Real-time shape evolution of nanoimprinted polymer structures during thermal annealing

The real-time shape evolution of nanoimprinted polymer patterns is measured as a function of annealing time and temperature using critical dimension small-angle X-ray scattering (CD-SAXS). Periodicity, line width, line height, and sidewall angle are reported with nanometer resolution for parallel line/space patterns in poly(methyl methacrylate) (PMMA) both below and above the bulk glass transition temperature (T _G). Heating these patterns below T _G does not produce significant thermal expansion, at least to within the resolution of the measurement. However, above T _G the fast rate of loss in pattern size at early times transitions to a reduced rate in longer time regimes. The time-dependent rate of polymer flow from the pattern into the underlying layer, termed pattern "melting", is consistent with a model of elastic recovery from stresses induced by the molding process. © 2006 American Chemical Society.