Carbon-based Spintronics Research Articles

Dirac Half-Semimetallicity and Antiferromagnetism in Graphene Nanoribbon/Hexagonal Boron Nitride Heterojunctions.

Half-metals have been envisioned as active components in spintronic devices by virtue of their completely spin-polarized electrical currents. Actual materials hosting half-metallic phases, however, remain scarce. Here, we predict that recently fabricated heterojunctions of zigzag nanoribbons embedded in two-dimensional hexagonal boron nitride are half-semimetallic, featuring fully spin-polarized Dirac points at the Fermi level. The half-semimetallicity originates from the transfer of charges from hexagonal boron nitride to the embedded graphene nanoribbon. These charges give rise to opposite energy shifts of the states residing at the two edges, while preserving their intrinsic antiferromagnetic exchange coupling. Upon doping, an antiferromagnetic-to-ferrimagnetic phase transition occurs in these heterojunctions, with the sign of the excess charge controlling the spatial localization of the net magnetic moments. Our findings demonstrate that such heterojunctions realize tunable one-dimensional conducting channels of spin-polarized Dirac fermions seamlessly integrated into a two-dimensional insulator, thus holding promise for the development of carbon-based spintronics.

Tunable spin and conductance in porphyrin-graphene nanoribbon hybrids

Recently, porphyrin units have been attached to graphene nanoribbons (Por-GNR) enabling a multitude of structures. Here we report first-principles calculations of two prototypical, experimentally feasible, Por-GNR hybrids, one of which displays a small band gap relevant as electrodes in devices. Embedding a Fe atom in the porphyrin causes spin-polarized ground state (S = 1). Using density functional theory and nonequilibrium Green’s function, we examine a 2-terminal setup involving a Fe-Por-GNR between small band gap, Por-GNR electrodes. The coupling between the Fe-d and GNR band states results in a Fano anti-resonance feature in the spin transport, making the conductance highly sensitive to the Fe spin state. We demonstrate how mechanical strain or chemical adsorption on the Fe give rise to spin-crossover to S = 2 and S = 0, directly reflected in the transmission. Our results provide a deep understanding which can open an avenue for carbon-based spintronics and chemical sensing.

Recent Advances in the Spintronic Application of Carbon-Based Nanomaterials.

The term "carbon-based spintronics" mostly refers to the spin applications in carbon materials such as graphene, fullerene, carbon nitride, and carbon nanotubes. Carbon-based spintronics and their devices have undergone extraordinary development recently. The causes of spin relaxation and the characteristics of spin transport in carbon materials, namely for graphene and carbon nanotubes, have been the subject of several theoretical and experimental studies. This article gives a summary of the present state of research and technological advancements for spintronic applications in carbon-based materials. We discuss the benefits and challenges of several spin-enabled, carbon-based applications. The advantages include the fact that they are significantly less volatile than charge-based electronics. The challenge is in being able to scale up to mass production.

An anomalous Hall effect in edge-bonded monolayer graphene.

An anomalous Hall effect (AHE) is usually presumed to be absent in pristine graphene due to its diamagnetism. In this work, we report that a gate-tunable Hall resistance Rxy can be obtained in edge-bonded monolayer graphene without an external magnetic field. In a perpendicular magnetic field, Rxy consists of a sum of two terms: one from the ordinary Hall effect and the other from the AHE (RAHE). Plateaus of Rxy ∼ 0.94h/3e2 and RAHE ∼ 0.88h/3e2 have been observed while the longitudinal resistance Rxx decreases at a temperature of 2 K, which are indications of the quantum version of the AHE. At a temperature of 300 K, Rxx shows a positive, giant magnetoresistance of ∼177% and RAHE still has a value of ∼400 Ω. These observations indicate the existence of a long-range ferromagnetic order in pristine graphene, which may lead to new applications in pure carbon-based spintronics.

Interplay between π-Conjugation and Exchange Magnetism in One-Dimensional Porphyrinoid Polymers.

