Dy adsorption on and intercalation under graphene on 6H-SiC(0001) surface from first-principles calculations

Han, Yong; Evans, James W.; Tringides, Michael C.

doi:10.1103/physrevmaterials.5.074004

Dy adsorption on and intercalation under graphene on 6H-SiC(0001) surface from first-principles calculations

Journal Article · Wed Jul 21 00:00:00 EDT 2021 · Physical Review Materials

DOI:https://doi.org/10.1103/physrevmaterials.5.074004· OSTI ID:1817655

^[1]; ^[1]; ^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States)

Previous experimental observations motivate clarification of configuration stabilities and kinetic processes for intercalation of guest atoms into a layered van der Waals material such as a graphene-SiC system. From our first-principles density functional theory (DFT) calculations, we analyze Dy adsorption and intercalation for graphene on a 6H-SiC(0001) surface, where the system includes two single-atom-thick graphene layers: the top-layer graphene (TLG) and the underling buffer-layer graphene (BLG) above the terminal Si layer. Our chemical potential analysis shows that intercalation of a single Dy atom into the gallery between TLG and BLG is more favorable than adsorption on TLG but that intercalation into the gallery underneath BLG is highly unfavorable. We obtain diffusion barriers of ~0.45 and 0.54 eV for a Dy atom diffusing on and under TLG, respectively. We find that the direct penetration of a Dy atom from the graphene top into the gallery under TLG is almost inhibited below a temperature of ~1400 K due to a large global barrier of at least ~3.5 eV. Instead, we find that a single Dy atom on TLG can easily intercalate by crossing a TLG step (e.g., a zigzag step presaturated by a Dy chain or a reconstructed zigzag step zz57). Additionally, we also perform DFT calculations for different Dy coverages to demonstrate how the favorability of Dy intercalation, as well as the corresponding interlayer spacings, depend on the coverage. Consequently, we can provide general insight and guidance for extensively studied systems involving intercalation of foreign atoms into graphene on a SiC substrate.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; AC02-07CH11358

OSTI ID:: 1817655

Report Number(s):: IS--J 10,554

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 7 Vol. 5; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (70)

