Improvement of electrochemical performance of Si thin film anode by rare-earth La PIII technique

Si thin film is considered a good candidate for rechargeable Li-ion thin film battery anode material because it possesses large lithium adsorption capacity, good thermal and chemical stability. However, the fast capacity decay upon charge-discharge cycling has hindered the application of Si thin films. In this investigation, Si thin films were sputtered on Cu foils and characterized. One of the explanations for the bad cycling characteristics is the poor adhesion between the Si film and the Cu substrate. Some Cu foils were treated by Plasma Immersion Ion Implantation (PIII) method using rare-earth La element to improve the adhesion strength between the Si thin films and the Cu substrate in order to enhance the cycling performance. Electrochemical analysis revealed that La PIII surface treatment on the Cu foil substrate was effective in strengthening the interface adhesion between the Si thin films and the Cu substrates. Subsequently, the electrochemical performance of the Si thin film anodes was improved.     

单晶Ge纳米薄膜面向热导率的分子动力学模拟

利用非平衡分子动力学模拟方法研究了单晶Ge薄膜的厚度以及温度对其面向热导率的影响规律。针对单晶Ge薄膜的结构特点和导热机制,采用Stillinger-Weber势能模型描述Ge粒子间的相互作用,并且建立面向稳态热传导模型。模拟结果显示,单晶Ge薄膜面向热导率具有明显尺寸效应,随薄膜厚度的增加而增大,随温度的升高而减小。与法向热导率的模拟结果进行比较,证明单晶Ge薄膜热导率具有各向异性的特点。     

Thermal conductivity of EB-PVD ZrO2-4 mol% Y2O3 films using the laser flash method

The variation in thermal conductivity and thermal diffusivity of ZrO₂-4 mol% Y₂O₃ coatings deposited onto Inconel substrates by EB-PVD is examined as a function of coating thickness using the laser flash method. The coatings are found to consist of columnar grains with a feather-like microstructure. The thermal conductivities of the coatings are calculated using two methods: the first involves separating the coating from the substrate and measuring the thermal diffusivity directly; the second uses thermal diffusion results from coatings still attached to the substrate and is based on the response function method. The results of both methods are in excellent agreement, and show that the thermal conductivities of the coatings increase with increasing coating thickness. The results also confirm that the double layer method can be used successfully to calculate the thermal conductivities of thin film coatings.     

Effect of substrate bias voltage on the texture and microstructure of Cu thin films deposited by ion beam deposition

Cu thin films deposited by non-mass separated ion beam deposition under various substrate bias voltages were investigated. The film textures and microstructure were analyzed by X-ray diffraction and field emission scanning electron microscopy, and the resistivity of the film was measured with the Van der Pauw method. It was found that the optimum negative substrate bias voltage for Cu films was −50 V. The Cu films deposited without substrate bias voltage showed a columnar grain structure with small grains and random orientation. However, when a substrate bias voltage of −50 V was applied, the Cu films had a non-columnar structure with a strong (111) texture and large grains. The electrical resistivity of the Cu films decreased remarkably with increasing negative substrate bias voltage, and reaching a minimum value of 1.8±0.13 μΩ cm at the substrate bias voltage of −50V.     

热处理对PI基板铜薄膜金属化TiN阻挡层的影响

聚酰业胺(PI)材料具有介电常数低，分解温度高及化学稳定性好等优点，是很有前途的电子封装材料。Cu具有低的电阻和高的抗电迁移能力，足PI基板金属化的首选材料。采用物理气相沉积(PVD)方法在PI基板上沉积Cu薄膜，利用TiN陶瓷薄膜阻挡Cu向PI基板内部扩散。研究热处理条件下TiN陶瓷薄膜阻挡层的阻挡效果、Cu膜电阻变化以及Cu膜的结合强度，俄歇谱图分析表明TiN可以有效地阻挡Cu向PI内的扩散。300℃热处理消除了Cu膜内应力，提高了Cu膜的结合强度。     

磁控溅射Cu膜屈服强度的有限元计算

采用离子辅助轰击共溅射设备，在Si基体的(111)晶面上制得了所需的铜膜。采用纳米压入实验，获得不同退火温度下Cu膜的弹性模量和硬度。再在纳米压入实验的基础上，结合有限元模型计算不同退火温度下磁控溅射得到的Cu膜屈服强度。发现Cu膜的屈服强度远高于整体Cu材料的屈服强度，并且退火温度对薄膜的屈服强度影响很大。通过XRD测量发现其主要原因是退火改变了晶粒尺寸和多晶Cu膜的晶粒取向分布，而导致Cu膜屈服强度的降低。     

