Using first-principles calculations based on density functional theory and the nonequilibrium Green function formalism, we studied the spin transport through metal-phthalocyanine (MPc, M=Ni, Fe, Co, Mn, Cr) molecules connected to aurum nanowire electrodes. We found that the MnPc, FePc, and CrPc molecular devices exhibit a perfect spin filtering effect compared to CoPc and NiPc. Moreover, negative differential resistance appears in FePc molecular devices. The transmission coefficients at different bias voltages were further presented to understand this phenomenon. These results would be useful in designing devices for future nanotechnology.
We investigate the adsorption of cobalt phthalocyanine (CoPc) molecules on a thin layer of cobalt oxide grown on Ir(100). To that end we compare the results of low-temperature scanning tunneling microscopy (STM) with those of ab-initio density functional theory (DFT) calculations and reveal the adsorption geometry. We find that the CoPc molecules lie flat on the surface and that their central cobalt atom forms a chemical bond to a substrate oxygen ion. However, this bond contributes only modestly to the adsorption energy, while van-der-Waals forces dominate the potential landscape and determin…
Kondo effect offers an important paradigm to understand strong correlated many-body physics. Although under intensive study, some of important properties of Kondo effect, in systems where both itinerant coupling and localized coupling play significant roles, are still elusive. Here we report evolution and universality of two stage Kondo effect, the simplest form where both couplings are important using single molecule transistor devices incorporating Manganese phthalocyanine molecules. Kondo temperature T* of two-stage Kondo effect evolves linearly against effective interaction of involved two…
Chirality in organic molecules has attracted considerable attention in the fields of chemistry, biology, and spintronics. This paper reports on perpendicular magnetization hysteresis loops of a multilayer consisting of ultrathin Fe (001), chiral phthalocyanine molecule ((P)- or (M)-PbPc-DTBPh), and MgO (001). We find a chirality-dependent shift of the hysteresis loop. Unlike the previously reported bias current induced phenomena, the result shows a chirality-induced effective magnetic field in the phthalocyanine molecule in the absence of a bias current in the system. This study opens up a new…
Pinning single molecules at desired positions can provide opportunities to fabricate bottom-up designed molecular machines. Using the combined approach of scanning tunneling microscopy and density functional theory, we report on tip-induced anchoring of Niphthalocyanine molecules on an Au(111) substrate. We demonstrate that the tip-induced current leads to the dehydrogenation of a benzene-like ligand in the molecule, which subsequently creates chemical bonds between the molecule and the substrate. It is also found that the diffusivity of Ni-phthalocyanine molecules is dramatically reduced when…
For a molecular radical to be stable, the environment needs to be inert. Furthermore, an unpaired electron is less likely to react chemically, when it is placed in an extended orbital. Here, we use the tip of a scanning tunneling microscope to abstract one of the pyrrolic hydrogen atoms from phthalocyanine (H2Pc) deposited on a single layer of molybdenum disulfide (MoS2) on Au(111). We show the successful dissociation reaction by current-induced three-level fluctuations reflecting the inequivalent positions of the remaining H atom in the pyrrole center. Tunneling spectroscopy reveals two narro…
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…
Microscopic resolution of the interplay of Kondo screening and superconducting pairing: Mn-phthalocyanine molecules adsorbed on superconducting Pb(111)
We demonstrate the tip induced control of the spin state of copper phthalocyanine (CuPc) on an insulator coated substrate. Accounting for electronic correlations, we find that, under the condition of energetic proximity of neutral excited states to the anionic groundstate, the system can undergo a population inversion towards these excited states. The resulting state of the system is accompanied by a change in the total spin quantum number. Experimental signatures of the crossover are the appearance of additional nodal planes in the topographical STM images as well as a strong suppression of t…
The interplay of exchange correlations and spin-orbit interaction (SOI) on the many-body spectrum of a copper phtalocyanine (CuPc) molecule and their signatures in transport are investigated. We first derive a minimal model Hamiltonian in a basis of frontier orbitals which is able to reproduce experimentally observed singlet-triplet splittings; in a second step SOI effects are included perturbatively. Major consequences of the SOI are the splitting of former degenerate levels and a magnetic anisotropy, which can be captured by an effective low-energy spin Hamiltonian. We show that STM-based ma…
The magnetic and transport properties of the metal phthalocyanine (MPc) and F$_{16}$MPc (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Ag) families of molecules in contact with S-Au wires are investigated by density functional theory within the local density approximation, including local electronic correlations on the central metal atom. The magnetic moments are found to be considerably modified under fluorination. In addition, they do not depend exclusively on the configuration of the outer electronic shell of the central metal atom (as in isolated MPc and F$_{16}$MPc) but also on the intera…
