TW201627452A - Adhesive sheet, adhesive sheet with dicing sheet and method of manufacturing semiconductor device - Google Patents

Adhesive sheet, adhesive sheet with dicing sheet and method of manufacturing semiconductor device Download PDF

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Publication number
TW201627452A
TW201627452A TW104137921A TW104137921A TW201627452A TW 201627452 A TW201627452 A TW 201627452A TW 104137921 A TW104137921 A TW 104137921A TW 104137921 A TW104137921 A TW 104137921A TW 201627452 A TW201627452 A TW 201627452A
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sheet
wafer
resin
bonding
adhesive
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TW104137921A
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Chinese (zh)
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TWI656189B (en
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Yuta Kimura
Sadahito Misumi
Kenji Onishi
Yuichiro Shishido
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Nitto Denko Corp
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27Manufacturing methods
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/44Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001Core members of the connector
    • H01L2224/45099Material
    • H01L2224/451Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144Gold (Au) as principal constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732Location after the connecting process
    • H01L2224/73251Location after the connecting process on different surfaces
    • H01L2224/73265Layer and wire connectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319Arrangement of the layer connectors prior to mounting
    • H01L2224/83191Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/91Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92Specific sequence of method steps
    • H01L2224/922Connecting different surfaces of the semiconductor or solid-state body with connectors of different types
    • H01L2224/9222Sequential connecting processes
    • H01L2224/92242Sequential connecting processes the first connecting process involving a layer connector
    • H01L2224/92247Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181Encapsulation

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Die Bonding (AREA)

Abstract

The purpose of the present invention is to provide an adhesive sheet that is possible to cure in a short period of time, reduce the poor bonding between the copper wire and the pad, and prevent from rupture of the semiconductor wafer, and an adhesive sheet with a dicing sheet. The present invention relates to an adhesive sheet, which is heated from 25DEG C to 175DEG C in 3 minutes and maintained at 175DEG C for 3 hours. Under this condition, the DSC curve depicted in a DSC measurement reveals that the time from the reach of 175DEG C to the disappearance of the reaction peak is less than 30 minutes. The cured product obtained by curing at 175DEG C and 10 Hz for 30 minutes is subject to viscoelasticity testing, and the tensile elastic coefficient measured at 200DEG C is more than 100 MPa. The present invention relates to an adhesive sheet with a dicing sheet, which includes a dicing sheet consisting of a substrate and an adhesive layer disposed on the substrate and an adhesive sheet disposed on the adhesive layer.

Description

接著薄片、附有切割薄片之接著薄片及半導體裝置之製造方法 Substrate, subsequent sheet with dicing sheet, and method of manufacturing semiconductor device

本發明係關於接著薄片、附有切割薄片之接著薄片及半導體裝置之製造方法。 The present invention relates to a bonding sheet, a bonding sheet with a dicing sheet, and a method of manufacturing a semiconductor device.

關於半導體裝置之方法,例如已知有包含:將半導體晶片用接著薄片固定在引線框等之被粘黏體上的步驟、與使接著薄片固化的步驟、與絲焊的步驟的半導體裝置之方法(例如參照專利文獻1)。 As a method of the semiconductor device, for example, a method of fixing a semiconductor wafer with a subsequent sheet to a adherend such as a lead frame, a method of curing a subsequent sheet, and a method of soldering a semiconductor device are known. (For example, refer to Patent Document 1).

近年來,進行了從使用金線的絲焊到使用廉價的銅線的絲焊的轉型。另外,從半導體裝置之小型化的要求考慮,進行了半導體晶片之小型化。 In recent years, the transition from wire bonding using gold wires to wire bonding using inexpensive copper wires has been carried out. Further, in consideration of the miniaturization of the semiconductor device, the semiconductor wafer has been miniaturized.

〔現有技術文獻〕 [Prior Art Literature] 〔專利文獻〕 [Patent Document]

〔專利文獻1〕日本特開2013-53190號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-53190

銅線由於容易氧化,因此難以與半導體晶片之焊盤接著,熔融球硬。因而,在使用了銅線的絲焊中,半導體晶片容易因從絲焊裝置中發出的超聲波而振動,容易產生銅線與焊盤的接合不良、晶片破裂。由於與引線框接觸的面積小的小型半導體晶片容易振動,因此特別容易產生接合不良、晶片破裂。 Since the copper wire is easily oxidized, it is difficult to follow the pad of the semiconductor wafer, and the molten ball is hard. Therefore, in the wire bonding using the copper wire, the semiconductor wafer is easily vibrated by the ultrasonic waves emitted from the wire bonding apparatus, and the bonding failure of the copper wire and the pad is likely to occur, and the wafer is broken. Since a small semiconductor wafer having a small area in contact with the lead frame is easily vibrated, it is particularly likely to cause bonding failure and wafer breakage.

本發明的目的在於,解決前述問題,提供可以在短時間內固化、可以減少銅線與焊盤的接合不良、半導體晶片之破裂的接著薄片、附有切割薄片之接著薄片。本發明的目的還在於,提供可以在短時間內使接著薄片固化、可以減少銅線與焊盤的接合不良、半導體晶片之破裂的半導體裝置之製造方法。 An object of the present invention is to solve the above problems and to provide a subsequent sheet which can be cured in a short period of time, which can reduce bonding failure between a copper wire and a pad, cracking of a semiconductor wafer, and a bonding sheet with a dicing sheet. Another object of the present invention is to provide a method of manufacturing a semiconductor device which can cure a bonding sheet in a short period of time, can reduce bonding failure between a copper wire and a pad, and break a semiconductor wafer.

本發明係關於半導體裝置之製造中所用的接著薄片。本發明的接著薄片具備以下的性質。即,在利用以3分鐘從25℃升溫到175℃、然後將175℃維持3小時的條件下藉由DSC測定所描繪的DSC曲線中,從到達175℃到反應峰消失的時間未達30分鐘。由於從到達175℃到反應峰消失的時間未達30分鐘,因此可以在短時間內使之固化。本發明的接著薄片更進一步具備以下的性質。即,在10Hz下對藉由在175℃下加熱30分鐘而固化得到的固化物的黏彈性進行測定,由此得到的200℃的伸張彈性係數為100MPa以上。由於200℃的伸張彈性係數 為100MPa以上,因此可以減少半導體晶片之振動,從而可以減少銅線與焊盤的接合不良、半導體晶片之破裂。 The present invention relates to a follower sheet used in the manufacture of a semiconductor device. The succeeding sheet of the present invention has the following properties. That is, in the DSC curve measured by DSC under the conditions of raising the temperature from 25 ° C to 175 ° C for 3 minutes and then maintaining 175 ° C for 3 hours, the time from reaching 175 ° C until the reaction peak disappeared was less than 30 minutes. . Since the time from the arrival of 175 ° C to the disappearance of the reaction peak is less than 30 minutes, it can be cured in a short time. The succeeding sheet of the present invention further has the following properties. That is, the viscoelasticity of the cured product obtained by curing at 175 ° C for 30 minutes was measured at 10 Hz, and the tensile modulus at 200 ° C obtained was 100 MPa or more. Due to the tensile modulus of 200 ° C Since it is 100 MPa or more, the vibration of the semiconductor wafer can be reduced, and the bonding failure of the copper wire and the pad and the crack of the semiconductor wafer can be reduced.

本發明的接著薄片較佳進一步具備以下的性質。即,利用將25℃~300℃的範圍中以每分鐘10℃升溫的條件下的DSC測定得到的反應熱較佳為80mJ/mg以上。 The succeeding sheet of the present invention preferably further has the following properties. In other words, the heat of reaction obtained by DSC measurement under the conditions of raising the temperature at 10 ° C per minute in the range of 25 ° C to 300 ° C is preferably 80 mJ / mg or more.

本發明之接著薄片較佳更進一步具備以下的性質。即,藉由於175℃下加熱30分鐘而固化得到的固化物的Tg較佳為150℃以上。 The succeeding sheet of the present invention preferably further has the following properties. That is, the Tg of the cured product obtained by curing at 175 ° C for 30 minutes is preferably 150 ° C or higher.

本發明的接著薄片較佳包含BET比表面積為4m2/g以上的二氧化矽填料。二氧化矽填料的含量較佳為50重量%以上。 The succeeding sheet of the present invention preferably contains a cerium oxide filler having a BET specific surface area of 4 m 2 /g or more. The content of the cerium oxide filler is preferably 50% by weight or more.

本發明的接著薄片包含樹脂成分。較佳樹脂成分包含環氧樹脂、酚醛樹脂及丙烯酸樹脂。更佳樹脂成分100重量%中的丙烯酸樹脂的含量為14重量%以下。酚醛樹脂的羥基當量較佳為120g/eq.以下。 The succeeding sheet of the present invention contains a resin component. The preferred resin component comprises an epoxy resin, a phenolic resin, and an acrylic resin. More preferably, the content of the acrylic resin in 100% by weight of the resin component is 14% by weight or less. The hydroxyl equivalent of the phenol resin is preferably 120 g/eq. or less.

本發明更進一步關於一種附有切割薄片之接著薄片,其包括具備基材及配置於基材上的黏著劑層的切割片、與配置於黏著劑層上的接著薄片。 The present invention still further relates to a back sheet comprising a dicing sheet comprising a dicing sheet comprising a substrate and an adhesive layer disposed on the substrate, and a back sheet disposed on the adhesive layer.

本發明更進一步關於一種半導體裝置之製造方法,其包含:準備附有切割薄片之接著薄片的步驟、與在接著薄片上壓接半導體晶圓之步驟;藉由切割配置於接著薄片上的半導體晶圓,而形成包括具備焊盤的半導體晶片及配置於半導體晶片上的接著薄膜的黏晶用晶片的步 驟、與藉由在具備端子部的被黏物上壓接黏晶用晶片而形成附有晶片的被黏物的步驟、與藉由加熱附有晶片的被黏物而使接著薄膜固化的步驟、與在使接著薄膜固化的步驟之後進行的包含將包含銅的金屬線的一端與焊盤接合的步驟及將金屬線的另一端與端子部接合的步驟。 The present invention further relates to a method of fabricating a semiconductor device, comprising: a step of preparing a subsequent sheet with a dicing sheet, and a step of crimping a semiconductor wafer on a subsequent sheet; and cutting a semiconductor crystal disposed on the subsequent sheet Step of forming a die-bonding wafer including a semiconductor wafer having a pad and an adhesive film disposed on the semiconductor wafer And a step of forming a wafer-attached adherend by crimping the die-bonding wafer on the adherend having the terminal portion, and a step of curing the adhesive film by heating the adherend to which the wafer is attached And a step of bonding one end of the metal wire including copper to the pad and a step of bonding the other end of the metal wire to the terminal portion, which is performed after the step of curing the adhesive film.

10‧‧‧附有切割薄片之接著薄片 10‧‧‧With a thin sheet of cut sheet

1‧‧‧切割片 1‧‧‧ cutting piece

11‧‧‧基材 11‧‧‧Substrate

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

3‧‧‧接著薄片 3‧‧‧ followed by thin slices

4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer

5‧‧‧半導體晶片 5‧‧‧Semiconductor wafer

501‧‧‧焊盤 501‧‧‧ pads

502‧‧‧晶片主體部 502‧‧‧ wafer main body

41‧‧‧黏晶用晶片 41‧‧‧Crystal wafer

6‧‧‧被黏物 6‧‧‧Adhesive

601‧‧‧端子部 601‧‧‧ Terminals

602‧‧‧主體部 602‧‧‧ Main body

61‧‧‧附有半導體晶片之被黏物 61‧‧‧ Attached with semiconductor wafers

7‧‧‧焊線 7‧‧‧welding line

8‧‧‧密封樹脂 8‧‧‧ Sealing resin

〔圖1〕是接著薄片的概略剖面圖。 Fig. 1 is a schematic cross-sectional view of a sheet.

〔圖2〕是附有切割薄片之接著薄片的概略剖面圖。 Fig. 2 is a schematic cross-sectional view of a succeeding sheet with a dicing sheet.

