Exciton-Scissoring Perfluoroarenes Trigger Photomultiplication in Full Color Organic Image Sensors.

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.

Isolation of relaxation times under open-circuit conditions: Toward prognosis of nascent short circuits in Li-ion batteries.

Li-ion battery mishaps are primarily attributed to short circuits, which missed early detection. In this study, a method is introduced to address this issue by analyzing the voltage relaxation, after initiating a rest period. The voltage equilibration arising from solid-concentration profile relaxation is expressed by a double-exponential model, whose time constants, τ1 & τ2, capture the initial, rapid exponential contour and the long-term relaxation, respectively. By tracking τ2, which is very sensitive to small leakage currents, it is possible to detect a short early on and estimate the short resistance. This method, validated with experiments on commercial batteries induced with short circuits of varying extents, has >90% prediction accuracy and enables clear differentiation between different short severities, while factoring in the influence of temperature, state of charge (SOC), state of health (SOH), and idle currents. The method is applicable across different battery chemistries and form factors, offering precise and robust nascent-stage short detection-estimation for on-device implementation.

Axion Dark Matter Search around 4.55 µeV with Dine-Fischler-Srednicki-Zhitnitskii Sensitivity.

We report an axion dark matter search at Dine-Fischler-Srednicki-Zhitnitskii sensitivity with the CAPP-12TB haloscope, assuming axions contribute 100% of the local dark matter density. The search excluded the axion-photon coupling g_{aγγ} down to about 6.2×10^{-16} GeV^{-1} over the axion mass range between 4.51 and 4.59 µeV at a 90% confidence level. The achieved experimental sensitivity can also exclude Kim-Shifman-Vainshtein-Zakharov axion dark matter that makes up just 13% of the local dark matter density. The CAPP-12TB haloscope will continue the search over a wide range of axion masses.

Critical Role of Non-Halogenated Solvent Additives in Eco-Friendly and Efficient All-Polymer Solar Cells.

Organic solar cells (OSCs) demonstrating high power conversion efficiencies have been mostly fabricated using halogenated solvents, which are highly toxic and harmful to humans and the environment. Recently, non-halogenated solvents have emerged as a potential alternative. However, there has been limited success in attaining an optimal morphology when non-halogenated solvents (typically o-xylene (XY)) were used. To address this issue, we studied the dependence of the photovoltaic properties of all-polymer solar cells (APSCs) on various high-boiling-point non-halogenated additives. We synthesized PTB7-Th and PNDI2HD-T polymers that are soluble in XY and fabricated PTB7-Th:PNDI2HD-T-based APSCs using XY with five additives: 1,2,4-trimethylbenzene (TMB), indane (IN), tetralin (TN), diphenyl ether (DPE), and dibenzyl ether (DBE). The photovoltaic performance was determined in the following order: XY + IN < XY + TMB < XY + DBE ≤ XY only < XY + DPE < XY + TN. Interestingly, all APSCs processed with an XY solvent system had better photovoltaic properties than APSCs processed with chloroform solution containing 1,8-diiodooctane (CF + DIO). The key reasons for these differences were unraveled using transient photovoltage and two-dimensional grazing incidence X-ray diffraction experiments. The charge lifetimes of APSCs based on XY + TN and XY + DPE were the longest, and their long lifetime was strongly associated with the polymer blend film morphology; the polymer domain sizes were in the nanoscale range, and the blend film surfaces were smoother, as the PTB7-Th polymer domains assumed an untangled, evenly distributed, and internetworked morphology. Our results demonstrate that the use of an additive with an optimal boiling point facilitates the development of polymer blends with a favorable morphology and can contribute to the widespread use of eco-friendly APSCs.

Nondestructive Photopatterning of Heavy-Metal-Free Quantum Dots.

Electroluminescence from quantum dots (QDs) is a suitable photon source for futuristic displays offering hyper-realistic images with free-form factors. Accordingly, a nondestructive and scalable process capable of rendering multicolored QD patterns on a scale of several micrometers needs to be established. Here, nondestructive direct photopatterning for heavy-metal-free QDs is reported using branched light-driven ligand crosslinkers (LiXers) containing multiple azide units. The branched LiXers effectively interlock QD films via photo-crosslinking native aliphatic QD surface ligands without compromising the intrinsic optoelectronic properties of QDs. Using branched LiXers with six sterically engineered azide units, RGB QD patterns are achieved on the micrometer scale. The photo-crosslinking process does not affect the photoluminescence and electroluminescence characteristics of QDs and extends the device lifetime. This nondestructive method can be readily adapted to industrial processes and make an immediate impact on display technologies, as it uses widely available photolithography facilities and high-quality heavy-metal-free QDs with aliphatic ligands.

First Results from an Axion Haloscope at CAPP around 10.7 µeV.

