On the spectra luminescence properties of charoite silicate

Charoite is a hydrous alkali calcium silicate mineral [K4NaCa7Ba0.75Mn0.2Fe0.05(Si6O15)2(Si2O7)Si4O9(OH)·3(H2O)] exhibiting an intense lilac colour related to Mn2+ and Fe3+ colour centres. These ions also contribute to a strong luminescence at ∼585 and 705 nm. This work studies the thermal dependence of these luminescent centres by (i) thermoluminescence (TL) of pre-heated and pre-irradiated charoite aliquots, (ii) by time-resolved cathodoluminescence (TRS-CL) at room and cryogenic temperatures (RT and CT), (iii) by spatially resolved spectra CL under scanning electron microscopy (SRS-CL-SEM) and (iv) by ion beam spectra luminescence (IBL) with H+, H2+ and 4He+ ions at RT and LT. The main peak, ∼585 nm, is linked to a transition 4T1,2 (G)→6A7(S) in Mn2+ ions in distorted six-fold coordination and the emission at ∼705 nm with Fe2+→Fe3+ oxidation in Si4+ lattice sites. Less intense UV-blue emissions at 340 and 390 nm show multi-order kinetic TL glow curves involving continuous processes of electron trapping and de-trapping along with an irreversible phase transition of charoite by de-hydroxylation and lattice shortening of Δa=0.219 Å, Δb=0.182 Å; Δc=0.739 Å. The Si-O stressed lattice of charoite has non-bridging oxygen or silicon vacancy-hole centres, and Si-O bonding defects which seem to be responsible for the 340 nm emission. Extrinsic defects such as the alkali (or hydrogen)-compensated [AlO4/M+] centres could be linked with the 390 nm emission. Large variations in 585 and 705 nm intensities are strongly temperature dependent, modifying local Fe-O and Mn-O bond distances, short-range-order luminescence centres being very resistant under the action of the heavy ion beam of 4He+. The SRS-CL demonstrates strong spatial heterogeneity in the luminescence of the charoite.