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Compositional modulation in ZnGa2O4 via Zn2+/Ge4+ co-doping to simultaneously lower sintering temperature and improve microwave dielectric properties

Abstract

AB2O4-type spinels with low relative permittivity (εr) and high quality factor (Q × f) are crucial to high-speed signal propagation systems. In this work, Zn2+/Ge4+ co-doping to substitute Ga3+ in ZnGa2O4 was designed to lower the sintering temperature and adjust the thermal stability of resonance frequency simultaneously. Zn1+xGa2−2xGexO4 (0.1 ⩽ x ⩽ 0.5) ceramics were synthesised by the conventional solid-state method. Zn2+/Ge4+ co-substitution induced minimal variation in the macroscopical spinel structure, which effectively lowered the sintering temperature from 1385 to 1250 °C. All compositions crystallized in a normal spinel structure and exhibited dense microstructures and excellent microwave dielectric properties. The compositional dependent quality factor was related to the microstructural variation, being confirmed by Raman features. A composition with x = 0.3 shows the best dielectric properties with εr ≈ 10.09, Q × f ≈ 112,700 THz, and τf ≈ −75.6 ppm/°C. The negative τf value was further adjusted to be near-zero through the formation of composite ceramics with TiO2.

References

  1. [1]

    Lin QB, Song KX, Liu B, et al. Vibrational spectroscopy and microwave dielectric properties of AY2Si3O10 (A=Sr, Ba) ceramics for 5G applications. Ceram Int 2020, 46: 1171–1177.

    CAS  Google Scholar 

  2. [2]

    Zhou D, Pang LX, Wang DW, et al. High permittivity and low loss microwave dielectrics suitable for 5G resonators and low temperature co-fired ceramic architecture. J Mater Chem C 2017, 5: 10094–10098.

    CAS  Google Scholar 

  3. [3]

    Du K, Song XQ, Li J, et al. Optimised phase compositions and improved microwave dielectric properties based on calcium tin silicates. J Eur Ceram Soc 2019, 39: 340–345.

    CAS  Google Scholar 

  4. [4]

    Huang FY, Su H, Li YX, et al. Low-temperature sintering and microwave dielectric properties of CaMg1−xLi2xSi2O6 (x = 0−0.3) ceramics. J Adv Ceram 2020, 9: 471–480.

    CAS  Google Scholar 

  5. [5]

    Li CC, Xiang HC, Xu MY, et al. Li2AGeO4 (A = Zn, Mg): Two novel low-permittivity microwave dielectric ceramics with olivine structure. J Eur Ceram Soc 2018, 38: 1524–1528.

    CAS  Google Scholar 

  6. [6]

    Zhang L, Zhang J, Yue ZX, et al. Thermally stable polymer-ceramic composites for microwave antenna applications. J Adv Ceram 2016, 5: 269–276.

    Google Scholar 

  7. [7]

    Wang D, Xiang HC, Tang Y, et al. A low-firing Ca5Ni4(VO4)6 ceramic with tunable microwave dielectric properties and chemical compatibility with Ag. Ceram Int 2016, 42: 15094–15098.

    CAS  Google Scholar 

  8. [8]

    Takahashi S, Kan A, Ogawa H. Microwave dielectric properties and crystal structures of spinel-structured MgAl2O4 ceramics synthesized by a molten-salt method. J Eur Ceram Soc 2017, 37: 1001–1006.

    CAS  Google Scholar 

  9. [9]

    Surendran KP, Santha N, Mohanan P, et al. Temperature stable low loss ceramic dielectrics in (1−x)ZnAl2O4xTiO2 system for microwave substrate applications. Eur Phys J B 2004, 41: 301–306.

    CAS  Google Scholar 

  10. [10]

    Belous A, Ovchar O, Durilin D, et al. High-Q microwave dielectric materials based on the spinel Mg2TiO4. J Am Ceram Soc 2006, 89: 3441–3445.

