Multivariate data analysis for depth resolved chemical classification and quantification of sulfur in SNMS

The quantification of elements in quadrupole based SNMS is hampered by superpositions of atomic and cluster signals. Moreover, the conventional SNMS data evaluation employs only atomic signals to determine elemental concentrations, which not allows any chemical specifications of the determined elements. Improvements in the elemental quantification and additional chemical information can be obtained from kinetic energy analysis and the inclusion of molecular signals into mass spectra evaluation. With the help of multivariate data analysis techniques, the combined information is used for the first time for a quantitative and chemically distinctive determination of sulfur. The kinetic energy analysis, used to solve the interference of sulfur with O₂ at masses 32-34 D, turned out to be highly important for the new type of evaluation.     

Characterisation of molybdenum intermediate layers in Cu-C system with SIMS method

In the design of new high-speed chip generations a huge problem is bleeding off process heat during their operation. The installation of heat sinks onto such chips is necessary. Possible materials are copper-coated carbon composites. They combine high thermal conductivity with low density and a tailorable coefficient of thermal expansion (CTE). The low wettability of copper onto carbon necessitates a surface pretreatment.Flat slices of nitrogen-plasma etched vitreous carbon (Sigradur G) made up as a model system for carbon fiber material. The later serial fabrication of these fibers includes a hot pressing step after the deposition joining them to solid composites. It is simulated by a heat treatment step of the compound. The first sample series consisted of samples with 100 nm molybdenum and 500 nm copper layers (sputter deposited), as deposited and heat treated. The second run concludes samples without molybdenum layer but an additional 50 nm cap layer deposited after heat treatment.All samples were investigated with secondary ion mass spectrometry (SIMS), showing a diffusion of carbon into the molybdenum layer. Measuring MCs⁺ secondary ions, both matrix elements and trace elements were detectable sufficiently.     

Laser vaporization of carbon in the presence of carbon dioxide

2 . The dependence of the ion production on the laser ablation parameters is investigated and the expansion dynamics of the ablated species is studied through time and space resolved measurements of the ion yield. We discuss our observations on the basis of reactions involving neutral and ionized carbon-based species. Received: 11 March 1997/Accepted: 30 June 1997     

Electronic structure and interactions in well-defined coadsorbate layers

A synopsis of results and models for weakly and strongly interacting, well-defined coadsorbate systems is presented. Some experimental examples are given for various adsorbates on Ni(111) representing weak (different N₂ states, Ar/Xe+N₂) as well as strong (N₂+K) interaction. Models for coadsorbate interaction, in particular between molecules (CO, N₂) and alkali atoms, are discussed.     

2D and 3D SIMS investigations on sintered steels

Powder metallurgy (PM) is a well-established method for manufacturing ferrous precision parts. Sintering is one of the important production steps and can be strongly enhanced (activated) by formation of a liquid phase during the sintering process. The liquid phase can be reached by the addition of alloying elements (e.g., copper) or sintering activators (e.g., phosphorus) and is formed by melting of eutectic phase mixtures or by incipient melting. The main investigations presented in this work are done by secondary ion mass spectrometry (SIMS): 2D and 3D elemental distribution. Additionally, impact energy and hardness measurements were performed in order to study the influence of phosphorus on mechanical properties. The concentration of P in different samples was varied between 0 and 1 weight percent (wt.%), the carbon content was consistently 0.5 wt.%. Nominal specimens were sintered at 1120 and 1250 °C in protective atmosphere of flowing nitrogen to determine the influence of sintering temperature.     

Enhancement of the reflectron TOF focusing energy range

The requirements for the geometrical dimensions and ion packet deflection angles to achieve a maximum resolution of the mass-reflection with a field-free gap introduced between its decelerating and reflecting gaps are considered. The results obtained demonstrate the capability of the device proposed to make TOF analysis of the ion packets with large ion energy spread. It is also shown that, if by some reasons, the energy range of the ions entering the routine reflection can be predetermined, the regime with slightly detuned deceleration voltage is preferable, as it provides better mass resolution.     

Investigations of corrosion phenomena on gold coins with SIMS

In order to establish a new handling procedure for contaminated coins, the Coin Cabinet and the Conservation Science Department of the Kunsthistorisches Museum, Vienna, initiated a research project on corrosion effects of gold coins. By now, investigations on historic and contemporary coins included optical microscopy, scanning electron microscopy (SEM), Auger electron microscopy (AES), X-ray photoelectron microscopy (XPS), and electrochemical methods showing the distribution of pollutants.This work focuses on secondary ion mass spectrometry (SIMS) investigations merely showing the distribution of electronegative elements, such as sulfur, oxygen, and chlorine on the surface. Sulfur is highly suspected of causing the observed corrosion phenomena, and is indeed enriched near polluting splints. Since SIMS is a destructive method, the investigated samples are test coins with intentionally added impurities. These coins were manufactured in cooperation with the Austrian Mint. They were treated with potassium polysulfide (K₂S_x) for 8 h gaining a rapid corrosion of the surface.SIMS mass spectra, depth profiles, and images were done (a) at non-polluted areas, (b) near polluted areas with slight coloring, and (c) directly at polluting stains showing enrichments of sulfur and chlorine. Due to the success of these investigations further studies on historic coins are intended.     

