Journal of Materials Science

, Volume 50, Issue 20, pp 6739–6747 | Cite as

Spectral change of simulated X-ray photoelectron spectroscopy from graphene to fullerene

  • Jungpil Kim
  • Yasuhiro YamadaEmail author
  • Miki Kawai
  • Takehiro Tanabe
  • Satoshi Sato
Original Paper


C1s X-ray photoelectron spectroscopy (XPS) spectra of graphene with two to eight pentagons and fullerene pentagons were simulated using density functional theory calculation. Peak shifts and full width at half maximum (FWHM) of calculated C1s spectra were compared with those of actual C1s spectra. Introduction of up to four isolated pentagons had no influence on shifts of the calculated peak maxima of graphene (284.0 eV), whereas the introduction of six or more pentagons shifted the calculated peak maximum toward low binding energies because the number of connected pentagons increased. The presence of pentagons also influenced FWHMs. Introduction of six pentagons increased the calculated FWHMs from 1.25 to 1.45 eV, whereas introduction of eight or more pentagons decreased the FWHMs. The FWHM reached at 1.15 eV by introducing twelve pentagons (fullerene). These calculated shifts and FWHMs were close to the actual shifts of graphite (284.0 eV) and fullerene (282.9 eV) and FWHMs of graphite (1.25 eV) and fullerene (1.15 eV). Based on the calculated and the actual results, we proposed peak shifts and FWHMs of graphene with the different number of pentagons, which can be utilized for analyzing actual XPS spectra. Proposed FWHMs can be adjusted by measuring actual FWHMs using each device.


Fullerene Peak Maximum Peak Shift Nuclear Magnetic Resonance Spectroscopy Valence Band Edge 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



Acknowledgments are made to Mr. Shingo Kubo at the Kagoshima University in Japan for measuring samples by XPS. Graphite was provided by Nippon Graphite Industries, Ltd.


This study was funded by the Japan Society for the Promotion of Science (JSPS) KAKENHI (Grant Number 26820348).

Conflict of interest

Yasuhiro Yamada has received a research grant from the Japan Society for the Promotion of Science (JSPS) and received graphite from Nippon Graphite Industries, Ltd.

Supplementary material

10853_2015_9229_MOESM1_ESM.docx (2.6 mb)
Supplementary material 1 (DOCX 2689 kb)


