Skip to main content
SpringerLink
Log in

Two-step heating synthesis of sub-3 millimeter-sized orthorhombic black phosphorus single crystal by chemical vapor transport reaction method

两步加热化学气相传输法合成~3 mm正交相黑磷单晶

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

A facile and green strategy to synthesize orthorhombic black phosphorus (o-BP) single crystals with high yield (~90%) and large size (sub-3 millimeter) is presented. The strategy was based on a two-step heating chemical vapor transport (CVT) reaction method, in which tin and iodine (Sn/I2) was used as mineralization additives and red phosphorus as precursor. Tin phosphide was the only by-product captured at the end of reaction, which greatly simplified the subsequent separation and purification processes of o-BP single crystals. The full width at half maximum (FWHM) of X-ray rocking curve of the as-grown o-BP was 21.65 arc sec, indicating its respectable crystalline quality. A bottom electrode structure field-effect transistor (FET) based on the multilayer phosphorene mechanically exfoliated from the as-grown o-BP single crystal was successfully fabricated through an all-dry transfer technique. Impressively, the FET based on a 6 nm thick multilayer (approximate 12 layers) phosphorene exhibited a record high hole mobility (µ p) of 1744 cm2 V-1 s-1 and an admirable on/off current switching ratio (I on/I off) of ~104, which further proved the high-quality of the o-BP single crystals synthesized by the twostep heating CVT reaction method using the simple Sn/I2/red phosphorus system.

摘要

本文采用一种温和的、绿色的两步加热化学气相传输反应方法合成了~3 mm正交相黑磷单晶, 产率高达~90%. 该反应体系由矿化剂金属 锡和单质碘以及前驱体红磷构成. 反应产物中, 磷化锡是唯一的副产物, 这大大地简化了正交相黑磷单晶后续的分离和纯化过程. 首次运用X射 线摇摆曲线研究了所合成的正交相黑磷单晶, 得到的摇摆曲线的半高峰宽为21.65弧秒, 揭示了其优异的单晶质量. 通过一种全干法转移技术制 备了基于机械剥离的少层磷烯的底电极结构的场效应晶体管. 在~6 nm厚的磷烯薄片上构筑的场效应晶体管表现出目前最高纪录的空穴迁移率 (1744 cm2V−1 s−1)和高的开关比(~104), 该结果进一步证明所发展的两步加热化学气相传输反应方法合成的正交相黑磷单晶具有优异的单晶质量.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Novoselov KS, Geim AK, Morozov SV, et al. Electric fiel d effect in atomically thin carbon films. Science, 2004, 306: 666–669

    Article  Google Scholar 

  2. Novoselov KS, Jiang D, Schedin F, et al. Two-dimension al atomic crystals. Prog Natl Acad Sci USA, 2005, 102: 10451–10453

    Article  Google Scholar 

  3. Wang QH, Kalantar-Zadeh K, Kis A, et al. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat Nanotechnol, 2012, 7: 699–712

    Article  Google Scholar 

  4. Huang X, Zeng Z, Zhang H. Metal dichalcogenide nanosheets: preparation, properties and applications. Chem Soc Rev, 2013, 42: 1934–1946

    Article  Google Scholar 

  5. Li L, Yu Y, Ye GJ, et al. Black phosphorus field-effect transistors. Nat Nanotechnol, 2014, 9: 372–377

    Article  Google Scholar 

  6. Churchill HOH, Jarillo-Herrero P. Phosphorus joins the family. Nat Nanotechnol, 2014, 9: 330–331

    Article  Google Scholar 

  7. Reich ES. Phosphorene excites materials scientists. Nature, 2014, 506: 19

    Article  Google Scholar 

  8. Liu H, Du Y, Deng Y, et al. Semiconducting black phosphorus: synthesis, transport properties and electronic applications. Chem Soc Rev, 2015, 44: 2732–2743

    Article  Google Scholar 

  9. Xia F, Wang H, Jia Y. Rediscovering black phosphorus as an anisotropic layered material for optoelectronics and electronics. Nat Commun, 2014, 5: 4458

    Google Scholar 

  10. Buscema M, Groenendijk DJ, Steele GA, et al. Photovoltaic effect in few-layer black phosphorus PN junctions defined by local electrostatic gating. Nat Commun, 2014, 5: 4651

