Phase stabilization and microstructural studies of lead lanthanum titanate thin films

Thin ferroelectric films of PLTx (Pb_1−xLa_xTi_1−x/4O₃) have been prepared by a sol-gel spin coating process. As deposited films were thermally treated for crystallization and formation of perovskite structure. Characterization of these films by X-ray diffraction (XRD) have been carried out for various concentrations of La (x = 0.04, 0.08 and 0.12) on ITO coated corning glass substrates. For a better understanding of the crystallization mechanism, the investigations were carried out on films annealed at temperatures (350, 450, 550 and 650 °C). Characterization of these films by X-ray diffraction shows that the films annealed at 650 °C exhibit tetragonal phase with perovskite structure. Atomic force microscope (AFM) images are characterized by slight surface roughness with a uniform crack free, densely packed structure. Fourier transform infrared spectra (FTIR) studies of PLTx thin films (x = 0.08) deposited on Si substrates have been carried out to get more information about the phase stabilization.     

Order-disorder phase transitions and high-temperature oxide ion conductivity of Er2+xTi2−xO7−δ (x = 0, 0.096)

The Er_2+xTi_2−xO_7−δ (x = 0.096; 35.5 mol% Er₂O₃) solid solution and the stoichiometric pyrochlore-structured compound Er₂Ti₂O₇ (x = 0; 33.3 mol% Er₂O₃) are characterized by X-ray diffraction (phase analysis and Rietveld method), thermal analysis and optical spectroscopy. Both oxides were synthesized by thermal sintering of co-precipitated powders. The synthesis study was performed in the temperature range 650-1690 °C. The amorphous phase exists below 700 °C. The crystallization of the ordered pyrochlore phase (P) in the range 800-1000 °C is accompanied by oxygen release. The ordered pyrochlore phase (P) exists in the range 1000−1200 °C. Heat-treatment at T ≥ 1600 °C leads to the formation of an oxide ion-conducting phase with a distorted pyrochlore structure (P2) and an ionic conductivity of about 10⁻³ S/cm at 740 °C. Complex impedance spectra are used to separately assess the bulk and grain-boundary conductivity of the samples. At 700 °C and oxygen pressures above 10⁻¹⁰ Pa, the Er_2+xTi_2−xO_7−δ (x = 0, 0.096) samples are purely ionic conductors.     

Microwave dielectric properties of (Pb1−3x/2Lax)(Mg1/2W1/2)O3

La modified Pb(Mg_1/2W_1/2)O₃ were prepared by solid-state reaction process, and the sintering behavior, microstructure and microwave dielectric properties were investigated by X-ray powder diffraction (XRD), Raman scattering and HP network analyzer in this paper. A series of single phase perovskite type solid solutions with A-site vacancies (Pb_1−3x/2La_x(Mg_1/2W_1/2)O₃ (0 ≤ x ≤ 2/3)) were formed. The solid solution took cubic perovskite type structure (Fm3m) with random distribution of A-site vacancies when 0 < x < 0.5, and tetragonal or orthorhombic structure with the ordering of A-site vacancies when 0.5 ≤ x ≤ 2/3. The dielectric constant and temperature coefficient of resonant frequency decrease with increasing La content. Relatively good combination microwave dielectric properties were obtained for x = 0.56: ?_r = 28.7; Q × f = 18098; and τ_f = −5.8 ppm/°C.     

Effects of La substitution for Nd in (Nd2−xLax)BaZnO5 solid solutions on microwave dielectric properties and crystal structure

The synthesis and microwave dielectric characterization of (Nd_2−xLa_x)BaZnO₅ solid solutions were studied. The samples obtained were single phase over the whole composition range and the lattice parameters of solid solutions were linearly increased with increasing the composition. Moreover, the expansion of the volume in the RO₈ (R=Nd and La) and BaO₁₀ polyhedra and ZnO₄ tetrahedron were recognized when Nd ions were substituted by La. These variations in the lattice parameters and volumes of the polyhedra are basically attributed to the differences in ionic radii between Nd³⁺ and La³⁺ ions. From the evaluation of microwave dielectric properties, it was shown that the appropriate τ_f values ranging from 4.6 to −5.0 ppm/°C are obtained by La substitution for Nd ion, and the highest Q · f value was 17,832 GHz at x=2.     

