基于稳定固溶体团簇模型的无扩散阻挡Cu合金薄膜的成分设计

随着超大规模集成电路的发展,器件特征尺寸不断缩小,必然会出现Cu互连扩散阻挡层厚度无法进一步减小等瓶颈问题。因此,开发新型无扩散阻挡层Cu合金薄膜(Cu种籽层)势在必行。该新型互连结构在长时间的中高温(400~500℃)后续工艺实施过程中,需同时具备高的稳定性(不发生互扩散反应)和低的电阻率。基于此,首先综述了目前无扩散阻挡层结构的研究现状及问题,然后对基于稳定固溶体团簇模型设计制备的无扩散阻挡Cu-Ni-M薄膜的研究工作进行了梳理,通过多系列薄膜微观结构、电阻率及稳定性的对比,深入探讨了第三组元M的选择原则及其对薄膜热稳定性的影响。为进一步验证稳定固溶体团簇模型的有效性,对第二组元的变化进行了相关讨论。结果证实,选取原子半径略大于Cu、难扩散且难溶的元素作为第三组元M,薄膜表现出良好的扩散阻挡能力;当M/Ni=1/12,即合金元素完全以团簇形式固溶于Cu基体时,薄膜综合性能达到最优,能够满足微电子行业的要求。所有研究表明,稳定固溶体团簇模型在无扩散阻挡层Cu合金薄膜的成分设计方面十分有效,该模型也有望在耐高温Cu合金及抗辐照材料成分设计方面推广使用。     

T4和T6热处理对Mg-2.5Zn-1.5Ca-0.22Zr合金组织和硬度的影响

采用光学显微镜、扫描电镜和显微硬度仪等研究了T4和T6热处理对Mg-2.5Zn-1.5Ca-0.22Zr镁合金显微组织及硬度的影响。结果表明:Mg-2.5Zn-1.5Ca-0.22Zr镁合金经T4热处理之后,网状结构的β-Ca2Mg6Zn3相逐渐分解并转变为不规则的团聚的块状结构,MgZn2相逐渐溶解于α-Mg基体中,硬度比铸态时显著提高,达到63.87 HV;经过不同时间的T6热处理之后,MgZn2相从α-Mg基体中重新析出,球状的Mg2Ca中间化合物均匀的分布于晶粒内且发生明显长大。随着时效时间的延长,MgZn2相增多,对位错的钉扎增强,合金的硬度提高,在"峰时效"时的硬度达到64.97 HV。410℃×24 h固溶处理后150℃×8 h时效处理为Mg-2.5Zn-1.5Ca-0.22Zr镁合金的最佳热处理工艺。     

Phase equilibria studies in the CaO–SiO2–Al2O3–MgO system with CaO/SiO2 ratio of 0.9

Phase equilibria and liquidus temperatures in the CaO–SiO₂–Al₂O₃–MgO system at a CaO/SiO₂ weight ratio of 0.9 in the liquid phase have been experimentally determined employing high-temperature equilibration and quenching technique followed by electron probe X-ray microanalysis. Isotherms at 1573, 1623, 1673, and 1773 K were determined and the primary phase fields of wollastonite, melilite, olivine, periclase, spinel, and corundum have been located. Compositions of the olivine and melilite solid solutions were analyzed and discussed. Comparisons between the newly constructed diagram, existing data, and FactSage predicted phase diagrams were performed and differences were discussed. The present study will be useful for guidance of industrial practices and further development of thermodynamic modeling.     

