TW201512380A - Underfill material, laminate sheet, and method for manufacturing semiconductor device - Google Patents

Underfill material, laminate sheet, and method for manufacturing semiconductor device Download PDF

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Publication number
TW201512380A
TW201512380A TW103119133A TW103119133A TW201512380A TW 201512380 A TW201512380 A TW 201512380A TW 103119133 A TW103119133 A TW 103119133A TW 103119133 A TW103119133 A TW 103119133A TW 201512380 A TW201512380 A TW 201512380A
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Taiwan
Prior art keywords
underfill material
weight
underfill
semiconductor wafer
semiconductor
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TW103119133A
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Chinese (zh)
Inventor
Akihiro Fukui
Naohide Takamoto
Hiroyuki Hanazono
Kosuke Morita
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Nitto Denko Corp
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Publication of TW201512380A publication Critical patent/TW201512380A/en

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    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Wire Bonding (AREA)
  • Polymers & Plastics (AREA)
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  • Medicinal Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Sealing Material Composition (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

Provided are: an underfill material including a flux component, the underfill material having heat storage stability allowing flux activity to be maintained even after loading by a heat history, and having excellent non-migrating properties such that migration over time to another adhesive layer is suppressed; a laminate sheet provided with the underfill material; and a method for manufacturing a semiconductor device. The present invention is an underfill material including, as a flux component, an aromatic compound having a molecular weight of at least 300 and having at least one ester bond within the molecule. The flux component undergoes a reduction in weight of less than 50% relative to the initial content after the underfill material has been heated for one hour at 100 DEG C.

Description

底部填充材、積層片及半導體裝置之製造方法 Underfill material, laminated sheet, and method of manufacturing semiconductor device

本發明係關於一種底部填充材、積層片及半導體裝置之製造方法。 The present invention relates to an underfill material, a laminate sheet, and a method of fabricating a semiconductor device.

近年來，更進一步追求半導體裝置及其封裝體之薄型化、小型化。作為實現其之對策，而廣泛利用藉由覆晶接合將半導體晶片等半導體元件安裝於基板上(覆晶連接)而得之覆晶型半導體裝置。覆晶連接係於半導體晶片之電路面與被黏著體之電極形成面對向之狀態下(面朝下)半導體晶片經由形成於其電路面之突起電極而被固定至被黏著體的安裝法。為了保護半導體元件表面或確保半導體元件與基板之間之連接可靠性，覆晶連接後對半導體元件與基板之間之空間進行密封樹脂填充。作為上述密封樹脂，雖然廣泛地使用液狀密封樹脂，但液狀密封樹脂難以調整注入位置或注入量。因此，業界提出有使用片狀密封樹脂填充半導體元件與基板之間之空間的技術。 In recent years, the semiconductor device and its package have been further reduced in thickness and size. As a countermeasure for achieving this, a flip-chip type semiconductor device obtained by mounting a semiconductor element such as a semiconductor wafer on a substrate by flip chip bonding (a flip chip connection) is widely used. The flip chip connection is a mounting method in which a semiconductor wafer is fixed to an adherend via a bump electrode formed on a surface of the circuit surface in a state in which the circuit surface of the semiconductor wafer and the electrode to be bonded face each other (face down). In order to protect the surface of the semiconductor element or ensure the connection reliability between the semiconductor element and the substrate, the space between the semiconductor element and the substrate is filled with a sealing resin after the flip chip connection. Although the liquid sealing resin is widely used as the sealing resin, it is difficult to adjust the injection position or the injection amount in the liquid sealing resin. Therefore, the industry has proposed a technique of filling a space between a semiconductor element and a substrate using a sheet-like sealing resin.

於半導體元件對被黏著體之覆晶安裝中，使設置於半導體元件之焊接凸塊等電極熔融而將兩者電性連接。此時，存在為了去除電極表面之氧化膜或提高焊料之潤濕性等而藉由助焊劑進行處理的情況。最近提出有亦將具有助焊劑活性之化合物添加至如上所述之片狀密封樹脂中之技術(專利文獻1)。 In the flip chip mounting of the semiconductor element to the adherend, electrodes such as solder bumps provided on the semiconductor element are melted to electrically connect the two. At this time, there is a case where the treatment is performed by a flux in order to remove the oxide film on the surface of the electrode or to improve the wettability of the solder or the like. A technique of adding a compound having flux activity to a sheet-like sealing resin as described above has recently been proposed (Patent Document 1).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

專利文獻1：日本專利特開2012-195414號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2012-195414

根據上述技術，可實現良好之焊接，半導體元件與被黏著體之間之空間亦被填充而獲得良好之連接可靠性。然而，例如於作為半導體裝置製造製程之一的晶片磊晶圓(CoW，chip on wafer)製程中，將多個半導體晶片覆晶連接於半導體晶圓上，結果於步驟之初期焊接之半導體晶片與最後焊接之半導體晶片中產生於100℃下1小時之熱歷程之差。因此，於初期焊接之半導體晶片之底部填充材中助焊劑成分因熱歷程之影響而消失或改性，其結果存在底部填充材不發揮充分之助焊劑活性之情形。又，於使底部填充材與背面研削用帶等具有黏著劑層之構件一體化而長期保存之情形時，存在底部填充材內之助焊劑成分向該黏著劑層轉移而於焊接時無法獲得充分之助焊劑活性的情形。 According to the above technique, good soldering can be achieved, and the space between the semiconductor element and the adherend is also filled to obtain good connection reliability. However, for example, in a wafer on wafer (CoW) process, which is one of semiconductor device manufacturing processes, a plurality of semiconductor wafers are flip-chip bonded to a semiconductor wafer, and as a result, the semiconductor wafer is soldered at the beginning of the step. The difference in thermal history at 1 hour at 100 ° C in the last soldered semiconductor wafer. Therefore, the flux component in the underfill of the semiconductor wafer which is initially soldered disappears or is modified by the influence of the heat history, and as a result, the underfill material does not exhibit sufficient flux activity. Further, when the underfill material and the member having the adhesive layer such as the back grinding belt are integrated and stored for a long period of time, the flux component in the underfill material is transferred to the adhesive layer, and sufficient soldering is not obtained at the time of soldering. The case of flux activity.

本發明係鑒於上述問題而成者，目的在於提供一種含有助焊劑成分並且具有即便承受熱歷程亦可維持助焊劑活性之耐熱保存性、及助焊劑成分向其他黏著劑層經時轉移受到抑制之良好非轉移性的底部填充材及具備其之積層片、以及半導體裝置之製造方法。 The present invention has been made in view of the above problems, and it is an object of the invention to provide a flux-containing component which has heat-resistant preservability for maintaining flux activity even when subjected to a thermal history, and inhibits transfer of flux components to other adhesive layers over time. A good non-transfer underfill material, a laminate sheet therewith, and a method of manufacturing a semiconductor device.

本申請案發明者等人潛心研究，結果發現，藉由採用下述構成可達成上述目的，從而完成本發明。 The inventors of the present application and others have intensively studied and found that the above object can be attained by adopting the following constitution, and the present invention has been completed.

即，本發明係一種底部填充材，其含有分子量為300以上且於分子內至少具有1個酯鍵之芳香族化合物作為助焊劑成分。 That is, the present invention is an underfill material containing an aromatic compound having a molecular weight of 300 or more and having at least one ester bond in a molecule as a flux component.

該底部填充材中使用特定之助焊劑成分，因此可發揮即便承受熱歷程亦可維持助焊劑活性之耐熱保存性，又，即便與其他黏著劑層貼合亦可抑制助焊劑成分向該黏著劑層之轉移而可發揮良好之非轉移性。其原因尚不明確，但推測是藉由將助焊劑成分之分子量設為300 以上而抑制由熱歷程引起之揮發或流出，並且藉由使用分子內導入有酯鍵之芳香族化合物，而助焊劑成分與形成底部填充材之樹脂成分之親和性提高，且助焊劑成分於底部填充材中之殘留性提高。又，一般認為酯鍵較羧基或羥基化學穩定之方面亦有助於耐熱保存性。然而，只要無損本發明之作用效果，助焊劑成分亦可含有羧基或羥基等反應性官能基。 Since the underfill material uses a specific flux component, it can exhibit heat-resistant storage stability by maintaining the flux activity even when subjected to a thermal history, and can suppress the flux component to the adhesive even if it is bonded to another adhesive layer. The transfer of layers can play a good non-transferability. The reason is not clear, but it is presumed that the molecular weight of the flux component is 300. In the above, the volatilization or the outflow caused by the heat history is suppressed, and by using an aromatic compound having an ester bond introduced therein, the affinity between the flux component and the resin component forming the underfill material is improved, and the flux component is at the bottom. The residual property in the filler is improved. Further, it is considered that the ester bond contributes to heat-resistant preservability in terms of chemical stability of the carboxyl group or the hydroxyl group. However, the flux component may contain a reactive functional group such as a carboxyl group or a hydroxyl group as long as the effects of the present invention are not impaired.

較佳為將上述底部填充材於100℃下加熱1小時後上述助焊劑成分相對於初期含量之重量減少率未達50%。藉由將於100℃下1小時之熱處理後之重量減少率抑制為未達50%，即便於承受熱歷程後底部填充材亦可發揮所需之助焊劑活性。 Preferably, the weight reduction rate of the flux component relative to the initial content after the underfill material is heated at 100 ° C for 1 hour is less than 50%. By suppressing the weight reduction rate after heat treatment at 100 ° C for 1 hour to less than 50%, the underfill material can exert the desired flux activity even after the heat history.

較佳為將上述底部填充材與黏著劑層積層而成之積層體於50℃下靜置72小時後上述底部填充材中之上述助焊劑成分相對於初期含量的重量減少率未達50%。藉此，例如即便為使底部填充材與具有黏著劑層之背面研削用帶一體化而使用之情況，助焊劑成分向黏著劑層之轉移受到抑制，因此可發揮優異之非轉移性。 Preferably, the laminate obtained by laminating the underfill material and the adhesive layer is allowed to stand at 50 ° C for 72 hours, and the weight reduction rate of the flux component in the underfill material relative to the initial content is less than 50%. Therefore, for example, even when the underfill material is used in combination with the back grinding belt having the pressure-sensitive adhesive layer, the transfer of the flux component to the pressure-sensitive adhesive layer is suppressed, so that excellent non-transferability can be exhibited.

相對於上述底部填充材中之上述助焊劑成分之重量與除上述助焊劑成分以外之成分之重量的合計重量，上述助焊劑成分之重量所占之比率較佳為1重量%以上且50重量%以下。藉由將助焊劑成分之重量比率設為1重量%以上，而底部填充材發揮充分之助焊劑活性，並且藉由設為50重量%以下，可確保作為底部填充材之原來之密封樹脂之功能。再者，於本說明書中，所謂「除助焊劑成分以外之成分」，意指底部填充材可含有之除助焊劑成分及溶劑以外之有機成分及無機成分。 The ratio of the weight of the flux component to the total weight of the flux component in the underfill material and the weight of the component other than the flux component is preferably 1% by weight or more and 50% by weight. the following. By setting the weight ratio of the flux component to 1% by weight or more, the underfill material exhibits sufficient flux activity, and by setting it to 50% by weight or less, the function as the original sealing resin of the underfill material can be ensured. . In the present specification, the term "component other than the flux component" means an organic component and an inorganic component other than the flux component and the solvent which the underfill material can contain.

本發明亦包括一種積層片，其具備具有基材及設置於該基材上之黏著劑層的黏著帶、及積層於上述黏著劑層上之該底部填充材。 The present invention also includes a laminated sheet comprising an adhesive tape having a substrate and an adhesive layer disposed on the substrate, and the underfill layer laminated on the adhesive layer.

藉由將該底部填充材與黏著帶一體地使用，可謀求半導體晶圓之加工至半導體元件之安裝之製造過程之效率化。 By using the underfill material integrally with the adhesive tape, it is possible to improve the efficiency of the manufacturing process of semiconductor wafer processing to mounting of semiconductor elements.

上述黏著帶可為半導體晶圓之背面研削用帶或切晶帶中之任一者。 The adhesive tape may be any one of a back grinding tape or a dicing tape of a semiconductor wafer.

本發明亦包括一種半導體裝置之製造方法，其係製造具備被黏著體、與該被黏著體電性連接之半導體元件、及填充該被黏著體與該半導體元件之間之空間之底部填充材的半導體裝置者，且該方法包括：準備將該底部填充材貼合於上述半導體元件而得之附有底部填充材之半導體元件的步驟，及連接步驟，其係將上述被黏著體與上述半導體元件之間之空間用上述底部填充材填充且將上述半導體元件與上述被黏著體電性連接。 The present invention also includes a method of fabricating a semiconductor device, which is characterized in that an underlying material having an adherend, a semiconductor element electrically connected to the adherend, and an underfill filling the space between the adherend and the semiconductor element is fabricated. a semiconductor device, comprising: a step of preparing a semiconductor element to which the underfill material is bonded to the semiconductor element and having an underfill material, and a connecting step of bonding the adherend to the semiconductor element The space between the pads is filled with the underfill material and the semiconductor element is electrically connected to the adherend.

該製造方法中使用含有特定助焊劑成分之底部填充材，因此即便於在使複數個半導體元件搭載於被黏著體之狀態下使底部填充材承受熱歷程的情形，底部填充材亦可發揮充分之助焊劑活性，而可獲得半導體元件與被黏著體之良好電性連接。 Since the underfill material containing a specific flux component is used in the production method, even if the underfill material is subjected to a heat history in a state in which a plurality of semiconductor elements are mounted on the adherend, the underfill material can be sufficiently used. The flux is active, and a good electrical connection between the semiconductor component and the adherend can be obtained.

1‧‧‧背面研削用帶 1‧‧‧Back grinding belt

1a、11a、41a‧‧‧基材 1a, 11a, 41a‧‧‧Substrate

1b、11b、41b‧‧‧黏著劑層 1b, 11b, 41b‧‧‧ adhesive layer

2、42‧‧‧底部填充材 2, 42‧‧‧ bottom filler

3、43‧‧‧半導體晶圓 3, 43‧‧‧ semiconductor wafer

3a‧‧‧半導體晶圓之形成有連接構件之電路面 3a‧‧‧The surface of the semiconductor wafer is formed with the circuit surface of the connecting member

3b‧‧‧半導體晶圓之與電路面相反側之面(背面) 3b‧‧‧Side of the semiconductor wafer on the opposite side of the circuit surface (back)

4、44‧‧‧連接構件 4, 44‧‧‧ connecting members

5、45‧‧‧半導體晶片(半導體元件) 5, 45‧‧‧ semiconductor wafer (semiconductor component)

10‧‧‧積層片 10‧‧‧Layered film

11、41‧‧‧切晶帶 11, 41‧‧ ‧ cutting ribbon

16、66‧‧‧被黏著體 16, 66‧‧‧Adhesive body

17‧‧‧導電材 17‧‧‧Electrical materials

20、60‧‧‧半導體裝置 20, 60‧‧‧ semiconductor devices

A‧‧‧積層體 A‧‧‧layer

B‧‧‧積層體 B‧‧‧Layer

圖1係表示本發明之一實施形態之積層片的剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing a laminated sheet according to an embodiment of the present invention.

圖2A係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 2A is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to an embodiment of the present invention.

圖2B係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 2B is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to an embodiment of the present invention.

圖2C係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 2C is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to an embodiment of the present invention.

圖2D係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 2D is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to an embodiment of the present invention.

圖2E係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 2E is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to an embodiment of the present invention.

圖2F係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 2F is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to an embodiment of the present invention.

