Site-specific deposition of single gold nanoparticles by individual growth in electrohydrodynamically-printed attoliter droplet reactors

Gold nanoparticles with unique electronic, optical and catalytic properties can be efficiently synthesized in colloidal suspensions and are of broad scientific and technical interest and utility. However, their orderly integration on functional surfaces and devices remains a challenge. Here we show that single gold nanoparticles can be directly grown in individually printed, stabilized metal-salt ink attoliter droplets, using a nanoscale electrohydrodynamic printing method with a stable high-frequency dripping mode. This enables controllable sessile droplet nanoreactor formation and sustenance on non-wetting substrates, despite simultaneous rapid evaporation. The single gold nanoparticles can be formed inside such reactors in situ or by subsequent thermal annealing and plasma ashing. With this non-contact technique, single particles with diameters tunable in the range of 5-35 nm and with narrow size distribution, high yield and alignment accuracy are generated on demand and patterned into arbitrary arrays. The nanoparticles feature good catalytic activity as shown by the exemplary growth of silicon nanowires from the nanoparticles and the etching of nanoholes by the printed nanoparticles.