Large-Area Printed Oxide Film Sensors Enabling Ultrasensitive and Dual Electrical/Colorimetric Detection of Hydrogen at Room Temperature.

Commercial hydrogen (H2) sensors operate at high temperatures, which increases power consumption and poses a safety risk owing to the flammable nature of H2. Here, a polymer-noble metal-metal oxide film is fabricated using the spin-coating and printing methods to realize a highly sensitive, low-voltage operation, wide-operating-concentration, and near-monoselective H2 sensor at room temperature. The H2 sensors with an optimized thickness of Pd nanoparticles and SnO2 showed an extremely high response of 16,623 with a response time of 6 s and a recovery time of 5 s at room temperature and 2% H2. At the same time, printed flexible sensors demonstrate excellent sensitivity, with a response of 2300 at 2% H2. The excellent sensing performance at room temperature is due to the optimal SnO2 thickness, corresponding to the Debye length and the oxygen and H2 spillover caused by the optimized coverage of the Pd catalyst. Furthermore, multistructures of WO3 and SnO2 films are used to fabricate a new type of dual-signal sensor, which demonstrated simultaneous conductance and transmittance, i.e., color change. This work provides an effective strategy to develop robust, flexible, transparent, and long-lasting H2 sensors through large-area printing processes based on polymer-metal-metal oxide nanostructures.

Amorphous Fluorinated Acrylate Polymer Dielectrics for Flexible Transistors and Logic Gates with High Operational Stability.

Fluorinated amorphous polymeric gate-insulating materials for organic thin-film transistors (OTFTs) not only form hydrophobic surfaces but also significantly reduce traps at the interface between the organic semiconductor and gate insulator. Therefore, these polymeric materials can enhance the OTFT's operation stability. In this study, we synthesized a new polymeric insulating material series composed of acrylate and fluorinated functional groups (with different ratios) named MBHCa-F and used them as gate insulators for OTFTs and in other applications. The insulating features of the MBHCa-F polymers, including surface energy, surface atomic content properties, dielectric constant, and leakage current, were clearly analyzed with respect to the content of the fluorinated functional groups. At higher fluorine-based functional group content, the polymeric series exhibited higher fluorine-based contents at the surface and superior electrical properties, such as field-effect mobility and driving stability, at OTFTs. Therefore, we believe that this study provides a substantial method for synthesizing polymeric insulating materials to enhance the operational stability and electrical performance of OTFTs.

Improving the Stability of Non-fullerene-Based Organic Photovoltaics through Sequential Deposition and Utilization of a Quasi-orthogonal Solvent.

The development of organic photovoltaic (OPV) devices based on non-fullerene acceptors (NFAs) has led to a rapid improvement in their efficiency. Despite these improvements, significant performance degradation in the early stages of operation, known as burn-in, remains a challenge for NFA-based OPVs. To address this challenge, this study demonstrates a stable NFA-based OPV fabricated using sequential deposition (SqD) and a quasi-orthogonal solvent. The quasi-orthogonal solvent, which is prepared by incorporating 1-chloronaphthalene (1-CN) into dichloromethane (DCM), reduces the vapor pressure of the solvent and allows for the efficient dissolution and penetration of the Y6 (one of efficient NFAs) into a PM6 polymer-donor layer without damaging the latter. The resulting bulk heterojunction (BHJ) is characterized by a higher degree of crystallinity in the PM6 domains than that prepared using a conventional single-step deposition (SD) process. The OPV fabricated using the SqD process exhibits a PCE of 14.1% and demonstrates superior thermal stability to the SD-processed OPV. This study conclusively reveals that the formation of a thermally stable interface between the photoactive layer and the electron-transport layer (ETL) is the primary factor contributing to the high thermal stability observed in the SqD-processed OPV.

Molecular Engineering of Printed Semiconducting Blends to Develop Organic Integrated Circuits: Crystallization, Charge Transport, and Device Application Analyses.

