Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination.

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl2-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl- counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl- counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.

Molecular Dynamics and Structure of Poly(Methyl Methacrylate) Chains Grafted from Barium Titanate Nanoparticles.

Core-shell nanocomposites comprising barium titanate, BaTiO3 (BTO), and poly(methyl methacrylate) (PMMA) chains grafted from its surface with varied grafting densities were prepared. BTO nanocrystals are high-k inorganic materials, and the obtained nanocomposites exhibit enhanced dielectric permittivity, as compared to neat PMMA, and a relatively low level of loss tangent in a wide range of frequencies. The impact of the molecular dynamics, structure, and interactions of the BTO surface on the polymer chains was investigated. The nanocomposites were characterized by broadband dielectric and vibrational spectroscopies (IR and Raman), transmission electron microscopy, differential scanning calorimetry, and nuclear magnetic resonance. The presence of ceramic nanoparticles in core-shell composites slowed down the segmental dynamic of PMMA chains, increased glass transition temperature, and concurrently increased the thermal stability of the organic part. It was also evidenced that, in addition to segmental dynamics, local ß relaxation was affected. The grafting density influenced the self-organization and interactions within the PMMA phase, affecting the organization on a smaller size scale of polymeric chains. This was explained by the interaction of the exposed surface of nanoparticles with polymer chains.

Effect of ß-Ketoiminato Ancillary Ligand Modification on Emissive Properties of New Iridium Complexes.

A series of new bis(benzo[h]quinolinato) Ir(III) complexes with modified ß-ketoiminato ancillary ligands were synthesized, and their electrochemical, photophysical properties were determined with the support of theoretical calculations. Moreover, all the synthesized heteroleptic Ir(III) complexes were examined as dopants of the host-guest type emissive layers in solution-processed phosphorescent organic light emitting diodes (PhOLEDs) of a simple structure. As expected on the basis of voltammetry measurements as well as DFT calculations, all the compounds appeared to be green emitters. Their examination showed that alteration of ß-ketoiminato ligand structure causes frontier orbitals' energy levels to be slightly changed, while significantly affecting photoluminescence and electroluminescence efficiencies of iridium phosphors containing these ligands. It was also found that modification of ancillary ligands might enhance charge trapping on the dopant, thus increasing its efficiency, especially in electroluminescence. From among the iridium complexes studied, the compound bearing 1-naphthyl group bonded to the nitrogen atom of the ancillary ligand proved to be the most efficient emitter. The PhOLED fabricated on the basis of this dopant has reached a luminance level of 16000 cd/m2, current efficiency close to 12 cd/A, and an external quantum efficiency around 3.2%.

Microstructure-Dependent Charge Carrier Transport of Poly(3-hexylthiophene) Ultrathin Films with Different Thicknesses.

Since the interfacial order of conjugated polymers plays an essential role for the performance of field-effect transistors, comprehensive understanding on the charge carrier transport in ultrathin semiconducting films below thicknesses of 10 nm is required for the development of transparent and flexible organic electronics. In this study, ultrathin films based on poly(3-hexylthiophene) as conjugated polymer model system with a thickness range from single monolayer up to several multilayers are investigated in terms of microstructure evolution and electrical properties of different molecular weights. Interestingly, a characteristic leap in field-effect mobility is observed for films with thickness greater than four layers. This threshold mobility regarding film thickness is attributed to the transition from 2D to 3D charge carrier transport along with an increased size of the P3HT aggregates in the upper layers of the film. These results disclose key aspects on the role of the film interlayer on the charge carrier transport through conjugated polymers in transistors.

Bottlebrush Polymers for Articular Joint Lubrication: Influence of Anchoring Group Chemistry on Lubrication Properties.

