Electronic Properties of Phthalocyanines Deposited on H-Si(111)

Im Rahmen dieser Arbeit wurden vier Phthalocyanine untersucht: Metallfreies-Phthalocyanin (H2Pc), Kupferphthalocyanin (CuPc) und Fluor-substituiertes Phthalocyanin (F4CuPc und F16CuPc). Das Ziel dieser Arbeit ist die Charakterisierung der elektronischen und chemischen Eigenschaften der Grenzflächen zwischen diesen Molekülen und Silizium. Die Moleküle wurden durch organische Molekularstrahldeposition (OMBD) im Ultrahochvakuum auf wasserstoffpassivierte Si(111)-Substrate aufgedampft. Oberflächensensitive Messmethoden wie Photoemissionsspektroskopie (PES), Bremsstrahlung Isochromaten Spektroskopie (BIS oder IPES - Inverse Photoemissionsspektroskopie) und Spektroskopie der Röntgen-Absorptions-Feinstruktur (NEXAFS – Near Edge X-Ray Absorption Fine Structure) wurden zur Charakterisierung eingesetzt. Um eine Zuordnung der verschiedenen Komponenten in PES und IPES zu ermöglichen, wurden Methoden der Dichtefunktionaltheorie zur theoretischen Berechnung eingesetzt. Die Energieniveauanpassung an der Grenzfläche zwischen der organischen Schicht und der H-Si-Grenzfläche, sowie die Transportbandlücke von H2Pc, CuPc, F4CuPc und F16CuPc wurden mit Hilfe von PES und IPES bestimmt. Die NEXAFS-Messungen ermöglichten eine genaue Bestimmung der Molekülorientierung relativ zum Substrat. Die Auswertung der Daten zeigte unterschiedliche Molekülorientierungen in dünnen und dicken Filmen. Diese Änderungen wurden mit dem bandverbiegungsähnlichen Verlauf der HOMO-und LUMO-Positionen in Verbindung gebracht. Zusätzlich zu diesem Verhalten wiesen die Grenzflächen auch einen Grenzflächendipol auf, welcher durch die unterschiedlichen Austrittsarbeiten der Kontaktmaterialien hervorgerufen wird. Der Einfluss des Grads der Flouridierung wird durch eine ähnlichen Zunahme der Elektronenaffinität (EA), der Austrittsarbeit (WF) und der Ionisierungsenergie (IE) bestätigt. Die elektronischen Eigenschaften von Metall/organische-Schicht-Grenzflächen und von organischen Schichten unter Sauerstoffeinfluss wurden mit Hilfe von PES und IPES untersucht. Die Ag/Pc Grenzflächen zeigten eine Mischung aus HOMO-LUMO-Verschiebungen und Grenzflächendipolbildung. An den Ag/H2Pc- und Ag/F16CuPc- Grenzflächen wurde ein Ladungstransferkomplex gebildet. Auf der CuPc-Schicht physisorbiert das Ag lediglich und im Fall von F4CuPc wird Ladung zu Ag transferiert, wobei eine andauernde n-Typ-Dotierung an der Grenzfläche erzeugt wird. In Analogie zum Fall der Pc/H-Si Grenzfläche wiesen die Dipole, die hier gefunden wurden, eine lineare Abhängigkeit von EA, WF und IE auf und können durch die Differenz zwischen den Austrittsarbeiten vorausgesagt werden. Das Verhalten der dicken organischen Schichten unter Sauerstoffeinfluss kann in zwei Gruppen eingeteilt werden. Eine Gruppe, bestehend aus H2Pc und F4CuPc, wies nur schwache Wechselwirkung auf und der Sauerstoff physisorbiert auf der Pc-Schicht. Die beiden anderen Moleküle, CuPc und F16CuPc konnten einer Gruppe starker Wechselwirkung zugeordnet werden. CuPc bildet einen Ladungstransferkomplex mit Sauerstoff und auf F16CuPc wird eine polarisierte Schicht gebildet.In the context of this work four Phthalocyanine were studied: Metal-free Phthalocyanine (H2Pc), Copper Phthalocyanine (CuPc) and fluorine-substituted Phthalocyanine (F4CuPc and F16CuPc). The goal of this work is the electronic and chemical characteristics of the interfaces. The molecules were deposited by organic molecular beam deposition (OMBD) in the ultra high vacuum on hydrogen-passivated Si(111)-Substrate. Surface sensitive techniques such as photoemission spectroscopy (PES), bremsstrahlung isochromate spectroscopy (BIS or IPES - inverse photoemission spectroscopy) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) were used for characterisation. Theoretical computations by density functional theory methods were employed, in order to assign different components in PES and IPES. The energy level alignment at the organic/H-Si interface, as well as the transport gap of H2Pc, CuPc, F4CuPc and F16CuPc were determined by PES and IPES. The NEXAFS measurements determine the exact molecular orientation with respect to the substrate. The evaluation of the data showed different molecular orientation in the thin and thick films. This change was correlated with the band bending like behaviours that emerged at these interfaces. In addition to the band bending like behaviour, the interfaces show also an interface dipole which is driven by the work function difference between the contact materials. The influence of the degree of fluorination is confirmed in the similar increase of the EA, WF and IE. The electronic properties of metal/organic layer interfaces and of organic layer under oxygen influence were examined by PES and IPES. The Ag/Pc interfaces show a mixture of HOMO-LUMO shifts and interface dipole formation. A charge transfer complex is formed in the case of Ag/H2Pc and Ag/F16CuPc interfaces. Ag is physisorbed atop the CuPc. Charge transfers from F4CuPc to Ag creating a continuous n-type doping at the interface. Similar to the Pc/H-Si interfaces the interface dipoles found here show a linear dependence on the EA, WF and IE and can be predicted by the difference in the work functions. The data evaluation of oxygen exposed thick films determined two groups of behaviours. The weak interaction group is represented by H2Pc and F4CuPc, Pcs on which oxygen is physisorbed. The strong interaction group contains the other two molecules CuPc and F16CuPc. CuPc forms a charge transfer complex with oxygen and on top of F16CuPc a polarized layer is formed

