Disentangling magnetic hardening and molecular spin chain contributions to exchange bias in ferromagnet/molecule bilayers

We performed SQUID and FMR magnetometry experiments to clarify the relationship between two reported magnetic exchange effects arising from interfacial spin-polarized charge transfer within ferromagnetic metal (FM)/molecule bilayers: the magnetic hardening effect, and spinterface-stabilized molecular spin chains. To disentangle these effects, both of which can affect the FM magnetization reversal, we tuned the metal phthalocyanine molecule central site's magnetic moment to selectively enhance or suppress the formation of spin chains within the molecular film. We find that both effects are distinct, and additive. In the process, we 1) extended the list of FM/molecule candidate pairs that are known to generate magnetic exchange effects, 2) experimentally confirmed the predicted increase in anisotropy upon molecular adsorption; and 3) showed that spin chains within the molecular film can enhance magnetic exchange. This magnetic ordering within the organic layer implies a structural ordering. Thus, by distengangling the magnetic hardening and exchange bias contributions, our results confirm, as an echo to progress regarding inorganic spintronic tunnelling, that the milestone of spintronic tunnelling across structurally ordered organic barriers has been reached through previous magnetotransport experiments. This paves the way for solid-state devices studies that exploit the quantum physical properties of spin chains, notably through external stimuli.Comment: Non

Altering the Static Dipole on Surfaces through Chemistry: Molecular Films of Zwitterionic Quinonoids

The adsorption of molecular films made of small molecules with a large intrinsic electrical dipole has been explored. The data indicate that such dipolar molecules may be used for altering the interface dipole screening at the metal electrode interface in organic electronics. More specifically, we have investigated the surface electronic spectroscopic properties of zwitterionic molecules containing 12π electrons of the <i>p</i>-benzoquinonemonoimine type, C₆H₂(<u>···</u>NHR)₂(<u>···</u>O)₂ (R = H (<b>1</b>), <i>n</i>-C₄H₉ (<b>2</b>), C₃H₆–S–CH₃ (<b>3</b>), C₃H₆–O–CH₃ (<b>4</b>), CH₂–C₆H₅ (<b>5</b>)), adsorbed on Au. These molecules are stable zwitterions by virtue of the meta positions occupied by the nitrogen and oxygen substituents on the central ring, respectively. The structures of <b>2</b>–<b>4</b> have been determined by single crystal X-ray diffraction and indicate that in these molecules, two chemically connected but electronically not conjugated 6π electron subunits are present, which explains their strong dipolar character. We systematically observed that homogeneous molecular films with thickness as small as 1 nm were formed on Au, which fully cover the surface, even for a variety of R substituents. Preferential adsorption toward the patterned gold areas on SiO₂ substrates was found with <b>4</b>. Optimum self-assembling of <b>2</b> and <b>5</b> results in ordered close packed films, which exhibit n-type character, based on the position of the Fermi level close to the conduction band minimum, suggesting high conductivity properties. This new type of self-assembled molecular films offers interesting possibilities for engineering metal–organic interfaces, of critical importance for organic electronics

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 molecule’s magnetization amplitude and direction can be tuned by varying the Cu–spacer thickness and evolves according to an interlayer exchange coupling mechanism. <i>Ab initio</i> calculations predict a highly spin-polarized density of states at the Fermi level of this metal-molecule interface, thereby strengthening prospective spintronics applications