS). The hydrothermal monazites are cogenetic to the primary gold mineralization where they are closely associated with gold-bearing sulfides. This new age implies that the early to middle Triassic mineralization event in the eastern SQO was related to the Triassic tectonic transition from compression to transpression in the Qinling Orogen after the closure of the Mianlue Ocean. This study highlights the 2-μm high spatial resolution SIMS monazite U-Th-Pb dating method as a powerful tool for determining the timing of SHDG deposits worldwide. It is crucial to examine monazite textures and their link to hydrothermal alteration before carrying out the isotopic dating of monazite. [ABSTRACT FROM AUTHOR]

David Michael Hercules, a renowned scientist, passed away in 2024 after a battle with cancer. He was born in 1932 and developed an early interest in science and music. He pursued a career in science, earning a Bachelor's degree from Juniata College and a Ph.D. in analytical chemistry from MIT. Throughout his career, Hercules made significant contributions to various fields, including chemiluminescence, surface science, materials characterization, and mass spectrometry. He mentored over 130 graduate students and post-docs and emphasized the importance of confirming measurements with reference techniques. Hercules also engaged in industrial collaborations and encouraged his students to build expansive networks. He was known for his authenticity, warmth, and dedication to his students. [Extracted from the article]

Rates of microbial growth are fundamental to understanding environmental geochemistry and ecology. However, measuring the heterogeneity of microbial activity at the single-cell level, especially within complex populations and environmental matrices, remains a forefront challenge. Stable isotope probing (SIP) is a method for assessing microbial growth and involves measuring the incorporation of an isotopic label into microbial biomass. Here, we assess Raman microspectroscopy as a SIP technique, specifically focusing on the measurement of deuterium (2H), a tracer of microbial biomass production. We correlatively measured cells grown in varying concentrations of deuterated water with both Raman spectroscopy and nanoscale secondary ion mass spectrometry (nanoSIMS), generating isotopic calibrations of microbial 2H. Relative to Raman, we find that nanoSIMS measurements of 2H are subject to substantial dilution due to rapid exchange of H during sample washing. We apply our Raman-derived calibration to a numerical model of microbial growth, explicitly parameterizing the factors controlling growth rate quantification and demonstrating that Raman–SIP can sensitively measure the growth of microorganisms with doubling times ranging from hours to years. The measurement of single-cell growth with Raman spectroscopy, a rapid, nondestructive technique, represents an important step toward application of single-cell analysis into complex sample matrices or cellular assemblages. [ABSTRACT FROM AUTHOR]

MAX phases, ternary transition metal carbides and nitrides, represent one of the largest families of layered materials. They also serve as precursors to MXenes, two‐dimensional (2D) carbides and nitrides. The possibility of oxygen substitution in the carbon sublattice, forming oxycarbide MAX phases and MXenes, was recently reported using secondary ion mass spectrometry. However, while the effect of oxygen substitution on the properties of MXenes was investigated, little is known about its effect on the properties of MAX phases. Here, we explore the influence of process parameters (e.g., particle size, synthesis temperature, annealing time, etc.) and oxygen presence in the lattice on the oxidation resistance of Ti3AlC2 MAX phase powders. We show that X‐ray diffraction measurements can identify oxygen substitution and assist in selecting MAX precursors to synthesize stable and highly conductive MXenes. Eliminating the substitutional oxygen from the MAX phase lattice increases the onset of oxidation by 400°C, from approximately 490 to 890°C. Finally, we discuss the impact of oxygen substitution in the MAX phases on the synthesis of MXenes and their resulting properties. [ABSTRACT FROM AUTHOR]

This study assesses the effect of chemical abrasion on in situ mass spectrometric isotopic and elemental analyses in zircon. Chemical abrasion improves the U–Pb systematics of SIMS (secondary ion mass spectrometry) analyses of reference zircons, while leaving other isotopic systems largely unchanged. SIMS 206Pb/238U ages of chemically abraded reference materials TEMORA-2, 91500, QGNG, and OG1 are precise to within 0.25 % to 0.4 % and are within uncertainty of chemically abraded TIMS (thermal ionization mass spectrometry) reference ages, while SIMS 206Pb/238U ages of untreated zircons are within uncertainty of TIMS reference ages where chemical abrasion was not used. Chemically abraded and untreated zircons appear to cross-calibrate within uncertainty using all but one possible permutation of reference materials, provided that the corresponding chemically abraded or untreated reference age is used for the appropriate material. In the case of reference zircons QGNG and OG1, which are slightly discordant, the SIMS U–Pb ages of chemically abraded and untreated material differ beyond their respective 95 % confidence intervals. SIMS U–Pb analysis of chemically abraded zircon with multiple growth stages is more difficult to interpret. Treated igneous rims on zircon crystals from the S-type Mount Painter Volcanics are much lower in common Pb than the rims on untreated zircon grains. However, the analyses of chemically abraded material show excess scatter. Chemical abrasion also changes the relative abundance of the ages of zircon cores inherited from the sedimentary protolith, presumably due to some populations being more likely to survive the chemical abrasion process than others. We consider these results from inherited S-type zircon cores to be indicative of results for detrital zircon grains from unmelted sediments. Trace element, δ18 O, and ε Hf analyses were also performed on these zircons. None of these systems showed substantial changes as a result of chemical abrasion. The most discordant reference material, OG1, showed a loss of OH as a result of chemical abrasion, presumably due to dissolution of hydrous metamict domains or thermal dehydration during the annealing step of chemical abrasion. In no case did zircon gain fluorine due to exchange of lattice-bound substituted OH or other anions with fluorine during the HF partial dissolution phase of the chemical abrasion process. As the OG1, QGNG, and TEMORA-2 zircon samples are known to be compositionally inhomogeneous in trace element composition, spot-to-spot differences dominated the trace element results. Even the 91500 megacrystic zircon pieces exhibited substantial chip-to-chip variation. The light rare earth elements (LREEs) in chemically abraded OG1 and TEMORA-2 were lower than in the untreated samples. Ti concentration and phosphorus saturation ((Y + REE) / P) were generally unchanged in all samples. [ABSTRACT FROM AUTHOR]

