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Photomultiplication (PM)-type organic photodetectors (OPDs), which typically form a homogeneous distribution (HD) of n-type dopants in a p-type polymer host (HD PM-type OPDs), have achieved a breakthrough in device responsivity by surpassing a theoretical limit of external quantum efficiency (EQE). However, they face limitations in higher dark current and slower dynamic characteristics compared to p-n heterojunction (p-n HJ) OPDs due to inherent long lifetime of trapped electrons. To overcome this, a new PM-type OPD is developed that demonstrates ultrafast dynamic properties through a vertical phase separation (VPS) strategy between the p-type polymer and n-type acceptor, referred to as VPS PM-type OPDs. Notably, VPS PM-type OPDs show three orders of magnitude increase in -3 dB cut-off frequency (120 kHz) and over a 200-fold faster response time (rising time = 4.8 µs, falling time = 8.3 µs) compared to HD PM-type OPDs, while maintaining high EQE of 1121% and specific detectivity of 2.53 × 1013 Jones at -10 V. The VPS PM-type OPD represents a groundbreaking advancement by demonstrating the coexistence of p-n HJ and PM modes within a single photoactive layer for the first time. This innovative approach holds the potential to enhance both static and dynamic properties of OPDs.
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High-performance organic photodiodes (OPDs) and OPD-based image sensors are primarily realized using solution processes based on various additives and coating methods. However, vacuum-processed OPDs, which are more compatible with large-scale production, have received little attention, thereby hindering their integration into advanced systems. This study introduces innovations in the material and device structures to prepare superior vacuum-processed OPDs for commercial applications. A series of vacuum-processable, low-cost p-type semiconductors is developed by introducing an electron-rich cyclopentadithiophene core containing various electron-accepting moieties to fine-tune the energy levels without any significant structural or molecular weight changes. An additional nanointerlayer strategy is used to control the crystalline orientation of the upper-deposited photoactive layer, compensating for device performance reduction in inverted, top-illuminated OPDs. These approaches yielded an external quantum efficiency of 70% and a specific detectivity of 2.0 × 1012 Jones in the inverted structures, which are vital for commercial applications. These OPDs enabled visible-light communications with extremely low bit error rates and successful X-ray image capture.
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A universal approach for enhancing water affinity in polymer photocatalysts by covalently attaching hydrophilic photocrosslinkers to polymer chains is presented. A series of bisdiazirine photocrosslinkers, each comprising bisdiazirine photophores linked by various aliphatic (CL-R) or ethylene glycol-based bridge chains (CL-TEG), is designed to prevent crosslinked polymer photocatalysts from degradation through a safe and efficient photocrosslinking reaction at a wavelength of 365 nm. When employing the hydrophilic CL-TEG as a photocrosslinker with polymer photocatalysts (F8BT), the hydrogen evolution reaction (HER) rate is considerably enhanced by 2.5-fold compared to that obtained using non-crosslinked F8BT photocatalysts, whereas CL-R-based photocatalysts yield HER rates comparable to those of non-crosslinked counterparts. Photophysical analyses including time-resolved photoluminescence and transient absorption measurements reveal that adding CL-TEG accelerates exciton separation, forming long-lived charge carriers. Additionally, the in-depth study using molecular dynamics simulations elucidates the dual role of CL-TEG: it enhances water penetration into the polymer matrix and stabilizes charge carriers after exciton generation against undesirable recombination. Therefore, the strategy highlights endowing a high-permittivity environment within polymer photocatalyst in a controlled manner is crucial for enhancing photocatalytic redox reactivity. Furthermore, this study shows that this hydrophilic crosslinker approach has a broad applicability in general polymer semiconductors and their nanoparticulate photocatalysts.
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Over the past decade, molecular-switch-embedded memory devices, particularly field-effect transistors (FETs), have gained significant interest. Molecular switches are integrated to regulate the resistance or current levels in FETs. Despite substantial efforts, realizing large memory window with a long retention time, a critical factor in memory device functionality, remains a challenge. This is due to the inability of an isomeric state of a molecular switch to serve as a stable deep trap state within the semiconductor layer. Herein, the study addresses this limitation by introducing chemical bonding between molecular switch and conjugated polymeric semiconductor, facilitating closed isomer of diarylethene (DAE) to operate as a morphologically stable deep trap state. Azide- and diazirine-anchored DAEs are synthesized, which form chemical bonds to the polymer through photocrosslinking, thereby implementing permanent and controllable trapping states nearby conjugated backbone of polymer semiconductor. Consequently, when diazirine-anchored DAE is blended with F8T2 and subjected to photocrosslinking, the resulting organic FETs exhibit remarkable memory performance, including a memory window of 22 V with a retention time over 106 s, a high photoprogrammable on/off ratio over 103, and a high operational stability over 100 photocycles. Further, photophore-anchored DAEs can achieve precise patterning, which enables meticulous control over the semiconductor layer structure.
