Contribution to the comprehension of dissipation phenomena in lead zirconate titanate: aliovalent doping effect

By the solid reaction method, undoped, potassium doped and niobium doped lead zirconate titanate (PZT) are elaborated. The mechanical losses measured in the range of the Hz as a function of temperature shows two peaks R₁ and R₂, and a ferroelectric transition peak P₁ between ferroelectric and para-electric states on the undoped PZT—Pb(Zr_0.54Ti_0.46)O₃—noted PZT54/46. Potassium doped PZT—Pb_1−xK_x(Zr_0.54Ti_0.46)O₃—shortly called PKZT 100x/54/46 shows an increase in the height of both the peaks at a doping content, x, less than 0.5 at.% but an opposite effect is observed above this value. Niobium doped PZT—Pb[(Zr_0.54Ti_0.46)_1−yNb_y]O₃—shortly called PNZT 100y/54/46, shows the vanish of the R₂ peak and the decrease of the height of the R₁ peak when the doping content increases.     

Glass formation and conductivity in the Pb2P2O7–Ag4P2O7–AgI system

A large glass-forming domain has been identified in the Pb₂P₂O₇–Ag₄P₂O₇–AgI system. The physical properties have been determined as a function of AgI content. The ionic conductivity has been studied as a function of the Ag⁺ ion total concentration and the Ag⁺ ion concentration issued from the AgI component. The structure and electrical properties of obtained glasses are compared with those of ionic glasses of the Ag₄P₂O₇–AgI system.     

Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

Magnetic behaviour of Cd and Cr substituted cobalt ferrites

Polycrystalline samples with general formula Cd_xCo_1−xFe_2−yCr_yO₄ (x=0, 0.25, 0.50, 0.75 and 1.00; y=0, 0.15 and 0.30) were prepared by standard ceramic techniques. The samples were characterized by XRD, IR, SEM and VSM techniques. The magnetic properties were studied at room temperature. The Neel's two-sublattice model is found to exist for lower concentration of Cd (x<0.25). Thereafter (x≥0.25) the canted spin model is found to exist for which Yafet–Kittel (Y–K) angles are calculated. The saturation magnetic moment is found to reduce with the substitution of Cr³⁺, and is explained on the basis of cation distribution. No magnetic transformation is observed for the samples with higher cadmium concentrations (for x=0.75 and 1.00).     

Effects of oxygen partial pressure on lead content of PLZT thin films produced by excimer laser deposition

Excimer laser ablation has been used to produce thin films of lanthanum-modified lead zirconate titanate (PLZT), or Pb_1−xLa_x(Zr_1−yTi_y)_1−x/4O₃. PLZT is an interesting class of materials since it has a wide range of compositionally dependent electro-optical properties and strong non-linear optical characteristics. PLZT thin films of 7/0/100, 28/0/100 and 0/0/100 compositions have been deposited onto crystalline Si100 and amorphous fused silica substrates. Effects of oxygen backfill pressure on the Pb:(Ti + La) ratios were investigated. The results indicate that controlling the oxygen backfill pressure during laser deposition strongly influences the stoichiometry and crystal structure of PLZT thin films.     

Optical properties and laser performance of neodymium doped fluoroapatites SrxCa5−x(PO4)3F (x = 0, 1, 2, 3, 4, and 5)

Nd doped fluoroapatites Sr_xCa_5−x(PO₄)₃F(S_xC_5−xPF, X = 0, 1, 2, 3, 4, and 5) single crystals have been grown by the Czochralski technique. Their polarized absorption and emission spectra have been recorded at room temperature and used to calculate the absorption and stimulated emission cross sections. Broadening of the absorption and emission bands is observed for Nd³⁺ in the solid solutions SPF-CPF compared to Nd³⁺ in CPF or SPF. 1% Nd:S_xC_5−xPF, X = 0, 2, 3, 4, and 5, laser rods have been tested in a cavity longitudinally pumped by a 1 W AlGaAs laser diode and compared to Nd:YAG and Nd:YVO₄ rods. All fluoroapatites exhibit very good laser performance with low thresholds and high slope efficiencies, higher than in the case of YAG and equal to the YVO₄ samples. The dependance of the laser output power versus the diode temperature has also been measured for all materials. The laser output was found to be as sensitive to the diode temperature fluctuations for fluoroapatites as for YAG.     

