Tetrathiafulvalene. VIII. Ethylenverbrückte polymere Tetrathiafulvalene

Tetrathiafulvalenes. VIII. Ethylene-bridged Polymer Tetrathiafulvalenes Syntheses and properties of ethylene-bridged polymer tetrathiafulvalenes are described. These polymers react with bromine, iodine or tetracyanoquinodimethane to form the radical cation salts, whose electrical conductivity are estimated by means of powder compactions. The polymer radical cation salts have a higher conductivity than the polymer TTF (σ_RT max. 10⁻⁵ Ω⁻¹cm⁻¹). The differences in the conductivity between polymer TTF-cationhalides and polymer TTF-TCNQ-salts are small.     

Tetrathiafulvalene. VII [1]. Arylenverbrückte polymere Tetrathiafulvalene

Tetrathiafulvalenes. VII. Arylene-bridged Polymeric Tetrathiafulvalenes Synthesis and properties of phenylene — and biphenylbridged polymeric tetrathiafulvalenes, which are substituted by two methyl-groups in the 3- and 6-position, are described. These polymers react with bromine, iodine or tetracyanoquinodimethane to form the radical cation salts, whose electrical conducticity are estimated by means of powder compactions. The differences in the conductivity of the TCNQ-salts and radical cation halides are very small. The phenylene-bridged polymer-salts show a higher conductivity than the bi-phenylylene-bridged ones up to values of 10⁻³Ω⁻¹ cm⁻¹. Surprisingly the monomer salts have a lower conductivity than the polymer salts.     

Thermal and electrical properties of copoly(1,3,4‐oxadiazole‐ethers) containing fluorene groups

A series of aromatic copolyethers containing 1,3,4‐oxadiazole rings and fluorene groups was prepared by nucleophilic substitution polymerization technique of 9,9‐bis(4‐hydroxyphenyl)fluorene, 1 , or of different amounts of 1 and an aromatic bisphenol, such as 4,4′‐isopropylidenediphenol or phenolphthalein, with 2,5‐bis(p‐fluorophenyl)‐1,3,4‐oxadiazole. The polymers were easily soluble in polar solvents like N‐methylpyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 425°C. The polymers exhibited a glass‐transition temperature in the range of 195–295°C, with a reasonable interval between glass‐transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20°C were in the range of 3.16–3.25. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Silicon‐containing heterocyclic polymers and thin films made therefrom

Thin films, in the range of tens of micrometers thickness, have been prepared by casting onto glass plates the chloroform or N‐methylpyrrolidone solutions of polyimides or poly(imide‐amide)s containing silicon and phenylquinoxaline units in the main chain. The polymers have been synthesized by solution polycondensation reaction of aromatic diamines having preformed phenylquinoxaline rings with bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride or with a diacid chloride resulting from the reaction of this dianhydride with p‐aminobenzoic acid. The polymers were easily soluble in polar aprotic solvents and showed high thermal stability. The free‐standing films exhibited good mechanical properties with tensile strengths in the range of 48–86 MPa, tensile modulus in the range of 1.25–2.22 GPa and elongation at break in the range of 3–37%. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz were in the range of 2.94–3.08 for polyimides and 3.89–4.49 for poly(imide‐amide)s. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3062–3068, 2006     

Molecular modeling and synthesis of polymers for use in applications requiring a low-k dielectric

As integrated circuits have become more and more complex and with smaller and smaller feature sizes several limitations have become apparent. One of these is the need for low-k dielectric materials as insulating layers. Recent work has reported promising materials for such insulators that include some fluorinated polymers. These dielectric materials were further improved by introducing porosity into the polymer films. One of the key factors in the dielectric constant of a material is its density. As the polarization of the material is related to the number of bonds, the dielectric constant will scale with the density. In this paper a series of molecular modeling calculations were conducted on various fluorine substituted polymers in order to predict their densities. A surprising result of these calculations was the prediction that some of the polymers would have densities less than 1 g/cm³. One of these polymers was synthesized and the density determined. The calculated density was in extremely good agreement with the experimental density. This paper will present the details of the molecular modeling technique as well as the synthesis and characterization of one of the polymers of interest.     

