Skip to main content
SpringerLink
Log in

Theoretical Studies of the Local Structure and EPR Parameters of Tetragonally Distorted Tetrahedral Cu2+ Sites in Phosphate Glasses

  • Published:
Glass Physics and Chemistry Aims and scope Submit manuscript

Abstract

In this work, we theoretically investigate the local structure and electronic paramagnetic resonance (EPR) parameters (g-factors gi and A-constants Ai, i = //, ⊥) of tetragonal Cu2+ centers in phosphate glasses (xCuO⋅(1 – x)[2P2O5⋅Na2O] (0.5< x < 5 mol %)) with the aid of the three-order perturbation formulae of these parameters for 3d9 ions in tetragonally distorted tetrahedra based on the cluster approach. In our calculations, both contributions to EPR parameters from the spin-orbit (SO) coupling interactions of the central Cu2+ ions and the ligand orbital and SO coupling interactions are included. The crystal-field parameters related to the splitting of d-orbitals are calculated from the superposition model and the local structures of the studied Cu2+ centers in the glasses. Based on the calculations, the local bond angle is found to be about 3.78° larger than that of the ideal tetrahedral site, resulting in a slightly compressed ligand tetrahedron. The relative contributions to the g-factors from the ligand orbital and SO coupling interactions are more important than those from the third-order perturbation terms. The theoretical results show good agreement with the experimental values. The signs and the less anisotropy (ΔA = |A//| – |A⊥| ) of A-constants for the tetrahedral Cu2+ centers are discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1.
Fig. 2.
Fig. 3.

Similar content being viewed by others

REFERENCES

  1. Wantana, N., Ruangtaweep, Y., Kaewnuam, E., Kang, S.C., Kim, H.J., Kothan, S., and Kaewkhao, J., Development of WO3–Gd2O3–B2O3 high density glasses doped with Dy3+ for photonics and scintillation materials application, Solid State Sci., 2020, vol. 101, 106135.

    Article  CAS  Google Scholar 

  2. Macrelli, G., Varshneya, A.K., and Mauro, J.C., Ultra-thin glass as a substrate for flexible photonics, Opt. Mater., 2020, vol. 106, 109994.

    Article  CAS  Google Scholar 

  3. Rajagukguk, J., Situmorang, R., Djamal, M., Rajaramakrishna, R., Kaewkhao, J., and Minh, P.H., Structural, spectroscopic and optical gain of Nd3+ doped fluorophosphate glasses for solid state laser application, J. Lumin., 2019, vol. 216, 116738.

    Article  CAS  Google Scholar 

  4. Jamalaiah, B.C., Madhu, N., Rao, K.V., Viswanadha, G., and Ram, D.V.R., Enhanced red luminescent PBTNAEu glasses for solid state lasers, J. Lumin., 2020, vol. 223, 117200.

    Article  CAS  Google Scholar 

  5. Lakshminarayana, G., Kaky, K.M., Baki, S.O., Lira, A., Meza-Rocha, A.N., Falcony, C., Caldiño, U., Kityk, I.V., Méndez-Blas, A., Abas, A.F., Alresheedi, M.T., and Mahdi, M.A., Nd3+-doped heavy metal oxide based multicomponent borate glasses for 1.06 μm solid-state NIR laser and O-band optical amplification applications, Opt. Mater., 2018, vol. 78, pp. 142–159.

    Article  CAS  Google Scholar 

  6. Shi, D.Y., Lin, S.B., Zhao, X.X., Feng, A.L., and Xu, Q., Near-infrared quantum cutting in Tm3+/Yb3+-doped phosphate glasses, Results Phys., 2020, vol. 19, 103411.

    Article  Google Scholar 

  7. Morshidy, H.Y., Abd El-Fattah, Z.M., Abul-Magd, A.A., Hassan, M.A., and Mohamed, A.R., Reevaluation of Cr6+ optical transitions through Gd2O3 doping of chromium-borate glasses, Opt. Mater., 2021, vol. 113, 110881.

    Article  CAS  Google Scholar 

  8. El-Adawy, A., Khaled, N.E., El-Sersy, A.R., Hussein, A., and Donya, H., TL dosimetric properties of Li2O-B2O3 glasses for gamma dosimetry, Appl. Radiat. Isotopes, 2010, vol. 68, no. 6, pp. 1132–1136.

