Inorganic Chemistry, Vol.52, No.22, 12972-12979, 2013
Crystal Structures and Properties of Europium Aluminum Oxynitride Eu2Al03.75N0.1 and Europium Aluminum Oxide EuAl2O4
The reactions among Eu2O3, AlN, and Al2O3 with the ratios Eu:Al = 2:1 and 1:2 at 1200 degrees C for 10 h yielded Eu2AlO3.75N0.1 and EuAl2O4, respectively. The powder X-ray diffraction pattern of the new oxynitride could be indexed as a monoclinic structure with the space group I2 (No. 5) (a = 3.7113(2) angstrom, b = 3.6894(2) angstrom, c = 12.3900(8) angstrom, and beta = 90.6860(5)degrees). This structure was found to be a novel distorted Ruddlesden-Popper type. For EuAl2O4, isostructural with monoclinic SrAl2O4 (space group P2(1), No. 4), a structural refinement was performed, indicating that the cell parameters were a = 8.44478(11) angstrom, b = 8.82388(12) angstrom, c = 5.15643(7) angstrom, and beta = 93.1854(12)degrees. Eu-151 Mossbauer spectra revealed that the divalent and trivalent Eu ions coexisted in Eu2AlO3.75N0.1, while Eu ions were in the divalent state in EuAl2O4. A photoluminescent mechanism due to 4f(7) (S-8(7/2)) <-> 4f(6)5d(1) of europium in EuAl2O4 was proposed on the basis of the calculated band structure, the band gap obtained from UV-vis diffuse reflectance spectra, and the photoluminescence spectra.