Dielectric, piezoelectric and elastic properties of tetragonal BiScO3-PbTiO3 single crystal with single domain

Modified BiScO₃-PbTiO₃ (BSPT) tetragonal single crystals were grown using high temperature solution method. The dielectric, piezoelectric and elastic properties of single domain BSPT crystals, after poling along [001] crystallographic direction, have been determined experimentally using the resonance method. The results showed that the BSPT tetragonal crystals possess good piezoelectric properties, with electromechanical coupling factor about 88% and piezoelectric coefficient over 400 pC/N at room temperature. BSPT tetragonal crystals have high Curie temperature around 436 °C and high coercive field ∼28 kV/cm, also, the crystal exhibited a very good temperature stability of the properties till 380 °C. For comparison, the material constants of tetragonal Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PZNT) single crystals were measured and listed in this paper.     

Electrical properties of high Curie temperature (1−x)Pb(In1/2Nb1/2)O3-xPbTiO3 single crystals grown by the solution Bridgman technique

0.65Pb(In_1/2Nb_1/2)O₃-0.35PbTiO₃ (PINT65/35) (starting composition) single crystals were grown successfully through the solution Bridgman technique using PbO flux and PMNT67/33 seed crystals. Because of the composition variation, the final composition of achievable crystals is in a range of 0.32-0.34 with the corresponding T_c range of 265-269 °C. The (001) plates of as-grown PINT66/34 single crystals show high Curie temperature (T_c=269 °C) and rhombohedral-tetragonal phase transition temperature (T_rt=134 °C). Besides, good electrical properties with high dielectric constant (ε>3000), low dielectric loss (tan δ∼1.2%), high piezoelectric constant (d₃₃∼2000 pC/N) and large electromechanical coupling factor (k_t≈59%) at room temperature have been obtained on the (001) plates. The sound velocity, acoustic impedance and other piezoelectric parameters were also measured on the (001) plates in this study, which provide us more detailed information about PINT66/34 single crystals.     

Electro-optic characterization of tetragonal (1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals by a modified Sénarmont setup

The refractive indices of tetragonal (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-xPT) single crystals were measured with a prism coupler and their linear electro-optic (EO) properties were investigated from 20 to 80 °C by the automated scanning Sénarmont system with an ac field. The composition and temperature effect on the EO coefficients were also discussed. It has been found that their EO coefficients are much larger than that of widely used LiNbO₃ single crystal and the calculated half-wave voltages are also much lower, which enable the operation at lower voltages and the smaller device dimensions. Since the excellent EO properties are very stable and such high quality single crystals with large-size have been obtained, the PMN-xPT single crystals are a very promising candidate for EO modulation applications. By linking to the polarization-related quadratic EO coefficients, we find that the linear EO properties are related with the spontaneous polarization and dielectric constants.     

Writing of two-dimensional crystal curved lines at the surface of Sm2O3-Bi2O3-B2O3 glass by samarium atom heat processing

Two-dimensional crystal curved lines consisting of the nonlinear optical Sm_xBi_1−xBO₃ phase are fabricated at the surface of 8Sm₂O₃·37Bi₂O₃·55B₂O₃ glass by continuous wave Nd:YAG laser (wavelength: 1064 nm) irradiation (samarium atom heat processing) with a power of ∼0.9 W and a laser scanning speed of 5 μm/s. The curved lines with bending angles of 0-90° or with sine-shapes are written by just changing the laser scanning direction. The polarized micro-Raman scattering spectra for the line after bending are the same as those for the line before bending, indicating that the crystal plane of Sm_xBi_1−xBO₃ crystals to the crystal growth direction might be maintained even after the change in the laser scanning direction. It is found from laser scanning microscope observations that the crystal lines at the surface are swelled out smoothly, giving a height of about 10 μm.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Some studies about the green and red light emitting structures in NaCl1−xBrx:Mn

In this work we present the results obtained from the luminescence spectra and X-ray diffraction as well as transmission electron microscopy, at room temperature on crystals of NaCl_1−xNaBr_x:MnCl₂:0.3% (x=0.00, 0.05, 0.25, and 0.50). The results suggest the existence of structures between the crystal planes (1 1 1) and (2 0 0), which may be associated with different types of Mn²⁺ arrangements, such as dipole complexes, octahedral and rhombohedral structures as well as other possible nanostructures that include mixtures of bromine/chlorine ions. These are responsible for the emission spectra of “as grown” crystals consisting of maxima around 500 nm and 600 nm. The green emission has been usually attributed to rhombohedral/tetrahedral symmetry sites; the present results point out that this is due to Mn–Cl/Br nanostructures with rhombohedral structure. On the other hand when the crystals are thermally quenched from 500 °C to room temperature the structures previously detected present changes. Only a red band appears around 620 nm if the samples are later annealed at 80 °C.     

