Houser Jerrod E, Hebert Kurt R
Department of Chemical and Biological Engineering, Iowa State University, Ames, Iowa 50011, USA.
Nat Mater. 2009 May;8(5):415-20. doi: 10.1038/nmat2423. Epub 2009 Apr 12.
Porous anodic alumina (PAA) films are widely used as templates for functional nanostructures, because of the high regularity and controllability of the pore morphology. However, growth mechanisms have not yet been developed that can explain quantitative relationships between processing conditions and oxide layer geometry. Here, we present a model for steady-state growth of these amorphous films, incorporating the novel feature that metal and oxygen ions are transported by coupled electrical migration and viscous flow. The oxide flow in the model arises near the film-solution interface at the pore bottoms, in response to the constraint of volume conservation. The hypothesis of viscous flow was successfully validated through detailed comparisons to observations of the motion of tungsten tracers in the film. Predictions of localized tensile stress near nanoscale ridges at the metal-film interface were supported by observations of voids at these sites. We suggest that the ordering of PAA may be explained by a mechanism in which metal-film interface motion is regulated by the combination of ionic migration in the oxide and stress-driven interface diffusion of metal atoms.
多孔阳极氧化铝(PAA)膜因其孔形态的高度规则性和可控性而被广泛用作功能性纳米结构的模板。然而,尚未开发出能够解释加工条件与氧化层几何形状之间定量关系的生长机制。在此,我们提出了一种用于这些非晶膜稳态生长的模型,该模型包含了金属和氧离子通过耦合电迁移和粘性流进行传输这一新颖特征。模型中的氧化物流在孔底部的膜 - 溶液界面附近产生,这是由于体积守恒的限制。通过与膜中钨示踪剂运动的观测结果进行详细比较,成功验证了粘性流假说。在这些位置观察到的空隙支持了金属 - 膜界面处纳米级脊附近局部拉伸应力的预测。我们认为,PAA的有序性可以通过一种机制来解释,即在这种机制中,金属 - 膜界面运动由氧化物中的离子迁移和金属原子的应力驱动界面扩散共同调节。