Enhanced relative permittivity in niobium and europium co-doped TiO2 ceramics

The appearance of colossal permittivity materials broadened the choice of materials for energy-storage applications. In this work, colossal permittivity in ceramics of TiO₂ co-doped with niobium and europium ions ((Eu_0.5Nb_0.5)_xTi_1-xO₂ ceramics) was reported. A large permittivity (ε_r ～ 2.01?×?10⁵) and a low dielectric loss (tanδ ～ 0.095) were observed for (Eu_0.5Nb_0.5)_xTi_1-xO₂ (x?=?1%) ceramics at 1?kHz. Moreover, two significant relaxations were observed in the temperature dependence of dielectric properties for (Eu, Nb) co-doped TiO₂ ceramics, which originated from defect dipoles and electron hopping, respectively. The low dielectric loss and high relative permittivity were ascribed to the electron-pinned defect-dipoles and electrons hopping. The (Eu_0.5Nb_0.5)_xTi_1-xO₂ ceramic with great colossal permittivity is one of the most promising candidates for high-energy density storage applications.     

Ionic conduction,colossal permittivity and dielectric relaxation behavior of solid electrolyte Li3xLa2/3-xTiO3 ceramics

Perovskite-type solid electrolyte lanthanum lithium titanate (LLTO), exhibiting high intrinsic ionic conductivity, has been attracting interests because of its potential use in all solid-state lithium-ion batteries. In this work, we prepared LLTO ceramics by solid state reaction method and studied their conductivity and dielectric properties systematically. It is found that the bulk conductivity of LLTO is several orders of magnitude higher than the grain boundary conductivity. In addition, colossal permittivity was observed in LLTO ceramics in wide frequency/temperature ranges. Two non-Debye type relaxation peaks were observed in the imaginary part of permittivity, resulting from Li⁺ ions motion and accumulation near interfaces of grains/grain boundaries/electrodes. It is suggested that colossal permittivity may originate from the lithium ion dipoles inside the samples and the interfacial polarization of lithium ion accumulation near the grain boundaries. These results clarify the relations among colossal permittivity, relaxation behavior and ionic conduction in solid ion conductor ceramics.     

Low dielectric loss,colossal permittivity,and high breakdown electric field in Al-doped Y2/3Cu3Ti4O12 ceramics

The miniaturization and high capacitance of electronic components are driving the development of high-performance electronic ceramic materials. In this work, we design a new strategy to achieve satisfactory dielectric properties with low loss, colossal permittivity, and a high breakdown electric field (E_b) in Al-doped Y_2/3Cu₃Ti₄O₁₂ (YCTO) ceramics prepared by a solid-phase synthesis method. The dielectric loss decreased with Al doping in the YCTO. The dielectric constant and the E_b were improved upon Al doping. With Al doping levels of 0.03 and 0.05, Y_2/3Al_0.03Cu_2.97Ti₄O₁₂ and Y_2/3Al_0.05Cu_2.95Ti₄O₁₂ ceramics displayed, respectively, a suppressed loss tangent of about 0.028 and 0.031, a high dielectric constant of approximately 9540 and 11792, and an E_b of approximately 4.32 and 4.54 kV/cm. The improved dielectric properties of the produced ceramics were closely linked to enhanced grain boundaries resistance. This study explores the physical mechanism behind the high performance of the YCTO-based ceramics, and also provides theoretical support for the application of devices comprising YCTO and related materials.     

Colossal dielectric permittivity in (Al+Nb) co-doped Ba0.4Sr0.6TiO3 ceramics

Stimulated by the outstanding colossal permittivity behavior achieved in trivalent and pentavalent cations co-doped rutile TiO₂ ceramics, the co-doping effects on the dielectric behavior of Ba_0.4Sr_0.6TiO₃ ceramics were further explored. In this work, (Al + Nb) co-doped Ba_0.4Sr_0.6TiO₃ ceramics were synthesized via a standard solid state ceramic route. The structural evolution was analyzed using X-ray diffraction patterns and Raman spectra. Dense microstructures with no apparent change of grain morphology were observed from the scanning electron microscopy. A huge enhancement of dielectric permittivity was obtained with 1 mol% (Al + Nb) doping and excellent dielectric performances (ε_r ∼ 20,000, tanδ ∼ 0.06 at 1 kHz) were achieved after further heat treatment. The formation of electron pinned defect dipoles localized in grains may account for the optimization of dielectric behaviors and the corresponding chemical valence states were confirmed from the XPS results.     

