Abnormal resistivity-temperature characteristics of semiconducting (Ba1-x Pb x )TiO3 materials prepared by microwave sintering

Abstract

(Ba_0.7Pb_0.3)TiO₃ and (Ba_0.4Pb_0.6)TiO₃ materials possessing double critical temperature (T_c ) and single high-T_c in resistivity-temperature (ρ-T) behavior, respectively, were obtained by microwave sintering at 1050°C for 5 minutes. These characteristics were ascribed to the existence of the dual phases with core-shell structure. The cooling-rate control modified the relative magnitude of low-T_c and high-T_c resistivity jumps, without altering the T_c -values. It occurred via the change in relative proportion of the core and shell phases.     

Modification on PTCR behavior of (Sr0.2Ba0.8)TiO3 materials by post-heat treatment after microwave sintering

Abstract

Effect of post-sintering treatment on PTCR behavior of (Sr_0.2Ba_0.8)TiO₃ materials prepared by microwave-sintering (ms) process was compared to that prepared by rapid thermal sintering (RTS) process. The microwave-sintering process needed only 1130°C-40 min to effectively densify (Sr_0.2Ba_0.8)TiO₃ materials. The grain size was around 6 μm and PTCR characteristics was around ρ_max/ρ_min≈ 10^1.75, with T_c = 50°C. Lowering the cooling rate after sintering substantially increases the resistivity jump (ρ_max/ρ_min) from 10² to 10^3.4, without altering the microstructure. The annealing at 1250°C for 2 h markedly increased the resistivity jump to (ρ_max/ρ_min)≈10⁶. On the other hand, the rapid thermal sintering (RTS) process required 1320°C-30 min to fully develop the good microstructure (～15 μm) and PTCR property (ρ_max/ρ_min ～ 10^3.0). Post-sintering process, including cooling rate control and annealing, did not improve the electrical properties of these samples, that is ascribed to the slow-cooling rate characteristics of RTS-process for a temperature lower than 800°C.     

Effect of CeO2 and Nd2O3 on the Microstructure and Microwave Dielectric Properties of (Zr0.8,Sn0.2)TiO4 Ceramics

(Zr_0.8,Sn_0.2)TiO₄ (ZST) ceramics were prepared by solid-state reaction method with 1 wt% ZnO and 0.5–1.5 wt% CeO₂ or Nd₂O₃ as sintering aids. The effect of processing parameters and additive concentration on the structure, microstructure and microwave dielectric properties of ZST ceramics were investigated. The dielectric constant (?_r) and temperature coefficient of the resonance frequency (τ_f) were not significantly affected by the addition of these additives. The unloaded quality factors (Q_u) were effectively promoted by CeO₂ and Nd₂O₃ additions. ?_r values of 40 and 38.3, Qxf_o values of 57,500 and 59,300 were obtained for the samples sintered with 1.5 and 0.5 wt% of CeO₂ and Nd₂O₃ respectively. The improvement in Qxf_o value is primarily attributed to the increase in uniform grain size and density.     

Control of Microwave Dielectric Properties in the System BaO ⋅ Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>—BaO ⋅ Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>

BaO ⋅ Nd₂O₃ ⋅ 4TiO₂—based ceramics were prepared by the mixed oxide route. Specimens were sintered at temperatures in the range 1200–1450^∘C. Microstructures were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM); microwave dielectric properties were determined at 3 GHz by the Hakki and Coleman method. Product densities were at least 95% theoretical. The addition of up to 1 wt% Al₂O₃ to the starting mixtures reduced the sintering temperatures by at least 100^∘C. Incorporation of small levels of Al into the structure (initially Ti sites) led to an increase in Q × f values, from 6200 to 7000 GHz, a decrease in relative permittivity (ε_r) from 88 to 78, and moved the temperature coefficient of resonant frequency (τ_f) towards zero. The addition of 0.5 wt% Al₂O₃ with 8 wt% Bi₂O₃ improved densification, increased both ε_r (to 88) and Q× f (to 8000 GHz) and moved τ_f closer to zero. Ceramics in the system (1 − x)BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + xBaO ⋅ Al₂O₃ ⋅ 4TiO₂ exhibited very limited solid solubility. The end member BaO ⋅ Al₂O₃ ⋅ 4TiO₂ was tetragonal in structure with the following dielectric properties: ε_r = 35; Q× f = 5000 GHz; τ_f = −15ppm/^∘C. Microstructures of the mixed Nd-Al compositions contained two distinct phases, Nd-rich needle-like grains and large Al-rich, lath-shaped grains. Products with near zero τ_f were achieved at compositions of approximately 0.14BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + 0.86BaO ⋅ Al₂O₃ ⋅ 4TiO₂, where Q× f = 8200 GHz and ε_r = 71.     

