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Photoelectron spectra were measured for films of self-assembled azobenzene-terminated alkanethiol monolayers on gold using synchroton radiation. As a result of the orientational order of the molecules within the films, it is possible to identify laser-induced optical switching of the molecules using combined laser and synchrotron pulses.

Research into the formation of negatively charged species in electroluminescent p-sexiphenyl by the use of ultraviolet photoelectron spectroscopy is described.

Strong molecular dopants for organic semiconductors that are stable against diffusion are in demand, enhancing the performance of organic optoelectronic devices. The conventionally used p-dopants based on 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its derivatives "F x TCN(N)Q", such as 2,3,4,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (F6TCNNQ), feature limited oxidation strength, especially for modern polymer semiconductors with high ionization energy (IE). These small molecular dopants also exhibit pronounced diffusion in the polymer hosts. Here, we demonstrate a facile approach to increase the oxidation strength of F x TCN(N)Q by coordination with four tris(pentafluorophenyl)borane (BCF) molecules using a single-step solution mixing process, resulting in bulky dopant complexes "F x TCN(N)Q-4(BCF)". Using a series of polymer semiconductors with IE up to 5.9 eV, we show by optical absorption spectroscopy of solutions and thin films that the efficiency of doping using F x TCN(N)Q-4(BCF) is significantly higher compared to that using F x TCN(N)Q or BCF alone. Electrical transport measurements with the prototypical poly(3-hexylthiophene-2,5-diyl) (P3HT) confirm the higher doping efficiency of F4TCNQ-4(BCF) compared to F4TCNQ. Additionally, the bulkier structure of F4TCNQ-4(BCF) is shown to result in higher stability against drift in P3HT under an applied electric field as compared to F4TCNQ. The simple approach of solution-mixing of readily accessible molecules thus offers access to enhanced molecular p-dopants for the community.

In perovskite solar cells (PSCs) energy level alignment and charge extraction at the interfaces are the essential factors directly affecting the device performance. In this work, we present a modified interface between all-inorganic CsPbI 3 perovskite and its hole-selective contact (spiro-OMeTAD), realized by the dipole molecule trioctylphosphine oxide (TOPO), to align the energy levels. On a passivated perovskite film, with n -octylammonium iodide (OAI), we created an upward surface band-bending at the interface by TOPO treatment. This improved interface by the dipole molecule induces a better energy level alignment and enhances the charge extraction of holes from the perovskite layer to the hole transport material. Consequently, a V oc of 1.2 V and a high-power conversion efficiency (PCE) of over 19% were achieved for inorganic CsPbI 3 perovskite solar cells. Further, to demonstrate the effect of the TOPO dipole molecule, we present a layer-by-layer charge extraction study by a transient surface photovoltage (trSPV) technique accomplished by a charge transport simulation., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The modern picture of negative charge carriers on conjugated polymers invokes the formation of a singly occupied (spin-up/spin-down) level within the polymer gap and a corresponding unoccupied level above the polymer conduction band edge. The energy splitting between these sublevels is related to on-site Coulomb interactions between electrons, commonly termed Hubbard U . However, spectral evidence for both sublevels and experimental access to the U value is still missing. Here, we provide evidence by n-doping the polymer P(NDI2OD-T 2 ) with [RhCp*Cp] 2 , [N-DMBI] 2 , and cesium. Changes in the electronic structure after doping are studied with ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). UPS data show an additional density of states (DOS) in the former empty polymer gap while LEIPES data show an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of ∼1 eV.

The wide band gap semiconductor κ-Ga 2 O 3 and its aluminum and indium alloys have been proposed as promising materials for many applications. One of them is the use of inter-sub-band transitions in quantum-well (QW) systems for infrared detectors. Our simulations show that the detection wavelength range of nowadays state of the art GaAs/Al x Ga 1- x As quantum-well infrared photodetectors (QWIPs) could be substantially excelled with about 1-100 μm using κ-([Al,In] x Ga 1- x ) 2 O 3 , while at the same time being transparent to visible light and therefore insensitive to photon noise due to its wide band gap, demonstrating the application potential of this material system. Our simulations further show that the QWIPs efficiency critically depends on the QW thickness, making a precise control over the thickness during growth and a reliable thickness determination essential. We demonstrate that pulsed laser deposition yields the needed accuracy, by analyzing a series of (In x Ga 1- x ) 2 O 3 QWs with (Al y Ga 1- y ) 2 O 3 barriers with high-resolution X-ray diffraction, X-ray photoelectron spectroscopy (XPS) depth profiling, and transmission electron microscopy (TEM). While the superlattice fringes of high-resolution X-ray diffraction only yield an average combined thickness of the QWs and the barrier and X-ray spectroscopy depth profiling requires elaborated modeling of the XPS signal to accurately determine the thickness of such QWs, TEM is the method of choice when it comes to the determination of QW thicknesses.

