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.

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.

Nanoscale Film Morphology and n-Type Digital Memory Characteristics of π-Conjugated Donor-Acceptor Alternating Copolymer Based on Thiophene and Thiadiazole Units.

Various molecular weight π-conjugated donor-acceptor polymers based on thiadiazole and thiophene units are investigated with respect to nanoscale film morphology and digital memory performance. Interestingly, all polymers reveal excellent n-type digital permanent memory characteristics, which are governed by the combination of Ohmic and trap-limited space charge limited conductions via a hopping process using thiadiazole and thiophene units as charge traps and stepping stones. The digital memory performance is significantly influenced by the film morphology details that vary with the polymer molecular weight as well as the film thickness. A higher population of face-on structure formation, as well as higher molecular weight, provides a wider film thickness window of digital memory operation. Overall, π-conjugated PBTDzTV polymers are suitable for the production of high-performance, programmable n-type permanent memory devices with very low power consumption.

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.

Folate ligand anchored liquid crystal microdroplets emulsion for in vitro detection of KB cancer cells.

A KB cancer cell-selective, liquid crystal microdroplets emulsion is prepared using folic acid-conjugated block copolymers (PS-b-PAA-FA) and sodium dodecyl sulfate (SDS) as a mediator to induce configurational transitions in 4-cyano-4'-pentylbiphenyl (5CB) liquid crystal microdroplets emulsion. The prepared liquid crystal microdroplets emulsion has shown a configurational transition from radial to bipolar on interacting with KB cancer cells, but no transition from radial to bipolar configuration is observed when liquid crystal microdroplets emulsion was allowed to interact with other normal cells such as fibroblast and osteoblast. The KB cancer cell selectivity of liquid crystal microdroplets emulsion has been considered due to the presence of KB cancer cell folate receptor-specific ligand (FA) at the surface of liquid crystal microdroplets, which allowed liquid crystal microdroplets to interact specifically with KB cancer cells. The ligand-receptor interactions have been considered responsible for triggering the configurational transitions from radial to bipolar in liquid crystal microdroplets emulsion. Thus, folate ligand anchored liquid crystal microdroplets emulsion has shown a potential to be used for in vitro detection of KB cancer cells in the early stage of tumor development.

Influence of nickel(II) oxide nanoparticle addition on the performance of organic field effect transistors.

Here, the improved performance of organic field effect transistors (OFET) by doping inorganic nanoparticles into a semiconducting polymer as a channel layer is briefly reported. Nickel(II) oxide nanoparticle (NiOnp) was used as an inorganic dopant while regioregular poly(3-hexylthiophene) (P3HT) was used as a matrix polymer for the channel layer in the OFETs. The doping ratio of NiOnp was made 1 wt.% so that it would minimally influence the nanostructure of the P3HT channel layer. The results showed that the optical absorption spectrum of the P3HT film was slightly red-shifted by the NiOnp doping, which reflects the improved crystallinity of the P3HT domains in the P3HT:NiOnp films. The drain current of the OFETs with the P3HT:NiOnp films was significantly enhanced ca. three-to-seven fold by the NiOnp doping under appying gate voltages while the hole mobility of the OFETs P3HT:NiOnp films was improved as much as three fold by the NiOnp doping. The enhanced performance has been assigned to the role of NiOnp that has relatively higher hole mobility than the P3HT polymer.

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.

Direct measurement of extracellular electrical signals from mammalian olfactory sensory neurons in planar triode devices.

An artificial nose was developed to mimic aspects of sensory transduction of the peripheral mammalian olfactory system. We directly cultured and differentiated rat olfactory sensory neurons (OSNs) on indium-tin oxide electrodes of planar triode substrates without a coupling agent. Direct voltage (~50 µV) and current (~250 nA) signals were measured simultaneously when OSNs on the planar triode substrates were exposed to odorant mixtures. The response signals were sensitive to the concentration of the odorant mixture, with a typical lifetime, shape, and adaptation profile as seen in responses upon repeated stimulation in vivo. We found that the rising time to the peak current was ~161 ms, while the signal back to baseline was in 1.8 s, which are in agreement with the natural intracellular electrophysiological responses. These results provide the first evidence that mature OSNs grown in a planar triode device are able to detect direct electrophysiological responses to odorants.

