Modified tunable dielectric properties by addition of MgO on BaZr0.25Ti0.75O3 ceramics

Phase composition, microstructure and tunable dielectric properties of (1 − x)BaZr_0.25Ti_0.75O₃-xMgO (BZTM) composite ceramics fabricated by solid-state reaction were investigated. It was found Mg not only existed in the matrix as MgO, there was also trace amount of Mg²⁺ ions dissolved in the BZT grains, which led to Curie temperature of the BZTM composites ceramics shifting to below −100 °C. Dielectric permittivity of the BZTM composite ceramics was reduced from thousands to hundreds by manipulating the content of MgO. Johnson's phenomenological equation based on Devonshire's theory was used to describe the nonlinear dielectric permittivity of the ceramics with increasing applied DC field. With increasing content of MgO, anharmonic constant α_(T) increased monotonously. Dielectric permittivity was 672, while dielectric tunability was as high as 30.0% at 30 kV/cm and dielectric loss was around 0.0016 for the 0.6BaZr_0.25Ti_0.75O₃-0.4MgO sample at 10 kHz and room temperature.     

Processing, dielectric properties and impedance characteristics of Na0.5Bi0.5Cu3Ti4O12 ceramics

Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure and dielectric properties of NBCTO ceramics sintered at various temperatures with different soaking time were investigated. Pure NBCTO phase could be obtained with increasing the temperature and prolonging the soaking time. High dielectric permittivity (13,495) and low dielectric loss (0.031) could be obtained when the ceramics were sintered at 1000 °C for 7.5 h. The ceramics sintered at 1000 °C for 7.5 h also showed good temperature stability (−4.00 to −0.69%) over a large temperature range from −50 to 150 °C. Complex impedances results revealed that the grain was semiconducting and the grain boundaries was insulating. The grain resistance (R_g) was 12.10 Ω cm and the grain boundary resistance (R_gb) was 2.009 × 10⁵ Ω cm when the ceramics were sintered at 1000 °C for 7.5 h.     

Synthesis and properties of Ba(Zn1/3Ta2/3)O3 for microwave and millimeter wave applications

High dielectric materials have gained an important position in microwave electronics by reducing the size and cost of components for a wide range of applications from mobile telephony to spatial communications. Ba(Zn_1/3Ta_2/3)O₃ (BZT) is an A(B′B″)O₃ type perovskite material, showing ultra high values of the quality factor Q. Ceramic-based BZT dielectric materials were prepared by solid state reaction. The samples were sintered at temperatures in the range 1400 ÷ 1600 °C for 4 h. Compositional, structural and morphological characterization were performed by using XRD, SEM and EDX analysis. The dielectric properties were measured in the microwave range (6 ÷ 7 GHz). An additional annealing at 1400 °C for 10 h has improved some dielectric parameters. For samples sintered at temperatures higher than 1500 °C, the permittivity values were obtained in the interval 30 ÷ 35 and almost do not change the value after the annealing. The Q × f product substantially increases up to about 135,000 GHz, exhibiting a low temperature coefficient of the resonant frequency (τ_f) in microwaves. The best parameters were obtained for the samples sintered at 1600 °C with additional annealing. The achieved high values of the Q × f product recommend these materials for microwave and millimeter wave applications.     

Tunable and microwave dielectric properties of Ba0.5Sr0.5TiO3-BaWO4 composite ceramics doped with Co2O3

Co₂O₃ doped BaWO₄-Ba_0.5Sr_0.5TiO₃ composite ceramics, prepared by solid-state route, were characterized systematically, in terms of their phase compositions, microstructure and microwave dielectric properties. Doping of Co₂O₃ promoted grain growth, reduced Curie temperature and broadened phase-transition temperature range of BaWO₄-Ba_0.5Sr_0.5TiO₃, which were attributed mainly to the substitution of Co³⁺ for Ti⁴⁺ at B site in the perovskite lattice. Dielectric diffusion behaviors of the composite ceramics were discussed. The composite ceramics all had dielectric tunability of higher than 10% at 30 kV/cm and 10 kHz, with promising microwave dielectric properties. Specifically, the sample doped with 0.2 wt.% Co₂O₃ exhibited a tunability of 20%, permittivity of 225 and Q of 292 (at 1.986 GHz), making it a suitable candidate for applications in electrically tunable microwave devices.     

