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. 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.

Interface properties of organic para-hexaphenyl/α-sexithiophene heterostructures deposited on highly oriented pyrolytic graphite.

It was recently reported, that heterostructures of para-hexaphenyl (p-6P) and α-sexithiophene (6T) deposited on muscovite mica exhibit the intriguing possibility to prepare lasing nanofibers of tunable emission wavelength. For p-6P/6T heterostructures, two different types of 6T emission have been observed, namely, the well-known red emission of bulk 6T crystals and additionally a green emission connected to the interface between p-6P and 6T. In this study, the origin of the green fluorescence is investigated by photoelectron spectroscopy (PES). As a prerequisite, it is necessary to prepare structurally similar organic crystals on a conductive surface, which leads to the choice of highly oriented pyrolytic graphite (HOPG) as a substrate. The similarity between p-6P/6T heterostructures on muscovite mica and on HOPG is evidenced by X-ray diffraction (XRD), scanning force microscopy (SFM), and optical spectroscopy. PES measurements show that the interface between p-6P and 6T crystals is sharp on a molecular level without any sign of interface dipole formation or chemical interaction between the molecules. We therefore conclude that the different emission colors of the two 6T phases are caused by different types of molecular aggregation.

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. The latter is clearly favored, suggesting strategies for the chemical design of more efficient molecular dopants.

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.

Epitaxy of rodlike organic molecules on sheet silicates--a growth model based on experiments and simulations.

During the last years, self-assembled organic nanostructures have been recognized as a proper fundament for several electrical and optical applications. In particular, phenylenes deposited on muscovite mica have turned out to be an outstanding material combination. They tend to align parallel to each other forming needlelike structures. In that way, they provide the key for macroscopic highly polarized emission, waveguiding, and lasing. The resulting anisotropy has been interpreted so far by an induced dipole originating from the muscovite mica substrate. Based on a combined experimental and theoretical approach, we present an alternative growth model being able to explain molecular adsorption on sheet silicates in terms of molecule-surface interactions only. By a comprehensive comparison between experiments and simulations, we demonstrate that geometrical changes in the substrate surface or molecule lead to different molecular adsorption geometries and needle directions which can be predicted by our growth model.

Crystal growth of para-sexiphenyl on clean and oxygen reconstructed Cu(110) surfaces.

The formation of crystalline para-sexiphenyl (6P) films on Cu(110) and Cu(110)-(2 × 1)O (Cu-O) has been studied by low energy electron diffraction, X-ray absorption spectroscopy and both in situ and ex situ X-ray diffraction methods to elucidate the transition from the initial monolayers to crystalline thin films. It is found that, for Cu-O, a single and, for Cu(110), a double wetting layer is formed which then acts as a template for the subsequent 3D crystal growth. For both substrates the orientation of the long molecular axes of the 6P molecules in the first layers is conserved for the molecules in the bulk crystals growing on them. The main difference between both systems is that on Cu-O the first monolayer assembles in a form close to that of a 6P bulk plane which can be easily continued by crystallites grown upon them, while on the Cu(110) surface the 6P mono- and bi-layers differ substantially from the bulk structure. The bi-layer forms a complex periodically striped phase. Thin 6P films grow with the 6P(203) crystal plane parallel to the Cu-O substrate surface. For this orientation, the 6P molecules are stacked in layers and the molecules demonstrate only one tilt of the mean molecular plane with respect to the sample surface. On clean Cu(110), a more complex 6P(629) plane is parallel to the substrate surface and this orientation is likely a consequence of the super-molecular long-range periodicity of the second molecular layer striped phase.

Tuning the ionization energy of organic semiconductor films: the role of intramolecular polar bonds.

For the prototypical conjugated organic molecules pentacene and perfluoropentacene, we demonstrate that the surface termination of ordered organic thin films with intramolecular polar bonds (e.g., -H versus -F) can be used to tune the ionization energy. The collective electrostatics of these oriented bonds also explains the pronounced orientation dependence of the ionization energy. Furthermore, mixing of differently terminated molecules on a molecular length scale allows continuously tuning the ionization energy of thin organic films between the limiting values of the two pure materials. Our study shows that surface engineering of organic semiconductors via adjusting the polarity of intramolecular bonds represents a generally viable alternative to the surface modification of substrates to control the energetics at organic/(in)organic interfaces.

Organic heterojunctions: Contact-induced molecular reorientation, interface states, and charge re-distribution.

