Secondary Ion Intensities Research Articles

Accurate determination of matrix composition in Cd x Zn 1 − x O semiconductor material using MS-SIMS and ToF-SIMS methods

Abstract This study focuses on the method for determining the exact composition for Cd x Zn 1 − x O semiconducting material using secondary ion mass spectrometry. The calibration curve method is employed to establish a quantitative relationship between the intensity of secondary ions and the concentrations of elements in Cd x Zn 1 − x O thin films. Additionally, the study compares the relative sensitivity factors with the calibration curve method for determining the value of x in Cd x Zn 1 − x O . A comparison between the performances of Time of Flight and Magnetic Sector SIMS in analyzing Cd x Zn 1 − x O thin films is also presented. This approach aims to enhance the accuracy and reliability of quantitative analysis in SIMS for Cd x Zn 1 − x O thin films.

Effects of Hydrogen Dissociation During Gas Flooding on Formation of Metal Hydride Cluster Ions in Secondary Ion Mass Spectrometry.

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.

Alkali-metal-based molecular-ion secondary ion mass spectrometry for precise quantitative analysis of low-dimensional materials without standards

Advancement in the understanding of fundamental aspects of Secondary Ion Mass Spectrometry (SIMS) has made this technique to be extremely powerful for quantitative materials analysis. The secondary ion emission process is a complex phenomenon involving various mechanisms to understand the mechanism. Among the existing mechanisms, the “electron-tunneling model” is the most accepted concept in the understanding of ionization probability for positive and negative ions. This model essentially concerns the survival probability of an ion emitted from the surface. As the intensity of secondary ions of a certain element depends strongly on the efficiency of ionization of a sputtered atom or molecule, the “local surface chemistry” plays a significant role in the secondary ion emission. This is purported as the “Matrix Effect” in SIMS, making the technique extremely challenging for quantification of materials in spite of the fact that it has the highest detection sensitivity (<ppb) and exceptional depth-resolution (<1[Formula: see text]nm). Therefore, it is required to correct the “matrix effect” for quantitative analysis. If the probing element (M) in its close proximity sees an alkali element (such as Li, Rb, K, Na and Cs, referred to as “A”) on the sample surface, the sputtered neutral atom (M0) of the probing element can attach an alkali-ion forming a quasi-molecular (MA)[Formula: see text] ion. Such a phenomenon can also occur if an alkali ion beam is chosen as the primary beam for sputtering. The MA[Formula: see text] molecular ion formation is directly related to the atomic polarizability of the element M. Since the sputtering of neutral atom (M0) is unconnected with the formation of MA[Formula: see text] ion, the “matrix effect” decreases dramatically in the analysis using MA[Formula: see text] ions. The phenomenon is very similar to the mechanism of “secondary neutral mass spectrometry” (SNMS). Although these (MA)[Formula: see text] molecular ions are potentially applicable in the direct quantification of materials without the need for “calibration standards”, it generally has a weak intensity. In such a case, the (MA)[Formula: see text] molecular ions are preferred in the analysis because of their higher detection sensitivity (by a few orders of magnitude in some cases), compared to that of (MA)[Formula: see text] molecular ions. Monitoring of the molecular ions is routinely preferred in conventional SIMS experiments to discriminate the sputtered ion species which are affected by mass interference or have poor dynamic ranges. For example, while making the SIMS analysis of GaAs, carbon as an impurity element is detected by monitoring (AsC)[Formula: see text] molecular ions instead of C− ions, because the C− ions have high background arising from the carbon-containing residual-gas species in the analysis chamber. Caesium is decidedly chosen for MCs[Formula: see text] or MCs[Formula: see text] molecular ions in SIMS because of the strongest reactivity and electropositive nature of caesium. This paper deals with a comprehensive discussion on the ion-emission phenomena in sputtering, the “matrix effect” and its compensation, and the potential application of the “MCs[Formula: see text]-SIMS” ([Formula: see text]) in the effective quantitative chemical analysis of materials. A special prominence has been given to the quantification of low-dimensional materials, superlattices and quantum-confined structures using this state-of-the-art “MCs[Formula: see text]-SIMS” approach in all complexities.

