Secondary Ion Research Articles

Tracing the Cross‐Talk Phenomenon of Vinylethylene Carbonate to Unveil its Counterintuitive Influence as an Electrolyte Additive on High‐Voltage Lithium‐Ion Batteries

AbstractThe formation of effective interphases is crucial to enable high‐performance lithium‐ion batteries. This can be facilitated by the introduction of electrolyte additives, ensuring improved stability and transport properties. The identification of proper additives requires a comprehensive understanding of the fundamental mechanisms of interfacial reactions governing interphase formation. This study presents a detailed investigation of widely known and less conventional interphase‐forming additives in high‐voltage LiNi0.6Mn0.2Co0.2O2, NMC622||artificial graphite cells. The electrochemical characterization shows that cells containing vinylethylene carbonate (VEC) significantly outperform all other investigated electrolyte formulations. Surprisingly, gas chromatography‐mass spectroscopy measurements of the electrolyte composition after cycling indicate the formation of an ineffective solid‐electrolyte interphase (SEI) in the presence of VEC. A thorough analysis of the interfacial composition via operando shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS) and surface‐enhanced Raman spectroscopy elucidates rather the formation of an effective cathode‐electrolyte interphase (CEI). This phenomenon results from the reductive reaction of VEC on the anode, followed by the product transfer and electro‐polymerization of reaction products on the cathode. Additionally, focused ion beam secondary ion mass spectrometry (FIB‐SIMS) with a time of flight (ToF)‐detector is used to analyze the elemental spatial distribution of Li‐species and Mn in the respective SEIs.

Effect of hydrogen poisoning on p-gate AlGaN/GaN HEMTs

In this work, we investigate the degradation behavior and mechanism of p-gate AlGaN/GaN high-electron mobility transistors (HEMTs) for the first time under hydrogen (H2) atmosphere. The experimental results reveal significant decrease in drain-to-source current, negative drift in threshold voltage, increase in off-state gate leakage current, and deterioration of subthreshold swing in the p-gate AlGaN/GaN HEMT after H2 treatment. The degradation of the electrical parameters is considered to hydrogen poisoning phenomenon. Through secondary ion mass spectrometry and variable temperature photoluminescence spectroscopy, we observe the increase in hydrogen concentration in the p-GaN layer and the formation of electrically inactive Mg–H complexes after H2 treatment. As results, the effective hole concentration decreases and the trap density of the device increases, which are confirmed by Hall effect measurement and low-frequency noise analysis, respectively. The detrimental effect of hydrogen on p-gate AlGaN/GaN HEMTs can be attributed primarily to the compensation of Mg doping and the generation of defects.

Multilayer Diamond‐Like Carbon Films on Monocrystalline Diamond

Multilayer films of diamond‐like carbon (DLC) on monocrystalline diamond substrates have been for the first time obtained by plasma‐chemical deposition. Their chemical composition and structural and morphological properties are studied. The DLC individual layers differ in their sp3 carbon content. The multilayer nature of the resulting coatings is confirmed by periodic density modulation on the small‐angle X‐ray reflectometry curve and modulations in the CsC8, CsC6, CsC4 lines on the crater depth profile of secondary ions of elements (secondary ion mass spectrometry). The dependence of the deposition rate of multilayer DLC films on diamond, their composition and properties on the argon additive to the reaction gas mixture, as well as on methane flow, pressure and growth time, are studied.

Nitrogen modified graphene nanowalls for retrieval of trace level cerium from aqueous medium

Removal of cerium from environmental and aqueous streams is essential in waste water rejuvenation processes. Nitrogen modified graphene nano walls (N-GNWs) have shown ultra-high sorption efficiency of trivalent cerium from aqueous medium (Kd > 2 × 107) and a large sorption capacity of ∼ 2500 mg/g is achieved. N-GNWs were deposited on carbon paper substrate using PECVD technique. The three-dimensional nature of N-GNWs are revealed from high resolution FESEM images. Raman spectroscopic studies have shown that GNWs are defective and possess a few layer graphene like structure. Secondary Ion Mass Spectroscopic studies of the Ce sorbed N-GNWs and optical emission spectroscopy of the residual solution confirm the sorptive retrieval of cerium. Visual Minteq based ionization model is introduced to explain high (>90 %) sorption of Ce at pH≥7 and the mechanistic aspects of sorption for standard Cerium solution is discussed. The sorption involves attachment of cerium hydroxyl ions to the active cites on the sorbent surface.

