TW202402549A - 可雷射釋放組成物之應用 - Google Patents
可雷射釋放組成物之應用 Download PDFInfo
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- TW202402549A TW202402549A TW111125507A TW111125507A TW202402549A TW 202402549 A TW202402549 A TW 202402549A TW 111125507 A TW111125507 A TW 111125507A TW 111125507 A TW111125507 A TW 111125507A TW 202402549 A TW202402549 A TW 202402549A
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- Prior art keywords
- sacrificial layer
- layer
- alkali
- substrate
- soluble polymer
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
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- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
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- C—CHEMISTRY; METALLURGY
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Abstract
本發明係提供一種暫時接合方法,其包含:提供一疊加物,該疊加物包含:一第一基板、一黏接層、一第二基板及一犧牲層;以及對該犧牲層施予雷射能量,以促進該第一基板與該第二基板分離。本發明中之犧牲層為鹼性水溶液可溶解者,因此,若有殘存之犧牲層,可輕易以鹼性水溶液移除,而避免損傷元件。
Description
本發明係關於一種可雷射釋放組成物,其係用於形成於暫時接合製程或於重分佈層形成過程中所使用之犧牲層。
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。為使晶圓在使用中能夠更加散熱、延長壽命並有利於後期系統封裝,通常需將元件晶圓減薄到小於50μm。一般而言,先將元件晶圓暫時性黏接至較厚的承載玻璃上,並在晶圓背面進行腐蝕、研磨等加工減薄,亦可進行穿矽通孔(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(需可承受環境溫度極高溫(大於250℃)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,再經過外界的光、電、熱使黏接層失效,元件晶圓自承載體分離(亦即,剝離),並再進一步操作進行清潔。
在習知技術中,暫時性黏接層主要有UV解黏膠、熱解黏膠、溶劑解黏膠與雷射解黏膠,但此UV解黏膠與熱解黏膠的耐熱溫度約為120-150℃,無法耐溫至260℃,容易受到外界影響,造成解黏反應提早發生。溶劑解黏膠的缺點在於耐溶劑性不佳,在製程上有所限制。雷射解黏的耐熱性及耐化性較佳,但在解黏過程中容易有殘膠產生,需使用高極性溶劑去除,可能造成元件上的其他材料被侵蝕,因此在使用上亦有所限制。
有鑑於上述技術問題,本發明之目的即係提供一種新穎的暫時接合方法,該接合方法可使用鹼性水溶液移除解黏過程中可能產生之殘膠,進而大幅降低元件被侵蝕之可能性。
本發明另一目的則係提供一種新穎形成微電子結構之方法,該方法可使用鹼性水溶液移除解黏過程中可能產生之殘膠,進而大幅降低元件被侵蝕之可能性。
為達上述目的,本發明係提供一種暫時接合方法,其包含:提供一疊加物,該疊加物包含:一第一基板,其具有上表面及一下表面;一黏接層,其係與該下表面接觸;一第二基板,其具有一第一表面;及一犧牲層,其係介於該第一表面及該黏接層之間, 以及對該犧牲層施予雷射能量,以促進該第一基板與該第二基板分離,其中, 該犧牲層係由一組成物所形成,該組成物係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
