Preparation and dielectric properties of compositionally graded （Ba, Sr）TiO3 thin film by sol-gel technique

Compositional graded BaxSr1-xTiO3 （x=0.6, 0.7, 0.8, 0.9, 1.0） （BST） thin films （less than 400 nm） were fabricated on Si and Pt/Ti/SiO2/Si substrates by sol-gel technique. A special heating treatment was employed to form the uniform composition gradients at 700 ℃. The microstructures of the films were studied by means of X-ray diffraction, atomic force microscope and field emission scanning electron microscopy. The results show that the films have uniform and crack-free surface morphology with perovskite structure phase. The small signal dielectric constant （εr） and dielectric loss （tanδ） are found to be 335 and 0.045 at room temperature and 200 kHz. The dielectric properties change significantly with applied dc bias, and the graded thin film show high tunability of 42.3% at an applied field of 250 kV/cm. All the results indicate that the graded BST thin films prepared by sol-gel technique have a promising candidate for microelectronic device.     

Effect of substrate temperature on microstructures and dielectric properties of compositionally graded BST thin films

Compositionally graded Ba1-xSrxTiO3 （BST） （x = 0-0.3） thin films were prepared on Pt/Ti/SiO2/Si substrate at different substrate temperatures ranging from 550 ℃ to 650 ℃ by radio-frequency （rf） magnetron sputtering. The effect of substrate temperature on the preferential orientation, microstructures and dielectric properties of compositionally graded BST thin films was investigated by X-ray diffraction, scanning electron microscopy and dielectric frequency spectra, respectively. As the temperature increases, the preferential orientation evolves in the order： randomly orientation→ （111） → highly oriented （111） （α（111）= 60.2%）. The surface roughness of the graded BST thin films varies with the substrate temperatures. No visible internal interface in the compositionally graded thin films can be observed in the cross-sectional SEM images. The graded BST thin films deposited at 650 ℃ possess the highest dielectric constant and dielectric loss, which are 408 and 0.013, respectively.     

Synthesis and electrochemical behavior of LiCoO2 recycled from incisors bound of Li-ion batteries

LiCoO2 was separated from AI foil with dimethyl acetamide（DMAC）, and then polyvinylidene fluoride（PVDF） and carbon powders in active material were eliminated by high temperature calcining. The content of the elements in the recovered powders were analyzed. Then the Li2CO3 was added in recycled powders to adjust molar ratio of Li to Co to 1.00, 1.03 and 1.05, respectively. The new LiCoO2 was obtained by calcining the mixture at 850 ℃ for 12 h in air. Structure and morphology of the recycled powders and resulted sample were observed by XRD and SEM technique, respectively. The layered structure of the LiCoO2 is improved with the decrease of molar ratio of Li to Co. The charge/discharge performance, and cyclic voltammograms performance were studied. The recycle-synthesized LiCoO2 powders, whose molar ratio of Li to Co is 1.0, is found to have the best characteristics as cathode material in terms of charge--discharge capacity and cycling performance. And the cyclic voltammograms（CV） curve shows the lithium extraction/insertion characteristics of the LiCoO2 well.     

Effect of annealing temperature on ferroelectric properties of （Bi, Nd）4（Ti, V）3O12 thin films

Thin films of Nd^3＋/V^5＋-cosubstituted bismuth titanate, （Bi3.sNd0.5）（ Ti2.96V0.04）O12 （BNTV）, were fabricated on the Pt（111）/Ti/SiO2/Si（100） substrates by a chemical solution deposition technique and annealed at different temperatures of 650, 700, 750 and 800 ℃. The surface morphology and ferroelectric properties of the samples were studied in detail. The result shows that the film annealed at 800 ℃ indicates excellent ferroelectricity with a remanent polarization of 2Pr=40.9 i.tC/cm^2, a coercive field （Ec） of 114 kV/cm at an applied electrical field of 375 kV/cm. The substitution of Ti-site ion by V^5＋ ions could improve the upper limit of the optimal annealing temperature by decreasing the space charge density in BNT thin film. Additionally, the mechanism concerning the dependence of ferroelectric properties of BNTV thin films on the annealing temperature was discussed.     

