X-ray and neutron reflectometry for the investigation of polymer diffusion

Summary X-ray and neutron reflectometry are novel tools for the investigation of polymer interfaces. For this method we demonstrate the high resolution on the vertical length scale which is normally better than 1 nm and the ideal applicability for the analysis of polymer diffusion by showing both simulations and measurements. The limits and difficulties are discussed. We look at the broadening of the interface between two polystyrene films during interdiffusion slightly above the glass transition temperature. For short times we prove two distinct time regimes for polymer diffusion. This is achieved with a double layer system consisting of a deuterated and a protonated polystyrene film. The roughness of the individual films is well below 1 nm.     

Determination of boron by the neutron depth profile (NDP) technique for VLSI processing application

Borophosphosilicate glass (BPSG) has been used for its improved reflow properties compared to low temperature oxide (LTO) in planar technology. Thin films of BPSG were deposited by a low-pressure chemical vapor deposition process. The boron content was determined by NDP. In addition from the NDP spectrum the depth profile of boron and the thickness of the film were also determined. In the NDP technique, samples, typically silicon wafers with 500 nm thick BPSG film, were exposed to a highly-thermalized neutron beam. Generated by the¹⁰B(n,)⁷ Li reaction, isotropically emitted monoenergetic particles of 1.47 MeV were counted in an evacuated in-beam analysis setup. The energy loss of the -articles in the film was proportional to the depth at which the nuclear reaction took place. The energy spectrum of the -articles, therefore, was a direct result of the boron depth profile, and the area under the curve was a measure of the total number of boron atoms in the film. This unique nuclear technique provided an excellent method for optimizing the composition of the BPSG film for device processing.     

Experimental determination of the composition depth profile of AuCu alloys via auger electron spectroscopy

Three methods enabling the determination of the first two atomic layers composition of binary metallic alloys via Auger electron spectroscopy are described and discussed. In the first one, the low and high energy Auger peak heights (APHs) for the both components of an alloy are measured which gives information on the composition of the superficial layer and the deeper one, respectively. In the second method, the ratios of different energy APHs for one component of an alloy are measured and fitted to those calculated for particular compositions of the first and second atomic layer and the bulk. In the third method, the ratio of the low energy APHs for both components of the alloy with the known bulk composition is measured with a retarding field analyzer for the incidence angle of the primary electron beam equal to 0 ° and 60 °. This ratio is fitted to the ratios calculated for both incidence angles and for particular compositions of the first and second atomic layers. Results for Au_xCu_1-x alloys, with x ranging from 0.1 to 0.9, obtained from both the above methods and the low energy ion scattering are collected in the paper. A comparison is also made with the theoretical predictions, based on the Monte Carlo simulations for the (001) and (111) terminated crystals of AuCu₃ and AuCu. A reasonable qualitative agreement between the experiment and theory is shown.     

Deuteration of molecules for neutron reflectometry on organic light-emitting diode thin films

Deuterated forms of aromatic charge transporting heterocycles 2 and 3 used in organic light-emitting diodes have been produced by hydrothermal reactions, catalyzed by Pt/C or Pd/C. Comprehensive analysis by mass spectroscopy, ¹H, ²H and ¹³C NMR enables determination of the overall quantity of D atoms present, as well as the level of deuteration at each molecular site. The roles of solubility and steric availability in deuteration are discussed in the light of these results. Neutron reflectometry indicates excellent scattering contrast between protonated and deuterated forms of these molecules, with nanoscale thin films showing the same density as in their bulk molecular forms. Although used for morphological studies of thin films typically used in OLEDs, the synthetic and analysis methods described here are generic and suitable for deuteration of other conjugated aromatic heterocycles and other optoelectronic devices.     

DNA as supramolecular scaffold for porphyrin arrays on the nanometer scale

Tetraphenyl porphyrin substituted deoxyuridine was used as a building block to create discrete multiporphyrin arrays via site specific incorporation into DNA. The successful covalent attachment of up to 11 tetraphenyl porphyrins in a row onto DNA shows that there is virtually no limitation in the amount of substituents, and the porphyrin arrays thus obtained reach the nanometer scale (approximately 10 nm). The porphyrin substituents are located in the major groove of the dsDNA and destabilize the duplex by deltaT(m) 5-7 degrees C per porphyrin modification. Force-field structure minimization shows that the porphyrins are either in-line with the groove in isolated modifications or aligned parallel to the nucleobases in adjacent modifications. The CD signals of the porphyrins are dominated by a negative peak arising from the intrinsic properties of the building block. In the single strands, the porphyrins induce stabilization of a secondary helical structure which is confined to the porphyrin modified part. This arrangement can be reproduced by force-field minimization and reveals an elongated helical arrangement compared to the double helix of the porphyrin-DNA. This secondary structure is disrupted above approximately 55 degrees C (T(p)) which is shown by various melting experiments. Both absorption and emission spectroscopy disclose electronic interactions between the porphyrin units upon stacking along the outer rim of the DNA leading to a broadening of the absorbance and a quenching of the emission. The single-stranded and double-stranded form show different spectroscopic properties due to the different arrangement of the porphyrins. Above T(p) the electronic properties (absorption and emission) of the porphyrins change compared to room temperature measurements due to the disruption of the porphyrin stacking at high temperature. The covalent attachment of porphyrins to DNA is therefore a suitable way of creating helical stacks of porphyrins on the nanometer scale.     

