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. 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 two distinctly different scenarios: the pairwise formation of both organic semiconductor and dopant ions on one hand and the emergence of ground state charge transfer complexes between organic semiconductor and dopant through supramolecular hybridization of their respective frontier molecular orbitals on the other hand. Evidence for the occurrence of these two scenarios is subsequently discussed on the basis of the characteristic and strikingly different signatures of the individual species involved in the respective doping processes in a variety of spectroscopic techniques. The critical importance of a statistical view of doping, rather than a bimolecular picture, is then highlighted by employing numerical simulations, which reveal one of the main differences between inorganic and organic semiconductors to be their respective density of electronic states and the doping induced changes thereof. Engineering the density of states of doped organic semiconductors, the Fermi-Dirac occupation of which ultimately determines the doping efficiency, thus emerges as key challenge. As a first step, the formation of charge transfer complexes is identified as being detrimental to the doping efficiency, which suggests sterically shielding the functional core of dopant molecules as an additional design rule to complement the requirement of low ionization energies or high electron affinities in efficient n-type or p-type dopants, respectively. In an extended outlook, we finally argue that, to fully meet this challenge, an improved understanding is required of just how the admixture of dopant molecules to organic semiconductors does affect the density of states: compared with their inorganic counterparts, traps for charge carriers are omnipresent in organic semiconductors due to structural and chemical imperfections, and Coulomb attraction between ionized dopants and free charge carriers is typically stronger in organic semiconductors owing to their lower dielectric constant. Nevertheless, encouraging progress is being made toward developi...

S. Duhm et al., Nature Materials, acceptedWhile an isolated individual molecule clearly has only one ionization potential, multiple values are found for molecules in ordered assemblies. Photoelectron spectroscopy of archetypical π-conjugated organic compounds on metal substrates combined with first-principles calculations and electrostatic modeling reveal the existence of a surface dipole built into molecular layers. Conceptually different from the surface dipole at metal surfaces, its origin lies in details of the molecular electronic structure and its magnitude depends on the orientation of molecules relative to the surface of an ordered assembly. Suitable pre-patterning of substrates to induce specific molecular orientations in subsequently grown films thus permits adjusting the ionization potential of one molecular species over up to 0.6 eV via control over monolayer morphology. In addition to providing in-depth understanding of this phenomenon, our study offers design guidelines for improved organic/organic heterojunctions, hole-or electron-blocking layers, and reduced barriers for charge-carrier injection in organic electronic devices. S. Duhm et al., Nature Materials, acceptedIt is well established that the work function (Φ) of metals depends on the crystal face 1-3 .Φ is defined as the energy difference between the Fermi level (E F ) and the electrostatic potential above the sample, the vacuum level (V vac ). For, e.g., copper, Φs of the (100), (110), and (111) surfaces are spread over a range of 0.5 eV 1,2 . As E F is constant, this observation has been explained by the difference in the intrinsic "surface dipole": Differences in the geometric and, consequently, electronic structure cause a different amount of the electronic cloud to spill out of the bulk into the vacuum 3, 4 . The resulting dipole raises V vac to a larger or smaller extent and thus impacts Φ 4, 5 . Note that this effect can only be observed for laterally extended surfaces, as the spatial region above the sample where V vac is raised reaches farther away from the surface with increasing sample size (i.e., area of the exposed surface) 6, 7 . Small metal clusters with multiple facets of different crystal orientations have only one well-defined work function 8, 9 .For van der Waals (i.e., non-covalent) crystals of non-dipolar molecules, surface dipoles and work-function anisotropy have not yet been explored 6 . While variations of the ionization potential (IP; the molecular equivalent of the work function) depending on the molecular orientation on a substrate have been reported before [10][11][12][13][14][15][16] , the prevalent interpretation in terms of variable photo-hole screening could never be satisfactorily quantified. Here, we propose a qualitatively different and novel explanation for the intriguing observation that one and the same molecule can have different -still welldefined -IPs if part of an ordered supramolecular structure. S. Duhm et al., Nature Materials, acceptedWe performed X-ray photoelectron spectroscopy (XPS) and u...