Crystal structure and EPR study of Mn-doped β-tricalcium phosphate

Mn-doped β-tricalcium phosphate was prepared by solid state reaction at 1100 °C. The crystal structure of Ca_2.85Mn_0.15(PO₄)₂, was determined by single crystal X-ray diffraction and found to be rhombohedral, R3c. Unit cell parameters are: a = 10.3419(3); c = 37.025(3) Å (hexagonal setting), Z = 21. Structure refinement data show that from the five Ca positions the Ca(4) site is only half filled and that the Mn²⁺ ions occupy the hexacoordinated Ca(5) site solely. EPR spectroscopy reveals that manganese in solid solutions Ca_3−xMn_x(PO₄)₂ (x = 0.1; 0.28; 0.6) is divalent and supports the structure refinement results that Mn occupies the Ca(5) site with a geometry very near to a regular octahedron.     

Structural characterization of 0.5PbMg1/3Nb2/3O3-0.5BaxPb(1−x)TiO3 powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5Pb(Mg_1/3Nb_2/3)O₃-0.5(Ba_xPb_(1−x)TiO₃) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 nm for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 °C for 4 h.     

Effect of substitution in the scheelite-like series, AxBa1−xBi2Mo4O16 (A = Ca, Sr, Pb)

A new series of solid solutions of the type, A_xBa_1−xBi₂Mo₄O₁₆ (A = Ca, Sr, Pb) have been isolated. The domain of the solid solutions is very narrow and is in the range (0.01 ≤ x ≤ 0.10). All the phases were synthesized by the solid-state technique. The crystal structure is similar to that of the monoclinic scheelite type BaBi₂Mo₄O₁₆. The structure consists of layers of [Bi₂O₂] units separated by (Ba/AO)₁₀ units and isolated MoO₄ tetrahedra. Their semiconductor band gaps render them as potential materials for photocatalysis.     

Synthesis and characterization of strontium-lanthanum apatites

Two series of strontium-lanthanum apatites, Sr_10−xLa_x(PO₄)_6−x(SiO₄)_xF₂ and Sr_10−xLa_x(PO₄)_6−x(SiO₄)_xO with 0 ≤ x ≤ 6, were synthesized by solid state reaction in the temperature range of 1200-1400 °C. The obtained materials were characterized by powder X-ray diffraction, infrared absorption spectroscopy and solid ³¹P Nuclear Magnetic Resonance. Pure solid solutions were obtained within a limited range of unsubstituted phosphate and silicate apatites. A variation of the lattice parameters was observed, with an increase of a and a decrease of c parameters, related to the radius of the corresponding substituted ions.     

Improved thermoelectric properties in directionally grown Bi2Sr2Co1.8Oy ceramics by Pb for Bi substitution

Thermoelectric performances of misfit cobaltites can be controlled by grain orientation and/or by cation substitution. Both processes have been simultaneously performed by directional solidification at 0.03 m/h, using the laser floating zone technique, of Bi_2−xPb_xSr₂Co_1.8O_y (with x = 0.0, 0.2, 0.4 and 0.6). The microstructure has shown two different main phases as a function of Pb content, a Co-poor phase for low Pb content (0.0 and 0.2) and a Co-rich one for higher Pb substitution. These microstructural changes are reflected on the thermoelectric properties leading to an important decrease on the resistivity and increase of thermopower for samples with 0.4Pb substitution. Both improvements lead to power factor values higher than usual in textured misfit cobaltites.     

Heterophase structures and their quantitative characteristics in (1 − x)Pb(Fe1/2Nb1/2)O3 − xPbTiO3 near the morphotropic phase boundary

Features of phase coexistence in solid solutions of (1 − x)Pb(Fe_1/2Nb_1/2)O₃ − xPbTiO₃ with the perovskite-type structure are studied at 0.05 ≤ x ≤ 0.08. The role of elastic matching of the tetragonal P4mm and monoclinic Cm phases of the ferroelectric nature is considered near the morphotropic phase boundary. Model concepts on the stress relief in heterophase structures are developed and applied to interpret the phase content in (1 − x)Pb(Fe_1/2Nb_1/2)O₃ − xPbTiO₃. Good agreement between the calculated and experimental dependences of the volume fraction of the tetragonal phase on x is observed. It is shown that the studied phase coexistence under conditions for the complete stress relief can take place at elastic matching of the single-domain monoclinic phase and the tetragonal phase split into two types of 90° domains.     

Synthesis of (1 − x)Ca2/5Sm2/5TiO3-xLi1/2Nd1/2TiO3 ceramic powder via ethylenediaminetetraacetic acid precursor

(1 − x)Ca_2/5Sm_2/5TiO₃-xLi_1/2Nd_1/2TiO₃ (CSLNT) ceramic powder was prepared by a liquid mixing method using ethylenediaminetetraacetic acid (EDTA) as the chelating agent. TG, DTA, XRD and TEM characterized the precursors and derived oxide powders. When x = 0.3, perovskite CSLNT was synthesized at 1000 °C for 3 h in air. The CSLNT (x = 0.3) ceramics sintered at 1200 °C for 3 h show excellent microwave dielectric properties of ?_r = 99, Q_f = 6200 GHz and τ_f = 9 × 10⁻⁶ °C⁻¹.     