Ferroelectric properties of dysprosium-doped Bi4Ti3O12 thin films crystallized in various atmospheres

Dysprosium-doped Bi4Ti3O12 （Bi3.4Dy0.6Ti3O12, BDT） ferroelectric thin films were deposited on Pt（111）/Ti/SiO2/Si（111） substrates by chemical solution deposition （CSD） and crystallized in nitrogen, air and oxygen atmospheres, respectively. X-ray diffraction （XRD） and scanning electron microscopy （SEM） were used to identify the crystal structure, the surface and cross-section morphology of the deposited ferroelectric films. The results show that the crystallization atmosphere has significant effect on determining the crystallization and ferroelectric properties of the BDT films. The film crystallized in nitrogen at a relatively low temperature of 650 ℃, exhibits excellent crystallinity and ferroelectricity with a remanent polarization of 2Pr = 24.9 ℃/cm^2 and a coercive field of 144.5 kV/cm. While the films annealed in air and oxygen at 650 ℃ do not show good crystallinity and ferroelectricity until they are annealed at 700 ℃. The structure evolution and ferroelectric properties of BDT thin films annealed under different temperatures （600-750 ℃） were also investigated. The crystallinity of the BDT films is improved and the average grain size increases when the annealing temperature increases from 600 ℃ to 750 ℃ at an interval of 50 ℃. However, the polarization of the films is not monotonous function of the annealing temperature.     

Fabrication of TiO2 nanotube arrays on biologic titanium alloy and properties

The vertically aligned highly ordered TiO2 nanotube arrays were fabricated by potentiostatic anodization of biologic Ti alloys（TLM） and pure Ti substrates, followed by annealing at 480 and 550 ℃ for 6 h. High-resolution scanning electron microscopy （SEM） was applied to characterize the original films. The phase of the film was characterized by XRD. The interfacial adhesion and bond strength between thin films coating and substrate were tested by scratch method. The results show that the films on the TLM alloy have high adhesion strength compared with them on pure Ti.     

Effect of Cr on high temperature oxidation of TiAl

The oxidation behavior of TiAl-Cr（mole fraction of Cr：0-20%） was investigated at 1 173 K in air. The microstructure and composition of the oxide scale were studied by X-ray diffractometry（XRD）, scanning electron microscopy（SEM） and electro-probe micro-analyses（EPMA）. The results show that with the addition of Cr content from 0 to 8%, the oxidation resistance decreases, especially at 3%, which is mainly attributed to the doping effect of Cr^3＋. TiAI-Cr（mole fraction of Cr： 15%-20%） has good oxidation resistance, and the protective alumina layer is preferentially formed on the surface of TiAI alloy, which is due to an increase of mole ratio of Al to Ti in TiAl-Cr alloys.     

Isothermal section at 927℃ of Cr-Ni-Ti system

The isothermal section at 927℃ of the Cr-Ni-Ti system was established using a high-efficiency diffusion couple approach, supplemented with eight equilibrated alloys. The alloy compositions were selected on the basis of the experimental results from the diffusion couple. Both the diffusion couple specimens and the alloys were examined by means of optical microscopy, scanning electron microscopy, and electron probe microanalysis. No ternary compound is found at 927℃. The following five three-phase equilibria are well determined： TiNi3＋（Cr）＋（Ni）, TiNia＋（Cr）＋TiNi, TiNi＋（Cr）＋Cr2Ti, Ti2Ni＋Cr2Ti＋TiNi and Ti2Ni＋Cr2Ti＋（Ti）. The solubilities of Cr in NiTi2, NiTi, and Ni3Ti are determined to be 7.5%, 14.5% and 11.4% （molar percent）, respectively, α-Cr2Ti and β-Cr2Ti dissolve about 9.2% and 13.9% Ni （molar percent）, respectively.     

