TWI827632B - 半導體裝置的製造方法、熱硬化性樹脂組成物及切晶黏晶一體型膜 - Google Patents

半導體裝置的製造方法、熱硬化性樹脂組成物及切晶黏晶一體型膜 Download PDF

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TWI827632B
TWI827632B TW108124517A TW108124517A TWI827632B TW I827632 B TWI827632 B TW I827632B TW 108124517 A TW108124517 A TW 108124517A TW 108124517 A TW108124517 A TW 108124517A TW I827632 B TWI827632 B TW I827632B
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adhesive
thermosetting resin
resin composition
film
semiconductor
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TW108124517A
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TW202017022A (zh
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山本和弘
國土由衣
藤尾俊介
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日商力森諾科股份有限公司
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C09J201/00—Adhesives based on unspecified macromolecular compounds
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
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    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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    • H01L25/04—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers
    • H01L25/065—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices not having separate containers the devices being of a type provided for in group H01L27/00
    • H01L25/0657—Stacked arrangements of devices
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    • H01L25/50—Multistep manufacturing processes of assemblies consisting of devices, each device being of a type provided for in group H01L27/00 or H01L29/00
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
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    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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Abstract

本揭示的一方面所涉及的半導體裝置的製造方法包括：準備切晶黏晶一體型膜的步驟，所述切晶黏晶一體型膜包括接著層、黏著層及基材膜，所述接著層包含120℃下的熔融黏度為3100 Pa·s以上的熱硬化性樹脂組成物；將切晶黏晶一體型膜的接著層側的面與半導體晶圓貼合的步驟；切割半導體晶圓的步驟；藉由使基材膜擴張而獲得帶有接著劑的半導體元件的步驟；自黏著層拾取帶有接著劑的半導體元件的步驟；將該半導體元件經由所述接著劑而與其他半導體元件積層的步驟；以及使所述接著劑熱硬化的步驟。

Description

半導體裝置的製造方法、熱硬化性樹脂組成物及切晶黏晶一體型膜
本揭示是有關於一種半導體裝置的製造方法、熱硬化性樹脂組成物及切晶黏晶一體型膜。
半導體裝置是經過以下的步驟而製造。首先，利用切割用黏著片將半導體晶圓固定，於該狀態下將半導體晶圓單片化為半導體晶片。其後，實施擴張(expand)步驟、拾取(pickup)步驟、黏晶(die bonding)步驟及回流(reflow)步驟等。
作為半導體裝置所要求的重要特性之一，可列舉連接可靠性。為了提升連接可靠性，正在進行考慮到耐熱性、耐濕性及耐回流性等特性的黏晶用膜狀接著劑的開發。例如，專利文獻1中揭示一種含有樹脂及填料的接著片，所述樹脂包含高分子量成分、及以環氧樹脂為主成分的熱硬化性成分。