Freestanding Ag2S/CuS PVA films with improved dielectric properties for organic electronics

The prime goal of this work is to synthesize free‐standing polyvinyl alcohol (PVA) films doped with Ag₂S, CuS, Ag₂S/CuS alloy, and Ag₂S/CuS nanocomposites through the sol–gel route. The dependence of Ag₂S content in the PVA nanocomposite films on both the real and imaginary parts of the complex permittivity and loss tangent values was examined. An enhanced dielectric constant was achieved with minimum dielectric loss due to the insulating silica layer. By changing the Ag₂S content in Ag₂S/CuS PVA films, the AC conductivity is improved with pure Ag₂S nanoparticles exhibiting highest values of the order of 10^?6?10^?9 S/cm. The Cole–Cole parameters were calculated and the semicircles observed in the plots indicate a single relaxation process. The results suggest that these composite films are potential materials for embedded capacitor applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43568.     

New photoimageable dielectric insulating copolyester thin films: Synthesis and characterization

In this article, we describe the synthesis and characterization of a new family of photoimageable dielectric insulating polymer films. Four different photoimageable thin films have been prepared from all-aromatic and aromatic/aliphatic copolyesters, which exhibit good photospeed (10–180 s, 15.5 mW/cm² intensity), resolution and line width (10 μm), thermal stability (330–400°C), adhesion on different substrates, mechanical strength, and reasonable glass transition temperature (120–150°C). One feature of the new photoimageable copolyester is the formation of a low dielectric constant film (2.5 at 1 kHz, 25°C) upon curing at temperatures up to 280°C. The low dielectric constant is a result of foaming arising from evolution of by-products during curing. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1199–1211, 1997     

Copoly(1,3,4-oxadiazole-ether)s containing phthalide groups and thin films made therefrom

A series of aromatic copolyethers containing 1,3,4-oxadiazole rings and phthalide groups was prepared by nucleophilic substitution polymerization technique of phenolphthalein, 1, or of an equimolecular amount of 1 and different bisphenols 2, such as: 4,4′-isopropylidenediphenol, 4,4′-(hexafluoroisopropylidene)diphenol, 4,4′-(1,4-phenylene-diisopropylidene)bisphenol, 4,4′-cyclohexylidene-bisphenol and 2,7-dihydroxynaphthalene, with 2,5-bis(p-fluorophenyl)-1,3,4-oxadiazole, 3. The polymers were easily soluble in polar solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and chloroform and can be cast from solutions into thin flexible films. They showed high thermal stability, with decomposition temperature being above 400 °C. The polymers exhibited a glass transition temperature in the range of 220-271 °C, with reasonable interval between glass transition and decomposition temperature. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz and 20 °C were in the range of 2.98-3.15.     

Synthesis of urethane acrylate based electromagnetic interference shielding materials

In this work, a new method, consists of synthesis of urethane acrylate (UA) followed by in situ polymerization of pyrrole using cerium (IV) as an oxidant and UV‐curing of the composites, for preparing polypyrrole–UA (PPy–UA) composite films was described. It appeared that dielectric constants of the composites increased with increasing the PPy content and decreased with increasing the frequency from 10^?2 to 10⁷, indicating an interfacial Maxwell–Wagner contribution to the permittivity. An incorporation of a small amount of PPy (15% Py) to UA matrix increased their dielectric constants more than 4 × 10⁴ (41,259) at 10^?2 Hz. So, the incorporation of PPy was very effective for enhancing the dielectric properties of UA matrix. Furthermore, the significant enhancement in dielectric properties (loss tangent and dielectric constant) contributes to the improvement in electromagnetic interference shielding efficiency. Composite films were characterized using Fourier transform infrared attenuated total reflectance (FTIR‐ATR) spectrophotometer and ¹H‐NMR. It was seen that PPy is blended with the UA matrix at the molecular level through H‐bonding interactions. A linear relationship was also observed between the characteristic groups' absorbances of PPy (from FTIR‐ATR) and dielectric constant values (from dielectric spectrometer). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Low Dielectric Polyimide/Fluorinated Ethylene Propylene (PI/FEP) Nanocomposite Film for High-Frequency Flexible Circuit Board Application

