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            Abstract Infrared photodiodes based on organic semiconductors are promising for low‐cost sensors that operate at room temperature. However, their realization remains hampered by poor device efficiency. Here, performance limitations are analyzed by evaluating the mobility‐lifetime products and charge collection efficiency of devices operating in the shortwave infrared with a peak absorption at 1550 nm. Through complementary impedance and current‐voltage measurements on devices with different donor‐to‐acceptor semiconductor ratios, a trade‐off between mobility and recombination time and the need to balance between transport and interfacial charge transfer are observed. Thus, this study revisits the mobility‐lifetime metric to shed new light on charge collection constraints in organic infrared photodiodes.more » « less
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            Abstract Space missions critically rely on sensors that operate throughout the near‐ to longwave infrared (NIR – LWIR, λ = 0.9–14 µm) regions of the electromagnetic spectrum. These sensors capture data beyond the capabilities of traditional optical tools and sensors, critical for the detection of thermal emissions, conducting atmospheric studies, and surveillance. However, conventional NIR‐LWIR detectors depend on bulky, cryogenically cooled semiconductors, making them impractical for broader space‐based applications due to their high cost, size, weight, and power (C‐SWaP) demands. Here, an IR photodetector using a solution‐processed narrow bandgap conjugated polymer is demonstrated. This direct bandgap photoconductor demonstrates exceptional infrared sensitivity without cooling and has minimal changes in figures‐of‐merit after substantial ionizing radiation exposure up to 1,000 krad – equivalent to three years in the most intense low Earth orbit (LEO). Its performance and resilience to radiation notably surpass conventional inorganic detectors, with a 7.7 and 98‐fold increase in radiation hardness when compared to epitaxial mercury cadmium telluride (HgCdTe) and indium gallium arsenide (InGaAs) photodiodes, respectively, offering a more affordable, compact, and energy‐efficient alternative. This class of organic semiconductors provides a new frontier for C‐SWaP optimized IR space sensing technologies, enabling the development of new spacecraft and missions with enhanced observational capabilities.more » « less
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            Abstract Photodetectors operating across the near‐ to short‐wave infrared (NIR–SWIR,λ= 0.9–1.8 µm) underpin modern science, technology, and society. Organic photodiodes (OPDs) based on bulk‐heterojunction (BHJ) active layers overcome critical manufacturing and operating drawbacks inherent to crystalline inorganic semiconductors, offering the potential for low‐cost, uncooled, mechanically compliant, and ubiquitous infrared technologies. A constraining feature of these narrow bandgap materials systems is the high noise current under an applied bias, resulting in specific detectivities (D*, the figure of merit for detector sensitivity) that are too low for practical utilization. Here, this study demonstrates that incorporating wide‐bandgap insulating polymers within the BHJ suppresses noise by diluting the transport and trapping sites as determined using capacitance‐frequency analysis. The resultingD*of NIR–SWIR OPDs operating from 600–1400 nm under an applied bias of −2 V is improved by two orders of magnitude, from 108to 1010 Jones (cm Hz1/2 W−1), when incorporating polysulfone within the blends. This broadly applicable strategy can reduce noise in IR‐OPDs enabling their practical operation and the realization of emerging technologies.more » « less
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            Abstract Organic retinomorphic sensors offer the advantage of in‐sensor processing to filter out redundant static backgrounds and are well suited for motion detection. To improve this promising structure, here, the key role of interfacial energetics in promoting charge accumulation to raise the inherent photoresponse of the light‐sensitive capacitor is studied. Specifically, incorporating appropriate interfacial layers around the photoactive layer is crucial to extend the carrier lifetime, as confirmed by intensity‐modulated photovoltage spectroscopy. Compared to its photodiode counterpart, the retinomorphic sensor shows better detectivity and response speed due to the additional insulating layer, which reduces the dark current and the RC time constant. Lastly, three retinomorphic sensors are integrated into a line array to demonstrate the detection of movement speed and direction, showing the potential of retinomorphic designs for efficient motion tracking.more » « less
