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dc.contributorTsong-Jen Yangen_US
dc.contributorHung-Chien Linen_US
dc.contributor.advisorSham-Tsong Shiueen_US
dc.contributor.authorChiou, Sheng-Cheen_US
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dc.description.abstract本文主要是以電漿輔助化學氣相沉積法製備氟化非晶質碳膜(a-C:F),並探討a-C:F碳膜性質之影響。以六氟乙烷(C2F6)、乙炔(C2H2)以及氬氣(Ar)做為前驅氣體。工作壓力、基板溫度以及射頻功率分別設定為33.3 Pa、293 K(20℃)以及100 W。此外,將C2H2以及(C2F6+Ar)之流量分別固定為10 sccm與10 sccm, 而C2F6/(C2F6+Ar)比例分別為0、20、40、60、80與100 %。實驗結果顯示,當C2F6/(C2F6+Ar)比例由0 %增加至100 %時,沉積速率會由111 nm/min增加至215 nm/min。當C2F6/(C2F6+Ar)比例由0 %增加至20 %時,C-C以及C-Hx鍵結會轉變為C-F鍵結。然而,當C2F6/(C2F6+Ar)比例由20 %增加至100 %時,C-F鍵結會轉變為C-F2以及C-F3鍵結。當C2F6/(C2F6+Ar)比例由0 %增加至100%時,光學能隙值會從0.84 eV上升至2.39 eV,水接觸角度會由61°增加至90°,不過表面能會從45.0 mN/m下降至20.6 mN/m。結果指出當C2F6加入至C2H2中,a-C:F薄膜會轉變為類高分子結構且變得更加具有疏水性。 當C2F6/(C2F6+Ar)比例為100 %時,射頻功率從50 W增加至150 W時,碳膜的沉積速率從159 nm/min增加至230 nm/min;碳膜結構中的C-Fx鍵結會增加,而光學能隙值會從2.25 eV上升至2.56 eV。此外,當射頻功率從150 W增加至250 W時,碳膜的沉積速率從230 nm/min減少至90 nm/min;碳膜結構中的C-Fx鍵結會減少而F2C=C鍵結會增加。光學能隙值從2.56 eV下降至2.00 eV,碳膜結構會趨向類石墨化結構。當C2F6/(C2F6+Ar)比例為100 %時,工作壓力從33.3 Pa增加至66.7 Pa時,電漿中的氣體自由平均路徑變小,導致結構較為無序化。而在工作壓力為66.7 Pa時,碳膜具有一最大水接觸角度102.3°,這個結果指出碳膜會趨向於疏水性質。zh_TW
dc.description.abstractThe properties of fluorinated amorphous carbon (a-C:F) films prepared by plasma enhanced chemical vapor deposition (PECVD) method are investigated. Hexafluorethane (C2F6), acetylene (C2H2), and argon (Ar) were used as the precursor gases. The mass flow rate of C2H2 and (C2F6+Ar) are fixed at 10 and 10 sccm, respectively. Additionally, the working pressure, substrate temperature, and radio-frequency power were 33.3 Pa, 293 K, and 100 W, respectively. Six kinds of (a-C:F) films were prepared with the C2F6/(C2F6+Ar) ratio of 0, 20, 40, 60, 80, and 100 %. Experimental results show that the deposition rate of