Nosenko V. Structure and properties of paramagnetic centers in wide-gap materials based on apatites, oxides, and A2B6

Українська версія

Thesis for the degree of Doctor of Science (DSc)

State registration number

0524U000174

Thesis Registration Form

0524U000174.pdf

Applicant for

Valentyna V. Nosenko

Specialization

01.04.07 - Фізика твердого тіла

Date of defense

29-05-2024

Specialized Academic Board

Д 26.199.01.

V. Lashkaryov Institute of Semiconductor Physics of National Academy

Essay

2. The purpose of the work was to determine the nature, properties, and evolution of paramagnetic defects in light-emitting and radiation-sensitive wide-gap materials, as well as to substantiate the physical basis for using these defects as structural probes in the materials under study. The objects of the research were the paramagnetic defects in wide-gap materials based on hydroxyapatites (HAP), oxides, and A2B6. Radiospectroscopic (electron paramagnetic resonance, optically detected magnetic resonance, double electron-nuclear resonance), optical (photoluminescence, Raman), structural (X-ray diffraction, scanning electron microscopy), electrical (volt-ampere characteristics) methods were used in the research. For spectra simulations the following instruments were used: Symphonia from the Bruker WinEPR package, Separator from the Visual EPR package, and Origin. The scientific novelty of the obtained results is: for the first time radiation-induced centers in nitrate-containing HAP ((N)HAP) or carbonate-nitrate-containing HAP ((C,N)HAP) were observed, they are: NO32 (І), NO32 (ІІ), NO32-(ІІІ), NO32-(IV), NO32-(V), Ox-; their radiospectroscopic parameters, structure, mechanisms of γ- and UV-induced formation of centers, transformations of centers under heat treatment were determined; selective generation (depending on the energy of the quantum of external irradiation (UV or )) of NO32- and СО2- paramagnetic centers in (C,N)HAP was proved; possibility to control radiation sensitivity of HAP by preliminary annealing is shown; optimal conditions for EPR dosimetry, namely, registration of СО33 centers signal in (C)HAP annealed at 700°С, were proposed; characteristic parameter - the ratio of axial to orthorhombic СО2 centers amounts – was found, its value depends on the age of the fossil biological HAP (tooth enamel) while does not depend on the dose rate, thus providing new possibilities for fossils dating; it is shown that the synthetic (C)HAP coating obtained by detonation spraying is the mixture of two chemically close compounds: apatite and tetracalcium phosphate, relative contributions of these phases being dependent on the technological conditions of deposition. Transformations of HAP structure occur predominantly along the 6-fold axis and in its close vicinity; nontrivial vibration features of the Raman spectra of HAP coatings are revealed (the broad band in the range of ~ 1000–4000 cm–1 and intense high-frequency bands at 5000 and 5027 cm–1), they were explained using the unified theoretical approach as the result of a complex anharmonic interaction between the fundamental vibration of OH, lattice phonons and overtone of bending vibrations; the parameters of the spin Hamiltonian for Mn2+ ions in Mg2TiO4 and MgTiO3 crystalline phases were determined, which provides a tool for analyzing the phase composition of multicomponent ceramics; regularities of Mn distribution in ZnO:Mn varistor ceramics were established, and the possibility of controlling Mn distribution by additional thermal annealing was demonstrated; manganese doping in the process of colloidal growth of CdS:Mn nanoparticles was shown to slow down their growth; it was proved that Mn2+ paramagnetic centers can be used as a probe to determine the different polytypes content in the mixed-polytype structure of micron and submicron ZnS powders. In nano-ZnS, by studying the EPR signal from Mn2+, non-local non-paramagnetic defects - planar packing defects - were revealed and shown to be typical lattice defects in cubic nano-ZnS. The practical significance of the obtained results is the following: (C,N)HAP was proposed for fabrication of selective detectors of electromagnetic radiation, i.e., the detectors distinguishing UV- and -rays exposures. The method to sensitize (C)HAP dosimetric material is proposed, namely to pre-anneal (C)HAP at 700°С and to use the signal from СО33 centers for registration. The physical basis for a new EPR dating method of HAP-containing fossils has been developed. This method is free from the drawback inherent to the well-known EPR dating method, namely, it does not require neither additional irradiation of the samples nor determining the annual radiation dose. The technological factors affecting the defects subsystem of biocompatible coatings produced by (C)HAP detonation spraying have been identified. The possibility of using the EPR signal from Mn2+ for express analysis of the phase composition of micropowders of mixed-polytype zinc sulfide, as well as for detecting local distortions of the crystal lattice (planar defects) in nano-ZnS, has been demonstrated

Official opponents

Olexander Gomonnai
Valery A. Skryshevskyy
Anna Morozovska

Reviewers

Andriy Konchyts
Georgiy Tarasov
Yuriy Naseka

Research papers

1. Vorona, I.P., Shanina, B.D., Dzhagan, V.M., Rudko, G.Yu., Nosenko, V.V., Raievska, O.Ye., Stroyuk, O.L. (2022). Size-dependent effects in optically detected magnetic resonance spectra of CdS nanocrystals. J. Phys. Chem. C // A, 126(36), 15465–15471. doi: 10.1021/acs.jpcc.2c04144

