TWI586811B - Lead - free solder bump joint construction - Google Patents
Lead - free solder bump joint construction Download PDFInfo
- Publication number
- TWI586811B TWI586811B TW102126826A TW102126826A TWI586811B TW I586811 B TWI586811 B TW I586811B TW 102126826 A TW102126826 A TW 102126826A TW 102126826 A TW102126826 A TW 102126826A TW I586811 B TWI586811 B TW I586811B
- Authority
- TW
- Taiwan
- Prior art keywords
- lead
- free solder
- solder bump
- intermetallic compound
- film thickness
- Prior art date
Links
- 229910000679 solder Inorganic materials 0.000 title claims description 265
- 238000010276 construction Methods 0.000 title description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 233
- 229910045601 alloy Inorganic materials 0.000 claims description 79
- 239000000956 alloy Substances 0.000 claims description 79
- 239000012535 impurity Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 description 148
- 239000010408 film Substances 0.000 description 123
- 238000010438 heat treatment Methods 0.000 description 46
- 238000012795 verification Methods 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 20
- 239000000758 substrate Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- 238000000879 optical micrograph Methods 0.000 description 14
- 230000004907 flux Effects 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 229910017482 Cu 6 Sn 5 Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 229910017944 Ag—Cu Inorganic materials 0.000 description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 description 3
- 229910020988 Sn—Ag Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 241000270295 Serpentes Species 0.000 description 2
- 229910020888 Sn-Cu Inorganic materials 0.000 description 2
- 229910019204 Sn—Cu Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
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- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
- H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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- H01L24/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K2101/00—Articles made by soldering, welding or cutting
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Description
本發明係關於無鉛銲料凸塊接合構造,例如適用於將第1電子構件的銅電極(以下、稱為Cu電極)、與第2電子構的Cu電極經由無鉛銲料凸塊接合的無鉛銲料凸塊接合構造。
電性連接電子機器等的電子構件之間的方法,已知使用於電極上形成而稱為凸塊的突起的方法。近年,因環境問題及EU(歐盟)RoHS指令(Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment)等,作為形成在Cu電極上的凸塊,多數採用不含Pb的無鉛銲料合金(參照例如,專利文獻1)。
此外,近年,隨著電子機器的小型化.高機能化,在半導體構裝要求高密度構裝。因此,對高密度構裝有利的覆晶構裝迅速地被採用,近年,要求其電極間距200[μm]以下的窄間距。如此之窄間距,亦需要凸塊的細微化,但另一方面,隨著最近的晶片的高性能化而電流量亦增大。
但是,以無鉛銲料合金之電子構件間的接合部(以下,僅稱為無鉛銲料接合部),當流過單位面積的電流(電流密度)上升,則在無鉛銲料接合部發生Cu的電遷移(以下,所謂
電遷移係指Cu的電遷移之意思。)現象,進而引起斷線之不良之虞。因此,近年,有事先在無鉛銲料接合部之Cu電極上形成Ni層,使該Ni層作用作為阻障層而抑制Cu由Cu電極擴散,即使電流密度變高,亦不容易發生電遷移現象之無鉛銲料凸塊接合構造之提案。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平5-50286號公報
但是,具有該構成之無鉛銲料凸塊接合構造,為抑制電遷移現象的發生,而在於第1電子構件的Cu電極上設置無鉛銲料球之前,事先在Cu電極表面形成作為阻障層之Ni層的同時,亦需於第2電子構件側之Cu電極上同樣地事先形成Ni層,Ni層的成膜步驟的部分,有使無鉛銲料凸塊接合構造之製造步驟變得繁瑣,而有增加成本等,有增加製造時之負擔的問題。
本發明係有鑑於如上所述的問題而完成者,以提供可減輕先前製造時之負擔,且可抑制發生電遷移現象之無鉛銲料凸塊接合構造為目標。
