TW202031480A - 用於3d ic應用的可雷射釋放接合材料 - Google Patents
用於3d ic應用的可雷射釋放接合材料 Download PDFInfo
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- TW202031480A TW202031480A TW109102434A TW109102434A TW202031480A TW 202031480 A TW202031480 A TW 202031480A TW 109102434 A TW109102434 A TW 109102434A TW 109102434 A TW109102434 A TW 109102434A TW 202031480 A TW202031480 A TW 202031480A
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Abstract
本發明提供了新型的以聚酮縮苯胺為主的組合物,其用作可雷射釋放組合物以用於暫時接合;以及提供了雷射剝離製程。本發明的組合物可使用波長約300nm到約360nm的各種UV雷射剝離,且幾乎不留下碎片。由此等組合物形成的層具有良好的熱穩定性,且耐半導體製程中使用的常見溶劑。組合物也可用作用於形成重分佈層的堆積層。
Description
本發明涉及可雷射釋放組合物,其用於暫時晶圓接合製程或在重分佈層形成過程中用作堆積層。
[相關申請案]
本申請案主張在2019年1月22日提出申請之美國臨時申請案第62/795,092號的優先權權益,該臨時申請案名為「用於3D IC應用的可雷射釋放接合材料(Laser-releasable Bonding Materials for 3-D IC Applications)」,並藉全文引用併入本文。
暫時晶圓接合(temporary wafer bonding;TWB)通常指藉由聚合接合材料將元件晶圓或微電子基板附著到載體晶圓或基板的製程。接合後,通常可將元件晶圓減薄到小於50µm及/或進行加工以在其背面形成穿矽通孔(through-silicon vias;TSV)、重分佈層、接合墊及其他電路特徵。在背面加工期間(需可涉及環境溫度及高溫(>250°C)之間重複循環、晶圓處理及轉移步驟產生的機械衝擊,及強大的機械力(諸如在用於使元件晶圓變薄的晶圓背面研磨製程中施加的力)),載體晶圓支撐易碎的元件晶圓。當所有此加工都完成後,元件晶圓通常附著在膜框架,接著自載體晶圓分離(亦即,剝離),並在進一步操作前進行清潔。
大多數TWB製程在元件基板及載體基板之間使用一或兩層。取決於TWB製程,可藉由多種分離方法分離元件及載體基板,諸如化學剝離、熱滑動剝離、機械剝離或雷射剝離,當中以雷射剝離為較佳的剝離方法。就單層雷射剝離系統而言,接合層會響應雷射或其他光源的輻射,這導致層本身的分解,從而導致結構內的接合完整性喪失並使其在不施加機械力的情況中分離。就兩層雷射剝離系統而言,通常在元件表面附近使用第二聚合物接合材料層。在對雷射敏感層進行後加工破壞並分離接合的晶圓對之後,可很容易地從元件晶圓表面清潔第二層。
雷射誘導釋放材料可用於在從紫外線波長(例如,248nm、308nm及355nm)到近紅外(例如,1,064nm)波長的波長範圍內操作。即使在大型面板上,雷射剝離技術在剝離過程中仍可提供高產量及低應力、有效處理薄基板且易於應用。可用於封裝領域中之不同應用,諸如暫時接合、扇出晶圓級封裝、層壓、使用穿矽通孔(TSV)的2.5D/3D積體、系統級封裝(system-in-packaging;SiP)、層疊封裝(package-on-package;PoP)及其他異質積體基礎結構的雷射釋放技術是為人所需的。這技術需要具有高靈敏度的雷射剝離材料,因此可使能耗更低、剝離時間更短、剝離後的碎屑更少。
本發明廣泛地包含一種暫時接合方法,其包含提供包含以下的堆疊:
第一基板,其具有後表面及前表面;
接合層,其與前表面相鄰;
第二基板,其具有第一表面;及
釋放層,其在第一表面及接合層之間,釋放層包含聚酮縮苯胺(polyketanil)。釋放層暴露於雷射能量以促使第一基板及第二基板的分離。
本發明也提供一種微電子結構,其包含:
第一基板,其具有後表面及前表面;
接合層,其與前表面相鄰;
第二基板,其具有第一表面;及
釋放層,其在第一表面及接合層之間,釋放層包含聚酮縮苯胺。
在另一個具體實例中,本發明也提供一種形成釋放層的方法。方法包含施加組合物到包含玻璃或其他透明材料的基板表面。組合物包含溶解或分散在溶劑系統中的聚酮縮苯胺。在約60°°C到約350°C的溫度下加熱組合物以形成釋放層。
在另一個具體實例中,本發明的方法包含形成堆積層在基板的表面上。堆積層包含聚酮縮苯胺,且具有遠離基板表面的上表面。第一重分佈層形成在上表面上,且任選地形成一或多個額外的重分佈層在第一重分佈層上。
在又一個具體實例中,一種微電子結構包含具有表面的基板。堆積層位在基板表面上,且堆積層包含聚酮縮苯胺,且具有遠離基板表面的上表面。在上表面上有第一重分佈層。
本發明涉及新型的可雷射釋放組合物或堆積組合物,以及涉及使用此等組合物的方法。
可雷射釋放或堆積聚合物及組成
1. 聚酮縮苯胺
用於本發明的組合物包含聚酮縮苯胺,其有時被稱為聚酮亞胺(polyketimine)。酮縮苯胺鍵為在酮基及胺基之間形成的鍵。此鍵較佳包含雙鍵鍵合至氮原子的碳原子。作為雙鍵的一部分的碳原子較佳鍵合至另外兩個碳原子(其一或兩者較佳為芳族結構的一部分),而作為雙鍵一部分的氮原子較佳鍵合到另一個碳原子,而另一個碳原子為芳族結構的一部分。前述芳族結構較佳為苯基。苯基的環員可為未經取代的或經取代的(例如,經-NH2
