Characterization of step-edge barrier crossing of para-sexiphenyl on the ZnO (101[combining macron]0) surface.

Mass transport processes of conjugated organic molecules (COMs) on inorganic surfaces are essential elements in thin film deposition for hybrid optoelectronic devices. Defects and in particular surface step-edges dictate the molecular nucleation and growth morphology, which itself determine many physical properties of the resulting hybrid interface. Here, we explore the detailed molecular kinetics and transport rates of a single physisorbed para-sexiphenyl (p-6P) molecule crossing a step-edge (a "hetero-Ehrlich-Schwoebel barrier") on the inorganic ZnO (101[combining macron]0) surface by a combination of all-atom molecular dynamics simulations and passage time theory.

The Optical Signature of Charges in Conjugated Polymers.

Electrical charge flowing through organic semiconductors drives many of today's mobile phone displays and television screens, suggesting an internally consistent model of charge-carrier properties in these materials to have manifested. In conjugated polymers, charges give rise to additional absorption of light at wavelengths longer than those absorbed by the electrically neutral species. These characteristic absorption bands are universally being related to the emergence of localized energy levels shifted into the forbidden gap of organic semiconductors due to local relaxation of the molecular geometry.

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

Today'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.

Energy-level alignment at organic heterointerfaces.

Today's champion organic (opto-)electronic devices comprise an ever-increasing number of different organic-semiconductor layers. The functionality of these complex heterostructures largely derives from the relative alignment of the frontier molecular-orbital energies in each layer with respect to those in all others. Despite the technological relevance of the energy-level alignment at organic heterointerfaces, and despite continued scientific interest, a reliable model that can quantitatively predict the full range of phenomena observed at such interfaces is notably absent.

Charge-transfer crystallites as molecular electrical dopants.

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.

Integer versus Fractional Charge Transfer at Metal(/Insulator)/Organic Interfaces: Cu(/NaCl)/TCNE.

Semilocal and hybrid density functional theory was used to study the charge transfer and the energy-level alignment at a representative interface between an extended metal substrate and an organic adsorbate layer. Upon suppressing electronic coupling between the adsorbate and the substrate by inserting thin, insulating layers of NaCl, the hybrid functional localizes charge. The laterally inhomogeneous charge distribution resulting from this spontaneous breaking of translational symmetry is reflected in observables such as the molecular geometry, the valence and core density of states, and the evolution of the work function with molecular coverage, which we discuss for different growth modes.

Structure and stoichiometry prediction of surfaces reacting with multicomponent gases.

Reactive interactions of molecules with solid surfaces are of key interest for catalysis and surface functionalization. Here, conceptual shortcomings of previous theoretical methods for the prediction of steady-state surface structures and stoichiometries from first-principles thermodynamics are identified. An extension is then proposed, which now enables the unconstrained description of an arbitrary number of mutually reacting gas-phase species.

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

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.

Seleno groups control the energy-level alignment between conjugated organic molecules and metals.

The charge injection from metallic electrodes into hole transporting layers of organic devices often suffers from deviations from vacuum-level alignment at the interface. Even for weakly interacting cases, Pauli repulsion causes an interface dipole between the metal and conjugated organic molecules (COMs) (so called "push-back" or "cushion" effect), which leads notoriously to an increase of the hole injection barrier. On the other hand, for chalcogenol self assembled monolayers (SAMs) on metal surfaces, chemisorption via the formation of chalcogen-metal bonds is commonly observed.

Band-bending in organic semiconductors: the role of alkali-halide interlayers.

Band-bending in organic semiconductors, occurring at metal/alkali-halide cathodes in organic-electronic devices, is experimentally revealed and electrostatically modeled. Metal-to-organic charge transfer through the insulator, rather than doping of the organic by alkali-metal ions, is identified as the origin of the observed band-bending, which is in contrast to the localized interface dipole occurring without the insulating buffer layer.

Doping of organic semiconductors: impact of dopant strength and electronic coupling.

Molecular doping: The standard model for molecular p-doping of organic semiconductors (OSCs) assumes integer charge transfer between OSC and dopant. This is in contrast to an alternative model based on intermolecular complex formation instead. By systematically varying the acceptor strength it was possible to discriminate the two models.

Epitaxial growth of π-stacked perfluoropentacene on graphene-coated quartz.

Chemical-vapor-deposited large-area graphene is employed as the coating of transparent substrates for the growth of the prototypical organic n-type semiconductor perfluoropentacene (PFP). The graphene coating is found to cause face-on growth of PFP in a yet unknown substrate-mediated polymorph, which is solved by combining grazing-incidence X-ray diffraction with theoretical structure modeling. In contrast to the otherwise common herringbone arrangement of PFP in single crystals and "standing" films, we report a π-stacked arrangement of coplanar molecules in "flat-lying" films, which exhibit an exceedingly low π-stacking distance of only 3.

Polarity switching of charge transport and thermoelectricity in self-assembled monolayer devices.

