Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

Gilbert, S. Matt; Dunn, Gabriel; Azizi, Amin; Pham, Thang; Shevitski, Brian; Dimitrov, Edgar; Liu, Stanley; Aloni, Shaul; Zettl, Alex

doi:10.1038/s41598-017-12684-x

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

Journal Article · Wed Nov 08 00:00:00 EST 2017 · Scientific Reports

DOI:https://doi.org/10.1038/s41598-017-12684-x· OSTI ID:1419454

Gilbert, S. Matt ^[1]; Dunn, Gabriel ^[1]; Azizi, Amin ^[2]; Pham, Thang ^[1]; Shevitski, Brian ^[3]; Dimitrov, Edgar ^[2]; Liu, Stanley ^[2]; Aloni, Shaul ^[4]; Zettl, Alex ^[5]

Univ. of Calirnia, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of Calirnia, Berkeley, CA (United States). Kavli Energy NanoScience Inst.
Univ. of Calirnia, Berkeley, CA (United States). Dept. of Physics; Univ. of Calirnia, Berkeley, CA (United States). Kavli Energy NanoScience Inst.
Univ. of Calirnia, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of Calirnia, Berkeley, CA (United States). Kavli Energy NanoScience Inst.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Univ. of Calirnia, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of Calirnia, Berkeley, CA (United States). Kavli Energy NanoScience Inst.

Here, we demonstrate the fabrication of individual nanopores in hexagonal boron nitride (h-BN) with atomically precise control of the pore shape and size. Previous methods of pore production in other 2D materials typically create pores with irregular geometry and imprecise diameters. In contrast, other studies have shown that with careful control of electron irradiation, defects in h-BN grow with pristine zig-zag edges at quantized triangular sizes, but they have failed to demonstrate production and control of isolated defects. In this work, we combine these techniques to yield a method in which we can create individual size-quantized triangular nanopores through an h-BN sheet. The pores are created using the electron beam of a conventional transmission electron microscope; which can strip away multiple layers of h-BN exposing single-layer regions, introduce single vacancies, and preferentially grow vacancies only in the single-layer region. We further demonstrate how the geometry of these pores can be altered beyond triangular by changing beam conditions. Precisely size- and geometry-tuned nanopores could find application in molecular sensing, DNA sequencing, water desalination, and molecular separation.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOD; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1419454

