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This study investigates the role of non-covalent interactions (NCIs) in stabilizing blends of the conjugated polymer PM6 with additives polyvinyl chloride (PVC) and chlorinated polyethylene (CPE). Using the NCI index, reduced density gradient analysis, and energy decomposition analysis (EDA), we quantify the contributions of van der Waals forces, hydrogen bonding, and steric repulsions in these systems. Our results reveal that PVC/PM6 blends exhibit stronger NCI, particularly C–H⋯π and C–Cl⋯π interactions, compared to CPE/PM6 blends. EDA further shows that dispersion forces and electrostatic interactions are the primary stabilizing factors in the PVC blend, with hydrogen bonding also playing a critical role. These findings highlight the importance of chlorine content in enhancing NCI and promoting the stability of polymer blends. The insights from this work provide valuable guidance for designing more stable polymer-additive systems in organic electronics and other material applications. [ABSTRACT FROM AUTHOR]

Organic electronics (OE) such as organic light-emitting diodes or organic solar cells represent an important and innovative research area to achieve global goals like environmentally friendly energy production. To accelerate OE material discovery, various computational methods are employed. For the initial generation of structures, a molecular cluster approach is employed. Here, we present a semi-automated workflow for the generation of monolayers and aggregates using the GFNn-xTB methods and composite density functional theory (DFT-3c). Furthermore, we present the novel D11A8MERO dye interaction energy benchmark with high-level coupled cluster reference interaction energies for the assessment of efficient quantum chemical and force-field methods. GFN2-xTB performs similar to low-cost DFT, reaching DFT/mGGA accuracy at two orders of magnitude lower computational cost. As an example application, we investigate the influence of the dye aggregate size on the optical and electrical properties and show that at least four molecules in a cluster model are needed for a qualitatively reasonable description. [ABSTRACT FROM AUTHOR]

Pentacene is an important model organic semiconductor in both the singlet exciton fission (SF) and organic electronics communities. We have investigated the effect of changing crystal structure on the SF process, generating multiple triplet excitons from an initial singlet exciton, and subsequent triplet recombination. Unlike for similar organic semiconductors that have strong SF sensitive to polymorphism, we find almost no quantitative difference between the kinetics of triplet pair (TT) formation in the two dominant polymorphs of pentacene. Both pairwise dimer coupling and momentum-space crystal models predict much faster TT formation from the bright singlet excited state of the Bulk vs ThinFilm polymorph, contrasting with the experiment. GW and Bethe–Salpeter equation calculations, including exciton–phonon coupling, reveal that ultrafast phonon-driven transitions in the ThinFilm polymorph compensate the intrinsically slower purely Coulomb-mediated TT formation channel, rationalizing the similarity in observed rates. Taking into account the influence of subtle structural distinctions on both the direct and phonon-mediated SF pathways reveals a predictive capability to these methods, expected to be applicable to a wide variety of molecular crystals. [ABSTRACT FROM AUTHOR]

Superior properties in organic mixed ionic-electronic conductors (OMIECs) over inorganic counterparts have inspired intense interest in biosensing, soft-robotics, neuromorphic computing, and smart medicine. However, slow ion transport relative to charge transport in these materials is a limiting factor. Here, it is demonstrated that hydrophilic molecules local to an interfacial OMIEC nanochannel can accelerate ion transport with ion mobilities surpassing electrophoretic transport by more than an order of magnitude. Furthermore, ion access to this interfacial channel can be gated through local surface energy. This mechanism is applied in a novel sensing device, which electronically detects and characterizes chemical reaction dynamics local to the buried channel. The ability to enhance ion transport at the nanoscale in OMIECs as well as govern ion transport through local chemical signaling enables new functionalities for printable, stretchable, and biocompatible mixed conduction devices.

Designing polymers with high intrinsic thermal conductivity (TC) is critically important for the thermal management of organic electronics and photonics. However, this is a challenging task owing to the diversity of the chemical space and the barriers to advanced synthetic experiments/characterization techniques for polymers. In this Tutorial, the fundamentals and implementation of combining classical molecular dynamics simulation and machine learning (ML) for the development of polymers with high TC are comprehensively introduced. We begin by describing the core components of a universal ML framework, involving polymer data sets, property calculators, feature engineering, and informatics algorithms. Then, the process of constructing interpretable regression algorithms for TC prediction is introduced, aiming to extract the underlying relationships between microstructures and TCs for polymers. We also explore the design of sequence-ordered polymers with high TC using lightweight and mainstream active learning algorithms. Lastly, we conclude by addressing the current limitations and suggesting potential avenues for future research on this topic. [ABSTRACT FROM AUTHOR]

Multiresonant fluorophores are a novel class of organic luminophores with a narrow emission spectrum. They can yield organic light-emitting devices, e.g., OLEDs, with high colour purity. In this study, we applied DFT and multiscale modelling to predict the electronic and optical properties of several novel derivatives of indolocarbazole pSFIAc, which had recently shown a high potential in deep-blue OLEDs. We found that the addition of phenyls to a certain position of the pSFIAc core can considerably increase the fluorescent rate, leaving other properties (HOMO, LUMO, lowest excited singlet and lowest triplet states' energies) virtually unaffected. This can improve the efficiency and stability of deep-blue organic light-emitting devices; the suggested phenyl-substituted indolocarbazoles have been shown to be compatible with two popular anthracene-based hosts. On the contrary, the addition of phenyls to another positions of the core is detrimental for optoelectronic properties. QM/MM and QM/EFP calculations yielded negligible inhomogeneous broadening of the emission spectrum of the studied luminophores when embedded as dopants in anthracene-based hosts, predicting high colour purity of the corresponding devices. On the basis of the obtained results, we selected one novel multiresonant indolocarbazole derivative that is most promising for organic light-emitting devices. We anticipate the revealed structure-property relationships will facilitate the rational design of efficient materials for organic (opto)electronics. [ABSTRACT FROM AUTHOR]

Photoresponsive conjugated polymers are a promising target for modern organic electronics. Numerous photoswitchable repeat units have been included covalently within polymeric structures to enable responsive chromic materials, most commonly through side‐chain appendages or through formal conjugation along a π‐conjugated backbone. We recently disclosed a new design whereby the photoswitch elements are cross conjugated to a conjugated polymer main chain. In this case, we found that the extent of photoconversion was dictated in part by competitive main chain light absorption, which could be suppressed by using a photoswitching motif that carried most of the frontier molecular orbital densities. Here, we report the modeling and synthesis of a series of thieno[3,4‐b]thiophene (TT)‐based photochromes with various aromatic flankers imparting varying degrees of steric bulk and π‐conjugation in order to elucidate the balancing act between steric and electronic factors to promote photochromism. These model systems provide a better understanding of the behavior of photochromic units within extended oligomeric and polymeric π‐conjugated materials. [ABSTRACT FROM AUTHOR]

