臺灣博碩士論文加值系統

半導體封裝過程中，銅導線架上廣泛地利用電鍍錫作為表面處理層，因為在導線架腳表面電鍍錫可以增加架腳的潤濕性及避免氧化，有助於架腳與印刷電鍍板(printed circuit board, PCB)的接合，但錫層表面會自發性成長錫鬚，導線架腳會因錫鬚成長相連接造成短路，降低電子產品的可靠度。然而在覆晶產品製作過程或使用期間，由於材料本身性質與外在環境的影響，會造成應力(stress)之產生。矽晶片與薄膜間由於熱膨脹係數(coefficient of thermal expansion, CTE)差異較大，容易造成銲點熱應力之生成，而應力之生成可能會影響覆晶及表面處理層在許多可靠度之表現。本研究設計黃銅模具，模擬矽晶片基材與鍍膜間熱膨脹係數差異所造成的應力對於錫鬚生長及錫/銅界面反應之影響。本研究主要在銅/錫薄膜上加入應力及溫度之因素，進而探討對錫鬚生長及錫/銅界面反應之影響。
實驗結果發現有無應力影響會導致錫鬚生長數量、速度及生長方向的差異。在室溫受外加拉伸應力影響下，不受應力及受拉伸應力較大區域的錫鬚生長為隨機方向生長，由錫膜表面朝上且沒有特定生長方向。受拉伸應力較小區域的錫鬚有特定生長方向，剛從錫膜表面冒出錫芽後就近乎平行於錫膜表面朝著特定方向生長。受拉伸應力的錫鬚生長速度較無應力慢且數量較少、平均長度較短，推測外加拉伸應力可將電鍍錫產生的壓縮應力加以釋放，緩和錫鬚成長，其中錫膜所受到外加拉伸應力越大效果越顯著，所以導線架腳的設計可以考量施以外加拉伸應力藉以緩和錫鬚生長。
於高溫熱處理研究中，將樣品置於80℃與150℃下進行熱處理30天∼80天，溫度對於錫鬚成長也有很大的影響，在高溫80 ℃及150 ℃錫鬚的型態由細絲狀(whisker)轉變為小丘狀(hillock)。但在高溫熱處理下外加拉伸應力對於小丘狀錫鬚的成長影響不如室溫下細絲狀錫鬚那麼顯著。
熱處理可以抑制細絲狀錫鬚生長，型態轉變為小丘狀錫鬚，而小丘狀錫鬚大小約為直徑5μm的凸塊，不像細絲狀錫鬚可以持續成長達數十或數百微米，可以利用熱處理程序避免導線架上鍍錫造成細絲狀錫鬚生長而造成精密電子產品短路。
錫/銅界面反應中，(45μm Sn/10μm Cu)在高溫熱處理下150℃、170℃、200℃下介金屬化合物(intermetallic compound, IMC)隨著時間增長而增厚，先生成Cu6Sn5再生成Cu3Sn。受拉伸應力及壓縮應力在相同時間下IMC生長速率均較不受應力快速，所以整體的IMC(Cu6Sn5+Cu3Sn)也較厚。IMC生長速率為受壓縮應力最快，受拉伸應力其次，不受應力生長速率最慢，所以受到外加壓縮及拉伸應力均會促進IMC生長。

In this study, for simplicity, externally applied tensile stress was exerted on a Sn thin film electrodeposited on a Cu substrate using three-point bending to simulate the condition of a Sn thin film subjecting to a tensile stress due to CTE (coefficient of thermal expansion) effect. To perform the bending experiments, a specifically designed three-point bending module made of brass was used to bend the samples.
Filamentary Sn whiskers were formed on an electrodeposited Sn thin film aged at room temperature. Sn whisker growth was significantly mitigated on the Sn thin film subjected to a tensile stress in bending. This mitigation growth suggests that part of the compressive stress in the Sn thin film was neutralized by the mechanically applied tensile stress. The growth orientation of Sn whiskers formed on the high tensile stress region was random but directional on the low tensile stress region. A potential mechanism was proposed to explain the directional growth of Sn whiskers. The vacancy concentration at the high tensile stress region is higher than that at the low tensile stress region. Driven by the vacancy concentration gradient, the Sn atoms migrate from the low tensile stress region to the high tensile stress region, making the Sn whiskers grow in a preferential orientation.