The role of carboxylic, aldehyde, or epoxide groups incorporated into bottlebrush macromolecules as anchoring blocks (or cartilage-binding blocks) is investigated by measuring their lubricating properties and cartilage-binding effectiveness. Mica modified with amine groups is used to mimic the cartilage surface, while bottlebrush polymers functionalized with carboxylic, aldehyde, or epoxide groups played the role of the lubricant interacting with the cartilage surface. We demonstrate that bottlebrushes with anchoring blocks effectively reduce the friction coefficient on modified surfaces by 75-95% compared to unmodified mica. The most efficient polymer appears to be the one with epoxide groups, which can react spontaneously with amines at room temperature. In this case, the value of the friction coefficient is the lowest and equals 0.009 ± 0.001, representing a 95% reduction compared to measurements on nonmodified mica. These results show that the presence of the functional groups within the anchoring blocks has a significant influence on interactions between the bottlebrush polymer and cartilage surface. All synthesized bottlebrush polymers are also used in the preliminary lubrication tests carried out on animal cartilage surfaces. The developed materials are very promising for future in vivo studies to be used in osteoarthritis treatment.

Surface-enhanced Raman scattering of water in aqueous dispersions of silver nanoparticles.

The resonance Raman effect (RRE) is a phenomenon which results in a strong selective enhancement of Raman signals from the samples. Previous studies showed that the RRE in liquid water directly corresponds to its supramolecular structure. It was also reported that the electric-field-induced orientation of water molecules on the electrode surface results in the surface-enhanced Raman scattering (SERS) effect. In this work, we show the SERS effect for water molecules in the dispersion of silver nanoparticles (AgNPs) without any external electrical field. An enhancement factor was estimated to be (4.8 ± 0.8) × 106 for an excitation wavelength of 514.5 nm and for AgNPs with an average size of 34 ± 14 nm. The temperature experiment results showed a higher enhancement with temperature increase. Performed simulation studies revealed a slowdown of the mobility of the water molecules close to the surface of AgNPs.

Effects of Counter Anions on AC and DC Electrical Conductivity in Poly(Dimethylsiloxane) Crosslinked by Metal-Ligand Coordination.

There is an urgent need for the development of elastic dielectric materials for flexible organic field effect transistors (OFETs). In this work, detailed analysis of the AC and DC electrical conductivity of a series of flexible poly(dimethylsiloxane) (PDMS) polymers crosslinked by metal-ligand coordination in comparison to neat PDMS was performed for the first time by means of broadband dielectric spectroscopy. The ligand was 2,2-bipyridine-4,4-dicarboxylic amide, and Ni2+, Mn2+, and Zn2+ were introduced for Cl-, Br-, and I- salts. Introduction of metal salt and creation of coordination bonds resulted in higher permittivity values increasing in an order: neat PDMS < Ni2+ < Mn2+ < Zn2+; accompanied by conductivity values of the materials increasing in an order: neat PDMS < Cl- < I- < Br-. Conductivity relaxation time plot as a function of temperature, showed Vogel-Fulcher-Tammann dependance for the Br- salts and Arrhenius type for the Cl- and I- salts. Performed study revealed that double-edged challenge can be obtained, i.e., dielectric materials with elevated value of dielectric permittivity without deterioration too much the non-conductive nature of the polymer. This opens up new perspectives for the production of flexible dielectrics suitable for gate insulators in OFETs. Among the synthesized organometallic materials, those with chlorides salts are the most promising for such applications.

Self-Aligned Bilayers for Flexible Free-Standing Organic Field-Effect Transistors.

Free-standing and flexible field-effect transistors based on 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene)/polystyrene bilayers are obtained by well-controlled phase separation of both components. The phase separation is induced by solvent vapor annealing of initially amorphous blend films, leading to crystallization of TIPS-pentacene as the top layer. The crystallinity and blend morphology strongly depend on the molecular weight of polystyrene, and under optimized conditions, distinct phase separation with a well-defined and trap-free interface between both fractions is achieved. Due to the distinct bilayer morphology, the resulting flexible field-effect transistors reveal similar charge carrier mobilities as rigid devices and additionally pronounced environmental and bias stress stabilities. The performance of the flexible transistors remains stable up to a strain of 1.8%, while above this deformation, a close relation between current and strain is observed that is required for applications in strain sensors.

