Low-temperature Maxwell-Wagner relaxation in (Na + Nb) co-doped rutile TiO2 colossal permittivity ceramics

The exact mechanism of the stunning colossal permittivity behavior found in (donor-acceptor) co-doped TiO₂ system still remains enigmatic. This behavior results from a thermally activated dielectric relaxation occurring below 50 K. Herein, thermally stimulated depolarization current analysis combined with dielectric investigation was used to disentangle this relaxation in (Na + Nb) co-doped TiO₂ ceramics. We find that this relaxation is related to frozen electrons and features the Vogel-Fulcher behavior and negative dielectric tunability. Our results reveal that this low-temperature relaxation is a new kind of Maxwell-Wagner relaxation. Differences between the low-temperature Maxwell-Wagner relaxation and its high-temperature counterpart are discussed. This study provides new insights into the physics of the eye-catching dielectric properties in co-doped TiO₂ system.     

Giant permittivity up to 100 MHz in La and Nb co-doped rutile TiO2 ceramics

Dielectric spectroscopy was carried out for reduced and stoichiometric La_0.0025Nb_0.0025Ti_0.995O₂ ceramics synthesized by sintering in different atmospheres. A giant permittivity (~1 × 10⁴) was obtained at a frequency of 100 MHz and temperature range from 170 to 350 K. Three dielectric relaxation mechanisms were observed within the temperature range of 10-300 K via dielectric spectroscopy. A low temperature dipole relaxation peak (in the temperature range of 10-30 K) in the spectra was identified to be associated with the giant permittivity specifically measured at 100 MHz. The origin of such giant permittivity was attributed to dipole orientation polarization. Hopping polaron and interfacial effect contributed to giant permittivity. After annealing treatment, all the relaxation contributions were weakened. Low dielectric loss was attributed to high resistance of grain and grain boundaries. Annealing in ambient conditions led to decreased relaxation times which gives the signature of decreased concentration of oxygen vacancies and Ti³⁺. Dipoles which were related to oxygen vacancies and Ti³⁺, resulted in giant permittivity up to 100 MHz.     

The dielectric properties for (Nb,In,B) co-doped rutile TiO2 ceramics

Recently, colossal permittivities (~10⁵) and low loss factors (<0.1) were reported in (Nb+In) co-doped rutile TiO₂ ceramics, which have attracted considerable attention. In this work, (Nb,In,B) co-doped rutile TiO₂ ceramics were investigated for achieving temperature- and frequency- stable dielectric properties in TiO₂ based colossal dielectric ceramics. The (Nb,In,B) co-doped rutile TiO₂ ceramics were prepared by conventional solid-state reaction method. The microstructures, dielectric properties and complex impedance of 1 mol.% (Nb+In) co-doped rutile TiO₂ (TINO) and xwt% B₂O₃ (x=0.5, 1, 2 and 4) doped TINO were systematically investigated and compared. It was found that by doping B₂O₃ the sintering temperature of TINO ceramics can be reduced by 100 °C. Meanwhile, the dielectric loss of TINO ceramics was decreased by doping B₂O₃. In the ₂wt% B₂O₃ doped TINO ceramics, the dielectric permittivity kept a high value of >2.0×10⁵ and the dielectric loss was lower than 0.1 in a frequency range of 10²−10⁵ Hz and a temperature range of 25–200 °C.     

Colossal permittivity of (Li,Nb) co-doped TiO2 ceramics

In this work, (Li, Nb) co-doped TiO₂ ceramics (LNTO_x, x?<?0.1), were synthesized through a conventional solid state reaction method. As revealed by X-ray diffraction (XRD) spectra, all LNTO ceramics exhibited pure tetragonal rutile structure. The LNTO_0.01 ceramic showed a colossal permittivity over 7000 and a low dielectric loss (tgδ?<?0.06) in a wide frequency range of 10²?Hz–10⁷?Hz. The dielectric spectra under DC biases were tested at different temperatures. The experimental data could fit the modified Debye equation well. It was found that there are multiple dielectric polarization mechanisms in LNTO ceramics including space charge polarization, relaxor-type relaxation, polaron hopping and dipole polarization related with localized electrons.     

Large-size-mismatch co-dopants for colossal permittivity rutile TiO2 ceramics with temperature stability

Colossal permittivity (CP) in donor-accepter co-doped rutile TiO₂ has attracted significant interest. Here, the CP behavior of (Ta?+?La) co-doped rutile TiO₂ ceramics were studied, where the ionic radii of Ta⁵⁺ and La³⁺ are much larger than that of Ti⁴⁺. The ceramics with an extremely low doping exhibit colossal dielectric permittivity (～2.6?×?10⁴) with an acceptable low dielectric loss (<0.07) in the frequency range from 40 to 10⁶?Hz. The CP properties obtained in (Ta?+?La) co-doped TiO₂ ceramics show excellent temperature stability over a wide temperature range of 20–400?°C. The X-ray diffraction analysis and the density functional theory calculation illustrates that the La₂³⁺${\text{V}}_{\text{o}}^{??}$Ti₂³⁺ and Ta₂⁵⁺Ti³⁺Ti⁴⁺ defect complexes with the lowest energy are responsible for the enhanced dielectric properties. Moreover, the defect complex formed by large-size trivalent substitutions and oxygen vacancy is very stable, and assists in improving temperature stability of the dielectric properties of co-doped rutile TiO₂ ceramics.     

