TW201308417A - Die bonding film, dicing die bonding film, and semiconductor apparatus - Google Patents
Die bonding film, dicing die bonding film, and semiconductor apparatus Download PDFInfo
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Abstract
Description
本發明關於將例如半導體晶片等半導體元件膠粘固定到基板或引線框(lead frame)等被粘物上時使用的晶片接合薄膜。另外，本發明關於該晶片接合薄膜與切割薄膜層疊而成的切割/晶片接合薄膜。另外，本發明關於使用該晶片接合薄膜或該切割/晶片接合薄膜製造的半導體裝置。 The present invention relates to a wafer bonding film which is used when a semiconductor element such as a semiconductor wafer is adhered and fixed to an adherend such as a substrate or a lead frame. Further, the present invention relates to a dicing/wafer bonding film in which the wafer bonding film and the dicing film are laminated. Further, the present invention relates to a semiconductor device manufactured using the wafer bonding film or the dicing/wafer bonding film.
以往，在半導體裝置的製造過程中，對引線框和電極構件的半導體晶片的固著採用銀漿。所述固著處理通過在引線框的晶片墊(die pad)等上塗布漿狀膠粘劑，在其上搭載半導體晶片並使漿狀膠粘劑層固化來進行。 Conventionally, in the manufacturing process of a semiconductor device, silver paste is used for fixing the semiconductor wafer of the lead frame and the electrode member. The fixing treatment is performed by applying a paste-like adhesive to a die pad or the like of a lead frame, mounting a semiconductor wafer thereon, and curing the paste-like adhesive layer.
但是，漿狀膠粘劑由於其粘度行為或劣化等而在塗布量或塗布形狀等方面產生大的偏差。結果，形成的漿狀膠粘劑厚度不均勻，因此半導體晶片的固著強度缺乏可靠性。即，漿狀膠粘劑的塗布量不足時半導體晶片與電極構件之間的固著強度降低，在後續的引線接合(wire bonding)工序中半導體晶片剝離。另一方面，漿狀膠粘劑的塗布量過多時漿狀膠粘劑流延到半導體晶片上而產生特性不良，從而成品率和可靠性下降。這樣的固著處理中的問題，伴隨半導體晶片的大型化變得特別顯著。因此，需要頻繁地進行漿狀膠粘劑的塗布量的控制，從而給作業性或生產率帶來問題。 However, the slurry adhesive has a large variation in coating amount, coating shape, and the like due to its viscosity behavior, deterioration, and the like. As a result, the thickness of the formed paste adhesive is not uniform, and thus the fixing strength of the semiconductor wafer lacks reliability. That is, when the coating amount of the slurry adhesive is insufficient, the fixing strength between the semiconductor wafer and the electrode member is lowered, and the semiconductor wafer is peeled off in the subsequent wire bonding step. On the other hand, when the coating amount of the slurry adhesive is too large, the slurry adhesive is cast onto the semiconductor wafer to cause poor properties, so that the yield and reliability are lowered. The problem in such a fixing process is particularly remarkable as the size of the semiconductor wafer is increased. Therefore, it is necessary to frequently control the amount of application of the slurry adhesive, which causes problems in workability or productivity.
在該漿狀膠粘劑的塗布工序中，有將漿狀膠粘劑分別 塗布到引線框或形成的晶片上的方法。但是，在該方法中，漿狀膠粘劑層難以均勻化，另外漿狀膠粘劑的塗布需要特殊裝置和長時間。因此，提出了在切割工序中膠粘保持半導體晶片、並且在安裝(mount)工序中還提供所需的晶片固著用膠粘劑層的切割薄膜(例如，參考專利文獻1)。 In the coating process of the paste adhesive, the paste adhesive is separately A method of coating onto a leadframe or formed wafer. However, in this method, the slurry adhesive layer is difficult to homogenize, and the application of the paste adhesive requires special equipment and a long time. Therefore, a dicing film in which a semiconductor wafer is adhered and held in a dicing process and a desired adhesive layer for wafer fixing is provided in a mounting process has been proposed (for example, refer to Patent Document 1).
該切割薄膜是在支撐基材上以可以剝離的方式設置有膠粘劑層，在該膠粘劑層的保持下將半導體晶片切割後，將支撐基材拉伸而將形成的晶片與膠粘劑層一起剝離並將其分別回收，然後通過該膠粘劑層固著到引線框等被粘物上。此時，通常在膠粘劑層與被粘物之間存在空隙。以往，通過利用密封樹脂進行的密封工序中的熱或壓力使空隙消失。 The dicing film is provided with an adhesive layer on the support substrate in a peelable manner, and after the semiconductor wafer is cut by the adhesive layer, the support substrate is stretched to peel the formed wafer together with the adhesive layer and They are separately recovered and then fixed to the adherend such as a lead frame by the adhesive layer. At this time, there is usually a gap between the adhesive layer and the adherend. Conventionally, voids are eliminated by heat or pressure in a sealing process by a sealing resin.
另一方面，近年來在製造多個半導體晶片多段層疊而得到的半導體裝置，具有對半導體晶片進行引線接合的引線接合工序、使晶片接合薄膜熱固化的工序等所花費的時間增加的傾向。而且，長時間暴露於高溫下時，具有在晶片接合薄膜與被粘物的邊界處的氣泡(空隙)在密封工序中不消失的傾向。該空隙會造成半導體晶片從被粘物上剝離，從而存在缺乏膠粘可靠性的問題。 On the other hand, in recent years, in a semiconductor device in which a plurality of semiconductor wafers are stacked in a plurality of stages, the time required for the wire bonding step of wire bonding the semiconductor wafer and the step of thermally curing the wafer bonding film tends to increase. Further, when exposed to a high temperature for a long period of time, there is a tendency that bubbles (voids) at the boundary between the wafer bonding film and the adherend do not disappear in the sealing step. This void causes the semiconductor wafer to be peeled off from the adherend, so that there is a problem of lack of adhesive reliability.
專利文獻1：日本特開昭60-57642號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 60-57642
本發明鑒於前述問題而創立，其目的在於提供晶片接 合薄膜、切割/晶片接合薄膜、以及使用該晶片接合薄膜或該切割/晶片接合薄膜製造的半導體裝置，其即使在高溫下進行長時間處理的情況下也可以減少晶片接合薄膜與被粘物的邊界處空隙的產生，並且可以抑制回流焊接(reflow)工序中的剝離。 The present invention has been made in view of the foregoing problems, and an object thereof is to provide a wafer connection a film, a dicing/wafer bonding film, and a semiconductor device fabricated using the wafer bonding film or the dicing/wafer bonding film, which can reduce the wafer bonding film and the adherend even when subjected to long-term processing at a high temperature The generation of voids at the boundary and the peeling in the reflow process can be suppressed.
本申請發明人為了解決前述的問題，對晶片接合薄膜以及該晶片接合薄膜與切割薄膜層疊而成的切割/晶片接合薄膜進行了研究。結果發現，在高溫下處理晶片接合薄膜時，由於晶片接合薄膜中所含的熱固化樹脂成分劇烈地反應，因此在晶片接合薄膜與被粘物的邊界處的氣泡(空隙)在密封工序中不消失。而且，通過採用下述構成，抑制晶片接合薄膜中所含的熱固化樹脂成分的反應，由此可以在密封工序中使空隙消失，並且完成了本發明。 In order to solve the above problems, the inventors of the present invention have studied a wafer bonding film and a dicing/wafer bonding film in which the wafer bonding film and the dicing film are laminated. As a result, it has been found that when the wafer bonding film is processed at a high temperature, since the thermosetting resin component contained in the wafer bonding film reacts violently, bubbles (voids) at the boundary between the wafer bonding film and the adherend are not in the sealing process. disappear. In addition, by suppressing the reaction of the thermosetting resin component contained in the wafer bonding film by the following configuration, the voids can be eliminated in the sealing step, and the present invention has been completed.
即，本發明的晶片接合薄膜，其特徵在於，含有含腈基(nitrile group)熱固性丙烯酸共聚物(acrylic copolymer)和固化劑，使用差示量熱計(differential calorimeter)，以10℃/分鐘的升溫速度從25℃到300℃進行測定時的放熱量為10mJ/mg以下。 That is, the wafer bonding film of the present invention is characterized by containing a nitrile group-containing thermosetting acrylic copolymer and a curing agent, using a differential calorimeter at 10 ° C / min. The calorific value at the time of measurement of the temperature increase rate from 25 ° C to 300 ° C was 10 mJ / mg or less.
根據前述構成，使用差示量熱計，以10℃/分鐘的升溫速度從25℃到300℃進行測定時的放熱量為10mJ/mg以下，從而所述熱固性樹脂成分與所述固化劑的反應受到抑制。因此，可以抑制晶片接合薄膜與被粘物的邊界處產生空隙。結果，即使在高溫下進行長時間的處理的情況下，也可以減少晶片接合薄膜與被粘物的邊界處空隙的產生。 另外，根據前述構成，由於含有腈基，因此凝聚力上升。結果，可以抑制回流焊接工序中的剝離。即，根據前述構成，可以同時實現空隙的抑制和回流焊接工序中剝離的抑制。 According to the above configuration, the calorific value at the time of measurement from 25 ° C to 300 ° C at a temperature increase rate of 10 ° C /min is 10 mJ / mg or less by using a differential calorimeter, whereby the thermosetting resin component reacts with the curing agent. Suppressed. Therefore, it is possible to suppress the occurrence of voids at the boundary between the wafer bonding film and the adherend. As a result, even in the case where the treatment is performed for a long period of time at a high temperature, the occurrence of voids at the boundary between the wafer bonding film and the adherend can be reduced. Further, according to the above configuration, since the nitrile group is contained, the cohesive force increases. As a result, peeling in the reflow soldering process can be suppressed. That is, according to the above configuration, the suppression of the voids and the suppression of the peeling in the reflow soldering process can be simultaneously achieved.
在前述構成中，優選：以在175℃熱固化5小時後為基準，失重5重量%的溫度為280℃以上，在175℃熱固化5小時後的吸水率為1重量%以下。通過實現以在175℃熱固化5小時後為基準失重5重量%的溫度為280℃以上，以及在175℃熱固化5小時後的吸水率為1重量%以下，可以防止在回流焊接工序中以所述空隙為起點的剝離。另外，失重5重量%的溫度是指：將在175℃熱固化5小時後的晶片接合薄膜以規定的升溫速度(例如10℃/分鐘)加熱，晶片接合薄膜的重量減少5%時的溫度(熱重量法；TGA法)。另外，回流焊接工序是指，組裝半導體封裝後，使用焊料(solder)將其安裝到印刷佈線板等上時所經過的工序，通常是加熱到約260℃的工序。 In the above configuration, it is preferable that the temperature at which the weight loss is 5% by weight is 280 ° C or higher and the water absorption after heat curing at 175 ° C for 5 hours is 1% by weight or less based on the heat curing at 175 ° C for 5 hours. By achieving a water absorption rate of 280 ° C or higher after the heat curing at 175 ° C for 5 hours as a basis weight loss of 5% by weight, and a water absorption rate of 1% by weight or less after heat curing at 175 ° C for 5 hours, it is possible to prevent the reflow soldering process from being performed in the reflow soldering process. The void is a peeling of the starting point. Further, the temperature at which the weight loss is 5% by weight means a temperature at which the wafer bonded film after heat curing at 175 ° C for 5 hours is heated at a predetermined temperature increase rate (for example, 10 ° C / minute), and the weight of the wafer bonded film is reduced by 5% ( Thermogravimetry; TGA method). The reflow soldering step is a step that is performed when a semiconductor package is assembled and then mounted on a printed wiring board or the like using a solder, and is usually heated to a temperature of about 260 ° C.
在前述構成中，優選：在175℃熱固化5小時後的260℃下的拉伸儲能彈性模量為0.5MPa以上。在175℃熱固化5小時後的260℃下的拉伸儲能彈性模量為0.5MPa以上時，可以進一步防止回流焊接工序中以所述空隙為起點的剝離。 In the above configuration, it is preferable that the tensile storage elastic modulus at 260 ° C after heat curing at 175 ° C for 5 hours is 0.5 MPa or more. When the tensile storage elastic modulus at 260 ° C after heat curing at 175 ° C for 5 hours is 0.5 MPa or more, peeling starting from the void in the reflow soldering step can be further prevented.
在前述構成中，優選：設所述含腈基熱固性丙烯酸共聚物的重量為x、所述固化劑的重量為y時，重量比(x/y)為2以上且20以下。所述重量比(x/y)為2以上時，容 易使所述放熱量為10mJ/mg以下。另一方面，所述重量比(x/y)為20以下時，在進行回流焊接工序時容易賦予抵抗剝離的凝聚力。 In the above configuration, when the weight of the nitrile group-containing thermosetting acrylic copolymer is x and the weight of the curing agent is y, the weight ratio (x/y) is preferably 2 or more and 20 or less. When the weight ratio (x/y) is 2 or more, the capacity is The heat release amount is preferably 10 mJ/mg or less. On the other hand, when the weight ratio (x/y) is 20 or less, it is easy to impart a cohesive force against peeling during the reflow soldering process.
在前述構成中，優選：所述含腈基熱固性丙烯酸共聚物的重均分子量為50萬以上。所述含腈基熱固性丙烯酸共聚物的重均分子量為50萬以上時，在進行回流焊接工序時容易進一步賦予抵抗剝離的凝聚力。 In the above configuration, it is preferable that the nitrile group-containing thermosetting acrylic copolymer has a weight average molecular weight of 500,000 or more. When the weight average molecular weight of the nitrile group-containing thermosetting acrylic copolymer is 500,000 or more, it is easy to further impart a cohesive force against peeling during the reflow soldering step.
在前述構成中，優選：所述含腈基熱固性丙烯酸共聚物含有環氧基，並且環氧值(epoxy value)為0.1eq/kg以上且1eq/kg以下。所述環氧值為0.1eq/kg以上時，即使在熱固化後也可以得到高溫下的充分的彈性模量。另一方面，所述環氧值為1eq/kg以下時，可以進一步抑制與固化劑的反應。 In the above configuration, it is preferable that the nitrile group-containing thermosetting acrylic copolymer contains an epoxy group and has an epoxy value of 0.1 eq/kg or more and 1 eq/kg or less. When the epoxy value is 0.1 eq/kg or more, a sufficient elastic modulus at a high temperature can be obtained even after heat curing. On the other hand, when the epoxy value is 1 eq/kg or less, the reaction with the curing agent can be further suppressed.
在前述構成中，優選：所述固化劑具有酚羥基(phenolic hydroxyl group)。所述固化劑具有酚羥基時，可以通過與環氧基的反應進一步提高凝聚力。 In the above configuration, preferably, the curing agent has a phenolic hydroxyl group. When the curing agent has a phenolic hydroxyl group, the cohesive force can be further improved by the reaction with the epoxy group.
另外，為了解決前述課題，本發明的切割/晶片接合薄膜的特徵在於，前述的晶片接合薄膜層疊在切割薄膜上。 Further, in order to solve the above problems, the dicing/wafer bonding film of the present invention is characterized in that the above-described wafer bonding film is laminated on a dicing film.
在前述構成中，優選：所述晶片接合薄膜的熱固化前的25℃下的拉伸儲能彈性模量為1MPa以上且5GPa以下。所述晶片接合薄膜的熱固化前的25℃下的拉伸儲能彈性模量為1MPa以上時，與切割薄膜的剝離力適度，可以改善拾取性。另一方面，所述晶片接合薄膜的熱固化前的25℃下的拉伸儲能彈性模量為5GPa以下時，操作性優良。 In the above configuration, it is preferable that the tensile storage elastic modulus at 25 ° C before thermal curing of the wafer bonding film is 1 MPa or more and 5 GPa or less. When the tensile storage elastic modulus at 25 ° C before thermal curing of the wafer bonding film is 1 MPa or more, the peeling force with the dicing film is moderate, and the pickup property can be improved. On the other hand, when the tensile storage elastic modulus at 25 ° C before thermal curing of the wafer bonding film is 5 GPa or less, the handleability is excellent.
另外，為了解決前述課題，本發明的半導體裝置的特徵在於，使用前述的晶片接合薄膜或者切割/晶片接合薄膜來製造。 Further, in order to solve the above problems, the semiconductor device of the present invention is characterized in that it is manufactured by using the above-described wafer bonding film or dicing/wafer bonding film.
為讓本發明之上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。 The above described features and advantages of the present invention will be more apparent from the following description.
以下對於本發明的一個實施方式的切割/晶片接合薄膜進行說明。圖1是表示本發明的一個實施方式的切割/晶片接合薄膜的示意剖視圖。圖2是表示本發明的另一實施方式的切割/晶片接合薄膜的示意剖視圖。 Hereinafter, a dicing/wafer bonding film according to an embodiment of the present invention will be described. 1 is a schematic cross-sectional view showing a dicing/wafer bonding film according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a dicing/wafer bonding film according to another embodiment of the present invention.
如圖1所示，切割/晶片接合薄膜10具有在切割薄膜11上層疊有晶片接合薄膜3的構成。切割薄膜11通過在基材1上層疊粘合劑層2而構成，晶片接合薄膜3設置在該粘合劑層2上。另外，本發明中，也可以如圖2所示的切割/晶片接合薄膜12這樣僅在粘合劑層2的工件粘貼部分2a形成有晶片接合薄膜3’的構成。 As shown in FIG. 1, the dicing/wafer bonding film 10 has a structure in which a wafer bonding film 3 is laminated on a dicing film 11. The dicing film 11 is formed by laminating the pressure-sensitive adhesive layer 2 on the substrate 1, and the wafer bonding film 3 is provided on the pressure-sensitive adhesive layer 2. Further, in the present invention, as in the dicing/wafer bonding film 12 shown in Fig. 2, only the wafer bonding film 3' may be formed on the workpiece bonding portion 2a of the pressure-sensitive adhesive layer 2.
