Self-assembly of C60 on a ZnTPP/Fe(001)-p(1 × 1)O substrate: observation of a quasi-freestanding C60 monolayer.

Fullerene (C60) has been deposited in ultrahigh vacuum on top of a zinc tetraphenylporphyrin (ZnTPP) monolayer self-assembled on a Fe(001)-p(1 × 1)O substrate. The nanoscale morphology and the electronic properties of the C60/ZnTPP/Fe(001)-p(1 × 1)O heterostructure have been investigated by scanning tunneling microscopy/spectroscopy and ultraviolet photoemission spectroscopy. C60 nucleates compact and well-ordered hexagonal domains on top of the ZnTPP buffer layer, suggesting a high surface diffusivity of C60 and a weak coupling between the overlayer and the substrate. Accordingly, work function measurements reveal a negligible charge transfer at the C60/ZnTPP interface. Finally, the difference between the energy of the lowest unoccupied molecular orbital (LUMO) and that of the highest occupied molecular orbital (HOMO) measured on C60 is about 3.75 eV, a value remarkably higher than those found in fullerene films stabilized directly on metal surfaces. Our results unveil a model system that could be useful in applications in which a quasi-freestanding monolayer of C60 interfaced with a metallic electrode is required.

An In-Depth Assessment of the Electronic and Magnetic Properties of a Highly Ordered Hybrid Interface: The Case of Nickel Tetra-Phenyl-Porphyrins on Fe(001)-p(1 × 1)O.

In this paper we focus on the structural, electronic, and magnetic properties of Ni tetra-phenyl-porphyrins (NiTPP) grown on top of Fe(001)-p(1 × 1)O. Ordered thin films of metal TPP molecules are potentially interesting for organic electronic and spintronic applications, especially when they are coupled to a ferromagnetic substrate. Unfortunately, porphyrin layers deposited on top of ferromagnetic substrates do not generally show long-range order. In this work, we provide evidence of an ordered disposition of the organic film above the iron surface and we prove that the thin layer of iron oxide decouples the molecules from the substrate, thus preserving the molecular electronic features, especially the HOMO-LUMO gap, even when just a few organic layers are deposited. The effect of the exposure to molecular oxygen is also investigated and an increased robustness against oxidation with respect to the bare substrate is detected. Finally, we present our results for the magnetic analysis performed by spin resolved spectroscopy, finding a null magnetic coupling between the molecules and the substrate.

Observation of a Metastable Honeycomb Arrangement of C60 on Ni(111) with (7 × 7) Periodicity: Tailoring an Interface for Organic Spintronics.

Hybrid nanostructures in which organic molecules are interfaced with metal surfaces hold promise for the discovery of intriguing physical and chemical phenomena, as well as for the development of innovative devices. In this frame, it is crucial to understand the interplay between the structural details of the interface and the electronic properties of the system. Here, an experimental investigation of the C60/Ni(111) interface is performed by means of scanning tunneling microscopy/spectroscopy (STM/STS) and low-energy electron diffraction (LEED). The deposition of C60 at room temperature, followed by high-temperature annealing, promotes the stabilization of two different phases. A hitherto unreported phase forming a (7 × 7) honeycomb overlayer coexists with the well-known (4 × 4) reconstruction. Highly resolved STM images disclose the adsorption geometry of the molecules for both phases. STS reveals that the electronic properties of C60/Ni(111) are strongly influenced by the morphology of the interface, suggesting the possibility of tuning the electronic properties of the organic/inorganic heterostructures by adjusting the structural coupling with the substrate. This achievement can be important for hybrid magnetic interfaces, where the harmonization between the molecular and the magnetic orders can enhance the development of hybrid magnetic states.

3-dimensional nucleation of Fe oxide induced by a graphene buffer layer.

Shaping the morphology of oxide nanolayers is of paramount importance in tailoring their physical and chemical properties. Here, the influence of a two dimensional graphene buffer layer on the growth of Fe oxide has been investigated by comparing the oxide deposition on a Ni(111) and a graphene/Ni(111) substrate. Scanning tunneling microscopy images acquired at a mesoscopic scale indicate that Fe oxide grows layer-by-layer on the bare Ni(111) surface, while the nucleation of three-dimensional clusters is induced by graphene. Atomically resolved images reveal that Fe oxide adopts an in-plane lattice constant similar to that of the FeO(111) surface when deposited on Ni(111) and graphene/Ni(111), indicating in both cases, a weak interaction between the overlayer and the substrate. Accordingly, it is suggested that the different growth mode is mainly driven by the graphene-induced lowering of the substrate surface free energy.