〔圖3〕是變形例的附有切割薄片之接著薄片的概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing a succeeding sheet with a dicing sheet according to a modification.

〔圖4〕是表示在附有切割薄片之接著薄片上配置了半導體晶圓之樣子的概略的剖面圖。 FIG. 4 is a schematic cross-sectional view showing a state in which a semiconductor wafer is placed on a subsequent sheet having a dicing sheet.

〔圖5〕是表示將半導體晶圓單片化之樣子的概略的剖面圖。 FIG. 5 is a schematic cross-sectional view showing a state in which a semiconductor wafer is singulated.

〔圖6〕是附有半導體晶片之被黏物的概略剖面圖。 Fig. 6 is a schematic cross-sectional view showing a adherend with a semiconductor wafer.

〔圖7〕是半導體裝置之概略剖面圖。 FIG. 7 is a schematic cross-sectional view of a semiconductor device.

〔圖8〕是實施例2的DSC曲線。 Fig. 8 is a DSC curve of Example 2.

〔用以實施本發明之形態〕 [Formation for carrying out the invention]

以下舉出實施方式,對本發明進行詳細說明,然而本發明並不僅限定於此等實施方式。 The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the embodiments.

〔實施方式1〕 [Embodiment 1] (接著薄片3) (following sheet 3)

如圖1所示,接著薄片3的形態為片狀。接著薄片3具備熱固性。 As shown in Fig. 1, the form of the sheet 3 is then in the form of a sheet. The sheet 3 is then thermoset.

接著薄片3更進一步具備以下的性質。即,在利用以3分鐘從25℃升溫到175℃、然後將175℃維持3小時的條件下藉由DSC測定所描繪的DSC曲線中,從到達175℃到反應峰消失的時間未達30分鐘。由於從到達175℃到反應峰消失的時間未達30分鐘,因此可以在短時間內使之固化。另外,可以在標準的絲焊條件下使之完全或大致完全地固化,從而可以減少半導體晶片之振動。從到達175℃到反應峰消失的時間較佳為未達25分鐘。另一方面,從到達175℃到反應峰消失的時間的下限例如為5分鐘、10分鐘、15分鐘等。 The sheet 3 is further provided with the following properties. That is, in the DSC curve measured by DSC under the conditions of raising the temperature from 25 ° C to 175 ° C for 3 minutes and then maintaining 175 ° C for 3 hours, the time from reaching 175 ° C until the reaction peak disappeared was less than 30 minutes. . Since the time from the arrival of 175 ° C to the disappearance of the reaction peak is less than 30 minutes, it can be cured in a short time. In addition, it can be completely or substantially completely cured under standard wire bonding conditions, thereby reducing the vibration of the semiconductor wafer. The time from the arrival of 175 ° C to the disappearance of the reaction peak is preferably less than 25 minutes. On the other hand, the lower limit of the time from the arrival of 175 ° C to the disappearance of the reaction peak is, for example, 5 minutes, 10 minutes, 15 minutes, or the like.

所謂「反應峰消失」,是指以使測定用樣品與參比用樣品的溫度相等的方式對兩者施加的每單位時間的熱能的輸入的差一定。 The phrase "the disappearance of the reaction peak" means that the difference in the input of the thermal energy per unit time applied to both of the sample for measurement and the temperature of the reference sample is constant.

從到達175℃到反應峰消失的時間可以利用固化促進劑的種類、固化促進劑的含量、樹脂的種類等來控制。 The time from the arrival of 175 ° C to the disappearance of the reaction peak can be controlled by the type of the curing accelerator, the content of the curing accelerator, the type of the resin, and the like.

接著薄片3較佳進一步具備以下的性質。即,利用將25℃~300℃的範圍中以每分鐘10℃升溫的條件下的DSC測定得到的反應熱量較佳為80mJ/mg以上, 更佳為85mJ/mg以上。另一方面,反應熱量較佳為300mJ/mg以下,更佳為200mJ/mg以下。 The sheet 3 is then preferably further provided with the following properties. In other words, the heat of reaction obtained by DSC measurement under the condition of raising the temperature at 10 ° C per minute in the range of 25 ° C to 300 ° C is preferably 80 mJ / mg or more. More preferably, it is 85 mJ/mg or more. On the other hand, the heat of reaction is preferably 300 mJ/mg or less, more preferably 200 mJ/mg or less.

所謂「反應熱」,是藉由將利用將25℃~300℃的範圍中以每分鐘10℃升溫的條件下的DSC測定所測定出的熱量除以試驗片的重量而算出的值。 The "reaction heat" is a value calculated by dividing the amount of heat measured by DSC measurement under the conditions of temperature increase of 10 ° C per minute in the range of 25 ° C to 300 ° C by the weight of the test piece.

藉由在10Hz下測定使接著薄片3固化而得的固化物的黏彈性所得到的200℃的伸張彈性係數為100MPa以上,較佳為200MPa以上。由於為100MPa以上,因此可以減少半導體晶片之振動,從而可以減少銅線與焊盤的接合不良、半導體晶片之破裂。200℃的伸張彈性係數較佳為1000MPa以下,更佳為700MPa以下。作為200℃的伸張彈性係數的上限,例如還可以例示出500MPa、400MPa等。 The tensile modulus at 200 ° C obtained by measuring the viscoelasticity of the cured product obtained by curing the succeeding sheet 3 at 10 Hz is 100 MPa or more, preferably 200 MPa or more. Since it is 100 MPa or more, the vibration of the semiconductor wafer can be reduced, and the bonding failure between the copper wire and the pad and the crack of the semiconductor wafer can be reduced. The tensile modulus at 200 ° C is preferably 1000 MPa or less, more preferably 700 MPa or less. As the upper limit of the tensile modulus of elasticity at 200 ° C, for example, 500 MPa, 400 MPa, or the like can be exemplified.

而且,固化物是藉由將接著薄片3在175℃加熱30分鐘、使之固化而得的物質。 Further, the cured product was obtained by heating the subsequent sheet 3 at 175 ° C for 30 minutes to cure it.

固化物的200℃的伸張彈性係數可以利用酚醛樹脂的羥基當量、二氧化矽填料的含量、二氧化矽填料的粒徑等來控制。例如,藉由使用羥基當量小的酚醛樹脂、增加二氧化矽填料的含量、使用粒徑小的二氧化矽填料,就可以提高200℃的伸張彈性係數。 The tensile modulus at 200 ° C of the cured product can be controlled by the hydroxyl equivalent of the phenol resin, the content of the ceria filler, the particle size of the ceria filler, and the like. For example, by using a phenol resin having a small hydroxyl equivalent, increasing the content of the cerium oxide filler, and using a cerium oxide filler having a small particle diameter, the tensile modulus of elasticity at 200 ° C can be improved.

固化物的Tg較佳為150℃以上,更佳為180℃以上。如果為150℃以上,則容易將固化物的200℃的伸張彈性係數設定為100MPa以上。另一方面,固化物的Tg較佳為250℃以下,更佳為220℃以下。 The Tg of the cured product is preferably 150 ° C or higher, more preferably 180 ° C or higher. When it is 150 ° C or more, it is easy to set the tensile modulus of elongation of 200 ° C of the cured product to 100 MPa or more. On the other hand, the Tg of the cured product is preferably 250 ° C or lower, more preferably 220 ° C or lower.

固化物的Tg(「玻璃轉變溫度」)可以利用酚醛樹脂的羥基當量等來控制。 The Tg ("glass transition temperature") of the cured product can be controlled by the hydroxyl equivalent of the phenol resin or the like.

接著薄片3包含樹脂成分。作為樹脂成分,可以舉出丙烯酸樹脂、環氧樹脂、酚醛樹脂等。 The sheet 3 then contains a resin component. Examples of the resin component include an acrylic resin, an epoxy resin, and a phenol resin.

作為丙烯酸樹脂,沒有特別限定,可以舉出以具有碳數30以下、特別是碳數4~18之直鏈或支鏈之烷基的丙烯酸或甲基丙烯酸的酯的1種或2種以上作為成分的聚合物(丙烯酸共聚物)等。作為前述烷基,例如可以舉出甲基、乙基、丙基、異丙基、正丁基、叔丁基、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、或十二烷基等。 The acrylic resin is not particularly limited, and one 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, may be mentioned. A polymer of a component (acrylic acid copolymer) or the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, a cyclohexyl group, and 2 -ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, octadecyl Alkyl, or dodecyl, and the like.

另外,作為形成聚合物(丙烯酸共聚物)的其他單體,並沒有特別限定,例如可以舉出丙烯酸、甲基丙烯酸、丙烯酸羧乙酯、丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸或巴豆酸等之各種含有羧基的單體、馬來酸酐或衣康酸酐等之各種的酸酐單體、(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)甲酯等之各種含有羥基的單體、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各種含有磺酸基的單體、或2-羥基乙基丙烯醯基磷酸酯等之各種含有磷酸基的單體。 Further, the other monomer forming the polymer (acrylic acid copolymer) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and rich. Various acid anhydride monomers such as a carboxyl group-containing monomer such as horse acid or crotonic acid, maleic anhydride or itaconic anhydride, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (meth)acrylic acid Various hydroxyl group-containing monomers such as 12-hydroxylauryl ester or (4-hydroxymethylcyclohexyl)methyl acrylate, styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2- Methylpropanesulfonic acid, (meth) acrylamide Various kinds of sulfonic acid group-containing monomers such as sulfonic acid, sulfopropyl (meth) acrylate or (meth) propylene phthaloxy naphthalene sulfonic acid, or 2-hydroxyethyl acryl decyl phosphate, etc. Monomer.

在丙烯酸樹脂當中,較佳重量均分子量為10萬以上的丙烯酸樹脂,更佳為30萬~300萬的丙烯酸樹脂,進一步較佳為50萬~200萬的丙烯酸樹脂。這是因為,如果是該數值範圍內,其接著性及耐熱性優異。又,重量均分子量是利用GPC(凝膠滲透色譜)進行測定並利用聚苯乙烯換算算出的值。 Among the acrylic resins, an acrylic resin having a weight average molecular weight of 100,000 or more, more preferably an acrylic resin of 300,000 to 3,000,000, more preferably an acrylic resin of 500,000 to 2,000,000 is preferable. This is because if it is within this numerical range, it is excellent in adhesion and heat resistance. Further, the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

丙烯酸樹脂較佳包含能夠與環氧基反應的官能基。由此,就可以使丙烯酸樹脂與環氧樹脂交聯。 The acrylic resin preferably contains a functional group capable of reacting with an epoxy group. Thereby, the acrylic resin and the epoxy resin can be crosslinked.

作為能夠與環氧基反應的官能基,例如可以舉出羧基、羥基等。其中,由於與環氧基的反應性高的理由,因此較佳羧基。 Examples of the functional group reactive with the epoxy group include a carboxyl group and a hydroxyl group. Among them, a carboxyl group is preferred because of its high reactivity with an epoxy group.

丙烯酸樹脂的酸值較佳為5mgKOH/g以上,更佳為10mgKOH/g以上。另一方面,丙烯酸樹脂的酸值較佳為40mgKOH/g以下,更佳為25mgKOH/g以下。 The acid value of the acrylic resin is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more. On the other hand, the acid value of the acrylic resin is preferably 40 mgKOH/g or less, more preferably 25 mgKOH/g or less.

而且,酸值可以利用JIS K 0070-1992中規定的中和滴定法來測定。 Further, the acid value can be measured by the neutralization titration method specified in JIS K 0070-1992.

樹脂成分100重量%中的丙烯酸樹脂的含量較佳為14重量%以下,更佳為12重量%以下,進一步較佳為11重量%以下。如果是14重量%以下,則可以提高200℃的伸張彈性係數。樹脂成分100重量%中的丙烯酸樹脂的含量較佳為5重量%以上,更佳為7重量%以上。 The content of the acrylic resin in 100% by weight of the resin component is preferably 14% by weight or less, more preferably 12% by weight or less, still more preferably 11% by weight or less. If it is 14% by weight or less, the tensile modulus of elasticity at 200 ° C can be increased. The content of the acrylic resin in 100% by weight of the resin component is preferably 5% by weight or more, and more preferably 7% by weight or more.

