TWI697412B - 附載體銅箔、附樹脂銅箔、及印刷電路板之製造方法 - Google Patents
附載體銅箔、附樹脂銅箔、及印刷電路板之製造方法 Download PDFInfo
- Publication number
- TWI697412B TWI697412B TW105141626A TW105141626A TWI697412B TW I697412 B TWI697412 B TW I697412B TW 105141626 A TW105141626 A TW 105141626A TW 105141626 A TW105141626 A TW 105141626A TW I697412 B TWI697412 B TW I697412B
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- Prior art keywords
- carrier
- layer
- copper foil
- resin
- silicon
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Links
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Images
Classifications
-
- 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
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4682—Manufacture of core-less build-up multilayer circuits on a temporary carrier or on a metal foil
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
本發明係提供一種附載體銅箔,特別適於在雷射加工及除沾污(desmear)處理後剝離載體之電路形成製程之附載體銅箔,亦即在載體的耐熱壓(hot-press)性(耐熱性)、雷射加工性、除沾污處理之載體的耐蝕性、除沾污處理之剝離層之耐蝕性、及載體剝離強度上優良之附載體銅箔。該附載體銅箔,其特徵係具備:由從聚萘二甲酸乙二醇酯樹脂(PEN)、聚醚碸樹脂(PES)、聚醯亞胺樹脂、及聚苯硫醚樹脂選擇出之至少1種樹脂所構成之載體,被設在載體上、主要包含矽而成之矽層,被設在矽層上、主要包含碳而成之碳層,與被設在碳層上之極薄銅層。
Description
本發明係有關附載體銅箔、附樹脂銅箔、印刷電路板之製造方法。
近年,作為適於電路微細化之印刷電路板之製造工法,廣泛採用改良半加成法製程(MSAP)法。MSAP法,係適於形成極為微細的電路之手法,為了發揮其特徵,採用附載體銅箔來進行。例如,以圖4及圖5所示之方式,將附載體銅箔的極薄銅層118,在具備內層導體126的核心層124上具備樹脂層122之樹脂基板,用底層塗料層(primer layer)119壓製使之密貼,將載體(未圖示)剝離(步驟(a))。其次,利用雷射加工形成通孔128,將通孔128內進行除沾污處理(步驟(b))。其次,在施以無電鍍銅130(步驟(c))後,藉由使用光阻劑131之曝光及顯像依指定的圖案遮罩(步驟(d)),施以電鍍銅132(步驟(e))。在去除光阻劑131而形成配線部分132a(步驟(f))後,將鄰接的配線部分132a間不要的極薄銅箔等跨該等的厚度全體利用沖洗蝕刻予以去除(步驟(g)),得到依指定的圖案被形
成之配線134。
可是,伴隨近年的攜帶用電子機器等的電子機器小型化及高功能化,對印刷電路板要求配線圖案的更加微細化(精細節距化)。為了對應這樣的要求,在印刷電路板製造用銅箔上最好是薄於從前的。於是,提出在附載體銅箔將銅箔層以濺鍍法等氣相法形成之手法。例如,在專利文獻1(日本專利第4726855號公報)揭示,在載體薄片的表面介著接合界面層具有銅箔層之附載體薄片銅箔;揭示該接合界面層,係由採用物理蒸鍍法形成之金屬層/碳層之2層所構成,銅箔層,係藉由在接合界面層上以物理蒸鍍法形成厚度10nm~300nm之第1銅層、再以電解法形成第2銅層而得到之層。此外,在該文獻記載,構成該接合界面層之金屬層,可以是任何由鉭、鈮、鋯、鎳、鉻、鈦、鐵、矽、鉬、釩、及鎢而被構成之層。根據專利文獻1所揭示之附載體銅箔等,即使負荷超過300℃之壓製加工溫度,載體銅箔與銅箔層,仍能夠達成工業上可以採用的安定剝離強度。
另一方面,習知作為載體使用樹脂薄膜之附載體銅箔。例如,在專利文獻2(日本專利特開2015-157472號公報)揭示,在離型膜的剝離層上設置銅層之附離型膜銅箔,記載在剝離層從膜側起依序形成金屬層及碳層。在該文獻,作為金屬層之最佳例,記載鋁、鋅、鈦、鉻、鐵、鈷、鎳、鍺、白金、金、及鉛,另一方面,作為構成薄膜的聚合物之最佳例,記載聚醯亞胺、聚對苯二甲
酸乙二醇酯、聚萘二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、對位性聚苯乙烯膜、芳香族聚醯胺膜、變性聚苯醚膜、氟系膜、及液晶聚合物膜。
[專利文獻1]日本特許4726855號公報
[專利文獻2]日本特開2015-157472號公報
可是,上述那樣的MSAP法係有以下那樣的問題點。第一,雷射加工時樹脂飛散物會附著在極薄銅層上,而有對配線圖案的形成帶來妨礙之虞。第二,極薄銅層薄薄之場合在精細圖案形成性上優良,但在載體剝離之後進行除沾污處理或無電解電鍍步驟(特別是其前處理之軟蝕刻(soft etching))時,有極薄銅層被蝕刻後容易產生針孔、發生配線圖案缺陷之疑慮。因而,如能在使載體層積之狀態下進行雷射加工及除沾污處理、之後將載體剝離的話是最合適的。亦即,連同載體將層積體一貫進行雷射穿孔及除沾污處理之手法。然而,該場合下,載體為銅箔等之金屬載體時雷射加工上就需要相當高的能量。例如,以紅外線波長、在比較低能量的二氧化碳雷射要對金屬載體開孔是困難的。於是,考慮採用更高能量的UV-YAG雷射或準分子雷射。實際上,在指向線寬間距比(L/S比)為
