Resolving the Chemically Discrete Structure of Synthetic Borophene Polymorphs

Campbell, Gavin P.; Mannix, Andrew J.; Emery, Jonathan D.; Lee, Tien -Lin; Guisinger, Nathan P.; Hersam, Mark C.; Bedzyk, Michael J.

doi:10.1021/acs.nanolett.7b05178

Title: Resolving the Chemically Discrete Structure of Synthetic Borophene Polymorphs

Journal Article · Fri Apr 13 00:00:00 EDT 2018 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.7b05178· OSTI ID:1482105

Campbell, Gavin P. ^[1];

^[2]; Emery, Jonathan D. ^[1]; Lee, Tien -Lin ^[3]; Guisinger, Nathan P. ^[4];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Diamond Light Source, Didcot (United Kingdom)
Argonne National Lab. (ANL), Argonne, IL (United States)

Atomically thin two-dimensional (2D) materials exhibit superlative properties dictated by their intralayer atomic structure, which is typically derived from a limited number of thermodynamically stable bulk layered crystals (e.g., graphene from graphite). The growth of entirely synthetic 2D crystals, those with no corresponding bulk allotrope, would circumvent this dependence upon bulk thermodynamics and substantially expand the phase space available for structure-property engineering of 2D materials. However, it remains unclear if synthetic 2D materials can exist as structurally and chemically distinct layers anchored by van der Waals (vdW) forces, as opposed to strongly bound adlayers. Here, we show that atomically thin sheets of boron (i.e., borophene) grown on the Ag(111) surface exhibit a vdW-like structure without a corresponding bulk allotrope. Using X-ray standing wave-excited X-ray photoelectron spectroscopy, the positions of boron in multiple chemical states are resolved with sub-angstrom spatial resolution, revealing that the borophene forms a single planar layer that is 2.4 angstrom above the unreconstructed Ag surface. Moreover, our results reveal that multiple borophene phases exhibit these characteristics, denoting a unique form of polymorphism consistent with recent predictions. Furthermore, this observation of synthetic borophene as chemically discrete from the growth substrate suggests that it is possible to engineer a much wider variety of 2D materials than those accessible through bulk layered crystal structures.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1482105

Journal Information:: Nano Letters, Vol. 18, Issue 5; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 41 works

Citation information provided by
Web of Science

References (37)

