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High-resolution X-ray photoelectron spectroscopy (XPS) has been applied to a series of free-base and Zn-porphyrin polymers in which the macrocycles are separated by oligo(phenylene vinylene) units (OPV) of different, controllable lengths. Neat films of all the Zn-porphyrin polymers unexpectedly reveal two peaks in the N 1s XPS region ( approximately 400 eV). The peak areas vary with the length of the OPV bridge, suggesting an intermolecular interaction between the porphyrin and linker subunits. A series of XPS analyses were performed to identify the different interactions taking place in these thin films. To inhibit interpolymer interactions, one of the polymers was incorporated into a nonconjugated PMMA matrix, collapsing the N1s spectrum to a single peak at 398.0 eV, relative to the neat film signals at 397.8 and 400.1 eV. In a conjugated matrix of OPV, two peaks remain at 401.7 and 399.5 eV. Extensive vacuum drying of the neat film leads to a single peak at 398.3 eV, suggesting loss of trapped solvent molecules. Ultimately, we attribute the lower energy signal of the neat films to solvent ligation, and the higher energy peak is attributed to interactions between the porphyrins and conjugated bridges on nearby polymer chains. This interpretation is successfully applied to the N 1s XPS data from a previously reported Zn-porphyrin oligomer-based multilayer array.

Standard dry surface modification reactions have been applied to partially deacetylated chitosan without affecting its bulk properties. Chitin, extracted from shells of Penaeus vannamei, yielded chitosan with a degree of acetylation of 70% and molecular weight of 250 000 D. The copolymer consists of (β‐(1‐4)‐2‐2‐acetamido‐D‐glucose) units linked to (β‐(1‐4)‐2‐amino‐D‐glucose) units. Since the main interest of this work was to study the surface properties of films on substrates, a method to cast this material onto Al‐coated silicon wafers had to be developed. X ray photoelectron spectroscopy (XPS) has been used to determine the surface composition of the unmodified films and to follow modification changes. The films were treated in either an oxygen plasma environment or under UV/ozone irradiation. Water advancing contact angle measurements and infrared spectroscopy (FTIR) were used to complement XPS measurements. The films appeared to orient on the silicon wafer surface in the type II chitin structure. The rates of oxidation are faster for the plasma process but they result in similar changes to those induced by UV/ozone treatment. Atomic force microscopy (AFM) clearly shows the advantage of the milder modification reaction without much change in surface morphology. The oxidation processes, as detected by XPS, proceed without much alteration of the amine nitrogen atoms but carbonyl containing moieties are formed as a function of treatment time. Specific reactions with a fluorosilane to measure the activity of hydroxyl groups indicate that at short treatment times, these groups are essentially inactive. The resulting surfaces can also serve as a potential way to induce silica‐like domains that can function as diffusion barriers. Irradiation of chitosan solutions shows that UV/ozone induces depolymerization. In both cases, i.e., plasma and UV/ozone reactions, the main active component to surface modification appears to be UV irradiation with a wavelength below 360 nm.AFM surface profile for oxygen plasma treated film in barrel etcher for 1 min.magnified imageAFM surface profile for oxygen plasma treated film in barrel etcher for 1 min.

This work shows that the coupling of voltammetry with an electrochemical quartz crystal microbalance furnishes firm evidence of the formation and reduction of a surface gold oxide layer which is accompanied by the adsorption of a reactive intermediate from dimethylamine borane ͑DMAB͒ solutions. The purpose of this study is to provide further insights into the identity and role of the reactive intermediate assumed in the mechanism of electroless gold in the DMAB bath. It was found that alkaline DMAB solutions exhibit a rapid mass increase at 0.2 V vs. Ag/AgCl, which is accompanied by the reduction of the gold oxide in hydroxide media. The anodic current and mass increase associated with gold oxide reduction is attributed to reactivation of DMAB oxidation. On the contrary, a frequency increase is observed at this potential in the absence of DMAB. X-ray photoelectron spectroscopy measurements further indicate that the adsorption/desorption of a borane-containing reactive intermediate onto the gold surface is short-lived. The intermediate is consequently eliminated from the surface after interaction with the gold oxide layer.