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Title: Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition

Abstract

Epitaxially oriented wafer-scale graphene grown directly on semiconducting Ge substrates is of high interest for both fundamental science and electronic device applications. To date, however, this material system remains relatively unexplored structurally and electronically, particularly at the atomic scale. To further understand the nature of the interface between graphene and Ge, we utilize ultrahigh vacuum scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) along with Raman and X-ray photoelectron spectroscopy to probe interfacial atomic structure and chemistry. STS reveals significant differences in electronic interactions between graphene and Ge(110)/Ge(111), which is consistent with a model of stronger interaction on Ge(110) leading to epitaxial growth. Raman spectra indicate that the graphene is considerably strained after growth, with more point-to-point variation on Ge(111). Furthermore, this native strain influences the atomic structure of the interface by inducing metastable and previously unobserved Ge surface reconstructions following annealing. These nonequilibrium reconstructions cover >90% of the surface and, in turn, modify both the electronic and mechanical properties of the graphene overlayer. Finally, graphene on Ge(001) represents the extreme strain case, where graphene drives the reorganization of the Ge surface into [107] facets. From this study, it is clear that the interaction between graphene and the underlyingmore » Ge is not only dependent on the substrate crystallographic orientation, but is also tunable and strongly related to the atomic reconfiguration of the graphene–Ge interface.« less

Authors:
 [1];  [2];  [1];  [3];  [3];  [2];  [3];  [4]
  1. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Wisconsin, Madison, WI (United States)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1245135
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 15; Journal Issue: 11; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Raman spectroscopy; chemical vapor deposition; epitaxy; scanning tunneling microscopy; scanning tunneling spectroscopy; surface reconstruction

Citation Formats

Kiraly, Brian T., Jacobberger, Robert M., Mannix, Andrew J., Campbell, Gavin P., Bedzyk, Michael J., Arnold, Michael S., Hersam, Mark C., and Guisinger, Nathan P. Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition. United States: N. p., 2015. Web. doi:10.1021/acs.nanolett.5b02833.
Kiraly, Brian T., Jacobberger, Robert M., Mannix, Andrew J., Campbell, Gavin P., Bedzyk, Michael J., Arnold, Michael S., Hersam, Mark C., & Guisinger, Nathan P. Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition. United States. https://doi.org/10.1021/acs.nanolett.5b02833
Kiraly, Brian T., Jacobberger, Robert M., Mannix, Andrew J., Campbell, Gavin P., Bedzyk, Michael J., Arnold, Michael S., Hersam, Mark C., and Guisinger, Nathan P. Tue . "Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition". United States. https://doi.org/10.1021/acs.nanolett.5b02833. https://www.osti.gov/servlets/purl/1245135.
@article{osti_1245135,
title = {Electronic and mechanical properties of graphene-germanium interfaces grown by chemical vapor deposition},
author = {Kiraly, Brian T. and Jacobberger, Robert M. and Mannix, Andrew J. and Campbell, Gavin P. and Bedzyk, Michael J. and Arnold, Michael S. and Hersam, Mark C. and Guisinger, Nathan P.},
abstractNote = {Epitaxially oriented wafer-scale graphene grown directly on semiconducting Ge substrates is of high interest for both fundamental science and electronic device applications. To date, however, this material system remains relatively unexplored structurally and electronically, particularly at the atomic scale. To further understand the nature of the interface between graphene and Ge, we utilize ultrahigh vacuum scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) along with Raman and X-ray photoelectron spectroscopy to probe interfacial atomic structure and chemistry. STS reveals significant differences in electronic interactions between graphene and Ge(110)/Ge(111), which is consistent with a model of stronger interaction on Ge(110) leading to epitaxial growth. Raman spectra indicate that the graphene is considerably strained after growth, with more point-to-point variation on Ge(111). Furthermore, this native strain influences the atomic structure of the interface by inducing metastable and previously unobserved Ge surface reconstructions following annealing. These nonequilibrium reconstructions cover >90% of the surface and, in turn, modify both the electronic and mechanical properties of the graphene overlayer. Finally, graphene on Ge(001) represents the extreme strain case, where graphene drives the reorganization of the Ge surface into [107] facets. From this study, it is clear that the interaction between graphene and the underlying Ge is not only dependent on the substrate crystallographic orientation, but is also tunable and strongly related to the atomic reconfiguration of the graphene–Ge interface.},
doi = {10.1021/acs.nanolett.5b02833},
journal = {Nano Letters},
number = 11,
volume = 15,
place = {United States},
year = {Tue Oct 27 00:00:00 EDT 2015},
month = {Tue Oct 27 00:00:00 EDT 2015}
}

