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    Elucidating Structure Formation in Highly Oriented Triple Cation Perovskite Films
    (Weinheim : Wiley-VCH, 2023) Telschow, Oscar; Scheffczyk, Niels; Hinderhofer, Alexander; Merten, Lena; Kneschaurek, Ekaterina; Bertram, Florian; Zhou, Qi; Löffler, Markus; Schreiber, Frank; Paulus, Fabian; Vaynzof, Yana
    Metal halide perovskites are an emerging class of crystalline semiconductors of great interest for application in optoelectronics. Their properties are dictated not only by their composition, but also by their crystalline structure and microstructure. While significant efforts are dedicated to the development of strategies for microstructural control, significantly less is known about the processes that govern the formation of their crystalline structure in thin films, in particular in the context of crystalline orientation. This work investigates the formation of highly oriented triple cation perovskite films fabricated by utilizing a range of alcohols as an antisolvent. Examining the film formation by in situ grazing-incidence wide-angle X-ray scattering reveals the presence of a short-lived highly oriented crystalline intermediate, which is identified as FAI-PbI2-xDMSO. The intermediate phase templates the crystallization of the perovskite layer, resulting in highly oriented perovskite layers. The formation of this dimethylsulfoxide (DMSO) containing intermediate is triggered by the selective removal of N,N-dimethylformamide (DMF) when alcohols are used as an antisolvent, consequently leading to differing degrees of orientation depending on the antisolvent properties. Finally, this work demonstrates that photovoltaic devices fabricated from the highly oriented films, are superior to those with a random polycrystalline structure in terms of both performance and stability.
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    Highly efficient modulation doping: A path toward superior organic thermoelectric devices
    (Washington, DC [u.a.] : Assoc., 2022) Wang, Shu-Jen; Panhans, Michel; Lashkov, Ilia; Kleemann, Hans; Caglieris, Federico; Becker-Koch, David; Vahland, Jörn; Guo, Erjuan; Huang, Shiyu; Krupskaya, Yulia; Vaynzof, Yana; Büchner, Bernd; Ortmann, Frank; Leo, Karl
    We investigate the charge and thermoelectric transport in modulation-doped large-area rubrene thin-film crystals with different crystal phases. We show that modulation doping allows achieving superior doping efficiencies even for high doping densities, when conventional bulk doping runs into the reserve regime. Modulation-doped orthorhombic rubrene achieves much improved thermoelectric power factors, exceeding 20 μW m−1 K−2 at 80°C. Theoretical studies give insight into the energy landscape of the heterostructures and its influence on qualitative trends of the Seebeck coefficient. Our results show that modulation doping together with high-mobility crystalline organic semiconductor films is a previosly unexplored strategy for achieving high-performance organic thermoelectrics.
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    Intermolecular charge transfer enhances the performance of molecular rectifiers
    (Washington, DC [u.a.] : Assoc., 2022) Sullivan, Ryan P.; Morningstar, John T.; Castellanos-Trejo, Eduardo; Bradford, Robert W.; Hofstetter, Yvonne J.; Vaynzof, Yana; Welker, Mark E.; Jurchescu, Oana D.
    Molecular-scale diodes made from self-assembled monolayers (SAMs) could complement silicon-based technologies with smaller, cheaper, and more versatile devices. However, advancement of this emerging technology is limited by insufficient electronic performance exhibited by the molecular current rectifiers. We overcome this barrier by exploiting the charge-transfer state that results from co-assembling SAMs of molecules with strong electron donor and acceptor termini. We obtain a substantial enhancement in current rectification, which correlates with the degree of charge transfer, as confirmed by several complementary techniques. These findings provide a previously enexplored method for manipulating the properties of molecular electronic devices by exploiting donor/acceptor interactions. They also serve as a model test platform for the study of doping mechanisms in organic systems. Our devices have the potential for fast widespread adoption due to their low-cost processing and self-assembly onto silicon substrates, which could allow seamless integration with current technologies.