Disappearance and recovery of colossal permittivity in (Nb+Mn) co-doped TiO2

We investigate the effects of doping and annealing on the dielectric properties of metal ions doped TiO₂ ceramics. Colossal permittivity (CP) above 10⁴ was observed in single Nb ion doped TiO₂, which was dominated by electron transport related interfacial polarization. Moreover, the CP can be dropped to 120 when simultaneously introducing Mn ion into the sample. The disappearance of CP behaviors maybe due to the multivalence of Mn which would inhibit the reduction of Ti⁴⁺ to Ti³⁺, and thus reduce delocalized electrons. Interestingly, the CP was recovered for the (Nb+Mn) co-doped TiO₂ after post-sintering heat treatment in N₂ atmosphere. The recovery of CP in the sample after annealing can be ascribed to the semiconducting grain and the insulating grain boundary, according to impedance spectroscopy. We therefore believe that this work can help us understand the mechanism of CP from a new perspective.     

Colossal permittivity in Ta-doped SrTiO3 ceramics induced by interface effects and defect structure: An experimental and theoretical study

The lack of systematic research on the phase structure, defect structure, and polarization mechanism hinders the full comprehension of the colossal permittivity (CP) behavior for SrTiO₃-based ceramics. For this purpose, Ta-doped SrTiO₃-based ceramics were synthesized in an N₂ atmosphere with a traditional method. When the appropriate amount of Ta was doped, colossal permittivity (ԑ_r ∼ 62505), low dielectric loss (tanδ ∼ 0.07), as well as excellent temperature stability (−70 °C–180 °C, ΔC/C_25°C ≤ ±15%) were obtained in the Sr_0.996Ta_0.004TiO₃ ceramic. The relationship between Ta doping, polarization mechanism, and dielectric performance was systematically researched according to experimental analysis and theoretical calculations. The first-principle calculations indicate that the Ta⁵⁺ ion prefers to replace the Sr-site. The defect dipoles and oxygen vacancies formed by heterogeneous-ion doping play an active role in regulating the dielectric performance of ceramics. In addition, the interface barrier layer capacitance (IBLC) effect associated with semi-conductive grains and insulating grain boundaries is the primary origin of colossal permittivity for Sr_1-xTa_xTiO₃ ceramics. The polarization mechanism and defect structure proposed in the study can be extended to the research of SrTiO₃ CP ceramics. The results have a good development prospect in colossal permittivity (CP) materials.     

Universal dielectric relaxation induced giant dielectric permittivity in Mn-doped PbZrO3 ceramics

Manganese-doped lead zirconate ceramics were prepared by a conventional solid reaction method. Although the doping content varies from 5% (mole) to 20% (mole), significantly enhanced universal dielectric relaxation occurs only in 5% Mn-doped lead zirconate. The behavior cannot be properly explained by Maxwell-Wagner relaxation, which is commonly used for explaining giant dielectric permittivity in electroceramics. It is found that the enhanced giant dielectric permittivity is related to hetero-valence cation doping induced universal dielectric relaxation.     

Co-doping effects of A-site Y3+ and B-site Al3+ on the microstructures and dielectric properties of CaCu3Ti4O12 ceramics

Different doping elements have been used to reduce the dielectric losses of CaCu₃Ti₄O₁₂ ceramics, but their dielectric constants usually are undesirably decreased. This work intends to reduce their dielectric losses and simultaneously enhance their dielectric constants by co-doping Y³⁺ as a donor at A site and Al³⁺ as an acceptor at B site for substituting Ca²⁺ and Ti⁴⁺, respectively. Samples with different doping concentrations x = 0, 0.01, 0.02, 0.03, 0.05 and 0.07 have been prepared. It has been shown that their dielectric losses are generally reduced and their dielectric constants are simultaneously enhanced across the frequency range up to 1 MHz. The doped sample with x = 0.05 exhibits the highest dielectric constant, which is well over 10⁴ for frequency up to 1 MHz and is about 20% higher than the undoped sample. Impedance spectra indicate that the doped samples have much higher grain boundary resistance than the undoped one.     

