Electrical properties of conventional polyimide films: Effects of chemical structure and water uptake

A series of conventional polyimide (CPI) films, based on pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylicdianhydride (BTDA), were prepared by a two step process, and their dielectrical constant, dielectrical loss, and DC conduction behaviors were studied at different frequencies and voltages. Their dielectrical breakdown voltage, water uptake, and solubility properties were also investigated. The effects of chemical structure and water uptake on the electrical properties of the films are discussed in detail. The dielectric constants of the CPI films vary between 2.93 and 3.72 at 1 MHz frequency and they are in the following decreasing order: BTDA‐DDS > BTDA‐DDE > PMDA‐DDS > PMDA‐DDE. The structure and thermal and oxidative stability of films were analyzed by FTIR‐ATR and TGA, respectively. The results showed that all CPI films have good insulating properties, such as high dielectric breakdown voltage, low dielectric constant with stability for long period of frequency, and low leakage density. Our results concerning electrical properties also suggest that electron hopping is responsible for AC conduction and Poole‐Frenkel mechanism is predominant for DC conduction of all CPI films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 810–818, 2006     

Structural,dielectric properties and electrical conduction behaviour of Dy substituted CaCu3Ti4O12 ceramics

Dy substituted CCTO ceramics were synthesized using solid state reaction method. Effect of Dy on structural, microstructural, dielectric and electrical properties has been studied over a wide temperature (300–500 K) and frequency range (100 Hz–1 MHz). Rietveld refinement, carried out on the samples, confirmed single phase formation and indicated overall decrease in lattice constant. Microstructure showed bimodal distribution of grains in CCTO with bigger grains surrounded by smaller grains. Dy substitution reduced grain size. Dy substitution in CCTO reduces the dielectric constant which may be attributed to increase of the Schottky potential barrier. The dielectric constant remains nearly constant in temperature range 300–400 K. The AC conductivity obeys a power law, σ_ac=A fⁿ, where n is the temperature dependent frequency exponent. The AC conductivity behaviour can be divided into three regions, over entire temperature range, depending on conduction processes. The relevant charge transport mechanisms have been discussed.     

Polyimide and polyhedral oligomeric silsesquioxane nanocomposites for low-dielectric applications

A novel polyimide (PI) hybrid nanocomposite containing polyhedral oligomeric silsesquioxane (POSS) with well defined architecture has been prepared by copolymerization of octakis(glycidyldimethylsiloxy)octasilsesquioxane (Epoxy-POSS), 4,4′-oxydianiline diamine (ODA), and 4,4′-carbonyldiphthalic anhydride (BTDA). In these nanocomposite materials, the equivalent ratio of the Epoxy-POSS and ODA are adjustable, and the resultant PI-POSS nanocomposites give variable thermal and mechanical properties. More importantly, we intend to explore the possibility of incorporating POSS moiety through the Epoxy-POSS into the polyimide network to achieve the polyimide hybrid with lower dielectric constant (low-k) and thermal expansion. The lowest dielectric constant achieved of the POSS/PI material (PI-10P) is 2.65 by incorporating 10 wt% Epoxy-POSS (pure PI, k=3.22). In addition, when contents of the POSS in the hybrids are 0, 3, 10 wt% (PI-0P, PI-3P, PI-10P), and the resultant thermal expansion coefficients (TEC) are 66.23, 63.28, and 58.25 ppm/°C, respectively. The reduction in the dielectric constants and the resultant thermal expansion coefficients of the PI-POSS hybrids can be explained in terms of creating silsesquioxane cores of the POSS and the free volume increase by the presence of the POSS-tethers network resulting in a loose PI structure.     

Structural, electrical and dielectric properties of Bi1.5Zn0.92Nb1.5−xTaxO6.92 pyrochlore ceramics

The micro-structural, compositional, temperature dependent dielectric and electrical properties of the Bi_1.5Zn_0.92Nb_1.5−xTa_xO_6.92 solid solution has been investigated. The increasing Ta content from 0.2 to 1.5 caused; single phase formation, a pronounced grain size reduction from ∼7.0 to 2.5 μm, sharp decrease in the dielectric constant from 198 to 88 and an increase in the electrical conductivity from 3.16 × 10⁻¹⁰ to 5.0 × 10⁻⁹ (Ω cm)⁻¹, respectively. The temperature dependent dielectric constant which is found to be frequency invariant in the frequency range of (0.0-2.0 MHz) exhibited a sharp change in the temperature coefficient of dielectric constant at a (doping independent) critical temperature of 395 K. The analysis of the measured data reflects a promising future for this type of pyrochlore to be used in high voltage passive device applications.     