Solution-based printing has contributed to the facile deposition of various types of materials, including the building blocks of printed electronics. In particular, solution-processable organic semiconductors (OSCs) are regarded as one of the most fascinating candidates for the fabrication of printed electronics. Herein, we report electrohydrodynamic (EHD) jet-printed p- and n-type OSCs, namely 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) and 6,13-bis((triisopropylsilyl)ethynyl)-5,7,12,14-tetraazapentacene (TIPS-TAP), and their use as single-OSC layers and as OSC mixed p-n layers to fabricate solution-processed p-, n-, and ambipolar-type organic field-effect transistors (OFETs). Use of the dragging mode of EHD jet printing, a process driven under a low electrostatic field with a short nozzle-to-substrate distance, was found to provide favorable conditions for growth of TIPS-PEN and TIPS-TAP crystals. In this way, the similar molecular structures of TIPS-PEN and TIPS-TAP yielded a homogeneous solid solution and showed ambipolar transport properties in OFETs. Therefore, the combination of single- and mixed-OSC layers enabled the preparation of various charge-transported devices from unit to integrated devices (NOT, NAND, NOR, and multivalued logic). Therefore, this fabrication technology can be useful for assisting in the production of OSC layers for practical applications in the near future.

Immobilization of Conjugated Polymer Domains for Highly Stable Non-Fullerene-Based Organic Solar Cells.

To commercialize organic solar cells (OSCs), changes in the optimized morphology of the photoactive layer caused by external stimuli that cause degradation must be addressed. This work improves OSC stability by utilizing the cross-linking additive 1,8-dibromooctane (DBO) and a sequential deposition process (XSqD) to fabricate the photoactive layer. The cross-linking additive in the donor polymer (PTB7-Th) improves polymer crystallinity and immobilizes the crystalline morphology by partial photo-cross-linking. Ellipsometry experiments confirm the increase in the glass transition temperature of cross-linked PTB7-Th. The polymer crystallinity is further improved after removal of non-cross-linked polymer and residual additive by chlorobenzene. The cross-linked polymer layer forms an efficient and stable heterojunction with a nonfullerene acceptor (IEICO-4F) layer via an XSqD process. The OSC based on the immobilized PTB7-Th exhibits excellent stability against light soaking and thermal aging.

Improving the Photostability of Small-Molecule-Based Organic Photovoltaics by Providing a Charge Percolation Pathway of Crystalline Conjugated Polymer.

Photostability of small-molecule (SM)-based organic photovoltaics (SM-OPVs) is greatly improved by utilizing a ternary photo-active layer incorporating a small amount of a conjugated polymer (CP). Semi-crystalline poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) and amorphous poly[(2,5-bis(2-decyltetradecyloxy)phenylene)-alt-(5,6-dicyano-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2CNBT) with similar chemical structures were used for preparing SM:fullerene:CP ternary photo-active layers. The power conversion efficiency (PCE) of the ternary device with PPDT2FBT (Ternary-F) was higher than those of the ternary device with PPDT2CNBT (Ternary-CN) and a binary SM-OPV device (Binary) by 15% and 17%, respectively. The photostability of the SM-OPV was considerably improved by the addition of the crystalline CP, PPDT2FBT. Ternary-F retained 76% of its initial PCE after 1500 h of light soaking, whereas Ternary-CN and Binary retained only 38% and 17% of their initial PCEs, respectively. The electrical and morphological analyses of the SM-OPV devices revealed that the addition of the semi-crystalline CP led to the formation of percolation pathways for charge transport without disturbing the optimized bulk heterojunction morphology. The CP also suppressed trap-assisted recombination and enhanced the hole mobility in Ternary-F. The percolation pathways enabled the hole mobility of Ternary-F to remain constant during the light-soaking test. The photostability of Ternary-CN did not improve because the addition of the amorphous CP inhibited the formation of ordered SM domains.

Solution-Processed PEDOT:PSS/MoS2 Nanocomposites as Efficient Hole-Transporting Layers for Organic Solar Cells.