In addition to traditional rubber applications, 1,4‐cis‐polyisoprene (cis‐PI) has been utilized in wearable electronics. While synthetic PI typically exhibits lower durability compared to natural rubber (NR), high‐molecular‐weight cis‐PI compensates by offering improved mechanical properties and chemical resistance. The group proposes using a commercial cis‐PI with high molecular weight of 250 000 g mol−1 (PI250K‐C) grafted onto modified nanoparticle structures including silicon dioxide (mSiO2), rutile titanium dioxide (mRTiO2), and anatase titanium dioxide (mATiO2) as an insulator in organic field effect transistors (OFETs) due to its naturally low dielectric constant. The nanoparticles are pretreated with a coupling agent to improve adhesion and prevent aggregation. Rubber composite films, designated X%‐mY‐PI250K‐C (where X = 10, 20, 30% and Y = mSiO2, mRTiO2, mATiO2), are fabricated using sulfur vulcanization. The modified films demonstrate excellent mechanical stress (1.15 ± 0.1 MPa) and elasticity, enduring 50 loading–unloading cycles without residual strain. In contrast, rubber composites produced from simple blending show half the mechanical stress at 0.7 ± 0.3 MPa, which is attributed to nanoparticle agglomeration observed in SEM and EDX results. Additionally, mRTiO2 nanoparticles significantly increase the dielectric constant of PI250K‐C from 2.12 to 12.93, enhancing electrical performance for TFT applications. This study underscores the effectiveness of the “grafting to” approach for producing robust rubber composites, highlighting the importance of nanoparticle selection and fabrication precision for stretchable organic electronics. [ABSTRACT FROM AUTHOR]

Materials combining stretchability and sensitivity to external stimuli are key for wearable electronics applications to enable the emergence of disruptive technologies in biosensing, health monitoring, photodetection and human motion recognition. Conductive organohydrogels have gained significant attention due to their high sensitivity and cost‐effective preparation. Biopolymers like gelatin and alginate offer unique opportunities for developing responsive wearable devices, owing to their biocompatibility and sensitivity toward environmental factors. Here sustainable bio‐inspired method is presented to produce alginategelatin organohydrogels combining transparency in the visible range, ionic conductivity, high stretchability, and multiresponsiveness. The controlled alginate's crosslinking with various metal cations like Mn2+, Cu2+, Fe3+, and Zr4+ enables modulating ionic conductivity as well as finely tuning the material's thermal and mechanical properties. These organohydrogels show responsiveness to temperature (from 10 to 50 degrees, with a sensitivity of 0.19 K−1), relative humidity (from 20 to 80%, with a sensitivity of 0.022 RH(%)−1), and strain (gauge factor >1.6), enabling real‐time monitoring of environmental and physiological parameters. Remarkably, they also exhibit photoresponsivity of 9.2 µA W−1 under visible light, a feature rarely reported in literature. The ease of tuning responsiveness to the chosen stimuli and the high sensitivities open perspectives for applying these materials as wearable stretchable sensors. [ABSTRACT FROM AUTHOR]

The increasing demand for the rapid identification of various pathogens and disease biomarkers makes it essential to develop selective and reliable biosensors. The three basic components of a biosensor are: (i) the bioreceptor that binds to the target analyte, (ii) the transducer that converts the signal, and (iii) a signal processing circuit. Integrating the biorecognition elements onto the transducer surface is a critical step that governs the selectivity and reliability of biosensors. Here, we present a novel approach for functionalizing aerosol jet-printed organic electrochemical transistors (OECTs) for biosensing applications. Our design utilizes a printed Au gate modified with N-heterocyclic carbene (NHC) linkers for biofunctionalization. NHC was selected due to its excellent stability and high binding affinity with transition metals, facilitating a robust biofunctionalization mechanism. Utilizing the NHC-Au surfaces, we developed OECT-based biosensors that successfully detected the biotin-streptavidin (biotin-SA) binding events as threshold voltage shift (ΔVT) of 193 ± 64 mV, which is approximately three-fold of that for bovine serum albumin (BSA) (62 ± 41 mV), indicating the NHC functionalized OECT-based biosensor is selective towards the target analyte. In addition, the NHC-Au electrode and the printed OECT both remained functional after 24 months of storage at room temperature, with comparable performances (ΔVT = 161 ± 30 mV for SA binding) as the freshly prepared ones, demonstrating outstanding long-term stability. To the best of our knowledge, this is the first study combining NHC and OECT for biosensing and showcasing 24-month long-term stability. Given the versatility of NHCs in forming highly stable covalent bonds with most transition metals, this study is an important demonstration of their application in bioelectronics. Thus, we have shown a prominent biosensor development technology based on carbenes and organic electronics, which can be adapted to various biomolecule detection and biomedical applications. The exceptional stability of the printed OECTs and NHC functionalized gate highlights their potential for long-term biosensing applications, paving the way for reliable bioelectronics. [ABSTRACT FROM AUTHOR]

Polydiacetylenes (PDAs) are versatile smart materials due to their unique optoelectronic properties and sensitivity to environmental changes such as temperature, pH, and pressure, leading to distinct color transitions. Despite advantageous features, the limited solubility and challenging processing of PDAs often restrict their application in sensor manufacturing. Addressing the limitations of PDAs, this work combines PDAs with oligosiloxanes to create a material exhibiting good solubility in common organic solvents, facilitating the formation of thin films through solution deposition. A meticulous characterization strategy is used, including Raman spectroscopy, optical spectroscopy, and differential scanning calorimetry, to explore the thermochromic and electronic properties of the new crosslinked materials for the fabrication of optical‐electronic temperature sensors. The synthesized material displayed reversible thermochromism from 25 to 47 °C and a nonreversible transition beyond this temperature range. Dual‐mode capacitive temperature sensors fabricated from the new materials exhibited sensitivity (0.1 pF/°C) in the 25–80 °C range. The hybrid sensing mechanism developed enhances accuracy and reliability by monitoring temperature changes through both colorimetric shifts and capacitance variation. The development of new PDA‐crosslinked oligosiloxane not only marks an advancement in smart material technology but also opens new possibilities for diverse sensor applications. [ABSTRACT FROM AUTHOR]