β-Rhombohedral Boron: At the Crossroads of the Chemistry of Boron and the Physics of Frustration Ogitsu, Tadashi; Schwegler, Eric; Galli, Giulia Chemical Reviews, Vol. 113, Issue 5 https://doi.org/10.1021/cr300356t	journal	March 2013
Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A. Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400310g	journal	February 2014
Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs Mannix, A. J.; Zhou, X. -F.; Kiraly, B. Science, Vol. 350, Issue 6267 https://doi.org/10.1126/science.aad1080	journal	December 2015
Experimental realization of two-dimensional boron sheets Feng, Baojie; Zhang, Jin; Zhong, Qing Nature Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/nchem.2491	journal	March 2016
Two-dimensional atomic crystals Novoselov, K. S.; Jiang, D.; Schedin, F. Proceedings of the National Academy of Sciences, Vol. 102, Issue 30, p. 10451-10453 https://doi.org/10.1073/pnas.0502848102	journal	July 2005
The rise of graphene Geim, A. K.; Novoselov, K. S. Nature Materials, Vol. 6, Issue 3, p. 183-191 https://doi.org/10.1038/nmat1849	journal	March 2007
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712 https://doi.org/10.1038/nnano.2012.193	journal	November 2012
The renaissance of black phosphorus Ling, Xi; Wang, Han; Huang, Shengxi Proceedings of the National Academy of Sciences, Vol. 112, Issue 15 https://doi.org/10.1073/pnas.1416581112	journal	March 2015
Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets Piazza, Zachary A.; Hu, Han-Shi; Li, Wei-Li Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4113	journal	January 2014
Two-Dimensional Boron Monolayers Mediated by Metal Substrates Zhang, Zhuhua; Yang, Yang; Gao, Guoying Angewandte Chemie International Edition, Vol. 54, Issue 44 https://doi.org/10.1002/anie.201505425	journal	September 2015
Systematic ab initio investigation of bare boron clusters:mDetermination of the geometryand electronic structures of $B_{n}$ (n=2–14) Boustani, Ihsan Physical Review B, Vol. 55, Issue 24 https://doi.org/10.1103/PhysRevB.55.16426	journal	June 1997
Novel Precursors for Boron Nanotubes: The Competition of Two-Center and Three-Center Bonding in Boron Sheets Tang, Hui; Ismail-Beigi, Sohrab Physical Review Letters, Vol. 99, Issue 11 https://doi.org/10.1103/PhysRevLett.99.115501	journal	September 2007
Polymorphism of Two-Dimensional Boron Penev, Evgeni S.; Bhowmick, Somnath; Sadrzadeh, Arta Nano Letters, Vol. 12, Issue 5 https://doi.org/10.1021/nl3004754	journal	April 2012
Two-Dimensional Boron Monolayer Sheets Wu, Xiaojun; Dai, Jun; Zhao, Yu ACS Nano, Vol. 6, Issue 8 https://doi.org/10.1021/nn302696v	journal	July 2012
Polyphony in B flat Zhang, Zhuhua; Penev, Evgeni S.; Yakobson, Boris I. Nature Chemistry, Vol. 8, Issue 6 https://doi.org/10.1038/nchem.2521	journal	April 2016
Graphene on Ir(111): Physisorption with Chemical Modulation Busse, Carsten; Lazić, Predrag; Djemour, Rabie Physical Review Letters, Vol. 107, Issue 3 https://doi.org/10.1103/PhysRevLett.107.036101	journal	July 2011
Atomic Scale Identification of Coexisting Graphene Structures on Ni(111) Bianchini, Federico; Patera, Laerte L.; Peressi, Maria The Journal of Physical Chemistry Letters, Vol. 5, Issue 3 https://doi.org/10.1021/jz402609d	journal	January 2014
Graphene on Ru(0001): a corrugated and chiral structure Martoccia, D.; Björck, M.; Schlepütz, C. M. New Journal of Physics, Vol. 12, Issue 4 https://doi.org/10.1088/1367-2630/12/4/043028	journal	April 2010
Structure and Growth of Hexagonal Boron Nitride on Ir(111) Farwick zum Hagen, Ferdinand H.; Zimmermann, Domenik M.; Silva, Caio C. ACS Nano, Vol. 10, Issue 12 https://doi.org/10.1021/acsnano.6b05819	journal	November 2016
Boron Nitride Nanomesh: Functionality from a Corrugated Monolayer Berner, Simon; Corso, Martina; Widmer, Roland Angewandte Chemie International Edition, Vol. 46, Issue 27 https://doi.org/10.1002/anie.200700234	journal	July 2007
Surface structure determination using x-ray standing waves Woodruff, D. P. Reports on Progress in Physics, Vol. 68, Issue 4 https://doi.org/10.1088/0034-4885/68/4/R01	journal	March 2005
Surface structure determination with X-ray standing waves Zegenhagen, J. Surface Science Reports, Vol. 18, Issue 7-8 https://doi.org/10.1016/0167-5729(93)90025-K	journal	October 1993
Substrate-Induced Nanoscale Undulations of Borophene on Silver Zhang, Zhuhua; Mannix, Andrew J.; Hu, Zhili Nano Letters, Vol. 16, Issue 10 https://doi.org/10.1021/acs.nanolett.6b03349	journal	September 2016
Synthesis and chemistry of elemental 2D materials Mannix, Andrew J.; Kiraly, Brian; Hersam, Mark C. Nature Reviews Chemistry, Vol. 1, Issue 2 https://doi.org/10.1038/s41570-016-0014	journal	January 2017
Corrugation in the Weakly Interacting Hexagonal-BN/Cu(111) System: Structure Determination by Combining Noncontact Atomic Force Microscopy and X-ray Standing Waves Schwarz, Martin; Riss, Alexander; Garnica, Manuela ACS Nano, Vol. 11, Issue 9 https://doi.org/10.1021/acsnano.7b04022	journal	September 2017
Chemically Resolved Interface Structure of Epitaxial Graphene on SiC(0001) Emery, Jonathan D.; Detlefs, Blanka; Karmel, Hunter J. Physical Review Letters, Vol. 111, Issue 21 https://doi.org/10.1103/PhysRevLett.111.215501	journal	November 2013
Determination of atomic positions in silicene on Ag(111) by low-energy electron diffraction Kawahara, K.; Shirasawa, T.; Arafune, R. Surface Science, Vol. 623 https://doi.org/10.1016/j.susc.2013.12.013	journal	May 2014
Potential Energy Landscape for Hot Electrons in Periodically Nanostructured Graphene Borca, B.; Barja, S.; Garnica, M. Physical Review Letters, Vol. 105, Issue 3 https://doi.org/10.1103/PhysRevLett.105.036804	journal	July 2010
Spin-Dependent Electron Scattering at Graphene Edges on Ni(111) Garcia-Lekue, A.; Balashov, T.; Olle, M. Physical Review Letters, Vol. 112, Issue 6 https://doi.org/10.1103/PhysRevLett.112.066802	journal	February 2014
Core level binding energies of functionalized and defective graphene Susi, Toma; Kaukonen, Markus; Havu, Paula Beilstein Journal of Nanotechnology, Vol. 5 https://doi.org/10.3762/bjnano.5.12	journal	January 2014
Angular distribution of the photoelectron yield excited by two coherently coupled photon beams Berman, Lonny E.; Bedzyk, Michael J. Physical Review Letters, Vol. 63, Issue 11 https://doi.org/10.1103/PhysRevLett.63.1172	journal	September 1989
X-ray standing wave study of iodine on Ge(111) Bedzyk, M. J.; Shen, Q.; Keeffe, M. E. Surface Science, Vol. 220, Issue 2-3 https://doi.org/10.1016/0039-6028(89)90243-4	journal	October 1989
Solution to the Surface Registration Problem Using X-Ray Standing Waves Golovchenko, J. A.; Patel, J. R.; Kaplan, D. R. Physical Review Letters, Vol. 49, Issue 8 https://doi.org/10.1103/PhysRevLett.49.560	journal	August 1982
Bonding of hexagonal BN to transition metal surfaces: An ab initio density-functional theory study Laskowski, Robert; Blaha, Peter; Schwarz, Karlheinz Physical Review B, Vol. 78, Issue 4 https://doi.org/10.1103/PhysRevB.78.045409	journal	July 2008
Direct evidence of metallic bands in a monolayer boron sheet Feng, Baojie; Zhang, Jin; Liu, Ro-Ya Physical Review B, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevB.94.041408	journal	July 2016
Discovery of 2D Anisotropic Dirac Cones Feng, Baojie; Zhang, Jin; Ito, Suguru Advanced Materials, Vol. 30, Issue 2 https://doi.org/10.1002/adma.201704025	journal	November 2017
Can Two-Dimensional Boron Superconduct? Penev, Evgeni S.; Kutana, Alex; Yakobson, Boris I. Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.6b00070	journal	March 2016

