2019, Ma, Ji, Zhang, Ke, Schellhammer, Karl Sebastian, Fu, Yubin, Komber, Hartmut, Xu, Chi, Popov, Alexey A., Hennersdorf, Felix, Weigand, Jan J., Zhou, Shengqiang, Pisula, Wojciech, Ortmann, Frank, Berger, Reinhard, Liu, Junzhi, Feng, Xinliang

Controlling the aromaticity and electronic properties of curved π-conjugated systems has been increasingly attractive for the development of novel functional materials for organic electronics. Herein, we demonstrate an efficient synthesis of two novel wave-shaped polycyclic hydrocarbons (PHs) 1 and 2 with 64 π-electrons. Among them, the wave-shaped π-conjugated carbon skeleton of 2 is unambiguously revealed by single-crystal X-ray crystallography analysis. The wave-shaped geometry is induced by steric congestion in the cove and fjord regions. Remarkably, the aromaticity of these two structural isomers can be tailored by the annulated direction of cyclopenta[b]fluorene units. Isomer 1 (Eoptg = 1.13 eV) behaves as a closed-shell compound with weakly antiaromatic feature, whereas its structural isomer 2 displays a highly stable tetraradical character (y0 = 0.23; y1 = 0.22; t1/2 = 91 days) with a narrow optical energy gap of 0.96 eV. Moreover, the curved PH 2 exhibits remarkable ambipolar charge transport in solution-processed organic thin-film transistors. Our research provides a new insight into the design and synthesis of stable functional curved aromatics with multiradical characters. © The Royal Society of Chemistry.

2020, Momper, R., Zhang, H., Chen, S., Halim, H., Johannes, E., Yordanov, S., Braga, D., Blülle, B., Doblas, D., Kraus, T., Kraus, T., Bonn, M., Wang, H.I., Riedinger, A.

Semiconductor nanoplatelets exhibit spectrally pure, directional fluorescence. To make polarized light emission accessible and the charge transport effective, nanoplatelets have to be collectively oriented in the solid state. We discovered that the collective nanoplatelets orientation in monolayers can be controlled kinetically by exploiting the solvent evaporation rate in self-assembly at liquid interfaces. Our method avoids insulating additives such as surfactants, making it ideally suited for optoelectronics. The monolayer films with controlled nanoplatelets orientation (edge-up or face-down) exhibit long-range ordering of transition dipole moments and macroscopically polarized light emission. Furthermore, we unveil that the substantial in-plane electronic coupling between nanoplatelets enables charge transport through a single nanoplatelets monolayer, with an efficiency that strongly depends on the orientation of the nanoplatelets. The ability to kinetically control the assembly of nanoplatelets into ordered monolayers with tunable optical and electronic properties paves the way for new applications in optoelectronic devices.

2023, Lapalikar, Vaidehi, Dacha, Preetam, Hambsch, Mike, Hofstetter, Yvonne J., Vaynzof, Yana, Mannsfeld, Stefan C. B., Ruck, Michael

Bismuth oxide iodide (BiOI) has been viewed as a suitable environmentally-friendly alternative to lead-halide perovskites for low-cost (opto-)electronic applications such as photodetectors, phototransistors and sensors. To enable its incorporation in these devices in a convenient, scalable, and economical way, BiOI thin films were investigated as part of heterojunctions with various p-type organic semiconductors (OSCs) and tested in a field-effect transistor (FET) configuration. The hybrid heterojunctions, which combine the respective functionalities of BiOI and the OSCs were processed from solution under ambient atmosphere. The characteristics of each of these hybrid systems were correlated with the physical and chemical properties of the respective materials using a concept based on heteropolar chemical interactions at the interface. Systems suitable for application in lateral transport devices were identified and it was demonstrated how materials in the hybrids interact to provide improved and synergistic properties. These indentified heterojunction FETs are a first instance of successful incorporation of solution-processed BiOI thin films in a three-terminal device. They show a significant threshold voltage shift and retained carrier mobility compared to pristine OSC devices and open up possibilities for future optoelectronic applications.

2008, Wang, L., Rastelli, A., Kiravittaya, S., Atkinson, P., Ding, F., Bof Bufon, C.C., Hermannstädter, C., Witzany, M., Beirne, G.J., Michler, P., Schmidt, O.G.

