TWI425069B - Adhesive film and semiconductor wafer processing tape - Google Patents
Adhesive film and semiconductor wafer processing tape Download PDFInfo
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- TWI425069B TWI425069B TW099139514A TW99139514A TWI425069B TW I425069 B TWI425069 B TW I425069B TW 099139514 A TW099139514 A TW 099139514A TW 99139514 A TW99139514 A TW 99139514A TW I425069 B TWI425069 B TW I425069B
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- 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
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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
- 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
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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
- 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
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- 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
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- 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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Dicing (AREA)
Description
本發明係關於將半導體晶圓切割成半導體晶片來製造半導體裝置所使用之黏著薄膜及半導體晶圓加工用膠帶。The present invention relates to an adhesive film and a semiconductor wafer processing tape used for manufacturing a semiconductor device by dicing a semiconductor wafer into a semiconductor wafer.
半導體裝置之製造程序所使用之半導體晶圓加工用膠帶,有人提出具有將接著劑層(粒接薄膜)疊層於黏著薄膜(切粒膜)之構造的半導體晶圓加工用膠帶(例如,參照專利文獻1),且已經實用化。For the semiconductor wafer processing tape used in the manufacturing process of the semiconductor device, a tape for semiconductor wafer processing having a structure in which an adhesive layer (granular film) is laminated on an adhesive film (grain film) has been proposed (for example, reference) Patent Document 1) has been put into practical use.
半導體裝置之製造程序時,於將半導體晶圓加工用膠帶貼附於半導體晶圓後,實施:利用切料刀片將半導體晶圓切割(切粒)成晶片單位的程序、擴展半導體晶圓加工用膠帶的程序、從黏著劑層拾取經過切割之晶片及接著劑層的程序、介由附著於晶片之接著劑層將晶片安裝至基板等之程序、以及在將接著於基板等之晶片進行密封後使其通過迴焊爐的程序。In the manufacturing process of the semiconductor device, after the semiconductor wafer processing tape is attached to the semiconductor wafer, a process of cutting (dicing) the semiconductor wafer into wafer units by a cutting blade, and expanding the semiconductor wafer processing are performed. The procedure of the tape, the process of picking up the diced wafer and the adhesive layer from the adhesive layer, the process of mounting the wafer to the substrate via the adhesive layer attached to the wafer, and the like, after sealing the wafer subsequent to the substrate or the like Let it pass the procedure of the reflow oven.
[專利文獻1]日本特開平02-32181號公報[Patent Document 1] Japanese Patent Laid-Open No. 02-32181
然而,上述專利文獻1所記載之半導體晶圓加工用膠帶時,從製造到使用為止之期間,黏著劑層與接著劑層之接觸時間較長的話,使用前,兩層互相膠合,拾取經過切割之晶片時,有時會以黏著劑附著於接著劑層之狀態進行拾取。若在該種狀態下,使接著於基板等之晶片在密封後通過迴焊爐時,有發生迴焊裂痕的問題。However, in the tape for processing a semiconductor wafer described in the above Patent Document 1, when the contact time between the adhesive layer and the adhesive layer is long from the time of manufacture to use, the two layers are bonded to each other before use, and are picked up and cut. In the case of a wafer, the adhesive may be picked up while the adhesive is attached to the adhesive layer. In this state, when the wafer which is next to the substrate or the like is passed through the reflow furnace after sealing, there is a problem that reflow cracking occurs.
所以,本發明之目的係在提供一種黏著薄膜及半導體晶圓加工用膠帶,即使黏著劑層與接著劑層發生膠合,拾取晶片時,即使在黏著劑附著於接著劑層之狀態進行拾取的情形下,亦可減少封裝之迴焊裂痕。Therefore, an object of the present invention is to provide an adhesive film and a semiconductor wafer processing tape which can be picked up even when the adhesive is attached to the adhesive layer even when the adhesive layer is bonded to the adhesive layer and the wafer is picked up. Under the same, it can also reduce the reflow crack of the package.
為了解決上述課題,本發明之黏著薄膜,係由基材薄膜及配設於該基材薄膜上之黏著劑層所構成之使用於半導體晶圓加工之黏著薄膜,其特徵為,以示差熱分析進行檢測,迴焊溫度之前述黏著劑層的重量減少為1.5%以下。In order to solve the above problems, the adhesive film of the present invention is an adhesive film for semiconductor wafer processing which is composed of a base film and an adhesive layer disposed on the base film, and is characterized by differential thermal analysis. The weight of the aforementioned adhesive layer at the reflow temperature was reduced by 1.5% or less.
此外,係由基材薄膜及配設於該基材薄膜上之黏著劑層所構成之使用於半導體晶圓加工之黏著薄膜,其特徵為,以示差熱分析進行檢測,260℃之前述黏著劑層的重量減少為1.5%以下。In addition, an adhesive film for semiconductor wafer processing consisting of a base film and an adhesive layer disposed on the base film, characterized in that the adhesive is detected by differential thermal analysis at 260 ° C. The weight of the layer is reduced to less than 1.5%.
此外,為了解決上述課題,本發明之半導體晶圓加工用膠帶,係具有:由基材薄膜及配設於該基材薄膜上之黏著劑層所構成之黏著薄膜、及配設於前述黏著劑層上之接著劑層的晶圓加工用膠帶,以示差熱分析進行檢測,迴焊溫度之前述黏著劑層的重量減少為1.5%以下。In addition, in order to solve the above problems, the tape for semiconductor wafer processing of the present invention has an adhesive film composed of a base film and an adhesive layer disposed on the base film, and is disposed on the adhesive. The wafer processing tape of the adhesive layer on the layer was examined by differential thermal analysis, and the weight of the adhesive layer at the reflow temperature was reduced to 1.5% or less.
此外,本發明之半導體晶圓加工用膠帶,係具有:由基材薄膜及配設於該基材薄膜上之黏著劑層所構成之黏著薄膜、及配設於前述黏著劑層上之接著劑層的晶圓加工用膠帶,以示差熱分析進行檢測,260℃之前述黏著劑層的重量減少為1.5%以下。Further, the tape for processing a semiconductor wafer of the present invention has an adhesive film composed of a base film and an adhesive layer disposed on the base film, and an adhesive disposed on the adhesive layer. The layer of wafer processing tape was examined by differential thermal analysis, and the weight of the adhesive layer at 260 ° C was reduced to 1.5% or less.
此外,本發明之半導體晶圓加工用膠帶,黏著劑層之重量平均分子量為100萬以上。Further, in the tape for semiconductor wafer processing of the present invention, the weight average molecular weight of the adhesive layer is 1,000,000 or more.
此外,本發明之半導體晶圓加工用膠帶,其特徵為,黏著劑層含有光聚合起始劑,前述光聚合起始劑之熱分解開始溫度為260℃以上。Further, the tape for semiconductor wafer processing of the present invention is characterized in that the adhesive layer contains a photopolymerization initiator, and the thermal decomposition initiation temperature of the photopolymerization initiator is 260 ° C or higher.
本發明之黏著薄膜及半導體晶圓加工用膠帶,拾取晶片時,即使於黏著劑附著於接著劑層之狀態進行拾取時,亦可減少封裝之迴焊裂痕。In the adhesive film and the semiconductor wafer processing tape of the present invention, when the wafer is picked up, even when the adhesive is attached to the adhesive layer, the solder reflow crack can be reduced.
