第五章 結果與討論
5.3.4 基板與銀界面擴散研究
由於低溫共燒陶瓷基板會因為銀的擴散造成功能的劣化，擴散嚴 重甚至會使電極導通而無法使用，因此將本研究所製得之基板進行銀 擴散試驗；圖5-41(a)為陶瓷+80wt%GA50 玻璃所製成之基板與 Ag 之 EDS 線掃描(line scan)結果，圖中可看到，銀未擴散至基板中；圖 5-41(b) 為陶瓷+80wt%GP5210 玻璃所製成之基板與 Ag 之 line scan 結果，同 樣可看到銀無擴散現象產生，因此兩種基板皆適於LTCC 之應用。
表5-1 純玻璃與純 Mg4Nb2O9陶瓷塊材之微波特性
材料 εr Q Tanδ (×10-4)
τf
(ppm/℃)
密度 (g/cm3)
GA50 玻璃塊材 4 20 2.15
GP5210 玻璃塊材 7.5 245 3.84
純陶瓷塊材 12 4621 6 -27.6 4.382
0 200 400 600 800 1000 1200 92
Temperature (oC)
Point A
Calcination at 1050oC
Intensity (a.u.)
20 30 40 50 60 70
Sintering at 1200oC~1400oC
圖 5-3 Mg4Nb2O9陶瓷在不同燒結溫度之 X-ray 繞射圖
1200 1250 1300 1350 1400
4.9
Sintering Temperature (oC)
13.8 13.9 14.0 14.1 14.2
a parameter (A) c parameter (A)
圖5-4 Mg4Nb2O9陶瓷晶格常數隨溫度之變化
1200 1250 1300 1350 1400
Bulk density ( g/cm3 )
Bulk Contraction (%)
Sintering Temperature (oC )
圖5-5 Mg4Nb2O9在不同燒結溫度之體收縮與體密度曲線圖
1200 1250 1300 1350 1400
90
Sintering Temperature ( oC )
圖5-6 Mg4Nb2O9在不同燒結溫度之體密度與體理論密度之比值
1200℃ 1300℃
1250℃ 1350℃
1400℃
圖5-7 Mg4Nb2O9陶瓷在不同燒結溫度之 SEM 圖
1200 1250 1300 1350 1400 0
10 20 30 40 50 60 70 80 90 100
Grain Size (μ m)
Temperature (oC)
圖5-8 Mg4Nb2O9陶瓷在不同燒結溫度之晶粒尺寸
12.14
1200 1250 1300 1350 1400
dielectric Constant @ 9GHz
Qualify Factor @ 9GHz
Temperature (oC)
9GHz
圖 5-10 Mg4Nb2O9陶瓷體在不同燒結溫度之介電性質(εr、Q)
1200 1250 1300 1350 1400
-40
Temperature (oC)
20 30 40 50 60
20 30 40 50 60
0 200 400 600 800 99.80
Temperature (oC)
Endothermic Weight Loss %
DTA
Temperature (oC)
Endothermic
DTA TGA
Point A
Weight Loss %
55 60 65 70 75 80
Volume contraction (%)
Glass fraction (wt%)
圖 5-17 陶瓷+不同配比玻璃之體收縮率曲線圖
Bulk density (g/cm3 )
Glass fraction (wt%)
55 60 65 70 75 80 0.1
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
GA50 (B2O3- SiO2) GP5210 (ZnO-B2O3- SiO2)
Densification Factor
Glass fraction (wt%)
圖5-19 陶瓷+不同配比玻璃之緻密化因子曲線圖
(a)硼矽玻璃(GA50)與陶瓷之接觸角
(b)鋅硼矽玻璃(GP5210)與陶瓷之接觸角
圖 5-20 875℃熔融玻璃與 Mg4Nb2O9陶瓷之接觸角 CeCerraammiicc
CeCerraammiicc GAGA5500
GPGP55221100
200μm
200μm 5
599..11o 2020..77o
700 750 800 850 900
Volume Contraction (%)
GP5210 (ZnO-B2O3- SiO2)
Bulk Density ( g/cm3 )
Sintering Temperature (oC )
圖5-21 陶瓷+80wt%鋅硼矽玻璃不同溫度之體收縮與體密度
700 750 800 850 900
0.55
Sintering Temperature (oC)
圖 5-22 陶瓷+80wt%鋅硼矽玻璃在不同溫度之緻密化因子
(a)55wt%GA50 (b)60wt%GA50
(c)65wt%GA50 (d)70wt%GA50
(e)75wt%GA50 (f)80wt%GA50
圖 5-23 陶瓷+不同配比硼矽玻璃(GA50)之 SEM 圖
B
(a)55wt%GP5210 (b)60wt%GP5210
(c)65wt%GP5210 (d)70wt%GP5210
(e)75wt%GP5210 (f)80wt%GP5210
圖 5-25 陶瓷+不同配比鋅硼矽玻璃(GP5210)之 SEM 圖
(a)二次電子模式(SEI)
(b)背向散射電子模式(BEI)