a-C:F films increases from 111 to 215 nm/min as the C2F6/(C2F6+Ar) ratio increases from 0 to 100 %. When the C2F6/(C2F6+Ar) ratio increases from 0 to 20 %, the C-C and C-Hx bonds are mainly changed to the C-F bonds. Nevertheless, when the C2F6/(C2F6+Ar) ratio increases from 20 to 100 %, the C-F bonds are changed to the C-F2 and C-F3 bonds. When the C2F6/(C2F6+Ar) ratio increases from 0 to 100 %, the optical band gap increases from 0.84 to 2.39 eV and the water contact angle increases from 61 to 90 degrees, but the surface free energy reduces from 45.0 to 20.6 mN/m. This result indicates that as C2F6 is added in C2H2, a-C:F films are shifting to polymer-like and become hydrophobic. As the C2F6/(C2F6+Ar) ratio is 100 %, the radio-frequency power increases from 50 to 150 W, the deposition rate of carbon films increases from 159 to 230 nm/min; the C-Fx bonds in the carbon films increase, and the energy band gap increases from 2.25 to 2.56 eV. Alternatively, as the radio-frequency power increases from 150 to 250 W, the deposition rate of carbon films decreases from 230 to 90 nm/min; the C-Fx bonds in the carbon films decrease, while the F2C=C bonds increase. The e energy band gap decreases from 2.56 to 2.00 eV, and the carbon films structure shifts to graphite-like. As the C2F6/(C2F6+Ar) ratio is 100 %, the working pressure increases from 33.3 to 66.7 Pa, the free path of plasmas gas decreases, and thus, the ordered degree of carbon films structure decreases. When the working pressure is 66.7 Pa, the carbon film has a maximum water contact angle of 102.3 degree, and thus the carbon film become hydrophobic.en_US