An efficient hole-transporting layer (HTL) based on functionalized two-dimensional (2D) MoS2-poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) composites has been developed for use in organic solar cells (OSCs). Few-layer, oleylamine-functionalized MoS2 (FMoS2) nanosheets were prepared via a simple and cost-effective solution-phase exfoliation method; then, they were blended into PEDOT:PSS, a conducting conjugated polymer, and the resulting hybrid film (PEDOT:PSS/FMoS2) was tested as an HTL for poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) OSCs. The devices using this hybrid film HTL showed power conversion efficiencies up to 3.74%, which is 15.08% higher than that of the reference ones having PEDOT:PSS as HTL. Atomic force microscopy and contact angle measurements confirmed the compatibility of the PEDOT:PSS/FMoS2 surface for active layer deposition on it. The electrical impedance spectroscopy analysis revealed that their use minimized the charge-transfer resistance of the OSCs, consequently improving their performance compared with the reference cells. Thus, the proposed fabrication of such HTLs incorporating 2D nanomaterials could be further expanded as a universal protocol for various high-performance optoelectronic devices.

Ternary Organic Photovoltaics Prepared by Sequential Deposition of Single Donor and Binary Acceptors.

Binary organic photovoltaics (OPVs) fabricated by single-step (SS) deposition of a binary blend of polymer (or small molecule) donor and fullerene acceptor (SS binary OPV) are widely utilized. To improve the OPV performance, SS ternary OPVs utilizing a ternary blend consisting of two (or one) electron donor(s) and one (or two) electron acceptor(s) have been studied. SS ternary OPVs require more sensitive and complex optimization processes to optimize bulk heterojunctions with bicontinuous nanoscale phase separation of the donor and acceptor. We demonstrated a novel ternary OPV fabricated by sequential (SQ) deposition of a single polymer donor and a binary mixture consisting of a phenyl-C71-butyric acid methyl ester (PCBM) and nonfullerene acceptor, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3- d:2,3'- d']- s-indaceno[1,2- b:5,6- b']dithiophene (ITIC). In the SQ ternary OPV, PCBM effectively created a bicontinuous pathway for charge transport with a polymer, and ITIC mainly enhanced light absorption and photovoltage. This complementary effect was not observed in an SS ternary OPV utilizing the same donor and acceptors. Due to these complementary effects, the SQ ternary OPV exhibited a power conversion efficiency of 6.22%, which was 52 and 37% higher than that of the SQ binary OPV and the SS ternary OPV, respectively. In addition, the thermal stability of the SQ ternary OPV was found to be superior to that of the SS ternary OPV.

Reducing Trap-Assisted Recombination in Small Organic Molecule-Based Photovoltaics by the Addition of a Conjugated Block Copolymer.

The performance of organic photovoltaics (OPVs) based on the small-molecule organic semiconductor p-DTS(FBTTh2 )2 is greatly improved by the addition of a conjugated block copolymer composed of difluoroquinoxaline and thienopyrrolodione blocks (D130). The power conversion efficiency (PCE) of the p-DTS(FBTTh2 )2 -based OPV is improved from 5.08% to 6.75% by the addition of 5 wt% D130 to the photoactive layer, which is composed of p-DTS(FBTTh2 )2 and a fullerene derivative. Current-voltage and grazing incidence wide-angle X-ray scattering analyses revealed that the addition of D130 significantly reduces the trap density of the device and changes the packing orientation of p-DTS(FBTTh2 )2 from mostly edge-on to partially face-on. These changes greatly improve the charge carrier mobility of the OPV, indicating that D130 is highly compatible with p-DTS(FBTTh2 )2 . Furthermore, the addition of D130 improve the photostability of the OPV by reducing the burn-in loss under a light soaking intensity of 1 sun. The D130-based OPV maintained 34% of its initial PCE after a light soaking test for 858 h. In contrast, the PCE of the OPV without D130 reduced to 14% of its initial efficiency in the same time period.

Thermally Stable Bulk Heterojunction Prepared by Sequential Deposition of Nanostructured Polymer and Fullerene.