The Center for Axion and Precision Physics Research at the Institute for Basic Science is searching for axion dark matter using ultralow temperature microwave resonators. We report the exclusion of the axion mass range 10.7126-10.7186 µeV with near Kim-Shifman-Vainshtein-Zakharov (KSVZ) coupling sensitivity and the range 10.16-11.37 µeV with about 9 times larger coupling at 90% confidence level. This is the first axion search result in these ranges. It is also the first with a resonator physical temperature of less than 40 mK.

p-CuInS2 /n-Polymer Semiconductor Heterojunction for Photoelectrochemical Hydrogen Evolution.

An inorganic p-type CuInS2 semiconductor was combined with the semiconducting polymer of PNDI3OT-Se1 and PNDI3OT-Se2 with different HOMO/LUMO levels for photoelectrochemical hydrogen production. Charge transfer behaviors at polymer/CuInS2 junctions were investigated by electrochemical impedance spectroscopy. The heterojunction of p-CuInS2 and n-type polymer (both PNDI3OT-Se1 and Se2) successfully made p-n junctions and showed improved charge transfer. However, we found that higher HOMO levels of polymer than valence band maximum (VBM) of CuInS2 spurred charge recombination at interfaces. As a result, CuInS2 /PNDI3OT-Se1/TiO2 /Pt, which has suitable energy levels matched between PNDI3OT-Se1 and CuInS2 , shows photocurrent (-15.67 mA cm-2 ) improved concretely when compared to a CuInS2 /TiO2 /Pt photoelectrode (-7.11 mA cm-2 ) at 0.0 V vs. RHE applied potential. Additionally, the photoelectrochemical stability of CuInS2 /PNDI3OT-Se1/TiO2 /Pt photoelectrode was also investigated.

High-resolution patterning of colloidal quantum dots via non-destructive, light-driven ligand crosslinking.

Establishing multi-colour patterning technology for colloidal quantum dots is critical for realising high-resolution displays based on the material. Here, we report a solution-based processing method to form patterns of quantum dots using a light-driven ligand crosslinker, ethane-1,2-diyl bis(4-azido-2,3,5,6-tetrafluorobenzoate). The crosslinker with two azide end groups can interlock the ligands of neighbouring quantum dots upon exposure to UV, yielding chemically robust quantum dot films. Exploiting the light-driven crosslinking process, different colour CdSe-based core-shell quantum dots can be photo-patterned; quantum dot patterns of red, green and blue primary colours with a sub-pixel size of 4 µm × 16 µm, corresponding to a resolution of >1400 pixels per inch, are demonstrated. The process is non-destructive, such that photoluminescence and electroluminescence characteristics of quantum dot films are preserved after crosslinking. We demonstrate that red crosslinked quantum dot light-emitting diodes exhibiting an external quantum efficiency as high as 14.6% can be obtained.

The Effect of a Flow Field on Chemical Detection Performance of Quadrotor Drone.

The determination of a suitable sensor location on quadrotor drones is a very important issue for chemical reconnaissance platforms because the magnitude and direction of air velocity is different for each location. In this study, we investigated a customized chemical reconnaissance system consisting of a quadrotor drone and a chip-sized chemical sensor for detecting dimethyl-methylphosphonate (DMMP; a Sarin simulant) and investigated the chemical detection properties with respect to the sensor position through indoor experiments and particle image velocimetry (PIV) analysis of the system. The PIV results revealed an area free of vortex-vortex interaction between the drone rotors, where there was distinctly stable and uniform chemical detection of DMMP. The proposed chemical reconnaissance system was found to be realistic for practical application.

Universal three-dimensional crosslinker for all-photopatterned electronics.

All-solution processing of large-area organic electronics requires multiple steps of patterning and stacking of various device components. Here, we report the fabrication of highly integrated arrays of polymer thin-film transistors and logic gates entirely through a series of solution processes. The fabrication is done using a three-dimensional crosslinker in tetrahedral geometry containing four photocrosslinkable azide moieties, referred to as 4Bx. 4Bx can be mixed with a variety of solution-processable electronic materials (polymer semiconductors, polymer insulators, and metal nanoparticles) and generate crosslinked network under exposure to UV. Fully crosslinked network film can be formed even at an unprecedentedly small loading, which enables preserving the inherent electrical and structural characteristics of host material. Because the crosslinked electronic component layers are strongly resistant to chemical solvents, micropatterning the layers at high resolution as well as stacking the layers on top of each other by series of solution processing steps is possible.

Functionalized Organic Material Platform for Realization of Ternary Logic Circuit.

