TW202300697A - 以不同電流密度電化學沉積銅之方法 - Google Patents
以不同電流密度電化學沉積銅之方法 Download PDFInfo
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- TW202300697A TW202300697A TW111111373A TW111111373A TW202300697A TW 202300697 A TW202300697 A TW 202300697A TW 111111373 A TW111111373 A TW 111111373A TW 111111373 A TW111111373 A TW 111111373A TW 202300697 A TW202300697 A TW 202300697A
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- Prior art keywords
- copper
- current density
- layer
- copper foil
- rolled
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000010949 copper Substances 0.000 title claims abstract description 131
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 18
- 239000011889 copper foil Substances 0.000 claims abstract description 83
- 238000000151 deposition Methods 0.000 claims abstract description 30
- 238000005530 etching Methods 0.000 claims abstract description 26
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims description 15
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 description 65
- 239000000243 solution Substances 0.000 description 21
- 239000011888 foil Substances 0.000 description 18
- 238000007747 plating Methods 0.000 description 17
- -1 polyethylene Polymers 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
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- 229920000642 polymer Polymers 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 235000001014 amino acid Nutrition 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000002243 precursor Substances 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
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- 229910000365 copper sulfate Inorganic materials 0.000 description 2
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- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
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- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
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- REJSMTWFWDLMQN-UHFFFAOYSA-N 3-(3-sulfopropylsulfanyl)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCSCCCS(O)(=O)=O REJSMTWFWDLMQN-UHFFFAOYSA-N 0.000 description 1
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 1
- LUENVHHLGFLMFJ-UHFFFAOYSA-N 4-[(4-sulfophenyl)disulfanyl]benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1SSC1=CC=C(S(O)(=O)=O)C=C1 LUENVHHLGFLMFJ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1614—Process or apparatus coating on selected surface areas plating on one side
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
本發明係關於一種用於電化學沉積銅之方法，其包含
-提供包含第一表面及第二表面之經軋製及退火銅箔，
-蝕刻該經軋製及退火銅箔的該第一表面，藉此產生第一經蝕刻表面，
-藉由無電鍍銅沉積在該第一經蝕刻表面上沉積銅，藉此在該第一經蝕刻表面上產生第一無電鍍銅層，
-藉由電化學沉積在該第一無電鍍銅層上沉積其他銅，藉此產生第一電化學銅層，其中在該電化學沉積中，在第一時段中施加第一電流密度且在第二時段中施加第二電流密度，其中該第二電流密度低於該第一電流密度；及可藉由該方法獲得之分層產品。
Description
本發明係關於一種用於將銅電化學沉積於RA箔上之方法，及可藉由該方法獲得之分層產品。
自印刷電路板領域中之先前技術已知經軋製及退火銅箔，亦稱為「軋製退火銅箔(rolled annealed copper foil/roll anneal copper foil)」且下文中亦縮寫為RA銅箔。RA銅箔應理解為經退火(亦即，經受退火處理)的軋製銅箔。軋製可藉由軋製銅塊或銅坯料以獲得具有所需厚度之箔來進行，較佳在高壓下進行。退火可藉由加熱軋輥進行，其可在未加熱軋輥之後佈置。經退火銅箔之製造揭示於例如US2009173414A1中。
已知RA銅箔用於可撓性印刷電路板及較小管線。RA銅箔最常用於金屬化次世代可撓性基板以作為可撓性印刷電路板(FPCB)。
可撓性印刷電路板(FPCB)在電子工業中之重要性愈來愈大。一種獲得高度可撓性銅箔之方法為軋製-退火(RA)方法，其根據箔(經高度退火，HA型銅箔)之平面產生約至多100 μm寬之具有大微晶之微觀結構。此等微晶經對齊，其[100]方向沿著軋製方向，且其[001]方向垂直於箔之表面(立方體紋理)。此微觀結構防止在彎曲時應力在晶界處積聚，且因此藉由使初始開裂點最小化來防止金屬疲勞。在生產FPCB時，RA箔層壓於如聚醯亞胺之可撓性聚合物或其他絕緣基板上。為產生多層撓性電路，需要一連串其他鍍銅步驟。在電鍍之前，使用無電鍍在電絕緣之部分表面上沉積銅。
然而，該特殊晶體結構，特定言之對於「超可撓」HA銅箔，需要複雜的電鍍溶液以便達成所需表面形態。一個主要挑戰為電解銅電鍍步驟之後的表面外觀。表面必須具有某種有光澤外觀，以便實現建構期間之均勻蝕刻且確保可靠的自動光學檢驗(AOI)。
RA箔之晶體結構展示半蝕刻製程之後的宏觀非均勻表面。此導致在無電鍍及隨後電化學Cu電鍍之後的無光澤Cu表面。
AOI及後續處理步驟需要有光澤Cu表面。同時，必須填充如盲微孔(BMV)及通孔(THF)之結構(若存在)。對於此類填充，通常至少在電化學銅沉積開始時使用低電流密度。然而，藉由此方法，僅達成無光澤表面外觀。咸信無光澤表面由蝕刻RA箔之預處理引起，該等RA箔具有如上文描述之宏觀非均勻表面。
發明目標本發明之問題為提供一種用於在包含RA銅層、無電鍍銅層及電化學沉積銅層之產品中製造更有光澤或光滑的銅表面之方法。
本發明提供一種用於電化學沉積銅之方法，其包含
- 提供包含第一表面及第二表面之經軋製及退火銅箔，
