TWI496867B - Adhesive film for semiconductor and semiconductor package using the same - Google Patents

Adhesive film for semiconductor and semiconductor package using the same Download PDF

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Publication number
TWI496867B
TWI496867B TW101149059A TW101149059A TWI496867B TW I496867 B TWI496867 B TW I496867B TW 101149059 A TW101149059 A TW 101149059A TW 101149059 A TW101149059 A TW 101149059A TW I496867 B TWI496867 B TW I496867B
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Taiwan
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adhesive film
group
weight
epoxy resin
curing agent
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TW101149059A
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Chinese (zh)
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TW201333150A (en
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Ah Ram Pyun
Min Kyu Hwang
In Cheon Han
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Cheil Ind Inc
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Publication of TWI496867B publication Critical patent/TWI496867B/en

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    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02002—Preparing wafers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material 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
    • H01L2224/13138—Material 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
    • H01L2224/13147—Copper [Cu] as principal constituent
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    • H01L2224/812—Applying energy for connecting
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    • H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Description

用於半導體的黏著劑膜以及使用其之半導體封裝體Adhesive film for semiconductor and semiconductor package using same 發明領域Field of invention

本發明有關用於半導體的黏著劑膜以及使用其之半導體封裝體。詳言之，本發明有關用於半導體的黏著劑膜，其可提供助熔活性及絕緣黏著劑層的固化控制，維持液態安定性而未造成在安裝後因酸殘留之缺陷且確保在低溫的流動性以預防氣泡型式之孔隙的產生同時能夠有充分的孔隙填充，以及使用其之半導體封裝體。The present invention relates to an adhesive film for a semiconductor and a semiconductor package using the same. In particular, the present invention relates to an adhesive film for a semiconductor which can provide a fluxing activity and a curing control of an insulating adhesive layer, maintain liquid stability without causing defects due to acid residue after mounting, and ensuring low temperature. The fluidity prevents the generation of pores of the bubble type while having sufficient pore filling, and a semiconductor package using the same.

發明背景Background of the invention

為了實現高容量的半導體元件，使用一質化方法例如在每單位面積上增加複數個元件的大規模整合，及一定量方法例如數個晶片疊合封裝以增加容量。In order to realize a high-capacity semiconductor element, a mass method is used, for example, a large-scale integration of a plurality of elements per unit area, and a certain amount of methods such as a plurality of wafer-stacked packages to increase the capacity.

如一封裝方法，通常使用一傳統多-晶片封裝體(MCP)，其中複數個晶片使用黏著劑堆疊，且上及下晶片經由導線接合電連接。然而，因為在疊合晶片的空間外，還有用於導線接合之空間而增加了整體封裝體大小，存在一不必要的空間。As a packaging method, a conventional multi-chip package (MCP) is generally used in which a plurality of wafers are stacked using an adhesive, and the upper and lower wafers are electrically connected via wire bonding. However, since there is room for wire bonding outside the space for laminating the wafer and the overall package size is increased, there is an unnecessary space.

為了克服MCP的缺點，引入一晶圓級堆疊封裝體 (WSP)。在WSP中，在一晶圓上形成一直通矽通道(TSV)，在該處形成一電路並以傳導材料充填以直接電性連接層。In order to overcome the shortcomings of MCP, a wafer level stacked package is introduced. (WSP). In the WSP, a through-channel (TSV) is formed on a wafer where a circuit is formed and filled with a conductive material to directly connect the layers.

MCP與WSP為定量方法以增加半導體元件的容量，其中複數個晶片黏合並使用黏著劑堆疊。MCP and WSP are quantitative methods to increase the capacity of semiconductor components in which a plurality of wafers are bonded together using an adhesive stack.

近來驅勢為較小且高度整合的電子組件，一在半導體元件安裝中使用一較小區域的倒裝晶片吸引較多的注意。在用於倒裝晶片安裝中的半導體元件之鋁電極上形成一凸塊且電性連接至一電路板上的線路。此凸塊通常由一焊料形成，且形成於鋁電極上的焊料凸塊曝露且經由沉積或電鍍連接至晶片內部電線。此外，使用一在線連接元件中形成的金柱凸塊。Recently, it has been driven by smaller and highly integrated electronic components, and the use of a smaller area of flip chip in the mounting of semiconductor components has attracted more attention. A bump is formed on the aluminum electrode of the semiconductor component used in the flip chip mounting and electrically connected to a circuit on a circuit board. The bumps are typically formed of a solder and the solder bumps formed on the aluminum electrodes are exposed and connected to the internal wires of the wafer via deposition or plating. In addition, gold stud bumps formed in an in-line connecting element are used.

當如同使用一經連接倒裝晶片的半導體元件，因為連接部份的電極曝露至空氣中且在晶片與板間的線性膨脹係數的差異大，在後續的製程如焊料迴流中因熱而施用很大的應力至凸塊的連接部份，因而造成一在安裝上的可靠性問題。為了解決此問題並改良凸塊連接至板後之連接部份的可靠性，在半導體元件與板間的孔隙填充一樹脂糊或一黏著劑膜並固化之，因此固定半導體元件至板上。此處，使用一傳統助熔活化劑例如有機酸以除去一在焊料上的氧化物層並以鬆弛金屬連接。然而，當助熔活化劑殘留時，產生氣泡，例如孔隙，因為酸成份而腐蝕接線而降低連接可靠性。因此，需要一去除殘留助熔活化劑的助熔製程。然而，當在半導體晶片與板間的空隙為小時，其難以清除殘留的助熔活化劑。因此，需要不會涉及額外助熔製 程的絕緣黏著劑層。When using a semiconductor device to which a flip chip is connected, since the electrode of the connection portion is exposed to the air and the difference in linear expansion coefficient between the wafer and the plate is large, it is applied greatly by heat in a subsequent process such as solder reflow. The stress is applied to the connecting portion of the bump, thus causing a reliability problem in mounting. In order to solve this problem and improve the reliability of the connection portion after the bump is attached to the board, the pores between the semiconductor element and the board are filled with a resin paste or an adhesive film and cured, thereby fixing the semiconductor element to the board. Here, a conventional flux activator such as an organic acid is used to remove an oxide layer on the solder and connect with a relaxed metal. However, when the flux activator remains, bubbles, such as voids, are generated, and the wiring is corroded by the acid component to lower the connection reliability. Therefore, a fluxing process for removing residual flux activator is required. However, when the gap between the semiconductor wafer and the board is small, it is difficult to remove the residual flux activator. Therefore, there is no need to involve additional fluxing The insulating adhesive layer of the process.

為了發展一不需要額外助熔製程的絕緣黏著劑層，在傳統方法中直接使用酸如羧酸及葵二酸。然而，酸的直接使用可造成絕緣黏著劑層的液態安定性及在膜形狀中於室溫的安定性上的降低。再者，因為酸，故未能適當控制此絕緣黏著劑層的固化，且在安裝於一產品後殘餘的酸可能造成缺陷如凸塊的腐蝕及離子遷移。In order to develop an insulating adhesive layer that does not require an additional fluxing process, acids such as carboxylic acids and azelaic acid are used directly in conventional processes. However, the direct use of the acid can result in a decrease in the liquid stability of the insulating adhesive layer and the stability at room temperature in the film shape. Furthermore, due to the acid, the curing of the insulating adhesive layer is not properly controlled, and the residual acid after mounting on a product may cause defects such as bump corrosion and ion migration.

再者，當此黏著劑組成物在具有凸塊之的疊合時未足夠固化，一上晶片因為偏差不能疊合至預定的位置，因而造成在凸塊間的連接失效。Further, when the adhesive composition is not sufficiently cured at the time of lamination with bumps, the upper wafer cannot be overlapped to a predetermined position due to the deviation, thereby causing connection failure between the bumps.

本發明之一態樣提供一用於半導體的黏著劑膜。One aspect of the present invention provides an adhesive film for a semiconductor.

在一實施例中，一種用於半導體的黏著劑膜可包括一丙烯酸樹脂；一環氧樹脂；及助熔活性固化劑，其中二放熱峰之面積比例(E1/E2)大於1，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積。In one embodiment, an adhesive film for a semiconductor may include an acrylic resin; an epoxy resin; and a fluxing active curing agent, wherein an area ratio (E1/E2) of the two exothermic peaks is greater than 1, which is when used. The differential scanning calorimeter (DSC) measures the amount of heat generated by the adhesive film during curing. E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is detected at a temperature of 200 ° C or higher. The area of the exothermic peak measured.

在另一實施例中，一種用於半導體的黏著劑膜在60℃具有1x104 泊(Poise)至15x104 泊的熔融黏度，及具有大於1的二放熱峰之面積比例(E1/E2)，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積。In another embodiment, an adhesive film for a semiconductor having a melt viscosity of 1x10 4 poise (the Poise) to 15x10 4 poise at 60 ℃, and two exothermic peaks having an area ratio of greater than 1 (E1 / E2), which In order to measure the heat generated by the adhesive film during curing using a differential scanning calorimeter (DSC), E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E 2 is at a temperature of 200 ° C or more. The area of the exothermic peak detected at high time.

在又一實施例中，一種用於半導體的黏著劑膜可包括一丙烯酸樹脂；一環氧樹脂；及一助熔活性固化劑，且在60℃具有1x104 泊(Poise)至15x104 泊的熔融黏度，及一在260℃固化10秒後約5%或更少的殘餘固化率，如以方程式1表示：殘餘固化率=(Hc/Hi)x 100----(1)，其中Hi為在黏著劑膜製備後產生的最初熱量，及Hc為在260℃固化10秒後產生的熱量。In yet another embodiment, a method for the adhesive film for a semiconductor may include an acrylic resin; an epoxy resin; and a flux active curing agent and having a melt 1x10 4 poises (the Poise) to 15x10 4 poise at 60 ℃ Viscosity, and a residual cure rate of about 5% or less after curing at 260 ° C for 10 seconds, as expressed by Equation 1: residual cure rate = (Hc / Hi) x 100 - (1), where Hi is The initial heat generated after the preparation of the adhesive film, and Hc is the heat generated after curing at 260 ° C for 10 seconds.