晶片接合薄膜3、3’僅包含膠粘劑層的單層，並且含有含腈基熱固性丙烯酸共聚物和固化劑。另外，本實施方式中，對於晶片接合薄膜3、3’僅包含膠粘劑層單層的情況進行說明，但是，本發明中，晶片接合薄膜3、3’的層疊結構沒有特別限制，例如，也可以為在芯材的單面或兩面形成有膠粘劑層的多層結構等結構。作為所述芯材，可以列舉：薄膜(例如，聚醯亞胺薄膜、聚酯薄膜、聚對苯 二甲酸乙二酯(polyethylene terephthalate)薄膜、聚2,6萘二甲酸乙二酯(polyethylene naphthalate)薄膜、聚碳酸酯(polycarbonate)薄膜等)、玻璃纖維或塑膠制不織纖維增強的樹脂基板、矽基板或玻璃基板等。 The wafer bonding film 3, 3' contains only a single layer of an adhesive layer, and contains a nitrile-containing thermosetting acrylic copolymer and a curing agent. In the present embodiment, the case where the wafer bonding films 3 and 3' include only a single layer of the adhesive layer will be described. However, in the present invention, the laminated structure of the die-bonding films 3 and 3' is not particularly limited, and for example, It is a structure of a multilayer structure in which an adhesive layer is formed on one side or both sides of a core material. As the core material, a film (for example, a polyimide film, a polyester film, a polyparaphenylene) can be cited. a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, a glass fiber or a plastic non-woven fiber reinforced resin substrate,矽 substrate, glass substrate, etc.
關於晶片接合薄膜3、3’，使用差示量熱計，以10℃/分鐘的升溫速度從25℃到300℃進行測定時的放熱量為10mJ/mg以下。所述放熱量優選為8mJ/mg以下，更優選5mJ/mg以下。另外，所述放熱量越小越優選，例如，為0.001mJ/mg以上。由於所述放熱量為10mJ/mg以下，因此可以抑制在晶片接合薄膜3、3’與被粘物6(參考圖3)的邊界處產生空隙。結果，即使在高溫下進行長時間處理的情況下，也可以減少晶片接合薄膜3、3’與被粘物的邊界處空隙的產生。作為將所述放熱量控制到10mJ/mg以下的方法，可以列舉：使熱固性丙烯酸共聚物與固化劑反應的方法、實質上不使用固化促進劑的方法等。 The wafer bonding films 3 and 3' were subjected to a calorimeter at a temperature increase rate of 10 ° C /min from 25 ° C to 300 ° C using a differential calorimeter to have an amount of heat generation of 10 mJ / mg or less. The heat release amount is preferably 8 mJ/mg or less, more preferably 5 mJ/mg or less. Further, the smaller the heat release amount, the more preferable, and it is, for example, 0.001 mJ/mg or more. Since the amount of heat generation is 10 mJ/mg or less, it is possible to suppress the occurrence of voids at the boundary between the wafer bonding films 3, 3' and the adherend 6 (refer to Fig. 3). As a result, even in the case where the treatment is performed for a long period of time at a high temperature, the generation of voids at the boundary between the wafer bonding films 3, 3' and the adherend can be reduced. The method of controlling the amount of heat release to 10 mJ/mg or less includes a method of reacting a thermosetting acrylic copolymer with a curing agent, a method of substantially not using a curing accelerator, and the like.
關於晶片接合薄膜3、3’，以在175℃熱固化5小時後為基準，失重5重量%的溫度優選為280℃以上，更優選290℃以上，進一步優選300℃以上。所述失重溫度越高越優選，例如，為450℃以下。 The temperature at which the wafer bonding films 3 and 3' are thermally cured at 175 ° C for 5 hours is preferably 280 ° C or higher, more preferably 290 ° C or higher, and still more preferably 300 ° C or higher. The higher the weight loss temperature, the more preferable, for example, 450 ° C or lower.
另外，關於晶片接合薄膜3、3’，在175℃熱固化5小時後的吸水率優選為1重量%以下，更優選0.9重量%以下，進一步優選0.8重量%以下。所述吸水率越小越好，例如，為0.05重量%以上。所述吸水率可以通過實施例記載的方法得到。 Further, the water absorption ratio of the wafer bonding films 3 and 3' after heat curing at 175 ° C for 5 hours is preferably 1% by weight or less, more preferably 0.9% by weight or less, still more preferably 0.8% by weight or less. The smaller the water absorption rate, the better, for example, 0.05% by weight or more. The water absorption rate can be obtained by the method described in the examples.
晶片接合薄膜3、3’，通過實現以在175℃熱固化5小時後為基準失重5重量%的溫度為280℃以上，以及在175℃熱固化5小時後的吸水率為1重量%以下，由此可以防止回流焊接工序中以所述空隙為起點的剝離。 The wafer bonding films 3 and 3' have a water absorption rate of 280° C. or more after the heat curing at 175° C. for 5 hours, and a water absorption rate of 1% by weight or less after heat curing at 175° C. for 5 hours. Thereby, peeling starting from the said gap in a reflow soldering process can be prevented.
關於晶片接合薄膜3、3’，在175℃熱固化5小時後的260℃下的拉伸儲能彈性模量優選為0.5MPa以上，更優選0.55MPa以上且3000MPa以下，進一步優選0.6MPa以上且2000MPa以下。在175℃熱固化5小時後的260℃下的拉伸儲能彈性模量為0.5MPa以上時，可以進一步防止回流焊接工序中以所述空隙為起點的剝離。 The tensile storage elastic modulus at 260 ° C of the wafer bonding films 3 and 3' after heat curing at 175 ° C for 5 hours is preferably 0.5 MPa or more, more preferably 0.55 MPa or more and 3,000 MPa or less, further preferably 0.6 MPa or more. Below 2000MPa. When the tensile storage elastic modulus at 260 ° C after heat curing at 175 ° C for 5 hours is 0.5 MPa or more, peeling starting from the void in the reflow soldering step can be further prevented.
關於晶片接合薄膜3、3’，當設所述含腈基熱固性丙烯酸共聚物的重量為x、所述固化劑的重量為y時，重量比(x/y)優選為2以上且20以下，更優選2.3以上且15.6以下，進一步優選3以上且11.5以下。所述重量比(x/y)為2以上時，所述放熱量容易為10mJ/mg以下。另一方面，所述重量比(x/y)為20以下時，在進行回流焊接工序時容易賦予抵抗剝離的凝聚力。 In the wafer bonding films 3 and 3', when the weight of the nitrile group-containing thermosetting acrylic copolymer is x and the weight of the curing agent is y, the weight ratio (x/y) is preferably 2 or more and 20 or less. It is more preferably 2.3 or more and 15.6 or less, still more preferably 3 or more and 11.5 or less. When the weight ratio (x/y) is 2 or more, the amount of heat generation is easily 10 mJ/mg or less. On the other hand, when the weight ratio (x/y) is 20 or less, it is easy to impart a cohesive force against peeling during the reflow soldering process.
所述含腈基熱固性丙烯酸共聚物，優選重均分子量為50萬以上，更優選80萬以上且200萬以下。所述含腈基熱固性丙烯酸共聚物的重均分子量為50萬以上時，在進行回流焊接工序時容易進一步賦予抵抗剝離的凝聚力。 The nitrile group-containing thermosetting acrylic copolymer preferably has a weight average molecular weight of 500,000 or more, more preferably 800,000 or more and 2,000,000 or less. When the weight average molecular weight of the nitrile group-containing thermosetting acrylic copolymer is 500,000 or more, it is easy to further impart a cohesive force against peeling during the reflow soldering step.
所述含腈基熱固性丙烯酸共聚物，優選含有環氧基，並且環氧值為0.1eq/kg以上且1eq/kg以下，更優選0.15eq/kg以上且0.8eq/kg以下，進一步優選0.2eq/kg以上 且0.6eq/kg以下。所述環氧值為0.1eq/kg以上時，即使在熱固化後也可以得到高溫下的充分的彈性模量。另一方面，所述環氧值為1eq/kg以下時，可以進一步抑制與固化劑的反應。 The nitrile group-containing thermosetting acrylic copolymer preferably contains an epoxy group and has an epoxy value of 0.1 eq/kg or more and 1 eq/kg or less, more preferably 0.15 eq/kg or more and 0.8 eq/kg or less, further preferably 0.2 eq. /kg or more And 0.6eq/kg or less. When the epoxy value is 0.1 eq/kg or more, a sufficient elastic modulus at a high temperature can be obtained even after heat curing. On the other hand, when the epoxy value is 1 eq/kg or less, the reaction with the curing agent can be further suppressed.
另外，所述含腈基熱固性丙烯酸共聚物的玻璃轉移點(glass-transition point)(Tg)，只要可以在晶片接合薄膜3、3’與被粘物(例如晶片)之間得到適度的膠粘性，則沒有特別限制，優選-15℃以上且40℃以下，更優選-10℃以上且35℃以下。這是因為：通過設定為-15℃以上，可以使對半導體晶片的膠粘性充分。另外，這是因為：通過設定為40℃以下，可以抑制發粘(tack)，提高操作性。另外，玻璃轉移點可以通過實施例所述的方法得到。 Further, the glass-transition point (Tg) of the nitrile-containing thermosetting acrylic copolymer is such that a moderate adhesion can be obtained between the wafer bonding film 3, 3' and an adherend such as a wafer. The nature is not particularly limited, but is preferably -15 ° C or higher and 40 ° C or lower, more preferably -10 ° C or higher and 35 ° C or lower. This is because the adhesion to the semiconductor wafer can be made sufficient by setting it to -15 ° C or higher. In addition, this is because by setting it to 40 degreeC or less, it can suppress a tack, and can improve operability. Alternatively, the glass transition point can be obtained by the method described in the examples.
作為所述含腈基熱固性丙烯酸聚合物，沒有特別限制，可以列舉：在以一種或兩種以上具有直鏈或支鏈烷基的丙烯酸或甲基丙烯酸的酯作為成分的聚合物(共聚物)中添加具有熱固性官能基(functional group)的單體而得到的聚合物。 The nitrile group-containing thermosetting acrylic polymer is not particularly limited, and examples thereof include a polymer (copolymer) containing one or two or more esters of acrylic acid or methacrylic acid having a linear or branched alkyl group as a component. A polymer obtained by adding a monomer having a thermosetting functional group.
作為所述烷基，可以列舉例如：甲基、乙基、丙基、異丙基、正丁基、叔丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基或二十烷基等。 Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl or eicosyl and the like.
作為所述含腈基熱固性丙烯酸聚合物的製造方法，沒有特別限制，可以列舉例如：將含腈基單體與丙烯酸類單 體和具有熱固性官能基的單體進行共聚的方法。另外，也可以列舉：在含腈基單體與丙烯酸類單體的共聚物中添加具有熱固性官能基的單體的方法。另外，作為另一方法，可以列舉：將丙烯酸類單體與具有第一官能基的單體共聚後，使具有能夠與所述第一官能基反應的官能基以及腈基的化合物在保持腈基的狀況下進行縮合或加成反應，然後添加具有熱固性官能基的方法。 The method for producing the nitrile group-containing thermosetting acrylic polymer is not particularly limited, and examples thereof include a nitrile group-containing monomer and an acrylic sheet. A method of copolymerizing a body and a monomer having a thermosetting functional group. Further, a method of adding a monomer having a thermosetting functional group to a copolymer of a nitrile group-containing monomer and an acrylic monomer may also be mentioned. Further, as another method, after copolymerizing an acrylic monomer with a monomer having a first functional group, a compound having a functional group capable of reacting with the first functional group and a nitrile group is maintained at a nitrile group. The condensation or addition reaction is carried out under the conditions, and then a method having a thermosetting functional group is added.
另外，所述含腈基熱固性丙烯酸聚合物可以為以腈基、熱固性官能基和一種或兩種以上具有直鏈或支鏈烷基的丙烯酸或甲基丙烯酸的酯作為成分的聚合物(共聚物)。此時，作為所述含腈基熱固性丙烯酸聚合物的製造方法，沒有特別限制，可以列舉例如：將含腈基單體、具有熱固性官能基的單體和丙烯酸類單體共聚的方法。 Further, the nitrile group-containing thermosetting acrylic polymer may be a polymer (copolymer) having a nitrile group, a thermosetting functional group, and one or two or more esters of acrylic or methacrylic acid having a linear or branched alkyl group as a component. ). In this case, the method for producing the nitrile group-containing thermosetting acrylic polymer is not particularly limited, and examples thereof include a method of copolymerizing a nitrile group-containing monomer, a monomer having a thermosetting functional group, and an acrylic monomer.
另外，作為所述含腈基熱固性丙烯酸聚合物的製造方法，可以列舉：(A)在將具有熱固性官能基的單體、丙烯酸類單體和具有第一官能基的單體共聚後，在保持腈基的狀況下使具有能夠與所述第一官能基反應的官能基及腈基的化合物縮合或加成的方法；(B)在將具有腈基的單體、丙烯酸類單體和具有第二官能基的單體共聚後，在保持熱固性官能基的狀況下使具有能夠與所述第二官能基反應的官能基及熱固性官能基的化合物縮合或加成的方法；(C)在將丙烯酸類單體、具有第二官能基的單體和 具有第一官能基的單體(共)聚合後，在保持熱固性官能基的狀況下使具有能夠與所述第二官能基反應的官能基及熱固性官能基的化合物縮合或加成並且在保持腈基的狀況下使具有能夠與所述第一官能基反應的官能基及腈基的化合物縮合或加成的方法。 Further, as a method for producing the nitrile group-containing thermosetting acrylic polymer, (A) after copolymerizing a monomer having a thermosetting functional group, an acrylic monomer, and a monomer having a first functional group, a method of condensing or adding a compound having a functional group capable of reacting with the first functional group and a nitrile group in the case of a nitrile group; (B) a monomer having a nitrile group, an acrylic monomer, and a a method of condensing or adding a compound having a functional group capable of reacting with the second functional group and a thermosetting functional group after copolymerization of a difunctional monomer; (C) a method of condensing acrylic acid Monomers, monomers having a second functional group, and After (co)polymerization of a monomer having a first functional group, a compound having a functional group capable of reacting with the second functional group and a thermosetting functional group is condensed or added while maintaining a thermosetting functional group and maintaining a nitrile A method of condensing or adding a compound having a functional group capable of reacting with the first functional group and a nitrile group in the case of a group.
作為所述含腈基單體，可以列舉(甲基)丙烯腈、氰基苯乙烯等。 Examples of the nitrile group-containing monomer include (meth)acrylonitrile and cyanostyrene.
作為所述具有熱固性官能基的單體，可以適當使用例如：具有縮水甘油基(glycidyl)並且具有可共聚的烯性不飽和鍵的單體，可以列舉例如：丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯等含縮水甘油基單體。另外，作為所述具有熱固性官能基的單體的其他例子，可以列舉馬來醯亞胺丙烯酸酯。 As the monomer having a thermosetting functional group, for example, a monomer having a glycidyl group and having a copolymerizable ethylenically unsaturated bond can be suitably used, and examples thereof include glycidyl acrylate and methacrylic acid shrinkage. A glycidyl group-containing monomer such as a glyceride. Further, as another example of the monomer having a thermosetting functional group, maleic imide acrylate may be mentioned.
構成所述含腈基熱固性丙烯酸聚合物的單體的混合比率，優選考慮玻璃轉移溫度、環氧值進行調節。特別地，作為所述含腈基熱固性丙烯酸聚合物中所述具有熱固性官能基的單體的含量，從玻璃轉移溫度、環氧值的觀點考慮，優選1~20莫耳%，更優選1~15莫耳%，進一步優選1~10莫耳%。所述含腈基熱固性丙烯酸聚合物的聚合方法沒有特別限制，可以採用例如溶液聚合法、本體聚合法、懸浮聚合法、乳液聚合法等現有公知的方法。 The mixing ratio of the monomers constituting the nitrile group-containing thermosetting acrylic polymer is preferably adjusted in consideration of the glass transition temperature and the epoxy value. In particular, the content of the monomer having a thermosetting functional group in the nitrile group-containing thermosetting acrylic polymer is preferably 1 to 20 mol%, more preferably 1 to 2, from the viewpoint of glass transition temperature and epoxy value. 15% by mole, further preferably 1 to 10% by mole. The polymerization method of the nitrile group-containing thermosetting acrylic polymer is not particularly limited, and a conventionally known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method can be employed.