關於本發明之申請專利範圍第1項之無鉛銲料凸塊接合構造,將第1電子構件的Cu電極與第2電子構件之Cu電極,經由無鉛銲料凸塊接合,電流密度為0.7×103[A/cm2]以
上的大電流經由上述無鉛銲料凸塊流過上述第1電子構件及上述第2電子構件之間,其特徵在於:上述無鉛銲料凸塊係以Sn作為主體之合金及不可避免雜質所構成,在與上述第1電子構件的Cu電極的境界及與上述第2電子構件的Cu電極的境界,形成金屬間化合物層,各上述金屬間化合物層係於與上述無鉛銲料凸塊的界面,膜厚為該金屬間化合物層之平均膜厚的30%以下的部分的谷部,及鄰接於該谷部之山部之高低差為4[μm]以上的凹凸形狀在0.02[個/μm]以下。
關於本發明之申請專利範圍第2項之無鉛銲料凸塊接合構造,係在於申請專利範圍第1項之無鉛銲料凸塊接合構造,上述無鉛銲料凸塊,將Ni、Co、Fe之1種以上,以總計包含0.005~0.2質量%。
關於本發明之申請專利範圍第3項之無鉛銲料凸塊接合構造,係在於申請專利範圍第1或2項之無鉛銲料凸塊接合構造,上述無鉛銲料凸塊,包含Ag:0~5質量%、Cu:0~2質量%。
關於本發明之申請專利範圍第4項之無鉛銲料凸塊接合構造,係在於申請專利範圍第1~3項之任何一項之無鉛銲料凸塊接合構造,上述無鉛銲料凸塊,進一步將P、Mg、Ge之1種以上,以總計包含0~0.01質量%。
關於本發明之申請專利範圍第5項之無鉛銲料凸塊接合構造,係在於申請專利範圍第1或4項之任何一項之無鉛銲料凸塊接合構造,上述無鉛銲料凸塊,包含Pd、Mn、Zn、
Al、Sb、In之1種以上,Pd、Mn、Al:0~1質量%;Zn:0~10質量%;Sb:0~3質量%;In:0~7質量%。
根據本發明之無鉛銲料凸塊接合構造,即使沒有如先前事先在第1電子構件及第2電子構件的各Cu電極表面上分別形成作為阻障層之Ni層,藉由使形成於與金屬間化合物層之Cu電極之界面之金屬間化合物層之凹凸形狀在0.02[個/μm]以下,使Cu不容易擴散,可抑制電遷移現象的發生。然而,省去於Cu電極表面形成作為阻障層之Ni層的成膜步驟的部分,可減輕製造時之負擔,故可提供較先前減輕製造時之負擔,且可抑制電遷移現象的發生的無鉛銲料凸塊接合構造。
B11‧‧‧無鉛銲料凸塊接合構造
2‧‧‧第1電子構件
3a、3b‧‧‧Cu電極
7a、7b‧‧‧金屬間化合物層
9‧‧‧第2電子構件
12‧‧‧IMC界面
第1圖係表示本發明之無鉛銲料凸塊接合構造之側剖面構成之SEM照片。
第2圖係第1圖所示之無鉛銲料凸塊接合構造之中,將無鉛銲料凸塊與Cu電極之境界部分放大之光學顯微鏡照片。
第3圖係供於著眼於IMC界面之耐電遷移性之提升效果之機構說明(1)之示意圖。
第4圖係供於著眼於IMC界面之耐電遷移性之提升效果之機構說明(2)之示意圖。
第5圖係供於IMC界面之平坦化之說明之示意圖。
第6圖係表示熱處理前與熱處理後之金屬間化合物層之側剖面構成(1)之示意圖。
第7圖係表示熱處理前與熱處理後之金屬間化合物層之側剖面構成(2)之示意圖。
第8圖係表示驗證用電路之全體構成之示意圖。
第9圖係表示比較例1之無鉛銲料凸塊接合構造之側剖面構成之SEM照片。
第10圖係第9圖所示無鉛銲料凸塊接合構造之中,將無鉛銲料凸塊與Cu電極之境界部分放大之光學顯微鏡照片。
第11圖係斷裂時間與電流密度之關係之圖表。
第12圖係對實施例1之無鉛銲料凸塊構造施以既定時間的熱處理時之金屬間化合物層之IMC界面之剖面光學顯微鏡照片。
第13圖係對比較例1之無鉛銲料凸塊構造施以既定時間的熱處理時之金屬間化合物層之IMC界面之剖面光學顯微鏡照片。
第14圖係表示電阻變化率與經過時間之關係之圖表。
第15圖係將改變Ni的添加量時之上側之IMC界面放大之光學顯微鏡照片。
第16圖係將改變Ni的添加量時之下側的IMC界面放大之光學顯微鏡照片。
第17圖係在於實施例7之無鉛銲料凸塊接合構造之IMC界面剖面之光學顯微鏡照片。
第1圖係本發明之無鉛銲料凸塊接合構造B11之SEM(Scanning Electron Microscope:掃描式電子顯微鏡)照片,
由於藉由無鉛銲料合金形成之無鉛銲料凸塊5,係形成於第1電子構件2之Cu電極3a與第2電子構件9之Cu電極3b之間,將相對之Cu電極3a、3b經由無鉛銲料凸塊5,物理及電性接合。再者,第1圖中,4a、4b係絕緣膜,Cu電極3a、3b係以絕緣膜4a、4b包圍的構成。
本發明之無鉛銲料凸塊接合構造B11,並沒有在Cu電極3a、3b表面形成作為阻障層之Ni層,藉由在製造過程進行之回銲,於無鉛銲料凸塊5及Cu電極3a、3b之各境界,形成可作用作為阻障層之金屬間化合物(IMC:Inter Metallic Compound)層7a、7b之點,與先前的無鉛銲料凸塊接合構造不同。
此外,加上此,形成於無鉛銲料凸塊接合構造B11之金屬間化合物層7a、7b,藉由與無鉛銲料凸塊5之界面之平坦化,提升在於Cu電極3a、3b及無鉛銲料凸塊5之間之耐電遷移性,可抑制Cu的電遷移現象為原因之斷線不良之構成。
特別是,本發明之無鉛銲料凸塊接合構造B11,係用於電流密度為0.7×103[A/cm2]以上的大電流,較佳的是電流密度為1.0×103[A/cm2]以上的大電流之電路者,即使是如此之大電流經由無鉛銲料凸塊5流過第1電子構件2及第2電子構件9之間,亦可抑制電遷移現象的發生。
此外,於無鉛銲料凸塊接合構造B11,例如,使用將無鉛銲料合金形成為球狀的無鉛銲料球形成無鉛銲料凸塊5時,使用直徑10~300[μm]程度的無鉛銲料球,圖謀無鉛銲料凸塊5的微小化,即使經由無鉛銲料凸塊5的第1電子構件2及
第2電子構件9的電流密度上升,亦不會發生斷線不良,可持續對第1電子構件2及第2電子構件9之間流放大電流。
Cu電極3a、3b表面的金屬間化合物層7a、7b,係在於製造過程,無鉛銲料合金Cu在電極3a、3b表面回銲,在形成無鉛銲料凸塊5時所形成者。於本發明,重點在於回銲所形成之金屬間化合物層7a、7b與無鉛銲料凸塊5之界面形狀,藉由使該界面形狀平坦化而膜厚大致均勻地形成,可使Cu電極3a、3b之Cu不容易在無鉛銲料凸塊5內擴散,而可抑制電遷移現象的發生。
在此,第2圖A及第2圖B,係第1圖所示之無鉛銲料凸塊接合構造B11之中,放大無鉛銲料凸塊5與Cu電極3a、3b之境界部分之光學顯微鏡照片。如第2圖A及第2圖B所示,金屬間化合物層7a、7b,在與無鉛銲料凸塊5之界面(以下,稱為IMC界面)12重點在於,膜厚為金屬間化合物層7a、7b之平均膜厚之30%以下的部分之谷部與鄰接於該谷部之山部之高低差為4[μm]以上的凹凸形狀為0.02[個/μm]以下,以0.01[個/μm]以下為佳。如此地,金屬間化合物層7a、7b,藉由使形成在IMC界面12之高低差較大的4[μm]以上的凹凸形狀在0.02[個/μm]以下,可說IMC界面12被平坦化,藉由如此之平坦化之界面形狀,可抑制Cu電極3a、3b之Cu擴散。
凹凸形狀為0.01[個/μm]以下,則金屬間化合物層7a、7b之IMC界面12更加平坦化,可更加抑制Cu電極3a、3b之Cu擴散,可進一步得到耐電遷移性之提升效果。另一方
面,凹凸形狀超過0.02[個/μm],則金屬間化合物層7a、7b之IMC界面12凹凸化,使谷部與山部之高低差與谷部寬幅變大,Cu電極3a、3b之Cu容易由IMC界面12深深地凹下的谷部擴散至無鉛銲料凸塊5內,而無法得到耐電遷移性之提升效果。
