Modification of carbon (nano)materials by swift heavy ions Andrzej Olejniczak1,2, Nadezhda A. Nebogatikova3, Zoran Jovanović4, and Michalina Milewicz-Zalewska1 1Nicolaus Copernicus University in Toruń (PL) 2FLNR JINR (RU) 3Rzhanov Institute of Semiconductor Physics SB RAS (RU) 4Vinča Institute of Nuclear Sciences (RS) NICA days 2017 Warsaw, November 6–10 A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Sektor N8: Ion-implantation nanotechnology and radiation materials science Aumayr et al. J. Phys.: Condens. Matter 23 (2011) 393001 Energy loss (keV/nm) Ion energy (MeV) A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

HOPG (structure and practical aspects) High temperature gas reactors TRISO coated particle fuel Allen, T., Busby, J., Meyer, M., & Petti, D. Materials today, (2010) 13, 14. Image source: nanoprobes.aist-nt.com HOPG - highly-ordered form of high-purity pyrolytic graphite sp2-hybridized C atoms with hexagonal symmetry stacked layers (basal planes) - Bernal ABAB stacking semimetal Fission product yields by mass for thermal neutron fission Image source: wikipedia A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

HOPG (earlier studies) A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

HOPG (structure and STM results) Image source: nanoprobes.aist-nt.com Xe 167 MeV, 1012 cm-2, Se = 17.3 keV/nm A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

HOPG (XAES and XRD results) single layer -> convolution of σ and π-state multilayer -> additional term πint – interlayer interaction Upon SHI-irradiation: interlayer distance increases, interlayer interaction -> 0 A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

HOPG (TEM) virgin 1012 ions/cm2 1013 ions/cm2 Image source: Shuffle the Cards, Your Guide to Playing Cards Like a Pro A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

HOPG (TEM and Raman spectroscopy) Figure source: A.C. Ferrari / Solid State Communications 143 (2007) 47–57 A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (models and properties) Inexpensive material, obtained by oxidation of graphite graphene sheets with covalently bonded oxygen-bearing groups epoxy and hydroxyl groups at the basal plane carbonyl, carboxylic acid, and lactol groups at the edges typical composition of fully oxidized graphene C6H2O3, C:O 2:1 no longer flat (sp2 -> sp3) higher interlayer distance ~ 9-10 Å easy exfoliation can be easily dispersed in water and polar solvents dielectric (band gap ~ 3.5 eV) can be easily reduced, sp3-> sp2 Kim, S., Zhou, S., Hu, Y., Acik, M., Chabal, Y. J., Berger, C., ... & Riedo, E. Nature materials (2012) , 11, 544 Dreyer, D. R., Todd, A. D., & Bielawski, C. W. Chemical Society Reviews (2014), 43, 5288 A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Fig. 1. Changes in atomic fraction of C atoms as functions of ion fluence (a) and deposited electronic energy density (b). The curves have been fitted according direct impact model. Variations in the ID/IG as functions of ion fluence (c) and deposited electronic energy density (d). A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Fig. 1. C1s core level XPS spectra of 167 MeV Xe ion-irradiated GO. Fig. 2. I-V characteristics of virgin and 48 MeV Ar ion-irradiated GO specimens (a); changes in the current recorded for lateral configuration at a voltage of 5 V as a function of ion fluence (line is guide to the eye) (b). A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Fig. 1. Raman spectra of 167 MeV Xe (a) and 200 keV Xe ion-irradiated GO. The signal of sp-hybridized carbon chains is shown in enlargement in (c). A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Graphene oxide, 200 keV Xe (Raman and XPS spectroscopy) Fig. 1. (top) Changes in the surface atomic fraction of C atoms for 200 keV Xe ion-irradiated GO films. Fig. 2. (left) Evolution of Raman spectral parameters of GO thin films irradiated to different fluences of XXX keV Xe ions. A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Graphene oxide, 107 MeV Kr (AFM) A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Graphene oxide, 200 keV Xe (AFM) A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Graphene oxide (XPS and Raman) Multi-graphene (AFM and SEM) multi-graphene on SiO2/Si substrate – we can „drill” nano-size pores (antidots) in the most upper layers of the films Milani et al. Beilstein Journal of Nanotechnology (2015) A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Glassy carbon (GC) models R. E. Franklin, Proc. R. Soc. A (1951) 209, 196 Harris, P. J. F. Philos. Mag.  (2004):, 84, 3159 Jenkins, G. M., and Kawamura, K., Nature (1971), 231, 175 A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Glassy carbon (GC) Raman depth profiling A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

GC - Electronic stopping power threshold for defect creation A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Summary SHI-irradiation of HOPG introduces point-like defects and leads to an increase in the interlayer spacing. At high fluences HOPG is transformed into loosely interacting, damaged graphene sheets that exhibit unusual Raman spectral behavior. One of the most important radiation-induced transformations of GO is its reduction to reduced graphene oxide (rGO) of improved electrical conductivity. Under SHI-irradiation the reduction process is highly localized, leading to the formation of nanometer-sized rGO spots. Assuming the localized reduction occurs along the ion trajectory through several GO sheets, the resulting structures can be considered as arrays of vertically-arranged graphene quantum dots embedded in a non-conducting matrix. For samples irradiated to high fluences with the most energetic ions the presence of sp-hybridized carbon chains was detected. No such structures were formed under low-energy ion bombardment, implying that sp-C formation takes place exclusively at the electronic stopping power regime. The above assumption was further confirmed by investigating the cross-sectional damage profile of GC samples. A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Acknowledgements Thanks to: Our Head V.A. Skuratov, PhD, DSc. UMCS Lublin, Ion Physics & Implantation Group (Dr. M. Kulik, Prof. J. Żuk) Prof. V.V. Uglov (BSU, Minsk) for XRD Jacques O'Connell (NMMU, SA) for TEM Financial support: This research was partially supported by the Grant and Cooperation Program between Polish scientific institutions and JINR (JINR Theme No. 04-5-1131-2017/2021) A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions

Thank you for your attention! Toruń by night Dubna - bird's-eye view A. Olejniczak et al. Modification of carbon (nano)materials by swift heavy ions