DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Fabricating Fe nanocrystals via encapsulation at the graphite surface

Abstract

In this paper, the authors describe the conditions under which Fe forms encapsulated nanocrystals beneath the surface of graphite, and they characterize these islands (graphite + Fe) thoroughly. The authors use the experimental techniques of scanning tunneling microscopy (STM) plus x-ray photoelectron spectroscopy (XPS) and the computational technique of density functional theory (DFT). Necessary conditions for encapsulation are preexisting ion-induced defects in the graphite substrate and elevated deposition temperature of 875–900 K. Evidence of encapsulation consists of atomically resolved STM images of a carbon lattice, both on top of the islands and on the sloping sides. The nature of the images indicates that this carbon lattice corresponds to a graphene blanket consisting of more than one graphene sheet that drapes continuously from the top of the island to the graphite substrate. The formation of iron carbide is not observed based on XPS. Shapes of the island footprints are consistent with metallic Fe, predominantly in the hcp or fcc form, though larger islands tend toward bcc. Island structures with hexagonally close-packed lateral hcp or fcc planes are stabilized by their excellent lattice match with the graphite substrate. Evolution of island density with prolonged deposition time provides evidence of coarsening, perhaps via Smoluchowski ripening. Themore » encapsulated Fe clusters are stable in air at room temperature, protected by smaller Fe clusters that decorate defect sites and block permeation of gases. DFT shows that two configurations of Fe are more stable within the gallery than adsorbed on top of the surface: a single atom of Fe and a film (slab) of metallic Fe. Comparison with other metals shows that encapsulated Fe is similar to Cu but dissimilar to Ru or Dy, leading the authors to conclude that carbon dissolution in the metal does not play a role in encapsulation.« less

Authors:
ORCiD logo [1];  [2];  [2];  [3];  [2];  [2];  [2]
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States); Univ. of Colorado, Boulder, CO (United States)
  2. Ames Lab., and Iowa State Univ., Ames, IA (United States)
  3. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1575206
Alternate Identifier(s):
OSTI ID: 1574079
Report Number(s):
IS-J-10093
Journal ID: ISSN 0734-2101
Grant/Contract Number:  
ACI-1548562; AC02-07CH11358; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Vacuum Science and Technology A
Additional Journal Information:
Journal Volume: 37; Journal Issue: 6; Journal ID: ISSN 0734-2101
Publisher:
American Vacuum Society / AIP
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Lii-Rosales, Ann, Han, Yong, Lai, King C., Jing, Dapeng, Tringides, Michael C., Evans, James W., and Thiel, Patricia A. Fabricating Fe nanocrystals via encapsulation at the graphite surface. United States: N. p., 2019. Web. doi:10.1116/1.5124927.
Lii-Rosales, Ann, Han, Yong, Lai, King C., Jing, Dapeng, Tringides, Michael C., Evans, James W., & Thiel, Patricia A. Fabricating Fe nanocrystals via encapsulation at the graphite surface. United States. https://doi.org/10.1116/1.5124927
Lii-Rosales, Ann, Han, Yong, Lai, King C., Jing, Dapeng, Tringides, Michael C., Evans, James W., and Thiel, Patricia A. Wed . "Fabricating Fe nanocrystals via encapsulation at the graphite surface". United States. https://doi.org/10.1116/1.5124927. https://www.osti.gov/servlets/purl/1575206.
@article{osti_1575206,
title = {Fabricating Fe nanocrystals via encapsulation at the graphite surface},
author = {Lii-Rosales, Ann and Han, Yong and Lai, King C. and Jing, Dapeng and Tringides, Michael C. and Evans, James W. and Thiel, Patricia A.},
abstractNote = {In this paper, the authors describe the conditions under which Fe forms encapsulated nanocrystals beneath the surface of graphite, and they characterize these islands (graphite + Fe) thoroughly. The authors use the experimental techniques of scanning tunneling microscopy (STM) plus x-ray photoelectron spectroscopy (XPS) and the computational technique of density functional theory (DFT). Necessary conditions for encapsulation are preexisting ion-induced defects in the graphite substrate and elevated deposition temperature of 875–900 K. Evidence of encapsulation consists of atomically resolved STM images of a carbon lattice, both on top of the islands and on the sloping sides. The nature of the images indicates that this carbon lattice corresponds to a graphene blanket consisting of more than one graphene sheet that drapes continuously from the top of the island to the graphite substrate. The formation of iron carbide is not observed based on XPS. Shapes of the island footprints are consistent with metallic Fe, predominantly in the hcp or fcc form, though larger islands tend toward bcc. Island structures with hexagonally close-packed lateral hcp or fcc planes are stabilized by their excellent lattice match with the graphite substrate. Evolution of island density with prolonged deposition time provides evidence of coarsening, perhaps via Smoluchowski ripening. The encapsulated Fe clusters are stable in air at room temperature, protected by smaller Fe clusters that decorate defect sites and block permeation of gases. DFT shows that two configurations of Fe are more stable within the gallery than adsorbed on top of the surface: a single atom of Fe and a film (slab) of metallic Fe. Comparison with other metals shows that encapsulated Fe is similar to Cu but dissimilar to Ru or Dy, leading the authors to conclude that carbon dissolution in the metal does not play a role in encapsulation.},
doi = {10.1116/1.5124927},
journal = {Journal of Vacuum Science and Technology A},
number = 6,
volume = 37,
place = {United States},
year = {Wed Nov 13 00:00:00 EST 2019},
month = {Wed Nov 13 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights
journal, February 2018

