Structure and stability of two dimensional phosphorene with O or NH functionalization

We investigate the stability and electronic properties of oxy-(O) or imine-(NH) functionalized monolayer phosphorene with either single-side or double-side functionalization based on density-functional theory calculations. Our thermodynamic analysis shows that oxy-functionalized phosphorene can be formed under the conditions ranging from ultrahigh vacuum to high concentrations of molecular O2, while the imide-functionalized phosphorene can be formed at relatively high concentrations of molecular N2H2. In addition, our Born–Oppenheimer molecular dynamics (BOMD) simulation shows that under ambient conditions both O2 and N2H2 can etch phosphorene away.

[1]  Gustavo E. Scuseria,et al.  Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] , 2006 .

[2]  F. Xia,et al.  Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics. , 2014, Nature communications.

[3]  M. Lazzeri,et al.  Structure and stability of graphene nanoribbons in oxygen, carbon dioxide, water, and ammonia , 2010, 1009.1808.

[4]  Jinlong Yang,et al.  Organometallic Hexahapto-Functionalized Graphene: Band Gap Engineering with Minute Distortion to the Planar Structure , 2013 .

[5]  A S Rodin,et al.  Strain-induced gap modification in black phosphorus. , 2014, Physical review letters.

[6]  Douglas M. Warschauer,et al.  Electrical and Optical Properties of Crystalline Black Phosphorus , 1963 .

[7]  M. Dion,et al.  van der Waals density functional for general geometries. , 2004, Physical review letters.

[8]  Wei Ji,et al.  High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus , 2014, Nature communications.

[9]  M. Chou,et al.  Structural and electronic properties of oxidized graphene. , 2009, Physical review letters.

[10]  R. Keyes.  The Electrical Properties of Black Phosphorus , 1953 .

[11]  D. Bowler,et al.  Van der Waals density functionals applied to solids , 2011, 1102.1358.

[12]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[13]  A. Morita,et al.  Band structure and optical properties of black phosphorus , 1984 .

[14]  Eugenie Samuel Reich,et al.  Phosphorene excites materials scientists , 2014, Nature.

[15]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[16]  Xianfan Xu,et al.  Phosphorene: an unexplored 2D semiconductor with a high hole mobility. , 2014, ACS nano.

[17]  Shoji Suzuki,et al.  Electronic band structure of black phosphorus studied by angle-resolved ultraviolet photoelectron spectroscopy , 1985 .

[18]  S. Rundqvist,et al.  Refinement of the crystal structure of black phosphorus , 1965 .

[19]  J. Elguero,et al.  Pnicogen bonds between X═PH3 (X = O, S, NH, CH2) and phosphorus and nitrogen bases. , 2014, The journal of physical chemistry. A.

[20]  Philip Kim,et al.  Reversible basal plane hydrogenation of graphene. , 2008, Nano letters.

[21]  P Taylor,et al.  Specificity and orientation of trigonal carboxyl esters and tetrahedral alkylphosphonyl esters in cholinesterases. , 1995, Biochemistry.

[22]  Jun Dai,et al.  Bilayer Phosphorene: Effect of Stacking Order on Bandgap and Its Potential Applications in Thin-Film Solar Cells. , 2014, The journal of physical chemistry letters.

[23]  Patterning nanoroads and quantum dots on fluorinated graphene , 2010, 1012.4217.

[24]  Thomas H. Bointon,et al.  Nanopatterning of fluorinated graphene by electron beam irradiation. , 2011, Nano letters.

[25]  P. W. Bridgman.  TWO NEW MODIFICATIONS OF PHOSPHORUS. , 1914 .

[26]  Xianfan Xu,et al.  Phosphorene: an unexplored 2D semiconductor with a high hole mobility. , 2014, ACS nano.

[27]  T. Inabe,et al.  Synthesis and characterization of black phosphorus intercalation compounds , 1987 .

[28]  J. C. Jamieson.  Crystal Structures Adopted by Black Phosphorus at High Pressures , 1963, Science.

[29]  Qiang Sun,et al.  Tuning electronic and magnetic properties of graphene by surface modification , 2009 .

[30]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[31]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[32]  Y. Kawazoe,et al.  Ferromagnetism in semihydrogenated graphene sheet. , 2009, Nano letters.

[33]  Xiaojun Wu,et al.  Phosphorene Nanoribbons, Phosphorus Nanotubes, and van der Waals Multilayers , 2014, 1403.6209.

[34]  M. Otyepka,et al.  Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. , 2012, Chemical reviews.

[35]  M. Hersam,et al.  Chemically homogeneous and thermally reversible oxidation of epitaxial graphene. , 2012, Nature chemistry.

[36]  R. Soklaski,et al.  Layer-controlled band gap and anisotropic excitons in few-layer black phosphorus , 2014 .

[37]  J. Robinson,et al.  Properties of fluorinated graphene films. , 2010, Nano letters.

[38]  K. Novoselov,et al.  Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane , 2008, Science.

[39]  Li Yang,et al.  Strain-Engineering Anisotropic Electrical Conductance of Phosphorene , 2014 .

[40]  G. Steele,et al.  Isolation and characterization of few-layer black phosphorus , 2014, 1403.0499.

[41]  Likai Li,et al.  Black phosphorus field-effect transistors. , 2014, Nature nanotechnology.

[42]  Francesco Mauri,et al.  Structure, stability, edge states, and aromaticity of graphene ribbons. , 2008, Physical review letters.

[43]  Jijun Zhao,et al.  Stability of graphene oxide phases from first-principles calculations , 2010 .

[44]  A. H. Castro Neto,et al.  Electric field effect in ultrathin black phosphorus , 2014 .

[45]  Li Yang,et al.  Strain-engineering the anisotropic electrical conductance of few-layer black phosphorus. , 2014, Nano letters.