Intercalation of Layered Materials from Bulk to 2D Stark, Madeline S.; Kuntz, Kaci L.; Martens, Sean J. Advanced Materials, Vol. 31, Issue 27 https://doi.org/10.1002/adma.201808213	journal	May 2019
Manipulation of Dirac cones in intercalated epitaxial graphene Kim, Minsung; Tringides, Michael C.; Hershberger, Matthew T. Carbon, Vol. 123 https://doi.org/10.1016/j.carbon.2017.07.020	journal	October 2017
Doping modulation of quasi-free-standing monolayer graphene formed on SiC(0001) through Sn1-Ge intercalation Kim, Hidong; Dugerjav, Otgonbayar; Lkhagvasuren, Altaibaatar Carbon, Vol. 144 https://doi.org/10.1016/j.carbon.2018.12.084	journal	April 2019
Structure of superconducting Ca-intercalated bilayer Graphene/SiC studied using total-reflection high-energy positron diffraction Endo, Y.; Fukaya, Y.; Mochizuki, I. Carbon, Vol. 157 https://doi.org/10.1016/j.carbon.2019.10.070	journal	February 2020
Calcium intercalation underneath N-layer graphene on 6H-SiC(0001) Zhang, Yuxi; Zhang, Hanjie; Cai, Yiliang Chemical Physics Letters, Vol. 703 https://doi.org/10.1016/j.cplett.2018.05.014	journal	July 2018
Intercalated rare-earth metals under graphene on SiC Anderson, Nathaniel A.; Hupalo, Myron; Keavney, David Journal of Magnetism and Magnetic Materials, Vol. 474 https://doi.org/10.1016/j.jmmm.2018.11.007	journal	March 2019
Growth morphology and properties of metals on graphene Liu, Xiaojie; Han, Yong; Evans, James W. Progress in Surface Science, Vol. 90, Issue 4 https://doi.org/10.1016/j.progsurf.2015.07.001	journal	December 2015
Functionalization of 2D materials by intercalation Daukiya, L.; Nair, M. N.; Cranney, M. Progress in Surface Science, Vol. 94, Issue 1 https://doi.org/10.1016/j.progsurf.2018.07.001	journal	February 2019
Morphological evolution during epitaxial thin film growth: Formation of 2D islands and 3D mounds Evans, J. W.; Thiel, P. A.; Bartelt, M. C. Surface Science Reports, Vol. 61, Issue 1-2 https://doi.org/10.1016/j.surfrep.2005.08.004	journal	April 2006
Surface energies, adhesion energies, and exfoliation energies relevant to copper-graphene and copper-graphite systems Han, Yong; Lai, King C.; Lii-Rosales, Ann Surface Science, Vol. 685 https://doi.org/10.1016/j.susc.2019.01.009	journal	July 2019
Metal-dielectric transition in Sn-intercalated graphene on SiC(0001) Niu, Y. R.; Zakharov, A. A.; Yakimova, R. Ultramicroscopy, Vol. 183 https://doi.org/10.1016/j.ultramic.2017.05.010	journal	December 2017
Freestanding n-Doped Graphene via Intercalation of Calcium and Magnesium into the Buffer Layer–SiC(0001) Interface Kotsakidis, Jimmy C.; Grubišić-Čabo, Antonija; Yin, Yuefeng Chemistry of Materials, Vol. 32, Issue 15 https://doi.org/10.1021/acs.chemmater.0c01729	journal	July 2020
Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights Lii-Rosales, Ann; Han, Yong; Evans, James W. The Journal of Physical Chemistry C, Vol. 122, Issue 8 https://doi.org/10.1021/acs.jpcc.7b12533	journal	February 2018
Thermodynamic Preference for Atom Adsorption on versus Intercalation into Multilayer Graphene Li, Wei; Huang, Li; Tringides, Michael C. The Journal of Physical Chemistry Letters, Vol. 11, Issue 22 https://doi.org/10.1021/acs.jpclett.0c02887	journal	November 2020
Superconducting Calcium-Intercalated Bilayer Graphene Ichinokura, Satoru; Sugawara, Katsuaki; Takayama, Akari ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b07848	journal	January 2016
Epitaxial Graphene Transistors: Enhancing Performance via Hydrogen Intercalation Robinson, Joshua A.; Hollander, Matthew; LaBella, Michael Nano Letters, Vol. 11, Issue 9 https://doi.org/10.1021/nl2019855	journal	September 2011
Quasi-Free-Standing Epitaxial Graphene on SiC (0001) by Fluorine Intercalation from a Molecular Source Wong, Swee Liang; Huang, Han; Wang, Yuzhan ACS Nano, Vol. 5, Issue 9 https://doi.org/10.1021/nn202910t	journal	August 2011
Dislocations in bilayer graphene Butz, Benjamin; Dolle, Christian; Niekiel, Florian Nature, Vol. 505, Issue 7484 https://doi.org/10.1038/nature12780	journal	December 2013
