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.

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.

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.

Structural, electrical, and magnetic study of La-, Eu-, and Er- doped bismuth ferrite nanomaterials obtained by solution combustion synthesis.

In this work, the multiferroic bismuth ferrite materials Bi0.9RE0.1FeO3 doped by rare-earth (RE = La, Eu, and Er) elements were obtained by the solution combustion synthesis. Structure, electrical, and magnetic properties of prepared samples were investigated by X-ray photoelectron spectroscopy, Mössbauer spectroscopy, electrical hysteresis measurement, broadband dielectric spectroscopy, and SQUID magnetometry. All obtained nanomaterials are characterized by spontaneous electrical polarization, which confirmed their ferroelectric properties. Investigation of magnetic properties at 300.0 K and 2.0 K showed that all investigated Bi0.9RE0.1FeO3 ferrites possess significantly higher magnetization in comparison to bismuth ferrites obtained by different methods. The highest saturation magnetisation of 5.161 emu/g at 300.0 K was observed for the BLaFO sample, while at 2.0 K it was 12.07 emu/g for the BErFO sample. Several possible reasons for these phenomena were proposed and discussed.

Effect of Metal-Ligand Coordination Complexes on Molecular Dynamics and Structure of Cross-Linked Poly(dimethylosiloxane).

Poly(dimethylosiloxane) (PDMS) cross-linked by metal-ligand coordination has a potential functionality for electronic devices applications. In this work, the molecular dynamics of bipyridine (bpy)-PDMS-MeCl2 (Me: Mn2+, Fe2+, Ni2+, and Zn2+) are investigated by means of broadband dielectric spectroscopy and supported by differential scanning calorimetry and density functional theory calculations. The study of molecular motions covered a broad range of temperatures and frequencies and was performed for the first time for metal-ligand cross-linked PDMS. It was found that the incorporation of bpy moieties into PDMS chain prevents its crystallization. The dielectric permittivity of studied organometallic systems was elevated and almost two times higher (ε' ~4 at 1 MHz) than in neat PDMS. BpyPDMS-MeCl2 complexes exhibit slightly higher glass transition temperature and fragility as compared to a neat PDMS. Two segmental type relaxations (α and αac) were observed in dielectric studies, and their origin was discussed in relation to the molecular structure of investigated complexes. The αac relaxation was observed for the first time in amorphous metal-ligand complexes. It originates from the lower mobility of PDMS polymer chains, which are immobilized by metal-ligand coordination centers via bipyridine moieties.