作為形成所述含腈基熱固性丙烯酸聚合物的其他單體，沒有特別限制，可以列舉例如：含羧基單體，如丙烯酸、甲基丙烯酸、丙烯酸羧乙酯(carboxyethyl acrylate)、 丙烯酸羧戊酯、衣康酸、馬來酸、富馬酸或巴豆酸等；酸酐單體，如馬來酸酐或衣康酸酐等；含羥基單體，如(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、(甲基)丙烯酸-6-羥基己酯、(甲基)丙烯酸-8-羥基辛酯、(甲基)丙烯酸-10-羥基癸酯、(甲基)丙烯酸-12-羥基月桂酯或甲基丙烯酸(4-羥甲基環己基)甲酯等；含磺酸基單體，如苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等；含磷酸基單體，如丙烯醯磷酸2-羥基乙酯等；或者苯乙烯單體。 The other monomer forming the nitrile group-containing thermosetting acrylic polymer is not particularly limited, and examples thereof include a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, or carboxyethyl acrylate. Carboxymethyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid; anhydride monomers such as maleic anhydride or itaconic anhydride; hydroxyl-containing monomers such as 2-hydroxyl (meth)acrylate Ethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate , (meth)acrylic acid 10-hydroxydecyl ester, (meth)acrylic acid-12-hydroxylauryl ester or methacrylic acid (4-hydroxymethylcyclohexyl) methyl ester, etc.; sulfonic acid group-containing monomer, such as benzene Ethylene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamido-2-methylpropane sulfonic acid, (meth) acrylamidopropane sulfonic acid, sulfopropyl (meth) acrylate or ( Methyl) propylene decyl naphthalene sulfonic acid or the like; a phosphoric acid group-containing monomer such as 2-hydroxyethyl acrylate or the like; or a styrene monomer.
所述固化劑，只要作為所述含腈基熱固性丙烯酸聚合物的固化劑起作用則沒有特別限制，特別地，與環氧基或縮水甘油基反應時，優選含有羧基、酚羥基(phenolic hydroxyl group)、氨(amino)基、酸酐，其中，優選酚羥基。可以列舉例如：苯酚酚醛清漆樹脂、苯酚聯苯(biphenyl phenol)樹脂、苯酚芳烷基(phenol aralkyl)樹脂、甲酚酚醛清漆樹脂、叔丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚醛樹脂、甲階(resol)酚醛樹脂型酚醛樹脂等酚醛樹脂、聚對羥基苯乙烯等聚羥基苯乙烯等、茜素(alizarin)、水楊酸(salicylic acid)等雙官能以上的低分子材料、通過熱而出現酚羥基的苯並噁嗪(benzoxazine)等。這些固化劑可以單獨使用或者兩種 以上組合使用。 The curing agent is not particularly limited as long as it acts as a curing agent for the nitrile-containing thermosetting acrylic polymer, and particularly, when reacting with an epoxy group or a glycidyl group, it preferably contains a carboxyl group and a phenolic hydroxyl group. ), an amino group, an acid anhydride, of which a phenolic hydroxyl group is preferred. Examples thereof include a phenol novolak resin, a phenol biphenyl phenol resin, a phenol aralkyl resin, a cresol novolak resin, a t-butyl phenol novolak resin, and a nonylphenol novolak resin. A phenol resin such as a varnish type phenol resin, a resol phenol resin type phenol resin, a polyhydroxy styrene such as polyparaxyl styrene, or the like having a difunctional or higher such as alizalin or salicylic acid. A molecular material, a benzoxazine or the like which exhibits a phenolic hydroxyl group by heat. These curing agents can be used alone or in two The above combination is used.
所述固化劑的重均分子量沒有特別限制，優選在100~3000的範圍內，更優選在150~2000的範圍內。重均分子量為100以上時，可以抑制固化中的揮發，抑制空隙的產生。另一方面，重均分子量為3000以下時，可以防止成為高粘度，可以改善晶片接合薄膜製作時的作業性。 The weight average molecular weight of the curing agent is not particularly limited, but is preferably in the range of from 100 to 3,000, more preferably in the range of from 150 to 2,000. When the weight average molecular weight is 100 or more, volatilization during curing can be suppressed, and generation of voids can be suppressed. On the other hand, when the weight average molecular weight is 3,000 or less, high viscosity can be prevented, and workability at the time of production of a wafer bonded film can be improved.
另外，晶片接合薄膜3、3’中，根據其用途可以適當配合填料。填料的配合可以賦予導電性或提高導熱性、調節彈性模量等。作為所述填料，可以列舉無機填料和有機填料，從提高操作性、提高熱電導性、調節熔融粘度、賦予觸變性等特性的觀點考慮，優選無機填料。作為所述無機填料，沒有特別限制，可以列舉例如：氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、矽酸鈣、矽酸鎂、氧化鈣、氧化鎂、氧化鋁、氮化鋁、硼酸鋁晶須、氮化硼、結晶二氧化矽、非晶二氧化矽等。這些填料可以單獨使用或者兩種以上組合使用。從提高熱電導性的觀點考慮，優選氧化鋁、氮化鋁、氮化硼、結晶二氧化矽、非晶二氧化矽。另外，從上述各特性平衡良好的觀點考慮，優選結晶二氧化矽或非晶二氧化矽。另外，為了賦予導電性、提高熱電導性等目的，也可以使用導電性物質(導電填料)作為無機填料。作為導電填料，可以列舉將銀、鋁、金、銅、鎳、導電性合金等形成為球狀、針狀、薄片狀而得到的金屬粉、氧化鋁等金屬氧化物、無定形炭黑、石墨等。 Further, in the wafer bonding films 3, 3', a filler may be appropriately blended depending on the application. The blending of the filler can impart conductivity or improve thermal conductivity, adjust elastic modulus, and the like. Examples of the filler include an inorganic filler and an organic filler, and an inorganic filler is preferred from the viewpoint of improving workability, improving thermoelectric conductivity, adjusting melt viscosity, and imparting characteristics such as thixotropy. The inorganic filler is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, and boric acid. Aluminum whiskers, boron nitride, crystalline cerium oxide, amorphous cerium oxide, and the like. These fillers may be used singly or in combination of two or more. From the viewpoint of improving thermal conductivity, alumina, aluminum nitride, boron nitride, crystalline cerium oxide, and amorphous cerium oxide are preferable. Further, from the viewpoint of a good balance of the above characteristics, crystalline ceria or amorphous ceria is preferred. Further, in order to impart conductivity, improve thermal conductivity, and the like, a conductive material (conductive filler) may be used as the inorganic filler. Examples of the conductive filler include metal powder obtained by forming silver, aluminum, gold, copper, nickel, or a conductive alloy into a spherical shape, a needle shape, or a sheet shape, a metal oxide such as alumina, amorphous carbon black, and graphite. Wait.
所述填料的平均粒徑優選為0.005~10μm，更優選 0.001~1μm。這是因為：通過將所述填料的平均粒徑設定為0.005μm以上，可以改善對被粘物的潤濕性以及膠粘性。另外，通過設定為10μm以下，可以充分實現用於賦予上述各特性而加入的填料的效果，並且可以確保耐熱性。另外，填料的平均粒徑例如為通過光度式粒度分佈計(HORIBA制，裝置名：LA-910)求出的值。 The average particle diameter of the filler is preferably 0.005 to 10 μm, more preferably 0.001~1μm. This is because the wettability to the adherend and the tackiness can be improved by setting the average particle diameter of the filler to 0.005 μm or more. In addition, by setting it to 10 μm or less, the effect of the filler added for imparting the above respective characteristics can be sufficiently achieved, and heat resistance can be ensured. Further, the average particle diameter of the filler is, for example, a value obtained by a photometric particle size distribution meter (manufactured by HORIBA, device name: LA-910).
所述填料的配合量，相對於晶片接合薄膜組合物(構成晶片接合薄膜的樹脂固體成分)整體優選為0~60重量%，更優選0~50重量%。 The blending amount of the filler is preferably 0 to 60% by weight, and more preferably 0 to 50% by weight based on the entire wafer bonding film composition (resin solid content constituting the wafer bonding film).
另外，晶片接合薄膜3、3’中，除了所述填料以外，根據需要還可以適當配合其他添加劑。作為其他添加劑，可以列舉例如：阻燃劑、矽烷偶聯劑或離子捕獲劑等。作為所述阻燃劑，可以列舉例如：三氧化二銻(antimony trioxide)、五氧化二銻、溴化環氧樹脂等。這些阻燃劑可以單獨使用或者兩種以上組合使用。作為所述矽烷偶聯劑，可以列舉例如：β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油基氧基丙基三甲氧基矽烷(γ-glycidoxypropyltrimethoxysilane)、γ-縮水甘油基氧基丙基甲基二乙氧基矽烷(γ-glycidoxypropylmethyldiethoxysilane)等。這些矽烷偶聯劑可以單獨使用或者兩種以上組合使用。作為所述離子捕獲劑，可以列舉例如：水滑石(hydrotalcite)類、氫氧化鉍等。這些離子捕獲劑可以單獨使用或者兩種以上組合使用。 Further, in the wafer bonding films 3, 3', in addition to the above filler, other additives may be appropriately blended as needed. Examples of other additives include a flame retardant, a decane coupling agent, an ion trapping agent, and the like. Examples of the flame retardant include an antimony trioxide, a tantalum pentoxide, a brominated epoxy resin, and the like. These flame retardants may be used singly or in combination of two or more. Examples of the decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Γ-glycidoxypropylmethyldiethoxysilane or the like. These decane coupling agents may be used singly or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and barium hydroxide. These ion trapping agents may be used singly or in combination of two or more.
晶片接合薄膜3、3’的厚度(層疊體的情況下為總厚度)沒有特別限制，例如，可以從5~100μm的範圍內選擇，優選5~50μm。 The thickness of the wafer bonded films 3, 3' (the total thickness in the case of a laminate) is not particularly limited, and may be, for example, selected from the range of 5 to 100 μm, preferably 5 to 50 μm.
所述切割/晶片接合薄膜10、12的晶片接合薄膜3、3’，優選由隔片進行保護(未圖示)。隔片具有在供給實用之前作為保護晶片接合薄膜3、3’的保護材料的功能。另外，隔片也可以作為將晶片接合薄膜3、3’向粘合劑層2轉印時的支撐基材使用。隔片在向切割/晶片接合薄膜的晶片接合薄膜3、3’上粘貼工件時剝離。作為隔片，可以使用聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、通過含氟型剝離劑、長鏈烷基丙烯酸酯型剝離劑等剝離劑進行表面塗布後的塑膠薄膜、紙等。 The wafer bonding films 3, 3' of the dicing/wafer bonding films 10, 12 are preferably protected by a spacer (not shown). The separator has a function as a protective material for protecting the wafer bonding films 3, 3' before being supplied for practical use. Further, the separator may be used as a supporting substrate when the wafer bonding films 3, 3' are transferred to the pressure-sensitive adhesive layer 2. The separator is peeled off when the workpiece is pasted onto the wafer bonding film 3, 3' of the dicing/wafer bonding film. As the separator, polyethylene terephthalate (PET), polyethylene, polypropylene, 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. , paper, etc.
所述基材1具有紫外線透射性，並且作為切割/晶片接合薄膜10、12的強度母體。可以列舉例如：聚烯烴如低密度聚乙烯、線性聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等、乙烯-乙酸乙烯酯共聚物、離聚物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨酯、聚酯如聚對苯二甲酸乙二酯、聚2,6萘二甲酸乙二酯等、聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、含氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素類樹脂、聚矽氧烷樹脂、金 屬(箔)、紙等。 The substrate 1 has ultraviolet transmittance and serves as a strength matrix for the dicing/wafer bonding films 10, 12. For example, polyolefins such as low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutylene Alkene, polymethylpentene, etc., ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating) copolymer, ethylene -butene copolymer, ethylene-hexene copolymer, polyurethane, polyester such as polyethylene terephthalate, polyethylene 2,6 naphthalate, etc., polycarbonate, polyimine, polyether Ether ketone, polyimide, polyether oximine, polyamine, wholly aromatic polyamine, polyphenylene sulfide, aromatic polyamine (paper), glass, glass cloth, fluorine resin, polychlorinated Ethylene, polyvinylidene chloride, cellulose resin, polyoxyalkylene resin, gold Genus (foil), paper, etc.
另外，作為基材1的材料，可以列舉前述樹脂的交聯體等聚合物。所述塑膠薄膜可以不拉伸而使用，也可以根據需要進行單軸或雙軸拉伸處理後使用。利用通過拉伸處理等而賦予了熱收縮性的樹脂片，通過在切割後使該基材1熱收縮，可以減小粘合劑層2與晶片接合薄膜3、3’的膠粘面積，從而可以容易地回收半導體晶片(半導體元件)。 In addition, as a material of the base material 1, a polymer such as a crosslinked body of the above resin may be mentioned. The plastic film may be used without stretching, or may be used after uniaxial or biaxial stretching treatment as needed. By using a resin sheet to which heat shrinkability is imparted by a stretching treatment or the like, by thermally shrinking the substrate 1 after dicing, the adhesive area of the pressure-sensitive adhesive layer 2 and the wafer bonding films 3 and 3' can be reduced, thereby The semiconductor wafer (semiconductor element) can be easily recovered.
為了提高與鄰接層的粘附性、保持性等，基材1的表面可以實施慣用的表面處理，例如，鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、電離射線處理等化學或物理處理、利用底塗劑(例如後述的粘合物質)的塗布處理。所述基材1可以適當地選擇使用同種或不同種類的材料，根據需要也可以使用將數種材料共混後的材料。 In order to improve the adhesion to the adjacent layer, the retention, and the like, the surface of the substrate 1 may be subjected to a conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, or the like. A coating treatment using a primer (for example, a binder described later). The substrate 1 may be appropriately selected from the same or different kinds of materials, and a material obtained by blending several materials may be used as needed.
基材1的厚度沒有特別限制，可以適當確定，一般為約5μm~約200μm。 The thickness of the substrate 1 is not particularly limited and can be appropriately determined, and is generally from about 5 μm to about 200 μm.
作為粘合劑層2的形成中使用的粘合劑沒有特別限制，可以使用例如丙烯酸類粘合劑、橡膠類粘合劑等一般的壓敏粘合劑。作為所述壓敏粘合劑，從半導體晶片或玻璃等避忌污染的電子部件的利用超純水或醇類等有機溶劑的清潔洗滌性等的觀點考慮，優選以丙烯酸類聚合物為基礎聚合物的丙烯酸類粘合劑。 The binder used for the formation of the pressure-sensitive adhesive layer 2 is not particularly limited, and a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive can be used. As the pressure-sensitive adhesive, it is preferable to use an acrylic polymer as a base polymer from the viewpoint of cleaning and washing property of an organic solvent such as ultrapure water or alcohol such as a semiconductor wafer or glass. Acrylic adhesive.
作為所述丙烯酸類聚合物，可以列舉例如：使用(甲基)丙烯酸烷基酯(例如，甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、仲丁酯、叔丁酯、戊酯、異戊酯、己酯、 庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷酯、十二烷酯、十三烷酯、十四烷酯、十六烷酯、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)及(甲基)丙烯酸環烷酯(例如，環戊酯、環己酯等)中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/或甲基丙烯酸酯，本發明的(甲基)全部表示相同的含義。 As the acrylic polymer, for example, an alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl) can be used. Ester, amyl ester, isoamyl ester, hexyl ester, Heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, decyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, tetradecyl ester, hexadecane a linear or branched alkyl ester of an alkyl group such as an ester, octadecyl ester or an eicosyl ester having 1 to 30 carbon atoms, particularly a carbon number of 4 to 18, and a cycloalkyl (meth)acrylate. One or two or more of (for example, cyclopentyl ester, cyclohexyl ester, etc.), an acrylic polymer or the like as a monomer component. Further, (meth) acrylate means acrylate and/or methacrylate, and (meth) of the present invention all means the same meaning.
為了改善凝聚力、耐熱性等，所述丙烯酸類聚合物根據需要可以含有與能夠同所述(甲基)丙烯酸烷基酯或環烷酯共聚的其他單體成分對應的單元。作為這樣的單體成分，可以列舉例如：含羧基單體，如丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸等；酸酐單體，如馬來酸酐、衣康酸酐等；含羥基單體，如(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥甲基環己基)甲酯等；含磺酸基單體，如苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺基-2-甲基丙磺酸、(甲基)丙烯醯胺基丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧萘磺酸等；含磷酸基單體，如丙烯醯磷酸-2-羥基乙酯等；丙烯醯胺、丙烯腈等。這些可共聚單體成分可以使用一種或兩種以 上。這些可共聚單體的使用量優選為全部單體成分的40重量%以下。 In order to improve cohesive force, heat resistance, and the like, the acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, as needed. As such a monomer component, for example, a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and rich may be mentioned. Horse acid, crotonic acid, etc.; anhydride monomers such as maleic anhydride, itaconic anhydride, etc.; hydroxyl-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (meth)acrylic acid 12 -hydroxylauryl ester, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc.; sulfonic acid group-containing monomer such as styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamide Benzyl-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxynaphthalene sulfonic acid, etc.; Acrylphosphonium phosphate 2-hydroxyethyl ester or the like; acrylamide, acrylonitrile, and the like. These copolymerizable monomer components can be used in one or two on. The amount of these copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.
另外，所述丙烯酸類聚合物為了進行交聯根據需要也可以含有多官能單體等作為共聚用單體成分。作為這樣的多官能單體，可以列舉例如：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯等。這些多官能單體也可以使用一種或兩種以上。多官能單體的使用量從粘合特性等觀點考慮優選為全部單體成分的30重量%以下。 Further, the acrylic polymer may contain a polyfunctional monomer or the like as a monomer component for copolymerization as needed in order to carry out crosslinking. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and new Pentandiol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, and the like. These polyfunctional monomers may also be used alone or in combination of two or more. The amount of use of the polyfunctional monomer is preferably 30% by weight or less based on the total of the monomer components from the viewpoint of adhesion properties and the like.