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.     

Influence of Zr dopant on polarization in rutile (In0.5Nb0.5)0.005(Ti1-xZrx)0.995O2 ceramics

(In_0.5Nb_0.5)_0.005(Ti_1-xZr_x)_0.995O₂ (INZT, x = 0-0.10) ceramics were synthesized using a conventional sintering method, and the effects of Zr content on the microstructures, dielectric properties and electron-pinned defect-dipoles (EPDD) polarization of the resultant products were investigated. The solubility limit of INZT was x = 0.075, and a secondary ZrTiO₄ phase appeared at x = 0.10. Ceramics with x = 0-0.10 exhibited excellent dielectric properties, ie, colossal permittivity (CP, εʹ > 10³) and low dielectric loss (tanδ < 0.1), over a wide range of frequencies (10⁰-10⁶ Hz at 300 K) and temperatures (50-350 K at 1 kHz). The dielectric spectra and XPS results confirmed that the CP property of the ceramics could be ascribed to their EPDD polarization. The activation energy (E_a) for EPDD polarization was continuously enhanced by increasing x values. EPDD relaxation parameters at different x values were revealed using Cole-Cole equation fitting. Moreover, α, which characterize the relaxation time τ distribution, increased with x values, thus indicating that Zr was involved in and affected electron localized states. The high E_a, temperature T_p of the peak εʹʹ at 1 kHz, and dielectric relaxation time τ_p at 30 K were related to increases in hopping distance of electrons among defect clusters with Zr addition.     

Effect of ionic radius on colossal permittivity properties of (A,Ta) co-doped TiO2 (A= alkaline-earth ions) ceramics

(A, B) co-doped TiO₂ ceramics attract great interests due to the excellent dielectric properties. In this work, the (A, Ta) co-doped TiO₂ ceramics were prepared by a solid state reaction process. The effect of the acceptors ionic radius on the structure and properties of TiO₂ ceramics was investigated. According to XRD analysis, the main phase is rutile TiO₂ for all samples. Due to the larger ionic radius, it is hard to replace Ti site in TiO₆ octahedron. As a result, the content of the secondary phase increased with increasing ionic radius. The dielectric properties were significantly enhanced by co-doping of alkaline-earth ions and tantalum ions, and the best dielectric constant obtained at 3% (Sr, Ta) co-doped compositions, where ε’ = 2.1 × 10⁵, tanδ = 0.21. Meanwhile, the XPS analysis suggested that the concentration of the defect dipoles exhibit a maximum in Sr-doped TiO₂ ceramics. The larger ionic radius of the acceptors leads to the more stability of the defect structure. However, for Ba ions, the replacement concentration decreased due to the excessive ionic radius, which in turn reduces the defect concentration. This work is meaningful for the further investigations on TiO₂-based colossal permittivity materials.     

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 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.     

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.     

(Ca,Ta)共掺杂TiO2陶瓷巨介电性能及机理

随着社会的飞速发展,微电子器件的功能不断向一体化方向发展,使开发具有高介电常数、低介电损耗、良好频率和温度稳定性的高介电陶瓷受到越来越多的关注.本工作通过固相反应烧结法制备了(Ca,Ta)共掺杂的TiO2陶瓷.采用X射线衍射仪(XRD)、扫描电镜(SEM)及能谱分析仪(EDS)、阻抗分析仪、X射线光电子能谱(XPS)等...     

Colossal permittivity and impedance analysis of tantalum and samarium co-doped TiO2 ceramics

In this study, (Ta_0.5Sm_0.5)_xTi_1−xO₂ (x = 0, 0.02, 0.06, 0.15) ceramics (referred to as TSTO) were fabricated by a standard solid-state reaction. As revealed by the X-ray diffraction (XRD) spectra, the TSTOs exhibit a tetragonal rutile TiO₂ structure. All the TSTO ceramics display colossal permittivity (~ 10²–10⁵). Moreover, the optimal ceramic, (Ta_0.5Sm_0.5)_0.02Ti_0.98O₂, exhibits high performance over a wide temperature range from 20 °C to 160 °C. At 1 kHz, the dielectric constant and dielectric loss are 2.30 × 10⁴ and 0.11 at 20 °C; they are 3.85 × 10⁴ and 0.64 at 160 °C. Dielectric and impedance spectra analyses for the TSTO ceramics indicate that the CP behavior over a broad temperature range in (Ta+Sm) co-doped TiO₂ could be explained by the internal barrier layer capacitance (IBLC) model, which consists of semiconducting grains and insulating grain boundaries.     

