Molecular doping is a key strategy to enhance the electrical conductivity of organic semiconductors. Typically, the electrical conductivity shows a maximum value upon increased doping, after which the conductivity decreases. This decrease in conductivity is commonly attributed to unfavorable changes in the morphology. However, in recent simulation work, has shown, that the conductivity-at high doping-is instead limited by electron-electron repulsion rather than by morphology, at least for some material combinations. Based on the simulations, this limitation is expected to show up in the dependence of the Seebeck coefficient versus carrier density: the Seebeck coefficient will follow Heike\'s formula if carrier-carrier repulsion limits the conductivity. Here, the electrical conductivity and Seebeck coefficient are measured as a function of doping for a series of n-type organic semiconductors. Additionally, the resulting carrier density is measured using metal-insulator-semiconductor diodes, which link dopant loading and the number of charge carriers. At high carrier densities, the Seebeck coefficient indeed follows Heike\'s formula, confirming that the conductivity is limited by carrier-carrier repulsion rather than by morphological effects. This study shows that current models of hopping transport in organic semiconductors may be incomplete. As a result, this study offers novel insights in the design of organic semiconductors.

Neuromorphic visual systems (NVSs) hold the potential to not only preserve but also enhance human visual capabilities. One such augmentation lies in harnessing polarization information from light reflected or scattered off surfaces like bees, which can disclose unique characteristics imperceptible to the human eyes. While creating polarization-sensitive optoelectronic synapses presents an intriguing avenue for equipping NVS with this capability, integrating functions like polarization sensitivity, photodetection, and synaptic operations into a singular device has proven challenging. This integration typically necessitates distinct functional components for each performance metric, leading to intricate fabrication processes and constraining overall performance. Herein, a pioneering linear polarized light sensitive synaptic organic phototransistor (OPT) based on 2D molecular crystals (2DMCs) with highly integrated, all-in-one functionality, is demonstrated. By leveraging the superior crystallinity and molecular thinness of 2DMC, the synaptic OPT exhibits comprehensive superior performance, including a linear dichroic ratio up to 3.85, a high responsivity of 1.47 × 104 A W-1, and the adept emulation of biological synapse functions. A sophisticated application in noncontact fingerprint detection achieves a 99.8% recognition accuracy, further highlights its potential. The all-in-one 2DMC optoelectronic synapse for polarization-sensitive NVS marks a new era for intelligent perception systems.

Opto-electronic properties and device performance of organic semiconductors are mainly determined by energy levels of their frontier molecular orbitals, e.g. lowest unoccupied molecular orbital (ELUMO) and highest occupied molecular orbital (EHOMO) in the ground state, first singlet state (ES1) and first triplet state (ET1) in the excited state. These energy levels are always intricately intertwined. Herein, we report a series of monodisperse oligomers based on double B←N bridged bipyridine (BNBP) units. With the increasing number of repeating units, the oligomers exhibit gradually downshifted ELUMO and nearly unchanged EHOMO due to the different distribution of the frontier molecular orbitals of the oligomers. Moreover, the oligomers exhibit gradually decreasing ES1 and nearly unchanged ET1 because of the different contributions of the charge transfer component in the excited state. This work provides new insight into energy level tuning of organic semiconductors, which is important for high-performance organic opto-electronic devices.

Neurostimulation employing photoactive organic semiconductors offers an appealing alternative to conventional techniques, enabling targeted action and wireless control through light. In this study, organic electrolytic photocapacitors (OEPC) are employed to investigate the effects of light-controlled electric stimulation on neuronal networks in vitro and in vivo. The interactions between the devices and biological systems are characterized. Stimulation of primary rat cortical neurons results in an elevated expression of c-Fos within a mature neuronal network. OEPC implantation for three weeks and subsequent stimulation of the somatosensory cortex leads to an increase of c-Fos in neurons at the stimulation site and in connected brain regions (entorhinal cortex, hippocampus), both in the ipsi- and contralateral hemispheres. Reactivity of glial and immune cells after semi-chronic implantation of OEPC in the rat brain is comparable to that of surgical controls, indicating minimal foreign body response. Device functionality is further substantiated through retained charging dynamics following explantation. OEPC-based, light-controlled electric stimulation has a significant impact on neural responsiveness. The absence of detrimental effects on both the brain and device encourages further use of OEPC as cortical implants. These findings highlight its potential as a novel mode of neurostimulation and instigate further exploration into applications in fundamental neuroscience.

The development of nonfullerene acceptors (NFAs), represented by ITIC, has contributed to improving the power conversion efficiency (PCE) of organic solar cells (OSCs). Although tuning the electronic structures to reduce the exciton binding energy (Eb) is considered to promote photocharge generation, a rational molecular design for NFAs has not been established. In this study, we designed and developed two ITIC-based NFAs bearing spiro-substituted bithiophene or biphenyl units (named SpiroT-DCI and SpiroF-DCI) to tune the frontier molecular orbital (FMO) distribution of NFAs. While the highest occupied molecular orbitals (HOMOs) of SpiroF-DCI and ITIC are delocalized in the main π-conjugated framework, the HOMO of SpiroT-DCI is distributed on the bithiophene unit. Reflecting this difference, SpiroT-DCI exhibits a smaller Eb than either SpiroF-DCI or ITIC, and exhibits greater external quantum efficiency in single-component OSCs. Furthermore, SpiroT-DCI shows improved PCEs for bulk-heterojunction OSCs with a donor of PBDB-T, compared with that of either SpiroT-DCI or ITIC. Time-resolved spectroscopy measurements show that the photo-induced intermolecular charge separation is effective even in pristine SpiroT-DCI films. This study highlights the introduction of spiro-substituted bithiophene units that are effective in tuning the FMOs of ITIC, which is desirable for reducing the Eb and improving the PCE in OSCs.

