Formation of crystalline dots and lines in lanthanum borogermanate glass by the low pulse repetition rate femtosecond laser

Abstract

Femtosecond lasers have become a powerful tool for 3D space-selective crystallization of glasses. A laser-induced cumulative heating effect required for crystal growth is usually considered to take place only at pulse repetition rate over 100 or 200 kHz and 200 kHz is known as the lowest repetition rate at which femtosecond laser-induced crystallization has been reported so far. We for the first time demonstrate precipitation of LaBGeO5 crystals in lanthanum borogermanate glass using a femtosecond laser emitting 1030 nm, 300 fs, 110 μJ pulses with adjustable repetition rate below 100 kHz. For the applied laser, minimal repetition rate enabling nucleation of ferroelectric LaBGeO5 crystals inside the glass was shown to be 9 kHz at maximal pulse energy of 110 μJ and growth of a crystalline line from the formed seed crystal was obtained starting from 8 kHz though smooth homogeneous oriented line which might be regarded as quasi-single-crystalline could be grown at 25 kHz or higher and corresponding pulse energy of 18 μJ. Thus, the pulse repetition rate sufficient for a cumulative heating effect and a stable crystal growth was reduced by an order of magnitude as compared to earlier publications due to relatively high pulse energy. Possibility and efficiency of cumulative heating and crystal growth and average time required for forming the seed crystal have been studied for various combinations of the pulse energy and the repetition rate. Obtained crystalline features have been studied by micro-Raman spectroscopy and Raman mapping which confirmed growth of stillwellite-like LaBGeO5 phase and orientation of its polar axis along the direction of the crystalline line.