Micro-Raman and micro-infrared spectroscopic studies of Pb- and Au-irradiated ZrSiO4: Optical properties, structural damage, and amorphization

The optical properties of damaged periodic and aperiodic domains created by Pb+ (280 keV) and Au4+ (10 MeV) implantation of zircon were studied using micro-infrared (IR) and micro-Raman spectroscopy. The Pb+ and Au4+ irradiations caused a dramatic decrease in the IR reflectivity similar to that observed for metamict natural zircon. The irradiation with 10 MeV Au4+ ions (to fluences of 1x1015 Au4+ ions/cm2) also results in the formation of an amorphized phase similar to that observed in metamict zircon. These results show that high-energy, heavy-ion irradiations provide a good simulation of the ballistic effects of the recoil nucleus of an alpha-decay event and, in both cases, the result is the creation of aperiodic domains. Additional IR and Raman features were recorded in samples irradiated with 280 keV Pb+ ions (to fluences of 1x1014 and 1x1015 Pb+ ions/cm2), indicating the formation of an irradiation-induced additional phase(s). The frequencies of the features are consistent with lead silicates, ZrO2, and SiO2. The results show that spectral features of the Au4+- and Pb+-irradiated zircon are different from those of quenched ZrSiO4 melts, and the finding further confirms that the amorphous state produced by high-energy ion irradiations is structurally different from the glassy state that results from quenching a high temperature melt. In contrast to significant changes in the frequency and width of the Raman ν3 band observed in metamict zircon, the Pb+ and Au4+ irradiations do not cause similar variations, indicating that the remaining zircon crystalline domains in irradiated samples have a crystalline structure with fewer defects than those of metamict zircon