Inkless microcontact printing on SAMs of Boc- and TBS-protected thiols.

We report a new inkless catalytic muCP technique that achieves accurate, fast, and complete pattern reproduction on SAMs of Boc- and TBS-protected thiols immobilized on gold using a polyurethane-acrylate stamp functionalized with covalently bound sulfonic acids. Pattern transfer is complete at room temperature just after one minute of contact and renders sub-200 nm size structures of chemically differentiated SAMs.

Photoelectrocatalysis: Principles, nanoemitter applications and routes to bio-inspired systems

An overview on processes that are relevant in light-induced fuel generation, such as water photoelectrolysis or carbon dioxide reduction, is given. Considered processes encompass the photophysics of light absorption, excitation energy transfer to catalytically active sites and interfacial reactions at the catalyst/solution phase boundary. The two major routes envisaged for realization of photoelectrocatalytic systems, e.g. bio-inspired single photon catalysis and multiple photon inorganic or hybrid tandem cells, are outlined. For development of efficient tandem cell structures that are based on non-oxidic semiconductors, stabilization strategies are presented. Physical surface passivation is described using the recently introduced nanoemitter concept which is also applicable in photovoltaic (solid state or electrochemical) solar cells and first results with p-Si and p-InP thin films are presented. Solar-to-hydrogen efficiencies reach 12.1% for homoepitaxial InP thin films covered with Rh nanoislands. In the pursuit to develop biologically inspired systems, enzyme adsorption onto electrochemically nanostructured silicon surfaces is presented and tapping mode atomic force microscopy images of heterodimeric enzymes are shown. An outlook towards future envisaged systems is given. © 2010 The Royal Society of Chemistry.

Nanotopography-induced changes in focal adhesions, cytoskeletal organization, and mechanical properties of human mesenchymal stem cells.

The growth of stem cells can be modulated by physical factors such as extracellular matrix nanotopography. We hypothesize that nanotopography modulates cell behavior by changing the integrin clustering and focal adhesion (FA) assembly, leading to changes in cytoskeletal organization and cell mechanical properties. Human mesenchymal stem cells (hMSCs) cultured on 350 nm gratings of tissue-culture polystyrene (TCPS) and polydimethylsiloxane (PDMS) showed decreased expression of integrin subunits alpha2, alpha , alpha V, beta2, beta 3 and beta 4 compared to the unpatterned controls. On gratings, the elongated hMSCs exhibited an aligned actin cytoskeleton, while on unpatterned controls, spreading cells showed a random but denser actin cytoskeleton network. Expression of cytoskeleton and FA components was also altered by the nanotopography as reflected in the mechanical properties measured by atomic force microscopy (AFM) indentation. On the rigid TCPS, hMSCs on gratings exhibited lower instantaneous and equilibrium Young's moduli and apparent viscosity. On the softer PDMS, the effects of nanotopography were not significant. However, hMSCs cultured on PDMS showed lower cell mechanical properties than those on TCPS, regardless of topography. These suggest that both nanotopography and substrate stiffness could be important in determining mechanical properties, while nanotopography may be more dominant in determining the organization of the cytoskeleton and FAs.

Diameter-selective solubilization of carbon nanotubes by lipid micelles

The one-step dispersion of HiPco single-walled carbon nanotubes in aqueous media with the use of a synthetic lyso-phosphatidylcholine was studied. Solubilization occurs through wrapping of lipid molecules around the circumference of the tubes, yielding lipid monolayers on the graphitic sidewalls as evidenced by atomic force microscopy imaging and dynamic light scattering measurements. Raman spectroscopy showed that the dispersion and centrifugation process leads to an effective enrichment of the stable aqueous suspension in carbon nanostructures with smaller diameters.

