Dielectric relaxation and morphologic properties of CaCu3Ti4O12 doped with GeO2

CaCu₃Ti₄O₁₂ (CCTO) is a material with giant dielectric constant, presenting good stability over a wide temperature and frequency ranges. The preparation method and doping has a great influence on the microstructure and dielectric properties of this material. In this work, doping CCTO with 2–10 wt% GeO₂ has been shown to increase the dielectric constant. We studied the prepared samples by X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy. X-ray diffraction shows the presence of nanocristals. Grains and grain boundaries compositions have been observed by scanning electron microscopy with energy dispersive X-ray spectrometry mapping. Impedance spectroscopy measurements, in the frequency range from 75 kHz to 30 MHz, and temperature from 250 to 325 K, have been performed. The data were analyzed using the Cole–Cole model of dielectric relaxation.     

Dielectric investigations of organic–inorganic hybrid based on (2-hydroxypropyl) cellulose with nanosheet crystallites of quasi-TiO2

In this paper, dielectric spectroscopy investigations of organic–inorganic hybrid composite obtained from (2-hydroxypropyl)cellulose (HPC) with nanosheet crystallites of quasi-TiO₂ are presented. This hybrid belongs to the class of composites, which have no covalent bonds between organic and inorganic constituents and the behaviour of composite is determined mainly by interface of two constituents. The analysis of the molecular dynamics of the hybrid system reveals the influence of the nanosheet crystallites of quasi-TiO₂ on the relaxation processes of HPC matrix. The relaxation strength of γ process strongly increases in composite as compared to neat HPC. A shift to higher temperature has been evidenced in the case of α and β processes. A higher value of the slope of the maximum frequency vs. the inverse temperature for the α-relaxation of the composite has been observed. At high temperatures the mesomorphic behaviour of HPC has been drastically reduced in the composite. The results of our investigations are interpreted in terms of a presence of intermolecular forces between HPC and nanosheet crystallites of quasi-TiO₂.     

Dielectric properties of polystyrene–CCTO composite

The control of the dielectric properties of polymer composites is a relevant tool to synthesize a material to a specific industrial application. Polystyrene (PS) is a suitable host because it is readily available, and is easy to cast into desired shapes, maintaining the mechanical integrity of the matrix. CaCu₃Ti₄O₁₂ (CCTO) is a well-known high dielectric constant material, very useful for capacitors and memory devices. In this work, we studied the dielectric properties of the composite PS–CCTO, in the frequency range 10 Hz to 100 kHz, for CaCu₃Ti₄O₁₂ grains concentrations up to 64% by volume. Different mixture laws were used to fit the data: Hanai, Wiener, Maxwell–Wagner, Kraszewsky, Looyenga and Generalized Looyenga. The last one presents the best results. The calculated exponent of this law was then correlated with the shape particles observed by scanning electron microscopy. Finally, using Generalized Looyenga law, we can carefully select the adequate CCTO concentration in order to tailor the desired behavior, producing interesting composites for potential applications.     

石墨烯/钛酸锶钡/聚偏氟乙烯复合薄膜介电性能研究

首先制备了硅烷偶联剂改性后的石墨烯和钛酸锶钡粉体,然后采用溶液混合法制备了石墨烯/钛酸锶钡/聚偏氟乙烯薄膜,并且对复合薄膜的微观结构、介电性能和热稳定性进行测定和分析.结果表明:硅烷偶联剂成功接枝到石墨烯和钛酸锶钡粉体表面,石墨烯和钛酸锶钡粉体能够较好的分散在聚偏氟乙烯基体中,石墨烯的加入可以大幅度提高材料的介电性能.在石墨烯质量分数为4.06;时,复合薄膜的介电常数达到515,介电损耗为0.6.在质量分数4.14;时发生了渗流现象,介电常数达到1500,介电损耗也达到了5左右.石墨烯的加人大幅度提升了复合材料的介电性能,并且在常用温度范围内具有良好的温度稳定性.     

Growth and characterization of 4‐Aminopyridinium‐4‐nitro phenolate single crystals

Organic optical material 4‐Aminopyridinium‐4‐nitro phenolate (4AP4NP) has been synthesized, and single crystals of size 20 x 14 x 6 mm³ have been grown from acetone solvent at room temperature by solvent evaporation technique. The grown crystals have been characterized by X‐ray diffraction to determine the cell parameters, and by FT‐IR technique to confirm the formation of the expected compound. The crystal belongs to monoclinic crystal system with space group P2₁/a.The structural perfection of the grown crystals has been analyzed by high‐resolution X‐ray diffraction (HRXRD) rocking curve measurements. The thermal stability of the compound has been determined by TG‐DTA curves. The transmittance of 4AP4NP has been used to determine the refractive index n; the extinction coefficient K and both the real ε_r and imaginary ε_i components of the dielectric constant as functions of photon energy. The optical band gap of 4AP4NP is 2.4 eV. The dielectric and mechanical behavior of the specimen was also studied. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and optical characterization of Rf-sputtered metal cluster doped silica thin films