The paradigm of Landau's Fermi liquid theory has been challenged with the finding of a strongly interacting Fermi liquid that cannot be adiabatically connected to a non-interacting system. A spin-1 two-channel Kondo impurity with anisotropy D has a quantum phase transition between two topologically different Fermi liquids with a peak (dip) in the Fermi level for D < Dc (D > Dc). Extending this theory to general multi-orbital problems with finite magnetic field, we reinterpret in a unified and consistent fashion several experimental studies of iron phthalocyanine molecules on Au(111) that were …
We investigate adsorption effects of copper phthalocyanine molecules on excitons and trions in air-suspended carbon nanotubes. Using photoluminescence excitation spectroscopy, we observe that exciton energy redshifts gradually with the molecular deposition thickness. The trion emission is also observed at large deposition amounts, which indicates charge transfer between the phthalocyanine molecules and carbon nanotubes. Analysis of the spectra for individual tubes reveal a correlation between the exciton-trion energy separation and the exciton emission energy, showing that the many-body intera…
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…
The organic spinterface describes the spin-polarized properties that develop, due to charge transfer, at the interface between a ferromagnetic metal (FM) and the molecules of an organic semiconductor. Yet, if the latter is also magnetic (e.g. molecular spin chains), the interfacial magnetic coupling can generate complexity within magnetotransport experiments. Also, assembling this interface may degrade the properties of its constituents (e.g. spin crossover or non-sublimable molecules). To circumvent these issues, one can separate the molecular and FM films using a less reactive nonmagnetic me…
We investigate the spectral evolution in different metal phthalocyanine molecules on NbSe$_2$ surface using scanning tunnelling microscopy (STM) as a function of the coupling with the substrate. For manganese phthalocyanine (MnPc), we demonstrate a smooth spectral crossover from Yu-Shiba-Rusinov (YSR) bound states to spin-flip excitations. This has not been observed previously and it is in contrast to simple theoretical expectations. We corroborate the experimental findings using numerical renormalization group calculations. Our results provide fundamental new insight on the behavior of atomic…
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…
Molecular spintronics hinges on the detailed understanding of electronic and magnetic properties of molecules interfaced with various materials. Here we demonstrate with ab-initio simulations that the prototypical Co-phthalocyanine (CoPc) molecule can surprisingly develop multi-spin states once deposited on the two-dimensional 2H-NbSe$_2$ layer. Conventional calculations based on density functional theory (DFT) show the existence of low, regular and high spin states, which reduce to regular and high spins states once correlations are incorporated with a DFT+$U$ approach. Depending on $U$, the …
A scanning tunneling microscope is used to generate the electroluminescence of phthalocyanine molecules deposited on NaCl/Ag(111). Photon spectra reveal an intense emission line at 1.9 eV that corresponds to the fluorescence of the molecules, and a series of weaker red-shifted lines. Based on a comparison with Raman spectra acquired on macroscopic molecular crystals, these spectroscopic features can be associated to the vibrational modes of the molecules and provide a detailed chemical fingerprint of the probed species. Maps of the vibronic features reveal sub- molecularly-resolved structures …
Understanding the intermolecular interactions and utilize these interactions to effectively control the transport behavior of single molecule is the key step from single molecule device to molecular circuits1-6. Although many single molecule detection techniques are used to detect the molecular interaction at single-molecule level1,4,5,7,8, probing and tuning the intermolecular interaction all by electrical approaches has not been demonstrated. In this work, we successful assemble a double molecule transistor incorporating two manganese phthalocyanine molecules, on which we probe and tune the …
Iron phthalocyanine (FePc) molecules were investigated on the topological insulator surface Bi2Se3 using scanning tunneling microscopy (STM) and spectroscopy (STS) at 77 K in ultra high vacuum (UHV). Sub-molecular resolution STM images provide the atomic scale registry of the adsorption site of the molecules, on-top or bridge, with reference to the top surface Se atoms of the Bi2Se3 surface. STS data reveal a slight shift in the HOMO and LUMO orbitals of the FePc molecules with respect to the specific binding site. Close to Fermi energy the STS measurements show that the Dirac point of Bi2Se3 …
We theoretically analyze spin filtering in two-terminal systems, induced by the spin-orbit interaction (SOI), as a possible origin of the ``chirality-induced spin selectivity'' (CISS) effect observed experimentally in chiral molecules, such as DNA. Due to Bardarson's theorem, spin filtering cannot be realized in a molecule containing one orbital-channel. However, when two orbitals are involved, SOI can induce spin filtering in a molecule coupled to two terminals without braking time-reversal symmetry. In particular, we provide an example of a $4 \times 4$ reflection matrix for a spinful electr…
We demonstrate that nanocavity plasmons generated a few nanometers away from a molecule can induce molecular motion. For this, we study the well-known rapid shuttling motion of zinc phthalocyanine molecules adsorbed on ultrathin NaCl films by combining scanning tunneling microscopy (STM) and spectroscopy (STS) with STM-induced light emission. Comparing spatially resolved single-molecule luminescence spectra from molecules anchored to a step edge with isolated molecules adsorbed on the free surface, we found that the azimuthal modulation of the Lamb shift is diminished in case of the latter. Th…
