Hydrogenation in amorphous silicon quantum dots (QDs) has a dramatic impact on the corresponding optical properties and band energy structure, leading to a quantum-confined composite material with unique characteristics. The synthesis of a-Si:H QDs is demonstrated with an atmospheric-pressure plasma process, which allows for accurate control of a highly chemically reactive non-equilibrium environment with temperatures well below the crystallization temperature of Si QDs (Adv. Mater. 27, 2015, 8011).