TW201500195A - 用於雷射燒蝕之具有影像加強的微孔載體 - Google Patents

用於雷射燒蝕之具有影像加強的微孔載體 Download PDF

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TW201500195A
TW201500195A TW103108063A TW103108063A TW201500195A TW 201500195 A TW201500195 A TW 201500195A TW 103108063 A TW103108063 A TW 103108063A TW 103108063 A TW103108063 A TW 103108063A TW 201500195 A TW201500195 A TW 201500195A
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Taiwan
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carrier
substrate
iel
layer
micropores
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TW103108063A
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TWI623426B (zh
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Rong-Chang Liang
Chin-Jen Tseng
Ta-Ching Wu
Jia Yen Leong
Zhi-Yao An
An-Yu Ma
Maung Kyaw Aung
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Trillion Science Inc
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  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

一種用於製造諸如各向異性導電膜之裝置或組件的載體帶。該載體帶包括具有犧牲影像加強層的基板。微孔係由雷射燒蝕通過該影像加強層而於該載體中形成。在該影像加強層移除之後，複數導電粒子分散在由雷射燒蝕形成於載體帶表面上之微孔陣列中，並轉移至黏接層。該影像加強層使能形成具細間距之微孔及具有高高寬比之間隔及分區。

Description

用於雷射燒蝕之具有影像加強的微孔載體
本發明關於製造諸如各向異性導電膜(ACF)之電子裝置及組件的方法。本發明代表Liang等人之美國公開申請案2010/0101700(「Liang’700」)中所揭露之發明改進，其中影像加強層(IEL)用以藉由雷射燒蝕形成載體網中之微孔。
為討論發明背景，可參考以上提及之Liang‘700，Liang‘700揭露藉由提供具有非隨機微孔陣列之載體網並將導電粒子分散於微孔中而製造具有導電粒子之非隨機陣列之ACF的方法。較佳地，粒子分散於載體網上使得實質上每一孔中有一粒子。載體網經傳輸接觸黏接膜，且粒子於接觸時便轉移至膜。
用以在載體網中形成微孔之一方法為使用例如穿過遮罩之KrF及ArF準分子雷射的雷射燒蝕微切削。詳以提及方式併入本文之共同受託之美國公開案2009/0053859；2010/0101700；及2012/0295098。
已報導將燒蝕之聚合物的局部表面溫度可達到大於1000°K，具通常數十至數百巴之相對高壓力燒蝕捲流。已觀察到因碎片再沉積及再凝固之橫向材料熔體流動的微結構形成。為尤其是高高寬比(即影像或影像間隔之高度/寬度或深度/寬度比)之細間距影像再生，因可歸因於使用之遮罩及光熱程序引發之上述材料熔體流動、碎片形成及再沉積的不希望之光衍射及散射，該等程序可達到之解析度通常嚴重退化。
亦已報導，藉由使用具連貫影像修正之投影遮罩、各式基板上各式波長之多脈衝照射、濾光照射、液體輔助或水下照射，可達到改進之高寬比及解析度。然而，在所有狀況下，影像間隔之窄間距間隔(約<5μm)及高高寬比(約>1)之細間距(約<15μm)影像的製造仍是主要挑戰，尤其是在捲裝進出程序。
