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Polycrystalline Ag, covered with a nm thin siloxane layer, was irradiated with ultraviolet light in vacuum at 500 K. Ag particles of different aspect ratios, 50–1000 nm in size, formed on the surface, including a small fraction of nanorods. Pressurized water vapor bubbles are created in the subsurface region by hydrogen radicals photo-chemically released by the siloxane layer. They provide the driving force for a diffusive material flux along grain boundaries to the surface. This mechanism was modeled and found to agree with the experimental timescale: approximately 300 h are required for a 1000 nm particle to form.