以下,參照圖式,針對本發明之實施形態進行詳細說明。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
本實施形態之半導體晶圓加工用膠帶15,如第1圖所示,係具有於基材薄膜11上疊層著黏著劑層12之黏著薄膜14且黏著劑層12上疊層著接著劑層13之切割粒接薄膜。此外,黏著劑層12及接著劑層13,亦可調合使用程序及裝置,而預先切割(預切)成特定形狀。疊層對應晶圓W(參照第2(a)圖)預切之接著劑層13時,用以貼合晶圓W之部分有接著劑層13,用以貼合切割用環框20(參照第2(a)圖)之部分則無接著劑層13而只存在著黏著劑層12。一般而言,因為接著劑層13不易被從被著體剝離,可以使用預切之接著劑層13將環框20貼合於黏著劑層12,而得到使用後之環框20不易產生殘膠之效果。此外,本發明之半導體晶圓加工用膠帶15,包含分別切割成晶圓1片份來進行疊層之形態、及將形成複數晶圓之長條狀的條片捲成滾筒狀的形態。以下,分別針對基材薄膜11、黏著劑層12、及接著劑層13進行詳細說明。As shown in Fig. 1, the tape for processing a semiconductor wafer according to the present embodiment has an adhesive film 14 on which an adhesive layer 12 is laminated on a base film 11, and an adhesive layer is laminated on the adhesive layer 12. 13 cut pellets. Further, the adhesive layer 12 and the adhesive layer 13 may be combined with a program and a device to be pre-cut (precut) into a specific shape. When the adhesive layer 13 (see FIG. 2(a)) is pre-cut, the adhesive layer 13 is bonded to the wafer W, and the adhesive layer 13 is bonded to the dicing ring frame 20 (see In the portion of Fig. 2(a), there is no adhesive layer 13 and only the adhesive layer 12 is present. In general, since the adhesive layer 13 is not easily peeled off from the adherend, the pre-cut adhesive layer 13 can be used to bond the ring frame 20 to the adhesive layer 12, and the ring frame 20 after use is less likely to generate residual glue. The effect. Further, the tape 15 for semiconductor wafer processing of the present invention includes a form in which one wafer is diced and laminated, and a strip having a plurality of wafers is wound into a roll shape. Hereinafter, the base film 11, the adhesive layer 12, and the adhesive layer 13 will be described in detail.
用以構成基材薄膜之材料,並無特別限制,然而,以從聚烯及聚氯乙烯選取為佳。此外,與黏著劑接觸之面的表面粗細度Ra以1μm以下為佳,最好為0.5μm以下。表面粗細度Ra為1μm以下,可以增加與黏著劑之接觸面積,而抑制黏著劑從基材薄膜之剝離。The material for constituting the base film is not particularly limited, however, it is preferably selected from the group consisting of polyolefin and polyvinyl chloride. Further, the surface roughness Ra of the surface in contact with the adhesive is preferably 1 μm or less, more preferably 0.5 μm or less. When the surface roughness Ra is 1 μm or less, the contact area with the adhesive can be increased, and the peeling of the adhesive from the base film can be suppressed.
上述聚烯,可以為聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚丁烯-1、聚-4-甲基戊烯-1、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、多離子聚合物等之α-烯烴之均聚合體或共聚物或該等之混合物等。The above polyene may be polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, A homopolymer or copolymer of an α-olefin such as an ethylene-methyl acrylate copolymer, an ethylene-acrylic acid copolymer, a polyionic polymer, or the like, or a mixture thereof.
後述之黏著劑層,使用以放射線照射進行硬化而使黏著力降低之類型時,基材薄膜應具有放射線透射性。基材薄膜之厚度,從強度及確保晶片拾取性之觀點而言,以50~300μm為佳。此外,基材薄膜之構成上,可以為單層或複數層。When the adhesive layer to be described later is cured by radiation irradiation to reduce the adhesive force, the base film should have radioelasticity. The thickness of the base film is preferably from 50 to 300 μm from the viewpoint of strength and ensuring wafer pick-up property. Further, the base film may be composed of a single layer or a plurality of layers.
黏著劑層,亦可將黏著劑塗佈於基材薄膜上來進行製造。黏著劑層並無特別限制,只要具有擴展時接著劑層及半導體晶圓不會剝離之程度的保持性、及拾取時容易剝離接著劑層之特性即可。為了提高拾取性,黏著劑層以放射線硬化性者為佳。The adhesive layer can also be produced by applying an adhesive to a substrate film. The adhesive layer is not particularly limited as long as it has such a property that the adhesive layer and the semiconductor wafer do not peel off when expanded, and the properties of the adhesive layer are easily peeled off at the time of pick-up. In order to improve the pick-up property, the adhesive layer is preferably radiation curable.
例如,以於使用於黏著劑之眾所皆知的氯化聚丙烯樹脂、丙烯酸樹脂、聚酯樹脂、聚胺酯樹脂、環氧樹脂、加成反應型有機聚矽氧烷系樹脂、聚矽系烷丙烯酸酯(silicon acrylate)樹脂、乙烯-醋酸乙烯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸共聚物、聚異戊二烯或苯乙烯‧丁二烯共聚物或其氫添加物等之各種彈性體等或其混合物適度調合輻射聚合性化合物來調製黏著劑為佳。此外,亦可添加各種界面活性劑及表面平滑化劑。黏著劑層之厚度並無特別限制,可以適度設定,然而,以1~30μm為佳。For example, a chlorinated polypropylene resin, an acrylic resin, a polyester resin, a polyurethane resin, an epoxy resin, an addition reaction type organic polyoxyalkylene resin, a polyfluorene-based alkane which are well known for use in an adhesive. Silicon acrylate resin, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, polyisoprene or styrene ‧ butadiene copolymer It is preferred to prepare the adhesive by appropriately blending the radiation-polymerizable compound with various elastomers or the like of the substance or its hydrogen additive or the like. In addition, various surfactants and surface smoothing agents can also be added. The thickness of the adhesive layer is not particularly limited and may be appropriately set. However, it is preferably 1 to 30 μm.
聚合性化合物係使用例如於光照射可導致三次元網狀化之分子內具有至少2個以上之光聚合性碳-碳雙鍵的低分子量化合物、或具有光聚合性碳-碳雙鍵基做為取代基之聚合物或寡聚物。具體而言,可以使用三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯,二季戊四醇一羥基五丙烯酸酯、二季戊四醇六丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯或寡酯丙烯酸酯等、聚矽系烷丙烯酸酯等、丙烯酸或各種丙烯酸酯類之共聚物等。The polymerizable compound is, for example, a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule which causes three-dimensional network formation by light irradiation, or a photopolymerizable carbon-carbon double bond group. A polymer or oligomer that is a substituent. Specifically, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1,6 hexanediol diacrylate, polyethylene glycol diacrylate or oligoester acrylate, etc., polyfluorene alkacrylate or the like, acrylic acid or a copolymer of various acrylates.
此外,除了上述丙烯酸酯系化合物以外,尚可以使用胺甲酸乙酯丙烯酸酯系寡聚物。胺甲酸乙酯丙烯酸酯系寡聚物,係使聚酯型或聚醚型等聚醇化合物與多價異氰酸酯化合物(例如,2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、1,3-苯二甲基二異氰酸酯、1,4-苯二甲基二異氰酸酯、二苯甲烷4,4-二異氰酸酯等)反應所得之末端異氰酸酯胺甲酸乙酯預聚合物、與具有羥基之丙烯酸酯或異丁烯酸酯(例如,2-羥乙基丙烯酸酯、2-羥乙基異丁烯酸酯、2-羥丙基丙烯酸酯、2-羥丙基異丁烯酸酯、聚乙二醇丙烯酸酯、聚乙二醇異丁烯酸酯等)進行反應而得到。此外,黏著劑層,亦可以為從上述樹脂所選取之2種以上混合者。此外,以上所列舉之黏著劑材料,除了表面自由能為40mJ/m2 以下以外,分子構造中以含有較多三氟基、二甲基甲矽烷基、長鏈烴基等之無極性基為佳。Further, in addition to the above acrylate-based compound, an urethane acrylate-based oligomer can be used. The urethane acrylate oligomer is a polyvalent isocyanate compound such as a polyester or a polyether, and a polyvalent isocyanate compound (for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1, A terminal isocyanate urethane prepolymer obtained by the reaction of 3-phenyldimethyl diisocyanate, 1,4- phenyldimethyl diisocyanate, diphenylmethane 4,4-diisocyanate or the like, and an acrylate having a hydroxyl group Or methacrylate (for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene A diol methacrylate or the like is obtained by a reaction. Further, the adhesive layer may be a mixture of two or more selected from the above resins. Further, in addition to the surface free energy of 40 mJ/m 2 or less, the above-mentioned adhesive material preferably has a polar group containing a large amount of a trifluoro group, a dimethylformyl group, a long-chain hydrocarbon group or the like in the molecular structure. .