Synthesis, structural and magnetic properties of La1−xCdxFeO3 (0.0 ≤ x ≤ 0.3) orthoferrites

Nanocrystalline La_1−xCd_xFeO₃ (0.0 ≤ x ≤ 0.3) solid solutions have been synthesized by a single-step solution combustion method at a relatively low temperature of 400 °C. The combustion-synthesized solid solutions were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and magnetic measurements. The crystal structure examined by XRD indicates that the samples were single-phase, and crystallize in an orthorhombic (space group, Pbnm no. 62) structure. The parent and doped compounds showed canted antiferromagnetic behavior associated with an increase in magnetic moment with Cd doping. The changes in magnetic properties of the materials are correlated to the changes in structural features resulting from the Rietveld structural refinement of the materials.     

Diffusion of Pb in carbon ion-implanted silicon: Discovery of a new crystalline phase after electron beam annealing

A novel phase has been discovered by dual low-energy ion implantation and high vacuum electron beam annealing. (100) p-type Si was implanted with (a) 20 keV ¹²C⁺ ions to the fluence of 6 × 10¹⁶ cm⁻² and (b) 7 keV Pb⁺ ions to the fluence of 4 × 10¹⁵ cm⁻². The ¹²C ion implantation results in an understoichiometric shallow SiC_x layer that intersects with the surface. The implanted Pb ions decorate a shallow subsurface region. High vacuum electron beam annealing at 1000 °C for 15 s using a temperature gradient of 5 °C s⁻¹ leads to the formation of large SiC nanocrystals on the surface with RBS measurements showing Pb has diffused into the deeper region affected by the ¹²C implantation. In this region, a new crystalline phase has been discovered by XRD measurements.     

Structure and negative thermal expansion of Pb1 −xBixTiO3

Pb_1-xBi_xTiO₃ (x = 0.0-0.1) compounds were prepared to study the unique dopant effect of bismuth in PbTiO₃. Their thermal expansions and structures were investigated by high-temperature X-ray diffraction and X-ray Rietveld method. The results indicated that Bismuth substitution evidently weakened the tetragonality of PbTiO₃ solid solution, but increased the spontaneous polarization. Both the enhanced spontaneous polarization and the decreased tetragonality led to small volume shrinkage with temperature rising, where the average volumetric thermal expansion coefficient changed from − 1.99 × 10^− 5/°C for pure PbTiO₃ to − 0.56 × 10^− 5/°C for Pb_0.90Bi_0.10TiO₃. The Curie point of Pb_1 − xBi_xTiO₃ was slightly raised compared to PbTiO₃ and permitted one to use it in a wide temperature range.     

Indium and gallium oxynitrides prepared in the presence of Zn by ammonolysis of the oxide precursors obtained via the citrate route

Ammonia nitridation of indium and gallium oxide precursors obtained through a soft solution route led to their oxynitrides [In_0.97□_0.03][N_0.92O_0.08] at 660 °C and [Ga_0.89□_0.11][N_0.66O_0.34] at 850 °C, respectively, where □ refers to a In or Ga vacancy. Cation vacancies in their wurtzite-type lattice were eliminated in similar preparations with the co-presence of Zn²⁺ by forming complete solid solutions of (InN)_1−x(ZnO)_x and (GaN)_1−y(ZnO)_y. The optical absorption edge shape was found to be relatively steep at the solid solution limits of x ≈ 0.23 and y ≈ 0.33 compared to the case without zinc.     

