We study the growth of two n-type small-molecule organic semiconductors from the perylene diimide family: N,N′-bis-(2-ethylhexyl)dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDIR-CN 2 ) and N,N′-1H,1Hperfluorobutyl-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDIF-CN 2 ) whose chemical structures differ only in the imide substituents, branched alkyl chains −C 8 H 16 and linear fluoroalkyl chains −C 4 F 7 H 2 , respectively. Both types of substituents introduce some degree of steric hindrance for intermolecular interactions, affecting solid-state packing during thin film formation, and thus induce specific structure-dependent optoelectronic properties in thin films. The transition from an amorphous structure to crystalline domains with strong intermolecular coupling was followed in situ and in real time during growth. We investigated the structural and morphological properties by X-ray diffraction and atomic force microscopy as a function of the substrate temperature and chemical structure. We examined the relationship between the structural properties and thin film optical signatures probed via differential reflectance spectroscopy, ellipsometry, and temperature-dependent photoluminescence. A new crystalline PDIR-CN 2 polymorph at high temperatures emerges. In addition, we observed in PDIF-CN 2 that the fluorinated chains contribute to crystallization inhibition because of the higher overall steric hindrance compared to the alkyl chains.

In this work, two novel donor/acceptor (D/A) complexes, namely, diindenoperylene (DIP)/1,3,4,5,7,8-hexafluoro-tetracyanonaphthoquinodimethane (F6TCNNQ) and alpha-sexithiophene (6T)/F6TCNNQ, are studied. The D/A complexes segregate in form of π–π stacked D/A cocrystals and can be observed by X-ray scattering. The different conformational degrees of freedom of the donor molecules, respectively, seem to affect the thin-film crystalline texture and composition of the D/A mixtures significantly. In equimolar mixtures, for DIP/F6TCNNQ, the crystallites are mostly uniaxially oriented and homogeneous, whereas for 6T/F6TCNNQ, a mostly 3D (isotropic) orientation of the crystallites and coexistence of domains of pristine compounds and D/A complex, respectively, are observed. Using optical absorption spectroscopy, we observe for each of the two mixed systems a set of new, strong transitions located in the near-IR range below the gap of the pristine compounds: such transitions are related to charge-transfer (CT) interactions between donor and acceptor. The optical anisotropy of domains of the D/A complexes with associated new electronic states is studied by ellipsometry. We infer that the CT-related transition dipole moment is perpendicular to the respective π-conjugated planes in the D/A complex.

The interaction between a graphene layer and pentacene (PEN) molecules leads to the formation of a lyingdown phase, which can improve charge transport for organic vertical field effect transistors and enhance the optical absorption for increased light harvesting in organic solar cells. Here, we present a comprehensive study of PEN growth on epitaxial graphene on silicon carbide (SiC). Simultaneous grazing-incidence small-and wide-angle X-ray scattering (GISAXS/GIWAXS) were used in situ for real-time monitoring of the PEN crystal growth with millisecond time resolution to identify two distinct anisotropic growth stages after the nucleation of the first monolayer (ML). In the first stage up to 1.5 nm, we observe rapid growth of pentacene domains along the ( 010) and ( 001) facets. This growth behavior is saturating after 1.5 nm. In a second stage, this is followed by continuous lateral crystal growth in only one in-plane direction (100) forming needle-shaped domains. In the second stage, an uninterrupted linear growth of the lying-down PEN phase is found based on the (001) diffraction up to 15 nm. Ex situ atomic force microscopy and polarized confocal Raman microscopy were used to further support the real-time observations of aligned PEN films on graphene.

Anthradithiophene (ADT) and its functionalized derivatives have proven to be attractive for high-performance electronic devices based on small-molecule organic semiconductors. In this manuscript we investigate the structural and optical properties of thin films of difluoroanthradithiophene (diF-ADT), an ADT derivative, grown by organic molecular beam deposition (OMBD). By grazing incidence X-ray diffraction and reciprocal space maps, we show that diF-ADT crystallizes in a thin film structure similar to the single crystal unit cell. In addition, we investigate the growth characteristics with atomic force microscopy (AFM) and show an increase of surface mound sizes with elevated substrate temperature. Optical absorption measurements reveal a clear vibronic progression in both solution and thin film spectra along with a distinct optical anisotropy related to the molecular orientation in thin films.

Abstract