5μm以下/5μm以下且通孔徑50μm以下之精細節距用途之場合,高能量的雷射由於是短波長而有利。然而,在利用這樣的高能量雷射對金屬載體開孔之場合,起因於高能量而形成使通孔形狀不容易作成同設計之形狀、通孔徑精確度差之,亦即雷射加工性差之物。此外,以高能量利用雷射穿孔來形成通孔之場合,由於雷射光的能量太強而貫通內層導體,會使有底通孔的安定形成變得困難。於是,從雷射加工性的提升、進而藉此的量產性及產量提升之觀點而言,考慮取代金屬載體而採用樹脂載體。該點,習知如專利文獻2所例舉之多種多樣的樹脂載體,該等多數是由耐熱性低的樹脂所構成的,在與基材壓製接合時的加熱下會導致劣化而使龜裂等發生。此外,還有樹脂載體該物本身沒有除沾污耐性、在除沾污步驟會溶出變形之問題,樹脂載體該物本身在除沾污步驟即使安定,但在除沾污步驟後樹脂載體以剝離層為起點浮起來之問題。
本發明人等,這次,得到藉由將載體用特定的樹脂構成,而且,將剝離層作成矽層及碳層之2層構成,可以提供特別適於雷射加工及除沾污處理後剝離載體之電路形成製程之附載體銅箔之想法。具體而言,得到可以提供一種在載體的耐熱壓(hot-press)性(耐熱性)、雷射加工性、除沾污處理之載體之耐蝕性、除沾污處理之剝離層之耐蝕性、及載體剝離強度上優良之附載體銅箔之想法。
從而,本發明之目的在於提供一種附載體銅
箔,特別適於在雷射加工及除沾污(desmear)處理後剝離載體之電路形成製程之附載體銅箔,亦即在載體的耐熱壓性(耐熱性)、雷射加工性、除沾污處理之載體的耐蝕性、除沾污處理之剝離層之耐蝕性、及載體剝離強度上優良之附載體銅箔。
根據本發明之一態樣,可提供具備:由從聚萘二甲酸乙二醇酯樹脂(PEN)、聚醚碸樹脂(PES)、聚醯亞胺樹脂(PI)、及聚苯硫醚樹脂(PPS)選擇出之至少1種樹脂所構成之載體,被設在前述載體上、主要包含矽而成之矽層,被設在前述矽層上、主要包含碳而成之碳層,與被設在前述碳層上之極薄銅層之附載體銅箔。
根據本發明之另一態樣,可提供具備上述的附載體銅箔、與被設在前述附載體銅箔之前述極薄銅層上之樹脂組成物層之附樹脂銅箔。
根據本發明之另一態樣,可提供包含:在至少核心層的單面依序層積樹脂層及上述附載體銅箔、或層積上述附樹脂銅箔,而形成附載體層積體之步驟;對前述附載體層積體施以雷射加工,形成通孔之步驟;去除前述通孔的污跡之除沾污處理步驟;與
前述除沾污處理步驟後,剝離前述載體之載體剝離步驟之印刷電路板之製造方法。
10‧‧‧附載體銅箔
12‧‧‧載體
14‧‧‧矽層
16‧‧‧碳層
18‧‧‧極薄銅層
20‧‧‧矽系密貼層
22‧‧‧樹脂層
24‧‧‧核心層
26‧‧‧內層導體
28‧‧‧通孔
圖1係顯示本發明之附載體銅箔之一態樣之模式剖面圖。
圖2係概念地圖示使用本發明之附載體銅箔之附載體層積體之雷射加工及除沾污(desmear)處理後之狀態。
圖3係本發明之印刷電路板之製造方法之說明圖。
圖4係供說明從前的MSAP法用之步驟流程圖,顯示前半之步驟(步驟(a)~(d))之圖。
圖5係供說明從前的MSAP法用之步驟流程圖,顯示後半之步驟(步驟(e)~(g))之圖。
圖6係概念地圖示使用本發明範圍外之附載體銅箔之附載體層積體之雷射加工及除沾污處理後之不良狀態之一例。
在圖1模式地顯示本發明之附載體銅箔。如圖1所示,本發明之附載體銅箔10,係依序具備載體12、矽層
14、碳層16、與極薄銅層18。載體12,係由從聚萘二甲酸乙二醇酯樹脂(PEN)、聚醚碸樹脂(PES)、聚醯亞胺樹脂(PI)及聚苯硫醚樹脂(PPS)選擇出之至少1種樹脂所構成。矽層14,被設在載體12上、主要包含矽而成之層。碳層16,被設在矽層14上、主要包含碳而成之層。矽層14與碳層16構成2層構成之剝離層。極薄銅層18,係由被設在碳層16上的銅所形成之層。因應必要,也可以在極薄銅層18上進而設置矽系密貼層20。此外,也可以作成在載體12的雙面以成為上下對稱之方式依序具備上述各種層之構成。附載體銅箔10,具備以由上述之特定的樹脂所構成之薄膜(以下,稱作樹脂膜)作為載體12,還有,以上述之矽層14及碳層16作為剝離層之外,採用公知之層構成即可並未被特別限定。可以藉由以此方式將載體12用特定的樹脂構成,而且,將剝離層作成矽層14及碳層16之2層構成,提供特別適於雷射加工及除沾污處理後剝離載體12之電路形成製程之附載體銅箔。具體而言,可以提供一種在載體12的耐熱壓性(耐熱性)、雷射加工性、除沾污處理之載體之耐蝕性、除沾污處理之剝離層之耐蝕性、及載體剝離強度上優良之附載體銅箔。
圖2係概念地顯示使用本發明之附載體銅箔10之附載體層積體之雷射加工及除沾污(desmear)處理後之狀態。如圖2所示方式,本發明之附載體銅箔10,在表面具備內層導體26之核心層24上,層積樹脂層22及附載體銅箔10,在附載體12下直接利用雷射加工形成通
孔28。於是,施以在該通孔28使過錳酸鹽溶液接觸來去除污跡之除沾污處理步驟。在該雷射加工及除沾污處理正常被進行之場合下,係如圖2所示,成為各層皆無異常溶解、各層皆無密貼不良之良好的狀態。相對於此,圖6概念地顯示使用本發明範圍外之附載體銅箔之附載體層積體之雷射加工及除沾污處理後之不良狀態之一例。該圖6所示之態樣係相當於採用樹脂載體及剝離層皆與本發明不同之構成之一例,在與圖1相同構成構件附以相同符號,另一方面,在與圖1相異之材質構成構件之載體、第一界面層及第二界面層附上別的編號之13、15及17。於是,在本發明範圍外之態樣,以下2個問題為典型地假設。
(i)載體之溶解(參照圖6被記為A之部分):當載體13於除沾污步驟溶解或膨潤剝離時,通孔28的肩(shoulder)部分的剝離層(亦即第一剝離層15及第二剝離層17)會露出來。於是,剝離層也會因為薄而容易崩壞,極薄銅層18便露出來。在該狀態下進行無電鍍銅的前處理步驟(軟蝕刻)時,通孔28的肩部分的極薄銅層18會消失。以該方式在給電層之極薄銅層18欠缺之狀態下被形成之通孔28係有發生在(做成上層配線層的一部分之)貫通端子(via land)部電鍍層不析出、或者發生樹脂層22與極薄銅層18之密貼不良等問題之疑慮。
(ii)剝離層的溶解或密貼不良(參照圖6記為B之部分):用除沾污液讓剝離層(第一剝離層15及第二剝離層17)溶解,或在載體12與剝離層之間發生剝離。在該類之
