臺灣博碩士論文加值系統

隨著抗菌材料應用越來越廣泛，人們對於抗菌材料的需求不只從生活用品，也漸漸發展到人體植入物的部分。而人體植入物必須重視的一點是，植入物是否會導致其它並發症。隨著所期望的植入時間日益增加以及植入位置變得對組織變形因素越來越敏感，會使得人體愈來愈排斥或無法順利地控制這些植入裝置，反而造成對人體一些不良的副作用;而在手術中，伴隨手術進行中侵入的微生物導致患部感染也是其中必須重視的問題之一。本篇研究藉由不同氧氣流量的反應共濺射來沉積Ag x O與TaOxNy-Ag薄膜，對薄膜的結構和機械性能進行研究，並測試樣品對大腸桿菌的抗菌行為。首先發現銀離子的溶解隨氧含量而變化，銀離子濃度隨著氧含量的增加將達到最大值後，達到平衡。與TaN-Ag膜相比，TaOxNy-Ag膜對大腸桿菌的抗菌效率可以大大提高，即更高的氧含量，有更好的抗菌效率。發現這是因為TaOxN y-Ag的金屬顆粒較小，更重要的是氧化銀的存在。通過測量金屬離子的溶解度，用ICP-OES證明了該結果。接著在溶液環境中通過大氣電漿處理退火的TaN-Ag薄膜。發現，在活化後，Ag離子的溶解速率可以顯著增加。因此，抗菌效率大大提高。

AgxO thin films were deposited by reactive co-sputtering with various oxygen flow rates.The films' structural and mechanical properties were examined. Then, the samples were tested for their antibacterial behaviors against Escherichia coli. It was first found that the dissolution of Ag ion was varied depending on oxygen contents. The Ag ion concentration would reach a maximum value with the increase of oxygen contents, then level off. The antibacterial efficiency of TaOxNy-Ag films against Escherichia coli could be much improved, comparing with that of TaN-Ag films, i.e. the higher oxygen content, the better antibacterial efficiency. The reasons for this were found to be due to smaller metal particles for TaOxNy-Ag, and, more importantly, the existence of silver oxide. This result was proved with ICP-OES by measuring the solubility of metal ions.
The annealed TaN-Ag thin films were then treated in either wet (immersed) environments by APPJ. It is found, after activation, the dissolution rate of Ag ions could be increased significantly. Hence the antibacterial efficiency was increased tremendously.

目錄
明志科技大學碩士學位論文口試委員審定書 I
誌謝 II
摘要 III
ABSTRACT IV
目錄 V
表目錄 VIII
圖目錄 IX
第1章 緒論 1
1.1. 前言 1
第2章 文獻回顧 3
2.1氮氧化鉭薄膜 3
2.1.1氮氧化鉭薄膜性質 3
2.2細菌 4
2.2.1分類 4
2.2.2細菌生長繁殖 5
2.2.3細菌細胞之代謝 5
2.2.4細菌細胞之運動 6
2.2.5影響細菌生殖的因素 6
2.2.6大腸桿菌 7
2.3抗菌介紹 8
2.3.1抗菌材料分類 8
2.3.2抗菌機制 10
2.3.3金屬離子抗菌效果 12
2.3.4抗菌材料的應用 14
2.4奈米薄膜 15
2.4.1薄膜成長機制 15
2.4.2奈米複合薄膜 16
2.4.3奈米複合薄膜之性能與特點 18
2.5大氣電漿 19
2.5.1大氣電漿源種類 19
2.5.2大氣電漿表面改質 21
2.5.3電漿制動活化水(Plasma activated water/PAW) 22
2.5.4 電漿制動活化水近年研究成果 23
2.6研究目的 25
第3章 實驗方法 26
3.1實驗流程與簡介 26
3.2實驗材料 27
3.2.1薄膜製程所需之材料 27
3.2.2大氣電漿處理所需之材料 27
3.2.3基材清洗程序 27
3.3實驗製程設備與量測儀器 28
3.3.1濺鍍系統介紹 28
3.3.2濺鍍參數 29
3.3.3快速退火爐簡介與退火參數 30
3.3.4大氣電漿處理系統 30
3.3.5薄膜分析與量測技術 31
3.3.6表面輪廓量測儀 (α-step) 31
3.3.7能量散佈分析儀 (Energy Dispersive Spectrometer, EDS) 32
3.3.8 X光繞射儀(X-Ray Diffraction, XRD) 33
3.3.9原子力顯微鏡 (Atomic Force Microscope, AFM) 34
3.3.10感應耦合電漿質譜儀 (Inductively Couple Plasma Optical Emission Spectrometry, ICP-OES) 35
3.3.11抗菌試驗 36
3.3.12 OH自由基化學劑量測定 39
3.3.13過氧化氫(H2O2)活性物質測定 40
第4章 實驗結果與討論 41
4.1 AGOX薄膜性質研究 41
4.1.1 AgOx薄膜結構與成份分析 41
4.1.2 AgOx薄膜粗糙度(Ra)分析 44
4.1.3 AgOx薄膜抗菌性質研究 45
4.1.4 AgOx薄膜溶解度分析 45
4.1.5 AgOx薄膜抗菌性分析 46
4.1.6 AgOx薄膜抑菌圈測試 47
4.2. TaNx-Ag薄膜與TaOxNy-Ag薄膜抗菌性分析 48
4.2.1 TaNx-Ag薄膜與TaOxNy-Ag薄膜溶解度分析 48
4.2.2 TaN-Ag薄膜與TaOxNy-Ag薄膜抗菌效果分析 49
4.2.3 TaOxNy-Ag化學鍵結能分析 50
4.3大氣電漿增強TaNx-Ag 薄膜抗菌性質分析 51
4.3.1 He/Ar大氣電漿光放射光譜分析 51
4.3.2. 大氣電漿活化水溶液中OH自由基定量分析 52
4.3.3. 大氣電漿活化水溶液中H2O2定量分析 53
4.3.4. 大氣電漿增強TaNx-Ag 薄膜溶解度分析 54
4.3.4. 大氣電漿增強TaNx-Ag 薄膜抗菌效果分析 55
第5章 結論及未來規劃 56
參考文獻 57