  1. 1.
    Huang C, Li C, Shi G (2012) Graphene based catalysts. Energy Environ Sci 5:8848–8868CrossRefGoogle Scholar
  2. 2.
    An B, Fukuyama S, Yokogawa K, Yoshimura M, Egashira M, Korai Y, Mochida I (2001) Single pentagon in a hexagonal carbon lattice revealed by scanning tunneling microscopy. Appl Phys Lett 78:3696–3698CrossRefGoogle Scholar
  3. 3.
    Tamura R, Tsukada M (1994) Disclinations of monolayer graphite and their electronic states. Phys Rev B 49:7697–7708CrossRefGoogle Scholar
  4. 4.
    Dubois SM, Lopez-Bezanilla A, Cresti A, Triozon F, Biel B, Charlier JC, Roche S (2010) Quantum transport in graphene nanoribbons: effects of edge reconstruction and chemical reactivity. ACS Nano 4:1971–1976CrossRefGoogle Scholar
  5. 5.
    Erickson K, Erni R, Lee Z, Alem N, Gannett W, Zettl A (2010) Determination of the local chemical structure of graphene oxide and reduced graphene oxide. Adv Mater 22:4467–4472CrossRefGoogle Scholar
  6. 6.
    Popov VN, Henrard L, Lambin P (2009) Resonant Raman spectra of graphene with point defects. Carbon 47:2448–2455CrossRefGoogle Scholar
  7. 7.
    Rocquefelte X, Rignanese GM, Meunier V, Terrones H, Terrones M, Charlier JC (2004) How to identify haeckelite structures: a theoretical study of their electronic and vibrational properties. Nano Lett 4:805–810CrossRefGoogle Scholar
  8. 8.
    Gakh AA, Romanovich AY, Bax A (2003) Thermodynamic rearrangement synthesis and NMR structures of C1, C3, and T isomers of C60H36. J Am Chem Soc 125:7902–7906CrossRefGoogle Scholar
  9. 9.
    Wohlers M, Bauer A, Rühle TH, Neitzel F, Werner H, Schlögl R (1997) The dark reaction of C60 and of C70 with molecular oxygen at atmosphere pressure and temperatures between 300 and 800 K. Fuller Sci Technol 5:49–83CrossRefGoogle Scholar
  10. 10.
    Zhu Y, Yi T, Zheng B, Cao L (1999) The interaction of C60 fullerene and carbon nanotube with Ar ion beam. Appl Surf Sci 137:83–90CrossRefGoogle Scholar
  11. 11.
    Kim J, Yamada Y, Suzuki Y, Ciston J, Sato S (2014) Pyrolysis of epoxidized fullerenes analyzed by spectroscopies. J Phys Chem C 118:7076–7084CrossRefGoogle Scholar
  12. 12.
    Barinov A, Malcioǧlu OB, Fabris S, Sun T, Gregoratti L, Dalmiglio M, Kiskinova M (2009) Initial stages of oxidation on graphitic surfaces: photoemission study and density functional theory calculations. J Phys Chem C 113:9009–9013CrossRefGoogle Scholar
  13. 13.
    Proctor A, Sherwood PMA (1982) X-ray photoelectron spectroscopic studies of carbon fiber surfaces. I. Carbon fiber spectra and the effects of heat treatment. J Electron Spectrosc Relat Phenom 27:39–56CrossRefGoogle Scholar
  14. 14.
    Boutique JP, Verbist JJ, Fripiat JG, Delhalle J, Pfister-Guillouzo G, Ashwell GJ (1984) 3,5,11,13-Tetraazacycl [3.3.3] azine: theoretical (ab initio) and experimental (X-ray and ultraviolet photoelectron spectroscopy) studies of the electronic structure. J Am Chem Soc 106:4374–4378CrossRefGoogle Scholar
  15. 15.
    Casanovas J, Ricart JM, Rubio J, Illas F, Jimenez-Mateos JM (1996) Origin of the large N1s binding energy in X-ray photoelectron spectra of calcined carbonaceous materials. J Am Chem Soc 118:8071–8076CrossRefGoogle Scholar
  16. 16.
    Souto S, Pickholz M, dos Santos MC, Alvarez F (1998) Electronic structure of nitrogen–carbon alloys (a-CNx) determined by photoelectron spectroscopy. Phys Rev B 57:2536–2540CrossRefGoogle Scholar
  17. 17.
    Ohta R, Lee KH, Saito N, Inoue Y, Sugimura H, Takai O (2003) Origin of N1s spectrum in amorphous carbon nitride obtained by X-ray photoelectron spectroscopy. Thin Solid Films 434:296–302CrossRefGoogle Scholar
  18. 18.