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            Abstract Metal cations are potent environmental pollutants that negatively impact human health and the environment. Despite advancements in sensor design, the simultaneous detection and discrimination of multiple heavy metals at sub‐nanomolar concentrations in complex analytical matrices remain a major technological challenge. Here, the design, synthesis, and analytical performance of three highly emissive conjugated polyelectrolytes (CPEs) functionalized with strong iminodiacetate and iminodipropionate metal chelates that operate in challenging environmental samples such as seawater are demonstrated. When coupled with array‐based sensing methods, these polymeric sensors discriminate among nine divalent metal cations (CuII, CoII, NiII, MnII, FeII, ZnII, CdII, HgII, and PbII). The unusually high and robust luminescence of these CPEs enables unprecedented sensitivity at picomolar concentrations in water. Unlike previous array‐based sensors for heavy metals using CPEs, the incorporation of distinct π‐spacer units within the polymer backbone affords more pronounced differences in each polymer's spectroscopic behavior upon interaction with each metal, ultimately producing better analytical information and improved differentiation. To demonstrate the environmental and biological utility, a simple two‐component sensing array is showcased that can differentiate nine metal cation species down to 500 × 10−12 min aqueous media and to 100 × 10−9 min seawater samples collected from the Gulf of Mexico.more » « less
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            Abstract Phosphate oxyanions play central roles in biological, agricultural, industrial, and ecological processes. Their high hydration energies and dynamic properties present a number of critical challenges limiting the development of sensing technologies that are cost‐effective, selective, sensitive, field‐deployable, and which operate in real‐time within complex aqueous environments. Here, a strategy that enables the fabrication of an electrolyte‐gated organic field‐effect transistor (EGOFET) is demonstrated, which overcomes these challenges and enables sensitive phosphate quantification in challenging aqueous environments such as seawater. The device channel comprises a composite layer incorporating a diketopyrrolopyrrole‐based semiconducting polymer and a π‐conjugated penta‐t‐butylpentacyanopentabenzo[25]annulene “cyanostar” receptor capable of oxyanion recognition and embodies a new concept, where the receptor synergistically enhances the stability and transport characteristics via doping. Upon exposure of the device to phosphate, a current reduction is observed, consistent with dedoping upon analyte binding. Sensing studies demonstrate ultrasensitive and selective phosphate detection within remarkably low limits of detection of 178 × 10−12m(17.3 parts per trillion) in buffered samples and stable operation in seawater. This receptor‐based doping strategy, in conjunction with the versatility of EGOFETs for miniaturization and monolithic integration, enables manifold opportunities in diagnostics, healthcare, and environmental monitoring.more » « less
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            Abstract While only few organic photodiodes have photoresponse past 1 µm, novel shortwave infrared (SWIR) polymers are emerging, and a better understanding of the limiting factors in narrow bandgap devices is critically needed to predict and advance performance. Based on state‐of‐the‐art SWIR bulk heterojunction photodiodes, this work demonstrates a model that accounts for the increasing electric‐field dependence of photocurrent in narrow bandgap materials. This physical model offers an expedient method to pinpoint the origins of efficiency losses, by decoupling the exciton dissociation efficiency and charge collection efficiency in photocurrent–voltage measurements. These results from transient photoconductivity measurements indicate that the main loss is due to poor exciton dissociation, particularly significant in photodiodes with low‐energy charge‐transfer states. Direct measurements of the noise components are analyzed to caution against using assumptions that could lead to an overestimation of detectivity. The devices show a peak detectivity of 5 × 1010Jones with a spectral range up to 1.55 µm. The photodiodes are demonstrated to quantify the ethanol–water content in a mixture within 1% accuracy, conveying the potential of organics to enable economical, scalable detectors for SWIR spectroscopy.more » « less
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            Abstract Supercapacitors have emerged as an important energy storage technology offering rapid power delivery, fast charging, and long cycle lifetimes. While extending the operational voltage is improving the overall energy and power densities, progress remains hindered by a lack of stable n‐type redox‐active materials. Here, a new Faradaic electrode material comprised of a narrow bandgap donor−acceptor conjugated polymer is demonstrated, which exhibits an open‐shell ground state, intrinsic electrical conductivity, and enhanced charge delocalization in the reduced state. These attributes afford very stable anodes with a coulombic efficiency of 99.6% and that retain 90% capacitance after 2000 charge–discharge cycles, exceeding other n‐dopable organic materials. Redox cycling processes are monitored in situ by optoelectronic measurements to separate chemical versus physical degradation mechanisms. Asymmetric supercapacitors fabricated using this polymer with p‐type PEDOT:PSS operate within a 3 V potential window, with a best‐in‐class energy density of 30.4 Wh kg−1at a 1 A g−1discharge rate, a power density of 14.4 kW kg−1at a 10 A g−1discharge rate, and a long cycle life critical to energy storage and management. This work demonstrates the application of a new class of stable and tunable redox‐active material for sustainable energy technologies.more » « less
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