Herein, a design strategy is explored for thermally activated delayed fluorescence (TADF) materials by employing the meta‐linkage of the spiral‐donors 10H‐spiro[acridine‐9,9'‐thioxanthene] (DspiroS) and 10',10'‐dimethyl‐10H,10'H‐spiro[acridine‐9,9'‐anthracene] (DspiroAc) to the robust acceptor 2,4,6‐triphenyl‐1,3,5‐triazine (TRZ). Two distinct TADF materials, m‐DspiroS‐TRZ and m‐DspiroAc‐TRZ, exhibiting unique photophysical properties and performance characteristics were synthesized. Interestingly, even subtle modifications in the molecular architecture can significantly impact the organization of materials in their aggregated state, thereby governing photophysical properties and inducing corresponding alterations in photoelectric characteristics. Notably, m‐DspiroS‐TRZ exhibits superior photophysical properties and exciton dynamics data, achieving a high photoluminescence quantum yield (PLQY) value of up to 95.9% and a rapid reverse intersystem crossing (RISC) rate (풌푹푰푺푪) of 1.0 × 106 s−1. This positions m‐DspiroS‐TRZ as a potentially excellent terminal emissive and sensitizing host material, inspiring further exploration of its applications in electroluminescence. Consequently, TADF organic light‐emitting device (TADF‐OLED) and TADF‐sensitized fluorescence (TSF‐OLED) based on m‐DspiroS‐TRZ have achieved maximum external quantum efficiencies (EQEs) of 31.8% and 34.5%, respectively, demonstrating the significant versatile potential of m‐DspiroS‐TRZ. [ABSTRACT FROM AUTHOR]

One grand challenge for printed organic electronics is the development of a knowledge platform that describes how polymer semiconductors assemble from solution, which requires a unified picture of the complex interplay of polymer solubility, mass transport, nucleation and, e.g., vitrification. One crucial aspect, thereby, is aggregate formation, i.e., the development of electronic coupling between adjacent chain segments. Here, it is shown that the critical aggregation temperatures in solution (no solvent evaporation allowed) and during film formation (solvent evaporation occurring) are excellent pointers to i) establish reliable criteria for polymer assembly into desired aggregates, and ii) advance mechanistic understanding of the overall polymer assembly. Indeed, important insights are provided on why aggregation occurs via a 1‐ or 2‐step process depending on polymer solubility, deposition temperature and solvent evaporation rate; and the selection of deposition temperatures for specific scenarios (e.g., good vs bad solvent) is demystified. Collectively, it is demonstrated that relatively straightforward, concurrent in situ time‐resolved absorbance and photoluminescence spectroscopies to monitor aggregate formation lead to highly useful and broadly applicable criteria for processing functional plastics. In turn, improved control over their properties and device performance can be obtained toward manufacturing sensors, energy‐harvesting devices and, e.g., bioelectronics systems at high yield. [ABSTRACT FROM AUTHOR]

Drosophila can rapidly and precisely detect changes in light in their surroundings and achieve acute perception of motion information with high energy efficiency and adaptivity owing to the cooperation of “ON” channel and the “OFF” channel in its visual system. Optical controlled bidirectional synaptic behavior of neuromorphic device is important for modeling parallel processing channels of Drosophila's visual system. In this study, an ambipolar transistor utilizing a bilayer architecture composed of p‐type pentacene and n‐type C60 as semiconductors is developed, with near‐infrared (NIR) PbS quantum dots serving as the charge‐trapping layer. This design enables a gate‐tunable positive and negative photoresponse, driven by photogating and photovoltaic effects at visible and NIR wavelengths. When regulated by a negative gate voltage, the device exhibits a suppressed photocurrent relaxation time exceeding 1000 s, demonstrating stable long‐term inhibitory characteristics. Consequently, high‐contrast excitatory and inhibitory synapses facilitate orientation and motion detection. Identification accuracies of up to 94.8% for motion direction and 98.1% for dynamic gestures are achieved. Practical applications such as intelligent monitoring and human–computer interaction stand to benefit significantly from these findings. [ABSTRACT FROM AUTHOR]

Incorporation of regular order pores/holes/defects into semimetalic graphene sheets can tune the band gap up to 1 eV or more introducing semiconducting property and therefore exhibiting promising applications for organic electronics such as field‐effect transistors (FETs), molecular sieve membranes, gas sensing, catalysis devices, etc. In this mini review, we focused on bottom‐up approaches to introduce periodic homogeneous pores into graphene and nanographene and graphene nanoribbons along with their characteristics and potential applications in various fields. [ABSTRACT FROM AUTHOR]

Star‐shaped conjugated materials exhibit monodisperses, well‐defined structures akin to small molecules while possessing the high molecular weights typical of polymers, making them appealing for organic electronics. Herein, a series of star‐shaped electron acceptors, labeled SP1‐Ph, SP2‐Ph, SP3‐Ph, SP4‐Ph, and SP6‐Ph correspond to one to six number of arms, have been synthesized for use in organic solar cells (OSCs). The acceptors have been synthesized through Williamson ether synthesis, utilizing OH‐substituted Y‐type precursors and (multiple‐substituted bromomethyl)benzene. An increase in the number of arms results in weakened crystallinity and different aggregation behavior. Therefore, different number of arms can efficiently tune phase separation sizes between the acceptors and donor polymer blended films, which dominates the charge generation process in OSCs. As a result, SP3‐Ph and SP4‐Ph, with modest phase separation size in binary blends, have achieved optimal efficiencies of 16.10% with high stability. However, SP6‐Ph‐based OSC exhibits oversized phase separation and low efficiency of 8.87%. Furthermore, the use of SP3‐Ph and SP4‐Ph in ternary OSCs leads to an impressive efficiency of 19.3%. These results highlight the ability of star‐shaped electron acceptors with varying arm numbers to precisely control the phase separation of photoactive layers, thereby advancing the development of highly efficient and stable OSCs. [ABSTRACT FROM AUTHOR]

Blocked copolymers are a versatile and powerful class of materials, and their properties can be modified by carefully designing the molecular architecture. Their ability to self‐assemble into nanoscale structures and their multifunctionality make them invaluable in advanced materials science, nanotechnology, and biomedical engineering. Compared to traditional blocked copolymer morphologies such as linear, cyclic, and branched, 2D layer‐blocked frameworks provide materials with clear structure, permanent porosity, favorable chemical and thermal stability, larger surface area, ultra‐high carrier mobility, efficient charge separation and migration, and excellent photoexcitation response. In this concept article, we summarized the design concepts and state‐of‐the‐art strategies for the construction of 2D layer‐blocked frameworks and reviewed the development of some 2D‐like blocked frameworks and their applications in semiconductor, catalysis, energy storage, and so forth. Finally, we also outlook for the challenges of these materials in preparation and applications across different research fields. [ABSTRACT FROM AUTHOR]