處觀察到除沾污液的滲入。這樣一來造成極薄銅層18的表面於無電解電鍍步驟暴露。在該狀態時,在無電鍍銅的前處理步驟(軟蝕刻)下通孔28的肩部分的極薄銅層18會消失。以該方式在給電層之極薄銅層18欠缺之狀態下被形成之通孔28係有發生在(做成上層配線層的一部分之)貫通端子(via land)部電鍍層不析出、或者發生樹脂層22與極薄銅層18之密貼不良等問題之疑慮。
該點,本發明之附載體銅箔,係藉由如圖2所示方式,作為載體12由從聚萘二甲酸乙二醇酯樹脂(PEN)、聚醚碸樹脂(PES)、聚醯亞胺樹脂(PI)及聚苯硫醚樹脂(PPS)選擇出之至少1種樹脂所構成,而且,將剝離層做成矽層14及碳層16之2層構成,而能夠同時解除上述2個問題。亦即,能夠使除沾污處理之載體的耐蝕性、及除沾污處理之剝離層的耐蝕性兩者提升。此外,上述特定的樹脂係在耐熱性(例如在220℃、最好是230℃、更好是260℃的耐熱性)及耐藥品性上優良,故而在載體12的耐熱壓性上優良。而且,因為載體12係樹脂製的緣故,相較於金屬製載體,在雷射加工性上格外優良(亦即使通孔徑精確度提高)。再者,利用上述特定樹脂製的載體12與上述2層構成的剝離層(亦即矽層14及碳層16)之組合,能夠實現雷射加工時或除沾污處理時不容易剝落,而且,除沾污處理後容易剝下,這樣極合適的載體剝離強度。
載體12,在可以賦予優良的耐熱性之點下,
係由從聚萘二甲酸乙二醇酯樹脂(PEN)、聚醚碸樹脂(PES)、聚醯亞胺樹脂(PI)、及聚苯硫醚樹脂(PPS)選擇出之至少1種樹脂所構成。在兼備耐熱性與耐蝕性之點,最好是聚醚碸樹脂(PES)、聚苯硫醚樹脂(PPS)、及該等之組合。載體12典型的形態係薄膜或薄片。載體之厚度係以10~100μm佳,為15~50μm更佳。厚度在這樣的範圍內時,載體12的操作上容易,因成膜時的熱導致的損傷少,另一方面,容易利用雷射加工高精確度地形成通孔。此外,載體12之至少極薄銅層18側的表面,遵照日本工業標準JIS B 0601-2001被測定之算術平均粗糙度Ra為5nm以上100nm以下,在保持其上被形成的極薄銅層18的平滑性之點上是理想的。又,在這樣的平滑的表面測定算術平均粗糙度Ra之場合,最好是採用利用非接觸式表面粗糙度‧形狀測定機(雷射顯微鏡等)之測定值。
矽層14,係主要包含矽而成之層。構成矽層14之矽典型上為非晶質矽。矽層14係以利用XPS被測定之矽濃度為60原子%以上佳、較佳為70原子%以上、更佳為80原子%以上、特佳為85原子%以上、最佳為90原子%以上。矽濃度的上限值並未特別限定而100原子%亦可,但現實上為98原子%以下。矽層,進而包含碳、氧、氫、或該等之組合亦可。構成矽層14之矽系材料,含起因於原料成分或成膜步驟等之不可避不純物質之B(硼)、P(磷)、Al(鋁)、Sb(銻)、As(砷)等亦可。例如,微量添加為了可以對濺鍍靶進行DC濺鍍用之硼等導電性摻
雜物之場合,此類之摻雜物之混入是被容許之物。此外,在不逸脫本發明之旨趣之範圍內,矽系密貼層也可以包含其他的摻雜物。此外,由於矽成膜後被暴露在大氣,因此而混入的氧的存在是被容許的。矽層14最好是利用濺鍍等氣相法被形成之層。矽層14最好是採用摻雜硼之矽靶並利用DC濺鍍等氣相法被形成之層。矽層14之厚度為1~50nm佳,3~20nm較佳,5~15nm更佳,為8~12nm最佳。該厚度,係設為將層剖面用穿透式電子顯微鏡的能量分散型X線分光分析器(TEM-EDX)加以分析而被測定之數值。
碳層16係主要包含碳而成之層,以主要由碳或碳化氫構成之層為佳,更好是由硬質碳膜之非晶碳所構成。碳層16係以利用XPS被測定之碳濃度為60原子%以上佳、較佳為70原子%以上、更佳為80原子%以上、特佳為85原子%以上。碳濃度的上限值並未特別限定而100原子%亦可,但現實上為98原子%以下。碳層16係可以包含不可避不純物(由例如氛圍等周圍環境而來的氧、碳、氫等)。此外,碳層16起因於極薄銅層18的成膜手法而可以混入銅原子。即使碳與載體之相互擴散性及反應性小,且承受超過300℃的溫度的壓製加工等,也可以防止銅箔層與接合界面之間因高溫加熱造成的金屬結合之形成,並維持載體的剝離去除容易之狀態。加上,利用與矽層14之組合,如上述方式,有助於用於印刷電路板的製造之場合之,配線圖案外緣的直進性的提升,與在極薄銅
層與載體之間因應製造階段之適度的密貼性及剝離容易性之實現。此碳層16也是利用濺鍍等氣相法被形成之層這從抑制非晶碳中過度的不純物之點、與前述的矽層14成膜之連續生產性之點等而言是好的。碳層的厚度以0.1~10nm為佳。該厚度,係設為將層剖面用穿透式電子顯微鏡的能量分散型X線分光分析器(TEM-EDX)加以分析而被測定之數值。
極薄銅層18,以如何的方法被製造出的皆可,例如,可以是利用無電鍍銅法及電解鍍銅法等之濕式成膜法、濺鍍及真空蒸鍍等之物理氣相成膜法、化學氣相成膜、或該等之組合而形成之銅箔。特佳的極薄銅層,從容易對應於因極薄化造成之精細節距化之觀點而言,係利用濺鍍法或/及真空蒸鍍等氣相法被形成之銅層,最好是利用濺鍍法被製造出的銅層。此外,極薄銅層,最好是無粗化的銅層,但印刷電路板製造時對配線圖案形成只要不帶來障礙因預備的粗化或軟蝕刻處理或洗淨處理、氧化還原處理造成二次的粗化發生者也可以。極薄銅層的厚度並未特別限定,而為了對應上述那樣的精細節距化,以50~2500nm為佳,75~2000nm較佳,90~1500nm更佳,100~1000nm特佳,最好是100~700nm或150~800nm或200~1000nm。這樣的範圍內的厚度的極薄銅層係在利用濺鍍法被製造出的成膜厚度的面內均一性、在薄片狀或捲筒狀下的生產性之觀點上佳。
極薄銅層18之與碳層16相反側的表面(矽系
密貼層20側的表面),係以具有遵照日本工業標準JIS B 0601-2001被測定之、算術平均粗糙度Ra之0.2~100nm為佳,較佳為1.0~50nm,更佳為3.0~35nm,特佳為4.0~30nm,最佳是5.0~25nm。以此方式算數平均粗糙度愈小,在用附載體銅箔10被製造之印刷電路板,成為適於形成線寬間距比(L/S比)達13μm以下/13μm以下(例如12μm/12μm~1μm/1μm)程度為止高度被微細化之配線圖案的形成。又,在這樣的平滑的表面測定算術平均粗糙度Ra之場合,最好是採用利用非接觸式表面粗糙度‧形狀測定機(雷射顯微鏡等)之測定值。
