Lead-free piezoelectric thin films of Mn-doped NaNbO3-BaTiO3 fabricated by chemical solution deposition

Lead-free piezoelectric thin films of NaNbO₃-BaTiO₃ were fabricated on Pt/TiO_x/SiO₂/Si substrates by chemical solution deposition. Perovskite NaNbO₃-BaTiO₃ single-phase thin films with improved leakage-current and ferroelectric properties were prepared at 650 °C by doping with a small amount of Mn. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ thin films showed slim ferroelectric P-E hysteresis and field-induced strain loops at room temperature. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ films showed remanent polarization values of 6.3 and 6.2 μC/cm², and coercive field of 41 and 55 kV/cm, respectively. From the slope of the field-induced strain loop, the effective piezoelectric coefficient (d₃₃) was found to be 40-60 pm/V.     

Phase transition and piezoelectric properties of (1 − x)K0.5Na0.5NbO3–xLiSbO3 ceramics by hydrothermal powders

KNbO₃, NaNbO₃ and LiSbO₃ powders were synthesized by a hydrothermal route have been used to prepare (1 ? x)K_0.5Na_0.5NbO₃–xLiSbO₃ (KNN–LS; x = 0.00–0.08) ceramics. The effects of LiSbO₃ doping on the structures of KNN–LS ceramics have been systematically investigated by X-ray diffraction (XRD) and Rietveld refined XRD patterns. A gradual phase transition from orthogonal to tetragonal with the increase of LiSbO₃ content is demonstrated. Thereinto, the monoclinic phase is identified for the KNN–LS ceramic with the LiSbO₃ content of x = 0.08. Meanwhile, the XRD pattern reveals that the intensity ratio of (200)/(002) crystal face of the ceramic with x = 0.08 was bigger than one, which is different from the tetragonal phase. The tetragonal phase is revealed in the KNN–LS ceramic in the vicinity of x = 0.07, accompanying with relatively higher piezoelectric and ferroelectric properties. Tetragonal phase is beneficial to improve the piezoelectric properties of the KNN–LS ceramics.     

Kinetic Properties of Orientational Phase Transition in Polymerized States of Fullerites C60

Abstract

In the present work, we have shown that at early stages of dimerization, which occur during synthesis of C₆₀ fullerite T _syn = 10–40°C and P _syn = 1.5–8 GPa, kinetics of the sc→fcc phase transition, may be well described by Avrami law with Avrami's exponent n _Avr = 3 (i.e., in this case we are dealing with martensite‐like transformation). Fullerite's samples produced at higher temperatures (40°C < T _syn < 120°C) exhibit different kinetics with lower Avrami‐exponent. This behavior we attribute to the transformation switching to diffusion‐controlled kinetics.     

Enhancement of dielectric and electrical properties of NaNbO3-modified BiFeO3

Solid solutions of BiFeO₃ (BFO) and NaNbO₃ [i.e., (Bi_1?xNa_x) (Fe_1?xNb_x)O₃] for x = 0.1, 0.2, 0.3 were prepared by a mixed-oxide method. X-ray diffraction analysis confirms the formation of a single-phase system within a certain limit of x, and indicates that with increase in concentration of NaNbO₃ there is structural transformation of BFO from the rhombohedral to the tetragonal phase. The dielectric constant and loss-tangent of samples increase with rise in temperature. It is found that with increase of concentration of NaNbO₃ in the solid solution, tangent loss of BFO is greatly reduced that can be useful for some industrial applications. The appearance of hysteresis loops of the samples at room temperature confirms the ferroelectric properties of the materials. As the electrical conductivity of the above system increases with rise in temperature, it follows the Arrhenius relation. The frequency and temperature dependence of conductivity of the above system obeys Joncher’s universal power law. Some voltage is induced with the application of magnetic field confirming the existence of multiferroics properties in the materials. Leakage current reduces with increase in content of NaNbO₃ in the solid-solutions.     

