Oleksandr Polonskyi

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.

Vacuum Thermal Degradation of Poly(ethylene oxide)

Thermal degradation of poly(ethylene oxide) (PEO) was studied under vacuum conditions. PEO macromolecules degrade predominantly by random chain scission of a backbone with elimination of oligomer fragments. The reactions include the mechanism of radical termination by disproportionation. The eliminated fragments form thin film deposits which have chemical composition close to the original PEO. Activation of the evaporated flux with a glow discharge leads to further fragmentation and recombination of the released species and can be used to tune the properties of the resulting thin films.

Localized Synthesis of Iron Oxide Nanowires and Fabrication of High Performance Nanosensors Based on a Single Fe2O3 Nanowire

A composed morphology of iron oxide microstructures covered with very thin nanowires (NWs) with diameter of 15-50 nm has been presented. By oxidizing metallic Fe microparticles at 255 °C for 12 and 24 h, dense iron oxide NW networks bridging prepatterned Au/Cr pads are obtained. X-ray photoelectron spectroscopy studies reveal formation of α-Fe2 O3 and Fe3 O4 on the surface and it is confirmed by detailed high-resolution transmission electron microscopy and selected area electron diffraction (SAED) investigations that NWs are single phase α-Fe2 O3 and some domains of single phase Fe3 O4 . Localized synthesis of such nano- and microparticles directly on sensor platform/structure at 255 °C for 24 h and reoxidation at 650 °C for 0.2-2 h, yield in highly performance and reliable detection of acetone vapor with fast response and recovery times. First nanosensors on a single α-Fe2 O3 nanowire are fabricated and studied showing excellent performances and an increase in acetone response by decrease of their diameter was developed. The facile technological approach enables this nanomaterial as candidate for a range of applications in the field of nanoelectronics such as nanosensors and biomedicine devices, especially for breath analysis in the treatment of diabetes patients.

Influence of reactive gas admixture on transition metal cluster nucleation in a gas aggregation cluster source

We quantitatively assessed the influence of reactive gases on the formation processes of transition metal clusters in a gas aggregation cluster source. A cluster source based on a 2 in. magnetron is used to study the production rate of titanium and cobalt clusters. Argon served as working gas for the DC magnetron discharge, and a small amount of reactive gas (oxygen and nitrogen) is added to promote reactive cluster formation. We found that the cluster production rate depends strongly on the reactive gas concentration for very small amounts of reactive gas (less than 0.1% of total working gas), and no cluster formation takes place in the absence of reactive species. The influence of discharge power, reactive gas concentration, and working gas pressure are investigated using a quartz micro balance in a time resolved manner. The strong influence of reactive gas is explained by a more efficient formation of nucleation seeds for metal-oxide or nitride than for pure metal.

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.

Stable production of TiOx nanoparticles with narrow size distribution by reactive pulsed dc magnetron sputtering

The pulsed dc magnetron technique was used for generating TiOx nanoparticles by sputtering from a titanium target in a gas aggregation source. It was observed that the deposition rate (DR) of nanoparticles shows a peak followed by a broad tail, even for constant operation conditions. As a key finding of the present investigation, we show that nanoparticle deposition can be stabilized at nonzero DR for the pulsed power regime. Monitoring the oxygen concentration by mass spectrometry provides insight into nanoparticle generation in different processes. Characterization of the nanoparticle film morphology based on transmission electron microscopy reveals a very narrow size distribution. Furthermore, the oxygen admixture has a significant influence on the size distribution and also on the mean size of the formed nanoparticles. In situ analysis of the chemical composition of the deposited films directly after preparation by x-ray photoelectron spectroscopy shows a major contribution by sub-oxide titanium compounds to nanoparticle production.

Nylon-sputtered nanoparticles: fabrication and basic properties

Nylon-sputtered nanoparticles were prepared using a simple gas aggregation cluster source based on a planar magnetron (Haberland type) and equipped with a nylon target. Plasma polymer particles originated in an aggregation chamber and travelled to a main (deposition) chamber with a gas flow through an orifice. The deposited nanoparticles were observed to have a cauliflower-like structure. The nanoparticles were found to be nitrogen-rich with N/C ratio close to 0.5. An increase in rf power from 60 to 100 W resulted in a decrease in mean particle size from 210 to 168 nm whereas an increase in their residence time in the cluster source from 0.7 to 4.6 s resulted in an increase in the size from 73 to 231 nm.

Role of oxygen admixture in stabilizing TiO x nanoparticle deposition from a gas aggregation source

For the use of a gas aggregation cluster source a high and stable deposition rate is desired. For many metals, nanoparticle formation is enhanced by admixture of reactive gases. Here, the role of reactive gas admixtures on the nanoparticle deposition rates is investigated for the case of reactive direct current magnetron sputtering of Ti in a gas aggregation chamber. The results show that, at low working gas (argon) pressures, stable cluster deposition at high rates can only be achieved for admixtures with a very narrow oxygen flow range. At higher pressures, stable deposition can be observed only after an intermediate maximum rate has been crossed or a stable deposition rate is not reached at all. For the different sputtering conditions, the partial pressure of oxygen was monitored with a mass spectrometer. The results are explained in terms of the competing roles of oxygen in cluster nucleation as well as in target poisoning. The cluster size distributions for different conditions were characterized by scanning electron microscopy.

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.

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.