作為環氧樹脂,沒有特別限定,例如可以使用雙酚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、芴型、苯酚酚醛型、鄰甲酚酚醛型、三羥基苯基甲烷型、四羥苯基乙烷型等之二官能環氧樹脂或多官能環氧樹脂、或者乙內醯脲型、三縮水甘油基異氰脲酸酯型或縮水甘油基胺型等之環氧樹脂。此等環氧樹脂中,特別佳酚醛型環氧樹脂、聯苯型環氧樹脂、三羥基苯基甲烷型樹脂或四羥苯基乙烷型環氧樹脂。此等因為,這些環氧樹脂富於與作為固化劑的酚醛樹脂的反應性,耐熱性等優異。 The epoxy resin is not particularly limited, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene can be used. a difunctional epoxy resin or a polyfunctional epoxy resin such as a hydrazine type, a phenol type, a phenol novolac type, an o-cresol novolac type, a trishydroxyphenylmethane type, a tetrahydroxyphenylethane type, or a beta-urea urea type, An epoxy resin such as a triglycidyl isocyanurate type or a glycidylamine type. Among these epoxy resins, a phenolic epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetrahydroxyphenylethane type epoxy resin is particularly preferred. Therefore, these epoxy resins are excellent in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

環氧樹脂的環氧當量較佳為120g/eq.以上,更佳為140g/eq.以上,進一步較佳為150g/eq.以上。另一方面,環氧樹脂的環氧當量較佳為250g/eq.以下,更佳為200g/eq.以下。 The epoxy equivalent of the epoxy resin is preferably 120 g/eq. or more, more preferably 140 g/eq. or more, still more preferably 150 g/eq. or more. On the other hand, the epoxy equivalent of the epoxy resin is preferably 250 g/eq. or less, more preferably 200 g/eq. or less.

又,環氧樹脂的環氧當量可以利用JIS K 7236-2009中規定的方法測定。 Further, the epoxy equivalent of the epoxy resin can be measured by the method specified in JIS K 7236-2009.

酚醛樹脂是作為環氧樹脂的固化劑發揮作用的物質,可以舉出例如苯酚酚醛樹脂、苯酚芳烷基樹脂、甲酚酚醛樹脂、叔丁基苯酚酚醛樹脂、壬基苯酚酚醛樹脂等之酚醛型酚醛樹脂、甲階酚醛型酚醛樹脂、聚對氧基苯乙烯等之聚氧基苯乙烯等。此等酚醛樹脂中,特別佳苯酚酚醛樹脂、苯酚芳烷基樹脂。這是因為,可以提高半導體裝置之連接可靠性。 The phenol resin is a substance which functions as a curing agent for an epoxy resin, and examples thereof include a phenol type such as a phenol novolac resin, a phenol aralkyl resin, a cresol novolac resin, a t-butyl phenol novolak resin, and a nonylphenol phenol resin. A phenolic resin, a resol type phenol resin, a polyoxystyrene such as polyparaphenylene or the like. Among these phenol resins, a phenol phenol resin and a phenol aralkyl resin are particularly preferable. This is because the connection reliability of the semiconductor device can be improved.

酚醛樹脂的羥基當量較佳為120g/eq.以下,更 佳為110g/eq.以下。如果是120g/eq.以下,則可以提高交聯密度,可以提高200℃的伸張彈性係數。另一方面,酚醛樹脂的羥基當量較佳為80g/eq.以上,更佳為90g/eq.以上。 The hydroxyl equivalent of the phenol resin is preferably 120 g/eq. or less, more Good is 110g/eq. below. If it is 120 g/eq. or less, the crosslinking density can be increased, and the tensile modulus of elasticity at 200 ° C can be improved. On the other hand, the hydroxyl equivalent of the phenol resin is preferably 80 g/eq. or more, more preferably 90 g/eq. or more.

對於環氧樹脂與酚醛樹脂的摻合比例,例如適合為以在環氧樹脂成分中的每1當量環氧基中使酚醛樹脂中的羥基為0.5~2.0當量的方式摻合。更適合為0.8~1.2當量。即因為,如果兩者的摻合比例脫離該範圍,則不能進行充分的固化反應,固化物的特性容易劣化。 The blending ratio of the epoxy resin to the phenol resin is, for example, suitably blended so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per 1 equivalent of the epoxy group in the epoxy resin component. More suitable for 0.8~1.2 equivalents. That is, if the blending ratio of the two is out of the range, a sufficient curing reaction cannot be performed, and the properties of the cured product are likely to deteriorate.

樹脂成分100重量%中的環氧樹脂及酚醛樹脂的合計含量較佳為86重量%以上,更佳為88重量%以上,進一步較佳為89重量%以上。如果是86重量%以上,則可以提高200℃的伸張彈性係數。另一方面,環氧樹脂及酚醛樹脂的合計含量較佳為95重量%以下,更佳為93重量%以下。 The total content of the epoxy resin and the phenol resin in 100% by weight of the resin component is preferably 86% by weight or more, more preferably 88% by weight or more, still more preferably 89% by weight or more. If it is 86% by weight or more, the tensile modulus of elasticity at 200 ° C can be increased. On the other hand, the total content of the epoxy resin and the phenol resin is preferably 95% by weight or less, and more preferably 93% by weight or less.

接著薄片3較佳包含BET比表面積為4m2/g以上的二氧化矽填料。 Next, the sheet 3 preferably contains a cerium oxide filler having a BET specific surface area of 4 m 2 /g or more.

二氧化矽填料的BET比表面積較佳為15m2/g以上。另一方面,二氧化矽填料的BET比表面積較佳為100m2/g以下,更佳為50m2/g以下。 The BET specific surface area of the cerium oxide filler is preferably 15 m 2 /g or more. On the other hand, the BET specific surface area of the cerium oxide filler is preferably 100 m 2 /g or less, more preferably 50 m 2 /g or less.

BET比表面積利用BET吸附法(多點法)測定。具體而言,將接著薄片3在大氣氣氛下在700℃強熱2小時而使之灰化。將所得的灰分在110℃進行6小時以上的真空脫氣後,使用Quantachrome製4連式比表面積‧孔徑 分佈測定裝置「NOVA-4200e型」,在氮氣中、77.35K的溫度下進行測定。 The BET specific surface area was measured by a BET adsorption method (multipoint method). Specifically, the succeeding sheet 3 was ashed by heating at 700 ° C for 2 hours in an air atmosphere. After the obtained ash was vacuum degassed at 110 ° C for 6 hours or more, a 4-connected specific surface area ‧ pore diameter made of Quantachrome was used. The distribution measuring device "NOVA-4200e type" was measured under nitrogen at a temperature of 77.35 K.

二氧化矽填料的新摩氏硬度較佳為4以上。如果是4以上,則可以高效地提高200℃的伸張彈性係數。二氧化矽填料的新摩氏硬度的上限沒有特別限定,然而例如為10。 The new Mohs hardness of the ceria filler is preferably 4 or more. If it is 4 or more, the tensile modulus of elasticity at 200 ° C can be efficiently improved. The upper limit of the new Mohs hardness of the cerium oxide filler is not particularly limited, but is, for example, 10.

接著薄片3中的二氧化矽填料的含量較佳為50重量%以上,更佳為51重量%以上。如果是50重量%以上,則可以提高200℃的伸張彈性係數。另一方面,二氧化矽填料的含量較佳為70重量%以下,更佳為65重量%以下。 The content of the cerium oxide filler in the sheet 3 is preferably 50% by weight or more, more preferably 51% by weight or more. If it is 50% by weight or more, the tensile modulus of elasticity at 200 ° C can be increased. On the other hand, the content of the cerium oxide filler is preferably 70% by weight or less, more preferably 65% by weight or less.

接著薄片3較佳包含固化促進劑。固化促進劑的含量相對於樹脂成分100重量份較佳為0.1~5重量份,更佳為0.1~3重量份。如果是0.1重量份以上,則可以在短時間內使之固化。 The sheet 3 then preferably comprises a curing accelerator. The content of the curing accelerator is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, per 100 parts by weight of the resin component. If it is 0.1 part by weight or more, it can be cured in a short time.

作為固化促進劑沒有特別限定,例如可以舉出咪唑系化合物、三苯基膦系化合物、胺系化合物、三苯基硼烷系化合物、三鹵代硼烷系化合物等。 The curing accelerator is not particularly limited, and examples thereof include an imidazole compound, a triphenylphosphine compound, an amine compound, a triphenylborane compound, and a trihaloborane compound.

作為咪唑系化合物,可以舉出2-甲基咪唑(商品名:2MZ)、2-十一烷基咪唑(商品名:C11Z)、2-十七烷基咪唑(商品名:C17Z)、1,2-二甲基咪唑(商品名:1.2DMZ)、2-乙基-4-甲基咪唑(商品名:2E4MZ)、2-苯基咪唑(商品名:2PZ)、2-苯基-4-甲基咪唑(商品名:2P4MZ)、1-苄基-2-甲基咪唑(商品名: 1B2MZ)、1-苄基-2-苯基咪唑(商品名:1B2PZ)、1-氰基乙基-2-甲基咪唑(商品名:2MZ-CN)、1-氰基乙基-2-十一烷基咪唑(商品名:C11Z-CN)、1-氰基乙基-2-苯基咪唑鎓偏苯三酸鹽(商品名:2PZCNS-PW)、2,4-二胺基-6-〔2’-甲基咪唑基-(1,)〕-乙基均三嗪(商品名:2MZ-A)、2,4-二胺基-6-〔2’-十一烷基咪唑基-(1’)〕-乙基均三嗪(商品名:C11Z-A)、2,4-二胺基-6-〔2’-乙基-4’-甲基咪唑基-(1’)〕-乙基均三嗪(商品名:2E4MZ-A)、2,4-二胺基-6-〔2’-甲基咪唑基-(1’)〕-乙基均三嗪異氰脲酸加成物(商品名:2MA-OK)、2-苯基-4,5-二羥基甲基咪唑(商品名:2PHZ-PW)、2-苯基-4-甲基-5-羥基甲基咪唑(商品名:2P4MHZ-PW)等(均為四國化成股份有限公司製)。 Examples of the imidazole-based compound include 2-methylimidazole (trade name: 2MZ), 2-undecylimidazole (trade name: C11Z), 2-heptadecylimidazole (trade name: C17Z), and 1, 2-Dimethylimidazole (trade name: 1.2DMZ), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), 2-phenylimidazole (trade name: 2PZ), 2-phenyl-4- Methylimidazole (trade name: 2P4MZ), 1-benzyl-2-methylimidazole (trade name: 1B2MZ), 1-benzyl-2-phenylimidazole (trade name: 1B2PZ), 1-cyanoethyl-2-methylimidazole (trade name: 2MZ-CN), 1-cyanoethyl-2- Undecylimidazole (trade name: C11Z-CN), 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2PZCNS-PW), 2,4-diamino-6 -[2'-methylimidazolyl-(1,)]-ethyl-s-triazine (trade name: 2MZ-A), 2,4-diamino-6-[2'-undecylimidazolyl -(1')]-ethyl s-triazine (trade name: C11Z-A), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1') ]-ethyl s-triazine (trade name: 2E4MZ-A), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl s-triazine isocyanuric acid Adduct (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxymethylimidazole (trade name: 2PHZ-PW), 2-phenyl-4-methyl-5-hydroxymethyl Imidazole (trade name: 2P4MHZ-PW), etc. (all manufactured by Shikoku Chemicals Co., Ltd.).

