TWI605159B - 粗化處理銅箔、貼銅層合板及印刷配線板 - Google Patents

粗化處理銅箔、貼銅層合板及印刷配線板 Download PDF

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Publication number
TWI605159B
TWI605159B TW105122915A TW105122915A TWI605159B TW I605159 B TWI605159 B TW I605159B TW 105122915 A TW105122915 A TW 105122915A TW 105122915 A TW105122915 A TW 105122915A TW I605159 B TWI605159 B TW I605159B
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Taiwan
Prior art keywords
copper foil
roughened
treatment
needle
metal
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TW105122915A
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English (en)
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TW201716641A (zh
Inventor
茂木暁
津吉裕昭
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三井金屬鑛業股份有限公司
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    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
    • C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
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    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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    • C—CHEMISTRY; METALLURGY
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H—ELECTRICITY
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    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/188—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by direct electroplating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer
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Description

粗化處理銅箔、貼銅層合板及印刷配線板
本發明係有關於粗化處理銅箔、貼銅層合板及印刷配線板。
作為適於微距電路之形成的印刷配線板銅箔，有人提出具備經過氧化處理及還原處理(以下有總稱為氧化還原處理)而形成之微細凹凸作為粗化處理面的粗化處理銅箔。
例如，專利文獻1(國際公開第2014/126193號)中揭露一種表面處理銅箔，其表面具備以由最大長度為500nm以下之銅複合化合物構成的針狀微細凹凸所形成的粗化處理層。又，專利文獻2(國際公開第2015/040998號)中揭露一種銅箔，其中至少一面具備：粗化處理層，係具有由銅複合化合物構成之最大長度為500nm以下之大小的針狀凸狀部所形成的微細凹凸；及該粗化處理層的表面上的矽烷偶合劑處理層。根據此等文獻之粗化處理銅箔，茲認為可藉由粗化處理層之微細凹凸所產生的錨定效應而獲得與絕緣樹脂基材之間的良好的密接 性，同時可達具備良好的蝕刻因數之微距電路的形成。專利文獻1及2所揭露之具有微細凹凸的粗化處理層，均是進行過鹼脫脂等的預處理後，再經過氧化還原處理而形成者。如此形成的微細凹凸係具有以銅複合化合物之針狀結晶所構成的特有形狀，而具備所述微細凹凸的粗化處理面，比起藉由微細銅粒之附著所形成的粗化處理面、或藉由蝕刻賦予凹凸的粗化處理面略更為微細。
