Phosphorene: Fabrication, Properties, and Applications.

Phosphorene, the single- or few-layer form of black phosphorus, was recently rediscovered as a two-dimensional layered material holding great promise for applications in electronics and optoelectronics. Research into its fundamental properties and device applications has since seen exponential growth. In this Perspective, we review recent progress in phosphorene research, touching upon topics on fabrication, properties, and applications; we also discuss challenges and future research directions. We highlight the intrinsically anisotropic electronic, transport, optoelectronic, thermoelectric, and mechanical properties of phosphorene resulting from its puckered structure in contrast to those of graphene and transition-metal dichalcogenides. The facile fabrication and novel properties of phosphorene have inspired design and demonstration of new nanodevices; however, further progress hinges on resolutions to technical obstructions like surface degradation effects and nonscalable fabrication techniques. We also briefly describe the latest developments of more sophisticated design concepts and implementation schemes that address some of the challenges in phosphorene research. It is expected that this fascinating material will continue to offer tremendous opportunities for research and development for the foreseeable future.

[1]  Lain‐Jong Li,et al.  Synthesis of Large‐Area MoS2 Atomic Layers with Chemical Vapor Deposition , 2012, Advanced materials.

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

[3]  Gang Zhang,et al.  Strong Thermal Transport Anisotropy and Strain Modulation in Single-Layer Phosphorene , 2014 .

[4]  G. Vaitheeswaran,et al.  Effect of van der Waals interactions on the structural and elastic properties of black phosphorus , 2012, 1211.3512.

[5]  Fan Yang,et al.  The strain effect on superconductivity in phosphorene: a first-principles prediction , 2015 .

[6]  Kailun Yao,et al.  Nine new phosphorene polymorphs with non-honeycomb structures: a much extended family. , 2015, Nano letters.

[7]  Mustafa Lotya,et al.  Solvent Exfoliation of Transition Metal Dichalcogenides: Dispersability of Exfoliated Nanosheets Varies Only Weakly between Compounds /v Sol (mol/ml) Characterisation of Dispersions , 2022 .

[8]  Zhen Zhu,et al.  Semiconducting layered blue phosphorus: a computational study. , 2014, Physical review letters.

[9]  Zhiyuan Zeng,et al.  An effective method for the fabrication of few-layer-thick inorganic nanosheets. , 2012, Angewandte Chemie.

[10]  Mohammad Asadi,et al.  High‐Quality Black Phosphorus Atomic Layers by Liquid‐Phase Exfoliation , 2015, Advanced materials.

[11]  Tianshu Li,et al.  Ideal strength and phonon instability in single-layer MoS 2 , 2012 .

[12]  Wei Kang,et al.  The potential application of phosphorene as an anode material in Li-ion batteries , 2014, 1408.3488.

[13]  Wei Huang,et al.  Black phosphorus quantum dots. , 2015, Angewandte Chemie.

[14]  Tom Nilges,et al.  Access and in situ growth of phosphorene-precursor black phosphorus , 2014 .

[15]  Zhuhua Zhang,et al.  Photoluminescence quenching and charge transfer in artificial heterostacks of monolayer transition metal dichalcogenides and few-layer black phosphorus. , 2015, ACS nano.

[16]  Qun Wei,et al.  Superior mechanical flexibility of phosphorene and few-layer black phosphorus , 2014, 1403.7882.

[17]  F. Xia,et al.  The renaissance of black phosphorus , 2015, Proceedings of the National Academy of Sciences.

[18]  Phaedon Avouris,et al.  Black phosphorus photodetector for multispectral, high-resolution imaging. , 2014, Nano letters.

[19]  Andres Castellanos-Gomez,et al.  Photovoltaic effect in few-layer black phosphorus PN junctions defined by local electrostatic gating. , 2014, Nature communications.

[20]  D. Coker,et al.  Oxygen defects in phosphorene. , 2014, Physical review letters.

[21]  Weiwei Zhao,et al.  Layer-by-layer thinning of MoS2 by plasma. , 2013, ACS nano.

[22]  James Hone,et al.  Measurement of mobility in dual-gated MoS₂ transistors. , 2013, Nature nanotechnology.

[23]  Alan J. H. McGaughey,et al.  Strongly anisotropic in-plane thermal transport in single-layer black phosphorene , 2015, Scientific Reports.

[24]  A. Balandin Thermal properties of graphene and nanostructured carbon materials. , 2011, Nature materials.

[25]  B. Sumpter,et al.  Electronic bandgap and edge reconstruction in phosphorene materials. , 2014, Nano letters.

[26]  Christian Kisielowski,et al.  Atomically thin hexagonal boron nitride probed by ultrahigh-resolution transmission electron microscopy , 2009 .

[27]  H. R. Krishnamurthy,et al.  Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. , 2008, Nature nanotechnology.

