Synthesis, phase transformation and dielectric properties of sol–gel derived Bi2Ti2O7 ceramics

Sol–gel derived Bi₂Ti₂O₇ ceramic powders have been prepared from methoxyethoxides of bismuth and titanium (molar ratio of Ti/Bi = 1.23 and water/alkoxides = 1.31). The Bi₂Ti₂O₇ phase was stable at a low temperature (700 °C), but it then transformed into mixed phases of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ at 850–1150 °C. The single phase of Bi₂Ti₂O₇ reoccurred at 1200 °C. Dielectric properties and ferroelectric behavior of samples sintered at 1150 and 1200 °C were examined. Under frequency of 1 MHz, samples sintered at 1150 and 1200 °C had a dielectric constant of 101.3 and 104.2, and a loss tangent of 0.0193 and 0.0145, respectively. Only the sample sintered at 1150 °C showed ferroelectric behavior, where remanent polarization is 3.77 μC cm⁻² and coercive field is 24 kV cm⁻¹. Thus, the Bi₂Ti₂O₇ did not exhibit ferroelectricity, but the mixed phase of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ did.     

Piezoelectric properties in (K0.5Bi0.5)TiO 3-(Na0.5Bi0.5)TiO3-BaTiO 3 lead-free ceramics

Lead-free piezoelectric ceramics with compositions around the morphotropic phase boundary (MPB) x(Na_0.5Bi_0.5)TiO _3-y(K_0.5Bi_0.5)TiO₃-zBaTiO ₃ [x + y + z = 1; y:z = 2:1] were synthesized using conventional, solid-state processing. Dielectric maximum temperatures of 280degC and 262degC were found for tetragonal 0.79(Na_0.5Bi_0.5)TiO₃-0.14(K_0.5 Bi_0.5)TiO₃-0.07BaTiO$ d3 (BNBK79) and MPB composition 0.88(Na_0.5Bi_0.5)TiO₃-0.08(K _0.5Bi_0.5)TiO₃-0.04BaTiO$ d3 (BNBK88), with depolarization temperatures of 224degC and 162degC, respectively. Piezoelectric coefficients d₃₃ were found to be 135 pC/N and 170 pC/N for BNBK79 and BNBK88, and the piezoelectric d₃₁ was determined to be -37 pC/N and -51 pC/N, demonstrating strong anisotropy. Coercive field values were found to be 37 kV/cm and 29 kV/cm for BNBK79 and BNBK88, respectively. The remanent polarization of BNBK88 (~40 muC/cm²) was larger than that of BNBK79 (~29 muC/cm²). The piezoelectric, electromechanical, and high-field strain behaviors also were studied as a function of temperature and discussed     

Preparation of highly c-axis-oriented Bi4Ti3O12 thin films and their crystallographic, dielectric and optical properties

Bismuth titanate (Bi₄Ti₃O₁₂) thin films with a high c-axis orientation up to 99% were prepared on (100)-oriented silicon wafers by r.f. planar magnetron sputtering using a Bi₂TiO₅ ceramic target at a substrate temperature of 600 °C. From the Auger electron spectroscopy depth profile of the film, there is no evidence of interdiffusion of a specific element between the film and the substrate. Relative dielectric constant of these films depends on film thickness. The behavior was explained assuming a low-dielectric-constant interface layer. Using this assumption, the relative dielectric constant of Bi₄Ti₃O₁₂ film was estimated to be approximately 140. This value is close to that along the c axis in a bulk form. The remanent polarization and the coercive field were 0.8 μC cm⁻² and 20 kV cm⁻¹, respectively.     

