近年來大氣常壓電漿被廣泛的應用於生醫相關的製程或療程上，因其相較於傳統電漿為低溫且溫和的放電形式，能減少對生物分子的影響，同時大氣常壓電漿並不需維持低壓的真空設備，能夠減少電漿設備的花費。本研究使用了介電質放電為基礎的遠距常壓電漿來進行薄膜沉積以固定蛋白質，因大氣常壓電漿在沉積薄膜時會把基材暴露在電漿放電區域內，蛋白質因此會直接受到電漿內因子如熱、反應粒子跟紫外光的影響而可能產生變性或是破壞，同時沉積薄膜的範圍也受到電極面積大小的限制。遠距電漿則是把基材置在電漿的放電區域外，如此一來電漿就不會直接影響基材或是蛋白質，同時還能借此達到大面積處理並改善薄膜的均勻性。

本研究中介電質遠距常壓電漿的系統主要由兩片垂直的平行介電質板構成，其間距約為2 mm，介電質外部貼上鋁膠帶做為正負兩端的電極 (面積50mm x 50 mm)，產生電漿的氣體為氦氣，使用的薄膜前驅物為乙烯，蛋白質則是使用牛血清蛋白。一開始會將氦氣通過配有蛋白質溶液的霧化器產生蛋白質水霧，並採用在電漿上游端混合乙烯與蛋白質、以及在電漿下游端混合蛋白質與和電漿反應聚合的聚乙烯分子等兩種不同的沉積方式來討論。蛋白質會在聚乙烯沉積的過程被包埋或是與薄膜上的官能基鍵結達到固定的效果。

實驗分析上使用了FTIR (傅立葉轉換遠紅外光譜)來檢測薄膜表面的鍵結，SEM (電子顯微鏡)則被用來觀看基材表面的薄膜沉積情形，同時對表面的微流清洗則用來檢驗蛋白質固定的效果，表面輪廓儀被用於檢測薄膜的厚度，以及利用螢光免疫分析法來觀察蛋白質是否依然保有活性。結果上我們成功檢測到蛋白質訊號與觀察到薄膜結構，並且在參數的討論中找到了一個適合沉積薄膜的參數調變。

In recent years, atmospheric pressure plasma (APP) has been widely used for bio-medical applications. APP can achieve non-thermal and mild discharge, reducing the heat influence to bio molecules. Without using vacuum systems, the cost of APP system can become lower. In this study, a dielectric-barrier-discharge based remote APP deposition (DBD RAPPD) system is used for protein immobilization. Since in APP system the deposition is occurred in the discharge region, protein may be denatured or damaged by the factors in the plasma, like heat, reactive species and UV. The deposition region is limited by area of the electrode in APP system. With remote plasma, deposition can occur at the downstream region of the plasma. Influence of plasma on protein can be reduce, large surface treatment and uniform coating can be achieve by this DBD RAPP system.

The DBD RAPP system used two parallel plate DBD, which has a 1mm distance between them. Aluminum tapes (50mm x 50 mm) are used as the electrodes. The working gas in plasma is helium, and the precursor is ethylene. The protein we used is BSA (Bovine serum albumin). Helium goes through the atomizer to generate protein aerosol. Ethylene reacts with plasma and becomes plasma-polymerized ethylene (ppE) then deposited onto the substrate. Upstream mixing (mixing BSA aerosol and ethylene before gas going through the discharge region) and downstream mixing (mixing BSA aerosol and ppE at the downstream region outside the discharge) are used for experiments discussions. BSA is immobilized by entrapment of ppE or bonded with functional groups.

FTIR was used for analyze the composite of coatings. SEM was used for investigate the morphology of coating surfaces. The coatings were rinsed by micro fluid to detect BSA adhesion. Surface profiler was used to analyze the thickness of coatings. Immunostaining was used for detecting the protein activity. In the result the signal and structure of BSA-ppE coating are detected and remained after rinse. Some appropriate experiment parameters for the immobilization are found.

