Низкотемпературно спекающаяся керамика для технологии LTCC: Обзор. Часть 2. Бесстекольная керамика

В последние годы значительно возрос интерес к микроволновой диэлектрической керамике, применяемой в антеннах, фильтрах, резонаторах и других компонентах систем беспроводной связи. Такие материалы обеспечивают передачу сигнала, резонансные и фильтрующие функции в микроволновых цепях, поэтому их диэлектрические характеристики напрямую влияют на рабочие параметры устройств. Для технологии низкотемпературной совместно обжигаемой керамики (LTCC) особенно важны низкая температура спекания T_сп, совместимость с Ag-электродами, низкая относительная диэлектрическая проницаемость ε_r , высокая добротность Q или произведение Q×fи близкий к нулю температурный коэффициент резонансной частоты τ_f . Керамические материалы для технологии LTCC можно разделить на три группы: стеклокерамические композиты, стеклокерамики и материалы с изначально низкой температурой спекания.
В данной части обзора рассмотрены бесстекольные керамики с низкой температурой спекания, разработанные за последние 20 лет для применения в технологии LTCC. Анализ литературы показывает, что это направление развивается за счет поиска составов, которые сочетают низкую температуру спекания T_сп, малые диэлектрические потери tgδ, приемлемую ε_r, стабильный τ_f и химическую совместимость с Ag-электродами.

1. Xie C. et al. Rational design of inorganic dielectric materials with expected permittivity // Scientific Reports. – 2015. – V. 5. – N 1. – Art. 16769.

2. Mei H. et al. Principal element design of garnets to access structure stability and excellent microwave dielectric properties // Journal of the American Ceramic Society. – 2022. – V. 105. – N 7. – P. 4805–4814.

3. Mei H. et al. Na2CaTi2Ge3O12: An anti-reductive garnet ceramic with high quality factor and chemical compatibility with Cu/Ag electrodes for low temperature co-fired application // Journal of Alloys and Compounds. – 2022. – V. 926. – P. 166960.

4. Ren J. et al. Novel Al2Mo3O12-based temperature-stable microwave dielectric ceramics for LTCC applications // Journal of Materials Chemistry C. – 2018. – V. 6. – N 42. – P. 11465–11470.

5. 5. Hao Y. Z. et al. Microwave dielectric properties of Li2TiO3 ceramics doped with LiF for LTCC applications // Journal of alloys and compounds. – 2013. – V. 552. – P. 173–179.

6. Hong W. B. et al. Room-temperature-densified H3BO3 microwave dielectric ceramics with ultra-low permittivity and ultra-high Qf value // Journal of Materiomics. – 2020. – V. 6. – N 2. – P. 233–239.

7. Yang H. et al. Synthesis of CaAl2xB2O4+3x: Novel microwave dielectric ceramics with low permittivity and low loss // Journal of the European Ceramic Society. – 2021. – V. 41. – N 4. – P. 2596–2601.

8. Shannon R. D. Dielectric polarizabilities of ions in oxides and fluorides // Journal of Applied physics. – 1993. – V. 73. – N 1. – P. 348–366.

9. Geyer R. G., Baker-Jarvis J., Krupka J. Dielectric characterization of single-crystal LiF, CaF2, MgF2, BaF2, and SrF2 at microwave frequencies // The 17th Annual Meeting of the IEEE Lasers and Electro-Optics Society. – 2004. – P. 493–497.

10. Song X. Q. et al. Low-fired fluoride microwave dielectric ceramics with low dielectric loss // Ceramics International. – 2019. – V. 45. – N 1. – P. 279–286.

11. Zhou M. F. et al. Ultra-low permittivity MgF2 ceramics with high Qf values and their role as microstrip patch antenna substrates // Ceramics International. – 2023. – V. 49. – N 1. – P. 369–374.

12. Chen X. et al. Low temperature fired CaF2-based microwave dielectric ceramics with enhanced microwave properties // Journal of the European Ceramic Society. – 2022. – V. 42. – N 12. – P. 4969–4973.

13. Wang H. et al. MgF2-based microwave dielectric ceramics with ultra-low sintering temperature and high thermal expansion coefficient // Journal of the European Ceramic Society. – 2024. – V. 44. – N 4. – P. 2150–2156.

14. Ding Y., Bian J. Structural evolution, sintering behavior and microwave dielectric properties of (1−x)Li2TiO3+xLiF ceramics // Materials Research Bulletin. – 2013. – V. 48. – N 8. – P. 2776–2781.

