Molecular parameters responsible for thermally activated transport in doped organic semiconductors.

Doped organic semiconductors typically exhibit a thermal activation of their electrical conductivity, whose physical origin is still under scientific debate. In this study, we disclose relationships between molecular parameters and the thermal activation energy (EA) of the conductivity, revealing that charge transport is controlled by the properties of host-dopant integer charge transfer complexes (ICTCs) in efficiently doped organic semiconductors. At low doping concentrations, charge transport is limited by the Coulomb binding energy of ICTCs, which can be minimized by systematic modification of the charge distribution on the individual ions. The investigation of a wide variety of material systems reveals that static energetic disorder induced by ICTC dipole moments sets a general lower limit for EA at large doping concentrations. The impact of disorder can be reduced by adjusting the ICTC density and the intramolecular relaxation energy of host ions, allowing an increase of conductivity by many orders of magnitude.

Electronic structure of dipeptides in the gas-phase and as an adsorbed monolayer.

Peptide-based molecular electronic devices are promising due to the large diversity and unique electronic properties of biomolecules. These electronic properties can change considerably with peptide structure, allowing diverse design possibilities. In this work, we explore the effect of the side-chain of the peptide on its electronic properties, by using both experimental and computational tools to detect the electronic energy levels of two model peptides. The peptides include 2Ala and 2Trp as well as their 3-mercaptopropionic acid linker which is used to form monolayers on an Au surface. Specifically, we compare experimental ultraviolet photoemission spectroscopy measurements with density functional theory based computational results. By analyzing differences in frontier energy levels and molecular orbitals between peptides in gas-phase and in a monolayer on gold, we find that the electronic properties of the peptide side-chain are maintained during binding of the peptide to the gold substrate. This indicates that the energy barrier for the peptide electron transport can be tuned by the amino acid compositions, which suggests a route for structural design of peptide-based electronic devices.

Self-Assembly of Tetraphenyldibenzoperiflanthene (DBP) Films on Ag(111) in the Monolayer Regime.

Tetraphenyldibenzoperiflanthene (DBP) is a promising candidate as a component of highly efficient organic photovoltaic cells and organic light-emitting diodes. The structural properties of thin films of this particular lander-type molecule on Ag(111) were investigated by complementary techniques. Highly ordered structures were obtained, and their mutual alignment was characterized by means of low-energy electron diffraction (LEED). Scanning tunneling microscopy (STM) images reveal two slightly different arrangements within the first monolayer (ML), both describable as specific herringbone patterns with two molecules per unit cell whose dibenzoperiflanthene framework is parallel to the surface. In contrast, single DBP molecules in the second ML were imaged with much higher intramolecular resolution, resembling the shape of the frontier orbitals in the gas phase as calculated by means of density functional theory (DFT). Further deposition leads to the growth of highly ordered bilayer islands on top of the first ML with identical unit cell dimensions and orientation but slightly inclined molecules. This suggests that the first ML acts as a template for the epitaxial growth of further layers. Simultaneously, a significant number of second-layer molecules mainly located at step edges or scattered over narrow terraces do not form highly ordered aggregates.

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. In these cases, the energy-level alignment is governed by chalcogen-derived interface states in the vicinity of the metal Fermi-level. In this work, we present X-ray and ultraviolet photoelectron spectroscopy data that demonstrate that the interfacial energy-level alignment mechanism found for chalcogenol SAMs also applies to seleno-functionalized COMs. This can be exploited to mitigate the push-back effect at metal contacts, notably also when COMs with low ionization energies are employed, permitting exceedingly low hole injection barriers, as shown here for the interfaces of tetraseleno-tetracene with Au(111), Ag(111), and Cu(111).

Understanding the adsorption of CuPc and ZnPc on noble metal surfaces by combining quantum-mechanical modelling and photoelectron spectroscopy.

Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

Recoil effects in valence band photoemission of organic solids.