較佳地,該方法係於對該犧牲層施予雷射能量之步驟後進一步包含以鹼性水溶液清洗該黏接層,以移除殘留於該黏接層表面上之該犧牲層。
較佳地,該鹼性水溶液係3~5重量%之鹼金屬氫氧化物水溶液或鹼金屬碳酸化物水溶液。
較佳地,該具羧基之二胺之二價殘基係包含以下基團:
、
或
,其中*係指示連接點。
較佳地,該犧牲層之熱膨脹係數係小於50 ppm/℃。
本發明另提供一種形成微電子結構之方法,其包含:於基板之表面上形成一犧牲層;及於該犧牲層上形成一重分佈層,其中該犧牲層係由一組成物所形成,該組成物係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
較佳地,該方法進一步包含於該重分佈層上形成一個或多個額外的重分佈層。
較佳地,該方法係於形成重分佈層後,進一步包含對該犧牲層施予雷射能量,以使該重分佈層與該基板分離。
較佳地,該方法係於對該犧牲層施予雷射能量後,進一步包含以鹼性水溶液清洗該重分佈層,以移除殘留於該重分佈層表面上之該犧牲層。
較佳地,該鹼性水溶液係3~5重量%之鹼金屬氫氧化物水溶液或鹼金屬碳酸化物水溶液。
較佳地,該具羧基之二胺之二價殘基係包含以下基團:
、
或
,其中*係指示連接點。
依據本發明,可獲得一種可以鹼性水溶液輕易移除解黏過程中所產生之殘膠之暫時接合方法及形成微電子結構之方法。
本發明係提供一種暫時接合方法,其包含:提供一疊加物,該疊加物包含:一第一基板,其具有上表面及一下表面;一黏接層,其係與該下表面接觸;一第二基板,其具有一第一表面;及一犧牲層,其係介於該第一表面及該黏接層之間, 以及對該犧牲層施予雷射能量,以促進該第一基板與該第二基板分離,其中, 該犧牲層係由一組成物所形成,該組成物係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
如前述,於本發明中,用以形成犧牲層之組成物(或稱可雷射釋放組成物)係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
該聚醯胺酸較佳係使用縮合聚合,藉由在特定溶劑中混合二酐與二胺單體,以形成聚醯胺酸前驅體溶液來合成。接著,較佳係添加封端劑以消除末端官能基,以便預防隨後可能的老化。該特定溶劑包含但不限於:環己酮、環戊酮、丙二醇單甲醚、N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、γ-丁內酯、3-乙氧基丙酸乙酯、丙二醇甲醚乙酸酯、乳酸乙酯、或前述二種以上之組合。
於一較佳實施態樣中,該聚醯亞胺主要由二酸酐單體與二胺單體聚合而成,且至少一二胺單體係具有羧基官能基。
於一較佳實施態樣中,該聚醯胺醯亞胺主要由二酸酐單體、二胺單體與芳香族二羰基單體聚合而成,且至少一二胺單體係具有羧基官能基,以及該芳香族二羰基單體之莫耳數占該二酸酐單體與該芳香族二羰基單體之總莫耳數的10%~50%。於一較佳實施態樣中,該犧牲層之熱膨脹係數係小於50ppm/℃。
於本發明中,該具羧基之二胺之二價殘基係包含以下基團:
、
或
,其中*係指示連接點。
其他適用於本發明之二胺單體包含但不限於:2-(三氟甲基)-1,4-亞苯基二胺、雙(三氟甲基)聯苯胺(TFDB)、二氨基二苯醚(4,4'-Oxydianiline,ODA)、對亞甲基二苯胺(para-Methylene Dianiline,pMDA)、間亞甲基二苯胺(meta-Methylene Dianiline,mMDA)、雙氨基苯氧基苯 (1,3-bis(3-aminophenoxy)benzene,133APB)、雙氨基苯氧基苯(1,3-bis(4-aminophenoxy)benzene,134APB)、雙氨基苯氧基苯六氟丙烷(2,2'-bis[4(4-aminophenoxy)phenyl]hexafluoropropane,4BDAF)、二氨基苯基六氟丙烷(2,2'-bis(3-aminophenyl)hexafluoropropane,33-6F)、二氨基苯基六氟丙烷(2,2'-bis(4-aminophenyl)hexafluoropropane,44-6F)、雙(4-氨基苯基)碸(bis(4-aminophenyl)sulfone,4DDS)、雙(3-氨基苯基)碸(bis(3-aminophenyl)sulfone,3DDS)、2,2-雙[4-(4-氨基苯氧基)-苯基)]丙烷(2,2-Bis[4-(4-aminophenoxy)-phenyl]propane,6HMDA)、2,2-雙(3-氨基-4-羥基苯基)六氟丙烷(2,2-Bis(3-amino-4-hydroxy-phenyl)-hexafluoropropane,DBOH)、4,4’-雙(3-氨基苯氧基)二苯基碸(4,4'-Bis(3-amino phenoxy)diphenyl sulfone,DBSDA)、9,9-雙(4-氨基苯基)芴(9,9-Bis(4-aminophenyl)fluorene,FDA)、9,9-雙(3-氟-4-氨基苯基)芴(9,9-Bis(3-fluoro-4-aminophenyl)fluorene,FFDA) 或前述兩種以上之組合。
適用於本發明中之二酸酐單體包含但不限於:4,4'-(4,4'-異丙基二烯二苯氧基)雙(鄰苯二甲酸酐) 、4,4'-(六氟異亞丙基)二鄰苯二甲酸酐、3,3’,4,4’-二苯基酮四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、4,4’-氧基二鄰苯二甲酸酐、3,3',4,4'-二苯基碸四羧酸二酐、雙羧苯基二甲基矽烷二酐、雙二羧基苯氧基二苯硫醚二酐、磺醯基二鄰苯二甲酸酐、1,2,3,4-環丁烷四羧酸二酐、環己烷-1,2,4,5-四羧酸二酐、1,1‘-聯(環己烷基)- 3,3’,4,4‘-四羧酸二酐、1,1’-聯(環己烷)-2,3,3’,4’-四羧酸二酐、1,1’-聯(環己烷)-2,2’,3,3’-四羧酸二酐、4,4’-亞甲基雙(環己烷-1,2-二羧酸酐)、4,4’-(丙烷-2,2-二基)雙(環己烷-1,2-二羧酸酐)、4,4’-氧基雙(環己烷-1,2-二羧酸酐)、4,4’-硫雙(環己烷-1,2-二羧酸酐)、4,4’-磺醯基雙(環己烷-1,2-二羧酸酐)、4,4’-(二甲基矽烷二基)雙(環己烷-1,2-二羧酸酐)、4,4’-(四氟丙烷-2,2-二基)雙(環己烷-1,2-二羧酸酐)、八氫戊搭烯-1,3,4,6-四羧酸二酐、雙環[2.2.1]庚烷-2,3,5,6-四羧酸二酐、(8aS)-六氫-3H-4,9-甲呋喃[3,4-g]異戊烯-1,3,5,7(3aH)-四酮、雙環[2.2.2]辛烷-2,3,5,6-四羧酸二酐、雙環[2.2.2]辛-5-烯-2,3,7,8-四羧酸二酐、三環[4.2.2.02,5]癸烷-3,4,7,8-四羧酸二酐、三環[4.2.2.02,5]癸-7-烯-3,4,9,10-四羧酸二酐、或前述兩種以上之組合。
適用於本發明之芳香族二羰基單體包含但不限於:4,4'-聯苯二甲醯氯(4,4'-biphenyldicarbonyl chloride,BPC)、間苯二甲醯氯(isophthaloyl chloride,IPC)、對苯二甲醯氯(terephthaloyl chloride,TPC)或前述兩種以上之組合。
如上所述,較佳使用封端劑以藉由封蓋末端胺且消耗反應溶液中過量的二胺來提高最終產物之穩定性。較佳使用芳族單酐作為封端劑。一種尤佳封端劑為鄰苯二甲酸酐。二酸酐單體、二胺單體及封端劑之莫耳供應比率較佳為約0.7:1:0.3至約0.98:1:0.02,更佳為約0.85:1:0.15至約0.95:1:0.05。
用於分散或溶解該鹼可溶之聚合物之溶劑包含但不限於環己酮、環戊酮、丙二醇單甲醚、N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、γ-丁內酯、3-乙氧基丙酸乙酯、丙二醇甲醚乙酸酯、乳酸乙酯或前述二種以上之混合物。
於本發明中,該組成物所形成之犧牲層係可藉由鹼性水溶液去除。該鹼性水溶液較佳係3~5重量%之鹼金屬氫氧化物水溶液或鹼金屬碳酸化物水溶液。於某些實施例中,該犧牲層之耐熱溫度為350至450℃。
