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J. Korean Ceram. Soc. > Volume 60(6); 2023 > Article
Journal of the Korean Ceramic Society 2023;60(6): 990-1009.
doi: https://doi.org/10.1007/s43207-023-00323-3
Cobalt-doped zinc glycolate as a precursor for the production of Zn1-xCoxO oxide with nanostructured octahedral particles: synthesis, crystal structure, thermal, spectral, and optical properties
V. N. Krasil’nikov1, A. P Tyutyunnik1, I. V. Baklanova1, O. I. Gyrdasova1, V. P. Zhukov1, E. V. Chulkov2,3,4
1Institute of Solid State Chemistry UB RAS, Ekaterinburg, Russia
2Laboratory of Electronic and Spin Structure of Nanosystems, St. Petersburg State University, St. Petersburg, 198504, Russia
3Departamento de Polímeros y Materiales Avanzados: Física, Química y Tecnología, Facultad de Ciencias Químicas, Universidad del País Vasco (UPV-EHU), Apdo. 1072, E-20080, San Sebastián/Donostia, Spain
4Donostia International Physics Center (DIPC), Paseo de Manuel Lardizabal 4, E-20018, San Sebastián/Donostia, Spain
Correspondence  I. V. Baklanova ,Email: baklanova_i@ihim.uran.ru
Received: August 24, 2023; Revised: August 1, 2023   Accepted: August 4, 2023.  Published online: August 22, 2023.
In this paper, the results of studying the formation conditions, crystal structure, thermal, spectral, and optical properties, as well as the electronic band structure of cobalt-doped zinc glycolate Zn1-xCox(OCH2CH2O) (0<x ≤ 0.2) are presented. Using X-ray powder diffraction data, it was shown that solid solutions are obtained by partial substitution of cobalt for zinc, while maintaining the crystal structure of Zn(OCH2CH2O). The vibrational spectra of Zn1-xCox(OCH2CH2O) are identical to those of Zn(OCH2CH2O) and correlate completely with the results of structural analysis. As a result of heating in air at 600–900 °C, glycolate Zn1-xCox(OCH2CH2O), where 0<x ≤ 0.1, turns into oxide of the composition Zn1-xCoxO with wurtzite structure, whose powders have a deep green color (Rinman’s green). The UV-Vis-NIR spectra of Zn1-xCoxO contain bands typical of Co2+ ion transitions in the tetrahedral environment. When Zn1-xCox(OCH2CH2O) is heated in helium atmosphere, composites (1-x)ZnO:xCo:nC are formed that include a phase with wurtzite structure, metallic cobalt, and elemental carbon. The electronic band structure, optical characteristics, and isosurfaces of wave functions of pure and cobalt-doped zinc glycolate and oxide were calculated. This allowed us to establish the reasons for the increase in the band gap width in glycolate compared to the oxide and its decrease during doping.
Key words: Zinc glycolate · Zinc oxide · Cobalt · Crystal structure · Optical properties · First-principle calculations
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