We report on the synthesis of semiconductor nanocrystals of PbS, ZnS, CdS, and MnS through a facile and inexpensive synthetic process. Metal-oleylamine complexes, which were obtained from the reaction of metal chloride and oleylamine, were mixed with sulfur. The reaction mixture was heated under appropriate experimental conditions to produce metal sulfide nanocrystals. Uniform cube-shaped PbS nanocrystals with particle sizes of 6, 8, 9, and 13 nm were synthesized. The particle size was controlled by changing the relative amount of PbCl(2) and sulfur. Uniform 11 nm sized spherical ZnS nanocrystals were synthesized from the reaction of zinc chloride and sulfur, followed by one cycle of size-selective precipitation. CdS nanocrystals that consist of rods, bipods, and tripods were synthesized from a reaction mixture containing a 1:6 molar ratio of cadmium to sulfur. Spherical CdS nanocrystals (5.1 nm sized) were obtained from a reaction mixture with a cadmium to sulfur molar ratio of 2:1. MnS nanocrystals with various sizes and shapes were synthesized from the reaction of MnCl(2) and sulfur in oleylamine. Rod-shaped MnS nanocrystals with an average size of 20 nm (thickness) x 37 nm (length) were synthesized from a 1:1 molar ratio of MnCl(2) and sulfur at 240 degrees C. Novel bullet-shaped MnS nanocrystals with an average size of 17 nm (thickness) x 44 nm (length) were synthesized from the reaction of 4 mmol of MnCl(2) and 2 mmol of sulfur at 280 degrees C for 2 h. Shorter bullet-shaped MnS nanocrystals were synthesized from a 3:1 molar ratio of MnCl(2) and sulfur. Hexagon-shaped MnS nanocrystals were also obtained. All of the synthesized nanocrystals were highly crystalline.

A new and simple method has been developed to synthesize large quantities of highly monodisperse tetragonal zirconia nanocrystals. In this synthesis, a nonhydrolytic sol-gel reaction between zirconium(IV) isopropoxide and zirconium(IV) chloride at 340 degrees C generated 4 nm sized zirconia nanoparticles. A high-resolution transmission electron microscopic (HRTEM) image showed that the particles have a uniform particle size distribution and that they are highly crystalline. These monodisperse nanoparticles were synthesized without any size selection process. X-ray diffraction studies combined with Rietveld refinement revealed that the ZrO(2) nanocrystals are the high-temperature tetragonal phase, and very close to a cubic phase. When zirconium(IV) bromide is used as a precursor instead of zirconium chloride, zirconia nanoparticles with an average size of 2.9 nm were obtained. The UV-visible absorption spectrum of 4 nm sized zirconia nanoparticles exhibited a strong absorption starting at around 270 nm. A fluorescence spectrum with excitation at 300 nm showed a broad fluorescence band centered around 370 nm. FTIR spectra showed indication of TOPO binding on the ZrO(2) nanoparticle surface. These optical studies also suggest that the nanoparticles are of high quality in terms of narrow particle size distribution and relatively low density of surface trap states.

Lead sulfide, PbS, nanoparticles have been synthesized using a number of surface capping agents including poly(vinyl-alcohol) (PVA), poly(vinyl-pyrrolidone) PVP, gelatin, DNA, polystyrene (PS), and poly(methylmethacrylate) (PMMA). The electronic absorption spectra and particle shapes have been found to depend on the capping molecules used. An excitonic feature at 580 nm was observed for capping with PVA and DNA, while no such excitonic feature was observed for PVP, PS or PMMA. A weak excitonic feature was observed for gelatin. The particle shape varied from cubic, needle to spherical as controlled by the capping agents. For the DNA-capped PbS nanocrystals, HRTEM demonstrated the presence of oval crystals with a diameter of 3-8 nm. Powder X-ray diffraction of the PbS-DNA nanocrystals showed the characteristic peaks for PbS at 2.97, 3.43, and 2.10 Å. The XRD suggested the size of the nanoparticles to be approximately 4 nm. The dynamics of photoinduced electrons in PbS nanoparticles have been determined using femtosecond laser spectroscopy. For all the samples studied the electronic relaxation has been found to be very similar and follow a double exponential decay with time constants of 1.2 and 45 ps. The fast decay can be attributed to trapping from the conduction band to shallow traps or from shallow traps to deep traps while the slower decay is most likely due to electron-hole recombination mediated by a high density of surface trap states that lie within the band gap. The decay profiles are independent of particle size, shape, surface capping, probe wavelength, and excitation intensity. The results seem to indicate a high density of surface states, consistent with no detectable fluorescence signal at room temperature.