圖3A係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 3A is a schematic cross-sectional view showing a step of a manufacturing process of a semiconductor device according to another embodiment of the present invention.

圖3B係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 3B is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

圖3C係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 3C is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

圖3D係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面示意圖。 Fig. 3D is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

<第1實施形態> <First embodiment>

以下，以底部填充材與背面研削用帶成為一體之積層片及使用其之半導體裝置之製造方法為例，對本發明之一實施形態進行說明。因此，於本實施形態中，使用背面研削用帶作為黏著帶。以下之說明基本上亦可應用於僅底部填充材之情形。 Hereinafter, an embodiment of the present invention will be described by taking, as an example, a laminated sheet in which an underfill material and a back grinding belt are integrated, and a method of manufacturing a semiconductor device using the same. Therefore, in the present embodiment, the back grinding belt is used as the adhesive tape. The following description can basically be applied to the case of only the underfill material.

於本實施形態中，使用具備積層於背面研削用帶上之底部填充材的積層片進行半導體晶圓之背面研削，其後進行切晶帶上之切晶、半導體元件之拾取，最後將半導體元件安裝於被黏著體。 In the present embodiment, the back surface of the semiconductor wafer is ground using a laminated sheet having an underfill layer laminated on the back grinding belt, and then the dicing on the dicing tape, the pick-up of the semiconductor element, and finally the semiconductor element are performed. Installed on the adherend.

本實施形態之代表性步驟包括：準備步驟，其係準備具備背面研削用帶與積層於該背面研削用帶上之底部填充材的積層片；貼合步驟，其係將半導體晶圓之形成有連接構件之電路面與上述積層片之底部填充材貼合；研削步驟，其係研削上述半導體晶圓之背面；固定步驟，其係將上述底部填充材與半導體晶圓自背面研削用帶剝離並將該 半導體晶圓貼附於切晶帶；切晶位置決定步驟，其係決定上述半導體晶圓中之切晶位置；切晶步驟，其係對上述半導體晶圓進行切晶而形成附有上述底部填充材之半導體元件；拾取步驟，其係將附有上述底部填充材之半導體元件自上述切晶帶剝離；對位步驟，其係使上述半導體元件與上述被黏著體之相對位置對準為彼此之預定連接位置；及連接步驟，其係將上述被黏著體與上述半導體元件之間之空間用上述底部填充材填充並且經由上述連接構件將上述半導體元件與上述被黏著體電性連接。 The representative step of the embodiment includes a preparation step of preparing a laminated sheet including a back grinding belt and an underfill layer laminated on the back grinding belt, and a bonding step of forming a semiconductor wafer a circuit surface of the connecting member is bonded to the underfill of the laminated sheet; a grinding step of grinding the back surface of the semiconductor wafer; and a fixing step of peeling the underfill material and the semiconductor wafer from the back grinding belt and Will a semiconductor wafer attached to the dicing tape; a dicing position determining step of determining a dicing position in the semiconductor wafer; and a dicing step of dicing the semiconductor wafer to form the underfill a semiconductor component; a pick-up step of stripping the semiconductor component with the underfill material from the dicing tape; and a aligning step of aligning the relative positions of the semiconductor component and the adherend to each other a predetermined connection position; and a connecting step of filling a space between the adherend and the semiconductor element with the underfill material and electrically connecting the semiconductor element to the adherend via the connection member.

[準備步驟] [Preparation steps]

於準備步驟中，準備具備背面研削用帶與積層於該背面研削用帶上之底部填充材的積層片。 In the preparation step, a laminated sheet including a back grinding belt and an underfill layer laminated on the back grinding belt is prepared.

(積層片) (layered film)

如圖1所示，積層片10具備背面研削用帶1及積層於背面研削用帶1上之底部填充材2。再者，底部填充材2如圖1所示以足以與半導體晶圓3(參照圖2A)貼合之尺寸設置即可，亦可積層於背面研削用帶1之整個面。 As shown in FIG. 1, the laminated sheet 10 is provided with the back grinding belt 1 and the underfill material 2 laminated on the back grinding belt 1. Further, the underfill material 2 may be provided in a size sufficient to be bonded to the semiconductor wafer 3 (see FIG. 2A) as shown in FIG. 1, or may be laminated on the entire surface of the back grinding tape 1.

(背面研削用帶) (back grinding belt)

背面研削用帶1具備基材1a及積層於基材1a上之黏著劑層1b。再者，底部填充材2係積層於黏著劑層1b上。 The back grinding belt 1 includes a base material 1a and an adhesive layer 1b laminated on the base material 1a. Further, the underfill material 2 is laminated on the adhesive layer 1b.

(基材) (substrate)

上述基材1a形成積層片10之強度母體。例如可列舉：低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴；乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺基甲酸酯、聚對苯二甲酸乙二 酯、聚萘二甲酸乙二酯等聚酯；聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素系樹脂、聚矽氧樹脂、金屬(箔)、紙等。於黏著劑層1b為紫外線硬化型之情形時，基材1a較佳為對紫外線具有透過性。 The base material 1a forms a strength matrix of the laminated sheet 10. For example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutene Polyolefin such as polymethylpentene; ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating) copolymer, Ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate Polyesters such as esters and polyethylene naphthalates; polycarbonates, polyimines, polyetheretherketones, polyimines, polyetherimine, polyamines, wholly aromatic polyamines, poly Phenylene sulfide, aromatic polyamine (paper), glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyxylene resin, metal (foil), paper, and the like. In the case where the adhesive layer 1b is of an ultraviolet curing type, the substrate 1a is preferably transparent to ultraviolet rays.

又，作為基材1a之材料，可列舉上述樹脂之交聯體等聚合物。上述塑膠膜可未經延伸而使用，亦可視需要使用實施過單軸或雙軸延伸處理者。 Moreover, as a material of the base material 1a, a polymer such as a crosslinked body of the above resin may be mentioned. The above plastic film can be used without extension, and a single-axis or biaxial stretching process can also be used as needed.

為了提高與鄰接之層之密接性、保持性等，基材1a之表面可實施慣用之表面處理，例如鉻酸處理、臭氧曝露、火焰曝露、高壓電擊曝露、電離輻射處理等化學處理或物理處理、利用底塗劑(例如下述黏著物質)之塗佈處理。 In order to improve adhesion to adjacent layers, retention, etc., the surface of the substrate 1a can be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, or the like. Coating treatment using a primer (for example, an adhesive described below).

上述基材1a可適當選擇同種或不同種基材而使用，視需要可使用混合數種基材而成者。又，為了對基材1a賦予抗靜電功能，可於上述之基材1a上設置由金屬、合金、該等之氧化物等形成之厚度為30~500Å左右之導電性物質之蒸鍍層。亦可藉由於基材中添加抗靜電劑而賦予抗靜電能力。基材1a可為單層或2種以上之複數層。 The substrate 1a can be appropriately selected from the same or different types of substrates, and a plurality of substrates can be used as needed. Moreover, in order to provide an antistatic function to the base material 1a, a vapor deposition layer of a conductive material having a thickness of about 30 to 500 Å formed of a metal, an alloy, or the like may be provided on the base material 1a. Antistatic ability can also be imparted by the addition of an antistatic agent to the substrate. The substrate 1a may be a single layer or a plurality of layers of two or more.

基材1a之厚度可適當決定，通常為5μm以上且200μm以下左右，較佳為35μm以上且120μm以下。 The thickness of the base material 1a can be appropriately determined, and is usually 5 μm or more and 200 μm or less, preferably 35 μm or more and 120 μm or less.

再者，基材1a中亦可於無損本發明之效果等之範圍內含有各種添加劑(例如著色劑、填充劑、塑化劑、抗老化劑、抗氧化劑、界面活性劑、阻燃劑等)。 Further, the substrate 1a may contain various additives (for example, a color former, a filler, a plasticizer, an anti-aging agent, an antioxidant, a surfactant, a flame retardant, etc.) within a range not impairing the effects of the present invention and the like. .

(黏著劑層) (adhesive layer)

黏著劑層1b之形成所使用之黏著劑只要為如下者則並無特別限制：於背面研削時經由底部填充材牢固地保持半導體晶圓，並且背面研削後使附有底部填充材之半導體晶圓向切晶帶轉移時可控制附有底 部填充材之半導體晶圓使之可剝離。例如，可使用丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性接著劑。作為上述感壓性接著劑，就半導體晶圓或玻璃等忌諱污染之電子零件之藉由超純水或酒精等有機溶劑之清潔洗淨性等方面而言，較佳為以丙烯酸系聚合物為基礎聚合物之丙烯酸系黏著劑。 The adhesive used for the formation of the adhesive layer 1b is not particularly limited as long as the semiconductor wafer is firmly held by the underfill at the time of back grinding, and the semiconductor wafer with the underfill is ground after the back grinding. Controlled with a bottom when transferring to a dicing tape The semiconductor wafer of the filler material makes it peelable. For example, a usual pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. As the pressure-sensitive adhesive, in terms of cleaning and cleaning properties of an organic solvent such as ultrapure water or alcohol, such as a semiconductor wafer or glass, it is preferable to use an acrylic polymer as an acrylic polymer. Acrylic adhesive for base polymers.

作為上述丙烯酸系聚合物，可列舉使用丙烯酸酯作為主單體成分者。作為上述丙烯酸酯，例如可列舉：使用(甲基)丙烯酸烷基酯(例如甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數為1~30、尤其是碳數為4~18之直鏈狀或支鏈狀烷基酯等)及(甲基)丙烯酸環烷基酯(例如環戊酯、環己酯等)之1種或2種以上作為單體成分的丙烯酸系聚合物等。再者，所謂(甲基)丙烯酸酯，意指丙烯酸酯及/或甲基丙烯酸酯，本發明之(甲基)均為相同之含義。 As the acrylic polymer, those using acrylate as a main monomer component can be mentioned. As the acrylate, for example, an alkyl (meth)acrylate (for example, a methyl ester, an ethyl ester, a propyl ester, an isopropyl ester, a butyl ester, an isobutyl ester, a second butyl ester, a third butyl ester, or the like) may be used. Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, decyl, isodecyl, undecyl, dodecyl, ten The alkyl group such as a trialkyl ester, a tetradecyl ester, a hexadecyl ester, an octadecyl ester or an eicosyl ester has a carbon number of 1 to 30, especially a linear chain having a carbon number of 4 to 18. One or two or more kinds of acrylic polymers such as a cycloalkyl ester (such as a cyclopentyl ester or a cyclohexyl ester) and a monomeric component. Further, the term "(meth)acrylate" means acrylate and/or methacrylate, and (meth) of the present invention has the same meaning.

為了凝聚力、耐熱性等之改質，上述丙烯酸系聚合物視需要亦可含有可與上述(甲基)丙烯酸烷基酯或環烷基酯共聚合之其他單體成分所對應的單位。作為上述單體成分，例如可列舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含羧基單體；順丁烯二酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含磺酸基 單體；2-羥基乙基丙烯醯基磷酸酯等含磷酸基單體；丙烯醯胺、丙烯腈等。該等可共聚合之單體成分可使用1種或2種以上。該等可共聚合之單體之使用量較佳為全部單體成分之40重量%以下。 In order to improve the cohesive force, heat resistance, and the like, the acrylic polymer may optionally contain a unit corresponding to another monomer component copolymerized with the alkyl (meth)acrylate or the cycloalkyl ester. Examples of the monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and fumaric acid. a carboxyl group-containing monomer such as crotonic acid; an acid anhydride monomer such as maleic anhydride or itaconic acid anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid 4-hydroxybutyl ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, a hydroxyl group-containing monomer such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methylpropanesulfonic acid , (meth) acrylamide, propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid, etc. a monomer; a phosphate group-containing monomer such as 2-hydroxyethyl acryloyl phosphate; acrylamide, acrylonitrile or the like. One or two or more kinds of these copolymerizable monomer components can be used. The amount of the copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.

進而，上述丙烯酸系聚合物為了進行交聯，亦可含有多官能性單體等作為視需要之共聚合用單體成分。作為上述多官能性單體，例如可列舉：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸聚酯、(甲基)丙烯酸胺基甲酸酯等。該等多官能性單體亦可使用1種或2種以上。多官能性單體之使用量就黏著特性等方面而言，較佳為全部單體成分之30重量%以下。 Further, the acrylic polymer may contain a polyfunctional monomer or the like as a monomer component for copolymerization as necessary in order to carry out crosslinking. Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and new Pentandiol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, epoxy (meth) acrylate, (meth) acrylate polyester, (meth) acrylate urethane, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer to be used is preferably 30% by weight or less based on the total of the monomer components in terms of adhesion characteristics and the like.

上述丙烯酸系聚合物可藉由使單一單體或2種以上單體混合物聚合而獲得。聚合可利用溶液聚合、乳化聚合、塊狀聚合、懸浮聚合等之任一方式進行。就防止對清潔之被黏著體之污染等方面而言，較佳為低分子量物質之含量較少。就該方面而言，丙烯酸系聚合物之數量平均分子量較佳為30萬以上，進而較佳為40萬~300萬左右。 The above acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more kinds of monomers. The polymerization can be carried out by any one of solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like. In terms of preventing contamination of the adherend to be cleaned, etc., it is preferred that the content of the low molecular weight substance is small. In this respect, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, and more preferably about 400,000 to 3,000,000.

又，為了提高作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量，上述黏著劑亦可適當採用外部交聯劑。作為外部交聯方法之具體方法，可列舉添加聚異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等所謂交聯劑並進行反應之方法。於使用外部交聯劑之情形時，其使用量可根據與應交聯之基礎聚合物之平衡、進而根據作為黏著劑之使用用途而適當決定。通常較佳為相對於上述基礎聚合物100重量份而調配5重量份左右以下，進而較佳為調配0.1~5重量份。進而，黏著劑視需要除上述成分以外亦可使用先前公知之各種黏著賦予劑、抗老化劑等添加劑。 Moreover, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used as the above-mentioned adhesive. As a specific method of the external crosslinking method, a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine-based crosslinking agent to carry out a reaction can be mentioned. In the case of using an external crosslinking agent, the amount thereof to be used may be appropriately determined depending on the balance with the base polymer to be crosslinked, and further depending on the use as the adhesive. It is usually preferably 5 parts by weight or less based on 100 parts by weight of the base polymer, and more preferably 0.1 to 5 parts by weight. Further, as the adhesive, an additive such as various conventionally known adhesion-imparting agents and anti-aging agents may be used in addition to the above components.

黏著劑層1b可藉由放射線硬化型黏著劑形成。放射線硬化型黏著劑可藉由照射紫外線等放射線而增大交聯度並容易地降低其黏著力，從而可容易地進行附有底部填充材之半導體晶圓之剝離。作為放射線，可列舉：X射線、紫外線、電子束、α射線、β射線、中子射線等。 The adhesive layer 1b can be formed by a radiation hardening type adhesive. The radiation-curable adhesive can easily peel off the semiconductor wafer with the underfill by irradiating radiation such as ultraviolet rays to increase the degree of crosslinking and easily lower the adhesion. Examples of the radiation include X-rays, ultraviolet rays, electron beams, α rays, β rays, and neutron rays.

放射線硬化型黏著劑可並無特別限制地使用具有碳-碳雙鍵等放射線硬化性官能基且顯示黏著性者。作為放射線硬化型黏著劑，例如可例示於上述丙烯酸系黏著劑、橡膠系黏著劑等通常之感壓性黏著劑中調配有放射線硬化性單體成分或低聚物成分之添加型放射線硬化性黏著劑。 The radiation-curable pressure-sensitive adhesive can be used without any particular limitation, and a radiation curable functional group such as a carbon-carbon double bond is used. The radiation curable adhesive is exemplified by an addition type radiation curable adhesive in which a radiation curable monomer component or an oligomer component is blended in a usual pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive. Agent.

