Probing the effects of oxygen-related defects on the optical and luminescence properties in CaCu3Ti4O12 ceramics

The formation of oxygen-related lattice defects and their influence on optical and electronic properties in CaCu₃Ti₄O₁₂ (CCTO) ceramics were studied by controlling the oxygen partial pressure during the sintering process at high temperatures. The samples were analyzed using complementary bulk spectroscopic techniques such as photoluminescence spectroscopy, ultraviolet-visible spectroscopy, Fourier-transform infrared spectroscopy, and electron paramagnetic resonance. Our comprehensive study shows that the oxygen content during sintering process exerts considerable control over the type and concentration of oxygen-related defects in the crystalline CCTO structure. Our results also suggest that the formation of different types of oxygen-related defects in the structure modifies electronic energy levels and thus directly affects the electronic and optical properties of the CCTO phase. These results provided further insight into the important role of oxygen in the crystalline defect arrangement in polycrystalline CCTO ceramics.     

High-resolution FIB-TEM-STEM structural characterization of grain boundaries in the high dielectric constant perovskite CaCu3Ti4O12

In this work, the grain boundaries composition of the polycrystalline CaCu₃Ti₄O₁₂ (CCTO) was investigated. A Focused Ion Beam (FIB)/lift-out technique was used to prepare site-specific thin samples of the grain boundaries interface of CCTO ceramics. Scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectrometry (EDXS) and Electron Energy Loss Spectroscopy (EELS) systems were used to characterize the composition and nanostructure of the grain and grain boundaries region. It is known that during conventional sintering, discontinuous grain growth occurs and a Cu-rich phase appears at grain boundaries. This Cu-rich phase may affect the final dielectric properties of CCTO but its structure and chemical composition remained unknown. For the first time, this high-resolution FIB-TEM-STEM study of CCTO interfacial region highlights the composition of the phases segregated at grain boundaries namely CuO, Cu₂O and the metastable phase Cu₃TiO_4.     

Influence of atmospheres on the dielectric properties of calcium copper titanate ceramics

Calcium Copper Titanate Ceramics (CaCu₃Ti₄O₁₂; CCTO) are useful as capacitors because of the large dielectric constant. This study investigated the effect of testing atmospheres such as air and dry N₂ on the stability and reproducibility of the electrical properties displayed by CCTO ceramics. Solid-state reaction method is used to synthesize phase pure CCTO powders, which are used to fabricate dense samples by sintering. Samples with different microstructures are obtained by sintering at different temperatures of 1070 and 1100°C. AC impedance spectroscopy is used to study the effects of testing atmospheres, temperatures, microstructures, and frequency on the dielectric properties of the sintered samples. Highly irreproducible dielectric properties are observed upon testing in ambient conditions. Stable and reproducible dielectric properties are only obtained in dry N₂. Re-exposing the same CCTO samples back into ambient air after treating in dry N₂ restored irreproducibility. The results from this study suggested that the role of moisture/air in the ambient on the dielectric properties should not be over-looked and is expected to play a key role in controlling the stability of dielectric properties of CCTO. This new approach of characterizing the CCTO ceramics can be used as guidelines to eliminate hysteresis due to ambient atmosphere and to produce stable and reproducible dielectric properties useful as capacitors.     

Effects of LiF addition on microstructure and dielectric properties of CaCu3Ti4O12 ceramics

The effects of small amounts of lithium fluoride sintering aid on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics were investigated. CCTO polycrystalline ceramics with 0.5 and 1.0 mol% LiF, and without additive were prepared by solid state synthesis. Good densification (>90% of the theoretical density) was obtained for all prepared materials. Specimens without the sintering aid and sintered at 1090 °C exhibit secondary phases as an outcome of the decomposition reaction. The mean grain size is controlled by the amount of LiF in specimens containing the additive. Impedance spectroscopy measurements on CaCu₃Ti₄O₁₂ ceramics evidence the electrically heterogeneous nature of this material consisting of semiconductor grains along with insulating grain boundaries. The activation energy for grain boundary conduction is lower for specimens prepared with the additive, and the electric permittivity reached 53,000 for 0.5 mol% LiF containing CCTO.     

