Access and in situ Growth of Phosphorene-Precursor Black Phosphorus

TL;DR

This paper demonstrates a method for growing high-quality black phosphorus crystals suitable for large-area phosphorene production, using a short transport reaction with in situ neutron diffraction analysis.

Contribution

It introduces a novel growth process for black phosphorus crystals from red phosphorus with in situ analysis confirming direct gas-phase formation.

Findings

Black phosphorus can be grown directly from red phosphorus.

Crystals of several millimeters with high purity are achievable.

Black phosphorus forms directly via gas phase without intermediates.

Abstract

Single crystals of orthorhombic black phosphorus can be grown by a short way transport reaction from red phosphorus and Sn/SnI4 as mineralization additive. Sizes of several millimeters can be realized with high crystal quality and purity, making a large area preparation of single or multilayer phosphorene possible. An in situ neutron diffraction study has been performed addressing the formation of black phosphorus. Black phosphorus is formed directly via gas phase without the occurrence of any other intermediate phase. Crystal growth was initiated after cooling the starting materials down from elevated temperatures at 500 {\deg}C.