於本發明,例如,將由金屬間化合物層7a、7b之一端至另一端的全寬側剖面形狀由剖面橫方向觀察,於該側剖面位置向寬方向x(與連結相對的Cu電極3a、3b之間的方向y正交的方向(第1圖))延伸的IMC界面12之全寬,鑑定有幾個膜厚為金屬間化合物層7a、7b之平均膜厚之30%以下的部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀。
觀察金屬間化合物層7a、7b之IMC界面剖面形狀時,使用以光學顯微鏡之光學顯微鏡照片之光學顯微觀察之外,亦可使用以SEM照片之SEM觀察。凹凸形狀的數量,係於金屬間化合物層7a、7b之任意側剖面之位置,於IMC界面12之全寬中,以目視或利用既定影像處理軟體鑑定有幾個上述凹凸形狀,由在於該側剖面位置之IMC界面12之全寬尺寸,及特定的凹凸形狀的個數,以線密度算出。再者,觀察金屬間化合物層7a、7b之IMC界面剖面形狀之全寬位置,無須為Cu電極3a、3b之直徑位置,亦可係由直徑位置偏離的位置。再者,於該實施形態之情形,Cu電極3a、3b,使電極徑之設計值為150[μm]。
金屬間化合物層7a、7b之平均膜厚,係例如,利用可僅將在於側剖面位置之金屬間化合物層7a、7b區域特定
萃取的影像處理軟體,或利用其他各種手法即可。其一例,將金屬間化合物層7a、7b之光學顯微鏡照片或SEM照片等的側剖面影像為基礎,將金屬間化合物層7a、7b之側剖面區域,以目視萃取,將萃取之區域內的面積,以影像分析軟體算出,由側剖面影像中的IMC界面12之全寬尺寸與面積,算出平均膜厚。接著,算出該平均膜厚之30%的膜厚值之後,鑑定Cu電極3a、3b與金屬間化合物層7a、7b之境界線,以該境界線作為基準沿著境界線拉平均膜厚的30%的30%平均線,鑑定低於30%平均線之深凹的谷部。然後,確認低於30%平均線的膜厚薄的部分之谷部,與鄰接於該谷部之山部之高低差有否4[μm]以上,鑑定高低差為4[μm]以上的凹凸形狀的數量,由IMC界面12之觀察位置之全寬尺寸,判斷線密度是否為0.02[個/μm]以下。
在此,於第2圖A,萃取金屬間化合物層7a之側剖面區域,以影像分析軟體(Image J)算出側剖面區域的面積,算出金屬間化合物層7a的平均膜厚,結果為3.4[μm](圖中,以平均=和3.4μm記述),平均膜厚的30%為1.02[μm](圖中,以30%平均=1.02μm記述)。於金屬間化合物層7a,以平均膜厚之30%之數值作為30%平均線,以Cu電極3a的境界為基準拉線,將上述凹凸形狀的數量以目視計數,結果為0[個/μm](0個/129[μm]),IMC界面為平坦化之的構成(圖中,作為4[μm]的長度的標準以雙向箭頭標示)。
此外,第2圖B亦同樣地,算出金屬間化合物層7b之平均膜厚,結果為2.9[μm](圖中,以平均=2.9μm記述),
平均膜厚的30%為0.87[μm](圖中,以30%平均=0.87μm記述)。金屬間化合物層7b,以平均膜厚之30%之數值作為30%平均線,以Cu電極3b的境界為基準拉線,將上述凹凸形狀數計數,結果為0[個/μm](0個/138[μm]),IMC界面12為平坦化的構成。
在此,著眼在金屬間化合物層7a、7b之IMC界面12之界面形狀,推想耐電遷移性的提升效果之機構。第3圖A,係表示平均膜厚之30%以下的膜厚部分的谷部與鄰接於該谷部之山部之高低差為4[μm]以上的凹凸形狀,在於IMC界面12形成較0.02[個/μm]多的金屬間化合物層7g的影像圖。如此地高低差大的凹凸形狀在於IMC界面12較0.02[個/μm]多的金屬間化合物層7g,存在很多山部與谷部的高低差大的凹凸形狀的份,使IMC界面12成不均勻的膜厚。
無鉛銲料凸塊5以Sn作為主成分時,形成於Cu電極上之金屬間化合物層7g將成薄的Cu3Sn層與Cu6Sn5。再者,於回銲之後形成於Cu側之Cu3Sn層較Cu6Sn5層薄,故未示於圖,但金屬間化合物層7g係合併Cu3Sn與Cu6Sn5者。此時,金屬間化合物層7g的之Cu6Sn5,由於電阻值較以Sn作為主成分之無鉛銲料凸塊5大,故大大地凹陷的而膜厚變薄的凹凸形狀之谷部V之電阻值變得較其他地方低。因此,如第3圖B所示,在於金屬間化合物層7g,由Cu電極3a的電流容易集中在凹凸形狀大大地凹陷的谷部V。金屬間化合物層7g,當電流集中在凹凸形狀的谷部V,則因電遷移而如第3圖C所示,Cu電極3a的Cu,或金屬間化合物層7g中的Cu的擴散被促進,結果如第3圖D所示,Cu亦由IMC界面12的谷部
周邊脫離,使空隙擴大。金屬間化合物層7g,將如第3圖E所示,空隙進一步擴大的同時,因此而電流密度亦上升,最終引起斷線不良。
對此,如第4圖A所示之本發明之金屬間化合物層7e,膜厚為平均膜厚之30%以下的部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上之凹凸形狀,於IMC界面為0.02[個/μm]以下,使IMC界面12平坦化而膜厚均勻化。藉此,於金屬間化合物層7e,如第4圖B所示由Cu電極3a的電流被分散而電流的集中之處變少,可抑制Cu電極3a之Cu,或金屬間化合物層7e中的Cu的擴散,而可得提升耐電遷移性之效果。
整理以上之點,則如第5圖A所示,不僅在於IMC界面12沒有凹凸之平面狀金屬間化合物層7c,如第5圖B所示在於IMC界面12,有高低差未滿4[μm]之淺的凹凸之金屬間化合物層7d,及如第5圖C所示,即使在於IMC界面12有多數凹凸,谷部與山部的高低差未滿4[μm]而凹凸很淺的金屬間化合物層7e,亦可說IMC界面12被平坦化,可抑制谷部周邊的Cu擴散,可得提升耐電遷移性之效果。
另一方面,如第5圖E所示,在於IMC界面12,高低差為4[μm]以上的很大的凹凸形狀遠超過0.02[個/μm]的多數之金屬間化合物層7g之外,如第5圖D所示,在於IMC界面12,即使高低差4[μm]以上的凹凸形狀稀疏,但凹凸形狀存在超過0.02[個/μm]的金屬間化合物層7g,無法說IMC界面12有被平坦化,容易由谷部周邊發生Cu擴散,無法得到耐電
遷移性之提升效果。
在此,形成無鉛銲料凸塊5及金屬間化合物層7a、7b之無鉛銲料合金,以Sn作為主體之合金及不可避免之雜質所組成者為佳。即使是以Sn作為主體之合金及不可避免之雜質所組成的無鉛銲料合金,於製作無鉛銲料凸塊接合構造之後,藉由以未滿無鉛銲料合金之固相溫度長時間熱處理(後述),可使金屬間化合物層7a、7b之IMC界面12平坦化,可得提升耐電遷移性之效果。再者,以Sn為主體,係指以構成無鉛銲料合金之組成物全體之質量為基準,含70質量%以上的Sn者。
上述無鉛銲料合金,於以Sn作為主體之合金及不可避免之雜質所組成之無鉛銲料合金之外,以如Sn-Ag-Cu系、Sn-Ag系、Sn-Cu系等地銲料成分系亦有效,此時,含有Ag:0~5質量%、Cu:0~2質量%為佳。作為Sn-Ag系或Sn-Ag-Cu系的無鉛銲料合金,包含Ag:1~5質量%時,於凝固組織中產生Ag3Sn金屬間化合物之網路,亦可提升無鉛銲料凸塊之強度與疲勞特性。
此外,於本發明,於製作無鉛銲料凸塊接合構造之後,即使未以未滿無鉛銲料合金之固相溫度長時間熱處理,藉由在以Sn作為主體之合金及不可避免之雜質所組成的無鉛銲料合金添加Ni、Co、Fe之1種以上,可使金屬間化合物層7a、7b之IMC界面12平坦化,可得提升耐電遷移性之效果。將Ni、Co、Fe等3d金屬元素作為添加元素添加於無鉛銲料合時,將Ni、Co、Fe的1種以上,以總計包含0.005~0.2質量%