[現有技術文獻]
[專利文獻]
專利文獻1：日本專利特開2016-190964號公報
本發明者等人正在進行於藉由將半導體元件積層為多段而高容量化的半導體裝置(例如三維反及(NAND)型記憶體)的製造製程中使用的熱硬化性接著劑的開發。三維NAND用晶圓由於包含複雜的電路層及較薄的半導體層(例如15μm~25μm左右)，因此具有將其單片化而得的半導體元件容易產生翹曲的課題。
圖5(a)是示意性表示半導體裝置的製造過程中的結構體的剖面圖。圖5(a)所示的結構體30包括：基板10及積層於基板10上的四個半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4。為了與形成於基板10的表面的電極(未圖示)連接，四個半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4是於在橫向(與積層方向正交的方向)上相互錯開的位置積層(參照圖1)。半導體元件S1藉由接著劑而接著於基板10，於三個半導體元件S2、半導體元件S3、半導體元件S4之間亦介入接著劑。
根據本發明者等人的研究，於半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4分別具有複雜的電路層(上表面側)及較薄的半導體層(下表面側)的情況下，如圖5(b)所示，在第一段的半導體元件S1與第二段的半導體元件S2之間容易產生剝離。關於其原因，本發明者等人推測如下。
．由於複雜的電路層及薄的半導體層，如上所述，半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4具有容易翹 曲的性質(翹曲應力)。
．藉由將多個半導體元件在橫向上錯開位置進行積層，而形成有外伸(overhang)部H。
．已確認於安裝第二段的半導體元件S2的階段不會發生剝離，因此藉由安裝第三段的半導體元件S3及第四段的半導體元件S4，於第二段的半導體元件S2的外伸部H，上方向上的力(在與第一段的半導體元件S1之間剝離的方向上的翹曲應力)增大。
本揭示是鑒於所述課題而成者，提供一種半導體裝置的製造方法，其中半導體裝置是積層有多個半導體元件的態樣的半導體裝置，且不易產生鄰接的半導體元件之間的剝離。另外，本揭示提供一種能夠適用於該製造方法中的熱硬化性樹脂組成物及切晶黏晶一體型膜。
本揭示的一方面提供一種積層有多個半導體元件的態樣的半導體裝置(例如三維NAND型記憶體)的製造方法。該製造方法包括：準備切晶黏晶一體型膜的步驟，所述切晶黏晶一體型膜依序包括接著層、黏著層及基材膜，所述接著層包含120℃下的熔融黏度為3100Pa．s以上的熱硬化性樹脂組成物；將切晶黏晶一體型膜的接著層側的面與半導體晶圓貼合的步驟；切割半導體晶圓的步驟；藉由使基材膜擴張而獲得將半導體晶圓及接著層單片化而成的帶有接著劑的半導體元件的步驟；自黏著層拾取帶有接著劑的半導體元件的步驟；將帶有接著劑的半導體元件，經由 該帶有接著劑的半導體元件的接著劑而與其他半導體元件積層的步驟；以及使接著劑熱硬化的步驟。
作為熱硬化性樹脂組成物，藉由採用120℃下的熔融黏度為3100Pa．s以上者，即便應接著的半導體元件具有較強的翹曲應力，亦可達成能夠耐受所述翹曲應力的界面接著力。藉此，即便積層多個半導體元件，亦可充分抑制鄰接的半導體元件之間的剝離。
如三維NAND用半導體晶圓般，為了將較薄的半導體晶圓單片化而獲得半導體元件，就良率高等觀點而言，於對半導體晶圓進行隱形切割(stealth dicing)或刀片切割(blade dicing)後，較佳為於冷卻條件下(例如-15℃~0℃)使基材膜擴張。
本揭示的一方面提供一種熱硬化性樹脂組成物，其用於半導體裝置的製造製程中，且120℃下的熔融黏度為3100Pa．s以上。該熱硬化性樹脂組成物能夠適用於所述半導體裝置的製造方法中。
熱硬化性樹脂組成物含有：熱硬化性樹脂、分子量為10萬~100萬的高分子量成分(例如丙烯酸樹脂)、及填料，以熱硬化性樹脂組成物的總質量為基準，高分子量成分的含量較佳為15質量%~50質量%，填料的含量較佳為25質量%~45質量%。藉由將高分子量成分及填料的含量設為所述範圍，於對半導體晶圓進行隱形切割或刀片切割後，藉由於冷卻條件下進行擴張及拾取，可更有效率且穩定地製作帶有接著劑的半導體元件。
本揭示提供一種切晶黏晶一體型膜，包括：黏著層；以及包含所述熱硬化性樹脂組成物的接著層。該一體型膜能夠適用於所述半導體裝置的製造方法中。就成本及接著強度的觀點而言，接著層的厚度例如為3μm~40μm。
根據本揭示，可提供一種半導體裝置的製造方法，其中半導體裝置是積層有多個半導體元件的態樣的半導體裝置，且不易產生鄰接的半導體元件之間的剝離。另外，根據本揭示，可提供一種能夠適用於所述製造方法中的熱硬化性樹脂組成物及切晶黏晶一體型膜。
1:基材膜
2:黏著層
3:膜狀接著劑的硬化物
3A:接著層
3P:膜狀接著劑
8:切晶黏晶一體型膜
10:基板
20:帶有接著劑的半導體元件
30:結構體
42:頂針
44:抽吸夾頭
50:密封層
100:半導體裝置
H:外伸部
R:改質區域
S1、S2、S3、S4:半導體元件
W:半導體晶圓
W1、W2、W3、W4:導線
圖1是示意性表示半導體裝置的一例的剖面圖。
圖2是示意性表示包含膜狀接著劑及半導體元件的帶有接著劑的半導體元件的一例的剖面圖。
圖3的(a)~圖3的(f)是示意性表示製造帶有接著劑的半導體元件的過程的剖面圖。
圖4是示意性表示製造圖1所示的半導體裝置的過程的剖面圖。