Enhanced performance of sandwich structure Pb0.8La0.1Ca0.1Ti0.975O3 thin film for pyroelectric applications

Using the advantages of low-temperature crystallization and high orientation in Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ (PLCT) film, a dense PLCT/porous PLCT/dense PLCT sandwich structure was obtained in the present study. It is found that dense PLCT layer can both sustain the porous density in the core layer and also lead to better preferential orientation of the sandwich structure. In the sandwich structure, low dielectric constant (ε_r = 43) and leakage current density (J < 9 × 10^− 5A/cm²) are simultaneously achieved. Because of high orientation in sandwich structure, the pyrocoefficient (p > 185 µC/m² K) is still keeping a relatively large value. The resulting high figure of merit (F_V′ = 4.5 µC/m² K, F_d′ = 228 µC/m² K) make the sandwich structure films good candidate for pyroelectric thin-film devices.     

Use of water vapor for suppressing the growth of unstable low-κ interlayer in HfTiO gate-dielectric Ge metal-oxide-semiconductor capacitors with sub-nanometer capacitance equivalent thickness

Annealing of high-permittivity HfTiO gate dielectric on Ge substrate in different gases (N₂, NH₃, NO and N₂O) with or without water vapor is investigated. Analysis by transmission electron microscopy indicates that the four wet anneals can greatly suppress the growth of a GeO_x interlayer at the dielectric/Ge interface, and thus decrease interface states, oxide charges and gate leakage current. Moreover, compared with the wet N₂ anneal, the wet NH₃, NO and N₂O anneals decrease the equivalent permittivity of the gate dielectric due to the growth of a GeO_xN_y interlayer. Among the eight anneals, the wet N₂ anneal produces the best dielectric performance with an equivalent relative permittivity of 35, capacitance equivalent thickness of 0.81 nm, interface-state density of 6.4 × 10¹¹ eV^− 1 cm^− 2 and gate leakage current of 2.7 × 10^− 4 A/cm² at V_g = 1 V.     

Influence of dc bias field on dielectric properties of high-k Y5V (Ba, La)(Ti, Ce)O3 ceramic

The influence of dc bias field (E_bias) on the dielectric properties of high-k Y5V (Ba_0.97La_0.03)(Ti_0.94Ce_0.05)O₃ ceramic (BL3TC5) was investigated. With increasing E_bias from 1 to 12.5 kV/cm, dielectric permittivity and dielectric loss were suppressed, and the permittivity maximum decreased linearly. Upon field heating and field cooling, the temperature of the permittivity maximum shifted to higher temperatures; however, the dielectric heat relaxation decreased with increasing E_bias. As E_bias ≥ 10 kV/cm, the frequency dispersion vanishes. The model of polar nano-domains is proposed to account for dielectric behavior under dc bias field. In addition, BL3TC5 shows high tunability (~ 67%) and low loss (< 0.008) at room temperature.     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

Piezoelectric shear-mode properties of Pb(Yb1/2Nb1/2)O3-PbTiO3 ceramics

A Pb(Yb_1/2Nb_1/2)O₃-PbTiO₃ [PYNT] solid solution was synthesized and characterized for its potential use. The shear-mode dielectric and piezoelectric behaviors of PYNT with a morphotropic phase boundary (MPB) composition were studied as a function of temperature. Dielectric permittivity K₁₁^T and loss were found to be 2310 and 2.5%, respectively, at room temperature. Piezoelectric coefficient d₁₅ and electromechanical coupling factor k₁₅ were calculated to be 710 pC/N and 0.70, respectively, maintaining nearly constant up to 300 °C, resistivity and RC time constant were observed to be 2.4 × 10⁹ Ω cm and 1.07 s, respectively, at 350 °C. These good piezoelectric properties, together with the high Curie temperature (T_c ∼ 370 °C), indicate that PYNT is a promising candidate for high temperature-shear sensor and inkjet actuator applications.     

Ba2Ti9O20-Ba1.85Sm4.1Ti9O24 layered dielectric resonators with adjustable effective dielectric constant

The layered dielectric resonator structures composed of Ba₂Ti₉O₂₀ (BTO) and Ba_1.85Sm_4.1Ti₉O₂₄ (BSTO) ceramic pellets were introduced to design new microwave dielectric materials with adjustable dielectric constant between 50 and 70. Good combination of microwave dielectric properties (?_r,eff = 50 ~ 70, Qf = 11,700-19,100 GHz and τ_f = − 4.3 to − 1.5 ppm/°C) was obtained by the present approach, and such combination could be optimized by adjusting the volume fraction of BSTO and stacking scheme. For practical applications, the BTO and BSTO layers could be bonded by low-loss adhesive, and the effects of the adhesive on the microwave dielectric properties were limited.     

