Crystal Structure And Photoluminescence Properties Of An Incommensurate Phase In Euo- And P2o5-Doped Ca2sio4

We have for the first time clarified the incommensurately modulated crystal structure as well as the photoluminescence properties of Eu2+ -activated Ca2SiO4 solid solution, the chemical formula of which is (Ca1.88Eu0.012+square(0.11))-(Si0.78P0.22)O-4, where square denotes vacancies in Ca sites with the replacement of Si4+ by P5+. The emission spectrum upon the 335 nm excitation showed a relatively broad band centered at ca. 490 nm and a full width at half-maximum of ca. 80 nm. The crystal structure was made up of the four types of beta-Ca2SiO4-like layers with one type of interlayer. The incommensurate modulation with superspace group Pnma(0 beta 0)00s was induced by the long-range stacking order of these layers. The modulation wavevector was 0.27404(2) x b*, with the basic unit-cell dimensions being a = 0.68355(2) nm, b = 0.54227(2) nm, and c = 0.93840(3) nm (Z = 4). The basic structure contained two nonequivalent Ca sites. One site was fully occupied by Ca2+ and free from Eu2+ in the overall incommensurate structure. The occupational modulation at the other site was so significant that the sum of site occupation factors for Ca2+ and Eu2+ as low as 0.5 was seen at the interlayer. This site was too large for accommodation of Ca2+ but was suitable for Eu2+. Thus, the Eu2+ ions would exclusively concentrate at the relevant site, which would cause the emission peak of the incommensurate phase to be shifted to the shorter wavelength ranges as compared with those of the other commensurate phases such as beta and alpha'(L).