因應必要,也可以在極薄銅層18上進而設置矽系密貼層20。矽系密貼層20,係包含矽而成之層,最好是主要包含矽而成之層。構成矽系密貼層20之矽,典型上為非晶質矽。矽系密貼層20,最好是利用XPS被測定之矽濃度為60~98原子%、碳濃度為1.0~35.0原子%且氧濃度為1.0~40.0原子%。藉由在銅箔之至少單面,形成上述碳濃度及/或上述氧濃度之矽系密貼層20,即使是利用濺鍍等蒸鍍法被形成那樣的極為平坦的銅箔表面也可以實現與樹脂層高的密貼強度。而且,在上述組成之矽系密貼層20下,也可以實現符合適於印刷電路板精細節距化之絕緣電阻,能夠藉此防止或減低被精細節距化的配線圖案之配線間的漏電流的發生。矽系密貼層之碳原子及氧原子,典型上是與矽原子結合。藉由依上述量使矽系密貼層含有碳及氫,能夠實現與樹脂層密貼性及絕緣電阻雙
方。構成矽系密貼層之矽系材料,也可以包含起因於原料成分或成膜步驟等而不可避免地混入之不可避不純物。例如,微量添加為了可以對濺鍍靶進行DC濺鍍用之硼等導電性摻雜物之場合,此類之摻雜物之混入是不可避免地得以混入矽系密貼層,而此類之不可避不純物之混入是可以被容許的。此外,在不逸脫本發明之旨趣之範圍內,矽系密貼層也可以包含其他的摻雜物。此外,由於矽成膜後被暴露在大氣,因此而混入的氧的存在是被容許的。
矽系密貼層20之碳濃度,在利用XPS(X光光電子能譜儀)被測定之場合,係以1.0~35.0原子%為佳,5.0~34.0原子%較佳,10.0~30.0原子%特佳,最佳是12.0~30.0原子%。矽系密貼層之氧濃度,在利用XPS被測定之場合,係以12.0~40.0原子%為佳,15.0~35.0原子%較佳,20.0~30.0原子%更佳,最佳為22.0~28.0原子%。碳濃度及氧濃度為上述範圍內時,可以有意義地提升與樹脂層之密貼性及絕緣電阻。該機制並不清楚,但藉由氧原子在矽系密貼層中某種程度存在而有助於絕緣電阻,另一方面,當氧原子過多時則會降低與樹脂層之密貼性。此外,藉由碳原子也在矽系密貼層中某種程度存在而有助於密貼性及絕緣電阻之提升。
在本說明書,矽層14、碳層16及矽系密貼層20之矽濃度、碳濃度及氧濃度,係利用XPS(X光光電子能譜儀)被測定的。利用XPS之測定,可以從剛成膜後的矽層14、碳層16或矽系密貼層20起進行。此外,即使
在附載體銅箔或使用此被製造出的附載體層積體、印刷電路板或電子零件之型態,也存在之場合,可以藉由使矽層14、碳層16或矽系密貼層20利用加工等而露出來,而進行上述之濃度測定及結合狀態之確認。
矽系密貼層20係以具有厚度0.1~100nm為佳,2~100nm較佳,2~20nm更佳,特佳是4~10nm。在如此的範圍內時,可以有意義地提升與樹脂層之密貼性及絕緣電阻。該厚度,係設為將層剖面用穿透式電子顯微鏡的能量分散型X線分光分析器(TEM-EDX)加以分析而被測定之數值。
根據本發明之附載體銅箔10,係可以藉由準備上述之載體12,在該載體的單面或雙面,形成矽層14、碳層16、極薄銅層18、及因應必要之矽系密貼層20而製造出。載體12,因應必要,也可以進行表面處理作為矽層14等成膜之前處理。表面處理步驟,包含電暈處理、電漿處理、UV臭氧處理等,典型上是在不增加表面粗糙度之範圍在異物的去除或表面的活性化等之目的下被進行。矽層14、碳層16、極薄銅層18、及因應必要被設置之矽系密貼層20等各層之形成,從容易對應因極薄化造成精細節距化之觀點而言,最好是利用氣相法來進行。作為氣相法之例,可列舉濺鍍法、真空蒸鍍法、及離子鍍法,從在0.05nm~5000nm這樣幅度廣的範圍下可以控制膜厚之
點,跨寬廣幅度或面積並確保膜厚均一性之點等而言,最好的是濺鍍法。特別是,藉由將矽層14、碳層16、極薄銅層18、及因應必要被設置之矽系密貼層20等所有層利用濺鍍法加以形成,製造效率會格外提高。利用氣相法之成膜係採用公知的氣相成膜裝置並依照公知的條件來進行即可,並未特別限定。例如,採用濺鍍法之場合,濺鍍方式,可以是磁控管濺鍍、2極濺鍍法等公知的種種方法,磁控管濺鍍,就成膜速度快且生產性高之點而言較佳。此外,濺鍍也可以用DC(直流)及RF(高頻)之任何電源來進行。
以下,針對矽層14、碳層16、極薄銅層18、及矽系密貼層20等各層之利用氣相法(最好是濺鍍法)成膜加以說明。
矽層14之利用氣相法成膜,最好是使用矽靶及/或碳化矽靶,在非氧化性氛圍下,與因應必要而包含碳源及氫源之至少1種添加成分一起進行。此時,添加成分,最好是以從甲烷、乙烷、丙烷、丁烷、乙炔、及四乙氧基矽烷所構成的群選擇出的至少1種氣體作為原料。該等原料由於都能夠以1個成分來發揮作為碳源及氫源兩方之任務而非常適宜。矽靶的純度最好是99.9%以上,但在進行DC濺鍍之場合,由於期望將矽靶的整體電阻降低(例如到0.01Ω‧cm以下為止)以使成膜效率提升,而最好是使用摻雜導電性摻雜物之矽靶。作為導電性摻雜物之最佳例,可列舉硼(B)、磷(P)、鋁(Al)、銻(Sb)、砷(As)及該等
之組合,最好是硼(B)。在矽靶摻雜硼等導電性摻雜物之場合,導電性摻雜物的添加量以設在0.01ppm~500ppm為佳,更好是0.01ppm~300ppm。此外,開始濺鍍之前真空室內的到達真空度最好設在1×10-4Pa未滿。作為用於濺鍍之氣體,最好是與氬等非活性氣體,一起並用應該成為添加成分的原料之氣體(最好是甲烷、乙烷、丙烷、丁烷、乙炔、四乙氧基矽烷或該等之任意組合)。最好的氣體是氬與甲烷之組合。氬之流量因應濺鍍真空室大小及成膜條件而斟酌決定即可並未特別限定。此外,自沒有異常放電或電漿照射不良等之運轉不良、且連續地成膜之觀點而言,成膜時的壓力最好是在0.1~2.0Pa的範圍下進行。此壓力範圍,藉由因應裝置構造、電容、真空泵之排氣容量、成膜電源的額定容量等,調整成膜電力、氬的流量而設定即可。此外,濺鍍電力係考慮成膜的膜厚均一性、生產性等而在靶的每單位面積0.05~10.0W/cm2的範圍內斟酌設定即可。
