Raman Scattering and Electron Spin Magnetism Features in Monocrystalline CVD Dia monds Irradiated with Fast Neutrons

The effect of reactor neutron irradiation on Raman scattering spectra and electron spin resonance (ESR) signals of CVD monocrystalline diamond films is studied. The presence of superparamagnetic clusters of spin radicals (ferrons) — regions of magnetic ordering of uncompensated electron spins (g-factor ≈4.65) in an external magnetic field — is revealed for the first time in neutron-irradiated (fluence 3 ꞏ 1018 cm–2) diamonds. It is established that thermal annealing at 400 °C for 1 h drastically reduces the ESR signal intensity of spinradical associates of radiation defects, while approximately doubles the amplitude of the ESR signal from single paramagnetic centers and narrows its linewidth by a factor of ≈4.6. Raman spectroscopy data indicate partial recovery of the crystal structure of diamond due to the annealing of both isolated radiation defects and nanoscale amorphized regions (ferrons). The types of defects responsible for the formation of ferrons in diamonds as a result of their irradiation with reactor neutrons are discussed.

1. G. A. Prinz. Science, 282, N 5394 (1998) 1660—1663, https://doi.org/10.1126/science.282.5394.1660

2. J. Narayan, A. Bhaumik, S. Gupta, A. Haque, R. Sachan. Mater. Res. Lett., 6, N 7 (2018) 353—364, https://doi.org/10.1080/21663831.2018.1458753

3. R. Höhne, P. Esquinazi, V. Heera, H. Weishart. Diamond Rel. Mater., 16, N 8 (2007) 1589—1596, https://doi.org/10.1016/j.diamond.2007.01.019

4. А. В. Хомич, Р. А. Хмельницкий, Н. А. Поклонский, Н. М. Лапчук, А. А. Хомич, В. А. Дравин, О. Н. Поклонская, Е. Е. Ашкинази, И. И. Власов, Е. В. Заведеев, В. Г. Ральченко. Журн. прикл. спектр., 79, № 4 (2012) 615—624 A. V. Khomich, R. A. Khmelnitsky, N. A. Poklonski, N. M. Lapchuk, A. A. Khomich, V. A. Dravin, O. N. Poklonskaya, E. E. Ashkinazi, I. I. Vlasov, E. V. Zavedeev, V. G. Ralchenko. J. Appl. Spectr., 79, N 6 (2012) 600—609, https://doi.org/10.1007/s10812-012-9646-7.

5. T. N. Makgato, E. Sideras-Haddad, M. A. Ramos, M. García-Hernández, A. Climent-Font, A. Zucchiatti, A. Muñoz-Martin, S. Shrivastava, R. Erasmus. J. Magn. Magn. Mater., 413 (2016) 76—80, https://doi.org/10.1016/j.jmmm.2016.04.030

6. N. A. Poklonski, A. A. Khomich, I. A. Svito, S. A. Vyrko, O. N. Poklonskaya, A. I. Kovalev, M. V. Kozlova, R. A. Khmelnitskii, A. V. Khomich. Appl. Sci., 13, N 10 (2023) 6221, https://doi.org/10.3390/app13106221

7. Y. Sakai, J. R. Chelikowsky, M. L. Cohen. Phys. Rev. Mater., 2, N 7 (2018) 074403, https://doi.org/10.1103/PhysRevMaterials.2.074403

8. Y. Gao, X. Feng, B.-C. Gong, C. Zhong, S.A. Yang, K. Liu, Z.-Y. Lu. Carbon, 177 (2021) 11—18, https://doi.org/10.1016/j.carbon.2021.01.153

9. N. A. Poklonski, S. A. Vyrko, A. G. Zabrodskii. Phys. Scripta, 100, N 12 (2025) 125914, https://doi.org/10.1088/1402-4896/ae2550

10. M. A. Garcia, E. Fernandez Pinel, J. de la Venta, A. Quesada, V. Bouzas, J.F. Fernández, J. J. Romero, M. S. Martín González, J. L. Costa-Krämer. J. Appl. Phys., 105 (2009) 013925, https://doi.org/10.1063/1.3060808