Double pentavalent (Sb5+, Nb5+) and trivalent (Sm3+, Y3+) co-doped Ti0.9Zr0.1O2 colossal dielectric permittivity multilayer ceramics for the miniaturization of the next-generation electronics

Materials with colossal dielectric permittivity (CP) are in the focus of interest for the development of miniaturization and integration of electronic components. Despite the extensive study of these new classes of co-doped TiO₂ CP materials, the preparation of multilayer ceramics using this kind of CP materials is still challenging work. Here, we synthesize a series of (Sb⁵⁺, Nb⁵⁺) and (Sm³⁺, Y³⁺) co-doped Ti_0.9Zr_0.1O₂ ceramics (SNSYTZO) through the conventional solid-state reaction method. XRD spectrum identifies that ceramics under x = 0.04 show a perfect rutile phase with the tetragonal crystal structure; however, minor brookite orthorhombic crystal structure appears when x > 0.04. FESEM images show the prepared ceramics have excellent densification and low porosity. Dielectric, modulus, and impedance spectrum are systematically explored the underlying CP mechanism and compared with each other to find the optimal materials composition to prepare further multilayer ceramics, which is fabricated by the industrial tape casting method. FESEM, together with surface element mapping, indicates that all doping elements are homogeneously distributed. Also, we investigate the dielectric response without/with DC bias. This work sheds light on a promising feasible route to prepare the miniaturization of the next-generation electronics via a large scale industrial tape casting method.     

Colossal dielectric properties of Na1/3Ca1/3Sm1/3Cu3Ti4O12 ceramics: Computational and experimental investigations

A modified sol?gel technique was used to synthesize a high dielectric ceramic, Na_1/3Ca_1/3Sm_1/3Cu₃Ti₄O₁₂. The crystal structure of this sintered ceramic matches the standard pattern of a body?centered cubic (bcc) system within the Im3 space group (JCPDS No. 75–2188). No impurity phases were observed. Interestingly, a high dielectric permittivity of ～1.14–1.35 × 10⁴ and a low loss tangent of ～0.027–0.039 were achieved in this sintered Na_1/3Ca_1/3Sm_1/3Cu₃Ti₄O₁₂ ceramic. Our DFT calculations disclosed that substitution of Na⁺ ions at Cu²⁺ sites causes an observed excess Cu concentration. As a result, metastable insulating phases were formed at a relatively high sintering temperature. Additionally, our electron density calculations revealed that Na ions lose their electrons to Sm ions, whereas the oxidation states of Cu and Ti are unaltered. Our results show that Cu⁺ and Ti³⁺ were observed after introducing an oxygen vacancy into this lattice. Significantly different values of R_g, R_gb, and E_g, E_gb support an internal barrier layer capacitor as the most likely origin of the giant dielectric properties of this ceramic. XPS results show mixed Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ in all ceramics, suggesting that electron hopping between Cu⁺?Cu²⁺ and Ti³⁺?Ti⁴⁺ is the probable origin of the n?type semiconducting state inside the grains.     

Abnormal dielectric relaxations and giant permittivity in SrTiO3 ceramic prepared by plasma activated sintering

In this study, the dielectric properties of SrTiO₃ ceramics prepared by plasma-activated sintering (PAS) were investigated. One of the striking findings is that the material exhibits giant room temperature permittivity (k∼3.5 × 10⁴) and low dielectric loss (∼0.05) at 1 kHz, with the permittivity exceeding that of the conventionally prepared SrTiO₃（ST） ceramics (k∼300) by two orders of magnitude. The enhancement of the polarizability was caused by the high concentration of defect dipoles. In this paper, two dielectric relaxation modes of the PAS ceramics below 0°C have been mainly discussed. One dielectric relaxation mode showed higher activation energy than that of the dielectric peak in the same temperature range for the conventional SrTiO₃-based ceramics. This mode was sensitive to humidity, and the strength of this mode was associated with the oxygen vacancies concentration in the ceramics. The other mode exhibited abnormal slowing down of relaxation rate with increasing temperature, which is contrary to the typical dielectric relaxation behavior, and the anomaly persisted over a narrow temperature range. Both modes were observed at the same interface between the grain and grain boundaries.     

Dielectric and electric relaxations induced by the complex defect clusters in (Yb+Nb) co‐doped rutile TiO2 ceramics

The effect of the Yb+Nb substitution for Ti on the microstructure, crystal structures, and dielectric properties of (Yb_1/2Nb_1/2)_xTi_1?xO₂ (0.01≤x≤0.1) ceramics is investigated in this study. The results reveal that the solid solubility limit of the (Yb_1/2Nb_1/2)_xTi_1?xO₂ ceramics is x=0.07, and the average grain sizes considerably decrease from 12 μm to 6 μm with x increasing from 0.01 to 0.1. Three types of dielectric relaxations are observed at temperature ranges of 10‐30 K, 80‐180 K, and 260‐300 K, caused by the electron‐pinned defect dipoles, polaron hopping, and interfacial polarizations, respectively. The conduction mechanism changes from nearest‐neighbor‐hopping to polaron hopping mechanism, which is confirmed by ac conductivity measurements. The present work indentifies the correlation between the colossal permittivity and polaron hopping process in the titled compound.     

