Nanostructured surfaces and self-assembly of nanocolloidal filmsNanostructured surfaces and selfassembly of nanocolloidal films
Introduction Nanostructured surfaces, films with morphological features in the nanometer range and ordered assemblies of nanometer-sized particles are an interesting class of nanomaterials with great technological potential. Innovative application fields for these new materials include high-density information storage media, biological sensor arrays, magnetic fluids, medical diagnostics and catalysts. Compared to conventional surface science techniques, such as gas-phase synthesis and nanostructuring or deposition of nanoparticles under ultrahigh-vacuum condition, the soft-matter approach is a scientifically and economically interesting alternative. In this approach self-organisation in the bottomup formation of nanostructured interfaces in liquid environment and self-assembled deposition of nanoparticles from colloidal suspension play a predominant role. In this research theme, the emphasis is on identifying and gaining control over the relevant growth and/or ordering parameters during and after the formation of structured interfaces or the deposition of nanometer-sized entities. A prerequisite for investigating the formation process of nanostructured surfaces is the ability to accurately characterise the surfaces in situ during and ex situ after the manufacture of well-defined surfaces and interfaces. 1. Unambiguous optical characterisation of nanocolloidal films The standard approach in the analysis of the spectroscopic ellipsometry experiments is to describe the dielectric properties of a heterogeneous layer, such as an adsorbed layer of colloids, with an effective medium approximation (EMA). However, with continuously decreasing feature sizes into the low nanometer range, the commonly used EMAs, such as those established by Bruggeman and MaxwellGarnett do not give adequate results. The so-called thin film theory developed by Bedeaux and Vlieger gives an excellent quantitative description of the optical response of nanocolloidal layers. In this theory, the incorporation of image dipoles and laterally interacting entities is essential. A prerequisite for the description of the optical properties of the nanocolloidal film is the knowledge of the optical characteristics of a single entity. The limited size of the gold colloids results in a different polarizability than that of bulk gold.

utwente. which arises from surface charges on the particles. and can be adequately described by the random sequential adsorption (RSA) model. Consequently. Additionally. it is tuneable via the ionic strength.http://www. the deposition kinetics of nanocolloidal gold particles is investigated using single wavelength reflectometry in a stagnation point flow geometry. Adsorption of citrate-stabilised gold colloids from suspension leads to a random spatial distribution of isolated particles. . Ionic strength dependent deposition of gold nanocrystals Atomic force microscopy (AFM) and scanning electron microscopy (SEM) are used to characterise nanocolloidal gold films deposited on APTES-derivatised silicon/silicon oxide surfaces.doc/ 2. The minimum distance between neighbouring nanocrystals is related to the extent of their repulsive interaction in

the cylinder fraction. Apart from the application of aluminum oxide films as filtration membranes. however. The ellipsometry spectra are analyzed using an anisotropic optical model.doc/ 3. making use of the motion of magnetic particles in magnetic field gradients. partly based on the original work by Bruggeman. Field-assisted nanocolloid self-assembly Apart from methods using bonding or self-organisation on the molecular level (e.utwente. tunable formation of extremely well-aligned cylindrical pores. Results on our film samples with a well-defined geometry show that anodization of aluminum is reproducible and results in a porous aluminum oxide network with randomly distributed. deposition on functionalised substrates or Langmuir-Blodgett techniques).and dip-coating or spray deposition). The formation of highly ordered colloidal layers was observed during EPD of micrometer-sized silica and polystyrene particles and nanometer-sized gold particles. We use spectroscopic ellipsometry and other standard techniwues to characterize porous aluminum oxide obtained by anodization of aluminum films. they are frequently used to fabricate nanowires with large aspect ratios. but perfectly aligned cylindrical pores perpendicular to the substrate. Structural and optical anisotropy in nanoporous anodic aluminium oxide Porous aluminum oxide has stimulated considerable interest as a nanostructural template.http://www. .g. the soft-matter approach for deposition of colloidal films includes established "physical" techniques (e. 4.g. magnetophoretic deposition (MPD) can be used to direct particles onto a substrate. Recent work. It is particularly useful for nanometer-sized particles for which gravitational forces are too small to direct the particles to a substrate. primarily because of the and the nanoporosity of the aluminum oxide matrix. Similarly. The model adequately describes the optical response of the anodized film in terms of three physically relevant parameters: the film thickness. spin. which offer only limited control over the deposition and ordering processes. Better control of layer growth can be achieved by electrophoretic deposition (EPD). has shown that the electric field is more than just a substitute for gravity. an established technique for depositing charged colloidal particles onto electrodes.

The experimental results indicate that the dielectric function of the PbSe nanocrystals is thickness-dependent.doc/ 5.utwente. To complement UV/Visible absorption spectroscopy. Surface plasmon resonance spectroscopy and spectroscopic ellipsometry measurements. In another study. poly(ferrocenyldimethylsilanes). In one study. These results are compared to electronic band structure calculations of the imaginary part of the dielectric function. spectroscopic ellipsometry is used to measure the development of film thickness with the number of bilayers. different from the position of the band-gap transition.http://www. are employed to determine thickness changes upon oxidizing and reducing the surface-grafted polymers. performed under electrochemical control. . composed of alternating ferrocene and dimethylsilane units in their main chain and featuring a thiol end group. It is demonstrated that the size-dependent variation of the dielectric function is affected by quantum confinement at well-identifiable points in the Brillouin zone. Optical characterization of self-assembled poly(ferrocenylsilane) films Spectroscopic ellipsometry experiments are employed to investigate films of different poly(ferrocenylsilane) films. 7. The optical properties of these nanocrystal films are investigated using spectroscopic ellipsometry. organometallic multilayer films are deposited electrostatically onto a variety of substrate using layer-by-layer self-assembly of polyanions and polycations. Microcontact printing to pattern nanocolloidal films 6. were self-assembled to redoxactive monolayers on Quantum confinement effects in the dielectric function of PbSe Monolayers of lead selenide (PbSe) of a few nanometers in height are made by electrodeposition on a Au(111) substrate. .