Nanopatterning Gold by Templated Solid State Dewetting on the Silica Warp and Weft of Diatoms

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The diatom,Nitzschia palea, exhibits complex silica shell (frustule) topography that resembles the warp and weft pattern of woven glass. The surface is perforated with a rhombic lattice of roughly oblong pores between periodically undulating transverse weft costae. Exfoliated frustules can be used to template gold nanoparticles by thermally induced dewetting of thin gold films. Acting as templates for the process, the frustules give rise to two coexisting hierarchies of particle sizes and patterned distributions of nanoparticles. By examining temperature dependent dewetting of 5, 10, and 15 nm Au films for various annealing times, we establish conditions for particle formation and patterning. The 5 nm film gives distributions of small particles randomly distributed over the surface and multiple particles at the rhombic lattice points in the pores. Thicker films yield larger faceted particles on the surface and particles that exhibit shapes that are roughly conformal with the shape of the pore container. The pores and costae are sources of curvature instabilities in the film that lead to mass transport of gold and selective accumulation in the weft valleys and pores. We suggest that, with respect to dewetting, the frustule comprises 2-dimensional sublattices of trapping sites. The pattern of dewetting is radically altered by interposing a self-assembled molecular adhesive of mercaptopropyltrimethoxysilane between the Au film overlayer and the frustule. By adjusting the interfacial energy in this manner, a fractal-like overlay of Au islands coexists with a periodic distribution of nanoparticles in the pores.