This Article reports measurements of the intra-and intermolecular ordering of tight-binding octylphosphonate ligands on the surface of colloidal CdSe quantum dots (QDs) within solid state films, and the dependence of this order on the size of the QDs. The order of the organic ligands, as probed by vibrational sum frequency generation (SFG) spectroscopy, decreases as the radius of the QDs decreases; this decrease is correlated with a decrease in the order of underlying Cd2+, as detected by X-ray photoelectron spectroscopy (XPS) line width measurements, for radii of the QDs, R > 2.4 nm, and is independent of the disorder of the Cd2+ for R < 2.4 nm. We believe that, for R < 2.4, the decreasing order of the ligands with decreasing size is due to an increase in the curvature of the QD surfaces. Disorder in the Cd2+ results from the presence of a shell of Cd2+- surfactant complexes that form during synthesis, so this work demonstrates the possibility for chemical control over molecular order within films of colloidal QDs by changing the surfactant mixture.
ASJC Scopus subject areas
- Colloid and Surface Chemistry