Real-Time Monitoring of Morphology and Optical Properties during Sputter Deposition for Tailoring Metal-Polymer Interfaces

摘要

The reproducible low-cost fabrication of functional metal polymer nanocomposites with tailored optoelectronic properties for advanced applications remains a major challenge in applied nanotechnology. To obtain full control over the nanostructural evolution at the metal polymer interface and its impact on optoelectronic properties, we employed combined in situ time-resolved microfocus grazing incidence small angle X-ray scattering (mu GISAXS) with in situ UV/vis specular reflectance spectroscopy (SRS) during sputter deposition of gold on thin polystyrene films. On the basis of the temporal evolution of the key scattering features in the real-time mu GISAXS experiment, we directly observed four different growth regimes: nucleation, isolated island growth, growth of larger aggregates via partial coalescence, and continuous layer growth. Moreover, their individual thresholds were identified with subnanometer resolution and correlated to the changes in optical properties. During sputter deposition, a change in optical reflectivity of the pristine gray-blue PS film was observed ranging from dark blue color due to the presence of isolated nanoclusters at the interface to bright red color from larger Au aggregates. We used simplified geometrical assumptions to model the evolution of average real space parameters (distance, size, density, contact angle) in excellent agreement with the qualitative observation of key scattering features. A decrease of contact angles was observed during the island-to-percolation transition and confirmed by simulations. Furthermore, a surface diffusion coefficient according to the kinetic freezing model and interfacial energy of Au on PS at room temperature were calculated based on a real-time experiment. The morphological characterization is complemented by X-ray reflectivity, optical, and electron microscopy. Our study permits a better understanding of the growth kinetics of gold clusters and their self-organization into complex nanostructures on polymer substrates. It opens up the opportunity to improve nanofabrication and tailoring of metal polymer nanostructures for optoelectronic applications, organic photovoltaics, and plasmonic-enhanced technologies.