Geometry Control of Source/Drain Electrodes in Organic Field-Effect Transistors by Electrohydrodynamic Inkjet Printing.

In this work we study the influence of dielectric surface and process parameters on the geometry and electrical properties of silver electrodes obtained by electrohydrodynamic inkjet printing. The cross-section and thickness of printed silver tracks are optimized to achieve a high conductivity. Silver overprints with cross-section larger than 4 µm2 and thickness larger than 90 nm exhibit the lowest resistivity. To fabricate electrodes in the desired geometry, a sufficient volume of ink is distributed on the surface by applying appropriate voltage amplitude. Single and multilayer overprints are incorporated as bottom contacts in bottom gate organic field-effect transistors (OFETs) with a semiconducting polymer as active layer. The multilayer electrodes result in significantly higher electrical parameters than single layer contacts, confirming the importance of a careful design of the printed tracks for reliable device performance. The results provide important design guidelines for precise fabrication of electrodes in electronic devices by electrohydrodynamic inkjet printing.

Inkjet Printing of an Electron Injection Layer: New Role of Cesium Carbonate Interlayer in Polymer OLEDs.

Among solution-processable techniques, inkjet printing is a potential method for manufacturing low-cost and high-resolution polymer organic light-emitting diodes (PLEDs) for displays/solid-state lighting applications. Herein, we demonstrate use of the inkjet printed cesium carbonate (Cs2CO3) film as an electron injection interlayer. We have elaborated the Cs2CO3 ink using an alcohol-based solvent for the industrial-grade printhead. The printed Cs2CO3 layer morphology was investigated by means of an optical microscope and an atomic force microscope. The PLEDs based on emissive polymer (Super Yellow) with printed Cs2CO3 interlayer show a remarkable current efficiency and luminance compared to the PLEDs made without the Cs2CO3 layer. Such results suggest that the Cs2CO3 is a promising material for the formulation of the electron injecting inkjet inks. The possibility of inkjet printing of an efficient electron injecting layer enables in situ patterning of PLEDs' emission area. Such a simple and flexible technique can be applied for a wide range of applications such as signage, pictograms, advertising, smart packaging, etc.

Inkjet Printing of Super Yellow: Ink Formulation, Film Optimization, OLEDs Fabrication, and Transient Electroluminescence.

Inkjet printing technique allows manufacturing low cost organic light emitting diodes (OLEDs) in ambient conditions. The above approach enables upscaling of the OLEDs fabrication process which, as a result, would become faster than conventionally used vacuum based processing techniques. In this work, we use the inkjet printing technique to investigate the formation of thin active layers of well-known light emitting polymer material: Super Yellow (poly(para-phenylene vinylene) copolymer). We develop the formulation of Super Yellow ink, containing non-chlorinated solvents and allowing stable jetting. Optimization of ink composition and printing resolution were performed, until good quality films suitable for OLEDs were obtained. Fabricated OLEDs have shown a remarkable characteristics of performance, similar to the OLEDs fabricated by means of spin coating technique. We checked that, the values of mobility of the charge carriers in the printed films, measured by transient electroluminescence, are similar to the values of mobility measured in spin coated films. Our contribution provides a complete framework for inkjet printing of high quality Super Yellow films for OLEDs. The description of this method can be used to obtain efficient printed OLEDs both in academic and in industrial settings.

Slot-Die Coating of Double Polymer Layers for the Fabrication of Organic Light Emitting Diodes.

