臺灣博碩士論文加值系統

本研究應用MFI-like或BEA-like二氧化矽奈米顆粒懸浮液(colloid)於研發抗腐蝕膜及低介電薄膜。
有關抗腐蝕膜研究方面，是添加二氧化矽奈米顆粒至GPTMS-TEOS(3-glycidoxypropyltrimethoxysilane and tetraethyl orthosilicate )鍍膜液中，以製備有機-無機混成抗腐蝕膜，期望藉由奈米顆粒表面Si-OH與GPTMS或矽烷(TEOS)水解後產生之Si-OH脫水縮合形成結構更緻密之膜。本研究已藉由增加鍍液攪拌時間、以及提升膜熱處理溫度探討添加顆粒後對抗腐蝕性及縮合程度的影響。除此之外，已利用HMDS (hexamethyldisilazane)表面修飾以及添加CF3CH2OH以提升膜之疏水性，藉由疏水基之增加而提升抗腐蝕性。研究結果發現添加MFI-like顆粒並鍍膜後，用來增加縮合反應的熱處理溫度是提升薄膜抗腐蝕性的重要關鍵。雖然鍍液攪拌時間增長，在膜熱處理溫度低時能改善薄膜之抗腐蝕性，但在熱處理溫度高時則無明顯影響，。而添加BEA-like顆粒後，隨鍍液攪拌時間增長，溶液黏度及鍍膜厚度都下降，且膜表面由粗糙轉為光滑平坦，抗腐蝕力卻些微下降。本研究藉由接觸角量測得知，各有機-無機混成抗腐蝕薄膜均具親水性，較不符抗腐蝕膜要求，因此行疏水性質改良。經HMDS表面修飾後，發現能提升疏水性及膜的抗腐蝕力，但較粗糙的膜因疏水性GPTMS凸塊形成於表面，能修飾之位置相對較少，因此修飾效果較差。有機-無機混成鍍液中添加CF3CH2OH以做性質修飾，所成的膜雖然疏水性能增加，但膜厚及硬度都會降低。不過對添加MFI-like顆粒薄膜的抗腐蝕力仍舊能提升，但對添加BEA-like顆粒的薄膜則因膜厚過於降低，而使抗腐蝕力不增反減。
本研究已結論出，添加MFI-like或BEA-like奈米顆粒於GPTMS-TEOS所成薄膜比不添加的，其抗腐蝕力要來得差。已由實驗證實，本研究添加奈米顆粒的方式會使顆粒中有機氨模板與GPTMS-TEOS鍍液中硝酸液反應產生鹽類，因而減弱薄膜抗腐蝕力，甚至使膜表面產生裂紋及裂縫造成硬度下降。未來應嘗試製備不含有機氨模板之奈米顆粒，以便進一步驗證相關奈米顆粒對抗腐蝕性影響。
有關研究低介電薄膜方面，是直接應用MFI-like二氧化矽奈米懸浮液為鍍膜液，製備介電係數小於2且高機械強度之孔洞型低介電薄膜。是探討製程中環境濕度，以及兩不同壁厚高壓釜所製備不同大小奈米粒，對低介電薄膜性質影響。
研究結果發現，環境濕度與k值呈正比相關。為降低濕度造成k值上升問題，利用加熱板提供熱源降低環境濕度，已可降低濕度約10%，並且加快HF蝕刻二氧化矽之速率，減少樣品暴露於空氣之時間，而有效降低薄膜介電值。另外發現，不同壁厚高壓釜會製備出不同大小奈米粒，但對低介電薄膜性質並無影響，皆可製備出介電係數小於2且高機械強度之孔洞型低介電薄膜。

The applications of MFI-like and BEA-like nano-particles in anti-corrosion films and in low-k films were studied.
For anti-corrosion application, the particles were added in GPTMS-TEOS (3-glycidoxypropyltrimethoxysilane and tetraethyl orthosilicate) solution to form an organic-inorganic anti-corrosion coating solution. It was expected that the hydroxyl groups on nano-particles surface can form chemical bonds with those of GPTMS through dehydration reaction, so that a better anti-corrosion property can be generated. It has been found from the research results that heat treatment of the resulting organic-inorganic films with the addition of MFI-like particles is an important factor to increase anti-corrosion property. Increasing stirring and mixing time of coating solution after the addition of nano-particles can also increase anti-corrosion of the films, which are heat treated at 130 ℃; Nevertheless, they cannot increase anti-corrosion significantly at higher film treatment temperatures. However, the stirring and mixing time can cause substantial difference of the films added with BEA-like particles. The viscosity of the coating solution, the thickness and the roughness of the resulting films all decreased with the increase of mixing time. Moreover, films anti-corrosion also decreased slightly with the increase of mixing time.
