Preparation and piezoelectric properties of CuO-added (Ag<Subscript>0.75</Subscript>Li<Subscript>0.1</Subscript>Na<Subscript>0.1</Subscript>K<Subscript>0.05</Subscript>)NbO<Subscript>3</Subscript> lead-free ceramics

CuO-doped (Ag_0.75Li_0.1Na_0.1K_0.05)NbO₃ (ALNKN-xCuO, x = 0–2mol%) lead-free piezoelectric ceramics were prepared by the solid-state reaction method in air atmosphere. The effects of CuO addition on the phase structure, microstructure, and piezoelectric properties of the ceramics were investigated. The experimental results show that the ALNKN ceramics without doping CuO possess rhombohedral phase along with K2Nb6O16-type phase and metallic silver phase. For all of the CuO-doped ALNKN ceramics, a pure perovskite structure with the orthorhombic phase was obtained by enclosing the samples in a corundum tube. A homogeneous microstructure with the grain size of about 1 μm was formed for the ceramics with 0.5mol% CuO. The grain size increases with increasing amount of CuO. The temperature dependence of dielectric properties indicates that the ferroelectric phase of the ALNKN-xCuO ceramics becomes less stable with the addition of CuO. The ceramics with x = 1mol% exhibit relatively good electrical properties along with a high Curie temperature. These results will provide a helpful guidance to preparing other AN-based ceramics by solid-state reaction method in air atmosphere.     

Effects of Excess Barium on the Structure and Electrical Properties of(Ba,Ca)TiO_3 Piezoelectric Ceramics with High Mechanical Quality Factors

Manganese-doped Ba_(0.925)Ca_(0.075)TiO_3 lead-free piezoelectric ceramics(abbreviated as BCT)with high mechanical quality factor were synthesized by conventional solid-state reaction method.The effects of excess Ba on the crystal structure,microstructure,and electrical properties of the ceramics were systematically investigated.X-ray diffraction and Raman spectra revealed that Ca~(2+)ions were pushed from Ba sites to Ti sites of BCT when 1.5 mol%extra Ba~(2+)ions were added after sintering.The grain size of the ceramics was decreased by adding extra Ba~(2+)ions.The mechanical quality factor and resistivity of the ceramics decreased dramatically when the excess Ba was more than 1.5 mol%.High piezoelectric coefficients(d_(33)=150-190 pC/N)and high mechanical quality factors(Q_m=1 000-1 200)were obtained in the ceramics when the excess of Ba was between 0.5 mol%and 1 mol%.These results indicated that the properties of BCT ceramics could be tailored by adjusting the content of Ba.     

Structural and electrical properties of high Curie temperature Aurivillius phase composite ceramics with largely enhanced piezoelectricity

High performance piezoelectric ceramics with high Curie temperatures(TC) are the bottle necks of relevant high temperature devices. In this study, the electrical performance and microstructure of Li and Mn codoped Aurivillius-type composite ceramics with a composition Ca_(0.99-x_Bi_(6.99+x)(Li Mn)_(0.01) Nb Ti_5O_(24)(x = 0–0.8) were systematically investigated. The results indicated that uniform intergrowth structure with a lattice similar to that of the end member CBT could be formed at a low x value(x 0.4). Phase separation occurred when more A-site Ca~(2+) ions were replaced by Bi~(3+) ions. Nevertheless, all composite samples showed d_(33) values about 2 to 3 times of that of the constituent phase Ca Bi_4Ti_4O_(15) and Bi_3 Ti NbO_9 with still a high depolarization temperature. The performance of the samples was found to be related to the density and larger lattice distortion along the polarization a axis. The results also demonstrated that formation of the compound system was an effective way in improving the performance of Aurivillius-type high TC piezoelectric ceramics.     

Improved Breakdown Strength in (Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>)<Subscript>0.85</Subscript>Bi<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> Ceramics with Addition of CaZrO<Subscript>3</Subscript> for Energy Storage Application

(Ba_0.6Sr_0.4)_0.85Bi_0.1TiO₃ ceramics doped with x wt%CaZrO₃ (x= 0-10) were synthesized by solid-state reaction method. The effects of CaZrO₃ amount on the dielectric properties and structure of (Ba_0.6Sr_0.4)_0.85Bi_0.1TiO₃ ceramics were investigated. X-ray diffraction results indicated a pure cubic perovskite structure for all samples and that the lattice parameter increased till x=5 and then slightly decreased. A homogenous microstructure was observed with the addition of CaZrO₃. Dielectric measurements revealed a relaxor-like characteristic for all samples and that the diffusivity γ reached the maximum value of 1.78 at x=5. With the addition of CaZrO₃, the dielectric constant dependence on electric field was weakened, insulation resistivity enhanced and dielectric breakdown strength improved obviously and reached 19.9 kV/mm at x=7.5. In virtue of low dielectric loss (tan δ<0.001 5), moderate dielectric constant (ε_r >1 500) and high breakdown strength (E_b >17.5 kV/mm), the CaZrO₃ doped (Ba_0.6Sr_0.4)_0.85Bi_0.1TiO₃ ceramic is a potential candidate material for high power electric applications.     