Indepth doping assessment of thick doped GaAs layer by scanning spreading resistance microscopy

Scanning spreading resistance microscopy (SSRM) measurements were performed on GaAs thick films grown by hydride vapor phase epitaxy technology under different growth conditions to evaluate their carrier concentrations. For this purpose, a calibration curve was established based on a multilayer staircase structure grown by molecular beam epitaxy. The dopant calibration range measured by secondary ion mass spectrometry is from 5 × 1016 to 1019 cm−3. An abnormal phenomenon in the calibration process was explained by taking into account the parasitic parallel resistance of the calibration samples. Finally, the calibration curve was used to quantitatively analyze the carriers inside the Zn doping p-type GaAs film from 4 × 1016 to 1018 cm−3 range. We demonstrate here the applicability of SSRM to the in-depth analysis of thick epilayers, providing new inputs for the control of thick film technologies.

Orbi‐SIMS Mediated Metabolomics Analysis of Pathogenic Tissue up to Cellular Resolution

AbstractTumors have a complex metabolism that differs from most metabolic processes in healthy tissues. It is highly dynamic and driven by the tumor cells themselves, as well as by the non‐transformed stromal infiltrates and immune components. Each of these cell populations has a distinct metabolism that depends on both their cellular state and the availability of nutrients. Consequently, to fully understand the individual metabolic states of all tumor‐forming cells, correlative mass spectrometric imaging (MSI) up to cellular resolution with minimal metabolite shift needs to be achieved. By using a secondary ion mass spectrometer (SIMS) equipped with an Orbitrap mass analyzer, we present a workflow to image primary murine tumor tissues up to cellular resolution and correlate these ion images with post acquisition immunofluorescence or histological staining. In a murine breast cancer model, we could identify metabolic profiles that clearly distinguish tumor tissue from stromal cells and immune infiltrates. We demonstrate the robustness of the classification by applying the same profiles to an independent murine model of lung cancer, which is accurately segmented by histological traits. Our pipeline allows metabolic segmentation with simultaneous cell identification, which in the future will enable the design of subpopulation‐targeted metabolic interventions for therapeutic purposes.

Metabolomic and Proteomic Analysis of ApoE4-Carrying H4 Neuroglioma Cells in Alzheimer's Disease Using OrbiSIMS and LC-MS/MS.

Growing clinical evidence reveals that systematic molecular alterations in the brain occur 20 years before the onset of AD pathological features. Apolipoprotein E4 (ApoE4) is one of the most significant genetic risk factors for Alzheimer's disease (AD), which is not only associated with the AD pathological features such as amyloid-β deposition, phosphorylation of tau proteins, and neuroinflammation but is also involved in metabolism, neuron growth, and synaptic plasticity. Multiomics, such as metabolomics and proteomics, are applied widely in identifying key disease-related molecular alterations and disease-progression-related changes. Despite recent advances in the development of analytical technologies, screening the entire profile of metabolites remains challenging due to the numerous classes of compounds with diverse chemical properties that require different extraction processes for mass spectrometry. In this study, we utilized Orbitrap Secondary Ion Mass Spectrometry (OrbiSIMS) as a chemical filtering screening tool to examine molecular alterations in ApoE4-carried neuroglioma cells compared to wild-type H4 cells. The findings were compared using liquid chromatography (LC)-MS/MS targeted metabolomics analysis for the confirmation of specific metabolite classes. Detected alterations in peptide fragments by OrbiSIMS provided preliminary indications of protein changes. These were extensively analyzed through proteomics to explore ApoE4's impact on proteins. Our metabolomics approach, combining OrbiSIMS and LC-MS/MS, revealed disruptions in lipid metabolism, including glycerophospholipids and sphingolipids, as well as amino acid metabolism, encompassing alanine, aspartate, and glutamate metabolism; aminoacyl-tRNA biosynthesis; glutamine metabolism; and taurine and hypotaurine metabolism. Further LC-MS/MS proteomics studies confirmed the dysfunction in amino acid and tRNA aminoacylation metabolic processes, and highlighted RNA splicing alterations influenced by ApoE4.

