Motivated by recent experimental studies on single molecular magnets grafted on graphene and single walled carbon nanotubes, we investigate the structural, electronic, and magnetic properties of an iron based magnetic molecule grafted on a graphene sheet using \textit{ab initio} calculations.
In particular, the induced charge transfer and magnetization are described in terms of the coupling between the molecule and the graphene orbitals.
This interaction and its effects on graphene electronic properties are determined and discussed in view of the potential utilization of graphene in spintronics.
Quantum transport reveals spin glass correlations in a 2D network of TbPc$_{2}$ single-molecule magnets grafted on graphene
Université Paris-Saclay（巴黎萨克雷大学）；CNRS（法国国家科学研究中心）；Laboratoire de Physique des Solides（固体物理实验室）；Institut des Sciences Moléculaires d’Orsay（奥赛分子科学研究所）；CEA（法国原子能和替代能源委员会）；NIMBE（纳米科学与集成材料国家研究中心）；LICSEN（界面化学与表面工程实验室）；Université Paris Cité（巴黎西岱大学）；Laboratoire Materiaux et Phénomènes Quantiques（材料与量子现象实验室）
Inducing magnetism in graphene holds great promises, such as controlling the exchange interaction with a gate electrode and generating exotic magnetic phases. Coating graphene with magnetic molecules or atoms has so far mostly lead to decreased graphene mobility. In the present work, we show that Pt-porphyrins adsorbed on graphene lead to an enhanced mobility and to gate-dependent magnetism. We report that porphyrins can be donor or acceptor, depending on graphene s initial doping. The porphyrins transfer charge and ionize around the charged impurities on graphene, decreasing the graphene dopi…
Chemical functionalization is a promising route to band gap engineering of graphene. We chemically grafted nitrophenyl groups onto exfoliated single-layer graphene sheets in the form of substrate-supported or free-standing films. Our transport measurements demonstrate that non-suspended functionalized graphene behaves as a granular metal, with variable range hopping transport and a mobility gap ~ 0.1 eV at low temperature. For suspended graphene that allows functionalization on both surfaces, we demonstrate tuning of its electronic properties from a granular metal to a gapped semiconductor, in…
Recent tribological experiments revealed that graphene is able to lubricate macroscale steel-on-steel sliding contacts very effectively both in dry and humid conditions. This effect has been attributed to a mechanical action of graphene related to its load-carrying capacity. Here we provide further insight into the functionality of graphene as lubricant by analysing its tribochemical action. By means of first principles calculations we show that graphene binds strongly to native iron surfaces highly reducing their surface energy. Thanks to a passivating effect, the metal surfaces coated by gra…
We study the interaction between graphene and a single-molecule-magnet, [Fe4(L)2(dpm)6]. Focusing on the closest Iron ion in a hollow position with respect to the graphene sheet, we derive a channel selective tunneling Hamiltonian, that couples different d orbitals of the Iron atom to precise independent combinations of sublattice and valley degrees of freedom of the electrons in graphene. When looking at the spin-spin interaction between the molecule and the graphene electrons, close to the Dirac point the channel selectivity results in a channel decoupling of the Kondo interaction, with two …
In this work, we have studied the chemical and magnetic interactions of Fe_n; n <= 6, clusters with a divacancy site in a graphene sheet by ab-initio density functional calculations. Our results show significant chemical interactions between the cluster and graphene. As a result, a complex distribution of magnetic moments appear on the distorted Fe clusters in presence of graphene and results in a lower average magnetic moments compared to the free clusters. The presence of cluster also prevents the formation of 5-8-5 ringed structure known to exhibit in a graphene sheet having a divacancy def…
Depositing magnetic insulators on graphene has been a promising route to introduce magnetism via exchange proximity interaction in graphene for future spintronics applications. Molecule-based magnets may offer unique opportunities because of their synthesis versatility. Here, we investigated the magnetic proximity effect of epitaxial iron phthalocyanine (FePc) molecules on high-quality monolayer and bilayer graphene devices on hexagonal boron nitride substrate by probing the local and non-local transport. Although the FePc molecules introduce large hole doping effects combined with mobility de…
Herein, intervalley scattering is exploited to account for anomalous antiresonances in the infrared spectra of doped and disordered single layer graphene. We present infrared spectroscopy measurements of graphene grafted with iodophenyl moieties in both reflection microscopy and transmission configurations. Asymmetric transparency windows at energies corresponding to phonon modes near the Γ and K points are observed, in contrast to the featureless spectrum of pristine graphene. These asymmetric antiresonances are demonstrated to vary as a function of the chemical potential. We propose a model …