Effect of Constituent Core-sizes on Microstructure and Dielectric Properties of BaTiO<Subscript>3</Subscript>@(0.6Ba-TiO<Subscript>3</Subscript>-0.4BiAlO<Subscript>3</Subscript>) Core-Shell Material

The fundamental characteristics of varied initial core-sizes of BaTiO₃(BT) and its influential role on the morphology and dielectric properties of BaTiO₃@0.6BaTiO₃-0.4BiAlO₃(BT@0.6BT-0.4BA) ceramic samples were studied. Alkoxide sol-precipitation method was adopted as revised chemical route to synthesize the constituent “core” BT powders in a dispersed phase, whereas the distinctive initial nano-sized particles were affected by the pre-calcination temperatures (600-900 °C).The microstructure of the uncoated BT ceramics revealed an exaggerated grain growth with an optimized dielectric constant (ε_max >9 000) whilst the coated ceramics behaved otherwise (grain growth inhibited) when sintered at an elevated temperature. Regardless of the previously studied solubility limit (about 0.1%) of BT-BA samples, BT@0.6BT-0.4BA maintained a maximum dielectric constant (ε_max) ranging from 1 592 to 1 708 and tan δ less than 2% under a unit mole ratio at room temperature. In view of all these analyses, the initial nanometer sizes of the as-prepared BT-core powders combined with the increase effect of cation substitutions of Bi³⁺ and Al³⁺ in the shell content, induced the diffuse transition phase of BT@0.6BT-0.4BA composition.     

Effects of electrode on resistance switching properties of ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> films deposited by magnetron sputtering

ZnMn₂O₄ films for resistance random access memory (RRAM) were fabricated with different device structures by magnetron sputtering. The effects of electrode on I-V characteristics, resistance switching behavior, endurance and retention characteristics of ZnMn₂O₄ films were investigated. The ZnMn₂O₄ films, using p-Si and Pt as bottom electrode, exhibit bipolar resistive switching (BRS) behavior dominated by the space-charge-limited conduction (SCLC) mechanism in the high resistance state (HRS) and the filament conduction mechanism in the low resistance state (LRS), but the ZnMn₂O₄ films using n-Si as bottom electrodes exhibit both bipolar and unipolar resistive switching behaviors controlled by the Poole-Frenkel (P-F) conduction mechanism in both HRS and LRS. Ag/ZnMn₂O₄/p-Si device possesses the best endurance and retention characteristics, in which the number of stable repetition switching cycle is over 1000 and the retention time is longer than 10⁶ seconds. However, the highest R _HRS/R _LRS ratio of 10⁴ and the lowest V _ON and V _OFF of 3.0 V have been observed in Ag/ZnMn₂O₄/Pt device. Though the Ag/ZnMn₂O₄/n-Si device also possesses the highest R _HRS/R _LRS ratio of 10⁴, but the highest values of V _ON,V _OFF, R _HRS and R _LRS, as well as the poor endurance and retention characteristics.     

Enhanced Ferroelectric Polarization in Laser-ablated Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films by Controlling Preferred Orientation

Polycrystalline Bi₄Ti₃O₁₂ thin films with various fractions of a-axis, c-axis and random orientations have been grown on Pt(111)/Ti/SiO₂/Si substrates by laser-ablation under different kinetic growth conditions. The relationship between the structure and ferroelectric property of the films was investigated, so as to explore the possibility of enhancing ferroelectric polarization by controlling the preferred orientation. The structural characterization indicated that the large growth rate and high oxygen background pressure were both favorable for the growth of non-c-axis oriented grains in the Bi₄Ti₃O₁₂ thin films. The films with high fractions of a-axis and random orientations, i e, f (a-sxis) = 28.3% and f (random) = 69.6%, could be obtained at the deposition temperature of 973 K, oxygen partial pressure of 15 Pa and laser fluence of 4.6 J/cm², respectively. It was also noted that the variation of ferroelectric polarization was in accordance with the evolution non-c-axis orientation. A large value of remanent polarization (2Pr = 35.5 μC/cm²) was obtained for the Bi₄Ti₃O₁₂ thin films with significant non-c-axis orientation, even higher than that of rare-earth-doped Bi₄Ti₃O₁₂ films.     