為佳,以0.01~0.1質量%更佳。未滿0.005質量%,則無法得到使金屬間化合物層的IMC界面平坦化的效果,結果無法得到提升耐電遷移性之效果,另一方面,超過0.2質量%,則會使熔點上升,而需要重新確認回銲條件有實用上的問題之虞。
在此,Ni係容易與Cu置換者,以置換金屬間化合物層7a、7b中的Cu的形式含於金屬間化合物層7a、7b。即,包含該添加元素之無鉛銲料合金,係藉由在於製造過程於Cu電極3a、3b表面進行之回銲,使含Ni的金屬間化合物均勻且細微而無縫隙地析出於Cu電極3a、3b之表面全體,以此為核均勻地成長Cu6Sn5,而可形成凹凸形狀平坦化成0.02[個/μm]以下之IMC界面12。再者,Co、Fe亦可認為係同樣的機構。
例如,以Sn作為主體之合金及不可避免之雜質所組成的無鉛銲料合金,含有Ni0.005~0.2質量%,以0.01~0.1質量%為佳時,例如,藉由在第1電子構件2之Cu電極3a上進行之回銲,在無鉛銲料合金之Sn與Cu電極3a之Cu反應之前,Ni與Sn反應,於金屬間化合物層的形成初期,使Ni3Sn4均勻且細微地析出在Cu電極3a表面。之後,由於在金屬間化合物層形成初期所析出的Ni3Sn4均勻且細微,以此作為核所成長之Cu6Sn5亦均勻地成長,而可於IMC界面12形成凹凸形狀在0.02[個/μm]以下之平坦化之金屬間化合物層7a。
再者,第1圖所示無鉛銲料凸塊接合構造B11,係以Sn作為主體之合金及不可避免之雜質所組成,使用包含Ag:1.2質量%、Cu:0.5質量%、Ni:0.05質量%之無鉛銲料合金(Sn-1.2Ag-0.5Cu-0.05Ni)形成無鉛銲料凸塊5及金屬間化
合物層7a、7b者,於無鉛銲料凸塊接合構造B11之製作之後,不進行長時間的熱處理,使IMC界面12平坦化者。
於上述無鉛銲料合金,亦可含有P、Mg、Ge之1種以上作為微量添加元素,總計含有0~0.01質量%。P、Mg、Ge,係藉由存在於Sn中,有減少Sn中的氧濃度的效果。氧化介在物存在於Cu電極界面附近,則該界面特性(例如,沾濕性等)將極端地下降。於本發明,藉由添加P、Mg、Ge之至少1種以上,可抑制因氧化介在物之自然氧化膜之成長,其結果於金屬間化合物層的形成初期,容易在Cu電極3a、3b表面全體析出均勻且細微的金屬間化合物,可於IMC界面12得到凹凸形狀在0.02[個/μm]以下之平坦化的金屬間化合物層7a、7b。
此外,於上述無鉛銲料合金,亦可含Pd、Mn、Zn、Al、Sb、In之1種以上作為添加元素。將該等Pd、Mn、Zn、Al、Sb、In之1種以上添加於無鉛銲料合金時,包含Pd、Mn、Al:0~1質量%、Sb:0~3質量%、In:0~7質量%、Zn:0~10質量%為佳。於本發明,在以Sn作為主體之合金及不可避免之雜質所組成的無鉛銲料合金,包含Pd、Mn、Zn、Al、Sb、In之1種以上時,藉由固溶強化或析出強化使銲料本身變硬,而可提升溫度循環特性。
一般上述之元素之組成,可例如,以ICP分析法或GD-MS法等測定。此外,本發明之無鉛銲料凸塊接合構造B11,即使使用在業界一般使用之流動銲料、回銲用銲料、線銲料等的任一銲料合金的形態所組成之無鉛銲料合金,亦可顯現該效果,再者,包含銲料粉之銲料膏或銲料球,亦可顯現該
效果。
因此,於該無鉛銲料凸塊接合構造B11,第1電子構件2之Cu電極3a形成為厚度40~80[μm]之柱狀,與此相對之第2電子構件9之Cu電極3b,形成為5~30[μm]之薄膜狀,惟第2電子構件9之Cu電極3b側之厚度,亦可形成30[μm]以上,此時,對Cu因電遷移之擴散,可得因Cu的量增加而可延長斷裂時間之效果,及可緩和接合在第2電子構件9之Cu電極3b之凸塊角部之電流集中的效果。
在於製作本發明之無鉛銲料凸塊接合構造B11,需要於第1電子構件2之Cu電極3a形成無鉛銲料凸塊5之步驟,及使形成於第1電子構件2之Cu電極3a之無鉛銲料凸塊5,進一步與第2電子構件9之Cu電極3b接合之步驟。此外,形成具有高低差在4[μm]以上的凹凸形狀在0.02[個/μm]以下之平坦化之IMC界面12之金屬間化合物層7a、7b之方法,有藉由在無鉛銲料合金包含Ni、Co、Fe之1種以上而實現的方法,及於製作無鉛銲料凸塊接合構造之後,以未滿無鉛銲料合金之固相溫度長時間熱將處理而實現的方法。
前段之藉由在無鉛銲料合金含有添加元素而實現IMC界面12之平坦化之方法,可例如於真空中、或非氧化性氣氛中,Ni、Co、Fe的1種以上,於以Sn作為主體的合金及不可避免雜質,以總計添加0.005~0.2質量%,以0.01~0.1質量%更佳,加熱使各成分金屬熔融之後,藉由冷卻固化製作無鉛銲料合金。如此之使用無鉛銲料合金製作無鉛銲料凸塊接合構造B11之方法,一般有藉由網版印刷的方法,及無鉛銲料球
之方法。於網版印刷,將上述無鉛銲料合金以噴霧法等作成細微的銲料粉之後,與助銲劑混合作為糊料,於Cu電極3a上使用金屬掩模,使用刮刀法,將一定量糊料載置於第1電子構件2之Cu電極3a上之後,進行後述之第1次預熱及回銲,於第1電子構件2之Cu電極3a上形成無鉛銲料凸塊5。
另一方面,由無鉛銲料合金製作無鉛銲料球時,以將熔解之無鉛銲料合金鑄塊拉絲,作成絲線狀之後,裁切成一定長度,在油中使之熔融,利用表面張力球狀化之切線法,或將熔解的無鉛銲料合金以既定的頻率振動之細微的孔噴出,於真空中或氣體氣氛中藉由振動波將熔融銲料以一定的體積裁切,以表面張力使之球狀化之氣中造粒法等之任一手法製作均可。以無鉛銲料球之製作方法,係將上述無鉛銲料設在塗佈助銲劑之第1電子構件2之Cu電極3a上,藉由進行第1次預熱及回銲,於第1電子構件2之Cu電極3a上形成無鉛銲料凸塊5。
在此,上述任一預熱,均係例如以150[℃]加熱70秒之預備加熱,而圖謀第1電子構件2全體之溫度之均勻化,且經由助銲劑(網版印刷法係含於糊料之助銲劑)使無鉛銲料離子擴散到Cu電極3a表面形成反應層。預熱之後進行的回銲,係以無鉛銲料合金之熔點以上之加熱(以260[℃]加熱40秒),使無鉛銲料球或糊料熔融,之後,藉由使之冷卻固化,於第1電子構件2之Cu電極3a表面形成無鉛銲料凸塊5者。
此時,於本發明,藉由回銲,於Cu電極3a表面之反應層,析出均勻且細微的金屬間化合物,以此為核使
Cu6Sn5均勻地成長,形成平坦化成凹凸形狀在0.02[個/μm]以下的IMC界面12之金屬間化合物層7a。再者,於Cu電極3a表面有氧化膜時,氧化膜的阻礙使Cu電極3a不容易與無鉛銲料凸塊5發生反應,金屬間化合物變得不容易形成於Cu電極3a表面上。因此,為了在Cu電極3a表面形成細微而均勻的金屬間化合物,預先將Cu電極3a之氧化膜去除較佳。在此,由於助銲劑具有去除氧化膜之效果,故在於製造過程使用助銲劑即可,其他,亦可藉由電漿處理、或使用硫酸等的蝕刻去除Cu電極3a、3b之氧化膜。
例如,使用無鉛銲料球之方法,係於Cu電極3a表面設置無鉛銲料球時,預先將助銲劑塗佈於Cu電極3a表面,可於回銲時將氧化膜去除,藉此可於Cu電極3a表面全體形成細微而均勻的金屬間化合物。此外,同樣的,雖於無鉛銲料球側亦有氧化膜,但可藉由助銲劑將該氧化膜去除,可於回銲之後的無鉛銲料凸塊5及Cu電極3a的界面不會介在氧化膜,而於Cu電極3a的表面形成均勻而細微的金屬間化合物。