Characteristics of polyimide/barium titanate composite films

In this study, the characteristics of the polyimide/BaTiO₃ composite films with various amounts of BaTiO₃ were evaluated. Modifier 1-methoxy-2-propyl acetate was added during composite preparation to disperse the BaTiO₃ particles in polyimide matrix. Conversion of polyamic acid (PAA) to polyimide was not completed for the composite film with a high BaTiO₃ loading (90 wt%). Dielectric constant of the film increases from 3.53 to 46.50, at the sweep frequency of 10 kHz, as the BaTiO₃ content increases from 0 to 90 wt% (0–67.5 vol.%), which is mainly due to the relatively high dielectric constant of BaTiO₃ particles in the polyimide matrix. The dielectric losses at 10 kHz is ranging from 0.005 to 0.015, which is due to the switching of the domain wall. Water absorption decreases considerably with increasing BaTiO₃ content. With 10 wt% (2.5 vol.%) BaTiO₃ addition, the water absorption of the composite film reduces 45% from that of pure polyimide. Also, high loading of BaTiO₃ is not beneficial to reduce the water absorption of the composite film.     

Frequency, temperature and In dependent electrical conduction in NiFe2O4 powder

A series of polycrystalline spinel ferrites with the composition NiIn_xFe_2-xO₄ (0 ≤ x ≤ 0.3) were prepared by the solid state reaction to study the effect of In³⁺ ions substitution on their dc electrical resistivity and dielectric properties. The dc resistivity has been investigated as a function of temperature and composition. The indium ion increases the dc resistivity and activation energy of the system. A study of the dielectric properties of these mixed ferrites, as a function of composition, frequency and temperature, has been undertaken. The dielectric constant (ε′), dielectric loss (ε″) and dielectric loss tangent (tanδ) all decreases with frequency as well as with the composition. The dielectric constant (ε′) and dielectric loss tangent (tanδ) were increases with increasing temperature. AC conductivity increases with increase in applied frequency. The dielectric behavior of the present samples is attributed to the Maxwell-Wagner type interfacial polarization. The conduction mechanism in these ferrites is due to electron hopping between Fe²⁺ and Fe³⁺ ions on adjacent octahedral sites.     

Ionic conductivity in Bi2Sn2O7 ceramics

Impedance spectroscopy measurements, in the temperature range from room temperature to 600 K, were performed in order to investigate the dielectric and ionic properties of Bi₂Sn₂O₇ ceramics. The results show that the conductivity in this pyrochlore is associated with the hopping of ions. An activation energy of 1.26 eV was observed and the dielectric constant exhibits a strong contribution from ionic conduction.     

Low-dielectric, nanoporous polyimide films prepared from PEO-POSS nanoparticles

Dielectric insulator materials that have low dielectric constants (k<2.5) are required as inter-level dielectrics to replace silicon dioxide (SiO₂) in future semiconductor devices. In this paper, we describe a novel method for preparing nanoporous polyimide films through the use of a hybrid PEO-POSS template. We generated these nanoporous foams are generated by blending polyimide as the major phase with a minor phase consisting of the thermally labile PEO-POSS nanoparticles. The labile PEO-POSS nanoparticles would undergoes oxidative thermolysis to releases small molecules as byproducts that diffuse out of the matrix to leave voids into the polymer matrix. We achieved significant reductions in dielectric constant (from k=3.25 to 2.25) for the porous PI hybrid films, which had pore sizes in the range of 10-40 nm.     

