Structure and surface termination of ZnO films grown on (0001)- and (112¯0)-oriented Al2O3

We have studied the surface termination of ZnO(0001¯) films grown on Al₂O₃ substrates with high epitaxial quality. The structural properties of the ZnO films were investigated by X-ray scattering, revealing a predominant (0001¯)ZnO out-of-plane texture with the [112¯0]_ZnO[0001]_Al2O3 and [112¯0]_ZnO[101¯0]_Al2O3 azimuthal orientations for (112¯0)Al₂O₃ and(0001)Al₂O₃ substrates, respectively. The surface termination was determined by X-ray photoemission spectroscopy (XPS) via pyridine (C₅H₅N) adsorption at the ZnO surface. XPS data recorded at different temperatures after exposure to pyridine revealed that for both orientations of the Al₂O₃ substrates the deposited ZnO films were terminated by oxygen atoms, i.e. corresponding to a ZnO (0001¯) surface.     

氟化镁基底上HfO2中间层对Al2O3薄膜微观组织和力学性能的影响

采用电子束蒸镀技术在氟化镁基底上制备了单层Al₂O₃薄膜和含有HfO₂中间层的HfO₂/Al₂O₃双层薄膜。在空气中对所制备的薄膜进行1 h 600℃的退火处理。通过掠入角X射线衍射仪(GIXRD)、场发射扫描电镜(FE-SEM)、傅里叶变换红外光谱仪(FTIR)、纳米压痕和划痕法对薄膜的微观结构、红外透过率和力学性能进行了表征。结果表明: 退火处理后HfO₂/Al₂O₃双层薄膜中形成了一层树枝状的新层, 这种新层的硬度大于17.5 GPa。这种高硬度的新层能够保护氟化镁基底不被划伤。从GIXRD图谱中只能找到单斜相HfO₂的衍射峰, 而Al₂O₃薄膜仍然保持非晶态。从这些结果中可以推断出HfO₂从非晶态向单斜相的转变促进了这种树枝状新层的产生, 也正是这种新层提高了保护薄膜的力学性能。     

Atomic layer deposition of calcium oxide and calcium hafnium oxide films using calcium cyclopentadienyl precursor

Calcium oxide and calcium hafnium oxide thin films were grown by atomic layer deposition on borosilicate glass and silicon substrates in the temperature range of 205–300 °C. The calcium oxide films were grown from novel calcium cyclopentadienyl precursor and water. Calcium oxide films possessed refractive index 1.75–1.80. Calcium oxide films grown without Al₂O₃ capping layer occurred hygroscopic and converted to Ca(OH)₂ after exposure to air. As-deposited CaO films were (200)-oriented. CaO covered with Al₂O₃ capping layers contained relatively low amounts of hydrogen and re-oriented into (111) direction upon annealing at 900 °C. In order to examine the application of CaO in high-permittivity dielectric layers, mixtures of Ca and Hf oxides were grown by alternate CaO and HfO₂ growth cycles at 230 and 300 °C. HfCl₄ was used as a hafnium precursor. When grown at 230 °C, the films were amorphous with equal amounts of Ca and Hf constituents (15 at.%). These films crystallized upon annealing at 750 °C, showing X-ray diffraction peaks characteristic of hafnium-rich phases such as Ca₂Hf₇O₁₆ or Ca₆Hf₁₉O₄₄. At 300 °C, the relative Ca content remained below 8 at.%. The crystallized phase well matched with rhombohedral Ca₂Hf₇O₁₆. The dielectric films grown on Si(100) substrates possessed effective permittivity values in the range of 12.8–14.2.     