碳層16之利用氣相法(最好是濺鍍法)成膜,最好是使用碳靶並在氬等非活性氣體氛圍下進行。碳靶最好是由石墨所構成,可以包含不可避不純物(由例如氛圍等周圍環境而來的氧、碳)。碳靶的純度係以99.99%以上為佳,更好是99.999%以上。此外,自沒有異常放電或電漿照射不良等之運轉不良、且連續地成膜之觀點而言,成膜時的壓力最好是在0.1~2.0Pa的範圍下進行。此壓力範圍,藉由因應裝置構造、電容、真空泵之排氣容量、成膜
電源的額定容量等,調整成膜電力、氬的流量而設定即可。此外,濺鍍電力係考慮成膜的膜厚均一性、生產性等而在靶的每單位面積0.05~10.0W/cm2的範圍內斟酌設定即可。
極薄銅層18之利用氣相法(最好是濺鍍法)成膜,最好是使用銅靶並在氬等非活性氣體氛圍下進行。銅靶最好是由金屬銅所構成,可以包含不可避不純物。銅靶的純度係以99.9%以上為佳,99.99%以上較佳,更佳是99.999%以上。極薄銅層18之氣相成膜時的溫度,最好是50℃以下。在40℃以下較佳,30℃以下更佳,特佳是25℃以下。在利用濺鍍法之成膜,可以採用旋轉料架方式或卷對卷方式。此外,也可以在成膜時將支撐樣本的載物台或罐輥(canroll)(在成膜時將樣本捲繞的輥)的溫度控制在指定溫度。成膜時,由於也有因氬電漿的影響使樣本溫度成為100℃以上,所以積極的冷卻機構是必要的。此外,自沒有異常放電或電漿照射不良等之運轉不良、且連續地成膜之觀點而言,成膜時的壓力最好是在0.1~2.0Pa的範圍下進行。此壓力範圍,藉由因應裝置構造、電容、真空泵之排氣容量、成膜電源的額定容量等,調整成膜電力、氬的流量而設定即可。此外,濺鍍電力係考慮成膜的膜厚均一性、生產性等而在靶的每單位面積0.05~10.0W/cm2的範圍內斟酌設定即可。
矽系密貼層20之利用氣相法成膜,最好是使用矽靶及/或碳化矽靶,在非氧化性氛圍下,與包含碳源
及氫源之至少1種添加成分一起進行。此時,添加成分,最好是以從甲烷、乙烷、丙烷、丁烷、乙炔、及四乙氧基矽烷所構成的群選擇出的至少1種氣體作為原料。該等原料由於都能夠以1個成分來發揮作為碳源及氫源兩方之任務而非常適宜。矽靶的純度最好是99.9%以上,但在進行DC濺鍍之場合,由於期望將矽靶的整體電阻降低(例如到0.01Ω‧cm以下為止)以使成膜效率提升,而最好是使用摻雜導電性摻雜物之矽靶。作為導電性摻雜物之最佳例,可列舉硼(B)、磷(P)、鋁(Al)、銻(Sb)、砷(As)及該等之組合,最好是硼(B)。在矽靶摻雜硼等導電性摻雜物之場合,導電性摻雜物的添加量以設在0.01ppm~500ppm為佳,更好是0.01ppm~300ppm。此外,開始濺鍍之前真空室內的到達真空度最好設在1×10-4Pa未滿。作為用於濺鍍之氣體,最好是與氬等非活性氣體,一起並用應該成為添加成分的原料之氣體(最好是甲烷、乙烷、丙烷、丁烷、乙炔、四乙氧基矽烷或該等之任意組合)。最好的氣體是氬與甲烷之組合。氬之流量因應濺鍍真空室大小及成膜條件而斟酌決定即可並未特別限定。此外,自沒有異常放電或電漿照射不良等之運轉不良、且連續地成膜之觀點而言,成膜時的壓力最好是在0.1~2.0Pa的範圍下進行。此壓力範圍,藉由因應裝置構造、電容、真空泵之排氣容量、成膜電源的額定容量等,調整成膜電力、氬的流量而設定即可。此外,濺鍍電力係考慮成膜的膜厚均一性、生產性等而在靶的每單位面積0.05~10.0W/cm2的範圍內斟
酌設定即可。
本發明之附載體銅箔也可以附樹脂銅箔的型態被提供。該場合,本發明之附樹脂銅箔,其特徵係具備本發明之附載體銅箔、與被設在附載體銅箔之極薄銅層上之樹脂組成物層而成。樹脂組成物層可以是在附樹脂銅箔一般上被使用之各種樹脂而並未特別被限定。樹脂組成物層可以是公知的在附樹脂銅箔一般上被採用的樹脂層,與有關印刷電路板之製造方法之後述之樹脂層22同樣地構成即可。
可以使用本發明之附載體銅箔製造出印刷電路板。以下,說明印刷電路板之最佳製造方法。此印刷電路板之製造方法,係至少包含:(1)附載體層積體之形成步驟、(2)雷射加工步驟、(3)除沾污處理步驟、(4)載體剝離步驟。依照該等步驟之印刷電路板之製造方法之一部分模式地顯示在圖3。
在至少核心層(未圖示)的單面依序層積樹脂層22及本發明之附載體銅箔10、或層積本發明之附樹脂銅箔,而形成附載體層積體11。在此,作為核心層之型態可列舉2個型態。(i)核心層之第一型態,係具有有底通孔之被用作堆積(build-up)層的表面層之核心層。作為該場合之
核心層之例,可列舉在表面具有被圖案加工的內層導體26之層積板、在表面具有未被圖案加工的內層導體26之無核心支撐體。(ii)核心層的第二型態,係被用作單面或雙面銅箔層積板之核心層。作為該場合之核心層之例,可列舉纖維狀強化材(玻璃纖維織物)被浸漬之預浸材、耐熱性樹脂薄膜、樹脂板、及玻璃板。總之,如圖3所示,最好是核心層及樹脂層22以位置在本發明之附載體銅箔10之極薄銅層18側(存在之場合下矽系密貼層20側)之方式被層積。
樹脂層22,係包含樹脂、最好是絕緣性樹脂而成。樹脂層最好是預浸材及/或樹脂薄片。所謂玻璃纖維膠片,是在合成樹脂板、玻璃板、玻璃纖維布、玻璃不織布、紙等基材含浸合成樹脂之複合材料的總稱。作為絕緣性樹脂之最佳例,可列舉環氧樹脂、氰酸鹽樹脂、雙馬來醯亞胺-三氮雜苯樹脂(BT樹脂)、聚伸苯醚樹脂、苯酚樹脂、聚4氟乙烯樹脂、氟樹脂等。此外,構成樹脂板的絕緣性樹脂之例,可以舉出環氧樹脂、聚醯亞胺樹脂、聚酯樹脂等絕緣樹脂。此外,樹脂層22從絕緣性提高等之觀點而言,也可以含有由二氧化矽、氧化鋁等各種無機粒子所構成之填充物粒子等。
對附載體層積體施以雷射加工,形成通孔28。在雷射加工在核心層具有內層導體26之場合,內層導體26穿
孔直到露出作為通孔底即可。或者,也可以利用雷射加工以貫通核心層之方式進行穿孔而形成貫通通孔。反正,雷射加工使用市售的雷射加工機來進行即可。可以使用的雷射種類並未特別限定,而最好可以使用例如二氧化碳雷射、UV-YAG雷射、準分子雷射等。特別是,由於本發明之載體12為樹脂製,而與金屬製載體之場合不同,也可以使用二氧化碳雷射等能量比較低的雷射。使用更高能量的UV-YAG雷射或準分子雷射也佳。由於此類之高能量的雷射係短波長,所以在線寬間距比(L/S比)為5μm以下/5μm以下且通孔徑50μm以下之精細節距用途上特別適合。總之,本發明之附載體銅箔係在雷射加工性上優良,能以極高精確度形成通孔。