Colossal permittivity and ultralow dielectric loss in (Nd0.5Ta0.5)xTi1-xO2 ceramics

Giant permittivity ceramic is one of the most significant classes of material to realize the miniaturization and integration of a high-performance capacitor. In this paper, to realize good giant dielectric properties, the (Nd_0.5Ta_0.5)_xTi_1-xO₂ ceramics (NTTO x = 0.005, 0.01, 0.03, 0.05) were synthesized by a standard conventional solid-state reaction. Comparing with the previous co-doped TiO₂ ceramics giant permittivity material system, NTTO ceramics perform extremely colossal permittivity and ultralow dielectric loss (1%NTTO: ε = 82052, tanδ = 0.008 at 1 kHz; 5%NTTO: ε = 170131, tanδ = 0.090 at 1 kHz). The broad distinction of the dielectric behavior between the (Nd_0.5Ta_0.5)_xTi_1-xO₂ ceramics can be explained by the impedance analysis and the calculated polarization activation energies. The main electron-pinned defect-dipole (denoted as EPDD) polarization corresponds to the ultralow loss, embodying in the maximum value of E_gb (the activation energy of the grain boundary), E_a2 (the EPDD polarization activation energies) and the minimum value of E_a1 (the total polarization activation energies). Though the interfacial polarization can cause the permittivity increase, it can also give rise to poor frequency stability and higher loss.     

Dielectric properties with high dielectric permittivity and low loss tangent and nonlinear electrical response of sol-gel synthesized Na1/2Sm1/2Cu3Ti4O12 perovskite ceramic

Giant dielectric ceramic, Na_1/2Sm_1/2Cu₃Ti₄O₁₂, was successfully prepared by a modified sol-gel method. X-ray diffraction experiments indicated that a body-centered cubic structure with a space group of Im3 was obtained. Our density functional theory calculations revealed that codoping Na and Sm in the CaCu₃Ti₄O₁₂ structure resulted in charge compensation between Na and Sm ions in this structure, whereas the oxidation states of Cu and Ti were unaltered. Giant dielectric permittivity ～7.21 × 10³ - 8.04 × 10³ and low dielectric loss tangent ～0.045–0.049 were accomplished at a sintering temperature of 1050 °C for 12–18 h. Nonlinear J - E property with breakdown electric field ～5.13 – 5.78 × 10³ V/cm and nonlinear coefficient ～6.08–6.82 were also achieved. The n-type semiconducting grain originated from short-range migrations of mixed Cu⁺/Cu²⁺ and Ti³⁺/Ti⁴⁺ charges. Finally, our charge analysis showed that the occurrence of Cu⁺ and Ti³⁺ was related to the existence of oxygen vacancy in these ceramics.     

High permittivity and low dielectric loss of the (Ca0.9Sr0.1)1-xLa2x/3Cu3Ti4O12 ceramics

In this work, we have systematically studied the effects of La³⁺/Sr²⁺ dopants on the crystal structure, microstructure, dielectric response and electrical properties of (Ca_0.9Sr_0.1)_1-xLa_2x/3Cu₃Ti₄O₁₂ (x = 0, 0.025, 0.05 and 0.075) ceramics. XRD results show that the lattice parameter increases with the increase in the La³⁺ content. SEM micrographs illustrate that a small amount added of La³⁺ can reduce the grain size of CCTO during sintering. With increasing La³⁺ content, the grains grow larger. Dielectric measurements indicated that all doped samples synthesized by the solid-state reaction exhibit giant dielectric constants ε'>10⁴ over a large frequency range (10 Hz to 1 MHz) and at any temperature below 600 K. In particular, the ceramic with x = 0.05 exhibits a colossal dielectric permittivity ～5.49 × 10⁴; which increases by about 50% compared to that of the undoped ceramic. In addition, the doped ceramic also presents a low dielectric loss ～ 0.08 at 20 °C and 0.6 kHz. The giant dielectric properties of these samples can be explained by the (IBLC) model.     

