Static Time-of-flight Secondary Ion Mass Spectrometry Research Articles

TOF-SIMS Analysis of Red Color Inks of Writing and Printing Tools on Questioned Documents.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a well-established surface technique that provides both elemental and molecular information from several monolayers of a sample surface while also allowing depth profiling or image mapping to be performed. Static TOF-SIMS with improved performances has expanded the application of TOF-SIMS to the study of a variety of organic, polymeric, biological, archaeological, and forensic materials. In forensic investigation, the use of a minimal sample for the analysis is preferable. Although the TOF-SIMS technique is destructive, the probing beams have microsized diameters so that only small portion of the questioned sample is necessary for the analysis, leaving the rest available for other analyses. In this study, TOF-SIMS and attenuated total reflectance Fourier transform infrared (ATR-FTIR) were applied to the analysis of several different pen inks, red sealing inks, and printed patterns on paper. The overlapping areas of ballpoint pen writing, red seal stamping, and laser printing in a document were investigated to identify the sequence of recording. The sequence relations for various cases were determined from the TOF-SIMS mapping image and the depth profile. TOF-SIMS images were also used to investigate numbers or characters altered with two different red pens. TOF-SIMS was successfully used to determine the sequence of intersecting lines and the forged numbers on the paper.

Characterization of Natural Dyes and Traditional Korean Silk Fabric by Surface Analytical Techniques.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) are well established surface techniques that provide both elemental and organic information from several monolayers of a sample surface, while also allowing depth profiling or image mapping to be carried out. The static TOF-SIMS with improved performances has expanded the application of TOF-SIMS to the study of a variety of organic, polymeric and biological materials. In this work, TOF-SIMS, XPS and Fourier Transform Infrared (FTIR) measurements were used to characterize commercial natural dyes and traditional silk fabric dyed with plant extracts dyes avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. Silk textiles dyed with plant extracts were then analyzed for chemical and functional group identification of their dye components and mordants. TOF-SIMS spectra for the dyed silk fabric showed element ions from metallic mordants, specific fragment ions and molecular ions from plant-extracted dyes. The results of TOF-SIMS, XPS and FTIR are very useful as a reference database for comparison with data about traditional Korean silk fabric and to provide an understanding of traditional dyeing materials. Therefore, this study shows that surface techniques are useful for micro-destructive analysis of plant-extracted dyes and Korean dyed silk fabric.

Excimer laser patterning of PEDOT:PSS thin-films on flexible barrier foils: A surface analysis study

Selective laser patterning of thin organic films is an important aspect in the roll-to-roll production of organic electronic devices such as organic light emitting diodes (OLEDs). An excimer laser is well suited for the patterning and structuring of polymer thin films as their UV absorption is significant. Selective removal of a transparent conducting polymer PEDOT:PSS (poly(3,4-ethylene dioxythiophene):polystyrene sulfonate) on a multilayered (inorganic–organic–inorganic) barrier and a flexible PEN (polyethylene napthalate) substrate has been studied using a KrF excimer laser. The ablation craters were characterized with electron microscopy and profilometry. For the first time, chemical surface analysis of the patterned area was performed with Time-Of-Flight Static Secondary Ion Mass Spectrometry (TOF-S-SIMS), providing a detailed insight of the surface composition after laser ablation and plasma post-treatments.

ToF-S-SIMS molecular 3D analysis of micro-objects as an alternative to ion beam erosion at large depth: application to single inkjet dots

