Correlating Optical Reflectance with the Topology of Aluminum Nanocluster Layers Growing on Partially Conjugated Diblock Copolymer Templates.

Large-scale fabrication of metal cluster layers for usage in sensor applications and photovoltaics is a huge challenge. Physical vapor deposition offers large-scale fabrication of metal cluster layers on templates and polymer surfaces. In the case of aluminum (Al), only little is known about the formation and interaction of Al clusters during sputter deposition. Complex polymer surface morphologies can tailor the deposited Al cluster layer. Here, a poly(methyl methacrylate)-block-poly(3-hexylthiophen-2,5-diyl) (PMMA-b-P3HT) diblock copolymer template is used to investigate the nanostructure formation of Al cluster layers on the different polymer domains and to compare it with the respective homopolymers PMMA and P3HT. The optical properties relevant for sensor applications are monitored with ultraviolet-visible (UV-vis) measurements during the sputter deposition. The formation of Al clusters is followed in situ with grazing-incidence small-angle X-ray scattering (GISAXS), and the chemical interaction is revealed by X-ray photoelectron spectroscopy (XPS). Furthermore, atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) yield topographical information about selective wetting of Al on the P3HT domains and embedding in the PMMA domains in the early stages, followed by four distinct growth stages describing the Al nanostructure formation.

Tailoring the Optical Properties of Sputter-Deposited Gold Nanostructures on Nanostructured Titanium Dioxide Templates Based on In Situ Grazing-Incidence Small-Angle X-ray Scattering Determined Growth Laws.

Gold/titanium dioxide (Au/TiO2) nanohybrid materials have been widely applied in various fields because of their outstanding optical and photocatalytic performance. By state-of-the-art polymer templating, it is possible to make uniform nanostructured TiO2 layers with potentially large-scale processing methods. We use customized polymer templating to achieve TiO2 nanostructures with different morphologies. Au/TiO2 hybrid thin films are fabricated by sputter deposition. An in-depth understanding of the Au morphology on the TiO2 templates is achieved with in situ grazing-incidence small-angle X-ray scattering (GISAXS) during the sputter deposition. The resulting Au nanostructure is largely influenced by the TiO2 template morphology. Based on the detailed understanding of the Au growth process, characteristic distances can be selected to achieve tailored Au nanostructures at different Au loadings. For selected sputter-deposited Au/TiO2 hybrid thin films, the optical response with a tailored localized surface plasmon resonance is demonstrated.

Real-time insight into nanostructure evolution during the rapid formation of ultra-thin gold layers on polymers.

Ultra-thin metal layers on polymer thin films attract tremendous research interest for advanced flexible optoelectronic applications, including organic photovoltaics, light emitting diodes and sensors. To realize the large-scale production of such metal-polymer hybrid materials, high rate sputter deposition is of particular interest. Here, we witness the birth of a metal-polymer hybrid material by quantifying in situ with unprecedented time-resolution of 0.5 ms the temporal evolution of interfacial morphology during the rapid formation of ultra-thin gold layers on thin polystyrene films. We monitor average non-equilibrium cluster geometries, transient interface morphologies and the effective near-surface gold diffusion. At 1 s sputter deposition, the polymer matrix has already been enriched with 1% gold and an intermixing layer has formed with a depth of over 3.5 nm. Furthermore, we experimentally observe unexpected changes in aspect ratios of ultra-small gold clusters growing in the vicinity of polymer chains. For the first time, this approach enables four-dimensional insights at atomic scales during the gold growth under non-equilibrium conditions.

Correlating Nanostructure, Optical and Electronic Properties of Nanogranular Silver Layers during Polymer-Template-Assisted Sputter Deposition.

Tailoring the optical and electronic properties of nanostructured polymer-metal composites demonstrates great potential for efficient fabrication of modern organic optical and electronic devices such as flexible sensors, transistors, diodes, or photovoltaics. Self-assembled polymer-metal nanocomposites offer an excellent perspective for creating hierarchical nanostructures on macroscopic scales by simple bottom-up processes. We investigate the growth processes of nanogranular silver (Ag) layers on diblock copolymer thin film templates during sputter deposition. The Ag growth is strongly driven by self-assembly and selective wetting on the lamella structure of polystyrene-block-poly(methyl methacrylate). We correlate the emerging nanoscale morphologies with collective optical and electronic properties and quantify the difference in Ag growth on the corresponding homopolymer thin films. Thus, we are able to determine the influence of the respective polymer template and observe substrate effects on the Ag cluster percolation threshold, which affects the insulator-to-metal transition (IMT). Optical spectroscopy in the UV-vis regime reveals localized surface plasmon resonance for the metal-polymer composite. Their maximum absorption is observed around the IMT due to the subsequent long-range electron conduction in percolated nanogranular Ag layers. Using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, we identify the oxidation of Ag at the acrylate side chains as an essential influencing factor driving the selective wetting behavior in the early growth stages. The results of polymer-templated cluster growth are corroborated by atomic force microscopy and field emission scanning electron microscopy.