作為所調配之放射線硬化性單體成分，例如可列舉：胺基甲酸酯低聚物、(甲基)丙烯酸胺基甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，放射線硬化性低聚物成分可列舉胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，較適當為其重量平均分子量為100~30000左右之範圍者。關於放射線硬化性單體成分或低聚物成分之調配量，可根據上述黏著劑層之種類適當地決定可降低黏著劑層之黏著力之量。通常，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為5~500重量份，較佳為40~150重量份左右。 Examples of the radiation curable monomer component to be blended include a urethane oligomer, a (meth)acrylic acid urethane, a trimethylolpropane tri(meth)acrylate, and a tetrahydroxy group. Methyl methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based polymer, and the weight average molecular weight thereof is suitably The range of 100~30000 or so. The amount of the radiation curable monomer component or the oligomer component can be appropriately determined according to the type of the above-mentioned adhesive layer to reduce the adhesion of the adhesive layer. In general, it is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

又，作為放射線硬化型黏著劑，除上文說明之添加型放射線硬化性黏著劑以外，可列舉使用於聚合物側鏈或主鏈中或者主鏈末端具有碳-碳雙鍵者作為基礎聚合物之內在型放射線硬化性黏著劑。內在型放射線硬化性黏著劑無需含有作為低分子成分之低聚物成分等，或不大量含有，因此無低聚物成分等經過一段時間於黏著劑中移動而可 形成層結構穩定之黏著劑層，因而較佳。 In addition, as the radiation-curable adhesive, in addition to the above-described additive-type radiation-curable adhesive, a base polymer having a carbon-carbon double bond in a polymer side chain or a main chain or a main chain terminal may be mentioned. An intrinsic type radiation curable adhesive. The intrinsic type radiation curable adhesive does not need to contain an oligomer component as a low molecular component, or is not contained in a large amount, so that no oligomer component or the like can be moved in the adhesive over a period of time. It is preferred to form an adhesive layer having a stable layer structure.

上述具有碳-碳雙鍵之基礎聚合物可並無特別限制地使用具有碳-碳雙鍵且具有黏著性者。作為上述基礎聚合物，較佳為以丙烯酸系聚合物作為基本骨架者。作為丙烯酸系聚合物之基本骨架，可列舉上述例示之丙烯酸系聚合物。 The base polymer having a carbon-carbon double bond described above can be used without any particular limitation, and has a carbon-carbon double bond and has adhesiveness. As the base polymer, an acrylic polymer is preferred as the basic skeleton. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.

向上述丙烯酸系聚合物導入碳-碳雙鍵之方法並無特別限制，可採用各種方法，碳-碳雙鍵導入至聚合物側鏈時容易進行分子設計。例如，可列舉如下方法：預先使於丙烯酸系聚合物中具有官能基之單體共聚合後，使具有可與該官能基反應之官能基及碳-碳雙鍵之化合物維持碳-碳雙鍵之放射線硬化性而直接進行縮合或加成反應。 The method of introducing the carbon-carbon double bond to the above acrylic polymer is not particularly limited, and various methods can be employed. When a carbon-carbon double bond is introduced into the polymer side chain, molecular design is facilitated. For example, a method of copolymerizing a monomer having a functional group in an acrylic polymer and maintaining a carbon-carbon double bond with a compound having a functional group reactive with the functional group and a carbon-carbon double bond can be mentioned. Radiation hardening and direct condensation or addition reaction.

作為該等官能基之組合之例，可列舉：羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸酯基等。於該等官能基之組合中，就追蹤反應之容易性而言，較佳為羥基與異氰酸酯基之組合。又，只要為藉由該等官能基之組合而生成上述具有碳-碳雙鍵之丙烯酸系聚合物的組合，則官能基可位於丙烯酸系聚合物與上述化合物之任一側，於上述較佳之組合中，較佳為丙烯酸系聚合物具有羥基且上述化合物具有異氰酸酯基之情形。於該情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，例如可列舉：甲基丙烯醯基異氰酸酯、異氰酸2-甲基丙烯醯氧基乙酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。又，作為丙烯酸系聚合物，可使用將上述例示之含羥基單體或2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚之醚系化合物等共聚合而成者。 Examples of the combination of these functional groups include a carboxyl group, an epoxy group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group. Among the combinations of such functional groups, a combination of a hydroxyl group and an isocyanate group is preferred in terms of easiness of tracking the reaction. Further, as long as the combination of the above-mentioned functional groups is used to form the above-mentioned acrylic polymer having a carbon-carbon double bond, the functional group may be located on either side of the acrylic polymer and the above compound, preferably in the above. In the combination, it is preferred that the acrylic polymer has a hydroxyl group and the above compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacrylonitrile isocyanate, 2-methylpropenyloxyethyl isocyanate, m-isopropenyl-α, α- Dimethylbenzyl isocyanate and the like. Further, as the acrylic polymer, copolymerization of the above-exemplified hydroxyl group-containing monomer, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether or the like can be used. Adult.

上述內在型放射線硬化性黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(尤其是丙烯酸系聚合物)，亦可以不使特性變差之程度調配上述放射線硬化性之單體成分或低聚物成分。放射線硬化性之低聚物成分等通常相對於基礎聚合物100重量份為30重量份之範圍內，較佳為0~10重量份之範圍。 The above-mentioned intrinsic radiation curable adhesive may be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, or may be formulated with the above-mentioned radiation curable monomer component or the degree of deterioration of properties. Oligomer component. The radiation curable oligomer component or the like is usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the base polymer.

於藉由紫外線等進行硬化之情形時，較佳為使上述放射線硬化型黏著劑中含有光聚合起始劑。作為光聚合起始劑，例如可列舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1-酮等苯乙酮系化合物；安息香***、安息香異丙醚、大茴香偶姻甲醚等安息香醚系化合物；苄基二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；9-氧硫、2-氯9-氧硫、2-甲基9-氧硫、2,4-二甲基9-氧硫、異丙基9-氧硫、2,4-二氯9-氧硫、2,4-二乙基9-氧硫、2,4-二異丙基9-氧硫等9-氧硫系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基磷酸酯等。光聚合起始劑之調配量相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為0.05~20重量份左右。 In the case of curing by ultraviolet rays or the like, it is preferred that the radiation curable adhesive contains a photopolymerization initiator. As the photopolymerization initiator, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, α-hydroxy-α,α'-dimethylacetophenone can be exemplified. , an α-keto alcohol compound such as 2-methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylbenzene Acetophenone-based compounds such as ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinylpropan-1-one a benzoin ether compound such as benzoin ethyl ether, benzoin isopropyl ether, fennel aceton methyl ether; a ketal compound such as benzyl dimethyl ketal; an aromatic sulfonium chloride compound such as 2-naphthalene sulfonium chloride; a photoactive lanthanide compound such as phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)anthracene; benzophenone, benzamidine benzoic acid, 3,3'-dimethyl- a benzophenone compound such as 4-methoxybenzophenone; 9-oxygen sulfur 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur Compound; camphorquinone; halogenated ketone; fluorenylphosphine oxide; thiol phosphate. The amount of the photopolymerization initiator to be added is, for example, about 0.05 to 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

再者，照射放射線時於發生由氧引起之硬化障礙之情形時，較理想為利用一些方法自放射線硬化型黏著劑層1b之表面阻隔氧(空氣)。例如可列舉：用隔片被覆上述黏著劑層1b之表面之方法，或於氮氣環境中進行紫外線等放射線之照射之方法等。 Further, in the case where the curing is caused by oxygen when the radiation is irradiated, it is preferable to block oxygen (air) from the surface of the radiation-curable adhesive layer 1b by some methods. For example, a method of coating the surface of the above-mentioned adhesive layer 1b with a separator or a method of irradiating radiation such as ultraviolet rays in a nitrogen atmosphere may be mentioned.

再者，黏著劑層1b中亦可於無損本發明之效果等之範圍內含有各種添加劑(例如，著色劑、增黏劑、增量劑、填充劑、黏著賦予劑、塑化劑、抗老化劑、抗氧化劑、界面活性劑、交聯劑等)。 Further, the adhesive layer 1b may contain various additives in the range which does not impair the effects of the present invention and the like (for example, a coloring agent, a tackifier, a bulking agent, a filler, an adhesion-imparting agent, a plasticizer, and an anti-aging agent). Agents, antioxidants, surfactants, crosslinkers, etc.).

黏著劑層1b之厚度並無特別限定，就同時實現防止半導體晶圓之研削面缺損、固定保持底部填充材2等觀點而言，較佳為1~50μm左右。較佳為5~40μm，進而較佳為10~30μm。 The thickness of the adhesive layer 1b is not particularly limited, and is preferably about 1 to 50 μm from the viewpoint of preventing the grinding surface of the semiconductor wafer from being damaged and fixing the underfill material 2 . It is preferably 5 to 40 μm, more preferably 10 to 30 μm.

(底部填充材) (underfill)

本實施形態中之底部填充材2可較佳地用作填充經表面安裝(例如覆晶安裝等)之半導體元件與被黏著體之間之空間的密封用膜。 The underfill material 2 in the present embodiment can be preferably used as a film for sealing which fills a space between a semiconductor element which is surface-mounted (for example, flip chip mounting) and the adherend.

底部填充材含有特定之助焊劑成分。作為其他除助焊劑成分以外之構成材料，視需要可列舉：樹脂成分、熱硬化促進觸媒、交聯劑、其他有機系添加劑等有機成分(溶劑除外)、或無機填充劑、其他無機系添加劑等無機成分等。作為樹脂成分，可列舉併用熱塑性樹脂與熱硬化性樹脂所獲得者。又，亦可單獨使用熱塑性樹脂或熱硬化性樹脂。 The underfill contains a specific flux component. Other constituent materials other than the flux component may, for example, be an organic component (excluding a solvent) such as a resin component, a thermosetting-promoting catalyst, a crosslinking agent, or other organic additives, or an inorganic filler or other inorganic additive. Inorganic ingredients, etc. As the resin component, those obtained by using a thermoplastic resin and a thermosetting resin in combination are mentioned. Further, a thermoplastic resin or a thermosetting resin may be used alone.

(助焊劑成分) (flux composition)

底部填充材2係為了去除焊錫凸塊表面之氧化膜而使半導體元件之安裝較為容易，而含有助焊劑成分。助焊劑成分為分子量為300以上、且分子內至少具有1個酯鍵之芳香族化合物(以下亦稱為「特定芳香族化合物」)。作為上述特定芳香族化合物，可列舉：酚酞、迷迭香酸、5-羧基螢光素、6-羧基螢光素、科里內酯(Corey lactone)、響尾蛇毒(crotalin)。該等之中，就耐熱保存性、非轉移性及獲取容易性之觀點而言，較佳為酚酞。 The underfill material 2 contains a flux component in order to remove the oxide film on the surface of the solder bump and to facilitate mounting of the semiconductor element. The flux component is an aromatic compound having a molecular weight of 300 or more and having at least one ester bond in the molecule (hereinafter also referred to as "specific aromatic compound"). Examples of the specific aromatic compound include phenolphthalein, rosmarinic acid, 5-carboxyfluorescein, 6-carboxyfluorescein, Corey lactone, and crotalin. Among these, phenolphthalein is preferred from the viewpoint of heat-resistant storage stability, non-metastatic property, and ease of availability.

助焊劑成分必須具有酯鍵。藉由含有反應性較低且化學性穩定之酯鍵，可抑制無意之反應，對耐熱保存性之提高有效。 The flux component must have an ester bond. By containing an ester bond which is less reactive and chemically stable, unintentional reaction can be suppressed, and the improvement of heat-resistant storage stability is effective.

底部填充材2中，只要無損本發明之作用效果，除上述特定芳香族化合物以外亦可含有其他助焊劑成分。其他助焊劑成分並無特別限定，可使用先前公知之具有助焊劑作用之化合物，例如可列舉：雙酚酸、己二酸、乙醯基水楊酸、苯甲酸、二苯羥乙酸、壬二酸、苄基苯甲酸、丙二酸、2,2-雙(羥基甲基)丙酸、水楊酸、鄰甲氧基苯甲酸(鄰大茴香酸)、間羥基苯甲酸、琥珀酸、2,6-二甲氧基甲基對甲酚、苯甲醯肼、碳醯肼、丙二醯肼、丁二醯肼、戊二醯肼、水楊醯肼、亞胺基 二乙酸二醯肼、伊康酸二醯肼、檸檬酸三醯肼、硫代碳醯肼、二苯甲酮腙、4,4'-氧代雙苯磺醯肼及己二酸二醯肼等。 In the underfill material 2, other flux components may be contained in addition to the specific aromatic compound as long as the effects of the present invention are not impaired. The other flux component is not particularly limited, and a conventionally known compound having a flux action can be used, and examples thereof include bisphenolic acid, adipic acid, acetylsalicylic acid, benzoic acid, diphenyl glycolic acid, and hydrazine. Acid, benzyl benzoic acid, malonic acid, 2,2-bis(hydroxymethyl)propionic acid, salicylic acid, o-methoxybenzoic acid (o-anisic acid), m-hydroxybenzoic acid, succinic acid, 2 ,6-dimethoxymethyl-p-cresol, benzamidine, carbonium, propylenediazine, diacetyl, pentane, salicylate, imino Diacetic acid dioxime, itaconic acid diterpene, tritium citrate, thiocarbonium, benzophenone oxime, 4,4'-oxobisbenzenesulfonate and diammonium adipate Wait.

助焊劑成分之添加量(含有複數種助焊劑成分之情形時為合計量)只要為可發揮上述助焊劑作用之程度即可，上述助焊劑成分之重量相對於上述底部填充材中上述助焊劑成分之重量與除上述助焊劑成分以外之成分之重量的合計重量所占之比率較佳為1重量%以上且50重量%以下，更佳為1重量%以上且25重量%以下，進而較佳為1重量%以上且10重量%以下。藉由設為上述下限以上而底部填充材可發揮充分之助焊劑活性，並且藉由設為上述上限以下而可確保底部填充材原本之作為密封樹脂之功能。 The amount of the flux component added (in the case where a plurality of flux components are contained) is sufficient as long as the flux function is sufficient, and the weight of the flux component is relative to the flux component in the underfill material. The ratio of the weight to the total weight of the components other than the flux component is preferably 1% by weight or more and 50% by weight or less, more preferably 1% by weight or more and 25% by weight or less, and still more preferably 1% by weight or more and 10% by weight or less. By setting the above-mentioned lower limit or more, the underfill material can exhibit sufficient flux activity, and by setting it as the above upper limit or less, it is possible to secure the function of the underfill material as a sealing resin.

將底部填充材於100℃下加熱1小時後助焊劑成分相對於初期含量之重量減少率較佳為未達50%，更佳為未達40%，進而較佳為未達30%。藉由將承受於100℃下1小時之熱歷程後之重量減少率抑制為未達上述上限，即便為晶片磊晶圓製程等使底部填充材承受熱歷程之製程，亦可發揮優異之耐熱保存性，而底部填充材可發揮所需之助焊劑活性。 The weight reduction rate of the flux component relative to the initial content after heating the underfill at 100 ° C for 1 hour is preferably less than 50%, more preferably less than 40%, still more preferably less than 30%. By suppressing the weight reduction rate after the heat history at 100 ° C for 1 hour to the above upper limit, even if the underfill material is subjected to a heat history process such as a wafer wafer process, excellent heat-resistant storage can be exhibited. The underfill material can exert the desired flux activity.

