臺灣博碩士論文加值系統

中 文 摘 要
在銲接過程當中，擴散阻障層扮演著一個相當重要的角色，它的功用主要是防止銲料與Cu層快速反應，除了低消耗速率的Ni以及Pt之外，NiCu合金是未來有可能用來使用的擴散阻障層之一。之前本實驗室的何政恩學長探討了錫銀銅無鉛銲料與Ni基材的液態反應，發現銲料中添加微量的Cu可大幅降低Ni基材的消耗，另外界面所生成的介金屬型態也會隨著銲料中Cu濃度不同而有所改變。

而本論文則是利用電鍍方式，在Cu層上電鍍NiCu合金作為擴散阻障層，並探討不同濃度的鍍層與Sn3Ag銲料間的反應情形。除了液態反應之外，本研究也深入探討固態反應時的反應行為，由結果發現當Cu濃度改變時，將會改變界面生成物的種類、型態以及反應過程的消耗行為。

本研究所採用的NiCu合金濃度為Ni-15 at.%Cu、Ni-40 at.%Cu、Ni-54 at.%Cu，另外也做了純Cu、純Ni作為比較組。在120 sec液態反應實驗中發現當鍍層為Ni-15 at.%Cu、Ni-40 at.%Cu時，與銲料反應後所生成的介金屬為(Ni1-xCux)3Sn4；鍍層為Ni-54 at.%Cu時，所生成的介金屬為(Ni1-xCux)3Sn4、(Cu1-xNix)6Sn5兩相共存；另外純Ni與銲料反應生成Ni3Sn4；純Cu則生成Cu6Sn5。在固態反應實驗中發現隨著熱處理溫度的增高以及時間的增長，鍍層為Ni-15 at.%Cu時界面的介金屬依然只以(Ni1-xCux)3Sn4存在；鍍層為Ni-40 at.%Cu時所生成的介金屬為(Ni1-xCux)3Sn4以及(Cu1-xNix)6Sn5兩相共存；然而鍍層為Ni-54 at.%Cu時介金屬則是以(Cu1-xNix)6Sn5為主。

在120 sec液態反應後發現，NiCu合金的消耗隨著Cu濃度的增加而增加；300 sec液態反應後，NiCu合金的消耗隨著Cu濃度的增加而增加，然而令人意外的是Ni-54 at.%Cu的消耗會比純Cu還快。而且在固態反應之後Ni-40 at.%Cu 、Ni-54 at.%Cu的消耗均會比純Cu還快。

由本研究結果發現，在電鍍液當中添加少量的硫酸銅，便會讓鍍層的Cu含量大幅提升，並使NiCu合金的消耗、界面的介金屬種類以及型態大幅的改變。

ABSTRACT
Diffusion barrier plays an important role in soldering, it can prevent fast reaction between tin and copper. Beside nickel and platinum, nickel-copper alloy is a possible diffusion barrier in the future. In the past, our labortoary investigated liquid/solid reaction between SnAgCu solder and nickel, it found that little copper added in solder can reduce consumption of nickel. Additionally, intermetallic compound at interface can also changed with copper added in solder.

In the experiment, we electroplated nickel-copper alloy on copper and investigated reaction between Sn3Ag solder and different concentration nickel-copper alloy. Beside liquid/solid reaction, we also investigated solid/solid reaction. According to the result, change of concentration in nickel-copper alloy will affect intermetallic compound phase and consumption.

Beside copper and nickel,we also electroplated Ni-15 at.%Cu,Ni-40 at.%Cu and Ni-54 at.%Cu. After 120 sec liquid/solid reaction, intermetallic compound between tin and Ni-15 at.%Cu is (Ni1-xCux)3Sn4；intermetallic compound between tin and Ni-40 at.%Cu is (Ni1-xCux)3Sn4；intermetallic compound between tin and Ni-54 at.%Cu is (Ni1-xCux)3Sn4 and (Cu1-xNix)6Sn5.After solid/solid reaction, intermetallic compound between tin and Ni-15 at.%Cu is (Ni1-xCux)3Sn4；intermetallic compound between tin and Ni-40 at.%Cu is (Ni1-xCux)3Sn4 and (Cu1-xNix)6Sn5；main intermetallic compound between tin and Ni-54 at.%Cu is (Cu1-xNix)6Sn5.

After 120 sec liquid/solid reaction, consumption of nickel-copper alloy will increase with copper concentration in alloy.Surprisingly, consumption of Ni-54 at.%Cu is faster than copper after 300 sec liquid-state reaction. After solid/solid reaction, consumption of Ni-40 at.%Cu and Ni-54 at.%Cu is even faster than copper.

In the research, we found that a little sulfur copper added in electrolyte will great affect copper concentration in nickel-copper alloy, intermetallic compound phase and consumption.

