本研究探討微波介電材料-透輝石相玻璃陶瓷(diopside, CaMgSi2O6)介電特性與電極匹配；透輝石相材料具有低介電常數(dielectric constant, k)、低成本、高品質因子(quality factor, Q*f)及900℃左右之燒結溫度，因此透輝石相玻璃陶瓷具有發展低溫共燒技術(LTCC, Low Temperature Co-fired Ceramic)之潛力；然而透輝石相不具有趨近於零的共振頻率溫度係數(temperature coefficient of resonance frequency,τf)，因此選擇MgTiO3陶瓷粉末添加進透輝石相，因燒結時的溫度產生置換反應生成CaTiO3和Mg2SiO4，前者補償了共振溫度頻率係數，後者提升了品質因子；此外，添加具有高品質因子之化合物(Zn(1-x)Mgx)2SiO4可提高結晶度和品質因子；接下來將改質後之透輝石材料系統於大氣下與電極(銀與銅)共燒，並探討共燒後之電極擴散之影響並進行抑制，也預期此材料系統可於還原氣氛下和電極進行共燒。
本論文第一部分添加ZnO進入透輝石相玻璃陶瓷，其使透輝石相玻璃陶瓷系統有抗還原的效果，且產生二次相Zn2SiO4和Mg2SiO4此二次相具有219,000和240,000 GHz之高品質因子，而後續於820℃~960℃進行熱處理，實驗結果發現，當840℃時具有明顯的品質因子提升，由7153提升至8163 GHz；且在SEM-EDS發現二次相Zn2SiO4和Mg2SiO4以塊狀分佈在透輝石相玻璃陶瓷中。其第二部分為在透輝石相玻璃陶瓷分別添加8wt%陶瓷粉體MgTiO3和8wt% (Zn0.6Mg0.4)2SiO4和兩者同時添加。在透輝石相玻璃陶瓷添加(Zn0.6Mg0.4)2SiO4可提升整體品質因子，後續於820℃~960℃進行熱處理，由實驗結果發現，當840℃同樣因超過透輝石相玻璃陶瓷的成核成長溫度有明顯的品質因子提升，且在熱處理溫度隨之提升，Zn2SiO4比例降低，Mg2SiO4提升，在熱處理940℃持溫兩小時後得到最佳特性為K:7.133, Q*f:8893GHz, τf:-72ppm/℃。另一方面，在透輝石相玻璃陶瓷添加8wt%陶瓷粉體MgTiO3，在820~900℃熱處理並無法燒結緻密，造成品質因子不佳，由Mapping和XRD可觀察到產生二次相CaTiO3和ZnTiO3修正共振溫度頻率係數。其介電特性為K:7.813, Q*f:7186, τf:-50ppm/℃。
電極擴散會影響元件之工作頻率及效率，而銀離子在燒結過程氧化後與玻璃鍵結且往透輝石相玻璃陶瓷基材擴散;因此添加陶瓷粉體MgTiO3和(Zn0.6Mg0.4)2SiO4抑制電極擴散，MgTiO3可均勻分布在透輝石玻璃陶瓷中且顆粒小，並有效阻隔銀離子繼續往基材擴散，效果比添加(Zn0.6Mg0.4)2SiO4更佳。
此外，銅電極膠易與共燒基材產生反應，進而影響介電特性，透輝石相玻璃陶瓷在960℃之還原氣氛下與銅共燒，由XRD分析可觀察到微小的二次相Ca2CuO3峰值，但也生成能提升品質因子的二次相Mg2SiO4，在Mapping觀察下銅並無明顯擴散進入基材。

This study focuses on a novel microwave dielectric material - diopside (CaMgSi2O6) glass-ceramic. Diopside material has a unique character of low dielectric constant (k), low cost, high quality factor (Qxf value) and lower than 900℃ sintering temperature. Therefore, diopside is a potential candidate material for LTCC (Low Temperature Co-fired Ceramic) process. However, the negative temperature coefficient of resonance frequency (τf) is too large to be applied in microwave dielectric components. In this case, MgTiO3 was chosen to compensate the large negative temperature coefficient of resonance frequency (τf) of diopside glass-ceramics. The as-sintered specimens consist of Mg2SiO4 and CaTiO3, which result in high quality factor and an improved temperature coefficient of resonant frequency, because the Mg2SiO4 and CaTiO3 possess ultra-high Qxf and positive τf characteristics, respectively. In addition, the addition of (Zn(1-x)Mgx)2SiO4 improves crystallinity and quality factor. Followed by this result, the microstructure analysis and electrode inhibition after co-fired with silver and copper electrode were carried out by SEM-EDS in this work. In addition, It appears that this material system can be co-fired with a copper electrode under a reducing atmosphere.
In the first part, in order to improve the sintering characteristic of diopside in reducing atmosphere, the addition of ZnO was carried out. The secondary phase Zn2SiO4 with a quality factor of 219,000 GHz is produced. Optimum processing temperature and microstructural development were investigated using heat treatment conditions of annealing from 820℃ to 960℃ for 2hrs. It has a significant quality factor improvement at 840℃, from 7153 to 8163 GHz. In addition, it was found in SEM-EDS that Zn2SiO4 and Mg2SiO4 were revealed in the diopside phase glass ceramics. The second part is to add 8wt% ceramic powder of MgTiO3 and/or 8wt% (Zn0.6Mg0.4)2SiO4 in diopside phase glass ceramics. Adding (Zn0.6Mg0.4)2SiO4 to the diopside phase glass ceramic can improve the quality factor of the dielectric material. We investigate the optimal annealing temperature and microstructures after the specimens were heat treated at a temperature from 820℃ to 960℃ for 2hrs. When 840℃/2hr was adopted, the material gains a significant quality factor increase due to nucleation and growth of the diopside phase glass phase ceramics. After heat treatment at 940℃/2hr, the best dielectrical properties of the material are K:7.133, Qxf: 8893 GHz, τf: -72 ppm /℃. In addition, 8 wt% of the ceramic powder MgTiO3 was added in the diopside phase glass ceramics, and processed at 820 to 900℃ and we observed the densities of the specimens were low. Materials need to be processed at temperatures higher than 900℃ to acquire better properties. From the X-ray mapping and structural analysis, it was observed that secondary phases CaTiO3 and ZnTiO3 was produced. Its best dielectric properties are K:7.813, Qxf: 7186, τf: -50ppm/℃.
Electrode diffusion affects the operating frequency and efficiency of the component, and silver ions are oxidized in the sintering process to bond with the glass and diffuse to the diopside glass ceramic substrate, and therefore degrading material properties. We thus add ceramic powders MgTiO3 and (Zn0.6Mg0.4)2SiO4 to suppress elemental diffusion of electrode materials. MgTiO3 can be evenly distributed in the diopside glass ceramics and the particles are small, and effectively block the diffusion of silver ions to the substrate, the effect is better than adding (Zn0.6Mg0.4)2SiO4. In addition, the copper easily reacts with the co-firing substrate. The diopside phase glass ceramic was co-fired with copper under a reducing atmosphere of 960 ° C, and the secondary phase of Ca2CuO3 was observed by XRD analysis, but the secondary phase of Mg2SiO4 that can improve the quality factor. There was no significant diffusion of copper into the substrate under the mapping observation.

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