The rising star of 2D black phosphorus beyond graphene: synthesis, properties and electronic applications

Black phosphorus, which is a relatively rare allotrope of phosphorus, was first discovered by Bridgman in 1914. Since the advent of two-dimensional (2D) black phosphorus (which is known as phosphorene due to its resembling graphene sheets) in early 2014, research interest in the arena of black phosphorus was reignited in the scientific and technological communities. Henceforth, a myriad of research studies on this new member of the 2D world have been extensively emerged. Fascinatingly, 2D black phosphorus exhibits a distinctive wrinkled structure with the high hole mobility up to 1000 cm2 V-1 s-1, excellent mechanical properties, tunable band structures, anisotropic thermal, electrical and optical properties, thus leading to its marvelous prospects in device applications. This review firstly introduces the state-of-the-art development, structural properties and preparation routes of black phosphorus. In particular, anisotropy involved in mechanical properties, thermal conductivity, carrier transport as well as optical properties is comprehensively discussed. Apart from discussing the recent progress in black phosphorus which is applied to devices (i.e. field effect transistors and optoelectronic), the review also highlights the bottlenecks encountered by the society and finally casts an invigorating perspective and insightful outlook on the future direction of the next-generation 2D black phosphorus by harnessing its remarkable characteristics for energy production.

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

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

[3]  L. Lauhon,et al.  Passivation of Exfoliated Black Phosphorus Transistors Against Ambient Degradation 1 SPENCER WELLS, JOSHUA WOOD, DEEP JARI- , 2015 .

[4]  P. Schmidt,et al.  Au3SnP7@black phosphorus: an easy access to black phosphorus. , 2007, Inorganic chemistry.

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

[6]  Y. Kawazoe,et al.  Native point defects in few-layer phosphorene , 2014, 1409.5171.

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

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

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

[10]  Kang L. Wang,et al.  High-speed graphene transistors with a self-aligned nanowire gate , 2010, Nature.

[11]  Zongfu Yu,et al.  Extraordinary photoluminescence and strong temperature/angle-dependent Raman responses in few-layer phosphorene. , 2014, ACS nano.

[12]  B. Yakobson,et al.  Two-dimensional mono-elemental semiconductor with electronically inactive defects: the case of phosphorus. , 2014, Nano letters.

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

[14]  A. Javey,et al.  High-performance single layered WSe₂ p-FETs with chemically doped contacts. , 2012, Nano letters.

[15]  Jacek B. Jasinski,et al.  Recent advances in synthesis, properties, and applications of phosphorene , 2017, npj 2D Materials and Applications.

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

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

[18]  M. Engel,et al.  High-Performance p-Type Black Phosphorus Transistor with Scandium Contact. , 2016, ACS nano.

[19]  M. Pumera,et al.  Few-layer black phosphorus nanoparticles. , 2016, Chemical communications.

[20]  T. Nilges,et al.  A fast low-pressure transport route to large black phosphorus single crystals , 2008 .

[21]  Junhong Chen,et al.  Ultrahigh sensitivity and layer-dependent sensing performance of phosphorene-based gas sensors , 2015, Nature Communications.

[22]  Yingying Wu,et al.  High-quality sandwiched black phosphorus heterostructure and its quantum oscillations , 2014, Nature Communications.

[23]  Youngki Yoon,et al.  How good can monolayer MoS₂ transistors be? , 2011, Nano letters.

[24]  Wei Yi,et al.  Surface Structures of Black Phosphorus Investigated with Scanning Tunneling Microscopy , 2009 .

[25]  N. Mott,et al.  Observation of Anderson Localization in an Electron Gas , 1969 .

[26]  Jun Wang,et al.  Liquid exfoliation of solvent-stabilized few-layer black phosphorus for applications beyond electronics , 2015, Nature Communications.

[27]  Bin Liu,et al.  Hysteresis in single-layer MoS2 field effect transistors. , 2012, ACS nano.

[28]  Yihong Wu,et al.  Hysteresis of electronic transport in graphene transistors. , 2010, ACS nano.

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

[30]  Peide D. Ye,et al.  Anisotropic in-plane thermal conductivity observed in few-layer black phosphorus , 2015, Nature Communications.

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

[32]  Highly Itinerant Atomic Vacancies in Phosphorene. , 2016, Journal of the American Chemical Society.

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

[34]  S. Clark,et al.  Compressibility of cubic white, orthorhombic black, rhombohedral black, and simple cubic black phosphorus , 2010 .

