Hendrik Glowatzki

Orientation-dependent ionization energies and interface dipoles in ordered molecular assemblies

Although an isolated individual molecule clearly has only one ionization potential, multiple values are found for molecules in ordered assemblies. Photoelectron spectroscopy of archetypical pi-conjugated organic compounds on metal substrates combined with first-principles calculations and electrostatic modelling reveal the existence of a surface dipole built into molecular layers. Conceptually different from the surface dipole at metal surfaces, its origin lies in details of the molecular electronic structure and its magnitude depends on the orientation of molecules relative to the surface of an ordered assembly. Suitable pre-patterning of substrates to induce specific molecular orientations in subsequently grown films thus permits adjusting the ionization potential of one molecular species over up to 0.6 eV via control over monolayer morphology. In addition to providing in-depth understanding of this phenomenon, our study offers design guidelines for improved organic-organic heterojunctions, hole- or electron-blocking layers and reduced barriers for charge-carrier injection in organic electronic devices.

Adsorption-induced intramolecular dipole: correlating molecular conformation and interface electronic structure.

The interfaces formed between pentacene (PEN) and perfluoropentacene (PFP) molecules and Cu(111) were studied using photoelectron spectroscopy, X-ray standing wave (XSW), and scanning tunneling microscopy measurements, in conjunction with theoretical modeling. The average carbon bonding distances for PEN and PFP differ strongly, that is, 2.34 A for PEN versus 2.98 A for PFP. An adsorption-induced nonplanar conformation of PFP is suggested by XSW (F atoms 0.1 A above the carbon plane), which causes an intramolecular dipole of approximately 0.5 D. These observations explain why the hole injection barriers at both molecule/metal interfaces are comparable (1.10 eV for PEN and 1.35 eV for PFP) whereas the molecular ionization energies differ significantly (5.00 eV for PEN and 5.85 eV for PFP). Our results show that the hypothesis of charge injection barrier tuning at organic/metal interfaces by adjusting the ionization energy of molecules is not always readily applicable.

Interdiffusion of molecular acceptors through organic layers to metal substrates mimics doping-related energy level shifts

Photoemission measurements reveal energy level shifts toward the Fermi level when a strong electron acceptor (tetrafluoro-tetracyanoquinodimethane, F4-TCNQ) is deposited on pristine layers of 4,4′,4″-tris(N,N-diphenyl-amino)triphenylamine (TDATA) or 4,4′-bis(N-carbazolyl)biphenyl (CBP). The shifts of the TDATA and CBP energy levels toward the Fermi level of the Au substrate could, in principle, arise from p-type doping of the intrinsic organic layers. While this indeed takes place in TDATA, doping of CBP by F4-TCNQ, i.e., charge transfer complex formation, does not occur. The shifts observed in CBP arise from the diffusion of F4-TCNQ toward the Au substrate, which modifies the buried metal surface potential, leading to a realignment of the energy levels of the organic overlayer.

Interface formation and electronic structure of α-sexithiophene on ZnO

Interface formation between the organic semiconductor α-sexithiophene (6T) and polar as well as nonpolar ZnO surfaces is investigated. The growth mode of the organic layer is strongly influenced by the orientation of the ZnO surface. No indication for chemisorption of 6T on ZnO is found by photoelectron spectroscopy. The energy level alignment at the 6T/ZnO interface is of type-II facilitating electron transfer from the organic to the inorganic part and hole transfer in the other direction, rendering this heterostructure interesting for photovoltaic applications.

Influence of alkyl chain substitution on sexithienyl-metal interface morphology and energetics

The interface between Ag(111) and vacuum sublimated α,ω-dihexylsexithienyl (DH6T) was investigated using ultraviolet photoelectron spectroscopy and atomic force microscopy. While the monolayer of DH6T is lying flat on the metal surface, we found that already in the second molecular layer the molecules are almost standing upright. This abrupt change in molecular orientation lowered the hole injection barrier (Δh) of DH6T/Ag by 0.5eV between monolayer and multilayer. Δh for DH6T multilayers was even lowered by 0.8eV compared to unsubstituted sexithienyl multilayers. The reduction of Δh is attributed to the electronic decoupling of molecules in the first from those in the second layer via the hexyl chains.

Spontaneous charge transfer at organic-organic homointerfaces to establish thermodynamic equilibrium

The energy level alignment of α,ω-dihexylsexithienyl (DH6T) mono- and multilayers on tetrafluorotetracyanoquinodimethane (F4-TCNQ) precovered Ag(111) and polycrystalline Au substrates was investigated with ultraviolet photoelectron spectroscopy. For certain F4-TCNQ precoverages molecular level pinning at DH6T monolayer-multilayer homointerfaces was observed. The pinning behavior shows that thermodynamic equilibrium can be established across hexyl chains via charge transfer, indicating the limited use of these short alkyl chains for insulation in the field of molecular electronics.

Energy level alignment of electrically doped hole transport layers with transparent and conductive indium tin oxide and polymer anodes

Using ultraviolet photoemission spectroscopy, we investigated the energy level alignment at the interfaces of typical anodes used in organic electronics, indium tin oxide (ITO) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), with the oligomeric hole transport material N,N,N′,N′-tetrakis(4-methoxyphenyl)-benzidine (MeO-TPD), and studied the influence of electrical interface doping by the strong electron acceptor tetrafluoro tetracyanoquinodimethane (F4-TCNQ). The fundamentally different anode materials with work functions of 4.40eV (ITO) and 4.85eV (PEDOT:PSS) show different hole injection barriers, which also depend on the thickness of the F4-TCNQ interface dopant layer. PEDOT:PSS anodes exhibit a consistently lower hole injection barrier to MeO-TPD compared to ITO by 0.1eV. We attribute this low hole injection barrier to additional charge transfer reactions at the PEDOT:PSS/MeO-TPD interface. In contrast, the deposition of the electron acceptor at the interface helps significantl...

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.

Orientation-Dependent Work-Function Modification Using Substituted Pyrene-Based Acceptors

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 (NO2-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 NO2-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.