In this paper the preparation and characterization of nanostructured materials via co-sputtering of SiO₂ and silver followed by a suitable heat-treatment for size and fill factor control is described. Transmission electron microscopy (TEM), X-ray and UV–Vis spectroscopy have been carried out to evaluate the cluster size and the optical properties of the composite films, which are a direct consequence of quantum and dielectric confinement effect. Computer simulations have been performed in order to compare the experimental data with theory. Tuning of cluster size and optical properties of the composite thin films is demonstrated by varying deposition conditions and following heat-treatments.     

Progress in the growth of CaCu3Ti4O12 and related functional dielectric perovskites

Calcium copper titanate, CaCu₃Ti₄O₁₂, (CCTO), a potential electro-ceramic is a member of a very important perovskite family and has been found to a show dielectric constant of the order of 10⁴–10⁵. It has a remarkable ability to undergo a series of cationic exchange reactions resulting in corresponding isomorphs. In the past decade there has been immense activity in the search of an isomorph of CCTO with high dielectric constant and low loss which enables its use as capacitor material for the storage of energy and miniaturization of electronic based equipment. Despite intensive research in the area there is no source of any literature that gives all the possible relevant information regarding various synthetic methods, characterizations, effect of sintering parameters (temperature, duration, and atmosphere). This review article is an effort to review the synthesis, grain growth, morphological evolution, effect of impurities, substitution and interface anisotropy on the dielectric constant, resistivity and other materials parameters.     

Low‐temperature elastic and dielectric properties of K3Na(SO4)2 crystals

Elastic and dielectric properties of glaserite K₃Na(SO₄)₂ single crystal were examined using the method of composite oscillators, Brillouin light scattering methods and dielectric spectroscopy. Measurements were performed in the temperature range from 18 K to 300 K. Anomalies in the temperature dependencies of Brillouin shift and dielectric permittivity at about 70 K confirmed the earlier predicted phase transition at 75 ± 25 K. Temperature dependences of the resonance frequency of the vibrating composite oscillator, Brillouin shift measured in the [110] direction, components of dielectric permittivity tensor reveal an anomaly at about 50 K. Moreover, thermal hysteresis of the dielectric permittivity suggested the presence of an incommensurate state between T ₁ = 50 K and T ₂ = 70 K. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,growth and characterization of l‐alaninium oxalate ‐ a novel organic NLO crystal

Nonlinear optical material of L‐alaninium oxalate (LAO) has been synthesized and single crystals are grown by slow evaporation technique. The solubility data of LAO is determined in water. Single crystal X‐ray diffraction study showed that LAO belongs to orthorhombic system with a non‐centrosymmetric space‐group P2₁2₁2₁. The functional groups have been identified from FT‐IR spectrum. The UV‐Vis‐NIR spectrum of LAO shows less optical absorption in the entire visible region. The second harmonic generation (SHG) in the material was estimated using Nd:YAG laser. The mechanical properties of the grown crystals are studied using Vickers microhardness tester. The AC and DC conductivity, and dielectric studies are also carried out and reported for the first time. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Exploration on nano-composite fumed silica-based composite polymer electrolytes with doping of ionic liquid

Fumed silica (SiO₂)-based composite polymer electrolytes were prepared by means of solution casing technique. Horizontal attenuated total reflectance-Fourier Transform Infrared (HATR-FTIR) study shows the complexation between polymer matrix and SiO₂. The highest ionic conductivity of (4.11 ± 0.01) × 10^? 3 Scm^? 1 is achieved upon inclusion of 8 wt.% of SiO₂. Three different regions have been observed in the frequency dependence–ionic conductivity study. The conductivity rises sharply with frequency at low frequency regime. It is followed by a frequency independent plateau region and sharp decrease in the conductivity at high frequency range. The dielectric permittivity (ε^') and dielectric loss (ε^") are decreased with increasing the frequency. This phenomenon is mainly attributed to the electrode polarization effect. The formation of electrical double layer has been proven in these dielectric permittivity studies. This indicates the non-Debye properties of the nano-composite polymer electrolytes.     