此外,亦可以於黏著劑層之樹脂,適度調合對基材薄膜照射放射線來使黏著劑層硬化之輻射聚合性化合物、以及丙烯系黏著劑、光聚合起始劑、硬化劑等,來調製黏著劑。Further, it is also possible to adjust the adhesion of the resin of the adhesive layer to a radiation-polymerizable compound which irradiates the base film with radiation to harden the adhesive layer, and a propylene-based adhesive, a photopolymerization initiator, a curing agent, and the like. Agent.
使用光聚合起始劑時,例如,可以使用異丙基安息香醚(isopropyl benzoin ether)、異丁基安息香醚、二苯基酮、米其勒酮、氯噻噸酮(chlorothioxanthone)、十二烷基噻噸酮(dodecyl chlorothioxanthone)、二甲基噻噸酮、二乙基噻噸酮、苯甲基二甲基縮醛(benzylic diethyl acetal)、α-羥基環己基苯基甲酮、2-羥甲基苯丙烷等。該等光聚合起始劑之調合量,相對於丙烯系共聚物100質量份,以0.01~30質量份為佳,最好為1~10重量份。When a photopolymerization initiator is used, for example, isopropyl benzoin ether, isobutyl benzoin ether, diphenyl ketone, octyl ketone, chlorothioxanthone, dodecane can be used. Dodecyl chlorothioxanthone, dimethyl thioxanthone, diethyl thioxanthone, benzylic diethyl acetal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxyl Methyl phenylpropane and the like. The blending amount of the photopolymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 1 to 10 parts by weight, per 100 parts by mass of the propylene-based copolymer.
此外,黏著劑中存在著低分子成份時,製造基材薄膜後,進行長期保管的期間,低分子成份可能移動至黏著劑層表面而使黏接著特性受損,膠體分率愈高愈好,通常為60%以上,最好為70%以上。此處,膠體分率係以下述方法計算者。秤取約0.05g之黏著劑層,將其於120℃浸漬於50ml之二甲苯中24小時後,以200網目之不鏽鋼製金屬網過濾,金屬網上之不溶解成份於110℃進行120分鐘乾燥。其次,進行經過乾燥之不溶解成份之質量的秤量,利用下式1進行膠體分率之計算。In addition, when a low molecular component is present in the adhesive, the low molecular component may move to the surface of the adhesive layer and the adhesive property may be impaired during the long-term storage after the base film is produced. The higher the colloid fraction, the better. It is usually 60% or more, preferably 70% or more. Here, the colloid fraction is calculated by the following method. Approximately 0.05 g of the adhesive layer was weighed and immersed in 50 ml of xylene at 120 ° C for 24 hours, then filtered through a 200 mesh stainless steel metal mesh, and the insoluble component of the metal mesh was dried at 110 ° C for 120 minutes. . Next, the mass of the dried insoluble component is weighed, and the colloidal fraction is calculated by the following formula 1.
膠體分率(%)=(不溶解成份之質量/秤取黏著劑層之質量)×100 (式1)Colloid fraction (%) = (quality of insoluble components / mass of adhesive layer) × 100 (Formula 1)
黏著劑層,於利用示差熱分析(TG-DTA)進行檢測之迴焊溫度之重量減少為1.5%以下。此處,迴焊溫度係封裝本體之最高溫度(Tp:peak package body temperature),半導體技術協會(JEDEC:Joint Electron Device Engineering Council)有訂定分類溫度(Tc:classification temperature)時,以該分類溫度做為最高溫度。黏著劑層的重量減少係執行迴焊之狀態之黏著劑層的重量減少。亦即,放射線硬化性黏著劑層時,因為迴焊係於照射放射線並硬化後才實施,該狀態之黏著劑,以迴焊溫度進行必要時間加熱時之重量減少為1.5%以下。以黏著劑層之迴焊溫度進行必要時間加熱時之重量減少為1.5%以下時,即使於黏著劑附著於接著劑層之狀態下進行迴焊,亦可抑制與黏著劑之熱分解同時之排氣的發生。結果,可以減少迴焊裂痕之發生。因為無鉛焊錫之迴焊溫度為260℃程度,以示差熱分析(TG-DTA)所檢測之黏著劑層之260℃的重量減少以1.5%以下為佳。The adhesive layer has a weight reduction of 1.5% or less in the reflow temperature by the differential thermal analysis (TG-DTA). Here, the reflow temperature is the highest package body temperature (Tp: peak package body temperature), and the JEDEC: Joint Electron Device Engineering Council has a classification temperature (Tc: classification temperature) at which the classification temperature is As the highest temperature. The weight reduction of the adhesive layer is a reduction in the weight of the adhesive layer in the state where the reflow is performed. In other words, in the case of the radiation curable adhesive layer, since the reflow is performed after the radiation is irradiated and hardened, the weight of the adhesive in this state is reduced by 1.5% or less when heated at the reflow temperature for a necessary period of time. When the weight is reduced by 1.5% or less when the reheating temperature of the adhesive layer is performed for a necessary period of time, even if the reflow is performed while the adhesive adheres to the adhesive layer, the thermal decomposition of the adhesive can be suppressed at the same time. The occurrence of gas. As a result, the occurrence of reflow cracks can be reduced. Since the reflow temperature of the lead-free solder is about 260 ° C, the weight reduction of 260 ° C of the adhesive layer detected by differential thermal analysis (TG-DTA) is preferably 1.5% or less.
為了抑制黏著劑因為加熱所導致之重量減少,黏著劑之原料聚合物之玻璃轉移溫度Tg應為-50℃以上,或者,黏著劑層之重量平均分子量應為100萬以上。此外,亦可以光聚合起始劑之分解溫度為260℃以上之方式來進行組合。In order to suppress the weight loss of the adhesive due to heating, the glass transition temperature Tg of the base polymer of the adhesive should be -50 ° C or higher, or the weight average molecular weight of the adhesive layer should be 1,000,000 or more. Further, the photopolymerization initiator may be combined in such a manner that the decomposition temperature is 260 ° C or higher.
接著劑層係具有以下之機能者,亦即,貼合著半導體晶圓進行切割後並拾取晶片時,切割之接著劑層從黏著劑層剝離而附著於晶片,當做將晶片固定於封裝基板或導線框固定時之結合膜來使用。The adhesive layer has the following functions, that is, when the semiconductor wafer is bonded and cut and the wafer is picked up, the dicing adhesive layer is peeled off from the adhesive layer and attached to the wafer, as the wafer is fixed on the package substrate or The bonding film is used when the lead frame is fixed.
接著劑層係預先將接著劑進行薄膜化者,例如,可以使用當做接著劑使用之眾所皆知的聚醯亞胺樹脂、聚醯胺樹脂、聚醚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚酯樹脂、聚酯醯亞胺樹脂、苯氧基樹脂、聚碸樹脂、聚醚碸樹脂、聚苯硫樹脂、聚醚酮樹脂、氯化聚丙烯樹脂、丙烯酸樹脂、聚胺酯樹脂。環氧樹脂、聚丙烯醯胺樹脂、三聚氰胺樹脂等或其混合物,然而,為了使接著劑層13具有良好之分割性,以含有丙烯系共聚物、環氧樹脂且丙烯系共聚物之Tg為10℃以上為佳。此外,以含有50%以上之無機填料為佳。此外,為了強化對晶片及導線框之接著力,應將矽烷偶合劑或鈦酸鹽偶合劑當做添加劑添加於前述材料或其混合物。接著劑層之厚度並無特別限制,然而,通常以5~100μm程度為佳。The subsequent layer is obtained by previously thinning the adhesive. For example, a polyimide resin, a polyamide resin, a polyether phthalimide resin, or a polyamidamine which is well known as an adhesive can be used. Amine resin, polyester resin, polyester phthalimide resin, phenoxy resin, polyfluorene resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, chlorinated polypropylene resin, acrylic resin, polyurethane resin. Epoxy resin, polypropylene decylamine resin, melamine resin, or the like, or a mixture thereof. However, in order to impart good detachability to the adhesive layer 13, the propylene-based copolymer and the epoxy resin are contained, and the Tg of the propylene-based copolymer is 10 Above °C is preferred. Further, it is preferred to contain more than 50% of an inorganic filler. In addition, in order to enhance the adhesion to the wafer and the lead frame, a decane coupling agent or a titanate coupling agent should be added as an additive to the aforementioned materials or a mixture thereof. The thickness of the subsequent layer is not particularly limited, but is usually about 5 to 100 μm.
