For more than 20 years, scientists have studied solar cells made from organic semiconductors. Throughout this time, device structures have evolved from bilayer devices to bulk heterojunction (BHJ) devices and even though efficiencies are approaching 10%, scientists still know relatively little about the transport of charge carriers and recombination mechanisms in these materials. Novel structures, based on lateral BHJ solar cells, have proven to be versatile tools to study transport and recombination mechanisms. In addition, these structures can easily be employed by researchers and solar cell manufacturers to determine the quality and measure the improvement of their materials. For these studies, poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C61-butyric acid methyl ester (PCBM) has been employed due to its wide use among researchers as well as potential for commercialization. DC photocurrent measurements as a function of device length have yielded the mobility-lifetime product and the generation rate of free carriers within these BHJ devices. In addition to these parameters, the recombination rate as a function of light intensity provides information about the mechanisms of recombination. For example, by measuring the recombination rate as a function of applied electric field and light intensity we have found that recombination is unimolecular in nature and shifts to bimolecular at increased electric field strengths. Additionally, the mobility-lifetime product, generation rate, and recombination mechanism have been studied as a function of applied electric field, illumination spectrum, illumination intensity, etc. This information has provided much insight on physics of the P3HT:PCBM material system which did not exist before these studies. / text

The increasing demand for energy and the pressure to reduce reliance on fossil fuels encourages the development of devices to harness clean and renewable energy. Solar energy is a large enough source to fulfill these demands, however, in order to overcome its daily and seasonal variability, it has been proposed that sunlight be harvested and stored in the form of chemical fuels. One potential approach is the photosynthetic splitting of water to store solar energy in the simplest chemical bond, H–H, using a device that includes: semiconducting microwire arrays as light harvesting components, redox catalysts, and a membrane barrier for separating the products of water redox reactions.. However, the harvested solar energy can be lost across the system and it is critical to characterize the electrical properties of each component within the system to quantify how much of this energy will ultimately be coupled to the water splitting reactions. The aim of this research is to develop approaches for characterization of a proposed system of this kind, incorporating individual semiconductor microwires as photoelectrodes (with no redox catalysts) embedded into a candidate conducting polymer membrane to form a single functional unit. Semiconductor microwires were isolated and using a novel contact formation approach with tungsten probes in a standard probe station, and their current versus voltage properties were characterized. This approach is of particular interest when ii considering the limitations of conventional contact formation approaches (e.g. thermal evaporation of contact metals), arising from the small dimensions of the microwires and also the incompatibility of these techniques with many microwire/polymer structures due to the unwanted interactions between polymers, photoresists, etchants and the high temperature lithographic processes. The electrical properties of different microwires and also the junctions between microwires and two candidate polymers were studied. Specifically, the combination of methyl-terminated silicon microwires and PEDOT:PSS:Nafion demonstrated promising behavior, with a total DC resistance of approximately 720 kΩ (i.e. losses < 16 mV at maximum available photocurrent), making it a suitable candidate for the use in the proposed system. The outcome of these research may be applied to many applications including semiconducting microstructures and conducting polymers.

A new class of electrodes with nanometer-scale contact spacing can be produced at the edge of patterned metal/insulator/metal this film structures. A key challenge is to produce insulator layers with low leakage current and have pristine metal contacts for controlled molecular contacts. Atomic layer deposition of high quality Al2O3 thin films onto Au electrodes was enabled by surface modification with a self-assembled monolayer of -OH groups that react with a monolayer of trimethylaluminum gas source. Ar ion milling was then used to expose the edge of the Au/dielectric/Au structure for molecular electrode contacts. The junctions are characterized by atomic force microscope and tunnel current properties. The Au/self-assembled monolayer/Al2O3/Au tunnel junction, with a very thin oxide insulator layer (15.4 Å), is stable and has a small tunneling current density of about 0.20 ~ 0.75 A/cm2 at 0.5 V. Organometalic cluster molecules were attached to bridge the electrodes. Through tunnel current modeling, low temperature and photo current measurements, molecular current was found to be consistent with direct tunneling through the organic tethers to available states at the metal center. This novel electrode was also used to study the efficiency of organic conducting thin films where the photovoltaic efficiency can be improved when the electrode separation distance is below the exciton diffusion length. Copper (II) phthalocyanine (CuPc) was thermally evaporated between the nano-gap electrodes formed by Au/Al2O3/Au tunnel junctions. A large photocurrent enhancement over 50 times that of bulk CuPc film was observed when the electrode gap distance approached 10 nm. CuPc diffusion length is seen to be 10 nm consistent with literature reports. All devices show diode I-V properties due to a large Schottky barrier contact resistance between the small top Au electrode and the CuPc film. To add another dimension of nm-scale patterning, nanowires can be used as line-of-sight shadowmasks provided that nanowire location and diameter can be controlled. Lateral ZnO nanowires were selectively grown from the edge of a Si/Al2O3/Si multi-layer structure for potential integration into devices utilizing Si processing technology. Microstructural studies demonstrate a 2-step growth process in which the tip region, with a diameter ~ 10 nm, rapidly grew from the Al2O3 surface. Later a base growth with a diameter ~ 22 nm overgrew the existing narrow ZnO nanowire halting further tip growth. Kinetics studies showed surface diffusion on the alumina seed surface determined ZnO nanowire growth rate.

