Characterization, optical and luminescence features of cobalt ions in multi-component PbO[sbnd]Al2O3[sbnd]TeO2[sbnd]GeO2[sbnd]SiO2 glass ceramics

Abstract

Glass ceramics of the composition PbOAl2O3TeO2GeO2SiO2 doped with CoO (ranging between 0 and 1.0 mol %) were prepared by melt quenching technique followed by heat treatment. The techniques such as XRD, SEM, EDS and DTA were employed for the characterization of the prepared samples. Conventional spectroscopic studies viz., optical absorption, photoluminescence, FTIR and Raman were also performed on these samples. The optical absorption spectra of the titled glass ceramics exhibited two principal absorption bands, one at about 594 nm and the second one consisting of multiplets with the meta centre at about 1455 nm ascribed to the 4A2 (4F) → 4T1 (4P) and 4A2 (4F) → 4T1 (4F) transitions of tetrahedrally coordinated Co2+ ions, respectively. Besides these, the spectra also exhibited two feeble bands at about 532 and 643 nm which are the characteristics of octahedrally coordinated Co2+ and Co3+ ions, respectively. Using Tanabe Sugano diagram the crystal field splitting parameter Dq, Racah parameters B, C and nephelauxetic ratio, β were evaluated for Co2+ ions. The photoluminescence spectra of the titled glass ceramics have exhibited two broad emission bands at 628 and 870 nm ascribed to 4T1 (4P) → 4A2 (4F) and 4T1 (4P) → 4T2 (4F) tetrahedral transitions of Co2+ ions, respectively. FTIR and Raman spectra of the titled samples exhibited various asymmetrical and symmetrical vibrational bands due to viz., silicate, germanate, PbO4, PbO6, AlO6, TeO4, TeO3 and CoIIIO vibrations in the glass ceramic matrix. The spectroscopic investigations on the titled glass ceramics have revealed that if CoO is present in small quantities the cobalt ions predominantly occupy the octahedral sites in the glass network, whereas the tetrahedrally coordinated Co2+ ions are found to increase if the concentration of nucleating agent CoO is gradually increased up to 1.0 mol%. As a result the degree of depolymerization of the glass network decreases which in turn enhances its rigidity with increasing the concentration of nucleating agent CoO. From these investigations we report that the glass ceramics doped with 1.0 mol% of CoO are suitable for insulating devices as well as for photonic devices.