Nebol'sin Valery A, Levchenko Elena V, Yuryev Vladimir, Swaikat Nada
Department of Radio Engineering and Electronics, Voronezh State Technical University, 14 Moskovsky Pr., 394026 Voronezh, Russia.
School of Information and Physical Sciences, College of Engineering, Science and Environment, University of Newcastle, Callaghan, NSW 2308, Australia.
ACS Omega. 2023 Feb 23;8(9):8263-8275. doi: 10.1021/acsomega.2c06475. eCollection 2023 Mar 7.
During the nanowire (NW) formation, the growth steps reaching the crystallization front (CF) under the catalytic drop are either absorbed by the three-phase line or accumulated in front of it, curving the surface of the front. In this paper, we have analyzed the conditions leading to a change of shape of the crystallization front of the NWs under the catalyst drop as well as the reasons for the formation of atomically smooth (singular) and curved (nonsingular) regions. A model explaining the curvature of the crystallization front under the drop in the process of NW growth is proposed. The model demonstrates that under conditions of good wettability of the crystalline surface with a catalytic liquid and nucleation at regular places of the growing NW face, a metastable equilibrium at the CF near the three-phase line is achieved due to the thermodynamic size effect of reduction of overcooling (supersaturation). This metastable equilibrium results in the curvature of the CF. The CF curvature depends on the NW radius and the level of overcooling (supersaturation) in the droplet. During this process, the low-index inclined facets adjacent to the wetting perimeter of the catalyst drop may appear on the curved CF.
在纳米线(NW)形成过程中,到达催化液滴下方结晶前沿(CF)的生长台阶要么被三相线吸收,要么在其前方累积,从而使前沿表面弯曲。在本文中,我们分析了导致催化剂液滴下方纳米线结晶前沿形状变化的条件,以及原子级光滑(奇异)和弯曲(非奇异)区域形成的原因。提出了一个解释纳米线生长过程中液滴下方结晶前沿曲率的模型。该模型表明,在晶体表面与催化液具有良好润湿性且在生长的纳米线表面规则位置成核的条件下,由于过冷(过饱和)降低的热力学尺寸效应,在三相线附近的结晶前沿实现了亚稳平衡。这种亚稳平衡导致了结晶前沿的曲率。结晶前沿的曲率取决于纳米线半径和液滴中的过冷(过饱和)水平。在此过程中,与催化剂液滴润湿周边相邻的低指数倾斜面可能会出现在弯曲的结晶前沿上。