Enhanced intrinsic permittivity and bulk response in Y2/3Cu3Ti4+xO12 ceramics

Considering the contribution of the mixed valence structure of Ti³⁺ and Ti⁴⁺ to the semiconductivity of grain, compositions with the formula of Y_2/3Cu₃Ti_4+xO₁₂ were designed and prepared. The dielectric bulk responses of Y_2/3Cu₃Ti_4+xO₁₂ ceramics were explored in detail. Changing Ti stoichiometry gives rise to an increase of the intrinsic permittivity. Y_2/3Cu₃Ti_3.925O₁₂ ceramic exhibits a higher intrinsic permittivity of ~120 at 60 MHz than that of pure Y_2/3Cu₃Ti₄O₁₂ ceramics (87 at 60 MHz). Additionally, the activation energies of bulk responses are significantly enhanced by changing Ti stoichiometry, which is closely linked with the increase of Ti³⁺/Ti⁴⁺.     

Colossal dielectric permittivity and relevant mechanism of Bi2/3Cu3Ti4O12 ceramics

Bi_2/3Cu₃Ti₄O₁₂ (BCTO) ceramics with pure perovskite phase were successfully prepared by traditional solid-state reaction technique. Uniformly distributed and dense grains with the grain size of 2–3 μm were observed by SEM. A giant low-frequency dielectric permittivity of ~3.3×10⁵ was obtained. The analysis of complex impedance revealed that Bi_2/3Cu₃Ti₄O₁₂ ceramics are electrically heterogeneous. There are three kinds of dielectric response detected in Bi_2/3Cu₃Ti₄O₁₂ ceramics, which existed in the low-frequency range, middle-frequency range, and high-frequency range, respectively. Through the study of dielectric spectrum at different temperatures, the relatively low activation energy of 0.30 eV for middle-frequency dielectric response was calculated, which suggested that this Middle-frequency dielectric response can be ascribed to grain boundaries response. In view of the analysis of dielectric spectrum at low temperatures, the activation energy of 0.07 eV for high frequency dielectric response was found. This value illustrated that dielectric response at high frequencies was associated with grains polarization effect. The comparison of dielectric spectra of Bi_2/3Cu₃Ti₄O₁₂ ceramics with different types of electrodes revealed that giant low-frequency dielectric constant was attributed to the electrode polarization effect.     

Perovskite stabilization in Fe- and Mg-doped Pb(Zn1/2W1/2)O3 and their dielectric characteristics

Stabilization of a perovskite structure by solid-state reaction in as-yet unreported Pb(Zn_1/2W_1/2)O₃ ceramics was attempted with compositional modification. A wide range of fractions of Pb(Fe_2/3W_1/3)O₃ were initially introduced into the host material, and 20?mol% Pb(Mg_1/2W_1/2)O₃ was subsequently added to the resulting composition in order to enhance perovskite formation. The perovskite development yield of 62.5% (without any fraction of Pb(Fe_2/3W_1/3)O₃ introduced) increased with Pb(Fe_2/3W_1/3)O₃ contents and finally reached 99.9%. The lattice parameters of the perovskite structure in the cubic symmetry range decreased steadily from 0.4002 to 0.3979?nm with increasing Pb(Fe_2/3W_1/3)O₃. The relative permittivity values of the ceramics increased from 72 to 4910 (1?MHz) with increasing Pb(Fe_2/3W_1/3)O₃. By contrast, the dielectric maximum temperatures in the cubic perovskite range changed only slightly from -111 to ?124?°C (1?MHz), quite insensitive to the compositional modification. Meanwhile, the phase transition changed gradually from sharp to diffuse modes with the Pb(Fe_2/3W_1/3)O₃ substitution.     

Composition dependent structure,dielectric and energy storage properties of Pb(Tm1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3 antiferroelectric ceramics

In order to stabilize the perovskite structure and improve the storage energy density (U) of Pb(Tm_1/2Nb_1/2)O₃ (PTmN) based materials, Pb(Mg_1/3Nb_2/3)O₃ (PMN) was introduced into PTmN to form binary (1-x)PTmN-xPMN solid solution ceramics. The XRD patterns show that all the compositions belong to orthorhombic phase with space group Pbnm. The Curie temperature (T_C) gradually decreases while the dielectric constant (ε') increases for (1-x)PTmN-xPMN with increasing PMN content. The ε' of each composition above T_C obeys the Curie-Weiss law. The appearance double hysteresis loop confirms the antiferroelectric nature of (1-x)PTmN-xPMN (x = 0.02–0.18) ceramics. With the increase of PMN concentration, the maximum polarization slowly increases from 8.58 μC/cm² to 29.5 μC/cm² while the threshold electric field (E_A-F) gradually declines from 290 kV/cm to 120 kV/cm. The maximum of U (3.12 J/cm³) is obtained in 0.92PTmN-0.08PMN ceramic with moderate E_A-F = 220 kV/cm, which makes (1-x)PTmN-xPMN ceramics safe in practical application.