Chemical Exfoliation of Black Phosphorus for Nanoelectronics Applications
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Chemical Exfoliation of Black Phosphorus for Nanoelectronics Applications Misook Min1, Gustavo A. Saenz1, Gang Qiu2, Adam Charnas2, Peide Ye2, and Anupama B. Kaul1* 1
Electrical and Computer Engineering Department, University of Texas at El Paso, El Paso, TX, USA. 2 Electrical and Computer Engineering Department, Purdue University, Lafayette, IN, USA. ABSTRACT Chemically exfoliated two-dimensional (2D) materials have shown promise in a variety of applications such as thin film transistors and photovoltaic devices. Here, we present a scalable method for preparing black phosphorus membranes via direct liquid-phase exfoliation of the bulk crystal in organic solvents. The black phosphorus sheets are characterized by Raman and Photoluminescence (PL) spectroscopy, and optical microscopy. The properties of these chemically exfoliated black phosphorus was compared to mechanically exfoliated nanomembranes. The liquid-phase exfoliation nonetheless yields the potential for large-area scalability. Our results highlight the important aspects of forming solution dispersions of 2D black phosphorus which can subsequently be the stepping stone for future work on the ink-jet printing of such dispersions over a wide range of substrates.
INTRODUCTION Two-dimensional (2D) materials including graphene [1, 2], MoS2 [3], WSe2 [4] and black phosphorus [5] have attracted significant interest in electronics [6], optoelectronic devices [7] and biosensors [8]. Among the various 2D materials, black phosphorus is a semiconductor with a thickness-dependent, direct band gap ranging from ~0.3 eV in the bulk to ~1.5 eV in the monolayer limit [9, 10]. Furthermore, mechanically exfoliated black phosphorus possesses high ON/OFF ratios (~104 ─ 105) [11] and room temperature mobility (~200 ─ 1000 cm2 V-1 s-1) [12]. Therefore, black phosphorus has great potential for various applications such as inkjet printing. As a powerful direct writing technique, inkjet printing has received increasing interest in electronics and other applications. Black phosphorus can be obtained by different approaches such as mechanical exfoliation [13], chemical vapor deposition, and liquid-phase exfoliation [14]. Liquid-phase exfoliation is a powerful technique to produce black phosphorus sheets in large quantities. However, black phosphorus is unstable because of degradation via chemical reaction with water and oxygen. Here, we present liquid exfoliation method to obtain black phosphorus by sonication in organic solvent such as N-Methyl-2-pyrrolidone (NMP) at ambient conditions. Here we compare the structural properties of black phosphorus through Raman Spectroscopy analysis, Photoluminescence (PL) and two-terminal electronic device measurements. The properties of the chemically exfoliated dispersions were compared to mechanically exfoliated samples of black phosphorus.
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