取代)。
在一個較佳的具體實例中,本發明中使用的聚酮縮苯胺由具有胺官能基及酮官能基的單體聚合而成。單體也包含芳族部分,且胺及酮官能基均鍵合至該芳族部分。此單體的較佳結構為:
其中:
R1
至R4
中的每一個可相同或不同;及
R1
至R4
各自選自由以下所組成的群組:氫、烷基(較佳為C1
-C10
且更佳為C1
-C6
)、烷氧基(較佳為C1
-C10
且更佳為C1
-C6
)、羥基及聚乙二醇鏈(較佳為C1
-C10
且更佳為C1
-C6
)。
在一些具體實例中,較佳為R1
至R4
中的一或多個為氫,因為太多或非常大的取代基會產生立體阻礙,從而阻礙聚酮縮苯胺形成反應。根據前述結構的特別較佳單體為4’-胺基苯乙酮(亦即,R1
至R4
各自為氫)。
用於本發明較佳的聚酮縮苯胺可為聚合的或低聚合的,但當聚合或低聚合時,單體應吸收約100nm到約500nm,更佳約300nm到約400nm波長的光,從而賦予聚酮縮苯胺上的光吸收特性。有利地,由聚酮縮苯胺結構形成的亞胺結構產生中等至高的共軛,從而在UV波長下提供強的雷射吸收。一種較佳的聚酮縮苯胺具有以下結構:
其中:
R1
至R4
中的每一個可相同或不同;及
R1
至R4
各自選自由以下所組成的群組:氫、烷基(較佳為C1
-C10
且更佳為C1
-C6
)、烷氧基(較佳為C1
-C10
且更佳為C1
-C6
)、羥基及聚乙二醇鏈(較佳為C1
-C10
且更佳為C1
-C6
)。
同樣地,在上述聚合結構中,特別較佳的是R1
至R4
各自為氫。
可使用希夫鹼反應合成上述聚酮縮苯胺。如上所述,聚酮縮苯胺通常藉由胺及酮之間的反應形成,以形成用於聚酮縮苯胺的重複結構的酮縮苯胺鍵。反應在酸性催化劑存在且高溫下進行,較佳超過約180°C。應從反應中去除水以推動反應向前並降低反應逆向的能力。
聚合過程中使用的合適的催化劑包括選自由硫酸、對甲苯磺酸(pTSA)、鹽酸、其他強酸及前述混合物所組成的群組的那些。具有高沸點的弱酸或金屬基的路易士酸(諸如氯化鋅)也為合適的。以單體莫耳數計,存在的催化劑的量通常為約0.1莫耳%到約5莫耳%,且較佳為約0.5莫耳%到約1.5莫耳%。
用於聚合系統的合適溶劑包括選自由以下所組成的群組的那些:γ-丁內酯(GBL)、n-甲基-2-吡咯啶酮(NMP)、二甲基乙醯胺(DMAc)、二甲基亞碸(DMSO)、苯甲醇、其他高沸點極性溶劑及其混合物。以反應混合物中所有組分的總重量為100重量%計,聚合期間,溶劑通常以約20重量%到約80重量%,較佳以約30重量%到約70重量%存在,其餘為固體。
聚合反應在約150°C到約300°C,且更佳約180°C到約200°C的溫度進行約12小時到約60小時,更佳約24小時到約48小時。較佳去除反應期間產生的水/溶劑混合物以使反應進行。較佳將粗製產物在醇中沉澱並以真空乾燥。
不論聚酮縮苯胺如何形成,如GPC所測定的,其重量平均分子量較佳為約1,000道耳吞到約100,000道耳吞,較佳為約1,500道耳吞到約50,000道耳吞,甚至更佳為約2,000道耳吞到約10,000道耳吞。
2. 聚酮縮苯胺組合物
用於本發明的可雷射釋放或堆積組合物為藉由將聚酮縮苯胺及任何任選的成分簡單地溶解在溶劑系統中而形成。合適的溶劑包括選自由以下所組成的群組的那些:乳酸乙酯、環戊酮、環己酮、丙二醇甲基醚乙酸酯(PGMEA)、丙二醇甲基醚(PGME)、GBL、苯甲醇及其混合物。較佳地,在攪拌同時,在約24小時的過程中進行溶解,從而產生實質上均勻的溶液。該溶液較佳在使用前過濾。
以組合物的總重量為100重量%計,最終的可雷射釋放或堆積組合物較佳包含約1重量%到約40重量%的固體,更佳約3重量%到約25重量%的固體,甚至更佳約5重量%到約20重量%的固體。此等固體通常為約100重量%的聚酮縮苯胺,然而,在一些情況中,以組合物中固體的總重量為100重量%計,固體可為約20重量%到約100重量%的聚酮縮苯胺,較佳約50重量%到約100重量%的聚酮縮苯胺,且更佳約75%到約100%的聚酮縮苯胺。
在一個具體實例中,除了聚酮縮苯胺及溶劑系統之外,組合物中不包括其他成分。也就是說,組合物在溶劑系統中實質上由聚酮縮苯胺所組成,或甚至由聚酮縮苯胺所組成。
在另一個具體實例中,組合物包含聚酮縮苯胺及分散或溶解在溶劑系統(諸如先前提到的溶劑)中的非聚酮縮苯胺的聚合物(或多於一種的聚合物)。在此具體實例中,固體及溶劑的含量如先前所述,但組合物包含:
以組合物中固體的總重量為100重量%計,0.1重量%到約99.9重量%的聚酮縮苯胺,更佳約10重量%到約90重量%的聚酮縮苯胺,甚至更佳約25重量%到約75重量%的聚酮縮苯胺;及
以組合物中固體的總重量為100重量%計,0.1重量%到約99.9重量%的除聚酮縮苯胺以外的聚合物,更佳約10重量%到約90重量%的除聚酮縮苯胺以外的聚合物,甚至更佳約25重量%到約75重量%的除聚酮縮苯胺以外的聚合物。
在另一個具體實例中,可將本文所述的聚酮縮苯胺組合物與市售組合物摻合,以調整該市售組合物的性質。舉例來說,可將在用戶目標波長(例如,約300nm到約400nm)下沒有足夠吸光度的市售組合物與聚酮縮苯胺組合物摻合,以增加該市售組合物在該波長下的吸光度。在此情況中,固體、溶劑、聚酮縮苯胺及除聚酮縮苯胺以外的聚合物的各自的量將與前段中描述的相同。
在一個具體實例中,組合物實質上不含交聯劑。也就是說,以組合物的總重量為100重量%計,組合物包含小於約3重量%,較佳小於約1重量%,甚至更佳約0重量%的交聯劑。在此具體實例中,如上所述,聚酮縮苯胺可為唯一的聚合物或聚合物摻合物中的一種,且其量可為先前所述。