Atomic force microscopy imaging of hair: correlations between surface potential and wetting at the nanometer scale

We report investigations of hair surface potential under wetting at the nanometric scale by atomic force microscopy (AFM). Surface potential imaging was used to characterize the electrostatic properties of the hair samples. We found that the surface potential noticeably increases along the edges of the cuticles. These results are correlated with wetting behavior of different liquids performed using AFM in noncontact mode.     

High-throughput screening for combinatorial thin-film library of thermoelectric materials

A high-throughput method has been developed to evaluate the Seebeck coefficient and electrical resistivity of combinatorial thin-film libraries of thermoelectric materials from room temperature to 673 K. Thin-film samples several millimeters in size were deposited on an integrated Al2O3 substrate with embedded lead wires and local heaters for measurement of the thermopower under a controlled temperature gradient. An infrared camera was used for real-time observation of the temperature difference Delta T between two electrical contacts on the sample to obtain the Seebeck coefficient. The Seebeck coefficient and electrical resistivity of constantan thin films were shown to be almost identical to standard data for bulk constantan. High-throughput screening was demonstrated for a thermoelectric Mg-Si-Ge combinatorial library.     

Instrumental neutron activation analysis applied to the determination of the chemical composition of metallic materials with study of interferences

Summary Instrumental neutron activation analysis was applied to evaluate the chemical composition of metallic materials, namely iron, steel, silicon and ferrosilicon certified reference materials. As, Co, Cr, Mn, Mo, Ni, V and W concentrations were analyzed in the iron and steel samples whereas 21 elements were determined in silicon and ferrosilicon samples. Accuracy and precision results of about 10% were achieved for most elements, indicating that the technique is suitable for the analysis of metallic materials. Interferences of Cr and Mn in V; Fe and Co in Mn; Co in Fe and Cr in Ti were quantified and only the last one was critical to the analysis of the materials employed in this work.     

A complex neutron activation method for the analysis of biological materials

The aim of the present work was to deal primarily with a few essential trace elements and to obtain reliable results of adequate accuracy and precision for the analysis of biological samples. A few other than trace elements were determined by the nondestructive technique as they can be well evaluated from the gamma-spectra. In the development of the method BOWEN's kale was chosen as model material. To confirm the reliability of the method two samples were analysed proposed by the IAEA in the frame of an international comparative analysis series. The comparative analysis shows the present method to be reliable, the precision and accuracy are good.     

Applications of neutron induced particle tracks for materials analysis

Thermal neutrons are captured by several elements which emit charged particles as reaction products. These particles leave etchable damage tracks in detector materials placed against a sample, creating a map of the distribution and concentration of the target element. The most common applications are for U using fission tracks and B using alpha tracks. Distributions of Li, N and possibly S and O can also be mapped. Applications discussed here include B in metals and coatings, Li in Al, N in polymers and nitrided glasses and U in contact with O-ring seals. Detection limits are better than 1·10^–11 g/g U, 1·10^–9 g/g for B, 1·10^–6 g/g for Li and 0.1 wt.% for N. Spatial resolution for mapping is about 25 m.This work performed at Sandia National Laboratories supported by the U.S. Department of Energy under contract number DE-AC-04-76P00789.     

Advancement of light-element neutron depth profiling at the University of Texas

The University of Texas (UT) at Austin has collaborated with the National Institute of Standards and Technology for comparisons of concentration versus depth profiles of samples containing ¹⁰B. Technology sharing from NIST has allowed UT to avoid many initial set backs such that significant advancements in the UT-NDP facility’s experimental and analytical methodology have been achieved. UT has analyzed two samples loaned to them from NIST. The collaborative effort between the two institutions has given the UT-NDP facility the proper tools to begin profiling more advanced samples in hopes of meeting the capabilities set by NIST in the NDP field. The UT-NDP facility was able to profile a borosilicate surface deposit onto silicon such that the concentrations of ¹⁰B at various depths of the deposit were determined and fit well to a Pearson distribution.     