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A multichannel/multicolor visible light communication (VLC) system using entirely organic components, including organic light emitting diodes (OLEDs) and organic photodiodes (OPDs), is developed to demonstrate indoor lighting applications where the integration of OLEDs and OPDs has significant potential. To achieve this, tricolor (Red/Green/Blue(R/G/B))-selective OPD arrays for the receiver and tricolor OLED arrays for the emitter are developed. For (R/G/B)-selective OPDs, a Fabry-Pérot electrode to enhance color selectivity and a thick junction structure to effectively accommodate a wide range of driving voltages are introduced. For tricolor OLEDs, fluorescent-emitting materials are used to enhance the operating frequency in addition to introducing a cavity structure to achieve narrow emission. Utilizing these spectrally refined tricolor OPDs/OLEDs, a VLC system is designed for indoor lighting applications, and a systematic analysis of their signal-to-interference ratio dependence on the distance or angle between the transmitter and receiver is performed. The study's findings indicate the importance of emission angle-dependent wavelength shift of the OLED and the luminosity function, which varies with wavelength, in the R/G/B mixed-white-light-based VLC systems. Finally, the feasibility of VLC using tricolor OPDs/OLEDs in the real-life context of indoor white-color lighting is demonstrated, showing that the transmitted data patterns well-matched the received data patterns.
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A novel approach for developing shortwave IR (SWIR) organic photodiodes (OPDs) using doped polymers is presented. SWIR OPDs are challenging to produce because of the limitations in extending the absorption of conjugated molecules and the high dark currents of SWIR-absorbing materials. Herein, it is shown that the conversion of bound polarons to free polarons by light energy can be utilized as an SWIR photodetection mechanism. To maximize the bound-polaron density and bound-to-free polaron ratio of the doped polymer film, the doping process is engineered and dopant molecules are diffused into the crystalline domain of the polymer matrix and a direct correlation between the bound-to-free polaron ratio and device performance is confirmed. The optimized double-doped SWIR OPD exhibits a high external quantum efficiency of 77â¯100% and specific detectivity of 1.11 × 1011 Jones against SWIR. These findings demonstrate the application potential of polarons as alternatives for Frenkel excitons in SWIR OPDs.
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In this study, it is demonstrated that CsPbBr3 perovskite nanocrystals (NCs) can enhance the overall performances of photomultiplication-type organic photodiodes (PM-OPDs). The proposed approach enables the ionic-polarizable CsPbBr3 NCs to be evenly distributed throughout the depletion region of Schottky junction interface, allowing the entire trapped electrons within the depletion region to be stabilized, in contrast to previously reported interface-limited strategies. The optimized CsPbBr3 -NC-embedded poly(3-hexylthiophene-diyl)-based PM-OPDs exhibit exceptionally high external quantum efficiency, specific detectivity, and gain-bandwidth product of 2,840,000%, 3.97 × 1015 Jones, and 2.14 × 107 Hz, respectively. 2D grazing-incidence X-ray diffraction analyses and drift-diffusion simulations combined with temperature-dependent J-V characteristic analyses are conducted to investigate the physics behind the success of CsPbBr3 -NC-embedded PM-OPDs. The results show that the electrostatic interactions generated by the ionic polarization of NCs effectively stabilize the trapped electrons throughout the entire volume of the photoactive layer, thereby successfully increasing the effective energy depth of the trap states and allowing efficient PM mechanisms. This study demonstrates how a hybrid-photoactive-layer approach can further enhance PM-OPD when the functionality of inorganic inclusions meets the requirements of the target device.
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Organic vertical transistors are promising device with benefits such as high operation speed, high saturation current density, and low-voltage operation owing to their short channel length. However, a short channel length leads to a high off-current, which is undesirable because it affects the on-off ratio and power consumption. This study presents a breakthrough in the development of high-performance organic Schottky barrier transistors (OSBTs) with a low off-current by utilizing a near-ideal source electrode with a web-like Ag nanowire (AgNW) morphology. This is achieved by employing a humidity- and surface-tension-mediated liquid-film rupture technique, which facilitates the formation of well-connected AgNW networks with large pores between them. Therefore, the gate electric field is effectively transmitted to the semiconductor layer. Also, the minimized surface area of the AgNWs causes complete suppression of the off-current and induces ideal saturation of the OSBT output characteristics. p- and n-type OSBTs exhibit off-currents in the picoampere range with on/off ratios exceeding 106 and 105, respectively. Furthermore, complementary inverters are prepared using an aryl azide cross-linker for patterning, with a gain of >16. This study represents a significant milestone in the development of high-performance organic vertical transistors and verifies their applicability in organic electronic circuitry.