We reveal the rather complex interplay of contact-induced re-orientation and interfacial electronic structure - in the presence of Fermi-level pinning - at prototypical molecular heterojunctions comprising copper phthalocyanine (H16CuPc) and its perfluorinated analogue (F16CuPc), by employing ultraviolet photoelectron and X-ray absorption spectroscopy. For both layer sequences, we find that Fermi-level (EF) pinning of the first layer on the conductive polymer substrate modifies the work function encountered by the second layer such that it also becomes EF-pinned, however, at the interface towards the first molecular layer. This results in a charge transfer accompanied by a sheet charge density at the organic/organic interface. While molecules in the bulk of the films exhibit upright orientation, contact formation at the heterojunction results in an interfacial bilayer with lying and co-facial orientation. This interfacial layer is not EF-pinned, but provides for an additional density of states at the interface that is not present in the bulk. With reliable knowledge of the organic heterojunction's electronic structure we can explain the poor performance of these in photovoltaic cells as well as their valuable function as charge generation layer in electronic devices.

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. We identify the limitations of previous attempts to formulate such a model and highlight inconsistencies in the interpretation of the experimental data they were based on. We then develop a theoretical framework, which we demonstrate to accurately reproduce experiment. Applying this theory, a comprehensive overview of all possible energy-level alignment scenarios that can be encountered at organic heterojunctions is finally given. These results will help focus future efforts on developing functional organic interfaces for superior device performance.

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. 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.

Tuning the Electronic Structure of Graphene by Molecular Dopants: Impact of the Substrate.

A combination of ultraviolet and X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and first principle calculations was used to study the electronic structure at the interface between the strong molecular acceptor 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (F6TCNNQ) and a graphene layer supported on either a quartz or a copper substrate. We find evidence for fundamentally different charge redistribution mechanisms in the two ternary systems, as a consequence of the insulating versus metallic character of the substrates. While electron transfer occurs exclusively from graphene to F6TCNNQ on the quartz support (p-doping of graphene), the Cu substrate electron reservoir induces an additional electron density flow to graphene decorated with the acceptor monolayer. Remarkably, graphene on Cu is n-doped and remains n-doped upon F6TCNNQ deposition. On both substrates, the work function of graphene increases substantially with a F6TCNNQ monolayer atop, the effect being more pronounced (∼1.3 eV) on Cu compared to quartz (∼1.0 eV) because of the larger electrostatic potential drop associated with the long-distance graphene-mediated Cu-F6TCNNQ electron transfer. We thus provide a means to realize high work function surfaces for both p- and n-type doped graphene.

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. 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.

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.

Interaction of Isophorone with Pd(111): A Combination of Infrared Reflection-Absorption Spectroscopy, Near-Edge X-ray Absorption Fine Structure, and Density Functional Theory Studies.

Atomistic level understanding of interaction of α,ß-unsaturated carbonyls with late transition metals is a key prerequisite for rational design of new catalytic materials with the desired selectivity toward C=C or C=O bond hydrogenation. The interaction of this class of compounds with transition metals was investigated on α,ß-unsaturated ketone isophorone on Pd(111) as a prototypical system. In this study, infrared reflection-absorption spectroscopy (IRAS), near-edge X-ray absorption fine structure (NEXAFS) experiments, and density functional theory calculations including van der Waals interactions (DFT+vdW) were combined to obtain detailed information on the binding of isophorone to palladium at different coverages and on the effect of preadsorbed hydrogen on the binding and adsorption geometry. According to these experimental observations and the results of theoretical calculations, isophorone adsorbs on Pd(111) in a flat-lying geometry at low coverages. With increasing coverage, both C=C and C=O bonds of isophorone tilt with respect to the surface plane. The tilting is considerably more pronounced for the C=C bond on the pristine Pd(111) surface, indicating a prominent perturbation and structural distortion of the conjugated π system upon interaction with Pd. Preadsorbed hydrogen leads to higher tilting angles of both π bonds, which points to much weaker interaction of isophorone with hydrogen-precovered Pd and suggests the conservation of the in-plane geometry of the conjugated π system. The results of the DFT+vdW calculations provide further insights into the perturbation of the molecular structure of isophorone on Pd(111).

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

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.

Color tuning of nanofibers by periodic organic-organic hetero-epitaxy.

