Synthesis and study of thermal and electrical behaviour of some polyaromatic amines

Samples of polyaromatic amines were synthesised by chemical and electrochemical methods, using different amounts of electrolytes for the purpose of doping the polymer. These polymers were found to show electrical conductivity in the range 10^?12–10^?6 S/cm. A study of conductivity at various temperatures indicates the semiconducting behaviour of these polymers. Thermal analysis shows that these polymers have high thermal stability.     

Highly efficient electroluminescent biphenylyl-substituted poly(p-phenylenevinylene)s through fine tuning the polymer structure

A series of novel biphenylyl-substituted PPV derivatives, polymers 1-4, with different substitution patterns, has been synthesized and characterized. These polymers possess excellent solubilities, good thermal stabilities, and high-photoluminescent efficiencies. ¹H NMR measurements indicated that the polymers contain negligible tolane-bisbenzyl (TBB) structural defects. Light-emitting diodes fabricated from the four polymers with the configuration of ITO/PEDOT:PSS (50 nm)/polymer (80 nm)/LiF (0.4 nm)/Ca (20 nm)/Ag emitted a saturated green light and demonstrated maximum current efficiencies of 5.1, 4.5, 4.7, and 1.4 cd/A for polymers 1-4, respectively. The much higher current efficiencies of polymers 1-3 than polymer 4 are ascribed to more balanced charge transport in the polymer layers of the three polymers, which has been confirmed by time of flight (TOF) charge mobility measurement. The hole mobilities of the polymers at the applied electric field of 2.0×10⁵ V/cm are 4.70×10⁻⁶, 3.83×10⁻⁶, 7.21×10⁻⁶, and 1.76×10⁻⁵ cm²/Vs for polymers 1-4. This research indicated that fine tuning the substitution pattern of the polymer side chains is an effective way to optimize the LED device performance by controlling the structural defects as well as balancing the charge mobility of the polymers.     

Soluble polystyrenes with pyrrole pendant groups and their electroactive properties

Summary Four soluble styrenic polymers containing 3-substituted pendant pyrrole rings with ester or amide arm spacer were synthesized. Their electroactive characteristics were investigated by cyclic voltammetry. The chemical oxidation was accomplished by adding FeCl₃ into a solution of styrenic polymers dissolved in 1:1 mixture of dimethylformamide (DMF) and acetonitrile (ACN). The electrical conductivities of the chemically oxidized black powder of the styrenic polymers were in the range of 10^-1010^-9 S/cm.     

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.     

Polyimides from diamines and dianhydrides

Novel polyimides have been synthesized by reacting 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride with three diamines having the general structure: Polyimide films obtained have been evaluated for their thermal and electrical properties. The dependence of the thermal stability of the polyimides on the structure of the diamine component has been established. The specific volume resistivity has been found to be of the order of 10¹⁵ Ω cm for all the polyimides.     

Preparation and characterization of aqueous dispersions of poly(3,4‐ethylenedithiathiophene‐co‐3,4‐ethylenedioxythiophene)/ poly(styrene sulfonate) and their conducting films

The chemical oxidative copolymerization of 3,4‐ethylenedithiathiophene (EDTT) with 3,4‐ethylenedioxythiophene (EDOT) and 2′‐hydroxymethyl‐3,4‐ethylenedioxythiophene in a poly(styrene sulfonic acid) aqueous solution was successfully carried out to form stable, dark blue colloidal dispersions in water. Coating these dispersions onto polypropylene substrates led to the formation of free‐standing copolymer films. The mechanical, electrical, and thermoelectrical properties of these films were investigated; the films showed superior properties in comparison with those of poly(3,4‐ethylenedithiathiophene) (PEDTT)/poly(styrene sulfonate) (PSS). The copolymer film based on EDTT and EDOT achieved a high electrical conductivity (8.2 × 10^?2 S cm^?1) at 298 K; this could be improved about 10 times through the addition of dimethyl sulfoxide (DMSO) or DMSO/isopropyl alcohol into the polymer dispersion with almost constant Seebeck coefficients of about 9 μV K^?1. On the contrary, these additives had almost no effect on the conductivity of PEDTT/PSS. The structure and morphology of the polymer films were studied by X‐ray diffraction and SEM analyses. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A varistor–polymer composite with nonlinear electrical-thermal switching properties

We studied the dependence of the E–J characteristics on the sintering conditions in varistor fillers, the filler content in the polymer matrix and for different polymers and suggest a possible nonlinear electrical-thermal switching mechanism. The nonlinear coefficient and breakdown field of a sample with 100 vol.% varistor fillers sintered at 950 °C for 5 h were 12.24 and 135 V/mm, separately. A decrease in the amount of filler content in polymeric matrix or using a fortified polymer improved the electrical properties by increasing the breakdown field to the 263–964 V/mm range and decreasing the leakage current density in the 1.06 × 10⁻⁵ to 1.13 × 10⁻¹⁰ A/cm² range. This varistor–polymer composite can exhibit two nonlinearities in electrical conductivity. In the conducting state above the varistor filler breakdown, the polymer matrix reduces the conductivity, if a critical temperature is reached. Thereby the over voltage is limited by the fillers (i.e. varistor effect) and the over current is limited by the polymer matrix (i.e. positive temperature coefficient effect).     

