Microstructures and electrical responses of pure and chromium-doped CaCu3Ti4O12 ceramics

Pure and chromium-doped CCTO (CaCu₃Ti₄O₁₂) ceramics were prepared by a conventional solid-state reaction method, and the effects of chromium doping on the microstructures and electrical properties of these ceramics were investigated. Efficient crystalline phase formation accompanied by dopant-induced lattice constant expansion was confirmed through X-ray diffraction studies. Scanning electron microscopy (SEM) results show that doping effectively enhanced grain growth or densification, which should increase the complex permittivity. The dielectric constant reached a value as high as 20,000 (at 1 kHz) at a chromium-doping concentration of 3%. The electrical relaxation and dc conductivity of the pure and chromium-doped CCTO ceramics were measured in the 300-500 K temperature range, and the electrical data were analyzed in the framework of the dielectric as well as the electric modulus formalisms. The obtained activation energy associated with the electrical relaxation, determined from the electric modulus spectra, was 0.50-0.60 eV, which was very close to the value of the activation energy for dc conductivity (0.50 ± 0.05 eV). These results suggest that the movement of oxygen vacancies at the grain boundaries is responsible for both the conduction and relaxation processes. The short-range hopping of oxygen vacancies as “polarons” is similar to the reorientation of the dipole and leads to dielectric relaxation. The proposed explanation of the electric properties of pure and chromium-doped CCTO ceramics is supported by the data from the impedance spectrum.     

Dielectric properties of soft chemical method derived CaCu3Ti4O12 thin films onto Pt/TiO2/Si(1 0 0) substrates

Calcium copper titanate, CaCu₃Ti₄O₁₂ (CCTO), thin film has been deposited by the soft chemical method on Pt/Ti/SiO₂/Si (1 0 0) substrates at 700 °C for 2 h. The peaks were indexed as cubic phase belonging to the Im−3 space group. The film exhibited a duplex microstructure consisting of large grains of 130 nm in length and regions of fine grains (less than 80 nm). The CCTO film capacitor showed a dielectric loss of 0.031 and a dielectric permittivity of 1020 at 1 MHz. The J-V behavior is completely symmetrical, regardless of whether the conduction is limited by interfacial barriers or by bulk-like mechanisms. Based on impedance analyses, the equivalent circuit of CCTO film consisting of a resistor connected in series with two resistor-capacitor (RC) elements.     

溶胶—凝胶法制备CaCu3Ti4O12-MgTiO3复合陶瓷的介电性能与IV特性

通过溶胶凝胶方法制备得到CaCu3Ti4O12-MgTiO3复合陶瓷粉料,并在1000,1050和1100℃3个温度点烧结成瓷。采用XRD、SEM等对得到的样品成分、结构进行了分析,发现材料为CCTO-MgTiO3/MgTi2O4复相体系。在此基础上,对材料的介电性能、IV非线性特性做了相关测试。复合陶瓷在1100℃下烧结后,其介电常数比纯的CCTO要提高3到4倍。对材料的IV测试发现,复合陶瓷的IV非线性系数可以通过复合体系的线性法则拟合得到,材料的非线性系数约为4.56。     

Thickness effects of Bi0.89Ti0.11FeO3 thin films deposited on PbZr0.2Ti0.79Nb0.01O3 buffer layers

Bi_0.89Ti_0.11FeO₃ thin films with the thicknesses of 200-440 nm were fabricated on the 40-nm-thick PbZr_0.2Ti_0.79Nb_0.01O₃ (PZTN)-buffered Pt(1 1 1)/Ti/SiO₂/Si substrates using a metal organic decomposition process. As a result of the good insulating property and high breakdown characteristic of the PZTN buffer layer, the leakage currents in the Bi_0.89Tb_0.11FeO₃ films are significantly reduced. All the films show well-saturated and rectangular P-E hysteresis loops without any evident leaky behavior. The remnant polarization P_r and coercive field E_c for all Bi_0.89Ti_0.11FeO₃ films are around 45-50 μC/cm² and 200 kV/cm, respectively, and show weak dependent on the film thickness. The 200-nm-thick Bi_0.89Ti_0.11FeO₃ film exhibits better fatigue-free characteristic and charge-retaining ability, and the domain backswitching is significantly restrained due to the strong anti-aging ability of the PZTN buffer layer.     

