Over 19% Efficient Inverted Organic Photovoltaics Featuring a Molecularly Doped Metal Oxide Electron-Transporting Layer.

Molecular doping is commonly utilized to tune the charge transport properties of organic semiconductors. However, applying this technique to electrically dope inorganic materials like metal oxide semiconductors is challenging due to the limited availability of molecules with suitable energy levels and processing characteristics. Herein, n-type doping of zinc oxide (ZnO) films is demonstrated using 1,3-dimethylimidazolium-2-carboxylate (CO2-DMI), a thermally activated organic n-type dopant. Adding CO2-DMI into the ZnO precursor solution and processing it atop a predeposited indium oxide (InOx) layer yield InOx/n-ZnO heterojunctions with increased electron field-effect mobility of 32.6 cm2 V-1 s-1 compared to 18.5 cm2 V-1 s-1 for the pristine InOx/ZnO bilayer. The improved electron transport originates from the ZnO's enhanced crystallinity, reduced hydroxyl concentrations, and fewer oxygen vacancy groups upon doping. Applying the optimally doped InOx/n-ZnO heterojunctions as the electron-transporting layers (ETLs) in organic photovoltaics (OPVs) yields cells with improved power conversion efficiency of 19.06%, up from 18.3% for devices with pristine ZnO, and 18.2% for devices featuring the undoped InOx/ZnO ETL. It is shown that the all-around improved OPV performance originates from synergistic effects associated with CO2-DMI doping of the thermally grown ZnO, highlighting its potential as an electronic dopant for ZnO and potentially other metal oxides.

Photocatalytic doping of organic semiconductors.

Chemical doping is an important approach to manipulating charge-carrier concentration and transport in organic semiconductors (OSCs)1-3 and ultimately enhances device performance4-7. However, conventional doping strategies often rely on the use of highly reactive (strong) dopants8-10, 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.

A Conjugated Carboranyl Main Chain Polymer with Aggregation-Induced Emission in the Near-Infrared.

Materials exhibiting aggregation-induced emission (AIE) are both highly emissive in the solid state and prompt a strongly red-shifted emission and should therefore pose as good candidates toward emerging near-infrared (NIR) applications of organic semiconductors (OSCs). Despite this, very few AIE materials have been reported with significant emissivity past 700 nm. In this work, we elucidate the potential of ortho-carborane as an AIE-active component in the design of NIR-emitting OSCs. By incorporating ortho-carborane in the backbone of a conjugated polymer, a remarkable solid-state photoluminescence quantum yield of 13.4% is achieved, with a photoluminescence maximum of 734 nm. In contrast, the corresponding para and meta isomers exhibited aggregation-caused quenching. The materials are demonstrated for electronic applications through the fabrication of nondoped polymer light-emitting diodes. Devices employing the ortho isomer achieved nearly pure NIR emission, with 86% of emission at wavelengths longer than 700 nm and an electroluminescence maximum at 761 nm, producing a significant light output of 1.37 W sr-1 m-2.

Conjugated Polymer Heteroatom Engineering Enables High Detectivity Symmetric Ambipolar Phototransistors.

Solution-processed high-performing ambipolar organic phototransistors (OPTs) can enable low-cost integrated circuits. Here, a heteroatom engineering approach to modify the electron affinity of a low band gap diketopyrrolopyrole (DPP) co-polymer, resulting in well-balanced charge transport, a more preferential edge-on orientation and higher crystallinity, is demonstrated. Changing the comonomer heteroatom from sulfur (benzothiadiazole (BT)) to oxygen (benzooxadiazole (BO)) leads to an increased electron affinity and introduces higher ambipolarity. Organic thin film transistors fabricated from the novel PDPP-BO exhibit charge carrier mobility of 0.6 and 0.3 cm2 Vs⁻1 for electrons and holes, respectively. Due to the high sensitivity of the PDPP-based material and the balanced transport in PDPP-BO, its application as an NIR detector in an OPT architecture is presented. By maintaining a high on/off ratio (9 × 104), ambipolar OPTs are shown with photoresponsivity of 69 and 99 A W⁻1 and specific detectivity of 8 × 107 for the p-type operation and 4 × 109 Jones for the n-type regime. The high symmetric NIR-ambipolar OPTs are also evaluated as ambipolar photo-inverters, and show a 46% gain enhancement under illumination.

