臺灣博碩士論文加值系統

　　電子產品要求尺寸越來越小，其優點：降低封裝的面積、更輕量化、更密集的連結密度、更高的可靠度，和在低電阻中表現更優異的電子性能。傳統印刷電路板電鍍通孔時，均擲力需達到100%。近年來雖然有人研究通孔電鍍，但電鍍結果效果不彰，吾人開發出新穎電鍍添加劑，利用陰極旋轉方式加上蝴蝶填孔技術，提高電流密度至9ASF，可縮短電鍍時間為2小時，完成填孔電鍍製程。
　　一般而言，平整劑是含四級銨 (N+) 的有機雜環化合物 (Azole Compound)，藉由電化學分析法證實於混合多種添加劑之間的協合效應，混合多種添加劑有助於提高電流密度的需求及加強抑制劑的濃度梯度；給予微弱且固定的強制對流情況下，有相輔相成的效果，同樣也營造出孔中先行銅沉積的行為。
　　在硫酸系統下，透過線性掃描伏安法和計時電位分析法，銅電極在不同轉速下的方法被利用來研究此添加劑的特徵。電化學分析結果可顯示添加劑在電極表面位置上的電化學吸附能力。根據電化學分析之結果發現，此添加劑抑制銅沉積之行為與其濃度成正比，濃度越高，其脫附電位愈負，表現出多層吸附或是電化學聚合的行為。
　　最後吾人利用開發的新穎配方直接填通孔電鍍。孔徑為50um，深度為380um，深寬比高達7.6，電鍍時間只需要9小時便可完全填充。

The size of electronic products is requested to be smaller and smaller. They provide several advantages such as reduced packaging area, light weight, higher interconnection density, high reliability, and excellent electrical performance with lower resistance. For traditional electroplating through hole, the throwing power of 100% have to achieve then it can meet the requirement. In recent years, many people studied the through hole electroplating. However, they need a conducting layer to be assembled at the bottom to improve the process. We consider to develop a new formula for filling through-hole by copper electroplating, and we use butterfly technology (BFT) to fill up the through hole. It can be processed at high current density, and reduce electroplating time to filling up.
In general, levelers bares tetrazolium compound, electrochemical analysis can characterize the additives’ interaction in between. High current density could be applied and when multi-component formula was employed. In addition, multi-component formula can enhance the concentration gradient in the through hole. The filling performance of the multi-component formula could be enhanced with which weak and fixed forced convection combined. It could result in center-up filling mode.
In sulfuric acid system, linear sweep voltammetry (LSV) and chronopotentiometry (CP) were employed to characterize these additives on copper electrode at different rotating speeds. The electrochemical analyses reveal the adsorptive ability of these additives on copper electrode. According to the electrochemical analyses, the inhibiting effect of the additive on copper deposition depends on the its concentration, that is, the higher the additive concentration, the more negative the desorption potential. This suggests that the adsorption of the additive may be multilayer or it may perform electrochemical polymerization on copper electrode.
Finally, the through hole was fully filled by copper electroplating using the as-developed new formula. The hole diameter was 50 μm, the hole depth was 380 μm and the aspect ratio was 7.6. The total plating time just took 9 hours.

摘要................................................ⅰ
Abstract............................................ⅱ
目錄................................................ⅲ
圖目錄..............................................ⅵ
表目錄..............................................xiii
第1章、 緒論.........................................1
第1-1節 前言.........................................1
第1-2節 研究動機與目的...............................3
第2章、 文獻回顧與電化學理論.........................5
第2-1節 銅製程技術...................................5
2-1.1 大馬士革雙鑲嵌技術 (Dual-damscene).............5
2-1.2 增層製程技術 (Build-up Process)................7
第2-2節 電鍍方式.....................................10
2-2.1 直流電電鍍.....................................10
2-2.2 脈衝式及反脈衝式電鍍...........................10
第2-3節 基礎電化學原理...............................12
2-3.1 電化學方法.....................................12
2-3.2 極化 (Polarization) 與過電壓 (Overpotential)...12
2-3.3 電子轉移與質傳控制.............................13
第2-4節 電鍍添加劑簡介...............................15
2-4.1 無機添加劑.....................................15
2-4.2 有機添加劑.....................................19
第2-5節 對流敏感性吸附理論...........................27
2-5.1 有電鍍添加劑...................................27
2-5.2 無電鍍添加劑...................................30
第2-6節 矽通孔(Through Silicon Via, TSV).............32
2-6.1 3D晶片堆疊發展.................................32
2-6.2 3D晶片填孔技術.................................34
第2-7節 不同平整劑藉由UV-vis 的量測..................38
第3章、 實驗藥品與實驗裝置、步驟.....................42
第3-1節 實驗藥品.....................................42
第3-2節 實驗裝置.....................................43
恆電位／電流儀.......................................45
金相顯微鏡...........................................46
紫外光- 可見光光譜儀 (Ultraviolet/ Visible, UV- vis).48
第3-3節 實驗步驟.....................................50
3-3.1 哈林試驗電鍍槽實驗.............................50
3-3.2 電化學分析實驗.................................51
第4章、 實驗結果與討論...............................53
第4-1節 基本電鍍液濃度...............................53
第4-2節 電鍍添加劑之電化學分析.......................54
4-2.1 循環伏安法.....................................54
4-2.2 計時電位法.....................................60
第4-3節 印刷電路板電鍍實驗...........................64
4-3.1 傳統電鍍添加劑對於電鍍銅沉積的影響.............65
4-3.2 對流對於電鍍添加劑吸附的影響...................68
第4-4節 矽晶圓電鍍實驗...............................75
4-4.1 不含電鍍添加劑 (只含氯離子)....................75
4-4.2 含電鍍添加劑...................................77
4-4.3 電化學分析.....................................87
第4-5節 新穎填充通孔電鍍配方之銅沉積模式.............91
第5章、 結論.........................................98
第6章、 未來發展方向.................................99
第7章、 參考文獻....................................100

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