  • Lii-Rosales, Ann; Han, Yong; Evans, James W.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpcc.7b12533

Reverse-engineering of graphene on metal surfaces: a case study of embedded ruthenium
journal, October 2018


Defect-mediated, thermally-activated encapsulation of metals at the surface of graphite
journal, February 2018


The C-Fe (carbon-iron) system
journal, October 1992


The solubility of C in solid Cu
journal, July 2004


Synthesis of novel Ru2C under high pressure–high temperature conditions
journal, August 2012

  • Sanjay Kumar, N. R.; Chandra Shekar, N. V.; Chandra, Sharat
  • Journal of Physics: Condensed Matter, Vol. 24, Issue 36
  • DOI: 10.1088/0953-8984/24/36/362202

Carbon coated face-centered cubic Ru–C nanoalloys
journal, January 2014

  • Zhao, Zhisheng; Meng, Chuanmin; Li, Peifang
  • Nanoscale, Vol. 6, Issue 17
  • DOI: 10.1039/C4NR02632B

Preparation and Crystal Structures of RuC and OsC
journal, November 1960

  • Kempter, Charles P.; Nadler, M. R.
  • The Journal of Chemical Physics, Vol. 33, Issue 5
  • DOI: 10.1063/1.1731449

Visualizing electronic interactions between iron and carbon by X-ray chemical imaging and spectroscopy
journal, January 2015

  • Chen, Xiaoqi; Xiao, Jianping; Wang, Jian
  • Chemical Science, Vol. 6, Issue 5
  • DOI: 10.1039/C5SC00353A

Formation and Structure of Graphene Waves on Fe(110)
journal, July 2012


A Controlled Carburization Process to Obtain Graphene-Fe3 C-Fe Composites
journal, July 2018

  • You, Yi; Yoshimura, Masamichi; Cholake, Sagar
  • Advanced Materials Interfaces, Vol. 5, Issue 16
  • DOI: 10.1002/admi.201800599

Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
journal, May 2009


Evolution of Graphene Growth on Ni and Cu by Carbon Isotope Labeling
journal, December 2009

  • Li, Xuesong; Cai, Weiwei; Colombo, Luigi
  • Nano Letters, Vol. 9, Issue 12
  • DOI: 10.1021/nl902515k

Graphene Islands on Cu Foils: The Interplay between Shape, Orientation, and Defects
journal, December 2010

  • Wofford, Joseph M.; Nie, Shu; McCarty, Kevin F.
  • Nano Letters, Vol. 10, Issue 12
  • DOI: 10.1021/nl102788f

A review of chemical vapour deposition of graphene on copper
journal, January 2011

  • Mattevi, Cecilia; Kim, Hokwon; Chhowalla, Manish
  • J. Mater. Chem., Vol. 21, Issue 10
  • DOI: 10.1039/C0JM02126A

Review of CVD Synthesis of Graphene: Review of CVD Synthesis of Graphene
journal, November 2013

  • Muñoz, Roberto; Gómez-Aleixandre, Cristina
  • Chemical Vapor Deposition, Vol. 19, Issue 10-11-12
  • DOI: 10.1002/cvde.201300051

Fast growth of inch-sized single-crystalline graphene from a controlled single nucleus on Cu–Ni alloys
journal, November 2015

  • Wu, Tianru; Zhang, Xuefu; Yuan, Qinghong
  • Nature Materials, Vol. 15, Issue 1
  • DOI: 10.1038/nmat4477

Coexistence of charge and ferromagnetic order in fcc Fe
journal, March 2016

  • Hsu, Pin-Jui; Kügel, Jens; Kemmer, Jeannette
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10949

Long-Range Electronic Perturbations Caused by Defects Using Scanning Tunneling Microscopy
journal, May 1989


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Chemical accuracy for the van der Waals density functional
journal, December 2009

  • Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
  • Journal of Physics: Condensed Matter, Vol. 22, Issue 2
  • DOI: 10.1088/0953-8984/22/2/022201