Free-standing graphene at atomic resolution Gass, Mhairi H.; Bangert, Ursel; Bleloch, Andrew L. Nature Nanotechnology, Vol. 3, Issue 11 https://doi.org/10.1038/nnano.2008.280	journal	September 2008
Semiconductor to metal transition in two-dimensional gold and its van der Waals heterostack with graphene Forti, Stiven; Link, Stefan; Stöhr, Alexander Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15683-1	journal	May 2020
Spin-induced band modifications of graphene through intercalation of magnetic iron atoms Sung, S. J.; Yang, J. W.; Lee, P. R. Nanoscale, Vol. 6, Issue 7 https://doi.org/10.1039/C3NR04178F	journal	January 2014
Tuning two-dimensional nanomaterials by intercalation: materials, properties and applications Wan, Jiayu; Lacey, Steven D.; Dai, Jiaqi Chemical Society Reviews, Vol. 45, Issue 24 https://doi.org/10.1039/C5CS00758E	journal	January 2016
Squeezed nanocrystals: equilibrium configuration of metal clusters embedded beneath the surface of a layered material Julien, Scott E.; Lii-Rosales, Ann; Wan, Kai-Tak Nanoscale, Vol. 11, Issue 13 https://doi.org/10.1039/C8NR10549A	journal	January 2019
Epitaxial graphene/silicon carbide intercalation: a minireview on graphene modulation and unique 2D materials Briggs, Natalie; Gebeyehu, Zewdu M.; Vera, Alexander Nanoscale, Vol. 11, Issue 33 https://doi.org/10.1039/C9NR03721G	journal	January 2019
Encapsulation of metal nanoparticles at the surface of a prototypical layered material Lii-Rosales, Ann; Han, Yong; Jing, Dapeng Nanoscale, Vol. 13, Issue 3 https://doi.org/10.1039/D0NR07024F	journal	January 2021
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
From Initial to Late Stages of Epitaxial Thin Film Growth: STM Analysis and Atomistic or Coarse-Grained Modeling Evans, J. W.; Han, Yong; Ünal, Bariş SELECTED TOPICS ON CRYSTAL GROWTH: 14th International Summer School on Crystal Growth, AIP Conference Proceedings https://doi.org/10.1063/1.3476231	conference	January 2010
Compressibility of SiC up to 68.4 GPa Bassett, W. A.; Weathers, M. S.; Wu, T. ‐C. Journal of Applied Physics, Vol. 74, Issue 6 https://doi.org/10.1063/1.354476	journal	September 1993
The elastic constants of silicon carbide: A Brillouin-scattering study of 4H and 6H SiC single crystals Kamitani, K.; Grimsditch, M.; Nipko, J. C. Journal of Applied Physics, Vol. 82, Issue 6 https://doi.org/10.1063/1.366100	journal	September 1997
Superconductivity in Ca-intercalated epitaxial graphene on silicon carbide Li, Kang; Feng, Xiao; Zhang, Wenhao Applied Physics Letters, Vol. 103, Issue 6 https://doi.org/10.1063/1.4817781	journal	August 2013
Competitive formation of intercalated versus supported metal nanoclusters during deposition on layered materials with surface point defects Han, Yong; Lii-Rosales, Ann; Tringides, Michael C. The Journal of Chemical Physics, Vol. 154, Issue 2 https://doi.org/10.1063/5.0037480	journal	January 2021
Energy barriers for Dy and H penetrating graphene on 6 H -SiC(0001) and freestanding bilayer graphene from first-principles calculations Han, Yong; Evans, James W.; Tringides, Michael C. Applied Physics Letters, Vol. 119, Issue 3 https://doi.org/10.1063/5.0056916	journal	July 2021
Ca intercalated bilayer graphene as a thinnest limit of superconducting C6Ca Kanetani, K.; Sugawara, K.; Sato, T. Proceedings of the National Academy of Sciences, Vol. 109, Issue 48 https://doi.org/10.1073/pnas.1208889109	journal	November 2012
Strain solitons and topological defects in bilayer graphene Alden, J. S.; Tsen, A. W.; Huang, P. Y. Proceedings of the National Academy of Sciences, Vol. 110, Issue 28 https://doi.org/10.1073/pnas.1309394110	journal	June 2013
Evidence for superconductivity in Li-decorated monolayer graphene Ludbrook, B. M.; Levy, G.; Nigge, P. Proceedings of the National Academy of Sciences, Vol. 112, Issue 38 https://doi.org/10.1073/pnas.1510435112	journal	September 2015
The Compressibility of Media under Extreme Pressures Murnaghan, F. D. Proceedings of the National Academy of Sciences, Vol. 30, Issue 9 https://doi.org/10.1073/pnas.30.9.244	journal	September 1944