Solution‐processed organic and hybrid semiconductor materials have great potential for ionizing radiation direct detection, as they combine high sensitivity, low‐power consumption, and flexibility. There is, however, an open challenge related to the stability in ambient/operational conditions of this class of devices. In this work, an air‐stable, solution‐processed and flexible X‐ray detector is reported, based on the integration of hybrid perovskite and organic thin films used as active layer and functional interlayers, respectively. The diode architecture and the engineering of the interface between the hybrid perovskite and the organic hole transporting material (solvent‐modified poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate) is the key to achieve enhanced detector's air stability and performance. The unencapsulated flexible device, measured in air and in passive operation (0 V), shows a limit‐of‐detection of 0.37 ± 0.04 µGy s−1 and a sensitivity as high as 5.2 µC Gy−1 cm−2, which is retained within 25% after 42 days exposure to ambient conditions. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

2D covalent organic frameworks (COFs) are highly porous crystalline materials with promising applications in organic electronics. Current methods involve either on‐surface synthesis (solid surface) or interfacial synthesis (liquid/liquid, liquid/gas interface) to create thin films for these applications, each with its drawbacks. On‐surface synthesis can lead to contamination from COF powder or unreacted chemicals, while interfacial synthesis risks damaging the film during post‐transfer processes. These challenges necessitate the development of alternative synthesis methods for high‐quality 2D COF films. This study presents a novel approach for synthesizing homogeneous 2D COF thin films by combining photochemistry and a liquid‐flowing system. Leveraging previous work on liquid flow systems to prevent contamination during solvothermal synthesis, this approach to the photochemical method, resulting in the synthesis of high‐crystalline 2D COF films with tunable thickness is adopted. The photochemical approach offers spatially controllable energy sources, enabling patternable COF synthesis. Notably, it is successfully fabricated ultrasmooth patterned 2D COF films on hexagonal boron nitride, offering a streamlined process for optoelectronic device fabrication without additional pre, post‐processing steps. [ABSTRACT FROM AUTHOR]

Conductive polymer composites (CPCs) are widely used in the field of organic electronics as the material basis of high-performance devices, due to their obvious advantages including electrical conductivity, lightness, processability and so on. Research on CPCs has focused on the enhancement of their electrical features and the exploration of their application prospects from conventional fields to heated emerging areas like flexible, stretchable, wearable, biological and biomedical electronics, where their mechanical properties are quite critical to determine their practical device performances. Also, a main challenge to ensure their safety and reliability is on the synergistic enhancement of their electrical behavior and mechanical properties. Herein, we systematically reviews the research progress of CPCs with different conductive fillers (metals and their oxides, carbon-based materials, intrinsically conductive polymers, MXenes, etc.) relying on rich material forms (hydrogel, aerogel, fiber, film, elastomer, etc.) in terms of mechanical property regulation strategies, mainly relying on optimized composite material systems and processing techniques. A summary and prospective overview of current issues and future developments in this field also has been presented. [ABSTRACT FROM AUTHOR]

With the goal of cultivating diverse and innovative technical talents, this study addresses the foundational and abstract nature of chemistry courses through teaching mode reforms. Diverse teaching methods are adopted, along with the establishment of an information-based second classroom. Additionally, the experimental component sees the inclusion of design-oriented and open-ended experiments, coupled with the implementation of diverse process-based assessment methods. Ultimately, these changes aim to enhance students' overall competence and innovation skills, contributing to the cultivation of more innovative scientific and technological talents in the field of organic electronics and information. [ABSTRACT FROM AUTHOR]

The creation of ordered structures of molecules assembled from solution onto a substrate is a fundamental technological necessity across various disciplines, spanning from crystallography to organic electronics. However, achieving macroscopic order poses significant challenges, since the process of deposition is inherently impacted by factors like solvent evaporation and dewetting flows, which hinder the formation of well‐organized structures. Traditional methods like drop casting or spin coating encounter limitations due to the rapid kinetics of solvent evaporation, leading to limited control over final uniformity and order. In response to these challenges, Solvent Vapour Annealing (SVA) has emerged as a promising solution for realizing ordered molecular structures at scales ranging from nano‐ to milli‐ meters. SVA decouples the self‐assembly stage from the deposition stage by utilizing solvent vapours which can enable rearrangement, movement, and diffusion of large molecules on the surface even on a macroscopic scale. Essentially acting as "molecular lubricants," solvent vapours enable the formation of well‐ordered molecular films. This review discusses the advancements, obstacles, and promising strategies associated with utilizing SVA for the development of innovative nanostructured thin films, and emphasizes the originality and effectiveness of molecular assembly on substrates achieved through this approach. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Tin oxide (SnO2) has been widely used as an electron transport layer (ETL) in optoelectronic devices. However, there are numerous surface or bulk defects in SnO2, working as charge recombination centers to degrade device. Here, an electroactive and self‐healing polyurethane (PHNN) was designed by integrating conjugated unit – naphthalene diimide (NDI) into a typical polyurethane backbone. Numerous hydrogen bonds and π interactions in PHNN work as non‐covalent interactions to endow this polymer with superior self‐healing properties. PHNN contains lots of aliphatic amine and carbonyl groups, which effectively passivate the defects in SnO2. The π stacking of NDI units will facilitate electron delocalization, endowing PHNN with electrical activity compared with traditional polyurethane. Doping SnO2 with PHNN can improve the conductivity and reduce the work function of SnO2 layer, which is conducive to efficient charge extraction and transport. Using PHNN doped SnO2 as ETL for PM6: Y6 and PM6: BTP‐eC9 based inverted organic solar cells can achieve a high efficiency of 17.16% and 17.51%, respectively. Devices containing doped SnO2 ETL show significantly improved efficiency and stability. Thus, the electroactive polyurethane doped SnO2 interlayers show high performance interfacial modification to align energy‐levels in solar cell devices, which have promising applications in organic electronics. [ABSTRACT FROM AUTHOR]

