Preparation of Black Phosphorus Single Crystals by a Completely Closed Bismuth-Flux Method and Their Crystal Morphology

Abstract

Needle-shaped and film- or plate-shaped black phosphorus single crystals were prepared by an improved bismuth-flux method. The conversion of red phosphorus to white phosphorus and the growth of black phosphorus single crystals from the solution of white phosphorus in liquid bismuth were performed in an evacuated quartz-glass apparatus without breaking the vacuum. Needle crystals measured about 5 mm in length and 10 to 100 µm in thickness. The thickness of film or plate crystals ranged from 1 to 10 µm and the width was usually above 100 µm, generally increasing with decreasing thickness. Some crystal morphologies were observed and analyzed crystallographically.

Electronic and Magnetic Properties of Black Phosphorus

“…The value for eV is obtained through fitting the curve. This value agrees well with the literature: eV and eV found in polycrystalline materials, eV, eV, eV and eV found in single crystals, therefore this regime is identified as the intrinsic one.…”

Black Phosphorus Rediscovered: From Bulk Material to Monolayers

“…[49] In this synthetic procedure,w hite phosphorus was treated with 30-40 at. [36,39] Ther eported procedure involved mixing Bi and white phosphorus at 400 8 8Cfor 20 hand then cooling the mixture at 18 8 8Ch À1 .T he crystallization of BP from aBimelt was further investigated by Baba et al [51] In 2007, the Nilges research group achieved significant progress in low-temperature methods for the synthesis of BP by using Sn and its alloys with Au. %b yt reating BP with Pb and Au under av acuum at elevated temperatures (300-440 8 8C).…”

Emerging Trends in Phosphorene Fabrication towards Next Generation Devices

“…[27] Table 1 depicts the different studies based on bulk growth of BP. BP in its bulk form can be synthesized through different methods such as the high-pressure route, [35,[103][104][105][106][107][108] recrystallization from bismuth (Bi) flux, [59,60,109] chemical vapor transport [110][111][112][113][114] and mechanical milling. [115,116] www.advancedscience.com Adv.…”

“…The entire process of converting the red P to white P and the crystallization of BP was carried out in an evacuated quartz-glass apparatus inside vacuum because white P should not be exposed to air as it is poisonous, highly reactive and inflammable in air. [109] A quartz ampoule containing the white P (with a melting point of 44.1 °C) was melted at 80 °C and then moved towards the Bi (heated to 300 °C). Later, the ampoule was placed in an electric furnace, heated to 400 °C for 48 h and finally cooled down.…”