ZnO-1.1TiO_2微波介质陶瓷的水热—固相法合成及低温烧结研究
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摘要
随着微波技术的高速发展,需要具有低温烧结的高性能的微波介质材料来满足微波元器件微型化发展要求。为满足此要求,利用低温共烧陶瓷(Low temperature cofired ceramic,LTCC)技术设计制造片式多层微波器件已成为当今的研究热点。低温共烧陶瓷以其优异的电子、机械、热学特性,已成为未来电子元件集成化、模组化的首选方式,在全球发展迅速,广泛用于基板、封装及微波器件等领域。ZnTiO3陶瓷具有介电常数高、介电损耗低、频率温度系数小等特点,如能提高钛酸锌陶瓷中ZnTiO3相的热稳定性,并和LTCC技术制造工艺匹配,将是理想的LTCC介质材料。
本文采用水热法合成ZnO-TiO2前驱体氧化物,并以此为原料通过传统氧化物固相煅烧法合成ZnO-1.1TiO2。实验发现,180℃反应8h、填充度为80%的水热条件下合成的物料,其合成偏钛酸锌的最佳温度为800～850℃。钛酸锌陶瓷的致密化行为主要发生在1020～1070℃。
在此基础上,我们分别添加V2O5-Bi2O3(简写为VB),CuO-V2O5(简写为CV)及CuO-V2O5-Bi2O3(简写为CVB),并利用X射线衍射(XRD)、扫描电镜(SEM)等技术手段研究了不同烧结温度下六方相ZnTiO3的热稳定性、显微形貌特征及微波介电性能等。结果表明:添加了0.5wt%V2O5-Bi2O3的ZnO-1.1TiO2陶瓷,谐振频率温度系数曲线经过零点,添加0.5wt%VB样品的微波介电性能为:εr≈25.3,Qf≈20860GHz,τf≈+2ppm/℃。CuO或V2O5的加入并没有影响钛酸锌陶瓷的相组成,870℃烧结添加CV样品的微波介电性能为:εr≈28,Qf≈20000GHz,τf≈+6ppm/℃。添加CuO-V2O5-Bi2O3能够抑制钛铁矿相ZnTiO3的分解,具有很好的降温作用,830℃烧结掺杂2wt%CVB的陶瓷的体积密度最大,为理论密度的98.8%,微波介电性能为:εr=30,Qf=33460GHz,τf=6ppm/℃。
As the rapid development of microwave technology, high performance microwave dielectric ceramics, which can be sintered at low temperature, are required by the microminiaturization of components. In order to fulfill these requirements, design and manufacture of multi-chip microwave components using low temperature cofired ceramics technology has become a research hotspot now. LTCC by its excellent electronic, machinery, thermal properties, has become the electronic components intergrated,modular preferred way, in the global development of rapid,widely used for substrate,packaging,and microwave devices and other fields.ZnTiO3 ceramics behaves high dielectric constant, low dielectric loss and stable temperature coefficient of resonant frequency, if can improve the thermal stability ZnTiO3 and with the LTCC technology manufacture craft match, will be the ideal LTCC dielectric materials.
In this thesis,ZnO-TiO2 composite oxide were prepared by hydrothermal method, and synthesizes ZnO-1.1TiO2 take this as raw material through conventional mixed-oxide method. It has been found experimentally that calcining the powder at different temperature after hydrothermal reaction at 180℃,8h and volumetric rate of 80%,the optimum synthesis temperature of zinc titanate was 800～850℃. Zinc titanium ceramic densification behavior mainly occurred in the 1020～1070℃.
On this basis, doped separately with V2O5-Bi2O3(hereinafter designated as VB) , CuO-V2O5 ( hereinafter designated as CV ) and CuO-V2O5-Bi2O3 ( hereinafter designated as CVB), thermal, microstructural and microwave dielectric properties of the hexagonal phase ZnTiO3 prepared were characterized or measured by means of XRD,SEM. As a result, ZnO-1.1TiO2 ceramics doped with V2O5-Bi2O3, its temperature coefficient of resonant frequency curve through zero, The dielectric properties of samples with 0.5wt% VB addition were:εr≈25.3,Qf≈20860GHz,τf≈+2ppm/℃.CuO or V2O5 addition have not affect the phase composition of zinc titanate ceramics, the dielectric properties of samples sintered at 870℃with CV addition were:εr≈28,Qf≈20000GHz,τf≈+6ppm/℃. Ilmenite phase did inhibit the decomposition with the addition of CuO-V2O5-Bi2O3,showing a very good effect of lowering sintering temperature. With 2wt% CVB addition,the ceramics sintered at 830℃get a relative density value of 98.8%,and microwave dielectric properties:εr=30,Qf=33460GHz,τf=6ppm/℃.