Enhancing the Conductivity and Thermoelectric Performance of Semicrystalline Conducting Polymers through Controlled Tie Chain Incorporation.

Conjugated polymers are promising materials for thermoelectric applications, however, at present few effective and well-understood strategies exist to further advance their thermoelectric performance. Here a new model system is reported for a better understanding of the key factors governing their thermoelectric properties: aligned, ribbon-phase poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) doped by ion-exchange doping. Using a range of microstructural and spectroscopic methods, the effect of controlled incorporation of tie-chains between the crystalline domains is studied through blending of high and low molecular weight chains. The tie chains provide efficient transport pathways between crystalline domains and lead to significantly enhanced electrical conductivity of 4810 S cm-1, which is not accompanied by a reduction in Seebeck coefficient or a large increase in thermal conductivity. Respectable power factors of 173 µW m-1 K-2 are demonstrated in this model system. The approach is generally applicable to a wide range of semicrystalline conjugated polymers and could provide an effective pathway for further enhancing their thermoelectric properties and overcome traditional trade-offs in optimization of thermoelectric performance.

Label-Free Metal-Oxide Transistor Biosensors for Metabolite Detection in Human Saliva.

Metabolites are essential molecules involved in various metabolic processes, and their deficiencies and excessive concentrations can trigger significant physiological consequences. The detection of multiple metabolites within a non-invasively collected biofluid could facilitate early prognosis and diagnosis of severe diseases. Here, a metal oxide heterojunction transistor (HJ-TFT) sensor is developed for the label-free, rapid detection of uric acid (UA) and 25(OH)Vitamin-D3 (Vit-D3) in human saliva. The HJ-TFTs utilize a solution-processed In2 O3 /ZnO channel functionalized with uricase enzyme and Vit-D3 antibody for the selective detection of UA and Vit-D3, respectively. The ultra-thin tri-channel architecture facilitates strong coupling between the electrons transported along the buried In2 O3 /ZnO heterointerface and the electrostatic perturbations caused by the interactions between the surface-immobilized bioreceptors and target analytes. The biosensors can detect a wide range of concentrations of UA (from 500 nm to 1000 µM) and Vit-D3 (from 100 pM to 120 nm) in human saliva within 60 s. Moreover, the biosensors exhibit good linearity with the physiological concentration of metabolites and limit of detections of ≈152 nm for UA and ≈7 pM for Vit-D3 in real saliva. The specificity is demonstrated against various interfering species, including other metabolites and proteins found in saliva, further showcasing its capabilities.

Reducing undesired solubility of squarephaneic tetraimide for use as an organic battery electrode material.

Locally aromatic alkyl-N-substituted squarephaneic tetraimide (SqTI) conjugated macrocycles are four-electron reducible, owing to global aromaticity and presumed global Baird aromaticity of the dianion and tetraanion states, respectively. However, their good solubility inhibits their application as a battery electrode material. By applying sidechain removal as a strategy to reduce SqTI solubility, we report the development of its unsubstituted derivative SqTI-H, which was obtained directly from squarephaneic tetraanhydride by facile treatment with hexamethyldisilazane and MeOH. Compared to alkyl-N-substituted SqTI-Rs, SqTI-H exhibited further improved thermal stability and low neutral state solubility in most common organic solvents, owing to computationally demonstrated hydrogen-bonding capabilities emanating from each imide position on SqTI-H. Reversible solid state electrochemical reduction of SqTI-H to the globally aromatic dianion state was also observed at -1.25 V vs. Fc/Fc+, which could be further reduced in two stages. Preliminary testing of SqTI-H in composite electrodes for lithium-organic half cells uncovered imperfect cycling performance, which may be explained by persistent solubility of reduced states, necessitating further optimisation of electrode fabrication procedures to attain maximum performance.

Fast Near-Infrared Photodetectors Based on Nontoxic and Solution-Processable AgBiS2.

