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This talk was given within the scope of the SIMS-22 conference in October 2019 in Kyoto (Japan). It deals with the surface analytical investigation of nanoparticles by PCS-assisted ToF-SIMS. This technique is applicable to core-shell nanoparticles, in order to distinguish a complete encapsulation from an incomplete encapsulation of the core by the shell material. Furthermore, the depletion process of organic nanoparticle coatings caused by UV-weathering is investigated. Finally, the significance of grouping studies for nanomaterials research and risk assessment is demonstrated.
Core–shell nanoparticles (CSNPs) have become indispensable in various industrial applications. However, their real internal structure usually deviates from an ideal core–shell structure. To control how the particles perform with regard to their specific applications, characterization techniques are required that can distinguish an ideal from a nonideal morphology. In this work, we investigated poly(tetrafluoroethylene)–poly(methyl methacrylate) (PTFE–PMMA) and poly(tetrafluoroethylene)–polystyrene (PTFE–PS) polymer CSNPs with a constant core diameter (45 nm) but varying shell thicknesses (4–50 nm). As confirmed by transmission scanning electron microscopy (T-SEM), the shell completely covers the core for the PTFE–PMMA nanoparticles, while the encapsulation of the core by the shell material is incomplete for the PTFE–PS nanoparticles. X-ray photoelectron spectroscopy (XPS) was applied to determine the shell thickness of the nanoparticles. The software SESSA v2.0 was used to analyze the intensities of the elastic peaks, and the QUASES software package was employed to evaluate the shape of the inelastic background in the XPS survey spectra. For the first time, nanoparticle shell thicknesses are presented, which are exclusively based on the analysis of the XPS inelastic background. Furthermore, principal component analysis (PCA)-assisted time-of-flight secondary-ion mass spectrometry (ToF-SIMS) of the PTFE–PS nanoparticle sample set revealed a systematic variation among the samples and, thus, confirmed the incomplete encapsulation of the core by the shell material. As opposed to that, no variation is observed in the PCA score plots of the PTFE–PMMA nanoparticle sample set. Consequently, the complete coverage of the core by the shell material is proved by ToF-SIMS with a certainty that cannot be achieved by XPS and T-SEM.
The damaging impact of hydrogen on the austenitic stainless steel AISI 304 L was analysed.
To this aim, samples were charged electrochemically with the hydrogen isotope deuterium (2H, D) and examined with time-of-flight secondary ion mass spectrometry (ToF-SIMS) and electron backscatter diffraction (EBSD). The fusion of the obtained chemical and structural information revealed local enrichment of deuterium in austenite, transformation into martensite, crack formation and severe roughening of the specimen surface. The results indicated that martensite was not only formed during charging but also during Desorption and ToF-SIMS examinations. Furthermore, cross-sections of deuterium-charged samples revealed that in preferred deformation bands a g/ε/a 0 evolution is taking place.
By means of microscopic analyses and carrier gas hot extraction (CGHE), it was found that the use of NaAsO2 as recombination poison decreased the uptake of hydrogen significantly and resulted in severe precipitation on the specimen surfaces. This is in contrast to the popular presumption that NaAsO2 enhances the uptake of hydrogen (and
deuterium) during electrochemical charging by hampering its recombination from Atoms to molecules.
During the energy transformation from fossil fuels to renewable energy sources, the use of hydrogen as fuel and energy storage can play a key role. This presents new challenges to industry and the scientific community alike. The storage and transport of hydrogen, which is nowadays mainly realized by austenitic stainless steels, remains problematic, which is due to the degradation of mechanical properties and the possibility of phase transformation by hydrogen diffusion and accumulation. The development of materials and technologies requires a fundamental understanding of these degradation processes. Therefore, studying the behavior of hydrogen in austenitic steel contributes to an understanding of the damage processes, which is crucial for both life assessment and safe use of components in industry and transportation. As one of the few tools that is capable of depicting the distribution of hydrogen in steels, time-of-flight secondary ion mass spectrometry was conducted after electrochemical charging. To obtain further information about the structural composition and cracking behavior, electron-backscattered diffraction and scanning electron microscopy were performed. Gathered data of chemical composition and topography were treated employing data fusion, thus creating a comprehensive portrait of hydrogen-induced effects in the austenite grade AISI 304L. Specimens were electrochemically charged with deuterium instead of hydrogen. This arises from the difficulties to distinguish between artificially charged hydrogen and traces existing in the material or the rest gas in the analysis chamber. Similar diffusion and permeation behavior, as well as solubility, allow nonetheless to draw conclusions from the experiments.
