Investigation of the thermoelectric response in conducting polymers doped by solid-state diffusion

The thermoelectric effect is a physical phenomenon which intricately relates the thermal energy of charge carriers to their charge transport. Understanding the mechanism of this interaction in different systems lies at the heart of inventing novel materials which can revolutionize thermoelectric power gener- ation technology. Despite a recent surge of interest in organic thermoelectric materials, the community has had difficulties in formulating the charge trans- port mechanism in the presence of a significant degree of disorder. Here, we analyze the thermoelectric properties of various conducting polymers doped by a solid-state diffusion of dopant molecules based on a transport model with a power-law energy-dependence of transport function. A fine control of the degree of doping via post-doping annealing provides an accurate empirical evidence of a strong energy dependence of the carrier mobility in the conducting polymers. A superior thermoelectric power factor of conducting polymers doped by solid-state diffusion to that of other doping methods can be attributed to a resulting higher intrinsic mobility and higher free carrier concentration.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement n 610115. Keehoon Kang thanks the for financial support from Samsung Scholarship Foundation and the National Creative Research Laboratory program (Grant No. 2012026372) through the National Research Foundation of Korea, funded by the Korean Ministry of Science and ICT. K.B. acknowledges funding by the German Research Foundation (BR 4869/1-1)

Strong Suppression of Thermal Conductivity in the Presence of Long Terminal Alkyl Chains in Low-Disorder Molecular Semiconductors

While the charge transport properties of organic semiconductors have been extensively studied over the recent years, the field of organics-based thermoelectrics is still limited by a lack of experimental data on thermal transport and of understanding of the associated structure–property relationships. To fill this gap, a comprehensive experimental and theoretical investigation of the lattice thermal conductivity in polycrystalline thin films of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (Cn-DNTT-Cn with n = 0, 8) semiconductors is reported. Strikingly, thermal conductivity appears to be much more isotropic than charge transport, which is confined to the 2D molecular layers. A direct comparison between experimental measurements (3ω–Völklein method) and theoretical estimations (approach-to-equilibrium molecular dynamics (AEMD) method) indicates that the in-plane thermal conductivity is strongly reduced in the presence of the long terminal alkyl chains. This evolution can be rationalized by the strong localization of the intermolecular vibrational modes in C8-DNTT-C8 in comparison to unsubstituted DNTT cores, as evidenced by a vibrational mode analysis. Combined with the enhanced charge transport properties of alkylated DNTT systems, this opens the possibility to decouple electron and phonon transport in these materials, which provides great potential for enhancing the thermoelectric figure of merit ZT

Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices

Unraveling unprecedented charge carrier mobility through structure property relationship of four isomers of didodecyl[1]benzothieno[3,2-b][1]benzothiophene

Since the dawn of organic electronics in the 1970’s, academic and industrial research efforts have led to dramatic improvements of the solubility, stability, and electronic properties of organic semiconductors (OSCs).[1, 2] The common benchmark to characterize the electrical performances of OSCs is their charge carrier mobility μ (cm2 V–1 s–1), defined as the drift velocity of the charge carrier (cm s–1) per unit of applied electric field (V cm–1). Reaching high mobilities in OSCs is highly desirable as it allows faster operation of transistors and energy savings by reduced calculation times.[2, 3] However, OSCs performances (conventional values usually range from 1 to 10 cm2 V–1 s–1, with highest values obtained with single-crystal devices mostly exempt of structural defects) are still not comparable to that of state-of-the-art inorganic semiconductors (e.g. metal oxides with µ = 20-50 cm2 V–1 s–1 and polycrystalline silicon with µ > 100 cm2 V–1 s–1) thereby hampering important potential technological applications such as flexible organic light-emitting diode (OLED) displays and wearable electronics.[3, 4

Design, synthesis, chemical stability, packing, cyclic voltammetry, ionisation potential, and charge transport of [1]benzothieno[3,2-b][1]benzothiophene derivatives

Five new molecular semiconductors that differ from dioctylbenzothienobenzothiophene, by the introduction of ether or thioether side chains, have been synthesized and obtained in good yields. Their availability in sufficient quantities has allowed investigation of their electrochemical behaviour in solution and their electronic properties in solid state. Both ether and thioether compounds oxidise rather easily in solution, but nevertheless, they exhibit rather high ionisation potentials. This is a consequence of their crystal structure. Dioctylthioetherbenzothienobenzothiophene is rather sensitive to oxidation and degrades easily in close to ambient conditions. Dioctylletherbenzothienobenzothiophene is more stable. Its charge carrier mobility remains however rather moderate, on the order of 0.5 cm2/V.s, whereas that of dioctylbenzothienobenzothiophene reached 4 cm2/V.s, in the same conditions. The difference is explained by intrinsic factors as shown by a theoretical modelling

Unraveling Unprecedented Charge Carrier Mobility through Structure Property Relationship of Four Isomers of Didodecylbenzothienol(3,2-b) (1) benzothiophene

peer reviewe

SSITKA-DRIFTS-MS study of the CO hydrogenation over Co-MgO catalysts

info:eu-repo/semantics/nonPublishe

An operando study showing the irrelevance of IR-observable formates in the formation of ethane from syngas over a Co-MgO catalyst

info:eu-repo/semantics/nonPublishe

DRIFTS/MS Studies during Chemical Transients and SSITKA of the CO/H-2 Reaction over Co-MgO Catalysts

International audienceDiffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) has been employed along with chemical and isotope transients to study the catalytic CO hydrogenation over Co/MgO catalysts in a single fixed-bed reactor at T = 523 K and ambient pressure conditions (H-2/CO = 3). According to the operando DRIFTS measurements, the catalyst surface contains hydroxyl groups, adsorbed CO, formate, and methylene groups in the steady-state of the reaction. Transient experiments following fast changes in the feed (chemical transient kinetics, CTK) or isotope composition (steady-state isotopic transient kinetic analysis, SSITKA) have been carried out during DRIFTS and demonstrate that the formate/methylene “seen by DRIFTS” plays no role as imminent intermediates of the ambient pressure Fischer-Tropsch (1717) reaction. The SSITKA experiments (replacing (CO)-C-12 by (CO)-C-13) show that the exchange rate of formate/methylene is significantly lower than that of ethane, which is one of the main reaction products of CO hydrogenation (followed by mass spectrometry). Formate is most probably bound as bidentate mu(2)-species to MgO or at the Co/MgO interface, while methylene stands for skeleton CH2 in either hydrocarbon or carboxylate