其次,對通孔28施以除沾污處理將污跡去除。該步驟利用除沾污處理溶液之除沾污處理為公知之手法,例如,利用使用過錳酸鹽溶液、或鉻酸鹽液等使除沾污處理溶液接觸通孔28之方法來進行即可。在能夠有效率地進行污跡去除、使往載體12的浸蝕極力減少之點上,除沾污處理溶液最好是過錳酸鹽溶液。此外,例如,在利用除沾污處理溶液之處理前,為了促進污跡去除,也可以使用有機溶劑、或者有機溶劑與鹼之混合溶液來進行膨潤處理。此外,在利用除沾污處理溶液之處理後,為了去除殘留的過錳酸鹽,也可以進行利用中和還原劑之還原處理
等。本發明之方法,係藉由如圖2所示方式,作為載體12由從聚萘二甲酸乙二醇酯樹脂(PEN)、聚醚碸樹脂(PES)、聚醯亞胺樹脂(PI)、及聚苯硫醚樹脂(PPS)選擇出之至少1種樹脂所構成,而且,將剝離層做成矽層14及碳層16之2層構成,而能夠同時解除如前述、有關(i)載體的溶解及(ii)界面層的溶解或密貼不良之問題。亦即,能夠使除沾污處理之載體的耐蝕性、及除沾污處理之剝離層的耐蝕性兩者提升。
除沾污處理步驟後,將載體12剝離。載體12的剝離,例如機械地進行即可。利用上述特定樹脂製的載體12與上述2層構成的剝離層(亦即矽層14及碳層16)之組合,能夠實現雷射加工時或除沾污處理時不容易剝落,而且,除沾污處理後容易剝下,這樣極合適的載體剝離強度。
如圖3所示方式,對載體12被剝離之層積體,進行無電鍍銅30之形成等即可。不過,無電鍍銅,可以是在除沾污處理步驟與載體剝離步驟之間進行,抑或如圖3所示方式在載體剝離步驟後進行。無電鍍銅後,可以依照公知的手法施以配線加工而得到印刷電路板。該印刷電路板之製造手法,係適於配線圖案微細化之MSAP法。在利用
MSAP法之印刷電路板製造,可以如圖4及圖5所示之方式,進行光阻劑131之形成(步驟(d))、電鍍銅132之附著(步驟(e))、光阻劑131之剝離(步驟(f))、及利用沖洗蝕刻將微細配線圖案132a間的極薄銅層118去除之配線134之形成(步驟(g))。本發明之附載體銅箔,係適於線寬間距比(L/S比)到13μm以下/13μm以下(例如12μm/12μm、10μm/10μm、5μm/5μm、2μm/2μm、1μm/1μm)這樣程度為止被高度地微細化之配線圖案之形成。
話雖如此,印刷電路板,除了用本發明之附載體銅箔10之極薄銅層18以外,可以採用公知之層構成。作為有關印刷電路板之具體例,可列舉:在作成使預浸材的單面或雙面黏接本發明之附載體銅箔10之極薄銅層18、硬化之層積體(CCL)之後電路形成之單面或雙面印刷電路板、或將該等多層化之多層印刷電路板等。此外,作為其他具體例,可列舉:在樹脂薄膜上形成本發明之附載體銅箔10之極薄銅層18並形成電路之可撓性‧印刷電路板、COF、TAB膠帶等。再作為其他具體例,可列舉:在本發明之附載體銅箔形成塗佈上述樹脂層之附樹脂銅箔(RCC),在將樹脂層作為絕緣黏接材層而層積在上述印刷電路板之後,以極薄銅層作為配線層的全部或一部分並用半加成法(SAP)、改良半加成法(MSAP)、減色法等手法而形成電路之堆積配線板,或往半導體積體電路上將附樹脂銅箔的層積與電路形成交互地反覆進行之direct build-up on wafer等。作為更加進展的具體例,可列舉:將上述附
樹脂銅箔層積在基材形成電路之天線元件、介著接著劑層而層積在玻璃或樹脂薄膜形成圖案之面板‧顯示裝置用電子材料或window glass用電子材料、在本發明之附載體銅箔10的極薄銅層18塗佈導電性接著劑之電磁波護板‧薄膜等。
進而藉由以下之例具體說明本發明。
如圖1所示,在作為載體12之樹脂薄膜上將矽層14、碳層16、極薄銅層18及矽系密貼層20依此順序成膜而製作出附載體銅箔10。具體的步驟如下。又,在以下之例被提及之算數平均粗糙度Ra係遵照日本工業標準JIS B 0601-2001並以非接觸表面形狀測定機(Zygo(股)公司製NewView5032)被測定之數值。
準備具有表面的算數平均粗糙度Ra1.8nm之厚度38μm之聚萘二甲酸乙二醇酯(PEN)薄膜(製品名:Q51、Teijin DuPont Films公司製)。
在載體12的表面,將厚度10nm的矽層14以以下的裝置及條件利用濺鍍而形成。
-裝置:自行式濺鍍裝置(HIRANO光音(股)公司製)
-靶:尺寸280mm×1580mm×厚度6mm之摻雜硼200ppm之矽靶
-到達真空度Pu:5×10-4Pa未滿
-氣體:氬(流量:500sccm)
-濺鍍壓:0.45Pa
-濺鍍電力:10kW(2.3W/cm2)
-搬送速度:4m/min
在矽層14上,將由非晶碳所構成之厚度2.7nm的碳層16以以下的裝置及條件利用濺鍍而形成。
-裝置:自行式濺鍍裝置(HIRANO光音(股)公司製)
-靶:尺寸280mm×1580mm×厚度6mm之碳靶(純度99.99%)
-運載氣體:氬(流量:500sccm)
-到達真空度Pu:5×10-4Pa未滿
-濺鍍壓PAr:0.45Pa
-濺鍍電力:6kW
-搬送速度:4m/min
在碳層16上,將膜厚0.3μm的極薄銅層18以以下的裝置及條件利用濺鍍而形成。得到的極薄銅層18之與碳層16相反側之表面(亦即外側表面)之算術平均粗糙度(Ra)係5.2nm。
-裝置:自行式濺鍍裝置(HIRANO光音(股)公司製)
-靶:尺寸280mm×1580mm×厚度10mm之銅靶(純度99.98%)
-到達真空度Pu:5×10-4Pa未滿
-氣體:氬(流量:500sccm)
-濺鍍壓:0.45Pa
-濺鍍電力:20kW(4.5W/cm2)
-搬送速度:0.4m/min
在極薄銅層18上,作為矽系密貼層20將厚度6nm的矽層以以下的裝置及條件利用濺鍍而形成,製作出附載體銅箔。
-裝置:自行式濺鍍裝置(HIRANO光音(股)公司製)
-靶:尺寸280mm×1580mm×厚度6mm之摻雜硼200ppm之矽靶
-到達真空度Pu:5×10-4Pa未滿
-氣體:氬(流量:500sccm)
甲烷(流量:5.0sccm)
二氧化碳(流量:0.5sccm)
-濺鍍壓:0.45Pa
-濺鍍電力:3kW(0.67W/cm2)