[先前技術文獻] [專利文獻]
[專利文獻1]國際公開第2014/126193號
[專利文獻2]國際公開第2015/040998號
然而，對於具備以藉由氧化還原處理形成的針狀結晶所構成之微細凹凸的粗化處理面，企望與絕緣樹脂之密接性、及可靠性之更進一步的改善。
本案發明人等近來獲得以下見解：對於在其中至少一側具有具備以針狀結晶構成之微細凹凸的粗化處理面的粗化處理銅箔，藉由使針狀結晶的表面整體由Cu金屬與Cu2O的混相所構成，可顯著提升與絕緣樹脂之密接性、及可靠性(例如吸濕耐熱性)。
因此，本發明之目的在於提供一種可顯著提 升與絕緣樹脂之密接性、及可靠性(例如吸濕耐熱性)的粗化處理銅箔。
根據本發明一形態，係提供一種粗化處理銅箔，其係在其中至少一側具有具備以針狀結晶構成之微細凹凸的粗化處理面之粗化處理銅箔，其中前述針狀結晶的表面係整體由Cu金屬與Cu2O的混相所構成。
根據本發明另一形態，係提供一種貼銅層合板，其係具備上述形態之粗化處理銅箔。
根據本發明又一形態，係提供一種印刷配線板，其係具備上述形態之粗化處理銅箔。
第1圖為拍攝構成例1中所得之粗化處理銅箔之粗化處理面的微細凹凸之剖面的剖面SEM影像。
第2圖為拍攝構成例1中所得之粗化處理銅箔之粗化處理面的微細凹凸(尤為針狀結晶)之剖面的STEM-HAADF像。
第3A圖拍攝構成例1中所得之粗化處理銅箔之粗化處理面的微細凹凸(尤為針狀結晶)之剖面的TEM影像。
第3B圖為第3圖所示之TEM影像的部分放大影像。
第4圖為一併顯示：顯示構成例1中所得之粗化處理銅箔之微細凹凸的針狀結晶的STEM-HAADF像、及在該影像之附有圓圈的針部分與銅箔主體之各部分取得的Cu- L2,3端相關之EELS之能譜的圖。
第5圖為一併顯示：顯示構成例1中所得之粗化處理銅箔之微細凹凸的針狀結晶之針前端部的STEM-HAADF像、及在該影像之附有圓圈的外周部分與芯之各部分取得的Cu-L2,3端相關之EELS之能譜的圖。
第6圖為顯示：構成例1中所得之粗化處理銅箔之微細凹凸的針狀結晶之針前端部的STEM-HAADF像、與該影像之以虛線框包圍之區域的STEM-EELS映射(氧及銅映射)的圖。
第7圖為一併顯示：顯示構成例2中所得之粗化處理銅箔之微細凹凸的針狀結晶之針前端部的STEM-HAADF像、及在該影像之附有圓圈的外周散佈部分、外周主要部分及芯部分之各部分取得的Cu-L2,3端相關之EELS之能譜的圖。
第8圖為顯示銅氧化物之O-K端及Cu-L2,3端相關之周知之EELS能譜的圖。
[實施發明之形態]
粗化處理銅箔
本發明之銅箔為粗化處理銅箔。該粗化處理銅箔係在其中至少一側具有粗化處理面。粗化處理面係具備以針狀結晶構成的微細凹凸，所述微細凹凸可經過氧化還原處理 而形成；典型上，可觀察到針狀結晶與銅箔面略呈垂直及/或朝斜向地繁茂生長之形狀(例如草地狀)。而且，該粗化處理面，針狀結晶的表面係整體由Cu金屬與Cu2O的混相所構成。如此，在具備以針狀結晶構成之微細凹凸的粗化處理面，藉由使針狀結晶的表面整體由Cu金屬與Cu2O的混相所構成，可顯著提升與絕緣樹脂之密接性、及可靠性(例如吸濕耐熱性)。特別是，以與絕緣樹脂之密接性而言，本發明之粗化處理銅箔不僅在常態下的密接性優良，在吸濕後或酸處理後的密接性亦優異，故可呈現不受步驟歷程影響的穩定之高密接性。又，以可靠性而言，本發明之粗化處理銅箔，在長時間放置於高濕度環境下後，實施高溫處理(例如在回流爐中的處理)，仍可發揮完全或幾乎不會呈現銅箔的變形(例如膨脹)之優良的吸濕耐熱性。就此點而言，就本案發明人等所確認，如專利文獻1所揭露之習知粗化處理銅箔中的針狀結晶的表面其主要部分係以Cu金屬所構成，Cu金屬與Cu2O的混相僅局部地散佈。相對於此，本發明之粗化處理銅箔的針狀結晶其表面係整體由Cu金屬與Cu2O的混相所構成，由此，比起習知粗化處理銅箔，可謂在針狀結晶的表面Cu2O以面狀普遍地存在。而且，一般認為Cu2O比Cu金屬更容易與絕緣樹脂形成化學鍵。如此，透過更容易與絕緣樹脂形成化學鍵的Cu2O在針狀結晶的表面以面狀普遍地存在，推測可顯著提升與絕緣樹脂之密接性或吸濕耐熱性等的可靠性。
