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.

Synthesis and Characterization of New Conjugated Azomethines End-Capped with Amino-thiophene-3,4-dicarboxylic Acid Diethyl Ester.

A new series of thiophene-based azomethines differing in the core structure was synthesized. The effect of the central core structure in azomethines on the thermal, optical and electrochemical properties was investigated. The obtained compounds exhibited the ability to form a stable amorphous phase with a high glass transition temperature above 100 °C. They were electrochemically active and undergo oxidation and reduction processes. The highest occupied (HOMO) and the lowest unoccupied molecular (LUMO) orbitals were in the range of -3.86--3.60 eV and -5.46--5.17 eV, respectively, resulting in a very low energy band gap below 1.7 eV. Optical investigations were performed in the solvents with various polarity and in the solid state as a thin film deposited on a glass substrate. The synthesized imines absorbed radiation from 350 to 600 nm, depending on its structure and showed weak emission with a photoluminescence quantum yield below 2.5%. The photophysical investigations were supported by theoretical calculations using the density functional theory. The synthesized imines doped with lithium bis-(trifluoromethanesulfonyl)imide were examined as hole transporting materials (HTM) in hybrid inorganic-organic perovskite solar cells. It was found that both a volume of lithium salt and core imine structure significantly impact device performance. The best power conversion efficiency (PCE), being about 35-63% higher compared to other devices, exhibited cells based on the imine containing a core tiphenylamine unit.

Fully inkjet-printed flexible organic voltage inverters as a basic component in digital NOT gates.

In relation to conventional vacuum-based processing techniques inkjet printing enables upscaling fabrication of basic electronic elements, such as transistors and diodes. We present the fully inkjet printed flexible electronic circuits, including organic voltage inverter which can work as a NOT logic gate. For this purpose the special ink compositions were formulated to preparation of gate dielectric layer containing poly (4-vinylphenol) and of the semiconductor layer poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)]. A printed photoxidized poly (3-hexyltiophene) semiconductor was used as the active layer of the resistors. The operation of the printed inverters and NOT logic gates was analyzed based on the DC current-voltage characteristics of the devices. The resistance of the devices to atmospheric air was also tested. Not encapsulated samples stored for three years under ambient conditions. Followed by annealing to remove moisture showed unchanged electrical parameters in comparison to freshly printed samples.

Polymerization and Structure of Opposing Polymer Brushes Studied by Computer Simulations.

A model of the polymerization process during the formation of a pair of polymer brushes was designed and investigated. The obtained system consisted of two impenetrable parallel surfaces with the same number of chains grafted on both surfaces. Coarse-grained chains embedded in nodes of a face-centered cubic lattice with excluded volume interactions were obtained by a 'grafted from' procedure. The structure of synthesized macromolecular systems was also studied. Monte Carlo simulations using the dynamic lattice liquid model were employed using dedicated parallel machine ARUZ in a large size and time scale. The parameters of the polymerization process were found to be crucial for the proper structure of the brush. It was found that for high grafting densities, chains were increasingly compressed, and there is surprisingly little interpenetration of chains from opposite surfaces. It was predicted and confirmed that in a polydisperse sample, the longer chains have unique configurations consisting of a stretched stem and a coiled crown.

Dynamics of Opposing Polymer Brushes: A Computer Simulation Study.

Opposing polymer brush systems were synthesized and investigated by molecular modeling. Chains were restricted to a face-centered cubic lattice with the excluded volume interactions only. The system was confined between two parallel impenetrable walls, with the same number of chains grafted to each surface. The dynamic properties of such systems were studied by Monte Carlo simulations based on the dynamic lattice liquid model and using a highly efficient parallel machine ARUZ, which enabled the study of large systems and long timescales. The influence of the surface density and mean polymer length on the system dynamic was discussed. The self-diffusion coefficient of the solvent depended strongly on the degree of polymerization and on the polymer concentration. It was also shown that it is possible to capture changes in solvent mobility that can be attributed to the regions of different polymer densities.

Electron Transport in Naphthalene Diimide Derivatives.

Two naphthalene diimides derivatives containing two different (alkyl and alkoxyphenyl) N-substituents were studied, namely, N,N'-bis(sec-butyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide (NDI-s-Bu) and N,N'-bis(4-n-hexyloxyphenyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide (NDI-4-n-OHePh). These compounds are known to exhibit electron transport due to their electron-deficient character evidenced by high electron affinity (EA) values, determined by electrochemical methods and a low-lying lowest unoccupied molecular orbital (LUMO) level, predicted by density functional theory (DFT) calculations. These parameters make the studied organic semiconductors stable in operating conditions and resistant to electron trapping, facilitating, in this manner, electron transport in thin solid layers. Current-voltage characteristics, obtained for the manufactured electron-only devices operating in the low voltage range, yielded mobilities of 4.3 × 10-4 cm2V-1s-1 and 4.6 × 10-6 cm2V-1s-1 for (NDI-s-Bu) and (NDI-4-n-OHePh), respectively. Their electron transport characteristics were described using the drift-diffusion model. The studied organic semiconductors can be considered as excellent candidates for the electron transporting layers in organic photovoltaic cells and light-emitting diodes.

Three Destinies of Solution-Processable Polymer Light-Emitting Diodes under Long-Time Operation.

The article describes three different ways of polymer light-emitting diode (PLED) degradation, caused by damage of the protective layer. The electroluminescence and charge-transport properties of a completely encapsulated diode, the diodes with a leaky protective layer and diodes without encapsulation were compared under long-time exploitation. The studied devices incorporated Super Yellow light-emitting poly-(1,4-phenylenevinylene) PPV copolymer as an electroluminescence component, and (poly-(3,4-ethylenedioxythiophene)-poly-(styrene sulfonate) (PEDOT:PSS) as a charge-transport layer between the indium tin oxide (ITO) anode and aluminum-calcium cathode. To analyze the PLED degradation mechanism regarding charge transport, impedance spectroscopy was used. The values of resistance and capacitance of the internal layers revealed an effect of applied voltage on charge carrier injection and recombination. The factors responsible for the device degradation were analyzed on a macromolecular level by comparing the plots of voltage dependence of resistance and capacitance at different operation times elapsed.

The Quinonoid Zwitterion Interlayer for the Improvement of Charge Carrier Mobility in Organic Field-Effect Transistors.

The interface between the semiconductor and the dielectric layer plays a crucial role in organic field-effect transistors (OFETs) because it is at the interface that charge carriers are accumulated and transported. In this study, four zwitterionic benzoquinonemonoimine dyes featuring alkyl and aryl N-substituents were used to cover the dielectric layers in OFET structures. The best interlayer material, containing aliphatic side groups, increased charge carrier mobility in the measured systems. This improvement can be explained by the reduction in the number of the charge carrier trapping sites at the dielectric active layer interface from 1014 eV-1 cm-2 to 2 × 1013 eV-1 cm-2. The density of the traps was one order of magnitude lower compared to the unmodified transistors. This resulted in an increase in charge carrier mobility in the tested poly [2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno [3,2-b]thiophene)] (DPPDTT)-based transistors to 5.4 × 10-1 cm2 V-1 s-1.

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.