接著,將形成無鉛銲料凸塊5之1電子構件2上下相反地翻過來,於塗佈有助銲劑之第2電子構件9之Cu電極3b上,將該無鉛銲料凸塊5定位設置,再度以與上述相同的條件進行第2次預熱及回銲,使無鉛銲料凸塊5接合於第2電子構件9之Cu電極3b上,製造如第1圖所示之無鉛銲料凸塊接合構造B11。即,於無鉛銲料凸塊接合構造B11,於製作將第1電子構件2之Cu電極3a側回銲2次,將第2電子構件9之Cu電極3b側回銲1次。
於第2次預熱,亦與上述同樣地,例如,藉由以150[℃]預佳熱70秒,經由助銲劑使無鉛銲料離子擴散到Cu電極3b表面形成反應層。此外,於該預熱之後進行之第2次回銲,亦藉由加熱至無鉛銲料合金之熔點以上,於Cu電極3b表面之反應層析出均勻且細微的金屬間化合物,以此為核使Cu6Sn5均勻地成長,於Cu電極3b表面形成平坦化成凹凸形狀在0.02[個/μm]以下之IMC界面12之金屬間化合物層7b。
接著,說明於無鉛銲料凸塊接合構造之製作之後,藉由進行長時間熱處理,實現IMC界面之平坦化之方法。於無鉛銲料凸塊接合構造的製作之後,進行長時間熱處理時,使無鉛銲料合金含有上述Ni、Co、Fe等的添加元素,亦可形成使IMC界面平坦化之金屬間化合物層。例如,準備以Sn作為主體之合金及不可避免之雜質所組成之無鉛銲料合金,以與上述相同方法製作無鉛銲料凸塊接合構造。
於此狀態,由於無鉛銲料合金並沒有添加元素,故在回銲時並沒有在Cu電極表面析出均勻而細微的金屬間化合物,故於回銲時所形成之金屬間化合物層之IMC界面將凹凸化。即,如第6圖A所示,長時間熱處理之前的金屬間化合物層7g,在於膜厚為平均膜厚之30%以下之膜厚部分之谷部鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,於IMC介面12形成較0.02[個/μm]為多,而無法得到耐電遷移之提升效果。
因此,於無鉛銲料凸塊接合構造之製作後進行長時間熱處理。長時間熱處理,係以150[℃]以上,以無鉛銲料
合金之固相溫度以下的加熱溫度將製作之後的無鉛銲料凸塊接合構造加熱70小時以上為佳。再者,所謂固相溫度,係指既定成分的無鉛銲料合金在升溫時,由固體的狀態最初開始融化時的溫度。
藉此,金屬間化合物層7g,按照加熱時間成長,如第6圖B所示,成為平均膜厚較厚的金屬間化合物層7h。金屬間化合物層7h,藉由使平均膜厚變厚,減少膜厚為平均膜厚之30%以下的部分之谷部,該谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀的數量亦減少而成為0.02[個/μm]以下,可使IMC界面12平坦化。結果,於長時間熱處理之後的金屬間化合物層7h,來自Cu電極3a之電流被分散化,電流集中處變少,可抑制Cu電極3a的Cu,或金屬間化合物層7h中的Cu的擴散,可得提升耐電遷移性之效果。
再者,如第7圖A所示,藉由添加Ni、Co、Fe之1種以上,使IMC界面12平坦化之金屬間化合物層7e,亦可於製作無鉛銲料凸塊接合構造之後,藉由長時間熱處理而成長,成為如第7圖所示,膜厚較厚的金屬間化合物層7i,隨此減少膜厚為平均膜厚之30%以下的部分之谷部,可使IMC界面12更加平坦化。
在於以上的構成,於本發明之無鉛銲料凸塊接合構造B11,第1電子構件2及第2電子構件9之各Cu電極3a、3b表面,即使沒有如先前分別預先形成Ni層作為阻障層,藉由使金屬間化合物層7a、7b之無鉛銲料凸塊5側的界面的凹凸形狀為0.02[個/μm]以下,Cu變得難以擴散,可抑制電遷移
現象的發生。因此,省去在Cu電極3a、3b表面形成Ni層作為阻障層之成膜步驟的部分,可減輕製造時之負擔,故可較先前減輕製造時的負擔,且可提供抑制電遷移現象的發生的無鉛銲料凸塊接合構造B11。
以下,以實施例,更具體說明本發明之效果。
[實施例]
以下,說明實施例。在此,如第8圖所示,製作將8個無鉛銲料凸塊接合構造B11~B41、B12~B42電性連接之驗證用電路21,驗證在於無鉛銲料凸塊接合構造B11之IMC界面之界面形狀,及無鉛銲料凸塊接合構造B11~B41、B12~B42之耐電遷移性。於驗證用電路21,將第1電子構件2之Cu電極3a,與第2電子構件9之Cu電極3b,以複數無鉛銲料凸塊5接合,於中央區域上製作4列2行共計8個無鉛銲料凸塊接合B11~B41、B12~B42。再者,於第8圖中,25係熱電偶元件。
於實施例1之驗證用電路21,係將由Si晶片切出的晶圓級封裝(WLP:Wafer Level Package)作為第1電子構件2,使用由BT樹脂(Bismaleimide-Triazine Resin:雙馬醯胺-三嗪樹脂)所組成之基板作為第2電子構件9。於實施例1之驗證用電路21,首先使用成分為Sn-1.2Ag-0.5Cu-0.05Ni之無鉛銲料合金,於第1電子構件2(WLP)之Cu電極3a上形成無鉛銲料凸塊5。實際上,作為第1電子構件2使用150[μm]φ尺寸的柱狀的Cu電極3a在中心區域以4列2行共計配置8個WLP,於Cu電極3a表面,不形成成為阻障層之Ni層,於各Cu電極3a塗佈助銲劑之後,直接於各Cu電極3a配置將上述
無鉛銲料合金作成球狀之無鉛銲料球,以150[℃]預熱70秒之後,以260[℃]回銲40秒,於Cu電極3a表面形成無鉛銲料凸塊5。
其次,將接合有無鉛銲料凸塊5之第1電子構件2上下相反地翻過來,於塗佈助銲劑之第2電子構件9(基板)之Cu電極3b直接設置無鉛銲料凸塊5,以150[℃]預熱70秒之後,以260[℃]回銲40秒,於Cu電極3b表面接合無鉛銲料凸塊5,製作於中央區域具備8個無鉛銲料凸塊接合構造B11~B41、B12~B42之實施例1之驗證用電路21。此外,實施例2之驗證用電路21,係將第1電子構件2由WLP改在基板,以與實施例1相同的成分為Sn-1.2Ag-0.5Cu-0.05Ni之無鉛銲料合金,以與上述相同的條件製作接合基板驗證用電路21。
再者,於比較例1之驗證用電路21,係使用成分係沒有添加Ni之Sn-3Ag-0.5Cu之無鉛銲料合金,以與上述相同的條件使WLP及基板接合,製作與實施例1,只有無鉛銲料合金的成分不同的驗證用電路21。此外,作為比較例2的驗證用電路21,使用於比較例1所使用的WLP基板,使用成分係沒有添加Ni之Sn-3Ag-0.5Cu之無鉛銲料合金,以與上述相同的條件,使基板相互接合製作驗證用電路21。
在此,將關於實施例1之無鉛銲料凸塊接合構造,以SEM拍攝無鉛銲料凸塊的任意位置之側剖面,得到如第1圖所示之SEM照片。此外,於該側剖面位置,拍攝將金屬間化合物層7a、7b放大的光學顯微鏡照片,得到第2圖A及第2圖B所示之光學顯微鏡照片。由該等照片,以目視萃取金屬
間化合物層7a、7b之側剖面區域,使用影像處理軟體(Image J)算出該側剖面區域的面積,算出金屬間化合物層7a、7b之平均膜厚,結果為3.4[μm]及2.9[μm]。
接著,算出金屬間化合物層7a、7b之平均膜厚之30%,係1.02[μm]及0.87[μm]。以該等平均膜厚之30%膜厚值作為30%平均線,拉Cu電極3a、3b之境界之基準,以目視計數該30%線以下的谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀的數量,結果1個也沒有確認到凹凸形狀。藉此,於實施例1,IMC界面12之凹凸形狀之線密度成0.02[個/μm]以下(0[個/μm]),確認金屬間化合物層7a、7b之任一IMC界面12均被平坦化。