The measurements of contact angle showed that the organic-inorganic films made in this research were hydrophilic. HMDS (hexamethyldisilazane) for surface modification and CF3CH2OH for modifying film property were applied respectively for improving hydrophobic property. It has been found that after films surface was modified by using HMDS, both hydrophobic and anti-corrosion properties can be increased. However, for the films with higher roughness and with GPTMS aggregation on the surface, the improvement is slight, because less hydroxyl group on the surface can be used for the HMDS modification. On the other hand, the addition of CF3CH2OH in the coating solution can also increase the resulting films hydrophobicity. Nevertheless, films thickness and hardness were deteriorated at the same time. For those added with MFI nanoparticles, the anti-corrosion property was increased. However, for those with BEA nanoparticles, the anti-corrosion was decreased due to the dramatic decrease of film thickness.
It has been concluded from this study that the addition of MFI-like or BEA-like particles in GPTMS-TEOS solution would decrease anti-corrosion property of the films. The reason is that there are tetrapropylammonium hydroxide in MFI-like particles and tetraethylammonium hydroxide in BEA-like particles. After the addition of the particles, nitric acid in GPTMS-TEOS solution can react with those ammonium hydroxides to form salts in coating solution. The presence of salts in the films decreases hydrophobic property and anti-corrosion properties; moreover, may cause the cracks in the films.
For the study of applications in low dielectric films, MFI-like colloid was used for preparation of porous low dielectric (low-k) films, which possess not only a k value below 2 but also a high mechanical strength. The effect of environmental humidity during low-k films processing and the effect of coating solutions made from different wall thicknesses of autoclaves on properties of low-k films were investigated. It has been found that environmental humidity can give negative influence on k values of the resulting films. It can be simply improved by using a hot plate as a heat source to lower the humidity during films processing. This approach can also accelerate HF etching rate on the films for the later films properties measurements. On the other hand, in spite that silica nanoparticles made by thin-wall autoclave were larger than the thick one, there was no influence on low-k films’ properties. Both were able to possess not only a k value below 2 but also a high mechanical strength.

中文摘要 i
英文摘要………………………………………………………………………………..iii
目錄…...…………………………………………………………………………………v
圖目錄 viii
表目錄 x
一、緒論 1
　　1-1 抗腐蝕研究背景 1
　　1-2 抗腐蝕塗層 1
1-2-1 阻障層 2
1-2-1-1鉻轉化塗佈 2
1-2-1-2金屬氧化物塗佈 3
1-2-1-3二氧化矽懸浮液塗佈 4
　　 1-2-1-4無機-有機混成塗佈 4
　　1-2-2 犧牲陽極 6
1-2-3 陽極氧化法 7
　　1-3 低介電薄膜研究背景 8
　　1-4 孔洞型二氧化矽低介電薄膜 9
　　　　1-4-1 氣凝膠/乾凝膠法 9
　　　　1-4-2 界面活性劑模板法 10
　　　　1-4-3 水熱法 11
　　1-5研究動機 13
　　1-6 研究目標 14
二、實驗 15
　　2-1 實驗藥品 15
　　2-2 實驗儀器 16
　　2-3 抗腐蝕膜實驗步驟 16
2-3-1 清洗基板 17
2-3-2 二氧化矽懸浮液製備 17
2-3-3 抗腐蝕膜製備 19
2-3-4 抗腐蝕膜疏水性改質 21
2-3-2 HMDS表面修飾 21
2-3-2 CF3CH2OH疏水性改質 22
　　2-4 低介電薄膜實驗步驟 23
　　　　2-4-1 清洗晶圓 23
　　　　2-4-2 低介電薄膜製備 23
　　2-5 實驗鑑定 25
2-5-1 溶液性質鑑定 25
2-5-1-1 動態雷射光散射分析 25
2-5-2 粉末性質鑑定 26
2-5-2-1矽譜固態核磁共振儀分析 26
2-5-2-2 熱重分析儀 26
2-5-3 薄膜性質鑑定 27
2-5-3-1 電子顯微鏡觀測 27
2-5-3-2 鉛筆硬度量測 27
2-5-3-3 接觸角量測 28
2-5-3-4 腐蝕之電化學量測 28
2-5-3-5 介電係數量測 29
2-5-3-6 奈米壓痕儀量測系統 31
三、結果與討論 32
　　3-1添加MFI-like顆粒鍍液之攪拌時間與成膜熱處理溫度對抗腐蝕影響 32
3-2添加BEA-like顆粒鍍液之攪拌時間與成膜熱處理溫度對抗腐蝕影響 36
3-2-1 不同結晶型態之沸石分析 36
3-2-2 添加BEA-like顆粒鍍液之成膜熱處理溫度對抗腐蝕性影響 39
3-2-3 鍍液攪拌時間對BEA顆粒添加之性質影響 40
　　3-3藉由固態Si-NMR鑑定溫度對薄膜縮合程度影響及薄膜接觸角鑑定 42
　　　　3-3-1 固態Si-NMR鑑定溫度對薄膜縮合程度影響 42
　　　　3-3-2 接觸角鑑定 45
　　3-4 疏水性提升對抗腐蝕影響 47
　　　　3-4-1 HMDS表面修飾改質 48
　　　　3-4-2 CF3CH2OH疏水性改質 51
　　3-5未添加顆粒之數據探討及修正 53
　　3-6添加顆粒後，造成抗腐蝕力下降探討以及改進 56
3-6-1 抗腐蝕力下降探討 56
3-6-2 添加MFI-like colloid酸化後對抗腐蝕影響 58
　　3-7環境濕度對介電係數影響 60
　　3-8室溫對膜厚影響 61
　　3-9不同顆粒大小之二氧化矽對介電值影響 62
四、結論 64
五、未來研究 65
六、參考文獻 67
七、附錄 71
　　7-1選用比色槽與粒徑量測問題 71
　　7-2水熱液粒徑溫控實驗 72
　　7-3電化學系統補充 75
　　　　7-3-1三用電極系統 75
　　　　7-3-2極化曲線圖 75

1.D. Wang and G. P. Bierwagen, Progress in Organic Coatings, 64 (2009) 327–338.
