不同衬底温度下生长的Bi1.5Zn1.0Nb1.5O7.0薄膜的XPS研究

采用固相反应法合成具有焦绿石立方结构的Bi1.5Zn1.0Nb1.5 O7(BZN)陶瓷靶材,采用脉冲激光沉积法在Pt/TiO2/SiO2/Si(100)基片制备立方BZN薄膜,衬底温度在500～ 700℃范围内变化.X射线衍射测量结果表明:当在500℃沉积BZN薄膜时,薄膜呈现出无定形态结构.随着衬底温度增加到550℃,薄膜开始晶化,并且显示出立方焦绿石结构.X射线光电子能谱也被用来研究BZN薄膜的结构状态和元素价态.测试得到的全谱表明:在BZN薄膜中,除了用于定标的C元素之外,只有Bi、Zn、Nb、O元素的特征峰,此外有Ti2p特征峰出现,可能来自底电极的TiO2缓冲层.各元素的窄谱扫描表明:Bi,Zn,Nb,O四种元素的化学价态分别是+3,+2,+5,-2.BZN薄膜在550℃结晶,随着衬底温度升高到600℃,金属阳离子的结合能的峰位向高能方向移动,然而O1s的特征峰位也向高能方向移动,这归因于薄膜中存在的氧空位.     

Sr_(0.5)Ba_(0.5)TiO_3/La_(0.5)Sr_(0.5)CoO_3双层薄膜的微观结构

采用脉冲激光沉积法在(001)LaAlO_3衬底上制备了Sr_(0.5)Ba_(0.5)TiO_3/La_(0.5)Sr_(0.5)CoO_3薄膜,利用透射电子显微镜对薄膜的微观结构进行了研究。结果表明,底电极La_(0.5)Sr_(0.5)CoO_3在LaAlO_3衬底上外延生长并形成立方-立方取向关系。不同于块体结构,LSCO薄膜发生了结构转变,形成一种氧缺位有序调制结构。整个薄膜由大量取向畴组成,其中包含一些层错与反相畴界等缺陷。生长温度为500℃时,Sr_(0.5)Ba_(0.5)TiO_3薄膜为柱状多晶结构;当温度升高至820℃时,薄膜为缺陷较少的单晶结构。     

脉冲激光沉积ZrW2O8薄膜的制备和性能

采用脉冲激光沉积法在石英基片上沉积制备了ZrW2O8薄膜.用X射线衍射仪(XRD)、原子力显微镜(AFM)研究了不同衬底温度对薄膜结构组分、表面粗糙度和形貌的影响,用台阶仪和分光光度计测量薄膜的厚度和不同衬底温度下制备薄膜的透射曲线,用变温XRD分析了ZrW2O8薄膜的负热膨胀特性.实验结果表明:在衬底温度为室温、550℃和650℃下脉冲激光沉积的ZrW2O8薄膜均为非晶态,非晶膜在1200℃保温3min后淬火得到立方相ZrW2O8薄膜;随着衬底温度的升高,ZrW2O8薄膜的表面粗糙度明显降低;透光率均约为80%,在20～600℃温度区间内,脉冲激光沉积制备的ZrW2O8薄膜的负热膨胀系数为-11.378×10-6 K-1.     

Bi1.5-xCaxZnNb1.5O7陶瓷结构、介电性能与结晶化学特性

采用固相反应法制备Bi1.5-xCaxZnNb1.5O7(0≤x≤0.50,BCZN)陶瓷,研究Ca2+替代Bi3+对Bi1.5ZnNb1.5O7陶瓷烧结特性、显微结构、介电性能和结晶化学特性的影响.结果表明:替代量x≤0.25 mol时,样品为单一的α-BZN相.随着Ca2+替代量增加,样品最佳烧结温度从1000℃升高到1020℃;致密度从7.011 g/cm3减小到6.353 g/cm3;样品晶粒尺寸、晶格常数、电阻率均减小;结晶化学参数键价和,AV(O’)[Bi4]、AV(O’)[Bi3Zn]、AV(O’)[Bi2Zn2]和AV(O’)[Ca3Zn]均增大,且该行为与其晶格常数、介电性能变化相吻合.     