在另一個具體實例中,組合物包括交聯劑。也就是說,以聚酮縮苯胺及任何其他聚合物的總重量為100重量%計,組合物包含約0.1重量%到約20重量%的交聯劑,更佳約0.5重量%到約10重量%的交聯劑,甚至更佳約1重量%到約5重量%的交聯劑。在此具體實例中,如上所述,聚酮縮苯胺可為唯一的聚合物或聚合物摻合物中的一種,且其量可為先前所述。
在另一個具體實例中,組合物包括一或多種包覆劑。包覆劑含有可與單體的胺官能基或酮官能基反應以減慢或停止聚合反應的官能基。合適的封端劑包括環狀酸酐(諸如馬來酸酐、鄰苯二甲酸酐及萘二甲酸酐)、單官能醛(諸如苯甲醛、反式-2-戊烯醛及桂皮醛)、單官能酮(諸如苯乙酮、覆盆子酮及2-乙醯基噻吩)、單官能初級胺(諸如苯胺、對甲氧苯胺及3-胺基-4-甲苯酚)及單官能羧酸(諸如苯甲酸、對甲苯甲酸及1-萘甲酸)。
無論確切配方為何,組合物可在暫時接合製程中用作可雷射釋放組合物,以使用以下所述的製程將元件基板暫時接合到載體基板。此外,可雷射釋放組合物可在重分佈層形成製程中用作堆積組合物,同樣如下所述。
使用可雷射釋放或堆積組合物的方法
1. 暫時接合具體實例
請參考圖1(a)(未按比例),示意性橫截面圖示出了前驅體結構10。結構10包括第一基板12。基板12具有前表面或元件表面14、後表面16及最外邊緣18。儘管基板12可為任何形狀,但其通常為圓形的。較佳的第一基板12包括元件晶圓,諸如元件表面包含選自由以下所組成的群組的元件陣列(未示出)的那些元件晶圓:積體電路;MEMS;微感測器;功率半導體;發光二極管;光子電路;中介層;嵌入式被動元件;以及在矽或其他半導體材料(諸如矽鍺、砷化鎵、氮化鎵、砷化鋁鎵、磷化鋁銦及磷化銦鎵)上或由其製造的微元件。此等元件的表面通常包含由以下一或多種材料所形成的結構(同樣未示出):矽、多晶矽、二氧化矽、氮(氧)化矽、金屬(例如,銅、鋁、金、鎢、鉭)、低k介電質、聚合物介電質及各種金屬氮化物與矽化物。元件表面14也可包括選自由以下所組成的群組的至少一種結構:焊料凸塊;金屬桿(metal post);金屬柱(metal pillar);以及選自由以下所組成的群組的材料所形成的結構:矽、多晶矽、二氧化矽、氮(氧)化矽、金屬、低k介電質、聚合物介電質、金屬氮化物及金屬矽化物。
如圖1(a)所示,施加組合物到第一基板12以形成接合層20在元件表面14上。接合層20具有遠離第一基板12的上表面21,且接合層20較佳直接相鄰元件表面14形成(亦即,接合層20及基板12之間無任何中間層)。儘管接合層20示出為覆蓋第一基板12的整個元件表面14,但應理解的是,其僅可存在於元件表面14的一部分或「區域」上,如以引用方式併入本文的美國專利公開第2009/0218560號所示。
可藉由任何已知的施加方法來施加接合組合物,包括浸塗、輥塗、狹縫塗布、模頭塗布、網板印刷、下引塗佈或噴塗。另外,可在塗層施加到元件基板或載體基板表面之前,將其形成為自支撐膜(free-standing film)。一種較佳的方法涉及以約200rpm到約5,000rpm的速度(較佳約500rpm到約3,000rpm)旋轉塗布組合物約5秒到約120秒的時間(較佳約30秒到約90秒)。
施加組合物後,較佳加熱其到約50°C到約250°C,更佳約80°C到約220°C的溫度,持續約60秒到約8分鐘的時間(較加約90秒到約6分鐘)。取決於用於形成接合層20的組成物,烘烤也可引發交聯反應以固化層20。在一些具體實例中,取決於所使用的組成物,較佳使層經受多階段烘烤製程。而且在一些情況中,可在組合物的另一等分試樣上重複上述施加及烘烤製程,從而第一接合層20以複數個步驟「堆積」在第一基板12上。所得接合層20的平均厚度(五個測量的平均值)應為約1µm到約200µm,更佳為約10µm到約150µm,且甚至更佳為約20µm到約120µm。
形成接合層20的材料應能與第一基板12形成牢固的黏合。如藉ASTM D4541/D7234所測定的,黏合強度大於約50psig,較佳為約80psig到約250psig,且更佳為約100psig到約150psig的任何材料,都希望用作接合層。
有利地,用於形成接合層20的組合物可選自可商購的接合組合物,其能夠形成具有上述黏合特性的層,同時可藉由加熱及/或溶劑去除。此等組合物典型為有機的,且包含溶解或分散在溶劑系統中的聚合物或低聚合物。聚合物或低聚合物通常選自由以下所組成的群組的聚合物或低聚合物:環烯烴類、環氧樹脂類、丙烯酸類、矽酮類、苯乙烯類、鹵乙烯類、乙烯酯類、聚醯胺類、聚醯亞胺類、聚碸類、聚醚碸類、環烯烴類、聚烯烴橡膠類、聚胺酯類、乙丙橡膠類、聚醯胺酯類、聚醯亞胺酯類、聚縮醛類、聚乙烯丁醛類,及前述混合物。典型溶劑系統取決於聚合物或低聚合物的選擇。以組合物的總重量為100重量%計,接合組合物的典型固體含量介於約1重量%到約60重量%,且較佳約3重量%到約40重量%的範圍。美國專利公開第2007/0185310、2008/0173970、2009/0038750及2010/0112305號描述了一些合適的組合物,每者均藉由引用併入本文。
圖1(a)也以示意性及橫截面圖示出第二前驅體結構22。第二前驅體結構22包括第二基板24。在此具體實例中,第二基板24為載體晶圓。也就是說,基板24具有前表面或載體表面26、後表面28及最外邊緣30。儘管第二基板24可為任何形狀,但其通常是圓形的,且尺寸類似於第一基板12。第二基板24較佳包括透明晶圓或任何其他透明的(對於雷射能量而言)透明的基板,其能允許雷射能量穿過載體基板,包括但不限於玻璃、Corning Gorilla玻璃及藍寶石。一種特別較佳的玻璃載體晶圓為Corning EAGLE XG玻璃晶圓。