Decrease in the dielectric loss of CaCu3Ti4O12 at high frequency by Ru doping

CaCu_3−xRu_xTi₄O₁₂ (x=0, 0.03, 0.05 and 0.07) electronic ceramics were fabricated using a conventional solid-state reaction method. The microstructure, grain sizes and dielectric properties as well as the impedance behaviours of the ceramics were carefully investigated. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) results indicate that ruthenium (Ru) dopant inhibits the growth of grains during the sintering process by promoting the formation of high melting point oxides of Ca and Ti. The study on the frequency dependence of dielectric properties suggests that Ru doping shifts the dielectric loss peak of CCTO to a much lower frequency, thereby reducing the dielectric loss of CCTO at high frequency (f>1.0 MHz) accordingly. When doped with proper amount of Ru, the high frequency dielectric loss of CCTO is reduced to a very low value (tanδ<0.05). Our study conclusively suggests that Ru-doped CCTO, with sufficiently low dielectric loss and decent permittivity, presents potential applications at high frequency.     

Electric transport properties of rare earth doped YbxCa1-xMnO3 ceramics (part I: Optimization of ceramic processing)

A comprehensive study was performed in order to find the effect of different calcination and sintering conditions on the physical properties of calcium manganite ceramics in dependence of temperature T and partial pressure of oxygen p(O₂). The eventual formation of oxygen vacancies during sintering was investigated and the results were confirmed by monitoring the release of oxygen using a ZrO₂ oxygen sensor. The phase transition behavior was studied using thermogravimetric analysis (TGA) in a wide range of p(O₂) ≈ 10^?1 MPa down to 10^-19 MPa at high temperatures accompanied by dilatometry- and XRD-measurements. Furthermore, the present study reveals for the first time a way for reducing and preventing crack formation that may occur during sintering. The present systematic research provides essential fundamental information before performing electrical measurements necessary in order to understand important factors about charge carriers and electrical transport mechanism.     

Origin of high dielectric performance in fine grain-sized CaCu3Ti4O12 materials

We report on high dielectric constant (8.3 × 10³, 10⁴ Hz), low dielectric loss (0.029, 10⁴ Hz) as well as fine grain size (∼840 nm) achieved in pure CaCu₃Ti₄O₁₂ (CCTO) ceramics through a combination of sol–gel method, spark plasma sintering and annealing process. By adjusting the sintering temperature and annealing conditions, the composition variations, valence states and microstructures of CCTO ceramics are systematically studied, which provide direct clues in understanding the origin of their excellent dielectric response. Through the studies on the dielectric, impedance, modulus and conductivity properties of CCTO ceramics, a modified brick-layer model based on two interfacial polarizations originating from sub-grain boundary and grain boundary barriers is proposed to explain their dielectric behaviors. The high dielectric constant of CCTO ceramics is mainly dominated by the sub-grain contribution; and the reduced dielectric loss is attributed to the decreases of electrical conductivity and relaxation loss.     

Gradient microstructure development and grain growth inhibition in high-entropy carbide ceramics prepared by reactive spark plasma sintering

High-entropy carbide ceramics (Ti_0.2Hf_0.2Nb_0.2Ta_0.2W_0.2)C is prepared from five transition metal oxides and graphite by reactive spark plasma sintering. X-ray diffraction indicates the synthesized ceramics with the single-phase face-centered cubic structure. The elemental distribution maps by energy dispersive spectroscopy demonstrate homogeneous distribution of the five metal elements in both central and circumferential regions of the sample. SEM and corresponding back scattered electron observations show the residual graphite particles locating at the grain boundaries of high-entropy carbide ceramics. Moreover, the content of the residual graphite decreases and the grain size of the high-entropy carbide phase increases from central to circumferential region of the sample. Thermodynamic calculation results indicate that gradient gas pressure inside the sample affects the carbothermal reduction reactions during sintering and consequently results in the existence of residual graphite with gradient distribution feature. This study points out an effective way to inhibit the grain growth of high-entropy carbide phase during sintering process by the incorporation of graphite as the second phase particles acting as grain growth inhibitor.     