Delamination of oil paints from acrylic grounds

Many modern artists paint in oil or oil-modified alkyd paints over acrylic grounds. In some cases the oil based paints do not remain adhered to the ground. In a set of composite samples of oil or alkyd paints, over acrylic grounds, naturally aged for nine years, some of the samples delaminated. Samples were analyzed with X-ray fluorescence (XRF), inductively coupled plasma (ICP), Fourier transform infrared - attenuated total reflectance (FTIR-ATR), scanning electron microscopy (SEM), pyrolysis gas-chromatography mass-spectrometry (PY-GC/MS), laser desorption/ionization mass-spectrometry (LDI-MS), atomic force microscopy (AFM) and other methods, in order to find what the delaminating ones have in common. In addition, two examples of severely delaminating paintings were examined, to confirm the results from the laboratory-prepared samples. Results indicate the main cause of delamination is metal soaps in the oil paint and particularly zinc soaps. There is some evidence that metal soaps were more concentrated at the interface between the layers and this disrupted the adhesion. The ground is a minor consideration as well, rougher grounds providing better adhesion than smooth ones.

Relationship between biomedical catheter surface properties and lubricity as determined using textural analysis and multiple regression analysis

In this study, the surface properties of and work required to remove 12 commercially available and developmental catheters from a model biological medium (agar), a measure of catheter lubricity, were characterised and the relationships between these properties were examined using multiple regression and correlation analysis. The work required for removal of catheter sections (7 cm) from a model biological medium (1% w/w agar) were examined using tensile analysis. The water wettability of the catheters were characterised using dynamic contact angle analysis, whereas surface roughness was determined using atomic force microscopy. Significant differences in the ease of removal were observed between the various catheters, with the silicone-based materials generally exhibiting the greatest ease of removal. Similarly, the catheters exhibited a range of advancing and receding contact angles that were dependent on the chemical nature of each catheter. Finally, whilst the microrugosities of the various catheters differed, no specific relationship to the chemical nature of the biomaterial was apparent. Using multiple regression analysis, the relationship between ease of removal, receding contact angle and surface roughness was defined as: Work done (N mm) 17.18 + 0.055 Rugosity (nm)-0.52 Receding contact angle (degrees) (r = 0.49). Interestingly, whilst the relationship between ease of removal and surface roughness was significant (r = 0.48, p = 0.0005), in which catheter lubricity increased as the surface roughness decreased, this was not the case with the relationship between ease of removal and receding contact angle (r = -0.18, p > 0.05). This study has therefore uniquely defined the contributions of each of these surface properties to catheter lubricity. Accordingly, in the design of urethral catheters. it is recommended that due consideration should be directed towards biomaterial surface roughness to ensure maximal ease of catheter removal. Furthermore, using the method described in this study, differences in the lubricity of the various catheters were observed that may be apparent in their clinical use. (C) 2003 Elsevier Ltd. All rights reserved.

Measurement and interpretation of the mid-infrared properties of single crystal and polycrystalline gold

The contribution of electron-phonon scattering and grain boundary scattering to the mid-IR (lambda = 3.392 mum) properties of An has been assessed by examining both bulk, single crystal samples-Au(1 1 1) and Au(1 1 0)-and thin film, polycrystalline An samples at 300 K and 100 K by means of surface plasmon polariton excitation. The investigation constitutes a stringent test for the in-vacuo Otto-configuration prism coupler used to perform the measurements, illustrating its strengths and limitations. Analysis of the optical response is guided by a physically based interpretation of the Drude model. Relative to the reference case of single crystal Au at 100 K (epsilon = - 568 + i17.5), raising the temperature to 300 K causes increased electron-phonon scattering that accounts for a reduction of similar to40 nm in the electron mean free path. Comparison of a polycrystalline sample to the reference case determines a mean free path due to grain boundary scattering of similar to 17 nm, corresponding to about half the mean grain size as determined from atomic force microscopy and indicating a high reflectance coefficient for the An grain boundaries. An analysis combining consideration of grain boundary scattering and the inclusion of a small percentage of voids in the polycrystalline film by means of an effective medium model indicates a value for the grain boundary reflection coefficient in the range 0.55-0.71. (C) 2005 Elsevier B.V. All rights reserved.