Recoil effects in valence band X-ray photoelectron spectroscopy (XPS) are studied for both abb-trifluorostyrene and styrene molecular crystal systems. The gradual changes of XPS spectra excited by several photon energies are theoretically investigated within the tight-binding approximation and harmonic approximation of lattice vibrations and have been explained in terms of not only atomic mass but also atomic orbital (AO) population. The recoil effect of valence band photoemission strongly depends on the population and partial photoionization cross section (PICS) of AOs as well as the masses of composite atoms. In abb-trifluorostyrene F 2p dominant bands show the recoil shift close to free F atom recoil shift, and C 2s dominant bands show that to free C atom recoil shift, whereas the mixed bands of C and F give rise to the peak asymmetries due to their different recoil shifts. For these systems, hydrogen contribution is negligibly small which is in contrast to our previous results for the crystals composed of small organic molecules. We also discuss some potential uses of the recoil shifts for these systems.

Gap states in pentacene thin film induced by inert gas exposure.

We studied gas-exposure effects on pentacene (Pn) films on SiO2 and Au(111) substrates by ultrahigh sensitivity photoelectron spectroscopy, which can detect the density of states of ∼10(16) states eV-1 cm-3 comparable to electrical measurements. The results show the striking effects for Pn/SiO2: exposure to inert gas (N2 and Ar) produces a sharp rise in gap states from ∼10(16) to ∼10(18) states eV-1 cm-3 and pushes the Fermi level closer to the valence band (0.15-0.17 eV), as does exposure to O2 (0.20 eV), while no such gas-exposure effect is observed for Pn/Au(111). The results demonstrate that these gap states originate from small imperfections in the Pn packing structure, which are induced by gas penetration into the film through the crystal grain boundaries.

Reversible single-molecule switching in an ordered monolayer molecular dipole array.

Making electronic devices using a single molecule has been the ultimate goal of molecular electronics. For binary data storage in particular, the challenge has been the ability to switch a single molecule in between bistable states in a simple and repeatable manner. The reversible switching of single molecules of chloroaluminum phthalocyanine (ClAlPc) dipolar molecules within a close-packed monolayer is demonstrated. By pulsing an scanning tunneling microscopy tip, read-write operations of single-molecular binary bits at ~40 Tb/cm(2) (~250 Tb/in(2)) are demonstrated.

Accessing surface Brillouin zone and band structure of picene single crystals.

We have experimentally revealed the band structure and the surface Brillouin zone of insulating picene single crystals (SCs), the mother organic system for a recently discovered aromatic superconductor, with ultraviolet photoelectron spectroscopy (UPS) and low-energy electron diffraction with a laser for photoconduction. A hole effective mass of 2.24m(0) and the hole mobility µ(h)≥9.0 cm(2)/V s (298 K) were deduced in the Γ-Y direction. We have further shown that some picene SCs did not show charging during UPS even without the laser, which indicates that pristine UPS works for high-quality organic SCs.

Accessing the Conduction Band Dispersion in CH3NH3PbI3 Single Crystals.

The conduction band dispersion in methylammonium lead iodide (CH3NH3PbI3) was studied by both angle-resolved two-photon photoelectron spectroscopy (AR-2PPE) with low photon intensity (∼0.0125 nJ/pulse) and angle-resolved low-energy inverse photoelectron spectroscopy (AR-LEIPS). Clear energy dispersion of the conduction band along the Γ-M direction was first observed by these independent methods under different temperatures, and the dispersion was found to be consistent with band calculation under the cubic phase. The effective mass of the electrons at the Γ point was estimated to be (0.20 ± 0.05)m0 at the temperature of 90 K. The observed conduction band energy was different between the AR-LEIPS and AR-2PPE, which was ascribed to the electronic-correlation-dependent difference of initial and final states probing processes. The present results also indicate that the surface structure in CH3NH3PbI3 provides the cubic-dominated electronic property even at lower temperatures.

Highest-occupied-molecular-orbital band dispersion of rubrene single crystals as observed by angle-resolved ultraviolet photoelectron spectroscopy.