Organische Halbleiter besitzen neue, bemerkenswerte Materialeigenschaften, die sie für die grundlegende Forschung wie auch aktuelle technologische Entwicklung (bsw. org. Leuchtdioden, org. Solarzellen) interessant werden lassen. Aufgrund der starken konformative Freiheit der konjugierten Polymerketten führt die Vielzahl der möglichen Anordnungen und die schwache intermolekulare Wechselwirkung für gewöhnlich zu geringer struktureller Ordnung im Festkörper. Die Morphologie hat gleichzeitig direkten Einfluss auf die elektronische Struktur der organischen Halbleiter, welches sich meistens in einer deutlichen Reduktion der Ladungsträgerbeweglichkeit gegenüber den anorganischen Verwandten zeigt. So stellt die Beweglichkeit der Ladungen im Halbleiter einen der limitierenden Faktoren für die Leistungsfähigkeit bzw. den Wirkungsgrad von funktionellen organischen Bauteilen dar. Im Jahr 2009 wurde ein neues auf Naphthalindiimid und Bithiophen basierendes Dornor/Akzeptor Copolymer vorgestellt [P(NDI2OD‑T2)], welches sich durch seine außergewöhnlich hohe Ladungsträgermobilität auszeichnet. In dieser Arbeit wird die Ladungsträgermobilität in P(NDI2OD‑T2) bestimmt, und der Transport durch eine geringe energetischer Unordnung charakterisiert. Obwohl dieses Material zunächst als amorph beschrieben wurde zeigt eine detaillierte Analyse der optischen Eigenschaften von P(NDI2OD‑T2), dass bereits in Lösung geordnete Vorstufen supramolekularer Strukturen (Aggregate) existieren. Quantenchemische Berechnungen belegen die beobachteten spektralen Änderungen. Mithilfe der NMR-Spektroskopie kann die Bildung der Aggregate unabhängig von optischer Spektroskopie bestätigt werden. Die Analytische Ultrazentrifugation an P(NDI2OD‑T2) Lösungen legt nahe, dass sich die Aggregation innerhalb der einzelnen Ketten unter Reduktion des hydrodynamischen Radius vollzieht. Die Ausbildung supramolekularen Strukturen nimmt auch eine signifikante Rolle bei der Filmbildung ein und verhindert gleichzeitig die Herstellung amorpher P(NDI2OD‑T2) Filme. Durch chemische Modifikation der P(NDI2OD‑T2)-Kette und verschiedener Prozessierungs-Methoden wurde eine Änderung des Kristallinitätsgrades und gleichzeitig der Orientierung der kristallinen Domänen erreicht und mittels Röntgenbeugung quantifiziert. In hochauflösenden Elektronenmikroskopie-Messungen werden die Netzebenen und deren Einbettung in die semikristallinen Strukturen direkt abgebildet. Aus der Kombination der verschiedenen Methoden erschließt sich ein Gesamtbild der Nah- und Fernordnung in P(NDI2OD‑T2). Über die Messung der Elektronenmobilität dieser Schichten wird die Anisotropie des Ladungstransports in den kristallographischen Raumrichtungen von P(NDI2OD‑T2) charakterisiert und die Bedeutung der intramolekularen Wechselwirkung für effizienten Ladungstransport herausgearbeitet. Gleichzeitig wird deutlich, wie die Verwendung von größeren und planaren funktionellen Gruppen zu höheren Ladungsträgermobilitäten führt, welche im Vergleich zu klassischen semikristallinen Polymeren weniger sensitiv auf die strukturelle Unordnung im Film sind. / Organic semiconductors are in the focus of recent research and technological development (eg. for organic light-emitting diodes and solar cells) due to their specific and outstanding material properties. The strong conformational freedom of conjugated polymer chains usually leads to a large number of possible geometric arrangements while weak intermolecular interactions additionally lead to poor structural order in the solid state. At the same time the morphology of those systems has direct influence on the electronic structure of the organic semiconductor which is accompanied by a significant reduction of the charge carrier mobility in contrast to their inorganic counterparts. In that way the transport of charges within the semiconductor represents one of the main limiting factors regarding the performance and efficiency of functional organic devices. In 2009 Facchetti and coworkers presented a novel conjugated donor/acceptor copolymer based on naphthalene diimide and bithiophene [P(NDI2OD‑T2)] which was characterized by an outstanding charge carrier mobility. In this work the mobility of electrons and holes in the bulk of P(NDI2OD‑T2) is determined by single carrier devices and the time-of-flight technique. The results imply a low energetic disorder in these polymer layers. While the material was initially expected to be mainly amorphous, a detailed study of the photophysical properties of P(NDI2OD‑T2) shows that precursors of supramolecular assemblies (aggregates) are already