cm0c02273_si_001.pdf (130.21 kB)
High Yield Synthesis of Violet Phosphorus Crystals
journal contribution
posted on 2020-08-28, 13:35 authored by Lihui Zhang, Mengyue Gu, Longren Li, Xuewen Zhao, Chengcheng Fu, Ting Liu, Xuequan Xu, Yonghong Cheng, Jinying ZhangViolet
phosphorus is the most stable phosphorus allotrope with
a layered structure. The corresponding violet phosphorene, a more
stable two-dimensional semiconducting structure than black phosphorene,
is a promising two-dimensional material for electronic and optoelectronic
devices. The synthesis of violet phosphorus is the key factor to its
experimental research. However, no clear evidence has been reported
for the synthesis of violet phosphorus since its first proposal in
1865. The violet phosphorus was even debated to be a metastable intermediate
phase. Until recently, the violet phosphorus crystals have just been
successfully produced and exfoliated to give violet phosphorene. High
yield synthesis of highly crystalline and pure violet phosphorus is
crucial for the further exploration of violet phosphorus and phosphorene.
In this work, highly crystalline and pure violet phosphorus crystals
have been produced with a yield as high as 80%. The vapor transport,
nucleation, crystal growth conditions, and synthesis mechanism have
been studied to obtain violet phosphorus instead of black phosphorus.
The mixture of transport agents and amorphous red phosphorus was heated
to 600 °C to form P–Sn–I vapor and transported
to the cooler zone (580 °C). The phosphorus was separated out
from the P–Sn–I composites after cooling down to 530
°C to form violet phosphorus nuclei. The nucleation time and
further cooling time correspond to the amount and crystallinity of
violet phosphorus crystals. The precipitation has been demonstrated
to be SnI2 crystals with a space group of C2/m (12) after the growth of violet phosphorus crystals.
The synthesis of highly crystalline and pure violet phosphorus with
high yield provides the application possibility of violet phosphorus
and phosphorene in mechanic, electronic, optoelectronic, catalysts,
and medical fields.