Spectral and Luminescent Properties of Alkaline Earth Thiogallate Crystals CaGa₂S₄:Tm,Yb at Room Temperature

The photoluminescence (PL) spectra and PL excitation spectra (PLES) of microcrystalline powders of CaGa₂S₄:5%Tm,5%Yb and CaGa₂S₄:5%Tm thiogallates were studied at room temperature. The PLES were measured in the wavelength range from 240 to 850 nm, and the PL spectra were measured in the range of 400–2100 nm with excitation in the UV and violet-blue spectral regions. Microcrystalline gadolinium oxychloride powder GdOCl:5%Tm, in which thulium ions are in the trivalent state (Tm³⁺), was used as a sample for comparison of properties. It was concluded that thiogallates contain thulium ions in both di- and trivalent states (Tm²⁺ and Tm³⁺). In this case, the absorption of excitation energy by the CaGa₂S₄:5%Tm crystal is ensured primarily by the 4_f–5_d transition of the Tm²⁺ ion, while in the CaGa₂S₄:5%Tm,5%Yb compound, it is additionally due to the formation of charge transfer states from CaGa₂S₄ ligand atoms to Yb³⁺ ions. It was shown that in CaGa₂S₄:5%Tm crystals co-activated with Yb³⁺ ions, the photoluminescence efficiency increases many times over compared to non-co-activated crystals, and the effective excitation range extends to 530 nm.

1. K. Eremeev. Broadband Emitting Materials Doped with Thulium and Holmium Ions for Solid-State Lasers at 2 μm and Beyond, Materials Science[cond-mat.mtrl-sci], Normandie Université, English (2024)

2. P. Loiko, J. L. Doualan, L. Guillemot, R. Moncorgé, F. Starecki, A. Benayad, E. Dunina, A. Kornienko, L. Fomicheva, A. Braud, P. Camy. J. Lumin., 225 (2020) 117279, doi: 10.1016/j.jlumin.2020.117279

3. R. Soulard, J. L. Doualan, A. Braud, M. Sahli, A. Benayad, G. Brasse, A. Hideur, A. Tyazhev, R. Moncorgé, P. Camy. Opt. Mater., 72 (2017) 578—582

4. P. A. Loiko, J. M. Serres, X. Mateos, M. P. Demesh, A. S. Yasukevich, K. V. Yumashev, V. Petrov, U. Griebner, M. Aguiló, F. Díaz. Opt. Mater., 51 (2016) 223—231

5. T. Peng, R. Pu, B. Wang, Z. Zhu, K. Liu, F. Wang, W. Wei, H. Liu, Q. Zhan. Biosensors, 11, N 5 (2021), doi: 10.3390/bios11050148

6. V. M. Igba, M. A. Garcia Lobato, C. E. Rodriguez Garcia, A. Garza Santibáñez, J. Oliva Uc, E. Hernández-Hernández, E. Viesca-Villanueva. ISSN 1392-1320 Materials Science (Medžiagotyra), 30, N 2 (2024)

7. P. Solarz, J. Komar, M. Głowacki, M. Berkowski, W. Ryba-Romanowski. RSC Adv., 7, N 34 (2017) 21085—21092, doi.org/10.1039/C7RA01282A

8. Q. Zhang, Z. Liao, L. Qiu, X. Wei, Y. Chen, M. Yin. Dalton Transact., 53, N 34 (2024) 14289—14299, https: doi.org/10.1039/D4DT01480D

9. R. Panda, M. Behera, M. Hegde, R. A. Kumar, G. Venugopal, P. Woźny, K. Soler-Carracedo, M. Runowski. J. Mater. Chem. C, 13 (2025) 8776—8791, doi:10.1039/D4TC05342G

10. I. V. Baklanova, V. N. Krasil’nikov, А. P. Tyutyunnik, Ya. V. Baklanova. J. Lumin., 281 (2025) 121189

11. V. Gaire, M. Y. Do, Y. Pei, A. Semenova, C. V. Parker. Phys. Rev. B, 108 (2023) 214101, https://doi.org/10.1103/PhysRevB.108.214101

12. M. R. N. Soares, M. Ferro, F. M. Costa, T. Monteiro. Nanoscale, 7 (2015) 19958—19969

13. D. Huang, T. Xiao, B. Fu, Sh. Xu, Y. Huang, W. Deng, Zh. Zhou. Crystals, 13, N 3 (2023), https://doi.org/10.3390/cryst13030460