We report on the fabrication, detailed characterization and modeling of lateral InGaAs quantum dot molecules (QDMs) embedded in a GaAs matrix and we discuss strategies to fully control their spatial configuration and electronic properties. The three-dimensional morphology of encapsulated QDMs was revealed by selective wet chemical etching of the GaAs top capping layer and subsequent imaging by atomic force microscopy (AFM). The AFM investigation showed that different overgrowth procedures have a profound consequence on the QDM height and shape. QDMs partially capped and annealed in situ for micro- photoluminescence spectroscopy consist of shallow but well-defined quantum dots (QDs) in contrast to misleading results usually provided by surface morphology measurements when they are buried by a thin GaAs layer. This uncapping approach is crucial for determining the QDM structural parameters, which are required for modeling the system. A single-band effective-mass approximation is employed to calculate the confined electron and heavy-hole energy levels, taking the geometry and structural information extracted from the uncapping experiments as inputs. The calculated transition energy of the single QDM shows good agreement with the experimentally observed values. By decreasing the edge-to-edge distance between the two QDs within a QDM, a splitting of the electron (hole) wavefunction into symmetric and antisymmetric states is observed, indicating the presence of lateral coupling. Site control of such lateral QDMs obtained by growth on a pre-patterned substrate, combined with a technology to fabricate gate structures at well-defined positions with respect to the QDMs, could lead to deterministically controlled devices based on QDMs. © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.

2018, Kaiser, Selina K., Lin, Ronghe, Mitchell, Sharon, Fako, Edvin, Krumeich, Frank, Hauert, Roland, Safonova, Olga V., Kondratenko, Vita A., Kondratenko, Evgenii V., Collins, Sean M., Midgley, Paul A., López, Núria, Pérez-Ramírez, Javier

Carbon-supported gold catalysts have the potential to replace the toxic mercuric chloride-based system applied industrially for acetylene hydrochlorination, a key technology for the manufacture of polyvinyl chloride. However, the design of an optimal catalyst is essentially hindered by the difficulties in assessing the nature of the active site. Herein, we present a platform of carbon supported gold nanostructures at a fixed metal loading, ranging from single atoms of tunable oxidation state and coordination to metallic nanoparticles, by varying the structure of functionalised carbons and use of thermal activation. While on activated carbon particle aggregation occurs progressively above 473 K, on nitrogen-doped carbon gold single atoms exhibit outstanding stability up to temperatures of 1073 K and under reaction conditions. By combining steady-state experiments, density functional theory, and transient mechanistic studies, we assess the relation between the metal speciation, electronic properties, and catalytic activity. The results indicate that the activity of gold-based catalysts correlates with the population of Au(i)Cl single atoms and the reaction follows a Langmuir-Hinshelwood mechanism. Strong interaction with HCl and thermodynamically favoured acetylene activation were identified as the key features of the Au(i)Cl sites that endow their superior catalytic performance in comparison to N-stabilised Au(iii) counterparts and gold nanoparticles. Finally, we show that the carrier (activated carbon versus nitrogen-doped carbon) does not affect the catalytic response, but determines the deactivation mechanism (gold particle aggregation and pore blockage, respectively), which opens up different options for the development of stable, high-performance hydrochlorination catalysts. © 2019 The Royal Society of Chemistry.

2016, Matsidik, Rukiya, Luzio, Alessandro, Hameury, Sophie, Komber, Hartmut, McNeill, Christopher R., Caironi, Mario, Sommer, Michael

To develop greener protocols toward the sustainable production of conjugated polymers, we combine the advantages of atom-economic direct arylation polycondensation (DAP) with those of the green solvent 2-methyltetrahydrofuran (MeTHF). The n-type copolymer PNDIT2 is synthesized from unsubstituted bithiophene (T2) and 2,6-dibromonapthalene diimide (NDIBr2) under simple DAP conditions in MeTHF. Extensive optimization is required to suppress nucleophilic substitution of NDIBr end groups, which severely limits molar mass. Different carboxylic acids, bases, palladium precursors and ligands are successfully screened to enable quantitative yield and satisfyingly high molar masses up to Mn,SEC ∼ 20 kDa. In contrast to PNDIT2 made via DAP in toluene with tolyl-chain termini, nucleophilic substitution of NDIBr chain ends in MeTHF finally leads to NDI-OH termination. The influence of different chain termini on the optical, thermal, structural and electronic properties of PNDIT2 is investigated. For samples with identical molecular weight, OH-termination leads to slightly reduced aggregation in solution and bulk crystallinity, a decreased degree of alignment in directionally deposited films, and a consequently reduced, but not compromised, electron mobility with promising values still close to 0.9 cm2 V−1 s−1.

