Alexander Hinz

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

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.

Huge increase in gas phase nanoparticle generation by pulsed direct current sputtering in a reactive gas admixture

Using reactive DC sputtering in a gas aggregation cluster source, we show that pulsed discharge gives rise to a huge increase in deposition rate of nanoparticles by more than one order of magnitude compared to continuous operation. We suggest that this effect is caused by an equilibrium between slight target oxidation (during “time-off”) and subsequent sputtering of Ti oxides (sub-oxides) at “time-on” with high power impulse.

Role of Sputter Deposition Rate in Tailoring Nanogranular Gold Structures on Polymer Surfaces

The reproducible low-cost fabrication of functional polymer-metal interfaces via self-assembly is of crucial importance in organic electronics and organic photovoltaics. In particular, submonolayer and nanogranular systems expose highly interesting electrical, plasmonic, and catalytic properties. The exploitation of their great potential requires tailoring of the structure on the nanometer scale and below. To obtain full control over the complex nanostructural evolution at the polymer-metal interface, we monitor the evolution of the metallic layer morphology with in situ time-resolved grazing-incidence small-angle X-ray scattering during sputter deposition. We identify the impact of different deposition rates on the growth regimes: the deposition rate affects primarily the nucleation process and the adsorption-mediated growth, whereas rather small effects on diffusion-mediated growth processes are observed. Only at higher rates are initial particle densities higher due to an increasing influence of random nucleation, and an earlier onset of thin film percolation occurs. The obtained results are discussed to identify optimized morphological parameters of the gold cluster ensemble relevant for various applications as a function of the effective layer thickness and deposition rate. Our study opens up new opportunities to improve the fabrication of tailored metal-polymer nanostructures for plasmonic-enhanced applications such as organic photovoltaics and sensors.

Influence of nanoparticle formation on discharge properties in argon-acetylene capacitively coupled radio frequency plasmas

This contribution presents experimental results regarding the influence of nanoparticle formation in capacitively coupled radio frequency (13.56 MHz) argon-acetylene plasmas. The discharge is studied using non-invasive 160 GHz Gaussian beam microwave interferometry and optical emission spectroscopy. Particularly, the temporal behavior of the electron density from microwave interferometry is analyzed and compared with the changing plasma emission and self-bias voltage caused by nanoparticle formation. The periodic particle formation with a cycle duration between 30 s and 140 s starts with an electron density drop over more than one order of magnitude below the detection limit (8 × 1014 m−3). The electron density reduction is the result of electron attachment processes due to negative ions and nanoparticle formation. The onset time constant of nanoparticle formation is five times faster compared to the expulsion of the particles from the plasma due to multi-disperse size distribution. Moreover, the intensit...

Single-step generation of metal-plasma polymer multicore@shell nanoparticles from the gas phase

Nanoparticles composed of multiple silver cores and a plasma polymer shell (multicore@shell) were prepared in a single step with a gas aggregation cluster source operating with Ar/hexamethyldisiloxane mixtures and optionally oxygen. The size distribution of the metal inclusions as well as the chemical composition and the thickness of the shells were found to be controlled by the composition of the working gas mixture. Shell matrices ranging from organosilicon plasma polymer to nearly stoichiometric SiO2 were obtained. The method allows facile fabrication of multicore@shell nanoparticles with tailored functional properties, as demonstrated here with the optical response.

Modification of a metal nanoparticle beam by a hollow electrode discharge

Treatment of nanoparticles (NPs) in complex environments, such as plasmas, is of interest for the fabrication of advanced nanomaterials with desired properties and also from a physical point of view. Here, the authors investigate the mutual interaction between silver NPs and a radio frequency (RF) plasma at different conditions by combining a cylindrical hollow electrode with a gas aggregation source. The investigation of the NP deposits and the morphology of the casted films shows that the applied RF discharge significantly changes the path of the NPs as well as the NP size distribution in the beam. Starting from a neutral NP beam, it is observed that most of the NPs leave the plasma region with negative charge(s), yet the fraction of positively charged NPs grows with power. Furthermore, the plasma characteristics are slightly influenced by the NP flux since the passing NPs collect the plasma charge carriers.

Electrical measurements for the control of nanoparticle growth in an acetylene plasma

Nanoparticles are not only of fundamental interest due to their remarkable properties but also of practicle importance in material processing. Controlling their growth in plasmas is regarded as a new route to prepare nanoparticles of well defined size and composition. However, the processes during their formation are yet to be fully understood. Especially the early stages of the particle growth are not well investigated since they are experimentally inaccessible by standard methods like Mie-scattering. A novel collection method based on neutral drag was tested in order to get a better insight into the early stages of particle growth. The experiments were performed in a capacitively coupled discharge, where multiple growth cycles can be obtained. Size distributions of the nanoparticles at different stages of the growth cycle were determined ex-situ by electron microscopy. The obtained size distributions were correlated with in-situ measurements of the bias voltage and the phase angle between discharge current and voltage. The observed correlations, which can be used for prediction of the particle growth, are qualitatively explained.