The mechanism involved in the photochemical immobilization of poly(4‐vinylphenol) (PVP) thin films was investigated. The films were fabricated by a simple procedure of UV irradiation and solvent extraction. A combination of ellipsometry, IR, and high‐resolution X‐ray photoelectron spectroscopy (XPS) was used to provide detailed and quantitative analysis of the composition of the photochemical reaction products. Upon irradiation at 260 nm, benzyl and phenoxy radicals are generated in the polymer. In the absence of oxygen, PVP films crosslinked via the combination of the benzyl radicals or phenoxy radicals. At lower irradiation doses, the photochemical process was dominated by crosslinking of the polymer backbone via the combination of benzyl radicals. At higher exposure doses, crosslinked quinoid structures were generated, and the concentration increased with the irradiation time. No oxidation or degradation products were observed. In the presence of oxygen, additional reactions of oxidation and degradation occurred. At lower doses, oxidation at the benzyl position produced the ketone structure evidenced by the drastic increase in the O content in the irradiated films. As the irradiation doses increased, further oxidation at the methylene position occurred, and in addition, volatile and degradation products were also generated. This photochemical process was successfully employed to fabricate patterned PVP structures.magnified image
A simple method for creating self-assembled nanostructures using a single polymer system is reported. When spin-coated polystyrene thin films were irradiated with UV light and treated with toluene, unique nanostructures were observed, evolving from star-shaped networks to arrays of concentric circles. The nanostructure formation is a result of differential responses of crosslinked and oxidized products to the solvent by a combined effect of phase separation and solvent swelling. The nanostructures were observed for polymers of different molecular weights, films of different thicknesses, and on various substrates.
The elastic mechanical response of a poly͑4-vinylpyridine͒ film is exploited to create nanostructures under ambient conditions via dip pen nanolithography. Using a pH 4 phosphate buffer solution as the "ink," a series of experimental results indicates that the nanometer-sized structures are due to local swelling of the film's pyridyl groups upon their protonation with the hydronium ions delivered by the tip. Control over the structures' height is gained by properly selecting the writing velocities or the dwell time, respectively.
We report the creation of nano-structures via Dip Pen Nanolithography by locally exploiting the mechanical response of polymer thin films to an acidic environment. Protonation of cross linked poly(4-vinylpyridine) (P4VP) leads to a swelling of the polymer. We studied this process by using an AFM tip coated with a pH 4 buffer. Protons migrate through a water meniscus between tip and sample into the polymer matrix and interact with the nitrogen of the pyridyl group forming a pyridinium cation. The increase in film thickness, which is due to Coulomb repulsion between the charged centers, was investigated using Atomic Force Microscopy. The smallest structures achieved had a width of about 40 nm. Different control experiments support our claim that the protonation is the reason for the swelling and therefore the formation of the structures. Kelvin probe force microscopy measurements suggest the presence of counter ions which compensate the positively charged pyridinium ions. We investigated the influence of the water meniscus on the structure formation by varying the relative humidity in the range from 5% to 60% for different dwell times. The diffusion of protons and counter ions is humidity-dependent and requires a water meniscus.
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