We report on the epitaxial growth of periodic para-hexaphenyl (p-6P)/α-sexi-thiophene (6T) multilayer heterostructures on top of p-6P nanotemplates. By the chosen approach, 6T molecules are forced to align parallel to the p-6P template molecules, which yields highly polarized photoluminescence (PL)-emission of both species. The PL spectra show that the fabricated multilayer structures provide optical emission from two different 6T phases, interfacial 6T molecules, and 3-dimensional crystallites. By a periodical deposition of 6T monolayers and p-6P spacers it is demonstrated that the strongly polarized spectral contribution of interfacial 6T can be precisely controlled and amplified. By analyzing the PL emission of both 6T phases as a function of p-6P spacer thickness (Δd(p-6P)) we have determined a critical value of Δd(p-6P )≈ 2.73 nm where interfacial 6T runs into saturation and the surplus of 6T starts to cluster in 3-dimensional crystallites. These results are further substantiated by UPS and XRD measurements. Moreover, it is demonstrated by morphological investigations, provided by scanning force microscopy and fluorescence microscopy, that periodical deposition of 6T and p-6P leads to a significant improvement of homogeneity in PL-emission and morphology of nanofibers. Photoluminescence excitation experiments in combination with time-resolved photoluminescence demonstrate that the spectral emission of the organic multilayer nanofibers is dominated by a resonant energy transfer from p-6P host- to 6T guest-molecules. The sensitization time of the 6T emission in the 6T/p-6P multilayer structures depends on the p-6P spacer thickness, and can be explained by well separated layers of host-guest molecules obtained by organic-organic heteroepitaxy. The spectral emission and consequently the fluorescent color of the nanofibers can be efficiently tuned from the blue via white to the yellow-green spectral range.

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 3.07 Å, giving rise to significant electronic band dispersion along the π-stacking direction, as evidenced by ultraviolet photoelectron spectroscopy. Our study underlines the high potential of graphene for use as a transparent electrode in (opto-)electronic applications, where optimized vertical transport through flat-lying conjugated organic molecules is desired.

Organic-organic heteroepitaxy of red-, green-, and blue-emitting nanofibers.

Self-assembly processes and organic-organic heteroepitaxy are powerful techniques to obtain highly ordered molecular aggregates. Here we demonstrate that combining both methods allows not only to fabricate highly crystalline and uniaxially oriented self-assembled nanofibers but also to tune their polarized emission. We show that submonolayer coverage of sexithiophene on top of para-sexiphenyl nanofibers is sufficient to change their emission color from blue to green. Triband emission in the red, green, and blue is generated in nanofibers with thicker sexithiophene coverage, where layers of co-oriented crystals are separated by green-emitting molecular sheets.

Structural order in perfluoropentacene thin films and heterostructures with pentacene.

Synchrotron x-ray diffraction reciprocal space mapping was performed on perfluoropentacene (PFP) thin films on SiO2 in order to determine the crystal structure of a novel, substrate-induced thin film phase to be monoclinic with unit cell parameters of a = 15.76 +/- 0.02 A, b = 4.51 +/- 0.02 A, c = 11.48 +/- 0.02 A, and beta = 90.4 +/- 0.1 degrees . Moreover, layered and co-deposited heterostructures of PFP and pentacene (P) were investigated by specular and grazing-incidence x-ray diffraction, atomic force microscopy, and Fourier-transform infrared spectroscopy. For a ca. three-monolayers-thick PFP film grown on a P underlayer, slightly increased lattice spacing was found. In contrast, co-deposited P/PFP films form a new mixed-crystal structure with no detectable degree of phase separation. These results highlight the structural complexity of these technically relevant molecular heterojunctions for use in organic electronics.

The molecular orientation of para-sexiphenyl on Cu(110) and Cu(110) p(2x1)O.

Controlling the molecular growth of organic semiconductors is an important issue to optimize the performance of organic devices. Conjugated molecules, used as building blocks, have an anisotropic shape and also anisotropic physical properties like charge transport or luminescence. The main challenge is to grow highly crystalline layers with molecules of defined orientation. The higher the crystallinity, the closer these properties reach their full intrinsic potential, while the orientation determines the physical properties of the film. Herein we show that the molecular orientation and growth can be steered by the surface chemistry, which tunes the molecule-substrate interaction. In addition, the oxygen reconstruction of the surface, demonstrates the flexibility of the organic molecules to adopt a given surface corrugation and their unique possibility to release stress by tilting.