TW201118145A - Thermosetting die bonding film - Google Patents

Thermosetting die bonding film Download PDF

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Publication number
TW201118145A
TW201118145A TW099134113A TW99134113A TW201118145A TW 201118145 A TW201118145 A TW 201118145A TW 099134113 A TW099134113 A TW 099134113A TW 99134113 A TW99134113 A TW 99134113A TW 201118145 A TW201118145 A TW 201118145A
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TW
Taiwan
Prior art keywords
film
thermosetting
resin
hardening
weight
Prior art date
Application number
TW099134113A
Other languages
Chinese (zh)
Inventor
Yuichiro Shishido
Naohide Takamoto
Original Assignee
Nitto Denko Corp
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Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of TW201118145A publication Critical patent/TW201118145A/en

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Abstract

Provided are a thermosetting die bonding film and a dicing/die bonding film, in which curing shrinkage after die bonding is inhibited and thereby an object to be adhered is prevented from warpage. The thermosetting die bonding film is utilized for sticking and fixing a semiconductor device to the object to be adhered, wherein a gel fraction of an organic constituent being thermoset by a thermal treatment of 120 DEG C for one hour is less than or equal to 20 wt%, and a gel fraction of the organic constituent being thermoset by a thermal treatment of 175 DEG C for one hour ranges between 10 wt% and 30 wt%.

Description

201118145 六 發明說明：. 【發明所屬之技術領域】 本發明涉及將例如半導體晶片等半導體元件 基板或引線框等被黏物上時使用的熱硬化型黏晶薄膜 外’ ίί日ϋ及該熱硬化型黏晶薄膜與切割薄膜層叠而成 到 的切割/黏晶薄膜 【先前技術】 以往，在半導«置的製造過財，使用在切割工庠 中膠黏保持半導體晶11、並且也提供安裝卫序所 片固著用膠黏劑層的切割/黏晶薄膜（參照以下專利^曰 1)。該切㈣膜，具有在支#基材上依次層疊黏合劑 層和膠黏劑層的結構。g卩，在膠黏劑層的保持下將半導體 晶圓切割後，拉伸支縣材，將半導體晶片與黏晶薄膜一 起拾取(pick-up)。再將半導體晶片通過黏晶薄膜黏晶到引 線框的晶片焊盤(die pad)上。 但是，近年來，隨著半導體晶圓的大型化和薄型化， 半，體晶片也薄型化。將這樣的半導體晶片通過黏晶薄膜 ，著到基板等絲物上並使其減化時(黏晶），由於黏晶 薄膜的熱硬化而硬化H結果，產生被黏她曲的問題。 現有技術文獻 專利文獻1 :日本特開昭6〇_57342號公報 【發明内容】 4 201118145 本發明是馨於上述問題而進行的，其目的在於提供可 以抑制黏晶後的硬化收縮、並且由此可以防止相對於被黏 物產生翹曲的熱硬化型黏晶薄膜、以及切割/黏晶薄膜。— ^本發明人為了解決上述現有的問題，對熱硬化型黏晶 薄膜及切割/黏晶薄膜進行了研究。結果發現，對於熱處理 後的熱硬化型黏晶薄膜，當其有機成分的凝膠分率(gei fractum)在一定的數值範圍内時能夠減小其硬化收縮，從而 完成了本發明。 即，本發明的熱硬化型黏晶薄膜，用於將半導體元件 膠黏固定到被黏物上，其特徵在於，通過12〇t、丨小時的 熱處理而熱硬化後有機成分的凝膠分率 的範圍㈣且觸聊、丨小_鱗理聽4== 機成分的凝膠分率在1〇〜30重量％的範圍内。 使用熱硬化型黏晶薄膜將半導體元件黏晶到被黏物 上時，從使半導體元件與被黏物的膠黏固定可靠的觀點考 慮優選使熱硬化型黏晶薄膜充分地熱硬化。但是，熱硬 化反應過度進行時，有時熱硬化型黏晶薄膜自身發生硬化 收縮本發明中，如上述構成所述，由於通過i2〇°c、1 小時的熱處理而熱硬化後有機成分的凝膠分率在2〇重量 /〇以下，並且通過175〇c、丨小時的熱處理而熱硬化後有機 成分的凝膠分率在1Q〜3〇重量％的範_，因此例如在將 半導體元件黏晶到被黏物上時’或者絲焊時進行的熱處理 中’抑制膜的完全熱硬化。由此，可以減小熱硬化型黏晶 薄膜的硬化收縮。結果，能夠抑制由於該硬化收縮而在被 201118145 產絲曲’從而在半導«置的製造中可以提高生 上述構巧的熱硬化型黏晶薄臈，優選其酸值在 4〜10 7下66上的範圍内。，由此，例如在通過12〇<t、1小時條 切麟斑*、处理來抑制被黏物上產生趣曲的同時能夠提高剪 切膠黏力。 ㈣^構成的熱硬化型黏晶薄膜’優選由熱硬化性樹脂 二1在1〇〜40 mgK〇H/g範圍内的熱塑性樹脂形成。由 匕’ ^黏晶時對熱硬化型黏晶薄臈進行的熱處理中，能夠 ”、、硬化型黏晶薄膜的熱硬化過度進行。 土述構成的熱硬化型黏晶薄膜中優選添加有熱硬化 ^ 例如，優選通過密封樹脂將在被黏物上黏晶的半 密封，並且在進行後硬化工序時’使熱硬化型黏 =膜充分熱硬化。本發明中，如上述構成所述通過添加 …硬化催化劑’在半導體元件黏晶到被黏物上時，熱硬化 至不產生硬化收縮的程度’在所述後硬化工序時可以使熱 硬化型黏晶薄膜的熱硬化充分進行。結果，可以製造將半 導體元件可靠地膠黏固定到被黏物上、且半導體元件不從 被黏物上剝離的半導體裝置。 所述構成中’通過12(TC、1小時的熱處理熱硬化後 的剪切膠黏力優選為0.2购以上。由此，例如即使進行 焊工序，也不會由於該工序中超聲波振動或加熱而在熱 硬化型黏晶薄膜與半導體元件紐祕的轉面上產生剪 6 201118145 切變形。即，半導體元件不會因絲焊時的超聲波振動而活 動’由此可以抑制絲焊成功率下降。 另外，所述構成中’熱硬化前的12(TC下的熔融黏度 優選在50〜1000 Pa.s的範圍内。通過使熱硬化型黏晶薄膜 的熱硬化别的k融黏度為50 Pa.s以上，可以使對被黏物的 检合性良好。結果，在與被黏物的膠黏面上，可以減少空 隙的產生。另外，通過使所述炼融黏度為1〇〇〇 pa.s以下， 可以抑制膠黏劑成分等從熱硬化型黏晶薄膜中滲出。結 果，可以防止被黏物或被黏物上膠黏固定的半導體元件的 污染。 所述構成中，通過175t、1小時熱處理而熱硬化後 的260°c下的儲能彈性模量優選為1 MPa以上。由此，例 如即使在耐濕回流知接试驗等中可靠性也高，可以製造 耐濕回流性優良的半導體裝置。 另外，本發明的切割/黏晶薄膜，為了解決上述問題， 其特徵在於，具有在切割薄膜上層疊有所述熱硬化型黏晶 薄膜的結構。 . 另外，本發明的半導體裝置，為了解決上述問題，其 - 特徵在於’使用上述熱硬化型黏晶薄膜、或上述切割/黏晶 薄膜而製造。 本發明通過上述說明過的方法，實現下述的效果。 即，根據本發明的熱硬化型黏晶薄膜，通過12〇。〇、！ 小時的熱處理而熱硬化後有機成分的凝膠分率為2〇重量 201118145 V A V-TL/li. 理而熱硬化後有機 將半導體=斑日,3G重1°/°的範圍内，因此，例如在 中上時或者絲烊時進行的熱處理 +中賴不a元王熱硬化。結果，可以減少㈣化 溥膜的硬化收縮，防止被點物 曰曰 體裝置的製造中生產量產4_’從而實現半導 為讓上述特徵和優點能㈣㈣懂，下文特 舉貫_，並配合所附圖式作詳細說明如下。 【實施方式】 ，於本實施方式的熱硬化型黏晶薄難下，稱為「黏 二缚膜」），下面以如圖卜标的在基材i上層疊有黏合劑' t的切割薄膜上層疊而成的切割/黏晶薄膜的方式為例 進行說明。 為上述黏晶薄膜3中，通過靴、1小時的熱處理而 熱硬化後有機成分的凝膠分率為2G重量％以下、優選為 (M5重$%、更優選為〇〜1()重量％的範肋。所述凝膠分 ^為2〇重量％以下時，例如，在黏晶時的熱處理中，黏晶 薄，3元全熱硬化’由此可以抑制硬化收缩。另外，通過 175C、：1小時的熱處理而熱硬化後有機成分的凝膠分率在 =〜30重量％、優選1〇〜25重量％、更優選1〇〜2〇重量％的 範圍内。所述凝膠分率為1〇〜3〇重量％時，例如即使在絲 焊時的熱處理巾，黏晶薄膜3也完全熱硬化，由此可以抑 制硬化收縮。 8 201118145 JOiOHpil 所述黏晶薄膜3的酸值優選在4〜1〇 mgK〇H/g的範圍 内’更優選6〜8mgKOH/g的範圍内。酸㈣4 mgKQH/g[Technical Field] The present invention relates to a thermosetting type adhesive film which is used when a semiconductor element substrate such as a semiconductor wafer or a lead frame is adhered to an adherend, and the heat hardening. A dicing/mulet film laminated with a dicing film and a dicing film [Prior Art] In the past, in the manufacture of semi-conductive materials, the semiconductor crystal 11 was adhered and used in a cutting process, and installation was also provided. The dicing/adhesive film of the adhesive layer is fixed (see the following patent ^曰1). The cut (four) film has a structure in which an adhesive layer and an adhesive layer are sequentially laminated on a support # substrate. That is, after the semiconductor wafer is cut under the holding of the adhesive layer, the branch material is stretched, and the semiconductor wafer and the die-bonded film are picked up together. The semiconductor wafer is then die bonded through a die attach film to a die pad of the lead frame. However, in recent years, with the increase in size and thickness of semiconductor wafers, semi-body wafers have also been thinned. When such a semiconductor wafer is passed through a die-bonding film to a filament such as a substrate and is reduced (adhesive crystal), the result of hardening H due to thermal hardening of the die-bonded film causes a problem of being stuck. CITATION LIST Patent Literature 1: Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. A thermosetting type adhesive film which can prevent warpage with respect to an adherend, and a dicing/mulet film can be prevented. - In order to solve the above-mentioned problems, the inventors of the present invention have studied thermosetting type die-bonding films and dicing/mulet films. As a result, it has been found that the heat-hardened type of the heat-curable type of the heat-curable type of the crystallized film can reduce the hardening shrinkage when the gel fraction (e) of the organic component is within a certain numerical range, thereby completing the present invention. That is, the thermosetting type adhesive crystal film of the present invention is used for adhering and fixing a semiconductor element to an adherend, and is characterized in that the gel fraction of the organic component after heat hardening by heat treatment at 12 〇t and 丨h is characterized. The range (4) and the chattering, small _ syllabus listening 4 = = machine component gel fraction in the range of 1 〇 ~ 30% by weight. When the semiconductor element is bonded to the adherend using a thermosetting type adhesive film, it is preferable to sufficiently thermally harden the thermosetting type crystal film from the viewpoint of reliably fixing the semiconductor element and the adherend. However, when the thermosetting reaction progresses excessively, the thermosetting type microcrystalline film itself may be hardened and shrunk. In the present invention, as described above, the organic component is coagulated by heat treatment by i2〇°c and heat treatment for 1 hour. The gel fraction is 2 〇/〇, and the gel fraction of the organic component after heat hardening by heat treatment at 175 〇c and 丨hour is in the range of 1Q to 3〇% by weight, so that, for example, the semiconductor element is stuck. When the crystal is applied to the adherend, or in the heat treatment performed during wire bonding, the film is completely thermally hardened. Thereby, the hardening shrinkage of the thermosetting type die-bonding film can be reduced. As a result, it is possible to suppress the occurrence of the above-described structure of the thermosetting type microcrystalline enamel which is produced by the 201118145 due to the hardening shrinkage, and preferably has an acid value of 4 to 10 7 Within the scope of 66. Thus, for example, it is possible to increase the shearing adhesive force by suppressing the occurrence of the fungus on the adherend by 12 〇 <t, 1 hour stripping, and treatment. (4) The thermosetting type microcrystalline film constituting ' is preferably formed of a thermoplastic resin having a thermosetting resin 1-2 in the range of 1 Torr to 40 mgK 〇H/g. In the heat treatment of the thermosetting type microcrystalline ruthenium in the case of 黏 ^ ^, the thermal hardening of the hard-formed viscous film can be excessively performed. The heat-hardened type of the morphological film is preferably added with heat. Hardening ^ For example, it is preferable to semi-hert the crystal on the adherend by a sealing resin, and to sufficiently heat-harden the thermosetting type adhesive film in the post-hardening step. In the present invention, the above-described constitution is added by The hardening catalyst 'heat hardens to the extent that hardening shrinkage occurs when the semiconductor element is bonded to the adherend'. In the post-hardening step, the thermosetting of the thermosetting type microcrystalline film can be sufficiently cured. A semiconductor device in which a semiconductor element is reliably adhered to an adherend and the semiconductor element is not peeled off from the adherend is manufactured. In the above configuration, 'through 12 (TC, 1 hour heat-treated hardened shear adhesive) The adhesive strength is preferably 0.2 or more. Thus, for example, even if the welding step is performed, the thermosetting type microcrystalline film and the semiconductor element are not subjected to ultrasonic vibration or heating in the step. On the turning surface, shearing is performed. 201118145 Shear deformation. That is, the semiconductor element does not move due to ultrasonic vibration during wire bonding', thereby suppressing the drop in the success rate of the wire bonding. In addition, in the above configuration, 12 before the thermal hardening ( The melt viscosity at TC is preferably in the range of 50 to 1000 Pa.s. By thermosetting the thermosetting type die-bonding film to have a k-melting viscosity of 50 Pa.s or more, the adhesion to the adherend can be made. As a result, the occurrence of voids can be reduced on the adhesive surface with the adherend. Further, by setting the smelting viscosity to 1 〇〇〇pa.s or less, it is possible to suppress the adhesive component and the like from thermal hardening. As a result, it is possible to prevent contamination of the semiconductor element adhered and fixed by the adherend or the adherend. In the above configuration, the storage at 260 ° C after heat hardening by 175 t, 1 hour heat treatment. The elastic modulus is preferably 1 MPa or more. Therefore, for example, even in a moisture-resistant reflow test, the reliability is high, and a semiconductor device excellent in moisture reflow resistance can be produced. Film, in order to solve the above problems The semiconductor device of the present invention has a structure in which the thermosetting type die-bonding film is laminated on the dicing film. Further, in order to solve the above problems, the semiconductor device of the present invention is characterized in that 'the above-mentioned thermosetting type die-bonding film is used. The present invention is produced by the above-described method of cutting/bonding a film. The present invention achieves the following effects by the method described above. That is, the thermosetting type die-bonding film according to the present invention is heat-treated by heat treatment of 12 Torr. After hardening, the gel fraction of the organic component is 2〇 weight 201118145 VA V-TL/li. After heat hardening, the organic semiconductor will be in the range of 1 day/°, and 3G is 1°/°, for example, in the middle and upper Or the heat treatment performed during the silk crucible + the thermal hardening of the alumite. As a result, the hardening shrinkage of the (4) bismuth film can be reduced, and the mass production of the 曰曰 曰曰 被 防止 防止 4 4 4 4 4 4 被 被 被 被Let the above features and advantages be understood by (4) and (4), and the following is a detailed description of the following. [Embodiment] In the case where the thermosetting type adhesive crystal of the present embodiment is difficult to be thin, it is referred to as "adhesive two-bonding film", and the following is shown on the dicing film in which the adhesive agent is laminated on the substrate i as shown in the figure. The method of laminating the dicing/mulet film is described as an example. In the above-mentioned microcrystalline film 3, the gel fraction of the organic component after heat curing by the heat treatment for 1 hour is 2 G% by weight or less, preferably (M5 is more than $%, more preferably 〇1 to 1% by weight). When the gel fraction is 2% by weight or less, for example, in the heat treatment at the time of die bonding, the cohesive crystal is thin, and the 3 member is fully heat-cured, thereby suppressing hardening shrinkage. Further, by 175C, : the heat-hardening after 1 hour of heat treatment, the gel fraction of the organic component is in the range of 〜30% by weight, preferably 1% to 25% by weight, more preferably 1% to 2% by weight. When it is 1 〇 to 3 〇% by weight, for example, even in the heat-treated towel at the time of wire bonding, the die-bonded film 3 is completely thermally cured, whereby the hardening shrinkage can be suppressed. 8 201118145 JOiOHpil The acid value of the die-bonding film 3 is preferably In the range of 4 to 1 〇 mgK 〇 H / g, more preferably in the range of 6 to 8 mg KOH / g. Acid (4) 4 mg KQH / g