Preparation and multi-properties of insulated single-phase BiFeO3 ceramics

Six types of BiFeO₃ ceramic samples, with subtle differences in synthesis conditions, were prepared. The comparison of their phases, electrical resistivity, and porosity revealed that the use of Bi₂O₃ and Fe₂O₃ powders of <1 μm size and a rapid liquid-phase sintering process of 855 °C for 5 min at 100 °C/s is beneficial to synthesize poreless single-phase BiFeO₃ samples with high electrical resistivity of ∼5×10¹² Ω cm. Deoxygenated Bi_xFe_yO_{1.5x+1.5y−δ} (x≠y, δ≥0) impurities were identified and found to be the main cause of low electrical resistivity and high porosity in the multi-phase samples. Large saturation polarization of 16.6 μC/cm² and low leakage current density of 30 mA/m², both at a high electric field of 145 kV/cm, were measured in the optimized single-phase samples at room temperature besides a large piezoelectric d₃₃ coefficient of 27 pC/N and an obvious canted antiferromagnetic behavior.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Theoretical investigation of the intrinsic piezoelectric properties for tetragonal BaTiO3 epitaxial films

The orientation dependences of the converse longitudinal piezoelectric constant d_33,f, and the in-plane converse piezoelectric constant e_31,f, are calculated for tetragonal barium titanate epitaxial films. The calculations demonstrate that both e_31,f and d_33,f have their maximum values along an axis close to the (1 1 1) direction of the pseudo-cubic system, which are similar to the orientation dependence results for a tetragonal BaTiO₃ single crystal. The calculated piezoelectric constants for a (1 1 1) oriented BaTiO₃ epitaxial film (e_31,f = −23 C/m², d_33,f = 124 pm/V) suggest that it is a good candidate material for lead-free MEMS applications.     

Spray-pyrolysis deposition of LaMnO3 and La1−xCaxMnO3 thin films

Ethylene glycol solutions of La-Mn(II) and La-Ca-Mn(II) citric complexes has been used as a starting material for spray-pyrolysis deposition of LaMnO₃ and La_1−xCa_xMnO₃ thin films on β-quartz, fused quartz, Si(0 0 1) and SrTiO₃(1 0 0) substrates heated during the deposition at 380 °C. At suitable post-deposition heating conditions highly uniform films, 0.1-1 μm in thickness, with good crystal structure were obtained. Highly textured LaMnO₃ films are obtained on SrTiO₃(1 0 0) substrate. Interaction between the layer and Si-containing substrates is observed during the post-deposition heating in static air.     

Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Low-temperature property investigation of the lead indium-niobate-lead nickel-niobate solid solution

The complex perovskite solid solution (1−x) Pb(In_1/2Nb_1/2)O₃-(x) Pb(Ni_1/3Nb_2/3)O₃ has been successfully prepared by the Columbite precursor method. The temperature dependencies of the dielectric constant and pyroelectric coefficient were measured between −261 and 200 °C. Relaxor ferroelectric behavior has been noticed in all compositions across the solid solution. The room-temperature electrostrictive coefficient, Q₃₃, was 1.83×10⁻² C²/m⁴ for x=0.10. No room-temperature piezoelectric activity was detected; however, upon cooling to −261 °C the maximum coupling coefficients k_p=29%, k_t=11%, and k₃₃=31% were observed for the composition x=1.00.     

Piezoelectric measurements on BiFeO3 single crystal by Raman scattering

The piezoelectric response of BiFeO₃ at low temperature has been investigated by Raman scattering measurements. The application of an external electric field at T=10 K induces frequency shifts of the lowest frequency mode related to the Bi-O bonds and corresponding to the soft mode of the ferroelectric transition. The piezoelectric effect is responsible for the softening of this mode via the tensile stress leading to the expansion of the crystal. The phonon deformation potential associated with the soft mode has been estimated around −200 cm⁻¹/strain units using the linear piezoelectric coefficient d₃₃=16 pm/V. It found in the range of the ones obtained for typical piezoelectrics.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

Role of the TiO6 octahedra on the ferroelectric and piezoelectric behaviour of the poled PbMg1/3Nb2/3O3-xPbTiO3 (PMN-PT) single crystal and textured ceramic

Field cooling (FC) poled/unpoled PMN-29%PT single crystal and room temperature (RT) poled/unpoled PMN-34.5%PT textured ceramic were investigated between ∼0 and 300 °C by thermal expansion, dielectric and Raman spectroscopy. New phase transitions are evidenced at 40, 91 and 180 °C in the case of FC PMN-29%PT as well as at 70 and 200 °C for RT PMN-34.5%PT and their order is discussed. The physical properties of the textured ceramics are rather similar to the ones observed for the single crystals that make them low-cost alternative for a wide range of applications. However, the temperatures and character of the phase transitions strongly depend on the kind of the poling conditions. Temperature dependences of the Raman line parameters show that the NbO₆ octahedra remain stable during temperature increase, while TiO₆ ones evolve quasi-continuously. The step transitions of the Pb²⁺ ion sublattice are evidenced. This suggests that the TiO₆ and Pb²⁺ sublattices are especially coupled. The role of the TiO₆ clusters on the structural phase transitions and dielectric properties of the PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-PT) system is discussed. The presence of the Raman modes above the maximum dielectric permittivity reveals that the local symmetry is lower than the cubic one (Pm3m). The decrease of the Raman line intensities vs. temperature indicates precisely the continuous evolution of the local symmetry towards the cubic one. The temperature evolution of the Rayleigh wing parameters appears sensitive to the phase transitions’ presence.     

