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Abstract Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)^1–3and ultimately enhances device performance^4–7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants^8–10, which are consumed during the doping process. Achieving efficient doping with weak and/or widely accessible dopants under mild conditions remains a considerable challenge. Here, we report a previously undescribed concept for the photocatalytic doping of OSCs that uses air as a weak oxidant (p-dopant) and operates at room temperature. This is a general approach that can be applied to various OSCs and photocatalysts, yielding electrical conductivities that exceed 3,000 S cm^–1. We also demonstrate the successful photocatalytic reduction (n-doping) and simultaneous p-doping and n-doping of OSCs in which the organic salt used to maintain charge neutrality is the only chemical consumed. Our photocatalytic doping method offers great potential for advancing OSC doping and developing next-generation organic electronic devices. 

While molecular doping is ubiquitous in all branches of organic electronics, little is known about the spatial distribution of dopants, especially at molecular length scales. Moreover, a homogeneous distribution is often assumed when simulating transport properties of these materials, even though the distribution is expected to be inhomogeneous. In this study, electron tomography is used to determine the position of individual molybdenum dithiolene complexes and their three-dimensional distribution in a semiconducting polymer at the sub-nanometre scale. A heterogeneous distribution is observed, the characteristics of which depend on the dopant concentration. At 5 mol% of the molybdenum dithiolene complex, the majority of the dopant species are present as isolated molecules or small clusters up to five molecules. At 20 mol% dopant concentration and higher, the dopant species form larger nanoclusters with elongated shapes. Even in case of these larger clusters, each individual dopant species is still in contact with the surrounding polymer. The electrical conductivity first strongly increases with dopant concentration and then slightly decreases for the most highly doped samples, even though no large aggregates can be observed. The decreased conductivity is instead attributed to the increased energetic disorder and lower probability of electron transfer that originates from the increased size and size variation in dopant clusters. This study highlights the importance of detailed information concerning the dopant spatial distribution at the sub-nanometre scale in three dimensions within the organic semiconductor host. The information acquired using electron tomography may facilitate more accurate simulations of charge transport in doped organic semiconductors. 

Abstract Operational stability is essential for the success of organic electrochemical transistors (OECTs) in bioelectronics. The oxygen reduction reaction (ORR) is a common electrochemical side reaction that can compromise the stability of OECTs, but the relationship between ORR and materials degradation is poorly understood. In this study, the impact of ORR on the stability and degradation mechanisms of thiophene‐based OECTs is investigated. The findings show that an increase in pH during ORR leads to the degradation of the polymer backbone. By using a protective polymer glue layer between the semiconductor channel and the aqueous electrolyte, ORR is effectively suppressed and the stability of the OECTs is significantly improved, resulting in current retention of nearly 90% for ≈2 h cycling in the saturation regime. 

Molecular doping of a polythiophene with oligoethylene glycol side chains is found to strongly modulate not only the electrical but also the mechanical properties of the polymer. An oxidation level of up to 18% results in an electrical conductivity of more than 52 S cm −1 and at the same time significantly enhances the elastic modulus from 8 to more than 200 MPa and toughness from 0.5 to 5.1 MJ m −3 . These changes arise because molecular doping strongly influences the glass transition temperature T g and the degree of π-stacking of the polymer, as indicated by both X-ray diffraction and molecular dynamics simulations. Surprisingly, a comparison of doped materials containing mono- or dianions reveals that – for a comparable oxidation level – the presence of multivalent counterions has little effect on the stiffness. Evidently, molecular doping is a powerful tool that can be used for the design of mechanically robust conducting materials, which may find use within the field of flexible and stretchable electronics. 

Abstract Organic electrochemical transistors (OECTs) hold promise for developing a variety of high‐performance (bio‐)electronic devices/circuits. While OECTs based on p‐type semiconductors have achieved tremendous progress in recent years, n‐type OECTs still suffer from low performance, hampering the development of power‐efficient electronics. Here, it is demonstrated that fine‐tuning the molecular weight of the rigid, ladder‐type n‐type polymer poly(benzimidazobenzophenanthroline) (BBL) by only one order of magnitude (from 4.9 to 51 kDa) enables the development of n‐type OECTs with record‐high geometry‐normalized transconductance (g_m,norm ≈ 11 S cm⁻¹) and electron mobility × volumetric capacitance (µC* ≈ 26 F cm⁻¹ V⁻¹s⁻¹), fast temporal response (0.38 ms), and low threshold voltage (0.15 V). This enhancement in OECT performance is ascribed to a more efficient intermolecular charge transport in high‐molecular‐weight BBL than in the low‐molecular‐weight counterpart. OECT‐based complementary inverters are also demonstrated with record‐high voltage gains of up to 100 V V⁻¹and ultralow power consumption down to 0.32 nW, depending on the supply voltage. These devices are among the best sub‐1 V complementary inverters reported to date. These findings demonstrate the importance of molecular weight in optimizing the OECT performance of rigid organic mixed ionic–electronic conductors and open for a new generation of power‐efficient organic (bio‐)electronic devices. 

Abstract Polar polythiophenes with oligoethylene glycol side chains are exceedingly soft materials. A low glass transition temperature and low degree of crystallinity prevents their use as a bulk material. The synthesis of a copolymer comprising 1) soft polythiophene blocks with tetraethylene glycol side chains, and 2) hard urethane segments is reported. The molecular design is contrary to that of other semiconductor‐insulator copolymers, which typically combine a soft nonconjugated spacer with hard conjugated segments. Copolymerization of polar polythiophenes and urethane segments results in a ductile material that can be used as a free‐standing solid. The copolymer displays a storage modulus of 25 MPa at room temperature, elongation at break of 95%, and a reduced degree of swelling due to hydrogen bonding. Both chemical doping and electrochemical oxidation reveal that the introduction of urethane segments does not unduly reduce the hole charge‐carrier mobility and ability to take up charge. Further, stable operation is observed when the copolymer is used as the active layer of organic electrochemical transistors.