Solution-processable near-infrared (NIR) photodetectors are urgently needed for a wide range of next-generation electronics, including sensors, optical communications and bioimaging. However, it is rare to find photodetectors with >300 kHz cut-off frequencies, especially in the NIR region, and many of the emerging inorganic materials explored are comprised of toxic elements, such as lead. Herein, solution-processed AgBiS2 photodetectors with high cut-off frequencies under both white light (>1 MHz) and NIR (approaching 500 kHz) illumination are developed. These high cut-off frequencies are due to the short transit distances of charge-carriers in the ultrathin photoactive layer of AgBiS2 photodetectors, which arise from the strong light absorption of this material, such that film thicknesses well below 120 nm are sufficient to absorb >65% of NIR to visible light. It is also revealed that ion migration plays a critical role in the photo-response speed of these devices, and its detrimental effects can be mitigated by finely tuning the thickness of the photoactive layer, which is important for achieving low dark current densities as well. These outstanding characteristics enable the realization of air-stable, real-time heartbeat sensors based on NIR AgBiS2 photodetectors, which strongly motivates their future integration in high-throughput systems.

Tissue Equivalent Curved Organic X-ray Detectors Utilizing High Atomic Number Polythiophene Analogues.

Organic semiconductors are a promising material candidate for X-ray detection. However, the low atomic number (Z) of organic semiconductors leads to poor X-ray absorption thus restricting their performance. Herein, the authors propose a new strategy for achieving high-sensitivity performance for X-ray detectors based on organic semiconductors modified with high -Z heteroatoms. X-ray detectors are fabricated with p-type organic semiconductors containing selenium heteroatoms (poly(3-hexyl)selenophene (P3HSe)) in blends with an n-type fullerene derivative ([6,6]-Phenyl C71 butyric acid methyl ester (PC70 BM). When characterized under 70, 100, 150, and 220 kVp X-ray radiation, these heteroatom-containing detectors displayed a superior performance in terms of sensitivity up to 600 ± 11 nC Gy-1  cm-2 with respect to the bismuth oxide (Bi2 O3 ) nanoparticle (NP) sensitized organic detectors. Despite the lower Z of selenium compared to the NPs typically used, the authors identify a more efficient generation of electron-hole pairs, better charge transfer, and charge transport characteristics in heteroatom-incorporated detectors that result in this breakthrough detector performance. The authors also demonstrate flexible X-ray detectors that can be curved to a radius as low as 2 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard ultra-low dark current of 0.03 ± 0.01 pA mm-2 .

A polymer library enables the rapid identification of a highly scalable and efficient donor material for organic solar cells.

The dramatic improvement of the PCE (power conversion efficiency) of organic photovoltaic devices in the past few years has been driven by the development of new polymer donor materials and non-fullerene acceptors (NFAs). In the design of such materials synthetic scalability is often not considered, and hence complicated synthetic protocols are typical for high-performing materials. Here we report an approach to readily introduce a variety of solubilizing groups into a benzo[c][1,2,5]thiadiazole acceptor comonomer. This allowed for the ready preparation of a library of eleven donor polymers of varying side chains and comonomers, which facilitated a rapid screening of properties and photovoltaic device performance. Donor FO6-T emerged as the optimal material, exhibiting good solubility in chlorinated and non-chlorinated solvents and achieving 15.4% PCE with L8BO as the acceptor (15.2% with Y6) and good device stability. FO6-T was readily prepared on the gram scale, and synthetic complexity (SC) analysis highlighted FO6-T as an attractive donor polymer for potential large scale applications.

p-Type Conjugated Polymers Containing Electron-Deficient Pentacyclic Azepinedione.

