Effects of Substituting Polyisoprenyl Carbanions for Ethoxyl Groups of Bis-[3-(triethoxysilyl)propyl] Tetrasulfide on the Properties of Carbon Black and Silica-Reinforced NR/SSBR.

The coupling agent TESPT (bis-[3-(triethoxysilyl)propyl] tetrasulfide) was modified by substituting polyisoprenyl (PI) carbanions for the ethoxyl groups on silicon for increasing the interaction of rubber with its fillers. The modification was carried out by the reaction of TESPT with polyisoprenyllithium, which had been previously prepared by anionic polymerization of isoprene using butyllithium. The success of the substitution was confirmed by Fourier-transform infrared spectroscopy, and the molecular weight of the modified TESPT (PI-TESPT) was determined from gel permeation chromatography measurements. The effects of tethered PI, as well as of its chain length, on the mechanical and dynamic properties of rubber compounds were examined using a universal testing machine and dynamic mechanical analysis (DMA). In rubber sample preparation, the amount of PI3-TESPT (PI of 2900 g/mol) used in rubber compounding is equal to that of the reference sample with TESPT (S TESPT). For S PI-TESPT samples, the amounts of PI6-TESPT (PI of 5500 g/mol) and PI14-TESPT (PI of 13,700 g/mol) used were calculated as molar ethoxyl groups which are nearly equivalent to those of PI3-TESPT. At the same wt % (parts per hundred, phr) of elemental sulfur in rubber compounds, despite the order of cross-linking density being S TESPT (sample prepared with TESPT) > S PI3-TESPT > S PI6-TESPT > S PI14-TESPT, the exhibited tensile strength is of the order of S PI3-TESPT > S PI6-TESPT > S TESPT ≈ S PI14-TESPT. The better mechanical properties of S PI3-TESPT, as opposed to those of S TESPT, could be attributed to the extra reinforcement from the PI-rubber chain linkage and better silica dispersion, as suggested by the mixing torque and Payne effect (ΔG') measurements. While the dynamic properties of S PI3-TESPT are inferior to those of S TESPT, these properties can be improved by adding more elemental sulfur to increase the cross-linking density.

Enhanced Performance of Organic Thin Film Transistor Devices Using Hydroxyethyl-Terminated P3HT as the Active Layer.

Hydroxyethyl-terminated poly(3-hexylthiophene) (P3HT-OH) have been synthesized via a catalyst-transfer polycondensation using Grignard metathesis mediated by a nickel-based catalyst. This hydrophilic P3HT-OH is compared against the hydrophobic P3HT when used as an active layer on silicon dioxide (SiO2) wafer for organic thin-film-transistor (OTFT) fabrication. Hydroxyl groups at a 7.5% weight content lead to more chain regularity when polymer is bonded to SiO2 wafer surface and thus enhance the performance of OTFT Device, such as an 114.2% increase in ON/OFF ratio, an 12.4% increase in mobility, a 23.3% decrease in threshold voltage and a 30.1% decrease in surface roughness. Analysis and measurements reported in this paper have illustrated for the first time the feasibility of imparting hydrophilicity to the active layer for improving the OTFT performance.

Synthesis and Evaluation of Self-Assembled Azido Monolayer as a Novel Dielectric Layer for Fabricating Pentacene-Based Organic Thin Film Transistors.

Self-assembled 3-azidopropyltriethoxysilane monolayer (SAM) is used as a dielectric layer to modify the interface between the silicon dioxide wafer and the pentacene semiconductor layer in an organic thin film transistor (OTFT), Au/pentacene/3-azidopropyltriethoxysilane/SiO2/Si. Compared to the commonly used alkyl siliane C18 dielectric, 3-azidopropyltriethoxysilane which possesses stable formal charges is far more effective in increasing the ON/OFF ratio of OTFT device with an improvement of nearly three orders of magnitude. Analysis and measurements reported in this paper have illustrated for the first time the improvement of OTFT performance by a SAM compound with stable formal charges.

Indium droplet formation in InGaN thin films with single and double heterojunctions prepared by MOCVD.

Indium gallium nitride (InGaN) samples with single heterojunction (SH) and double heterojunction (DH) were prepared using metal-organic chemical vapor deposition. SH has a layer of InGaN thin film (thicknesses, 25, 50, 100, and 200 nm) grown on an uGaN film (thickness, 2 µm). The DH samples are distinguished by DH uGaN film (thickness, 120 nm) grown on the InGaN layer. Reciprocal space mapping measurements reveal that the DH samples are fully strained with different thicknesses, whereas the strain in the SH samples are significantly relaxed with the increasing thickness of the InGaN film. Scanning electron microscopy results show that the surface roughness of the sample increases when the sample is relaxed. High-resolution transmission electron microscopy images of the structure of indium droplets in the DH sample indicate that the thickness of the InGaN layer decreases with the density of indium droplets. The formation of these droplets is attributed to the insufficient kinetic energy of indium atom to react with the elements of group V, resulting to aggregation. The gallium atoms in the GaN thin film will not be uniformly replaced by indium atoms; the InGaN thin film has an uneven distribution of indium atoms and the quality of the epitaxial layer is degraded.

