Kaname Kanai

How annealing influences the morphology of a highly regioregular poly(3‐hexylthiophene) (RR‐P3HT) film at the substrate interface as well as the lateral inhomogeneity in the electronic structure of the film are elucidated. Whereas previous studies have reported that high‐molecular‐weight (MW) RR‐P3HT films tend to show low crystallinity even after annealing, it is found that high‐MW RR‐P3HT does show high crystallinity after annealing at high temperature for a long time. Photoemission electron microscopy (PEEM), X‐ray photoemission spectroscopy, and ultraviolet photoemission spectroscopy results clearly resolve a considerable lateral inhomogeneity in the morphology of RR‐P3HT film, which results in a variation of the electronic structure depending on the local crystallinity. The PEEM results show how annealing facilitates crystal growth in a high‐MW RR‐P3HT film.

The fullerene (C₆₀)/copper phthalocyanine (CuPc) interface is one of the widely used donor/acceptor (DA) interfaces for organic photovoltaics (OPVs), and information on the electronic structure at the interface is essential for fully understanding the energetics of excitons and carriers in OPVs. Here, an investigation into the energy levels at the C₆₀/CuPc interface is made using UV photoelectron, X‐ray photoelectron, and inverse photoemission spectroscopies. The vacuum level and core levels rise with C₆₀ deposition on the CuPc film, which indicates that the interfacial dipole is formed with the negative charge on the C₆₀ side. The interfacial dipole can be formed by the electron transfer from CuPc to C₆₀ in the ground state at the interface, which is indicated by the analysis of the UV–vis–NIR absorption spectrum of the CuPc/C₆₀ blended film. On the other hand, the highest occupied and lowest unoccupied molecular orbitals of CuPc and C₆₀ shift in opposite directions at the interface. This is attributed to the changes of the polarization energies of CuPc and C₆₀ at the interface. The formation of the interfacial dipole and the change of the polarization energy result in the anomalous energy band offsets at the C₆₀/CuPc interface, which are entirely different from those in inorganic p–n junctions.

The electronic structure and film structure of poly(3-hexylthiophene) (P3HT) have been studied by X-ray diffraction (XRD) measurements, ultraviolet-visible (UV-vis) absorption spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) measurements, ultraviolet photoemission spectroscopy (UPS) and inverse photoemission spectroscopy (IPES). As reported in previous works, XRD results show that the crystallinity of the film with regioregular P3HT is significantly improved by annealing at 170 °C. The effects of annealing on the electronic structure strongly depend on the substrate and the degree of regioregularity of the P3HT polymer backbone. Even in the case of the regiorandom sample, annealing considerably changes the vacuum level energy, which is the result of changes in the conformation of the hexyl groups at the free surface of the film. The π- and π*-band onsets uniformly shift downward by the annealing resulting in an increased hole-injection barrier at the electrode interface. The effects of annealing on the electronic structure of regioregular samples are more complex and depend on multiple factors. It is necessary to take into account variations in the π- and π*-band widths and the polarization energy to determine the effects of annealing. The former is associated with the conformation of the backbones of the polymer chains, and the latter is associated with the packing density of the conjugated polymer planes. The combination of these variations determines the effects of annealing on the electronic structure of the regioregular film. This is a possible reason for the strong dependence of the effects of annealing on the surface roughness of the substrate, since substrate roughness has a considerable effect on the morphology and crystallinity of regioregular P3HT films.

The electronic structure of the thiazyl diradical, 4,4′-bis(1,2,3,5-dithiadiazolyl) (BDTDA), has been investigated by ultraviolet photoemission spectroscopy. Stacked BDTDA dimers showed an energy band dispersion of about 0.3 eV for the highest occupied molecular orbital in the direction of the surface normal of the BDTDA solid film. The π-orbital overlap between the stacked dimers therefore evolves into a quasi one-dimensional energy band along the dimer stacking direction.

We report our study on the current-voltage characteristics of single layer devices employing pure and heavily tetrathianaphthacene (TTN)-doped tris(8-hydroxy-quinoline) aluminum (Alq₃) films as active layers. Sandwich structures with magnesium (Mg) top and bottom electrodes were employed in the devices. In the undoped device, the current increases exponentially with the applied voltage, and is concluded to be limited by the carrier injection at the Mg/Alq₃ interface with a small injection barrier. With the same device structure, both the bulk-doped and interface-doped devices show a bulk-limited current flow, which is much larger than that in the undoped device and behaves as trap-free space-charge-limited current (SCLC) with a field-independent mobility. The improvement of the current is ascribed to the large enhancement of carrier injection by the doping. An increase of the magnitude of the interfacial dipole has been proposed as the possible cause for the enhancement of carrier injection.

The atmospheric effect on the ionization energy (I) of titanyl phthalocyanine (TiOPc) thin film was investigated by photoemission yield spectroscopy developed for the measurement of I for the same specimen both in vacuum and under gaseous atmosphere. The variation of I of TiOPc thin film induced by exposure to air was observed.