Biomedical applications, including functional biomaterials, carbohydrate-arrays, and glycan-based biosensors.
The chemistry of glycan immobilization plays an essential role in the bioavailability and function of surface bound carbohydrate moieties. For biomedical applications the stability over time (shelf life) of glycan arrays is a crucial factor. Herein we report on approaches for surface and interface characterization relevant to the needs of production of glycan microarrays which were tested using model carbohydrate surfaces. For detailed characterization of glycan model surfaces we used a combination of X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and ToF SIMS which are complementary techniques of surface chemical analysis. Links to fluorescence spectroscopy often used for characterization in the microarray community were established as well. In detail, amine-reactive silicon oxide and glass surfaces were used for anchoring oligosaccharides with an amino linker. The amount of surface bound carbohydrates was estimated by X-ray photoelectron spectroscopy (XPS). Glycan immobilization was investigated using lectins, which are glycan-binding molecules. A shelf life study of model glycan microarrays on epoxy-coated glass surfaces was done over a period of 160 days under different storage conditions utilizing fluorescence, ToF-SIMS and XPS analysis. It was shown that glycan activity of the models used can be maintained at least for half a year of storage at 4 °C.
This paper describes austenitic-ferritic duplex stainless steels, SAF 2205, in the presence of hydrogen. The duplex stainless steels (DSS) properties include excellent resistance to stress corrosion cracking, high strength and good weldability. Those steels are preferably used in industries combining hydrogen and loads. Hydrogen location in addition to hydrogen binding energy with the steel's defects are of great importance for the analysis of hydrogen embrittlement model in that steel. It is known from previously published works that the susceptibility to hydrogen embrittlement will depend on the competition between reversible and irreversible traps; meaning a direct relation to the hydrogen's state and position in the steel. In this work, we examine the local hydrogen concentration, trapping and distribution by two modern and advanced techniques: thermal desorption spectrometry (TDS) and we support it by time of flight-secondary ion mass spectrometer (ToF-SIMS). In this paper, we support and give for the first time new insights and better understanding to the hydrogen embrittlement mechanism in SAF 2205. The trapping energies levels were calculated using TDS and Lee and Lee's model. This model revealed reversible in addition to irreversible trapping sites. Also the trapping controlling mechanism was found to be a combination of detrapping controlled mechanism and diffusion controlled mechanism. The use of ToF-SIMS for local imaging the distribution of hydrogen species supports the discussion of the different hydrogen traps in this type of steel. The hydrogen embrittlemet phenomenon in SAF 2205 will be discussed in details in that paper.
The effect of electrochemical charging of hydrogen on the structure of a lean duplex stainless steel LDX 2101® (EN 1.4162, UNS S32101) was examined by both Time-of-Flight secondary ion mass spectrometry and electron back-scatter diffraction. The goal is to correlate hydrogen concentration and induced structural changes. Chemical and structural characterizations were done for the same region at the sample's surface with sub-micron spatial resolution. Regions of interest were varying in size between 50 × 50 μm and 100 × 100 μm. The results show a phase transformation of austenite to mainly a defect-rich BCC and scarcely a HCP phase. The phase transformation occurred in deuterium rich regions in the austenite.
High resolution ToF-SIMS imaging of deuterium permeation and cracking in duplex stainless steels
(2017)
Fundamental understanding and elucidation of hydrogen assisted degradation and trapping mechanisms is dependent on sufficient imaging techniques for respective hydrogen interactions, in particular with multi-phase metallic microstructures. The present work shows the progress in elucidating the deuterium behavior in austenitic-ferritic duplex stainless steels under the consideration that deuterium behaves in many ways similarly to hydrogen. A novel combination of deuterium permeation and in-situ Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) imaging technique is compared with post charging ToF-SIMS imaging experiments. As a step beyond state-of-the-art, integration of chemo-metric and high resolution structural characterization techniques with computational multivariate data analysis (MVA) and data fusion is presented.
