Substituting carbon with silicon in organic molecules and materials has long been an attractive way to modify their electronic structure and properties. Silicon-doped graphene-based materials are known to exhibit exotic properties, yet conjugated organic materials with atomically precise Si substitution have remained difficult to prepare. Here we present the on-surface synthesis of one- and two-dimensional covalent organic frameworks whose backbones contain 1,4-disilabenzene (C4Si2) linkers. Silicon atoms were first deposited on a Au(111) surface, forming a AuSix film on annealing. The subsequent deposition and annealing of a bromo-substituted polyaromatic hydrocarbon precursor (triphenylene or pyrene) on this surface led to the formation of the C4Si2-bridged networks, which were characterized by a combination of high-resolution scanning tunnelling microscopy and photoelectron spectroscopy supported by density functional theory calculations. Each Si in a hexagonal C4Si2 ring was found to be covalently linked to one terminal Br atom. For the linear structure obtained with the pyrene-based precursor, the C4Si2 rings were converted into C4Si pentagonal siloles by further annealing.

Thickness and substrate dependence of film growth, morphology, unit-cell structure, and electronic structures was thoroughly investigated for picene, the zigzag connected 5-ring molecule, by employing complementary techniques of in situ real-time X-ray reflectivity/diffraction, in situ electron spectroscopies, and atomic force microscopy. A different kind of thickness dependent structural transition was observed on SiO2 and graphite, resulting in a distinct electronic structure. On SiO2 picene films with 3D crystalline domains are formed with nearly upright molecular orientation from the initial growth stage. With increasing the film thickness the in-plane dimensions of the unit cell in the initially grown domains become smaller (in other words, more compressed), and, at the same time, crystalline domains with a more relaxed structure are nucleating on top of the compressed domains. In spite of such structural changes, the electronic structure, namely energy position of the highest occupied molecular orbital and threshold ionization potential (IPT), is not significantly altered. On graphite, on the other hand, we found a transition from a 2D (layer) to a 3D (island) growth mode with a variation of the molecular orientation from flat-lying to tilted one. The IPT changes significantly between the 2D and 3D growth regime in contrast to the SiO2 system. The origin of the different IPTs of these picene thin films is discussed. The present results are compared with other planar π-conjugated compounds, in particular pentacene which is a structural isomer of picene and shows electronic properties strongly different from picene thin films.

Well-defined monolayers with single-crystalline-like molecular arrangements of dinaphtho­[2,3-b:2′,3′-f]­thieno­[3,2-b]-thiophene (DNTT) and picene, which are a new class of organic semiconductors with enhanced intermolecular interactions, were fabricated and characterized. Although both molecules initially form a loosely packed monolayer with a flat-lying molecule, they undergo phase transition into a densely packed monolayer with single-crystalline-like molecular arrangements with increasing molecular density. Upon the phase transition of the monolayer, the highest occupied molecular orbital (HOMO) level of these molecules splits into two features, as suggested from both the ultraviolet photoelectron spectroscopy and density functional theory calculations. The splitting of the HOMO level was observed to be similar to that expected for the molecular arrangement in the single crystal. This splitting, which has not been observed in the polycrystalline film, suggests a substantial overlap of the HOMO in the well-ordered monolayers.

We fabricated a well-ordered homogeneous monolayer of disk-shaped, carbazolyl dicyanobenzene (CDCB)-based thermally activated delayed fluorescence (TADF) molecule, i.e., 4CzIPN((4s,6s)-2,4,5,6-tetra(9Hcarbazol-9-yl)isophthalonitrile) at room temperature on flat Ag(111), Au(111), and Cu(111) surfaces. The second layer of the 4CzIPN was also found to be well ordered. The electronic states of the well-ordered monolayer and multilayer of 4CzIPN were found to be nearly unchanged from that of the isolated molecule calculated by the density functional theory (DFT), suggesting that the ordered layers retain the TADF properties. Indeed, we demonstrated the delayed fluorescence and the nearly perfect in-plane alignment of the transition dipole moment of a 4CzIPN thin film on glass substrate even in an ambient condition. These results indicate that the well-ordered films of the disc-shaped carbazole-based TADF molecules could potentially be utilized in organic light-emitting diode (OLED) devices with high light outcoupling efficiency.

Adsorptions of alkali metals (such as K and Li) on monolayers of coronene and picene realize the formation of ordered phases, which serve as well-defined model systems for metal-intercalated aromatic superconductors. Upon alkali-doping of the monolayers of coronene and picene, scanning tunneling microscopy and X-ray absorption spectroscopy revealed the rearrangement of the entire molecular layer. The K-induced reconstruction of both monolayers resulted in the formation of a structure with a herringbone-like arrangement of molecules, suggesting the intercalation of alkali metals between molecular planes. Upon reconstruction, a shift in both the vacuum level and core levels of coronene was observed as a result of a charge transfer from alkali metals to coronene. In addition, a new density of states near the Fermi level was formed in both the doped coronene and the doped picene monolayers. This characteristic electronic feature of the ordered monolayer has been also reported in the multilayer picene films, ensuring that the present monolayer can model the properties of the metal-intercalated aromatic hydrocarbons. It is suggested that the electronic structure near the Fermi level is sensitive to the molecular arrangement, and that both the strict control and determinations of the molecular structure in the doped phase should be important for the determination of the electronic structure of these materials.