利用電漿增強化學氣相沉積技術製作超親水自清潔氧化鈦薄膜之研究

The study of a titanium oxide film with self-cleaning ability prepared by plasma enhanced chemical vapor deposition technique

黃炳文(Bing-wen Huang)

國立虎尾科技大學/電機資訊學院/光電與材料科技研究所/碩士(2007年)

摘要

本研究利用電漿增強化學氣相沉積法於室溫下在塑膠基板上沉積具有親水特性及硬化效果之薄膜，研究中主要以有機材料-四異丙烷氧化鈦及氧氣氣體為源材料，沉積具有超親水自清潔功能之氧化鈦薄膜，接著，再於製程過程中通入四甲基矽烷有機氣體，沉積氧化鈦-氧化矽複合薄膜，增強氧化鈦薄膜之機械強度。研究結果顯示，於室溫環境下，使用電漿增強化學氣相沉積法，可以在最佳化製程條件下，製備具有親水特性(水滴接觸角小於20o )之非晶氧化鈦薄膜(a-TiOX:O-H)，然而此非晶氧化鈦薄膜放置於一般大氣環境暗處下，水滴接觸角特性會隨時間增加而上升，由於氧化鈦薄膜所具有之光觸媒特性，經由紫外線燈照射後，使得氧化鈦薄膜具有優異超親水特性(5o以下)。為了進一步觀察氧化鈦薄膜之結晶特性與光觸媒效應之關係，本研究藉由升溫製程以及後續熱處理製程，優化氧化鈦薄膜之結構與結晶特性，研究結果顯示，升溫製程可以使得薄膜緻密性提升，並且使氧化鈦薄膜之化學組成接近二氧化鈦之化學計量比，而針對上述室溫及升溫製程所製備之非晶氧化鈦薄膜進行後續熱處理後，可以發現，熱處理溫度到達400 oC時，非晶氧化鈦薄膜轉變為具有(101)、(112)、(200)及(211)等銳鈦礦結晶相之多晶二氧化鈦薄膜，光觸媒效果有顯著的提升，經過紫外線燈(1 mW/cm2)照射一小時後，水滴接觸角特性皆趨近於0o，具有超親水自清潔的效果。為了進一步提升氧化鈦薄膜的結構特性與機械強度，本研究藉由掺入四甲基矽烷氣體，改善非晶氧化鈦之薄膜硬度，研究結果顯示，未掺雜之氧化鈦薄膜其鉛筆硬度小於H，而當製程過程中掺入適當四甲基矽烷氣體流量後，薄膜中有較為明顯的矽-氧-矽及矽-氧-鈦鍵結形成，可以有效提昇氧化鈦薄膜之鉛筆硬度，沉積在PMMA及PC基板上分別可達到 5 H及 2 H，水滴接觸角為25o，利用奈米壓痕儀量測後，其硬度可達1.8 GPa(PC 基板)，並且經由紫外線燈照射後，氧化鈦-氧化矽薄膜具有優異的親水特性(10o以下)。

並列摘要

In the study, amorphous TiOX -SiOX composite film were formed on plastic substrate by plasma enhanced chemical vapor deposition at room temperature from mixtures titanium tetraisopropoxide (TTIP)、 Tertramethylsilane (TMS) and oxygen. Plasma enhanced CVD process enables the film preparation in low temperature process, which expands the kinds of substrates widely. PECVD of TiOX -SiOX composite films has been evaluated with various process parameters. The contact angle, crystal structure, hardness and chemical bonding configuration of the as-deposited and annealing TiOX -SiOX films were analyzed using Contact angle measure, X-ray diffraction(XRD), pencil hardness measure, Nano indenter and Fourier transform infrared spectroscopy(FTIR). The as-deposited TiOx film at room temperature show hydrophilicity(water contact angle below 17°) that deteriorated after long time storage in a dark ambient air (water contact angle of 45o). By UV light irradiation, the film surface recovered its super hydrophilicity (below 5°).In crystal structure , The diffractive angles 2θ of the samples annealed at the temperature range from 400 to 900 oC are 25.7, 38.2, 48.4 and 55.4 , which are attributed to anatase (101), (112), (200), (211), respectively. The annealing temperature from 400 OC to 600 OC, the contact angle becomes nearly 0 O , On the other hand, from pencil hardness test and Contact angle measure , pencil hardness of the TiOx film was less than H, hardness and contact angle of the films with TMS of 10 sccm are PMMA : 5H, PC : 2H (water contact angle of 25o) and 1.8 GPa, by UV light irradiation, the film surface recovered its hydrophilicity (below 10°). vibration increased with an increase of the TMS content.

參考文獻

[2]. M. Nakamura, D. Korzec, T. Aoki, J. Engemann, Y. Hatanaka, “Characterization of TiOx film prepared by plasma enhanced chemical vapor deposition using a multi-jet hollow cathode plasma source”, Appl. Surf. Sci. , 697, pp.175-176 (2001).

[3]. M. Nakamura, L. Sirghi, T. Aoki, J. Engemann, Y. Hatanaka, “Study of hydrophilic property of hydro-oxygenated amorphous TiOx:OH thin films”, Surf. Sci., 507-510, p.778 (2002).

[4]. M. Nakamura, K. Makino, L. Sirghi, T. Aoki, Y. Hatanaka, “Hydrophilic properties of hydro-oxygenated TiOx films prepared by plasma enhanced chemical vapor deposited”, Surf. Coat. Technol., 169-170, pp.699-702 (2003).

[6]. M. Maeda, T. Watanabe, “Evaluation of photocatalytic properties of titanium oxide films prepared by plasma-enhanced chemical vapor deposition”, Thin Solid Film, 489, pp.320-324 (2005)

[7]. X-P. Wang, Y. Yu, X-F,Hu, L. Gao, “hydrpphilicity of TiO2 films prepared by liquid phase deposition”, Thin Solid Film, 371, pp.148-152 (2000).