No Sn whisker growth took place as the aging temperature was raised to 80 and 150℃, while Sn hillocks grew instead. More surprisingly, no noticeable Sn hillock(or whisker) growth was observed on the tensily-bent Sn film aged at 80 and 150℃, indicating that the combined effects of tensile stress and aging can effectively inhibit the Sn hillock(or whisker) growth.
Effects of applied stresses on the copper/tin thin film interfacial reaction were investigated. A three-point bending was used and in-plane bending induced compressive and tensile stresses. The sample was solid-state aged at temperatures of 150℃, 170℃ and 200℃ for 2days to 17days. The results revealed that mechanically applied stress can influence the IMC (intermetallic compound) growth behavior. Both compressive and tensile stresses can accelerate the IMC growth, and the IMC thickness under compressive stress is the thickest.

目次

誌謝-------------------------------------------------------- Ι
摘要-------------------------------------------------------- ΙΙ英文摘要---------------------------------------------------- ΙII
目次-------------------------------------------------------- ΙV
表目次------------------------------------------------------ VI
圖目次----------------------------------------------------- VII
一、 前言--------------------------------------------------- 1
二、 文獻回顧----------------------------------------------- 2
2.1錫鬚
（一） 錫鬚簡介------------------------------------------ 4
（二） 錫鬚生長機制-------------------------------------- 5
（三） 外加因素促進錫鬚成長------------------------------ 19
2.2界面反應
（一） 覆晶封裝製程-------------------------------------- 24
（二） 熱應力-------------------------------------------- 26
（三） 相變化引發的應力---------------------------------- 31
（四） 外加應力----------------------------------------- 34
（五） 界面反應------------------------------------------ 38
三、 實驗方法----------------------------------------------- 52
3.1錫鬚
（一） 樣品的製備---------------------------------------- 52
（二） 測量殘餘應力-------------------------------------- 57
（三） 錫鬚生長機制-------------------------------------- 57
（四） 錫鬚的生長---------------------------------------- 57
（五） 電子顯微鏡樣品的製備及分析------------------------ 57
（六） XRD繞射分析------------------------------------- 58
3.2界面反應
（一） 熱處理（固／固界面反應）------------------------------ 58
（二） 電子顯微鏡樣品的製備及分析------------------------ 58

四、 實驗結果與討論----------------------------------------- 64
4.1外加應力對錫鬚成長之影響
（一）溫度及外加應力對錫鬚成長之影響--------------------- 64
1. 電鍍錫膜初始之表面結構---------------------------- 64
2. 錫鬚生長機制-------------------------------------- 66
3. 不受應力------------------------------------------ 71
4. 受拉伸應力區域1----------------------------------- 74
5. 受拉伸應力區域2----------------------------------- 77
6. 錫鬚受溫度及外加應力的影響之討論------------------ 80
（二）錫鬚成長之方向性---------------------------------- 85
1. 不受應力------------------------------------------ 85
2. 受拉伸應力區域1----------------------------------- 86
3. 受拉伸應力區域2----------------------------------- 87
4. 錫鬚生長方向之討論-------------------------------- 89
4.2外加應力對界面反應之影響
（一）3μmSn/3μmCu界面反應------------------------------ 92
1. 80℃固/固界面反應---------------------------------- 92
