There is considerable current interest in developing methods to integrate nanoparticles into optical, electronic, and biological systems due to their unique size-dependent properties and controllable shape. We report herein a versatile new approach for covalent immobilization of nanoparticles onto substrates modified with photoactive, phthalimide-functional, self-assembled monolayers. Upon illumination with UV radiation, the phthalimide group abstracts a hydrogen atom from a neighboring organic molecule, leading to radical-based photografting reactions. The approach is potentially "universal" since virtually any polymeric or organic-inorganic hybrid nanoparticle can be covalently immobilized in this fashion. Because grafting is confined to illuminated regions that undergo photoexcitation, masking provides a simple and direct method for nanoparticle patterning. To illustrate the technique, nanoparticles formed from diblock copolymers of poly(styrene-b-polyethylene oxide) and laden with Hostasol Red dye are photografted and patterned onto glass and silicon substrates modified with photoactive phthalimide-silane self-assembled monolayers. Atomic force microscopy and X-ray photoelectron spectroscopy are applied to characterize the grafted nanoparticle films while confocal fluorescence microscopy is used to image patterned nanoparticle deposition.
