At the desired growth temperature (900°C), carbothermally reduced Zn vapors are generated and efficiently captured by Au nanoparticles. The capturing processes occur on the Au droplets since Zn vapor #EPZ 6438 randurls[1|1|,|CHEM1|]# trapping is energetically more favorable at these sites than at the SiC surface. The supply of Zn vapors is expected to either condense directly into the Au nanoparticle or be transported from adjacent regions on
the growth substrate into the Au droplets/clusters to form clusters of Au-Zn alloys. The eutectic temperature of Au-Zn systems was estimated to be around 683°C [29] with a Zn maximum solubility in Au of 33.5 at%. However, throughout this present investigation, the growth temperatures (850 or 900°C) were well above the eutectic temperature for Au-Zn systems. As such, Au and Zn can be expected to be molten alloy droplets on the substrates. The formation of such droplets can be well described by the following expression [30]. Figure 8 Schematic of growth mechanism for ZnO nanoarchitectures. Schematic of the growth mechanism for ZnO nanoarchitectures at 900°C with (a) high density of Au nanoparticles and (b) low density of Au nanoparticles. (1) With increasing growth time, the continual supply of Zn vapors results in an increase in Zn concentration in Au-Zn alloy clusters. The process of Zn condensation/dissolution within the Au-Zn alloy system continues until
the supersaturation point, where click here a solid crystal of ZnO nucleates check details out of the molten alloy droplet [30]. However, the present experimental work shows that depending on the system (growth) temperature, ZnO nucleation can occur either on the Au-Zn alloy droplets (850°C, Figure 6c) or away from the Au-Zn alloy droplet (900°C). At 900°C, Zn-rich clusters that are precipitated on Au-Zn alloy droplets experience a drift as a result of the high thermal energy [19]. In our system, it was observed that at 700
sccm of Ar flow, the Zn cluster drift phenomenon can be significant above 850°C. As can be seen in Figure 8b (ii), the Zn cluster appears to drift with no preferential direction. The Zn cluster drift was subsequently halted either by (1) merging with other moving Zn cluster traces and/or Au-Zn alloy droplets (Figure 8a (ii) for the high density of Au nanoparticle case), (2) sticking on a substrate defect site, and/or (3) reduction in the local substrate temperature (Figure 8b (ii) for the low density of Au nanoparticle case). With continual supply of Zn vapors and residual oxygen atoms inside the growth chamber, precipitation of ZnO NWs via self-catalyzed VLS process is established (Figure 8 (iii)). Beyond this stage, NW growth is effectively controlled by a non-catalytic-assisted VLS mechanism and the Au nanoparticles play no further role in the evolution of the growth process [16, 22].