In the present work, the influence of deuterium on the microstructure of a duplex stainless steel type EN 1.4462 has been characterized by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) supported by scanning electron microscopy (SEM), focused ion beam (FIB), electron back scattered diffraction(EBSD) and energy dispersive x-ray (EDX) investigations. Characterization has been carried out before and after electrochemical charging with deuterium which has been used as a tracer, due to its similar behavior to hydrogen in the steel microstructure. In a first approach, the distribution of the deuterium occurring at temperatures above 58 °C has been visualized. Further it turned out that sub-surface micro blisters are formed in the ferrite-austenite interface, followed by the formation of needle shaped plates and subsequent cracking at the ferrite surface. In the austenite phase, parallel cracking alongside twins and hexagonal close packed (martensitic) regions has been observed. In both phases and even in the apparent interface, cracking has been associated with high deuterium concentrations, as compared to the surrounding undamaged microstructure. Sub-surface blistering in the ferrite has to be attributed to the accumulation and recombination of deuterium at the ferrite-austenite interface underneath the respective ferrite grains and after fast diffusing through this phase. Generally, the present application of chemometric imaging and structural analyses allows characterization of hydrogen assisted degradation at a sub-micron lateral resolution.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and high-resolution scanning electron microscopy are well-acknowledged tools in materials characterization. The ability to map chemical species on the surface of an investigated sample with often low mass detection limits makes ToF-SIMS an essential tool in fields where many question marks concerning Degradation processes and damage mechanisms exist. The aim of this paper is to describe the power of data fusion of ToF-SIMS and high-resolution scanning electron microscopy results employing computational methods for multivariate data Analysis such as principal component analysis. As a case study the investigation of hydrogen distribution in an artificially charged Duplex stainless steel microstructure is presented aiming on a better understanding of hydrogen embrittlement.
Deuterium permeation and cracking in duplex steels as viewed by ToF-SIMS and HR-SEM with data fusion
(2016)
Better understanding of hydrogen assisted degradation and trapping mecha-nisms requires sufficient imaging techniques for respective hydrogen-microstructure interaction studies, in particular with multi-phase metallic micro-structures [1]. The present work is focusing on the elucidation of deuterium be-havior in two austenitic-ferritic duplex stainless steels (DSS) under the assumption that deuterium behaves in many ways similarly to hydrogen [2]. For case studies standard 2205 and lean 2101 DSSs were chosen due to the extensive use of these steels in industry [3]. The analyses were conducted by using a novel in-situ permeation and Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) imaging technique or by ex-situ ToF-SIMS imaging following electrochemical charging experiments. Another pioneering procedure was data fusion (including chemometry) of results of powerful laterally resolved chemical analysis and high resolution structural characterization techniques .
Results for the ex-situ observations showed a different influence of deuterium loading on the two steel grades as well as different damage mechanisms in each phase. Formation of sub-surface blisters between the ferrite and austenite were obtained in both the standard and the lean DSS. In both steels, an increased deuterium concentration was observed around deformed regions such as cracks, confirming that they originate from the presence of deuterium [4]. The formation of parallel cracks was obtained only in the austenite within the standard duplex whereas in the lean duplex the highest intensity of deuterium was obtained in the austenite along the ferrite-austenite interphase.
In comparison, application of the novel in-situ permeation technique enabled to register and record the deuterium permeation through the material and the respective saturation sequence of the two phases as well as the interfaces. Faster diffusion of the deuterium was observed in the ferrite and a direct proof for deuterium enrichment at the austenite-ferrite interface has been given [1]. The integration of the specified techniques gives a better insight into the processes leading to hydrogen induced failure. These two experimental techniques provide very valuable tools for elucidation of respective metallurgical failure mechanisms that can be used for the validation of respective numerical models for hydrogen assisted cracking (HAC).
Modifying or controlling surface chemistry is important in new product development, quality control and research. This is particularly true where functionality of surfaces, thin films and interfaces are key to the application, such as organic solar cells and devices for medical diagnostics. Surface chemical analysis aims to provide quantitative elemental, chemical state and functional group information from the surface of materials, but requires comparable test data and improved measurement traceability.