Molecular depth profiling is needed to develop high-tech materials optimised to the μm or even up to the nm scale. Recent progress in time-of-flight static secondary ion mass spectrometry (ToF-S-SIMS) offers perspectives to molecular depth profiling. However, at this moment, the methodology is not yet capable to deal with a range of materials science applications because of the limited depth range, the loss of intensity in the subsurface and the loss of depth resolution at large distances from the original surface. Therefore, the purpose of this paper is to develop a complementary approach for the molecular 3D analysis at large depth, using a combination of ultra-low angle microtomy (ULAM) and surface analysis of the sectioned material with ToF-S-SIMS. Single inkjet dots with a diameter of 100 μm and height of 22 μm on a PET substrate have been used as a test system for the methodology. It is demonstrated that the use of a diamond knife allows the molecular composition and distribution of components within the microscopic feature to be probed with a lateral resolution of 300 nm. Hence the methodology approaches the physical limit for ion imaging of organic components with local concentrations in the % range. In practice, the achievable depth resolution with ULAM-S-SIMS is ultimately limited by the surface roughness of the section. Careful optimisation of the ULAM step has resulted in a surface roughness within 6 nm (R(a) value) at a depth of 21 μm. This offers perspective to achieve 3D analysis with a depth resolution as good as 18 nm at such a large distance from the surface. Furthermore, the ULAM-S-SIMS approach is applicable to materials unamenable to ion beam erosion. However, the method is limited to dealing with, for instance, Si or glass substrates that cannot be sectioned with a microtomy knife. Furthermore, sufficient adhesion between stacked layers or between the coating and substrate is required. However, it is found that the approach is applicable to a wide variety of industrially important (multi)layers of polymers on a polymer substrate.

Surface Measurement of GLSI Wafer with Copper Interconnects after CMP

Chemical mechanical polishing (CMP) is the best global planarization technology of GLSI process. After CMP process, there may appear large roughness, micro scratch, dishing pit, erosion pit, with-in-wafer-non-uniformity (WIWNU), organic contamination, particles and metal ions pollution on wafer with copper interconnects. Surface measurement of CMP process on the wafer mainly involves the test of roughness, defects and the contaminations. Atomic force profiler (AFP) combined with the resolution of the AFM and long-range-scan ability of the steps instrument (100 mm), is suitable for CMP process which needs to measure both the planarization of long-range scanning and tungsten plug and copper interconnects with high resolution imaging. Optical detection technology combined with the advantages of dark and bright view detection is suitable for detection of particles, crystal originated pits (COP), defects, etc. The time-of-flight static secondary ion mass spectrometry (TOF-SIMS) and total reflection X-ray fluorescence (TXRF) are applicable to detect metal ions. The selection and use of advanced data analysis theory and method can help to improve the speed of analysis and to find the main factors of influence surface quality. Pareto diagram analysis is very beneficial for study polishing effects and the main reason of the surface state for Cu-CMP wafer. Nine sampling method and five sampling method fit to analysis the uniform surface distribution, on the contrast isometric sampling can reflect the distribution of the surface state along the radius difference.

A solvation-based screening approach for metabolite arrays

This paper explores a new method for screening metabolites in an array format based on relative polarity using selective solvent dissolution. A synthetic cocktail of metabolites was spotted onto a hydrophobic silicon surface, and solubilised with solvents of varying polarity. The metabolites retained on the silicon surface after the solvent treatments were detected using time-of-flight static secondary ion mass spectrometry (ToF-sSIMS). Solvent-specific metabolite retention was clearly evident on multivariate analysis of the dataset, using principal component analysis. Selective removal of metabolites was observed when solvents with different polarity were used, with the metabolite retention or removal in most cases correlating to the polarity of the solvent used, although consideration of other forces in operation may be needed to arrive at fully predictable behaviours. This approach provides the basis for development of a technique to separate complex metabolites into simpler constituents in a metabolite array prior to identification and quantification using mass spectrometry. It is an analytical approach that is intermediate between the more rapid but less informative direct analysis methods (such as DIMS) that do not involve any analyte separations and the more comprehensive but time consuming methods (such as GC- and LC-MS) that involve chromatographic or electrophoretic separations. The approach has the potential to be successfully developed for rapid, yet informative screening of metabolomes.

