O. V. Molodtsova

Graphene Synthesis on Cubic SiC/Si Wafers. Perspectives for Mass Production of Graphene-Based Electronic Devices

The outstanding properties of graphene, a single graphite layer, render it a top candidate for substituting silicon in future electronic devices. The so far exploited synthesis approaches, however, require conditions typically achieved in specialized laboratories and result in graphene sheets whose electronic properties are often altered by interactions with substrate materials. The development of graphene-based technologies requires an economical fabrication method compatible with mass production. Here we demonstrate for the fist time the feasibility of graphene synthesis on commercially available cubic SiC/Si substrates of >300 mm in diameter, which result in graphene flakes electronically decoupled from the substrate. After optimization of the preparation procedure, the proposed synthesis method can represent a further big step toward graphene-based electronic technologies.

Transition metal phthalocyanines: Insight into the electronic structure from soft x-ray spectroscopy

Transition metal phthalocyanines (MPcs) are an interesting class of material, and their magnetic and electronic properties are determined by the orbital occupation of the transition metal 3d orbitals incorporated in the molecules center. Thus, the ground state configuration of the transition metal center is very important for a complete understanding of these materials. We present experimental data taken using x-ray absorption and x-ray photoemission spectroscopy together with a theoretical interpretation of MPc series with M=Zn, Cu, Ni, Co, Fe, and Mn. The combination of these methods allows us to narrow down possible dominating ground state configurations and shed a brighter light on the electronic structure of these complexes.

Spin and Orbital Ground State of Co in Cobalt Phthalocyanine

The 3d orbital ground state of transition-metal ions that are incorporated in a molecular matrix determines the total spin of the transition-metal ion as well as the spin anisotropy and thus the essential magnetic properties of the corresponding molecule. However, there is little known to date on the exact 3d ground state of many molecular systems, including quite complex molecular magnets as well as relatively simple systems such as, for instance, cobalt phthalocyanine (CoPc). For the latter, there are contradictory theoretical predictions with respect to the occupation of the various Co 3d electronic levels. We demonstrate that polarization-dependent X-ray absorption spectroscopy in combination with a simulation of the spectra is able to shed a brighter light on the spin and orbital ground state of the transition-metal ion in CoPc. Our results reveal a temperature-dependent ground state and emphasize the importance of taking 3d correlation effects properly into account.

Electronic structure of the organic semiconductor copper phthalocyanine: experiment and theory.

The electronic structure of the organic semiconductor copper-phthalocyanine (CuPc) has been determined by a combination of conventional and resonant photoemission, near-edge x-ray absorption, as well as by the first-principles calculations. The experimentally obtained electronic valence band structure of CuPc is in very good agreement with the calculated density of states results, allowing the derivation of detailed site specific information.

Continuous wafer-scale graphene on cubic-SiC(001)

AbstractThe atomic and electronic structure of graphene synthesized on commercially available cubic-SiC(001)/Si(001) wafers have been studied by low energy electron microscopy (LEEM), scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and angle resolved photoelectron spectroscopy (ARPES). LEEM and STM data prove the wafer-scale continuity and uniform thickness of the graphene overlayer on SiC(001). LEEM, STM and ARPES studies reveal that the graphene overlayer on SiC(001) consists of only a few monolayers with physical properties of quasi-freestanding graphene. Atomically resolved STM and micro-LEED data show that the top graphene layer consists of nanometersized domains with four different lattice orientations connected through the 〈110〉-directed boundaries. ARPES studies reveal the typical electron spectrum of graphene with the Dirac points close to the Fermi level. Thus, the use of technologically relevant SiC(001)/Si(001) wafers for graphene fabrication represents a realistic way of bridging the gap between the outstanding properties of graphene and their applications.

Prediction of the Equilibrium Structures and Photomagnetic Properties of the Prussian Blue Analogue RbMn(Fe(CN)6) by Density Functional Theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT <--> LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Bulk and Surface Switching in Mn−Fe-Based Prussian Blue Analogues

Many Prussian Blue Analogues are known to show a thermally induced phase transition close to room temperature and a reversible, photo-induced phase transition at low temperatures. This work reports on magnetic measurements, X-ray photoemission and Raman spectroscopy on a particular class of these molecular heterobimetallic systems, specifically on Rb0.81Mn[Fe(CN)6]0.95_1.24H2O, Rb0.97Mn[Fe(CN)6]0.98_1.03H2O and Rb0.70Cu0.22Mn0.78[Fe(CN)6]0.86_2.05H2O, to investigate these transition phenomena both in the bulk of the material and at the sample surface. Results indicate a high degree of charge transfer in the bulk, while a substantially reduced conversion is found at the sample surface, even in case of a near perfect (Rb:Mn:Fe=1:1:1) stoichiometry. Thus, the intrinsic incompleteness of the charge transfer transition in these materials is found to be primarily due to surface reconstruction. Substitution of a large fraction of charge transfer active Mn ions by charge transfer inactive Cu ions leads to a proportional conversion reduction with respect to the maximum conversion that is still stoichiometrically possible and shows the charge transfer capability of metal centers to be quite robust upon inclusion of a neighboring impurity. Additionally, a 532 nm photo-induced metastable state, reminiscent of the high temperature Fe(III)Mn(II) ground state, is found at temperatures 50-100 K. The efficiency of photo-excitation to the metastable state is found to be maximized around 90 K. The photo-induced state is observed to relax to the low temperature Fe(II)Mn(III) ground state at a temperature of approximately 123 K.

Unoccupied electronic states in an organic semiconductor probed with x-ray spectroscopy and first-principles calculations

High-quality films of copper phthalocyanine (CuPc) prepared in situ were used as a model to characterize unoccupied states of organic molecular semiconductors. We demonstrate that a combination of high-resolution near-edge x-ray absorption together with first-principles calculations constitutes a reliable tool for the detection and identification of particular molecular orbitals.

The unoccupied electronic structure of potassium doped copper phthalocyanine studied by near edge absorption fine structure

The unoccupied electronic structure of potassium doped copper-phthalocyanine thin films has been studied using x-ray absorption spectroscopy. The data reveal filling of the lowest unoccupied molecular orbital upon doping and related changes of the core level absorption spectra. The spectral changes can be rationalized taking into account the core level binding energies which also depend on doping.

Properties of hybrid organic-inorganic systems: Au nanoparticles embedded into an organic CuPc matrix

The evolution of the morphology and the electronic structure of the hybrid organic-inorganic system composed of gold nanoparticles (NPs) distributed in an organic matrix—copper phthalocyanine (CuPc)—as a function of nominal gold content was studied by transmission electron microscopy and by surface and bulk sensitive spectroscopic methods. The gold atoms deposited onto the CuPc surface diffuse into the organic matrix and self-assemble to NPs. There is no formation of a continuous metallic Au film on top of the CuPc film up to large nominal coverage of about 130 A considered in the present study. The gold is assembled in well defined NPs with metallic properties.