Journal Information:: Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 7; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Atomic Defects in Two Dimensional Materials Rasool, Haider I.; Ophus, Colin; Zettl, Alex Advanced Materials, Vol. 27, Issue 38 https://doi.org/10.1002/adma.201500231	journal	May 2015
Growth and Etching of Monolayer Hexagonal Boron Nitride Wang, Lifeng; Wu, Bin; Jiang, Lili Advanced Materials, Vol. 27, Issue 33 https://doi.org/10.1002/adma.201501166	journal	July 2015
Chemistry at the Edge of Graphene Bellunato, Amedeo; Arjmandi Tash, Hadi; Cesa, Yanina ChemPhysChem, Vol. 17, Issue 6 https://doi.org/10.1002/cphc.201500926	journal	December 2015
Vacancy growth and migration dynamics in atomically thin hexagonal boron nitride under electron beam irradiation Alem, Nasim; Erni, Rolf; Kisielowski, Christian physica status solidi (RRL) - Rapid Research Letters, Vol. 5, Issue 8 https://doi.org/10.1002/pssr.201105262	journal	July 2011
Inelastic electron irradiation damage in hexagonal boron nitride Cretu, Ovidiu; Lin, Yung-Chang; Suenaga, Kazutomo Micron, Vol. 72 https://doi.org/10.1016/j.micron.2015.02.002	journal	May 2015
Engineering and Localization of Quantum Emitters in Large Hexagonal Boron Nitride Layers Choi, Sumin; Tran, Toan Trong; Elbadawi, Christopher ACS Applied Materials & Interfaces, Vol. 8, Issue 43 https://doi.org/10.1021/acsami.6b09875	journal	October 2016
Plasmonic Nanopores for Trapping, Controlling Displacement, and Sequencing of DNA Belkin, Maxim; Chao, Shu-Han; Jonsson, Magnus P. ACS Nano, Vol. 9, Issue 11 https://doi.org/10.1021/acsnano.5b04173	journal	October 2015
Water Desalination across Nanoporous Graphene Cohen-Tanugi, David; Grossman, Jeffrey C. Nano Letters, Vol. 12, Issue 7, p. 3602-3608 https://doi.org/10.1021/nl3012853	journal	June 2012
Graphene Nanopore with a Self-Integrated Optical Antenna Nam, SungWoo; Choi, Inhee; Fu, Chi-cheng Nano Letters, Vol. 14, Issue 10 https://doi.org/10.1021/nl503159d	journal	September 2014
Transfer of CVD-Grown Monolayer Graphene onto Arbitrary Substrates Suk, Ji Won; Kitt, Alexander; Magnuson, Carl W. ACS Nano, Vol. 5, Issue 9 https://doi.org/10.1021/nn201207c	journal	August 2011
Atomic Resolution Imaging and Topography of Boron Nitride Sheets Produced by Chemical Exfoliation Warner, Jamie H.; Rümmeli, Mark H.; Bachmatiuk, Alicja ACS Nano, Vol. 4, Issue 3 https://doi.org/10.1021/nn901648q	journal	February 2010
Graphene as a subnanometre trans-electrode membrane Garaj, S.; Hubbard, W.; Reina, A. Nature, Vol. 467, Issue 7312, p. 190-193 https://doi.org/10.1038/nature09379	journal	August 2010
Water desalination with a single-layer MoS2 nanopore Heiranian, Mohammad; Farimani, Amir Barati; Aluru, Narayana R. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9616	journal	October 2015
Detecting the translocation of DNA through a nanopore using graphene nanoribbons Traversi, F.; Raillon, C.; Benameur, S. M. Nature Nanotechnology, Vol. 8, Issue 12 https://doi.org/10.1038/nnano.2013.240	journal	November 2013
A direct transfer of layer-area graphene Regan, William; Alem, Nasim; Alemán, Benjamín Applied Physics Letters, Vol. 96, Issue 11 https://doi.org/10.1063/1.3337091	journal	March 2010
Atom-by-atom nucleation and growth of graphene nanopores Russo, C. J.; Golovchenko, J. A. Proceedings of the National Academy of Sciences, Vol. 109, Issue 16, p. 5953-5957 https://doi.org/10.1073/pnas.1119827109	journal	April 2012
Molecule-hugging graphene nanopores Garaj, S.; Liu, S.; Golovchenko, J. A. Proceedings of the National Academy of Sciences, Vol. 110, Issue 30 https://doi.org/10.1073/pnas.1220012110	journal	July 2013
Slowing the translocation of double-stranded DNA using a nanopore smaller than the double helix Mirsaidov, Utkur; Comer, Jeffrey; Dimitrov, Valentin Nanotechnology, Vol. 21, Issue 39 https://doi.org/10.1088/0957-4484/21/39/395501	journal	September 2010
