TWI462671B - 印刷電路電板 - Google Patents

印刷電路電板 Download PDF

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Publication number
TWI462671B
TWI462671B TW97105763A TW97105763A TWI462671B TW I462671 B TWI462671 B TW I462671B TW 97105763 A TW97105763 A TW 97105763A TW 97105763 A TW97105763 A TW 97105763A TW I462671 B TWI462671 B TW I462671B
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TW
Taiwan
Prior art keywords
coating
printed circuit
circuit board
pcb
composition
Prior art date
Application number
TW97105763A
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English (en)
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TW200843590A (en
Inventor
Frank Ferdinandi
Rodney Edward Smith
Mark Robson Humphries
Original Assignee
Semblant Ltd
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Publication of TW200843590A publication Critical patent/TW200843590A/zh
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Publication of TWI462671B publication Critical patent/TWI462671B/zh

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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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
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    • H01L24/80—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
    • H01L24/85—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 wire connector
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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Description

印刷電路電板
本發明係關於諸如彼等包括塗覆有一鹵代烴聚合物之印刷電路電板之製品。
印刷電路電板(PCB)在電子產業中用於電零件及電子零件之機械支撐及電連接。一PCB包括一電板或由一絕緣材料製成之其他基板，在該基板上存在多個導電印製線(通常由銅製成)。該等導電印製線用作稍後藉由(舉例而言)軟銲方式附裝至該電板上之電零件之間的導線。PCB之一大部分係藉由如下方式製造：沈積或以其他方式將一層銅黏附於該基板電板上，然後藉由化學蝕刻去除多餘之銅，使銅印製線保持呈所需組態。在藉由軟銲方法將電子零件附裝至該PCB上之前，通常可能將空白PCB儲存在此階段達不定之時間段，可能多達數月。
