TY  - JOUR
A1  - He, Tao
A1  - Stolte, Matthias
A1  - Burschka, Christian
A1  - Hansen, Nis Hauke
A1  - Musiol, Thomas
A1  - Kälblein, Daniel
A1  - Pflaum, Jens
A1  - Tao, Xutang
A1  - Brill, Jochen
A1  - Würthner, Frank
T1  - Single-crystal field-effect transistors of new Cl\(_{2}\)-NDI polymorph processed by sublimation in air
JF  - Nature Communications
N2  - Physical properties of active materials built up from small molecules are dictated by their molecular packing in the solid state. Here we demonstrate for the first time the growth of n-channel single-crystal field-effect transistors and organic thin-film transistors by sublimation of 2,6-dichloro-naphthalene diimide in air. Under these conditions, a new polymorph with two-dimensional brick-wall packing mode (\(\beta\)-phase) is obtained that is distinguished from the previously reported herringbone packing motif obtained from solution (\(\alpha\)-phase). We are able to fabricate single-crystal field-effect transistors with electron mobilities in air of up to 8.6 cm\(^{2}\)V\(^{-1}\)s\(^{-1}\) (\(\alpha\)-phase) and up to 3.5 cm\(^{2}\)V\(^{-1}\)s\(^{-1}\) (\(\beta\)-phase) on n-octadecyltriethoxysilane-modified substrates. On silicon dioxide, thin-film devices based on \(\beta\)-phase can be manufactured in air giving rise to electron mobilities of 0.37 cm\(^{2}\)V\(^{-1}\)s\(^{-1}\). The simple crystal and thin-film growth procedures by sublimation under ambient conditions avoid elaborate substrate modifications and costly vacuum equipment-based fabrication steps.
KW  - thin-film transistors
KW  - carrier transport
KW  - \(\beta\)-phase
KW  - organic semiconductors
KW  - induced phase transition
KW  - charge transport
KW  - materials design
KW  - \(\alpha\)-phase
KW  - mobility
KW  - pentacene
Y1  - 2015
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-149255
VL  - 6
IS  - 5954
ER  - 
TY  - JOUR
A1  - Müller, Ulrich
A1  - Spenst, Peter
A1  - Kagerer, Philipp
A1  - Stolte, Matthias
A1  - Würthner, Frank
A1  - Pflaum, Jens
T1  - Photon‐Correlation Studies on Multichromophore Macrocycles of Perylene Dyes
JF  - Advanced Optical Materials
N2  - Organic dyes offer unique properties for their application as room temperature single photon emitters. By means of photon‐correlation, the emission characteristics of macrocyclic para‐xylylene linked perylene bisimide (PBI) trimers and tetramers dispersed in polymethyl methacrylate matrices are analyzed. The optical data indicate that, despite of the strong emission enhancement of PBI trimers and tetramers according to their larger number of chromophores, the photon‐correlation statistics still obeys that of single photon emitters. Moreover, driving PBI trimers and tetramers at higher excitation powers, saturated emission behavior for monomers is found while macrocycle emission is still far‐off saturation but shows enhanced fluctuations. This observation is attributed to fast singlet–singlet annihilation, i.e., faster than the radiative lifetime of the excited S1 state, and the enlarged number of conformational arrangements of multichromophores in the polymeric host. Finally, embedding trimeric PBI macrocycles in active organic light‐emitting diode matrices, electrically driven bright fluorescence together with an indication for antibunching at room temperature can be detected. This, so far, has only been observed for phosphorescent emitters that feature much longer lifetimes of the excited states and, thus, smaller radiative recombination rates. The results are discussed in the context of possible effects on the g(2) behavior of molecular emitters.