This study presents the slot-die coating process of two layers of organic materials for the fabrication of organic light emitting diodes (OLEDs). Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), which is commonly used in OLEDs and in organic photovoltaic devices as the hole injection layer (HIL), has been deposited via slot-die coating. Uniform films of PEDOT:PSS were obtained after optimizing the slot-die processing parameters: substrate temperature, coating speed, and ink flow rate. The film quality was examined using optical microscopy, profilometry, and atomic force microscopy. Further, poly(9,9-dioctylfluorene) (F8) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT), a well know polymer blend F8:F8BT, which is used as an emissive layer in OLEDs, has been slot-die coated. The optoelectronic properties of the slot-die coated F8:F8BT films were examined by means of photoluminescence (PL) and electroluminescence (EL) studies. The fabricated OLEDs, consisting of slot-die coated PEDOT:PSS and F8:F8BT films, were characterized to record the brightness and current efficiency.

Realizing 20% External Quantum Efficiency in Electroluminescence with Efficient Thermally Activated Delayed Fluorescence from an Exciplex.

The investigation of nondoped exciplex blends of 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T), working as the one-electron acceptor molecule, with different electron donors is reported. The emissions of these exciplexes span from the blue to orange-red regions, showing clear contribution from thermally activated delayed fluorescence (TADF) and delayed fluorescence originated from nongeminate recombination of charge carriers created by the dissociation of optically generated exciplexes. We focus our studies on the properties of TADF in these systems, covering in particular the physical meaning of the different transient components observed in their luminescence decays. Our results unravel the intricate role of reverse intersystem crossing due to spin-orbit coupling and possibly also due to hyperfine interactions and internal conversion, which affect the efficiency of the TADF mechanism. Remarkable performances are obtained in prototype organic light-emitting diodes fabricated with some of these blends. Green exciplex blends, in particular, exhibited the current efficiency of 60 cd A-1, power efficiency of 71 lm W-1, and external quantum efficiency of 20%. We believe that our results will contribute significantly to highlight the potential advantages of intermolecular exciplexes in the area of organic light-emitting diodes.

Raman resonance effect in liquid water.

Raman spectroscopy is a technique preferably used for studies of water structure because the proportions of intensities of main OH stretching modes are thought to reflect well a network of "intermonomer" hydrogen bonds as well as its disturbance by the presence of some solutes. The work presented herein demonstrates how the intensity ratio of two main components (around 3200 and 3400 cm (-1)) depends on the excitation wavelength in the visible range. Polarized Raman spectra indicate that the component at ca. 3200 cm (-1) is in resonance with light from the red range, which is in agreement with the presence of vibrational overtones in UV-vis absorption spectrum of water. These results are the first report on the occurrence of the Raman resonance effect in liquid water.

Nonhalogenated Solvent-Processed All-Polymer Solar Cells over 7.4% Efficiency from Quinoxaline-Based Polymers.

Two conjugated polymers, with different side chains of alkoxy-substituted difluorobenzene and alkyl-substituted difluorobenzene based on quinoxaline (Qx) as the electron acceptor unit and benzodithiophene as the electron donor unit, named HFQx-T and HFAQx-T, were used as electron donor polymers to fabricate all-polymer solar cells (all-PSCs) with a naphthalenediimide-bithiophene n-type semiconducting polymer (N2200). Usually, halogenated solvents are harmful to natural environment and human beings, and solvent additives were disadvantageous in the process of roll-to-roll technology. The Qx-based polymers are successfully used to fabricate high-performance all-PSCs, which processed with the nonhalogenated solvent tetrahydrofuran (THF) at room temperature. With THF as the processing solvent, the active layer showed a higher absorption coefficient, better phase separation, exciton dissociation, and charge carrier mobilities than that processed with CHCl3. Moreover, the photovoltaic properties have been dramatically improved with THF. The optimized device of HFAQx-T:N2200 processed with THF delivered an efficient power conversion efficiency (PCE) of 7.45%, which is the highest PCE for all-PSCs from Qx-based polymers processed by a nonhalogenated solvent.

Parylene C as a versatile dielectric material for organic field-effect transistors.

