Shacham Ronen, Mandler Daniel, Avnir David
Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Chemistry. 2004 Apr 19;10(8):1936-43. doi: 10.1002/chem.200305469.
A novel electrochemical method for deposition of ZrO(2) thin films is described. The films, 50-600 nm thick, were obtained by applying moderate positive or negative potentials (+2.5 V to -1.5 V versus SHE) on conducting surfaces immersed in a 2-propanol solution of zirconium tetra-n-propoxide [Zr(OPr)(4)] in the presence of minute quantities of water (water/monomer molar ratios in the range of 10(-5) to 10(-1)), which was the limiting reagent. Oxidative electrochemical formation of solvated H(+) and reductive formation of OH(-) catalyze the hydrolysis and condensation of the metal alkoxide precursor. The magnitude of the applied potential and its duration provide a convenient way of controlling the film thickness. The films consist of an amorphous phase, as revealed by XRD measurements. The effects of different parameters, such as the applied potential and its duration, the amount of added water and the current-time characteristics, were studied. A mechanism for the electrodeposition of the zirconia films which is in accordance with our findings is proposed.
描述了一种用于沉积ZrO(2)薄膜的新型电化学方法。通过在浸入含有微量水(水/单体摩尔比在10(-5)至10(-1)范围内)的四正丙氧基锆[Zr(OPr)(4)]的2-丙醇溶液中的导电表面上施加适度的正电位或负电位(相对于标准氢电极,+2.5 V至-1.5 V)来获得厚度为50-600 nm的薄膜,水是限量试剂。溶剂化H(+)的氧化电化学形成和OH(-)的还原形成催化金属醇盐前体的水解和缩合。施加电位的大小及其持续时间提供了一种控制薄膜厚度的便捷方法。如XRD测量所示,薄膜由非晶相组成。研究了不同参数的影响,如施加电位及其持续时间、添加水的量和电流-时间特性。提出了一种与我们的发现相符的氧化锆薄膜电沉积机制。