The certified reference material BAM-L200, a nanoscale stripe pattern for length calibration and specification of lateral resolution, is described. BAM-L200 is prepared from a cross-sectioned epitaxially grown layer stack of AlxGa1–xAs and InxGa1–xAs on a GaAs substrate. The surface of BAM-L200 provides a flat pattern with stripe widths ranging down to 1 nm. Calibration distances, grating periods and stripe widths have been certified by TEM with traceability to the length unit. The combination of gratings, isolated narrow stripes and sharp edges of wide stripes offers plenty of options for the determination of lateral resolution, sharpness and calibration of length scale at selected settings of imaging surface-analytical instruments. The feasibility of the reference material for an analysis of the lateral resolution is demonstrated in detail by evaluation of ToF-SIMS, AES and EDX images. Other applications developed in the community are summarized, too. BAM-L200 fully supports the implementation of the revised International Standard ISO 18516 (in preparation) which is based on knowledge outlined in the Technical Report ISO/TR 19319:2013.
The production of high-quality self-assembled monolayers (SAMs) followed by layer-by-layer (LbL) self-assembly of macrocycles is essential for nanotechnology applications based on functional surface films. To help interpret the large amount of data generated by a standard ToF-SIMS measurement, principal component analysis (PCA) was used. For two examples, the advantages of a combination of ToF-SIMS and PCA for quality control and for the optimization of layer-by-layer self-assembly are shown. The first example investigates how different cleaning methods influence the quality of SAM template formation. The second example focuses on the LbL self-assembly of macrocycles and the corresponding stepwise surface modification.
Argon cluster sputtering of an organic multilayer reference material consisting of two organic components, 4,4'-bis[N-(1-naphthyl-1-)-N-phenyl- amino]-biphenyl (NPB) and aluminium tris-(8-hydroxyquinolate) (Alq3), materials commonly used in organic light-emitting diodes industry, was carried out using time-of-flight SIMS in dual beam mode. The sample used in this study consists of a ~400-nm-thick NPB matrix with 3-nm marker layers of Alq3 at depth of ~50, 100, 200 and 300 nm. Argon cluster sputtering provides a constant sputter yield throughout the depth profiles, and the sputter yield volumes and depth resolution are presented for Ar-cluster sizes of 630, 820, 1000, 1250 and 1660 atoms at a kinetic energy of 2.5 keV. The effect of cluster size in this material and over this range is shown to be negligible.
Nitrogen rich plasma polymer films (L-PPE:N) were prepared by low-pressure RF plasma using a 1:1 mixture of ethylene and ammonia and aged for 345 d in four different ambient conditions: (i) at room temperature (RT) in air; (ii) at RT in nitrogen; (iii) at -20?°C in air and; (iv) at –20 °C in nitrogen. The films were analyzed by X-ray photoelectron spectroscopy (XPS) and by time-of-flight secondary ion mass spectrometry (ToF-SIMS) at various intervals over the duration of the experiment. The ageing of primary amines, NH2, was followed by chemical derivatization with 4-trifluoromethyl benzaldehyde. Storage at –20 °C, mostly independently of ambient atmosphere, slowed down ageing to almost undetectable levels as evaluated by the analytical methods used for this study.
Coordination chemistry was applied to deposit pyridine-functionalized gold nanoparticles on silicon substrates. The particles were synthesized through the Brust/Schiffrin route with a subsequent ligand exchange reaction yielding well-defined particles of two different sizes. Multilayer deposition was carried out on a pyridine-terminated SAM, anchored on a hydroxyl-terminated silicon surface. Analogously, Hunter/Vögtle-type tetralactam macrocycle multilayers were deposited as well as mixed layers containing both either in an alternating sequence or as a macrocycle multilayer with a terminating nanoparticle layer. These composite layers were examined with respect to their ability to bind squaraine axles in the macrocycle cavities. The amount of guest bound is higher for the composite layer with alternating macrocycles and nanoparticles.