請參閱圖1(a),其示意說明本發明提供一疊加物之步驟。同時併參圖1(b),其示意說明本發明該疊加物之結構。該疊加物100可藉由以下步驟提供:提供一疊加物前驅物50,其包含第一基板10及黏接層20;及透過犧牲層30將該疊加物前驅物50與第二基板40予以接合。如圖1(a)所示,該第一基板10係具有上表面12及與上表面12相對之下表面14,該黏接層20係以其上表面22與該第一基板10之下表面14直接接觸(即二層之間不存在任何中間層),該第二基板40之上表面(第一表面)42則係透過犧牲層30被接合於該黏接層20之下表面24。
於本發明中,第一基板可為元件晶圓,包含但不限於微機電系統(MEMS)、微感測器、積體電路、功率半導體。第一基板的下表面24可具有焊料凸塊、金屬桿(metal post)、金屬柱(metal pillar)等結構。
用以形成黏接層20之組合物並無特別限制,可選自可商購的黏接組合物,只要其能夠形成具有上述黏接特性之層,且同時可藉由加熱去除溶劑即可。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可選自: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、聚乙烯丁醛類或前述之混合物。典型溶劑系統取決於聚合物或低聚合物的選擇。
黏接層20可藉由任何已知的塗布工藝來施作於第一基板10的下表面14,包括但不限於:浸塗、輥塗、狹縫塗布、模頭塗布、網板印刷或噴塗等。另外,可在塗層施加到第一基板或第二基板表面之前,將其形成為自支撐膜(free-standing film),利用轉貼方式將黏接層20施作於第一基板10的下表面14。
黏接層20塗佈於第一基板10的下表面14後,藉由加熱約50℃到150℃持續約60秒到約10分鐘的時間將溶劑去除。再以施加壓力方式將黏接層20接合於位於第二基板40上之犧牲層30,再經過烘烤使黏接層20產生固化,如此即可獲得圖1(b)所示之疊加物100。所得黏接層20的厚度約1µm到約50µm。
於本實施例中,第二基板40為作為載體基板之載體晶圓。該基板40具有第一表面42(上表面)及與之相對之第二表面44(下表面)。第二基板40較佳包括透明晶圓或任何其他的透明(對於雷射能量而言)基板,其能允許雷射能量穿透載體基板。該第二基板40之實例包括但不限於:玻璃、Corning Gorilla玻璃、藍寶石。
如圖1(a)所示,另一疊加物前驅物(第二前驅物)60包含第二基板40及位於其上之犧牲層30。可藉任何已知的塗布方法將用以形成犧牲層之組成物施加到第二基板40,以於其第一表面42上形成犧牲層30。該組成物被施加至第一表面42後,對該組成物進行加熱,使其溫度到約60℃到約150℃,持續約30秒到約20分鐘,以移除溶劑。接著,再經過200-350℃持續約20分鐘到約90分鐘進行熟化。黏接層20再經過熱壓方式貼合於位於第二基板40上之犧牲層30後,再經過固化步驟即可將第一基板10黏貼至第二基板40,亦可形成圖1(b)所示之疊加物100。
視情況,可對該疊加物100進行加工。在經過其他加工程序後,即可藉由雷射分解或燒蝕將全部或部分犧牲層30解黏,以分離第一基板10及第二基板40。合適的雷射波長為約200nm到約400nm,較佳為約300nm到約360nm。分離後,可使用鹼性水溶液去除黏接層20上殘留的犧牲層物質。於本實施例中,如圖1(c)中箭號方向所示,雷射是穿透該第二基板40而被施予,以使犧牲層30暴露於雷射,進而使犧牲層失去黏性,而使第一基板10與第二基板40分離。
本文所述的用以形成犧牲層之組成物亦可用於重分佈層(「RDL」)形成時的雷射釋放犧牲層,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。
因此,本發明另提供一種形成微電子結構之方法。該方法包含:於基板之表面上形成一犧牲層;及於該犧牲層上形成一重分佈層,其中該犧牲層係由一組成物所形成,該組成物係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