發明之一表現為在製造諸如ACF、薄膜覆晶(COF)或玻璃覆晶(COG)之裝置組件中有所助益之載體，其中，載體包括可移除犧牲IEL，經此而藉由雷射燒蝕在載體上形成微孔。
已觀察到在本發明之若干實施例中產生之微孔陣列，如以上專利申請案中所提出及圖2中所描繪，在微孔載體膜之製造及固定陣列ACF之捲裝進出製造的粒子填充及轉移，提供顯著改進之再生性及更寬處理窗口。已觀察到在填充程序中填充效率(即微孔捕捉粒子之百分比)及粒子轉移程序中微孔網或環從黏接層之釋放效率的顯著改進。雖然不受理論所縛，咸信犧牲IEL有效地預防碎片及低分子量雷射退化或光解/熱解材料熔體直接接觸基板或形成強附著/內聚。低分子量雷射退化或光解/熱解材料傾向於相當極性及有時充電。其傾向於相當黏但於溶解或剝除IEL之後續影像顯影程序中被移除或洗去。結果，本發明之微孔載體網或環顯示針對粒子轉移程序中之黏接層顯著較佳釋放屬性。另一方面，在粒子填充程序中所觀察之改進咸信為使用IEL所獲得之較佳定義孔間隔及輪廓之直接結果，其可於捲裝進出射流粒子填充程序期間較佳包含粒子。
發明之一表現為載體帶，其包含基板及被覆基板之影像加強層(IEL)，其中，IEL為雷射可燒蝕並預防雷射退化材料干擾微孔形成，及可產生具有細間距、高解析度及高高寬比之微孔載體。
發明之另一表現為使用具有藉由雷射燒蝕而於載體中形成微孔陣列之載體片、網或帶而製造諸如ACF之電子裝置的程序。微孔填充導電粒子，且載體網係以類似於Liang‘700文獻中所揭露之程序或捲裝進出程序中之網的方式使用。
發明之另一表現為具有IEL之載體片、帶或網，其中微孔係以非隨機但可變的型態配置以減少週期性缺陷影響。
本發明之再另一表現為具高解析度及高孔密度之微孔的非隨機微孔載體片、帶或網，用於微流控裝置、微流控裝配程序及應用。
10‧‧‧載體
12‧‧‧基板
14‧‧‧影像加強層
16‧‧‧中間孔形成層
18‧‧‧微孔
60‧‧‧雷射光束
61‧‧‧網
62‧‧‧光束定形光學器件
64‧‧‧光罩
66‧‧‧雷射光束
68‧‧‧投影透鏡系統
100‧‧‧合成膜
100"‧‧‧膜
110‧‧‧導電粒子
120‧‧‧黏接層
125‧‧‧微孔陣列
130‧‧‧第一基板
140‧‧‧第二基板
160‧‧‧射流填充步驟
170‧‧‧載體網
180‧‧‧層壓站
190‧‧‧載體網
圖1A-1B為依據本發明之一實施例之載體片、網或帶的截面示意圖。
圖1C及1D為圖1A及1B之載體片、網或帶的示意截面圖，顯示依據本發明之二實施例之藉由雷射燒蝕而形成於基板中之微孔的位置。
圖1E-1至圖1E-15為使用具5μm直徑及3μm寬分區之重複圓形開口的交錯6-8μm間距光罩，具或不具約0.5μm被覆之IEL之各式PET基板的SEM顯微照片。除非清楚指明，在所有狀況下調整雷射能量以產生具有約4-5μm深度之孔的微孔載體。圖中所示之所有SEM照片係在IEL剝除後拍攝。
依據本發明之一實施例，圖1E-1係提供用於比較，為形成於包含著色PET(DuPont Teijin Films之MELINEX 339®)之載體(其不包括IEL)中之微孔的SEM照片，且圖1E-2為形成於預塗約0.5μm厚度之IEL(形成自PKFE(南卡羅來納州InChem公司之苯氧基樹脂))之MELINEX 339®基板上之微孔的SEM照片。
圖1E-3為形成於透明PET MELINEX 454®膜上之微孔的SEM照片，及圖1E-4至1E-15為形成於預塗約0.5μm厚度之IEL之MELINEX 454®膜上之微孔的照片，其中IEL係形成自：苯氧基樹脂PKHB(圖1E-4)及PKCP(圖1E-5)，二者來自InChem公司；酚醛樹脂RezicureTM 3500(圖1E-6)及3100(圖1E-7)，二者來自紐約州SI Group；聚苯乙烯，Mw=35,000(圖1E-8)、聚苯乙烯-馬來酸酐共聚物，Mw=1,700(圖1E-9)、聚(苯乙烯-共-甲基丙烯酸甲酯)，Mw=30,000(圖1E-10)、PMMA，Mw=350,000(圖1E-11)、聚乙烯 醇，88%水解，Mw=30,000(圖1E-12)、聚乙烯醇縮丁醛，Mw=50,000(圖1E-13)、乙酸丁酸纖維素，Mw=50,000(圖1E-14)，以上均來自Sigma-Aldrich；及PE-Wax ME48040M2(圖1E-15)，來自俄亥俄州Michelman公司。
圖1F-1及1F-2為形成於聚萘二甲酸乙二醇(來自DuPont Teijin Films之PEN Q51膜)上之微孔的SEM照片，分別不具有或具有形成自PKHB之約0.5μm厚度的IEL。