2014, Reiche, M., Kittler, M., Erfurth, W., Pippel, E., Sklarek, K., Blumtritt, H., Haehnel, A., Uebensee, H.

A detailed knowledge of the electronic properties of individual dislocations is necessary for next generation nanodevices. Dislocations are fundamental crystal defects controlling the growth of different nanostructures (nanowires) or appear during device processing. We present a method to record electric properties of single dislocations in thin silicon layers. Results of measurements on single screw dislocations are shown for the first time. Assuming a cross-section area of the dislocation core of about 1 nm2, the current density through a single dislocation is J = 3.8 × 1012 A/cm2 corresponding to a resistivity of ρ ≅ 1 × 10-8 Ω cm. This is about eight orders of magnitude lower than the surrounding silicon matrix. The reason of the supermetallic behavior is the high strain in the cores of the dissociated dislocations modifying the local band structure resulting in high conductive carrier channels along defect cores.

2020, Shipulin, I., Richter, S., Thomas, A.A., Nielsch, K., Hühne, R., Martovitsky, V.

We performed a detailed structural, magnetotransport, and superconducting analysis of thin epitaxial Ba(Fe1-xNix)2As2 films with Ni doping of x = 0.05 and 0.08, as prepared by pulsed laser deposition. X-ray diffraction studies demonstrate the high crystalline perfection of the films, which have a similar quality to single crystals. Furthermore, magnetotransport measurements of the films were performed in magnetic fields up to 9 T. The results we used to estimate the density of electronic states at the Fermi level, the coefficient of electronic heat capacity, and other electronic parameters for this compound, in their dependence on the dopant concentration within the framework of the Ginzburg-Landau-Abrikosov-Gorkov theory. The comparison of the determined parameters with measurement data on comparable Ba(Fe1-xNix)2As2 single crystals shows good agreement, which confirms the high quality of the obtained films.

2021, Bannies, J., Razzoli, E., Michiardi, M., Kung, H.-H., Elfimov, I.S., Yao, M., Fedorov, A., Fink, J., Jozwiak, C., Bostwick, A., Rotenberg, E., Damascelli, A., Felser, C.

Several early transition metal dipnictides (TMDPs) have been found to host topological semimetal states and exhibit large magnetoresistance (MR). In this paper, we use angle-resolved photoemission spectroscopy (ARPES) and magnetotransport to study the electronic properties of a TMDP ZrP2. We find that ZrP2 exhibits an extremely large and unsaturated MR of up to 40 000% at 2 K, which originates from an almost perfect electron-hole (e-h) compensation. Our band structure calculations further show that ZrP2 hosts a topological nodal loop in proximity to the Fermi level. Based on the ARPES measurements, we confirm the results of our calculations and determine the surface band structure. This paper establishes ZrP2 as a platform to investigate near-perfect e-h compensation and its interplay with topological band structures.

2022, Castillo-Seoane, Javier, Gonzalez-Garcia, Lola, Obrero-Perez, José M., Aparicio, Francisco J., Borrás, Ana, González-Elipe, Agustín R., Barranco, Ángel, Sanchez-Valencia, Juan R.

The opto-electronic properties of small-molecules and functional dyes usually differ when incorporated into solid matrices with respect to their isolated form due to an aggregation phenomenon that alters their optical and fluorescent properties. These spectroscopic modifications are studied in the framework of the exciton theory of aggregates, which has been extensively applied in the literature for the study of molecular aggregates of the same type of molecules (homoaggregation). Despite the demonstrated potential of the control of the heteroaggregation process (aggregation of different types of molecules), most of the reported works are devoted to intramolecular aggregates, complex molecules formed by several chromophores attached by organic linkers. The intramolecular aggregates are specifically designed to hold a certain molecular structure that, on the basis of the exciton theory, modifies their optical and fluorescent properties with respect to the isolated chromophores that form the molecule. The present article describes in detail the incorporation of Rhodamine 6G (Rh6G) and 800 (Rh800) into polymeric matrices of poly-(methyl methacrylate), PMMA. The simultaneous incorporation of both dyes results in an enhanced fluorescent emission in the near-infrared (NIR), originating from the formation of ground-state Rh6G–Rh800 intermolecular heteroaggregates. The systematic control of the concentration of both rhodamines provides a model system for the elucidation of the heteroaggregate formation. The efficient energy transfer between Rh6G and Rh800 molecules can be used as wavelength shifters to convert effectively the light from visible to NIR, a very convenient wavelength range for many practical applications which make use of inexpensive commercial detectors and systems.