    Kim S, Zhou S, Hu Y, Acik M, Chabal YJ, Berger C, de Heer W, Bongiorno A, Riedo E (2012) Room-temperature metastability of multilayer graphene oxide films. Nat Mater 11:544–549CrossRefGoogle Scholar
  19. 19.
    Zhang W, Carravetta V, Li Z, Luo Y, Yang J (2009) Oxidation states of graphene: insights from computational spectroscopy. J Chem Phys 131:244505CrossRefGoogle Scholar
  20. 20.
    Susi T, Kaukonen M, Havu P, Ljungberg MP, Ayala P, Kauppinen EI (2014) Core level binding energies of functionalized and defective graphene. Beilstein J Nanotechnol 5:121–132CrossRefGoogle Scholar
  21. 21.
    Yamada Y, Yasuda H, Murota K, Nakamura M, Sodesawa T, Sato S (2013) Analysis of heat-treated graphite oxide by X-ray photoelectron spectroscopy. J Mater Sci 48:8171–8198. doi: 10.1007/s10853-013-7630-0 CrossRefGoogle Scholar
  22. 22.
    Yamada Y, Kim J, Matsuo S, Sato S (2014) Nitrogen-containing graphene analyzed by X-ray photoelectron spectroscopy. Carbon 70:59–74CrossRefGoogle Scholar
  23. 23.
    Zhou KG, Zhang YH, Wang LJ, Xie KF, Xiong YQ, Zhang HL, Wang CW (2011) Can azulene-like molecules function as substitution-free molecular rectifiers? Phys Chem Chem Phys 13:15882–15890CrossRefGoogle Scholar
  24. 24.
    Frisch MJ, Trucks GW, Schlegel HB et al (2009) Gaussian 09, Revision D.01. Gaussian, Inc., WallingfordGoogle Scholar
  25. 25.
    Bagus PS, Ilton ES, Nelin CJ (2013) The interpretation of XPS spectra: insights into materials properties. Surf Sci Rep 68:273–304CrossRefGoogle Scholar
  26. 26.
    Bagus PS, Illas F, Pacchioni G, Parmigiani F (1999) Mechanisms responsible for chemical shifts of core-level binding energies and their relationship to chemical bonding. J Electron Spectrosc Relat 100:215–236CrossRefGoogle Scholar
  27. 27.
    Bellafont NP, Illas F, Bagus PS (2015) Validation of Koopmans’ theorem for density functional theory binding energies. Phys Chem Chem Phys 17:4015–4019CrossRefGoogle Scholar
  28. 28.
    Kojima I, Fukumoto N, Kurahashi M (1986) Analysis of X-ray photoelectron spectrum with asymmetric Gaussian-Lorentzian mixed function. Bunseki Kagaku 35:T96–T100CrossRefGoogle Scholar
  29. 29.
    Yang S, Zhou P, Chen L, Sun Q, Wang P, Ding S, Jiang A, Zhang DW (2014) Direct observation of the work function evolution of graphene-two-dimensional metal contacts. J Mater Chem C 2:8042–8046CrossRefGoogle Scholar
  30. 30.
    Kwon KC, Choi KS, Kim SY (2012) Increased work function in few-layer graphene sheets via metal chloride doping. Adv Funct Mater 22:4724–4731CrossRefGoogle Scholar
  31. 31.
    Ikeo N, Iijima Y, Niimura N, Sigematsu M, Tazawa T, Matsumoto (1991) Handbook of X-ray photoelectron spectroscopy. JEOL, Tokyo, p 196Google Scholar
  32. 32.
    Endo K, Matsumoto D, Takagi Y, Shimada S, Ida T, Mizuno M, Goto K, Okamura H, Kato N, Sasakawa K (2008) X-ray photoelectron spectral analysis for carbon allotropes. J Surf Anal 14:348–351Google Scholar
  33. 33.
    Li WY, Iburahim AA, Goto K, Shimizu R (2005) The absolute AES is coming; work functions and transmission of CMA. J Surf Anal 12:109–112Google Scholar
  34. 34.
    Shiraishi M, Ata M (2001) Work function of carbon nanotubes. Carbon 39:1913–1917CrossRefGoogle Scholar
  35. 35.
    Briggs D, Grant JT (2003) Surface analysis by Auger and X-ray photoelectron spectroscopy. IM Publications and Surface Spectra Ltd., Manchester, p 39Google Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Jungpil Kim
    • 1
  • Yasuhiro Yamada
    • 1
    Email author
  • Miki Kawai
    • 1
  • Takehiro Tanabe
    • 1
  • Satoshi Sato
    • 1
  1. 1.Graduate School of EngineeringChiba UniversityChibaJapan

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