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 permittivity in TiO2 co‐doped by donor Nb and isovalent Zr

Effect of isovalent Zr dopant on the colossal permittivity (CP) properties was investigated in (Zr + Nb) co‐doped rutile TiO₂ ceramics, i.e., Nb_0.5%Zr_xTi_1?xO₂. Compared with those of single Nb‐doped TiO₂, the CP properties of co‐doped samples showed better frequency‐stability with lower dielectric losses. Especially, a CP up to 6.4 × 10⁴ and a relatively low dielectric loss (0.029) of x = 2% sample were obtained at 1 kHz and room temperature. Moreover, both dielectric permittivity and loss were nearly independent of direct current bias, and measuring temperature from room temperature to around 100°C. Based on X‐ray photoelectron spectroscopy, the formation of oxygen vacancies was suppressed due to the incorporation of Zrions. Furthermore, it induced the enhancement of the conduction activation energy according to the impedance spectroscopy. The results will provide a new routine to achieve a low dielectric loss in the CP materials.     

Influence of the electric field on flash-sintered (Zr + Ta) co-doped TiO2 colossal permittivity ceramics

In the preparation process for advanced ceramics, how to reduce the sintering temperature, shorten the processing time and refine grains is the key to obtaining high-performance ceramic materials. The flash sintering (FS) provides an effective method to solve this issue. Here, (Zr + Ta) co-doped TiO₂ colossal permittivity ceramics were successfully fabricated by conventional sintering (CS) and flash sintering under electric fields from 500 V/cm to 800 V/cm. The flash behavior, sintered crystal structure and microstructure, dielectric properties, and varistor characteristics were systematically investigated. The effects of the applied electric fields on the above behaviors were discussed. The results show that flash sintering can reduce the sintering temperature by 200 °C, decrease the processing time by 10 times and reduce grain sizes in TiO₂ ceramics. All sintered samples were single rutile structures. Flash sintering led to similar electrical properties to conventional sintering. In the flash-sintered samples, with increasing the electric field, the permittivity of co-doped TiO₂ ceramics increased at a frequency of 10³–10⁴ Hz. The flash-sintered sample under an electric field of 800 V/cm possessed the best comprehensive properties, a dielectric permittivity of >10⁵, a dielectric loss of ～0.77 at 10³ Hz, and a nonlinear coefficient of 5.2.     

An investigation into the enhanced permittivity properties of Zr co-doped (Ga0.5Nb0.5)0.03Ti0.97O2 ceramics

Dielectric materials with high permittivity and low dielectric loss have a range of promising applications within electronic devices. Here, we report on Zr co-doped (Ga_0.5Nb_0.5)_0.03Ti_0.97O₂ ceramics, fabricated using a solid-state reaction. The colossal permittivity (CP) of (Ga_0.5Nb_0.5)_0.03-(Zr_xTi_1-x)_0.97O₂ ceramics was investigated (x = 0%, 1%, 4%, 6%, 10%, 20%). When the doping value of Zr was 4%, the dielectric loss was reduced to 0.098 and, at room temperature and at a frequency of 1000 Hz, the dielectric permittivity was recorded as 2420. In addition, the material's dielectric permittivity exhibited good stability at temperatures ranging from −50 °C to 200 °C. Using X-ray photoelectron spectroscopy (XPS) and Scanning electron microscopy (SEM), we have observed that Zr doping reduces grain size and increases grain boundary regions. According to our XPS and impedance analysis, Zr doping also reduces the concentration of oxygen vacancies, which are considered to be the main cause of dielectric loss. We believe that the Zr doping is an effective method for reducing the dielectric loss of CP materials.     

Giant permittivity in (Nb0.5La0.5)xTi1-xO2 ceramics prepared by slip casting in a strong magnetic field

A series of textured (Nb_0.5La_0.5)_xTi_1-xO₂ (x = 0, 0.0025, 0.005, 0.01) ceramics were sintered in a nitrogen environment after magnetic slip casting (12 T). Component x ranges from 0.0025 to 0.01 while the degree of orientation increases from 0.49 to 0.88. (Nb_0.5La_0.5)_0.01Ti_0.99O₂ ceramics in the parallel magnetic field's plane have a high permittivity ɛ_r ≈ 1.6 × 10⁴ and the ultralow dielectric loss tanδ ≈ 0.0038 at 10⁴ Hz. The temperature coefficient value of η ≤ ± 7.1% between 218–473 K, fulfilling the X9R requirements. The giant permittivity properties of textured ceramics are mainly derived from internal barrier layer capacitor impacts, electron hopping, and electron-pinned defect-dipoles polarization. The microstructure evolution of sintered ceramics was modified by texturing in a magnetic field, leading to higher activation energies of dielectric relaxations and resistance of grain boundaries and grains. This excellent performance is expected to show great potential in electronic devices' miniaturization and high-density energy storage.