將積層有上述底部填充材與黏著劑層之積層體於50℃下靜置72小時後，上述底部填充材中之上述助焊劑成分相對於初期含量之重量減少率較佳為未達50%，更佳為未達40%，進而較佳為未達30%。藉此，例如，即便為使底部填充材與具備黏著劑層之背面研削用帶一體化而使用之情形，助焊劑成分向黏著劑層之轉移亦受到抑制，因此可發揮優異之非轉移性。 After the laminate of the underfill and the adhesive layer is allowed to stand at 50 ° C for 72 hours, the weight reduction rate of the flux component in the underfill material relative to the initial content is preferably less than 50%. More preferably, it is less than 40%, and further preferably less than 30%. Therefore, for example, even when the underfill material is used in combination with the back grinding belt having the pressure-sensitive adhesive layer, the transfer of the flux component to the pressure-sensitive adhesive layer is suppressed, so that excellent non-transferability can be exhibited.

(熱塑性樹脂) (thermoplastic resin)

作為上述熱塑性樹脂，可列舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性 聚醯亞胺樹脂、6-尼龍或6,6-尼龍等聚醯胺樹脂、苯氧基樹脂、丙烯酸系樹脂、PET(polyethylene terephthalate，聚對苯二甲酸乙二酯)或PBT(polybutylene terephthalate，聚對苯二甲酸丁二酯)等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、或氟樹脂等。該等熱塑性樹脂可單獨使用或併用2種以上。該等熱塑性樹脂之中，尤佳為離子性雜質較少、耐熱性較高且可確保半導體元件之可靠性的丙烯酸系樹脂。 Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Diene resin, polycarbonate resin, thermoplastic Polyimine resin, polyamine resin such as 6-nylon or 6,6-nylon, phenoxy resin, acrylic resin, PET (polyethylene terephthalate) or PBT (polybutylene terephthalate) A saturated polyester resin such as polybutylene terephthalate), a polyamidamine resin, or a fluororesin. These thermoplastic resins may be used alone or in combination of two or more. Among these thermoplastic resins, an acrylic resin having less ionic impurities, high heat resistance, and reliability of a semiconductor element can be preferably used.

作為上述丙烯酸系樹脂，並無特別限定，可列舉以1種或2種以上具有碳數30以下、尤其是碳數4~18之直鏈或支鏈烷基之丙烯酸或甲基丙烯酸之酯作為成分的聚合物等。作為上述烷基，例如可列舉：甲基、乙基、丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基或二十烷基等。 The acrylic resin is not particularly limited, and examples thereof include one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having a carbon number of 30 or less, particularly a carbon number of 4 to 18. The polymer of the component, etc. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl or eicosyl and the like.

又，作為形成上述聚合物之其他單體，並無特別限定，例如可列舉：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸或丁烯酸等含羧基單體；順丁烯二酸酐或伊康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或丙烯酸(4-羥基甲基環己基)甲酯等含羥基單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等含磺酸基單體；或2-羥基乙基丙烯醯基磷酸酯等含磷酸基單體；丙烯腈等含氰基單體等。 Further, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and antibutene. a carboxyl group-containing monomer such as a diacid or a crotonic acid; an acid anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, 12-hydroxy (meth) acrylate a hydroxyl group-containing monomer such as lauryl ester or (4-hydroxymethylcyclohexyl)methyl acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, a sulfonic acid group-containing monomer such as (meth)acrylonitrile or propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryloxynaphthalenesulfonic acid; or 2-hydroxyethylpropenyl phosphate Such as a phosphoric acid group-containing monomer; a cyano group-containing monomer such as acrylonitrile.

(熱硬化性樹脂) (thermosetting resin)

作為上述熱硬化性樹脂，可列舉：酚系樹脂、胺基樹脂、不飽 和聚酯樹脂、環氧樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂或熱硬化性聚醯亞胺樹脂等。該等樹脂可單獨使用或併用2種以上。尤其使半導體元件腐蝕之離子性雜質等之含量較少之環氧樹脂較佳。又，作為環氧樹脂之硬化劑，較佳為酚系樹脂。 Examples of the thermosetting resin include a phenol resin, an amine resin, and an insufficient And polyester resin, epoxy resin, polyurethane resin, polyoxyn resin or thermosetting polyimide resin. These resins may be used alone or in combination of two or more. In particular, an epoxy resin having a small content of ionic impurities or the like which causes corrosion of a semiconductor element is preferable. Further, as the curing agent for the epoxy resin, a phenol resin is preferable.

上述環氧樹脂只要為通常可用作接著劑組合物者，則並無特別限定，例如可使用雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、茀型、苯酚酚醛清漆型、鄰甲酚酚醛清漆型、三羥基苯基甲烷型、四酚基乙烷型等二官能環氧樹脂或多官能環氧樹脂；或乙內醯脲型、異氰脲酸三縮水甘油酯型或縮水甘油胺型等環氧樹脂。該等可單獨使用或併用2種以上。該等環氧樹脂之中，尤佳為酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三羥基苯基甲烷型樹脂或四酚基乙烷型環氧樹脂。其原因在於：該等環氧樹脂富於與作為硬化劑之酚系樹脂之反應性且耐熱性等優異。 The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition. For example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol can be used. A type, bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol novolac type, trishydroxyphenylmethane type, tetraphenol ethane type, etc. An epoxy resin such as a polyfunctional epoxy resin; or a urecyanium type, an isocyanuric acid triglycidyl ester type or a glycidylamine type. These may be used alone or in combination of two or more. Among these epoxy resins, a novolak type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetraphenol ethane type epoxy resin is particularly preferable. This is because these epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

進而，上述酚系樹脂係作為上述環氧樹脂之硬化劑而發揮作用者，例如可列舉：苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚系樹脂、可溶酚醛型酚系樹脂、聚對羥基苯乙烯等聚氧苯乙烯等。該等可單獨使用或併用2種以上。該等酚系樹脂之中，尤佳為苯酚酚醛清漆樹脂、苯酚芳烷基樹脂。其原因在於：該等樹脂可使半導體裝置之連接可靠性提高。 Further, the phenol-based resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, and a third butyl phenol novolak resin. A novolak type phenol type resin such as a nonylphenol novolak resin, a novolac type phenol type resin, or a polyoxystyrene such as polyparaxyl styrene. These may be used alone or in combination of two or more. Among these phenolic resins, a phenol novolac resin and a phenol aralkyl resin are particularly preferable. The reason for this is that the resins can improve the connection reliability of the semiconductor device.

關於上述環氧樹脂與酚系樹脂之調配比率，例如較佳為以相對於上述環氧樹脂成分中每1當量環氧基而酚系樹脂中之羥基為0.5~2.0當量之方式進行調配。更佳為0.8~1.2當量。即，其原因在於：若兩者之調配比率偏離上述範圍，則無法進行充分之硬化反應，環氧樹脂硬化物之特性容易變差。 The blending ratio of the epoxy resin and the phenol resin is preferably, for example, 0.5 to 2.0 equivalents per one equivalent of the epoxy group in the epoxy resin component and the hydroxyl group in the phenol resin. More preferably, it is 0.8 to 1.2 equivalents. That is, the reason is that if the blending ratio of the two is out of the above range, a sufficient curing reaction cannot be performed, and the properties of the cured epoxy resin are likely to be deteriorated.

再者，於本發明中，尤佳為使用環氧樹脂、酚系樹脂及丙烯酸 系樹脂之底部填充材。該等樹脂由於離子性雜質較少且耐熱性較高，因此可確保半導體元件之可靠性。關於該情形時之調配比，相對於丙烯酸系樹脂成分100重量份，環氧樹脂與酚系樹脂之混合量為50~500重量份。 Furthermore, in the present invention, it is particularly preferred to use an epoxy resin, a phenol resin, and acrylic acid. A resin underfill. Since these resins have few ionic impurities and high heat resistance, the reliability of the semiconductor element can be ensured. In this case, the blending ratio of the epoxy resin and the phenol resin is 50 to 500 parts by weight based on 100 parts by weight of the acrylic resin component.

(熱硬化促進觸媒) (thermal hardening promotes catalyst)

作為環氧樹脂與酚系樹脂之熱硬化促進觸媒，並無特別限制，可自公知之熱硬化促進觸媒中適當選擇而使用。熱硬化促進觸媒可單獨使用或組合2種以上使用。作為熱硬化促進觸媒，例如可使用胺系硬化促進劑、磷系硬化促進劑、咪唑系硬化促進劑、硼系硬化促進劑、磷-硼系硬化促進劑等。 The thermosetting-promoting catalyst of the epoxy resin and the phenol resin is not particularly limited, and can be appropriately selected from known thermal hardening catalysts. The thermosetting-suppressing catalyst may be used singly or in combination of two or more. As the thermosetting-promoting catalyst, for example, an amine-based curing accelerator, a phosphorus-based curing accelerator, an imidazole-based curing accelerator, a boron-based curing accelerator, a phosphorus-boron-based curing accelerator, or the like can be used.

(交聯劑) (crosslinking agent)

於預先使本實施形態之底部填充材2某種程度交聯之情形時，製作時可添加與聚合物之分子鏈末端之官能基等反應之多官能性化合物作為交聯劑。藉此，可使高溫下之接著特性提高且實現耐熱性之改善。 When the underfill material 2 of the present embodiment is crosslinked to some extent in advance, a polyfunctional compound which reacts with a functional group at the end of the molecular chain of the polymer or the like may be added as a crosslinking agent at the time of production. Thereby, the subsequent characteristics at a high temperature can be improved and the improvement in heat resistance can be achieved.

作為上述交聯劑，尤其是甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、對苯二異氰酸酯、1,5-萘二異氰酸酯、多元醇與二異氰酸酯之加成物等聚異氰酸酯化合物更佳。作為交聯劑之添加量，相對於上述聚合物100重量份，通常較佳為設為0.05~7重量份。若交聯劑之量多於7重量份，則接著力下降，因而欠佳。另一方面，若少於0.05重量份，則凝聚力不足，因而欠佳。又，亦可與上述聚異氰酸酯化合物一併視需要而含有環氧樹脂等其他多官能性化合物。 As the above-mentioned crosslinking agent, a polyisocyanate compound such as toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, or an adduct of a polyhydric alcohol and a diisocyanate is more preferable. The amount of the crosslinking agent to be added is usually preferably 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. If the amount of the crosslinking agent is more than 7 parts by weight, the subsequent force is lowered, which is not preferable. On the other hand, if it is less than 0.05 part by weight, the cohesive strength is insufficient, which is not preferable. Further, other polyfunctional compounds such as an epoxy resin may be contained together with the above polyisocyanate compound as needed.

(無機填充劑) (inorganic filler)

又，底部填充材2中可適當調配無機填充劑。無機填充劑之調配可賦予導電性或提高導熱性、調節儲存模數。 Further, an inorganic filler can be appropriately formulated in the underfill material 2. The formulation of the inorganic filler can impart conductivity or improve thermal conductivity and adjust the storage modulus.

作為上述無機填充劑，例如可列舉：二氧化矽、黏土、石膏、 碳酸鈣、硫酸鋇、氧化鋁、氧化鈹、碳化矽、氮化矽等陶瓷類；鋁、銅、銀、金、鎳、鉻、鉛、錫、鋅、鈀、焊料等金屬或合金類；以及包含碳等之各種無機粉末。該等可單獨使用或併用2種以上。其中，可較佳地使用二氧化矽、尤其是熔融二氧化矽。 Examples of the inorganic filler include cerium oxide, clay, and gypsum. Ceramics such as calcium carbonate, barium sulfate, aluminum oxide, barium oxide, tantalum carbide, tantalum nitride; metals or alloys such as aluminum, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, solder; It contains various inorganic powders such as carbon. These may be used alone or in combination of two or more. Among them, cerium oxide, especially molten cerium oxide, can be preferably used.

無機填充劑之平均粒徑雖然並無特別限定，但較佳為0.005~10μm之範圍內，更佳為0.01~5μm之範圍內，進而較佳為0.05~2.0μm。若上述無機填充劑之平均粒徑低於0.005μm，則存在容易發生粒子之凝聚而難以形成底部填充材之情形。又，亦成為底部填充材之可撓性下降之原因。另一方面，若上述平均粒徑超過10μm，則容易發生無機粒子嵌入底部填充材與被黏著體之接合部，因此有半導體裝置之連接可靠性下降之虞。又，有因粒子之粗大化而霧度上升之虞。再者，於本發明中，亦可將平均粒徑相互不同之無機填充劑彼此組合而使用。又，平均粒徑係藉由光度式粒度分佈計(HORIBA製造，裝置名：LA-910)所求出之值。 The average particle diameter of the inorganic filler is not particularly limited, but is preferably in the range of 0.005 to 10 μm, more preferably in the range of 0.01 to 5 μm, still more preferably 0.05 to 2.0 μm. When the average particle diameter of the inorganic filler is less than 0.005 μm, aggregation of particles tends to occur, and it is difficult to form an underfill material. Moreover, it also becomes a cause of the decrease in the flexibility of the underfill material. On the other hand, when the average particle diameter exceeds 10 μm, the inorganic particles are likely to be embedded in the joint portion between the underfill material and the adherend, and thus the connection reliability of the semiconductor device is lowered. In addition, there is a rise in haze due to coarsening of particles. Further, in the present invention, inorganic fillers having different average particle diameters from each other may be used in combination with each other. Further, the average particle diameter is a value obtained by a photometric particle size distribution meter (manufactured by HORIBA, device name: LA-910).

上述無機填充劑之調配量係相對於樹脂成分100重量份較佳為10~400重量份，更佳為50~250重量份。若無機填充劑之調配量未達10重量份，則存在儲存模數下降而封裝體之應力可靠性嚴重受損之情形。另一方面，若超過400重量份，則存在底部填充材2之流動性下降不能充分地埋入至基板或半導體元件之凹凸而成為空隙或龜裂之原因的情形。 The amount of the inorganic filler to be added is preferably 10 to 400 parts by weight, more preferably 50 to 250 parts by weight, per 100 parts by weight of the resin component. If the amount of the inorganic filler is less than 10 parts by weight, there is a case where the storage modulus is lowered and the stress reliability of the package is seriously impaired. On the other hand, when it exceeds 400 parts by weight, the fluidity of the underfill material 2 may not be sufficiently buried in the unevenness of the substrate or the semiconductor element to cause voids or cracks.

(其他添加劑) (other additives)

再者，底部填充材2中除上述無機填充劑以外，視需要亦可適當調配其他添加劑。作為其他添加劑，例如可列舉：阻燃劑、矽烷偶合劑或離子捕捉劑等。作為上述阻燃劑，例如可列舉：三氧化銻、五氧化銻、溴化環氧樹脂等。該等可單獨使用或併用2種以上。作為上述矽烷偶合劑，例如可列舉：β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ- 縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷等。該等化合物可單獨使用或併用2種以上。作為上述離子捕捉劑，例如可列舉：鋁碳酸鎂類、氫氧化鉍等。該等可單獨使用或併用2種以上。 Further, in addition to the above inorganic filler, the underfill material 2 may be appropriately blended with other additives as needed. Examples of other additives include a flame retardant, a decane coupling agent, and an ion scavenger. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. These may be used alone or in combination of two or more. Examples of the above decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane and γ-. Glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, and the like. These compounds may be used alone or in combination of two or more. Examples of the ion scavenger include aluminum magnesium carbonate and barium hydroxide. These may be used alone or in combination of two or more.