Investigation of atomic-scale decorations on mixed conducting oxides via time-of-flight secondary ion mass spectrometry (ToF-SIMS)

Sub-nanometer modifications of mixed ionic electronic conducting (MIEC) materials, like the perovskite La0.6Sr0.4CoO3-δ (LSC), represent a promising approach to improving their oxygen exchange kinetics and degradation stability. The complex interactions between decoration layers and the host material are still not fully understood and are a subject of current research. Under these circumstances, a novel approach using time-of-flight secondary ion mass spectrometry (ToF-SIMS) was developed to gain deeper insight into the electronic and chemical interactions of LSC with different oxidic decorations. The investigated samples were prepared by pulsed laser deposition (PLD) on YSZ single crystals, starting with a 100 nm thin LSC layer, which was then modified by sub-nm decorations of CaO, TiO2, and SnO2 (nominally 0.05–0.5 nm) on top. By using ToF-SIMS with a sampling depth of 1–2 nm, it was possible to extract information simultaneously on the decoration layer and the host oxide. Significant differences in secondary ion (SI) intensities of the host material LSC were found that can be attributed to the formation of surface-near dipoles as a consequence of the acidic or basic nature of the decoration oxide. Further, relative stoichiometric variations of the La+, Sr+, and Co+ signals depending on the decoration oxide were observed, suggesting different preferential decoration sites on the LSC surface.

Stability of MeV primary ion induced secondary ions

We report on the analysis of the onset and the intensity of metastable secondary ions, which are desorbed from the target material as a result of bombarding organic samples with MeV primary ions. The bimodal time-of-flight mass spectrometer, which can analyze secondary ion in linear and reflectron modes, was used for detection and characterization of such ions. The use of the bimodal mass spectrometer for this specific purpose is demonstrated on amino acid arginine, where three main fragments were detected. We have also analyzed the influence of the primary ion beam on the intensity of metastable ion signal. Results from chlorine ion beams with energies between 3 and 10 MeV have exhibited the importance of electronic sputtering on the product/precursor ion peak intensity ratio, which is significantly decreased when using primary ions with higher energy.

Surface chemistry of atmospheric nanoparticles during a haze episode in Beijing by TOF-SIMS

The atmospheric aerosol particles have a potential heavy burden on environment, climate, and human health, which were closely related to the surface physicochemical properties. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) technique is a powerful tool to obtain detailed surface chemical information since it has high surface sensitivity for both elements and molecular ions, and high mass resolution. In this work, size-fractioned aerosol particles in the range of 0.43–10 µm during a severe haze episode in Beijing were analyzed by TOF-SIMS, the variation characteristics of chemical species corresponding to particle size and air pollution level was investigated by the normalization of secondary ion intensities, the possible sources were identified through principal component analysis (PCA), and the influence of meteorological factors and air mass transmission were also investigated. The study results showed that the surface chemical components of PM2.5 were more complicated during haze episode than on clean days. A total of 17 organic and inorganic species were detected, including crustal elements, heavy metals, sulfate, nitrate, siliceous compounds, hydrocarbons, oxygen-containing organics, and nitrogen-containing organics. In general, the particle surface mainly contained crustal elements, hydrocarbons, and carbon-containing inorganics. Organic and secondary ions significantly increased in heavy-polluted days, indicating the aging process of particles. Inorganic compounds had a higher percentage in coarse mode, while organic compounds were higher in accumulation mode. PCA results indicated that urban aerosol during this haze episode mainly came from vehicle emissions (24.7%), coal-fired combustion (22.4%), organic aerosol (19.3%), and dust resuspension (19.6%). The northern air mass could facilitate the dilution of air pollutants with the surface secondary formed components of particles significantly decreased.