圖 5-26 陶瓷+75wt%鋅硼矽玻璃(GP5210)之兩種模式 SEM 圖 A A →→
← ← B B
C C → →
20 25 30 35 40
T T T T T T
70wt%
80wt%
75wt%
2θ (degree)
: ZnNb2O6 MgNb2O6
T : Zn2SiO4
圖 5-27 陶瓷+70~80wt%GP5210 玻璃之 XRD 分析圖
(a)700℃ (b)750℃
(c)800℃ (d)850℃
(e)900℃
圖 5-28 陶瓷+80wt%鋅硼矽玻璃(GP5210)不同燒結溫度之 SEM 圖
圖 5-29 陶瓷+80wt%鋅硼矽玻璃在 875℃燒結之 TEM 明視野影像
AA22 <1<11100>>
C C
BB11
AA11
BB22
AA22
圖5-31 (ZnxMg1-x)Nb2O6之高解析度影像圖(HRTEM)
55 60 65 70 75 80
dielectric Constant @ 9GHz
Glass Fraction (wt%)
GA50 (B2O3- SiO2) GP5210 (ZnO-B2O3- SiO2) calculate GA50
圖 5-32 陶瓷+不同配比玻璃之介電常數曲線圖
Glass Fraction (wt%)
圖 5-33 陶瓷+不同配比玻璃之介電損失曲線圖
55 60 65 70 75 80 -33
-30 -27 -24 -21 -18 -15 -12 -9
-6 GA50(B2O3-SiO2)
GP5210(ZnO-B2O3-SiO2)
τ f (ppm/o C)
Glass Fraction (wt%)
Mg4Nb2O9
圖5-34 陶瓷+不同配比玻璃之共振頻率溫係數曲線圖
700 750 800 850 900
16 80wt% GP5210
Dielectric Constant @ 9GHz
Sintering Temperature (oC)
圖5-35 陶瓷+80wt%GP5210 玻璃在不同溫度之介電常數
700 750 800 850 900
0.003 80wt% GP5210 -12
tanδ @ 9GHz
Sintering Temperature (oC)
τ f (ppm/o C)
圖 5-36 陶瓷+80wt%GP5210 玻璃在不同溫度之介電損失與 τf
(a)陶瓷+80wt%硼矽玻璃(GA50)
(b)陶瓷+80wt%鋅硼矽玻璃(GP5210)
圖5-37 生胚薄帶疊壓後經 875℃燒結之基板 SEM 圖
(a)100MHz~1GHz 基板之介電常數
(b)15GHz~40GHz 基板之介電常數
2x108 4x108 6x1088x108109
(a)100MHz~1GHz 基板之介電損失
(b)15GHz~40GHz 基板之介電損失
2x108 4x108 6x1088x108109
15 20 25 30 35 40 0
20000 40000 60000 80000
Quality Factor
Frequency (GHz)
GA50(B2O3-SiO2) GP5210(ZnO-B2O3-SiO2) Al2O3
圖 5-40 基板在不同頻率之品質因子
(a)Ceramic+GA50 / Ag
(b) Ceramic+GP5210 / Ag
圖5-41 基板與 Ag 之 EDS 線掃描(line scan)分析 CeCerraammiicc ++ GGPP55221100
AgAg C
Ceerraammiicc ++ GGAA5500
AgAg
第六章 結論
本研究內容主要分三部分：利用固態反應法製備Mg4Nb2O9微波 介電陶瓷；利用添加玻璃助熔劑製備低溫共燒陶瓷塊材；並利用薄帶 成型法製作低溫共燒基板，針對實驗所得之結果，歸納出以下的幾項 結論：
1. Mg4Nb2O9 陶瓷粉末經由固態反應法所製備，將混合之 MgO 與 Nb2O5粉末在1050℃煆燒，可得具有純 Mg4Nb2O9相之陶瓷粉末。
2. 經固態反應法所製備之 Mg4Nb2O9微波介電陶瓷在1300℃燒結可 到達98%之高緻密化程度，在此溫度得到適當之晶粒尺寸，且具 有較佳之介電特性：εr = 11.7，Q = 4633(9 GHz) ，τf = -27.1 ppm/℃。
3. 將 Mg4Nb2O9陶瓷粉末加入 80wt%硼矽玻璃(GA50)，在 875℃燒 結後沒有新相生成，結晶相仍為 Mg4Nb2O9陶瓷相；在玻璃含量 80wt%得到最佳緻密程度(0.9)及優良介電特性：εr = 4.5，Q = 1788 (9 GHz) ，τf = -16.9 ppm/℃。
4. 將 Mg4Nb2O9陶瓷粉末加入80wt%鋅硼矽玻璃(GP5210)，在 875℃
燒結後陶瓷與玻璃反應產生結晶相，有助於品質因子之提升；在 玻璃含量80wt%得到最佳緻密化程度及較佳介電特性：εr = 6.6，
5. 陶瓷加入鋅硼矽玻璃 GP5210，在 875℃時結晶轉變為玻璃陶瓷，
產生超晶格有序結構，因此相較於硼矽玻璃(GA50)，陶瓷加入鋅 硼矽玻璃GP5210 具有較高之品質因子。
6. 基於微波介電特性考量，均選擇陶瓷加 80wt%玻璃進行低溫共燒 基板研究。陶瓷加80wt%GA50 玻璃於 Open Resonator 下量測之 εr = 4.3，Q = 12388 (15 GHz)，陶瓷加 80wt%GP5210 玻璃之 εr = 6.6，Q = 19532(15 GHz)，已符合實用上之需求。
7. 兩種基板與銀在 875℃熱處理後，皆無擴散現象產生，因此適合 於LTCC 基板之應用。
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