Niobium pentoxides have received considerable attention and are promising anode materials for lithium-ion batteries (LIBs), due to their fast Li storage kinetics and high capacity. However, their cycling stability and rate performance are still limited owing to their intrinsic insulating properties and structural degradation during charging and discharging. Herein, a series of mesoporous Nb 2 O 5 @TiO 2 core-shell spherical heterostructures have been prepared for the first time by a sol-gel method and investigated as anode materials in LIBs. Mesoporosity can provide numerous open and short pathways for Li + diffusion; meanwhile, heterostructures can simultaneously enhance the electronic conductivity and thus improve the rate capability. The TiO 2 coating layer shows robust crystalline skeletons during repeated lithium insertion and extraction processes, retaining high structural integrity and, thereby, enhancing cycling stability. The electrochemical behavior is strongly dependent on the thickness of the TiO 2 layer. After optimization, a mesoporous Nb 2 O 5 @TiO 2 core-shell structure with a ∼13 nm thick TiO 2 layer delivers a high specific capacity of 136 mA h g -1 at 5 A g -1 and exceptional cycling stability (88.3% retention over 1000 cycles at 0.5 A g -1 ). This work provides a facile strategy to obtain mesoporous Nb 2 O 5 @TiO 2 core-shell spherical structures and underlines the importance of structural engineering for improving the performance of battery materials.

The ability to insolubilize doped semiconducting polymer layers can help enable the fabrication of efficient multilayer solution-processed electronic and optoelectronic devices. Here, we present a promising approach to simultaneously n-dope and largely insolubilize conjugated polymer films using tetrakis[{4-(1,3-dimethyl-2,3-dihydro-1 H -benzo[ d ]imidazol-2-yl)phenoxy}methyl]methane (tetrakis-O-DMBI-H), which consists of four 2,3-dihydro-1 H -benzoimidazole (DMBI-H) n-dopant moieties covalently linked to one another. Doping a thiophene-fused benzodifurandione-based oligo( p -phenylenevinylene)- co -thiophene polymer (TBDOPV-T) with tetrakis-O-DMBI-H results in a highly n-doped film with bulk conductivity of 15 S cm -1 . Optical absorption spectra provide evidence for film retention of ∼93% after immersion in o -dichlorobenzene for 5 min. The optical absorption signature of the charge carriers in the n-doped polymer decreases only slightly more than that of the neutral polymer under these conditions, indicating that the exposure to solvent also results in negligible dedoping of the film. Moreover, thermal treatment studies on a tetrakis-O-DMBI-H-doped TBDOPV-T film in contact with another undoped polymer film indicate immobilization of the molecular dopant in TBDOPV-T. This is attributed to the multiple electrostatic interactions between each dopant tetracation and up to four nearby anionic doped polymer segments.

Surface-defect passivation is key to achieving a high photoluminescence quantum yield in lead halide perovskite nanocrystals. However, in perovskite light-emitting diodes, these surface ligands also have to enable balanced charge injection into the nanocrystals to yield high efficiency and operational lifetime. In this respect, alkaline halides have been reported to passivate surface trap states and increase the overall stability of perovskite light emitters. On the one side, the incorporation of alkaline ions into the lead halide perovskite crystal structure is considered to counterbalance cation vacancies, whereas on the other side, the excess halides are believed to stabilize the colloids. Here, we report an organic lithium salt, viz. LiTFSI, as a halide-free surface passivation on perovskite nanocrystals. We show that treatment with LiTFSI has multiple beneficial effects on lead halide perovskite nanocrystals and LEDs derived from them. We obtain a higher photoluminescence quantum yield and a longer exciton lifetime and a radiation pattern that is more favorable for light outcoupling. The ligand-induced dipoles on the nanocrystal surface shift their energy levels toward a lower hole-injection barrier. Overall, these effects add up to a 4- to 7-fold boost of the external quantum efficiency in proof-of-concept LED structures, depending on the color of the used lead halide perovskite nanocrystal emitters.

Heterostructures made from metal oxide semiconductors (MOS) are fundamental for the development of high-performance gas sensors. Since their importance in real applications, a thorough understanding of the transduction mechanism is vital, whether it is related to a heterojunction or simply to the shell and core materials. A better understanding of the sensing response of heterostructured nanomaterials requires the engineering of heterojunctions with well-defined core and shell layers. Here, we introduce a series of prototypes CNT- n MOS, CNT- p MOS, CNT- p MOS- n MOS, and CNT- n MOS- p MOS hierarchical core-shell heterostructures (CSHS) permitting us to directly relate the sensing response to the MOS shell or to the p-n heterojunction. The carbon nanotubes are here used as highly conductive substrates permitting operation of the devices at relatively low temperature and are not involved in the sensing response. NiO and SnO 2 are selected as representative p- and n-type MOS, respectively, and the response of a set of samples is studied toward hydrogen considered as model analyte. The CNT- n,p MOS CSHS exhibit response related to the n,p MOS-shell layer. On the other hand, the CNT- p MOS- n MOS and CNT- n MOS- p MOS CSHS show sensing responses, which in certain cases are governed by the heterojunctions between n MOS and p MOS and strongly depends on the thickness of the MOS layers. Due to the fundamental nature of this study, these findings are important for the development of next generation gas sensing devices.