核燃料用γ-U合金的成分规律

铀合金作为一种重要核燃料,其体心立方结构的高温稳定的γ-U合金具有较好的综合性能,是合金设计所追求的目标。本文引入描述稳定固溶体结构的"团簇加连接原子"模型,用于建立γ-U固溶体合金的结构模型和相应成分式,指出其结构单元为体心立方第一近邻配位多面体团簇加3个连接原子构成。进而利用该结构单元对现有合金成分进行了解析,能够稳定形成体心立方bcc结构的合金均满足上述模型,如[Mo-U14]Mo3(U-10.7Mo),[Zr-U14]Nb3(U-7.5Nb-2.5Zr,即不锈铀)等,这些合金实际上均在各自体系中具有最优良的结构稳定性,显示出优异的耐蚀性。本文证实,基于团簇加连接原子模型的成分设计方法在预测γ-U合金成分与性能上具有重要指导价值。     

NiCrAlFe精密电阻合金中的L12有序结构研究

有序结构的形成是决定NiCrAlFe精密电阻合金电学性能的关键因素。本文利用第一性原理赝势平面波方法，计算了合金处于无序固溶体结构和形成L12型有序结构时的结合能、态密度、晶格常数等参数，并利用高分辨透射电子显微镜（HRTEM）对合金进行了结构表征，还测试了固溶态和时效态的电阻率。从结合能来看，该合金形成L12有序结构时比无序固溶体更加稳定；态密度以及部分态密度计算结果则表明，在L12有序结构中，Ni、Cr、Al、Fe会强烈成键而使得整个合金体系变得稳定；HRTEM分析结果证明固溶态合金经过和时效处理后出现了L12有序结构，而且该有序结构的晶格常数与计算值基本一致。对比无序固溶体与L12型有序结构费米能级处的态密度值发现，当形成L12有序结构时合金的导电能力较无序固溶体下降，电阻率升高，与实际测试结果吻合。     

Microstructure and mechanical properties of squeeze-cast Al−5.0Mg−3.0Zn−1.0Cu alloys in solution-treated and aged conditions

The microstructure and mechanical properties at different depths of squeeze-cast, solution-treated and aged Al−5.0Mg−3.0Zn−1.0Cu alloy were investigated. For squeeze-cast alloy, from casting surface to interior, the grain size of α(Al) matrix and width of T-Mg₃₂(AlZnCu)₄₉ phase increase significantly, while the volume fraction of T phase decreases. The related mechanical properties including ultimate tensile strength (UTS) and elongation decrease from 243.7 MPa and 2.3% to 217.9 MPa and 1.4%, respectively. After solution treatment at 470 °C for 36 h, T phase is dissolved into matrix, and the grain size increases so that the UTS and elongation from surface to interior are respectively reduced from 387.8 MPa and 18.6% to 348.9 MPa and 13.9%. After further peak-aging at 120 °C for 24 h, numerous G.P. II zone and η′ phase precipitate in matrix. Consequently, UTS values of the surface and interior increase to 449.5 and 421.4 MPa, while elongation values decrease to 12.5% and 8.1%, respectively.     

方腔内耦合传热传质非对称流动数值模拟

对带有质热源的方腔内流体传热传质进行数值研究。针对不同Ra、Nc、Sr和Df，探究对称方腔内流体传热传质的分岔特性。结果表明：存在临界Ra_c使流体流动形态发生转变，当Ra<Ra_c时，流体流线、温度场和浓度场对称分布；当Ra>Ra_c时，流体发生偏斜。增大浮升力，流体更易发生分岔现象。增强Soret和Dufour效应可增强传热对称性并增大流体发生分岔的临界Rayleigh数。     

Robust,low haze and graded porous anti-reflective glass by Tailoring the Nanostructures

