Phase Behavior and dewetting for polymer blend films studied by in situ AFM and XPS: From thin to ultrathin films

In this work, the film thickness (l(0)) effect on the phase and dewetting behaviors of the blend film of poly(methyl methacrylate)/poly (styrene-ran-acrylonitrile) (PMMA/SAN) has been studied by in situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The thinner film shows the more compatibility of the blend, and the phase separation of the film occurs at l(0) > 5R(g) (radius of gyration). An initially time-independent q*, the characteristic wavenumber of the phase image, which is in good agreement of Cahn's linearized theory for the early stage of spinodal decomposition, has been obtained in real space and discussed in detail. For 5R(g) > l(0) > 3R(g), a "pseudo-dewetting/(phase separation + wetting)" behavior occurs, where the pseudo-wetting is driven by the concentration fluctuation mechanism. For 10 < 3R(g), a "real dewetting/(phase separation + wetting)" behavior occurs.

IN-SITU AFM STUDY OF THE SURFACE-MORPHOLOGY OF POLYPYRROLE FILM

In this paper we focus on the surface morphology of polypyrrole film by using in situ atomic force microscopy (AFM). The formation process of polypyrrole film and the transformation process of the film from the oxidized to reduced state were clearly observed.

In situ study of nanostructure and morphological development during the crystal-mesophase transition of poly(di-n-hexylsilane) and poly(di-n-butylsilane) by X-ray and hot-stage AFM

Nanostructure and morphology and their development of poly(di-n-hexylsilane) (PDHS) and poly(di-n-butylsilane) (PDBS) during the crystal-mesophase transition are investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction and hot-stage atomic force microscopy. At room temperature, PDHS consists of stacks of lamellae separated by mesophase layers, which can be well accounted using an ideal two-phase model. During the crystal-mesophase transition, obvious morphological changes are observed due to the marked changes in main chain conformation and intermolecular distances between crystalline phase and mesophase. In contrast to PDHS, the lamellae in PDBS barely show anisotropy in dimensions at room temperature. The nonperiodic structure and rather small electronic density fluctuation in PDBS lead to the much weak SAXS. The nonperiodic structure is preserved during the crystal-mesophase transition because of the similarity of main chain conformation and intermolecular distances between crystalline phase and mesophase.

In situ evaluation of anticancer drug methotrexate-DNA interaction using a DNA-electrochemical biosensor and AFM characterization

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Characterization of resistivity of Sb2S3 semiconductor nanowires by conductive AFM and in-situ methods

Conductive AFM and in situ methods were used to determine contact resistance and resistivity of individual Sb2S3 nanowires. Nanowires were deposited on oxidized Si surface for in situ measurements and on Si surface with macroelectrodes for conductive AFM (C-AFM) measurements. Contact resistance was determined by measurement of I(V) characteristics at different distances from the nanowire contact with the macroelectrode and resistivity of nanowires was determined. Sb2S3 is a soft material with low adhesion force to the surface and therefore special precautions were taken during measurements.

Graphene-type sheets of Nb1-xWxS2 : synthesis and in situ functionalization

Enlightened by the discovery of graphenes, a variety of inorganic analogues have been synthesized and characterized in recent years. Solvated Nb1-xWxS2 analogues of graphene-type sheets were prepared by lithiation and exfoliation of multistacked Nb1-xWxS2 coin roll nanowires (CRNWs), followed by in situ functionalization with gold nanoparticles to synthesize gold-loaded Nb1-xWxS2/Au nanocomposites. The Nb1-xWxS2 nanosheets and the corresponding Nb1-xWxS2/Au nanocomposites were characterized by high resolution electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and scanning force microscopy (AFM). The graphene-type sheets are stable in water and other solvents and can be functionalized similarly as chalcogen-terminated surfaces (e.g. with Au nanoparticles).

Electrochemical Reduction of Oriented Graphene Oxide Films: An in Situ Raman Spectroelectrochemical Study

Graphene oxide (GO) is assembled on a gold substrate by a layer-by-layer technique using a self-assembled cystamine monolayer. The negatively charged GO platelets are attached to the positively charged cystamine monolayer through electrostatic interactions. Subsequently, it is shown that the GO can be reduced electrochemically using applied DC bias by scanning the potential from 0 to -1 V vs a saturated calomel electrode in an aqueous electrolyte. The GO and reduced graphene oxide (RGO) are characterized by Raman spectroscopy and atomic force microscopy (AFM). A clear shift of the G band from 1610 cm-1 of GO to 1585 cm-1 of RGO is observed. The electrochemical reduction is followed in situ by micro Raman spectroscopy by carrying out Raman spectroscopic studies during the application of DC bias. The GO and RGO films have been characterized by conductive AFM that shows an increase in the current flow by at least 3 orders of magnitude after reduction. The electrochemical method of reducing GO may open up another way of controlling the reduction of GO and the extent of reduction to obtain highly conducting graphene on electrode materials.