環氧樹脂只要進行硬化即可產生接著作用者即可,並無特別限制,然而,應使用雙官能基以上之分子量為不足5000者,最好為不足3000之環氧樹脂。此外,應使用分子量為500以上者,最好為800以上之環氧樹脂。The epoxy resin is not particularly limited as long as it can be cured by curing. However, an epoxy resin having a molecular weight of at least 5,000 or more, preferably less than 3,000, should be used. Further, an epoxy resin having a molecular weight of 500 or more, preferably 800 or more, should be used.
例如,可以使用雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、環脂肪族環氧樹脂、脂肪族鎖狀環氧樹脂、酚酚醛樹脂型環氧樹脂、甲酚酚醛樹脂型環氧樹脂、雙酚A合成酚醛樹脂型環氧樹脂、雙酚之二氧化丙烯醚化物、萘二酚之二氧化丙烯醚化物、酚類之二氧化丙烯醚化物、乙醇類之二氧化丙烯醚化物、及該等之烴基取代物、鹵化物、氫添加物等之雙官能環氧樹脂、合成酚醛樹脂型環氧樹脂。此外,亦可適用多官能環氧樹脂或含雜環基環氧樹脂等一般所熟知者。可以單獨或組合二種類以上來使用。此外,在無損特性之範圍內,亦可含有環氧樹脂以外之成份的雜質。For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a cycloaliphatic epoxy resin, an aliphatic lock epoxy resin, a phenol novolac type epoxy resin can be used. , cresol novolac resin epoxy resin, bisphenol A synthetic phenolic resin epoxy resin, bisphenol propylene oxide etherate, naphthalenediol propylene oxide etherate, phenolic propylene oxide etherate, ethanol A difunctional epoxy resin such as a propylene oxide etherate or a hydrocarbyl substituent, a halide or a hydrogen additive, or a synthetic phenol resin epoxy resin. Further, generally known as a polyfunctional epoxy resin or a heterocyclic group-containing epoxy resin can be used. They can be used singly or in combination of two or more types. In addition, impurities other than the epoxy resin may be contained within the range of non-destructive properties.
丙烯系共聚物,例如,可以使用含環氧基丙烯共聚物。含環氧基丙烯共聚物、係含有0.5~6重量%之具有環氧基的丙烯酸縮水甘油酯或甲基丙烯酸環氧丙酯。為了得到高接著力,應為0.5重量%以上,若為6重量%以下,可以抑制膠化。As the propylene-based copolymer, for example, an epoxy group-containing propylene copolymer can be used. The epoxy group-containing propylene copolymer contains 0.5 to 6% by weight of glycidyl acrylate having an epoxy group or glycidyl methacrylate. In order to obtain a high adhesion, it should be 0.5% by weight or more, and if it is 6% by weight or less, gelation can be suppressed.
當做官能基單體使用之丙烯酸縮水甘油酯或甲基丙烯酸環氧丙酯之量為0.5~6重量%之共聚物比。亦即,本發明時,含環氧基丙烯共聚物係指當做原料使用之丙烯酸縮水甘油酯或甲基丙烯酸環氧丙酯相對於所得到之共聚物為0.5~6重量%之量的共聚物。可以使用其餘部分為甲基丙烯酸酯、甲基丙烯酸甲酯等具有碳數為1~8之烴基的烷基丙烯酸酯、甲基丙烯酸烷酯、及苯乙烯或丙烯腈等之混合物。於該等中,又以甲基丙烯酸乙酯及/或甲基丙烯酸丁酯最好。混合比率應考慮共聚物之Tg來進行調整。聚合方法並無特別限制,然而,例如,利用珠狀聚合、溶液聚合等方法所得到之共聚物。含環氧基丙烯共聚物之重量平均分子量為10萬以上,若為該範圍,則接著性及耐熱性較高,30萬~300萬更佳,最好為50萬~200萬。300萬以下時,可以減少流動性降低所導致之因配合需要而對由貼附著半導體元件之支持構件所形成之配線電路之充填性降低的可能性。The amount of the glycidyl acrylate or the glycidyl methacrylate used as the functional group monomer is from 0.5 to 6% by weight of the copolymer ratio. That is, in the present invention, the epoxy group-containing propylene copolymer means a copolymer of glycidyl acrylate or glycidyl methacrylate used as a raw material in an amount of 0.5 to 6% by weight based on the copolymer obtained. . The remainder may be a mixture of an alkyl acrylate having a hydrocarbon group having 1 to 8 carbon atoms such as methacrylate or methyl methacrylate, an alkyl methacrylate, and styrene or acrylonitrile. Among these, ethyl methacrylate and/or butyl methacrylate are preferred. The mixing ratio should be adjusted in consideration of the Tg of the copolymer. The polymerization method is not particularly limited, however, for example, a copolymer obtained by a method such as bead polymerization or solution polymerization. The weight average molecular weight of the epoxy group-containing propylene copolymer is 100,000 or more. When it is in this range, the adhesiveness and heat resistance are high, and it is more preferably 300,000 to 3,000,000, more preferably 500,000 to 2,000,000. When it is 3,000,000 or less, it is possible to reduce the possibility that the filling property of the wiring circuit formed by the supporting member to which the semiconductor element is attached is lowered due to the necessity of blending due to the decrease in fluidity.
此外,本說明書中,重量平均分子量係以膠透層析術(GPC)、利用標準聚苯乙烯之檢量線的聚苯乙烯換算值。Further, in the present specification, the weight average molecular weight is a value obtained by a gel permeation chromatography (GPC) using a polystyrene equivalent of a standard polystyrene.
無機填料並無特別限制,例如,可以使用氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶、氮化硼、晶矽石、非晶矽石等。亦可以使用1種或併用2種以上。為了提高熱傳導性,以氧化鋁、氮化鋁、氮化硼、晶矽石、非晶矽石等為佳。從特性平衡之觀點而言,以矽石為佳。The inorganic filler is not particularly limited, and for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate crystal, or the like can be used. Boron nitride, crystalline vermiculite, amorphous vermiculite, and the like. It is also possible to use one type or two or more types in combination. In order to improve thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline vermiculite, amorphous vermiculite or the like is preferred. From the point of view of the balance of characteristics, it is preferable to use vermiculite.
填料之平均粒徑應為0.002~2μm,0.008~0.5μm更佳,最好為0.01~0.05μm。填料之平均粒徑為0.002μm以下時,呈現對被著體之濕潤性降低、接著性降低之傾向,超過2μm時,填料添加所造成之補強效果較小,呈現耐熱性降低之傾向。此處,平均粒徑係指從以TEM、SEM等所檢測之100個填料之粒徑所求取的平均值。The average particle diameter of the filler should be 0.002 to 2 μm, more preferably 0.008 to 0.5 μm, still more preferably 0.01 to 0.05 μm. When the average particle diameter of the filler is 0.002 μm or less, the wettability to the object is lowered and the adhesion is lowered. When the thickness exceeds 2 μm, the reinforcing effect by the addition of the filler is small, and the heat resistance tends to be lowered. Here, the average particle diameter means an average value obtained from the particle diameters of 100 fillers detected by TEM, SEM, or the like.