Remarkable improvement of ferroelectric properties and leakage current in BiFeO<Subscript>3</Subscript> thin films by nd modification

Ferroelectric and leakage properties are important for ferroelectric applications. Pure and Nd-doped (x=0.05-0.20) BiFeO3 thin films were fabricated by sol-gel method on FTO substrates. The phase structure, surface morphology, leakage current, ferroelectric properties, and optical properties of BiFeO₃^- based thin films were investigated. The substitution of Nd³⁺ ions for the Bi3+ site converts the structure from rhombohedral to coexisting tetragonal and orthorhombic. Nd doping improves the crystallinity of BiFeO₃ thin films. The leakage current of Nd-doped BiFeO₃ decreases by two to three orders of magnitude compared with that of pure BiFeO₃. Among the samples, 15% Nd-doped BiFeO₃ exhibits the strongest ferroelectric polarization of 17.96 μC/cm². Furthermore, the absorption edges of Bi_1-xNd _x FeO₃ thin films show a slight red-shift after Nd doping.     

Crystallization and luminescence properties of Sm<Superscript>3+</Superscript>-doped SrO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

The Sm³⁺-doped SrO-Al₂O₃-SiO₂ (SAS) glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian (SrAl₂Si₂O₈) and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm³⁺-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the ⁴G_5/2→⁶ H _j/2 (j=5, 7, 9, 11) transitions of Sm³⁺, respectively. Besides, by increasing the crystallization temperature or the concentration of Sm³⁺, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that the Sm³⁺-doped SAS glass-ceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.     

Composition dependence of phase structure and electrical properties of (1−y)Bi1−xNdxFeO3−yBiScO3 ceramics

In this work, we have studied a new lead-free ceramic of(1-y)Bi_(1-x)Nd_xFeO_(3-y)BiScO_3(0.05≤x≤0.15 and 0.05≤y≤0.15) prepared by a conventional solid-state method, and the influences of Nd and Sc content on their phase structure and electrical properties were investigated in detail. The ceramics with 0.05≤x≤0.10 and 0.05≤y≤0.15 belong to an R3 c phase, and the rhombohedral-like and orthorhombic multiphase coexistence is established in the composition range of 0.125≤x≤0.15 and y=0. The electrical properties of the ceramics can be enhanced by modifying x and y values. The highest piezoelectric coefficient(d33~51 p C/N) is obtained in the ceramics with x=0.075 and y=0.125, which is superior to that of a pure BiFeO_3 ceramic. In addition, a lowest dielectric loss(tan δ~0.095%, f=100 k Hz) is shown in the ceramics with x=0.15 and y=0 due to the involvement of low defect concentrations, and the improved thermal stability of piezoelectricity at 20–600oC is possessed in the ceramics. We believe that the ceramics can play a meaningful role in the high-temperature lead-free piezoelectric applications.     

Density function theory study of electronic,optical and thermodynamic properties of CaN<Subscript>2</Subscript>, SrN<Subscript>2</Subscript> and BaN<Subscript>2</Subscript>

We put forward a first-principles density-functional theory about the impact of pressure on the structural and elastic properties of bulk CaN₂, SrN₂ and BaN₂. The ground state properties of three alkaline earth diazenides were obtained, and these were in good agreement with previous experimental and theoretical data. By using the quasi-harmonic Debye model, the thermodynamic properties including the debye temperature Θ _D, thermal expansion coefficient α, and grüneisen parameter γ are successfully obtained in the temperature range from 0 to 100 K and pressure range from 0 to 100 GPa, respectively. The optical properties including dielectric function ε(?), absorption coefficient α(?), reflectivity coefficient R(?), and refractive index n(?) are also calculated and analyzed.     