The synthesis of novel polymeric materials with porphyrinoid compounds as key components of the repeating units attracts widespread interest from several scientific fields in view of their extraordinary variety of functional properties with potential applications in a wide range of highly significant technologies. The vast majority of such polymers present a closed-shell ground state, and, only recently, as the result of improved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalization along the conjugation length has been achieved. Here, we present a combined strategy toward the fabrication of one-dimensional porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force microscopy describe the thermal-activated intra- and intermolecular oxidative ring closure reactions as well as the controlled tip-induced hydrogen dissociation from the porphyrinoid units. In addition, scanning tunneling spectroscopy measurements, complemented by computational investigations, reveal the open-shell character, that is, the antiferromagnetic singlet ground state (S = 0) of the formed polymers, characterized by singlet–triplet inelastic excitations observed between spins of adjacent porphyrinoid units. Our approach sheds light on the crucial relevance of the π-conjugation in the correlations between spins, while expanding the on-surface synthesis toolbox and opening avenues toward the synthesis of innovative functional nanomaterials with prospects in carbon-based spintronics.

Substrate Impact on MR Characteristics of Carbon Nano Films Explored via AFM and Raman Analysis.

Recent advances in the fabrication and classification of amorphous carbon (a-Carbon) thin films play an active part in the field of surface materials science. In this paper, a pulsed laser deposition (PLD) technique through controlling experimental parameters, including deposition time/temperature and laser energy/frequency, has been employed to examine the substrate effect of amorphous carbon thin film fabrication over SiO2 and glass substrates. In this paper, we have examined the structural and magnetoresistance (MR) properties of these thin films. The intensity ratio of the G-band and D-band (ID/IG) were 1.1 and 2.4, where the C(sp2) atomic ratio for the thin films samples that were prepared on glass and SiO2 substrates, were observed as 65% and 85%, respectively. The MR properties were examined under a magnetic field ranging from −9 T to 9 T within a 2-K to 40-K temperature range. A positive MR value of 15% was examined at a low temperature of 2 K for the thin films grown on SiO2 substrate at a growth temperature of 400 °C using a 300 mJ/pulse laser frequency. The structural changes may tune the magnetoresistance properties of these a-Carbon materials. These results were demonstrated to be highly promising for carbon-based spintronics and magnetic sensors.

Synthesis and Characterization of π-Extended Triangulene.

The electronic and magnetic properties of nanographenes strongly depend on their size, shape and topology. While many nanographenes present a closed-shell electronic structure, certain molecular topologies may lead to an open-shell structure. Triangular-shaped nanographenes with zigzag edges, which exist as neutral radicals, are of considerable interest both in fundamental science and for future technologies aimed at harnessing their intrinsic high-spin magnetic ground states for spin-based operations and information storage. Their synthesis, however, is extremely challenging owing to the presence of unpaired electrons, which confers them with enhanced reactivity. We report a combined in-solution and on-surface synthesis of π-extended triangulene, a non-Kekulé nanographene with the structural formula C33H15, consisting of ten benzene rings fused in a triangular fashion. The distinctive topology of the molecule entails the presence of three unpaired electrons that couple to form a spin quartet ground state. The structure of individual molecules adsorbed on an inert gold surface is confirmed through ultrahigh-resolution scanning tunneling microscopy. The electronic properties are studied via scanning tunneling spectroscopy, wherein unambiguous spectroscopic signatures of the spin-split singly occupied molecular orbitals are found. Detailed insight into its properties is obtained through tight-binding, density functional and many-body perturbation theory calculations, with the latter providing evidence that π-extended triangulene retains its open-shell quartet ground state on the surface. Our work provides unprecedented access to open-shell nanographenes with high-spin ground states, potentially useful in carbon-based spintronics.

