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

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.

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

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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.

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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

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Keywords

  • orthorhombic black phosphorus
  • single crystal
  • chemical vapor transport
  • two-step heating
  • field-effect transistors