11. A. P. Bolshakov, V. Yu. Yurov, I. A. Fedorova, A. K. Martyanov, P. V. Fedotov, A. F. Popovich, V. G. Ralchenko,B. Dai. DiamondRel.Mater.,150(2024)111721,https://doi.org/10.1016/j.diamond.2024.111721

12. J. A. Weil, J. R. Bolton. Electron Paramagnetic Resonance: Elementary Theory and Practical Applications, Hoboken, Wiley (2007) https://doi.org/10.1002/0470084987

13. A. A. Khomich, A. A. Averin, O. N. Poklonskaya, S. N. Bokova-Sirosh, A. N. Dzeraviaha, R. A. Khmelnitsky, I. I. Vlasov, O. Shenderova, N. A. Poklonski, A. V. Khomich. J. Phys.: Conf. Ser., 1400 (2019) 044017, https://doi.org/10.1088/1742-6596/1400/4/044017

14. Properties, Growth and Applications of Diamond, Eds. M. H. Nazaré, A. J. Neves, London, INSPEC, IEE (2001)

15. A. Bosak, M. Krisch. Phys. Rev. B, 72, N 22 (2005) 224305, https://doi.org/10.1103/PhysRevB.72.224305

16. S. Osswald, V. N. Mochalin, M. Havel, G. Yushin, Y. Gogotsi. Phys. Rev. B, 80 (2009) 075419, https://doi.org/10.1103/PhysRevB.80.075419

17. A. A. Khomich, R. A. Khmelnitsky, A. V. Khomich. Nanomaterials, 10, N 6 (2020) 1166, https://doi.org/10.3390/nano10061166

18. J. O. Orwa, K. W. Nugent, D. N. Jamieson, S. Prawer. Phys. Rev. B, 62, N 9 (2000) 5461—5472, https://doi.org/10.1103/PhysRevB.62.5461

19. О. Н. Поклонская, С. А. Вырко, А. А. Хомич, А. А. Аверин, А. В. Хомич, Р. А. Хмельницкий, Н. А. Поклонский. Журн. прикл. спектр., 81, № 6 (2014) 879—887 O. N. Poklonskaya, S. A. Vyrko, A. A. Khomich, A. A. Averin, A. V. Khomich, R. A. Khmelnitsky, N. A. Poklonski. J. Appl. Spectr., 81, N 6 (2015) 969—977, https://doi.org/10.1007/s10812-015-0037-8.

20. S. Prawer, I. Rosenblum, J. O. Orwa, J. Adler. Chem. Phys. Lett., 390, N 4-6 (2004) 458—461, https://doi.org/10.1016/j.cplett.2004.04.027

21. S. V. Nistor, M. Stefan, V. G. Ralchenko, A. V. Khomich, D. Schoemaker. J. Appl. Phys., 87, N 12 (2000) 8741—8746, https://doi.org/10.1063/1.373604

22. J. Isoya, H. Kanda, I. Sakaguchi, Y. Morita, T. Ohshima. Rad. Phys. Chem., 50, N 4 (1997) 321—330, https://doi.org/10.1016/S0969-806X(97)00070-4

23. S. K. Misra. In: Electron Paramagnetic Resonance in Modern Carbon-Based Nanomaterials, Eds. D. Savchenko, A. H. Kassiba, Sharjah, UAE, Bentham Science Publishers (2018) 1—35, https://doi.org/10.2174/9781681086934118010004

24. N. Nunn, S. Milikisiyants, E. O. Danilov, M. D. Torelli, L. Dei Cas, A. Zaitsev, O. Shenderova, A. I. Smirnov, A. I. Shames. J. Appl. Phys., 132, N 7 (2022) 075106, https://doi.org/10.1063/5.0103313

25. О. Н. Поклонская. Докл. НАН Беларуси, 57, № 5 (2013) 49—54, https://elibrary.ru/item.asp?id=26472015

26. О. Н. Поклонская. Вестн. БГУ. Сер. 1: Физ. Мат. Информ., № 2 (2013) 60—65, http://elib.bsu.by/handle/123456789/95908