圖1G-1及1G-2為形成於Kapton®聚醯亞胺VN-300膜(來自DuPont)上之微孔的SEM照片，分別不具有或具有形成自PKHB之約0.5μm厚度的IEL。
圖2示意描繪依據本發明之一實施例之製造程序，其中載體網或帶係用於在捲裝進出轉移程序中形成ACF，其中如Liang‘700中所揭露，導電粒子係從微孔轉移至並置黏接層。
圖3示意描繪本發明之一實施例中用於形成載體網中微孔之雷射投影系統。
Liang‘700整個內容以提及之方是併入本文。
圖1A為依據本發明之一實施例之載體片、網或帶10的截面圖。載體片10包括被覆IEL 14之基板12，IEL 14可直接黏接至基板12。在另一實施例中，如圖1B中所示，載體10可選地包括中間孔形成層16，其可插入IEL層14及基板12之間。在特定實施例中，基板12係由聚對苯二甲酸乙二酯(PET)、PEN、聚醯亞胺等形成，及IEL 14為諸如PKFE及PKHB苯氧基樹脂(以下識別)之成像加強犧牲層的薄被覆。微孔可提供極細間距及間隔。
圖1C及1D描繪微孔18藉由雷射燒蝕形成於載體10中之後，及如虛線所示移除IEL層14之後，圖1A中所示之載體。
為於基板12或孔形成層16上形成IEL，形成IEL之材料可溶解或分散於溶劑中，諸如水、乙醇、乙酸乙酯、乙酸異丙酯、丙酮、丁酮、環己酮、十二烷基硫酸鈉、烷氧基醚、及甲苯等， 並藉由例如刮墨刀、線棒、槽或縫模、凹板、逆轉輥及淋幕式塗佈而被覆至基板。真空沉積、化學蒸氣沉積、構形及電漿被覆亦可用於薄被覆。在若干狀況下，亦可以膠乳或乳液形式被覆。諸如Silwet、Triton、及Pluronic表面活性劑之潤濕劑可選地用以改進被覆品質。除非清楚指明，塗料厚度可控制至約0.05至4μm，較佳地約0.2至2μm，甚至更佳地約0.5至1.5μm。過薄被覆傾向於導致針孔及不足之障壁屬性來抵抗燒蝕程序期間產生之材料熔體流動。另一方面，過厚被覆可能導致雷射能量浪費或較窄開口或較淺深度之微孔。燒蝕後，藉由溶劑或清洗液及/或使用諸如德克薩斯州Surface Armor之膠帶Tape 364的物理剝離而將IEL及燒蝕碎片剝除，以於基板或孔形成層上形成微孔陣列。
在一實施例中，可修改類似於Liang‘700之圖3中所示之ACF生產站的程序以包括雷射燒蝕裝置，取代在ACF生產站之第一階段藉由雷射燒蝕製造複數微孔之壓花裝置。微孔陣列可如圖1A中所示直接形成於基板12上，或如圖1B中所示直接形成於預先施加於基板12之孔形成層16上。在一實施例中，用於基板之適當材料包括但不侷限於聚酯，諸如聚對苯二甲酸乙二酯(PET)及聚萘二甲酸(PEN)、聚碳酸酯、聚醯胺、聚丙烯酸酯、聚碸、聚醚、聚醯亞胺(PI)、及液晶聚合物及其摻合物、複合材料、層狀材料或夾層膜。
發現以薄的可燒蝕犧牲影像加強層14被覆將燒蝕基板可獲得影像解析度及對比之顯著改進。未限於任何理論，咸信可移除犧牲IEL減少(1)因來自遮罩之散射或衍射光的不利影響，及/或(2)碎片或重新沉積熔體材料及基板間形成強附著力或內聚力之可能性。高解析度及對比之影像，特別是極細間隔(例如，間距小於約15μm及間隔小於約5μm)及高高寬比(例如，在微孔、微孔隔牆、或微孔間之間隔方面大於約1)者，可藉由使用諸如溶劑溶解/清洗之濕式顯影程序或諸如剝離或乾式蝕刻之乾式顯影程序移除IEL而顯影。在圖1E-1及1E-15及1F-1及1F-2及1G-1及1G-2中可清楚見到解析度、影像銳度及對比之改進。
在本發明之一實施例中，IEL被覆層可為約0.05至約4μm，在特定實施例中，為約0.2至約2μm。在本發明之選擇實施例中，基板層為約10μm至200μm厚，更特定地約50μm至150μm厚。在一實施例中，IEL樹脂係選自包括苯氧基樹脂、酚醛樹脂、聚碳酸酯、聚苯乙烯、聚芳醚、聚芳碸及其共聚物或摻合物之群組。苯氧基及酚醛樹脂特別有所助益，因為其為可燒蝕且為大部分準分子雷射光之波長中的強消光係數。其亦提供針對基板12或孔形成層16(若存在)之極佳附著力及其針對雷射燒蝕期間形成之碎片熔體流動的阻力。在燒蝕後，如之前所說明，剝除IEL以及燒蝕碎片以顯露高對比之微孔、高高寬比之隔牆及平滑表面。該些微孔特別有助於ACF及高產量微流控粒子分散程序。