Doping and electrical characteristics of in-situ heavily B-doped Si1−x−yGexCy films epitaxially grown using ultraclean LPCVD

Doping and electrical characteristics of in-situ heavily B-doped Si_1−x−yGe_xC_y (0.22<x<0.6, 0<y<0.02) films epitaxially grown on Si(100) were investigated. The epitaxial growth was carried out at 550°C in a SiH₄–GeH₄–CH₃SiH₃–B₂H₆–H₂ gas mixture using an ultraclean hot-wall low-pressure chemical vapor deposition (LPCVD) system. It was found that the deposition rate increased with increasing GeH₄ partial pressure, and only at high GeH₄ partial pressure did it decrease with increasing B₂H₆ as well as CH₃SiH₃ partial pressures. With the B₂H₆ addition, the Ge and C fractions scarcely changed and the B concentration (C_B) increased proportionally. The C fraction increased proportionally with increasing CH₃SiH₃ partial pressures. These results can be explained by the modified Langmuir-type adsorption and reaction scheme. In B-doped Si_1−x−yGe_xC_y with y=0.0054 or below, the carrier concentration was nearly equal to C_B up to approximately 2×10²⁰ cm⁻³ and was saturated at approximately 5×10²⁰ cm⁻³, regardless of the Ge fraction. The B-doped Si_1−x−yGe_xC_y with high Ge and C fractions contained some electrically inactive B even at the lower C_B region. Resistivity measurements show that the existence of C in the film enhances alloy scattering. The discrepancy between the observed lattice constant and the calculated value at the higher Ge and C fraction suggests that the B and C atoms exist at the interstitial site more preferentially.     

Growth of lithium doped silver niobate single crystals and their piezoelectric properties

Lithium doped silver niobate (Ag_1−xLi_xNbO₃, 0 < x < 0.1) is one of the candidate materials for lead-free piezoelectric materials. In this study, Ag_1−xLi_xNbO₃ single crystals were successfully grown by a slow cooling method. Crystal structure was assigned to perovskite-type orthorhombic (monoclinic) phase. Dielectric properties were measured as a function of temperature. As a result, with increasing lithium contents, the phase transition at around 60 °C was shifted to lower temperature while the phase transition at around 400 °C was shifted to higher temperature. On the basis of these peak shifts, the lithium contents in Ag_1−xLi_xNbO₃ single crystals were determined. Moreover, P–E hysteresis measurement revealed that pure silver niobate crystal was weak ferroelectrics with P_r of 0.095 μC/cm² while Ag_0.9Li_0.1NbO₃ (ALN10) crystal was normal ferroelectrics with P_r of 10.68 μC/cm². About this ALN10 crystal, polling treatment was performed and finally piezoelectric properties were measured. As a result, high electromechanical coupling coefficient k₃₁ over 70% was observed.     

Structural characterization of ion-beam-induced epitaxially crystallized thin layers of III–V and IV–IV semiconductors

