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Title: Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure

Abstract

The surface structure of black phosphorus materials is determined using surface-sensitive dynamical microspot low energy electron diffraction ( μ LEED ) analysis using a high spatial resolution low energy electron microscopy (LEEM) system. Samples of (i) crystalline cleaved black phosphorus (BP) at 300 K and (ii) exfoliated few-layer phosphorene (FLP) of about 10 nm thickness which were annealed at 573 K in vacuum were studied. In both samples, a significant surface buckling of 0.22 Å and 0.30 Å, respectively, is measured, which is one order of magnitude larger than previously reported. As direct evidence for large buckling, we observe a set of (for the flat surface forbidden) diffraction spots. Using first-principles calculations, we find that the presence of surface vacancies is responsible for the surface buckling in both BP and FLP, and is related to the intrinsic hole doping of phosphoresce materials previously reported.

Authors:
 [1];  [2];  [1];  [1];  [3];  [2];  [2];  [2];  [1];  [2];  [1]
  1. Univ. of New Hampshire, Durham, NH (United States)
  2. Columbia Univ., New York, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1425024
Alternate Identifier(s):
OSTI ID: 1416443
Report Number(s):
BNL-200011-2018-JAAM
Journal ID: ISSN 2475-9953; PRMHAR; TRN: US1802006
Grant/Contract Number:  
SC0012704; FG 02-04-ER-46157; SC0016424
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 7; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Dai, Zhongwei, Jin, Wencan, Yu, Jie-Xiang, Grady, Maxwell, Sadowski, Jerzy T., Kim, Young Duck, Hone, James, Dadap, Jerry I., Zang, Jiadong, Osgood, Richard M., and Pohl, Karsten. Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure. United States: N. p., 2017. Web. doi:10.1103/PhysRevMaterials.1.074003.
Dai, Zhongwei, Jin, Wencan, Yu, Jie-Xiang, Grady, Maxwell, Sadowski, Jerzy T., Kim, Young Duck, Hone, James, Dadap, Jerry I., Zang, Jiadong, Osgood, Richard M., & Pohl, Karsten. Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure. United States. doi:10.1103/PhysRevMaterials.1.074003.
Dai, Zhongwei, Jin, Wencan, Yu, Jie-Xiang, Grady, Maxwell, Sadowski, Jerzy T., Kim, Young Duck, Hone, James, Dadap, Jerry I., Zang, Jiadong, Osgood, Richard M., and Pohl, Karsten. Fri . "Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure". United States. doi:10.1103/PhysRevMaterials.1.074003. https://www.osti.gov/servlets/purl/1425024.
@article{osti_1425024,
title = {Surface buckling of black phosphorus: Determination, origin, and influence on electronic structure},
author = {Dai, Zhongwei and Jin, Wencan and Yu, Jie-Xiang and Grady, Maxwell and Sadowski, Jerzy T. and Kim, Young Duck and Hone, James and Dadap, Jerry I. and Zang, Jiadong and Osgood, Richard M. and Pohl, Karsten},
abstractNote = {The surface structure of black phosphorus materials is determined using surface-sensitive dynamical microspot low energy electron diffraction ( μ LEED ) analysis using a high spatial resolution low energy electron microscopy (LEEM) system. Samples of (i) crystalline cleaved black phosphorus (BP) at 300 K and (ii) exfoliated few-layer phosphorene (FLP) of about 10 nm thickness which were annealed at 573 K in vacuum were studied. In both samples, a significant surface buckling of 0.22 Å and 0.30 Å, respectively, is measured, which is one order of magnitude larger than previously reported. As direct evidence for large buckling, we observe a set of (for the flat surface forbidden) diffraction spots. Using first-principles calculations, we find that the presence of surface vacancies is responsible for the surface buckling in both BP and FLP, and is related to the intrinsic hole doping of phosphoresce materials previously reported.},
doi = {10.1103/PhysRevMaterials.1.074003},
journal = {Physical Review Materials},
number = 7,
volume = 1,
place = {United States},
year = {2017},
month = {12}
}

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Free Publicly Available Full Text
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Cited by: 2 works
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Figures / Tables:

Figure 1 Figure 1: (a)-(c) BP bulk crystal structure. (d) side view of BP and FLP relaxed surface structure, along dashed line in (b). Dotted square in (b) indicates the unit cell of BP, containing 8 P atoms.

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.