有用之苯氧基樹脂的代表範例包括但不侷限於InChem公司之PKFE、PKHB及PKCP。代表酚醛樹脂包括但不侷限於來自Shipley,MA及Georgia-Pacific及RezicureTM甲酚之酚醛氫漆樹脂，或SI Group之其他烷基酚酚醛樹脂。有用之IEL樹脂的其他範例包括但不侷限於聚苯、聚碳酸酯、聚芳醚、聚芳碸、及其共聚物或摻合物。圖1E-1(著色PET)、圖1E-3(透明PET)、圖1F-1(PEN)及圖1G-1(PI)中顯示藉由直接在基板上燒蝕而無任何IEL所獲得之6-8μm間距、5μm直徑及3-4μm深度之微孔的SEM顯微照片。基於缺少聚醯亞胺(圖1G-1)，該等細間距微孔陣列的隔牆藉由燒蝕程序而嚴重失真。儘管聚醯亞胺基板之燒蝕顯示較少嚴重失真，觀察到直接在聚醯亞胺膜上燒蝕產生顯著量不希望有的暗碎片，其難以藉由燒蝕程序期間真空及/或吹氣移除。相反地，在被覆聚醯亞胺膜之IEL上燒蝕期間形成之碎片顯示顯著較少黏附IEL層之傾向，並相對易於藉由吹氣或真空移除。使用聚醯亞胺膜上IEL之方式改進連續燒蝕程序之效率無需清潔基板或自動捲裝進出視覺識別程序中用於對準之光學器件。為了比較，圖1E-2(著色PET/PKFE)、圖1E-4(PET/PKHB)、圖1E-5(PET/PKCP)、圖1E-6(PET/酚醛清漆Resicure 3500)、圖1E-7(PET/酚醛清漆Resicure 3100)、圖1F-2(PEN/PKHB)及圖1G-2(聚醯亞胺/PKHB)顯示與具約0.5μm厚度之苯氧基或酚 醛/酚醛清漆IEL被覆相同基板之SEM顯微照片。在所有狀況下，以苯氧基或酚醛IEL被覆產生之微孔顯示對比、高寬比及IEL剝除後之隔牆平滑的顯著改進。IEL提供微流控粒子分散程序之顯著更寬處理窗口。亦觀察到於燒蝕期間產生之碎片可容易地藉由真空及/或吹氣移除。同樣重要地，以IEL產生之微孔網或環亦顯示顯著較佳釋放屬性，且在非隨機陣列ACF之製造中以粒子轉移程序中更寬處理窗口導致顯著高良率。
表1 IEL在燒蝕基板相對於膠帶Polyken 781之附著力的影響在所有狀況下，可清楚見到使用IEL(約0.5μm厚度之PKHB)減少燒蝕基板相對於膠帶之附著力。導致粒子轉移程序之處理窗口的顯著改進。
圖1E-8(PET/PS(聚苯乙烯))、圖1E-9 PET/SMA(聚苯乙烯-共-馬來酸酐))、圖1E-10(PET/聚苯乙烯-共-甲基丙烯酸甲酯)、圖1E-11(PET/PMMA(聚甲基丙烯酸甲酯))、圖1E-12(PET/PVA(聚乙烯醇))、圖1E-13(PET/PVB(聚乙烯醇縮丁醛))、圖1E-14 PET/CAB(乙酸丁酸纖維素))及圖1E-15(PET/PE蠟)中顯示以透明PET上各式IEL被覆產生之微孔的更多SEM顯微照片。 儘管其均提供較無被覆之控制樣本更易清潔燒蝕碎片，在聚苯乙烯及相關共聚物之狀況下僅觀察到微孔對比或隔牆失真的有限改進。並未受限於理論，儘管提供碎片及基板間之障壁，咸信具雷射輸出波長範圍中低消光係數之該些材料(PMMA、PVA、PVB、CAB及PE)未展現針對光散射或衍射之對比加強效果。
可選地，載體可包括可燒蝕孔形成層，其插入基板之間及被覆之IEL之下。孔形成層可包括但不侷限於熱塑性材料、熱固性材料或其先質、正或負光阻、或無機材料。該等孔形成層之代表範例包括但不侷限於聚碳酸酯、聚醯亞胺(PI)、聚芳基醚、聚芳酯s、聚碸、聚芳基矽樹脂及其共聚物或摻合物/複合材料。
圖2描繪依據本發明之一實施例之可重複使用載體網或帶190，其具有其表面上之微孔陣列125。載體網190包括基板。在一實施例中，微孔陣列125係直接形成於載體網190上。在另一實施例中，微孔陣列125係形成於其下基板載體網170上之孔形成層160中。載體網170之適當材料包括但不侷限於聚酯，諸如聚對苯二甲酸乙二酯(PET)及聚萘二甲酸(PEN)、聚碳酸酯、聚醯胺、聚丙烯酸酯、聚碸、聚醚、聚醯亞胺(PI)、及液晶聚合物及其摻合物、複合材料、層狀材料或夾層膜。在一實施例中，載體網為VN300TM，其係DuPont之Kapton®(芳香聚醯亞胺)膜。
在本發明之一實施例中，為達成高產量粒子轉移，在燒蝕載體以形成微孔之後，載體網之表面可處理為釋放材料薄層(未顯示)以減少微孔載體網190及黏接層120間之附著力。可選地，可藉由微孔形成步驟之前或之後的被覆、印刷、噴塗、蒸氣沉積、熱轉移、或電漿聚合/交聯而施加剝離層。如Liang‘700中所揭露，剝離層之適當材料包括但不侷限於含氟聚合物或低聚物、矽油、含氟矽樹脂、聚烯烴、蠟、聚(環氧乙烷)、聚(環氧丙烷)、具長鏈疏水性嵌段或分支之表面活性劑、或其共聚物或摻合物。