2.C.-T Hsieh, J.-M Chen, and R.-R Kuo, Applied Surface Science, 240 (2005) 318-326.
3.L. Calabrese, L. Bonaccorsi, A. Caprì, E. Proverbio, Progress in Organic Coatings, 77 (2014) 1341-1350.
4.D. Quéré, Nature Material, 1 (2002) 14-15.
5.A. Yabuki and R. Kaneda, Materials and Corrosion, 60 (2009) 444-449.
6.P. A. Srensen, S. Kiil, K. Dam-Johansen, and C. E. Weinell, Journal of Coatings Technology and Research, 6 (2009) 135–176.
7.Y-C Xin, et al., Journal of Materials Research, 23 (2008) 312-319..
8.張明倫，林新智，陳敏璋，以氧化鋁薄膜保護純銅之研究，台灣大學材料科學與工程研究所.
9.M.L. Zheludkevich, R. Serra, M.F. Montemor, I.M. Miranda Salvado, and M.G.S. Ferreira, Surface & Coatings Technology, 200 (2006) 3084–3094.
10.湯偉鉦，台灣奈米資訊電子報，2014年，六月，第46-52頁。
11.R.L. Twite, G.P. Bierwagen, Progress in Organic Coatings, 33 (1998) 91–100
12.J. R. Waidrop, J. Electrochem. Soc., 145 1 (1998) L11-L13
13.Jun Zhao, J. Electrochem. Soc., 145 7 (1998) 2258-2264
14.Rossana Grilli, Corrosion Science, 53 (2011) 1214–1223
15.Gerald S. Frankel, Air Force Office of Scientific Research Contract No. F49620-96-1-0479, (2001).
16.G. Bhargava and F. Allen, Metal Finishing, 110 (2012) 32-38.
17.K. Ogle and R.G. Buchheit, Encyclopedia of Electrochemistry, 4 (2003) 460-499.
18.周淑金、王正全，「綠色表面處理-六價鉻替代技術的發展」，中華民國電子零件認證委員會，第五十卷，2006，第25-32頁。
19.X. Cheng, Z. Wang and Y. Yan, Electrochemical and Solid-State Letters, 4 (2001) B23–B26.
20.A. Mitra, Z. Wang, T. Cao, H. Wang, L. Huang and Y. Yan, Journal of The Electrochemical Society, 149 (2002) B472–B478.
21.D. E. Beving, A. M. P. McDonnell, W. Yang, and Y. Yan, Journal of The Electrochemical Society, 153 (2006) B325–B329.
22.R. Cai and Y. Yan, Corrosion, 64 (2008) 271–278.
23.Y. Dong, Y. Peng, G. Wang, Z. Wang, and Y. Yan, Journal of Industrial & Engineering Chemistry Research, 51 (2012), 3646–3652.
24.W-C, Changhean, T-C, Tsai, Thin solid films, 529 (2013) 327-332.
25.H.B. Pande and P.A. Parikh, Journal of Materials Engineering and Performance, 22 (2013) 190-199.
26.X. Guo, M. An, P. Yang, C. Su, and Y. Zhou, J Sol-Gel Sci Technol 52 (2009) 335-347.
27.L. Calabrese, L. Bonaccorsi, and E. Proverbio, Journal of Coatings Technology and Research, 9 (2012) 597–607.
28.S.A.S. Dias, S.V. Lamaka, C.A. Nogueira, T.C. Diamantino, and M.G.S. Ferreira, Corrosion Science, 62 (2012) 153–162.
