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.     

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.     

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).     

Effect of La doping on microstructure and ferroelectric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by sol-gel method

The Bi4Ti3Oi2 and Bi3.25La0.75Ti3O12 thin films were prepared on the Pt/Ti/SiO2/Si substrate using the sol-gel method. The effect of La doping on the microstructure and ferroelectric properties of Bi4Ti3O12 films were investigated. Both the Bi4Ti3O12 and Bi3.25La0.75Ti3O12 thin films exhibited typical bismuth layered perovskite structure. The 2Pr （remanent polarization） value of Bi3.25La0.75Ti3O12 thin films is 18.6 μC/cm^2, which is much larger than that of Bi4Ti3O12 thin films. And the Bi3.2eLa0.75Ti3O12 films show fatigue-free behavior, while the Bi4Ti3O12 thin films exhibit the fatigue problem. The mechanism of improvement of La doping was discussed.     

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.     

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.     

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).     

Orientation of Bi<Subscript>3.2</Subscript>La<Subscript>0.8</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films with different annealing schedules

Fatigue-free Bi_3.2La_0.8Ti₃O₁₂ ferroelectric thin films were successfully prepared on p-Si (100) substrates using metalorganic solution deposition process. The orientation and formation of 5-layers thin films were studied under different processing conditions using XRD. Experimental results indicate that increase in annealing time at 700 °C after preannealing for 10 min at 400 °C can remarkably increase (200)-orientation of the films derived from the precursor solutions with two contents of citric acid. Meanwhile, high content of citric acid increases the film thickness and is conducive to the a-orientation of the films with the preannealing, and low concentration of the solution is conducive to the c-orientation of the films without the preannealing.     

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.     

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 oxygen partial pressure on epitaxial growth and properties of laser-ablated AZO thin films

Al-doped ZnO (AZO) thin films were grown on c-sapphire substrates by laser ablation under different oxygen partial pressures (P _O2). The effect of PO2 on the crystal structure, preferred orientation as well as the electrical and optical properties of the films was investigated. The structure characterizations indicated that the as-grown films were single-phased with a wurtzite ZnO structure, showing a significant c-axis orientation. The films were well crystallized and exhibited better crystallinity and denser texture when deposited at higher P _O2. At the optimum oxygen partial pressures of 10 - 15 Pa, the AZO thin films were epitaxially grown on c-sapphire substrates with the (0001) plane parallel to the substrate surface, i e, the epitaxial relationship was AZO (000 1) // Al₂O₃ (000 1). With increasing P _O2, the value of Hall carrier mobility was increased remarkably while that of carrier concentration was decreased slightly, which led to an enhancement in electrical conductivity of the AZO thin films. All the films were highly transparent with an optical transmittance higher than 85 %.     

Preparation and ferroelectric properties of Bi<Subscript>3.4</Subscript>Ce<Subscript>0.6</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films grown by sol-gel method

We have investigated the preparation and properties of Bi_3.4Ce_0.6Ti₃O₁₂ thin films. The Bi_3.4Ce_0.6Ti₃O₁₂ thin films were fabricated on the Pt/Ti/SiO₂/Si substrates using sol-gel method. The structure and morphology of the films were characterized using X-ray diffraction and atomic force microscopy. The thin films showed a perovskite phase and dense microstructure. The dielectric constant and the dissipation factor of the Bi_3.4Ce_0.6Ti₃O₁₂ thin films were about 172 and 0.031 at 1 kHz, respectively. The 2P _r and 2E _c of the Bi_3.4Ce_0.6Ti₃O₁₂ thin films were 67.1 μC/cm² and 299.7 kV/cm, respectively, under an applied field of 600 kV/cm. The Bi_3.4Ce_0.6Ti₃O₁₂ film did not show fatigue up to 4.46×10⁹ switching cycles at a frequency of 1 MHz, and showed good insulating behavior according to the test of leakage current. Supported by the Natural Science Foundation of Hubei Province (Grants No. 2004ABA082)     

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.     

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.     

Ferroelectric properties of Bi<Subscript>4</Subscript>Zr<Subscript>0.5</Subscript>Ti<Subscript>2.5</Subscript>O<Subscript>12</Subscript> thin films prepared on LaNiO<Subscript>3</Subscript> bottom electrode by sol-gel method

The Bi4Zr0.5Ti2.5O12 (BZT) thin films were fabricated on the LaNiO3 bottom electrode using sol-gel method. The structure and morphology of the films were characterized using X-ray diffraction, AFM and SEM. The results show that the films have a perovskite phase and dense microstructure. The 2Pr and 2Vc of the Pt/BZT/LaNiO3 capacitor are 28.2 μC/cm2 and 14.7 V respectively at an applied voltage of 25 V. After the switching of 1×1010 cycles, the Pr value decreases to 87% of its pre-fatigue values. The dielectric constant (ε) and the dissipation factor (tanδ) of the BZT thin films are about 204 and 0.029 at 1 kHz, respectively. The films show good insulating behavior according to the test of leakage current. The clockwise C-V hysteresis curve observed shows that the Pt/BZT/LaNiO3 structure has a memory effect because of the BZT film's ferroelectric polarization.     

Electronic structure and transport coefficients of the thermoelectric materials Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> from first-principles calculations

The electronic structures of bulk Bi₂Te₃ crystals were investigated by the first-principles calculations. The transport coefficients including Seeback coefficient and power factor were then calculated by the Boltzmann theory, and further evaluated as a function of chemical potential assuming a rigid band picture. The results suggest that p-type doping in the Bi₂Te₃ compound may be more favorable than n-type doping. From this analysis results, doping effects on a material will exhibit high ZT. Furthermore, we can also find the right doping concentration to produce more efficient materials, and present the “advantage filling element map” in detail.     

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.     

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.     

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.     

Microstructures and fatigue-free properties of the La<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by modified sol-gel technique

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) and Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were fabricated on Pt/TiO₂/SiO₂/Si (100) substrates by a modified sol-gel technique. X-ray diffraction indicated that these films were of single phase with random polycrystalline orientations. The surface morphologies of the films were observed by scanning electron microscope, showing uniform, dense films with grain size of 50–100 nm. Well-saturated hysteresis loops of the films were obtained in metal-ferroelectric-metal type capacitors with Cu top electrodes at an applied voltage of 400 kV/cm, giving the remanent polarization (2P _r) and coercive field (2E _c) values of the films of 25.1 μC/cm² and 203 kV/cm for BLT, and 44.2 μC/cm² and 296 kV/cm for BNT, respectively. Moreover, these capacitors did not show fatigue behaviors after up to 1.75×10¹⁰ switching cycles at the test frequency of 1 MHz, suggesting a fatigue-free character. The influences of the La³⁺ and Nd³⁺ doping on the properties of the films were comparatively discussed. Supported by the National Key Basic Research and Development Program of China (Grant No. 2006CB932305) and the Natural Science Foundation of Hubei Province, China (Grant No. 2004ABA082)