St例如’通過12Q°C、1小時條件下的熱處理抑制被 黏物上產生赵曲的同時，可以提高剪切膠黏力。另一方面， ，值為H) mgK0H/g以下時，可以抑制常溫保存時的黏晶 薄膜3的黏度上升。 作為所述黏晶薄膜3的構成材料，優選由熱硬化性樹 月曰和熱塑性樹脂形&。另夕卜’所述熱塑性樹脂中，優選包 含酸值優選為10〜40 mgKOH/g、更優選2〇〜4〇 mgK〇H/g、 進一步優選25〜35 mgKOH/g的熱塑性樹脂。酸值低於1〇 mgKOH/g時’有時i2〇c、1小時的熱處理後的剪切膠黏 力不充分。另一方面，酸值超過4〇 mgK〇H/g時，有時保 存性變差。 作為所述熱塑性樹脂，可以列舉：天然橡膠、丁基橡 膠、異戊一稀橡膠、氯丁橡膠、乙烯-醋酸乙烯酯共聚物、 乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹 脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、尼龍6或尼龍 6,6等聚醯胺樹脂、苯氧基樹脂、丙烯酸類樹脂、pET或 PBT等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、或者含氟樹脂 等。這些熱塑性樹脂可以單獨使用或者兩種以上組合使 用。這些熱塑性樹脂中，特別優選離子性雜質少、.耐熱性 南、能夠確保半導體元件的可靠性的丙稀酸類樹脂。 作為所述丙烯酸類樹脂，沒有特別限制，可以列舉： 以一種或兩種以上具有碳原子數30以下、特別是碳原子數 201118145 j〇io*tpn 4〜18的直鏈或支鏈烷基的丙烯酸酯或曱基丙烯酸酯為成 分的聚合物等。作為所述烷基，可以列舉例如：曱基、乙 基、丙基、異丙基、正丁基、叔丁基、異丁基、戊基、異 戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、 壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三 烷基、十四烷基、硬脂基、十八烷基或者十二烷基等。 另外’作為形成所述聚合物的其他單體，沒有特別限 制，可以列舉例如：丙烯酸、曱基丙烯酸、丙烯酸竣乙醋、 丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸或巴豆酸等含緩 基單體；馬來酸酐或衣康酸酐等酸酐單體；（曱基)丙稀酸 -2-經基乙S旨、（曱基）丙烯酸-2-經基丙醋、（甲基)丙埽酸_4_ 經基丁酯、（曱基）丙稀酸-6-經基己酯、（曱基）丙烯酸>8-經 基辛酯、（曱基)丙烯酸-10-羥基癸酯、（曱基)丙烯酸_12_經 基月桂酯或丙烯酸(4-羥曱基環己基）曱酯等含羥基單體； 苯乙稀續酸、烯丙基續酸、2-(曱基）丙稀醯胺基_2_甲基丙 磺酸、（曱基)丙烯醯胺基丙磺酸、（曱基)丙烯酸磺丙酯或（甲 基）丙烯醯氧基萘磺酸等含磺酸基單體；或者丙烯醯磷酸 -2-羥基乙酯等含磷酸基單體。另外，（曱基)丙烯酸_2_羥基 乙酯是指丙烯酸-2-羥基乙酯和/或曱基丙烯酸_2_羥基乙 醋’本發明的（曱基)全部具有同樣的含義。 作為所述熱硬化性樹脂’可以列舉：酴搭樹脂、氨基 樹脂、不飽和聚酯樹脂、環氧樹脂、聚氨酯樹脂、聚矽氧 烷樹脂或熱硬化性聚醯亞胺樹脂等。這些樹脂可以單獨使 用或者兩種以上組合使用。特別優選使半導體元件腐蝕的St, for example, can suppress the occurrence of scratch on the adherend by heat treatment at 12Q ° C for 1 hour, and the shear adhesive strength can be improved. On the other hand, when the value is H) mgK0H/g or less, the increase in the viscosity of the die-bonding film 3 at the time of storage at normal temperature can be suppressed. As a constituent material of the die-bonding film 3, a thermosetting tree and a thermoplastic resin are preferably used. Further, the thermoplastic resin preferably contains a thermoplastic resin having an acid value of preferably 10 to 40 mgKOH/g, more preferably 2 to 4 mg, mg K 〇 H/g, still more preferably 25 to 35 mg KOH/g. When the acid value is less than 1 〇 mgKOH/g, the shear adhesive strength after heat treatment of i2〇c and 1 hour is insufficient. On the other hand, when the acid value exceeds 4 〇 mgK 〇 H / g, the storage property may be deteriorated. Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Alkene resin, polycarbonate resin, thermoplastic polyimide resin, nylon 6 or nylon 6,6, etc. polyamide resin, phenoxy resin, acrylic resin, saturated polyester resin such as pET or PBT, polyamidoxime Imine resin, or fluorine-containing resin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin having a small amount of ionic impurities, heat resistance, and reliability of a semiconductor element is particularly preferable. The acrylic resin is not particularly limited, and one or two or more kinds of linear or branched alkyl groups having a carbon number of 30 or less, particularly, a carbon number of 201118145 j〇io*tpn 4 to 18 may be mentioned. A polymer or the like having an acrylate or a mercapto acrylate. Examples of the alkyl group include a mercapto group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl or dodecyl and the like. Further, 'the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, mercaptoacrylic acid, ethyl acetonate, carboxy amyl acrylate, itaconic acid, maleic acid, fumaric acid or croton. An acid anhydride or the like containing a slow-acting monomer; an anhydride monomer such as maleic anhydride or itaconic anhydride; (mercapto)acrylic acid-2-alkyl group, (mercapto)acrylic acid-2-pyridyl vinegar, Methyl)propionic acid _4_ butyl butyl ketone, (mercapto) acrylic acid-6- hexyl hexyl acrylate, (mercapto) acrylic acid > 8- octyl octyl ester, (fluorenyl) acrylic acid -10- Hydroxy oxime ester, (mercapto)acrylic acid _12_ hydroxylauryl ester such as lauric acid ester or 4-hydroxyindole cyclohexyl acrylate; styrene benzoic acid, allyl carboxylic acid, 2-( Mercapto) acrylamide 2-methylpropanesulfonic acid, (mercapto) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate or (meth) propylene phthaloxy naphthalene sulfonic acid a sulfonic acid group-containing monomer; or a phosphoric acid group-containing monomer such as acryloylphosphonium-2-hydroxyethyl ester. Further, (mercapto)acrylic acid 2-hydroxyethyl ester means 2-hydroxyethyl acrylate and/or methacrylic acid _2 hydroxyacetate. The thiol groups of the present invention all have the same meanings. Examples of the thermosetting resin □ are a resin, an amino resin, an unsaturated polyester resin, an epoxy resin, a urethane resin, a polyoxymethylene resin, or a thermosetting polyimide resin. These resins may be used singly or in combination of two or more. Particularly preferred to corrode semiconductor components

201118145 JUIU*tpU 離子性雜質等的含量少的 的硬化劑，優選祕樹;;减翻旨。另外，作為環氧樹脂 产負;樹月日’只要是作為膠黏劑組合物通常使用的 二F ’可以使用例如：雙盼人型、雙 阶AT刑S ^ '填化雙盼Α型、氫化雙紛Α型、雙 紛AF型、聯笨型、鼓刑 紛祕清漆型、：經;ΐ甲3、苯酿清漆型、鄰甲 At ' —焱本基曱烷型、四苯酚基乙烷型等雙官 給^日或多& ^氧樹脂、或者乙内醯脲型、異氰脲 水料㈣缝水料胺㈣環氧娜。這些環氧 ί，曰^早獨使用或者兩種以上組合使用。這些環氧樹脂 —寸別優選祕清漆型環氧樹脂、聯苯型環氧樹脂、三 經苯基氧樹脂或四苯錄乙财環氧樹脂。這是 因為、.k麵、氧樹脂與作為硬化獅祕難的反應性 T ’並且耐熱性等優良。另外，環氧樹脂中腐钱半導體元 件的離子性雜質等的含量少。 另外’所述酚醛樹脂作為所述環氧樹脂的硬化劑起作 用’可以列举例如：苯_料漆樹脂、苯料燒基樹脂、 甲齡祕清漆翻旨、叔了基紐祕清漆概、壬基苯紛 酴搭清漆獅等祕清漆型轉脂，可溶魏樹脂(咖 ，紛樹脂^對縣苯乙烯等料基苯乙烯等。這些祕 樹脂可以單獨使用或者兩種以上組合使用。這些酚醛樹脂 中優選由下述化學式表示的聯苯型苯酚酚醛清漆樹脂、苯 =芳烷基樹脂。這是因為可以提高半導體裝置的連^可靠 11 201118145 j〇io*tpn201118145 JUIU*tpU A curing agent having a small content of ionic impurities or the like is preferably a secret tree; In addition, as an epoxy resin, the tree can be used as long as it is used as an adhesive composition. For example, it can be used, for example, a double-preferred human type, a double-order AT, a S ^ 'filled double-injection type, Hydrogenated double-difference type, double-distributed AF type, double-studded type, dying varnish type: warp; armor 3, benzene varnish type, ortho-At'-purine-based decane type, tetraphenol-based The alkane type or the like is given to the day or more & oxy resin, or the carbendazim type, the isocyanurate water material (4) the sulphide amine (4) epoxide. These epoxy 曰, 曰 ^ used alone or in combination of two or more. These epoxy resins are preferably selected from the group consisting of a secret varnish type epoxy resin, a biphenyl type epoxy resin, a triphenyl phenyl oxy resin or a tetraphenyl epoxide epoxy resin. This is because the .k surface, the oxygen resin and the reactive T ′ which is difficult to harden the lion are excellent in heat resistance and the like. Further, the content of ionic impurities or the like of the rotted semiconductor element in the epoxy resin is small. Further, 'the phenolic resin acts as a curing agent for the epoxy resin', for example, benzene-lacquer resin, benzene-based resin, enamel varnish, and uncle-based varnish, 壬The base benzene is mixed with varnish lion and other secret varnish-type trans fats, soluble Wei resin (coffee, varnish, styrene, etc.). These secret resins can be used alone or in combination of two or more. Among the resins, a biphenyl type phenol novolak resin represented by the following chemical formula, and a benzene = aralkyl resin are preferable. This is because the reliability of the semiconductor device can be improved. 11 201118145 j〇io*tpn