- 蝕刻該經軋製及退火銅箔的該第一表面，藉此產生第一經蝕刻表面，
- 藉由無電鍍銅沉積在該第一經蝕刻表面上沉積銅，藉此在該第一經蝕刻表面上產生第一無電鍍銅層，
- 藉由電化學沉積在該第一無電鍍銅層上沉積其他銅，藉此產生第一電化學銅層，其中在該電化學沉積中，在第一時段中施加第一電流密度且在第二時段中施加第二電流密度，其中該第二電流密度低於該第一電流密度。
本發明進一步提供一種分層產品，其包含：
- 包含第一經蝕刻表面及第二表面的經軋製及退火銅箔，
- 第一無電鍍銅層，其存在於該經軋製及退火銅箔的該第一經蝕刻表面上，
- 第一電化學銅層，其存在於該第一無電鍍銅層上，
其中該第一電化學銅層具有在60°入射角下具有至少400光澤單位之光澤度的外表面。
本發明之解決方案為具有至少兩種不同電流密度之用具
1. 高起始電流密度持續短時間。在不希望受理論束縛的情況下，咸信此處形成薄障壁層，其避免即使在下一層(第一電化學沉積銅層)中，RA銅上的第一無電鍍銅層仍保持其無光澤度。
2. 較低電鍍電流密度持續第二時段，較佳地為電化學銅沉積之剩餘時間。此處，結構(若存在)填充有銅，且達成銅在包括結構之整個區域上方的分佈，其中分佈可為均勻的，且結構可經填充而無凹痕或過度填充。
在其一般或在特定實施例中，本發明提供以下優點中之一或多者：
- 已展示藉由本發明之方法可獲得電化學沉積銅之光滑/有光澤的表面。
- 所達到之光澤度有益於銅表面之檢驗、表面之外觀及用於其他方法步驟，諸如藉由例如半加成方法構造銅表面。
- 本發明之方法適合於生產用於可撓性印刷電路板之前驅產品。
- 無氣泡之無電鍍銅沉積
- 本發明之方法實現良好的覆蓋範圍及較厚的無電鍍銅沉積物，亦覆蓋在關鍵點處諸如盲微孔(BMV)角落或在通孔內之經暴露黏著層上。
- 本發明之方法允許即使在光滑基板(如由PI製成之支撐層)上亦得到無電鍍沉積銅層的極佳且無氣泡的黏著。
現將詳細參考實施例，其實例在隨附圖式中示出。將參考隨附圖式描述例示性實施例的效果及特徵及其實施方法。如本文所用，術語「及/或」包括一或多個相關聯的所列項目中的任一者及所有組合。另外，在描述本發明之實施例時，「可」的使用係指「本發明之一或多個實施例」。
在本發明之實施例的以下描述中，除非上下文另外明確地指示，否則單數形式的術語可包括複數形式，例如若使用『銅箔(copper foil)』，則包括『銅箔(copper foils)』。
RA銅箔應理解為經軋製及退火(亦即，經受軋製及退火處理)之銅箔。較佳地，晶體之所獲得形狀為層狀結構,且由根據箔平面之粒度為100 µm的巨大晶體組成。較佳地，RA銅將具有平行於加工方向的長型晶粒結構或長型晶體結構，該加工方向為軋製製程之方向，亦即銅箔的輸送方向。較佳地，經軋製及退火銅箔包含經對齊之銅微晶，其[100]方向沿著軋製方向，且其[001]方向垂直於箔之表面(立方體紋理[100])。軋製可藉由軋製銅塊或銅坯料以獲得具有所需厚度之箔來進行，較佳在高壓下進行。退火可藉由加熱軋輥進行，其可在未加熱軋輥之後佈置。本發明並不關於並非由銅塊或銅坯料製成之銅箔，尤其由電流方法製成之如ECD銅箔形式之銅箔在本發明之意義上排除。
術語RA銅箔應理解為涵蓋所謂高度退火之銅箔，下文亦簡稱為HA銅箔。HA銅箔具有較大的晶粒及高度均一的晶向。HA銅箔展示極高可撓性。
在應用蝕刻步驟之前，經軋製及退火銅箔較佳具有6至30 µm、更佳10至20 µm、甚至更佳12至18 µm之厚度。
在一個實施例中，在進行蝕刻步驟之前，所提供之經軋製及退火銅箔與支撐層層壓以獲得層壓基板。在此實施例中，支撐層可包含第一表面及第二表面。這意謂在蝕刻步驟之前，所提供之經軋製及退火銅箔的第二表面與支撐層的第一表面層壓以獲得層壓基板。支撐層較佳地為可撓性非導電塑膠層，更佳為塑膠箔。可撓性非導電塑膠層例如選自如聚醯亞胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚碳酸酯(PC)、液晶聚合物(LCP)及環烯烴共聚物(COC)之可撓性非導電聚合物。可撓性非導電塑膠層可為可撓性塑膠複合層或前述聚合物之摻合層，更佳為聚醯亞胺或聚醯亞胺之摻合物。
在另一實施例中，可將另一經軋製及退火銅箔層壓於該支撐層之第二表面上(該支撐層之第二表面可與該另一經軋製及退火銅箔的第一表面層壓)。在此狀況下，本發明之方法可用層壓於支撐層之該兩個表面上的經軋製及退火銅箔中之兩者來進行，以便獲得層壓基板。
所獲得之一或兩個銅箔與一個支撐層的層壓基板可用作用於製造例如行動電話中之可撓性電路板的前驅產品。