Synthesis and rheological properties of oligoimide/montmorillonite nanocomposites

We report a facile strategy for preparing polyimides (PI)/montmorillonite (MMT) nanocomposites at moderate temperatures that avoids thermal degradation of organically-modified MMT (organo-MMT) that is commonly observed during conventional melt-blending of organo-MMT with commercial high molecular weight PI at elevated temperatures. Novel polyimides of low molecular weight (oligoimides) based on 1,3-bis(3′,4,-dicarboxyphenoxy)benzene and 4,4′ bis(4″-aminophenoxy)diphenylsulfone were synthesized and subsequently melt-blended at temperatures ranging from 150 to 250 °C with special organically-modified montmorillonite clay nanoparticles to form new polyimide/organo-MMT nanocomposites with special combination of physical and chemical properties for diverse applications such as microelectronic components where chemical inertness, high temperature stability, low dielectric constant, mechanical toughness and processability are primary requirements. It was found that application of a strong shearing flow near the glass transition temperature of the oligoimide to the oligoimide/organo-MMT nanocomposite melt blend containing 6±2 vol% of the organo-MMT resulted in three orders of magnitude increase in the viscosity. Partial exfoliation of the organo-MMT together with constrained deformation of the polymer between the rigid nanoparticle layers (as evidenced by formation of the network structure or fractal gel) are thought to be responsible for this observed viscosity behavior. The viscosity behavior is typical for model xylene/MMT system where the MMT particles were dispersed in xylene solvent homogeneously via ultrasonic mixing. This study suggests that the rheological methods used here may provide a valuable analytical tool to accelerate efforts to develop useful polyimide nanocomposites from synthetic oligoimides containing ceramic nanoparticles having different shapes and sizes. Further, because of their facile synthesis and desirable characteristics these polyimide/MMT clay nanocomposites are expected to be excellent model systems for exploring feasibility of new routes for driving organic polymers to self-assemble into useful nanocomposites.     

Microstructure and properties of polyimide/poly(vinylsilsesquioxane) hybrid composite films

Polyimide (PI)/poly(vinylsilsesquioxane) (PVSSQ) (PI/PVSSQ) hybrid composite films were prepared from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA)-4,4′-oxydianiline (ODA) polyamic acid and triethoxyvinylsilane (TEVS or VSSQ) via sol-gel process and thermal imidization. The presence of the PVSSQ showed a remarkable effect on the microstructure and properties of the polyimide based hybrid films. The transparency of the hybrid films decreased with increasing the content of the PVSSQ. The compatibility and interfacial interaction of the hybrid composites were evaluated by scanning electron microscope (SEM) and atomic force microscope (AFM), respectively. The PI/PVSSQ hybrids showed nanocomposite formation when the contents of PVSSQ was less than 20 wt%. It was found that the surface topography was influenced by the composition of the PVSSQ. Incorporating of the PVSSQ increased the thermal stability and T_g of hybrid composites. The dielectric constant of the hybrid composites was reduced by adding PVSSQ up to a certain content, showed a minimum and then found to be increased. The dielectric constant values of the hybrid composites ranged from 2.59 to 3.78. The presence of the PVSSQ also showed significant effects on the mechanical properties of the polyimide films.     

Influence of frequency, grade, moisture and temperature on Green River oil shale dielectric properties and electromagnetic heating processes

Development of in situ electromagnetic (EM) retorting technologies and design of specific EM well logging tools requires an understanding of various process parameters (applied frequency, mineral phases present, water content, organic content and temperature) on oil shale dielectric properties. In this literature review on oil shale dielectric properties, we found that at low temperatures (< 200 °C) and constant oil shale grade, both the relative dielectric constant (ε′) and imaginary permittivity (ε″) decrease with increased frequency and remain constant at higher frequencies. At low temperature and constant frequency, ε′ decreases or remains constant with oil shale grade, while ε″ increases or shows no trend with oil shale grade. At higher temperatures (> 200 °C) and constant frequency, ε′ generally increases with temperature regardless of grade while ε″ fluctuates. At these temperatures, maximum values for both ε′ and ε″ differ based upon oil shale grade. Formation fluids, mineral-bound water, and oil shale varve geometry also affect measured dielectric properties. This review presents and synthesizes prior work on the influence of applied frequency, oil shale grade, water, and temperature on the dielectric properties of oil shales that can aid in the future development of frequency- and temperature-specific in situ retorting technologies and oil shale grade assay tools.     

