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The surfaces of polymer and interfaces between polymer and inorganic particles are of particular importance for the properties of polymers and composites. However, the determination of the properties of surfaces and interfaces poses many challenges due to their extremely small dimensions. Herein, polystyrene and polymethyl methacrylate thin film on silicon wafer was used as a model system for the measurement of the properties of the polymer near free surface and at the polymer-solid interface. Two different methods, i.e., nanoindentation using atomic force microscopy (AFM) and the gold nanoparticle embedding technique, were used for these measurements. The results showed the elastic modulus of PS near the free surface determined by nanoindentation was lower than the bulk value. Based on contact mechanics analysis, nanoparticle embedding also revealed the existence of a lower-modulus, non-glassy layer near the free surface at temperatures below the bulk glass transition temperature ( T  g ). However, near the polymer-solid interface, the AFM nanoindentation method is not applicable due to the geometry confinement effect. On the other hand, the nanoparticle embedding technique can still correctly reflect the interactions between the polymer and the substrate when compared to the ellipsometry results.

Comparison of AFM Nanoindentation and Gold Nanoparticle Embedding Techniques for Measuring the Properties of Polymer Thin Films