(底部填充材之其他性狀) (Other properties of the underfill)

於本實施形態中，熱硬化處理前上述底部填充材較佳為具有100~200℃下之黏度成為20000Pa．s以下之區域，更佳為具有成為100Pa．s以上且10000Pa．s以下之區域。藉由於上述溫度範圍內具有特定之黏度區域，可使連接構件4(參照圖2A)容易地進入至底部填充材2。又，可防止於半導體元件5之電性連接時產生空隙及底部填充材2自半導體元件5與被黏著體16之間之空間溢出(參照圖2F)。 In the present embodiment, the underfill material before the thermosetting treatment preferably has a viscosity at 100 to 200 ° C of 20,000 Pa. The area below s, better to have become 100Pa. s above and 10000Pa. s below the area. By having a specific viscosity region within the above temperature range, the connecting member 4 (refer to FIG. 2A) can be easily introduced into the underfill material 2. Further, it is possible to prevent voids from occurring during electrical connection of the semiconductor element 5 and overflow of the underfill material 2 from the space between the semiconductor element 5 and the adherend 16 (see FIG. 2F).

熱硬化處理前，上述底部填充材於100~200℃下之最低黏度較佳為0.1Pa．s以上且10000Pa．s以下，更佳為1Pa．s以上且5000Pa．s以下，進而較佳為10Pa．s以上且3000Pa．s以下。藉此，可於底部填充材與半導體晶圓貼合時使連接構件容易進入至底部填充材。又，可防止半導體元件之電性連接時產生空隙及底部填充材自半導體元件與被黏著體之間之空間溢出。 Before the heat hardening treatment, the minimum viscosity of the underfill material at 100 to 200 ° C is preferably 0.1 Pa. s above and 10000Pa. Below s, more preferably 1Pa. Above s and 5000Pa. s is below, and further preferably 10 Pa. s above and 3000Pa. s below. Thereby, the connecting member can be easily accessed to the underfill material when the underfill material is bonded to the semiconductor wafer. Further, it is possible to prevent voids from occurring in electrical connection of the semiconductor element and overflow of the underfill material from the space between the semiconductor element and the adherend.

又，熱硬化前之上述底部填充材2於23℃下之黏度較佳為0.01MPa．s以上且100MPa．s以下，更佳為0.1MPa．s以上且10MPa．s以下。熱硬化前之底部填充材藉由具有上述範圍之黏度，可使背面研削時之半導體晶圓3(參照圖2B)之保持性或作業時之使用性提高。再者，上述最低黏度及黏度之測定可按照實施例記載之順序進行。 Moreover, the viscosity of the underfill material 2 before thermal hardening at 23 ° C is preferably 0.01 MPa. s above and 100MPa. Below s, more preferably 0.1 MPa. s above and 10MPa. s below. By having the viscosity in the above range, the underfill material before the heat hardening can improve the retentivity of the semiconductor wafer 3 (see FIG. 2B) at the time of back grinding or the workability at the time of work. Further, the measurement of the minimum viscosity and the viscosity described above can be carried out in the order described in the examples.

進而，熱硬化前之上述底部填充材2於溫度23℃、濕度70%之條件下之吸水率較佳為1重量%以下，更佳為0.5重量%以下。底部填充材2藉由具有如上所述之吸水率而抑制水分於底部填充材2中之吸收，可更有效率地抑制安裝半導體元件5時產生空隙。再者，上述吸水率 之下限越小越佳，較佳為實質上為0重量%，更佳為0重量%。 Further, the water absorption rate of the underfill material 2 before the thermal curing at a temperature of 23 ° C and a humidity of 70% is preferably 1% by weight or less, more preferably 0.5% by weight or less. The underfill material 2 suppresses the absorption of moisture in the underfill material 2 by having the water absorption rate as described above, and it is possible to more effectively suppress the occurrence of voids when the semiconductor element 5 is mounted. Furthermore, the above water absorption rate The lower limit is preferably as small as possible, and is preferably substantially 0% by weight, more preferably 0% by weight.

底部填充材2之厚度(於複數層之情形時為總厚)並無特別限定，但若考慮到底部填充材2之強度或半導體元件5與被黏著體16之間之空間之填充性，亦可為10μm以上且100μm以下左右。再者，底部填充材2之厚度考慮半導體元件5與被黏著體16之間之間隙或連接構件之高度而適當設定即可。 The thickness of the underfill material 2 (the total thickness in the case of the plurality of layers) is not particularly limited, but in consideration of the strength of the underfill material 2 or the filling property of the space between the semiconductor element 5 and the adherend 16 It can be about 10 μm or more and about 100 μm or less. Further, the thickness of the underfill material 2 may be appropriately set in consideration of the gap between the semiconductor element 5 and the adherend 16 or the height of the connecting member.

積層片10之底部填充材2較佳為受隔片保護(未圖示)。隔片具有作為保護底部填充材2直至供於實際使用前的保護材之功能。隔片係於積層片之底部填充材2上貼著半導體晶圓3時被剝離。作為隔片，亦可使用藉由聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯或氟系剝離劑、長鏈烷基丙烯酸酯系剝離劑等剝離劑塗佈表面之塑膠膜或紙等。 The underfill 2 of the laminated sheet 10 is preferably protected by a spacer (not shown). The separator has a function as a protective material for protecting the underfill material 2 until it is actually used. The separator is peeled off when the semiconductor wafer 3 is attached to the underfill material 2 of the laminated sheet. As the separator, a plastic film coated on the surface by a release agent such as polyethylene terephthalate (PET), polyethylene, polypropylene or a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used. Or paper, etc.

(積層片之製造方法) (Manufacturing method of laminated sheet)

本實施形態之積層片10例如可藉由分別製作背面研削用帶1及底部填充材2並於最後將該等貼合而製成。具體而言，可按照如下所述之順序而製作。 The laminated sheet 10 of the present embodiment can be produced, for example, by separately forming the back grinding tape 1 and the underfill material 2 and bonding them at the end. Specifically, it can be produced in the order described below.

首先，基材1a可藉由先前公知之製膜方法而製膜。作為該製膜方法，例如可例示壓延製膜法、有機溶劑中之流延法、密閉系統中之吹脹擠出法、T型模頭擠出法、共擠出法、乾式層壓法等。 First, the substrate 1a can be formed into a film by a conventionally known film forming method. Examples of the film forming method include a calender film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, a dry lamination method, and the like. .

繼而，製備黏著劑層形成用之黏著劑組合物。黏著劑組合物中調配有黏著劑層一項中說明之樹脂或添加物等。將所製備之黏著劑組合物塗佈於基材1a上形成塗佈膜後，使該塗佈膜於特定條件下乾燥(視需要使其加熱交聯)而形成黏著劑層1b。塗佈方法並無特別限定，例如可列舉：輥塗敷、網版塗敷、凹版塗敷等。又，作為乾燥條件，例如可於乾燥溫度80~150℃、乾燥時間0.5~5分鐘之範圍內進行。又，亦可於隔片上塗佈黏著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成黏著劑層1b。其後將黏著劑層1b與隔片一併 貼合至基材1a上。藉此，可製作具備基材1a及黏著劑層1b之背面研削用帶1。 Then, an adhesive composition for forming an adhesive layer is prepared. A resin or an additive described in the section of the adhesive layer is formulated in the adhesive composition. After the prepared adhesive composition is applied onto the substrate 1a to form a coating film, the coating film is dried under specific conditions (heat-crosslinking if necessary) to form an adhesive layer 1b. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions can be carried out, for example, at a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Further, after the adhesive composition is applied onto the separator to form a coating film, the coating film is dried under the above drying conditions to form the adhesive layer 1b. Thereafter, the adhesive layer 1b is combined with the separator. It is bonded to the substrate 1a. Thereby, the back grinding belt 1 provided with the base material 1a and the adhesive layer 1b can be manufactured.

底部填充材2例如可以如下所述之方式製作。首先，製備作為底部填充材2之形成材料之接著劑組合物。如底部填充材之項中說明般，該接著劑組合物中調配有熱塑性成分或環氧樹脂、各種添加劑等。 The underfill material 2 can be produced, for example, as follows. First, an adhesive composition as a forming material of the underfill material 2 is prepared. As described in the item of the underfill, the adhesive composition is formulated with a thermoplastic component or an epoxy resin, various additives, and the like.

繼而，將所製備之接著劑組合物以成為特定厚度之方式塗佈於基材隔片上而形成塗佈膜後，使該塗佈膜於特定條件下乾燥而形成底部填充材。塗佈方法並無特別限定，例如可列舉：輥塗敷、網版塗敷、凹版塗敷等。又，作為乾燥條件，例如可於乾燥溫度70~160℃、乾燥時間1~5分鐘之範圍內進行。又，亦可於隔片上塗佈接著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成底部填充材。其後將底部填充材與隔片一併貼合至基材隔片上。 Then, the prepared adhesive composition is applied onto a substrate separator so as to have a specific thickness to form a coating film, and then the coating film is dried under specific conditions to form an underfill. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions can be carried out, for example, at a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Further, after applying the adhesive composition to the separator to form a coating film, the coating film is dried under the above drying conditions to form an underfill material. Thereafter, the underfill material is attached to the substrate separator together with the separator.

繼而，自背面研削用帶1及底部填充材2分別剝離隔片，以底部填充材與黏著劑層成為貼合面之方式貼合兩者。貼合例如可藉由壓接而進行。此時，層壓溫度並無特別限定，例如較佳為30~100℃，更佳為40~80℃。又，線壓並無特別限定，例如較佳為0.98~196N/cm，更佳為9.8~98N/cm。繼而，將底部填充材上之基材隔片剝離而獲得本實施形態之積層片。 Then, the separator is peeled off from the back grinding belt 1 and the underfill 2, and the underfill and the pressure-sensitive adhesive layer are bonded to each other. The bonding can be performed, for example, by crimping. In this case, the laminating temperature is not particularly limited, and is, for example, preferably from 30 to 100 ° C, more preferably from 40 to 80 ° C. Further, the linear pressure is not particularly limited, and is, for example, preferably 0.98 to 196 N/cm, more preferably 9.8 to 98 N/cm. Then, the base sheet on the underfill material was peeled off to obtain a laminated sheet of the present embodiment.

[貼合步驟] [Finishing step]

於貼合步驟中，將半導體晶圓3之形成有連接構件4之電路面3a與上述積層片10之底部填充材2貼合(參照圖2A)。 In the bonding step, the circuit surface 3a of the semiconductor wafer 3 on which the connection member 4 is formed is bonded to the underfill material 2 of the laminated sheet 10 (see FIG. 2A).

(半導體晶圓) (semiconductor wafer)

半導體晶圓3之電路面3a形成有複數個連接構件4(參照圖2A)。作為凸塊或導電材等連接構件之材質，並無特別限定，例如可列舉：錫-鉛系金屬材、錫-銀系金屬材、錫-銀-銅系金屬材、錫-鋅系金屬材、 錫-鋅-鉍系金屬材等焊料類(合金)、或金系金屬材、銅系金屬材等。連接構件之高度亦可根據用途而決定，通常為15~100μm左右。當然，半導體晶圓3中之各個連接構件之高度可相同亦可不同。 A plurality of connection members 4 are formed on the circuit surface 3a of the semiconductor wafer 3 (see FIG. 2A). The material of the connecting member such as a bump or a conductive material is not particularly limited, and examples thereof include a tin-lead metal material, a tin-silver metal material, a tin-silver-copper metal material, and a tin-zinc metal material. , A solder (alloy) such as a tin-zinc-bismuth metal material, a gold-based metal material, or a copper-based metal material. The height of the connecting member can also be determined depending on the application, and is usually about 15 to 100 μm. Of course, the heights of the respective connecting members in the semiconductor wafer 3 may be the same or different.

於本實施形態之半導體裝置之製造方法中，作為底部填充材之厚度，較佳為形成於半導體晶圓表面之連接構件之高度X(μm)與上述底部填充材之厚度Y(μm)滿足下述關係。 In the method of manufacturing a semiconductor device of the present embodiment, it is preferable that the thickness of the underfill material is such that the height X (μm) of the connection member formed on the surface of the semiconductor wafer and the thickness Y (μm) of the underfill material are satisfied. Relationship.

0.5≦Y/X≦2 0.5≦Y/X≦2

藉由使上述連接構件之高度X(μm)與上述硬化膜之厚度Y(μm)滿足上述關係，可充分地填充半導體元件與被黏著體之間之空間，並且可防止底部填充材自該空間之過度溢出，可防止由底部填充材污染半導體元件等。再者，於各連接構件之高度不同之情形時，以最高之連接構件之高度為基準。 By satisfying the above relationship between the height X (μm) of the connecting member and the thickness Y (μm) of the cured film, the space between the semiconductor element and the adherend can be sufficiently filled, and the underfill can be prevented from the space. Excessive overflow prevents contamination of semiconductor components and the like by the underfill material. Furthermore, in the case where the heights of the respective connecting members are different, the height of the highest connecting member is used as a reference.

(貼合) (fit)

首先，適當地剝離任意地設置於積層片10之底部填充材2上之隔片，並如圖2A所示，使上述半導體晶圓3之形成有連接構件4之電路面3a與底部填充材2對向，而將上述底部填充材2與上述半導體晶圓3貼合(安裝)。 First, the separator arbitrarily disposed on the underfill material 2 of the laminated sheet 10 is appropriately peeled off, and as shown in FIG. 2A, the circuit surface 3a of the semiconductor wafer 3 on which the connecting member 4 is formed and the underfill material 2 are formed. The underfill material 2 is bonded (mounted) to the semiconductor wafer 3 in the opposite direction.

貼合之方法並無特別限定，較佳為藉由壓接之方法。壓接通常藉由壓接輥等公知之按壓器件負以較佳為0.1~1MPa、更佳為0.3~0.7MPa之壓力一面按壓一面進行。此時，亦可一面加熱至40~100℃左右一面壓接。又，為了提高密接性，亦較佳為於減壓下(1~1000Pa)壓接。 The method of bonding is not particularly limited, and is preferably a method of crimping. The pressure bonding is usually carried out by pressing a known pressing device such as a pressure roller at a pressure of preferably 0.1 to 1 MPa, more preferably 0.3 to 0.7 MPa. At this time, it is also possible to press it while heating to about 40 to 100 °C. Further, in order to improve the adhesion, it is also preferred to press under pressure (1 to 1000 Pa).

[研削步驟] [grinding step]

於研削步驟中，對上述半導體晶圓3之與電路面3a相反側之面(即背面)3b進行研削(參照圖2B)。半導體晶圓3之背面研削所使用之薄型加工機並無特別限定，例如可例示研削機(背面研磨機)、研磨墊等。 又，亦可利用蝕刻等化學方法進行背面研削。背面研削係進行至半導體晶圓成為所需之厚度(例如700~25μm)。 In the grinding step, the surface (ie, the back surface) 3b of the semiconductor wafer 3 opposite to the circuit surface 3a is ground (see FIG. 2B). The thin processing machine used for the back grinding of the semiconductor wafer 3 is not particularly limited, and examples thereof include a grinding machine (back grinding machine), a polishing pad, and the like. Further, back grinding can be performed by a chemical method such as etching. The back grinding is performed to the desired thickness of the semiconductor wafer (for example, 700 to 25 μm).