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Suppressing the dark current density (Jd) while maintaining sufficient charge transport is important for improving the specific detectivity (D*) and dynamic characteristics of organic photodetectors (OPDs). In this study, we synthesized three novel small-molecule acceptors (SMAs) densely surrounded by insulating alkyl side chains to minimize the Jd in OPDs. Introducing trialkylated N-annulated perylene diimide as a terminal moiety to the alkylated π-conjugated core structure was highly efficient in suppressing Jd in the devices, resulting in an extremely low Jd of 4.60 × 10-11 A cm-2 and 10-100 times improved D* values in the devices. In addition, SMAs with a geometrically aligned backbone structure exhibited better intermolecular ordering in the blended films, resulting in 3-10 times as high responsivity (R) values in the OPDs. Outstanding OPD performances with a D* of 8.09 × 1012 Jones, -3 dB cutoff frequency of 205.2 kHz, and rising response time of 16 µs were achieved under a 530 nm illumination in photoconductive mode. Geometrically aligned core-terminal SMAs densely surrounded by insulating alkyl side chains are promising for improving the static and dynamic properties of OPDs.
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Mechanically deformable photodetectors (PDs) are key device components for wearable health monitoring systems based on photoplethysmography (PPG). Achieving high detectivity, fast response time, and an ultrathin form factor in the PD is highly needed for next-generation wearable PPG systems. Self-powered operation without a bulky power-supply unit is also beneficial for point-of-care application. Here, we propose ultrathin self-powered PDs using heavy-metal-free Cu-In-Se quantum dots (QDs), which enable high-performance wearable PPG systems. Although the light-absorbing QD layer is extremely thin (â¼40 nm), the developed PD exhibits excellent performance (specific detectivity: 2.10 × 1012 Jones, linear dynamic range: 102 dB, and spectral range: 250-1050 nm at zero bias), which is comparable to that of conventional rigid QD-PDs employing thick Pb-chalcogenide QD layers. This is attributed to material and device strategiesâmaterials that include Cu-In-Se QDs, a MoS2-nanosheet-blended poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) hole transport layer, a ZnO nanoparticle electron transport layer, Ag and ITO electrodes, and an ultrathin form factor (â¼120 nm except the electrodes) that enable excellent mechanical deformability. These allow the successful application of QD-PDs to a wearable system for real-time PPG monitoring, expanding their potential in the field of mobile bioelectronics.
Asunto(s)
Metales Pesados , Nanopartículas , Puntos Cuánticos , Dispositivos Electrónicos Vestibles , Suministros de Energía Eléctrica , ElectrodosRESUMEN
An unprecedented but useful functionality of perfluoroarenes to enable exciton scissoring in photomultiplication-type organic photodiodes (PM-OPDs) is reported. Perfluoroarenes that are covalently connected to polymer donors via a photochemical reaction enable the demonstration of high external quantum efficiency and B-/G-/R-selective PM-OPDs without the use of conventional acceptor molecules. The operation mechanism of the suggested perfluoroarene-driven PM-OPDs, how covalently bonded polymer donor:perfluoroarene PM-OPDs can perform as effectively as polymer donor:fullerene blend-based PM-OPDs, is investigated. By employing a series of arenes and conducting steady-state/time-resolved photoluminescence and transient absorption spectroscopy analyses, it is found that interfacial band bending between the perfluoroaryl group and polymer donor is responsible for exciton scissoring and subsequent electron trapping, which induces photomultiplication. Owing to the acceptor-free and covalently interconnected photoactive layer in the suggested PM-OPDs, superior operational and thermal stabilities are observed. Finally, finely patterned B-/G-/R-selective PM-OPD arrays that enable the construction of highly sensitive passive matrix-type organic image sensors are demonstrated.