2. 150℃固/固界面反應--------------------------------- 94
3. 170℃固/固界面反應--------------------------------- 96
（二）45μmSn/10μmCu界面反應----------------------------100
1. 150℃固/固界面反應---------------------------------100
2. 170℃固/固界面反應---------------------------------102
3. 200℃固/固界面反應---------------------------------104
（三）外加應力對Sn/Cu界面反應影響之機制-----------------108
五、 結論---------------------------------------------------110
六、 參考文獻-----------------------------------------------112






表目次
表3.1錫電鍍液組成------------------------------------------- 54
表3.2電鍍錫溶液操作條件------------------------------------- 54
表3.3銅電鍍液組成------------------------------------------- 54
表3.4電鍍銅溶液操作條件------------------------------------- 54
表3.5下層模具之尺寸----------------------------------------- 55
表3.6上層模具之尺寸----------------------------------------- 55表3.7曲率半徑與外加應力值----------------------------------- 55
表4.1薄膜厚度與殘餘應力值----------------------------------- 65
表4.2受拉伸應力與不受應力不同時間下錫鬚之平均長度、最大長度、平均密度及平均生長速------------------------------------- 81
表4.3 80℃不同時間下受應力及不受應力IMC成長厚度------------ 92
表4.4 150℃不同時間下受應力及不受應力IMC成長厚度----------- 94
表4.5 170℃不同時間下受應力及不受應力IMC成長厚度----------- 96










圖目次
圖1.1：銅導線架腳表面電鍍錫(a)簡圖(b)SEM-----------------------2
圖1.2：錫鬚生長至足夠長度與鄰近導線接觸造成短路----------------3
圖1.3：覆晶接合------------------------------------------------3
圖2.1：各種不同型態的錫鬚--------------------------------------4
圖2.2：室溫下Cu-Sn反應生成Cu6Sn5及錫鬚------------------------5
圖2.3：錫膜表面沒有氧化層沒有錫鬚生長-------------------------5
圖2.4：錫鬚由氧化層最薄的點擠出釋放錫膜內部應力--------------- 6
圖2.5：錫鬚形狀(a,b)直線狀、(c,d)彎曲扭結狀---------------------- 6
圖2.6：FIB截面圖(a) Sn-Cu、(b) Sn ------------------------------7
圖2.7：錫鬚成長由錫膜內部擠出---------------------------------8
圖2.8：錫鬚俯視圖(a) Sn-Cu膜、(b) Sn膜---------------------------9
圖2.9：銅原子擴散產生壓縮應力造成錫鬚生長示意圖---------------9
圖2.10：錫鬚俯視圖(a)有氧化層、(b)沒有氧化層-------------------10
圖2.11：FeNi42導線架經過TC 600 cycle(a)Sn、(b)Sn-Cu、(c)Sn-Bi ---11
圖2.12：Cu導線架經過(50°C/ambient humidity)六個月(a)Sn、(b)Sn-Cu、(c)Sn-Bi----------------------------------------------12
圖2.13：Sn(Cu)表面錫鬚SEM俯視圖(a)Sn、(b)Sn0.7Cu、(c)Sn1.8Cu、
(d)Sn3.0Cu--------------------------------------------15
圖2.14：Sn(Cu)處理層和Ni反應之SEM截面圖(a)Sn、(b)Sn0.7Cu、
(c)Sn1.8Cu、(d)Sn3.0Cu---------------------------------15
圖2.15：FIB截面圖3000 h THT(a) as-fabricated、(b) annealed、(c) reflowed -----------------------------------------------------16
圖2.16：OM截面圖(a)as-fabricated、(b) annealed-------------------17
圖2.17：OM截面圖reflowed樣品(a)厚的等軸層狀、(a)薄的圓柱狀---17
圖2.18：FIB截面圖(a)Sn、(b)Sn-Cu------------------------------18
圖2.19：室溫熱處理截面圖(a) as reflow、(b) 3天、(c) 7天、(d) 14天
----------------------------------------------------19
圖2.20：150℃熱處理截面圖 (a) as reflow、(b) 15分鐘、(c) 30分鐘、(d)45分鐘-------------------------------------------------20
圖2.21：室溫下針狀錫鬚(a)48小時、(b)240小時-------------------21
圖2.22：150℃下小丘狀錫鬚(a)10分鐘、(b)90分鐘-----------------21
圖2.23：錫膜表面俯視(a) ZrO2球壓痕、(b)為圖(a)箭頭位置放大圖---22
圖2.24：(a)FIB截面圖((變形/未變形)區域)、(b)為圖(a)示意簡圖------23
圖2.25：受機械變形後微結構發展機制圖-------------------------23
圖2.26：毛細現象填膠-----------------------------------------24
圖2.27：填膠示意圖-------------------------------------------24