Fluorescence and preparation of Sr2（P2O7）：Ce,Tb phosphate by co-precipitation method

The micron-sized Sr2（P2OT）：Ce,Tb green phosphors were prepared by being annealed at different temperatures with its precursors synthesized by co-pre-cipitates of （NH4）2HPO4 at ambient temperature. The phase structure, grain size, surface morphology, and luminescent properties of phosphors were investigated by X-ray diffraction, scanning electron microscope, trans-mission electron microscope, and fluorescence spectrum. The results show that the product of precursor annealed at 1,100 ℃ is Sr2（P2O7）：Ce,Tb, which belongs to ortho-rhombic phase. The powder is spherical and the size dis-tribution is in micron grade. The sample with the molar ratio of Sr/Tb/Ce of 100.0：0.4：0.6 shows the best fluores-cence effect annealed at 1,100 ℃ for 3 h. The phosphors produce green fluorescence by being excitated with ultra-violet radiation of 254 nm wavelength, and the main emission peak is at 547 nm. The Sr2（P2O7）：Ce,Tb phos-phors synthesized by co-precipitation method of precursors at ambient temperature is a kind of efficient green-emitting phosphors.     

Kinetic Monte Carlo simulation of growth of BaTiO3 thin film via pulsed laser deposition

Considering the characteristics of perovskite structure, a kinetic Monte Carlo（KMC） model, in which Born-Mayer- Huggins（BMH） potential was introduced to calculate the interatomic interactions and the bonding ratio was defined to reflect the crystallinity, was developed to simulate the growth of BaTiO3 thin film via pulsed laser deposition（PLD）. Not only the atoms deposition and adatoms diffusion, but also the bonding of adatoms were considered distinguishing with the traditional algorithm. The effects of substrate temperature, laser pulse repetition rate and incident kinetic energy on BaTiO3 thin film growth were investigated at submonolayer regime. The results show that the island density decreases and the bonding ratio increases with the increase of substrate temperature from 700 to 850 K. With the laser pulse repetition rate increasing, the island density decreases while the bonding ratio increases. With the incident kinetic energy increasing, the island density decreases except 6.2 eV〈Ek〈9.6 eV, and the bonding ratio increases at Ek〈9.6 eV. The simulation results were discussed compared with the previous experimental results.     

Tunable characteristics of (Ba0.5Sr0.5) TiO3 (BST) capacitors using (Ba0.5Sr0.5) RuO3 (BSR) interfacial layers onto Pt/Ti/SiO2/Si substrates

The conducting oxide electrodes (Ba, Sr) RuO₃ (BSR) similar in structure and chemical composition to (Ba, Sr) TiO₃ (BST) were deposited by metalorganic chemical vapor deposition (MOCVD) onto Pt/Ti/SiO₂/Si substrates to improve the structural and dielectric properties of BST films. The BSR interfacial layers between the BST and Pt bottom electrode influenced the preferred orientation, surface morphologies, and dielectric properties of BST films. The structural and dielectric properties of BST films depended on the thickness of the BSR layers. BST films with (100) texturing up to 150 Å thickness of BSR showed a smoother and smaller grain size than those without interfacial layers, and a tunability and dielectric constant of about 70% and 1300 at an interfacial layer of 150 Å, respectively. On the other hand, BST films with above 300 Å thickness in BSR layers showed a (110) texturing similar to those without BSR layers and a slight decrease of tunability and dielectric constant compared with those of (100) texturing BST films. The increase of the dielectric loss of BST films with BSR layers was attributed to the carbon contamination diffused from MOCVD-BSR layers.     

PTCR characteristics and microstructure of porous (Ba,Sr)TiO<Subscript>3</Subscript> ceramics prepared by spark plasma sintering

Porous Y-doped (Ba,Sr)TiO₃ ceramics were prepared by the spark plasma sintering of (Ba,Sr)TiO₃ powders with different amounts of carbon black, and by subsequently burning out the carbon black acting as a pore precursor. The microstructure, PTCR and gas-sensing characteristics for porous Y-doped (Ba,Sr)TiO₃ ceramics were investigated. Spark plasma sintered (Ba,Sr)TiO₃ ceramics revealed a very fine microstructure containing submicron-sized grains with a cubic phase and revealed an increased porosity after the carbon black was burned out. As a result of reoxidation treatment, the grain size of the (Ba,Sr)TiO₃ ceramics increased to a few μm and the cubic phase transformed into a tetragonal phase. The phase transformation of (Ba,Sr)TiO₃ ceramics was affected by grain size. The PTCR jump in the (Ba,Sr)TiO₃ ceramics prepared by adding 40 vol.% carbon black showed an excellent value of 4.72 × 10⁶, which was ten times higher than the PTCR jump in (Ba,Sr)TiO₃ ceramics. The electrical resistivity of the porous (Ba,Sr)TiO₃ ceramics was recovered as the atmosphere changed from a reducing gas (N₂) to an oxidizing gas (O₂) under consecutive heating and cooling cycles.     

