Size-selecting effect of water on fluorescent silicon clusters

Silicon clusters were produced by gas aggregation in vacuum and co-deposited with water vapour onto a cold target where the water vapour froze. Melting of the ice yielded fluorescent silicon nanoparticles suspended in water which were investigated by photoluminescence spectroscopy (PL) and atomic force microscopy (AFM). The PL spectrum showed a prominent band at 420 nm and other, less intense bands at shorter wavelengths. No fluorescence was observed below 275 nm. The shortest wavelength observed was related to a silicon cluster diameter of 0.9 nm using a simple particle-in-a-box model. Drops of the suspension were also deposited on freshly cleaved HOPG and investigated by AFM. The images showed single and agglomerated clusters with heights of typically 0.6 up to 2 nm. The sizes displayed by our measurements are not correlated to the average sizes that result from gas aggregation, indicating a size-selecting effect of the water suspension. The cluster-cluster interaction in water is governed by repulsion due to thermal energy and attraction due to van der Waals forces. For very small clusters repulsion dominates; at 3 nm diameter the two forces are balanced. We identify this stable phase of small clusters as the origin of exceptionally stable fluorescence.