Electrical properties of garnet-like lithium ionic conductors Li5+xSrxLa3--xBi2O12 fabricated by spark plasma sintering method

A typical approach involving Pechini method and spark plasma sintering (SPS) method was presented for the preparation of high density Li_5+xSr_xLa_3--xBi₂O₁₂ (x = 0, 1) ceramics. Phase formation, microstructure, grain size and electrical properties of the specimens were examined using XRD, SEM and alternating current impedance spectroscopy (ACIS). Dense Li₅La₃Bi₂O₁₂ and Li₆SrLa₂Bi₂O₁₂ ceramics with pure garnet-like phase, relative density of 97% and average grain size of about 5 μm were fabricated using this approach. The total conductivities at 298 K of Li₅La₃Bi₂O₁₂ and Li₆SrLa₂Bi₂O₁₂ ceramics prepared by the SPS method are 5.1×10^-5 and 6.8×10^-5 S/cm, respectively, 2 times higher than that of samples prepared by the conventional sintering method.     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

Crystal growth and spectral properties of pure and Co-doped Mg3B2O6 crystal

Novel pure and cobalt-doped magnesium borate crystals (Mg₃B₂O₆) have been grown successfully by the Czochralski technique for the first time. Crystal growth, X-ray powder diffraction (XRD) analysis, absorption spectrum, fluorescence spectrum as well as fluorescence decay curve of Co²⁺:Mg₃B₂O₆ (MBO) were described. From the absorption peaks for the octahedral Co²⁺ ions, the crystal-field parameter Dq and the Racah parameter B were estimated to be 943.3 cm⁻¹ and 821.6 cm⁻¹, respectively. The fluorescence lifetime of the transition ⁴T₁(⁴P) → ⁴T₂ centered at 717 nm was measured to be 9.68 ms.     

PrBi4Fe0.5Co0.5Ti3O15多铁陶瓷的性能研究

采用传统固相反应法与两步合成法制备了PrBi₄Fe_0.5Co_0.5Ti₃O₁₅陶瓷, 研究了Pr与Co共掺杂对Bi₅FeTi₃O₁₅陶瓷的结构、磁性能以及介电性能的影响。X射线衍射分析显示, 传统固相反应法制备的样品比两步法制备的样品更容易形成单相结构。铁电和磁性测量证明样品具有多铁性, 并且Pr与Co共掺杂能大幅提高材料的磁性能, 固相反应法与两步合成法制备的样品在室温下的剩余磁化强度(2M_r)分别为0.315, 0.576 Am²/kg, 比文献报道的Bi₅FeTi₃O₁₅陶瓷的2M_r ( 2.7 Am²/kg ) 高5个数量级, 比掺Co的Bi₅Fe_0.5Co_0.5Ti₃O₁₅陶瓷2M_r ( 7.8×10^-3 Am²/kg ) 高2个数量级。     

Influence of rare-earth oxides on structure and crystallization properties of Bi2O3–B2O3 glass

Bi₂O₃·B₂O₃ glasses doped with rare-earth oxides (RE₂O₃) (RE³⁺ = La³⁺, Pr³⁺, Sm³⁺, Gd³⁺, Er³⁺ and Yb³⁺) were prepared by the melting–quenching method. The relationships between composition and properties were demonstrated by IR, DSC, XRD and SEM analysis. The results show that the network structure resembles that of undoped Bi₂O₃·B₂O₃ glass, composing of [BO₃], [BO₄] and [BiO₆] units. RE₂O₃ stabilizes the glass structure as a modifier. Transition temperature (T_g) increases linearly with cationic field strength (CFS) of RE³⁺. La₂O₃, Pr₂O₃, Sm₂O₃ and Gd₂O₃ are benefit to promote the formation of BiBO₃ crystal. When Er₂O₃ and Yb₂O₃ are introduced, respectively, the main crystal phase changes to Bi₆B₁₀O₂₄. Transparent surface crystallized samples are obtained by reheating at 460–540 °C for 5 h. In this case, needle like BiBO₃ crystal or rare-earth-doped BiBO₃ crystal (Pr_xBi_1−xBO₃ and Gd_xBi_1−xBO₃) are observed, which is promising for non-linear optical application.     

