V. Davesne

Robust spin crossover and memristance across a single molecule

A nanoscale molecular switch can be used to store information in a single molecule. Although the switching process can be detected electrically in the form of a change in the molecules conductance, adding spin functionality to molecular switches is a key concept for realizing molecular spintronic devices. Here we show that iron-based spin-crossover molecules can be individually and reproducibly switched between a combined high-spin, high-conduction state and a low-spin, low-conduction state, provided the individual molecule is decoupled from a metallic substrate by a thin insulating layer. These results represent a step to achieving combined spin and conduction switching functionality on the level of individual molecules.

Exchange bias and room-temperature magnetic order in molecular layers

Molecular semiconductors may exhibit antiferromagnetic correlations well below room temperature. Although inorganic antiferromagnetic layers may exchange bias single-molecule magnets, the reciprocal effect of an antiferromagnetic molecular layer magnetically pinning an inorganic ferromagnetic layer through exchange bias has so far not been observed. We report on the magnetic interplay, extending beyond the interface, between a cobalt ferromagnetic layer and a paramagnetic organic manganese phthalocyanine (MnPc) layer. These ferromagnetic/organic interfaces are called spinterfaces because spin polarization arises on them. The robust magnetism of the Co/MnPc spinterface stabilizes antiferromagnetic ordering at room temperature within subsequent MnPc monolayers away from the interface. The inferred magnetic coupling strength is much larger than that found in similar bulk, thin or ultrathin systems. In addition, at lower temperature, the antiferromagnetic MnPc layer induces an exchange bias on the Co film, which is magnetically pinned. These findings create new routes towards designing organic spintronic devices.

Hysteresis and change of transition temperature in thin films of Fe{[Me2Pyrz]3BH}2, a new sublimable spin-crossover molecule.

Thin films of the spin-crossover (SCO) molecule Fe{[Me2Pyrz]3BH}2 (Fe-pyrz) were sublimed on Si/SiO2 and quartz substrates, and their properties investigated by X-ray absorption and photoemission spectroscopies, optical absorption, atomic force microscopy, and superconducting quantum interference device. Contrary to the previously studied Fe(phen)2(NCS)2, the films are not smooth but granular. The thin films qualitatively retain the typical SCO properties of the powder sample (SCO, thermal hysteresis, soft X-ray induced excited spin-state trapping, and light induced excited spin-state trapping) but present intriguing variations even in micrometer-thick films: the transition temperature decreases when the thickness is decreased, and the hysteresis is affected. We explain this behavior in the light of recent studies focusing on the role of surface energy in the thermodynamics of the spin transition in nano-structures. In the high-spin state at room temperature, the films have a large optical gap (∼5 eV), decreasing at thickness below 50 nm, possibly due to film morphology.

Control of defect-mediated tunneling barrier heights in ultrathin MgO films

The impact of oxygen vacancies on local tunneling properties across rf-sputtered MgO thin films was investigated by optical absorption spectroscopy and conducting atomic force microscopy. Adding O2 to the Ar plasma during MgO growth alters the oxygen defect populations, leading to improved local tunneling characteristics such as a lower density of current hotspots and a lower tunnel current amplitude. We discuss a defect-based potential landscape across ultrathin MgO barriers.

Spin crossover in Fe(phen)2(NCS)2 complexes on metallic surfaces

In this review, we give an overview on the spin crossover of Fe(phen)2(NCS)2 complexes adsorbed on Cu(100), Cu2N/Cu(100), Cu(111), Co/Cu(111), Co(100), Au(100), and Au(111) surfaces. Depending on the strength of the interaction of the molecules with the substrates, the spin crossover behavior can be drastically changed. Molecules in direct contact with non-magnetic metallic surfaces coexist in both the high- and low-spin states but cannot be switched between the two. Our analysis shows that this is due to a strong interaction with the substrate in the form of a chemisorption that dictates the spin state of the molecules through its adsorption geometry. Upon reducing the interaction to the surface either by adding a second molecular layer or inserting an insulating thin film of Cu2N, the spin crossover behavior is restored and molecules can be switched between the two states with the help of scanning tunneling microscopy. Especially on Cu2N, the two states of single molecules are stable at low temperature ...

Spin-Dependent Hybridization between Molecule and Metal at Room Temperature through Interlayer Exchange Coupling

We experimentally and theoretically show that the magnetic coupling at room temperature between paramagnetic Mn within manganese phthalocyanine molecules and a Co layer persists when separated by a Cu spacer. The molecules magnetization amplitude and direction can be tuned by varying the Cu-spacer thickness and evolves according to an interlayer exchange coupling mechanism. Ab initio calculations predict a highly spin-polarized density of states at the Fermi level of this metal-molecule interface, thereby strengthening prospective spintronics applications.

