Formation of Large Crystalline Domains in a Semiconducting Polymer with Semi-fluorinated Alkyl Side Chains and Application to High-Performance Thin-Film Transistors.

The semi-fluorinated alkyl (SFA) side chain introduced thienylenevinylene (TV)-based p-type polymer, PC12TVC5F7T, was synthesized for use in organic thin-film transistors (OTFTs). Herein, we investigated the influence of SFA side chains on the morphology, molecular orientation, and crystalline structure using a combination of atomic force microscopy (AFM), scanning electron microscopy (SEM), two-dimensional (2D) grazing-incidence wide-angle X-ray scattering (GIWAXS), and density functional theory (DFT) calculations. Interestingly, the incorporation of SFA side chains led to the evolution of plate-like large-sized domains and also strongly intermolecular stacked high crystalline structures. Furthermore, due to the strong interactions between SFA side chains, several (00h) peaks could be observed for PC12TVC5F7T, in spite of their fairly large dihedral angle. As a result, due to the well-developed microstructure of PC12TVC5F7T, the OTFT devices based on it exhibited a high hole mobility of 1.91 cm2 V-1 s-1, which is an outstanding value among the poly(thiophene) derivative polymers. These observations indicate that large-sized domains and strongly intermolecular stacked high crystalline structures, which are beneficial for charge carrier transport, could be attained by the introduction of SFA side chains, further enhancing the performance of the OTFTs.

Orthogonal Printable Reduced Graphene Oxide 2D Materials as Hole Transport Layers for High-Performance Inverted Polymer Solar Cells: Sheet Size Effect on Photovoltaic Properties.

Creating an orthogonal printable hole-transporting layer (HTL) without damaging the underlying layer is still a major challenge in fabricating large-area printed inverted polymer solar cells (PSCs). In this study, we prepared orthogonal-processable fluorine-functionalized reduced graphene oxide (FrGO) series with various two-dimensional sheet sizes such as large-sized FrGO (1.1 µm), medium-sized FrGO (0.7 µm), and small-sized FrGO (0.3 µm) and systematically investigated the size effect of FrGOs on the hole transport properties of PSCs. The FrGOs exhibit highly stable dispersion without change over 90 days in 2-propanol solvent, indicating very high dispersion stability. Decreasing the sheet size of FrGOs enhanced hole-transporting properties, resulting in power conversion efficiencies (PCEs) of 9.27 and 9.02% for PTB7-Th:EH-IDTBR- and PTB7-Th:PC71BM-based PSCs, respectively. Compared to devices with solution-processed poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), a 14% enhancement of PCEs was achieved. Interestingly, the PCEs of devices with the smallest FrGO sheet are higher than the PCE of 8.77% of a device with vacuum-deposited MoO3. The enhancement in the performance of PSCs is attributed to the enhanced charge collection efficiency, decreased leakage current, internal resistance, and minimized charge recombination. Finally, small-sized FrGO HTLs were successfully coated on the photoactive layer using the spray coating method, and they also exhibited PCEs of 9.22 and 13.26% for PTB7-Th:EH-IDTBR- and PM6:Y6-based inverted PSCs, respectively.

In Situ Self-Formed Nanosheet MoS3/Reduced Graphene Oxide Material Showing Superior Performance as a Lithium-Ion Battery Cathode.

Although lithium-sulfur (Li-S) batteries have 5-10 times higher theoretical capacity (1675 mAh g-1) than present commercial lithium-ion batteries, Li-S batteries show a rapid and continuous capacity fading due to the polysulfide dissolution in common electrolytes. Here, we propose the use of a sulfur-based cathode material, amorphous MoS3 and reduced graphene oxide (r-GO) composite, which can be substituted for the pure sulfur-based cathodes. In order to enhance kinetics and stability of the electrodes, we intentionally pulverize the microsized MoS3 sheet into nanosheets and form an ultrathin nano-SEI on the surface using in situ electrochemical methods. Then, the pulverized nanosheets are securely anchored by the oxygen functional group of r-GO. As a result, the electrochemically treated MoS3/r-GO electrode shows superior performance that surpasses pure sulfur-based electrodes; it exhibits a capacity of about 900 mAh g-1 at a rate of 5C for 2500 cycles without capacity fading. Moreover, a full-cell battery employing the MoS3/r-GO cathode with a silicon-carbon composite anode displays a 3-5 times higher energy density (1725 Wh kg-1/7100 Wh L-1) than present LIBs.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution.