Line shape of mass peaks in a reflectron with plane metal grids

The line shape of the TOF peaks in the reflectrons of various relative deceleration gap widths was calculated under conditions where the main limiting factor of reflectron mass resolution is ion scattering by the reflectron grids. The analysis shows that the line shape of mass peaks in a reflectron with highly transparent grids is generally far from Gaussian. In the cases where the mesh size of one of the grids is by some reason a few times larger than that of the other grid, two satellites of minor amplitude were found to occur in the vicinity of the true mass peak.     

Mass-reflectron as an ion energy analyzer

The possibility of using the mass-reflectron as an analyzer for the kinetic energy of charged particles is demonstrated. The reflectron operating regime can be changed by varying the voltage across the reflecting system. The geometry of the system, in some cases, can remain the same. The time-of-flight focusing property of the analyzer is demonstrated for the case where ions of various initial energies simultaneously escape the same equipotential surface of the simple acceleration system.     

Cat's-eye reflectron

A new version of the non-magnet time-of-flight mass spectrometer reflectron is described. The method of operation, which allows to separate packets of ions with different masses both by their time-of-flight and by their deflection angle in the deflection system, the operation of which is synchronizes the arrival time of the ions with the focusing plane of this time-of-flight mass spectrometer is outlined.     

Positive secondary Ion emission from Si1−xGex bombarded by O2

The positive secondary ion yields of B⁺ (dopant), Si⁺ and Ge⁺ were measured for Si_1−xGe_x (0 ≤ x ≤ 1) sputtered by 5.5 keV ¹⁶O₂⁺ and ¹⁸O₂⁺. It is found that the useful yields of Ge⁺ and B⁺ suddenly drop by one order of magnitude by varying the elemental composition x from 0.9 to 1 (pure Ge). In order to clarify the role of oxygen located near surface regions, we determined the depth profiles of ¹⁸O by nuclear resonant reaction analysis (NRA: ¹⁸O(p,α)¹⁵N) and medium energy ion scattering (MEIS) spectrometry. Based on the useful yields of B⁺, Si⁺ and Ge⁺ dependent on x together with the elemental depth profiles determined by NRA and MEIS, we propose a probable surface structure formed by 5.5 keV O₂⁺ irradiation.     

Surface characterisation and interface studies of high-k materials by XPS and TOF-SIMS

High-k dielectric LaAlO₃ (LAO) films on Si(100) were studied by TOF-SIMS and XPS to look for diffusion processes during deposition and additional thermal treatment and for the formation and composition of possible interfacial layers. The measurements reveal the existence of SiO₂ at the LAO/Si interface. Thermal treatment strengthens this effect indicating a segregation of Si. However, thin LAO layers show no interfacial SiO₂ but the formation of a La-Al-Si-O compound. In addition, Pt diffusion from the top coating into the LAO layers occurs. Within the LAO layer C is the most abundant contamination (10²¹ at/cm³). Its relatively high concentration could influence electric characteristics. XPS shows that CO₃²⁻ is intrinsic to the LAO layer and is due to the adsorption of CO₂ of the residual gas in the deposition chamber.     

Spectroscopy in our age

The development of modern spectroscopy is summarized from Bunsen’s detection of atoms as the beginning of spectral analysis to modern molecular spectroscopies including new high resolution techniques for molecular ions. Recent experiments involving long range charge migration in peptides and proteins are outlined. Received: 2 October 2000 / Published online: 11 October 2000     

Analysis of ionic fragments from 308 nm photoablation of polyimide

The ionic products from excimer laser photoablation (=308 nm) of polyimide (Kapton) film have been studied as a function of fluence. Large ion masses up to about 900a.m.u. are easily observed, the mass distribution depending strongly on the fluence. Velocities of the emitted particles lie between 1400 and 10 000 ms^–1, again dependent on the fluence. A mechanism to explain the high velocities is suggested consisting of ionisation of the surface polymer molecules followed by a Coulomb explosion combined with expansion of the high density gas formed by the photoablation.     

