Electrosprayed droplet impact/secondary ion mass spectrometry

A new ionization method, electrosprayed droplet impact ionization (EDI), has been developed for mass spectrometry. The charged droplets formed by electrospraying 1 M acetic acid aqueous solution are sampled through an orifice with a diameter of 400 μm into the first vacuum chamber, transported into a quadrupole ion guide and accelerated by 10 kV after exiting the ion guide. The m/z of the primary droplet projectiles range from 10 000 to 50 000. The droplets impact on a dry solid sample deposited on a stainless steel substrate. No matrix was used for the sample preparation. The secondary ions formed by the impact are transported to a second quadrupole ion guide and mass-analyzed by an orthogonal TOF-MS. Intense molecular-related ions are detected for drugs, amino acids, peptides and proteins. EDI is found to be very sensitive to molecules present near the surface of the sample.     

Gold nanoparticle-enhanced secondary ion mass spectrometry and its bio-applications

Enhancement of signals in time-of-flight secondary ion mass spectrometry (ToF-SIMS) studies is necessary to many biological applications. We have developed an efficient method of enhancing the signals of secondary ions from peptides using gold nanoparticles (AuNPs) attached to a well-controlled surface such as self-assembled monolayers (SAMs). AuNPs function as both signal enhancers and effective binding sites for peptides, which allow the high signal intensity from the peptides to produce well-contrasted ToF-SIMS images of peptides that are micropatterned on the surface of the AuNPs. For application, this AuNP-enhanced SIMS (NE-SIMS) provided the basis for the spectrum and images to assay protein kinases and their inhibitors. Phosphorylation efficiency and inhibitor effect were quantified by detecting mass change of the peptide substrates by kinase reaction. Maximum efficiency of phosphorylation was achieved from cysteine-tethered peptides with a spacer linker, indicating that accessibility of kinase was dependent on the surface orientation and length of the peptide substrate on the three-dimensional AuNPs. The activities of other enzymes such as phosphatase and protease could also be assayed using NE-SIMS. Our study shows that NE-SIMS can be applied as a useful tool for enzyme assay in biochip surfaces.     

Adsorption of gases studied by secondary ion emission mass spectrometry

The adsorption of an active gas, like oxygen, on the surface of a metal or an alloy leads to an intensification of the positive ion emission produced by sputtering. In the present paper this phenomenon (called chemical ion emission) is observed by blowing the gas on the surface of the sample while it is sputtered. The general features of the chemical effect on M⁺ ion production are discussed in terms of coverage resulting from equilibrium between the rate of atoms sticking to the surface and the sputtering rate of adsorbed atoms, and in terms of ionization probability depending upon the coverage. Examples are given for pure metals (Al, W, Ni) and alloys (NiCr, CuBe, CuAl, …). Attention is drawn to the effects observed on nickel single crystals (100) and (110). At a critical coverage an incorporation process takes place, producing both changes in the work function and in the ionization probability. These results, largely consistent with those obtained by classical methods, show that secondary ion emission can be used for adsorption studies. Finally, investigations of metal-oxygen interaction by the dynamic method (present work) and the static method of secondary ion mass analysis will be discussed and compared.     

Depth-profiling of Cu-Ni sandwich samples by secondary ion mass spectrometry

SIMS depth profiles of copper-nickel thin film targets were measured with argon and nitrogen primary ions. While pronounced cone formation is observed in case of argon irradiation the erosion is much more uniform with nitrogen projectiles, probably due to formation of nitride surface layers.     

The use of secondary ion mass spectrometry in surface analysis

Secondary ion mass spectrometry (SIMS) is based on the bombardment of solids by ions and subsequent mass analysis of the sputtered ions or of the post-ionized neutrals. Various models have been proposed for the emission of secondary ions from the target. These models can roughly be grouped into two categories: (a) lonization takes place outside the target; the sputtered particles are assumed to leave the target in an excited or super-excited state; ionization can then result from such processes as Auger de-excitation or resonance ionization. (b) Ions are generated inside the target by collision cascades initiated by a primary impinging ion. Experimental data of the element- and matrix-dependent ion yield and estimates of the minimum detectable concentrations are shown as well as the rate of consumption of the target. Methods for efficient use of the sputtered material will be discussed. Examples of the wide range of applications of SIMS for determination of the chemical composition and structure of the surface layer and for imaging of the distribution of elements in the surface are given. The SIMS results are compared with those of Auger and Ion Scattering Spectrometry. The essentially non-destructive method of static SIMS is shown to be a powerful tool for the investigation of the outermost atomic layers of a solid.     

