Metal–oxide interfaces play a fundamental role in determining the functional properties of artificial layered heterostructures, which are at the root of present and future technological applications. Magnetic exchange and magnetoelectric coupling, spin filtering, metal passivation, catalytic activity of oxide-supported nano-particles are just few examples of physical and chemical processes arising at metal–oxide hybrid systems, readily exploited in working devices. These phenomena are strictly correlated with the chemical and structural characteristics of the metal–oxide interfacial region, making a thorough understanding of the atomistic mechanisms responsible of its formation a prerequisite in order to tailor the device properties. The steep compositional gradient established upon formation of metal–oxide heterostructures drives strong chemical interactions at the interface, making the metal–oxide boundary region a complex system to treat, both from an experimental and a theoretical point of view. However, once properly mastered, interfacial chemical interactions offer a further degree of freedom for tuning the material properties. The goal of the present review is to provide a summary of the latest achievements in the understanding of metal/oxide and oxide/metal layered systems characterized by reactive interfaces. The influence of the interface composition on the structural, electronic and magnetic properties will be highlighted. Particular emphasis will be devoted to the discussion of ultra-thin epitaxial oxides stabilized on highly oxidizable metals, which have been rarely exploited as oxide supports as compared to the much more widespread noble and quasi noble metallic substrates. In this frame, an extensive discussion is devoted to the microscopic characterization of interfaces between epitaxial metal oxides and the Fe(001) substrate, regarded from the one hand as a prototypical ferromagnetic material and from the other hand as a highly oxidizable metal.

金属氧化物界面在确定人造层状异质结构的功能特性中起着根本性的作用，而这些结构是当前和未来技术应用的根本。氧化物负载的纳米粒子的磁交换和磁电耦合，自旋过滤，金属钝化，催化活性只是在金属-氧化物混合系统中发生的物理和化学过程的几个例子，在工作设备中很容易被利用。这些现象与金属-氧化物界面区域的化学和结构特征紧密相关，因此，全面了解导致其形成的原子机理是调整设备性能的前提。从金属-氧化物异质结构的形成建立的陡峭的成分梯度驱动了界面处的强烈化学相互作用，从实验和理论的角度来看，使金属-氧化物边界区域成为要处理的复杂系统。但是，一旦正确掌握，界面化学相互作用将为调节材料特性提供更​​大的自由度。本综述的目的是概述在了解以反应性界面为特征的金属/氧化物和氧化物/金属层状体系方面的最新成就。界面组成对结构，电子和磁性能的影响将被重点介绍。将特别着重讨论稳定在高度可氧化金属上的超薄外延氧化物，与更广泛的贵金属和准贵金属基底相比，它们很少被用作氧化物载体。在此框架中，广泛讨论了外延金属氧化物与Fe（001）衬底之间的界面的微观表征，一方面将其视为典型的铁磁材料，另一方面将其视为高度可氧化的金属。