Space Charge Transfer in Hybrid Inorganic/Organic Systems

We discuss density functional theory calculations of hybrid inorganic/organic systems (HIOS) that explicitly include the global effects of doping (i.e. position of the Fermi level) and the formation of a space-charge layer. For the example of tetrafluoro-tetracyanoquinodimethane (F4TCNQ) on the ZnO(000$\bar{1}$) surface we show that the adsorption energy and electron transfer depend strongly on the ZnO doping. The associated work function changes are large, for which the formation of space-charge layers is the main driving force. The prominent doping effects are expected to be quite general for charge-transfer interfaces in HIOS and important for device design

the path to silicon-singlet fission heterojunction devices

Singlet exciton fission is an exciton multiplication process that occurs in certain organic materials, converting the energy of single highly-energetic photons into pairs of triplet excitons. This could be used to boost the conversion efficiency of crystalline silicon solar cells by creating photocurrent from energy that is usually lost to thermalisation. An appealing method of implementing singlet fission with crystalline silicon is to incorporate singlet fission media directly into a crystalline silicon device. To this end, we developed a solar cell that pairs the electron-selective contact of a high-efficiency silicon heterojunction cell with an organic singlet fission material, tetracene, and a PEDOT:PSS hole extraction layer. Tetracene and n-type crystalline silicon meet in a direct organic–inorganic heterojunction. In this concept the tetracene layer selectively absorbs blue-green light, generating triplet pairs that can dissociate or resonantly transfer at the organo-silicon interface, while lower-energy light is transmitted to the silicon absorber. UV photoemission measurements of the organic–inorganic interface showed an energy level alignment conducive to selective hole extraction from silicon by the organic layer. This was borne out by current–voltage measurements of devices subsequently produced. In these devices, the silicon substrate remained well-passivated beneath the tetracene thin film. Light absorption in the tetracene layer created a net reduction in current for the solar cell, but optical modelling of the external quantum efficiency spectrum suggested a small photocurrent contribution from the layer. This is a promising first result for the direct heterojunction approach to singlet fission on crystalline silicon

Subtle Fluorination of Conjugated Molecules Enables Stable Nanoscale Assemblies on Metal Surfaces

In molecular self-assembly on surfaces, the structure is governed by the intricate balance of attractive and repulsive forces between molecules as well as between molecules and the substrate. Frequently, repulsive interactions between molecules adsorbed on a metal surface dominate in the low-coverage regime, and dense self-assembled structures can only be observed close to full monolayer coverage. Here, we demonstrate that fluorination at selected positions of conjugated molecules provides for sufficiently strong, yet nonrigid, H···F bonding capability that (i) enables the formation of stable nanoscale molecular assemblies on a metal surface and (ii) steers the assemblies’ structure. This approach should be generally applicable and will facilitate the construction and study of individual nanoscale molecular assemblies with structures that are not attainable in the high-coverage regime

Simulation of SVPWM Based Multivariable Control Method for a DFIG Wind Energy System

This paper deals with a variable speed device toproduce electrical energy on a power network based on adoubly-fed induction machine used in generating mode(DFIG) in wind energy system by using SVPWM powertransfer matrix. This paper presents a modeling and controlapproach which uses instantaneous real and reactive powerinstead of dq components of currents in a vector controlscheme. The main features of the proposed model comparedto conventional models in the dq frame of reference arerobustness and simplicity of realization. The sequential loopclosing technique is adopted to design a multivariable controlsystem including six compensators for a DFIG wind energysystem to capture the maximum wind power and to inject therequired reactive power to the generator. In this paperSVPWM method is used for better controlling of converters.It also provides fault ride through method to protect theconverter during a fault. The time-domain simulation of thestudy system is presented by using MATLAB Simulink to testthe system robustness, to validate the proposed model and toshow the enhanced tracking capability

Electronic and structural properties of conjugated molecules at molecular hetero-interfaces and on metal surfaces

