Sizing, stoichiometry and optical absorbance variations of colloidal cadmium sulphide nanoparticles

Simple preparative methods were used to synthesise cadmium sulphide particles in the size ranges larger than those associated with quantum confinement. UV/visible absorption spectra were measured. Rayleigh and Mie theories were used to analyse normalised absorption spectra to allow estimates of particle size and number to be obtained simultaneously. Each model was utilised in an appropriate size and wavelength range. Surprisingly, Mie calculations were found to over-estimate the absorbance of particles below 50 nm radius. Powder X-ray diffraction results showed the crystallites to be independent of particle size and suggested that the particles grew through aggregation of smaller bodies. The Mie results could therefore be interpreted in terms of changes in the particles' optical indicatrix with radius. Large poly-crystalline particles (>50 nm radius) should possess a near spherical indicatrix, fulfilling the assumptions of the Mie theory. The indicatrix of particles smaller than 50 nm should become increasingly anisotropic with decreasing size, leading to discrepancies between the Mie model and measured data. Although the results could also be explained through changes in the magnitude of the particle refractive index, compositional (Auger electron spectroscopy, energy dispersive X-ray analysis) and structural (powder X-ray diffraction) analyses of the particles complicate the hypothesis. Energy dispersive X-ray results showed that small cadmium sulphide particles possessed a large excess of sulphur suggesting a change in effective cadmium sulphide stoichiometry.