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Works referenced in this record:

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


Large-scale pattern growth of graphene films for stretchable transparent electrodes
journal, January 2009


Large Area, Few-Layer Graphene Films on Arbitrary Substrates by Chemical Vapor Deposition
journal, January 2009

  • Reina, Alfonso; Jia, Xiaoting; Ho, John
  • Nano Letters, Vol. 9, Issue 1
  • DOI: 10.1021/nl801827v

The rise of graphene
journal, March 2007

  • Geim, A. K.; Novoselov, K. S.
  • Nature Materials, Vol. 6, Issue 3, p. 183-191
  • DOI: 10.1038/nmat1849

Solid-source growth and atomic-scale characterization of graphene on Ag(111)
journal, November 2013

  • Kiraly, Brian; Iski, Erin V.; Mannix, Andrew J.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3804

Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum
journal, January 2012

  • Gao, Libo; Ren, Wencai; Xu, Huilong
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1702

Uniform hexagonal graphene flakes and films grown on liquid copper surface
journal, April 2012

  • Geng, D.; Wu, B.; Guo, Y.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 21
  • DOI: 10.1073/pnas.1200339109

Growth of graphene from solid carbon sources
journal, November 2010


High-Quality Large-Area Graphene from Dehydrogenated Polycyclic Aromatic Hydrocarbons
journal, October 2012

  • Wan, Xi; Chen, Kun; Liu, Danqing
  • Chemistry of Materials, Vol. 24, Issue 20
  • DOI: 10.1021/cm301993z

Low-Temperature Growth of Graphene by Chemical Vapor Deposition Using Solid and Liquid Carbon Sources
journal, March 2011

  • Li, Zhancheng; Wu, Ping; Wang, Chenxi
  • ACS Nano, Vol. 5, Issue 4, p. 3385-3390
  • DOI: 10.1021/nn200854p

Growth of Graphene from Food, Insects, and Waste
journal, August 2011

  • Ruan, Gedeng; Sun, Zhengzong; Peng, Zhiwei
  • ACS Nano, Vol. 5, Issue 9
  • DOI: 10.1021/nn202625c

Tailoring Electrical Transport Across Grain Boundaries in Polycrystalline Graphene
journal, May 2012


The Role of Surface Oxygen in the Growth of Large Single-Crystal Graphene on Copper
journal, October 2013


Epitaxial Graphene on Cu(111)
journal, September 2010

  • Gao, Li; Guest, Jeffrey R.; Guisinger, Nathan P.
  • Nano Letters, Vol. 10, Issue 9
  • DOI: 10.1021/nl1016706

Epitaxial graphene on ruthenium
journal, April 2008

  • Sutter, Peter W.; Flege, Jan-Ingo; Sutter, Eli A.
  • Nature Materials, Vol. 7, Issue 5, p. 406-411
  • DOI: 10.1038/nmat2166

Graphene Growth Dynamics on Epitaxial Copper Thin Films
journal, March 2013

  • Jacobberger, Robert M.; Arnold, Michael S.
  • Chemistry of Materials, Vol. 25, Issue 6
  • DOI: 10.1021/cm303445s

Tailoring the Growth Rate and Surface Facet for Synthesis of High-Quality Continuous Graphene Films from CH 4 at 750 °C via Chemical Vapor Deposition
journal, May 2015

  • Jacobberger, Robert M.; Levesque, Pierre L.; Xu, Feng
  • The Journal of Physical Chemistry C, Vol. 119, Issue 21
  • DOI: 10.1021/jp5116355

