多级时效对Al-Mg-Si(Cu)合金力学性能和显微结构的影响

本文通过透射电镜观察、差示扫描量热分析(DSC)和硬度测试等方法研究了6061铝合金在多级时效处理过程中力学性能和显微结构演变的规律.其中,T6I6热处理为先进行固溶处理,淬火后进行180℃预时效,然后在65℃中断时效,最后在180℃再次时效,120/T6I6热处理则将预时效温度改为120℃.结果表明,T6I6热处理不会明显提高合金的峰值硬度,合金强度与析出相类型、尺寸和分布有关系.120℃预时效后中断时效时继续形成GP区或β″前驱相,而180℃预时效后中断时效对显微结构的影响较小.120/T6I6的中断时效过程析出的主要是尺寸较小的GP区或β″前驱相,它们在再时效阶段不能成为析出相的形核点.T6I6在中断时效前GP区和β″前驱相基本全部析出.T6I6热处理和120/T6I6热处理均没有使峰值硬度明显增加,而且120/T6I6会拖延峰值时间.     

Mg/Si含量比值对Al-Mg-Si合金析出行为的影响

采用显微硬度计、扫描电子显微镜(SEM)、高分辨透射电子显微镜(HRTEM)及能谱仪,研究了不同Mg/Si含量比的Al-Mg-Si合金在不同时效温度下的时效析出行为.合金为Mg含量相同,Mg/Si摩尔比接近2.0、1.0和0.5的三种A、B和C合金(合金总含量依次增多).结果表明:Mg/Si含量比对析出动力学有很大影响,温度越高Mg/Si摩尔比对时效动力学影响越大.SEM分析表明:Si含量越高的合金,晶界析出相越连续且尺寸越大,并有一定的晶界无析出带.HRTEM分析表明:过时效阶段,β′相的形成跟Mg/Si比和温度有关;两种时效温度下,在A合金中均析出β′相;而B和C合金在180℃时效主要析出β″相,250℃时效时,B合金中易形成TypeB相,C合金可析出TypeA、TypeB和TypeC三种相.     

AlCuMgAg合金时效后的择优纳米析出相

Al-Cu-Mg系合金是一种时效强化型合金。该系合金作为航空航天工业中的基础材料已有几十年的历史，但它还在不断的发展和完善。在高Cu：Mg比率的Al-Cu-Mg合金中加入微量的舷，会促进在{111}。面上形成一种均匀分布的片状Ω相，不但会提高时效强化效果，而且会改变合金的时效过程。细小的Ω相的均匀分布使得Al-Cu-Mg-Ag系合金在200℃时具有良好的热稳定性，因此该系合金被广泛用于航空航天结构材料。     

铝—锂合金中δ‘（Al3Li）沉淀相时效粗化行为及体积分数的测定

对经固溶处理的二种Ａｌ－Ｌｉ合金（１．９４ｗｔ．％Ｌｉ和２．７５ｗｔ．％Ｌｉ）的时效过程进行了研究。结果表明：δ＇的生长速率遵从Ｏｓｔｗａｒｄ粗化动力学。１．９４ｗｔ．％Ｌｉ合金δ＇产生于时效过程中，而２．７５ｗｔ．％Ｌｉ合金的δ＇产生于时效的前期阶段。前者的表观体积分数明显大于根据相图估算的数值，真实体积分数则与此值接近；后者的体积分数低于根据相图估算的数值，这可能归咎于δ＇固相线的位置、统计学     

Cu含量对电场快速烧结W-Cu合金的影响

采用Gleeble—3500D热模拟机,在烧结温度为800℃,烧结时间为3 min的条件下,借助金相显微镜、扫描电镜、显微硬度测试计分析,研究了电场对烧结W-xCu(x=10%,20%,30%和40%)(质量分数)体系的影响。结果表明:本条件下,可得到密度较高、组织较均匀细小的烧结体;并且随着Cu含量的增加,烧结体致密化程度逐步提高,组织更加均匀,晶粒更加细小,平均晶粒尺寸从1.0μm降到0.3μm;但烧结体的硬度会相应降低。     

Cu-Cr-Zr合金时效析出相的研究

利用高分辨电子显微镜（HRTEM）及系列欠焦像出射波函数重构技术,探明了在大气环境下,Cu-Cr-Zr合金峰值时效时存在氧化物析出相。研究结果表明：Cu-Cr-Zr合金经950℃×1.5 h固溶处理、450℃时效6 h硬度达峰值;此时样品中除早期的具有花瓣状应变场衬度的共格析出相外,另一类强化相为圆盘状形貌的CuCrO2;该氧化物析出相为三方晶系,空间群为R 3 m（166）,与基体具有特定取向关系：[011]Cu//[010]CuCrO2,（111）Cu//（003）CuCrO2,惯习面为{111}Cu。     

Mg-Gd-Y合金时效初期析出结构的形成和演变

本文利用原子分辨的高角环形暗场扫描透射电镜(HADDF-STEM)成像技术并结合第一性原理计算的方法研究了Mg97 Gd2 Y1(at.％)合金200℃时效初期结构的形成和演变过程.结果表明,合金时效初期优先形成与富稀土原子柱近邻组合关联的各种纳米级细小富稀土团簇.这些由富稀土原子柱构建的团簇可以通过分解、重组而转变成...     