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的混合物聚合來得到。聚合可以通過溶液聚合、乳液聚合、本體聚合、懸浮聚合等任意方式進行。從防止對潔淨被粘物的污染等觀點考慮，優選低分子量物質的含量少的丙烯酸類聚合物。從該點考慮，丙烯酸類聚合物的數均分子量優選為約30萬以上，更優選約40萬~約300萬。 The acrylic polymer can be obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can be carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization or the like. From the viewpoint of preventing contamination of a clean adherend, etc., an acrylic polymer having a small content of a low molecular weight substance is preferable. From this point of view, the number average molecular weight of the acrylic polymer is preferably about 300,000 or more, and more preferably about 400,000 to about 3,000,000.
另外，為了提高作為基礎聚合物的丙烯酸類聚合物等的數均分子量，所述粘合劑中也可以適當採用外部交聯劑。外部交聯方法的具體手段可以列舉：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， 其使用量根據與應交聯的基礎聚合物的平衡以及作為粘合劑的使用用途而適當確定。一般而言，相對於所述基礎聚合物100重量份優選配合約5重量份以下，更優選配合0.1~5重量份。另外，根據需要，在粘合劑中除前述成分以外也可以使用以往已知的各種增粘劑、抗老化劑等添加劑。 Further, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used in the binder. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine crosslinking agent, and reacting the same. When using an external cross-linking agent, The amount thereof to be used is appropriately determined depending on the balance with the base polymer to be crosslinked and the use as a binder. In general, it is preferably blended in an amount of about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, if necessary, in addition to the above-described components, additives such as various tackifiers and anti-aging agents known in the prior art may be used.
粘合劑層2可以由輻射線固化型粘合劑形成。輻射線固化型粘合劑可以通過紫外線等輻射線的照射使交聯度增大從而容易降低其粘合力，通過僅對圖2所示的粘合劑層2的與工件粘貼部分對應的部分2a照射輻射線，可以設置與其他部分2b的粘合力之差。 The adhesive layer 2 may be formed of a radiation curable adhesive. The radiation-curable adhesive can be made to increase the degree of crosslinking by irradiation with radiation such as ultraviolet rays, thereby easily reducing the adhesion thereof, by only the portion corresponding to the workpiece-attached portion of the adhesive layer 2 shown in FIG. 2a illuminates the radiation, and the difference in adhesion to the other portions 2b can be set.
另外，通過按照圖2所示的晶片接合薄膜3’使輻射線固化型的粘合劑層2固化，可以容易地形成粘合力顯著下降的所述部分2a。由於晶片接合薄膜3’粘貼在固化而粘合力下降的所述部分2a上，因此粘合劑層2的所述部分2a與晶片接合薄膜3’的界面界面具有拾取時容易剝離的性質。另一方面，未照射輻射線的部分具有充分的粘合力，形成所述部分2b。 Further, by curing the radiation-curable pressure-sensitive adhesive layer 2 in accordance with the wafer bonding film 3' shown in Fig. 2, the portion 2a in which the adhesive strength is remarkably lowered can be easily formed. Since the wafer bonding film 3' is pasted on the portion 2a where the adhesion is lowered by curing, the interface interface between the portion 2a of the adhesive layer 2 and the wafer bonding film 3' has a property of being easily peeled off at the time of picking up. On the other hand, the portion where the radiation is not irradiated has sufficient adhesive force to form the portion 2b.
如前所述，圖1所示的切割/晶片接合薄膜10的粘合劑層2中，由未固化的輻射線固化型粘合劑形成的所述部分2b與晶片接合薄膜3粘合，從而可以確保切割時的保持力。這樣，輻射線固化型粘合劑可以以良好的膠粘-剝離的平衡來支撐用於將晶片狀工件(半導體晶片)固著到被粘物上的晶片接合薄膜3。圖2所示的切割/晶片接合薄膜11 的粘合劑層2中，所述部分2b可以將貼片環(wafer ring)固定。 As described above, in the adhesive layer 2 of the dicing/wafer bonding film 10 shown in FIG. 1, the portion 2b formed of the uncured radiation-curable adhesive is bonded to the wafer bonding film 3, thereby It ensures the retention force during cutting. Thus, the radiation curable adhesive can support the wafer bonding film 3 for fixing the wafer-like workpiece (semiconductor wafer) to the adherend with a good balance of adhesion-peeling. The dicing/wafer bonding film 11 shown in FIG. In the adhesive layer 2, the portion 2b can fix a wafer ring.
輻射線固化型粘合劑可以沒有特別限制地使用具有碳-碳雙鍵等輻射線固化性官能基、並且顯示粘合性的輻射線固化型粘合劑。作為輻射線固化型粘合劑，可以例示例如：在所述丙烯酸類粘合劑、橡膠類粘合劑等一般的壓敏粘合劑中配合有輻射線固化性的單體成分或低聚物(oligomer)成分的添加型輻射線固化型粘合劑。 The radiation curable adhesive can be a radiation curable adhesive having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness without any particular limitation. As a radiation-curable pressure-sensitive adhesive, for example, a radiation-curable monomer component or oligomer is blended in a general pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive or the rubber pressure-sensitive adhesive. An added radiation curable adhesive of an (oligomer) component.
作為用於配合的輻射線固化性單體成分，可以列舉例如：胺甲酸乙酯(urethane)低聚物、胺甲酸乙酯(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。另外，輻射線固化性低聚物成分可以列舉胺甲酸乙酯類、聚醚類、聚酯類、聚碳酸酯類、聚丁二烯類等各種低聚物，其分子量在約100~約30000的範圍內是適當的。輻射線固化性單體成分或低聚物成分的配合量可以根據所述粘合劑層的種類適當地確定能夠降低粘合劑層的粘合力的量。一般而言，相對於構成粘合劑的丙烯酸類聚合物等基礎聚合物100重量份，例如為約5重量份~約500重量份，優選約40重量份~約150重量份。 Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, and trimethylolpropane tri(meth)acrylic acid. Ester, tetramethylol methane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol six (a) Acrylate, 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as urethanes, polyethers, polyesters, polycarbonates, and polybutadienes, and the molecular weight thereof is from about 100 to about 30,000. The scope is appropriate. The blending amount of the radiation curable monomer component or the oligomer component can be appropriately determined according to the kind of the pressure-sensitive adhesive layer to reduce the adhesive strength of the pressure-sensitive adhesive layer. In general, it is, for example, about 5 parts by weight to about 500 parts by weight, preferably about 40 parts by weight to about 150 parts by weight, per 100 parts by weight of the base polymer such as the acrylic polymer constituting the binder.
另外，作為輻射線固化型粘合劑，除了前面說明過的添加型輻射線固化型粘合劑以外，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內在型輻射線固化型粘合劑。內在型輻射線固化型粘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粘合劑中移動，可以形成穩定的層結構的粘合劑層，因此優選。 Further, as the radiation curable pressure-sensitive adhesive, in addition to the addition type radiation-curable pressure-sensitive adhesive described above, it is also used in polymerization. An intrinsic type radiation-curable adhesive having a polymer having a carbon-carbon double bond in the side chain or the main chain or in the main chain as a base polymer. The intrinsic radiation curable adhesive does not need to contain or contain a large amount of an oligomer component or the like as a low molecular weight component, so that the oligomer component or the like does not move in the binder over time, and a stable layer structure can be formed. The adhesive layer is therefore preferred.
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-碳雙鍵並且具有粘合性的聚合物。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。 As the base polymer having a carbon-carbon double bond, a polymer having a carbon-carbon double bond and having adhesiveness can be used 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.
所述丙烯酸類聚合物中碳-碳雙鍵的引入方法沒有特別限制，可以採用各種方法，將碳-碳雙鍵引入聚合物側鏈的方法在分子設計上比較容易。可以列舉例如：預先將具有官能基的單體與丙烯酸類聚合物共聚後，使具有能夠與該官能基反應的官能基和碳-碳雙鍵的化合物在保持碳-碳雙鍵的輻射線固化性的狀況下進行縮合或加成反應的方法。 The method of introducing the carbon-carbon double bond in the acrylic polymer is not particularly limited, and various methods can be employed. The method of introducing a carbon-carbon double bond into the polymer side chain is relatively easy in molecular design. For example, a copolymer having a functional group and an acrylic polymer are copolymerized in advance, and a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is cured by radiation which maintains a carbon-carbon double bond. A method of performing a condensation or addition reaction under a sexual condition.
作為這些官能基的組合例，可以列舉例如：羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸酯基等。這些官能基的組合中，考慮反應跟蹤的容易性，優選羥基與異氰酸酯基的組合。另外，只要是通過這些官能基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，則官能基可以在丙烯酸類聚合物與所述化合物中的任意一個上，對於 所述的優選組合而言，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-碳雙鍵的異氰酸酯化合物，可以列舉例如：甲基丙烯醯異氰酸酯、2-甲基丙烯醯氧乙基異氰酸酯、間異丙烯基-α,α-二甲基苄基(benzyl)異氰酸酯等。另外，作為丙烯酸類聚合物，可以使用共聚有前面例示的含羥基單體或2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚這樣的醚類化合物等的聚合物。 Examples of the combination of these functional groups include a carboxyl group, an epoxy group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group. Among the combinations of these functional groups, the ease of reaction tracking is considered, and a combination of a hydroxyl group and an isocyanate group is preferred. Further, as long as a combination of the acrylic polymers having a carbon-carbon double bond is produced by a combination of these functional groups, the functional group may be on either of the acrylic polymer and the compound, In the preferred combination, it is preferred 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 methacryl oxime isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl ( Benzyl) isocyanate and the like. Further, as the acrylic polymer, an ether group such as a hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether copolymerized as described above can be used. a polymer such as a compound.
所述內在型輻射線固化型粘合劑可以單獨使用所述具有碳-碳雙鍵的基礎聚合物(特別是丙烯酸類聚合物)，也可以在不損害特性的範圍內配合所述輻射線固化性單體成分或低聚物成分。輻射線固化性低聚物成分等相對於基礎聚合物100重量份通常在30重量份的範圍內，優選0~10重量份的範圍。 The intrinsic radiation curable adhesive may be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, or may be blended in a range that does not impair the properties. A monomer component or an oligomer component. The radiation curable oligomer component or the like is usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the base polymer.
在通過紫外線等固化時，所述輻射線固化型粘合劑中可以含有光聚合起始劑。作為光聚合起始劑，可以列舉例如：α-酮醇(α-ketol)類化合物，如4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等；苯乙酮(acetophenone)類化合物，如甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮等；苯偶姻醚(benzoin ether)類化合物，如苯偶姻***、苯偶姻異丙醚、茴香偶姻甲醚等；縮酮(ketal)類化合物，如苄基二甲基縮酮(benzyl dimethyl ketal)等；芳香族磺醯氯類化合物，如2-萘磺醯氯等；光活性肟類化合物，如1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟等；二苯甲酮(benzophenone)類化合物，如二苯甲酮、苯甲醯苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等；噻噸酮類化合物，如噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸酯等。光聚合起始劑的配合量相對於構成粘合劑的丙烯酸類聚合物等基礎聚合物100重量份，例如為約0.05重量份~約20重量份。 The photocurable starter may be contained in the radiation curable adhesive when cured by ultraviolet rays or the like. The photopolymerization initiator may, for example, be an α-keto alcohol compound such as 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone or α-. Hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, etc.; acetophenone-like compounds such as methoxyphenyl Ketone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinopropan-1-one; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, fennel dimethyl ether, etc.; ketal compounds Benzyl dimethyl ketal Dimethyl ketal); aromatic sulfonium chloride compounds such as 2-naphthalenesulfonium chloride; photoactive terpenoids such as 1-phenyl-1,2-propanedione-2-(O-ethoxyl) Carbonyl)anthracene; benzophenone-like compounds such as benzophenone, benzamidine benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, etc.; Compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.; camphorquinone; halogenated ketone; fluorenylphosphine oxide; decylphosphonate. The amount of the photopolymerization initiator to be added is, for example, about 0.05 part by weight to about 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the binder.
另外，作為輻射線固化型粘合劑，可以列舉例如：日本特開昭60-196956號公報中所公開的、含有具有2個以上不飽和鍵的加聚性化合物、具有環氧基的烷氧基矽烷等光聚合性化合物、和羰基化合物、有機硫化合物、過氧化物、胺、鎓鹽(onium salt)類化合物等光聚合起始劑的橡膠類粘合劑或丙烯酸類粘合劑等。 In addition, as a radiation-curable pressure-sensitive adhesive, for example, a polyaddition compound having two or more unsaturated bonds and an alkoxy group having an epoxy group, which are disclosed in JP-A-60-196956, may be mentioned. A photopolymerizable compound such as a decane or a rubber-based binder or an acrylic binder such as a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine or an onium salt compound.
所述輻射線固化型的粘合劑層2中，根據需要也可以含有通過照射輻射線而著色的化合物。通過在粘合劑層2中含有通過照射輻射線而著色的化合物，可以僅將照射輻射線的部分著色。即，可以將圖1所示的與工件粘貼部分3a對應的部分2a著色。由此，可以通過肉眼直接判斷粘合劑層2是否被照射了輻射線，可以容易識別工件粘貼部分3a，工件的粘貼也容易。另外，在利用光感測器等檢測半導體元件時，其檢測精度高，從而在半導體元件的拾取 時不產生誤操作。 The radiation curable pressure-sensitive adhesive layer 2 may contain a compound colored by irradiation with radiation as needed. By including the compound colored by irradiation of the radiation in the adhesive layer 2, only the portion irradiated with the radiation can be colored. That is, the portion 2a corresponding to the workpiece sticking portion 3a shown in Fig. 1 can be colored. Thereby, it is possible to directly judge whether or not the adhesive layer 2 is irradiated with radiation by the naked eye, and the workpiece sticking portion 3a can be easily recognized, and the sticking of the workpiece is also easy. In addition, when a semiconductor element is detected by a photo sensor or the like, the detection accuracy is high, so that the semiconductor element is picked up. No misoperations occur.
通過照射輻射線而著色的化合物，為在照射輻射線前無色或淺色、但是通過照射輻射線而有色的化合物。作為所述化合物的優選具體例，可以列舉無色(leuco)染料。作為無色染料，可以優選使用慣用的三苯基甲烷類、螢光黃母體(fluoran)類、酚噻嗪(phenothiazine)類、金胺類、螺吡喃類無色染料。具體地可以列舉：3-[N-(對甲苯基氨基)]-7-苯胺基螢光黃母體、3-[N-(對甲苯基)-N-甲基氨基]-7-苯胺基螢光黃母體、3-[N-(對甲苯基)-N-乙基氨基]-7-苯胺基螢光黃母體、3-二乙氨基-6-甲基-7-苯胺基螢光黃母體、結晶紫內酯、4,4’,4”-三(二甲氨基)三苯基甲醇、4,4’,4”-三(二甲氨基)三苯基甲烷等。 A compound colored by irradiation with radiation is a compound which is colorless or light-colored before irradiation of radiation but colored by irradiation of radiation. Preferable specific examples of the compound include a leuco dye. As the leuco dye, a conventional triphenylmethane type, a fluorescent yellow type, a phenothiazine type, a gold amine type, or a spiropyran type leuco dye can be preferably used. Specifically, a 3-[N-(p-tolylamino)]-7-anilinofluorescent yellow precursor, 3-[N-(p-tolyl)-N-methylamino]-7-anilinofluorene Light yellow precursor, 3-[N-(p-tolyl)-N-ethylamino]-7-anilinyl fluorescent yellow precursor, 3-diethylamino-6-methyl-7-anilinyl fluorescent yellow matrix , crystal violet lactone, 4,4',4"-tris(dimethylamino)triphenylmethanol, 4,4',4"-tris(dimethylamino)triphenylmethane, and the like.
作為優選與這些無色染料一起使用的顯色劑，可以列舉一直以來使用的酚醛樹脂的預聚物、芳香族羧酸衍生物、活性白土等電子受體，另外，在使色調變化時，可以將各種發色劑組合使用。 The coloring agent to be used together with these leuco dyes is preferably an electron acceptor such as a prepolymer of a phenol resin, an aromatic carboxylic acid derivative or an activated clay which has been used conventionally, and when the color tone is changed, A variety of coloring agents are used in combination.
這樣的通過照射輻射線而著色的化合物，可以先溶解於有機溶劑等中後再包含到輻射線固化型粘合劑中，另外，也可以以細粉末形式包含在該粘合劑中。該化合物的使用比例期望在粘合劑層2中為10重量%以下，優選0.01~10重量%，更優選0.5~5重量%。該化合物的比例超過10重量%時，照射到粘合劑層2的輻射線被該化合物過度吸收，因此粘合劑層2的所述部分2a的固化不充分，有時粘合力下降不充分。另一方面，為了充分著色，優選將 該化合物的比例設定為0.01重量%以上。 Such a compound colored by irradiation with radiation may be dissolved in an organic solvent or the like and then incorporated into a radiation-curable pressure-sensitive adhesive, or may be contained in the pressure-sensitive adhesive as a fine powder. The use ratio of the compound is desirably 10% by weight or less, preferably 0.01 to 10% by weight, and more preferably 0.5 to 5% by weight in the pressure-sensitive adhesive layer 2. When the ratio of the compound exceeds 10% by weight, the radiation applied to the pressure-sensitive adhesive layer 2 is excessively absorbed by the compound. Therefore, the curing of the portion 2a of the pressure-sensitive adhesive layer 2 is insufficient, and the adhesion may be insufficiently lowered. . On the other hand, in order to fully color, it is preferred to The ratio of the compound is set to 0.01% by weight or more.
