Self-assembled and etched cones on laser ablated polymer surfaces

At least two different routes lead to conical structures on laser ablated polymer surfaces. These were investigated by studying laser ablation on the surfaces of different classes of polymers. Cones appeared readily in strongly absorbing polymers such as poly(ethylene terephthalate) (PET) and polyimide (PI), but only within narrow laser parameters in nylon 6, and rarely in poly(chlorotrifluoroethylene), the last two being weak ultraviolet (UV) absorbers. Self-assembled, close-packed cones occurred in PET, in which heat generated due to absorbed laser energy creates a thin, chemically stable, viscoelastic, highly compliant layer (above the glass transition temperature). Surface structure in such polymers evolves from nodules through donuts into ripples and finally to cones as the energy deposited per unit area on the surface (total fluence) is increased using a combination of single pulse fluence and number of pulses. A phase transition from a ripple phase to a cone phase is thought to occur as the thickness of the viscoelastic surface layer increases above a critical value. Cones began to appear from almost the beginning of the irradiation process at random locations in PI, a polymer whose surface irreversibly turns into a hard solid upon exposure to either or both UV and heat. It is proposed that the radiation hardened spots serve as nuclei, a cone "grows" out of this as the material surrounding this nuclei is ablated. The initial sparse occurrence of cones in PI-like polymers, and the increase in their number density with total fluence until the surface is densely packed with cones can be explained by a nucleation and growth model.