OrbiSIMS metrology Part I: Optimisation of the target potential and collision cell pressure

In 2017, we introduced the OrbiSIMS instrument that features a dual analyser configuration with a time‐of‐flight (ToF) mass spectrometer (MS) and an Orbitrap MS, which confer advantages of speed and high‐performance mass spectrometry, respectively. The ability to combine the MS performance usually found in a state‐of‐the‐art proteomics and metabolomics MS with 3D imaging at the microscale and from nanolayers of <10 nm of material has proved popular in a broad field of application from organic electronics to drug discovery. There are now several instruments in operation around the world, and metrology is needed to help ensure repeatability and reproducibility of the intensity scale. We conduct a systematic study of two key parameters, the target potential, VT, and the collision cell pressure, P, in the transfer optics on the transmitted secondary ion intensities. We measure VT–P maps of the ions across the mass range for Ag as a representative of inorganic materials and two different organic materials, Irganox 1010 and NPB (N,N′‐Di[1‐naphthyl]‐N,N′‐diphenyl‐4,4′‐biphenyldiamine). The manufacturer's defaults for these values ensure very good transmission for a broad range of analyte classes. However, the maps reveal a sometimes complex behaviour and indicate the possibility for additional separation of ions based on their shape, labile nature and kinetics of formation. Guidance is provided on how to optimise these parameters for sensitivity for different material classes and also the need for optimisation to improve spectral repeatability and reproducibility.

New SIMS method to characterize hydrogen in polysilicon films

A new analysis protocol for profiling the hydrogen (H) concentration depth distributions in polysilicon (poly-Si) thin films on Si oxide was developed by using secondary ion mass spectrometry (SIMS). Traditional SIMS determination of H concentrations in poly-Si films is to monitor and collect the atomic H−, but this analysis method presents some challenges for providing stable and repeatable H depth profiles, especially, for shallow profiling in thinner poly-Si films on thicker Si oxide films. In this paper, we present a thorough study of the SIMS characterization of H levels in poly-Si thin films on Si oxide. We describe an approach for the use of cluster SiH− instead of atomic H− to determine the H concentrations. The utilization of the SiH− cluster ion minimizes both H adsorption effects on the film surface regions and sample surface charging effects arising from the Si oxide layer underneath, thus enhancing the secondary ion signal stability in poly-Si films, as discussed with secondary ion energy distribution on the samples. This method differs from the conventional SIMS analysis of H in thin films and significantly improves the data quality and accuracy. Fourier transform infrared spectroscopy analysis was used to study the Si–H chemical bonding information for investigating the nature of the SIMS collected SiH− cluster ions. Both the H implant sample with no significant Si–H bonding and the poly-Si samples with high levels of H and the weak Si–H bonding exhibited strong SiH− secondary cluster ion intensities in our studies. This indicates the cluster ion signals arise from either the combination of Si and H ions through the physics formation process or weak chemically bonded Si and H.

Interface and material properties of wide band gap a-SiCx:H thin films for solar cell applications

A thin intrinsic hydrogenated amorphous silicon carbide ((i) a-SiCx:H) layer with a wide band gap attracts attention as an alternative passivation layer instead of intrinsic hydrogenated amorphous silicon ((i) a-Si:H) for heterojunction photovoltaic applications. The optical band gap of (i) a-SiCx:H can be widened up to 2.24eV. An increase in the optical band gap makes this layer appropriate as the window material by reducing the parasitic absorption. However, the deposition regime should be investigated to understand the incorporation of carbon. The influence of several deposition parameters such as precursor gasses flow rates and plasma power density on the (i) a-SiCx:H layers were investigated in optical, electrical, and elemental aspects. Relatively high interface trap densities were detected related to carbon piling up at the interface. An increase in the amount of C in the interface affected the passivation quality and fixed charge density of the layer. The ratio of secondary ion intensities measured by time of flight-secondary ion mass spectroscopy presents general hydrogen filling of possible dangling bonds and the bonding preferentiality between the silicon or carbon atoms. The passivation quality of the (i) a-SiCx:H layer partially enhanced by stack layer deposition of (i) a-Si:H/(i) a-SiCx:H resulting effective lifetime above 100 μs.