dc.description.tableofcontents總目錄 致謝 I 摘要 III Abstract V 總目錄 VII 圖目錄 XI 表目錄 XVII 第一章 緒論 1 1-1 前言 1 1-2 非晶質碳膜介紹 2 1-2-1 類鑽碳膜(Diamond-like Amorphous Carbon) 4 1-2-2 類石墨碳膜(Graphite-like Amorphous Carbon) 5 1-2-3 類高分子碳膜(Polymer-like Amorphous Carbon) 5 1-3 不同前驅氣體之氫碳比對非晶質碳膜性質之影響 6 1-4 氟化非晶質碳膜介紹 7 1-4-1 氟化非晶質碳膜之成膜機制 9 1-5 疏水性薄膜介紹 9 1-6 研究動機 11 1-7 論文概要 12 第二章 實驗步驟與儀器原理 13 2-1 試片準備與前處理 14 2-2 氟化非晶質碳膜的製備 16 2-2-1 沉積條件 16 2-2-2 簡介射頻電漿輔助化學氣相沉積系統 20 2-3 碳膜厚度量測 23 2-4 電漿診斷分析[58] 24 2-5 碳膜微觀結構分析 27 2-5-1 拉曼散射光譜儀(Raman Scattering Spectrometer, RSS) 27 2-5-2 X光光電子能譜儀(X-ray photoelectron spectroscopy, XPS)[67] 30 2-5-3傅立葉轉換紅外光光譜儀(Fourier Transform Infrared Spectroscopy, FTIR)[67,69] 35 2-6 碳膜光學性質量測 37 2-7 碳膜表面特性量測 38 2-7-1 原子力顯微鏡(Atomic Force Microscopy, AFM) 38 2-7-2 接觸角(Contact Angle, CA)量測儀 40 第三章 結果與討論 44 3-1 六氟乙烷比例對非晶質碳膜性質之影響 44 3-1-1電漿診斷分析 44 3-1-2 六氟乙烷比例對於非晶質碳膜沉積速率的影響 48 3-1-3 六氟乙烷比例對於非晶質碳膜微結構的影響 48 (a) 拉曼散射光譜儀 48 (b) 傅立葉轉換紅外光光譜儀 51 (c) X光光電子能譜儀 53 3-1-4 六氟乙烷比例對於非晶質碳膜光學性質的影響 59 3-1-5 六氟乙烷比例對於非晶質碳膜表面性質的影響 62 (a) 原子力顯微鏡 62 (b) 接觸角 65 3-2射頻功率對非晶質碳膜性質之影響 72 3-2-1電漿診斷分析 72 3-2-2射頻功率對於非晶質碳膜沉積速率的影響 75 3-2-3 射頻功率對於非晶質碳膜微結構的影響 77 (a) 拉曼散射光譜儀 77 (b) 傅立葉轉換紅外光光譜儀 79 3-2-4 射頻功率對於非晶質碳膜光學性質的影響 81 3-2-5 射頻功率對於非晶質碳膜表面性質的影響 84 (a) 原子力顯微鏡 84 (b) 接觸角 87 3-3工作壓力對非晶質碳膜性質之影響 89 3-3-1電漿診斷分析 89 3-3-2工作壓力對於非晶質碳膜沉積速率的影響 91 3-3-3 工作壓力對於非晶質碳膜微結構的影響 94 (a) 拉曼散射光譜儀 94 (b) 傅立葉轉換紅外光光譜儀 96 3-3-4 工作壓力對於非晶質碳膜光學性質的影響 98 3-3-5 工作壓力對於非晶質碳膜表面性質的影響 100 (a) 原子力顯微鏡 100 (b) 接觸角 103 第四章 結論 106 第五章 未來工作 109 參考資料 110   圖目錄 圖1-1 sp3、sp2以及sp1混成鍵結示意圖[20]。 2 圖1-2 含氫非晶質碳的三相平衡圖[21]。 4 圖1-3 以PECVD成長含氫非晶質碳膜時,沉積速率對前驅氣體離化能之關係圖[1,30]。 6 圖1-4 不同元素比例非晶質碳膜之水接觸角角度變化[14]。 11 圖2-1 實驗流程圖(不同六氟乙烷/(六氟乙烷+氬氣)比例)。 13 圖2-2 實驗流程圖(不同射頻功率以及工作壓力)。 14 圖2-3 製程中試片放置示意圖。 20 圖2-4 射頻電漿輔助化學氣相沉積系統外觀示意圖。 22 圖2-5 射頻電漿輔助化學氣相沉積系統腔體剖面示意圖。 22 圖2-6 射頻電漿輔助化學氣相沉積系統之反應腔體內部構造示意圖。 23 圖2-7 表面輪廓儀(α-step profile meter)外觀圖。 24 圖2-8 OES儀器外觀圖、光纖以及高速USB 2.0/1.1傳輸線。 25 圖2-9 OES儀器內部結構示意圖[59]。 26 圖2-10 OES儀器裝置圖。 26 圖2-11 (a) D band與(b) G band之振動模式示意圖[62]。 28 圖2-12 拉曼散射光譜儀(Raman Scattering Spectrometer, RSS)外觀圖。 