Al2O3保护层对高温下Pt/ZnO/Al2O3电极导电稳定性的影响

本工作研究了Al₂O₃保护层的厚度对高温下声表面波器件电极导电稳定性的影响, 采用激光分子束外延方法在Pt/ZnO/Al₂O₃电极上制备了不同厚度的Al₂O₃保护层。通过测量样品高温环境中的实时电阻, 发现Al₂O₃缓冲层的厚度对电极在高温下的导电稳定性的影响非常大。结果表明, 没有Al₂O₃保护层时, Pt/ZnO/Al₂O₃电极的电阻升温至800 ℃时开始急剧地增加。当包覆40 nm的Al₂O₃保护层时, 电极在升温至900 ℃以上才出现电阻值剧烈增加的现象。而随着Al₂O₃保护层厚度的增加, 电极的电阻在高温下的导电性能也更加稳定。SEM测试结果表明, 经过1000 ℃、1 h的高温测试后, Al₂O₃保护层越薄的Pt/ZnO/Al₂O₃电极, 结块形成的Pt颗粒越大与不连续的Pt空洞更多。这些结果为制备高温下稳定工作的声表面波器件提供了一条新的思路。     

纳米Al_2O_3分布对Al_2O_3/PE-EVA复合材料导热性能与力学性能的影响

旨在将纳米Al2O3分散在聚乙烯(PE)和乙烯醋酸乙烯共聚物(EVA)的共混物中,构建具有选择性分布结构的局域高粒子浓度导热复合材料。采用纳米Al2O3为导热填料,以PE和EVA为基体树脂,使用熔融共混法制备了Al2O3/PE-EVA导热复合材料。利用选择性溶液萃取方法和SEM研究了PE-EVA共混物的相结构及纳米Al2O3在共混物中的分布,评价了Al2O3/PE-EVA复合材料的导热性能与力学性能。结果表明:在PE与EVA质量比为1∶1时可获得具有两相共连续结构的共混物;在两相共连续PE-EVA共混物中引入纳米Al2O3后,发现纳米Al2O3主要分布在PE相中;纳米Al2O3的分布行为及共连续结构的形成有助于提高复合材料的导热性能,在纳米Al2O3质量分数为50%时,与Al2O3/PE复合材料相比,具有选择分布和相连续结构的Al2O3/PEEVA复合材料的热导率提高了21.2%;随着纳米Al2O3质量分数的增加,Al2O3/PE-EVA复合材料的拉伸强度与Al2O3/PE复合材料的拉伸强度相近,同时由于EVA相的增韧作用,其断裂伸长率优于Al2O3/PE复合材料。     

Study of the densification of a nanostructured composite powder: Part 1: Effect of compaction pressure and reinforcement addition

Al/Al₂O₃ composite coating was prepared by plasma spraying and characterized by XRD and SEM. Some thermal–mechanical properties of the composite coating including thermal diffusivity, microhardness, fracture toughness and sliding wear rate were measured. The results showed that the Al/Al₂O₃ composite coating, compared with Al₂O₃ coating, exhibits denser structure and developed splat interface. The coexistence of Al metal phase and Al₂O₃ ceramic phase effectively increased the fracture toughness and thermal diffusivity of composite coating, in spite of the slight decrease in microhardness. Furthermore, the wear resistance of Al/Al₂O₃ composite coating is superior to that of Al₂O₃ coating.     

Growth of SrTiO3 thin epitaxial films by aerosol MOCVD

SrTiO₃ thin films were prepared by aerosol metal-organic chemical vapour deposition on (001) MgO, R-plane Al₂O₃ and (001) Si single-crystal substrates. Strontium tetramethyl heptadionate and titanium n-butoxide dissolved in diethyleneglycol dimethyl ether were used as precursors. The structure of the films was investigated by X-ray diffraction and transmission electron microscopy. Epitaxial films with [001] and [111] orientation perpendicular to the substrate surface were obtained on MgO and Al₂O₃, respectively. The epitaxial films on the MgO substrate were found to be in a relaxed state with lattice parameters corresponding to the bulk values. SrTiO₃ films on the Si substrate were grown as highly textured in the [011]direction and randomly oriented in the plane parrallel to the substrate surface.     