可使用雷射燒蝕程序於網中形成微孔。在一實施例中，於聚醯亞胺或PET網上使用UV準分子雷射燒蝕穿過光罩而製造不同形狀及尺寸圖案。產生之微米圖案的形狀及尺寸及圖案配置係由 光罩設計預先決定。美國公開案2006/0280912及Liang’700中揭露圖案尺寸、形狀及間隔之變化。固定陣列圖案可改變。在圓形微孔之狀況下，可使用代號X-Y代表圖案，其中X為孔之直徑及Y為鄰近孔間之邊緣至邊緣距離，單位為微米。典型微孔圖案間距包括5-3、5-5、5-7、及6-2圖案。選擇之圖案將部分取決於每一電極所需粒子數。為增加粒子密度及/或減少電極之最小黏接面積，微孔圖案可交錯。
圖3顯示遮罩基雷射投影燒蝕系統之一範例，其中雷射光束60通過光束定形光學器件62以均衡雷射強度。所欲微孔圖案配置係通過光罩64產生以製造具有所欲尺寸及形狀的複數雷射光束66。光束強度或光束脈衝數係結合投影透鏡系統68調整以於具有所欲開口及深度的網61中產生微孔。透鏡系統68可用於減少光。在一實施例中，可以控制方式偏移或隨機孔至孔距離以減少黏接期間定期線缺陷的影響。在一實施例中，可選擇孔之尺寸使得每一孔僅容納一導電粒子。在一實施例中，在非圓形孔的狀況下，導電粒子及微孔為直徑約2至10微米。
依據本發明之一實施例，微孔經定位以減少導電粒子圖案中定期/重複線缺陷的影響。在微孔之位置實施控制但可變之調整以預防以提及之方式併入本文之美國申請案序號13/233,360中所揭露之缺陷。
導電粒子110之沉積可由施加射流粒子分散程序及陷入程序影響，其中每一導電粒子陷入單一微孔125。可使用若干陷入程序。例如，捲裝進出連續射流粒子分散程序可用以使每一微孔僅陷入一導電粒子。
在一實施例中，微孔環係置於具懸臂輥之粒子填充塗料器上。異丙醇(IPA)中導電粒子之3至6重量%分散係由機械攪拌混合，及由射流程序分散，經由例如狹縫塗佈模、霧幕、或噴嘴通過具Cole Parmer之Masterflex泵的L/S 13管道。導電粒子係使用100%針織滌綸括刷器纏輥填入微孔。使用具真空裝置之Shima American公司的聚氨酯輥小心地移除過度粒子(微孔外)以回收導電粒子。恢復之粒子可收集及再循環至供應料斗而重新施加至網190。 在一實施例中，可採用一個以上之分配站110以確保導電粒子112陷入每一微孔125中，並藉以最小化或減少未包含粒子之微孔數量。
陷入之粒子110接著可從微孔陣列轉移至黏接層120上之預定位置。典型地，該些轉移之導電粒子間之距離必須大於滲濾閾值，其為密度閾值，導電粒子於此成為連接或聚集。通常，滲濾閾值為微孔陣列結構之結構/圖案的函數並針對複數導電粒子。
例如，在射流裝配後，可希望採用一或多程序以移除過度導電粒子。捲裝進出連續射流粒子分散程序可包括清潔程序以從微孔陣列頂部移除過度導電粒子。清潔程序可為非接觸清潔程序、接觸清潔程序、或非接觸及接觸清潔程序之有效組合。
粒子清潔程序之某些例示實施例採用非接觸清潔程序，包括但不侷限於吸氣程序、吹氣程序、或溶劑噴塗程序之一或多者。移除之過度導電粒子可藉由例如吸氣裝置累積而回收或重新使用。配送清潔液可進一步協助非接觸吸氣程序，諸如但不侷限於噴塗溶劑或溶劑混合物，以改進清潔效率。本發明之某些其他例示實施例可採用接觸清潔程序以從微孔陣列之表面移除過度導電粒子。接觸清潔程序包括使用無縫毛氈、括刷器、刮墨刀、黏接材料、或黏輥。當使用無縫毛氈時，吸氣程序亦可用以從無縫毛氈表面回收導電粒子並刷新毛氈表面。在此黏結/吸氣程序中，毛細力及吸力以從無縫毛氈內部施加之吸力拖拉過度導電粒子，以移除及回收過度粒子。配送清潔液、溶劑、或溶劑混合物可進一步協助吸氣程序以改進清潔效率。
在射流填充步驟160之後，微孔中之導電粒子可轉移至基板130，其係以未固化黏合劑120預先被覆或其係被覆於處理管路上。藉由重複粒子填充及轉移步驟而重新使用微孔帶190。
如圖2中所示，黏合劑成分120係提供於基板或釋放膜130上。黏合劑成分可為環氧樹脂成分。在一實施例中，可為美國公開申請案2010/0317545、2010/0101700、2009/0181165；美國專利7,923,488、4,740,657、6,042,894、6,352,775、6,632,532；J.ApplPolymer Sci.,56,769(1995)；及J.Mater.Sci.,(2008)43,3072-3093中所揭露之成分，其內容以提及之方式併入本文。在一實施例中，黏合 劑包含核-殼橡膠粒子，諸如Dow Chemical公司EXL2335，或熱塑性彈性體，諸如賓夕法尼亞州Arkema公司之NanostrengthR丙烯酸系嵌段共聚物，約0.5至10重量%之量，作為成分之增韌劑或相容劑。
