Using photon-in photon-out soft x-ray absorption and emission spectroscopy, the electronic structure of silicon nanoclusters embedded in an electrically insulating SiO₂ host matrix is investigated as a function of nanocluster size. Using the new method of cluster preparation the size of the Si clusters is well controlled. The diameter of the nanoclusters was less than 5nm.

We find the nanoclusters to be of a core-shell structure with a crystalline Si core and a thin transition layer of a suboxide. Based on the spectroscopic data the electronic structure of the Si core and the chemical content of the suboxide shell are studied. The presented results are in agreement with photoluminescence measurements.

Effects of electronic quantum confinement are detected in the Si cores. We find that the influence of confined excitonic states and the presence of SiO₂ matrix manifests itself predominantly in the unoccupied electronic states.

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