A two‐point calibration method for quantifying organic binary mixtures using secondary ion mass spectrometry in the presence of matrix effects

Quantification of the composition of binary mixtures in secondary ion mass spectrometry (SIMS) is required in the analyses of technological materials from organic electronics to drug delivery systems. In some instances, it is found that there is a linear dependence between the composition, expressed as a ratio of component volumes, and the secondary ion intensities, expressed as a ratio of intensities of ions from each component. However, this ideal relationship fails in the presence of matrix effects and linearity is observed only over small compositional ranges, particularly in the dilute limits. In this paper, we assess an empirical method, which introduces a power law dependence between the intensity ratio and the volume fraction ratio. A previously published physical model of the organic matrix effect is employed to test the limits of the method and a mixed system of 3,3′‐bis(9‐carbazolyl) biphenyl and tris(2‐phenylpyridinato)iridium (III) is used to demonstrate the method. This paper introduces a two‐point calibration, which determines both the exponent in the power law and the sensitivity factor for the conversion of ion intensity ratio into volume fraction ratio. We demonstrate that this provides significantly improved accuracy, compared with a one‐point calibration, over a wide compositional range in SIMS quantification and with a weak dependence on matrix effects. Because the method enables the use of clearly identifiable secondary ions for quantitative purposes and mitigates commonly observed matrix effects in organic materials, the two‐point calibration method could be of significant benefit to SIMS analysts.

SIMS studies of hydrogen interaction with the TiFe alloy surface: hydrogen influence on secondary ion yields

Secondary ion mass spectrometry is a powerful analytical tool that offers great capabilities for studying hydrogen interaction with metallic materials. Yet its utilization for the in situ studies of hydrogen interaction with a sample has not been well established. In this research we study the influence of hydrogen partial pressure (5 × 10−9 – 5 × 10−5 Torr) in the sample chamber, the sample temperature (305–900K), and primary ion current density on the emission intensity of various secondary ions for the hydrogen-storage TiFe alloy sample bombarded with 12 or 20 keV Ar+ primary ions. Presence of chemisorbed hydrogen on the alloy surface results in the presence of a variety of positive and negative hydrogen-containing secondary ions in mass spectra. Analysis of the influence of the varied experimental parameters has shown that the secondary ion yield changes reflect only changes of hydrogen concentration regardless of which varied parameter induced a concentration change. The yield dependences on concentration in general are different for different ions and tend to be more substantial for the ions containing a larger number of hydrogen atoms. The ions containing one hydrogen atom have similar and likely linear yield dependences when the concentration is low. At higher concentrations, the yield dependences for these ions diverge: their relation to concentration is discussed. For not hydrogen-containing secondary ions, hydrogen saturation of the surface resulted in an 80-400% increase of the yields of Ti+ and Ti-containing positive secondary ions, no yield change for other positive ions, and 2–3-times decrease of yields of negative ions. As for hydrogen interaction processes with the alloy surface, the obtained dependence of the ion yields only on hydrogen concentration indicates that the alloy surface is rather homogeneous i.e. without large parts that have different characteristics of interaction with hydrogen and different ratios of secondary ion yields. The results of the sample temperature influence indicate that the chemisorption probability of hydrogen molecules is temperature independent at least in the ∼300-500 K range. The substantial decrease in concentration at temperatures above 450 K is a result of associative desorption of hydrogen, although a possible contribution of other processes is not excluded by the presented results.