此外,同樣的,關於比較例1之無鉛銲料凸塊接合構造,亦將第1列第1行之無鉛銲料凸塊接合構造之任意位置拍攝側剖面構造之SEM照片,得到如第9圖所示之SEM照片。此外,如第9圖所示之無鉛銲料凸塊接合構造B11'之中,拍攝將無鉛銲料凸塊105與Cu電極3a、3b之境界部分之金屬間化合物層107a、107b放大之光學顯微鏡照片,得到如第10圖A及第10圖B之光學顯微鏡照片。
由第10圖A萃取金屬間化合物層107a之側剖面區域,以影像分析軟體(Image J)算出面積,算出金屬間化合物層107a之平均膜厚,結果為3.8[μm](圖中,以平均=3.8μm記述),平均膜厚之30%為1.14[μm](圖中,以30%平均=1.14μm記述)。於金屬間化合物層107a,以平均膜厚之30%數值作為30%平均線,拉Cu電極3a之境界之基準,計數該30%線以下
的谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀的數量,結果為0.036[個/μm](5個/139[μm],圖中,將凹凸形狀處以↓表示)。
此外,關於下側的金屬間化合物層107b,亦同樣的,由第10圖B算出平均膜厚,結果為2.7[μm](圖中,以平均=2.7μm記述),平均膜厚之30%為0.81[μm](圖中,以30%平均=0.81μm記述)。於金屬間化合物層107b,以平均膜厚之30%數值作為30%平均線,拉Cu電極3b之境界之基準,計數該30%線以下的谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀的數量,結果為0.030[個/μm](4個/133[μm],圖中,將凹凸形狀處以↑表示)。如此地,於任一金屬間化合物層107a、107b,IMC界面12之凹凸形狀的數量較0.02[個/μm]多,確認到IMC界面12被凹凸化。
接著,使用該等實施例1、實施例2、比較例1、比較例2之各驗證用電路21進行耐電遷移性的驗證試驗。於耐電遷移性的驗證試驗,係對驗證用電路21之中央區域之4列2行共計8個無鉛銲料凸塊接合構造B11~B41、B12~B42由電流源23流放電流,分別計測直到因電遷移現象而發生斷線不良之斷裂時間。
再者,此時,於各驗證用電路21,首先開始對在於的第1行的4個無鉛銲料凸塊接合構造B11~B41,由下側的基板向WLP(於實施例2、比較例2係上側之基板)、由WLP(於實施例2、比較例2係上側之基板)向下側的基板,使之上下蛇行依序流放電流之後,對其次之第2行的4個無鉛銲料凸塊接
合構造B12~B42,亦接著由下側的基板向WLP(於實施例2、比較例2係上側之基板)、由WLP(於實施例2、比較例2係上側之基板)向下側的基板,使之上下蛇行流放電流,將第1行與第2行連接流放電流。
然後,將流放第1行及第2行的電流之末端的無鉛銲料凸塊接合構造B11、B41(B12、B42)間的電壓值以電壓計24測量,確認隨著電遷移現象的電壓(電阻)變化,得到如第11圖所示之結果。再者,第11圖係以縱軸係通常的時間單位,橫軸係電流密度,表示斷裂時間與電流密度的關係之圖表,將實施例1以◇表示、實施例2以◆表示、比較例1以□表示、比較例2係以■表示。
由第11圖,確認以添加Ni的無鉛銲料合金所組成之無鉛銲料凸塊5使Cu電極3a、3b接合之實施例1及實施例2,較無鉛銲料合金沒有添加Ni的比較例1及比較例2,發生斷線不良的時間較長而可得提升耐電遷移性之效果。
接著,進行無鉛銲料凸塊接合構造在於製作後之熱處理之IMC界面之平坦化之驗證。在此,確認使用上述的實施例1及比較例1之驗證用電路21,將該等驗證用電路21進一步以150[℃]熱處理既定時間時之無鉛銲料凸塊接合構造之IMC界面的狀態。在此,第12圖A,係表示於製作實施例1之無鉛銲料凸塊接合構造之後,將此熱處理255小時之後之金屬間化合物層7r、7s之IMC界面剖面之光學顯微鏡照片。此外,第12圖B,係表示於製作實施例1之無鉛銲料凸塊構造之後,將此熱處理1356小時之後之金屬間化合物層7t、7u
之IMC界面剖面之光學顯微鏡照片。
由第12圖A,可知於上側之金屬間化合物層7r,平均膜厚為5.1[μm](圖中,以平均=5.1μm記述)、平均膜厚的30%為1.53[μm](圖中,以30%平均=1.53μm記述),另一方面,下側的金屬間化合物層7s,係平均膜厚為3.8[μm](圖中,以平均=3.8μm記述),平均膜厚的30%為1.14[μm](圖中,以30%平均=1.14μm記述)。可確認如此地,於製作無鉛銲料凸塊接合構造之後進行熱處理,則膜厚會變得較進行熱處理前之金屬間化合物層7a、7b(第2圖A及第2圖B)厚。
此外,由進一步使熱處理時間變長的第12圖B,算出金屬間化合物層7t、7u之平均膜厚及該這平均膜厚之30%,可知於上側之金屬間化合物層7t,平均膜厚為11.8[μm](圖中,以平均=11.8μm記述),平均膜厚的30%為3.54[μm](圖中,以30%平均=3.54μm記述),另一方面,下側的金屬間化合物層7u之平均膜厚為6.9[μm](圖中,以平均=6.9μm記述),平均膜厚的30%為2.07[μm](圖中,以30%平均=2.07μm記述)。由此可確認,將在於製作無鉛銲料凸塊接合構造之後的熱處理時間拉長,則膜厚會依照熱處理時間變厚。
然而,於長時間熱處理後的金屬間化合物層7r、7s、7t、7u,膜厚為平均膜厚之30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀為0[個/μm](於金屬間化合物層7r於任意側剖面位置為0個/141μm,於金屬間化合物層7s於任意側剖面位置為0個/145μm,於金屬間化合物層7t於任意側剖面位置為0個/133μm,金屬間化
合物層7u於任意側剖面位置為0個/136μm),IMC界面12之凹凸形狀為0.02[個/μm]以下。
其次,以光學顯微鏡照片為基礎確認對比較例1的驗證用電路21做熱處理時之IMC界面的狀態。第13圖A係表示於製作比較例1之無鉛銲料凸塊接合構造之後,熱處理265小時後之金屬間化合物層7v、7w之IMC界面剖面之光學顯微鏡照片。此外,第13圖B係表示於製作比較例1之無鉛銲料凸塊構造之後,熱處理1118小時熱後之金屬間化合物層7x、7y之IMC界面剖面之光學顯微鏡照片。
由第13圖A,可知於上側金屬間化合物層7v,平均膜厚為6.1[μm](圖中,以平均=6.1μm記述),平均膜厚的30%為1.83[μm](圖中,以30%平均=1.83μm記述),另一方面,下側的金屬間化合物層7w之平均膜厚為5.0[μm](圖中,以平均=5.0μm記述),平均膜厚的30%為1.5[μm](圖中,以30%平均=1.5μm記述)。如此地,確認即使是未於鉛銲料合金添加Ni之情形,於製作無鉛銲料凸塊接合構造之後進行熱處理,則膜厚會變得較熱處理前的金屬間化合物層107a、107b(第10圖A及第10圖B)厚。
然後,長時間熱處理之後的金屬間化合物層7v、7w之膜厚為平均膜厚之30%的部分的谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀為0[個/μm](於金屬間化合物層7v於任意側剖面位置為0個/140μm,於金屬間化合物層7w於任意側剖面位置為0個/146μm),因此,IMC界面12之凹凸形狀均為全都0.02[個/μm]以下,可確認在於熱處理