Growth of La2Mo2O9 films on porous Al2O3 substrates by radio frequency magnetron sputtering

Synthesis conditions of La₂Mo₂O₉ thin film by radio frequency (RF) sputtering technique on Al₂O₃ ceramic substrates are studied. It is found that the deposition temperature and oxygen partial pressure are the most important factors for obtaining pure La₂Mo₂O₉ films. Varying both parameters, Mo-rich, stoichiometric, and Mo-deficient films are obtained. With increasing the La:Mo ratio, films become denser. A crust layer is observed on top of the Mo-rich and the Mo-deficient films. The formation of the La₂Mo₂O₉ phase is discussed with respect to the sputtering mechanism.     

纳米Al_2O_3/聚酰亚胺复合薄膜的介电与力学性能

采用原位聚合与热亚胺化的方法,成功制备了一系列不同纳米Al_2O_3粒子质量分数的纳米Al_2O_3/聚酰亚胺(PI)复合薄膜。通过SEM、TEM、XRD、FTIR、LCR数字电桥、高压电源及电子万能材料试验机对纳米Al_2O_3/PI复合薄膜的微观结构、介电性能及力学性能进行了表征和测试。结果表明:纳米Al_2O_3粒子在均匀地分散在PI基体中;当纳米Al_2O_3粒子质量分数为8%时,纳米Al_2O_3/PI复合薄膜的击穿强度和拉伸强度均达到了最大值;纳米Al_2O_3/PI复合薄膜的介电常数随纳米Al_2O_3质量分数的增加而增加。     

Characterization and properties of r.f.-sputtered thin films of the alumina–titania system

Thin films of the aluminum oxide (Al₂O₃)–titanium oxide (TiO₂) system including Al₂O₃, TiO₂, and Al₂O₃/TiO₂ were prepared by radio-frequency (r.f.) magnetron sputtering using ceramic targets of Al₂O₃, TiO₂, and Al₂O₃/TiO₂ composites with different Al₂O₃/TiO₂ ratio. These films were studied at different substrate temperatures, r.f. powers, and annealing temperatures. Composition, microstructure, thermomechanical property of internal stress, and mechanical property of scratch adhesion, were evaluated. A thin film with a dielectric constant of 62 and a loss tangent of 0.012 was obtained at 500 °C from a 10/90 target. This thin film remained the high dielectric constant of TiO₂, but had an improvement in the dielectric loss tangent. Al₂O₃-containing films had a higher resistivity and breakdown field, which was improved further by annealing. Optical properties, such as refractive index and optical transmittance, were also investigated.     

铁电相BiFeO3对多铁复合薄膜CoFe2O4-BiFeO3铁磁性能的影响

为了研究铁电相BiFeO₃对复合薄膜磁性能的影响,在LaNiO₃ (LNO)缓冲层的Si (100)衬底上旋涂制备了含有0、6、9、10层等不同厚度BiFeO₃的层状CoFe₂O₄-BiFeO₃ (CFO-BFO) 多铁复合薄膜。采用XRD、SEM以及TEM对其结构和形貌进行了表征,采用振动样品磁强计测量磁性,研究了不同厚度BFO对复合薄膜磁性的影响。结果表明: CFO和BFO在异质结构薄膜中共存。缓冲层LNO和铁磁相CFO薄膜具有精细微观结构及明显界面。铁电相BFO的厚度对CFO-BFO复合薄膜的磁性能产生了很大影响。在含有不同层数铁电相BFO的复合薄膜中,含有9层BFO复合薄膜的饱和磁化强度最大,达到了230 emu·cm^-3,相比无铁电相BFO的薄膜,饱和磁化强度提高了18.6%。初步讨论认为: 随着铁电相BFO厚度的增加,CFO与BFO之间的应力传导引起了复合薄膜饱和磁化强度的提高。     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

New LaCu0.5Mn0.5O3 thin films deposited by the sol-gel process on different substrates

New LaCu_0.5Mn_0.5O₃ thin films deposited by the sol-gel process on ceramic Al₂O₃ and ZrO₂, glass ceramic and 101 single-crystal quartz, using the sol-gel process. It was found in all cases that the films are polycrystalline and single phase without preferred orientation. The morphology of the films depends strongly on the nature of the substrate. The films deposited on Al₂O₃ exhibit morphological characteristics making them suitable as possible sensors and catalysts.     