Spontaneously reactive plasma polymer micropatterns

A combination of spontaneous reactive chemical domains bounded by non-fouling zones provides a means to covalently immobilize biomolecules in structured, spatially defined arrays. These arrays have application in a wide range of biotechnologies including tissue engineering, proteomics, and diagnostics. In this paper, we describe the fabrication of multi-chemistry micropatterns from plasma polymers. X-ray photoelectron spectroscopy (XPS), together with Time-of-Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) and confocal imaging has been utilized to confirm the reactivity and integrity of micropatterns fabricated from amine-reactive maleic anhydride (ppMA) on non-fouling tetraglyme (ppTg). The covalent immobilization of antibodies via the formation of amide linkages with the anhydride groups occurs only in the ppMA domains, while antibody activity is confirmed via their ability to attract specific fluorescent antigens. These micropatterns therefore provide a convenient and effective platform for covalently immobilizing biomolecules in spatially defined areas without the need for multiple step wet chemical immobilization strategies.

Ultra‐low‐angle microtomy to back up S‐SIMS molecular depth profiling with C60+ and Bin+ for the nanoscale analysis of high‐tech industrial materials

AbstractPolyatomic projectiles such as C60+ have been used for molecular sputter depth profiling in time‐of‐flight static secondary ion mass spectrometry (ToF‐S‐SIMS). However, the practical application for nanoscale analysis problems still depends on the likely change of secondary ion yield with depth. Therefore, ultra‐low‐angle microtomy (ULAM) has been applied in conjunction with dual beam depth profiling (Bi3+C60+ + +) on polymer systems relevant to printing industry.Sputter depth profiles have been recorded from two 200 nm poly(methyl methacrylate) (PMMA) layers with additives. Furthermore, also a poly(vinyl pyrrolidone) (PVP)‐PMMA bilayer on Si (thickness of each layer 200 nm) was analyzed using sputter depth profile measurements. Identical samples have been prepared using UV‐cured acrylate as substrate allowing ULAM to be performed. The exposed surfaces have been analyzed using Binq+ liquid metal ion gun (LMIG). Use of a cutting angle of 0.3° and 0.1° makes that, in principle, surface analysis off the section with a spot of 150 nm characterises a depth range of 0.3–0.8 nm in the initial sample.The results show that ULAM is a valuable tool to complement the exploratory use of direct sputter depth profiling. To the best of our knowledge, this feasibility study is the first to show the experimental verification of molecular C60+ sputter depth profiles. Copyright © 2010 John Wiley & Sons, Ltd.

Plasma Polymerization of Maleic Anhydride: Just What Are the Right Deposition Conditions?

Maleic anhydride plasma polymers enable amine-containing biomolecules and polymers to be covalently coupled to a surface from an aqueous solution without any intermediate chemistry. The challenge in developing these functionally active plasma polymers lies in determining the optimal deposition conditions for producing a stable, highly active film. Unlike many previous studies that explore highly varied pulsed and continuous wave (CW) deposition conditions, this paper focuses on the comparison of films deposited under the same low nominal power conditions (1 W) and compares a range of CW, millisecond, and microsecond pulsing parameters that can be used to produce this power condition. The use of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) has enabled the quantitative examination of the effects of processing parameters on the chemical functionality of the films. For the first time, the molecular specificity, surface sensitivity, and high mass resolution of time-of-flight static secondary ion mass spectrometry (ToF-SSIMS) has been exploited to compare these films and multivariate analysis techniques used to explore the relationships between plasma processing parameters and surface chemistry. The results of the studies clearly demonstrate that a range of conditions can produce maleic anhydride films, with optimal functionality seen under microsecond pulsing regimes. Critically, the study demonstrates that the tight control and monitoring of the deposition parameters is critical if these films are to be manufactured with optimal functionality, stability, and minimum processing time.