其次,參照第2圖,針對使用第1圖所示之本發明之半導體晶圓加工用膠帶15來製造附有接著劑層之半導體晶片的方法進行說明。Next, a method of manufacturing a semiconductor wafer with an adhesive layer using the tape for semiconductor wafer processing of the present invention shown in Fig. 1 will be described with reference to Fig. 2 .
首先,如第2(a)圖所示,將半導體晶圓W之背面貼合於半導體晶圓加工用膠帶15之接著劑層13,同時,將環框20貼合於黏著劑層12之特定位置。First, as shown in Fig. 2(a), the back surface of the semiconductor wafer W is bonded to the adhesive layer 13 of the semiconductor wafer processing tape 15, and the ring frame 20 is bonded to the specific layer of the adhesive layer 12. position.
從基材薄膜12面側,利用吸附台22吸附支持晶圓加工用膠帶15,使用未圖示之刀片,進行半導體晶圓W之機械切割,分割成複數之半導體晶片C(第2(b)圖)。此外,此時,亦同時對接著劑層13、黏著劑層12、及基材薄膜11之一部分進行適度地切割。The wafer processing tape 15 is adsorbed and supported by the adsorption stage 22 from the surface of the base film 12, and the semiconductor wafer W is mechanically cut by a blade (not shown) to be divided into a plurality of semiconductor wafers C (second (b) Figure). Further, at this time, a part of the adhesive layer 13, the adhesive layer 12, and the base film 11 is also appropriately cut.
其次,從基材薄膜11下面對黏著劑層12照射放射線使黏著劑層12硬化。因為硬化之黏著劑層12的黏著力降低,故可剝離黏著劑層12上之接著劑層13。此外,以複數層構成黏著劑層時,為了從黏著劑層12剝離接著劑層13,不必使黏著劑層整體硬化,而只使對應晶圓之黏著劑層部分硬化亦可。Next, the adhesive layer 12 is irradiated with radiation from the underside of the base film 11 to harden the adhesive layer 12. Since the adhesive force of the hardened adhesive layer 12 is lowered, the adhesive layer 13 on the adhesive layer 12 can be peeled off. Further, when the adhesive layer is formed of a plurality of layers, in order to peel the adhesive layer 13 from the adhesive layer 12, it is not necessary to cure the entire adhesive layer, and only the adhesive layer of the corresponding wafer may be partially cured.
照射程序之後,將保持著經過分割之複數半導體晶片C之半導體晶圓加工用膠帶15載置於擴展裝置之工作台21上。其次,如第2(c)圖所示,使中空圓柱形狀之頂上構件23,從半導體晶圓加工用膠帶15之下面側上昇,將上述基材薄膜11朝環框20之直徑方向及圓周方向拉伸。After the irradiation process, the semiconductor wafer processing tape 15 holding the divided plurality of semiconductor wafers C is placed on the stage 21 of the expansion device. Then, as shown in Fig. 2(c), the top member 23 having a hollow cylindrical shape is raised from the lower surface side of the semiconductor wafer processing tape 15, and the base film 11 is oriented in the radial direction and the circumferential direction of the ring frame 20. Stretching.
實施擴展程序後,在黏著薄膜擴展之狀態下,實施拾取晶片C之拾取程序。具體而言,從黏著劑薄膜14之下側以銷(未圖示)將晶片頂上,同時,從黏著劑薄膜14之上面側以吸附治具(未圖示)吸附晶片C,將單片化之晶片C與接著劑層13一起拾取。After the expansion program is implemented, the pickup process of picking up the wafer C is carried out while the adhesive film is expanded. Specifically, the wafer is topped by a pin (not shown) from the lower side of the adhesive film 14, and the wafer C is adsorbed from the upper side of the adhesive film 14 by an adsorption jig (not shown) to be singulated. The wafer C is picked up together with the adhesive layer 13.
其次,實施拾取程序後,實施粒接程序。具體而言,利用於拾取程序與晶片C一起拾取之接著劑層,將半導體晶片接著於導線框及封裝基板等。Next, after the picking process is implemented, the splicing process is performed. Specifically, the semiconductor wafer is attached to the lead frame, the package substrate, and the like by the adhesive layer picked up by the pick-up program together with the wafer C.
將載置著半導體晶片之基板等以密封材密封後,熔融配設於半導體晶片焊球等之焊錫,為了使半導體晶片與基板等導通,使其通過迴焊爐,而得到半導體裝置。此處,因為黏著劑層以示差熱分析所檢測之迴焊溫度之黏著劑層的重量減少為1.5%以下,即使黏著劑附著於接著劑層之狀態下實施迴焊,亦可抑制黏著劑熱分解所導致之排氣的發生。After the substrate or the like on which the semiconductor wafer is mounted is sealed with a sealing material, the solder is melted and placed on a semiconductor wafer solder ball or the like, and the semiconductor wafer and the substrate are electrically connected to each other to pass through a reflow furnace to obtain a semiconductor device. Here, since the weight of the adhesive layer of the adhesive layer is less than 1.5% by the reflow temperature detected by differential thermal analysis, the adhesive heat can be suppressed even if the adhesive is adhered to the adhesive layer and reflow is performed. Decomposition caused by the occurrence of exhaust.
如以上所示,拾取晶片時,即使黏著劑附著於接著劑層之狀態拾取時,亦可減少封裝之迴焊裂痕的發生。As described above, when the wafer is picked up, even if the adhesive is attached to the adhesive layer, the occurrence of reflow cracks in the package can be reduced.
其次,針對本發明之實施例進行說明,然而,本發明並未受限於該等實施側。Next, an embodiment of the present invention will be described, however, the present invention is not limited to the implementation side.
首先,調製黏著劑組成物1~9後,於厚度100μm之乙烯-醋酸乙烯共聚物薄膜(基材薄膜)上以黏著劑組成物之乾燥後厚度為10μm之方式分別塗佈黏著劑組成物1~9,以110℃實施3分鐘乾燥後,於23±5℃、45%環境下靜置3星期得到黏著薄膜。其次,調製接著劑組成物1~2,於以經過脫模處理之接著劑組成物之聚乙烯-對苯二甲酸酯薄膜所構成之釋放襯墊,分別塗佈乾燥後厚度為20μm之接著劑組成物1~2,以110℃實施3分鐘乾燥來製作接著薄膜。其次,將黏著薄膜及接著薄膜分別切割成直徑370mm、320mm之圓形,以表1所示之組合將接著薄膜之接著劑層貼合於黏著薄膜之黏著劑層側,製作實施例1~6及比較例1~3之切割‧粒接薄膜。以下,係黏著劑組成物1~8及接著劑組成物1~2的調整方法。First, after the adhesive compositions 1 to 9 were prepared, the adhesive composition was applied to the ethylene-vinyl acetate copolymer film (base film) having a thickness of 100 μm so that the thickness of the adhesive composition after drying was 10 μm. After ~9, it was dried at 110 ° C for 3 minutes, and then allowed to stand at 23 ± 5 ° C and 45% environment for 3 weeks to obtain an adhesive film. Next, the adhesive compositions 1 and 2 were prepared by applying a release liner composed of a polyethylene-terephthalate film of a release-treated adhesive composition to a thickness of 20 μm after drying. The composition 1 to 2 was dried at 110 ° C for 3 minutes to prepare a film. Next, the adhesive film and the adhesive film were respectively cut into a circular shape having a diameter of 370 mm and 320 mm, and the adhesive layer of the adhesive film was bonded to the adhesive layer side of the adhesive film in the combination shown in Table 1, and Examples 1 to 6 were produced. And the cut ‧ grain film of Comparative Examples 1 to 3. Hereinafter, the method of adjusting the adhesive compositions 1 to 8 and the adhesive compositions 1 to 2 will be employed.