High-temperature oxidation of CrN/AlN multilayer coatings

Experiments are reported on sputter depth profiling of CrN/AlN multilayer abrasive coatings by secondary ion mass spectrometry (SIMS) coupled with sample current measurements (SCM). The coatings were deposited by a closed-field unbalanced magnetron sputtering. It is shown that after oxidation tests, performed in air at 900 °C for 2 h and at 1100 °C for 4 h, the layered structure begins to degrade but is not destroyed completely. Oxidation at 1100 °C for 20 h causes total destruction of the coatings that can be attributed to a fast diffusion of oxygen, nickel, manganese and other elements along defect paths (grain boundaries, dislocations, etc.) in the coating. There are practically no nitrides in the near-surface layer after such a treatment and all the metallic components are in the oxidized form as follows from the data obtained by X-ray photoelectron spectroscopy (XPS). According to XPS and mass-resolved ion scattering spectrometry (MARISS), the surface content of Al in the heat-treated coatings has decreased in comparison with the as-received sample and that of Cr increased. Both XPS and MARISS data exhibit real increase in superficial concentration of the substrate materials (Mn and Ni) that is controversial if using SIMS alone. SCM turned out to be an informative depth profiling method complementary to more expensive and complicated SIMS, being particularly useful for structures with different secondary electron emission properties of the layers. SCM with predetermined SIMS calibration allows a routine characterization of coatings and other multilayer structures, particularly, in situations where the expenses of analysis can be justified.     

Quantitative XPS imaging—new possibilities with the delay-line detector

X-ray photoelectron spectroscopy (XPS, ESCA) is an ideal tool for identifying differences in surface chemistry. In the past, it has lacked the spatial resolution as well as the performance of elemental or even chemical state imaging, to be of significant use in detecting most microscopic surface phenomena. The recent development of improved micro- or small spot-XPS systems with near-micron spatial resolution as well as outstanding chemical state image performance has opened up a significant opportunity to undertake more detailed studies of micro-structured or micro-patterned surfaces or technical samples with locally distributed impurities. The introduction of a new detector type, the delay-line detector (DLD), to XPS-equipments allows for the first time the acquisition of quantifiable XPS images. This study is intended primarily to explore the capabilities of quantitative ESCA-imaging with respect to the possibilities and limits.     

High resolution quantitative SIMS analysis of shallow boron implants in silicon using a bevel and image approach

Secondary ion mass spectrometry (SIMS) is frequently used as the preferred tool for dopant profiling due to its sensitivity and depth resolution. However, as dopant profiles become shallower most, if not all of the implant profile lies in the pre-equilibrium or transient region of an SIMS depth profile. In this region sputter yield and ionisation rate vary making accurate quantification of the implant profile very difficult. These problems can be reduced through the use of much lower beam energies or oxygen flooding of the sample. However, most SIMS instruments do not have these capabilities. In this paper an alternative technique for producing an accurate depth profile of a shallow implant, using existing SIMS technology is presented.Through the fabrication of bevels with very small slope angles on a shallow boron implanted silicon via a chemical etch, SIMS ion imaging is performed on the exposed surface. Ion image data is then summed, and in conjunction with accurate measurement of the bevel morphology, a shallow boron implant profile produced. The ‘bevel-image’ profile compares very well with a profile obtained using a 1 keV oxygen beam. To ensure a good dynamic range on the ‘bevel-image’ profile it is important to clean the bevel with a HF etch, prior to imaging.     

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.     

Gas-phase aggregation of fullerenes by laser ablation of fullerenes in reactive and nonreactive matrices

60 molecules, whereas little or no coalescence was found in the nonreactive mixture. In the negative ion TOF channel the maximum peak of twice C₆₀ coalescence by laser desorption was always located at masses greater than 120 carbon mass units, which is different from all previous reports. We suggest that the formation mechanism was due to strong interactions between the C₆₀ molecules and silica particles or surface species such as the H or OH group existing in the matrix. Received: 6 May 1996/Revised version: 22 July 1996     

A combined SNMS and EFTEM/EELS study on focused ion beam prepared vanadium nitride thin films

We investigated the diffusion profiles and core-loss fine-structures (ELNES) of thin vanadium nitride films by electron energy-loss spectroscopy (EELS) and energy filtering transmission electron microscopy (EFTEM). The nitride layers have been produced by rapid thermal processing in a NH₃ or N₂ atmosphere and have then been cross-sectioned with a focused ion beam instrument (FIB) under mild milling conditions to maintain crystallography. For the high-resolution electron energy-loss spectroscopy studies (HREELS), a recently developed TEM gun monochromator, implemented into a 200 kV field emission gun column was used in combination with a new post-column spectrometer. It was found that, dependent on substrate and atmosphere, layers with different vanadium and nitrogen content were formed, showing distinct differences in their ELNES. With an energy resolution at the 0.2 eV level and a TEM beam spot size of approximately 2 nm these layers could be unambiguously identified when compared to theoretical ELNES simulations from the literature.