2D materials advances: from large scale synthesis and controlled heterostructures to improved characterization techniques, defects and applications Lin, Zhong; McCreary, Amber; Briggs, Natalie 2D Materials, Vol. 3, Issue 4 https://doi.org/10.1088/2053-1583/3/4/042001	journal	December 2016
Electron knock-on damage in hexagonal boron nitride monolayers Kotakoski, J.; Jin, C. H.; Lehtinen, O. Physical Review B, Vol. 82, Issue 11 https://doi.org/10.1103/physrevb.82.113404	journal	September 2010
Fabrication of a Freestanding Boron Nitride Single Layer and Its Defect Assignments Jin, Chuanhong; Lin, Fang; Suenaga, Kazu Physical Review Letters, Vol. 102, Issue 19 https://doi.org/10.1103/physrevlett.102.195505	journal	May 2009
Selective Molecular Sieving through Porous Graphene Koenig, Steven P.; Wang, Luda; Pellegrino, John arXiv https://doi.org/10.48550/arxiv.1208.4135	text	January 2012
Identification of single nucleotides in MoS2 nanopores Feng, Jiandong; Liu, Ke; Bulushev, Roman D. arXiv https://doi.org/10.48550/arxiv.1505.01608	text	January 2015
Molecular Valves for Controlling Gas Phase Transport Made from Discrete Angstrom-Sized Pores in Graphene Wang, Luda; Drahushuk, Lee W.; Cantley, Lauren arXiv https://doi.org/10.48550/arxiv.1506.06693	text	January 2015
Boron Nitride Nanopores: Highly Sensitive DNA Single-Molecule Detectors Liu, Song; Lu, Bo; Zhao, Qing Advanced Materials, Vol. 25, Issue 33 https://doi.org/10.1002/adma.201301336	journal	June 2013
Atomic Structure of Graphene Subnanometer Pores Robertson, Alex W.; Lee, Gun-Do; He, Kuang ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/ACSNANO.5B05700	journal	October 2015
DNA Translocation through Graphene Nanopores Merchant, Christopher A.; Healy, Ken; Wanunu, Meni Nano Letters, Vol. 10, Issue 8, p. 2915-2921 https://doi.org/10.1021/NL101046T	journal	August 2010
DNA Translocation through Graphene Nanopores Schneider, Grégory F.; Kowalczyk, Stefan W.; Calado, Victor E. Nano Letters, Vol. 10, Issue 8, p. 3163-3167 https://doi.org/10.1021/NL102069Z	journal	August 2010
Electrochemical Reaction in Single Layer MoS ₂ : Nanopores Opened Atom by Atom Feng, J.; Liu, K.; Graf, M. Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/acs.nanolett.5b00768	journal	April 2015
Formation and Dynamics of Electron-Irradiation-Induced Defects in Hexagonal Boron Nitride at Elevated Temperatures Pham, Thang; Gibb, Ashley L.; Li, Zhenglu Nano Letters, Vol. 16, Issue 11 https://doi.org/10.1021/acs.nanolett.6b03442	journal	October 2016
Monolayer WS ₂ Nanopores for DNA Translocation with Light-Adjustable Sizes Danda, Gopinath; Masih Das, Paul; Chou, Yung-Chien ACS Nano, Vol. 11, Issue 2 https://doi.org/10.1021/acsnano.6b08028	journal	February 2017
Selective Ion Passage through Functionalized Graphene Nanopores Sint, Kyaw; Wang, Boyang; Král, Petr Journal of the American Chemical Society, Vol. 130, Issue 49, p. 16448-16449 https://doi.org/10.1021/ja804409f	journal	December 2008
Selective Ion Passage through Functionalized Graphene Nanopores Sint, Kyaw; Wang, Boyang; Král, Petr Journal of the American Chemical Society, Vol. 131, Issue 27 https://doi.org/10.1021/ja903655u	journal	July 2009
Selective Ionic Transport through Tunable Subnanometer Pores in Single-Layer Graphene Membranes O’Hern, Sean C.; Boutilier, Michael S. H.; Idrobo, Juan-Carlos Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl404118f	journal	February 2014
Gold Nanorod Translocations and Charge Measurement through Solid-State Nanopores Venta, Kimberly E.; Zanjani, Mehdi B.; Ye, Xingchen Nano Letters, Vol. 14, Issue 9 https://doi.org/10.1021/nl502448s	journal	August 2014
Selective Sputtering and Atomic Resolution Imaging of Atomically Thin Boron Nitride Membranes Meyer, Jannik C.; Chuvilin, Andrey; Algara-Siller, Gerardo Nano Letters, Vol. 9, Issue 7 https://doi.org/10.1021/nl9011497	journal	July 2009
Holes with an edge Bayley, Hagan Nature, Vol. 467, Issue 7312 https://doi.org/10.1038/467164a	journal	September 2010
Fabrication of solid-state nanopores with single-nanometre precision Storm, A. J.; Chen, J. H.; Ling, X. S. Nature Materials, Vol. 2, Issue 8, p. 537-540 https://doi.org/10.1038/nmat941	journal	July 2003