Tb3+ luminescence enhancement of YAG:Tb3+ nanocrystals embedded in silica xerogel

The luminescence behavior of composite materials consisting of nanocrystals of Y_3?xAl₅O₁₂:Tb (YAG:Tb³⁺) embedded into silica xerogel has been studied. Blue and green luminescence of the materials is due to a cross-relaxation effect in Tb³⁺ ions doped into a YAG lattice. The materials with YAG:Tb³⁺ nanocrystals immobilized in silica exhibit enhancement of Tb³⁺ luminescence in comparison with the macrocrystalline YAG:Tb³⁺ powder. The Tb³⁺ luminescence intensity of a composite material dried at room temperature can be improved when higher aliphatic alcohols are applied in a one-pot procedure during a sol–gel synthesis. On the other hand, the Tb³⁺ luminescence is quenched in the presence of Ag nanoparticles in the material. The composite material (YAG:Tb³⁺ in silica) exhibits thermal stability at higher temperatures and achieves the highest emission intensity after having been annealed at 700 °C.     

Dielectric properties of Zr-Sn-Ti-O thin films prepared by pulsed laser deposition

Zr_0.26Sn_0.23Ti_0.51O₂ (ZSTO) films with a dielectric constant of about 40 have been prepared directly on silicon substrates by pulsed laser deposition at 600 °C. TEM observation showed that the as-deposited films are amorphous. Differential thermal analysis showed that the ZSTO films crystallize at about 620 °C. Capacitance-voltage (C-V) characteristics of metal-oxide-semiconductor (MOS) composed of Pt/ZSTO/Si prepared at different deposition temperature have been measured. The EOT of the MOS structures with the same ZSTO physical thickness increased slightly when the deposition temperature increased. The EOT is about 4.2 nm for the 40 nm ZSTO deposited at 600 °C. The leakage current characteristics of ZSTO films for the as deposited, post-annealed in oxygen ambient and post-annealed in nitrogen ambient by rapid thermal annealing have been studied comparatively. The films post-annealed in nitrogen ambient have the lowest leakage current and the as-deposited films have the largest leakage current characteristics. It is proposed that amorphous Zr-Sn-Ti oxide stabilized at 600 °C is a potential dielectric material for dynamic random access memory and high k dielectric gate applications.     

Flux growth and low temperature dielectric relaxation in piezoelectric Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals

Single crystals of Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT 91/9) have been grown by flux method after modifications in temperature profile, flux ratio and addition of excess ZnO/B₂O₃ which resulted in enhanced perovskite yield (more than 95%). Only a few crystals showed the presence of pyrochlore phase/variation in composition. A comparative characterization of these crystals were carried out in respect of piezoelectric charge coefficient d₃₃, dielectric constant, ac conductivity and hysteresis loop after cutting and poling the crystals along [001] direction. The total activation energy for conduction has been found to increase with Ti‐content in the sample. The effect of ZnO on growth behavior has been analyzed. A detailed analysis of PZNT (91:9) has been carried out at low temperature in respect of the various thermodynamic parameters related to the dielectric relaxation mechanism, like optical dielectric constant, static dielectric constant, free energy of activation for dipole relaxation, enthalpy of activation and relaxation time, have been calculated in the vicinity of transition temperature in the lower temperature region. The activation energy for relaxation at ‐10 and ‐49 °C have been found to be 0.09 and 0.02 eV respectively. The results were analyzed and a detailed dielectric analysis and low temperature relaxation behavior of PZNT crystals were interpreted. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Time‐dependent dielectric behaviour in incommensurate TlInS2 crystal

The results of measurements of temperature and time dependencies of the dielectric constant of TlInS₂ in the temperature interval of successive incommensurate and commensurate phase transitions have been presented. Considerable decrease of the dielectric constant in a temperature interval including successive phase transitions was observed after annealing the sample at a fixed temperature in the ferroelectric state. Additionally, it has been revealed that the time dependencies of the real part of dielectric susceptibility and dielectric losses angle tangent of TlInS₂ crystal in the incommensurate phase exhibits an unusual behaviour, which is accompanied by exponential decreasing of the dielectric constant and increasing of dielectric losses angle tangent by time. The observed effects are qualitatively explained using defect‐density‐wave model and phenomenological theory of incommensurate systems containing discommensurations undergoing nucleation and evolution processes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric characteristics of Ce3+ doped Sr0.61Ba0.39Nb2O6 with Cole‐Cole plots technique