The deposition of palladium on a novel, reversibly protonatable, pyridyl-terminated self-assembled monolayer on gold substrates has been studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS spectroscopy) and time of flight-secondary ion mass spectrometry (ToF-SIMS). For this purpose, 12-(pyridin-4-yl)dodecane-1-thiol, consisting of a surface-active head group, an unfunctionalized hydrocarbon backbone and a terminal pyridyl group, has been synthesized and deposited on gold surfaces. Coordination of Pd(II) ions to the pyridyl group was examined. Furthermore, a reversible protonation/deprotonation cycle has been applied, and the relation between protonation and the amount of complexed palladium was studied. Investigation of the SAM by angle-resolved NEXAFS spectroscopy revealed the aliphatic backbone to be preferentially upright oriented with the aromatic head group being not preferentially oriented. The palladium layer was further coordinated with a CF3-labeled terpyridine ligand in order to prove the accessibility of the Pd(II) ions to further complexation and the platform useful for deposition of further layers toward a multi-layered system.
We investigated the ageing of amine-terminated
self-assembled monolayers (amine-SAMs) on different silica
substrates due to exposure to different ambient gases,
pressures, and/or temperatures using time-of-flight secondary
ion mass spectrometry (ToF-SIMS) with principal component
analysis and complementary methods of surface
analysis as X-ray photoelectron spectroscopy (XPS) and
near edge X-ray absorption fine structure (NEXAFS). The
goal of this study is to examine the durability of primary
amine groups of amine-SAMs stored in a user laboratory
prior to being used as supports for biomolecule immobilization
and other applications. We prepared amine-SAMs on
the native oxides of silicon wafers and glass slides using 3-
aminopropyl triethoxysilane, by using optimized conditions
such as anhydrous organic solvent and reaction time scale of
hours to avoid multilayer growth. Selected commercial
amine-SAM slides have been investigated, too. When the
amine-SAMs are exposed to air, oxygen incorporation
occurs, followed by formation of amide groups. The formation
of oxygen species due to ageing was proved by ToFSIMS,
XPS, and NEXAFS findings such as CNO- secondary
ion emission at m/z 42, observation of the N 1s HNC=O
component peak at 400.2400.3 eV in XPS, and, last but not
least, by formation of a π*(HNC=O) resonance at 401 eV in
the N K-edge X-ray absorption spectrum. It is concluded
that the used multi-method approach comprising complementary
ToF-SIMS, XPS, and NEXAFS analyses is well
suited for a thorough study of chemical aspects of ageing
phenomena of amine-SAM surfaces.
A combined XPS, NEXAFS, and ToF-SIMS chemical surface characterization of carbohydrate-functionalized gold and glass surfaces is presented. Spot shape and chemical composition across a spot surface are provided by surface-sensitive methods as ToF-SIMS and XPS, used in their imaging modes. Moreover, the feasibility of this multimethod approach to control relevant production steps of a carbohydrate microarray prototype is demonstrated.
Carbohydrate films on gold based on dimannoside thiols (DMT) were prepared, and a complementary surface chemical analysis was performed in detail by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), near-edge X-ray absorption fine structure (NEXAFS), FT-IR, and contact angle measurements in order to verify formation of ω-carbohydrate-functionalized alkylthiol films. XPS (C 1s, O 1s, and S 2p) reveals information on carbohydrate specific alkoxy (C–O) and acetal moieties (O–C–O) as well as thiolate species attached to gold. Angle-resolved synchrotron XPS was used for chemical speciation at ultimate surface sensitivity. Angle-resolved XPS analysis suggests the presence of an excess top layer composed of unbound sulfur components combined with alkyl moieties. Further support for DMT attachment on Au is given by ToF-SIMS and FT-IR analysis. Carbon and oxygen K-edge NEXAFS spectra were interpreted by applying the building block model supported by comparison to data of 1-undecanethiol, poly(vinyl alcohol), and polyoxymethylene. No linear dichroism effect was observed in the angle-resolved C K-edge NEXAFS.