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (-157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution.

Diketopyrrolopyrrole-Based Metallated Polymer for Bulk-Heterojunction Solar Cells and Organic Field-Effect Transistors.

We report the synthesis and optoelectronic properties of novel platinum-based polymers (p-Pt-DPP) incorporating 3,6-di-2-thienyl-2,5-dihydro-2,5-diethylhexylpyrrolo[3,4-c]pyrrole-1,4-dione. The synthesized amorphous metallated polymer exhibited long wavelength absorption in the range of 500­684 nm and a band-gap as low as 1.75 eV. Organic field-effect transistors (OFETs) fabricated from p-Pt-DPP showed hole mobility of 1.6 × 10⁻³ cm² · V⁻¹s⁻¹ and an on/off ratio of 5 × 104. In addition, polymer solar cells (PSCs) based on p-Pt-DPP and PC71BM exhibited a photovoltaic efficiency of 1.22% under AM 1.5 G conditions with an illumination of 100 mW·cm−2 without any annealing process.

Planar heterojunction perovskite solar cells with superior reproducibility.

Perovskite solar cells (PeSCs) have been considered one of the competitive next generation power sources. To date, light-to-electric conversion efficiencies have rapidly increased to over 10%, and further improvements are expected. However, the poor device reproducibility of PeSCs ascribed to their inhomogeneously covered film morphology has hindered their practical application. Here, we demonstrate high-performance PeSCs with superior reproducibility by introducing small amounts of N-cyclohexyl-2-pyrrolidone (CHP) as a morphology controller into N,N-dimethylformamide (DMF). As a result, highly homogeneous film morphology, similar to that achieved by vacuum-deposition methods, as well as a high PCE of 10% and an extremely small performance deviation within 0.14% were achieved. This study represents a method for realizing efficient and reproducible planar heterojunction (PHJ) PeSCs through morphology control, taking a major step forward in the low-cost and rapid production of PeSCs by solving one of the biggest problems of PHJ perovskite photovoltaic technology through a facile method.

An approach for an advanced anode interfacial layer with electron-blocking ability to achieve high-efficiency organic photovoltaics.

The interfacial properties of PEDOT:PSS, pristine r-GO, and r-GO with sulfonic acid (SR-GO) in organic photovoltaic are investigated to elucidate electron-blocking property of PEDOT:PSS anode interfacial layer (AIL), and to explore the possibility of r-GO as electron-blocking layers. The SR-GO results in an optimized power conversion efficiency of 7.54% for PTB7-th:PC71BM and 5.64% for P3HT:IC61BA systems. By combining analyses of capacitance-voltage and photovoltaic-parameters dependence on light intensity, it is found that recombination process at SR-GO/active film is minimized. In contrast, the devices using r-GO without sulfonic acid show trap-assisted recombination. The enhanced electron-blocking properties in PEDOT:PSS and SR-GO AILs can be attributed to surface dipoles at AIL/acceptor. Thus, for electron-blocking, the AIL/acceptor interface should be importantly considered in OPVs. Also, by simply introducing sulfonic acid unit on r-GO, excellent contact selectivity can be realized in OPVs.

Stable charge storing in two-dimensional MoS2 nanoflake floating gates for multilevel organic flash memory.