印刷電路電板上之導電印製線可由任何導電材料製成。印製線之較佳材料係銅。銅係較佳導電印製線材料之原因主要在於其高導電性，但遺憾地是，銅易於在空氣中氧化，從而在金屬表面上產生一層氧化銅或使金屬表面晦暗。如果在空白PCB之製造與該電零件之附裝之間已經過一長時間段，則氧化會尤其明顯。該等零件係藉由軟銲進行附裝，但銅印製線上存在一氧化層可降低軟銲之有效性。尤其可形成在裝置運行期間往往發生故障之幹接縫及具有低機械強度之弱接縫。有時，該接縫將無法實現電接 觸在一起。當導電印製線包括除銅以外之導電材料時，會出現類似問題。
為最大程度地減少該等問題，PCB製造商對需要進行軟銲之區域實施一系列塗覆或表面漆面。通常使用諸如錫、銀或一鎳/金組合物等金屬。實施該等漆面之製程皆係耗時、需要使用額外金屬，伴隨有隨之產生之環境問題。可能會存在與某些製程及材料相關之健康問題。而且，所用之某些金屬(例如，金)係非常昂貴。一類似方法涉及：以一包括諸如苯并咪唑及銲料可濕金屬或銲料之微粒(參見(舉例而言)WO 97/39610)等有機化合物塗層塗覆該印製線，從而防止印製線暴露於氧化條件下。接軟銲期間，簡單移除該有機層。該等有機塗層通常無法經受得住多次熱循環，且在處理之前具有一相對短之儲存壽命。
很明顯，製造商目前所採用之技術或者昂貴或者耗時(包括製造製程中之額外步驟)、或者兩者兼具，並消耗不可再生資源(包括貴金屬)。存在對一在藉由軟銲附裝電零件之前防止導電印製線氧化之更便宜及/或更高效能之方法的需要。
一個別問題係PCB通常為用於非常惡劣及腐蝕環境中之裝置所需。在此等條件下，PCB上之導電印製線可能被腐蝕，導致電路電板之使用壽命比通常期待之壽命短得多。舉例而言，當裝置在一非常潮濕之環境下使用時，尤其在含有已溶解氣體(例如，二氧化硫、氫硫化物、二氧化氮、氯化氫、氯及水蒸氣)之顯微水滴形成一腐蝕性溶液 之環境中，可能會出現此等情況。此外，潮濕滴液可能會在PCB上之導電印製線之間形成一很可能造成短路之薄膜或腐蝕沈積。在PCB製造商設計將該等裝置用於惡劣條件中之情況下，其往往以一共形聚合物塗層塗覆經組裝之PCB，該塗層形成一環境阻擋層。然而，塗施此等塗層非常昂貴，且待PCB組裝完畢後在製造過程中需要一額外步驟來塗施該塗層，及通常稍後需要一額外步驟來移除該塗層。當再次處理一受損或故障之PCB時，或在測試以確定其效能及查找一故障問題期間亦可能引起問題。製造商將會對一更便宜及/或高性能之環境保護經完成之PCB之方法具有極大的興趣。
在將電子零件軟銲於一PCB上之後可能會出現之另一問題係在軟銲接合(solder joint)上形成金屬化合樹枝晶。該等樹枝晶可能會因觸點之間短路而造成經組裝之PCB故障。樹枝晶係電遷移所致之沿一表面之細微金屬生長，其形成蕨類植物狀型樣。人們透徹地瞭解樹脂晶之形成機理，其與"錫須"不同，且需要產生金屬離子之濕氣之存在，隨後金屬離子會藉由存在一電磁場之電子遷移而被重新分配。本發明之塗層藉由阻止濕氣達到PCB之表面來防止樹枝晶之形成，PCB表面通常是樹枝晶生長之位置。該塗層提供額外保護，因為樹枝晶材料具有對低表面塗層的黏附力，從而減少觸點與零件之間的樹脂晶的形成。
本發明提供一種通常局部銲料連接之印刷電路電板，該 印刷電路電板表面具有一包括一個或多個鹵代烴聚合物之組合物之塗層(一層或多層)，其厚度為一單層之厚度(通常為幾埃(A))至10微米，其中該塗層組合物與該印刷電路電板之導電印製線之間沒有銲料或基本上沒有銲料。關於聚合物，其包括由下列各項就地形成之聚合物：單個或多個單體、直鏈、具支鏈、接枝及交聯共聚物、寡聚物、多元聚合物、多單體聚合物、聚合物混合物、接枝共聚物、聚合物之摻合物及合金、及互穿網絡聚合物(IPN)。