[28]  Adalberto Fazzio,et al.  Switching a normal insulator into a topological insulator via electric field with application to phosphorene. , 2015, Nano letters.

[29]  Zhen Zhu,et al.  Phase coexistence and metal-insulator transition in few-layer phosphorene: a computational study. , 2014, Physical review letters.

[30]  J. Coleman,et al.  Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials , 2011, Science.

[31]  Liangzhi Kou,et al.  Anisotropic Ripple Deformation in Phosphorene. , 2015, The journal of physical chemistry letters.

[32]  Ryan Soklaski,et al.  Enhanced thermoelectric efficiency via orthogonal electrical and thermal conductances in phosphorene. , 2014, Nano letters.

[33]  Xiaolong Zou,et al.  Electro-mechanical anisotropy of phosphorene. , 2015, Nanoscale.

[34]  Qing Tang,et al.  Small molecules make big differences: molecular doping effects on electronic and optical properties of phosphorene , 2015, Nanotechnology.

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

[36]  Gengchiau Liang,et al.  Thermoelectric performance of MX2 (M = Mo,W; X = S,Se) monolayers , 2013 .

[37]  Marcel Demarteau,et al.  Ambipolar phosphorene field effect transistor. , 2014, ACS nano.

[38]  Xianfan Xu,et al.  Black phosphorus-monolayer MoS2 van der Waals heterojunction p-n diode. , 2014, ACS nano.

[39]  Qing Hua Wang,et al.  Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. , 2012, Nature nanotechnology.

[40]  Mircea Dragoman,et al.  Giant thermoelectric effect in graphene , 2007 .

[41]  Jun Dai,et al.  Electron-Transport Properties of Few-Layer Black Phosphorus. , 2015, The journal of physical chemistry letters.

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

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

[44]  Qun Wei,et al.  Strain-engineered direct-indirect band gap transition and its mechanism in two-dimensional phosphorene , 2014 .

[45]  Yu-Chuan Lin,et al.  Growth of large-area and highly crystalline MoS2 thin layers on insulating substrates. , 2012, Nano letters.

[46]  S. Banerjee,et al.  Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils , 2009, Science.

[47]  Guangyuan Zheng,et al.  Formation of stable phosphorus-carbon bond for enhanced performance in black phosphorus nanoparticle-graphite composite battery anodes. , 2014, Nano letters.

[48]  H. Thurn,et al.  Crystal Structure of Violet Phosphorus , 1966 .

[49]  L. Lauhon,et al.  Effective passivation of exfoliated black phosphorus transistors against ambient degradation. , 2014, Nano letters.

[50]  Li Yang,et al.  Scaling laws for the band gap and optical response of phosphorene nanoribbons , 2014 .

[51]  Bing-Lin Gu,et al.  Tunable Magnetism in Transition-Metal-Decorated Phosphorene , 2015 .

[52]  Bin Li,et al.  A First-Principles Study on Electron Donor and Acceptor Molecules Adsorbed on Phosphorene , 2015 .

[53]  Harold S. Park,et al.  Negative poisson’s ratio in single-layer black phosphorus , 2014, Nature Communications.

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

[55]  W. D. de Heer,et al.  The growth and morphology of epitaxial multilayer graphene , 2008 .

[56]  Takashi Taniguchi,et al.  Quantum oscillations in a two-dimensional electron gas in black phosphorus thin films. , 2015, Nature nanotechnology.

[57]  Zhiyuan Zeng,et al.  Single-layer semiconducting nanosheets: high-yield preparation and device fabrication. , 2011, Angewandte Chemie.

[58]  Yi Cui,et al.  Physical and chemical tuning of two-dimensional transition metal dichalcogenides. , 2015, Chemical Society reviews.

[59]  Andras Kis,et al.  Stretching and breaking of ultrathin MoS2. , 2011, ACS nano.

[60]  Zhenhua Ni,et al.  Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization , 2014, Nano Research.

[61]  P. Feng,et al.  Design of Black Phosphorus 2D Nanomechanical Resonators by Exploiting the Intrinsic Mechanical Anisotropy , 2015, 1504.01060.

[62]  D.D.L. Chung,et al.  Exfoliation of graphite , 1987 .

[63]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[64]  Gang Su,et al.  Hinge-like structure induced unusual properties of black phosphorus and new strategies to improve the thermoelectric performance , 2014, Scientific Reports.

[65]  Jisang Hong,et al.  First-Principles Study of Metal Adatom Adsorption on Black Phosphorene , 2015 .

[66]  Andres Castellanos-Gomez,et al.  Environmental instability of few-layer black phosphorus , 2014, 1410.2608.

[67]  J. Coleman,et al.  Liquid Exfoliation of Layered Materials , 2013, Science.

[68]  H. Wang,et al.  The management of white phosphorus burns. , 2001, Burns : journal of the International Society for Burn Injuries.

