經真空熱處理之氮化鈦鋯薄膜氧化行為研究

Oxidation Behavior of Vacuum Annealed TiZrN Thin Film

吳柏賢

指導教授 ： 喻冀平 ； 黃嘉宏

國立清華大學/原子科學院/工程與系統科學系/碩士(2013年)

摘要

本研究的目的在真空高溫下不同成分的TiZrN薄膜的氧化行為。首先利用非平衡濺鍍法鍍著TiZrN薄膜在(001)的矽基板上，再分別進行700~1000度的真空熱處理，為了研究不同成分的影響，使用Zr/(Zr+Ti)=0.3, 0.5, 0.7 三種不同比例的TiZrN薄膜，在經過700~900度的熱處理後，薄膜的晶粒大小及晶格常數沒有明顯的改變，亦沒有氧化物的生成，也沒有TiN和ZrN的析出物生成，也就是說，沒有相分離產生，在經過700~900的退火後，薄膜的硬度從29 GPa下降至25 GPa，而薄膜的殘留壓應力則大約下降40%。然而，當熱處理溫度升到1000度，則在薄膜觀察到ZrO2的生成，且TiZrN薄膜的抗氧化會隨著含鈦量增加而提升，在TiZrN的元素縱深分析中，可以知道在氧化層是由氮化物以及氧化物所組成，鈦對鈦加鋯比例為0.3的TiZrN薄膜經過1000度三小的熱處理，氧化相比例大約為26%且氧化層成長速率約為每小時成長45nm，且從顆粒狀的氧化層結構可以得知，ZrO2的氧化層是具有保護性的。

關鍵字

氮化鈦鋯薄膜 ； 磁控濺鍍 ； 熱處理 ； 氧化行為

並列摘要

The purpose of this study is to research the oxidation behavior for different composition TiZrN thin film at high temperature in vacuum. A series of TiZrN film were deposited on Si (001) substrates using unbalanced magnetron sputtering. Specimens were later annealed respectively at different temperature ranging from 700°C to 1000°C in vacuum. In order to research effect of composition of TiZrN thin film, this study used content of Zr/(Zr+Ti)=0.3, 0.5 and 0.7 TiZrN film. After heat treatment, TiZrN thin film have no apparent changes in grain size and lattice parameter, and no oxide observed on the surface of thin film at 700°C to 900°C. After heat treatment for 700°C to 900°C, there is no separation X-ray diffraction peaks to split into TiN and ZrN; in other words, there is no spinodal decomposition at vacuum annealed temperature. The hardness of TiZrN thin film decreases from 29 GPa to 25GPa and the residual compressive stress of the film decreases about 40% for all series samples. However, at 1000°C, there is ZrO2 observed on the surface of TiZrN thin films. The oxidation resistance of TiZrN thin films in vacuum at 1000°C was enhanced by incorporation of titanium. After annealing 1000°C for 1 hour to 4 hours, there are partial oxide layers on the top of film. In the composition depth profile in AES, there are ZrO2 phase and TiZrN phase in the partial oxide layer. The growth rate of partial oxide layer is 45 nm/hr and the oxide phase ratio is 26.3% with Ti/(Zr+Ti)=0.3 of TiZrN thin films at 1000°C for 3 hours.

並列關鍵字

TiZrN thin film ； magnetron sputtering ； heat treatment ； oxidation behavior

參考文獻

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