This study delves into the impact of oxidation conditions on the orientation of titanium nitride (TiN) films grown by atomic layer deposition (ALD) and its subsequent effects on optical and electrical properties. Through systematic variations in oxygen exposure during ALD processes, the interplay among titanium, oxygen, and nitrogen is investigated. X-ray diffraction (XRD) analysis reveals distinct modifications in crystallographic orientation, particularly the (111) and (002) preferred orientations, influenced by different oxidation processes. Characterization techniques, including spectroscopic ellipsometry and secondary ion mass spectrometry (SIMS), provide insights into the thickness, refractive index, and chemical composition of the TiN films. Notably, the study observes a correlation between oxygen concentration, crystallographic orientation, and sheet resistance. Samples subjected to integrated oxidation processes exhibit lower (111) texture coefficients, indicating enhanced oxygen incorporation and altered crystalline structures. Conversely, samples with surface oxidation processes display comparable (111) texture coefficients and higher growth per cycle (GPC) values to the reference sample, underscoring the nuanced influence of oxidation timing. The study's findings offer valuable insights into tailoring the properties of TiN films through controlled oxidation conditions, crucial for optimizing their performance in various applications. [ABSTRACT FROM AUTHOR]

Microbially induced corrosion (MIC) is an emerging topic that has huge environmental impacts, such as long-term evaluation of microbial interactions with radioactive waste glass, environmental cleanup and disposal of radioactive material, and weathering effects of microbes. Time-of-flight secondary ion mass spectrometry (ToF-SIMS), a powerful mass spectral imaging technique with high surface sensitivity, mass resolution, and mass accuracy, can be used to study biofilm effects on different substrates. Understanding how to prepare biofilms on MIC susceptible substrates is critical for proper analysis via ToF-SIMS. We present here a step-by-step protocol for preparing bacterial biofilms for ToF-SIMS analysis, comparing three biofilm preparation techniques: no desalination, centrifugal spinning (CS), and water submersion (WS). Comparisons of two desalinating methods, CS and WS, show a decrease in the media peaks up to 99% using CS and 55% using WS, respectively. Proper desalination methods also can increase biological signals by over four times for fatty acids using WS, for example. ToF-SIMS spectral results show chemical compositional changes of the glass exposed in a Paenibacillus polymyxa SCE2 biofilm, indicating its capability to probe microbiologically induced corrosion of solid surfaces. This represents the proper desalination technique to use without significantly altering biofilm structure and substrate for ToF-SIMS analysis. ToF-SIMS spectral results showed chemical compositional changes of the glass exposed by a Paenibacillus bacterial biofilm over 3-month inoculation. Possible MIC products include various phosphate phase molecules not observed in any control samples with the highest percent increases when experimental samples were compared with biofilm control samples. [ABSTRACT FROM AUTHOR]

OrbiSIMS is a secondary ion mass spectrometry method with dual mass analyzers: a time-of-flight (ToF) mass spectrometer for high-speed imaging and an Orbitrap™ for high mass resolving power and mass accuracy. Originally developed for biological imaging, there is now growing interest in the application to semiconductor materials to resolve peak interferences that obfuscate analysis in traditional SIMS depth profiling experiments. We use a new method to calibrate the Orbitrap intensity scale to true counts, which allows comparison of the useful yield and duty cycle with a magnetic sector instrument and a time-of-flight instrument using an Sb implant in the silicon sample. The useful yield of the Orbitrap and magnetic sector instruments (for one detected peak) are similar. However, since the magnetic sector instrument has serial mass detection, its useful yield reduces as more peaks are analyzed. While the ToF instrument has parallel detection, it has a low duty cycle and the useful yield is two orders of magnitude lower for 1000 eV Cs+ sputtering. The depth resolution was also compared from the measurement of the downslope from depth profiles of an Sb delta multilayer. For 1000 eV Cs+ sputtering, the downslopes are 3.9, 2.3, and 2.7 nm/decade for Orbitrap, magnetic sector, and ToF instruments, respectively. Ion trajectory simulation shows that the poorer depth resolution of the OrbiSIMS is in part due to ion beam distortion at low energy. [ABSTRACT FROM AUTHOR]

The paper describes a simple analytical model that allows the calculation of hydrogen surface coverage under the influence of several processes that can co-occur during the ion-beam bombardment/sputter analysis of a sample surface, in particular during analysis by secondary ion mass spectrometry (SIMS). The model considers processes of dissociative adsorption, desorption, absorption from the surface into the sample volume, and removal by ion bombardment. After describing the model, we provide some examples of its practical applications for interpretation of the experimental results obtained during in situ SIMS studies of hydrogen interaction with the hydrogen-storage alloys TiFe, Zr2Fe, and with nickel. In the examples, some quantitative characteristics of surface-related processes involving hydrogen, such as hydrogen sputtering rate, activation energy of hydrogen desorption and absorption, have been successfully determined using various model approaches.

Introduction: Taxus species contain the anticancer alkaloid paclitaxel, as well as other taxanes similar in structure and potentially in effect to paclitaxel. Tissue-specific distribution patterns and seasonal variations of taxanes in some Taxus species have been reported; however, it is still under-presented for the taxanes in Taxus cuspidata. Methods: The radial distributions of eight taxanes in the transverse surface of freeze-fixed T. cuspidata stems from the late summer and the spring seasons were investigated by cryo-time-of-flight secondary ion mass spectrometry and scanning electron microscopy (cryo-TOF-SIMS/SEM) visualization and liquid chromatography-mass spectrometry (LC-MS) quantitative analysis. By optical microscopic observation, seasonal differences in the amounts and distribution patterns of target taxanes were further characterized in specific tissues. Results and Discussion: The overall amount of taxanes was higher in the late summer than in the spring. Also, taxanes' radial distribution was generally found at higher concentration in the phloem, the cambium and lower level in the periderm, the latest-forming xylem, with different taxanes showing several patterns with distinction between seasons, which were considered related to seasonal plant physiological behaviors. In addition, the distribution of baccatin III (BAC) was investigated at the cellular level, which was regarded in specific cells suggesting its transport in the radial and axial directions in the T. cuspidata stem. Characterizing the microscopic distribution of taxanes in the T. cuspidata stem is expected to play a role in the further study of their biosynthesis and in planta behaviors. [ABSTRACT FROM AUTHOR]