請參閱圖2,其係一流程圖,用以示意說明本發明之形成微電子結構之方法。如圖2(a)所示,將用以形成犧牲層之組成物施加於載體基板240之上表面242,以形成上表面242設有可雷射釋放之犧牲層230之載體基板240。可依照上述暫時接合方法所述之任何方法,包括製程條件及所得特性,來形成疊加物250(其包含載體基板240及犧牲層230)。該犧牲層230較佳係直接形成於載體基板240之上表面242上,亦即,彼此之間不具任何中間層,如本實施例所示。疊加物250係具有遠離載體基板240的上表面252。
接著,如圖2(b)所示,按照常規方法沉積種子層220在上表面252上。接著,可再次按照已知方法,將種子層220經光阻劑塗布、圖案化及電鍍等步驟,以形成圖2(c)所示的結構,即種子層220上具有金屬234及光阻劑232。接著,除去光阻劑並蝕刻金屬,以形成圖2(d)。接著,進行塗布、圖案化及固化介電層236,以形成如圖2(e)所示之結構。如此,即可獲致第一RDL 225(由種子層220、金屬234及金屬237組成)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(亦即,圖2(f)中所示的具體實例中的2個RDL)。於此實施例中,金屬234與金屬237為相同金屬。
請參閱圖2(g),已形成期望數量的RDL後,再次按照常規方法將焊球206附接到最上面的(最後形成的)RDL。將裸晶204接合到焊球206,接著施加及研磨常規的環氧樹脂模製層210,以形成扇出晶圓級封裝結構208。最後,再施加雷射到載體基板240,以分解或燒蝕全部或部分可雷射釋放犧牲層230。施加雷射之後,載體基板240將被釋放並與扇出晶圓級封裝結構208分離,而得扇出晶圓級封裝結構208(圖2(h)),並以鹼水溶液去除任何剩餘的犧牲層230。
上述用於形成扇出晶圓級封裝結構的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。
為突顯本案功效,發明人特依下文所載方式完成實施例及比較例。以下實施例及比較例將對本發明做進一步說明,然該些實施例及比較例並非用以限制本發明之範圍,任何熟悉本發明技術領域者,在不違背本發明之精神下所為之改變及修飾,均屬本發明之範圍。
實施例1:用於形成犧牲層之聚醯胺酸
在此實施例中,在250mL三頸圓底燒瓶中,將7.61公克3,5-二胺苯甲酸溶解於113.16公克γ-丁內酯(GBL)中。隨後,11.11公克2,2'-雙-(二羧基苯基)六氟丙烷二酐(6FDA)與6.2公克雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐以固體狀添加至反應混合物中。反應在室溫下在攪拌下進行24小時。
實施例2:用於形成犧牲層之聚醯胺酸
在此實施例中,在250mL三頸圓底燒瓶中,將7.61公克3,5-二胺苯甲酸溶解於113.16公克γ-丁內酯(GBL)中。隨後,11.11公克2,2'-雙-(二羧基苯基)六氟丙烷二酐(6FDA)與7.36 公克 3,3',4,4'-聯苯四羧酸二酐(BPDA)以固體狀添加至反應混合物中。反應在室溫下在攪拌下進行24小時。
實施例3:用於形成犧牲層之聚醯胺酸
在此實施例中,在250mL三頸圓底燒瓶中,將14.31公克6,6'-雙氨基-3,3'-甲叉基二苯甲酸溶解於113.16公克γ-丁內酯(GBL)中。隨後,11.11公克2,2'-雙-(二羧基苯基)六氟丙烷二酐(6FDA)與8.06 公克 3,3',4,4'-二苯甲酮四甲酸二酐(BTDA)以固體狀添加至反應混合物中。反應在室溫下在攪拌下進行24小時。
實施例4:用於形成犧牲層之聚醯亞胺
在此實施例中,在250mL三頸圓底燒瓶中,將14.31公克6,6'-雙氨基-3,3'-甲叉基二苯甲酸溶解於113.16公克γ-丁內酯(GBL)中。隨後,12.41公克雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐以固體狀添加至反應混合物中。加入1.67公克的異喹啉後升溫至180度進行脫水反應,反應4小時。
實施例5:用於形成犧牲層之聚醯胺醯亞胺