Mechanical properties and microstructures of Al-Cu Thin films with various heat treatments

The relationship between microstructure and mechanical properties has been investigated in Al-Cu thin films. The Cu content in Al-Cu samples used in this study ranges from 0 to 2 wt.% and substrate curvature measurement was used to measure film stress. In thin films, the constraints on the film by the substrate influence the microstructure and mechanical properties. Al-Cu thin films cooled from high temperatures have a large density of dislocations due to the plastic deformation caused by the thermal mismatch between the film and substrate. The high density of dislocations in the thin film enables precipitates to form inside the grain even during a very rapid quenching. The presence of a large density of dislocations and precipitates will in turn cause precipitation hardening of the Al-Cu films. The precipitation hardening is dominant at lower temperatures, and solid solution hardening is observed at higher temperatures in the tensile regime. Pure Al films showed the same values of tensile and compressive yield stresses at a given temperature during stress-temperature cycling.     

热处理效应对Sn-Al与Sn-Ca纳米薄膜的电磁屏蔽机制

利用溅镀Sn-Al纳米薄膜和Sn-Cu纳米薄膜讨论结晶机制与膜厚对电磁波屏蔽特性的影响,比较了Sn-Al和Sn-Cu薄膜的高温显微组织、导电性与电磁波屏蔽性能。结果表明,高温处理提高了Sn-Al纳米薄膜的电磁波屏蔽性。在低频条件下,高Cu摩尔浓度的Sn-Cu纳米薄膜不能有效改善电磁波屏蔽性;高温处理后,低Cu摩浓度的Sn-Cu纳米薄膜能提高低频的电磁波屏蔽性,而高频下的电磁波屏蔽性则呈相反趋势。     

电泳法制备择优取向钛酸薄膜

以钛酸的纳米单片层为前驱体,采用电泳沉积法在Pt极板上制备择优取向钛酸薄膜,并通过热处理使其转换成TiO2薄膜。考察了悬浮介质和沉积电压对钛酸薄膜形貌及结构的影响,通过XRD、SEM对薄膜进行了表征。结果表明:在乙醇:水为1:1的悬浮介质中沉积制得的钛酸薄膜均匀、平整、致密,具有很强的b轴取向;薄膜的厚度随电压的升高而增厚;经500℃热处理后,钛酸薄膜转变成具有(101)择优取向的锐钛矿相结构的TiO2薄膜,颗粒尺寸分布均匀,平均粒度约40nm。     

Au / Ni / Cu 多层薄膜热带海洋气候腐蚀失效机制研究

目的了解Au/Ni/Cu多层金属薄膜在热带海洋气候下的失效机制,为研究电子元器件表面腐蚀失效的早期预警提供参考。方法采用磁控溅射法在p型单晶Si(100)基片上沉积Au/Ni/Cu薄膜,在热带海洋气候环境下进行时效实验,采用原子力显微镜及俄歇电子能谱对薄膜失效表面与界面结构微观变化进行研究。结果时效实验初期,Au/Ni/Cu薄膜表面发生了Au原子聚集,形成了不再连续的岛状结构,岛与岛之间产生了表面微裂纹。随着时效时间的延长,表面形成腐蚀洞,腐蚀洞附近有Ni和Cu扩散至Au层表面。时效时间进一步延长后,腐蚀洞的数量增加,面积增大,此时样品处于腐蚀末期;与此同时,在未产生腐蚀洞的区域,Au/Ni/Cu薄膜界面未出现明显粗化。结论 Au/Ni/Cu薄膜在热带海洋气候中的失效主要是通过表面产生的腐蚀洞进行的。     

工艺条件对溅射薄膜附着性的影响

溅射薄膜材料应用很广泛，其中薄膜的附着性是影响薄膜材料质量的重要因素，膜／基界面结合强度是制约薄膜材料实际应用的关键之一。本文综述了关于溅射薄膜附着性能的研究进展，总结了影响附着性的主要工艺因素，为改善薄膜质量提供参考依据。     

Yield surface of polycrystalline thin films as revealed by non-equibiaxial loadings at small deformation

A biaxial device developed at DiffAbs beamline of the SOLEIL synchrotron facility has been employed to determine the applied strains in film–substrate composites using both X-ray diffraction and digital image correlation measurements. Such an experimental combination is used for the first time to determine the yield surface of a polycrystalline thin film deposited on a polyimide substrate. In situ biaxial tensile tests under different biaxial planar load ratios were performed on W/Cu nanocomposite thin films deposited on flexible substrates. The effect of loading path on the yield stress of W/Cu nanocomposites is presented by considering a large range of proportional loadings. By comparing experimental results with theoretical models, this study reveals the brittle behaviour of W/Cu nanocomposite thin films at small deformations.     