Background: Magnetotactic bacteria (MTB) are a unique group of microorganisms that sense and navigate through the geomagnetic field by biomineralizing magnetic nanoparticles. MTB from the phylum Nitrospirota (previously known as Nitrospirae) thrive in diverse aquatic ecosystems. They are of great interest due to their production of hundreds of magnetite (Fe3O4) magnetosome nanoparticles per cell, which far exceeds that of other MTB. The morphological, phylogenetic, and genomic diversity of Nitrospirota MTB have been extensively studied. However, the metabolism and ecophysiology of Nitrospirota MTB are largely unknown due to the lack of cultivation techniques. Methods: Here, we established a method to link the morphological, genomic, and metabolic investigations of an uncultured Nitrospirota MTB population (named LHC-1) at the single-cell level using nanoscale secondary-ion mass spectrometry (NanoSIMS) in combination with rRNA-based in situ hybridization and target-specific mini-metagenomics. Results: We magnetically separated LHC-1 from a freshwater lake and reconstructed the draft genome of LHC-1 using genome-resolved mini-metagenomics. We found that 10 LHC-1 cells were sufficient as a template to obtain a high-quality draft genome. Genomic analysis revealed that LHC-1 has the potential for CO2 fixation and NO3− reduction, which was further characterized at the single-cell level by combining stable-isotope incubations and NanoSIMS analyses over time. Additionally, the NanoSIMS results revealed specific element distributions in LHC-1, and that the heterogeneity of CO2 and NO3− metabolisms among different LHC-1 cells increased with incubation time. Conclusions: To our knowledge, this study provides the first metabolic measurements of individual Nitrospirota MTB cells to decipher their ecophysiological traits. The procedure constructed in this study provides a promising strategy to simultaneously investigate the morphology, genome, and ecophysiology of uncultured microbes in natural environments. 6gfJ7qtcG81szcFZGMmDYd Video Abstract [ABSTRACT FROM AUTHOR]

We demonstrate aluminum-on-silicon planar transmon qubits with time-averaged T1 energy relaxation times of up to 270 μs, corresponding to Q = 5 million, and a highest observed value of 501 μs. Through materials analysis techniques and numerical simulations we investigate the dominant source of energy loss, and devise and demonstrate a strategy toward its mitigation. Growing aluminum films thicker than 300 nm reduces the presence of oxide, a known host of defects, near the substrate-metal interface, as confirmed by time-of-flight secondary ion mass spectrometry. A loss analysis of coplanar waveguide resonators shows that this results in a reduction of dielectric loss due to two-level system defects. The correlation between the enhanced performance of our devices and the film thickness is due to the aluminum growth in columnar structures of parallel grain boundaries: transmission electron microscopy shows larger grains in the thicker film, and consequently fewer grain boundaries containing oxide near the substrate-metal interface. [ABSTRACT FROM AUTHOR]

Hydrothermal treatments of soda–lime silicate glass cause a remarkable improvement in the resistance to flaw formation with an increase of the critical load to ≈1 kgf. This remarkable effect is achieved even if the reaction layer between the glass and water solution is well below 1 µm. Positron Doppler broadening spectroscopy (DBS) reveals that the hydrothermal treatment causes a drop in the free volume of the glass network near the surface connected with the diffusion of molecular water whose presence was further confirmed by Fourier transformed infrared (FTIR) spectroscopy and secondary ion mass spectrometry (SIMS). Based on FTIR and SIMS, we also argue that the hydrothermal ion exchange is a double‐step process: first H+ substitutes Na+ in the network, and following molecular water permeates the system. Moreover, we show that the presence of water in the network is fundamental in stabilizing the modified glass surface leading to toughening. Once molecular water is released, the network is quickly polymerized and becomes more brittle. Hydrothermal toughening is only a partially reversible process, once water is released it is not possible to reobtain the same properties with a second treatment. Finally, it is shown that air and tin side of the float glass perform differently as a result of different water diffusion kinetics related to dissimilarities in the network density. [ABSTRACT FROM AUTHOR]

Guaymas Basin, located in the Gulf of California, is a hydrothermally active marginal basin. Due to steep geothermal gradients and localized heating by sill intrusions, microbial substrates like short-chain fatty acids and hydrocarbons are abiotically produced from sedimentary organic matter at comparatively shallow depths. We analyzed the effect of hydrocarbons on uptake of hydrocarbons by microorganisms via nano-scale secondary ion mass spectrometry (NanoSIMS) and microbial sulfate reduction rates (SRR), using samples from two drill sites sampled by IODP Expedition 385 (U1545C and U1546D). These sites are in close proximity of each other (ca. 1 km) and have very similar sedimentology. Site U1546D experienced the intrusion of a sill that has since then thermally equilibrated with the surrounding sediment. Both sites currently have an identical geothermal gradient, despite their different thermal history. The localized heating by the sill led to thermal cracking of sedimentary organic matter and formation of potentially bioavailable organic substrates. There were low levels of hydrocarbon and nitrogen uptake in some samples from both sites, mostly in surficial samples. Hydrocarbon and methane additions stimulated SRR in near-seafloor samples from Site U1545C, while samples from Site U1546D reacted positively only on methane. Our data indicate the potential of microorganisms to metabolize hydrocarbons even in the deep subsurface of Guaymas Basin. [ABSTRACT FROM AUTHOR]

In order to gain insights on the conditions of aqueous alteration on asteroid Ryugu and the origin of water in the outer solar system, we developed the measurement of water content in magnetite at the micrometer scale by secondary ion mass spectrometry (NanoSIMS) and determined the H and Si content of coarse‐grained euhedral magnetite grains (polyhedral magnetite) and coarse‐grained fibrous (spherulitic) magnetite from the Ryugu polished section A0058‐C1001. The hydrogen content in magnetite ranges between ~900 and ~3300 wt ppm equivalent water and is correlated with the Si content. Polyhedral magnetite has low and homogenous silicon and water content, whereas fibrous magnetite shows correlated Si and water excesses. These excesses can be explained by the presence of hydrous Si‐rich amorphous nanoinclusions trapped during the precipitation of fibrous magnetite away from equilibrium and testify that fibrous magnetite formed from a hydrous gel with possibly more than 20 wt% water. An attempt to determine the water content in sub‐μm framboids indicates that additional calibration and contamination issues must be addressed before a safe conclusion can be drawn, but hints at elevated water content as well. The high water content in fibrous magnetite, expected to be among the first minerals to crystallize at low water–rock ratio, points to the control of water content by local conditions of magnetite precipitation rather than large‐scale alteration conditions. Systematic lithological variations associated with water‐rich and water‐poor magnetite suggest that the global context of alteration may be better understood if local water concentrations are compared with millimeter‐scale distribution of the various morphologies of magnetite. Finally, the high water content in the magnetite precursor gel indicates that the initial O isotopic composition in alteration water must not have been very different from that of the earliest magnetite crystals. [ABSTRACT FROM AUTHOR]

