title: Real-Time Monitoring of Morphology and Optical Properties during Sputter Deposition for Tailoring Metal-Polymer Interfaces.
abstract: 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 (μGISAXS) 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 μGISAXS 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.
authors.affiliation: †Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Schwartzkopf
authors.affiliation: †Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: Gonzalo
authors.initials: G
authors.lastname: Santoro
authors.affiliation: †Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: Calvin J
authors.initials: CJ
authors.lastname: Brett
authors.affiliation: †Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: André
authors.initials: A
authors.lastname: Rothkirch
authors.affiliation: ‡Lehrstuhl für Materialverbunde, Institut für Materialwissenschaft, Christian Albrechts-Universität zu Kiel, Kaiserstr.2, D-24143 Kiel, Germany.
authors.forename: Oleksandr
authors.initials: O
authors.lastname: Polonskyi
authors.affiliation: ‡Lehrstuhl für Materialverbunde, Institut für Materialwissenschaft, Christian Albrechts-Universität zu Kiel, Kaiserstr.2, D-24143 Kiel, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Hinz
authors.affiliation: §Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München, James-Franck-Str. 1, D-85748 Garching, Germany.
authors.forename: Ezzeldin
authors.initials: E
authors.lastname: Metwalli
authors.affiliation: §Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München, James-Franck-Str. 1, D-85748 Garching, Germany.
authors.forename: Yuan
authors.initials: Y
authors.lastname: Yao
authors.affiliation: ‡Lehrstuhl für Materialverbunde, Institut für Materialwissenschaft, Christian Albrechts-Universität zu Kiel, Kaiserstr.2, D-24143 Kiel, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Strunskus
authors.affiliation: ‡Lehrstuhl für Materialverbunde, Institut für Materialwissenschaft, Christian Albrechts-Universität zu Kiel, Kaiserstr.2, D-24143 Kiel, Germany.
authors.forename: Franz
authors.initials: F
authors.lastname: Faupel
authors.affiliation: §Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München, James-Franck-Str. 1, D-85748 Garching, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Müller-Buschbaum
authors.affiliation: †Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, D-22607 Hamburg, Germany.
authors.forename: Stephan V
authors.initials: SV
authors.lastname: Roth
keywords: UV/vis specular reflectance spectroscopy; gold cluster growth kinetics; in situ GISAXS; metal−polymer nanocomposites; sputter deposition