Radical-Induced Changes in Transition Metal Interfacial Magnetic Properties: A Blatter Derivative on Polycrystalline Cobalt.

In this work, we study the interface obtained by depositing a monolayer of a Blatter radical derivative on polycrystalline cobalt. By examining the occupied and unoccupied states at the interface, using soft X-ray techniques, combined with electronic structure calculations, we could simultaneously determine the electronic structure of both the molecular and ferromagnetic sides of the interface, thus obtaining a full understanding of the interfacial magnetic properties. We found that the molecule is strongly hybridized with the surface. Changes in the core level spectra reflect the modification of the molecule and the cobalt electronic structures inducing a decrease in the magnetic moment of the cobalt atoms bonded to the molecules which, in turn, lose their radical character. Our method allowed us to screen, beforehand, organic/ferromagnetic interfaces given their potential applications in spintronics.

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 Al2O3(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.

Island shape and electronic structure in diindenoperylene thin films deposited on Au(110) single crystals.

We have investigated diindenoperylene (DIP) thin films deposited on Au(110) single crystals, by using a multi-technique approach based on X-ray photoemission spectroscopy (XPS), resonant photoemission spectroscopy (RPES), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, atomic force microscopy (AFM) and photoemission electron microscopy (PEEM). DIP molecules are physisorbed on gold, with image-charge screening playing the major role as an interface phenomenon. DIP thin films show Stranski-Krastanov growth mode and the structural herringbone arrangement mimics the arrangement found in DIP single crystals. These results are common with the (100) and (111) gold substrate geometries. On the contrary, the island aggregation is substrate geometry-dependent. This paves the way to exploit the degree of anisotropy in different lattice geometries as a tool for molecular patterning of inorganic surfaces, keeping the electronic structure preserved.

Long-Term Degradation Mechanisms in Application-Implemented Radical Thin Films.

Blatter radical derivatives are very attractive due to their potential applications, ranging from batteries to quantum technologies. In this work, we focus on the latest insights regarding the fundamental mechanisms of radical thin film (long-term) degradation, by comparing two Blatter radical derivatives. We find that the interaction with different contaminants (such as atomic H, Ar, N, and O and molecular H2, N2, O2, H2O, and NH2) affects the chemical and magnetic properties of the thin films upon air exposure. Also, the radical-specific site, where the contaminant interaction takes place, plays a role. Atomic H and NH2 are detrimental to the magnetic properties of Blatter radicals, while the presence of molecular water influences more specifically the magnetic properties of the diradical thin films, and it is believed to be the major cause of the shorter diradical thin film lifetime in air.

Role of the substrate in electronic structure, molecular orientation, and morphology of organic thin films: diindenoperylene on rutile TiO2(110).

The results of our multitechnique investigation performed on diindenoperylene thin films deposited on rutile TiO2(110) show island growth, with crystallites nucleating preferentially along the [110] substrate crystallographic axis. The findings evidence that the films' properties at the interface are common to those found for a number of organic molecules deposited on the same substrate, revealing that the structural and morphological properties of organic thin films on rutile TiO2(110) are completely driven by its surface morphology.

Intercorrelation of Electronic, Structural, and Morphological Properties in Nanorods of 2,3,9,10-Tetrafluoropentacene.

We evidence the intercorrelation of electronic, structural, and morphological properties in nanorods of a substituted fluorine-based pentacene, 2,3,9,10-tetrafluoropentacene, deposited on gold single crystals by using photoemission and X-ray absorption spectroscopy investigations. Our investigations show changes in the XPS spectroscopy lines, and NEXAFS features correlate with the specific structure of the assemblies and their morphology. Consequently, the chemical structure affects not only the molecular electronic structure and the way the molecules assemble in a film but also the film morphology leading to specific thin film electronic properties.

Paramagnetic nitronyl nitroxide radicals on Al2O3(11-20) single crystals: nanoscale assembly, morphology, electronic structure, and paramagnetic character toward future applications.

Aiming at future technological applications, we describe the interface and the thin film processes of a pyrene-substituted nitronyl nitroxide radical deposited on Al2O3(11-20) single crystals. Electronic properties, chemical environment at the interface, and morphology of the thin films have been investigated by a multitechnique approach. Spectroscopic and morphologic analyses indicate a Stranski-Krastanov growth mode and weak physisorption of the molecules on the surface. The deposition does not affect the paramagnetic character of the molecules. The results presented in this paper show not only that the investigated system is a promising candidate as a model for understanding thin film processes in purely organic-based magnets, but its characteristics are worth its future use in electronics, because the radical character of the molecules is completely preserved in the thin films.