formed in polymer solution. Quantum-chemical calculations support the occurring optical changes. NMR spectroscopy was applied to independently prove the formation of chain aggregates in commonly used organic solvents. The investigation of P(NDI2OD‑T2) solutions by analytical ultracentrifugation implies that aggregation mainly proceeds within single polymer chains by reduction of the hydrodynamic radius. To understand the influence of the chemical structure, pre-aggregation and crystal packing of conventional regioregular P(NDI2OD-T2) on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, a quantitatively characterization of the aggregation, crystallization, and backbone orientation of all of the polymer films was possible, which was then correlated to the electron mobilities in electron-only diodes. The anisotropy of the charge transport along the different crystallographic directions is demonstrated and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene).

Polyaromatic molecules functionalized with carboxylic groups have served as model systems for the growth of organic semiconducting films on a large variety of substrates. Most non-reactive substrates allow for a growth mode compatible with the bulk phase of the molecular crystal with two molecules in the unit cell, but some more reactive substrates including Ag(111) and Ag(110) can induce substantial changes in the first monolayer (ML). In the specific case of Ag(110), the adsorbate unit cell of both NTCDA and PTCDA resembles a brickwall structure, with a single molecule in the unit cell. From this finding, it can be concluded that the adsorbate-substrate interaction is stronger than typical inter-molecular binding energies in the respective bulk phases. In the present work, the interactions between small Ag(110) clusters and a single NTCDA or PTCDA molecule are investigated with different ab initio techniques. Four major ingredients contribute to the binding between adsorbate and substrate: Directional bonds between Ag atoms in the topmost layer and the oxygen atoms of the molecule, Pauli repulsion between filled orbitals of molecule and substrate, an attractive van-der-Waals interaction, and a negative net charge on the molecule inducing positive image charges in the substrate, resulting therefore in an attractive Coulomb interaction between these opposite charges. As both Hartree-Fock theory and density functional theory with typical gradient-corrected density functional do not contain any long range correlation energy required for dispersion interactions, we compare these approaches with the fastest numerical technique where the leading term of the van-der-Waals interaction is included, i.e. second order Møller-Plesset theory (MP2). Both Hartree-Fock and density functional theories result in bended optimized geometries where the adsorbate is interacting mainly via the oxygen atoms, with the core of the molecule repelled from the substrate. Only at the MP2 level, the inclusion of the major part of the attractive van-der-Waals interaction brings the adsorbate back to an arrangement close to parallel to the substrate, with very small differences in height between the different subunits. With respect to experimental data obtained on Ag(111), the calculated distance between adsorbate and substrate is somewhat smaller, indicating that the open Ag(110) surface interacts more strongly with the organic compounds. This is consistent with the fact that only Ag(110) induces a brickwall unit cell of the adsorbate, a clear sign for a particularly large adsorption energy. The resulting model geometries are analysed in terms of cohesive energy, Mulliken charges, core level shifts, and vibrational properties. / Polyaromatische Moleküle, die mit Carboxylgruppen funktionalisiert wurden, haben als Modellsysteme für das Wachstum von organischen Halbleiterfilmen für eine breite Palette von Substraten gedient. Für die meisten nichtreaktiven Substrate ist ein zum molekularen Kristall kompatibles Wachstum mit zwei Monolagen pro Einheitszelle möglich, jedoch erzeugen reaktivere Substrate wie z.B. Ag(111) oder Ag(110) bereits substanzielle Modifikationen in der ersten Monolage. Im speziellen Fall von Ag(110) bildet die Adsorbateinheitszelle sowohl von NTCDA als auch PTCDA eine sogenannte brickwall structure heraus mit einem einzigen Molekül pro Einheitszelle. Aus dieser Beobachtung kann geschlussfolgert werden, dass die Adsorbat-Substrat-Wechselwirkung stärker ist als die typischen intermolekularen Bindungsenergien in der entsprechenden Bulk-Phase. In der vorliegenden Arbeit werden