臺灣博碩士論文加值系統

本研究採用固態合成法合成製備出(Ba0.97Ca0.03)(Ti0.96Sn0.005Hf0.035)O3無鉛壓電陶瓷，並摻雜不同比例的ZnO與Fe2O3來降低其燒結溫度並有效提升在還原氣氛中燒結之壓電特性，分別探討在空氣中與還原氣氛中燒結對無鉛壓電陶瓷的各項電特性(壓電、鐵電、介電以及電熱)，再以刮刀成型及網印製程技術製備成生胚陶瓷薄帶，再與卑金屬銅電極在還原氣氛中進行共燒製作出積層壓電陶瓷，探討內電極層數對其壓電特性之影響，並將其應用於壓電微掃描面鏡致動平台，且透過ANSYS模擬得出元件之共振頻率及驅動電壓。
BCTSH在摻雜0.20 wt%ZnO並在燒結溫度1080°C下可以得到最佳特性如下： d33 = 328 pC/N，kp = 0.437，Qm = 359。後續再摻雜0.1 wt%Fe2O3並在空氣中燒結溫度1000°C下可以得到最佳特性如下：d33 = 335 pC/N，kp = 0.40，Qm = 337；在還原氣氛中(PO2 = 10-12 atm)燒結溫度1000°C下可以得到最佳電特性與電熱特性如下：d33 = 364 pC/N，kp = 0.35，Qm = 339，ΔT = 0.612 K，ΔT/ΔE = 0.204 Kmm/kV。與銅電極在燒結溫度1000°C，PO2 = 10-12 atm下進行還原氣氛共燒，堆疊4層下，可得到d33 = 1698 pC/N，kp = 0.19，Qm = 209之積層壓電陶瓷，可應用於目前電子產品中的積層致動器。
以ANSYS模擬後可得出當共振頻率為297.8 Hz時，驅動電壓為197.6 V，振動位移量為1.53 μm。

關鍵字：無鉛壓電陶瓷、卑金屬共燒、熱電效應、微掃描鏡

In this study, (Ba0.97Ca0.03)(Ti0.96Sn0.005Hf0.035)O3 lead-free piezoelectric ceramics were synthesized by the solid-state method. Through doping with varying proportions of ZnO and Fe2O3, the sintering temperatures are decreased and piezoelectric properties in a reducing atmosphere are effectively enhanced. For sintering in air atmosphere and in reducing atmosphere, the electrical properties (piezoelectric, ferroelectric, dielectric and thermoelectric) of lead-free piezoelectric ceramics were investigated, respectively. By the doctor blade and screen-printing processes, the ceramics green sheets are prepared and then were co-fired with a base metal copper electrode in a reducing atmosphere to form multilayer piezoelectric ceramics. In addition, the inference of the number of internal electrode layers was also investigated. These ceramics will be utilized to construct a platform for a stacked ceramic actuator which is combined with a scanning mirror. Finally, the resonance frequency and driving voltage were simulated by the ANSYS simulation software.
For the 0.2wt%ZnO-doped BCTSH and sintered at 1080C in air, we can obtain the best characteristic: d33 = 328 pC/N, kp = 0.437, Qm = 359. And after further doping with 0.1wt%Fe2O3 and sintered in air at 1000C, we can obtain the best characteristic: d33 = 335 pC/N, kp = 0.40, Qm = 337. Furthermore, for sintered in a reducing atmosphere (PO2 = 10-12 atm) at 1000C, it can be obtained the best electric and electrocaloric characteristics of d33 = 364 pC/N, kp = 0.35, Qm = 339, ΔT = 0.612 K, and ΔT/ΔE = 0.204 K·mm/kV. For the laminated piezoelectric ceramics with 4 layers of copper electrodes and co-fired in a reducing atmosphere (PO2 = 10-12 atm) at 1000C, it can be obtained the best characteristics of d33 = 1698 pC/N, kp = 0.19, and Qm = 209, which can be applied to the multilayer actuators for the modern electronic products.
As the resonance frequency is 297.8 Hz, we used the ANSYS simulation software to simulate and the simulated results were: vibration displacement is 1.53 μm and drive voltage is 197.6 V.

