Challenges and Prospects of Molecular Spintronics

Molecular spintronics,as an emerging field that makes full use of the advantage of ultralong room-temperature spin lifetime and abundant electrical-optical-magnetic properties of molecular semiconductors,has gained wide attention for its great potential for further commercial applications.Despite the significant progress that has been made,there remain several huge challenges that limit the future development of this field.This Perspective provides discussions on the spin transport mechanisms and performances of molecular semiconductors,spinterface effect,and related spin injection in spintronic devices,and current spin-charge interactive functionalities,along with the summarization of the main obstacles of these aspects.Furthermore,we particularly propose targeted solutions,aiming to enhance the spin injection and transport efficiency by molecular design and interface engineering and explore diverse spinrelated functionalities.Through this Perspective,we hope it will help the spintronic community identify the research trends and accelerate the development of molecular spintronics.

An introduction to molecular spintronics

We review the progress and future possibilities in the emerging area of molecular spintronics. We first provide an overview of the different transport regimes in which electronic nanodevices can operate, then briefly overview the important characteristics of molecular magnetic materials that can be useful for application in spintronics and we eventually present several schemes to include such systems into spintronic nanodevices. We hightlight the importance of a chemical approach to the area, and in the last section we showcase some approaches to the creation of hybrids made of carbon nanostructures and molecular magnets, which are gaining increasing attention.

Cornerstone of molecular spintronics: Strategies for reliable organic spin valves

Organic spin valve (OSV), one of the most promising and representative devices involving spin injection, transport and detection, has drawn tremendous attention owing to their ultra-long spin relaxation time in the field of molecular spintronics. Since the first demonstration of truly worked vertical OSV device in 2004, efforts in enhancement of high performance and pursuit of spin-related nature have been devoted in related field. It offers a new opportunity to develop the integrated flexible multi-functional arrays based on spintronics in the future. However, the unreliable working state in OSVs due to the lack of exploration on interface control will cause severe impact on the performance evaluation and further restrict their practical application. Herein, we focus on the recent progress in strategies for reliable fabrication and evaluation of typical OSVs in vertical configuration. Firstly, the challenges in protection of two spin interface properties and identification of spin-valve-like signals were proposed. Then, three points for attention including selection of bottom electrodes, optimization of organic spacer, and prevention of metal penetration to improve the device performance and reliability were mentioned. Particularly, various modified strategies to solve the “dead layer” issue were highlighted. Furthermore, we discussed the general protocols in the reliable evaluation of OSVs’ performance and transport mechanism identification. Notably, several key fundamentals resulting in spurious magnetoresistance (MR) response were illustrated. Finally, we also highlighted the future perspectives on spintronic devices of organic materials.

High-performance spin-filtering and spin-rectifying effects in Blatter radical-based molecular spintronic device

We design a Blatter radical-based molecular spintronic device, and investigate its spin-polarized transport properties using density functional theory and non-equilibrium Green's function technique. High-performance spin-rectifying and spin-filtering effects are realized. The physical mechanism is explained by the spin-resolved bias voltage-dependent transmission spectra, the energy levels of the corresponding molecular projected self-consistent Hamiltonian orbitals, and their spatial distributions. The results demonstrate that the Blatter radical has great potential in the development of highperformance multifunctional molecular spintronic devices.

Anisotropic spin transport and photoresponse characteristics detected by tip movement in magnetic single-molecule junction

Orientation-dependent transport properties induced by anisotropic molecules are enticing in single-molecule junctions.Here,using the first-principles method,we theoretically investigate spin transport properties and photoresponse characteristics in trimesic acid magnetic single-molecule junctions with different molecular adsorption orientations and electrode contact sites.The transport calculations indicate that a single-molecule switch and a significant enhancement of spin transport and photoresponse can be achieved when the molecular adsorption orientation changes from planar geometry to upright geometry.The maximum spin polarization of current and photocurrent in upright molecular junctions exceeds 90%.Moreover,as the Ni tip electrode moves,the tunneling magnetoresistance of upright molecular junctions can be increased to 70%.The analysis of the spin-dependent PDOS elucidates that the spinterfaces between organic molecule and ferromagnetic electrodes are modulated by molecular adsorption orientation,where the molecule in upright molecular junctions yields higher spin polarization.Our theoretical work paves the way for designing spintronic devices and optoelectronic devices with anisotropic functionality base on anisotropic molecules.

Recent spinterfacial studies targeted to spin manipulation in molecular spintronic devices

Molecular spintronics is an emerging field which evoked wide research attention since the first molecule-based spintronic device has been reported at 2002. Due to the active study over the last few years, it is found that the interfaces in spintronic device, so called spinterface, is of critical importance for many key issues in molecular spintronics, such as enhancing spin injection, lengthening spin transport distance, as well as manipulating spin signals in molecular spintronic devices. Here in this review, recent studies regarding spinterface in molecular devices, especially those impressive efforts devoted on spin manipulation, have been systematically summarized and discussed.