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.

Self-assembled monolayers (SAMs) of organic molecules generally modify the surface properties when covalently linked to substrates. In organic electronics, SAMs are used to fine-tune the work functions of inorganic electrodes, thereby minimizing the energy barriers for injection or extraction of charge carriers into or out of an active organic layer; a detailed understanding of the interface energetics on an atomistic scale is required to design improved interfaces. In the field of molecular electronics, the SAM itself (or, in some cases, one or a few molecules) carries the entire device functionality; the interface then essentially becomes the device and the alignment of the molecular energy levels with those of the electrodes defines the overall charge-transport characteristics. This Account provides a review of recent theoretical studies of the interface energetics for SAMs of π-conjugated molecules covalently linked to noble metal surfaces. After a brief description of the electrostatics of dipole layers at metal/molecule interfaces, the results of density functional theory calculations are discussed for SAMs of representative conjugated thiols on Au(111). Particular emphasis is placed on the modification of the work function of the clean metal surface upon SAM formation, the alignment of the energy levels within the SAM with the metal Fermi level, and the connection between these two quantities. To simplify the discussion, we partition the description of the metal/SAM system into two parts by considering first an isolated free-standing layer of molecules and then the system obtained after molecule-metal bond formation. From an electrostatic standpoint, both the isolated monolayer and the metal-molecule bonds can be cast in the form of dipole layers, which lead to steps in the electrostatic potential energy at the interface. While the step due to the isolated molecular layer impacts only the work function of the SAM-covered surface, the step arising from the bond formation influences both the work function and the alignment of the electronic levels in the SAM with respect to the metal Fermi energy. Interestingly, headgroup substitutions at the far ends of the molecules forming the SAM are electrostatically decoupled from the metal-thiol interface in densely packed SAMs; as a result, the nature of these substituents and the binding chemistry between the metal and the molecules are two largely unrelated handles with which to independently tune the work function and the level alignment. The establishment of a comprehensive atomistic picture regarding the impact of the individual components of a SAM on the interface energetics at metal/organic junctions paves the way for clear guidelines to design improved functional interfaces in organic and molecular electronics.

The energetics at the interfaces between metal and monolayers of covalently bound organic molecules is studied theoretically. Despite the molecules under consideration displaying very different frontier orbital energies, the highest occupied molecular levels are found to be pinned at a constant energy offset with respect to the metal Fermi level. In contrast, the molecular properties strongly impact the metal work function. These interfacial phenomena are rationalized in terms of charge fluctuations and electrostatics at the atomic length scale as determined by first-principles calculations.

Self-assembled monolayers (SAMs) of organic molecules provide an important tool to tune the work function of electrodes in plastic electronics and significantly improve device performance. Also, the energetic alignment of the frontier molecular orbitals in the SAM with the Fermi energy of a metal electrode dominates charge transport in single-molecule devices. On the basis of first-principles calculations on SAMs of pi-conjugated molecules on noble metals, we provide a detailed description of the mechanisms that give rise to and intrinsically link these interfacial phenomena at the atomic level. The docking chemistry on the metal side of the SAM determines the level alignment, while chemical modifications on the far side provide an additional, independent handle to modify the substrate work function; both aspects can be tuned over several eV. The comprehensive picture established in this work provides valuable guidelines for controlling charge-carrier injection in organic electronics and current-voltage characteristics in single-molecule devices.

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.

Interface energetics are of fundamental importance in organic and molecular electronics. By combining complementary experimental techniques and first-principles calculations, we resolve the complex interplay among several interfacial phenomena that collectively determine the electronic structure of the strong electron acceptor tetrafluoro-tetracyanoquinodimethane chemisorbed on copper. The combination of adsorption-induced geometric distortion of the molecules, metal-to-molecule charge transfer, and molecule-to-metal back transfer leads to a net increase of the metal work function.