Enhanced ferrimagnetism in auxetic NiFe2O4 in the crossover to the ultrathin film limit

We investigate the sensitive interplay between magnetic, electronic and structural properties in the ferrimagnetic oxide NiFe2O4. Emphasis is placed on the impact of reduced dimensionality in the crossover from bulk-like to ultrathin films. We observed an enhanced saturation magnetization $M_S$ for ultrathin NiFe2O4 films on Nb-SrTiO3 (001) substrates that co-occurs with a reduced out-of-plane lattice constant under compressive in-plane epitaxial strain. We found a bulk-like cationic coordination of the inverse spinel lattice independent of the NiFe2O4 film thickness -- thus ruling out a cationic inversion that nominally could account for an enhanced $M_S$. Our study instead uncovers a reduction of the unit cell volume, i.e. an auxetic behavior in ultrathin NiFe2O4 films, which may result in an enhanced magnetic exchange caused by an increased interatomic electronic localization.Comment: 8 pages, 6 figure

Assessment of Chemical and Electronic Surface Properties of the Cu2ZnSn(SSe)4 after Different Etching Procedures by Synchrotron-based Spectroscopies

Kesterite Cu2ZnSn(S,Se)4 absorber layers with different [S]/([S]+[Se]) ratios were studied using XPS, UPS, Hard X-ray (HIKE) photoemission and the Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS). The samples were prepared by IREC using sequentially sputtered metallic precursor stacks with metal ratios of [Cu]/([Zn]+[Sn])=0.80, [Zn]/[Sn]=1.20 followed by annealing under S+Se+Sn atmosphere. Different etching procedures were used depending on the sample's composition. It is shown that the surface composition varies from that of the bulk, especially for the Se-rich samples. Contamination with sulfur is detected after using a Na2S etching solution for the pure Se kesterite. A Cu-depleted surface was found for all samples before and after etching. HIKE measurements show a higher [Zn]/[Sn] ratio in the near surface region than on the very surface. This is explained by the fact, the etching procedure removes secondary phases from the very few surface layers, while some of ZnS(e) is still buried underneath. In order to investigate the band gap transition from the pure sulfide (1.5 eV) to the pure selenide (1eV), the valence and conduction band of the respective absorbers were probed. According to UPS and HIKE measurements, the relative distance between Fermi level (Ef) and valance band maximum (VBM) for sulfide sample was 130 meV larger than for selenide. Using NEXAFS on the copper, zinc and tin edges, the development of the conduction band with increasing [S]/([S]+[Se]) ratios was studied. Stoichiometric powder samples were used as reference materials. © 2015 Published by Elsevier Ltd.Peer ReviewedPostprint (published version

Interface characterization of Co2MnGe/Rh2CuSn Heusler multilayers

All-Heusler multilayer structures have been investigated by means of high kinetic x-ray photoelectron spectroscopy and x-ray magnetic circular dichroism, aiming to address the amount of disorder and interface diffusion induced by annealing of the multilayer structure. The studied multilayers consist of ferromagnetic Co$_2$MnGe and non-magnetic Rh$_2$CuSn layers with varying thicknesses. We find that diffusion begins already at comparably low temperatures between 200 $^{\circ}$C and 250 $^{\circ}$C, where Mn appears to be most prone to diffusion. We also find evidence for a 4 {\AA} thick magnetically dead layer that, together with the identified interlayer diffusion, are likely reasons for the small magnetoresistance found for current-perpendicular-to-plane giant magneto-resistance devices based on this all-Heusler system