Physical vs Photolithographic Patterning of Plasma Polymers: An Investigation by ToF−SSIMS and Multivariate Analysis

Physical and photolithographic techniques are commonly used to create chemical patterns for a range of technologies including cell culture studies, bioarrays and other biomedical applications. In this paper, we describe the fabrication of chemical micropatterns from commonly used plasma polymers. Atomic force microscopy (AFM) imaging, time-of-flight static secondary ion mass spectrometry (ToF-SSIMS) imaging, and multivariate analysis have been employed to visualize the chemical boundaries created by these patterning techniques and assess the spatial and chemical resolution of the patterns. ToF-SSIMS analysis demonstrated that well-defined chemical and spatial boundaries were obtained from photolithographic patterning, while the resolution of physical patterning via a transmission electron microscopy (TEM) grid varied depending on the properties of the plasma system including the substrate material. In general, physical masking allowed diffusion of the plasma species below the mask and bleeding of the surface chemistries. Multivariate analysis techniques including principal component analysis (PCA) and region of interest (ROI) assessment were used to investigate the ToF-SSIMS images of a range of different plasma polymer patterns. In the most challenging case, where two strongly reacting polymers, allylamine and acrylic acid were deposited, PCA confirmed the fabrication of micropatterns with defined spatial resolution. ROI analysis allowed for the identification of an interface between the two plasma polymers for patterns fabricated using the photolithographic technique which has been previously overlooked. This study clearly demonstrated the versatility of photolithographic patterning for the production of multichemistry plasma polymer arrays and highlighted the need for complementary characterization and analytical techniques during the fabrication plasma polymer micropatterns.

A ToF-SSIMS study of plasma polymer-based patterned metal affinity surfaces

Abstract Polymers that exhibit an affinity to metal ions are important for separation science and sensor applications. In this paper, we describe the creation of surface micropatterns with three plasma polymers, acrylic acid (ppAAc), allylamine (ppAAm) and tetraglyme (ppTG). Time-of-Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) imaging has been used to visualise the chemical specificity and selectivity of the plasma polymers as substrates for immoblised metal affinity protein separation. This technique provides the necessary spatial resolution to chemically resolve the multiple components present on these surfaces. Enzyme-linked immunosorbent assay (ELISA) was also employed to confirm the biological specificity of these surfaces. The results clearly demonstrate that under the correct solvent conditions, ppAAc-modified surfaces coordinate gallium and are able to selectively attract phosphoproteins. Critically, it is possible to then remove the protein from the surface and regenerate the chemistry using a simple elevated pH washing step. These results indicate the potential of these surfaces for implementation in microfluidic devices for the rapid isolation or pre-concentration of phosphopeptides/proteins.

The ability of static secondary ion mass spectrometry to discriminate submonolayer from multilayer adsorption of thiol collectors

Experiments have been carried out to establish whether static time-of-flight secondary ion mass spectrometry (ToF-SIMS) alone is able to differentiate monolayer and multilayer coverage of thiol collectors on sulfide minerals. The systems investigated were those for which X-ray photoelectron spectroscopy is able to provide an independent determination of the extent of coverage, and included diethyldithiophosphate (DTP) and 2-mercaptobenzothiazole (MBT) on chalcocite, DTP on Ag 2+ ∂ S, and iso-butyl xanthate (BX) and MBT on galena. For adsorption of a thiol collector (TC) on copper and silver sulfides, TC and metal(TC)H ions were detected for both monolayer and multilayer coverage. For multilayer coverage only, metal(TC) 2 ions were evident, notwithstanding the fact that other spectroscopic measurements had revealed the stoichiometry of the principal multilayer species to be metal(TC). For adsorption on galena, TC and metal(TC) ions were observed for both monolayer and multilayer coverage, whereas for multilayer coverage only, fragment ions from Pb(TC) 2 and (TC) 2 species were evident. Indeed, for all the systems studied, static ToF-SIMS was able to distinguish monolayer from multilayer coverage. However, differentiation was reliable only when both positive and negative secondary ion spectra were determined, and possible only because the multilayer species on copper and silver sulfides included a low concentration of metal dithiolate. In light of those findings, unequivocal differentiation by means of static SIMS is expected to be possible for all thiol collector/sulfide systems.