本文采用水热法合成ZnO-TiO2前驱体氧化物,并以此为原料通过传统氧化物固相煅烧法合成ZnO-1.1TiO2。实验发现,180℃反应8h、填充度为80%的水热条件下合成的物料,其合成偏钛酸锌的最佳温度为800～850℃。钛酸锌陶瓷的致密化行为主要发生在1020～1070℃。
在此基础上,我们分别添加V2O5-Bi2O3(简写为VB),CuO-V2O5(简写为CV)及CuO-V2O5-Bi2O3(简写为CVB),并利用X射线衍射(XRD)、扫描电镜(SEM)等技术手段研究了不同烧结温度下六方相ZnTiO3的热稳定性、显微形貌特征及微波介电性能等。结果表明:添加了0.5wt%V2O5-Bi2O3的ZnO-1.1TiO2陶瓷,谐振频率温度系数曲线经过零点,添加0.5wt%VB样品的微波介电性能为:εr≈25.3,Qf≈20860GHz,τf≈+2ppm/℃。CuO或V2O5的加入并没有影响钛酸锌陶瓷的相组成,870℃烧结添加CV样品的微波介电性能为:εr≈28,Qf≈20000GHz,τf≈+6ppm/℃。添加CuO-V2O5-Bi2O3能够抑制钛铁矿相ZnTiO3的分解,具有很好的降温作用,830℃烧结掺杂2wt%CVB的陶瓷的体积密度最大,为理论密度的98.8%,微波介电性能为:εr=30,Qf=33460GHz,τf=6ppm/℃。
As the rapid development of microwave technology, high performance microwave dielectric ceramics, which can be sintered at low temperature, are required by the microminiaturization of components. In order to fulfill these requirements, design and manufacture of multi-chip microwave components using low temperature cofired ceramics technology has become a research hotspot now. LTCC by its excellent electronic, machinery, thermal properties, has become the electronic components intergrated,modular preferred way, in the global development of rapid,widely used for substrate,packaging,and microwave devices and other fields.ZnTiO3 ceramics behaves high dielectric constant, low dielectric loss and stable temperature coefficient of resonant frequency, if can improve the thermal stability ZnTiO3 and with the LTCC technology manufacture craft match, will be the ideal LTCC dielectric materials.
In this thesis,ZnO-TiO2 composite oxide were prepared by hydrothermal method, and synthesizes ZnO-1.1TiO2 take this as raw material through conventional mixed-oxide method. It has been found experimentally that calcining the powder at different temperature after hydrothermal reaction at 180℃,8h and volumetric rate of 80%,the optimum synthesis temperature of zinc titanate was 800～850℃. Zinc titanium ceramic densification behavior mainly occurred in the 1020～1070℃.
On this basis, doped separately with V2O5-Bi2O3(hereinafter designated as VB) , CuO-V2O5 ( hereinafter designated as CV ) and CuO-V2O5-Bi2O3 ( hereinafter designated as CVB), thermal, microstructural and microwave dielectric properties of the hexagonal phase ZnTiO3 prepared were characterized or measured by means of XRD,SEM. As a result, ZnO-1.1TiO2 ceramics doped with V2O5-Bi2O3, its temperature coefficient of resonant frequency curve through zero, The dielectric properties of samples with 0.5wt% VB addition were:εr≈25.3,Qf≈20860GHz,τf≈+2ppm/℃.CuO or V2O5 addition have not affect the phase composition of zinc titanate ceramics, the dielectric properties of samples sintered at 870℃with CV addition were:εr≈28,Qf≈20000GHz,τf≈+6ppm/℃. Ilmenite phase did inhibit the decomposition with the addition of CuO-V2O5-Bi2O3,showing a very good effect of lowering sintering temperature. With 2wt% CVB addition,the ceramics sintered at 830℃get a relative density value of 98.8%,and microwave dielectric properties:εr=30,Qf=33460GHz,τf=6ppm/℃.
引文
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