Skip to main content

Trivalent Gadolinium-Doped Diopside (CaMgSi2O6) for Photoluminescence and EPR Investigation

Abstract

Gd3+-doped CaMgSi2O6 phosphors with varying dopant content were processed successfully using sol-gel preparation. Prepared products were verified by x-ray diffraction data, which indicated the formation of a monoclinic phase. Scanning electron microscopy suggested the formation of tightly aggregated phosphor particles. A strong photoluminescence emission peak of 6P7/2 → 8S7/2 at 313 nm was observed in the studied phosphors under 273-nm excitation. The changes in emission intensity were also monitored with respect to the concentration of Gd3+. X-band electron paramagnetic resonance (EPR) spectra of the phosphors revealed the fine structure lines of Gd3+ ions typical of orthorhombic or lower symmetry. In addition, the intensity of the EPR spectrum from Gd3+ showed saturation beyond 0.03 mol of Gd3+ doping.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

References

  1. H. Zhang, X. Zhang, Z. Cheng, Y. Xu, J. Yang, and F. Meng, Tunable Luminescence of K2MgSi3O8:Ce3+, Tb3+ Phosphors Through Energy Transfer. Ceram. Int. 44, 2547 (2018).

    CAS  Article  Google Scholar 

  2. J. Zhang, X. Li, and G. Chen, Upconversion Luminescence of Ba9Y2Si6O24:Yb3+-Ln3+ (Ln = Er, Ho, and Tm) Phosphors for Temperature Sensing. Mater. Chem. Phys. 206, 40 (2018).

    CAS  Article  Google Scholar 

  3. F. Wang, W. Wang, and Y. Jin, Photoluminescence Properties of Ce3+/Mn2+ Doped Calcium Zirconium Silicate Phosphors with Energy Transfer for White LEDs. Ceram. Int. 42, 16626 (2016).

    CAS  Article  Google Scholar 

  4. P. Dewangan, D.P. Bisen, N. Brahme, R.K. Tamrakar, K. Upadhyay, S. Sharma, and I.P. Sahu, Studies on Thermoluminescence Properties of Alkaline Earth Silicate Phosphors. J. Alloys Compd. 735, 1383 (2018).

    CAS  Article  Google Scholar 

  5. L. Jiang, C. Chang, D. Mao, and B. Zhang, A New Long Persistent Blue-Emitting Sr2ZnSi2O7:Eu2+, Dy3+ Prepared by Sol-Gel Method. Mater. Lett. 58, 1825 (2004).

    CAS  Article  Google Scholar 

  6. K. Oguri, N. Funamori, F. Sakai, T. Kondo, T. Uchida, and T. Yagi, High-Pressure and High-Temperature Phase Relations in Diopside CaMgSi2O6. Phys. Earth Planet. Inter. 104, 363 (1997).

    CAS  Article  Google Scholar 

  7. M.-W. Chang, S.H. Lyoo, H.S. Choo, and J.M. Lee, Properties of Glasses Based on the CaO-MgO-SiO2 System for Low-Temperature Co-Fired Ceramic. Ceram. Int. 35, 2513 (2009).

    CAS  Article  Google Scholar 

  8. H. Takei, T. Miura, and M. Morioka, Czochralski Growth of Diopside (CaMgSi2O6) Crystals. J. Cryst. Growth 60, 453 (1982).

    CAS  Article  Google Scholar 

  9. H. Wang, S. Xu, S. Zhai, D. Deng, and H. Ju, Effect of B2O3 Additives on the Sintering and Dielectric Behaviors of CaMgSi2O6 Ceramics. J. Mater. Sci. Technol. 26, 351 (2010).

    Article  Google Scholar 

  10. B.K. Choi and E.S. Kim, Effects of Crystallization Behavior on Microwave Dielectric Properties of CaMgSi2O6 Glass-Ceramics. J. Kor. Ceram. Soc. 50, 70 (2013).

    CAS  Article  Google Scholar 

  11. T. Joseph, M.T. Sebastian, H. Sreemoolanadhan, and V.K.S. Nageswari, Effect of Glass Addition on the Microwave Dielectric Properties of CaMgSi2O6 Ceramics. Appl. Cram. Soc. Technol. 7, 98 (2010).

    Article  Google Scholar 

  12. R.Q. Wang, Tb3+ Doped CaMgSi2O6-Based Green Phosphor. Adv. Mater. Res. 187, 394 (2011).

    CAS  Article  Google Scholar 

  13. L. Jiang, C. Chang, D. Mao, and C. Feng, Luminescent Properties of CaMgSi2O6-Based Phosphors co-Doped with Different Rare Earth Ions. J. Alloys. Compd. 377, 211 (2014).