Electronic doping in organic materials has remained an elusive concept for several decades. It drew considerable attention in the early days in the quest for organic materials with high electrical conductivity, paving the way for the pioneering work on pristine organic semiconductors (OSCs) and their eventual use in a plethora of applications. Despite this early trend, however, recent strides in the field of organic electronics have been made hand in hand with the development and use of dopants to the point that are now ubiquitous. Here, we give an overview of all important advances in the area of doping of organic semiconductors and their applications. We first review the relevant literature with particular focus on the physical processes involved, discussing established mechanisms but also newly proposed theories. We then continue with a comprehensive summary of the most widely studied dopants to date, placing particular emphasis on the chemical strategies toward the synthesis of molecules with improved functionality. The processing routes toward doped organic films and the important doping-processing-nanostructure relationships, are also discussed. We conclude the review by highlighting how doping can enhance the operating characteristics of various organic devices.

A comprehensive understanding of the energy level alignment mechanisms between two-dimensional (2D) semiconductors and electrodes is currently lacking, but it is a prerequisite for tailoring the interface electronic properties to the requirements of device applications. Here, we use angle-resolved direct and inverse photoelectron spectroscopy to unravel the key factors that determine the level alignment at interfaces between a monolayer of the prototypical 2D semiconductor MoS 2 and conductor, semiconductor, and insulator substrates. For substrate work function (Φ sub ) values below 4.5 eV we find that Fermi level pinning occurs, involving electron transfer to native MoS 2 gap states below the conduction band. For Φ sub above 4.5 eV, vacuum level alignment prevails but the charge injection barriers do not strictly follow the changes of Φ sub as expected from the Schottky-Mott rule. Notably, even the trends of the injection barriers for holes and electrons are different. This is caused by the band gap renormalization of monolayer MoS 2 by dielectric screening, which depends on the dielectric constant (ε r ) of the substrate. Based on these observations, we introduce an expanded Schottky-Mott rule that accounts for band gap renormalization by ε r -dependent screening and show that it can accurately predict charge injection barriers for monolayer MoS 2 . It is proposed that the formalism of the expanded Schottky-Mott rule should be universally applicable for 2D semiconductors, provided that material-specific experimental benchmark data are available.

The electronic properties of semiconducting inorganic lead sulfide (PbS) nanocrystals (NCs) and organic linker molecules are dependent on the size of NCs as well as the used ligands. Here, we demonstrate that a weakly binding ligand can be successfully attached to PbS NCs to form a coupled organic-inorganic nanostructure (COIN) by mixing with a strong binding partner. We use the weakly binding zinc β-tetraaminophthalocyanine (Zn4APc) in combination with the strongly binding 1,2-ethanedithiol (EDT) as a mixed ligand system and compare its structural, electronic, and (photo-)electrical properties with both single-ligand COINs. It is found that binding of Zn4APc is assisted by the presence of EDT leading to improved film homogeneity, lower trap density, and enhanced photocurrent of the derived devices. Thus, the mixing of ligands is a versatile tool to achieve COINs with improved performance.

Ligands in ligand-protected metal clusters play a crucial role, not only because of their interaction with the metal core, but also because of the functionality they provide to the cluster. Here, we report the utilization of secondary phosphine oxide (SPO), as a new family of functional ligands, for the preparation of an undecagold cluster Au11-SPO . Different from the commonly used phosphine ligand (i.e., triphenylphosphine, TPP), the SPOs in Au11-SPO work as electron-withdrawing anionic ligands. While coordinating to gold via the phosphorus atom, the SPO ligand keeps its O atom available to act as a nucleophile. Upon photoexcitation, the clusters are found to inject holes into p-type semiconductors (here, bismuth oxide is used as a model), sensitizing the p-type semiconductor in a different way compared to the photosensitization of a n-type semiconductor. Furthermore, the Au11-SPO /Bi 2 O 3 photocathode exhibits a much higher activity toward the hydrogenation of benzaldehyde than a TPP-protected Au 11 -sensitized Bi 2 O 3 photocathode. Control experiments and density functional theory studies point to the crucial role of the cooperation between gold and the SPO ligands on the selectivity toward the hydrogenation of the C═O group in benzaldehyde.

The mechanism and the nature of the species formed by molecular doping of the model polymer poly(3-hexylthiophene) (P3HT) in its regioregular (rre-) and regiorandom (rra-) forms in solution are investigated for three different dopants: the prototypical π-electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ), the strong Lewis acid tris(pentafluorophenyl)borane (BCF), and the strongly oxidizing complex molybdenum tris[1-(methoxycarbonyl)-2-(trifluoromethyl)ethane-1,2-dithiolene] (Mo(tfd-CO 2 Me) 3 ). In a combined optical and electron paramagnetic resonance study, we show that the doping of rreP3HT in solution occurs by integer charge transfer, resulting in formation of P3HT radical cations (polarons) for all of the dopants considered here. Remarkably, despite the different chemical nature of the dopants and dopant-polymer interaction, the formed polarons exhibit essentially identical optical absorption spectra. The situation is very different for the doping of rraP3HT, where we observe formation of a charge-transfer complex with F 4 TCNQ and of a "localized" P3HT polaron on nonaggregated chains upon doping with BCF, while there is no indication of dopant-induced species in the case of Mo(tfd-CO 2 Me) 3 . We estimate the ionization efficiency of the respective dopants for the two polymers in solution and report the molar extinction coefficient spectra of the three different species. Finally, we observe increased spin delocalization in regioregular compared to regiorandom P3HT by electron nuclear double resonance, suggesting that the ability of the charge to delocalize on aggregates of planarized polymer backbones plays a significant role in determining the doping mechanism.