[固定步驟] [fixed step]

研削步驟後，於貼附有底部填充材2之狀態下將半導體晶圓3自背面研削用帶1剝離，並將半導體晶圓3與切晶帶11貼合(參照圖2C)。此時，以半導體晶圓3之背面3b與切晶帶11之黏著劑層11b對向之方式貼合。因此，貼合於半導體晶圓3之電路面3a的底部填充材2成為露出之狀態。再者，切晶帶11具有於基材11a上積層有黏著劑層11b之構造。基材11a及黏著劑層11b可使用上述背面研削用帶1之基材1a及黏著劑層1b之項中所示之成分及製法而較佳地製作。 After the grinding step, the semiconductor wafer 3 is peeled off from the back grinding tape 1 in a state in which the underfill material 2 is attached, and the semiconductor wafer 3 is bonded to the dicing tape 11 (see FIG. 2C). At this time, the back surface 3b of the semiconductor wafer 3 is bonded to the adhesive layer 11b of the dicing tape 11 so as to face each other. Therefore, the underfill material 2 bonded to the circuit surface 3a of the semiconductor wafer 3 is exposed. Further, the dicing tape 11 has a structure in which an adhesive layer 11b is laminated on the substrate 11a. The base material 11a and the pressure-sensitive adhesive layer 11b can be preferably produced by using the components and the production method shown in the items of the base material 1a and the pressure-sensitive adhesive layer 1b of the back grinding belt 1.

自背面研削用帶1剝離半導體晶圓3時，於黏著劑層1b具有放射線硬化性之情形時，對黏著劑層1b照射放射線使黏著劑層1b硬化，藉此可容易地進行剝離。放射線之照射量考慮所使用之放射線之種類或黏著劑層之硬化度等而適當設定即可。 When the semiconductor wafer 3 is peeled off from the back-grinding tape 1, when the adhesive layer 1b has radiation curability, the adhesive layer 1b is irradiated with radiation to cure the adhesive layer 1b, whereby peeling can be easily performed. The amount of radiation to be irradiated may be appropriately set in consideration of the type of radiation to be used, the degree of hardening of the adhesive layer, and the like.

本實施形態之積層片較佳為上述底部填充材自上述背面研削用帶之剝離力為0.03~0.10N/20mm。藉由上述輕剝離力，可防止自背面研削用帶剝離時底部填充材之斷裂或變形，並且可防止半導體晶圓之變形。 In the laminated sheet of the present embodiment, it is preferable that the underfill material has a peeling force of 0.03 to 0.10 N/20 mm from the back grinding belt. By the above-described light peeling force, it is possible to prevent breakage or deformation of the underfill material when peeling off from the back side grinding tape, and to prevent deformation of the semiconductor wafer.

上述剝離力之測定係自積層片切下寬度20mm之樣片，將樣片貼附於載置於40℃之加熱板上之矽鏡面晶圓。放置約30分鐘，使用拉伸試驗機測定剝離力。測定條件設為剝離角度：90°、拉伸速度：300mm/min。再者，剝離力之測定係於溫度23℃、相對濕度50%之環境下進行。然而，於黏著劑層為紫外線硬化型之情形時，於與上述相同之條件下貼附於矽鏡面晶圓，放置約30分鐘後，以如下所述之方式設定紫外線之照射條件而自積層片側進行紫外線照射，並進行此時之剝離力之測定。 The peeling force was measured by cutting a swatch having a width of 20 mm from the laminated sheet, and attaching the swatch to a enamel mirror wafer placed on a hot plate at 40 °C. The peeling force was measured using a tensile tester for about 30 minutes. The measurement conditions were a peeling angle: 90° and a tensile speed: 300 mm/min. Further, the measurement of the peeling force was carried out in an environment of a temperature of 23 ° C and a relative humidity of 50%. However, when the adhesive layer is of an ultraviolet curing type, it is attached to the 矽 mirror wafer under the same conditions as described above, and after being left for about 30 minutes, the ultraviolet irradiation conditions are set as described below from the laminated sheet side. Ultraviolet irradiation was performed, and the peeling force at this time was measured.

<紫外線之照射條件> <Ultraviolet irradiation conditions>

紫外線(UV)照射裝置：高壓水銀燈 Ultraviolet (UV) irradiation device: high pressure mercury lamp

紫外線照射累積光量：500mJ/cm2 Accumulated light amount by ultraviolet irradiation: 500mJ/cm 2

輸出：75W Output: 75W

照射強度：150mW/cm2 Irradiation intensity: 150mW/cm 2

[切晶步驟] [Cutting step]

於切晶步驟中，基於利用直接光或間接光、紅外線等所求出之切晶位置如圖2D所示對半導體晶圓3及底部填充材2進行切晶，而形成附有經切晶之底部填充材的半導體元件5。藉由經過切晶步驟，將半導體晶圓3切割成特定尺寸而單片化(小片化)，製造半導體晶片(半導體元件)5。此處所得之半導體晶片5與被切割成該形狀之底部填充材2成為一體。切晶係自半導體晶圓3之貼合有底部填充材2之電路面3a依照常法進行。 In the dicing step, the semiconductor wafer 3 and the underfill material 2 are diced as shown in FIG. 2D based on the dicing position determined by direct light or indirect light, infrared ray, or the like, and the dicing is formed. The semiconductor component 5 of the underfill. The semiconductor wafer 3 (semiconductor element) 5 is manufactured by dicing the semiconductor wafer 3 into a specific size and dicing it in a dicing step. The semiconductor wafer 5 obtained here is integrated with the underfill material 2 cut into the shape. The dicing system is performed from the semiconductor wafer 3 to which the circuit surface 3a of the underfill material 2 is bonded in accordance with a conventional method.

於本步驟中，例如可採用利用切晶刀片切入至切晶帶11為止的被稱為全切之切割方式等。本步驟中所使用之切晶裝置並無特別限定，可使用先前公知者。又，半導體晶圓係被切晶帶11以優異之密接性接著固定，因此可抑制晶片缺損或晶片鼓出，並且亦可抑制半導體晶圓之破損。再者，若底部填充材由含有環氧樹脂之樹脂組合物形成，則即便藉由切晶被切割，亦可抑制或防止於該切割面產生底部填充材之底部填充材之糊劑溢出。其結果為，可抑制或防止切割面彼此再附著(黏連)，可進一步良好地進行下述拾取。 In this step, for example, a cutting method called a full cut using a dicing blade to cut into the dicing tape 11 can be employed. The crystal cutting device used in this step is not particularly limited, and those known in the prior art can be used. Further, since the semiconductor wafer is fixed by the dicing tape 11 with excellent adhesion, it is possible to suppress wafer defects or wafer bulging, and it is also possible to suppress breakage of the semiconductor wafer. Further, when the underfill material is formed of a resin composition containing an epoxy resin, even if it is cut by dicing, the paste overflow of the underfill material of the underfill material can be suppressed or prevented from occurring on the cut surface. As a result, it is possible to suppress or prevent the cut surfaces from reattaching (adhesion) to each other, and the following pick-up can be performed more satisfactorily.

再者，於繼切晶步驟後進行切晶帶之擴展之情形時，該擴展可使用先前公知之擴展裝置而進行。擴展裝置具有經由切晶環可將切晶帶向下方按壓之環狀外圈、及直徑小於外圈且支持切晶帶之內圈。藉由該擴展步驟，於下述拾取步驟中可防止相鄰之半導體晶片彼此接觸而破損。 Further, in the case where the dicing band is expanded after the dicing step, the expansion can be carried out using a previously known expansion device. The expansion device has an annular outer ring that can press the dicing tape downward through the dicing ring, and an inner ring that has a smaller diameter than the outer ring and supports the dicing band. By this expansion step, adjacent semiconductor wafers can be prevented from coming into contact with each other and broken in the pickup step described below.

[拾取步驟] [pickup step]

為了回收接著固定於切晶帶11之半導體晶片5，如圖2E所示，拾取附有底部填充材2之半導體晶片5，將半導體晶片5與底部填充材2之積層體A自切晶帶11剝離。 In order to recover the semiconductor wafer 5 which is then fixed to the dicing tape 11, as shown in FIG. 2E, the semiconductor wafer 5 with the underfill 2 is picked up, and the laminated body A of the semiconductor wafer 5 and the underfill 2 is self-cutting. Stripped.

拾取之方法並無特別限定，可採用先前公知之各種方法。例如可列舉如下方法等：藉由針將各個半導體晶片自切晶帶之基材側頂起，藉由拾取裝置拾取被頂起之半導體晶片。再者，所拾取之半導體晶片5與貼合於電路面3a之底部填充材2成為一體而構成積層體A。 The method of picking up is not particularly limited, and various methods previously known can be employed. For example, a method in which each of the semiconductor wafers is lifted from the substrate side of the dicing tape by the needle, and the lifted semiconductor wafer is picked up by the pickup device. Further, the semiconductor wafer 5 picked up is integrated with the underfill material 2 bonded to the circuit surface 3a to form a laminated body A.

於黏著劑層11b為紫外線硬化型之情形時，拾取係於對該黏著劑層11b照射紫外線後進行。藉此，黏著劑層11b對半導體晶片5之黏著力下降，半導體晶片5之剝離變容易。其結果為，可不損傷半導體晶片5而將其拾取。照射紫外線時之照射強度、照射時間等條件並無特別限定，只要視需要適當設定即可。又，作為紫外線照射所使用之光源，例如可使用低壓水銀燈、低壓高輸出燈、中壓水銀燈、無電極水銀燈、氙氣閃光燈、準分子燈、紫外LED等。 In the case where the adhesive layer 11b is of an ultraviolet curing type, the pickup is performed by irradiating the adhesive layer 11b with ultraviolet rays. Thereby, the adhesive force of the adhesive layer 11b to the semiconductor wafer 5 is lowered, and the peeling of the semiconductor wafer 5 becomes easy. As a result, the semiconductor wafer 5 can be picked up without damaging it. The conditions such as the irradiation intensity and the irradiation time when the ultraviolet ray is irradiated are not particularly limited, and may be appropriately set as necessary. Further, as the light source used for the ultraviolet irradiation, for example, a low pressure mercury lamp, a low pressure high output lamp, a medium pressure mercury lamp, an electrodeless mercury lamp, a xenon flash lamp, an excimer lamp, an ultraviolet LED, or the like can be used.

[安裝步驟] [installation steps]

於安裝步驟中，藉由直接光或間接光、紅外線等預先求出半導體元件5之安裝位置，按照所求得之安裝位置，用底部填充材2填充被黏著體16與半導體元件5之間之空間，並且經由連接構件4將半導體元件5與被黏著體16電性連接(參照圖2F)。具體而言，使積層體A之半導體晶片5以半導體晶片5之電路面3a與被黏著體16對向之形態依照常法固定於被黏著體16。例如，使形成於半導體晶片5之凸塊(連接構件)4與被接著於被黏著體16之連接墊的接合用導電材17(焊料等)接觸，一面按壓一面使導電材熔融，藉此，可確保半導體晶片5與被黏著體16之電性連接，並使半導體晶片5固定於被黏著體16。半導體晶片5之電路面3a上貼附有底部填充材2，因此半導體晶片5與被黏著體16電性連 接，同時半導體晶片5與被黏著體16之間之空間被底部填充材2填充。 In the mounting step, the mounting position of the semiconductor element 5 is obtained in advance by direct light, indirect light, infrared light or the like, and the underfill material 2 is filled between the adherend 16 and the semiconductor element 5 in accordance with the obtained mounting position. The space and the semiconductor element 5 are electrically connected to the adherend 16 via the connecting member 4 (refer to FIG. 2F). Specifically, the semiconductor wafer 5 of the laminated body A is fixed to the adherend 16 in a conventional manner in such a manner that the circuit surface 3a of the semiconductor wafer 5 faces the adherend 16 . For example, the bump (connection member) 4 formed on the semiconductor wafer 5 is brought into contact with the bonding conductive material 17 (solder or the like) which is next to the connection pad of the adherend 16, and the conductive material is melted while being pressed. The semiconductor wafer 5 can be electrically connected to the adherend 16 and the semiconductor wafer 5 can be fixed to the adherend 16. The underlying material 2 is attached to the circuit surface 3a of the semiconductor wafer 5, so that the semiconductor wafer 5 is electrically connected to the adherend 16 At the same time, the space between the semiconductor wafer 5 and the adherend 16 is filled with the underfill material 2.

通常，安裝步驟中之加熱條件為100~300℃，加壓條件為0.5~500N。又，亦可以多階段進行安裝步驟中之熱壓接處理。例如，可採用於150℃、100N下處理10秒後於300℃、100~200N下處理10秒的順序。藉由以多階段進行熱壓接處理，可高效率地去除連接構件與墊間之樹脂，可獲得更良好之金屬間接合。 Usually, the heating conditions in the mounting step are 100 to 300 ° C, and the pressing conditions are 0.5 to 500 N. Further, the thermocompression bonding process in the mounting step may be performed in multiple stages. For example, the order of treatment at 100 ° C for 10 seconds at 100 ° C and 100 ° C for 100 seconds may be employed. By performing the thermocompression bonding treatment in multiple stages, the resin between the connecting member and the mat can be efficiently removed, and a better intermetallic joining can be obtained.

作為被黏著體16，可使用半導體晶圓、導線架或電路基板(配線電路基板等)等各種基板、其他半導體元件。作為基板之材質，並無特別限定，可列舉陶瓷基板或塑膠基板。作為塑膠基板，例如可列舉：環氧基板、雙順丁烯二醯亞胺三基板、聚醯亞胺基板、玻璃環氧基板等。安裝於1個被黏著體之半導體元件之數量亦無限定，可為1個或複數個之任一者。底部填充材2亦可較佳地用於在半導體晶圓上安裝多個半導體晶片之晶片磊晶圓製程。 As the adherend 16, various substrates such as a semiconductor wafer, a lead frame, or a circuit board (such as a printed circuit board) and other semiconductor elements can be used. The material of the substrate is not particularly limited, and examples thereof include a ceramic substrate and a plastic substrate. As the plastic substrate, for example, an epoxy substrate, bis-methylenediimide, and the like are mentioned. A substrate, a polyimide substrate, a glass epoxy substrate, or the like. The number of semiconductor elements mounted on one of the adherends is not limited, and may be one or plural. The underfill material 2 can also be preferably used in a wafer wafer wafer process in which a plurality of semiconductor wafers are mounted on a semiconductor wafer.

再者，於安裝步驟中，使連接構件及導電材之一者或兩者熔融而使半導體晶片5之連接構件形成面3a之凸塊4與被黏著體16之表面之導電材17連接，作為該凸塊4及導電材17之熔融時之溫度，通常為260℃左右(例如250℃~300℃)。本實施形態之積層片藉由利用環氧樹脂等形成底部填充材2，可製成具有亦可耐受該安裝步驟中之高溫之耐熱性者。 Further, in the mounting step, one or both of the connecting member and the conductive material are melted to connect the bump 4 of the connecting member forming surface 3a of the semiconductor wafer 5 to the conductive material 17 on the surface of the adherend 16 as The temperature at which the bump 4 and the conductive material 17 are melted is usually about 260 ° C (for example, 250 ° C to 300 ° C). The laminated sheet of the present embodiment can be formed into an underfill material 2 by using an epoxy resin or the like, and can have a heat resistance which can withstand the high temperature in the mounting step.

[底部填充材硬化步驟] [Bottom filler hardening step]

進行半導體元件5與被黏著體16之電性連接後，藉由加熱使底部填充材2硬化。藉此，可保護半導體元件5之表面，並且可確保半導體元件5與被黏著體16之間之連接可靠性。用以使底部填充材硬化之加熱溫度並無特別限定，為150~250℃左右即可。再者，於藉由安裝步驟中之加熱處理而底部填充材硬化之情形時，本步驟可省略。 After the semiconductor element 5 is electrically connected to the adherend 16, the underfill material 2 is cured by heating. Thereby, the surface of the semiconductor element 5 can be protected, and the connection reliability between the semiconductor element 5 and the adherend 16 can be ensured. The heating temperature for hardening the underfill material is not particularly limited and may be about 150 to 250 °C. Furthermore, this step can be omitted when the underfill material is hardened by the heat treatment in the mounting step.