Organic thin-film-transistor Au/poly(3-hexylthiophene)/ (bilayer dielectrics)/Si having carbon nanotubes chemically bonded to poly(3-hexylthiophene) in the active layer.

Using poly(3-hexylthiophene) (P3HT) covalently bonded with carbon nanotubes (CNT) as an active layer in a bottom-gate/top contact, Au/(P3HT)/(bilayer dielectric)/Si OTFT device has resulted in an enhanced charge transport. The CNTs were firstly functionalized via ligand exchange with ferrocene, next lithiated by sec-butyllithium (s-BuLi) and then linked anionically with P3HT which has been synthesized via the modified Grignard metathesis method. Compared to the pristine P3HT, the CNTs-containing P3HT composite material has a higher energy level of HOMO and a smaller electrochemical bandgap E(g)(chem). The smaller bandgap enhances the charge carrier transport and the higher HOMO energy level indicates a reduced barrier and an increased injection rate for charge carriers at the source contact. Furthermore, the threshold voltage V(T) of CNTs-containing P3HT samples is lower and its saturation current I(D) and the the field-effect mobility are higher. An OTFT device fabricated with such a composite sample containing 1.16% CNTs has a carrier mobility and saturation current three to five times higher than pristine P3HT.

Synthesis and optoelectronic properties of nanocomposites comprising of poly(9,9-dioctylfluorene)-block-poly(3-hexylthiophene) block copolymer and graphene nanosheets.

A novel conjugated block copolymer, poly(9,9-dioctylfluorene)-block-poly(3-hexylthiophene) (PFBPT) and its nanocomposite containing graphene sheets were synthesized for enhancing optoelectronic performance. Graphene sheets were in-situ formed in the polymer matrix via a reduction of octadecylamine-functionalized graphite oxide, where the graphite oxide came from acidification and exfoliation of graphite. The blue-green light-emitting poly(9,9-dioctylfluorene) block and red-orange light-emitting poly(3-hexylthiophene) block exhibit a combined white electroluminescence when the composite materials were fabricated as the emitting layer of a polymeric light-emitting diode (PLED). Graphene does not alter the optical characteristics wavelength of PFBPT but electric conductivity increases with the amount of graphene. The HOMO and LUMO were measured and the band gap is smaller with existence of graphene. The threshold voltage decreases with an increase in the graphene content. The device fabricated with PFBPT/graphene nanocomposite containing 1% graphene has a maximum white-light luminescence at a voltage of 9.0 V.

Enhanced performance of Au/P3HT/ (bilayer dielectrics)/Si thin-film-transistor having gold nanoparticles chemically bonded to P3HT.

The charge transport enhancement of using poly(3-hexylthiophene) covalently bonded with gold nanoparticles as an active layer in a bottom-gate/top contact, Au/(P3HT)/(bilayer dielectric)/Si OTFT device has been studied. P3HT was synthesized via the modified Grignard metathesis method and functionalized to have a thiol terminal (P3HT(SH)). Gold nanoparticles (AuNPs) with sizes ranging from 2 to 10 nm were then formed via a reduction of HAuCl4 in the presence of P3HT(SH). Compared to the pristine P3HT, the AuNPs-containing P3HT composite materials have a higher energy level of HOMO and a smaller electrochemical bandgap E(g)chem. The smaller bandgap enhances the charge carrier mobility and the higher HOMO energy level indicates a reduced barrier and an increased injection rate for charge carrier at the source contact. Furthermore, the threshold voltage V(T) of AuNPs-containing P3HT samples remain nearly unchanged and their saturation current I(D) and the field-effect mobility are higher. An OTFT device fabricated with a composite sample containing 1.30% AuNPs has a carrier mobility and saturation current nearly two time higher than pristine P3HT.

Enhanced performance of P3HT/TiO2 bilayer heterojunction photovoltaic device having gold nanoparticles in the donor layer.

The photovoltaic effects of blending gold nanoparticles (AuNPs) into the donor layer of a poly(3-hexylthiophene) (P3HT)/TiO2 bilayer heterojunction device have been studied. P3HT was synthesized via the modified Gragnard metathesis method and AuNPs with sizes ranging from 12 to 15 nm were formed via a reduction of HAuCl4. The blending of AuNPs into P3HT caused a lower photoluminescence (PL) intensities and a decreased energy level of the highest occupied molecular orbital (HOMO) than the pristine P3HT owing to the good electron-accepting nature of AuNPs. Upon the use of P3HT-AuNPs as the donor layer, the decreased HOMO(donor) resulted in an increased open circuit voltage (V(OC)) and thus enabled the fabricated (P3HT-AuNPs)/TiO2 bilayer heterojunction photovoltaic device to have an improved power conversion efficiency of solar energy. V(OC) as well as the overall power conversion efficiency increased with an increase in the AuNP content as a result of additional interfaces which facilitated the charge separation of excitons and percolation pathways which enhanced the electron transfer to the TiO2 acceptor. Furthermore, unannealed P3HT-AuNPs exhibited nanoholes and provided photovoltaic devices a power conversion efficiency nearly two time higher than annealed P3HT-AuNPs.