Organic Electronic platforms for biosensing are being demonstrated at a fast pace, especially in healthcare applications where the use of organic (semi‐)conductive materials leads to devices that efficiently interface living matter. Nevertheless, interesting properties of organic (semi‐)conductors are usually neglected in the development of (bio‐)sensors. Among these, the non‐linear response when operated under dynamic biasing conditions (i.e., with pulsed driving voltages), thus mimicking synaptic plasticity phenomena, offers promising and largely unexplored possibilities for bio‐sensing. The artificial synaptic response's figures of merit reflect the composition of the surrounding environment and, ultimately, the ion concentration and dynamics at the organic (semi‐)conductor/electrolyte interface. Therefore, new sensing strategies that rely on the effect of target analytes on the short‐term plasticity response of Organic Neuromorphic Devices are being demonstrated. This work presents the development of a label‐free Single Electrode Neuromorphic Device (SEND) specifically designed for in vivo real‐time mapping of dopamine concentration. The device response is investigated as a function of the driving frequency, resulting in the determination of the optimal operational configuration for minimally invasive neuromorphic devices. It exhibits stable multi‐parametric response in complex fluids, in brain's mechanical models and in vivo, enabling monitoring of local variations of dopamine concentration in the rat brain. [ABSTRACT FROM AUTHOR]

There is increasing interest in using specialized circuits based on emerging technologies to develop a new generation of smart devices. The process and device variability exhibited by such materials, however, can present substantial challenges for designing circuits. Three models are considered here: a physical compact model, an empirical look‐up table, and an empirical surrogate model based on a multilayer perceptron (MLP) regression. Each one is fit to measurements of discrete organic thin film transistors in the low voltage regime. It is shown that the models provide consistent results when designing artificial neuron circuits, but that the MLP regression provides the highest accuracy and is much simpler to fit compared to the compact model. The targeted technology exhibits non‐ideal behavior such as variable threshold voltage and hysteresis. Using the MLP regression model, the effect of such variability on the performance of an artificial neuron circuit is compared. It is found that these effects alter the neuron firing rate and change the time spent in the on/off states but do not change the basic operation. [ABSTRACT FROM AUTHOR]

Organic electroactive materials, particularly semiconducting polymers, are at the forefront of emerging organic electronics. Among the plethora of unique features, the possibility to formulate inks out of these materials is particularly promising for the large‐scale manufacturing of electronics at lower cost on a variety of soft substrates. While solution deposition of semiconducting materials is promising for developing printed electronics, the environmental footprint of the materials and related devices needs to be considered to achieve sustainable manufacturing. Towards the development of greener printed electronics, this work investigates the utilization of a non‐toxic, environmentally‐friendly solvent, namely branched polyethylene (BPE), to formulate semiconducting inks. Focusing on a diketopyrrolopyrrole‐based (DPP) semiconducting polymer, shellac as dielectric, and BPE as the solvent, solutions were prepared in different concentrations and their rheological properties were characterized. Then, printing on polyethylene terephthalate (PET) substrates using two different techniques was performed to fabricate organic field‐effect transistors (OFETs). Both printing techniques yielded OFETs with good performance and device characteristics, averaging approximately 10−2 and 10−4 cm2 V−1 s−1, respectively, for slot‐die coating and direct‐ink writing deposition. Notably, despite some difference in threshold voltages, OFETs produced via slot‐die coating and direct‐ink writing showed comparable charge mobilities to previously reported OFETs prepared from similar materials, particularly those prepared on silicon dioxide wafers. Overall, this work confirms the suitability of BPE to formulate semiconducting inks to develop printed electronics in a greener manner. The printing methodology developed in this work also open new avenues for the design of functional printed electronics and related technologies. [ABSTRACT FROM AUTHOR]

In organic light-emitting diodes (OLEDs), hole transport is typically about two orders of magnitude faster than electron transport. This leads to carrier complexation near the cathode and exciton bursting on the cathode metal surface, greatly reducing the luminescence efficiency of the device. To solve this problem, we constructed a composite buffer layer of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) synergized with silver nanoparticles (Ag NPs) and introduced it between the anode and the organic layer, which allows the holes to diffuse laterally under the influence of the concentration gradient, so that the luminescent region extended beyond the overlap of the cathode–anode. The lateral diffusion of holes can reduce the accumulation of holes in the device and improve the device stability. More importantly, adding the material C70 with a high highest occupied molecular orbital (HOMO) energy level to form a heterojunction in this buffer layer can further control the lateral diffusion distance and the longitudinal injection rate of holes; when the ratio of the two is 1:1, the carrier balance of the OLED is optimal, and the optical performance is excellent. This work provides a new strategy for OLED current balancing and opens up a new avenue for fabricating high-efficiency OLEDs. [ABSTRACT FROM AUTHOR]

A key component of organic bioelectronics is electrolyte‐gated organic field‐effect transistors (EG‐OFETs), which have recently been used as sensors to demonstrate label‐free, single‐molecule detection. However, these devices exhibit limited stability when operated in direct contact with aqueous electrolytes. Ultrahigh stability is demonstrated to be achievable through the utilization of a systematic multifactorial approach in this study. EG‐OFETs with operational stability and lifetime several orders of magnitude higher than the state of the art have been fabricated by carefully controlling a set of intricate stability‐limiting factors, including contamination and corrosion. The indacenodithiophene‐co‐benzothiadiazole (IDTBT) EG‐OFETs exhibit operational stability that exceeds 900 min in a variety of widely used electrolytes, with an overall lifetime exceeding 2 months in ultrapure water and 1 month in various electrolytes. The devices were not affected by electrical stress‐induced trap states and can remain stable even in voltage ranges where electrochemical doping occurs. To validate the applicability of our stabilized device for biosensing applications, the reliable detection of the protein lysozyme in ultrapure water and in a physiological sodium phosphate buffer solution for 1500 min was demonstrated. The results show that polymer‐based EG‐OFETs are a viable architecture not only for short‐term but also for long‐term biosensing applications. [ABSTRACT FROM AUTHOR]

Carbazoles and their derivatives are ubiquitous in organic electronics since these compounds combine relatively low cost, chemical and thermal stability, and good hole transport properties, along with a tunable electronic structure. Thus, the application of carbazole molecules in the development of optoelectronic and photovoltaic devices, such as OLEDs and solar cells, has been explored with different patterns of functionalization (N-substitution, di- and polyfunctionalization) in the quest for increased efficiencies. In this review, we provide a brief overview of the basic aspects related to solar cells and OLEDs with a focus on the applications involving these versatile and promising building blocks. [ABSTRACT FROM AUTHOR]

Advancements in organic electronics are propelling the development of new material systems, where organic materials stand out for their unique benefits, including tunability and cost‐effectiveness. Organic single crystals stand out for their ordered structure and reduced defects, enhancing the understanding of the relationship between structure and performance. Organic cocrystal engineering builds upon these foundations, exploring intermolecular interactions within multicomponent‐ordered crystalline materials to combine the inherent advantages of single‐component crystals. However, the path to realizing the full potential of organic cocrystals is fraught with challenges, including structural mismatches, unclear cocrystallization mechanisms, and unpredictable property alterations, which complicate the effective cocrystallization between different molecules. To deepen the understanding of this promising area, this review introduces the mechanism of organic cocrystal formation, the various stacking modes, and different growth techniques, and highlights the advancements in cocrystal engineering for multifunctional applications. The goal is to provide comprehensive guidelines for the cocrystal engineering of high‐performance molecular materials, thereby expanding the applications of organic cocrystals in the fields of optoelectronics, photothermal energy, and energy storage and conversion. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Tin oxide (SnO2) has been widely used as an electron transport layer (ETL) in optoelectronic devices. However, there are numerous surface or bulk defects in SnO2, working as charge recombination centers to degrade device. Here, an electroactive and self‐healing polyurethane (PHNN) was designed by integrating conjugated unit – naphthalene diimide (NDI) into a typical polyurethane backbone. Numerous hydrogen bonds and π interactions in PHNN work as non‐covalent interactions to endow this polymer with superior self‐healing properties. PHNN contains lots of aliphatic amine and carbonyl groups, which effectively passivate the defects in SnO2. The π stacking of NDI units will facilitate electron delocalization, endowing PHNN with electrical activity compared with traditional polyurethane. Doping SnO2 with PHNN can improve the conductivity and reduce the work function of SnO2 layer, which is conducive to efficient charge extraction and transport. Using PHNN doped SnO2 as ETL for PM6: Y6 and PM6: BTP‐eC9 based inverted organic solar cells can achieve a high efficiency of 17.16% and 17.51%, respectively. Devices containing doped SnO2 ETL show significantly improved efficiency and stability. Thus, the electroactive polyurethane doped SnO2 interlayers show high performance interfacial modification to align energy‐levels in solar cell devices, which have promising applications in organic electronics. [ABSTRACT FROM AUTHOR]

Abstract Organic electronics represent a promising frontier in the research and development of flexible, lightweight, and cost-effective electronic devices. However, their broader adoption is currently impeded by several critical challenges, including material stability, low charge carrier mobility, difficulties in controlling crystallization and morphology, and overall device reliability. This article provides a detailed analysis of these challenges, and discusses how they affect the performance and longevity of organic electronic devices. It then explores the incorporation of polystyrene (PS) as a polymer additive, highlighting its effectiveness in mitigating these issues. PS, when blended with organic semiconductor materials, has been shown to significantly enhance device performance by improving molecular ordering, reducing defect density, and stabilizing interfaces. In thin film transistors, PS contributes to better mechanical stability and higher charge carrier mobility by promoting favorable phase segregation and crystallization. In phototransistors and sensors, PS enhances sensitivity and selectivity while also improving environmental resistance. Additionally, in memory devices, PS facilitates better charge storage and retention characteristics. This article underscores the critical role of PS in advancing organic electronics, and demonstrates how its strategic use can overcome some of the most persistent challenges in the field, paving the way for unlocking the full potential of organic electronic devices in commercial applications.

In this study, analytical models for space charge limited current (SCLC) transport in a porous (or disordered) trap-limited dielectric cylindrical configuration are developed. The method used in this paper is first verified by reproducing the well-known analytical results for planar cases developed decades ago based on the traditional approach. By considering the porous solid as a fractional object characterized by a parameter α ≤ 1 , we formulate its fractional capacitance and determine the SCLC transport by using the transit time approach. At α = 1 , it will recover the well-known Mott–Gurney law and Mark–Helfrich law for trap-free and trap-limited cases, respectively. For cylindrical geometry, our findings show an analytical form that is not available from the traditional methods. We anticipate that the proposed analytical model will serve as a useful tool for characterizing the current–voltage measurements in SCLC transport in dielectric breakdown and organic electronics, where spatial porosity of the materials is inevitable. The introduced fractional parameter α extracted from such characterization can facilitate the quantitative determination of the relationship between spatial porosity and charge mobility. [ABSTRACT FROM AUTHOR]

Piperazine‐2,5‐dione (glycine anhydride, GA) has recently emerged as a valuable precursor for high‐performance π‐conjugated polymer semiconductors in organic electronics. We utilized GA to design a novel bisindolin‐dihydropiperazine (IDHP)‐based conjugated polymer, PIDHPTT, for aqueous chemical sensing. In the isatin‐flanked monomer, GA exists as a non‐conjugated lactam (DHP‐NH) but converts to a conjugated lactim (DHP‐OH) form within the polymer. Density functional theory (DFT) calculations show that this conversion is driven by energy minimization via extended π‐conjugation. Neighboring DHP units in the lactim form facilitate this process through π‐bridges, demonstrating a vinylogous effect, which has previously only been observed in small molecules. This is the first study to report such a long‐range vinylogous effect in a polymer due to the collective synergy of numerous functional groups. The OH groups in the lactim DHP interact more strongly with fluoride ions than other halides. PIDHPTT exhibits significant changes in optical absorption, electrochemical impedance, and charge transport in response to fluoride ions, which differ from responses to other halides. A water‐gated organic field‐effect transistor based on PIDHPTT shows excellent sensitivity and selectivity for fluoride ions, demonstrating the potential of this polymer design for chemical sensing applications. [ABSTRACT FROM AUTHOR]

Over the past decades, organic electronics have attracted wide research attention in transistors. One of the devices is organic field effect transistors (OFET), which brought a great revolution for their excellent mechanical flexibility, lightweight, low-temperature deposition, low manufacturing cost and conformable large coverage area, in contrast to conventional silicon-based transistors. This paper highlights the overview of OFET structure, operation and electrical parameters that affect the performance. The influence of gate dielectric thickness, electrode width and channel length on the behavior of transistors in terms of threshold voltage, current ratio and saturation mobility value has also been discussed. The progress in the development of organic semiconductor materials is also outlined, which helps to resolve the power consumption issue. [ABSTRACT FROM AUTHOR]