於溶媒之甲苯400g,適度調整滴下量來添加異辛基丙烯酸酯340g、甲基丙烯酸甲酯13g、羥基丙烯酸酯60g、甲基丙烯酸酯0.5g、以及當做聚合起始劑之過氧化苯甲醯之混合液,調整反應溫度及反應時間,得到重量平均分子量80萬之化合物(1)溶液。以示差掃描熱析儀(DSC:Differential scanning calorimetry)檢測化合物(1)之Tg,為-49℃。其次,於化合物(1)之溶液,以相對於溶液中之化合物(1)100重量份,添加2重量份之CORONATE L(NIPPON POLYURETHANE INDUSTRY CO.,LTD.製)做為聚異氰酸酯、300重量份之聚異氰酸酯做為溶媒,進行攪拌而得到黏著劑組成物1。Into the solvent toluene 400g, moderately adjust the amount of dripping to add 340g of isooctyl acrylate, 13g of methyl methacrylate, 60g of hydroxy acrylate, 0.5g of methacrylate, and benzamidine peroxide as a polymerization initiator The mixture was adjusted to adjust the reaction temperature and the reaction time to obtain a compound (1) solution having a weight average molecular weight of 800,000. The Tg of the compound (1) was measured by a differential scanning calorimetry (DSC) to -49 °C. Next, in the solution of the compound (1), 2 parts by weight of CORONATE L (manufactured by NIPPON POLYURETHANE INDUSTRY CO., LTD.) was added as a polyisocyanate, 300 parts by weight, based on 100 parts by weight of the compound (1) in the solution. The polyisocyanate was used as a solvent and stirred to obtain an adhesive composition 1.
於上述化合物(1)之溶液,適度調整滴下量來添加2-甲基丙烯酸異氰基乙酯(isocyanatoethylmethacrylate)2.5g做為具有放射性硬化性碳-碳雙鍵及官能基之化合物、及做為聚合禁止劑之對苯二酚,調整反應溫度及反應時間,得到具有放射性硬化性碳-碳雙鍵之化合物(2)溶液。以DSC檢測化合物(2)之Tg,為-49℃。其次,於化合物(2)之溶液,添加相對於溶液中之化合物(2)100重量份為2重量份之CORONATE L做為聚異氰酸酯,添加1重量份之ILGACURE-184(NIHON CIBA-GEIGY製)做為光聚合起始劑,添加300重量份之聚異氰酸酯做為溶媒,進行攪拌而得到黏著劑組成物2。In the solution of the above compound (1), 2.5 g of isocyanatoethylmethacrylate is added as a compound having radioactive hardening carbon-carbon double bond and functional group, and as a compound The hydroquinone of the polymerization inhibitor is adjusted, and the reaction temperature and reaction time are adjusted to obtain a solution of the compound (2) having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (2) was measured by DSC to -49 °C. Next, in the solution of the compound (2), 2 parts by weight of CORONATE L based on 100 parts by weight of the compound (2) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-184 (manufactured by NIHON CIBA-GEIGY) is added. As a photopolymerization initiator, 300 parts by weight of a polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 2.
於溶媒之甲苯400g中,適度調整滴下量來添加異辛基丙烯酸酯340g、甲基丙烯酸甲酯3g、羥基丙烯酸酯60g、甲基丙烯酸酯0.5g、以及做為聚合起始劑之過氧化苯甲醯之混合液,調整反應溫度及反應時間,得到重量平均分子量50萬之化合物後,適度調整滴下量來添加2-甲基丙烯酸異氰基乙酯2.5g做為具有放射性硬化性碳-碳雙鍵及官能基之化合物、添加對苯二酚做為聚合禁止劑,調整反應溫度及反應時間,得到具有放射性硬化性碳-碳雙鍵之化合物(3)溶液。以DSC檢測化合物(3)之Tg,為-52℃。其次,於化合物(3)之溶液,添加相對於溶液中之化合物(3)100重量份為0.7重量份之CORONATE L做為聚異氰酸酯,添加1重量份之ILGACURE-184做為光聚合起始劑,添加300重量份之聚異氰酸酯做為溶媒,進行攪拌而得到黏著劑組成物3。In 400 g of toluene in a solvent, 340 g of isooctyl acrylate, 3 g of methyl methacrylate, 60 g of hydroxy acrylate, 0.5 g of methacrylate, and benzoic acid as a polymerization initiator were added as appropriate. A mixture of formazan, adjusting the reaction temperature and reaction time to obtain a compound having a weight average molecular weight of 500,000, and then appropriately adjusting the amount of dropwise addition to add 2.5 g of 2-cyanoethyl methacrylate as a radioactive hard carbon-carbon. A compound having a double bond and a functional group, and hydroquinone added as a polymerization inhibitor, the reaction temperature and the reaction time are adjusted to obtain a compound (3) solution having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (3) was measured by DSC to -52 °C. Next, in the solution of the compound (3), 0.7 parts by weight of CORONATE L based on 100 parts by weight of the compound (3) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-184 is added as a photopolymerization initiator. 300 parts by weight of polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 3.
於甲苯400g中,適度調整滴下量來添加n-丙烯酸丁酯443g、甲基丙烯酸甲酯80g、羥基丙烯酸酯100g、甲基丙烯酸酯7g、以及做為聚合起始劑之過氧化苯甲醯之混合液,調整反應溫度及反應時間,得到重量平均分子量20萬之化合物後,適度調整滴下量來添加做為具有放射性硬化性碳-碳雙鍵及官能基之化合物之2-甲基丙烯酸異氰基乙酯2.5g、做為聚合禁止劑之對苯二酚,調整反應溫度及反應時間,得到具有放射性硬化性碳-碳雙鍵之化合物(4)溶液。以DSC檢測化合物(4)之Tg,為-36℃。其次,於化合物(4)之溶液,添加相對於溶液中之化合物(4)100重量份為0.5重量份之CORONATE L做為聚異氰酸酯,添加1重量份之ILGACURE-184做為光聚合起始劑,添加300重量份之聚異氰酸酯做為溶媒,進行攪拌而得到黏著劑組成物4。In 400 g of toluene, 443 g of n-butyl acrylate, 80 g of methyl methacrylate, 100 g of hydroxy acrylate, 7 g of methacrylate, and benzammonium peroxide as a polymerization initiator were added to the toluene in an appropriate amount. Mixing solution, adjusting reaction temperature and reaction time to obtain a compound having a weight average molecular weight of 200,000, and then appropriately adjusting the amount of dropwise addition to add 2-methacrylic acid isocyanide as a compound having a radioactive hardening carbon-carbon double bond and a functional group. 2.5 g of ethyl ethyl ester, hydroquinone as a polymerization inhibiting agent, and the reaction temperature and reaction time were adjusted to obtain a compound (4) solution having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (4) was measured by DSC to -36 °C. Next, in the solution of the compound (4), 0.5 parts by weight of CORONATE L based on 100 parts by weight of the compound (4) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-184 is added as a photopolymerization initiator. 300 parts by weight of polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 4.
於上述化合物(4)之溶液,添加相對於溶液中之化合物(4)100重量份為0.7重量份之CORONATE L做為聚異氰酸酯,添加1重量份之ILGACURE-2959做為光聚合起始劑,添加300重量份之聚異氰酸酯做為溶媒,進行攪拌而得到黏著劑組成物5。To the solution of the above compound (4), 0.7 parts by weight of CORONATE L relative to 100 parts by weight of the compound (4) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-2959 is added as a photopolymerization initiator. 300 parts by weight of polyisocyanate was added as a solvent, and the mixture was stirred to obtain an adhesive composition 5.
