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The optical properties of lead sulfide quantum dots (QDs) of different sizes embedded in a nanoporous silicate glass matrix (NSM) are investigated by steady-state and transient photoluminescence spectroscopy. The use of this matrix allows the fabrication of samples with reproducible optical characteristics, for both isolated and close-packed QDs. Low-temperature PL analysis of isolated QDs with sizes of 3.7 and 4.5 nm shows that the coefficient of temperature shift of the PL position changes sign with reducing QD size because of size-dependent contributions from thermal expansion, mechanical strain, and electron–phonon coupling. The PL intensity is determined by size-dependent splitting of the lowest energy electronic state.

X-ray structural analysis, together with steady-state and transient optical spectroscopy, is used for studying the morphology and optical properties of quantum dot superlattices (QDSLs) formed on glass substrates by the self-organization of PbS quantum dots with a variety of surface ligands. The diameter of the PbS QDs varies from 2.8 to 8.9 nm. The QDSL's period is proportional to the dot diameter, increasing slightly with dot size due to the increase in ligand layer thickness. Removal of the ligands has a number of effects on the morphology of QDSLs formed from the dots of different sizes: for small QDs the reduction in the amount of ligands obstructs the self-organization process, impairing the ordering of the QDSLs, while for large QDs the ordering of the superlattice structure is improved, with an interdot distance as low as 0.4 nm allowing rapid charge carrier transport through the QDSLs. QDSL formation does not induce significant changes to the absorption and photoluminescence spectra of the QDs. However, the luminescence decay time is reduced dramatically, due to the appearance of nonradiative relaxation channels.

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