An Amorphous Donor-Acceptor Conjugated Polymer with Both High Charge Carrier Mobility and Luminescence Quantum Efficiency.

Organic semiconducting polymers play a pivotal role in the development of field-effect transistors (OFETs) and organic light-emitting diodes (OLEDs), owing to their cost-effectiveness, structural versatility, and solution processability. However, achieving polymers with both high charge carrier mobility (μ) and photoluminescence (PL) quantum yield (Φ) remains a challenge. In this work, we present the design and synthesis of a novel donor-acceptor π-conjugated polymer, TTIF-BT, featuring a di-Thioeno[3,2-b] ThioenoIndeno[1,2-b] Fluorene (TTIF) backbone as the donor component.

Impact of Dilute DIO Additive on Local Microstructure of Fluorinated, pNDI-Based Polymer Solar Cells.

The performance of all-polymer solar cells is often enhanced by incorporating solvent additives during solution processing. In particular, blends based on the model all-polymer system PBDBT:N2200 have been shown to have increased short-circuit current and fill factor when processed with dilute diiodooctane (DIO). However, the morphological mechanism that drives the increase in performance is often not well understood due to limitations in common characterization techniques.

Role of aggregates and microstructure of mixed-ionic-electronic-conductors on charge transport in electrochemical transistors.

Synthetic efforts have delivered a library of organic mixed ionic-electronic conductors (OMIECs) with high performance in electrochemical transistors. The most promising materials are redox-active conjugated polymers with hydrophilic side chains that reach high transconductances in aqueous electrolytes due to volumetric electrochemical charging. Current approaches to improve transconductance and device stability focus mostly on materials chemistry including backbone and side chain design.

Impact of Side-Chain Hydrophilicity on Packing, Swelling, and Ion Interactions in Oxy-Bithiophene Semiconductors.

Exchanging hydrophobic alkyl-based side chains to hydrophilic glycol-based side chains is a widely adopted method for improving mixed-transport device performance, despite the impact on solid-state packing and polymer-electrolyte interactions being poorly understood. Presented here is a molecular dynamics (MD) force field for modeling alkoxylated and glycolated polythiophenes. The force field is validated against known packing motifs for their monomer crystals.

Unraveling the Unconventional Order of a High-Mobility Indacenodithiophene-Benzothiadiazole Copolymer.

A new class of donor-acceptor (D-A) copolymers found to produce high charge carrier mobilities competitive with amorphous silicon (>1 cm V s) exhibit the puzzling microstructure of substantial local order, however lacking long-range order and crystallinity previously deemed necessary for achieving high mobility. Here, we demonstrate the application of low-dose transmission electron microscopy to image and quantify the nanoscale and mesoscale organization of an archetypal D-A copolymer across areas comparable to electronic devices (≈9 μm). The local structure is spatially resolved by mapping the backbone (001) spacing reflection, revealing nanocrystallites of aligned polymer chains throughout nearly the entire film.

High-Performance Humidity Sensing in π-Conjugated Molecular Assemblies through the Engineering of Electron/Proton Transport and Device Interfaces.

The development of systems capable of responding to environmental changes, such as humidity, requires the design and assembly of highly sensitive and efficiently transducing elements. Such a challenge can be mastered only by disentangling the role played by each component of the responsive system, thus ultimately achieving high performance by optimizing the synergistic contribution of all functional elements. Here, we designed and synthesized a novel [1]benzothieno[3,2-][1]benzothiophene derivative equipped with hydrophilic oligoethylene glycol lateral chains (OEG-BTBT) that can electrically transduce subtle changes in ambient humidity with high current ratios (>10) at low voltages (2 V), reaching state-of-the-art performance.

Engineering Optically Switchable Transistors with Improved Performance by Controlling Interactions of Diarylethenes in Polymer Matrices.

The integration of photochromic molecules into semiconducting polymer matrices via blending has recently attracted a great deal of attention, as it provides the means to reversibly modulate the output signal of electronic devices by using light as a remote control. However, the structural and electronic interactions between photochromic molecules and semiconducting polymers are far from being fully understood. Here we perform a comparative investigation by combining two photochromic diarylethene moieties possessing similar energy levels yet different propensity to aggregate with five prototypical polymer semiconductors exhibiting different energy levels and structural order, ranging from amorphous to semicrystalline.

Energetic Control of Redox-Active Polymers toward Safe Organic Bioelectronic Materials.

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side-products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox-active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side-reactions with molecular oxygen during device operation.

Modification of Indacenodithiophene-Based Polymers and Its Impact on Charge Carrier Mobility in Organic Thin-Film Transistors.

The polymer indacenodithiophene--benzothiadiazole (IDT-BT) has been thoroughly studied for its use in p-type organic thin-film transistors over the course of the past decade. While a variety of modifications have been made to its structure, few analogues have been able to match or surpass the hole mobility that can be obtained by IDT-BT. Here, we discuss the rationale behind the chemical modifications that have been utilized and suggest design principles toward high-mobility indacenodithiophene-based polymers.

The Effect of Ring Expansion in Thienobenzo[]indacenodithiophene Polymers for Organic Field-Effect Transistors.

A fused donor, thienobenzo[]indacenodithiophene (), was designed and synthesized using a novel acid-promoted cascade ring closure strategy, and then copolymerized with a benzothiadiazole () monomer. The backbone of is an expansion of the well-known indacenodithiophene () unit and was expected to enhance the charge carrier mobility by improving backbone planarity and facilitating short contacts between polymer chains. However, the optimized field-effect transistors demonstrated an average saturation hole mobility of 0.

Enhanced n-Doping Efficiency of a Naphthalenediimide-Based Copolymer through Polar Side Chains for Organic Thermoelectrics.

N-doping of conjugated polymers either requires a high dopant fraction or yields a low electrical conductivity because of their poor compatibility with molecular dopants. We explore n-doping of the polar naphthalenediimide-bithiophene copolymer p(gNDI-gT2) that carries oligoethylene glycol-based side chains and show that the polymer displays superior miscibility with the benzimidazole-dimethylbenzenamine-based n-dopant N-DMBI. The good compatibility of p(gNDI-gT2) and N-DMBI results in a relatively high doping efficiency of 13% for n-dopants, which leads to a high electrical conductivity of more than 10 S cm for a dopant concentration of only 10 mol % when measured in an inert atmosphere.