作為三苯基膦系化合物,沒有特別限定,例如可以舉出三苯基膦、三丁基膦、三(對甲基苯基)膦、三(壬基苯基)膦、二苯基甲苯基膦等之三有機基膦、四苯基溴化鏻(商品名:TPP-PB)、甲基三苯基鏻(商品名:TPP-MB)、甲基三苯基氯化鏻(商品名:TPP-MC)、甲氧基甲基三苯基鏻(商品名:TPP-MOC)、苄基三苯基氯化鏻(商品名:TPP-ZC)等(均為北興化學公司製)。 The triphenylphosphine-based compound is not particularly limited, and examples thereof include triphenylphosphine, tributylphosphine, tris(p-methylphenyl)phosphine, tris(nonylphenyl)phosphine, and diphenyltolyl. Triorganophosphine such as phosphine, tetraphenylphosphonium bromide (trade name: TPP-PB), methyltriphenylphosphonium (trade name: TPP-MB), methyltriphenylphosphonium chloride (trade name: TPP-MC), methoxymethyltriphenylphosphonium (trade name: TPP-MOC), benzyltriphenylphosphonium chloride (trade name: TPP-ZC), etc. (all manufactured by Beixing Chemical Co., Ltd.).

作為三苯基硼烷系化合物,沒有特別限定,例如可以舉出三(對甲基苯基)膦等。另外,作為三苯基硼烷系化合物,更進一步包含具有三苯基膦結構的化合 物。作為具有三苯基膦結構及三苯基硼烷結構的化合物,沒有特別限定,例如可以舉出四苯基鏻四苯基硼酸鹽(商品名:TPP-K)、四苯基鏻四-對三硼酸鹽(商品名:TPP-MK)、苄基三苯基鏻四苯基硼酸鹽(商品名:TPP-ZK)、三苯基膦三苯基硼烷(商品名:TPP-S)等(均為北興化學公司製)。 The triphenylborane-based compound is not particularly limited, and examples thereof include tris(p-methylphenyl)phosphine. Further, as the triphenylborane-based compound, a compound having a triphenylphosphine structure is further included. Things. The compound having a triphenylphosphine structure and a triphenylborane structure is not particularly limited, and examples thereof include tetraphenylphosphonium tetraphenylborate (trade name: TPP-K) and tetraphenylphosphonium tetra-pair. Triborate (trade name: TPP-MK), benzyltriphenylphosphonium tetraphenylborate (trade name: TPP-ZK), triphenylphosphine triphenylborane (trade name: TPP-S), etc. (All are manufactured by Beixing Chemical Co., Ltd.).

作為胺基系化合物,沒有特別限定,例如可以舉出單乙醇胺三氟硼酸鹽(Stella-Chemifa股份有限公司製)、雙氰醯胺(Nacalai Tesque股份有限公司製等。 The amine-based compound is not particularly limited, and examples thereof include monoethanolamine trifluoroborate (manufactured by Stella-Chemifa Co., Ltd.) and dicyandiamide (manufactured by Nacalai Tesque Co., Ltd.).

作為三鹵代硼烷系化合物,沒有特別限定,例如可以舉出三氯硼烷等。 The trihalogenated borane-based compound is not particularly limited, and examples thereof include trichloroborane and the like.

接著薄片3也可以在前述成分以外,還適當地含有在膜製造中普遍使用的摻合劑,例如交聯劑等。 The sheet 3 may be appropriately contained in addition to the above-mentioned components, and a blending agent commonly used in film production, such as a crosslinking agent or the like, may be appropriately contained.

接著薄片3可以利用通常的方法製造。例如,可以製作含有前述各成分的接著劑組合物溶液,在以達到規定厚度的方式將接著劑組合物溶液塗佈於基材隔膜上而形成塗佈膜後,使塗佈膜乾燥,由此製造接著薄片3。 The sheet 3 can then be produced by a usual method. For example, a solution of an adhesive composition containing each of the above components can be prepared, and a solution of the adhesive composition can be applied onto a substrate separator so as to have a predetermined thickness to form a coating film, and then the coating film can be dried. The subsequent sheet 3 is produced.

作為接著劑組合物溶液中所用的溶劑,沒有特別限定,較佳可以將前述各成分均勻地溶解、混煉或分散的有機溶劑。例如可以舉出二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮、丙酮、甲乙酮、環己酮等之酮系溶劑、甲苯、二甲苯等。塗佈方法沒有特別限定。作為溶劑塗敷的方法,例如可以舉出模塗佈、凹版塗佈、輥塗佈、 反向塗佈、逗點塗佈、管刀塗佈、絲網印刷等。其中,從塗佈厚度的均勻性高的方面考慮,較佳模塗佈。 The solvent to be used in the solution of the adhesive composition is not particularly limited, and an organic solvent in which the above components are uniformly dissolved, kneaded or dispersed can be preferably used. For example, a ketone solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone or cyclohexanone, toluene or xylene may be mentioned. The coating method is not particularly limited. Examples of the method of solvent coating include die coating, gravure coating, and roll coating. Reverse coating, comma coating, tube coating, screen printing, and the like. Among them, die coating is preferred from the viewpoint of high uniformity of coating thickness.

作為基材隔膜,可以使用聚對苯二甲酸乙二醇酯(PET)、聚乙烯、聚丙烯、或利用氟系剝離劑、長鏈烷基丙烯酸酯系剝離劑等之剝離劑進行了表面塗佈的塑膠膜或紙等。作為接著劑組合物溶液的塗佈方法,可以舉出例如輥塗敷、絲網塗敷、凹版塗敷等。另外,塗布膜的乾燥條件沒有特別限定,例如可以在70~160℃的乾燥溫度、以1~5分鐘的乾燥時間進行。 As the substrate separator, surface coating can be carried out using polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate release agent. Plastic film or paper of cloth. Examples of the coating method of the adhesive composition solution include roll coating, screen coating, gravure coating, and the like. Further, the drying conditions of the coating film are not particularly limited, and for example, it can be carried out at a drying temperature of 70 to 160 ° C for a drying time of 1 to 5 minutes.

作為接著薄片3的製造方法,例如也適合為將前述各成分利用混合器器混合、將所得的混合物壓製成形而製造接著薄片3的方法等。作為混合器,可以舉出行星式攪拌器等。 As a method of producing the succeeding sheet 3, for example, a method in which the above-described respective components are mixed by a mixer, and the obtained mixture is press-molded to produce the succeeding sheet 3 is also suitable. As a mixer, a planetary stirrer etc. are mentioned.

接著薄片3的厚度沒有特別限定,其較佳為5μm以上,更佳為15μm以上。如果小於5μm,則會有出現翹曲的半導體晶圓或產生與半導體晶片不接著的部位,會有接著面積變得不穩定的情況。另外,接著薄片3的厚度較佳為100μm以下,更佳為50μm以下。如果大於100μm,則會因晶片黏接的載荷而使接著薄片3過度地伸出,從而會有污染焊盤的情況。 The thickness of the sheet 3 is not particularly limited, and is preferably 5 μm or more, and more preferably 15 μm or more. If it is less than 5 μm, there may be a case where a warped semiconductor wafer or a portion which does not follow the semiconductor wafer is generated, and the subsequent area may become unstable. Further, the thickness of the sheet 3 is preferably 100 μm or less, more preferably 50 μm or less. If it is larger than 100 μm, the subsequent sheet 3 is excessively protruded due to the load of the wafer bonding, and there is a case where the pad is contaminated.

接著薄片3被用於半導體裝置之製造中。具體而言,被作為用於將引線框等被黏物與半導體晶片接著的膜(以下稱作「晶片貼裝膜」)使用。作為被黏物,可以舉出引線框、內插板、半導體晶片等。 The sheet 3 is then used in the manufacture of a semiconductor device. Specifically, it is used as a film for adhering an adherend such as a lead frame to a semiconductor wafer (hereinafter referred to as a "wafer mounting film"). Examples of the adherend include a lead frame, an interposer, and a semiconductor wafer.

接著薄片3較佳以附有切割薄片之接著薄片的形態使用。 The sheet 3 is then preferably used in the form of a sheet with a dicing sheet attached thereto.

(附有切割薄片之接著薄片10) (with the sheet 10 of the cut sheet)

對於附有切割薄片之接著薄片10進行說明。 The following sheet 10 with the dicing sheet attached will be described.

如圖2所示,附有切割薄片之接著薄片10具備切割片1及配置於切割片1上的接著薄片3。切割片1具備基材11及配置於基材11上的黏著劑層12。接著薄片3被配置於黏著劑層12上。 As shown in FIG. 2, the succeeding sheet 10 with the dicing sheet is provided with the dicing sheet 1 and the contiguous sheet 3 disposed on the dicing sheet 1. The dicing sheet 1 includes a base material 11 and an adhesive layer 12 disposed on the base material 11. The sheet 3 is then placed on the adhesive layer 12.

如圖3所示,附有切割薄片之接著薄片10可以是僅在工件(半導體晶圓4等)貼附部分形成有接著薄片3的構成。 As shown in FIG. 3, the succeeding sheet 10 to which the dicing sheet is attached may be a structure in which the subsequent sheet 3 is formed only on the attached portion of the workpiece (semiconductor wafer 4 or the like).

基材11是成為附有切割薄片之接著薄片10的強度母體,較佳具有紫外線透過性的材料。作為基材11,例如可以舉出低密度聚乙烯、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、聚甲基戊烯等之聚烯烴、乙烯-乙酸乙烯酯共聚物、離聚物樹脂、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、聚胺酯、聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等之聚酯、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、芳綸(紙)、玻璃、玻璃纖維布、氟樹脂、聚氯乙烯、聚 偏二氯乙烯、纖維素系樹脂、矽酮樹脂、金屬(箔)、紙等。 The base material 11 is a strength matrix which is a back sheet 10 to which a dicing sheet is attached, and is preferably a material having ultraviolet ray permeability. Examples of the substrate 11 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, and homopolymerization. Polyolefins such as propylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random) , alternating) copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate, polyester, polycarbonate, poly Yttrium, polyetheretherketone, polyimine, polyetherimide, polyamine, wholly aromatic polyamine, polyphenylene sulfide, aramid (paper), glass, fiberglass cloth, fluororesin , polyvinyl chloride, poly A vinylidene chloride, a cellulose resin, an anthrone resin, a metal (foil), paper, or the like.

對於基材11的表面,為了提高與相鄰的層的密著性、保持性等,可以實施慣用的表面處理,例如鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離射線處理等之化學或物理的處理、借助底塗劑(例如後述的粘合物質)的塗佈處理。 The surface of the substrate 11 can be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high-voltage shock exposure, ionizing radiation treatment, etc., in order to improve adhesion to adjacent layers, retention, and the like. Chemical or physical treatment, coating treatment by a primer (for example, a binder described later).

基材11的厚度沒有特別限制,可以適當地決定,然而一般為5~200μm左右。 The thickness of the substrate 11 is not particularly limited and may be appropriately determined, but is generally about 5 to 200 μm.

作為黏著劑層12的形成中所用的黏著劑沒有特別限制,例如可以使用丙烯酸系黏著劑、橡膠系黏著劑等之一般的壓敏性接著劑。作為壓敏性接著劑,從半導體晶圓或玻璃等忌諱污染的電子零件的利用超純水或醇等之有機溶劑的清潔清洗性等方面考慮,較佳以丙烯酸系聚合物作為基礎聚合物的丙烯酸系黏著劑。 The adhesive used for the formation of the adhesive layer 12 is not particularly limited, and for example, a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. As a pressure-sensitive adhesive, it is preferable to use an acrylic polymer as a base polymer from the viewpoints of cleaning and cleaning properties of an organic solvent such as ultrapure water or alcohol, such as a semiconductor wafer or glass. Acrylic adhesive.

作為丙烯酸聚合物,例如可以舉出將(甲基)丙烯酸烷基酯(例如甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、仲丁酯、叔丁酯、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、二十烷基酯等之烷基的碳數為1~30、特別是碳數為4~18的直鏈狀或支鏈狀的烷基酯等)及(甲基)丙烯酸環烷基酯(例如環戊基酯、環己基酯等)的1種或2種以上作為單體成分使用的丙烯酸系聚 合物等。又,所謂(甲基)丙烯酸酯,是指丙烯酸酯及/或甲基丙烯酸酯,本發明的所謂(甲基)全都是相同的意思。 As the acrylic polymer, for example, an alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, or amyl ester) may be mentioned. , isoamyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, decyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecane The alkyl group of the ester, the tetradecyl ester, the hexadecyl ester, the octadecyl ester, the eicosyl ester or the like has a carbon number of 1 to 30, particularly a linear chain having a carbon number of 4 to 18. Acrylic polymerization using one or more of a cycloalkyl (meth)acrylate (for example, a cyclopentyl ester or a cyclohexyl ester) as a monomer component. Compounds, etc. Further, the term "(meth)acrylate" means acrylate and/or methacrylate, and the so-called (meth) of the present invention means the same.

