Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/97959
標題: 鈦鋯鉿鋁矽硼氮化物多元複合硬質薄膜之微結構與特性研究
Microstructure and characteristics of (TiZrHfAlSiB)N multi-element composite hard films
作者: 陳柏誠
Bo-Cheng Chen
關鍵字: 鈦;鋯;鉿;鋁;矽;硼;氮化物;硬質薄膜;Ti;Zr;Hf;Al;Si;B;hard films
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摘要: 
現今硬膜的研究及應用中,不再以超高硬度作為唯一取向,而是考量到不同應用需求,往多功能的面向發展,其中透明硬膜為具被透明且硬的特性,並使用於各項光學應用中,如反射鏡、熱鏡及太陽能吸收膜等,作為玻璃或金屬薄膜之保護層。而AlN、Si3N4、BN三者氮化物皆為寬能隙材料,同時具有高的抗氧化能力及化學穩定性,另外也具有各不同之特性,其中AlN擁有良好的介電特性,Si3N4則在破裂韌性表現上非常傑出,而BN因其低摩擦係數,對於磨損有極佳的抵抗能力。TiZrHf三者主要是具備金屬特性,是用來改變薄膜的光學特性,其中TiN和ZrN有良好的化學穩定性,HfN有高反射率。
本實驗以等莫耳比AlSiB三元素合金以及TiZrHf三元素合金為靶材,固定氮分壓=20%,基板溫度400 ℃,薄膜厚度1 m,於不同靶材功率下鍍製(AlSiBTiZrHf)N複合硬膜,探討其晶體結構、形貌、機械性質及光學特性等變化,並於大氣環境下退火至1300 ℃持溫2個小時,進行抗氧化性評估及相變化。
本研究主要分為兩個部分:第一部分為TiZrHf摻雜至(AlSiB)N複合硬質薄膜,實驗結果顯示,其結構皆為非晶結構。在機械性質方面,隨著TiZrHf靶材功率的增加,硬度、彈性模數也隨之增加,分別達到28.5 GPa和259.2GPa。在光學性質方面,可發現薄膜反射率隨之增加,吸收邊界紅移,薄膜顏色轉趨為金黃色。在抗氧化性方面,(AlSiB)N薄膜具有最佳的抗氧化能力,溫度達 1200 ℃以上時才全氧化,隨著TiZrHf靶材功率的增加,抗氧化能力隨之減弱。第二部分為AlSiB摻雜至(TiZrHf)N複合硬質薄膜,(TiZrHf)N薄膜結構為FCC結構,隨著AlSiB靶材功率增加,薄膜結晶性先增後減,最終轉為非晶結構。在機械性質方面,薄膜硬度與彈性模數也先增後減,在AlSiB靶材功率增加至40W時,其硬度和彈性模數達到最高分別為34.0 GPa和271.3 GPa。在光電性質,薄膜反射率隨之減少,甚至逐漸在紅外光區段展現透明特性,而薄膜電阻率則隨之上升。在抗氧化性方面,(TiZrHf)N薄膜抗氧化性較弱,約600 oC時便完全氧化,隨著AlSiB靶材功率的增加,抗氧化能力隨之增加。

Research and application of hard film, the ultra-high hardness is no longer the only orientation nowdays.The different application requirements are considered, and the development of multi-functionality in which characteristic of transparent hard film is transparent and hard.Film is used for various optics, such as mirrors, heat mirrors, and solar absorption films, as a protective layer for glass or metal films. AlN, Si3N4 and BN are all wide-gap materials, and have high oxidation resistance and chemical stability. They also have different characteristics. Among them, AlN has good dielectric properties, and Si3N4 performs well in fracture toughness.BN has excellent resistance due to its low coefficient of friction.TiZrHf mainly performs metal properties and is used to change the optical properties of the film. TiN and ZrN have good chemical stability, and HfN has high reflectivity.
  In this experiment, AlSiB three-element alloy(the molar ratio is equal to 1) and TiZrHf three-element alloy(the molar ratio is equal to 1) were used as targets, fixed nitrogen partial pressure=20%, substrate temperature 400 °C, film thickness 1 m, and plated under different target power (AlSiBTiZrHf) N composite hard film.Its crystal structure, morphology, mechanical properties and optical properties were investigated, and annealed to 1300 °C for 2 hours under atmospheric conditions for oxidation resistance evaluation and phase change.
  This study is mainly divided into two parts: the first part is TiZrHf doped to (AlSiB)N composite hard film, the experimental results show that the structure is amorphous. In terms of mechanical properties, as the power of the TiZrHf target increases, the hardness and elastic modulus increases, reaching 28.5 GPa and 259.2 GPa, respectively. In terms of optical properties, it was found that the reflectance of the film increased, the absorption boundary was red-shifted, and the color of the film turned golden yellow. In terms of oxidation resistance, the (AlSiB)N film has the best oxidation resistance. When the temperature is above 1200 °C, it is fully oxidized. As the power of the TiZrHf target increases, the oxidation resistance decreases.The second part is AlSiB doped to (TiZrHf)N composite hard film. The structure of (TiZrHf)N film is FCC structure. As the power of AlSiB target increases, the crystallinity of the film increases first and then decreases, and finally turns into amorphous structure. In terms of mechanical properties, the hardness and elastic modulus of the film also increased first and then decreased. When the power of the AlSiB target increased to 40 W, the hardness and elastic modulus reached a maximum of 34.0 GPa and 271.3 GPa, respectively.In the photoelectric properties, the reflectance of the film reduces, and even the transparent property is gradually exhibited in the infrared light section, and the film resistivity increases. In terms of oxidation resistance, the (TiZrHf)N film has weak oxidation resistance and is completely oxidized at about 600 °C. As the power of the AlSiB target increases, the antioxidant capacity increases.
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