Crystal morphology and growth mechanism of reinforcements synthesized by direct melt reaction in the system Al–Zr–O

In-situ Al₃Zr and Al₂O₃ particulates reinforced aluminum matrix composites were fabricated by the direct melt reaction (DMR) technique in the system Al–Zr–O. Microstructures of the composites and crystal morphology of in-situ formed Al₃Zr and Al₂O₃ particulates were analyzed by scanning-electron microscope (SEM) and transmission electron microscope (TEM). Results indicated that in-situ formed Al₃Zr and Al₂O₃ particles were finer and well distributed in aluminum matrix. Al₃Zr particulates with a tetragonal structure are mainly in the shape of polyhedron. A few of them are rectangular. The length/width ratio of the rectangular Al₃Zr is less than 2.0 and the maximum size is 4 μm. In addition, submicro Al₂O₃ particles with a hexagonal structure were also found in this system. Furthermore, it is found that twin may appear in the Al₃Zr crystal. The twin plane is (1 ). The twinning direction is [2 1].     

Growth of calcium carbonate by the atomic layer chemical vapour deposition technique

Thin films of CaCO₃ (calcite) have been grown with the atomic layer chemical vapour deposition (ALCVD) technique, using Ca(thd)₂ (Hthd=2,2,6,6-tetramethylheptan-3,5-dione), CO₂, and ozone as precursors. Pulse parameters for the ALCVD-type growth are found and self-limiting reaction conditions are established between 200 and 400 °C. Calcium carbonate films have been deposited on soda-lime glass, Si(100), -Al₂O₃(001), -Al₂O₃(012), -SiO₂(001), and MgO(100) substrates. The observed textures were: in-plane oriented films with [100](001)CaCO₃ [100](001)Al₂O₃ and [100](001)CaCO₃[110](001)Al₂O₃ on -Al₂O₃(001), amorphous films on -Al₂O₃(012) when grown at 250 °C, and columnar oriented films on soda-lime glass, Si(001), -SiO₂(001), and MgO(100) substrates with (00l) and (104) parallel to the substrate plane at 250 and 350 °C, respectively. The film topography was studied by atomic force microscopy and AC impedance characteristics were measured on as-deposited films at room temperature. The films were found to be insulating with a dielectric constant (_r) typically approximately 8. Thin films of CaO were obtained by heat treatment of the carbonate films at 670 °C in a CO₂-free atmosphere, but the thermal decomposition led to a significant increase in surface roughness.     

α籽晶促进低温反应溅射沉积α-Al2O3薄膜

分别使用反应溅射Al+α-Al₂O₃(15% α-Al₂O₃,质量分数)复合靶和在金箔基体表面预植α-Al₂O₃籽晶,促进α-Al₂O₃薄膜的低温沉积。使用扫描电子显微镜(SEM)、掠入射X射线衍射(GIXRD)和能谱仪(EDS)等方法表征薄膜样品的表面形貌、相结构和元素组成。结果表明,在射频反应溅射Al+α-Al₂O₃复合靶、沉积温度为560℃条件下能在Si(100)基体上沉积出化学计量比的单相α-Al₂O₃薄膜;使用射频反应溅射Al靶、沉积温度为500℃条件下能在预植α-Al₂O₃籽晶(籽晶密度为10⁶/cm²)的金箔表面沉积出化学计量比的单相α-Al₂O₃薄膜。两种研究方案的结果均表明,α-Al₂O₃籽晶能促进低温沉积单相α-Al₂O₃薄膜。     

Microstructure, crystallinity, and properties of low-pressure MOCVD-grown europium oxide films