Si(111)衬底上生长的立方MgxZn1-x晶体薄膜

在国际上第一次采用电子束反应蒸发法在Si(111)衬底上生长了MgxZn1-xO晶体薄膜。能量色散X射线(EDX)特征能谱及X射线衍射(XRD)分析表明薄膜呈立方结构，薄膜的晶面取向依赖于生长温度，在200℃温度下生长得到高度(200)取向的立方MgxZn1-xO薄膜，温度过高时得到多晶薄膜。对高度(200)取向的立方MgxZn1-xO薄膜的光荧光激发谱(PLE)分析表明其光学带隙为4．20eV，相对于MgO的带隙红移量为3．50eV。XRD分析还表明立方MgxZn1-xO薄膜与MgO衬底之间的晶格失配仅为0．16％。这使得高质量立方MgxZn1-xO多量子阱材料的制备成为可能。     

退火温度对Bi3.15(Eu0.7Nd0.15)Ti3O12铁电薄膜力学性能的影响

利用金属有机物分解法(MOD)在Pt/Ti/SiO2/Si(111)衬底上制备了Bi3.15(Eu0.7Nd0.15)Ti3O12(BENT)薄膜,并经600℃、650℃、700℃、750℃退火处理。通过纳米压痕法测试了薄膜的硬度和弹性模量,采用X射线衍射(XRD)测量了薄膜的残余应力。BENT薄膜的晶粒尺寸随着退火温度的升高而不断变大。当晶粒尺寸从37 nm增大到46 nm时,薄膜的硬度值从8.4 GPa减少到3.1 GPa,弹性模量从171.5 GPa减小到141.6 GPa。随着退火温度从600℃升高到750℃时,薄膜的残余压应力值从–743 MPa减小到了–530 MPa。退火温度为600℃的BENT薄膜具有最大的硬度和弹性模量。     

固体氧化物燃料电池Ce_(0.8)Sm_(0.2)O_2电解质与Mn_(1.5)Co_(1.5)O_4的稳定性

本文面向管状固体氧化物燃料单电池串联中连接极与电解质界面稳定性展开研究,以氧化钐掺杂氧化铈(Ce_(0.8)Sm_(0.2)O_2,SDC)和Mn_(1.5)Co_(1.5)O_4(MCO)为原料,采用XRD、SEM和EDS来表征、探讨了SDC和MCO两种材料在不同运行和制备温度下的化学稳定性和结构稳定性。研究结果表明,SDC和MCO两种材料具有良好的化学相容性。当烧结温度低于1000℃时,难以获得致密的复合材料,而当处理温度为1400℃时,由于热力学温度过高,将导致颗粒迅速长大。     

锂离子电池正极材料LiNi0.5Mn1.5O4的制备及性能研究

以Li(CH3COO).2H2O、Ni(CH3COO)2.4H2O、Mn(CH3COO)2.4H2O和H2C2O4.2H2O为原料,聚乙二醇20000为分散剂,采用化学合成法制备了具有立方尖晶石结构的锂离子电池正极材料LiNi0.5Mn1.5O4。通过XRD、SEM和充放电测试对样品进行表征。850℃下焙烧制备的LiNi0.5Mn1.5O4样品电化学性能最佳,在3.5～4.9V电压范围内以0.2、0.5、1、2和5C充放电,其首次放电比容量分别为132.9、117.3、111.2、104.8和91mAh/g,20次循环后容量保持率分别为93.2%、98.9%、97.4%、97.3%和95.5%。     

影响Bi1.5ZnNb1.5O7纳米粉体水热合成因素的研究

以分析纯的Bi（N03）3·5H2O，ZnO和Nb2O5为反应物，KOH为矿化剂，采用水热法合成立方焦绿石结构的Bi1.5ZnNb1.5O7纳米粉体，通过XRD对合成粉体进行物相分析，并通过Scherrer公式计算粉体晶粒的尺寸；TEM分析所合成粉体的形貌。研究水热反应温度、时间、前躯体的含量、KOH的浓度以及有无搅拌等水热合成条件的变化对合成粉体的物相的影响，从而初步确定水热合成立方焦绿石结构的Bi1.5ZnNb1.5O7纳米粉体的温度区间、时间范围、前驱体含量和KOH浓度等工艺参数，并讨论了其反应过程。研究结果表明，在Nb：Bi=2.0、KOH浓度为1.8mol／L、反应温度为220℃、反应时间为24h、充分搅拌的情况下，水热反应进行得最彻底，可以合成单相的Bi1.5ZnNb1.5O7纳米粉体。     