All-polymer solar cells with bulk heterojunction nanolayers of chemically doped electron-donating and electron-accepting polymers.

We report the improved performance of all-polymer solar cells with bulk heterojunction nanolayers of an electron-donating polymer (poly(3-hexylthiophene) (P3HT)) and an electron-accepting polymer (poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT)), which were both doped with 4-ethylbenzenesulfonic acid (EBSA). To choose the doping ratio of P3HT for all-polymer solar cells, various EBSA doping ratios (0, 1, 3, 5, 10, 20 wt%) were tested by employing optical absorption spectroscopy, photoluminescence spectroscopy, photoelectron yield spectroscopy, and space-charge-limited current (SCLC) mobility measurement. The doping reaction of P3HT with EBSA was followed by observing the colour change in solutions. The final doping ratio for P3HT was chosen as 1 wt% from the best hole mobility measured in the thickness direction, while that for F8BT was fixed as 10 wt% (F8BT-EBSA). The polymer:polymer solar cells with bulk heterojunction nanolayers of P3HT-EBSA (EBSA-doped P3HT) and F8BT-EBSA (EBSA-doped F8BT) showed greatly improved short circuit current density (J(SC)) and open circuit voltage (V(OC)), compared to the undoped solar cells. As a result, the power conversion efficiency (PCE) was enhanced by ca. 300% for the 6 : 4 (P3HT-EBSA : F8BT-EBSA) composition and ca. 400% for the 8 : 2 composition. The synchrotron-radiation grazing incidence angle X-ray diffraction (GIXD) measurement revealed that the crystallinity of the doped nanolayers significantly increased by EBSA doping owing to the formation of advanced phase segregation morphology, as supported by the surface morphology change measured by atomic force microscopy. Thus the improved PCE can be attributed to the enhanced charge transport by the formation of permanent charges and better charge percolation paths by EBSA doping.

Characteristics of protein-polymer nanobiocomposite films for protein devices.

Here we report the characteristics of protein-polymer nanobiocomposite films and their solid state devices. The protein-polymer nanobiocomposite films (thickness = approximately 125 nm) were prepared by spin-coating the solution of cytochrome c (cyt c) and poly(vinyl alcohol) (PVA) (cyt c:PVA = 3:1 by weight). To understand the characteristics of the cyt c-PVA films (nanolayers), we employed the optical absorption and surface morphology measurement and then fabricated planar diode-type solid state devices. The optical absorption measurement showed that the heme part of cyt c in the cyt c-PVA nanolayer was well kept after the coating process, while the crack-like surface was found from the atomic force microscopy measurement. The planar device showed an ohmic type dark current, but the current gradually increased as the incident light intensity increased. In particular, the (photo) current was strongly dependent upon the voltage, which was assigned to the insulating role of cyt c surrounding groups and PVA. This trend was supported by the slow rise and decay time via photo-switching experiment.

Effect of inorganic nanoparticle addition to the hole-collecting buffer layers in polymer solar cells.

We investigated the influence of nickel oxide (NiO) nanoparticles that are incorporated into the hole-collecting buffer layer [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)] on the performance of polymer:fullerene solar cells. To understand the optimum composition of NiO nanoparticles, the composition of NiO nanoparticles was varied from 0 wt% to 23 wt%. Results showed that the optical transmittance was gradually decreased as the NiO content increased. However, the device performance (short circuit current density, fill factor, series resistance, power conversion efficiency) exhibited a two stage trend in a boundary of approximately 9 wt% NiO content. This trend was in good agreement with the trend of sheet resistance in the presence of slight discrepancy owing to the different charge transport geometry.

Two-dimensional photonic crystal arrays for polymer:fullerene solar cells.

We report the application of two-dimensional (2D) photonic crystal (PC) array substrates for polymer:fullerene solar cells of which the active layer is made with blended films of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The 2D PC array substrates were fabricated by employing a nanosphere lithography technique. Two different hole depths (200 and 300 nm) were introduced for the 2D PC arrays to examine the hole depth effect on the light harvesting (trapping). The optical effect by the 2D PC arrays was investigated by the measurement of optical transmittance either in the direction normal to the substrate (direct transmittance) or in all directions (integrated transmittance). The results showed that the integrated transmittance was higher for the 2D PC array substrates than the conventional planar substrate at the wavelengths of ca. 400 nm, even though the direct transmittance of 2D PC array substrates was much lower over the entire visible light range. The short circuit current density (J(SC)) was higher for the device with the 2D PC array (200 nm hole depth) than the reference device. However, the device with the 2D PC array (300 nm hole depth) showed a slightly lower J(SC) value at a high light intensity in spite of its light harvesting effect proven at a lower light intensity.