Negative differential resistance/transconductance (NDR/NDT) has been attracting significant attention as a key functionality in the development of multivalued logic (MVL) systems that can overcome the limits of conventional binary logic devices. A high peak-to-valley current ratio (PVCR) and more than double-peak transfer characteristics are required to achieve a stable MVL operation. In this study, an organic NDR (ONDR) device with double-peak transfer characteristics and a high peak-to-valley current ratio (PVCR; >102) is fabricated by utilizing an organic material platform for the development of a key element device for MVL applications. The organic NDT (ONDT) device is fabricated using a series connection of electron-dominant (P(NDI2OD-Se2)) and hole-dominant (P(DPP2DT-T2)) channel ambipolar organic field-effect transistors (AOFETs), and the NDR feature is achieved via correlated biasing of the ONDT device. The PVCR of the ONDT device can reach up to 13,000 via carrier transfer modulation of the AOFETs by varying the PMMA:P(VDF-TrFE) ratio of the mixed layer that is used as the top-gate dielectric of each AOFET. Further, ternary latch circuit operation is demonstrated using the developed ONDR device that stores three logic states with three distinct and controllable output states by adjusting the PMMA:P(VDF-TrFE) ratio of the dielectric layer.

Regio-regular alternating diketopyrrolopyrrole-based D1-A-D2-A terpolymers for the enhanced performance of polymer solar cells.

We designed and synthesized regio-regular alternating diketopyrrolopyrrole (DPP)-based D1-A-D2-A terpolymers (PDPPF2T2DPP-T2, PDPPF2T2DPP-TVT, and PDPPF2T2DPP-DTT) using a primary donor (D1) [3,3'-difluoro-2,2'-bithiophene (F2T2)] and a secondary donor (D2) [2,2'-bithiophene (T2), (E)-1,2-di(thiophen-2-yl)ethene (TVT), or dithieno[3,2-b:2',3'-d]thiophene (DTT)]. A PDPP2DT-F2T2 D-A polymer was synthesized as well to compare optical, electronic, and photovoltaic properties. The absorption peaks of the terpolymers (PDPPF2T2DPP-T2, PDPPF2T2DPP-TVT, and PDPPF2T2DPP-DTT) were longer (λ max = 801-810 nm) than the peak of the PDPP2DT-F2T2 polymer (λ max = 799 nm), which is associated with the high-lying HOMO levels of the terpolymers (-5.08 to -5.13 eV) compared with the level of the PDPP2DT-F2T2 polymer (-5.38 eV). The photovoltaic properties of these DPP-based polymers were investigated under simulated AM 1.5G sunlight (100 mW cm-2) with a conventional structure (ITO/PEDOT:PSS/polymer:PC71BM/Al). The open-circuit voltages (V oc) of photovoltaic devices containing the terpolymers were slightly lower (0.68-0.70 V) than the V oc of the device containing the PDPP2DT-F2T2 polymer (0.79 V). The short-circuit current (J sc) of the PDPPF2T2DPP-DTT device was significantly improved (14.14 mA cm-2) compared with that of the PDPP2DT-F2T2 device (8.29 mA cm-2). As a result, the power conversion efficiency (PCE) of the PDPPF2T2DPP-DTT device (6.35%) was increased by 33% compared with that of the simple D-A-type PDPP2DT-F2T2 device (4.78%). The highest J sc and PCE values (the PDPPF2T2DPP-DTT device) were attributed to an optimal nanoscopically mixed morphology and strong interchain packing with a high face-on orientation in the blend film state. The study demonstrated that our strategy of using multiple donors in a regio-regular alternating fashion could fine-tune the optical, electronic, and morphological properties of D-A-type polymers, enhancing the performance of polymer solar cells.

Simple Solvent Engineering for High-Mobility and Thermally Robust Conjugated Polymer Nanowire Field-Effect Transistors.

Electron donor (D)-acceptor (A)-type conjugated polymers (CPs) have emerged as promising semiconductor candidates for organic field-effect transistors. Despite their high charge carrier mobilities, optimization of electrical properties of D-A-type CPs generally suffers from complicated post-deposition treatments such as high-temperature thermal annealing or solvent-vapor annealing. In this work, we report a high-mobility diketopyrrolopyrrole-based D-A-type CP nanowires, self-assembled by a simple but very effective solvent engineering method that requires no additional processes after film deposition. In situ grown uniform nanowires at room temperature were shown to possess distinct edge-on chain orientation that is beneficial for lateral charge transport between source and drain electrodes in FETs. FETs based on the polymer nanowire networks exhibit impressive hole mobility of up to 4.0 cm2 V-1 s-1. Moreover, nanowire FETs showed excellent operational stability in high temperature up to 200 °C because of the strong interchain interaction and alignment.

Structure-Property Relationships of Semiconducting Polymers for Flexible and Durable Polymer Field-Effect Transistors.