SIMS depth profile analysis for investigations of the lithium-diffusion in hydrogenated amorphous silicon

Summary SIMS depth profiling, using an oxygen primary beam at close to normal incidence, was applied to study lithium diffusion in thin films of hydrogenated amorphous silicon (a-Si:H) as well as in layered structures of doped and undoped silicon-based alloys. A strongly increasing decay length of the lithium profiles was observed for increasing primary beam energies and is attributed to the Li accumulation at the SiO_x/Si interface. The stability of the lithium incorporation in a-Si:H is found to depend on the presence of charged acceptors or defects and of doping gradient related electrical fields.     

Encoding of stoichiometric constraints in the composition depth profile reconstruction from angle resolved X‐ray photoelectron spectroscopy data

The inversion of angle resolved XPS data is a difficult problem, due to mathematical complexity of accurate model of electron transport, sensitivity to noise and small number of measured points limiting the depth resolution and the accuracy of the calculated depth profiles. Extended maximum entropy model for the calculation of apparent compositions (measured intensity ratios) is presented which allows to encode linear relationship between element concentrations. These can be used to calculate a solution with additional stoichiometric relationships and analyze, simultaneously, signals from several synthetic peak components. The synthetic peak components used in the model can represent various core level energy shifts, which are otherwise difficult to determine unambiguously from the measured signal. Element concentrations linked with stoichiometric relationships are used to identify compound materials with known density and inelastic scattering properties. The new model, thus allows self‐consistent recovery of depth profiles using maximum entropy method without the assumption of homogeneous density. The improved accuracy of the recovered depth profiles is demonstrated on the analysis of HfON/SiON overlayers. Various artefacts in the depth profiles obtained with standard maximum entropy model, which assumes constants density are identified. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface tailoring for controlled protein adsorption: effect of topography at the nanometer scale and chemistry

Protein adsorption behavior is at the heart of many of today's research fields including biotechnology and materials science. With understanding of protein-surface interactions, control over the conformation and orientation of immobilized species may ultimately allow tailor-made surfaces to be generated. In this contribution protein-surface interactions have been examined with particular focus on surface curvature with and without surface chemistry effects. Silica spheres with diameters in the range 15-165 nm with both hydrophilic and hydrophobic surface chemistries have been used as model substrates. Two proteins differing in size and shape, bovine serum albumin (BSA) and bovine fibrinogen (Fg), have been used in model studies of protein binding with detailed secondary structure analysis being performed using infrared spectroscopy (IR) on surface-bound proteins. Although trends in binding affinity and saturation values were similar for both proteins, albumin is increasingly less ordered on larger substrates, while fibrinogen, in contrast, loses secondary structure to a greater extent when adsorbing onto particles with high surface curvature. These effects are compounded by surface chemistry, with both proteins becoming more denatured on hydrophobic surfaces. Both surface chemistry and topography play key roles in determining the structure of the bound proteins. A model of the binding characteristics of these two proteins onto surfaces having differing curvature and chemistry is presented. We propose that properties of an adsorbed protein layer may be guided through careful consideration of surface structure, allowing the fabrication of materials/surface coatings with tailored bioactivity.     

Real-time monitoring of polymer swelling on the nanometer scale by atomic force microscopy

The swelling of a polymer surface has been monitored in real time on the nanometer scale by atomic force microscopy (AFM). After modification by oxygen plasma treatment, poly(p-phenylene terephthalamide) (PPTA) displays a characteristic nanostructured surface morphology consisting of high-lying features alternating with topographically depressed areas. Selective swelling of the least cross-linked, depressed areas after the adsorption of ambient water or water from saturated humid atmospheres was observed by tapping mode AFM operated in the attractive interaction regime. The swollen areas could be distinguished from the nonswollen ones by local variations in the sample indentation made by the AFM tip when imaging in the tapping mode repulsive interaction regime. Monitoring the swelling of the plasma-treated polymer surface provided a means to reveal the nanometer-scale heterogeneity that this type of treatment creates on the polymer surface, which is something that would not be possible otherwise. Measurement of AFM tip-sample adhesion forces evidenced rapid water adsorption onto the oxygen plasma-treated surface, supporting the idea of water-induced swelling. This high hydrophilicity was interpreted as arising from the incorporation of polar oxygen functionalities, as demonstrated by X-ray photoelectron spectroscopy (XPS).     

Multielement standards for instrumental neutron activation analysis of biological materials

Standards for instrumental neutron activation analysis (INAA) of biological materials are proposed. The standards are multielement solid solutions in phenol-formaldehyde resole resin (PFR) moulded as pellets weighing 30 to 50 mg. The concentrations of trace elements in the standards are selected so that, firstly, they are commensurable with their concentrations in the biological materials and, secondly, that the analytical lines of each of the elements incorporated in PFR are resolved with the aid of modern equipment. The principal standard contains 21 trace elements from among those of greatest interest for INAA of biological materials. This standard is recommended for work on high-resolution equipment. At the same time, standards of simpler trace element composition have been prepared and studied which can be used in work on simpler equipment or in solving particular problems in determination of certain groups of chemical elements.