SPIN

Organic spintronics, extended the conventional spintronics with metals, oxides and semiconductors, has opened new routes to explore the important process of spin-injection, transport, manipulation and detection, holding significant promise of revolutionizing future spintronic applications in high density information storage, multi-functional devices, seamless integration, and quantum computing. Here we survey this fascinating field from some new viewpoints on research hotspots and emerging trends. The main achievements and challenges arising from spin injection and transport, in organic materials are highlighted, as well as prospects of novel organic spintronic devices are also emphasized.

Magnetic molecules are auspicious candidates to act as functional units in molecular spintronics. Integrating molecules into a device environment providing mechanical support and electrical contacts requires their deposition as intact entities onto substrates. Thermal sublimation is a very clean deposition process that, however, thermally decomposes molecules of insufficient stability leading to the deposition of molecular fragments. Here, we show that the molecule-surface interaction of chemisorbed molecules affects the intramolecular bonding and can lead depending on the surface reactivity to either molecular decomposition or enhanced stability. We study the integrity of single bis(phthalocyaninato)-neodymium(III) molecules (NdPc₂) deposited by sublimation on differently reactive surfaces, namely Au(111), Cu(100), and two atomic layers of Fe on W(110), on the single molecular level by scanning tunneling microscopy (STM) and spectroscopy. We find a strongly substrate-dependent tendency of the NdPc₂ molecules to decompose into two Pc molecules. Surprisingly, the most reactive Fe/W(110) surface shows the lowest molecular decomposition probability, whereas there are no intact NdPc₂ molecules at all on the least reactive Au(111) surface. We attribute these findings to substrate-dependent partial charge transfer from the substrate to the Pc ligands of the molecule, which strengthens the intramolecular bonding mediated predominantly by electrostatic interaction.

We report the successful fabrication of lateral organic spin valves (OSVs) using polycrystalline pentacene as spacer and half-metallic La_0.7Sr_0.3MnO₃ (LSMO) as two electrodes. The distance between two electrodes ranges from 30 nm to 100 nm. The current–voltage characteristics follow the power law relation, which are attributed to the space charge limited current behavior. The devices with a spacing of 30 nm exhibits clear spin-valve characteristics with a magnetoresistance (MR) ratio of ~ 2% at 9 K. The MR effects disappear for electrode spacing about 100 nm, suggesting that the spin diffusion length is less than 100 nm.

Recent experimental reports suggest the formation of a highly spin-polarized interface ("spinterface") between a ferromagnetic (FM) Cobalt (Co) electrode and a metal-phthalocyanine (Pc) molecule. Another report shows an almost 60% giant magnetoresistance (GMR) response measured on Co/H₂Pc-based single molecule spin valves. In this paper, we compare the spin injection and transport properties of organic spin valves with two different organic spacers, namely Tris(8-hydroxyquinolinato) aluminum (Alq₃) and CoPc sandwiched between half-metallic La_0.7Sr_0.3MnO₃ (LSMO) and Co electrodes. Alq₃-based spin valves exhibit clear and reproducible spin valve switching with almost 35% negative GMR at 10 K, in accordance with previous reports. In contrast, cobalt-pthalocyanine (CoPc)-based spin valves fail to show clear GMR response above noise level despite high expectations based on recent reports. Investigations of electronic, magnetic and magnetotransport properties of electrode/spacer interfaces of LSMO/CoPc/Co devices offer three plausible explanations for the absence of GMR: (1) CoPc films are strongly chemisorbed on the LSMO surface. This improves the LSMO magnetic properties but also induces local traps at the LSMO interface for spin-polarized charge carriers. (2) At the Co/CoPc interface, diffusion of Co atoms into the organic semiconductor (OS) layer and chemical reactivity between Co and the OS deteriorates the FM properties of Co. This renders the Co/CoPc interface as unsuitable for efficient spin injection. (3) The presence of heavy Co atoms in CoPc leads to large spin–orbit coupling in the spacer. The spin relaxation time in the CoPc layer is therefore considerably smaller compared to Alq₃. Based on these findings, we suggest that the absence of GMR in CoPc-based spin valves is caused by a combined effect of inefficient spin injection from FM contacts and poor spin transport in the CoPc spacer layer.