通過輻射線固化型粘合劑形成粘合劑層2的情況下，優選對粘合劑層2的一部分進行輻射線照射，使得粘合劑層2中所述部分2a的粘合力<其他部分2b的粘合力。 In the case where the adhesive layer 2 is formed by a radiation curable adhesive, it is preferred to irradiate a part of the adhesive layer 2 with radiation so that the adhesive force of the portion 2a in the adhesive layer 2 is <Other portions 2b adhesion.
作為在所述粘合劑層2中形成所述部分2a的方法，可以列舉：在基材1上形成輻射線固化型粘合劑層2後，對所述部分2a局部地照射輻射線使其固化的方法。局部的輻射線照射可以通過形成有與工件粘貼部分3a以外的部分3b等對應的圖案的光罩(photomask)來進行。另外，可以列舉點(spot)狀照射紫外線進行固化的方法等。輻射線固化型粘合劑層2的形成可以通過將設置在隔片上的輻射線固化型粘合劑層轉印到支撐基材1上來進行。局部的輻射線固化也可以對設置在隔片上的輻射線固化型粘合劑層2進行。 As a method of forming the portion 2a in the pressure-sensitive adhesive layer 2, after the radiation-curable pressure-sensitive adhesive layer 2 is formed on the substrate 1, the portion 2a is partially irradiated with radiation. The method of curing. The local radiation irradiation can be performed by a photomask in which a pattern corresponding to the portion 3b or the like other than the workpiece pasting portion 3a is formed. Further, a method in which a spot is irradiated with ultraviolet rays for curing is exemplified. The formation of the radiation curable pressure-sensitive adhesive layer 2 can be carried out by transferring the radiation curable pressure-sensitive adhesive layer provided on the separator to the support substrate 1. Localized radiation curing can also be performed on the radiation curable adhesive layer 2 provided on the separator.
另外，通過輻射線固化型粘合劑形成粘合劑層2的情況下，可以使用對支撐基材1的至少單面的、與工件粘貼部分3a對應的部分以外的部分的全部或局部進行遮光的基材，並在該基材上形成輻射線固化型粘合劑層2後進行輻射線照射，使與工件粘貼部分3a對應的部分固化，從而形成粘合力下降的所述部分2a。作為遮光材料，可以通過印刷或蒸鍍等在支撐薄膜上製作能夠成為光罩的材料。通過所述製造方法，可以有效地製造本發明的切割/晶片接合薄膜10。 Further, when the pressure-sensitive adhesive layer 2 is formed of a radiation curable pressure-sensitive adhesive, it is possible to use all or part of the portion other than the portion corresponding to the workpiece attachment portion 3a on at least one side of the support substrate 1 to be shielded from light. The substrate is formed on the substrate, and the radiation-curable pressure-sensitive adhesive layer 2 is formed on the substrate, and then irradiated with radiation to cure the portion corresponding to the workpiece sticking portion 3a, thereby forming the portion 2a having a reduced adhesive force. As the light shielding material, a material that can be used as a photomask can be formed on the support film by printing, vapor deposition, or the like. The dicing/wafer bonding film 10 of the present invention can be efficiently produced by the above manufacturing method.
另外，進行輻射線照射時因氧產生固化障礙的情況 下，優選利用任意方法從輻射線固化型粘合劑層2的表面隔絕氧(空氣)。可以列舉例如：用隔片將粘合劑層2的表面覆蓋的方法或者在氮氣氛圍中進行紫外線等輻射線的照射的方法等。 In addition, when the radiation is irradiated, the curing obstacle due to oxygen is generated. Next, oxygen (air) is preferably isolated from the surface of the radiation-curable adhesive layer 2 by any method. For example, a method of covering the surface of the pressure-sensitive adhesive layer 2 with a separator or a method of irradiating radiation such as ultraviolet rays in a nitrogen atmosphere may be mentioned.
粘合劑層2的厚度沒有特別限制，從同時實現防止晶片切割面的缺損和膠粘層的固定保持等觀點考慮，優選為約1μm至約50μm。優選2μm~30μm、更優選5μm~25μm。 The thickness of the pressure-sensitive adhesive layer 2 is not particularly limited, and is preferably from about 1 μm to about 50 μm from the viewpoint of simultaneously preventing the chip cut surface defect and the fixing of the adhesive layer. It is preferably 2 μm to 30 μm, and more preferably 5 μm to 25 μm.
本實施方式的切割/晶片接合薄膜10、12，例如如下進行製作。 The dicing/wafer bonding films 10 and 12 of the present embodiment are produced, for example, as follows.
首先，基材1可以通過現有公知的制膜方法制膜。作為該制膜方法，可以例示例如：壓延制膜法、有機溶劑中的澆注法、密閉體系中的吹塑擠出法、T形模頭擠出法、共擠出法、幹式層壓法等。 First, the substrate 1 can be formed into a film by a conventionally known film forming method. Examples of the film forming method include a calender film forming method, a casting method in an organic solvent, a blow molding method in a closed system, a T-die extrusion method, a co-extrusion method, and a dry lamination method. Wait.
接著，在基材1上塗布粘合劑組合物溶液形成塗膜，然後在預定條件下將該塗膜乾燥(根據需要加熱交聯)而形成粘合劑層2。作為塗布方法，沒有特別限制，可以列舉例如：輥塗、網版塗布(screen coating)、凹版塗布等。另外，作為乾燥條件，可以在例如：乾燥溫度80~150℃、乾燥時間0.5~5分鐘的範圍內進行。另外，也可以在隔片上塗布粘合劑組合物形成塗膜後在所述乾燥條件下將塗膜乾燥來形成粘合劑層2。然後，將粘合劑層2與隔片一起粘貼到基材1上。由此，製作切割薄膜11。 Next, the adhesive composition solution is applied onto the substrate 1 to form a coating film, and then the coating film is dried under predetermined conditions (heat crosslinking as needed) to form the pressure-sensitive adhesive layer 2. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, gravure coating, and the like. Further, the drying conditions can be carried out, for example, at a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Alternatively, the pressure-sensitive adhesive layer 2 may be formed by applying a pressure-sensitive adhesive composition to a separator to form a coating film, and then drying the coating film under the drying conditions. Then, the adhesive layer 2 is attached to the substrate 1 together with the separator. Thereby, the dicing film 11 is produced.
晶片接合薄膜3、3’例如如下進行製作。 The wafer bonding films 3, 3' are produced, for example, as follows.
首先，製作作為切割/晶片接合薄膜3、3’的形成材料 的膠粘劑組合物溶液。在該膠粘劑組合物溶液中，如前所述，配合有所述膠粘劑組合物、填料、其他各種添加劑等。 First, a forming material as the dicing/wafer bonding film 3, 3' is produced. Adhesive composition solution. In the adhesive composition solution, as described above, the adhesive composition, the filler, various other additives, and the like are blended.
然後，以得到預定厚度的方式將膠粘劑組合物溶液塗布到基材隔片上形成塗膜，然後在預定條件下將該塗膜乾燥，形成膠粘劑層。作為塗布方法沒有特別限制，可以列舉例如：輥塗、網版塗布、凹版塗布等。另外，作為乾燥條件，例如在乾燥溫度70~160℃、乾燥時間1~5分鐘的範圍內進行。另外，也可以在隔片上塗布粘合劑組合物溶液而形成塗膜後，在前述乾燥條件下將塗膜乾燥而形成膠粘劑層。然後，將膠粘劑層與隔片一起粘貼到基材隔片上。 Then, the adhesive composition solution is applied onto the substrate separator to form a coating film in such a manner as to obtain a predetermined thickness, and then the coating film is dried under a predetermined condition to form an adhesive layer. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions are carried out, for example, at a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Further, after the pressure-sensitive adhesive composition solution is applied onto the separator to form a coating film, the coating film may be dried under the drying conditions to form an adhesive layer. The adhesive layer is then adhered to the substrate separator together with the separator.
接著，從切割薄膜11和膠粘劑層上分別將隔片剝離，以膠粘劑層與粘合劑層作為粘貼面的方式將兩者粘貼。粘貼例如可以通過壓接來進行。此時，層壓溫度沒有特別限制，例如優選30~50℃，更優選35~45℃。另外，線壓也沒有特別限制，例如優選0.1~20kgf/cm，更優選1~10kgf/cm。然後，將膠粘劑層上的基材隔片剝離，得到本實施方式的切割/晶片接合薄膜。 Next, the separator was peeled off from the dicing film 11 and the adhesive layer, respectively, and the adhesive layer and the pressure-sensitive adhesive layer were used as a bonding surface. Pasting can be performed, for example, by crimping. At this time, the lamination temperature is not particularly limited, and is, for example, preferably 30 to 50 ° C, more preferably 35 to 45 ° C. Further, the linear pressure is not particularly limited, and is, for example, preferably 0.1 to 20 kgf/cm, more preferably 1 to 10 kgf/cm. Then, the substrate separator on the adhesive layer is peeled off to obtain a dicing/wafer bonding film of the present embodiment.
本發明的切割/晶片接合薄膜10、12，適當地將任意設置在晶片接合薄膜3、3’上的隔片剝離並如下使用。以下，參考圖3以使用切割/晶片接合薄膜10的情況為例進行說明。圖3是表示通過圖1所示的切割/晶片接合薄膜中的膠粘劑層安裝半導體晶片的例子的示意剖視圖。 The dicing/wafer bonding films 10 and 12 of the present invention are suitably peeled off from the spacers arbitrarily provided on the wafer bonding films 3, 3' and used as follows. Hereinafter, a case where the dicing/wafer bonding film 10 is used will be described with reference to FIG. 3 is a schematic cross-sectional view showing an example in which a semiconductor wafer is mounted by an adhesive layer in the dicing/wafer bonding film shown in FIG. 1.
首先，將半導體晶圓4壓接到切割/晶片接合薄膜10 中的晶片接合薄膜3的半導體晶片粘貼部分3a上，將其膠粘保持而固定(粘貼工序)。本工序利用壓接輥等擠壓手段擠壓來進行。安裝時的粘貼溫度沒有特別限制，優選例如在20~80℃的範圍內。 First, the semiconductor wafer 4 is crimped to the dicing/wafer bonding film 10 The semiconductor wafer bonding portion 3a of the wafer bonding film 3 is adhered and fixed by the bonding (paste step). This step is carried out by extrusion using a pressing means such as a pressure roller. The sticking temperature at the time of mounting is not particularly limited, and is preferably, for example, in the range of 20 to 80 °C.
然後，進行半導體晶圓4的切割。由此，將半導體晶圓4切割為預定尺寸而小片化，製作半導體晶片5。切割例如按照常規方法從半導體晶圓4的電路面側進行。另外，本工序中，例如，可以採用切入到切割/晶片接合薄膜10的、稱為全切割的切割方式等。本工序中使用的切割裝置沒有特別限制，可以採用現有公知的切割裝置。另外，半導體晶片由切割/晶片接合薄膜10膠粘固定，因此可以抑制晶片缺損或晶片飛散，並且可以抑制半導體晶圓4的破損。 Then, the dicing of the semiconductor wafer 4 is performed. Thereby, the semiconductor wafer 4 is cut into a predetermined size and diced, and the semiconductor wafer 5 is produced. The cutting is performed from the circuit surface side of the semiconductor wafer 4, for example, in accordance with a conventional method. Further, in this step, for example, a cutting method called full cutting which is cut into the dicing/wafer bonding film 10 may be employed. The cutting device used in this step is not particularly limited, and a conventionally known cutting device can be employed. Further, since the semiconductor wafer is adhesively fixed by the dicing/wafer bonding film 10, wafer defects or wafer scattering can be suppressed, and breakage of the semiconductor wafer 4 can be suppressed.
為了剝離由切割/晶片接合薄膜10膠粘固定的半導體晶片，進行半導體晶片5的拾取。拾取方法沒有特別限制，可以採用現有公知的各種方法。可以列舉例如：用針將各個半導體晶片5從切割/晶片接合薄膜10側上推，並利用拾取裝置拾取上推的半導體晶片5的方法等。 In order to peel off the semiconductor wafer adhered and fixed by the dicing/wafer bonding film 10, picking up of the semiconductor wafer 5 is performed. The picking method is not particularly limited, and various conventionally known methods can be employed. For example, a method in which each semiconductor wafer 5 is pushed up from the dicing/wafer bonding film 10 side by a needle, and the push-up semiconductor wafer 5 is picked up by a pick-up device can be cited.
在此，粘合劑層2為紫外線固化型的情況下，在對該粘合劑層2照射紫外線後進行拾取。由此，粘合劑層2對晶片接合薄膜3的粘合力下降，使半導體晶片5容易剝離。結果，可以在不損傷半導體晶片5的情況下進行拾取。紫外線照射時的照射強度、照射時間等條件沒有特別限制，可以根據需要適當設定。另外，作為紫外線照射時使用的 光源，可以使用前述的光源。 Here, when the pressure-sensitive adhesive layer 2 is of an ultraviolet curing type, the pressure-sensitive adhesive layer 2 is irradiated with ultraviolet rays and then picked up. Thereby, the adhesive force of the pressure-sensitive adhesive layer 2 to the wafer bonding film 3 is lowered, and the semiconductor wafer 5 is easily peeled off. As a result, pickup can be performed without damaging the semiconductor wafer 5. Conditions such as the irradiation intensity and the irradiation time at the time of ultraviolet irradiation are not particularly limited, and can be appropriately set as needed. In addition, it is used when it is irradiated with ultraviolet rays. For the light source, the aforementioned light source can be used.
拾取的半導體晶片5通過晶片接合薄膜3膠粘固定到被粘物6上(晶片接合(die bonding))。 The picked semiconductor wafer 5 is adhesively fixed to the adherend 6 by die bonding film 3 (die bonding).
晶片接合的條件沒有特別限制，可以適當設定。例如，可以設定為晶片接合溫度80~160℃、晶片接合壓力5N~15N、晶片接合時間1~10秒的範圍內。 The conditions for wafer bonding are not particularly limited and can be appropriately set. For example, it can be set to a wafer bonding temperature of 80 to 160 ° C, a wafer bonding pressure of 5 N to 15 N, and a wafer bonding time of 1 to 10 seconds.
作為被粘物6，可以列舉引線框、TAB薄膜、基板或者獨立製作的半導體晶片等。被粘物6例如可以是容易變形的變形型被粘物，也可以是難以變形的非變形型被粘物(半導體晶片等)。 Examples of the adherend 6 include a lead frame, a TAB film, a substrate, or a separately fabricated semiconductor wafer. The adherend 6 may be, for example, a deformed adherend that is easily deformed, or may be a non-deformable adherend (a semiconductor wafer or the like) that is difficult to deform.
作為所述基板，可以使用現有公知的基板。另外，所述引線框可以使用Cu引線框、42合金引線框等金屬引線框或包含玻璃環氧、BT(雙馬來醯亞胺-三嗪)、聚醯亞胺等的有機基板。但是，本發明不限於此，也包括安裝半導體元件並與半導體元件電連接而可以使用的電路板。 As the substrate, a conventionally known substrate can be used. Further, as the lead frame, a metal lead frame such as a Cu lead frame or a 42 alloy lead frame or an organic substrate containing glass epoxy, BT (bismaleimide-triazine), polyimine or the like can be used. However, the present invention is not limited thereto, and includes a circuit board in which a semiconductor element is mounted and electrically connected to the semiconductor element.
晶片接合薄膜3為熱固化型時，通過加熱固化，將半導體晶片5膠粘固定在被粘物6上，使耐熱強度提高。可以在加熱溫度為80~180℃、優選100~175℃、更優選100~150℃下進行。另外，可以在加熱時間為0.1~24小時、優選0.1~3小時、更優選0.1~1小時下進行。 When the wafer bonding film 3 is of a thermosetting type, the semiconductor wafer 5 is adhered and fixed to the adherend 6 by heat curing, and the heat resistance is improved. The heating can be carried out at a heating temperature of 80 to 180 ° C, preferably 100 to 175 ° C, more preferably 100 to 150 ° C. Further, the heating time can be carried out in the range of 0.1 to 24 hours, preferably 0.1 to 3 hours, more preferably 0.1 to 1 hour.
熱固化後的晶片接合薄膜3對被粘物6的剪切膠粘力優選為0.02MPa以上，更優選0.03~10MPa。晶片接合薄膜3的剪切膠粘力為至少0.02MPa以上時，在進行引線接合工序時，不會因該工序中的超聲波振動或加熱而在晶片 接合薄膜3與半導體晶片5或被粘物6的膠粘面上產生剪切變形。即，半導體元件不會因引線接合時的超聲波振動而活動，由此，可以防止引線接合的成功率下降。 The shear adhesive strength of the wafer bonded film 3 after heat curing to the adherend 6 is preferably 0.02 MPa or more, and more preferably 0.03 to 10 MPa. When the shear adhesive strength of the wafer bonding film 3 is at least 0.02 MPa or more, the wafer bonding process is not performed on the wafer due to ultrasonic vibration or heating in the process. Shear deformation occurs on the bonding surface of the bonding film 3 and the semiconductor wafer 5 or the adherend 6. In other words, the semiconductor element does not move due to ultrasonic vibration during wire bonding, and thus it is possible to prevent the success rate of wire bonding from being lowered.