First glimpse of the soft x-ray induced excited spin-state trapping effect dynamics on spin cross-over molecules

The dynamics of the soft x-ray induced excited spin state trapping (SOXIESST) effect of Fe(phen)2(NCS)2 (Fe-phen) powder have been investigated by x-ray absorption spectroscopy (XAS) using the total electron yield method, in a wide temperature range. The low-spin (LS) state is excited into the metastable high-spin (HS) state at a rate that depends on the intensity of the x-ray illumination it receives, and both the temperature and the intensity of the x-ray illumination will affect the maximum HS proportion that is reached. We find that the SOXIESST HS spin state transforms back to the LS state at a rate that is similar to that found for the light induced excited spin state trapping (LIESST) effect. We show that it is possible to use the SOXIESST effect in combination with the LIESST effect to investigate the influence of cooperative behavior on the dynamics of both effects. To investigate the impact of molecular cooperativity, we compare our results on Fe-phen with those obtained for Fe{[Me2Pyrz]3BH}2 (Fe-pyrz) powder, which exhibits a similar thermal transition temperature but with a hysteresis. We find that, while the time constant of the dynamic is identical for both molecules, the SOXIESST effect is less efficient at exciting the HS state in Fe-pyrz than in Fe-phen.

Localized states in advanced dielectrics from the vantage of spin- and symmetry-polarized tunnelling across MgO

Research on advanced materials such as multiferroic perovskites underscores promising applications, yet studies on these materials rarely address the impact of defects on the nominally expected materials property. Here, we revisit the comparatively simple oxide MgO as the model material system for spin-polarized solid-state tunnelling studies. We present a defect-mediated tunnelling potential landscape of localized states owing to explicitly identified defect species, against which we examine the bias and temperature dependence of magnetotransport. By mixing symmetry-resolved transport channels, a localized state may alter the effective barrier height for symmetry-resolved charge carriers, such that tunnelling magnetoresistance decreases most with increasing temperature when that state is addressed electrically. Thermal excitation promotes an occupancy switchover from the ground to the excited state of a defect, which impacts these magnetotransport characteristics. We thus resolve contradictions between experiment and theory in this otherwise canonical spintronics system, and propose a new perspective on defects in dielectrics.

Oxygen-vacancy driven tunnelling spintronics across MgO

The conservation of an electron’s spin and symmetry as it undergoes solid-state tunnelling within magnetic tunnel junctions (MTJs) is thought to be best understood using MgO-based MTJs1. Yet the very large experimental values of tunnelling magnetoresistance (TMR) that justify this perception are often associated with tunnelling barrier heights well below those suggested by the MgO optical band gap. This combination of high TMR and low RA-product, while spawning spin-transfer/spin-orbit torque experiments and considerable industrial interest, cannot be explained by standard theory. Noting the impact of a tunnel barrier’s altered stoichiometry on TMR2, we reconcile this 10+year-old contradiction between theory and experiment by considering the impact of the MgO barrier’s structural defects3–5. We find that the ground and excited states of oxygen vacancies can promote localized states within the band gap with differing electronic character. By setting symmetry- and temperature-dependent tunnelling barrier heights, they alter symmetry-polarized tunnelling and thus TMR. We will examine how annealing, depending on MgO growth conditions, can alter the nature of these localized states. This oxygen vacancy paradigm of inorganic tunnelling spintronics opens interesting perspectives into endowing the MTJ with additional functionalities, such as optically manipulating the MTJ’s spintronic response.

Simple and advanced ferromagnet/molecule spinterfaces

Spin-polarized charge transfer between a ferromagnet and a molecule can promote molecular ferromagnetism 1, 2 and hybridized interfacial states3, 4. Observations of high spin-polarization of Fermi level states at room temperature5 designate such interfaces as a very promising candidate toward achieving a highly spin-polarized, nanoscale current source at room temperature, when compared to other solutions such as half-metallic systems and solid-state tunnelling over the past decades. We will discuss three aspects of this research. 1) Does the ferromagnet/molecule interface, also called an organic spinterface, exhibit this high spin-polarization as a generic feature? Spin-polarized photoemission experiments reveal that a high spin-polarization of electronics states at the Fermi level also exist at the simple interface between ferromagnetic cobalt and amorphous carbon6. Furthermore, this effect is general to an array of ferromagnetic and molecular candidates7. 2) Integrating molecules with intrinsic properties (e.g. spin crossover molecules) into a spinterface toward enhanced functionality requires lowering the charge transfer onto the molecule8 while magnetizing it1,2. We propose to achieve this by utilizing interlayer exchange coupling within a more advanced organic spinterface architecture. We present results at room temperature across the fcc Co(001)/Cu/manganese phthalocyanine (MnPc) system9. 3) Finally, we discuss how the Co/MnPc spinterface’s ferromagnetism stabilizes antiferromagnetic ordering at room temperature onto subsequent molecules away from the spinterface, which in turn can exchange bias the Co layer at low temperature10. Consequences include tunnelling anisotropic magnetoresistance across a CoPc tunnel barrier11. This augurs new possibilities to transmit spin information across organic semiconductors using spin flip excitations12.