ABSTRACT
The spontaneous growth of lamellar metal-alkanethiolates (LMAs) on reactive ferromagnetic surfaces as a result of surface oxidation has been observed. When alkanethiol self-assembled monolayers (SAMs) grown under an inert atmosphere over cobalt or permalloy (Ni80Fe20) are exposed to air, oxygen diffuses through the molecular layer. This induces an oxidation of metal atoms at the metal surface and a release of the resulting metal cations that migrate coordinated by the alkanethiol molecules to form lamellar structures over the SAMs. This process has been imaged in real-time, under ambient conditions, by means of different microscopy techniques. The influence of the alkyl chain length, the nature of the ferromagnet, the temperature and the atmospheric moisture on the number, area and height of the resulting features has been systematically evaluated. Remarkably, the possibility to follow the migration in real-time makes it a promising model system for the study of surface/molecule interface processes. Most importantly, the composition and crystallinity of these LMAs have been studied, evidencing that real 2D coordination polymers are formed on the surface. Hence, one could envision this strategy as a new method for the assembly of more complex low-dimensional (2D) magnetic materials based on coordination polymers.
ABSTRACT
A challenge in molecular spintronics is to control the magnetic coupling between magnetic molecules and magnetic electrodes to build efficient devices. Here we show that the nature of the magnetic ion of anchored metal complexes highly impacts the exchange coupling of the molecules with magnetic substrates. Surface anchoring alters the magnetic anisotropy of the cobalt(II)-containing complex (Co(Pyipa)2), and results in blocking of its magnetization due to the presence of a magnetic hysteresis loop. In contrast, no hysteresis loop is observed in the isostructural nickel(II)-containing complex (Ni(Pyipa)2). Through XMCD experiments and theoretical calculations we find that Co(Pyipa)2 is strongly ferromagnetically coupled to the surface, while Ni(Pyipa)2 is either not coupled or weakly antiferromagnetically coupled to the substrate. These results highlight the importance of the synergistic effect that the electronic structure of a metal ion and the organic ligands has on the exchange interaction and anisotropy occurring at the molecule-electrode interface.
ABSTRACT
Chemically functionalized surfaces are studied for a wide range of applications going from medicine to electronics. Whereas non-magnetic surfaces have been widely studied, functionalization of magnetic surfaces is much less common and has almost never been used for spintronics applications. In this article we present the functionalization of La2/3Sr1/3MnO3, a ferromagnetic oxide, with self-assembled monolayers for spintronics. La2/3Sr1/3MnO3 is the prototypical half-metallic manganite used in spintronics studies. First, we show that La2/3Sr1/3MnO3 can be functionalized by alkylphosphonic acid molecules. We then emphasize the use of these functionalized surfaces in spintronics devices such as magnetic tunnel junctions fabricated using a nano-indentation based lithography technique. The observed exponential increase of tunnel resistance as a function of alkyl chain length is a direct proof of the successful connection of molecules to ferromagnetic electrodes. For all alkyl chains studied we obtain stable and robust tunnel magnetoresistance, with effects ranging from a few tens to 10 000%. These results show that functionalized electrodes can be integrated in spintronics devices and open the door to a molecular engineering of spintronics.