飞秒激光直写铜微电极研究

随着柔性电子产品对高效热管理的需求不断增长,近年来制备高导电性柔性薄膜越来越受到人们的广泛关注. 以聚酰亚胺(PI)为基底,采用激光直写技术制备铜(Cu)和铜-银(Cu-Ag)薄膜,并对制备的Cu-Ag薄膜进行了物相分析和结构表征. 结果表明,铜纳米颗粒和银纳米线在激光辐照的作用下表面局部熔化,进而烧结;通过比较直写制备的铜薄膜和Cu-Ag薄膜在不同温度下7 天内电阻的变化,得出银的引入提高了复合材料整体的抗氧化性;对Cu/PI和Cu-Ag/PI两种复合材料的热扩散系数和热导率进行测试,得出银的引入提高了复合薄膜的热导率,Cu-Ag/PI薄膜表现出比Cu/PI薄膜更好的热性能. 为制备具有良好热稳定性的Cu /PI和Cu-Ag /PI复合材料提供了一种快速简便、经济节约的方法.

     

Performance of Chemical Vapor Deposited Boron-Doped AlN Thin Film as Thermal Interface Materials for 3-W LED: Thermal and Optical Analysis

Boron-doped aluminum nitride(B-Al N)thin films were synthesized on Al substrates by using chemical vapor deposition method by changing the synthesis parameters and were used as thermal interface material for high power light emitting diode(LED).The B-Al N thin film-coated Al substrate was used as heat sink and studied the performance of high power LED at various driving currents.The recorded transient cooling curve was evaluated to study the rise in junction temperature(T_j),total thermal resistance(R_(th-tot))and the substrate thermal resistance(R_(th-sub))of the given LED.From the results,the B-Al N thin film(prepared at process 4)interfaced LED showed low R_(th-tot)and T_jvalue for all driving currents and observed high difference in R_(th-tot)(DR_(th-tot)=2.2 K/W)at 700 m A when compared with the R_(th-tot)of LED attached on bare Al substrates(LED/Al).The T_jof LED was reduced considerably and observed 4.7°C as DT_jfor the film prepared using process 4 condition when compared with LED/Al boundary condition at 700 m A.The optical performance of LED was also tested for all boundary conditions and showed improved lux values for the given LED at 700 m A where B-Al N thin film was synthesized using optimized flow of Al,B and N sources with minimized B and N content.The other optical parameters such as color correlated temperature and color rendering index were also measured and observed low difference for all boundary conditions.The observed results are suggested to use B-Al N thin film as efficient solid thin film thermal interface materials in high power LED.     

靶基距对Cu/Si(100)薄膜结构和残余应力的影响

采用高功率调制脉冲磁控溅射(MPPMS)技术在 Si(100)基体上沉积 Cu 薄膜,SEM 观察薄膜厚度及生长特征、XRD 分析薄膜晶体结构、nanoindentor 测量薄膜纳米硬度和弹性模量、Stoney 公式计算薄膜残余应力,研究沉积过程靶基距对 Cu / Si(100)薄膜沉积速率、微结构及残余应力的影响。 随着靶基距的增大,薄膜沉积速率降低,薄膜的生长结构由致密 T 区向 I 区转变,Cu(111)择优生长的晶粒逐渐减小,薄膜纳米硬度和弹性模量也相应降低,残余拉应力约为 400 MPa。 较小靶基距时增加的沉积离子通量和能量,决定了薄膜晶粒合并长大体积收缩过程的主要生长形式,导致了 Cu / Si(100)薄膜具有的残余拉应力状态。 MPPMS 工艺的高沉积通量和粒子能量可实现对 Cu / Si(100)薄膜残余应力的调控。     

Induced effects of Cu underlayer on（111） orientation of Fe50 Mn50 thin films

Effects of Cu underlayer on the structure of Fe50 Mn50 films were studied. Samples with a structure of Fe50 Mn50 (200 nm)/Cu(tcu) were prepared by rnagnetron sputtering on thermally oxidized silicon substrates at room temperature. The thickness of Cu underlayer varied from 0 to 60 nm in the intervals of 10 nm. High-vacuum annealing treatments, at different temperatures of 200, 300 and 400℃ for 1 h, respectively, on the Fe50Mn50 (200 nm)/Cu(20 nm) thin films were performed. The surface morphologies and textures of the samples were measured by field emission scan electronic microscope (FE-SEM) and X-ray diffraction(XRD). Energy dispersive X-ray spectroscopy (EDX) and Auger electron spectroscopy(AES) were used to analyze the compositional distribution. It is found that Cu underlayer has an obvious induce effect on (111) orientation of Fe50 Mn50 thin films. The induce effects of Cu on (111) orientation of Fe50 Mn50 changed with the increase of Cu layer thickness and the best effect was obtained at the Cu layer thickness of 20 nm. High-vacuum annealing treatments cause the migration of Mn atoms towards surface of the film and interface between Cu layer and substrate. With the increasing annealing temperature, migration of Mn atoms is more obvious, which leads to a Fe-riched Fe-Mn alloy film.     

