Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/10148
標題: Preparation of TiN thin films by physical vapor deposition using air/Ar mixtures
以物理氣相沈積法通入空氣/氬氣製備TiN薄膜
作者: Yang, Chun-Hui
楊浚揮
關鍵字: PVD;物理氣相沈積法;TiN;air;DSSC;dye-sensitization solar cells;氮化鈦;空氣;太陽電池
出版社: 材料科學與工程學系所
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摘要: 
TiN的用途廣泛,在過去文獻中以物理氣相沈積法(PVD)製備TiN薄膜者,都是會先抽除腔體中的空氣,再以氮氣做為反應性氣體製備TiN。由於近年來溫室效應與能源議題日益受到重視,本研究希望能改善製備TiN的過程,而達到節能環保目的,本研究主要探討以空氣取代氮氣鍍著TiN薄膜之可能性,並藉此縮短生產時抽真空所耗費的時間,以達到節能環保及降低製程設備及材料成本的目的。
本研究主要以PVD在鍍著功率200 W、偏壓-50 V,背景壓力5×10-6 torr,工作壓力1×10-3 torr下,控制空氣/氬氣流量比值在(9~12)/100時,製備薄膜之後分別以色度計進行顏色的分析,並針對所鍍著之薄膜的結晶相,以X光繞射儀(XRD)作分析,並以場發射電子顯微鏡(FE-SEM)觀察薄膜的微結構,另以歐傑電子能譜儀(AES)及X光光電子能譜儀(XPS)進行薄膜化學組態分析,此外以四點探針進行薄膜的電阻率分析,及以奈米壓痕儀進行薄膜的硬度分析。結果薄膜為金黃色(L*:76.0~78.2,a*:1.2~2.4,b*:25.9~28.4)岩鹽(rock-salt)型結晶相,微結構為柱狀晶,其電阻率為40~178 μΩ-cm,硬度為20~23 GPa,氧含量為10.2~16.7 at%,與文獻所報導的TiN性質比對後,證實能以空氣成功製備出TiN薄膜;進一步以背景壓力1×10-4 torr,控制空氣/氬氣流量比值在(9~10)/100時,也能成功製備出電阻率為99~107 μΩ-cm、硬度為21~22 GPa之TiN薄膜,根據本研究之設備抽背景真空度5×10-6 torr約需要25~30分鐘,而1×10-4 torr只需要3~4分鐘,兩者的抽氣時間差異極大,因此能省去抽真空的時間,達到環保節能的目的;然而本研究也發現,當鍍著功率升高時,要製備出金黃色TiN所通入的空氣流量比值也必須增加。在空氣中可製備出TiN膜之結果與熱力學之預期在300 K~1273 K於空氣中會形成TiO2結果不符,但能確定鈦在電漿環境下與空氣產生氮化確是動力學控制的結果。
此外本研究改變不同空氣/氬氣流量比值時,薄膜顏色會有銀白色→金黃色→紅銅色→土黃色→酒紅色→紫藍色等變化,此方法能取代過去文獻曾經報導,控制N2/O2之比值來達到色彩多元的目的。另外本研究首次嘗試將TiN應用於染料敏化太陽電池上,實驗過程發現TiN經陽極氧化後,所製備出的奈米多層TiO2,製作成染料敏化太陽能電池後,在持續照光的條件下,電池所量測到的開環電壓(Voc)為0.45 V,短路電流(Jsc)為0.04 mA。因此在綠能概念下本研究的方法所製備之TiN於環保與染料敏化太陽能電池上將更具有優勢。

TiN films have been widely applied in industry. The films are commonly prepared by physical vapor deposition (PVD), during which a high vacuum is required and nitrogen is conventionally used as a reactive gas. The greenhouse effect and the energy issues have received much attension in recent years. This research is to improve the manufacture process of TiN to achieve the goal of saving energy and cost reduction. The object is to replace nitrogen by air in preparing TiN, which has advantages of green process and low manufacturing cost.
The main parameters used in PVD are: direct current power 200 W, and biased voltage -50 V, base pressure 5×10-6 torr, and working pressure 1×10-3 torr. The flow rate ratio of air/Ar(9 ~ 12)/100. The color of the films was analyzed by a colorimeter. Crystal phases were analyzed by X-ray diffraction, micro structures were examined by field-emission scanning electron microscopy, and chemical compositions were determined by Auger electron spectroscopy and X-ray photoelectron spectroscopy. In addition, electrical resistivity was measured by a four-point probe system, and hardness was measured by a nanoindeter. TiN films were golden (L *: 76.0 ~ 78.2, a *: 1.2 ~ 2.4, b *: 25.9 ~ 28.4), and exhibited a rock-salt phase. Columnar structure was present. Electrical resistivity ranged from 40 to 178 μΩ-cm, the hardness was about 20 to 23 GPa, and the oxygen content was 10.2 to 16.7 at%. It is confirmed that the films fulfill the characteristies of TiN. Increasing the base pressure to 1×10-4 and varing the air/Ar ratio (9 ~ 10)/100 could also successfully prepare TiN films with the electrical resistivity of 99~107 μΩ-cm and hardness of 21~22 GPa. It is normally takes 25 to 30 minutes to achieve a base pressure 5×10-6 torr, while it takes only 3 to 4 minutes to reach 1×10-4 torr. Cost would be reduced gretly. However, the flow rate ratio of the air/Ar increased with direct current power. From thermodynamics predictions, TiO2 will be formed in the range of 300 - 1273 K in air. In the research, TiN could be formed in air. The nitridation of Ti in air under plasma environment is kineticsly controlled.
Varying the rate ratio of air and argon caused the color changing from silver color → golden color → coppery color → brown color → wine red color → indigo color. Various colors could be present by controlling the rate of air and argon. Synthesis of nano-multilayer TiO2 films on TiN films by anodic oxidation. Through this method, this TiO2 films can be applied on dye-sensitized solar cells. The open circuit voltage was 0.45 V and the short-circuit current was 0.04 mA under the light. Therefore, anodic oxide of TiN can be used in dye-sensitization solar cells.
URI: http://hdl.handle.net/11455/10148
其他識別: U0005-0906200611292100
Appears in Collections:材料科學與工程學系

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