圖5(a)是示意性表示製造圖1所示的半導體裝置的過程的剖面圖，圖5(b)是表示在第一段的半導體元件與第二段的半導體元件之間產生了剝離的結構體的剖面圖。
圖6是示意性表示製造圖1所示的半導體裝置的過程的剖面圖。
圖7是示意性表示半導體裝置的另一例的剖面圖。
以下，參照圖式來對本揭示的實施形態進行詳細說明。於以下的說明中，對相同或相當部分標註相同符號，並省略重覆的說明。另外，上下左右等位置關係只要無特別說明，則是指基於圖式所示的位置關係者。進而，圖式的尺寸比率並不限於圖示的比率。再者，本說明書中「(甲基)丙烯酸」的記載是指「丙烯酸」及與其相對應的「甲基丙烯酸」。
<半導體裝置>
圖1是示意性表示本實施形態的半導體裝置的剖面圖。該圖所示的半導體裝置100包括：基板10；積層於基板10的表面上的四個半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4；將基板10的表面上的電極(未圖示)與四個半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4電性連接的導線W1、導線W2、導線W3、導線W4；以及將該些密封的密封層50。
基板10例如為有機基板，亦可為引線框架等金屬基板。關於基板10，就抑制半導體裝置100的翹曲的觀點而言，基板10的厚度例如為90μm~180μm，亦可為90μm~140μm。
四個半導體元件S1、半導體元件S2、半導體元件S3、 半導體元件S4經由膜狀接著劑3P(參照圖2)的硬化物3而積層。俯視時半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4的形狀例如為矩形(正方形或長方形)。半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4的一邊的長度例如為5mm以下，亦可為2mm~4mm或1mm~4mm。半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4的厚度例如為10μm~170μm，亦可為10μm~30μm。再者，四個半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4的一邊的長度可相同，亦可相互不同，關於厚度亦同樣。
<帶有接著劑的半導體元件>
圖2是示意性表示帶有接著劑的半導體元件的一例的剖面圖。圖2所示的帶有接著劑的半導體元件20包含膜狀接著劑3P及半導體元件S1。如圖2所示，膜狀接著劑3P與半導體元件S1實質上為相同尺寸。關於膜狀接著劑3P與半導體元件S2、半導體元件S3、半導體元件S4，亦同樣如此。如以下所說明般，帶有接著劑的半導體元件20是經過切割(dicing)步驟及拾取步驟而製作。
參照圖3的(a)~圖3的(f)，對圖2所示的帶有接著劑的半導體元件20(膜狀接著劑3P與半導體元件S1的積層體)的製作方法的一例進行說明。首先，準備切晶黏晶一體型膜8(以下視情況稱為「膜8」)，將其配置於規定的裝置(未圖示)。膜8依序包括基材膜1、黏著層2及接著層3A。基材膜1例如為聚對 苯二甲酸乙二酯膜(polyethylene terephthalate film，PET膜)。半導體晶圓W例如為厚度10μm~100μm的薄型半導體晶圓。半導體晶圓W可為單晶矽，亦可為多晶矽、各種陶瓷、砷化鎵等化合物半導體。
如後述般，接著層3A包含熱硬化性樹脂組成物。就成本及硬化物的接著強度的觀點而言，接著層3A的厚度例如為3μm~40μm，亦可為3μm~30μm或3μm~25μm。
如圖3的(a)及圖3的(b)所示，以接著層3A與半導體晶圓W的其中一個面接觸的方式貼附膜8。該步驟較佳為於50℃~100℃、更佳為60℃~80℃的溫度條件下實施。若溫度為50℃以上，則可獲得半導體晶圓W與接著層3A的良好的密接性，若為100℃以下，則可於該步驟中抑制接著層3A過度流動。
藉由沿著半導體晶圓W的切斷預定線照射雷射光，如圖3的(c)所示，於半導體晶圓W形成改質區域R(隱形切割)。亦可代替隱形切割，藉由刀片切割而於半導體晶圓形成切口。再者，亦可於對半導體晶圓W進行雷射光照射或刀片切割之前，藉由對半導體晶圓W進行磨削而薄膜化。
如圖3的(d)所示，藉由於常溫或冷卻條件下使基材膜1擴張而於改質區域R使半導體晶圓W分割。藉此，將半導體晶圓W單片化為多個半導體元件S1，並且將接著層3A單片化為膜狀接著劑3P。於黏著層2例如為紫外線(ultraviolet，UV)硬化型的情況下，如圖3的(e)所示，於藉由擴張而使帶有接著劑 的半導體元件20相互分離的狀態下，藉由對黏著層2照射紫外線而使黏著層2硬化，從而使黏著層2與膜狀接著劑3P之間的黏著力降低。於紫外線照射後，藉由利用頂針42將其頂起而使帶有接著劑的半導體元件20自黏著層2剝離，並且利用抽吸夾頭44抽吸並拾取帶有接著劑的半導體元件20(參照圖3的(f))。以該方式獲得圖2所示的帶有接著劑的半導體元件20。
就適當地分割接著層3A而獲得規定形狀及尺寸的膜狀接著劑3P的觀點而言，基材膜1的擴張較佳為於冷卻條件下進行。該溫度條件例如可為-15℃~0℃。
<半導體裝置的製造方法>
參照圖4~圖6，對半導體裝置100的製造方法進行說明。首先，如圖4所示，於基板10的表面上壓接第一段的半導體元件S1。即，經由帶有接著劑的半導體元件20的膜狀接著劑3P而將半導體元件S1壓接於基板10的規定位置。該壓接處理例如較佳為於80℃~180℃、0.01MPa~0.50MPa的條件下，實施0.5秒~3.0秒。其次，藉由加熱而使膜狀接著劑3P硬化。該硬化處理例如較佳為於60℃~175℃、0.01MPa~1.0MPa的條件下歷時5分鐘以上來實施。藉此，膜狀接著劑3P硬化而成為硬化物3。就減少空隙的觀點而言，膜狀接著劑3P的硬化處理亦可於加壓環境下實施。
