Ag–Ga–S quantum dots (QDs) are obtained by colloidal synthesis in aqueous solutions with glutathione ligands at mild conditions. The QDs can be assigned to metastable orthorhombic, rhombohedral, or rocksalt‐type phases, assuming a significant internal pressure within crystallites, while the conventional tetragonal AgGaS2 phase is less likely formed. Similarly to these metastable phases, the QDs reveal a relatively narrow indirect bandgap contrary to the wide and direct bandgap of tetragonal AgGaS2. Size‐selected fractions of the colloidal solutions are separated by repeated centrifuging with addition of 2‐propanol. The QD size is evaluated from atomic force microscopy, while the crystallite size determined using the Scherrer formula is underestimated. X‐ray photoemission spectroscopy reveals that the QD composition changes from nearly stoichiometric for the fraction with the largest QDs toward Ag deficient and S rich for smaller QDs. The synthesized QDs are characterized by the absorption edge blueshift with decreasing QD size. A blueshift of the photoluminescence (PL) peak with decreasing QD size is observed as well as a nonmonotonous size dependence of the PL intensity. Raman spectra of the Ag–Ga–S QDs are discussed compared to those of bulk crystals and a strong contribution of surface phonons is revealed.
Colloidal AgInS2 quantum dots (QDs) with intense broadband photoluminescence (PL) were synthesized in aqueous solutions in the presence of glutathione at mild conditions. Size-selective fractioning of QDs was performed by repeated centrifugation of the colloidal solution with the addition of 2-propanol. Based on the optical absorption and PL data, the dependences of the band gap and the PL maximum position on the QD size are analyzed. The Raman spectra of AgInS2 QDs exhibit only a slight variation with decreasing QD size explained by phonon confinement. Changes in the Raman spectra with increasing laser power density are most likely related to photoinduced oxidation of the AgInS2 QD surface with the formation of S-O bonds.
Properties of CdSe nanocrystals (NCs) fabricated in aqueous solutions at relatively mild conditions in the presence of gelatine and stabilized in polymer (gelatine, gelatine + polyvinylpyrrolidone, polyvinyl alcohol) matrices are characterized by Raman, optical absorption and photoluminescence spectroscopies. The effect of heating of the reaction mixture on the average NC size is discussed.
Size-selected series of copper-deficient colloidal Cu–In–S quantum dots (QDs) stabilized with glutathione are obtained by the exchange reaction in aqueous solutions under mild synthesis conditions. The optical bandgap and photoluminescence maximum position shift toward higher energies with decreasing QD size. Based on X-ray diffraction data, the QDs are assigned to a tetragonal chalcopyrite-type structure. The average size of QDs, estimated from the Scherrer formula and from the comparison with the absorption edge-based sizing curves, exhibits a fair agreement, being in the interval of 1.2–2.9 nm. The Raman spectra of Cu–In–S QDs are analyzed with the account for the QD structure, confinement-related effects, non-stoichiometry, and possible existence of secondary phases.
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