黏著劑膜可具有環氧樹脂對助熔活性固化劑的當量比例(環氧樹脂當量重/助熔活性固化劑當量重)為在0.7至1.6間。The adhesive film may have an equivalent ratio of epoxy resin to fluxing active curing agent (epoxy equivalent weight / fluxing active curing agent equivalent weight) of between 0.7 and 1.6.

此用於半導體的黏著劑膜可更包含一咪唑化合物。The adhesive film for a semiconductor may further comprise an imidazole compound.

此助熔活性固化劑的存在量為基於黏著劑膜總重的5wt%至20wt%。The fluxing active curing agent is present in an amount of from 5 wt% to 20 wt%, based on the total weight of the adhesive film.

此咪唑化合物的存在量為基於黏著劑膜總重的0.5wt%至5wt%。This imidazole compound is present in an amount of from 0.5% by weight to 5% by weight based on the total weight of the adhesive film.

此用於半導體的黏著劑膜可包括20wt%至50wt%的丙烯酸樹脂；20wt%至50wt%的環氧樹脂；5wt%至20wt%的助熔活性固化劑；及15wt%至40wt%的填充劑。The adhesive film for a semiconductor may include 20% by weight to 50% by weight of an acrylic resin; 20% by weight to 50% by weight of an epoxy resin; 5% by weight to 20% by weight of a fluxing active curing agent; and 15% by weight to 40% by weight of a filler .

此助熔活性固化劑可包括至少一由化學式1至3表示之助熔活性固化劑：[化學式1] 其中[A]表示一含有酸酐基及可選擇地包括1至3雙鍵的C4至C8環結構；[B]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R1 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；及n為一由0至2範圍的整數； 其中[C]表示一含有酸酐基及可選擇地包括1至3雙鍵的C4至C8環結構；[D]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R2 為選自由鹵素原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；及n為一由1至4範圍的整數；[化學式3] 其中[E]表示一含有酸酐基及可選擇地包括1至3雙鍵的C4至C8環結構；[F]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R3 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；R4 為選自由下列化學式(i)至(viii)表示之化合物；及n為一由1至4範圍的整數， The fluxing active curing agent may include at least one fluxing active curing agent represented by Chemical Formulas 1 to 3: [Chemical Formula 1] Wherein [A] represents a C4 to C8 ring structure containing an acid anhydride group and optionally a 1 to 3 double bond; [B] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group. R 1 is a group selected from the group consisting of a hydrogen atom, a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and n is a group from 0 to 0. 2 range of integers; Wherein [C] represents a C4 to C8 ring structure containing an acid anhydride group and optionally a 1 to 3 double bond; [D] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group. R 2 is a group selected from the group consisting of a halogen atom, a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and n is a group from 1 to 1 4 range of integers; [Chemical Formula 3] Wherein [E] represents a C4 to C8 ring structure containing an acid anhydride group and optionally a 1 to 3 double bond; [F] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group. And R 3 is a group selected from the group consisting of a hydrogen atom, a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and R 4 is selected from the following chemical formula; (i) to (viii) a compound; and n is an integer ranging from 1 to 4,

咪唑化合物可由化學式4表示： 其中R1 與R2 各自獨立為C1至C10伸烷基。The imidazole compound can be represented by Chemical Formula 4: Wherein R 1 and R 2 are each independently a C1 to C10 alkylene group.

此咪唑化合物可具有200℃至270℃的熔點。This imidazole compound may have a melting point of from 200 ° C to 270 ° C.

b對c的比例可在1.2至5：1範圍內，其中c為助熔活性固化劑的量而b為環氧樹脂的量。The ratio of b to c may range from 1.2 to 5:1, where c is the amount of fluxing active curing agent and b is the amount of epoxy resin.

此黏著劑膜可更包括一矽烷偶合劑。The adhesive film may further comprise a decane coupling agent.

本發明的另一態樣為提供一使用用於半導體元件的黏著劑膜黏合之半導體封裝體。此半導體封裝體包括：一基材；一第一半導體晶片，其安裝在該基材上；一第二半導體晶片，其安裝在該第一半導體晶片上；及一黏著劑膜，其充填在該第一半導體晶片與該第二半導體晶片間的空間，其中該黏著劑膜具有一大於1的放熱峰之二面積比例(E1/E2)，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積。Another aspect of the present invention provides a semiconductor package in which an adhesive film for a semiconductor element is bonded. The semiconductor package includes: a substrate; a first semiconductor wafer mounted on the substrate; a second semiconductor wafer mounted on the first semiconductor wafer; and an adhesive film filled in the a space between the first semiconductor wafer and the second semiconductor wafer, wherein the adhesive film has a two-area ratio (E1/E2) of an exothermic peak greater than one, which is used to measure adhesion when using a differential scanning thermal card (DSC) When the film is heated during curing, E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is the area of the exothermic peak detected at a temperature of 200 ° C or higher.

此半導體封裝體可更包括一在該黏著劑膜中形成的導體，其電性連接該第一半導體晶片至該第二半導體晶片。The semiconductor package may further include a conductor formed in the adhesive film electrically connecting the first semiconductor wafer to the second semiconductor wafer.

10‧‧‧第一半導體晶片10‧‧‧First semiconductor wafer

11‧‧‧導體11‧‧‧Conductor

15‧‧‧黏著劑膜15‧‧‧Adhesive film

20‧‧‧第二半導體晶片20‧‧‧Second semiconductor wafer

50‧‧‧基材50‧‧‧Substrate

100‧‧‧半導體封裝體100‧‧‧Semiconductor package

圖1為本發明一實施例的半導體封裝體之剖面示意圖。1 is a cross-sectional view showing a semiconductor package in accordance with an embodiment of the present invention.

較佳實施例之詳細說明Detailed description of the preferred embodiment

現詳述本發明的實施例。應瞭解後述實施例為 僅用於說明之用而非用以任何方式解釋以限制本發明。Embodiments of the invention are now described in detail. It should be understood that the embodiment described later is It is for illustrative purposes only and is not intended to be construed as limiting the invention.

除非特別限制，每一組份的含量為以固態含量表示。Unless otherwise specified, the content of each component is expressed in terms of solid content.

依本發明，一種用於半導體的黏著劑膜可包括一丙烯酸樹脂；一環氧樹脂；及一助熔活性固化劑。According to the present invention, an adhesive film for a semiconductor may include an acrylic resin; an epoxy resin; and a fluxing active curing agent.

丙烯酸樹脂Acrylic

丙烯酸樹脂可只包括(甲基)丙烯酸酯共聚物或包括(甲基)丙烯酸酯共聚物與其他聚物樹脂的混合物。較佳地，此(甲基)丙烯酸酯共聚物可包括一環氧基。在某些實施例中，丙烯酸樹脂可具有約500g/eq至約5000g/eq的環氧樹脂當量重。在此範圍內，黏著劑膜確保優良的可靠性。The acrylic resin may include only a (meth) acrylate copolymer or a mixture including a (meth) acrylate copolymer and other polymer resins. Preferably, the (meth) acrylate copolymer may comprise an epoxy group. In certain embodiments, the acrylic resin can have an epoxy equivalent weight of from about 500 g/eq to about 5000 g/eq. Within this range, the adhesive film ensures excellent reliability.

此丙烯酸樹脂具有一約50,000g/mol至約5,000,000g/mol的重量平均分子量，較佳約100,000g/mol至約1,000,000g/mol。在此範圍內，丙烯酸樹脂確保在黏著劑膜之膜成形性、機械性質及孔隙移除能力方面的優良性質。The acrylic resin has a weight average molecular weight of from about 50,000 g/mol to about 5,000,000 g/mol, preferably from about 100,000 g/mol to about 1,000,000 g/mol. Within this range, the acrylic resin ensures excellent properties in terms of film formability, mechanical properties, and void removal ability of the adhesive film.

在一實施例中，此丙烯酸樹脂可為一烷基(甲基)丙烯酸酯單體與一環氧丙基(甲基)丙烯酸酯單體的共聚物。In one embodiment, the acrylic resin can be a copolymer of a monoalkyl (meth) acrylate monomer and a mono-glycidyl (meth) acrylate monomer.

烷基(甲基)丙烯酸酯單體做為賦予膜黏合性且可含有一C1至C20烷基(甲基)丙烯酸酯。此烷基(甲基)丙烯酸酯單體的範例可包括2-乙基己基甲基丙烯酸酯、異辛基丙烯酸酯、2-乙基己基丙烯酸酯、乙基丙烯酸酯、n-丁基 丙烯酸酯、異-丁基丙烯酸酯、十八基甲丙烯酸酯及其相似者，但未限制於此。The alkyl (meth) acrylate monomer serves as a film imparting adhesive and may contain a C1 to C20 alkyl (meth) acrylate. Examples of the alkyl (meth) acrylate monomer may include 2-ethylhexyl methacrylate, isooctyl acrylate, 2-ethylhexyl acrylate, ethyl acrylate, n-butyl Acrylate, iso-butyl acrylate, octadecyl methacrylate and the like, but are not limited thereto.

此環氧丙基(甲基)丙烯酸酯單體的範例包括環氧丙基甲基丙烯酸酯、環氧丙基丙烯酸酯及其相似者，但未限制於此。Examples of the epoxy propyl (meth) acrylate monomer include propylene methacrylate, epoxy acrylate, and the like, but are not limited thereto.

在其他的實施例中，合宜地，此丙烯酸樹脂可在共聚作用中可更包括一含羥基(甲基)丙烯酸酯單體。此含羥基之(甲基)丙烯酸酯單體可包括2-羥基乙基甲基丙烯酸酯、2-羥基乙基丙烯酸酯、3-羥基丙基甲基丙烯酸酯、3-羥基丙基丙烯酸酯、羥基丙基(甲基)丙烯酸酯、4-羥基丁基丙烯酸酯、N-(羥基甲基)丙烯酸酯、3-氯-2-羥基丙基甲基丙烯酸酯及其相似者，但未限制於此。In other embodiments, conveniently, the acrylic resin may further comprise a hydroxyl-containing (meth) acrylate monomer in the copolymerization. The hydroxyl group-containing (meth) acrylate monomer may include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, Hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, N-(hydroxymethyl) acrylate, 3-chloro-2-hydroxypropyl methacrylate, and the like, but not limited thereto this.