FeCrAl合金中碳化物的时效析出和钇的影响

ＴＥＭ研究表明,低碳（０．０１－０．０３ｗｔ．％Ｃ）Ｆｅ－（１５．２５）Ｃｒ－（４,５）Ａｌ合金经１２００℃固溶处理后再于４７５－５４０℃时效时,碳化物迅速在晶界、位错等昌体缺陷处析出,晶界碳化物近于连续,晶界两侧形成析出带,析出相的衍谱与Ｃｒ２３Ｃ６和Ｃｒ７Ｃ３基本吻合,在含０．４ｗｔ．％Ｙ的ＦｅＣｒＡｌ合金中,含２相的衍射谱与六方α－Ｆｅ１７Ｙ２相的谱吻合,该相俘获碳原子的作用使合金在时效时不     

铜(钛)和铜(铬)自形成阻挡层性能表征

采用直流磁控溅射法分别将Cu (Ti)和Cu (Cr)合金层沉积在SiO2/Si衬底上,随后将制得的样品在真空(2×10-3 Pa)中退火1h,退火温度为300 ～ 700℃.对Cu (Ti)及Cu (Cr)自形成阻挡层进行对比研究,通过X射线衍射(XRD)、X射线光电子能谱(XPS)和透射电子显微镜(TEM)观察并表征样品的微观结构.通过半导体分析仪测试样品的电学性能,并分析了其热稳定性.结果表明,在Cu膜中分别加入少量的Ti或Cr可使Cu沿〈111〉晶向择优取向生长.两种样品交界面处的Cu及Si元素含量迅速下降,表明在交界面处自形成阻挡层,抑制了Cu与Si元素之间的扩散.Cu (Ti) /SiO2/Si和Cu (Cr) /SiO2/Si样品漏电流测试结果表明,Cr自形成的阻挡层具有更好的热稳定性.     

The microstructure,mechanical stress,texture, and electromigration behavior of Al-Pd alloys

As the minimum feature size of interconnect lines decreases below 0.5 urn, the need to control the line microstructure becomes increasingly important. The alloy content, deposition process, fabrication method, and thermal history all determine the microstructure of an interconnect, which, in turn, affects its performance and reliability. The motivation for this work was to characterize the microstructure of various sputtered Al-Pd alloys (Al-0.3wt.%Pd, Al-2Cu-0.3Pd, and Al-0.3Nb-0.3Pd) vs sputtered Al-Cu control samples (Al-0.5Cu and Al-2Cu) and to assess the role of grain size, mechanical stress, and crystallographic texture on the electromigration behavior of submicrometer wide lines. The grain size, mechanical stress, and texture of blanket films were measured as a function of annealing. The as-deposited film stress was tensile and followed a similar stress history on heating for all of the films; on cooling, however, significant differences were observed between the Al-Pd and Al-Cu films in the shape of their stress-temperature-curves. A strong (111) crystallographic texture was typically found for Al-Cu films deposited on SiO₂. A stronger (111) texture resulted when Al-Cu was deposited on 25 nm titanium. Al-0.3Pd films, however, exhibited either a weak (111) or (220) texture when deposited on SiO₂, which reverted to a strong (111) texture when deposited on 25 nm titanium. The electromigration lifetimes of passivated, ≈0.7 μm wide lines at 250°C and 2.5 × 10⁶ A/cm² for both single and multi-level samples (separated with W studs) are reported. The electromigration behavior of Al-0.3Pd was found to be less dependent on film microstructure than on the annealing atmosphere used, i.e. forming gas (90% N₂-10%H₂) annealed Al-0.3Pd films were superior to all of the alloys investigated, while annealing in only N₂ resulted in poor lifetimes.     

The effect of Mo back contact ageing on Cu(In,Ga)Se2 thin‐film solar cells

In this work, we investigate the effect of ageing Mo‐coated substrates in a dry and N₂ flooded cabinet. The influence was studied by preparing Cu(In,Ga)Se₂ solar cells and by comparing the electrical performance with devices where the Mo layer was not aged. The measurements used for this study were current–voltage (J‐V), external quantum efficiency (EQE), secondary ion mass spectroscopy (SIMS) and capacitance–voltage (C‐V). It was concluded that devices prepared with the aged Mo layer have, in average, an increase of 0.8% in efficiency compared with devices that had a fresh Mo layer. Devices with aged Mo exhibited a nominal increase of 12.5 mV of open circuit voltage, a decrease of 1.1 mA/cm⁻² of short circuit current and a fill factor increase of 2.4%. Heat treatment of fresh Mo layers in oxygen atmosphere was also studied as an alternative to ageing and was shown to provide a similar effect to the aged device's performance. Copyright © 2013 John Wiley & Sons, Ltd.     