Concurrent bandgap narrowing and polarization enhancement in epitaxial ferroelectric nanofilms

Abstract

Perovskite-type ferroelectric (FE) crystals are wide bandgap materials with technologically valuable optical and photoelectric properties. Here, versatile engineering of electronic transitions is demonstrated in FE nanofilms of KTaO₃, KNbO₃ (KNO), and NaNbO₃ (NNO) with a thickness of 10–30 unit cells. Control of the bandgap is achieved using heteroepitaxial growth of new structural phases on SrTiO₃ (001) substrates. Compared to bulk crystals, anomalous bandgap narrowing is obtained in the FE state of KNO and NNO films. This effect opposes polarization-induced bandgap widening, which is typically found for FE materials. Transmission electron microscopy and spectroscopic ellipsometry measurements indicate that the formation of higher-symmetry structural phases of KNO and NNO produces the desirable red shift of the absorption spectrum towards visible light, while simultaneously stabilizing robust FE order. Tuning of optical properties in FE films is of interest for nanoscale photonic and optoelectronic devices.     

Structural and optical properties of phosphate-zinc-nickel oxide glasses for narrow band pass absorption filters

Novel two phosphate glass systems with compositions 50P₂O₅–30ZnO–20NiO and 50P₂O₅–30ZnO–20[NiCl_2–6H₂O] were prepared using a conventional melt-quench technique. The absorbance and transmittance were measured using a spectrophotometer in the spectral range between 190 and 1100 nm. The data demonstrates that the system acts as a narrow bandpass optical absorption filter, with a transmission band in the UV region of 311–376 nm, which is centred at 350 nm and has a full width half maximum (FWHM) of almost 34 nm, whereas, the red region is the UV region of 617–684 nm, and centred at 650 nm and has a full width half maximum (FWHM) of nearly 32 nm. However, the refractive index (n), optical band gap (E_opt), non-linear refractive index n₂, third order non-linear susceptibility χ⁽³⁾ and non-linear absorption coefficient β were also calculated. It was apparent that the non-linear refractive index, third order non-linear susceptibility and non-linear absorption coefficient increases by decreasing the optical energy gap. Finally, we investigated the structure of the prepared glasses by using Raman and FTIR spectra. We found that the local network structure based mainly on Q¹ and Q² tetrahedron units connected by P–O–P linkages.     

Equilibre de phases et caracterisation dielectrique des niobates mixtes de strontium et de sodium

Phase equilibrium and dielectric characterisation of the binary system SrNb₂O₆-NaNbO₃ were investigated through DTA, crystallographic, Curie point, and hysteresis loop measurements. Similarly to previous results on alkaline-alkaline earth niobates, ferroelectric solid solutions with the tungsten bronze structure are stable at room temperature between 69 and 79 mol.% SrNb₂O₆. In the 65–69 % range a tungsten bronze phase occurs at high temperature. On the other hand, a new compound with cubic symmetry at room temperature is determined for 33 mol.% SrNb₂O₆, which undergoes a phase transition at ? 100°C into a ferroelectric state. The solubility range of this compound extends to 14 mol.% SrNb₂O₆. Between 14 and 33 % ferroelectric solid solutions have a slightly distorted cubic symmetry below their Curie temperature, which is found-to vary from ? 100°C to + 200°C. Finally it has been shown that small amounts of SrNb₂O₆ incorporated in NaNbO₃ (2,5 mol.% SrNb₂O₆) drive ferroelectric the room temperature antiferroelectric phase of NaNbO₃.     

Concurrent bandgap narrowing and polarization enhancement in epitaxial ferroelectric nanofilms

Perovskite-type ferroelectric (FE) crystals are wide bandgap materials with technologically valuable optical and photoelectric properties. Here, versatile engineering of electronic transitions is demonstrated in FE nanofilms of KTaO₃, KNbO₃ (KNO), and NaNbO₃ (NNO) with a thickness of 10–30 unit cells. Control of the bandgap is achieved using heteroepitaxial growth of new structural phases on SrTiO₃ (001) substrates. Compared to bulk crystals, anomalous bandgap narrowing is obtained in the FE state of KNO and NNO films. This effect opposes polarization-induced bandgap widening, which is typically found for FE materials. Transmission electron microscopy and spectroscopic ellipsometry measurements indicate that the formation of higher-symmetry structural phases of KNO and NNO produces the desirable red shift of the absorption spectrum towards visible light, while simultaneously stabilizing robust FE order. Tuning of optical properties in FE films is of interest for nanoscale photonic and optoelectronic devices.     

