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標題: 以低溫水熱-化學電池法於鍍氮化鋯膜矽基材上製備鋯酸鋇膜之研究
Synthesis of BaZrO3 films on ZrN-coated Si by a low temperature hydrothermal-galvanic couple method
作者: 鄧煥平
Teng, Huan-Ping
關鍵字: barium zirconate;鋯酸鋇;ZrN;hydrothermal;galvanic couple;thin films;氮化鋯;水熱化學電池法;水熱法
出版社: 材料工程學系所
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本研究主要是利用新穎之水熱-化學電池之製程方法,於鍍氮化鋯膜矽基材 (ZrN/Si) 上在低溫的水熱環境下 (<100˚C) 製備BaZrO3膜,而文獻中從未使用過此方法或基材來進行BaZrO3膜之製備或研究。實驗中是以0.5 M醋酸鋇 (Ba(CH3COO)2) 與2 M氫氧化鈉(NaOH) 之混合溶液做為反應溶液,並探討改變反應時間及溫度對於BaZrO3膜成長之影響。在本研究中亦使用水熱法與水熱-化學電池法結果比較。另外亦選用不同的基材,如鍍鋯膜矽基材 (Zr/Si) 和Zr塊材與ZrN/Si基材結果之對照比較。經由X光繞射分析結果確認,利用水熱法及水熱-化學電池法均可以於ZrN/Si上在小於100˚C之低溫環境,製備出具有優選方向之結晶BaZrO3膜。以場發射掃描式電子顯微鏡觀察試片反應後之厚度以及橫截面與表面形貌影像,在研究中顯示出於ZrN/Si製備BaZrO3膜時,單以水熱法在90˚C反應24小時後,可形成800 nm厚之BaZrO3膜,其表面為塊狀形貌。若以水熱-化學電池法製備,則於90˚C反應8小時後,就已形成將近1μm厚之BaZrO3膜,其表面則呈現奈米顆粒形貌;當反應15小時後,生成BaZrO3之膜厚更高達2μm以上,為目前文獻所得膜厚約七倍,並形成之BaZrO3膜具有奈米層狀結構。當溫度固定時,所形成BaZrO3之顆粒與其膜厚隨著反應時間增加而增加,而且BaZrO3膜之生成量與ZrN基材之消耗量符合化學計量之關係,從中顯示出本研究方法可以使絕大部分ZrN基材轉變成BaZrO3膜。綜合實驗結果,利用水熱-化學電池法比水熱法更能明顯降低BaZrO3膜生成之溫度以及縮短反應時間,原因在於水熱-化學電池的方法乃藉由兩極之電位差形成加速離子遷移之驅動力,進而促使氧化還原加速反應,因此可以降低傳統水熱法的反應溫度與時間。而使用Zr/Si和Zr塊材當做與ZrN之反應基材對照,研究中發現不論是以水熱法或是水熱-化學電池法,在溫度95˚C反應24小時後,皆無法於Zr/Si與Zr塊材上生成BaZrO3膜,其中的原因可能與基材的晶粒大小和ZrN中之N原子在反應過程的參與有關。

The objective of this research is to synthesize barium zirconate (BaZrO3, BZO) films on ZrN-coated Si (ZrN/Si) by a low temperature (<100˚C) hydrothermal-galvanic couple method. ZrN/Si specimens were soaked in 0.5 M Ba(CH3COO)2 and 2 M NaOH mixed alkaline solutions with a galvanic couple setup in the temperatures range of 55-95 ˚C for 1-24 h. The hydrothermal method was also conducted for comparison. Meanwhile, bulk-Zr and Zr-coated Si (Zr/Si) would also be used as substrates for comparison.
X-ray diffraction results confirmed that cubic BZO films with preferred orientation were successfully prepared on ZrN/Si below 100˚C by both the hydrothermal method and the hydrothermal-galvanic couple method. The surface morphology and thickness of obtained BZO films was investigated by field-emission scanning electron microscopy. The thickness of obtained BZO films with irregular morphology was about 800 nm at 90˚C for 24 h by the hydrothermal method. As for the hydrothermal-galvanic couple method, the thickness of obtained BZO films with fine particles could reach 1 μm at 90˚C for 8 h. The BZO layer thickness increased up to 2 μm after 15 h. The particle size and thickness of BZO films increased rapidly with increasing temperature. Most of ZrN could be converted into BZO films during the reaction.
The hydrothermal-galvanic couple method compared to the hydrothermal method could reduce the reaction time and temperature for forming BZO films, which is due to the potential difference between the electrodes. The voltage drop could enhance the oxidation rate. In comparation BZO films could not be formed on the Zr/Si and bulk-Zr substrates even at 95 C for 24 h by both the hydrothermal method and the hydrothermal-galvanic couple method. The grain size of the substrates and N atoms may play an important role in the reaction between ZrN and alkaline solutions.
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