| Summary: | Microfluidic chips and optical elements can be fabricated based on the nonlinear photosensitivity in photo–thermo–refractive (PTR) glass by controlling the growth of nanocrystals in the femtosecond (fs) laser–irradiated region. Here, we focus on CeO<sub>2</sub> and Sb<sub>2</sub>O<sub>3</sub> that play important roles in UV irradiation, experimentally investigate the effects of the dopants on the nonlinear photochemical process in PTR glass triggered by fs Gaussian–Bessel beams. The results show that the generation of Ag<sup>0</sup> atoms and the Ag nanoparticles can be improved by CeO<sub>2</sub> and Sb<sub>2</sub>O<sub>3</sub> co–doping. Besides, each multivalent ion in PTR glass possibly participates in the electron transfer processes and contributes to the generation of Ag<sup>0</sup> atoms. Finally, X–ray diffraction analysis reveals the precipitation of NaF nanocrystals with an average size of 10 to 12 nm after laser irradiation and thermal treatment, which is unrelated to the dopants.
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