此丙烯酸樹脂可具有一約-30℃至約80℃的玻璃轉化溫度，較佳由約0℃至約60℃，更較佳由約5℃至約35℃。在此範圍內，高流動性可確保提供良好的孔隙移除能力，且可獲得黏著劑膜的高黏著性及可靠性。The acrylic resin may have a glass transition temperature of from about -30 ° C to about 80 ° C, preferably from about 0 ° C to about 60 ° C, more preferably from about 5 ° C to about 35 ° C. Within this range, high fluidity ensures good pore removal and high adhesion and reliability of the adhesive film.

此丙烯酸樹脂可具有在25℃為約1,000cps至約30,000cps的黏度。在此範圍內，黏著劑膜可呈現尺寸均一性及膜的成形性。The acrylic resin may have a viscosity of from about 1,000 cps to about 30,000 cps at 25 °C. Within this range, the adhesive film can exhibit dimensional uniformity and film formability.

丙烯酸樹脂的存在量基於黏著劑膜的總固體含量為20wt%至約50wt%，較佳約22wt%至約45wt%，更較佳約23wt%至約40wt%。在此範圍內，此黏著劑膜可呈現良好的可靠性及確保氣泡型態之孔隙的令人滿意的移除。The acrylic resin is present in an amount of from 20% by weight to about 50% by weight, based on the total solids of the adhesive film, preferably from about 22% by weight to about 45% by weight, more preferably from about 23% by weight to about 40% by weight. Within this range, the adhesive film can exhibit good reliability and ensure satisfactory removal of the pores of the bubble shape.

環氧樹脂Epoxy resin

此環氧樹脂用於實現硬化及黏著功能且可為液態環氧樹脂、固態環氧樹脂或其等之混合物。The epoxy resin is used for hardening and adhesion functions and may be a liquid epoxy resin, a solid epoxy resin or a mixture thereof.

當一環氧樹脂在室溫(25℃)具有一固相或一接近固相時，此樹脂稱為一固態環氧樹脂，且當一環氧樹脂在室溫(25℃)具有液相時，此樹脂稱為液態環氧樹脂。When an epoxy resin has a solid phase or a near solid phase at room temperature (25 ° C), the resin is called a solid epoxy resin, and when an epoxy resin has a liquid phase at room temperature (25 ° C) This resin is called a liquid epoxy resin.

液態環氧樹脂的範例可包括但未限制為雙酚A-型液態環氧樹脂、雙酚F-型液態環氧樹脂、三-或以上之官能的多官能液態環氧樹脂、橡膠改質之液態環氧樹脂、胺基甲酸酯改質之液態環氧樹脂、丙烯酸改質之液態環氧樹脂及光敏性液態環氧樹脂。此些環氧樹脂可單獨使用或以其等之混合物使用。較佳地，使用雙酚A-型液態環氧樹脂。Examples of liquid epoxy resins may include, but are not limited to, bisphenol A-type liquid epoxy resin, bisphenol F-type liquid epoxy resin, tri- or higher functional polyfunctional liquid epoxy resin, rubber modified Liquid epoxy resin, urethane modified liquid epoxy resin, acrylic modified liquid epoxy resin and photosensitive liquid epoxy resin. These epoxy resins may be used singly or in a mixture thereof. Preferably, a bisphenol A-type liquid epoxy resin is used.

此液態環氧樹脂(b1)可具有一約100至約1500g/eq的環氧樹脂當量重，較佳約150至約800g/eq，且更較佳約為150至400g/eq。在此範圍內，硬化的產品可呈現良好的黏著性，維持一玻璃轉化溫度及具有優良的抗熱性。The liquid epoxy resin (b1) may have an epoxy equivalent weight of from about 100 to about 1500 g/eq, preferably from about 150 to about 800 g/eq, and more preferably from about 150 to 400 g/eq. Within this range, the hardened product exhibits good adhesion, maintains a glass transition temperature, and has excellent heat resistance.

此外，液態環氧樹脂可具有一約100g/mol至約1,000g/mol的重量平均分子量。在此範圍內，此樹脂呈現良好的流動性。Further, the liquid epoxy resin may have a weight average molecular weight of from about 100 g/mol to about 1,000 g/mol. Within this range, this resin exhibits good fluidity.

至於固態環氧樹脂，可使用一具有在室溫為固相或接近固相且具有至少一官能基的環氧樹脂。較佳地，使用一具有軟化點(SP)為約30℃至約100℃的環氧樹脂。例如，固態環氧樹脂可包括雙酚環氧樹脂、酚-酚醛環氧 樹脂、鄰甲酚-酚醛環氧樹脂、多官能環氧樹脂、胺環氧樹脂、含雜環之環氧樹脂、被取代之環氧樹脂、萘酚環氧樹脂及其等之衍生物。As the solid epoxy resin, an epoxy resin having a solid phase or a near solid phase at room temperature and having at least one functional group can be used. Preferably, an epoxy resin having a softening point (SP) of from about 30 ° C to about 100 ° C is used. For example, solid epoxy resins may include bisphenol epoxy resins, phenol-phenolic epoxy Resins, o-cresol-phenolic epoxy resins, polyfunctional epoxy resins, amine epoxy resins, heterocyclic epoxy resins, substituted epoxy resins, naphthol epoxy resins, and the like.

商業可取得的固態環氧樹脂產品包括下列者。雙酚環氧樹脂的範例包括YD-017H、YD-020、YD020-L、YD-014、YD-014ER、YD-013K、YD-019K、YD-019、YD-017R、YD-017、YD-012、YD-011H、YD-011S、YD-011、YDF-2004及YDF-2001(Kukdo Chemical公司)。酚醛環氧樹脂的範例包括EPIKOTE 152及EPIKOTE 154(Yuka-Shell環氧樹脂公司)、EPPN-201、EPPN-501H(Nippon Kayaku公司)、DN438(Dow Chemical公司)及YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644及YDPN-631(Kukdo Chemical公司)。鄰甲酚酚醛環氧樹脂的範例包括YDCN-500-1P、YDCN-500-2P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-8P、YDCN-500-10P、YDCN-500-80P、YDCN-500-80PCA60、YDCN-500-80PBC60、YDCN-500-90P、YDCN-500-90PA75(Kukdo Chemical公司)、EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027(Nippon Kayaku公司)、YDCN-701、YDCN-702、YDCN-703、YDCN-704(Tohto Kasei公司)、及EPICLON N-665-EXP(Dainippon Ink & Chemicals公司)。雙酚系酚醛環氧樹脂的範例KBPN-110、KBPN-120、及KBPN-115(Kukdo Chemical有 限公司)。多官能環氧樹脂的範例包括EPON 1031S(Yuka-Shell環氧樹脂公司)、Araldite 0163(Ciba Specialty Chemical公司)、Dentacol EX-611、Dentacol EX-614、Dentacol EX-614B、Dentacol EX-622、Dentacol EX-512、Dentacol EX-521、Dentacol EX-421、Dentacol EX-411、Dentacol EX-321(Nagase ChemteX公司)、及EP-5200R、KD-1012、EP-5100R、KD-1011、KDT-4400A70、KDT-4400、YH-434L、YH-434及YH-300(Kukdo Chemical公司)。胺環氧樹脂的範例包括EPIKOTE 604(Yuka-Shell Epoxy公司)、YH-434(Tohto Kasei公司)、TETRAD X及TETRAD C(Mitsubishi Gas Chemical公司)、及ELM-120(住友化學公司)。一含雜環的環氧樹脂之範例為Araldite PT-810(Ciba Specialty Chemical公司)。被取代環氧樹脂之範例包括ERL-4234、ERL-4299、ERL-4221、及ERL-4206(Union Carbide公司)。萘酚環氧樹脂之範例包括EPICLON HP-4032、EPICLON HP-4032D、EPICLON HP-4700、及EPICLON 4701(Dainippon Ink & Chemicals公司)。此些環氧樹脂可單獨使用或其等之二或二以上的組合使用。Commercially available solid epoxy products include the following. Examples of bisphenol epoxy resins include YD-017H, YD-020, YD020-L, YD-014, YD-014ER, YD-013K, YD-019K, YD-019, YD-017R, YD-017, YD- 012, YD-011H, YD-011S, YD-011, YDF-2004 and YDF-2001 (Kukdo Chemical). Examples of the phenolic epoxy resin include EPIKOTE 152 and EPIKOTE 154 (Yuka-Shell Epoxy Co., Ltd.), EPPN-201, EPPN-501H (Nippon Kayaku Co., Ltd.), DN438 (Dow Chemical Co.), YDPN-641, YDPN-638A80, YDPN-638, YDPN-637, YDPN-644 and YDPN-631 (Kukdo Chemical). Examples of o-cresol novolac epoxy resin include YDCN-500-1P, YDCN-500-2P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-8P, YDCN-500- 10P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P, YDCN-500-90PA75 (Kukdo Chemical), EOCN-102S, EOCN-103S, EOCN-104S, EOCN -1012, EOCN-1025, EOCN-1027 (Nippon Kayaku), YDCN-701, YDCN-702, YDCN-703, YDCN-704 (Tohto Kasei), and EPICLON N-665-EXP (Dainippon Ink & Chemicals) ). Examples of bisphenol novolac epoxy resins KBPN-110, KBPN-120, and KBPN-115 (Kukdo Chemical has Limited company). Examples of multifunctional epoxy resins include EPON 1031S (Yuka-Shell Epoxy Co., Ltd.), Araldite 0163 (Ciba Specialty Chemical Co.), Dentacol EX-611, Dentacol EX-614, Dentacol EX-614B, Dentacol EX-622, Dentacol EX-512, Dentacol EX-521, Dentacol EX-421, Dentacol EX-411, Dentacol EX-321 (Nagase ChemteX), and EP-5200R, KD-1012, EP-5100R, KD-1011, KDT-4400A70, KDT-4400, YH-434L, YH-434 and YH-300 (Kukdo Chemical). Examples of the amine epoxy resin include EPIKOTE 604 (Yuka-Shell Epoxy Co., Ltd.), YH-434 (Tohto Kasei Co., Ltd.), TETRAD X and TETRAD C (Mitsubishi Gas Chemical Co., Ltd.), and ELM-120 (Sumitomo Chemical Co., Ltd.). An example of a heterocyclic-containing epoxy resin is Araldite PT-810 (Ciba Specialty Chemical Co.). Examples of substituted epoxy resins include ERL-4234, ERL-4299, ERL-4221, and ERL-4206 (Union Carbide). Examples of naphthol epoxy resins include EPICLON HP-4032, EPICLON HP-4032D, EPICLON HP-4700, and EPICLON 4701 (Dainippon Ink & Chemicals). These epoxy resins may be used singly or in combination of two or more thereof.