Improved dielectric and nonlinear properties of CaCu3Ti4O12 ceramics with Cu-rich phase at grain boundary layers

The formation and compositions of grain boundary layers are very important factors to improve the electrical properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics. In present work, the dielectric and nonlinear properties of the CCTO ceramics are enhanced by controlling the Cu-rich phase degree at grain boundary layers. The dense CCTO ceramics were prepared successfully through mixing the nanometer and micrometer powders and using the cold isostatic pressing process. The average grain size of these CCTO ceramics is about 30.71(±11.76) ∼ 62.01(±32.16) μm, and their grain microstructures show the Cu-rich phases at grain boundary layers. The CCTO ceramics with the mass ratios of nanometer and micrometer powders 7:3 display a giant dielectric constant of 5.4 × 10⁴, low dielectric loss of 0.048 at 10³ Hz, enhanced nonlinear coefficients of 11.12, as well as the noteworthy breakdown field of 4466.17 V/cm. The complex impedance spectroscopy results indicate that the giant dielectric behavior is due to the electrically heterogeneous grain/grain boundary characteristics from internal barrier layer capacitance (IBLC) model. The lower dielectric loss and the higher breakdown field are attributed to the high resistance grain boundary layers with the Cu-rich phase. The improved nonlinear properties are related to the increased Schottky barrier height at grain boundary. This work may provide a potential way to design the CCTO ceramics with excellent electrical properties from the viewpoint of controlling the response of the Cu-rich phase grain boundary.     

Stability properties and microstructure properties of microwave-sintered CeO2 doped zirconia ceramics

Nanosized CeO₂–ZrO₂ powders prepared by atmospheric pressure pyrolysis were used as raw materials to prepare CeO₂–ZrO₂ ceramics using microwave sintering. The samples were characterised using bulk density measurements, X-ray diffraction (XRD), Fourier Transform Infrared Spectrometer (FT-IR), Raman, and scanning electron microscopy (SEM). The purpose was to determine the optimised microwave sintering process for CeO₂–ZrO₂ ceramics and reveal the corresponding mechanism. The results show that with a CeO₂ addition content above 5 mol%, the tetragonal phase peak appeared obviously in the sample. The results show that the tetragonal phase peak appears when the CeO₂ content is more than 5 mol%. The dopants, namely CeO₂, have reduced the solid solution's phase transformation temperature with the assistance of microwave heating. Additionally, the grain size of the CeO₂–ZrO₂ ceramics has shown a negative relationship with Ce content at a temperature of 900 °C. The reason is that the rapid sintering due to microwave sintering and the oxygen vacancies generated by CeO₂ can effectively inhibit grain growth. The regulation mechanism on microwave sintering of CeO₂–ZrO₂ ceramic was clarified, and the technical prototype of controlled prepared CeO₂–ZrO₂ ceramics by microwave sintering was constructed.     

Nonlinear I–V electrical behaviour of doped CaCu3Ti4O12 ceramics

In this work a comparative study of undoped CaCu₃Ti₄O₁₂ (CCTO) and doped with Fe³⁺(CCTOF) and Nb⁵⁺(CCTON) ceramics, was aimed to modify the electronic transport. XRD patterns, FE-SEM microstructural analysis, impedance spectroscopy and I–V response curves were afforded to correlate the microstructure with the nonlinear I–V behaviour. The appearance of nonlinear behaviour in doped CCTO samples has been correlated with the ceramic microstructure that consists in n-type semiconductor grains, surrounded by a grain boundary phase based on CuO. The presence of this secondary grain boundary phase is the responsible of the assisted liquid phase sintering in CCTO ceramics. Doped samples showed cleaner grain boundaries than CCTO and nonlinearity in the I–V response.     

Enhanced resistivity and strain stability of BiFeO3–BaTiO3 ceramics by hot-press sintering in oxygen atmosphere

Even though BiFeO₃–BaTiO₃ (BF–BT) with high Curie temperature and excellent piezoelectric properties is very suitable for high-temperature applications, its rapid reduction in resistivity with temperature limits its further application. So far, there is no effective method to improve the resistivity of BF–BT at a high-temperature state. In this work, hot-press sintering combined with an oxygen atmosphere was used to prepare (1 − x)BF–xBT (x = 0.2–0.33) ceramics for the first time, which reduced the sintering temperature from 1000 to 920°C. The controllable grain size can be achieved by adjusting the sintering temperature and the applied pressure. The X-ray photoelectron spectroscopy results confirmed that using hot-press sintering effectively avoided the generation of heterovalent Fe ions, and the resistivity of BF–BT ceramics at the high-temperature stage was improved by two orders of magnitude. It was found that hot-press sintering can cause the oriented growth of the sample along the (1 1 0) direction, and further refined X-ray diffraction was used to accurately analyze the changes in the lattice structure. The hot-press sintered samples obtained larger polarization strength, especially the electro-induced strain showed excellent temperature stability in the wide temperature range of 30–170°C. Hot-pressing sintering combined with an oxygen atmosphere is more suitable for preparing high insulation and electrical breakdown resistance ceramics.     