表目錄
表2-1抗菌材料分類 9
表2-2各金屬離子抗菌能力 13
表2-3金屬離子的最低抑菌濃度 14
表2-4抗菌材料應用領域 14
表3-1 AgOx薄膜濺鍍製程參數 29
表3-2 TaNx-Ag/TaOxNy-Ag薄膜濺鍍製程參數 30
表3-3TaNx-Ag薄膜大氣電漿處理參數 31
表3-4固態培養基配置參數 39

圖目錄
圖2-1革蘭氏陽性菌的結構圖。 4
圖2-2細菌常見分類。 4
圖2-3電子顯微鏡下之大腸桿菌。 8
圖2-4帶正電離子與帶負電細菌接觸產生拉力，導致細胞壁破洞影響繁殖。 11
圖2-5大腸桿菌於抗菌前後SEM形貌圖，(a)抗菌前，(b)抗菌後。 13
圖2-6薄膜成長機制示意圖。 15
圖2- 7純氦氣與氦氣+空氣大氣電漿處理之抗菌效果比較 24
圖2-8 (a)水和PB，和(b)鹽水和PBS形成TBARS，電漿處理後5小時對於大腸桿菌抗菌效果 24
圖3-1沉積AgOx薄膜與TaNx-Ag/TaOxNy-Ag薄膜實驗流程示意圖。 26
圖3-2 TaNx-Ag薄膜經大氣電漿處理實驗流程示意圖。 26
圖3-3輪廓儀工作原理示意圖。 32
圖3-4電子束與試片間交互作用。 32
圖3-5 X光對晶體繞射示意圖(θ:布拉格角)。 33
圖3-6作用力與距離間的關係示意圖。 34
圖3-7離子激發能階圖。 36
圖3-8酸鹼度測定儀。 37
圖3-9離心機。 37
圖3-10生化分析光譜儀。 38
圖3-11 螢光光譜儀 40
圖3-12 TA與OH自由基反應後形成為HTA 40
圖4-1 EDS對不同氧流量之AgOx薄膜成份分析。 41
圖4-2 XRD對不同氧流量之AgOx薄膜結構分析。 42
圖4-3 AgOx薄膜X射線光電子能譜圖。 43
圖4- 4AgOx薄膜中氧化銀電子能譜圖曲線下面積比率 43
圖4-5 AFM對不同氧流量之AgOx薄膜粗糙度分析。 44
圖4-6 AFM對不同氧流量之AgOx薄膜表面形貌分析。 44
圖4-7 ICP-OES對氧化銀薄膜溶解度分析。 45
圖4-8 ICP-OES在短效時間內對氧化銀薄膜溶解度分析。 46
圖4-9 AgOx薄膜在不同抗菌時段殺菌效果。 46
圖4-10短效時間內對氧化銀薄膜抗菌測試分析。 47
圖4-11 AgOx薄膜抑菌圈測試。 47
圖4- 12　 TaNx-Ag薄膜與TaOxNy-Ag薄膜溶解度分析 48
圖4- 13 TaNx-Ag薄膜與TaOxNy-Ag薄膜抗菌效果分析 49
圖4- 14 TaNx-Ag薄膜與TaOxNy-Ag薄膜抗菌效果分析 49
圖4- 15AgOx薄膜X射線光電子能譜圖。 50
圖4- 16 AgOx薄膜X射線光電子能譜曲線下面積 50
圖4- 17 He/Ar大氣電漿光放射光譜分析 51
圖4- 18 OH自由基定量分析 52
圖4- 19 大氣電漿活化水溶液中H2O2定量分析 53
圖4- 20　大氣電漿增強TaNx-Ag 薄膜抗菌溶解度分析 54
圖4- 21　大氣電漿增強TaNx-Ag 薄膜抗菌效果分析 55
圖4- 22　大氣電漿處理水溶液抗菌效果分析 55

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