該塗層之厚度典型係1奈米－2 2微米，更典型係1奈米－500奈米，再更典型係3奈米－500奈米，再更典型係10奈米－500奈米，最典型係10奈米－250奈米。該塗層係較佳在一10奈米－100奈米之厚度上，在各種梯度中，其中100奈米係一較佳厚度。於另一實施例中，該塗層厚度係10奈米－30奈米。然而，該塗層之最佳厚度將取決於PCB所需之性質。舉例而言，如果需要非常高之環境韌性(高抗腐蝕性及耐磨性)，則可能採用一較厚塗層。此外，端視哪一特徵最佳(舉例而言，環境保護與Z軸導電性之對比)，在PCB之不同位置採用不同厚度，可使塗層厚度最佳化。可改變塗層厚度及銲劑組合物來最優化環境保護特性及提供特別堅固之軟銲接合。
該鹵代烴塗層可係連續、大致上連續(特別是在欲進行軟銲之表面及在其之間或毗鄰其之非軟銲表面上，及尤其在PCB之大致上全部暴露且易損之表面上)或不連續。一非常高水平之環境保護，可能需要一大致上連續之塗層。然 而，對於其他用途，一不連續塗層可能已足夠。
鹵代烴聚合物係指一具有一直鏈或具直鏈或環狀碳結構之聚合物，其中該結構中0、1、2或3個鹵素原子連接至每一碳原子。該等鹵素原子可以係相同鹵素(舉例而言，氟)或鹵素原子之混合物(舉例而言，氟及氯)。本文所用術語"鹵代烴聚合物"包括包含一個或多個不飽和基團之聚合物(例如碳碳雙鍵及三鍵)及包含一個或多個雜原子(非C、H或鹵素之原子，舉例而言，N、S或O)之聚合物。然而，目前我們更喜歡該聚合物大致上不包含不飽和物(因為不飽和物通常會降低穩定性)及大致上不包含此等共原子。較佳地，該聚合物包含不超過5%之共原子作為該聚合物中原子總數之一部分。較佳地，該聚合物包含不超過5%之碳－碳雙鍵或三鍵作為碳－碳鍵之總數之一部分。該聚合物之分子量係較佳大於1000 amu。
該等聚合物鏈可係直鏈或具直鏈，且在聚合物鏈之間可能存在交聯。鹵素可指氟、氯、溴或碘。較佳地，該聚合物係一氟代烴聚合物、一氯代烴聚合物、或一氯氟烴聚合物，其中在鏈中，0、1、2或3氟或氯原子結合至每一碳原子。
較佳聚合物實例包括：－PTFE、PTFE類材料、氟化烴、氯氟化烴、鹵化烴、鹵代烴或共聚物、寡聚物、多元聚合物、多單體聚合物、聚合物混合物、摻合物、合金、具直鏈、接枝共聚物、該等材料亦及互穿網絡聚合物(IPN)之交聯變體。
－PCTFE(聚三氟氯乙烯)和共聚物、寡聚物、多元聚合物、、多單體聚合物、聚合物混合物、摻合物、合金、具直鏈、接枝共聚物、該材料亦及互穿網絡聚合物(IPN)之交聯變體。
－EPCTFE(聚三氟氯乙烯之乙烯共聚物)和共聚物、寡聚物、多元聚合物、多單體聚合物、聚合物混合物、摻合物、合金、具直鏈、接枝共聚物、該材料亦及互穿網絡聚合物(IPN)之交聯變體。
－其他氟塑膠，其包括下列材料和共聚物、寡聚物、多元聚合物、多單體聚合物、聚合物混合物、摻合物、合金、具支鏈、接枝共聚物、該等材料及互穿網絡聚合物(INP)之交聯變體：ETFE(乙烯和四氟乙烯之共聚物)、FEP(四氟乙烯和六氟丙烯之共聚物)、PFA(四氟乙烯和全氟乙烯醚之共聚物)、PVDF(偏氟乙烯之聚合物)、THV(四氟乙烯、六氟丙烯和偏氟乙烯之共聚物)PVDFHFP(偏氟乙烯和六氟丙烯之共聚物)、MFA(四氟乙烯和全氟乙烯醚之共聚物)、EFEP(乙烯、四氟乙烯和六氟丙烯之共聚物)、THE(六氟丙烯、四氟乙烯和乙烯之共聚物)或偏氟乙烯和氯三氟乙烯之共聚物及其他氟塑料。
最佳地，該聚合物係一聚四氟乙烯(PTFE)類材料，及特定而言係聚四氟乙烯(PTFE)。
一更低可濕性可藉由使用一塗層來實現，在該塗層中，該鹵代烴係一高支化聚合物、一共聚物、聚合物摻合物或一聚合物混合物。
期望該塗層組合物具有下列性質中之任何一者或多者及較佳地大致上所有性質：能夠沈積為連續薄膜，無裂縫、孔洞或瑕疵；相對低之透氣性，該低透氣性提供一重要氣體滲透屏障且避免氣體腐蝕及氧化'透過'該塗層；能夠在無需事先清除之情況下穿透性地進行選擇性軟銲並能夠獲得較其他目前可用之表面漆面為佳之良好軟銲接合；能夠耐受多個熱循環；對腐蝕氣體之耐化學性、液體及鹽溶液，尤其是環境污染物；顯示低表面能量和'濕潤度'；在正常PCB溫度下係穩定的惰性材料；具有良好的機械性質，其包括與PCB材料之良好黏附性及良好之抗機械耐磨性；改良之靜電保護；相對低之液體及鹽溶液滲透性，以避免液體腐蝕"透過"該塗層；及當該應用中使用時，與現有製程相比通常對環境有益。