[35]  Qinsheng Wang,et al.  Dynamical Evolution of Anisotropic Response in Black Phosphorus under Ultrafast Photoexcitation. , 2015, Nano letters.

[36]  A. R. T. Nugraha,et al.  Anisotropic Electron-Photon and Electron-Phonon Interactions in Black Phosphorus. , 2016, Nano letters.

[37]  Jinlong Yang,et al.  Point defects in lines in single crystalline phosphorene: directional migration and tunable band gaps. , 2016, Nanoscale.

[38]  H. Krebs,et al.  Über die Struktur und Eigenschaften der Halbmetalle. VIII. Die katalytische Darstellung des schwarzen Phosphors , 1955 .

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

[40]  Kenji Watanabe,et al.  Gate tunable quantum oscillations in air-stable and high mobility few-layer phosphorene heterostructures , 2014, 1412.0717.

[41]  Ning Wei,et al.  Thermal conductivities of single- and multi-layer phosphorene: a molecular dynamics study. , 2016, Nanoscale.

[42]  A. Splendiani,et al.  Emerging photoluminescence in monolayer MoS2. , 2010, Nano letters.

[43]  M. Hersam,et al.  Solvent exfoliation of electronic-grade, two-dimensional black phosphorus. , 2015, ACS nano.

[44]  S. Koester,et al.  Atomic and electronic structure of exfoliated black phosphorus , 2015 .

[45]  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.

[46]  Suhuai Wei,et al.  Engineering Grain Boundaries in Cu2ZnSnSe4 for Better Cell Performance: A First‐Principle Study , 2014 .

[47]  K Watanabe,et al.  Quality Heterostructures from Two-Dimensional Crystals Unstable in Air by Their Assembly in Inert Atmosphere. , 2015, Nano letters.

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

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

[50]  J. Kong,et al.  Integrated circuits based on bilayer MoS₂ transistors. , 2012, Nano letters.

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

[52]  Jundong Shao,et al.  From Black Phosphorus to Phosphorene: Basic Solvent Exfoliation, Evolution of Raman Scattering, and Applications to Ultrafast Photonics , 2015 .

[53]  P. Kim,et al.  Thermoelectric and magnetothermoelectric transport measurements of graphene. , 2008, Physical review letters.

[54]  T. G. Worlton,et al.  Effect of pressure on bonding in black phosphorus , 1979 .

[55]  Y. Akahama,et al.  Far-Infrared Cyclotron Resonance Absorptions in Black Phosphorus Single Crystals , 1983 .

[56]  Gang Zhang,et al.  Coexistence of size-dependent and size-independent thermal conductivities in phosphorene , 2014, 1409.1967.

[57]  Jun Dai,et al.  Edge-Modified Phosphorene Nanoflake Heterojunctions as Highly Efficient Solar Cells. , 2016, Nano letters.

[58]  D. Mitzi,et al.  Structure and electronic properties of grain boundaries in earth-abundant photovoltaic absorber Cu2ZnSnSe4. , 2011, ACS nano.

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

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

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

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

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

[64]  Chun Zhang,et al.  Heterostructures of phosphorene and transition metal dichalcogenides for excitonic solar cells: A first-principles study , 2016 .

[65]  M. Fuhrer,et al.  Creating a Stable Oxide at the Surface of Black Phosphorus. , 2015, ACS applied materials & interfaces.

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

[67]  Shen Lai,et al.  Plasma-Treated Thickness-Controlled Two-Dimensional Black Phosphorus and Its Electronic Transport Properties. , 2015, ACS nano.

[68]  Large Electronic Anisotropy and Enhanced Chemical Activity of Highly Rippled Phosphorene , 2016, 1610.07688.

[69]  Jing Lu,et al.  Monolayer Phosphorene–Metal Contacts , 2016 .

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

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

[72]  Dongdong Liu,et al.  Sandwiched Thin-Film Anode of Chemically Bonded Black Phosphorus/Graphene Hybrid for Lithium-Ion Battery. , 2017, Small.

[73]  Li Tao,et al.  Toward air-stable multilayer phosphorene thin-films and transistors , 2014, Scientific Reports.

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

[75]  Kai Liu,et al.  Anisotropic in-plane thermal conductivity of black phosphorus nanoribbons at temperatures higher than 100 K , 2015, Nature Communications.

[76]  SUPARNA DUTTASINHA,et al.  Van der Waals heterostructures , 2013, Nature.