Keywords: Lead-free Piezoelectric Ceramics, Base-Metal Co-Firing, Electrocaloric Effect, Micro Scanning Mirror

摘要 I
Abstract II
致謝 IV
目錄 V
表目錄 IX
圖目錄 X
1 第一章 緒論 1
1.1 前言 1
1.2 研究背景與動機 2
1.3 論文架構 3
2 第二章 基礎理論與文獻回顧 4
2.1 壓電材料 4
2.1.1 壓電效應原理 4
2.1.2 壓電諧振體 6
2.1.3 壓電單晶體 7
2.1.4 壓電多晶體 7
2.1.5 壓電複合材料 8
2.2 壓電晶體結構 8
2.2.1 晶格與晶系 8
2.2.2 壓電晶體起源 10
2.2.3 容忍因子 11
2.3 壓電特性參數 12
2.3.1 壓電材料操作方向與模式 12
2.3.2 壓電方程式 13
2.4 介電效應 16
2.4.1 介電理論 16
2.4.2 介電損耗 17
2.5 鐵電效應 20
2.5.1 鐵電遲滯曲線 20
2.6 電熱效應 21
2.7 鈦酸鋇基無鉛壓電材料 24
2.8 積層壓電陶瓷 25
2.9 微型掃描鏡 27
2.9.1 光達系統介紹 27
2.9.2 壓電式致動之掃描微鏡 31
3 第三章 實驗步驟及量測 32
3.1 壓電陶瓷體原料之製作 32
3.1.1 壓電陶瓷粉末的製備 32
3.1.2 壓電陶瓷塊材的製程 32
3.2 積層壓電陶瓷之製程 34
3.2.1 漿料配置 34
3.2.2 生胚薄帶之製程 34
3.2.3 網印製程(Screen printing) 35
3.2.4 切割成型與熱水均壓 35
3.2.5 去黏劑(Binder burn out)及燒結(Sintering) 36
3.3 壓電陶瓷體特性量測及分析 39
3.3.1 密度量測 39
3.3.2 XRD分析量測 39
3.3.3 變溫介電量測 40
3.3.4 SEM分析 41
3.3.5 介電、壓電及鐵電電性量測 42
3.3.6 壓電溫度穩定性 47
4 第四章 實驗結果與討論 48
4.1 空氣中燒結之BCTSH+3%MnCO3+3%LiF+x wt%ZnO 49
4.1.1 空氣中燒結x wt%ZnO之XRD、SEM、晶粒尺寸分布與密度 49
4.1.2 空氣中燒結x wt%ZnO SEM、晶粒尺寸與密度 51
4.1.3 空氣中燒結x wt%ZnO之介電、壓電及鐵電特性 52
4.2 空氣中燒結之BCTSH+3%MnCO3+3%LiF+0.2 wt%ZnO+x wt% Fe2O3 56
4.2.1 空氣中燒結x wt% Fe2O3之XRD分析 56
4.2.2 空氣中燒結x wt% Fe2O3之SEM、晶粒尺寸與密度 57
4.2.3 空氣中燒結x wt% Fe2O3之介電、壓電及鐵電特性 58
4.3 還原氣氛燒結之BCTSH+3%MnCO3+3%LiF+0.2 wt%ZnO+x wt% Fe2O3 62
4.3.1 還原氣氛中燒結x wt% Fe2O3 之XRD 62
4.3.2 還原氣氛中燒結x wt% Fe2O3 之SEM 63
4.3.3 還原氣氛中燒結x wt% Fe2O3 之介電、壓電及鐵電特性 65
4.3.4 還原氣氛中燒結x wt% Fe2O3 之電熱特性 68
4.3.5 還原氣氛中燒結x wt% Fe2O3 之Cole-cole plot與活化能分析 72
4.4 還原氣氛燒結並改變燒結溫度之BCTSH+3%MnCO3+3%LiF+0.2 wt%ZnO+0.10 wt% Fe2O3 79
4.4.1 還原氣氛中改變燒結溫度BCTSH+3%MnCO3+3%LiF+0.2 wt%ZnO+0.10 wt% Fe2O3之XRD 79
4.4.2 還原氣氛中改變燒結溫度BCTSH+3%MnCO3+3%LiF+0.20 wt%ZnO+0.10 wt% Fe2O3之SEM 81
4.4.3 還原氣氛中改變燒結溫度BCTSH+3%MnCO3+3%LiF+0.2 wt%ZnO+0.10 wt% Fe2O3之介電、壓電及鐵電特性 83
4.5 銅金屬積層BCTSH+3%MnCO3+3%LiF+0.2 wt%ZnO+0.10 wt% Fe2O3 陶瓷在PO2=10-12atm下共燒 86
4.5.1 積層壓電BCTSH-MLZF陶瓷之XRD與SEM分析 86
4.5.2 積層壓電BCTSH-MLZF陶瓷改變銅電極層數之壓電、介電、鐵電特性 87
4.6 壓電陶瓷致動器平台元件模擬及設計 90
4.6.1 積層壓電致動器微鏡之ANSYS模擬及設計分析 90
5 第五章 結論與未來展望 93
5.1 結論 93
5.2 未來展望 94
參考文獻 95

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