Effects of reduction treatment on the photorefractive properties of Pb0.5Ba0.5Nb2O6

Lead barium niobate is a new photorefractive material of high interest for a variety of applications including holographic storage. Pb_0.5Ba_0.5Nb₂O₆ crystals have been grown by the Bridgman method, and the effects of heat treatments on their photorefractive properties were investigated using Ar ion laser at λ=514.5 nm. The color and absorption spectrum of the crystals varied depending on the oxygen partial pressure during heat treatment. The oxygen diffusivity was estimated to be in the order of 10⁻⁶ and 10⁻⁵ cm²/h at 425 and 550 °C, respectively. Reduction treatment at an oxygen pressure of 215 mTorr increased the effective density of photorefractive charges about three times from 8.0×10¹⁵ to 2.2×10¹⁶ cm⁻³ and made the charge transport more electron-dominant. As a result, the maximum gain coefficient improved from 5.5 to 13.8 cm⁻¹. A diffraction efficiency as high as 70% was achieved in a reduced crystal.     

Preparation and characterization of LiAl0.23Mn1.77O4 for supercapacitor electrodes

LiAl_0.23Mn_1.77O₄ was synthesized by high temperature solid-state reaction. The structure and morphology of LiAl_0.23Mn_1.77O₄ were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS). The supercapacitive performances of LiAl_0.23Mn_1.77O₄ materials were studied using galvanostatic charge/discharge measurements, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods in 2 mol L⁻¹ (NH₄)₂SO₄ solution. The results show that the LiAl_0.23Mn_1.77O₄ electrode exhibits typical supercapacitive characteristics in aqueous (NH₄)₂SO₄ electrolyte. The specific capacitance is up to 185 F g⁻¹ at current density of 2 mA cm⁻². The ohmic resistance (R_sol) is only 0.22 Ω. Besides, the electrodes showed a stable cycle life in the potential range of 0–1.0 V and retained 93% of initial specific capacitance over 100 cycles.     

Fabrication of robust Bi3.25La0.75Ti3O12 thin film resistant to hydrogen damage

Ferroelectric bismuth lanthanum titanate (Bi_3.25La_0.75Ti₃O₁₂; BLT) thin films were deposited on Pt/TiO₂/SiO₂/Si substrate by chemical solution deposition method. The films were crystallized in the temperature range of 600–700 °C. The spontaneous polarization (P_s) and the switching polarization (2P_r) of BLT film annealed at 700 °C for 30 min were 22.6 μC/cm² and 29.1 μC/cm², respectively. Moreover, the BLT capacitor did not show any significant reduction of hysteresis for 90 min at 300 °C in the forming gas atmosphere.     

Sol–gel synthesis and luminescence of unexpected microrod crystalline Ca5La5(SiO4)3(PO4)3O2:Dy phosphors employing different silicate sources

Ca₅La₅(SiO₄)₃(PO₄)₃O₂ doped with Dy³⁺ were synthesized by sol–gel technology with hybrid precursor employed four different silicate sources, 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM diagraphs show that there exist some novel unexpected morphological structures of microrod owing to the crosslinking reagents than TEOS as silicate source for their amphipathy template effect. X-ray pictures confirm that Ca₅La₅(SiO₄)₃(PO₄)₃O₂:Dy³⁺ compound is formed by a pure apatitic phase. The Dy³⁺ ions could emit white light in Ca₅La₅(SiO₄)₃(PO₄)₃O₂ compound, and the ratio of Y/B is 1.1, when the Dy³⁺ doped concentration is 1.0 mol%.     

Observation of ferroelectric domains in bismuth-layer-structured ferroelectrics using Raman spectroscopy

Raman spectroscopy has been used to investigate the domain structures in bismuth-layered-structured ferroelectrics (BLSFs). In Bi₄Ti₃O₁₂ single crystal, the lowest frequency mode (soft mode) at 30 cm⁻¹ appears exclusively for the xx polarization configuration (xpolar axis). We found that the polarization dependence of the Raman signal exhibits spatial symmetries that reflect the presence of different domain variants present in Bi₄Ti₃O₁₂. This highly anisotropic character of the soft mode shares with other BLSFs such as Bi_3.25La_0.75Ti₃O₁₂ and SrBi₂Ta₂O₉, which demonstrate the usefulness of the soft-mode spectroscopy for the study of ferroelectric domain structures in BLSFs. We also applied Raman spectroscopy to in situ observation of domain structures in Bi₄Ti₃O₁₂ under applied electric field.     