支撐層較佳具有20至70 µm之厚度，更佳為30至50 µm。
在一個實施例中，經軋製及退火銅箔的厚度為6至30 µm。銅箔層壓於厚度為20至70 µm的聚醯亞胺支撐層上。
在一個實施例中，層壓基板(包含一個或兩個銅箔)可例如藉由雷射鑽孔而結構化以獲得盲微孔及視情況存在之通孔。在結構化之後，層壓基板包含穿過銅箔且終止於層壓支撐層上之盲微孔，及視情況包含完全貫穿銅箔及支撐層之通孔。換言之，層壓基板包含盲微孔，其自銅箔的第一表面穿過且終止於支撐層的第一表面上或支撐層內，且視情況包含通孔，其完全貫穿銅箔及支撐層。結構化可後接去污製程，且結構化可在蝕刻步驟之前或在蝕刻步驟之後進行。
在一個實施例中，盲微孔之寬度與深度之比為約1:2至約2.5:1。較佳寬度介於50至150 µm之範圍內，且較佳深度介於30至100 µm之範圍內，更佳地盲微孔具有以下寬度與深度之比：100與40 µm直至70與30 µm範圍內。
在通孔之情況下，較佳縱橫比率(寬度比深度)為1至3，較佳1至1.5。較佳寬度介於50至80 µm之範圍內，更佳為70 µm，且較佳深度介於100至200 µm之範圍內，更佳為110 µm。
蝕刻：蝕刻RA銅箔之表面亦稱為「半蝕刻」。在此步驟中，部分移除RA銅箔之銅，其中形成粗糙銅表面。
蝕刻步驟藉由已知蝕刻溶液進行，其可包含氧化劑，如例如有機或無機過氧化物及無機酸，如硫酸或鹽酸，例如較佳蝕刻溶液包含過氧化氫及硫酸。另外，蝕刻溶液可包含一或多種添加劑及一或多種鹵化物以維持蝕刻穩定性。可使用包含H
2O
2/H
2SO
4及氯離子之標準蝕刻溶液。
蝕刻溶液可藉由例如噴塗或浸沒來施加。
在蝕刻步驟期間，銅層之厚度較佳地減少2至10 µm，更佳減少3至6 µm。
無電鍍銅沉積在蝕刻步驟之後，藉由已知的無電鍍水溶液進行無電鍍銅沉積步驟，該等已知水溶液於例如EP 2784181 B1中所揭示。無電鍍銅電鍍溶液將最有效地形成銅，較佳地形成純銅層(純意謂99重量%或更高之銅含量)，或銅合金層，較佳地在經蝕刻的經軋製及退火銅箔的表面上形成銅層(第一無電鍍銅層)。
大體而言，無電鍍溶液包含如硫酸銅、氯化銅、硝酸銅、乙酸銅、甲烷磺酸銅、氫氧化銅之銅離子來源；用於銅或合金金屬離子之還原劑及錯合劑來源。還原劑之來源可為甲醛、多聚甲醛、乙醛酸、NaBH
4、KBH
4、NaH
2PO
2、肼、福馬林、多醣(諸如葡萄糖)及其混合物，且錯合劑之來源可為乙二胺四乙酸(EDTA)、N'-(2-羥乙基)-乙二胺、N,N,N'-三乙酸(HEDTA)、環己二胺四乙酸、二伸乙三胺五乙酸及N,N,N',N'-四(2-羥丙基)乙二胺(Quadrol)。其他視情況選用之組分為無機酸或鹼、穩定劑、共溶劑、潤濕劑及其他功能性添加劑，諸如光亮劑、促進劑、抑制劑、抗失澤劑。此類溶液及組分為此項技術中已知的。無電鍍銅電鍍浴可進一步包含合金金屬離子來源，如鎳離子、或鈷離子及其混合物。
無電鍍銅電鍍溶液為公眾已知的且可購買，例如購自Atotech Deutschland GmbH。
| 方法 | 化學物質 | 設定值 [mL/L] | 溫度 [ ℃ ] | 停留時間 [min] |
| 無電鍍銅 (MV TP1) | Printoganth MV基礎TP1 | 140 | 34 | 20 |
| Printoganth MV銅TP1 | 85 | |||
| Printoganth MV調節劑TP1 | 3 | |||
| Printoganth MV穩定劑TP1 | 0.6 mL/L (MU) | |||
| 銅還原溶液 | 16 | |||
| pH值校正溶液CC | 7 mL/L (3 g/L) |
典型的無電鍍銅電鍍溶液亦可包含鎳離子且可添加氰離子。電鍍溶液藉由充氣穩定，且在沉積期間用電磁攪拌器攪拌溶液。藉由電鍍30分鐘調節新近製備之電鍍溶液。
較佳藉由使經蝕刻之表面與用於無電鍍銅沉積之銅溶液(亦稱為銅浴)接觸來進行無電鍍沉積。
銅之電化學沉積對於銅之電化學沉積，較佳地使用含水酸性銅電鍍浴。此類浴自先前技術已知，諸如EP2922985及EP3511444。
第二電流密度低於第一電流密度之陳述較佳意謂第二電流密度比第一電流密度低至少0.2 ASD或更多(安培/平方分米；A/dm
2)，較佳低至少0.2至0.5 ASD。
第一電流密度及/或第二電流密度可變化，其中第二電流密度始終低於第一電流密度。第一電流密度及/或第二電流密度可具有下降或傾斜斜坡的形狀。在第一電流密度及/或第二電流密度變化的情況下，較佳第二電流密度的最高值比第一電流密度的最低值低至少0.2 ASD或更多，較佳低至少0.2至0.5 ASD。