The use of polyethylenimine (PEI) as a thin interlayer between cathodes and organic semiconductors in order to reduce interfacial Ohmic losses has become an important approach in organic electronics. It has also been shown that such interlayers can form spontaneously because of vertical phase separation when spin-coating a blended solution of PEI and the semiconductor. Furthermore, bulk doping of semiconducting polymers by PEI has been claimed. However, to our knowledge, a clear delineation of interfacial from bulk effects has not been published. Here, we report a study on thin films formed by spin-coating blended solutions of PEI and poly{[ N , N '-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T 2 )] on indium tin oxide. We observed the vertical phase separation in such films, where PEI accumulates at the bottom and the top, sandwiching the semiconductor layer. The PEI interlayer on ITO reduces the electron injection barrier to the minimum value determined by Fermi level pinning, which, in turn, reduces the contact resistance by 5 orders of magnitude. Although we find no evidence for doping-induced polarons in P(NDI2OD-T 2 ) upon mixing with PEI from optical absorption, more sensitive electron paramagnetic resonance measurements provide evidence for doping and an increased carrier density, at a very low level. This, in conjunction with an increased charge carrier mobility due to trap filling, results in an increase in the mixed polymer conductivity by 4 orders of magnitude relative to pure P(NDI2OD-T 2 ). Consequently, both interfacial and bulk effects occur with notable magnitude in thin films formed from blended semiconductor polymer/PEI solution. Thus, this facile one-step procedure to form PEI interlayers must be applied with attention, as modification of the bulk semiconductor polymer (here doping) may occur simultaneously and might go un-noticed if not examined carefully.

Charge transfer at organic/inorganic interfaces critically influences the properties of molecular adlayers. Although for metals such charge transfers are well documented by experimental and theoretical results, in the case of semiconductors, clear and direct evidence for a transfer of electrons or holes from oxides with their typically high ionization energy is missing. Here, we present data from infrared reflection-absorption spectroscopy demonstrating that despite a high ionization energy, electrons are transferred from ZnO into a prototype strong molecular electron acceptor, hexafluoro-tetracyano-naphthoquinodimethane (F 6 -TCNNQ). Because there are no previous studies of this type, the interpretation of the pronounced vibrational red shifts observed in the experiment was aided by a thorough theoretical analysis using density functional theory. The calculations reveal that two mechanisms govern the pronounced vibrational band shifts of the adsorbed molecules: electron transfer into unoccupied molecular levels of the organic acceptor and also the bonding between the surface Zn atoms and the peripheral cyano groups. These combined experimental data and the theoretical analysis provide the so-far missing evidence of interfacial electron transfer from high ionization energy inorganic semiconductors to molecular acceptors and indicates that n-doping of ZnO plays a crucial role., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Perovskite solar cells are among the most exciting photovoltaic systems as they combine low recombination losses, ease of fabrication, and high spectral tunability. The Achilles heel of this technology is the device stability due to the ionic nature of the perovskite crystal, rendering it highly hygroscopic, and the extensive diffusion of ions especially at increased temperatures. Herein, we demonstrate the application of a simple solution-processed perfluorinated self-assembled monolayer (p-SAM) that not only enhances the solar cell efficiency, but also improves the stability of the perovskite absorber and, in turn, the solar cell under increased temperature or humid conditions. The p-i-n-type perovskite devices employing these SAMs exhibited power conversion efficiencies surpassing 21%. Notably, the best performing devices are stable under standardized maximum power point operation at 85 °C in inert atmosphere (ISOS-L-2) for more than 250 h and exhibit superior humidity resilience, maintaining ∼95% device performance even if stored in humid air in ambient conditions over months (∼3000 h, ISOS-D-1). Our work, therefore, demonstrates a strategy towards efficient and stable perovskite solar cells with easily deposited functional interlayers.