(所迷n為〇〜10的自然數）。 的自=^卜，所述n優選為0〜10的自然數，更優選為0〜5 的流Sit。通過在所述數值範圍内，可以確保黏晶薄膜3 環氡2述環氧樹脂與酚醛樹脂，以所述熱硬化性成分中的 耳數二的莫耳數相對於熱硬化性樹脂成分中的酚羥基的莫 … 比例為15〜6的範圍内的方式進行調配。另外， ^匕例優選為15〜4，更優選為2〜3。通過使所述比例為 .曰、上、可以減小熱硬化型黏晶薄膜自身的拉伸彈性才^ 、可以減少硬化收縮。另外，通過使所述比例為6以下: 可以防止環氧樹脂的熱硬化反應不充分。 、另外，本實施方式的黏晶薄膜3，如果由作為熱硬化 性成分的環氧樹脂及酚醛樹脂形成，則也可以含有其他熱 硬化性成分。作為這樣的其他熱硬化性成分，可以列舉例' 如.氨基樹脂、不飽和聚酯樹脂、聚氨酯樹脂、有機矽樹 脂或熱硬化性聚醯亞胺樹脂等。另外，脫溶劑化、片化、 B階化的熱硬化性樹脂是適合的。這些樹脂可以單獨使用 12 201118145 或者兩種以上組合使用。所述其他熱硬化性成分的調配比 例，相對於100重量份熱硬化性成分，優選為〇1〜1〇重量 份的範圍内’更優選為0.4〜5重量份的範圍内。 在此，使用丙稀酸類樹脂作為熱塑性樹脂時，與環氧 樹脂及紛酸樹脂的調配比例是：相對於100重量份丙稀酸 類樹脂，環氧樹脂及驗搭樹脂的混合量優選為川〜重 量份的範圍内，更優選為20〜600重量份的範圍内。另外， 環氧樹脂、酚醛樹脂及丙烯酸類樹脂由於離子性雜質少， 耐熱性高，因此可以確保半導體元件的可靠性。 所述熱硬化性樹脂成分中的環氧基的莫耳數相對於 熱硬化性樹脂成分中的酚羥基的莫耳數的比例為15〜6的 情況下，可以使用熱硬化催化劑作為黏晶薄膜3的構成材 料。作為其調配比例，相對於1〇()重量份有機成分，優選 在0.01〜3.5重量份的範圍内’更優選在MM重量份的範 圍内，特別優選在0.01〜0.5重量份的範圍内。通過使調配 比例為0.01重量份以上，黏晶時未反應的環氧基之間聚合 直至例如後硬化工序，可以減少或消除該未反應的環氧 基。結果，可以製造使半導體元件可靠地膠黏固定到被黏 • 物(詳細情況如後所述)上且無剝離的半導體裝置。另一方 面，通過將調配比例設定為3.5重量份以下，可以防止產 生硬化障礙。 作為所述熱硬化催化劑，沒有特別限制，可以列舉例 如：咪唑類化合物、三苯基膦類化合物、胺類化合物、三 苯基硼烷類化合物、三鹵代硼烷類化合物等。這些物質可 13 201118145 ^OlDHpil 以早獨使用或者兩種以上組合使用。 作為所述咪唑類化合物，可以列舉：2-曱基咪唑(商品 名：2MZ)、2-十一烷基咪唑(商品名：C11Z)、2-十七烧基 σ米唾(商品名·· C17Z)、1，2-二甲基味嗤(商品名：1 2DMZ)、 2_乙基-4-甲基17米σ坐(商品名：2Ε4ΜΖ)、2-苯基味σ坐(商品名： 2ΡΖ)、2-苯基-4-甲基咪唑(商品名：2Ρ4ΜΖ)、1-节基·2_甲 基咪°坐（商品名.1Β2ΜΖ)、1-苄基-2-苯基咪。坐（商品名： 1Β2ΡΖ)、1-氰基乙基-2-甲基咪唾（商品名：2MZ-CN)、1_ 氰基乙基-2-十一烷基咪唑(商品名：C11Z-CN)、1-氰基乙 基-2-笨基咪唑鑌偏苯三酸鹽（商品名：2pzcNS_pw>、 二氨基-6-[2’-甲基咪唑基（1，)]乙基-均三嗪（商品名’： 2MZ-A)、2,4-二氨基-6-P’·十一烷基咪唑基(Γ)]乙基均三 嗪(商品名：C11Z-A)、2,4-二氨基-6-[2，-乙基_4，_甲基咪唑 基(1，)]乙基-均三嗪(商品名：2Ε4ΜΖ-Α)、2 4_二氨基冬[2，_ 曱基咪唑基（1 )]乙基-均三嗪異氰脲酸加成物（商品名： 2ΜΑ-ΟΚ)、2·苯基·4,5_二羥基甲基咪唑（商品名： 2PHZ-PW)、2-苯基_4-曱基_5_羥曱基咪唑（商品名： 2Ρ4ΜΗΖ·ΡW)等(均為四國化成有限公司製）。 作為所述三苯基膦類化合物，沒有特別限制，可 tit膦三苯3、三丁基膦、三(對甲基苯基)膦、三(壬 5 = 苯基膦等三有機膦;四苯基漠化鱗(商 口口名.ΤΡΡ-ΡΒ)、甲基三苯基鱗(商品名· τρρ_Μ 商品名:TPP_MC)、甲氧基甲基三苯基鱗二 °口名P_M0C) 1基三苯基氣化鱗(商品名：TPP_ZC) 201118145 -»u t \j-rpii. 等(均為北興化學公司製）。另外，作為所述三笨基膦類化 合物，優選為對環氧樹脂實質上顯示非溶解性的化合物。 對環氧樹脂為非溶解性時，可以抑制熱硬化過度進行。作 • 為具有三苯基膦結構、並且對環氧樹脂實質上顯示非溶解 性的熱硬化催化劑，可以列舉例如：曱基三笨基鱗(商品 名：TPP-MB)等。另外，所述「非溶解性」，是指包含三 苯基膦類化合物的熱硬化催化劑在包含環氧樹脂的溶劑中 為不溶性，更具體而言，是指在溫度1〇〜4〇ΐ範圍内不溶 解10重量％以上。 作為所述二苯基硼烷類化合物，沒有特別限制，可以 列舉例如三(對甲基苯基)膦等。另外，作為三苯基硼烷類 化δ物還包3具有二笨基膦結構的化合物。作為該具有 二苯基膦結構及三苯基硼烷結構的化合物，沒有特別限 制’可以列舉例如：四苯基鱗四苯基硼酸鹽（商品名： 四苯基鱗四對三硼酸鹽(商品名：τρρ_Μκ)、苄基 二苯基鱗四苯基硼酸鹽（商品名：τρρ_ζκ)、三苯基膦三笨 基硼烷(商品名：Tpp-s)等(均為北興化學公司製）。— 作為所述胺類化合物，没有特别限制，可以列举例 = 乙醇胺二氟删酸鹽(Steiia chemifa有限公司製}、雙 - 氰胺(Nacalai Tesque有限公司製）等。 作為所述三鹵代硼烷類化合物，沒有特別限制，可以 列舉例如三氯硼烷等。 一在使本發㈣膜3預先進行某種程度的交聯的 月况下’在製作時可以添加與聚合物的分子鏈末端的官能 15 201118145 joionpn 團等反應的多官能化合物作為交聯劑。由此，可以提高高 溫下的膠黏特性，改善耐熱性。 作為所述交聯劑，可以使用現有公知的交聯劑。特別 是更優選為甲苯二異氰酸酯、二苯基曱烧二異氰酸酯、對 笨二異氰酸醋、1，5-秦二異氰酸S旨、多元醇與二異氰酸醋 的加成物等多異氰酸酯化合物。作為交聯劑的添加量，相 對於所述聚合物100重量份通常優選設定為〇〇5〜7重量 份。交聯劑的量超過7重量份時，膠黏力下降，因此不優 選。另一方面，低於0.05重量份時，凝聚力不足，因此不 優選。另外，根據需要’可以與這樣的多異氰酸醋化合物 一同含有環氧樹脂等其他多官能化合物。 土首古^夕!/黏晶薄膜3中’根據其用途可以適當調配無相 接古道;機。#機填充劑的調配可以賦予導電性忌 鋇、氧化紹、氧化鈹、礙二、黏/、石**、碳酸詞、_ 銀、金、錦、絡，、^切、氮化石夕等陶究類；銘、銅' 金類；以及碳等私種焊錫等金屬、或私 或者兩種以上組合使…機叔末。這些填料可以單獨使用 優選使用炫融二^ °其中’優選使用二氧化發，特別 選在0.1〜80帅的範另外’無機填充劑的平均粒徑優 對於有機樹脂成分i 所述無機填充劑的調配量，相 特別優選為〇〜7〇重量佟里份優選設定為0〜80重量份。(The n is the natural number of 〇~10). From n = ^, the n is preferably a natural number of 0 to 10, more preferably a stream Sit of 0 to 5. By being within the above numerical range, it is possible to ensure that the epoxy resin and the phenol resin are in the ring-shaped film 3, and the number of moles of the number of ears in the thermosetting component is relative to that in the thermosetting resin component. The phenolic hydroxyl group is blended in such a manner that the ratio is in the range of 15 to 6. Further, the example is preferably 15 to 4, and more preferably 2 to 3. By making the ratio 曰, upper, the tensile elasticity of the thermosetting type die-bonding film itself can be reduced, and the hardening shrinkage can be reduced. Further, by setting the ratio to 6 or less, it is possible to prevent the thermosetting reaction of the epoxy resin from being insufficient. Further, the die-bonded film 3 of the present embodiment may contain another thermosetting component if it is formed of an epoxy resin or a phenol resin as a thermosetting component. Examples of such other thermosetting component include an amino resin, an unsaturated polyester resin, a polyurethane resin, an organic eucalyptus resin, or a thermosetting polyimide resin. Further, a thermosetting resin which is desolvated, tableted, or B-staged is suitable. These resins can be used alone 12 201118145 or a combination of two or more. The blending ratio of the other thermosetting component is preferably in the range of 〇1 to 1 〇 by weight, more preferably 0.4 to 5 parts by weight, per 100 parts by weight of the thermosetting component. Here, when an acrylic resin is used as the thermoplastic resin, the blending ratio with the epoxy resin and the sulphuric acid resin is preferably such that the blending amount of the epoxy resin and the test resin is 100 parts by weight of the acrylic resin. In the range of parts by weight, it is more preferably in the range of 20 to 600 parts by weight. Further, since the epoxy resin, the phenol resin, and the acrylic resin have few ionic impurities and high heat resistance, the reliability of the semiconductor element can be ensured. When the ratio of the number of moles of the epoxy group in the thermosetting resin component to the number of moles of the phenolic hydroxyl group in the thermosetting resin component is 15 to 6, a thermosetting catalyst can be used as the die-bonding film. 3 constituent materials. The blending ratio is preferably in the range of 0.01 to 3.5 parts by weight, more preferably in the range of MM by weight, and particularly preferably in the range of 0.01 to 0.5 part by weight, based on 1 part by weight of the organic component. By setting the compounding ratio to 0.01 part by weight or more, the unreacted epoxy group can be reduced or eliminated by polymerization between unreacted epoxy groups at the time of die bonding until, for example, a post-hardening step. As a result, it is possible to manufacture a semiconductor device in which the semiconductor element is reliably adhered to the adherend (details will be described later) without peeling off. On the other hand, by setting the blending ratio to 3.5 parts by weight or less, it is possible to prevent the occurrence of sclerosis. The thermosetting catalyst is not particularly limited, and examples thereof include an imidazole compound, a triphenylphosphine compound, an amine compound, a triphenylborane compound, and a trihaloborane compound. These substances can be used as early or in combination of two or more in combination with 201118145 ^OlDHpil. Examples of the imidazole compound include 2-mercaptoimidazole (trade name: 2MZ), 2-undecylimidazole (trade name: C11Z), and 2-pyranyl sigma-salt (trade name·· C17Z), 1,2-dimethyl miso (trade name: 1 2DMZ), 2_ethyl-4-methyl 17 m σ sitting (trade name: 2Ε4ΜΖ), 2-phenyl taste σ sitting (trade name) : 2ΡΖ), 2-phenyl-4-methylimidazole (trade name: 2Ρ4ΜΖ), 1-pyramid·2_methylimine sitting (trade name: 1Β2ΜΖ), 1-benzyl-2-phenylimene . Sitting (trade name: 1Β2ΡΖ), 1-cyanoethyl-2-methylmeridene (trade name: 2MZ-CN), 1_cyanoethyl-2-undecylimidazole (trade name: C11Z-CN , 1-cyanoethyl-2-phenylimidazolium trimellitate (trade name: 2pzcNS_pw>, diamino-6-[2'-methylimidazolyl(1,)]ethyl-all three Azine (trade name ': 2MZ-A), 2,4-diamino-6-P'·undecylimidazolyl (oxime)]ethyl s-triazine (trade name: C11Z-A), 2, 4 -Diamino-6-[2,-ethyl_4,-methylimidazolyl (1,)]ethyl-s-triazine (trade name: 2Ε4ΜΖ-Α), 2 4_diamino winter [2,_ Mercaptomidazolyl (1 )] ethyl-s-triazine isocyanuric acid adduct (trade name: 2ΜΑ-ΟΚ), 2·phenyl·4,5-dihydroxymethylimidazole (trade name: 2PHZ- PW), 2-phenyl-4-indoleyl-5-hydroxyindoleimidazole (trade name: 2Ρ4ΜΗΖ·ΡW), etc. (all manufactured by Shikoku Chemicals Co., Ltd.). As the triphenylphosphine compound, there is no Particularly limited, tit phosphine triphenyl 3, tributylphosphine, tris(p-methylphenyl) phosphine, tris(壬5 = phenylphosphine and other triorganophosphine; tetraphenyl desertification scale (Shangkoukou name. ΤΡΡ-ΡΒ), methyl three Phenyl scale (trade name · τρρ_Μ trade name: TPP_MC), methoxymethyl triphenyl scale two ° mouth name P_M0C) 1 base triphenyl gasification scale (trade name: TPP_ZC) 201118145 -»ut \j- Rpii. etc. (both manufactured by Kitachem Chemical Co., Ltd.). Further, as the tris-phosphoryl compound, a compound which exhibits substantially no solubility to an epoxy resin is preferable. Inhibition of thermal hardening is carried out. For the thermosetting catalyst having a triphenylphosphine structure and exhibiting substantially insolubility to the epoxy resin, for example, a mercapto-based tribasic scale (trade name: TPP-MB) can be cited. In addition, the term "insoluble" means that the thermosetting catalyst containing a triphenylphosphine compound is insoluble in a solvent containing an epoxy resin, and more specifically, at a temperature of 1 〇 to 4 Torr. The diphenylborane compound is not particularly limited, and examples thereof include tris(p-methylphenyl)phosphine and the like, and triphenylborane-based δ. The compound also has a compound having a di-phenylphosphine structure. The compound having a structure of a diphenylphosphine structure and a triphenylborane structure is not particularly limited, and examples thereof include tetraphenylphosphinium tetraphenylborate (trade name: tetraphenylsulfonate tetra-triborate). Name: τρρ_Μκ), benzyl diphenyl quaternary tetraphenyl borate (trade name: τρρ_ζκ), triphenylphosphine triphenyl borane (trade name: Tpp-s), etc. (all manufactured by Beixing Chemical Co., Ltd.). The amine compound is not particularly limited, and examples thereof include ethanolamine difluoro-decarboxylate (manufactured by Steiia Chemifa Co., Ltd.), bis-cyanamide (manufactured by Nacalai Tesque Co., Ltd.), and the like. The trihalogenated borane compound is not particularly limited, and examples thereof include trichloroborane. In the case where the film (3) of the present invention (4) is subjected to a certain degree of crosslinking in advance, a polyfunctional compound which reacts with a functional group at the end of the molecular chain of the polymer, such as a functional group, may be added as a crosslinking agent. Thereby, the adhesive property at a high temperature can be improved and the heat resistance can be improved. As the crosslinking agent, a conventionally known crosslinking agent can be used. In particular, it is more preferably toluene diisocyanate, diphenyl sulfonium diisocyanate, p-diisopropyl isocyanate, 1,5-methyl diisocyanate, an adduct of a polyhydric alcohol and a diisocyanate, and the like. Polyisocyanate compound. The amount of the crosslinking agent to be added is usually preferably 〇〇5 to 7 parts by weight based on 100 parts by weight of the polymer. When the amount of the crosslinking agent exceeds 7 parts by weight, the adhesive strength is lowered, so that it is not preferable. On the other hand, when the amount is less than 0.05 part by weight, the cohesive strength is insufficient, which is not preferable. Further, other polyfunctional compounds such as an epoxy resin may be contained together with such a polyisocyanate compound as needed. Tushou Gu ^ Xi! / Muscle film 3 in the 'depending on its use can be properly equipped with no connection ancient road; machine. #机充剂配配配 can give conductivity avoidance, oxidation, bismuth oxide, hinder two, sticky /, stone **, carbonated words, _ silver, gold, Jin, Luo, ^ cut, nitrite and other pottery Research; Ming, copper 'gold'; and carbon and other private solders and other metals, or private or a combination of two or more to make the machine uncle. These fillers can be used alone, preferably in the form of a smelting solution, wherein 'preferably using a hair oxidizing agent, particularly in the range of 0.1 to 80 Å, and the 'average particle diameter of the inorganic filler is superior to the inorganic filler of the organic resin component i. The blending amount is particularly preferably 〇~7〇, and the aliquot is preferably set to 0 to 80 parts by weight.

