Growth of silver nanowires from solutions: a cyclic penta-twinned-crystal growth mechanism

Silver nanowires are synthesized by simple reduction of the silver ions with reductants such as glucose, sodium citrate, and sodium hypophosphite, etc., in the absence of the so-called surfactants or capping reagents at the temperature from 80 to 200 degrees C. Regardless of the reductants, the nanowires prepared at a given temperature are uniform in diameters, ranging from 30 to 50 nm at 100 degrees C. Nanoparticles coexist with nanowires in the products with larger diameters (usually larger than 50 nm). We find that all the silver nanowires in the as-prepared products are of cyclic penta-twinned structure, where five crystallites bond by the {111} facets. We propose that the intrinsic factor of the cyclic penta-twinned structure, i.e., the angular mismatch of the five crystallites in forming a gapless rod, controls the size of the nanowires and guides the directional growth of the nanowires with {110} as the active facets. The nanoparticles in the products are aggregates of imperfect penta-twinned crystals, which inhibits them from growing into nanowires and results in larger size. From the structural information of the nanoparticles synthesized at room temperature, we propose that the formation of the cyclic penta-twinned structure is due to the stacking fault and the intrinsic equilibrium structures of the lower energy.