如圖1(a)所示,將如上所述的聚酮縮苯胺組合物施加到第二基板24,以在載體表面26上形成雷射釋放層32。或者,可提供已形成的結構22。釋放層32具有遠離第二基板24的上表面33,以及與第二基板24相鄰的下表面36。較佳地,釋放層32直接相鄰載體表面26形成(亦即,第二接合層32及第二基板24之間無任何中間層)。
可雷射釋放的組合物可藉任何已知的施加方法施加,其中一種較佳的方法為在約500rpm到約3,000rpm的速度(較佳約1,000rpm到約2,000rpm)旋轉塗布組合物,持續約10秒到約120秒的時間(較佳約30秒到約90秒)。施加組合物後,較佳加熱其到約60°C到約350°C,且更佳約140°C到約250°C的溫度,持續約30秒到約20分鐘,更佳約1分鐘到15分鐘的時間。接著,使釋放層32在約250°C到約350°C,且更佳約280°C到約320°C的溫度,並持續較佳約2分鐘到約60分鐘,更佳約10分鐘的時間內經受高溫最終烘烤。
在一個具體實例中,此最終烘烤藉由使在雷射釋放層32中存在的兩個或更多個聚酮縮苯胺鏈中發生鏈增長反應而使聚合反應完成。因此,在此等情況中,加熱後存在的聚酮縮苯胺鏈比加熱前存在的鏈具有更高的分子量。在其中包括交聯劑的具體實例中,一或兩個加熱階段將引起發生交聯,從而在釋放層32中產生經交聯的聚酮縮苯胺。
在一些具體實例中,取決於所使用的組成物,較佳使釋放層32經受多階段烘烤製程。而且在一些情況中,可在組合物的另一等分試樣上重複上述施加及烘烤製程,從而雷射釋放層以複數個步驟「堆積」在第二基板上。
無論具體實例為何,加熱後,釋放層32較佳具有約10nm到約5,000nm,更佳約100nm到約1,000nm,且甚至更佳約150nm到約750nm的平均厚度。可使用任何膜厚測量工具來測量本文所使用的厚度,其中一種較佳的工具為紅外線干涉光譜儀,諸如SUSS Microtec或Foothill出售者。
在另一個具體實例中,根據本發明的聚酮縮苯胺組合物可形成為預製的乾膜,而非作為可流動的組合物使用。在此情況中,組合物形成了無支撐的自持膜(self-sustaining film),即使無支撐其也不會塌陷或變形(無施加力或能量)。接著,可將此膜黏附到第二基底以形成釋放層32。
雷射釋放層32在期望的波長(亦即,用於剝離或分解接合層20的波長)處的k值至少為約0.1,較佳至少為約0.2,更佳至少為約0.24,且甚至更佳為約0.24到約0.5。雷射釋放層32的n值至少為約1.4,較佳至少為約1.5,更佳至少為約1.6,且甚至更佳為約1.7到約2。
請再次參考圖1(a)的結構22,儘管釋放層32被示出為覆蓋第二基板24的整個表面26,但應理解的是,其僅可存在於載體表面26的一部分或「區域」上,類似於對接合層20所描述的。
接著,將結構10及22壓合在一起而呈現面對面的關係,使得接合層20的上表面21與釋放層32的上表面33接觸(圖1(b))。在壓合的同時,施加足夠的壓力及熱並持續足夠的時間,以將兩個結構10及22接合在一起,從而形成經接合的堆疊34。接合參數將根據形成接合層20的組成物而變化,但此步驟期間的典型溫度在約25°C到約250°C的範圍,且較佳在約150°C到約220°C的範圍;典型壓力在約1,000N到約25,000N的範圍,且較佳從約3,000N到約10,000N的範圍;持續時間約30秒到約20分鐘,且較佳約3分鐘到約10分鐘。
在替代具體實例中,將理解的是,可使用先前描述的施加製程將接合層20施加到釋放層32的上表面33,而非施加到第一基板12的表面14。在此情況中,接著使第一基板12經受上述接合製程,以將第一基板12的表面14接合至接合層20(其預先形成在釋放層32的上表面33)。
經接合堆疊的TTV應小於總平均厚度的約10%,較佳小於總平均厚度的約5%(在整個基板的五個位置處測量),且甚至更佳小於經接合堆疊的總平均厚度的約3%。也就是說,若經接合堆疊的平均厚度為100µm,則TTV小於約10%將為約10µm或更小。
無論使用何具體實例形成經接合堆疊34,現在都可安全地處理第一基板12並使其經受進一步處理(否則其可能早已損壞第一基板12而無接合到第二基板24)。因此,可安全地使結構經受背面加工,諸如背面研磨、化學機械拋光(「CMP」)、蝕刻、金屬沉積(亦即,金屬化)、介電質沉積、圖案化(例如,光刻、通孔蝕刻)、鈍化、退火及其組合,而不會發生基板12及24的分離,也不會滲入此等後續加工步驟中遇到的任何化學物質。接合層20及釋放層32不僅可承受住此等加工,且也可承受高達約300°C,較佳約150°C到280°C,且更佳約180°C到約250°C的加工溫度,並持續至少約60分鐘,且較佳約90分鐘到約15小時的時間。
一旦完成加工,即可藉使用雷射分解或燒蝕全部或部分雷射釋放層32,以分離基板12及24。合適的雷射波長包括約200nm到約400nm,且較佳約300nm到約360nm的那些波長。為了使雷射釋放層32剝離,以步進重複(stand-and-repeat)方法或線掃描方法在基板24的整個表面上掃描雷射,以暴露整個晶圓。例示性的雷射剝離工具包括SUSS MicroTec Lambda STEEL 2000雷射剝離機及Kingyoup雷射剝離機。基板24較佳以雷射點掃描,其範圍大小約40×40µm到約12.5×4mm。使基板12、24剝離的合適通量為約100mJ/cm2
到約400mJ/cm2