Structural and superconducting properties of neodymium added (Bi,Pb)2Sr2CaCu2Oy

The effects of neodymium (Nd) addition on the phase evolution, structural and superconducting properties of (Bi,Pb)₂Sr₂CaCu₂O_y [(Bi,Pb)-2212] prepared by solid state synthesis in bulk polycrystalline form were studied. The Nd content was varied from x = 0 to 0.5 on a general stoichiometry of Bi_1.7Pb_0.4Sr_2.0Ca_1.1Cu_2.1Nd_xO_y. The samples were characterized by differential thermal analysis (DTA), powder X-ray diffraction, scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysis (EDX), resistance-temperature (R-T) measurements and superconductivity measurements at 64 K. It was found that the melting temperature of (Bi,Pb)-2212 slightly increases and the endotherm broadens due to the Nd-addition. The c-lattice parameter initially decreases and then increases with Nd addition. The critical temperature (T_C) and the critical current density (J_C) of the added samples are highly enhanced. The added sample shows a maximum onset critical temperature (T_C-onset) of 95.56 K (x = 0.3) and a maximum critical current density of 719 A/cm² at 64 K (x = 0.2) against 76.7 K and 100 A/cm², respectively, for the pure sample. The results show that the enhancement in superconducting properties are not due to any improvement in microstructure or grain growth, but due to a decrease in hole concentration as a result of Nd doping, which changes the system from ‘over-doped condition’ to ‘optimally doped condition’.     

Polymeric citrate precursor route to the synthesis of nano-sized barium lead titanates

Monophasic oxides of the formula, Ba_1−xPb_xTiO₃ (0≤x≤1.0) were obtained at temperatures close to 500 °C from polymeric precursors formed using citric acid and ethylene glycol. These oxides were found to be tetragonal for all values of x, the distortion increasing with Pb content. Differential scanning calorimetry (DSC) shows that the decomposition of the precursor to the oxides varies with composition and the decomposition temperature is highest (530 °C) for the x=0.5 composition. X-ray line broadening studies of 900 °C sintered samples show grain size of 50-54 nm in all compositions. TEM studies show agglomerated grains of the size, 40-60 nm. The dielectric constant (ε) decreases with lead-doping having a value 70 for PbTiO₃. The dielectric loss (D) for different compositions varied between 0.005 and 0.01 at 100 kHz. The dielectric constant and loss show excellent frequency stability.     

Nonlinear optical diagnostic of semimagnetic semiconductors Pb1−xYbxX (X = S, Se, Te)

Nonlinear optical measurements were performed to elucidate the influence of magnetic ions on the behavior of charge carriers in magnetic semiconductors—Pb_1−xYb_xX (X = S, Se, Te at x = 1-3%). It was shown that nonlinear optical methods could be used as sensitive tools for investigations of electron-phonon anharmonicity near low-temperature semiconductor-insulator phase transitions. There exists a difference between surface and bulk-like contributions to the nonlinear optical effects. It was shown that only low-temperature Two Photon Absorption (TPA) oscillator may be related to the number of the electron-phonon anharmonic modes responsible for the observed phase transformation. The explanation of the anomalous temperature dependences is given in accordance with dipole momentum's behaviors determined by low-temperature spin-spin interactions and by electron-phonon anharmonic interactions. We have discovered that low-temperature dependence of specific heat of Pb_1−xR_xTe (R = Yb, Pr with x = 3% and 1.6%, respectively) exhibits a non-magnetic order caused by large electron-phonon contributions and structural disorder effects.     

Hydrochemical synthesis, structure, semiconductor properties of films of substitutional Pb1 − xSnxSe solid solutions

The region of lead and tin selenide co-deposition using selenourea has been examined by calculation of the ionic equilibrium in the citrate-ammonia system. The formal kinetic equations for the rates of formation of the lead and tin selenides have been determined. Thin films of substitutional Pb_1 − xSn_xSe (0 < x < 0.093) solid solutions were produced from aqueous solutions. The composition, crystal lattice spacing, thermal band gap and conductivity of the films have been analysed.     

Re-examination of the structural properties of solid solutions SrxCa1−xCO3

We have re-examined the evolution of orthorhombic cell parameters as a function of the substitution parameter x in solid solutions Sr_xCa_1−xCO₃ in order to clarify contradictory results found in the literature. Calcium carbonate has been synthesized in the presence of Sr²⁺ ions (Sr/Ca molar ratio ranging from 10⁻² to 1), using experimental conditions that previously allowed us to obtain monophasic aragonite. The precipitates obtained have been analysed using powder X-ray diffractometry (XRD) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The powder XRD data confirm the occurrence of purely monophasic strontian-aragonites. Moreover, the cell parameters as well as the substitution parameter x have been refined for 0 < x < 0.5 against powder XRD data through Rietveld refinement. On the other hand, x was deduced from chemical analysis by ICP-AES. The agreement between both techniques is very satisfactory. The evolution of the cell parameters as a function of x is found to be linear within the studied range, this feature being confirmed for the overall domain (0 ≤ x ≤ 1) if one takes into account the cell parameters of aragonite CaCO₃ and strontionite SrCO₃. This result, that is consistent with the existence of continuous solid solutions obeying the Vegard's law in the Sr_xCa_1−xCO₃ system, contradicts previously published assertions.