Spontaneous Magnetic Transitions and Corresponding Magnetoelastic Properties of Intermetallic Compounds <Emphasis Type="Italic">R</Emphasis>Mn<Subscript>2</Subscript>Ge<Subscript>2</Subscript> (<Emphasis Type="Italic">R</Emphasis>=Gd,Tb and Dy)

The spontaneous magnetic transitions and corresponding magnetoelastic properties of intermetallic compounds RMn₂Ge₂ (R=Gd, Tb and Dy) were investigated by using the X-ray diffraction method and magnetic measurement. The results showed that the compounds experience two magnetic transitions, namely the second-order paramagnetic to antiferromagnetic transition at temperature T_N (T_N=368, 423 and 443 K for GdMn₂Ge₂, TbMn₂Ge₂ and DyMn₂Ge₂, respectively) and the first-order antiferromagnetic - ferrimagnetic transition at temperature T_t (T_t=96, 80 and 40 K for GdMn₂Ge₂, TbMn₂Ge₂ and DyMn₂Ge₂, respectively) as the temperature decreases. The temperature dependence of the lattice constant a(T) displays a negative magnetoelastic anomaly at the second-order transition point T_N and, at the first-order transition T_t, a increases abruptly for GdMn₂Ge₂ and TbMn₂Ge₂, Δa/a about 10^-3. Nevertheless, the lattice constant c almost does not change at these transition points indicating that such magnetoelastic anomalies are mainly contributed by the Mn-sublattice. The transitions of the magnetoelastic properties are also evidenced on the temperature dependence of magnetic susceptibility χ. The first-order transition behavior at T_t is explained by the Kittel mode of exchange inversion.     

Microstructure and erosion resistance of in-situ SiAlON reinforced BN-SiO<Subscript>2</Subscript> composite ceramics

BN-SiO₂-SiAlON composite ceramics were successfully prepared by the means of hot pressed sintering. Xe plasma flow generated by Hall Thruster was used for sputtering the surface of the samples in order to evaluate the plasma erosion resistance. XRD, TEM, SEM, and LSCM were used to characterize the phase composition and morphologies of as-made composite ceramics before and after Xe plasma erosion. The ceramics were composed of h-BN, fused silica, and SiAlON, which maintained structural stability during the process of Xe plasma sputtering. In conclusion, comparing with BN-SiO₂ composite ceramics, the plasma erosion rate of BN-SiO₂-SiAlON composite ceramics decreases significantly at first then rises with the increase of AlN addition. Erosion pits can be observed by using SEM on the surface after plasma sputtering, which demonstrates that the BN grains have dropped off the surface. In addition, mechanical denudation by high-speed Xe ions is recognized as the injury mechanism for the BN-matrix composite materials.     

Low temperature synthesis of amorphous La<Subscript>0.7</Subscript>Zn<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> films grown on p<Superscript>+</Superscript>-Si substrates and its resistive switching properties

Amorphous La_0.7Zn_0.3MnO₃ (LZMO) films were deposited on p⁺-Si substrates by sol-gel method at low temperature of 450 °C. The Ag/LZMO/p⁺-Si device exhibits invertible bipolar resistive switching and the R _HRS/R _LRS was about 10⁴-10⁶ at room temperature which can be kept over 10³ switching cycles. Better endurance characteristics were observed in the Ag/LZMO/p⁺-Si device, the V _Set and the V _Reset almost remained after 10³ endurance switching cycles. According to electrical analyses, the conductor mechanism was in low resistor state (LRS) governed by the filament conductor and in the high state (HRS) dominated by the traps-controlled space-charge-limited current (SCLC) conductor.     

Effects of annealing processes on Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript> thin films

The Cu _x Si_1-x thin films have been grown by pulsed laser deposition (PLD) with in situ annealing on Si (001) and Si (111), respectively. The transformation of phase was detected by X-ray diffraction (XRD). The results showed that the as-deposited films were composed of Cu on both Si (001) and Si (111). The annealed thin films consisted of Cu + η”-Cu₃Si on Si (001) while Cu + η’-Cu₃Si on Si (111), respectively, at annealed temperature (T _a) = 300-600 °C. With the further increasing of T _a, at T _a= 700 °C, there was only one main phase, η”-Cu₃Si on Si (001) while η’-Cu₃Si on Si (111), respectively. The annealed thin films transformed from continuous dense structure to scattered-grain morphology with increasing T _a detected by field emission scanning electron microscope (FESEM). It was also showed that the grain size would enlarge with increasing annealing time (t _a).     

Crystal growth,structure and properties of bismuth triborate BiB<Subscript>3</Subscript>O<Subscript>6</Subscript> crystal

BiB₃O₆ (BIBO) single crystals with size of 46×23×10 mm³ and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB₃O₆ is C2 and the cell parameters are a=7.1203(7) Å, b=4.9948(7) Å, c=6.5077(7) Å, β=105.586(8)″, and V=222.93(5) ų. The density of BIBO is 4.8965 g/cm³. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB₃O₆ is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB₃O₆ is a kind of excellent nonlinear optical (NLO) crystal.     

