RESUMEN
A current challenge in silicon chemistry is to perform liquid-phase synthesis of silicon nanoparticles, which would permit the use of colloidal synthesis techniques to control size and shape. Herein we show how silicon nanoparticles were synthesized at ambient temperature and pressure in organic solvents through a redox reaction. Specifically, a hexacoordinated silicon complex, bis(N,N'-diisopropylbutylamidinato)dichlorosilane, was reduced by a silicon Zintl phase, sodium silicide (Na4Si4). The resulting silicon nanoparticles were crystalline with sizes tuned from a median particle diameter of 15 nm to 45 nm depending on the solvent. Photoluminescence measurements performed on colloidal suspensions of the 45 nm diameter silicon nanoparticles indicated a blue emission signal, attributed to the partial oxidation of the Si nanocrystals or to the presence of nitrogen impurities.
RESUMEN
Crystalline silicon particles sustaining Mie resonances are readily obtained from the thermal processing of hydrogen silsesquioxane (HSQ). Here, the mechanisms involved in silicon particle formation and growth from HSQ are investigated through real-time in situ analysis using an environmental transmission electron microscope and X-ray diffractometer. The nucleation of Si nanodomains is observed starting around 1000 °C. For the first time, a highly mobile intermediate phase is experimentally observed, thus demonstrating a previously unknown growth mechanism. At least two growth processes occur simultaneously: the coalescence of small particles into larger particles and growth mode by particle displacement through the matrix toward the HSQ grain surface. Postsynthetic characterization by scanning electron microscopy further supports the latter growth mechanism. The gaseous environment employed during synthesis impacts particle formation and growth under both in situ and ex situ conditions, impacting the particle yield and structural homogeneity. Understanding the formation mechanisms of particles provides promising pathways for reducing the energy cost of this synthetic route.
