Marek Havlicek

A facile protection–deprotection route for obtaining indigo pigments as thin films and their applications in organic bulk heterojunctions

Indigo and its derivatives are industrially-important dyes known for centuries. The low solubility of these compounds limits their applications and hinders potential synthetic chemistry using indigo as a building-block. Herein we report attachment of the tert-butoxy carbonyl (tBOC) thermolabile protecting group to indigos, allowing their processing into neat thin films as well as mixed films with a semiconducting polymer. Photoinduced charge transfer is observed to and from these pigments and the polymer.

Hydrogen-Bonded Organic Semiconductor Micro- And Nanocrystals: From Colloidal Syntheses to (Opto-)Electronic Devices

Organic pigments such as indigos, quinacridones, and phthalocyanines are widely produced industrially as colorants for everyday products as various as cosmetics and printing inks. Herein we introduce a general procedure to transform commercially available insoluble microcrystalline pigment powders into colloidal solutions of variously sized and shaped semiconductor micro- and nanocrystals. The synthesis is based on the transformation of the pigments into soluble dyes by introducing transient protecting groups on the secondary amine moieties, followed by controlled deprotection in solution. Three deprotection methods are demonstrated: thermal cleavage, acid-catalyzed deprotection, and amine-induced deprotection. During these processes, ligands are introduced to afford colloidal stability and to provide dedicated surface functionality and for size and shape control. The resulting micro- and nanocrystals exhibit a wide range of optical absorption and photoluminescence over spectral regions from the visible to the near-infrared. Due to excellent colloidal solubility offered by the ligands, the achieved organic nanocrystals are suitable for solution processing of (opto)electronic devices. As examples, phthalocyanine nanowire transistors as well as quinacridone nanocrystal photodetectors, with photoresponsivity values by far outperforming those of vacuum deposited reference samples, are demonstrated. The high responsivity is enabled by photoinduced charge transfer between the nanocrystals and the directly attached electron-accepting vitamin B2 ligands. The semiconducting nanocrystals described here offer a cheap, nontoxic, and environmentally friendly alternative to inorganic nanocrystals as well as a new paradigm for obtaining organic semiconductor materials from commercial colorants.

Doping-Induced Absorption Bands in P3HT: Polarons and Bipolarons†

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p-type doping (oxidation) of the organic semiconductor poly(3- hexylthiophene-2,5-diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near-IR range as well as in the mid-IR range. In the low-oxidation regime, two absorption bands related to sub-gap transitions appear, one in the UV/Vis range and another one in the mid-IR range. The UV/Vis absorption gradually decreases upon further doping while the mid-IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p-type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.

Role of recombination, dissociation, and competition between exciton-charge reactions in magnetoconductance of polymeric semiconductor device

Magnetoelectrical measurements were performed on a diode structure, based on an anthracene-containing poly(arylene-ethynylylene)-alt-poly(arylene-vinylene) denoted AnE-PVstat, to clarify the role of the recombination and dissociation of electron-hole (e-h) pairs in the magnetoconductance (MC). We report the observed MC under a weak magnetic field (<1 T) at room and low temperatures. Positive MC is observed and reaches up to 2% at a magnetic field of 450 mT at room temperature. It is found that with the increase of the voltage, the MC effect decreases. We also report the difference in MC between perpendicular (θ = 90°) and parallel (θ = 0°) alignment of magnetic field with respect to the current direction. The experimental data were analyzed in the context of the e-h pair model, based on the Stochastic Liouville Equation. To interpret the experimental results on magnetoconductance measurements, anisotropic hyperfine interaction has been introduced through an anisotropic hyperfine field. The dissociation ra...

EPR line shape and magnetometry?chances and pitfalls

Electron paramagnetic resonance (EPR) may permit chemical identification of paramagnetic defects and their atomic arrangement within a crystalline solid. EPR, being a spectroscopic method, can also be used to evaluate the number of paramagnetic centres of microscopically identified contributions to the magnetic susceptibility in contrast to conventional susceptometry which yields only integral information. Complications may arise, however, in the evaluation as exemplified in this paper. We discuss two aspects: (i) the occurrence of spin excitation mechanisms other than magnetic dipole transitions and (ii) the specific shape of the resonance line. In conducting samples (i), the spin resonance absorption due to a spin-dependent electric conductivity can easily exceed the absorption originating from magnetic dipole transitions. The Rashba coupling leads to (a) spin excitations by an electric current and (b) dependence of the conductivity on spin polarization, which varies at the resonance, and thus causes a polarization signal. There is also a dispersive contribution to the EPR signal which can be attributed to the spin–orbit interaction as well. In addition, we review some mechanisms of line broadening or line shift (ii) leading to the occurrence of very long tails of the resonance line. Such non-uniform distributions can lead to a large error in the evaluation of the integrated amplitude of electron spin resonance.

Explaining the Cyclic Voltammetry of a Poly(1,4-phenylene-ethynylene)-alt-poly(1,4-phenylene-vinylene) Copolymer upon Oxidation by using Spectroscopic Techniques.

Poly(1,4-phenylene-ethynylene)-alt-poly(1,4-phenylene-vinylene) (PPE-PPV) copolymers have attracted quite a lot of attention in the last few years for electronic device applications owing to their enhanced fluorescence. In this work, we focus on one particular PPE-PPV copolymer with dissymmetrically substituted 1,4-phenylene-ethynylene and symmetrically substituted 1,4-phenylene-vinylene building units. Six successively performed cyclic voltammograms are presented, measured during the oxidation reactions. As the oxidation onset of the electrochemical reaction shifts to lower potentials in each cycle, this behavior is elucidated by using spectroscopic techniques ranging from UV/Vis/near-IR to mid-IR including spin-resonance techniques. Hence, these findings help to explain some of the copolymers most advantageous properties in terms of possible oxidation products.