Consortia of multicellular magnetotactic bacteria (MMB) are currently the only known example of bacteria without a unicellular stage in their life cycle. Because of their recalcitrance to cultivation, most previous studies of MMB have been limited to microscopic observations. To study the biology of these unique organisms in more detail, we use multiple culture-independent approaches to analyze the genomics and physiology of MMB consortia at single-cell resolution. We separately sequenced the metagenomes of 22 individual MMB consortia, representing 8 new species, and quantified the genetic diversity within each MMB consortium. This revealed that, counter to conventional views, cells within MMB consortia are not clonal. Single consortia metagenomes were then used to reconstruct the species-specific metabolic potential and infer the physiological capabilities of MMB. To validate genomic predictions, we performed stable isotope probing (SIP) experiments and interrogated MMB consortia using fluorescence in situ hybridization (FISH) combined with nanoscale secondary ion mass spectrometry (NanoSIMS). By coupling FISH with bioorthogonal noncanonical amino acid tagging (BONCAT), we explored their in situ activity as well as variation of protein synthesis within cells. We demonstrate that MMB consortia are mixotrophic sulfate reducers and that they exhibit metabolic differentiation between individual cells, suggesting that MMB consortia are more complex than previously thought. These findings expand our understanding of MMB diversity, ecology, genomics, and physiology, as well as offer insights into the mechanisms underpinning the multicellular nature of their unique lifestyle. Multicellular magnetotactic bacteria (MMB) are unique in having no unicellular stage in their life cycle. This study characterizes the genomics and physiology of MMB consortia at single cell resolution, revealing that individual cells are not genetically identical and exhibit significant metabolic differentiation, highlighting their level of complexity. [ABSTRACT FROM AUTHOR]

Alleviating the decomposition of the electrolyte is of great significance to improving the cycle stability of cathodes, especially for LiCoO2 (LCO), its volumetric energy density can be effectively promoted by increasing the charge cutoff voltage to 4.6 V, thereby supporting the large‐scale application of clean energy. However, the rapid decomposition of the electrolyte under 4.6 V conditions not only loses the transport carrier for lithium ion, but also produces HF and insulators that destroy the interface of LCO and increase impedance. In this work, the decomposition of electrolyte is effectively suppressed by changing the adsorption force between LCO interface and EC. Density functional theory illustrates the LCO coated with lower electronegativity elements has a weaker adsorption force with the electrolyte, the adsorption energy between LCO@Mg and EC (0.49 eV) is weaker than that of LCO@Ti (0.73 eV). Meanwhile, based on the results of time of flight secondary ion mass spectrometry, conductivity‐atomic force microscopy, in situ differential electrochemical mass spectrometry, soft X‐ray absorption spectroscopy, and nuclear magnetic resonance, as the adsorption force increases, the electrolyte decomposes more seriously. This work provides a new perspective on the interaction between electrolyte and the interface of cathode and further improves the understanding of electrolyte decomposition. [ABSTRACT FROM AUTHOR]

There are likely many undiscovered impact structures on Earth, but several challenges prevent their detection, including possible concealment beneath large ice sheets. In recent years, geophysical, geochemical, and microphysical evidence has mounted for a ca. 58 Ma impact structure under the Hiawatha Glacier, northwest Greenland. Here, we report evidence for a second, much older hypervelocity impact event in this region, recorded in an impact melt rock sample collected from a glaciofluvial deposit in Inglefield Land. Secondary ion mass spectrometry U-Pb analyses of shock metamorphosed zircon grains yielded a previously unrecorded, Proterozoic best estimate impact age of 1039 ± 16 Ma (mean square of weighted deviates = 2.9). Based on Archean-Proterozoic target rock U-Pb ages obtained from unshocked zircon grains and the location of the melt rock sample along the ice margin, we suggest this sample was derived from a hypervelocity impact structure farther inland, concealed by the Greenland Ice Sheet. This study demonstrates the ability to uncover new impact events in some of the most inaccessible areas on Earth and the possibility of sampling multiple impact structures from one location when examining ex situ material. Our results have implications for current and future Martian and lunar returned samples that demonstrably bear complex impact histories. [ABSTRACT FROM AUTHOR]

Since the early days of time of flight secondary ion mass spectrometry (ToF-SIMS), increasing the ion signal has been crucial. It is even more crucial when performing tandem mass spectrometry experiments. To achieve this goal, many developments have been made over the years, which are divided into two categories: instrumental development and sample modification. The latter involves sample metallization, matrix deposition, or changing the temperature of the measurement. In this study, the possibility of using matrices to enhance the signals of organic light emitting device (OLED) molecules was explored. Seven molecules commonly used in OLEDs were separately deposited on Si wafers: Alq3, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile, Ir(mppy)3, N,N′-bis(naphthalene-1-yl)-N,N′-bis(phenyl)benzidine, 2,2′,7,7′-tetra(N,N-ditolyl)-amino-spiro-bifluor (STTB), and tris(4-carbazoyl-9-ylphenyl)amine. Using the same solvent, three different matrices with different thicknesses, common in matrix assisted light desorption ionization time of flight mass spectrometry, α-cyano-4-hydroxycinnamic acid, 2,5-dihydrobenzoic acid (DHB), and dihydrochloride N-(1-Naphthyl)ethylenediamine, were sprayed on these surfaces. Spectra were acquired for all compounds and spraying conditions in static ToF-SIMS experiments for Alq3 chemical imaging and depth profiling were performed. This allowed the investigation of the fragmentation pattern of the chosen matrices in ToF-SIMS and, thus, obtained a reference for these molecules. The results show that matrices can enhance the signal of fragments of the studied molecules, for example, the signal of STTB is increased with DHB spraying. Samples sprayed only with the solvent were also prepared to verify the impact of the matrices on the signal. Spraying with the solvent alone can enhance the signal even more than the matrices up to four times in the case of Alq3. This result opens new possibilities in the field of matrix-enhanced ToF-SIMS in terms of applications and matrix choices. [ABSTRACT FROM AUTHOR]