    Article  Google Scholar 

  14. W.B. Im, J.H. Kang, D.C. Lee, S. Lee, D.Y. Jeon, Y.C. Kang, and K.Y. Jung, Origin of PL Intensity Increase of CaMgSi2O6:Eu2+ Phosphor After Baking Process for PDPs Application. Solid State Commun. 133, 197 (2005).

    CAS  Article  Google Scholar 

  15. K.Y. Jung, K.H. Han, Y.C. Kang, and H.-K. Jung, Preparation of CaMgSi2O6: Eu Blue Phosphor Particles by Spray Pyrolysis and its VUV Characteristics. Mater. Chem. Phys. 98, 330 (2006).

    CAS  Article  Google Scholar 

  16. A.U. Pawar, A.P. Jadhav, U. Pal, B.Y.K. Kim, and Y.S. Kang, Blue and Red Dual Emission Nanophosphor CaMgSi2O6:Eun+; Crystal Structure and Electronic Configuration. J. Lumin. 132, 659 (2012).

    CAS  Article  Google Scholar 

  17. U. Pawar, A.P. Jadhav, C.W. Kim, H.Y. Cha, U. Pal, and Y.S. Kang, Emission Controlled Dual Emitting Eu-Doped CaMgSi2O6 Nanophosphors. J. Lumin. 157, 131 (2015).

    CAS  Article  Google Scholar 

  18. S. Choi, S.W. Tae, J.H. Seo, and H.K. Jung, Preparation of Blue-Emitting CaMgSi2O6:Eu2+ Phosphors in Reverse Micellar System and their Application to Transparent Emissive Display Devices. J. Solid State Chem. 184, 1540 (2011).

    CAS  Article  Google Scholar 

  19. C. Rosticher, B. Viana, G. Laurent, P. Le Griel, and C. Chanéa, Insight into CaMgSi2O6:Eu2+, Mn2+, Dy3+ Nanoprobes: Influence of Chemical Composition and Crystallinity on Persistent Red Luminescence. Eur. J. Inorg. Chem. 2015, 3681 (2015).

    CAS  Article  Google Scholar 

  20. P. Chandrakar, D.P. Bisen, R.N. Baghel, and B.P. Chandra, Synthesis and Optical Properties of CaMgSi2O6:Ce3+ Phosphors. J. Electron. Mater. 44, 3450 (2015).

    CAS  Article  Google Scholar 

  21. J. Kong, Z. Liu, D. Cai, Y. Fan, P. Zhao, X. Liu, P. Pu, L. Song, and C. He, A Gadolinium-Based Magnetic Resonance Imaging Contrast Agent for Nucleotides Sensing. Sens. Actuators B Chem. 256, 913 (2018).

    CAS  Article  Google Scholar 

  22. F. Zheng, X. Ou, Q. Pan, X. Xiong, C. Yang, Z. Fu, and M. Liu, Nanoscale Gadolinium Doped Ceria (GDC) Surface modification of Li-Rich Layered Oxide as a High Performance Cathode Material for Lithium Ion Batteries. Chem. Eng. J. 334, 497 (2018).

    CAS  Article  Google Scholar 

  23. R.R. Kanna, N. Lenin, K. Sakthipandi, and A.S. Kumar, Structural, Optical, Dielectric and Magnetic Studies of Gadolinium-Added Mn-Cu Nanoferrites. J. Magn. Magn. Mater. 453, 78 (2018).

    CAS  Article  Google Scholar 

  24. A.O. Chauhan, N.S. Bajaj, and S.K. Omanwar, Synthesis and Photoluminescence Study of Narrow-Band UVB-Emitting LiSr4(BO3)3:Gd3+, Pr3+ Phosphor. Bull. Mater. Sci. 40, 1 (2017).

    CAS  Article  Google Scholar 

  25. C.H. Huang, T.M. Chen, and B.M. Cheng, Luminescence Investigation on Ultraviolet-Emitting Rare-Earth-Doped Phosphors Using Synchrotron Radiation. Inorg. Chem. 50, 6552 (2011).

    CAS  Article  Google Scholar 

  26. P.P. Mokoena, I.M. Nagpure, V. Kumar, R.E. Kroon, E.J. Olivier, J.H. Neethling, H.C. Swart, and O.M. Ntwaeaborw, Enhanced UVB Emission and Analysis of Chemical States of Ca5(PO4)3OH:Gd3+, Pr3+ Phosphor Prepared by Co-Precipitation. J. Phys Chem Solids 75, 998 (2014).