The low dielectric polymer films have drawn great attention to the application as the dielectric insulating materials in high-frequency circuit boards, while the weak adhesion to the copper foils and the poor processability resulted from the fluorinated or rigid structures limited their high-frequency application. In this work, the low dielectric and high adhesive polyimide/fluorinated ethylene propylene (PI/FEP) nanocomposite film for high-frequency flexible circuit board application is developed. It is indicated that the fluorocarbon surfactants can significantly improve the dispersion of FEP in PI substrate, and thus, the PI/FEP nanocomposite film exhibits excellent mechanical properties, including the tensile strength increases to 46.6 MPa and the elongation at the break increases to 13.7%. Importantly, at the high-frequency of 10 GHz, the 60 wt% FEP filled PI nanocomposite film displays an ultralow dielectric loss (0.006) and a reduced dielectric constant (2.69). In addition, the high-frequency flexible circuit board with the PI/FEP film as the dielectric insulating layer has a high peel strength of 0.75 N mm⁻¹, indicating this PI/FEP nanocomposite film can meet the requirements of the high-frequency flexible circuit board application.     

Electrical conduction in plasma polymerized thin films of γ‐terpinene

Plasma polymerized γ‐terpinene (pp?GT) thin films are fabricated using RF plasma polymerization. MIM structures are fabricated and using the capacitive structures dielectric properties of the material is studied. The dielectric constant values are found to be in good agreement with those determined from ellipsometric data. At a frequency of 100 kHz, the dielectric constant varies with RF deposition power, from 3.69 (10 W) to 3.24 (75 W). The current density–voltage (J?V) characteristics of pp–GT thin films are investigated as a function of RF deposition power at room temperature to determine the resistivity and DC conduction mechanism of the films. At higher applied voltage region, Schottky conduction is the dominant DC conduction mechanism. The capacitance and the loss tangent are found to be frequency dependent. The conductivity of the pp?GT thin films is found to decrease from 1.39 × 10^?12 S/cm (10 W) to 1.02 × 10^?13 S/cm (75 W) and attributed to the change in the chemical composition and structure of the polymer. The breakdown field for pp–GT thin films increases from 1.48 MV/cm (10 W) to 2 MV/cm (75 W). A single broad relaxation peak is observed indicating the contribution of multiple relaxations to the dielectric response for temperature dependent J?V. The distribution of these relaxation times is determined through regularization methods. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42318.     

Electro-optical performances of nanostructured SrTiOx films: The effect of plasma power,Ar/O2 ratio and annealing

The present work evaluates the effects of plasma power and oxygen mixing ratios (OMRs) on structural, morphological, optical, and electrical properties of strontium titanate SrTiO_x (STO) thin films. STO thin films were grown by magnetron sputtering, and later thermal annealing at 700°C for 1 h was applied to improve film properties. X-ray diffraction analysis indicated that as-deposited films have amorphous microstructure independent of deposition conditions. The films deposited at higher OMR values and later annealed also showed amorphous structure while the films deposited at lower OMR value and annealed have nanocrystallinity. In addition, all as-deposited films were highly transparent (~80%–85%) in the visible spectrum and exhibited well-defined main absorption edge, while the annealing improved transparency (90%) within the same spectrum. The calculated direct and indirect optical band gaps for films were in the range of 3.60-4.30 eV as a function of deposition conditions. The refractive index of the films increased with OMRs and the postdeposition annealing. The frequency dependent capacitance measurements at 100 kHz were performed to obtain film dielectric constant values. High dielectric constant values reaching up to 100 were obtained. All STO samples exhibited more than 2.5 μC/cm² charge storage capacity and low dielectric loss (less than 0.07 at 100 kHz). The leakage current density was relatively low (3 × 10⁻⁸Acm⁻² at +0.8 V) indicating that STO films are promising for future dynamic random access memory applications.     