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Cdx Hg1- x Se/HgS/Cdy Zn1- y S core/multi-shell quantum dots (QDs) exhibiting bright tissue-penetrating shortwave infrared (SWIR; 1000-1700 nm) photoluminescence (PL) are engineered. The new structure consists of a quasi-type-II Cdx Hg1- x Se/HgS core/inner shell domain creating luminescent bandgap tunable across SWIR window and a wide-bandgap Cdy Zn1- y S outer shell boosting the PL quantum yield (QY). This compositional sequence also facilitates uniform and coherent shell growth by minimizing interfacial lattice mismatches, resulting in high QYs in both organic (40-80%) and aqueous (20-70%) solvents with maximum QYs of 87 and 73%, respectively, which are comparable to those of brightest visible-to-near infrared QDs. Moreover, they maintain bright PL in a photocurable resin (QY 40%, peak wavelength ≈ 1300 nm), enabling the fabrication of SWIR-luminescent composites of diverse morphology and concentration. These composites are used to localize controlled amounts of SWIR QDs inside artificial (Intralipid) and porcine tissues and quantitatively evaluate the applicability as luminescent probes for deep-tissue imaging.
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Recent improvements in the performance of solution-processed semiconductor materials and optoelectronic devices have shifted research interest to the diversification/advancement of their functionality. Embedding a molecular switch capable of transition between two or more metastable isomers by light stimuli is one of the most straightforward and widely accepted methods to potentially realize the multifunctionality of optoelectronic devices. A molecular switch embedded in a semiconductor can effectively control various parameters such as trap-level, dielectric constant, electrical resistance, charge mobility, and charge polarity, which can be utilized in photoprogrammable devices including transistors, memory, and diodes. This review classifies the mechanism of each optoelectronic transition driven by molecular switches regardless of the type of semiconductor material or molecular switch or device. In addition, the basic characteristics of molecular switches and the persisting technical/scientific issues corresponding to each mechanism are discussed to help researchers. Finally, interesting yet infrequently reported applications of molecular switches and their mechanisms are also described.
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To separately explore the importance of hydrophilicity and backbone planarity of polymer photocatalyst, a series of benzothiadiazole-based donor-acceptor alternating copolymers incorporating alkoxy, linear oligo(ethylene glycol) (OEG) side chain, and backbone fluorine substituents is presented. The OEG side chains in the polymer backbone increase the surface energy of the polymer nanoparticles, thereby improving the interaction with water and facilitating electron transfer to water. Moreover, the OEG-attached copolymers exhibit enhanced intermolecular packing compared to polymers with alkoxy side chains, which is possibly attributed to the self-assembly properties of the side chains. Fluorine substituents on the polymer backbone produce highly ordered lamellar stacks with distinct π-π stacking features; subsequently, the long-lived polarons toward hydrogen evolution are observed by transient absorption spectroscopy. In addition, a new nanoparticle synthesis strategy using a methanol/water mixed solvent is first adopted, thereby avoiding the screening effect of surfactants between the nanoparticles and water. Finally, hydrogen evolution rate of 26 000 µmol g-1 h-1 is obtained for the copolymer incorporated with both OEG side chains and fluorine substituents under visible-light irradiation (λ > 420 nm). This study demonstrates how the glycol side chain strategy can be further optimized for polymer photocatalysts by controlling the backbone planarity.
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We propose a highly efficient crosslinking strategy for organic-inorganic hybrid dielectric layers using azide-functionalized acetylacetonate, which covalently connect inorganic particles to polymers, enabling highly efficient inter- and intra-crosslinking of organic and inorganic inclusions, resulting in a dense and defect-free thin-film morphology. From the optimized processing conditions, we obtained an excellent dielectric strength of over 4.0 MV cm-1, a high dielectric constant of ~14, and a low surface energy of 38 mN m-1. We demonstrated the fabrication of exceptionally high-performance, hysteresis-free n-type solution-processed oxide transistors comprising an In2O3/ZnO double layer as an active channel with an electron mobility of over 50 cm2 V-1 s-1, on/off ratio of ~107, subthreshold swing of 108 mV dec-1, and high bias-stress stability. From temperature-dependent I-V analyses combined with charge transport mechanism analyses, we demonstrated that the proposed hybrid dielectric layer provides percolation-limited charge transport for the In2O3/ZnO double layer under field-effect conditions.
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When the intensity of the incident light increases, the photocurrents of organic photodiodes (OPDs) exhibit relatively early saturation, due to which OPDs cannot easily detect objects against strong backlights, such as sunlight. In this study, this problem is addressed by introducing a light-intensity-dependent transition of the operation mode, such that the operation mode of the OPD autonomously changes to overcome early photocurrent saturation as the incident light intensity passes the threshold intensity. The photoactive layer is doped with a strategically designed and synthesized molecular switch, 1,2-bis-(2-methyl-5-(4-cyanobiphenyl)-3-thienyl)tetrafluorobenzene (DAB). The proposed OPD exhibits a typical OPD performance with an external quantum efficiency (EQE) of <100% and a photomultiplication behavior with an EQE of >100% under low-intensity and high-intensity light illuminations, respectively, thereby resulting in an extension of the photoresponse linearity to a light intensity of 434 mW cm-2 . This unique and reversible transition of the operation mode can be explained by the unbalanced quantum yield of photocyclization/photocycloreversion of the molecular switch. The details of the operation mechanism are discussed in conjunction with various photophysical analyses. Furthermore, they establish a prototype image sensor with an array of molecular-switch-embedded OPD pixels to demonstrate their extremely high sensitivity against strong light illumination.
