The physicochemical properties of thin metal oxide layers strongly depend on the layer thickness and thus differ significantly from their bulk counterpart. In this work, we present the growth of defined thin layers of CeO₂ within mesostructured ZrO₂ thin films using atomic layer deposition (ALD). The prepared films consist of a cubic ordered arrangement of 15 nm spherical mesopores induced by the used diblock copolymer poly(isobutylene)-block-poly(ethylene oxide) (PIB₅₀-b-PEO₄₅), which allows studying the growth process and the successful coating of the interior pore surfaces via the combination of scanning electron microscopy (SEM), time-of-flight mass spectrometry (ToF-SIMS), and laser ellipsometry. These methods prove the CeO₂ layer growth and impregnation of the pores up to 100 ALD cycles, at which the interconnecting channels between the mesopore layers are filled completely impeding further transport of the gaseous CeO₂ precursors. X-ray photoelectron spectroscopy (XPS) and diffractometry (XRD) measurements point out the increased amount of Ce³⁺ after a low number of ALD cycles and show the presence of cubic CeO₂ with increasing amount of ALD cycles, respectively. Impedance spectroscopic investigation further proves the formation of a continuous CeO₂ path through the entire porous network of the insulating ZrO₂ film and shows a strong influence of the layer thickness on the conductivity. All in all, our work presents the preparation of novel hybrid CeO₂/ZrO₂ model systems, which enable us to tailor their physicochemical properties by changing the thickness of the active oxide layer, and promises improvements for their use as catalysts in oxidation reactions such as the HCl oxidation reaction or as a three-way catalytic converter in automotives.

中文翻译：

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有序介孔ZrO ₂薄膜中纳米CeO ₂层的原子层沉积及其对离子/电子电导率的影响

薄金属氧化物层的物理化学性质在很大程度上取决于层的厚度，因此与它们的体相显着不同。在这项工作中，我们介绍了使用原子层沉积（ALD）在介孔结构的ZrO ₂薄膜内生长CeO ₂定义的薄层。将制备的膜包括由所使用的二嵌段共聚物的聚（异丁烯）诱导的15和纳米的球形介孔的立方有序排列的-嵌段-聚（环氧乙烷）（PIB ₅₀ - b -PEO ₄₅），可以结合扫描电子显微镜（SEM），飞行时间质谱（ToF-SIMS）和激光椭圆仪研究生长过程和内部孔表面的成功涂层。这些方法证明了CeO ₂层的生长和孔的浸渍直至100个ALD循环，中孔层之间的互连通道被填充，完全阻碍了气态CeO ₂前体的进一步传输。X射线光电子能谱（XPS）和衍射（XRD）测量指出，在少量ALD循环后，Ce ³⁺的含量增加，并显示出立方CeO ₂的存在。分别增加ALD循环次数。阻抗谱研究进一步证明了贯穿绝缘ZrO ₂膜整个多孔网络的连续CeO ₂路径的形成，并显示了层厚对电导率的强烈影响。总而言之，我们的工作提出了新颖的混合CeO ₂ / ZrO ₂模型系统的制备，这些系统使我们能够通过改变活性氧化物层的厚度来定制其理化性质，并有望改善它们在氧化反应中作为催化剂的用途。在汽车中用作HCl氧化反应或三元催化转化器。