Core-protective half-metallicity in trilayer graphene nanoribbons

Half-metals, playing an important role in spintronics, can be described as materials that enable fully spin-polarized electrical current. Taking place in graphene-based materials, half-metallicity has been shown in zigzag-edged graphene nanoribbons (ZGNRs) under an electric field. Localized electron states on the edge carbons are a key to enabling half-metallicity in ZGNRs. Thus, modification of the localized electron states is instrumental to the carbon-based spintronics. Our simple model shows that in a trilayer ZGNRs (triZGNRs) only the middle layer may become half-metallic leaving the outer layers insulating in an electric field, as confirmed by our density functional theory (DFT) calculations. Due to the different circumstances of the edge carbons, the electron energies at the edge carbons are different near the Fermi level, leading to a layer-selective half-metallicity. We believe that triZGNRs can be the tiniest electric cable (nanocable) form and can open a route to graphene-based spintronics applications.

Layer-selective half-metallicity in bilayer graphene nanoribbons.

Half-metallicity recently predicted in the zigzag-edge graphene nanoribbons (ZGNRs) and the hydrogenated carbon nanotubes (CNTs) enables fully spin-polarized electric currents, providing a basis for carbon-based spintronics. In both carbon systems, the half-metallicity arises from the edge-localized electron states under an electric field, lowering the critical electric field Dc for the half-metallicity being an issue in recent works on ZGNRs. A properly chosen direction of the electric field alone has been predicted to significantly reduce Dc in the hydrogenated CNTs, which in this work turned out to be the case in narrow bilayer ZGNRs (biZGNRs). Here, our simple model based on the electrostatic potential difference between the edges predicts that for wide biZGNRs of width greater than ~2.0 nm (10 zigzag carbon chains), only one layer of the biZGNRs becomes half-metallic leaving the other layer insulating as confirmed by our density functional theory (DFT) calculations. The electric field-induced switching of the spin-polarized current path is believed to open a new route to graphene-based spintronics applications.

Magnetoresistance sign change in iron-doped amorphous carbon films at low temperatures

Positive and negative magnetoresistance (MR) is observed in iron-doped amorphous carbon films at low temperatures. The MR of these films changes between positive and negative values by adjusting metallic doping, the temperature and the magnetic field. Wave-function shrinkage and spin-dependent scattering are found to be responsible for these changes. The former contributes to the positive MR, while the latter contributes to the negative one. These two factors compete with each other, resulting in different MR values with opposite signs. The results may be beneficial to carbon-based spintronics.

RKKY interaction between adsorbed magnetic impurities in graphene: Symmetry and strain effects

The growing interest in carbon-based spintronics has stimulated a number of recent theoretical studies on the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction in graphene, with the aim of determining the most energetically favorable alignments between embedded magnetic moments. The RKKY interaction in undoped graphene decays faster than expected for conventional two-dimensional materials, and recent studies suggest that the adsorption configurations favored by many transition-metal impurities may lead to even shorter-ranged decays and possible sign-changing oscillations. Here, we show that these features emerge in a mathematically transparent manner when the symmetry of the configurations is included in the calculation. Furthermore, we show that by breaking the symmetry of the graphene lattice, via uniaxial strain, the decay rate, and hence the range, of the RKKY interaction can be significantly altered. Our results suggest that magnetic interactions between adsorbed impurities in graphene can be manipulated by careful strain engineering of such systems.

Carbon-based spintronics

Carbon-based spintronics refers mainly to the spin injection and transport in carbon materials including carbon nanotubes, graphene, fullerene, and organic materials. In the last decade, extraordinary development has been achieved for carbon-based spintronics, and the spin transport has been studied in both local and nonlocal spin valve devices. A series of theoretical and experimental studies have been done to reveal the spin relaxation mechanisms and spin transport properties in carbon materials, mostly for graphene and carbon nanotubes. In this article, we provide a brief review on spin injection and transport in graphene, carbon nanotubes, fullerene and organic thin films.

Dynamic RKKY interaction in graphene

The growing interest in carbon-based spintronics has stimulated a number of recent theoretical studies on the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction in graphene, based on which the energetically favorable alignment between magnetic moments embedded in this material can be calculated. The general consensus is that the strength of the RKKY interaction in undoped graphene decays as $1/{D}^{3}$ or faster, where $D$ is the separation between magnetic moments. Such an unusually fast decay for a two-dimensional system suggests that the RKKY interaction may be too short ranged to be experimentally observed in graphene. Here we show in a mathematically transparent form that a far more long ranged interaction arises when the magnetic moments are taken out of their equilibrium positions and set in motion. We not only show that this dynamic version of the RKKY interaction in graphene decays far more slowly but also propose how it can be observed with currently available experimental methods.