Bisthienoazepinedione (BTA) has been reported for constructing high-performing p-type conjugated polymers in organic electronics, but the ring extended version of BTA is not well explored. In this work, we report a new synthesis of a key building block to the ring expanded electron-deficient pentacyclic azepinedione (BTTA). Three copolymers of BTAA with benzodithiophene substituted by different side chains are prepared. These polymers exhibit similar energy levels and optical absorption in solution and solid state, while significant differences are revealed in their film morphologies and behavior in transistor and photovoltaic devices. The best-performing polymers in transistor devices contained alkylthienyl side chains on the BDT unit (pBDT-BTTA-2 and pBDT-BTTA-3) and demonstrated maximum saturation hole mobilities of 0.027 and 0.017 cm2 V-1 s-1. Blends of these polymers with PC71BM exhibited a best photovoltaic efficiency of 6.78% for pBDT-BTTA-3-based devices. Changing to a low band gap non-fullerene acceptor (BTP-eC9) resulted in improved efficiency of up to 13.5%. Our results are among the best device performances for BTA and BTTA-based p-type polymers and highlight the versatile applications of this electron-deficient BTTA unit.

Biorenewable Solvents for High-Performance Organic Solar Cells.

With the advent of nonfullerene acceptors (NFAs), organic photovoltaic (OPV) devices are now achieving high enough power conversion efficiencies (PCEs) for commercialization. However, these high performances rely on active layers processed from petroleum-based and toxic solvents, which are undesirable for mass manufacturing. Here, we demonstrate the use of biorenewable 2-methyltetrahydrofuran (2MeTHF) and cyclopentyl methyl ether (CPME) solvents to process donor: NFA-based OPVs with no additional additives in the active layer. Furthermore, to reduce the overall carbon footprint of the manufacturing cycle of the OPVs, we use polymeric donors that require a few synthetic steps for their synthesis, namely, PTQ10 and FO6-T, which are blended with the Y-series NFA Y12. High performance was achieved using 2MeTHF as the processing solvent, reaching PCEs of 14.5% and 11.4% for PTQ10:Y12 and FO6-T:Y12 blends, respectively. This work demonstrates the potential of using biorenewable solvents without additives for the processing of OPV active layers, opening the door to large-scale and green manufacturing of organic solar cells.

Enhanced sub-1 eV detection in organic photodetectors through tuning polymer energetics and microstructure.

One of the key challenges facing organic photodiodes (OPDs) is increasing the detection into the infrared region. Organic semiconductor polymers provide a platform for tuning the bandgap and optoelectronic response to go beyond the traditional 1000-nanometer benchmark. In this work, we present a near-infrared (NIR) polymer with absorption up to 1500 nanometers. The polymer-based OPD delivers a high specific detectivity D* of 1.03 × 1010 Jones (-2 volts) at 1200 nanometers and a dark current Jd of just 2.3 × 10-6 ampere per square centimeter at -2 volts. We demonstrate a strong improvement of all OPD metrics in the NIR region compared to previously reported NIR OPD due to the enhanced crystallinity and optimized energy alignment, which leads to reduced charge recombination. The high D* value in the 1100-to-1300-nanometer region is particularly promising for biosensing applications. We demonstrate the OPD as a pulse oximeter under NIR illumination, delivering heart rate and blood oxygen saturation readings in real time without signal amplification.

Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity via cross-coupling reactions.

Conjugated macrocycles can exhibit concealed antiaromaticity; that is, despite not being antiaromatic, under specific circumstances, they can display properties typically observed in antiaromatic molecules due to their formal macrocyclic 4n π-electron system. Paracyclophanetetraene (PCT) and its derivatives are prime examples of macrocycles exhibiting this behaviour. In redox reactions and upon photoexcitation, they have been shown to behave like antiaromatic molecules (requiring type I and II concealed antiaromaticity, respectively), with such phenomena showing potential for use in battery electrode materials and other electronic applications. However, further exploration of PCTs has been hindered by the lack of halogenated molecular building blocks that would permit their integration into larger conjugated molecules by cross-coupling reactions. Here, we present two dibrominated PCTs, obtained as a mixture of regioisomers from a three-step synthesis, and demonstrate their functionalisation via Suzuki cross-coupling reactions. Optical, electrochemical, and theoretical studies reveal that aryl substituents can subtly tune the properties and behaviour of PCT, showing that this is a viable strategy in further exploring this promising class of materials.

Non-invasive, ultrasensitive detection of glucose in saliva using metal oxide transistors.

Transistor-based biosensors represent an emerging technology for inexpensive point-of-care testing (POCT) applications. However, the limited sensitivity of the current transistor technologies hinders their practical deployment. In this study, we developed tri-channel In2O3/ZnO heterojunction thin-film transistors (TFTs) featuring the surface-immobilized enzyme glucose oxidase to detect glucose in various biofluids. This unusual channel design facilitates strong coupling between the electrons transported along the buried In2O3/ZnO heterointerface and the electrostatic perturbations caused by the interactions between glucose and surface-immobilized glucose oxidase. The enzyme selectively binds to glucose, causing a change in charge density on the channel surface. By exploring this effect, the solid-state biosensing TFT (BioTFT) can selectively detect glucose in artificial and real saliva over a wide range of concentrations from 500 nM to 20 mM with limits of detection of ∼365 pM (artificial saliva) and ∼416 nM (real saliva) in less than 60 s. The specificity of the sensor towards glucose has been demonstrated against various interfering species in artificial saliva, further highlighting its unique capabilities. Moreover, the BioTFTs exhibited good operating stability upon storage for up to two weeks, with relative standard deviation (RSD) values ranging from 2.36% to 6.39% for 500 nM glucose concentration. Our BioTFTs are easy to manufacture with reliable operation, making them ideal for non-invasive POCT applications.

Enhanced Organic Electrochemical Transistor Performance of Donor-Acceptor Conjugated Polymers Modified with Hybrid Glycol/Ionic Side Chains by Postpolymerization Modification.

Emergent bioelectronic technologies are underpinned by the organic electrochemical transistor (OECT), which employs an electrolyte medium to modulate the conductivity of its organic semiconductor channel. Here we utilize postpolymerization modification (PPM) on a conjugated polymer backbone to directly introduce glycolated or anionic side chains via fluoride displacement. The resulting polymers demonstrated increased volumetric capacitances, with subdued swelling, compared to their parent polymer in p-type enhancement mode OECTs. This increase in capacitance was attributed to their modified side chain configurations enabling cationic charge compensation for thin film electrochemical oxidation, as deduced from electrochemical quartz crystal microbalance measurements. An overall improvement in OECT performance was recorded for the hybrid glycol/ionic polymer compared to the parent, owing to its low swelling and bimodal crystalline orientation as imaged by grazing-incidence wide-angle X-ray scattering, enabling its high charge mobility at 1.02 cm2·V-1·s-1. Compromised device performance was recorded for the fully glycolated derivative compared to the parent, which was linked to its limited face-on stacking, which hindered OECT charge mobility at 0.26 cm2·V-1·s-1, despite its high capacitance. These results highlight the effectiveness of anionic side chain attachment by PPM as a means of increasing the volumetric capacitance of p-type conjugated polymers for OECTs, while retaining solid-state macromolecular properties that facilitate hole transport.

Tunable control of the performance of aqueous-based electrochemical devices by post-polymerization functionalization.

Functionalized polymeric mixed ionic-electronic conductors (PMIECs) are highly desired for the development of electrochemical applications, yet are hindered by the limited conventional synthesis techniques. Here, we propose a "graft-onto-polymer" synthesis strategy by post-polymerization functionalization (GOP-PPF) to prepare a family of PMIECs sharing the same backbone while functionalized with varying ethylene glycol (EG) compositions (two, four, and six EG repeating units). Unlike the typical procedure, GOP-PPF uses a nucleophilic aromatic substitution reaction for the facile and versatile attachment of functional units to a pre-synthesized conjugated-polymer precursor. Importantly, these redox-active PMIECs are investigated as a platform for energy storage devices and organic electrochemical transistors (OECTs) in aqueous media. The ion diffusivity, charge mobility and charge-storage capacity can be significantly improved by optimizing the EG composition. Specifically, g2T2-gBT6 containing the highest EG density gives the highest charge-storage capacity exceeding 180 F g-1 among the polymer series, resulting from the improved ion diffusivity. Moreover, g2T2-gBT4 with four EG repeating units exhibits a superior performance compared to its two analogues in OECTs, associated with a high µC* up to 359 F V-1 cm-1 s-1, owing to the optimal balance between ionic-electronic coupling and charge mobility. Through the GOP-PPF, PMIECs can be tailored to access desirable performance metrics at the molecular level.