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A conjugated polymer particle in an aqueous phase is covalently networked in 3D by crosslinking with azide groups, leading to significantly enhanced activity-a high photocatalytic H2 evolution rate (11 024 µmol g-1 h-1 (λ > 420 nm)) and a high apparent quantum yield (up to 0.8%). The reaction between the photoactive azide and the alkyl chains of the conjugated polymer provides more intact intermolecular polymeric interactions in the colloidal state, thus preventing physical swelling and inhibiting the recombination of photoproduced carriers. The covalent network efficiently promotes exciton diffusion, which greatly facilitates charge separation and transfer. The azide photo-crosslinking also leads to more compact and better-packed nanoparticles in the aqueous phase and efficient transfer of excitons to the outer surface of the nanoparticles, where photocatalytic reactions occur. These results show that photo-crosslinking can suppress the adverse effects of alkyl chains which inhibit photocatalytic performance. Therefore, covalent crosslinking is a promising strategy for the development of solar and hydrogen energy.
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Obtaining a photomultiplication-type organic photodiode with a high gain-bandwidth product is challenging. We show that a newly designed regioregular polymer enables the formation of a highly oriented face-on structure with a low trap density, leading to a high EQE and a fast response time. As a result, a gain-bandwidth product of over 4 × 105 Hz is achieved.
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A photomultiplication-type organic photodiode (PM-OPD), where an electric double layer (EDL) is strategically embedded, is demonstrated, with an exceptionally high external quantum efficiency (EQE) of 2 210 000%, responsivity of 11 200 A W-1 , specific detectivity of 2.11 × 1014 Jones, and gain-bandwidth product of 1.92 × 107 Hz, as well as high reproducibility. A polymer electrolyte, poly(9,9-bis(3'-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide is employed as a work-function-modifying layer of indium tin oxide (ITO) to construct an EDL-embedded Schottky junction with p-type polymer semiconductor, poly(3-hexylthiophene-diyl), resulting in not only advantageous tuning of the work function of ITO but also an enhancement of the electron-trapping efficiency due to electrostatic interaction between exposed cations and trapped electrons within isolated acceptor domains. The effects of the EDL on the energetics of the trapped electron states and thus on the gain generation mechanism are confirmed by numerical simulations based on the drift-diffusion approximation of charge carriers. The feasibility of the fabricated high-EQE PM-OPD especially for weak light detection is demonstrated via a pixelated prototype image sensor. It is believed that this new OPD platform opens up the possibility for the ultrahigh-sensitivity organic image sensors, while maintaining the advantageous properties of organics.
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In this study, it is shown that fluorinated azide, employed as a functional additive to photomultiplication-type organic photodiodes (PM-OPDs), can not only enhance the operational stability by freezing the morphology consisting of matrix polymer/localized acceptor but also stabilize the trapped electron states such that the photomultiplication mechanism can be accelerated further, leading to exceptionally high external quantum efficiency (EQE). The consequent semitransparent OPD consisting of molybdenum oxide (MoO3)/Au/MoO3/photoactive layer/polyethyleneimine ethoxylated/indium tin oxide (ITO) rendered a maximum EQE of over 500 000% and 370 000% under bottom and top illumination, respectively. Owing to the remarkably high EQE, high specific detectivity of 5.6 × 1013 Jones and low noise-equivalent power of 5.35 × 10-15 W Hz-0.5 were also demonstrated. Furthermore, the OPD demonstrated stable performance during 20 h of continuous operation and minimal performance degradation even after the damp heat test. To fully visualize the advantages of the proposed high-EQE, top-illuminated, semitransparent OPD with spectral asymmetry between absorption and detection, a reflection-type fingerprint platform consisting of 1 OPD-1 oxide field-effect transistor complementary metal-oxide-semiconductor backplane (300 ppi) is designed and fabricated. The successful recognition of the fingerprint of one of the authors is demonstrated, which indicates the feasibility of the proposed PM-OPD for sensing weak light intensity.