Vapor phase deposition of functional nanocomposite thin films and their modification by ion beam irradiation
Nanocomposite thin film coatings with a wide range of metal volume fractions were prepared by co–sputtering of TiO2/Teﬂon and Ag/Au from two different magnetron sources simultaneously in a home made deposition chamber under high vacuum conditions. Two different types of host materials a polymeric (PTFE) and a ceramic (TiO2) were studied in this work. Morphology, optical and antibacterial properties of these nanocomposites were examined. The formation of metallic nanoparticles upon vapor phase co–deposition of a metal and a dielectric matrix component can be understood in terms of the high cohesive energy of the metal and the low metal-matrix interaction energy which lead to high metal atom mobility on the growing composite surface and metal aggregation whenever metal atoms encounter each other or a metal cluster. Unlike the case of polymers, in the case of Ag nanoparticles on TiO2, segregation of the clusters on the surface also provides a fast pathway for Ostwald ripening without any restrictions by elastic distortions at least for those clusters which are in direct contact with the surface. 3D electron tomography was employed on the TiO2 based nanocomposite thin films to explain the two step model for the particle size distribution. First step involved the formation of small nanoparticles during vacuum phase deposition or on the growing surface. Second step after the deposition process involved the formation of larger particles through particle coarsening by Ostwald ripening and surface segregation. In bimetallic nanocomposites based on sandwich geometry in polymer system, the changes in the particle plasmon spectra of sandwiched Au nanoclusters as a result of the presence of Ag nanoclusters in their vicinity and vice versa was studied. Also, the optimum dielectric barrier thickness for the observation of equal intensity double plasmon resonance was reported. Also efforts towards tuning of the double plasmon resonances by tailoring the dielectric separation were carried out. Special attention was laid on the swift heavy ion irradiation (SHI) of the nanocomposites. The SHI beamlines from both the Hahn–Meitner–Institute in Berlin, Germany and the Inter University Accelerator Center in New–Delhi, India, were employed in this work. The TiO phase formation on SHI irradiation with increasing ﬂuence was understood by the interaction of two different counteracting mechanisms, where at lower ﬂuences, the tendency towards the formation of TiO existed with the larger unaffected areas and at higher ﬂuences, the destruction of the evolved TiO phase into fragments was evident. This served as an evidence for the counter play between "hit" and "no–hit", "single–hit" and "multiple–hit" processes. A comparative study involving the in–situ heating of the TiO2 based nanocomposites in the TEM confirms the absence of the formation of TiO. Changes of the microstructure of the nanocomposite film upon annealing allowed demonstrating the absence of the formation of TiO but rather only the crystallization of the TiO2. SHI irradiation of Ag nanoparticles embedded in PTFE matrix shows a marginal dissolution of Ag nanoparticles along with a slight agglomeration of nanoparticles. At higher ﬂuences, carbon rich areas were observed, which were as a result of the carbonization along the ion tracks. Functionality of the nanocomposites in terms of the antibacterial properties was studied. Cultures of B.megaterium, S.aureus, S.epidermidis and E.coli were used to study the effect on the Ag–TiO2 nanocomposites. Additionally, silver ion release studies were carried out at dfferent MVFs by using X-ray photoelectron and UV-Vis/NIR spectroscopies. Enhancement of the silver ion release after SHI irradiation at a ﬂuence was observed to the fact that the ion trajectories after irradiation provide better silver ion release.
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