Influence of pH on passivation of mild steel in simulated concrete pore solution: Electrochemical, ToF-SIMS and ReaxFF study

The passivation evolution of mild steels in simulated concrete pore solutions with varying pH were systematically investigated in present study. Based on electrochemical, time-of-flight secondary ion mass spectrometry, and ReaxFF molecular dynamics simulation, a plausible model with high logical coherence and theoretical soundness was proposed to elucidate the underlying passivation mechanism. The results depict that the steels within concrete pore solution with high pH facilitates quick and compact film formation, leading to superior passivation performance. Spontaneously-induced passive film of mild steel demonstrates a dual-layer structure composed of an inner layer rich in Fe(II) and an outer layer rich in Fe(III).

Tof-SIMS spectra of historical inorganic pigments: Copper-, zinc-, arsenic-, and phosphorus-containing pigments in negative polarity

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 eight pigments containing copper, zinc, arsenic, or phosphate, all manufactured following historical recipes. The negative polarity ToF-SIMS reference spectra using a Bi3+ primary ion species are presented here. Presented together, these spectra and corresponding tables of secondary ions provide a valuable help in differentiating these pigments because copper, zinc, arsenic, or phosphate, combined with oxygen, share many mass interferences.

Effect of chemical abrasion of zircon on SIMS U–Pb, δ18O, trace element, and LA-ICPMS trace element and Lu–Hf isotopic analyses

Abstract. 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, δ18O, and εHf 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.

Internal Standard Addition System for Online Breath Analysis.

Breath analysis with secondary electrospray ionization (SESI) coupled to mass spectrometry (MS) is a sensitive method for breath metabolomics. To enable quantitative assessments using SESI-MS, a system was developed to introduce controlled amounts of gases into breath samples and carry out standard addition experiments. The system combines gas standard generation through controlled evaporation, humidification, breath dilution, and standard injection with the help of mass-flow controllers. The system can also dilute breath, which affects the signal of the detected components. This response can be used to filter out contaminating compounds in an untargeted metabolomics workflow. The system's quantitative capabilities have been shown through standard addition of pyridine and butyric acid into breath in real time. This system can improve the quality and robustness of breath data.

Depth profile study of LaAl1‐xCrxO3/SrTiO3 (x = 0, 0.2, 0.6, and 1) using time of flight secondary ion mass spectrometry (TOF‐SIMS)

The conducting two‐dimensional electron gas (2DEG) behavior in LaAlO3 (LAO)/SrTiO3 (STO) and their associated mechanisms from various aspects have brought tremendous attention in the concerned area of research. To correlate the 2DEG behavior with their compositions, we have performed time of flight secondary ion mass spectrometry (TOF‐SIMS) depth profile analysis of thin films of Cr‐doped LAO/STO system as LaAl1‐xCrxO3 (x = 0, 0.2, 0.6 and 1) deposited over TiO2 terminated STO substrate, which includes two parent compounds LAO/STO (metallic) and LCO/STO (insulating). The uniform decrease of La and Al concentration at the interface of LAO/STO (metallic) system and in the contrary the nonuniformity of La and Cr concentration in LCO/STO (insulating) system have been highlighted. The uniform variation of ionic concentration at the interface of LAO/STO may increase the career concentrations to make the system metallic. The upward and downward diffusion at the interfaces of intermediate compositions varies differently from their parent ones due to the mixing of Al and Cr. Our results may help to understand the conducting nature of LAO/STO system for future developments and applications in such system.

Surface segregation phenomena encountered during solid carbon active screen plasma nitrocarburizing of AISI 316L

Plasma nitrocarburizing of an austenitic stainless steel AISI 316L was performed in an N2-H2 atmosphere (50 % H2 and 50 % N2) with a carbon-fiber reinforced carbon (CFC) active screen. The experimental concept of a plasma-discharged CFC active screen in conjunction with a substrate holder at floating potential ensures that no charged particles are present on the sample surface and no sputtering occurs. As a result, carbon contaminations are formed on the surface which were studied in detail with a combination of scanning electron microscopy (SEM) and secondary ion mass spectrometry (SIMS). The results indicate that a layer of about 25–50 nm of carbon is formed. At the same time, a strong segregation of Mn, Ni and Cr is observed below the coating within the steel substrate. Both effects progress with treatment time and there exists a clear correlation between the formation of the carbon layer and the segregation effect.