Insulating polyimide films containing n‐type perylenediimide moieties

Oxadiazole‐containing polyperyleneimides were prepared by high‐temperature solution polycondensation reaction of an aromatic diamino‐oxadiazole with a mixture of two dianhydrides, one containing a perylene moiety and the other containing a hexafluoroisopropylidene unit. Flexible films having good mechanical properties were made therefrom. The structure of the polymer films was confirmed using X‐ray photoelectron spectroscopy. Some polymer films were subjected to measurements of electrical insulating properties. The variation of the real and imaginary parts of the dielectric permittivity with frequency and temperature was recorded. The values of the dielectric constant, dielectric loss and specific resistance were obtained at 25 °C and in the frequency domain from 1 Hz to 130 kHz. The dielectric spectroscopy data showed distinct γ and β subglass transitions for these polymers at low activation energies. Electronic conduction through a hopping mechanism in these polyimide films was determined from AC conductivity measurements. Copyright © 2012 Society of Chemical Industry     

Electrical properties of nanoporous F doped SiO2 low-k thin films prepared by sol-gel method with catalyst HF

Using hydrofluoric acid as acid catalyst, F doped nanoporous low-k SiO₂ thin films were prepared through sol-gel method. Compared with the hydrochloric acid catalyzed film, the films showed better micro structural and electrical properties. The capacitance-voltage and current-voltage characteristics of F doped SiO₂ thin films were then studied based on the structures of metal-SiO₂-semiconductor and metal-SiO₂-metal, respectively. The density of state (DOS) of samples deposited on metal is found to decrease to a level of 2 × 10¹⁷ eV^?1 cm^?3. The values of mobile ions, fix positive charges, trapped charges and the interface state density between the SiO₂/Si interfaces also decrease obviously, together with the reduction of the leakage current density and the dielectric constant, which imply the improvement of the electrical properties of thin films. After annealing at a temperature of 450^°C, the lower values of the leakage current density and dielectric constant could be obtained, i.e. 1.06 × 10^?9 A/cm² and 1.5, respectively.     

Dielectric Properties of Sol–Gel‐Derived Bi12SiO20 Thin Films

In this paper the dielectric properties of crack‐free, Bi₁₂SiO₂₀ thin films were investigated. The films were prepared on Pt/TiO₂/SiO₂/Si and corundum substrates using the sol–gel method. The formation of a pure Bi₁₂SiO₂₀ phase was observed at a temperature of 700°C. The Bi₁₂SiO₂₀ thin films, heat treated at 700°C for 1 h, had a dense microstructure with an average roughness (R_a) of 50 nm. The dielectric properties of the film were characterized by using both low‐ and microwave‐frequency measurement techniques. The low‐frequency measurements were conducted with a parallel capacitor configuration. The dielectric constant and dielectric losses were 44 and 7.5 × 10^?3, respectively. The thin‐film dielectric properties at the microwave frequency were measured using the split‐post, dielectric resonator method (15 GHz) and the planar capacitor configuration (1–5 GHz). The dielectric constant and the dielectric losses measured at 15 GHz were 40 and 17 × 10^?3, respectively, while the dielectric constant and the dielectric losses measured with the planar capacitor configuration were 39 and 65 × 10^?3, respectively.     

Enhanced dielectric and mechanical properties of polylactic acid/polycaprolactone blends by introducing double-layer carbon nanofillers

To overcome the issues of poor toughness and low dielectric constant associated with PLA, which limit its application in the electronics industry, we introduced an insulating polydopamine (PDA) layer on the surface of core-shell nickel-coated carbon nanotube (Ni-CNT) and nickel-coated graphene (Ni-GRA). Through a double-layer structural design approach, we successfully prepared polylactic acid (PLA)/polycaprolactone (PCL) blends that exhibit high dielectric constant (ε’) and low dielectric loss (tanδ). This innovative design led to impressive impact strengths of 29.41 kJ/m² for PLA/PCL/4Ni-GRAs and 22.54 kJ/m² for PLA/PCL/4Ni-CNTs. PDA enhanced the interfacial interactions between the filler and matrix, which improved the dispersion of Ni-CNTs and Ni-GRAs and contributed to the mechanical properties of the PLA/PCL blends. Simultaneously, PLA/PCL/4Ni-CNTs and PLA/PCL/4Ni-GRAs exhibited commendable integrated dielectric properties. The PDA@fillers form microcapacitors with the polymer matrix and the conductive Ni layer enhances ε’ and reduces the conductivity difference between fillers. Furthermore, the insulating PDA layer contributed to improved dispersion, inhibition of charge carrier migration, and reduction in tanδ. At 1000 Hz, the ε′ of PLA/PCL/4Ni-CNTs and PLA/PCL/4Ni-GRAs increased to 88.3 and 124.6, respectively, and the tanδ values remained below 1, indicating minimal dielectric loss. This provides a promising direction for eco-friendly materials with enhanced dielectric and mechanical properties.     