    CAS  Google Scholar 

  11. [11]

    Lyu XS, Li LX, Sun H, et al. A novel low-loss spinel microwave dielectric ceramic CoZnTiO4. J Mater Sci: Mater Electron 2015, 26: 8663–8666.

    CAS  Google Scholar 

  12. [12]

    Xue JJ, Wu SP, Li JH. Synthesis, microstructure, and microwave dielectric properties of spinel ZnGa2O4 ceramics. J Am Ceram Soc 2013, 96: 2481–2485.

    CAS  Google Scholar 

  13. [13]

    Lu XC, Bian WJ, Quan B, et al. Compositional tailoring effect on ZnGa2O4-TiO2 ceramics for tunable microwave dielectric properties. J Alloys Compd 2019, 792: 742–749.

    CAS  Google Scholar 

  14. [14]

    Lu XC, Bian WJ, Min CF, et al. Cation distribution of high-performance Mn-substituted ZnGa2O4 microwave dielectric ceramics. Ceram Int 2018, 44: 10028–10034.

    CAS  Google Scholar 

  15. [15]

    Lu XC, Bian WJ, Li YY, et al. Cation distributions and microwave dielectric properties of Cu-substituted ZnGa2O4 spinel ceramics. Ceram Int 2017, 43: 13839–13844.

    CAS  Google Scholar 

  16. [16]

    Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst Sect A 1976, 32: 751–767.

    Google Scholar 

  17. [17]

    Allix M, Chenu S, Véron E, et al. Considerable improvement of long-persistent luminescence in germanium and tin substituted ZnGa2O4. Chem Mater 2013, 25: 1600–1606.

    CAS  Google Scholar 

  18. [18]

    Bae SY, Lee J, Jung H, et al. Helical structure of single-crystalline ZnGa2O4 nanowires. J Am Chem Soc 2005, 127: 10802–10803.

    CAS  Google Scholar 

  19. [19]

    Magomedov MN. On the deviation from the Vegard’s law for the solid solutions. Solid State Commun 2020, 322: 114060.

    CAS  Google Scholar 

  20. [20]

    Yin CZ, Tang Y, Chen JQ, et al. Phase evolution, far-infrared spectra, and ultralow loss microwave dielectric ceramic of Zn2Ge1+xO4+2x (−0.1 ⩽ x ⩽ 0.2). J Mater Sci: Mater Electron 2019, 30: 16651–16658.

    CAS  Google Scholar 

  21. [21]

    Shannon RD. Dielectric polarizabilities of ions in oxides and fluorides. J Appl Phys 1993, 73: 348–366.

    CAS  Google Scholar 

  22. [22]

    Pei CJ, Tan JJ, Li Y, et al. Effect of Sb-site nonstoichiometry on the structure and microwave dielectric properties of Li3Mg2Sb1−xO6 ceramics. J Adv Ceram 2020, 9: 588–594.

    CAS  Google Scholar 

  23. [23]

    Yoon SH, Kim DW, Cho SY, et al. Investigation of the relations between structure and microwave dielectric properties of divalent metal tungstate compounds. J Eur Ceram Soc 2006, 26: 2051–2054.

    CAS  Google Scholar 

  24. [24]

    Du K, Fan J, Zou ZY, et al. Crystal structure, phase compositions, and microwave dielectric properties of malayaite-type Ca1−xSrxSnSiO5 ceramics. J Am Ceram Soc 2020, 103: 6369–6377.

    CAS  Google Scholar 

  25. [25]

    Yin CZ, Xiang HC, Li CC, et al. Low-temperature sintering and thermal stability of Li2GeO3-based microwave dielectric ceramics with low permittivity. J Am Ceram Soc 2018, 101: 4608–4614.

    CAS  Google Scholar 

  26. [26]

    Yin CZ, Li CC, Yang GJ, et al. NaCa4V5O17: A low-firing microwave dielectric ceramic with low permittivity and chemical compatibility with silver for LTCC applications. J Eur Ceram Soc 2020, 40: 386–390.