-搬送速度:0.4m/min
將矽層14、碳層16及矽系密貼層20之組成分析利用X光光電子能譜儀(XPS)來進行。該利用XPS之組成分析,係使用X光光電子能譜儀(XPS)裝置(ULVAC-PHI(股)公司製、Quantum2000),並依照輸出:40W、X光源:Al(使用單色儀)、X光光束徑:200μm、能量範圍:0~1400eV、通能:58.7eV、步幅:1.0eV、測定設定時間:5分鐘、survey測定的條件進行。將採用得到的survey光譜之對象元素的定量化、以用相對感度係數法之軟體來進行。如此一來藉由進行XPS測定,決定矽濃度、碳濃度等(原子%)。
又,為了測定的方便,矽層14與碳層16之組成分析,係藉由作為組成分析監視器用之樣本,而在裝置內設置遮蔽板並在薄膜基材上僅將矽層14在與上述(1b)同樣的條件下成膜、或者在薄膜基材上僅將碳層16在與上述(1c)同樣的條件下成膜,對各個的表面進行上述組成分析來進行。如此一來掌握實際上被多層化的附載體銅薄之矽層14與碳層16之組成。另一方面,矽系密貼層20之組成分析,係對在上述(1e)最終得到之附載體銅箔的表面進行。
結果,矽層14的矽濃度係96原子%、碳層16的碳濃度係86原子%。此外,矽系密貼層20,矽濃度為72.6原子%、碳濃度為12.4原子%、氧濃度為15.0原子%。
除了i)作為載體12使用具有表面的算術平均粗糙度Ra2.5nm之聚醚碸(PES)(製品名:SUMIKAEXCEL、住友化學(Sumitomo Chemical)公司製),及ii)將碳層16的厚度設定在3.0nm以外,與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係6.3nm。此外,矽層14、碳層16、及矽系密貼層20之組成係與例1大致相同。
除了取代矽層14而以以下之方式形成鋁層以外,係與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。又,極薄銅層之與碳層相反側之表面之算術平均粗糙度Ra係4.6nm。此外,碳層16、及矽系密貼層20之組成係與例1大致相同。
在載體12的表面,將厚度7.0nm的鋁層以以下的裝
置及條件利用DC濺鍍而形成。
-裝置:自行式濺鍍裝置(HIRANO光音(股)公司製)
-靶:尺寸280mm×1580mm×厚度6mm之鋁靶(純度99.99%)
-運載氣體:氬(流量:500sccm)
-濺鍍壓:0.45Pa
-濺鍍電力:1.8W/cm2
除了作為載體12使用具有表面的算術平均粗糙度Ra7.5nm之聚苯硫醚(PPS)薄膜(製品名:TORELINA、TORAY公司製)以外,與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係10.3nm。此外,矽層14、碳層16、及矽系密貼層20之組成係與例1大致相同。
除了i)作為載體12使用以以下之方式被製作之電解銅箔、及ii)取代矽層14而以以下之方式形成鈦層以外,係與例1同樣作法,進行附載體銅箔之製作及評價。又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係61.7nm。此外,碳層16及矽系密貼層20之組成係與例1大致相同。
準備具有光澤面的算術平均粗糙度Ra60~70nm之厚度18μm的電解銅箔(Mitsui Mining & Smelting(股)公司製)作為載體12。將該載體進行酸洗處理。該酸洗處哩,係藉由將載體在硫酸濃度150g/l、液溫30℃的稀硫酸溶液浸漬30秒鐘後將表面氧化膜被去除、水洗後加以乾燥來進行。
在酸洗處理後的載體(電解銅箔)的光澤面側,將厚度6.0nm的鈦層以以下的裝置及條件利用濺鍍而形成。
-裝置:自行式濺鍍裝置(HIRANO光音(股)公司製)
-靶:尺寸280mm×1580mm×厚度6mm之鈦靶(純度99.96%)
-運載氣體:氬(流量:500sccm)
-濺鍍壓:0.45Pa
-濺鍍電力:1.8W/cm2
除了作為載體12使用具有表面的算術平均粗糙度Ra1.7nm之厚度50μm的聚對苯二甲酸乙二醇酯(PET)薄膜(製品名:Lumirror、TORAY公司製)以外,與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。
又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係5.8nm。此外,矽層14、碳層16、及矽系密貼層20之組成係與例1大致相同。
除了i)取代矽層14而與例5同樣作法形成厚度6.0nm鈦層、及ii)將碳層16的厚度作成0.5nm以外,係與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係4.5nm。此外,碳層16及矽系密貼層20之組成係與例1大致相同。
除了i)作為載體12使用具有表面的算術平均粗糙度Ra3.7nm之厚度38μm的聚醚碸(PES)薄膜、ii)取代矽層14而與例5同樣作法形成厚度6.0nm鈦層、及iii)將碳層16的厚度作成5.0nm以外,係與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係8.5nm。碳層16及矽系密貼層20之組成係與例1大致相同。
除了作為載體12使用具有表面的算術平均粗糙度
Ra3.8nm之厚度35μm的聚醯亞胺(PI)薄膜(製品名:UPILEX-S、UBE INDUSTRIES(股)公司製)在成膜面進行電暈處理以外,與例1同樣作法,進行附載體銅箔之製作及評價。結果如表1所示。又,極薄銅層18之與碳層16相反側之表面之算術平均粗糙度Ra係6.9nm。矽層14、碳層16、及矽系密貼層20之組成係與例1大致相同。
針對例1~9之附載體銅箔,如以下所示,進行各種評價。評價結果如表1所示。
應該評價載體12的熱壓耐性,單體地準備在各例使用之載體12,調查其耐熱性。具體而言,將載體12載置在熱板,於大氣氛圍下從室溫起加熱使溫度逐漸上升,在從200℃起每10℃溫度到達之階段,觀察載體12發生之龜裂有無發生,根據以下之順位給予評價。
