Self-catalytic solution-liquid-liquid-solid (SLLS) growth of tapered SnS nanorods

Taper-shaped SnS nanorods were synthesized via mild chemistry, and the self-catalytic solution-liquid-liquid-solid (SLLS) process was proposed as a crystal growth mechanism. There exists a distinct difference in our SLLS growth compared to the well-known SLS growth in that we injected Sn precursors into a hot trioctylphosphine sulfide (TOPS) solution, which is a reverse process of the general SLS growth. This reverse process could prevent the oxidation of Sn precursors and thus it could facilitate the growth of SnS nanorods, since the surface of Sn clusters and droplets could be momentarily passivated by TOPS molecules. Without addition of extra catalyst nanoparticles, the nucleation and growth of SnS nanorods was induced by liquid Sn droplets. Spherical Sn tips existing at the top of the nanorods evidence the self-catalytic growth. The SLLS growth was proposed based upon the large Sn clusters existing at the bottom of the SnS nanorods in an intermediate stage (5 s) of the growth and the tapered morphology of the nanorods. The growth of SnS nanorods could progress by the upward diffusion of Sn atoms from large liquid Sn clusters along the surface of the SnS nanorods to the interfacial liquid layers (neck area) and the diffusion of S decomposed from TOPS in the solution to the neck area. SnS nanorods showed a direct energy band gap of ∼1.6 eV, determined by using the Kubelka-Munk transformation of UV-visible spectra. This self-catalytic SLLS growth produced high-quality and single crystalline SnS nanorods within only 15 s at 290 °C.