,且較佳為約150mJ/cm2
到約350mJ/cm2
。使基板12、24剝離的合適功率為約0.5W到約6W,且較佳為約1W到約2W。
雷射曝光後,基板12及24將容易分離。分離後,可以電漿蝕刻或能溶解接合層20的溶劑去除任何剩餘的接合層20。
對於電漿清潔而言,可以100W或更高的功率單獨使用O2
電漿,或者使用O2
電漿及氟化氣體的組合(其比例為約1:1到約10:1)。
可藉浴或旋轉清潔製程實施溶劑清潔。適用於非極性接合材料的溶劑包括但不限於右旋檸檬烯、均三甲苯(mesitylene)、1-十二烯及其組合。適用於清潔極性接合材料的溶劑包括GBL、環戊酮、苯甲醇、DMSO、環己酮、PGME、PGMEA、NMP、1,3-二氧戊環及其組合。
當使用旋轉清潔製程時,較佳實施約1分鐘到約15分鐘的清潔時間。在旋轉清潔製程中,藉由覆液及浸泡循環的組合將溶劑噴灑到晶圓的中心,接著將其旋轉掉。對於覆液及浸泡循環而言,將溶劑噴灑到晶圓的中心,接著以約20rpm到約150rpm的旋轉速度將其浸出,並在無溶劑噴灑或晶圓旋轉的情況中浸泡約30秒到約90秒。在最後步驟中,將溶劑分配在基板的中心,接著以約750rpm到約1,500rpm的旋轉速度旋轉基板。
在上述具體實例中,釋放層32被示出在作為載體晶圓的第二基板24上,而接合層20被示出在作為元件晶圓的第一基板12上。應理解的是,可顛倒此基板/層結構。也就是說,釋放層32可形成在第一基板12(元件晶圓)上,而接合層20形成在第二基板24(載體晶圓)上。除了選擇接合層20使得雷射能量在穿過第二基板24之後可穿過接合層20以外,可施加如上所述的該等相同組成物及加工條件到此具體實例,從而使雷射能量與釋放層32接觸。
另外,將理解的是,接合層20及釋放層32可與以下一同使用或用作以下:額外的接合材料、結構支撐層、層合輔助層、連結層(用於黏附到初始基板)、汙染控制層及清潔層。較佳的結構及應用技術將由應用及操作流程決定。
2. 堆積層具體實例
在另一個具體實例中,本文所述的聚酮縮苯胺組合物可用作用於重分佈層(「RDL」)形成的堆積層,特別是在晶圓或面板級製程中的先RDL/後晶片封裝(RDL-first/chip-last packaging)中,其對於最小化或甚至避免封裝過程中合格裸晶減損(known-good die loss)非常有用。圖2示出此製程的示意圖。
如圖2(a)所示,將如先前所述的聚酮縮苯胺組合物施加到載體基底40的上表面38,以形成可雷射釋放堆積層42在載體表面38上。按照關於以上暫時接合具體實例描述的任何方法,包括製程條件及所得特性,來形成堆積層42。堆積層42具有遠離載體基板40的上表面44,且堆積層42較佳直接形成在載體基板40的上表面38上(亦即,堆積層42及基板40之間無任何中間層)。
接著,按照常規方法沉積種子層46在上表面44上(圖2(b))。接著,可再次按照已知方法,種子層46可經光阻劑塗布、圖案化及電鍍,以形成圖2(c)所示的結構。請參照圖2(d),除去光阻劑並蝕刻金屬,接著塗布、圖案化及固化介電層。如圖2(e)所示,此導致第一RDL 48的形成。可根據需要重複圖2(b)到圖2(e)的步驟多次,以產生多個RDL(48(a)-(d),亦即,圖2(f)中所示的具體實例中的4個RDL)。
請參照圖2(g),已形成期望數量的RDL後,再次按照常規方法將焊球50附接到最上面的(最後形成的)RDL。將裸晶52接合到焊球50,接著施加及研磨常規的環氧樹脂模製層54以形成扇出晶圓級封裝結構56。最後,按照先前描述的雷射分離條件,將雷射能量施加到載體基板40,以分解或燒蝕全部或部分可雷射釋放堆積層42。施加雷射之後,載體基板40將被釋放並與扇出晶圓級封裝結構56分離(圖2(h)),並以溶劑去除任何剩餘的堆積層42。
應當注意的是,用於形成扇出晶圓級封裝結構的上述製程僅為可使用本發明的組合物作為堆積層來執行的此類製程的一個實施例,且可根據使用者需要對此製程的進行變化。舉例來說,可根據需要改變RDL層的數量以及焊球及裸晶的數量與位置。本發明所屬技術領域中具有通常知識者將理解及訂製此等配置。
從上述可看出,本發明具有許多優點。在各種波長下,包括主要用於雷射解剝離(約300nm到約400nm)直至整個可見光範圍的波長,聚酮縮苯胺(以及由此形成的層)都具有高吸光度。另外,聚酮縮苯胺的高吸光度使得能在晶圓上澆鑄更薄的薄膜,同時仍能吸收大部分到所有雷射能量,以防止元件損壞。高吸光度也有利於減少剝離晶圓所需的雷射能量及時間。除了對雷射剝離的直接好處之外,此等材料也可用於先RDL製程。聚合物可利用各種單體,從而使結構因可交聯基團或鏈延長而變得不溶。這類聚合物可提供300°C或更高的熱穩定性、可提供對矽及玻璃基板良好的接合性,且可藉由乾蝕刻(電漿蝕刻)以與聚醯亞胺相似的蝕刻速率去除。最後,由於需要更薄的膜的緣故,可因此減少矽及玻璃基板上的應力及彎曲。
藉由閱讀本文的揭示及以下實施例,各種具體實例的其他優點對於本發明所屬技術領域中具有通常知識者將是顯而易見的。將理解的是,除非本文另外指出,否則本文描述的各種具體實例不必然相互排斥。舉例來說,在一個具體實例中描述或描繪的特徵也可包括在其他具體實例中,但不必然包括在其中。因此,本發明涵蓋本文描述的特定具體實例的各種組合及/或整合。
除非另外指出,否則當包含在上述的組合物或層中時,「聚酮縮苯胺」旨在包括單一類型的聚酮縮苯胺基以及兩種或更多種不同類型的聚酮縮苯胺。另外,如本文中所用,當在兩個或多個項目的列舉中使用時,片語「及/或」表示所列出的項目中的任何一個可單獨使用,或者可使用兩個或更多個所列出的項目的任何組合。舉例來說,若描述組合物為含有或不包括組分A、B及/或C,則該組合物可:單獨含有或不包括A、單獨含有或不包括B、單獨含有或不包括C、含有或不包括A及B的組合、含有或不包括A及C的組合、含有或不包括B及C的組合,或含有或不包括A、B及C的組合。
