Thermally stimulated and dynamic effects in identification and study of carbon materials by Raman spectroscopy

S.I. Isaenko*, T.G. Shumilova**

Institute of Geology, Komi Science Center, Ural Branch, Russian Academy of Sciences, Syktyvkar, 167982 Russia

E-mail: *s.i.isaenko@gmail.com, **tg_shumilova@mail.ru

Received November 16, 2020


ORIGINAL ARTICLE

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DOI: 10.26907/2542-064X.2021.1.72-87

For citation: Isaenko S.I., Shumilova T.G. Thermally stimulated and dynamic effects in identification and study of carbon materials by Raman spectroscopy. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2021, vol. 163, no. 1, pp. 72–87. doi: 10.26907/2542-064X.2021.1.72-87. (In Russian)

Abstract

In this paper, the aspects of studying micron-sized carbon material substances using Raman spectroscopy with laser excitation were discussed. The relevance of the study is determined by the fact that the positions of diagnostic lines in the Raman spectra of carbon materials are significantly affected as the analyzed sample region is heated during the process of spectra recording, thereby resulting in a shift of the diagnostic lines and bands, up to the burnout of the analyzed particle region or to the complete combustion of the sample. To assess the influence of the laser radiation power on the position of diagnostic lines in the Raman spectra of carbon materials, we studied the position of the lines depending on the laser power and sample size of both natural and man-made carbon phases of various structures: highly crystalline graphite, glassy carbon, cubic monocrystalline diamond, hexagonal monocrystalline diamond (lonsdaleite), and ultrananocrystalline diamond. The study was performed by Raman spectroscopy with the use of a high-resolution LabRam HR800 microspectrometer (Horiba, Jobin Yvon). For mono-, nano-, and ultrananocrystalline diamonds, a number of examples were provided to demonstrate that the exciting laser power during Raman spectroscopy measurements of carbon materials must be especially carefully monitored in particles of 10 μm or less in size. For highly crystalline graphite particles, the laser power must be controlled in samples smaller than 4 μm in size. When the Raman spectra were registered during the controlled laser heating, it was found that the samples of a black carbon variety between coal and diamond (described as togorite by V.A. Yezersky V.A. (1986)) had intergrowths of diamond and glassy carbon, a diamond core with a glass-like carbon shell. The results obtained show that the controlled use of the thermal effect of laser radiation can be helpful in identification of the detailed spectroscopic characteristics that occur during the intensive heating of samples, as well as in recovering mineral individuals from aggregates.

Keywords: Raman spectroscopy, laser heating, carbon materials, glassy carbon, highly crystalline graphite, lonsdaleite, ultrananocrystalline diamond, impactites

Acknowledgments. The study was performed as part of the R&D project of the state assignment (SR no. AAAA-A17-117121270036-7) for Institute of Geology, Komi Science Center, Ural Branch, Russian Academy of Sciences.

Figure Captions

Fig. 1. Shift of the relative wave number (arrows) and the corresponding coefficients of displacement of the main diagnostic lines for diamond (a) and graphite (b) depending on the external pressure or temperature.

Fig. 2. Red shift characteristics of the G-band in the Raman spectrum of the Ceylon graphite: a – dependence of the G-band shift on the size of particles under the maximum laser power; b – enlarged region of the area with small-sized particles. Designations: square markers and dashed line – laser excitation of 514.5 nm (Р = 100 MW); triangular marker and solid line – laser excitation of 632.8 nm (Р = 20 MW).

Fig. 3. Data of the Raman spectroscopy for glassy carbon (GC 2000): a – Raman spectra of glassy carbon depending on the power (P) of laser (λ = 514.5 nm); b – dependence of the red shift of the D-band on the laser power; c – dependence of the red shift of the G-band on the laser power.

Fig. 4. Raman spectra of the lonsdaleite particle (D0-B4-P30) in case of the dynamic registration scheme. Dashed line – Raman spectrum at the laser power of 1 MW (1332 cm–1 line). Solid lines – spectra registered at certain time intervals (time (min(')sec(") is given on the left) with the laser power increased up to 10 times. An optical image of the particle is given at the upper right; dashed line shows the particle contours.

Fig. 5. Raman spectra of nanocrystalline diamond in a glass-like carbon shell during the experiment on shell burning: a – Raman spectra of the KR-15-41-P14 particle at different laser power values (488 nm) during the registration of spectra (from bottom to top), time interval (min(')sec(")) from the beginning of the experiment is given on the left, laser power is indicated on the right; b – detailed Raman spectra of the KR-15-41-P14 particle at different laser power values in the beginning of the experiment with the break-down into components, an optical image of the source particle is given below, an image of the same particle after the laser impact is provided at the top; c – recurrent detailed Raman spectra after the glassy-carbon shell burning at different laser power values for the same analysis stage.

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