The electronic structure of rubrene single crystals was studied by angle-resolved ultraviolet photoelectron spectroscopy. A clear energy dispersion of the highest occupied molecular orbital-derived band was observed, and the dispersion width was found to be 0.4 eV along the well-stacked direction. The effective mass of the holes was estimated to be 0.65(+/-0.1)m0. The present results suggest that the carrier conduction mechanism in rubrene single crystals can be described within the framework of band transport.

Peculiar Rashba splitting originating from the two-dimensional symmetry of the surface.

A peculiar Rashba effect is found at a point in the Brillouin zone, where the time-reversal symmetry is broken, though this symmetry was believed to be a necessary condition for Rashba splitting. This finding obtained experimentally by photoemission measurements on a Bi/Si(111)-(sqrt(3) x sqrt(3)) surface is fully confirmed by a first-principles theoretical calculation. We found that the peculiar Rashba effect is simply understood by the two-dimensional symmetry of the surface, and that this effect leads to an unconventional nonvortical Rashba spin structure at a point with time-reversal invariance.

Single-Crystal Pentacene Valence-Band Dispersion and Its Temperature Dependence.

The electronic structures of the highest occupied molecular orbital (HOMO) or the HOMO-derived valence bands dominate the transport nature of positive charge carriers (holes) in organic semiconductors. In the present study, the valence-band structures of single-crystal pentacene and the temperature dependence of their energy-momentum dispersion relations are successfully demonstrated using angle-resolved ultraviolet photoelectron spectroscopy (ARUPS). For the shallowest valence band, the intermolecular transfer integral and effective mass of the holes are evaluated as 43.1 meV and 3.43 times the electron rest mass, respectively, at room temperature along the crystallographic direction for which the widest energy dispersion is expected. The temperature dependence of the ARUPS results reveals that the transfer integral values (hole effective mass) are enhanced (reduced) by ∼20% on cooling the sample to 110 K.

Radiation damage to alkyl chain monolayers on semiconductor substrates investigated by electron spectroscopy.

Monolayers of alkyl chains, attached through direct Si-C bonds to Si(111), via phosphonates to GaAs(100) surfaces, or deposited as alkyl-silane monolayers on SiO2, are investigated by ultraviolet and inverse photoemission spectroscopy and X-ray absorption spectroscopy. Exposure to ultraviolet radiation from a He discharge lamp, or to a beam of energetic electrons, leads to significant damage, presumably associated with radiation- or electron-induced H-abstraction leading to carbon-carbon double-bond formation in the alkyl monolayer. The damage results in an overall distortion of the valence spectrum, in the appearance of (occupied) states above the highest occupied molecular orbital of the alkyl molecule, and in a characteristic (unoccupied state) pi resonance at the edge of the carbon absorption peak. These distortions present a serious challenge for the interpretation of the electronic structure of the monolayer system. We show that extrapolation to zero damage at short exposure times eliminates extrinsic features and allows a meaningful extraction of the density of state of the pristine monolayer from spectroscopy measurements.

High-resolution core-level photoemission measurements on the pentacene single crystal surface assisted by photoconduction.

Upon charge carrier transport behaviors of high-mobility organic field effect transistors of pentacene single crystal, effects of ambient gases and resultant probable 'impurities' at the crystal surface have been controversial. Definite knowledge on the surface stoichiometry and chemical composites is indispensable to solve this question. In the present study, high-resolution x-ray photoelectron spectroscopy (XPS) measurements on the pentacene single crystal samples successfully demonstrated a presence of a few atomic-percent of (photo-)oxidized species at the first molecular layer of the crystal surface through accurate analyses of the excitation energy (i.e. probing depth) dependence of the C1s peak profiles. Particular methodologies to conduct XPS on organic single crystal samples, without any charging nor damage of the sample in spite of its electric insulating character and fragility against x-ray irradiation, is also described in detail.