Effect of in situ thermal treatment during growth on crystal quality of GaN epilayer grown on sapphire substrate by MOVPE

GaN epilayers on sapphire substrate grown by metalorganic vapor-phase epitaxy (MOVPE) in a horizontal-type low-pressure two-channel reactor were investigated. Samples were characterized by X-ray diffraction (XRD), Raman scattering, atomic force microscopy (AFM) and photoluminescence (PL) measurements. The influence of the temperature changes between low temperature (LT) deposited GaN buffer and high temperature (WT) grown GaN epilayer on crystal quality of epilayer was extensively studied. The effect of in situ thermal annealing during the growth on improving the GaN layer crystal quality was demonstrated and the possible mechanism involved in such a growth process was discussed. (C) 2001 Elsevier Science B.V. All rights reserved.

A systematic study of carbon fibre surface grafting via in situ diazonium generation for improved interfacial shear strength in epoxy matrix composites

A recently established means of surface functionalization of unsized carbon fibres for enhanced compatibility with epoxy resins was optimised and evaluated using interfacial shear stress measurements. Interfacial adhesion has a strong influence on the bulk mechanical properties of composite materials. In this work we report on the optimisation of our aryl diazo-grafting methodology via a series of reagent concentration studies. The fibres functionalised at each concentration are characterised physically (tensile strength, modulus, coefficient of friction, and via AFM), and chemically (XPS). The interfacial shear strength (IFSS) of all treated fibres was determined via the single fibre fragmentation test, using the Kelly-Tyson model. Large increases in IFSS for all concentrations (28-47%) relative to control fibres were observed. We show that halving the reagent concentration increased the coefficient of friction of the fibre and the interfacial shear strength of the composite while resulting in no loss of the key performance characteristics in the treated fibre.

A highly conductive porous graphene electrode prepared via in situ reduction of graphene oxide using Cu nanoparticles for the fabrication of high performance supercapacitors

Herein, a new graphene/Cu nanoparticle composite was prepared via the in situ reduction of GO in the presence of Cu nanoparticles which was then utilized as a sacrificing template for the formation of flexible and porous graphene capacitor electrodes by the dissolution of the intercalated Cu nanoparticle in a mixed solution of FeCl<inf>3inf> and HCl. The porous RGO electrode was characterized by atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The as-prepared graphene/Cu nanoparticle composite and the pure graphene film after removal of Cu nanoparticles possessed high conductivity of 3.1 × 10³ S m^-1 and 436 S m^-1 respectively. The porous RGO can be used as the electrode for the fabrication of supercapacitors with high gravimetric specific capacitances up to 146 F g^-1, good rate capability and satisfactory electrochemical stability. This environmentally friendly and efficient approach to fabricating porous graphene nanostructures could have enormous potential applications in the field of energy storage and nanotechnology.

Study of the growth process of in situ polyaniline deposited films

Polyaniline (PAni) thin films were deposited onto BK7 glass substrates using the in situ deposition technique. The control of the time and the aniline concentration in the PAni polymerization reaction on the film deposition allowed us to prepare films with different thickness, down to similar to 25 nm. The film growth process was monitored by measuring the UV-vis spectra and the AFM height profiles of the film surface. The curves of adsorption kinetics were analyzed with the Avrami's model, yielding an exponent it n = 3, thus indicating nucleation of spheroids at the initial stages of polymerization that grow through a diffusion process. AFM images of the surface height profiles corroborate this hypothesis, with spheroids growing with no preferred orientation during the in situ deposition. (C) 2007 Elsevier B.V. All rights reserved.

Nano- and macroscale structural and mechanical properties of in situ synthesized bacterial cellulose/PEO-b-PPO-b-PEO biocomposites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

In-situ-Präparation von komplexen supraleitenden und ferroelektrischen Heterostrukturen mittels gepulster Laser-Deposition

