Hybrid electronic properties between the molecular and solid state limits: Lead sulfide and silver halide crystallites

Tiny single PbS crystals of ∼25 A diameter are synthesized and studied optically in low‐temperature colloidal solutions. Electron microscopic examination shows a simple cubic rock salt structure with a lattice constant unchanged, within experimental error, from the bulk value. These crystallites lack the near infrared electronic absorption characteristic of bulk PbS. The small crystallite absorbance in the visible rises more steeply than does the bulk absorbance. These results reflect electron and hole localization if one considers the variation in effective mass across the band structure. A simple discussion of localization anywhere in the Brillouin zone is given. For the first time, crystallite syntheses are carried out in solvent mixtures that form transparent glasses upon cooling. The PbS spectra are independent of temperature (at current experimental resolution) down to 130 K, in contrast to earlier results for quantum size exciton peaks in ∼20 A ZnS crystallites. Previously published observations of...