Unlocking the Potential of Liquid Plasma Polymer Films: Characterizing Aging Effects and Their Impact on the Wrinkling Phenomenon.

Here, we present the study of the intricate dynamics between the physicochemical properties of liquid propanethiol plasma polymer films (PPFs) and the formation of wrinkles in PPF/Al bilayers. The study investigates the effect of liquid PPF aging in the air before top Al layer deposition by magnetron sputtering on the wrinkling phenomenon for 4 days. Thanks to atomic force microscopy, the wrinkle dimensions were found to decrease by approximately 55% in amplitude and 66% in wavelength, correlated with an increase in the viscosity of the PPF over the aging duration (i.e., from less than 107 to 1010 Pa·s). This behavior is not linked to alterations in cross-linking degree as evidenced by time-of-flight secondary ion mass spectrometry experiments but rather to network densification driven by the inherent molecular chain mobility due to the viscous state of the PPF. X-ray photoelectron spectroscopy measurements emphasizing the absence of oxidation of the PPF over the aging duration support this, revealing a unique aging mechanism distinct from other plasma polymer families. Overall, this study offers valuable insights into the design and application of mechanically responsive PPFs involved in bilayer systems, paving the way for advancements in nanotechnology and related fields.

Unveiling niobium pentoxide and cerium oxide-dispersed ferritic stainless steel for solid oxide fuel cells interconnects

Herein, the effect of niobium pentoxide (Nb2O5) and nano-sized cerium oxide (CeO2) on oxidation behavior and area specific resistance (ASR) of the ferritic stainless steel has been investigated for the development of robust metallic interconnects. An oxide-dispersed ferritic stainless steel alloy is fabricated using the powder metallurgy (PM) process. The morphologies of the alloy before and after oxidation are observed through Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscopy (STEM) and Secondary Ion Mass Spectrometry (SIMS) analyses. Addition of Nb2O5 in the alloy formed a C14 Laves phase of (Fe, Cr)2(Nb, Si). The Laves phase and CeO2 controlled the oxidation behavior of the ferritic stainless steels, consequently reducing the oxide scale thickness and improving the ASR. An alloy with 1 wt% Nb2O5 and 3 wt% CeO2 showed an ASR value of 27.1 mΩ cm2 at 800 °C for 1000 h, which is similar to the ASR value of the commercial Fe–Cr alloy. The results of this study indicate that Nb2O5 and CeO2-dispersed ferritic stainless steel using the PM process can be more advantageous than the conventional process for manufacturing metallic interconnects with complex shapes and reducing production costs.

Spatially Resolved Functional Group Analysis of OLED Materials Using EELS and ToF-SIMS.

Electron energy-loss spectroscopy (EELS) is widely used in analyzing the electronic structure of inorganic materials at high spatial resolution. In this study, we use a monochromator to improve the energy resolution, allowing us to analyze the electronic structure of organic light-emitting diode (OLED) materials with greater precision. This study demonstrates the use of the energy-loss near-edge structure to map the nitrogen content of organic molecules and identify the distinct bonding characteristics of aromatic carbon and pyridinic nitrogen. Furthermore, we integrate EELS with time-of-flight secondary ion mass spectrometry for molecular mapping of three different bilayers composed of OLED materials. This approach allows us to successfully map functional groups in the by-layer OLED and measure the thickness of two OLED layers. This study introduces spatially resolved functional group analysis using electron beam spectroscopy and contributes to the development of methods for complete nanoscale analysis of organic multilayer architectures.

Towards a scalable production of β-Li3PS4-based all-solid-state batteries: Optimizing pressing parameters of the tape-casted solid electrolyte and composite cathode films

Pressing of all-solid-state batteries (ASSBs) components is one of the most important processes for scalable production. Henceforth, pressing parameters (pressure and temperature) for β-Li3PS4 (β-LPS) solid electrolyte (SE) separator films and LiNi0.6Co0.2Mn0.2 (NCM622)/β-LPS composite cathode films prepared by a slurry-based process were investigated and optimized. Compression of the β-LPS film at a temperature of 100 °C led to higher ionic conductivity than cold-pressed films. Raman and X-ray photoelectron spectroscopic analyses revealed no changes in the chemical nature of β-LPS material after hot pressing. Interestingly, time-of-flight secondary ion mass spectrometric (ToF-SIMS) analyses indicated a binder enrichment in the upper layers of the hot-pressed film. In a similar trend, increasing compression and temperature resulted in higher densification of NCM622/β-LPS composite cathode films. Based on galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) measurements, hot-pressed composite cathode at 200 MPa/100 °C exhibited a higher coverage percent of catholyte on cathode active material and a greater Li+ diffusion coefficient (DLi+) than cold-pressed one at 200 MPa/20 °C. Cycling tests of “Li–In│β-LPS│NCM/β-LPS” ASSBs with hot-pressed films displayed better cycling performance than that with cold-pressed ones, attributed to the higher concentration of electrochemically active NCM in close contact with β-LPS catholyte.

