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Silicon‐rich silicon nitride films with different stoichiometry were grown on the silicon substrate using the plasma‐enhanced chemical vapor deposition. The excess silicon content in the films was monitored via varying the NH3/SiH4 gas flow ratio from 0.45 up to 1.0. High‐temperature annealing was employed to produce the silicon nanocrystals (NCs) in the films and to enhance the photoluminescence...