丙烯酸系聚合物也可以出於凝聚力、耐熱性等改性的目的,根據需要,包含對應於能夠與前述(甲基)丙烯酸烷基酯或環烷基酯共聚的其他單體成分的單元。作為此種單體成分,例如可以舉出丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等之含有羧基的單體:馬來酸酐、衣康酸酐等酸酐單體:(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)甲酯等之含有羥基的單體: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)丙烯酸磺內酯、(甲基)丙烯醯氧基萘磺酸等之含有磺酸基的單體:2-羥基乙基丙烯醯基磷酸酯等之含有磷酸基的單體:丙烯醯胺、丙烯腈等。此等可以共聚的單體成分可以使用1種或2種以上。此等可以共聚的單體的使用量較佳為全部單體成分的40重量%以下。 The acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, as needed, for the purpose of modification such as cohesive force and heat resistance. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. A carboxyl group-containing monomer: an anhydride monomer such as maleic anhydride or itaconic anhydride: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Ester, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (methyl) a hydroxyl group-containing monomer such as (4-hydroxymethylcyclohexyl)methyl acrylate: styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, a sulfonic acid group-containing monomer such as methyl acrylamide propyl sulfonic acid, (meth) sultone, or (meth) propylene phthaloxy naphthalene sulfonic acid: 2-hydroxyethyl propylene decyl phosphate A monomer containing a phosphate group, such as acrylamide or acrylonitrile. These monomer components which can be copolymerized may be used alone or in combination of two or more. The amount of such copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.

此外,為了使丙烯酸系聚合物交聯,也可以根據需要作為共聚用單體成分包含多官能性單體等。作為 此等多官能性單體,例如可以舉出己二醇二(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、聚酯(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯等。此等多官能性單體也可以使用1種或2種以上。對於多官能性單體的使用量,從黏著特性等方面考慮,較佳為全部單體成分的30重量%以下。 Further, in order to crosslink the acrylic polymer, a polyfunctional monomer or the like may be contained as a monomer component for copolymerization as needed. As Examples of such a 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, polyester (meth) acrylate, urethane (meth) acrylate, 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 from the viewpoint of adhesion characteristics and the like.

丙烯酸系聚合物可以藉由將單一單體或2種以上的單體混合物聚合而得到。聚合可以利用溶液聚合、乳液聚合、本體聚合、懸浮聚合等之任意的方式來進行。從防止對清潔的被黏物的污染等方面考慮,較佳低分子量物質的含量小的丙烯酸系聚合物。從這一點考慮,丙烯酸系聚合物的數平均分子量較佳為30萬以上,更佳為40萬~300萬左右。 The 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 method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization or the like. From the viewpoint of preventing contamination of the cleaned adherend, etc., an acrylic polymer having a small content of a low molecular weight substance is preferred. From this point of view, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably about 400,000 to 3,000,000.

另外,在前述黏著劑中,為了提高作為基礎聚合物的丙烯酸系聚合物等的數平均分子量,也可以適當地採用外部交聯劑。作為外部交聯方法的具體方法,可以舉出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有的交聯劑並使之反應的方法。在使用外部交聯劑的情況下,其使用量可以根據與要交聯的基礎聚合物的均衡,此外,更進一步根據作為黏著 劑的使用用途適當地決定。一般而言,相對於前述基礎聚合物100重量份,較佳摻合5重量份左右以下,更佳摻合0.1~5重量份。此外,在黏著劑中,根據需要,在前述成分以外,也可以使用以往公知的各種增黏劑、防老化劑等添加劑。 Further, in the above-mentioned adhesive, 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 a specific method of the external crosslinking method, a method of adding a crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or a melamine crosslinking agent, and reacting them may be mentioned. In the case of using an external crosslinking agent, the amount used may be based on the equilibrium with the base polymer to be crosslinked, and further, based on adhesion The use of the agent is appropriately determined. In general, it is preferably blended in an amount of about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, in the adhesive, if necessary, additives such as various conventionally known tackifiers and anti-aging agents may be used in addition to the above components.

黏著劑層12可以利用輻射線固化型黏著劑來形成。放射線固化型黏著劑可以利用紫外線等之放射線的照射使交聯度增大而使其黏著力容易地降低。 The adhesive layer 12 can be formed using a radiation curable adhesive. The radiation-curable adhesive can be irradiated with radiation such as ultraviolet rays to increase the degree of crosslinking and to easily reduce the adhesion.

藉由僅對圖2所示的黏著劑層12的與工件貼附部分對應的部分12a進行放射線照射,就可以設置與其他部分12b的黏著力的差。該情況下,由未固化的放射線固化型黏著劑形成的前述部分12b與接著薄片3黏著,可以確保切割時的保持力。 By irradiating only the portion 12a of the adhesive layer 12 corresponding to the workpiece attachment portion shown in Fig. 2 with radiation, the difference in adhesion to the other portion 12b can be set. In this case, the portion 12b formed of the uncured radiation-curable adhesive adheres to the succeeding sheet 3, and the holding force at the time of cutting can be ensured.

另外,藉由與圖3所示的接著薄片3對應地使放射線固化型的黏著劑層12固化,就可以形成黏著力明顯降低的前述部分12a。該情況下,可以將晶圓環固定在由未固化的放射線固化型黏著劑形成的前述部分12b上。 Further, by curing the radiation-curable adhesive layer 12 corresponding to the succeeding sheet 3 shown in Fig. 3, the portion 12a in which the adhesive force is remarkably lowered can be formed. In this case, the wafer ring can be fixed to the aforementioned portion 12b formed of an uncured radiation-curable adhesive.

即,在利用放射線固化型黏著劑形成黏著劑層12的情況下,較佳以使黏著劑層12中的前述部分12a的黏著力<其他部分12b的黏著力的方式對前述部分12a進行放射線照射。 In other words, in the case where the adhesive layer 12 is formed by the radiation-curable adhesive, it is preferable to irradiate the portion 12a with the adhesion of the portion 12a in the adhesive layer 12 to the adhesion of the other portion 12b. .

放射線固化型黏著劑可以沒有特別限制地使用具有碳-碳雙鍵等之放射線固化性的官能基、並且顯示 出黏著性的黏著劑。作為放射線固化型黏著劑,例如可以例示出在前述丙烯酸系黏著劑、橡膠系黏著劑等之一般的壓敏性黏著劑中摻合有放射線固化性的單體成分或低聚物成分的添加型的放射線固化型黏著劑。 The radiation-curable adhesive can be used without any particular limitation, and a radiation-curable functional group having a carbon-carbon double bond or the like can be used and displayed. Adhesive adhesive. As a radiation-curable adhesive, for example, an additive type in which a radiation-curable monomer component or an oligomer component is blended in a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be exemplified. Radiation-curing adhesive.

作為所摻合的放射線固化性的單體成分,例如可以舉出胺基甲酸酯低聚物、胺基甲酸酯(甲基)丙烯酸酯、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。另外,放射線固化性的低聚物成分可以舉出胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物,其分子量適合為100~30000左右的範圍。放射線固化性的單體成分或低聚物成分的摻合量可以根據前述黏著劑層的種類適當地決定能夠降低黏著劑層的黏著力的量。一般而言,相對於構成黏著劑的丙烯酸系聚合物等之基礎聚合物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 urethane (meth) acrylate, and a trimethylolpropane tri(meth) acrylate. , tetramethylol methane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (methyl) ) acrylate, 1,4-butanediol di(meth)acrylate, and the like. In addition, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the molecular weight thereof is preferably 100~. The range is around 30,000. The blending amount of the radiation-curable monomer component or the oligomer component can be appropriately determined according to the type of the pressure-sensitive adhesive layer to reduce the adhesion of the pressure-sensitive adhesive layer. In general, it is, for example, 5 to 500 parts by weight, preferably about 40 to 150 parts by weight, per 100 parts by weight of the base polymer of the acrylic polymer or the like constituting the pressure-sensitive adhesive.

另外,作為放射線固化型黏著劑,除了前述說明的添加型的放射線固化型黏著劑以外,還可以舉出作為基礎聚合物使用了在聚合物側鏈或主鏈中或主鏈末端具有碳-碳雙鍵的聚合物的內在型的放射線固化型黏著劑。內在型的放射線固化型黏著劑不需要含有作為低分子成分的低聚物成分等,或者不大量包含,因此低聚物成分等不 會隨時間推移而在粘合劑中移動,可以形成穩定的層結構的黏著劑層,因而較佳。 In addition, as the radiation-curable adhesive, in addition to the above-described additive-type radiation-curable adhesive, carbon-carbon having a carbon-carbon in a polymer side chain or a main chain or a main chain end may be used as a base polymer. An intrinsic type of radiation-curable adhesive of a double bond polymer. The intrinsic radiation-curable adhesive does not need to contain an oligomer component or the like as a low molecular component, or is not contained in a large amount, and thus the oligomer component or the like is not It is preferred to move in the adhesive over time to form a stable layer structure of the adhesive layer.

前述具有碳-碳雙鍵的基礎聚合物可以沒有特別限制地使用具有碳-碳雙鍵、並且具有黏著性的聚合物。作為此等基礎聚合物,較佳以丙烯酸系聚合物作為基本骨架的聚合物。作為丙烯酸系聚合物的基本骨架,可以舉出前述例示過的丙烯酸系聚合物。 The aforementioned base polymer having a carbon-carbon double bond can be a polymer having a carbon-carbon double bond and having adhesiveness without particular limitation. As such a base polymer, a polymer having an acrylic polymer as a basic skeleton is preferred. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.

碳-碳雙鍵向前述丙烯酸系聚合物中的導入法沒有特別限制,可以採用各種方法,但向聚合物側鏈中導入碳-碳雙鍵容易進行分子設計。例如,可以舉出預先將丙烯酸系聚合物中具有官能基的單體共聚後、使具有能夠與該官能基反應的官能團及碳-碳雙鍵的化合物在維持碳-碳雙鍵的放射線固化性的同時進行縮合或加成反應的方法。 The introduction method of the carbon-carbon double bond to the acrylic polymer is not particularly limited, and various methods can be employed. However, introduction of a carbon-carbon double bond into the polymer side chain facilitates molecular design. For example, a method in which a monomer having a functional group in an acrylic polymer is copolymerized, and a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is maintained in the radiation curing property of the carbon-carbon double bond is maintained. A method of performing a condensation or addition reaction at the same time.

作為此等官能基的組合的例子,可以舉出羧酸基與環氧基、羧酸基與氮丙啶基、羥基與異氰酸酯基等。此等官能基的組合當中從反應追蹤的容易度考慮,適合為羥基與異氰酸酯基的組合。另外,利用此等官能基的組合,如果是生成前述具有碳-碳雙鍵的丙烯酸系聚合物的組合,則官能基可以處於丙烯酸系聚合物和前述化合物的任意一側,但在之較佳的組合中,適合為丙烯酸系聚合物具有羥基、前述化合物具有異氰酸酯基的情況。該情況下,作為具有碳-碳雙鍵的異氰酸酯化合物,例如可以舉出甲基丙烯醯基異氰酸酯、2-甲基丙烯醯氧基乙基異氰酸 酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。另外,作為丙烯酸系聚合物,使用將前述例示的含有羥基的單體或2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚的醚系化合物等共聚而得的聚合物。 Examples of the combination of such functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is suitable from the viewpoint of easiness of reaction tracking. Further, by using a combination of these functional groups, if a combination of the above-mentioned acrylic polymer having a carbon-carbon double bond is produced, the functional group may be on either side of the acrylic polymer and the above compound, but it is preferred. In the combination, the acrylic polymer has a hydroxyl group, and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate and 2-methyl propylene methoxyethyl isocyanate. Ester, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, a hydroxyl group-containing monomer exemplified above, an ether compound of 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether, or the like is used. Copolymerized polymer.

