Attaining 2D Black Phosphorus and Investigations into Floating-Electrode Dielectric Barrier Discharge Treatment of Solutions
Authors:   , Smith Joshua Benjamin , Ji Haifeng 
Published: July 2021

Since the discovery and isolation of the 2D carbon allotrope, graphene, research into additional 2D materials has significantly expanded. Electrical components continue to decrease in size so there is an ever-growing need for smaller circuitry to keep up with the demand. Research with graphene and additional 2D layered materials, such as transition metal dichalcogenides, brought about a realization of many unique properties that have never been previously explored for applications in electronics, photonics, and optoelectronics. Phosphorene, a novel 2D material isolated from bulk black phosphorus, is an intrinsic p-type material with a variable band gap for a variety of applications. However, these applications are limited by the inability to isolate films of phosphorene. This work investigates some of the previously found techniques for use with graphene isolation and their adaptations to phosphorene. Isolation of phosphorene from black phosphorus was investigated by exfoliation from bulk, chemical vapor deposition, and thin film conversion. Mechanical exfoliation with a tape method, drawing method, and tape/drawing method were used to isolate few-layer black phosphorus samples from bulk material. These methods were also briefly compared to liquid exfoliation of black phosphorus. A chemical vapor deposition approach led to the discovery of a novel method for growth of amorphous red phosphorus thin films from bulk red phosphorus/black phosphorus. An in situ chemical vapor deposition type approach was developed using these thin films for growth of a variety of 2D phosphorus allotropes. Successful conversion has provided fibrous phosphorus wires and hexagons, along with violet phosphorus and eventually black phosphorus. This approach demonstrates progress towards direct growth of 2D black phosphorus onto substrates with average areas >3 [mu]m2 and thicknesses representing samples around 4 layers. Thicker samples were also observed with average areas >100 [mu]m2. X-ray diffraction, transmission electron microscopy, and Raman spectroscopy have confirmed successful growth of 2D black phosphorus from red phosphorus thin films for potential uses in 2D semiconductor applications. Additionally, this work discusses some of the chemistry occurring in solution as a result of nonthermal plasma treatment from a floating-electrode dielectric barrier discharge (FE-DBD) configuration. Nonthermal plasma generation allows for the treatment of heat sensitive materials. This has opened up the field to numerous clinical applications of nonthermal plasma treatment including sterilization and wound healing along with potentials in dentistry, dermatology, and even food industries. FE-DBD plasma treatment of water was found to provide a wide-range antimicrobial solution that remained active following 2 years of aging. This plasma-treated water was found to generate a number of ROS/RNS and the formation of these components was studied and verified with UV/Vis and ESR spectroscopy. Enhanced effects were observed when cell culture medium was plasma treated, suggesting the formation of additional reactive species from the plasma treatment of a variety of biomolecules. It is essential to understand these effects for a number of reasons. The possibility to generate a wide range of antimicrobial solutions from air, water, and basic biomolecules could provide a solution for those bacteria that have developed antibiotic resistances. Simultaneously, information into the reaction mechanisms of this FE-DBD plasma treatment can be investigated. All of the applications mentioned above involve complex networks of basic biomolecules, from skin tissue to bacteria cell walls. This work analyzes the effects of plasma treatment on several biomolecule solutions and simultaneously takes aim at understanding some of the potential mechanisms of plasma treatment. Studies were carried out using NMR and GC/MS. This information was used to investigate the possible targeted areas for FE-DBD plasma treatment and to simultaneously explain the antimicrobial effects.