[77]  Yuerui Lu,et al.  Optical tuning of exciton and trion emissions in monolayer phosphorene , 2015, Light: Science & Applications.

[78]  T. Kikegawa,et al.  An X‐ray diffraction study of lattice compression and phase transition of crystalline phosphorus , 1983 .

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

[80]  Mo Li,et al.  Black phosphorus mid-infrared photodetectors , 2017 .

[81]  Yi Shi,et al.  Supercritical carbon dioxide-assisted rapid synthesis of few-layer black phosphorus for hydrogen peroxide sensing. , 2016, Biosensors & bioelectronics.

[82]  Hao Li,et al.  Near-Infrared Photodetector Based on MoS2/Black Phosphorus Heterojunction , 2016 .

[83]  Qiangfei Xia,et al.  Black Phosphorus Mid-Infrared Photodetectors with High Gain. , 2016, Nano letters.

[84]  Wei Hu,et al.  Defects in Phosphorene , 2014, 1411.6986.

[85]  Nathan Youngblood,et al.  Waveguide-integrated black phosphorus photodetector with high responsivity and low dark current , 2014, Nature Photonics.

[86]  Yan Li,et al.  Modulation of the Electronic Properties of Ultrathin Black Phosphorus by Strain and Electrical Field , 2014 .

[87]  Phaedon Avouris,et al.  Origin of photoresponse in black phosphorus phototransistors , 2014, 1407.7286.

[88]  Y. Chang,et al.  Long-term stability study of graphene-passivated black phosphorus under air exposure , 2016 .

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

[90]  W. Choi,et al.  Air-stable few-layer black phosphorus phototransistor for near-infrared detection , 2017, Nanotechnology.

[91]  Jijun Zhao,et al.  Atomic structures and electronic properties of phosphorene grain boundaries , 2016 .

[92]  The Critical Role of Substrate in Stabilizing Phosphorene Nanoflake: A Theoretical Exploration. , 2016, Journal of the American Chemical Society.

[93]  A. Castellanos-Gómez,et al.  Black Phosphorus: Narrow Gap, Wide Applications. , 2015, The journal of physical chemistry letters.

[94]  Chongwu Zhou,et al.  Mechanical and Electrical Anisotropy of Few-Layer Black Phosphorus. , 2015, ACS nano.

[95]  Lihong Liu,et al.  Nonradiative Relaxation of Photoexcited Black Phosphorus Is Reduced by Stacking with MoS2: A Time Domain ab Initio Study. , 2016, The journal of physical chemistry letters.

[96]  Mingqiang Huang,et al.  Broadband Black‐Phosphorus Photodetectors with High Responsivity , 2016, Advanced materials.

[97]  Soon-Chang Lee,et al.  Triangular Black Phosphorus Atomic Layers by Liquid Exfoliation , 2016, Scientific Reports.

[98]  R. Pidaparti,et al.  Fracture patterns and the energy release rate of phosphorene. , 2016, Nanoscale.

[99]  Changfeng Chen,et al.  Phosphorene: Fabrication, Properties, and Applications. , 2015, The journal of physical chemistry letters.

[100]  J. Chen,et al.  Ultrafast Preparation of Black Phosphorus Quantum Dots for Efficient Humidity Sensing. , 2016, Chemistry.

[101]  A. Geim,et al.  Nonlocal Response and Anamorphosis: The Case of Few-Layer Black Phosphorus. , 2015, Nano letters.

[102]  Fatemeh Khalili-Araghi,et al.  Stable and Selective Humidity Sensing Using Stacked Black Phosphorus Flakes. , 2015, ACS nano.

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

[104]  Yong-Wei Zhang,et al.  Layer-dependent Band Alignment and Work Function of Few-Layer Phosphorene , 2014, Scientific reports.

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

[106]  D. Late Liquid exfoliation of black phosphorus nanosheets and its application as humidity sensor , 2016 .

[107]  Y. Maruyama,et al.  Synthesis and some properties of black phosphorus single crystals , 1981 .

[108]  K. Alam,et al.  Monolayer $\hbox{MoS}_{2}$ Transistors Beyond the Technology Road Map , 2012, IEEE Transactions on Electron Devices.

[109]  Xiao Cheng Zeng,et al.  Intrinsic Ferroelasticity and/or Multiferroicity in Two-Dimensional Phosphorene and Phosphorene Analogues. , 2016, Nano letters.

[110]  D. Tománek,et al.  Strain-controlled fundamental gap and structure of bulk black phosphorus , 2016, 1606.07789.