另外，黏晶薄膜3由 A 、，除了所述無機填充劑以外，根 201118145 VTu.. 據需要可以適當調配其他添加劑。作 述阻燃劑，可以列舉例如:三氧化録、作為所 氧樹脂等。這些阻燃劑可以單獨使用或者兩種^上環 為所述石规偶聯劑，可以列舉例如：Ν34_^ί 己基)乙基二甲氧齡烧、γ_環氧丙氧二衣 烧观丙氧基丙基甲基二乙氧基魏等 3以早獨使用或者兩觀上組合使用。 :如:水滑石類、氣氧化降這些= 獲背i可以單獨使用或者兩種以上組合使用。 所述切割/黏晶薄膜10、u的黏晶薄膜3，優選由隔 片（separator)保護(未圖示）。隔片具有在供實際使用之前作 為保護黏晶薄膜3的保護材料的功能。另外，隔片還可以 作為將黏晶薄膜3轉印到黏合劑層2上時的支撐基材使 用。卩w片在向切割/黏晶薄膜的黏晶薄膜3上黏貼工件時剝 離。作為隔片，可以使用聚對苯二甲酸乙二醇酯(pET)、聚 乙烯、聚丙烯或者利用含氟剝離劑、長鏈烷基丙烯酸酯類 剝離劑等剝離劑進行表面塗布後的塑膠薄膜或紙等。 另外’所述黏晶薄膜3的熱硬化前的not：下的熔融 黏度優選為50〜1000 pa.s，更優選為i〇〇〜8〇〇 Pa.s，特別優 選為200〜600Pa_s。通過將所述熔融黏度設定為50Pa.s以 上’可以使對基板等被黏物的密合性變良好。結果，在與 被黏物的膠黏面上’可以減少空隙的產生。另一方面，通 過將所述熔融黏度設定為1000 Pa.s以下，可以抑制膠黏劑 17 201118145 成分等從熱硬化型黏晶薄膜中滲出。結果，可以防止被黏 物或者膠黏固定在被黏物上的半導體元件的污染。另外， 所述熔融黏度通過以下測定方法測定並計算。即，可以使 用流變儀(HAAKE公司製，商品名：RS-1)，通過平行板法 測定。即’在加熱到l〇(TC的板上，放置取自黏晶薄膜3 的〇· 1 g試樣，並開始測定。將測定開始12〇秒後的熔融 黏度的平均值作為熔融黏度。另外，板間的間隙為〇1 mm。 所述黏晶薄膜3的熱硬化後260°C下的儲能彈性模量 優選為1 MPa以上，更優選為5〜100 MPa，特別優選為 10〜100 MPa。由此，例如，在密封工序中可以防止半導體 元件傾斜，另外，在回鱗接玉料，可以社黏晶薄膜 與被黏物之間產生剝離。另外，在此所說的黏晶薄膜3的 …、更化，疋私在140C進行2小時熱處理後，再在175。〇下 進行1小時誠理時的狀態。另外，儲能彈性模量的測定 例如可以使用固體黏彈性測定裝置(Rheometric Scientific 么司製’型號：RSA-m)。即，將試樣尺寸設定為長·mm X寬lOmmx厚2〇0μιη’將測定試樣安裝在薄膜拉伸測定用 -50:3二，产V圍溫速度咖分鐘的條件下測定 旦、、:又乾，下的抵伸儲能彈性模量及損耗彈性模 里’通過讀取26(TC下⑽能彈性模量(E，)而得到。、 黏晶薄膜3的厚度(層疊體情 別限制，例如為約5卿〜吻_ 1U度卜又有特 約100Km’優選為約5μπι〜約50 另外，黏晶薄膜3例如可以僅由 膠黏劑層單層構成 〇 201118145 另外，通過將_轉移溫度不同的熱塑性継、熱硬化溫 度不同的熱硬化㈣鴻適當組合，可⑽成兩層以上的多 層結構。半導體晶_蝴工序巾使用侧水，因此，有 ，黏晶薄膜3吸濕’含水率達到常態以上。如果在這樣的 同3水率的狀恶下膠黏在基板等上，則在後硬化階段膠黏 介面處滯留錢汽’有時產生翹起。因此，作為黏晶薄膜 3’通過形成由膠_層夾住高透濕性芯材的結構，在後硬 化階段水蒸汽透過薄膜而擴散，從而可以避免所述問題。 從該觀點考慮’黏晶_3可轉时芯材的單面或雙面 上形成有膠黏劑層的多層結構。 為所述芯材’可以列舉：薄膜(例如聚醯亞胺薄膜、 西:二膜、苯二甲酸乙二醇酯薄膜、聚萘二甲酸乙二 維Ξ 樹旨薄膜等)、用玻璃纖維或塑膠製不織纖 曰里认a土板、鏡面矽晶圓、矽基板或玻璃基板等。 且古ϋ黏晶薄膜3，優選由隔片（未圖示)保護。隔片 二有t實際使用之前作為保護黏晶薄膜的保護 :時轉印到切割薄模 類剝離劑等Ζί者利用含氟剝離劑、長鏈烷基丙烯酸酯 進行表面塗布後的轉薄膜或紙等。 1乍為所述切割薄膜 有黏合劑層2的切 二舉在基板1上層叠 上。另外，如圖3層疊在黏合劑層2 圖2所不’可以是僅在半導體晶圓黏貼部分 201118145 形成黏晶薄膜3,的結構。 、所述基材1作為切割/黏晶薄膜10、11的強度母體。 可以，舉例如：低密度聚乙烯、線性聚乙烯、中密度聚乙 =高密度聚乙稀、超低密度聚乙烯、無規共聚聚丙稀、 ，段共聚聚丙烯、均聚丙烯、聚丁烯、聚曱基戊烯等聚烯 =、乙烯-乙酸乙烯醋共聚物、離子聚合物樹脂、乙稀 土）丙烯共聚物、乙烯_(甲基)丙稀酸g旨(無規、交替）丑聚 物y乙彿-丁稀共聚物、乙晞_己稀共聚物、聚氨醋/聚對 t-曱酸乙二_旨、聚萘二曱酸乙二醇料㈣旨、聚碳酸 ^聚，亞胺、聚縫咖同、聚醯亞胺、聚鱗酿亞胺、聚酿 胺、全芳族聚醯胺、聚苯硫輕、芳族聚醯胺(紙）、玻璃、 3布、含氟樹脂、聚氯乙烯、聚偏二氣乙烯、纖維素類 树月曰I矽氧烷樹脂、金屬（落）、紙等 外線硬切時，優縣材丨對料線具有透雜θ。為紫 另外，作為基材1的材料，可以列舉上述樹脂的交聯 體等聚合物。所述歸薄膜可以不拉伸而使用，也可以根 據，要進行單軸或雙脉伸處理後錢。觀通過拉伸處 理等而賦竹熱收縮性的樹脂#，在切割後通過使該基材 ^熱收縮，可以減小黏合劑層2與黏晶薄膜3的膠黏面積， 從而可以容易地回收半導體晶片。 為^提高與鄰接層的密合性、保持性等，基材i的表 面了以貝知丨貝用的表面處理，例如鉻酸處理、臭氧暴露、 火焰暴露、③壓電擊暴露、游離輻射處理等化學或物理處 理、利用底塗劑(例如後述的黏合物質）的塗布處理。 20 201118145 所述基材1可以適當地選擇使用同種或不同種類的材 料’根據$要也可以使用將多種材料共混後的材料4外， 為了賦予基材〗防靜電性能，可以在所述基材丨上設置包 3金屬σ金、匕們的氧化物等的厚度為約a〜約遍入 2電物質的絲層。基材丨可以是單層或者兩種以上的 多層。 基材1的厚度沒有特別限制，可以適當確定，一般為 約 5 μιη〜約 200 μπι。 另外，在不知害本發明的效果等的範圍内，基材^中 添加劑(例如，著色劑、填充劑、增塑劑、抗 老化劑、抗氧化劑、界面活性劑、阻燃劑等）。 在黏合劑層2的形成中使用的黏合劑，只要能夠可 製黏晶薄膜3則沒有特別限制。例如，可以使用丙 版類黏合劑、橡膠_合_ —般的壓敏雜劑。作為 所述壓__，從半導虹圓或子 Γ牛::超純水ί醇等有機溶劑的清心 ^。類聚合物為基礎聚合物的丙烯酸類黏合 酸歸合物，可關舉❹_酸醋為 蚀：聚合物。作為所述丙烯酸醋，可以列舉例如: ，用（甲基)丙烯舰基6旨(例如 r=、異丁si、仲丁略、叔獨、戊醋、異搞、、己 :::，、辛η乙基己醋、異辛醋、壬醋、癸醋、異 a m十二喊、十三舰、十四如旨、十六 21 201118145 JW 1 烧酉旨、十八烷酯、二十烷酯等烷基的碳原子數1〜30、特別 是碳原子數4〜18的直鏈或支鏈烷基酯等）以及（曱基)丙稀 酸環烷酯（例如，環戊酯、環己酯等）的一種或兩種以上作 為單體成分的丙烯酸類聚合物等。另外，（甲基)丙烯酸酯 表示丙烯酸酯和/或曱基丙烯酸酯，本發明的（曱基)全部表 示相同的含義。 所述丙烯酸類聚合物，為了改善凝聚力'耐熱性等 根據需要可以含有與能夠與所述（曱基)丙烯酸烷基酯或老 烷酯共聚的其他單體成分對應的單元。作為這樣的單體^ 分，可以列舉例如：丙烯酸、甲基丙烯酸、（甲基）丙烯酉 羧乙酯、（曱基)丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸 巴豆目文寻含緩基單體，馬來酸酐、衣康酸酐等酸軒單 基)丙烯酸-2-羥基乙酯、（甲基)丙烯酸_2_羥基丙酯、（甲基 =烯酸-4-Μ基丁g旨、（曱基)㈣酸_6_經基己_、（甲基^ 烯酸各經基辛醋、（甲基)丙烯酸*經基癸酉旨、（甲基^ 酸-I2-經基月桂g旨、（甲基)丙婦酸(4_經甲基環己基 =基單體；苯乙闕酸、稀丙俩，甲基)丙_胺曰^ :基丙續酸、（甲基)丙烯醯胺丙侦、（甲基)丙稀酸⑤ :、（甲基)丙烯醯氧基萘雜等含魏基單體；丙婦 經基乙S旨等含磷酸基單體；丙制胺、丙烯猜等。 =共聚單體成分可以使用—種或兩$ 早體的使用量優選為全部單體成分的4〇重量％以;^、5 可二;======= 22 201118145 i υτρίΑ 多官能單體，可以列舉例如：己二醇二（甲基)丙稀酸酿、⑻ 乙二醇曱基)丙稀酸醋、（聚)丙二醇二（甲基)丙稀酸醋、 新戊二醇二（甲基)丙烯酸酯、季戊四醇二（曱基）丙烯酸酯、 二羥曱基丙烷三（曱基)丙烯酸酯、季戊四醇三（曱基)丙烯酸 醋、二季戊四醇六（甲基)丙烯酸醋、環氧（曱基)丙稀酸醋、 聚酯（曱基）丙烯酸酯、氨基曱酸酯（甲基)丙烯醆酯等。這些 多g旎單體可以使用一種或兩種以上。多官能單體的使用 畺，k黏合特性等觀點考慮，優選為全部單體成分的川 重量％以下。 时所述丙烯酸類聚合物可以通過將單一單體或兩種以 上單體混合物聚合來得到。聚合可以通過溶液聚合、乳液 I口本體聚合、懸浮聚合等任意方式進行。從防止對潔 淨的被黏物的污染等觀點考慮，優選低分子量物質的含量 少。從該觀點考慮，丙烯酸類聚合物的數均分子量優選為 約30萬以上’更優選為約40萬〜約300萬。 另外，為了提南作為基礎聚合物的丙稀酸類聚合物等 的數均分子量，所述黏合劑中也可以適當採用外部交聯 劑。作為外部交聯方法的具體方法，可以列舉··添加多異 氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺類 交聯劑等所謂的交聯劑並使其反應的方法。使用外部交聯 劑時，其使用量通過與欲交聯的基礎聚合物的平衡並且根 據作為黏合劑的使用用途來適當確定。一般而言，相對於 所述基礎聚合物100重量份’優選為5重量份以下，更優 選為調配0.1〜5重量份。另外，根據需要，在黏合劑中除 23 201118145 外也可以使用以往公知的各種增黏劑、抗老化 層2可以由輕射線硬化型黏合劑形成。輻射線 f化型黏合劑通過紫外線等輻射線的照射，使交聯产辦 以容易地降低其黏合力。例如，通過僅對圖曰2 部分2a照射输線，可以設置與部分 2b之間的黏合力差。 、1刀 劑声通過與Ϊ晶薄膜Γ相符地使輻射線硬化型黏合 由^鮮’可以谷易地形成黏合力顯著下降的部分2a。 硬化且黏合力下降的部分2a上黏貼黏晶薄膜3,， :Γ:另2=晶1膜3,的介面具有在拾取時容易剝離 力，Lt二未照獅她 如前所述，® 1所示的切割/黏晶薄膜1〇的黏合劑層 中，由未硬化的輻射線硬化型黏合劑形成的所述部分& 二黏晶薄膜3黏合’可以確保切割時的保持力。這樣，幸5 射線硬化型黏合劑能夠以良好的膠黏剝 ^ ，他片(半導體晶片等)固著到基板等被:物二 阳薄膜3。圖2所示的切割/黏晶薄膜u的黏合劑層2中， 所述部分2b可以固定晶圓環(wafer ring)。 山輻射線硬化型黏合劑可以沒有特別限制地使用具有 碳-碳雙鍵等輻射線硬化性官能團、並且顯示黏合性的輻射 線硬化型黏合劑。作為輻射線硬化型黏合劑 ，可以例示例 如·在所述丙烯酸類黏合劑、橡膠類黏合劑等一般的壓敏 24 201118145 黏合劑中調配有輕射線硬化性的單體成分或低聚物成分的 添加型輕射線硬化型黏合劑。 作為調配的所述輻射線硬化性單體成分，可以列舉例 如：氨基甲酸自旨低聚物、氨基甲_旨（甲基）两烯酸醋、多 經甲基丙炫二（甲基）丙稀酸酯、四羥甲基甲燒四（甲基）丙姊 酸酯、季戊四醇三（甲基)丙烯酸酯、季戊四醇四（曱基）丙烯 酸酯、二季戊四醇單羥基五（甲基）丙烯酸酯、二季戊四酵 八（甲基)丙烯酸S曰、1，4-丁二醇二（曱基）丙稀酸酯等。另外， 輕射線硬化性低聚物成分’可以列舉：氨基甲酸酯類、聚 醚類、聚酯類、聚碳酸酯類、聚丁二烯類等各種低聚物， 其重均分子量在約100〜約30000的範圍内是適當的。輻射 線硬化性單體成分或低聚物成分的調配量，可以根據所述 黏合劑層的種類適當地確定能夠降低黏合劑層的黏合力的 里。一般而言，相對於構成黏合劑的丙稀酸類聚合物等基 礎聚合物100重量份，例如為約5重量份〜約5〇〇重量份， 優選為約40重量份〜約150重量份。 另外’作為輻射線硬化型黏合劑’除了前面說明的添 加型的輻射線硬化型黏合劑以外，還可以列舉使用在聚合 物側鏈或主鏈中或者主鏈末端具有碳-碳雙鍵的聚合物作 為基礎聚合物的内在型的輻射線硬化型黏合劑。内在型的 輻射線硬化型黏合劑無需含有或者不大量含有作為低分子 量成分的低聚物成分等，因此低聚物成分等不會隨時間推 移在黏合劑中移動，可以形成穩定的層結構的黏合劑層， 因此優選。 25 201118145 所述具有碳-碳雙鍵的基礎聚合物’可以沒有特別限制 地使用具有碳-碳雙鍵並且具有黏合性的聚合物。作為這樣 的基礎聚合物，優選以丙烯酸類聚合物作為基本骨架的聚 合物。作為丙烯酸類聚合物的基本骨架，可以列舉前面例 示過的丙烯酸類聚合物。 所述丙烯酸類聚合物中碳_碳雙鍵的導入方法沒有特 別限制，可以採用各種方法，而將碳-碳雙鍵導入聚合物側 鏈在分子設計上比較容易。可以列舉例如如下方法：預先 將在丙烯酸類聚合物中具有官能團的單體共聚後，使具有 能夠與該官能團反應的官能團和碳_碳雙鍵的化合物在保 持碳-碳雙鍵的輻射線硬化性的狀態下進行縮合或加成反 應。 作為這些官能團的組合例，可以列舉··叛基與環氧 基、羧基與氮丙啶基、羥基與異氰酸酯基等。這些官能團 的組合中，考慮到反應追蹤的容易性，優選為羥基與異氰 酸酯基的組合。另外，如果是通過這些官能團的組合而生 成所述具有碳-碳雙鍵的丙烯酸類聚合物的組合，則官能團 可以在丙烯酸類聚合物和所述化合物的任意一側，在所述 的優選組合中’優選丙烯酸類聚合物具有羥基、所述化合 物具有異氰酸酯基的情況。此時，作為具有碳_碳雙鍵的異 氰酸醋化合物’可以列舉例如：曱基丙烯醯異氰酸酯、2_ 曱基丙烯醯氧乙基異氰酸酯 '間異丙烯基_α，α_二甲基聯笨 醯異氰酸酯等。另外，作為丙烯酸類聚合物，可以使用將 前面例示的含羥基單體或2-羥基乙基乙烯基醚、4_羥基丁 26 201118145 V & V/ > ^*·*· 基乙婦基醚、二乙二醇單乙烯基醚_類化合物等共聚而 得到的聚合物。 所述内在型的輻射線硬化型黏合劑可以單獨使用 述具有碳-碳雙鍵的基礎聚合物（特別是丙炼酸類聚合 • 2)，也可以在不够特性的範H㈣輯賴射線硬化性 單體成分或低聚物成分。輕射線硬化性低聚物成分等，相 對於基礎聚合物100重量份通常在％重量份的範圍内，優 選在0〜10重量份的範圍。 所述1¾射線硬化魏合劑在通過紫外線等硬化時優 選含有光聚合引㈣。作為光聚合引發劑，可以列舉例如： 4-(2-祕乙氧基)笨基(2_經基_2_丙基)嗣、α_經基二 :基笨副、2·甲基_2_減苯_、⑽基環己基苯基酮 ^酮醇類化合物；曱氧基苯乙酮、2,2·二曱氧基-2-苯基 =乙鋼、2,2-二乙氧基苯乙_、2_f基邻_(甲硫基)-苯 f]-2-嗎琳基丙院」，等苯乙酮類化合物；苯偶姻⑽、 求偶姻異丙醚、.菌香偶姻曱基峻等苯偶姻_化合物；笨 偶酿二甲基縮酮等縮酮類化合物；2_蔡顧氯等芳香族石黃 酿氯類化合物；1-苯基_U_丙二_·2_(〇_乙氧基魏基)將等光 活性賴化合物；二苯曱酮、苯甲酿基笨甲酸、^，-二甲 土 4曱氧基一笨曱@同等二笨曱酮類化合物；〇塞〇頓酮、2'氯 塞頓酮:2-曱基嘆嘲_、2,4-二甲基β塞嘴酮、異丙基嘆嘲酮、 =，4_—氯噻噸酮、2,4-二乙基噻噸酮、2,4_二異丙基噻噸酮 等塞镇酮類化合物；樟腦酉昆；齒代酮；醢基鱗氧化物；醯 基膦酸醋等。光聚合引發劑的調配量，相對於構成黏合劑 27 201118145 類聚合物等基礎聚合物刚重量份，例如為約 0.05重置份〜約20重量份。 ㈣射線硬化型黏合劑形成黏合劑2的情況下，優 劑層2的—部分進行魏線照射使得部分2a的黏 二分2b的黏合力。圖2的切割/黏晶薄膜中，例如’ 9 物的SUS304板(#2000抛光)的關係，為部分 2a的黏合力 < 部分沘的黏合力。 可以合劑層2中形成所述部分仏的方法， 所、十、部1在基材1上形成輻射線硬化型黏合劑層2後對 =:2概照射輻射線使其硬化的方法。局部的輻 ==二隔著形成有與轉體晶圓黏貼部…外 ^圖案的光罩來進行。另外，可以列舉點 2 、進仃硬化的方法等。輻·魏型黏合劑層 成可以通過將設置在隔片上的歸線硬化i黏= ‘在進行。局部的輻射線硬化也可以對設 置在隔片上的輻射線硬化型黏合劑層2進行。 另卜通過#射線硬化型點合劑形 整體或局部進行遮光 輪射線照射，使與半導體晶_ =進订 化，從而形成黏合力下降的所立;=應的部分硬 在支#賴上印刷或蒸鍍等能夠成為 來1作。通過所職造方法，可叫效轉造本發明的t 28 201118145 割/黏晶薄膜10。 優選::任線照射時因氧而產生硬化障礙的情況下， 雜射線硬化型黏合劑層2的表面阻斷 矣面的t、、i_可以列舉例如.用隔片包覆所述黏合劑層2的 射的方法等。、4者錢氣氛圍中進行紫外線_射線的照 ，。韻2的厚度沒有特別限制，從同 為5叫〜25^進一步優選為2哗〜30_、更優選 填充劑、^. 者色劑、增稠劑、增量劑、 本實施方式的切割/黏晶薄膜，可以 以切割/黏晶薄膜10為例進行說明。首先，其7/ 過現有公知的製膜方法來製膜：2基材1可以通 示例如:壓延製膜法、有機二m，可以例 的吹塑擠出法、τ形模頭擠：中法、密閉體系中 等。 去、共擠出法、乾式層壓法 接著，在基材1上塗耗合劑組合物並 加熱交聯）而形成黏合劑層2。作. (根據而要 轉塗、絲網塗布、凹版塗布等。乍2布：式，可以列舉： 材1上進行，也可以塗布到表^卜’塗布可以直接在基 到表面進行了_處理的剝離紙 29 201118145 等上’然後轉印到基材1上。 紙上Ϊ布:二::於形成黏晶薄膜3的形成材料在剝離 居。通再在預定條件下進行乾燥而形成塗 ❹另外述黏合劑層2上，形成黏晶薄 Ϊ 下進行ί燥’由此也可以形成黏晶薄膜3。通 ,.'可以侍到本發明的切割/黏晶薄膜10。 (半導體裝置的製造方法） 的方用本實施方式的黏晶薄膜製造半導體裝置 件的鮮^ 圖3是表科難㈣駭裝半導體元 仵的例子的示意剖面圖。 晶薄式的半導體裝置的製造方法，具有：通過黏 體曰片η道:圓黏貼部分3a(以下稱為黏晶薄膜3a)將半導 行件)5固著到被黏物6上的固著工序;和進 曰曰片、s 焊工序。另外’具有：用密封樹脂8將半導體 ^化工脂密封卫序和賴密封概8後硬化的後 作為所述被黏物6，可以列舉引線框、TAB薄膜、基 =另外製作的半導體晶片等。被黏物6例如可以是容易 卵彳錄物’也可以是難以變形的錢形型被黏 導體㈣等）。作為所述基板，可贼μ往公知的 人=另外，作為所述引線框，可以使用&引線框、Μ 亞吐弓!_線框等金屬引線框或者由玻璃環氧、bt(雙馬來醯 •二唤）、聚酿亞胺等製成的有機基板。但是，本發明 30 201118145 -/V * 不限於這些’也包括在安裝半導體元件、與半導體元件電 連接後可以使用的電路基板。 所述固著工序，如圖1所示，是通過黏晶薄膜3a將 半導體晶片5黏晶到被黏物6上的工序。該工序通過在預 定條件下進行熱處理使黏晶薄膜3 a熱硬化，而將半導體晶 片5完全膠黏到被黏物6上。進行熱處理時的溫度，優選 為100〜200°C，更優選在120〜180°C的範圍内。另外，熱 處理時間優選為0.25小時〜10小時，更優選為0.5小時〜8 小時。作為將半導體晶片5固著到被黏物6上的方法，可 以列舉例如：將黏晶薄膜3a層疊到被黏物6上後、將半導 體晶片5以絲焊面為上側依次層疊在黏晶薄膜3&上而進行 固著的方法。另外，也可以將預先固著有黏晶薄膜3a的半 導體晶片5固著到被黏物6上並層疊。 所述絲烊工序，是用谭線7將被黏物6的端子部（内部 引線)的刖&與半導體晶片5上的電極焊盤(未圖示）電連接 的工序。作為所述焊線7，可以使用例如金線、鋁線或銅 線等。絲焊在溫度為80〜250°C、優選為80〜220。(：的範圍 内進行。另外，其加熱時間為數秒〜數分鐘。連接線在加 熱達到所述溫度範圍内的狀態下，通過組合使用超聲波的 振動能與加壓的壓接能來進行。 所述樹脂密封工序，是利用密封樹脂8將半導體晶片 5密封的工序。本工序是為了保護搭載在被黏物6上:半 導體晶片5和焊線7而進行的。本工序通過用模具將密封 用樹脂成形來進行。作為密封樹脂8，例如可以使用環氧 31 201118145 樹脂。在樹脂密封時通常在175°C的加熱溫度下進行60〜90 秒，但是，本發明不限於此，例如也可以在165〜185。(：下 進行數分鐘硬化。由此，使密封樹脂硬化。本發明中，在 黏晶工序中’即使在為了使黏晶薄膜3a熱硬化而進行熱處 理的情況下，在密封樹脂工序後，也能夠使黏晶薄膜3a 與被黏物6之間的空隙消失。 所述後硬化工序中，使在所述密封工序中硬化不充分 的密封樹脂8完全硬化。本工序中的加熱溫度根據密封樹 脂的種類而不同，例如在165〜185t的範圍内，加熱時間 為約0.5小時〜約8小時。另外，本工序中，可以使黏晶薄 膜3a完全熱硬化。此時，優選在黏晶薄膜％中調配所述 熱硬化催_。由此’使殘㈣未反應環氧基之間相互進 仃聚合反應，再進行黏晶薄膜3a的熱硬化。結果，可以 過黏晶薄膜3 a將半導體晶片5可靠地固定到被黏物上。 眭半導體封裝’例如進行耐濕回流焊接試驗 =、’也具有⑶夠耐受該試驗的高可靠性。耐濕回流焊接試 驗通過以往公知的方法進行。 另外，本發明的切割/黏晶薄膜，如圖4所示 體晶片層疊而進行三維絲的情況。圖 疋表不通過黏Ba賴三維絲轉體晶片關子 剖面圖。在® 4所示的三維安? _ = 與半導體晶片同樣尺寸的至少;J首先將切割為 .L ., , , , y 個黏晶薄M 3a固著至，丨妯 ===膜以_晶…其絲 飞進订固者。岐，韻半導體晶片5的 32 201118145 ，極焊盤部分來固著黏晶薄们3。進而， 著將另-半導體晶片15以其絲焊面為上側的方日曰式進行固 5及序。由此，用焊線7將半導體晶片 接 片15中各自的電極焊盤触黏物6電連 封工序，使密封樹脂硬化。並且利 寻=二在 /、牛導體Βθ片5之間固者。另外’利用黏 導5與另-半導體晶片15之間也固著、 工序後，可以進行後硬化工序。 在封 即使在半導體晶片的二维定酤ΑΑ 黏晶薄膜3a、n的純^ =的情町，由於不進行 古点4 m 此可以簡化製造工序和提 回成如率。另外，被黏物6不產生輕曲，並且半導體晶片 5及另一半導體晶片15不產生 元件的進-步_化。纟1文，因此可以實現半導體 膜屙2ΰ广圖5所不’可以在半導體晶片間通過黏晶薄 rer)來進行三維安裝。圖5是表示隔著塾片 ^黏^日雜將_科體βΘβ>^維钱_子的示意剖 l6j 圖。 =5所示的三維安裝的情況下，首先在被黏物6上 薄膜3a、,半導體晶片5及黏晶薄膜21並暫 膜21逢J；日而在黏晶薄膜21上依次層疊塾片9、黏晶薄 膜黏明賴3a及半導體晶片5並固著。 33 201118145 ^υιυ*+ριι 然後，如圖5所示，進行絲谭工序。由此 將半導，晶片5中的電極焊盤與被黏物6電連接。、、· 接著，進行利用密封樹脂8將半導體晶 ，序，使密封樹脂8硬化。由此，得到半 =、 2 =序優選僅將半導體晶片5—側單面密封的性密 封法(batch sealmg method)。密封是為了保護 的半導體晶片5而進行的，.其代表性方法片上黏貼 8在模具中成形的方法。此時===封樹脂 的上模和下模構成的模具，同時進二::有多個腔室 時的加熱溫度優選例如在17〇〜赋的=:=密： 後，也可以進行後硬化工序。 畨i工序 另外，作為所述塾# 9，沒有特別限制，可 如現有公知的⑪晶片、聚酿亞胺薄膜等。另外， 述 ^片古^可以使用芯材。作為怒材沒有特別限制，;以使 用現有公知的芯材。具體而言，可錢㈣ 胺薄膜、聚醋薄膜、聚對苯二甲酸乙二醇酉旨薄膜、^亞 Γ乙二醇酯薄膜、聚碳酸酯薄膜等）、用玻璃纖維ΪΪΐ g織纖維增強的樹脂基板、鏡面石夕晶圓、石夕基板或玻璃 表面=路板上，將上述的半導體封裝體進行 ，面女裝。作為表面安裝的方法，可以列舉例如：預先 ^刷電=板上供給特後，通聽鱗加熱 作為加熱方法，列舉熱風回流二 線回以。糾，可以是整體加熱、局部加熱的任意方式。 34 201118145 加熱溫度優選為240〜265°C，加熱時間優選在i秒〜2〇秒 的範圍内。 (其他事項） 在所述基板等上三維安裝半導體元件時，在形成半導 體元件的電路的一面形成緩衝塗膜。作為該緩衝塗膜，可 以列舉例如：由氮化矽膜或聚醯亞胺樹脂等耐熱樹脂形成 的緩衝塗膜》 +另外，半導體元件的三維安裝時，各階段使用的黏晶 薄膜不限於由同一組成構成，根據製造條件或用途等也可 以適當變更。 另外，上述的實施方式中，對於將多個半導體元件層 疊到基板等上以後一次性進行絲焊工序的方式進行了說 明’但疋’本發明不限於此。例如，也可以在每次將半導 體元件層疊到基板等上時都進行絲焊工序。 實例 以下’對本發明的優選實例進行例示地詳細說明，但 疋，該男、例中§己載的材料或調配量等，只要沒有特別限定 的δ己載，則本發明並不限於此。另外，份是指重量份。 (實例1) 將以丙烯酸乙酯-曱基丙烯酸曱酯為主成分的丙烯酸 酯類聚合物(Nagase ChemteX’s有限公司製，WS-023，酸 值20 mgKOH/g)7.5重量％、環氧樹脂A(JER有限公司製， Epicoat 1004)18.6重量％、環氧樹脂B(JER有限公司製， 35 201118145 V X NJTLfli.Further, the die-bonding film 3 is composed of A and, in addition to the inorganic filler, 201118145 VTu.. Other additives may be appropriately formulated as needed. Examples of the flame retardant include, for example, a trioxide recording, an oxygen resin, and the like. These flame retardants may be used singly or in combination with two kinds of ring-forming agents, for example, Ν34_^ί hexyl)ethyldimethoxy-aged, γ-glycidoxy-oxygenated The propylmethyldiethoxy Wei and the like 3 are used alone or in combination. : Such as: hydrotalcites, gas oxidation drop these = can be used alone or in combination of two or more. The die-cut film 3 of the dicing/mulet film 10, u is preferably protected by a separator (not shown). The separator has a function as a protective material for protecting the die-bonding film 3 before being actually used. Further, the separator can also be used as a supporting substrate when the die-bonding film 3 is transferred onto the adhesive layer 2. The 卩w sheet is peeled off when it is adhered to the dicing film of the dicing/mulet film. As the separator, polyethylene terephthalate (pET), polyethylene, polypropylene, or a plastic film surface-coated with a release agent such as a fluorine-containing release agent or a long-chain alkyl acrylate release agent can be used. Or paper, etc. Further, the melt viscosity of the under-layer before the thermal curing of the die-bonded film 3 is preferably 50 to 1000 pa.s, more preferably i 〇〇 8 〇〇 Pa.s, and particularly preferably 200 to 600 Pa s. By setting the melt viscosity to 50 Pas or more, the adhesion to an adherend such as a substrate can be improved. As a result, the generation of voids can be reduced on the adhesive surface with the adherend. On the other hand, by setting the melt viscosity to 1000 Pa.s or less, it is possible to suppress the leakage of the adhesive 17 201118145 component or the like from the thermosetting type adhesive crystal film. As a result, it is possible to prevent contamination of the semiconductor element adhering to the adherend by the adhesive or the adhesive. Further, the melt viscosity was measured and calculated by the following measurement method. That is, it can be measured by a parallel plate method using a rheometer (manufactured by HAAKE Co., Ltd., trade name: RS-1). That is, 'on the plate of TC, the sample of 〇·1 g taken from the die-bonded film 3 was placed and measurement was started. The average value of the melt viscosity after 12 seconds from the start of the measurement was taken as the melt viscosity. The gap between the plates is 〇1 mm. The storage elastic modulus at 260 ° C after thermal curing of the die-bonded film 3 is preferably 1 MPa or more, more preferably 5 to 100 MPa, and particularly preferably 10 to 100. MPa. Thus, for example, in the sealing step, the tilting of the semiconductor element can be prevented, and in the case where the scale is joined to the jade material, peeling can be caused between the adhesive film and the adherend. 