另外，本發明的半導體裝置的製造方法，可以在不經過晶片接合薄膜3的利用加熱處理進行的熱固化工序的情況下進行引線接合，再用密封樹脂將半導體晶片5密封，並將該密封樹脂後固化。此時，晶片接合薄膜3暫時固著時對被粘物6的剪切膠粘力優選為0.02MPa以上，更優選0.03~10MPa。晶片接合薄膜3暫時固著時的剪切膠粘力為至少0.02MPa以上時，即使在不經過加熱工序的情況下進行引線接合工序，也很少會因該工序中的超聲波振動或加熱而在晶片接合薄膜3與半導體晶片5或被粘物6的膠粘面上產生剪切變形。即，半導體元件不會因引線接合時的超聲波振動而活動，由此，可以防止引線接合的成功率下降。 Further, in the method of manufacturing a semiconductor device of the present invention, wire bonding can be performed without undergoing a heat curing process by the heat treatment of the die bond film 3, and the semiconductor wafer 5 can be sealed with a sealing resin, and the sealing resin can be sealed. After curing. At this time, the shear adhesive strength to the adherend 6 when the wafer bonding film 3 is temporarily fixed is preferably 0.02 MPa or more, and more preferably 0.03 to 10 MPa. When the shear adhesive strength at the time of temporarily fixing the wafer bonding film 3 is at least 0.02 MPa or more, even if the wire bonding step is performed without a heating step, the ultrasonic vibration or heating in the step is rarely caused. Shear deformation occurs on the adhesive surface of the wafer bonding film 3 and the semiconductor wafer 5 or the adherend 6. In other words, the semiconductor element does not move due to ultrasonic vibration during wire bonding, and thus it is possible to prevent the success rate of wire bonding from being lowered.
所述引線接合是利用焊線7將被粘物6的端子部(內部引線)的前端與半導體晶片5上的電極焊盤(未圖示)電連接的工序(參考圖3)。作為所述焊線7，可以使用例如：金線、鋁線或銅線等。進行引線接合時的溫度在80~250℃、優選80~220℃的範圍內進行。另外，其加熱時間進行幾秒~幾分鐘。接線是在所述溫度範圍內加熱的狀態下，通過組合使用超聲波振動能和施加壓力而產生的壓接能來進行的。本工序可以在不進行晶片接合薄膜3的熱固化的情況下進行。 The wire bonding is a step of electrically connecting the tip end of the terminal portion (internal lead) of the adherend 6 to an electrode pad (not shown) on the semiconductor wafer 5 by the bonding wire 7 (refer to FIG. 3). As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The temperature at the time of wire bonding is performed in the range of 80 to 250 ° C, preferably 80 to 220 ° C. In addition, the heating time is carried out for a few seconds to several minutes. The wiring is performed in a state where the temperature is heated within the temperature range by a combination of ultrasonic vibration energy and pressure application. This step can be carried out without performing heat curing of the wafer bonding film 3.
所述密封工序是利用密封樹脂8將半導體晶片5密封的工序(參考圖3)。本工序是為了保護搭載在被粘物6上的半導體晶片5或焊線7而進行的。本工序通過用模具將密封用的樹脂成型來進行。作為密封樹脂8，例如可以使用環氧類樹脂。樹脂密封時的加熱溫度通常在175℃下進行60~90秒，但是，本發明不限於此，例如，也可以在165~185℃下固化幾分鐘。由此，在使密封樹脂固化的同時通過晶片接合薄膜3將半導體晶片5與被粘物6固著。即，本發明中，即使在不進行後述的後固化工序的情況下，本工序中也可以利用晶片接合薄膜3進行固著，從而可以有助於減少製造工序數及縮短半導體裝置的製造時間。 The sealing step is a step of sealing the semiconductor wafer 5 with the sealing resin 8 (refer to FIG. 3). This step is performed to protect the semiconductor wafer 5 or the bonding wires 7 mounted on the adherend 6. This step is carried out by molding a resin for sealing with a mold. As the sealing resin 8, for example, an epoxy resin can be used. The heating temperature at the time of resin sealing is usually carried out at 175 ° C for 60 to 90 seconds, but the present invention is not limited thereto, and for example, it may be cured at 165 to 185 ° C for several minutes. Thereby, the semiconductor wafer 5 and the adherend 6 are fixed by the wafer bonding film 3 while the sealing resin is cured. In other words, in the present invention, even when the post-curing step to be described later is not performed, the wafer bonding film 3 can be fixed in this step, which contributes to a reduction in the number of manufacturing steps and a reduction in the manufacturing time of the semiconductor device.
所述後固化工序中，使在前述密封工序中固化不足的密封樹脂8完全固化。即使在密封工序中晶片接合薄膜3未完全熱固化的情況下，在本工序中也可以與密封樹脂8一起實現晶片接合薄膜3的完全熱固化。本工序中的加熱溫度因密封樹脂的種類而異，例如，在165℃~185℃的範圍內，加熱時間為約0.5小時~約8小時。 In the post-curing step, the sealing resin 8 which is insufficiently cured in the sealing step is completely cured. Even in the case where the wafer bonding film 3 is not completely thermally cured in the sealing step, complete thermal curing of the wafer bonding film 3 can be achieved together with the sealing resin 8 in this step. The heating temperature in this step varies depending on the type of the sealing resin. For example, in the range of 165 ° C to 185 ° C, the heating time is from about 0.5 hours to about 8 hours.
然後，在印刷佈線板上表面安裝所述半導體封裝。表面安裝的方法可以列舉例如：在印刷佈線板上預先供給焊料後，利用溫風等進行加熱熔融而進行焊接的回流焊接(回流焊接工序)。作為加熱方法，可以列舉熱風回流、紅外線回流等。另外，可以為整體加熱、局部加熱中的任意一種方式。加熱溫度優選為230℃~280℃，加熱時間優選在1~360秒的範圍內。 Then, the semiconductor package is surface mounted on the printed wiring board. For the surface mounting method, for example, after the solder is supplied in advance on the printed wiring board, the solder is heated and melted by warm air or the like to perform reflow soldering (reflow soldering step). Examples of the heating method include hot air reflux, infrared reflux, and the like. Further, it may be any one of overall heating and local heating. The heating temperature is preferably from 230 ° C to 280 ° C, and the heating time is preferably in the range of from 1 to 360 seconds.
另外，本發明的切割/晶片接合薄膜，如圖4所示，也可以適當用於將多個半導體晶片層疊進行三維安裝的情況。圖4是表示通過圖1所示的切割/晶片接合薄膜中的膠粘劑層三維安裝半導體晶片的例子的示意剖視圖。圖4所示的三維安裝的情況下，首先，將切割為與半導體晶片相同尺寸的至少一個晶片接合薄膜3晶片接合到被粘物6上，然後，通過晶片接合薄膜3將半導體晶片5以其引線接合面為上側的方式進行晶片接合。然後，避開半導體晶片5的電極焊盤部分將晶片接合薄膜13進行晶片接合。進而，將另一個半導體晶片15以其引線接合面為上側的方式晶片接合到晶片接合薄膜13上。 Further, as shown in FIG. 4, the dicing/wafer bonding film of the present invention can be suitably used in a case where a plurality of semiconductor wafers are stacked and three-dimensionally mounted. 4 is a schematic cross-sectional view showing an example in which a semiconductor wafer is three-dimensionally mounted by an adhesive layer in the dicing/wafer bonding film shown in FIG. 1. In the case of the three-dimensional mounting shown in FIG. 4, first, at least one wafer bonding film 3 cut into the same size as the semiconductor wafer is die-bonded to the adherend 6, and then the semiconductor wafer 5 is passed through the wafer bonding film 3 Wafer bonding is performed such that the wire bonding surface is the upper side. Then, the wafer bonding film 13 is wafer bonded by avoiding the electrode pad portion of the semiconductor wafer 5. Further, another semiconductor wafer 15 is wafer-bonded to the wafer bonding film 13 with its wire bonding surface as the upper side.
然後，進行晶片接合薄膜3、3’的熱固化，然後進行引線接合工序。由此，用焊線7將半導體晶片5及另一半導體晶片15中各自的電極焊盤與被粘物6電連接。 Then, thermal curing of the wafer bonding films 3, 3' is performed, and then a wire bonding step is performed. Thereby, the electrode pads of the semiconductor wafer 5 and the other semiconductor wafer 15 are electrically connected to the adherend 6 by the bonding wires 7.
接著，利用密封樹脂8進行將半導體晶片5等密封的密封工序，並使密封樹脂固化。另外，在密封工序後可以進行後固化工序。 Next, a sealing step of sealing the semiconductor wafer 5 or the like is performed by the sealing resin 8, and the sealing resin is cured. Further, a post-cure step can be performed after the sealing step.
進行半導體晶片的三維安裝的情況下，將半導體晶片5、15與被粘物6連接的焊線7數量增多，因此具有引線接合工序中所花費的時間增加的傾向，從而在高溫下長時間暴露。但是，通過晶片接合薄膜3、13，即使在高溫下長時間暴露，也可以抑制熱固化反應的進行。 When the three-dimensional mounting of the semiconductor wafer is performed, the number of bonding wires 7 that connect the semiconductor wafers 5 and 15 to the adherend 6 is increased. Therefore, the time taken in the wire bonding step tends to increase, and the exposure is long at a high temperature. . However, the wafer bonding films 3 and 13 can suppress the progress of the heat curing reaction even when exposed to a high temperature for a long period of time.
另外，可以如圖5所示進行在半導體晶片間通過晶片接合薄膜層疊墊片的三維安裝。圖5是表示使用圖1所示 的切割/晶片接合薄膜，隔著墊片利用膠粘劑層將兩個半導體晶片三維安裝的例子的示意剖視圖。 Further, three-dimensional mounting of the wafer-bonded film laminated spacer between the semiconductor wafers can be performed as shown in FIG. Figure 5 is a diagram showing the use of Figure 1 A dicing/wafer bonding film, a schematic cross-sectional view of an example in which two semiconductor wafers are three-dimensionally mounted using an adhesive layer via a gasket.
圖5所示的三維安裝的情況下，首先，在被粘物6上依次層疊晶片接合薄膜3、半導體晶片5和晶片接合薄膜21。另外，在晶片接合薄膜21上，依次層疊隔片9、晶片接合薄膜21、晶片接合薄膜3和半導體晶片5進行晶片接合。 In the case of the three-dimensional mounting shown in FIG. 5, first, the wafer bonding film 3, the semiconductor wafer 5, and the wafer bonding film 21 are sequentially laminated on the adherend 6. Further, on the wafer bonding film 21, the separator 9, the wafer bonding film 21, the wafer bonding film 3, and the semiconductor wafer 5 are sequentially laminated to perform wafer bonding.
然後，進行晶片接合薄膜3、21的熱固化，然後，如圖5所示進行引線接合工序。由此，利用焊線7將半導體晶片5中的電極焊盤與被粘物6電連接。 Then, thermal curing of the wafer bonding films 3 and 21 is performed, and then a wire bonding process is performed as shown in FIG. Thereby, the electrode pads in the semiconductor wafer 5 are electrically connected to the adherend 6 by the bonding wires 7.
接著，進行利用密封樹脂8將半導體晶片5密封的密封工序，並使密封樹脂固化。由此，得到半導體封裝。密封工序優選僅將半導體晶片5側單面密封的一次密封法。密封是為了保護粘貼在粘合片上的半導體晶片5而進行的，其方法以使用密封樹脂8在模具中成型為代表。此時，一般是使用具有多個腔室的由上模和下模構成的模具，同時進行密封工序。樹脂密封時的加熱溫度例如優選在170~180℃的範圍內。密封工序後，可以進行後固化工序。 Next, a sealing step of sealing the semiconductor wafer 5 with the sealing resin 8 is performed, and the sealing resin is cured. Thereby, a semiconductor package is obtained. The sealing step is preferably a one-time sealing method in which only one side of the semiconductor wafer 5 is sealed. The sealing is performed to protect the semiconductor wafer 5 attached to the adhesive sheet, and the method is represented by molding using a sealing resin 8 in a mold. At this time, a mold composed of an upper mold and a lower mold having a plurality of chambers is generally used, and a sealing process is simultaneously performed. The heating temperature at the time of resin sealing is preferably, for example, in the range of 170 to 180 °C. After the sealing process, a post-cure process can be performed.
另外，作為所述墊片9，沒有特別限制，例如可以使用現有公知的矽晶片、聚醯亞胺薄膜等。另外，可以使用芯材作為所述墊片。作為芯材沒有特別限制，可以使用現有公知的芯材。具體而言，可以使用薄膜(例如，聚醯亞胺薄膜、聚酯薄膜、聚對苯二甲酸乙二酯薄膜、聚2,6萘二甲酸乙二酯薄膜、聚碳酸酯薄膜等)、由玻璃纖維或塑 膠製不織纖維增強的樹脂基板、鏡面矽晶片、矽基板或玻璃基板等。 Further, the spacer 9 is not particularly limited, and for example, a conventionally known tantalum wafer, a polyimide film, or the like can be used. In addition, a core material may be used as the gasket. The core material is not particularly limited, and a conventionally known core material can be used. Specifically, a film (for example, a polyimide film, a polyester film, a polyethylene terephthalate film, a polyethylene 2,6 naphthalate film, a polycarbonate film, etc.) may be used. Fiberglass or plastic A non-woven fiber reinforced resin substrate, a mirror enamel wafer, a ruthenium substrate, or a glass substrate.
然後，在印刷佈線板上將所述半導體封裝表面安裝。表面安裝的方法可以列舉例如：在印刷佈線板上預先供給焊料後，利用溫風等進行加熱熔融而進行焊接的回流焊接。作為加熱方法，可以列舉熱風回流、紅外線回流等。另外，可以為整體加熱、局部加熱中的任意一種方式。加熱溫度優選為230~280℃，加熱時間優選在1~360秒的範圍內。 Then, the semiconductor package surface is mounted on a printed wiring board. For the surface mounting method, for example, after the solder is supplied in advance on the printed wiring board, the solder is heated and melted by warm air or the like to perform reflow soldering. Examples of the heating method include hot air reflux, infrared reflux, and the like. Further, it may be any one of overall heating and local heating. The heating temperature is preferably 230 to 280 ° C, and the heating time is preferably in the range of 1 to 360 seconds.
以下，例示性地詳細說明本發明的優選實施例。但是，該實施例中記載的材料、配合量等，如果並非特別限定性的記載，則不僅僅將本發明限於此。另外，“份”是指重量份。 Hereinafter, preferred embodiments of the present invention will be exemplarily described in detail. However, the materials, the compounding amounts, and the like described in the examples are not limited to the above, unless otherwise specified. In addition, "part" means a part by weight.
本實施例、比較例中使用的含腈基熱固性丙烯酸共聚物的環氧值根據JIS K 7236進行計算。具體而言，將4g含腈基熱固性丙烯酸共聚物稱量到100ml的錐形瓶中，在其中加入10ml氯仿將其溶解。再加入30ml乙酸、5ml四乙基溴化銨和5滴結晶紫指示劑，在用磁力攪拌器攪拌的同時用0.1mol/L的過氯酸乙酸(perchloric acid acetic acid)規度溶液進行滴定。通過同樣方法進行空白試驗，並利用下式計算環氧值。 The epoxy value of the nitrile group-containing thermosetting acrylic copolymer used in the examples and the comparative examples was calculated in accordance with JIS K 7236. Specifically, 4 g of the nitrile-containing thermosetting acrylic copolymer was weighed into a 100 ml Erlenmeyer flask, and 10 ml of chloroform was added thereto to dissolve it. Further, 30 ml of acetic acid, 5 ml of tetraethylammonium bromide and 5 drops of crystal violet indicator were added, and the mixture was titrated with a 0.1 mol/L perchloric acid acetic acid solution while stirring with a magnetic stirrer. The blank test was carried out in the same manner, and the epoxy value was calculated by the following formula.
環氧值=[(V-B)×0.1×F]/W Epoxy value = [(V-B) × 0.1 × F] / W
W：稱量的試樣的克數 W: grams of sample weighed
B：空白試驗所需要的0.1mol/L過氯酸乙酸規度溶液的毫升數 B: The number of milliliters of 0.1 mol/L perchloric acid acetic acid solution required for the blank test
V：試樣的滴定所需要的0.1mol/L過氯酸乙酸規度溶液的毫升數 V: milliliters of 0.1 mol/L perchloric acid acetate solution required for titration of the sample
F：0.1mol/L過氯酸乙酸規度溶液的因數 F: factor of 0.1 mol/L perchloric acid acetate solution
本實施例、比較例中使用的含腈基熱固性丙烯酸共聚物的玻璃轉移溫度，使用粘彈性測定裝置(Rheometric Scientific公司製造，RSA-III)，由升溫速度10℃/分鐘、頻率1MHz下的Tan(E”(損耗彈性模量)/E’(儲能彈性模量))來測定。 The glass transition temperature of the nitrile group-containing thermosetting acrylic copolymer used in the examples and the comparative examples was measured by a viscoelasticity measuring apparatus (RSA-III, manufactured by Rheometric Scientific Co., Ltd.) at a temperature rising rate of 10 ° C/min and a frequency of 1 MHz. (E" (loss elastic modulus) / E' (storage elastic modulus)) was measured.