第二時段可緊跟在第一時段後。
在第一時段轉換至第二時段時，第一電流密度與第二電流密度之間的差值可為至少0.2 ASD或更多，較佳至少0.2至0.5 ASD。
在一個實施例中，第二電流密度在第一電流密度之5至80%範圍內，較佳在20至70%範圍內，更佳在30至40%範圍內。
在一個實施例中，第二電流密度在0.5至2.1 ASD、較佳0.8至1.6 ASD、更佳1.0至1.3 ASD範圍內。
在一個實施例中，第一電流密度在1至10 ASD、較佳1至4 ASD範圍內。如可見，第一電流密度/第二電流密度之較佳範圍可重疊。然而，根據本發明，第二電流密度始終低於第一電流密度。因此，若例如第一電流密度選擇為1 ASD，則第二電流密度低於1 ASD。
在一個實施例中，第一時段之長度在第二時段之長度的1至25%範圍內，較佳1至10%範圍內，更佳第二時段之長度的8%。
在一個實施例中，第一時段在0.5至5分鐘、較佳1至4分鐘、更佳2至4分鐘範圍內。
在一個實施例中，第二時段在20至60分鐘、較佳30至40分鐘範圍內，最佳50分鐘。
可參考盲微孔或通孔之幾何形狀設定第一電流密度之量值，其中在較小結構，尤其具有較小寬度或較小寬度與深度之比的結構的狀況下，較佳選擇較低第一電流密度，且反之亦然。
在一個實施例中，使用用於沉積之電化學銅溶液，其包含
- 銅離子來源，
- 酸
- 調平劑添加物，及
- 視情況存在之以下組分中之一或多者：促進劑-光亮劑添加物、載劑-抑制劑添加物及/或鹵素離子。
溶液(亦稱為含水酸性銅電鍍浴)較佳地具有≤2、更佳≤1之pH值。
銅離子來源較佳選自包含硫酸銅及磺酸烷基銅(諸如甲烷磺酸銅)之群。含水酸性銅電鍍浴中之銅離子濃度較佳在4 g/l至90 g/l範圍內，更佳在10 g/L至70 g/L範圍內，再更佳在30 g/L至65 g/L範圍內。
酸較佳選自包含硫酸、氟硼酸、磷酸及甲磺酸之群，且較佳以10 g/l至400 g/l，更佳20 g/l至300 g/l，再更佳30 g/L至300 g/L之濃度添加。
調平劑添加物較佳選自一或多種選自由以下組成之群的化合物：伸脲基聚合物、含氮有機化合物諸如聚乙二亞胺、烷氧基化聚乙二亞胺、烷氧基化內醯胺及其聚合物、二伸乙基三胺及六亞甲基四胺、帶有聚伸乙亞胺之肽、帶有聚伸乙亞胺之胺基酸、帶有聚乙烯醇之肽、帶有聚乙烯醇之胺基酸、帶有聚烷二醇之肽、帶有聚烷二醇之胺基酸、帶有胺基伸烷基之吡咯及帶有胺基伸烷基之吡啶、脲基聚合物、有機染料(諸如詹納斯(Janus)綠B、俾斯麥(Bismarck)棕Y及酸性紫7)、含有硫之胺基酸(諸如半胱胺酸)、啡·離子鹽及其衍生物。該視情況選用之調平劑添加物以0.1 mg/l至100 mg/l之量(總計)添加至含水酸性銅電鍍浴中。所提及伸脲基聚合物較佳為如EP2922985A中所揭示之伸脲基聚合物。
促進劑-光亮劑添加物較佳選自一或多種選自由以下組成之群的化合物：有機硫醇化合物、硫化物化合物、二硫化物化合物及聚硫化物化合物，較佳選自由以下組成之群：3-(苯并噻唑基-2-硫基)-丙基磺酸、3-巰基丙烷-1-磺酸、伸乙基二硫丙基磺酸、雙(對磺基苯基)-二硫化物、雙(ω-磺丁基)-二硫化物、雙(ω-磺羥丙基)-二硫化物、雙(ω-磺丙基)-二硫化物、雙(ω-磺丙基)-硫化物、甲基-(ω-磺丙基)-二硫化物、甲基-(ω-磺丙基)-三硫化物、O-乙基-二硫碳酸-S-(ω-磺丙基)酯、硫乙醇酸、硫代磷酸-O-乙基-雙(ω-磺丙基)酯、3-N,N-二甲基胺基二硫代胺甲醯基-1-丙磺酸、3,3'-硫基雙(1-丙磺酸)、硫代磷酸-參(ω-磺丙基)酯及其對應鹽。視情況存在於含水酸性銅浴組合物中之所有促進劑-光亮劑添加物之濃度(總計)較佳在0.01 mg/l至100 mg/l範圍內，更佳在0.05 mg/l至10 mg/l範圍內，再更佳在0.1 mg/L至5 mg/L範圍內。
載劑-抑制劑添加物較佳選自一或多種選自由以下組成之群的化合物：聚乙烯醇、羧甲基纖維素、聚乙二醇、聚丙二醇、硬脂酸聚二醇酯、烷氧基化萘酚、油酸聚二醇酯、硬脂醯基醇聚二醇醚、壬基酚聚二醇醚、辛醇聚伸烷基二醇醚、辛二醇-雙-(聚伸烷基二醇醚)、聚(乙二醇-
無規-丙二醇)、聚(乙二醇)-
嵌段-聚(丙二醇)-
嵌段-聚(乙二醇)，及聚(丙二醇)-
嵌段-聚(乙二醇)-