In this study, we investigated chemically exfoliated two-dimensional (2-D) nanoflakes of molybdenum disulfide (MoS2) as charge-storing elements for use in organic multilevel memory devices (of the printed/flexible non-volatile type) based on organic field-effect transistors (OFETs) containing poly(3-hexylthiophene) (P3HT). The metallic MoS2 nanoflakes were exfoliated in 2-methoxyethanol by the lithium intercalation method and were deposited as nano-floating gates between polystyrene and poly(methyl methacrylate), used as bilayered gate dielectrics, by a simple spin-coating and low temperature (<150 °C) process. In the developed OFET memory devices, electrons could be trapped/detrapped in the MoS2 nano-floating gates by modulating the charge carrier density in the active channel through gate bias control. Optimal memory characteristics were achieved by controlling the thickness and concentration of few-layered MoS2 nanoflakes, and the best device showed reliable non-volatile memory properties: a sufficient memory window of ∼23 V, programming-reading-erasing cycling endurance of >10(2) times, and most importantly, quasi-permanent charge-storing characteristics, i.e., a very long retention time (longer than the technological requirement of commercial memory devices (>10 years)). In addition, we successfully developed multilevel memory cells (2 bits per cell) by controlling the gate bias magnitude.

Fluorine-functionalized and simultaneously reduced graphene oxide as a novel hole transporting layer for highly efficient and stable organic photovoltaic cells.

A one-step reduction and functionalization of graphene oxide (FrGO) was easily achieved using a novel phenylhydrazine-based reductant containing fluorine atoms, which can induce p-type doping due to its high electronegativity. The FrGO-based OPV exhibited a high power conversion efficiency of ∼6.71% and a superior OPV-stability to commercial PEDOT:PSS.

A novel thermally reversible soluble-insoluble conjugated polymer with semi-fluorinated alkyl chains: enhanced transistor performance by fluorophobic self-organization and orthogonal hydrophobic patterning.

SFA-PQT exhibits self-assembly via a fluorophobic effect in a non-fluorous solvent, which leads to an enhanced electrical performance. Ambipolar transistors and inverters with p- and n- type bilayers are enabled by the unique thermally reversible soluble-insoluble properties of SFA-PQT. More importantly, the hydrophobicity of SFA-PQT facilitates orthogonal hydrophobic patterning and a patterned inverter exhibits low voltage dissipation, a narrow transition zone, a high gain value, and negligible hysteresis.

Significant vertical phase separation in solvent-vapor-annealed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composite films leading to better conductivity and work function for high-performance indium tin oxide-free optoelectronics.

In the present study, a novel polar-solvent vapor annealing (PSVA) was used to induce a significant structural rearrangement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films in order to improve their electrical conductivity and work function. The effects of polar-solvent vapor annealing on PEDOT:PSS were systematically compared with those of a conventional solvent additive method (SAM) and investigated in detail by analyzing the changes in conductivity, morphology, top and bottom surface composition, conformational PEDOT chains, and work function. The results confirmed that PSVA induces significant phase separation between excess PSS and PEDOT chains and a spontaneous formation of a highly enriched PSS layer on the top surface of the PEDOT:PSS polymer blend, which in turn leads to better 3-dimensional connections between the conducting PEDOT chains and higher work function. The resultant PSVA-treated PEDOT:PSS anode films exhibited a significantly enhanced conductivity of up to 1057 S cm(-1) and a tunable high work function of up to 5.35 eV. The PSVA-treated PEDOT:PSS films were employed as transparent anodes in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs). The cell performances of organic optoelectronic devices with the PSVA-treated PEDOT:PSS anodes were further improved due to the significant vertical phase separation and the self-organized PSS top surface in PSVA-treated PEDOT:PSS films, which can increase the anode conductivity and work function and allow the direct formation of a functional buffer layer between the active layer and the polymeric electrode. The results of the present study will allow better use and understanding of polymeric-blend materials and will further advance the realization of high-performance indium tin oxide (ITO)-free organic electronics.