本實施例、比較例中使用的含腈基熱固性丙烯酸共聚物的重均分子量，通過凝膠滲透色譜法測定。凝膠滲透色譜法中，將TSK G2000H HR、G3000H HR、G4000H HR、及GMH-H HR這4根柱(均為東曹有限公司製)串聯連接使用，使用四氫呋喃作為洗脫液，在流速1ml/分鐘、溫度40℃、試樣濃度0.1重量%四氫呋喃溶液、試樣注射量500μl的條件下進行，檢測器使用差示折光計。 The weight average molecular weight of the nitrile group-containing thermosetting acrylic copolymer used in the examples and the comparative examples was measured by gel permeation chromatography. In the gel permeation chromatography, four columns (all manufactured by Tosoh Co., Ltd.) of TSK G2000H HR, G3000H HR, G4000H HR, and GMH-H HR were used in series, and tetrahydrofuran was used as an eluent at a flow rate of 1 ml. The temperature was 40 ° C, the sample concentration was 0.1% by weight of tetrahydrofuran solution, and the sample injection amount was 500 μl. The detector used a differential refractometer.
將100份含腈基熱固性丙烯酸共聚物(a-1)、5.2份作為固化劑的酚醛樹脂(b-1)溶解到甲乙酮中，製備濃度23.6重量%的膠粘劑組合物溶液。作為實施例1中的含腈 基熱固性丙烯酸共聚物(a-1)，使用以丙烯腈-丙烯酸乙酯-丙烯酸丁酯為主要成分、並且含有4.1莫耳%丙烯酸縮水甘油酯的丙烯酸酯類聚合物(根上工業有限公司製造，ND系列，懸浮聚合物，環氧值0.41，玻璃轉移點(Tg)12℃、重均分子量50萬)。另外，丙烯腈在含腈基熱固性丙烯酸共聚物(a-1)中所占的含量，相對於共聚物的總重量為28重量%。另外，作為實施例1中的固化劑的酚醛樹脂(b-1)，使用明和化成有限公司製造的“MEH7851”。 100 parts of a nitrile-based thermosetting acrylic copolymer (a-1) and 5.2 parts of a phenol resin (b-1) as a curing agent were dissolved in methyl ethyl ketone to prepare a solution of an adhesive composition having a concentration of 23.6% by weight. As the nitrile in Example 1 The base thermosetting acrylic copolymer (a-1) is an acrylate polymer containing acrylonitrile-ethyl acrylate-butyl acrylate as a main component and containing 4.1 mol% of glycidyl acrylate (manufactured by Roots Industrial Co., Ltd.). ND series, suspension polymer, epoxy value 0.41, glass transfer point (Tg) 12 ° C, weight average molecular weight 500,000). Further, the content of acrylonitrile in the nitrile group-containing thermosetting acrylic copolymer (a-1) was 28% by weight based on the total weight of the copolymer. Further, as the phenol resin (b-1) as the curing agent in Example 1, "MEH7851" manufactured by Minghe Chemical Co., Ltd. was used.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫模處理後的厚度50μm的聚對苯二甲酸乙二酯薄膜構成的脫模處理薄膜(剝離襯墊)上，然後在130℃乾燥2分鐘。由此，製作厚度25μm的晶片接合薄膜A。 The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after demoldin treatment, and then dried at 130 ° C for 2 minutes. . Thus, a wafer bonding film A having a thickness of 25 μm was produced.
將100份含腈基熱固性丙烯酸共聚物(a-2)、10.3份作為固化劑的酚醛樹脂(b-2)溶解到甲乙酮中，製備濃度23.6重量%的膠粘劑組合物溶液。作為實施例2中的含腈基熱固性丙烯酸共聚物(a-2)，使用以丙烯腈-丙烯酸乙酯-丙烯酸丁酯為主要成分、並且含有4.1莫耳%丙烯酸縮水甘油酯的丙烯酸酯類聚合物(根上工業有限公司製造，ND系列，懸浮聚合物，環氧值0.41，玻璃轉移點(Tg)9℃、重均分子量105萬)。另外，丙烯腈在含腈基熱固性丙烯酸共聚物(a-2)中所占的含量，相對於共聚物的總重量為24重量%。另外，作為實施例2中的固化劑的酚醛樹脂(b-2)，使用明和化成有限公司製造的“MEH7851”。 100 parts of a nitrile-based thermosetting acrylic copolymer (a-2) and 10.3 parts of a phenol resin (b-2) as a curing agent were dissolved in methyl ethyl ketone to prepare a binder composition solution having a concentration of 23.6% by weight. As the nitrile group-containing thermosetting acrylic copolymer (a-2) in Example 2, an acrylate polymerization containing acrylonitrile-ethyl acrylate-butyl acrylate as a main component and containing 4.1 mol% of glycidyl acrylate was used. (manufactured by Roots Industrial Co., Ltd., ND series, suspension polymer, epoxy value 0.41, glass transfer point (Tg) 9 ° C, weight average molecular weight 1.05 million). Further, the content of acrylonitrile in the nitrile group-containing thermosetting acrylic copolymer (a-2) was 24% by weight based on the total weight of the copolymer. Further, as the phenol resin (b-2) as the curing agent in Example 2, "MEH7851" manufactured by Minghe Chemical Co., Ltd. was used.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫模處理後的厚度50μm的聚對苯二甲酸乙二酯薄膜構成的脫模處理薄膜(剝離襯墊)上，然後在130℃乾燥2分鐘。由此，製作厚度25μm的晶片接合薄膜B。 The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after demoldin treatment, and then dried at 130 ° C for 2 minutes. . Thus, a wafer bonding film B having a thickness of 25 μm was produced.
將100份含腈基熱固性丙烯酸共聚物(a-3)、48.5份作為固化劑的酚醛樹脂(b-3)溶解到甲乙酮中，製備濃度23.6重量%的膠粘劑組合物溶液。作為實施例3中的含腈基熱固性丙烯酸共聚物(a-3)，使用以丙烯腈-丙烯酸乙酯-丙烯酸丁酯為主要成分、並且含有4.1莫耳%丙烯酸縮水甘油酯的丙烯酸酯類聚合物(根上工業有限公司製造，ND系列，懸浮聚合物，環氧值0.41，玻璃轉移點(Tg)0℃、重均分子量110萬)。另外，丙烯腈在含腈基熱固性丙烯酸共聚物(a-3)中所占的含量，相對於共聚物的總重量為20重量%。另外，作為實施例3中的固化劑的酚醛樹脂(b-3)，使用明和化成有限公司製造的“MEH7851”。 100 parts of a nitrile-based thermosetting acrylic copolymer (a-3) and 48.5 parts of a phenol resin (b-3) as a curing agent were dissolved in methyl ethyl ketone to prepare a binder composition solution having a concentration of 23.6% by weight. As the nitrile group-containing thermosetting acrylic copolymer (a-3) in Example 3, an acrylate polymerization containing acrylonitrile-ethyl acrylate-butyl acrylate as a main component and containing 4.1 mol% of glycidyl acrylate was used. (manufactured by Roots Industrial Co., Ltd., ND series, suspension polymer, epoxy value 0.41, glass transfer point (Tg) 0 ° C, weight average molecular weight 1.1 million). Further, the content of acrylonitrile in the nitrile group-containing thermosetting acrylic copolymer (a-3) was 20% by weight based on the total weight of the copolymer. Further, as the phenol resin (b-3) as the curing agent in Example 3, "MEH7851" manufactured by Minghe Chemical Co., Ltd. was used.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫模處理後的厚度50μm的聚對苯二甲酸乙二酯薄膜構成的脫模處理薄膜(剝離襯墊)上，然後在130℃乾燥2分鐘。由此，製作厚度25μm的晶片接合薄膜C。 The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after demoldin treatment, and then dried at 130 ° C for 2 minutes. . Thus, a wafer bonding film C having a thickness of 25 μm was produced.
將100份含腈基熱固性丙烯酸類共聚物(a-4)、10.3份作為固化劑的1,2,4-三羥基苯(b-4)溶解到甲乙酮中，進一步在其中分散40份平均粒徑500nm的球狀二氧化矽 (ADMATECHS有限公司製，SO-25R)，製備濃度23.6重量%的膠粘劑組合物溶液。作為實施例4中的含腈基熱固性丙烯酸共聚物(a-4)，使用以丙烯腈-丙烯酸乙酯-丙烯酸丁酯為主要成分、並且含有2.4莫耳%丙烯酸縮水甘油酯的丙烯酸酯類聚合物(根上工業有限公司製造，ND系列，懸浮聚合物，環氧值0.23，玻璃轉移點(Tg)0℃、重均分子量105萬)。另外，丙烯腈在含腈基熱固性丙烯酸共聚物(a-4)中所占的含量，相對於共聚物的總重量為20重量%。另外，作為實施例4中的固化劑的1,2,4-三羥基苯(b-4)，使用東京化成有限公司製造的產品。 100 parts of the nitrile-based thermosetting acrylic copolymer (a-4) and 10.3 parts of 1,2,4-trihydroxybenzene (b-4) as a curing agent were dissolved in methyl ethyl ketone, and further 40 parts of the average granules were dispersed therein. Spherical cerium oxide with a diameter of 500 nm (manufactured by ADMATECHS Co., Ltd., SO-25R), a solution of an adhesive composition having a concentration of 23.6% by weight was prepared. As the nitrile group-containing thermosetting acrylic copolymer (a-4) in Example 4, an acrylate polymerization containing acrylonitrile-ethyl acrylate-butyl acrylate as a main component and containing 2.4 mol% of glycidyl acrylate was used. (manufactured by Roots Industrial Co., Ltd., ND series, suspension polymer, epoxy value 0.23, glass transfer point (Tg) 0 ° C, weight average molecular weight 1.05 million). Further, the content of acrylonitrile in the nitrile group-containing thermosetting acrylic copolymer (a-4) was 20% by weight based on the total weight of the copolymer. Further, as the 1,2,4-trihydroxybenzene (b-4) as the curing agent in Example 4, a product manufactured by Tokyo Chemical Industry Co., Ltd. was used.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫模處理後的厚度50μm的聚對苯二甲酸乙二酯薄膜構成的脫模處理薄膜(剝離襯墊)上，然後在130℃乾燥2分鐘。由此，製作厚度25μm的晶片接合薄膜D。 The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after demoldin treatment, and then dried at 130 ° C for 2 minutes. . Thus, a wafer bonding film D having a thickness of 25 μm was produced.
將100份熱固性丙烯酸共聚物(a-5)、5.2份作為固化劑的酚醛樹脂(b-3)溶解到甲乙酮中，製備濃度23.6重量%的膠粘劑組合物溶液。作為比較例1中的熱固性丙烯酸共聚物(a-5)，使用以丙烯酸乙酯-丙烯酸丁酯為主要成分、並且含有4.1莫耳%丙烯酸縮水甘油酯的丙烯酸酯類聚合物(根上工業有限公司製造，ND系列，懸浮聚合物，環氧值0.41，玻璃轉移點(Tg)12℃、重均分子量90萬)。另外，作為比較例1中的固化劑的酚醛樹脂(b-5)，使用明和化成有限公司製造的“MEH7851”。 100 parts of the thermosetting acrylic copolymer (a-5) and 5.2 parts of the phenol resin (b-3) as a curing agent were dissolved in methyl ethyl ketone to prepare a solution of the adhesive composition having a concentration of 23.6% by weight. As the thermosetting acrylic copolymer (a-5) in Comparative Example 1, an acrylate polymer containing ethyl acrylate-butyl acrylate as a main component and containing 4.1 mol% of glycidyl acrylate was used (Gone Industrial Co., Ltd.) Manufactured, ND series, suspension polymer, epoxy value 0.41, glass transfer point (Tg) 12 ° C, weight average molecular weight 900,000). Further, as the phenol resin (b-5) as the curing agent in Comparative Example 1, "MEH7851" manufactured by Minghe Chemical Co., Ltd. was used.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫模處理後的厚度50μm的聚對苯二甲酸乙二酯薄膜構成的脫模處理薄膜(剝離襯墊)上，然後在130℃乾燥2分鐘。由此，製作厚度25μm的晶片接合薄膜E。 The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after demoldin treatment, and then dried at 130 ° C for 2 minutes. . Thus, a wafer bonding film E having a thickness of 25 μm was produced.
將100份含腈基熱固性丙烯酸共聚物(a-6)、10.3份作為固化劑的酚醛樹脂(b-6)和5份固化催化劑(四國化成有限公司製造，C11-Z)溶解到甲乙酮中，製備濃度23.6重量%的膠粘劑組合物溶液。作為比較例2中的含腈基熱固性丙烯酸共聚物(a-6)，使用以丙烯腈-丙烯酸乙酯-丙烯酸丁酯為主要成分、並且含有4.1莫耳%丙烯酸縮水甘油酯的丙烯酸酯類聚合物(根上工業有限公司製造，ND系列，懸浮聚合物，環氧值0.41，玻璃轉移點(Tg)9℃、重均分子量105萬)。另外，丙烯腈在含腈熱固性丙烯酸共聚物(a-6)中所占的含量，相對於共聚物總重量為24重量%。另外，作為比較例2中的固化劑的酚醛樹脂(b-6)，使用明和化成有限公司製造的“MEH7851”。 100 parts of a nitrile-based thermosetting acrylic copolymer (a-6), 10.3 parts of a phenol resin (b-6) as a curing agent, and 5 parts of a curing catalyst (manufactured by Shikoku Chemical Co., Ltd., C11-Z) were dissolved in methyl ethyl ketone. A solution of the adhesive composition having a concentration of 23.6% by weight was prepared. As the nitrile group-containing thermosetting acrylic copolymer (a-6) in Comparative Example 2, an acrylate polymerization containing acrylonitrile-ethyl acrylate-butyl acrylate as a main component and containing 4.1 mol% of glycidyl acrylate was used. (manufactured by Roots Industrial Co., Ltd., ND series, suspension polymer, epoxy value 0.41, glass transfer point (Tg) 9 ° C, weight average molecular weight 1.05 million). Further, the content of acrylonitrile in the nitrile-containing thermosetting acrylic copolymer (a-6) was 24% by weight based on the total weight of the copolymer. Further, as the phenol resin (b-6) as the curing agent in Comparative Example 2, "MEH7851" manufactured by Minghe Chemical Co., Ltd. was used.
將該膠粘劑組合物溶液塗布到經聚矽氧烷脫模處理後的厚度50μm的聚對苯二甲酸乙二酯薄膜構成的脫模處理薄膜(剝離襯墊)上，然後在130℃乾燥2分鐘。由此，製作厚度25μm的晶片接合薄膜F。 The adhesive composition solution was applied onto a release-treated film (release liner) composed of a polyethylene terephthalate film having a thickness of 50 μm after demoldin treatment, and then dried at 130 ° C for 2 minutes. . Thus, a wafer bonding film F having a thickness of 25 μm was produced.
放熱量測定中，使用差示掃描量熱計(SII Nano Technology公司製造，DSC6220)。首先，將試樣(晶片 接合薄膜A~F)10mg投入到帶褶鋁鍋(Al)中，在氮氣氣氛下，以10℃/分鐘的升溫速度從25℃(室溫)升溫到300℃。在升溫過程中得到的DSC曲線(放熱峰)中畫基線，由基線與DSC曲線圍成的部分的面積計算熱量。圖6是表示通過差示掃描量熱測定得到的典型的差示量熱曲線的圖。所述熱量由圖6中所示的基線B與差示量熱曲線L圍成的區域的面積來計算。 In the calorific value measurement, a differential scanning calorimeter (manufactured by SII Nano Technology, DSC6220) was used. First, the sample (wafer 10 mg of the bonding films A to F) were placed in a pleated aluminum pan (Al), and the temperature was raised from 25 ° C (room temperature) to 300 ° C at a temperature elevation rate of 10 ° C / min in a nitrogen atmosphere. The baseline is drawn in the DSC curve (exothermic peak) obtained during the temperature rise, and the heat is calculated from the area of the portion surrounded by the baseline and the DSC curve. Fig. 6 is a view showing a typical differential calorimetry curve obtained by differential scanning calorimetry. The heat is calculated from the area of the area surrounded by the baseline B and the differential calorimetry curve L shown in FIG.
然後，由下式計算放熱量。 Then, the amount of heat generation is calculated by the following formula.
(放熱量(mJ/mg))=(熱量(mJ))/(測定試樣的重量(mg)) (Exothermic heat (mJ/mg)) = (heat (mJ)) / (measured sample weight (mg))
另外，這些操作和計算全自動進行。結果如表1所示。 In addition, these operations and calculations are fully automated. The results are shown in Table 1.
將晶片接合薄膜A~F用切刀切割為長度22.5mm(測定長度)×寬度10mm的條狀，使用固體粘彈性測定裝置(RSA-III，Rheometric Scientific有限公司製造)，測定-50~300℃的拉伸儲能彈性模量。測定條件是，頻率1Hz，升溫速度10℃/分鐘。此時的50℃的拉伸儲能彈性模量的值如表1所示。 The wafer bonding films A to F were cut into strips having a length of 22.5 mm (measured length) × width of 10 mm by a cutter, and measured by a solid viscoelasticity measuring apparatus (RSA-III, manufactured by Rheometric Scientific Co., Ltd.) at -50 to 300 ° C. The tensile storage elastic modulus. The measurement conditions were a frequency of 1 Hz and a temperature increase rate of 10 ° C / min. The values of the tensile storage elastic modulus at 50 ° C at this time are shown in Table 1.
