RESUMO
The intriguing photophysical properties of monolayer stacks of different transition-metal dichalcogenides (TMDs), revealing rich exciton physics including interfacial and moiré excitons, have recently prompted an extension of similar investigations to hybrid systems of TMDs and organic films, as the latter combine large photoabsorption cross sections with the ability to tailor energy levels by targeted synthesis. To go beyond single-molecule photoexcitations and exploit the excitonic signatures of organic solids, crystalline molecular films are required. Moreover, a defined registry on the substrate, ideally an epitaxy, is desirable to also achieve an excitonic coupling in momentum space. This poses a certain challenge as excitonic dipole moments of organic films are closely related to the molecular orientation and film structure, which critically depend on the support roughness. Using X-ray diffraction, optical polarization, and atomic force microscopy, we analyzed the structure of pentacene (PEN) multilayer films grown on WSe2(001) and WS2(001) and identified an epitaxial alignment. While (022)-oriented PEN films are formed on both substrates, their azimuthal orientations are quite different, showing an alignment of the molecular L-axis along the ⟨110⟩WSe2 and ⟨100⟩WS2 directions. This intrinsic epitaxial PEN growth depends, however, sensitively on the substrates surface quality. While it occurs on exfoliated TMD single crystals and multilayer flakes, it is hardly found on exfoliated monolayers, which often exhibit bubbles and wrinkles. This enhances the surface roughness and results in (001)-oriented PEN films with upright molecular orientation but without any azimuthal alignment. However, monolayer flakes can be smoothed by AFM operated in contact mode or by transferring to ultrasmooth substrates such as hBN, which again yields epitaxial PEN films. As different PEN orientations result in different characteristic film morphologies (elongated mesa islands vs pyramidal dendrites), which can be easily distinguished by AFM or optical microscopy, this provides a simple means to judge the roughness of the used TMD surface.
RESUMO
Organic semiconductors combine flexible tailoring of their optoelectronic properties by synthetic means with strong light-matter coupling, which is advantageous for organic electronic device applications. Although spatially selective deposition has been demonstrated, lateral patterning of organic films with simultaneous control of molecular and crystalline orientation is lacking as traditional lithography is not applicable. Here, a new patterning approach based on surface-localized F-centers (halide vacancies) generated by electron irradiation of alkali halides is presented, which allows structural control of molecular adlayers. Combining optical and atomic force microscopy, X-ray diffraction, and density functional theory (DFT) calculations, it is shown that dinaphthothienothiophene (DNTT) molecules adopt an upright orientation on pristine KCl surfaces, while the F-centers stabilize a recumbent orientation, and that these orientations are maintained in thicker films. This specific nucleation results also in different crystallographic morphologies, namely, densely packed islands and jagged fibers, each epitaxially aligned on the KCl surface. Spatially selective surface irradiation can also be used to create patterns of F-centers and thus laterally patterned DNTT films, which can be further transferred to any (including elastomer) substrate due to the water solubility of the alkali halide growth templates.
RESUMO
Charge-transfer excitons (CTXs) at organic donor/acceptor interfaces are considered important intermediates for charge separation in photovoltaic devices. Crystalline model systems provide microscopic insights into the nature of such states as they enable microscopic structure-property investigations. Here, we use angular-resolved UV/vis absorption spectroscopy to characterize the CTXs of crystalline pentacene:perfluoro-pentacene (PEN:PFP) films allowing determination of the polarization of this state. This analysis is complemented by first-principles many-body calculations, performed on the three-dimensional PEN:PFP cocrystal, which confirm that the lowest-energy excitation is a CTX. Analogous simulations performed on bimolecular clusters are unable to reproduce this state. We ascribe this failure to the lack of long-range interactions and wave function periodicity in these cluster calculations, which appear to remain a valid tool for modeling properties of organic materials ruled by local intermolecular couplings.
RESUMO
Combining 2D materials with functional molecular films enables the fabrication of van der Waals bound organic/inorganic hybrids that are of interest for future device architectures. Recently, the 2D dielectric hexagonal boron nitride (hBN) has received particular attention since exfoliation allows the preparation of crystalline layers which have been utilized as ultrathin dielectrics in electronic devices. Here, we have studied the formation and structure of molecular films of the prototypical organic semiconductors pentacene (PEN) and perfluoropentacene (PFP) on hBN. Special attention was paid to the influence of substrate surface defects on the film formation by comparing molecular films that were grown on hBN substrates of various quality, including single crystals (representing the most ideal surface), briefly ion bombarded substrates, and exfoliated flakes. While X-ray diffraction (XRD) yields precise information about the crystalline structure of films grown on (large) single crystals, it is hardly applicable to analyze the films formed on exfoliated flakes because of their small size. Here, we demonstrate that in the case of flakes detailed structural analyses of the molecular films are possible by combining atomic force microscopy (AFM) with microspot UV/vis spectroscopy and optical polarization microscopy. On well-ordered hBN single crystal surfaces both acenes form very smooth and epitaxial crystalline films where molecules adopt a recumbent orientation (even in 100 nm thick films). By contrast, both materials adopt an upright molecular orientation and different polymorphs on defective hBN surfaces and reveal distinctly different film morphologies. On exfoliated flakes, PFP shows a film structure similar to that on the hBN single crystals, while PEN films exhibit a structure as on defective hBN substrates. In addition, a pronounced decoration of defect steps, which are probably created by the exfoliation process, was observed for PEN leading to the formation of tall and extended fibers where molecules adopt a recumbent orientation. The present study reveals different robustness in film growth on exfoliated hBN flakes for various molecules, which has to be considered in their device integration, especially with regard to their optoelectronic properties such as light absorption or charge transport, which depend critically on the molecular orientation and crystalline order.
RESUMO
Light-matter interactions with two-dimensional materials gained significant attention in recent years, leading to the reporting of weak and strong coupling regimes and effective nanolaser operation with various structures. Particularly, future applications involving monolayer materials in waveguide-coupled on-chip-integrated circuitry and valleytronic nanophotonics require controlling, directing, and optimizing photoluminescence. In this context, photoluminescence enhancement from monolayer transition-metal dichalcogenides on patterned semiconducting substrates becomes attractive. It is demonstrated in our work using focused-ion-beam-etched GaP and monolayer WS2 suspended on hexagonal boron nitride buffer sheets. We present an optical microcavity approach capable of efficient in-plane and out-of-plane confinement of light, which results in a WS2 photoluminescence enhancement by a factor of 10 compared to that of the unstructured substrate at room temperature. The key concept is the combination of interference effects in both the horizontal direction using a bull's-eye-shaped circular Bragg grating and in the vertical direction by means of a multiple-reflection model with optimized etch depth of circular air-GaP structures for maximum constructive interference effects of the applied pump and expected emission light.