In this paper, we have investigated two‐relaxator mechanism and dielectric characteristics of Ce³⁺ doped Sr_0.61Ba_0.39Nb₂O₆ with dielectric spectroscopy measurements. The crystal undergoes a ferroelectric phase transition at 340 K. The temperature dependence of the real and imaginer part of the complex dielectric susceptibility in vicinity of ferroelectric‐paraelectric phase transition has been studied in the frequency region 0.1 kHz–10 MHz. The measurements of the dielectric constant of the real and imaginer parts show strongly frequency dependence. The investigations of the dielectric constant revealed a non‐Debye type dielectric relaxation for Ce⁺³ doped SBN61 by using Cole‐Cole plots. It reveals the coexistence of the two dielectric relaxators in vicinity of the phase transition. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,characterization, and crystal structure of macrocyclic nickel(II) complexes bearing a,e-cis-1,4-chdc and e,e-trans-1,4-chdc (chdc = cyclohexanedicarboxylate) ligands

ABSTRACT

The Lead Zirconate-titane(PZT) ceramic is known by its piezoelectric characteristic, but also by its stiffness. The use of a composite based on a polyurethane (PU) matrix charged by a piezoelectric material, enable to generate a large deformation of the material, therefore harvesting more energy. This new material will provide a competitive alternative and low cost manufacturing technology of autonomous systems (smart clothes, car seat, boat sail, flag …). A thin film of the PZT/PU composite was prepared using up to 80 vol. % of ceramic. Due to the dielectric nature of the PZT,inclusions of this one in a PU matrix raise the permittivity of the composite. For the most of industrial applications, the composite will not be used at room temperature, and as the energy harvested from this new materials have a direct relation with their permittivity we have made a study about the variation of the permittivity at different temperature and frequencies.     

Ferroelectric and ferroelastic properties of Rb2MnCl4·2H2O

Rb₂MnCl₄·2H₂O crystal belonging to the family of tetrahalogeno‐metallates dihydrates has been subjected to thermal, optical and dielectric studies. At room temperature the optical study under a polarization microscope has revealed a ferroelastic domain structure. At 240 K a dielectric anomaly, characteristic of the week ferroelectric phase transition, has been also observed. Moreover, below the temperatures of the phase transitions dielectric dispersion has appeared. Ferroic properties of Rb₂MnCl₄·2H₂O crystal have been compared to those of other tetrachlorides dehydrates. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of La3Ga5.5Ta0.5O14 crystal

La₃Ga_5.5Ta_0.5O₁₄ (LGT) crystal was grown by using the Czochralski method. The as‐grown crystal is transparent, free from inclusions and with no cracks. Specific heat, thermal expansion, dielectric constants, transmission spectrum and optical damage threshold of LGT have been measured, and the results show general properties of LGT are similar to that of La₃Ga₅SiO₁₄ (LGS) crystal. The experiment to research the Q‐switch properties of LGT has been performed and the results show LGT possesses smaller electrooptic coefficients than that of LGS and may not be an ideal material used as a Q‐switch. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

GeO2 based high k dielectric material synthesized by sol–gel process

Recently, there has been lot of research on new high dielectric constant (high k) materials for use in future generations of ultra-large scale integrated circuits (ULSI). There are number of requirements for the new high k materials, such as high dielectric constant, thermal stability (400 °C or higher), high mechanical strength, and good adhesion to neighboring layers. Keeping in view the properties required for the replacement of existing SiO₂ dielectrics, new high k dielectric material based on GeO₂ has been synthesized. Polycrystalline GeO₂ thin films have been deposited by simple, and cost effective sol–gel spin coating process. The obtained xerogel films of germanium oxide have been annealed at 400 °C, 600 °C and 800 °C for 3 h in argon atmosphere. Elemental composition, morphology, and phase analysis have been measured by employing X-ray photoelectron spectroscopy, scanning electron microscopy, and X-ray diffraction techniques, respectively. The formation of the hexagonal GeO₂ phase at and above 400 °C has been reported. The composition of the annealed films have been measured and found to be 68 at.% of O, 32 at.% of Ge for GeO₂, which are close to the stoichiometry of the GeO₂.     

Optical properties of 2‐aminopyridinium nitrato silver

Crystals of 2‐aminopyridinium nitrato silver have been synthesized by slow evaporation method. Grown crystals have been subjected to FTIR, Single crystal X‐Ray diffraction and UV‐Visible studies in order to investigate the structural and optical properties of the crystal. The FTIR spectrum reveals the presence of the functional group that corresponds to both 2‐aminopyridine and silver nitrate, suggesting the formation of the compound, 2‐aminopyridinium nitrato silver. From XRD it is observed that the crystal crystallizes in the structure of monoclinic with the space group of P2₁/c. The optical transmittance spectrum shows the maximum transparency of about 95% in the visible region is in consistent with the wide band gap, estimated as 4.738 eV. The optical constants n and k has also been determined from the transmittance data. The static dielectric constant is found to be 0.851. The wide band gap and the less dielectric constant suggest the suitability of this compound material for photoconductive applications. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)