Sputtering of Oxides from LaNi5 Surface

The changes in chemical composition of the intermetallic alloy LaNi5 surface monolayers were studied using secondary ion mass spectrometry (SIMS) in the process of the alloy interaction with oxygen. The investigated samples were pellets made by pressing the fine-grained LaNi5 alloy. Ar+ ions having energies of 10-18 keV were used as primary ions. The primary beam current density was 9-17 μA·cm-2, which corresponds to the dynamic SIMS mode. The emission intensities of secondary ions were measured within the dynamic range of at least 6 orders of magnitude. Before the measurements, the samples were annealed in residual vacuum at a temperature of ~ 1000 K. After the annealing, the sample surface was cleaned using the primary ion beam until the mass-spectrum composition and secondary ion emission intensity stabilized completely. The gas phase composition was monitored using a gas mass spectrometer. The conducted studies showed that a complex chemical structure including oxygen, lanthanum, and nickel is formed on the surface and in the near-surface region of LaNi5 as a result of its exposure to oxygen. Oxygen forms strong chemical bonds in such a structure with both components of the alloy. This is evidenced by the presence of a large set of oxygen containing emissions of positive and negative secondary ions with lanthanum, with nickel, and oxygen containing lanthanum-nickel cluster secondary ions in mass spectra. The resulting oxide compounds have a bulk structure and occupy dozens of monolayers. In such a bulk oxide structure, the outer monolayers are characterized by the highest ratio of oxygen atom number to the number of matrix atoms. This ratio decreases along the transition from the surface to the underlying monolayers. This process occurs uniformly, without any phase transformation. The observed secondary ions are not a product of association between sputtered surface fragments and oxygen in the gas phase at the fly-off stage after sputter-ejection, but they are products of the oxide compounds being sputtered, hence they characterize the composition of surface and near-surface region.

Examination of beauty ingredient distribution in the human skin by time-of-flight secondary ion mass spectrometry.

In this study, the authors evaluated the distribution of low-abundance beauty ingredients in human skin tissues. The distribution of collagen tripeptide, a beauty ingredient, in the human skin was evaluated by applying multivariate curve resolution (MCR) to the time-of-flight secondary ion mass spectrometry mapping data, including reference information. The intensity of the secondary ion peaks was increased by the accumulation of secondary ion intensity in the depth direction obtained by argon cluster sputtering. Consequently, the collagen tripeptide distribution in the skin was evaluated by separating it from collagen peptide, although the conventional analysis was difficult because of the dilution of the collagen tripeptide in the skin. Additionally, the distribution of the collagen tripeptide in the skin may be determined with an autoencoder. In this study, the distribution of small amounts of beauty ingredients (the collagen tripeptide) in the skin was observed by integrating the secondary ion intensity in the depth direction with Ar cluster sputtering and applying MCR or autoencoder.

Анализ углеродсодержащих материалов методом вторично-ионной масс-спектрометрии: содержание атомов углерода в sp-=SUP=-2-=/SUP=-- и sp-=SUP=-3-=/SUP=--гибридных состояниях

A new approach to the analysis of carbon-containing materials by the method of secondary ion mass spectrometry is studied, which allows one to determine the concentration of carbon atoms in the states of sp2 and sp3 hybridization. It is proposed to use the ratio of the intensities of cluster secondary ions C8/C7 as the main parameter of the mass spectra of secondary ions characterizing the concentration of N(sp3). From measurements of several test structures, a calibration dependence of N (sp3) on the C8/C7 ratio was obtained. The N(sp3) profiles of diamond-like carbon samples grown on diamond and silicon substrates were measured, showing an N(sp3) concentration of 0.3 to 0.6 for different growth modes and an inhomogeneous distribution of the N(sp3) concentration over the thickness of the samples.

A method for quantitative nanoscale imaging of dopant distributions using secondary ion mass spectrometry: an application example in silicon photovoltaics

A method for rapid quantitative imaging of dopant distribution using secondary ion mass spectrometry (SIMS) is described. The method is based on SIMS imaging of the cross-section of a reference sample with a known concentration profile. It is demonstrated for the case of boron quantification in silicon in a SIMS imaging mode. A nonlinear relationship between the secondary ion intensity and the concentration is observed. A detection limit of 3 (±2) × 1017 at./cm3 (~6 ppm) is determined with 39 nm pixel-size for the used experimental conditions. As an application example, a boron concentration profile in a passivating contact deposited on a textured Si surface is analyzed.