The Elastic Behaviour of a Crystalline Aggregate Hill, R. Proceedings of the Physical Society. Section A, Vol. 65, Issue 5 https://doi.org/10.1088/0370-1298/65/5/307	journal	May 1952
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
Reverse-engineering of graphene on metal surfaces: a case study of embedded ruthenium Lii-Rosales, Ann; Han, Yong; Yu, Ka Man Nanotechnology, Vol. 29, Issue 50 https://doi.org/10.1088/1361-6528/aae1e3	journal	October 2018
Shapes of Fe nanocrystals encapsulated at the graphite surface Lii-Rosales, Ann; Han, Yong; Julien, Scott E. New Journal of Physics, Vol. 22, Issue 2 https://doi.org/10.1088/1367-2630/ab687a	journal	February 2020
Mini-Dirac cones in the band structure of a copper intercalated epitaxial graphene superlattice Forti, S.; Stöhr, A.; Zakharov, A. A. 2D Materials, Vol. 3, Issue 3 https://doi.org/10.1088/2053-1583/3/3/035003	journal	July 2016
Lattice Constants of Graphite at Low Temperatures Baskin, Y.; Meyer, L. Physical Review, Vol. 100, Issue 2 https://doi.org/10.1103/PhysRev.100.544	journal	October 1955
Finite Elastic Strain of Cubic Crystals Birch, Francis Physical Review, Vol. 71, Issue 11 https://doi.org/10.1103/PhysRev.71.809	journal	June 1947
Structure of Gd, Dy, and Er at Low Temperatures Banister, J. R.; Legvold, S.; Spedding, F. H. Physical Review, Vol. 94, Issue 5 https://doi.org/10.1103/PhysRev.94.1140	journal	June 1954
Tuning the doping level of graphene in the vicinity of the Van Hove singularity via ytterbium intercalation Rosenzweig, Philipp; Karakachian, Hrag; Link, Stefan Physical Review B, Vol. 100, Issue 3 https://doi.org/10.1103/PhysRevB.100.035445	journal	July 2019
Energy barriers for Pb adatom diffusion on stepped ultrathin Pb(111) quantum nanofilms: First-principles calculations Han, Yong; Evans, James W.; Liu, Feng Physical Review B, Vol. 100, Issue 19 https://doi.org/10.1103/PhysRevB.100.195405	journal	November 2019
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Heteroepitaxial graphite on 6 H − SiC ( 0001 ) : Interface formation through conduction-band electronic structure Forbeaux, I.; Themlin, J. -M.; Debever, J. -M. Physical Review B, Vol. 58, Issue 24 https://doi.org/10.1103/PhysRevB.58.16396	journal	December 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Stacking domains of epitaxial few-layer graphene on SiC(0001) Hibino, H.; Mizuno, S.; Kageshima, H. Physical Review B, Vol. 80, Issue 8 https://doi.org/10.1103/PhysRevB.80.085406	journal	August 2009
Electronic decoupling of an epitaxial graphene monolayer by gold intercalation Gierz, Isabella; Suzuki, Takayuki; Weitz, R. Thomas Physical Review B, Vol. 81, Issue 23 https://doi.org/10.1103/PhysRevB.81.235408	journal	June 2010
Decoupling graphene from SiC(0001) via oxidation Oida, S.; McFeely, F. R.; Hannon, J. B. Physical Review B, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevB.82.041411	journal	July 2010
Electronic and geometric structure of graphene/SiC(0001) decoupled by lithium intercalation Bisti, F.; Profeta, G.; Vita, H. Physical Review B, Vol. 91, Issue 24 https://doi.org/10.1103/PhysRevB.91.245411	journal	June 2015
Charge neutrality in epitaxial graphene on 6 H -SiC(0001) via nitrogen intercalation Caffrey, Nuala M.; Armiento, Rickard; Yakimova, Rositsa Physical Review B, Vol. 92, Issue 8 https://doi.org/10.1103/PhysRevB.92.081409	journal	August 2015
Energetics of Cu adsorption and intercalation at graphite step edges Han, Yong; Lii-Rosales, Ann; Tringides, Michael C. Physical Review B, Vol. 99, Issue 11 https://doi.org/10.1103/PhysRevB.99.115415	journal	March 2019
Quasi-Free-Standing Epitaxial Graphene on SiC Obtained by Hydrogen Intercalation Riedl, C.; Coletti, C.; Iwasaki, T. Physical Review Letters, Vol. 103, Issue 24 https://doi.org/10.1103/PhysRevLett.103.246804	journal	December 2009
Extended van Hove Singularity and Superconducting Instability in Doped Graphene McChesney, J. L.; Bostwick, Aaron; Ohta, Taisuke Physical Review Letters, Vol. 104, Issue 13 https://doi.org/10.1103/PhysRevLett.104.136803	journal	April 2010