本發明亦可提供具有此一塗層且在其上進行軟銲連接之其他電裝置及/或電子裝置或其他製品(例如，管道或其他管件設備)。舉例而言，本發明可用於塗覆線接合技術中所用之裸線(尤其是銅線)。線接合係一在一呈裸晶片形式之積體電路與該積體電路內之導線架之間或該裸晶體與一PCB之間進行互連之方法。所用之電線傳統上係金或鋁的，但最近對使用銅線產生了相當大的興趣，原因有很多，包括其與金之相當大之成本差值。在線接合中，通常採用兩種接合方法：楔形結合及球形結合，上述兩種方法均使用熱、壓力及超聲能量之不同結合在該電線之任一端或兩端進行一銲接。為實現一良好結合，電線及其結合之 銲墊兩者必須均沒有污染物，包括氧化物。標準實踐係向銲墊施塗一金漆面來防止氧化。銅銲墊上本發明塗層亦將提供一不氧化表面，其允許藉由楔形結合或球形結合使用金、鋁或銅線但以一明顯低於銲墊上之標準金漆面之成本形成線接合接縫。若正使用銅線，則向該電線塗覆該鹵代烴塗層來防止該導線在生產出之後及儲存之前被氧化亦非常有益。而且，該鹵代烴塗層在結合製程期間提供其他氧化防護。另一選擇係，於本發明之另一實施例中，可塗覆該電零件之電極。該聚合物塗層較佳地對大氣氣體、液體，最重要的是對氧氣之滲透提供一良好屏障，氧氣通常會與該導電印製線(典型地係銅印製線)發生反應以在印製線表面上形成一失澤(典型地係氧化銅)層。因此，該經塗覆之電路電板可儲存一長時間段(多達數月或數年)，而該等導電印製線不會發生損壞氧化。已採用了光學顯微鏡方法、掃描電子顯微鏡方法及反向散射電子成像來研究該塗層之性質、連續性及厚度。已採用藉由X－射線之能量分散分析來映射塗層中鹵素水平與分佈。利用化學溶劑溶液測量之表面活化及表面可濕性提供用作一保護塗層之潛力之指示。
一旦製造商準備好於該空白PCB上安裝零件時，無需在軟銲製程之前清潔該PCB或去除該塗層。出現該情況乃因所用鹵代烴聚合物令人驚訝地提供一具有不尋常性質之塗層，其可被軟銲穿透以在電板上之導電印製線與電零件之間形成一軟銲接縫。該軟銲技術中通常需要銲劑。極端 地，可使用一單獨使用熱量之軟銲製程(舉例而言，雷射銲)來選擇性地"去除"該塗層。更多選擇係銲接、雷射強化銲接、超聲波熔銲接或使用導電黏合劑。另一可能技術係波銲，該技術可能要求選擇性銲劑。所用銲料可係鉛銲料或無鉛銲料。如所期望，通常不會降低軟銲接縫強度，事實上，在某些情況下，該軟銲接合可能強於一標準軟銲接合。而且，在某些情況下，本發明可防止在軟銲結合上形成樹枝晶，尤其當使用無鉛銲料時。
因此，本發明提供一種替代技術來向PCB之導電印製線塗施金屬(例如，錫、銀、鎳及金)表面塗層來防止軟銲前導電印製線之氧化。本發明具有如下優勢：其基於一低成本製程、其不使用有毒金屬(例如，鎳)，其係環境友好及其比目前之產業金屬噴鍍製程更安全。本發明亦簡化了PCB製造製程且與目前之產業軟銲製程相容。此外，本發明具有"銲透"性質之額外益處，藉此可避免在軟銲前去除該塗層之需要。
該鹵代烴聚合物塗層之再一特徵係僅去除實施軟銲及/或銲劑區域內之塗層。因此，在藉由選擇性軟銲不進行零件附裝之PCB區域中，塗層保持完好，保留該電板及導電印製線上之一保護層，該保護層對大氣氣體(例如，二氧化硫、硫化氫、二氧化氮、氯化氫、氯氣及水蒸汽)及其他腐蝕材料之腐蝕提供一屏障，從而避免被環境污染物腐蝕。鹵代烴聚合物塗層亦大致上不滲透液體及腐蝕性液體。因此，可藉由一系列其間具有明顯時間間隔之步驟將 零件安裝至該電路電板上，此能為製造商提供許多有利條件。除經選定之軟銲區域外，該塗層並未被該軟銲製程破壞，所以，在非軟銲區域中，該PCB可藉由稍後步驟中之軟銲進行再加工及/或再處理。而且，在該PCB之組裝完成之後，該PCB之該未軟銲區域仍塗覆有該鹵代烴聚合物，該聚合物形成對環境腐蝕之一永久屏障。無需進一步高代價之塗覆步驟(例如，保形塗覆)。