First-principles calculations of the effect of carbon coverage on the atomic, electronic and magnetic structure of nickel and iron substrates demonstrate insignificant changes in the interatomic distances and magnetic moments on the atoms of the metallic substrates. The coverage of the iron surface by mono- and few-layer graphene induces significant changes in the orbital occupancies and exchange interactions between the layers in contrast to the case of a nickel substrate for which changes in the orbital ordering and exchange interactions are much smaller. Experimental measurements demonstrat…
Inspired by recent experimental realizations of monolayer Fe membranes in graphene perforations, we perform ab initio calculations of Fe monolayers and membranes embedded in graphene in order to assess their structural stability and magnetization. We demonstrate that monolayer Fe has a larger spin magnetization per atom than bulk Fe and that Fe membranes embedded in graphene exhibit spin magnetization comparable to monolayer Fe. We find that free-standing monolayer Fe is structurally more stable in a triangular lattice compared to both square and honeycomb lattices. This is contradictory to th…
Graphene - transition metal phthalocyanine (G-MPc) hybrid systems constitute promising platforms for densely-packed single-molecule magnets (SMMs). Here, we selected iron(II) phthalocyanine (FePc) and investigated its interaction with pristine and defective graphene layers employing density functional theory. Our calculations indicate that thorough proper dehydrogenation of the benzol rings in the FePc molecule its adsorption to graphene is thermodynamically favorable. In general, the presence of anchoring sites on the graphene layer, i.e. point defects, additionally facilitates the adsorption…
X-ray magnetic circular dichroism (XMCD) measurements of iron nano-islands grown on graphene and covered with a Au film for passivation reveal that the oxidation through defects in the Au film spontaneously leads to the formation of magnetite nano-particles (i.e, $Fe_3$$O_4$). The Fe nano-islands (20 and 75 monolayers; MLs) are grown on epitaxial graphene formed by thermally annealing 6H-SiC(0001) and subsequently covered, in the growth chamber, with nominal 20 layers of Au. Our X-ray absorption spectroscopy and XMCD measurements at applied magnetic fields show that the thin film (20 ML) is to…
Based on a low temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. These studies showed that the cycloaddition reactions can be carried out on the basal plane of graphene, even when there are no pre-existing defects. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken and local sp3 bonds were created. The grafted molecules perturbed the graphene lattice, generating a standing-wave pattern with an…
Metal nanostructures confined between sp2 hybridized 2D materials and solid supports are attracting attention for their potential application in new nanotechnologies. Model studies under well-defined conditions are valuable for understanding the fundamental aspects of the phenomena under 2D covers. In this work we investigate the intercalation of iron atoms through a single layer of mixed graphene and hexagonal boron nitride on Pt(111) using a combination of spectroscopic and microscopic techniques. Thermally activated diffusion of iron proceeds preferentially under graphene and only partially…
The electronic structure and magnetic properties of the graphene/Fe/Ni(111) system were investigated via combination of the density functional theory calculations and electron-spectroscopy methods. This system was prepared via intercalation of thin Fe layer (1 ML) underneath graphene on Ni(111) and its inert properties were verified by means of photoelectron spectroscopy. Intercalation of iron in the space between graphene and Ni(111) changes drastically the magnetic response from the graphene layer that is explained by the formation of the highly spin-polarized $3d_{z^2}$ quantum-well state i…
Magnetic materials have found wide application ranging from electronics and memories to medicine. Essential to these advances is the control of the magnetic order. To date, most room-temperature applications have a fixed magnetic moment whose orientation is manipulated for functionality. Here we demonstrate an iron-oxide and graphene oxide nanocomposite based device that acts as a tunable ferromagnet at room temperature. Not only can we tune its transition temperature in a wide range of temperatures around room temperature, but the magnetization can also be tuned from zero to 0.011 A.m$^2$/kg …
We demonstrate that a sizable chiral charge pumping can be achieved at room temperature in graphene/Yttrium Iron Garnet (YIG) bilayer systems. The effect, which cannot be attributed to the ordinary spin pumping, reveals itself in the creation of a dc electric field/voltage in graphene as a response to the dynamic magnetic excitations (spin waves) in an adjacent out-of-plane magnetized YIG film. We show that the induced voltage changes its sign when the orientation of the static magnetization is reversed, clearly indicating the broken spatial inversion symmetry in the studied system. The streng…
The electronic structure of carbon shells of carbon encapsulated iron nanoparticles carbon encapsulated Fe@C has been studied by X-ray resonant emission and X-ray absorption spectroscopy. The recorded spectra have been compared to the density functional calculations of the electronic structure of graphene. It has been shown that an Fe@C carbon shell can be represented in the form of several graphene layers with Stone-Wales defects. The dispersion of energy bands of Fe@C has been examined using the measured C Ka resonant X-ray emission spectra.
