Magnetic molecules are potential building blocks for the design of spintronic devices. Moreover, molecular materials enable the combination of bottom-up processing techniques, for example with conventional top-down nanofabrication. The development of solid-state spintronic devices based on the giant magnetoresistance, tunnel magnetoresistance and spin-valve effects has revolutionized magnetic memory applications. Recently, a significant improvement of the spin-relaxation time has been observed in organic semiconductor tunnel junctions, single non-magnetic molecules coupled to magnetic electrodes have shown giant magnetoresistance and hybrid devices exploiting the quantum tunnelling properties of single-molecule magnets have been proposed. Herein, we present an original spin-valve device in which a non-magnetic molecular quantum dot, made of a single-walled carbon nanotube contacted with non-magnetic electrodes, is laterally coupled through supramolecular interactions to TbPc(2) single-molecule magnets (Pc=phthalocyanine). Their localized magnetic moments lead to a magnetic field dependence of the electrical transport through the single-walled carbon nanotube, resulting in magnetoresistance ratios up to 300% at temperatures less than 1 K. We thus demonstrate the functionality of a supramolecular spin valve without magnetic leads. Our results open up prospects of new spintronic devices with quantum properties.

Supramolecular spin valves

Organic semiconductors are attractive candidates for spintronics applications because of their long spin lifetimes. But few studies have investigated how to optimize the injection of spin into these materials. A new study suggests that the metal/organic interface is key.

Unravelling the role of the interface for spin injection into organic semiconductors

The field of molecular magnetism is rapidly evolving towards the use of magnetic molecules and molecule-based magnetic materials in physics-driven and nanotechnology-driven fields, in particular molecular spintronics, quantum technologies, metal–organic frameworks (MOFs) and 2D materials. In molecular spintronics, the goal is the development of a new generation of spintronic devices based on molecular materials or, in the longer term, on one or a few molecules. In the area of quantum technologies, the milestones reached in the design of molecular spin qubits with long quantum coherence times and in the implementation of quantum operations have raised expectations for the use of molecular spin qubits in quantum computation. MOFs and 2D materials are two classes of materials for which magnetism has been, until very recently, an elusive property; molecular materials with attractive properties and functionalities are now starting to be developed in both areas. In MOFs, single-molecule magnets and spin crossover complexes can be integrated into the nodes of the framework, within the pores or both, sometimes giving rise to smart magnetic materials or to hybrid materials exhibiting synergistic combinations of properties. 2D molecular-based magnets can provide a platform to study magnetism in the 2D limit and exhibit superior properties compared with their inorganic analogues in terms of chemical stability and tunability. This Review discusses the expansion of the field of molecular magnetism from the chemical design and physical study of single-molecule magnets and multifunctional magnetic materials towards physics- and nanotechnology-driven areas, in particular molecular spintronics, quantum technologies, metal–organic frameworks and 2D materials.

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Molecular magnetism: from chemical design to spin control in molecules, materials and devices

The origin of the effect that a magnetic field has on various electronic properties of organic semiconductors is still controversial. It is now shown that substituting hydrogen for deuterium in conducting polymers changes the response to a magnetic field substantially, proving the essential part played by hyperfine interaction in this effect.

Isotope effect in spin response of pi-conjugated polymer films and devices.

V.F.C. and A.F. contributed equally to this work. The authors thank the FCT—Fundacao para a Ciencia e Tecnologia—for financial support under framework of the Strategic Funding UID/FIS/04650/2013, project PTDC/ EEI-SII/5582/2014 and project UID/EEA/04436/2013 by FEDER funds through the COMPETE 2020—Programa Operacional Competitividade e Internacionalizacao (POCI). Funds provided by FCT in the framework of EuroNanoMed 2016 call, Project LungChek ENMed/0049/2016 are also gratefully acknowledged. V.F.C., A.F., C.R., and P.M. also thank the FCT for the grants SFRH/BPD/98109/2013, SFRH/BPD/104204/2014, SFRH/ BPD/90870/2012 and SFRH/BPD/96227/2013, respectively. Finally, the authors acknowledge funding by the Spanish Ministry of Economy and Competitiveness (MINECO) through the project MAT2016-76039C4-3-R (AEI/FEDER, UE) and from the Basque Government Industry Department under the ELKARTEK program.

