Polymer crystallization of ultrathin films on solid substrates

Recently, polymer crystallization in ultrathin films (thickness less than 100 nm) on solid substrates has attracted increased attention. As it can be considered to be a quasi-two-dimensional (2D) system with one-dimensional (1D) confinement along the substrate normal, ultrathin polymer film offers unique possibilities for testing the theories of crystallization and for studying the effects of confinement and interface which may invoke new mechanisms other than those applied in bulk crystallization of polymers. In this article, we will summarize the important results of ultrathin film crystallization of polymers obtained in the past decades. The morphologies, the crystallization kinetics, and the transformation between monolayer crystals with various metastabilities are reviewed in depth, with an attempt at discussing the ultrathin polymer film crystallization in the general framework of thermodynamics and kinetics of crystallization.