Mechanism for doping induced p type C60 using thermally evaporated molybdenum trioxide (MoO3) as a dopant.

Thermally evaporated molybdenum trioxide (MoO3) doped C60 films, which could change n type features of pristine C60 to form a p type mixed C60 layer, are investigated by x-ray and ultraviolet photoelectron spectroscopy. It is found that C60 HOMO progressively shifts closer to the Fermi level after increased MoO3 doping concentration, and final onset of C60 HOMO is pinned at binding energy of 0.20 eV, indicating the formation of p type C60 films. It is proposed that in charge transfer induced p type C60 formation, due to large electron affinity of MoO3 (6.37 eV), electrons from HOMO of C60 could easily transfer to MoO3 to form cations and therefore increase hole concentration, which could gradually push C60 HOMO to the Fermi level and finally form p type C60 films. Moreover, clear different types of C60 species have been confirmed from UPS spectra in highly doped films.

Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes.

Epitaxial Growth of an Organic p-n Heterojunction: C60 on Single-Crystal Pentacene.

Designing molecular p-n heterojunction structures, i.e., electron donor-acceptor contacts, is one of the central challenges for further development of organic electronic devices. In the present study, a well-defined p-n heterojunction of two representative molecular semiconductors, pentacene and C60, formed on the single-crystal surface of pentacene is precisely investigated in terms of its growth behavior and crystallographic structure. C60 assembles into a (111)-oriented face-centered-cubic crystal structure with a specific epitaxial orientation on the (001) surface of the pentacene single crystal. The present experimental findings provide molecular scale insights into the formation mechanisms of the organic p-n heterojunction through an accurate structural analysis of the single-crystalline molecular contact.

Energy level realignment in weakly interacting donor-acceptor binary molecular networks.

Understanding the effect of intermolecular and molecule-substrate interactions on molecular electronic states is key to revealing the energy level alignment mechanism at organic-organic heterojunctions or organic-inorganic interfaces. In this paper, we investigate the energy level alignment mechanism in weakly interacting donor-acceptor binary molecular superstructures, comprising copper hexadecafluorophthalocyanine (F16CuPc) intermixed with copper phthalocyanine (CuPc), or manganese phthalocynine (MnPc) on graphite. The molecular electronic structures have been systematically studied by in situ ultraviolet photoelectron spectroscopy (UPS) and low-temperature scanning tunneling microscopy/spectroscopy (LT-STM/STS) experiments and corroborated by density functional theory (DFT) calculations. As demonstrated by the UPS and LT-STM/STS measurements, the observed unusual energy level realignment (i.e., a large downward shift in donor HOMO level and a corresponding small upward shift in acceptor HOMO level) in the CuPc-F16CuPc binary superstructures originates from the balance between intermolecular and molecule-substrate interactions. The enhanced intermolecular interactions through the hydrogen bonding between neighboring CuPc and F16CuPc can stabilize the binary superstructures and modify the local molecular electronic states. The obvious molecular energy level shift was explained by gap-state-mediated interfacial charge transfer.

Pentacene on Ag(111): correlation of bonding distance with intermolecular interaction and order.

We report coverage and temperature dependent bonding distances of vacuum-sublimed pentacene (PEN) submonolayers on Ag(111) obtained by the X-ray standing wave technique. The average vertical bonding distance of 2.98 Å at room temperature for 0.50 monolayer (ML) coverage increases to 3.12 Å for 0.75 ML due to competing intermolecular and adsorbate-substrate interactions. In contrast, decreasing the temperature from 295 to 145 K does not impact the bonding distance despite the concomitant transition from a "liquidlike" to an ordered molecular arrangement. In combination with X-ray photoelectron spectroscopy results, we could identify "soft chemisorption" with a subtle balance of molecule-molecule and substrate-molecule interactions as being responsible for this special adsorption behavior. Thus our study sheds light not only on the interface between PEN and Ag(111), but also on fundamental adsorption processes of organic adsorbates on metals in the context of chemi- and physisorption.