臺灣博碩士論文加值系統

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.

目錄
摘要 I
Abstract III
目錄 VI
圖目錄 VIII
表目錄 XII
第一章 緒論 1
第二章 文獻回顧 4
2-1微波介電材料特性與原理 4
2-1-1介電常數 5
2-1-2品質因子 7
2-1-3共振頻率溫度係數 9
2-2微波介電材料系統發展與開發 10
2-2-1高溫共燒陶瓷系統之微波介電材料 10
2-2-2低溫共燒陶瓷系統之微波介電材料 12
2-3透輝石相玻璃陶瓷材料系統設計 13
2-4玻璃陶瓷製程與成長機制 15
2-4-1玻璃陶瓷之製程 15
2-4-2成核機制 16
2-4-3結晶成長機制 19
2-5常用電極種類與特性 20
第三章 實驗流程與分析方法 21
3-1實驗程序 21
3-2實驗儀器與規格 28
3-3材料性質檢測手法 28
3-3-1 XRD分析 28
3-3-2 SEM微觀分析 29
3-3-3 品質因子與介電常數測量 30
第四章 實驗結果與討論 32
4-1透輝石相玻璃陶瓷添加ZnO之分析結果 32
4-1-1透輝石相玻璃陶瓷添加不同ZnO比例之電性與XRD分析 32
4-1-2透輝石相玻璃陶瓷添加ZnO在不同熱處理溫度之分析 34
4-2透輝石相添加陶瓷粉體之特性研究 40
4-2-1添加(Zn0.6Mg0.4)2SiO4陶瓷粉體之分析結果 40
4-2-2添加MgTiO3陶瓷粉體之分析結果 46
4-2-3添加 (Zn0.6Mg0.4)2SiO4和MgTiO3陶瓷粉體之分析結果 56
4-3透輝石相玻璃陶瓷添加陶瓷粉體與電極共燒之特性研究 60
4-3-1銀膠與銅膠之TGA分析 61
4-3-2透輝石相玻璃陶瓷添加陶瓷粉末之微結構 62
4-3-3透輝石相玻璃陶瓷添加陶瓷粉體與銀電極共燒之微觀結構 64
4-3-4透輝石相玻璃陶瓷與銅電極共燒之微觀結構 67
第五章 結論 70
第六章 參考文獻 73
圖目錄
圖2- 1電磁波能譜圖及頻率應用[1] 4
圖2- 2不同極化機制與頻率之關係 7
圖2- 3在介電材料上施加電壓時，極化之強度及電荷量和時間關係 8
圖2- 4為電容器充電時的相位關係圖 9
圖2- 5 SiO2-CaO-MgO之三元相圖[41] 15
圖2- 6玻璃陶瓷製程、(b)玻璃陶瓷淬火與時間關係、(c)玻璃陶瓷成核速率與溫度關係 [44] 16
圖2- 7成核及結晶成長速率與溫度的關係圖[45] 20

圖3- 1透輝石相玻璃陶瓷製備及在不同溫度燒結之實驗流程 23
圖3- 2輝石相玻璃陶瓷添加陶瓷粉體在不同溫度燒結之實驗流程 25
圖3- 3透輝石相玻璃陶瓷添加陶瓷粉體與電極共燒之實驗流程 27
圖3- 4 Bruker D2 Phaser 29
圖3- 5樣品鍍白金機(左)與電子顯微鏡機台(右) 29
圖3- 6圓柱型共振量測夾具之示意圖 30
圖3- 7圓柱型共振量模具 31

