Martin Oehzelt

Bio: Martin Oehzelt is an academic researcher from Helmholtz-Zentrum Berlin. The author has contributed to research in topics: Organic semiconductor & Pentacene. The author has an hindex of 35, co-authored 83 publications receiving 4638 citations. Previous affiliations of Martin Oehzelt include Johannes Kepler University of Linz & University of Graz.

Nitrogen-Doped Graphene: Efficient Growth, Structure, and Electronic Properties

Abstract: A novel strategy for efficient growth of nitrogen-doped graphene (N-graphene) on a large scale from s-triazine molecules is presented. The growth process has been unveiled in situ using time-dependent photoemission. It has been established that a postannealing of N-graphene after gold intercalation causes a conversion of the N environment from pyridinic to graphitic, allowing to obtain more than 80% of all embedded nitrogen in graphitic form, which is essential for the electron doping in graphene. A band gap, a doping level of 300 meV, and a charge-carrier concentration of ∼8 × 1012 electrons per cm2, induced by 0.4 atom % of graphitic nitrogen, have been detected by angle-resolved photoemission spectroscopy, which offers great promise for implementation of this system in next generation electronic devices.

Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules

Abstract: ConspectusToday’s information society depends on our ability to controllably dope inorganic semiconductors, such as silicon, thereby tuning their electrical properties to application-specific demands. For optoelectronic devices, organic semiconductors, that is, conjugated polymers and molecules, have emerged as superior alternative owing to the ease of tuning their optical gap through chemical variability and their potential for low-cost, large-area processing on flexible substrates. There, the potential of molecular electrical doping for improving the performance of, for example, organic light-emitting devices or organic solar cells has only recently been established. The doping efficiency, however, remains conspicuously low, highlighting the fact that the underlying mechanisms of molecular doping in organic semiconductors are only little understood compared with their inorganic counterparts.Here, we review the broad range of phenomena observed upon molecularly doping organic semiconductors and identify ...

Organic semiconductor density of states controls the energy level alignment at electrode interfaces.

Abstract: Minimizing charge carrier injection barriers and extraction losses at interfaces between organic semiconductors and metallic electrodes is critical for optimizing the performance of organic (opto-) electronic devices. Here, we implement a detailed electrostatic model, capable of reproducing the alignment between the electrode Fermi energy and the transport states in the organic semiconductor both qualitatively and quantitatively. Covering the full phenomenological range of interfacial energy level alignment regimes within a single, consistent framework and continuously connecting the limiting cases described by previously proposed models allows us to resolve conflicting views in the literature. Our results highlight the density of states in the organic semiconductor as a key factor. Its shape and, in particular, the energy distribution of electronic states tailing into the fundamental gap is found to determine both the minimum value of practically achievable injection barriers as well as their spatial profile, ranging from abrupt interface dipoles to extended band-bending regions.

Charge-transfer crystallites as molecular electrical dopants

Abstract: Ground-state integer charge transfer is commonly regarded as the basic mechanism of molecular electrical doping in both, conjugated polymers and oligomers. Here, we demonstrate that fundamentally different processes can occur in the two types of organic semiconductors instead. Using complementary experimental techniques supported by theory, we contrast a polythiophene, where molecular p-doping leads to integer charge transfer reportedly localized to one quaterthiophene backbone segment, to the quaterthiophene oligomer itself. Despite a comparable relative increase in conductivity, we observe only partial charge transfer for the latter. In contrast to the parent polymer, pronounced intermolecular frontier-orbital hybridization of oligomer and dopant in 1:1 mixed-stack co-crystallites leads to the emergence of empty electronic states within the energy gap of the surrounding quaterthiophene matrix. It is their Fermi-Dirac occupation that yields mobile charge carriers and, therefore, the co-crystallites-rather than individual acceptor molecules-should be regarded as the dopants in such systems.

Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors

Abstract: Polymer transistors are being intensively developed for next-generation flexible electronics. Blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix have simultaneously shown superior performance and environmental stability in organic field-effect transistors compared with the neat semiconductor. Here we show that such blends actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping. Structural investigations show that these blend layers feature nanometre-scale semiconductor domains and a vertical composition gradient. This particular morphology enables a quasi three-dimensional spatial distribution of semiconductor pathways within the insulating matrix, in which charge accumulation and depletion via a gate bias is substantially different from neat semiconductor, and where high on-current and low off-current are simultaneously realized in the stable doped state. Adding only 5 wt% of a semiconducting polymer to a polystyrene matrix, we realized an environmentally stable inverter with gain up to 60.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

Abstract: Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Heteroatom-doped graphene materials: syntheses, properties and applications

Abstract: Heteroatom doping can endow graphene with various new or improved electromagnetic, physicochemical, optical, and structural properties. This greatly extends the arsenal of graphene materials and their potential for a spectrum of applications. Considering the latest developments, we comprehensively and critically discuss the syntheses, properties and emerging applications of the growing family of heteroatom-doped graphene materials. The advantages, disadvantages, and preferential doping features of current synthesis approaches are compared, aiming to provide clues for developing new and controllable synthetic routes. We emphasize the distinct properties resulting from various dopants, different doping levels and configurations, and synergistic effects from co-dopants, hoping to assist a better understanding of doped graphene materials. The mechanisms underlying their advantageous uses for energy storage, energy conversion, sensing, and gas storage are highlighted, aiming to stimulate more competent applications.

Integrated materials design of organic semiconductors for field-effect transistors

Abstract: The past couple of years have witnessed a remarkable burst in the development of organic field-effect transistors (OFETs), with a number of organic semiconductors surpassing the benchmark mobility of 10 cm2/(V s). In this perspective, we highlight some of the major milestones along the way to provide a historical view of OFET development, introduce the integrated molecular design concepts and process engineering approaches that lead to the current success, and identify the challenges ahead to make OFETs applicable in real applications.

Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst

Abstract: Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical to renewable energy conversion and storage technologies. Heteroatom-doped carbon nanomaterials have been reported to be efficient metal-free electrocatalysts for ORR in fuel cells for energy conversion, as well as ORR and OER in metal-air batteries for energy storage. We reported that metal-free three-dimensional (3D) graphene nanoribbon networks (N-GRW) doped with nitrogen exhibited superb bifunctional electrocatalytic activities for both ORR and OER, with an excellent stability in alkaline electrolytes (for example, KOH). For the first time, it was experimentally demonstrated that the electron-donating quaternary N sites were responsible for ORR, whereas the electron-withdrawing pyridinic N moieties in N-GRW served as active sites for OER. The unique 3D nanoarchitecture provided a high density of the ORR and OER active sites and facilitated the electrolyte and electron transports. As a result, the as-prepared N-GRW holds great potential as a low-cost, highly efficient air cathode in rechargeable metal-air batteries. Rechargeable zinc-air batteries with the N-GRW air electrode in a two-electrode configuration exhibited an open-circuit voltage of 1.46 V, a specific capacity of 873 mAh g−1, and a peak power density of 65 mW cm−2, which could be continuously charged and discharged with an excellent cycling stability. Our work should open up new avenues for the development of various carbon-based metal-free bifunctional electrocatalysts of practical significance.

Crumpled Nitrogen‐Doped Graphene Nanosheets with Ultrahigh Pore Volume for High‐Performance Supercapacitor

Abstract: Continuous scientifi c endeavors have been directed toward the optimization of graphene by manipulating its electronic, mechanical, chemical, and structural properties, such as surface area, pore geometry, and functional sites, in order to advance various potential applications, including nanoelectronics, energy storage/conversion, and catalysis. [ 1 ] The structural reformation of graphene, from pore generation to morphology transformation, is receiving growing attention, because the reconstruction of graphene could potentially result in localized highly reactive regions and thus unexpected properties for specifi c applications. [ 2 ] For instance, it was reported that crumpled graphene allows for the fabrication of polymer-graphene nanocomposite fi lms with low O 2 permeability and effective reduction of transparency. [ 3 ] Chemical functionalization of graphene (e.g., graphene oxide or GO) is another effective method for manipulating physical and chemical properties of graphene, because enriched reactive oxygen functional groups in GO can provide ample covalent bonding sites for the chemical functionalization. The functionalized GO can be easily converted to graphene-like materials through chemical or thermal reduction of GO. [ 4 ] For instance, nitrogen-doped graphene (NG) can be synthesized through thermal annealing of GO in ammonia, and the resulting NG showed some unique properties including improved conductivity and excellent catalytic activity. Actually, NG has been intensively investigated as electrode materials for lithium-ion batteries, catalysts for oxygen reduction reac-