諸如上述，粗化處理面的微細凹凸係以針狀 結晶構成。針狀結晶的高度(即針狀結晶的根部至沿垂直方向測得的高度)較佳為50~400μm，更佳為100~400μm，再更佳為150~350μm。此種針狀結晶的高度，比起習知粗化處理銅箔中的針狀結晶係較低。縱為如此較低的針狀結晶之高度，如上述透過使針狀結晶的表面整體由Cu金屬與Cu2O的混相所構成，反而可實現高密接性。如此較低的針狀結晶之高度，可謂起因於供形成以表面整體由Cu金屬與Cu2O的混相所構成之針狀結晶構成的微細凹凸的氧化還原處理所賦予者。又，經過所述氧化還原處理所形成的微細凹凸，典型上針狀結晶的前端係略帶圓形。特別是，基於提升與絕緣樹脂之密接性的觀點，較佳為針狀結晶隨機且密集地形成極富空隙的粗化層而成；更佳的是，極富空隙的粗化層係具有針狀結晶密集形成草地狀之形態。
此外，針狀結晶的表面之Cu金屬與Cu2O的混相的存在可藉由使用STEM(掃描穿透電子顯微鏡)的EELS(電子能量損失能譜法)(下稱STEM-EELS)，取得Cu-L端的電子能量損失能譜並進行鑑定來確認。歸屬於Cu金屬/Cu2O混相之能譜的鑑定將於後述之實施例中更詳細地說明；原則上，可透過確認滿足以下之i)~iv)來進行。此外，以下之基準中所記載的「XeV附近」(X係取任意值)之用語，係可容許X±5eV之範圍的變動。
i)在約938eV附近有峰P938。
ii)在約959eV附近亦有峰P959。
iii)峰P938的強度I938與峰P959的強度I959約略相同程度或者相近似(即I938≒I959)或比強度I938高(即I938<I959)。
iv)結果P938與P959之間成為波谷。
針狀結晶的表面之Cu金屬與Cu2O的混相的厚度典型上為10nm以下，更典型為1~5nm。若為此種厚度，則可提升針狀結晶與絕緣樹脂的反應性，不僅可提升常態下的密接性，還可提升吸濕後或酸處理後的密接性。該混相的厚度之下限值不特別限定，係1個原子的量或能以分析儀器確認的最小值。
另一方面，位於以該混相構成的表面之內側的針狀結晶之內部，典型上係以Cu金屬的單相所構成。「針狀結晶之內部係以Cu金屬的單相所構成」，可藉由STEM-EELS取得Cu-L端的電子能量損失能譜並進行鑑定來確認之。歸屬於Cu金屬之能譜的鑑定，原則上可透過確認滿足以下之1)~4)來進行。
1)在約938eV附近有峰P938。
2)在約959eV附近亦有峰P959。
3)峰P959的強度I959係高於峰P938的強度I938(即I938<I959)。
4)在940~950eV附近進一步有2個峰。
本發明之粗化處理銅箔的厚度不特別限定，較佳為0.1~35μm，更佳為0.5~18μm。此外，本發明之粗化處理銅箔不限於對一般的銅箔的表面進行過粗化處理 者，亦可為對附載體銅箔的銅箔表面進行過粗化處理者。
製造方法
本發明之粗化處理銅箔可為藉由各種的方法製造而成者，惟較佳為經過氧化還原處理所製造者。以下，茲說明本發明之粗化處理銅箔的較佳製造方法的一例。該較佳製造方法係包含準備銅箔的步驟、及對上述表面依序進行第1前處理、第2前處理、氧化處理及還原處理的粗化步驟(氧化還原處理)而成。
(1)銅箔的準備
作為粗化處理銅箔之製造所使用的銅箔，可使用電解銅箔及軋製銅箔此兩者，更佳為電解銅箔。又，銅箔可為未經粗化之銅箔，也可為實施過預粗化者。銅箔的厚度不特別限定，較佳為0.1~35μm，更佳為0.5~18μm。當銅箔以附載體銅箔之形態準備時，銅箔可為藉由無電解鍍銅法及電解鍍銅法等的濕式成膜法、濺鍍及化學蒸鍍等的乾式成膜法、或彼等之組合所形成者。
進行粗化處理所成之銅箔的表面較佳具有依據JIS B0601-2001測得之十點平均粗糙度Rzjis為1.5μm以下的表面，更佳為1.3μm以下，再更佳為1.0μm以下。下限值不特別限定，例如為0.1μm以上。
(2)粗化處理(氧化還原處理)
較佳為如此對上述銅箔的表面實施依序進行第1前處理、第2前處理、氧化處理及還原處理之採用濕式的粗化處理。特別是，透過以使用溶液的濕式法對銅箔的表面進行氧化處理，而於銅箔表面形成含有CuO的銅化合物。其後，藉由對該銅化合物實施還原處理使CuO轉換為Cu金屬或Cu2O，便可將以針狀結晶構成的微細凹凸形成於銅箔的表面，該針狀結晶係內部為Cu金屬且表面整體由Cu金屬與Cu2O的混相所構成。於此，微細凹凸係在對銅箔的表面以濕式法進行氧化處理的階段，藉由以CuO為主成分的銅化合物所形成。而且，對該銅化合物進行還原處理時，在大致維持該藉由銅化合物所形成之微細凹凸之形狀的狀態下，CuO經轉換為Cu金屬或Cu2O，便形成其表面整體由Cu金屬與Cu2O的混相所構成的微細凹凸。如此對銅箔的表面以濕式法實施適切的氧化處理後，藉由實施還原處理，可形成本發明特有的微細凹凸。
(2a)第1前處理