摘要 iii
Abstract v
誌謝 vii
目錄 ix
表圖目錄 xii
第一章、 緒論 1
1.1 研究背景 1
1.1.1 蛋白質固定技術簡介 1
1.1.2 電漿原理和應用 1
1.1.3 介電質放電簡介 2
1.2 文獻回顧 2
1.2.1 兩階段介電質常壓電漿固定法 （Two-step DBD APP） 2
1.2.2 單步介電質常壓電漿固定法 （One-step DBD APP） 3
1.2.3 遠距電漿 3
1.3 研究動機與目標 4
1.4 論文架構 5
第二章、 實驗原理與檢測儀器 6
2.1 化學氣相沉積 （Chemical vapor deposition, CVD） 6
2.2 電漿化學氣相沉積 （Plasma-enhanced chemical vapor deposition, PECVD） 6
2.3 介電質放電遠距常壓電漿聚合沉積 (Dielectric barrier discharge remote atmospheric pressure plasma deposition, DBD-RAPPD) 7
2.4 實驗量測系統與分析儀器 9
2.4.1 傅里葉轉換紅外光譜儀 （Fourier transform infrared spectroscopy, FTIR） 9
2.4.2 掃描式電子顯微鏡 （Scanning electron microscope, SEM） 10
2.4.3 螢光免疫分析法 11
第三章、 實驗方法 13
3.1 實驗設備和實驗準備 14
3.1.1 介電質遠距常壓電漿沉積系統 14
3.1.2 電源供應器 16
3.1.3 氣體管路系統 18
3.1.4 微流清洗系統 20
3.1.5 實驗準備 21
3.2 實驗參數 22
3.2.1 Upstream mixing實驗 22
3.2.1.1 試片擺放位置對沉積結果的影響 22
3.2.1.2 脈衝輸出和正弦輸出比較分析 23
3.2.1.3 不同實驗條件下的沉積結果比較 23
3.2.2 Downstream mixing實驗 23
3.2.2.1 抽氣有無對沉積結果的影響 24
3.2.2.2 Mesh有無對沉積結果的影響 24
3.2.2.3 不同基材距離下的沉積結果比較 24
3.2.2.4 工作氣體流量對沉積的影響 24
3.2.2.5 穩流設計對沉積之影響 25
3.2.2.6 不同電壓頻率下的沉積表現 25
3.2.2.7 比較Upstream mixing和Downstream mixing的差異 26
3.2.3 螢光免疫分析法 27
3.2.4 氣體溫度量測 27
3.2.5 薄膜厚度量測 27
第四章、 實驗結果與討論 28
4.1 Upstream mixing之實驗結果 28
4.1.1 試片擺放位置實驗 28
4.1.2 脈衝輸出和正弦輸出沉積比較分析 29
4.1.2.1 脈衝輸出 30
4.1.2.2 正弦輸出 31
4.1.3 不同實驗條件下的沉積結果比較 33
4.1.3.1 純乙烯氣體和去離子水水霧 33
4.1.3.2 純BSA水霧 34
4.1.3.3 乙烯氣體和BSA水霧 36
4.2 Downstream mixing之實驗結果 37
4.2.1 抽氣有無對沉積的影響 37
4.2.2 加了Mesh結構對沉積之影響 40
4.2.3 基材和氣體出口之間的距離變化對沉積的影響 42
4.2.4 工作氣體流量對沉積的影響 44
4.2.5 加設穩流構造對沉積的影響 47
4.2.6 在不同電壓頻率下的沉積結果表現 49
4.3 Upstream mixing和Downstream mixing之結果比較 53
4.3.1 薄膜表面和厚度比較 53
4.3.2 螢光強度比較 55
4.3.3 混合氣體溫度比較 56
第五章、 結論與未來研究內容 58
5.1 結論 58
5.2 未來研究內容 59
參考文獻 60
附錄 62