Effect of MgWO4 content on properties of Ba0.5Sr0.5TiO3 composite ceramics for tunable microwave applications

xMgWO₄-(1 − x) Ba_0.5Sr_0.5TiO₃ (x = 0.0, 5.0, 15.0, 25.0 and 35.0 wt%) composite ceramics were prepared via solid state reaction processing. Their structural and dielectric properties were systematically characterized. A significant increase in grain size was observed with increasing MgWO₄ content, which was accompanied by obvious variations in dielectric properties of the composite ceramics. It is found that the permittivity peaks of the samples gradually shifted to low temperatures with increasing MgWO₄ content. At the same time, tunabilities of the composite ceramics decreased, but their Q values increased. The sample with 35 wt% MgWO₄ possesses a high tunability of 16.8% (∼10 kHz), a low permittivity of 65 and an appropriate Q value of 309 (∼4.303 GHz), which meet the requirements of high power and impedance matching, thus making it a promising candidate for applications as electrically tunable microwave devices.     

Ferroelectric properties of lithia-doped (Bi0.95Na0.75K0.20)0.5Ba0.05TiO3 ceramics

Lead-free piezoelectric (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics have been prepared by conventional process for different lithium substitutions. The SEM images show that the ceramics are well sintered at 1428 K. Dielectric and ferroelectric measurements have been performed. With the increasing of lithium substitution, the Curie temperature of the (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics shifts from 570 K to 620 K, but the maximum value of the dielectric constant decreases from 6700 to 4700 correspondingly. A relatively larger remanent polarization of 36.8 μC/cm² has been found in the x = 0.05 sample. The coercive field decreases as the lithium substitution amount increases. An optimized d₃₃ = 194 × 10^− 12 C/N and a relative dielectric constant ε_r = 1510 have been obtained in (Bi_0.95Na_0.75K_0.15Li_0.05)_0.5Ba_0.05TiO₃.     

Interfacial characteristics and dielectric properties of Ba0.65Sr0.35TiO3 thin films

Ba_0.65Sr_0.35TiO₃ (BST) thin films were deposited on Pt/Ti/SiO₂/Si substrates by radio frequency magnetron sputtering technique. X-ray photoelectron spectroscopy (XPS) depth profiling data show that each element component of the BST film possesses a uniform distribution from the outermost surface to subsurface, but obvious Ti-rich is present to BST/Pt interface because Ti⁴⁺ cations are partially reduced to form amorphous oxides such as TiO_x (x < 2). Based on the measurement of XPS valence band spectrum, an energy band diagram in the vicinity of BST/Pt interface is proposed. Dielectric property measurements at 1 MHz reveal that dielectric constant and loss tangent are 323 and 0.0095 with no bias, while 260 and 0.0284 with direct current bias of 25 V; furthermore, tunability and figure of merit are calculated to be 19.51% and 20.54, respectively. The leakage current density through the BST film is about 8.96 × 10^− 7 A/cm² at 1.23 V and lower than 5.66 × 10^− 6 A/cm² at 2.05 V as well as breakdown strength is above 3.01 × 10⁵ V/cm.     

The influence of annealing temperatures on the properties of Bi2VO5.5/LaNiO3/Si thin films

Bi₂VO_5.5 ferroelectric thin films were fabricated on LaNiO₃/Si(100) substrate via chemical solution deposition. Ferroelectric and dielectric properties of the thin films annealed at 500-700 °C were studied. The thin film annealed at 700 °C exhibited more favorable ferroelectric and dielectric properties than those annealed at lower temperatures. The values of remnant polarization 2P_r and coercive field E_c for the film annealed at 700 °C are 10.62 µC/cm² and 106.3 kV/cm, respectively. The leakage current of the film is about 1.92 × 10^− 8 A/cm² at 6 V. The possible mechanism of the dependence of electrical properties of the films on the annealing temperature was discussed.     

