Effect of Pulse Repetition Rate on Ultrafast Laser-Induced Modification of Sodium Germanate Glass

We report an unexpected pulse repetition rate effect on ultrafast-laser modification of sodium germanate glass with the composition 22Na₂O 78GeO₂. While at a lower pulse repetition rate (~≤250 kHz), the inscription of nanogratings possessing form birefringence is observed under series of 10⁵-10⁶ pulses, a higher pulse repetition rate launches peripheral microcrystallization with precipitation of the Na₂Ge₄O₉ phase around the laser-exposed area due to the thermal effect of femtosecond pulses via cumulative heating. Depending on the pulse energy, the repetition rate ranges corresponding to nanograting formation and microcrystallization can overlap or be separated from each other. Regardless of crystallization, the unusual growth of optical retardance in the nanogratings with the pulse repetition rate starting from a certain threshold has been revealed instead of a gradual decrease in retardance with the pulse repetition rate earlier reported for some other glasses. The repetition rate threshold of the retardance growth is shown to be inversely related to the pulse energy and to vary from ~70 to 200 kHz in the studied energy range. This effect can be presumably assigned to the chemical composition shift due to the thermal diffusion of sodium cations occurring at higher pulse repetition rates when the thermal effect of the ultrashort laser pulses becomes noticeable.