圖2.28：覆晶受溫度變化所產生的變形---------------------------25
圖2.29：樣品之示意圖-----------------------------------------28
圖2.30：(a)試樣未加熱之橫截面圖、(b)試樣加熱後之橫截面圖、(c)試樣
加熱後冷卻至室溫之橫截面圖---------------------------28
圖2.31：(a)電子顯微鏡觀察樣品之厚度、(b)曲率半徑之示意---------28
圖2.32：(a)矽晶片背面生成二氧化矽之後沉積鈦或鎳示意圖、( b)矽晶片
背面生成氮化矽或矽化鈷之後沉積鈦或鎳示意-------------30
圖2.33：矽化物與晶片背面生成物之關係-------------------------31
圖2.34：應力與熱處理時間關係圖-------------------------------33
圖2.35：(a)循環熱處理Ni(11.7P)、(b)循環熱處理Ni( P) -------------34
圖2.36：(a)樣品的示意圖、(b)橫截面示意圖-----------------------35
圖2.37：(a)拉伸情況下、(b)沒有彎曲下、(c)壓縮情況下-------------36
圖2.38：C-ring模具圖-----------------------------------------36
圖2.39：σs=10MPa,125℃,4000h IMC微結構(a)Tension、(b)Compression- -----------------------------------------------------37
圖2.40：σs=5MPa,125℃,4000h IMC微結構(a)Tension、(b)Compression-- -----------------------------------------------------37
圖2.41：壓縮應力促使Cu及Ni擴散進入銲料-------------------- 37
圖2.42：錫/銅二元平衡等溫相圖-------------------------------- 39
圖2.43：錫鉛銲料與銅之界面反應(a)兩次回焊、(b)圖a放大、(c)熱處理 170℃500小時、(d)熱處理170℃1000小時----------------40
圖2.44 :不同銲料與銅基材作界面反應(a)共晶錫鉛、(b)Sn-3.5Ag、(c)Sn-3.8Ag-0.7Cu、(d) Sn-0.7Cu ----------------------------41
圖2.45：固態熱處理之銅擴散之路徑圖---------------------------42
圖2.46：不同銲料與銅基材作反應之俯視圖(a)純錫、(b)共晶錫鉛銲料-42
圖2.47：反應偶樣品示意圖-------------------------------------43
圖2.48：200°C Sn-Cu-Ni 三元相圖-------------------------------43
圖2.49：熱處理250℃(a) Sn-3.5Ag-0.7Cu、(b)Sn-3.5Ag-0.5Cu-0.07Ni-0.01Ge
------------------------------------------------------44
圖2.50：(a)Sn-0.7wt%與Al/Ni之反應於250℃,30秒、(b)Sn-3wt%與Al/ Cu之反應於250℃,30秒--------------------------------44
圖2.51：銅基材與錫膜之界面反應(a)回焊8分鐘的top view、(b)回焊4
分鐘的橫截面-----------------------------------------45
圖2.52：(a)錫銀-鎳/銅於250℃,60秒、(b)錫銀-鈷/銅於250℃,60秒---45圖2.53：熱處理150℃ Cu6Sn5微結構(a)0.5hr、(b)1hr、(c)2hr、(d)26hr------------------------------------------------------47
圖2.54：Cu6Sn5在錫晶界中成長機制圖---------------------------48
圖2.55：Ni/(100μm Sn)/Cu熱處理160℃, 30 min(a)Ni側界面、(b)Cu側界面---------------------------------------------------49
圖2.56：Ni/(100μm Sn)/Cu熱處理160℃,1000 hr(a)Ni側界面、(b)Cu側界面---------------------------------------------------50
圖2.57：熱處理160℃ 1000hr (a)Ni/Sn界面、(b)Sn/Cu界面-----------51
圖2.58：Ni/(400μm Sn)/Cu熱處理160℃,1000 hr(a)Ni側界面、(b)Cu側界面---------------------------------------------------51
圖3.1：電鍍樣品之示意圖--------------------------------------53
圖3.2：電鍍設備示意圖----------------------------------------53
圖3.3：模具之示意圖(a)下層模具、(b)上層模具、(c)樣品彎曲之示意圖、 (d)樣品彎曲之橫截面(受拉伸應力)、(d)樣品彎曲之橫截面(受壓縮應力)-----------------------------------------------56
圖3.4：高溫爐示意圖------------------------------------------59
圖3.5：模具升溫曲線圖----------------------------------------59
圖3.6：實驗流程圖(1)------------------------------------------60
圖3.7：實驗流程圖(2)------------------------------------------61
圖3.8：實驗流程圖(3)------------------------------------------62
圖3.9：實驗流程圖(4)------------------------------------------63
圖4.1：(a)剛電鍍完錫膜SEM表面俯視圖、(b)圖(a)中白色實線內電鍍錫
膜表面放大圖------------------------------------------64
圖4.2：150℃熱處理時間VS殘餘應力----------------------------65
圖4.3：ITO玻璃電鍍錫膜樣品圖--------------------------------66
圖4.4：ITO玻璃剛電鍍完錫膜SEM表面俯視圖-------------------66
