Changes in the optical absorption and the formation of point defects in three types of synthetic SiO2 glasses, wet (OH content; 120 ppm), dry (OH content <1 ppm), and fluorine (F)-doped (∼1 mol %) SiO2 glasses, by irradiation with fluorine dimer (F2) excimer laser light pulses (∼8 mJ/cm2/pulse×3.6×105 pulses) were examined by various spectroscopic methods. Intense optical absorptions were induced in the wet and dry silicas in the range of 4–8 eV, whereas the intensity of absorptions induced in the F-doped silica was smaller by an order of magnitude than that in the F-free glasses. The optical transmission at the wavelength of 157 nm after the irradiation was F-doped silica≫wet silica>dry silica. The dominant electron spin resonance-active defect in the irradiated specimens was the nonbridging oxygen-hole center (NBOHC) for the wet silica, or the E′ center in the dry silica. The concentration of NBOHCs or E′ centers in the F-doped silica was lower by an order of magnitude than that in the wet or dry silica. The present results suggest the possibility of using F-doped silica glasses as photomask materials for F2 laser lithography.
ZnO polycrystals doped with Li, Cu or Al were prepared by solid-state reactions and their
cathodoluminescence (CL) and electron spin resonance (ESR) spectra were measured. A strong
yellow emission centered at 2.0 eV was observed for the Al-doped specimen and its intensity was
higher than that of the green emission observed for the Al-free samples. The intensity of the green
emission was independent of the annealing atmosphere. On the other hand, the intensity of the
yellow emission was enhanced by annealing in Ar gas but was suppressed by annealing in O2 gas.
The increase of the intensity of the ESR signal at g≈1.96 was parallel to the increase in the yellow
emission intensity. The effect of Al-doping upon CL spectra was discussed on the basis of the
assignment that the yellow emission is due to a donor-acceptor pair transition.
Color-center formation in F-doped, OH-free synthetic SiO(2) glasses by irradiation with F(2) excimer lasers (157 nm) was examined as a function of the F content. The concentration of photoinduced E(') centers was reduced to approximately 1/20 by 1 mol.% F(2) doping and remained almost constant on further doping to 7.3 mol. %. The absorption edge was considerably shifted to a lower wavelength (157.4 nm -->153 nm for a 5-mm-thick sample) by 1-mol. % doping and decreased only slightly on further doping. The intensities of the Raman bands that are due to three- and four-membered ring structures were significantly reduced by 1-mol. % F doping. These results strongly suggest that elimination of strained Si-O-Si bonds by F doping plays a central role in the improvement of radiation resistance of SiO(2) glasses to F(2) laser light.
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