We report on the synthesis and optical and structural characterization of ultrasmall (<2 nm) CdS nanoparticles with a narrow size distribution of 10% prepared in aqueous and alcohol solutions of polyethyleneimine (PEI). The PEI-stabilized CdS nanoparticles reveal a structured absorption band with the first excitonic maximum at 3.5 eV and broad-band photoluminescence with quantum yields of 12−14% in water, 18−20% in ethanol (80 vol %), and up to 60−70% in solid PEI films at room temperature. The nature of the photoluminescence was studied by using the time- and wavelength-dependent emission measurements. The role of precursor cadmium(II)−PEI complex in the formation of uniform and ultrasmall luminescent CdS nanoparticles, as well as the dynamic emission quenching by water, are discussed. A study of the photochemical properties of PEI-stabilized CdS nanoparticles both under continuous and nanosecond pulse illumination showed excellent stability of solid PEI films incorporating CdS nanoparticles toward UV illumination and reductive character of the CdS nanoparticle photocorrosion in aqueous solutions.
The above-bandgap illumination of colloidal ZnO nanoparticles (NPs) in ethanol solutions is found to lead to reversible shifts of the absorption and photoluminescence (PL) excitation spectra, indicating charging of the nanoparticles with electrons. A rapid drop of deep-level PL intensity at the early stage of illumination is observed simultaneously with the splitting-off and growth of a new red-shifted near-band-edge PL band. Such a splitting of the near-bandgap PL band under illumination is observed for the first time and corroborates with the previous assumptions about the behavior of the NP ensemble emission upon gradual NPs’ charging with electrons. The possible relation between the new PL band and photoinduced charging of NPs with excess electrons is discussed on the basis of the dependence of the PL spectrum evolution and absorption band shift relaxation on the NP size and controllable access of oxygen during illumination.
Thermal treatment of graphitic carbon nitride (g-CN) in aqueous solutions of tetraethyl ammonium hydroxide at ∼100 °C yields colloidal solutions retaining stability at a CN concentration of up to 50 g L−1 and upon dilution by a factor of 103.
Stable colloidal solutions of zinc oxide in dimethylsulfoxide were synthesized via interaction between zinc(II) acetate and tetraalkylammonium hydroxides (alkyl-ethyl, propyl, butyl, and pentyl). Colloids of ZnO emit photoluminescence in a broad band with a maximum at 2.3-2.4 eV with quantum yields of up to 9-10% at room temperature and 15-16% at 80 K. The photoluminescence is supposed to originate from the radiative recombination of conduction band electrons with holes captured by deep traps having corresponding states in the band gap 1.0-1.2 eV above the valence band edge. The size of colloidal ZnO nanocrystals depends on the duration and temperature of the post-synthesis treatment and varies in the range of 3-6 nm. Growth of the ZnO nanocrystals can be terminated at any moment of the thermal treatment by freezing the colloidal solution or by addition of tetraethyl orthosilicate which hydrolyses forming core-shell ZnO@SiO2 particles. ZnO nanocrystals introduced into polyethyleneimine films can be used as an active component of an LED emitting at an applied voltage higher than 13 V.
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