Conduction and valence band offsets are among the most crucial material parameters for semiconductor heterostructure device design, such as for high-electron mobility transistors or quantum well infrared photodetectors (QWIP). Because of its expected high spontaneous electrical polarization and the possibility of polarization doping at heterointerfaces similar to the AlGaN/InGaN/GaN system, the metastable orthorhombic κ-phase of Ga 2 O 3 and its indium and aluminum alloy systems are a promising alternative for such device applications. However, respective band offsets to any dielectric are unknown, as well as the evolution of the bands within the alloy systems. We report on the valence and conduction band offsets of orthorhombic κ-(Al x Ga 1- x ) 2 O 3 and κ-(In x Ga 1- x ) 2 O 3 thin films to MgO as reference dielectric by X-ray photoelectron spectroscopy. The thin films with compositions x In ≤ 0.27 and x Al ≤ 0.55 were grown by pulsed laser deposition utilizing tin-doped and radially segmented targets. The determined band alignments reveal the formation of a type I heterojunction to MgO for all compositions with conduction band offsets of at least 1.4 eV, providing excellent electron confinement. Only low valence band offsets with a maximum of ∼300 meV were observed. Nevertheless, this renders MgO as a promising gate dielectric for metal-oxide-semiconductor transistors in the orthorhombic modification. We further found that the conduction band offsets in the alloy systems are mainly determined by the evolution of the band gaps, which can be tuned by the composition in a wide range between 4.1 and 6.2 eV, because the energy position of the valence band maximum remains almost constant over the complete composition range investigated. Therefore, tunable conduction band offsets of up to 1.1 eV within the alloy systems allow for subniveau transition energies in (Al x Ga 1- x) 2 O 3 /(In x Ga 1- x ) 2 O 3 /(Al x Ga 1- x ) 2 O 3 quantum wells from the infrared to the visible regime, which are promising for application in QWIPs.

Controlled substitutional doping of two-dimensional transition-metal dichalcogenides (TMDs) is of fundamental importance for their applications in electronics and optoelectronics. However, achieving p -type conductivity in MoS 2 and WS 2 is challenging because of their natural tendency to form n -type vacancy defects. Here, we report versatile growth of p -type monolayer WS 2 by liquid-phase mixing of a host tungsten source and niobium dopant. We show that crystallites of WS 2 with different concentrations of substitutionally doped Nb up to 10 14 cm -2 can be grown by reacting solution-deposited precursor film with sulfur vapor at 850 °C, reflecting the good miscibility of the precursors in the liquid phase. Atomic-resolution characterization with aberration-corrected scanning transmission electron microscopy reveals that the Nb concentration along the outer edge region of the flakes increases consistently with the molar concentration of Nb in the precursor solution. We further demonstrate that ambipolar field-effect transistors can be fabricated based on Nb-doped monolayer WS 2 .

The tremendous success of metal-halide perovskites, especially in the field of photovoltaics, has triggered a substantial number of studies in understanding their optoelectronic properties. However, consensus regarding the electronic properties of these perovskites is lacking due to a huge scatter in the reported key parameters, such as work function (Φ) and valence band maximum (VBM) values. Here, we demonstrate that the surface photovoltage (SPV) is a key phenomenon occurring at the perovskite surfaces that feature a non-negligible density of surface states, which is more the rule than an exception for most materials under study. With ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe, we evidence that even minute UV photon fluxes (500 times lower than that used in typical UPS experiments) are sufficient to induce SPV and shift the perovskite Φ and VBM by several 100 meV compared to dark. By combining UV and visible light, we establish flat band conditions (i.e., compensate the surface-state-induced surface band bending) at the surface of four important perovskites, and find that all are p-type in the bulk, despite a pronounced n-type surface character in the dark. The present findings highlight that SPV effects must be considered in all surface studies to fully understand perovskites' photophysical properties.

Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 ), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.

Engineering the interface between the perovskite absorber and the charge-transporting layers has become an important method for improving the charge extraction and open-circuit voltage ( V OC ) of hybrid perovskite solar cells. Conjugated polymers are particularly suited to form the hole-transporting layer, but their hydrophobicity renders it difficult to solution-process the perovskite absorber on top. Herein, oxygen plasma treatment is introduced as a simple means to change the surface energy and work function of hydrophobic polymer interlayers for use as p-contacts in perovskite solar cells. We find that upon oxygen plasma treatment, the hydrophobic surfaces of different prototypical p-type polymers became sufficiently hydrophilic to enable subsequent perovskite junction processing. In addition, the oxygen plasma treatment also increased the ionization potential of the polymer such that it became closer to the valance band energy of the perovskite. It was also found that the oxygen plasma treatment could increase the electrical conductivity of the p-type polymers, facilitating more efficient charge extraction. On the basis of this concept, inverted MAPbI 3 perovskite devices with different oxygen plasma-treated polymers such as P3HT, P3OT, polyTPD, or PTAA were fabricated with power conversion efficiencies of up to 19%.

Using photoemission spectroscopy, we show that the surface electronic structure of VO 2 is determined by the temperature-dependent metal-insulator phase transition and the density of oxygen vacancies, which depends on the temperature and ultrahigh vacuum (UHV) conditions. The atomically clean and stoichiometric VO 2 surface is insulating at room temperature and features an ultrahigh work function of up to 6.7 eV. Heating in UHV just above the phase transition temperature induces the expected metallic phase, which goes in hand with the formation of oxygen defects (up to 6% in this study), but a high work function >6 eV is maintained. To demonstrate the suitability of VO 2 as hole injection contact for organic semiconductors, we investigated the energy-level alignment with the prototypical organic hole transport material N, N'-di(1-naphthyl)- N, N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB). Evidence for strong Fermi-level pinning and the associated energy-level bending in NPB is found, rendering an Ohmic contact for holes.

