Nanoscale Pattern Decay Monitored Line by Line via In Situ Heated Atomic Force Microscopy

We combine in situ heated atomic force microscopy (AFM) with automated line-by-line spectral analysis to quantify the relaxation or decay phenomenon of nanopatterned composite polymer films above the glass-transition temperature of the composite material. This approach enables assessment of pattern fidelity with a temporal resolution of ≈1 s, providing the necessary data density to confidently capture the short-time relaxation processes inaccessible to conventional ex situ measurements. Specifically, we studied the thermal decay of nanopatterned poly(methyl methacrylate) (PMMA) and PMMA nanocomposite films containing unmodified and PMMA-grafted silica nanoparticles (SiO₂ NP) of varying concentrations and film thicknesses using this new approach. Features imprinted on neat PMMA films were seen to relax at least an order of magnitude faster than the NP-filled films at decay temperatures above the glass transition of the PMMA matrix. It was also seen that patterned films with the lowest residual thickness (34 nm) filled with unmodified SiO₂ NP decayed the slowest. The effect of nanoparticle additive was almost negligible in reinforcing the patterned features for films with the highest residual thickness (257 nm). Our in situ pattern decay measurement and the subsequent line-by-line spectral analysis enabled the investigation of various parameters affecting the pattern decay such as the underlying residual thickness, type of additive system, and temperature in a timely and efficient manner.