Poly(9,9-dioctylfluorene-alt-thiophene)/graphene nanocomposite: effects of graphene on optoelectronic characteristics.

Nanocomposite comprising Poly(9,9-dioctylfluorene-alt-thiophene) (PDOFT) and graphene sheets was synthesized for the purpose of investigating its enhanced optoelectronic performance caused by the graphene. UV/Vis and photoluminescence spectra of PDOFT/graphene nanocomposite show that the existence of graphene does not alter the optical characteristics wavelength of PDOFT, and both solution samples and thin films emit green light. Meanwhile, the insignificant change in PL quantum efficiency indicates that graphene does not have significant effects on the transfer of excitation energy, the occurrence of self-quenching and the formation of excimer. However, the electric conductivity increases with an increase in the amount of graphene. The ionization potential(HOMO) and the electron affinity(LUMO) measured from the cyclic voltammetry lead to the determination of the optical band gap (Eg(chem)). When used to fabricate an optoelectronic device, the threshold voltage decreases with an increase in the graphene content until an excessive amount of graphene causes an unbalance on the electron and hole mobilities. The device fabricated with PDOFT/graphene with a 5% graphene content has a maximum luminescence of 5908 cd/m2 at a voltage of 9.5 V. The corresponding power efficiency at this maximum luminescence is 0.38 cd/A which is much higher than the device fabricated with pristine PDOFT. From the Admittance spectroscopy of the device, the electron mobility has been proved to increase with the graphene content.

Morphological and optoelectronic characteristics of nanocomposites comprising graphene nanosheets and poly(3-hexylthiophene).

P3HT/graphene nanocomposite was prepared via in-situ reduction of exfoliated graphite oxide in the P3HT polymer matrix, where the exfoliated graphite oxide was formed beforehand via the oxidation of graphite via the Hummers method. The oxidation reaction not only imparts functional groups, such as C=O, C-OH, and C-O-C, to graphite but also causes exfoliation of the resulting graphite oxide. The functional groups render graphite oxide an additional, lower thermal degradation temperature (T(d)) and the exfoliation shifts the XRD pattern towards a much smaller angle. The oxidation of graphite into graphite oxide creates a pleated flaking morphology for graphite oxide as opposed to that of graphite. UV/Vis and photoluminescence (PL) spectra of P3HT/graphene nanocomposite indicate that the existence of graphene does not alter the UV/Vis and PL excitation characteristics of P3HT, and the P3HT/graphene composite has higher electron mobility, a smaller band gap and higher conductivity than the pristine P3HT.

Thermal and spectroscopic properties of polystyrene/gold nanocomposite containing well-dispersed gold nanoparticles.

The thermal and spectroscopic properties of polystyrene/(gold particles) (PS(SH)/Au) nanocomposite materials containing uniformly dispersed nanoparticles in a polymer matrix have been studied. The nanocomposite comprises the thiol-terminated polystyrene (PS(SH)) which was produced by capping a living polystyrene with ethylene sulfide and the nano-sized gold particles (AuNPs) which were in-situ formed in the presence of PS(SH). The PS(SH) was characterized by NMR and the bonding between thiols and AuNPs was verified by X-ray Photoelectron Spectroscopy. Based on the transmission electron microscopy and the UV-vis absorption spectra, PS(SH) with a lower molecular weight leads to the formation of bigger AuNPs. The T(D) of the nanocomposite (PS(SH)/Au) increases with an increase in the Au content and at a constant Au content the PS(SH) with a higher molecular weight affords PS(SH)/Au a higher T(D). While PS(SH)/Au has a higher T(g) than the corresponding pristine PS(SH), the difference reduces with an increase in Au content (i.e., a decrease in the PS(SH):Au weight ratio) because of the formation of larger AuNPs which provide a smaller total surface area for PS(SH) to anchor or to cover.

Application of gold nanoparticles to microencapsulation of thioridazine.

Thioridazine-containing ethyl cellulose (EC) microcapsules were prepared in the presence of gold nanoparticles via the W/O/W emulsification solvent-evaporation method. The gold nanoparticles have been verified as human safe and the nondestructive physisorption of thioridazine on gold nanoparticles was corroborated with the time-of-flight second ion mass spectrometry measurements. The morphology of the formed microcapsules (ETA, containing EC, Thioridazine and Au) changed substantially because of the presence of gold nanoparticles. In addition to a prolonged controlled release, these ETA microcapsules had an enhanced thioridazine encapsulation with an efficiency over one and half times that of the microcapsules (ET) containing no nanogold particles. While data of the release kinetics for ET microcapsules fitted the apparent first-order model, corresponding data for ETA microcapsules agreed better with the Higuchi model indicating a uniform distribution of thioridazine in the monolithic-type microcapsules.