The effects of process conditions and substrate on copper MOCVD using liquid injection of (hfac)Cu(vtmos)

Copper MOCVD (metalorganic chemical vapor deposition) using liquid injection for effective delivery of the (hfac)Cu(vtmos) [1,1,1,5,5,5-hexafluoro-2,4-pentadionato(vinyltrimethoxysilane) copper(I)] precursor has been performed to clarify growth behavior of copper films onto TiN, <100> Si, and Si₃N₄ substrates. Especially, we have studied the influences of process conditions and the substrate on growth rates, impurities, microstructures, and electrical characteristics of copper films. As the reactor pressure was increased, the growth rate was governed by a pick-up rate of (hfac)Cu(vtmos) in the vaporizer. The apparent activation energy for copper growth over the surface-reaction controlled regime from 155°C to 225°C was in the range 12.7–32.5 kcal/mol depending upon the substrate type. It revealed that H₂ addition at 225°C substrate temperature brought about a maximum increase of about 25% in the growth rate compared to pure Ar as the carrier gas. At moderate deposition temperatures, the degree of a <111> preferred orientation for the deposit was higher on the sequence of <Cu/Si<Cu/TiN<Cu/Si₃N₄. The relative impurity content within the deposit was in the range 1.1 to 1.8 at.%. The electrical resistivity for the Cu films on TiN illustrated three regions of the variation according to the substrate temperature, so the deposit at 165°C had the optimum resistivity value. However, the coarsened microstructures of Cu on TiN prepared above 275°C gave rise to higher electrical resistivities compared to those on Si and Si₃N₄ substrates.     

Impact of compositional grading and overall Cu deficiency on the near‐infrared response in Cu(In,Ga)Se2 solar cells

Highly efficient thin film solar cells based on co‐evaporated Cu(In,Ga)Se₂ (CIGS) absorbers are typically grown with a [Ga]/([Ga] + [In]) (GGI) gradient across the thickness and a Cu‐poor composition. Upon increasing the Cu content towards the CIGS stoichiometry, lower defect density is expected, which should lead to increased absorption in the near‐infrared (NIR), diffusion length and carrier collection. Further, optimization of the GGI grading is expected to increase the NIR response. In this contribution [Cu]/([In] + [Ga]) (CGI) values are increased by shortening the deposition stage after the first stoichiometric point. In order to obtain comparable Ga contents at the interface for proper band alignment, the front GGI gradings were actively modified. With a relative CGI increase of 7%, we observe an increased photocurrent, originating from an improved NIR external quantum efficiency response. By characterizing the modified absorber properties by reflection‐transmission spectroscopy, we attribute the observed behavior to changes in the optical properties rather than to improved carrier collection. Cu‐dependent modifications of the NIR‐absorption coefficients are likely to be responsible for the variations in the optical properties, which is supported by device simulations. Adequate re‐adjustments of the co‐evaporation process and of the alkali‐fluorides post‐deposition treatments allow maintaining V_oc and FF values, yielding an overall increase of efficiency as compared to a reference baseline. © 2016 The Authors. Progress in Photovoltaics : Research and Applications published by John Wiley & Sons Ltd.     

Effect of Cu content on interfacial reactions between Sn(Cu) alloys and Ni/Ti thin-film metallization

The effect of Cu content in Sn(Cu) alloys on the interfacial reaction between Ni thin film and Sn(Cu) alloys has been investigated. We have found that the variation of Cu content has a strong influence on the spalling of the Ni thin film. With small Cu additives in the Sn, spalling was deferred to longer reflowing time. When the Cu content increased to about 1.0 wt.%, a layer of Cu-Sn compound formed on the Ni thin film, and no spalling was observed after 20-min reflowing. The possible mechanism of spalling deferring is proposed. A Cu flux from the solder to the interface compensated the ripening flux of the semispherical compound grains; therefore, spalling was retarded. The driving force of the Cu flux was attributed to the reduction of Cu solubility caused by the presence of Ni at the interface of the Ni thin film. The Cu flux from solder to the interface is calculated to be in the same order with the ripening flux of the Cu₆Sn₅ compound grains, which confirms the proposed mechanism of spalling deferring. For the Sn(Cu) alloys having Cu content over 1.0 wt.%, the Cu-Sn compound layer grew so fast that the surface of the interfacial compound layer was free of Ni. There was no Cu flux to compensate the ripening flux; therefore, the ripening flux dominated, and spalling occurred after a short reflowing time.     