The selection of suitable polymers is pivotal in influencing the electrical performance and the thermal/electrical stabilities of organic electronics. Here, the superior properties induced by deuteration in polymer/2,8‐difluoro‐5,11‐bis(triethylsilylethynyl)anthradithiophene (diF‐TES ADT) blends are systematically investigated. By employing a combination of experimental and computational analyses, the critical factors underlying charge transport and device stabilities in deuterated polymers (d‐polymers) compared to protonated polymers are elucidated. Deuterated polymers exhibit increased mass due to the substitution of hydrogen with deuterium, reducing the zero‐point vibration energy by 1/√2. This reduction leads to enhanced energetic stabilization and the formation of stronger D─C bonds than H─C bonds. Consequently, deuterated polymers exhibit enhanced thermal properties, along with improved insulating properties, which are intrinsically linked to improved device performance. Additionally, the correlation between the electrical properties and bias stability using deuterated poly(methyl methacrylate) (d‐PMMA) and polystyrene (d‐PS) blends are analyzed. Utilizing complementary neutron & X‐ray reflectivity, and photoexcited charge‐collection spectroscopy (PECCS), phase separation and trap dynamics are delved, providing a comprehensive understanding of these relationships. These findings reveal that d‐polymers significantly enhance the electrical performance and stability of the blends, offering valuable insights for the design of advanced materials in organic electronics. [ABSTRACT FROM AUTHOR]

Acenes are notable for their optoelectronic properties and applications in organic electronics. Starphenes are structurally related molecules possessing three acene arms that radiate linearly from a central benzene ring (i. e., linearly annellated triphenylenes). Large starphenes have been prepared using convergent syntheses involving transition metal catalyzed cyclotrimerizations of either preformed acenes or arynes. Here, we report a one‐pot divergent synthesis of a 13‐ring triquinone that is readily converted to a [4.4.4]tridecastarphene derivative. The one‐pot procedure involves the sequential reactions of three 1,4‐anthraquinones with o‐quinodimethane derivatives that are generated sequentially from a stable, trisulfone precursor. The resulting [4.4.4]tridecastarphene derivative bearing p‐(t‐butyl)phenyl substituents was characterized by 1H NMR, 13C NMR and UV‐vis spectroscopies, as well as mass spectrometry, cyclic voltammetry and differential pulse voltammetry. Theoretical and experimental studies reveal a relatively high‐lying HOMO orbital (about −4.70 to −4.86 eV) and a relatively small HOMO‐LUMO gap (2.1 eV), suggesting utility as a p‐type organic semiconductor. Our [4.4.4]tridecastarphene derivative photooxidizes in a CH2Cl2 solution exposed to ambient light and air with a half‐life of 150 minutes at room temperature, but shows no sign of degradation after 12 months in the solid‐state. Our [4.4.4]tridecastarphene derivative also shows excellent solubility in a number of organic solvents including dichloromethane, chloroform and toluene, potentially enabling printed electronic applications. [ABSTRACT FROM AUTHOR]

The development of blue electroluminescent (EL) materials remains a significant challenge in organic light‐emitting diode (OLED) technology. In this study, a novel design strategy is proposed for blue hot exciton (HE) materials, which involves utilizing a “cross” shaped molecular structure characterized by substantial steric hindrance and a highly twisted conformation. The unique cross‐shaped molecular architecture with distinct “arms” enables flexible control over the excited state properties of the molecule, thereby facilitating precise modulation of high‐lying triplet and low‐lying singlet excited state energy levels. Furthermore, the 3D spatial configuration of the molecule effectively reduces close molecular packing, thereby minimizing the risk of material concentration quenching. The proof‐of‐concept HE emitters CN‐PI and TP‐PI exhibit non‐π‐π stacking configurations in single crystals, achieving high photoluminescence quantum yield (PLQY) values up to 51.3% and 46.5% in non‐doped thin films, respectively, along with rapid radiation decay rates and reasonable distribution of Tm (m ≤ 5) and S1 states. Non‐doped OLEDs incorporating these emitters demonstrate exceptional external quantum efficiencies (EQE), reaching 7.3% and 6.4%, respectively, while exhibiting minimal efficiency roll‐off at high luminance. This research introduces a promising approach for developing high‐performance blue HE emitters. [ABSTRACT FROM AUTHOR]

ABSTRACT The structural, optoelectronic and charge transport properties of porphyrin and its analogues are investigated using the density functional theoretical methods. Most of the above molecules absorb in visible region with high light harvesting efficiency. The small energy gap between the frontier molecular orbitals (FMOs) suggests that porphyrin and its derivatives can be used in organic semiconductors. Electronic properties such as ionization potential, electron affinity, reorganization energy and the charge transfer integral are calculated to obtain their charge transport properties. It is revealed that porphyrin, porphyrazine and phthalocyanine act as hole transporters, whereas corrole and corrolazine act as electron transporters. [ABSTRACT FROM AUTHOR]

Organic electrochemical transistors (OECTs) represent a promising approach for flexible, wearable, biomedical electronics, and sensors integrated with diverse substrates. Their ability to operate at low voltages and interact effectively with biological systems makes them particularly suitable for neuromorphic applications. For neuromorphic devices, OECTs must enhance electrical performance, biocompatibility, and signal storage/erasure capabilities. While UV cross‐linking methods with various side effects on organic semiconductors are predominant in improving mobility and current retention time, thermal cross‐linking based on the solution process has not been extensively explored. Additionally, despite significant research on the modification of electrolyte property, the ionic charge compensation mechanisms between multiple electrolytes are still unclear. This study employs a cross‐linking strategy involving the chemical reaction of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) with di‐tert‐butyl‐peroxide (DTBP) to create a cross‐linked P3HT active layer. Furthermore, a dual ion gel structure combining a conventional ion gel with a chitosan‐based ion gel is investigated for increased ionic transport to enhance OECT performance. Using the above two methods, the enhanced electrical performance showing the mobility of 25 F cm−1 V−1 s−1 and synaptic properties showing long‐term plasticity of cross‐linked OECTs with a dual ion gel structure are demonstrated, suggesting their potential application as high‐performance neuromorphic devices. [ABSTRACT FROM AUTHOR]