Spin-filter effect and spin-polarized optoelectronic properties in annulene-based molecular spintronic devices

Using Fe, Co or Ni chains as electrodes, we designed several annulene-based molecular spintronic devices and investigated the quantum transport properties based on density functional theory and non-equilibrium Green＇s function method.Our results show that these devices have outstanding spin-filter capabilities and exhibit giant magnetoresistance effect,and that with Ni chains as electrodes, the device has the best transport properties. Furthermore, we investigated the spinpolarized optoelectronic properties of the device with Ni electrodes and found that the spin-polarized photocurrents can be directly generated by irradiating the device with infrared, visible or ultraviolet light. More importantly, if the magnetization directions of the two electrodes are antiparallel, the photocurrents with different spins are spatially separated, appearing at different electrodes. This phenomenon provides a new way to simultaneously generate two spin currents.

Kondo effect in a deformed molecule coupled asymmetrically to ferromagnetic electrodes

The nonequilibrium Kondo effect is studied in a molecule quantum dot coupled asymmetrically to two ferromagnetic electrodes by employing the nonequilibrium Green function technique. The current-induced deformation of the molecule is taken into account, modeled as interactions with a phonon system, and phonon-assisted Kondo satellites arise on both sides of the usual main Kondo peak. In the antiparallel electrode configuration, the Kondo satellites can be split only for the asymmetric dot-lead couplings, distinguished from the parallel configuration where splitting also exists, even though it is for symmetric case. We also analyze how to compensate the splitting and restore the suppressed zero-bias Kondo resonance. It is shown that one can change the TMR ratio significantly from a negative dip to a positive peak only by slightly modulating a local external magnetic field, whose value is greatly dependent on the electron-phonon coupling strength.

Current spin polarization of a platform molecule with compression effect

Using the first-principles method,the spin-dependent transport properties of a novel platform molecule containing a freestanding molecular wire is investigated by simulating the spin-polarized scanning tunneling microscope experiment with Ni tip and Au substrate electrodes.Transport calculations show that the total current increases as the tip gradually approaches to the substrate,which is consistent with the conductance obtained from previous experiment.More interestingly,the spin polarization(SP)of current modulated by compression effect has the completely opposite trend to the total current.Transmission analyses reveal that the reduction of SP of current with compression process originates from the promotion of spin-down electron channel,which is controlled by deforming the molecule wire.In addition,the density of states shows that the SP of current is directly affected by the organic–ferromagnetic spinterface.The weak orbital hybridization between the Ni tip and propynyl of molecule results in high interfacial SP,whereas the breaking of the C≡C triple of propynyl in favor of the Ni–C–C bond induces the strong orbital hybridization and restrains the interfacial SP.This work proposes a new way to control and design the SP of current through organic–ferromagnetic spinterface using functional molecular platform.

Molecular design for enhanced spin transport in molecular semiconductors

Molecular semiconductors(MSCs),characterized by a longer spin lifetime than most of other materials due to their weak spin relaxation mechanisms,especially at room temperature,together with their abundant chemical tailorability and flexibility,are regarded as promising candidates for spintronic applications.Molecular spintronics,as an emerging subject that utilizes the unique properties of MSCs to study spin-dependent phenomena and properties,has attracted wide attention.In molecular spintronic devices,MSCs play the role as medium for information transport,process,and storage,in which the efficient spin inject–transport process is the prerequisite.Herein,we focus mainly on summarizing and discussing the recent advances in theoretical principles towards spin transport of MSCs in terms of the injection of spin-polarized carriers through the ferromagnetic metal/MSC interface and the subsequent transport within the MSC layer.Based on the theoretical progress,we cautiously present targeted design strategies of MSCs that contribute to the optimization of spin-transport efficiency and give favorable approaches to exploring accessional possibilities of spintronic materials.Finally,challenges and prospects regarding current spin transport are also presented,aiming to promote the development and application of the rosy and energetic field of molecular spintronics.

Room-Temperature Single-Molecule Conductance Switch via Confined Coordination-Induced Spin-State Manipulation

The emergence of molecular spintronics offers a unique chance for the design of molecular devices with different spin-states,and the control of spin-state becomes essential for molecular spin switches.However,the intrinsic spin switching from low-to high-spin state is a temperature-dependent process with a small energy barrier where low temperature is required to maintain the low-spin state.Thus,the room-temperature operation of single-molecule devices has not yet been achieved.Herein,we present a reversible single-molecule conductance switch by manipulating the spin states of the molecule at room temperature using the scanning tunneling microscope break-junction(STM-BJ)technique.The manipulation of the spin states between S=0 and S=1 is achieved by complexing or decomplexing the pyridine derivative molecule with a square planar nickel(Ⅱ)porphyrin.The bias-dependent conductance evolution proves that the strong electric field between the nanoelectrodes plays a crucial role in the coordination reaction.The density functional theory(DFT)calculations further reveal that the conductance changes come from the geometric changes of the porphyrin ring and spin-state switching of the Ni(Ⅱ)ion.Our work provides a new avenue to investigate room-temperature spin-related sensors and molecular spintronics.