氧化铝掺杂对Ba0.6Sr0.4(Zr0.2Ti0.8)O3陶瓷介电性能的影响

Zr4+取代Ti4+的Ba0.6Sr0.4(Zr0.2Ti0.8)O3固溶体在降低介电常数的同时,保持了BST固溶体优异的可调性。为降低BST材料的介电损耗和介电常数,以氧化铝为改性剂对Ba0.6Sr0.4(Zr0.2Ti0.8)O3材料(BSZT材料)进行了掺杂。随着氧化铝掺杂质量分数从1%到10%增加,BSZT材料的介电常数从5000降低到了1550(100kHz),介电损耗降低到0.001(100kHz)以下,而材料的介电可调性保持在35%左右(1.5kV/mm)。X射线衍射图谱表明,烧结后得到的BSZT材料具有典型的钙钛矿结构。扫描电子显微镜观察表明,氧化铝的掺杂使得陶瓷致密度较高,晶粒均匀。     

溶胶凝胶法制备Zn-Si-B-O掺杂钛酸锶钡(Ba0.60Sr0.40TiO3)玻璃陶瓷的制备及其介电性能研究

采用溶胶凝胶方法制备Zn-Si-B-O掺杂Ba0.6Sr0.4TiO3玻璃陶瓷.研究Zn-Si-B-O玻璃组分从5%～50%(摩尔分数,下同)掺杂Ba0.6Sr0.4TiO3玻璃陶瓷的相结构与介电性能.分析Zn-Si-B-O玻璃组分对Ba0.6 Sr0.4TiO3玻璃陶瓷结构及其介电性能的影响.结果表明:Zn-Si-B-O掺杂Ba0.6Sr0.4TiO3玻璃陶瓷的烧结温度低于传统工艺.Zn-Si-B-O掺杂Ba0.6Sr0.4TiO3玻璃陶瓷的相结构为立方钙钛矿相结构(≤40%),不存在第二相.Zn-Si-B-O掺杂Ba 0.6 Sr 0.4TiO3玻璃陶瓷的介电常数ε随着烧结温度升高而增大,介电损耗tanδ随测试温度的增加而降低.Zn-Si-B-O玻璃相聚集在晶粒边界区域,其作用稀释降低了玻璃陶瓷的介电常数,阻止晶粒生长,并降低了介电损耗tanδ.随着晶粒平均尺寸的减小,Zn-Si-B-O掺杂Ba 0.6Sr 0.4TiO3玻璃陶瓷样品的介电峰变低,平坦,宽化的现象.     

Ce掺杂Ba0.6Sr0.4TiO3薄膜表面结构XPS研究

用改进的溶胶-凝胶法制备铈(Ce)掺杂和非掺杂2种钛酸铝钡(Ba_(0.6)Sr_(0.4)TiO_3,BST)薄膜,用X射线光电子能谱(XPS)研究薄膜的表面结构.XPS结果表明,BST薄膜的表面结构由钙钛矿结构和非钙钛矿结构组成,铈掺杂显著地减少了非钙钛矿结构.扫描电镜及原子力显微镜观察表明,掺杂BST薄膜光滑致密无裂纹.电压-电容曲线表明,掺杂BST薄膜的介电性能大幅度提高,在40V外加电压下介电调谐率达60.8%,零偏压下的介电损耗为0.0265.同时,就非钙钛矿结构的成因及Ce掺杂BST薄膜的有关改善机制进行了讨论.     

