Optical and structural characterization of femtosecond laser written micro-structures in germanate glass.

We report on direct femtosecond laser writing in zinc barium gallo-germanate glasses. A combination of spectroscopic techniques allows to progress in the understanding of the mechanisms taking place depending on the energy. In the first regime (type I, isotropic local index change) up to 0.5 µJ, the main occurrence is the generation of charge traps inspected by luminescence, together with separation of charges detected by polarized second harmonic generation measurements. At higher pulse energies notably at the threshold corresponding to 0.8 µJ or in the second regime (type II modifications corresponding to nanograting formation energy domain), the main occurrence is a chemical change and re-organization of the network evidenced by the appearance of molecular O2 seen in the Raman spectra. In addition, the polarization dependence of the second harmonic generation in type II indicates that the organization of nanogratings may be perturbed by the laser-imprinted electric field.

Mercury Thiogermanate Glasses HgS-GeS2: Vibrational, Macroscopic, and Electric Properties.

Glasses in the pseudo-binary system (HgS)x (GeS2)1-x were synthesized over the concentration range of 0.0 ≤ x ≤ 0.5. The fundamental glass properties (macroscopic, electric, and vibrational) were studied using differential scanning calorimetry (DSC), direct current (dc) electrical measurements, Raman spectroscopy supported by DFT modeling, and X-ray diffraction. Mercury species in thiogermanate glasses essentially form chain-like (HgS2/2) fragments substituting bridging sulfur between corner- and edge-sharing GeS4/2 tetrahedra. This structural evolution results in a significant monotonic decrease of the glass transition temperatures from 480 to 270 °C. The room-temperature dc conductivity changes non-monotonically with increasing HgS content x over a limited range of 4 × 10-15 to 7 × 10-13 S cm-1. The electronic transport in insulating HgS-GeS2 glasses occurs via extended electronic states. Tetrahedral HgS4/4 fragments also appear in the glass network with increasing x. Their exact population needs further advanced structural studies using diffraction techniques.