die Wechselwirkungen zwischen kleinen Ag(110)-Clustern und einem einzelnen NCTDA oder PTCDA-Molekül mit verschiedenen ab initio-Techniken untersucht. Im Wesentlichen tragen vier Hauptbestandteile zur Bindung zwischen Adsorbat und Substrat bei: Gerichtete Bindungen zwischen Ag-Atomen in der obersten Substratschicht und den Sauerstoffatomen des Moleküls, Pauli-Abstoßung zwischen besetzten Orbitalen von Molekül und Substrat, eine anziehende Van-der-Waals-Wechselwirkung sowie einer negativen Ladung des Moleküls und der dazugehörigen positiven Spiegelladung im Substrat, die zu einer anziehenden Coulombwechselwirkung führen. Da weder die Hartree-Fock-Theorie noch die Dichtefunktionaltheorie mit dem typischen gradientenkorrigierten Dichtefunktional die für Dispersionswechselwirkungen benötigte langreichweitige Korrelationsenergie beinhalten, vergleichen wir diese beiden Ansätze mit der schnellsten numerischen Methode, die den dominierenden Term der Van-der-Waals-Wechselwirkung beinhaltet, nämlich der Møller-Plesset-Theorie zweiter Ordnung (MP2). Sowohl die Hartree-Fock-Theorie als auch die Dichtefunktionaltheorie sagen verbogene optimierte Geometrien voraus, die vorwiegend durch die Sauerstoffatome interagieren, wohingegen die zentralen Teile des Moleküls vom Substrat abgestoßen werden. Lediglich die MP2, die den wesentlichen Teil der anziehenden Van-der-Waals-Wechselwirkung beinhaltet, sagt eine beinahe parallele Anordnung des Moleküls an das Substrat voraus, wobei die einzelnen Untereinheiten des Moleküls nur unwesentlich verschiedene Abstände zum Substrat haben. Im Vergleich zu experimentellen Daten für Ag(111) ist die berechnete Distanz zwischen Adsorbat und Substrat etwas kleiner, woraus sich schlussfolgern lässt, dass die offene Ag(110)-Oberfläche stärker mit den organischen Verbindungen interagiert. Das ist im Einklang mit der Tatsache, dass nur Ag(110) die brickwall-Struktur des Adsorbats besitzt, was ein deutliches Zeichen für eine hohe Adsorptionsenergie ist. Die resultierenden Modellgeometrien wurden bezüglich ihrer Kohäsionsenergie, Mullikenladungen, Kernelektronenniveauverschiebungen und vibrationeller Eigenschaften untersucht.

The increasing demand for energy and the pressure to reduce reliance on fossil fuels encourages the development of devices to harness clean and renewable energy. Solar energy is a large enough source to fulfill these demands, however, in order to overcome its daily and seasonal variability, it has been proposed that sunlight be harvested and stored in the form of chemical fuels. One potential approach is the photosynthetic splitting of water to store solar energy in the simplest chemical bond, H–H, using a device that includes: semiconducting microwire arrays as light harvesting components, redox catalysts, and a membrane barrier for separating the products of water redox reactions.. However, the harvested solar energy can be lost across the system and it is critical to characterize the electrical properties of each component within the system to quantify how much of this energy will ultimately be coupled to the water splitting reactions. The aim of this research is to develop approaches for characterization of a proposed system of this kind, incorporating individual semiconductor microwires as photoelectrodes (with no redox catalysts) embedded into a candidate conducting polymer membrane to form a single functional unit. Semiconductor microwires were isolated and using a novel contact formation approach with tungsten probes in a standard probe station, and their current versus voltage properties were characterized. This approach is of particular interest when ii considering the limitations of conventional contact formation approaches (e.g. thermal evaporation of contact metals), arising from the small dimensions of the microwires and also the incompatibility of these techniques with many microwire/polymer structures due to the unwanted interactions between polymers, photoresists, etchants and the high temperature lithographic processes. The electrical properties of different microwires and also the junctions between microwires and two candidate polymers were studied. Specifically, the combination of methyl-terminated silicon microwires and PEDOT:PSS:Nafion demonstrated promising behavior, with a total DC resistance of approximately 720 kΩ (i.e. losses < 16 mV at maximum available photocurrent), making it a suitable candidate for the use in the proposed system. The outcome of these research may be applied to many applications including semiconducting microstructures and conducting polymers.

