skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Optimized Substrates and Measurement Approaches for Raman Spectroscopy of Graphene Nanoribbons

Abstract

The on-surface synthesis of graphene nanoribbons (GNRs) allows for the fabrication of atomically precise narrow GNRs. Despite their exceptional properties which can be tuned by ribbon width and edge structure, significant challenges remain for GNR processing and characterization. In this work, Raman spectroscopy is used to characterize different types of GNRs on their growth substrate and track their quality upon substrate transfer. A Raman-optimized (RO) device substrate and an optimized mapping approach are presented that allow for the acquisition of high-resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substrates. This approach is well suited to routinely monitor the geometry-dependent low-frequency modes of GNRs. In particular, the radial breathing-like mode (RBLM) and the shear-like mode (SLM) for 5-, 7-, and 9-atom-wide armchair GNRs (AGNRs) are tracked and their frequencies are compared with first-principles calculations.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [3];  [6]; ORCiD logo [6]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [3]; ORCiD logo [5]; ORCiD logo [1]; ORCiD logo [2]
  1. Empa, Swiss Federal Lab. for Materials Science and Technology, Dübendorf (Switzerland); Univ. of Basel (Switzerland)
  2. Empa, Swiss Federal Lab. for Materials Science and Technology, Dübendorf (Switzerland)
  3. Rensselaer Polytechnic Inst., Troy, NY (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  5. Empa, Swiss Federal Lab. for Materials Science and Technology, Dübendorf (Switzerland); Univ. of Bern (Switzerland)
  6. Max Planck Inst. for Polymer Research, Mainz (Germany)
  7. Max Planck Inst. for Polymer Research, Mainz (Germany); Johannes Gutenberg Univ., Mainz (Germany)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
Swiss National Science Foundation (SNF); European Union’s Horizon 2020; US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Science (SC); Max Planck Society; Binning and Rohrer Nanotechnology Center (BRNC)
OSTI Identifier:
1607085
Grant/Contract Number:  
AC05-00OR22725; 20PC21_155644; 785219; 754364
Resource Type:
Accepted Manuscript
Journal Name:
Physica Status Solidi B. Basic Solid State Physics
Additional Journal Information:
Journal Volume: 256; Journal Issue: 12; Journal ID: ISSN 0370-1972
Publisher:
Wiley-Blackwell
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; graphene nanoribbons; Raman-optimized substrates; Raman spectroscopy; substrate transfer; vibrational modes

Citation Formats

Overbeck, Jan, Borin Barin, Gabriela, Daniels, Colin, Perrin, Mickael L., Liang, Liangbo, Braun, Oliver, Darawish, Rimah, Burkhardt, Bryanna, Dumslaff, Tim, Wang, Xiao-Ye, Narita, Akimitsu, Müllen, Klaus, Meunier, Vincent, Fasel, Roman, Calame, Michel, and Ruffieux, Pascal. Optimized Substrates and Measurement Approaches for Raman Spectroscopy of Graphene Nanoribbons. United States: N. p., 2019. Web. https://doi.org/10.1002/pssb.201900343.
Overbeck, Jan, Borin Barin, Gabriela, Daniels, Colin, Perrin, Mickael L., Liang, Liangbo, Braun, Oliver, Darawish, Rimah, Burkhardt, Bryanna, Dumslaff, Tim, Wang, Xiao-Ye, Narita, Akimitsu, Müllen, Klaus, Meunier, Vincent, Fasel, Roman, Calame, Michel, & Ruffieux, Pascal. Optimized Substrates and Measurement Approaches for Raman Spectroscopy of Graphene Nanoribbons. United States. https://doi.org/10.1002/pssb.201900343
Overbeck, Jan, Borin Barin, Gabriela, Daniels, Colin, Perrin, Mickael L., Liang, Liangbo, Braun, Oliver, Darawish, Rimah, Burkhardt, Bryanna, Dumslaff, Tim, Wang, Xiao-Ye, Narita, Akimitsu, Müllen, Klaus, Meunier, Vincent, Fasel, Roman, Calame, Michel, and Ruffieux, Pascal. Wed . "Optimized Substrates and Measurement Approaches for Raman Spectroscopy of Graphene Nanoribbons". United States. https://doi.org/10.1002/pssb.201900343. https://www.osti.gov/servlets/purl/1607085.
@article{osti_1607085,
title = {Optimized Substrates and Measurement Approaches for Raman Spectroscopy of Graphene Nanoribbons},
author = {Overbeck, Jan and Borin Barin, Gabriela and Daniels, Colin and Perrin, Mickael L. and Liang, Liangbo and Braun, Oliver and Darawish, Rimah and Burkhardt, Bryanna and Dumslaff, Tim and Wang, Xiao-Ye and Narita, Akimitsu and Müllen, Klaus and Meunier, Vincent and Fasel, Roman and Calame, Michel and Ruffieux, Pascal},
abstractNote = {The on-surface synthesis of graphene nanoribbons (GNRs) allows for the fabrication of atomically precise narrow GNRs. Despite their exceptional properties which can be tuned by ribbon width and edge structure, significant challenges remain for GNR processing and characterization. In this work, Raman spectroscopy is used to characterize different types of GNRs on their growth substrate and track their quality upon substrate transfer. A Raman-optimized (RO) device substrate and an optimized mapping approach are presented that allow for the acquisition of high-resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substrates. This approach is well suited to routinely monitor the geometry-dependent low-frequency modes of GNRs. In particular, the radial breathing-like mode (RBLM) and the shear-like mode (SLM) for 5-, 7-, and 9-atom-wide armchair GNRs (AGNRs) are tracked and their frequencies are compared with first-principles calculations.},
doi = {10.1002/pssb.201900343},
journal = {Physica Status Solidi B. Basic Solid State Physics},
number = 12,
volume = 256,
place = {United States},
year = {2019},
month = {10}
}