本說明書也使用數值範圍來量化與本發明的各種具體實例有關的某些參數。應當理解的是,當提供數值範圍時,將解釋此等範圍為對僅記載該範圍較低值的申請專利範圍限制及對僅記載該範圍較高值的申請專利範圍限制提供文字支持。舉例來說,揭示的約10到約100的數值範圍對記載「大於約10」(無上限)的申請專利範圍及對記載「小於約100」(無下限)的申請專利範圍限制提供文字支持。
實施例
以下實施例闡述了根據本發明的方法。然而,應理解的是,此等實施例僅作為舉例說明而提供,且當中的任何內容均不應視為對本發明總體範圍的限制。
實施例1
聚合作用形成聚酮縮苯胺
在此步驟中,在一個四頸1公升的圓底燒瓶中,將13.07g的4’-胺基苯乙酮(Alfa Aesar, Haverhill, MA)溶解於20.76g的γ-丁內酯(GBL;Sigma Aldrich, St. Louis, MO)。該燒瓶配有加熱罩、溫度控制器、熱探針、Dean-Stark分水器及帶有攪拌子及槳式混合器的頂置式攪拌器。將冷凝器連接到Dean-Stark分水器。開始向燒瓶中通入氮氣流,並將反應加熱到110°C。接著將加0.06g(0.18%)96%的硫酸(KMG Chemicals, Ft. Worth, TX)加入溶液,並接著將溶液加熱到185°C。將水及GBL混合物收集在Dean-Stark分水器中(約佔溶液總重量的7%),且不加回到系統中。使溶液反應48小時,並接著冷卻到室溫。所得溶液具有約35%固體,且為暗紅色、略帶黏稠的溶液。接著將冷卻的溶液裝瓶以便進一步使用。
實施例2
聚酮縮苯胺組合物的製備
在實施例中,以頂置攪拌馬達將實施例1的634.20g的溶液與665.86g的乳酸乙酯(KMG Chemicals, Ft. Worth, TX)混合。攪拌混合物直到所有固體溶解。接著使用0.2-µm的Meissner過濾器過濾所得溶液。
實施例3
聚酮縮苯胺組合物的特性分析
1. 光學性質
將實施例2中製備的材料塗布在100-mm的Si晶圓上。藉由以1,500rpm/s的加速度以1,500rpm的轉速旋轉塗布60秒來完成此塗布。接著將載體晶圓在150°C中烘烤2分鐘,在220°C中烘烤2分鐘,在250°C中烘烤5分鐘,及在300°C中烘烤10分鐘。接著將經塗布的晶圓在VASE M2000橢圓偏光儀上運行以獲取原始光學數據。接著擬合數據以獲取厚度及光學特性(n及k值)。感興趣的波長為308nm、343nm及355nm。表1總結結果,且圖3示出全光譜。
表1:光學常數
2. 厚度、分子量及多分散性指數
波長(nm) | n | k |
308 | 1.84 | 0.43 |
343 | 1.87 | 0.26 |
355 | 1.86 | 0.24 |
將實施例2中製備的材料塗布在200-mm的玻璃晶圓上。藉由以1,500rpm/s的加速度以1,500rpm的轉速旋轉塗布60秒來完成此塗布。接著將載體晶圓在150°C中烘烤2分鐘,在220°C中烘烤2分鐘,在250°C中烘烤5分鐘,及在300°C中烘烤10分鐘。接著在FRT Microprof® 300工具上使用1x1mm解析度的點圖掃描分析經塗布的晶圓,得到的平均厚度值為673.48nm,TTV為32.89nm,高低數據排除率為1%。
使用NMP、THF、乙酸及溴化鋰及1ml/min的移動相流速,以由Waters 717液體層析系統實施GPC。使用Waters 410示差分折射率檢測器完成檢測,並使用與聚苯乙烯標準品的相對校準對信號進行積分及定量。表2示出此等結果。
表2:平均分子量及多分散性指數(「PDI」)
實施例4
使用實施例2的調配物進行接合
Mw(道耳吞) | Mn(道耳吞) | Mz(道耳吞) | PDI |
2,809 | 1,623 | 4,682 | 1.73 |
將實施例2中製備的材料塗布在200-mm的作為載體晶圓的玻璃晶圓上。藉由以1,500rpm/s的加速度以1,500rpm的轉速旋轉塗布60秒來完成此塗布。接著將載體晶圓在60°C中烘烤2分鐘,在120°C中烘烤2分鐘,在250°C中烘烤5分鐘,及在300°C中烘烤10分鐘。將實驗性的以苯氧基為主的熱塑性接合材料(Brewer Science, Rolla, MO)塗布在200-mm的矽晶圓上作為模擬元件晶圓。藉由以3,000rpm/s的加速度以1,500rpm的轉速旋轉塗布30秒來完成此塗布。接著將載體晶圓在60°C中烘烤5分鐘,在160°C中烘烤5分鐘,及在220°C中烘烤5分鐘。藉由在EVG®
510接合系統((EV Group))及真空(<5mbar)中,以200°C、3000 N接合3分鐘,將經塗布的載體晶圓接合到經塗布的元件晶圓。
實施例5
使用實施例2的調配物進行雷射剝離及清潔
藉由使用工業上目前使用的三種主要的UV雷射波長,成功剝離經接合的晶圓對。每個波長使用不同的剝離設備,且該設備為:SUSS ELD12雷射剝離機(Garching bei München, Germany);EVG半自動剝離系統(St. Florian/Inn, Austria);及Kingyoup LD-Semi Automatic 200/300(New Taipei City, Taiwan)。表3、4及5分別顯示SUSS、Kingyoup及EVG剝離機的雷射剝離參數及結果。
