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 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.     

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.     

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.     

Optimization and temperature effects on sandwich betavoltaic microbattery

The design scheme of a sandwich-structure betavoltaic microbattery based on silicon using63Ni is presented in this paper.This structure differs from a monolayer energy conversion unit.The optimization of various physical parameters and the effects of temperature on the microbattery were studied through MCNP.For the proposed optimization design,P-type silicon was used as the substrate for the betavoltaic microbattery.Based on the proposed theory,a sandwich microbattery with a shallow junction was fabricated.The temperature dependence of the device was also measured.The open-circuit voltaic(Voc)temperature dependence of the optimized sandwich betavoltaic microbattery was linear.However,the Voc of the betavoltaic microbattery with a high-resistance substrate exponentially decreased over the range of room temperature in the experiment and simulation.In addition,the sandwich betavoltaic microbattery offered higher power than the monolayer betavoltaic one.The results of this paper provide a significant technical reference for optimizing the design and studying temperature effects on betavoltaics of the same type.     

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.     

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.     

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.     

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).     

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.     

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.     

Reaction mechanism and microstructure evolution of reaction sintered <Emphasis Type="Italic">h</Emphasis>-BN

Hexagonal boron nitride ceramic (h-BN) based on the nitridation of B powders was obtained by reaction sintering method. The effects of sintering temperature on the mechanical properties and microstructure of the resultant products were investigated and the reaction mechanism was discussed. Results showed that the reaction between B and N₂ occurred vigorously at temperatures ranging from 1 000 °C to 1 300 °C, which resulted in the generation of t-BN. When the temperature exceeded 1 450 °C, transformation from t-BN to h-BN began to occur. As the sintering temperature increased, the spherical particles of t-BN gradually transformed into fine sheet particles of h-BN. These particles subsequently displayed a compact arrangement to achieve a more uniform microstructure, thereby increasing the strength.     

Preparation and Properties of Sapphire by Edge-defined Film-fed Growth (EFG) Method with Different Growth Directions

Sapphire, belonging to hexagonal crystal system, is typically anisotropic which makes it direction-sensitive. To research the effects of growth directions on properties of sapphire, c-[0001] seed(c-sapphire) and a-[11-20] seed(a-sapphire) were used to prepare sapphire by edge-defined film-fed growth(EFG) method. The samples were analyzed through lattice integrity, dislocation and corrosion performance by double-crystal XRD, OM, AFM, SEM and EDX. It was shown that the lattice integrities of two growth-direction crystals were both well due to the small FWHM values. While the average densities of dislocation in c-sapphire and a-sapphire were 9.2×103 and 3.9×103 cm-2 respectively, the energy of dislocation in c-sapphire was lower than that in a-sapphire. During Strong Phosphoric Acid(SPA) etching, the surface of c-sapphire basically kept smooth but in a-sapphire there were many point-like corrosion pits where aluminum and oxygen atoms lost by 2:1. Our work means that it will be promising for growing c-[0001] seed sapphire by EFG if aided by parameter optimization.     

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.     

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.     

Synthesis of MnxZn（1-x）Fe2O4 Nanopartieles by Ball-milling Hydrothermal Method

SMnxZn1-xFe2O4 （x=1,0.9,0.8,0.7,0.6,0.5,0.25,0） nanoparticles were prepared by ball-milling hydrothermal and investigated by X-ray diffraction, DTG and TEM. Nanocrystallite grain size was determined by X-ray linewidth to be from 63 A to 274 A. The thermal properties indicate absorbed water still remain at low temperature, crystalline wate will be decomposed from 230 ℃ to 260 ℃, partial Mn^2＋ will be oxidized near 730 ℃. TEM shows the ferrite particles pocess a spherical morphology and uniform nanosize.     

Morphology study of oriented SmBCO film deposited by MOCVD

c-axis-oriented SmBa_2Cu_3O_7(SmBCO) films have been deposited on(100)- LaA1O_3(LAO)substrate by metal organic chemical vapor deposition(MOCVD) technique.The effects of deposition temperature(T_(dep)) and total pressure(P_(tot)) on the orientation and microstructure of SmBCO films were investigated.The orientation of SmBCO films transformed from α-axis to c-axis with increasing of T_(dep) from 900 to 1 100℃.At T_(dep)=1 050℃,SmBCO films had c-axis orientation and tetragon surface.At P_(tot)~(dep)=400-800 Pa and T_(dep)=1 050 ℃,totally c-axis-oriented SmBCO films were obtained.The R_(dep) of SmBCO films increased firstly and then decreased with increasing P_(tot).The surface of SmBCO films exhibited tetragon morphology at 1 050 ℃ and400 Pa.Maximum thickness of SmBCO film deposited was 1.2μm at P_(tot)= 600 Pa,and the corresponding R_(dep)was 7.2 μm·h~(-1).     

Effect of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> on structure and properties of calcium aluminate glasses

The effect of Ga₂O₃ on the structure and properties of calcium aluminate glasses fabricated by vacuum melting process was investigated by Raman spectrum, differential scanning calorimeter (DSC), and infrared spectrum methods. The results show that calcium aluminate glass network only consists of [AlO₄] tetrahedral units. With the gradual addition of Ga₂O₃, the quantity of [GaO₄] tetrahedral units increases. Substitution of Ga₂O₃ for Al₂O₃ results in a decrease in T _g T _x, and T _p, and an increase in the thermal stable index ΔT. Similarly, the absorption band around 3.0 μm obviously reduces and the transparency in 4.0-6.0 μm rapidly increases with increasing Ga₂O₃ content. However, the chemical stability of calcium aluminate glasses decreases if Ga₂O₃ is introduced due to the increasing of [GaO₄] units in the glass network.     

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.     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg<Subscript>12</Subscript>-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg₁₂-type LaMg₁₁Ni + x wt% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter (DSC) connected with a H₂ detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability (HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.