A study of growth, structure, and properties of Eu₂O₃ thin films were carried out. Films were grown at 500–600 °C temperature range on Si(1 0 0) and fused quartz from the complex of Eu(acac)₃·Phen by low pressure metalorganic chemical vapor deposition technique which has been rarely used for Eu₂O₃ deposition. These films were polycrystalline. Depending on growth conditions and substrates employed, these films had also possessed a parasitic phase. This phase can be removed by post-deposition annealing in oxidizing ambient. Morphology of the films was characterized by well-packed spherical mounds. Optical measurements exhibited that the bandgap of pure Eu₂O₃ phase was 4.4 eV. High frequency 1 MHz capacitance–voltage (C–V) measurements showed that the dielectric constant of pure Eu₂O₃ film was about 12. Possible effects of cation and oxygen deficiency and parasitic phase on the optical and electrical properties of Eu₂O₃ films have been briefly discussed.     

实验优化设计中频反应溅射Al2O3:Ce薄膜发光性质研究

为了得到最优发光的薄膜材料成分参数,采用均匀设计和二次通用旋转组合设计相结合的方法建立发光强度与薄膜中氧含量和Ce³⁺ 离子掺杂浓度的回归方程,并用遗传算法求其取最大值时的解。用中频反应磁控溅射技术制备了相应成分的Al₂O₃:Ce非晶薄膜。在320nm光激发下,获得了较理想的发射光谱,对薄膜发光机理分析表明:薄膜的光致发光来自于Ce³⁺ 离子的5d1激发态向基态4f1的两个劈裂能级的跃迁。发光强度强烈的依赖于薄膜的掺杂浓度和氧元素含量。XPS检测表明,Al₂O₃:Ce薄膜中存在Ce³⁺ 。Ce³⁺ 含量和薄膜的化学成分是通过X射线散射能谱(EDS)测量的。薄膜试样的晶体结构应用X射线衍射分析。     

ZrO_2增韧Al_2O_3陶瓷的力学性能和增韧机制

对通过热压烧结法制备的3种陶瓷99.5vol%Al2O3(AD995)、ZrO2(15vol%)/Al2O3和ZrO2(25vol%)/Al2O3的力学性能和增韧机制进行了实验和理论研究。基于复合材料细观力学理论并考虑ZrO2的相变特性,建立了描述ZrO2/Al2O3陶瓷力学性能的本构模型。结果表明:ZrO2的加入细化了基体Al2O3晶粒,ZrO2/Al2O3陶瓷的致密性得到提高;3种陶瓷试件的破坏呈现小变形到脆性破坏的特点,压缩加载下试件应力-应变曲线近似为线性关系;AD995陶瓷的断裂韧性为5.65 MPa·m1/2,ZrO2(25vol%)/Al2O3陶瓷的断裂韧性为8.42 MPa·m1/2,提高了近50%;随ZrO2增韧相含量的增加,ZrO2/Al2O3陶瓷的弹性模量降低而断裂韧性增加,这一变化趋势与实验结果有良好的一致性。     

陶瓷添加物对Ti_3SiC_2基复合材料抗氧化性的影响

为研究陶瓷添加物对Ti3SiC2基复合材料性能的影响,首先,采用反应热压烧结法制备了Ti3SiC2材料及陶瓷添加物含量均为30wt%的SiC/Ti3SiC2、Al2O3/Ti3SiC2和MgAl2O4/Ti3SiC2复合材料。然后,测试了材料的力学性能和导电性,在1 373~1 773K温度范围内对Ti3SiC2基复合材料的抗氧化性进行了研究,并对其烧结试样的物相组成和显微结构等进行了表征。结果表明:Ti3SiC2在高温氧化后的主要产物为TiO2和SiO2;氧化层分为内外2层,内层由TiO2与SiO2这2相混合组成,外层为TiO2;氧化层中存在大量显气孔,结构较为疏松,导致抗氧化性较差。与Al2O3/Ti3SiC2和MgAl2O4/Ti3SiC2复合材料相比,SiC/Ti3SiC2复合材料具有更好的抗氧化性。