    Article  CAS  Google Scholar 

  9. Inês Teixeira, M., da Costa, Z.M., da Costa, C.R., Pontuschka, W.M., and Caldas, L.V.E., Study of the gamma radiation response of watch glasses, Radiat. Meas., 2008, vol. 43, no. 2, pp. 480–482.

    Article  Google Scholar 

  10. Kawano, N., Kawaguchi, N., Okada, G., Fujimoto, Y., and Yanagida, T., Scintillation and dosimetric properties of Ce-doped strontium aluminoborate glasses, J. Non-Cryst. Solids, 2018, vol. 482, pp. 154–159.

    Article  CAS  Google Scholar 

  11. Ding, C.C., Wu, S.Y., Wu, L.N., Zhang, L.J., Peng, L., Wu, M.H., and Teng, B.H., Theoretical study of the local structures and the EPR parameters for RLNKB glasses with VO2+ and Cu2+ dopants, J. Phys. Chem. Solids, 2018, vol. 113, pp. 102–107.

    Article  CAS  Google Scholar 

  12. Chahine, A., Et-tabirou, and Pascal, J.L., FTIR and Raman spectra of the Na2O–CuO–Bi2O3–P2O5 glasses, Mater. Lett., 2004, vol. 58, pp. 2776–2780.

    Article  CAS  Google Scholar 

  13. Silva, A.M.B., Queiroz, C.M., Agathopoulos, S., Correia, R.N., Fernandes, M.H.V., and Oliveira, J.M., J. Mol. Struct., 2011, vol. 986, pp. 16–21.

    Article  CAS  Google Scholar 

  14. Ahmed, M.R. and Shareefuddin, M., EPR, optical, physical and structural studies of strontium alumino-borate glasses containing Cu2+ ions, SN Appl. Sci., 2019, vol. 1, no. 3, 209.

    Article  Google Scholar 

  15. Kaur, A., Khanna, A., Bhatt, H., Gónzález-Barriuso, M., González, F., Chen, B.H., and Deo, M.N., BO and TeO speciation in bismuth tellurite and bismuth borotellurite glasses by FTIR, 11B MAS-NMR and Raman spectroscopy, J. Non-Cryst. Solids, 2017, vol. 470, pp. 19–26.

    Article  CAS  Google Scholar 

  16. Srinivas, B., Hameed, A., Ramadevudu, G., Chary, M.N., and Shareefuddin, M., Evaluation of EPR parameters for compressed and elongated local structures of VO2+ and Cu2+ spin probes in BaO–TeO2–B2O3 glasses, J. Phys. Chem. Solids, 2019, vol. 129, pp. 22–30.

    Article  CAS  Google Scholar 

  17. Bale, S. and Rahman, S., Studies of mixed former effect in EPR and optical absorption in xZnO–(75 – x)Bi2O3–15B2O3–10Li2O glasses, Phys. B (Amsterdam, Neth.), 2013, vol. 418, pp. 52–57.

    Google Scholar 

  18. Sangeetha, G., Sekhar, K.C., Hameed, A., Ramadevudu, G., Chary, M.N., and Shareefuddin, M., Influence of CaO on the structure of zinc sodium tetra borate glasses containing Cu2+ ions, J. Non-Cryst. Solids, 2021, vol. 563, 120784.

    Article  CAS  Google Scholar 

  19. Wang, Y.M., Wu, S.Y., Jiang, S.J., Luo, Y.J., Zhu, Q.S., and Han, M., Investigations of defect structures for V4+ in CBPB glasses with distinct V2O5 contents, J. Non-Cryst. Solids, 2021, vol. 566, 120879.

    Article  CAS  Google Scholar 

  20. Wang, Y.M., Wu, S.Y., Jiang, S.J., Zhu, Q.S., and Han, M., Studies on spin Hamiltonian parameters and local structures for V4+ in BaCl2–BaO–B2O3 glasses at various BaCl2 compositions, Philos. Mag., 2020, vol. 100, no. 21, pp. 2772–2784.