    CAS  Google Scholar 

  27. [27]

    Brese NE, O’Keeffe M. Bond-valence parameters for solids. Acta Crystallogr Sect B 1991, 47: 192–197.

    Google Scholar 

  28. [28]

    Brown ID, Altermatt D, Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database. Acta Crystallogr Sect B 1985, 41: 244–247.

    Google Scholar 

  29. [29]

    Park HS, Yoon KH, Kim ES. Relationship between the bond valence and the temperature coefficient of the resonant frequency in the complex perovskite (Pb1−xCax)[Fe0.5(Nb1−yTay)0.5]O3. J Am Ceram Soc 2001, 84: 99–103.

    CAS  Google Scholar 

  30. [30]

    Kim ES, Chun BS, Freer R, et al. Effects of packing fraction and bond valence on microwave dielectric properties of A2+B6+O4 (A2+: Ca, Pb, Ba; B6+: Mo, W) ceramics. J Eur Ceram Soc 2010, 30: 1731–1736.

    CAS  Google Scholar 

  31. [31]

    Yin CZ, Yu ZZ, Shu LL, et al. Alow-firing melilite ceramic Ba2CuGe2O7 and compositional modulation on microwave dielectric properties through Mg substitution. J Adv Ceram 2021, 10: 108–119.

    CAS  Google Scholar 

  32. [32]

    Li CC, Yin CZ, Deng M, et al. Tunable microwave dielectric properties in SrO-V2O5 system through compositional modulation. J Am Ceram Soc 2020, 103: 2315–2321.

    CAS  Google Scholar 

  33. [33]

    Kim ES, Chun BS, Yoon KH. Dielectric properties of [Ca1−x(Li1/2Nd1/2)x]1−yZnyTiO3 ceramics at microwave frequencies. Mater Sci Eng: B 2003, 99: 93–97.

    Google Scholar 

  34. [34]

    Song XQ, Lu WZ, Wang XC, et al. Sintering behaviour and microwave dielectric properties of BaAl2−2x(ZnSi)xSi2O8 ceramics. J Eur Ceram Soc 2018, 38: 1529–1534.

    CAS  Google Scholar 

  35. [35]

    Zhou D, Pang LX, Wang DW, et al. High quality factor, ultralow sintering temperature Li6B4O9 microwave dielectric ceramics with ultralow density for antenna substrates. ACS Sustain Chem Eng 2018, 6: 11138–11143.

    CAS  Google Scholar 

  36. [36]

    Barber DJ, Moulding KM, Zhou J, et al. Structural order in Ba(Zn1/3Ta2/3)O3, Ba(Zn1/3Nb2/3)O3 and Ba(Mg1/3Ta2/3)O3 microwave dielectric ceramics. J Mater Sci 1997, 32: 1531–1544.

    CAS  Google Scholar 

  37. [37]

    Bayer G. New perovskite-type compounds A2BTeO6. J Am Ceram Soc 1963, 46: 604–605.

    CAS  Google Scholar 

  38. [38]

    Mohaček-Grošev V, Vrankić M, Maksimović A, et al. Influence of titanium doping on the Raman spectra of nanocrystalline ZnAl2O4. J Alloys Compd 2017, 697: 90–95.

    Google Scholar 

  39. [39]

    Fraas LM, Moore JE, Salzberg JB. Raman characterization studies of synthetic and natural MgAl2O4 crystals. J Chem Phys 1973, 58: 3585–3592.

    CAS  Google Scholar 

  40. [40]

    Laguna-Bercero MA, Sanjuán ML, Merino RI. Raman spectroscopic study of cation disorder in poly- and single crystals of the nickel aluminate spinel. J Phys Condens Matter 2007, 19: 186217.