[111]  Russell F. Loane,et al.  Annular dark-field imaging: Resolution and thickness effects , 1993 .

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

[113]  Yoshihiro Iwasa,et al.  Ambipolar insulator-to-metal transition in black phosphorus by ionic-liquid gating. , 2015, ACS nano.

[114]  I. Shirotani Growth of Large Single Crystals of Black Phosphorus at High Pressures and Temperatures, and its Electrical Properties , 1982 .

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

[116]  Hsin-Ying Chiu,et al.  Exceptional and Anisotropic Transport Properties of Photocarriers in Black Phosphorus. , 2015, ACS nano.

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

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

[119]  D. Late,et al.  Humidity Sensing and Photodetection Behavior of Electrochemically Exfoliated Atomically Thin-Layered Black Phosphorus Nanosheets. , 2016, ACS applied materials & interfaces.

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

[121]  Large and tunable photothermoelectric effect in single-layer MoS2. , 2013, Nano letters.

[122]  W. Mi,et al.  Black phosphorene/monolayer transition-metal dichalcogenides as two dimensional van der Waals heterostructures: a first-principles study. , 2016, Physical chemistry chemical physics : PCCP.

[123]  A. Geim,et al.  Two-dimensional gas of massless Dirac fermions in graphene , 2005, Nature.

[124]  Mohammad Ziaur Rahman,et al.  2D phosphorene as a water splitting photocatalyst: fundamentals to applications , 2016 .

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

[126]  P. Ye,et al.  Channel length scaling of MoS2 MOSFETs. , 2012, ACS nano.

[127]  Zongfu Yu,et al.  Producing air-stable monolayers of phosphorene and their defect engineering , 2016, Nature Communications.

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

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

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

[131]  J. Burdett,et al.  The pressure-induced black phosphorus to A7 (arsenic) phase transformation: An analysis using the concept of orbital symmetry conservation , 1982 .

[132]  Joshua B Smith,et al.  Growth of 2D black phosphorus film from chemical vapor deposition , 2016, Nanotechnology.

[133]  L. Zhen,et al.  Elastic properties of suspended black phosphorus nanosheets , 2016 .

[134]  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.

[135]  Neng Li,et al.  Photocatalytic fixation of nitrogen to ammonia: state-of-the-art advancements and future prospects , 2018 .

[136]  Blatter,et al.  Carrier transport through grain boundaries in semiconductors. , 1986, Physical review. B, Condensed matter.

[137]  K. Zhou,et al.  The role of H 2 O and O 2 molecules and phosphorus vacancies in the structure instability of phosphorene , 2016, 1610.07512.

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

[139]  Young Tack Lee,et al.  Nonvolatile Ferroelectric Memory Circuit Using Black Phosphorus Nanosheet-Based Field-Effect Transistors with P(VDF-TrFE) Polymer. , 2015, ACS nano.

[140]  M. Burghard,et al.  Thin-layer black phosphorus/GaAs heterojunction p-n diodes , 2015 .

[141]  Jing Chen,et al.  Scalable Clean Exfoliation of High‐Quality Few‐Layer Black Phosphorus for a Flexible Lithium Ion Battery , 2016, Advanced materials.

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

[143]  Mark C Hersam,et al.  Chemically Tailoring Semiconducting Two-Dimensional Transition Metal Dichalcogenides and Black Phosphorus. , 2016, ACS nano.

[144]  Zhengxiao Guo,et al.  Compressive straining of bilayer phosphorene leads to extraordinary electron mobility at a new conduction band edge. , 2015, Nano letters.

[145]  P. Avouris,et al.  2D materials: Properties and devices , 2017 .

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

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

[148]  Harold S. Park,et al.  Mechanical strain effects on black phosphorus nanoresonators. , 2015, Nanoscale.

[149]  M. Kamalakar,et al.  Low Schottky barrier black phosphorus field-effect devices with ferromagnetic tunnel contacts. , 2015, Small.

[150]  Aaron M. Jones,et al.  Highly anisotropic and robust excitons in monolayer black phosphorus. , 2014, Nature nanotechnology.

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

[152]  Jun Hu,et al.  Phosphorene: Synthesis, Scale-Up, and Quantitative Optical Spectroscopy. , 2015, ACS nano.

[153]  Rishabh Jain,et al.  Phosphorene for energy and catalytic application—filling the gap between graphene and 2D metal chalcogenides , 2017 .