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.

Influence of Acid-Doped Poly(ethylene imine) Interlayers on the Performance of Polymer:Nonfullerene Solar Cells.

This work reports that ultrathin polymeric films doped with organic acid molecules can act as an electron-transporting interfacial layer in polymer:nonfullerene solar cells. The polymeric interfacial layers, which consist of poly(ethylene imine) (PEI) doped with 3-hydroxypropane-1-sulfonic acid (HPSA) at various HPSA molar ratios, are introduced between transparent indium-tin oxide (ITO) electrodes and polymer:nonfullerene bulk heterojunction layers. The HPSA-doped PEI (PEI:HPSA) films are optically translucent in the wavelength range of ≈300-800 nm, while the acidity of PEI solutions reached ≈pH = 7 at HPSA = 30 mol%. The power conversion efficiency of solar cells is improved by doping 20 mol% HPSA due to the increased short circuit current density without open circuit voltage reduction. The improvement in solar cell performances is attributed to an adequate control of HPSA doping ratios, which spares undoped amine units of PEI for making sufficient net dipole layers with ITO surfaces and makes permanent charges for high electrical conductivity in the layers. The surface morphology and doped states are characterized with atomic force microscopy and X-ray photoelectron spectroscopy.

Water-Soluble Reactive Polymer Blends for Stable Memory Layers in Low-Voltage Nonvolatile Organic Memory Transistors with High Mobility and Data-Retention Characteristics.

Here low-voltage nonvolatile organic memory transistors, featuring high charge-carrier mobility and outstanding data-retention characteristics, by employing water-soluble reactive polymer blends as a gate-insulating memory layer are demonstrated. Blend films of poly(vinyl alcohol) (PVA) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA) (PVA:PAMPSA) are prepared from their aqueous solutions with various molar ratios of PAMPSA (0-18 mol%) and thermally annealed at 70 and 110 °C. Organic field-effect transistors (OFETs) are fabricated by depositing poly(3-hexylthiophene) (P3HT) channel layers on the thermally treated PVA:PAMPSA films. Results show that the hole mobility of OFETs is remarkably increased (≈294 times at 70 °C and ≈42 times at 110 °C) by adding only 2 mol% PAMPSA to the PVA films and further improved at 10 mol% PAMPSA (>11.7 cm2  V-1 s-1 at 70 °C and >3.8 cm2  V-1  s-1 at 110 °C). The hysteresis characteristics are rather strengthened for the PVA:PAMPSA layers by annealing at 110 °C due to the formation of cross-linking sites, even though the OFETs with the pristine PVA layers do almost lose hysteresis characteristics at 110 °C. The optimized OFETs with the PVA:PAMPSA layers (10 mol%, 110 °C) deliver excellent data retention characteristics during >10 000 memory cycles at a voltage range of -5 to +5 V.

Performance and Stability of Polymer:Nonfullerene Solar Cells with 100 °C-Annealed Electron-Collecting Combination Layers.

Invited for this month's cover is the group of Youngkyoo Kim at the Kyungpook National University. The image shows the improved electron transfer by hybrid combination layers featuring peculiar morphology for better efficiency and stability in polymer solar cells. The Full Paper itself is available at 10.1002/cssc.202100841.

Performance and Stability of Polymer : Nonfullerene Solar Cells with 100 °C-Annealed Electron-Collecting Combination Layers.

Inverted-type organic solar cells, fabricated with low-temperature-processed combination layers of hybrid electron-collecting buffer layers (ECBLs) consisting of zinc oxide (ZnO) and poly(2-ethyl-2-oxazoline) (PEOz) and additional PEOz interlayers, showed improved performance and stability. The ZnO : PEOz precursor films with various PEOz compositions (0-12 wt %) were prepared and thermally treated at 100 °C, leading to the ECBLs on which the PEOz interlayers were subsequently deposited before coating of polymer : nonfullerene bulk heterojunction layers. Results showed that the power conversion efficiency of solar cells reached approximately 9.38 and 10.11 % (average) in case of the ZnO/PEOz and ZnO : PEOz(6 wt % PEOz)/PEOz combination layers, respectively, despite the low-temperature thermal annealing process. A continuous irradiation test for 12 h under one sun condition (air mass 1.5G, 100 mW cm-2 ) disclosed that the devices with the ZnO : PEOz(6 wt % PEOz)/PEOz combination layers were more stable than those with the ZnO/PEOz layers.