Matrix-enhanced secondary ion mass spectrometry: The Alchemist's solution?

Because of the requirements of large molecule characterization and high-lateral resolution SIMS imaging, the possibility of improving molecular ion yields by the use of specific sample preparation procedures has recently generated a renewed interest in the static SIMS community. In comparison with polyatomic projectiles, however, signal enhancement by a matrix might appear to some as the alchemist's versus the scientist's solution to the current problems of organic SIMS. In this contribution, I would like to discuss critically the pros and cons of matrix-enhanced SIMS procedures, in the new framework that includes polyatomic ion bombardment. This discussion is based on a short review of the experimental and theoretical developments achieved in the last decade with respect to the three following approaches: (i) blending the analyte with a low-molecular weight organic matrix (MALDI-type preparation procedure); (ii) mixing alkali/noble metal salts with the analyte; (iii) evaporating a noble metal layer on the analyte sample surface (organic molecules, polymers).     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Imaging of aerosols using time of flight secondary ion mass spectrometry

Interest in environmental aerosol chemistry has grown over the last decade as a result of its role in both climate change and troposheric pollution. In this work, the combination of ToF-SIMS and SEM/EDX was employed to explore the surface chemistry of aerosols. The capabilities and limitations of ToF-SIMS were investigated using particles of known composition and size produced by a vibrating orifice aerosol generator (VOAG). Principal component analysis (PCA) proved to help in the distinction of particles of different types by consolidating the information generated by ToF-SIMS.     

On the abundance of molecular ions in secondary ion mass spectrometry

Changes in molecular secondary ion intensities brought about by working in an environment of oxygen can be rationalised in simple statistical terms.     

In-depth concentration profiling of garnet epilayers using secondary ion mass spectrometry

Rapid and reliable SIMS profiling of insulators can be achieved by using negative primary ions and a diaphragm placed on the specimen for charge compensation. Results with garnet LPE layers demonstrate the compositional variations arising from non-steady state growth conditions.     

Analysis of solids by secondary ion and sputtered neutral mass spectrometry

A mass spectrometer is described, which allows the analysis of sputtered neutral and charged particles as well as of residual gas composition. This combined SIMS, SNMS, and RGA instrument consists of a scanning primary ion beam column, an electron impact ionizer, an electrostatic energy filter and an rf quadrupole mass analyzer.Various examples of surface and bulk analysis are presented which demonstrate the beneficial complementary features of these techniques. These are, in particular: a substantial reduction of the matrix effect and fewer complications with samples of low electrical conductivity in SNMS, and the possibility of measuring the depth distribution of gases included in small cavities in the solid in the SNMS/RGA mode. SIMS, on the other hand, allows in many cases higher detection sensitivities.EURATOM Association     

On the bond breaking model of polyatomic ion emission in secondary ion mass spectrometry

The cluster size distribution (number of clusters versus number of atoms in the cluster) resulting from a simple nearest neighbor Bond Breaking Model (BBM) of Secondary Ion Mass Spectroscopy (SIMS) is studied for one- and two-dimensional and Bethe lattices. In one dimension, the distribution is monotonic. In two dimensions, however, irregularities can occur as a function of the probability β of breaking any given bond. These irregularities differentiate between square, honeycomb, and triangular lattices and are most pronounced if the overall probability of breaking any bond in the lattice is small.     

Depth profiling using secondary ion mass spectrometry and sample current measurements

The features of the method for measuring the total current in the sample circuit in combination with secondary ion mass spectrometry (SIMS) depth profiling of various thin-film structures are discussed in detail. The results on depth profiling of multilayer CrN/AlN coatings magnetron-deposited on the surface of a nickel alloy, titanium dioxide films on stainless steel, and corrosion layers formed on the magnesium alloy surface during the interaction with an ionic liquid are considered. These results give grounds to consider the proposed method for measuring the sample current as an efficient and informative addition to the conventional SIMS.     

Molecular ion yield enhancement induced by gold deposition in static secondary ion mass spectrometry

Static ToF-SIMS was used to evaluate the effect of gold condensation as a sample treatment prior to analysis. The experiments were carried out with a model molecular layer (Triacontane M = 422.4 Da), upon atomic (In⁺) and polyatomic (Bi₃⁺) projectile bombardment. The results indicate that the effect of molecular ion yield improvement using gold metallization exists only under atomic projectile impact. While the quasi-molecular ion (M+Au)⁺ signal can become two orders of magnitude larger than that of the deprotonated molecular ion from the pristine sample under In⁺ bombardment, it barely reaches the initial intensity of (M−H)⁺ when Bi₃⁺ projectiles are used. The differences observed for mono- and polyatomic primary ion bombardment might be explained by differences in near-surface energy deposition, which influences the sputtering and ionization processes.     

