Quantitative low energy depth profiling of SiGe laterally nonuniform structures

In cells containing Li{sub 1.05}(Ni{sub 1/3}Co{sub 1/3}Mn{sub 1/3}){sub 0.95}O{sub 2}-based positive and graphite-based negative electrodes, a significant portion of cell impedance rise on aging is known to be from the negative electrode. One possible reason for this impedance rise is the dissolution of transition-metal elements from the oxide electrode that accumulate and create a high-impedance layer at the negative electrode-electrolyte interface. This article details dynamic secondary ion mass spectrometry (SIMS) measurements, which provide a relative comparison of Mn, Co, and Ni contents on fresh, formed, and aged graphite electrodes. The data clearly indicate that these transition-metal elements accumulate at the electrode surface and diffuse into the electrode during cell aging.

We demonstrate that dynamic secondary ion mass spectrometry (SIMS)-based ion microscopy can provide a means of measuring (13)C assimilation into individual bacterial cells grown on (13)C-labelled organic compounds in the laboratory and in field soil. We grew pure cultures of Pseudomonas putida NCIB 9816-4 in minimal media with known mixtures of (12)C- and (13)C-glucose and analysed individual cells via SIMS imaging. Individual cells yielded signals of masses 12, 13, 24, 25, 26 and 27 as negative secondary ions indicating the presence of (12)C(-), (13)C(-), (24)((12)C(2))(-), (25)((12)C(13)C)(-), (26)((12)C(14)N)(-) and (27)((13)C(14)N)(-) ions respectively. We verified that ratios of signals taken from the same cells only changed minimally during a approximately 4.5 min period of primary O(2)(+) beam sputtering by the dynamic SIMS instrument in microscope detection mode. There was a clear relationship between mass 27 and mass 26 signals in Pseudomonas putida cells grown in media containing varying proportions of (12)C- to (13)C-glucose: a standard curve was generated to predict (13)C-enrichment in unknown samples. We then used two strains of Pseudomonas putida able to grow on either all or only a part of a mixture of (13)C-labelled and unlabelled carbon sources to verify that differential (13)C signals measured by SIMS were due to (13)C assimilation into cell biomass. Finally, we made three key observations after applying SIMS ion microscopy to soil samples from a field experiment receiving (12)C- or (13)C-phenol: (i) cells enriched in (13)C were heterogeneously distributed among soil populations; (ii) (13)C-labelled cells were detected in soil that was dosed a single time with (13)C-phenol; and (iii) in soil that received 12 doses of (13)C-phenol, 27% of the cells in the total community were more than 90% (13)C-labelled.

High detection sensitivity in bulk analysis or depth profiling by secondary ion mass spectrometry (SIMS) can only be achieved, for positively charged ions, if the nearsurface regions of the sputter eroded sample are fully oxidized. Using oxygen primary ions, a stationary oxidation state is established after some time of bombardment during which period the sputtering yield decreases and the ionization probability increases. The physical and chemical processes occurring during the transient period are reviewed with emphasis on the results for impurity analysis in silicon, i.e. the matrix material that has been studied most thoroughly in the past. The transient decrease in sputtering yield gives rise to a depth scale offset and an associated apparent shift of impurity profiles towards the surface. The effect is largest at normal beam incidence, ca. 1 nm /keV (O + 2 ), in which case silicon is fully oxidized. The transition depth, i.e. the depth sputtered before achieving a stable ion yield is about twice as large and increases as the impact angle is turned away from normal. The shift and the depth scale offset can be measured safely using thin (delta) layers of isotopically pure tracers, for example 30 Si in 28 Si. Boron delta layers can serve as secondary standards because this impurity behaves almost the same as the host silicon atoms. The profile shift observed with other common dopants may contain contributions due to unidirectional relocation, often driven by segregation away from the surface. At O + 2 energies below about 0.7 keV the transition depths fall below the thickness of typical native oxides, so that the transient changes in sputtering yield and ionization probability can disappear. The transient phenomena may be described by a simple sputtering-oxidation model that connects the depth scale offset to other observable parameters like the initial and final sputtering yield, the transition fluence and the oxide thickness.

Progress in analytical imaging of the cell by dynamic secondary ion mass spectrometry (SIMS microscopy)

The technique of dynamic secondary ion mass spectrometry (SIMS) has, during the 1980s, become a firmly established tool in the microanalytical and microstructural characterization of dental hard tissues. SIMS has proved to be outstandingly suited for charting the distributions of most elements, even at extremely low concentrations, in tooth and bone materials. In-depth concentration profiles as well as surface distribution maps of elements have been recorded with excellent (sub-micron) morphologic resolution. In spite of documented success, only relatively few teams, in a handful of countries, are presently engaged, to any significant extent, in conducting tooth or bone research by the application of SIMS. For dental-medical-surgical laboratories, a partial reason for non-communication is a lack of information about SIMS and its particular assets. Another reason may be connected with an essentially groundless reputation, among non-specialists, of SIMS being an exclusive and expensive technique. Among SIMS laboratories, on the other hand, the inertia in tackling biomineralization is partly due to some particular artifacts of analysis, hitherto not generally known and controlled. The present paper briefly sketches the chief principles of modern SIMS, emphasizing factors of special relevance in the characterization of biomineralized tissues. Examples of recent applications are provided. Present procedures and their limitations are discussed, especially with regard to elemental quantification and imaging. Suggestions for relatively simple modifications to existing routines are offered with the aim of enhancing the ease and availability of SIMS in odontological and surgical research.

