Solvent vapor annealing is as an effective and versatile alternative to thermal annealing to equilibrate and control the assembly of polymer chains in thin films. Here, we present scientific and practical aspects of the solvent vapor annealing method, including the discussion of such factors as non-equilibrium conformational states and chain dynamics in thin films in the presence of solvent. Homopolymer and block copolymer films have been used in model studies to evaluate the robustness and the reproducibility of the solvent vapor processing, as well as to assess polymer-solvent interactions under confinement. Advantages of utilizing a well-controlled solvent vapor environment, including practically interesting regimes of weakly saturated vapor leading to poorly swollen states, are discussed. Special focus is given to dual temperature control over the set-up instrumentation and to the potential of solvo-thermal annealing. The evaluated insights into annealing dynamics derived from the studies on block copolymer films can be applied to improve the processing of thin films of crystalline and conjugated polymers as well as polymer composite in confined geometries.
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