圖4- 1透輝石相玻璃陶瓷添加4mol%ZnO在960℃/2hr之XRD分析[47] 33
圖4- 2透輝石相玻璃陶瓷添加x mol% ZnO經960℃/2hr之電性分析[47] 33
圖4- 3透輝石相玻璃陶瓷添加4mol% ZnO經不同熱處理溫度持溫兩小時之XRD (A)960℃:20~30o (B)960℃:29~38o分析 35
圖4- 4透輝石相玻璃陶瓷添加4mol% ZnO經不同熱處理溫度持溫兩小時之介電性質分析 36
圖4- 5透輝石玻璃融塊進行DTA(熱差分析儀)分析[50] 36
圖4- 6透輝石相玻璃陶瓷於850℃熱處理持溫不同時間的XRD繞射圖譜[50] 37
圖4- 7透輝石相玻璃陶瓷添加ZnO熱處理之SEM-EDS成分及微觀結構分析 38
圖4- 8 39
圖4- 9 Zn2SiO4與Mg2SiO4相圖[52] 41
圖4- 10(ZnxMg1-x)2SiO4陶瓷(x=0~1.0) XRD分析 [53] 41
圖4- 11(ZnxMg1-x)2SiO4經大氣下1250℃/2hr熱處理之介電特性 [55] 42
圖4- 12透輝石相玻璃陶瓷添加x wt% (Zn0.6Mg0.4)2SiO4經960℃/2hr熱處理之介電特性[55] 42
圖4- 13透輝石相玻璃陶瓷添加8wt% (Zn0.6Mg0.4)2SiO4之SEM-BEI微觀結構 43
圖4- 14透輝石相玻璃陶瓷添加8wt% (Zn0.6Mg0.4)2SiO4經不同熱處理溫度持溫兩小時之XRD (A)20~29o (B)29~40o分析 44
圖4- 15透輝石相玻璃陶瓷添加8wt% (Zn0.6Mg0.4)2SiO4經不同熱處理溫度持溫兩小時之介電性質分析 45
圖4- 16透輝石相玻璃陶瓷添加不同比例的MgTiO3經950℃燒結持溫兩小時之XRD分析[56] 47
圖4- 17透輝石相玻璃陶瓷添加不同比例的MgTiO3經950℃燒結持溫兩小時之密度與介電特性分析[56] 47
圖4- 18透輝石相玻璃陶瓷添加8wt% MgTiO3經900℃持溫兩小時之SEM-EDS元素分析及微結構 49
圖4- 19透輝石相玻璃陶瓷添加8wt% MgTiO3經900℃持溫兩小時之Mapping元素分析 50
圖4- 20透輝石相玻璃陶瓷添加8wt% MgTiO3經960℃持溫兩小時之Mapping元素分析 51
圖4- 21透輝石相玻璃陶瓷添加8wt% MgTiO3經不同熱處理溫度持溫兩小時之SEM微觀分析 52
圖4- 22 MgTiO3之XRD分析 53
圖4- 23透輝石相玻璃陶瓷添加8wt% MgTiO3經不同燒結溫度持溫兩小時之XRD (A)29~38o (B)48~65o分析 54
圖4- 24透輝石相玻璃陶瓷添加8wt% MgTiO3經不同燒結溫度持溫兩小時之介電性質分析 55
圖4- 25透輝石相玻璃陶瓷添加8wt% MgTiO3和8wt% (Zn0.6Mg0.4)2SiO4經不同熱處理溫度持溫兩小時之SEM微觀分析 57
圖4- 26透輝石相玻璃陶瓷添加8wt% MgTiO3和8wt% (Zn0.6Mg0.4)2SiO4經900℃持溫兩小時之SEM-EDS元素分析 58
圖4- 27透輝石相玻璃陶瓷添加8wt% MgTiO3和8wt% (Zn0.6Mg0.4)2SiO4經不同熱處理溫度持溫兩小時之XRD分析 59
圖4- 28透輝石相玻璃陶瓷添加8wt% MgTiO3和8wt% (Zn0.6Mg0.4)2SiO4經不同熱處理溫度持溫兩小時之介電性質分析 59
圖4- 29銀膠TGA分析 61
圖4- 30銅膠TGA分析 61
圖4- 31透輝石相玻璃陶瓷與銀共燒之剖面Mapping分析[64] 62
圖4- 32透輝石相玻璃陶瓷添加不同陶瓷粉體經900℃持溫兩小時之SEM微觀結構比較 63
圖4- 33透輝石相玻璃陶瓷無添加(左)和添加8wt% (Zn0.6Mg0.4)2SiO4(右)與銀膠於900℃共燒之SEM微觀結構比較 64
圖4- 34透輝石相玻璃陶瓷添加8wt% (Zn0.6Mg0.4)2SiO4(左)和添加8wt% MgTiO3(右)與銀膠於900℃共燒共燒之SEM微觀結構比較 64
圖4- 35透輝石相玻璃陶瓷添加8wt% (Zn0.6Mg0.4)2SiO4與銀膠於900℃共燒持溫兩小時之Mapping元素分析 65
圖4- 36透輝石相玻璃陶瓷添加8wt% MgTiO3與銀膠於900℃共燒持溫兩小時之Mapping元素分析 66
圖4- 37透輝石相玻璃陶瓷與銅膠於還原氣氛下960℃共燒持溫兩小時之XRD分析 67
圖4- 38透輝石相玻璃陶瓷與銅膠於還原氣氛下960℃共燒持溫兩小時之SEM-EDS元素分析和微結構 68
圖4- 39透輝石相玻璃陶瓷與銅膠於還原氣氛下960℃共燒持溫兩小時之Mapping元素分析 69





表目錄
表2- 1四種不同極化機制關係 6
表2- 2不同極化機制與頻率之關係 6
表2- 3共振頻率溫度係數證明公式及關係 10
表2- 4低介電常數矽酸鹽、鉬酸鹽、鎢酸鹽類微波介電陶瓷材料 11
表2- 5低介電常數鎂鈣矽系統微波介電陶瓷材料 12
表2- 6常見商用電極系統[46] 20

表3- 1使用藥品規格與來源廠商 22
表3- 2各種使用儀器來源與規格 28

表4- 1透輝石相玻璃陶瓷添加ZnO熱處理之SEM-EDS成分分析(A區)(B區)(C區) 38
表4- 2透輝石相玻璃陶瓷添加8wt% MgTiO3經900℃持溫兩小時之SEM-EDS元素分析(A區) (B區) 49
表4- 3透輝石相玻璃陶瓷添加8wt% MgTiO3和8wt% (Zn0.6Mg0.4)2SiO4經900℃持溫兩小時之SEM-EDS元素分析(A區)(B區)(C區) 58
表4- 4各種內電極之比較 60
表4- 5透輝石相玻璃陶瓷與銅膠於還原氣氛下960℃共燒持溫兩小時之SEM-EDS元素分析(A區) (B區) 68

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