Structural properties of ion-beam-induced epitaxial crystallization (IBIEC) for amorphous layers of GaAs on GaAs(100), BP on BP(100) and Si_1−xGe_x and Si_1−x−yGe_xC_y on Si(100) have been investigated. Crystallization was induced by ion bombardment with 400 keV Ne, Ar or Kr at 150 °C for GaAs and at 350 °C for BP. Epitaxial crystallization up to the surface was observed both in GaAs and BP at temperatures much below those required for the solid phase epitaxial growth (SPEG). The growth rate per nuclear energy deposition density has shown a larger dependence on ion dose rate in cases of heavier ion bombardments both for GaAs and BP. Crystallization of a-GaAs with ions whose projected ranges are within the amorphous layer thickness was also observed at 150 °C. Epitaxial crystallization of Si_1−xGe_x and Si_1−x−yGe_xC_y layers (x = 0.13 and y = 0.014 at peak concentration) on Si(100) formed by high-dose implantation of 80 keV Ge and 17 keV C ions has been observed in the IBIEC process with 400 keV Ar ion bombardments at 300–400 °C. Crystalline growth by IBIEC has shown a larger growth rate in Si_1−x−yGe_xC_y/Si} than in Si_1−xGe_x/Si} with the same Ge concentration for all bombardments under investigation. X-ray rocking-curve measurements have shown a strain-compensated growth in Si_1−x−yGe_xC_y/Si}, whereas Si_1−xGe_x/Si} samples have shown a growth with strain accommodation.     

Optical band gap studies on xPb3O4–(1−x)P2O5 lead[(II, IV)] phosphate glasses

A series of glasses in the xPb₃O₄–(1−x)P₂O₅ (red lead phosphate) (RLP) system with ‘x' varying from 0.075 to 0.4 were prepared by the single-step melt quenching process from Pb₃O₄ and NH₄H₂PO₄. The optical absorption spectra of these glasses have been recorded in the ultraviolet region from 200 to 400 nm and the fundamental absorption edges have been identified. The optical band gap E_opt values have been determined for all the glasses using the known theories. The (E_opt) values vary from 4.90 to 3.21 eV the highest being 4.57 eV, corresponding to the most stable glass of x=0.225. The absorption edge is attributed to the indirect transitions and the origin of the Urbach energy ΔE is suggested to be thermal vibrations. These glasses promise as potential candidates for application in optical technology compared to simple xPbO–(1−x)P₂O₅ (lead phosphate) (LP) glasses.     

Structural investigation of bulk and thin film PLZT using X-ray absorption spectroscopy

Thin film electro-optic and non-linear optical materials are of interest for applications in high-speed integrated optical devices. Materials of the system Pb_1−x/100La_x/100(Zr_y/100 Ti_1−y/100)_1−x/400O₃ or PLZT x/y/(100−y) are attractive since they can be integrated into Si and GaAs substrates using suitable deposition techniques. In this investigation we examine the structural properties of r.f. magnetron sputter-deposited PLZT using X-ray absorption near-edge spectroscopy (XANES). For XANES analysis, four samples were selected: (1) a highly oriented PLZT 28/0/100 film of ≈ 4500 Å deposited on SiO₂; (2) a highly oriented PLZT 28/0/100 film of ≈ 4500 Å deposited on a 2 ωm SiO₂ buffer layer over a Si(100) substrate; (3) a highly oriented PLZT 28/0/100 film of ≈4500 Å deposited on Al₂O₃ (1 02); and (4) a commercial ceramic wafer of PLZT 9/65/35. The XANES experiments were performed at the Stanford Synchrotron Radiation Laboratory (SSRL) using electron yield and fluorescence techniques. Data was taken at the Ti K-edge (4966.4eV) and compared to reference spectra. Of the reference spectra, the Ti K-edge spectra of the PLZT most closely resemble perovskite (SrTiO₃). The surface and bulk thin film are similar and all the 28/0/100 spectra resemble the spectra of 9/65/35, indicating similar cubic perovskite structures for these materials.     

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.     