[密封步驟] [sealing step]

繼而，為了保護具備經安裝之半導體晶片5之半導體裝置20整體，亦可進行密封步驟。密封步驟可使用密封樹脂而進行。此時之密封條件並無特別限定，通常藉由於175℃下進行60秒~90秒之加熱，而進行密封樹脂之熱硬化，但本發明並不限定於此，例如可於165℃~185℃下固化數分鐘。 Then, in order to protect the entire semiconductor device 20 having the mounted semiconductor wafer 5, a sealing step may be performed. The sealing step can be carried out using a sealing resin. The sealing condition at this time is not particularly limited, and the sealing resin is usually thermally cured by heating at 175 ° C for 60 seconds to 90 seconds. However, the present invention is not limited thereto, and may be, for example, 165 ° C to 185 ° C. Cure for a few minutes.

作為上述密封樹脂，只要為具有絕緣性之樹脂(絕緣樹脂)則並無特別限制，可自公知之密封樹脂等密封材中適當選擇而使用，更佳為具有彈性之絕緣樹脂。作為密封樹脂，例如可列舉含有環氧樹脂之樹脂組合物等。作為環氧樹脂，可列舉上述所例示之環氧樹脂等。又，作為由含有環氧樹脂之樹脂組合物所獲得之密封樹脂，作為樹脂成分，除環氧樹脂以外，亦可含有環氧樹脂以外之熱硬化性樹脂(酚系樹脂等)或熱塑性樹脂等。再者，酚系樹脂亦可用作環氧樹脂之硬化劑，作為上述酚系樹脂，可列舉上述所例示之酚系樹脂等。 The sealing resin is not particularly limited as long as it is an insulating resin (insulating resin), and can be appropriately selected from known sealing materials such as sealing resins, and more preferably an insulating resin having elasticity. The sealing resin may, for example, be a resin composition containing an epoxy resin. Examples of the epoxy resin include the epoxy resins exemplified above. In addition, the sealing resin obtained from the epoxy resin-containing resin composition may contain, as a resin component, a thermosetting resin (such as a phenol resin) other than an epoxy resin, or a thermoplastic resin, in addition to the epoxy resin. . In addition, the phenolic resin can also be used as a curing agent for an epoxy resin, and examples of the phenolic resin include the phenolic resins exemplified above.

[半導體裝置] [semiconductor device]

繼而，一面參照圖式一面對使用該積層片所得之半導體裝置進行說明(參照圖2F)。本實施形態之半導體裝置20中，半導體元件5與被黏著體16係經由形成於半導體元件5上之凸塊(連接構件)4及設置於被黏著體16上之導電材17而電性連接。又，於半導體元件5與被黏著體16之間以填充該空間之方式配置有底部填充材2。半導體裝置20可利用採用特定底部填充材2及由光照射獲得之定位的上述製造方法而獲得，因此可於半導體元件5與被黏著體16之間達成良好之電性連接。因此，半導體元件5之表面保護、半導體元件5與被黏著體16之間之空間之填充、及半導體元件5與被黏著體16之間之電性連接分別成為充分之級別，作為半導體裝置20可發揮較高之可靠性。 Next, a semiconductor device obtained by using the laminated sheet will be described with reference to the drawings (see FIG. 2F). In the semiconductor device 20 of the present embodiment, the semiconductor element 5 and the adherend 16 are electrically connected via a bump (connection member) 4 formed on the semiconductor element 5 and a conductive material 17 provided on the adherend 16. Further, the underfill material 2 is disposed between the semiconductor element 5 and the adherend 16 so as to fill the space. The semiconductor device 20 can be obtained by the above-described manufacturing method using the specific underfill material 2 and the positioning obtained by light irradiation, so that a good electrical connection can be achieved between the semiconductor element 5 and the adherend 16. Therefore, the surface protection of the semiconductor element 5, the filling of the space between the semiconductor element 5 and the adherend 16 , and the electrical connection between the semiconductor element 5 and the adherend 16 are respectively sufficient levels, and the semiconductor device 20 can be used. Play a higher level of reliability.

<第2實施形態> <Second embodiment>

第1實施形態中使用單面形成有電路之半導體晶圓，與此相對 地，本實施形態中使用兩面形成有電路之半導體晶圓製造半導體裝置。又，本實施形態中所使用之半導體晶圓具有目標厚度，因此省略研削步驟。因此，作為第2實施形態中之積層片，使用具備切晶帶與積層於該切晶帶上之特定底部填充材的積層片。作為較第2實施形態中之對位步驟前之代表性步驟，可列舉：準備步驟，其係準備上述積層片；貼合步驟，其係將兩面形成有具有連接構件之電路面之半導體晶圓與上述積層片之底部填充材貼合；切晶步驟，其係對上述半導體晶圓進行切晶而形成附有上述底部填充材之半導體元件；拾取步驟，其係將附有上述底部填充材之半導體元件自上述積層片剝離。其後，進行對位步驟以後之步驟而製造半導體裝置。 In the first embodiment, a semiconductor wafer in which a circuit is formed on one side is used. In the present embodiment, a semiconductor device is fabricated using a semiconductor wafer having circuits formed on both sides. Further, since the semiconductor wafer used in the present embodiment has a target thickness, the grinding step is omitted. Therefore, as the laminated sheet in the second embodiment, a laminated sheet having a dicing tape and a specific underfill layer laminated on the dicing tape is used. The representative step before the alignment step in the second embodiment includes a preparation step of preparing the laminated sheet, and a bonding step of forming a semiconductor wafer having a circuit surface having a connecting member on both sides. Bonding to the underfill of the laminated sheet; a dicing step of dicing the semiconductor wafer to form a semiconductor component with the underfill; and a picking step of attaching the underfill The semiconductor element is peeled off from the laminated sheet. Thereafter, a semiconductor device is manufactured by performing the steps after the alignment step.

[準備步驟] [Preparation steps]

於準備步驟中，準備具備切晶帶41與積層於該切晶帶41上之特定底部填充材42的積層片(參照圖3A)。切晶帶41具備基材41a及積層於基材41a上之黏著劑層41b。再者，底部填充材42係積層於黏著劑層41b上。作為上述切晶帶41之基材41a及黏著劑層41b、以及底部填充材42，可使用與第1實施形態相同者。 In the preparation step, a laminated sheet having a dicing tape 41 and a specific underfill material 42 laminated on the dicing tape 41 is prepared (see FIG. 3A). The dicing tape 41 is provided with a base material 41a and an adhesive layer 41b laminated on the base material 41a. Further, the underfill material 42 is laminated on the adhesive layer 41b. The base material 41a, the adhesive layer 41b, and the underfill material 42 of the above-described dicing tape 41 can be the same as those of the first embodiment.

[貼合步驟] [Finishing step]

於貼合步驟中，如圖3A所示，將兩面形成有具有連接構件44之電路面的半導體晶圓43與上述積層片之底部填充材42貼合。再者，經薄型化至特定厚度之半導體晶圓之強度較弱，因此有時為了強化而將半導體晶圓經由暫時固定材固定於支持玻璃等支持體(未圖示)。於該情形時，亦可包括於半導體晶圓與底部填充材之貼合後將支持體與暫時固定材一起剝離的步驟。將半導體晶圓43之何電路面與底部填充材42貼合係根據目標半導體裝置之結構進行變更即可。 In the bonding step, as shown in FIG. 3A, the semiconductor wafer 43 having the circuit surface having the connection member 44 formed on both sides thereof is bonded to the underfill material 42 of the laminated sheet. Further, since the strength of the semiconductor wafer which is thinned to a specific thickness is weak, the semiconductor wafer may be fixed to a support such as a support glass (not shown) via a temporary fixing material for reinforcement. In this case, the step of peeling the support together with the temporary fixing material after bonding the semiconductor wafer and the underfill material may be included. The circuit surface of the semiconductor wafer 43 and the underfill material 42 may be bonded to each other according to the structure of the target semiconductor device.

半導體晶圓43兩面形成有具有連接構件44之電路面且具有特定厚度，除此方面以外，與第1實施形態之半導體晶圓相同。半導體晶 圓43之兩面之連接構件44彼此可電性連接，亦可不連接。連接構件44彼此之電性連接可列舉藉由被稱作TSV形式之經由通孔之連接的連接等。作為貼合條件，可較佳地採用第1實施形態中之貼合條件。 The semiconductor wafer 43 has the circuit surface having the connection member 44 formed on both surfaces thereof and has a specific thickness, and is the same as the semiconductor wafer of the first embodiment. Semiconductor crystal The connecting members 44 on both sides of the circle 43 may or may not be electrically connected to each other. The electrical connection of the connecting members 44 to each other may be exemplified by a connection called a connection via a through hole in the form of TSV or the like. As the bonding conditions, the bonding conditions in the first embodiment can be preferably used.

[切晶步驟] [Cutting step]

於切晶步驟中，對上述半導體晶圓43及底部填充材42進行切晶，而形成附有上述底部填充材之半導體元件45(參照圖3B)。作為切晶條件，可較佳地採用第1實施形態中之諸條件。再者，切晶係對半導體晶圓43露出之電路面進行，因此切晶位置之檢測較容易，但視需要亦可照射光而確認切晶位置後進行切晶。 In the dicing step, the semiconductor wafer 43 and the underfill material 42 are diced to form a semiconductor element 45 with the underfill material (see FIG. 3B). As the dicing conditions, the conditions in the first embodiment can be preferably employed. Further, since the dicing system is performed on the circuit surface on which the semiconductor wafer 43 is exposed, it is easy to detect the dicing position, but it is also possible to illuminate the light to confirm the dicing position and then perform dicing.

[拾取步驟] [pickup step]

於拾取步驟中，將附有上述底部填充材42之半導體元件45自上述切晶帶41剝離(圖3C)。作為拾取條件，可較佳地採用第1實施形態中之諸條件。 In the pickup step, the semiconductor element 45 to which the underfill material 42 is attached is peeled off from the dicing tape 41 (Fig. 3C). As the pickup conditions, the conditions in the first embodiment can be preferably employed.

本實施形態之積層片中，上述底部填充材自上述切晶帶之剝離力較佳為0.03~0.10N/20mm。藉此，可容易地進行附有底部填充材之半導體元件之拾取。 In the laminated sheet of the embodiment, the peeling force of the underfill material from the dicing tape is preferably 0.03 to 0.10 N/20 mm. Thereby, pickup of the semiconductor element with the underfill material can be easily performed.

[安裝步驟] [installation steps]

於安裝步驟中，將被黏著體66與半導體元件45之間之空間用底部填充材42填充，並且經由連接構件44將半導體元件45與被黏著體66電性連接(參照圖3D)。安裝步驟中之條件可較佳地採用第1實施形態中之諸條件。藉此，可製造本實施形態之半導體裝置60。 In the mounting step, the space between the adherend 66 and the semiconductor element 45 is filled with the underfill material 42, and the semiconductor element 45 is electrically connected to the adherend 66 via the connection member 44 (refer to FIG. 3D). The conditions in the mounting step can preferably be those in the first embodiment. Thereby, the semiconductor device 60 of this embodiment can be manufactured.

以下，亦可與第1實施形態相同地視需要進行底部填充材硬化步驟及密封步驟。 Hereinafter, the underfill hardening step and the sealing step may be performed as needed in the same manner as in the first embodiment.

<第3實施形態> <Third embodiment>

第1實施形態中使用背面研削用帶作為積層片之構成構件，但本實施形態中不設置該背面研削用帶之黏著劑層而單獨使用基材。因 此，作為本實施形態之積層片，成為於基材上積層有底部填充材之狀態。本實施形態中，研削步驟可任意地進行，但拾取步驟前之紫外線照射因省略黏著劑層而不進行。藉由經過除了該等方面而其他與第1實施形態相同之步驟，可製造特定之半導體裝置。 In the first embodiment, the back grinding belt is used as the constituent member of the laminated sheet. However, in the present embodiment, the adhesive layer of the back grinding belt is not provided, and the base material is used alone. because As a result of the laminated sheet of the present embodiment, the underfill material is laminated on the substrate. In the present embodiment, the grinding step can be carried out arbitrarily, but the ultraviolet irradiation before the picking step is not performed because the adhesive layer is omitted. A specific semiconductor device can be manufactured by performing the same steps as those of the first embodiment except for these aspects.

<其他實施形態> <Other Embodiments>

於第1實施形態至第3實施形態中，於切晶步驟中採用使用切晶刀片之切晶，亦可採用下述所謂的隱形切晶進行代替：藉由雷射照射於半導體晶圓內部形成改質部分，沿著該改質部分對半導體晶圓進行分割而進行單片化。 In the first embodiment to the third embodiment, the dicing using the dicing blade is used in the dicing step, and the so-called stealth dicing may be used instead of: forming the inside of the semiconductor wafer by laser irradiation. The modified portion is divided into semiconductor wafers along the modified portion to be singulated.

[實施例] [Examples]

以下，例示性且詳細地對該發明之較佳實施例進行說明。其中，該實施例所記載之材料或調配量等只要無特別限定之記載，則本發明之宗旨並非將該發明之範圍僅限定於上述記載。又，記為份之情況意指重量份。 Hereinafter, preferred embodiments of the invention will be described by way of example and in detail. However, the materials, the blending amounts, and the like described in the examples are not intended to limit the scope of the invention to the above description unless otherwise specified. Also, the case of being divided into parts means parts by weight.

[實施例1~3及比較例1~2] [Examples 1 to 3 and Comparative Examples 1 to 2]

(積層片之製作) (production of laminates)

將以下之成分按照表1所示之比率溶解於甲基乙基酮中，而製備固形物成分濃度為25.4~60.6重量%之接著劑組合物之溶液。 The following components were dissolved in methyl ethyl ketone at a ratio shown in Table 1 to prepare a solution of the adhesive composition having a solid content concentration of 25.4 to 60.6% by weight.

丙烯酸系聚合物：以丙烯酸乙酯-甲基丙烯酸甲酯作為主成分之丙烯酸酯系聚合物(商品名「Pagoclone W-197CM」，根上工業股份有限公司製造) Acrylic polymer: an acrylate polymer containing ethyl acrylate-methyl methacrylate as a main component (trade name "Pagoclone W-197CM", manufactured by Gensei Industrial Co., Ltd.)

環氧樹脂1：商品名「Epikote 1004」，JER股份有限公司製造 Epoxy resin 1: trade name "Epikote 1004", manufactured by JER Co., Ltd.

環氧樹脂2：商品名「Epikote 828」，JER股份有限公司製造 Epoxy resin 2: trade name "Epikote 828", manufactured by JER Co., Ltd.

酚系樹脂：商品名「Milex XLC-4L」，三井化學股份有限公司製造 Phenolic resin: trade name "Milex XLC-4L", manufactured by Mitsui Chemicals Co., Ltd.

助焊劑(實施例1~3)：酚酞 Flux (Examples 1-3): Phenolphthalein

助焊劑(比較例1)：2-苯氧基苯甲酸 Flux (Comparative Example 1): 2-phenoxybenzoic acid

助焊劑(比較例2)：商品名「RIKACID MH-700」，新日本理化股份有限公司製造 Flux (Comparative Example 2): Trade name "RIKACID MH-700", manufactured by New Japan Physical and Chemical Co., Ltd.

無機填充劑：球狀二氧化矽(商品名「SO-25R」，Admatechs股份有限公司製造) Inorganic filler: spherical cerium oxide (trade name "SO-25R", manufactured by Admatechs Co., Ltd.)

熱硬化促進觸媒：咪唑觸媒(商品名「2PHZ-PW」，四國化成股份有限公司製造) Thermal hardening promoting catalyst: Imidazole catalyst (trade name "2PHZ-PW", manufactured by Shikoku Chemicals Co., Ltd.)