為達成從微孔環至黏接層120之高產量粒子轉移，黏接層120之內聚力應不小於黏接層及微孔陣列125間之附著力；黏接層120及微孔陣列110間之附著力應小於黏接層120及攜帶黏接層120之基板130(剝離襯裡)間之附著力。黏接至微孔陣列膜或剝離襯裡之附著力可由釋放塗料及微孔陣列膜之屬性、黏合劑成分、及使用包括電暈及電漿處理或其組合之表面處理控制。
依據本發明之一實施例，被覆之黏合劑可於接觸微孔帶之前預先調節或退火。預先調節溫度典型地高於用於黏合劑中之聚合物的熱失真或玻璃化轉變溫度，並低於黏合劑開始固化之起效溫度。在一實施例中，形成黏合劑之聚合物或樹脂的玻璃化轉變溫度為約10℃至20℃，黏合劑之起效固化溫度為約60℃至75℃，二者係以DSC在5℃/min加熱速率下測量。在該些狀況下，約20至30℃之預先調節或退火溫度有所助益。
在若干狀況下，有利地使用展現跨越黏接厚度之模數梯度的黏接層，在剝離襯裡側具較高模數及在黏接側具較低模數。藉由從導電粒子分散程序導入微量溶劑、藉由調整轉移程序期間導入之溫度梯度、或藉由以上二者，可達成模數梯度。藉由施加表面加熱源、藉由從剝離襯裡使用散熱器、或藉由以上二者，可達成溫度梯度。表面加熱源可不侷限於加熱輥源、紅外源、熱空氣源、或線源。該些例示源之適當組合亦為適宜。
在一實施例中，黏接層120可置於ACF基板130上，諸如聚對苯二甲酸乙二酯(PET)及聚萘二甲酸(PEN)、聚碳酸酯、聚醯胺、聚丙烯酸酯、聚碸、聚醚、聚醯亞胺(PI)、及液晶聚合物膜。在導電粒子轉移後，膜被切割及捲繞為捲筒。基板之背側接著接觸黏合劑之頂面。在這種情況下，黏合劑及基板背面間之附著力應低於黏合劑及基板正面(被覆側)間之附著力，以確保ACF之適當握持能力。
導電粒子轉移程序之非侷限例示實施例可採用黏接層及微孔陣列間之微分剪切程序。微分剪切係藉由黏接被覆剝離襯裡及微孔陣列間之網速度差異達成。剝離襯裡之網速度可略高或略低於微孔陣列之網速度。
在導電粒子轉移至黏接層之後，粒子可部分嵌入黏接層。該些部分嵌入之導電粒子可改進ACF黏接性能而具較高附著力，特別是當使用低黏接壓力、減少之空間、及較低接觸阻力時。可選地，在導電粒子轉移至黏接層之後，黏接層可進一步處理以具有模數梯度及跨越黏接層建立之黏性梯度，且承載導電粒子之黏接表面側擁有較高模數及較高黏性。較高模數及較高黏性可有助於維持導電粒子於ACF黏接應用期間處於其非隨機陣列位置。跨越黏接層之黏性梯度可藉由施加加熱程序達成，包括但不侷限於表面輻射、紅外輻射、UV輻射、或加熱輥加熱程序。該些加熱程序之適當組合亦可有效。
如Liang‘700中所揭露，第二基板140可選地施加於黏接層頂側以保護及改進黏合劑之釋放特性。黏接層120及第一基板130或第二基板140間之附著力必須弱於黏接層之內聚力。黏接層120及第一基板130間之附著力必須強於黏接層120及第二基板140間之附著力。黏接層120及第一基板130間之附著力必須弱於黏接層及黏接基板(未顯示)間之附著力，諸如印刷電路板、彈性印刷電路板、聚合物膜、玻璃等，可於ACF黏接應用之預先黏接程序後釋放基板。
合成膜100可直接用作非隨機陣列ACF，其中，導電粒子110是在黏接膜120之頂部，未被黏合劑完全覆蓋。可選地，黏接層之額外薄層可被超被覆至轉移之粒子層，以改進非隨機陣列ACF膜之膠黏，特別是當粒子濃度高時。可將與黏接膜120不同之黏合劑用於被覆。
膜100"可在層壓站180以基板140進一步層壓，基板140可選地預塗黏合劑以導致夾於二基板130及140間之非隨機陣列ACF 100。黏接膜120及二基板130及140間之附著力應低於黏合 劑之內聚力。為利黏接期間二基板與黏合劑之連續剝離，較佳的是其中一者之附著力實質上大於另一者。
