Synthesis, Structure and Optical Properties of β- and β"-Gallates

Abstract

<p> β- and β"-gallates are analogs of β-Al2O3 family. K-β"-gallate was directly synthesized via solid state reaction with β-Ga2O3 (β-gallia) precursor. When α-Ga2O3 is used as starting material, K-β-gallate forms in spite of incorporation of aliovalent ions, i.e., Li+, Zn2+ and Cd2+. It is suggested that oxygen packing sequence in the Ga2O3 precursor plays an important role on the formation of K-β- or β"- gallates. β-Ga2O3 has the ABCABC oxygen packing sequence, similar to β"-gallate structure, thus β-Ga2O3 leads to form pure K-β"-gallate; α-Ga2O3 has the hexagonal structure with ABAB oxygen packing sequence. K-β-gallate forms around the α-Ga2O3 --> β-Ga2O3 phase transformation (≈700°C). This low reaction temperature negates the aliovalent ions to stabilize β"-structure when α-Ga2O3 precursor is employed.</p> <p> K-β- or β"-gallates show good ionic conductivity. Both can be fully ion-exchanged with Ba2+ and Sr2+. Sr-β-gallate is metastable and transforms to magnetoplumbite structure after annealing at 1200°C. But Ion-exchanged Ba-β-gallate is stable. Zn2+ doped Ba-β-gallate can be directly formed at 1300°C via solid state reaction.</p> <p> Mn2+ ion-exchanged K-β-or β"-gallates exhibit green photo luminescence. Mn2+ can also locate in the spinel block to confer green photo luminescence. Eu3+, Ce3+ and Eu2+ can not be ion-exchanged into the conduction plane of K-β-gallate. There is no luminescence observed for directly synthesized BaZnGa10O17 doped with Eu3+, Ce3+ and Eu2+ due to photoionization effect. When half Ga3+ is substituted by Al3+, directly formed BaZnAl5Ga5O17: Eu3+ shows red emission upon UV excitation (254nm). Blue emission of 485nm wavelength was observed for BaZnAl5Ga5O17: Eu2+.</p> <p> The structure of β- or β"-gallates was refined by Rietveld neutron powder diffraction. Zn2+ was detected on the Ga(2) site in β-K1.64Ga10.36Zn0.64O17. Extra K+ is balanced by Zn2+. K+ is distributed between BR (2(c)) and MO (6(h)) sites. Ba2+ was detected at MO sites, slightly shift from the BR sites in β-BaZnGa10O17. Extra K+ is also compensated by Zn2+ in β"-K1.67Ga10.33Zn0.67O17. In undoped K-β-gallate, VGa(1)Ga(5)i is introduced to balance extra K+. Extra K+ in undoped K-β"-gallate is supposed to be balanced by the formation of Ga+.</p>