甩胶喷雾热分解法制备ITO薄膜及光电性能研究

按In:Sn(物质的量比)=9:1,InCl3·4H2O和SnCl4·5H2O为前驱物,采用自制甩胶喷雾热分解制备薄膜装置在普通玻璃衬底上沉积了ITO薄膜,结果表明,采用自制甩胶喷雾热分解制备薄膜新装置成功制备出ITO薄膜。该装置结构简单、操作方便。制备ITO薄膜优化条件为:甩胶转速800r/min、衬底温度250℃、退火温度450℃、载气为空气、流量为7L/min、液体雾化速度0.2ml/min、雾粒速度3.5m/s。薄膜的沉积时间为5min,薄膜厚度约1000nm,最低电阻率为0.75*10-4Ω·cm,薄膜在可见光范围(波长在400-700nm)内平均透光率为87.2%。衬底温度在200℃以上时呈现立方相结构。     

Structure and microwave dielectric properties of Bi1.5Zn1.0Nb1.5O7 thin films deposited on alumina substrates by pulsed laser deposition

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were deposited on polycrystalline alumina substrates by pulsed laser deposition at different substrate temperatures. The phase structure and surface morphology were characterized using X-ray diffractometer (XRD) and atomic force microscopy. Microwave dielectric properties were performed using split-post dielectric resonator method at spot frequencies of 10, 15 and 19 GHz, respectively. The XRD results indicate that the as-deposited Bi_1.5Zn_1.0Nb_1.5O₇ thin films deposited at 650 °C are amorphous in nature. The dielectric permittivity and loss tangent of the amorphous BZN thin films are 75.5 and 0.013 at 10 GHz, respectively. As the measure frequency increased to 19 GHz, the dielectric permittivity slightly decreases and loss tangent slightly increases. BZN thin films were crystallized after the post-annealing by a rapid thermal annealing in air for 30 min. The crystallized BZN thin films exhibit the excellent dielectric properties and frequency responses. The dielectric permittivity and loss tangent of the crystallized BZN thin films are 154 and 0.038 at 10 GHz, respectively.     

Influences of post-annealing on structural and electrical properties of Bi1.5Zn1.0Nb1.5O7 thin films prepared by pulsed laser deposition

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were prepared on Pt/TiO₂/SiO₂/Si(100) substrates at 650 °C under an oxygen pressure of 10 Pa by using pulsed laser deposition process. The crystallinity, microstructure and electrical properties of BZN thin films were investigated to verify the influences of post-annealing thermal process on them. The X-ray diffractometer (XRD) results indicate that all Bi_1.5Zn_1.0Nb_1.5O₇ thin films without post-annealing process or with post-annealing in situ vacuum chamber and in oxygen ambient exhibit a cubic pyrochlore structure. The improved crystallinity of BZN thin films through post-annealing was confirmed by XRD and scanning electron microscope (SEM) analysis. Dielectric constant and loss tangent of the as-deposited BZN thin films are 160 and 0.002 at 10 kHz, respectively. After annealing, dielectric properties of thin films are significantly improved. Dielectric constant and loss tangent of the in situ annealed films are 181 and 0.0005 at 10 kHz, respectively. But the films post-annealed in O₂ oven show the largest dielectric constant of 202 and the lowest loss tangent of 0.0002, which may attribute to the increase in grain size and the elimination of oxygen vacancies. Compared with the as-deposited BZN thin films, the post-annealed films also show the larger dielectric tunability and the lower leakage current density.     

