X-ray emission and photoluminescence spectroscopy of nanostructured silica with implanted copper ions

Quartz glass samples and compacted SiO₂ nanopowders have been studied by x-ray emission (CuL _{2, 3} transition 3d4s → 2p _{1/2, 3/2}) and photoluminescence spectroscopy following pulsed Cu⁺ ion implantation (energy, 30 keV; pulse current up to 0.5 A; pulse duration, 400 μs; irradiation doses, 10¹⁵, 10¹⁶, and 2 × 10¹⁷ cm^?2). It has been established that ion irradiation gives rise to the formation of glassy and compacted SiO₂ samples of nanosized metallic and oxide phases in the structure. An analysis of CuL x-ray emission spectra has shown that copper nanoparticles are thermodynamically metastable and chemically active because ion beam bombardment transfers them readily to the oxide form. This results from the radiation-stimulated fracture of regular Si-O-Si bonds in amorphous SiO₂ and the formation of defective Si-Si bonds, followed by capture of oxygen by copper atoms. The enhanced degree of oxidation of copper ions in SiO₂ nanostructured pellets can be reduced by coimplantation and thermal annealing. Optical spectroscopy studies suggest that, in glasses and SiO₂ nanostructured pellets, there exist metallic Cu _n ⁰ nanoclusters, which at low temperatures exhibit quantum-confined photoluminescence with a characteristic stepped excitation spectrum.