該第1前處理係藉由將上述銅箔浸漬於硫酸系水溶液後再用水加以清洗來進行。硫酸系水溶液的硫酸濃度不特別限定，較佳為1~20質量%。可使硫酸系水溶液進一步含有過氧化氫，此時，硫酸系水溶液中的過氧化氫濃度較佳為1~5質量%。硫酸系水溶液的液溫較佳為20~50℃。銅箔對硫酸系水溶液的浸漬時間較佳為2秒~5分。
(2b)第2前處理
該第2前處理係藉由將實施過上述第1前處理的銅箔浸漬於氫氧化鈉水溶液而進行鹼脫脂處理後，再用水加以清洗來進行。氫氧化鈉水溶液的NaOH濃度較佳為20~60g/L。氫氧化鈉水溶液的液溫較佳為30~60℃。對氫氧化鈉水溶液的浸漬時間較佳為2秒~5分。
(2c)氧化處理
對實施過上述第2前處理的銅箔使用氫氧化鈉溶液等的鹼溶液進行氧化處理。透過以鹼溶液將銅箔的表面氧化，便可將以針狀結晶構成的微細凹凸形成於銅箔的表面，該針狀結晶係由以CuO為主成分的銅複合化合物所構成。此時，鹼溶液的溫度較佳為60~85℃，鹼溶液的pH較佳為10~14更佳為12~14。又，基於氧化之觀點，鹼溶液較佳包含氯酸鹽、亞氯酸鹽、次氯酸鹽、過氯酸鹽，其濃度較佳為100~500g/L。氧化處理較佳藉由將銅箔浸漬於鹼溶液來進行，其浸漬時間(即氧化時間)較佳為10秒~20分鐘，更佳為30秒~10分。
氧化處理所使用的鹼溶液較佳進一步包含氧化抑制劑。換言之，藉由鹼溶液對銅箔的表面實施氧化處理時，有時該凸狀部會過度生長，超過所要的長度，而不易形成所要的微細凹凸。因此，為了形成上述微細凹凸，較佳使用包含可抑制銅箔表面之氧化的氧化抑制劑的鹼溶 液。作為較佳之氧化抑制劑的實例，可舉出胺基系矽烷偶合劑。透過使用包含胺基系矽烷偶合劑的鹼溶液對銅箔表面實施氧化處理，該鹼溶液中的胺基系矽烷偶合劑便吸附於銅箔的表面，而能夠抑制鹼溶液所致之銅箔表面的氧化。其結果，可抑制氧化銅之針狀結晶的生長，而能夠形成具備極微細之凹凸的較佳之粗化處理面。作為胺基系矽烷偶合劑的具體例，可舉出N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷等，特佳為N-苯基-3-胺基丙基三甲氧基矽烷。此等均可溶解於鹼性溶液，在鹼性溶液中穩定地保持，同時可發揮抑制上述之銅箔表面的氧化的效果。鹼溶液中之胺基系矽烷偶合劑(例如N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷)的較佳濃度為0.01~20g/L，更佳為0.02~20g/L。
(2d)還原處理
對實施過上述氧化處理的銅箔(下稱氧化處理銅箔)使用還原處理液進行還原處理。藉由還原處理使CuO轉換為Cu金屬或Cu2O，由此可將以針狀結晶構成的微細凹凸形成於銅箔的表面，該針狀結晶係內部為Cu金屬且表面整體由Cu金屬與Cu2O的混相所構成。該還原處理只要藉由使氧化處理銅箔接觸還原處理液來進行即可，較佳藉 由使氧化處理銅箔浸漬於還原處理液中的手法、或對氧化處理銅箔以淋洗器沖淋還原處理液的手法來進行，其處理時間較佳為2~60秒，更佳為5~30秒。此外，較佳之還原處理液為二甲基胺硼烷水溶液，該水溶液係較佳以10~40g/L的濃度含有二甲基胺硼烷。又，二甲基胺硼烷水溶液較佳使用碳酸鈉與氫氧化鈉調整成pH12~14。此時的水溶液的溫度不特別限定，可為室溫。如此進行過還原處理的銅箔較佳經過水洗、乾燥。此時的乾燥溫度較佳設為80~125℃，更佳為110~120℃。乾燥時間可為3~60秒等的短時間，更佳為5~30秒。
(3)矽烷偶合劑處理
亦可視需求對銅箔實施矽烷偶合劑處理，而形成矽烷偶合劑層。藉此可提升耐濕性、耐藥品性及與接著劑等之密接性等。矽烷偶合劑層可藉由將矽烷偶合劑適當稀釋並進行塗佈，再使其乾燥而形成。作為矽烷偶合劑之實例，可舉出4-縮水甘油基丁基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷等的環氧官能性矽烷偶合劑，或3-胺基丙基三乙氧基矽烷、N-2(胺基乙基)3-胺基丙基三甲氧基矽烷、N-3-(4-(3-胺基丙氧基)丁氧基)丙基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷等的胺基官能性矽烷偶合劑，或3-巰基丙基三甲氧基矽烷等的巰基官能性矽烷偶合劑或乙烯基三甲氧基矽烷、乙烯基苯基三甲氧基矽烷等的烯烴官能性矽烷偶合劑，或3-甲基丙烯醯氧 丙基三甲氧基矽烷等的丙烯酸官能性矽烷偶合劑，或咪唑矽烷等的咪唑官能性矽烷偶合劑，或三嗪矽烷等的三嗪官能性矽烷偶合劑等。
貼銅層合板