Surface energies, adhesion energies, and exfoliation energies relevant to copper-graphene and copper-graphite systems
journal, July 2019


The Structure of Graphite
journal, December 1924

  • Bernal, J. D.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 106, Issue 740
  • DOI: 10.1098/rspa.1924.0101

Energetics of Cu adsorption and intercalation at graphite step edges
journal, March 2019


Ab initio full-potential study of the structural and magnetic phase stability of iron
journal, August 1999


Precision Determination of Lattice Constants
journal, October 1935

  • Jette, Eric R.; Foote, Frank
  • The Journal of Chemical Physics, Vol. 3, Issue 10
  • DOI: 10.1063/1.1749562

The effect of high pressure on the martensitic reaction in iron-carbon alloys
journal, March 1962


Effect of Pressure on Crystal Structure and Lattice Parameters of Iron up to 300 kbar
journal, January 1967

  • Mao, Ho‐Kwang; Bassett, William A.; Takahashi, Taro
  • Journal of Applied Physics, Vol. 38, Issue 1
  • DOI: 10.1063/1.1708965

Missing Atom as a Source of Carbon Magnetism
journal, March 2010


On the STM imaging contrast of graphite: towards a “true’' atomic resolution
journal, January 1999

  • Atamny, F.; Spillecke, O.; Schlögl, R.
  • Physical Chemistry Chemical Physics, Vol. 1, Issue 17
  • DOI: 10.1039/a904657g

Scanning tunneling microscopy on epitaxial bilayer graphene on ruthenium (0001)
journal, March 2009

  • Sutter, E.; Acharya, D. P.; Sadowski, J. T.
  • Applied Physics Letters, Vol. 94, Issue 13
  • DOI: 10.1063/1.3106057

Scanning tunneling microscopy of graphene on Ru(0001)
journal, August 2007


Evidence of strong interaction between iron particles and an activated carbon support
journal, September 1987

  • Hegenberger, E.; Wu, N. L.; Phillips, J.
  • The Journal of Physical Chemistry, Vol. 91, Issue 19
  • DOI: 10.1021/j100303a037

Review Graphite
journal, January 2002


Study of the oxide/carbide transition on iron surfaces during catalytic coke formation
journal, January 2002

  • Bonnet, F.; Ropital, F.; Lecour, P.
  • Surface and Interface Analysis, Vol. 34, Issue 1
  • DOI: 10.1002/sia.1330

Magnetic Moment of fcc Fe(111) Ultrathin Films by Ultrafast Deposition on Cu(111)
journal, March 1998


Growth, structure, and magnetism of fcc Fe ultrathin films on Cu(111) by pulsed laser deposition
journal, February 1999


The effect of spatial confinement on magnetism: films, stripes and dots of Fe on Cu(111)
journal, December 2002


Structure and growth of crystalline superlattices: From monolayer to superlattice
journal, March 1986


Surface energies of elemental crystals
journal, September 2016

  • Tran, Richard; Xu, Zihan; Radhakrishnan, Balachandran
  • Scientific Data, Vol. 3, Issue 1
  • DOI: 10.1038/sdata.2016.80

First-principles study of the relaxation and energy of bcc-Fe, fcc-Fe and AISI-304 stainless steel surfaces
journal, August 2009


Transition metals on the (0 0 0 1) surface of graphite: Fundamental aspects of adsorption, diffusion, and morphology
journal, August 2014


Reshaping, Intermixing, and Coarsening for Metallic Nanocrystals: Nonequilibrium Statistical Mechanical and Coarse-Grained Modeling
journal, October 2018


Calculations of electron inelastic mean free paths. IX. Data for 41 elemental solids over the 50 eV to 30 keV range
journal, February 2011

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 43, Issue 3
  • DOI: 10.1002/sia.3522

Characterization of the “native” surface thin film on pure polycrystalline iron: A high resolution XPS and TEM study
journal, February 2007


Native Oxide Layers Formed on the Surface of Ultra High-Purity Iron and Copper Investigated by Angle Resolved XPS
journal, January 1997


XPS analysis of oleylamine/oleic acid capped Fe3O4 nanoparticles as a function of temperature
journal, June 2014


High performance of Fe nanoparticles/carbon aerogel sorbents for H2S Removal
journal, April 2017


A Fundamental Equation of State for Heavy Water
journal, January 1982

  • Hill, P. G.; MacMillan, R. D. Chris; Lee, V.
  • Journal of Physical and Chemical Reference Data, Vol. 11, Issue 1
  • DOI: 10.1063/1.555661

Dy adsorption and penetration on defected graphene by first-principles calculations
journal, February 2018


Formation of dysprosium carbide on the graphite (0001) surface
journal, July 2017