Water vapor-impermeable AlON/HfOx bilayer films were constructed through a hybrid high-power impulse magnetron sputtering (HiPIMS) and radio-frequency magnetron sputtering process (RFMS), applied as an encapsulation of flexible electronics such as organic photovoltaics. The deposition of monolithic and amorphous AlON films through HiPIMS was investigated by varying the duty cycles from 5% to 20%. At an accelerated test condition, 60 °C, and 90% relative humidity, a 100 nm thick monolithic AlON film prepared using a duty cycle of 20% exhibited a low water vapor transmission rate (WVTR) of 0.0903 g m−2 day−1 after testing for 336 h. Furthermore, after introducing a nanocrystalline HfOx film through RFMS, a 214 nm thick AlON/HfOx bilayer film reached the lowest WVTR of 0.0126 g m−2 day−1. [ABSTRACT FROM AUTHOR]

Polymeric mixed ionic–electronic conductors hold great potential for advancing high‐performance organic electronics due to their exceptional electrical conductivity achieved through ion–electron coupling. However, the widespread adoption of these conductors faces obstacles due to their reliance on environmentally harmful solvents during processing and the potential performance degradation under various conditions. In this study, a practical solution to these challenges is proposed by incorporating monomers with ionic liquid‐behaving pendant groups into conjugated polymers. The copolymerization of these charged monomers not only improves solubility in environmentally friendly solvents but also imparts long‐term stability against humidity, high temperatures, and mechanical deformation. The immobilized ion species foster highly selective interactions of these polymers with nitrogen dioxide, paving the way for the development of stretchable sensing devices capable of functioning at exceptionally high temperatures. [ABSTRACT FROM AUTHOR]

Over the past two decades, deep eutectic solvents (DESs) have captured significant attention as an emergent class of solvents that have unique properties and applications in differing fields of chemistry. One area where DES systems find utility is the design of polymeric gels, often referred to as "eutectogels," which can be prepared either using a DES to replace a traditional solvent, or where monomers form part of the DES themselves. Due to the extensive network of intramolecular interactions (e.g., hydrogen bonding) and ionic species that exist in DES systems, polymeric eutectogels often possess appealing material properties—high adhesive strength, tuneable viscosity, rapid polymerization kinetics, good conductivity, as well as high strength and flexibility. In addition, non‐covalent crosslinking approaches are possible due to the inherent interactions that exist in these materials. This review considers several key applications of polymeric eutectogels, including organic electronics, wearable sensor technologies, 3D printing resins, adhesives, and a range of various biomedical applications. The design, synthesis, and properties of these eutectogels are discussed, in addition to the advantages of this synthetic approach in comparison to traditional gel design. Perspectives on the future directions of this field are also highlighted. [ABSTRACT FROM AUTHOR]

Hot exciton emitters based on 9,10‐substituted anthracenes are a well‐investigated class of molecules featuring thermally activated delayed fluorescence (TADF). TADF converts triplet excitons into singlet excitons and improves the internal quantum efficiency of electroluminescent devices to performance beyond the limit of spin‐statistics of conventional emitters. In this paper, we compare different 1,8‐functionalized donor/acceptor‐substituted anthracenes and compare these to established 9,10‐functionalized hot exciton emitters. Interestingly, our new 1,8‐substituted anthracenes make use of a beneficial hot exciplex pathway, resulting in improved emission characteristics and higher photoluminescence quantum yield. [ABSTRACT FROM AUTHOR]

The hierarchically coordinated processing of visual information with the data degradation characteristic embodies the energy consumption minimization and signal transmission efficiency maximization of brain activities. This inspires machine vision to handle the explosively increased data in real-time. In this contribution, we demonstrate the possibility of constructing a coordinated perceptive computing paradigm with dual-mode organic memristors to emulate the visual processing capability of the brain systems. The 32-state modulation of the device photoresponsivity and conductance via photo-induced molecular reconfiguration and electrochemical redox activities enables the execution of computing-in-sensor and computing-in-memory tasks, respectively, which in turn allows the homogeneous hardware integration of a single-layer perceptron and a convolutional neural network for high-efficiency hierarchical visual processing. Compared to the sole optoelectronic CIS mode to recognize visual targets, the dual-mode organic memristor-based coordinated computing scheme demonstrates a 24.5% improvement in the recognition accuracy and 45.8% reduction in the network size. [ABSTRACT FROM AUTHOR]

Achieving low threshold voltage (Vth) in organic electrochemical transistors (OECTs) is essential for minimizing power consumption and enhancing sensitivity in bioelectronic devices. However, obtaining OECT materials with ultra‐low Vth, close to 0 V for n‐type conjugated polymers remains challenging. Here, a conjugated polymer FBDOPV‐CNTVT is introduced, which features a rigid backbone structure and high electron deficiency, leading to an exceptionally low lowest unoccupied molecular orbital (LUMO) energy level of −4.67 eV, achieved through dual electron‐withdrawing substitutions. With its ultra‐low LUMO energy level, FBDOPV‐CNTVT exhibits high susceptibility to electrochemical doping, even demonstrating efficient doping near 0 V. Consequently, the OECT device employing FBDOPV‐CNTVT as the active material shows an ultra‐low Vth of 7.5 mV, setting a new record for the Vth of n‐type OECT devices. Furthermore, FBDOPV‐CNTVT exhibits a µC* value of 6.13 F cm−1 V−1 s−1 and retains ≈85% of its current after 2000 s cycling. This study highlights the potential of conjugated polymers with dual electron‐withdrawing substitutions to achieve ultra‐low LUMO energy levels, effectively reducing the Vth of n‐type OECT devices and promising advancements in bioelectronics. [ABSTRACT FROM AUTHOR]

휋‐Conjugated polymers, including those based on acetylenic repeating units, are an exciting class of materials that offer narrow optical band gaps and tunable frontier orbital energies that lead to their use in organic electronics. This work expands the knowledge of structure‐property relationships of acetylenic polymers through the synthesis and characterization of a series of Glaser‐Hay‐coupled model compounds and random copolymers comprised of BF2 formazanate, fluorene, and/or bis(alkoxy)benzene units. The model compounds and copolymers synthesized exhibit redox activity associated with the reversible reduction of the BF2 formazanate units and the irreversible reduction of the fluorene and bis(alkoxy)benzene units. The copolymers exhibit absorption profiles characteristic or intermediate of their respective models and homopolymers, leading to broad absorption of UV–vis light. The alkyne linkages of the model compounds and copolymers are reacted with [Co2(CO)8] to convert the alkyne functional groups into cobalt carbonyl clusters. This transformation leads to blue‐shifted absorption profiles due to a decrease in π‐conjugation, demonstrating the ability to tune the properties of these materials through post‐polymerization functionalization. The redox activity and broad absorption bands of the polymers reported make them excellent candidates for use in photovoltaics and other light‐harvesting applications. [ABSTRACT FROM AUTHOR]