29.N. Idusuyi, O.O. Oluwole, International Journal of Science and Technology, 2 (2012) 561-566.
30.G.-L Song, N.J. Dudney, J. Li, R Sacci, and J.K. Thomson, Corrosion Science, 87 (2014) 11-14.
31.A.Y. Musa, Corrosion Protection of Al Alloys: Organic Coatings and Inhibitors, (2012) p.53.
32.S. Ono, The Journal of the Vacuum Society of Japan, 52 (2009) 637-644.
33.T. He, Y. Wang, and Y. Zhang, Corrosion Science, 51 (2009) 1757-1761.
34.F. Zhang, L. Zhao, H. Chen, S. Xu, D.G. Evans, and X. Duan, Angewandte Chemie International Edition, 47 (2008) 2466 –2469.
35.Y. Zuo, P.-H Zhao, J.-M Zhao, Surface and Coatings Technology, 166 (2003) 237-242.
36.Bakoglu, H.B. and J.D. Meindl, IEEE Transactions on, 32 (1985) 903-909.
37.P.S. Ho, J. Leu, and W.W. Lee, Overview on Low Dielectric Constant Materials for IC Applications, in Low Dielectric Constant Materials for IC Applications, P. Ho, J. Leu, and W. Lee, Editors. (2003) 1-21.
38.D. Edelstein, et al.. Technical Digest., International. (1997).
39.W. W. Lee, P.S.H., MRS Bulletin., 22 (1997) 19-24.
40.Semiconductors, T.I.T.R.f., http://www.itrs.net/Links/2012ITRS/Home2012.htm, 2012.
41.H. Xiao, Introduction to semiconductor manufacturing technology. (2001) 481.
42.C.-T. Tsai, et al., Thin Solid Films, 517 (2009) 2039-2043.
43.R.F. Pease, et al., Microelectron. Eng., 53 (2000) 55-60.
44.C. Murray, et al., Microelectronic Engineering, 60 (2002) 133-141.
45.S. Baskaran, et al., Advanced Materials, 12 (2000) 291-294.
46.Y. Yan, et al., Advanced Materials, (13) 2001 746.
47.K. Maex, et al., Journal of Applied Physics, 93 (2003) 8793-8841.
48.S.M. Zhu, et al., Ceramics International, 33 (2007) 115-118.
49.蔡承宗, 改良孔洞型二氧化矽低介電係數薄膜機械性質，國立台灣大學化學工程學系碩士論文，2004.
50.Li, Z.J., et al., Advanced Functional Materials, 14 (2004) 1019-1024.
51.Lu, H.-Y., et al., Industrial & Engineering Chemistry Research, 49 (2010) 6279-6286.
52.Lu, H.-Y., et al., Industrial & Engineering Chemistry Research, 50 (2011) 3265-3273..
53.T.L Metroke, O. Kachurina, E.T. Knobbe, Progress in Organic Coatings 44 (2002) 295–305.
54.R.B. Bird, W.E.S., E.N. Lightfoot, Transport phenomena, (2001).
55.卓冠宏，具階層式結構超疏水表面的研究，國立台灣大學化學工程研究所博士論文，2012。
56.A. Naraghi and N. Grahmann, U.S. patent 5611992 (1997).
57.丁志華，奈米通訊(NDL), 9 (2002) 4-10.
58.黃瀚友，以不同的四烷基氫氧化銨為鹼性試劑製備孔洞型二氧化矽低介電薄膜，國立台灣大學化學工程學系碩士論文，2012。
59.K.H. Wu, Surface & Coatings Technology, 201 (2007) 5782–5788.
60.Vladimir M. Gun’ko, Nuclear Magnetic Resonance Studies of interfacial phenomena, (2013) p338.
61.M.K. Bhan, Thin Solid Film, 308-309 (1997) 507-511.
62.J.P. Reynard, Microelectronic Engineering, 60 (2002) 113-118.
63.K. Kamiya, Journal of Materials Science, 21 (1986) 842.
64.Lide, D.R. and T.J. Bruno, CRC handbook of chemistry and physics. 2012: CRC PressI Llc.
65.P.T., Liu, Journal of the Electrochemical Society, 148 (2001) F30-F34.
66.郭佳璋，矽鍺微小結構的製作，國立中興大學物理研究所碩士論文，2003。
67.李庭逸，以純氧化矽沸石奈米顆粒製備低介電膜及抗腐蝕膜之研究，國立台灣大學化學工程學系博士論文，2014。
68.G.P. Bierwagen and D.E. Tallman, Progress in Organic Coatings 41 (2001) 201–216.
69.G.E. Badea, journal of sustanable energy, 1 (2010).
70.Z.M. Gasem, Corrosion Engineering Chap.5 - Polarization Methods for Corrosion Rate Measurements , King Fahd University of Petroleum and Minerals.