Saffron, renowned for its aroma and flavor, is susceptible to adulteration due to its high value and demand. Current detection methods, including ISO standards, often fail to identify specific adulterants such as safflower or turmeric up to 20% (w/w). Therefore, the quest continues for robust screening methods using advanced techniques to tackle this persistent challenge of safeguarding saffron quality and authenticity. Advanced techniques such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), with its molecular specificity and high sensitivity, offer promising solutions. Samples of pure saffron and saffron adulterated with safflower and turmeric at three inclusion levels (5%, 10%, and 20%) were analyzed without prior treatment. Spectral analysis revealed distinct signatures for pure saffron, safflower, and turmeric. Through principal component analysis (PCA), TOF-SIMS effectively discriminated between pure saffron and saffron adulterated with turmeric and safflower at different inclusion levels. The variation between the groups is attributed to the characteristic peaks of safflower and the amino group peaks and mineral peaks of saffron. Additionally, a study was conducted to demonstrate that semi-quantification of the level of safflower inclusion can be achieved from the normalized values of its characteristic peaks in the saffron matrix. [ABSTRACT FROM AUTHOR]

[Display omitted] Hydrogen in materials has attracted tremendous interest as its incorporation leads to significant alterations in nanoscale structure, composition, and chemistry, impacting functional properties. It has also been integral to nuclear fusion reactors and is considered a future clean energy source. However, nanoscale characterization and manipulation of hydrogen in materials are challenging as only a selected few analytical techniques can readily detect hydrogen, among which time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a unique and powerful one due to its excellent detection limit along with decent depth and lateral resolutions. In this review, we discuss, using selected examples, how to detect and quantify hydrogen in materials by ToF-SIMS and its impact on revealing the hydrogenation/protonation-induced novel functional states in different classes of materials. In addition, we present our protocols on sample preparation and experimental conditions optimization, allowing us to achieve the best possible results. Finally, we highlight future research directions that can lead to the discovery of novel functional states and ultimately provide a deeper understanding of scientific questions in materials science. [ABSTRACT FROM AUTHOR]

The growth of high-composition GeSn films in the future will likely be guided by algorithms. In this study, we show how a logarithmic-based algorithm can be used to obtain high-quality GeSn compositions up to 16% on GaAs (001) substrates via molecular beam epitaxy. Herein, we use composition targeting and logarithmic Sn cell temperature control to achieve linearly graded pseudomorph Ge1−xSnx compositions up to 10% before partial relaxation of the structure and a continued gradient up to 16% GeSn. In this report, we use X-ray diffraction, simulation, secondary ion mass spectrometry, and atomic force microscopy to analyze and demonstrate some of the possible growths that can be produced with the enclosed algorithm. This methodology of growth is a major step forward in the field of GeSn development and the first ever demonstration of algorithmically driven, linearly graded GeSn films. [ABSTRACT FROM AUTHOR]

Self-diffusion in amorphous germanium is studied at temperatures between 325 and 370 °C utilizing amorphous isotopically controlled germanium multilayer structures. The isotope multilayer is epitaxially grown on a single crystalline germanium-on-insulator structure by means of molecular beam epitaxy and subsequently amorphized by self-ion implantation. After heat treatment, the diffusional broadening of the isotope structure is measured with time-of-flight secondary ion mass spectrometry. The temperature dependence of self-diffusion is accurately described by the Arrhenius equation with the activation enthalpy Q = (2.21 ± 0.12) eV and pre-exponential factor D 0 = (2.3 2 − 2.10 + 20.79 ) cm2 s−1. The activation enthalpy equals the activation enthalpy of solid phase epitaxial recrystallization (SPER). This agreement suggests that self-diffusion in amorphous germanium is similar to SPER, also mainly mediated by local bond rearrangements. Classical molecular dynamics simulations with a modified Stillinger–Weber-type interatomic potential yield results that are consistent with the experimental data and support the proposed atomic mechanism. [ABSTRACT FROM AUTHOR]

The marine subsurface is a long-term sink of atmospheric carbon dioxide with significant implications for climate on geologic timescales. Subsurface microbial cells can either enhance or reduce carbon sequestration in the subsurface, depending on their metabolic lifestyle. However, the activity of subsurface microbes is rarely measured. Here, we used nanoscale secondary ion mass spectrometry (nanoSIMS) to quantify anabolic activity in 3,203 individual cells from the thermally altered deep subsurface in the Guaymas Basin, Mexico (3-75 m below the seafloor, 0-14°C). We observed that a large majority of cells were active (83%-100%), although the rates of biomass generation were low, suggesting cellular maintenance rather than doubling. Mean single-cell activity decreased with increasing sediment depth and temperature and was most strongly correlated with porewater sulfate concentrations. Intracommunity heterogeneity in microbial activity decreased with increasing sediment depth and age. Using a dual-isotope labeling approach, we determined that all active cells analyzed were heterotrophic, deriving the majority of their cellular carbon from organic sources. However, we also detected inorganic carbon assimilation in these heterotrophic cells, likely via processes such as anaplerosis, and determined that inorganic carbon contributes at least 5% of the total biomass carbon in heterotrophs in this community. Our results demonstrate that the deep marine biosphere at Guaymas Basin is largely active and contributes to subsurface carbon cycling primarily by not only assimilating organic carbon but also fixing inorganic carbon. Heterotrophic assimilation of inorganic carbon may be a small yet significant and widespread underappreciated source of labile carbon in the global subsurface. [ABSTRACT FROM AUTHOR]