DNA molecules and configurations in a solid-state nanopore microscope Li, Jiali; Gershow, Marc; Stein, Derek Nature Materials, Vol. 2, Issue 9 https://doi.org/10.1038/nmat965	journal	August 2003
Selective molecular sieving through porous graphene Koenig, Steven P.; Wang, Luda; Pellegrino, John Nature Nanotechnology, Vol. 7, Issue 11 https://doi.org/10.1038/nnano.2012.162	journal	October 2012
Molecular valves for controlling gas phase transport made from discrete ångström-sized pores in graphene Wang, Luda; Drahushuk, Lee W.; Cantley, Lauren Nature Nanotechnology, Vol. 10, Issue 9 https://doi.org/10.1038/nnano.2015.158	journal	August 2015
Identification of single nucleotides in MoS2 nanopores Feng, Jiandong; Liu, Ke; Bulushev, Roman D. Nature Nanotechnology, Vol. 10, Issue 12 https://doi.org/10.1038/nnano.2015.219	journal	September 2015
Graphene nanodevices for DNA sequencing Heerema, Stephanie J.; Dekker, Cees Nature Nanotechnology, Vol. 11, Issue 2 https://doi.org/10.1038/nnano.2015.307	journal	February 2016
Water desalination using nanoporous single-layer graphene Surwade, Sumedh P.; Smirnov, Sergei N.; Vlassiouk, Ivan V. Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.37	journal	March 2015
DNA Translocation through Hydrophilic Nanopore in Hexagonal Boron Nitride Zhou, Zhi; Hu, Ying; Wang, Hao Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03287	journal	November 2013
Atomic-scale dynamics of triangular hole growth in monolayer hexagonal boron nitride under electron irradiation Ryu, Gyeong Hee; Park, Hyo Ju; Ryou, Junga Nanoscale, Vol. 7, Issue 24 https://doi.org/10.1039/C5NR01473E	journal	January 2015
Modeling the conductance and DNA blockade of solid-state nanopores Kowalczyk, Stefan W.; Grosberg, Alexander Y.; Rabin, Yitzhak Nanotechnology, Vol. 22, Issue 31 https://doi.org/10.1088/0957-4484/22/31/315101	journal	July 2011
Slowing single-stranded DNA translocation through a solid-state nanopore by decreasing the nanopore diameter Akahori, Rena; Haga, Takanobu; Hatano, Toshiyuki Nanotechnology, Vol. 25, Issue 27 https://doi.org/10.1088/0957-4484/25/27/275501	journal	June 2014
Atomically thin hexagonal boron nitride probed by ultrahigh-resolution transmission electron microscopy Alem, Nasim; Erni, Rolf; Kisielowski, Christian Physical Review B, Vol. 80, Issue 15 https://doi.org/10.1103/PhysRevB.80.155425	journal	October 2009
Electron knock-on damage in hexagonal boron nitride monolayers Kotakoski, J.; Jin, C. H.; Lehtinen, O. Physical Review B, Vol. 82, Issue 11 https://doi.org/10.1103/PhysRevB.82.113404	journal	September 2010
From point to extended defects in two-dimensional MoS 2 : Evolution of atomic structure under electron irradiation Komsa, Hannu-Pekka; Kurasch, Simon; Lehtinen, Ossi Physical Review B, Vol. 88, Issue 3 https://doi.org/10.1103/PhysRevB.88.035301	journal	July 2013
Fabrication of a Freestanding Boron Nitride Single Layer and Its Defect Assignments Jin, Chuanhong; Lin, Fang; Suenaga, Kazu Physical Review Letters, Vol. 102, Issue 19 https://doi.org/10.1103/PhysRevLett.102.195505	journal	May 2009
Structure and Local Chemical Properties of Boron-Terminated Tetravacancies in Hexagonal Boron Nitride Cretu, Ovidiu; Lin, Yung-Chang; Koshino, Masanori Physical Review Letters, Vol. 114, Issue 7 https://doi.org/10.1103/PhysRevLett.114.075502	journal	February 2015
Graphene at the Edge: Stability and Dynamics Girit, C. O.; Meyer, J. C.; Erni, R. Science, Vol. 323, Issue 5922 https://doi.org/10.1126/science.1166999	journal	March 2009
The structure and local chemical properties of boron-terminated tetravacancies in hexagonal boron-nitride Cretu, Ovidiu; Lin, Yung-Chang; Koshino, Masanori arXiv https://doi.org/10.48550/arxiv.1411.6722	text	January 2014
Engineering and localization of quantum emitters in large hexagonal boron nitride layers Choi, Sumin; Tran, Toan Trong; ElBadawi, Christopher arXiv https://doi.org/10.48550/arxiv.1608.04108	preprint	January 2016