An emerging new technology, organic electronics, is approaching the stage of large-scale industrial application. This is due to a remarkable progress in synthesis of a variety of organic semiconductors, allowing one to design and to fabricate, so far on a laboratory scale, different organic electronic devices of satisfactory performance. However, a complete technology requires upgrading of fabrication procedures of all elements of electronic devices and circuits, which not only comprise active layers, but also electrodes, dielectrics, insulators, substrates and protecting/encapsulating coatings. In this review, poly(chloro-para-xylylene) known as Parylene C, which appears to become a versatile supporting material especially suitable for applications in flexible organic electronics, is presented. A synthesis and basic properties of Parylene C are described, followed by several examples of use of parylenes as substrates, dielectrics, insulators, or protecting materials in the construction of organic field-effect transistors.

Balanced Ambipolar Organic Field-Effect Transistors by Polymer Preaggregation.

Ambipolar organic field-effect transistors (OFETs) based on heterojunction active films still suffer from an imbalance in the transport of electrons and holes. This problem is related to an uncontrolled phase separation between the donor and acceptor organic semiconductors in the thin films. In this work, we have developed a concept to improve the phase separation in heterojunction transistors to enhance their ambipolar performance. This concept is based on preaggregation of the donor polymer, in this case poly(3-hexylthiophene) (P3HT), before solution mixing with the small-molecular-weight acceptor, phenyl-C61-butyric acid methyl ester (PCBM). The resulting heterojunction transistor morphology consists of self-assembled P3HT fibers embedded in a PCBM matrix, ensuring balanced mobilities reaching 0.01 cm2/V s for both holes and electrons. These are the highest mobility values reported so far for ambipolar OFETs based on P3HT/PCBM blends. Preaggregation of the conjugated polymer before fabricating binary blends can be regarded as a general concept for a wider range of semiconducting systems applicable in organic electronic devices.

Harnessing ICl reduction processes for synthesis of different BEDT-TTF-based molecular conductors.

Both calculations and experimental data, showing the possibility of formation of I3-, I2Cl-, and ICl2- anions through ICl reduction processes, are described in detail. The above processes were used successfully for the preparation of different molecular conductors based on trihalide anions and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF). The reaction between ICl and BEDT-TTF occurring in a strong polar reaction media (epsilon > or = 34.8 D) results in the formation of novel molecular conductors containing different sets of the I3-, I2Cl-, and ICl2- anions: beta-(BEDT-TTF)2[(I3)0.4(I2Cl)0.6], beta'BEDT-TTF)2[(I2Cl)0.2(ICl2)0.8], and beta' '-('-(BEDT-TTF)2[(I3)0.075(I2Cl)0.150(ICl2). These molecular conductors reveal semiconducting (beta'-phase) as well as metallic (beta- and beta' '-phases) transport properties. It is also shown that in the reaction media with polarity less than 18.4 D only the I3- anion is incorporated in the BEDT-TTF-based molecular crystals. This fact is an unexpected outcome of our study.

Evolution of high-temperature molecular relaxations in poly(2-(2-methoxyethoxy)ethyl methacrylate) upon network formation.

Copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (poly(MEO2MA)) are regarded as bioinert replacements of poly(N-isopropylacrylamide) in some biomedical applications. Networks of poly(MEO2MA) of various architecture form thermo-responsive hydrogels. Here, we present dielectric and mechanical spectroscopy studies on segmental motions and network relaxation processes in linear poly(MEO2MA) and its networks - bare network and the network grafted with short poly(MEO2MA) chains. We show that the α process assigned to the segmental motions of poly(MEO2MA) is independent on the polymer topology and the glass transition temperature, Tg, associated with this process equals 235-236 K for all investigated systems. The α' relaxation observed above Tg by dynamical mechanical analysis is assigned to the sub-Rouse process. It strongly depends on the polymer network architecture and slows down by four orders of magnitude upon network formation.

Poly(vinyl methyl ether) hydrogels at temperatures below the freezing point of water-molecular interactions and states of water.

Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the pre-melting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above -60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting.