Controlled electroluminescence of n-ZnMgO/p-GaN light-emitting diodes

Effective control of room-temperature electroluminescence of n-ZnMgO/p-GaN light-emitting diodes (LEDs) over both emission intensity and wavelength is demonstrated. With varied Mg concentration, the intensity of LEDs in the near-ultraviolet region is increased due to the effective radiative recombination in the ZnMgO layer. Furthermore, the emission wavelength is shifted to the green/yellow spectral region by employing an indium-tin-oxide thin film as the dopant source, where thermally activated indium diffusion creates extra deep defect levels for carrier recombination. These results clearly demonstrate the effectiveness of controlled metal incorporation in achieving high energy efficiency and spectral tunability of the n-ZnMgO/p-GaN LED devices.

Mechanisms of mono- and poly-ubiquitination : ubiquitination specificity depends on compatibility between the E2 catalytic core and amino acid residues proximal to the lysine

Ubiquitination involves the attachment of ubiquitin to lysine residues on substrate proteins or itself, which can result in protein monoubiquitination or polyubiquitination. Ubiquitin attachment to different lysine residues can generate diverse substrate-ubiquitin structures, targeting proteins to different fates. The mechanisms of lysine selection are not well understood. Ubiquitination by the largest group of E3 ligases, the RING-family E3 s, is catalyzed through co-operation between the non-catalytic ubiquitin-ligase (E3) and the ubiquitin-conjugating enzyme (E2), where the RING E3 binds the substrate and the E2 catalyzes ubiquitin transfer. Previous studies suggest that ubiquitination sites are selected by E3-mediated positioning of the lysine toward the E2 active site. Ultimately, at a catalytic level, ubiquitination of lysine residues within the substrate or ubiquitin occurs by nucleophilic attack of the lysine residue on the thioester bond linking the E2 catalytic cysteine to ubiquitin. One of the best studied RING E3/ E2 complexes is the Skp1/Cul1/F box protein complex, SCFCdc4, and its cognate E2, Cdc34, which target the CDK inhibitor Sic1 for K48-linked polyubiquitination, leading to its proteasomal degradation. Our recent studies of this model system demonstrated that residues surrounding Sic1 lysines or lysine 48 in ubiquitin are critical for ubiquitination. This sequence-dependence is linked to evolutionarily conserved key residues in the catalytic region of Cdc34 and can determine if Sic1 is mono- or poly-ubiquitinated. Our studies indicate that amino acid determinants in the Cdc34 catalytic region and their compatibility to those surrounding acceptor lysine residues play important roles in lysine selection. This may represent a general mechanism in directing the mode of ubiquitination in E2 s.

Yhh1p/Cft1p directly links poly(A) site recognition and RNA polymerase II transcription termination

RNA polymerase II (pol II) transcription termination requires co‐transcriptional recognition of a functional polyadenylation signal, but the molecular mechanisms that transduce this signal to pol II remain unclear. We show that Yhh1p/Cft1p, the yeast homologue of the mammalian AAUAAA interacting protein CPSF 160, is an RNA‐binding protein and provide evidence that it participates in poly(A) site recognition. Interestingly, RNA binding is mediated by a central domain composed of predicted β‐propeller‐forming repeats, which occurs in proteins of diverse cellular functions. We also found that Yhh1p/Cft1p bound specifically to the phosphorylated C‐terminal domain (CTD) of pol II in vitro and in a two‐hybrid test in vivo. Furthermore, transcriptional run‐on analysis demonstrated that yhh1 mutants were defective in transcription termination, suggesting that Yhh1p/Cft1p functions in the coupling of transcription and 3′‐end formation. We propose that direct interactions of Yhh1p/Cft1p with both the RNA transcript and the CTD are required to communicate poly(A) site recognition to elongating pol II to initiate transcription termination.

Improved energy harvesting capability of poly(vinylidene fluoride) films modified by reduced graphene oxide

Piezoelectric energy harvesters can be used to convert ambient energy into electrical energy and power small autonomous devices. In recent years, massive effort has been made to improve the energy harvesting ability in piezoelectric materials. In this study, reduced graphene oxide was added into poly(vinylidene fluoride) to fabricate the piezoelectric nanocomposite films. Open-circuit voltage and electrical power harvesting experiments showed remarkable enhancement in the piezoelectricity of the fabricated poly(vinylidene fluoride)/reduced graphene oxide nanocomposite, especially at an optimal reduced graphene oxide content of 0.05 wt%. Compared to pristine poly(vinylidene fluoride) films, the open-circuit voltage, the density of harvested power of alternating current, and direct current of the poly(vinylidene fluoride)/reduced graphene oxide nanocomposite films increased by 105%, 153%, and 233%, respectively, indicating a great potential for a broad range of applications.

Photophysical characterization of light-emitting poly(indenofluorene)s

Time-resolved photoluminescence spectroscopy experiments of three poly(2,8-indenofluorene) derivatives bearing different pendant groups are presented. A comparison of the photophysical properties of dilute solutions and thin films provides information on the chemical purity of the materials. The photophysical properties of poly(2,8-indenofluorene)s are correlated with the morphological characteristics of their corresponding films. Wide-angle X-ray scattering experiments reveal the order in these materials at the molecular level. The spectroscopic results confirm the positive impact of a new synthetic approach on the spectral purity of the poly(indenofluorene)s. It is concluded that complete side-chain substitution of the bridgehead carbon atoms C-6 and C-12 in the indenofluorene unit, prior to indenofluorene ring formation, reduces the probability of keto formation. Due to the intrinsic chemical purity of the arylated derivative, identification of a long-delayed spectral feature, other than the known keto band, is possible in the case of thin films. Controlled doping experiments on the arylated derivative with trace amounts of an indenofluorene-monoketone provide quantitative information on the rates of two major photophysical processes, namely, singlet photoluminescence emission and singlet photoluminescence quenching. These results allow the determination of the minimum keto concentration that can affect the intrinsic photophysical properties of this polymer. The data suggest that photoluminescence quenching operates in the doped films according to the Stern-Volmer formalism.

A high mobility P-type DPP-thieno[3,2-b]thiophene copolymer for organic thin-film transistors

A copolymer comprising 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) and thieno[3,2-b]thiophene moieties, PDBT-co-TT, shows high hole mobility of up to 0.94 cm2 V-1 s-1 in organic thin-film transistors. The strong intermolecular interactions originated from π-π stacking and donor-acceptor interaction lead to the formation of interconnected polymer networks having an ordered lamellar structure, which have established highly efficient pathways for charge carrier transport.

A furan-containing conjugated polymer for high mobility ambipolar organic thin film transistors

Furan substituted diketopyrrolopyrrole (DBF) combined with benzothiadiazole based polymer semiconductor PDPP-FBF has been synthesized and evaluated as an ambipolar semiconductor in organic thin-film transistors. Hole and electron mobilities as high as 0.20 cm 2 V -1 s -1 and 0.56 cm 2 V -1 s -1, respectively, are achieved for PDPP-FBF.

Solution processable low bandgap diketopyrrolopyrrole (DPP) based derivatives : novel acceptors for organic solar cells

Novel low bandgap solution processable diketopyrrolopyrrole (DPP) based derivatives functionalized with electron withdrawing end capping groups (trifluoromethylphenyl and trifluorophenyl) were synthesized, and their photophysical, electrochemical and photovoltaic properties were investigated. These compounds showed optical bandgaps ranging from 1.81 to 1.94 eV and intense absorption bands that cover a wide range from 300 to 700 nm, attributed to charge transfer transition between electron rich phenylene-thienylene moieties and the electron withdrawing diketopyrrolopyrrole core. All of the compounds were found to be fluorescent in solution with an emission wavelength ranging from 600 to 800 nm. Cyclic voltammetry indicated reversible oxidation and reduction processes with tuning of HOMO-LUMO energy levels. Bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor with these new acceptors were used for fabrication. The best power conversion efficiencies (PCE) using 1:2 donor-acceptor by weight mixture were 1% under simulated AM 1.5 solar irradiation of 100 mW cm-2. These findings suggested that a DPP core functionalized with electron accepting end-capping groups were a promising new class of solution processable low bandgap n-type organic semiconductors for organic solar cell applications.

Furan containing diketopyrrolopyrrole copolymers : synthesis, characterization, organic field effect transistor performance and photovoltaic properties

In this work, we report design, synthesis and characterization of solution processable low band gap polymer semiconductors, poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-phenylene} (PDPP-FPF), poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene} (PDPP-FNF) and poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-anthracene} (PDPP-FAF) using the furan-containing 3,6-di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBF) building block. As DBF acts as an acceptor moiety, a series of donor-acceptor (D-A) copolymers can be generated when it is attached alternatively with phenylene, naphthalene or anthracene donor comonomer blocks. Optical and electrochemical characterization of thin films of these polymers reveals band gaps in the range of 1.55-1.64 eV. These polymers exhibit excellent hole mobility when used as the active layer in organic thin-film transistor (OTFT) devices. Among the series, the highest hole mobility of 0.11 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices using PDPP-FNF. When these polymers are used as a donor and [70]PCBM as the acceptor in organic photovoltaic (OPV) devices, power conversion efficiencies (PCE) of 2.5 and 2.6% are obtained for PDPP-FAF and PDPP-FNF polymers, respectively. Such mobility values in OTFTs and performance in OPV make furan-containing DBF a very promising block for designing new polymer semiconductors for a wide range of organic electronic applications.

Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.

Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

Furan substituted diketopyrrolopyrrole and thienylenevinylene based low band gap copolymer for high mobility organic thin film transistors

A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4- c]pyrrole-1,4-dione-alt-thienylenevinylene} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (Eoptg) calculated from the polymer film absorption onset is around 1.37 eV. The π-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 °C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10 6-10 7. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

Water-based nanoparticulate solar cells using a diketopyrrolopyrrole donor polymer

Organic photovoltaic devices with either bulk heterojunction (BHJ) or nanoparticulate (NP) active layers have been prepared from a 1:2 blend of (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) (PDPP-TNT) and the fullerene acceptor, ([6,6]-phenyl C71-butyric acid methyl ester) (PC70BM). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been used to investigate the morphology of the active layers of the two approaches. Mild thermal treatment of the NP film is required to promote initial joining of the NPs in order for the devices to function, however the NP structure is retained. Consequently, whereas gross phase segregation of the active layer occurs in the BHJ device spin cast from chloroform, the nanoparticulate approach retains control of the material domain sizes on the length scale of exciton diffusion in the materials. As a result, NP devices are found to generate more than twice the current density of BHJ devices and have a substantially greater overall efficiency. The use of aqueous nanoparticulate dispersions offers a promising approach to control the donor acceptor morphology on the nanoscale with the benefit of environmentally- friendly, solution-based fabrication. © 2014 the Owner Societies.

Nanoscale phase domain structure and associated device performance of organic solar cells based on a diketopyrrolopyrrole polymer

We investigate the blend morphology and performance of bulk heterojunction organic photovoltaic devices comprising the donor polymer, pDPP-TNT (poly{3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene}) and the fullerene acceptor, [70]PCBM ([6,6]-phenyl C71-butyric acid methyl ester). The blend morphology is heavily dependent upon the solvent system used in the fabrication of thin films. Thin films spin-coated from chloroform possess a cobblestone-like morphology, consisting of thick, round-shaped [70]PCBM-rich mounds separated by thin polymer-rich valleys. The size of the [70]PCBM domains is found to depend on the overall film thickness. Thin films spin-coated from a chloroform:dichlorobenzene mixed solvent system are smooth and consist of a network of pDPP-TNT nanofibers embedded in a [70]PCBM-rich matrix. Rinsing the films in hexane selectively removes [70]PCBM and allows for analysis of domain size and purity. It also provides a means for investigating exciton dissociation efficiency through relative photoluminescence yield measurements. Devices fabricated from chloroform solutions show much poorer performance than the devices fabricated from the mixed solvent system; this disparity in performance is seen to be more pronounced with increasing film thickness. The primary cause for the improved performance of devices fabricated from mixed solvents is attributed to the greater donor-acceptor interfacial area and resulting greater capacity for charge carrier generation.