Synthesis, structure refinement and characterization of tetrahydrated acid gadolinium diphosphate HGdP2O7·4H2O

Synthesis and single crystal structure are reported for a new gadolinium acid diphosphate tetrahydrate HGdP₂O₇·4H₂O. This salt crystallizes in the monoclinic system, space group P2₁/n, with the following unit-cell parameters: a = 6.6137(2) Å, b = 11.4954(4) Å, c = 11.377(4) Å, β = 87.53(2)° and Z = 4. Its crystal structure was refined to R = 0.0333 using 1783 reflections. The corresponding atomic arrangement can be described as an alternation of corrugated layers of monohydrogendiphosphate groups and GdO₈ polyhedra parallel to the () plane. The cohesion between the different diphosphoric groups is provided by strong hydrogen bonding involving the W4 water molecule.

IR and Raman spectra of HGdP₂O₇·4H₂O confirm the existence of the characteristic bands of diphosphate group in 980–700 cm⁻¹ area. The IR spectrum reveals also the characteristic bands of water molecules vibration (3600–3230 cm⁻¹) and acidic hydrogen ones (2340 cm⁻¹). TG and DTA investigations show that the dehydration of this salt occurs between 79 and 900 °C. It decomposes after dehydration into an amorphous phase. Gadolinium diphosphate Gd₄(P₂O₇)₃ was obtained by heating HGdP₂O₇·4H₂O in a static air furnace at 850 °C for 48 h.     

Li/Ce/La共掺杂对CaBi2Nb2O9陶瓷晶体结构及电学性能的影响

采用固相反应法制备(Li_0.5Ce_0.25La_0.25)_xCa_1-xBi₂Nb₂O₉铋层状结构压电陶瓷, 分析多元稀土元素掺杂对CaBi₂Nb₂O₉(CBN)陶瓷晶体结构、微观形貌及电学性能的影响。Rietveld结构精修表明, 多元稀土元素进入晶格内部形成固溶体, 掺杂使晶体结构有由斜方晶系向四方晶系转变的趋势, 反位缺陷中A位的Bi ³⁺具备6s2孤对电子, 抑制这种变化趋势。SEM照片显示, 掺杂主要抑制晶粒沿垂直c轴平面生长, 这是由于稀土氧化物具备较高的熔点, 在烧结过程中不易扩散。准同型相界附近, 垂直b轴方向的a滑移面被打破, 极化方向沿a轴和b轴, 导致压电性能增强。其中, (Li_0.5Ce_0.25La_0.25)_0.17Ca_0.83Bi₂Nb₂O₉陶瓷具备最优异的性能: 居里温度为913 ℃, 压电系数高达16.4 pC/N; 经850 ℃退火2 h, 其d₃₃值为14.0 pC/N, 约为原始值的85.4%。     

Thermomechanical processing and transport current density of Ag-sheathed (Tl,Cr)Sr2(Ca0.9,Pr0.1)Cu2O7 superconductor tapes

Powders with nominal composition (Tl,Cr_0.15)Sr₂(Ca_0.9,Pr_0.1)Cu₂O₇ (Tl-1212) and T_c90 K were used to fabricate Ag-sheathed superconducting tapes employing the powder-in-tube (PIT) method. The tapes were subjected to intermediate mechanical rolling or pressing. Conditions that enhance the transport critical current density (J_c) of the tapes were investigated. Optimum annealing temperature and period together with uniaxial pressing are necessary to increase J_c of the Tl-1212/Ag tapes. Annealing at 910 °C for 0.5–1 h enhanced the 1212 phase formation and improved intergranular connectivity between grains, as well as to provide healing for the fractured structure caused by deformation process. A relatively longer annealing time at higher temperature gave rise to secondary phases and resulted in the decrease of J_c. Mechanical uniaxial pressing greatly densified the tapes core and thus led to closer contact between grains. At liquid nitrogen temperature and zero field, J_c of the pressed tapes annealed at 910 °C for 1 h is 3060±127 A cm⁻². The initial drastic drop of J_c in low fields (<0.06 T) indicates the performance of the tapes is limited by weak links. No significant anisotropic transport properties were observed in applied magnetic field. This is due to the absence of texturing in the tapes as the grains are randomly oriented revealed through SEM micrographs.     