前述內在型的放射線固化型黏著劑可以單獨地使用前述具有碳-碳雙鍵的基礎聚合物(特別是丙烯酸系聚合物),然而也可以以不使特性惡化的程度摻合前述放射線固化性的單體成分或低聚物成分。放射線固化性的低聚物成分等通常相對於基礎聚合物100重量份為30重量份的範圍內,較佳為0~10重量份的範圍。 The above-mentioned intrinsic radiation-curable adhesive may be a base polymer (particularly an acrylic polymer) having a carbon-carbon double bond as described above, but may be blended with the above-mentioned radiation curable to such an extent that the properties are not deteriorated. Monomer component or 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.

在前述放射線固化型黏著劑中,在利用紫外線等使之固化的情況下含有光聚合引發劑。作為光聚合引發劑,例如可以舉出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之α-乙酮醇系化合物: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-嗎啉代丙烷-1-苯乙酮系化合物:苯偶姻乙醚、苯偶姻異丙醚、茴香偶姻甲醚等之苯偶姻醚系化合物:苯偶醯二甲基縮酮等縮酮系化合物:2-萘磺醯氯等之芳香族磺醯氯系化合物:1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟等之光活性肟系化合物:二苯甲酮、苯甲醯苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等之二苯甲酮系化合物:噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二 氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮系化合物:樟腦醌:鹵化酮:醯基膦氧化物:醯基膦酸酯等。光聚合引發劑的摻合量相對於構成黏著劑的丙烯酸系聚合物等之基礎聚合物100重量份例如為0.05~20重量份左右。 In the radiation-curable pressure-sensitive adhesive, a photopolymerization initiator is contained when it is cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone and α-hydroxy-α,α'-dimethylacetophenone. α-Ethyl alcohol compound such as 2-methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone: methoxyacetophenone, 2,2-dimethoxy-2-phenylbenzene Ethyl ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropan-1-acetophenone-based compound: A benzoin ether compound such as benzoin ethyl ether, benzoin isopropyl ether or fennel dimethyl ether: a ketal compound such as benzoin dimethyl ketal: an aromatic compound such as 2-naphthalenesulfonium chloride a sulfonium chloride compound: a photoactive lanthanide compound such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)anthracene: benzophenone, benzamidine benzoic acid, 3, a benzophenone compound such as 3'-dimethyl-4-methoxybenzophenone: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethyl Thiophenone, isopropyl thioxanthone, 2,4-di Thioxanone compounds such as chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.: camphorquinone: halogenated ketone: mercaptophosphine oxide: mercaptophosphine Acid esters, etc. The blending amount of the photopolymerization initiator 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.

另外,作為放射線固化型黏著劑,例如可以舉出日本特開昭60-196956號公報中公開的、含有具有2個以上的不飽和鍵的加成聚合性化合物、具有環氧基的烷氧基矽烷等之光聚合性化合物、與羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽系化合物等之光聚合引發劑的橡膠系黏著劑或丙烯酸系黏著劑等。 In addition, examples of the radiation-curable adhesive include an addition polymerizable compound having two or more unsaturated bonds and an alkoxy group having an epoxy group, which are disclosed in JP-A-60-196956. A photopolymerizable compound such as decane, a rubber-based adhesive such as a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine or a phosphonium salt compound, or an acrylic adhesive.

在前述放射線固化型的黏著劑層12中,根據需要,也可以含有利用放射線照射而著色的化合物。藉由使黏著劑層12中含有利用放射線照射而著色的化合物,就可以僅對被放射線照射的部分進行著色。利用放射線照射而著色的化合物是在放射線照射前為無色或淡色、因放射線照射而變為有色的化合物,例如可以舉出隱色染料等。利用放射線照射而著色的化合物的使用比例可以適當地設定。 In the radiation-curable adhesive layer 12, a compound colored by radiation irradiation may be contained as needed. By including the compound colored by the radiation irradiation in the adhesive layer 12, it is possible to color only the portion irradiated with the radiation. The compound which is colored by radiation irradiation is a colorless or pale color before radiation irradiation, and becomes a colored compound by radiation irradiation, and examples thereof include a leuco dye. The ratio of use of the compound colored by radiation irradiation can be appropriately set.

黏著劑層12的厚度沒有特別限定,然而從兼顧防止晶片切割面的缺口或保持接著薄片3的固定等方面考慮,較佳為1~50μm左右。較佳為2~30μm,更佳為5~25μm。 The thickness of the adhesive layer 12 is not particularly limited, but is preferably about 1 to 50 μm from the viewpoint of preventing the chipping of the wafer cut surface or the fixing of the sheet 3. It is preferably 2 to 30 μm, more preferably 5 to 25 μm.

附有切割薄片之接著薄片10較佳由隔膜保護 (未圖示)。即,較佳在接著薄片3上配置有隔膜。隔膜具有作為在用於實際使用前保護接著薄片3的保護材料的功能。隔膜在向接著薄片3上貼附工件時被剝離。作為隔膜,也可以使用聚對苯二甲酸乙二醇酯(PET)、聚乙烯、聚丙烯、或利用氟系剝離劑、長鏈烷基丙烯酸酯系剝離劑等之剝離劑進行了表面塗佈的塑膠膜或紙等。 The backing sheet 10 with the dicing sheet is preferably protected by a diaphragm (not shown). That is, it is preferable to arrange a separator on the subsequent sheet 3. The separator has a function as a protective material for protecting the succeeding sheet 3 before being used for actual use. The separator is peeled off when the workpiece is attached to the succeeding sheet 3. As the separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used for surface coating. Plastic film or paper.

附有切割薄片之接著薄片10可以利用通常的方法製造。例如,藉由將切割片1的黏著劑層12與接著薄片3貼合,就可以製造附有切割薄片之接著薄片10。 The succeeding sheet 10 to which the cut sheet is attached can be manufactured by a usual method. For example, by bonding the adhesive layer 12 of the dicing sheet 1 to the subsequent sheet 3, the succeeding sheet 10 with the dicing sheet can be manufactured.

在剝離溫度25℃、剝離速度300mm/min的條件下,將接著薄片3從切割片1中拉剝離時的剝離力較佳為0.1N/10mm以上。如果小於0.1N/10mm,則有可能產生晶片飛出。另一方面,剝離力較佳為0.2N/10mm以下。如果大於0.2N/10mm,則會有拾取變得困難的趨勢。 At a peeling temperature of 25 ° C and a peeling speed of 300 mm/min, the peeling force when the sheet 3 is peeled off from the dicing sheet 1 is preferably 0.1 N/10 mm or more. If it is less than 0.1 N/10 mm, it is possible to cause the wafer to fly out. On the other hand, the peeling force is preferably 0.2 N/10 mm or less. If it is larger than 0.2 N/10 mm, there is a tendency that picking becomes difficult.

(半導體裝置之製造方法) (Method of Manufacturing Semiconductor Device)

如圖4所示,在附有切割薄片之接著薄片10上壓接半導體晶圓4。作為半導體晶圓4,可以舉出矽晶圓、碳化矽晶圓、化合物半導體晶圓等。作為化合物半導體晶圓,可以舉出氮化鎵晶圓等。 As shown in FIG. 4, the semiconductor wafer 4 is crimped onto the subsequent sheet 10 to which the dicing sheet is attached. Examples of the semiconductor wafer 4 include a tantalum wafer, a tantalum carbide wafer, and a compound semiconductor wafer. As the compound semiconductor wafer, a gallium nitride wafer or the like can be given.

作為壓接方法,例如可以舉出利用壓接輥等之擠壓機構進行擠壓的方法等。 As the pressure bonding method, for example, a method of pressing by a pressing mechanism such as a pressure roller or the like can be given.

壓接溫度(貼附溫度)較佳為35℃以上,更佳為37℃以上。壓接溫度的上限越低越好,較佳為50℃ 以下,更佳為45℃以下。藉由在低溫下壓接,可以防止對半導體晶圓4的熱影響,從而可以抑制半導體晶圓4的翹曲。另外,壓力較佳為1×105Pa~1×107Pa,更佳為2×105Pa~8×106Pa。 The crimping temperature (attachment temperature) is preferably 35 ° C or higher, more preferably 37 ° C or higher. The lower limit of the crimping temperature is preferably as low as possible, and is preferably 50 ° C or lower, more preferably 45 ° C or lower. By the pressure bonding at a low temperature, the thermal influence on the semiconductor wafer 4 can be prevented, and the warpage of the semiconductor wafer 4 can be suppressed. Further, the pressure is preferably from 1 × 10 5 Pa to 1 × 10 7 Pa, more preferably from 2 × 10 5 Pa to 8 × 10 6 Pa.

如圖5所示,藉由切割半導體晶圓4,形成黏晶用晶片41。黏晶用晶片41具備半導體晶片5及配置於半導體晶片5上的接著膜31。半導體晶片5具備晶片主體部502及配置於晶片主體部502上的焊盤501。焊盤501為電極焊盤。作為焊盤501的材料,可以舉出鋁等。本步驟中,可以採用切入至附有切割薄片之接著薄片10的被稱作全切的切割方式等。作為切割裝置沒有特別限定,可以使用以往公知的裝置。另外,半導體晶圓4由於由附有切割薄片之接著薄片10接著固定,因此可以抑制晶片缺口或晶片飛散,並且還可以抑制半導體晶圓4的破損。 As shown in FIG. 5, the die wafer 41 is formed by cutting the semiconductor wafer 4. The die bond wafer 41 includes a semiconductor wafer 5 and an adhesive film 31 disposed on the semiconductor wafer 5. The semiconductor wafer 5 includes a wafer main body portion 502 and a pad 501 disposed on the wafer main body portion 502. The pad 501 is an electrode pad. As a material of the pad 501, aluminum etc. are mentioned. In this step, a cutting method called a full cut that cuts into the succeeding sheet 10 with the cut sheet may be employed. The cutting device is not particularly limited, and a conventionally known device can be used. Further, since the semiconductor wafer 4 is subsequently fixed by the succeeding sheet 10 with the dicing sheet attached, it is possible to suppress wafer notch or wafer scattering, and it is also possible to suppress breakage of the semiconductor wafer 4.

對黏晶用晶片41進行拾取。作為拾取的方法沒有特別限定,可以採用以往公知的各種方法。例如可以舉出將各個半導體晶片5從附有切割薄片之接著薄片10側用針頂起、然後用拾取裝置來拾取黏晶用晶片41的方法等。 The wafer 41 for the die bonding is picked up. The method of picking up is not particularly limited, and various conventionally known methods can be employed. For example, a method in which each of the semiconductor wafers 5 is lifted from the side of the succeeding sheet 10 with the dicing sheet, and then the wafer 41 is picked up by the pick-up device.

在黏著劑層12為紫外線固化型的情況下,在向黏著劑層12照射紫外線後進行拾取。由此,由於黏著劑層12對黏晶用晶片41的黏著力降低,因此可以容易地拾取黏晶用晶片41。紫外線照射時的照射強度、照射時 間等條件沒有特別限定,只要適當地根據需要設定即可。 When the adhesive layer 12 is of an ultraviolet curing type, the adhesive layer 12 is irradiated with ultraviolet rays and then picked up. Thereby, since the adhesive force of the adhesive layer 12 to the die-bonding wafer 41 is lowered, the die-bonding wafer 41 can be easily picked up. Irradiation intensity when irradiated with ultraviolet light, when irradiated The conditions such as the interval are not particularly limited, and may be appropriately set as needed.

如圖6所示,藉由將黏晶用晶片41壓接在被黏物6上而得到附有半導體晶片之被黏體61。附有半導體晶片之被黏物61具備被黏物體6、配置於被黏物6上的接著膜31及配置於接著膜31上之半導體晶片5。被黏物6具備主體部602及配置於主體部602上的端子部601。 As shown in FIG. 6, the adherend 61 with the semiconductor wafer is obtained by crimping the die-bonding wafer 41 against the adherend 6. The adherend 61 with the semiconductor wafer is provided with the adherend 6 , the adhesive film 31 disposed on the adherend 6 , and the semiconductor wafer 5 disposed on the adhesive film 31 . The adherend 6 includes a main body portion 602 and a terminal portion 601 disposed on the main body portion 602.