2. Bacherikov, Yu.Yu., Vorona, I.P., Gilchuk, A.V., Goroneskul, V.Yu., Zhuk, A.G., Kladko, V.P., Nosenko, V.V., Okhrimenko, O.B., Ponomarenko, V.V., Polishchuk, Yu.O. (2022). Metamorphosis of the properties of the gas-phase fraction of ZnS:Mn obtained by the method of self-propagating high-temperature synthesis from the charge with a different Zn/S ratio. Journal of Luminescence // A, 251, 119184. doi: 10.1016/j.jlumin.2022.119184;

3. Markevich, I., Korsunska, N., Vorona, I., Nosenko, V., Kolomys, O., Strelchuk, V., Stara, T., Bondarenko, V., Melnichuk, O., Melnichuk, L. (2020). Mn distribution in ZnO:Mn ceramics: influence of sintering process and thermal annealing. ECS J. Solid State Sci. Technol. // A, 9, 103001. doi: 10.1149/2162-8777/abba06

4. Borkovska, L., Khomenkova, L., Vorona, I., Nosenko, V., Stara, T., Gudymenko, O., Kladko, V., Labbé, C., Cardin, J., Kryvko, A., Kryshtab, T. (2020). The role of excess MgO in the intensity increase of red emission of Mn4+-activated Mg2TiO4 phosphors. Journal of Materials Science: Materials in Electronics // A, 31, 7564. doi:10.1007/s10854-020-03143-x

5. Nosenko, V.V., Rudko, G.Yu., Yaremko, A.M., Yukhymchuk, V.O., Hreshchuk, O.M. (2018). Anharmonicity and Fermi resonance in the vibrational spectra of a CO2 molecule and CO2 molecular crystal: similarity and distinctions. Journal of Raman Spectroscopy// A, 49(3), 559-568. doi:10.1002/jrs.5297;

6. Nosenko, V., Vorona, I., Grachev, V., Ishchenko, S., Baran, N., Bacherikov, Yu., Zhuk, A., Polishchuk, Yu., Kladko, V., Selishchev, A. (2016). The Crystal Structure of Micro- and Nanopowders of ZnS Studied by EPR of Mn2+ and XRD. Nanoscale Research Letters // A, 11, 517(6 pages). doi: 10.1186/s11671-016-1739-4

7. Vorona, I.P., Nosenko, V.V., Baran, N.P., Ishchenko, S.S., Lemishko, S.V., Zatovsky, I.V., Strutynska, N.Yu. (2016). EPR study of radiation-induced defects in carbonate-containing hydroxyapatite annealed at high temperature. Radiation Measurements // A, 87, 49-55. doi: 10.1016/j.radmeas.2016.02.020

8. Nosenko, V.V., Yaremko, A.M., Dzhagan, V.M., Vorona, I.P., Romanyuk, Yu.A., Zatovsky, I.V. (2016). Nature of some features in Raman spectra of hydroxyapatite-containing materials. Journal of Raman Spectroscopy // A, 47, 726–730. doi: 10.1002/jrs.4883

9. Nosenko, V., Strutynska, N., Vorona, I., Zatovsky, I., Dzhagan, V., Lemishko, S., Epple, M., Prymak, O., Baran, N., Ishchenko, S., Slobodyanik, N., Prylutskyy, Yu., Klyui, N., Temchenko, V. (2015). Structure of Biocompatible Coatings Produced from Hydroxyapatite Nanoparticles by Detonation Spraying. Nanoscale Research Letters // A, 10, 464(7 pages). doi: 10.1186/s11671-015-1160-4

10. Nosenko, V.V., Vorona, I.P., Baran, N.P., Ishchenko, S.S., Vysotskyi, B.V., Krakhmalnaya, T.V., Semenov, Yu.A. (2015). Comparative EPR study CO2- radicals in modern and fossil tooth enamel, Radiation Measurements // A, 78, 53-57. doi: 10.1016/j.radmeas.2014.09.004

11. Nosenko, V., Rudko, G., Fediv, V., Savchuk, A., Gule, E., Vorona, I. (2014). Retardation of nanoparticles growth by doping. Nanoscale Research Letters // A, 9, 683 (5 pages). doi: 10.1186/1556-276X-9-683

12. Nosenko, V.V., Vorona, I.P., Ishchenko, S.S., Baran, N.P., Zatovsky, I.V., Gorodilova, N.A., Povarchuk, V.Yu. (2012). Effect of pre-annealing on NO32− centers in synthetic hydroxyapatite. Radiation Measurements // A, 47, 970-973. doi: 10.1016/j.radmeas.2012.08.008