環氧樹脂的存在量以固體含量計佔的黏著劑膜總量之約20wt%至約50wt%，較佳約25wt%至約45wt%，且更較佳約30wt%至約42wt%。在此範圍內，環氧樹脂可確保黏著劑膜的優良可靠性與機械性質。在某些實施例中，當環氧樹脂的量以b表示時，且聚合物樹脂在固相的含量 以a表示時，a可小於b(a<b)。在此狀況下，可獲得優良的可靠性。The epoxy resin is present in an amount of from about 20% by weight to about 50% by weight based on the total amount of the adhesive film, preferably from about 25% by weight to about 45% by weight, and more preferably from about 30% by weight to about 42% by weight. Within this range, the epoxy resin ensures excellent reliability and mechanical properties of the adhesive film. In certain embodiments, when the amount of epoxy resin is represented by b, and the content of the polymer resin in the solid phase When denoted by a, a may be smaller than b (a < b). In this case, excellent reliability can be obtained.

助熔活性固化劑Fusible active curing agent

此黏著劑組成物包括至少一由化學式1至3表示之助熔活性固化劑： 其中[A]表示一含有酸酐基及可選擇地包括1至3雙鍵的C4至C8環結構；[B]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R1 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；及n為一由0至2範圍的整數； 其中[C]表示一含有酸酐基及可選擇地包括1至3雙鍵的C4至C8環結構；[D]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R2 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯 基、及丙烯基組成之組群中；及n為一由1至4範圍的整數；及 其中[E]表示一含有酸酐基及可選擇地包括1至3雙鍵的C4至C8環結構；[F]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R3 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；R4 為選自由下列化學式(i)至(viii)表示之化合物；及n為一由1至4範圍的整數。The adhesive composition includes at least one fluxing active curing agent represented by Chemical Formulas 1 to 3: Wherein [A] represents a C4 to C8 ring structure containing an acid anhydride group and optionally a 1 to 3 double bond; [B] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group. R 1 is a group selected from the group consisting of a hydrogen atom, a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and n is a group from 0 to 0. 2 range of integers; Wherein [C] represents a C4 to C8 ring structure containing an acid anhydride group and optionally a 1 to 3 double bond; [D] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group. R 2 is a group selected from the group consisting of a hydrogen atom, a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and n is a group from 1 to 1 4 range of integers; and Wherein [E] represents a C4 to C8 ring structure containing an acid anhydride group and optionally a 1 to 3 double bond; [F] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group. And R 3 is a group selected from the group consisting of a hydrogen atom, a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and R 4 is selected from the following chemical formula; (i) to (viii) a compound; and n is an integer ranging from 1 to 4.

此助熔活性固化劑的例示可包括但未限制為3,4-二羧基-1,2,3,4-四氫-1-萘丁二酸二酐、順-5-原冰片烯-內-2,3-二羧酐、聯苯酐、雙環[2,2,2]辛-7-烯-2,3,5,6-四羧二酐、酞酐、二苯甲酮-3,3,'4,4'-四羧二酐、內-雙環[2.2.2]辛-5-烯-2,3-二羧酐、升酞酐、反-1,2-環己烷二羧酐、及順-5-原冰片烯-外-2,3-二羧酐，但未限制於此。Examples of such fluxing active curing agents may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, cis-5-formylene-inner -2,3-dicarboxylic anhydride, biphenyl anhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, phthalic anhydride, benzophenone-3,3 , '4,4'-tetracarboxylic dianhydride, endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, decanoic anhydride, trans-1,2-cyclohexane dicarboxylic anhydride And cis-5-formylene-exo-2,3-dicarboxylic anhydride, but is not limited thereto.

在某些實施例中，助熔活性固化劑具有100℃至300℃的熔點，較佳120℃至250℃。在此範圍內，助熔活性固化劑確保在高速攪拌期間的液態安定性。In certain embodiments, the fluxing active curing agent has a melting point of from 100 ° C to 300 ° C, preferably from 120 ° C to 250 ° C. Within this range, the fluxing active curing agent ensures liquid stability during high speed agitation.

此助熔活性固化劑無羧酸。This fluxing active curing agent has no carboxylic acid.

在某些實施例中，助熔活性固化劑的存在量為以固態含量計之黏著劑膜總量的5wt%至20wt%，較佳為5wt%至18wt%。在此範圍內，助熔活性固化劑與環氧樹脂的反應性可充分調整以允許當呈現助熔活性時易於連接。再者，因為助熔活性固化劑提供高流動性，在凸塊間可確保優良的連接性。在一實施例中，當助熔活性固化劑的含量以c表示而環氧樹脂的含量以b表示時，b：c可在約1.2~5：1範圍內，尤以約1.5~4：1為佳。在此範圍內，助熔活性固化劑提供良好的助熔活性與黏著性。In certain embodiments, the fluxing active curing agent is present in an amount from 5 wt% to 20 wt%, preferably from 5 wt% to 18 wt%, based on the total amount of the adhesive film. Within this range, the reactivity of the fluxing active curing agent with the epoxy resin can be sufficiently adjusted to allow for easy attachment when presenting fluxing activity. Furthermore, since the fluxing active curing agent provides high fluidity, excellent connectivity can be ensured between the bumps. In one embodiment, when the content of the fluxing active curing agent is represented by c and the content of the epoxy resin is represented by b, b:c may be in the range of about 1.2 to 5:1, especially about 1.5 to 4:1. It is better. Within this range, the fluxing active curing agent provides good fluxing activity and adhesion.

較佳地，環氧樹脂對助熔活性固化劑的當量比例(環氧樹脂的當量重/助熔活性固化劑的當量重，E/H)可在0.7至1.6範圍間。在此範圍內，黏著劑膜在260℃以10秒短時間接著時具有充足的固化結構，因而當確保充足流動性時，呈現不僅優良的最初黏合性且於濕氣吸收後的黏著性與連接性。較佳地，當量比例E/H在0.72至1.55範圍間。Preferably, the equivalent ratio of the epoxy resin to the fluxing active curing agent (equivalent weight of the epoxy resin / equivalent weight of the fluxing active curing agent, E/H) may range from 0.7 to 1.6. Within this range, the adhesive film has a sufficient solidified structure at 260 ° C for a short time of 10 seconds, so that when sufficient fluidity is ensured, not only excellent initial adhesion but also adhesion and adhesion after moisture absorption are exhibited. Sex. Preferably, the equivalent ratio E/H is in the range of 0.72 to 1.55.

咪唑化合物Imidazole compound

在本發明中，咪唑化合物具有約200℃或更多的熔點。當使用一具有熔點小於200℃的咪唑化合物時，黏著劑膜的固化反應相當早啟始，因而造成在凸塊間之黏著劑膜與接點的流動性劣化。較佳地，咪唑化合物具有約 200℃至約270℃的熔點，尤以約210℃至約265℃為佳。In the present invention, the imidazole compound has a melting point of about 200 ° C or more. When an imidazole compound having a melting point of less than 200 ° C is used, the curing reaction of the adhesive film starts relatively early, thereby causing deterioration in fluidity of the adhesive film and the joint between the bumps. Preferably, the imidazole compound has about The melting point of from 200 ° C to about 270 ° C is particularly preferably from about 210 ° C to about 265 ° C.

咪唑化合物能與環氧樹脂達到固化反應同時呈現助熔活性。尤其，咪唑化合物可滿足用於TSV與具有在特定範圍內之熔融黏度與環氧樹脂當量重的環氧樹脂之絕緣黏著劑膜組成物的熔融性質及快速固化。The imidazole compound can exhibit a fluxing activity while achieving a curing reaction with the epoxy resin. In particular, the imidazole compound satisfies the melting properties and rapid curing of the insulating adhesive film composition for the TSV and the epoxy resin having a specific range of melt viscosity and epoxy equivalent weight.

在某些實施例中，咪唑化合物可由化學式4表示： In certain embodiments, the imidazole compound can be represented by Chemical Formula 4:

其中R1 與R2 各自獨立為C1至C10伸烷基。Wherein R 1 and R 2 are each independently a C1 to C10 alkylene group.

較佳地，R1 及R2 各自獨立為C1至C5伸烷基，更較佳為C1至C3伸烷基。Preferably, R 1 and R 2 are each independently a C1 to C5 alkylene group, more preferably a C1 to C3 alkylene group.

咪唑化合物的存在量以固體含量計佔的黏著劑膜總量之約0.1wt%至約5wt%，較佳約0.5wt%至約3wt%。咪唑化合物在此範圍內的，則黏著劑膜可呈現良好的黏著性、氣泡型式之孔隙產生最小化及不會遭受連接失效及濕氣吸收。The imidazole compound is present in an amount of from about 0.1% by weight to about 5% by weight, based on the total amount of the adhesive film, preferably from about 0.5% by weight to about 3% by weight. If the imidazole compound is in this range, the adhesive film can exhibit good adhesion, the bubble type of the bubble type is minimized, and the connection failure and moisture absorption are not suffered.