15. Zhang Z. et al. Li5Ti2O6F: a new low-loss oxyfluoride microwave dielectric ceramic for LTCC app lications // Journal of Materials Science. – 2020. – V. 55. – N 1. – P. 107–115.

16. Liu K. et al. Sintering behavior, structural evolution, and dielectric properties of Li2+xMgTiO4Fx microwave dielectric ceramics // Journal of the European Ceramic Society. – 2023. – V. 43. – N 14. – P. 6098-6106.

17. Zhai S., Liu P., Wu S. Novel ultra-low loss and low-fired Li8MgxTi3O9+xF2 microwave dielectric ceramics for resonator antenna applications // Journal of the European Ceramic Society. – 2023. – V. 43. – N 8. – P. 3331–3337.

18. Chu X. et al. A new high-Q×f Li4NbO4F microwave dielectric ceramic for LTCC applications // Ceramics International. – 2021. – V. 47. – N 3. – P. 4344–4351.

19. Zhai S., Liu P., Zhang S. A novel high-Q oxyfluoride Li4Mg2NbO6F microwave dielectric ceramic with low sintering temperature // Journal of the European Ceramic Society. – 2021. – V. 41. – N 8. – P. 4478–4483.

20. Zhai S. et al. Novel series of high-Q oxyfluoride microwave dielectric ceramics for LTCC applications // Journal of Alloys and Compounds. – 2022. – V. 899. – P. 163145.

21. Wei M. et al. Solid-solution assisted densification and microwave/millimeter-wave dielectric properties of BaF2-SrF2 ceramics for high-reliability LTCC applications // Ceramics International. – 2025. – V. 51. – N 1. – P. 1055–1062.

22. Li R. et al. Ultra-low loss Li4+xTi2Mg7O13Fx (0≤x≤175) system microwave dielectric ceramics for LTCC applications // Ceramics International. – 2025. – V. 51. – N 7. – P. 8824–8831.

23. Mei H. et al. Compositional design, structure stability, and microwave dielectric properties in Ca3MgBGe3O12 (B= Zr, Sn) garnet ceramics with tetravalent cations on B-site // Ceramics International. – 2022. – V. 48. – N 4. – P. 4658–4664.

24. Xiang H. et al. Low-firing and microwave dielectric properties of Na2YMg2V3O12 ceramic // Ceramics International. – 2016. – V. 42. – N 2. – P. 3701–3705.

25. Li C. et al. Ultralow-temperature synthesis and densification of Ag2CaV4O12 with improved micro wave dielectric performances // ACS Sustainable Chemistry & Engineering. – 2021. – V. 9. – N 43. – P. 14461–14469.

26. Hu Y. et al. Crystal structure, Raman spectra and microwave – 2025. – V. 51. – N 18 (B). – P. 25944–25950.

27. Zhai S. et al. Novel series of high-Q oxyfluoride microwave dielectric ceramics for LTCC applications // Journal of Alloys and Compounds. – 2022. – V. 899. – P. 163145.

28. Sun Z. et al. Effects of 0.5B2O3–0.5CuO on the microwave dielectric properties of low-temperature sintered ZZNT ceramics // Ceramics International. – 2022. – V. 48. – N 5. – P. 7153–7158.

29. Du J. et al. Low temperature sintered Ca1-x(Li0.5Bi0.5)xWO4 ceramics with enhanced microwave dielectric properties for LTCC applications // Ceramics International. – 2022. – V. 48. – N 23. – P. 34446–34453.

30. Huang B. et al. Microwave dielectric properties of Li2WO4-added SrWO4 ceramics for LTCC app lications // Journal of Materials Science: Materials in Electronics. – 2022. – V. 33. – N 27. – P. 21925–21934.

31. Liu Y. et al. LiF-Modulated Sintering Behavior and Microwave Dielectric Performance of Scheelite-Type NaLa(WO4)2 Ceramics for 5G-Oriented LTCC Applications // Ceramics International. – 2025. – V. 51. – Is. 24. – Part A. – P. 40841–40849.

32. Gupta R. et al. Structural, microstructural, and microwave dielectric properties of (Al1-xBx)2 Mo3O12 ceramics with low dielectric constant and low dielectric loss for LTCC applications // Ceramics International. – 2023. – V. 49. – Is. 14. – Part A. – P. 22690–22701.