-評價AA:在290℃以上龜裂未發生。
-評價A:在260℃以上290℃未滿下龜裂發生。
-評價B:在230℃以上260℃未滿下龜裂發生。
-評價C:在230℃未滿下龜裂發生(不可)。
將附載體銅箔10的矽系密貼層20側、層積在厚度
30μm之附樹脂銅箔(RCC)(材質:環氧樹脂、Mitsui Mining & Smelting(股)公司製)的樹脂面並在220℃、以90分鐘30kgf/cm2的壓力壓製。對於得到的銅箔層積板,在載體12依以下條件照射UV-YAG雷射,形成到達附樹脂銅箔(RCC)內的銅層之通孔。
-裝置:UV-YAG雷射加工機(LUC-2K21、Via Mechanics(股)公司製)
-製程:叢發模式(Burst mode)
-輸出:0.93W(例1~4及6~8)或5.26W(例5)
-脈衝重複率:50kHz
-照射數:42(例1~4及6~8)或30(例5)
-目標徑:30μm
對於形成之通孔,計測以目標徑(30μm)為基準之通孔徑的加工精確度,按以下的基準給予評價。
-評價A:±3μm的範圍內之加工精確度
-評價B:±5μm的範圍內之加工精確度(但,排除符合評價A者)
-評價C:±10μm的範圍內之加工精確度(但,排除符合評價A及B者)
應該評價除沾污處理之載體12的耐蝕性,單體地準
備在各例使用之載體12,調查其耐過錳酸鈉性。具體而言,將載體12於80℃下浸漬在過錳酸鈉溶液(過錳酸鈉濃度:12Vol%、製品名:MLB213、Atotech公司製)30分鐘後測定因載體的溶出導致之重量減少,按以下的基準給予評價。
-評價A:5重量%未滿
-評價B:5重量%以上10重量%以下
-評價C:10重量%以上(不可)
應該評價因除沾污處理造成之剝離層(亦即矽層14及碳層16)的耐蝕性,利用上述雷射加工性試驗對被形成通孔的銅箔層積板進行用過錳酸鈉溶液之除沾污處理,評價從通孔端起的藥液的浸蝕量。
該除沾污處哩,係使用Rohm and Haas Electronic Materials(股)公司所製之以下所示之處理液,並藉由依序進行以下各處理來實施。
-處理液:20體積%(800mL/4L)之CIRCUPOSIT MLB CONDITIONER 211及10體積%(400mL/4L)之CIRCUPOSIT Z
-處理條件:於75℃下浸漬5分鐘
-處理液:12體積%(480mL/4L)之CIRCUPOSIT MLB PROMOTER 213A-1及15體積%(600mL/4L)之CIRCUPOSIT MLB PROMOTER 213B-1
-處理條件:於80℃下浸漬5分鐘、10分鐘、20分鐘、或30分鐘
-處理液:5體積%(200mL/4L)CIRCUPOSIT MLB NEUTRALIZER 216-5
-處理條件:於45℃下浸漬5分鐘
將利用上述除沾污處理所得到之銅箔層積板於120℃下乾燥5分鐘。自銅箔層積板將載體12剝離,藉由用顯微鏡觀察在極薄銅層18與附樹脂銅箔(RCC)的界面之浸蝕量而加以測定。極薄銅層18與附樹脂銅箔(RCC)的界面之過錳酸鈉溶液侵入之領域會變色。因而,上述浸蝕量的測定,係觀察這樣被實施除沾污處理的銅箔層積板的通孔周邊,並將自通孔端起的藥液的浸蝕量,藉由計測因藥液的浸蝕所造成之變色領域之自通孔端起的最大到達距離依照以下的基準加以評價。
評價A:自通孔端起的藥液浸蝕量為10μm以下
評價B:自通孔端起的藥液浸蝕量為10μm超過、50μm以下
評價C:自通孔端起的藥液浸蝕量為50μm超過(不
可)
以以下之方式進行測定附載體銅箔之真空熱壓後的剝離強度。將附載體銅箔10的矽系密貼層20側、層積在厚度30μm之附樹脂銅箔(RCC)(材質:環氧樹脂、Mitsui Mining & Smelting(股)公司製)的樹脂面並在220℃、以90分鐘30kgf/cm2的壓力壓製。對得到的銅箔層積板,遵照日本工業標準JIS C 6481-1996,測定剝離載體箔時的剝離強度(gf/cm)。此時,測定幅設為50mm、測定長度設為20mm。將這樣作法得到的剝離強度(平均值)、按以下的基準給予評價。
評價A:剝離強度為10~30gf/cm
評價B:剝離強度為5~50gf/cm
評價C:剝離強度為未滿5gf/cm或超過50gf/cm(不可)
綜合上述各種的評價,按以下的順位進行給予評價。
評價A:無C評價(不可)、無B評價
評價B:無C評價(不可)、有B評價
評價C:有C評價(不可)
10‧‧‧附載體銅箔
12‧‧‧載體
14‧‧‧矽層
16‧‧‧碳層
18‧‧‧極薄銅層
20‧‧‧矽系密貼層
Claims (7)
- 一種附載體銅箔,其特徵係具備:由從聚萘二甲酸乙二醇酯樹脂、聚醚碸樹脂、及聚苯硫醚樹脂選擇出之至少1種樹脂所構成之載體,被設在前述載體上、包含矽而成,矽濃度係60原子%以上之矽層,被設在前述矽層上、包含碳而成,碳濃度係60原子%以上之碳層,與被設在前述碳層上,具有50~2500nm的厚度之極薄銅層。
- 如申請專利範圍第1項記載之附載體銅箔,其中前述矽層係具有1~50nm之厚度。
- 如申請專利範圍第1項記載之附載體銅箔,其中前述碳層係具有0.1~10nm之厚度。
- 如申請專利範圍第1項記載之附載體銅箔,其中前述極薄銅層之與前述碳層相反側之表面,係具有依據日本工業標準JIS B 0601-2001測定之0.2~100nm的算術平均粗糙度Ra。
- 一種附樹脂銅箔,其特徵係具備申請專利範圍第1~4項任一項記載之附載體銅箔、與被設在前述附載體銅箔之前述極薄銅層上之樹脂組成物層。
- 一種印刷電路板之製造方法,其特徵係 包含:至少在核心層的單面依序層積樹脂層及申請專利範圍第1~4項任一項記載之附載體銅箔,或層積申請專利範圍第5項記載之附樹脂銅箔,形成附載體層積體之步驟;對前述附載體層積體施以雷射加工,形成通孔之步驟;去除前述通孔的污跡之除沾污處理步驟;與前述除沾污處理步驟後,剝離前述載體之載體剝離步驟。
- 如申請專利範圍第6項記載之印刷電路板之製造方法,其中在前述除沾污處理步驟與前述載體剝離步驟之間、或前述載體剝離步驟後,進而包含進行無電鍍銅之步驟。
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