Laser writing of nonlinear optical properties in silver-doped phosphate glass

The formation of both local second- and third-harmonic generations (SHG and THG) induced by a train of femtosecond laser pulses in silver-doped phosphate glasses is addressed. Based on modeling calculations, including various diffusion and kinetic processes, THG is shown to result from the formation of silver clusters. The latter organize into a ring-shape structure, leading to the emergence of a static electric field. By breaking the glass centro-symmetry, this field gives rise to a local effective second-order susceptibility, inducing SHG. Both theoretically predicted SHG and THG evolutions with respect to the number of pulses in the train are in good agreement with experimental observations. In particular, the observed reaching of a maximum in the nonlinear optical responses after a few thousands of pulses is explained by the competition of various physical processes. A cooling of the glass is shown to improve the process efficiency of the laser writing of second-order nonlinearity.