    Article  Google Scholar 

  11. Qiao J, Kong X, Hu ZX, et al. High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus. Nat Commun, 2014, 5: 4475

    Google Scholar 

  12. Miao J, Zhang S, Cai L, et al. Ultrashort channel length black phosphorus field-effect transistors. ACS Nano, 2015, 9: 9236–9243

    Article  Google Scholar 

  13. Zhu W, Yogeesh MN, Yang S, et al. Flexible black phosp horus ambipolar transistors, circuits and AM demodulator. Nano Lett, 2015, 15: 1883–1890

    Article  Google Scholar 

  14. Park CM, Sohn HJ. Black phosphorus and its composite for lithium rechargeable batteries. Adv Mater, 2007, 19: 2465–2468

    Article  Google Scholar 

  15. Sun LQ, Li MJ, Sun K, et al. Electrochemic al activity of black phosphorus as an anode material for lithium-ion batteries. J Phys Chem C, 2012, 116: 14772–14779

    Article  Google Scholar 

  16. Yao Q, Huang C, Yuan Y, et al. Theoretical predicti on of phosphorene and nanoribbons as fast charging Li ion battery anode materials. J Phys Chem C, 2015, 119: 6923–6928

    Article  Google Scholar 

  17. Hembram KPSS, Jung H, Yeo BC, et al. Unraveling th e atomistic sodiation mechanism of black phosphorus for sodium ion batteries by first-principles calculations. J Phys Chem C, 2015, 119: 15041–15046

    Article  Google Scholar 

  18. Li W, Yang Y, Zhang G, et al. Ultrafast and directional diffusion of lithium in phosphorene for high-performance lithium-ion battery. Nano Lett, 2015, 15: 1691–1697

    Article  Google Scholar 

  19. Engel M, Steiner M, Avouris P. Black phosphorus photodetector for multispectral, high-resolution imaging. Nano Lett, 2014, 14: 6414–6417

    Article  Google Scholar 

  20. Viti L, Hu J, Coquillat D, et al. Black phosphorus terahertz photodetectors. Adv Mater, 2015, 27: 5567–5572

    Article  Google Scholar 

  21. Wu J, Koon GKW, Xiang D, et al. Colossal ultr aviolet photoresponsivity of few-layer black phosphorus. ACS Nano, 2015, 9: 8070–8077

    Article  Google Scholar 

  22. Kou L, Frauenheim T, Chen C. Phosphorene as a superior gas sensor: selective adsorption and distinct I-V response. J Phys Chem Lett, 2014, 5: 2675–2681

    Article  Google Scholar 

  23. Abbas AN, Liu B, Chen L, et al. Black phospho rus gas sensors. ACS Nano, 2015, 9: 5618–5624

    Article  Google Scholar 

  24. Li P, Zhang D, Liu J, et al. Air-stable black phosphorus devices for ion sensing. ACS Appl Mater Interfaces, 2015, 7: 24396–24402

    Article  Google Scholar 

  25. Yasaei P, Behranginia A, Foroozan T, et al. Stable and se lective humidity sensing using stacked black phosphorus flakes. ACS Nano, 2015, 9: 9898–9905

    Article  Google Scholar 

  26. Zhang X, Xie H, Liu Z, et al. Black phosphorus quantum dots. Angew Chem Int Ed, 2015, 54: 3653–3657

    Article  Google Scholar 

  27. Sa B, Li YL, Qi J, et al. Strain engineering for phosphorene: the potential application as a photocatalyst. J Phys Chem C, 2014, 118: 26560–26568

    Article  Google Scholar 

  28. Dai J, Zeng XC. Bilayer phosphorene: effect of stacking order on bandgap and its potential applications in thin-film solar cells. J Phys Chem Lett, 2014, 5: 1289–1293

    Article  Google Scholar 

  29. Yasaei P, Kumar B, Foroozan T, et al. High-quality black phosphorus atomic layers by liquid-phase exfoliation. Adv Mater, 2015, 27: 1887–1892

    Article  Google Scholar 

  30. Kang J, Wood JD, Wells SA, et al. Solvent exfol iation of electronic-grade, two-dimensional black phosphorus. ACS Nano, 2015, 9: 3596–3604