與半導體元件S1相對於基板10的安裝同樣地，於半導體元件S1的表面上安裝第二段的半導體元件S2。進而，藉由安裝第三段的半導體元件S3及第四段的半導體元件S4，而製作圖5 (a)所示的結構體30。於利用導線W1、導線W2、導線W3、導線W4將半導體元件S1、半導體元件S2、半導體元件S3、半導體元件S4與基板10電性連接後(參照圖6)，藉由密封層50而將半導體元件及導線密封，藉此製成圖1所示的半導體裝置100。
<熱硬化性樹脂組成物>
對構成膜狀接著劑3P的熱硬化性樹脂組成物進行說明。再者，膜狀接著劑3P為將接著層3A單片化而得者，兩者包含相同的熱硬化性樹脂組成物。該熱硬化性樹脂組成物例如為經過半硬化(B階段)狀態，且藉由其後的硬化處理而可呈完全硬化物(C階段)狀態者。
熱硬化性樹脂組成物的120℃下的熔融黏度為3100Pa．s以上。藉由使用熱硬化性樹脂組成物，即便應接著的半導體元件具有較強的翹曲應力，亦可達成能夠耐受所述翹曲應力的界面接著力。藉此，即便積層多個半導體元件，亦可充分抑制鄰接的半導體元件之間的剝離。熱硬化性樹脂組成物的120℃下的熔融黏度可為3100Pa．s~40000Pa．s，亦可為5000Pa．s~35000Pa．s。該熔融黏度的下限值可為13000Pa．s，亦可為14000Pa．s。再者，熔融黏度是指下述情況下的測定值：使用先進流變擴展系統(Advanced Rheometric Expansion System，ARES)(TA儀器(TA Instruments)公司製造)，一邊對成形為膜狀的熱硬化性樹脂組成物賦予5%的應變，一邊以5℃/分鐘的升溫速度升溫同時進行測定。
熱硬化性樹脂組成物(硬化處理前)的例如35℃下的儲 存彈性係數為70MPa以上。藉由使用該熱硬化性樹脂組成物，即便應接著的半導體元件具有較強的翹曲應力，亦可達成能夠耐受所述翹曲應力的凝聚力。藉此，即便積層多個半導體元件，亦可充分抑制鄰接的半導體元件之間的剝離。熱硬化性樹脂組成物的35℃下的儲存彈性係數可為70MPa~1000MPa，亦可為80MPa~900MPa。再者，儲存彈性係數是指藉由以下的裝置及條件下的測定而獲得的值。
．動態黏彈性測定裝置：里歐傑爾(Rheogel)E-4000(UBM股份有限公司製造)
．測定對象：成形為膜狀的熱硬化性樹脂組成物
．升溫速度：3℃/分鐘
．頻率：10Hz
熱硬化性樹脂組成物較佳為包含以下成分。
(a)熱硬化性樹脂(以下有時簡稱為「(a)成分」)
(b)高分子量成分(以下有時簡稱為「(b)成分」)
(c)填料(以下有時簡稱為「(c)成分」)
本實施形態中，於(a)熱硬化性樹脂包含環氧樹脂(以下有時簡稱為「(a1)成分」)的情況下，(a)熱硬化性樹脂較佳為包含可作為環氧樹脂的硬化劑的酚樹脂(以下有時簡稱為「(a2)成分」)。再者，於(b)高分子量成分具有與酚樹脂進行熱硬化的官能基(縮水甘油基等)的情況下，作為(a)熱硬化性樹脂，亦可不另外使用環氧樹脂。
熱硬化性樹脂組成物可更包含以下成分。
(d)偶合劑(以下有時簡稱為「(d)成分」)
(e)硬化促進劑(以下有時簡稱為「(e)成分」)
以熱硬化性樹脂組成物的總質量為基準，(a)成分的含量例如為30質量%以下，亦可為5質量%~30質量%。以熱硬化性樹脂組成物的總質量為基準，(b)成分的含量例如為15質量%~66質量%，亦可為15質量%~50質量%。以熱硬化性樹脂組成物的總質量為基準，(c)成分的含量例如為25質量%~50質量%，亦可為25質量%~45質量%。藉由將(b)成分及(c)成分的含量設為所述範圍，於對半導體晶圓進行隱形切割或刀片切割後，藉由於冷卻條件下進行擴張及拾取，可更有效率且穩定地製作帶有接著劑的半導體元件。
具體而言，藉由(b)成分的含量為66質量%以下，當於冷卻條件下進行了擴張時，有可獲得優異的分割性的傾向(參照圖3的(d))。另外，藉由(b)成分的含量為15質量%以上且(c)成分的含量為50質量%以下，冷卻條件下的整體強度(bulk intensity)足夠高，容易藉由擴張而分割為規定的形狀及尺寸。再者，為了使熱硬化性樹脂組成物的120℃下的熔融黏度為所述範圍內，只要適當調整(a)熱硬化性樹脂、(b)高分子量成分及(c)填料的量即可。
就連接可靠性的觀點而言，熱硬化性樹脂組成物的硬化物(C階段)的150℃下的儲存彈性係數較佳為10MPa以上，更 佳為25MPa以上，亦可為50MPa以上或100MPa以上。再者，儲存彈性係數的上限值例如為600MPa，亦可為500MPa。熱硬化性樹脂組成物的硬化物的150℃下的儲存彈性係數可將使熱硬化性樹脂組成物於175℃的溫度條件下硬化而成者作為試樣，並使用動態黏彈性裝置進行測定。
以下，對熱硬化性樹脂組成物所含的各成分進行說明。
．(a)熱硬化性樹脂
(a1)成分只要為分子內具有環氧基者則可並無特別限制地使用。作為(a1)成分，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、含二環戊二烯骨架的環氧樹脂、二苯乙烯型環氧樹脂、含三嗪骨架的環氧樹脂、含芴骨架的環氧樹脂、三苯酚甲烷型環氧樹脂、聯苯型環氧樹脂、伸二甲苯基型環氧樹脂、聯苯芳烷基型環氧樹脂、萘型環氧樹脂、多官能苯酚類、蒽等多環芳香族類的二縮水甘油醚化合物等。該些可單獨使用一種或將兩種以上組合使用。該些中，就耐熱性的觀點而言，(a1)成分可為甲酚酚醛清漆型環氧樹脂、雙酚F型環氧樹脂、或雙酚A型環氧樹脂。
