Fine-Tuning of the film thickness of ultrathin multilayer films composed of consecutively alternating layers of anionic and cationic polyelectrolytes

We have recently introduced a new method of creating ultrathin films [1–3] based on the electrostatic attraction between opposite charges. Consecutively, alternating adsorption of anionic and cationic polyelectrolytes leads to the formation of multilayer assemblies. Multilayer buildup is easily monitored by small angle x-ray scattering (SAXS). The total thickness of the multilayer assemblies increases linearly with the number of adsorbed layers, indicating a stepwise and regular deposition process. — Here, we report on the fine-tuning of the total film thickness by changing the ionic strength of the solvent from which the polyelectrolytes are adsorbed. When the anionic polyelectrolyte is ad…

Hydrophilic/Hydrophobic Nanostripes in Lipopolymer Monolayers

Poly(styrene sulfonate) self-organization: electrostatic and secondary interactions

We investigate the self-organization of PSS in brushes and polyelectrolyte multilayers with X-ray, neutron and optical reflectivity. The electrostatic force dominates brush phases and adsorption behavior, additionally we find evidence of a strong hydrophobic force: (i) within amphiphilic diblock copolymer monolayers, a PSS monolayer adsorbs flatly to the hydrophobic block, (ii) on temperature increase (and with screened electrostatic forces), more PSS is adsorbed onto oppositely charged surfaces, and (iii) a polyelectrolyte multilayers shrinks when heated at 100% r.h. The latter two effects are consistent with the well-known increase of the hydrophobic force on heating: The increased PSS su…

Proof of multilayer structural organization in self-assembled polycation-polyanion molecular films

Abstract Multilayer organization of ultrathin polycation-polyanion self-assembled films is demonstrated using two approaches. (1) Fabrication of polyion superlattices with alternation of three different polyelectrolytes in (ABCB) n fashion, which gives rise to a Bragg peak in X-ray reflectivity. The spacing d=93.4 A corresponds to the repeat unit (ABCB) n . (2) Drying-induced manipulation of the film surface at regular intervals. Normally the layer-by-layer adsorption is carried out by keeping the film wet throughout all deposition cycles. Alternatively the film surface can be manipulated by gently drying the film in a stream of nitrogen or air after the adsorption of every layer. When the …

Reversible swelling of polyanion/polycation multilayer films in solutions of different ionic strength

Immersion of consecutively adsorbed polyanion/polycation multilayer films in solutions of different ionic strength causes reversible thickness changes. Swelling of the films up to 18% was observed after soaking the films in aqueous solutions of NaCl at concentrations up to 1.0 mol/l. X-ray reflectivity clearly shows that the thickness changes are reversible within experimental error and that the films seem to get smoother after several cycles of immersion in salt solutions and in pure water. The extent of swelling depends on the internal film structure, namely on the number of polyanion/polycation interfaces in a film of a given thickness. Interestingly, the swelling levels off at salt conc…

Metal nanoparticle/polymer superlattice films: Fabrication and control of layer structure

Layer-by-layer deposited multilayer assemblies of polyelectrolytes and proteins: from ultrathin films to protein arrays

We have recently introduced a new method of creating ultrathin films of polyelectrolytes based on the electrostatic attraction between opposite charges. Multilayer assemblies are adsorbed in a layer-by-layer fashion from aqueous solutions of the polymers. The total film thickness can easily be adjusted by varying the ionic strength of the solution. Here, we report on the temperature stability and the water content of the multilayer assemblies. Furthermore, we have extended our concept to the incorporation of protein layers into films of synthetic polyelectrolytes. The well established system biotin/streptavidin was used to construct such multilayers, also by biospecific recognition. Adsorpt…

Characterization of Zirconium Phosphate/Polycation Thin Films Grown by Sequential Adsorption Reactions

Monolayer and multilayer thin films consisting of anionic α-zirconium phosphate (α-ZrP) sheets and polycations (poly(allylamine hydrochloride) (PAH), cytochrome c) were characterized by transmission electron microscopy (TEM), ellipsometry, UV−visible absorbance spectroscopy, reflectance FT-IR, XPS, and X-ray diffraction. Titration and powder X-ray diffraction experiments confirm that exfoliation of α-ZrP begins to occur when enough tetra(n-butylammonium) hydroxide (TBA+OH-) has been added to exceed single-layer packing of TBA+ ions (x ≈ 0.50) in the intercalation compound Zr(HPO4)2-x(TBA+PO4-)x·nH2O. The identical contrast of many sheets in TEM micrographs suggests that the suspension is un…

Buildup of ultrathin multilayer films by a self-assembly process: III. Consecutively alternating adsorption of anionic and cationic polyelectrolytes on charged surfaces

A solid substrate with a positively charged planar surface is immersed in a solution containing an anionic polyelectrolyte and a monolayer of the polyanion is adsorbed. Since the adsorption is carried out at relatively high concentrations of polyelectrolyte, a large number of ionic residues remain exposed to the interface with the solution and thus the surface charge is effectively reversed. After rinsing in pure water the substrate is immersed in the solution containing a cationic polyelectrolyte. Again a monolayer is adsorbed but now the original surface charge is restored. By repeating both steps in a cyclic fashion, alternating multilayer assemblies of both polymers are obtained. The bu…

Layer-by-Layer Adsorption: The Solid/Liquid-Interface as a Template for the Controlled Growth of Well-Defined Nanostructures of Polyelectrolytes, Proteins, DNA and Polynucleotides

This report describes the construction of ultrathin films whose structure can be tailored on the molecular scale. The resulting supramolecular film architectures may include functional biological macromolecules such as proteins or polynucleotides. The average distances of two functional layers can be adjusted on the nanometer scale (from less than lnm to several tens of nanometers), with a precision of approximately 0.1 nm. This control is achieved by varying the number and the thickness of the polyelectrolyte interlayers and requires the capability of steering each adsorption step with high accuracy. A crucial factor is the fabrication and manipulation of the film surface at each adsorptio…

The Swelling Behavior of Polyelectrolyte Multilayers in Air of Different Relative Humidity and in Water

The swelling properties of physisorbed polyelectrolyte multilayer self-assemblies with alternating polyion charge in humid air and in aqueous environment were investigated via X-ray and neutron reflectometry as well as optically, using surface plasmon spectroscopy. The sorption behavior was similar to that found for neutral polymers and was related to an internal screening of the charges of the adjacent layers owing to the high entanglement of the polyelectrolyte chains and the resulting low mobility of the polymer segments. The screening was found to be incomplete only in the top layer, resulting in a net charged surface.

Chemical modification of Topaz surfaces

In chemisorption, one is typically faced with the problem that the two-dimensional structure of the organic layer does not match the structure of the inorganic substrate. This work describes the first steps toward an induced epitaxial correlation of organic compounds on an inorganic surface. The idea of this work was to use a single crystal with a two-dimensional surface structure, Topaz (001), that matches an alkyl chain lattice better than existing substrates. X-ray reflectivity and FTIR experiments prove the surface modification of the Topaz, which is probably an etherification of the reactive OH-groups on the Topaz (001) surface.