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Oxidation behavior of AlN films at high temperatures under controlled atmospheres
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本研究主要是探討氮化鋁薄膜於不同氮氧含量之氣氛(空氣、氮氣、氮氫(N2/H2=9)混合氣)及真空高溫熱處理後的行為，溫度範圍為700~1300℃ (真空範圍300~1100℃)，持溫時間為2~12小時 (真空時間為2小時)。其中使用X光繞射儀 (XRD)與微拉曼光譜儀 (Micro Raman spectrometer)來分析其結晶相變化，並使用場發射式電子顯微鏡 (FESEM)來觀察其表面形貌。不同氮氧含量之氣氛熱處理後的現象包含了氧化造成的顏色變化以及氧化鋁的相轉變，而真空熱處理方面則包含其薄膜應力變化的情形。
在空氣下，時間2小時，由FESEM圖知在700℃以下仍然呈現與剛鍍著相同的粒狀形貌，在1050℃時出現兩種截然不同的氧化鋁表面形貌(塊狀及緻密結構)同時有晶界的出現，由Micro Raman解析出此塊狀結構為δ-Al2O3而緻密結構為α-Al2O3。而晶界的產生是由於燒結行為的發生。同樣的在氮氣下，1050～1100℃之間表面形貌也存在著兩種結構(塊狀：δ-Al2O3與緻密狀：α-Al2O3)。然而氮氫混合氣下，因為此氣氛氧分壓相當低 (10-24~10-16 atm)，所以能看到氮化鋁薄膜隨著溫度增高其表面形貌緩慢變化的情形。在1050℃表面形貌由原先的粒狀改變為片狀，到達1200℃時表面形貌同樣也存在著塊狀及緻密狀結構。
氮化鋁薄膜於真空下300~1100℃熱處理2小時後其微結構與結晶相都與剛鍍著時相同。使用XRD法量測剛鍍著之氮化鋁薄膜應力，其值為－0.4 Gpa，隨著溫度的增加應力由原先的壓應力轉變成張應力，其應力的轉變可能與薄膜內部缺陷與孔洞有關。更進一步，比較XRD與雷射曲率法所量測到剛鍍著之氮化鋁薄膜應力值，其量測到之應力分別為-0.4 Gpa與-0.8 Gpa，其差異的可能原因為XRD法在低應力的薄膜中敏感度較低，造成與雷射曲率法求得之應力有所差距，所以XRD方法並不適合用來量測低應力薄膜。
In this research, oxidation behavior of aluminum nitride films in the atmosphere with different nitrogen/oxygen ratios (air、nitrogen、N2/H2=9) and vacuum has been investigated. The studied temperature was range was 700-1300 oC (in the atmosphere and was 300-1100 oC in vacuum.), and the soaking time was in the range of 2-12 h (vacuum: 2 h). Changes in the crystalline phase of aluminum nitride films were analyzed by X-ray diffraction (XRD) and Micro Raman spectroscopy. The surface morphology of aluminum nitride films before and after annealing was examined by field emission scanning electron microscopy (FESEM). Oxidation of aluminum nitride films resulted in color changes and phase transformation. In vacuum residual stress was also determined.
Annealing below 700℃ for 2 h in air retained original granular structure as shown by FESEM analyse. At 1050 oC, oxidized aluminum nitride surface showed entirely different morphology (flaky and dense structures); grain boundaries were clearly visible on the surface. Resultant alumina structure was examined by Micro Raman spectroscopy. Based on the results, the flaky and dense structures were δ-Al2O3 and α-Al2O3, respectively. The visible grain boundarues were due to the sintering process. Oxidization between 1050℃ and 1100℃ for 2 h in nitrogen also resulted in similar structures (flaky structure: δ-Al2O3 and dense structure: α-Al2O3). Much slower oxidation of aluminum nitride films was observed in N2/H2=9 atmosphere because the oxygen partial pressure was considerbly low. At 1050℃, the surface morphology changed from a granular structure to a sliced; at 1200oC both fla and flaky dense structures showed up.
The crystalline structure of aluminum nitride films treated in vacuum at 300-1100oC for 2 h was similar to that of as-deposited films. Residual stresses of the aluminum nitride film were determined by XRD. The measured residual stress of as deposited films was -0.4GPa. The stress changed from a compressive stress to a tensile stress with increasing temperature. Different stress measurements method (XRD and laser-based stress measurement), resulted in different values -0.4GPa from XRD and -0.8GPa from laser curvatuse measurement. This is because XRD measurement has a lower sensitivity at lower stress. Consequently, the XRD method is not suitable for the lower stress films.
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