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

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Sample fabrication and characterization. a: STM image of aligned 9-AGNRs (top) and a sketch of the ribbons grown parallel to the Au(788) terraces (bottom). b: Sketch of the electrochemical delamination transfer (top) and a picture of the on-going transfer (bottom). c: Image of a Raman-optimized (RO) device substratemore » with a transferred PMMA/GNR film on top (dashed outline). Optical zoom-in with Raman G-intensity map as overlay (top). Raman spectra of three different transfers illustrating the sample-to-sample variation of the RBLM, CH/D and G modes (bottom).« less

Save / Share:

Works referenced in this record:

Energy Gaps in Graphene Nanoribbons
journal, November 2006


Graphene oxide as a chemically tunable platform for optical applications
journal, November 2010

  • Loh, Kian Ping; Bao, Qiaoliang; Eda, Goki
  • Nature Chemistry, Vol. 2, Issue 12
  • DOI: 10.1038/nchem.907

Multiphonon Raman Spectrum of Silicon
journal, April 1973


The evolution of Raman spectrum of graphene with the thickness of SiO 2 capping layer on Si substrate
journal, November 2013

  • Liu, Chu; Ma, Yaoguang; Li, Weisen
  • Applied Physics Letters, Vol. 103, Issue 21
  • DOI: 10.1063/1.4832063

Making graphene visible
journal, August 2007

  • Blake, P.; Hill, E. W.; Castro Neto, A. H.
  • Applied Physics Letters, Vol. 91, Issue 6
  • DOI: 10.1063/1.2768624

On-Surface Synthesis of Atomically Precise Graphene Nanoribbons
journal, February 2016

  • Talirz, Leopold; Ruffieux, Pascal; Fasel, Roman
  • Advanced Materials, Vol. 28, Issue 29
  • DOI: 10.1002/adma.201505738

Raman Fingerprints of Atomically Precise Graphene Nanoribbons
journal, May 2016


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


Influence of the Atomic Structure on the Raman Spectra of Graphite Edges
journal, December 2004


Making Graphene Nanoribbons Photoluminescent
journal, April 2017


Interference-enhanced Raman scattering of F 16 CuPc thin films
journal, February 2016


Evolution of the Raman spectra from single-, few-, and many-layer graphene with increasing disorder
journal, September 2010

  • Martins Ferreira, E. H.; Moutinho, Marcus V. O.; Stavale, F.
  • Physical Review B, Vol. 82, Issue 12
  • DOI: 10.1103/PhysRevB.82.125429

Seamless Staircase Electrical Contact to Semiconducting Graphene Nanoribbons
journal, September 2017


Interference enhanced Raman scattering from very thin absorbing films
journal, January 1980

  • Connell, G. A. N.; Nemanich, R. J.; Tsai, C. C.
  • Applied Physics Letters, Vol. 36, Issue 1
  • DOI: 10.1063/1.91304

Optical Interference Substrates for Nanoparticles and Two-Dimensional Materials
journal, January 2013

  • Bacsa, Wolfgang S.; Pavlenko, Ekaterina; Tishkova, Victoria
  • Nanomaterials and Nanotechnology, Vol. 3
  • DOI: 10.5772/57464

Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons
journal, September 2017

  • Llinas, Juan Pablo; Fairbrother, Andrew; Borin Barin, Gabriela
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-00734-x

Bottom-up graphene nanoribbon field-effect transistors
journal, December 2013

  • Bennett, Patrick B.; Pedramrazi, Zahra; Madani, Ali
  • Applied Physics Letters, Vol. 103, Issue 25
  • DOI: 10.1063/1.4855116

Ultra-narrow metallic armchair graphene nanoribbons
journal, December 2015

  • Kimouche, Amina; Ervasti, Mikko M.; Drost, Robert
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms10177

High vacuum synthesis and ambient stability of bottom-up graphene nanoribbons
journal, January 2017

  • Fairbrother, Andrew; Sanchez-Valencia, Juan-Ramon; Lauber, Beat
  • Nanoscale, Vol. 9, Issue 8
  • DOI: 10.1039/C6NR08975E

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


First principles phonon calculations in materials science
journal, November 2015


Vibrational properties of graphene nanoribbons by first-principles calculations
journal, October 2009


Atomically precise bottom-up fabrication of graphene nanoribbons
journal, July 2010

  • Cai, Jinming; Ruffieux, Pascal; Jaafar, Rached
  • Nature, Vol. 466, Issue 7305
  • DOI: 10.1038/nature09211

Graphene nanoribbon heterojunctions
journal, September 2014

  • Cai, Jinming; Pignedoli, Carlo A.; Talirz, Leopold
  • Nature Nanotechnology, Vol. 9, Issue 11
  • DOI: 10.1038/nnano.2014.184

Raman Spectrum of Graphite
journal, August 1970

  • Tuinstra, F.; Koenig, J. L.
  • The Journal of Chemical Physics, Vol. 53, Issue 3
  • DOI: 10.1063/1.1674108

Linear optical properties in the projector-augmented wave methodology
journal, January 2006


Raman-active modes in graphene nanoribbons
journal, September 2010

  • Gillen, Roland; Mohr, Marcel; Maultzsch, Janina
  • physica status solidi (b), Vol. 247, Issue 11-12
  • DOI: 10.1002/pssb.201000354

On-Surface Growth Dynamics of Graphene Nanoribbons: The Role of Halogen Functionalization
journal, December 2017


Field-Effect Transistors Based on Networks of Highly Aligned, Chemically Synthesized N = 7 Armchair Graphene Nanoribbons
journal, March 2018

  • Passi, Vikram; Gahoi, Amit; Senkovskiy, Boris V.
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 12
  • DOI: 10.1021/acsami.8b01116

Surface-Synthesized Graphene Nanoribbons for Room Temperature Switching Devices: Substrate Transfer and ex Situ Characterization
journal, March 2019

  • Borin Barin, Gabriela; Fairbrother, Andrew; Rotach, Lukas
  • ACS Applied Nano Materials, Vol. 2, Issue 4
  • DOI: 10.1021/acsanm.9b00151

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Electronic Structure of Atomically Precise Graphene Nanoribbons
journal, July 2012

  • Ruffieux, Pascal; Cai, Jinming; Plumb, Nicholas C.
  • ACS Nano, Vol. 6, Issue 8
  • DOI: 10.1021/nn3021376

Theoretical study of the vibrational edge modes in graphene nanoribbons
journal, November 2008


On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons
journal, February 2017


Oxidized nitinol substrate for interference enhanced Raman scattering of monolayer graphene
journal, January 2016

  • Abidi, Irfan Haider; Cagang, Aldrine Abenoja; Tyagi, Abhishek
  • RSC Advances, Vol. 6, Issue 9
  • DOI: 10.1039/C5RA24842F

First-principles Raman spectra of MoS2, WS2 and their heterostructures
journal, January 2014


Perspectives on Carbon Nanotubes and Graphene Raman Spectroscopy
journal, March 2010

  • Dresselhaus, Mildred S.; Jorio, Ado; Hofmann, Mario
  • Nano Letters, Vol. 10, Issue 3
  • DOI: 10.1021/nl904286r

Interference effect on Raman spectrum of graphene on SiO 2 / Si
journal, September 2009


Engineering of robust topological quantum phases in graphene nanoribbons
journal, August 2018


Structure-dependent electrical properties of graphene nanoribbon devices with graphene electrodes
journal, May 2019


Dual Path Mechanism in the Thermal Reduction of Graphene Oxide
journal, November 2011

  • Larciprete, Rosanna; Fabris, Stefano; Sun, Tao
  • Journal of the American Chemical Society, Vol. 133, Issue 43
  • DOI: 10.1021/ja205168x

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.