    CAS  Article  Google Scholar 

  27. S. Rast, A. Borel, L. Helm, E. Belorizky, P.H. Fries, and A.E. Merbach, EPR Spectroscopy of MRI-Related Gd(III) Complexes: Simultaneous Analysis of Multiple Frequency and Temperature Spectra, Including Static and Transient Crystal Field Effects. J. Am. Chem. Soc. 123, 2637 (2001).

    CAS  Article  Google Scholar 

  28. V. Singh, G. Sivaramaiah, J.L. Rao, S.H. Kim, Optical and EPR Studies of Gd2Zr2O7 Phosphors Prepared via Solution Combustion Method, Physica B, 416, 101 (2013).

  29. V. Singh, G. Sivaramaiah, J.L. Rao, S. Watanabe, T.G. Rao, S.S. Jagtap, and P.K. Singh, New Ultraviolet B Emission from Gadolinium Activated BaZrO3 Phosphor-An Electron Paramagnetic Resonance and Optical Study. J. Alloys Compd. 648, 1083 (2015).

    CAS  Article  Google Scholar 

  30. G. Krishna Reddy, A. Jagannatha Reddy, R. Hari Krishna, B.M. Nagabhushana, and G.R. Gopal, Luminescence and Spectroscopic Investigations on Gd3+ Doped ZnO Nanophosphor. J. Asian Ceram. Soc. 5, 350 (2017).

    Article  Google Scholar 

  31. A.D. Gorlov, Temperature Dependences of the Parameters of the Initial Splitting of Gd3+ in CaMoO4 (Lattice and Spin–Phonon Contributions). Phys. Solid State 59, 578 (2017).

    CAS  Article  Google Scholar 

  32. S. Tomboli, R.M. Kadam, and S.J. Dhoble, Photoluminescence and Electron Paramagnetic Resonance Properties of a Potential Phototherapic Agent: MMgF4:Gd3+ (M = Ba, Sr) Sub-Microphosphors. Luminescence 31, 1321 (2016).

    Article  Google Scholar 

  33. V. Singh, G. Sivaramaiah, J.L. Rao, R. Senthil Kumaran, P.K. Singh, T.S. Kim, and L.K. Kim, Luminescence and EPR Studies of Ultraviolet Light Emitting La2Zr2O7: Gd3+ Phosphor Powder. J. Mater. Sci. Mater. Electron. 26, 5195 (2015).

    CAS  Article  Google Scholar 

  34. M.S. Pathak, N. Singh, V. Singh, S. Watanabe, T.G. Rao, and J.K. Lee, Narrowband Ultraviolet B Emission from Gadolinium Activated Y3Ga5O12 Nano-Garnets. Mater. Res. Bull. 97, 512 (2018).

    CAS  Article  Google Scholar 

  35. K. Momma and F. Izumi, VESTA 3 for Three-Dimensional Visualization of Crystal, Volumetric and Morphology Data. J. Appl. Crystallogr. 44, 1272 (2011).

    CAS  Article  Google Scholar 

  36. B.N. Sherikar, B. Sahoo, and A.M. Umarji, One-Step Synthesis of diopside (CaMgSi2O6) Ceramic Powder by Solution Combustion Method. Adv. Powder Technol. 31, 3492 (2020).

    CAS  Article  Google Scholar 

  37. M. Raudsepp, F.C. Hawthorne, and A.C. Turnock, Crystal Chemistry of Synthetic Pyroxenes on the Join CaNiSi2O6-CaMgSi2O6 (Diopside); A RIETVELD Structure Refinement Study. Am. Miner. 75, 1274 (1990).

    CAS  Google Scholar 

  38. Y. Hu, B. Kiefer, C.R. Bina, D. Zhang, and P.K. Dera, High-Pressure γ-CaMgSi2O6: Does Penta-Coordinated Silicon Exist in the Earth’s Mantle. Geophys. Res. Lett. 44, 11340 (2017).

    Article  Google Scholar 

Download references

Acknowledgments

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (No. 2021R1A2C1092509). This paper was supported by the KU Research Professor Program of Konkuk University.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Vijay Singh.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 798 KB)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Singh, V., Nandyala, S.H., Natarajan, V. et al. Trivalent Gadolinium-Doped Diopside (CaMgSi2O6) for Photoluminescence and EPR Investigation. J. Electron. Mater. 51, 5521–5527 (2022). https://doi.org/10.1007/s11664-022-09856-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11664-022-09856-5

Keywords

  • Luminescence
  • EPR
  • Gd3+
  • CaMgSi2O6
  • phosphor
  • sol–gel