Metastable carbon allotropes in picosecond-laser-modified diamond
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In this paper, we report on the bulk modifications of type IIa single-crystal diamond with visible 10-ps pulses (at λ = 532 nm) and microstructural changes characterized by the appearance of several ‘unidentifiable’ vibrational modes in the frequency range of 1000–1400 cm−1 in the Raman spectra of laser-modified diamond. It is found that the new Raman modes are strongly pronounced in the spectra of high-stress regions in immediate proximity to the bulk microstructures in the absence of the G mode at ~1580 cm−1 characteristic of the sp2 phase. The high internal stresses are determined from the splitting of the triply degenerate diamond Raman line. The revealed structure transformation is localized within a narrow bulk layer near the bulk microstructures formed, and the stress relaxation is found to result in disappearance of the detected vibrational modes in the spectra. It is suggested that the formation of bulk regions with a sp3 carbon structure consisting of Z-carbon and hexagonal diamond is responsible for the appearance of new Raman modes in the spectra of laser-modified diamond. These findings evidence that the stress-assisted formation of novel metastable carbon phases or defect structures occur in the course of bulk modification of diamond with ps-laser pulses. In addition, we report the results of simulations of internal stresses in the system ‘graphitized cylinder-in-diamond’ to show (1) the effect of the mechanical properties of laser-modified diamond on the resulting stresses and (2) formation of bulk microscopic regions with high stresses of >10 GPa, i.e., the conditions at which various sp3 carbon allotropes and defect structures become more stable than graphite.
KeywordsRaman Spectrum Raman Band Raman Line Raman Mode Bulk Region
The work was partly supported by the SNSF project IZ73Z0-128088/1.
- 5.J.B. Ashcom, PhD thesis (Harvard University, 2003); http://mazur-www.harvard.edu/sentFiles/Mazurpubs_309.pdf
- 13.S.M. Pimenov, A.A. Khomich, I.I. Vlasov, E.V. Zavedeev, B. Neuenschwander, B. Jäggi, V. Romano, ALT Proceedings, vol. 1 (2012). doi: 10.12684/alt.1.50
- 31.R.P. Mildren, Intrinsic Optical Properties of Diamond, in Optical Engineering of Diamond, ed. by R.P. Mildren, J.R. Rabeau (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2013)Google Scholar
- 37.L.D. Landau, E.M. Lifshitz, Theory of Elasticity (Volume 7 of A Course of Theoretical Physics) (Pergamon Press, Oxford, 1970)Google Scholar
- 40.H.O. Pierson, Handbook of Carbon, Graphite, Diamond and Fullerenes (Properties, Processing and Applications), P.A. Thrower, Editor-in-Chief. (Noyes Publications, Park Ridge, 1993), p. 417Google Scholar
- 47.S.M. Pimenov, V.V. Kononenko, T.V. Kononenko, V.I. Konov, P. Fischer, V. Romano, H.P. Weber, A.V. Khomich, R.A. Khmelnitskiy, New Diam. Front. Carbon Technol. 14(1), 21 (2004)Google Scholar