Observation of Exchange Interaction in Iron(II) Spin Crossover Molecules in Contact with Passivated Ferromagnetic Surface of Co/Au(111).

Spin crossover (SCO) complexes sensitively react on changes of the environment by a change in the spin of the central metallic ion making them ideal candidates for molecular spintronics. In particular, the composite of SCO complexes and ferromagnetic (FM) surfaces would allow spin-state switching of the molecules in combination with the magnetic exchange interaction to the magnetic substrate. Unfortunately, when depositing SCO complexes on ferromagnetic surfaces, spin-state switching is blocked by the relatively strong interaction between the adsorbed molecules and the surface. Here, the Fe(II) SCO complex [FeII (Pyrz)2 ] (Pyrz = 3,5-dimethylpyrazolylborate) with sub-monolayer thickness in contact with a passivated FM film of Co on Au(111) is studied. In this case, the molecules preserve thermal spin crossover and at the same time the high-spin species show a sizable exchange interaction of > 0.9 T with the FM Co substrate. These observations provide a feasible design strategy in fabricating SCO-FM hybrid devices.

Organic Monolayer Protected Topological Surface State.

Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)/Bi2Se3 and Fe/PTCDA/Bi2Se3 heterointerfaces are investigated using scanning tunneling microscopy and spectroscopy. The close-packed self-assembled PTCDA monolayer possesses big molecular band gap and weak molecule-substrate interactions, which leaves the Bi2Se3 topological surface state intact under PTCDA. Formation of Fe-PTCDA hybrids removes interactions between the Fe dopant and the Bi2Se3 surface, such as doping effects and Coulomb scattering. Our findings reveal the functionality of PTCDA to prevent dopant disturbances in the TSS and provide an effective alternative for interface designs of realistic TI devices.

Tuning molecule-substrate coupling via deposition of metal adatoms.

Organic-inorganic hybrids constitute an important class of functional materials. The fundamentals at the molecular levels are, however, relatively unexplored. PTCDA (perylene-3,4,9,10-tetracarboxylic dianhydride) is a colorant and extensively applied in organic-based optoelectronic devices. PTCDA/Cu(111) and Fe-PTCDA/Cu(111) metal-organic hybrid monolayers are studied by low temperature scanning tunneling microscopy and spectroscopy (STS) and density functional theory (DFT). The former exhibits Moiré pattern-modulated molecular density of states while the latter adapts a commensurate adlattice. Both imaging and spectroscopic results suggest a strong hybridization between PTCDA molecules and Cu(111) substrate. Weak PTCDA-Cu(111) coupling can be obtained by the introduction of Fe adatoms. Compared to PTCDA/Cu(111), STS spectra of Fe-PTCDA/Cu(111) exhibit a higher energy and sharper features of the frontier orbitals. Together with the DFT results, we found that the PTCDA-Cu(111) coupling is attenuated by the presence of Fe adatoms and Fe-PTCDA coordination.

Scanning tunneling microscopy/spectroscopy of picene thin films formed on Ag(111).

Using ultrahigh-vacuum low-temperature scanning tunneling microscopy and spectroscopy combined with first principles density functional theory calculations, we have investigated structural and electronic properties of pristine and potassium (K)-deposited picene thin films formed in situ on a Ag(111) substrate. At low coverages, the molecules are uniformly distributed with the long axis aligned along the [112̄] direction of the substrate. At higher coverages, ordered structures composed of monolayer molecules are observed, one of which is a monolayer with tilted and flat-lying molecules resembling a (11̄0) plane of the bulk crystalline picene. Between the molecules and the substrate, the van der Waals interaction is dominant with negligible hybridization between their electronic states; a conclusion that contrasts with the chemisorption exhibited by pentacene molecules on the same substrate. We also observed a monolayer picene thin film in which all molecules were standing to form an intermolecular π stacking. Two-dimensional delocalized electronic states are found on the K-deposited π stacking structure.

Reduction in magnetic coercivity of Co nanomagnets by Fe alloying.