Fracture behaviour of poly(ethylene terephthalate) fiber toughened epoxy composites

Abstract Thermoplastic poly(ethylene terephthalate) (PET) fibers have been used to toughen an intrinsically brittle epoxy resin with high glass transition temperature. The morphologies and chemical properties of the as-received and the surface-modified PET fibers are comparatively investigated by scanning electron microscopy (SEM) and time-of-flight static secondary ion mass spectrometry (ToF-SIMS). Strong fiber–matrix adhesion is successfully achieved by optimizing surface modification of PET fibers with NaOH. Compared with neat epoxy resin, the fracture toughness of PET fibers filled epoxy composites is almost doubled when loading only 1 wt% chemically treated fiber. The fracture behavior and toughening mechanisms are studied by SEM observations on the fracture surfaces. Good correlation is found between the surface morphologies of the treated fibers, the fracture surfaces and the observed fracture toughness. SEM shows that fiber pullout, fiber breakage and formation of step structures due to fiber addition are among the operative toughening mechanisms observed.

Surface analysis of plasma-deposited polymer films by Time of Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) before and after exposure to ambient air

Pulsed plasma deposited styrene and ethylene films were studied by Time of Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma deposited films was investigated. Approaches for the interpretation of SSIMS spectra of organic materials were reviewed and applied to the evaluation of SSIMS data of plasma deposited films. From these data, information on the chemical character of the plasma deposited films was derived.When the plasma polymers are exposed to air oxygen incorporation occurs. The oxygen uptake is high at the beginning and then it levels of.A relation that “higher the regularity of the film lower is the oxygen uptake” was found. Harder plasma conditions, which could be obtained by applying higher plasma power or lower monomer flow rate, result in higher oxygen uptake and vice versa.

Comparative study of organic dyes with time‐of‐flight static secondary ion mass spectrometry and related techniques

A series of cationic, zwitterionic and anionic fluorinated carbocyanine dyes, spin-coated on Si substrates, were measured with time-of-flight static secondary ion mass spectrometry (TOF-S-SIMS) under Ga(+) primary ion bombardment. Detailed fragmentation patterns were developed for all dyes measured. In the positive mode, the resulting spectra showed very intense signals for the precursor ions of the cationic dyes, whereas the protonated signals of the anionic dyes were hardly detected. Differences of three orders of magnitude were repeatedly observed for the secondary ion signal intensities of cationic and anionic dyes, respectively. All measured dyes yielded mass spectra containing several characteristic fragment ions. Although the secondary ion yields were still higher for the cationic than the anionic dye fragments, the difference was reduced to a factor of < or =10. This result and the fact that M(+), [M + H](+) or [M + 2H](+) are even-electron species make it very likely that the recorded fragments were not formed directly out of the (protonated) parent ions M(+), [M + H](+) or [M + 2H](+). In the negative mode, none of the recorded spectra contained molecular information. Only signals originating from some characteristic elements of the molecules (F, Cl), the anionic counter ion signal and some low-mass organic ions were detected. A comparative study was made between TOF-S-SIMS, using Ga(+) primary ions, and other mass spectrometric techniques, namely fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). The measurements showed that MALDI, ESI and FAB all give rise to spectra containing molecular ion signals. ESI and FAB produced M(+) and [M + H](+) signals, originating from the cationic and zwitterionic dyes, in the positive mode and M(-) and [M - H](-) signals of the anionic and zwitterionic dyes in the negative mode. With MALDI, molecular ion signals were measured in both modes for all the dyes. Structural fragment ions were detected for FAB, ESI and MALDI in both the positive and negative modes. Compared with the other techniques, TOF-S-SIMS induced a higher degree of fragmentation.

Microscale chemical and electrostatic surface patterning of Dow Cyclotene by N 2 plasma

Using TEM grids as masks, we have chemically modified selected areas of the surface of Dow Cyclotene, a low permittivity polymer, by a N 2 plasma (chemical surface patterning), grafting a maximum of ∼3% N; this was verified by XPS (X-ray photoelectron spectroscopy) and TOF-S-SIMS (time-of-flight static secondary ion mass spectrometry) chemical imaging. Contact mode AFM (atomic force microscopy) studies of the modified surface morphology show unexpected, initially large, values of both etch depth and friction in the treated areas, which decrease on exposure to atmosphere; similar results were absent in tapping mode images. When Cu, which forms nanoclusters on Cyclotene, was deposited by evaporation onto freshly etched Cyclotene, the large etch depth and friction in the etched areas decreased to much lower values. The depth and friction differences occurring on surface modification, which were revealed through our use of patterning, are apparent, and are, in fact, caused by enhanced electrostatic interaction of the chemically modified surface with the AFM tip, as confirmed by the tapping mode data. Some of the electrostatic surface charge, introduced by the positively charged species chemically modifying the Cyclotene surface, is reduced by subsequent charge neutralization. XPS has shown this to be due to the oxidation of these surface charges on atmospheric exposure, initially ∼70%, to form alcohol, carbonyl and carboxylic acid groups. Contact mode AFM imaging of plasma-patterned surfaces is revealed as an excellent tool for the high-resolution characterization of such surfaces.

Surface Analysis of Plasma‐Deposited Polymer Films, 1

AbstractSummary: Pulsed plasma‐deposited polystyrene films were studied by time‐of‐flight static secondary ion mass spectrometry (ToF‐SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma‐deposited polystyrene films was investigated. From these data, information on the chemical character of the plasma polystyrene films was derived. In the range of deposition conditions applied in this study, the fragmentation of styrene is a minor process. The main process is probably the radical chain propagation to polymers. All the polystyrene plasma polymers, relying on ToF‐SIMS, seem to be rather similar to a reference polystyrene oligomer sample. When the plasma polymers are exposed to air, extensive oxygen incorporation occurs. Oxygen uptake was found to alter the emission probabilities of secondary ions. A relation between the regularity of the plasma polymers and the amount of oxygen incorporation was found. The result was that the chemical regularity of the plasma polystyrene decreases when the effective power in the plasma is increased.ToF‐SSIMS spectra of PP‐PS‐1 before exposure (left) and after two weeks exposure (right) to air. The intensity of the oxygen containing fragments increase indicating an increase on the amount of oxygen incorporation.magnified imageToF‐SSIMS spectra of PP‐PS‐1 before exposure (left) and after two weeks exposure (right) to air. The intensity of the oxygen containing fragments increase indicating an increase on the amount of oxygen incorporation.

Characterization of poly(L-lysine)-graft-poly(ethylene glycol) assembled monolayers on niobium pentoxide substrates using time-of-flight secondary ion mass spectrometry and multivariate analysis.