該印刷電路電板上之該等導電印製線可包括任何導電材料。製成該等導電印製線之可能材料係金屬，例如銅、銀、鋁或錫、或導電聚合物或導電油墨。該等印製線之較佳材料係銅。導電聚合物往往會吸收水並膨脹，因此，具有一鹵代烴聚合物層之塗層導電聚合物可防止水之吸收。
本發明經塗覆PCB之另一特徵係沿z－軸之阻抗與x－及y－軸之阻抗相比非常低。z－軸係指指向該PCB平面之軸。該塗層沿x－及y－軸顯示高阻抗，從而展示了良好之絕緣性質。然而，沿z－軸之阻抗相對低。這使得能夠在不必去除該塗層之情況下透過該塗層進行電接觸。此對於諸如鍵盤、開關觸點、測試點及類似物之應用尤其有利。該特點可藉由控制該塗層之性質進一步最佳化，例如，藉由控制層之厚度、其組合物及塗覆製程中的製程條件及塗覆製程之性質。
概言之，本發明防止了空白PCB之導電印製線之氧化及/或其他環境損壞，例如，熱穩定性之調變、刮傷、耐腐蝕性及耐化學性及高屏障效應，且通常以給空白PCB塗覆一 鹵代烴聚合物之一個原始步驟來提供該經組裝PCB之環境保護。
本發明亦提供一種保護一印刷電路電板之方法，該方法包括：提供一具有一暴露於環境之表面之空白印刷電路電板，該印刷電路電板在該暴露於環境之表面上無銲料或基本上無銲料；藉由一薄膜沈積技術向彼表面塗施一厚度為一單層(通常為幾埃())至10微米之包括一鹵代烴聚合物之組合物，該薄膜沈積技術如，電漿沈積、化學汽相沈積(CVD)、分子束磊晶生長(MBE)、互穿聚合物網路(IPN)之創建、用以形成原位聚合物之單體聚合物之單層表面吸收(SAM)、聚合物合金或濺鍍。> 替代沈積技術係：電漿強化－化學汽相沈積(PE－CVD)、高壓/大氣電漿沈積、有機金屬化學汽相沈積(MO－CVD)及雷射強化－化學汽相沈積(LE－CVD)。液體塗覆技術，例如液體浸鍍、噴塗、旋塗及溶膠/凝膠技術係更多選擇。
較佳方法取決於所需之塗層厚度。液體塗層可較佳地用於較厚塗層，而電漿沈積技術可較佳地用於較薄塗覆。塗層厚度典型地係1奈米至2微米，更典型地自1奈米至500奈米，再更典型地自3奈米至500奈米，再更典型自10奈米至500奈米，及最典型地自10奈米至250奈米。該塗層較佳處於自10奈米至100奈米之厚度，其中最佳厚度係100奈米。該鹵代烴聚合物較佳係一氟代烴聚合物、一氯代烴聚合物或一氯氟烴聚合物，其亦可能包含細緻色素粒子及少量其他效能添加劑(係聚合物產業中之常見實踐)，且可能(舉例 而言)係聚四氟乙烯(PTFE)類材料。向該空白PCB施塗該鹵代烴聚合物之較佳方法係電漿沈積，當然上述所有其他技術亦將適用。
電漿沈積在廣大產業應用中廣泛用於塗層之沈積。該方法係一利用一乾燥及環境友好技術沈積連續薄膜塗層之有效方法。該等PCB係在一產生一氣體電漿之真空室內塗覆，該氣體電漿包括經電離之氣體離子、電子、原子及中性粒子。在該方法中，將該PCB引入首先被抽吸至壓力通常在10"－10 mbar範圍內之真空室中。然後，將一氣體引入至真空室中以產生一穩定氣體電漿，然後將一個或多個前體化合物引入該電漿作為一氣體或者液體使沈積製程能夠進行。
該等前體化合物典型地係經選擇以提供期望之塗層性質之含鹵素之烴材料。當被引入至該氣體電漿時，該等前體化合物亦經電離/分解產生一系列活性物質，該等活性物質將典型藉由一聚合製程在該PCB之表面發生反應，來產生一薄鹵代烴塗層。較佳前體化合物係全氟烷烴、全氟烯烴、全氟炔烴、氟代烷烴、氟代烯烴、氟炔烴、氟氯烷烴、氟氯烯烴、氟氯炔烴或任何其他氟化及/或氯化有機材料(例如，氟代烴、氟碳化合物、氯氟烴及氯氟碳化合物)。