Challenges of biological sample preparation for SIMS imaging of elements and molecules at subcellular resolution

The Ar gas cluster ion beam (Ar-GCIB) technique is advantageous for soft sputtering of large organic molecules. However, in secondary ion mass spectrometry (SIMS) measurements using Ar-GCIB, the secondary ion yield is typically very low. Matrix-enhanced (ME)-SIMS is a technique that has the potential to enhance the yield. In a previous study on ME-SIMS, aromatic compounds that are typically employed for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were used for the matrix. Although aromatic rings are involved in soft ionization by absorption of energy from the laser probe in MALDI-MS, aromatic rings may not be required for ME-SIMS, which does not use a laser probe. In this study, the effect of non-aromatic matrices was investigated. The results indicated that some nonaromatic compounds are effective for enhancing sensitivity and that the degree of enhancement depends on the molecular weight of analytes. To investigate the reason for this, it was assumed that the yield in SIMS measurements is simply determined by the sputtering yield, the survival rate, and the ionization probability, each of which has molecular weight dependence. Under these assumptions, the SIMS yield is found to be dependent on the matrix species.

The development of organic optoelectronic devices relies on controlling interfaces during thin-film deposition and requires an accurate characterization of the film composition at these interfaces. Dynamic secondary ion mass spectrometry (SIMS) is widely used to investigate multilayer thin-film structures. Routine analysis protocols are well established for classical semiconductor samples, but for organic or mixed metallic–organic samples the limitations of the technique are less well established. In the current work, low-energy dynamic SIMS is used on metal–organic multilayered model structures similar to those in organic optoelectronic devices to study the origin of diffusion of metal into the organic layer (e.g., irradiation-induced diffusion during SIMS analysis or during the deposition process). Samples contain silver and organic compounds sequentially deposited by thermal evaporation in vacuum onto a Si substrate. They are analyzed using a 250 eV to 1 keV Cs+ primary ion beam. It is found that the m...

3D chemical microscopy is one of the emerging applications of secondary ion mass spectrometry (SIMS) in biology. Tissues, cells, extracellular matrices, and polymer films can be imaged at present with a lateral resolution of 50 nm and depth resolution of 1 nm using the latest generation of CAMECA magnetic sector NanoSIMS 50 or with a lower lateral resolution (above 100 nm) using IMS 4f Cameca SIMS equipped with cold stage. Dynamic mode SIMS analysis is performed in ultrahigh vacuum and thus requires specific and careful preparation of biological samples aimed at preserving and minimizing destruction of the original structural and chemical properties of the samples. Here we describe a methodology based on the ultrafast plunge-freezing of biological tissues, preparation of the sample for SIMS analyses and transfer to the SIMS cold stage without interruption of the cold chain during the mounting procedure and subsequent SIMS analyses. Using this strategy, SIMS chemical microscopy can be performed on biological tissue in which unwanted molecular and/or structural reorganization, loss of constituents and chemical modifications are minimized and in which structures are therefore optimally preserved.

Secondary ion mass spectrometry (SIMS) is based upon the energetic ion bombardment of surfaces resulting in in the emission of sputtered particles, including both atomic and molecular ions. The use of mass spectrometric detection provides a highly versatile and sensitive tool for surface and thin film microanalysis. The scope of the technique includes a diversity of analysis modes including: 1. Elemental Depth Profiling (dynamic SIMS), 2. Laterally Resolved Imaging (ion microprobe or ion microscope analysis), 3. Image Depth Profiling (combination of modes 1 and 2 providing 3-D images), 4. Molecular Monolayer Analysis and Imaging (static SIMS), 5. Sputtered Neutral Mass Spectrometry (post-ionization). Much of the early work in dynamic SIMS centered on depth profiling and imaging techniques, with an emphasis on applications to electronic materials. SIMS has made extensive contributions to semiconductor materials science since the 1960's, including the development of new devices and processes, and in failure analysis.

Depth profiles of Si nanocrystals formed in sapphire by ion implantation and the effect of charging during X-ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) measurements have been studied. Atomic concentration and the chemical environment of Si, Al, and O have been measured as a function of depth from the sample surface by SIMS and XPS. Both as-implanted and annealed samples have been analyzed to understand the effect of nanocrystal formation on the depth distribution, chemical structure, and the charging effect before and after the formation process. SIMS measurements have revealed that the peak position of the Si concentration shifts to deeper values with implantation dose. This is explained by the fact that the structure of the matrix undergoes a phase transformation from pure sapphire to a Si rich amorphous Al2O3 with heavy dose implantation. Formation of Si nanocrystals has been observed by XPS by an increase in the Si-Si signal and a decrease in Si-O bond concentrations after the annealing. Variation in binding energies of Si and O with Si concentration (i.e., with depth) has been studied in terms of chemical environments and charging effects. It is found that binding energy of these elements shifts to lower values with increasing Si content. This is a result of less charging due to the presence of easy discharge paths in the Si rich regions of the matrix. Nanocrystal formation leads to even less charging which is probably due to the further increase in conductivity with the formation.