3, ..., and smuggling, after heat treatment at 140 C for 2 hours, and then at 175 〇 under the conditions of 1 hour of honesty. For the measurement of the storage elastic modulus, for example, a solid viscoelasticity measuring device (for example) can be used. Rheometric Scientific's model number: RSA-m. That is, the sample size is set to length·mm X width lOmmx thickness 2〇0μιη'. The measurement sample is mounted on the film tensile measurement -50:3 V-temperature and speed are measured under the conditions of coffee, and the denier is measured. The elastic modulus and the loss elastic modulus are obtained by reading 26 (TC (10) elastic modulus (E,). The thickness of the adhesive film 3 (the laminated body is limited, for example, about 5 qing ~ kiss _ 1 U 卜 卜 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约 约Different thermal hardening (four) appropriate combination, can be (10) into a multi-layer structure of two or more layers. The semiconductor crystal _ butterfly process towel uses side water, therefore, there is a moisture absorption film 3 moisture absorption 'normality above the normal state. If in this When the glue is adhered to the substrate or the like with the water content of 3, the retained vapor in the adhesive interface at the post-hardening stage sometimes causes warping. Therefore, as the adhesive film 3' is formed by the glue layer The structure of the highly permeable core material is such that water vapor is diffused through the film in the post-hardening stage, so that the problem can be avoided. From this point of view, it is considered that the single-sided or double-sided surface of the core material is formed when the die-bonding_3 can be rotated. a multilayer structure of the adhesive layer. The material 'is exemplified by a film (for example, a polyimide film, a west film, a film of ethylene glycol, a film of a polyethylene naphthalate film, a film of a polyethylene naphthalate film, etc.), and a nonwoven fabric made of glass fiber or plastic. In the fiber, the earth plate, the mirror enamel wafer, the ruthenium substrate or the glass substrate are recognized, and the ruthenium film 3 is preferably protected by a separator (not shown). The separator 2 has a protective viscosity before it is actually used. Protection of crystalline film: transfer to a thin film-type release agent, etc., using a fluorine-containing release agent, long-chain alkyl acrylate, surface-coated transfer film or paper, etc. The second layer of the agent layer 2 is laminated on the substrate 1. Further, as shown in Fig. 3, the adhesive layer 2 is laminated, and the structure of the adhesive film 3 is formed only in the semiconductor wafer pasting portion 201118145. The substrate 1 serves as a strength matrix of the dicing/mulet film 10, 11. For example, low density polyethylene, linear polyethylene, medium density polyethylene = high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, segment copolymer polypropylene, homopolypropylene, polybutene Polyurethane such as polydecylpentene, ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene rare earth) propylene copolymer, ethylene_(meth)acrylic acid g (random, alternating) ugly y 乙乙佛-butylene copolymer, acetonitrile _ hexane copolymer, polyurethane/poly(p-citric acid), polyethylene naphthalate (4), polycarbonate Imine, poly selenium, polyamidimide, polyaluminium, polyamine, fully aromatic polyamine, polyphenylene sulfide, aromatic polyamine (paper), glass, 3 cloth, containing When the outer line of fluororesin, polyvinyl chloride, polyvinylidene gas, cellulose sulphate I oxime resin, metal (falling), paper, etc. is hard cut, the Yuxian material 具有 has a θ. Further, as the material of the substrate 1, a polymer such as a crosslinked body of the above resin may be mentioned. The return film may be used without stretching, or may be subjected to uniaxial or double pulse stretching treatment. The resin # which is heat-shrinkable by stretching treatment or the like can reduce the adhesive area of the adhesive layer 2 and the die-bonding film 3 by heat-shrinking the substrate after dicing, so that it can be easily recovered. Semiconductor wafer. In order to improve the adhesion to the adjacent layer, retention, etc., the surface of the substrate i is treated with a surface treatment such as chromic acid treatment, ozone exposure, flame exposure, 3 piezoelectric shot exposure, and free radiation treatment. The chemical or physical treatment or coating treatment using a primer (for example, an adhesive described later). 20 201118145 The substrate 1 can be appropriately selected to use the same kind or different kinds of materials. According to the material 4 which can be blended with a plurality of materials, in order to impart antistatic properties to the substrate, the base can be used. A layer of metal σ gold, a oxide of the like, or the like is provided on the material layer to have a thickness of about a to about two layers of the electric substance. The substrate 丨 may be a single layer or a multilayer of two or more. The thickness of the substrate 1 is not particularly limited and may be appropriately determined, and is generally from about 5 μm to about 200 μm. Further, in the range in which the effects of the present invention are not impaired, additives (e.g., colorants, fillers, plasticizers, anti-aging agents, antioxidants, surfactants, flame retardants, etc.) are added to the substrate. The binder used in the formation of the binder layer 2 is not particularly limited as long as it can produce the crystal film 3. For example, a C-type adhesive, a rubber-like pressure sensitive dopant can be used. As the pressure __, from the semi-conducting rainbow or sub-yak:: ultra-pure water, such as the pure solvent of organic solvents. Acrylic acid-based acid-based compounds based on polymer-based polymers can be used as a polymer. Examples of the acryl vinegar include: (meth) propylene group 6 (for example, r=, isobutyl s, zhongdingluo, singly, valerate, singular, hex:::, Xin η ethyl hexane vinegar, iso vinegar vinegar, vinegar vinegar, vinegar vinegar, different yam twelve shouts, thirteen ships, fourteen assault, sixteen 21 201118145 JW 1 burnt, octadecyl ester, eicosane a linear or branched alkyl ester having an alkyl group such as an ester having 1 to 30 carbon atoms, particularly a carbon number of 4 to 18, and a cycloalkyl ester of (mercapto) acrylate (for example, a cyclopentyl ester or a ring). One or two or more acrylic polymers such as hexyl ester or the like are used as a monomer component. Further, (meth) acrylate means acrylate and/or methacrylate, and (mercapto) of the present invention all have the same meaning. The acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth) acrylate or the acylate, as needed, in order to improve the cohesive force, heat resistance and the like. Examples of such a monomer include acrylic acid, methacrylic acid, (meth)acryloyl carboxyethyl ester, (mercapto) carboxy amyl acrylate, itaconic acid, maleic acid, and fumaric acid croton. Wenzhi contains slow-acting monomers, maleic anhydride, itaconic anhydride, etc. 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (methyl = enoic acid-4- Μ基丁g, (曱基) (tetra) acid _6_ via hexyl _, (methyl enoic acid each via octyl vinegar, (meth)acrylic acid * by basis, (methyl acid - I2-based laurel g, (methyl) propyl benzoic acid (4_methylcyclohexyl=based monomer; phenylacetic acid, dilute propyl, methyl) propylamine : : : , (meth) acrylamide, Methyl acrylate, (meth) acrylate 5 :, (meth) propylene methoxy naphthene, etc., containing a thiol group; Body; propylamine, propylene guess, etc. = comonomer component can be used - or two of the early body is preferably used in an amount of 4% by weight of all monomer components; ^, 5 can be two; ==== === 22 201118145 i υτρίΑ Polyfunctional monomer, for example, hexanediol Di(meth)acrylic acid brewing, (8) ethylene glycol fluorenyl acrylate vinegar, (poly) propylene glycol di(meth) acrylate vinegar, neopentyl glycol di(meth) acrylate, pentaerythritol II (fluorenyl) acrylate, dihydroxymercaptopropane tris(decyl) acrylate, pentaerythritol tris(decyl) acrylate vinegar, dipentaerythritol hexa(meth) acrylate vinegar, epoxy (mercapto) acrylate vinegar, Polyester (mercapto) acrylate, amino decanoate (meth) decyl acrylate, etc. These poly-g-monomers may be used alone or in combination of two or more. The use of polyfunctional monomers 畺, k adhesion characteristics, etc. Preferably, the acrylic polymer is obtained by polymerizing a single monomer or a mixture of two or more kinds of monomers. The polymerization can be carried out by solution polymerization, emulsion bulk polymerization, suspension. It is preferable that the content of the low molecular weight substance is small from the viewpoint of preventing contamination of the clean adherend, etc. From this viewpoint, the number average molecular weight of the acrylic polymer is preferably about 300,000 or more. for Further, in order to increase the number average molecular weight of the acrylic polymer or the like as a base polymer, an external crosslinking agent may be suitably used in the binder. Specific method as an external crosslinking method A method of adding a so-called cross-linking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or a melamine-based crosslinking agent to a reaction may be mentioned. When an external crosslinking agent is used, the amount of the crosslinking agent used is The balance of the crosslinked base polymer is appropriately determined depending on the use as the binder. In general, it is preferably 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, if necessary, in addition to 23 201118145, various conventional tackifiers and anti-aging layers 2 may be used in the adhesive, and may be formed of a light ray-curable adhesive. Radiation The f-type adhesive is irradiated with radiation such as ultraviolet rays to make the cross-linking production easy to reduce its adhesion. For example, by irradiating the transmission line only to the portion 2a of Fig. 2, the difference in adhesion between the portion 2b and the portion 2b can be set. The one-knife sound is fused by the radiation hardening type in conformity with the twin film Γ, and the portion 2a in which the adhesive force is remarkably lowered can be easily formed. The hardened and adhesively-reduced portion 2a is adhered to the die-bonding film 3, : : 另: the other 2 = the crystal 1 film 3, the interface has an easy peeling force at the time of picking up, Lt II is not lion, she is as described above, ® 1 In the adhesive layer of the dicing/mulet film 1 所示 shown, the portion & bismuth film 3 formed by the uncured radiation-curable adhesive can ensure the holding force at the time of cutting. Thus, fortunately, the 5-ray hardening type adhesive can be adhered to a substrate such as a substrate by a good adhesive peeling, and a sheet (semiconductor wafer or the like). In the adhesive layer 2 of the dicing/mulet film u shown in Fig. 2, the portion 2b can fix a wafer ring. The radiation-curable adhesive of the mountain radiation-curable adhesive can be used without any particular limitation, and a radiation-curable adhesive having a radiation-hardening functional group such as a carbon-carbon double bond and exhibiting adhesion can be used. Examples of the radiation-curable adhesive include, for example, a light-curable monomer component or an oligomer component in a general pressure sensitive 24 201118145 adhesive such as the acrylic adhesive or the rubber adhesive. Addition type light ray hardening type adhesive. Examples of the radiation curable monomer component to be blended include, for example, a carbamic acid-based oligomer, a carbamide, a methyl methacrylate, and a methyl methacrylate. Dilute ester, tetramethylolmethicone tetrakis(methyl)propionate, pentaerythritol tri(meth)acrylate, pentaerythritol tetrakis(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, Diquat, fermented octadecyl (meth) acrylate, 1,4-butanediol bis(indenyl) acrylate, and the like. In addition, examples of the light ray curable oligomer component include various oligomers such as urethanes, polyethers, polyesters, polycarbonates, and polybutadienes, and the weight average molecular weight thereof is about 100. ~ Appropriate range of about 30,000. The blending amount of the radiation curable monomer component or the oligomer component can be appropriately determined according to the type of the binder layer to reduce the adhesive strength of the binder layer. In general, it is, for example, about 5 parts by weight to about 5 parts by weight, preferably about 40 parts by weight to about 150 parts by weight, based on 100 parts by weight of the base polymer such as an acrylic polymer constituting the binder. Further, 'as a radiation hardening type binder', in addition to the addition type radiation-curable type adhesive described above, a polymerization using a carbon-carbon double bond in a polymer side chain or a main chain or at a main chain end may be mentioned. An intrinsic type of radiation hardening adhesive that acts as a base polymer. Since the intrinsic type radiation-curable adhesive does not need to contain or contain a large amount of an oligomer component as a low molecular weight component, the oligomer component or the like does not move in the binder over time, and a stable layer structure can be formed. A binder layer is therefore preferred. 25 201118145 The base polymer having a carbon-carbon double bond can use a polymer having a carbon-carbon double bond and having adhesiveness without particular limitation. As such a base polymer, a polymer having an acrylic polymer as a basic skeleton is preferable. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above. The method of introducing the carbon-carbon double bond in the acrylic polymer is not particularly limited, and various methods can be employed, and introduction of a carbon-carbon double bond into the polymer side chain is relatively easy in molecular design. For example, a method in which a monomer having a functional group in an acrylic polymer is copolymerized in advance, and a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is subjected to radiation hardening for maintaining a carbon-carbon double bond. The condensation or addition reaction is carried out in a sexual state. Examples of the combination of these functional groups include a thiol group and an epoxy group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group. Among these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is preferred in view of easiness of reaction tracking. Further, if a combination of the acrylic polymer having a carbon-carbon double bond is formed by a combination of these functional groups, the functional group may be on either side of the acrylic polymer and the compound, in the preferred combination It is preferable that the acrylic polymer has a hydroxyl group and the compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include, for example, mercaptopropene isocyanate, 2-mercaptopropenyloxyethyl isocyanate, m-isopropenyl group, α-dimethyl group. Clumsy isocyanate and the like. Further, as the acrylic polymer, a hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether exemplified above, 4-hydroxybutyl group 26 201118145 V & V/ > A polymer obtained by copolymerization of an ether, a diethylene glycol monovinyl ether compound or the like. The intrinsic type of radiation hardening type adhesive can be used alone as a base polymer having a carbon-carbon double bond (especially a propylene sulphonate polymerization 2), or in a range of insufficient characteristics (H). Body composition or oligomer component. The light ray curable oligomer component or the like is usually in the range of 0 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the base polymer. The 13⁄4 ray hardening weiwei agent preferably contains a photopolymerization primer (4) when it is hardened by ultraviolet rays or the like. The photopolymerization initiator may, for example, be 4-(2-Ethyloxy)phenyl (2-trans- 2 -propyl) fluorene, α-trans-base 2: phenyl group, 2 methyl group 2_ benzene-reduced, (10)-cyclohexyl phenyl ketone ketone alcohol compound; decyloxyacetophenone, 2,2. dimethoxy-2-phenyl = ethylene steel, 2,2-diethoxy Benzophenone _, 2_f-based o-(methylthio)-benzene f]-2-morphinyl propylamine", and other acetophenone compounds; benzoin (10), cumin isopropyl ether, bacterium曱 曱 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ · 2_(〇_ethoxy weiwei) will be a photoactive lysine compound; diphenyl fluorenone, benzoic acid, benzoic acid, ^, - dimethyl benzene, 4 methoxy, awkward @ equivalent bicone Compound; ketone ketone, 2' chlorhexidone: 2-mercapto sneak _, 2,4-dimethyl beta sinone, isopropyl succinone, =, 4 _ chlorothioxanthone , 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other ketone ketone compounds; camphorquinone; tooth ketone; sulfhydryl squamous oxide; fluorenylphosphonic acid vinegar, etc. . The amount of the photopolymerization initiator to be formulated is, for example, from about 0.05 parts by weight to about 20 parts by weight based on the parts by weight of the base polymer constituting the binder of the type 201118145. (4) In the case where the radiation hardening type adhesive forms the adhesive 2, the part of the layer 2 of the superior layer is irradiated with the Wei line so that the adhesion of the part 2a is 2b. In the dicing/mulet film of Fig. 2, for example, the relationship of the SUS304 plate (#2000 polishing) of the -9 is the adhesion of the portion 2a < The method of forming the partial ruthenium in the mixture layer 2, the method of forming the radiation-curable adhesive layer 2 on the substrate 1 and then irradiating the radiation to the =2 is hardened. The local spokes == are formed by a photomask formed with a pattern of the outer surface of the swivel wafer. Further, a method of point 2, a method of hardening, and the like can be cited. The spoke-Wei-type adhesive layer can be cured by the hardening of the line-up on the spacer. Localized radiation hardening can also be carried out on the radiation hardening adhesive layer 2 provided on the separator. In addition, through the #ray hardening type spotting agent, the whole or part of the light-shielding ray irradiation is performed, so that the semiconductor crystal _ = is customized, thereby forming a standing of the adhesive force; = the part is hard printed or The vapor deposition or the like can be used for one. The t 28 201118145 cut/mulet film 10 of the present invention can be transferred by the method of the job. Preferably, when the curing failure occurs due to oxygen at the time of the irradiation of the line, the surface of the hybrid ray-curable adhesive layer 2 is blocked from the surface t, i_, for example, the adhesive is coated with a separator. The method of shooting the layer 2, and the like. The ultraviolet rays ray are taken in the atmosphere of the four people. The thickness of the rhyme 2 is not particularly limited, and is preferably 5 to 25^, more preferably 2 to 30, more preferably a filler, a toner, a thickener, an extender, and a cutting/sticking of the present embodiment. The crystal film can be described by taking the dicing/mulet film 10 as an example. First, it is formed by a conventionally known film forming method: 2 The substrate 1 can be exemplified by a calendering film forming method, an organic filming method, a blow molding method as an example, and a τ-shaped die pressing: Law, closed system, etc. De-extrusion method, dry lamination method Next, the binder composition is applied onto the substrate 1 and heated to crosslink to form the binder layer 2. (According to the need for transfer coating, screen coating, gravure coating, etc. 乍 2 cloth: formula, can be listed: material 1 can also be applied to the table ^ b 'coating can be directly on the surface to the surface _ treatment The release paper 29 201118145 etc. is then transferred onto the substrate 1. The paper is draped: 2: The material forming the adhesive film 3 is peeled off, and then dried under predetermined conditions to form a coating. On the adhesive layer 2, a viscous crystal is formed to form a viscous film 3, whereby a dicing film 3 can be formed. The dicing film 10 can be applied to the dicing film 10 of the present invention. Fig. 3 is a schematic cross-sectional view showing an example of a semiconductor device using a die-bonded film of the present embodiment. Fig. 3 is a schematic cross-sectional view showing an example of a semiconductor device having a thin-film semiconductor device. The 曰 黏 黏 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Further, there is a case where the semiconductor resin sealant and the seal are hardened by the sealing resin 8, and the adherend 6 may be a lead frame, a TAB film, or a semiconductor wafer produced separately. The adherend 6 may be, for example, an easy egg plaque or a money-shaped viscous conductor (four) which is difficult to deform. As the substrate, a thief can be known to a person = otherwise, as the lead frame, a metal lead frame such as a lead frame, a 吐 吐 bow, a wire frame, or a glass epoxy, bt (double horse) can be used. An organic substrate made of 醯•二唤), 聚亚亚胺, etc. However, the present invention is not limited to these, and includes a circuit board which can be used after mounting a semiconductor element and electrically connecting the semiconductor element. As shown in Fig. 1, the fixing step is a step of adhering the semiconductor wafer 5 to the adherend 6 through the die-bonding film 3a. This step thermally cures the die-bonded film 3a by heat treatment under predetermined conditions, and completely bonds the semiconductor wafer 5 to the adherend 6. The temperature at the time of heat treatment is preferably from 100 to 200 ° C, more preferably from 120 to 180 ° C. Further, the heat treatment time is preferably from 0.25 hours to 10 hours, more preferably from 0.5 hours to 8 hours. As a method of fixing the semiconductor wafer 5 to the adherend 6, for example, after laminating the die-bonded film 3a onto the adherend 6, the semiconductor wafer 5 is sequentially laminated on the die-bonded surface on the bonded surface. 3& Further, the semiconductor wafer 5 to which the die-bonded film 3a is fixed in advance may be fixed to the adherend 6 and laminated. In the wire winding step, a step of electrically connecting the terminal portion (internal lead) of the adherend 6 to the electrode pad (not shown) on the semiconductor wafer 5 by the wire 7 is electrically connected. As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire or the like can be used. The wire bonding is carried out at a temperature of 80 to 250 ° C, preferably 80 to 220. Further, the heating time is from several seconds to several minutes. The connection line is carried out by using the vibration energy of the ultrasonic wave in combination with the pressure contact pressure in a state where the heating reaches the temperature range. The resin sealing step is a step of sealing the semiconductor wafer 5 with the sealing resin 8. This step is performed to protect the semiconductor wafer 5 and the bonding wires 7 mounted on the adherend 6. This step is performed by using a mold for sealing. As the sealing resin 8, for example, epoxy 31 201118145 resin can be used. In the case of resin sealing, it is usually carried out at a heating temperature of 175 ° C for 60 to 90 seconds, but the present invention is not limited thereto, and for example, 165 to 185. (: The curing is performed for several minutes. Thereby, the sealing resin is cured. In the present invention, in the case of the die bonding step, even in the case of heat treatment for thermally curing the die-bonded film 3a, the sealing resin is used. After the step, the void between the die-bonded film 3a and the adherend 6 can be eliminated. In the post-hardening step, the sealing tree which is insufficiently hardened in the sealing step is provided. The grease 8 is completely cured. The heating temperature in this step varies depending on the type of the sealing resin, for example, in the range of 165 to 185 t, and the heating time is from about 0.5 to about 8 hours. Further, in this step, a die-bonding film can be obtained. 3a is completely thermally hardened. At this time, it is preferred to formulate the heat hardening _ in the % of the die-bonding film. Thus, the residual (four) unreacted epoxy groups are mutually polymerized, and then the heat of the die-bonding film 3a is performed. As a result, the semiconductor wafer 5 can be reliably fixed to the adherend through the die-bonding film 3 a. The semiconductor package is subjected to, for example, a moisture-resistant reflow soldering test =, and also has (3) high reliability to withstand the test. The moisture-resistant reflow soldering test is carried out by a conventionally known method. Further, the dicing/mulet film of the present invention is obtained by laminating a bulk wafer as shown in Fig. 4, and the three-dimensional filament is used. The cross section of the bulk wafer. The three-dimensional security shown in ® 4 is at least the same size as the semiconductor wafer; J is first cut into .L ., , , , y viscous thin M 3a fixed to 丨妯=== Membrane to _ crystal... its silk fly Into the subscriber, 岐, rhyme semiconductor wafer 5 of 32 201118145, the pad portion is fixed to the die bond 3. In addition, the other semiconductor wafer 15 with its wire surface as the upper side of the sunday Thus, the bonding of the respective electrode pad contacts 6 in the semiconductor wafer tabs 15 by the bonding wires 7 is performed to harden the sealing resin, and the search is made for the second electrode. In addition, the post-hardening step can be performed after the adhesion between the adhesion guide 5 and the other semiconductor wafer 15 is completed. The two-dimensionally fixed tantalum film 3a of the semiconductor wafer is sealed. In the case of the pure ^ of the n, it is possible to simplify the manufacturing process and bring back the rate because it does not carry the ancient point of 4 m. Further, the adherend 6 does not produce a slight curvature, and the semiconductor wafer 5 and the other semiconductor wafer 15 do not cause further progression of the element. In this case, it is possible to realize a three-dimensional mounting of a semiconductor film, which can be performed by a thin crystal rer) between semiconductor wafers. Fig. 5 is a schematic cross-sectional view showing a cross section of a 塾 ^ _ _ & & & & & & & & 。 。 。 。 。 。 。 。 。 。 。 。. In the case of the three-dimensional mounting shown in Fig. 5, first, the film 3a, the semiconductor wafer 5, and the die-bonding film 21 are temporarily laminated on the adherend 6, and the film 9 is laminated on the die-bonded film 21 in this order. The adhesive film is adhered to the 3a and the semiconductor wafer 5 and fixed. 33 201118145 ^υιυ*+ριι Then, as shown in Fig. 5, the silk tantalum process is carried out. Thereby, the semiconductor pads in the wafer 5 are electrically connected to the adherend 6 by the semiconductor. Then, the semiconductor resin is crystallized by the sealing resin 8 to cure the sealing resin 8. Thus, it is preferable to obtain a half seal method using a half seal and a single seal on the semiconductor wafer 5 side. The sealing is performed for the protection of the semiconductor wafer 5, and a representative method of the method of forming the sheet 8 in the mold. At this time, === the mold composed of the upper mold and the lower mold of the sealing resin, and at the same time, the heating temperature when there are a plurality of chambers is preferably, for example, after 17〇~fu====: Hardening process. Further, the 塾# 9 is not particularly limited, and may be, for example, a conventionally known 11 wafer or a polyimide film. In addition, the core piece can be used. The anger material is not particularly limited; and a conventionally known core material is used. Specifically, the carbon (4) amine film, the polyester film, the polyethylene terephthalate film, the ethylene glycol film, the polycarbonate film, etc.) are reinforced with glass fiber ΪΪΐ g woven fiber. The above-mentioned semiconductor package is carried out on a resin substrate, a mirror surface wafer, a stone substrate or a glass surface = a road surface. As a method of surface mounting, for example, the brushing is performed in advance, the plate is supplied, and the scale is heated as a heating method, and the hot air is returned to the second line. Correction can be any way of overall heating or local heating. 34 201118145 The heating temperature is preferably 240 to 265 ° C, and the heating time is preferably in the range of i seconds to 2 〇 seconds. (Others) When the semiconductor element is three-dimensionally mounted on the substrate or the like, a buffer coating film is formed on one surface of the circuit on which the semiconductor element is formed. The buffer coating film may, for example, be a buffer coating film formed of a heat resistant resin such as a tantalum nitride film or a polyimide resin. In addition, when the semiconductor element is three-dimensionally mounted, the die-bonding film used in each stage is not limited to The same composition may be appropriately changed depending on the production conditions, use, and the like. In the above-described embodiment, the method of performing the wire bonding process once after laminating a plurality of semiconductor elements on a substrate or the like has been described. However, the present invention is not limited thereto. For example, the wire bonding process may be performed each time the semiconductor component is laminated on a substrate or the like. EXAMPLES Hereinafter, preferred embodiments of the present invention will be exemplarily described in detail, but the present invention is not limited thereto, as long as the materials or the amounts of the materials contained in the male and the exemplified articles are not particularly limited. In addition, parts mean parts by weight. (Example 1) An acrylate-based polymer (manufactured by Nagase ChemteX's Co., Ltd., WS-023, acid value: 20 mgKOH/g) containing urethane acrylate-mercapto acrylate as a main component, 7.5 wt%, epoxy resin A (made by JER Co., Ltd., Epicoat 1004) 18.6% by weight, epoxy resin B (manufactured by JER Co., Ltd., 35 201118145 VX NJTLfli.