    Article  Google Scholar 

  31. Sresht V, Pádua AAH, Blankschtein D. Liquid-phase exfoliation of phosphorene: design rules from molecular dynamics simulations. ACS Nano, 2015, 9: 8255–8268

    Article  Google Scholar 

  32. Woomer AH, Farnsworth TW, Hu J, et al. Phosphorene: synthesis, scale-up, and quantitative optical spectroscopy. ACS Nano, 2015, 9: 8869–8884

    Article  Google Scholar 

  33. Bridgman PW. Two new modifications of phosphorus. J Am Chem Soc, 1914, 36: 1344–1363.

    Article  Google Scholar 

  34. Bridgman PW. Further note on black phosphorus. J Am Chem Soc, 1916, 38: 609–612

    Article  Google Scholar 

  35. Hultgren R, Gingrich NS, Warren BE. The atomic distribution in red and black phosphorus and the crystal structure of black phosphorus. J Chem Phys, 1935, 3: 351–355

    Article  Google Scholar 

  36. Jacobs RB. Phosphorus at high temperatures and pressures. J Chem Phys, 1937, 5: 945–953.

    Article  Google Scholar 

  37. Keyes RW. The electrical properties of black phosphorus. Phys Rev, 1953, 92: 580–584

    Article  Google Scholar 

  38. Shirotani I, Maniwa R, Sato H, et al. Preparation, growth of large single crystals, and physicochemical properties of black phosphorus at high pressures and temperatures. Nippon Kagaku Kaishi, 1981, 10: 1604–1609

    Article  Google Scholar 

  39. Shirotani I. Growth of large single crystals of black phosphorus at high pressures and temperatures, and its electrical properties. Mol Cryst Liq Cryst, 1982, 86: 203–211

    Article  Google Scholar 

  40. Endo S, Akahama Y, Terada S, et al. Growth of large sin gle crystals of black phosphorus under high pressure. Jpn J Appl Phys, 1982, 21: L482–L484

    Article  Google Scholar 

  41. Krebs VH, Weitz H, Worms KH. Über die struktur und eigenschaften der halbmetalle. Viii. Die katalytische darstellung des schwarzen phosphors. Z Anorg Allg Chem, 1955, 280: 119–133

    Article  Google Scholar 

  42. Maruyama Y, Suzuki S, Kobayashi K, et al. Synthesis and some properties of black phosphorus single crystals. Physica B, 1981, 105B: 99–102

    Google Scholar 

  43. Brown A, Rundqvist S. Refinement of the crystal structure of black phosphorus. Acta Crystallogr, 1965, 19: 684–685

    Article  Google Scholar 

  44. Baba M, Izumida F, Takeda Y, et al. Preparation of black phosphorus single crystals by a completely closed bismuth-flux method and their crystal morphology. Jpn J Appl Phys, 1989, 28: 1019–1022

    Article  Google Scholar 

  45. Lange S, Schmidt P, Nilges T. Au3SnP7@black phosphorus: an easy access to black phosphorus. Inorg Chem, 2007, 46: 4028–4035

    Article  Google Scholar 

  46. Nilges T, Kersting M, Pfeifer T. A fast low-pressure transport route to large black phosphorus single crystals. J Solid State Chem, 2008, 181: 1707–1711

    Article  Google Scholar 

  47. Köpf M, Eckstein N, Pfister D, et al. Access and in situ growth of phosphorene-precursor black phosphorus. J Cryst Growth, 2014, 405: 6–10

    Article  Google Scholar 

  48. Zhao M, Qian H, Niu X, et al. Growth mechanism and enhanced yield of black phosphorus microribbons. Cryst Growth Des, 2016, 16: 1096–1103

  49. Schmidt P, Binnewies M, Glaum R, Schmidt M. Chemical vapor trans port reactions–methods, materials, modeling. In: Ferreira SO (Ed). Advanced Topics on Crystal Growth. Rijeka: InTech, 2013: 227–306

    Google Scholar 

  50. Castellanos-Gomez A, Buscema M, Molenaar R, et al. Deterministic transfer of two-dimensional materials by all-dry viscoelastic stamping. 2D Mater, 2014, 1: 011002

  51. Zhang CD, Lian JC, Yi W, et al. Surface structures of black phosphorus investigated with scanning tunneling microscopy. J Phys Chem C, 2009, 113: 18823–18826