Dielectric properties of BaTiO3–Bi(Zn1/2Ti1/2)O3–NaNbO3 solid solutions

In order to develop dielectric ceramics with temperature-stable permittivity characteristics, perovskite BaTiO₃–Bi(Zn_1/2Ti_1/2)O₃–NaNbO₃ ceramic solid solutions were investigated with a particular focus on effects of BaTiO₃ and NaNbO₃ contents on the dielectric properties of ternary compounds. Keeping the ratios of the other two constituents constant, decreasing the BaTiO₃ content leads to a broadening of the temperature-dependent permittivity maximum and a decrease in the overall permittivity. For compositions of constant BaTiO₃ content, replacing Bi(Zn_1/2Ti_1/2)O₃ with NaNbO₃ shifts the temperature of the maximum permittivity to lower temperatures (e.g., to ?103 °C for a composition of 70BT–5BZT–25NN) while maintaining a broad permittivity peak with temperature, which for the 50BT–25BZT–25NN composition also satisfies the X9R standard. Thus, the investigation of BT–BZT–NN compounds resulted in promising dielectric properties with broad temperature ranges of high permittivity, which is of interest for advanced capacitor applications.     

Synthesis of nanometric LaCr0.5Mn0.5O3 perovskite at low temperature by the polyvinyl alcohol gel combustion method

Nanosized LaCr_0.5Mn_0.5O₃ perovskite was synthesised with relatively high surface area (15.5 m²/g) at low temperature (650 °C) by the combustion method using polyvinyl alcohol (PVA) and corresponding metal nitrates. The perovskite was characterised by X-ray diffraction, thermogravimetric and differential thermal analysis, field emission scanning electron microscopy and Brunauer–Emmett–Teller technique. The optimal preparative conditions were PVA/metals 3:1 by mole, pH = 3–4 and 80 °C for gel formation. Perovskite exhibits a good catalytic activity in total oxidation of m-xylene at the low temperature of reaction (250 °C).     

Ferroelectric and piezoelectric properties of new NaNbO<Subscript>3</Subscript>–Bi<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> lead-free ceramics

New lead-free ceramics (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ have been fabricated by the conventional ceramic sintering technique, and their ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ diffuses into the NaNbO₃ lattices to form a new perovskite-type solid solution with orthorhombic symmetry. The addition of a small amount of Bi_0.5K_0.5TiO₃ (x ≥ 0.025) transforms the ceramics from antiferroelectric to ferroelectric. The ceramic with x = 0.10 possesses the largest remanent polarization P _r and thus exhibits the optimum piezoelectric properties, giving d ₃₃ = 71 pC/N, k _p = 16.6% and k _t = 39.7%. The ceramics with low doping level of Bi_0.5K_0.5TiO₃ are normal ferroelectrics and the ferroelectric-paraelectric phase transition becomes diffusive gradually with the doping level x of Bi_0.5K_0.5TiO₃ increasing. Our results show the (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ ceramics is one of the good candidates for lead-free piezoelectric and ferroelectric materials.     

Antiferroelectric-ferroelectric transition in binary systems of solid solutions based on sodium niobate

The dielectric properties of the (1−x)NaNbO_3−x KNbO₃ and (1− x)NaNbO_3−x PbTiO₃ systems are investigated. The antiferroelectric-ferroelectric transition regions are determined. It is established that in the (1−x)NaNbO_3−x KNbO₃ system the antiferroelectric phase is stable for x≤0.01 and the ferroelectric phase is stable for x≥0.0175; the transition from one phase into another occurs in the concentration range 0.01<x<0.0175. In the (1− x)NaNbO_3−x PbTiO₃ system the transition region lies in the range 0.07<x<0.11. Pis’ma Zh. Tekh. Fiz. 25, 1–5 (October 12, 1999)     

High thermally stable BiFeO3–PbTiO3–BaTiO3 ceramics with improved ferroelectric properties

High temperature (0.9-x)BiFeO₃–(x)PbTiO₃–0.1BaTiO₃ (BF–PT–BT) ceramics at MPBs (x = 0.18, 0.20 and 0.22) were synthesized by solid-state reaction technique. Well-saturated P–E loops were obtained and an enhanced ferroelectric behavior of P_r ~60 μC/cm² and E_c ~50 kV/cm was observed in 0.68BiFeO₃–0.22PbTiO₃–0.10BaTiO₃ ceramics, which was much higher than those of reported BiFeO₃–PbTiO₃-based and BiFeO₃–BaTiO₃-based ceramics. The temperature stability of the ceramics was also investigated, showing a high resistivity to thermal depoling, with a degradation temperature T_d of ~500 °C. Our results suggested that BF–PT–BT was a good lead-reduced high-temperature ferroelectric ceramics.     

