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研究生：	范駿威 Fan, Chun-wei
論文名稱：	以射頻濺鍍法沉積5B、6B族過渡金屬氮化物薄膜之表面自由能效應研究 Effects in surface free energy of sputter-deposited 5B、6B transitional metal nitride films
指導教授：	李世欽 Lee, Shih-chin
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2008
畢業學年度：	96
語文別：	中文
論文頁數：	101
中文關鍵詞：	接觸角、表面自由能、過渡金屬氮化物、IC封裝、抗沾黏、射頻濺鍍法
外文關鍵詞：	Water contact angle, Surface free energy, IC packaging, Transitional metal nitride, Non-sticking, RF sputtering
相關次數：	點閱：112 下載：0
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本論文利用射頻濺鍍法生長疏水性、抗沾黏、硬度高、熱穩定度高和防腐蝕的VNx、NbNx、TaNx、MoNx、WNx功能性薄膜，探討其薄膜組成、溫度(20-170 ℃)和表面粗糙度對表面自由能之影響，作為電子封裝模具表面被覆層之應用參考。實驗的結果顯現，隨著氮含量的增加，在20 ℃時的接觸角也跟著增加，表面自由能則下降，在VN1.73、NbN1.71、TaN1.58、MoN2.07、WN1.91時有一接觸角最大值101.4o~119.2o，和表面自由能最小值29.8~39.6 mN/m，之後接觸角就呈下降趨勢，表面能則呈上升趨勢。這可能是因為這五種成分比值接近最穩定的化合成分，造成水滴最不易與其形成氫橋，接觸角最大，表面的能量也最低。而氫橋會影響薄膜表面能，大接觸角代表弱的氫橋，表面自由能自然較低。而總自由能和極性自由能有相同的趨勢。五種薄膜皆有好的抗沾黏能力(接觸角>100o，表面自由能<40 mN/m)。高溫也有助於接觸角及表面能的降低，因為溫度的增高，氫橋開始斷裂，水開始蒸發，也可由Gibbs 熱力學關係式來說明，但它也增加了成本。表面自由能也和薄膜表面粗糙度有正比關係，因為表面越粗糙時，薄膜表面積較大，形成氫橋的可能性增加，因此增加了表面能，這也符合了原理的推導結果。

This study describes depositing VNx, NbNx, TaNx, MoNx and WNx coatings using RF sputtering to develop wear resistant, non-sticking, high hardness, thermal stable and corrosion resistant coatings for IC molding tools. It is focused on the influence to the surface free energy (SFE) by film composition, surface temperature and surface roughness.
The experimental results show that with increasing N content in the deposited films, the water contact angle ultimately increase to 101.4o~119.2o, and SFE decrease to 29.8~39.6 mN/m. This corresponds to the film composition VN1.73, NbN1.71, TaN1.58, MoN2.07, WN1.91. Because these five compositions are close the most stoichiometric compositions. It is therefore elucidated that the hydrogen bridge between water and the coating surface is difficult to formed. The SFE of the five coatings present the same trend to polar component of SFE, which seems the reason for these five coating materials presenting non-sticking characteristic (contact angle>100o, SFE<40 mN/m).
Contact angle and SFE are also found to decrease when surface temperature is increased. This is due to water desorption of the surface that break hydrogen bridges and fit Gibbs equation. SFE also has a direct influence by the surface roughness of these coatings. A rougher surface increases surface area and likely to ease hydrogen bridge formation, and thereby increases SFE.

目錄
封面.....................................................1
授權書...................................................2
中文合格證明.............................................3
英文合格證明.............................................4
中文摘要.................................................5
英文摘要.................................................6
誌謝.....................................................8
目錄.....................................................9
圖目錄..................................................11
表目錄..................................................15
第一章 序論.............................................16
1-1 前言................................................16
1-2 動機與目的..........................................17
第二章 原理.............................................18
2-1 表面自由能應用之領域................................18
2-2 鍍膜................................................22  
2-2-1 電漿..............................................22
2-2-2 濺鍍..............................................24
2-2-3 二極濺鍍..........................................27
2-2-4 射頻濺鍍..........................................27
2-3 接觸角與表面自由能之關聯性..........................30
2-4 溫度與表面自由能之關聯性............................36
2-5 薄膜粗糙度與表面自由能之關聯性......................37
第三章 實驗.............................................39
3-1 薄膜成長............................................39
3-2 試片製備............................................43
3-3 成分分析............................................44
3-4 接觸角與表面自由能之關聯性..........................45
3-5 溫度與表面自由能之關聯性............................49
3-6 薄膜粗糙度與表面自由能之關聯性......................52
第四章 結果與討論.......................................55
4-1 接觸角與表面自由能之關聯性..........................55
4-2 溫度與表面自由能之關聯性............................64
4-3 薄膜粗糙度與表面自由能之關聯性......................86
第五章 結論.............................................93
參考文獻................................................95
自述...................................................101