Cited By (6)

Inorganic Boron-Based Nanostructures: Synthesis, Optoelectronic Properties, and Prospective Applications Tian, Yan; Guo, Zekun; Zhang, Tong Nanomaterials, Vol. 9, Issue 4 https://doi.org/10.3390/nano9040538	journal	April 2019
Boron Nanosheets for Efficient All‐Optical Modulation and Logic Operation Guo, Qiangbing; Wu, Kan; Shao, Zhengpeng Advanced Optical Materials https://doi.org/10.1002/adom.201900322	journal	May 2019
2D Boron Sheets: Structure, Growth, and Electronic and Thermal Transport Properties Li, Dengfeng; Gao, Junfeng; Cheng, Peng Advanced Functional Materials, Vol. 30, Issue 8 https://doi.org/10.1002/adfm.201904349	journal	August 2019
Geometric imaging of borophene polymorphs with functionalized probes Liu, Xiaolong; Wang, Luqing; Li, Shaowei Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09686-w	journal	April 2019
Borophene layers on an Al(111) surface – the finding of a borophene layer with hexagonal double chains and B ₉ nonagons using ab initio calculations Karthikeyan, J.; Ranawat, Yashasvi S.; Murugan, P. Nanoscale, Vol. 10, Issue 36 https://doi.org/10.1039/c8nr04638g	journal	January 2018
Freestanding Borophene and Its Hybrids Ranjan, Pranay; Sahu, Tumesh Kumar; Bhushan, Rebti Advanced Materials, Vol. 31, Issue 27 https://doi.org/10.1002/adma.201900353	journal	May 2019

Similar Records

Borophene Synthesis on Au(111)

Journal Article · Thu Mar 07 00:00:00 EST 2019 · ACS Nano · OSTI ID:1482105

Kiraly, Brian; Liu, Xiaolong; Wang, Luqing; +6 more

Borophene as a prototype for synthetic 2D materials development

Journal Article · Wed Jun 06 00:00:00 EDT 2018 · Nature Nanotechnology · OSTI ID:1482105

Mannix, Andrew J.; Zhang, Zhuhua; Guisinger, Nathan P.; +2 more

Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs

Journal Article · Thu Dec 17 00:00:00 EST 2015 · Science · OSTI ID:1482105

Mannix, A. J.; Zhou, X. -F.; Kiraly, B.; +12 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
boron
borophene
two-dimensional materials
x-ray photoelectron spectroscopy
x-ray standing wave

Title: Resolving the Chemically Discrete Structure of Synthetic Borophene Polymorphs

Citation Formats

References (37)

Cited By (6)

Similar Records

Related Subjects