上述程序中使用之黏合劑可為熱塑性材料、熱固性材料、或其先質。有用之黏合劑包括但不侷限於壓力敏感性黏合劑、熱熔體黏合劑、熱或輻射固化黏合劑。黏合劑可包含例如環氧、酚醛樹脂、胺-甲醛樹脂、聚苯並惡嗪、聚氨酯、氰酸酯、丙烯酸樹脂、丙烯酸酯、甲基丙烯酸酯、硫醇-烯、乙烯基聚合物、諸如聚(苯乙烯-並-二烯)及其嵌段共聚物之橡膠、聚烯烴、聚酯、不飽和聚酯、乙烯基酯、聚己內酯、聚醚、及聚醯胺。環氧、氰酸酯及多功能丙烯酸酯特別有用。包括潛在性固化劑之催化劑或固化劑可用以控制黏合劑之固化動力。環氧樹脂之有用之固化劑包括但不侷限於雙氰胺(DICY)、己二酸二醯肼、2-甲基咪唑及其封裝產品(諸如來自Asahi Chemical Industry分散於液態雙酚A環氧樹脂中之Novacure HX)、胺(諸如乙二胺、二乙烯三胺、三亞乙基四胺、三氟化硼胺加成物、來自Ajinomoto之Amicure)、鋶鹽(諸如二氨基二苯碸、對-羥基苯基芐基甲基鋶六氟銻酸鹽)。偶聯劑包括但不侷限於鈦酸、鋯及矽烷偶聯劑，諸如環氧丙氧基丙基三甲氧基矽烷，且3-氨基丙基三甲氧基矽烷亦可用以改進ACF之耐久性。固化劑及偶聯劑對於環氧樹脂基ACF之性能的影響可見於S.Asai等人之「J.Appl.Polym.Sci.,56,769(1995)」。全文以提及之方式併入本文。
本發明之一實施例的適當導電粒子為窄粒子尺寸，以小於約10%的標準偏差分散，較佳地小於約5%，甚至更佳地小於約3%。粒子尺寸較佳地介於約1μm至約250μm範圍，更佳地較約2μm至約50μm，甚至更佳地約2μm至約6μm。選擇微孔及導電粒子之尺寸使得每一微孔具有有限空間而僅包含一導電粒子。為利粒子填充及轉移，可如Liang‘700中所示，採用具有傾斜壁且頂部開口較底部開口寬之微孔。
包含聚合物核心及金屬殼之導電粒子特別佳。有用之聚合物核心包括但不侷限於聚苯乙烯、聚丙烯酸酯、聚甲基丙烯酸酯、聚乙烯、環氧樹脂、聚氨酯、聚醯胺、酚醛、聚二烯烴、聚烯烴、 諸如三聚氰胺甲醛之氨基塑料、脲醛、苯代三聚氰胺甲醛及其低聚物、共聚物、摻合物或複合材料。若複合材料用作核心，則碳、二氧化矽、氧化鋁、BN、TiO2及黏土之奈米粒子或奈米管較佳地作為核心中之填料。金屬殼之適當材料包括但不侷限於Au、Pt、Ag、Cu、Fe、Ni、Sn、Al、Mg及其合金。諸如Ni/Au、Ag/Au、或Ni/Ag/Au之具有互穿金屬殼的導電粒子對於最佳硬度、導電性及抗腐蝕性特別有用。諸如Ni、碳、石墨之具有剛性尖峰的粒子有助於藉由穿透腐蝕膜(若存在)而改進連接腐蝕敏感電極之可靠性。
對於本發明有所助益之狹窄分散聚合物粒子可由例如美國專利4,247,234、4,877,761、5,216,065中所提及之晶種乳液聚合，及如Adv.,Colloid Interface Sci.,13,101(1980)、J.Polym.Sci.,72,225(1985)及Martinus Nijhoff Publisher中El-Aasser及Fitch等人之「高分子膠體之未來方向」(“Future Directions in Polymer Colloids”)，p.355(1987)中所說明之Ugelstad膨脹粒子程序準備。在本發明之一較佳實施例中，約5μ直徑之單分散聚苯乙烯膠乳粒子用作可變形彈性核心。粒子首先於溫和攪拌之甲醇中處理，以移除過度表面活性劑及於聚苯乙烯膠乳粒子上製造微孔表面。因而處理之粒子接著在包含PdCl2、HCl及SnCl2之溶液中激活，之後以水清洗及過濾以移除Sn4.sup.+，接著浸入約90℃之包含Ni複合物及磷酸二氫基之無電鍍Ni溶液(例如來自Surface Technology Inc,Trenton,N.J.)達約30分鐘至約50分鐘。鍍Ni之厚度係由電鍍溶液濃度及電鍍狀況(溫度及時間)控制。
Ni被覆膠乳粒子接著置於約90℃之包含四氯氫及乙醇之沈浸Au電鍍溶液(例如來自Enthone公司)中達約10分鐘至約30分鐘，以形成互穿Au/Ni殼，具有約1μm之總金屬(Ni+Au)厚度。接著以水清洗Au/Ni電鍍膠乳粒子並準備用於射流填充程序。藉由無電及/或電鍍於粒子上被覆導電殼之程序係於例如美國專利No.6,906,427(2005)、美國專利No.6,770,369(2004)、美國專利No.5,882,802(1999)、美國專利No.4,740,657(1988)、美國專利申請案20060054867、及Chem.Mater.,11,2389-2399(1999)中提及。
IC晶片之射流裝配或顯示材料之基板或網之凹陷區域或孔內之焊球已於例如美國專利6,274,508、6,281,038、6,555,408、6,566,744及6,683,663中揭露。壓花網之微杯內電泳或液晶液之填充及頂部密封係於例如美國專利6,672,921、6,751,008、6,784,953、6,788,452及6,833,943中揭露。藉由填入壓花載體網之凹部而具有精確間隔之研磨物的準備，包含分散於硬化黏合劑先質中之複數研磨粒子的研磨複合漿料亦於例如美國專利5,437,754、5,820,450及5,219,462中揭露。所有上述美國專利案以提及之方式併入本文。在上述技藝中，凹部、孔、或微杯係藉由例如壓花、沖壓、或平版印刷程序而形成於基板上。各種材料接著填入凹部或孔進行各式應用，包括主動矩陣薄膜電晶體(AM TFT)、球柵陣列(BGA)、電泳及液晶顯示。