Advances in Magnetic Nanoparticles for Biomedical Applications.

Organic semiconductors are characterized by a very low spin–orbit interaction, which, together with their chemical flexibility and relatively low production costs, makes them an ideal materials system for spintronics applications. The first experiments on spin injection and transport occurred only a few years ago, and since then considerable progress has been made in improving performance as well as in understanding the mechanisms affecting spin-related phenomena. Nevertheless, several challenges remain in both device performance and fundamental understanding before organic semiconductors can compete with inorganic semiconductors or metals in the development of realistic spintronics applications. In this article we summarize the main experimental results and their connections with devices such as light-emitting diodes and electronic memory devices, and we outline the scientific and technological issues that make organic spintronics a young but exciting field.

Spin routes in organic semiconductors

This Perspective discusses the spin-dependent properties emerging at the interfaces of molecular and inorganic materials, and describes possible future developments for spin-based technologies. The miniaturization trend in the semiconductor industry has led to the understanding that interfacial properties are crucial for device behaviour. Spintronics has not been alien to this trend, and phenomena such as preferential spin tunnelling, the spin-to-charge conversion due to the Rashba–Edelstein effect and the spin–momentum locking at the surface of topological insulators have arisen mainly from emergent interfacial properties, rather than the bulk of the constituent materials. In this Perspective we explore inorganic/molecular interfaces by looking closely at both sides of the interface. We describe recent developments and discuss the interface as an ideal platform for creating new spin effects. Finally, we outline possible technologies that can be generated thanks to the unique active tunability of molecular spinterfaces.

Activating the molecular spinterface.

Magnetic silk fibroin protein (SFP) scaffolds integrating magnetic materials and featuring magnetic gradients were prepared for potential utility in magnetic-field assisted tissue engineering. Magnetic nanoparticles (MNPs) were introduced into SFP scaffolds via dip-coating methods, resulting in magnetic SFP scaffolds with different strengths of magnetization. Magnetic SFP scaffolds showed excellent hyperthermia properties achieving temperature increases up to 8 °C in about 100 s. The scaffolds were not toxic to osteogenic cells and improved cell adhesion and proliferation. These findings suggest that tailored magnetized silk-based biomaterials can be engineered with interesting features for biomaterials and tissue-engineering applications.

Biomimetic magnetic silk scaffolds.

We investigate spin precession (Hanle effect) in the prototypical organic spintronic giant magnetoresistance device La0.7Sr0.3MnO3/tris(8-hydroxyquinoline)/AlOx/Co. The Hanle effect is not observed in measurements taken by sweeping a magnetic field at different angles from the plane of the device. As possible explanations we discuss the tilting out of plane of the magnetization of the electrodes, exceptionally high mobility, or hot spots. Our results call for a greater understanding of spin injection and transport in such devices.

Hanle effect missing in a prototypical organic spintronic device

We investigate spin precession (Hanle effect) in the prototypical organic spintronic giant magnetoresistance (GMR) device La0.7Sr0.3MnO3(LSMO)/tris(8-hydroxyquinoline)(Alq3)/AlOx/Co. The Hanle effect is not observed in measurements taken by sweeping a magnetic field at different angles from the plane of the device. As possible explanations we discuss the tilting out of plane of the magnetization of the electrodes, exceptionally high mobility or hot spots. Our results call for a greater understanding of spin injection and transport in such devices.

V. Alek Dediu

Papers

Spin routes in organic semiconductors

Activating the molecular spinterface.

Biomimetic magnetic silk scaffolds.

Hanle effect missing in a prototypical organic spintronic device

Hanle effect missing in a prototypical organic spintronic device