Diese Arbeit behandelt elektronische und strukturelle Eigenschaften dünner Schichten aus konjugierten organischen Molekülen (COMs), aufgebracht auf Metalloberflächen per Vakuum-Sublimation. Diese Eigenschaften sind essenziell für Funktionsrealisierung und -optimierung organischer Elektronikbauteile. Teil 1 diskutiert zwei Ansätze zur Energieniveauanpassung (ELA) an Organik-Metall-Grenzflächen zur Einstellung der dortigen Löcherinjektionsbarrieren (HIBs) durch (Über-)Kompensation des abträglichen "Push-back"-Effekts: - Ausnutzung der besonderen ELA bei Chalkogen-Metall-Bindungen, hier gezeigt mit Hilfe von Röntgen- und Ultraviolettphotoelektronenspektroskopie (UPS/XPS) für ein Seleno-funktionalisiertes COM - Einfügen von COMs mit ausgeprägtem Elektronen-Akzeptorcharakter vor dem Aufbringen der aktiven Schicht. UPS-Messungen zeigen, dass beide Ansätze HIBs von ca. 0.3 eV ermöglichen. Teil 2 untersucht ausgewählte organische Heterostrukturen auf Metallen. Die Untersuchungen identifizieren einen Ladungstransfer vom Metall zur Überschicht (MOCT) als verantwortlich dafür, das System bei Ferminiveau-Pinning in den Gleichgewichtszustand zu überführen. Detaillierte Untersuchungen gestatten die Identifikaton von ganzzahligem Ladungstransfer zu einem Teil der Moleküle in der ersten Überschichtlage und den Einfluss der Dipol-Abstoßung in der Überschicht. In Teil 3 dienen Metalloberflächen als Auflage für supramolekulare Architekturen mit dipolaren Bausteinen. Rastertunnelmikroskopie (STM) an einer Serie von teils partiell fluorierten, stäbchenförmigen COMs mit unterschiedlich großen Dipolmomenten ermöglicht die Entflechtung von Dipol-Dipol- und konkurierenden Wechselwirkungen physisorbierter Submonolagen auf Ag(111). Ein anderes, stark dipolares COM bildet bei Monolagenbedeckung auf Au(111) sechs Phasen, alle mit antiferroelektrischer Einheitszellen. UPS-Messungen ergeben eine bevorzugte Ausrichtung der Moleküle in Multilagen.In this thesis, the electronic and structural properties of thin films of conjugated organic molecules (COMs) vacuum-deposited on metal surfaces are studied. These properties are essential for realization and optimization of device functionalities in the field of organic electronics. Part 1 discusses two approaches for engineering the energy-level alignment (ELA), and, thereby, optimizing hole injection barriers (HIBs), at organic/metal interfaces via (over)compensation of the detrimental "push-back": - Exploiting the peculiar ELA at chalcogen-metal bonds, shown here (with X-ray and ultraviolet photoelectron spectroscopy, UPS/XPS) for a seleno-functionalized COM - inserting electron-accepting COMs prior to deposition of active layers. UPS shows that both approaches realize HIBs into the active COM as low as 0.3 eV. Part 2 studies selected organic/organic heterostructures on metal surfaces. These studies allow to propose that metal to overlayer charge transfer (MOCT), is responsible for achieving electronic equilibrium when such systems are Fermi-level pinned. Detailed investigations allowed identifying integer charge transfer to a fraction of the molecules in the first overlayer and the influence of the dipole-repulsion on the overlayer. In Part 3, metal surfaces are used as support for supramolecular architecture with polar building blocks. Scanning tunneling microscopy (STM) of a series of rod-like COMs with and without partial fluorination and with different dipole moments help disentangling the delicate balance dipole-dipole and competing interactions for sub-monolayer films physisorbed on Ag(111). For another, highly-polar COM at ca. monolayer coverage on Au(111), STM identifies six phases. All phases are found to exhibit anti-ferroelectric unit cells. UPS evidences a preferential alignment of multilayer molecules

Tetracene Ultrathin Film Growth on Hydrogen Passivated Silicon

Inorganic organic interfaces are important for enhancing the power conversion efficiency of silicon based solar cells through singlet exciton fission SF . We elucidated the structure of the first monolayers of tetracene Tc , a SF molecule, on hydrogen passivated Si 111 [H Si 111 ] and hydrogenated amorphous Si a Si H by combining near edge X ray absorption fine structure NEXAFS and X ray photoelectron spectroscopy XPS experiments with density functional theory DFT calculations. For samples grown at or below substrate temperatures of 265 K, the resulting ultrathin Tc films are dominated by almost upright standing molecules. The molecular arrangement is very similar to the Tc bulk phase, with only slightly higher average angle between the conjugated molecular plane normal and the surface normal alpha around 77 . Judging from carbon K edge X ray absorption spectra, the orientation of the Tc molecules are almost identical when grown on H Si 111 and a Si H substrates as well as for sub mono to several monolayer coverages. Annealing to room temperature, however, changes the film structure towards a smaller alpha of about 63 . A detailed DFT assisted analysis suggests that this structural transition is correlated with a lower packing density and requires a well chosen amount of thermal energy. Therefore, we attribute the resulting structure to a distinct monolayer configuration that features less inclined, but still well ordered molecules. The larger overlap with the substrate wavefunctions makes this arrangement attractive for an optimized interfacial electron transfer in SF assisted silicon solar cell

Unveiling the Hybrid n‑Si/PEDOT:PSS Interface

We investigated the <i>buried</i> interface between monocrystalline n-type silicon (n-Si) and the highly conductive polymer poly­(3,4-ethylenedioxythiophene)-poly­(styrenesulfonate) (PEDOT:PSS), which is successfully applied as a hole selective contact in hybrid solar cells. We show that a post-treatment of the polymer films by immersion in a suitable solvent reduces the layer thickness by removal of excess material. We prove that this post-treatment does not affect the functionality of the hybrid solar cells. Through the thin layer we are probing the chemical structure at the n-Si/PEDOT:PSS interface with synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). From the HAXPES data we conclude that the Si substrate of a freshly prepared hybrid solar cell is already oxidized immediately after preparation. Moreover, we show that even when storing the sample in inert gas such as, e.g., nitrogen the n-Si/SiO_<i>x</i>/PEDOT:PSS interface continues to further oxidize. Thus, without further surface treatment, an unstable Si suboxide will always be present at the hybrid interface

Tuning the Electronic Structure of Graphene by Molecular Dopants Impact of the Substrate

A combination of ultraviolet and X ray photoelectron spectroscopy, X ray absorption spectroscopy and first principle calculations was used to study the electronic structure at the interface between the strong molecular acceptor 1,3,4,5,7,8 hexafluorotetracyano naphthoquinodimethane F6TCNNQ and a graphene layer supported on either a quartz or a copper substrate. We find evidence for fundamentally different charge re distribution mechanisms in the two ternary systems, as a consequence of the insulating versus metallic character of the substrates. While electron transfer occurs exclusively from graphene to F6TCNNQ on the quartz support p doping of graphene , the Cu substrate electron reservoir induces an additional electron density flow to graphene decorated with the acceptor monolayer. Remarkably, graphene on Cu is ndoped, and remains n doped upon F6TCNNQ deposition. On both substrates, the work function of graphene increases substantially with a F6TCNNQ monolayer atop, the effect being more pronounced 1.3 eV on Cu compared to quartz 1.0 eV because of the larger electrostatic potential drop associated with the long distance graphene mediated Cu F6TCNNQ electron transfer. We thus provide means to realize high work function surfaces for both p and n type doped graphen