Low haze and anti-reflective glass has high potential applications in automobile and optoelectronic fields. Etching is a novel and effective method to fabricate gradient refractive index anti-reflective layer on glass surface. However, the gradient layer on glass surface prepared by the etching method usually characterizes rough porous structure, and the structural defect results in high haze and low abrasion resistance to restrict its applications. In this paper, a hydrothermal etching method has been explored to prepare anti-reflective glass. It has demonstrated to be a new and facile method successfully to tailor the porous nanostructure of gradient refractive index layer and largely decrease the haze of the glass, by adding complex compound in the etching solution. Compared with the etching solution containing NaOH, adding the complex compound of C₆H₅Na₃O₇ in the etching solution has the advantage to overcome the defects. The grain diameter of the graded porous anti-reflective film decreases from ~63 nm to ~18 nm, the etched film thickness increases from 0.44 μm to 1.55 μm, the haze decreases drastically from 23.76% to 1.00%, the reflectivity decreases from 5.88% to 1.08% and the abrasion resistance greatly increases. However, when changing the complex compound from C₆H₅Na₃O₇ to Na₂HPO₄, the haze is 23.44% and has no effect on decreasing haze. Structural characterizations show that the grain size in the porous gradient layer can be easily tailored by changing the ion radius of complex anion in the etching solution, and the optical properties can be controlled. The paper provides new insights into the nanostructures and the preparation approach of anti-reflective glass.     

镀锌层硅酸盐+虫胶复合转化膜的制备和表征

目的阻碍热镀锌板出现白锈,提高镀锌层的耐腐蚀性能。方法采用正交试验法优化出添加虫胶水溶液的有机无机复合钝化液。通过电化学Tafel极化曲线、交流阻抗(EIS)、乙酸铅点滴和中性盐雾试验,对比分析基体、硅酸盐+虫胶复合钝化膜与铬酸盐钝化膜的耐腐蚀性能。采用摩擦法测试对比分析基体和无铬钝化膜试样的附着性能,并通过扫描电子显微镜、X射线光电子能谱和红外光谱对形貌和结构进行分析。结果添加虫胶水溶液的复合钝化膜表面平整致密,72 h中性盐雾试验后的腐蚀面积小于10%。乙酸铅点滴试验和电化学测试显示,复合钝化膜的耐腐蚀性能较基体好。附着力试验测试显示,复合钝化膜具有良好的附着能力。结论因为复合钝化液中的虫胶与硅酸盐交织为O—Si—CH_2结构,与金属离子结合生成致密的膜层附着在镀锌层表面,使得复合钝化膜致密平整,且使腐蚀过程得到了强烈的抑制。     

Synthesis of “walnut-like” BiOCl/Br solid solution photocatalyst by electrostatic self-assembly method

In this paper, under the control strategy of surface charge of BiOCl photocatalyst and the electrostatic adsorption of anions and cations in potassium bromide (KBr) and polyvinylpyrrolidone (PVP), the self-assembly of “walnut-like” BiOCl/Br solid solution nanophotocatalyst at a lower temperature water bath was proposed for the first time. X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy-dispersive system (EDS), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), UV-Vis, photoluminescence spectroscopy (PL) and Mott-Schottky curve, transient photocurrent densities, and electrochemical impedance spectroscopy (EIS) were used to analyze the properties of materials, including its morphology, element distribution and chemical states, specific surface area, electrochemical property, and photogenic charge transfer. Based on the degradation performance of RhB dye wastewater and phenol in visible and ultraviolet light, and the band structure of BiOCl/Br solid solution, the reason for the improved photocatalytic activity was deeply discussed, and the possible degradation mechanism was also put forward. The above results show that Br⁻ can be inserted into the crystal lattice of BiOCl under the effect of electrostatic adsorption to form solid solution by the interaction between atomic orbitals, which not only reduces the bandgap width but also improves the separation and mobility of photogenic electrons and holes, causing the absorbed light to shift red to the visible region. In addition, when the n_Br⁻/n_Cl⁻ = 0.67, “walnut-like” BiOCl/Br solid solution was formed, and this kind of special core-shell structure not only can increase the specific surface area, increase the number of active sites, but also can make the light reflect and refract many times in the cavity and further increase the utilization rate of light energy, and then the best photocatalytic activity was achieved. This study provides an new method to enhance the photocatalytic performance of BiOCl and be conducive to the development of modern material science.