30 圖2-13 原子內部電子被光子擊出之示意圖[63]。 31 圖2-14 光電子激發原理之各能量相關性示意圖。 32 圖2-15 X光光電子能譜儀(X-ray photoelectron spectroscope, XPS)外觀圖。 34 圖2-16 傅立葉轉換紅外光光譜儀(Fourier Transform Infrared Spectroscopy, FTIR)外觀圖。 36 圖2-17 紫外-可見光光譜儀(UV-Visible Spectrophotometer, UV/Vis)之外觀圖。 38 圖2-18 原子間作用力與距離的關係。 39 圖2-19 原子力顯微鏡(Atomic Force Microscopy, AFM)之外觀圖。 40 圖2-20 液體與固體表面呈現一接觸角[68]。 42 圖2-21 接觸角(Contact Angle, CA)量測儀之外觀圖。 43 圖3-1 不同C2F6/(C2F6+Ar)比例下,OES光譜圖。 46 圖3-2(a) 不同C2F6/(C2F6+Ar)比例下,電漿活性物種含量變化。(b) 不同C2F6/(C2F6+Ar)比例下,C2、C、CH以及CF2物種含量變化。 47 圖3-3 不同C2F6/(C2F6+Ar)比例下,碳膜沉積速率的變化。 48 圖3-4 不同C2F6/(C2F6+Ar)比例下,碳膜拉曼散射光譜圖。 50 圖3-5 不同C2F6/(C2F6+Ar)比例下,碳膜ωD、ωG、FWHMD、FWHMG以及ID/IG 的變化。 51 圖3-6(a)、(b) 不同C2F6/(C2F6+Ar)比例下,紅外光光譜圖的變化。 52 圖3-7 不同C2F6/(C2F6+Ar)比例下,碳膜的XPS全能譜圖。 53 圖3-8 不同C2F6/(C2F6+Ar)比例下,碳膜F/C比例的變化。 54 圖3-9 不同C2F6/(C2F6+Ar)比例下,(a) 碳膜的C1s軌域圖,(b) 碳膜的F1s軌域圖。 55 圖3-10 不同C2F6/(C2F6+Ar)比例下,(a)碳膜C1s軌域分峰圖,(b) 碳膜F1s軌域分峰圖。 57 圖3-11 不同C2F6/(C2F6+Ar)比例下,碳1s軌域中不同碳原鍵結含量百分比。 58 圖3-12 不同C2F6/(C2F6+Ar)比例下,氟1s軌域中不同碳原子鍵結含量百分比。 58 圖3-13 不同C2F6/(C2F6+Ar)比例下,碳膜光學能隙值的求法。 61 圖3-14 不同C2F6/(C2F6+Ar)比例下,碳膜光學能隙值(E04以及Eg)的變化。 62 圖3-15 不同C2F6/(C2F6+Ar)比例下,碳膜表面粗糙度的變化。 63 圖3-16 不同C2F6/(C2F6+Ar)比例下,碳膜表面形貌之3D立體圖。 64 圖3-17 不同C2F6/(C2F6+Ar)比例下,水接觸角的變化。 67 圖3-18 不同C2F6/(C2F6+Ar)比例下,乙二醇接觸角的變化。 67 圖3-19 不同C2F6/(C2F6+Ar)比例下,甲醯胺接觸角的變化。 68 圖3-20 不同C2F6/(C2F6+Ar)比例下,水接觸角示意圖。 69 圖3-21 不同C2F6/(C2F6+Ar)比例下,碳膜的Rrms與水接觸角的變化。 70 圖3-22 不同C2F6/(C2F6+Ar)比例下,碳膜表面能的變化,(a) 水與乙二醇,(b) 甲醯胺與乙二醇。 71 圖3-23 不同射頻功率下,OES光譜圖。 73 圖3-24(a) 不同射頻功率下,電漿活性物種含量變化。(b) 不同射頻功率下,C2、CH以及CF2物種含量變化。 74 圖3-25 不同射頻功率下,碳膜沉積速率的變化。 76 圖3-26 不同射頻功率下,自身負偏壓的變化。 76 圖3-27 射頻功率1/2次方與自身負偏壓的變化。 77 圖3-28 不同射頻功率下,碳膜拉曼散射光譜圖。 78 圖3-29 不同射頻功率下,碳膜ωD、ωG、FWHMD、FWHMG以及ID/IG 的變化。 79 圖3-30 不同射頻功率下,碳膜紅外光光譜的變化。 80 圖3-31 不同射頻功率下,碳膜紅外光光譜分峰圖。 81 圖3-32 不同射頻功率下,碳膜光學能隙值得求法。 83 圖3-33 不同射頻功率下,碳膜光學能隙值(E04以及Eg)的變化。 84 圖3-34 不同射頻功率下,碳膜表面粗糙度的變化。 