嵌段-聚(丙二醇)。該等視情況選用之載劑-抑制劑添加物之濃度(總計)較佳在0.005 g/l至20 g/l範圍內，更佳在0.01 g/L至20 g/L範圍內，再更佳在0.01 g/l至5 g/l範圍內。
視情況存在之鹵化物離子較佳選自Cl、Br及/或I。在氯化物之情況下，鹵化物離子較佳以10至200 mg/L，更佳20至80 mg/L或30至60 mg/L添加。若選擇其他鹵化物離子，則較佳選擇各別莫耳量，或若選擇不同鹵化物，則選擇各別總莫耳量。
在根據本發明之方法中，較佳地在15℃至50℃範圍內之溫度下，更佳地在25℃至40℃範圍內之溫度下藉由將電流施加至基板及至少一個陽極，操作含水酸性銅電鍍浴。
若需要，可在上述步驟之間進行額外步驟作為沖洗步驟，例如使用DI水、清潔器之步驟；預浸漬步驟；及/或乾燥步驟。
本發明之方法可包含以下步驟中之一或多者，按任何次序
- 自動光學檢驗
- 藉由使用已知光微影方法構造銅表面
- 另一蝕刻步驟
- 一或多個其他金屬層之沉積，諸如Cu、Ni、Au等。
在另一態樣，本發明涉及經由本發明的方法獲得或可獲得的分層產品。
在分層產品之一個實施例中，電化學沉積銅層具有沿RA銅箔之加工方向(MD)量測在60°入射角下具有至少400光澤單位之光澤度的外表面。用於量測光澤度之方法在實例部分中給出。光澤度較佳為400至800光澤單位、更佳400至600光澤單位、再更佳400至500光澤單位。
在另一態樣中，本發明提供一種分層產品，其包含：
- 包含第一經蝕刻表面及第二表面的經軋製及退火銅箔，
- 第一無電鍍銅層，其存在於該經軋製及退火銅箔的該第一經蝕刻表面上，
- 第一電化學銅層，其存在於該第一無電鍍銅層上，
其中該第一電化學銅層具有一外表面，該外表面沿RA銅箔之加工方向(MD)量測在60°入射角下具有至少400光澤單位之光澤度。用於量測光澤度之方法在實例部分中給出。光澤度較佳為400至800光澤單位、更佳400至600光澤單位、再更佳400至500光澤單位。
以60°之反射角反射的光束之強度可使用例如BYK-Gardner GmbH之Micro Gloss 60°光澤計量測，其符合DIN 67530、ISO 2813、ASTM D523及BS 3900 D5部分。
此產品可根據本發明方法獲得或可獲得。因此，關於本方法所描述之所有特徵可單獨或組合地為產品之特徵。另一方面，本發明之方法可包含關於產品描述之一或多個特徵。
第一無電鍍銅層可藉由無電鍍銅沉積獲得或可獲得，其已於先前描述。
第一電化學銅層可藉由電化學銅沉積獲得或可獲得，其已於先前描述。在藉由電化學沉積製備該第一電化學銅層時，在第一時段施加第一電流密度且在第二時段施加第二電流密度，其中該第二電流密度低於該第一電流密度。就此而言，吾等亦參考方法及電流密度之上文描述。
第一無電鍍銅層較佳地具有0.1 µm至4 µm、更佳0.2 µm至2 µm之厚度。
第一電化學銅層較佳具有2 µm至15 µm、更佳4 µm至12 µm、最佳5 µm至10 µm之厚度。
該第一電化學銅層較佳比該第一無電鍍銅層厚。第二銅層與第一銅層之厚度的比較佳在30:1至3:1範圍內。
可將經軋製及退火銅箔層壓至支撐層，其較佳為可撓性非導電塑膠層，諸如聚醯亞胺層，如先前所描述。因此，在分層產品之一個實施例中，經軋製及退火銅箔的第二表面與支撐層之第一表面層壓。就此而言，吾等參考關於支撐層之先前揭示內容。在此實施例中，分層產品可用作可撓性電路板之前驅產品。
實例光澤度之測定：
如下量測光澤度。量測光束沿著RA銅箔之加工方向(MD)以60°之入射角施加至經表面處理之電解銅箔的表面。加工方向為軋製製程之方向，亦即銅箔之輸送方向。以60°之反射角反射的光束之強度使用BYK-Gardner GmbH之Micro Gloss 60°光澤計量測，其符合DIN 67530、ISO 2813、ASTM D523及BS 3900 D5部分。
圖1顯示用於製造RA箔之方法流程圖。在減徑軋輥2之間引入銅錠1以減少厚度。接著將所獲得之箔引入於加熱軋輥之間以供退火，且接著獲得RA銅箔4且將其捲起。
圖2展示根據先前技術，在不同基板上之銅沉積方法的流程圖。流程圖中之上列展示銅沉積於藉由電化學沉積製成之銅箔5 (ECD銅箔5)上。下列展示銅在RA銅箔6上的沉積。在第一步驟A (其在本發明之方法中並非必選的)中，ECD銅箔5及RA銅箔6經層壓至塑膠箔7 (例如聚醯亞胺箔)上。接著，進行所謂的半蝕刻步驟B，在銅上產生粗糙表面。可看出，由於RA銅之特定結構(具有定向於軋製方向上之大晶體/晶粒結構)，經蝕刻之RA銅箔6上的表面比經蝕刻之ECD銅箔5上的表面更加不均勻。由於銅晶體結構及其原始生產方法，在半蝕刻製程B之後，RA/HA箔之晶體結構展示宏觀尺度之非均勻表面。在下一步驟C中，進行無電鍍銅沉積，且獲得薄無電鍍銅層8。藉此保持RA銅箔6上之非均勻表面結構。在最後步驟D中，藉由電化學沉積以一個電流密度沉積銅且獲得銅層9。藉此，在蝕刻B之後的RA銅箔6上之不均勻表面結構仍保持且在銅層9之表面上前進。
