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A method of fabricating an optical fibre or an optical device doped with reduced metal ion, in particular reduced rare earth metal ions, comprising the steps of : forming a partially sintered fine structure in a base material for fabricating the optical fibre or the optical device; soaking the fine structure in a doping solution containing a reducing agent together with a metal ion; then drying and sintering the fine structure. The reducing agent may be glucose, sucrose, glycerine, dextrin, benzene, phenol, hexane, toluene, naphthalene, or an alkoxide such as an tetraethyl orthosilicate or tetramethyl orthocarbonate. The valency of the metal ion is reduced, e.g. from Tm to Tm, thus changing the spectroscopic characteristics of the glass. The doped optical device may be used in optical switching and optical amplification applications.