Katharina Broch

High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives

Due to their low-temperature processing properties and inherent mechanical flexibility, conjugated polymer field-effect transistors (FETs) are promising candidates for enabling flexible electronic circuits and displays. Much progress has been made on materials performance; however, there remain significant concerns about operational and environmental stability, particularly in the context of applications that require a very high level of threshold voltage stability, such as active-matrix addressing of organic light-emitting diode displays. Here, we investigate the physical mechanisms behind operational and environmental degradation of high-mobility, p-type polymer FETs and demonstrate an effective route to improve device stability. We show that water incorporated in nanometre-sized voids within the polymer microstructure is the key factor in charge trapping and device degradation. By inserting molecular additives that displace water from these voids, it is possible to increase the stability as well as uniformity to a high level sufficient for demanding industrial applications.

2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion

Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

Solution-Processable Singlet Fission Photovoltaic Devices

We demonstrate the successful incorporation of a solution-processable singlet fission material, 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), into photovoltaic devices. TIPS-pentacene rapidly converts high-energy singlet excitons into pairs of triplet excitons via singlet fission, potentially doubling the photocurrent from high-energy photons. Low-energy photons are captured by small-bandgap electron-accepting lead chalcogenide nanocrystals. This is the first solution-processable singlet fission system that performs with substantial efficiency with maximum power conversion efficiencies exceeding 4.8%, and external quantum efficiencies of up to 60% in the TIPS-pentacene absorption range. With PbSe nanocrystal of suitable bandgap, its internal quantum efficiency reaches 170 ± 30%.

Photoluminescence spectroscopy of pure pentacene, perfluoropentacene, and mixed thin films

We report detailed temperature dependent photoluminescence (PL) spectra of pentacene (PEN), perfluoropentacene (PFP), and PEN:PFP mixed thin films grown on SiO(2). PEN and PFP are particularly suitable for this study, since they are structurally compatible for good intermixing and form a model donor/acceptor system. The PL spectra of PEN are discussed in the context of existing literature and compared to the new findings for PFP. We analyze the optical transitions observed in the spectra of PEN and PFP using time-dependent density functional theory calculations. Importantly, for the mixed PEN:PFP film we observe an optical transition in PL at 1.4 eV providing evidence for coupling effects in the blend. We discuss a possible charge-transfer (CT) and provide a tentative scheme of the optical transitions in the blended films.

Controlling the Texture and Crystallinity of Evaporated Lead Phthalocyanine Thin Films for Near-Infrared Sensitive Solar Cells

To achieve organic solar cells with a broadened spectral absorption, we aim to promote the growth of the near-infrared (NIR)-active polymorph of lead phthalocyanine (PbPc) on a relevant electrode for solar cell applications. We studied the effect of different substrate modification layers on PbPc thin film structure as a function of thickness and deposition rate (rdep). We characterized crystallinity and orientation by grazing incidence X-ray diffraction (GIXD) and in situ X-ray reflectivity (XRR) and correlated these data to the performance of bilayer solar cells. When deposited onto a self-assembled monolayer (SAM) or a molybdenum oxide (MoO3) buffer layer, the crystallinity of the PbPc films improves with thickness. The transition from a partially crystalline layer close to the substrate to a more crystalline film with a higher content of the NIR-active phase is enhanced at low rdep, thereby leading to solar cells that exhibit a higher maximum in short circuit current density (JSC) for thinner donor layers. The insertion of a CuI layer induces the formation of strongly textured, crystalline PbPc layers with a vertically homogeneous structure. Solar cells based on these templated donor layers show a variation of JSC with thickness that is independent of rdep. Consequently, without decreasing rdep we could achieve JSC=10 mA/cm2, yielding a bilayer solar cell with a peak external quantum efficiency (EQE) of 35% at 900 nm, and an overall power conversion efficiency (PCE) of 2.9%.