Structural and electrical properties of (Na0.85K0.15)0.5Bi0.5TiO3 thin films deposited on LaNiO3 and Pt bottom electrodes

(Na_0.85K_0.15)_0.5Bi_0.5TiO₃ thin films were deposited on LaNiO₃(LNO)/SiO₂/Si(1 0 0) and Pt/Ti/SiO₂/Si(1 0 0) substrates by metal-organic decomposition, and the effects of bottom electrodes LNO and Pt on the ferroelectric, dielectric and piezoelectric properties were investigated by ferroelectric tester, impedance analyzer and scanning probe microscopy, respectively. For the thin films deposited on LNO and Pt electrodes, the remnant polarization 2P_r are about 22.6 and 8.8 μC/cm² under 375 kV/cm, the dielectric constants 238 and 579 at 10 kHz, the dielectric losses 0.06 and 0.30 at 10 kHz, the statistic d_33eff values 95 and 81 pm/V. The improved piezoelectric properties could make (Na_1−xK_x)_0.5Bi_0.5TiO₃ thin film as a promising candidate for piezoelectric thin film devices.     

Effect of fabrication parameters on the electrical conductivity of YxSr1−xTiO3 for anode materials

Yttrium-doped strontium titanate (Y_xSr_1−xTiO₃), as probable anode material for SOFC, was prepared by solid-state reaction. The solubility of yttrium in SrTiO₃ at different temperatures was examined and the electrical conductivities of Y_xSr_1−xTiO₃ were measured from 500 to 1000 °C. The effects of doping amount, fabrication atmosphere, and sintering temperature on the electrical conductivity of Y_xSr_1−xTiO₃ were investigated. Y_xSr_1−xTiO₃ with x=0.08 was found to give the maximum electrical conductivity, 71 S/cm at 800 °C in pure hydrogen. Reducing atmospheres and appropriate sintering temperatures play a positive role in improving the electrical conductivity.     

Growth of large La2−xSrxCuO4 single crystals using tilting-mirror-type infrared heating image furnace

Large single crystals of La_2−xSr_xCuO₄ (LSCO) high-T_c superconductors were grown by the infrared heating floating zone (IR-FZ) method using a tilting-mirror-type image furnace. The maximum diameter of the LSCO crystals increased to 10 mm in the tilting-mirror-type image furnace from 6 mm in the conventional image furnace. CuO rich feeds were required for the crystal growth using the tilting-mirror-type image furnace to compensate for the lack of CuO caused by the significant evaporation of CuO during the growth. The evaporation of CuO was affected by the tilting angle of the mirrors of the image furnace and by feed diameter. The optimized growth conditions were as follows: mirror tilting angle, 20°; feed diameter, 10 mm∅; and feed composition 50.7 mol% CuO.     

Crystal structure,dielectric and piezoelectric properties of Ta/W codoped Bi3TiNbO9 Aurivillius phase ceramics

Aurivillius phase Bi₃Ti_1−xTa_xNb_1−xW_xO₁₂ high temperature piezoceramics were prepared by a conventional solid state reaction method. The crystal structure, dielectric, electrical conduction and piezoelectric properties were systematically studied. Pure or modified Bi₃TiNbO₉ ceramics revealed the presence of only two-layered Aurivillius phase, indicating that Ta/W doping entered into the B-site of pseudo-perovskite structure and formed solid solutions. The Curie temperature had a strong reliance on the structural distortion. Furthermore, Ta/W dopants act as a donor doping, decrease the number of oxygen vacancies and facilitate the domain wall motion. As a result, Ta/W modifications significantly increase the DC resistivity and piezoelectric properties. Bi₃Ti_0.98Ta_0.02Nb_0.98W_0.02O₁₂ ceramics possess the optimum d₃₃ value (∼12.5 pC/N) together with a high T_C point (∼893 °C). Moreover, the resonance–antiresonance spectra demonstrate that the Ta/W-BTN ceramics are indeed piezoelectric in nature at 600 °C. The d₃₃ value of BTTNW-2 ceramic remains ∼12.2 pC/N after annealing at 700 °C. These factors suggest that the BTTNW-based ceramic is a promising candidate for ultra-high temperature sensor applications.