Phthalonitrile‐containing poly(amide imide)s with nanoactuation properties

A series of aromatic poly(amide imide)s containing pendant phthalonitrile groups was prepared by solution polycondensation reaction of 4,4′‐diamino‐4″‐(3,4‐dicyanophenoxy)triphenylmethane, 1, or of different amounts of 1 and 1,3‐bis(4‐aminophenoxy)benzene, with a fluorinated imide diacid chloride, 2,2‐bis[N‐(4‐chloroformylphenyl)phthalimidyl]hexafluoroisopropane. The polymers were easily soluble in polar organic solvents, such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide, and dimethylsulfoxide. They can be cast from solutions into thin flexible films showing nanoactuation properties in the range of 120–450 nm, depending on the nitrile group content, when an electric voltage is applied on their surface. Electrical insulating properties of the polymer films were evaluated on the basis of dielectric permittivity and dielectric loss and their variation with the frequency and temperature. The values of the dielectric permittivity at 10 kHz and 20°C were in the range of 3.01–3.43. All polymers exhibited high thermal stability, decomposition temperature being above 420°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Electrical properties of nanoporous F doped SiO2 low-k thin films prepared by sol-gel method with catalyst HF

Using hydrofluoric acid as acid catalyst, F doped nanoporous low-k SiO₂ thin films were prepared through sol-gel method. Compared with the hydrochloric acid catalyzed film, the films showed better micro structural and electrical properties. The capacitance-voltage and current-voltage characteristics of F doped SiO₂ thin films were then studied based on the structures of metal-SiO₂-semiconductor and metal-SiO₂-metal, respectively. The density of state (DOS) of samples deposited on metal is found to decrease to a level of 2 × 10¹⁷ eV⁻¹ cm⁻³. The values of mobile ions, fix positive charges, trapped charges and the interface state density between the SiO₂/Si interfaces also decrease obviously, together with the reduction of the leakage current density and the dielectric constant, which imply the improvement of the electrical properties of thin films. After annealing at a temperature of 450^∘C, the lower values of the leakage current density and dielectric constant could be obtained, i.e. 1.06 × 10⁻⁹ A/cm² and 1.5, respectively.     

Effects of annealing temperature on structure and electrical properties of sol–gel derived 0.65PMN-0.35PT thin film

0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (0.65PMN-0.35PT) thin films were deposited on Pt/Ti/SiO₂/Si substrates annealed from 550 to 700 °C using sol-gel process. The effects of annealing temperature on microstructure, insulating, ferroelectric and dielectric properties were characterized. The result reveals that 0.65PMN-0.35PT thin films possess a polycrystalline structure, matching well with the perovskite phase despite the existence of a slight pyrochlore phase. The film samples annealed at all temperatures exhibit relatively dense surfaces without any large voids and the grain size increases generally with the increase of the annealing temperature. Meanwhile, pyrochlore phase is considerably generated because of the deformation of perovskite phase caused by volatilization of Pb at an excessive high-temperature. The film annealed at 650 °C exhibits superior ferroelectricity with a remanent polarization (P_r) value of 13.31 μC/cm², dielectric constant (ε_r) of 1692 and relatively low dielectric loss (tanδ) of 0.122 at 10⁴ Hz due to the relatively homogeneous large grain size of 130 nm and low leakage current of approximately 10^-6 A/cm².     

Studies on the preparation and properties of conductive polymers. III. Metallized polymer films by retroplating out

A novel method to prepare polymer metallized films was found by using polymer metal chelate films treated with wetted metal plates (or metal powders). The polymer metal chelate films were prepared by metal salts mixed with the polymers containing a functional group, such as poly(vinyl alcohol) (PVA), polyamide, polyacrylamide (PAAm), and polyurethane (PU). This novel method is called the retroplating-out method. Polymer metallized films exhibited low surface resistivity around 10^?1 Ω/cm² by using this novel method. The surfaces of these films were shown to be metallized by means of X-ray analysis. The conduction mechanism was verified reasonably well by using scanning electron microscope (SEM) and UV-visible absorption data.