Control of protein adsorption onto solid surfaces is a critical area of biomaterials and biosensors research. Application of high performance surface analysis techniques to these problems can improve the rational design and understanding of coatings that control protein adsorption. We have used static time-of-flight secondary ion mass spectrometry (TOF-SIMS) to investigate several poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) adlayers adsorbed electrostatically onto negatively charged niobium pentoxide (Nb(2)O(5)) substrates. By varying the PEG graft ratio (i.e., the number of lysine monomers per grafted PEG chain) and the molecular weights of the PLL and PEG polymers, the amount of protein adsorption can be tailored between 1 and 300 ng/cm(2). Detailed multivariate analysis using principal component analysis (PCA) of the positive and negative ion TOF-SIMS spectra showed changes in the outermost surface of the polymer films that were related to the density and molecular weight of the PEG chains on the surface. However, no significant differences were noted due to PLL molecular weight, despite observed differences in the serum adsorption characteristics for adlayers of PLL-g-PEG polymers with different PLL molecular weights. From the PCA results, multivariate peak intensity ratios were developed that correlated with the thickness of the adlayer and the enrichment of the PEG chains and the methoxy terminus of the PEG chains at the outermost surface of the adlayer. Furthermore, partial least squares regression was used to correlate the TOF-SIMS spectra with the amount of protein adsorption, resulting in a predictive model for determining the amount of protein adsorption on the basis of the TOF-SIMS spectra. The accuracy of the prediction of the amount of serum adsorption depended on the molecular weight of the PLL and PEG polymers and the PEG graft ratio. The combination of multivariate analysis and static TOF-SIMS provides detailed information on the surface chemistry and insight into the mechanism for protein resistance of the coatings.

Poly-dimethyl-siloxane (PDMS) contamination of polystyrene (PS) oligomers samples: a comparison of time-of-flight static secondary ion mass spectrometry (TOF-SSIMS) and X-ray photoelectron spectroscopy (XPS) results

Pure and PDMS contaminated PS oligomers films were investigated both by time-of-flight static secondary ion mass spectrometry (TOF-SSIMS) and X-ray photoelectron spectroscopy (XPS).The secondary ion spectra from the PDMS contaminated PS oligomers were almost completely related to PDMS. XPS revealed a PDMS contamination characterized by a silicon surface concentration of 6at.%. Obviously siloxane contaminants existing on the surface of a silicon wafer may diffuse towards the PS oligomers outermost surface resulting in a rather high PDMS surface concentration of about 85%. Due to the known differences in the information depth and sensitivity of SSIMS and XPS very different detection limits are to be considered.In elimination of siloxane contaminants by ultrasonication in hexane was found to be an effective way. Another common organic cleaning procedure, which is ultrasonication in trichloroethylene (TCE), subsequently in isopropanol and finally in acetone was found to be ineffective for cleaning of PDMS contaminated silicon wafers.

Stainless steel modified with poly(ethylene glycol) can prevent protein adsorption but not bacterial adhesion

The surface of AISI 316 grade stainless steel (SS) was modified with a layer of poly(ethylene glycol) (PEG) (molecular weight 5000) with the aim of preventing protein adsorption and bacterial adhesion. Model SS substrates were first modified to introduce a very high density of reactive amine groups by the adsorption of branched poly(ethylenimine) (PEI) from water. Methoxy-terminated aldehyde-poly(ethylene glycol) (M-PEG-CHO) was then grafted onto the PEI layers using reductive amination at the lower critical solution temperature (LCST) of the PEG in order to optimize the graft density of the linear PEG chains. The chemical composition and uniformity of the surfaces were determined using X-ray photoelectron spectroscopy (XPS) and time-of-flight static secondary ion mass spectrometry (ToF-SSIMS) in the imaging mode. The effects of PEI concentration and different substrate pre-cleaning methods on the structure and stability of the final PEG layer was examined. Piranha solution proved to be the most effective method for removing adventitious hydrocarbon contamination, compared to cleaning with ultrasonication in organic solvents, and was the SS substrate that produced the most stable and thickest PEI layer. The surface density of PEI was shown to increase with increasing PEI concentration (up to 30 mg/ml), as determined from XPS measurements, and subsequently produced the PEG layer with the highest density of attached chains. In model experiments using β-lactoglobulin no protein adsorption was detected on the optimized PEG surface as determined by XPS and ToF-SSIMS analysis. However, neither the adhesion of a Gram-negative ( Pseudomonas sp.) nor a Gram-positive ( Listeria monocytogenes) bacterium was affected by the coating as equal numbers adhered to all surfaces tested. Our results show that preventing protein adsorption is not a prerequisite stopping bacterial adhesion, and that other mechanisms most likely play a role.