表3:SUSS剝離機的雷射剝離參數及結果
表4:Kingyoup剝離機的結果
表5:EVG剝離機的結果
實施例6
聚酮縮苯胺與低吸收性材料的摻合
通量(mJ/cm2 ) | 結果 (光束尺寸為12.5 x 4mm,重疊部分為100-200µm) |
160 | 成功剝離;觀察到低殘留物 |
200 | 成功剝離;觀察到較高殘留物 |
功率(W) | 掃描速度(m/s) | 線距(µm) | 掃描時間(s) | 結果 (光束尺寸為60µm) |
2 | 3.5 | 70 | 128.2 | 成功剝離 |
1.5 | 3.4 | 69 | 133.9 | 成功剝離 |
1.2 | 2.6 | 53 | 228.0 | 成功剝離 |
通量(mJ/cm2 ) | 結果 (光束尺寸為40x40µm,且間距尺寸為40µm) |
750 | 成功剝離;顯示非常低的碳殘留物 |
500 | 成功剝離;顯示無碳殘留物且無UV膠帶穿透 |
進行該步驟以示出如何將本發明的聚合物及組合物與其他聚合物組合物摻合,以改善該等聚合物組合物的性能。在此情況中,另一種聚合物組合物包括在GBL-環戊酮溶劑混合物(其稱為「聚醯亞胺溶液」)中的12重量%的市售聚醯亞胺溶液,其在300-400nm處為低吸收的。
將17.5重量%的實施例1中製備的材料的溶液與環戊酮(獲自FujiFilm)以1:1的重量比混合(其稱為「聚酮縮苯胺添加劑」)。將聚酮縮苯胺添加劑與聚醯亞胺溶液以不同的比例摻合,表6總結每者的重量。
表6:摻合的聚酮縮苯胺添加劑及聚醯亞胺溶液的重量
聚酮縮苯胺添加劑的重量(g) | 聚醯亞胺溶液的重量(g) | 添加劑百分率* |
1.03 | 5.14 | 16.7% |
2.08 | 5.07 | 29.1% |
3.02 | 5.02 | 37.5% |
4.03 | 5.16 | 43.8% |
旋轉塗布經製備的溶液來獲得足夠薄的膜,以測量在100nm到500nm厚度範圍的吸光度(k)。藉由以1,500rpm/s的加速度以1,500rpm的轉速旋轉塗布60秒來完成此塗布。接著將晶圓在60°C中烘烤2分鐘,在150°C中烘烤2分鐘,及在220°C中烘烤5分鐘。接著將經塗布的晶圓在VASE M2000橢圓偏光儀上運行以獲取原始光學數據。接著擬合數據以獲取厚度及光學特性(n及k值)。感興趣的波長為308nm、343nm及355nm。表7總結此等結果。
表7:不同聚酮縮苯胺添加劑比例的主要波長處k值的變化
聚酮縮苯胺添加劑% | 308nm處的k值 | 343nm處的k值 | 355nm處的k值 |
0.00% | 0.08 | 0.03 | 0.03 |
43.84% | 0.27 | 0.15 | 0.14 |
37.51% | 0.21 | 0.13 | 0.12 |
29.13% | 0.19 | 0.11 | 0.10 |
16.72% | 0.14 | 0.07 | 0.07 |
無
[圖1]為根據本發明的一個具體實例的暫時接合製程的示意圖的橫截面圖。
[圖2]為示出根據本發明另一具體實例的形成重分佈層的示意圖;及
[圖3]為示出實施例3中測定的n值及k值的光譜的圖。
10:前驅體結構
12:第一基板
14:前表面或元件表面
16:後表面
18:最外邊緣
20:接合層
21:上表面
22:第二前驅體結構
24:第二基板
26:前表面或載體表面
28:後表面
30:最外邊緣
32:雷射釋放層
33:上表面
34:經接合的堆疊
36:下表面
Claims (31)
- 一種暫時接合方法,包含: 提供堆疊,其包含: 第一基板,其具有後表面及前表面; 接合層,其與該前表面相鄰; 第二基板,其具有第一表面;及 釋放層,其在該第一表面及該接合層之間,該釋放層包含聚酮縮苯胺 (polyketanil);及 暴露該釋放層於雷射能量,以促使該第一基板及該第二基板分離。
- 如請求項1之方法,其中該聚酮縮苯胺為經交聯的。
- 如請求項1之方法,其中該聚酮縮苯胺為包含胺官能基、酮官能基及芳族部分的單體的聚合物,其中該胺官能基及該酮官能基鍵合至該芳族部分。
- 如請求項3之方法,其中該重複單體為4-胺基苯乙酮。
- 如請求項1之方法,其進一步包含以下一或兩者: 該前表面為元件表面,其包含選自由以下所組成的群組的元件陣列:積體電路;MEMS;微感測器;功率半導體;發光二極管;光子電路;中介層;嵌入式被動元件;以及在矽、矽鍺、砷化鎵、氮化鎵及前述組合之上或由其製造的微元件;或 該第一表面為元件表面,其包含選自由以下所組成的群組的元件陣列:積體電路;MEMS;微感測器;功率半導體;發光二極管;光子電路;中介層;嵌入式被動元件;以及在矽、矽鍺、砷化鎵、氮化鎵及前述組合之上或由其製造的微元件。
- 如請求項1之方法,其中該第一基板或該第二基板中的一或兩者包含玻璃或其他透明材料。
- 如請求項1之方法,其進一步包含以下一或兩者: 該前表面為元件表面,其包含選自由以下所組成的群組的至少一種結構:焊料凸塊;金屬桿(metal post);金屬柱(metal pillar);以及選自由以下所組成的群組的材料所形成的結構:矽、多晶矽、二氧化矽、氮(氧)化矽、金屬、低k介電質、聚合物介電質、金屬氮化物、金屬矽化物,及其前述的組合;或 該第一表面為元件表面,其包含選自由以下所組成的群組的至少一種結構:焊料凸塊;金屬桿;金屬柱;以及選自由以下所組成的群組的材料所形成的結構:矽、多晶矽、二氧化矽、氮(氧)化矽、金屬、低k介電質、聚合物介電質、金屬氮化物、金屬矽化物,及其前述的組合。