Synthesis and characterization of novel fluorinated polyimides derived from 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl)ethylidene]diphthalic anhydride and aromatic diamines

A novel fluorinated aromatic dianhydride, 4,4′-[2,2,2-trifluoro-1-(3,5-ditrifluoromethylphenyl) ethylidene] diphthalic anhydride (9FDA), was synthesized, which was employed to polycondense with various aromatic diamines, including 4,4′-oxydianiline, 1,4-bis(4-aminophenoxy) benzene, 3,4′-oxydianiline and 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene to produce a series of fluorinated aromatic polyimides. The fluorinated polyimides obtained had inherent viscosities ranged of 0.61-1.14 dL/g and were easily dissolved both in polar aprotic solvents and in low boiling point common solvents. High quality polyimide films could be prepared by casting the polyimide solution on glass plate followed by thermal baking to remove the organic solvents and volatile completely. Experimental results indicated that the fluorinated polyimides exhibited good thermal stability with glass transition temperature ranged of 245-283 °C and temperature at 5% weight loss of 536-546 °C. Moreover, the polyimide films showed outstanding mechanical properties with the tensile strengths of 87.7-102.7 MPa and elongation at breaks of 5.0-7.8%, good dielectric properties with low dielectric constants of 2.71-2.97 and low dissipation factor in the range of 0.0013-0.0028.     

Phase development and dielectric responses in PMN–BNT ceramics

(1 − x)Pb(Mg_1/3Nb_2/3)O₃–x(Bi_0.5Na_0.5)TiO₃ ceramics were prepared by the conventional mixed-oxide method. All compositions show complete perovskite solid solutions and the structure to change from cubic to rhombohedral at x = 0.5. The dielectric constant and dielectric loss tangent were measured as a function of both temperature and frequency. The results indicated a relaxor ferroelectric behavior for all ceramics. The temperature at maximum of the dielectric constant of PMN–BNT ceramics were seen to increase with increasing BNT content. Moreover, the broadest dielectric peak occurs at x = 0.9, which leads to a morphotropic phase boundary in this system.     

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.     

Effect of polymer structure on the morphologies and dielectric properties of nanoporous polyimide films

Low dielectric constant polyimide (PI) films have potential applications in integrated circuit. In this study, poly(methyl methacrylate), poly(ethylene oxide), and polystyrene as thermally labile materials were used as templates to generate PI films with nanopores by first mixing the polymer templates with the precursor of PI, poly(amic acid), followed by imidization of poly(amic acid) together with degradation of the polymer templates. The sizes of the formed pores, the thermal and dielectric constant of the nanofoamed PI films were studied and compared in detail. It is concluded that the dielectric constant of PI films using poly(ethylene oxide) as pore template is more stable because of the formation of uniform pores which is from the great accordance of imidization temperature of poly(amic acid) with the degradation temperature of poly(ethylene oxide). But that using poly(methyl methacrylate) as pore template is frequency dependent as the influence of inhomogeneous pores and PMMA residue from incompletely degradation of poly(methyl methacrylate). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41480.     

Role of initial potassium excess on the properties of potassium tantalate ceramics

Potassium tantalate (KTaO₃ - KT) ceramics with controlled initial K/Ta ratio = 1, 1.02 and 1.05 were synthesised by solid-state reaction. Crystal structure and microstructure of the sintered ceramics were examined by XRD and SEM/EDS, respectively. Their dielectric properties were then studied as a function of the temperature over the radio frequency range. Ceramics with K/Ta ratio = 1 exhibits potassium-poor secondary phases, in contrast to ceramics with initial K/Ta ratio = 1.05, where no secondary phases are detected. Moreover, the grain size increases dramatically with K/Ta ratio >1. The quantum paraelectric behaviour of KT ceramics is weakly affected by the variation of K/Ta ratio and their dielectric response is well described by Barrett's equation. Though, no anomaly is induced in the dielectric permittivity by potassium excess, it yields an increase of its lowest temperature magnitude up to ∼4000, which is to the best of our knowledge, the highest value ever reported for KT ceramics.     