Substrate temperature effects on the electron field emission properties of nitrogen doped ultra-nanocrystalline diamond

For the purpose of improving the electron field emission properties of ultra-nanocrystalline diamond (UNCD) films, nitrogen species were doped into UNCD films by microwave plasma chemical vapor deposition (MPCVD) process at high substrate temperature ranging from 600° to 830 °C, using 10% N₂ in Ar/CH₄ plasma. Secondary ion mass spectrometer (SIMS) analysis indicates that the specimens contain almost the same amount of nitrogen, regardless of the substrate temperature. But the electrical conductivity increased nearly 2 orders of magnitude, from 1 to 90 cm^− 1 Ω^− 1, when the substrate temperature increased from 600° to 830 °C. The electron field emission properties of the films were also pronouncedly improved, that is, the turn-on field decreased from 20 V/μm to 10 V/μm and the electron field emission current density increased from less than 0.05 mA/cm² to 15 mA/cm². The possible mechanism is presumed to be that the nitrogen incorporated in UNCD films are residing at grain boundary regions, converting sp³-bonded carbons into sp²-bonded ones. The nitrogen ions inject electrons into the grain boundary carbons, increasing the electrical conductivity of the grain boundary regions, which improves the efficiency for electron transport from the substrate to the emission sites, the diamond grains.     

A local field emission study of partially aligned carbon-nanotubes by atomic force microscope probe

Atomic force microscopy (AFM) was used to study the field emission (FE) properties of a dense array of long and vertically quasi-aligned multi-walled carbon nanotubes grown by catalytic chemical vapor deposition on a silicon substrate. The use of nanometric probes enables local field emission measurements to be made allowing the investigation of effects that are not detectable with a conventional parallel plate setup, where the emission current is averaged over a large sample area. The micrometric inter-electrode distance allows one to achieve high electric fields with a modest voltage. These features made us able to characterize field emission for macroscopic electric fields up to 250 V/μm and attain current densities larger than 10⁵ A/cm². FE behaviour is analyzed in the framework of the Fowler–Nordheim theory. A field enhancement factor γ ≈ 40–50 and a turn-on field E_turn-on 15 V/μm at an inter-electrode distance of 1 μm are estimated. Current saturation observed at high voltages in the I-V characteristics is explained in terms of a series resistance of the order of MΩ. Additional effects, such as electrical conditioning, CNT degradation, response to laser irradiation and time stability are investigated and discussed.     

Synthesis and characterization of metal polymeric phthalocyanine from 3,3′,4,4−benzophenonetetracarboxylic dianhydride

Metal polymeric phthalocyanines were prepared by reaction of 3,3,4,4-benzophenonetetracarboxylic dianhydride with urea, metal salts and ammonium molybdate. The structure of these polymers was characterized by infrared spectra, visible spectra and X-ray powder diffraction. The electrical conductivity of the polymers after iodine doping was in the range of 10^–4 10^–7 S/cm. Thermogravimetric analyses showed that these polymers have good thermal stability, and have different break mechanism under nitrogen and air condition.     

Preparation of siloxane–silsesquioxane hybrid thin films for large‐scale‐integration interlayer dielectrics with excellent mechanical properties and low dielectric constants

Several kinds of homogeneous organic–inorganic hybrid polymer thin films were designed with improved mechanical properties and low dielectric constants (<3.0). Novel soluble siloxane–silsesquioxane hybrid polymers were synthesized with cyclic and/or cage silane monomers, which had triorganosiloxy (R₃Si_1/2), diorganosiloxane (R₂SiO_2/2), and organosilsesquioxane (RSiO_3/2) moieties with ethylene bridges at the molecular level, by the hydrolysis and condensation of 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane (a cyclic monomer). The electrical properties of these films, including the dielectric constant (～2.51), leakage current (6.4 × 10^?11 A/cm² at 0.5 MV/cm), and breakdown voltage (～5.4 MV/cm) were fairly good. Moreover, the mechanical properties of the hybrid films, including the hardness (～7 GPa), modulus (～1.2 GPa), and crack‐free thickness (<2 μm), were excellent in comparison with those of previous spin‐on‐glass materials with low dielectric constants. The excellent mechanical properties were proposed to be due to the high contents of Si? OH groups (>30%) and the existence of ethylene bridge and siloxane moieties in the hybrid polymer precursors. In addition, the mechanical properties of the hybrid films were affected by the contents of the cagelike structures. The more cagelike structures a hybrid film contained, the worse its mechanical properties were. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 626–634, 2003     