在反應容器內加入10 mmole的6,6'-雙氨基-3,3'-甲叉基二苯甲酸,並將之溶於二甲基乙醯胺。於氮氣環境下攪拌,溶劑量相當於總固體重量成分濃度為15 重量%。待完全溶解後,再加入2 mmole的1,2,3,4-環丁烷四羧酸二酐(CBDA)和3mmole的6FDA,攪拌4小時溶解及反應,然後將溶液的溫度維持在15℃,並加入5mmole的對苯二甲醯氯(TPC),再繼續攪拌反應12小時。接著加入15mmole的吡啶和30mmole的乙酸酐,攪拌30分鐘後,再升溫至70℃下攪拌1小時,然後冷卻至常溫。最後以大量的甲醇進行沉澱,並以粉碎機將沉澱的固體進行粉碎,再以真空乾燥方式乾燥成粉。
實施例6:用於形成犧牲層之聚醯胺醯亞胺
在反應容器內加入10 mmole的6,6'-雙氨基-3,3'-甲叉基二苯甲酸,並將之溶於二甲基乙醯胺。於氮氣環境下攪拌,溶劑量相當於總固體重量成分濃度為15 重量%。待完全溶解後,再加入4 mmole的CBDA和5mmole的6FDA,攪拌4小時溶解及反應,然後將溶液的溫度維持在15℃,並加入1mmole的TPC,再繼續攪拌反應12小時。接著加入15mmole的吡啶和30mmole的乙酸酐,攪拌30分鐘後,再升溫至70℃下攪拌1小時,然後冷卻至常溫。最後以大量的甲醇進行沉澱,並以粉碎機將沉澱的固體進行粉碎,再以真空乾燥方式乾燥成粉。
將實施例1至6之鹼可溶之聚合物分散或溶解於二甲基乙醯胺中,以約1 μm的厚度塗佈在700 μm的玻璃上,再放入烘箱中以150℃烘烤2分鐘,令表面乾燥,之後再以300℃烘烤半小時,如此可以得到暫時放置在玻璃表面上的暫時性接合用組成物薄膜(A)。當從玻璃取下後,可獲得本發明的暫時性接合用組成物薄膜(B),厚度約1 μm。
鍍鈦銅測試
實施例1至6製成的薄膜(A),於薄膜(A)上設置Ti/Cu層(Ti/Cu的厚度分別為100 nm/500 nm)。經鍍鈦銅測試,若鍍銅膜面經過溫度230℃下進行2小時的高溫熟化後無裂痕為通過(V),若有裂痕者為失敗(X)。
熱裂解溫度
實施例1至6製成的薄膜(B),藉由熱重分析儀(thermogravimetric analyzer,TGA),在空氣環境中以10℃/min速率從25℃升至700℃,測定薄膜(B)於損失5重量%時的溫度,此為Td5熱裂解溫度。
熱膨脹係數(CTE)
用熱機械分析儀(TA Instrument TMA Q400EM)量測50℃至200 ℃的CTE值與玻璃轉移溫度。在熱分析前,所有暫時性接合用組成物薄膜(B)先在220 ℃熱處理1小時,再以TMA測定玻璃轉移溫度,在薄膜模式下,以10℃/分鐘之加熱速率並以30 mN恆定施加荷重。相同地,以TMA測定溫度50~200℃線性熱膨脹係數,其負載應變為30 mN,加熱速率為10 ℃/min。
密著性
以實施例1至6製成的薄膜(A),密著性的評估方法採用百格密著性測試,測試方法是用百格刀在測試樣本(玻璃材料)表面劃10×10個(100個)1 mm×1 mm小網格,每一條劃線深及底層。之後,用毛刷將測試區域的碎片刷乾淨,再用膠紙牢牢黏住被測試小網格,並用橡皮擦用力擦拭膠帶,以加大膠帶與被測區域的接觸面積及力度。接著,用手抓住膠帶一端,在垂直方向迅速扯下膠紙。評估結果如下方表5所示,其中測試結果為5B即代表具有良好密著性。
解黏測試
實施例1至6製成的薄膜(A),以能量為230 mJ/cm
2、波長為308 nm的雷射光照射進行解黏。若解黏後膜可成功剝離則為通過(V),若無法剝離則為失敗(X)。
耐化性測試
以實施例1至6製成的薄膜(A),將薄膜(A)以下方表3中所列出的不同化學藥劑浸泡10分鐘,再以拉力計進行測量。當測量結果高於300 g/cm時,則代表具有良好的耐化性。
表1
實施例1 | 實施例2 | 實施例3 | 實施例4 | 實施例5 | 實施例6 | |
鍍鈦銅測試 | V | V | V | V | V | V |
Td5 | 440 | 480 | 483 | 420 | 462 | 460 |
CTE | 45 | 39 | 41 | 55 | 10 | 42 |
解黏測試 | V | V | V | V | V | V |
密著性 | 5B | 5B | 5B | 5B | 5B | 5B |
耐化性 | g/cm | g/cm | g/cm | g/cm | g/cm | g/cm |