Exploring grain size as a cause for dead-layer effects in thin film capacitors

Pulsed laser deposition was used to make a series of Au/Ba0.5Sr0.5TiO3 (BST)/SrRuO3/MgO thin film capacitors with dielectric thickness ranging from similar to15 nm to similar to1 mum. Surface grain size of the dielectric was monitored as a function of thickness using both atomic force microscopy and transmission electron microscopy. Grain size data were considered in conjunction with low field dielectric constant measurements. It was observed that the grain size decreased with decreasing thickness in a manner similar to the dielectric constant. Simple models were developed in which a functionally inferior layer at the grain boundary was considered as responsible for the observed dielectric behavior. If a purely columnar microstructure was assumed, then constant thickness grain-boundary dead layers could indeed reproduce the series capacitor dielectric response observed, even though such layers would contribute electrically in parallel with unaffected bulk- like BST. Best fits indicated that the dead layers would have a relative dielectric constant similar to40, and thickness of the order of tens of nanometers. For microstructures that were not purely columnar, models did not reproduce the observed dielectric behavior well. However, cross-sectional transmission electron microscopy indicated columnar microstructure, suggesting that grain boundary dead layers should be considered seriously in the overall dead-layer debate. (C) 2002 American Institute of Physics.

Toward Self-Assembled Ferroelectric Random Access Memories: Hard-Wired Switching Capacitor Arrays with Almost Tb/in.2 Densities

We report on the successful fabrication of arrays of switchable nanocapacitors made by harnessing the self-assembly of materials. The structures are composed of arrays of 20-40 nm diameter Pt nanowires, spaced 50-100 nm apart, electrodeposited through nanoporous alumina onto a thin film lower electrode on a silicon wafer. A thin film ferroelectric (both barium titanate (BTO) and lead zirconium titanate (PZT)) has been deposited on top of the nanowire array, followed by the deposition of thin film upper electrodes. The PZT nanocapacitors exhibit hysteresis loops with substantial remnant polarizations, while although the switching performance was inferior, the low-field characteristics of the BTO nanocapacitors show dielectric behavior comparable to conventional thin film heterostructures. While registration is not sufficient for commercial RAM production, this is nevertheless an embryonic form of the highest density hard-wired FRAM capacitor array reported to date and compares favorably with atomic force microscopy read-write densities.

Creation of damage-free ferroelectric nanocapacitors via focused ion beam milling

We present a novel method for creating damage-free ferroelectric nanostructures with a focused ion beam milling machine. Using a standard e-beam photoresist followed by a dilute acid wash, nanostructures ranging in size from 1 mu m down to 250 nm were created in a 90 nm thick lead zirconate titanate ( PZT) wafer. Transmission electron microscopy and piezoresponse force microscopy ( PFM) confirmed that the surfaces of the nanostructures remained damage free during fabrication, and showed no gallium implantation, and that there was no degradation of ferroelectric properties. In fact DC strain loops, obtained using PFM, demonstrated that the nanostructures have a higher piezoresponse than unmilled films. As the samples did not have any top hard mask, the method presented is unique as it allows for imaging of the top surface to understand edge effects in well-defined nanostructures. In addition, as no post-mill annealing was necessary, it facilitates investigation of nanoscale domain mechanisms without process-induced artefacts.

Plasma chloriding of thin-film silver - A novel process in silver-silver chloride reference electrode fabrication

Silver thin films were modified using a novel plasma modification process for the development of thin-film silver-silver chloride reference electrodes. The surface, physical, and electrochemical properties of these electrodes were investigated by atomic force microscopy, thickness and resistivity measurement techniques, as well as impedance spectroscopy and potentiometry. After plasma treatment, thin-film growth was observed and the electrodes, in general, exhibited low interface impedance and a roughened surface. Evidence of a complex surface reorganization was found. Correlating plasma conditions with film properties suggested that increasing pressure and exposure duration increased species availability, therefore governing the reaction rates, while input power appeared to influence the type of surface chemical reactions. Results also indicated that Ar/Cl-2 mixtures should be employed rather than pure chlorine plasmas. (C) 2002 The Electrochemical Society.