Sputter deposition of thin films on different substrate materials analyzed by means of modulated IR radiometry

Modulated IR radiometry, which is usually applied to sputter-deposited thin films and coatings, to determine the thermal transport properties of the thin films, is applied in this work to analyze the effects of different substrate materials and the effects of the interface coating-substrate on the resulting multi-layer system. For this purpose, a small number of ZrN films of different thickness were deposited on different substrate materials (stainless steel, Si, and glass) and were analyzed with the help of modulated IR radiometry, using heating modulation frequencies in the range from 1 Hz to 100 kHz, allowing depth-resolved thermal measurement from the sub-micron range to the millimeter range. The effects of pre-treatment of the substrates and of the interface between thin films and substrate were also analyzed. Compositional and structural properties of the thin films were obtained by RBS, XRD, and SEM.Preliminary results on the effects of substrates of limited thickness and three-dimensional heat transport, at the transition from coatings of good thermal transport properties to substrates of low thermal transport properties, are reported. A biasing effect related to the deposition process was also identified.     

Thermal performance of sputtered Cu films containing insoluble Zr and Cr for advanced barrierless Cu metallization

Pure Cu films and Cu alloy films containing insoluble substances(Zr and Cr)were deposited on Si(100)substrates,in the presence of interfacial native suboxide(SiOx),by magnetron sputtering.Samples were vacuum annealed between 300℃and 500 ℃to investigate effects of Zr and Cr additions on the thermal performance of Cu films.After annealing,copper silicides were found in the Cu(Zr)films,while no detectable silicides were observed in Cu and Cu(Cr)films.Upon annealing,Zr accelerated the diffusion and reaction between the film and the substrate,and lowered the thermal stability of Cu(Zr)alloy films on Si substrates,which was ascribed to the‘purifying effect’of Zr on the Si substrates.Whereas,Cr prohibited the agglomeration of Cu films at 500℃and decreased the surface roughness.As a result,the diffusion of Cu in Si substrates for Cu(Cr)films was effectively inhibited.In contrast to the high resistivity of Cu(Zr)films,the final resistivity of about 2.76μΩ·cm was achieved for the Cu(Cr)film.These results indicate that Cu(Cr)films have higher thermal stability than Cu(Zr)films on Si substrates and are preferable in the advanced barrierless Cu metallization.     

Dislocation accumulation and strengthening in Cu thin films

An analysis that addresses the strain-hardening behavior of thin metallic films on substrates is presented. Stress measurements were made on 0.5 μm thick Cu films on Si substrates during thermal cycling, during stress relaxation at room temperature (RT), and after quenching in liquid nitrogen. Significant strengthening was observed in the thermal cycle during cooling. The stress relaxation at RT shows a decrease of the stress from 360 MPa to 290 MPa within 15 months. A theoretical approach to the strengthening phenomenon is made on the basis of the Peach–Koehler dislocation-interaction forces. It shows that adding threading dislocations into a parallel array of dislocations at the film–substrate interface can contribute significantly to the strain hardening of thin films. The calculated strain hardening accounts for a large portion of the observed strengthening.     

Enhanced adhesion of Cu-W thin films by ion beam assisting bombardment implanting

Cu-W thin film with high W content was deposited by dual-target DC-magnetron co-sputtering technology. Effects of the substrates surface treating technique on the adhesive strength of Cu-W thin films were studied. It is found that the technique of ion beam assisting bombardment implanting of W particles can remarkably improve the adhesive property of Cu-W thin films. Indentation and scratching test show that, the critical load is doubled over than the sample only sputter-cleaned by ion beam. The enhancing mechanism of ion beam assisting bombardment implanting of Cu-W thin films was analyzed. With the help of mid-energy Ar^＋ ion beam, W atoms can diffuse into the Fe-substrate surface layer; Fe atoms in the substrate surface layer and W atoms interlace with one another; and microcosmic mechanical meshing and diffusing combination on atom-scale among the Fe and W atoms through the film/substrate interface can be formed. The wettability and thermal expansion properties of the W atoms diffusion zone containing plentiful W atoms are close to those of pure W or W-based Cu-W film.