1. Q. Luo, N. D’angelo, R. Merlino, Physics of Plasmas. 1998, 5, 2868.
2. A. Von Engel,J. Cozens, Flame plasmas, in Advances in electronics and electron physics. 1965, Elsevier. p. 99.
3. M. Laroussi, IEEE Trans Plasma Sci. 2008, 36, 1612.
4. U. Kogelschatz, Plasma chemistry and plasma processing. 2003, 23, 1.
5. G. Daeschlein, S. Scholz, R. Ahmed, T. von Woedtke, H. Haase, M. Niggemeier, E. Kindel, R. Brandenburg, K.-D. Weltmann, M. Juenger, Journal of Hospital Infection. 2012, 81, 177.
6. T.C. Montie, K. Kelly-Wintenberg, J.R. Roth, IEEE Transactions on plasma science. 2000, 28, 41.
7. P. Heyse, A. Van Hoeck, M.B. Roeffaers, J.P. Raffin, A. Steinbüchel, T. Stöveken, J. Lammertyn, P. Verboven, P.A. Jacobs, J. Hofkens, Plasma Processes and Polymers. 2011, 8, 965.
8. N. Dorraki, N.N. Safa, M. Jahanfar, H. Ghomi, S.-O. Ranaei-Siadat, Applied Surface Science. 2015, 349, 940.
9. P. Heyse, M.B. Roeffaers, S. Paulussen, J. Hofkens, P.A. Jacobs, B.F. Sels, Plasma Processes and Polymers. 2008, 5, 186.
10. G. Da Ponte, E. Sardella, F. Fanelli, S. Paulussen, P. Favia, Plasma Processes and Polymers. 2014, 11, 345.
11. N. Inagaki. Surface modification of polymeric materials by remote plasma. in Macromolecular symposia. 2000. Wiley Online Library.
12. F. Fanelli, P. Bosso, A.M. Mastrangelo, F. Fracassi, Japanese Journal of Applied Physics. 2016, 55, 07LA01.
13. A.H.R. Castro, F.V. Kodaira, V. Prysiazhnyi, R.P. Mota, K.G. Kostov, Surface and Coatings Technology. 2017, 312, 13.
14. R. Schropp, B. Stannowski, A. Brockhoff, P. Van Veenendaal, J. Rath, Mater. Phys. Mech. 2000, 1, 73.
15. J. Friedrich, Plasma Processes and Polymers. 2011, 8, 783.
16. G. Stancu, F. Kaddouri, D. Lacoste, C. Laux, Journal of Physics D: Applied Physics. 2010, 43, 124002.
17. P. Heyse, R. Dams, S. Paulussen, K. Houthoofd, K. Janssen, P.A. Jacobs, B.F. Sels, Plasma Processes and Polymers. 2007, 4, 145.
18. C.-P. Hsiao, C.-C. Wu, Y.-H. Liu, Y.-W. Yang, Y.-C. Cheng, F. Palumbo, G. Camporeale, P. Favia, J.-S. Wu, IEEE Transactions on Plasma Science. 2016, 44, 3091.
19. M.D. Larrañaga, R.A. Lewis, G.G. Hawley, Hawley's condensed chemical dictionary. 2016: John Wiley & Sons.
20. A. Fridman, Plasma Chemistry. 2008, Cambridge: Cambridge University Press.
21. S. Yao, E. Suzuki, N. Meng, A.J.E. Nakayama, fuels, 2001, 15, 1300.
22. A. Jahanmiri, M. Rahimpour, M.M. Shirazi, N. Hooshmand, H.J.C.e.j. Taghvaei, 2012, 191, 416.
23. Y.W. Yang, G. Camporeale, E. Sardella, G. Dilecce, J.S. Wu, F. Palumbo, P. Favia, Plasma Processes and Polymers. 2014, 11, 1102.