之前凹凸化IMC界面12,藉由熱處理而平坦化。
此外,由進一步使熱處理時間變長的第13圖B,算出金屬間化合物層7x、7y之平均膜厚,與該這平均膜厚之30%,可知上側金屬間化合物層7x之平均膜厚為6.6[μm](圖中,以平均=6.6μm記述)、平均膜厚的30%為1.98[μm](圖中,以30%平均=1.98μm記述),,一方面,下側的金屬間化合物層7y平均膜厚6.7[μm](圖中,以平均=6.7μm記述),平均膜厚的30%為2.01[μm](圖中,以30%平均=2.01μm記述)。由此,確認即使以使用沒有添加Ni的無鉛銲料合金的無鉛銲料凸塊接合構造,加長製作後的熱處理時間,則膜厚會依照熱處理時間變厚。
如此之金屬間化合物層7x、7y,膜厚為平均膜厚之30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀為0[個/μm](於金屬間化合物層7x於任意側剖面位置為0個/135μm,於金屬間化合物層7y於任意側剖面位置為0個/144μm),IMC界面12的凹凸形狀均為0.02[個/μm]以下,確認IMC界面12可藉由熱處理而平坦化。
其次,進行於無鉛銲料凸塊接合構造之製作進行熱處理使IMC界面平坦化時之耐電遷移性之驗證試驗。在此,如上所述,使用實施例1之驗證用電路21,使WLP側之金屬間化合物層之膜厚為6[μm],將該驗證用電路21以150[℃]加熱450小時,而製作實施例3之證用電路21。此外,如上所述使用比較例1之驗證用電路21,使WLP側之金屬間化合物層之膜厚為6[μm],將該驗證用電路21以150[℃]加熱325小時,
而製作實施例4之驗證用電路21。
此外,別於此,準備3個比較例1之驗證用電路21。然後,對該等實施例3、實施例4、比較例1之各驗證用電路21,由電流源23流放2.5[A]的電流(電流密度14.15[kA/cm2]),計測直到無鉛銲料凸塊接合構造之任一因電遷移現象而發生斷線不良之斷裂時間,得到如第14圖所示之結果。第14圖,係表示對驗證用電路21內之無鉛銲料凸塊接合構造之任一發生電遷移現象而發生斷線不良時所發生的電阻變化率,而當電阻變化率急速上升時,可知因電遷移現象而發生斷線不良。
比較例1之3個驗證用電路21發生斷線不良之平均時間為497小時。另一方面,亦對實施例3及實施例4之驗證用電路21同樣地測量直到發生斷線不良的時間,實施例3在906小時發生斷線不良,實施例4在793小時發生斷線不良。由該結果,於實施例3的驗證用電路21,與於製作後沒有熱處理之實施例1之發生斷線不良之時間並未看到很大的變化。對此,實施例4之驗證用電路21,確認到發生斷線不良之時間,與於製作後沒有熱處理之比較例1相比,變長很多,確認於製作後的熱處理,可得提升耐電遷移性之效果。
其次,驗證改變含於無鉛銲料合金含之Ni的添加量時之IMC界面之剖面形狀。在此,使Sn、Ag、Cu的含量相同,僅改變Ni的添加量。具體而言,準備,包含0.15質量%Ni的Sn-1.2Ag-0.5Cu-0.15Ni作為成分的無鉛銲料合金、包含0.10質量%Ni的Sn-1.2Ag-0.5Cu-0.10Ni作為成分的無鉛銲料合
金、及不包含Ni的Sn-1.2Ag-0.5Cu作為成分的無鉛銲料合金。然後,以與上述實施例1及比較例1完全相同的製作方法及製作條件分別製作驗證用電路21。
然後,對設置包含0.15質量%Ni的Sn-1.2Ag-0.5Cu-0.15Ni所組成之無鉛銲料合金所製作之無鉛銲料凸塊之實施例5之驗證用電路21、設置包含0.10質量%Ni的Sn-1.2Ag-0.5Cu-0.10Ni所組成之無鉛銲料合金所製作之無鉛銲料凸塊之實施例6之驗證用電路21、設置不包括Ni的Sn-1.2Ag-0.5Cu所組成之無鉛銲料合金所製作之無鉛銲料凸塊之比較例2之驗證用電路21,拍攝各無鉛銲料凸塊接合構造之IMC界面剖面之光學顯微鏡照片。
結果,於使用添加0.15質量%Ni之無鉛銲料合金之實施例5,可確認到如第15圖A及第16圖A所示,金屬間化合物層7j、7k,沿著Cu電極表面3a、3b形成於無鉛銲料凸塊35a內。此外,於使用添加0.10質量%Ni之無鉛銲料合金之實施例6,可確認到如第15圖B及第16圖B所示,金屬間化合物層7l、7m,沿著Cu電極表面3a、3b,形成於無鉛銲料凸塊35b內。再者,使用沒有添加Ni之Sn-1.2Ag-0.5Cu之無鉛銲料合金之比較例2,可確認到如第15圖C及第16圖C所示,金屬間化合物層7n、7o,沿著Cu電極表面3a、3b,形成於無鉛銲料凸塊35c內。
添加0.15質量%Ni之實施例5之情形,由第15圖A,上側之金屬間化合物層7j,平均膜厚為4.7[μm](圖中,以平均=4.7μm記述),平均膜厚的30%為1.41[μm](圖中,以
30%平均=1.41μm記述),計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0[個/μm](0個/133[μm])。此外,由第16圖A,下側之金屬間化合物層7k之平均膜厚為2.9[μm](圖中,以平均=2.9μm記述),平均膜厚的30%為0.87[μm](圖中,以30%平均=0.87μm記述),計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0[個/μm](0個/139[μm])。
如此地使用包含0.15質量%Ni之無鉛銲料合金之實施例5之無鉛銲料凸塊接合構造,金屬間化合物層7j、7k之膜厚為平均膜厚之30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀為0.02[個/μm]以下,確認金屬間化合物層7j、7k之IMC界面12均有平坦化。
添加0.10質量%Ni之實施例6之情形,由第15圖B,上側之金屬間化合物層7l,平均膜厚為4.5[μm](圖中,以平均=4.5μm記述),平均膜厚的30%為1.35[μm](圖中,以30%平均=1.35μm記述),計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0.0076[個/μm](1個/132[μm],圖中凹凸形狀處以↓表示)。此外,由第16圖B,下側之金屬間化合物層7m之平均膜厚為3.2[μm](圖中,以平均=3.2μm記述),平均膜厚的30%為0.96[μm](圖中,以30%平均=0.96μm記述),計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0.0074[個/μm](1
個/136[μm],圖中凹凸形狀處以↑表示)。
如此地使用包含0.10質量%Ni之無鉛銲料合金之實施例6之無鉛銲料凸塊接合構造,金屬間化合物層7l、7m之膜厚為平均膜厚之30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀為0.02[個/μm]以下,均為0.008[個/μm]以下,確認金屬間化合物層7l、7m之IMC界面12均有平坦化。