Direct Growth of Graphene Film on Germanium Substrate
journal, August 2013

  • Wang, Gang; Zhang, Miao; Zhu, Yun
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02465

Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium
journal, April 2014


Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004


Experimental observation of the quantum Hall effect and Berry's phase in graphene
journal, November 2005

  • Zhang, Yuanbo; Tan, Yan-Wen; Stormer, Horst L.
  • Nature, Vol. 438, Issue 7065, p. 201-204
  • DOI: 10.1038/nature04235

Two-dimensional gas of massless Dirac fermions in graphene
journal, November 2005

  • Novoselov, K. S.; Geim, A. K.; Morozov, S. V.
  • Nature, Vol. 438, Issue 7065, p. 197-200
  • DOI: 10.1038/nature04233

Optical Phonons in Twisted Bilayer Graphene with Gate-Induced Asymmetric Doping
journal, January 2015

  • Chung, Ting-Fung; He, Rui; Wu, Tai-Lung
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl504318a

Boron nitride substrates for high-quality graphene electronics
journal, August 2010

  • Dean, C. R.; Young, A. F.; Meric, I.
  • Nature Nanotechnology, Vol. 5, Issue 10, p. 722-726
  • DOI: 10.1038/nnano.2010.172

Observation of electron–hole puddles in graphene using a scanning single-electron transistor
journal, November 2007

  • Martin, J.; Akerman, N.; Ulbricht, G.
  • Nature Physics, Vol. 4, Issue 2
  • DOI: 10.1038/nphys781

Substrate-limited electron dynamics in graphene
journal, May 2008


Quasi-Free-Standing Epitaxial Graphene on SiC Obtained by Hydrogen Intercalation
journal, December 2009


Oxygen Switching of the Epitaxial Graphene–Metal Interaction
journal, October 2012

  • Larciprete, Rosanna; Ulstrup, Søren; Lacovig, Paolo
  • ACS Nano, Vol. 6, Issue 11
  • DOI: 10.1021/nn302729j

The Backside of Graphene: Manipulating Adsorption by Intercalation
journal, October 2013

  • Schumacher, Stefan; Wehling, Tim O.; Lazić, Predrag
  • Nano Letters, Vol. 13, Issue 11
  • DOI: 10.1021/nl402797j

Charge density waves in the graphene sheets of the superconductor CaC6
journal, September 2011

  • Rahnejat, K. C.; Howard, C. A.; Shuttleworth, N. E.
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1574

Strong Coulomb drag and broken symmetry in double-layer graphene
journal, October 2012

  • Gorbachev, R. V.; Geim, A. K.; Katsnelson, M. I.
  • Nature Physics, Vol. 8, Issue 12
  • DOI: 10.1038/nphys2441

Cloning of Dirac fermions in graphene superlattices
journal, May 2013

  • Ponomarenko, L. A.; Gorbachev, R. V.; Yu, G. L.
  • Nature, Vol. 497, Issue 7451
  • DOI: 10.1038/nature12187

Hofstadter’s butterfly and the fractal quantum Hall effect in moiré superlattices
journal, May 2013


Massive Dirac Fermions and Hofstadter Butterfly in a van der Waals Heterostructure
journal, May 2013


Detecting topological currents in graphene superlattices
journal, September 2014


Tight-binding approach to uniaxial strain in graphene
journal, July 2009


Tilted anisotropic Dirac cones in quinoid-type graphene and α ( BEDT-TTF ) 2 I 3
journal, July 2008


Strain-Induced Pseudo-Magnetic Fields Greater Than 300 Tesla in Graphene Nanobubbles
journal, July 2010


Designer Dirac fermions and topological phases in molecular graphene
journal, March 2012

  • Gomes, Kenjiro K.; Mar, Warren; Ko, Wonhee
  • Nature, Vol. 483, Issue 7389
  • DOI: 10.1038/nature10941

Strain engineering the properties of graphene and other two-dimensional crystals
journal, January 2014

