The phosphor powders of Ca(m/2)−xEuxSi12−(m+n)Alm+nOnN16−n (m = 1.6, n = 0.8, x in the range of 0–0.08) were synthesized by means of a solid state reaction in flowing nitrogen in a carbon resistant furnace and the influence of Eu concentration on the crystal structure and photoluminescent properties was thoroughly studied. The optical properties of selected α-sialon:Eu2+ samples at temperatures in the range of 10 to 500 K and pressures up to 240 kbar are presented. The crystal lattice parameters were affected by doping with europium and some increase of the unit cell volume was observed up to 6 mol % of Eu. The higher concentration of europium led to subtle changes in the overall structure of the produced sialon phosphors. It was shown that the chemical composition of Ca, Eu-α-sialon phosphor was slightly different from the designed one and the phosphor powders were contaminated by AlN. The phosphor particle surface showed significant europium and oxygen enrichment with Eu3+ but below the thin surface layer Eu2+ was dominant and higher nitrogen content was observed. After examination of absorption, excitation, and emission spectra it was found that the emission peak position shifted toward longer wavelengths with rising Eu2+ concentration from 565 nm (0.1 mol % Eu2+) to 585 nm (10 mol % Eu2+). The quantum yield of the phosphors reached the maximum at a rather low concentration of 4 mol % of Eu. Excitation spectra depend on the monitored wavelength which is typical for multisite Eu2+. The existence of many Eu2+ sites in the sample was supported by the dependence of the decay time on the monitored wavelength.