Effects of strontium/lanthanum co-doping on the dielectric properties of CaCu3Ti4O12 prepared by reactive sintering

The extremely high dielectric constant of the cubic perovskite CaCu₃Ti₄O₁₂ (CCTO) has attracted increasing attention for a variety of capacitive elements in microelectronic device applications. In this research, the influence of Sr and La replacing Ca and Cu, respectively, to simultaneously controlling the intrinsic properties of grain boundaries in a co-doped CCTO ceramic has been investigated. The preparation was done using high purity compounds milled and mixed by mechano-synthesis and further consolidated by reactive sintering without calcination. Characterization by XRD confirmed the formation of single-phase CCTO ceramic and a residual amount CaTiO₃. The microstructure and composition analyzed by SEM/EDX showed a smaller grain size for the co-doped CCTO. Impedance measurements indicated the smallest dielectric loss for the co-doped ceramics compare to pure and single-doped CCTO, while reaching a higher dielectric permittivity than single-doped ceramics. The CCTO-SrLa sample also showed high thermal stability of the dielectric permittivity between 100 and 470?K, and the lowest loss between 200 and 300?K. This behavior was attributed to the lower bulk resistance exhibited by the co-doped sample.     

Phase formation during liquid phase sintering of ZnO ceramics

ZnO doped with Bi₂O₃ and Sb₂O₃ (ZBS), is the basic system for ceramic varistors. Phase formation during sintering of ZBS was measured in situ, using 1 mm thick samples and synchrotron X-rays. Sintering shrinkage was measured in different atmospheres by an optical method. Thermodynamic calculations were performed to explain phase formation, composition, stability of additive oxides and influence of the oxygen fugacity on sintering. Sb₂O₄, pyrochlore, trirutile and spinel were formed at temperatures of 500–800 °C. The oxidation of antimony was controlled by the oxygen partial pressure and affected both, phase formation and sintering kinetics, in the ZBS system.     

Effects of sintering temperature on the internal barrier layer capacitor (IBLC) structure in CaCu3Ti4O12 (CCTO) ceramics

The formation of the internal barrier layer capacitor (IBLC) structure in CaCu₃Ti₄O₁₂ (CCTO) ceramics was found to be facilitated by the ceramic heat treatment. Electrically insulating grain boundary (GB) and semi-conducting grain interior areas were characterized by impedance spectroscopy to monitor the evolution of the IBLC structure with increasing sintering temperature T_S (975–1100 °C). The intrinsic bulk and GB permittivity increased by factors of ≈2 and 300, respectively and the bulk resistivity decreased by a factor of ≈10³. These trends were accompanied by increased Cu segregation from the CCTO ceramics as detected by scanning electron microscopy and quantitative energy dispersive analysis of X-rays. The chemical changes due to possible Cu-loss in CCTO ceramics with increasing T_S are small and beyond the detection limits of X-ray absorption spectroscopy near Cu and Ti K-edges and Raman Spectroscopy.     

Evolution of the intergranular phase during sintering of CaCu3Ti4O12 ceramics

CaCu₃Ti₄O₁₂ (CCTO) ceramics have been processed by solid state reaction and sintered at 1100 °C for different times. A clear increase of the dielectric constant of the material up to values of 6 × 10⁴ has been observed with the sintering time. This increase is accompanied by a limited grain growth and intergranular Cu-oxide phase thickness reduction. The disappearance of the Cu-oxide phase is caused by the incorporation of Cu cations into the grains, contributing to the increase of the dielectric constant. Raman spectroscopy shows the decrease of TiO₆ octahedral rotational modes with the sintering time due to the incorporation of Cu cations into the CCTO grains. XANES measurements show that the Cu main oxidation state is Cu²⁺ and does not change with the sintering time. The fitting of the experimental dielectric constant to the Internal Barrier Layer Capacitance (IBLC) model reveals the change of the intergranular phase dielectric constant, caused by a compositional change due to the incorporation of Cu into the CCTO grains.     