Preparation and characterization of lithium nickel cobalt oxide powders via a wet chemistry processing

Nickel-rich phases of the solid solutions, LiNi_1−yCo_yO₂ (y=0.1, 0.2, 0.3), were synthesized by a sol–gel method with citric acid as a chelating agent. Various initial conditions were studied in order to find the optimal conditions for the synthesis of LiNi_0.8Co_0.2O₂. The discharge capacity for the compound synthesized under an optimal synthesis condition of 800 °C for 12 h was found to be 187 mAh g⁻¹ in the 1st cycle and it was 176 mAh g⁻¹ after 10 cycles. The other nickel-rich phases, namely, LiNi_0.9Co_0.1O₂ and LiNi_0.7Co_0.3O₂ showed 1st-cycle discharge capacities of 144 and 163 mAh g⁻¹, respectively. The corresponding capacity values were 140 and 159 mAh g⁻¹ in the 10th cycle. Excess lithium stoichiometric phases, Li_xNi_0.8Co_0.2O₂, where x=1.10, 1.15 and 1.20, resulted in decreased capacity. Structural and electrochemical properties of the synthesized compounds were compared with those of a commercial LiNi_0.8Co_0.2O₂ sample. The effect of calcination temperature and duration, excess lithium stoichiometry and divalent strontium doping in LiNi_0.8Co_0.2O₂ are described. Doping with strontium improved both the capacity and cycling performance of LiNi_0.8Co_0.2O₂.     

Bond-lengths of the atomic nearest-neighbor and next-nearest-neighbor in A1−xBxC1−yDy III–V solid solutions

On the basis of the FDUC model and the hypothesis of the constant covalent radii, the expressions of the atomic nearest-neighbor and the next-nearest-neighbor bond-lengths were derived for A_1−xB_xC_1−yD_y III–V quaternary solid solutions. This set of bond-length expressions predicts the averaged bond-lengths and bond angles at any concentration (x, y) for the III–V pseudobinary and quaternary solid solutions, which are only dependent on the lattice parameters and the concentrations of the pure end compounds. When x=0, 1 or y=0, 1, A_1−xB_xC_1−yD_y III–V quaternary solid solutions degenerate into the relative pseudobinary solid solutions, in which the nearest-neighbor and the next-nearest-neighbor bond-lengths agree well with the experimental results. Further discussion and comparison with other theoretical models are also given in this paper.     

High-resolution and analytical transmission electron microscopy of epitaxial YBa2Cu3O7−x thin films and YBa2Cu3O7/PrBa2Cu3O7 superlattices

Transmission electron microscopy (TEM) studies of epitaxial YBa₂Cu₃O_7−x thin films and YBa₂Cu₃O₇/PrBa₂Cu₃O₇ superlattices are summarized. High-resolution imaging of cross-sections and plan views and energy-dispersive X-ray microanalysis and electron energy loss spectroscopy in the transmission electron microscope were the methods applied. In the first section results on YBa₂Cu₃O_7−x thin films With varying oxygen stoichiometry deposited onto SrTiO₃ are discussed. Then, YBa₂Cu₃O₇/PrBa₂Cu₃O₇ superlattices deposited onto SrTiO₃ and MgO are investigated. Finally, an interface analysis of high-quality YBa₂Cu₃O_7−x thin films deposited onto sapphire with yttrium-stabilized zirconia buffer layers is presented.     

Optical properties of a-(Se70Te30)100−x(Se98 Bi2)x thin films

Measurements of optical constants (absorption coefficient, refractive index, extinction coefficient, real and imaginary part of the dielectric constant) have been made on a-(Se₇₀Te₃₀)_100−x (Se₉₈Bi₂)_x thin films (where x=0, 5, 10, 15 and 20) of thickness 2000 Å in the wavelength range 450–1000 nm. It is found that the optical bandgap decreases with the increase of Se₉₈Bi₂ concentration in the a-(Se₇₀Te₃₀)_100−x(Se₉₈Bi₂)_x system. The value of refractive index (n) decreases, while the extinction coefficient (k) increases with increasing photon energy. The results are interpreted in terms of concentration of localized states varying effective Fermi level.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Influence of thermal treatments on the elastic parameters in iron rich metallic glasses

