Molecular semiconductors and the Ioffe–Regel criterion: A terahertz study on band transport in DBTTT

Terahertz electromodulation spectroscopy provides insight into the physics of charge carrier transport in molecular semiconductors. The work focuses on thin-film devices of dibenzothiopheno[6,5-b:6′,5′-f]thieno[3,2-b]thiophene. Frequency-resolved data show a Drude-like response of the hole gas in the accumulation region. The temperature dependence of the mobilities follows a T1/2 power law. This indicates that the thermal mean free path of the charge carriers is restricted by disorder. Only a fraction of approximately 5% of the injected carriers fulfills the Ioffe–Regel criterion and participates in band transport.info:eu-repo/semantics/publishe

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)

A Novel Mitigation Mechanism for Photo-Induced Trapping in an Anthradithiophene Derivative Using Additives

© 2020 Wiley-VCH GmbH A novel trap mitigation mechanism using molecular additives, which relieves a characteristic early turn-on voltage in a high-mobility p-type acene-based small-molecule organic semiconductor, when processed from hydrous solvents, is reported. The early turn-on voltage is attributed to photo-induced trapping, and additive incorporation is found to be very effective in suppressing this effect. Remarkably, the molecular additive does not disturb the charge transport properties of the small-molecule semiconductor, but rather intercalates in the crystal structure. This novel technique allows for the solution-processing of small molecular semiconductors from hydrous solvents, greatly simplifying manufacturing processes for large-area electronics. Along with various electric and spectroscopic characterization techniques, simulations have given a deeper insight into the trap mitigation effect induced by the additive

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

Reducing dynamic disorder in small-molecule organic semiconductors by suppressing large-amplitude thermal motions.

Thermal vibrations and the dynamic disorder they create can detrimentally affect the transport properties of van der Waals bonded molecular semiconductors. The low-energy nature of these vibrations makes it difficult to access them experimentally, which is why we still lack clear molecular design rules to control and reduce dynamic disorder. In this study we discuss the promising organic semiconductors rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothio-phene and 2,9-di-decyl-dinaphtho-[2,3-b:20,30-f]-thieno-[3,2-b]-thiophene in terms of an exceptionally low degree of dynamic disorder. In particular, we analyse diffuse scattering in transmission electron microscopy, to show that small molecules that have their side chains attached along the long axis of their conjugated core are better encapsulated in their crystal structure, which helps reduce large-amplitude thermal motions. Our work provides a general strategy for the design of new classes of very high mobility organic semiconductors with a low degree of dynamic disorder.S.I. acknowledges funding from the EPSRC, the Winton Programme for the Physics of Sustainability and the Cambridge Home and EU scholarship scheme (CHESS). G. S. acknowledges postdoctoral fellowship support from the Wiener-Anspach Foundation. We acknowledge the support of Nippon Kayaku in providing the materials C8-BTBT and C10-DNTT. We acknowledge Dr John Morrison for synthesis of TMTES-P and Marie Beatrice for her work that resulted in the thin-film structure of TMTES-P. We acknowledge Audrey Richard and Christian Ruzié for the synthesis of ditBu-BTBT and diTMS-BTBT.This is the final version of the article. It first appeared from Nature Publishing Group via https://doi.org/10.1038/ncomms1073

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

Mechanical Properties of Organic Electronic Polymers on the Nanoscale

Funder: Belgian National Fund for Scientific Research; Id: http://dx.doi.org/10.13039/501100002661Abstract: Organic semiconducting polymers have attractive electronic, optical, and mechanical properties that make them materials of choice for large area flexible electronic devices. In these devices, the electronically active polymer components are micrometers in size, and sport negligible performance degradation upon bending the centimeter‐scale flexible substrate onto which they are integrated. A closer look at the mechanical properties of the polymers, on the grain‐scale and smaller, is not necessary in large area electronic applications. In emerging micromechanical and electromechanical applications where the organic polymer elements are flexed on length scales spanning their own micron‐sized active areas, it becomes important to characterize the uniformity of their mechanical properties on the nanoscale. In this work, the authors use two precision nanomechanical characterization techniques, namely, atomic force microscope based PeakForce quantitative nanomechanical mapping (PF‐QNM) and nanoindentation‐based dynamical mechanical analysis (nano‐DMA), to compare the modulus and the viscoelastic properties of organic polymers used routinely in organic electronics. They quantitatively demonstrate that the semiconducting near‐amorphous organic polymer indacenodithiophene‐co‐benzothiadiazole (C16‐IDTBT) has a higher carrier mobility, lower modulus, and greater nanoscale modulus areal uniformity compared to the semiconducting semicrystalline organic polymer poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (C14‐PBTTT). Modulus homogeneity appears intrinsic to C16‐IDTBT but can be improved in C14‐PBTTT upon chemical doping

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