Bridgmanite, the most abundant mineral in the lower mantle, can play an essential role in deep-Earth hydrogen storage and circulation processes. To better evaluate the hydrogen storage capacity and its substitution mechanism in bridgmanite occurring in nature, we have synthesized high-quality single-crystal bridgmanite with a composition of (M g 0.88 F e 0.05 2 + F e 0.05 3 + A l 0.03) (S i 0.88 A l 0.11 H 0.01) O 3 at nearly water-saturated environments relevant to topmost lower mantle pressure and temperature conditions. The crystallographic site position of hydrogen in the synthetic (Fe,Al)-bearing bridgmanite is evaluated by a time-of-flight single-crystal neutron diffraction scheme, together with supporting evidence from polarized infrared spectroscopy. Analysis of the results shows that the primary hydrogen site has an OH bond direction nearly parallel to the crystallographic b axis of the orthorhombic bridgmanite lattice, where hydrogen is located along the line between two oxygen anions to form a straight geometry of covalent and hydrogen bonds. Our modeled results show that hydrogen is incorporated into the crystal structure via coupled substitution of Al3+ and H+ simultaneously exchanging for Si4+, which does not require any cation vacancy. The concentration of hydrogen evaluated by secondary-ion mass spectrometry and neutron diffraction is ~0.1 wt% H2O and consistent with each other, showing that neutron diffraction can be an alternative quantitative means for the characterization of trace amounts of hydrogen and its site occupancy in nominally anhydrous minerals. [ABSTRACT FROM AUTHOR]

The narrow pH application range and lower utilization of ferrous ions (Fe(II)) restrict the application of Fe(II)/persulfate (PS) technology. In this paper, simulated sunlight and citric acid (Cit) as a chelator were introduced in an Fe(II)/PS system to overcome the drawbacks and enhance the degradation of typical antibiotic sulfamethoxazole (SMX) in secondary wastewater. The degradation kinetics, mechanism, and influence factors of SMX in a sunlight/Fe(II)/Cit/PS system and a sunlight/Fe(II)/Cit system as a comparable system were investigated. The removal efficiency of SMX can reach 71.15% and 85.25% in the sunlight/Fe(II)/Cit system and sunlight/Fe(II)/Cit/PS system with 0.1 mM Fe(II), 0.6 mM Cit, and 1 mM PS. The increase of Fe(II) concentration in both systems proved that sunlight promoted the regeneration of Fe(II) from the ferric ion chelates. However, the Fe(II) concentration decreased after 30 min in the sunlight/Fe(II)/Cit/PS system because of the decomposition of Cit. Radical quencher experiments indicated that SO4·−, ·OH, and O2·− contributed 2.48%, 88.43%, and 6.91% to the removal of SMX, respectively. Electron paramagnetic resonance spectra also proved the formation of ·OH and O2·−. The degradation of SMX was proposed to proceed via isomerization, cleavage of S–N bond, and hydroxylation. Overall, the sunlight/Fe(II)/Cit/PS process can be used as an advanced treatment technology for antibiotics in municipal wastewater. [ABSTRACT FROM AUTHOR]

Surface Science Spectra (SSS) is a journal that provides high-quality, peer-reviewed spectra from various techniques, including SIMS (secondary ion mass spectrometry). The journal accepts SIMS positive and negative ion spectral data, but not SIMS image or depth profile data. The guidelines for submitting SIMS data to SSS are detailed and specific, including instructions on calibrating the data, measuring mass resolving power, and identifying peaks in the spectra. The submission should include calibrated data saved as text files, figures that follow formatting guidelines, and a spectral features table. The editors of SSS are available to answer any questions and provide assistance in preparing a successful submission. [Extracted from the article]

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used to analyze cultural heritage materials because it can simultaneously detect organic and inorganic materials while mapping them on a surface. The precise identification of a pigment in a specific layer of a painting or of remaining color on a statue can inform about the technique used or the time of manufacture as well as expose possible forgeries when anachronistic ingredients are identified. Reference spectra are required to confidently identify a given pigment using ToF-SIMS. This database focuses on six white pigments made from calcium-rich natural or synthetized materials, prepared following traditional processes. Such pigments are frequently found in the preparation layers, namely, "ground," separating the support from the observable paint layers, and providing a smooth surface to hold the paint on while preventing its absorption by the substrate. Differentiating between these pigments is helpful to better describe the painting practice. Here, ToF-SIMS reference spectra using a Bi3+ primary ion species are presented for both polarities. [ABSTRACT FROM AUTHOR]

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used to analyze cultural heritage materials because it can simultaneously detect organic and inorganic materials while mapping them on a surface. The precise identification of a pigment in a specific layer of a painting or of remaining color on a statue can inform about the technique used or the time of manufacture as well as expose possible forgeries when anachronistic ingredients are identified. Reference spectra are required to confidently identify a given pigment using ToF-SIMS. This paper focuses on four blue pigments manufactured following historical recipes: two natural ground and processed lapis lazuli pigments, one synthetic ultramarine pigment, and the blue-colored ground cobalt glass pigment smalt. The positive and negative polarity ToF-SIMS reference spectra using a Bi3+ primary ion species are presented. Differentiating these family of pigments is of interest as they have similar compositions but are used in very different contexts. It is particularly noteworthy that the two natural lapis lazuli pigments can be distinguished from the synthetic counterpart ultramarine using ToF-SIMS. [ABSTRACT FROM AUTHOR]

We report positive and negative ion time-of-flight secondary ion mass spectrometry (ToF-SIMS) spectra of metal-halide perovskite (MHP) films used for photovoltaic applications. This ToF-SIMS spectral library is of importance because it identifies the major peaks in most MHP films from organic [formamidinium (FA+)] and inorganic (Cs+) cations and anions (I− and Br−). [ABSTRACT FROM AUTHOR]

Static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed for acquiring the high-resolution surface spectra of four types of synthesized imidazolium ionene membranes. These novel membranes have aromatic ether–ketone–ether linkages inspired by poly(ether ether ketone) (PEEK). The PEEK-ionenes synthesized for this study have imidazolium cations placed in the polymeric backbone with bistriflimide [Tf2N]− counterions. The attention given to synthetically modified PEEK derivatives, such as PEEK-ionenes, is considerable due to their ability to selectively capture CO2 molecules and other light gases. Therefore, it is important to characterize the surface of these synthesized novel PEEK-ionenes. In this work, characteristic and unique peaks were identified in the positive spectra of each sample. The differences in mass spectra among the samples provide insights for optimizing or fine-tuning the PEEK-ionenes synthesis to achieve a high-performance CO2 separation membrane with enhanced permeability, selectivity, and mechanical stability. The SIMS spectra and identified characteristic peaks of these synthesized ionenes will serve as a reference in the positive mode, complementing the corresponding spectra reported in the negative ion mode (Paper II). [ABSTRACT FROM AUTHOR]

