Ionization energy and electron affinity in organic solids are understood in terms of a single molecule perturbed by solid-state effects such as polarization energy, band dispersion, and molecular orientation as primary factors. However, no work has been done to determine the individual contributions experimentally. In this work, the electron affinities of thin films of pentacene and perfluoropentacene with different molecular orientations are determined to a precision of 0.1 eV using low-energy inverse photoemission spectroscopy. Based on the precisely determined electron affinities in the solid state together with the corresponding data of the ionization energies and other energy parameters, we quantitatively evaluate the contribution of these effects. It turns out that the bandwidth as well as the polarization energy contributes to the ionization energy and electron affinity in the solid state while the effect of the surface dipole is at most a few eV and does not vary with the molecular orientation. As a result, we conclude that the molecular orientation dependence of the ionization energy and electron affinity of organic solids originates from the orientation-dependent polarization energy in the film.

Solution processibility is a unique advantage of organic semiconductors, permitting the low-cost production of flexible electronics under ambient conditions. However, the solution affinity to substrate surfaces remains a serious dilemma; liquid manipulation is more difficult on highly hydrophobic surfaces, but the use of such surfaces is indispensable for improving device characteristics. Here we demonstrate a simple technique, which we call ‘push coating’, to produce uniform large-area semiconducting polymer films over a hydrophobic surface with eliminating material loss. We utilize a poly(dimethylsiloxane)-based trilayer stamp whose conformal contact with the substrate enables capillarity-induced wetting of the surface. Films are formed through solvent sorption and retention in the stamp, allowing the stamp to be peeled perfectly from the film. The planar film formation on hydrophobic surfaces also enables subsequent fine film patterning. The technique improves the crystallinity and field-effect mobility of stamped semiconductor films, constituting a major step towards flexible electronics production.

Silver nanocolloid, a dense suspension of ligand-encapsulated silver nanoparticles, is an important material for printing-based device production technologies. However, printed conductive patterns of sufficiently high quality and resolution for industrial products have not yet been achieved, as the use of conventional printing techniques is severely limiting. Here we report a printing technique to manufacture ultrafine conductive patterns utilizing the exclusive chemisorption phenomenon of weakly encapsulated silver nanoparticles on a photoactivated surface. The process includes masked irradiation of vacuum ultraviolet light on an amorphous perfluorinated polymer layer to photoactivate the surface with pendant carboxylate groups, and subsequent coating of alkylamine-encapsulated silver nanocolloids, which causes amine–carboxylate conversion to trigger the spontaneous formation of a self-fused solid silver layer. The technique can produce silver patterns of submicron fineness adhered strongly to substrates, thus enabling manufacture of flexible transparent conductive sheets. This printing technique could replace conventional vacuum- and photolithography-based device processing.

The electronic structure of [6,6]-phenyl-${\text{C}}_{61}$ -butyric acid methyl ester (PCBM) was studied using ultraviolet photoelectron spectroscopy of vapor and thin film and inverse photoemission spectroscopy of thin film. The threshold ionization energy of PCBM was found to be $7.17\pm 0.04\text{eV}$ in gas phase and $5.96\pm 0.02\text{eV}$ in solid phase. The threshold electron affinity was $3.9\pm 0.1\text{eV}$ in solid phase. These values are $0.4-0.6\text{eV}$ smaller than ${\text{C}}_{60}$ . The density functional theory calculations gave consistent results with these trends and suggested that the electron donation from the side chain to ${\text{C}}_{60}$ backbone raised the ${\text{C}}_{60}$ -backbone-derived $\pi$ orbitals of PCBM. The polarization energy of PCBM is 1.21 eV, which is almost the same as ${\text{C}}_{60}$ but is about 0.5 eV smaller than the value of typical aromatic hydrocarbons.