14. A. Bessiere, P. Dorenbos, C. W. E. Van Eijk, E. Yamagishi, C. Hidaka, T. Takizawa. J. Electrochem. Soc., 151, N 12 (2004) H254—H260

15. A. N. Georgobiani, B. G. Tagiev, O. B. Tagiev, R. B. Jabbarov, N. N. Musaeva, U. F. Kasumov. Jpn. J. Appl. Phys., 39 (2000) 434—439, https://doi:10.7567/JJAPS.39S1.434

16. C. Chartier, R. Jabbarov, M. Jouanne, Jean-Francois Morhange, P. Benalloul, C. Barthou, Jean-Marc Frigerio, B. Tagiev, E. Gambarov. J. Phys.: Cond. Matter., 14 (2002) 13693—13703, https://doi:10.1088/0953-8984/14/49/324

17. Sole, L.E. Bausa, D. J. Garcıa Jacque. An Introduction to the Optical Spectroscopy of Inorganic Solids, Chichester, Wiley (2005) 181—191, 199—210

18. M. S. Leanenia, E. V. Lutsenko, M. V. Rzheutski, V. N. Pavlovskii, G. P. Yablonskii, T. G. Naghiyev, B. G. Tagiev, S. A. Abushev, O. B. Tagiyev. J. Lumin., 181 (2017) 121—127

19. Le Thi Thuy My, My Hanh Nguyen Thi, Hoang Thinh Nhan. J. Electron. Eng. Comp. Science, 32, N 1 (2023) 90—97, https://doi:10.11591/ijeecs.v32pp90-97

20. M. C. Nostrand, R. H. Page, S. A. Payne, W. F. Krupke, P. G. Shunemann. Opt. Lett., 24, N 17 (1999) 1215—1217, https://doi.org/10.1364/OL.24.001215

21. P. P. Pershukevich, O. B. Tagiev, T. Sh. Ibragimova, F. A. Kazimova, M. V. Belkov, A. A. Tabolich, E. V. Lutsenko, V. N. Pavlovskii, G. P. Yablonskii. J. Lumin., 275, 120818 (2024), doi: 10.1016/j.jlumin.2024.120818

22. P. P. Pershukevich, O. B. Tagiev, E. G. Asadov, T. Sh. Ibragimova, F. A. Kazimova, M. V. Belkov, E. V. Lutsenko, A. V. Mudryi, V. N. Pavlovskii, G. P. Yablonskii. J. Appl. Spectr., 92 (2025) 256—264

23. Е. Nakazawa. Chem. Phys. Lett., 56 (1978) 161—163

24. L. van Pieterson, M. Heeroma, E. de Heer, A. Meijerink. J. Lumin., 91, N 3-4 (2000) 177—193

25. Y. H. Kim, Un-Ch. Paek, W.-T. Han. Opt. Soc. Am., Opt. Express, 2673, N 21 (2003) 3065

26. J. Grimm, K. W. Krämer, H. U. Güdel. J. Lumin., 126, N 2 (2007) 590—596

27. M. Karbowiak, R. Lisiecki, P. Solarz, J. Komar, W. Ryba-Romanowski. J. Alloys and Compd., 74 (2018) 1165—1171

28. M. P. Plokker, S. Vlaar, A. H. J. Bakx, Erik van der Kolk, P. Dorenbos, H. T. Hintzen. J. Phys. Chem. C, 127 (2023) 19017—19026

29. C. Schornig, M. Stef, G. Buse, M. Poienar, Ph. Veber, D. Vizman. Materials, 17, N 20 (2024) 4965, https://doi.org/10.3390/ma17204965

30. E. Radzhabov, R. Shendrik, V. Pankratov. J. Lumin., 252 (2022) 119271, https://doi.org/10.1016/j.jlumin.2022.119271

31. T. M. Kozhan, V. V. Kuznetsova, P. P. Pershukevich, I. I. Sergeev, V. S. Khomenko, V. A. Chernyavskii. J. Appl. Spectr., 71, N 6 (2004) 829—836

32. Y. Li, Y. Li, R. Wang, Y. Xu, W. Zheng. New. J. Chem., 41 (2017) 7116—7122, https://doi.org/10.1039/c7nj01358b