Bi1.5Zn1.0Nb1.5O7 thin films deposited at low temperature and post-annealed for crystallization

Near-stoichiometric Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films were prepared on Pt/TiO₂/SiO₂/Si (100) substrates at 400 °C under an oxygen pressure of 10 Pa by using pulsed laser deposition process. The as-deposited BZN thin films were post-annealed at 700 °C for 30 min in situ vacuum chamber (in situ) and in oxygen ambient oven (ex situ). The crystallinity, microstructure and electrical properties of BZN thin films were investigated. The X-ray diffractometer results indicate that BZN thin films deposited at 400 °C are amorphous in nature and the post-annealed thin films exhibit a cubic pyrochlore structure. The as-deposited BZN thin films show permittivity of 68 and loss tangent of 0.0011 at 10 kHz, respectively. After a post-annealing at 700 °C for 30 min, the dielectric properties of thin films are significantly improved. Permittivity and loss tangent of the in situ annealed films are 127 and 0.005 at 10 kHz, respectively. And the films post-annealed in O₂ oven show the largest permittivity of 170 and tangent of 0.006. The improved dielectric properties can attribute to the crystallization of thin films. BZN thin films deposited at low temperature and crystallized at high temperature show the dielectric tunability without an electric breakdown to the maximum measurement bias voltage. And BZN thin films also show the excellent leakage current properties.     

Ferroelectric and dielectric multilayer heterostructures based on KTa0.65Nb0.35O3 and Bi1.5-xZn0.92-yNb1.5O6.92-1.5x-y grown by pulsed laser deposition and chemical solution deposition for high frequency tunable devices

Epitaxial growth of Bi_1.5-xZn_0.92-yNb_1.5O_6.92-1.5x-y (BZN) thin films was achieved on (100)_pc LaAlO₃ substrate by pulsed laser deposition (PLD) and by chemical solution deposition based on Pechini process. Effect of bismuth and zinc deficiency on the BZN thin films obtained by PLD was discussed, in relation with the starting target composition. Dielectric permittivity and bandgap values were determined from electrical and spectroscopic ellipsometry measurements performed on randomly oriented films grown on Pt/Si substrate. BZN thin films obtained by PLD exhibit, at 100 kHz, a dielectric constant of ε_r = 203 and quite low dielectric losses of tanδ = 5 × 10^− 2. Epitaxial ferroelectric − dielectric KTa_0.65Nb_0.35O₃ (KTN) − Bi_1.5-xZn_0.92-yNb_1.5O_6.92-1.5x-y (KTN on BZN and BZN on KTN) bilayers were obtained by PLD on (100)_pc LaAlO₃ with the insertion of a suitable buffer layer of KNbO₃ in the case of KTN on BZN. Such multilayer heterostructures with an epitaxial growth control of each layer are promising candidates for potential integration in microwave devices.     

Large nonlinear optical response of a Bi1.5Zn1.0Nb1.5O7 thin film fabricated by pulsed laser deposition

The Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin film has been fabricated on MgO (001) substrate by pulsed laser deposition. The nonlinear optical properties of the BZN film were investigated using Z-scan technique at a wavelength of 532 nm with 25 ps pulse duration. The two-photon absorption coefficient and the nonlinear refractive index of the BZN film were obtained to be 4.2 × 10^− 6 cm/W and 1.6 × 10^− 10 cm²/W respectively, which are comparable with those of some representative nonlinear optical materials. The large and fast response optical nonlinearities indicated that the BZN film is a promising candidate for future photonics devices.     

Thickness-ratio-dependent dielectric properties of Bi1.5Zn1.0Nb1.5O7/Ba0.5Sr0.5TiO3 bilayered thin films

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN)/Ba_0.5Sr_0.5TiO₃ (BST) thin films were prepared on Pt/Ti-coated sapphire substrates by radio frequency magnetron sputtering. The specific relationship between the dielectric properties and the thickness ratio of the BZN thickness to the BST thickness was investigated. The presence of BZN films effectively reduced the dielectric loss of the thin films. The thickness-ratio-dependent dielectric constant and dielectric loss behaviors were in good accordance with the simulation results based on the series connection theory. The optimum thickness ratio was determined to be around 0.5, exhibiting a maximum commutation quality factor of about 16,000. The built-in electric field at the region near the BZN–BST interface may be responsible for the asymmetric characteristic of the electric-field-dependent dielectric properties of the BZN/BST thin films.     