於本發明之另一態樣中，該PCB之導電印製線上之塗層可包括一層非常薄(例如，5奈米或更薄)之直接接觸該金屬表面之金屬鹵化物(較佳地一金屬氟，例如氟化銅)。於一 個實施例中，該金屬鹵化物層可係一單層或大致上一單層，或幾個單層，或在表面上包括一金屬鹵化物層帶。此一金屬鹵化物層可係極其堅固且具有惰性，並防止氧化層或其他阻止有效軟銲之失澤層之形成。當氣體電漿中之活性物質與該金屬表面反應時，可能會形成該金屬鹵化物層或可應用一更高濃度度之氟物質強化該金屬鹵化物層。然後，可結合該金屬鹵化物層沈積該鹵代烴層。該兩層可軸向或空間分離，或替代地可存在自金屬鹵化物至鹵代烴之分級過渡。該金屬鹵化物層可保護該金屬不被氧化，而該鹵代烴層針對腐蝕氣體及/或液體提供環境保護以及氧化保護。而且，若該塗層最終因機械磨損而被磨掉，則下伏金屬氟化物層將會防止氧化增進，使仍然能夠進行接觸。電漿沈積塗層之性質及組合物取決於多個條件：所選電漿氣體；所用前體化合物；電漿壓力；塗覆時間；電漿電源；室電極佈置；輸入PCB之製備；及該室之大小及幾何形狀。典型地，該電漿沈積技術可用於沈積自一單層(通常幾埃())至10微米(較佳至5微米)之薄膜，其相依於上述設置及條件。該電漿技術自身通常只影響該PCB之最上表面及典型地與該PCB自身完全相容，不會造成損害或其他不期望之影響。電漿塗層技術之一優勢在於沈積塗層觸及該PCB之所有表面，因此亦將覆蓋垂直表面(諸如僅經由該PCB中之孔方可觸及之彼等表面)及任何懸垂面。如果該PCB之一特定區域(舉例而言該PCB之邊緣之金觸點)不應塗覆有聚合物，則在電漿沈澱製程期間可將該等區域罩 住。
在一電漿製程之一變化形式中，在使用一活性氣體電漿進行電漿沈積之前，可應用該電漿方法就地清潔該PCB表面。在該變化形式中，在引入前體化合物進入電漿沈積階段之前，通常在該同一室中使用一活性氣體電漿進行PCB清潔。該活性氣體電漿係基於一穩定氣體，例如氫氣、氧氣、氮氣、氬氣、甲烷、乙烷、其他碳氫化合物、四氟甲烷(CF4 )、六氟乙烷(C2 F6 )、四氯甲烷(CCI4 )、其他氟化或氯化烴、其他稀有氣體或上述氣體之一混合。於一個特定實施例中，該PCB可藉由與欲沈積之材料相同之材料進行清潔。舉例而言，在該電漿方法中，可應用一氟化或氯化烴(例如，四氟甲烷(CF4 )或六氟乙烷(C2 F6 )或六氟丙烯(C3 F6 )或八氟丙烷(C3 F8 ))既清潔PCB表面又沈積一層鹵代烴聚合物及/或一層金屬氟化物(或氯化物)。
本發明亦提供一種連接一印刷電路電板之方法，該印刷電路電板塗覆有一包括一鹵代烴聚合物之組合物，該方法包括以一溫度將銲料及銲劑應用到該印刷電路電板達一段時間，以使該銲料結合至該金屬，且該組合物被局部分散及/或吸收及/或汽化及/或分解及/或反應。銲劑及升高之溫度之作用單獨地通常將與鹵代烴聚合物相互作用來局部去除該PCB之將施加銲劑之區域的塗層。該溫度通常係200℃－300℃，較佳係240℃－280℃，及最佳係260℃。於一個實施例中，該鹵代烴聚合物可藉由該銲劑分解及/或吸收。人們已經發現，在所需溫度與銲劑之酸性或其他腐蝕 性之間通常存在一平衡。因此，若應用的溫度較高，則較溫和之銲劑即可足夠，反之亦然。於另一實施例中，我們可利用銅表面之氟化銅之自熔性作用及聚合物塗層之任何分解來釋放氟化物及/或HF以起始熔融(自熔融)。在極個別情況下，我們發現在特定情況下，如果使用一足夠高之溫度且採用相當局部化之加熱，則可本發明可省卻銲劑。令人吃驚地，通常僅具體地自施加銲料及/或銲劑之區域中移除該組合物，所以該組合物仍附裝至該PCB之表面上直至軟銲接合。該為PCB之導電印製線提供有利之環境保護直至軟銲接合。
本發明中所用之銲劑可係一樹脂/松香銲劑、一有機銲劑、一無機銲劑、一無鹵素銲劑、一免清洗銲劑、一低殘留銲劑或一低固含量銲劑。一樹脂/松香銲劑可(舉例而言)係一合成樹脂或一天然松香。一有機銲劑可(舉例而言)係：一有機酸(例如，乳酸)或一丙烯酸；一有機鹽(例如，二甲基氯化銨(DMA HCI))；或一有機胺(例如，尿素)。一無機銲劑可(舉例而言)係：一無機鹽，例如氯化鋅、氯化鈉、氯化鉀或氟化鉀；或一無機酸，例如鹽酸或硝酸。一免清洗銲劑之一實例係一松香銲劑。亦可將其他更廣泛地用於諸如一般軟銲、銅銲及銲接或清潔或蝕刻一金屬表面(舉例而言，硼酸)等產業應用之其他銲劑用於本發明中。該方法中所用之銲劑通常係一不需要一隨後清潔該PCB之步驟之溫和銲劑，例如一"免清洗"銲劑。該銲劑可選地係一銲藥之一部分。銲劑之選擇取決於塗層性質，特定而言 係塗層之厚度及組合物。一較厚、更具抵抗力之塗層可能要求使用一更具侵蝕性之銲劑。一包括用於自該電板去除鹵代烴組合物之活性組份或銲劑組份之組合物亦可替代銲劑用於本發明中。