硒化温度对Cu(In, Al)Se2薄膜结构和光学性质的影响

采用了磁控溅射制备Cu-In-Al金属前驱体薄膜,后硒化快速退火得到铜铟铝硒(Cu(In,Al)Se2,CIAS)薄膜.研究了硒化温度对CIAS薄膜晶体结构和光学性质的影响.研究发现CIAS薄膜的晶体结构依赖于硒化温度,其禁带宽度随硒化温度升高发生红移.研究结果表明,CIAS薄膜的最佳硒化温度为540℃,其晶体结构为纯黄铜矿结构,禁带宽度为.34 eV,对应太阳电池理论最大效率的吸收层材料禁带宽度     

The effect of O<Subscript>2</Subscript> ambient annealing on the microstructure of Cu(Mg) in the form of a Cu(Mg)/SiO<Subscript>2</Subscript>/Si multilayer

The effect of annealing in an O₂ ambient on Cu(Mg)/SiO₂/Si multilayer films was investigated. As-deposited Cu(Mg)/SiO₂/Si multilayer samples with film thicknesses in the 1,000–3,000 ? range were annealed for 30 min in oxygen ambients at pressures ranging from vacuum to 100 mtorr. The results showed that annealing in an 8-mtorr O₂ ambient significantly decreased the electrical resistivity of a 1,000 ? sample from 10.5 μΩ-cm to 3.7 μΩ-cm. Annealing in the O₂ ambient enhanced Mg diffusion to the surface in comparison to vacuum annealing. Furthermore, O₂ ambient annealing leads to excessive grain growth. However, the effect of O₂ ambient annealing on resistivity is less when the thickness of the film increases.     

A theoretical study of phosphorescent Cu(I) complexes with 2-(2'quinolyl)imidazole and POP mixed ligands

We herein report a theoretical study using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods to investigate Cu(I) complexes with 2-(2′-pyridyl/quinolyl)imidazole and bis[2-(diphenylphosphino)phenyl]ether mixed ligands. Based on the experimental data for complexes 1 and 2, we first benchmarked different functionals with different HF% and found B3PW91 to be the optimal functional for this system. The computational results indicate that complex 1, with a pyridyl unit, has a much larger radiative decay rate (k_r) than complex 2, which has a quinolyl unit. This difference is presumably due to higher HOMO electronic distribution in the d_x²-_y² orbital, which leads to a markedly shortened CuN₂ bond, enhancing the metal-ligand interaction. However, a much smaller experimental value was found for the non-radiative decay rate (k_nr) in complex 2, rendering 1 a slightly weaker emitter than 2. We conclude that the difference is due to more effective suppression of deformation when the quinolyl unit is used instead of pyridyl. We sought to increase the photoluminescence quantum yield (PLQY) through modifying the ligand on complex 2, with the goal being to keep the small k_nr value while simultaneously increasing k_r. The computational results indicate that our designed complexes 2a-2c, which possess modified ligands with electron-donating or withdrawing alkyl substituents on N₃, increased the distributions of d_x²-_y² and decreased that of the d_yz compared to 2. Their coordinating abilities were therefore enhanced, with the k_r values being 1.34, 22.70, and 0.16 times that of 2 for 2a, 2b and 2c, respectively. Higher PLQYs were achieved in 2a and 2b with the addition of electron-donating alkyl substituents on the ligands, which yielded complexes with significantly shortened CuN₂ bonds and enhanced metal-ligand interaction. This investigation on the microscopic mechanism of the photoluminescent properties of these complexes can provide useful knowledge for experimentalists.     

Effects of Substrate Materials on Self-Formation of Ti-Rich Interface Layers in Cu(Ti) Alloy Films

In our previous studies, thin Ti-rich layers were found to uniformly cover SiO₂/Si substrate surfaces at the interface with Cu(Ti) alloy films after annealing at elevated temperature. These Ti-rich layers were also found to prevent intermixing between the Cu(Ti) alloy films and the substrate, resulting in a simple barrier formation technique, called “self-formation of the diffusion barrier,” which is attractive for fabrication of ultra-large scale integrated (ULSI) interconnect structures. In the present study, to understand the mechanism of self-formation of the Ti-rich barrier layers on the substrate surface, the effects of SiO₂/Si, SiN/SiO₂/Si and NaCl substrate materials on the interfacial microstructure were investigated. The microstructures were analyzed by transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS), and correlated with the electrical properties of the Cu(Ti) interconnects. It was concluded that the chemical reaction of Ti with the substrate materials was essential for the self-formation of the Ti-rich layers.