Short-Wave Infrared-Sensing Organic Phototransistors with a Triarylamine-Based Polymer Doped with a Lewis Acid-Type Small Molecule.

Here, we report that a triarylamine-based polymer, poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine] (PolyTPD), is effectively doped with tris(pentafluorophenyl)borane (BCF) and the doping level is dependent on the molar ratio of BCF to PolyTPD (repeating unit). The doping reaction is performed at 25 °C at the solution states using chlorobenzene solvent by varying the BCF molar ratio up to 2.0. The resulting PolyTPD:BCF films show new broad optical absorption peaks at a wavelength of λ = 1000-3300 nm, covering the full range of short-wave infrared (SWIR, λ = 1400-3000 nm), which is stronger at a higher BCF molar ratio. Spectroscopic characterizations confirm the generation of radicals (single electrons) in PolyTPD by BCF doping, which resulted in a gradual shift of the highest occupied molecular orbital (HOMO) energy level with the BCF molar ratio. The PolyTPD:BCF films are applied as a gate-sensing layer (GSL) in the geometry of organic field-effect transistors (OFETs), leading to SWIR-sensing organic phototransistors (OPTRs). The optimized SWIR-OPTRs with the PolyTPD:BCF GSLs (BCF molar ratio = 0.5) can detect SWIR light with maximum photoresponsivities of 583.4 mA/W (λ = 1500 nm), 695.4 mA/W (λ = 2000 nm), and 829.4 mA/W (λ = 2500 nm).

Near-Infrared Organic Phototransistors with Polymeric Channel/Dielectric/Sensing Triple Layers.

A new type of near-infrared (NIR)-sensing organic phototransistor (OPTR) was designed and fabricated by employing a channel/dielectric/sensing (CDS) triple layer structure. The CDS structures were prepared by inserting poly(methyl methacrylate) (PMMA) dielectric layers (DLs) between poly(3-hexylthiophene) (P3HT) channel layers and poly[{2,5-bis-(2-octyldodecyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2'-(2,1,3-benzothiadiazole)-5,5'-diyl}] (PODTPPD-BT) top sensing layers. Two different thicknesses of PMMA DLs (20 nm and 50 nm) were applied to understand the effect of DL thickness on the sensing performance of devices. Results showed that the NIR-OPTRs with the CDS structures were operated in a typical n-channel mode with a hole mobility of ca. 0.7~3.2 × 10-4 cm2/Vs in the dark and delivered gradually increased photocurrents upon illumination with an NIR light (905 nm). As the NIR light intensity increased, the threshold voltage was noticeably shifted, and the resulting transfer curves showed a saturation tendency in terms of curve shape. The operation of the NIR-OPTRs with the CDS structures was explained by the sensing mechanism that the excitons generated in the PODTPPD-BT top sensing layers could induce charges (holes) in the P3HT channel layers via the PMMA DLs. The optically modulated and reflected NIR light could be successfully detected by the present NIR-OPTRs with the CDS structures.

Low-Voltage Organic Nonvolatile Memory Transistors with Water-Soluble Polymers Containing Thermally Induced Radical Dipoles.

A water-soluble acidic polymer, poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA), was applied as a gate-insulating layer for organic field-effect transistors (OFETs). Before depositing the poly(3-hexylthiophene) (P3HT) channel layers, the PAMPSA layers were subjected to thermal treatment at various temperatures from 140 to 230 °C. The OFET performance was greatly enhanced by thermal treatment between 140 and 170 °C, whereas it became very poor at higher temperatures (200-230 °C). In particular, the transfer curves showed pronounced hysteresis phenomena at 170 °C. Various measurements including thermogravimetric analysis and X-ray photoelectron spectroscopy disclosed that the PAMPSA chains underwent thermal degradation from ca. 160 °C and could generate carbon radicals leading to the formation of dipoles with the nitrogen lone pair electrons. The carbon-nitrogen dipoles delivered hysteresis phenomena to the OFETs with the PAMPSA layers treated at 170 °C, which exhibited excellent memory retention characteristics up to 10 000 cycles even at -1 V. Hence, it is expected that the thermally treated PAMPSA layers can be used as one of the viable gate-insulating memory materials for low-voltage transistor-type organic memory devices (TOMDs).