Cited By (13)

Comparing Current Noise in Biological and Solid-State Nanopores Fragasso, Alessio; Schmid, Sonja; Dekker, Cees ACS Nano, Vol. 14, Issue 2 https://doi.org/10.1021/acsnano.9b09353	journal	February 2020
Novel Porous Boron Nitride Nanosheet with Carbon Doping: Potential Metal‐Free Photocatalyst for Visible‐Light‐Driven Overall Water Splitting Wan, Qiang; Wei, Fenfei; Ma, Zuju Advanced Theory and Simulations, Vol. 2, Issue 4 https://doi.org/10.1002/adts.201800174	journal	January 2019
Recent advances in 2D nanopores for desalination Ramanathan, A. A.; Aqra, M. W.; Al-Rawajfeh, A. E. Environmental Chemistry Letters, Vol. 16, Issue 4 https://doi.org/10.1007/s10311-018-0745-4	journal	May 2018
High-harmonic generation from spin-polarised defects in solids Mrudul, M. S.; Tancogne-Dejean, Nicolas; Rubio, Angel npj Computational Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41524-020-0275-z	journal	January 2020
Addressing the isomer cataloguing problem for nanopores in two-dimensional materials Govind Rajan, Ananth; Silmore, Kevin S.; Swett, Jacob Nature Materials, Vol. 18, Issue 2 https://doi.org/10.1038/s41563-018-0258-3	journal	January 2019
Exploring the pore charge dependence of K ⁺ and Cl ⁻ permeation across a graphene monolayer: a molecular dynamics study Guardiani, Carlo; Gibby, William A. T.; Barabash, Miraslau L. RSC Advances, Vol. 9, Issue 35 https://doi.org/10.1039/c9ra03025e	journal	January 2019
Graphene/hexagonal boron nitride heterostructures: Mechanical properties and fracture behavior from nanoindentation simulations Mallick, Govind; Elder, Robert M. Applied Physics Letters, Vol. 113, Issue 12 https://doi.org/10.1063/1.5047782	journal	September 2018
Fast water desalination by carbon-doped boron nitride monolayer: transport assisted by water clustering at pores Loh, G. C. Nanotechnology, Vol. 30, Issue 5 https://doi.org/10.1088/1361-6528/aaf063	journal	December 2018
Alternative stacking sequences in hexagonal boron nitride Gilbert, S. Matt; Pham, Thang; Dogan, Mehmet 2D Materials, Vol. 6, Issue 2 https://doi.org/10.1088/2053-1583/ab0e24	journal	March 2019
Blue-light-emitting color centers in high-quality hexagonal boron nitride Shevitski, Brian; Gilbert, S. Matt; Chen, Christopher T. Physical Review B, Vol. 100, Issue 15 https://doi.org/10.1103/physrevb.100.155419	journal	October 2019
Quantitative insights into the growth mechanisms of nanopores in hexagonal boron nitride Mouhoub, Ouafi; Martinez-Gordillo, Rafael; Nelayah, Jaysen Physical Review Materials, Vol. 4, Issue 1 https://doi.org/10.1103/physrevmaterials.4.014005	journal	January 2020
Strain-controlled Graphene-Polymer Angular Actuator Gilbert, S. Matt; Molnar, Adam; Horton-Bailey, Donez MRS Advances, Vol. 4, Issue 40 https://doi.org/10.1557/adv.2019.276	journal	January 2019
Blue-Light-Emitting Color Centers in High-Quality Hexagonal Boron Nitride Shevitski, Brian; Gilbert, S. Matt; Chen, Christopher T. arXiv https://doi.org/10.48550/arxiv.1904.12107	text	January 2019

Similar Records

Electron beam-induced nanopores in Bernal-stacked hexagonal boron nitride

Journal Article · Sun Jul 12 20:00:00 EDT 2020 · Applied Physics Letters · OSTI ID:1639008

Magnetism and interlayer bonding in pores of Bernal-stacked hexagonal boron nitride

Journal Article · Mon Aug 22 20:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1906708

Scalable Bottom-Up Synthesis of Nanoporous Hexagonal Boron Nitride (h-BN) for Large-Area Atomically Thin Ceramic Membranes

Journal Article · Thu Feb 13 19:00:00 EST 2025 · Nano Letters · OSTI ID:2516776

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
Nanopores
Two-dimensional materials

Fabrication of Subnanometer-Precision Nanopores in Hexagonal Boron Nitride

Citation Formats

References (56)

Cited By (13)

Similar Records

Related Subjects