High-fluence implantation of negative metal ions into polymers for surface modification and nanoparticle formation

Negative ion implantation has been applied to polymers in order to modify the surface and to fabricate nanoparticles. Metal nanoparticles in the vicinity of a polymeric surface are promising for biomedical applications as well as nonlinear optical applications. Substrates of polymethyl methacrylate (PMMA) were implanted with Ag− and Cu− of 60 keV at 3 μA/cm2 up to 3×1017 ions/cm2. Optical absorption spectra of the implanted PMMA were measured in a photon range from 0.5 to 4.5 eV. A peak of surface plasmon resonance (SPR) emerges in the absorption spectra above about 1×1017 ions/cm2, both for the Ag− and Cu− cases. A coexisting absorption slope, due mostly to defects, increases but tends to saturate with ion fluence. The SPR peak of Ag-implanted PMMA is much broader than that of the Cu-implanted one. Corresponding to the SPR spectra, metal nanoparticles are observed by cross-sectional TEM. With increasing ion fluence, the Ag nanoparticles spread out towards the surface, in contrast to the localized Cu nanoparticles. The results demonstrate that metal nanoparticle fabrication in polymers is capable by using appropriate low-energy ions and provides a variety of spatial distributions dependent on ion species and fluence. In particular, Ag− ion implantation fabricates surface-exposed/gradient nanoparticles, which are suitable for biomedical applications such as anti-microbial effects.