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介孔TiO2以其独特的结构和优异的性能备受关注,但却存在起始钛源成本高、脱模不理想并易引起孔结构破坏坍塌、骨架晶型差等问题。笔者以钛铁矿酸解得到的工业TiOSO4液作为起始钛源,在复合表面活性剂自组装形成的超分子结构模板诱导作用下进行水解,控制水解产物的结构,形成介孔TiO2前驱体之后,采用氧化、萃取和焙烧相结合的方式脱除前驱体中的表面活性剂模板,制备出比表面积大、结构稳定的锐钛矿型介孔TiO2。重点研究了以下几个与介孔TiO2合成工艺及形成机理有关的问题:(1)合成介孔TiO2前驱体的工艺条件对介孔结构的形成及晶型至关重要,尤其是表面活性剂、反应pH值、温度等。采用复合模板(CTAB/P123)为结构导向剂,由工业TiOSO4液水解合成介孔前驱体,多步焙烧脱除模板,得到孔径分布窄、结构稳定的锐钛型介孔TiO2分子筛,平均孔径为3.0nm,SBET为132.6m2/g。(2)介孔TiO2前驱体合成中引入外场作用能促进产物的晶体结构完善和孔结构形成,使产物的SBET和稳定性均显著提高。超声辐照和微波辐照利于提高介孔结构的有序度;微波辐照所得产物的SBET达146.6m2/g;水热合成强化了无机物种与表面活性剂的相互作用,同时使孔壁缩聚晶化,提高了介孔结构的稳定性。(3)采用臭氧氧化、多次萃取、多步焙烧的综合脱模路线脱除有机复合模板剂CTAB/P123较完全,得到SBET高(133m2/g),平均孔径大(4.65nm)的锐钛矿型介孔TiO2。臭氧氧化使模板剂氧化成短链、小分子有机物,可减小后续脱模过程的阻力;盐酸/无水乙醇的多次萃取使孔道中模板剂的表面活性降低,与骨架结构的作用减弱,有效降低了后期热处理强度;多步焙烧方式可减小因长时间高温焙烧容易造成的无机骨架网络收缩、骨架结构损坏、骨架电荷平衡破坏所致的分子筛孔结构破坏坍塌的负效应。(4)介孔TiO2的锐钛矿晶型,较大的SBET和小的颗粒尺寸,表面吸附和键合的少量SO4使其具有良好的催化活性。介孔TiO2在光氧化分解亚甲基蓝和乙酸乙醇酯化反应中有较高的催化活性,降解率和酯化率分别达98.4%和91%;介孔TiO2对催化高酸值麻疯油与甲醇预酯化反应也表现出一定催化活性。(5)在强酸性水体系中通过CTAB/P123复合模板的超分子诱导自组装合成路线制备出2D六方孔道、SBET大(205.7m2/g)、孔径分布窄的锐钛型介孔TiO2。介孔TiO2前驱体的形成过程属协同作用机理,其特征归纳为如下几点:1)反应体系pH值对钛水解初级粒子与模板剂协同作用影响较大,二者通过静电作用(S+I–)和氢键作用(N0I0)两种方式在界面协同作用;2)调控pH值不仅使钛离子水解缩聚的速率与表面活性剂自组装速率相匹配,且能控制杂质的析出;3)适当提高合成温度有利于大孔径介孔材料的形成;4)增长复合表面活性剂疏水链有助于大孔径介孔材料的合成;5)无机强电解质阴、阳离子的加入有一定的扩孔作用;6)介孔TiO2前驱体合成体系中钛水比和酸钛比对无机钛离子水解速率(H)或抑制速率(p)影响较大,TiOSO4液合成体系大的H/p比值导致钛离子水解加速,胶束尺寸变小,使介孔材料孔径缩小。(6)介孔TiO2脱模过程中,界面作用的变化对晶体结构和微观应变造成一定影响,同时产生原子缺位。萃取脱模对晶体结构影响远弱于焙烧处理,增大萃取脱模量可有效降低焙烧强度,提高介孔TiO2的稳定性。2– 相似文献
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Development of different copper seed layers with respect to the copper electroplating process 总被引:1,自引:0,他引:1
K. Weiss S. Riedel S. E. Schulz M. Schwerd H. Helneder H. Wendt T. Gessner 《Microelectronic Engineering》2000,50(1-4):433-440
Two types of copper seed layers deposited by MOCVD and long throw sputtering (LTS) onto a tantalum barrier layer were used for electroplating (EP) of copper in the forward pulsed mode. MOCVD and PVD copper seed layers were compared with respect to step coverage, electrical resistivity, texture and adhesion behaviour. The different properties induce different electroplating fill attributes, including grain size and adhesion behaviour. MOCVD Cu seed layers show high step coverage, but do not adhere to the Ta barrier after the Cu EP. LTS Cu reveal strong (111) texture and excellent adhesion before and after Cu EP. Therefore, a CMP process could only be performed on patterned wafers with PVD/EP copper to obtain electrical data. The fabricated Cu lines show a high yield with respect to opens and shorts and standard deviations of the line resistance across the wafer. 相似文献