    Article  CAS  Google Scholar 

  21. Liu, X.S., Wu, S.Y., Shen, G.Q., Yu, X.Y., Zhu, Q.S., and Li, X.Y., Theoretical analysis on lead halides content dependences of defect structures and spin Hamiltonian parameters in lead halo borate glass composites with V2O5 dopants, Composites, Part A, 2021, vol. 146, 106414.

    Article  CAS  Google Scholar 

  22. Pujari, N., Birampally, K., Edukondalu, A., and Vardhani, C.P., Effect of Li2O content on structural and optical properties of Li2O–TeO2–As2O3–B2O3 glasses, J. Phys. Chem. Solids, 2021, vol. 148, 109627.

    Article  CAS  Google Scholar 

  23. Li, Y.D., Chen, B.J., Zhang, H.M., and Feng, C.D., Theoretical study of the local distortions and the EPR parameters for VO2+ and Cu2+ centers in oxyfluoroborate glasses, J. Lumin., 2021, vol. 234, 117973.

    Article  CAS  Google Scholar 

  24. Sreehari Sastry, S., Prasad, M.V.V., K., Venkateswara Rao, B.R., and Sivaramakrishna, J., Effect of alkali modifier ion on spectroscopic properties of Cu2+-doped lead zinc phosphate glass system, Indian J. Phys., 2015, vol. 89, no. 11, pp. 1169–1175.

    Article  CAS  Google Scholar 

  25. Bogomolova, L.D., Zhachkin, V.A., and Pavlushkina, T.K., Development of green light filters based on high-resistance oxide glasses colored by transition elements, Glass. Ceram., 2012, vol. 69, no. 1, pp. 50–54.

    Article  CAS  Google Scholar 

  26. Cozar, O. and Ardelean, I., The local symmetry of Cu2+ ions in phosphate glasses, J. Non-Cryst. Solids, 1987, vol. 92, no. 2, pp. 278–281.

    Article  CAS  Google Scholar 

  27. Cozar, O. and Ardelean, I., Local structure and metal-metal interaction in some phosphate glasses, J. Optoelectron. Adv. Mater., 2003, vol. 5, no. 1, pp. 177–183.

    CAS  Google Scholar 

  28. Cozar, O., Ardelean, I., Simon, V., David, L., Vedean, N., and Mih, V., EPR studies of Cu2+ and V4+ ions in phosphate glasses, Appl. Magn. Reson., 1999, vol. 16, no. 4, pp. 473–480.

    Article  CAS  Google Scholar 

  29. Cozar, O., Magdas, D.A., and Ardelean, I., EPR study of molybdenum-lead-phosphate glasses, J. Non-Cryst. Solids, 2008, vol. 354, no. 10, pp. 1032–1035.

    Article  CAS  Google Scholar 

  30. Garbarczyk, J.E., Machowski, P., Wasiucionek, M., Tykarski, L., Bacewicz, R., and Aleksiejuk, A., Studies of silver-vanadate-phosphate glasses by Raman, EPR and impedance spectroscopy methods, Solid State Ionics, 2000, vols. 136–137, pp. 1077–1083.

    Article  Google Scholar 

  31. De Vicente, F.S., Santos, F.A., Simões, B.S., Dias, S.T., and Siu Li, M., EPR, optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses, Opt. Mater., 2014, vol. 38, pp. 119–125.

    Article  CAS  Google Scholar 

  32. Giridhar, G., Rangacharyulu, M., Ravikumar, R.V.S., and Rao, P.S., Electron paramagnetic resonance and optical absorption studies on copper ions in mixed alkali cadmium phosphate glasses, J. Mater. Sci. Technol., 2009, vol. 25, no. 4, pp. 531–534.

    CAS  Google Scholar 

  33. Sumalatha, B., Omkaram, I., Rao, T.R., and Raju, C.L., Alkaline earth zinc borate glasses doped with Cu2+ ions studied by EPR, optical and IR techniques, J. Non-Cryst. Solids, 2011, vol. 357, no. 16, pp. 3143–3152.

    Article  CAS  Google Scholar 

  34. Siva Ramaiah, G. and Lakshmana Rao, J., Electron spin resonance and optical absorption spectroscopic studies of Cu2+ ions in aluminium lead borate glasses, J. Alloys Compd., 2013, vol. 551, pp. 399–404.

