Bromine doping of silica glass is demonstrated. Bromine doping can be achieved with SiBr4 as a precursor. Bromine doping can occur during heating, consolidation or sintering of a porous silica glass body. Doping concentrations of bromine increase with increasing pressure of the doping precursor and can be modeled with a power law equation in which doping concentration is proportional to the square root of the pressure of the doping precursor. Bromine is an updopant in silica and the relative refractive index of silica increases approximately linearly with doping concentration. Bromine can be used as a dopant for optical fibers and can be incorporated in the core and/or cladding regions. Core doping concentrations of bromine are sufficient to permit use of undoped silica as an inner cladding material in fibers having a trench in the refractive index profile. Co-doping of silica glass with bromine and chlorine is also demonstrated.