85 圖3-35 不同射頻功率下,碳膜表面形貌之3D立體圖。 86 圖3-36 不同射頻功率下,水接觸角的變化。 87 圖3-37 不同射頻功率下,水接觸角示意圖。 88 圖3-38 不同工作壓力下,OES光譜圖。 90 圖3-39(a) 不同工作壓力下,電漿活性物種含量變化。(b) 不同工作壓力下,C2、C、CH以及CF2物種含量變化。 91 圖3-40 不同工作壓力下,碳膜沉積速率的變化。 92 圖3-41 不同工作壓力下,自身負偏壓的變化。 93 圖3-42 射頻功率(-1/2)次方與自身負偏壓的變化。 93 圖3-43 不同工作壓力下,碳膜拉曼散射光譜圖。 95 圖3-44 不同工作壓力下,碳膜ωD、ωG、FWHMD、FWHMG以及ID/IG 的變化。 96 圖3-45 不同工作壓力下,紅外光光譜的變化。 97 圖3-46 不同工作壓力下,碳膜紅外光光譜分峰圖。 98 圖3-47 不同工作壓力下,碳膜光學能隙值得求法。 99 圖3-48 不同工作壓力下,光學能隙值(Eg與E04)的變化。 100 圖3-49 不同工作壓力下,碳膜表面粗糙度的變化。 101 圖3-50 不同工作壓力下,碳膜表面形貌之3D立體圖。 102 圖3-51 不同工作壓力下,水接觸角的變化。 103 圖3-52 不同工作壓力下,水接觸角示意圖。 104 圖3-53 液滴與氟化非晶質碳膜的介面示意圖[53]。 105   表目錄 表1-1 非晶質碳和鑽石、石墨、碳60與聚乙烯材料之主要性質比較[1]。 3 表2-1 以不同六氟乙烷/(六氟乙烷+氬氣)比例的製程參數。 17 表2-2 以不同射頻功率的製程參數。 18 表2-3 以不同工作壓力的製程參數。 19 表2-4 近、中、遠紅外光範圍。 35 表3-1 電漿中活性物種之波長位置[69-76]。 45 表3-2 不同C2F6/(C2F6+Ar)比例下,電漿活性物種含量百分比。 47 表3-3 氟化非晶質碳膜紅外光譜吸收波長和C-F鍵結型態。 52 表3-4 不同C2F6/(C2F6+Ar)比例下,碳膜的F/C比例。 54 表3-5 C1s軌域中不同碳鍵結型態的束縛能。 56 表3-6 F1s軌域中不同碳鍵結型態的束縛能。 56 表3-7 碳1s軌域中不同C2F6/(C2F6+Ar)比例下,鍵結型態的比例。 57 表3-8 氟1s軌域中不同C2F6/(C2F6+Ar)比例下,鍵結型態的比例。 57 表3-9 不同C2F6/(C2F6+Ar)比例下,碳膜的光學能隙值。 61 表3-10 不同C2F6/(C2F6+Ar)比例下,碳膜表面粗糙度之關係。 63 表3-11 純水、乙二醇以及甲醯胺之表面張力數據。 66 表3-12 不同射頻功率下,電漿活性物種含量百分比。 74 表3-13 不同射頻功率下,碳膜C-F以及C-F2鍵結含量變化。 80 表3-14 不同射頻功率下,碳膜的光學能隙值。 83 表3-15 不同射頻功率下,碳膜表面粗糙度之關係。 85 表3-16 不同射頻功率下,水接觸角角度值。 88 表3-17 不同工作壓力下,電漿活性物種含量百分比。 91 表3-18 不同工作壓力下,碳膜C-F以及C-F2鍵結含量變化。 97 表3-19 不同工作壓力下,碳膜的光學能隙值。 100 表3-20 不同工作壓力下,碳膜表面粗糙度之關係。 101 表3-21 不同工作壓力,水接觸角角度值。 104zh_TW
dc.subjectPlasma enhanced chemical vapor depositionen_US
dc.subjectFluorinated amorphous carbonen_US
dc.titleEffects of process parameters on the properties of fluorinated amorphous carbon films prepared by plasma enhanced chemical vapor depositionen_US
dc.typeThesis and Dissertationzh_TW
Appears in Collections:材料科學與工程學系


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