Effects of structural characteristics on microwave dielectric properties of (1−x)CaWO4 –xLaNbO4 ceramics

Dependences of microwave dielectric properties on the structural characteristics of (1−x)CaWO₄–xLaNbO₄ ceramics were investigated as a function of LaNbO₄ content (0.0 ≤ x ≤ 0.5). A single phase with tetragonal scheelite structure was obtained up to x = 0.35, and then the mixture phases with scheelite and fergusonite structure were detected. With the increase of LaNbO₄, the deviation of the observed dielectric polarizabilities calculated by the Clausius-Mosotti equation from the theoretical values calculated by the additivity rule of dielectric polarizability, was decreased due to the decrease of oxygen bond valence in ABO₄ scheelite structure. Dielectric constant (K) and temperature coefficient of resonant frequency (TCF) were increased with LaNbO₄ content due to the decrease of oxygen bond valence. Q ⋅ fvalue was dependent on the atomic packing fraction of unit cell as well as the grain size. Typically, K = 13.3, Qf = 50,000 GHz and TCF = −8.7 ppm/^oC were obtained for the specimens with 0.3 mol of LaNbO₄ sintered at 1150^oC for 3 h.     

Synthesis and Characterization of Zn-Doped TiO2 Nanoparticles via Sonochemical Method

Zn-doped TiO₂ nanoparticles were successfully fabricated using sonochemical method accompanying post calcination process. Titanium isopropoxide (Ti[OC₃H₇]₄) and Zinc chloride (ZnCl₂) were used as starting precursors for Ti and Zn sources, respectively. The homogeneous mixing solution of different Zn (0–1 mol%) and Ti ratio were irradiated in high intensity ultrasound sonometer (750 W 20 kHz) for 30 min at room temperature to obtain as-synthesized Zn-doped TiO₂ nanoparticles followed by calcination at 400–700°C. To evaluate the structure and phase identification of prepared powders, the X-ray diffraction (XRD) and Raman spectroscopy were employed. The results reveal that the as-synthesized Zn-doped TiO₂ nanoparticles are in anatase phase and their crystallinity increases with increasing calcined temperature. The morphology of as-synthesized powders was investigated by transmission electron microscope (TEM). The effect of Zn content and calcinations temperature on TiO₂ properties was also discussed.     

Synthesis and sintering properties of (La0.8Ca0.2−x Sr x )CrO3 perovskite materials for SOFC interconnect

Synthesis and sintering properties of the (La_0.8Ca_0.2−x Sr _x )CrO₃ samples doped by two alkaline earth metals in comparison to the doped only by one alkaline earth metal were evaluated by phase analysis, sintering properties, thermal expansion behaviors, and electrical conductivity. The sintered (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, and 0.1) and (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0.2) were found to have orthorhombic and rhombohedral symmetries, respectively. Relative density of the (La_0.8Sr_0.2)CrO₃ sample sintered at 1500^∘C for 5 h was lower than that of the (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, and 0.1) sample. TECs of the (La_0.8Ca_0.2−x Sr _x )CrO₃ (x = 0, 0.05, 0.1, and 0.2) in air were 11 × 10⁻⁶/^∘C, 11.2 × 10⁻⁶/^∘C, 11.2 × 10⁻⁶/^∘C, and 11.3 × 10⁻⁶/^∘C, respectively. The electric conductivity of the (La_0.8Ca_0.2−x Sr _x )CrO₃ sample was determined.     