Enhanced superoxide sensitivity in organic field-effect transistor sensors by introducing nanoclay-polyphenol-polymer hybrid sensing channels.

Here we report that nanoclay-polyphenol-polymer hybrid sensing channels can greatly enhance the sensitivity for hazardous reactive oxygen species (ROS) in organic field-effect transistor (OFET) sensors. The hybrid layers were prepared by introducing nanoclay into the binary mixtures of poly(3-hexylthiophene) (P3HT) and rutin (a polyphenol) at various weight ratios. The presence of nanoclay improved the P3HT crystallinity in the hybrid films, which contributed to the increased drain current and well-maintained hole mobility even at the reduced amount of charge-transporting P3HT part. At the best composition (P3HT:rutin:nanocaly = 10:1:2 by weight), the OFETs with the hybrid layers were able to sense even 1 nM superoxide (a ROS) and exhibited pronouncedly enhanced sensitivity compared to those without nanoclay. The morphology investigation disclosed that rutin-nanoclay complexes formed in the hybrid films might be responsible for the enhanced sensitivity, because they let more rutin molecules protrude on the surface of channel layers for reactions with superoxide.

Ultrasensitive detection of hazardous reactive oxygen species using flexible organic transistors with polyphenol-embedded conjugated polymer sensing layers.

Here we report that superoxide, one of the hazardous reactive oxygen species (ROS), can be quickly detected by flexible organic field-effect transistors (OFETs) with the polyphenol-embedded conjugated polymer micro-channels. Rutin, one of the abundant polyphenols found in a variety of plants, was employed as a sensing molecule and embedded in the poly(3-hexylthiophene) (P3HT) matrix. The rutin-embedded P3HT layers showed randomly distributed micro-domains, which became bigger as the rutin content increased. The best transistor performance was achieved at the rutin content of 10 wt%, while the OFETs exhibited proper and controllable transistor performances even in the phosphate buffer solutions. The sensing test revealed that the present OFET sensors could stably detect superoxide using very small amount (<10 µl) of samples at extremely low concentrations (500 pM), while they exhibited outstanding stability and durability upon repeated detection and storage-reuse tests. Finally, the present flexible OFET sensors could deliver confident sensing results for the detection of superoxide generated from the mouse RAW264.7 macrophages.

Influence of Weak Base Addition to Hole-Collecting Buffer Layers in Polymer:Fullerene Solar Cells.

We report the effect of weak base addition to acidic polymer hole-collecting layers in normal-type polymer:fullerene solar cells. Varying amounts of the weak base aniline (AN) were added to solutions of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The acidity of the aniline-added PEDOT:PSS solutions gradually decreased from pH = 1.74 (AN = 0 mol% ) to pH = 4.24 (AN = 1.8 mol %). The electrical conductivity of the PEDOT:PSS-AN films did not change much with the pH value, while the ratio of conductivity between out-of-plane and in-plane directions was dependent on the pH of solutions. The highest power conversion efficiency (PCE) was obtained at pH = 2.52, even though all devices with the PEDOT:PSS-AN layers exhibited better PCE than those with the pristine PEDOT:PSS layers. Atomic force microscopy investigation revealed that the size of PEDOT:PSS domains became smaller as the pH increased. The stability test for 100 h illumination under one sun condition disclosed that the PCE decay was relatively slower for the devices with the PEDOT:PSS-AN layers than for those with pristine PEDOT:PSS layers.

Strong Composition Effects in All-Polymer Phototransistors with Bulk Heterojunction Layers of p-type and n-type Conjugated Polymers.

We report the composition effect of polymeric sensing channel layers on the performance of all-polymer phototransistors featuring bulk heterojunction (BHJ) structure of electron-donating (p-type) and electron-accepting (n-type) polymers. As an n-type component, poly(3-hexylthiopehe-co-benzothiadiazole) end-capped with 4-hexylthiophene (THBT-4ht) was synthesized via two-step reactions. A well-studied conjugated polymer, poly(3-hexylthiophene) (P3HT), was employed as a p-type polymer. The composition of BHJ (P3HT:THBT-4ht) films was studied in detail by varying the THBT-4ht contents (0, 1, 3, 5, 10, 20, 30, 40, and 100 wt %). The best charge separation in the P3HT:THBT-4ht films was measured at 30 wt % by the photoluminescence (PL) study, while the charge transport characteristics of devices were improved at the low THBT-4ht contents (<10 wt %). The photosensing experiments revealed that the photosensivity of all-polymer phototransistors was higher than that of the phototransistors with the pristine P3HT layers and strongly dependent on the BHJ composition. The highest (corrected) responsivity (RC) was achieved at 20 wt %, which can be attributable to the balance between the best charge separation and transport states, as investigated for crystal nanostructures and surface morphology by employing synchrotron-radiation grazing-incidence wide-angle X-ray scattering, high-resolution/scanning transmission electron microscopy, and atomic force microscopy.