Mechanism of MCs+ formation in Cs based secondary ion mass spectrometry

Quantitative analysis using MCs⁺ secondary ions has long been impossible because sample loading with Cs could not be controlled adequately. Using recently developed, advanced instrumentation, it can be shown that, at low levels of Cs loading, ionization and formation probabilities of MCs⁺ ions arrive at a constant, maximum level. On the basis of results obtained in three independent studies, involving three vastly different methods of controlling the sample loading with Cs, evidence is provided that MCs⁺ ions are emitted as such, independent of the number of atoms sputtered in the same impact event. Taken together, these findings finally pave the way for quantification of secondary ion signals without matrix effects.     

Three dimensional imaging using secondary ion mass spectrometry and atomic force microscopy

With the breakthroughs in lateral resolution with regards to secondary ion mass spectroscopy in recent years, new areas of research with much promise have opened up to the scientific community. Even though the much improved lateral resolution of 50 nm can effectively deliver more accurate 3D-images, the traditional 3D reconstructions, consisting of compiling previously acquired successive secondary ion mass spectrometry images into a 3D-stack, do not represent the real localized chemical distribution of the sputtered volume. Based on samples initially analyzed on the Cameca NanoSIMS 50 instrument, this paper portrays the advantages of combining the topographical information from atomic force microscopy and the chemical information from secondary ion mass spectrometry. Taking account of the roughness evolution within the analyzed zone, 3D reconstructions become a lot more accurate and allow an easier interpretation of results. On the basis of an Al/Cu sample, a comparison between traditional 3D imaging and corrected 3D reconstructions is given and the advantages of the newly developed 3D imaging method are explained.     

Diffusion of iron in lithium niobate: a secondary ion mass spectrometry study

Iron-doped X-cut lithium niobate crystals were prepared by means of thermal diffusion from thin film varying in a systematic way the process parameters such as temperature and diffusion duration. Secondary Ion Mass Spectrometry was exploited to characterize the iron in-depth profiles. The evolution of the composition of the Fe thin film in the range between 600°C and 800°C was studied, and the diffusion coefficient at different temperatures in the range between 900°C and 1050°C and the activation energy of the diffusion process were estimated.     

Oxygen distribution in nickel silicide films analyzed by time-of-flight secondary ion mass spectrometry

The oxygen distribution in Ni₂Si and NiSi films formed during a two-step silicidation process was analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS). TOF-SIMS mass spectra revealed that both silicon and nickel reacted with oxygen at the Ni₂Si surface. In addition, silicon nitride was formed at the surface by the reaction of silicon with nitrogen in the TiN capping layer during the first silicidation annealing. The amount of nitrogen at the NiSi surface varied with silicidation annealing temperature and with the formation conditions of the TiN capping layer. We also showed that a small amount of oxygen was penetrated into the NiSi film and strongly affected the level of junction leakage current in n⁺–p junctions in n-channel MOSFETs. The oxygen concentration in the NiSi film decreased with an increase in the amount of nitrogen at the NiSi surface.     

Sputter depth profiling by secondary ion mass spectrometry coupled with sample current measurements

Ion-induced secondary electron emission determined via sample current measurements (SCM) was employed as a useful adjunct to conventional secondary ion mass spectrometry (SIMS). This paper reports on the results of 3-6 keV O₂⁺ SIMS-SCM sputter depth profiling through CrN/AlN multilayer coatings on nickel alloy, titanium dioxide films deposited on stainless steel, and corrosion layers formed onto surface of magnesium alloy after long-term interaction with an ionic liquid. For Au/AlNO/Ta films on silicon, in addition to SIMS-SCM profiles, the signal of mass-energy separated backscattered Ne⁺ ions was monitored as a function of the depth sputtered as well. The results presented here indicate that secondary electron yields are less affected by “matrix effect” than secondary ion yields, and at the same time, more sensitive to work function variations and surface charging effects. SCM depth profiling, with suppression of “the crater effect” by electronic gating of the registration system is capable of monitoring interfaces in the multilayer structure, particularly, metal-dielectric boundaries. In contrast to SIMS, SCM data are not influenced by the angle and energy windows of an analyser. However, the sample current measurements provide lower dynamic range of the signal registration than SIMS, and SCM is applicable only to the structures with different secondary electron emission properties and/or different conductivity of the layers. To increase the efficiency, SCM should be accompanied by SIMS measurements or predetermined by proper calibration using other elemental-sensitive techniques.