將黏晶用晶片41壓接在被黏物6上的溫度(以下稱作「晶片貼裝溫度」)較佳為80℃以上,更佳為90℃以上。另外,晶片貼裝溫度較佳為150℃以下,更佳為130℃以下。 The temperature at which the die bond wafer 41 is pressure-bonded to the adherend 6 (hereinafter referred to as "wafer mounting temperature") is preferably 80 ° C or higher, more preferably 90 ° C or higher. Further, the wafer mounting temperature is preferably 150 ° C or lower, more preferably 130 ° C or lower.

藉由將附有半導體晶片之被黏物61在加壓下加熱而使接著薄膜31固化。由此,使半導體晶片5固著於被黏物6。藉由在加壓下使接著薄膜31固化,就可以使存在於接著薄膜31與被黏物6之間的空隙消失,從而可以確保接著薄膜31與被黏物6接觸的面積。 The adhesive film 31 is cured by heating the adherend 61 with the semiconductor wafer under pressure. Thereby, the semiconductor wafer 5 is fixed to the adherend 6. By curing the adhesive film 31 under pressure, the void existing between the adhesive film 31 and the adherend 6 can be eliminated, and the area in which the film 31 is in contact with the adherend 6 can be secured.

作為在加壓下進行加熱的方法,例如可以舉出對配置在填充有惰性氣體的腔室內的附有半導體晶片之被黏物61進行加熱的方法等。加壓氣氛的壓力較佳為0.5kg/cm2(4.9×10-2MPa)以上,更佳為1kg/cm2(9.8×10-2MPa)以上,進一步較佳為5kg/cm2(4.9×10-1MPa)以上。如果是0.5kg/cm2以上,則可以使存在於接著薄膜31與被黏物6之間的空隙容易地消失。加壓氣氛的壓力較佳為20kg/cm2(1.96MPa)以下,更佳為18kg/cm2 (1.77MPa)以下,進一步較佳為15kg/cm2(1.47MPa)以下。如果是20kg/cm2以下,則可以抑制由過度的加壓造成的接著薄膜31的伸出。 As a method of heating under pressure, for example, a method of heating the adherend 61 with a semiconductor wafer placed in a chamber filled with an inert gas may be mentioned. The pressure of the pressurized atmosphere is preferably 0.5 kg/cm 2 (4.9 × 10 -2 MPa) or more, more preferably 1 kg/cm 2 (9.8 × 10 -2 MPa) or more, further preferably 5 kg/cm 2 (4.9). ×10 -1 MPa) or more. If it is 0.5 kg/cm 2 or more, the void existing between the adhesive film 31 and the adherend 6 can be easily eliminated. Pressure of the pressurized atmosphere is preferably 20kg / cm 2 (1.96MPa) or less, more preferably 18kg / cm 2 (1.77MPa) or less, more preferably 15kg / cm 2 (1.47MPa) or less. If it is 20 kg/cm 2 or less, the protrusion of the adhesive film 31 caused by excessive pressurization can be suppressed.

加熱溫度較佳為80℃以上,更佳為120℃以上,進一步較佳為150℃以上,特別佳為170℃以上。如果是80℃以上,則可以將接著薄膜31設為適度的硬度,可以利用加壓熟化使空隙有效地消失。加熱溫度較佳為260℃以下,更佳為200℃以下,更佳為180℃以下。如果是260℃以下,則可以防止接著膜31的分解。 The heating temperature is preferably 80 ° C or higher, more preferably 120 ° C or higher, further preferably 150 ° C or higher, and particularly preferably 170 ° C or higher. When it is 80 ° C or more, the adhesive film 31 can be set to an appropriate hardness, and the voids can be effectively eliminated by pressurization and aging. The heating temperature is preferably 260 ° C or lower, more preferably 200 ° C or lower, more preferably 180 ° C or lower. If it is 260 ° C or less, decomposition of the adhesive film 31 can be prevented.

加熱時間較佳為0.1小時以上,更佳為0.2小時以上。加熱時間較佳為24小時以下,更佳為3小時以下,進一步較佳為1小時以下,特別佳為30分鐘以下。 The heating time is preferably 0.1 hour or longer, more preferably 0.2 hour or longer. The heating time is preferably 24 hours or shorter, more preferably 3 hours or shorter, further preferably 1 hour or shorter, and particularly preferably 30 minutes or shorter.

如圖7所示,進行將焊盤501與端子部601用焊線7電連接的絲焊步驟。作為焊線7的材料,可以舉出銅等。 As shown in FIG. 7, a wire bonding step of electrically connecting the pad 501 and the terminal portion 601 with the bonding wires 7 is performed. As a material of the bonding wire 7, copper etc. are mentioned.

絲焊步驟包含將焊線7的一端與焊盤501接合的步驟、將焊線7的另一端與端子部601接合的步驟等。 The wire bonding step includes a step of joining one end of the bonding wire 7 to the pad 501, a step of bonding the other end of the bonding wire 7 to the terminal portion 601, and the like.

對於將焊線7的一端與焊盤501接合的步驟,具體而言,是藉由在將焊線7的一端壓接在焊盤501上的同時對焊線7施加超聲波而將焊線7與焊盤501接合的步驟。 For the step of bonding one end of the bonding wire 7 to the pad 501, specifically, the bonding wire 7 is applied by applying ultrasonic waves to the bonding wire 7 while crimping one end of the bonding wire 7 onto the pad 501. The step of bonding the pads 501.

較佳在175℃以上、更佳在200℃以上進行接合。另一方面,較佳在300℃以下、更佳在260℃以下進 行接合。 Bonding is preferably carried out at 175 ° C or higher, more preferably at 200 ° C or higher. On the other hand, it is preferably at least 300 ° C, more preferably below 260 ° C. Line bonding.

對於將焊線7的另一端與端子部601接合的步驟,具體而言,是藉由在將焊線7的另一端壓接在端子部601上的同時對焊線7施加超聲波而將焊線7與端子部601接合的步驟。 For the step of joining the other end of the bonding wire 7 to the terminal portion 601, specifically, the bonding wire is applied to the bonding wire 7 while the other end of the bonding wire 7 is crimped onto the terminal portion 601. 7 is a step of joining the terminal portion 601.

在進行絲焊步驟後,進行利用密封樹脂8將半導體晶片5密封的密封步驟。本步驟是為了保護搭載於被黏物6上的半導體晶片5、焊線7而進行的。本步驟是藉由將密封用的樹脂用模具成型而進行。作為密封樹脂8,例如使用環氧系的樹脂。樹脂密封時的加熱溫度較佳為165℃以上,更佳為170℃以上,加熱溫度較佳為185℃以下,更佳為180℃以下。 After the wire bonding step, a sealing step of sealing the semiconductor wafer 5 with the sealing resin 8 is performed. This step is performed to protect the semiconductor wafer 5 and the bonding wires 7 mounted on the adherend 6. This step is carried out by molding a resin for sealing with a mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is preferably 165 ° C or higher, more preferably 170 ° C or higher, and the heating temperature is preferably 185 ° C or lower, more preferably 180 ° C or lower.

根據需要,也可以在密封後再進行加熱(後固化步驟)。由此,就可以使密封步驟中固化不足的密封樹脂8完全地固化。加熱溫度可以適當地設定。 Heating may also be carried out after sealing as needed (post-cure step). Thereby, the sealing resin 8 which is insufficiently cured in the sealing step can be completely cured. The heating temperature can be set as appropriate.

如上所述,可以利用包括如下步驟的方法來製造半導體裝置,即,準備附有切割薄片之接著薄片10的步驟、與在接著薄片3上壓接半導體晶圓4的步驟、藉由切割配置於接著薄片3上之半導體晶圓4而形成具備包含焊盤501的半導體晶片5及配置於半導體晶片5上的接著薄膜31的黏晶用晶片41的步驟、與藉由在具備端子部601的被黏物6上壓接黏晶用晶片41而形成附有晶片的被黏物61的步驟、與藉由加熱附有晶片的被黏物61而使接著膜31固化的步驟、與在使接著膜31固化的步驟後進 行的包含將包含銅的焊線7的一端與焊盤501接合的步驟及將焊線7的另一端與端子部601接合的步驟。 As described above, the semiconductor device can be manufactured by a method including the steps of preparing the succeeding sheet 10 with the dicing sheet attached thereto, and the step of crimping the semiconductor wafer 4 on the succeeding sheet 3 by dicing Next, a step of forming the semiconductor wafer 5 including the pad 501 and the die-bonding wafer 41 of the bonding film 31 disposed on the semiconductor wafer 5 on the semiconductor wafer 4 on the sheet 3, and the step of including the terminal portion 601 The step of forming the wafer-attached adherend 61 by crimping the die-bonding wafer 41 onto the adherend 6 and the step of curing the adhesive film 31 by heating the adherend 61 with the wafer, and the bonding film 31 curing steps after the advance The row includes a step of bonding one end of the bonding wire 7 including copper to the pad 501 and a step of bonding the other end of the bonding wire 7 to the terminal portion 601.

〔實施例〕 [Examples]

以下,使用實施例對本發明進行詳細說明,然而本發明只要不超出其主旨,就不限定於以下的實施例。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples as long as the invention is not exceeded.

對實施例中使用的成分進行說明。 The components used in the examples will be described.

丙烯酸橡膠:Nagase ChemteX公司製的Teisan Resin SG-708-6(包含羧基及羥基之丙烯酸酯共聚物、Mw:70萬、酸值:9mgKOH/g、玻璃化轉變溫度:4℃) Acrylic rubber: Teisan Resin SG-708-6 manufactured by Nagase ChemteX Co., Ltd. (acrylate copolymer containing carboxyl group and hydroxyl group, Mw: 700,000, acid value: 9 mgKOH/g, glass transition temperature: 4 ° C)

環氧樹脂1:日本化藥公司製的EPPN-501HY(環氧當量169g/eq.的環氧樹脂) Epoxy Resin 1: EPPN-501HY (epoxy equivalent 169g/eq. epoxy resin) manufactured by Nippon Kayaku Co., Ltd.

環氧樹脂2:日本化藥公司製的EOCN-1020(環氧當量198g/eq.的環氧樹脂) Epoxy Resin 2: EOCN-1020 (epoxy equivalent 198 g/eq. epoxy resin) manufactured by Nippon Kayaku Co., Ltd.

環氧樹脂3:三菱化學公司製的jER828(環氧當量190g/eq.的環氧樹脂) Epoxy Resin 3: jER828 (epoxy equivalent: 190 g/eq. epoxy resin) manufactured by Mitsubishi Chemical Corporation

酚醛樹脂1:明和化成公司製的MEH-7851S(羥基當量209g/eq.的酚醛樹脂) Phenolic Resin 1: MEH-7851S (phenolic resin having a hydroxyl equivalent of 209 g/eq.) manufactured by Minghe Chemical Co., Ltd.

酚醛樹脂2:荒川化學公司製的P-180(羥基當量105g/eq.的酚醛樹脂) Phenolic Resin 2: P-180 (phenolic resin having a hydroxyl equivalent of 105 g/eq.) manufactured by Arakawa Chemical Co., Ltd.