另一方面,不包含Ni的Sn-1.2Ag-0.5Cu之比較例2之情形,由第15圖C,上側之金屬間化合物層7n,平均膜厚為5.0[μm](圖中,以平均=5.0μm記述),平均膜厚的30%為1.5[μm](圖中,以30%平均=1.5μm記述),計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0.104[個/μm](14個/135[μm],圖中凹凸形狀處以↓表示)。此外,由第16圖C,下側之金屬間化合物層7o平均膜厚3.9[μm](圖中,以平均=3.9μm記述),平均膜厚的30%1.17[μm](圖中,以30%平均=1.17μm記述),計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0.072[個/μm](10個/138[μm],圖中凹凸形狀處以↑表示)。
如此地使用完全沒有添加Ni之無鉛銲料合金之比較例2之無鉛銲料凸塊接合構造,金屬間化合物層7n、7o之膜厚為平均膜厚之30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀超過0.02[個/超過μm],金屬間化合物層7n、7o之IMC界面12均凹凸化。
整理以上的點,則於無鉛銲料合金含有0.15質量%、0.10質量%Ni時,可使金屬間化合物層7j、7k、7l、7m、7n、7o之IMC界面12平坦化,結果,抑制由IMC界面12之谷部周邊之Cu擴散,可得提昇耐電遷移性之效果。
接著,對使用在以Sn作為主體之合金及不可避免的雜質,添加0.05質量%Ni的無鉛銲料合金(Sn-0.05Ni)之實施例7之驗證用電路21,拍攝無鉛銲料凸塊接合構造之IMC界面剖面之光學顯微鏡照片。第17圖,係沿著無鉛銲料凸塊35d內之下側之Cu電極3b形成之金屬間化合物層7z之IMC界面剖面之光學顯微鏡照片。由第17圖,下側之金屬間化合物層7z,平均膜厚為4.7[μm](圖中,以平均=4.7μm記述),平均膜厚的30%為1.41[μm](圖中,以30%平均=1.41μm記述)。再者,於該實施形態之情形,Cu電極3b,係以240[μm]電極徑設計值製作者,於製作時,無鉛銲料合金於Cu電極3b上沾濕擴大而底襟部分變長。
於該實施例7之無鉛銲料凸塊接合構造,關於僅進行1次回銲之下側之金屬間化合物層7z,計數膜厚為平均膜厚的30%以下之部分之谷部與鄰接於該谷部之山部之高低差在4[μm]以上的凹凸形狀,結果為0[個/μm](0個/258[μm])。如此地,於實施例7,IMC界面12的凹凸形狀為0.02[個/μm]以下,確認IMC界面12有平坦化。由以上,可說即使是在不包含Ag及Cu以Sn作為主體之無鉛銲料合金含有0.05質量%Ni時,可使金屬間化合物層7z之IMC界面12平坦化,結果,抑制Cu由IMC界面12之谷部周邊之擴散,可得提昇耐電遷移
性之效果。
接著,使用如下第1~5表所示之成分所組成之無鉛銲料合金,以與上述相同的條件將接合WLP及基板接合,製作只有無鉛銲料合金的成分不同的複數種驗證用電路21。然後,於驗證用電路21以與上述同樣的將第1行與第2行連接流放電流。此時,以電壓計量測流於第1行及第2行之電流之末端的無鉛銲料凸塊接合構造B11、B41(B12、B42)間的電壓值,確認伴隨電遷移現象之電壓(電阻)變化。再者,任一驗證用試驗21,製造後沒有進行長時間熱處理(追加的熱處理)。
EM耐性評估,係以凸塊徑150[μm],使電流為2.5[A](電流密度14.15[kA/cm2])評估樣品。於第1表~第5表之EM耐性之欄,未滿500小時發生伴隨電遷移現象之斷線不良時評估為×,在500小時以上,未滿600小時發生時評估為△,進一步在600小時以上,未滿700小時發生時評估為○,在700小時以上未滿800小時發生時評估為○○,在800小時以上,未滿900小時發生時評估為○○○,以900小時以上發生時評估為○○○○。
於上述第1表~第5表以Sn作為主體之合金含有Ni、Co、Fe之任1種0.005~0.2質量%,則可確認會提升EM耐性。此外,以Sn-Ag系、Sn-Cu系或Sn-Ag-Cu系,亦含有Ni、Co、Fe之任1種0.005~0.2質量%,則可確認會提升EM耐性。再者,由第1表之實施例10、1、11及第2表之實施例28、29、30,可知於無鉛銲料合金含有超過0.02質量%,未滿0.100質量%之Ni,則可更加提昇EM耐性。
接著,說明TCT(溫度循環試驗)特性評估用的驗證用電路。使用各組成的銲料材製作直徑300[μm]之無鉛銲料球,準備4[cm]四方的玻璃環氧樹脂基板作為基板,準備1[cm]角的WLP作為晶面。使用於基板及晶片上,形成240個直徑250[μm]的電極者,藉由回銲收先於晶片側形成各種銲料材的無鉛銲料凸塊,之後,藉由覆晶接合製作驗證用電路。再者,WLP的Cu電極的後厚度,基板的Cu電極厚度、回銲條件,以與實施例1相同的條件。在此,對TCT特性評估用的驗證用電路,施加溫度調查TCT特性,得到如第1表~第5表所之結果。
於第1表~第5表之TCT特性之驗證試驗,係反覆施加溫度-40~125[℃](各溫度15分鐘)之熱循環,驗證無鉛銲料接合部(WLP及基板之間的接合部)在哪個階段發生斷裂。於第1表~第5表之TCT特性之欄,於500循環以上亦未發生無鉛銲料接合部之斷裂之試驗片以○表示,於1000循環以上亦未發生無鉛銲料接合部之斷裂之試驗片以○○表示,進一步於1500循環以上亦未發生無鉛銲料接合部之斷裂之試驗片以
○○○表示。由第1表~第5表確認TCT特性均優良。
接著,在於各驗證用電路21,藉由評估回銲後的凸塊表面的氧化膜厚,調查「表面氧化」特性,得到第1表~第5表所示結果。於第1表~第5表之表面氧化之欄,表示將表面氧化膜厚由歐傑分析結果評估之結果。表面氧化膜厚,在7[nm]以下以○表示,在5[nm]以下以○○表示,在3[nm]以下以○○○表示。由該等第1表~第5表,確認均有抑制表面氧化膜之成長。
3a、3b‧‧‧Cu電極
7a、7b‧‧‧金屬間化合物層
12‧‧‧IMC界面
5‧‧‧無鉛銲料凸塊
Claims (4)
- 一種無鉛銲料凸塊接合構造,將第1電子構件的Cu電極與第2電子構件之Cu電極,經由無鉛銲料凸塊接合,電流密度為0.7×103[A/cm2]以上的大電流經由上述無鉛銲料凸塊流過上述第1電子構件及上述第2電子構件之間,其特徵在於:上述無鉛銲料凸塊,係以Sn作為主體之合金及不可避免雜質所構成,在與上述第1電子構件的Cu電極的境界及與上述第2電子構件的Cu電極的境界,形成金屬間化合物層,各上述金屬間化合物層,係於與上述無鉛銲料凸塊的界面,谷部及鄰接於該谷部之山部之高低差為4[μm]以上的凹凸形狀在0.02[個/μm]以下,該谷部是膜厚為該金屬間化合物層之平均膜厚的30%以下的部分,其中上述無鉛銲料凸塊,將Ni、Co、Fe之1種以上,以總計包含0.005~0.2質量%。
- 根據申請專利範圍第1項之無鉛銲料凸塊接合構造,其中上述無鉛銲料凸塊,包含Ag:0~5質量%、Cu:0~2質量%。
- 根據申請專利範圍第1項之無鉛銲料凸塊接合構造,其中上述無鉛銲料凸塊,進一步將P、Mg、Ge之1種以上,以總計包含0~0.01質量%。
- 根據申請專利範圍第1項之無鉛銲料凸塊接合構造,其中上述無鉛銲料凸塊,包含Pd、Mn、Zn、Al、Sb、In之1種以上,Pd、Mn、Al:0~1質量%;Zn:0~10質量%;Sb:0~3質量%;In:0~7質量%。
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