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We investigated the effects of a magnetic field on the electroplated copper films for the ULSI processes. The magnetic field was induced vertical to the electrodes and varied ranging from 0 to 600 G. The electroplating process was performed with on-off square pulse current source. The variation of the magnetic field vertical to the electrodes affected the deposition rate of the electroplated copper film, step coverage and gap filling in trench. As the intensity of the magnetic field increased, the deposition rate of the copper film increased, and also the resistance of electromigration increased. However, the magnetic field did not affect resistivity and surface morphology of the electroplated Cu film. At higher intensity of the magnetic field, good step coverage was obtained. 相似文献
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Thus far, no any effective countermeasure against plating-induced poor uniformity exists in the global packaging market. In this paper, we aim to develop an effective polishing process to improve the poor uniformity existing in advanced double-layer copper pillars. After polishing, the wafer and chip uniformities of copper pillars could be reduced from the original values of 6.8-3.5% and 2.9-0.9%; after reflow, the wafer and chip uniformities of copper pillars reached 3.0% and 1.7%. Excellent uniformity in copper pillars ensures accurate joints, good reliability, high yields, and flexible layouts. 相似文献
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在PCB电镀生产过程中主要缺陷有以下几种,铜粒,凹痕﹑凹点﹑板面烧焦﹑层次电镀﹑表面氧化等;在这几种表面缺陷中铜粒的影响极为严重,且难以修理和返工。现对全板硫酸铜电镀后出现的一种有规律的板面铜颗粒的产生原因,及其反应机理分析,以便解决此类问题。 相似文献
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现有的HDI和IC基板的芯层填通孔方法是一个基于在已敷形的通孔的金属化与整平后,用环氧树脂进行机械填充,及在随后附加介质层积层之前形成一层铜涂覆层的多步流程。新的填通孔技术消除了填充,整平和封装步骤的分离,缩短了电路板制造的流程。讨论了对于一系列基板厚度和孔径的铜通孔填充性能随化学参数,工艺变量和电镀设备设计的变化进行了透析。 相似文献
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Three-dimensional (3D) integration, which employs through-silicon-vias (TSVs) to electrically interconnect multiple-stacked chips, is a promising technology for significant reduction in interconnect delay and for hetero-integration of different technologies. To fabricate void-free TSVs, this paper presents a copper electroplating technique with the assistance of ultrasonic agitation to fill blind-vias, and discusses the influence of ultrasonic agitation on copper electroplating. Blind-vias with an aspect ratio of 3:1 are used for copper electroplating with both direct current (DC) and pulse-reverse current modes, combined with either ultrasonic agitation or mechanical agitation. Experimental results show that blind-vias with small aspect ratio can be completely filled using pulse-reverse current, regardless of the agitation methods. For DC, ultrasonic agitation is superior to mechanical agitation for copper electroplating in filling void-free vias. These results indicate that agitation, though is a secondary control factor to pulse-reverse current, can enhance mass transfer in blind-vias during copper electroplating and can improve the filling capability of copper electroplating. 相似文献