Cationization agent affects the stability of secondary ions in MeV-SIMS

The work presents studies of the cationization agent effect on the ionization efficiency, and on the stability of secondary molecules, which are desorbed from the surface as a result of bombardment by MeV primary ions. Different organic molecule standards were mixed with various trifluoroacetate (TFA) salts, namely AgTFA, LiTFA, NaTFA and KTFA, with Ag, Li, Na and K being common cationization agents of secondary ions besides hydrogen. Results show modest differences in ionization efficiency, and significant variation of secondary ions’ stability when different cationization agents are attached to the molecule. For all reference samples, lithium provided the most stable secondary ions with almost none detected fragmentations after the desorption, while secondary ions with attached potassium were measured as much less stable, and the ratio between neutrals (fragments) and normal positive ions is estimated to be more than 0.2. However, even potassium – ionized molecules were recognized as more stable than protonated molecules.

High-pressure mafic granulite and supracrustal rocks in the southern Hengshan area, North China Craton: Metamorphic P-T-t evolution and geotectonic significance

Amphibolite- to granulite-facies rocks are widely distributed in the Hengshan Complex, middle Trans-North China Orogen, and the high-pressure (HP) mafic granulite has been recently identified in the southern Hengshan area. The HP mafic granulite and amphibolite occur as rootless tectonic boudins/lenses within the TTG (tonalite–trondhjemite–granodiorite) gneiss/metapelite, indicative of typical “block-in-matrix” texture of metamorphic-tectonic mélange. Three to four generations of metamorphic mineral assemblages that correspond to the prograde (M1), peak (M2), and retrograde (M3-M4) stages, are recognized in these rocks. Conventional geothermobarometry and phase equilibrium modeling yield peak P–T conditions of 10.8–13.8 kbar/754–799 °C for the HP mafic granulite and 7.3–9.0 kbar/690–725 °C for the supracrustal rocks, respectively. A clockwise P–T path with near-isothermal decompression (ITD) and subsequent near-isobaric cooling (IBC) segments is reconstructed for the HP mafic granulite, indicating a dynamic subduction–collision–exhumation process that unfolded during an orogenic event. Secondary ion mass spectrometry (SIMS) U-Pb dating of zircon yields metamorphic ages of ca. 1.91–1.83 Ga, representing the long-lived tectono-metamorphic event caused by collision between the Eastern and Western Blocks along the Trans-North China Orogen. It is hypothesized that the tectono-metamorphic mélange in the area originated from the tectonically juxtaposition of metamorphic rocks that had diverse protoliths, different peak P–T conditions and discrepant metamorphic ages. This complexity may be a hallmark of Paleoproterozoic orogens, drawing intriguing parallels with the intricate characteristics observed in Phanerozoic orogenic belts.

Performance improvement of 1.3 μm InAlGaAs MQW modulators grown by MOVPE using C-doped InAl(Ga)As cladding layers

We propose a novel epitaxial layer structure to prevent Zn from diffusing into a multiple quantum well (MQW) layer of an electro-absorption modulator (EAM). Zn is practically employed as a p-type dopant in an InP material system, but there is a technical issue of unintentional Zn diffusion. In this work, we introduce a novel C-doped p-type layer between a Zn-doped p-cladding layer of InP and MQW to both reduce Zn diffusion and accurately define a p-i-n junction interface. The Zn concentrations in the MQW for each device are compared by measuring secondary ion mass spectrometry (SIMS). To clarify how the reduction of diffused Zn affects the EAM characteristics, we fabricate the EAMs with each epitaxial structure and compare their extinction ratio characteristics. The evaluation of extinction ratio per EAM capacitance successfully demonstrates that employing the C-doped layer effectively improves the EAM characteristics.