(a1)成分的環氧當量可為90g/eq~300g/eq、110g/eq~290g/eq、或130g/eq~280g/eq。若(a1)成分的環氧當量為此種範圍，則有可維持膜狀接著劑的整體強度並且確保流動性的傾 向。
相對於(a)成分、(b)成分及(c)成分的總質量100質量份而言，(a1)成分的含量可為50質量份以下、5質量份~50質量份、10質量份~40質量份、或20質量份~30質量份。若(a1)成分的含量為5質量份以上，則有膜狀接著劑的埋入性更良好的傾向。若(a1)成分的含量為50質量份以下，則有可進一步抑制滲出的發生的傾向。
(a2)成分只要為分子內具有酚性羥基者則可並無特別限制地使用。作為(a2)成分，例如可列舉：使苯酚、甲酚、間苯二酚(resorcin)、鄰苯二酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類與甲醛等具有醛基的化合物於酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由烯丙基化雙酚A、烯丙基化雙酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等酚類及/或萘酚類與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等。該些可單獨使用一種或將兩種以上組合使用。該些中，就吸濕性及耐熱性的觀點而言，(a2)成分可為苯酚芳烷基樹脂、萘酚芳烷基樹脂、或酚醛清漆型酚樹脂。
(a2)成分的羥基當量可為80g/eq~250g/eq、90g/eq~200g/eq、或100g/eq~180g/eq。若(a2)成分的羥基當量為此種範圍，則有可保持膜狀接著劑的流動性並且更高地維持接著力的傾向。
(a2)成分的軟化點可為50℃~140℃、55℃~120℃、或60℃~100℃。
相對於(a)成分、(b)成分及(c)成分的總質量100質量份而言，(a2)成分的含量可為5質量份~50質量份、10質量份~40質量份、或20質量份~30質量份。若(a2)成分的含量為5質量份以上，則有可獲得更良好的硬化性的傾向。若(a2)成分的含量為50質量份以下，則有膜狀接著劑的埋入性更良好的傾向。
就硬化性的觀點而言，(a1)成分的環氧當量與(a2)成分的羥基當量的比((a1)成分的環氧當量/(a2)成分的羥基當量)可為0.30/0.70~0.70/0.30、0.35/0.65~0.65/0.35、0.40/0.60~0.60/0.40、或0.45/0.55~0.55/0.45。若該當量比為0.30/0.70以上，則有可獲得更充分的硬化性的傾向。若該當量比為0.70/0.30以下，則可防止黏度變得過高，可獲得更充分的流動性。
．(b)高分子量成分
(b)成分較佳為玻璃轉移溫度(Tg)為50℃以下者。作為(b)成分，例如可列舉：丙烯酸樹脂、聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、矽酮樹脂、丁二烯樹脂、丙烯腈樹脂及該些的改質體等。
就流動性的觀點而言，(b)成分可包含丙烯酸樹脂。此處，所謂丙烯酸樹脂，是指包含源自(甲基)丙烯酸酯的結構單元的聚合物。丙烯酸樹脂較佳為包含源自具有環氧基、醇性或酚性羥 基、羧基等交聯性官能基的(甲基)丙烯酸酯的結構單元作為結構單元的聚合物。另外，丙烯酸樹脂亦可為(甲基)丙烯酸酯與丙烯腈的共聚物等丙烯酸橡膠。
丙烯酸樹脂的玻璃轉移溫度(Tg)可為-50℃~50℃或-30℃~30℃。若丙烯酸樹脂的Tg為-50℃以上，則有可防止接著劑組成物的柔軟性變得過高的傾向。藉此，於晶圓切割時容易將膜狀接著劑切斷，能夠防止毛邊(burr)的產生。若丙烯酸樹脂的Tg為50℃以下，則有可抑制接著劑組成物的柔軟性下降的傾向。藉此，當將膜狀接著劑貼附於晶圓時，有容易將空隙充分埋入的傾向。另外，能夠防止由晶圓的密接性的下降所導致的切割時的碎化(chipping)。此處，玻璃轉移溫度(Tg)是使用示差掃描熱量計(Differential Scanning Calorimeter，DSC)(例如理學股份有限公司製造的「Thermo Plus 2」)所測定出的值。
丙烯酸樹脂的重量平均分子量(Mw)例如為10萬~300萬，且可為10萬~100萬、10萬~80萬、或30萬~200萬。若丙烯酸樹脂的Mw為此種範圍，則可適當地控制膜形成性、膜狀時的強度、可撓性、黏性等，並且回流性優異，可提升埋入性。此處，Mw是指藉由凝膠滲透層析法(gel permeation chromatography，GPC)進行測定，並使用基於標準聚苯乙烯的校準曲線進行換算而得的值。
作為丙烯酸樹脂的市售品，例如可列舉：SG-70L、SG-708-6、WS-023 EK30、SG-P3、SG-280 EK23、HTR-860P-3CSP、 HTR-860P-3CSP-3DB(均為長瀨化成(Nagase ChemteX)股份有限公司製造)。
相對於(a)成分、(b)成分及(c)成分的總質量100質量份而言，(b)成分的含量可為5質量份~70質量份、10質量份~50質量份、或15質量份~30質量份。若(b)成分的含量為5質量份以上，則可使成形時的流動性的控制及高溫下的操作性更進一步良好。若(b)成分的含量為70質量份以下，則可使埋入性更進一步良好。
．(c)填料
作為(c)成分，例如可列舉：氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶鬚、氮化硼、二氧化矽等無機填料。該些可單獨使用一種或將兩種以上組合使用。該些中，就與樹脂的相容性的觀點而言，(c)成分可為二氧化矽。
就提升接著性的觀點而言，(c)成分的平均粒徑可為0.005μm~1μm或0.05μm~0.5μm。此處，平均粒徑是指藉由根據布厄特(Brunauer-Emmett-Teller，BET)比表面積進行換算而求出的值。
相對於(a)成分、(b)成分及(c)成分的總質量100質量份而言，(c)成分的含量可為5質量份~50質量份、15質量份~45質量份、或25質量份~40質量份。若(c)成分的含量為5質量份以上，則有膜狀接著劑的流動性進一步提升的傾向。若(c) 成分的含量為50質量份以下，則有膜狀接著劑的切割性更良好的傾向。
．(d)偶合劑
(d)成分可為矽烷偶合劑。作為矽烷偶合劑，例如可列舉：γ-脲基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、3-苯基胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷等。該些可單獨使用一種或將兩種以上組合使用。
相對於(a)成分、(b)成分及(c)成分的總質量100質量份而言，(d)成分的含量可為0.01質量份~5質量份。
．(e)硬化促進劑
(e)成分並無特別限定，可使用通常所使用者。作為(e)成分，例如可列舉：咪唑類及其衍生物、有機磷系化合物、二級胺類、三級胺類、四級銨鹽等。該些可單獨使用一種或將兩種以上組合使用。該些中，就反應性的觀點而言，(e)成分可為咪唑類及其衍生物。
作為咪唑類，例如可列舉：2-甲基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑等。該些可單獨使用一種或將兩種以上組合使用。
相對於(a)成分、(b)成分及(c)成分的總質量100質量份而言，(e)成分的含量可為0.01質量份~1質量份。
<切晶黏晶一體型膜及其製造方法>
對圖3的(a)所示的切晶黏晶一體型膜8及其製造方法進行 說明。膜8的製造方法包括：將含有溶劑的接著劑組成物的清漆塗佈於接著層用的基材膜(未圖示)上的步驟；以及藉由於50℃~150℃下對所塗佈的清漆進行加熱乾燥而形成接著層3A的步驟。
接著劑組成物的清漆例如可藉由將(a)成分~(c)成分、視需要的(d)成分及(e)成分於溶劑中進行混合或混煉而製備。混合或混煉可使用通常的攪拌機、擂潰機、三輥磨機(three-rod roll mill)、球磨機(ball mill)等分散機，將該些適當組合而進行。
用於製作清漆的溶劑只要為可將所述各成分均勻地溶解、混煉或分散者則可無限制地使用現有公知者。作為此種溶劑，例如可列舉：丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮系溶媒；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、甲苯、二甲苯等。就乾燥速度快、且價格低的方面而言，較佳為使用甲基乙基酮、環己酮等。
作為接著層用的基材膜，並無特別限制，例如可列舉：聚酯膜、聚丙烯膜(OPP膜等)、聚對苯二甲酸乙二酯膜、聚醯亞胺膜、聚醚醯亞胺膜、聚醚萘二甲酸酯膜、甲基戊烯膜等。
作為將清漆塗佈於基材膜的方法，可使用公知的方法，例如可列舉：刮塗法、輥塗法、噴塗法、凹版塗佈法、棒塗法、簾塗法等。加熱乾燥的條件只要為所使用的溶劑充分揮發的條件則無特別限制，例如可於50℃~150℃下加熱1分鐘~30分鐘來 進行。加熱乾燥可以50℃~150℃的範圍內的溫度階段性地升溫來進行。藉由加熱乾燥而使清漆中所含的溶劑揮發，藉此可獲得基材膜與接著層3A的積層膜。
藉由將以所述方式獲得的積層膜與切割膜(基材膜1與黏著層2的積層體)貼合，可獲得膜8。作為基材膜1，例如可列舉：聚四氟乙烯膜、聚對苯二甲酸乙二酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚醯亞胺膜等塑膠膜等。另外，基材膜1視需要可進行底塗塗佈、UV處理、電暈放電處理、研磨處理、蝕刻處理等表面處理。黏著層2可為UV硬化型，亦可為感壓型。膜8可為更包括覆蓋黏著層2的保護膜(未圖示)者。
以上，對本揭示的實施形態進行了詳細說明，但本發明並不限定於所述實施形態。例如，於所述實施形態中，例示出積層四個半導體元件的態樣的封裝體，但所積層的半導體元件的個數並不限定於此。另外，於所述實施形態中，例示出在與半導體元件的積層方向正交的方向上錯開位置而積層多個半導體元件的態樣，但亦可如圖7所示，不錯開位置地積層半導體元件。
[實施例]
以下，列舉實施例對本揭示進行更具體的說明。但本發明並不限定於以下實施例。
(實施例1~實施例12及比較例1~比較例5)
以如下方式製備包含表1~表4所示的成分的清漆(共計17種)。即，於包含作為熱硬化性樹脂的環氧樹脂及酚樹脂、以及填 料的組成物中添加環己酮，進行攪拌。於其中添加作為高分子量成分的丙烯酸橡膠並進行攪拌後，進而添加偶合劑及硬化促進劑來進行攪拌，直至各成分充分變均勻，藉此獲得清漆。
表1~表4中所記載的成分如下所述。
(環氧樹脂)
．YDCN-700-10：甲酚酚醛清漆型環氧樹脂，新日鐵住金化學股份有限公司製造，環氧當量為210，軟化點為75℃~85℃
．EXA-830CRP(商品名)：雙酚F型環氧樹脂，迪愛生(DIC)股份有限公司製造，環氧當量為162，常溫下為液體
．YDF-8170C：雙酚F型環氧樹脂，新日鐵住金化學股份有限公司製造，環氧當量為159，常溫下為液體