本發明之粗化處理銅箔較佳使用於印刷配線板用貼銅層合板的製作。亦即，根據本發明較佳形態，係提供一種具備上述粗化處理銅箔的貼銅層合板、或使用上述粗化處理銅箔所得的貼銅層合板。該貼銅層合板係具備本發明之粗化處理銅箔、及與該粗化處理銅箔之粗化處理面密接地設置的樹脂層而成。粗化處理銅箔可設於樹脂層的單面，也可設置於兩面。樹脂層係包含樹脂，較佳為絕緣性樹脂而成。樹脂層較佳為預浸體及/或樹脂片。預浸體係指使合成樹脂板、玻璃板、玻璃織布、玻璃不織布、紙等的基材含浸合成樹脂而成的複合材料之總稱。作為絕緣性樹脂的較佳實例，可舉出環氧樹脂、氰酸酯樹脂、雙馬來醯亞胺三嗪樹脂(BT樹脂)、聚苯醚樹脂、酚樹脂等。又，作為構成樹脂片之絕緣性樹脂的實例，可舉出環氧樹脂、聚醯亞胺樹脂、聚酯樹脂等的絕緣樹脂。又，樹脂層中，基於提升絕緣性等觀點，亦可含有由二氧化矽、氧化鋁等各種無機粒子所構成的填料粒子等。樹脂層的厚度不特別限定，較佳為1~1000μm，更佳為2~400μm，再更佳為3~200μm。樹脂層亦能以複數層構成。預浸體及/或樹脂片等的樹脂層可介隔著預先塗佈於銅箔表面的底塗樹脂層設 置於粗化處理銅箔上。
印刷配線板
本發明之粗化處理銅箔較佳使用於印刷配線板的製作。亦即，根據本發明較佳形態，係提供一種具備上述粗化處理銅箔的印刷配線板、或使用上述粗化處理銅箔所得的印刷配線板。本形態之印刷配線板係包含依序層合樹脂層與銅層的層構成而成。又，就樹脂層而言，關於貼銅層合板係如上述。無論為何者，印刷配線板皆可採用周知之層構成。作為與印刷配線板有關的具體例，可舉出作成在預浸體的單面或兩面接著本發明之粗化處理銅箔並硬化而成的層合體後進行電路形成的單面或兩面印刷配線板、或將此等多層化的多層印刷配線板等。又，作為其他的具體例，亦可舉出在樹脂薄膜上設置本發明之粗化處理銅箔並形成電路的可撓性印刷配線板、COF、TAB膠帶等。作為另外其他的具體例，可舉出在本發明之粗化處理銅箔形成塗佈有上述之樹脂層的附有樹脂之銅箔(RCC)，將樹脂層作為絕緣接著劑層層合於上述之印刷基板後，將粗化處理銅箔作為配線層的全部或一部分以改良半加成(MSAP)法、減成法等的手法形成電路的增層配線板、或去除粗化處理銅箔後以半加成(SAP)法形成電路的增層配線板、交互重複附有樹脂之銅箔在半導體積體電路上的積層與電路形成的晶圓上直接增層等。
[實施例]
根據以下各例對本發明具體加以說明。此外，在以下各例中，電解銅箔的「電極面」係指在電解銅箔製作時與陰極相接之一側的面；另一方面，電解銅箔的「析出面」則指在電解銅箔製作時持續析出電解銅之一側的面，即未與陰極相接之一側的面。
例1
如下進行本發明之粗化處理銅箔的製作。
(1)電解銅箔的製作
作為銅電解液係使用以下所示組成的硫酸銅溶液，陰極使用表面粗糙度Ra為0.20μm的鈦製旋轉電極，陽極使用DSA(尺寸穩定性陽極)，以溶液溫度45℃、電流密度55A/dm2進行電解，得到厚度18μm的電解銅箔。以後述之手法測定該電解銅箔的十點平均粗糙度Rzjis的結果，析出面為0.6μm、電極面為1.3μm。
<硫酸銅溶液的組成>
- 銅濃度：80g/L
- 硫酸濃度：260g/L
- 雙(3-磺丙基)二硫醚濃度：30mg/L
- 二烯丙基二甲基氯化銨聚合物濃度：50mg/L
- 氯濃度：40mg/L
(2)粗化處理(氧化還原處理)
對上述所得之電解銅箔的兩面，依以下所示4階段程序進行粗化處理(氧化還原處理)。亦即，依序進行以下所示之第1前處理、第2前處理、氧化處理及還原處理。
(a)第1前處理
將上述(1)中所得之電解銅箔，在液溫40℃下浸漬於硫酸濃度為5質量%的硫酸系水溶液1分鐘後，用水加以清洗。
(b)第2前處理
將實施過第1前處理的電解銅箔，在液溫40℃下浸漬於NaOH濃度50g/L的氫氧化鈉水溶液1分鐘後，用水加以清洗。
(c)氧化處理
對實施過上述預處理的電解銅箔進行氧化處理。此氧化處理係藉由使該電解銅箔浸漬於液溫75℃、pH=13、亞氯酸濃度為180g/L、N-苯基-3-胺基丙基三甲氧基矽烷濃度為15g/L的氫氧化鈉溶液2分鐘來進行。如此，即在電解銅箔的兩面形成以針狀結晶構成的微細凹凸，該針狀結晶係由以CuO為主成分的銅複合化合物所構成。
(d)還原處理
對實施過上述氧化處理的電解銅箔進行還原處理。此還原處理係透過將藉由上述氧化處理而形成有微細凹凸的電解銅箔浸漬於使用碳酸鈉與氫氧化鈉調整成pH=12之二甲基胺硼烷濃度為20g/L的水溶液1分鐘來進行。此時的水溶液的溫度係設為35℃。用水清洗如此進行過還原處理的電解銅箔，在110℃乾燥10秒。藉由此等步驟，將電解銅箔之兩面的CuO還原而形成Cu金屬或Cu2O，而作成具有由銅複合化合物構成之微細凹凸的粗化處理面，該銅複合化合物其表面係整體由Cu金屬Cu2O的混相所構成。如此即得到在至少其中一側具有具備以針狀結晶構成之微細凹凸的粗化處理面的粗化處理銅箔。
