Primary relaxation processes at the band edge of ${\mathrm{SiO}}_2$

The kinetics of photoinduced defect formation in high-purity silicas has been studied by femtosecond transient absorption spectroscopy in the visible and ultraviolet. Band edge two-photon excitation produces singlet excitons which decay in 0.25 ps into defects with the absorption spectra of nonbridging oxygen hole centers (≡Si-O⋅) and silicon E’ centers (≡Si⋅). We identify these defect pairs with the self-trapped triplet exciton and the 0.25 ps decay with the motion of the photoexcited oxygen atom. Similar results were obtained with both crystalline and amorphous silica samples.