圖4.5：室溫下50天不受應力樣品SEM表面俯視圖(a,b) Sn/Cu、(c,d) Sn/ITO------------------------------------------------67
圖4.6：150℃,50天Sn/Cu (a) SEM表面俯視圖、(b)圖(a)框內放大圖--68
圖4.7：150℃,50天Sn/ITO SEM表面俯視圖----------------------68
圖4.8：Sn/Cu試片XRD分析圖(室溫、150℃)---------------------69
圖4.9：Sn/ITO及ITO試片在150℃下XRD分析圖-----------------70
圖4.10：室溫下50天(a)不受應力樣品SEM表面俯視圖、(b)圖(a)中白色實線內錫鬚放大圖-------------------------------------71
圖4.11：室溫下80天(a)不受應力樣品SEM表面俯視圖、(b)圖(a)中白色實線內錫鬚放大圖-------------------------------------72
圖4.12：不受應力樣品SEM表面俯視圖(a,b)熱處理80℃下、(c,d)熱處理
150℃下----------------------------------------------73
圖4.13：室溫下50天(a)受拉伸應力樣品區域1 SEM表面俯視圖、(b)圖(a)
中白色實線內錫鬚放大圖--------------------------------74
圖4.14：室溫下80天(a)受拉伸應力樣品區域1 SEM表面俯視圖、(b)圖(a)
中白色實線內錫鬚放大圖--------------------------------75
圖4.15：受拉伸應力區域1 SEM表面俯視圖(a,b)熱處理80℃下、(c,d) 熱
處理150℃下----------------------------------------- 76
圖4.16：室溫下50天(a)受拉伸應力樣品區域2 SEM表面俯視圖、(b)圖(a)
中白色實線內錫鬚放大圖--------------------------------77
圖4.17：室溫下80天(a)受拉伸應力樣品區域2 SEM表面俯視圖、(b)圖(a)
中白色實線內錫鬚放大圖--------------------------------78
圖4.18：受拉伸應力區域2 SEM表面俯視圖(a)熱處理80℃下、(b) 熱處
理150℃下------------------------------------------- 79圖4.19：電鍍錫膜表面錫晶粒微結構示意圖(a)不受應力試片、(b)受應力
試片-------------------------------------------------82
圖4.20：矽晶片電鍍錫膜試片XRD分析圖------------------------83
圖4.21：室溫下不受應力樣品SEM表面俯視圖(a,b) 50天、(c,d) 80天-------------------------------------------------------85
圖4.22：室溫下受拉伸應力樣品區域1 SEM表面俯視圖(a,b) 50天、(c,d) 80
天----------------------------------------------------86
圖4.23：室溫下50天受拉伸應力區域2 SEM表面俯視圖-----------87
圖4.24：室溫下80天受拉伸應力區域2 SEM表面俯視圖-----------88
圖4.25：應力模擬簡圖-----------------------------------------90
圖4.26：錫膜表面應力分佈-------------------------------------90
圖4.27：受拉伸應力錫鬚成長方向示意圖-------------------------91
圖4.28：80℃介金屬化合物橫截面圖(OM) ------------------------93
圖4.29：150℃介金屬化合物橫截面圖(OM)------------------------95
圖4.30：170℃介金屬化合物橫截面圖(OM)------------------------97
圖4.31：80℃、150℃、170℃受拉伸應力及不受應力(IMC厚度VS時間)
-----------------------------------------------------98
圖4.32：80℃、150℃、170℃拉伸應力及不受應力(IMC厚度VS時間0.5)圖---------------------------------------------------98
圖4.33：受拉伸應力及不受應力(lnk VS 1/T)圖--------------------99
圖4.34：150℃受壓縮、拉伸應力及不受應力(IMC厚度VS熱處理時間)
----------------------------------------------------100
圖4.35：150℃受壓縮、拉伸應力及不受應力介金屬化合物SEM橫截面圖
----------------------------------------------------101
圖4.36：170℃受壓縮、拉伸應力及不受應力(IMC厚度VS熱處理時間)
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圖4.37：170℃受壓縮、拉伸應力及不受應力介金屬化合物SEM橫截面圖
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圖4.38：200℃受壓縮、拉伸應力及不受應力(IMC厚度VS熱處理時間)
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圖4.39：200℃受壓縮、拉伸應力及不受應力介金屬化合物SEM橫截面圖
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圖4.40：150℃、170℃、200℃受拉伸應力及不受應力(IMC厚度VS時間)
----------------------------------------------------106
圖4.41：150℃、170℃、200℃受拉伸應力及不受應力(IMC厚度VS
時間0.5)圖-------------------------------------------106
圖4.42：受拉伸應力及不受應力(lnk VS 1/T)圖-------------------107
圖4.43：Sn/Cu界面反應機制示意圖(a)不受應力、(b)外拉伸應力、(c)外加壓縮應力---------------------------------------------109

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