Self-affine crossover length in a layered silicate deposit

Self-affine dehydrated colloidal deposits on fresh mica surfaces of the synthetic layered silicate 2:1 smectite clay laponite have been studied by means of atomic force microscopy (AFM). AFM images of these prepared assemblies of sol and gel aggregates have been analyzed both by means of standard AFM Fourier software and a wavelet method. The deposited surfaces show a persistence to antipersistent crossover with a clay concentration dependent crossover length. It is concluded that the crossover length is associated with aggregate size, and further that the persistent roughness at small length scales signals near compact clusters of fractal dimension three, whereas the antipersistent roughness at large length scales signals a sedimentation process.

Domain Bundle Boundaries in Single Crystal BaTiO3 Lamellae: Searching for Naturally Forming Dipole Flux-Closure / Quadrupole Chains

Naturally occurring boundaries between bundles of 90o stripe domains, which form in BaTiO3 lamellae on cooling through the Curie Temperature, have been characterised using both piezoresponse force microscopy (PFM) and scanning transmission electron microscopy (STEM). Detailed interpretation of the dipole configurations present at these boundaries (using data taken from PFM) shows that, in the vast majority of cases, they are composed of simple zigzag 180° domain walls. Topological information from STEM shows that, occasionally, domain bundle boundaries can support chains of dipole flux closure and quadrupole nanostructures, but these kinds of boundaries are comparatively rare; when such chains do exist, it is notable that singularities at the cores of the dipole structures are avoided. The symmetry of the boundary shows that diads and centres of inversion exist at positions where core singularities should have been expected.

Scaling of Superdomain Bands in Ferroelectric Dots

Bundles of 90° stripe domains have been observed to form into distinct groups, or bands, in mesoscale BaTiO3 single crystal dots. Vector piezoresponse force microscopy (PFM) shows that each band region, when considered as a single entity, possesses a resolved polarization that lies approximately along the pseudocubic direction; antiparallel alignment of this resultant polarization in adjacent bands means that these regions can be considered as 180° “superdomains.” For dots with sidewall dimensions below ~2 microns, Landau–Kittel like scaling in the width of these superdomains was observed, strongly suggesting that they form in response to lateral depolarizing fields. In larger dot structures, scaling laws break down. We have rationalized these observations by considering changes in the driving force for the adoption of equilibrium superdomain periodicities implied by Landau–Kittel-free energy models; we conclude that the formation of ordered bands of superdomains is a uniquely meso/nanoscale phenomenon. We also note that the superdomain bands found by PFM imaging in air contrast with the quadrant arrangements seen previously by Schilling et al. (Nano Lett., 9, 3359 (2009)) through transmission electron microscopy imaging in vacuum. The importance of the exact nature of the boundary conditions in determining the domain patterns that spontaneously form in nanostructures is therefore clearly implied.

Mesoscale flux-closure domain formation in single-crystal BaTiO3

Over 60 years ago, Charles Kittel predicted that quadrant domains should spontaneously form in small ferromagnetic platelets. He expected that the direction of magnetization within each quadrant should lie parallel to the platelet surface, minimizing demagnetizing fields, and that magnetic moments should be configured into an overall closed loop, or flux-closure arrangement. Although now a ubiquitous observation in ferromagnets, obvious flux-closure patterns have been somewhat elusive in ferroelectric materials. This is despite the analogous behaviour between these two ferroic subgroups and the recent prediction of dipole closure states by atomistic simulations research. Here we show Piezoresponse Force Microscopy images of mesoscopic dipole closure patterns in free-standing, single-crystal lamellae of BaTiO3. Formation of these patterns is a dynamical process resulting from system relaxation after the BaTiO3 has been poled with a uniform electric field. The flux-closure states are composed of shape conserving 90° stripe domains which minimize disclination stresses.