  • Bissett, Mark A.; Tsuji, Masaharu; Ago, Hiroki
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 23
  • DOI: 10.1039/c3cp55443k

Charged defects on Ge(111)-c(2×8): characterization using STM
journal, August 2000


The Ge(001) surface
journal, December 2003


The influence of edge structure on the electronic properties of graphene quantum dots and nanoribbons
journal, February 2009

  • Ritter, Kyle A.; Lyding, Joseph W.
  • Nature Materials, Vol. 8, Issue 3
  • DOI: 10.1038/nmat2378

Imaging the interface of epitaxial graphene with silicon carbide via scanning tunneling microscopy
journal, December 2007


Atomic-Scale Evidence for Potential Barriers and Strong Carrier Scattering at Graphene Grain Boundaries: A Scanning Tunneling Microscopy Study
journal, December 2012

  • Koepke, Justin C.; Wood, Joshua D.; Estrada, David
  • ACS Nano, Vol. 7, Issue 1
  • DOI: 10.1021/nn302064p

Origin of spatial charge inhomogeneity in graphene
journal, August 2009

  • Zhang, Yuanbo; Brar, Victor W.; Girit, Caglar
  • Nature Physics, Vol. 5, Issue 10
  • DOI: 10.1038/nphys1365

Scanning tunnelling microscopy and spectroscopy of ultra-flat graphene on hexagonal boron nitride
journal, February 2011

  • Xue, Jiamin; Sanchez-Yamagishi, Javier; Bulmash, Danny
  • Nature Materials, Vol. 10, Issue 4
  • DOI: 10.1038/nmat2968

Separation-Dependent Electronic Transparency of Monolayer Graphene Membranes on III−V Semiconductor Substrates
journal, September 2010

  • He, Kevin T.; Koepke, Justin C.; Barraza-Lopez, Salvador
  • Nano Letters, Vol. 10, Issue 9
  • DOI: 10.1021/nl101527e

Local Electronic Properties of Graphene on a BN Substrate via Scanning Tunneling Microscopy
journal, June 2011

  • Decker, Régis; Wang, Yang; Brar, Victor W.
  • Nano Letters, Vol. 11, Issue 6
  • DOI: 10.1021/nl2005115

Micrometer-Scale Ballistic Transport in Encapsulated Graphene at Room Temperature
journal, June 2011

  • Mayorov, Alexander S.; Gorbachev, Roman V.; Morozov, Sergey V.
  • Nano Letters, Vol. 11, Issue 6
  • DOI: 10.1021/nl200758b

Optical Probing of the Electronic Interaction between Graphene and Hexagonal Boron Nitride
journal, January 2013

  • Ahn, Gwanghyun; Kim, Hye Ri; Ko, Taeg Yeoung
  • ACS Nano, Vol. 7, Issue 2
  • DOI: 10.1021/nn305306n

Optical separation of mechanical strain from charge doping in graphene
journal, January 2012

  • Lee, Ji Eun; Ahn, Gwanghyun; Shim, Jihye
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2022

Many-electron singularity in X-ray photoemission and X-ray line spectra from metals
journal, February 1970


Excitonic Effects in Core-Hole Screening
journal, December 1979


X‐ray photoemission of carbon: Lineshape analysis and application to studies of coals
journal, October 1982

  • Cheung, T. T. P.
  • Journal of Applied Physics, Vol. 53, Issue 10
  • DOI: 10.1063/1.330025

Works referencing / citing this record:

Production and processing of graphene and related materials
journal, January 2020


Driving chemical interactions at graphene-germanium van der Waals interfaces via thermal annealing
journal, November 2018

  • Kiraly, Brian; Mannix, Andrew J.; Jacobberger, Robert M.
  • Applied Physics Letters, Vol. 113, Issue 21
  • DOI: 10.1063/1.5053083

Remote epitaxy through graphene enables two-dimensional material-based layer transfer
journal, April 2017

  • Kim, Yunjo; Cruz, Samuel S.; Lee, Kyusang
  • Nature, Vol. 544, Issue 7650
  • DOI: 10.1038/nature22053