We measured the magnetic hysteresis and coercivity of individual Co and Co0.8Fe0.2 bilayer nano-sized island structures formed on Cu (111) substrate using spin-polarized scanning tunneling microscopy. From the hysteresis taken on various sizes of islands, we found that the alloyed islands are ferromagnetic with out-of-plane magnetic anisotropy, same as the pure islands. Coercivity of the alloy islands, which is dependent on their size, was significantly reduced to ≈40% of that of the pure islands. Based on the Stoner-Wohlfarth model, we evaluated the amount of magnetic anisotropic energy and anisotropy constant for both pure and alloy islands. Since tunneling spectra taken on the alloy islands show upward shifts of the valence electronic states as compared to the pure ones, fewer electrons populated in the valence band of the alloy islands are presumably responsible for the reduction in the magnetic anisotropic energy.

Scanning tunneling microscopy on cleaved Mn3Sn(0001) surface.

We have studied in-situ cleaved (0001) surfaces of the magnetic Weyl semimetal Mn3Sn by low-temperature scanning tunneling microscopy and spectroscopy (STM/S). It was found that freshly cleaved Mn3Sn surfaces are covered with unknown clusters, and the application of voltage pulses in the tunneling condition was needed to achieve atomically flat surfaces. STM topographs taken on the flat terrace show a bulk-terminated 1 × 1 honeycomb lattice with the Sn site brightest. First-principles calculations reveal that the brightest contrast at the Sn site originates from the surrounding surface Mn d orbitals. Tunneling spectroscopy performed on the as-cleaved and voltage-pulsed surfaces show a prominent semimetal valley near the Fermi energy.

Bulk ferromagnetic tips for spin-polarized scanning tunneling microscopy.

We characterized the performance of electrochemically etched bulk Fe and Ni tips as a probe of spin-polarized scanning tunneling microscopy (SP-STM). Through the observation of the striped contrast on the conical spin-spiral structure formed in Mn double layers on a W(110) substrate, the capability of both the tips to detect the magnetic signal was clarified. We also confirmed that the magnetized direction of the Fe and Ni tips can be flipped between the two out-of-plane directions by external magnetic fields. Our results demonstrate that the ex-situ prepared tips are reliable in SP-STM for the samples that are not susceptible to a stray magnetic field.

Spin-Dependent Molecule Symmetry at a Pentacene-Co Spinterface.

Incorporating spin-polarized scanning tunneling microscopy (SP-STM) measurements and first-principles calculations, we resolve spin-polarized states and consequent features in a pentacene(PEN)-Co hybrid system. Symmetry reduction of PEN clarifies the PEN adsorption site and the Co stacking methods. Near the Fermi energy, the molecular symmetry is spin-dependently recovered and an inversion of spin-polarization in PEN with respect to Co is observed. The experimental findings and calculation results are interpreted by a pz-d hybridization model, in which spin-dependent bonding-antibonding splitting of molecular orbitals happens at metal-organic spinterfaces.

Mapping polarization induced surface band bending on the Rashba semiconductor BiTeI.

Surfaces of semiconductors with strong spin-orbit coupling are of great interest for use in spintronic devices exploiting the Rashba effect. BiTeI features large Rashba-type spin splitting in both valence and conduction bands. Either can be shifted towards the Fermi level by surface band bending induced by the two possible polar terminations, making Rashba spin-split electron or hole bands electronically accessible. Here we demonstrate the first real-space microscopic identification of each termination with a multi-technique experimental approach. Using spatially resolved tunnelling spectroscopy across the lateral boundary between the two terminations, a previously speculated on p-n junction-like discontinuity in electronic structure at the lateral boundary is confirmed experimentally. These findings realize an important step towards the exploitation of the unique behaviour of the Rashba semiconductor BiTeI for new device concepts in spintronics.

Digitized charge transfer magnitude determined by metal-organic coordination number.

Well-ordered metal-organic nanostructures of Fe-PTCDA (perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride) chains and networks are grown on a Au(111) surface. These structures are investigated by high-resolution scanning tunneling microscopy. Digitized frontier orbital shifts are followed in scanning tunneling spectroscopy. By comparing the frontier energies with the molecular coordination environments, we conclude that the specific coordination affects the magnitude of charge transfer onto each PTCDA in the Fe-PTCDA hybridization system. A basic model is derived, which captures the essential underlying physics and correlates the observed energetic shift of the frontier orbital with the charge transfer.