    Article  CAS  Google Scholar 

  35. Kuang, M.Q., Wang, L.D., and Duan, S.K., Local distortion and EPR parameters of copper(II) in borate glasses, J. Phys. Chem. Solids, 2017, vol. 111, pp. 41–46.

    Article  CAS  Google Scholar 

  36. Xu, Y.Q., Wu, S.Y., Zhang, L.J., and Ding, C.C., Investigations on the EPR parameters and defect structures for Cu2+ in alkaline earth zinc borate glasses, Optik, 2016, vol. 127, no. 20, pp. 9167–9171.

    Article  CAS  Google Scholar 

  37. Zhang, H.M., Duan, J.H., Xiao, W.B., and Wan, X., Theoretical studies of the local structure of Cu2+ center in aluminium lead borate glasses by their EPR and optical spectra, J. Non-Cryst. Solids, 2015, vol. 425, pp. 173–175.

    Article  CAS  Google Scholar 

  38. Wu, Y. and Chen, Z., Investigation of the local structure of Cu2+ ions doped in alkali lead tetraborate glasses by their electron paramagnetic resonance and optical spectra, Radiat. Eff. Defects Solids, 2014, vol. 169, no. 6, pp. 485–489.

    Article  CAS  Google Scholar 

  39. Bogomolova, L.D., Fedorov, A.G., Jachkin, V.A., Lazukin, V.N., and Pavlushkina, T.K., A new paramagnetic center of copper ion in γ-irradiated phosphate glasses, J. Non-Cryst. Solids, 1981, vol. 44, no. 1, pp. 191–194.

    Article  CAS  Google Scholar 

  40. Bogomolova, L.D., Federov, A.G., Jachkin, V.A., and Lazukin, V.N., EPR spectra of irradiated oxide glasses containing copper, J. Non-Cryst. Solids, 1980, vols. 38–39, pp. 159–161.

    Article  Google Scholar 

  41. Zhang, H.M. and Xiao, W.B., Investigations on the EPR parameters and defect structures due to Jahn-Teller effect for the Cu2+ and Ni+ centers in LiNbO3, J. Alloys Compd., 2018, vol. 745, pp. 586–591.

    Article  CAS  Google Scholar 

  42. Zhang, H.M., Li, Y.D., Chen, B.J., Feng, C.D., and Fu, Y.J., Theoretical studies on the spin Hamiltonian parameters and the local structure for Cu2+ in rutile, J. Alloys Compd., 2020, vol. 827, 154294.

    Article  CAS  Google Scholar 

  43. Wei, L.H., Wu, S.Y., Zhang, Z.H., Wang, H., and Wang, X.F., Investigations on the local structure and the EPR parameters for Cu2+-doped GaN, Mod. Phys. Lett. B, 2008, vol. 22, no. 18, pp. 1739–1747.

    Article  CAS  Google Scholar 

  44. Wu, S.Y., Zhang, H.M., Dong, H.N., Wang, X.F., and Hu, Y.X., Theoretical investigations of the local structures and the g factors for 3d9 ions in CdS, Phys. Chem. Miner., 2009, vol. 36, no. 9, pp. 483–487.

    Article  CAS  Google Scholar 

  45. Wu, S.Y., Zhang, H.M., Xu, P., and Zhang, S.X., Studies on the defect structure for Cu2+ in CdSe nanocrystals, Spectrochim. Acta, Part A, 2010, vol. 75, no. 1, pp. 230–234.

    Article  Google Scholar 

  46. Bates, C.A., Moore, W.S., Standley, K.J., and Stevens, K.W.H., Paramagnetic resonance of Cu2+ion in a tetrahedral crystal field, Proc. Phys. Soc., 1962, vol. 79, no. 1, pp. 73–83.

    Article  CAS  Google Scholar 

  47. Abragam, A. and Bleaney, B., Electron Paramagnetic Resonance of Transition Ions, Oxford: Clarendon, 1970, pp. 417–465.

    Google Scholar 

  48. Newman, D.J. and Ng, B., The superposition model of crystal fields, Rep. Prog. Phys., 1989, vol. 52, no. 6, pp. 699–762.