- 如請求項1之方法,其進一步包含在分離該第一基板及該第二基板之前,使該堆疊經受選自由以下所組成的群組的處理:背面研磨、化學機械拋光、蝕刻、金屬化、介電質沉積、圖案化、鈍化、退火及其組合。
- 如請求項1之方法,其中該提供包含將該第一基板及該第二基板接合在一起,以形成該堆疊。
- 一種微電子結構,其包含: 第一基板,其具有後表面及前表面; 接合層,其與該前表面相鄰; 第二基板,其具有第一表面;及 釋放層,其在該第一表面及該接合層之間,該釋放層包含聚酮縮苯胺。
- 如請求項10之結構,其中該聚酮縮苯胺為經交聯的。
- 如請求項10之結構,其中該聚酮縮苯胺為包含胺官能基、酮官能基及芳族部分的單體的聚合物,其中該胺官能基及該酮官能基鍵合至該芳族部分。
- 如請求項12之結構,其中該重複單體為4-胺基苯乙酮。
- 如請求項10之結構堆疊,其進一步包含以下一或兩者: 該前表面為元件表面,其包含選自由以下所組成的群組的元件陣列:積體電路;MEMS;微感測器;功率半導體;發光二極管;光子電路;中介層;嵌入式被動元件;以及在矽、矽鍺、砷化鎵、氮化鎵及前述組合之上或由其製造的微元件;或 該第一表面為元件表面,其包含選自由以下所組成的群組的元件陣列:積體電路;MEMS;微感測器;功率半導體;發光二極管;光子電路;中介層;嵌入式被動元件;以及在矽、矽鍺、砷化鎵、氮化鎵及前述組合之上或由其製造的微元件。
- 如請求項10之結構,其中該第一基板或該第二基板中的一或兩者包含玻璃或其他透明材料。
- 如請求項10之結構,其進一步包含以下一或兩者: 該前表面為元件表面,其包含選自由以下所組成的群組的至少一種結構:焊料凸塊;金屬桿;金屬柱;以及選自由以下所組成的群組的材料所形成的結構:矽、多晶矽、二氧化矽、氮(氧)化矽、金屬、低k介電質、聚合物介電質、金屬氮化物、金屬矽化物,及其前述的組合;或 該第一表面為元件表面,其包含選自由以下所組成的群組的至少一種結構:焊料凸塊;金屬桿;金屬柱;以及選自由以下所組成的群組的材料所形成的結構:矽、多晶矽、二氧化矽、氮(氧)化矽、金屬、低k介電質、聚合物介電質、金屬氮化物、金屬矽化物,及其前述的組合。
- 一種形成釋放層的方法,其包含: 施加組合物到包含玻璃或其他透明材料的基板表面,該組合物包含溶解或分散在溶劑系統中的聚酮縮苯胺;及 在約60°C到約350°C的溫度下加熱該組合物以形成該釋放層。
- 如請求項17之方法,其中該組合物包含複數個聚酮縮苯胺鏈,且該加熱使具有初始分子量(A)的第一聚酮縮苯胺鏈與具有初始分子量(B)的第二聚酮縮苯胺鏈進行鏈延長反應,以形成分子量大於該第一聚酮縮苯胺鏈的該初始分子量(A)且大於該第二聚酮縮苯胺鏈的該初始分子量(B)的聚合物。
- 如請求項18之方法,其中該加熱引起該複數個聚酮縮苯胺鏈間的複數個該等鏈延長反應。
- 如請求項17之方法,其中該聚酮縮苯胺為包含胺官能基、酮官能基及芳族部分的單體的聚合物,其中該胺官能基及該酮官能基鍵合至該芳族部分。
- 一種形成微電子結構的方法,該方法包含: (I)形成堆積層在基板的表面上,該堆積層包含聚酮縮苯胺且具有遠離該基板的該表面的上表面; (II)形成第一重分佈層在該上表面上;及 (III)任選地形成一或多個額外的重分佈層在該第一重分佈層上。
- 如請求項21之方法,其進一步包含暴露該堆積層於雷射能量,且分離該基板及該扇出晶圓級封裝結構。
- 如請求項21之方法,其中該聚酮縮苯胺為包含胺官能基、酮官能基及芳族部分的單體的聚合物,其中該胺官能基及該酮官能基鍵合至該芳族部分。
- 一種微電子結構,其包含: 基板,其具有表面; 堆積層,其在該基板表面上,該堆積層包含聚酮縮苯胺且具有遠離該基板表面的上表面;及 第一重分佈層,其在該上表面上。
- 如請求項24之結構,其中該基板包含玻璃或其他透明材料。
- 如請求項24之結構,其中該聚酮縮苯胺為經交聯的。
- 如請求項24之結構,其中該聚酮縮苯胺為包含胺官能基、酮官能基及芳族部分的單體的聚合物,其中該胺官能基及該酮官能基鍵合至該芳族部分。
- 如請求項27之結構,其中該重複單體為4-胺基苯乙酮。
- 如請求項29之聚合物,其中每個R為氫。
- 如請求項29之聚合物,其中該聚合物的重量平均分子量為約1,000道耳吞到約100,000道耳吞。
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CN113439112B (zh) * | 2019-01-22 | 2024-01-05 | 布鲁尔科技公司 | 用于3-d ic用途的可激光剥离的结合材料 |
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CN113439112B (zh) | 2024-01-05 |
US11610801B2 (en) | 2023-03-21 |
SG11202107879PA (en) | 2021-08-30 |
EP3914663A1 (en) | 2021-12-01 |
KR20210108482A (ko) | 2021-09-02 |
US20200234993A1 (en) | 2020-07-23 |
US20230187257A1 (en) | 2023-06-15 |
EP3914663A4 (en) | 2022-09-14 |
CN113439112A (zh) | 2021-09-24 |
WO2020154225A1 (en) | 2020-07-30 |
JP2022522974A (ja) | 2022-04-21 |
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