若產生盲微孔或溝槽，則此在步驟A之後且在B之前(亦即，在半蝕刻之後)或在步驟B之後且在步驟C之前(在無電鍍銅沉積之前)進行。接著可應用清潔及活化步驟(例如用Pd)。
實例 1 ( 比較 )比較實例示意性地展示於圖2中之下列中。
用以下溶液進行RA銅箔之蝕刻B：150 ml/L 50% H
2SO
4、120 ml/L 30% H
2O
2、2 mg/L氯化物(NaCl)。
接著，用以下銅浴進行無電鍍銅沉積C：
表1：浴及操作條件：
| 含量 | |||
| [Cu 2+] | 2.2 g/L | ||
| [KNaC 4H 4O 6⸳4H 2O] | 35 g/L | ||
| [HCHO] | 4.4 g/L | ||
| [NaOH] | 9 g/L | ||
| [Ni 2+] | 0.5 g/L | ||
| [NaCN] | 0.01 g/L | ||
| 溫度 | 32℃ | ||
| pH | 12.5 15 – 20分鐘 | ||
| 電鍍時間 | |||
用自EP 2922985 A已知之酸性銅浴進行銅之電化學沉積D，該酸性銅浴為：含水酸性銅電解質，其包含55 g/L銅離子、50 g/L硫酸、50 mg/L氯離子、3 ml/L SPS。
電化學沉積以0.7 ASD進行4分鐘且以1.3 ASD進行48分鐘。
實例 2 ( 比較 )與實例1中使用相同的程序，不同之處在於以1.3 ASD進行電化學沉積50分鐘。
實例 2 ( 本發明 )除電化學沉積以2.6 ASD (第一電流密度)進行4分鐘(第一時段)且接著以1.3 ASD (第二電流密度)進行42分鐘(第二時段)以外，使用與實例1及2相同的程序。
結果根據上文描述的方法量測光澤度。
在圖3中展示結果。自左至右展示實例1、實例2及實例3。可看到，在本發明之實例中，達成約425單位之外部銅表面之光澤度，而分別地，在實例1中僅達成約60單位之光澤度，且在實例2中僅達成約120單位之光澤度。此等結果表明本發明之作用，當在第一時段中施加第一電流密度且在第二時段中施加第二電流密度時，其中第二電流密度低於第一電流密度，可獲得具有較高光澤度之表面。
另外，可發現：
– 起始(4分鐘)電流密度愈高，光澤度愈高
– 經半蝕刻之樣本比未經蝕刻樣本對參數變化更加敏感
1:銅錠
2:減徑軋輥
3:加熱軋輥
4:RA銅箔
5:銅箔/ECD銅箔
6:RA銅箔
7:塑膠箔
8:薄無電鍍銅層
9:銅層
圖1展示用於製造RA箔之方法流程圖；
圖2展示在不同基板上之銅沉積方法的流程圖；
圖3展示根據本發明之實例相較於比較實例中光澤度之實驗資料。
Claims (15)
- 一種用於電化學沉積銅之方法，其包含以下步驟： 提供包含第一表面及第二表面之經軋製及退火銅箔， 蝕刻該經軋製及退火銅箔的該第一表面，藉此產生第一經蝕刻表面， 藉由無電鍍銅沉積在該第一經蝕刻表面上沉積銅，藉此在該第一經蝕刻表面上產生第一無電鍍銅層， 藉由電化學沉積在該第一無電鍍銅層上沉積其他銅，藉此產生第一電化學銅層，其中在該電化學沉積中，在第一時段中施加第一電流密度且在第二時段中施加第二電流密度，其中該第二電流密度低於該第一電流密度。
- 如請求項1之方法，其中第二電流密度在該第一電流密度之1%至50%範圍內。
- 如請求項1或2之方法，其中第二電流密度在0.5 ASD至2.1 ASD範圍內。
- 如請求項1或2之方法，其中第一電流密度在1 ASD至10 ASD範圍內。
- 如請求項1或2之方法，其中該第一時段之長度在該第二時段之長度的1%至25%範圍內。
- 如請求項1或2之方法，其中該第一時段在0.5分鐘至5分鐘範圍內。
- 如請求項1或2之方法，其中該第二時段在20分鐘至45分鐘範圍內。
- 如請求項1或2之方法，其中在蝕刻步驟之前，所提供之經軋製及退火銅箔的該第二表面與支撐層之第一表面層壓以獲得層壓基板。
- 如請求項8之方法，其中該層壓基板的該銅箔包含盲微孔，其自該銅箔的該第一表面穿過且終止於支撐層的該第一表面上或該支撐層內，且視情況包含通孔，其完全貫穿該銅箔及該支撐層。