A comparative study of electric properties of nano-structured and bulk Mn-Mg spinel ferrite

A series of nano-sized particles of Mn_1−xMg_xFe₂O₄ (x = 0.0, 0.1, 0.2 and 0.25) have been synthesized by co-precipitation method. The effect of Mg-substitution on structural and dielectric properties is reported in this paper. X-ray diffraction analysis for both nanosize and bulk samples revealed the nanocrystalline nature in the prepared ferrite samples. The crystallite size increases from 3-6 nm in nanosamples to 63.9-85.5 nm in bulk samples. The dielectric properties for all the samples have been studied as a function of frequency in the range 10-10⁵ Hz at different temperatures. Dielectric properties such as dielectric constant (?′) dielectric loss (?″), dielectric loss tangent (tan δ) and ac conductivity have been studied for the investigated samples as a function of frequency. The data indicated that, the dielectric constant and the loss factor values of our former are ten orders of magnitude than those of the later. The low dielectric behavior makes ferrite materials useful in high frequency applications.     

A chemically amplified positive-working photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) and poly(amic acid)

We prepared a novel chemically amplified photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) (PAAE) and poly(amic acid); this blend produces polyimide (PI) films with improved mechanical properties after imidization with photoacid generator (PAG). PAAE and poly(amic acid) were end-capped with 5-norbornene-2,3-dicarboxylic dianhydride and 2,3-dimethyl maleic anhydride, respectively, to lower their molecular weights without compromising the properties of the resulting PI films. As a result of the blending of these PI precursors, the mechanical properties of the PI films were found to be less affected by the strong acid generated from the PAG than PI films fabricated by imidization of PAAE alone. The relatively high solubility of the blended PI precursor film in basic aqueous solutions was found to be effectively controlled by the use of a high-temperature post-exposure bake process to partially imidize the end-capped PAA. It was found that a 10-μm-thick film of the PSPI precursor system containing 13 wt% PAGs exhibits a sensitivity (D⁰) of 700 mJ/cm² when developed with 2.38 wt% aqueous tetramethyl ammonium hydroxide solution at room temperature. A fine positive pattern was fabricated in a 12 μm thick film with 1000 mJ/cm² of i-line exposure. The resultant PI film was also found to exhibit excellent mechanical and thermal properties, which are critical to its practical use as a stress buffer layer in semiconductor packaging.     

In situ preparation of polyimide/titanium carbide composites with enhanced dielectric constant

A series of polyimide/titanium carbide (PI/TiC) composites with different TiC contents were prepared using the ultrasonic dispersion and in situ polymerization method. Atomic force microscopy (AFM), X‐ray diffraction (XRD), scanning electron microscope (SEM), mechanical, and electrometer were used to characterize the structure and properties of the obtained composites. The morphological study of composites by AFM and SEM showed that TiC particles had a homogeneous dispersion in polyimide matrix with nanoscale at low filler dosage (≤10% volume content). X‐ray diffractions (XRDs) indicated that the doping of TiC slightly reduced the packing density of polyimide and destructed the aggregation structure of polyimide molecules. Experimental results showed that the obtained PI/TiC composites exhibited appropriate mechanical properties and moderate electric breakdown strength. Dielectric investigation evidenced that the dielectric constant and the dielectric loss of these composites increased with the increase of the volume fraction of TiC particles. The composite with 20 vol% TiC particles showed a highest dielectric constant of 37 while retaining an appropriate dielectric loss of 0.026, as compared with the dielectric constant (3–4) of neat polyimide resin. In addition, the dielectric properties of the composites displayed good stability within a wide range of frequency. The results of this work demonstrate the potential use of a PI/TiC composite film in an embedded capacitor. POLYM. COMPOS., 125–130, 2016. © 2014 Society of Plastics Engineers     

Preparation of carbon fiber web from electrostatic spinning of PMDA-ODA poly(amic acid) solution

Pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA) were copolymerized in a tetrahydrofuran (THF)/methanol (MeOH) mixed solvent to form a 12 wt.% poly(amic acid) (PAA) solution. It was electrostatically spun at 13-15 kV to form a PAA web of fine fibers with diameters less than 2-3 μm. The PAA web was heated to 150-250 °C to induce cyclization, transforming the PAA web into polyimide (PI) web. Then, the PI web was heat-treated at 700, 800, 900, 1000 and 2200 °C. The carbonization yield decreased monotonically from 64% at 700 °C to 53% at 1000 °C. The electrical conductivity of carbonized PI webs also increased with increasing heat treatment temperature, exhibiting 2.5 and 5.3 S/cm at 1000 and 2200 °C, respectively. The tensile strength and modulus of the carbonized web were 5.0 and 73.9 MPa, respectively.