[69]  A Kis,et al.  Reply to 'Measurement of mobility in dual-gated MoS₂ transistors'. , 2013, Nature nanotechnology.

[70]  Salvador Ordóñez,et al.  Adsorption of volatile organic compounds onto carbon nanotubes, carbon nanofibers, and high-surface-area graphites. , 2007, Journal of colloid and interface science.

[71]  J. Coleman,et al.  High-yield production of graphene by liquid-phase exfoliation of graphite. , 2008, Nature nanotechnology.

[72]  R. Hultgren,et al.  The Atomic Distribution in Red and Black Phosphorus and the Crystal Structure of Black Phosphorus , 1935 .

[73]  Gang Zhang,et al.  Ultrafast and directional diffusion of lithium in phosphorene for high-performance lithium-ion battery. , 2015, Nano letters.

[74]  Hugen Yan,et al.  Anomalous lattice vibrations of single- and few-layer MoS2. , 2010, ACS nano.

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

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

[77]  Qun Wei,et al.  Edge effects on the electronic properties of phosphorene nanoribbons , 2014 .

[78]  Jun Dai,et al.  Structure and stability of two dimensional phosphorene with O or NH functionalization , 2014 .

[79]  Zhixian Zhou,et al.  Polarized photocurrent response in black phosphorus field-effect transistors. , 2014, Nanoscale.

[80]  Harold S. Park,et al.  Mechanical properties of single-layer black phosphorus , 2014, 1404.0232.

[81]  Satyaprakash Sahoo,et al.  Temperature-Dependent Raman Studies and Thermal Conductivity of Few-Layer MoS2 , 2013 .

[82]  D. Akinwande,et al.  Flexible black phosphorus ambipolar transistors, circuits and AM demodulator. , 2015, Nano letters.

[83]  Andre K. Geim,et al.  Two-dimensional atomic crystals. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

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

[85]  S. Haigh,et al.  Production of few-layer phosphorene by liquid exfoliation of black phosphorus. , 2014, Chemical communications.

[86]  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.

[87]  Takashi Taniguchi,et al.  Air-stable transport in graphene-contacted, fully encapsulated ultrathin black phosphorus-based field-effect transistors. , 2014, ACS Nano.

[88]  Thomas Frauenheim,et al.  Phosphorene as a Superior Gas Sensor: Selective Adsorption and Distinct I-V Response. , 2014, The journal of physical chemistry letters.

[89]  P. Ming,et al.  Ab initio calculation of ideal strength and phonon instability of graphene under tension , 2007 .

[90]  Zheng Wang,et al.  Hydrothermal synthesis of macroscopic nitrogen-doped graphene hydrogels for ultrafast supercapacitor , 2013 .

[91]  P. Ye,et al.  Semiconducting black phosphorus: synthesis, transport properties and electronic applications. , 2014, Chemical Society Reviews.

[92]  Fengnian Xia,et al.  Plasmons and screening in monolayer and multilayer black phosphorus. , 2014, Physical review letters.

[93]  Hanna Enriquez,et al.  Epitaxial growth of a silicene sheet , 2010, 1204.0523.

[94]  J. Shan,et al.  Atomically thin MoS₂: a new direct-gap semiconductor. , 2010, Physical review letters.

[95]  A. Ziletti,et al.  Phosphorene oxides: Bandgap engineering of phosphorene by oxidation , 2014, 1410.3906.

[96]  G. Fudenberg,et al.  Ultrahigh electron mobility in suspended graphene , 2008, 0802.2389.

[97]  Cheng-Cheng Liu,et al.  Quantum spin Hall effect in silicene and two-dimensional germanium. , 2011, Physical review letters.

[98]  Atanu Samanta,et al.  Semiconductor to metal transition in bilayer phosphorene under normal compressive strain , 2014, Nanotechnology.

[99]  Gang Zhang,et al.  Electronic Properties of Phosphorene/Graphene and Phosphorene/Hexagonal Boron Nitride Heterostructures , 2015, 1505.07545.

[100]  E. Johnston-Halperin,et al.  Progress, challenges, and opportunities in two-dimensional materials beyond graphene. , 2013, ACS nano.

[101]  Xiaoming Xie,et al.  Layer-by-layer thinning of graphene by plasma irradiation and post-annealing , 2012, Nanotechnology.

[102]  Xiaoyu Han,et al.  Strain and orientation modulated bandgaps and effective masses of phosphorene nanoribbons. , 2014, Nano letters.

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

[104]  Gyu-Tae Kim,et al.  Few-layer black phosphorus field-effect transistors with reduced current fluctuation. , 2014, ACS nano.

[105]  Weichao Yu,et al.  Hydrothermal Synthesis of MoS2 and Its Pressure-Related Crystallization , 2001 .

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

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

[108]  C. D. Walle,et al.  Effects of strain on band structure and effective masses in MoS$_2$ , 2012 .