Co-Modification of Ba5NdTi3Ta7O30 Dielectric Ceramics by Substitution and Introducing Secondary Phase

Co-modification of Ba₅NdTi₃Ta₇O₃₀ dielectrics ceramics was investigated through Pb substitution for Ba and introducing Bi₄Ti₃O₁₂ secondary phase. The dielectric constant increased from 150 to 283, the temperature coefficient of the dielectric constant decreased from –2500 ppm/°C to –1279 ppm/°C, and the dielectric loss decreased to 0.0007 at 1 MHz. Meanwhile, the bi-phase ceramics were investigated to achieve temperature stable ceramics with high dielectric constant and low dielectric loss. As the composition x varied from 0.4 to 0.7 for (1 – x)(Ba_0.8Pb_0.2)₅NdTi₃Ta₇O₃₀/xBi₄Ti₃O₁₂, the temperature coefficient of the dielectric constant changed from negative to zero to positive.     

Preparation of (PbxBa1-x)TiO3 thin films by MOCVD using an aerosol-assisted liquid delivery system

Abstract

Thin films of PbTiO₃, BaTiO₃ and (Pb_xBa_1-x)TiO₃ (PBT) have been prepared by metal-organic chemical vapor deposition using a horizontal reactor with an aerosol-assisted liquid delivery system. Structural and electrical properties have been investigated as a function of the lead content x. First results on PBT thin films grown on platinized silicon substrates show, for x < 0.8, an increasing tetragonal distortion of the lattice cell (c/a >1), and accompanying ferroelectric behavior which is similar to the bulk material. For smaller lead content (x < 0.8) no ferroelectric behavior is established and a small tetragonal distortion of opposite type (c/a <1) is observed. This distortion is attributed to a thermally induced tensile film stress and may be responsible for the suppression of the ferroelectric phase transition.     

SnO2 nanocrystallines decorated g-C3N4 composites with enhanced visible-light photocatalytic activity

Abstract

A series of SnO₂ nanocrystallines decorated g-C₃N₄ architectures were synthesized using a facile solvothermal method. The structural, morphological, and optical properties of the as-prepared nanocomposites were characterized in detail, indicating that SnO₂ nanocrystallines with diameter ～ 4?nm were well-dispersed on the surface of g-C₃N_4. The photocatalytic activity of the composites was investigated by degrading rhodamine B (RhB) under visible light irradiation. The CNS2 heterostructure exhibits enhanced photocatalytic activity than bare SnO₂ and g-C₃N₄. Kinetic study revealed a promising degradation rate constant of 0.0593?min^?1 for the CNS2, which is 118 and 7 times higher than that of pure SnO₂ and g-C₃N₄, respectively. What’s more, the CNS2 still retained the photocatalytic activity after three cycle measurements. The enhanced photocatalytic performances of the nanocomposite may be due to its large surface area (116.2 m²/g), appropriate ratio of SnO₂/g-C₃N₄ and the compact structure of the junction between the SnO₂ nanocrystallines and the g-C₃N₄, which inhibits the recombination of photogenerated electrons and holes.     

Dielectric Properties and Sintering Characteristics of CaTiO<Subscript>3</Subscript>-(Li<Subscript>1/2</Subscript>Nd<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript> Ceramics

The dielectric properties and the sintering effect upon microstructure of (1–x) CaTiO₃-x(Li_1/2Nd_1/2)-TiO₃ Ceramics are investigated in this paper. Nd³⁺ and Mg^{2 +} ions co-substitution for Ca^{2 +} on A site improves the sintering characteristic of CaTiO₃ ceramics with forming orthorhombic perovskite structure. The structure of (1 – x) CaTiO₃-x(Li_1/2Nd_1/2)TiO₃ changes from orthorhombic to tetragonal as (Li_1/2Nd_1/2)TiO₃ addition increasing. Limited solubility of (Li_1/2Nd_1/2)TiO₃ in CaTiO₃ forming a part solid solution compound achieves the adjustment of for CaTiO₃ at low sintering temperature. The proper dielectric properties with = 78, tan = 0.0006, = +7 ppm/C are obtained for 0.8Ca_0.67(Nd,Mg)_0.22TiO₃-0.2(Li_1/2Nd_1/2)TiO₃ ceramics.     