Effects of MnO2 and sintering temperature on microstructure, ferroelectric, and piezoelectric properties of Ba0.85Ca0.15Ti0.90Zr0.10O3 lead-free ceramics

Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ + xmol% MnO₂ lead-free ceramics have been prepared by a conventional sintering method and the effects of MnO₂ and sintering temperature on microstructure, ferroelectric, and piezoelectric properties of Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ lead-free ceramics have been studied. The addition of 0.25 mol% MnO₂ promotes grain growth, improves the ferroelectricity of the ceramics and strengthens ferroelectric tetragonal–ferroelectric orthorhombic phase transition near 40 °C. Because of the coexistence of tetragonal and orthorhombic phases and the combinatory effects of soft and hard doping of Mn ions, the ceramic with x = 0.25 exhibits the optimum piezoelectric properties (d ₃₃ = 306 pC/N and k _p = 42.2 %, respectively). Excess MnO₂ inhibits the grain growth and degrades the ferroelectric and piezoelectric properties of the ceramics. Sintering temperature has an important influence on the microstructure, tetragonal–orthorhombic phase transition near 40 °C, ferroelectric and piezoelectric properties of the ceramics. The increase in sintering temperature leads to large grains and more noticeable tetragonal–orthorhombic phase transition near 40 °C, enhances ferroelectricity and thus improves effectively the piezoelectricity of the ceramics. The Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ ceramic sintered at 1350 °C possesses the optimum piezoelectric constant d ₃₃ value of 373 pC/N.     

EDTA-assisted phase conversion synthesis of (Gd0.95RE0.05)PO4 nanowires (RE = Eu,Tb) and investigation of photoluminescence

Abstract

Hexagonal (Gd_0.95RE_0.05)PO₄·nH₂O nanowires ~300 nm in length and ~10 nm in diameter have been converted from (Gd_0.95RE_0.05)₂(OH)₅NO₃·nH₂O nanosheets (RE = Eu, Tb) in the presence of monoammonium phosphate (NH₄H₂PO₄) and ethylene diamine tetraacetic acid (EDTA). They were characterized by X-ray diffraction, thermogravimetry, electron microscopy, and Fourier transform infrared and photoluminescence spectroscopies. It is shown that EDTA played an essential role in the morphology development of the nanowires. The hydrothermal products obtained up to 180 °C are of a pure hexagonal phase, while monoclinic phosphate evolved as an impurity at 200 °C. The nanowires undergo hexagonal→monoclinic phase transformation upon calcination at ≥600 °C to yield a pure monoclinic phase at ~900 °C. The effects of calcination on morphology, excitation/emission, and fluorescence decay kinetics were investigated in detail with (Gd_0.95Eu_0.05)PO₄ as example. The abnormally strong ⁵D₀→⁷F₄ electric dipole Eu³⁺ emission in the hexagonal phosphates was ascribed to site distortion. The process of energy migration was also discussed for the optically active Gd³⁺ and Eu³⁺/Tb³⁺ ions.     

Some New Aspects of Chlorination of Fullerenes

Abstract

The effect of the reagent ratio, reaction time and power of the reagent on the product composition in chlorination of [60]fullerene was studied. Chlorofullerenes C₆₀Cl₆, C₆₀Cl₈, C₆₀Cl₁₀, C₆₀Cl₁₂, C₆₀Cl₁₄, and C₆₀Cl₂₆ were synthesized and characterized by chemical analysis, FTIR, ¹³C NMR, and MALDI TOF mass spectrometry. The experimental data supported the coexistence of several isomers of C₆₀Cl _n (n = 8, 10, 12, 14, 26); the mixtures were not separated so far. Semiempirical calculations (AM1, PM3) were used to analyze the addition patterns and resulted in the most favorable structures of C₆₀Cl_8–26. Chlorination of C₇₀ under various conditions invariably yielded C₇₀Cl₁₀.     