Isoindigo, an electron-withdrawing building block for polymeric field-effect transistors, has long been considered to be non-fluorescent. Moreover, using electron-deficient heterocycle to replace the phenyl ring in the isoindigo core for better electron transport behaviour is synthetically challenging. Here we report the syntheses of a series of tetraazaisoindigos, including pyrazinoisoindigo (PyrII), pyrimidoisoindigo (PymII) and their hybrid (PyrPymII), and the investigation on their photophysical and electric properties. Proper flanking groups need to be chosen to stabilize these highly electron-deficient bislactams. Both PyrII and PymII derivatives show lower LUMO energy levels than that of naphthalene bisimide (NDI). Interestingly, PyrII is instinctively unstable and can be easily reduced, while both PymII derivatives are stable. More surprisingly, PymII derivatives are highly fluorescent and their photoluminescence quantum yields are around 40%, 133 times higher than that of reported isoindigo derivatives. UV-vis spectroscopic results and theoretical calculations show that strong intramolecular hydrogen-bond exists in PymII, which prohibits it from non-radiative decay and accounts for its fluorescent behaviour.  PymII deriviatives are n-type semiconductors, while Ph-PyrII and the hybrid show balanced ambipolar charge transport behaviour, all among the best isoindigo derivatives. Our study not only discloses the structure-property relationship of tetraazaisoindigos, but also provides electron-deficient monomers for conjugated polymers.

Small molecule/polymer semiconductor blends are promising solutions for the development of high-performing organic electronics. They are able to combine ease in solution processability, thanks to the tunable rheological properties of polymeric inks, with outstanding charge transport properties thanks to high crystalline phases of small molecules. However, because of charge injection issues, so far such good performances are only demonstrated in ad-hoc device architectures, not suited for high-frequency applications, where transistor dimensions require downscaling. Here, the successful integration of the most performing blend reported to date, based on 2,7-dioctyl[1] benzothieno[3,2-b][1]benzothiophene (C8-BTBT) and poly(indacenodithiophene-co-benzothiadiazole) (C16IDT-BT), in OFETs characterized by channel and overlap lengths equal to 1.3 and 1.9 µm, respectively, is demonstrated, enabling a transition frequency of 23 MHz at -8 V. Two key aspects allowed such result: molecular doping, leading to width-normalized contact resistance of only 260 Ωcm, allowing to retain an apparent field-effect mobility as high as 3 cm2/(Vs) in short channel devices, and the implementation of a high capacitance dielectric stack, enabling the reduction of operating voltages below 10 V and the overcoming of self-heating issues. These results represent a fundamental step for the future development of low-cost and high-speed printed electronics for IoT applications.

Organic synaptic transistors are a promising technology for advanced electronic devices with simultaneous computing and memory functions and for the application of artificial neural networks. In this study, the neuromorphic electrical characteristics of organic synaptic electrolyte-gated transistors are correlated with the microstructural and interfacial properties of the active layers. This is accomplished by utilizing a semiconducting/insulating polyblend-based pseudobilayer with embedded source and drain electrodes, referred to as PB-ESD architecture. Three variations of poly(3-hexylthiophene) (P3HT)/poly(methyl methacrylate) (PMMA) PB-ESD-based organic synaptic transistors are fabricated, each exhibiting distinct microstructures and electrical characteristics, thus serving excellent samples for exploring the critical factors influencing neuro-electrical properties. Poor microstructures of P3HT within the active layer and a flat active layer/ion-gel interface correspond to typical neuromorphic behaviors such as potentiated excitatory postsynaptic current (EPSC), paired-pulse facilitation (PPF), and short-term potentiation (STP). Conversely, superior microstructures of P3HT and a rough active layer/ion-gel interface correspond to significantly higher channel conductance and enhanced EPSC and PPF characteristics as well as long-term potentiation behavior. Such devices were further applied to the simulation of neural networks, which produced a good recognition accuracy. However, excessive PMMA penetration into the P3HT conducting channel leads to features of a depressed EPSC and paired-pulse depression, which are uncommon in organic synaptic transistors. The inclusion of a second gate electrode enables the as-prepared organic synaptic transistors to function as two-input synaptic logic gates, performing various logical operations and effectively mimicking neural modulation functions. Microstructure and interface engineering is an effective method to modulate the neuromorphic behavior of organic synaptic transistors and advance the development of bionic artificial neural networks.

Shortwave-infrared (SWIR) photodetectors are vital for many scientific and industrial applications including surveillance, quality control and inspection. In recent decades, photodetectors based on organic semiconductors have emerged, demonstrating potential to add real value to broadband and narrowband imaging and sensing scenarios, where factors such as thermal budget sensitivity, large area aperture necessity, cost considerations, and lightweight and conformal flexibility demands are prioritized. It is now recognized that the performance of organic photodetectors (OPDs), notably their specific detectivity, is ultimately limited by trap states, universally present in disordered semiconductors. This work adopts an approach of utilizing these mid-gap states to specifically create a SWIR photo-response. To this end, this work introduces a somewhat counter-intuitive approach of \"trap-doping\" in bulk heterojunction (BHJs) photodiodes, where small quantities of a guest organic molecule are intentionally incorporated into a semiconducting donor:acceptor host system. Following this approach, this work demonstrates a proof-of-concept for a visible-to-SWIR broadband OPD, approaching (and, to some extent, even exceeding) state-of-the-art performance across critical photodetector metrics. The trap-doping approach is, even though only a proof-of-concept currently, broadly applicable to various spectral windows. It represents a new modality for engineering photodetection using the unconventional strategy of turning a limitation into a feature.

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.