(3)分析及評估
對製作之粗化處理銅箔試樣進行以下所示之分析及評估。
(a)粗化處理面(微細凹凸)的觀察
藉由剖面SEM觀察構成粗化處理銅箔之粗化處理面的微細凹凸(析出面側)的結果，得到第1圖所示之剖面SEM影像。如第1圖所示，可確認粗化處理面係由以無數個針狀結晶構成的微細凹凸所構成。又，藉由穿透型電子顯微鏡(TEM)(日本電子股份有限公司製JEM-ARM200F)以20萬倍的倍率觀察微細凹凸(尤為針狀結晶)的剖面的結 果，得到第2圖所示之STEM-HAADF像。進而，藉由上述穿透型電子顯微鏡觀察微細凹凸(尤為針狀結晶)的結果，得到第3A圖及第3B圖所示之TEM影像。第3B圖為第3A圖所示之TEM影像的部分放大影像。由如此取得之STEM-HAADF像測定針狀結晶的高度(與箔垂直之方向的長度)。此時，將在1μm×1μm的區域取10處測定所得之值的平均值作為各試樣的針狀結晶高度。結果係如表1所示。
(b)藉由STEM-EELS之針狀結晶的組成分析
對構成粗化處理銅箔試樣表面之微細凹凸的針狀結晶的組成按照以下程序進行組成分析。
(b-1)試料的前處理
對粗化處理銅箔的表面使用接著劑進行樹脂包埋後，藉由超薄切片法製作EELS測定用之超薄切片。此時，目標厚度係設為20nm。
(b-2)EELS能譜的取得
對製作之試料使用穿透型電子顯微鏡(TEM)(日本電子股份有限公司製JEM-ARM200F)，藉由電子能量損失能譜法(EELS)取得Cu-L端的電子能量損失能譜。具體而言，係取得粗化處理面之包含針狀結晶的部分的STEM(掃描穿透電子顯微鏡)-HAADF像(高角度散射暗視野像)(下稱 STEM-HAADF像)後，指定規定的部位取得電子能量損失能譜。該測定係在STEM-HAADF像中，針對包含銅箔主體部分(即針狀結晶以外之銅箔的主要部分)、針狀結晶的內部部分(即芯的部分)、及針狀結晶的表面(即外周部分)的多處進行。STEM觀察時的加速電壓係設為200kV、電子束點徑係設為約0.15nm。取得之能量區域係取具有Cu-L端之包含900~1000eV的範圍。第4圖中一併顯示：顯示構成粗化處理銅箔之微細凹凸的針狀結晶的STEM-HAADF像、及在該影像之附有圓圈的針部分與銅箔主體之各部分取得的Cu-L2,3端相關之EELS之能譜。又，第5圖中一併顯示：顯示針狀結晶之針前端部的STEM-HAADF像、及在該影像之附有圓圈的外周部分與芯之各部分取得的Cu-L2,3端相關之EELS之能譜。特別針對針狀結晶的表面，任意對5點進行測定，取得各點之EELS能譜。
(b-3)EELS能譜數據的解析
比較所得之Cu-L端之電子能量損失能譜的銅箔主體部分(即針狀結晶以外之銅箔的主要部分)的能譜、與Cu金屬的標準試料的能譜，若Cu-L端的能量位置偏移則視需求進行校正。藉由將如此視需求經過校正的能譜，與藉由後述之峰特性而表徵之Cu金屬、Cu2O及CuO的標準之Cu-L端的電子能量損失能譜使用後述之鑑定手法進行比較，來進行測定位置之組成的鑑定。其後，針對針狀結 晶的表面，對測得的5點之各點進行EELS能譜的鑑定，彼等全部係判定為Cu金屬/Cu2O混相。進而，亦進行針狀結晶之前端部的EELS映射，結果如第6圖所示，亦確認最表層的整體存在有氧。綜合參酌這些結果，判定針狀結晶的表面係整體由Cu金屬/Cu2O混相所構成。
此外，EELS能譜數據的解析中的Cu金屬、Cu2O、及CuO的鑑定係採用以下所示程序來進行。惟，以下所示能量值(eV)係基於藉由本實施例中所採用之測定裝置所測得的值，應留意與周知文獻所揭露的值之間可能產生最大5eV為止的偏移。從而，以下之基準中所記載的「XeV附近」(X係取任意值)之用語，係可容許X±5eV之範圍的變動。
<Cu金屬之能譜的鑑定>
歸屬於Cu金屬之能譜的鑑定，原則上可透過確認滿足以下之1)~4)來進行。
1)在約938eV附近有峰P938。
2)在約959eV附近亦有峰P959。
3)峰P959的強度I959係高於峰P938的強度I938(即I938<I959)。
4)在940~950eV附近進一步有2個峰。
<Cu2O之能譜的鑑定>
歸屬於Cu2O之能譜的鑑定，原則上可透過確認滿足 以下之5)~8)來進行。
5)在約936eV附近有峰P936。
6)在約957eV附近亦有峰P957。