Preparation and Properties of Al2O3-doping LiNi1/3Co1/3Mn1/3O2 Cathode Materials

LiNi_1/3Co_1/3-xMn_1/3O₂ doped with Al₂O₃ (x = 0%, 2.5%, 5%, 10%) was synthesized by co-precipitation of Ni, Co, and Mn acetates. The influence of Al₂O₃ doping on structure and electrochemical performances of LiNi_1/3Co_1/3Mn_1/3O₂ was studied using X-ray diffraction (XRD) analysis, scanning electron microscopy, charge/discharge tester, and electrochemical workstation. It was found that the materials achieved the best electrochemical properties when x was 5%. The first discharge capacity was 156.3 mAh · g^?1(0.1 C, 2.0–4.8 V), which was close to the un-doped sample (156.8 mAh · g^?1). After 20 cycles, the capacity retention ratios at the C-ratios of 0.1C, 0.2C, and 0.5 C were 96.1%, 94.9%, and 89.4%, respectively, while the capacity retention ratios of the un-doped samples were only 92.6% (0.1 C), 91.8% (0.2 C), and 88.7% (0.5C). The alternating current impedance shows that the charge transfer in the electrode interface was the easiest when x was 5%.     

Synthesis of anisotropic NaNbO<Subscript>3</Subscript> seed crystals and fabrication of textured (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-based ceramics

High aspect ratio patelike NaNbO₃ particles with pure perovskite structure have been successfully synthesized by topochemical microcrystal conversion (TMC) from plate-like precursor particles of the layer-structured Bi_2.5Na_3.5Nb₅O₁₈. By changing the Bi_2.5Na_3.5Nb₅O₁₈/Na₂CO₃ ratio, large and thin NaNbO₃ particles with a thickness of approximately 0.5 μm and a width of approximately 20 μm were obtained. The obtained NaNbO₃ particles is quite suitable for fabricating textured (K_0.5Na_0.5)NbO₃-based ceramics. Using the fine platelike NaNbO₃ particles as templates, dense <001> -oriented (K_0.5Na_0.5)NbO₃-0.5 mol %MnO₂ ceramics with high texture quality (Lotgering factor F ₀₀₁ = 87 %) and excellent piezoelectric properties were produced by templated grain growth. Compared with randomly oriented ceramics, textured samples show greatly enhanced properties. The room-temperature strain S, the piezoelectric coefficient d ₃₃ ^* and d ₃₃ reach up to 0.093 %, 233 pm/V and 195pC/N, respectively, which are all about 1.5 times larger than those of non-textured ceramics.     

Special features of the distributed feedback lasers based on gyrotropic cubic crystals

The oscillation conditions were determined for the distributed feedback lasers based on gyrotropic cubic crystals. The frequencies of clockwise (counterclockwise) polarized longitudinal eigenmodes decrease (increase) by ω_ρ=ρc/n (ρ is the specific optical rotation of the crystal, n is the index of refraction, c is the speed of light in vacuum) relative to the Bragg frequency ω₀=πc/Λn (Λ is the phase grating period). The gain threshold is higher for the clockwise than for the counterclockwise polarized waves.     

Effect of mechanical depoling on piezoelectric properties of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–<Emphasis Type="Italic">x</Emphasis>BaTiO<Subscript>3</Subscript> in the morphotropic phase boundary region

The effect of mechanical stress on the direct piezoelectric properties of pre-poled (1 ? x)(Na_0.5Bi_0.5)TiO₃–xBaTiO₃ (NBT–xBT) in the range 4% ≤ x ≤ 13% was studied in situ using a mechanical load frame. Prior to mechanical loading, compositions near the morphotropic phase boundary (MPB, x = 6–7% BT) exhibited enhanced ferroelectric and piezoelectric properties compared to compositions further from the MPB. Specifically, the lowest ferroelectric coercive field and highest piezoelectric coefficient within this composition range occur at x = 7% BT. During mechanical compression, the MPB compositions exhibited the lowest depoling stress. The results demonstrate that, while favorable piezoelectric and ferroelectric properties can be obtained at compositions near the MPB, these compositions are also the most susceptible to the effects of mechanical depoling. Ferroelastic domain wall motion is suggested as the primary factor that may be responsible for these behaviors.