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to analyze poly(ether ether ketone) (PEEK) based membranes. PEEK membranes have been shown to be effective in the separation of CO2 from flue gases (post-combustion technique). The PEEK membranes were synthesized using novel aromatic ether-ketone linkages inspired by PEEK with polymeric backbone bistriflimide [Tf2N]− counterions. One of the keys to advancing this technology is developing membranes that are selective and permeable toward CO2, in which PEEK based membranes have been shown to be. Furthermore, the compatibility between various water lean solvents also needs to be investigated. Surface analytical techniques such as x-ray photoelectron spectroscopy and ToF-SIMS are useful for investigating chemical changes between membranes. Herein, we present ToF-SIMS data obtained in the negative ion mode for four different PEEK membranes designed for use in CO2 capture systems. Positive ion mode spectra are reported in Paper I. [ABSTRACT FROM AUTHOR]

Tectonic mélanges, characterized by conditions reflective of modern subduction fault zones, preserve mineral veins formed through mass transfer, a mechanism influencing the slip behavior of subduction megathrusts. In this study, we apply secondary ion mass spectrometry quartz‐calcite oxygen isotope thermometry and clumped isotope thermometry to examine the temperatures of vein formations in six mélange units in the Cretaceous Shimanto belt and one mélange in the Kodiak accretionary prism. Calcite in the veins exhibits δ13CPDB values ranging from −17.2‰ to −6.8‰, indicative of a carbon source mixing with sedimentary carbonate and organic matter. δ18OSMOW values of calcite range from +11.1‰ to +17.2‰; quartz yields δ18OSMOW values of +14.9‰ to +21.7‰. Oxygen isotopic signatures in minerals reveal that most vein‐forming fluids are significantly affected by rock buffering, while some retain isotopic compositions of seawater and meteoric water. Temperature estimates, derived from both thermometers, fall within the range of 100–250°C. Notably, vein temperatures remain constant across diverse vein types and mélange units with distinct maximum temperatures. The combined temperature records and fluid isotopic compositions imply vein formations at shallower depths linked to the incorporation of seawater, meteoric water, and fluid released from early dehydration reactions. At greater depths, vein formations are associated with fluid released from clay dehydration and long‐distance fluid flow. Reduced vein formations between 250 and 350°C may correlate with a shift to fluid‐unsaturated conditions resulting from clay hydration reactions. Our study highlights potential mechanical and hydraulic variations within the thermal conditions of 100–350°C along the plate boundary driven by fluid‐mineral interactions. Plain Language Summary: Temperature influences the processes responsible for triggering earthquakes at subduction zones. This inference is supported by the observed concentration of seismic activities within a specific temperature range along the plate interface. To investigate the topic, we examine a distinctive rock type known as tectonic mélanges, which has undergone subduction in the past and has since been exposed. These mélanges contain mineral veins formed through the movement of materials; a factor that has shown correlation with the occurrence of earthquakes at subduction zones. To determine the temperatures at which the mechanism operates, leading to the formation of the veins, we employ two methodologies: quartz‐calcite oxygen isotope thermometry and clumped isotope thermometry. Our findings indicate that, regardless of the geographical locations or the types of veins, they formed within a temperature range of 100–250°C. This consistency implies the existence of a consistent depth range within subduction zones, where fluids are predominantly present, facilitating material movement and consequently, the development of these mineral veins. Key Points: Quartz‐calcite veins in ancient accretionary prisms record temperatures of 100–250°C, implying a fluid‐rich zone along plate interfacesFluid isotopic compositions suggest rock‐buffered fluids as major vein‐forming fluids derived from the dehydration of host rocksReduced vein formation, along with clay hydration at 250–350°C, may cause a shift in hydrogeology and mechanics of subduction fault zones [ABSTRACT FROM AUTHOR]

This work presents a comprehensive analysis of the synthesis, structural–spectroscopic characterization, thermal stability, and luminescent attributes of Sm3+-activated LiZnPO4 phosphors with diverse Sm3+ doping percentiles that work towards developing luminescent materials for white-light-emitting diode (WLED) applications. The polycrystalline samples of LiZn(1 − x) Smx3+PO4 (x = 0, 0.01, 0.03, 0.05, 0.07, 0.09, and 0.10) phosphor were synthesized using a solid-state reaction (SSR) technique. X-ray diffraction (XRD) and Rietveld refinement indicate a single-phase monoclinic structure of all compositions with the C1c1 space group. Phase purity and stoichiometry of elemental composition were validated by Fourier transform infrared (FTIR) spectroscopy and energy-dispersive spectroscopy (EDS) examination. Field-emission scanning electron microscopy (FE-SEM) images indicate irregular and nonuniform microstructures for all compositions with a mean dimension of 1.252 µm. The investigation of diffuse reflectance (DR) spectra with the Kubelka–Munk function F(R∞) determines the compound's bandgap to be 3.1 eV. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) indicates various ions are regularly distributed across the surface. Further, the photometric analysis reveals that the Commission Internationale de l'Éclairage (CIE) coordinates are roughly (0.55, 0.44), and color purity is greater than 82% in all compositions. These results, along with the photoluminescence (PL) spectral analysis, lifetime analysis, and thermal stability, indicate that Sm3+-doped LiZnPO4 is a viable orange-red-emitting phosphor candidate for creating white-light-emitting diodes (WLEDs). [ABSTRACT FROM AUTHOR]

In situ X-ray diffraction (XRD) was used to compare nitrogen low-energy ion implantation (LEII) into austenitic stainless steel 316Ti and super austenitic stainless steel 904L. While the diffusion and layer growth were very similar, as derived from the decreasing intensity of the substrate reflection, strong variations in the observed lattice expansion—as a function of orientation, the steel alloy, and nitriding temperature—were observed. Nevertheless, a similar resulting nitrogen content was measured using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Furthermore, for some conditions, the formation of a double layer with two distinct lattice expansions was observed, especially for steel 904L. Regarding the stability of expanded austenite, 316Ti had already decayed in CrN during nitriding at 500 °C, while no such effect was observed for 904L. Thus, the alloy composition has a strong influence only on the lattice expansion and the stability of expanded austenite—but not the diffusion and nitrogen content. [ABSTRACT FROM AUTHOR]

