Selective anisotropic growth of Bi₂S₃ nanoparticles with adjustable optical properties

We report on the controlled synthesis and functionalization in two steps of elongated Bi₂S₃ nanoparticles within a wide range of sizes. First, we show the effect of the temperature and reaction time on the synthesis of two series of nanoparticles by the reaction of thioacetamide with bismuth(III) neodecanoate in the presence of organic surfactants. At 105 °C and long reaction times, nanoneedles of about 45 nm in length containing larger crystallites are obtained, while highly crystalline nanorods of about 30 nm in length are dominant at 165 °C, regardless of the reaction time. The optical properties of both types of nanoparticles show an enhancement of the band gap compared to bulk Bi₂S₃. This is likely to arise from quantum confinement effects caused by the small particle dimensions relative to the typical exciton size, together with an increase in near-infrared absorption due to the anisotropic particle shape. Second, a ligand exchange approach has been developed to transfer the Bi₂S₃ nanoparticles to aqueous solutions by grafting dimercaptosuccinic acid onto the surface of the particles. The as-prepared coated nanoparticles show good stability in water, in a wide biological pH range, and in phosphate-buffered saline solutions. Overall, this work highlights the controlled design at all levels - from the inorganic core to the organic surface coating - of elongated Bi₂S₃ nanoparticles, leading to a tunable optical response by tuning their morphology and size.