- 如請求項9之方法，其中該等盲微孔具有1:2至2.5:1之寬度與深度的比。
- 如請求項9之方法，其中該等盲微孔具有50 µm至150 µm之寬度及30 µm至100 µm之深度。
- 如請求項8之方法，其中該支撐層為可撓性非導電塑膠層。
- 如請求項8之方法，其中該支撐層具有20 µm至70 µm之厚度。
- 一種分層產品，其包含： 包含第一經蝕刻表面及第二表面的經軋製及退火銅箔， 第一無電鍍銅層，其存在於該經軋製及退火銅箔的該第一經蝕刻表面上， 第一電化學銅層，其存在於該第一無電鍍銅層上， 其中該第一電化學銅層具有在60°入射角下具有至少400光澤單位之光澤度的外表面。
- 如請求項14之分層產品，其中該經軋製及退火銅箔的該第二表面與支撐層之第一表面層壓。
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| EP21164953.8A EP4063533A1 (en) | 2021-03-25 | 2021-03-25 | A process for electrochemical deposition of copper with different current densities |
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| TWI263461B (en) * | 2003-12-26 | 2006-10-01 | Ind Tech Res Inst | Enhanced flexible copper foil structure and fabrication method thereof |
| TW200738913A (en) * | 2006-03-10 | 2007-10-16 | Mitsui Mining & Smelting Co | Surface treated elctrolytic copper foil and process for producing the same |
| WO2008153185A1 (ja) * | 2007-06-15 | 2008-12-18 | Meltex Inc. | プリント配線板製造用の埋設銅めっき方法及びその埋設銅めっき方法を用いて得られるプリント配線板 |
| US20090173414A1 (en) | 2008-01-08 | 2009-07-09 | Takemi Muroga | Rolled Copper Foil and Manufacturing Method of Rolled Copper Foil |
| EP2735627A1 (en) | 2012-11-26 | 2014-05-28 | ATOTECH Deutschland GmbH | Copper plating bath composition |
| EP2784181B1 (en) | 2013-03-27 | 2015-12-09 | ATOTECH Deutschland GmbH | Electroless copper plating solution |
| KR101887791B1 (ko) * | 2013-12-10 | 2018-08-10 | 제이엑스금속주식회사 | 표면 처리 동박, 구리 피복 적층판, 프린트 배선판, 전자 기기 및 프린트 배선판의 제조 방법 |
| US10512174B2 (en) * | 2016-02-15 | 2019-12-17 | Rohm And Haas Electronic Materials Llc | Method of filling through-holes to reduce voids and other defects |
| EP3511444B1 (en) | 2018-01-16 | 2020-07-22 | ATOTECH Deutschland GmbH | Metal or metal alloy deposition composition and plating compound |
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| JP2024510819A (ja) | 2024-03-11 |
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