    Article  CAS  Google Scholar 

  49. David, R.L., CRC Handbook of Chemistry and Physics, Boca Raton: CRC, 2005, pp. 12–14.

    Google Scholar 

  50. Fang, W. and Zheng, W.C., Studies of the spin-Hamiltonian parameters and the defect structure for Cu2+ at the rhombic Be2+ site of beryl crystal, Phys. B (Amsterdam, Neth.), 2009, vol. 404, no. 14, pp. 2025–2027.

  51. McGarvey, B.R., The isotropic hyperfine interaction, J. Phys. Chem., 1967, vol. 71, no. 1, pp. 51–66.

    Article  CAS  Google Scholar 

  52. Karlsson, K., Linear trends aiding interpretation and prediction of optical spectra of transition metal ions, Scr. Mater., 1973, vol. 3, no. 5, pp. 201–205.

    CAS  Google Scholar 

  53. Jorgensen, C.K., Absorption Spectra and Chemical Bonding in Complexes, New York: Pergamon, 1962, p. 113.

    Google Scholar 

  54. Clementi, E. and Raimondi, D.L., Atomic screening constants from SCF functions, J. Chem. Phys., 1963, vol. 38, no. 11, pp. 2686–2689.

    Article  CAS  Google Scholar 

  55. Clementi, E., Raimondi, D.L., and Reinhardt, W.P., Atomic screening constants from SCF functions. II. Atoms with 37 to 86 electrons, J. Chem. Phys., 1967, vol. 47, no. 4, pp. 1300–1307.

    Article  CAS  Google Scholar 

  56. Tominaga, H., Ono, Y., and Keii, T., Spectroscopic study of Cu(II) ions supported on silica gel by cation exchange method, J. Catal., 1975, vol. 40, pp. 197–202.

    Article  CAS  Google Scholar 

  57. Cozar, O., Znamirovschi, V., and Gridan, M., ESR study of the dispersion mode of Cu(II) and VO(II) ions adsorbed on SiO2 and Al2O3 surfaces, Rev. Roum. Phys., 1982, vol. 27, pp. 389–394.

    CAS  Google Scholar 

  58. Guo, J.X., Wu, S.Y., Kuang, M.Q., Peng, L., and Wu, L.N., Theoretical studies of the local structures and spin Hamiltonian parameters for Cu2+ in alkaline earth alumino borate glasses, Mod. Phys. Lett. B, 2017, vol. 32, no. 02, 1750331.

    Article  Google Scholar 

  59. Wei, W.H., Lu, M., Hou, C.J., Liu, W.Q., and Pan, X.Q., Theoretical investigation of the spin-Hamiltonian parameters and optical spectra for the doped Cu2+ in ZnCdO nanopowder, Radiat. Eff. Defects Solids, 2014, vol. 169, no. 11, pp. 913–918.

    Article  CAS  Google Scholar 

Download references

Funding

This research was funded by the scientific research startup fund of Jiangsu University of Science and Technology (Grant no. 120170003) and University Natural Science Research Project of Anhui Province (Grant no. KJ2019A0049).

Author information

Authors and Affiliations

  1. Department of Electronic Information Engineering, Suzhou Institute of Technology, Jiangsu University of Science and Technology, 215600, Zhangjiagang, P. R. China

    B. F. Zhang

  2. Department of Physics, Suzhou Institute of Technology, Jiangsu University of Science and Technology, 215600, Zhangjiagang, P. R. China

    J. Z. Lin, Y. Zhao & Y. F. Zhang

  3. School of Mathematics and Physics, AnHui University of Technology, 243032, Ma’anshan, P. R. China

    Y. F. Han

Authors
  1. B. F. Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. Z. Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Y. Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Y. F. Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Y. F. Han
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to J. Z. Lin.

Ethics declarations

The authors declare that they have no conflicts of interest.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, B.F., Lin, J.Z., Zhao, Y. et al. Theoretical Studies of the Local Structure and EPR Parameters of Tetragonally Distorted Tetrahedral Cu2+ Sites in Phosphate Glasses. Glass Phys Chem 48, 511–518 (2022). https://doi.org/10.1134/S1087659621100461

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1087659621100461

Keywords:

Search

Navigation