In der vorliegenden Arbeit ist die Konstruktion und der Aufbau eines Systems zur gepulsten Laserablation von dünnen Schichten beschrieben. Die hohe Flexibilität der Anlage wird ermöglicht durch einen sechsfach-Targethalter und eine Heizerkonstruktion, die einfachen Substrateinbau, hohe Temperaturhomogenität und einen zugänglichen Temperaturbereich von bis zu 1000°C erlaubt. Durch eine komplexe Laser-Optik, die eine homogene Energiedichte auf dem Target sicherstellt, wird eine optimale Filmqualität erreicht.Durch die Entwicklung einer zweistufigen Prozeßführung für Y-stabilisiertes ZrO2 wird eine Wachstumsbasis hoher kristalliner Qualität für funktionale Oxidschichten auf Silizium zur Verfügung gestellt. Es zeigt sich, daß die dielektrischen Eigenschaften der YSZ Schicht stark vom Sauerstoffgehalt, der Grenzflächenmorphologie sowie der Dicke der ersten Schicht abhängig sind. Basierend auf dieser Schicht wurde BaZrO3 als zusätzliche Pufferschicht für den Hochtemperatursupraleiter (HTSL) YBa2Cu3O7 ? untersucht. Unter Verwendung von SrTiO3 Substraten konnte die dielektrische Konstante von BaZrO3 zu ? ? 65 bestimmt sowie das Dispersionsverhalten mittels modifizierter Debye-Gleichungen erklärt werden. Vergleichende Messungen auf einkristallinen SrTiO3 Substraten zeigen eine erhöhte Übergangstemperatur von 90.2 K und eine wesentliche Verbesserung der Oberflächenrauhigkeit des HTSL von 2 nm (rms) durch die Verwendung von BaZrO3 Schichten hoher Qualität. Eine nur wenige Monolagen dicke zusätzliche BaZrO3 Pufferschicht auf YSZ-gepufferten Silizium Substraten verhindert die Ausbildung von ?9° rotierten YBCO Körnern, die üblicherweise bei der direkten Deposition auf YSZ beobachtet werden. Resistive Messungen mit Übergangstemperaturen oberhalb 89 K sind vergleichbar zu Ergebnissen, die für CeO2/YSZ Pufferschichtkombinationen erreicht werden. Durch kontinuierliche Gitteranpassung wurde eine neue Schichtabfolge YBCO/CeO2/YSZ/BaZrO3 für die Erzeugung bi-epitaxialer Korngrenzen-Josephson Kontake gefunden und deren Epitaxiebeziehungen geklärt. Eine in-situ deponierte Schichtabfolge zeigt mit einer Übergangstemperatur von 91.7 K und einer Übergangsbreite von 0.15 K supraleitende Eigenschaften vergleichbar zu den besten bisher auf diesem Gebiet erreichten Ergebnissen. Voruntersuchungen zur Realisierung eines Josephsonkontaktes mit dieser Schichtabfolge zeigen jedoch, daß die erreichten Eigenschaften für die technologische Anwendung nicht ausreichend sind.Die Verwendung einer YSZ/CeO2 Pufferschichtkombination ermöglicht die Herstellung von c Achsen orientiertem ferroelektrischem SrBi2Ta2O9 auf Silizium. Im Gegensatz hierzu führt die direkte Deposition auf Silizium zu polykristallinem SrBi2Ta2O9 oder zur Ausbildung der Pyrochlor Phase, wenn nur YSZ als Pufferschicht verwendet wird. Obwohl die Polarisierung von SrBi2Ta2O9 in der ab-Ebene liegt, konnte in MFIS Strukturen ein Speicherfenster von maximal 0.87 V beobachtet werden, was eine Verbesserung um nahezu einen Faktor drei im Vergleich zu polykristallinem SrBi2Ta2O9 bedeutet. Messungen an ferroelektrischen Kondesatorstrukturen ergeben Hystereseschleifen mit einer remanenten Polarisierung von Pr = 6.5 µC/cm2 sowie einem Koerzitivfeld von Ec = 35 kV/cm. AFM Messungen im Piezo-Response Modus zeigen ferroelektrische Domänen, die durch Anlegen einer Gleichspannung reversibel umpolarisiert werden können. Im Nicht-Kontakt AFM Modus wurde die lokale Polarisierung der Schichten zu 3.4 µC/cm2 bestimmt. Weiterhin wurde eine alternative Pufferschichtkombination SrZrO3/YSZ zur Erzeugung von a-Achsen orientiertem SrBi2Ta2O9 untersucht. SrZrO3 zeigt a Achsen Orientierung in vier Wachstumsdomänen, die durch ein Model erklärt werden können. Die SrBi2Ta2O9 Schicht zeigt a Achsen sowie (116)-orientierte Körner mit derselben Domänenstruktur. Die dielektrische Konstanten von SrZrO3 und SrBi2Ta2O9 wurden zu ? ? 29 und ? ? 20 bestimmt. Die beobachteten Speicherfenster sind allerdings nicht ferroelektrischer Natur, sondern wahrscheinlich durch mobile Ionen und Ladungsfangstellen in den Pufferschichten verursacht. Die stark abgesenkte dielektrische Konstante von SrBi2Ta2O9 kann durch die im Vergleich zu polykristallinem verkleinerte Korngröße erklärt werden.