Structure and dielectric properties of Cu and (K,Na) doped SrBi2Nb2O9 ferroelectric ceramics

Ferroelectric ceramics, SrBi₂Nb₂O₉ (SBN), Sr_0.8Cu_0.2Bi₂Nb₂O₉ (SCBN) and Sr_0.8K_0.1Na_0.1Bi₂Nb₂O₉ (SKNBN) were prepared by a solid state reaction process. X-ray diffraction analysis shows that the alkali and Cu almost diffuse into the SBN lattice to form a solid solution during sintering and some slight secondary phases was detected. The effect of alkali and Cu on dielectric properties of the SBN ceramics was discussed. The dielectric loss factor of (K,Na) doped SBN ceramics degraded considerably to 0.01 and their frequency and temperature stabilities were enhanced. The dielectric constant was enhanced by approximately 60% and the Curie temperature (Tc) was also improved for Cu doped SrBi₂Nb₂O₉ ceramics.     

Epitaxial Pb(Zr,Ti)O<Subscript>3</Subscript> Capacitors on Si by Liquid Delivery Metalorganic Chemical Vapor Deposition

La_0.5Sr_0.5CoO₃/Pb(Zr_xTi_1–x)O₃/La_0.5Sr_0.5CoO₃ capacitors have been successfully fabricated by liquid delivery metalorganic chemical vapor deposition on Si wafers using SrTiO₃ thin layer (20 nm) as a template. Zr(dmhd)₄ in tetrahydrofuran was used as Zr precursor for compatible thermal behavior with Pb(thd)₂ and Ti(OiPr)₂(thd)₂ precursors. The dependence of the ferroelectric film composition on the precursor mixing ratio and growth temperature has been systematically studied by Rutherford Backscattering (RBS). Ferroelectric and piezoelectric properties at the composition close to morphotropic phase boundary region (Pb(Zr_0.5Ti_0.5)O₃) have been investigated for application in nonvolatile ferroelectric random access memories and microelectromechanical system (MEMS). These capacitors show desirable ferroelectric properties, which proves that this approach is very promising for both fundamental study and potential applications. The changes of spontaneous polarization (P_s) and piezoelectric coefficient (d₃₃) with Ti/(Zr + Ti) ratio are also presented and compared with theoretical values.     

Photocatalytic property of TiO2 loaded with SnO2 nanoparticles

2.5 nm-sized SnO₂ nanoparticles in rutile phase were loaded on the surface of 25 nm-sized TiO₂ (Degussa P-25) to form SnO₂/TiO₂ nano-composite structure. Up to 10 mol%, the loaded SnO₂ nanoparticles were well-dispersed on the surface of TiO₂ without mutual agglomeration. The SnO₂/TiO₂ with 1 mol% of SnO₂ demonstrated 1.5–1.7 times of photocatalytic activity compared to the pure TiO₂ in decomposing gaseous 2-propanol and in evolving CO₂. The role of SnO₂ nanoparticles on TiO₂ surface is considered to be retardation of recombination rate between electrons and holes by trapping the photo-excited electrons from the conduction band of TiO₂.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Dielectric and Ferroelectric Characterization of Na(Ta,Nb)O<Subscript>3</Subscript> Solid Solution Ceramics

Ceramics in the Na(Ta_{1 − x}Nb_x)O₃ system were prepared by a solid state reaction approach, and their dielectric characteristics were evaluated together with the structures. The complete solid solution with orthorhombic structures was observed in the present system, and three supposed phase transitions at about 475, 580 and 650^∘C were observed by DTA. Only one dielectric anomaly was observed at high temperature for x = 0.2 and 0.4, and alternative dielectric anomaly (a diffused dielectric peak) was observed around 170 and 380^∘C for x = 0.6 and 0.8, respectively. The compositions of 0.6 and 0.8 are weakly ferroelectric and those of 0.2 and 0.4 are supposed to be antiferroelectric at room temperature.     