The change of magnetoelastic properties after thermal treatments has been investigated for two groups of metallic glasses. (Fe₇₉Co₂₁)_75+xSi_15−1.4xB_10+0.4x (x (at.%)=0, 2, 4, 6, 8, 10) has been studied both in the as-prepared state and after thermal annealing in an applied magnetic field, to achieve a particular domain structure, at temperatures well below the crystallization temperatures. Changes in the ΔE effect, magnetomechanical coupling (k) and internal friction coefficient (Q⁻¹) are reported, reaching values of about 60% of the saturation value E_S. Fe₆₄Ni₁₀Nb₃Cu₁Si₁₃B₉ alloys annealed in vacuum for 1 h in the temperature range 350–550 °C showed maximum values of the ΔE effect and k of 61% and 0.85, respectively, accompanied by a minimum value of Q of around 2 for the sample annealed at 460 °C. These variations are related to the progress of nanocrystalization. The properties achieved are among the best reported for magnetomechanical applications.     

(La1-xMgx)2Ce2O7-x的合成与热物理性能

Mg对La₂Ce₂O₇的掺杂可提高其热膨胀系数、降低其热导率, 从而改善其作为热障涂层材料的性能。采用溶胶-凝胶法制备了(La_1-xMg_x)₂Ce₂O_7-x系列组成样品。X射线测试表明: 当 0≤x≤0.4时, 所有(La_1-xMg_x)₂Ce₂O_7-x 样品均与La₂Ce₂O₇具有相同的缺陷萤石结构, 且晶胞参数随x的增大而递减; 当x?0.4时, 样品中出现MgO的峰。在组成相同的情况下, 样品(La_1-xMg_x)₂Ce₂O_7-x (0≤x≤0.4)的热膨胀系数随温度升高而增大, 而热导率随温度升高而降低。在相同温度下, 不同组成样品(La_1-xMg_x)₂Ce₂O_7-x (0≤x≤0.4)的热膨胀系数随x的增大而增大; 而样品的热导率则随Mg掺杂量的增加呈先增大后减小的趋势。在此基础上, 探讨了Mg掺杂对La₂Ce₂O₇的物相、晶胞参数、热膨胀系数以及热导率的影响机理。     

Investigation on the cross sensitivity of NO2 sensors based on In2O3 thin films prepared by sol-gel and vacuum thermal evaporation

In₂O₃ thin films have been prepared from commercially available pure In₂O₃ powders by high vacuum thermal evaporation (HVTE) and from indium iso-propoxide solutions by sol-gel techniques (SG). The films have been deposited on sapphire substrates provided with platinum interdigital sputtered electrodes. The as-deposited HVTE and SG films have been annealed at 500°C for 24 and 1 h, respectively. The film morphology, crystalline phase and chemical composition have been characterised by SEM, glancing angle XRD and XPS techniques. After annealing at 500°C the films’ microstructure turns from amorphous to crystalline with the development of highly crystalline cubic In₂O_3−x (JCPDS card 6-0416). XPS characterisation has revealed the formation of stoichiometric In₂O₃ (HVTE) and nearly stoichiometric In₂O_3−x (SG) after annealing. SEM characterisation has highlighted substantial morphological differences between the SG (highly porous microstructure) and HVTE (denser) films. All the films show the highest sensitivity to NO₂ gas (0.7–7 ppm concentration range), at 250°C working temperature. At this temperature and 0.7 ppm NO₂ the calculated sensitivities (S=R_g/R_a) yield S=10 and S=7 for SG and HVTE, respectively. No cross sensitivity have been found by exposing the In₂O₃ films to CO and CH₄. Negligible H₂O cross has resulted in the 40–80% relative humidity range, as well as to 1 ppm Cl₂ and 10 ppm NO. Only 1000 ppm C₂H₅OH has resulted to have a significant cross to the NO₂ response.