Optimization of the depth resolution for profiling SiO2/SiC interfaces by dual‐beam TOF‐SIMS combined with etching

To examine precise depth profiles at the interface of SiO2/SiC, a high resolution that can detect slight discrepancies in the distribution is needed. In this study, an experimental method to achieve a high resolution of less than 1 nm was developed by using dual‐beam time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS). The analysis was preceded by the following three steps: (1) determination of the optimal analytical conditions of the analysis beam (Bi+) and sputtering beam (Cs+), (2) verification of the etching methods to thin the SiO2 layer, and (3) confirmation of the benefits of the low‐energy sputtering beam directed toward SiO2/SiC samples. By using the secondary ion intensity peak‐to‐valley ratio of BN− and BO− of a sample with delta‐doped boron multilayers, the appropriate Bi+/Cs+ condition for a high depth resolution was determined for each energy level of the sputtering beam. Upon verification of the etching methods to thin the SiO2 layer, slight discrepancies were found between samples that were obtained with different etching methods. The difference in the roughness values of the etched surfaces was proactively utilized for the performance confirmation of the low‐energy sputtering beam by means of precise observation of the profiles at the SiO2/SiC interface. The use of a Cs beam with a low energy between 0.25 and 0.5 keV enabled the detection of slight discrepancies in the roughness of less than 1 nm between samples. The aforementioned method has the potential to accurately detect discrepancies in the intrinsic distribution at the SiO2/SiC interface among samples.

Effect of energy per atom (E/n) on the Ar gas cluster ion beam (Ar-GCIB) and O2+ cosputter process.

Gas cluster ion beam (GCIB) is a promising technique for preserving molecular structures during ion sputtering and successfully profiling biological and soft materials. However, although GCIB yields lower damage accumulation compared with C60+ and monoatomic ion beams, the inevitable alteration of the chemical structure can introduce artifacts into the resulting depth profile. To enhance the ionization yield and further mask damage, a low-energy O2+ (200-500 V) cosputter can be applied. While the energy per atom (E/n) of GCIB is known to be an important factor influencing the sputter process, the manner through which E/n affects the GCIB-O2+ cosputter process remains unclear. In this study, poly(ethylene terephthalate) (PET) was used as a model material to investigate the sputter process of 10-20 kV Ar1000-4000+ (E/n = 2.5-20 eV per atom) with and without O2+ cosputter at different energies and currents. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) with Bi32+ as the primary ion was used to examine surfaces sputtered at different fluences. The sputter craters were also measured by alpha-step and atomic force microscopy in quantitative imaging mode. The SIMS results showed that the steady-state cannot be obtained with E/n values of less than 5 eV per atom due to damage accumulation using single GCIB sputtering. With a moderate E/n value of 5-15 eV per atom, the steady-state can be obtained, but the ∼50% decay in intensity indicated that damage cannot be masked completely despite the higher sputter yield. Furthermore, the surface Young's modulus decreased with increasing E/n, suggesting that depolymerization occurred. At an E/n value of 20 eV per atom, a failed profile was obtained with rapidly decreased sputter rate and secondary ion intensity due to the ion-induced crosslink. With O2+ cosputtering and a moderate E/n value, the oxidized species generated by O2+ enhanced the ionization yield, which led to a higher ion intensity at steady-state in general. Because higher kinetic energy or current density of O2+ led to a larger interaction volume and more structural damage that suppressed molecular ion intensity, the enhancement from O2+ was most apparent with low-energy-high-current (200 V, 80 μA cm-2) or high-energy-low-current (500 V, 5 μA cm-2) O2+ cosputtering with 0.5 μA cm-2 GCIBs. In these cases, little or no intensity drop was observed at the steady-state.

Simultaneous In Situ Analysis of Carbon and Nitrogen Isotope Ratios in Organic Matter by Secondary Ion Mass Spectrometry