Self-assembled monolayer devices can exhibit drastically different charge-transport characteristics and thermoelectric properties despite being composed of isomeric molecules with essentially identical frontier-orbital energies. This is rationalized by the cooperative electrostatic action of local intramolecular dipoles in otherwise nonpolar species, thus revealing new challenges but also new opportunities for the targeted design of functional building blocks in future nanoelectronics.

Intermolecular hybridization governs molecular electrical doping.

Current models for molecular electrical doping of organic semiconductors are found to be at odds with other well-established concepts in that field, like polaron formation. Addressing these inconsistencies for prototypical systems, we present experimental and theoretical evidence for intermolecular hybridization of organic semiconductor and dopant frontier molecular orbitals. Common doping-related observations are attributed to this phenomenon, and controlling the degree of hybridization emerges as a strategy for overcoming the present limitations in the yield of doping-induced charge carriers.

Electronic structure of pyridine-based SAMs on flat Au(111) surfaces: extended charge rearrangements and Fermi level pinning.

Density functional theory calculations are used to investigate the electronic structure of pyridine-based self-assembled monolayers (SAMs) on an Au(111) surface. We find that, when using pyridine docking groups, the bonding-induced charge rearrangements are frequently found to extend well onto the molecular backbone. This is in contrast to previous observations for the chemisorption of other SAMs, e.

Analysis of Bonding between Conjugated Organic Molecules and Noble Metal Surfaces Using Orbital Overlap Populations.

The electronic structure of metal-organic interfaces is of paramount importance for the properties of organic electronic and single-molecule devices. Here, we use so-called orbital overlap populations derived from slab-type band-structure calculations to analyze the covalent contribution to the bonding between an adsorbate layer and a metal. Using two prototypical molecules, the strong acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) on Ag(111) and the strong donor 1H,1'H-[4,4']bipyridinylidene (HV0) on Au(111), we present overlap populations as particularly versatile tools for describing the metal-organic interaction.

The electronic structure of mixed self-assembled monolayers.

The electronic structure of mixed self-assembled monolayers (SAMs) on Au(111) surfaces is modeled using slab-type density-functional theory calculations. The studied molecules have a dipolar character induced by polar and electron donating or accepting tail-group substituents. The resulting electronic structure of mixed layers is found to differ qualitatively from a simple superposition of those of the respective pure layers.

Modeling the electronic properties of pi-conjugated self-assembled monolayers.

The modification of electrode surfaces by depositing self-assembled monolayers (SAMs) provides the possibility for controlled adjustment of various key parameters in organic and molecular electronic devices. Most important among them are the work function of the electrode and the relative alignment of its Fermi level with the conducting states in the SAM itself and with those in a subsequently deposited organic semiconductor. For the efficient application of such interface modifications it is crucial to reach a proper understanding of the relation between the chemical structure of a molecule, its molecular electronic characteristics, and the properties of the SAM formed by such molecules.

Self-assembled monolayers of polar molecules on Au(111) surfaces: distributing the dipoles.

Quantum-mechanical calculations are performed to investigate the interface between Au(111) surfaces and self-assembled monolayers (SAMs) of organic thiols. Dipolar pyrimidine units act as building blocks to systematically tune the molecular dipole moments via the number of repeat units. The resulting work-function modifications and the energetic alignment of the frontier electronic states in the SAM with the Fermi level are analyzed.

Is there a Au-S bond dipole in self-assembled monolayers on gold?

Self-assembled monolayers (SAMs) of functionalized thiols are widely used in organic (opto)electronic devices to tune the work function, Phi, of noble-metal electrodes and, thereby, to optimize the barriers for charge-carrier injection. The achievable Phi values not only depend on the intrinsic molecular dipole moment of the thiols but, importantly, also on the bond dipole at the Au-S interface. Here, on the basis of extensive density-functional theory calculations, we clarify the ongoing controversy regarding the existence, the magnitude, and the nature of that bond dipole.

Understanding the electronic structure of metal/SAM/organic-semiconductor heterojunctions.

Computational modeling is used to describe the mechanisms governing energy level alignment between an organic semiconductor (OSC) and a metal covered by various self-assembled monolayers (SAMs). In particular, we address the question to what extent and under what circumstances SAM-induced work-function modifications lead to an actual change of the barriers for electron and hole injection from the metal into the OSC layer. Depending on the nature of the SAM, we observe clear transitions between Fermi level pinning and vacuum-level alignment regimes.

A high molecular weight donor for electron injection interlayers on metal electrodes.

The molecular donor 9,9'-ethane-1,2-diylidene-bis(N-methyl-9,10-dihydroacridine) (NMA) has been synthesized, and its electronic properties were characterized both in solution using cyclic voltammetry and optical absorption spectroscopy, and at interfaces to metals with photoelectron spectroscopy (PES). The optical energy gap of NMA in solution increases by 0.10 eV when the compound is doubly oxidized.