    Article  Google Scholar 

  52. Liu Y, Yang Z, Cui D, et al. Two-inch-size d perovskite CH3NH3PbX3 (X = Cl, Br, I) crystals: growth and characterization. Adv Mater, 2015, 27: 5176–5183

    Article  Google Scholar 

  53. Ferrari AC, Basko DM. Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol, 2013, 8: 235–246

    Article  Google Scholar 

  54. Sugai S, Shirotani I. Raman and infrared reflection spectroscopy in black phosphorus. Solid State Commun, 1985, 53: 753–755

    Article  Google Scholar 

  55. Fei R, Yang L. Lattice vibrational modes and Raman scattering spectra of strained phosphorene. Appl Phys Lett, 2014, 105: 083120

    Article  Google Scholar 

  56. Castellanos-Gomez A, Vicarelli L, Prada E, et al. Isolation and characterization of few-layer black phosphorus. 2D Mater, 2014, 1: 025001

    Article  Google Scholar 

  57. Tauc J, Grigorovici R, Vancu A. Optical properties and electronic structure of amorphous germanium. Phys Status Solidi, 1966, 15: 627–637

    Article  Google Scholar 

  58. Tsunekawa S, Fukuda T, Kasuya A. Blue shift in ultraviolet absorption spectra of monodisperse CeO2-x nanoparticles. J Appl Phys, 2000, 87: 1318–1321

    Article  Google Scholar 

  59. Flores E, Ares JR, Castellanos-Gomez A, et al. Thermoelectric power of bulk black-phosphorus. Appl Phys Lett, 2015, 106: 022102

    Article  Google Scholar 

  60. Ziletti A, Carvalho A, Campbell DK, et al. Oxygen defects in phosphorene. Phys Rev Lett, 2015, 114: 046801

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Ziming Zhang  (张子明), Qingfeng Yan  (严清峰) & Qiang Li  (李强)

  2. Institute of Microelectronics, Tsinghua University, Beijing, 100084, China

    Xin Xin  (辛鑫), Yi Yang  (杨轶) & Tian-Ling Ren  (任天令)

  3. Tsinghua National Laboratory for Information Science and Technology (TNList), Tsinghua University, Beijing, 100084, China

    Xin Xin  (辛鑫), Yi Yang  (杨轶) & Tian-Ling Ren  (任天令)

Authors
  1. Ziming Zhang  (张子明)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xin Xin  (辛鑫)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Qingfeng Yan  (严清峰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Qiang Li  (李强)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yi Yang  (杨轶)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Tian-Ling Ren  (任天令)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Qingfeng Yan  (严清峰) or Tian-Ling Ren  (任天令).

Additional information

These two authors contributed equally to this work.

Ziming Zhang is currently a PhD candidate under the supervision of Prof. Qingfeng Yan at the Department of Chemistry, Tsinghua University. His research interests focus on the synthesis and application of black phosphorus-based 2D materials.

Xin Xin is a Master student under the supervision of Prof. Tian-Ling Ren at the Institute of Microelectronics, Tsinghua University. His research interest is novel devices based on 2D materials.

Qingfeng Yan received his PhD degree from the Institute of Semiconductors, Chinese Academy of Sciences in 2003. He joined the Department of Chemical & Biomolecular Engineering, National University of Singapore as a research fellow in 2003. From 2006, he worked with the School of Materials Science and Engineering, Nanyang Technological University and the Department of Materials Science and Engineering, Massachusetts Institute of Technology as a joint postdoctoral fellow. He joined the Department of Chemistry, Tsinghua University as an associate professor in 2008. His current research interest focuses on synthetic single crystals and chemical self-assembly approach to functional thin films.

Tian-Ling Ren is a full professor of the Institute of Microelectronics, Tsinghua University since 2003. He received his PhD degree in solid-state physics from the Department of Modern Applied Physics, Tsinghua University, China in 1997. His main research interests include new material based micro/nano devices and systems, flexible electronics, non-volatile memory.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, Z., Xin, X., Yan, Q. et al. Two-step heating synthesis of sub-3 millimeter-sized orthorhombic black phosphorus single crystal by chemical vapor transport reaction method. Sci. China Mater. 59, 122–134 (2016). https://doi.org/10.1007/s40843-016-0122-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-016-0122-1

Keywords

Search

Navigation