Approaching Truly Freestanding Graphene: The Structure of Hydrogen-Intercalated Graphene on 6 H − SiC ( 0001 ) Sforzini, J.; Nemec, L.; Denig, T. Physical Review Letters, Vol. 114, Issue 10 https://doi.org/10.1103/PhysRevLett.114.106804	journal	March 2015
Charge-Density Wave in Ca-Intercalated Bilayer Graphene Induced by Commensurate Lattice Matching Shimizu, Ryota; Sugawara, Katsuaki; Kanetani, Kohei Physical Review Letters, Vol. 114, Issue 14 https://doi.org/10.1103/PhysRevLett.114.146103	journal	April 2015
Ab Initio Study of Graphene on SiC Mattausch, Alexander; Pankratov, Oleg Physical Review Letters, Vol. 99, Issue 7 https://doi.org/10.1103/PhysRevLett.99.076802	journal	August 2007
Nucleation and growth kinetics for intercalated islands during deposition on layered materials with isolated pointlike surface defects Han, Yong; Lii-Rosales, A.; Zhou, Y. Physical Review Materials, Vol. 1, Issue 5 https://doi.org/10.1103/PhysRevMaterials.1.053403	journal	October 2017
Intercalated europium metal in epitaxial graphene on SiC Anderson, Nathaniel A.; Hupalo, Myron; Keavney, David Physical Review Materials, Vol. 1, Issue 5 https://doi.org/10.1103/PhysRevMaterials.1.054005	journal	October 2017
Intrinsic stacking domains in graphene on silicon carbide: A pathway for intercalation de Jong, T. A.; Krasovskii, E. E.; Ott, C. Physical Review Materials, Vol. 2, Issue 10 https://doi.org/10.1103/PhysRevMaterials.2.104005	journal	October 2018
Adsorption, intercalation, diffusion, and adhesion of Cu at the 2 H − Mo S 2 (0001) surface from first-principles calculations Han, Yong; Tringides, Michael C.; Evans, James W. Physical Review Research, Vol. 2, Issue 1 https://doi.org/10.1103/PhysRevResearch.2.013182	journal	February 2020
Search for encapsulation of platinum, silver, and gold at the surface of graphite Lii-Rosales, Ann; Han, Yong; Jing, Dapeng Physical Review Research, Vol. 2, Issue 3 https://doi.org/10.1103/PhysRevResearch.2.033175	journal	July 2020
Structure refinement of the silicon carbide polytypes 4 H and 6 H : unambiguous determination of the refinement parameters Bauer, A.; Reischauer, Ph.; Kräusslich, J. Acta Crystallographica Section A Foundations of Crystallography, Vol. 57, Issue 1 https://doi.org/10.1107/S0108767300012915	journal	January 2001
Fabricating Fe nanocrystals via encapsulation at the graphite surface Lii-Rosales, Ann; Han, Yong; Lai, King C. Journal of Vacuum Science & Technology A, Vol. 37, Issue 6 https://doi.org/10.1116/1.5124927	journal	December 2019
Controlling the Electronic Structure of Bilayer Graphene Ohta, Taisuke; Bostwick, Aaron; Seyller, Thomas Science, Vol. 313, Issue 5789 https://doi.org/10.1126/science.1130681	journal	August 2006
Quantum Hall Effect and Carrier Scattering in Quasi-Free-Standing Monolayer Graphene Tanabe, Shinichi; Takamura, Makoto; Harada, Yuichi Applied Physics Express, Vol. 5, Issue 12 https://doi.org/10.1143/APEX.5.125101	journal	November 2012
The 6H-SiC structure model: Further refinement from SCXRD data from a terrestrial moissanite Capitani, G. C.; Di Pierro, S.; Tempesta, G. American Mineralogist, Vol. 92, Issue 2-3 https://doi.org/10.2138/am.2007.2346	journal	February 2007

Similar Records

Thermodynamics and kinetics of H adsorption and intercalation for graphene on 6H-SiC(0001) from first-principles calculations

Journal Article · Mon Dec 06 19:00:00 EST 2021 · Journal of Vacuum Science and Technology A · OSTI ID:1835555

Energy barriers for Dy and H penetrating graphene on 6H-SiC(0001) and freestanding bilayer graphene from first-principles calculations

Journal Article · Mon Jul 19 20:00:00 EDT 2021 · Applied Physics Letters · OSTI ID:1817665

Related Subjects

36 MATERIALS SCIENCE
graphene
interface & surface thermodynamics
potential energy surfaces
surface growth

Dy adsorption on and intercalation under graphene on 6H-SiC(0001) surface from first-principles calculations

Citation Formats

References (70)

Similar Records

Related Subjects