熔盐合成技术制备片状(Sr,Ba)TiO3晶粒

以KCl为助熔剂,采用熔盐合成技术制备片状（Sr,Ba）TiO3晶粒,研究不同前驱体及反应方式对产物相组成和形貌的影响。结果表明：BaO与片状SrTiO3反应可获得以（Sr,Ba）TiO3为主相的产物,产物相在SrTiO3表面无规则析出且非取向长大,经烧结后形成片状多晶团聚体;片状Sr3Ti2O7与BaO和TiO2反应所得产物也以（Sr,Ba）TiO3为主,同时生成少量（Sr,Ba）3Ti2O7相,产物中除片状（Sr,Ba）TiO3晶粒外,还通过Sr^2＋置换由BaO与TiO2反应所得块状BaTiO3晶粒中的Ba^2＋、以及反应物溶解？反应？析出生成许多块状和无规则状小晶粒;对于两步合成工艺,Sr3Ti2O7先与BaO反应可得到片状（Sr,Ba）3Ti2O7,与TiO2二次反应后得到片状（Sr,Ba）TiO3晶粒;由于此方式没有生成块状BaTiO3这一过程,产物中非片状晶粒数量大幅度减少。     

Effects of growth temperature on structure and electrical properties of dielectric (Ba,Sr)TiO3 capacitors with transparent conducting oxide electrodes

200 nm-thick BST thin films were grown on Zr-doped In₂O₃/SrTiO₃ (1 0 0) substrates at 550-750 °C. X-ray diffraction results show that the as-deposited BST films were polycrystalline with random crystallographic orientations. X-ray diffraction patterns reveal that the BST film grown at 650 °C had the best crystalline quality of all the deposition temperatures. Atomic force microscopy and secondary ion mass spectrometry showed that the surface and interface structures of the BST films became rough as the growth temperature increased. The BST film grown at 650 °C showed the best electrical properties, with a dielectric constant of 420 at 1 MHz, dielectric tunability of 32.1%, dielectric loss of 0.015 at 300 kV/cm, and a mean optical transmittance in visible wavelength of 71.3%.     

Dielectric properties of low-temperature sintered Ba0.6Sr0.4TiO3 thick films prepared by reactive sintering method

Screen printed Ba_0.6Sr_0.4TiO₃ (BST6/4) thick films were fabricated by reactive sintering at a low temperature below 900 °C. The dielectric properties in radio frequency range were measured on samples of sandwich structure MIM capacitors by impedance analyzer, while that in microwave frequency range were measured on samples of thick films without top and bottom electrodes by split-post dielectric resonator method. The thick films exhibited a low permittivity, while at the same time, maintained a high tunability. The permittivity and dielectric loss at 1 MHz were 228.8 and 0.007, respectively. The corresponding values measured at 9.9 GHz were 82.24 and 0.109, respectively. The tunability was as high as 72.4% (150 kV/cm, 10 kHz). This method provides a simple and effective route to obtain thick films with great potential in applications in Low Temperature Co-fired Ceramic (LTCC) and microwave tunable devices.     

Microstructure and PTCR characteristics of porous BaTiO3-based ceramics prepared by adding activated carbon

As a pore precursor, activated carbon of different contents (0 to 30 vol%) was added to (Ba,Sr)TiO₃ powder. Porous (Ba,Sr)TiO₃ ceramics were prepared by pressureless sintering at 1350 °C for 1 h in air. The effects of the activated carbon content on the microstructure and positive temperature coefficient of resistivity (PTCR) characteristics in porous (Ba,Sr)TiO₃ ceramics were investigated. The porosity of the porous (Ba,Sr)TiO₃ ceramics increased from 6.5% to 33.5%. The PTCR jump of the porous (Ba,Sr)TiO₃ ceramics prepared with activated carbon was > 10⁵ and increased slightly with increasing activated carbon concentration. These results correspond to the Heywang model of the PTCR effect in (Ba,Sr)TiO₃ ceramics, suggesting that activated carbon is an effective additive for preparing porous BaTiO₃-based ceramics. The newly prepared (Ba,Sr)TiO₃ ceramics can be used as a gas sensor.