High frequency response to the impedance complex properties of Nb-doped CaCu3Ti4O12 electroceramics

Impedance analyses was performed on undoped and Nb-doped CaCu₃Ti₄O₁₂ (CaCu₃Ti_4−xNb_xO_12+x/2; x = 0, 0.01, 0.03, 0.05, 0.1) to investigate their electrical properties. The pellet samples were prepared using the solid state reaction method. Silver electrode was deposited on both pellets’ surfaces for electrical measurement. The thermally etched samples showed tiny bumped domains within the grains. The existence of both domain and grain boundaries are believed to strongly influence the dielectric constant of CaCu₃Ti₄O₁₂ (CCTO). Undoped CCTO showed two arcs of impedance complex plane while Nb-doped samples have three arcs. Each arc represents the constituent elements of the CCTO. The highest frequency arc is evidence that CCTO consists of conductive domains which measure about 1 Ω and are insulated by two types of barriers, i.e. domain boundary and grain boundary.     

CaCu3Ti4O12 ceramics from basic co-precipitation (BCP) method: Fabrication and properties

High dielectric CaCu₃Ti₄O₁₂ (CCTO) ceramics have been successfully prepared by a novel basic co-precipitation (BCP) method. Compared with the conventional solid-state and/or soft chemistry methods, the BCP method has many advantages such as relatively lower sintering temperature, shorter sintering time and lower costs. The XRD patterns confirm the formation of CCTO crystal phase in the as-prepared samples. Influences of initial ingredients and sintering condition on phase composition, microstructure and dielectric property have been investigated through series of trials. The correlation between the process of the grain growth and dielectric properties of final products has been explored. The final products exhibit the dielectric constants higher than 10,000 and the dielectric losses lower than 0.15 at 1 KHz.     

Stress and defect induced enhanced low field magnetoresistance and dielectric constant in La0.7Sr0.3MnO3 thin films

Colossal magnetoresistive manganite La_0.7Sr_0.3MnO₃ (LSMO) films were prepared by pulsed laser deposition on three different single crystal substrates using different deposition parameters. Characterizations of their surface morphologies, structural, magnetic and magneto-transport properties show that films on MgO single crystal substrates contain higher amount of structural defects compared to those on SrTiO₃ (STO) and NdGaO₃ (NGO) substrates. Low deposition rate and thicker films give rise to polycrystallinity and grain boundaries. The films on MgO substrate showed a broad paramagnetic (PM) to ferromagnetic (FM) transition accompanied with metal-insulator transition (MIT) much below their Curie temperature (T_C) indicating growth of strained structures due to large lattice mismatch (9%) between the substrate and the film. The deposited films on STO and NGO show least effect of substrate induced strain exhibiting sharper PM-FM transition and metallic behavior below T_C. The magnetoresistance (MR) measured with 300 mT field clearly shows two contributions, one due to grain boundary tunneling and the other due to colossal MR effect. The highest low field MR effect of 17% was achieved for the film on MgO with the highest thickness and surface roughness indicating the presence of grain boundary related defects. Also a high dielectric constant was observed for the same film at room temperature up to 100 kHz frequency. Coexistence of defect induced large low-field MR and abnormally high dielectric constant can give rise to different exciting applications.     

Charge compensation, electrical and dielectric behavior of lanthanum doped CaCu3Ti4O12

Mechanism of charge compensation on lanthanum, (La³⁺) substitution on Ca site in calcium copper titanate (CaCu₃Ti₄O₁₂), and its effect on resulting electrical and dielectric properties has been studied in the present investigation. For this purpose samples were prepared according to two stoichiometries viz. La_xCa_(1−3x/2)Cu₃Ti₄O₁₂ (x ≤ 0.09) and La_xCa_(1−x)Cu₃Ti₄O₁₂ (x = 0.03) by solid state ceramic route. The former represents ionic compensation while the later is in accordance with electronic compensation. Nature of charge carriers is identified by measuring Seebeck coefficient which is found to be negative in the entire range of measurement. In order to understand the mechanism of conduction, ac conductivity is measured as a function of temperature and frequency. Space charge polarization is the dominant polarization mechanism phenomenon at low frequency and high temperature while orientation polarization dominates at low temperature and high frequency. Impedance analysis confirms the formation of internal barrier layers which is responsible for high dielectric constant in these samples.     

Multiferroic properties of Bi3.15Nd0.85Ti3O12-CoFe2O4 bilayer films derived by a sol-gel processing

Multiferroic Bi_3.15Nd_0.85Ti₃O₁₂ (BNT)-CoFe₂O₄ (CFO) bilayer films with different preferential orientations and thickness fractions for the BNT layer were prepared on Pt/Ti/SiO₂/Si substrate by a sol-gel processing. The experimental results showed that the bilayer films with preferentially a-axis oriented and thicker BNT layer have better ferroelectric properties. The magnetoelectric coupling response is weak when the degree of a-axis orientation of the BNT layer is low or the leakage current is high, while it is mainly controlled by the thickness fraction in other cases.     