We report high-performance top-gate bottom-contact flexible polymer field-effect transistors (FETs) fabricated by flow-coating diketopyrrolopyrrole (DPP)-based and naphthalene diimide (NDI)-based polymers (P(DPP2DT-T2), P(DPP2DT-TT), P(DPP2DT-DTT), P(NDI2OD-T2), P(NDI2OD-F2T2), and P(NDI2OD-Se2)) as semiconducting channel materials. All of the polymers displayed good FET characteristics with on/off current ratios exceeding 107. The highest hole mobility of 1.51 cm2 V-1 s-1 and the highest electron mobility of 0.85 cm2 V-1 s-1 were obtained from the P(DPP2DT-T2) and P(NDI2OD-Se2) polymer FETs, respectively. The impacts of the polymer structures on the FET performance are well-explained by the interplay between the crystallinity, the tendency of the polymer backbone to adopt an edge-on orientation, and the interconnectivity of polymer fibrils in the film state. Additionally, we demonstrated that all of the flexible polymer-based FETs were highly resistant to tensile stress, with negligible changes in their carrier mobilities and on/off ratios after a bending test. Conclusively, these high-performance, flexible, and durable FETs demonstrate the potential of semiconducting conjugated polymers for use in flexible electronic applications.

A Nonchlorinated Solvent-Processable Fluorinated Planar Conjugated Polymer for Flexible Field-Effect Transistors.

High carrier mobilities have recently been achieved in polymer field effect transistors (FETs). However, many of these polymer FET devices require the use of chlorinated solvents such as chloroform (CF), chlorobenzene (CB), and o-dichlorobenzene (DCB) during fabrication. The use of these solvents is highly restricted in industry because of health and environmental issues. Here, we report the synthesis of a low band gap (1.43 eV, 870 nm) semiconducting polymer (PDPP2DT-F2T2) having a planar geometry, which can be readily processable with nonchlorinated solvents such as toluene (TOL), o-xylene (XY), and 1,2,4-trimethylbenzene (TMB). We performed structural characterization of PDPP2DT-F2T2 films prepared from different solvents, and the electrical properties of the films were measured in the context of FETs. The devices exhibited an ambipolar behavior with hole dominant transport. Hole mobilities increased with increasing boiling point (bp) of the nonchlorinated solvents: 0.03, 0.05, and 0.10 cm2 V-1 s-1 for devices processed using TOL, XY, and TMB, respectively. Thermal annealing further improved the FET performance. TMB-based polymer FETs annealed at 200 °C yielded a maximum hole mobility of 1.28 cm2 V-1 s-1, which is far higher than the 0.43 cm2 V-1 s-1 obtained from the CF-based device. This enhancement was attributed to increased interchain interactions as well as improved long-range interconnection between fibrous domains. Moreover, all of the nonchlorinated solutions generated purely edge-on orientations of the polymer chains, which is highly beneficial for carrier transport in FET devices. Furthermore, we fabricated an array of flexible TMB-processed PDPP2DT-F2T2 FETs on the plastic PEN substrates. These devices demonstrated excellent carrier mobilities and negligible degradation after 300 bending cycles. Overall, we demonstrated that the organized assembly of polymer chains can be achieved by slow drying using high bp nonchlorinated solvents and a post thermal treatment. Furthermore, we showed that polymer FETs processed using high bp nonhalogenated solvents may outperform those processed using halogenated solvents.

Photoresponsive Transistors Based on a Dual Acceptor-Containing Low-Bandgap Polymer.

In this Article, low-bandgap pTTDPP-BT polymers based on electron-accepting pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) and benzothiadiazole (BT) and electron-donating thienothiophene (TT) moieties were synthesized. Phototransistors have been fabricated using ambipolar-behaving pTTDPP-BT polymers as active channel materials. The electrical and photoresponsive properties of the pTTDPP-BT phototransistors were strongly dependent on the film annealing temperature. As-spun pTTDPP-BT phototransistors exhibited a low hole mobility of 0.007 cm2/(V·s) and a low electron mobility of 0.005 cm2/(V·s), which resulted in low photocurrent detection due to the limited transport of the charge carriers. Thermal treatment of the polymer thin films led to a significant enhancement in the carrier mobilities (hole and electron mobilities of 0.066 and 0.115 cm2/(V·s), respectively, for 200 °C annealing) and thus significantly improved photoresponsive properties. The 200 °C-annealed phototransistors showed a wide-range wavelength (405-850 nm) of photoresponse, and a high photocurrent/dark-current ratio of 150 with a fast photoswitching speed of less than 100 ms. This work demonstrates that a dual acceptor-containing low band gap polymer can be an important class of material in broadband photoresponsive transistors, and the crystallinity of the semiconducting polymer layer has a significant effect on the photoresponse characteristics.