KW  - multichromophores
KW  - organic light emitting diodes
KW  - perylene dyes
KW  - photon‐correlation
KW  - single photon emission
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-287219
VL  - 10
IS  - 14
ER  - 
TY  - JOUR
A1  - Hattori, Yohei
A1  - Michail, Evripidis
A1  - Schmiedel, Alexander
A1  - Moos, Michael
A1  - Holzapfel, Marco
A1  - Krummenacher, Ivo
A1  - Braunschweig, Holger
A1  - Müller, Ulrich
A1  - Pflaum, Jens
A1  - Lambert, Christoph
T1  - Luminescent Mono-, Di-, and Tri-radicals: Bridging Polychlorinated Triarylmethyl Radicals by Triarylamines and Triarylboranes
JF  - Chemistry - A European Journal
N2  - Up to three polychlorinated pyridyldiphenylmethyl radicals bridged by a triphenylamine carrying electron withdrawing (CN), neutral (Me), or donating (OMe) groups were synthesized and analogous radicals bridged by tris(2,6‐dimethylphenyl)borane were prepared for comparison. All compounds were as stable as common closed‐shell organic compounds and showed significant fluorescence upon excitation. Electronic, magnetic, absorption, and emission properties were examined in detail, and experimental results were interpreted using DFT calculations. Oxidation potentials, absorption and emission energies could be tuned depending on the electron density of the bridges. The triphenylamine bridges mediated intramolecular weak antiferromagnetic interactions between the radical spins, and the energy difference between the high spin and low spin states was determined by temperature dependent ESR spectroscopy and DFT calculations. The fluorescent properties of all radicals were examined in detail and revealed no difference for high and low spin states which facilitates application of these dyes in two‐photon absorption spectroscopy and OLED devices.
KW  - density functional calculations
KW  - fluorescence
KW  - NIR OLED
KW  - radical
KW  - two-photon absorption
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-208162
VL  - 25
IS  - 68
ER  - 
TY  - JOUR
A1  - Geiger, Michael
A1  - Acharya, Rachana
A1  - Reutter, Eric
A1  - Ferschke, Thomas
A1  - Zschieschang, Ute
A1  - Weis, Jürgen
A1  - Pflaum, Jens
A1  - Klauk, Hagen
A1  - Weitz, Ralf Thomas
T1  - Effect of the Degree of the Gate‐Dielectric Surface Roughness on the Performance of Bottom‐Gate Organic Thin‐Film Transistors
JF  - Advanced Materials Interfaces
N2  - In organic thin‐film transistors (TFTs) fabricated in the inverted (bottom‐gate) device structure, the surface roughness of the gate dielectric onto which the organic‐semiconductor layer is deposited is expected to have a significant effect on the TFT characteristics. To quantitatively evaluate this effect, a method to tune the surface roughness of a gate dielectric consisting of a thin layer of aluminum oxide and an alkylphosphonic acid self‐assembled monolayer over a wide range by controlling a single process parameter, namely the substrate temperature during the deposition of the aluminum gate electrodes, is developed. All other process parameters remain constant in the experiments, so that any differences observed in the TFT performance can be confidently ascribed to effects related to the difference in the gate‐dielectric surface roughness. It is found that an increase in surface roughness leads to a significant decrease in the effective charge‐carrier mobility and an increase in the subthreshold swing. It is shown that a larger gate‐dielectric surface roughness leads to a larger density of grain boundaries in the semiconductor layer, which in turn produces a larger density of localized trap states in the semiconductor.
KW  - grain boundaries
KW  - organic thin‐film transistors
KW  - surface roughness
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-214830
VL  - 7
IS  - 10
ER  - 
TY  - JOUR
A1  - Goel, Mahima
A1  - Siegert, Marie
A1  - Krauss, Gert
A1  - Mohanraj, John
A1  - Hochgesang, Adrian
A1  - Heinrich, David C.