13. Ishchenko, S.S., Vorona, I.P., Okulov, S.M., Baran, N.P., Rudko, V.V. (2011). ENDOR study of CO2− radicals in hydroxyapatite of γ-irradiated bone. Radiation Measurements // A, 46, 37-39. doi: 10.1016/j.radmeas.2010.07.025

14. Vorona, I., Nosenko, V., Okulov, S., Savchenko, D., Petrenko, T., Stara, T., Labbé, C., Borkovska, L. (2022). EPR Study of the Mn-Doped Magnesium Titanate Ceramics. ECS Journal of Solid State Science and Technology // A, 11, 013005. doi: 10.1149/2162-8777/ac4a80

15. Vorona, I.P., Ishchenko, S.S., Okulov, S.M., Nosenko, V.V. (2020). Some features of Mn2+ EPR spectra in cubic nano-ZnS. Semiconductor physics, quantum electronics and optoelectronics // A, 23, 60-65. doi: 10.15407/spqeo23.01.060

16. Vorona, I.P., Ishchenko, S.S., Grachev, V.G., Baran, N.P., Okulov, S.M., Nosenko, V.V., Selishchev, A.V. (2019). EPR of Mn2+ in Nano-Sized Zinc Sulfide with Planar Lattice Defect. Journal of Applied Spectroscopy // A, 89, 146-150. doi: 10.1007/s10812-019-00792-7

Vorona, I.P., Grachev, V.G., Ishchenko, S.S., Baran, N.P., Bacherikov, Yu.Yu., Zhuk, A.G., Nosenko, V.V. (2016). Crystal Structure Determination of Low-Dimensional ZnS Powders Using EPR of Mn2+ Ions. Journal of Applied Spectroscopy // A, 83, 51-55. doi: 10.1007/s10812-016-0241-1

18. Strutynska, N., Slobodyanik, N., Malyshenko, A., Zatovsky, I., Vorona, I., Prylutskyy, Yu., Prymak, O., Baran, N., Ishchenko, S., Nosenko, V. (2015). Synthesis, characterization and EPR investigation of γ-induced defects for nanoparticals of (MI, CO3)-containing (MI – Na, K) apatites. Solid State Phenomena // A, 230, 133-139. doi: 10.4028/www.scientific.net/SSP.230.133;

19. Vorona, I.P., Ishchenko, S.S., Baran, N.P., Nosenko, V.V., Zatovsky, I.V., Malyshenko, A.I., Povarchuk, V.Yu. (2013). Radiation-induced defects in annealed carbonate-containing hydroxyapatite. Physics of the Solid State// A, 55, 2543-2548. doi: 10.1134/S1063783413120329

20. Baran, N.P., Vorona, I.P., Ishchenko, S.S., Nosenko, V.V., Zatovsky, I.V., Gorodilova, N.A., Povarchuk, V.Yu. (2011). NO32 and СО2 centers in synthetic hydroxyapatite: Features of the formation under γ- and UV-irradiation. Physics of the Solid State // A, 53, 1891-1894. doi: 10.1134/S106378341109006X

21. Vorona, I.P., Ishchenko, S.S., Baran, N.P., Rudko, V.V., Zatovsky, I.V., Gorodilova, N.A., Povarchuk, V.Yu. (2010). NO32− centers in synthetic hydroxyapatite. Physics of the Solid State // A, 52, 2364-2368. doi: 10.1134/S1063783410110235

22. Nosenko, V., Korsunska, N., Vorona, I., Stara, T., Bondarenko, V., Melnichuk, O., Melnichuk, L., Kryvko, A., Markevich, I. (2020). The mechanism of formation of interface barriers in ZnO:Mn ceramics. SN Applied Sciences // A, 2, 979. doi: 10.1007/s42452-020-2754-8;

23. Strutynska, N., Slobodyanik, N., Malyshenko, A., Zatovsky, I., Vorona, I., Epple, M., Prymak, O., Baran, N., Ishchenko, S., Nosenko, V. (2014). Synthesis, characterization and EPR investigation of γ-induced defects for nanoparticals of (MI, CO3)-containing (MI – Na, K) apatites. International Conference on Oxide Materials for Electronic Engineering - Fabrication, Properties and Applications, OMEE 2014 - Book of Conference Proceedings // A, 75–76. doi: 10.1109/OMEE.2014.6912346

24. Rudko, G.Yu., Fediv, V.I., Savchuk, А.I., Gule, E.G., Vorona, I.P., Nosenko, V.V. Nucleation and growth kinetics of colloidal nanoparticles CdS:Mn in aqueous solution of polyvinyl alcohol. (2014). Semiconductor Physics, Quantum Electronics and Optoelectronics // Б, 17, 222-226;

25. Затовський, І.В., Ворона, І.П., Малишенко, А.І., Слободяник, М.С., Іщенко, С.С., Баран, М.П., Носенко, В.В. (2013). γ- й УФ-індуковні парамагнітні центри у відпаленому синтетичному гідроксіапатиті. Доповiдi Нацiональної академiї наук України // Б, 6, 127-132.

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