二氧化矽填料:Admatechs公司製的SO-25R(BET比表面積為6.5m2/g、新摩氏硬度為7的球狀二氧化矽) Ceria filler: SO-25R manufactured by Admatechs Co., Ltd. (spherical cerium oxide having a BET specific surface area of 6.5 m 2 /g and a new Mohs hardness of 7)

催化劑:北興化學工業股份有限公司製的TPP-MK (四苯基鏻四對甲苯基硼酸鹽) Catalyst: TPP-MK manufactured by Beixing Chemical Industry Co., Ltd. (tetraphenylphosphonium tetra-p-tolyl borate)

〔接著薄片及附有切割薄片之接著薄片之製作〕 [Following of the sheet and the subsequent sheet with the cut sheet]

依照表1中記載的摻合比,將表1中記載的各成分及溶劑(甲乙酮)加入混合動力混合器(Kyence製HM-500)的攪拌釜中,以攪拌模式進行3分鐘攪拌、混合。將所得的清漆用模塗機塗佈在脫模處理膜(三菱樹脂股份有限公司製的MRA50)上後,使之乾燥,得到厚度20μm的接著薄片。從接著薄片中切出直徑230mm的圓形的接著薄片,將圓形的接著薄片在25℃貼附在切割片(日東電工股份有限公司製的P2130G)的黏著劑層上,製作出附有切割薄片之接著薄片。 The components and the solvent (methyl ethyl ketone) described in Table 1 were placed in a stirred tank of a hybrid mixer (HM-500 manufactured by Kyence) in accordance with the blending ratios shown in Table 1, and stirred and mixed in a stirring mode for 3 minutes. The obtained varnish was applied onto a release-treated film (MRA50, manufactured by Mitsubishi Plastics Co., Ltd.) by a die coater, and then dried to obtain a subsequent sheet having a thickness of 20 μm. A circular backing sheet having a diameter of 230 mm was cut out from the succeeding sheet, and a circular succeeding sheet was attached to an adhesive layer of a dicing sheet (P2130G manufactured by Nitto Denko Corporation) at 25 ° C to prepare a cut sheet. The next sheet of the sheet.

〔評估〕 [assessment]

對所得的接著薄片、附有切割薄片之接著薄片,進行了以下的評估。將結果表示於表1中。 The following evaluation was performed on the obtained succeeding sheet and the succeeding sheet with the cut sheet. The results are shown in Table 1.

(彈性係數及Tg的測定) (Measurement of elastic modulus and Tg)

在60℃貼合接著薄片而得到厚度400μm的層合薄片。藉由將層合薄片加工為10mm×30mm×400μm的尺寸而得到加工品。藉由將加工品在175℃加熱30分鐘而使之固化。在固化後使用動態黏彈性系測定裝置(TA Instruments公司製的RSA III)測定加工品的黏彈性。測定條件是在溫度範圍-10℃~285℃、升溫速度10℃/min、 卡盤間距22.5mm、10Hz下進行。根據所得的彈性係數資料,讀取200℃的彈性係數。另外將所得的tanδ的峰的溫度設為Tg。 The laminated sheet was bonded at 60 ° C to obtain a laminated sheet having a thickness of 400 μm. The processed product was obtained by processing the laminated sheet into a size of 10 mm × 30 mm × 400 μm. The processed product was cured by heating at 175 ° C for 30 minutes. After curing, the viscoelasticity of the processed product was measured using a dynamic viscoelasticity measuring apparatus (RSA III manufactured by TA Instruments). The measurement conditions are in the temperature range of -10 ° C to 285 ° C, the temperature increase rate is 10 ° C / min, The chuck spacing was 22.5 mm at 10 Hz. According to the obtained elastic coefficient data, the elastic coefficient of 200 ° C was read. Further, the temperature of the peak of the obtained tan δ was defined as Tg.

(反應熱之測定) (Measurement of reaction heat)

從接著薄片中切出10mg的試驗片。將試驗片用鋁盤夾持,從而準備了測定樣品。還準備了僅包含鋁盤的參比用樣品。使用差示掃描熱量測定裝置(Seiko Instruments公司製的DSC6220),以升溫速度10℃/min、溫度範圍25℃~300℃進行了測定。藉由將所得的發熱反應峰的熱量除以樣品的重量而算出反應熱。 10 mg of the test piece was cut out from the subsequent sheet. The test piece was sandwiched with an aluminum pan to prepare a measurement sample. A reference sample containing only an aluminum pan was also prepared. The measurement was carried out using a differential scanning calorimeter (DSC6220 manufactured by Seiko Instruments Co., Ltd.) at a temperature elevation rate of 10 ° C/min and a temperature range of 25 ° C to 300 ° C. The heat of reaction was calculated by dividing the heat of the obtained exothermic reaction peak by the weight of the sample.

(峰消失時間之測定) (Measurement of peak disappearance time)

從接著薄片中切出10mg的試驗片。將試驗片用鋁盤夾持,從而準備了測定用樣品。還準備了僅包含鋁盤的參比用樣品。使用差示掃描熱量測定裝置(Seiko Instruments公司製的DSC6220),在以3分鐘從25℃升溫到175℃、然後將175℃維持3小時的條件下進行了DSC測定。從DSC曲線中讀取從到達175℃到反應峰消失的時間。而且,所謂「反應峰消失」,是指以使測定用樣品與參比用樣品的溫度相等的方式對兩者施加的每單位時間的熱能的輸入的差一定。將實施例2的DSC曲線表示於圖8中。 10 mg of the test piece was cut out from the subsequent sheet. The test piece was sandwiched with an aluminum pan to prepare a sample for measurement. A reference sample containing only an aluminum pan was also prepared. DSC measurement was carried out under the conditions of raising the temperature from 25 ° C to 175 ° C for 3 minutes and then maintaining 175 ° C for 3 hours using a differential scanning calorimeter (DSC 6220 manufactured by Seiko Instruments Co., Ltd.). The time from the arrival of 175 ° C to the disappearance of the reaction peak was read from the DSC curve. In addition, "the disappearance of the reaction peak" means that the difference in the input of the thermal energy per unit time applied to both of the sample for measurement and the temperature of the reference sample is constant. The DSC curve of Example 2 is shown in Fig. 8.

(絲焊性) (wire solderability)

研削對一面進行了鋁蒸鍍的晶圓,從而得到厚度100μm的切割用晶圓。將切割用晶圓貼附在附有切割薄片之接著薄片上,然後切割為2mm見方,由此得到附有接著薄片的晶片。將帶有接著薄片的晶片在120℃、0.1MPa、1sec的條件下晶片貼裝在Cu引線框上。藉由在175℃加熱30分鐘而使接著薄片固化。使用絲焊裝置(K & S公司製的Maxum Plus),在一個晶片上焊接5條線直徑20μm的Cu金屬線。在輸出80Amp、時間10ms及載荷50g的條件下將Cu金屬線接在Cu引線框上。在200℃、輸出125Amp、時間10ms及載荷80g的條件下將Cu金屬線接在晶片上。將無法將5條Cu金屬線中的1條以上焊接在晶片上的情況判定為×,將可以將5條Cu金屬線中的5條焊接在晶片上的情況判定為○。 A wafer on which aluminum vapor deposition was performed on one side was ground to obtain a wafer for dicing having a thickness of 100 μm. The dicing wafer was attached to the subsequent sheet with the dicing sheet, and then cut into 2 mm squares, thereby obtaining a wafer with the subsequent sheet. The wafer with the succeeding sheet was placed on the Cu lead frame at 120 ° C, 0.1 MPa, and 1 sec. The subsequent sheet was cured by heating at 175 ° C for 30 minutes. Five wire metal wires having a wire diameter of 20 μm were welded on one wafer using a wire bonding apparatus (Maxum Plus manufactured by K & S). The Cu metal wire was attached to the Cu lead frame under the conditions of output 80 Amp, time 10 ms, and load 50 g. The Cu metal wire was attached to the wafer at 200 ° C, output of 125 Amp, time of 10 ms, and load of 80 g. The case where one of the five Cu metal wires could not be soldered to the wafer was judged as ×, and the case where five of the five Cu metal wires could be soldered to the wafer was judged as ○.

3‧‧‧接著薄片 3‧‧‧ followed by thin slices

Claims (9)

一種半導體裝置之製造所使用之接著薄片,在利用以3分鐘從25℃升溫到175℃、然後將175℃維持3小時的條件下藉由DSC測定所描繪的DSC曲線中,從到達175℃到反應峰消失的時間未達30分鐘,在10Hz下測定藉由於175℃下加熱30分鐘使固化而得的固化物的黏彈性,所得到的200℃的伸張彈性係數為100MPa以上。 A follow-up sheet used in the manufacture of a semiconductor device, which was measured by DSC under conditions of a temperature increase from 25 ° C to 175 ° C for 3 minutes and then 175 ° C for 3 hours, from reaching 175 ° C to The time at which the reaction peak disappeared was less than 30 minutes, and the viscoelasticity of the cured product obtained by curing at 175 ° C for 30 minutes was measured at 10 Hz, and the obtained tensile modulus at 200 ° C was 100 MPa or more. 如請求項1之接著薄片,其中,利用將25℃~300℃的範圍中以每分鐘10℃升溫的條件下的DSC測定得到的反應熱為80mJ/mg以上。 In the subsequent sheet of the claim 1, the heat of reaction obtained by DSC measurement under the condition of raising the temperature at 10 ° C per minute in the range of 25 ° C to 300 ° C is 80 mJ / mg or more. 如請求項1之接著薄片,其中,藉由於將175℃加熱30分鐘使固化而得之固化物的Tg為150℃以上。 The subsequent sheet of claim 1 wherein the cured product obtained by curing at 175 ° C for 30 minutes has a Tg of 150 ° C or higher. 如請求項1之接著薄片,其包含BET比表面積為4m2/g以上的二氧化矽填料,前述二氧化矽填料的含量為50重量%以上。 The succeeding sheet of claim 1, which comprises a cerium oxide filler having a BET specific surface area of 4 m 2 /g or more, and the content of the cerium oxide filler is 50% by weight or more. 如請求項1之接著薄片,其包含羥基當量為120g/eq.以下之酚醛樹脂。 A subsequent sheet of claim 1 comprising a phenolic resin having a hydroxyl equivalent weight of 120 g/eq. or less. 如請求項1之接著薄片,其包含樹脂成分,前述樹脂成分包含環氧樹脂、酚醛樹脂及丙烯酸樹脂, 前述樹脂成分100重量%中之前述丙烯酸樹脂的含量為14重量%以下。 An adhesive sheet according to claim 1, which comprises a resin component, and the resin component comprises an epoxy resin, a phenol resin, and an acrylic resin. The content of the acrylic resin in 100% by weight of the resin component is 14% by weight or less. 如請求項6之接著薄片,其中,前述酚醛樹脂之羥基當量為120g/eq.以下。 The subsequent sheet of claim 6, wherein the phenolic resin has a hydroxyl equivalent of 120 g/eq. or less. 一種附有切割薄片之接著薄片,具備:切割片,其具備基材及配置於前述基材上的黏著劑層、與請求項1之接著薄片,其配置於前述黏著劑層上。 A succeeding sheet with a dicing sheet, comprising: a dicing sheet comprising a substrate, an adhesive layer disposed on the substrate, and a subsequent sheet of the claim 1 disposed on the adhesive layer. 一種半導體裝置之製造方法,包含:準備請求項8之附有切割薄片之接著薄片之步驟、與於前述接著薄片壓接半導體晶圓之步驟、與藉由切割配置於前述接著薄片上之前述半導體晶圓,而形成具備焊盤之半導體晶片及配置於前述半導體晶片上之接著薄膜之黏晶用晶片之步驟、與藉由於具備端子部的被黏著體壓接前述黏晶用晶片而形成附有晶片之被黏著體之步驟、與藉由加熱前述附有晶片之被黏著體而使前述接著薄膜固化之步驟、與於使前述黏著薄膜固化之步驟之後進行的包含將包含銅的金屬線之一端與前述焊盤接合的步驟及將前述金屬線的另一端與前述端子部接合之步驟。 A method of manufacturing a semiconductor device, comprising: preparing a step of attaching a dicing sheet with a dicing sheet, a step of crimping a semiconductor wafer with the splicing sheet, and splicing the semiconductor disposed on the splicing sheet a step of forming a semiconductor wafer having a pad and a die-bonding wafer disposed on the semiconductor wafer, and a wafer bonded to the die-bonding body by a bonding body having a terminal portion a step of adhering the wafer, a step of curing the adhesive film by heating the bonded body attached to the wafer, and a step of curing the adhesive film to include one end of a metal wire containing copper a step of bonding to the pad and a step of bonding the other end of the wire to the terminal.
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