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Title: Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights

Abstract

Here in this paper, we present an extensive experimental study of the conditions under which Cu forms encapsulated islands under the top surface layers of graphite, as a result of physical vapor deposition of Cu on argon-ion-bombarded graphite. When the substrate is held at 800 K during deposition, conditions are optimal for formation of encapsulated multilayer Cu islands. Deposition temperatures below 600 K favor adsorbed Cu clusters, while deposition temperatures above 800 K favor a different type of feature that is probably a single-layer intercalated Cu island. The multilayer Cu islands are characterized with respect to size and shape, thickness and continuity of the graphitic overlayer, relationship to graphite steps, and stability in air. The experimental techniques are scanning tunneling microscopy and X-ray photoelectron spectroscopy. We also present an extensive study using density functional theory to compare stabilities of a wide variety of configurations of Cu atoms, Cu clusters, and Cu layers on/under the graphite surface. The only configuration that is significantly more stable under the graphite surface than on top of it, is a single Cu atom. This analysis leads us to conclude that formation of encapsulated Cu islands is kinetically driven, rather than thermodynamically driven.

Authors:
 [1]; ORCiD logo [2];  [3];  [2];  [2];  [4];  [2]; ORCiD logo [4]; ORCiD logo [5]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
  2. Ames Lab., Ames, IA (United States)
  3. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Physics and Astronomy, and Dept. of Mathematics
  4. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Physics and Astronomy
  5. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1422772
Report Number(s):
IS-J-9545
Journal ID: ISSN 1932-7447; TRN: US1801660
Grant/Contract Number:  
AC02-07CH11358; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Lii-Rosales, Ann, Han, Yong, Evans, James W., Jing, Dapeng, Zhou, Yinghui, Tringides, Michael C., Kim, Minsung, Wang, Cai-Zhuang, and Thiel, Patricia A. Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.7b12533.
Lii-Rosales, Ann, Han, Yong, Evans, James W., Jing, Dapeng, Zhou, Yinghui, Tringides, Michael C., Kim, Minsung, Wang, Cai-Zhuang, & Thiel, Patricia A. Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights. United States. https://doi.org/10.1021/acs.jpcc.7b12533
Lii-Rosales, Ann, Han, Yong, Evans, James W., Jing, Dapeng, Zhou, Yinghui, Tringides, Michael C., Kim, Minsung, Wang, Cai-Zhuang, and Thiel, Patricia A. 2018. "Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights". United States. https://doi.org/10.1021/acs.jpcc.7b12533. https://www.osti.gov/servlets/purl/1422772.
@article{osti_1422772,
title = {Formation of Multilayer Cu Islands Embedded beneath the Surface of Graphite: Characterization and Fundamental Insights},
author = {Lii-Rosales, Ann and Han, Yong and Evans, James W. and Jing, Dapeng and Zhou, Yinghui and Tringides, Michael C. and Kim, Minsung and Wang, Cai-Zhuang and Thiel, Patricia A.},
abstractNote = {Here in this paper, we present an extensive experimental study of the conditions under which Cu forms encapsulated islands under the top surface layers of graphite, as a result of physical vapor deposition of Cu on argon-ion-bombarded graphite. When the substrate is held at 800 K during deposition, conditions are optimal for formation of encapsulated multilayer Cu islands. Deposition temperatures below 600 K favor adsorbed Cu clusters, while deposition temperatures above 800 K favor a different type of feature that is probably a single-layer intercalated Cu island. The multilayer Cu islands are characterized with respect to size and shape, thickness and continuity of the graphitic overlayer, relationship to graphite steps, and stability in air. The experimental techniques are scanning tunneling microscopy and X-ray photoelectron spectroscopy. We also present an extensive study using density functional theory to compare stabilities of a wide variety of configurations of Cu atoms, Cu clusters, and Cu layers on/under the graphite surface. The only configuration that is significantly more stable under the graphite surface than on top of it, is a single Cu atom. This analysis leads us to conclude that formation of encapsulated Cu islands is kinetically driven, rather than thermodynamically driven.},
doi = {10.1021/acs.jpcc.7b12533},
url = {https://www.osti.gov/biblio/1422772}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 8,
volume = 122,
place = {United States},
year = {Tue Feb 06 00:00:00 EST 2018},
month = {Tue Feb 06 00:00:00 EST 2018}
}