已詳細說明本發明並參照其特定實施例，將顯而易見的是可進行許多變化及修改而未偏離下列申請項之精神及範圍。
100‧‧‧合成膜
100"‧‧‧膜
110‧‧‧導電粒子
120‧‧‧黏接層
125‧‧‧微孔陣列
130‧‧‧第一基板
140‧‧‧第二基板
160‧‧‧射流填充步驟
170‧‧‧載體網
180‧‧‧層壓站
190‧‧‧載體網

Claims (20)

  1. 一種載體，其為片、網或帶狀，用於形成包含基板及影像加強層(IEL)之微孔，該基板及該IEL為雷射可燒蝕，該影像加強層係直接沉積於該基板上或沉積於插入該IEL及該基板間之微孔形成層上。
  2. 如申請專利範圍第1項之載體，其中該IEL為選自包含苯氧基樹脂、酚醛樹脂、聚碳酸酯、聚芳醚、聚芳碸、聚芳基矽、聚芳酯、聚芳、聚芳香醯胺、聚芳丙烯酸酯、聚芳香醯亞胺、聚苯乙烯、聚(甲基苯乙烯)、及其共聚物或摻合物之群組的材料層。
  3. 如申請專利範圍第2項之載體，其中該IEL為苯氧基樹脂或酚醛樹脂之層。
  4. 如申請專利範圍第2項之載體，其中該IEL為PKFE、PKHB、或PKCP，或其摻合物之層。
  5. 如申請專利範圍第3項之載體，其中該IEL為苯酚酚醛清漆、甲酚酚醛、甲階酚醛清漆、烷基酚酚醛清漆或其共聚物或摻合物之層。
  6. 如申請專利範圍第1項之載體，其中該載體另外包括雷射燒蝕為該IEL及該其下基板之微孔陣列。
  7. 如申請專利範圍第6項之載體，其中該微孔間隔小於約15μm。
  8. 如申請專利範圍第7項之載體，其中該微孔間隔小於約5μm。
  9. 如申請專利範圍第8項之載體，其中該微孔之隔牆具有大於約0.5之高寬比。
  10. 如申請專利範圍第9項之載體，其中該微孔之該隔牆具有大於約1之高寬比。
  11. 一種載體，其為片、網或帶狀，包含基板及影像加強層，該些層之每一者為雷射可燒蝕，該影像加強層係直接沉積於該基板上或沉積於插入該IEL及該基板間之微孔形成層上，且微孔之陣列被雷射燒蝕為該IEL及該基板或該微孔形成層。
  12. 一種方法，包含：將複數導電粒子分散於形成於載體帶表面上之微孔陣列中，該載體帶包含基板及影像加強層，該些層之每一者為雷射可燒蝕，該對比加強層係直接沉積於該基板上或沉積於插入該IEL及該基板間之微孔形成層上，且微孔陣列雷射燒蝕為該IEL及該基板或該微孔形成層；旋轉攜帶該導電粒子之該帶，同時傳輸黏接層表面接觸該旋轉帶之該表面；將該導電粒子從該帶上之該微孔轉移至相應於該帶上該微孔陣列之該黏接層中預定位置之該黏接層；以及將該黏接層從該帶之該表面分離。
  13. 如申請專利範圍第12項之方法，其中將複數導電粒子置入微孔陣列之步驟包括將導電粒子個別陷入單一微孔。
  14. 如申請專利範圍第13項之方法，其中該固化黏合劑或塗料係選自矽樹脂，多異氰酸酯、聚氨酯、多功能環氧樹脂、丙烯酸酯、甲基丙烯酸酯、硫醇-烯、乙烯基醚、乙烯基酯及氰酸酯、硫化熱塑性彈性體、及不飽和橡膠。
  15. 如申請專利範圍第14項之方法，其中該固化黏合劑或塗料包含多功能環氧化物、氰酸酯或丙烯酸酯。
  16. 如申請專利範圍第12項之方法，其中該基板係從選自下列群組之材料形成，包含聚對苯二甲酸乙二酯(PET)、聚萘二甲酸(PEN)、聚碳酸酯、聚醯胺、聚丙烯酸酯、聚碸、聚醚、聚醯亞胺(PI)、及液晶聚合物及其摻合物、複合材料、層狀材料或夾層膜。
  17. 如申請專利範圍第12項之方法，其中微孔陣列包括彼此分離一距離之孔，該距離係以控制方式變化，以減少或預防週期性缺陷的影響。
  18. 如申請專利範圍第12項之方法，其中該方法包括於該黏接層之該表面接觸攜帶該導電粒子之該旋轉帶之該表面之前，退火該黏接層之額外步驟。
  19. 如申請專利範圍第11項之載體，其中該微孔陣列在形成微流控裝置中有所助益。
  20. 如申請專利範圍第11項之載體，其中該微孔陣列在形成各向異性導電膜中有所助益。
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