ToF-SIMS has been used to study the surface functionalization of polypropylene and polyethylene samples by exposure to low-pressure ammonia plasma. Static secondary ion mass spectrometry is an appropriate tool to determine hydrogen isotopes as elements and in fragment ions with high sensitivity and selectivity. Specifically the exchange of hydrogen isotopes and the incorporation of N-containing moieties in the near-surface layer of the polyolefins have been studied in ND3 plasma experiments with conventional polypropylene (h-PP) and polyethylene (h-PE) and NH3 plasma experiments with deuterated polyethylene (d-PE). Considering the exchange of hydrogen between the plasma and the polymer surface studied by using deuterated ammonia and polyolefin samples the conclusion has been derived that polypropylene with its side chain methyl groups is more susceptible to hydrogen exchange reactions. For ND3 plasma treatment of polyethylene and polypropylene similar N-containing fragments were obtained and the measured semi-quantitative ToF-SIMS N-uptake data are rather similar. The observation of a wide range of characteristic mixed CkNlHmDn+ secondary fragment ions suggests complex and manifold reaction pathways at the polymer–plasma interface besides simple grafting of –ND2 or –NH2 moieties formed by ammonia fragmentation in the plasma. Finally, indications of an isotopic effect for hydrogen isotopes in the plasma process have been observed by comparison of ND3/h-PE results with those of NH3/d-PE.
Microarrays are a versatile platform for diagnostics and high-throughput analysis. Carbohydrate microarrays are valuable tools to investigate interactions with other molecules since many glycans are involved in fundamental biological processes. A combined X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) surface analysis was used to investigate the basic steps in the production of carbohydrate microarrays. The preparation included coupling of a thiol-terminated mannoside to maleimide-functionalized glass surfaces derived from γ-aminopropyl silane (GAPS) slides. XPS results clearly demonstrate successful chemical modification in each fabrication step, and ToF-SIMS imaging revealed immobilized carbohydrates in the spotted regions of the final microarray.
Recently, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) instrumentation has been used to address areas of interest within micro-fluidic devices providing full access to the surface chemistry established at the bottom of micro-channels therein. After careful calibration, information on surface chemistry as obtained by ToF-SIMS or XPS can be interpreted in terms of wettability expressed as contact angles which are then characteristic for the inner walls of micro-channels. Standard contact angle measurement is not applicable in micro-channels. The approach has been demonstrated to be successful with two different micro-fluidic devices hot embossed into high-end quality poly(methyl methacrylate) (PMMA) or Polycarbonate wafers. A pre-selected surface chemistry at micro-channel walls can be established by plasma technologies but ageing and rinsing effects have to be under control. A combination of ToF-SIMS, XPS and contact angle measurement techniques has been demonstrated to provide the required information. Finally, it is shown by ToF-SIMS and XPS analysis that in the production of micro-fluidic parts during practical processing using hot embossing technologies, material originating from cover foils will reside on the polymer wafer's surface. Moreover, residues of releasing agents as silicone oil used during processing can be detected by ToF-SIMS. Both cover foil residues and silicones are issues of trouble shooting in micro-fluidics because they will change contact angles efficiently.
The chemical composition of the functional surfaces of substrates used for microarrays is one of the important parameters that determine the quality of a microarray experiment. In addition to the commonly used contact angle measurements to determine the wettability of functionalized supports, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are more specific methods to elucidate details about the chemical surface constitution. XPS yields information about the atomic composition of the surface, whereas from ToF-SIMS, information on the molecular species on the surface can be concluded. Applied on printed DNA microarrays, both techniques provide impressive chemical images down to the micrometer scale and can be utilized for label-free spot detection and characterization. Detailed information about the chemical constitution of single spots of microarrays can be obtained by high-resolution XPS imaging.
It is known that aminosilanized Si wafers may be used as microarray platforms. Results of an XPS study of a cleaning applied to Si wafers prior to aminosilanization are presented and discussed. Furthermore, the results of an aminosilanization protocol optimized in terms of nitrogen chemistry are described. After optimization of the protocol a free amine content of 94% was reached. The surface chemistry was investigated in this study by using XPS, time of flight (ToF)-SIMS and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Reference to aminosilanization protocols reported in the literature has been made.