Epicoat 827)12.0 重量％、酚醛Epicoat 827) 12.0% by weight, phenolic

Mirex XLC-4L)21.7重量％、球曰U井化學有限公司製’ 有限公司製，so_25r)39.9 重;^二氧切(ADMATECHs 石夕有限公司製，KBM.3G3)G29里:魏偶聯劑(信越有機 :化成有限公司製 化石夕以外的有機成们〇〇 ^量 二J於除球❿-氧 乙酮中，製備濃度23.6重量7重置份)溶解於甲 里0的膠黏劑组合物（豆中，從上 述有機成分中除去曱乙酮）。另外 ^ v , ^ ^ }另外，（膠黏劑組合物的熱硬 ，性成》中_氧基的莫耳數__組合物的熱硬化性 成分中的酚羥基的莫耳數)為1 5。 將該膠黏劑組合物溶液塗布到聚石夕氧烧脫模處理後 的厚度50 μΐη的聚對苯二曱酸乙二醇醋薄膜製成的脫模處 理薄膜(剝離襯墊)上’然後在13(rc乾燥2分鐘。由此，製 作厚度25 μιη的熱硬化型黏晶薄膜。 (實例2) 將以丙烯酸乙酯-曱基丙烯酸曱酯為主成分的丙烯酸 酯類聚合物(Nagase ChemteX’s有限公司製，SG-700AS， 酸值36 mgKOH/g)7.5重量％、環氧樹脂a(JER有限公司 製，Epicoat 1004)18.6重量％、環氧樹脂b(JER有限公司 製，Epicoat 827)12.0重量％、酚醛樹脂(三井化學有限公司 製，Mirex XLC-4L)21.7重量。/〇、球形二氧化矽 (ADMATECHS有限公司製，SO-25R)39.9重量％、矽烷偶 聯劑(信越有機矽有限公司製，KBM-303)0.29重量％和熱 硬化催化劑（四國化成有限公司製，C11 _Z)0.01重量％(相對 36 201118145 於除球形二氧化矽以外的有機成分100重量份為0017重 量份)溶解於曱乙酮中，製備濃度23.6重量％的膠黏劑组合 物(其中，從上述有機成分中除去曱乙酮）。另外，（膠黏劑 組合物的熱硬化性成分中的環氧基的莫耳數)/(膠黏劑組合 物的熱硬化性成分中的酚羥基的莫耳數)為1.5。 將該膠黏劑組合物溶液塗布到聚矽氧烷脫模處理後 的f度50 μιη的聚對苯二曱酸乙二醇酯薄膜製成的脫模處 理薄膜(剝離襯墊)上，然後在13〇。〇乾燥2分鐘。由此，製 作厚度25 μιη的熱硬化型黏晶薄膜。 (實例3) 將以丙烯酸乙酯-曱基丙烯酸甲酯為主成分的丙烯酸 酯類聚合物(Nagase ChemteX，s有限公司製，sg_7〇〇as 改，酸值5〇 mgKOH/g)7.5重量％、環氧樹脂A(舰有限 公司製’Epicoat 1004)18.6重量％、環氧樹脂B(舰有限 公司製’ Epicoat 827)12.0重量％、祕樹脂(三井化學有限 =司製，Mlrex XLC-4L)21.7重量％、球形二氧化石夕 (DMATECHS 有限公司製’ s〇_25R)39 9 重 聯劑(信越有機矽有限公司製，κβμ_3〇3)〇29 硬化催化劑（四國化成有限公司製，cll_z)〇〇 ^ ° 口射 於除球形二氧化料外的有機成分⑽重量份^ 7 ^ 量份)溶解於曱乙酮中，製備濃度2 = . * 物(盆中，從卜行、古德占八士入 的膠黏劑组合 中除去曱乙酮）。另外，（膠黏劑 、、且&物的熱硬化性成分中的環H 乂 物的熱硬化性成分中的心為數△(膠黏劑組合 37 201118145 ^υιυηριι 將該膠黏劑組合物溶液塗布到聚石夕氧烧脫模處理後 的厚度50哗的聚對苯二甲酸乙二醇醋薄膜製成的脫模處 理=膜(剝離襯塾)上’然後在13(rc乾燥2分鐘。由此，製 作厚度25 μιη的熱硬化型黏晶薄膜。 、 (比較例1) 將以丙稀酸乙自旨.甲基丙触甲g旨為主成分的丙稀酸 酯類聚合物(Nagase ChemteX’s有限公司製，SG_7〇L，酸 值4 mgKOH/g)7.5重量％、環氧樹脂A(JER有限公司製， Epicoat 10〇4)18.6重量％、環氧樹脂B(JER有限公司製， Epicoat 827)12.0重量％、酚醛樹脂(三井化學有限公司製， Μ職 XLC-4L)21.7 重；f%、球形二氧化破(ADMatechs 有限公司製’ SO-25R)39.9重量％、魏偶聯劑(信越有機 石夕有限公司製’ ΚΒΜ·3_·29重量％和熱硬化催化劑(四 國化成有限公司製’ C11-Z)G.G1重量％(相對於除球形二氧 化矽以外的有機成分1〇〇重量份為〇 〇17重量份)溶解於甲 乙酮中，製備濃度23.6重量％的膠黏劑组合物(其中，從上 述有機成分中除去曱乙酮）。另外，（膠黏劑組合'物的熱硬 化性成分中的環氧基的莫耳數)/(膠黏劑組合物的熱硬化性 成分中的酚羥基的莫耳數)為1.5。 … 將該膠黏劑組合物溶液塗布到聚矽氧烷脫模處理後 的厚度50 μπι的聚對苯二曱酸乙二醇醋薄膜製成的脫模處 理薄膜(剝離襯墊)上，然後在13(TC乾燥2分鐘。由此，製 作厚度25 μιη的熱硬化型黏晶薄膜。 (凝膠分率的測定） 38 201118145 -»vrx VTwxji 對於上述實例及比較例中製作的熱硬化型黏晶薄 膜，如下所述測定凝膠分率。即，從熱硬化前的各熱硬化 型黏晶薄膜中取約1 g的試樣，將它們在750°C進行2小 時的空燒。之後，在室溫下冷卻。另外，稱取到坩鋼中， 用燃燒器煆燒至不產生煙為止。接著’在750°C煆燒0.5 小時’使其灰化。在室温下冷卻，測定坩鍋中殘留的灰分 的重量。由試樣灰化前後的重量求出灰分的重量％。將此 時的灰分的重量％作為熱硬化型黏晶薄膜中的無機成分的 重量％。 另外，從實例和比較例製作的熱硬化前的各熱硬化型 黏晶薄膜中分別取〇.3 g(初始重量）的試樣，將它們用厚度 0.2 μιη的Teflon(註冊商標）片包裹，然後浸潰到4〇虹的 THF中放置7天。之後，將不溶成分連同Teflon片一起重 新，20 mLTHF洗滌二次，然後乾燥成固體。將其稱量得 燥重！。另外’由試樣的前後重量，用下式求 雜所得郷分料減切述錢成分的重 :I仏’作為熱硬化型黏晶薄膜的有機成分的凝膠 刀平。'、、口果如下表1所示。 重量(：二率(重量%)=(試樣的乾燥重量(.(試樣的初始 (熔融黏度的測定） 型黏晶相，分\=财製作的熱硬化前的各熱硬化 卞仃板法測定熔融黏度。從 39 201118145Mirex XLC-4L) 21.7 wt%, ball 曰 U Well Chemical Co., Ltd. made by Ltd., so_25r) 39.9 weight; ^ dioxotomy (ADMATECHs Shi Xi Co., Ltd., KBM.3G3) G29: Wei coupling agent (Xin Yue Organic: Chemicals other than the fossils of Huacheng Co., Ltd., the amount of 2J in the deuterium-oxyethyl ketone, the preparation of a concentration of 23.6 wt% (replacement part) of the adhesive composition dissolved in Kerry 0 ( In the beans, the ethyl ketone is removed from the above organic components. Further, ^ v , ^ ^ } In addition, (the thermosetting property of the adhesive composition, the mole number of the oxy group, the molar number of the phenolic hydroxyl group in the thermosetting component of the composition) is 1 5. Applying the solution of the adhesive composition to a release-treated film (release liner) made of a polyethylene terephthalate film having a thickness of 50 μΐ after the demolding treatment, and then It was dried at 13 (rc for 2 minutes. Thus, a thermosetting type microcrystalline film having a thickness of 25 μm was produced. (Example 2) An acrylate-based polymer mainly composed of ethyl acrylate-mercapto acrylate (Nagase ChemteX's) Co., Ltd., SG-700AS, acid value 36 mgKOH/g) 7.5% by weight, epoxy resin a (JE Co., Ltd., Epicoat 1004), 18.6% by weight, epoxy resin b (manufactured by JER Co., Ltd., Epicoat 827) 12.0 % by weight, phenolic resin (Mirex XLC-4L, manufactured by Mitsui Chemicals Co., Ltd.) 21.7 wt./〇, spherical cerium oxide (manufactured by ADMATECHS Co., Ltd., SO-25R) 39.9 wt%, decane coupling agent (Shin-Etsu Organic Co., Ltd.) Company, KBM-303) 0.29 wt% and thermosetting catalyst (C11_Z, manufactured by Shikoku Chemicals Co., Ltd.) 0.01% by weight (relative to 36 201118145, 100 parts by weight of the organic component other than spherical ceria is 0017 parts by weight) Dissolved in acetophenone to prepare a concentration of 23.6 % by weight of the adhesive composition (wherein the ethyl ketone is removed from the above organic component). (In addition, the number of moles of epoxy groups in the thermosetting component of the adhesive composition) / (adhesive) The molar number of the phenolic hydroxyl group in the thermosetting component of the composition is 1.5. The adhesive composition solution is applied to the poly-p-benzoic acid B at a degree of 50 μm after the release treatment of the polyoxyalkylene oxide. A release-treated film (release liner) made of a diol ester film was then dried at 13 Torr for 2 minutes, thereby producing a thermosetting type die-bonding film having a thickness of 25 μm. (Example 3) Acrylic acid was used. Ethyl ester-methyl methacrylate-based acrylate polymer (Nagase ChemteX, sg_7〇〇as, acid value 5〇mgKOH/g) 7.5% by weight, epoxy resin A (ship Co., Ltd. 'Epicoat 1004) 18.6% by weight, epoxy resin B (Econcoat 827, 'Econcoat 827) 12.0% by weight, secret resin (Mitsui Chemical Co., Ltd., Mlrex XLC-4L) 21.7 wt%, spherical dioxide Shi Xi (" 〇 _25R" made by DMATECHS Co., Ltd. 39 9 re-linking agent (made by Shin-Etsu Organic Co., Ltd.) , κβμ_3〇3)〇29 hardening catalyst (manufactured by Shikoku Chemical Co., Ltd., cll_z) 〇〇^ ° Oral injection of organic components other than spherical dioxide (10 parts by weight ^ 7 ^ parts by weight) dissolved in acetophenone , Preparation of concentration 2 = . * (in the pot, from the line, Gudzhan Baoshi into the adhesive combination to remove ethidium). Further, (the amount of the core in the thermosetting component of the ring H 中 in the thermosetting component of the adhesive, and the & object is Δ (adhesive combination 37 201118145 ^υιυηριι the adhesive composition solution) It was applied to a release treatment of a 50 Å polyethylene terephthalate film having a thickness of 50 Å after the demolding treatment, and the film was peeled off on a film (removed lining) and then dried at 13 (rc for 2 minutes). Thus, a thermosetting type die-bonding film having a thickness of 25 μm was produced. (Comparative Example 1) An acrylate polymer (Nagase) containing acrylic acid as a main component of methyl methacrylate Manufactured by ChemteX's Co., Ltd., SG_7〇L, acid value 4 mgKOH/g) 7.5 wt%, epoxy resin A (manufactured by JER Co., Ltd., Epicoat 10〇4), 18.6 wt%, epoxy resin B (manufactured by JER Co., Ltd., Epicoat) 827) 12.0% by weight, phenolic resin (manufactured by Mitsui Chemicals Co., Ltd., XL XL XXL-4L) 21.7 重量; f%, spherical dioxide oxidized (ADHAtechs Co., Ltd. 'SO-25R) 39.9 wt%, Wei coupling agent (Shinoshi Organic Shixi Co., Ltd. made 'ΚΒΜ·3_·29% by weight and thermosetting catalyst (Four Guohuacheng Co., Ltd.) Preparation of 'C11-Z) G.G1 wt% (with respect to 1 part by weight of the organic component excluding spherical cerium oxide, 〇〇17 parts by weight) was dissolved in methyl ethyl ketone to prepare a binder composition having a concentration of 23.6% by weight. (In the case of removing the ethyl ketone from the above organic component), (the molar number of the epoxy group in the thermosetting component of the adhesive composition) / (the thermosetting property of the adhesive composition) The molar number of the phenolic hydroxyl group in the component is 1.5. The solution of the adhesive composition is applied to a polyethylene terephthalate film having a thickness of 50 μm after the release treatment of the polyoxyalkylene oxide. The release-treated film (release liner) was then dried at 13 (TC for 2 minutes. Thus, a thermosetting type microcrystalline film having a thickness of 25 μm was produced. (Measurement of gel fraction) 38 201118145 -»vrx VTwxji With respect to the thermosetting type die-bonding film produced in the above examples and comparative examples, the gel fraction was measured as follows. That is, about 1 g of the samples were taken from each of the thermosetting type die-shaped film before thermosetting, and they were taken. The air was burned at 750 ° C for 2 hours. After that, it was cooled at room temperature. In steel, burn with a burner until no smoke is generated. Then ash at 750 ° C for 0.5 hour to ash. Cool at room temperature, determine the weight of ash remaining in the crucible. The weight % of the ash was determined by the weight of the front and the back. The weight % of the ash at this time was made into the weight % of the inorganic component in the thermosetting type microcrystalline film. Moreover, each thermosetting type before thermosetting by the Example and the comparative example. A sample of .3 g (initial weight) was taken from the die-bonded film, and they were wrapped with Teflon (registered trademark) sheets having a thickness of 0.2 μm, and then immersed in 4 Torr of THF for 7 days. Thereafter, the insoluble components were reconstituted together with the Teflon tablets, washed twice with 20 mL of THF, and then dried to a solid. Weigh it dry! . Further, from the front and rear weights of the sample, the weight of the money component was reduced by the following formula to obtain the weight of the component: I仏' as the gel level of the organic component of the thermosetting type microcrystalline film. ',, the fruit is shown in Table 1. Weight (: second rate (% by weight) = (dry weight of the sample (. (initial of the sample (measurement of the melt viscosity) type of the crystal phase, the sub-hardness of each of the thermosetting slabs before the thermosetting Method for determining the melt viscosity. From 39 201118145

