Covalent Functionalization and Passivation of Exfoliated Black Phosphorus via Aryl Diazonium Chemistry

Abstract

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical, and electronic properties. Exfoliated black phosphorus, a layered two-dimensional semiconductor exhibiting favorable charge carrier mobility, tunable bandgap, and highly anisotropic properties, is chemically reactive and degrades rapidly in ambient conditions. In contrast, here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated black phosphorus even following weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent, and alters the electronic properties of exfoliated black phosphorus, ultimately yielding a strong, tunable p-type doping that simultaneously improves field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated black phosphorus, thus improving its prospects for nanoelectronic applications.

In print; 27 pages with supporting information in Nature Chemistry 2016

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Cited by in corpus (29)

• Degradation of Black Phosphorus (BP): The Role of Oxygen and Water
• Electronic Transport in Two-Dimensional Materials
• Atomically thin p-n junctions based on two-dimensional materials
• Post Graphene 2D Chemistry: The Emerging Field of Molybdenum Disulfide and Black Phosphorus Functionalization
• Noncovalent Functionalization of Black Phosphorus
• Low-Symmetry Two-Dimensional Materials for Electronic and Photonic Applications
• Field Effect Optoelectronic Modulation of Quantum-Confined Carriers in Black Phosphorus
• Decoration of exfoliated black phosphorus with nickel nanoparticles and application in catalysis
• Multilayer InSe-Te van der Waals heterostructures with ultrahigh rectification ratio and ultrasensitive photoresponse
• Polymer-based black phosphorus (bP) hybrid materials by in situ radical polymerization: an effective tool to exfoliate bP and stabilize bP nanoflakes
• A Perspective on Recent Advances in Phosphorene Functionalization and its Application in Devices
• NaSn2As2: An Exfoliatable Layered van der Waals Zintl Phase
• Single-step exfoliation and functionalization of few-layers black phosphorus and its application for polymer composites
• Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles
• Modelling Strategies for the Covalent Functionalization of 2D Phosphorene
• Monolayer black phosphorus by sequential wet-chemical surface oxidation
• Edge-Epitaxial Growth of InSe Nanowires toward High-Performance Photodetectors
• Thermal Sublimation: a Scalable and Controllable Thinning Method for the Fabrication of Few-Layer Black Phosphorus
• Covalent Functionalized Black Phosphorus Quantum Dots
• The 2D pn Junction Driven Out-of-Equilibrium
• Long-Term Environmental Stability of Nitrogen-Healed Black Phosphorus
• Idiosyncratic Approach to Visualize Degradation of Black Phosphorus
• Angstrom-wide conductive channels in black phosphorus by Cu intercalation
• Lattice Opening Upon Bulk Reductive Covalent Functionalization of Black Phosphorus
• Single-Crystalline Metallic Films Induced by van der Waals Epitaxy on Black Phosphorus
• Electronic structure and conductivity in functionalized multilayer black phosphorene
• Anisotropy of the Optical Properties of Pentacene:Black Phosphorus Interfaces
• Electronic structure and transport in materials with flat bands: 2D materials and quasicrystals
• Liquid phase mass production of air-stable black phosphorus/phospholipids nanocomposite with ultralow tunneling barrier