Synthesis of Atomically Thin Boron Films on Copper Foils.

Two-dimensional boron materials have recently attracted extensive theoretical interest because of their exceptional structural complexity and remarkable physical and chemical properties. However, such 2D boron monolayers have still not been synthesized. In this report, the synthesis of atomically thin 2D γ-boron films on copper foils is achieved by chemical vapor deposition using a mixture of pure boron and boron oxide powders as the boron source and hydrogen gas as the carrier gas. Strikingly, the optical band gap of the boron film was measured to be around 2.25 eV, which is close to the value (2.07 eV) determined by first-principles calculations, suggesting that the γ-B28 monolayer is a fascinating direct band gap semiconductor. Furthermore, a strong photoluminescence emission band was observed at approximately 626 nm, which is again due to the direct band gap. This study could pave the way for applications of two-dimensional boron materials in electronic and photonic devices.

[1]  Probing the synthesis of two-dimensional boron by first-principles computations. , 2013, Angewandte Chemie.

[2]  Ya-Fan Zhao,et al.  Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets , 2014, Nature Communications.

[3]  Lester Andrews,et al.  Reactions of boron atoms with molecular oxygen. Infrared spectra of BO, BO2, B2O2, B2O3, and BO−2 in solid argon , 1991 .

[4]  A. Paxton,et al.  Boron in copper: A perfect misfit in the bulk and cohesion enhancer at a grain boundary , 2007, 0711.1629.

[5]  L. Dubrovinsky,et al.  Pressure-induced isostructural phase transformation in γ -B 28 , 2010 .

[6]  L. Dubrovinsky,et al.  Polarized Raman spectroscopy of high-pressure orthorhombic boron phase , 2009 .

[7]  Yunqi Liu,et al.  Monolayer Hexagonal Boron Nitride Films with Large Domain Size and Clean Interface for Enhancing the Mobility of Graphene‐Based Field‐Effect Transistors , 2014, Advanced materials.

[8]  J. Gillespie Crystallization of Massive Amorphous Boron , 1966 .

[9]  Lain-Jong Li,et al.  Recent advances in controlled synthesis of two-dimensional transition metal dichalcogenides via vapour deposition techniques. , 2015, Chemical Society reviews.

[10]  Madan Dubey,et al.  Beyond Graphene: Progress in Novel Two-Dimensional Materials and van der Waals Solids , 2015 .

[11]  Jun Li,et al.  The B35 cluster with a double-hexagonal vacancy: a new and more flexible structural motif for borophene. , 2014, Journal of the American Chemical Society.

[12]  Ruitao Lv,et al.  Transition metal dichalcogenides and beyond: synthesis, properties, and applications of single- and few-layer nanosheets. , 2015, Accounts of chemical research.

[13]  V. Gurin,et al.  Raman effect in icosahedral boron-rich solids , 2010, Science and technology of advanced materials.

[14]  H. Hillebrecht,et al.  Bor – elementare Herausforderung für Experimentatoren und Theoretiker , 2009 .

[15]  Mark C Hersam,et al.  The reemergence of chemistry for post-graphene two-dimensional nanomaterials. , 2015, ACS nano.

[16]  Zhichuan J. Xu,et al.  One-dimensional boron nanostructures: Prediction, synthesis, characterizations, and applications. , 2010, Nanoscale.

[17]  Qiang Zhu,et al.  Semimetallic Two-Dimensional Boron Allotrope with Massless Dirac Fermions , 2013, 1309.2596.

[18]  S. Bhowmick,et al.  Polymorphism of two-dimensional boron. , 2012, Nano letters.

[19]  A. Krasheninnikov,et al.  Electron knock-on damage in hexagonal boron nitride monolayers , 2010 .

[20]  Lai‐Sheng Wang,et al.  Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality. , 2014, Accounts of chemical research.

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

[22]  L. Dubrovinsky,et al.  Synthesis of an orthorhombic high pressure boron phase , 2008, Science and technology of advanced materials.

[23]  C. Rao,et al.  Graphen‐analoge anorganische Schichtmaterialien , 2013 .

[24]  Madan Dubey,et al.  Silicene field-effect transistors operating at room temperature. , 2015, Nature nanotechnology.

[25]  H. Zeng,et al.  Atomically thin arsenene and antimonene: semimetal-semiconductor and indirect-direct band-gap transitions. , 2015, Angewandte Chemie.

[26]  J. Joannopoulos,et al.  Electronic and mechanical properties of planar and tubular boron structures , 2005 .

[27]  Sean C. Smith,et al.  Structural and Electronic Properties of Layered Arsenic and Antimony Arsenide , 2015 .

[28]  Giuseppe Iannaccone,et al.  Electronics based on two-dimensional materials. , 2014, Nature nanotechnology.

[29]  Alexander Quandt,et al.  Broad boron sheets and boron nanotubes: An ab initio study of structural, electronic, and mechanical properties , 2006 .

[30]  L. Dubrovinsky,et al.  Superhard semiconducting optically transparent high pressure phase of boron. , 2009, Physical review letters.

[31]  Yanming Ma,et al.  Ionic high-pressure form of elemental boron , 2009, Nature.

[32]  B. Hammer,et al.  Bandgap opening in graphene induced by patterned hydrogen adsorption. , 2010, Nature materials.

[33]  C. Rao,et al.  Graphene analogues of inorganic layered materials. , 2013, Angewandte Chemie.

[34]  Xiaojun Wu,et al.  Two-dimensional boron monolayer sheets. , 2012, ACS nano.

[35]  Zhuhua Zhang,et al.  Two-Dimensional Boron Monolayers Mediated by Metal Substrates. , 2015, Angewandte Chemie.

[36]  Elizabeth Gibney,et al.  The super materials that could trump graphene , 2015, Nature.

[37]  I. Boustani,et al.  New quasi-planar surfaces of bare boron , 1997 .

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

[39]  Binghai Yan,et al.  Large-gap quantum spin Hall insulators in tin films. , 2013, Physical review letters.

[40]  H. Hillebrecht,et al.  Boron: elementary challenge for experimenters and theoreticians. , 2009, Angewandte Chemie.

[41]  M. Trenary,et al.  The oxidation of the β-rhombohedral boron (111) surface , 1991 .

[42]  H. Mao,et al.  Superconductivity in Boron , 2001, Science.

[43]  Yu Zhang,et al.  Chemical vapour deposition of group-VIB metal dichalcogenide monolayers: engineered substrates from amorphous to single crystalline. , 2015, Chemical Society reviews.

[44]  A. Radenović,et al.  Single-layer MoS2 transistors. , 2011, Nature nanotechnology.

[45]  X. Zou,et al.  Temperature dependence of Raman spectra of vitreous and molten B2O3 , 1997 .

[46]  Jijun Zhao,et al.  From Boron Cluster to Two-Dimensional Boron Sheet on Cu(111) Surface: Growth Mechanism and Hole Formation , 2013, Scientific Reports.

[47]  E. Akturk,et al.  Two- and one-dimensional honeycomb structures of silicon and germanium. , 2008, Physical review letters.

[48]  Rodney S. Ruoff,et al.  Crystalline Boron Nanoribbons: Synthesis and Characterization , 2004 .