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. However, the traditional view on these energy levels and their occupation is incompatible with expected changes in electron removal and addition energies upon charging molecules. Here, I demonstrate that local Coulomb repulsion, as captured by nonempirically optimized electronic-structure calculations, restores compatibility and suggests a different origin of the charge-induced optical transitions. These results challenge a widely accepted and long-established picture, but an improved understanding of charge carriers in molecular materials promises a more targeted development of organic and hybrid organic/inorganic (opto-)electronic devices.
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 developing a unifying picture that captures the entire range of doping induced phenomena, from ion-pair to complex formation, in both conjugated polymers and molecules. Once completed, such a picture will provide viable guidelines for synthetic and supramolecular chemistry that will enable further technological advances in organic and hybrid organic/inorganic 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.
Progress in the field of organic electronics depends on the synthesis of new π-conjugated molecules to further improve the performance of, for example, organic light-emitting diodes, organic ...photovoltaic cells, and organic field-effect transistors. However, the interrelation between the properties of isolated molecules on one hand and close-packed thin films on the other hand is far from trivial. Here, we review recent progress in the understanding of electrostatic phenomena, which originate in the collective action of the anisotropic charge distribution in typical conjugated molecules. Both the π-electron systems and polar end-group substitutions exposed at the surface of a molecular or polymeric film are seen to form dipole layers, which critically impact the device-relevant ionization energy and electron affinity of that film. After briefly revisiting electrostatic fundamentals and critically assessing related experimental methods, the energies of the frontier electronic states in organic thin films are shown to depend appreciably on the orientation of the constituent molecules with respect to device-relevant interfaces. For films of preferentially “standing” or “edge-on” molecules, this opens the possibility for electronic-structure engineering with intramolecular polar bonds. On the basis of these findings, additional insights into the working principles of organic electronic devices are provided and valuable guidelines for the synthesis of improved organic semiconductors are derived.
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.
Zinc oxide (ZnO) is regarded as a promising alternative material for transparent conductive electrodes in optoelectronic devices. However, ZnO suffers from poor chemical stability. ZnO also has a ...moderate work function (WF), which results in substantial charge injection barriers into common (organic) semiconductors that constitute the active layer in a device. Controlling and tuning the ZnO WF is therefore necessary but challenging. Here, a variety of phosphonic acid based self‐assembled monolayers (SAMs) deposited on ZnO surfaces are investigated. It is demonstrated that they allow the tuning the WF over a wide range of more than 1.5 eV, thus enabling the use of ZnO as both the hole‐injecting and electron‐injecting contact. The modified ZnO surfaces are characterized using a number of complementary techniques, demonstrating that the preparation protocol yields dense, well‐defined molecular monolayers.
The tuning of the ZnO work function from 4.1 to 5.7 eV is realized by the application of a variety of phosphonic acid based self‐assembled monolayers (SAMs). This enables the use of ZnO as both the electron‐ and hole‐injecting contact. The homogenous dense packing of the SAMs is thoroughly characterized using a range of complementary techniques.
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.
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. We found that the amount of charge transfer is determined, to a significant extent, by the ratio of the lateral spacing of the molecules and their distance to the metal. Therefore, charge transfer does not only depend on the electronic structure of the individual components but, just as importantly, on the interface geometry.
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