Substantial variations in the electronic structure and thus possibly conflicting energetics at interfaces between hybrid perovskites and charge transport layers in solar cells have been reported by the research community. In an attempt to unravel the origin of these variations and enable reliable device design, we demonstrate that donor-like surface states stemming from reduced lead (Pb 0 ) directly impact the energy level alignment at perovskite (CH 3 NH 3 PbI 3-x Cl x ) and molecular electron acceptor layer interfaces using photoelectron spectroscopy. When forming the interfaces, it is found that electron transfer from surface states to acceptor molecules occurs, leading to a strong decrease in the density of ionized surface states. As a consequence, for perovskite samples with low surface state density, the initial band bending at the pristine perovskite surface can be flattened upon interface formation. In contrast, for perovskites with a high surface state density, the Fermi level is strongly pinned at the conduction band edge, and only minor changes in surface band bending are observed upon acceptor deposition. Consequently, depending on the initial perovskite surface state density, very different interface energy level alignment situations (variations over 0.5 eV) are demonstrated and rationalized. Our findings help explain the rather dissimilar reported energy levels at interfaces with perovskites, refining our understanding of the operating principles in devices comprising this material.

The adsorption of molecular acceptors is a viable method for tuning the work function of metal electrodes. This, in turn, enables adjusting charge injection barriers between the electrode and organic semiconductors. Here, we demonstrate the potential of pyrene-tetraone (PyT) and its derivatives dibromopyrene-tetraone (Br-PyT) and dinitropyrene-tetraone (NO 2 -PyT) for modifying the electronic properties of Au(111) and Ag(111) surfaces. The systems are investigated by complementary theoretical and experimental approaches, including photoelectron spectroscopy, the X-ray standing wave technique, and density functional theory simulations. For some of the investigated interfaces the trends expected for Fermi-level pinning are observed, i.e., an increase of the metal work function along with increasing molecular electron affinity and the same work function for Au and Ag with monolayer acceptor coverage. Substantial deviations are, however, found for Br-PyT/Ag(111) and NO 2 -PyT/Ag(111), where in the latter case an adsorption-induced work function increase of as much as 1.6 eV is observed. This behavior is explained as arising from a face-on to edge-on reorientation of molecules in the monolayer. Our calculations show that for an edge-on orientation much larger work-function changes can be expected despite the prevalence of Fermi-level pinning. This is primarily ascribed to a change of the electron affinity of the adsorbate layer that results from a change of the molecular orientation. This work provides a comprehensive understanding of how changing the molecular electron affinity as well as the adsorbate structure impacts the electronic properties of electrodes.

Two-dimensional (2D) semiconductors offer a convenient platform to study 2D physics, for example, to understand doping in an atomically thin semiconductor. Here, we demonstrate the fabrication and unravel the electronic properties of a lateral doped/intrinsic heterojunction in a single-layer (SL) tungsten diselenide (WSe 2 ), a prototype semiconducting transition metal dichalcogenide (TMD), partially covered with a molecular acceptor layer, on a graphite substrate. With combined experiments and theoretical modeling, we reveal the fundamental acceptor-induced p-doping mechanism for SL-WSe 2 . At the 1D border between the doped and undoped SL-WSe 2 regions, we observe band bending and explain it by Thomas-Fermi screening. Using atomically resolved scanning tunneling microscopy and spectroscopy, the screening length is determined to be in the few nanometer range, and we assess the carrier density of intrinsic SL-WSe 2 . These findings are of fundamental and technological importance for understanding and employing surface doping, for example, in designing lateral organic TMD heterostructures for future devices.

Transition-metal phosphides (TMPs) have recently emerged as efficient and inexpensive electrocatalysts for electrochemical water splitting. The synthesis of nanostructured phosphides often involves highly reactive and hazardous phosphorous-containing compounds. Herein, we report the synthesis of nickel phosphides through thermal treatment under H 2 (5%)/Ar of layered nickel phenylphosphonate (NiPh) or methylphosphonate (NiMe) that act as single-source precursors. Ni 12 P 5 , Ni 12 P 5 -Ni 2 P, and Ni 2 P nanoparticles (NPs) with sizes of ca. 15-45 nm coated with a thin shell of carbonaceous material were produced. Thermogravimetric analysis coupled with mass spectrometry (TG-MS) showed that H 2 , H 2 O, P 2 , and -C 6 H 5 are the main compounds formed during the transformation of the precursor under argon and no hazard phosphorous-containing compounds are created, making this a simple and relatively safe route for fabricating nanostructured TMPs. The H 2 most likely reacts with the -PO 3 groups of the precursor to form H 2 O and P 2 , and the latter subsequently reacts with the metal to produce the phosphide. The Ni 12 P 5 -Ni 2 P and Ni 2 P NPs efficiently catalyze the hydrogen evolution reaction (HER), with Ni 2 P showing the best performance and generating a current density of 10 mA cm -2 at an overpotential of 87 mV and exhibiting long-term stability. Co 2 P and CoP NPs were also synthesized following this method. This approach may be utilized to explore the rich metal phosphonate chemistry for fabricating phosphide-based materials for electrochemical energy conversion and storage applications.