We report studies of magnetic field effect (MFE) in polymer light-emitting electrochemical cells (PLEC) using the "super-yellow" poly-(phenylene vynilene) (SY-PPV) polymer in vertical and planar device configurations. The purpose is to discern the existing MFE mechanisms in organic light emitting diodes (OLEDs) where the current and electroluminescence are strongly modulated by a small applied magnetic field. In particular, we investigate the mutual relationship between magneto-conductance (MC) and magneto-electroluminescence (MEL) by studying the role of polaron density dissociated from polaron pairs (PP) on these magnetic responses. In general, the dissociated polaron density is determined by the PP dissociation rate and the PP density. For the planar PLEC, which possesses a small dissociation rate, we observe small and negative MC at all applied voltages regardless of the emission intensity, while MEL becomes positive when electroluminescence quantum efficiency increases. The MC has a much narrower width than the MEL, indicating that the MC and MEL do not share a common origin. However, MC reverses and has the same width as MEL when the device is exposed to a threshold laser power. For the vertical PLEC, characterized by a large dissociation rate, MC and MEL are positive and have the same width. We discuss the results using the existing MFE mechanism in OLEDs. We show that the PP model can explain the positive MEL and MC, while the negative MC can be explained by the bipolaron model. Finally, we present a possibility to complete an all-organic PLEC magnetic sensor by using an inkjet printer.

Spin-dependent transport through a family of biphenyl-dithiolate molecules was investigated theoretically. Torsion angles ϕ between the two phenyl rings in these molecules can be chemically tuned. Calculated conductances of molecular junctions are proportional to cos²ϕ, but their magnetoresistances are nearly independent on ϕ. Calculation results indicate that resistances and magnetoresistances of molecular junctions can be engineered separately.

We studied the changes in the magneto-conductance (MC) response in bipolar and unipolar organic diodes based on the π-conjugated polymer poly[2-methoxy-5-(2-ethylhexyl-oxy)-1,4-phenylene-vinylene] (MEH-PPV), upon prolonged illumination of light in the Visible–UV range. We found that the MC response in the hole-unipolar device gradually changes sign from negative to positive upon illumination, caused by the photogeneration of metastable donor-like defects in the MEH-PPV layer. This conclusion is supported by photoinduced absorption spectroscopy of pristine MEH-PPV film. In contrast, we found very little change in the MC response upon illumination of electron-unipolar devices; however, the MC response substantially increases in bipolar devices. We interpret the sign change in the MC response of hole-unipolar devices as due to illumination induced change in the spin-pairs that participate in the MC, from spin pairs of same charge to spin pairs of opposite charges.

Understanding the interaction of organic molecules adsorbed on magnetic surfaces has shown considerable progress in recent years. The creation of hybridized interface between carbon-based aromatic molecule and the magnetic surface is observed to give rise to new interface states with unique electronic and magnetic character. This study has opened up a molecular-design initiative to tailor the spin dependent electronic and magnetic functionalities of the hybrid interface. The purpose of this article is to provide a fundamental understanding of the spin-chemistry and spin-physics associated with the formation of such ferromagnet-molecule hybrid interfaces. We also discuss the recent progress in this field using state-of-the-art experiments and theoretical calculations with focus on the magnetic properties of the molecule and the magnetic surface. The study reveals several interesting interface phenomena: formation of induced molecular moment and exchange coupling with the magnetic surface, and molecular spin-filters. It also demonstrates significant changes in the magnetic anisotropy and inter-atomic magnetic exchange coupling of the magnetic surface. These studies open the possibilities of exploring new molecular functionalities toward further research in the subfield of interface-assisted molecular spintronics.

The frequency-dependent impedance of a series of ferromagnet (FM)/organic semiconductor (OSC)/FM tri-layered organic spin valves (OSV) is investigated in the frequency range of 10 Hz–1 MHz. An equivalent resistor–capacitor (RC) parallel network model is employed to analyze the magnetoresistance (MR) and magnetocapacitance (MC) effects. Fitting with the model yields field-dependent parameters and the resistive parameters agree with the experimental results. The analysis of the impedance spectra indicates an effective magnetotransport mechanism dominated by the charge accumulation at the organic–FM interfaces.

Using nonequilibrium Green's functions (NEGFs) combined with the density functional theory (DFT), we study the electronic transport properties of a single molecule magnet Co(dmit)₂, which is sandwiched between two monatomic chain electrodes, and the different electrode materials carbon, iron and gold, have been considered. The results show that the electrodes play a crucial role in the spin-dependent transport of the Co(dmit)₂ molecular device, and some interesting phenomenon, such as perfect spin-filtering effect, rectifying and negative differential resistance (NDR) can be observed. We demonstrated that the magnetic Fe electrode can lead to high spin-flittering effect, and the different hybridization and alignment of energy levels between the molecule and the electrodes may be responsible for the rectification performance, and the distributions (delocalization or localization) of the frontier molecular orbitals under different bias result in the NDR behaviors. These characteristics could be used in the study of spin physics and the realization of nanospintronic devices.