Search for: All records

Abstract Organic electrochemical transistors are a promising technology for bioelectronic devices, with applications in neuromorphic computing and healthcare. The active component enabling an organic electrochemical transistor is the organic mixed ionic-electronic conductor whose optimization is critical for realizing high-performing devices. In this study, the influence of purity and molecular weight is examined for a p-type polythiophene and an n-type naphthalene diimide-based polymer in improving the performance and safety of organic electrochemical transistors. Our preparative GPC purification reduced the Pd content in the polymers and improved their organic electrochemical transistor mobility by ~60% and 80% for the p- and n-type materials, respectively. These findings demonstrate the paramount importance of removing residual Pd, which was concluded to be more critical than optimization of a polymer’s molecular weight, to improve organic electrochemical transistor performance and that there is readily available improvement in performance and stability of many of the reported organic mixed ionic-electronic conductors. 

N-type semiconducting polymers have been recently utilized in thermoelectric devices, however they have typically exhibited low electrical conductivities and poor device stability, in contrast to p-type semiconductors, which have been much higher performing. This is due in particular to the n-type semiconductor's low doping efficiency, and poor charge carrier mobility. Strategies to enhance the thermoelectric performance of n-type materials include optimizing the electron affinity (EA) with respect to the dopant to improve the doping process and increasing the charge carrier mobility through enhanced molecular packing. Here, we report the design, synthesis and characterization of fused electron-deficient n-type copolymers incorporating the electron withdrawing lactone unit along the backbone. The polymers were synthesized using metal-free aldol condensation conditions to explore the effect of enlarging the central phenyl ring to a naphthalene ring, on the electrical conductivity. When n-doped with N-DMBI, electrical conductivities of up to 0.28 S cm −1 , Seebeck coefficients of −75 μV K −1 and maximum Power factors of 0.16 μW m −1 K −2 were observed from the polymer with the largest electron affinity of −4.68 eV. Extending the aromatic ring reduced the electron affinity, due to reducing the density of electron withdrawing groups and subsequently the electrical conductivity reduced by almost two orders of magnitude. 

Conjugated polymers have gained momentum as serious contenders for next‐generation flexible electronics, but their susceptibility to water represents a major problem. Atmospheric water is ubiquitous and its inadvertent diffusion into polymeric devices generates charge carrier traps, reducing their performance and stability. A good understanding of the physical processes associated with the presence of water is therefore necessary in order to be able to suppress the related trapping events and enable stable, high‐performance devices. Here, evidence is shown that water introduces traps in the bandgap of organic semiconductors and the impact of these traps on the electrical properties of polymer organic field‐effect transistors (OFETs) based on indacenodithiophene‐co‐benzothiadiazole (IDT‐BT) is investigated. Monitoring device parameters and the trap density of states (t‐DOS) during moisture extrication reveals the existence of two types of water‐related traps: shallow traps originating from water inhabiting the voids of the polymer film and deeper traps arising from chemisorbed water present at the dielectric/polymer interface. A trap passivation method based on flame‐annealing is introduced to eliminate the interfacial traps. As a result, stable OFETs, with threshold voltage shifts less than ΔV_th = −0.3 V and constant mobilities (<10% variation) after three months of storage, are fabricated.

 

Crosslinking is a ubiquitous strategy in polymer engineering to increase the thermomechanical robustness of solid polymers but has been relatively unexplored in the context of π‐conjugated (semiconducting) polymers. Notwithstanding, mechanical stability is key to many envisioned applications of organic electronic devices. For example, the wide‐scale distribution of photovoltaic devices incorporating conjugated polymers may depend on integration with substrates subject to mechanical insult—for example, road surfaces, flooring tiles, and vehicle paint. Here, a four‐armed azide‐based crosslinker (“4Bx”) is used to modify the mechanical properties of a library of semiconducting polymers. Three polymers used in bulk heterojunction solar cells (donors J51 and PTB7‐Th, and acceptor N2200) are selected for detailed investigation. In doing so, it is shown that low loadings of 4Bx can be used to increase the strength (up to 30%), toughness (up to 75%), hardness (up to 25%), and cohesion of crosslinked films. Likewise, crosslinked films show greater physical stability in comparison to non‐crosslinked counterparts (20% vs 90% volume lost after sonication). Finally, the locked‐in morphologies and increased mechanical robustness enable crosslinked solar cells to have greater survivability to four degradation tests: abrasion (using a sponge), direct exposure to chloroform, thermal aging, and accelerated degradation (heat, moisture, and oxygen).

 

Solution‐processable organic semiconductors can serve as the basis for new products including rollable displays, tattoo‐like smart bandages for real‐time health monitoring, and conformable electronics integrated into clothing or even implanted in the human body. For such exciting commercial applications to become a reality, good device performance and uniformity over large areas are necessary. The design of new materials has progressed at an astonishing pace, but accessing their intrinsic, efficient electrical properties in large‐area flexible device arrays is difficult. The development of protocols that allow integration with industrial‐scale processing for high‐throughput manufacturing, without the need to compromise on performance, is the key for transitioning these materials to real‐life applications. In this work, large‐area arrays of organic thin‐film transistors obtained by spray‐coating the high‐mobility polymer indacenodithiophene‐co‐benzothiadiazole (IDTBT) are demonstrated. A maximum charge carrier mobility of 2.3 cm²V⁻¹s⁻¹, with a very narrow performance distribution, is obtained over surface areas of 10 cm × 10 cm. The devices retain their electrical properties when bent multiple times and at different curvatures. In addition, large arrays of highly sensitive (0.25% change in mobility for 1% humidity variation), reusable, near‐identical humidity sensors are produced in a one‐step fabrication and calibrated from 0% to 94% relative humidity.

 

For wearable and implantable electronics applications, developing intrinsically stretchable polymer semiconductor is advantageous, especially in the manufacturing of large‐area and high‐density devices. A major challenge is to simultaneously achieve good electrical and mechanical properties for these semiconductor devices. While crystalline domains are generally needed to achieve high mobility, amorphous domains are necessary to impart stretchability. Recent progresses in the design of high‐performance donor–acceptor polymers that exhibit low degrees of energetic disorder, while having a high fraction of amorphous domains, appear promising for polymer semiconductors. Here, a low crystalline, i.e., near‐amorphous, indacenodithiophene‐co‐benzothiadiazole (IDTBT) polymer and a semicrystalline thieno[3,2‐b]thiophene‐diketopyrrolopyrrole (DPPTT) are compared, for mechanical properties and electrical performance under strain. It is observed that IDTBT is able to achieve both a high modulus and high fracture strain, and to preserve electrical functionality under high strain. Next, fully stretchable transistors are fabricated using the IDTBT polymer and observed mobility ≈0.6 cm²V⁻¹s⁻¹at 100% strain along stretching direction. In addition, the morphological evolution of the stretched IDTBT films is investigated by polarized UV–vis and grazing‐incidence X‐ray diffraction to elucidate the molecular origins of high ductility. In summary, the near‐amorphous IDTBT polymer signifies a promising direction regarding molecular design principles toward intrinsically stretchable high‐performance polymer semiconductor.