Acceleration and inhibition effects on via filling electrodeposition were discussed

讨论了通孔填充电沉积的加速和抑制作用

• 批准号: 13650781
• 负责人: KONDO Kazuo
• 金额: $ 2.11万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650781/
• 关键词: COPPER CONCUCTOR; COPPER ELECTRODEPOSITION; ADDITIVES; INHIBITION EFFECT; ACCELERATION EFFECT; MECHANISM

Acceleration and inhibition effects on via filling electrodeposition were discussed.1.Acceleration effect(1) Through mask electrode of electrode only at via bottom was used to measure the via bottom acceleration effects. The via bottom current increases with additives of Chloride(Cl^-), Polyethylen Glycol (PEG), Janus green B(JGB) and Bis(3-sulfopropyl) disulfide(SPS) if compared with Cl^-, PEG and JGB. With increasing via aspect ratio, the via bottom current also increases.(2) The via bottom current also increases with narrower via opening size. The cross section of electrodeposits deposited on via bottom electrode was observed. These elctrodeposits are always flat and does not show the curvature even with the narrower via opening size which shows the acceleration effects. This contradicts with the adsorption model proposed by T.Moffat et. Al..(3) This indicates that the free accelerator, not the adsorbed, shows the via bottom acceleration effect.2.Inhibition effect(1) Inhibition addi … More tives of PEG molecules was discussed next. The granular deposit shows higher FEAUGER peak intensity if compared with other flat areas. The PEG molecule is polymer containing oxygen and the granular deposits observed with the secondary electron image are the PEG molecules.(2) The QCM substrates which has been pre deposited with copper was dipped into the PEG and Cl^- containing copper electrolytes. The differential frequency increases with the increase in the dipping time. With 200 second dipping time, numerous fine 10nm in diameter PEG molecules can be observed.(3) The current shows constant and lower value of 4.3mA/cm^2 with the PEG and Cl^- containing copper electrolytes regardless of electrodepositiontime. With adding 1ppm of SPS, however, the current increased drastically. SPS has the acceleration effect of increasing current. Before adding 1ppm of SPS, the copper electrodeposit surface has numerous PEG molecules. However, no PEG molecules could be observed on the copper electrodeposit surface of 3000second and 5400sedond. The copper electrodeposits also show refinement of granular size to 100nm. The SPS additive has the PEG molecules removing and copper electrodeposit refinement effects.*Three dimensional packaging technology is to stack the silicon chips in three dimensions. Through chip electrodes form on the silicon chips and these high aspect ratio vias are filled by copper electrodeposition. As an application of the research, we developed complete electrodeposition of these high aspect ratio vias. We achieved extremely short electrodeposition time of 2.5hrs. Less

1.加速效应（1）采用只在通孔底部电极的掩模电极来测量通孔底部加速效应。与Cl^-、PEG和JGB相比，Cl^-、PEG、JGB和SPS的加入使过孔底部电流增大。随着通孔深宽比的增加，通孔底部电流也增加。(2)过孔底部电流也随着过孔开口尺寸的减小而增大。观察了沉积在通孔底电极上的沉积物的横截面。这些电沉积物总是平坦的，并且不显示曲率，即使具有显示加速效应的较窄通孔开口尺寸。这与T.Moffat等人提出的吸附模型相矛盾。Al.. (3)这表明，自由的促进剂，而不是吸附的促进剂，显示了通过底部加速效应。 ...更多信息 接下来讨论了PEG分子的性质。如果与其它平坦区域相比，颗粒状存款显示出更高的FEAUGER峰强度。PEG分子是含氧聚合物，用二次电子图像观察到的颗粒状沉积物是PEG分子。(2)将已经用铜预沉积的QCM基底浸入含PEG和Cl 2的铜电解质中。微分频率随着浸渍时间的增加而增加。在200秒的浸渍时间下，可以观察到许多直径为10 nm的细小PEG分子。(3)在含PEG和Cl ~-的铜电解液中，电流显示恒定且较低的值，为4.3mA/cm ~ 2，与电沉积时间无关。然而，随着添加1 ppm的SPS，电流急剧增加。SPS具有增加电流的加速作用。在添加1 ppm SPS之前，铜电沉积物表面具有大量PEG分子。而在3000秒和5400秒的铜电沉积表面上没有观察到PEG分子。铜镀层的晶粒细化到100 nm。SPS添加剂具有去除PEG分子和细化铜镀层的作用。三维封装技术是将硅片进行三维堆叠。通过芯片电极形成在硅芯片上，并且这些高深宽比通孔通过铜电沉积来填充。作为研究的应用，我们开发了这些高深宽比通孔的完全电沉积。我们实现了2.5小时的极短电沉积时间。少

项目成果

K.Kondo, N.Yamakawa, Z.Tanaka and K.Hayashi: "Copper Damascene Electrodeposition and Additives"Journal of Analytical Electrochemistry. [In Print].

K.Kondo、N.Yamakawa、Z.Tanaka 和 K.Hayashi：“铜镶嵌电沉积和添加剂”分析电化学杂志。

K.Kondo, T.Okamura, S-J Oh, T.Yonezawa, M.Tomisaka, H.Yonemura, M.Hoshino, Y.Taguchi, K.Takahashi: "Via filling electrodeposition used for the high aspect ratio through electrode of three dimensional packaging"JIEP. [In Print].

K.Kondo、T.Okamura、S-J Oh、T.Yonezawa、M.Tomisaka、H.Yonemura、M.Hoshino、Y.Taguchi、K.Takahashi：“用于三维高深宽比贯通电极的通孔填充电沉积

KazuoKondo, Lili Deligianni, Electronics Division: "Future Targets of Electrodeposition Technologies"Ch.E.Japan. 10 (2002)

KazuoKondo、Lili Deligianni，电子部门：“电镀技术的未来目标”Ch.E.Japan。

近藤和夫: "実装プロセス工学の最新研究分野"ケミカルエンジニアリング. 146. 64-70 (2001)

近藤一夫：《包装工艺工程的最新研究领域》《化学工程》146. 64-70 (2001)。

岡村拓治, 田中善之助, 近藤和夫: "穴埋めっきにおける開口寸法の影響"第11回マイクロエレクトロニクスシンポジウム、阪大. 10月. 95-100 (2001)

Takuji Okamura、Zennosuke Tanaka、Kazuo Kondo：“孔径尺寸对孔填充的影响”第 11 届微电子研讨会，大阪大学 95-100（2001 年）。