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In recent years, the applications of polyelectrolyte multilayer films, built by alternating adsorption of anionic and cationic polyelectrolytes, have grown in various fields. Transport of drugs or active molecules coupled to the polyelectrolytes is of interest for biomedical applications, such as controlled release. In polyelectrolyte films having a thickness exponentially growing with the number of deposited layer pairs, at least one of the polyelectrolytes diffuses “in” and “out” of the films during their buildup.