Phosphorene

Phosphorene is a two-dimensional material and allotrope of phosphorus. Phosphorene can be viewed as a single layer of black phosphorus, much in the same way that graphene is a single layer of graphite. Phosphorene is predicted to be a strong competitor to graphene because, in contrast to graphene, phosphorene has a band gap. Phosphorene was first isolated in 2014 by mechanical exfoliation. In the 1960s black phosphorus, a layered semiconducting allotrope of phosphorus, was synthesized, which exhibited high carrier mobility. In 2014, several groups introduced single-layer phosphorene, a monolayer of black phosphorus. It attracted renewed attention because of its potential in optoelectronics and electronics due to its band gap, which can be tuned via modifying its thickness, anisotropic photoelectronic properties and high carrier mobility. Phosphorene was initially prepared using mechanical cleavage, a commonly used technique in graphene production that is difficult to scale up. Liquid exfoliation is a promising method for scalable phosphorene production. Synthesis of phosphorene is a significant challenge. Currently, there are two main ways of phosphorene production: scotch-tape-based microcleavage and liquid exfoliation, while several other methods are being developed as well. Phosphorene production from plasma etching is also reported. In scotch-tape-based microcleavage, phosphorene is mechanically exfoliated from a bulk of black phosphorus crystal using scotch-tape. Phosphorene is then transferred on a Si/SiO2 substrate, where it is then cleaned with acetone, isopropyl alcohol and methanol to remove any scotch tape residue. The sample is then heated to 180 °C to remove solvent residue. In the liquid exfoliation method first reported by Brent et al. in 2014 and modified by others, bulk black phosphorus is first ground in a mortar and pestle and then sonicated in deoxygenated, anhydrous organic liquids such as NMP under inert atmosphere using low-power bath sonication. Suspensions are then centrifuged for 30 minutes to filter out the unexfoliated black phosphorus. Resulting 2D monolayer and few-layer phosphorene unoxidized and crystalline structure, while exposure to air oxidizes the phosphorene and produces acid. Another variation of liquid exfoliation is “basic N-methyl-2-pyrrolidone (NMP) liquid exfoliation”. Bulk black phosphorene is added to a saturated NaOH/NMP solution, which is further sonicated for 4 hours to conduct liquid exfoliation. The solution is then centrifuged twice, first for 10 minutes to remove any unexfoliated black phosphorus and then for 20 minutes at higher speed to separate thick layers of phosphorene (5–12 layers) from NMP. The supernatant then is centrifuged again at higher speed for another 20 minutes to separate thinner layers of phosphorene (1–7 layers). The precipitate from centrifugation is then redispersed in water and washed several times by deionized water. Phosphorene/water solution is dropped onto silicon with a 280-nm SiO2 surface, where it is further dried under vacuum. NMP liquid exfoliation method was shown to yield phosphorene with controllable size and layer number, excellent water stability and in high yield. The high yield production of phosphorene has been demonstrated by many groups in solvents, but to realize the potential applications of this material, it is crucial to deposit these free-standing nanosheets in solvents systematically on substrates. H. Kaur et al. demonstrated the synthesis, interface driven alignment and subsequent functional properties of few layer semiconducting phosphorene using Langmuir-Blodgett assembly. This is the first study which provides a straightforward and versatile solution towards the challenge of assembling nanosheets of phosphorene onto various supports and subsequently use these sheets in an electronic device. Therefore, wet assemblies techniques like Langmuir-Blodgett serves as a very valuable new entry point for the exploration of electronic as well as opto-electronic properties of phosphorene as well as other 2D layered inorganic materials. It is still a challenge to directly epitaxially grow 2D phosphorene because the stability of black phosphorene is highly sensitive to substrate, which is understanding by theoretical simulations.