The performance of organic optoelectronic devices depends a lot on interface structure and width. Dynamic secondary ion mass spectrometry (SIMS) has been widely used to investigate interfaces in classical semiconductor devices and limitations are quite well understood. For low-energy dynamic SIMS on organic optoelectronic devices, sputter-induced diffusion processes and roughness formation have only been investigated sparsely. In this work we use low-energy dynamic SIMS depth profiling on metal-organic multilayered model samples with compositions similar to organic optoelectronic devices to investigate limitations in the calculation of interface widths due to sputter-induced roughness formation. The samples consist of silver and organic compounds (e.g., tris(8-hydroxyquinolinato) aluminum (Alq(3)) and metal phthalocyanines) sequentially deposited by thermal evaporation in vacuum onto a Si substrate. They are analyzed by a 500 eV Cs(+) primary ion beam. Surface roughness at the SIMS crater bottoms is characterized by AFM as a function of crater depth. We find that the roughness in SIMS craters is limited to approximately 1.5 nm, which is much smaller than the interface width of the as-deposited interfaces. Thus, for the studied organic-inorganic interfaces, low-energy dynamic SIMS can yield accurate information about interface morphology, allowing the study of its dependence on sample preparation conditions and its implication on device properties.

Many important processes such as catalysis, corrosion, and adhesion depend on the elemental and molecular composition of the surface or interfacial region. The focus of this article is specifically surface applications of secondary ion mass spectrometry (SIMS). Conceptually, SIMS is a very simple technique consisting of a primary ion bombardment step, an energy transfer step, a particle desorption step, and an ion detection step. SIMS experiments are carried out in either a dynamic or a static mode. The two modes are distinguished on the basis of ion dose. Dynamic SIMS uses high primary ion beam doses and is generally used for elemental depth profiling. Static SIMS uses low primary ion beam doses (≤1 × 10 12 ions cm −2 ) and is generally used for the chemical characterization of surfaces. The major advantages of SIMS include high sensitivity (parts per million detection limits for some elements), the ability to obtain molecular information, isotopic analysis, lateral characterization (imaging), and analysis of low‐atomic‐number elements such as H and Li. These characteristics combine to make SIMS a very powerful analytical tool. The key disadvantages of SIMS are that the instrumentation is relatively expensive and that the data can be complex. Related analytical techniques for surface analysis include X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), Scanning Auger Microscopy (SAM), and laser desorption mass spectrometry (LDMS).

Optimization of secondary ion mass spectrometry for quantitative trace analysis

Recently, a report raised the possibility of shrapnel-induced chronic beryllium disease from long-term exposure to the surface of retained aluminum shrapnel fragments in the body. Since the shrapnel fragments contained trace beryllium, methodological developments were needed for beryllium quantification and to study its spatial distribution in relation to other matrix elements, such as aluminum and iron, in metallurgic samples. In this work, we developed methodology for quantification of trace beryllium in samples of shrapnel fragments and other metallurgic sample-types with main matrix of aluminum (aluminum cans from soda, beer, carbonated water and aluminum foil). Sample preparation procedures were developed for dissolving beryllium for its quantification with the fluorescence detection method for homogenized measurements. The spatial distribution of trace beryllium on the sample surface and in 3D was imaged with a dynamic secondary ion mass spectrometry instrument, CAMECA IMS 3f secondary ion mass spectrometry ion microscope. The beryllium content of shrapnel (∼100 ppb) was the same as the trace quantities of beryllium found in aluminum cans. The beryllium content of aluminum foil (∼25 ppb) was significantly lower than cans. SIMS imaging analysis revealed beryllium to be distributed in the form of low micron-sized particles and clusters distributed randomly in X-Y- and Z dimensions, and often in association with iron, in the main aluminum matrix of cans. These observations indicate a plausible formation of Be-Fe or Al-Be alloy in the matrix of cans. Further observations were made on fluids (carbonated water) for understanding if trace beryllium in cans leached out and contaminated the food product. A direct comparison of carbonated water in aluminum cans and plastic bottles revealed that beryllium was below the detection limits of the fluorescence detection method (∼0.01 ppb). These observations indicate that beryllium present in aluminum matrix was either present in an immobile form or its mobilization into the food product was prevented by a polymer coating on the inside of cans, a practice used in food industry to prevent contamination of food products. The lack of such coating in retained shrapnel fragments renders their surface a possible source of contamination for long-term exposure of tissues and fluids and induction of disease, as characterized in a recent study. Methodological developments reported here can be extended to studies of beryllium in electronics devices and components.