Electric and optical properties of Tm3+/Yb3+co-doped PZN–9PT crystals

  • Ying Li
  • Zengzhe XiEmail author
  • Pinyang Fang
  • Xiaojuan Li
  • Wei Long
  • Aiguo He
  • Wei Zhao


Tm3+/Yb3+co-doped Pb(Zn1/3Nb2/3)O3–9PbTiO3 (PZN–9PT) single crystals were grown by high-temperature flux technique. The effects of Tm3+/Yb3+ ions doping on phase structure, dielectric, ferroelectric and UC luminescence properties were investigated. The XRD, Raman spectrum and TEM results reveal that the Tm3+/Yb3+ ions can diffuse into the lattice of the PZN–9PT and increase the lattice constants. The Curie temperature Tc increases from 170 °C for pure PZN–9PT to 182.5 °C for PZN–9PT: Tm3+/Yb3+. Meanwhile, the coercive field Ec of Tm3+/Yb3+ co-doped PZN–9PT reaches to 12.1 kV/cm which is nearly four times higher than that of PZN–9PT crystal. Under a 980 nm laser excitation, crystals modified by the Tm3+/Yb3+ produce UC with three colors: blue (480 nm, 1G4 → 3H6), strong near-infrared (NIR, 804 nm, 3H4 → 3H6) and weak red (652 nm, 1G4 → 3F4). Our results can provide a new way for the design of multifunctional materials used in optical-electrical devices.



This work was supported by the National Natural Science Foundation of China (Grant No. 51772235), the National Basic Research Program of China (973 Program) (Grant No. 2013CB632900),the Shaanxi Key Laboratory Fundament Research Foundation (Grant No. 14JK1333) and Shaanxi Key Laboratory of Optoelectronic Functional Materials and Devices (Grant No. 2015SZSJ-59-5).