The photosensitive molecule adsorption on titanium dioxide (TiO2) forms the so-called “dye sensitized TiO2” system, a typical organic/oxide heterojunction, which is of great interest in catalysis and energy applications, e.g. dye-sensitized solar cell (DSSC). Traditionally, the transition metal complex dyes are the focus of the study. However, as the fast development of the organic semiconductors and invention of new pure organic dyes, it is necessary to expand the research horizon to cover these molecules and concrete the fundamental understanding of their basic properties, especially during sensitization.In this work, we focus on two different photosensitive molecules: phthalocyanines and triphenylamine-based dyes. Phthalocyanines are organic semiconductors with symmetric macro aromatic molecular structures. They possess good photoelectrical properties and good thermal and chemical stability, which make them widely used in the organic electronic industries. Triphenylamine-based dyes are new types of pure organic dyes which deliver high efficiency and reduce the cost of DSSC. They can be nominated as one of the strong candidates to substitute the ruthenium complex dyes in DSSC. The researches were carried out using classic surface science techniques on single crystal substrates and under ultrahigh vacuum condition. The photosensitive molecules were deposited by organic molecular beam deposition. The substrate reconstruction and ordering were checked by low energy electron diffraction. The molecular electronic, geometric structures and charge transfer properties were characterized by photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and resonant photoelectron spectroscopy (RPES). Scanning tunneling microscopy is used to directly image the molecular adsorption.For phthalocyanines, we select MgPc, ZnPc, FePc and TiOPc, which showed a general charge transfer from molecule to the substrate when adsorbed on rutile TiO2(110) surface with 1×1 and 1×2 reconstructions. This charge transfer can be prevented by modifying the TiO2 surface with pyridine derivatives (4-tert-butyl pyridine (4TBP), 2,2’-bipyridine and 4,4’-bipyridine), and furthermore the energy level alignment at the interface is modified by the surface dipole established by the pyridine molecules. Annealing also plays an important role to control the molecular structure and change the electronic structure together with the charge transfer properties, shown by TiOPc film. Special discussions were done for 4TBP for its ability to shift the substrate band bending by healing the oxygen vacancies, which makes it an important additive in the DSSC electrolyte. For the triphenylamine-based dye (TPAC), the systematic deposition enables the characterization of the coverage dependent changes of molecular electronic and geometric structures. The light polarization dependent charge transfer was revealed by RPES. Furthermore, the iodine doped TPAC on TiO2 were investigated to mimic the electrolyte/dye/TiO2 interface in the real DSSC.The whole work of this thesis aims to provide fundamental understanding of the interaction between photosensitive molecules on TiO2 surfaces at molecular level in the monolayer region, e.g. the formation of interfacial states and the coverage dependent atomic and electronic structures, etc. We explored the potential of the application of new dyes and modified of the existing system by identifying their advantage and disadvantage. The results may benefit the fields of dye syntheses, catalysis researches and designs of organic photovoltaic devices. / QC 20111114

[pt] Neste trabalho é apresentado um estudo da influência das técnicas de deposição de filmes finos nas propriedades físicas de dois sistemas moleculares orgânicos. O estudo foi realizado através da análise das características ópticas e elétricas de filmes finos e dispositivos OLEDs crescidos utilizando os sistemas orgânicos: (1) DCM2:Alq3 e (2) [Sm(tta)3(dppmo):Eu(tta)3(dppmo)]. Em ambos os casos um material é utilizado como matriz (Alq3 ou complexo de Sm3+) e outro como dopante (DCM2 ou complexo de Eu3+). A análise das propriedades físicas do sistema (1), crescido por co-deposição térmica e por spin-coating, permitiram mostrar que a resposta do sistema muda em função da técnica de deposição usada. Por exemplo, o processo de transferência de energia molecular entre a matriz (Alq3) e o dopante (DCM2) varia de uma técnica para outra, sendo menos eficiente na técnica onde o filme crescido permite obter uma separação maior entre as moléculas. O estudo também mostrou que a transferência de energia pode ser inibida por meio de um processo de fotodegradação do sistema com luz UV. A