An in situ measurement method for simultaneous determination of carbon and nitrogen isotope ratios in organic matter was developed by secondary ion mass spectrometry with a spatial resolution of ~ 12 μm. Secondary ion intensities of 12C−2, 12C13C−, 12C14N− and 12C15N− were simultaneously measured by three Faraday cups and one electron multiplier. Ions of 12C2H− were measured to monitor hydride interferences and to correct for mass bias. The analytical precisions of δ13C and δ15N values of a reference material (UWLA‐1 anthracite) were 0.16‰ and 0.56‰, respectively (2s). A negative correlation was observed between the mass bias of carbon and 12C2H−/12C−2 ratios of examined reference materials. In contrast, there was no correlation between mass bias and hydrogen concentration for nitrogen. The δ13CVPDB and δ15NAir values of twenty‐two individual globules of organic matter, found in carbonate rock of the 1878 Ma Gunflint Formation, were determined by the new procedure, ranging from −33.8‰ to −33.3‰ and +4.2‰ to 5.8‰, respectively. Means of δ13CVPDB and δ15NAir values, −33.5 ± 0.25‰ and +5.2 ± 0.81‰, are consistent with reported values from bulk sample analysis within analytical precision.

Evaluation of matrix effects on TOF-SIMS data of leu-enkephalin and 1,2-dioleoyl-sn-glycero-3-phosphocholine mixed samples.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is one of the most powerful methods to analyze biomolecules in biological tissues and cells because it provides detailed chemical structure information and chemical images with a high spatial resolution. However, in terms of quantitative analysis, there are issues such as matrix effects that often cause secondary ion intensity changes regardless of the actual concentration in a sample. For instance, the intensity of secondary ions related to peptides is generally suppressed when lipids coexist. Since the evaluation of biomolecules is crucial to understand biological phenomena, it is required to analyze peptides or lipids without matrix effects. Therefore, the mechanism of matrix effects regarding peptides and lipids in TOF-SIMS was investigated in this study. Leu-enkephalin (YGGFL, molecular weight of 555.3 Da) and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC, C44H84NO8P, molecular weight 785.6 Da) were employed to prepare model samples. Model samples contain different weight ratios of these two molecules. The intensity of secondary ions related to the peptide or the lipid was compared with control samples containing pure leu-enkephalin or DOPC. As a result, it is indicated that the intensity of DOPC related secondary ions is strongly enhanced by coexisting leu-enkephalin, while the intensity of leu-enkephalin related secondary ions is suppressed by coexisting DOPC especially in a low concentration range of the peptide.

Integration of paper-based microarray and time-of-flight secondary ion mass spectrometry (ToF-SIMS) for parallel detection and quantification of molecules in multiple samples automatically

With its low-cost fabrication and ease of modification, paper-based analytical devices have developed rapidly in recent years. Microarrays allow automatic analysis of multiple samples or multiple reactions with minimal sample consumption. While cellulose paper is generally used, its high backgrounds in spectrometry outside of the visible range has limited its application to be mostly colorimetric analysis. In this work, glass-microfiber paper is used as the substrate for a microarray. The glass-microfiber is essentially chemically inert SiOx, and the lower background from this inorganic microfiber can avoid interference from organic analytes in various spectrometers. However, generally used wax printing fails to wet glass microfibers to form hydrophobic barriers. Therefore, to prepare the hydrophobic-hydrophilic pattern, the glass-microfiber paper was first modified with an octadecyltrichlorosilane (OTS) self-assembled monolayer (SAM) to make the paper hydrophobic. A hydrophilic microarray was then prepared using a CO2 laser scriber that selectively removed the OTS layer with a designed pattern. One microliter of aqueous drops of peptides at various concentrations were then dispensed inside the round patterns where OTS SAM was removed while the surrounding area with OTS layer served as a barrier to separate each drop. The resulting specimen of multiple spots was automatically analyzed with a time-of-flight secondary ion mass spectrometer (ToF-SIMS), and all of the secondary ions were collected. Among the various cluster ions that have developed over the past decade, pulsed C60+ was selected as the primary ion because of its high secondary ion intensity in the high mass region, its minimal alteration of the surface when operating within the static-limit and spatial resolution at the ∼μm level. In the resulting spectra, parent ions of various peptides (in the forms [M+H]+ and [M+Na]+) were readily identified for parallel detection of molecules in a mixture. By normalizing the ion intensity of peptides with respect to the glass-microfiber matrix ([SiOH]+), a linear calibration curve for each peptide was generated to quantify these components in a mixture.