Electrical and third-order nonlinear optical properties of poly(2-fluoro-1,4-phenylenevinylene) and its copolymers

Summary Poly(2-fluoro-1,4-phenylenevinylene), PFPV, and its copolymers have been synthesized via water soluble precursor route and their electrical and optical propreties were measured. It seems that electron-withdrawing fluorine substituent on phenylene ring increases the band-gap of PFPV and it affects electrical and optical properties. The conductivity values of FeCl₃-doped drawn polymer films ranged from 10^-1 to 10¹ Scm^-1 depending on their composition, and were 10 times larger than those of undrawn ones. The ⁽³⁾ value for undrawn PFPV, using THG technique at 1907nm fundamental wavelength, was 4.76x10^-12 esu.     

Effect of excess Bi2O3 on structures and dielectric properties of Bi1.5Zn1.0Nb1.5O7 thin films deposited at room temperature by RF magnetron sputtering

To compensate for bismuth loss that occurred during the film deposition process, Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were deposited at room temperature from the ceramic targets containing various excess amounts of bismuth (0–20 mol%) on Pt/TiO₂/SiO₂/Si substrates by using RF magnetron sputtering technique. The effect of bismuth excess content on the microstructure and electrical properties of BZN thin films was studied. The microstructure and chemical states of the thin films were studied by SEM and XPS. EPMA was employed to assess the film stoichiometry. The X-ray diffraction analysis reveals that the BZN thin films exhibit the amorphous structure in nature. An appropriate amount of excess bismuth improves the dielectric and electrical properties of BZN thin films, while too much excess bismuth leads to deterioration of the properties. BZN thin film with 5 mol% excess bismuth exhibits a dielectric constant of 61 with a loss of 0.4% at 10 kHz and leakage current of 7.26×10^?7 A/cm² at an electric field of 200 kV/cm.     

Polymerizations of nitrogen-containing heterophanes by vapor deposition method,transformation to polymeric films bearing a conjugated structure,and their properties

Summary The polymerizations of three nitrogen-containing heterophanes such as [2.2](2,5)pyridinophane (1), [2.2](2,5)pyrazinophane (2) and N, N-dimethyl-[2.2](2,5)pyrrolophane (3) by the vapor deposition method were carried out. Compounds1, 2 and3 gave poly(2,5-pyridinediyl-ethylene), poly(2,5-pyrazinediylethylene), and poly(N-methyl-2,5-pyrrolediyl-ethylene) as tough films, respectively. The transformation of the ethylene unit in the polymer films to the vinylene one by the dehydrogenation reaction using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) failed in the former two polymeric films and succeded to a certain extent in the latter one. The electrical conductivity of a poly(N-methyl-2,5-pyrrolediyl-vinylene) film obtained by the dehydrogenation reaction was measured to be 4×10^-4 S/cm at room temperature and increased up to 1×10^-2 S/cm on doping with iodine.     

Synthesis of laterally attached side-chain liquid crystalline poly(p-phenylene vinylene) and polyfluorene derivatives for the application of polarized electroluminescence

Two series of poly(p-phenylene vinylene) and polyfluorene derivatives (PPV1-PPV4 and PF1-PF5) containing laterally attached penta(p-phenylene) mesogenes were synthesized and characterized. These polymers show nematic liquid crystalline behavior. The optical properties of the polymers were investigated by UV-vis absorption and photoluminescence spectrometers and these polymers were fabricated to form the polarized electroluminescent devices using poly(ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT-PSS) as an alignment layer. In the series of poly(p-phenylene vinylene) derivatives, polymer PPV4 offered the best EL device performance. It emitted yellow light at 588 nm at 4 V. The maximum brightness was about 1337 cd/m² at 9 V with a polarized ratio of 2.6. In another series of polyfluorene derivatives, PF4 offered the best EL device performance with the polarized ratio of 12.4 and a maximum luminescence of 1855 cd/m². In the case of polarized white light, as a consequence of blending small amount of PF4 and PF5 with a host polymer PF2, polarized ratio of up to 10.2 and a maximum brightness of 2454 cd/m² have been attained. The aligned films exhibited pronounced polarized ratio, implying that the polymers exhibit potential for linearly polarized LED application.     

