Experimental results and a discussion of possible chemical pathways in the formation of thermally stable chemical composition gratings in optical fibers are presented. Gratings are formed through high-temperature treatment of UV-exposed hydrogen-loaded fibers. The final refractive-index modulation is ascribed to variations in fluorine concentration attained by periodically increased diffusion of fluorine. The mechanism behind this increase is the formation of mobile hydrogen fluoride from chemical reactions of fluorine and UV-induced hydroxyl, which occur with the spatial periodicity of the UV pattern. A hydroxyl-assisted increase in fluorine diffusion has been verified by time-of-flight secondary-ion mass spectroscopy. Formation of ultrastable grating by periodic variation of oxygen concentration through diffusion of molecular water is also discussed.
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