The impact of alkyl side‐chain substituents on conjugated polymers on the photovoltaic properties of bulk heterojunction (BHJ) solar cells has been studied extensively, but their impact on small molecules has not received adequate attention. To reveal the effect of side chains, a series of star‐shaped molecules based on a triphenylamine (TPA) core, bithiophene, and dicyanovinyl units derivatized with various alkyl end‐capping groups of methyl, ethyl, hexyl and dodecyl is synthesiyed and studied to comprehensively investigate structure‐properties relationships. UV‐vis absorption and cyclic voltammetry data show that variations of alkyl chain length have little influence on the absorption and highest occupied molecular orbital (HOMO)‐lowest unoccupied molecular orbital (LUMO) levels. However, these seemingly negligible changes have a pronounced impact on the morphology of BHJ thin films as well as their charge carrier separation and transportation, which in turn influences the photovoltaic properties of these small‐molecule‐based BHJ devices. Solution‐processed organic solar cells (OSCs) based on the small molecule with the shortest methyl end groups exhibit high short circuit current (Jsc) and fill factor (FF), with an efficiency as high as 4.76% without any post‐treatments; these are among the highest reported for solution‐processed OSCs based on star‐shaped molecules.
Here we report the application of the Electron Spin Resonance (ESR) spectroscopy as a highly sensitive analytical technique for assessment of the electronic quality of organic semiconductor materials, particularly conjugated polymers. It has been shown that different batches of the same conjugated polymer might contain substantially different amounts of radical species which were attributed to structural defects and/or impurities behaving as traps for mobile charge carriers. Good correlations between the concentrations of radicals in various batches of conjugated polymers and their performances in organic solar cells have been revealed.
Dynamic disorder manifested in fluctuations of charge transfer integrals considerably hinders charge transport in high-mobility organic semiconductors. Accordingly, strategies for suppression of the dynamic disorder are highly desirable. In this...
We present a structural comparison of monolayers on a SiO2 substrate of two asymmetrically substituted sexithiophenes (6T). Molecule 1 consists of 6T with a branched alkyl chain at one end only and shows a crystalline structure. In molecule 2, the bifunctional 6T has in addition at the other end a linear alkyl chain. It displays thermotropic liquid crystalline (LC) behavior. Both compounds form readily single molecular layers from solution. Remarkably, full monolayer coverage can be achieved before multilayer growth starts. LC properties promote preordering near the interface as well as exchange of molecules between the growing domains, thus regulating the domain sizes. As a result, the LC compound 2 forms single-molecule islands with larger domain sizes compared to compound 1. Surface X-ray investigations indicate that the 6T cores are tilted relative to the layer normal. The tilt angle is as large as 54° for compound 2 compared to 28° for compound 1. For molecule 2, interfacial constraints and packing requirements because of the asymmetric substitution cause a rather loosely organized core structure.
Ultrathin organic field effect transistors (OFETs) demonstrate great potential as highly sensitive gas sensors since its electrical performance strongly depends on the environment. However, fabrication of high performance OFETs with reliable operational stability for continuous measurements by fast, rather simple, and inexpensive technique is still a challenge. Herein, electrical and sensing properties of ultrathin OFETs based on siloxane dimers of benzothieno[3,2‐b][1]benzothiophene (BTBT) with different aliphatic spacer lengths fabricated by Langmuir–Blodgett, Langmuir–Schaefer (LS) or spin‐coating techniques are studied, compared and optimized. Investigation of the influence of interface dielectric layer on electrical performance and operational stability of the devices allowed obtaining uniform low‐defect ultrathin semiconducting layers responsible for improved electrical performance. Field‐effect mobility up to 0.47 cm2 V−1 s−1 is achieved for the devices based on the dimer with undecylenic spacer between the BTBT core and disiloxane central fragment fabricated by LS method on the top of poly(methyl methacrylate) interface layer. Promising operational stability lead to advanced sensory properties demonstrated by sensing of ethanethiol with the limit of detection of 30 ppb in the humid air, which is a record value for portable sensing technologies.
Requirements
of speed and simplicity in testing stimulate the development
of modern biosensors. Electrolyte-gated organic field-effect transistors
(EGOFETs) are a promising platform for ultrasensitive, fast, and reliable
detection of biological molecules for low-cost, point-of-care bioelectronic
sensing. Biosensitivity of the EGOFET devices can be achieved by modification
with receptors of one of the electronic active interfaces of the transistor
gate or organic semiconductor surface. Functionalization of the latter
gives the advantage in the creation of a planar architecture and compact
devices for lab-on-chip design. Herein, we propose a universal, fast,
and simple technique based on doctor blading and Langmuir–Schaefer
methods for functionalization of the semiconducting surface of C8-BTBT-C8, allowing the fabrication of a large-scale
biorecognition layer based on the novel functional derivative of BTBT-containing
biotin fragments as a foundation for further biomodification. The
fabricated devices are very efficient and operate stably in phosphate-buffered
saline solution with high reproducibility of electrical properties
in the EGOFET regime. The development of biorecognition properties
of the proposed biolayer is based on the streptavidin–biotin
interactions between the consecutive layers and can be used for a
wide variety of receptors. As a proof-of-concept, we demonstrate the
specific response of the BTBT-based biorecognition layer in EGOFETs
to influenza A virus (H7N1 strain). The elaborated approach to biorecognition
layer formation is appropriate but not limited to aptamer-based receptor
molecules and can be further applied for fabricating several biosensors
for various analytes on one substrate and paves the way for “electronic
tongue” creation.
Friedel-Crafts acylation of tetrathienoacene (TTA) following by reduction reaction resulting in various octyl-substituted TTA derivatives is described for the first time. Varying conditions of the acylation reaction allowed controlling the...
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