填充劑Filler

填充劑可包括金屬，例如金粉末、銀粉末、銅 鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、氧化矽、氮化硼、二氧化鈦、玻璃、氧化鐵、及陶瓷。有利地，可使用氧化矽。The filler may include a metal such as gold powder, silver powder, copper Magnesium, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, cerium oxide, boron nitride, titanium dioxide, glass, iron oxide, and ceramics. Advantageously, cerium oxide can be used.

雖然填充劑可以有任何形狀及任何大小，但可使用約5nm至約20μm大小的球形氧化矽及非晶形氧化矽。Although the filler may have any shape and any size, spherical cerium oxide and amorphous cerium oxide having a size of from about 5 nm to about 20 μm may be used.

填充劑的存在量為以固態含量計之黏著劑組成物總量的15wt%至40wt%，較佳20wt%至35wt%。在此範圍內，填充劑可確保良好的流動性、膜成形性及黏著性。The filler is present in an amount of from 15% by weight to 40% by weight, preferably from 20% by weight to 35% by weight based on the total mass of the adhesive composition. Within this range, the filler ensures good fluidity, film formability, and adhesion.

偶合劑Coupler

偶合劑提供的功能為做為黏合促進劑，其於黏著劑組成物製備時藉由在一無機材料如氧化矽與一有機材料間的化學鍵結促進黏著性。The coupling agent provides a function as a adhesion promoter which promotes adhesion during the preparation of the adhesive composition by chemical bonding between an inorganic material such as cerium oxide and an organic material.

至於偶合劑，可使用任何型式的矽烷偶合劑，例如一含環氧基矽烷偶合劑，如2-(3,4-環氧環己基)-乙基三甲氧基矽烷、3-去水甘油氧基三甲氧基矽烷及3-去水甘油氧基丙基三乙氧基矽烷；一含胺基矽烷偶合劑，如N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基丁二烯)丙基胺及N-苯基-3-胺基丙基三甲氧基矽烷；一含巰基矽烷偶合劑，如3-巰基丙基甲基二甲氧基矽烷及3-巰基丙基三乙氧基矽烷；及含異氰酸酯之矽烷偶合劑，如3-異氰酸酯丙基三乙氧基矽烷，其等可單獨或二或二以上組合使用。As the coupling agent, any type of decane coupling agent such as an epoxy group-containing decane coupling agent such as 2-(3,4-epoxycyclohexyl)-ethyltrimethoxynonane or 3-dehydroglyceryl oxide may be used. Trimethoxy decane and 3-dehydroglyceryloxypropyl triethoxy decane; an amine-containing decane coupling agent such as N-2-(aminoethyl)-3-aminopropylmethyldi Methoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutadiene)propylamine and N-phenyl-3-aminopropyltrimethoxydecane; a mercapto-containing decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane and 3-mercaptopropyltriethoxydecane; A decane coupling agent of an isocyanate such as 3-isocyanate propyl triethoxy decane may be used singly or in combination of two or more.

此偶合劑的存在量為以固態含量計之黏著劑組成物總量的0.1wt%至10wt%，較佳為0.5wt%至5wt%，及更較佳0.7wt%至3wt%。在此範圍內，偶合劑在減少氣泡時可提供良好的黏合可靠度。The coupling agent is present in an amount of from 0.1% by weight to 10% by weight, based on the total amount of the adhesive composition, preferably from 0.5% by weight to 5% by weight, and more preferably from 0.7% by weight to 3% by weight. Within this range, the coupling agent provides good adhesion reliability when reducing air bubbles.

此黏著劑膜可更包括一有機溶劑。此有機溶劑降低用於半導體元件的黏著劑組成物之黏性並促進膜的形成。有機溶劑的範例可包括但未限制為甲苯、二甲苯、丙二醇單甲基醚乙酸酯、苯、酮、甲基乙基酮、四氫呋喃、二甲基甲醯胺及環己酮。The adhesive film may further comprise an organic solvent. This organic solvent lowers the viscosity of the adhesive composition for a semiconductor element and promotes film formation. Examples of the organic solvent may include, but are not limited to, toluene, xylene, propylene glycol monomethyl ether acetate, benzene, ketone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide, and cyclohexanone.

此黏著劑膜在260℃可具有約2x104 至約15x104 泊的熔融黏度。在此範圍中，此黏著劑組成物可允許一金屬凸塊平滑的接觸一焊料，因此促進電性連接。較佳地，黏著劑膜的熔融黏度在約3x104 至約15x104 泊範圍間，尤以在5.5x104 至14x104 泊間為宜。The adhesive film may have a melt viscosity of from about 2 x 10 4 to about 15 x 10 4 poise at 260 °C. Within this range, the adhesive composition allows a metal bump to smoothly contact a solder, thereby facilitating electrical connection. Preferably, the melt viscosity of the adhesive film is in the range between about 3x10 4 to about 15x10 4 poise, particularly preferably between 5.5x10 4 to 14x10 4 poise.

用於半導體的黏著劑膜可具有5%或更少的殘餘固化率，尤以3%或更少為宜，如以方程式1表示：殘餘固化率=(Hc/Hi)x 100----(1)，其中Hi為在黏著劑膜製備後產生的最初熱量，及Hc為在260℃固化10秒後產生的熱量。The adhesive film for a semiconductor may have a residual curing rate of 5% or less, particularly preferably 3% or less, as expressed by Equation 1: Residual curing rate = (Hc/Hi) x 100---- (1), where Hi is the initial heat generated after the preparation of the adhesive film, and Hc is the heat generated after curing at 260 ° C for 10 seconds.

此外，此用於半導體的黏著劑膜當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，可具有大於1的二放熱峰之面積比例(E1/E2)，其中E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積。特別地，當在 溫度小於200℃時允許酸酐固化劑藉由咪唑觸媒與環氧樹脂反應的最初放熱峰之面積大於在溫度為200℃或更高時允許環-開環氧樹脂與其他的環氧樹脂連續反應之第二放熱峰面積(E1/E2>1或E1>E2)時，此黏著劑已促進最初的黏著性且可預防黏著性經濕氣吸收而劣化。即使在咪唑觸媒的存在量與酸酐固化劑相比為足夠量的情況下，此黏著劑膜因為不足量的酸酐固化劑而具有一低的最初放熱峰，且因此即使在260℃接合10秒不能具有一充足的固化結構，因而造成在最初黏合的劣化。此造成在後續的晶片接合製程中不安定的支撐結構。同時，當酸酐固化劑的存在量為一適當量但咪唑觸媒與酸固化劑相比並沒有充足的量時，此黏著劑膜具有一低的最初放熱峰且因此即使在260℃接合10秒不能具有一充足的固化結構，因為濕氣吸收而未與環氧樹脂反應的酸酐之濕氣吸收，因而造成不僅是最初黏著性且在後固化黏著性的劣化。因此，經分析於DSC熱圖譜上偵測的放熱峰，藉由在200℃或較低之最初酯化反應獲得的最初放熱峰之面積大於藉由在200℃或更高之酯化反應獲得的第二放熱峰之面積面積(E1/E2>1或E1>E2)，以獲得安定的最初黏著性同時防止因為濕氣吸收而未反應之酸酐在黏著性上的劣化。In addition, the adhesive film for a semiconductor may have an area ratio (E1/E2) of two exothermic peaks greater than 1 when the heat generated by the adhesive film is measured using a differential scanning calorimeter (DSC), wherein E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is the area of the exothermic peak detected at a temperature of 200 ° C or higher. Especially when When the temperature is less than 200 ° C, the initial exothermic peak of the anhydride curing agent by reacting the imidazole catalyst with the epoxy resin is allowed to be larger than the continuous reaction of the epoxy resin with other epoxy resins at a temperature of 200 ° C or higher. When the second exothermic peak area (E1/E2>1 or E1>E2), the adhesive promotes the initial adhesion and prevents the adhesion from deteriorating by moisture absorption. Even in the case where the amount of the imidazole catalyst present is a sufficient amount compared to the acid anhydride curing agent, the adhesive film has a low initial exothermic peak due to an insufficient amount of the acid anhydride curing agent, and thus even if it is joined at 260 ° C for 10 seconds It does not have a sufficient curing structure, thus causing deterioration in the initial bonding. This results in an unstable support structure in the subsequent wafer bonding process. Meanwhile, when the acid anhydride curing agent is present in an appropriate amount but the imidazole catalyst is not in sufficient amount compared to the acid curing agent, the adhesive film has a low initial exothermic peak and thus is bonded even at 260 ° C for 10 seconds. It is not possible to have a sufficient curing structure because the moisture absorbed by the acid gas which is not absorbed by the epoxy resin is absorbed, thereby causing not only the initial adhesion but also the deterioration of the post-curing adhesiveness. Therefore, by analyzing the exothermic peak detected on the DSC heat map, the area of the initial exothermic peak obtained by the initial esterification reaction at 200 ° C or lower is greater than that obtained by the esterification reaction at 200 ° C or higher. The area area of the two exothermic peaks (E1/E2>1 or E1>E2) to obtain the initial adhesion of the stability while preventing the deterioration of the unreacted acid anhydride due to moisture absorption.

本發明的黏著劑膜形成一黏著劑層，其滿足在凸塊晶片間的連接的可靠性同時能夠有一助熔製程以除去Cu凸塊與焊料之氧化層。此外，本發明的黏著劑膜允許凸塊與焊料在晶片接合的加熱與壓縮時有足夠的連接。再 者，本發明的黏著劑膜呈現良好的黏著性且可在凸塊與焊料間形成一足夠面積的介金屬化合物(IMC)層而沒有產生氣泡型式之孔隙。The adhesive film of the present invention forms an adhesive layer which satisfies the reliability of the connection between the bump wafers while having a fluxing process to remove the oxide bumps of the Cu bumps and the solder. Furthermore, the adhesive film of the present invention allows the bumps and solder to have sufficient connections during heating and compression of the wafer bond. again The adhesive film of the present invention exhibits good adhesion and can form a sufficient area of the intermetallic compound (IMC) layer between the bump and the solder without generating a bubble type of void.

