Nanoscale Studies of Organic Radicals: Surface, Interface, and Spinterface.

In the last decade technology has brought significant changes to our lives, including new habits and a new view on social relationships. These technological innovations are based on several factors, one of which is miniaturization. This was made possible also due to the discovery and synthesis of new materials with characteristics at the nanoscale that are designed for specific purposes. This "on purpose" approach, joined to the development of preparation and growth methods, has led to use of thin films rather than bulk materials in devices. Using thin films makes devices easier to produce, and using films for coating protects the devices and gives specific properties to surfaces. For several decades thin films, surfaces, and interfaces have been intensively investigated. Indeed, device performances rely on the optimized match of thin films of different natures, such as organic and inorganic semiconductors and metals for contacts. Surprisingly, in comparison, little attention has been devoted to the deposition of organic radicals on a substrate. This might be because these materials are considered not stable enough for evaporation. In this work, we demonstrate that it is possible to evaporate and deposit organic radicals onto well-defined surfaces under controlled conditions, without degradation. Using soft X-ray spectroscopies, performed also at synchrotrons, we investigate thin film processes, surfaces, and interfaces at the nanoscale, when organic radicals are deposited on metal and metal oxide surfaces. We suggest how to design organic radicals bearing in mind the thermodynamic factors that govern thin film stability, with the purpose of obtaining not only a chemically stable radical, but also stable thin films. We investigate the thermal and air stability of the deposited films, and we explore the influence of the surface/radical chemical bond and the role of surface defects on the magnetic moment at the interface. We find that organic radicals are physisorbed and keep their magnetic moment on inert and passivated surfaces such as Au(111) and Al2 O3 (112̅0) single crystals, SiO2 , and ideal TiO2 (110) single crystals, while defective sites such as oxygen vacancies or the presence of OH groups lead to chemisorption of the organic radicals on the surface with quenching of their magnetic moment. Our work shows that the use of X-ray based techniques represents a powerful approach to reveal the mechanisms governing complex interfaces, such as radical/metal and radical/metal-oxide, where it is important to describe both charge and spin behavior (spinterfaces). It also makes it possible to conceive new experiments to investigate the magnetic character of the thin films versus their structural properties, toward tuning the arrangement of the molecules in films. Controlling the molecular arrangement will give the opportunity to tune the mutual position and orientation of the molecules, that is, of the single magnetic moments in the films, "imprinting" their magnetic properties. A deep understanding of stable radical/inorganic spinterfaces may open the way to use radicals in solid state devices or as quantum bits with dedicated configurations, as proposed for other molecular quantum bits, and in spin-based electronics.