Leveraging Insulator's Tacticity in Semiconducting Polymer Blends.

Blending conjugated polymers with insulating matrices is often utilized for engineering extrinsic properties in organic electronics. Semiconductor/insulator blends are typically processed to form a uniformly distributed network of conductive domains within the insulating matrix, marrying electronic and physical properties from individual components. Understanding of polymer-polymer interactions in such systems is thus crucial for property co-optimization. One of the commonly overlooked parameters is the structural configuration of the insulator on the resulting properties, especially the electronic properties. This study investigated how the tacticity of the matrix polymer, among other relevant parameters in play, impacts solid state crystallization in semiconductor/matrix blends and hence the resulting charge transport properties. We found an intricate dependence of the film morphology, aggregation behavior, electronic charge transport, and mixed ionic-electronic coupling properties on the insulator's tacticity. Our experimentally iterative approach shows that for a given application, when selecting semiconductor/insulator combinations, the tacticity of the matrix can be leveraged to optimize performance and vary solid-state structure.

Robust Chemiresistive Behavior in Conductive Polymer/MOF Composites.

Metal-organic frameworks (MOFs) are promising materials for gas sensing but are often limited to single-use detection. A hybridization strategy is demonstrated synergistically deploying conductive MOFs (cMOFs) and conductive polymers (cPs) as two complementary mixed ionic-electronic conductors in high-performing stand-alone chemiresistors. This work presents significant improvement in i) sensor recovery kinetics, ii) cycling stability, and iii) dynamic range at room temperature. The effect of hybridization across well-studied cMOFs is demonstrated based on 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaiminotriphenylene (HITP) ligands with varied metal nodes (Co, Cu, Ni). A comprehensive mechanistic study is conducted to relate energy band alignments at the heterojunctions between the MOFs and the polymer with sensing thermodynamics and binding kinetics. The findings reveal that hole enrichment of the cMOF component upon hybridization leads to selective enhancement in desorption kinetics, enabling significantly improved sensor recovery at room temperature, and thus long-term response retention. This mechanism is further supported by density functional theory calculations on sorbate-analyte interactions. It is also found that alloying cPs and cMOFs enables facile thin film co-processing and device integration, potentially unlocking the use of these hybrid conductors in diverse electronic applications.

Polymer-Based Thermally Stable Chemiresistive Sensor for Real-Time Monitoring of NO2 Gas Emission.

We present a thermally stable, mechanically compliant, and sensitive polymer-based NO2 gas sensor design. Interconnected nanoscale morphology driven from spinodal decomposition between conjugated polymers tethered with polar side chains and thermally stable matrix polymers offers judicious design of NO2-sensitive and thermally tolerant thin films. The resulting chemiresitive sensors exhibit stable NO2 sensing even at 170 °C over 6 h. Controlling the density of polar side chains along conjugated polymer backbone enables optimal design for coupling high NO2 sensitivity, selectivity, and thermal stability of polymer sensors. Lastly, thermally stable films are used to implement chemiresistive sensors onto flexible and heat-resistant substrates and demonstrate a reliable gas sensing response even after 500 bending cycles at 170 °C. Such unprecedented sensor performance as well as environmental stability are promising for real-time monitoring of gas emission from vehicles and industrial chemical processes.

Molecularly Hybridized Conduction in DPP-Based Donor-Acceptor Copolymers toward High-Performance Iono-Electronics.

Iono-electronics, that is, transducing devices able to translate ionic injection into electrical output, continue to demand a variety of mixed ionic-electronic conductors (MIECs). Though polar sidechains are widely used in designing novel polymer MIECs, it remains unclear to chemists how much balance is needed between the two antagonistic modes of transport (ion permeability and electronic charge transport) to yield high-performance materials. Here, the impact of molecularly hybridizing ion permeability and charge mobility in semiconducting polymers on their performance in electrochemical and synaptic transistors is investigated. A series of diketopyrrolopyrrole (DPP)-based copolymers are employed to demonstrate the multifunctionality attained by controlling the density of polar sidechains along the backbone. Notably, efficient electrochemical signal transduction and reliable synaptic plasticity are demonstrated via controlled ion insertion and retention. The newly designed DPP-based copolymers further demonstrate unprecedented thermal tolerance among organic mixed ionic-electronic conductors, a key property in the manufacturing of organic electronics.