在本發明的另一態樣中提供一用於半導體的藉由黏著劑膜接合之半導體封裝體。為本發明一實施例的半導體封裝體之剖面示意圖。如此處所見，一半導體封裝體100包括一基材50；一第一半導體晶片10，其安裝在基材50上；一第二半導體晶片20其安裝在該第一半導體晶片10上；及一充填第一半導體晶片10及第二半導體晶片20間的黏著劑膜15，其中該黏著劑膜15具有一大於1的放熱峰之二面積比例(E1/E2)，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積。In another aspect of the invention, a semiconductor package for bonding a semiconductor film by an adhesive film is provided. A schematic cross-sectional view of a semiconductor package in accordance with an embodiment of the present invention. As seen herein, a semiconductor package 100 includes a substrate 50; a first semiconductor wafer 10 mounted on the substrate 50; a second semiconductor wafer 20 mounted on the first semiconductor wafer 10; and a fill An adhesive film 15 between the first semiconductor wafer 10 and the second semiconductor wafer 20, wherein the adhesive film 15 has a two-area ratio (E1/E2) of an exothermic peak greater than one, which is when a differential scanning calorimeter is used (DSC) When measuring the heat generated by the adhesive film during curing, E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is the area of the exothermic peak detected at a temperature of 200 ° C or higher. .

半導體封裝體100可包括一在該黏著劑膜15中形成的導體11，其電性連接該第一半導體晶片10至該第二半導體晶片20。The semiconductor package 100 can include a conductor 11 formed in the adhesive film 15 electrically connected to the first semiconductor wafer 10 to the second semiconductor wafer 20.

本發明可由下列實施例及比較實施例而顯見。此些實施例僅為用於說明之用而非用以任何方式解釋以限制由後附申請專利範圍中所界定之本發明。The invention is apparent from the following examples and comparative examples. The examples are for illustrative purposes only and are not to be construed as limiting the invention as defined in the appended claims.

實施例Example

在下列實施例及比較實施例中使用的組份如下：The components used in the following examples and comparative examples are as follows:

(A)丙烯酸樹脂：SG-P3(Nagase Chemtex公司)(A) Acrylic resin: SG-P3 (Nagase Chemtex)

(B)環氧樹脂(B) Epoxy resin

(b1)固態環氧樹脂(EPPN-501H，Nippon Kayaku公司)(b1) Solid epoxy resin (EPPN-501H, Nippon Kayaku)

(b2)液態環氧樹脂(KDS-8128，Kukdo Chemical公司)(b2) Liquid epoxy resin (KDS-8128, Kukdo Chemical)

(C)助熔活性固化劑：3,4-二羧基-1,2,3,4-四氫-1-萘丁二酸二酐(TCI)(C) fluxing active curing agent: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (TCI)

(D)咪唑化合物：2PHZ(m.p.：230℃，Shikoku Chemicals公司)(D) Imidazole compound: 2PHZ (m.p.: 230 ° C, Shikoku Chemicals)

(E)填充劑：球形氧化矽(SC-2500SQ，Admatechs)(E) Filler: spherical cerium oxide (SC-2500SQ, Admatechs)

(F)矽烷偶合劑：環氧樹脂矽烷偶合劑(KBM-303，Shin-Etsu Chemical公司)(F) decane coupling agent: epoxy resin decane coupling agent (KBM-303, Shin-Etsu Chemical Co., Ltd.)

(G)溶劑：甲基乙基酮(Samchun Chemical公司)(G) Solvent: methyl ethyl ketone (Samchun Chemical Co., Ltd.)

實施例1至6及比較實施例1至4Examples 1 to 6 and Comparative Examples 1 to 4

在一裝設有高速攪拌器的圓柱形燒瓶中一起加入前述組份與甲基乙基酮為一溶劑以具有一25%的固體含量，在2000rpm緩慢分散10分鐘，並接著在5000rpm快速分散30分鐘，因而製備黏著劑膜的組成物。接著，使用50μm囊式過濾器過濾每一組成物並使用一塗佈器在一PET膜上塗佈20μm厚度，因而製備一黏著劑膜。此黏著劑膜在90℃乾燥10分鐘，進一步在110℃乾燥5分鐘，並在室溫靜置1天。The above components were added together with methyl ethyl ketone as a solvent in a cylindrical flask equipped with a high-speed stirrer to have a solid content of 25%, slowly dispersed at 2000 rpm for 10 minutes, and then rapidly dispersed at 5000 rpm. Minutes, thus preparing a composition of the adhesive film. Next, each composition was filtered using a 50 μm capsule filter and coated on a PET film to a thickness of 20 μm using an applicator, thereby preparing an adhesive film. The adhesive film was dried at 90 ° C for 10 minutes, further dried at 110 ° C for 5 minutes, and allowed to stand at room temperature for 1 day.

在實施例1至6及比較實施例1至4製備的黏著劑膜如下評估。The adhesive films prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated as follows.

(1)E/H比例：計算在每一組成物中環氧樹脂對助熔活性固化劑的當量比例(環氧樹脂的當量重/助熔活性固化劑 的當量重)。(1) E/H ratio: Calculate the equivalent ratio of epoxy resin to fluxing active curing agent in each composition (equivalent weight of epoxy resin / fluxing active curing agent) Equivalent weight).

(2)放熱峰(E1/E2)的面積比例：黏著劑膜固化時產生的熱量使用示差掃瞄熱卡計(DSC)測量，其以10℃/min速率自30℃掃瞄至500℃。在一偵測得的熱圖譜上計算放熱峰的面積比例。此處，此二放熱峰的比例(E1/E2)經由將200℃或更少的溫度酯化獲得之最初放熱峰之面積(E1)除以在200℃或更高的溫度酯化獲得之一放熱峰之面積(E2)計算之。(2) Area ratio of exothermic peak (E1/E2): The heat generated when the adhesive film was cured was measured using a differential scanning calorimeter (DSC), which was scanned from 30 ° C to 500 ° C at a rate of 10 ° C/min. The area ratio of the exothermic peak is calculated on a detected heat map. Here, the ratio of the two exothermic peaks (E1/E2) is obtained by dividing the area of the initial exothermic peak (E1) obtained by esterification at a temperature of 200 ° C or less by the esterification at a temperature of 200 ° C or higher. The area of the peak (E2) is calculated.

(3)黏著性(kgf/晶片)：一塗覆有二氧化物膜之第一725μm厚晶圓切成具有5x5mm大小的晶片，其依續在60℃與各自黏著劑膜層合。接著，切割此層合物只留下接合的部份。一上晶片(5x5mm)與一黏著劑膜層合並置於第二725μm厚晶片(10x10mm)上，此疊合的晶片在260℃進行一1.0kgf負載10秒，並在260℃測量剪力強度。(3) Adhesion (kgf/wafer): A first 725 μm thick wafer coated with a dioxide film was cut into wafers having a size of 5 x 5 mm, which were successively laminated with respective adhesive films at 60 °C. Next, the laminate is cut leaving only the joined portion. An upper wafer (5 x 5 mm) was bonded to an adhesive film layer on a second 725 μm thick wafer (10 x 10 mm). The laminated wafer was subjected to a 1.0 kgf load at 260 ° C for 10 seconds, and the shear strength was measured at 260 ° C.

(4)在濕氣吸收後的黏著性(kgf/晶片)：一塗覆有二氧化物膜之第一725μm厚晶圓切成具有5x5mm大小的晶片，其依續在60℃與各自黏著劑膜層合。接著，切割此層合物只留下接合的部份。一上晶片(5x5mm)與一黏著劑膜層合並置於第二725μm厚晶片(10x10mm)上，此疊合的晶片在260℃進行一1.0kgf負載10秒，並於PCT中在uHAST條件(130℃/85%RH)下進行三次IR-回流96小時。接著，在260℃測量剪力強度。(4) Adhesion after moisture absorption (kgf/wafer): A first 725 μm thick wafer coated with a dioxide film was cut into wafers having a size of 5×5 mm, which was continued at 60 ° C with respective adhesives. Film lamination. Next, the laminate is cut leaving only the joined portion. An upper wafer (5 x 5 mm) was bonded to an adhesive film layer on a second 725 μm thick wafer (10 x 10 mm). The laminated wafer was subjected to a 1.0 kgf load at 260 ° C for 10 seconds and in PCT under uHAST conditions (130 Three IR-reflows were carried out for 96 hours at ° C / 85% RH). Next, the shear strength was measured at 260 °C.

(5)在60℃的熔融黏度(x104 (P))：為黏著劑膜的熔融黏度，每一黏著劑膜於60℃堆疊至複數層並切成直徑為8mm 的圓形試樣。此試樣具有400至450μm的厚度。當以5℃/min速度將試樣自30℃加熱至300℃，測量此熔融黏度。表1及2顯示一在60℃的eta值，其估算晶片裝設在黏著劑膜上時於60℃的流度。當膜裝設至晶片時，若膜的熔融黏度大於或等於一預定值，此膜不能充分填充在凸塊間的空間，因而造成在後續晶片接合及固化製程中的孔隙失效。(5) Melt viscosity at 60 ° C (x10 4 (P)): the melt viscosity of the adhesive film, each of the adhesive films was stacked at 60 ° C to a plurality of layers and cut into a circular sample having a diameter of 8 mm. This sample has a thickness of 400 to 450 μm. The melt viscosity was measured by heating the sample from 30 ° C to 300 ° C at a rate of 5 ° C / min. Tables 1 and 2 show an eta value at 60 ° C which estimates the fluidity at 60 ° C when the wafer is mounted on the adhesive film. When the film is attached to the wafer, if the film has a melt viscosity greater than or equal to a predetermined value, the film does not sufficiently fill the space between the bumps, thereby causing void failure in subsequent wafer bonding and curing processes.

(6)在60℃的安裝孔隙：為了評估當安裝時在凸塊上產生的孔隙，一具有凸塊的晶片於60℃安裝在黏著劑膜上，接著經由一顯微鏡觀察在凸塊周圍的孔隙產生。沒有孔隙發生標示為○，部份發生細微的孔隙標示為△，而嚴重發生的孔隙標示為×。(6) Mounting Pore at 60 ° C: In order to evaluate the voids generated on the bumps during mounting, a wafer having bumps was mounted on the adhesive film at 60 ° C, and then the pores around the bumps were observed through a microscope. produce. No pores are marked as ○, some fine pores are marked as △, and severely occurring pores are marked as ×.