Investigations of the electrical conduction mechanisms of polyaniline‐DBSA/poly(acrylonitrile‐butadiene styrene) blends

The electrical properties of Al/PANI‐DBSA/ABS/Au blend with PANI (5%) w/w have been investigated by using of current‐voltage (I‐V) measurements, in a temperature range of 100–313 K. The analysis of I‐V characteristics in the forward direction was based on thermionic emission mechanism for applied electrical field till ～3 × 10² V/cm. The thickness dependence of the current‐voltage relationship, clearly demonstrates that the electrical current for larger fields is space charge limited current (SCLC). Temperature dependences of the ideality factor, barrier height, and series resistance have been calculated. The mobility of carriers which is temperature dependent was calculated using the trap free SCLC as 1.53 × 10^?4 cm² V^?1 s^?1 at room temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40688.     

Improvement of field emission performance on nitrogen ion implanted ultrananocrystalline diamond films through visualization of structure modifications

The relationship between the electron field emission properties and structure of ultra-nanocrystalline diamond (UNCD) films implanted by nitrogen ions or carbon ions was investigated. The electron field emission properties of nitrogen-implanted UNCD films and carbon-implanted UNCD films were pronouncedly improved with respect to those of as-grown UNCD films, that is, the turn-on field decreased from 23.2 V/μm to 12.5 V/μm and the electron field emission current density increased from 10E−5 mA/cm² to 1 × 10E−2 mA/cm². The formation of a graphitic phase in the nitrogen-implanted UNCD films was demonstrated by Raman microscopy and cross-sectional high-resolution transmission electron microscopy. The possible mechanism is presumed to be that the nitrogen ion irradiation induces the structure modification (converting sp³-bonded carbons into sp²-bonded ones) in UNCD films.     

Methacrylate based side chain liquid crystalline polymers with pendant cholesterol group: Preparation and investigation of electrical conductivity mechanism

Methacrylate based side‐chain liquid crystalline polymers (SCLCP) bearing cholesterol pendant moieties with various lengths of aliphatic spacer were synthesized and their electrical conductivity mechanism was studied for their possible applications in elastic microelectronic devices. All the polymers exhibited liquid crystalline behavior of broken focal‐conic fan texture of smectic phase. The dielectric properties of polymers were investigated by impedance spectroscopic technique in the frequency range of 100 Hz to 15 MHz at room temperature. Alternating current (AC) conductivity ( ) of the liquid crystalline polymeric films was observed to vary with angular frequency, ω as ω^S with s < 2. Detailed conductivity analysis revealed that the conductivity of the polymeric films follows quantum mechanical tunneling and correlated barrier hoping conductivity mechanisms at low frequency regime, whereas it obeys super linear power law and direct current conductivity mechanisms at high frequency region. The investigation of the SCLC polymeric films helped to propose a model system for their possible potential applications. In the light of this study, the SCLC polymers will be employed as the gate insulator for organic field effect transistor applications, such as large area flexible arrays or as other advanced microelectronic devices that have superior performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45207.     

Transport studies on thin films of Ag7I4VO4 solid electrolyte

Deposition of thin films of the solid electrolyte Ag₇I₄VO₄ by an electrodeposition technique is discussed. The X-ray diffraction technique has been used for the characterization of the films. Measurement of a.c. electrical conductivity in the temperature range 300–400 K showed that films deposited at 313 K and at a current density of 8 mAcm^–2 are of the best quality, having a typical conductivity of 1.5 x 10^-3-1cm^-1 at room temperature (305K) with an activation energy of 0.2eV. Dielectric studies carried out on the best quality films showed that Ag₇I₄VO₄ possesses a high value of dielectric constant ( 10⁵). The frequency dependence of the dielectric constant is explained as due to an interfacial polarization phenomenon. The behaviour of the dielectric ion suggests a Debye-type relaxation.     

Synthesis and electrical properties of poly[2-(2-(4-trifluoromethyl)phenyl)ethenyl-1,4-phenylenevinylene] and PPV copolymers

Summary Poly[2-(2-(4-(trifluoromethyl)phenyl)ethenyl)-5-methoxy-1,4-phenylenevinylene] (PFEMPV) and a series of PPV copolymers containing 1,4-phenylenevinylene (PV) units were synthesized through a water-soluble precursor route, and their electrical and third-order nonlinear optical properties were studied. The PFEMPV films could not be doped with I₂, but FeCl₃-doped films showed an electrical conductivity of 5.0x10^-4 S/cm. The conductivities of FeCl₃-doped copolymer films ranged from 2.0x10^-3 to 2.0 S/cm depending on their copolymer compositions. The third-order nonlinear optical susceptibility, ⁽³⁾(–;,,–), was also investigated by the degenerate four wave mixing technique at 602 nm. The ⁽³⁾ value of PFEMPV was 6.9x10^-11 esu. The photoluminescence spectrum of PFEMPV shows its emission maximum at 550 nm.