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.

9-(Bis-p-tert-octylphenyl)-amino-perylene-3,4-dicarboxy anhydride (BOPA-PDCA) is a strongly dipolar molecule representing a group of asymmetrically substituted perylenes that are employed in dye-sensitized solar cells and hold great promise for discotic liquid crystal applications. Thin BOPA-PDCA films with orientated dipole moments can potentially be used to tune the energy-level alignment in electronic devices and store information. To help assessing these prospects, we here elucidate the molecular self-assembly and electronic structure of BOPA-PCDA employing room temperature scanning tunneling microscopy and spectroscopy in combination with ultraviolet and X-ray photoelectron spectroscopies. BOPA-PCDA monolayers on Au(111) exclusively form in-plane antiferroelectric phases. The molecular arrangements, the increase of the average number of molecules per unit cell via ripening, and the rearrangement upon manipulation with the STM tip indicate an influence of the dipole moment on the molecular assembly and the rearrangement. A slightly preferred out-of-plane orientation of the molecules in the multilayer induces a surface potential of 1.2 eV. This resembles the giant surface potential effect that was reported for vacuum-deposited tris(8-hydroxyquinoline)aluminum and deemed applicable for data storage. Notably, the surface potential in the case of BOPA-PDCA can in part be reversibly removed by visible light irradiation.

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.

A stable and durable electrochemical water oxidation catalyst based on CoO functionalized ZnO nanorods (NRs) is introduced. ZnO NRs were grown on fluorine-doped tin oxide (FTO) by using a low-temperature chemical solution method and were functionalized with cobalt oxide by electrochemical deposition. The electrochemical water oxidation performance of cobalt oxide functionalized ZnO NRs was studied under alkaline (pH = 10) conditions. From these studies, it is noticed that cobalt oxide functionalized ZnO NRs show electrocatalytic activity toward water oxidation with current density on the order of several mA cm(-2). Further, 30 s CoO deposited ZnO nanorods exhibited excellent galvanostatic stability at a current density of 1 mA cm(-2) and potentiostatic stability at 1.25 V vs Ag/AgCl over an electrolysis period of 1 h.

Direct and inverse photoemission were used to study the impact of alkali fluoride postdeposition treatments on the chemical and electronic surface structure of Cu(In,Ga)Se2 (CIGSe) thin films used for high-efficiency flexible solar cells. We find a large surface band gap (E(g)(Surf), up to 2.52 eV) for a NaF/KF-postdeposition treated (PDT) absorber significantly increases compared to the CIGSe bulk band gap and to the Eg(Surf) of 1.61 eV found for an absorber treated with NaF only. Both the valence band maximum (VBM) and the conduction band minimum shift away from the Fermi level. Depth-dependent photoemission measurements reveal that the VBM decreases with increasing surface sensitivity for both samples; this effect is more pronounced for the NaF/KF-PDT CIGSe sample. The observed electronic structure changes can be linked to the recent breakthroughs in CIGSe device efficiencies.

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.

Here we present the formation of predominantly sp(2)-coordinate carbon with magnetic- and heteroatom-induced structural defects in a graphene lattice by a stoichiometric dehalogenation of perchlorinated (hetero)aromatic precursors [hexachlorobenzene, C6Cl6 (HCB), and pentachloropyridine, NC5Cl5 (PCP)] with transition metals such as copper in a combustion synthesis. This route allows the build-up of a carbon lattice by a chemistry free of hydrogen and oxygen compared to other pyrolytic approaches and yields either nitrogen-doped or -undoped graphene domains depending on the precursor. The resulting carbon was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, photoelectron spectroscopy (XPS), and SQUID magnetometry to gain information on its morphological, chemical, and electronic structure and on the location of the nitrogen atoms within the carbon lattice. A significant lowering of the magnetization was observed for the nitrogen-doped carbon obtained by this method, which exhibits less ordered graphene domains in the range of approximately 10-30 nm as per TEM analysis compared to the nondoped carbon resulting from the reaction of HCB with larger graphene domains as per TEM and the presence of a 2D mode in the Raman spectra. The decrease of the magnetization by nitrogen doping within the sp(2)-coordinate carbon lattice can be attributed to an increase in pyrrole-type defects along with a reduction in radical defects originating from five-membered carbon ring structures as well as changes in the π-electron density of edge states.

We used aromatic phosphonates with substituted phenyl rings with different molecular dipole moments to form self-assembled monolayers (SAMs) on the Zn-terminated ZnO(0001) surface in order to engineer the energy-level alignment at hybrid inorganic/organic semiconductor interfaces, with an oligophenylene as organic component. The work function of ZnO was tuned over a wide range of more than 1.7 eV by different SAMs. The difference in the morphology and polarity of the SAM-modified ZnO surfaces led to different oligophenylene orientation, which resulted in an orientation-dependent ionization energy that varied by 0.7 eV. The interplay of SAM-induced work function modification and oligophenylene orientation changes allowed tuning of the offsets between the molecular frontier energy levels and the semiconductor band edges over a wide range. Our results demonstrate the versatile use of appropriate SAMs to tune the energy levels of ZnO-based hybrid semiconductor heterojunctions, which is important to optimize its function, e.g., targeting either interfacial energy- or charge-transfer.