7)峰P936的強度I936與峰P957的強度I957約略相同程度或者相近似(即I936≒I957)。此外，當I936>I957時則鑑定為CuO。此2個峰的關係可藉由參照例如第8圖所示之來自周知文獻(Hofer&Golob,Ultramicroscopy 21(1987)379)之Cu2O與CuO之能譜中的2個峰的強度比(在第8圖中由2個峰上方之輔助線的斜率強調之)而進一步獲得視覺上的理解。
8)結果P936與P957之間成為波谷。
<Cu金屬/Cu2O混相的鑑定>
再者，就Cu金屬/Cu2O混相，因Cu金屬之能譜與Cu2O之能譜經複合化而某種程度承繼此等能譜之特徵，惟其呈現不易嚴謹地分類為任一者之特有的能譜。具體而言，其雖具有上述1)及2)所記載的峰P938及P959，但上述3)之I959>I938的峰強度比消失，而且上述4)之940~950eV附近的2個峰亦不易指定。另一方面，上述5)及6)所記載的峰P936及峰P957，分別被能量位置與彼等相近之上述1)及2)所記載的峰P938及P959混入的結果，實質上消失。取而代之，有別於上述3)，反而是以依據上述7)之形式，峰P938的強度I959與峰P959的強度I938約略相同程度或者相近似(即I938≒I959)、或是如上述3)所示，峰 P959的強度I959高於峰P938的強度I938(即I938<I959)。無論為何，結果均以依據上述8)之形式P938與P959之間成為波谷。若將此等彙整，則歸屬於Cu金屬/Cu2O混相之能譜的鑑定，原則上可透過確認滿足以下之i)~iv)來進行。
i)在約938eV附近有峰P938(與上述1)相同)
ii)在約959eV附近亦有峰P959(與上述2)相同)
iii)峰P938的強度I938與峰P959的強度I959約略相同程度或者相近似(即I938≒I959)(取代上述3)而依據上述7))或比強度I938高(即I938<I959)(與上述3)相同)。
iv)結果P938與P959之間成為波谷(取代上述4)而依據上述8))。
亦即，歸屬於Cu金屬/Cu2O混相之能譜，可謂2個峰(即P938及P959)的位置與Cu金屬的能譜一致，但可謂2個峰的強度比或2個峰間的形狀反而與Cu2O的能譜一致。從而，歸屬於Cu金屬/Cu2O混相之能譜的鑑定，可透過I)由2個峰(即P938及P959)的位置鑑定Cu金屬；II)由此2個峰之強度(即I938及I959)的比與此等峰之間的形狀鑑定Cu2O；III)在針狀結晶表面的多處(例如5處)全體滿足上述I)及II)及/或藉由氧映射確認最表層整體存在有氧來進行。
(c)與樹脂之密接性的評估
對粗化處理銅箔，為了評估與絕緣樹脂基材之密接 性，而如下進行常態剝離強度、吸濕後剝離強度、及酸處理後剝離強度的測定。
(c-1)常態剝離強度
作為絕緣樹脂基材，準備2片預浸體(Panasonic股份有限公司製R1551，厚度100μm)，予以堆疊。對該堆疊之預浸體層合粗化處理銅箔，使其粗化處理面與預浸體抵接，並使用真空壓機，在沖壓壓力2.9MPa、溫度200℃、沖壓時間90分的條件下進行沖壓而製成貼銅層合板。其次，對該貼銅層合板，藉由蝕刻法，製作寬0.8mm之具備剝離強度測定用直線電路的試驗基板。將如此形成的直線電路，依據JIS C6481-1996由絕緣樹脂基材上剝除，並測定常態剝離強度(kgf/cm)。結果係如表1所示。
(c-2)吸濕後剝離強度
除在剝離強度的測定前，將具備直線電路的試驗基板浸漬於沸水2小時以外，係根據與上述之常態剝離強度同樣的程序測定吸濕後剝離強度(kgf/cm)。結果係如表1所示。
(c-3)酸處理後剝離強度
除在剝離強度的測定前，將具備直線電路的試驗基板浸漬於4N鹽酸30分鐘以外，係根據與上述之常態剝離強度同樣的程序測定酸處理後剝離強度(kgf/cm)。結果係如 表1所示。
(d)吸濕耐熱性試驗
將使用粗化處理銅箔以與上述同樣方式製作的貼銅層合板，在溫度60℃且濕度60%的環境下放置120小時後，對貼銅層合板在回流爐中以峰值溫度270℃、30秒進行加熱，進行此加熱10次。在回流爐中加熱10次後，觀察加熱所致之貼銅層合板表面的膨脹之有無。將未觀察到膨脹的情況判定為合格，採用進行5次之試驗當中判定為合格的次數作為吸濕耐熱性的指標。結果係如表1所示。
例2(比較)
如下進行相當於專利文獻1之實施例1所揭露之粗化處理銅箔的粗化處理銅箔的製作。
(1)電解銅箔的製作
以與例1之(1)同樣的方式製作電解銅箔。
(2)粗化處理(氧化還原處理)
對上述所得之電解銅箔的兩面，依以下所示4階段程序進行粗化處理(氧化還原處理)。亦即，依序進行以下所示之第1前處理、第2前處理、氧化處理及還原處理。
(a)第1前處理