NMP | 355 | 320 | 370 | 400 | 380 | 340 |
30% HCl | 323 | 348 | 360 | 380 | 400 | 360 |
3%NaOH | 溶解 | 溶解 | 溶解 | 溶解 | 溶解 | 溶解 |
PGMEA | 331 | 329 | 373 | 389 | 373 | 350 |
TMAH 2.38% | 340 | 330 | 362 | 382 | 388 | 360 |
甲醇 | 335 | 340 | 375 | 392 | 390 | 365 |
丙酮 | 326 | 332 | 368 | 397 | 387 | 355 |
自上可知,本發明中之犧牲層係不僅具有良好耐熱性、耐化性及解黏性,亦具有低熱膨脹係數,而且可輕易以鹼性水溶液移除,因此,極適用於暫時接合製程及重分佈層製程。
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即只要是依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。
10:第一基板
12:上表面
14:下表面
20:黏接層
22:上表面
30:犧牲層
40:第二基板
42:上表面(第一表面)
44:下表面
50:疊加前驅物
60:另一疊加前驅物
100:疊加物
204:裸晶
206:焊球
208:扇出晶圓級封裝結構
210:環氧樹脂模製層
220:種子層
225:RDL
230:犧牲層
232:光阻劑
234:金屬
236:介電層
237:金屬
240:載體基板
242:上表面
250:疊加物
252:上表面
圖1係一流程圖,用以示意說明本發明之暫時接合方法。
圖2係一流程圖,用以示意說明本發明之形成微電子結構之方法。
10:第一基板
12:上表面
14:下表面
20:黏接層
22:上表面
30:犧牲層
40:第二基板
42:上表面(第一表面)
44:下表面
50:疊加前驅物
60:另一疊加前驅物
Claims (11)
- 一種暫時接合方法,其包含: 提供一疊加物,該疊加物包含: 一第一基板,其具有上表面及一下表面; 一黏接層,其係與該下表面接觸; 一第二基板,其具有一第一表面;及 一犧牲層,其係介於該第一表面及該黏接層之間, 以及 對該犧牲層施予雷射能量,以促進該第一基板與該第二基板分離, 其中, 該犧牲層係由一組成物所形成,該組成物係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
- 如請求項1所述之方法,其係於對該犧牲層施予雷射能量之步驟後進一步包含以鹼性水溶液清洗該黏接層,以移除殘留於該黏接層表面上之該犧牲層。
- 如請求項2所述之方法,其中該鹼性水溶液係3~5重量%之鹼金屬氫氧化物水溶液或鹼金屬碳酸化物水溶液。
- 如請求項1所述之方法,其中該具羧基之二胺之二價殘基係包含以下基團: 、 或 ,其中*係指示連接點。
- 如請求項1所述之方法,其中該犧牲層之熱膨脹係數係小於50 ppm/℃。
- 一種形成微電子結構之方法,其包含: 於基板之表面上形成一犧牲層;及 於該犧牲層上形成一重分佈層, 其中該犧牲層係由一組成物所形成,該組成物係包含一鹼可溶之聚合物;及用於分散或溶解該鹼可溶之聚合物之溶劑,其中該鹼可溶之聚合物係含有具羧基之二胺之二價殘基,且該鹼可溶之聚合物係包含聚醯胺酸、聚醯亞胺或聚醯胺醯亞胺。
- 如請求項6所述之方法,其進一步包含於該重分佈層上形成一個或多個額外的重分佈層。
- 如請求項6所述之方法,其係於形成重分佈層後,進一步包含對該犧牲層施予雷射能量,以使該重分佈層與該基板分離。
- 如請求項8所述之方法,其係於對該犧牲層施予雷射能量後,進一步包含以鹼性水溶液清洗該重分佈層,以移除殘留於該重分佈層表面上之該犧牲層。
- 如請求項9所述之方法,其中該鹼性水溶液係3~5重量%之鹼金屬氫氧化物水溶液或鹼金屬碳酸化物水溶液。
- 如請求項6所述之方法,其中該具羧基之二胺之二價殘基係包含以下基團: 、 或 ,其中*係指示連接點。
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