(7)於260℃10秒之殘餘固化率：每一黏著劑膜切成10mm×30mm試樣，其依續於60℃層合在一載玻片上，由黏著劑膜移除一覆蓋膜。接著，除去一PET膜，此黏著劑膜在一熱板上於260℃固化10秒並由載玻片移除，使用Q20(TA Instrument)在當温度以10℃/min速率自30℃增加至400℃時測量當固化時產生的熱。接著，殘餘固化率依下列方程式1經由將在固化後產生的熱量除以在黏著劑膜製備後產生的最初熱量而計算之。殘餘固化率依黏著劑組成物的固化密度增加而減少，因此提供黏著劑組成物良好可靠性。(7) Residual curing rate at 260 ° C for 10 seconds: Each adhesive film was cut into a 10 mm × 30 mm sample, which was laminated on a glass slide at 60 ° C to remove a cover film from the adhesive film. Next, a PET film was removed and the adhesive film was cured on a hot plate at 260 ° C for 10 seconds and removed by the slide, using Q20 (TA Instrument) at a temperature of 10 ° C / min from 30 ° C to 30 ° C to The heat generated when curing was measured at 400 °C. Next, the residual solidification rate is calculated by dividing the heat generated after curing by the initial heat generated after the preparation of the adhesive film according to the following Equation 1. The residual curing rate is reduced depending on the increase in the curing density of the adhesive composition, thus providing good reliability of the adhesive composition.

殘餘固化率=(Hc/Hi)x 100---(1)，(其中Hi為在黏著劑膜製備後產生的最初熱量，及Hc 為在260℃固化10秒後產生的熱量。)Residual cure rate = (Hc / Hi) x 100 - (1), (where Hi is the initial heat generated after the adhesive film is prepared, and Hc The heat generated after curing at 260 ° C for 10 seconds. )

(8)氣泡型式之孔隙：一塗覆有二氧化物膜之第一80μm厚晶圓切成具有10x10mm大小的晶片，其依續在60℃與各自黏著劑膜層合。接著，切割此層合物只留下接合的部份。一第一晶圓晶片(10x10mm)與一黏著劑膜層合並置於第二725μm厚晶圓晶片(10x10mm)，此疊合的晶片在100℃及接著260℃進行一1.0kgf負載10秒。接著，使用掃瞄式超音波拓撲(SAT)評估氣泡型式孔隙之發生。在晶圓上沒有氣泡型式孔隙發生標示為O，部份發生細微的孔隙標示為△，而嚴重發生的孔隙標示為X。(8) Bubble type pores: A first 80 μm thick wafer coated with a dioxide film was cut into wafers having a size of 10 x 10 mm, which were successively laminated with respective adhesive films at 60 °C. Next, the laminate is cut leaving only the joined portion. A first wafer (10 x 10 mm) was bonded to an adhesive film layer on a second 725 μm thick wafer (10 x 10 mm), and the stacked wafer was subjected to a 1.0 kgf load at 100 ° C and then 260 ° C for 10 seconds. Next, the occurrence of bubble-type pores was evaluated using a scanning ultrasonic topology (SAT). No bubble type pores on the wafer are marked as O, some fine pores are marked as △, and severely occurring pores are marked as X.

(9)焊料/Cu凸塊連接性：依黏著劑組成物評估凸塊對凸塊的連接性，使用一製造用於評估一焊料凸塊及一Cu凸塊間連接性的晶片。優良的連接標示為O，部份不連接標示為△，及未連接標示為X。(9) Solder/Cu bump connectivity: The bump-to-bump connection was evaluated based on the adhesive composition, and a wafer for evaluating the connectivity between a solder bump and a Cu bump was used. The excellent connection is marked as O, the part not connected is marked as △, and the unconnected is marked as X.

(10)在焊料/Cu間IMC層的存在：當一氧化物層當在焊料凸塊與Cu凸塊間連接時經由助熔活性去除，產生一介金屬化合物(IMC)層(Journal of Alloys and Compounds 381(2004)，第151~157頁)。為了評估氧化物層去除的效能，黏著劑膜與焊料球(Sn96.8Ag3.0Cu0.2，760μm)置於一Cu箔上，接者經由在260℃壓縮成型以製備一試樣。此試樣進行一側表面抛光以經由SEM觀察在Cu箔與焊料球間的IMC層。有IMC層存在標示為○及無IMC層存在標示為×。(10) The presence of an IMC layer between the solder/Cu: when an oxide layer is removed by fluxing activity when it is connected between the solder bump and the Cu bump, an intermetallic compound (IMC) layer is produced (Journal of Alloys and Compounds) 381 (2004), pp. 151-157). In order to evaluate the effectiveness of oxide layer removal, an adhesive film and a solder ball (Sn96.8Ag3.0Cu0.2, 760 μm) were placed on a Cu foil, and a sample was prepared by compression molding at 260 °C. This sample was subjected to one side surface polishing to observe the IMC layer between the Cu foil and the solder ball via SEM. The existence of the IMC layer is marked as ○ and the presence of no IMC layer is indicated as ×.

如表1及表2顯示，在比較實施例1的黏著劑膜中，其具有一不預期的E/H比例，酸酐固化劑的量與環氧樹脂量相比為過度的低。因此，此黏著劑膜當在260℃接合一很短的10秒不能提供一足夠的固化結構，因而呈現低 最初之黏著劑強度。此外，在比較實施例2的黏著劑膜中，其具有一不預期的E/H比例，酸酐固化劑的量與環氧樹脂量相比為過度的高，故此黏著劑膜呈現足夠的最初黏著強度。然而，因為在組成物中過量的酸酐固化劑易受到濕氣吸收，比較實施例2的黏著劑膜於濕氣吸收後在黏著劑強度劣化，且因為過度固化而具有低連接性。在比較實施例3的黏著劑膜中，其具有一不預期的E/H比例，此不足量的咪唑觸媒造成低的反應速率且不能提供最初黏著劑強度。此外，比較實施例3的黏著劑膜因為經未反應酸酐固化劑的濕氣吸收而在黏著劑強度劣化。在比較實施例4的黏著劑膜中，咪唑觸媒的量與酸酐固化劑量相比為過度的高。因此，比較實施例4的黏著劑膜因為藉由咪唑觸媒的快速最初反應性而具有高的最初黏著劑強度而未遭受因濕氣吸收而在黏著劑強度的劣化。然而，此黏著劑膜呈現快速的固化反應以致於不能確保在凸塊間連接間的足夠流動性，且因此遭受在連接性的劣化。雖然比較實施例5的黏著劑膜在固化時滿足了E/H比例與放熱峰之面積比例的要求，此黏著劑膜不含有液態環氧樹脂且因此在凸塊間具有孔隙，其長成氣泡型式之孔隙，此係歸因為當安裝時於低溫的不足流動性。為了製造在後接合及熱固化製程中無缺陷的產品，黏著劑膜需要確保足夠的孔隙填充而在最初安裝時在凸塊區域中無氣泡產生。As shown in Tables 1 and 2, in the adhesive film of Comparative Example 1, it had an unexpected E/H ratio, and the amount of the acid anhydride curing agent was excessively low as compared with the amount of the epoxy resin. Therefore, the adhesive film does not provide a sufficient curing structure when bonded at 260 ° C for a short 10 seconds, thus exhibiting a low Initial adhesive strength. Further, in the adhesive film of Comparative Example 2, which had an unexpected E/H ratio, the amount of the acid anhydride curing agent was excessively high as compared with the amount of the epoxy resin, so that the adhesive film exhibited sufficient initial adhesion. strength. However, since the excess acid anhydride curing agent in the composition is easily absorbed by moisture, the adhesive film of Comparative Example 2 deteriorates in strength of the adhesive after moisture absorption, and has low connectivity due to excessive curing. In the adhesive film of Comparative Example 3, it had an unexpected E/H ratio, and this insufficient amount of the imidazole catalyst caused a low reaction rate and could not provide the initial adhesive strength. Further, the adhesive film of Comparative Example 3 deteriorated in adhesive strength due to moisture absorption by the unreacted acid anhydride curing agent. In the adhesive film of Comparative Example 4, the amount of the imidazole catalyst was excessively high as compared with the curing amount of the acid anhydride. Therefore, the adhesive film of Comparative Example 4 had high initial adhesive strength by the rapid initial reactivity of the imidazole catalyst, and did not suffer from deterioration of the adhesive strength due to moisture absorption. However, this adhesive film exhibits a rapid curing reaction so that sufficient fluidity between the joints between the bumps cannot be ensured, and thus suffers from deterioration in connectivity. Although the adhesive film of Comparative Example 5 satisfies the requirement of the ratio of the E/H ratio to the area ratio of the exothermic peak at the time of curing, the adhesive film does not contain a liquid epoxy resin and thus has pores between the bumps, and it grows into a bubble pattern. The porosity is attributed to insufficient fluidity at low temperatures when installed. In order to produce a defect-free product in the post-bonding and thermal curing process, the adhesive film needs to ensure sufficient pore filling without the generation of bubbles in the bump regions during initial installation.

雖然本文已揭露了某些實施例，但應瞭解此些實施例僅為提供說明之用，而在未偏離本發明技術思想及 範疇下可進行多種的修飾、改變、及變化。因此，本發明的範疇僅由後附的申請專利範圍及等效物限制。Although certain embodiments have been disclosed herein, it should be understood that these embodiments are provided for illustrative purposes only and not A variety of modifications, changes, and changes are possible within the scope. Therefore, the scope of the invention is limited only by the scope of the appended claims and the equivalents.

