Syntheses And Characterization Of Bismuth And Lead Chalcogenides And Their Ternary Alloys From Single Source Precursors

This research describes the syntheses and characterization of lead and bismuth chalcogenide nanoparticles and thin films from single source precursors. The single source precursors used were dithiocarbonates, dithio- and diselenoureas, and dithiocarbamates. These precursors were characterized using micro-elemental analyses, thermogravimetric analyses, infrared spectroscopy, nuclear magnetic resonance spectrometry and mass spectrometry. The single crystal structures of bismuth ethyl xanthate and its 1, 10 phenanthroline adduct were determined. The complexes were used for the syntheses of nanoparticles using the hot injection and thin films using the spin coating technique. The as-synthesized nanoparticles and thin films were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, inductively coupled plasma, energy dispersive X-ray spectroscopy and absorption measurements. Optical band gaps were estimated from the absorption data using Tauc’s plots. For the PbS thin films from lead dithiocarbonates, the effect of the alkyl chain length on the morphology and size of the nanocrystals were investigated. There was a change in morphology from cubes to fibrous structures as the alkyl chain changed from ethyl to dodecyl, thus confirming the anisotropic nature of PbS. SEM analyses of Bi2S3 thin films also showed a change in shape from nanowires of the bismuth ethyl xanthate to clusters of nanorods (triethylamine, pyridine) and nanodots (1,10 phenanthroline) depending on the choice of nitrogen adduct. Ternary PbSxSe(1-x) thin films deposited from lead xanthate and lead selenourea showed a gradual shift in p-XRD pattern to lower 2 theta values as the mole fraction of the lead selenourea complex in the coating mixture changed from 0 to 1 at an interval of 0.1. Estimated optical band gaps for the parent binaries (PbS and PbSe) and their ternary alloys (PbSxSe(1-x)) were all blue shifted from their respective bulk materials. PbSxSe(1-x) nanoparticles synthesized from lead thio- and selenourea complexes also exhibited a similar trend in both p-XRD and optical band gap. EDX analyses confirmed the presence of Pb, S and Se in all the PbSxSe(1-x) alloys formed at different atomic percentages depending on the ratios of the starting materials. The effects of different concentrations of Bi doping on the optical and structural properties of PbS nanoparticles have been investigated. Morphological studies showed cubes at 50% Bi doping suggesting the incorporation of the Bi atoms into the crystal lattice of the PbS nanoparticles. However, an interplay between rods and cubes were seen at 80% Bi doping. The estimated band gaps for PbS and Bi2S3 were 0.72 and 1.94 eV respectively with the alloy having band gaps in between the two binaries.