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Cited by: 25 works
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Works referenced in this record:

Growth morphology and properties of metals on graphene
journal, December 2015


Graphene-based synthetic antiferromagnets and ferrimagnets
journal, September 2017


Intercalation of metal islands and films at the interface of epitaxially grown graphene and Ru(0001) surfaces
journal, October 2011


Electronic structure of alkali metal overlayers on graphite
journal, December 1986


Alkali metal adsorption on graphite: a review
journal, August 2005


Intercalation compounds of graphite
journal, January 2002


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


Vacancy clusters as entry ports for cesium intercalation in graphite
journal, October 2011


Review of Chemical Vapor Deposition of Graphene and Related Applications
journal, November 2012


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


Copper intercalation at the interface of graphene and Ir(111) studied by scanning tunneling microscopy
journal, November 2014


Intercalation of copper underneath a monolayer of graphite on Ni(111)
journal, June 2001


Impermeable Atomic Membranes from Graphene Sheets
journal, August 2008


Wetting transparency of graphene
journal, January 2012


Formation of Pt and Rh Nanoclusters on a Graphene Moiré Pattern on Cu(111)
journal, October 2015


Epitaxial Graphene on Cu(111)
journal, September 2010


Reactivities of transition metals with carbon: Implications to the mechanism of diamond synthesis under high pressure
journal, January 1997


Gas-phase copper carbide clusters
journal, March 1993


Stability of bulk and surface carbide layers and their relation to the Fischer-Tropsch hydrocarbon synthesis
journal, November 1988


The thermochemistry of transition metal carbides
journal, April 1979


Determining whether metals nucleate homogeneously on graphite: A case study with copper
journal, November 2014


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


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


Projector augmented-wave method
journal, December 1994


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


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


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


Triangular versus honeycomb structure in atomic-resolution STM images of graphite
journal, March 2001


Revealing the hidden atom in graphite by low-temperature atomic force microscopy
journal, September 2003


Determination of α and β site defects on graphite using C60-adsorbed STM tips
journal, October 1998


Observations of Anisotropic Electron Scattering on Graphite with a Low-Temperature Scanning Tunneling Microscope
journal, March 1999


Scattering and Interference in Epitaxial Graphene
journal, July 2007


Structure and stability of hydrogenated carbon atom vacancies in graphene
journal, October 2014


Surface superstructures in highly oriented pyrolytic graphite surfaces after Ar+ bombardment
journal, February 2008


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


Ripple topography of ion-beam–eroded graphite: A key to ion-beam–induced damage tracks
journal, April 2000


Ion beam erosion of graphite surfaces studied by STM: Ripples, self-affine roughening and near-surface damage accumulation
journal, March 2000


Atomic-scale control of graphene magnetism by using hydrogen atoms
journal, April 2016


Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn
journal, November 2010


Strain Lattice Imprinting in Graphene by C 60 Intercalation at the Graphene/Cu Interface
journal, October 2015


Shape Transition in Growth of Strained Islands
journal, March 1999


AC/AB Stacking Boundaries in Bilayer Graphene
journal, June 2013


Dislocations in bilayer graphene
journal, December 2013


Chemical information from XPS—applications to the analysis of electrode surfaces
journal, April 1981


Self-assembled monolayers of n-alkanethiolates on copper are barrier films that protect the metal against oxidation by air
journal, November 1992


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


Oxidation Resistance of Graphene-Coated Cu and Cu/Ni Alloy
journal, January 2011


Adsorption of dysprosium on the graphite (0001) surface: Nucleation and growth at 300 K
journal, December 2016


Embedding Transition-Metal Atoms in Graphene: Structure, Bonding, and Magnetism
journal, March 2009


Greatly enhanced adsorption and catalytic activity of Au and Pt clusters on defective graphene
journal, May 2010


Adsorption and desorption kinetics of Cu and Au on (0001) graphite
journal, May 1973


Thermally activated diffusion of copper into amorphous carbon
journal, November 2017

  • Appy, David; Wallingford, Mark; Jing, Dapeng
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 35, Issue 6
  • https://doi.org/10.1116/1.4991519

Works referencing / citing this record:

Spontaneous selective deposition of iron oxide nanoparticles on graphite as model catalysts
journal, January 2019


Delamination of a Thin Film Driven by a Flat Cylindrical Shaft
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