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）
The induction of unconventional superconductivity by twisting two layers of graphene a small angle was groundbreaking1, and since then has attracted widespread attention to novel phenomena caused by lattice or angle mismatch between two-dimensional (2D) materials2. While many studies address the influence of angle mismatch between layered 2D materials3-5 , the impact of the absorption alignment on the physical properties of planar molecules on 2D substrates has not been studied in detail. Using scanning probe microscopy (SPM) we show that individual cobalt phthalocyanine (CoPc) molecules adsor…
Coupling between a magnetic impurity and an external bath can give rise to many-body quantum phenomena, including Kondo and Hund's impurity states in metals, and Yu-Shiba-Rusinov states in superconductors. While advances have been made in probing the magnetic properties of d-shell impurities on surfaces, the confinement of f orbitals makes them difficult to access directly. Here we show that a 4f driven Kondo resonance can be modulated spatially by asymmetric coupling between a metallic surface and a molecule containing a 4f-like moment. Strong hybridisation of dysprosium double-decker phthalo…
The reversible control of a single spin of an atom or a molecule is of great interest in Kondo physics and a potential application in spin based electronics.Here we demonstrate that the Kondo resonance of manganese phthalocyanine molecules on an Au(111) substrate have been reversibly switched off and on via a robust route through attachment and detachment of single hydrogen atom to the magnetic core of the molecule. As further revealed by density functional theory calculations, even though the total number of electrons of the Mn ion remains almost the same in the process, gaining one single hy…
Generating efficient and highly spin-polarized currents through nanoscale junctions is essential in the field of nanoelectronics and spintronics. In this paper, using $ab$ $initio$ electron transport calculations, we predict highly conductive and perfect spin filtering of nickel atomic contacts in a nitrogen environment, where a single N$_2$ molecule sits in parallel (energetically most favorable) between two nickel electrodes. Such a particular performance is due to the wave function orthogonality between majority spin $s$-like states of ferromagnetic electrodes and the lowest unoccupied mole…
Metalated phthalocyanines (Pc's) are robust and versatile molecular complexes, whose properties can be tuned by changing their functional groups and central metal atom. The electronic structure of magnesium Pc (MgPc) - structurally and electronically similar to chlorophyll - adsorbed on the Ag(100) surface is investigated by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), non-contact atomic force microscopy (ncAFM) and density functional theory (DFT). Single, isolated MgPc's exhibit a flat, four-fold rotationally symmetric morphology, with doubly degenerate, partial…
Obtaining highly spin-polarized currents in molecular junctions is crucial and desirable for nanoscale spintronics devices. Motivated by our recent symmetry-based theoretical argument for complete blocking of one spin conductance channel in atomic-scale junctions [A. Smogunov and Y. J. Dappe, Nano Lett. 15, 3552 (2015)], we explore the generality of the proposed mechanism and the degree of achieved spin-polarized current for various ferromagnetic electrodes (Ni, Co, Fe) and two different molecules, quaterthiophene and p-quaterphenyl. A simple analysis of the spin-resolved local density of stat…
Probing up-conversion electroluminescence of decoupled porphyrin molecules in a plasmonic nanocavity
Max-Planck-Institut für Festkörperforschung（马克斯·普朗克固体研究所）；Institut de Physique, École Polytechnique Fédéral Lausanne（洛桑联邦理工学院物理研究所）；Gleb Wataghin Institute of Physics - University of Campinas - UNICAMP（坎皮纳斯大学格莱布·瓦塔金物理研究所）；Nanjing University（南京大学）
The functionality of many biological systems depends on reliable electron transfer with minimal heating. Unlike man-made electric circuits, nature realizes electron transport via insulating chiral molecules. Here we include spin into the analysis of tunneling through these molecules, and demonstrate its importance for efficient transport. We show that the helical geometry induces robust spin filtering accompanied by, and intimately related to, strongly enhanced transmission. Thus, we resolve two key questions posed by transport measurements through organic molecules, demonstrating their common…
Unlike the two-terminal device, in which the time-reversal invariant spin-orbit interaction alone cannot polarize the spins, such a polarization can be generated when electrons from one source reservoir flow into two (or more) separate drain reservoirs. We present analytical solutions for two examples. First, we demonstrate that the electrons transmitted through a "diamond" interferometer into two drains can be simultaneously fully spin-polarized along different tunable directions, even when the two arms of the interferometer are not identical. Second, we show that a single helical molecule at…
We investigate the spatial evolution of Yu-Shiba-Rusinov (YSR) states resulting from the interaction between Copper phthalocyanine molecules and a superconducting Vanadium (100) surface with submolecular resolution. Each molecule creates several YSR states at different energies showing distinctly different spatial intensity patterns. Surprisingly, on the molecules the largest YSR intensities are found not at the metal center, but close to one of the pyrrolic N-atoms, demonstrating strong molecular substrate interactions via the organic ligands. Energy resolved YSR maps reveal that the differen…
