The spectroscopic properties, structure and interconversions of optically active oxygen-deficiency-related point defects in vitreous silica are reviewed. These defects, the E′-centers (oxygen vacancies with a trapped hole or 3-fold-coordinated silicons), different variants of diamagnetic `ODCs' (oxygen-deficiency centers), and their Ge-related analogs play a key role in the fiber-optic Bragg grating writing processes. The controversy surrounding the structural models for the Si- and Ge-related ODCs is discussed and the similarity between the bulk and surface point defects in silica is emphasized. The possible interconversion mechanisms between 2-fold-coordinated Si, neutral oxygen vacancies and E′-centers are discussed. The effects of glassy disorder have a profound effect on defect properties and interconversion processes in silica.

Optically active oxygen-deficiency-related centers in amorphous silicon dioxide

Interface states and electron spin resonance centers have been observed and compared in thermally oxidized (111) and (100) silicon wafers subjected to various processing treatments. The ESR Pb signal, previously assigned to interface ⋅Si≡Si3 defects on (111) wafers, was found to have two components on (100): an ⋅Si≡Si3 center oriented in accord with (100) face structure, and an unidentified center consistent with ⋅Si≡Si2O. The quantitative proportionality of Pb spin concentration to midgap interface trap density Dit is maintained on (100), and both are lower by a factor of about 3 compared to (111). This correlation persists over the range of oxidation temperatures 800–1200°C, for both n‐ and p‐doped silicon, cooled by fast pull in oxygen, and cooled or annealed in nitrogen or argon. The correlation is independent of doping level. In samples with different oxide thickness, neither Pb nor Dit varied significantly over the range 100–2000 A, but Pb was smaller at 50 A. In general, ESR is judged to offer prom...

Interface states and electron spin resonance centers in thermally oxidized (111) and (100) silicon wafers

The present paper reviews a quarter of a century of electron spin resonance (ESR) studies in glasses. Specific subtopics addressed include transition-group ions, radiation-induced defect centers, ferromagnetic precipitates, and photo-induced centers. For brevity, most of the examples in the first three categories are confirmed to the familiar oxide glass systems and only the most concrete conclusions are elaborated. The section treating radiation-induced defects is further abridged in light of several reviews of this topic in the current literature. Even within these limitations of scope, a great diversity of material is summarized. Most of the studies cited provide information concerning the atomic scale structure of the host glasses and several have immediate impact on practical problems ranging from glass technology to geochemistry.

Electron spin resonance in glasses

The ESR Pb center has been observed in thermally oxidized single‐crystal silicon wafers, and compared with oxide fixed charge Qss and oxidation‐induced interface states Nst. The Pb center is found to be located near the interface on (111) wafers. Its g anisotropy is very similar to that of known bulk silicon defects having SiIII bonded to three other Si atoms; the Pb unpaired electron orbital, however, is exclusively oriented normal to the (111) surface. The Pb center cannot be identified with any other known defect in Si or SiO2; in particular, it is totally unlike the common E′ center of SiO2. In contrast to Qss, both Pb and Nst were found to be greatly reduced by steam oxidation and hydrogen annealing. Both Pb and Nst may be regenerated by subsequent N2 anneals at 500 °C. In a graded series of samples, Pb and Nst are found to be proportional and nearly equal in concentration. This possible confirmation of SiIII at the interface, and correlation with Nst, support the theoretical indication of an SiIII b...

ESR centers, interface states, and oxide fixed charge in thermally oxidized silicon wafers

A review is made of recent literature dealing with radiation‐induced point defects distributed volumetrically in thermally grown SiO2‐on‐Si or superficially at the silicon interface, with particular emphasis on the results of electron‐spin‐resonance experimentation. The observed defect types and their anneal kinetics are then compared with recent advances in the understanding of similar species and processes in irradiated bulk fused silica. It is concluded that radiolytic molecular hydrogen is formed in thermally grown SiO2 layers, just as it is in bulk fused silica, and that the diffusion of this hydrogen determines the temperature and time dependencies of the post‐irradiation interface state buildups.

G.H. Sigel

Papers

Observation and analysis of the primary 29Si hyperfine structure of the E′ center in non-crystalline SiO2