γ-BaB2O4: High-Pressure High-Temperature Polymorph of Barium Borate with Edge-Sharing BO4 Tetrahedra.

Abstract

The α- and β-modifications of barium metaborate are important functional materials used in optoelectronic devices. A new theoretically predicted modification of BaB2O4 has been synthesized under conditions of 3 GPa and 900 °C, using the DIA-type apparatus. The new high-pressure modification, γ-BaB2O4, crystallizes in a centrosymmetrical group of monoclinic syngony (P21/n (#14), a = 4.6392(4) Å, b = 10.2532(14) Å, c = 7.066(1) Å, β = 91.363(10)°, Z = 4). A distinctive feature of the γ-BaB2O4 structure is the presence of edge-sharing tetrahedra [B2O6] which form infinite double chains ∞[B4O4O8/2] stretching along the a axis. The number of known structural types with the [B2O6] group is limited. Phase γ-BaB2O4 has the shortest distance between boron atoms of shared tetrahedra among all currently known compounds. The [B2O6] group angles are 95.5° and 105.5°. Thermodynamic stability and electronic properties of the γ-BaB2O4 modification were studied. The width of the band gap, calculated using the HSE06 functional, is 7.045 eV which implies transparency in the deep-UV region. Experimental and numerical methods which demonstrate a good match were used to the study the Raman spectra of γ-BaB2O4 and β-BaB2O4 modifications. In the Raman spectra of γ-BaB2O4, the most intense band at a frequency of 853 cm-1 was found to correspond to the symmetric bending mode of the B-O-B-O ring in edge-sharing tetrahedra.