Quantum anomalous Hall state is expected to emerge in Dirac electron systems such as graphene under both sufficiently strong exchange and spin-orbit interactions. In pristine graphene, neither interaction exists; however, both interactions can be acquired by coupling graphene to a magnetic insulator (MI) as revealed by the anomalous Hall effect. Here, we show enhanced magnetic proximity coupling by sandwiching graphene between a ferrimagnetic insulator yttrium iron garnet (YIG) and hexagonal-boron nitride (h-BN) which also serves as a top gate dielectric. By sweeping the top-gate voltage, we o…
All-electrical writing and reading of spin states attract considerable attention for their promising applications in energy-efficient spintronics devices. Here we show, based on rigorous first-principles calculations, that the spin properties can be manipulated and detected in molecular spinterfaces, where an iron tetraphenyl porphyrin (FeTPP) molecule is deposited on boron-substituted graphene (B-G). Notably, a reversible spin switching between the $S=1$ and $S=3/2$ states is achieved by a gate electrode. We can trace the origin to a strong hybridization between the Fe-$d_{{z}^2}$ and B-$p_z$…
This article shows that the spin-to-charge current conversion in single-layer graphene (SLG) by means of the inverse Rashba-Edelstein effect (IREE) is made possible with the integration of this remarkable 2D-material with the unique ferrimagnetic insulator yttrium iron garnet (YIG = $Y_{3}Fe_{5}O_{12}$) as well as with the ferromagnetic metal permalloy (Py = $Ni_{81}Sb_{19}$). By means of X-ray absorption spectroscopy (XAS) and magnetic circular dichroism (XMCD) techniques, we show that the carbon atoms of the SLG acquires an induced magnetic moment due to the proximity effect with the magneti…
We demonstrate the existence of Giant proximity magnetoresistance (PMR) effect in a graphene spin valve where spin polarization is induced by a nearby magnetic insulator. PMR calculations were performed for yttrium iron garnet (YIG), cobalt ferrite (CFO), and two europium chalcogenides EuO and EuS. We find a significant PMR (up to 100%) values defined as a relative change of graphene conductance with respect to parallel and antiparallel alignment of two proximity induced magnetic regions within graphene. Namely, for high Curie temperature (Tc) CFO and YIG insulators which are particularly impo…
A colossal magnetoresistance ($\sim 100\times10^3\%$) and an extremely large magnetoresistance ($\sim 1\times10^6\%$) have been previously explored in manganite perovskites and Dirac materials, respectively. However, the requirement of an extremely strong magnetic field (and an extremely low temperature) makes them not applicable for realistic devices. In this work, we propose a device that can generate even larger changes in resistance in a zero-magnetic field and at a high temperature. The device is composed of a graphene under two strips of yttrium iron garnet (YIG), where two gate voltages…
We report the results of an experimental study of thermal and magnetic properties of nanostructured ferrimagnetic iron oxide composites with graphene and graphite fillers synthesized via the current activated pressure assisted densification. The thermal conductivity was measured using the laser-flash and transient plane source techniques. It was demonstrated that addition of 5 wt. % of equal mixture of graphene and graphite flakes to the composite results in a factor of x2.6 enhancement of the thermal conductivity without significant degradation of the saturation magnetization. The microscopy …
One of the primary objectives in molecular nano-spintronics is to manipulate the spin states of organic molecules with a d-electron center, by suitable external means. In this letter, we demonstrate by first principles density functional calculations, as well as second order perturbation thoery, that a strain induced change of the spin state, from S=1 $\to$ S=2, takes place for an iron porphyrin (FeP) molecule deposited at a divacancy site in a graphene lattice. The process is reversible in a sense that the application of tensile or compressive strains in the graphene lattice can stabilize FeP…
We report a systematic first-principles investigation of the influence of different magnetic insulators on the magnetic proximity effect induced in graphene. Four different magnetic insulators are considered: two ferromagnetic europium chalcogenides namely EuO and EuS and two ferrimagnetic insulators yttrium iron garnet (YIG) and cobalt ferrite (CFO). The obtained exchange-splitting varies from tens to hundreds of meV. We also find an electron doping induced by YIG and europium chalcogenides substrates, that shift the Fermi level up to 0.78 eV and 1.3 eV respectively, whereas hole doping up to…
In this paper, we have done a comparative study of electronic and magnetic properties of iron phthalocyanine (FePc) and cobalt phthalocyanine (CoPc) molecules physisorbed on monolayer of MoS$_2$ and graphene by using density functional theory. Various different types of physisorption sites have been considered for both surfaces. Our calculations reveal that the $M$Pc molecules prefer the S-top position on MoS$_2$. However, on graphene, FePc molecule prefers the bridge position while CoPc molecule prefers the top position. The $M$Pc molecules are physisorbed strongly on the MoS$_2$ surface than…
Oxygen-induced Fe surface segregation at the $L1_0$-FePd(001)/graphene heterointerface for spintronics devices: a first-principles study
Kobe University（神户大学）；ENS Paris-Saclay（巴黎萨克雷高等师范学院）；The University of Tokyo（东京大学）；National Institute of Advanced Industrial Science and Technology (AIST)（产业技术综合研究所）；Nagoya University（名古屋大学）
