中文摘要………………………………………………………………...I 英文摘要………………………………………………………………..III 目錄……………………………………………………………………. .V 圖目錄………………………………………………………………...VIII 表目錄…………………………………………………………………..XI 第一章 緒論……………………………………………………………..1 第二章 理論基礎………………………………………………………..3 2-1 燃料電池簡介……………………………………………………….3 2-1-1燃料電池之原理…………………………………………………...3 2-1-2燃料電池的分類…………………………………………………...5 2-1-3燃料電池之優點及應用…………………………………………...5 2-2 固態氧化物燃料電池之結構與反應…………………………….....9 2-3 固態氧化物電解質………………………………………………...10 2-4 固態陰極材料………………………………………………...........12 2-5 射頻磁控濺鍍原理………………………………………………...15 2-6薄膜成核沉積理論………………………………………………....15 2-7 薄膜成長模式………………………………………………...........17 2-8 研究目的………………………………………………...................18 第三章 實驗方法與步驟………………………………………………20 3-1 實驗流程………………………………………………...................20 3-2 濺鍍系統設計………………………………………………...........25 3-3 原料選擇………………………………………………...................27 3-4 鍍膜參數及步驟……………………………………………….......28 3-4-1鍍膜參數..……………………………………………….............28 3-4-2鍍膜步驟..……………………………………………….............28 3-5 鍍膜熱處理..……………………………………………….............28 3-6 薄膜性質分析..……………………………………………….........29 3-6-1 X光繞射分析..……………………………………………….....29 3-6-2 SEM觀察..………………………………………………............29 3-6-3 感應式偶合電漿分析儀(ICP-AES) ..………………………….29 3-7 薄膜電性量測..……………………………………………….........29 3-7-1 四點探針電阻分析儀(four point probe) ..……………………..29 3-7-2 電極極化之量測 (over potential) ..……………………………30 3-7-3 交流阻抗分析 (ac-impedance analyze) ..……………………..30 第四章 結果與討論..…………………………………………………..33 一 LSCu薄膜分析..……………………………………………………33 4-1 LSCu薄膜之晶體結構分析..……………………………………...33 4-2 LSCu薄膜之微觀型態.……………………………………............35 4-3 LSCu薄膜之成長速率.……………………………………............37 4-4 LSCu薄膜之成分 …...……………………………………............37 二 LSCu薄膜電性分析…...……………………………………...........42 4-5 LSCu薄膜的導電性…...…………………………………….......42 4-6 陰極過電壓量測…...……………………………………................45 4-6-1 溫度對LSCu薄膜陰極過電壓的影響…………................47 4-6-2 LSCu薄膜厚度對陰極過電壓的影響…………..................47 4-6-3 LSCu電極的反應機制…………..........................................50 4-6-4 LSCu薄膜的鍶離子添加量對陰極極化現象之影響..........51 4-6-5 LSCu薄膜之晶粒大小對陰極極化現象之影響..................54 4-7 交流阻抗分析…...……………………………………....................60 4-7-1 LSCu薄膜不同厚度的電荷轉移電阻…………..................56 4-7-2 LSCu薄膜不同厚度的氧離子擴散電阻………..................64 4-8 LSCu之氧離子導電率……….........................................................67 第五章 結論………................................................................................71 參考文獻………......................................................................................73 誌謝……………………………………………………………………..76 圖目錄 Fig. 2-1 Schematic of fuel cell……………………………………………4 Fig. 2-2 Schematic of the typical electrochemical reactions in fuel cell.…………………………………………………………………….....8 Fig.2-3 Schematic of solid oxide fuel ell………………………………..11 Fig. 2-4 The perovskite structure………………………………………..14 Fig. 2-5 The plane circle of magnetron structure ……………................16 Fig. 2-6 The three crystal growth modes.………………………….........19 Fig. 3-1 The flow chart of the experiment………………….……...……20 Fig. 3-2The flow chart of target…………………………………………21 Fig. 3-3 The flow chart of substrate …………………….……………...22 Fig. 3-4 The sintering curve of target…………………………………...23 Fig. 3-5 The sintering curve of substrate………………………...……...24 Fig. 3-6 The RF magnetron sputtering measurement …………………..26 Fig. 3-7 The schematic of four point probe……………….………….....31 Fig. 3-8 The current interrupt method ……………………..…………...32 Fig.4-1 The XRD patterns of LSCu thin films on YSZ substrate of (a) as-deposited and heat treatment at (b) 500℃ (c) 600℃ (d) 700℃ (e) 800℃for 1 hour in air.…………………………………………………..34 Fig.4-2 The top view SEM images of LSCu films on YSZ substrate (a) as-deposition, and heat treatment at (b) 500℃ (c) 600℃ (d) 700℃ (e) 800℃ for 1 hour. The cross section SEM of LSCu thin on YSZ substrate and heat treatment at (f) 700 ℃ for 1 hour.…………………….……….36 Fig.4-3 The thickness of LSCu films were in range from 60W to 120W RF power………………………………………………………….…….38 Fig. 4-4 The growth rate of LSCu films were at different RF power.......40 Fig.4-5 The electrical conductivity of LSCu films that were heat-treated at various temperatures from 500oC to 800oC…………………………..44 Fig. 4-6 The top view(a) and cross-section(b) images of testing sample, and schematic diagrams of YSZ-supported half cell for electrochemical analyses.………………………………………………………………....46 Fig.4-7 Cathodic polarization of LSCu dense film electrodes measured in the temperature range of 550~700℃ in air……………………………..48 Fig. 4-8 Cathodic polarization of LSCu dense film electrodes measured in the LSCu film thickness range of 1~4μm………………………………49 Fig. 4-9 Schematic of the cathodic reaction on dense electrode………..52 Fig. 4-10 Cathodic polarization of LSCu and LSM dense film electrodes measured at 700℃……………………………………………...............53 Fig. 4-11 Cathodic polarization of LSCu dense film electrodes measured at 700℃ in different heat treatment time…………………………..……55 Fig. 4-12 The top view SEM images of RF magnetron sputtered LSCu films on YSZ were heat treatment at 700℃ for (a)1 hour (a)6 hour (a)12 hour (a)24 hour in air.…………………………………………………...57 Fig. 4-13 AC impedance spectra measured for dense LSCu electrode in the temperature range of (a)400℃, (b)450℃, (c)500℃ and (d)550℃ in air………………………………………………………………………..58 Fig.4-14. The equivalent circuit of the LSCu film on YSZ substrate…...61 Fig. 4-15 The charge transfer resistances plotted as the temperature in various thickness of dense LSCu electrodes……………………………62 Fig. 4-16 The charge transfer resistance of LSCu film was as a function of inverse absolute temperature.………………………………………...63 Fig. 4-17 The oxygen ion diffusion resistances obtained from impedance spectra in different thicknesses.……………………………………..…..65 Fig. 4-18 The oxygen ion diffusion resistance of LSCu film was as a function of inverse absolute temperature.………………………..……...66 Fig.4-19 Schematic of the ionic conductivity measurement…………....68 Fig. 4-20 The ionic conductivity of LSCu plotted as a function of temperature from 873K to 1073K.……………………………………...70 表目錄 Table. 2-1 The fundamental characteristicof the fuel cells…………….…6 Table. 2-2 The anode and cathode reaction of the fuel cells……………..7 Table. 4-1 The growth rate of LSCu films were at different RF power....39 Table. 4-2 The composition of La1-xSrxCuO2.5-δ film……………..……..41 Table. 4-3 Summary of the equivalent circuit model results.…………...60