High photon energy spectroscopy of NiO: experiment and theory

We have revisited the valence band electronic structure of NiO by means of hard x-ray photoemission spectroscopy (HAXPES) together with theoretical calculations using both the GW method and the local density approximation + dynamical mean-field theory (LDA+DMFT) approaches. The effective impurity problem in DMFT is solved through the exact diagonalization (ED) method. We show that the LDA+DMFT method alone cannot explain all the observed structures in the HAXPES spectra. GW corrections are required for the O bands and Ni-s and p derived states to properly position their binding energies. Our results establish that a combination of the GW and DMFT methods is necessary for correctly describing the electronic structure of NiO in a proper ab-initio framework. We also demonstrate that the inclusion of photoionization cross section is crucial to interpret the HAXPES spectra of NiO.We argue that our conclusions are general and that the here suggested approach is appropriate for any complex transition metal oxide.Comment: 16 pages, 5 figure

Doping dependence of the chemical potential and surface electronic structure in YBa2Cu3O6+x and La2-xSrxCuO4 using hard x-ray photoemission spectroscopy

The electronic structure of YBa2Cu3O6+x and La2-xSrxCuO4 for various values of x has been investigated using hard x-ray photoemission spectroscopy. The experimental results establish that the cleaving of YBa2Cu3O6+x compounds occurs predominantly in the BaCuO3 complex leading to charged surfaces at higher x and to uncharged surfaces at lower x values. The bulk component of the core level spectra exhibits a shift in binding energy as a function of x, from which a shift of the chemical potential as a function of hole concentration in the CuO2 layers could be derived. The doping dependence of the chemical potential across the transition from a Mott-Hubbard insulator to a Fermi-liquid-like metal is very different in these two series of compounds. In agreement with previous studies in the literature the chemical potential shift in La2-xSrxCuO4 is close to zero for small hole concentrations. In YBa2Cu3O6+x, similar to all other doped cuprates studied so far, a strong shift of the chemical potential at low hole doping is detected. However, the results for the inverse charge susceptibility at small x shows a large variation between different doped cuprates. The results are discussed in view of various theoretical models. None of these models turns out to be satisfactory.Comment: 18 pages, 15 figure

Оценивание финансово-экономической безопасности предприятий молокоперерабатывающей отрасли

The essence of the concept “financial and economic security of the enterprise” is covered. Methodological approaches to the enterprise financial and economic security evaluation are considered, enabling the method of index numberrating score of the enterprise financial and economic security to be found. Dynamics of milk anddairy production in Ukraine has been studied. Ukrainian regions leading in liquid processed milk production have been identified. Dynamics of milk and dairy production per man has been analyzed which allowed to find out the annual increase in demand per man. Integrated index of the dairy enterprise financial and economic security has been evaluated. As a result, the ways to increase the managerial efficiency of financial and economic security of the following enterprises:PJSC "Dubnomoloko", PJSC "Kupyans'ki milk canning plant", PJSC the "Yagotyns'ki creamery", PJSC the "Pervomais'ki milk canning plant" are offered.У статті розкрито сутність поняття фінансово-економічної безпеки підприємства. Розглянуто методичні підходи щодо оцінювання фінансово-економічної безпеки підприємства, що дозволило виявити підхід рейтингової оцінки показника фінансово-економічної безпеки підприємства. Досліджено динаміку виробництва молока та молочних продуктів України. Виявити області України, які є лідерами з виробництва молока рідкого обробленого. Проаналізовано динаміку виробництва молока та молочних продуктів на одну особу, що дозволило встановити щорічне зростання попиту на одну особу. Визначено підприємства молокопереробної галузі. Проведено оцінку інтегрального показника фінансово-економічної безпеки підприємств молокопереробної галузі. За результатами оцінки запропоновано шляхи підвищення ефективності управління фінансово-економічної безпеки таких підприємств, як: ПАТ «Дубномолоко», ПАТ «Куп’янський молочноконсервний комбінат», ПАТ «Яготинський маслозавод», ПАТ «Первомайський молочноконсервний комбінат».В статье раскрыто сущность понятия финансово-экономическая безопасность предприятия. Рассмотрено методические подходы относительно оценивания финансово-экономической безопасности предприятия, что позволило выявить поход рейтинговой оценки показателя финансово-экономической безопасности предприятия. Исследовано динамику производства молока и молочных продуктов Украины. Выявлены области Украины, которые являются лидерами по производству молока жидкого обработанного. Проанализировано динамику производства молока и молочных продуктов на одного человека, что позволило установить ежегодный рост спроса на одного человека. Определены предприятия молокоперерабатывающей отрасли. Проведена оценка интегрального показателя финансово-экономической безопасности предприятий молокоперерабатывающей отрасли. По результатам оценки предложены пути повышения эффективности управления финансово-экономической безопасности таких предприятий, как: ПАО «Дубномолоко», ПАО «Купянский молочноконсервный комбинат», ПАО «Яготинский маслозавод», ПАО «Первомайский молочноконсервный комбинат»

Determination of vertical phase separation in a polyfluorene copolymer:fullerene derivative solar cell blend by X-ray photoelectron spectroscopy

A vertical phase separation is evidenced using high-kinetic-energy X-ray photoelectron spectroscopy at different photon energies in a polyfluorene copolymer:C(60) derivative blend relevant for photovoltaic application