目 錄 頁數
中文摘要………………………………………………………………Ⅰ
英文摘要………………………………………………………………Ⅲ
目錄……………………………………………………………………Ⅴ
圖目錄………………………………………………………………..Ⅷ
表目錄…………………………………………………………………
第一章 緒論………………………………………………………….1
1.1電子構裝…………..…………………………………………...1
1.1.1電子構裝的功能…………………………………...........1
1.1.2電子構裝四層次…………………………………….........3
1.1.3連線技術…………………………………………….........5
1.1.4銲錫凸塊結構與製程技術………………………….........7
1.2電子構裝之趨勢……………………………………………....10
1.2.1覆晶封裝的廣泛使用……………………………..........11
1.2.2無鉛銲料取代鉛錫銲料……………………………........12
1.3擴散阻障層的重要性………………………………………....15
1.4研究目的……………………………………………………....18

第二章 文獻回顧……………………………………………………19
2.1 Sn/Ni、Sn/Cu反應文獻回顧………………………………...19
2.1.1 Sn/Cu反應文獻回顧………………………………........19
2.1.2 Sn/Ni反應文獻回顧……………………………..........21
2.2 SnAgCu solder/Ni反應文獻回顧……………………….....22
2.3 Sn/NiCu Alloy反應文獻回顧……………………………....29

第三章 實驗方法及步驟……………………………………………39
3.1 NiCu合金製備…………………………………………….....39
3.2 NiCu 合金元素組成分析…………………………………....41
3.3 NiCu 合金XRD繞射分析……………………………….......42
3.4 Sn3Ag銲料與NiCu合金液固界面反應………………........43
3.5 Sn3Ag銲料與NiCu合金固固界面反應…………………......45

第四章 NiCu合金組成分析之實驗結果與討論……………………48
4.1 NiCu合金元素組成分析………………………………….....48
4.2 NiCu合金表面型態……………………………………….....52
4.3 NiCu合金XRD繞射分析…………………………………......53

第五章Sn3Ag銲料與NiCu合金液固界面反應之實驗結果與討論..55
5.1 Sn3Ag銲料與NiCu合金液固界面反應…………………......55
5.1.1 Sn/Ni之液固界面反應……………………………........55
5.1.2 Sn/Ni-15 at.%Cu之液固界面反應………………........56
5.1.3 Sn/Ni-40 at.%Cu之液固界面反應……………..........56
5.1.4 Sn/Ni-54 at.%Cu之液固界面反應………………........57
5.1.5 Sn/Cu之液固界面反應……………………………........59
5.2 液固界面反應介金屬種類比較………………………….....60
5.3 液固界面反應墊層消耗比較…………………………….....61

第六章Sn3Ag銲料與NiCu合金固固界面反應之實驗結果與討論..62
6.1 Sn3Ag銲料與NiCu合金固固界面反應…………………......62
6.1.1 200 ℃之固固界面反應………………………….........62
6.1.2 190 ℃之固固界面反應………………………….........65
6.1.3 180 ℃之固固界面反應………………………….........67
6.1.4 160 ℃之固固界面反應………………………….........69
6.2 Sn3Ag銲料與NiCu合金反應過程示意圖………………......71
6.2.1 Sn3Ag/Ni銲料反應示意圖……………………….........71
6.2.2 Sn3Ag/Ni-15 at.%Cu銲料反應示意圖………….........71
6.2.3 Sn3Ag/Ni-40 at.%Cu銲料反應示意圖………….........72
6.2.4 Sn3Ag/Ni-54 at.%Cu銲料反應示意圖………….........72
6.2.5 Sn3Ag/Cu銲料反應示意圖……………………….........73
6.3固固界面反應介金屬種類比較……………………………....74
6.4固固界面反應墊層消耗比較………………………………....77
6.4.1.200 ℃固固界面反應墊層消耗比較…………….........77
6.4.2 190 ℃固固界面反應墊層消耗比較…………….........78
6.4.3 180 ℃固固界面反應墊層消耗比較…………….........79
6.4.4 160 ℃固固界面反應墊層消耗比較…………….........80
6.5墊層與介金屬之質量平衡關係……………………………....82
6.5.1介金屬與Ni-14.2 at.%Cu墊層之質量平衡關係…........82
6.5.2介金屬與Ni-46.5 at.%Cu墊層之質量平衡關係…........84
6.5.3介金屬與Ni-58.2 at.%Cu墊層之質量平衡關係…........87

第七章 結論…………………………………………………………89
7.1 NiCu合金組成及XRD分析………………………………......89
7.2 Sn3Ag銲料與NiCu合金之液固界面反應………………......90
7.3 Sn3Ag銲料與NiCu合金之固固界面反應………………......91

參考文獻…………………………………………………………….92

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