The role of carbon nanotubes on the stability of tetragonal zirconia polycrystals

The effect of single walled carbon nanotubes (SWNT) at zirconia grain boundaries on the stability of a tetragonal zirconia polycrystalline matrix has been explored in as–sintered composites and after low–temperature hydrothermal degradation (LTD) experiments. For this purpose, highly–dense 3?mol% Y₂O₃–doped tetragonal zirconia polycrystalline (3YTZP) ceramics and SWNT/3YTZP composites were prepared by spark plasma sintering (SPS). Quantitative X–ray diffraction analysis and microstructural observations point out that an increasing amount of well–dispersed SWNT bundles surrounding zirconia grains decreases the metastable tetragonal phase retention in the ceramic matrix after sintering. In contrast, the tetragonal ceramic grains in composites with SWNTs are less sensitive to the presence of water, i.e. to undergo a martensitic transformation under LTD conditions, than monolithic 3YTZP ceramics. The SWNT incorporation diminishes micro–cracking due to tetragonal to monoclinic ZrO₂ phase transformation in the composites.     

Development of a lead‐free copper co‐fired BNT‐based piezoceramic sintered at low temperature

Compatibility of Bi‐based piezoelectric ceramic and copper electrodes is demonstrated by co‐firing 0.88Bi_1/2Na_1/2TiO₃–0.08Bi_1/2K_1/2TiO₃–0.04BaTiO₃ (BNKBT88) with copper. A combination of Bi₂O₃, CuO, ZnO, Li₂CO₃, and B₂O₃ are used as additives to reduce firing temperature to 900°C with minimal effect on the electromechanical properties compared to sintering at 1150°C without additives. Co‐firing with copper electrodes requires controlled oxygen sintering at low temperature. The atmosphere is controlled using carbon dioxide and hydrogen gas to maintain an oxygen partial pressure of 6.1 × 10^?8 atm, which is necessary for the coexistence of Cu metal and Bi₂O₃. The thermodynamic activity of bismuth oxide in BNKBT88 is calculated to be 0.38. BNKBT88 ceramics were successfully co‐fired with internal as well as surface Cu metal electrodes. The copper co‐fired ceramics were successfully polarized and the dielectric and piezoelectric properties are evaluated.     

Giant dielectric constant,dielectric relaxations,and tunable properties of Sm2/3Cu3Ti4O12 ceramics

The polycrystalline Sm_2/3Cu₃Ti₄O₁₂ (SCTO) ceramics have been prepared by solid-state reaction. The crystallinity of the compound has been investigated by Rietveld refinement which has revealed a cubic structure with space group Im3. It is observed that at low frequencies, SCTO ceramic exhibits tremendously high values of dielectric permittivity ε′, larger than 32,000, at room temperature. Two distinct, thermally triggered, dielectric relaxations have been noted. This mechanism has been confirmed through impedance analysis of the ceramics. The complex impedance plane shows three semicircles, which confirm the existence of two dielectric relaxations in SCTO ceramics. In general, the electrical as well as dielectric behavior of SCTO ceramics are seen to be reasonably analogous to those of CaCu₃Ti₄O₁₂ (CCTO) ceramics. The emergence of the enormous dielectric constant in SCTO ceramic is accredited to the combined effect of polarization both at the sample-electrode interface as well as at the insulating grain boundary interface. The SCTO ceramics are identical to the CCTO ceramics in their structure and composition and hence, as the above results indicate, the IBLC effect mechanism, originally put forward for CCTO ceramics, is furthermore plausible to account for the mammoth values of dielectric constant in SCTO ceramics.     

Influence of Zn doping on microstructures and dielectric properties in CaCu3Ti4O12 ceramic synthesised by semiwet route

Abstract

A single phase of calcium copper titanate [CaCu₃Ti₄O₁₂ (CCTO)] was produced at lower temperature and shorter calcination time via a novel semiwet route. Undoped CCTO and zinc doped CaCu_3?xZn_xTi₄O₁₂ samples with x?=?0·10, 0·20 and 0·30 were prepared by this method for the first time using solid TiO₂ powder in metal nitrate solutions. The CaCu_3?xZn_xTi₄O₁₂ ceramics were characterised by thermogravimetric/differential thermal analysis, X-ray diffraction, SEM and EDX techniques. The SEM images of the sintered CaCu_3?xZn_xTi₄O₁₂ ceramics showed average grain size in the ranges of 2–6, 8–13, 12–16 and 14–20 μm for x?=?0·00, 0·10, 0·20 and 0·30 respectively. Energy dispersive X-ray spectroscopy studies confirm the purity of parent and Zn doped CCTO ceramics. At room temperature, the dielectric constants of Zn doped CCTO are always higher than pure CCTO. CaCu_3?xZn_xTi₄O₁₂ (x?=?0·20) ceramic has the maximum value of ?_r≈4347 along with the minimum value of tan?δ≈0·14 at 1 kHz.