Thermal transitions in semi-crystalline polymer thin films studied via spectral reflectance

Giovanni M. Kelly, James F. Elman, Zhang Jiang, Joseph Strzalka, Julie N.L. Albert

Index: 10.1016/j.polymer.2018.04.017

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Abstract

Herein we report the finding that spectral reflectance (SR) can be used to identify thermal transitions in semi-crystalline polymer thin films. By studying film thickness as a function of temperature, we found that semi-crystalline polymers exhibit characteristic expansion and contraction profiles during the melting (Tm) and crystallization (Tc) transitions, respectively. Prior to this discovery, studies on the crystalline Tm in thin films have involved more expensive and complex techniques such as atomic force microscopy (AFM), ellipsometry, and grazing-incidence wide-angle X-ray scattering (GIWAXS). We correlate Tm and Tc as measured by SR with differential scanning calorimetry (DSC) in the bulk and temperature-controlled GIWAXS or AFM in thin films. We show that SR is accurate for measuring changes in films with thicknesses of 500 nm down to 21 nm and for detecting melting point depression due to thin film confinement. Thus, we demonstrate that SR is a powerful tool for measuring thermal transitions in semi-crystalline polymer films with single-degree resolution.