Mixed Ionic-Electronic Conduction, a Multifunctional Property in Organic Conductors.

Organic mixed ionic-electronic conductors (OMIECs) have gained recent interest and rapid development due to their versatility in diverse applications ranging from sensing, actuation and computation to energy harvesting/storage, and information transfer. Their multifunctional properties arise from their ability to simultaneously participate in redox reactions as well as modulation of ionic and electronic charge density throughout the bulk of the material. Most importantly, the ability to access charge states with deep modulation through a large extent of its density of states and physical volume of the material enables OMIEC-based devices to display exciting new characteristics and opens up new degrees of freedom in device design. Leveraging the infinite possibilities of the organic synthetic toolbox, this perspective highlights several chemical and structural design approaches to modify OMIECs' properties important in device applications such as electronic and ionic conductivity, color, modulus, etc. Additionally, the ability for OMIECs to respond to external stimuli and transduce signals to myriad types of outputs has accelerated their development in smart systems. This perspective further illustrates how various stimuli such as electrical, chemical, and optical inputs fundamentally change OMIECs' properties dynamically and how these changes can be utilized in device applications.

Semiconducting polymer blends that exhibit stable charge transport at high temperatures.

Although high-temperature operation (i.e., beyond 150°C) is of great interest for many electronics applications, achieving stable carrier mobilities for organic semiconductors at elevated temperatures is fundamentally challenging. We report a general strategy to make thermally stable high-temperature semiconducting polymer blends, composed of interpenetrating semicrystalline conjugated polymers and high glass-transition temperature insulating matrices. When properly engineered, such polymer blends display a temperature-insensitive charge transport behavior with hole mobility exceeding 2.0 cm2/V·s across a wide temperature range from room temperature up to 220°C in thin-film transistors.

Attaining Melt Processing of Complementary Semiconducting Polymer Blends at 130 °C via Side-Chain Engineering.

Complementary semiconducting polymer blends (c-SPBs) have been proposed and tested to achieve melt-processed high-performance organic field-effect transistors (OFETs). Prior to this study, melt processing requires temperatures as high as 180 °C. To implement this technique into low-cost and large-area thin-film manufacturing for flexible organic electronics, semiconducting materials meltable at temperatures tolerable by ubiquitous plastic substrates are still needed. We report here the design and melt processing of a c-SPB consisting of a matrix polymer (DPP-C5) and its fully conjugated analogue. By utilizing a siloxane-terminated alkyl chain and a branched alkyl chain as solubilizing groups, the matrix polymer DPP-C5 presents a melting temperature of 115 °C. The resulting c-SPB containing as low as 5% of the fully conjugated polymer could be melt-processed at 130 °C. The obtained OFET devices exhibit hole mobility approaching 1.0 cm2/(V s), threshold voltages below 5 V, and ION/IOFF around 105. This combination of efficient charge-carrier transport and considerably low processing temperatures bode well for melt processing of semiconducting polymer-based organic electronics.

Symmetry Breaking in Side Chains Leading to Mixed Orientations and Improved Charge Transport in Isoindigo-alt-Bithiophene Based Polymer Thin Films.

The selection of side chains is important in design of conjugated polymers. It not only affects their intrinsic physical properties, but also has an impact on thin film morphologies. Recent reports suggested that a face-on/edge-on bimodal orientation observed in polymer thin films may be responsible for a three-dimensional (3D) charge transport and leads to dramatically improved mobility in donor-acceptor based conjugated polymers. To achieve a bimodal orientation in thin films has been seldom explored from the aspect of molecular design. Here, we demonstrate a design strategy involving the use of asymmetric side chains that enables an isoindigo-based polymer to adopt a distinct bimodal orientation, confirmed by the grazing incidence X-ray diffraction. As a result, the polymer presents an average high mobility of 3.8 ± 0.7 cm2 V-1 s-1 with a maximum value of 5.1 cm2 V-1 s-1, in comparison with 0.47 and 0.51 cm2 V-1 s-1 obtained from the two reference polymers. This study exemplifies a new strategy to develop the next generation polymers through understanding the property-structure relationship.

Melt-Processing of Complementary Semiconducting Polymer Blends for High Performance Organic Transistors.

Melt-processing of complementary semiconducting polymer blends provides an average charge carrier mobility of 0.4 cm2 V-1 s-1 and current on/off ratios higher than 105 , a record performance for melt-processed organic field-effect transistors.