於溶媒之甲苯400g中,適度調整滴下量來添加丙烯酸月桂酯(lauryl acrylate)200g、2-乙基己基丙烯酸酯(ethylhexylacrylate)100g、甲基丙烯酸酯10g、以及做為聚合起始劑之過氧化苯甲醯之混合液,調整反應溫度及反應時間,得到重量平均分子量80萬之化合物後,適度調整滴下量來添加做為具有放射性硬化性碳-碳雙鍵及官能基之化合物的2-甲基丙烯酸異氰基乙酯2.5g、做為聚合禁止劑之對苯二酚,調整反應溫度及反應時間,得到具有放射性硬化性碳-碳雙鍵之化合物(5)溶液。以DSC檢測化合物(5)之Tg,為-20℃。其次,於化合物(5)之溶液,添加相對於溶液中之化合物(5)100重量份為1重量份之CORONATE L做為聚異氰酸酯,添加1重量份之ILGACURE-907做為光聚合起始劑,得到黏著劑組成物6。In 400 g of toluene in a solvent, 200 g of lauryl acrylate, 100 g of ethylhexylacrylate, 10 g of methacrylate, and peroxidation as a polymerization initiator were added as appropriate. a mixture of benzamidine, adjusting the reaction temperature and reaction time to obtain a compound having a weight average molecular weight of 800,000, and then appropriately adjusting the amount of dropping to add a compound which is a compound having a radioactive hardening carbon-carbon double bond and a functional group. 2.5 g of isocyanoethyl acrylate and hydroquinone as a polymerization inhibitor, the reaction temperature and the reaction time were adjusted to obtain a compound (5) solution having a radioactive hardenable carbon-carbon double bond. The Tg of the compound (5) was measured by DSC to be -20 °C. Next, in the solution of the compound (5), 1 part by weight of CORONATE L based on 100 parts by weight of the compound (5) in the solution is added as a polyisocyanate, and 1 part by weight of ILGACURE-907 is added as a photopolymerization initiator. , the adhesive composition 6 was obtained.
於溶媒之甲苯400g中,適度調整滴下量來添加n-丙烯酸丁酯340g、羥基丙烯酸酯70g、甲基丙烯酸酯3.5g、以及做為聚合起始劑之過氧化苯甲醯之混合液,調整反應溫度及反應時間,得到重量平均分子量90萬之化合物後,適度調整滴下量來添加做為具有放射性硬化性碳-碳雙鍵及官能基之化合物之2-甲基丙烯酸異氰基乙酯2.5g、做為聚合禁止劑之對苯二酚,調整反應溫度及反應時間,得到具有放射性硬化性碳-碳雙鍵之化合物(6)溶液。以DSC檢測化合物(6)之Tg,為-49℃。其次,於化合物(6)之溶液,添加相對於溶液中之化合物(6)100重量份之1重量份之ILGACURE-651做為光聚合起始劑,得到黏著劑組成物7。In 400 g of toluene in a solvent, the amount of dripping was adjusted appropriately, and 340 g of n-butyl acrylate, 70 g of hydroxy acrylate, 3.5 g of methacrylate, and a mixture of benzammonium peroxide as a polymerization initiator were added and adjusted. After the reaction temperature and the reaction time are obtained, a compound having a weight average molecular weight of 900,000 is obtained, and the amount of the dropwise addition is appropriately adjusted to add 2-isocyanoethyl 2-methacrylate as a compound having a radioactive hardening carbon-carbon double bond and a functional group. g. Hydroquinone as a polymerization inhibitor, adjusting the reaction temperature and reaction time to obtain a compound (6) solution having a radioactive hardening carbon-carbon double bond. The Tg of the compound (6) was measured by DSC to -49 °C. Next, in the solution of the compound (6), 1 part by weight of ILGACURE-651 is added as a photopolymerization initiator to 100 parts by weight of the compound (6) in the solution to obtain an adhesive composition 7.
於溶媒之甲苯400g中,適度調整滴下量來添加n-丙烯酸丁酯340g、甲基丙烯酸甲酯13g、羥基丙烯酸酯7g、甲基丙烯酸酯0.5g、以及當做聚合起始劑之過氧化苯甲醯之混合液,調整反應溫度及反應時間,得到重量平均分子量5萬之化合物(7)溶液。以DSC檢測化合物(7)之Tg,為-52℃。其次,於化合物(7)之溶液,添加相對於溶液中之化合物(7)100重量份為2重量份之CORONATE L做為聚異氰酸酯,添加300重量份之聚異氰酸酯做為溶媒,進行攪拌得到黏著劑組成物8。In 400 g of toluene in a solvent, 340 g of n-butyl acrylate, 13 g of methyl methacrylate, 7 g of hydroxy acrylate, 0.5 g of methacrylate, and benzoyl peroxide as a polymerization initiator were added as appropriate. The mixture of hydrazine was adjusted to the reaction temperature and the reaction time to obtain a solution of the compound (7) having a weight average molecular weight of 50,000. The Tg of the compound (7) was measured by DSC to -52 °C. Next, in the solution of the compound (7), 2 parts by weight of CORONATE L based on 100 parts by weight of the compound (7) in the solution is added as a polyisocyanate, 300 parts by weight of polyisocyanate is added as a solvent, and stirring is carried out to obtain an adhesive. Composition 8.
各光聚合起始劑之熱分解開始溫度,只有ILGACURE-2959為260℃以上,ILGACURE-907、651、184為不足260 ℃。The thermal decomposition onset temperature of each photopolymerization initiator was only 260 ° C or higher for ILGACURE-2959, and less than 260 ° C for ILGACURE-907, 651, and 184.
係將部分具有當做環氧樹脂之甲酚酚醛樹脂型環氧樹脂(環氧化物當量197、分子量1200、軟化點70℃)15重量份、丙烯酸樹脂(質量平均分子量:80萬、玻璃轉移溫度-17℃)70重量份、當做硬化劑之酚酚醛樹脂樹脂(羥基當量104、軟化點80℃)15重量份、當做促進劑之1份CUREZOL 2PZ(SHIKOKU CHEMICALS CORPORATION製、商品名稱:2-苯咪唑(phenylimidazole))於有機溶劑中攪拌而得到接著劑組成物1。A part of the cresol novolac type epoxy resin (epoxide equivalent 197, molecular weight 1200, softening point 70 ° C) as an epoxy resin is 15 parts by weight, and an acrylic resin (mass average molecular weight: 800,000, glass transition temperature - 17 parts by weight of a phenolic phenol resin resin (hydroxyl group equivalent 104, softening point 80 ° C) as a curing agent, 15 parts by weight of CUREZOL 2PZ (manufactured by SHIKOKU CHEMICALS CORPORATION, trade name: 2-benzimidazole) (phenylimidazole)) was stirred in an organic solvent to obtain an adhesive composition 1.
係將部分具有當做環氧樹脂之甲酚酚醛樹脂型環氧樹脂(環氧化物當量197、分子量1200、軟化點70℃)5重量份、當做矽烷偶合劑之3-縮水甘油丙基三甲氧基矽烷(glycidoxypropyltrimethoxysilane)0.5質量份、平均粒徑1.0μm之矽石填料50質量份、2,2’-雙[4-(4-胺基苯氧基)苯基]丙烷、由3,3’,4,4’-二苯基四羧酸二酸酐(diphenyltetracarboxylic dianhydride)及苯均四酸酐所合成之質量平均分子量5萬之聚醯亞胺樹脂40質量份、做為硬化劑之酚酚醛樹脂樹脂(羥基當量104、軟化點80℃)5重量份、做為促進劑之1份之CUREZOL 2PZ於有機溶劑中攪拌而得到接著劑組成物2。A part of a cresol novolac type epoxy resin (epoxide equivalent 197, molecular weight 1200, softening point 70 ° C) as an epoxy resin, 5 parts by weight as a decane coupling agent, 3-glycidylpropyltrimethoxy group 0.5 parts by mass of glycidoxypropyltrimethoxysilane, 50 parts by mass of vermiculite filler having an average particle diameter of 1.0 μm, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane, and 3,3′, 40 parts by mass of a polyamidene resin having a mass average molecular weight of 50,000 synthesized by 4,4'-diphenyltetracarboxylic dianhydride and pyromellitic anhydride, and a phenol novolac resin as a hardener 5 parts by weight of a hydroxyl group equivalent 104, a softening point of 80 ° C), and 1 part of CUREZOL 2PZ as a promoter were stirred in an organic solvent to obtain an adhesive composition 2.