10‧‧‧第一半導體晶片10‧‧‧First semiconductor wafer

11‧‧‧導體11‧‧‧Conductor

15‧‧‧黏著劑膜15‧‧‧Adhesive film

20‧‧‧第二半導體晶片20‧‧‧Second semiconductor wafer

50‧‧‧基材50‧‧‧Substrate

100‧‧‧半導體封裝體100‧‧‧Semiconductor package

Claims (15)

一種用於半導體的黏著劑膜，其包含：一丙烯酸樹脂；一環氧樹脂；及助熔活性固化劑，其中二放熱峰之面積比例(E1/E2)大於1，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積；且其中該黏著劑膜具有環氧樹脂對助熔活性固化劑的當量比例(環氧樹脂當量重/助熔活性固化劑當量重)為在0.7至1.6間。 An adhesive film for a semiconductor comprising: an acrylic resin; an epoxy resin; and a fluxing active curing agent, wherein an area ratio (E1/E2) of the two exothermic peaks is greater than 1, which is when using differential scanning heat The card gauge (DSC) measures the amount of heat generated by the adhesive film during curing. E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is the exotherm detected at a temperature of 200 ° C or higher. The area of the peak; and wherein the adhesive film has an equivalent ratio of the epoxy resin to the fluxing active curing agent (epoxy resin equivalent weight / fluxing active curing agent equivalent weight) of between 0.7 and 1.6. 一種黏著劑膜，其在60℃具有1x104 泊(Poise)至15x104 泊的熔融黏度，及具有大於1的二放熱峰之面積比例(E1/E2)，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積。One kind of adhesive film having at 60 ℃ 1x10 4 poises (the Poise) to the melt viscosity of 15x10 4 poise, and has an area ratio of two exothermic peak is greater than 1 (E1 / E2), using a differential scanning calorimeter that when (DSC) When measuring the heat generated by the adhesive film during curing, E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is the area of the exothermic peak detected at a temperature of 200 ° C or higher. . 一種用於半導體的黏著劑膜，其包含：一丙烯酸樹脂；一環氧樹脂；及一助熔活性固化劑，該黏著劑膜在60℃具有1x104 泊(Poise)至15x104 泊的熔融黏度，及一在260℃固化10秒後約5%或更少的殘餘固化率，如以方程式1表示：殘餘固化率=(Hc/Hi)x 100---(1)， 其中其中Hi為在黏著劑膜製備後產生的最初熱量，及Hc為在260℃固化10秒後產生的熱量。One kind of the adhesive film for a semiconductor, comprising: an acrylic resin; an epoxy resin; and a fluxing agent reactive curing, the adhesive film having a melt viscosity of 1x10 4 poise (the Poise) to 15x10 4 poise at 60 ℃, And a residual curing rate of about 5% or less after curing at 260 ° C for 10 seconds, as expressed by Equation 1: residual curing rate = (Hc / Hi) x 100 - (1), wherein Hi is in adhesion The initial heat generated after the preparation of the film, and Hc is the amount of heat generated after curing at 260 ° C for 10 seconds. 如申請專利範圍第1至3項任一項之黏著劑組成物，其更包含：一咪唑化合物。 The adhesive composition according to any one of claims 1 to 3, further comprising: an imidazole compound. 如申請專利範圍第1至3項任一項之黏著劑組成物，其中該助熔活性固化劑的存在量為基於黏著劑膜總重的5wt%至20wt%。 The adhesive composition according to any one of claims 1 to 3, wherein the fluxing active curing agent is present in an amount of from 5 wt% to 20 wt%, based on the total mass of the adhesive film. 如申請專利範圍第1至3項任一項之黏著劑組成物，其中該咪唑化合物的存在量為基於黏著劑膜總重的0.5wt%至5wt%。 The adhesive composition according to any one of claims 1 to 3, wherein the imidazole compound is present in an amount of from 0.5% by weight to 5% by weight based on the total mass of the adhesive film. 如申請專利範圍第1至3項任一項之黏著劑組成物，其包含：20wt%至50wt%的丙烯酸樹脂；20wt%至50wt%的環氧樹脂；5wt%至20wt%的助熔活性固化劑；及15wt%至40wt%的填充劑。 An adhesive composition according to any one of claims 1 to 3, which comprises: 20% by weight to 50% by weight of an acrylic resin; 20% by weight to 50% by weight of an epoxy resin; and 5% by weight to 20% by weight of a fluxing active curing And 15% to 40% by weight of a filler. 如申請專利範圍第1至3項任一項之黏著劑組成物，其中該助熔活性固化劑包括至少一由化學式1至3表示之助熔活性固化劑： 其中[A]表示一含有酸酐基的C4至C8環結構；[B]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳 族基；R1 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；及n為一由0至2範圍的整數； 其中[C]表示一含有酸酐基的C4至C8環結構；[D]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R2 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；及n為一由1至4範圍的整數；及 其中[E]表示一含有酸酐基的C4至C8環結構；[F]表示一具有C4至C8環結構的脂環基、未飽和脂環基或芳族基；R3 為選自由氫原子、C1至C6烷基、C6至C12芳基、C6至C12之被取代芳基、乙烯基、及丙烯基組成之組群中；R4 為選自由下列化學式(i)至(viii)表示之化合物；及n為一由1至4範圍的整數； The adhesive composition according to any one of claims 1 to 3, wherein the fluxing active curing agent comprises at least one fluxing active curing agent represented by Chemical Formulas 1 to 3: Wherein [A] represents a C4 to C8 ring structure containing an acid anhydride group; [B] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group; and R 1 is selected from a hydrogen atom, a group consisting of C1 to C6 alkyl, C6 to C12 aryl, C6 to C12 substituted aryl, vinyl, and propylene; and n is an integer ranging from 0 to 2; Wherein [C] represents a C4 to C8 ring structure containing an acid anhydride group; [D] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group; and R 2 is selected from a hydrogen atom, a group consisting of C1 to C6 alkyl, C6 to C12 aryl, C6 to C12 substituted aryl, vinyl, and propylene; and n is an integer ranging from 1 to 4; Wherein [E] represents a C4 to C8 ring structure containing an acid anhydride group; [F] represents an alicyclic group having an C4 to C8 ring structure, an unsaturated alicyclic group or an aromatic group; and R 3 is selected from a hydrogen atom, a group consisting of a C1 to C6 alkyl group, a C6 to C12 aryl group, a C6 to C12 substituted aryl group, a vinyl group, and a propylene group; and R 4 is a compound selected from the following chemical formulas (i) to (viii) ; and n is an integer ranging from 1 to 4; 如申請專利範圍第8項之黏著劑組成物，其中該[A]、[C]及[E]中任一者所代表的環結構係包括1至3個雙鍵。 The adhesive composition of claim 8, wherein the ring structure represented by any one of [A], [C], and [E] includes 1 to 3 double bonds. 如申請專利範圍第4項之黏著劑組成物，其中該咪唑化合物由化學式4表示： 其中R1 與R2 各自獨立為C1至C10伸烷基。An adhesive composition according to claim 4, wherein the imidazole compound is represented by Chemical Formula 4: Wherein R 1 and R 2 are each independently a C1 to C10 alkylene group. 如申請專利範圍第4項之黏著劑組成物，其中該咪唑化合物具有200℃至270℃的熔點。 The adhesive composition of claim 4, wherein the imidazole compound has a melting point of from 200 ° C to 270 ° C. 如申請專利範圍第1至3項任一項之黏著劑組成物，其中b對c的比例可在1.2至5：1範圍內，其中c為助熔活性固化劑的量而b為環氧樹脂的量。 The adhesive composition according to any one of claims 1 to 3, wherein the ratio of b to c is in the range of 1.2 to 5:1, wherein c is the amount of the fluxing active curing agent and b is the epoxy resin. The amount. 如申請專利範圍第1至3項任一項之黏著劑組成物，其更 包含：一矽烷偶合劑。 An adhesive composition according to any one of claims 1 to 3, which further Contains: a decane coupling agent. 一種半導體封裝體，其包含：一基材；一第一半導體晶片，其安裝在該基材上；一第二半導體晶片，其安裝在該第一半導體晶片上；及一黏著劑膜，其充填在該第一半導體晶片與該第二半導體晶片間的空間，其中該黏著劑膜具有一大於1的二放熱峰之面積比例(E1/E2)，其為當使用示差掃瞄熱卡計(DSC)測量黏著劑膜在固化時產生的熱量時，E1為在溫度小於200℃偵測到的最初放熱峰之面積，而E2為在溫度為200℃或更高時偵測到的放熱峰之面積；且其中該黏著劑膜具有環氧樹脂對助熔活性固化劑的當量比例(環氧樹脂當量重/助熔活性固化劑當量重)為在0.7至1.6間。 A semiconductor package comprising: a substrate; a first semiconductor wafer mounted on the substrate; a second semiconductor wafer mounted on the first semiconductor wafer; and an adhesive film filled a space between the first semiconductor wafer and the second semiconductor wafer, wherein the adhesive film has an area ratio (E1/E2) of two exothermic peaks greater than one, when a differential scanning calorimeter (DSC) is used When measuring the heat generated by the adhesive film during curing, E1 is the area of the initial exothermic peak detected at a temperature of less than 200 ° C, and E2 is the area of the exothermic peak detected at a temperature of 200 ° C or higher; The adhesive film has an equivalent ratio (epoxy equivalent weight / fluxing active curing agent equivalent weight) of the epoxy resin to the fluxing active curing agent of from 0.7 to 1.6. 如申請專利範圍第14項之半導體封裝體，其更包含：一在該黏著劑膜中形成的導體，其電性連接該第一半導體晶片至該第二半導體晶片。The semiconductor package of claim 14, further comprising: a conductor formed in the adhesive film electrically connecting the first semiconductor wafer to the second semiconductor wafer.
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US20220352116A1 (en) * 2019-09-30 2022-11-03 Showa Denko Materials Co., Ltd. Adhesive for semiconductor, production method therefor, and semiconductor device and production method therefor
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JP2009278054A (en) * 2008-05-19 2009-11-26 Sumitomo Bakelite Co Ltd Connection method between terminals, aggregation method of conductive particles, and semiconductor device manufacturing method using the same
TW201031730A (en) * 2008-12-24 2010-09-01 Sumitomo Bakelite Co Adhesive film, multi-layer circuit board, semiconductor component and semiconductor device

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