而且，本發明提供一種包括一鹵代烴聚合物之組合物環境保護一印刷電路電板之使用，在存在一銲劑之情況下，無需預先去除該組合物而視需要藉由對該組合物之分散及/或吸收及/或汽化來透過該組合物對該印刷電路電板實施一軟銲連接。
環境中可包含氣體介質，例如二氧化硫、硫化氫、二氧化氮、氯化氫、氯氣、臭氧或水蒸汽，或液體諸如水，上述腐蝕性氣體溶解於其中的水、鹽溶液或其他流溢物。此等氣體共存於高度污染環境中，例如存在大氣污染問題之城市中。本發明保護PCB免受之一個特定環境危害係大氣水分，上文所列之腐蝕性氣體中之一者或多者可溶解於大氣水分中。我們發現，本發明亦能夠保護PCB免遭此惡劣環境影響。
本發明亦提供一種包括一鹵代烴聚合物之組合物為一待進行軟銲連接之空白印刷電路電板提供長期儲存穩定性之使用。如上文所述，如果使其暴露於大氣中，則PCB上之導電印製線往往會氧化。該氧化反應通常藉由與大氣氧氣之反應而形成金屬氧化物，但亦包括其他氧化反應，舉例而言銅金屬被氧化成(舉例而言)Cu＋ 或Cu2＋ 之情況。本發明之組合物防止該等氧化反應，從而可將一空白PCB儲存一 長時間段而不會發生導電印製線之氧化。因此，經過長期儲存後，可藉由標準軟銲技術，較佳地在存在銲劑之情況下不實施任何預清洗步驟即可進行對PCB之良好之軟銲連接。
本發明亦提供一種包括鹵代烴聚合物之組合物在對該等導電印製線實施軟銲及/或形成一軟銲連接之前防止一空白印刷電路電板之導電印製線氧化及/或腐蝕的應用。
 實例
經塗覆印刷電路電板之製備 自一製造商處獲得經蝕刻及清洗但尚未實施表面漆面之印刷電路電板。然後，藉由電漿沈積處理該等板以產生該含有齒素之塗層。將該PCB引入至首先降壓至10－3 －10 mbar範圍內之壓力之真空室中。然後，將一氣體引入至該真空室以產生一穩定氣體電漿，且然後將一含有鹵素之前體碳氫化合物引入至該電漿中以使該沈積製程能夠進行。當被引入至該氣體電漿時，該前體化合物亦經分解/電離產生一系列活性物質，該等活性物質在該PCB表面反應以產生一薄含鹵素塗層。在該等經處理板上執行多個試驗。
實例1 手動將一市售含鉛銲藥自一注射器塗施至該PCB一側之多個零件銲墊上。將若干積體電路置於其上具有銲藥之銲墊上。然後，將該PCB放入一迴銲爐中，在該迴銲爐中，已如圖1中所示設定軟銲分佈。隨後，使用一顯微鏡目視 檢查該等接縫，其中發現該等接縫具有良好的浸濕特性。然後，藉由使用一工具撬開該零件來拉開某些接縫。在每一將該積體電路之插腳從該銲料中拔出之情況下，皆使至該PCB片銲墊之接縫保持完好。
實例2 使用無鉛銲藥以圖2中所示之一經修改之回流銲分佈重複上述測試，所得結果相似。
實例3 將銲劑塗施於兩個PCB之區域中，將該兩個PCB之區域加熱至260℃分別達10秒鐘及5分鐘。實驗顯示，在該等PCB之任一者之已塗施銲劑之區域中皆不再存在塗層。然而，在尚未塗施銲劑之區域中該塗層保持完好。
實例4 剪切強度測試 製備8個具四個PCB漆面之組件進行剪切測試。每一PCB漆面具有兩個組件。每一組件均組裝有7個1206晶片電阻器及4個0805晶片電容器。對每一組件漆面之14個1206電阻器及8個0805電容器進行剪切測試，以確定每一漆面組件之軟銲接合之最終剪切強度(USS)。
測試條件 將該電板安裝在一剪切測試器中。該PCB表面上鑿具之支架高度係80微米，鑿具寬度係2毫米。每一測試期間，該剪切工具以一100 μM/S之界定速度向前移動對撞該測試零件，監視該力直至軟銲接合附裝破裂。所用之剪切測試 器係Dage Series 4000，帶有一DS 100測試頭。
實例5 下文PCB表面能量表顯示隨著塗覆製程時間增強之疏水性：