Polymer Nanodot-Hybridized Alkyl Silicon Oxide Nanostructures for Organic Memory Transistors with Outstanding High-Temperature Operation Stability.

Organic memory devices (OMDs) are becoming more important as a core component in flexible electronics era because of their huge potentials for ultrathin, lightweight and flexible plastic memory modules. In particular, transistor-type OMDs (TOMDs) have been gradually spotlighted due to their structural advantages possessing both memory and driving functions in single devices. Although a variety of TOMDs have been developed by introducing various materials, less attention has been paid to the stable operation at high temperatures. Here we demonstrate that the polymer nanodot-embedded alkyl silicon oxide (ASiO) hybrid materials, which are prepared by sol-gel and thermal cross-linking reactions between poly(4-vinylphenol) (PVP) and vinyltriethoxysilane, can deliver low-voltage (1~5 V) TOMDs with outstanding operation stability (>4700 cycles) at high temperatures (150 °C). The efficient low-voltage memory function is enabled by the embedded PVP nanodots with particular lattice nanostructures, while the high thermal stability is achieved by the cross-linked ASiO network structures.

Broadband All-Polymer Phototransistors with Nanostructured Bulk Heterojunction Layers of NIR-Sensing n-Type and Visible Light-Sensing p-Type Polymers.

We report 'broadband light-sensing' all-polymer phototransistors with the nanostructured bulk heterojunction (BHJ) layers of visible (VIS) light-sensing electron-donating (p-type) polymer and near infrared (NIR) light-sensing electron-accepting (n-type) polymer. Poly[{2,5-bis-(2-ethylhexyl)-3,6-bis-(thien-2-yl)-pyrrolo[3,4-c]pyrrole-1,4-diyl}-co-{2,2'-(2,1,3-benzothiadiazole)]-5,5'-diyl}] (PEHTPPD-BT), which is synthesized via Suzuki coupling and employed as the n-type polymer, shows strong optical absorption in the NIR region (up to 1100 nm) in the presence of weak absorption in the VIS range (400~600 nm). To strengthen the VIS absorption, poly(3-hexylthiophene) (P3HT) is introduced as the p-type polymer. All-polymer phototransistors with the BHJ (P3HT:PEHTPPD-BT) layers, featuring a peculiar nano-domain morphology, exhibit typical p-type transistor characteristics and efficiently detect broadband (VIS~NIR) lights. The maximum corrected responsivity (without contribution of dark current) reaches up to 85~88% (VIS) and 26~40% (NIR) of theoretical responsivity. The charge separation process between P3HT and PEHTPPD-BT components in the highest occupied molecular orbital is proposed as a major working mechanism for the effective NIR sensing.

Liquid crystal-gated-organic field-effect transistors with in-plane drain-source-gate electrode structure.

We report planar liquid crystal-gated-organic field-effect transistors (LC-g-OFETs) with a simple in-plane drain-source-gate electrode structure, which can be cost-effectively prepared by typical photolithography/etching processes. The LC-g-OFET devices were fabricated by forming the LC layer (4-cyano-4'-pentylbiphenyl, 5CB) on top of the channel layer (poly(3-hexylthiophene), P3HT) that was spin-coated on the patterned indium-tin oxide (ITO)-coated glass substrates. The LC-g-OFET devices showed p-type transistor characteristics, while a current saturation behavior in the output curves was achieved for the 50-150 nm-thick P3HT (channel) layers. A prospective on/off ratio (>1 × 10(3)) was obtained regardless of the P3HT thickness, whereas the resulting hole mobility (0.5-1.1 cm(2)/(V s)) at a linear regime was dependent on the P3HT thickness. The tilted ordering of 5CB at the LC-P3HT interfaces, which is induced by the gate electric field, has been proposed as a core point of working mechanism for the present LC-g-OFETs.