Search Results
Energy-level alignment at interfaces between manganese phthalocyanine and C60
2017-4-25, Waas, Daniel, Rückerl, Florian, Knupfer, Martin, Büchner, Bernd
We have used photoelectron spectroscopy to determine the energy-level alignment at organic heterojunctions made of manganese phthalocyanine (MnPc) and the fullerene C60. We show that this energy-level alignment depends upon the preparation sequence, which is explained by different molecular orientations. Moreover, our results demonstrate that MnPc/C60 interfaces are hardly suited for application in organic photovoltaic devices, since the energy difference of the two lowest unoccupied molecular orbitals (LUMOs) is rather small.
Exciton dispersion in para-quaterphenyl: Significant molecular interactions beyond Coulomb coupling
2021, Graf, Lukas, Krupskaya, Yulia, Büchner, Bernd, Knupfer, Martin
We have experimentally determined the momentum dependence of the electronic excitation spectra of para-quaterphenyl single crystals. The parallel arrangement of para-quaterphenyl molecules results in a strong Coulomb coupling of the molecular excitons. Such crystals have been considered to be a very good realization of the Frenkel exciton model, including the formation of H-type aggregates. Our data reveal an unexpected exciton dispersion of the upper Davydov component, which cannot be rationalized in terms of inter-molecular Coulomb coupling of the excitons. A significant reduction of the nearest neighbor coupling due to additional charge-transfer processes is able to provide an explanation of the data. Furthermore, the spectral onset of the excitation spectrum, which represents a heavy exciton resulting from exciton-phonon coupling, also shows a clear dispersion, which had been unknown so far. Finally, an optically forbidden excitation about 1 eV above the excitation onset is observed. © 2021 Author(s).
Observation of strontium segregation in LaAlO3/SrTiO3 and NdGaO3/SrTiO3 oxide heterostructures by X-ray photoemission spectroscopy
2014, Treske, Uwe, Heming, Nadine, Knupfer, Martin, Büchner, Bernd, Koitzsch, Andreas, Di Gennaro, Emiliano, Scotti di Uccio, Umberto, Miletto Granozio, Fabio, Krause, Stefan
LaAlO3 and NdGaO3 thin films of different thicknesses have been grown by pulsed laser deposition on TiO2-terminated SrTiO3 single crystals and investigated by soft X-ray photoemission spectroscopy. The surface sensitivity of the measurements has been tuned by varying photon energy hν and emission angle Θ. In contrast to the core levels of the other elements, the Sr 3d line shows an unexpected splitting for higher surface sensitivity, signaling the presence of a second strontium component. From our quantitative analysis we conclude that during the growth process Sr atoms diffuse away from the substrate and segregate at the surface of the heterostructure, possibly forming strontium oxide
Loss spectroscopy of molecular solids: Combining experiment and theory
2013, Roth, Friedrich, Cudazzo, Pierluigi, Mahns, Benjamin, Gatti, Matteo, Bauer, Johannes, Hampel, Silke, Nohr, Markus, Berger, Helmuth, Knupfer, Martin, Rubio, Angel
The nature of the lowest-energy electronic excitations in prototypical molecular solids is studied here in detail by combining electron energy loss spectroscopy (EELS) experiments and state-of-the-art many-body calculations based on the Bethe–Salpeter equation. From a detailed comparison of the spectra in picene, coronene and tetracene we generally find a good agreement between theory and experiment, with an upshift of the main features of the calculated spectrum of 0.1–0.2 eV, which can be considered the error bar of the calculation. We focus on the anisotropy of the spectra, which illustrates the complexity of this class of materials, showing a high sensitivity with respect to the three-dimensional packing of the molecular units in the crystal. The differences between the measured and the calculated spectra are explained in terms of the small differences between the crystal structures of the measured samples and the structural model used in the calculations. Finally, we discuss the role played by the different electron–hole interactions in the spectra. We thus demonstrate that the combination of highly accurate experimental EELS and theoretical analysis is a powerful tool to elucidate and understand the electronic properties of molecular solids.
New charge-transfer states in blends of ZnPC with F8ZnPC
2021, Graf, Lukas, Ortstein, Katrin, Doctor, Louis P., Naumann, Marco, Beyer, Jan, Heitmann, Johannes, Leo, Karl, Knupfer, Martin
With the aim of pushing the knowledge and understanding on mixed films of organic semiconductors forward, blends of ZnPC and F8ZnPC in different ratios are manufactured. The films have a polycrystalline structure, as indicated by electron diffraction profiles and infrared-spectroscopy. Photoluminescence data show completely different spectra for the blends, compared to the pure materials, which can be ascribed to the suppressing of excimer formation and the appearance of a new charge-transfer excitation between the two different molecules in the blends. This new excitation can also be seen in optical absorption. Momentum dependent measurements of the electronic excitations by electron energy-loss spectroscopy confirm the localized character of the new charge-transfer excitation in the blends. Our experimental data help understand the important issue of donor/acceptor coupling in organic semiconductors.
Integrated molecular diode as 10 MHz half-wave rectifier based on an organic nanostructure heterojunction
2020, Li, Tianming, Bandari, Vineeth Kumar, Hantusch, Martin, Xin, Jianhui, Kuhrt, Robert, Ravishankar, Rachappa, Xu, Longqian, Zhang, Jidong, Knupfer, Martin, Zhu, Feng, Yan, Donghang, Schmidt, Oliver G.