  1. 1.
    T. Li, X.F. Long, M. Ye, H.R. Wang, H.T. Huang, X.R. Zeng, S.M. Ke, Growth and properties of (1–x)Pb(Zn1/3Nb2/3)O3xPbTiO3 (x = 0.07–0.11) ferroelectric single crystals by a top-seeded solution growth method. Ceram. Int. 41, 14427–14434 (2015)CrossRefGoogle Scholar
  2. 2.
    L.A. Reznitchenko, I.A. Verbenko, O.N. Razumovskaya, L.A. Shilkina, Preparation, structure and piezoelectric properties of PZN-PMN-PT ceramics in the composition range of large PZN concentrations. Ceram. Int. 38, 3835–3839 (2012)CrossRefGoogle Scholar
  3. 3.
    S.J. Zhang, L. Lebrun, D.Y. Jeong, C.A. Randall, Q.M. Zhang, Growth and characterization of Fe-doped Pb(Zn1/3Nb2/3)O3-PbTiO3 single crystals. J. Appl. Phys. 93, 9257–9262 (2003)CrossRefGoogle Scholar
  4. 4.
    H.X. Fu, R.E. Cohen, Polarization rotation mechanism for ultrahigh electromechanical response in single-crystal piezoelectrics. Nature 403, 281–283 (2000)CrossRefGoogle Scholar
  5. 5.
    H. Cao, V.H. Schmidt, R. Zhang, W.W. Cao, H.S. Luo, Elastic, piezoelectric, and dielectric properties of 0.58Pb(Mg1/3Nb2/3)O3–0.42PbTiO3 single crystal. J. Appl. Phys. 96, 549–554 (2004)CrossRefGoogle Scholar
  6. 6.
    J. Yin, B. Jiang, W. Cao, Determination of elastic, piezoelectric and dielectric properties of Pb(Zn1/3Nb2/3)O3-PbTiO3 single crystals. Proc. SPIE. 3664, 239–246 (1999)CrossRefGoogle Scholar
  7. 7.
    W.H. He, Q. Li, N.N. Luo, Y.L. Zhang, Q.F. Yan, Temperature-dependent phase transition in orthorhombic [001]c - oriented low In3+ doping 19PIN-45PMN-36PT single crystals. Mater. Res. Bull. 75, 121–126 (2016)CrossRefGoogle Scholar
  8. 8.
    C.F.V. Raigoza, R.H.G.A. Kiminami, J.A. Eiras, D. Garcia, Effect of atmosphere on the formation of perovskite phase in 0.90Pb(Zn1/3Nb2/3)O3-0.10PbTiO3 (PZN-10PT) powders. Mater. Chem. Phys. 190, 102–107 (2017)CrossRefGoogle Scholar
  9. 9.
    L. Li, X.B. Li, X.Y. Zhao, B. Ren, Q. Xu, H.Q. Xu, H.S. Luo, X. Li, X.M. Shao, Enhanced dielectric, pyroelectric and ferroelectric properties of Mn-doped 0.15Pb(In1/2Nb1/2)O3 – 0.55Pb(Mg1/3Nb2/3)O3 – 0.30PbTiO3 single crystals. J. Alloy. Compd. 595, 120–124 (2014)CrossRefGoogle Scholar
  10. 10.
    Q. Liu, Y.X. Li, X.N. Chai, H.F. Zhao, X.S. Wang, X. Yao, Up-conversion luminescence and electric properties of Tm3+/Yb3+ co-doped (0.94Na0.5Bi0.5TiO3-0.06BaTiO3) ceramics. J. Mater. Sci. Mater. Electron. 27, 7174–7279 (2016)CrossRefGoogle Scholar
  11. 11.
    Z.Z. Xi, A.M. Han, P.Y. Fang, W. L, X.J. Li, Q.Q. Bu, Structural and electrical properties of Ho3+-modified Pb(Zn1/3Nb2/3)O3-9PbTiO3 single crystals. J. Mater. Sci. Mater. Electron. 27, 4223–4229 (2016)CrossRefGoogle Scholar
  12. 12.
    J.H. Chung, J.H. Ryu, S.Y. Lee, S.H. Kang, K.B. Shim, Effect of Yb3+ and Tm3+ concentrations on blue and NIR upconversion luminescence in Yb3+, Tm3+ co-doped CaMoO4. Ceram. Inter. 39, 1951–1956 (2013)CrossRefGoogle Scholar
  13. 13.
    V.K. Tikhomirov, V.D. Rodrı´guez, J. Me´ndez-Ramos, J. Del-Castillo, D. Kirilenko, G.Van Tendeloo, V.V. Moshchalkov, Optimizing Er/Yb ratio and content in Er-Yb co-doped glass-ceramics for enhancement of the up- and down- conversion luminescence. Sol. Energy Mat. Sol. C. 100, 209–215 (2012)CrossRefGoogle Scholar
  14. 14.
    J. Pisarska, R. Lisiecki, W. Ryba-Romanowski, G. Dominiak-Dzik, W.A. Pisarski, Up-converted luminescence in Yb-Tm co-doped lead fluoroborate glasses. J. Alloys Compd. 451, 226–228 (2008)CrossRefGoogle Scholar
  15. 15.
    V. Lojpur, M. Nikolic, L. Mancic, O. Milosevic, M.D. Dramicanin, Y2O3:Yb,Tm and Y2O3: Yb,Ho powders for low-temperature thermometry based on up-conversion fluorescence. Ceram. Inter. 39, 1129–1134 (2013)CrossRefGoogle Scholar
  16. 16.
    A.F. Pereira, K.U. Kumar, W.F. Silva, W.Q. Santos, D. Jaque, C. Jacinto, Yb3+/Tm3+ co-doped NaNbO3 nanocrystals as three-photon-excited luminescent nanothermometers. Sens. Actuators B. Chem. 213, 65–71 (2015)CrossRefGoogle Scholar
  17. 17.
    J. Xie, L. Mei, J. Deng, H. Liu, B. Ma, M. Guan, L. Liao, G. Lv, Up-conversion luminescence properties and energy transfer of Tm3+/Yb3+ co-doped BaLa2ZnO5. J. Solid State Chem. 231, 212–216 (2015)CrossRefGoogle Scholar
  18. 18.
    C. Regmi, Y.K. Kshetri, S.K. Ray, R.P. Pandey, S.W. Lee, Utilization of visible to NIR light energy by Yb+ 3, Er+ 3 and Tm+ 3 doped BiVO4 for the photocatalytic degradation of methylene blue. Appl. Surf. Sci. 392, 61–70 (2017)CrossRefGoogle Scholar
  19. 19.