Graphene as an Ideal Buffer Layer for the Growth of High-Quality Ultrathin Cr2O3 Layers on Ni(111).

Metal-oxide nanostructures play a fundamental role in a large number of technological applications, ranging from chemical sensors to data storage devices. As the size of the devices shrinks down to the nanoscale, it is mandatory to obtain sharp and good quality interfaces. Here, it is shown that a two-dimensional material, namely, graphene, can be exploited as an ideal buffer layer to tailor the properties of the interface between a metallic substrate and an ultrathin oxide. This is proven at the interface between an ultrathin film of the magnetoelectric antiferromagnetic oxide Cr2O3 and a Ni(111) single crystal substrate. The chemical composition of the samples has been studied by means of X-ray photoemission spectroscopy, showing that the insertion of graphene, which remains buried at the interface, is able to prevent the oxidation of the substrate. This protective action leads to an ordered and layer-by-layer growth, as revealed by scanning tunneling microscopy data. The structural analysis performed by low-energy electron diffraction indicates that the oxide layer grown on graphene experiences a significant compressive strain, which strongly influences the surface electronic structure observed by scanning tunneling spectroscopy.

Enhanced Magnetic Hybridization of a Spinterface through Insertion of a Two-Dimensional Magnetic Oxide Layer.

Interfaces between organic semiconductors and ferromagnetic metals offer intriguing opportunities in the rapidly developing field of organic spintronics. Understanding and controlling the spin-polarized electronic states at the interface is the key toward a reliable exploitation of this kind of systems. Here we propose an approach consisting in the insertion of a two-dimensional magnetic oxide layer at the interface with the aim of both increasing the reproducibility of the interface preparation and offering a way for a further fine control over the electronic and magnetic properties. We have inserted a two-dimensional Cr4O5 layer at the C60/Fe(001) interface and have characterized the corresponding morphological, electronic, and magnetic properties. Scanning tunneling microscopy and electron diffraction show that the film grows well-ordered both in the monolayer and multilayer regimes. Electron spectroscopies confirm that hybridization of the electronic states occurs at the interface. Finally, magnetic dichroism in X-ray absorption shows an unprecedented spin-polarization of the hybridized fullerene states. The latter result is discussed also in light of an ab initio theoretical analysis.

Controlling the Electronic and Structural Coupling of C60 Nano Films on Fe(001) through Oxygen Adsorption at the Interface.

C60 molecules coupled to metals form hybrid systems exploited in a broad range of emerging fields, such as nanoelectronics, spintronics, and photovoltaic solar cells. The electronic coupling at the C60/metal interface plays a crucial role in determining the charge and spin transport in C60-based devices; therefore, a detailed understanding of the interface electronic structure is a prerequisite to engineering the device functionalities. Here, we compare the electronic and structural properties of C60 monolayers interfaced with Fe(001) and oxygen-passivated Fe(001)-p(1 × 1)O substrates. By combining scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy, photoemission and inverse photoemission spectroscopies, we are able to elucidate the striking effect of oxygen on the interaction between Fe(001) and C60. Upon C60 deposition on the oxygen-passivated surface, the oxygen layer remains buried at the C60/Fe(001)-p(1 × 1)O interface, efficiently decoupling the fullerene film from the metallic substrate. Tunneling and photoemission spectroscopies reveal the presence of well-defined molecular resonances for the C60/Fe(001)-p(1 × 1)O system, with a large HOMO-LUMO gap of about 3.4 eV. On the other hand, for the C60/Fe(001) interface, a strong hybridization between the substrate states and the C60 orbitals occurs, resulting in broader molecular resonances.

Combined spectroscopic characterization of electron transfer at hybrid CuPcF(16)/GaAs semiconductor interfaces.

We characterize photoinduced charge injection at the interface between a fluorinated copper phthalocyanine (CuPcF(16)) film deposited over a GaAs(100) wafer by means of pump-probe spectroscopy combined with ultraviolet photoemission spectroscopy (UPS) and electromodulated transmission spectroscopy. UPS characterization of the hybrid interface demonstrates that the CuPcF(16) 's lowest unoccupied molecular level (LUMO) is almost aligned with the GaAs conduction band. Upon photoexcitation of the hybrid interface with 150 fs pulses we observe an efficient photoinduced electron transfer from CuPcF(16) to GaAs. The evolution of interfacial CuPcF(16) charges appear to be strongly influenced by energy level alignment at the GaAs/CuPcF(16) heterojunction.