尽管矿化法已被用于制备黑磷单晶中,但目前对无气相运输条件下黑磷的生长过程还鲜有报道。以锡和碘为矿化剂,采用矿化法成功地在石英管中制备出高质量的大颗粒正交黑磷单晶。基于不同的升降温工艺,研究了无气相输运条件下黑磷单晶的生长过程。结果表明:采用矿化法可制备出高质量的正交黑磷单晶;在降温过程中,可在620~500 ℃温度区间生成紫磷;500 ℃是黑磷生长的关键温度,适当延长保温时间,有利于黑磷单晶的生长。此外,阐明了无气相输运条件下黑磷的生长过程。

Although single-crystal black phosphorus (BP) can be prepared by the mineralization method, there have been few reports on the growth process of BP under non-vapor transport conditions. In this paper, a simple synthetic approach based on Sn-I-assisted mineralization is developed to produce high-quality orthorhombic single-crystal BP in a quartz tube. Through different temperature variations, we study the growth process of single-crystal BP under non-vapor transport conditions. The results show that by using the appropriate conditions, the mineralization method can be used to produce high-quality orthorhombic single-crystal BP. During the cooling process from 620 ℃ to 500 ℃, Hittorf’s phosphorus is formed. It is shown that 500 ℃ is a critical temperature for BP growth, which properly prolongs the holding time, promoting the growth of single-crystal BP. Finally, the growth process of BP under non-vapor transport conditions is clarified.