We investigate hybrid charge transfer states (HCTS) at the planar interface between α-NPD and ZnO by spectrally resolved electroluminescence (EL) and external quantum efficiency (EQE) measurements. Radiative decay of HCTSs is proven by distinct emission peaks in the EL spectra of such bilayer devices in the NIR at energies well below the bulk α-NPD or ZnO emission. The EQE spectra display low energy contributions clearly red-shifted with respect to the α-NPD photocurrent and partially overlapping with the EL emission. Tuning of the energy gap between the ZnO conduction band and α-NPD HOMO level (Eint) was achieved by modifying the ZnO surface with self-assembled monolayers based on phosphonic acids. We find a linear dependence of the peak position of the NIR EL on Eint, which unambiguously attributes the origin of this emission to radiative recombination between an electron on the ZnO and a hole on α-NPD. In accordance with this interpretation, we find a strictly linear relation between the open-circuit voltage and the energy of the charge state for such hybrid organic-inorganic interfaces.

Thermally induced chemical vapor deposition (CVD) was used to study the formation of nitrogen-doped graphene and carbon films on copper from aliphatic nitrogen-containing precursors consisting of C1- and C2-units and (hetero)aromatic nitrogen-containing ring systems. The structure and quality of the resulting films were correlated to the influence of the functional groups of the precursor molecules and gas phase composition. They were analyzed with SEM, TEM, EDX, XPS, and Raman spectroscopy. The presence of (N-doped) graphene was confirmed by the 2D mode of the Raman spectra. The isolated graphene films obtained from nitrogen-containing precursors reveal a high conductivity and transparency compared to standard graphene CVD samples. Precursors with amine functional groups (e.g., methylamine) can lead to a direct formation of graphene even without additional hydrogen present in the gas phase. This is not observed for, e.g., methane under comparable CVD conditions. Therefore, the intermediate gas phase species (e.g., amine radicals) can significantly enhance the graphene film growth kinetics. Kinetic and thermodynamic effects can be invoked to discuss the decay of the precursors.

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.

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.

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.

A novel fluorinated copolymer (F-PCPDTBT) is introduced and shown to exhibit significantly higher power conversion efficiency in bulk heterojunction solar cells with PC(70)BM compared to the well-known low-band-gap polymer PCPDTBT. Fluorination lowers the polymer HOMO level, resulting in high open-circuit voltages well exceeding 0.7 V. Optical spectroscopy and morphological studies with energy-resolved transmission electron microscopy reveal that the fluorinated polymer aggregates more strongly in pristine and blended layers, with a smaller amount of additives needed to achieve optimum device performance. Time-delayed collection field and charge extraction by linearly increasing voltage are used to gain insight into the effect of fluorination on the field dependence of free charge-carrier generation and recombination. F-PCPDTBT is shown to exhibit a significantly weaker field dependence of free charge-carrier generation combined with an overall larger amount of free charges, meaning that geminate recombination is greatly reduced. Additionally, a 3-fold reduction in non-geminate recombination is measured compared to optimized PCPDTBT blends. As a consequence of reduced non-geminate recombination, the performance of optimized blends of fluorinated PCPDTBT with PC(70)BM is largely determined by the field dependence of free-carrier generation, and this field dependence is considerably weaker compared to that of blends comprising the non-fluorinated polymer. For these optimized blends, a short-circuit current of 14 mA/cm(2), an open-circuit voltage of 0.74 V, and a fill factor of 58% are achieved, giving a highest energy conversion efficiency of 6.16%. The superior device performance and the low band-gap render this new polymer highly promising for the construction of efficient polymer-based tandem solar cells.

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.

We present a novel core-shell-surface multifunctional structure for dendrimers using a blue fluorescent pyrene core with triphenylene dendrons and triphenylamine surface groups. We find efficient excitation energy transfer from the triphenylene shell to the pyrene core, substantially enhancing the quantum yield in solution and the solid state (4-fold) compared to dendrimers without a core emitter, while TPA groups facilitate the hole capturing and injection ability in the device applications. With a luminance of up to 1400 cd/m(2), a saturated blue emission CIE(xy) = (0.15, 0.17) and high operational stability, these dendrimers belong to the best reported fluorescence-based blue-emitting organic molecules.

C60 adsorbed on a monolayer of hexaazatriphenylene-hexanitrile (HATCN) on Ag(111) is investigated by ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling microscopy. UPS and quantum-mechanical modeling show that HATCN chemisorbed on Ag(111) displays metallic character. This metallic molecular layer decouples C60 electronically from the Ag substrate and simultaneously acts both as template for the stable adsorption of isolated C60 molecules at room temperature and as "soft" metallic contact for subsequently deposited molecules.

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.