This study involved direct doping of In2O3 into silicon carbide (SiC) powder, resulting in 8.0 at% In-doped SiC powder. Subsequently, heating at 500 °C was performed to form a target, followed by the utilization of electron beam (e-beam) technology to deposit the In-doped SiC thin films with the thickness of approximately 189.8 nm. The first breakthrough of this research was the successful deposition of using e-beam technology. The second breakthrough involved utilizing various tools to analyze the physical and electrical properties of In-doped SiC thin films. Hall effect measurement was used to measure the resistivity, mobility, and carrier concentration and confirm its n-type semiconductor nature. The uniform dispersion of In ions in SiC was as confirmed by electron microscopy energy-dispersive spectroscopy and secondary ion mass spectrometry analyses. The Tauc Plot method was employed to determine the Eg values of pure SiC and In-doped SiC thin films. Semiconductor parameter analyzer was used to measure the conductivity and the I-V characteristics of devices in In-doped SiC thin films. Furthermore, the third finding demonstrated that In2O3-doped SiC thin films exhibited remarkable current density. X-ray photoelectron spectroscopy and Gaussian-resolved spectra further confirmed a significant relationship between conductivity and oxygen vacancy concentration. Lastly, depositing these In-doped SiC thin films onto p-type silicon substrates etched with buffered oxide etchant resulted in the formation of heterojunction p-n junction. This junction exhibited the rectifying characteristics of a diode, with sample current values in the vicinity of 102 mA, breakdown voltage at approximately −5.23 V, and open-circuit voltage around 1.56 V. This underscores the potential of In-doped SiC thin films for various semiconductor devices. [ABSTRACT FROM AUTHOR]

Cells are the most basic structural and functional unit of living organisms. In recent years, people have paid more attention to cell heterogeneity. In order to characterize the heterogeneity of cells and prevent the life information in an individual cell from being overwhelmed by the average level of the population gained from traditional cell biology research, many new analytical techniques have been developed for single-cell analysis. However, single-cell analysis is extremely challenging due to the minimal cell volume, low content and wide variety of analytes in single cells, some of analytes change rapidly in cells and others may interfere with each other during analysis. Mass spectrometry has gradually become an ideal tool for single-cell analysis due to its high sensitivity, high resolution and high selectivity. In this review, several techniques of single-cell analysis based on mass spectrometry in the recent five years were systematically summarized and discussed including electrospray ionization mass spectrometry (ESI-MS), laser desorption ionization mass spectrometry (LDI-MS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS). Finally, this review also looked into future developments of these mass spectrometry-based techniques. With the development of cell biology, the requirement for single-cell analysis technology is increasing as well. In the meanwhile, single-cell analysis, which focuses on studying the mechanisms of cellular and molecular behavior, has aroused more and more attention from various branches of life sciences in recent years. Although higher spatial resolution and detection sensitivity have become the development trends for single-cell mass spectrometry, none of these mass spectrometry-based techniques can be recognized flawless, which means they all have certain flaws to some extent. Consequently, single-cell analysis technology based on mass spectrometry is developing towards methodological diversification. On the one hand, it is of great importance to choose one suitable mass spectrometry-based technique according to the research purpose and actual conditions. On the other hand, it should be also emphasized that different methods can complement each other and jointly provide a more comprehensive analysis environment for single-cell mass spectrometry, thereby improving and innovating existing single-cell analysis techniques based on mass spectrometry. This review will provide insights into better understanding on and development of single-cell analysis by mass spectrometry. [ABSTRACT FROM AUTHOR]

In Xinjiang, China, a female corpse dating back to the Han Dynasty was discovered adorned in splendid attire crafted from wool fibers dyed in vibrant shades of red, blue, and light yellow. This study utilized fabric fragments as research specimens to analyze the dyes present, primarily employing time of flight secondary ion mass spectrometry (TOF-SIMS), in conjunction with optical microscopy, ultra-high performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) and a mercury vapor analyzer for precise characterization. The TOF-SIMS analysis revealed the presence of mercury isotopic ions (202Hg+ and 199Hg+), mercury-sulfur ions (HgS+, m/z 234), sulfur isotopic ions (32S− and 34S−) on the surface of the red fiber samples. These findings suggest the utilization of cinnabar (HgS), a naturally occurring inorganic mineral dye, in the red fibers. Moreover, mercury content measurements indicated a significant enrichment of mercury in the red fibers, with the Hg content of 84 ng/g, markedly higher than the average Hg content of other fibers, which stood at 31 ng/g. Analysis of the blue fiber samples detected the quasi-molecular ion m/z 263 ([M+H]+) and a series of reasonable fragment ions, such as m/z 235 (C15H11N2O+) and m/z 247 (C16H11N2O+), indicative of the presence of indigo, a natural plant-based organic dye. UPLC-HRMS analysis further confirmed the presence of indigo in the blue fabric samples, providing cross-validation of the dye used. The light yellow fiber samples did not yield detections of common organic dyes like turmeric or inorganic pigments such as iron-yellow (Fe2O3H2O). The yellow hue observed in these fibers may be attributed to the natural aging of the original white wool, remaining undyed. Additionally, granular water-soluble inorganic ions such as NaCl, carbonate, and sulfate were detected within the yellow fabric samples. This study underscores the efficacy of the TOF-SIMS method for in-situ microanalysis and ultra-high sensitivity detection, rendering it is suitable for the analysis of both organic dye and inorganic dye. Moreover, TOF-SIMS will be widely used in archaeological and museum collections related research. [ABSTRACT FROM AUTHOR]

Accurate monitoring and, thus, control of rapid thermal anneal (RTA) are critical for manufacturing semiconductor devices. In this work, we developed a method by using secondary ion mass spectrometry (SIMS) aimed to improve long-term repeatability in monitoring RTA. We used a test wafer in a batch implant as SIMS reference for the remaining wafers in the same batch and eliminated the impact from wafer aging and test wafer variation from lot to lot as often encountered in sheet resistance monitoring. In addition, the use of the normalized peak concentration of boron as measured by SIMS allows for repeatable analyses to capture 1 °C or lower drift in an RTA temperature higher than 1000 °C. The benefit of this SIMS approach has been validated by improvement in the device yield since the implementation of monitoring. [ABSTRACT FROM AUTHOR]