Graphene-based bipolar spin diode and spin transistor: Rectification and amplification of spin-polarized current

Using nonequilibrium Green's function method combined with density functional theory we report bipolar spin diode behavior in zigzag graphene nanoribbons (ZGNRs). Nearly $\ifmmode\pm\else\textpm\fi{}100%$ spin-polarized current can be generated and tuned by a source-drain voltage and/or magnetic configurations in these two-terminal bipolar spin diodes. This unique transport property is attributed to the intrinsic transmission selection rule of the wave function of spin subbands near the Fermi level in ZGNRs. Moreover, the bias voltage and magnetic configurations of the two-terminal ZGNR-based spin diodes provide a rich variety of ways to control the spin current, which can be used to design three-terminal spin transistors. These ZGNRs-based components make possible the manipulation of spin-polarized current such as rectification and amplification for carbon-based spintronics.

Hydrogenated graphene nanoribbons for spintronics

We show how hydrogenation of graphene nanoribbons at small concentrations can open venues toward carbon-based spintronics applications regardless of any specific edge termination or passivation of the nanoribbons. Density-functional theory calculations show that an adsorbed H atom induces a spin density on the surrounding $\ensuremath{\pi}$ orbitals whose symmetry and degree of localization depends on the distance to the edges of the nanoribbon. As expected for graphene-based systems, these induced magnetic moments interact ferromagnetically or antiferromagnetically depending on the relative adsorption graphene sublattice, but the magnitude of the interactions are found to strongly vary with the position of the H atoms relative to the edges. We also calculate, with the help of the Hubbard model, the transport properties of hydrogenated armchair semiconducting graphene nanoribbons in the diluted regime and show how the exchange coupling between H atoms can be exploited in the design of novel magnetoresistive devices.

On the Question of Ferromagnetism in Proton and He-Irradiated Carbon

Carbon-based materials are the promising candidates for future applications in novel electronics. Carbon nanotube transistors and logic gates, conducting carbon-based polymers have been already demonstrated. In addition some forms of pure carbon should reveal magnetic properties, which in principle might be use in carbon-based spintronics. There are some theoretical predictions about carbon nano-stripes, schwarzite structures, H-doped graphite, in which electron spins on π-orbitals or broken sp 3 -bonds have (in some cases) ferromagnetic alignment. The experiments seeking for ferromagnetism were performed but many of them have failed due to the presence of ferromagnetic impurities (mostly iron). Nevertheless some of the experiments demonstrated ferromagnetism in pure carbon, particularly in carbon nano-foam [1] and proton-irradiated highly oriented pyrolitic graphite (HOPG) [2]. In 2003 Esquinazi used a MeV proton beam and discovered that it trigged ferromagnetism of the HOPG sample. After irradiation the hysteresis loop was observed over the irradiated area using Magnetic Force Microscopy and SQUID measurements. Such magnetic system seems to be very interesting for both: basic science and possible application points of view. However, hardly any other experimental group has confirmed such experimental observation. This situation is embarrassing, because it is not clear if nobody tried to verify the discoveries of Esquinazi et al. or nobody has succeeded in this verification. And since the lack of the phenomenon is difficult to be publish in any paper (vide the rumor of “cold fusion” in 90-ties) there are no information about the efforts of other groups. We have tried to repeat this discovery of the gropup of Esquinazi et al. We have used He + and H + beams focused on graphite sample. The amount of charge deposited in the sample was comparable to the amount of charge used by Esquinazi. Magnetic measurements were performed in SQUID magnetometer. The magnetization of the samples before and after irradiation was compared. Unfortunately we did not observe any ferromagnetic enhancement of magnetization of our irradiated samples. Even if experiment was not the same as Esqinazi’s one, we can exclude some of the mechanisms of ferromagnetism proposed by Esquinazi.