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.
Spindependent hybridization at the ferromagnet/molecule interface has recently unveiled a promising new potential for spintronics. By projecting the spintronic properties (i.e. induced spin polarization) from a given ferromagnet electrode to the highly versatile and tailorable molecular layer, spindependent hybridization has opened up new opportunities to tailor spintronic device properties at the molecular scale. Here we focus on the potential and impact of this hybridization on spintronic devices. Depending on the coupling strength at the ferromagnet/molecule interface, the induced spin polarization can be enhanced or even inversed. In the first part of the paper, we introduce the concept of spindependent hybridization and, in particular, we show that it allows the magnetoresistive response of spintronic devices to be tuned. In the second part, we review the experimental evidence emphasizing spindependent hybridization in molecular layers and single molecules. In the last part, we highlight how this spindependent hybridization can play a key role in tunnelling magnetoresistance and tunnelling anisotropic magnetoresistance.
Molecular and organic spintronics is an emerging research field which combines the versatility of chemistry with the non-volatility of spintronics. Organic materials have already proved their potential as tunnel barriers (TBs) or spacers in spintronics devices showing sizable spin valve like magnetoresistance effects. In the last years, a large effort has been focused on the optimization of these organic spintronics devices. Insertion of a thin inorganic tunnel barrier (Al2O3 or MgO) at the bottom ferromagnetic metal (FM)/organic interface seems to improve the spin transport efficiency. However, during the top FM electrode deposition, metal atoms are prone to diffuse through the organic layer and potentially short-circuit it. This may lead to the formation of a working but undesired FM/TB/FM magnetic tunnel junction where the organic plays no role. Indeed, establishing a protocol to demonstrate the effective spin dependent transport through the organic layer remains a key issue. Here, we focus on Co/Al2O3/Alq3/Co junctions and show that combining magnetoresistance and inelastic electron tunnelling spectroscopy measurements one can sort out working “organic” and short-circuited junctions fabricated on the same wafer.
Organic spintronics is a new emerging field that promises to offer the full potential of chemistry to spintronics, as for example high versatility through chemical engineering and simple low cost processing. However, one key challenge that remains to be unlocked for further applications is the high incompatibility between spintronics key materials such as high Curie temperature Co, Ni, Fe (and their alloys) and wet chemistry. Indeed, the transition metal proneness to oxidation has so far hampered the integration of wet chemistry processes into the development of room temperature organic spintronics devices. As a result, they had mainly to rely on high vacuum physical processes, restraining the choice of available organic materials to a small set of sublimable molecules. In this letter, focusing on cobalt as an example, we show a wet chemistry method to easily and selectively recover a metallic surface from an air exposed oxidized surface for further integration into spintronics devices. The oxide etching process, using a glycolic acid based solution, proceeds without increasing the surface roughness and allows the retrieval of an oxygen-free chemically active cobalt layer. This unlocks the full potential of wet chemistry processes towards room temperature molecular spintronics with transition metals electrodes. We demonstrate this by the grafting of alkylthiols self-assembled monolayers on recovered oxidized cobalt surfaces. C 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. [http://dx.
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.
An imaging technique associating a slowly intermittent contact mode of atomic force microscopy (AFM) with a home-made multi-purpose resistance sensing device is presented. It aims at extending the widespread resistance measurements classically operated in contact mode AFM to broaden their application fields to soft materials (molecular electronics, biology) and fragile or weakly anchored nano-objects, for which nanoscale electrical characterization is highly demanded and often proves to be a challenging task in contact mode. Compared with the state of the art concerning less aggressive solutions for AFM electrical imaging, our technique brings a significantly wider range of resistance measurement (over 10 decades) without any manual switching, which is a major advantage for the characterization of materials with large on-sample resistance variations. After describing the basics of the set-up, we report on preliminary investigations focused on academic samples of self-assembled monolayers with various thicknesses as a demonstrator of the imaging capabilities of our instrument, from qualitative and semi-quantitative viewpoints. Then two application examples are presented, regarding an organic photovoltaic thin film and an array of individual vertical carbon nanotubes. Both attest the relevance of the technique for the control and optimization of technological processes.
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