33. Ramarao S.D., Kiran S. R., Murthy V. R. K. Structural, lattice vibrational, optical and microwave dielectric studies on Ca1−xSrxMoO4 ceramics with scheelite structure // Materials Research Bulletin. – 2014. – V. 56. – P. 71–79.

34. Mullens B.G. et al. Long-range A-site cation disorder in NaA(MO4)2 (M= Mo, W) double scheelite oxides // Journal of Solid State Chemistry. – 2023. – V. 321. – P. 123871.

35. Pang L. X. et al. Microwave dielectric properties of (Li0.5Ln0.5) MoO4 (ln= Nd, Er, Gd, Y, Yb, Sm, and Ce) ceramics // Journal of the American Ceramic Society. – 2015. – V. 98. – N 1. – P. 130–135.

36. Xi H. et al. Microwave dielectric properties of low firing scheelite-related (Na0.5La0.5)MoO4 ceramic // Materials Letters. – 2015. – V. 142. – P. 221–224.

37. Zhou D. et al. Low temperature firing microwave dielectric ceramics (K0.5Ln0.5)MoO4 (Ln= Nd and Sm) with low dielectric loss // Journal of the European Ceramic Society. – 2011. – V. 31. – N 15. – P. 2749-2752.

38. Liu W., Zuo R. A novel low-temperature firable La2Zr3(MoO4)9 microwave dielectric ceramic // Journal of the European Ceramic Society. – 2018. – V. 38. – N 1. – P. 339–342.

39. Gao P. et al. Sintering behavior, phase structure and microwave dielectric properties of novel glassfree low-temperature cofiring NaCaLn(MoO4)3 (Ln = Nd, Sm) ceramics // Ceramics International. – 2024. – V. 50. – N 4. – P. 6508–6516.

40. Yao G. G. et al. Synthesis and microwave dielectric properties of Li2MgTiO4 ceramics // Ceramics International. – 2015. – V. 41. – P. S563–S566.

41. Li C. et al. Ultra-low loss microwave dielectric ceramic Li2Mg2TiO5 and low-temperature firing via B2O3 addition // Journal of Electronic Materials. – 2018. – V. 47. – N 11. – P. 6383–6389.

42. Fu Z. et al. Novel series of ultra-low loss microwave dielectric ceramics: Li2Mg3BO6 (B= Ti, Sn, Zr) // Journal of the European Ceramic Society. – 2016. – V. 36. – N 3. – P. 625–629.

43. Bi J. X. et al. Crystal structure, infrared spectra and microwave dielectric properties of ultra lowloss Li2Mg4TiO7 ceramics // Materials Letters. – 2017. – V. 196. – P. 128–131.

44. Bi J., Niu Y., Wu H. Li4Mg3Ti2O9: a novel low-loss microwave dielectric ceramic for LTCC applications // Ceramics International. – 2017. – V. 43. – N10. – P. 7522–7530.

45. Zhang Y. et al. Phase Composition and Microwave Dielectric Properties of Li2 (1+x)Mg3Ti4O12 Ceramics with Inverse Spinel Structure // Journal of Electronic Materials. – 2024. – V. 53. – N 10. – P. 6553-6562.

46. Ohashi M. et al. Microwave dielectric properties of low-temperature sintered Li3AlB2O6 ceramic // Journal of the European Ceramic Society. – 2005. – V. 25. – N 12. – P. 2877–2881.

47. Zhang R. Z., Reece M. J. Review of high entropy ceramics: design, synthesis, structure and properties // Journal of Materials Chemistry A. – 2019. – V. 7. – N 39. – P. 22148–22162.

48. Xiang H. et al. Microwave dielectric high-entropy ceramic Li(Gd0.2Ho0.2Er0.2Yb0.2Lu0.2)GeO4 with stable temperature coefficient for low-temperature cofired ceramic technologies // Journal of Materials Science & Technology. – 2021. – V. 93. – P. 28–32.

49. Shao P. et al. Synthesis, microstructure, and dielectric properties of novel dual-phase high-entropy (Ba0.2Ca0.2Sr0.2Na0.2Bi0.2)WO4 ceramics for LTCC applications // Journal of the European Ceramic Society. – 2024. – V. 44. – Is. 8. – P. 5203–5210.

50. Liu H. et al. High-entropy processed high quality and low-temperature cofired LiMgPO4-based dielectric ceramics for low-loss packaged millimeter-wave filters // Journal of the European Ceramic Society. – 2025. – V. 45. – N 2. – P. 116957.