(酚樹脂)
．米萊斯(Mirex)XLC-LL(「Mirex」為註冊商標)：三井化學股份有限公司製造，羥基當量為175，軟化點為77℃
．菲諾萊特(Phenolite)LF-4871(「Phenolite」為註冊商標)：DIC股份有限公司製造，羥基當量為118，軟化點為130℃
(高分子量成分)
．HTR-860P：長瀨化成股份有限公司製造，丙烯酸橡膠，重量平均分子量為80萬，Tg為-7℃
(填料)
．SC-2050-HLG：雅都瑪(Admatechs)股份有限公司製造，二氧化矽填料分散液，平均粒徑為0.50μm，最大粒徑為1.0μm 以下
．艾羅西爾(Aerosil)R972(「Aerosil」為註冊商標)：日本艾羅西爾(Aerosil)股份有限公司製造，二氧化矽粒子，平均粒徑為0.016μm，最大粒徑為1.0μm以下
(偶合劑)
．A-189：γ-巰基丙基三甲氧基矽烷，日本邁圖高新材料(Momentive Performance Materials Japan)有限責任公司製造
．A-1160：γ-脲基丙基三乙氧基矽烷，日本邁圖高新材料有限責任公司製造
(硬化促進劑)
．固唑(Curezol)2PZ-CN(「Curezol」為註冊商標)：1-氰基乙基-2-苯基咪唑，四國化成工業股份有限公司製造
利用500目(mesh)的過濾器過濾清漆，並進行真空脫泡。將真空脫泡後的清漆塗佈於已實施脫模處理的聚對苯二甲酸乙二酯(PET)膜(厚度38μm)上。以90℃下5分鐘、繼而140℃下5分鐘的兩階段對所塗佈的清漆進行加熱乾燥。如此而獲得於作為基材膜的PET膜上包括處於B階段狀態的膜狀接著劑(厚度7μm)的接著膜。
(膜狀接著劑的熔融黏度的測定)
膜狀接著劑的120℃下的熔融黏度是藉由以下方法進行測定。即，藉由將厚度為7μm的膜狀接著劑積層多層而使厚度為約300μm，並將其衝壓為10mm×10mm的尺寸，藉此獲得測定用的 試樣。於動態黏彈性裝置ARES(TA儀器公司製造)上安置直徑為8mm的圓形鋁板夾具，進而在此處安置所述試樣。其後，一邊以35℃賦予5%的應變，一邊以5℃/分鐘的升溫速度升溫至130℃來進行測定，並記錄120℃時的熔融黏度的值。將結果示於表1~表4中。
(膜狀接著劑的儲存彈性係數的測定)
使用UBM股份有限公司製造的動態黏彈性測定裝置(Rheogel E-4000)測定膜狀接著劑的35℃下的儲存彈性係數。即，藉由將厚度為7μm的膜狀接著劑積層多層而使厚度為約170μm，並將其成為寬度4mm×長度33mm的尺寸，藉此獲得測定用的試樣。將試樣安置於動態黏彈性測定裝置(製品名：Rheogel E-4000，UMB股份有限公司製造)並施加拉伸負荷，以頻率10Hz、升溫速度3℃/分鐘進行測定，測定35℃下的儲存彈性係數。將結果示於表1~表4中。
[膜狀接著劑的分割性評價]
藉由將實施例及比較例的各膜狀接著劑(厚度120μm)與切割用黏著膜(麥克賽爾(Maxell)股份有限公司製造)貼合而製作切晶黏晶一體型膜。
如下所述，於藉由對半導體晶圓照射雷射而形成改質區域後，於低溫條件下實施擴張步驟，藉此評價膜狀接著劑的分割性。即，準備半導體晶圓(矽晶圓，厚度為50μm，外徑為12吋)。為了使膜狀接著劑密接於半導體晶圓的其中一個面，而對半導體 晶圓貼合切晶黏晶一體型膜。使用雷射切割裝置(東京精密股份有限公司製造，瑪霍切割機(MAHOHDICING MACHINE))，對包含半導體晶圓的積層體(半導體晶圓/膜狀接著劑/黏著劑層/基材層)進行隱形切割。條件如下所述。
．雷射光源：半導體雷射激發Nd(釹)(釔鋁石榴石(yttrium aluminum garnet，YAG)雷射)
波長：1064nm
雷射光點剖面積：3.14×10-8cm2
振盪形態：Q開關脈衝
重覆頻率：100kHz
脈衝寬度：30ns
輸出：20μJ/脈衝
雷射光品質：橫向電磁波(transverse electromagnetic wave，TEM)00
偏光特性：直線偏光
．聚光用透鏡倍率：50倍
．數值孔徑(numerical aperture，NA)：0.55
．對雷射光波長的透射率：60%
．載置半導體晶圓的台的移動速度：100mm/秒
將包含改質區域形成後的半導體晶圓的積層體(半導體晶圓/接著劑層/黏著劑層/基材層)固定於擴張裝置。繼而，藉由於以下條件下使切割膜(黏著劑層/基材層)擴張，而將膜狀接著 劑及半導體晶圓分割。藉此，獲得帶有接著劑的半導體元件。
裝置：迪思科(Disco)(股)製造的DDS2300(全自動晶粒分離機(Fully Automatic Die Separator))
冷擴張條件：溫度：-15℃、高度(Height)：9mm、冷卻時間：60秒
速度：300mm/秒、待機時間(Waiting time)：0秒
對於擴張步驟後的黏著劑層，自基材層側，以照度70mW/cm2歷時3秒照射紫外線。使用瑞薩東日本半導體(Renesas Eastern Japan Semiconductor)公司製造的可撓性黏晶機(flexible die bonder)DB-730(商品名)，對帶有接著劑的半導體元件的拾取性進行評價。拾取用夾頭使用微型機械(Micromechanics)公司製造的橡膠頭(RUBBER TIP)13-087E-33(商品名，尺寸：5mm×5mm)。上頂銷使用微型機械公司製造的推針(EJECTOR NEEDLE)SEN2-83-05(商品名，直徑：0.7mm，前端形狀：直徑350μm的半圓)。上頂銷以銷中心間隔4.2mm配置有5根。拾取的條件如下所述。
