Fluorination of CVD graphene films by inductively coupled plasma CF4
E.P. Neustroev, I.I. Kurkina
North-Eastern Federal University named after M.K. Ammosov
DOI: 10.26456/pcascnn/2025.17.109
Original article
Abstract: Synthesis of nanometer-thick dielectric films is one of the key tasks in nano- and optoelectronics, which is associated with growing requirements for miniaturization and functionality of devices. This paper presents the results of a study of optical and electrical properties of graphene fluorinated by inductively coupled plasma CF4. Fluorination was carried out in plasma with a power of 125 to 200 W for duration of up to 1 min. Two methods of arranging samples in the plasma chamber were used: 1) with a graphene film facing plasma and 2) with a substrate facing plasma. The methods of Raman spectroscopy, X-ray energy-dispersive spectroscopy, and current-voltage characteristics were used in the study. It was shown that the direct plasma action on the samples in position 1 results in graphene etching until the film is completely removed. In position 2, no intensive etching is observed during treatments lasting up to 1 min. In this case, fluorination of the graphene film occurs. As a result, the ratio of the number of fluorine atoms to carbon reaches a value of ~0,2. As a result of plasma treatment, there is a significant increase in the electrical resistance of graphene. The increase in surface resistance was from several kΩ/sq for the initial graphene to hundreds of GΩ/sq and tens of MΩ/sq for the samples subjected to plasma action in positions 1 and 2, respectively. The increase in the electrical resistance may be due to both the appearance of defects during plasma treatment and the fluorination process, which forms sp3-hybridized C-F bonds that distort the flat structure of graphene. Repeated conductivity assessments carried out after three weeks showed a decrease in resistance by two orders of magnitude for samples treated in plasma in position 2. This decrease may be due to the processes of defluorination and restoration of the flat structure of graphene.
Keywords: graphene, chemical vapor deposition, fluorination, plasma, carbon tetrafluoride, electrical resistance
- Efim P. Neustroev – Ph. D., Docent, Department of Radiophysics and Electronic Systems, North-Eastern Federal University named after M.K. Ammosov
- Irina I. Kurkina – Ph. D., senior researcher, Institute of Physics and Technologies, North-Eastern Federal University named after M.K. Ammosov
For citation:
Neustroev E.P., Kurkina I.I. Ftorirovanie plenok CVD-grafena v induktivno svyazannoj plazme CF4 [Fluorination of CVD graphene films by inductively coupled plasma CF4], Fiziko-khimicheskie aspekty izucheniya klasterov, nanostruktur i nanomaterialov [Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials], 2025, issue 17, pp. 109-117. DOI: 10.26456/pcascnn/2025.17.109. ⎘
Full article (in Russian): download PDF file
References:
1. Ao Z., Jiang Q., Li S. et al. Enhancement of the stability of fluorine atoms on defective graphene and at graphene/fluorographene Interface, ACS Applied Materials & Interfaces, 2015, vol. 7, issue 35, pp. 19659-19665. DOI: 10.1021/acsami.5b04319.
2. Feng W., Long P., Feng Y., Li Y. Two-dimensional fluorinated graphene: synthesis, structures, properties and applications, Advanced Science, 2016, vol. 3, issue 7, art. no. 1500413, 22 p. DOI: 10.1002/advs.201500413.
3. Zhou S., Sherpa S. D., Hess D. W., Bongiorno A. Chemical bonding of partially fluorinated graphene, The Journal of Physical Chemistry C, 2014, vol. 118, issue 45, pp. 26402-26408. DOI: 10.1021/jp508965q.
4. Nair R.R., Ren W., Jalil R. et al. Fluorographene: a two‐dimensional counterpart of Teflon, Small, 2010, vol. 6, issue 24, pp. 2877-2884. DOI: 10.1002/smll.201001555.
5. Withers F., Russo S., Dubois M., Craciun M. F. Tuning the electronic transport properties of graphene through functionalisation with fluorine, Nanoscale Research Letters, 2011, vol. 6, art. no. 526, issue 1, 11 p. DOI: 10.1186/1556-276X-6-526.
6. Ahmad Y., Batisse N., Chen X., Dubois M. Preparation and applications of fluorinated graphenes, Journal of Fluorine Chemistry, 2021, vol. 7, issue 1, art. no. 20, 23 p. DOI: 10.3390/c7010020.
7. Padamata S. K., Yasinskiy A., Stopic S., Friedrich B. Fluorination of two-dimensional graphene: a review, Journal of Fluorine Chemistry, 2022, vol. 255-256, art. no.109964, 14 p. DOI: 10.1016/j.jfluchem.2022.109964.
8. Chen X., Fan K., Liu Y. et al. Recent advances in fluorinated graphene from synthesis to applications: critical review on functional chemistry and structure engineering, Advanced Materials, 2022, vol. 34, issue 1, art.no. 2101665, 44 p. DOI: 10.1002/adma.202101665.