Alignment of semiconducting graphene nanoribbons on vicinal Ge(001)
journal, January 2019

  • Jacobberger, Robert M.; Murray, Ellen A.; Fortin-Deschênes, Matthieu
  • Nanoscale, Vol. 11, Issue 11
  • DOI: 10.1039/c9nr00713j

Fabrication and characterization of SiC/Ge/graphene heterojunction with Ge micro-nano structures
journal, January 2020


Graphene on Group‐IV Elementary Semiconductors: The Direct Growth Approach and Its Applications
journal, February 2019

  • Lee, Jae‐Hyun; Kang, Seog‐Gyun; Jang, Hyeon‐Sik
  • Advanced Materials, Vol. 31, Issue 34
  • DOI: 10.1002/adma.201803469

The graphene/n-Ge(110) interface: structure, doping, and electronic properties
journal, January 2018

  • Tesch, Julia; Paschke, Fabian; Fonin, Mikhail
  • Nanoscale, Vol. 10, Issue 13
  • DOI: 10.1039/c8nr00053k

Single-step growth of graphene and graphene-based nanostructures by plasma-enhanced chemical vapor deposition
journal, February 2019


Reactive intercalation and oxidation at the buried graphene-germanium interface
journal, July 2019

  • Braeuninger-Weimer, Philipp; Burton, Oliver; Weatherup, Robert S.
  • APL Materials, Vol. 7, Issue 7
  • DOI: 10.1063/1.5098351

Dynamics of Antimonene–Graphene Van Der Waals Growth
journal, April 2019

  • Fortin‐Deschênes, Matthieu; Jacobberger, Robert M.; Deslauriers, Charles‐Antoine
  • Advanced Materials, Vol. 31, Issue 21
  • DOI: 10.1002/adma.201900569

Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates
journal, September 2018

  • Khan, Afzal; Islam, Sk Masiul; Ahmed, Shahzad
  • Advanced Science, Vol. 5, Issue 11
  • DOI: 10.1002/advs.201800050

Electronic and Interface Properties in Graphene Oxide/Hydrogen-Passivated Ge Heterostructure
journal, October 2018

  • Wang, Qian; Li, Xiang; Wu, Liyuan
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 13, Issue 2
  • DOI: 10.1002/pssr.201800461

Proton-assisted growth of ultra-flat graphene films
journal, January 2020


Morphological and Radio Frequency Characterization of Graphene Composite Films
journal, May 2018

  • Quaranta, Simone; Miscuglio, Mario; Bayat, Ahmad
  • C, Vol. 4, Issue 2
  • DOI: 10.3390/c4020032

Orientation-Dependent Strain Relaxation and Chemical Functionalization of Graphene on a Cu(111) Foil
journal, January 2018


Reactive intercalation and oxidation at the buried graphene-germanium interface
text, January 2019

  • Braeuninger-Weimer, Philipp; Burton, Oliver; Weatherup, Robert
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.41038

Production and processing of graphene and related materials
text, January 2020

  • Backes, C.; Abdelkader, Am; Alonso, C.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.63418

Production and processing of graphene and related materials
text, January 2020


Direct CVD Growth of Graphene on Technologically Important Dielectric and Semiconducting Substrates
journal, September 2018

  • Khan, Afzal; Islam, Sk Masiul; Ahmed, Shahzad
  • Advanced Science, Vol. 5, Issue 11
  • DOI: 10.1002/advs.201800050

CVD graphene/Ge interface: morphological and electronic characterization of ripples
journal, August 2019

  • Mendoza, Cesar D.; Figueroa, Neileth S.; Maia da Costa, Marcelo E. H.
  • Scientific Reports, Vol. 9, Issue 1
  • DOI: 10.1038/s41598-019-48998-1

Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns
journal, August 2016

  • Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep31407

Pattern Pick and Place Method for Twisted Bi- and Multi-Layer Graphene
journal, November 2019

  • Lim, Jae-Young; Jang, Hyeon-Sik; Yoo, Hyun-Jae
  • Materials, Vol. 12, Issue 22
  • DOI: 10.3390/ma12223740