    Z.Z. Xi, A.M. Han, P.Y. Fang, X.J. Li, W. Long, Electrical properties and upconversion luminescence of the Er3+-modified PZN-9PT crystals. J. Mater. Res. 31, 3044–3049 (2016)CrossRefGoogle Scholar
  20. 20.
    K.K. Mishra, A.K. Arora, S.N. Tripathy, D. Pradhan, Dielectric and polarized Raman spectroscopic studies on 0.85Pb(Zn1/3Nb2/3)O3-0.15PbTiO3 single crystal. J. Appl. Phys. 112, 073521-1–073521-7 (2012)Google Scholar
  21. 21.
    H. Zhou, T. Li, N. Zhang, M. Mai, M. Ye, P. Lin, C. Huang, X. Zeng, H. Huang, S. Ke, A Diagram of the structure evolution of Pb(Zn1/3Nb2/3) O3-9%PbTiO3 relaxor ferroelectric crystals with excellent piezoelectric properties. Crystals 7(5), 130 (2017)CrossRefGoogle Scholar
  22. 22.
    B. Srimathy, R. Jayavel, S. Ganesamoorthy, I. Bhaumik, A.K. Karnal, V. Natarajan, E. Varadarajan, Crystal growth of PZN-PT single crystals and critical issues for higher piezoelectric coefficient. Cryst. Res. Technol. 47, 523–529 (2012)CrossRefGoogle Scholar
  23. 23.
    J. Ajay, D.K.R. Sunaja, P. Dephan, N.S. Lakshmi, Electrochemical synthesis, photodegradation and antibacterial properties of PEG capped zinc oxide nanoparticles. J. Photochem. Photobiol. B 187, 25–34 (2018)CrossRefGoogle Scholar
  24. 24.
    Z.H. Du, T.S. Zhang, M.M. Zhu, Direct crystallization of perovskite phase in PMN-PT thin films prepared by polyvinylpyrrolidone modified sol-gel processing and their properties. J. Solid State Chem. 182, 1780–1785 (2009)CrossRefGoogle Scholar
  25. 25.
    C.Q. Li, J.Z. Zhang, L.P. Xu, J.J. Zhu, Z.H. Duan, Z.G. Hu, J.H. Chu, Temperature dependent optical dispersion and electronic transitions of highly a-axis oriented 0.8Pb(Zn1/3Nb2/3)O3-0.2PbTiO3 films on SrTiO3 crystals: An ellipsometric evidence. Thin Solid Films 603, 14–20 (2016)CrossRefGoogle Scholar
  26. 26.
    E.W. Sun, X.D. Qi, Z.Y. Yuan, S.J. Sang, R. Zhang, B. Yang, W.W. Cao, L.C. Zhao, Relaxation behavior in 0.24Pb(In1/2Nb1/2)O3-0.49Pb(Mg1/3Nb2/3)O3-0.27PbTiO3 ferroelectric single crystal. Ceram. Int. 42, 4893–4898 (2016)CrossRefGoogle Scholar
  27. 27.
    B. Srimathy, R. Jayavel, I. Bhaumik, S. Ganesamoorthy, A.K. Karnal, Role of dopant induced defects on the properties of Nd and Cr doped PZNT single crystals. Mater. Sci. Eng. B 185, 60–66 (2014)CrossRefGoogle Scholar
  28. 28.
    L.D. Ai, X.Z. Li, Z.J. Wang, Y. Liu, C. He, T. Li, T. Chu, D.F. Pang, H. Tailor, X.F. Long, Preparation, structure, and electric properties of the Pb(Zn1/3Nb2/3)O3-Pb(Yb1/2Nb1/2)O3- PbTiO3 ternary ferroelectric system ceramics near the morphotropic phase boundary. J. Eur. Ceram. Soc. 33, 2155–2165 (2013)CrossRefGoogle Scholar
  29. 29.
    J.D. Bobić, M.M. Vijatović Petrović, J. Banys, B.D. Stojanović, Effect of La substitution on the structural and electrical properties of BaBi1–xLaxTi4O15. Ceram. Int. 39, 8049–8057 (2013)CrossRefGoogle Scholar
  30. 30.
    G. Sui, B. Chen, J. Zhang, X. Li, S. Xu, J. Sun, Y. Zhang, L. Tong, X. Luo, H. Xi, Examination of Judd-Ofelt calculation and temperature self-reading for Tm3+ and Tm3+/Yb3+ doped LiYF4 single crystals. J. Lumin. 198, 77–83 (2018)CrossRefGoogle Scholar
  31. 31.
    F.G. Rego-Filho, N.O. Dantas, A.C.A. Silva, M.V.D. Vermelho, C. Jacinto, A.S. Gouveia-Neto, IR-to-visible frequency upconversion in Yb3+/Tm3+ co-doped phosphate glass. Opt. Mater. 73, 1–6 (2017)CrossRefGoogle Scholar
  32. 32.
    W.C. Wang, J. Yuan, X.Y. Liu, D.D. Chen, Q.Y. Zhang, Z.H. Jiang, An efficient 1.8 µm emission in Tm3+ and Yb3+/Tm3+ doped fluoride modified germanate glasses for a diode-pump mid-infrared laser. J. Non-Cryst. Solids 404, 19–25 (2014)CrossRefGoogle Scholar
  33. 33.
    Y.O.U. Junhua, M. LI, Q.U. Yingdong, L.I. Rongde, L.I.U. Xuanwen, G.U.O. Rui, UC/DC luminescence of Ho3+ doped pyrochlore structured La2(1–x)Yb2xTiO5 phosphor synthesized by sol-gel method. J. Rare Earth. 34, 235–239 (2016)CrossRefGoogle Scholar
  34. 34.
    Ai.G. He, Z.Z. Xi, X.J. Li, W. Long, P.Y. Fang, J. Zhao, H.B. Yu, Y.L. Kong, Optical properties of Ho3+- and Ho3+/Yb3+-modified PSN-PMN-PT crystals. Mater. Lett. 219, 64–67 (2018)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Ying Li
    • 1
  • Zengzhe Xi
    • 1
    Email author
  • Pinyang Fang
    • 1
  • Xiaojuan Li
    • 1
  • Wei Long
    • 1
  • Aiguo He
    • 1
  • Wei Zhao
    • 1
  1. 1.Shaanxi Key Laboratory of Photoelectric Functional Materials and Devices, School of materials and Chemical EngineeringXi’an Technological UniversityXi’anChina

Personalised recommendations