π-Conjugated Polymers Incorporating a Novel Planar Quinoid Building Block with Extended Delocalization and High Charge Carrier Mobility.

Two novel conjugated polymers incorporating quinoidal thiophene are successfully synthesized. By combining 1D nuclear magnetic resonance (NMR) and 2D nuclear Overhauser effect spectroscopy analyses, the isomeric form of the major quinoid monomer is clearly identified as the asymmetric Z, E-configuration. The quinoidal polymers are synthesized via Stille polymerization with thiophene or bithiophene. Both quinoidal polymers exhibit the low band gap of 1.45 eV and amphoteric redox behavior, indicating extended conjugation owing to the quinoidal backbone. These quinoidal polymers show ambipolar behaviors with high charge carrier mobilities when applied in organic field-effect transistors. In addition, the radial alignment of polymer chains achieved by off-center spin-coating leads to further improvement of device performance, with poly(quinoidal thiophene-bithiophene) exhibiting a high hole mobility of 8.09 cm2 V-1 s-1 , which is the highest value among the quinoidal polymers up to now. Microstructural alteration via thermal annealing or off-center spin-coating is found to beneficially affect charge transport. The enhancement of crystallinity with strong π-π interactions and the nanofibrillar structure arising from planar well-delocalized quinoid units is considered to be responsible for the high charge carrier mobility.

Distinguishing Zigzag and Armchair Edges on Graphene Nanoribbons by X-ray Photoelectron and Raman Spectroscopies.

Graphene nanoribbons (GNRs) have recently emerged as alternative 2D semiconductors owing to their fascinating electronic properties that include tunable band gaps and high charge-carrier mobilities. Identifying the atomic-scale edge structures of GNRs through structural investigations is very important to fully understand the electronic properties of these materials. Herein, we report an atomic-scale analysis of GNRs using simulated X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Tetracene with zigzag edges and chrysene with armchair edges were selected as initial model structures, and their XPS and Raman spectra were analyzed. Structurally expanded nanoribbons based on tetracene and chrysene, in which zigzag and armchair edges were combined in various ratios, were then simulated. The edge structures of chain-shaped nanoribbons composed only of either zigzag edges or armchair edges were distinguishable by XPS and Raman spectroscopy, depending on the edge type. It was also possible to distinguish planar nanoribbons consisting of both zigzag and armchair edges with zigzag/armchair ratios of 4:1 or 1:4, indicating that it is possible to analyze normally synthesized GNRs because their zigzag to armchair edge ratios are usually greater than 4 or less than 0.25. Our study on the precise identification of GNR edge structures by XPS and Raman spectroscopy provides the groundwork for the analysis of GNRs.

Investigation of Thermally Induced Degradation in CH3NH3PbI3 Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis.

In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI3 perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI3 perovskite film changes to an intermediate phase and decomposes to CH3I, NH3, and PbI2 after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CH3NH3+ organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI3 perovskites. These results provide important progress towards improved understanding of the thermal degradation mechanisms in perovskite materials and will facilitate improvements in the design and fabrication of perovskite solar cells with better thermal stability.

Selective Morphology Control of Bulk Heterojunction in Polymer Solar Cells Using Binary Processing Additives.

We report the effect of binary additives on the fabrication of polymer solar cells (PSCs) based on a bulk heterojunction (BHJ) system. The combination of 1,8-diiodooctane (DIO), a high-boiling and selective solvent, for fullerene derivatives and poly(dimethylsiloxane) (PDMS) precursor, a nonvolatile insulating additive, affords complementary functions on the effective modulation of BHJ morphology. It was found that DIO and PDMS precursor each play different roles in the control of BHJ morphology, and thus, the power conversion efficiency (PCE) can be further enhanced to 7.6% by improving the fill factor (FF) from 6.8% compared to that achieved using a conventional device employing only a DIO additive. In the BHJ of the active layer, DIO suppressed the large phase separation of PBDTTT-CF and PC71BM while allowing the formation of continuous polymer networks in the donor polymer through phase separation of the PDMS precursor and BHJ components. The appropriate amount of PDMS precursor does not disturb charge transport in the BHJ despite having insulating properties. In addition, the dependence of photovoltaic parameters on different light intensities reveals that the charge recombination in the device with DIO and PDMS precursor decreases compared to that achieved using the device with only DIO.

Solution-processed barium salts as charge injection layers for high performance N-channel organic field-effect transistors.

N-channel organic field-effect transistors (OFETs) have generally shown lower field-effect mobilities (µFET) than their p-type counterparts. One of the reasons is the energetic misalignment between the work function (WF) of commonly used charge injection electrode, i.e. gold (Au), and the lowest unoccupied molecular orbital (LUMO) of n-channel electron-transporting organic semiconductors. Here, we report barium salts as solution-processed interlayers, to improve the electron-injection and/or hole-blocking in top-gate/bottom-contact n-channel OFETs, based on poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-dithiophene)} (P(NDI2OD-T2)) and phenyl-C61-butyric acid methyl ester (PC61BM). Two different barium salts, barium hydroxide (Ba(OH)2) and barium chloride (Ba(Cl)2), are employed as the ultrathin interlayer (∼2 nm); and they effectively tune the WF of Au from 4.9 eV, to as low as 3.5 eV. The resulting n-channel OFETs exhibit significantly improved µFET, approaching 2.6 cm(2)/(V s) and 0.1 cm(2)/(V s) for the best P(NDI2OD-T2) and PC61BM devices, respectively, with Ba(OH)2 as interlayer.

Inkjet-printing-based soft-etching technique for high-speed polymer ambipolar integrated circuits.

Here, we report the so-called soft-etching process based on an inkjet-printing technique for realizing high-performance printed and flexible organic electronic circuits with conjugated polymer semiconductors. The soft-etching process consists of selective etching of the gate made of a dielectric polymer and deposition of another gate dielectric layer. The method enables the use of a more desirable polymer dielectric layer for the p-channel and n-channel organic field-effect transistors (OFETs) in complementary integrated circuits. We fabricated high-performance ambipolar complementary inverters and ring oscillators (ROs) using poly([N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)) (P(NDI2OD-T2)) as the active layer as well as poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) and polystyrene ((PS)/P(VDF-TrFE)) as dielectric materials for the p-channel (pull-up transistor) and n-channel (pull-down transistor) OFETs, respectively. The PS dielectric polymer was selectively etched by inkjetting of n-butyl acetate as an orthogonal solvent for P(NDI2OD-T2). Employing this methodology, the five-stage ambipolar ROs with P(NDI2OD-T2) exhibited an oscillation frequency of ∼16.7 kHz, which was much higher than that of non-soft-etched ROs with a single dielectric layer (P(VDF-TrFE); ∼3 kHz).