A water-based route has been demonstrated for synthesizing ZnSe and Cd-doped ZnSe (Zn(x)Cd(1-x)Se, 0 < x < 1) quantum dots (QDs) that have tunable and narrow photoluminescence (PL) peaks from the ultraviolet A (UVA) to the blue range (350-490 nm) with full-width at half-maximum (fwhm) values of 24-36 nm. Hydrazine (N(2)H(4)) was used to maintain oxygen-free conditions, allowing the reaction vessel to be open to air. The properties of the QDs were controlled using the thiol ligands, 3-mercaptopropionic acid (MPA), thiolglycolic acid (TGA), and l-glutathione (GSH). On the basis of optical spectra, linear three-carbon MPA attenuated nucleation and growth, yielding small ZnSe QDs with a high density of surface defects. In contrast, TGA and GSH produced larger ZnSe QDs with lower surface defect densities. The absorption spectra show that growth was more uniform and better controlled with linear two-carbon TGA than branched bifunctional GSH. After 20 min of growth TGA-capped ZnSe had an average diameter of 2.5 nm based on high-resolution transmission electron microscopy images; these nanocrystals had an absorbance peak maximum of approximately 340 nm (3.65 eV) and a band gap PL emission peak at 372 nm (3.34 eV). Highly fluorescent Zn(x)Cd(1-x)Se QDs were fabricated by adding a Cd-thiol complex directly to ZnSe QD solutions; PL peaks were tuned in the blue range (400-490 nm) by changing the Zn to Cd ratio. The Cd-bearing nanocrystals contained proportionally more Se based on X-ray photoelectron spectroscopy, and Cd-Se bonds had ionic character, in contrast to primarily covalent Zn-Se bonds.
We report the first synthesis of high-quality binary and ternary Sb(2)Se(3-x)S(x) nanotubes across the entire compositional range from x = 0 to 3 via a simple, low-cost, colloidal synthetic method of injection of Sb(III)-complex solution into a hot paraffin liquid containing Se, S, or a mixture thereof. In contrast to the classic rolling mechanism, the modular formation of the reported nanotubes follows a four-stage self-seeding process: (i) amorphous nanospheres, (ii) short crystalline nanotubes growing out of relatively large amorphous nanospheres, (iii) long crystalline nanotubes attached to small amorphous nanospheres, and (iv) single-crystal nanotubes. The obtained single-crystal nanotubes have tunable composition, orthorhombic phase, well-defined rectangular cross sections, and growth direction along [001], as revealed by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and selected area electron diffraction studies. UV-vis-NIR absorption spectroscopy reveals that the optical bandgap energy of the Sb(2)Se(3-x)S(x) (0 < or = x < or = 3) nanotubes increases quadratically with the sulfur concentration x with these bandgap energies falling in the range from 1.18 to 1.63 eV at the red edge of the solar spectrum. The present study opens a new avenue to low-cost, large-scale synthesis of high quality semiconductor nanotubes with technological applications in solar energy conversion and also for a wide range of optical nanodevices operating in the near-infrared.
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