各實例或比較例中製作的熱硬化型黏晶薄膜中取〇.丨g的 s式樣’投入到預先在l〇〇°C加熱的板上。然後，將測定開 始300秒後的值作為熔融黏度。板間的間隙設定為〇1 Π1Π1。結果如下表1所示。 (四周後的熔融黏度的測定） 對於各實例和比較例中製作的熱硬化前的各熱硬化 型黏晶薄膜，在23°c的環境下放置672小時。然後，分別 測定120°C的熔融黏度。即，使用流變儀(HAAKE公司製， R S -1)通過平行板法測定熔融黏度。從各實例或比較例中製 作的熱硬化型黏晶薄膜中取〇_1 g的試樣，投入到預先在 100°C加熱的板上。然後，將測定開始300秒後的值作為炫 融黏度。板間的間隙設定為0.1 mm。結果如下表1所示。 (熱硬化型黏晶薄膜的酸值的測定） 各實例及比較例中製作的熱硬化型黏晶薄膜的酸值 的測定，根據JIS K 0070的中和滴定法進行。 具體而言’首先將各熱硬化型黏晶薄膜切割為約lcm 見方的尺寸，製成測定用試樣。然後，準嫁地稱量所述測 疋用s式樣’將其1 g與曱乙鋼1 〇〇 mL —起加入到容積200 mL的錐形瓶中。之後，進行20分鐘的超聲波溶解，分別 製成試樣溶液。 接著，對所述試樣溶液，使用0.025mol/L的氫氧化鉀 乙醇溶液(指示劑：1%酚酞)作為滴定液，進行酸值的測定。 即’在各試樣溶液中加入數滴酚酞溶液，在水浴上進行充 分地振搖混合至試樣完全溶解。再用氫氧化鉀乙醇溶液進 201118145 ^οιοπριι 行滴定，將指示劑的淡紅色持續30秒的時刻作為終點。 (260°C的儲能彈性模量） 。將各實例和比較例中製作的各熱硬化型黏晶薄膜在 120 C加熱處理1小時後，再在175X：進行1小時的加熱處 理，使其熱硬化。接著’將熱硬化後的各熱硬化型黏晶薄 膜用切割刀切剎為厚度2〇〇 、長度4〇〇 mm、寬度1〇 的條狀。然後，使用固體黏彈性測定裝置（RSAIn， Rheometric Scientific公司製），在頻率j Hz、升溫速度1〇 /分鐘的條件下，測定這些試樣的_5〇〜3〇〇<t下的拉伸儲 能彈性模量以及損耗彈性模量。儲能彈性模量(E，)通過讀 取該測定時的260°C的值而得到。結果如下表i所示。 (剪切膠黏力） 上述實例及比較例中製作的熱硬化型黏晶薄膜的剪 切膠黏力如下進行測定。 首先’使用層壓機將各熱硬化型黏晶薄膜黏貼到半導 體兀件(長5 mmx寬5 mmx厚0.5 mm)上。黏貼條件是：溫 度50C ’層壓機速度10 mm/秒，壓力〇 15 Mpa。另外， 在另一半導體元件(長l〇mmx寬10mm>〇!| 〇 5 mm)上通過 熱硬化型黏晶薄膜黏貼上述半導體元件。黏貼條件是：溫 度50°C，層壓機速度1〇 mm/&，壓力〇 15 MPa。接著， 在120°C、1小時的條件下進行熱處理，進行熱硬化型黏晶 薄膜的熱硬化。 熱硬化後’使用膠黏試驗機(Dagy公司製，#4000)， 測定平臺溫度175Ϊ、頭高1〇〇 μιη、速度〇·5 mm/秒下的 201118145 ^oio^pir 剪切膠黏力。結果如下表丨所示。 (鍾曲量） 將各實例和比較例中製作的各熱硬化型黏晶薄膜分 S3 4〇t的條件下黏貼到1〇醜見方、厚度50 ^ 導體晶片上。另外’通過各熱硬化型黏晶薄膜將半導 體晶片安裝到帶有阻焊_樹脂基板(朗環氧縣板，基 板厚度0.23細)上。此時的條件是：溫度12(η：，壓力〇 2 MP^2秒。另外，將安裝有半導體晶片的所述樹脂基板 用乾城在峨崎2小賴處理，健硬 膜熱硬化。 土鄉日日存 接著，將所得材料以所述樹脂基板為下側的方式設置 在平板上，測定半導體晶片的對角線上的凹凸。由此，測 ^平板趟起的半導體晶片的高度，_曲量(㈣。測 疋時’將半導體晶片的對角線上的兩端部校正至平衡 〇)。另外，測定使用表面粗糙度計（Veec〇公司製: DEKTA，8) ’在測定速度i 5晒/秒、載荷！ g的條件下進 订。測疋結果，將㈣量為5G_以下評 5〇 μη!評價為χ。結果如下表丨所示。 "文過 (結果） 如下表1中的貫例1〜3的結果可知，#塑性樹脂的酸 值為20、36 mgKOH/g時，可以使在12〇t、i小時條件下 熱硬化的熱硬化型黏晶薄膜的剪切膠黏力為〇5恤以 上。另外，在實例1和2中，對於四周制120t的熔融 黏度’也可以抑制其增力σ，確認保存性優良。另外，帶有 42 201118145 JOlDHpll 阻焊劑的樹脂基板的翹曲量均為5〇 μπι以下，確認熱硬化 型黏晶薄膜的硬化收縮受到抑制。 另—方面’在比較例1中，熱塑性樹脂的酸值為4 mgKOH/g時，能夠抑制四周後的i2(rc的熔融黏度增大， 但在12〇ΐ、1小時條件下熱硬化後的剪切膠黏力停留在 〇·1 MPa ’確認膠黏性差。 表1 實例1 實例2 實例3 比較例1 熱塑性樹脂的酸值(mgKOH/g) 20 36 50 4 120°C、1小時下的凝膠分率(重量％) 7.5 10.1 15.2 5.2 175°C ' 1小時下的凝膠分率(重量 15.6 18.8 26.7 8.1 剪切膠黏力(MPa) 0.6 1.1 1.7 0.1 炼融黏度(Pa.s) 342 364 398 362 熱硬化型黏晶薄膜的酸值(mgKOH/g) 4.4 8.0 11.1 1.0 儲能彈性模量(Mpa) ------ 四周後的熔融黏度(Pa.s) >1.0 >1.0 >1.0 <1.0 387 523 >1000 372 鐘曲量(μηι) 10 20 25 5 雖然本發明已以實施例揭露如上，然其並非用以限定 本發明’任何所屬技術領域中具有通常知識者，在不脫離 本發明之精神和範圍内，當可作些許之更動與濶錦，故本 發明之保護範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 ’ 圖1是表示本發明的一個實施方式的切割/點晶薄膜 43 201118145 juiunpn 的示意剖面圖。 圖2是表示本發明的另一實施方式的切割/黏晶薄膜 的示意剖面圖。 圖3是表示通過本發明的一個實施方式的黏晶薄膜安 裝半導體晶片的例子的示意剖面圖。 圖4是表示通過所述黏晶薄膜三維安裝半導體晶片的 例子的示意剖面圖。 圖5是表示使用上述黏晶薄膜、通過隔片三維安裝兩 個半導體晶片的例子的示意剖面圖。 圖6是表示對於通過熱硬化型黏晶薄膜黏晶在具有阻 焊膜的樹脂基板上的半導體晶片、用於說明其翹曲量的測 定方法的說明圖。 【主要元件符號說明】 1 :基材 2:黏合劑層 2a、2b、3b :部分 3、3’、13、21 :黏晶薄膜 3 a .部分(黏晶薄膜） 5:半導體晶片 6 :被黏物 7 :焊線 8:密封樹脂 44 201118145 9 :墊片 10、11 :切割/黏晶薄膜 15 :半導體晶片 45In the thermosetting type die-bonding film produced in each of the examples or the comparative examples, the s pattern of 〇.丨g was put into a plate heated in advance at 10 °C. Then, the value after the start of 300 seconds was measured as the melt viscosity. The gap between the plates is set to 〇1 Π1Π1. The results are shown in Table 1 below. (Measurement of Melt Viscosity After Four Weeks) Each of the thermosetting type die-shaped films before thermal hardening prepared in each of the examples and the comparative examples was allowed to stand in an environment of 23 ° C for 672 hours. Then, the melt viscosity at 120 ° C was measured, respectively. Specifically, the melt viscosity was measured by a parallel plate method using a rheometer (manufactured by HAAKE Co., Ltd., R S -1). A sample of 〇_1 g was taken from the thermosetting type microcrystalline film produced in each of the examples or the comparative examples, and placed on a plate heated at 100 °C in advance. Then, the value after 300 seconds from the start of the measurement was taken as the viscous viscosity. The gap between the plates is set to 0.1 mm. The results are shown in Table 1 below. (Measurement of Acid Value of Thermosetting Type Oxygen Film) The measurement of the acid value of the thermosetting type die-bonding film produced in each of the examples and the comparative examples was carried out in accordance with the neutralization titration method of JIS K 0070. Specifically, each of the thermosetting type adhesive crystal films was first cut into a size of about 1 cm square to prepare a sample for measurement. Then, weighed the sample with the s-type, and weighed 1 g of it with 1 〇〇 mL of 曱乙钢 into a conical flask of 200 mL volume. Thereafter, ultrasonic dissolution was carried out for 20 minutes to prepare a sample solution. Next, the sample solution was measured for acid value using 0.025 mol/L potassium hydroxide ethanol solution (indicator: 1% phenolphthalein) as a titration solution. Namely, a few drops of the phenolphthalein solution were added to each sample solution, and the mixture was shaken thoroughly on a water bath until the sample was completely dissolved. The potassium hydroxide ethanol solution was further titrated into 201118145 ^οιοπριι, and the time when the indicator's reddish color lasted for 30 seconds was used as the end point. (Storage elastic modulus at 260 ° C). Each of the thermosetting type adhesive crystal films produced in each of the examples and the comparative examples was heat-treated at 120 C for 1 hour, and then heat-treated at 175X for 1 hour to thermally harden. Then, each of the thermosetting type adhesive films after heat curing was cut into a strip having a thickness of 2 〇〇, a length of 4 mm, and a width of 1 用 by a cutter. Then, using a solid viscoelasticity measuring apparatus (RSAIn, manufactured by Rheometric Scientific Co., Ltd.), the sample was measured at a frequency of j Hz and a temperature increase rate of 1 Torr/min, and the _5 〇 3 〇〇 t pull of these samples was measured. The storage elastic modulus and the loss elastic modulus. The storage elastic modulus (E,) was obtained by reading the value of 260 ° C at the time of the measurement. The results are shown in Table i below. (Shear adhesive strength) The shear adhesive strength of the thermosetting type adhesive crystal film produced in the above examples and comparative examples was measured as follows. First, each thermosetting type die-bonding film was adhered to a semiconductor element (length 5 mm x width 5 mm x thickness 0.5 mm) using a laminator. The bonding conditions are: temperature 50 C ' laminator speed 10 mm / sec, pressure 〇 15 Mpa. Further, the above semiconductor element was bonded to the other semiconductor element (length l mmx width 10 mm > 〇! | 〇 5 mm) by a thermosetting type adhesive film. The bonding conditions were: temperature 50 ° C, laminator speed 1 〇 mm / & pressure 〇 15 MPa. Subsequently, heat treatment was carried out under the conditions of 120 ° C for 1 hour to thermally harden the thermosetting type adhesive crystal film. After heat hardening, the adhesive strength of the machine was measured using a tack tester (manufactured by Dagy Co., Ltd., #4000) at a platform temperature of 175 Å, a head height of 1 〇〇 μιη, and a speed of 〇·5 mm/sec at 201118145 ^oio^pir. The results are shown in the table below. (Clock amount) Each of the thermosetting type die-bonding films produced in each of the examples and the comparative examples was adhered to a ruthenium-thick, 50-cm conductor wafer under the conditions of S3 4 〇t. Further, the semiconductor wafer was mounted on a solder resist-resin substrate (Lang Epoxy plate, substrate thickness 0.23 fine) by each thermosetting type die-bonding film. The condition at this time is: temperature 12 (η:, pressure 〇2 MP^2 sec. Further, the resin substrate on which the semiconductor wafer is mounted is processed by the shovel in the Sakizaki 2, and the hard film is thermally hardened. Next, the material is placed on the flat plate so that the resin substrate is on the lower side, and the unevenness on the diagonal of the semiconductor wafer is measured. Thus, the height of the semiconductor wafer picked up by the flat plate is measured. The amount ((4). When measuring the '", the both ends of the diagonal line of the semiconductor wafer were corrected to the balance 〇). The measurement was performed using a surface roughness meter (manufactured by Veec Corporation: DEKTA, 8) 'at the measurement speed i 5 / sec, load! Under the condition of g, the test results, the (four) amount is 5G_ below 5〇μη! The evaluation is χ. The results are shown in the following table. "文过(Results) as shown in Table 1 below According to the results of the examples 1 to 3, when the acid value of the plastic resin is 20 or 36 mgKOH/g, the shear adhesive of the thermosetting type microcrystalline film which is thermally hardened under the conditions of 12 〇t and i hours can be obtained. The force is more than 5 shirts. In addition, in Examples 1 and 2, the melt viscosity of 120t is also used for the circumference. The reinforcing force σ can be suppressed, and the storage stability is excellent. The warpage amount of the resin substrate with 42 201118145 JOlDHpll solder resist is 5 〇μπι or less, and it is confirmed that the hardening shrinkage of the thermosetting type die-bonding film is suppressed. In the comparative example 1, when the acid value of the thermoplastic resin is 4 mgKOH/g, it is possible to suppress i2 (the melt viscosity of rc increases after four weeks, but the shear after thermal hardening under conditions of 12 Torr and 1 hour) Adhesive force stayed at 〇·1 MPa 'Confirmed poor adhesion. Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Acid value of thermoplastic resin (mgKOH/g) 20 36 50 4 120 ° C, 1 hour gel Fraction (% by weight) 7.5 10.1 15.2 5.2 175 °C 'The gel fraction at 1 hour (weight 15.6 18.8 26.7 8.1 Shear adhesion (MPa) 0.6 1.1 1.7 0.1 smelting viscosity (Pa.s) 342 364 Acid value of 398 362 thermosetting type die-bonding film (mgKOH/g) 4.4 8.0 11.1 1.0 Storage elastic modulus (Mpa) ------ melt viscosity after four weeks (Pa.s) >1.0 >1.0 >1.0 <1.0 387 523 >1000 372 bell volume (μηι) 10 20 25 5 Although the present invention has been disclosed by way of example, The invention is intended to be limited to the scope of the invention, and the scope of protection of the present invention is intended to be attached thereto without departing from the spirit and scope of the invention. The scope is defined. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a dicing/dot film 43 201118145 juiunpn according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a dicing/mulet film according to another embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing an example of mounting a semiconductor wafer by a die-bonding film according to an embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing an example in which a semiconductor wafer is three-dimensionally mounted by the die-bonding film. Fig. 5 is a schematic cross-sectional view showing an example in which two semiconductor wafers are three-dimensionally mounted through a separator using the above-mentioned die-bonding film. Fig. 6 is an explanatory view showing a method of measuring the amount of warpage of a semiconductor wafer which is bonded to a resin substrate having a solder resist film by a thermosetting type die-bonding film. [Explanation of main component symbols] 1 : Substrate 2: Adhesive layer 2a, 2b, 3b: Part 3, 3', 13, 21: Amorphous film 3 a. Part (adhesive film) 5: Semiconductor wafer 6 : Viscous 7 : Wire bond 8 : Sealing resin 44 201118145 9 : Gasket 10, 11 : Cutting / die-bonding film 15 : Semiconductor wafer 45

Claims (1)

201118145201118145 七、申請專利範圍： L 一種熱硬化型黏晶薄膜，用於將半導體元件膠黏固 定到被黏物上，其中， 通過12〇t、1小時的熱處理而熱硬化後有機成分的 凝膠分率在20重量％以下的範圍内，並且通過175。(：、1 小時的熱處理而熱硬化後有機成分的凝膠分率在10〜30重 量％的範圍内。 2.如申請專利範圍第1項所述的熱硬化型黏晶薄 膜’其中’酸值在4〜10 mgKOH/g的範圍内。 * 3.如申請專利範圍第1項或第2項所述的熱硬化型黏 ，薄膜’其是由熱硬化性樹脂與酸值在10〜40 mgKOH/g 範圍内的熱塑性樹脂形成。 4·如申請專利範圍第1項至第3項中任一項所述的熱 硬化型黏晶薄膜’其中，添加有熱硬化催化劑。 5.如申請專利範圍第丨項至第4項中任一項所述的熱 硬化型黏晶薄膜’其中，通過峨、H、時的熱處理而熱 硬化後剪切膠黏力為〇 2 MPa以上。 6·如申請專利範圍第以至以項中任—項所述的孰 ，化型黏晶_ ’其中，熱硬化前的12叱下的溶融黏度 在50〜1000 Pa.s的範圍内。 7.如申請專利範圍第！項至第6項中任一項 埶 硬化型黏晶薄膜，其中，通過175t、！小時的熱處理而^ 硬化後的260 C下的儲能彈性模量為1MPa以上。 46 201118145 \_ι i 8. —種切割/黏晶薄膜，其具有在切割薄膜上層疊有 如申請專利範圍第1項至第7項中任一項所述的熱硬化型 黏晶薄膜的結構。 9. 一種半導體裝置，其使用如申請專利範圍第1項至 第7項中任一項所述的熱硬化型黏晶薄膜或者如申請專利 範圍第8項所述的切割/黏晶薄膜而製造。 47VII. Patent application scope: L A thermosetting type adhesive crystal film for bonding and fixing a semiconductor component to an adherend, wherein the gel component of the organic component is thermally hardened by heat treatment at 12 Torr for 1 hour. The rate is in the range of 20% by weight or less and passes through 175. (:: 1 hour heat treatment and heat hardening, the gel fraction of the organic component is in the range of 10 to 30% by weight. 2. The thermosetting type microcrystalline film as described in claim 1 of the 'sour acid' The value is in the range of 4 to 10 mgKOH/g. * 3. The thermosetting type of the film as described in claim 1 or 2, which is made of a thermosetting resin and having an acid value of 10 to 40. The thermoplastic resin in the range of mg KOH / g is formed. The thermosetting type microcrystalline film according to any one of the above claims, wherein the thermosetting catalyst is added. The thermosetting type microcrystalline film according to any one of the items 4 to 4, wherein the shearing adhesive strength after hot-hardening by heat treatment of 峨, H, and time is 〇2 MPa or more. The scope of the patent application is as follows: the bismuth, the viscous viscous crystal _ ', wherein the melt viscosity at 12 前 before thermal hardening is in the range of 50 to 1000 Pa.s. Any of the 埶 hardening type viscous films of the range from item to item 6, wherein 175t, ! hours of heat is passed Rationally ^ The storage elastic modulus at 260 C after hardening is 1 MPa or more. 46 201118145 \_ι i 8. A dicing/mulet film having a laminate on the dicing film as disclosed in the first to the first The structure of the thermosetting type die-bonding film according to any one of the preceding claims, wherein the thermosetting type die-bonding film according to any one of claims 1 to 7 is used. Alternatively, it may be produced by cutting/bonding a film as described in claim 8.
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