A survey is given on how a combination of modern methods of surface analysis with appropriate data evaluation procedures can be used to provide a thorough chemical characterization of plasma polymerized organic films often called plasma polymers. Technologically relevant parameters can be monitored versus variation of plasma process parameters and during ageing of the films on air. The level of development of analytical approaches reached during the last ten years opens many options which are useful to be applied in plasma process development, optimization and control. However, in a number of important cases further development of analytical methods is required. Another future challenge is to develop standards with metrological underpinning to reach comparability of measurements in the community.
Translated Abstract
Chemische Oberflächencharakterisierung von Plasmapolymerschichten: Was leisten die Messverfahren heute?
Es wird ein Überblick gegeben, wie mit dem kombinierten Einsatz moderner Methoden der Oberflächenanalytik und fortgeschrittener Datenreduktionsverfahren eine umfassende chemische Charakterisierung von plasmachemisch abgeschiedenen organischen Schichten, oft als Plasmapolymere bezeichnet, erreicht werden kann. Die chemischen Eigenschaften sind bestimmend für wichtige technologische Parameter der Schichten und können sowohl durch Plasmaprozessparameter als auch von der Liegezeit bestimmt werden. Eine Standardisierung von Prozeduren der Oberflächenanalytik zur Charakterisierung von Plasmapolymeren und ihre metrologische Begründung sind Schwerpunkte in der weiteren Entwicklung.
The wettability of the surfaces inside the microchannels of a microfluidic device is an important property considering a liquid flows through them. Contact angle measurements usually applied to test the wettability of surfaces cannot be used for an analysis of microchannel walls within microfluidic devices. A workaround is the use of surface analytical methods, which are able to reach points of interest in microchannels and may provide information on the surface chemistry established there. In calibrating these methods by using flat polymer wafers, where the contact angle can be measured as usual, data measured in real microchannels can be evaluated in terms of wetting properties. Reference wafers of bisphenol-A polycarbonate, a polymeric material that is often used in fluidic microdevice fabrication, were treated under different oxygen plasma conditions. The modified surfaces were characterized by using XPS, time of flight (ToF)-SIMS and atomic force microscope (AFM). Surface chemistry and surface topography have been correlated with contact angle measurements. In addition, effects of ageing or rinsing after plasma treatment have also been investigated.
Imaging ToF-SIMS has been applied to characterize the surface chemistry variations across small areas produced by a DBD-type plasma printing technique on a BOPP substrate using pure nitrogen and a nitrogen-hydrogen gas mixture. CH4N+ and CNO- secondary ions are detected with high yields remote from the discharge region. They are discussed to be due to surface modifications of the substrate by metastable gas-phase species. On the other hand, surface species exist that are preferentially formed by reactions of the substrate with short-lived species which are only present close to the plasma discharge region. A C3H8O+ secondary fragment ion is assumed to be a key fragment of such a surface species.
Plasma deposited styrene/allyl alcohol and ethylene/allyl alcohol copolymer films were prepared and characterized using XPS, NEXAFS and ToF-SIMS. The relative partial flow rates of the co-monomers are used as deposition process parameters to vary and all other process parameters were constrained to conditions optimized for retention of functional groups. By doing this it is possible to control certain chemical properties of the copolymer films such as unsaturation, oxygen and hydroxyl group relative surface contents. The aging behavior of the plasma copolymer films on air was studied, too. Non-linear variations of relative oxygen contents, contents of C—OR species and contents of carbonyl species are obtained vs. variation of feed gas composition for both monomer combinations. The chemical character of the plasma copolymer films varies between the limits given by the respective plasma homopolymers. The observed non-linear correlations are discussed in terms of approaches developed for classic radical copolymerization. The aging behavior of the different plasma copolymers films depends on the feed gas composition. Principally these aging phenomena known from plasma polymer aging studies of that respective monomer which dominates the character of the plasma copolymer are observed.
The formation of plasma-deposited materials made from organic molecules is a technologically attractive way to obtain films with unique properties, e.g. adhesion, wettability, conductivity or selected chemical functionalization. A detailed chemical characterization of these films is a great challenge for the analyst because of the co-existence of a large number of chemical species in plasma-deposited films. We investigated these types of organic films using photoelectron spectroscopy for chemical analysis (ESCA, XPS), near edge X-ray absorption fine structure (NEXAFS) spectroscopy at synchrotron radiation source BESSY II and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). A dedicated plasma preparation chamber was designed and added to the main analysis chamber of the respective spectrometers. This approach offers the possibility of studying plasma-deposited films without exposure to air before analysis (often called in-situ analysis) and the influence of post-plasma reactions, i.e. the ageing process. The present investigations are aimed at finding correlations between basic chemical properties of the deposited films and the plasma deposition parameters, e.g. duty cycle in pulsed plasmas and the power of discharge.