圖1顯示一使用一市售含鉛銲藥之迴銲爐之軟銲分佈。
圖2顯示一使用一無鉛市售銲藥之迴銲爐之軟銲分佈。
圖3係一表面帶水滴之本發明之一經塗覆PCB之影像，其展示表面塗層之低表面能量、低可濕性、液體不滲透性。
圖4係一藉由本發明之透過一PCB上之塗層進行軟銲所獲得堅固軟銲接合之截面影像。
圖5係一本發明之一PCB上形成之堅固軟銲接合之截面影像，其展示更低銅表面之上側上之優質銅－錫金屬間化合物之形成。
圖6係一本發明一PCB上厚1微米之塗層聚合物邊緣之SEM(掃描式電子顯微鏡)影像，該影像以x3 0,000之放大率顯示。
圖7係一顯示一本發明經塗覆PCB之一實例區域之BEI影像(反向散射電子影像)，其展示超過99.8%覆蓋率之塗覆連續性。
圖8係一顯示藉由處於一溫度之銲劑之作用有選擇地去除本發明一PCB之一標稱1微米厚度之塗層之區域之SEM/EDX影像。左邊影像顯示已選擇性地塗施銲劑之位置。右邊影像顯示塗施了銲劑之區域內之塗層已被有選擇性地去除。
圖9係一顯示本發明之一PCB之銅上塗層之碳/氟組合物之EDX圖譜。
圖10係從本發明之一經軟銲PCB撕下之IC零件腳之影像，其展示堅固軟銲接合。在嚴格的測試中，該等軟銲接合最終因銅銲墊至電板基板之結合而非在軟銲接合處之破 裂而失效。
圖11係一自本發明之經軟銲PCB上撕下經軟銲銲墊之影像，其展示堅固之軟銲接合。在嚴格的測試下，該等軟銲接合最終因銅銲墊結合至電板基板之結合而非在軟銲接合處之破裂而失效。
圖12係一SEM圖及一EDX影像，其顯示本發明之一PCB上形成之直至一軟銲接合邊緣之聚合物塗層之存在。
圖13係一顯示形成於本發明一PCB上之一系列優質軟銲接合之光顯微鏡影像。
圖14a係本發明之一組薄塗層之XPS圖譜，其顯示來自C－F及Cu－F材料之各種作用。
圖14b係一XPS圖譜，其顯示含有用於一厚塗層之C－F之材料。
(無元件符號說明)

Claims (10)

  1. 一種待進行一軟銲連接之印刷電路電板，該印刷電路電板表面具有一塗層，該塗層由一厚度為1奈米至10微米且包括一種或多種鹵代烴聚合物之組合物構成，其中在該印刷電路電板之該塗層與導電印製線之間不存在銲料，且其中實施該軟銲連接無需預先移除該塗層。
  2. 如請求項1之印刷電路電板，其具有一塗層，該塗層由一厚度為10奈米至100奈米且包括一種或多種鹵代烴聚合物之組合物構成。
  3. 如請求項1或2之印刷電路電板，其中該聚合物係一氟代烴。
  4. 如請求項1或2之印刷電路電板，其中該印刷電路電板之表面具有一由一金屬氟化物構成之塗層，該金屬氟化物塗層之厚度為最多5奈米，及位於該金屬氟化物塗層上之一組合物構成之一塗層，該組合物包括一種或多種鹵代烴聚合物，且該組合物塗層之厚度為1奈米至10微米。
  5. 一種保護待被製作一軟銲連接之一印刷電路電板之方法，該方法包括提供一具有一暴露於環境之表面之印刷電路電板，且該印刷電路電板在該暴露於環境之表面上不存在銲料，且然後藉由一薄膜沈積技術，將一包括一鹵代烴聚合物之組合物塗施至彼表面達1奈米至10微米之一厚度，其中實施該軟銲連接無需預先移除該塗層。
  6. 如請求項5之方法，其中該沈積技術係電漿沈積、化學 汽相沈積、分子束磊晶生長或濺鍍。
  7. 如請求項6之方法，其中該沈積技術係電漿沈積。
  8. 一種實施一連接至一印刷電路電板之方法，該印刷電路電板具有一包括一鹵代烴聚合物之組合物之一塗層，實施該連接無需預先移除該塗層，該方法包括向該印刷電路電板塗施銲料及銲劑，以使該銲料結合至金屬，且局部分散及/或吸收及/或汽化該塗層。
  9. 一種至一印刷電路電板之連接，其係以請求項8之方法獲得。
  10. 一種包括一鹵代烴聚合物之組合物用於環境保護一印刷電路電板之用途，在存在一銲劑之情況下，無需預先移除該組合物即可視需要藉由該組合物之分散及/或吸收及/或汽化來透過該組合物對該印刷電路電板進行一軟銲連接。
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