Optical evidence for intermolecular coupling in mixed films of pentacene and perfluoropentacene

We present optical absorption spectra of mixed films of pentacene (PEN) and perfluoropentacene (PFP) grown on SiO2. We investigated the influence of intermolecular coupling between PEN and PFP on the optical spectra by analyzing samples with five different mixing ratios of PFP:PEN with variable angle spectroscopic ellipsometry (VASE) and differential reflectance spectroscopy (DRS). The data show how the spectral shape is influenced by changes in the volume ratio of the two components. By comparison with the pure film spectra an attempt is made to distinguish transitions due to intermolecular coupling between PEN and PFP from transitions caused by interactions of PEN (PFP) with other molecules of the same type. We observe a new transition at 1.6 eV which is not found in the pure film spectra and which we assign to coupling of PFP and PEN.

Parallel Fabrication of Plasmonic Nanocone Sensing Arrays

A fully parallel approach for the fabrication of arrays of metallic nanocones and triangular nanopyramids is presented. Different processes utilizing nanosphere lithography for the creation of etch masks are developed. Monolayers of spheres are reduced in size and directly used as masks, or mono- and double layers are employed as templates for the deposition of aluminum oxide masks. The masks are transferred into an underlying gold or silver layer by argon ion milling, which leads to nanocones or nanopyramids with very sharp tips. Near the tips the enhancement of an external electromagnetic field is particularly strong. This fact is confirmed by numerical simulations and by luminescence imaging in a confocal microscope. Such localized strong fields can amongst others be utilized for high-resolution, high-sensitivity spectroscopy and sensing of molecules near the tip. Arrays of such plasmonic nanostructures thus constitute controllable platforms for surface-enhanced Raman spectroscopy. A thin film of pentacene molecules is evaporated onto both nanocone and nanopyramid substrates, and the observed Raman enhancement is evaluated.

Optical properties of fully and partially fluorinated rubrene in films and solution

We present the optical properties of fully (C42F28, PF-RUB) and half-fluorinated (C42F14H14, F14-RUB) rubrene, both in thin films and as monomers in solution and compare them to hydrogenated rubrene (C42H28, RUB). All three compounds show similar optical absorption bands and photoluminescence line shapes. The results are interpreted with density functional calculations of the orbital energies and time-dependent density functional theory for the HOMO-LUMO transition. Red shifts induced by the surrounding solvent or organic thin films remain much smaller than for polyacenes, in keeping with previous observations for rubrene and existing models for the solvatochromic shifts.

Epitaxial Growth of an Organic p–n Heterojunction: C60 on Single-Crystal Pentacene

Designing molecular p-n heterojunction structures, i.e., electron donor-acceptor contacts, is one of the central challenges for further development of organic electronic devices. In the present study, a well-defined p-n heterojunction of two representative molecular semiconductors, pentacene and C60, formed on the single-crystal surface of pentacene is precisely investigated in terms of its growth behavior and crystallographic structure. C60 assembles into a (111)-oriented face-centered-cubic crystal structure with a specific epitaxial orientation on the (001) surface of the pentacene single crystal. The present experimental findings provide molecular scale insights into the formation mechanisms of the organic p-n heterojunction through an accurate structural analysis of the single-crystalline molecular contact.

Topography-Correlated Confocal Raman Microscopy with Cylindrical Vector Beams for Probing Nanoscale Structural Order

Cylindrical vector beams, such as radially or azimuthally polarized doughnut beams, are combined with topography studies of pentacene thin films, allowing us to correlate Raman spectroscopy with intermolecular interactions depending on the particular pentacene polymorph. Polarization-dependent Raman spectra of the C-H bending vibrations are resolved layer by layer within a thin film of ∼20 nm thickness. The variation of the Raman peak positions indicates changes in the molecular orientation and in the local environment at different heights of the pentacene film. With the assistance of a theoretical model based on harmonic oscillator and perturbation theory, our method reveals the local structural order and the polymorph at different locations within the same pentacene thin film, depending mainly on its thickness. In good agreement with the crystallographic structures reported in the literature, our observations demonstrate that the first few monolayers grown in a structure are closer to the thin-film phase, but for larger film thicknesses, the morphology evolves toward the crystal-bulk phase with a larger tilting angle of the pentacene molecules against the substrate normal.