氧化鋯分子膜在氣液界面行為及其LB膜製備之探討

The Preparation of ZrO2 Langmuir-Blodgett Film

朱盛民(Sheng-Ming Chu)

指導教授 ： 林昇佃

元智大學/工程學院/化學工程與材料科學學系/碩士(2005年)

摘要

本研究探討四丁氧基鋯溶液滴入氣液界面後水解-縮合反應及擴散速度的行為，目的在探討影響氧化鋯表面層均勻性的因素，進而以Langmuir-Blodgett (LB)技術製備氧化鋯薄膜。
實驗中比較四丁氧基鋯經溶劑稀釋、2.4-Heneicosadiynoic Acid(HA)界面活性劑添加與改變水相subphase的pH值對四丁氧基鋯生成氣液界面層（Langmuir film）的影響，結果發現四丁氧基鋯經溶劑（己烷）稀釋後，可增加溶液的擴散速度，當隨著滴入溶液的體積增加或濃度增加時，溶液在水面上擴散速度相對於水解-縮合反應速度較慢；溶液中添加界面活性劑HA後，可穩定表面溶液的分佈特性而使生成表面層具有較佳再現性；利用聚丙烯酸及氫氧化鈉水溶液改變subphase的pH值或是改變水相溫度（5-35℃範圍），對於表面層的水解-縮合反應及擴散速度行為並無顯著的影響。
綜合上述條件後以四丁氧基鋯/己烷與四丁氧基鋯/己烷/HA兩溶液滴入水面製作LS膜，以SEM觀察表面型態發現液面層的氧化鋯LS膜在表面壓力為30 mN/m時具有緊密性，實驗中以此壓力條件在玻璃基材上沈積30次，LB沈積膜並無法均勻覆蓋玻璃基材，使得LB膜結構表面呈現片狀堆疊，觀察片狀薄膜的表面已有相當程度平整及緊密，但還是有裂縫的存在，而由AFM觀察表面起伏，發現經由添加界面活性劑及高溫鍛燒後，裂縫則會縮小而提高了表面LB膜的緻密性，經過溫鍛燒後的LB膜表面可見具有規則性及方向性的結晶顆粒產生。

關鍵字

二氧化鋯薄膜 ； Langmuir-Blodgett膜 ； π-A等溫線 π-A等溫線

並列摘要

This study examines the spread of Zirconium (Ⅳ) butoxide at the gas/liquid interface. The main purpose is to find out parameters that can affect the ZrO2 Langmuir film, and subsequently to make a smooth ZrO2 Langmuir-Blodgett (LB) film.
The formation of Langmuir film from Zr(OBu)4 is by (i)the dilution of Zr(OBu)4 using a suitable solvent, (ii)adding a surfactant, e.g. 2.4-Hen- eicosadiynoic Acid (HA), and (iii)changing the pH value of the subphase. Experimental results show that using a hexane-diluted Zr(OBu)4 solution can speed up the spreading of the solution. When the adding volume or the concentration of the solution is increased, the hydrolysis and condens- ation of the Zr(OBu)4 became more significant comparing to the diffusing velocity of the solution on the water surface. Adding HA into the Zr(OBu)4 solution resulted in a more stable Langmuir film with better reproductivity. No significant impact was formed on the Langmuir film when the pH value of the subphase is changed by adding polyacrylic acid, HNO3 or NaOH. Neither did the subphase temperature significantly change the π-Α isotherm of the Langmuir film.
The Zr(OBu)4/Hexane and the Zr(OBu)4/Hexane/HA solution were dripped onto the water surface to make LB film. The surface layer was observed by SEM via Langmuir-Schaeffer (LS) deposition. The ZrO2 LS film is not homogeneous but is compact under a surface pressure of 30 mN/m. Under the same surface pressure, LB deposition was made with 30 up-and-down motions on to a glass slide. The LB films remain in- homogeneous and the LB film structure appears like a stack of sheets. Cracks and vacancy between overlapped sheets can be formed in the ZrO2 LB film. The the addition of HA and a sintering at high temperatures seemed to smooth the edges. Crystalline particles of regular shape and orientation can be observed via AFM on the ZrO2 LB film after a high-temperature sintering.

並列關鍵字

Zirconia Thin Film ； Langmuir-Blodgett Film ； π-A Isotherm