An aqueous-solution based low-temperature pathway to synthesize giant dielectric CaCu3Ti4O12—Highly porous ceramic matrix and submicron sized powder

A simple, cost-effective and environment-friendly pathway for preparing highly porous matrix of giant dielectric material CaCu₃Ti₄O₁₂ (CCTO) through combustion of a completely aqueous precursor solution is presented. The pathway yields phase-pure and impurity-less CCTO ceramic at an ultra-low temperature (700 °C) and is better than traditional solid-state reaction schemes which fail to produce pure phase at as high temperature as 1000 °C (Li, Schwartz, Phys. Rev. B 75, 012104). The porous ceramic matrix on grinding produced CCTO powder having particle size in submicron order with an average size 300 nm. On sintering at 1050 °C for 5 h the powder shows high dielectric constants (>10⁴ at all frequencies from 100 Hz to 100 kHz) and low loss (with 0.05 as the lowest value) which is suitable for device applications. The reaction pathway is expected to be extended to prepare other multifunctional complex perovskite materials.     

Effect of V doping on phase composition and electrical properties of K0.4Na0.6Nb1−xVxO3 thin films

Lead-free K_0.4Na_0.6Nb_1−xV_xO₃ thin films were prepared by chemical solution deposition method. The effects of V doping on the phase composition and electrical properties of the films were studied at room temperature. The results indicate that the films are composed of orthorhombic and tetragonal phases, and the phase composition is affected by V content. It is also found that the ferroelectric and dielectric properties are improved by V doping (2P_rmax = 35.5 μC/cm, ?_max = 1189). The enhanced electrical properties are attributed to the more T-phase content and better quality of K_0.4Na_0.6Nb_1−xV_xO₃ (x = 0.015) film.     

Structural, ferroelectric and dielectric properties of In2O3:Sn (ITO) on PbZr0.53Ti0.47O3 (PZT)/Pt and annealing effect

Ferroelectric indium tin oxide (ITO) on PbZr_0.53Ti_0.47O₃ (PZT)/Pt structure, prepared by RF sputtering onto SiO₂/Si substrates, is studied in order to investigate the effect of ITO as a top electrode in these systems. X-ray diffraction, scanning electron microscopy (SEM) and atomic force microscopy (AFM) experiments were performed to study the structure and the surface morphology of the samples. From X-ray diffraction, we observe that the ITO thin film grows with the (1 1 1) texture and the peaks attributed to PZT are all from the perovskite phase. The average roughness (RMS) of the PZT surface is found to be 1.650 nm from AFM experiment. The ferroelectric and dielectric properties were inferred from polarization hysteresis loops, capacitance and dielectric constant measurements. These properties have been compared to those of the widely studied Pt/PZT/Pt system prepared under the same conditions. The effect of ITO/PZT/Pt annealing has been studied. Annealing at 400 °C leads to 13% increase in the dielectric constant ?_r.     

Phenomenological model of grain boundary behaviour under a bias field in Nb-doped CaCu3Ti4O12 ceramics

In this work, the dielectric behaviour and capacitance-voltage (C-V) curves under an applied DC bias field of 1 wt% Nb-doped CaCu₃Ti₄O₁₂ ceramics have been studied. The dielectric properties reveal the existence of grain boundaries of different electrical nature. A new model is proposed to simultaneously explain the presence of insulating and conducting grain boundaries. At low frequency, the capacity curve of the material exhibits a double metal oxide semiconductor (MOS) capacitor-like behaviour and as the frequency is increased, the curve suffers an inversion showing a ferroelectric-like response. This behaviour does not correspond to ferroelectric domain movement phenomena but seems associated to charge accumulation on grain boundary regions.     

In situ synthesis and characterization of polyaniline–CaCu3Ti4O12 nanocrystal composites

High dielectric constant (ca. 2.4 × 10⁶ at 1 kHz) nanocomposite of polyaniline (PANI)/CaCu₃Ti₄O₁₂ (CCTO) was synthesized using a simple procedure involving in situ polymerization of aniline in dil. HCl. The PANI and the composite were subjected to X-ray diffraction, Fourier transform infrared, thermo gravimetric, scanning electron microscopy and transmission electron microscopy analyses. The presence of the nanocrystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. Frequency dependent characteristics of the dielectric constant, dielectric loss and AC conductivity were studied for the PANI and the composites. The dielectric constant increased as the CCTO content increased in PANI but decreased with increasing frequency (100 Hz–1 MHz) of measurement. The dielectric loss was two times less than the value obtained for pure PANI around 100 Hz. The AC conductivity increased slightly up to 2 kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers.     

