Oxide Films at the Nanoscale: New Structures, New Functions, and New Materials

We all make use of oxide ultrathin films, even if we are unaware of doing so. They are essential components of many common devices, such as mobile phones and laptops. The films in these ubiquitous electronics are composed of silicon dioxide, an unsurpassed material in the design of transistors. But oxide films at the nanoscale (typically just 10 nm or less in thickness) are integral to many other applications. In some cases, they form under normal reactive conditions and confer new properties to a material: one example is the corrosion protection of stainless steel, which is the result of a passive film. A new generation of devices for energy production and communications technology, such as ferroelectric ultrathin film capacitors, tunneling magnetoresistance sensors, solar energy materials, solid oxide fuel cells, and many others, are being specifically designed to exploit the unusual properties afforded by reduced oxide thickness. Oxide ultrathin films also have tremendous potential in chemistry, representing a rich new source of catalytic materials. About 20 years ago, researchers began to prepare model systems of truly heterogeneous catalysts based on thin oxide layers grown on single crystals of metal. Only recently, however, was it realized that these systems may behave quite differently from their corresponding bulk oxides. One of the phenomena uncovered is the occurrence of a spontaneous charge transfer from the metal support to an adsorbed species through the thin insulating layer (or vice versa). The importance of this property is clear: conceptually, the activation and bond breaking of adsorbed molecules begin with precisely the same process, electron transfer into an antibonding orbital. But electron transfer can also be harnessed to make a supported metal particle more chemically active, increase its adhesion energy, or change its shape. Most importantly, the basic principles underlying electron transfer and other phenomena (such as structural flexibility, electronic modifications, and nanoporosity) are now largely understood, thus paving the way for the rational design of new catalytic systems based on oxide ultrathin films. Many of the mechanisms involved (electron tunneling, work function changes, defects engineering, and so forth) are typical of semiconductor physics and allow a direct link between the two fields. A related conceptual framework, the electronic theory of catalysis, was proposed a long time ago but has been largely neglected by the catalytic community. A renewed appreciation of this catalytic framework, together with spectacular advances in modeling and electronic structure methods, now makes it possible to combine theory with advanced experimental setups and meet the challenge of designing new materials with tailored properties. In this Account, we discuss some of the recent advances with nanoscale oxide films, highlighting contributions from our laboratory. Once mastered, ultrathin oxide films on metals will provide vast and unforeseen opportunities in heterogeneous catalysis as well as in other fields of science and technology.