Infrared optical properties of Bi2Ti2O7 thin films by spectroscopic ellipsometry

Bi₂Ti₂O₇ thin films have been grown directly on n-type GaAs (1 0 0) by the chemical solution decomposition technique. X-ray diffraction analysis shows that the Bi₂Ti₂O₇ thin films are polycrystalline. The optical properties of the thin films are investigated using infrared spectroscopic ellipsometry (3.0–12.5 μm). By fitting the measured ellipsometric parameter (Ψ and Δ) data with a three-phase model (air/Bi₂Ti₂O₇/GaAs), and Lorentz–Drude dispersion relation, the optical constants and thickness of the thin films have been obtained simultaneously. The refractive index and extinction coefficient increase with increasing wavelength. The fitted plasma frequency ω_p is 1.64×10¹⁴ Hz, and the electron collision frequency γ is 1.05×10¹⁴ Hz, and it states that the electron average scattering time is 0.95×10⁻¹⁴ s. The absorption coefficient variation with respect to increasing wavelength has been obtained.     

Optically active Er–Yb codoped Y2O3 films produced by pulsed laser deposition

Optically active Er³⁺:Yb³⁺ codoped Y₂O₃ films have been produced on c-cut sapphire substrates by pulsed laser deposition from ceramic Er:Yb:Y₂O₃ targets having different rare-earth concentrations. Stoichiometic films with very high rare-earth concentrations (up to 5.5 × 10²¹ at cm^− 3) have been achieved by using a low oxygen pressure (1 Pa) during deposition whereas higher pressures lead to films having excess of oxygen. The crystalline structure of such stoichiometric films was found to worsen the thicker the films are. Their luminescence at 1.53 μm and up-conversion effects have been studied by pumping the Yb³⁺ at 0.974 μm. The highest lifetime value (up to 4.6 ms) is achieved in films having Er concentrations of ≈ 3.5 × 10²⁰ at cm^− 3 and total rare-earth concentration ≈ 1.8 × 10²¹ at cm^− 3. All the stoichiometric films irrespective of their rare-earth concentration or crystalline quality have shown no significant up-conversion.     

Effect of CeO2 addition on structure and electrical properties of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics prepared by citric method

(Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃ ceramics added with 0–0.8 wt.% CeO₂ were prepared by a citrate method, and the influence of the CeO₂ addition on the structure and electrical properties was investigated. The specimens containing various amounts of CeO₂ show the coexistence of rhombohedral and tetragonal phases, with the relative content of the tetragonal phases gradually enhancing with increasing amount of CeO₂. Compared with (Na_0.5Bi_0.5)_0.93Ba_0.07TiO₃, the specimen added with a small amount of CeO₂ (≤0.2 wt.%) display a slightly improved electromechanical coupling factor (k_p) and piezoelectric constant (d₃₃) in conjunction with a reduced dielectric loss (tg δ) and an enhanced mechanical quality factor (Q_m), while higher CeO₂ amounts led to a rapid deterioration of the piezoelectric and ferroelectric properties. The variation of the electrical properties with the CeO₂ addition was tentatively interpreted with respect to doping effect, crystal-structural evolution and stability of ferroelectric domains.     

Preparation and characterization of Bi2Ti2O7 thin films by chemical solution deposition technique

Transparent and crack-free Bi₂Ti₂O₇ thin films with strong (111) orientation were successfully prepared on n-Si(100) by chemical solution deposition (CSD) using bismuth nitrate and titanium butoxide as starting materials. The structural properties were studied by X-ray diffraction. The dielectric constant at 100 kHz at room temperature was 118 and loss factor was 0.074, for a 0.4-μm-thick film annealed at 500°C for 30 min. The leakage current density was 4.06×10⁻⁷ A/cm² at an applied voltage of 15 V.