Static ToF-SIMS analysis of plasma chemically deposited ethylene/allyl alcohol co-polymer films
(2006)
A plasma co-polymerization of ethylene as a chain extending monomer and allyl alcohol as a carrier monomer for hydroxyl groups was studied. The composition of the feed gas was systematically varied and the plasma co-polymers were analyzed in terms of their relative concentrations of OH functional groups by static Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) immediately after their preparation without any air contact, i.e., under so called in situ conditions.
The relative OH group concentration involved in the CH2OH groups was derived from the normalized yields of the CH3O+ secondary fragment ion. The density of functional groups in the plasma co-polymers was found to vary non-linearly with respect to the mole percentage of the monomers in the feed gas.
Co-polymerization phenomena, i.e. chemical interactions and recombination reactions taking place between monomer molecules in the plasma and/or during the deposition process, become evident in ToF-SIMS spectra.
The effect of the composite plasma parameter P/F, where P is the plasma power and F is the monomer flow rate, on the chemical character of pulsed plasma deposited allyl alcohol films was investigated by ToF-SSIMS. Information on the unsaturated character, the cross-linked and/or branched character of the plasma polymer films was derived in detail. The problem of the retention of OH groups in plasma deposited allyl alcohol films was elucidated in detail using SSIMS data. The lowest conversion rate from the monomer's hydroxyl groups to other oxygen functionalities in the plasma was concluded for the plasma polymer film produced at a P/F ratio of 0.05 W · sccm-1. It was found that the overall oxygen content of the films decreased vs. increasing P/F ratio. Because the freshly prepared films were investigated without air exposure, ageing on ambient air could be studied in detail. It was found that in the case of plasma deposited allyl alcohol films the ageing on air is probably based on two competing processes which are discussed in detail. Additionally, a review of literature data on the characterization of plasma deposited allyl alcohol films is given.
Pulsed-plasma-deposited 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 ethylene films was investigated. From these data, information on the chemical character of the plasma-deposited ethylene films was derived. The investigation of the effect of external plasma parameters on the chemical character of the plasma-deposited ethylene films revealed that there were some drastic changes in the secondary ion mass spectra of the films. It was found that fragmentation and re-arrangement of the monomer molecules in the plasma, which affects the chemical character of the deposited films, vary according to the external plasma parameters. When the plasma polymers are exposed to air, extensive oxygen incorporation occurs. The oxygen uptake is high at the beginning and then it levels of. Some indications for the formation and decay of peroxy radicals (COO) and, subsequently, hydroperoxides (COOH) are found. It was observed that the oxygen uptake of the plasma deposited ethylene films increase when the plasma conditions become harder.
Depth profiling of electrically non-conductive layered samples by RF-GDOES and HFM plasma SNMS
(2001)
The work is intended to compare the capabilities of two similar depth profiling techniques to analyse electrically non-conductive samples. In order to get a better evaluation of the depth resolution, various multilayer sandwiches, such as SiO2/TiO2 and Si3N4/SiO2 deposited on glass substrates have been investigated. Optimised depth profiles are presented for both methods, glow discharge optical emission spectrometry (GDOES) and radiofrequency mode (known as HFM in the SNMS literature) of plasma secondary neutral mass spectrometry (SNMS). The optimisation procedure, necessary to get the best set of plasma parameters, which result in the optimal depth resolution, is also described for one selected sample. Additionally, sputtering crater profilometry was carried out in order to check out the flatness of the sputtered crater. The influence of the thickness of the sample substrate on the sputtering rate is discussed. Finally, advantages and disadvantages of the use of these two depth profiling methods, especially for the non-conductive samples, are concluded from this comparative study. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of a cross-sectioned sample was carried out in order to get supplementary information.