將該接著劑組合物之溶液塗佈於作為剝離襯墊(隔片)的經聚矽氧脫模處理之厚度為50μm、由聚對苯二甲酸乙二酯膜形成的脫模處理膜上後，於130℃下乾燥2分鐘，藉此製作厚度35μm之底部填充材。 The solution of the adhesive composition was applied onto a release-treated film formed of a polyethylene terephthalate film having a thickness of 50 μm as a release liner (separator). It was dried at 130 ° C for 2 minutes to prepare an underfill having a thickness of 35 μm.

<耐熱保存性(助焊劑成分之消失或改性)之評價> <Evaluation of heat-resistant storage stability (disappearance or modification of flux components)>

對所製作之底部填充材實施以下處理，而製備試樣a及b。 Samples a and b were prepared by subjecting the produced underfill to the following treatment.

試樣a：於大氣環境下、於室溫下靜置1小時 Sample a: allowed to stand at room temperature for 1 hour under atmospheric conditions

試樣b：於大氣環境下、於100℃下靜置1小時 Sample b: allowed to stand at 100 ° C for 1 hour under atmospheric conditions

繼而，將試樣a及b分別切割為約1cm見方左右，將切割片置於螺旋管中進行稱量。於其中添加四氫呋喃5mL，於室溫下振盪12小時以上使試樣膨潤後，添加磷酸緩衝液/乙腈混合溶液15mL使聚合物類再沈澱。利用傾析法採取上清液，利用薄膜過濾器(孔徑：0.2μm)對其進行過濾。利用溶析液稀釋濾液而製成樣液，於以下之條件下對該樣液進行高效液相層析法(HPLC)測定。 Then, the samples a and b were each cut to about 1 cm square, and the cut piece was placed in a spiral tube for weighing. 5 mL of tetrahydrofuran was added thereto, and the sample was swollen by shaking at room temperature for 12 hours or more, and then 15 mL of a phosphate buffer/acetonitrile mixed solution was added to reprecipitate the polymer. The supernatant was taken by a decantation method, and filtered using a membrane filter (pore size: 0.2 μm). The filtrate was diluted with a leach solution to prepare a sample solution, and the sample solution was subjected to high performance liquid chromatography (HPLC) measurement under the following conditions.

<測定裝置> <Measurement device>

HPLC：Agilent Technologies，1100 HPLC: Agilent Technologies, 1100

<測定條件> <Measurement conditions>

管柱：Inertsil ODS-3(4.6mm×250mm、5μm) Column: Inertsil ODS-3 (4.6mm × 250mm, 5μm)

溶析液組成：磷酸緩衝液/乙腈之梯度條件 Composition of the solution: gradient conditions of phosphate buffer / acetonitrile

流量：1.0mL/min Flow rate: 1.0mL/min

檢測器：DAD(190nm~400nm、230nm、280nm提取) Detector: DAD (190nm~400nm, 230nm, 280nm extraction)

管柱溫度：40℃ Column temperature: 40 ° C

注入量：10μL Injection volume: 10μL

根據標準品(助焊劑成分)之調整濃度與波峰面積製作校準曲線，根據來自試樣a及b的樣液之HPLC測定之波峰面積算出各試樣中之助焊劑成分重量。將所算出之各助焊劑成分重量除以稱量之處理前之切割片所含的助焊劑成分重量(根據調配量求出)而使其標準化，將來自試樣a之經標準化之助焊劑成分重量Wa設為初期含量，將來自試樣b之經標準化之助焊劑成分重量Wb設為承受熱歷程後之含量，基於下述式算出重量減少率。將重量減少率未達50重量%者記作「○」，將重量減少率為50重量%以上者記作「×」，而進行評價。於該測定中，消失或改性之助焊劑成分未以HPLC測定中之波峰之形式顯現或以與原來不同之波峰之形式顯現，並不包含於維持初期形態之助焊劑成分之波峰中，因此，基於該方面而判斷助焊劑成分之消失或改性。將評價結果示於表1。 A calibration curve was prepared based on the adjusted concentration of the standard (flux component) and the peak area, and the weight of the flux component in each sample was calculated from the peak area of the HPLC measurement of the sample liquids from the samples a and b. Dividing the calculated flux component weight by the weight of the flux component (determined according to the blending amount) contained in the dicing sheet before the weighing process, and normalizing the flux component from the sample a W a as an initial content by weight, of the flux component from the sample normalized b b W is the weight of the content after subjected to heat history, the following formula was calculated based on the rate of weight loss. When the weight reduction rate is less than 50% by weight, it is referred to as "○", and the weight reduction rate of 50% by weight or more is referred to as "X", and evaluation is performed. In this measurement, the flux component that disappears or is modified does not appear as a peak in the HPLC measurement or appears as a peak different from the original, and is not included in the peak of the flux component that maintains the initial form. Based on this aspect, the disappearance or modification of the flux component is judged. The evaluation results are shown in Table 1.

重量減少率={(Wa-Wb)/Wa}×100(%) Weight reduction rate = {(W a - W b ) / W a } × 100 (%)

<非轉移性(助焊劑成分向黏著劑層之轉移)之評價> <Non-transferability (transfer of flux component to adhesive layer)>

對所製作之底部填充材實施以下處理，而製備試樣c及d。 Samples c and d were prepared by subjecting the produced underfill to the following treatment.

試樣c：於大氣環境下、於50℃下靜置72小時 Sample c: allowed to stand at 50 ° C for 72 hours under atmospheric conditions

試樣d：使用手壓輥將所製作之底部填充材貼合於具備由丙烯酸系黏著劑形成之黏著劑層的背面研削用帶(商品名「UB3083D」，日東電工股份有限公司製造)之黏著劑層上而製作積層片，將該積層片於大氣環境下、於50℃下靜置72小時 Sample d: The underfill material to be bonded to the back side grinding tape (trade name "UB3083D", manufactured by Nitto Denko Corporation) having an adhesive layer formed of an acrylic adhesive was bonded by a hand roller. A laminate is prepared on the agent layer, and the laminate is allowed to stand at 50 ° C for 72 hours under atmospheric conditions.

繼而，為了削弱背面研削用帶之黏著力，而自背面研削用帶側照射紫外線，將試樣c及d分別切割為約1cm見方左右，將切割片置於螺旋管中進行稱量。再者，關於試樣d，自積層片剝離底部填充材， 自經剝離之底部填充材獲得切割片。於投入有切割片之螺旋管中添加四氫呋喃5mL，於室溫下振盪12小時以上使試樣膨潤後，添加磷酸緩衝液/乙腈混合溶液15mL使聚合物類再沈澱。利用傾析法採取上清液，利用薄膜過濾器(孔徑：0.2μm)對其進行過濾。利用溶析液稀釋濾液而製成樣液，於以下之條件下對該樣液進行高效液相層析法(HPLC)測定。 Then, in order to weaken the adhesive force of the back grinding belt, the ultraviolet rays were irradiated from the side of the back grinding belt, and the samples c and d were cut into about 1 cm square, respectively, and the cut sheets were placed in a spiral tube and weighed. Furthermore, regarding the sample d, the underfill material is peeled off from the laminated sheet, A cut piece was obtained from the peeled underfill. 5 mL of tetrahydrofuran was added to the spiral tube into which the dicing sheet was placed, and the sample was swollen by shaking at room temperature for 12 hours or more, and then 15 mL of a phosphate buffer/acetonitrile mixed solution was added to reprecipitate the polymer. The supernatant was taken by a decantation method, and filtered using a membrane filter (pore size: 0.2 μm). The filtrate was diluted with a leach solution to prepare a sample solution, and the sample solution was subjected to high performance liquid chromatography (HPLC) measurement under the following conditions.

<測定裝置> <Measurement device>

HPLC：Agilent Technologies，1100 HPLC: Agilent Technologies, 1100

<測定條件> <Measurement conditions>

管柱：Inertsil ODS-3(4.6mm×250mm、5μm) Column: Inertsil ODS-3 (4.6mm × 250mm, 5μm)

溶析液組成：磷酸緩衝液/乙腈之梯度條件 Composition of the solution: gradient conditions of phosphate buffer / acetonitrile

流量：1.0mL/min Flow rate: 1.0mL/min

檢測器：DAD(190nm~400nm、230nm、280nm提取) Detector: DAD (190nm~400nm, 230nm, 280nm extraction)

管柱溫度：40℃ Column temperature: 40 ° C

注入量：10μL Injection volume: 10μL

根據標準品(助焊劑成分)之調整濃度與波峰面積製作校準曲線，根據來自試樣c及d的樣液之HPLC測定之波峰面積算出各試樣中之助焊劑成分重量。將所算出之各助焊劑成分重量除以稱量之處理前之切割片所含的助焊劑成分重量(根據調配量求出)而將其標準化，將來自試樣c之經標準化之助焊劑成分重量Wc設為初期含量，將來自試樣d之經標準化之助焊劑成分重量Wd設為承受熱歷程後之含量，基於下述式算出重量減少率。將重量減少率未達50重量%者記作「○」，將重量減少率為50重量%以上者記作「×」，而進行評價。將評價結果示於表1。 A calibration curve was prepared based on the adjusted concentration of the standard (flux component) and the peak area, and the weight of the flux component in each sample was calculated from the peak area of the HPLC measurement of the sample liquids from the samples c and d. The calculated weight of each flux component is divided by the weight of the flux component contained in the dicing sheet before the weighing process (determined according to the blending amount), and normalized, and the standardized flux component from the sample c is obtained. W is the weight of a flux component d to the initial content by weight W c, d from the sample normalized to the sum of the content after receiving thermal history, the weight reduction rate was calculated by the following formula based. When the weight reduction rate is less than 50% by weight, it is referred to as "○", and the weight reduction rate of 50% by weight or more is referred to as "X", and evaluation is performed. The evaluation results are shown in Table 1.

重量減少率={(Wc-Wd)/Wc}×100(%) Weight reduction rate = {(W c - W d ) / W c } × 100 (%)

<100℃~200℃下之最低黏度之測定> <Measurement of the lowest viscosity at <100 ° C ~ 200 ° C>

使用流變計(HAAKE公司製造，RS-1)，藉由平行板法進行測定。詳細而言，設為間隙100μm、旋轉平皿直徑20mm、旋轉速度5s-1、升溫速度10℃/分鐘之條件，自80℃升溫，藉由底部填充材之硬化反應而黏度上升，進行測定直至最終旋轉平皿無法旋轉之溫度(再者，所有實施例及比較例中為200℃以上)。將此時之100℃至200℃之範圍內之黏度之最低值設為最低黏度。將結果示於表1。 The measurement was performed by a parallel plate method using a rheometer (manufactured by HAAKE Co., Ltd., RS-1). Specifically, the conditions are as follows: a gap of 100 μm, a rotating plate diameter of 20 mm, a rotation speed of 5 s -1 , and a temperature increase rate of 10 ° C/min. The temperature is raised from 80 ° C, and the viscosity is increased by the hardening reaction of the underfill material, and the measurement is performed until the final measurement. The temperature at which the rotating plate could not be rotated (further, in all examples and comparative examples, 200 ° C or higher). The lowest value of the viscosity in the range of 100 ° C to 200 ° C at this time is set as the lowest viscosity. The results are shown in Table 1.

根據表1可知，於所有實施例中耐熱保存性及非轉移性良好，即便底部填充材承受熱歷程或與其他黏著劑層積層，亦可發揮所需要之助焊劑活性。另一方面，比較例1中，雖然耐熱保存性良好，但產生向黏著劑層之轉移而非轉移性較差。比較例2中，耐熱保存性、非轉移性均較差。 According to Table 1, it was found that the heat-resistant storage stability and non-metastatic property were good in all of the examples, and the required flux activity was exhibited even if the underfill material was subjected to thermal history or layering with other adhesives. On the other hand, in Comparative Example 1, although the heat-resistant storage stability was good, the transfer to the adhesive layer was caused, but the transfer property was inferior. In Comparative Example 2, both heat-resistant storage stability and non-metastatic property were inferior.

2‧‧‧底部填充材 2‧‧‧Bottom filler

4‧‧‧連接構件 4‧‧‧Connecting components

5‧‧‧半導體元件 5‧‧‧Semiconductor components

16‧‧‧被黏著體 16‧‧‧Adhesive body

17‧‧‧導電材 17‧‧‧Electrical materials

20‧‧‧半導體裝置 20‧‧‧Semiconductor device

Claims (7)

一種底部填充材，其係含有分子量為300以上、且於分子內至少具有1個酯鍵之芳香族化合物作為助焊劑成分。 An underfill material containing an aromatic compound having a molecular weight of 300 or more and having at least one ester bond in a molecule as a flux component. 如請求項1之底部填充材，其中將上述底部填充材於100℃下加熱1小時後上述助焊劑成分相對於初期含量之重量減少率未達50%。 The underfill material of claim 1, wherein the weight reduction rate of the flux component relative to the initial content after the underfill material is heated at 100 ° C for 1 hour is less than 50%. 如請求項1之底部填充材，其中將上述底部填充材與黏著劑層積層而成之積層體於50℃下靜置72小時後上述底部填充材中之上述助焊劑成分相對於初期含量的重量減少率未達50%。 The underfill material of claim 1, wherein the laminate of the underfill material and the adhesive layer is allowed to stand at 50 ° C for 72 hours, and the weight of the flux component in the underfill material relative to the initial content is The reduction rate is less than 50%. 如請求項1之底部填充材，其中相對於上述底部填充材中之上述助焊劑成分之重量與除上述助焊劑成分以外之成分之重量的合計重量，上述助焊劑成分之重量所占之比率為1重量%以上且50重量%以下。 The bottom filler of claim 1, wherein the ratio of the weight of the flux component to the total weight of the weight of the flux component in the underfill material and the weight of the component other than the flux component is 1% by weight or more and 50% by weight or less. 一種積層片，其具備具有基材及設置於該基材上之黏著劑層之黏著帶、及積層於上述黏著劑層上之如請求項1之底部填充材。 A laminated sheet comprising an adhesive tape having a substrate and an adhesive layer disposed on the substrate, and an underfill material as claimed in claim 1 laminated on the adhesive layer. 如請求項5之積層片，其中上述黏著帶為半導體晶圓之背面研削用帶或切晶帶。 The laminated sheet of claim 5, wherein the adhesive tape is a back grinding tape or a dicing tape of a semiconductor wafer. 一種半導體裝置之製造方法，其係製造具備被黏著體、與該被黏著體電性連接之半導體元件、及填充該被黏著體與該半導體元件之間之空間之底部填充材的半導體裝置者，且該製造方法包括：準備將如請求項1至4中任一項之底部填充材貼合於上述半導體元件而成之附有底部填充材之半導體元件的步驟，及連接步驟，其係將上述被黏著體與上述半導體元件之間之空 間以上述底部填充材予以填充，並且將上述半導體元件與上述被黏著體電性連接。 A method of manufacturing a semiconductor device, comprising: manufacturing a semiconductor device including an adherend, a semiconductor element electrically connected to the adherend, and an underfill filling a space between the adherend and the semiconductor element; And the manufacturing method includes the steps of: preparing the semiconductor element with the underfill material obtained by bonding the underfill material of any one of claims 1 to 4 to the semiconductor element, and a connecting step, which is The space between the adherend and the above semiconductor component The underfill material is filled with the above-mentioned underfill material, and the semiconductor element is electrically connected to the adherend.
TW103119133A 2013-06-07 2014-05-30 Underfill material, laminate sheet, and method for manufacturing semiconductor device TW201512380A (en)

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