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To study the property of proton conduction for electrolyte thin film inside catalyst layer, model ionomer thin films were prepared on different surfaces such as carbon and platinum substrates. An atomic force microscopy coupled with electrochemical technique (e-AFM) demonstrated that proton conduction reduced with film thickness, and abruptly decreased when film thickness was less than 10 nm for both carbon and platinum substrate. This indicates that number of active proton conductive pathway and/or connectivity of proton path network change with film thickness, and is though that the morphology of thin film is essentially different from that of a bulk membrane.

Solutions of Nafion® with an ion exchange capacity (IEC) of 0.91 meq g(-1), which are on the verge of the formation of SO(3)H nanoclusters, were spin coated on silicon (Si), glassy carbon (GC) and platinum/silicon (Pt/Si) substrates to form films of up to 256 nm thickness. Nanostructure of the films was studied using Doppler broadening of annihilation radiation (DBAR), positron annihilation lifetime (PAL), X-ray photoelectron spectroscopy (XPS), an atomic force microscope (AFM) and contact angle measurements. Contact angles as low as 10 degrees indicate that the surface of dry ultrathin Nafion® films on Si is highly hydrophilic. XPS data of 10 nm thick, ultrathin film on Si show that oxygen concentration is enhanced and the SO(3)H group concentration, in other words, IEC on the surface is much higher than other films. The S parameter measured by DBAR of an ultrathin Nafion® film on Si is much higher than that of the films on the other substrates. We consider that a large number of hydrophilic, reversed micelle like SO(3)H groups are on the surface of the ultrathin Nafion® film on Si but not on the surface of other films. Positrons implanted into the film are trapped by the SO(3)H clusters, annihilating with the electrons of oxygen and exhibit the high S parameter. The SO(3)H concentration on the surface of thin Nafion® films on GC and Pt/Si substrates may not be so high as the threshold for the formation of a large number of SO(3)H clusters. Positrons implanted into the films annihilate mostly with fluorine atoms, resulting in a low S parameter. The film-substrate interaction plays an essential role in nanostructuring of Nafion® thin films, which may also be the case for Nafion® on the catalysts of polymer electrolyte fuel cells.

The behavior of positrons that do not form positronium in dry fluorinated polymer electrolyte membranes (Nafion®, Fumapem® and Aquivion®) with various ion exchange capacities (IECs) was studied by the combined use of Doppler broadening of annihilation radiation (DBAR) and the positron lifetime technique. The drastic increase of the S parameter, measured by DBAR, with increasing IEC above 0.91 meq/g indicates that increasing numbers of positrons are trapped by oxygen atoms and annihilate with the electrons bound in them. Reversed micelle like SO3H nanoclusters to trap positrons possibly appear at IEC = 0.91 meq/g and their concentration increases with increasing IEC.

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