．銷的頂起速度：10mm/秒
．頂起高度：200μm
於隱形切割步驟後目視觀察有無未分割的帶有接著劑的半導體元件，按照以下基準進行評價。將結果示於表1~表4中。
A：無未分割的帶有接著劑的半導體元件。
B：未分割的帶有接著劑的半導體元件為一個以上。
[四段積層後有無剝離]
使用將膜狀接著劑適當地分割的試樣(帶有接著劑的半導體元件)，對於實施例或比較例，製作與圖5(a)所示的結構體相同構成的結構體。於積層第四段的半導體元件後，目視觀察第一段與第二段之間是否產生了剝離，按照以下基準進行評價。將結果示於表1~表4中。
A：所有試樣中未產生剝離。
B：產生了剝離的試樣為一個以上。
[耐回流性的評價]
於為了評價有無剝離而製作的試料中，使用未產生剝離的試料，藉由以下方法進行耐回流性的評價。即，利用模製用密封材(日立化成(股)製造，商品名「CEL-9750ZHF10」)將積層為四段的半導體元件密封，藉此獲得評價用的封裝體。再者，樹脂密封的條件設為175℃/6.7MPa/90秒，硬化的條件設為175℃、5小時。
準備20個所述封裝體，將該些暴露於由電子設備工程聯合委員會(Joint Electron Device Engineering Council，JEDEC)所規定的環境下(等級3、30℃、60%RH、192小時)來進行吸濕。繼而，使吸濕後的封裝體於紅外(infrared，IR)回流爐(260℃、最高溫度265℃)中經過三次。按照以下基準進行評價。將結果示於表1~表4中。
A：20個封裝體中未有一個觀察到封裝體的破損、厚度的變化、膜狀接著劑與半導體元件的界面處的剝離等。
B：20個封裝體中至少有一個觀察到封裝體的破損、厚度的變化、膜狀接著劑與半導體元件的界面處的剝離等。
Figure 108124517-A0305-02-0029-1
Figure 108124517-A0305-02-0029-2
Figure 108124517-A0305-02-0030-3
Figure 108124517-A0305-02-0030-4
Figure 108124517-A0305-02-0031-5
Figure 108124517-A0305-02-0031-6
Figure 108124517-A0305-02-0032-7
[產業上之可利用性]
根據本揭示，可提供一種半導體裝置的製造方法，其中半導體裝置是積層有多個半導體元件的態樣的半導體裝置，且不易產生鄰接的半導體元件之間的剝離。另外，根據本揭示，可提供一種能夠適用於所述製造方法中的熱硬化性樹脂組成物及切晶黏晶一體型膜。
3:膜狀接著劑的硬化物
10:基板
50:密封層
100:半導體裝置
S1、S2、S3、S4:半導體元件
W1、W2、W3、W4:導線

Claims (13)

  1. 一種半導體裝置的製造方法，包括：準備切晶黏晶一體型膜的步驟，所述切晶黏晶一體型膜依序包括接著層、黏著層及基材膜，所述接著層包含120℃下的熔融黏度為13000Pa．s以上的熱硬化性樹脂組成物；將所述切晶黏晶一體型膜的所述接著層側的面與半導體晶圓貼合的步驟；切割所述半導體晶圓的步驟；藉由使所述基材膜擴張而獲得將所述半導體晶圓及所述接著層單片化而成的帶有接著劑的半導體元件的步驟；自所述黏著層拾取所述帶有接著劑的半導體元件的步驟；將所述帶有接著劑的半導體元件，經由所述帶有接著劑的半導體元件的接著劑而與其他半導體元件積層的步驟；以及使所述接著劑熱硬化的步驟。
  2. 如申請專利範圍第1項所述的半導體裝置的製造方法，其中所述接著層的35℃下的儲存彈性係數為70MPa以上。
  3. 如申請專利範圍第1項或第2項所述的半導體裝置的製造方法，其中藉由隱形切割及刀片切割的其中一者而將所述半導體晶圓單片化，並且於冷卻條件下使所述基材膜擴張。
  4. 如申請專利範圍第1項或第2項所述的半導體裝置的製造方法，其中所述熱硬化性樹脂組成物含有：熱硬化性樹脂、分子量為10萬~100萬的高分子量成分、及填料，且 以所述熱硬化性樹脂組成物的總質量為基準，所述高分子量成分的含量為15質量%~66質量%。
  5. 如申請專利範圍第4項所述的半導體裝置的製造方法，其中以所述熱硬化性樹脂組成物的總質量為基準，所述填料的含量為25質量%~45質量%。
  6. 如申請專利範圍第1項或第2項所述的半導體裝置的製造方法，其為製造三維反及型記憶體的方法。
  7. 一種熱硬化性樹脂組成物，其用於半導體裝置的製造製程中，且120℃下的熔融黏度為13000Pa．s以上。
  8. 如申請專利範圍第7項所述的熱硬化性樹脂組成物，其35℃下的儲存彈性係數為70MPa以上。
  9. 如申請專利範圍第7項或第8項所述的熱硬化性樹脂組成物，其含有：熱硬化性樹脂、分子量為10萬~100萬的高分子量成分、及填料，且以所述熱硬化性樹脂組成物的總質量為基準，所述高分子量成分的含量為15質量%~66質量%。
  10. 如申請專利範圍第9項所述的熱硬化性樹脂組成物，其中以所述熱硬化性樹脂組成物的總質量為基準，所述填料的含量為25質量%~45質量%。
  11. 如申請專利範圍第7項或第8項所述的熱硬化性樹脂組成物，其用於三維反及型記憶體的製造製程中。
  12. 一種切晶黏晶一體型膜，包括：黏著層；以及接著層，所述接著層包含如申請專利範圍第7項至第11項中任一項所述的熱硬化性樹脂組成物。
  13. 如申請專利範圍第12項所述的切晶黏晶一體型膜，其中所述接著層的厚度為3μm~40μm。
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