基于MEMS超级电容器的高介电常数CaCu3Ti4O12薄膜制备及电学特性研究

相对于电化学超级电容器,静电式电容器具有更高的功率密度和可靠性,但能量密度过低。本文提出制备基于高介电常数薄膜CaCu₃Ti₄O₁₂(CCTO)的高能量密度MEMS静电式超级电容器。首先,以硅片为基底,通过溶胶-凝胶法在不同烧结温度(700℃、800℃、900℃)下制备CCTO薄膜,分别采用X射线衍射仪(XRD)和场发射扫描电镜(FE-SEM)对薄膜的形貌、组分和结晶状况进行表征,发现在800℃烧结温度下CCTO薄膜结晶状况最佳。然后,利用金属-绝缘层-半导体结构测试其I-V和C-V特性,计算得到薄膜的最大阈值电压和能量密度分别为47V和3.2J/cm₃。同时,首次对高介电常数介质膜中存在的介质充电现象进行了研究,并分析了介质充电对静电式超级电容器性能的影响。     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

Improved dielectric and non-ohmic properties of Ca2Cu2Ti4O12 ceramics prepared by a polymer pyrolysis method

Non-ohmic and dielectric properties of Ca₂Cu₂Ti₄O₁₂ (CaCu₃Ti₄O₁₂/CaTiO₃ composite) ceramics prepared by a polymer pyrolysis method (PP-ceramic samples) are investigated. The PP-ceramics show a highly dense structure and improved non-ohmic and dielectric properties compared to the ceramics obtained by a solid state reaction method (SSR-ceramic samples). ?′ (tan δ) of the PP-ceramic samples is found to be higher (lower) than that of the SSR-ceramic samples. Interestingly, the PP-ceramic sintered at 1050 °C for 10 h exhibits the high ?′ of 2530 with weak frequency dependence below 1 MHz, the low tan δ less than 0.05 in the frequency range of 160 Hz-177 kHz, and the little temperature coefficient, i.e., |Δ?′| ≤ 15 % in the temperature range from −55 to 85 °C. These results indicate that the CaCu₃Ti₄O₁₂/CaTiO₃ composite system prepared by PP method is a promising high-?′ material for practical capacitor application.     

Dielectric properties of iron doped calcium copper titanate, CaCu2.9Fe0.1Ti4O12

CaCu_2.9Fe_0.1Ti₄O₁₂ (CCFTO) has been prepared by a novel semi-wet route and its dielectric properties have been studied in the temperature range 300-500 K. It is found that dielectric constant (?) decreases drastically in the frequency range 100 Hz to 1 MHz. Complex plane impedance and modulus analysis was done to understand this drastic decrease in ?. Oxidation state of various ions was studied using X-ray photoelectron spectroscopy (XPS). The decrease in the permittivity of CCFTO can be attributed to two factors: the suppression of the Ca/Cu disorder in CCFTO which is observed in CaCu₃Ti₄O₁₂ (CCTO) and the absence of the grain boundary internal barrier layer capacitance mechanism.     

Formation of Al2O3-Bi4Ti3O12 nanocomposite oxide films on low-voltage etched aluminum foil by sol-gel processing

A water-based bismuth titanate Bi₄Ti₃O₁₂ (BTO) sol was synthesized by mixing bismuth nitrate, tetra-n-butyl titanate, lactic acid, acetic acid and distilled water. The sol was applied to low-voltage etched aluminum foil by dip-coating. The crystallization process of Bi₄Ti₃O₁₂ on low-voltage etched aluminum foil was measured by thermal gravimetry-differential scanning calorimetry (TG-DSC) and high-temperature X-ray diffraction (HT-XRD). It was found that Bi₄Ti₃O₁₂ sol first converted into intermediate phase Bi_1.74Ti₂O_6.624, then transformed into perovskite phase Bi₄Ti₃O₁₂. After annealed at 600 °C for 30 min in air, the low-voltage etched aluminum foil covered with Bi₄Ti₃O₁₂ sol was anodized galvanostatically in 15 wt.% ammonium adipate solution. The voltage-time variation during anodizing was monitored and recorded. The structure and composition of samples were investigated by field emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray analysis (EDAX). Results showed that the anodic composite oxide film was composed of an inner Al₂O₃ layer and an outer Bi₄Ti₃O₁₂ layer. The specific capacitance and the product of specific capacitance and withstanding voltage of samples with a BTO coating were about 56.64% and 43.77% larger than that without a BTO coating.