Covalent functionalization of few-layer black phosphorus using iodonium salts and comparison to diazonium modified black phosphorus

Thumbnail Image
6587_BP_Accepted.pdf(1.02 MB)
Accepted version
van Druenen, Maart
Davitt, Fionán
Collins, Timothy W.
Glynn, Colm
O'Dwyer, Colm
Holmes, Justin D.
Collins, Jillian
Journal Title
Journal ISSN
Volume Title
American Chemical Society (ACS)
Research Projects
Organizational Units
Journal Issue
Since the isolation of two-dimensional (2D) phosphorene, black phosphorus (BP) has gained popularity due to its high carrier mobility and tunable bandgap. Poor ambient stability of BP remains a key issue and impedes its use in electronic applications. Here we report a new stabilization strategy based on covalent functionalization of liquid exfoliated few-layer BP using aryl iodonium salts. Arylation of BP using iodonium salts enables covalent modification without inducing oxidation and alters the degradation chemistry of BP by inhibiting bridged oxygen formation through attachment to surface oxygen sites. In comparison, functionalization using aryl diazonium salts results in oxidation and aryl multilayer formation and does not adequately disrupt noncovalent solvent passivation. Aryl functionalization of BP using iodonium salts displays superior ambient stability compared to arylation using diazonium salts associated with greater covalent functionalization as characterized using X-ray photoelectron spectroscopy, scanning transmission electron microscopy, photoluminescence, and attenuated total reflectance infrared spectroscopy.
Salts , Aromatic compounds , Chemical reactions , High resolution transmission electron microscopy , Infrared spectroscopy , Phosphorus , Scanning electron microscopy , Transmission electron microscopy , X ray photoelectron spectroscopy , Covalent functionalizations , Covalent modifications , Degradation chemistry , Electronic application , High carrier mobility , Multilayer formation , Scanning transmission electron microscopy , Two Dimensional (2 D)
van Druenen, M., Davitt, F., Collins, T., Glynn, C., O’Dwyer, C., Holmes, J. D. and Collins, G. (2018) 'Covalent Functionalization of Few-Layer Black Phosphorus Using Iodonium Salts and Comparison to Diazonium Modified Black Phosphorus', Chemistry of Materials, 30(14), pp. 4667-4674. doi: 10.1021/acs.chemmater.8b01306
© 2018 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see