Luminescence of isoelectronically ion-implanted SiO2 layers

Scanning electron microscopy (SEM) and cathodoluminescence (CL) in combination with scanning transmission electron microscopy (STEM) have been used to investigate thermally grown amorphous silicon dioxide layers implanted isoelectronically with group IV ions (C+, Si+, Ge+, Sn+, Pb+) as well as with group VI ions (O+, S+, Se+). Besides the main luminescent centers in a-SiO2 layers: the red R luminescence (650 nm; 1.9 eV) of the non-bridging oxygen hole centers (NBOHC), the blue B (460 nm; 2.7 eV) and the UV (290 nm; 4.3 eV) band of the oxygen deficient centers (ODC), in ion implanted silica additional emission bands are observed. E.g. in Ge+ implanted layers a huge violet band appears at 410 nm (3.1 eV) increasing with the thermal annealing process due to formation of Ge dimers, trimers or higher aggregates, finally leading to destruction of the luminescence centers by further growing to Ge nanoclusters. The Ge cluster size is shown by STEM cross section micrographs.
Generally, group IV element implantation and partial substitution of silicon increases the luminescence in the blue/violet region whereas group VI elements and additional oxygen increase the intensity in the red region, confirming the association of the blue and the red luminescence with oxygen deficient centers and oxygen excess centers, respectively. Thus, the cathodoluminescence spectra of sulfur and oxygen implanted SiO2 layers under special conditions show besides the characteristic luminescence bands a multimodal structure beginning in the green region at 500 nm and extending up to the near infrared region at 820 nm. The energy step differences of the sublevels amount in the average 120 meV and indicate vibronic-electronic transitions, probably of O − interstitial molecules.