Surface Modification of Black Phosphorus with Group 13 Lewis Acids for Ambient Protection and Electronic Tuning.

Herein we introduce a facile, solution-phase protocol to modify the Lewis basic surface of few-layer black phosphorus (bP) and demonstrate its effectiveness at providing ambient stability and tuning of electronic properties. Commercially available group 13 Lewis acids that range in electrophilicity, steric bulk, and Pearson hard/soft-ness are evaluated. The nature of the interaction between the Lewis acids and the bP lattice is investigated using a range of microscopic (optical, atomic force, scanning electron) and spectroscopic (energy dispersive, X-ray photoelectron) methods. Al and Ga halides are most effective at preventing ambient degradation of bP (>84 h for AlBr3 ), and the resulting field-effect transistors show excellent IV characteristics, photocurrent, and current stability, and are significantly p-doped. This protocol, chemically matched to bP and compatible with device fabrication, opens a path for deterministic and persistent tuning of the electronic properties in bP.

Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling.

Surface functionalization of two-dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced herein is a mild, surface-specific protocol for the surface functionalization of few-layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational, X-ray photoelectron, solid state 31 P NMR, and UV-vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy, 15 N-labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.

Adverse Effect of PTFE Stir Bars on the Covalent Functionalization of Carbon and Boron Nitride Nanotubes Using Billups-Birch Reduction Conditions.

The functionalization of nanomaterials has long been studied as a way to manipulate and tailor their properties to a desired application. Of the various methods available, the Billups-Birch reduction has become an important and widely used reaction for the functionalization of carbon nanotubes (CNTs) and, more recently, boron nitride nanotubes. However, an easily overlooked source of error when using highly reductive conditions is the utilization of poly(tetrafluoroethylene) (PTFE) stir bars. In this work, we studied the effects of using this kind of stir bar versus using a glass stir bar by measuring the resulting degree of functionalization with 1-bromododecane. Thermogravimetric analysis studies alone could deceive one into thinking that reactions stirred with PTFE stir bars are highly functionalized; however, the utilization of spectroscopic techniques, such as Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, tells otherwise. Furthermore, in the case of CNTs, we determined that using Raman spectroscopy alone for analysis is not sufficient to demonstrate successful chemical modification.