Structure and Electrical Properties of （Na0.5Bi0.5）0.94Ba0.06TiO3 Ceramicwith0.5wt% of MnO

The structure and electrical properties of （Na0.5Bi0.5）0.94Ba0.06TiO3 ceramic doped with 0.5 wt% of MnO were investigated in comparison with those of （Na0.5Bi0.5）0.94Ba0.06TiO3 ceramic. It was ascertained that the MnO addition did not cause remarkable change in crystal structure and microstructure. The MnO addition mainly displayed a hard effect on the electrical properties, an increase of coercive field （E） and mechanical quality factor （Qm） together with a decrease of dielectric constant （εr） and piezoelectric constant （d33）. An enhancement of electromechanical coupling factor （kp） with the MnO addition was obtained too. An essential relation between the piezoelectric properties and ferroelectric nature of the ceramics was detected. It was found that the piezoelectric properties of the ceramics highly depended on the corporative contribution of remanent polarization （Pt） and coercive field.     

Dielectric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics by impedance spectroscopic method

Various lead-free ceramics have been investigated in search for new high-temperature dielectrics. In particular, Bi₄Ti₃O₁₂ is a type of ferroelectric ceramics, which is supposed to replace leadcontaining ceramics for its outstanding dielectric properties in the near future. Ferroelectric ceramics of Bi₄Ti₃O₁₂ made by conventional mixed oxide route have been studied by impedance spectroscopy in a wide range of temperature. X-ray diffraction patterns show that Bi₄Ti₃O₁₂ ceramics are a single-phase of ferroelectric Bi-layered perovskite structure whether it is calcined at 800 °C or after sintering production. This study focused on the effect of the grain size on the electric properties of BIT ceramics. The BIT ceramics with different grain sizes were prepared at different sintering temperatures. Grain becomes coarser with the sintering temperature increasing by 50 °C, relative permittivity and dielectric loss also change a lot. When sintered at 1 100 °C, r values peak can reach 205.40 at a frequency of 100 kHz, the minimum dielectric losses of four different frequencies make no difference, all close to 0.027. The values of E _a range from 0.52 to 0.68 eV. The dielectric properties of the sample sintered at 1 100 °C are relatively better than those of the other samples by analyzing the relationship of the grain, the internal stresses, the homogeneity and the dielectric properties. SEM can better explain the results of the dielectric spectrum at different sintering temperatures. The results show that Bi₄Ti₃O₁₂ ceramics are a kind of dielectrics. Thus, Bi₄Ti₃O₁₂ can be used in high-temperature capacitors and microwave ceramics.     

Resistive switching behavior of Ag/Mg<Subscript>0.2</Subscript>Zn<Subscript>0.8</Subscript>O/ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/p<Superscript>+</Superscript>-Si heterostructure devices for nonvolatile memory applications

The Ag/Mg_0.2Zn_0.8O/ZnMn₂O₄/p⁺-Si heterostructure devices were fabricated by sol-gel spin coating technique and the resistive switching behavior, conduction mechanism, endurance characteristic, and retention properties were investigated. A distinct bipolar resistive switching behavior of the devices was observed at room temperature. The resistance ratio R _HRS/R _LRS of high resistance state and low resistance state is as large as four orders of magnitude with a readout voltage of 2.0 V. The dominant conduction mechanism of the device is trap-controlled space charge limited current (SCLC). The devices exhibit good durability under 1×10³ cycles and the degradation is invisible for more than 10⁶ s.     

Effect of Cu-Ti-C reaction composition on reinforcing particles size of TiC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Cu composites

TiC _x /Cu composites were fabricated by combustion synthesis and hot press technology. Using XRD, SEM, EDS, FESEM analysis methods, the effects of various carbon sources and different Cu contents on the microstructures of TiC _x /Cu composites and the size of TiC _x particles were investigated. Results showed that TiC _x reinforcing particles size increases with decreasing Cu content in Cu-Ti-C reaction system. With carbon nanotubes (carbon black) serving as carbon source, the generated TiC _x particles size transits from nanometer to submicron when Cu content corresponding to the reaction system is reduced to 60 vol% (70 vol%); while graphite serves as carbon source, there is no clear limiting concentration. C particles with smaller size, larger specific surface area and better distribution result in finer TiC _x particles, which is more beneficial to generating nano-sized TiC _x /Cu composites.