    CAS  Google Scholar 

  41. [41]

    Malavasi L, Galinetto P, Mozzati MC, et al. Raman spectroscopy of AMn2O4 (A = Mn, Mg and Zn) spinels. Phys Chem Chem Phys 2002, 4: 3876–3880.

    CAS  Google Scholar 

  42. [42]

    Krüger H, Többens DM, Tropper P, et al. Single-crystal structure and Raman spectroscopy of synthetic titanite analog CaAlSiO4F. Miner Petrol 2015, 109: 631–641.

    Google Scholar 

  43. [43]

    Li H, Zhang PC, Yu SQ, et al. Structural dependence of microwave dielectric properties of spinel structured Mg2(Ti1−xSnx)O4 solid solutions: Crystal structure refinement, Raman spectra study and complex chemical bond theory. Ceram Int 2019, 45: 11639–11647.

    CAS  Google Scholar 

  44. [44]

    Liu B, Li L, Liu XQ, et al. Structural evolution of SrLaAl1−x(Zn0.5Ti0.5)xO4 ceramics and effects on their microwave dielectric properties. J Mater Chem C 2016, 4: 4684–4691.

    CAS  Google Scholar 

  45. [45]

    Yang HC, Zhang SR, Yang HY, et al. Influence of (Al1/3W2/3)5+ co-substitution for Nb5+ in NdNbO4 and the impact on the crystal structure and microwave dielectric properties. Dalton Trans 2018, 47: 15808–15815.

    CAS  Google Scholar 

  46. [46]

    Zhang J, Zuo RZ. Raman scattering and infrared reflectivity study of orthorhombic/monoclinic LaTiNbO6 microwave dielectric ceramics by A/B-site substitution. Ceram Int 2018, 44: 16191–16198.

    CAS  Google Scholar 

  47. [47]

    Guo J, Zhou D, Wang L, et al. Infrared spectra, Raman spectra, microwave dielectric properties and simulation for effective permittivity of temperature stable ceramics AMoO4-TiO2 (A = Ca, Sr). Dalton Trans 2013, 42: 1483–1491.

    CAS  Google Scholar 

  48. [48]

    Wu SP, Xue JJ, Wang R, et al. Synthesis, characterization and microwave dielectric properties of spinel MgGa2O4 ceramic materials. J Alloys Compd 2014, 585: 542–548.

    CAS  Google Scholar 

  49. [49]

    Lu XP, Zheng Y, Huang Q, et al. Structural dependence of microwave dielectric properties of spinel-structured Li2ZnTi3O8 ceramic: Crystal structure refinement and Raman spectroscopy study. J Electron Mater 2016, 45: 940–946.

    CAS  Google Scholar 

  50. [50]

    Fukuda K, Kitoh R, Awai I. Microwave characteristics of TiO2Bi2O3 dielectric resonator. Jpn J Appl Phys 1993, 32: 4584–4588.

    CAS  Google Scholar 

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Acknowledgements

Chunchun Li gratefully acknowledges the financial support from the National Natural Science Foundation of China (No. 62061011), the Guangxi Zhuang Autonomous Region (Nos. 2018GXNSFAA281253 and 2019GXNSFGA245006), and the High-Level Innovation Team and Outstanding Scholar Program of Guangxi Institutes. The authors would also like to thank the administrators in the IR beamline workstation of the National Synchrotron Radiation Laboratory (NSRL) for their help in the IR measurement.

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Correspondence to Chunchun Li.

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Compositional modulation in ZnGa2O4 via Zn2+/Ge4+ co-doping to simultaneously lower sintering temperature and improve microwave dielectric properties

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Xiong, Y., Xie, H., Rao, Z. et al. Compositional modulation in ZnGa2O4 via Zn2+/Ge4+ co-doping to simultaneously lower sintering temperature and improve microwave dielectric properties. J Adv Ceram 10, 1360–1370 (2021). https://doi.org/10.1007/s40145-021-0511-0

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Keywords

  • ceramics
  • spinel
  • composition modulation
  • dielectric properties