CuCl microcrystals‐doped SiO2 glass is prepared by the co‐sputtering method using extremely pure CuCl source materials as well as a pure SiO2 target. Low temperature optical absorption spectra (2 K) show the shift of the Z1,2 as well as the Z3 exciton peaks, indicating that the mean radius of the microcrystals is about 5.8 nm.

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