Effect of film thickness in hybrid polymer/polymer solar cells with zinc oxide nanoparticles.

We briefly report the effect of film thickness on the performance of hybrid polymer/polymer solar cells that were made using poly(3-hexylthiophene), poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT), and zinc oxide (ZnO) nanoparticles. The ZnO nanoparticles were introduced to improve the electron transport property of P3HT/F8BT blend films. Results showed that the open circuit voltage (V(OC)) was remarkably decreased by adding only approximately 0.5 wt% ZnO nanoparticles though the optical absorption spectra were not much changed due to the small amount of ZnO nanoparticles in the ternary blend films (approximately 1.9%). In contrast, the fill factor (FF) of devices was improved for the ternary blend devices with the ZnO nanoparticles due to the improved electron transport as evidenced by the reduced series resistance. The short circuit current density of devices was not much changed because of the enhanced charge transport. However, the addition of ZnO nanoparticles decreased the power conversion efficiency of devices owing to the larger influence of V(OC) compared to the FF improvement.

Pressing effect in polymer solar cells with bulk heterojunction nanolayers.

We report the effect of pressing light-absorbing layers on the performance of polymer solar cells. The light-absorbing active layer was prepared on the transparent conducting oxide coated substrates from solutions that contain a mixture of regioregular poly(3-hexylthiophene) and soluble fullerene molecules. The active layers were pressed using a home-built micro-press system by controlling temperature and pressure, followed by the top electrode deposition. The surface of the active layers pressed was examined using atomic force microscope, while the photovoltaic characteristics of devices were measured under simulated solar light illumination (air mass 1.5 G, 100 mW/cm2). Results showed that the dark current of devices was noticeably increased by pressing the active layer without respect to the pressing temperature. The highest power conversion efficiency was achieved for the device with the active layer pressed under 10 kgf at 70 degrees C. The result was explained in terms of surface morphology and thermophysical effect.

Effect of side groups in polynorbornene films for transparent conductive substrates.

The imide-functionalized polynorbornene films exhibited excellent optical transparency in the visible range as well as high thermal stability over 200 degrees C. The indium tin oxide (ITO) thin films were coated on the imide-functionalized polynorbornene films at various deposition temperatures by employing radio-frequency (r.f.) planar magnetron sputtering system. The resulting ITO-coated imide-functionalized polynorbornene substrates showed good electrical and optical properties, while the figure of merit examination revealed that the present substrates are comparable to conventional ITO-glass substrates. This was confirmed from the preliminary result of organic light-emitting devices fabricated using the imide-functionalized polynorbornene substrates.

Persistent electrical energy generation from organic diodes under constant pressure: toward organic gravity nanogenerators.

Here it is demonstrated that electricity can be continuously generated by pressing organic diodes with the poly(3-hexylthiophene) (P3HT) layers which are sandwiched between indium-tin oxide and aluminum (Al) electrodes. The optimized single devices with the 150-nm-thick P3HT layers are able to generate 60 µV and 45 µA by pressing, while persistent voltage (50 µV) and current (45 µA) generations are achieved by continuous pressing for 7 days. The charge generation by pressing of organic diodes is supported by the current density-voltage and capacitance measurements, while the friction of pi-orbital electrons in the P3HT chains upon pressing is proposed for the mechanism of persistent electricity generation. Organic diode modules with 14 sub-cells in series deliver ca. 0.4 V and ca. 20 µW. The present technology is expected to pave the way for next-generation energy conversion devices, organic gravity nanogenerators that enable continuous electricity generation by gravitational forces.

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).

Preface to the Special Issue of ChemSusChem on Advanced Organic Solar Cells.

Organic solar cells have garnered much interest as an Earth-abundant and low-energy-production renewable energy source. In their Editorial to the Special Issue on Advanced Organic Solar Cells, Guest Editors Christoph Brabec, Martin Heeney, Youngkyoo Kim, and Christine Luscombe introduce this exciting field and discuss some of the Special Issue's contents.

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.

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.