實施例及比較例之評估以下述方式實施。The evaluation of the examples and comparative examples was carried out in the following manner.
利用以黏著劑組成物所製作之黏著薄膜,只刮取黏著劑,以膠透層析術(GPC)利用標準聚苯乙烯之檢量線並以聚苯乙烯換算值來檢測。檢測條件如下所示。Using an adhesive film made of an adhesive composition, only the adhesive was scraped off, and a standard polystyrene calibration line was used for gel permeation chromatography (GPC) and detected in terms of polystyrene. The detection conditions are as follows.
GPC裝置:TOSOH CORPORATION製HLC-8120GPCGPC device: HLC-8120GPC manufactured by TOSOH CORPORATION
管柱:TSK gel SuperH5000、流量:0.6ml/minColumn: TSK gel SuperH5000, flow: 0.6ml/min
濃度:0.3質量%、注入量:20μlConcentration: 0.3% by mass, injection amount: 20 μl
管柱溫度:40℃、溶析液:四氫呋喃。Column temperature: 40 ° C, eluent: tetrahydrofuran.
對實施例1~6及比較例1~3之切割‧粒接薄膜之黏著劑層,以空冷式高壓水銀燈(80W/cm、照射距離10cm)、200mJ/cm2 照射紫外線。針對實施例1及紫外線照射後之實施例2~6、比較例1~3,以熱重量檢測進行示差熱分析(TG-DTA),一邊將檢測容器內之溫度從室溫改變至300℃一邊進行重量減少之檢測,求取220℃及260℃之重量減少。樣本量為約10mg,以溫度10℃/min之速度進行變化。其結果如表1所示。The adhesive layers of the ‧ granule films of Examples 1 to 6 and Comparative Examples 1 to 3 were irradiated with ultraviolet rays by an air-cooled high-pressure mercury lamp (80 W/cm, irradiation distance: 10 cm) and 200 mJ/cm 2 . With respect to Example 1 and Examples 2 to 6 and Comparative Examples 1 to 3 after ultraviolet irradiation, differential thermal analysis (TG-DTA) was performed by thermogravimetric detection, and the temperature in the detection container was changed from room temperature to 300 ° C. The weight reduction test was performed to obtain a weight loss of 220 ° C and 260 ° C. The sample size was about 10 mg and was varied at a rate of 10 ° C/min. The results are shown in Table 1.
於厚度200μm之矽晶圓背面,貼附實施例及比較例之切割‧粒接薄膜之接著劑層,切割成7.5mm×7.5mm,將附有接著劑層之晶片從黏著劑層剝離並拾取後,以XPS(X射線光電子光譜法),將緣自黏著劑之轉印汚染物之碳增加量空白試樣進行比較,選出20個5Atomic%以上之晶片,以180℃、10N、5秒之條件固定於玻璃環氧基板之上。此外,以密封材(KYOCERA CHEMICAL CORPORATION製)進行模製來製作迴焊樣本。將密封材之樣本,以85℃/85%RH之恆溫恆濕層實施168小時的處理後,對應共晶焊錫處理進行220℃、60秒間加熱,或對應無鉛焊錫處理進行260℃、60秒間加熱,以日立建機株式會社製超音波成像儀(SAT)進行觀察,調查有無封裝裂痕。對全部20個封裝,所觀測到之封裝裂痕的封裝個數如表1所示。On the back surface of the wafer having a thickness of 200 μm, the adhesive layer of the ‧ grain film of the embodiment and the comparative example was attached, and cut into 7.5 mm × 7.5 mm, and the wafer with the adhesive layer was peeled off from the adhesive layer and picked up. Then, XPS (X-ray photoelectron spectroscopy) is used to compare the carbon increase blanks of the transfer contaminants from the adhesive, and select 20 wafers of 5 Atomic% or more, at 180 ° C, 10 N, 5 seconds. The conditions are fixed on the glass epoxy substrate. Further, a reflowed sample was produced by molding with a sealing material (manufactured by KYOCERA CHEMICAL CORPORATION). The sample of the sealing material is treated with a constant temperature and humidity layer of 85 ° C / 85% RH for 168 hours, and then heated at 220 ° C for 60 seconds corresponding to the eutectic solder treatment, or heated at 260 ° C for 60 seconds corresponding to the lead-free solder treatment. The ultrasonic imager (SAT) manufactured by Hitachi Construction Machinery Co., Ltd. was observed to investigate the presence or absence of cracks in the package. The number of packages of package cracks observed for all 20 packages is shown in Table 1.
比較例時,因為220℃、260℃之重量減少皆超過1.5%,大部分的封裝都觀測到裂痕。相對於此,實施例1~6時,220℃、260℃之重量減少皆為1.5%以下,全部封裝皆未觀測到裂痕。In the comparative example, since the weight loss at 220 ° C and 260 ° C exceeded 1.5%, cracks were observed in most of the packages. On the other hand, in Examples 1 to 6, the weight loss at 220 ° C and 260 ° C was 1.5% or less, and no crack was observed in all of the packages.
如以上所示,拾取晶片時,即使黏著劑附著於接著劑層之狀態進行拾取時,亦可減少封裝之迴焊裂痕。As described above, when the wafer is picked up, even if the adhesive is attached to the adhesive layer and picked up, the reflow crack of the package can be reduced.
11...基材薄膜11. . . Substrate film
12...黏著劑層12. . . Adhesive layer
13...接著劑層13. . . Subsequent layer
14...黏著劑薄膜14. . . Adhesive film
15...半導體晶圓加工用膠帶15. . . Semiconductor wafer processing tape
20...環框20. . . Ring frame
21...工作台twenty one. . . Workbench
22...吸附台twenty two. . . Adsorption station
23...頂上構件twenty three. . . Top member
第1圖係本發明之半導體晶圓加工用膠帶之一例的剖面圖。Fig. 1 is a cross-sectional view showing an example of a tape for processing a semiconductor wafer of the present invention.
第2(a)圖係將半導體晶圓W及環框貼合於半導體晶圓加工用膠帶之狀態的剖面圖,(b)係切割後之半導體晶圓加工用膠帶及半導體晶圓的剖面圖,(c)係擴展後之半導體晶圓加工用膠帶及半導體晶圓的剖面圖。Fig. 2(a) is a cross-sectional view showing a state in which a semiconductor wafer W and a ring frame are bonded to a semiconductor wafer processing tape, and (b) a sectional view of the semiconductor wafer processing tape and the semiconductor wafer after the dicing (c) is a cross-sectional view of the expanded semiconductor wafer processing tape and the semiconductor wafer.
11...基材薄膜11. . . Substrate film
12...黏著劑層12. . . Adhesive layer
13...接著劑層13. . . Subsequent layer
14...黏著劑薄膜14. . . Adhesive film
15...半導體晶圓加工用膠帶15. . . Semiconductor wafer processing tape
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JP2008027960A (en) * | 2006-07-18 | 2008-02-07 | Nitto Denko Corp | Heat-resistance dicing tape or sheet |
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JP2008277796A (en) * | 2007-04-02 | 2008-11-13 | Hitachi Chem Co Ltd | Adhesive film for semiconductor, semiconductor device, and method of manufacturing the semiconductor device |
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JP2009146974A (en) * | 2007-12-12 | 2009-07-02 | Sekisui Chem Co Ltd | Double-sided adhesive tape for semiconductor processing |
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US5538771A (en) * | 1991-06-28 | 1996-07-23 | Furukawa Electric Co., Ltd. | Semiconductor wafer-securing adhesive tape |
JP2008027960A (en) * | 2006-07-18 | 2008-02-07 | Nitto Denko Corp | Heat-resistance dicing tape or sheet |
JP2008143924A (en) * | 2006-12-06 | 2008-06-26 | Nitto Denko Corp | Repeelable adhesive composition, and adhesive tape or sheet |
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