Enhanced tunable dielectric properties of Ba0.5Sr0.5TiO3/Bi1.5Zn1.0Nb1.5O7 multilayer thin films by a sol-gel process

Ba_0.5Sr_0.5TiO₃(BST)/Bi_1.5Zn_1.0Nb_1.5O₇(BZN) multilayer thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol-gel method. The structures and morphologies of BST/BZN multilayer thin films were analyzed by X-ray diffraction (XRD) and field-emission scanning electron microscope. The XRD results showed that the perovskite BST and the cubic pyrochlore BZN phases can be observed in the multilayer thin films annealed at 700 °C and 750 °C. The surface of the multilayer thin films annealed at 750 °C was smooth and crack-free. The BST/BZN multilayer thin films annealed at 750 °C exhibited a medium dielectric constant of around 147, a low loss tangent of 0.0034, and a relative tunability of 12% measured with dc bias field of 580 kV/cm at 10 kHz.     

Growth and characterization of Bi2Se3 thin films by pulsed laser deposition using alloy target

Bi₂Se₃ thin films were deposited on the (100) oriented Si substrates by pulsed laser deposition technique at different substrate temperatures (room temperature −400 °C). The effects of the substrate temperature on the structural and electrical properties of the Bi₂Se₃ films were studied. The film prepared at room temperature showed a very poor polycrystalline structure with the mainly orthorhombic phase. The crystallinity of the films was improved by heating the substrate during the deposition and the crystal phase of the film changed to the rhombohedral phase as the substrate temperature was higher than 200 °C. The stoichiometry of the films and the chemical state of Bi and Se elements in the films were studied by fitting the Se 3d and the Bi 4d5/2 peaks of the X-ray photoelectron spectra. The hexagonal structure was seen clearly for the film prepared at the substrate temperature of 400 °C. The surface roughness of the film increased as the substrate temperature was increased. The electrical resistivity of the film decreased from 1 × 10⁻³ to 3 × 10⁻⁴ Ω cm as the substrate temperature was increased from room temperature to 400 °C.     

High-permittivity and low-loss dielectric tunable pyrochlore thin films deposited by radio frequency magnetron sputtering from a lead zinc niobate target

Since Bi₂O₃-ZnO-Nb₂O₅ (BZN) pyrochlore thin films have been introduced as a tunable dielectric, the substitution of Bi with Pb could be a reasonable choice. The PbO-ZnO-Nb₂O₅ (PZN) cubic pyrochlore thin films were produced by radio frequency sputtering, and their dielectric properties, in terms of tunability, were measured. Up to 33.4% of tunability and comparable K factors with BZN films were obtained. The effects of film crystallization, along with substrate heating and post-annealing on the dielectric properties, were similar to those of BZN. However, strong texturing developed in the PbO-ZnO-Nb₂O₅ (PZN) films deposited at a high substrate temperature, which caused degradation of the loss tangent and K factor.     

Low voltage ZnO thin-film transistors with Ti-substituted BZN gate insulator for flexible electronics

We report the fabrication of ZnO based thin-film transistors (TFTs) with high-k gate insulator of Ti-substituted Bi_1.5ZnNb_1.5O₇ (BZN) films. (Bi_1.5Zn_0.5)(Zn_0.4Nb_1.43Ti_0.3O₇) film deposited on Pt/Ti/SiO₂/Si substrate by pulsed laser deposition at room temperature exhibits high dielectric constant of 73 at 100 kHz, while BZN film shows much lower dielectric constant of 50, respectively. The increasing dielectric constant with increasing Ti substitution can be attributed to the presence of a highly polarizable TiO₆ octahedra and its strong correlation with the NbO₆ octahedra. All room temperature processed ZnO based TFTs using Ti-substituted BZN gate insulator exhibited filed effect mobility of 0.75 cm²/Vs and low voltage device performance less than 2.5 V.