圖目錄
Fig. 2-1 Applications in surface free energy............20
Fig. 2-2 Cavity bar for IC packing......................21
Fig. 2-3 The interaction between Ar ion gas and the target surface.................................................26
Fig. 2-4 RF-sputter deposition system used in this study...................................................29
Fig. 2-5 Galileo’s explanation for the floating of thin sheets gold on water....................................31
Fig. 2-6 Geometric parameters for determining interfacial energy..................................................32
Fig. 3-1 The growth mechanism of the coating............40
Fig. 3-2 The Thornton Structure-Zone model of sputter deposited layers........................................42
Fig. 3-3 Schematic representation of step sequence for coating deposition......................................43
Fig. 3-4 The process of the contact angle measurement...46
Fig. 3-5 Dataphysics OCA-20 contact angle analyzer......47
Fig. 3-6 The apparatus of atomic force microscopy (AFM)...................................................53
Fig. 3-7 Schematic representation of AFM operation......53 
Fig. 3-8 The AFM topographies of various RMS coatings...54
Fig. 4-1 Contact angle images of test liquids on the TaNx films at 20℃...........................................56
Fig. 4-2 Effect of film composition on surface free energy (SFE) components of VNx thin films at 20℃..............58
Fig. 4-3 Effect of film composition on surface free energy (SFE) components of NbNx thin films at 20℃.............59
Fig. 4-4 Effect of film composition on surface free energy (SFE) components of TaNx thin films at 20℃.............60
Fig. 4-5 Effect of film composition on surface free energy (SFE) components of MoNx thin films at 20℃.............61
Fig. 4-6 Effect of film composition on surface free energy (SFE) components of WNx thin films at 20℃..............62
Fig. 4-7 Contact angle images of test liquids on the TaN1.58 film at 20-95 ℃................................65
Fig. 4-8(a) Effect of film surface temperature on the Total SFE of VNx thin films prepared at different composition.............................................71 
Fig. 4-8(b) Effect of film surface temperature on the Dispersive SFE of VNx thin films prepared at different composition.............................................72 
Fig. 4-8(c) Effect of film surface temperature on the Polar SFE of VNx thin films prepared at different composition.............................................73 
Fig. 4-9(a) Effect of film surface temperature on the Total SFE of NbNx thin films prepared at different composition.............................................74 
Fig. 4-9(b) Effect of film surface temperature on the Dispersive SFE of NbNx thin films prepared at different composition.............................................75 
Fig. 4-9(c) Effect of film surface temperature on the Polar SFE of NbNx thin films prepared at different composition.............................................76
Fig. 4-10(a) Effect of film surface temperature on the Total SFE of TaNx thin films prepared at different composition.............................................77
Fig. 4-10(b) Effect of film surface temperature on the Dispersive SFE of TaNx thin films prepared at different composition.............................................78
Fig. 4-10(c) Effect of film surface temperature on the Polar SFE of TaNx thin films prepared at different composition.............................................79 
Fig. 4-11(a) Effect of film surface temperature on the Total SFE of MoNx thin films prepared at different composition.............................................80 
Fig. 4-11(b) Effect of film surface temperature on the Dispersive SFE of MoNx thin films prepared at different composition.............................................81
Fig. 4-11(c) Effect of film surface temperature on the Polar SFE of MoNx thin films prepared at different composition.............................................82 
Fig. 4-12(a) Effect of film surface temperature on the Total SFE of WNx thin films prepared at different composition.............................................83 
Fig. 4-12(b) Effect of film surface temperature on the Dispersive SFE of WNx thin films prepared at different composition.............................................84
Fig. 4-12(c) Effect of film surface temperature on the Polar SFE of WNx thin films prepared at different composition.............................................85 
Fig. 4-13 Relationship between surface free energy and surface roughness of TaNx films at 20 ℃ by SEM.........87
Fig. 4-14 Relationship between surface free energy and surface roughness of VNx films at 20 ℃.................88
Fig. 4-15 Relationship between surface free energy and surface roughness of NbNx films at 20 ℃................89
Fig. 4-16 Relationship between surface free energy and surface roughness of TaNx films at 20 ℃................90
Fig. 4-17 Relationship between surface free energy and surface roughness of MoNx films at 20 ℃................91
Fig. 4-18 Relationship between surface free energy and surface roughness of WNx films at 20 ℃.................92

表目錄
Table 3-1 The composition of VNx、NbNx、TaNx、MoNx、WNx films...................................................44 
Table 3-2 Test liquids and their surface tension components at 20℃.................................................46
Table 3-3 Test liquids and their surface tension components..............................................50
Table 4-1 Contact angles of test liquids on the films at 20℃....................................................57
Table 4-2 Contact angles of test liquids on the VNx films...................................................66
Table 4-3 Contact angles of test liquids on the NbNx films...................................................67
Table 4-4 Contact angles of test liquids on the TaNx films...................................................68
Table 4-5 Contact angles of test liquids on the MoNx films...................................................69
Table 4-6 Contact angles of test liquids on the WNx films...................................................70
                                    

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