Dielectric and Piezoelectric Properties of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-K<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-NaNbO<Subscript>3</Subscript>Lead-Free Ceramics

The ternary lead-free piezoelectric ceramics system of (1 – x) [0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃] – xNaNbO₃(x = 0, 0.02, 0.04, 0.06, 0.08, 0.10) were synthesized by conventional solid state reaction method. The crystal structure, dielectric, piezoelectric properties and P-E hysteresis loops were investigated. The crystalline structure of all compositions is mono-perovskite phase ascertained by XRD, and the lattice constant was calculated from the XRD data. Temperature dependence of dielectric constant _r and dissipation factor tan measurement revealed that all compositions experienced two phase transitions: from ferroelectric to anti-ferroelectric and from anti-ferroelectric to paraelectric, and these two phase transitions have relaxor characteristics. Both transition temperatures T_d and T_m are lowered due to introduction of NaNbO₃. P-E hysteresis loops show that 0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃ ceramics has the maximum P_r and E_c corresponding to the maximum values of electromechanical coupling factor K_p and piezoelectric constant d_33. The piezoelectric constant d₃₃ and electromechanical coupling factor K_p decrease a little, while the dielectric constant ₃₃^T/₀ improves much more when the concentration of NaNbO₃ is 8 mol%.     

Microwave Tunable Properties of Ni-Doped (Ba0.5Sr0.5)TiO3 Thin Films Grown by Pulsed Laser Deposition

(Ba_0.5Sr_0.5)TiO₃ (BST) thin films were deposited by pulsed laser deposition (PLD) and investigated as a function of Ni dopant concentration in low and high frequency regions. In low frequency region (<10 MHz), the Ni-dopant concentration in BST films has a strong influence on the material properties including dielectric and tunable properties. Ni-doped (≤3 mol%) BST films showed denser, smoother morphologies and smaller grain sizes than those with 6 and 12 mol% Ni. Dielectric constant and loss of 3 mol% Ni-doped BST films were about 980 and 0.3%, respectively. In addition, tunability and figure of merit of 3 mol% doped BST films showed maximum values of approximately 39% and 108, respectively. In high frequency region (>1 GHz), the frequency tunability range at center frequency of undoped BST and 3 mol% Ni-doped BST coplanar waveguide (CPW) resonators showed 102 and 152 MHz, respectively at 30 V dc bias. The Ni-doped BST thin films are possible in applications of microwave tunable capacitors.     

Control of 0.2CaTiO3-0.8Li0.5Nd0.5TiO3 microwave dielectric ceramics by additions of Bi2Ti2O7

Ceramics of 0.2CaTiO₃-0.8Li_0.5Nd_0.5TiO₃) have been prepared by the mixed oxide route using additions of Bi₂O₃-2TiO₂ (up to 15 wt%). Powders were calcined 1100^∘C; cylindrical specimens were fired at temperatures in the range 1250–1325^∘C. Sintered products were typically 95% dense. The microstructures were dominated by angular grains 1–2 μm in size. With increasing levels of Bi₂O₃-2TiO₂ additions, needle and lath shaped second phases developed. For Bi₂Ti₂O₇ additions up to 5 wt%, the relative permittivity increased from 95 to 131, the product of dielectric Q value and measurement frequency increased from 2150 to 2450 GHz and the temperature coefficient of resonant frequency (τ _f ) increased from −28pp/^∘C to +22pp/^∘C. A product with temperature stable τ _f could be obtained at ∼2 wt% Bi₂Ti₂O₇ additions. For high levels of additives, there is minimal change in relative permittivity, the Qxf values degrade and τ _f becomes increasingly negative.     

Electrical Properties of Acceptor Doped BaTiO3

Electrical properties of acceptor (Mn, Mg or Mn+Mg)-doped BaTiO₃ ceramic have been studied in terms of oxygen vacancy concentration, various doping levels and electrical degradation behaviors. The solubility limit of Mn on Ti sites was confirmed to be close to or less than 1.0 mol%. Oxygen vacancy concentration of Ba(Ti_{0.995 –x}Mg_0.005Mn_x)O_{2.995 –y} (x = 0, 0.005, 0.01) was estimated to be 50 times greater than that of the un-doped BaTiO₃. The leakage current of 0.5 mol% Mn-doped BaTiO₃ was stable with time, which was much lower than that of the un-doped BaTiO₃. The BaTiO₃ specimen co-doped with 0.5 mol% Mg and 1.0 mol% Mn showed the lowest leakage current below 10^{– 10}A. It was confirmed that leakage currents of Mg-doped and un-doped BaTiO₃ under dc field are effectively suppressed by Mn co-doping as long as the Mn doping level is greater than Mg contents.