9. Felten A., Eckmann A., Pireaux J.J. et al. Controlled modification of mono-and bilayer graphene in O2, H2 and CF4 plasmas, Nanotechnology, 2013, vol. 24, issue 35, art. no. 355705, 8 p. DOI: 10.1088/0957-4484/24/35/355705.
10. Neustroev E.P., Nogovitcyna M.V., Popov V.I., Timofeev V.B. Modification of thermally reduced graphene oxide by the SF6/Ar plasma treatment, Inorganic Materials: Applied Research, 2017, vol. 8, issue 5, pp. 763-768. DOI: 10.1134/S2075113317050215.
11. Shen C., Huang G., Cheng Y. et al. Thinning and functionalization of few-layer graphene sheets by CF4 plasma treatment, Nanoscale Research Letters, 2012, vol. 7, issue 1, art. no. 268, 8 p. DOI: 10.1186/1556-276X-7-268.
12. Baraket M., Walton S.G., Lock E.H. et al. The functionalization of graphene using electron-beam generated plasmas, Applied Physics Letters, 2010, vol. 96, issue 23, pp. 231501-1-231501-3. DOI: 10.1063/1.3436556.
13. Tahara K., Iwasaki T., Matsutani A., Hatano M. Effect of radical fluorination on mono-and bi-layer graphene in Ar/F2 plasma, Applied Physics Letters, 2012, vol. 101, issue 16, pp. 163105-1-163105-4. DOI: 10.1063/1.4760268.
14. Cheng L., Jandhyala S., Mordi G. et al. Partially fluorinated graphene: structural and electrical characterization, ACS Applied Materials & Interfaces, 2016, vol. 8, issue 7, pp. 5002-5008. DOI: 10.1021/acsami.5b11701.
15. Wang B., Wang J., Zhu J. Fluorination of graphene: a spectroscopic and microscopic study, ACS Nano, 2014, vol. 8, issue 2, pp. 1862-1870. DOI: 10.1021/nn406333f.
16. Chen M., Zhou H., Qiu C. et al. Layer-dependent fluorination and doping of graphene via plasma treatment, Nanotechnology, 2012, vol. 23, issue 11, art. no. 115706, 6 p. DOI: 10.1088/0957-4484/23/11/115706.
17. Struzzi C., Scardamaglia M., Reckinger N. et al. Probing plasma fluorinated graphene via spectromicroscopy, Physical Chemistry Chemical Physics, 2017, vol. 19, issue 46, pp. 31418-31428. DOI:10.1039/C7CP05305C.
18. Chen M., Qiu C., Zhou H. et al. Fluorination of edges and central areas of monolayer graphene by SF6 and CHF3 plasma treatments, Journal of Nanoscience and Nanotechnology, 2013, vol. 13, issue 2, pp. 1331-1334. DOI: 10.1166/jnn.2013.5996.
19. Zhang H., Fan L., Dong H. et al. Spectroscopic investigation of plasma-fluorinated monolayer Ggraphene and application for gas sensing, ACS Applied Materials & Interfaces, 2016, vol. 8, issue 13, pp. 8652-8661. DOI: 10.1021/acsami.5b11872.
20. Sherpa S.D., Paniagua S.A., Levitin G. Photoelectron spectroscopy studies of plasma-fluorinated epitaxial graphene, Journal of Vacuum Science & Technology B, 2012, vol. 30, issue 3, pp. 03D102-1-03D102-7. DOI:10.1116/1.3688760.
21. Yoon M.A., Kim C., Kim J.H. et al. Surface properties of CVD-grown graphene transferred by wet and dry transfer processes, Sensors, 2022, vol. 22, issue 10, art. no. 3944, 11 p. DOI: 10.3390/s22103944.
22. Ferrari A.C., Meyer, J.C., Scardaci V. Raman spectrum of graphene and graphene layers, Physical Review Letters, 2006, vol. 97, issue 18, pp. 187401-1-187401-4. DOI: 10.1103/PhysRevLett.97.187401.
23. Anusuya T., Pathak D. K., Kumar R., Kumar V. Deconvolution and quantification of defect types from the first order Raman spectra of graphene oxide derivatives, FlatChem, 2022, vol. 35, art. no. 100422, 9 p. DOI: 10.1016/j.flatc.2022.100422.
24. Liu W., Wei J., Sun X., Yu H. A study on graphene–metal contact, Crystals, 2013, vol. 3, issue 1, pp. 257-274. DOI: 10.3390/cryst3010257.
25. Stine R., Lee W. K., Whitener Jr, K. E. et al. Chemical stability of graphene fluoride produced by exposure to XeF2, Nano Letters, 2013, vol. 13, issue 9, pp. 4311-4316. DOI: 10.1021/nl4021039.