將晶片接合薄膜A~F在175℃熱固化5小時。然後，將熱固化後的晶片接合薄膜A~F用切刀切割為長度22.5mm(測定長度)×寬度10mm的條狀，使用固體粘彈性測定裝置(RSA-III，Rheometric Scientific有限公司製 造)，測定-50~300℃的拉伸儲能彈性模量。測定條件是，頻率1Hz，升溫速度10℃/分鐘。此時的260℃的拉伸儲能彈性模量的值如表1所示。 The wafer bonding films A to F were thermally cured at 175 ° C for 5 hours. Then, the thermally bonded wafer-bonding films A to F were cut into strips having a length of 22.5 mm (measured length) × width of 10 mm by a cutter, and a solid viscoelasticity measuring apparatus (RSA-III, manufactured by Rheometric Scientific Co., Ltd.) was used. Manufacture), the tensile storage elastic modulus of -50 to 300 ° C is measured. The measurement conditions were a frequency of 1 Hz and a temperature increase rate of 10 ° C / min. The values of the tensile storage elastic modulus at 260 ° C at this time are shown in Table 1.
對於在175℃熱固化5小時後的晶片接合薄膜A~F，通過熱重量法測定失重5重量%的溫度。結果如表1所示。 For the wafer bonded films A to F which were thermally cured at 175 ° C for 5 hours, the temperature at which the weight loss was 5% by weight was measured by a thermogravimetric method. The results are shown in Table 1.
對於晶片接合薄膜A~F，由在85℃、85%RH的恒溫恒濕槽中放置168小時前後的重量減少率測定在175℃熱固化5小時後的吸水率。結果如表1所示。 With respect to the wafer bonded films A to F, the water absorption rate after heat curing at 175 ° C for 5 hours was measured by a weight reduction rate of 168 hours before and after being placed in a constant temperature and humidity chamber at 85 ° C and 85% RH. The results are shown in Table 1.
將各實施例和比較例中得到的晶片接合薄膜A~F在40℃的條件下粘貼到5mm見方的半導體元件上，然後在溫度120℃、壓力0.1MPa、時間1秒的條件下安裝到BGA(球柵陣列，ball grid array)基板上。再用乾燥機將其在150℃熱處理1小時，然後在120℃實施10小時的熱處理。然後，使用成型機(TOWA Press公司製造，manual press(手動壓力機)Y-1)，在成形溫度175℃、夾緊壓力184kN、傳送壓力5kN、時間120秒、密封樹脂GE-100(日東電工有限公司製造)的條件下進行密封工序。使用超聲波圖像裝置(日立Fine Tech公司製造，FS200II)觀察密封工序後的晶片接合薄膜與BGA基板的界面界面。使用二值化 軟體(WinRoof ver.5.6)計算觀察的圖像中空隙所占的面積。空隙所占的面積相對於晶片接合薄膜的表面積小於30%的情況評價為“○”，30%以上的情況評價為“×”。結果如表1所示。 The wafer bonding films A to F obtained in the respective Examples and Comparative Examples were attached to a 5 mm square semiconductor element under conditions of 40 ° C, and then mounted to a BGA at a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second. (ball grid array) on the substrate. Further, it was heat-treated at 150 ° C for 1 hour with a dryer, and then subjected to heat treatment at 120 ° C for 10 hours. Then, using a molding machine (manufactured by TOWA Press, manual press Y-1), at a forming temperature of 175 ° C, a clamping pressure of 184 kN, a transfer pressure of 5 kN, a time of 120 seconds, and a sealing resin GE-100 (Nitto Denko) The sealing process is carried out under the conditions of the company. The interface interface between the wafer bonding film and the BGA substrate after the sealing step was observed using an ultrasonic image apparatus (manufactured by Hitachi Fine Chemical Co., Ltd., FS200II). Use binarization The software (WinRoof ver. 5.6) calculates the area occupied by the voids in the observed image. The case where the area occupied by the voids is less than 30% with respect to the surface area of the wafer bonding film is evaluated as "○", and in the case of 30% or more, it is evaluated as "X". The results are shown in Table 1.
將各實施例和比較例中得到的晶片接合薄膜A~F在40℃的條件下粘貼到5mm見方的半導體元件上，然後在溫度120℃、壓力0.1MPa、時間1秒的條件下安裝到BGA(球柵陣列)基板上。再用乾燥機將其在150℃熱處理1小時，然後在175℃實施1小時的熱處理。然後，使用成型機(TOWA Press公司製造，manual press Y-1)，在成形溫度175℃、夾緊壓力184kN、傳送壓力5kN、時間120秒、密封樹脂GE-100(日東電工有限公司製造)的條件下進行密封工序。使用超聲波圖像裝置(日立Fine Tech公司製造，FS200II)觀察密封工序後的晶片接合薄膜與BGA基板的介面。使用二值化軟體(WinRoof ver.5.6)計算觀察的圖像中空隙所占的面積。空隙所占的面積相對於晶片接合薄膜的表面積小於30%的情況評價為“○”，30%以上的情況評價為“×”。結果如表1所示。 The wafer bonding films A to F obtained in the respective Examples and Comparative Examples were attached to a 5 mm square semiconductor element under conditions of 40 ° C, and then mounted to a BGA at a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second. (Ball grid array) on the substrate. Further, it was heat-treated at 150 ° C for 1 hour with a dryer, and then subjected to heat treatment at 175 ° C for 1 hour. Then, using a molding machine (manufactured by TOWA Press, manual press Y-1), at a forming temperature of 175 ° C, a clamping pressure of 184 kN, a transfer pressure of 5 kN, a time of 120 seconds, and a sealing resin GE-100 (manufactured by Nitto Denko Co., Ltd.) The sealing process is carried out under the conditions. The interface between the wafer bonding film and the BGA substrate after the sealing step was observed using an ultrasonic image apparatus (manufactured by Hitachi Fine Chemical Co., Ltd., FS200II). The area occupied by the voids in the observed image was calculated using a binarized software (WinRoof ver. 5.6). The case where the area occupied by the voids is less than 30% with respect to the surface area of the wafer bonding film is evaluated as "○", and in the case of 30% or more, it is evaluated as "X". The results are shown in Table 1.
將各實施例和比較例中得到的晶片接合薄膜A~F在40℃下粘貼到5mm見方的半導體晶片上，然後在溫度120 ℃、壓力0.1MPa、時間1秒的條件下安裝到BGA基板上。再用乾燥機將其在150℃熱處理1小時，然後在120℃實施10小時的熱處理。然後，使用成型機(TOWA Press公司製造，manual press Y-1)，在成形溫度175℃、夾緊壓力184kN、傳送壓力5kN、時間120秒、密封樹脂GE-100(日東電工有限公司製造)的條件下進行密封工序。然後，在溫度85℃、濕度60%RH、時間168小時的條件下進行吸濕操作，再將樣品通過以將260℃以上的溫度保持30秒的方式進行溫度設定的IR回流爐。對於9個半導體元件，使用超聲波顯微鏡觀察晶片接合薄膜與BGA基板的邊界處是否產生剝離，並計算產生剝離的比例(%)。結果如表1所示。 The wafer bonding films A to F obtained in the respective Examples and Comparative Examples were attached to a 5 mm square semiconductor wafer at 40 ° C, and then at a temperature of 120. It was mounted on a BGA substrate under the conditions of ° C, pressure of 0.1 MPa, and time of 1 second. Further, it was heat-treated at 150 ° C for 1 hour with a dryer, and then subjected to heat treatment at 120 ° C for 10 hours. Then, using a molding machine (manufactured by TOWA Press, manual press Y-1), at a forming temperature of 175 ° C, a clamping pressure of 184 kN, a transfer pressure of 5 kN, a time of 120 seconds, and a sealing resin GE-100 (manufactured by Nitto Denko Co., Ltd.) The sealing process is carried out under the conditions. Then, the moisture absorption operation was carried out under the conditions of a temperature of 85 ° C, a humidity of 60% RH, and a time of 168 hours, and the sample was passed through an IR reflow furnace in which the temperature was set to be maintained at a temperature of 260 ° C or higher for 30 seconds. With respect to the nine semiconductor elements, whether or not peeling occurred at the boundary between the wafer bonding film and the BGA substrate was observed using an ultrasonic microscope, and the ratio (%) at which peeling occurred was calculated. The results are shown in Table 1.
將各實施例和比較例中得到的晶片接合薄膜A~F在40℃的條件下粘貼到5mm見方的半導體晶片上，然後在溫度120℃、壓力0.1MPa、時間1秒的條件下安裝到BGA基板上。再用乾燥機將其在150℃熱處理1小時，然後在175℃實施1小時的熱處理。然後，使用成型機(TOWA Press公司製造，manual press Y-1)，在成形溫度175℃、夾緊壓力184kN、傳送壓力5kN、時間120秒、密封樹脂GE-100(日東電工有限公司製造)的條件下進行密封工序。然後，在溫度85℃、濕度60%RH、時間168小時的條件下進行吸濕操作，再將樣品通過以將260℃以上的溫 度保持10秒的方式進行溫度設定的IR回流爐。對於9個半導體元件，使用超聲波顯微鏡觀察晶片接合薄膜與BGA基板的邊界處是否產生剝離，並計算產生剝離的比例(%)。結果如表1所示。 The wafer bonding films A to F obtained in the respective Examples and Comparative Examples were attached to a 5 mm square semiconductor wafer under conditions of 40 ° C, and then mounted to a BGA at a temperature of 120 ° C, a pressure of 0.1 MPa, and a time of 1 second. On the substrate. Further, it was heat-treated at 150 ° C for 1 hour with a dryer, and then subjected to heat treatment at 175 ° C for 1 hour. Then, using a molding machine (manufactured by TOWA Press, manual press Y-1), at a forming temperature of 175 ° C, a clamping pressure of 184 kN, a transfer pressure of 5 kN, a time of 120 seconds, and a sealing resin GE-100 (manufactured by Nitto Denko Co., Ltd.) The sealing process is carried out under the conditions. Then, the moisture absorption operation was carried out under the conditions of a temperature of 85 ° C, a humidity of 60% RH, and a time of 168 hours, and the sample was passed to adjust the temperature above 260 ° C. The IR reflow oven was set to maintain the temperature for 10 seconds. With respect to the nine semiconductor elements, whether or not peeling occurred at the boundary between the wafer bonding film and the BGA substrate was observed using an ultrasonic microscope, and the ratio (%) at which peeling occurred was calculated. The results are shown in Table 1.
對於實施例1~4的晶片接合薄膜而言，即使在晶片接合後在高溫下長時間進行熱處理(120℃下10小時或175℃下1小時)的情況下，在作為此後的工序的密封工序後，觀察晶片接合薄膜與被粘物的邊界時，氣泡(空隙)也少。另外，耐濕試驗中也顯示良好的結果。 In the wafer bonded film of Examples 1 to 4, even if heat treatment (10 hours at 120 ° C or 1 hour at 175 ° C) is performed at a high temperature for a long time after wafer bonding, the sealing process as a subsequent step is performed. Thereafter, when the boundary between the wafer bonding film and the adherend is observed, bubbles (voids) are also small. In addition, good results were also shown in the moisture resistance test.
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內，當可作些許之更動與潤飾，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。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧粘合劑層 2‧‧‧Adhesive layer
2a‧‧‧粘合劑層的部分 2a‧‧‧Parts of the adhesive layer
2b‧‧‧粘合劑層的其他部分 2b‧‧‧Other parts of the adhesive layer
3、3’‧‧‧晶片接合薄膜(熱固型晶片接合薄膜) 3, 3'‧‧‧ wafer bonding film (thermosetting wafer bonding film)
3a‧‧‧晶片接合薄膜與工件粘貼部分 3a‧‧‧ wafer bonding film and workpiece pasting part
3b‧‧‧晶片接合薄膜的與工件粘貼部分以外的部分 3b‧‧‧Parts other than the pasted part of the wafer bonding film
4‧‧‧半導體晶片 4‧‧‧Semiconductor wafer
5‧‧‧半導體晶片 5‧‧‧Semiconductor wafer
6‧‧‧被粘物 6‧‧‧sticky objects
7‧‧‧焊線 7‧‧‧welding line
8‧‧‧密封樹脂 8‧‧‧ Sealing resin
9‧‧‧隔片、墊片 9‧‧‧Separators, gaskets
10、12‧‧‧切割/晶片接合薄膜 10,12‧‧‧Cutting/wafer bonding film
11‧‧‧切割薄膜 11‧‧‧ cutting film
13‧‧‧晶片接合薄膜(熱固型晶片接合薄膜) 13‧‧‧ wafer bonding film (thermosetting wafer bonding film)
15‧‧‧半導體晶片 15‧‧‧Semiconductor wafer
21‧‧‧晶片接合薄膜(熱固型晶片接合薄膜) 21‧‧‧ wafer bonding film (thermosetting wafer bonding film)
圖1是表示本發明的一個實施方式的切割/晶片接合薄膜的示意剖視圖。 1 is a schematic cross-sectional view showing a dicing/wafer bonding film according to an embodiment of the present invention.
圖2是表示本發明的另一實施方式的切割/晶片接合薄膜的示意剖視圖。 Fig. 2 is a schematic cross-sectional view showing a dicing/wafer bonding film according to another embodiment of the present invention.
圖3是表示通過圖1所示的切割/晶片接合薄膜中的膠粘劑層安裝半導體晶片的例子的示意剖視圖。 3 is a schematic cross-sectional view showing an example in which a semiconductor wafer is mounted by an adhesive layer in the dicing/wafer bonding film shown in FIG. 1.
圖4是表示通過圖1所示的切割/晶片接合薄膜中的膠粘劑層三維安裝半導體晶片的例子的示意剖視圖。 4 is a schematic cross-sectional view showing an example in which a semiconductor wafer is three-dimensionally mounted by an adhesive layer in the dicing/wafer bonding film shown in FIG. 1.
圖5是表示使用圖1所示的切割/晶片接合薄膜，隔著墊片利用膠粘劑層三維安裝兩個半導體晶片的例子的示意剖視圖。 Fig. 5 is a schematic cross-sectional view showing an example in which two semiconductor wafers are three-dimensionally mounted by an adhesive layer via a spacer using the dicing/wafer bonding film shown in Fig. 1 .
圖6是表示通過差示掃描量熱測定得到的典型的差示量熱曲線的圖。 Fig. 6 is a view showing a typical differential calorimetry curve obtained by differential scanning calorimetry.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧粘合劑層 2‧‧‧Adhesive layer
2a‧‧‧粘合劑層的部分 2a‧‧‧Parts of the adhesive layer
2b‧‧‧粘合劑層的其他部分 2b‧‧‧Other parts of the adhesive layer
3‧‧‧晶片接合薄膜(熱固型晶片接合薄膜) 3‧‧‧ wafer bonding film (thermosetting wafer bonding film)
3a‧‧‧晶片接合薄膜與工件粘貼部分 3a‧‧‧ wafer bonding film and workpiece pasting part
3b‧‧‧晶片接合薄膜的與工件粘貼部分以外的部分 3b‧‧‧Parts other than the pasted part of the wafer bonding film
4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer
10‧‧‧切割/晶片接合薄膜 10‧‧‧Cutting/wafer bonding film
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| JP7017334B2 (en) * | 2017-04-17 | 2022-02-08 | 日東電工株式会社 | Dicing die bond film |
| JP7038575B2 (en) * | 2018-03-08 | 2022-03-18 | 日東電工株式会社 | Sealing sheet |
| JP7033003B2 (en) * | 2018-05-23 | 2022-03-09 | 日東電工株式会社 | Dicing die bond film |
| CN112234019B (en) * | 2020-10-20 | 2023-01-17 | 广东省科学院半导体研究所 | Transfer film, transfer assembly and micro device curved surface transfer method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE55238B1 (en) * | 1983-08-03 | 1990-07-04 | Nat Starch Chem Corp | Carrier film with conductive adhesive for dicing of semiconductor wafers |
| JPH0616524B2 (en) * | 1984-03-12 | 1994-03-02 | 日東電工株式会社 | Adhesive thin plate for fixing semiconductor wafers |
| EP2161739A4 (en) * | 2007-06-22 | 2010-08-25 | Sumitomo Bakelite Co | Adhesive film and semiconductor device obtained with the same |
| JP2009124135A (en) * | 2007-10-24 | 2009-06-04 | Hitachi Chem Co Ltd | Adhesive member for semiconductor and semiconductor device |
| JP2010006912A (en) * | 2008-06-25 | 2010-01-14 | Shin-Etsu Chemical Co Ltd | Adhesive composition, adhesive film, and dicing die attach film |
| JP4994429B2 (en) * | 2008-08-04 | 2012-08-08 | 日東電工株式会社 | Dicing die bond film |
| JP4778078B2 (en) * | 2009-02-06 | 2011-09-21 | 信越化学工業株式会社 | Adhesive composition, adhesive sheet, dicing die attach film, and semiconductor device |
| JP5143196B2 (en) * | 2009-09-28 | 2013-02-13 | 日東電工株式会社 | Film for semiconductor devices |
| JP4976481B2 (en) * | 2009-12-04 | 2012-07-18 | 日東電工株式会社 | Thermosetting die bond film, dicing die bond film, and semiconductor device |
| JP5398083B2 (en) * | 2011-03-11 | 2014-01-29 | 日東電工株式会社 | Die bond film and its use |
-
2011
- 2011-08-03 JP JP2011170254A patent/JP5930625B2/en active Active
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2012
- 2012-07-31 TW TW101127630A patent/TWI552216B/en active
- 2012-08-03 CN CN201210275227.8A patent/CN102911616B/en active Active
- 2012-08-03 CN CN201510901642.3A patent/CN105505244A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP5930625B2 (en) | 2016-06-08 |
| CN105505244A (en) | 2016-04-20 |
| JP2013038097A (en) | 2013-02-21 |
| TWI552216B (en) | 2016-10-01 |
| CN102911616B (en) | 2016-01-20 |
| CN102911616A (en) | 2013-02-06 |
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