27. D. J. Twitchen, M. E. Newton, J. M. Baker, O. D. Tucker, T. R. Anthony, W. F. Banholzer. Phys. Rev. B, 54, N 10 (1996) 6988—6998, https://doi.org/10.1103/PhysRevB.54.6988

28. А. Б. Дровосеков, Н. М. Крейнес, Д. А. Зигануров, А. В. Ситников, С. Н. Николаев, В. В. Рыльков. ЖЭТФ, 164, № 4(10) (2023) 650—661 A. B. Drovosekov, N. M. Kreines, D. A. Ziganurov, A. V. Sitnikov, S. N. Nikolaev, V. V. Rylkov. J. Exp. Theor. Phys., 137, N 4 (2023) 562—571, https://doi.org/10.1134/S1063776123100023.

29. A. B. Drovosekov, M. Yu. Dmitrieva, A. V. Sitnikov, S. N. Nikolaev, V. V. Rylkov. ЖЭТФ, 169, № 2 (2026) 212—224, http://jetp.ras.ru/cgi-bin/e/index/r/169/2/p212?a=list

30. В. Ю. Осипов, К. В. Богданов, F. Treussart, A. Rampersaud, А. В. Баранов. Опт. и спектр., 130, № 2 (2022) 332—341 V. Yu. Osipov, K. V. Bogdanov, F. Treussart, A. Rampersaud, A. V. Baranov. Opt. Spectrosc., 131, N 1 (2023) 38—47, https://doi.org/10.1134/S0030400X2303013X.

31. A. V. Nikolaev, M. Ye. Zhuravlev, L. L. Tao. J. Magn. Magn. Mater., 588, Pt. A (2023) 171394, https://doi.org/10.1016/j.jmmm.2023.171394

32. A. Sorkin, J. Adler, R. Kalish. Phys. Rev B, 70, N 6 (2004) 064110, https://doi.org/10.1103/PhysRevB.70.064110

33. B. A. Fairchild, S. Rubanov, D. W. M. Lau, M. Robinson, I. Suarez-Martinez, N. Marks, A. D. Greentree, D. McCulloch, S. Prawer. Adv. Mater., 24, N 15 (2012) 2024—2029, https://doi.org/10.1002/adma.201104511

34. E. K. Nshingabigwi, T. E. Derry, S. R. Naidoo, J. H. Neethling, E. J. Olivier, J. H. O’Connell, C. M. Levitt. Diamond Rel. Mater., 49 (2014) 1—8, https://doi.org/10.1016/j.diamond.2014.07.010

35. J. Zhang, F. Huang, S. Li, G. Yu, Z. Xu, L. Hei, F. Lv, A. Horne, P. Wang, M. Qi. Diamond Rel. Mater., 154 (2025) 112189, https://doi.org/10.1016/j.diamond.2025.112189

36. M. E. Newton. In: Electron Paramagnetic Resonance, 20, Eds. B. C. Gilbert, M. J. Davies, D. M. Murphy, Cambridge, RSC (2007) 131—156

37. Handbook of Magnetism and Magnetic Materials, Eds. J. M. D. Coey, S. S. P. Parkin, Cham, Springer (2021), https://doi.org/10.1007/978-3-030-63210-6

38. Н. А. Поклонский, Т. М. Лапчук, Н. И. Горбачук. Журн. прикл. спектр., 68, № 4 (2001) 419—422 N. A. Poklonskii, T. M. Lapchuk, N. I. Gorbachuk. J. Appl. Spectr., 68, N 4 (2001) 543—547, https://doi.org/10.1023/A:1012511517323.

39. A. Sommerfeld. Electrodynamics: Lectures on Theoretical Physics, III, New York, Academic Press (1959)

40. J. A. Osborn. Phys. Rev., 67, N 11-12 (1945) 351—357, https://doi.org/10.1103/PhysRev.67.351

41. M. Jonas. Rad. Meas., 27, N 5-6 (1997) 943—973, https://doi.org/10.1016/S1350-4487(97)00202-3