2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film

We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis. Copyright © 2020 American Chemical Society

Large positive in-plane magnetoresistance induced by localized states at nanodomain boundaries in graphene

Graphene supports long spin lifetimes and long diffusion lengths at room temperature, making it highly promising for spintronics. However, making graphene magnetic remains a principal challenge despite the many proposed solutions. Among these, graphene with zig-zag edges and ripples are the most promising candidates, as zig-zag edges are predicted to host spin-polarized electronic states, and spin-orbit coupling can be induced by ripples. Here we investigate the magnetoresistance of graphene grown on technologically relevant SiC/Si(001) wafers, where inherent nanodomain boundaries sandwich zig-zag structures between adjacent ripples of large curvature. Localized states at the nanodomain boundaries result in an unprecedented positive in-plane magnetoresistance with a strong temperature dependence. Our work may offer a tantalizing way to add the spin degree of freedom to graphene

Study of the Formation and Properties of In–CuPcF4_4 Nanocomposite Materials in the Mode of the Millisecond Recording of Photoelectron Spectra

A study of the formation processes and properties of nanocomposite materials consisting of indium nanoparticles in a thin film of the organic semiconductor copper tetrafluorophthalocyanine (CuPcF$_4$) is presented. The results are obtained by the new setup for dynamic photoelectron spectroscopy, which allows the recording of spectra in a millisecond interval using the ARGUS photoelectron spectrometer and synchrotron radiation (PETRA III/DESY, Germany). The evolution of the core level (CL) spectra: C1s, N1s, and In3d$_{5/2}$ recorded directly during the deposition of indium onto the CuPcF$_4$ surface under ultrahigh vacuum conditions is traced. The thickness of the indium coating during deposition increased from 0 to 5 nm. In this range of coatings, more than 150 spectra are recorded for each CL with a recording rate of 0.1 s/spectrum. The following is established: the significant diffusion of indium atoms deep into the organic matrix is observed; in fact, no chemical interaction of indium with carbon atoms is found; indium atoms are located in places close to pyrrole nitrogen of the CuPcF$_4$ molecule. Apparently, during the interaction of In atoms and pyrrole nitrogen atoms, a negative charge is transferred from indium to the CuPcF$_4$ molecule. Thus, data on the fast-flowing processes of the formation of organometallic In–CuPcF$_4$ interfaces are obtained

Hybrid organic-inorganic systems formed by self-assembled gold nanoparticles in CuPcF4 molecular crystal

In this work we have fabricated and studied hybrid organic-inorganic nanocomposite system formed by gold nanoparticles self-assembled in organic semiconductor thin film - copper tetrafluorophthalocyanine (CuPcF4). By means of Photoelectron Spectroscopy and Transmission Electron Microscopy (TEM) the evolution of the morphology and electronic structure of the system as a function of nominal gold content have been investigated. The gold atoms, deposited onto the CuPcF4 surface, diffuse into the organic matrix and self-assemble to nanoparticles in a well-defined manner with a narrow size distribution, which depends on the amount of deposited gold. Using High-Resolution TEM, we were able to observe the atomic planes of single gold nanoparticles and their coalescence processes. Photoelectron spectroscopy has not revealed any detectable chemical reaction between gold and organic. However, the strong upward band bending, induced by gold nanoparticles in the organic film, takes place

2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film

We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF$_4$). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF$_4$ at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis

Temperature-Dependent Change of the Electronic Structure in the Kondo Lattice System YbRh2Si2YbRh_{2}Si_{2}

The heavy-fermion behavior in intermetallic compounds manifests itself in a quenching of local magnetic moments by developing Kondo spin-singlet many-body states combined with a drastic increase of the effective mass of conduction electrons, which occurs below the lattice Kondo temperature $T_K$. This behavior is caused by interactions between the strongly localized 4f electrons and itinerant electrons. A controversially discussed question in this context is how the localized electronic states contribute to the Fermi surface upon changing the temperature. One expects that hybridization between the local moments and the itinerant electrons leads to a transition from a small Fermi surface in a non-coherent regime at high temperatures to a large Fermi surface once the coherent Kondo lattice regime is realized below $T_K$. We demonstrate, using hard X-ray angle-resolved photoemission spectroscopy that the electronic structure of the prototypical heavy fermion compound YbRh$_2$Si$_2$ changes with temperature between 100 and 200 K, i.e. far above the Kondo temperature of this system. Our results suggest a transition from a small to a large Fermi surface with decreasing temperature. This result is inconsistent with the prediction of the dynamical mean-field periodic Anderson model and supports the idea of an independent energy scale governing the change of band dispersion

Layer-by-Layer Graphene Growth on β-SiC/Si(001)

The mechanism of few-layer graphene growth on the technologically relevant cubic-SiC/Si(001) substrate is uncovered using high-resolution core-level and angle-resolved photoelectron spectroscopy, low-energy electron microscopy, and microspot low-energy electron diffraction. The thickness of the graphitic overlayer supported on the silicon carbide substrate and related changes in the surface structure are precisely controlled by monitoring the progress of the surface graphitization in situ during high-temperature graphene synthesis, using a combination of microspectroscopic techniques. The experimental data reveal gradual changes in the preferential graphene lattice orientations at the initial stages of the few-layer graphene growth on SiC(001) and can act as reference data for controllable growth of single-, double-, and triple-layer graphene on silicon carbide substrates