Low-temperature sintering of (Zn0.8 Mg0.2)2SiO4-TiO2 ceramics

Effect of Li₂O-B₂O₃-SiO₂ (LBS) glass on the sintering behavior and the microwave dielectric properties of (Zn_0.8 Mg_0.2)₂SiO₄-TiO₂ (ZMST) ceramics were investigated. The Li₂O-B₂O₃-SiO₂ glass lowered the sintering temperature of ZMST ceramics effectively from 1250 to 870 °C. The unknown second phase, which was formed in the ZMST ceramics increased with the addition of LBS glass. With increasing the LBS glass content, the bulk density, dielectric constant (ε_r) and the maximum Q × f value decreased, and the temperature coefficient of resonant frequency (τ_f) shifted to a negative value. (Zn_0.8 Mg_0.2)₂SiO₄-TiO₂ ceramics with 3 wt.% Li₂O-B₂O₃-SiO₂ glass sintered at 870 °C for 2 h shows excellent dielectric properties: ε_r = 8.48, Q × f = 11500 GHz, and τ_f = 0 ppm/°C.     

Phase evolution and dielectric properties of MgTi2O5 ceramic sintered with lithium borosilicate glass

Phase evolution, densification, and dielectric properties of MgTi₂O₅ dielectric ceramic, sintered with lithium borosilicate (LBS) glass, were studied. Reaction between LBS glass and MgTi₂O₅ was significant in forming secondary phases such as TiO₂ and (Mg,Ti)₂(BO₃)O. The glass addition was not necessarily deleterious to the dielectric properties due to the formation of TiO₂: permittivity increased and temperature coefficient of resonance frequency could be tuned to zero with the addition of LBS glass, although the inevitable glass-induced decrease of quality factor was not retarded by the formation of TiO₂. The sintered specimen with 10 wt% LBS fired at 950 °C for 2 h showed permittivity of 19.3, quality factor of 6800 GHz, and τ_f of −16 ppm/°C.     

Exceptionally large third-order optical susceptibility in Ag:SrBi2Nb2O9 composite films

Thin films of SrBi₂Nb₂O₉ with and without the inclusion of Ag nanocrystals were prepared on MgO (001) substrates by alternative pulsed laser ablation of SrBi₂Nb₂O₉ ceramic and Ag metal in a nitrogen atmosphere. The size of the Ag nanocrystals can be brought down to ca. 5.0 nm, as revealed by transmission electron microscopy and X-ray diffraction. We measured the third-order susceptibility χ⁽³⁾ of the deposits by single beam z-scan technique at a wavelength of 532 nm. It is found that SrBi₂Nb₂O₉ is an effectively nonlinear optical medium, exhibiting a very large χ⁽³⁾. With the inclusion of Ag nanocrystals the χ⁽³⁾ was nearly doubled (Reχ⁽³⁾ = 8.052 × 10^− 7 esu, and Imχ⁽³⁾ = − 1.717 × 10^− 7 esu), which comes very close to the maximum value available in the current time. This indicates that the Ag:SrBi₂Nb₂O₉ composite structure can be an excellent candidate for nonlinear optical applications. A general approach for further enhanced third-order susceptibility by tailoring the dielectric constant of the metal inclusion is briefly discussed.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Effects of Y2O3 addition on microwave dielectric characteristics of Al2O3 ceramics

Microwave dielectric characteristics of alumina ceramics with yttria addition were investigated. The sintering temperature was lowered, and the dielectric constant (ε_r) did not remarkably change by adding yttria. The microwave dielectric loss (tan δ) increased from 8.4 × 10^− 5 to 2.2 × 10^− 4, due to the presence of Al₅Y₃O₁₂ secondary phase. The grain size had significant effects on the dielectric loss, and there was an optimum grain size where the dielectric loss reached the minimum.     

Effect of Na/K excess on the electrical properties of Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3 thin films prepared by sol-gel processing

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (NKBT) thin films derived from different amounts of Na/K excess content were fabricated via an aqueous sol-gel method on a Pt(111)/Ti/SiO₂/Si substrate, and the effect of Na/K excess content on the microstructure and electrical properties of the NKBT thin films was investigated. A second phase appears when Na/K excess content is below 20 mol%. Appropriated Na/K excess can enhance the polarization and dielectric properties due to compensation of Na/K loss that occurred during heat treatment. The 20 mol% excess derived NKBT thin film exhibits the best ferroelectric and dielectric properties with a remnant polarization (Pr) of 13.6 μC/cm², and a coercive field (Ec) of 104.8 KV/cm, together with a dielectric constant of 406 and a dissipation factor of 0.064. Similar to the dielectric response change with Na/K excess content, the decreasing concentration of charged defects is the main reason resulting in the increase of the piezoelectric property. The film with a 20 mol% excess content exhibited an effective d₃₃^? of about 56 pm/V. Also, the NKBT with a 20 mol% excess content exhibits the lowest current density of 5.6 × 10^− 5 A/cm² at 10 V.