將上述(1)中所得之電解銅箔，在液溫25℃下浸漬於NaOH濃度50g/L的氫氧化鈉水溶液5分鐘後，用水加以清洗。
(b)第2前處理
將實施過第1前處理的電解銅箔，在液溫25℃下浸漬於過氧化氫濃度為1質量%、硫酸濃度為5質量%的硫酸系水溶液5分鐘後，用水加以清洗。
(c)氧化處理
對實施過上述預處理的電解銅箔進行氧化處理。此氧化處理係藉由使該電解銅箔浸漬於液溫70℃、pH=12、亞氯酸濃度為150g/L、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷的濃度為10g/L的氫氧化鈉溶液2分鐘來進行。如此，即在電解銅箔的兩面形成以針狀結晶構成的微細凹凸，該針狀結晶係由以CuO為主成分的銅複合化合物所構成。
(d)還原處理
對實施過上述氧化處理的試料進行還原處理。此還原處理係透過將藉由上述氧化處理而形成有微細凹凸的電解銅箔浸漬於使用碳酸鈉與氫氧化鈉調整成pH=12之二甲基胺硼烷濃度為20g/L的水溶液1分鐘來進行。此時的水溶液的溫度係設為35℃。用水清洗如此進行過還原處理 的電解銅箔，在130℃乾燥20秒。如此即得到在兩面具有具備以針狀結晶構成之微細凹凸的粗化處理面的粗化處理銅箔。
(3)分析及評估
對製作之粗化處理銅箔試樣，進行與例1同樣的分析及評估。結果係如表1所示。又，第8圖中一併顯示：顯示構成本例中所得之粗化處理銅箔之微細凹凸的針狀結晶之針前端部的STEM-HAADF像、及在該影像之附有圓圈的外周散佈部分、外周主要部分及芯部分之各部分取得的Cu-L2,3端相關之EELS之能譜。如第7圖所示，針狀結晶的外周主要部分係以Cu金屬構成，而在針狀結晶的表面則局部地散佈有Cu金屬/Cu2O混相。
例3(比較)
如下進行相當於專利文獻1之比較例所揭露之粗化處理銅箔的粗化處理銅箔的製作。
(1)電解銅箔的製作
以與例1之(1)同樣的方式製作電解銅箔。
(2)粗化處理(氧化還原處理)
對上述所得之電解銅箔的兩面，依以下所示4階段程序進行粗化處理(氧化還原處理)。亦即，依序進行以下所 示之第1前處理、第2前處理、氧化處理及還原處理。
(a)第1前處理
將上述(1)中所得之電解銅箔，在液溫25℃下浸漬於NaOH濃度50g/L的氫氧化鈉水溶液5分鐘後，用水加以清洗。
(b)第2前處理
將實施過第1前處理的電解銅箔，在液溫25℃下浸漬於過氧化氫濃度為1質量%、硫酸濃度為5質量%的硫酸系水溶液5分鐘後，用水加以清洗。
(c)氧化處理
對實施過上述預處理的電解銅箔進行氧化處理。此氧化處理係藉由將上述電解銅箔浸漬於含有10vol%之屬ROHM AND HAAS電子材料股份有限公司製之氧化處理液的「PRO BOND 80A OXIDE SOLUTION」及20vol%之「PRO BOND 80B OXIDE SOLUTION」之液溫85℃的水溶液5分鐘來進行。如此，即在電解銅箔的兩面形成以針狀結晶構成的微細凹凸，該針狀結晶係由以CuO為主成分的銅複合化合物所構成。
(d)還原處理
對實施過上述氧化處理的試料進行還原處理。此還原 處理係透過將實施過上述氧化處理的電解銅箔浸漬於含有6.7vol%之屬ROHM AND HAAS電子材料股份有限公司製之還原處理液的「CIRCUPOSIT PB OXIDE CONVERTER 60C」、1.5vol%之「CUPOSIT Z」的水溶液5分鐘來進行。此時的水溶液的溫度係設為35℃。用水清洗如此進行過還原處理的電解銅箔，在130℃乾燥20秒。如此即得到在兩面具有具備以針狀結晶構成之微細凹凸的粗化處理面的粗化處理銅箔。
(3)分析及評估
對製作之粗化處理銅箔試樣，進行與例1同樣的分析及評估。結果係如表1所示。
[表1]

Claims (7)

  1. 一種粗化處理銅箔，其係在其中至少一側具有具備以針狀結晶構成之微細凹凸的粗化處理面之粗化處理銅箔，其中前述針狀結晶的表面係整體由Cu金屬與Cu2O的混相所構成。
  2. 如請求項1之粗化處理銅箔，其中前述針狀結晶的高度為50~400nm。
  3. 如請求項1之粗化處理銅箔，其中前述針狀結晶的表面之前述混相的厚度為10nm以下。
  4. 如請求項1之粗化處理銅箔，其中前述微細凹凸係經過氧化還原處理而形成者。
  5. 如請求項1之粗化處理銅箔，其中前述針狀結晶的內部係以Cu金屬的單相所構成。
  6. 一種貼銅層合板，其係具備如請求項1~5中任一項之粗化處理銅箔。
  7. 一種印刷配線板，其係具備如請求項1~5中任一項之粗化處理銅箔。
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