A1  - Fried, Martina
A1  - Pflaum, Jens
A1  - Thelakkat, Mukundan
T1  - HOMO–HOMO Electron Transfer: An Elegant Strategy for p‐Type Doping of Polymer Semiconductors toward Thermoelectric Applications
JF  - Advanced Materials
N2  - Unlike the conventional p‐doping of organic semiconductors (OSCs) using acceptors, here, an efficient doping concept for diketopyrrolopyrrole‐based polymer PDPP[T]\(_{2}\)‐EDOT (OSC‐1) is presented using an oxidized p‐type semiconductor, Spiro‐OMeTAD(TFSI)\(_{2}\) (OSC‐2), exploiting electron transfer from HOMO\(_{OSC-1}\) to HOMO\(_{OSC-2}\). A shift of work function toward the HOMO\(_{OSC-1}\) upon doping is confirmed by ultraviolet photoelectron spectroscopy (UPS). Detailed X‐ray photoelectron spectroscopy (XPS) and UV–vis–NIR absorption studies confirm HOMO\(_{OSC-1}\) to HOMO\(_{OSC-2}\) electron transfer. The reduction products of Spiro‐OMeTAD(TFSI)\(_{2}\) to Spiro‐OMeTAD(TFSI) and Spiro‐OMeTAD is also confirmed and their relative amounts in doped samples is determined. Mott–Schottky analysis shows two orders of magnitude increase in free charge carrier density and one order of magnitude increase in the charge carrier mobility. The conductivity increases considerably by four orders of magnitude to a maximum of 10 S m\(^{-1}\) for a very low doping ratio of 8 mol%. The doped polymer films exhibit high thermal and ambient stability resulting in a maximum power factor of 0.07 µW m\(^{-1}\) K\(^{-2}\) at a Seebeck coefficient of 140 µV K\(^{-1}\) for a very low doping ratio of 4 mol%. Also, the concept of HOMO\(_{OSC-1}\) to HOMO\(_{OSC-2}\) electron transfer is a highly efficient, stable and generic way to p‐dope other conjugated polymers.
KW  - molecular doping
KW  - Mott–Schottky analysis
KW  - organic semiconductors
KW  - polymer thermoelectrics
KW  - ultraviolet photoelectron spectroscopy
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-217850
VL  - 32
IS  - 43
ER  - 
TY  - JOUR
A1  - Frank, Maximilian
A1  - Pflaum, Jens
T1  - Tuning Electronic and Ionic Transport by Carbon–Based Additives in Polymer Electrolytes for Thermoelectric Applications
JF  - Advanced Functional Materials
N2  - Thermoelectric materials utilizing ionic transport open-up entirely new possibilities for the recuperation of waste heat. Remarkably, solid state electrolytes which have entered the focus of battery research in recent years turn-out to be promising candidates also for ionic thermoelectrics. Here, the dynamics of ionic transport and thermoelectric properties of a methacrylate based polymer blend in combination with a lithium salt is analyzed. Impedance spectroscopy data indicates the presence of just one transport mechanism irrespective of lithium salt concentration. In contrast, the temperature dependent ionic conductivity increases with salt concentration and can be ascribed to a Vogel–Fulcher–Tammann (VFT) behavior. The obtained Seebeck coefficients of 2 mV K\(^{−1}\) allow for high power outputs while the polymer matrix maintains the temperature gradient by its low thermal conductivity. Adding multi-walled carbon nanotubes to the polymer matrix allows for variation of the Seebeck coefficient as well as the ionic and electronic conductivities. As a result, a transition between a high temperature VFT regime and a low temperature Arrhenius regime appears at a critical temperature, T\(_{c}\), shifting upon addition of salt. The observed polarity change in Seebeck voltage at T\(_{c}\) suggests a new mode of thermoelectric operation, which is demonstrated by a proof-of-concept mixed electronic-ionic-thermoelectric generator.
KW  - carbon nanotubes
KW  - thermoelectric generators
KW  - thermoelectric characterization
KW  - polymer electrolytes
KW  - impedance spectroscopy
KW  - electrochemistry
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-318908
SN  - 1616-301X
VL  - 32
IS  - 32
ER  -