Considerable efforts have been made to realize nanoscale diodes based on single molecules or molecular ensembles for implementing the concept of molecular electronics. However, so far, functional molecular diodes have only been demonstrated in the very low alternating current frequency regime, which is partially due to their extremely low conductance and the poor degree of device integration. Here, we report about fully integrated rectifiers with microtubular soft-contacts, which are based on a molecularly thin organic heterojunction and are able to convert alternating current with a frequency of up to 10 MHz. The unidirectional current behavior of our devices originates mainly from the intrinsically different surfaces of the bottom planar and top microtubular Au electrodes while the excellent high frequency response benefits from the charge accumulation in the phthalocyanine molecular heterojunction, which not only improves the charge injection but also increases the carrier density.
Charge transfer from and to manganese phthalocyanine: bulk materials and interfaces
2017-8-4, Rückerl, Florian, Waas, Daniel, Büchner, Bernd, Knupfer, Martin, Zahn, Dietrich R. T., Haidu, Francisc, Hahn, Torsten, Kortus, Jens
Manganese phthalocyanine (MnPc) is a member of the family of transition-metal phthalocyanines, which combines interesting electronic behavior in the fields of organic and molecular electronics with local magnetic moments. MnPc is characterized by hybrid states between the Mn 3d orbitals and the π orbitals of the ligand very close to the Fermi level. This causes particular physical properties, different from those of the other phthalocyanines, such as a rather small ionization potential, a small band gap and a large electron affinity. These can be exploited to prepare particular compounds and interfaces with appropriate partners, which are characterized by a charge transfer from or to MnPc. We summarize recent spectroscopic and theoretical results that have been achieved in this regard.
Optical Anisotropy and Momentum-Dependent Excitons in Dibenzopentacene Single Crystals
2022, Graf, Lukas, Liu, Fupin, Naumann, Marco, Roth, Friedrich, Debnath, Bipasha, Büchner, Bernd, Krupskaya, Yulia, Popov, Alexey A., Knupfer, Martin
High-quality single crystals of the organic semiconductor (1,2;8,9)-dibenzopentacene were grown via physical vapor transport. The crystal structure─unknown before─was determined by single-crystal X-ray diffraction; polarization-dependent optical absorption measurements display a large anisotropy in the ac plane of the crystals. The overall Davydov splitting is ∼110 meV, which is slightly lower than that in the close relative pentacene (120 meV). Momentum-dependent electron energy-loss spectroscopy measurements show a clear exciton dispersion of the Davydov components. An analysis of the dispersion using a simple 1D model indicates smaller electron- and hole-transfer integrals in dibenzopentacene as compared to pentacene. The spectral weight distribution of the excitation spectra is strongly momentum-dependent and demonstrates a strong momentum-dependent admixture of Frenkel excitons, charge-transfer excitons, and vibrational modes.
On-chip integrated process-programmable sub-10 nm thick molecular devices switching between photomultiplication and memristive behaviour
2022, Li, Tianming, Hantusch, Martin, Qu, Jiang, Bandari, Vineeth Kumar, Knupfer, Martin, Zhu, Feng, Schmidt, Oliver G.
Molecular devices constructed by sub-10 nm thick molecular layers are promising candidates for a new generation of integratable nanoelectronic applications. Here, we report integrated molecular devices based on ultrathin copper phthalocyanine/fullerene hybrid layers with microtubular soft-contacts, which exhibit process-programmable functionality switching between photomultiplication and memristive behaviour. The local electric field at the interface between the polymer bottom electrode and the enclosed molecular channels modulates the ionic-electronic charge interaction and hence determines the transition of the device function. When ions are not driven into the molecular channels at a low interface electric field, photogenerated holes are trapped as electronic space charges, resulting in photomultiplication with a high external quantum efficiency. Once mobile ions are polarized and accumulated as ionic space charges in the molecular channels at a high interface electric field, the molecular devices show ferroelectric-like memristive switching with remarkable resistive ON/OFF and rectification ratios.
Negative plasmon dispersion in 2H-NbS2 beyond the charge-density-wave interpretation
2016, Cudazzo, Pierluigi, Müller, Eric, Habenicht, Carsten, Gatti, Matteo, Berger, Helmuth, Knupfer, Martin, Rubio, Angel, Huotari, Simo
We examine the experimental and theoretical electron-energy loss spectra in 2H-${\mathrm{Cu}}_{0.2}$NbS2 and find that the 1 eV plasmon in this material does not exhibit the regular positive quadratic plasmon dispersion that would be expected for a normal broad-parabolic-band system. Instead we find a nearly non-dispersing plasmon in the momentum-transfer range $q\lt 0.35$ Å−1. We argue that for a stoichiometric pure 2H-NbS2 the dispersion relation is expected to have a negative slope as is the case for other transition-metal dichalcogenides. The presence of Cu impurities, required to stabilize the crystal growth, tends to shift the negative plasmon dispersion into a positive one, but the doping level in the current system is small enough to result in a nearly-non-dispersing plasmon. We conclude that a negative-slope plasmon dispersion is not connected with the existence of a charge-density-wave order in transition metal dichalcogenides.