análise do sistema (2), crescido pelas técnicas de co-deposição térmica e deposição térmica de moléculas misturadas na fase sólida, mostrou que a resposta deste sistema é independente do método de deposição utilizado. Além disso, a dopagem da matriz Sm(tta)3(dppmo) com um complexo de európio que possui os mesmos ligantes orgânicos, permitiu observar uma transferência de energia intermolecular entre os dois complexos, assim como um aumento da intensidade de emissão de algumas das transições do íon Eu3+. Estes sistemas foram usados na fabricação de dispositivos orgânicos eletroluminescentes e o sistema molecular 1 como sensor de radiação UV. / [en] This dissertation reports the study of the influence of different deposition techniques on the physical properties of two molecular organic systems: (1) DCM2:Alq3 e (2) [Sm(tta)3(dppmo):Eu(tta)3(dppmo)]. The investigation was carried out by analyzing the optical and electrical characteristics of thin films and organic light-emitting devices (OLEDs) based on the two organic systems. In both systems, one of the compounds was used as the host (Alq3 and Sm-based complex) and the other as the dopant (DCM2 and Eu-based complex). Analysis of the system (1) physical properties, showed that the system response varies as a function of the used deposition technique (in this case, thermal codeposition and spin-coating). For example, the molecular energy-transfer process between the matrix (Alq3) and the dopant (DCM2) varies from one technique to the other, being less efficient in the one where the molecular separation is larger. The study also demonstrated that the energy transfer can be inhibited by means of UV photodegradation process. System (2) was grown by thermal codeposition as well as thermal deposition of molecules mixed in solid phase. In this case, the results indicated that the response of this system is independent of the deposition technique chosen. Besides, doping the Sm(tta)3(dppmo) host with an europium complex allowed to observe not only an intermolecular energytransfer between the two complexes but also an increasing in the emission intensity of some Eu3+ transitions. Both systems can be applied to UV radiation sensors’ fabrication and organic light-emitting devices.

This thesis focuses on the characterization of PEDOT:DBSA, a new semiconducting polymer for use in bioelectronic devices. It also deals with possibilities of surface treatment in order to enhance its biocompatibility and stability in aqueous environments. For this purpose, the organic polymer films were crosslinked with two crosslinking agents – GOPS and DVS. The ability of these agents to prevent leaching of some fractions of the polymer films in an aqueous environment and the ability to bind polymer molecules to each other as well as to the glass substrate was studied using the delamination test. Subsequently, the effects of these crosslinking agents on the film properties essential for the proper functions of bioelectronics made of these materials, was studied by contact angle measurements and four-point probes respectively. Moreover, several OECTs were prepared using original and crosslinked material as an active layer and were characterized by measuring transconductance and volumetric capacitance. PEDOT:DBSA has been shown to be a suitable material for use in bioelectronics, but its thin layers need to be stabilized in an aqueous environment. The agent DVS appears to be unsuitable for this purpose, mainly due to its insufficient film stabilization and its increased hydrophilicity of the film surface, thus increased tendency to interact with water, resulting in degradation of these thin layers. In contrast, GOPS, despite some reduction in film conductivity, has been able to stabilize the polymer layer over the long term, and thus appears to be a suitable way to stabilize PEDOT:DBSA.

Using X-ray photoelectron (XPS) and X-ray absorbtion spectroscopy (XAS) we demonstrate charge transfer at an interface between two transition metal phthalocyanines, MnPc and F16CoPc, resulting in charged MnPc + and F16CoPc -, species. Density functional theory calculations reveal that a hybrid state is formed between the two types of phthalocyanines, which causes this charge transfer. For the hybrid state the Mn3dxz interacts with the Co 3dz2 orbital leading to a two-level system. Moreover, we have prepared mixed films out of this pair, which were characterized also by means of electron energy-loss spectroscopy. Our data reveal the formation of MnPc/F16CoPc charge transfer dimers in analogy to the heterojunction. The electronic excitation spectrum of these blends is characterized by a new low energy excitation at 0.6 eV.