RESUMO
We study structural and morphological transformations caused by multipulse femtosecond-laser exposure of Bridgman-grown ϵ-phase GaSe crystals, a van der Waals semiconductor promising for nonlinear optics and optoelectronics. We unveil, for the first time, the laser-driven self-organization regimes in GaSe allowing the formation of regular laser-induced periodic surface structures (LIPSSs) that originate from interference of the incident radiation and interface surface plasmon waves. LIPSSs formation causes transformation of the near-surface layer to amorphous Ga2Se3 at negligible oxidation levels, evidenced from comprehensive structural characterization. LIPSSs imprinted on both output crystal facets provide a 1.2-fold increase of the near-IR transmittance, while the ability to control local periodicity by processing parameters enables multilevel structural color marking of the crystal surface. Our studies highlight direct fs-laser patterning as a multipurpose application-ready technology for precise nanostructuring of promising van der Waals semiconductors, whose layered structure restricts application of common nanofabrication approaches.
RESUMO
Ba5(BO3)3F single crystals of high optical quality and up to 1.5 cm in diameter were grown. Its transparency range is 0.23 to 6.6 µm (on 10% level). Direct allowed electronic transitions at the Γ-point give band gap values of 5.31 and 5.40 eV at 300 and 80 K, respectively. Luminescence is excited in the near-edge absorption bands near 265 and 365 nm. X-ray irradiation induces an additional absorption in dominant 252, 317 and 710 nm bands. Combined electron spin-resonance spectroscopy and theoretical analysis allow one to associate the three absorption peaks with O(5-), O(1-) and e6(-) (fluorine vacancy), respectively. The original transparency is restored after heating the crystal to 400 K and charge carrier release from traps with ET = 0.87 eV and s = 10(12) s(-1). Dispersion curves for the refractive indices were calculated and Sellmeier equations were built. Theoretical analysis shows strong localization of the Ba 5s and F 2s orbitals, strong ionicity of the Ba cations and strong covalency of the B-O bond. The optical properties of Ba5(BO3)3F are dominantly determined by electron transitions within the (BO3)(3-) groups, despite the transition between barium and oxygen also having a little contribution.