A morphologically-stable polymer/fullerene heterojunction has been prepared by minimizing the intermixing between polymer and fullerene via sequential deposition (SqD) of a polymer and a fullerene solution. A low crystalline conjugated polymer of PCPDTBT (poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]) has been utilized for the polymer layer and PC71BM (phenyl-C71-butyric-acid-methyl ester) for the fullerene layer, respectively. Firstly, a nanostructured PCPDTBT bottom layer was developed by utilizing various additives to increase the surface area of the polymer film. The PC71BM solution was prepared by dissolving it in the 1,2-dichloroethane (DCE), exhibiting a lower vapor pressure and slower diffusion into the polymer layer. The deposition of the PC71BM solution on the nanostructured PCPDTBT layer forms an inter-digitated bulk heterojunction (ID-BHJ) with minimized intermixing. The organic photovoltaic (OPV) device utilizing the ID-BHJ photoactive layer exhibits a highly reproducible solar cell performance. In spite of restricted intermixing between the PC71BM and the PCPDTBT, the efficiency of ID-BHJ OPVs (3.36%) is comparable to that of OPVs (3.87%) prepared by the conventional method (deposition of a blended solution of polymer:fullerene). The thermal stability of the ID-BHJ is superior to the bulk heterojunction (BHJ) prepared by the conventional method. The ID-BHJ OPV maintains 70% of its initial efficiency after thermal stress application for twelve days at 80 °C, whereas the conventional BHJ OPV maintains only 40% of its initial efficiency.

Ruthenium based nanostructures driven by morphological controls as efficient counter electrodes for dye-sensitized solar cells.

We introduce a facile approach to use ruthenium dioxide (RuO2) and ruthenium (Ru) nanostructures as effective counter electrodes instead of using platinum (Pt) for dye-sensitized solar cells (DSSCs). RuO2 and Ru nanostructure layers on the FTO glass can be readily prepared by a simple annealing process followed by the spin coating process of the mixture solution containing amorphous RuO2·xH2O precursor and poly(ethylene oxide) (PEO) as a dispersion matrix at low temperature in air. The Ru metal nanostructure layer prepared by the reduction of RuO2 with H2 shows the highest efficiency of 6.77% in DSSC operation, which is comparable to the efficiency of the Pt electrode (7.87%).

Enhanced performance in inverted polymer solar cells with D-π-A-type molecular dye incorporated on ZnO buffer layer.

We report the superior characteristics of a ZnO buffer layer covered with a phenothiazine-based, π-conjugated donor-acceptor (D-π-A)-type organic dye (called "d-ZnO"). The use of this system for the performance enhancement of inverted bulk heterojunction polymer solar cells (PSCs) with the configuration of indium tin oxide/d-ZnO/polymer:PC71 BM/MoO3 /Ag (PC71 BM=[6,6]-phenyl C71 butyric acid methyl ester) is investigated. The layer of organic dyes anchored on the ZnO surface through carboxylate bonding reduces the shunt path on bare ZnO surface and provides better interfacial contacts and energy level alignments between the ZnO layer and the photoactive layer. This phenomenon consequently leads to highly enhanced photovoltaic parameters (fill factor, open-circuit voltage, and short-circuit current density) and power conversion efficiencies (PCEs). Inverted solar cells containing the d-ZnO layer not only revealed about 34% (PCE: 4.37%) and 18% (PCE: 7.11%) improvement in the PCEs of the representative poly-3(hexylthiophene) (P3HT) and low-band-gap poly{[4,8-bis-(2-ethyl-hexyl-thiophene-5-yl)-benzo[1,2-b:4,5-b']dithiophene-2,6-diyl]-alt-[2-(2'-ethylhexanoyl)-thieno[3,4-b]thiophen-4,6-diyl]} (PBDTTT-C-T) polymer systems, respectively, but also showed 2-4 times longer device lifetimes than their counterparts without the organic dye layer. These results demonstrate that this simple approach used in inverted PSCs with a metal oxide buffer layer could become a promising procedure to fabricate highly efficient and stable PSCs.

Tandem Blaise-Nenitzescu reaction: one-pot synthesis of 5-hydroxy-α-(aminomethylene)benzofuran-2(3H)-ones from nitriles.

In contrast to the reaction of benzoquinones with ß-enaminoesters providing indoles (Nenitzescu reaction), the tandem one-pot reaction of the Blaise reaction intermediate, zinc bromide complex of ß-enaminoesters, with benzoquinone affords 5-hydroxy-α-(aminomethylene)benzofuran-2(3H)-ones in good to excellent yields (tandem Blaise-Nenitzescu reaction).

One-pot synthesis of 2-pyridones via chemo- and regioselective tandem Blaise reaction of nitriles with propiolates.

The Blaise reaction intermediate, generated in situ from Reformatsky reagent and nitrile, reacted with propiolates in a chemo- and regioselective manner to afford 2-pyridone derivatives in good to excellent yields.