TW202039627A - Semiconductor device and manufacturing method thereof - Google Patents
Semiconductor device and manufacturing method thereof Download PDFInfo
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- TW202039627A TW202039627A TW108147585A TW108147585A TW202039627A TW 202039627 A TW202039627 A TW 202039627A TW 108147585 A TW108147585 A TW 108147585A TW 108147585 A TW108147585 A TW 108147585A TW 202039627 A TW202039627 A TW 202039627A
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- Taiwan
- Prior art keywords
- insulating film
- interlayer insulating
- semiconductor device
- general formula
- layer
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 216
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
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Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49838—Geometry or layout
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
- H01L21/4853—Connection or disconnection of other leads to or from a metallisation, e.g. pins, wires, bumps
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
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- H—ELECTRICITY
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- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
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- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
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Abstract
Description
本發明係關於一種半導體裝置及其製造方法。The invention relates to a semiconductor device and a manufacturing method thereof.
半導體裝置中之半導體封裝方法有各種方法。作為半導體封裝方法,例如有如下封裝方法:以密封材(塑模樹脂)覆蓋半導體晶片,形成元件密封材,進而形成與半導體晶片電性連接之再配線層。半導體封裝方法中,近年來,稱為扇出(Fan-Out)之半導體封裝方法成為主流。There are various methods for semiconductor packaging in semiconductor devices. As a semiconductor packaging method, for example, there is a packaging method in which a semiconductor wafer is covered with a sealing material (molding resin) to form an element sealing material, and then a rewiring layer electrically connected to the semiconductor wafer is formed. Among semiconductor packaging methods, in recent years, a semiconductor packaging method called Fan-Out has become the mainstream.
於扇出型之半導體封裝中,藉由以密封材覆蓋半導體晶片,形成大於半導體晶片之晶片尺寸之晶片密封體。進而,形成到達半導體晶片及密封材之區域之再配線層。再配線層係以較薄之膜厚形成。又,再配線層可形成至密封材之區域,故而可增多外部連接端子之數目。In the fan-out semiconductor package, the semiconductor chip is covered with a sealing material to form a chip encapsulation body larger than the chip size of the semiconductor chip. Furthermore, a rewiring layer reaching the region of the semiconductor wafer and the sealing material is formed. The rewiring layer is formed with a thinner film thickness. In addition, the rewiring layer can be formed to the area of the sealing material, so the number of external connection terminals can be increased.
例如,作為扇出型之半導體裝置,已知下述專利文獻1。 [先前技術文獻] [專利文獻]For example, as a fan-out type semiconductor device, the following Patent Document 1 is known. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本專利特開2011-129767號公報[Patent Document 1] Japanese Patent Laid-Open No. 2011-129767
[發明所欲解決之問題][The problem to be solved by the invention]
對扇出型之半導體裝置要求再配線層中之層間絕緣膜與密封材之間具有較高之密接性。然而,先前之扇出型之半導體裝置中,再配線層中之層間絕緣膜與密封材之間之密接性並不充分。又,於天線一體型模組等中,存在電特性下降之傾向。For fan-out semiconductor devices, high adhesion between the interlayer insulating film and the sealing material in the rewiring layer is required. However, in the conventional fan-out semiconductor device, the adhesion between the interlayer insulating film in the rewiring layer and the sealing material is insufficient. In addition, in antenna-integrated modules, etc., there is a tendency for electrical characteristics to decrease.
本發明係鑒於該方面而完成者,其目的在於提供一種再配線層中之層間絕緣膜與密封材之密接性優異、電特性優異之半導體裝置及其製造方法。 [解決問題之技術手段]The present invention was made in view of this aspect, and its object is to provide a semiconductor device with excellent adhesion between the interlayer insulating film and the sealing material in the rewiring layer and excellent electrical characteristics, and a method of manufacturing the same. [Technical means to solve the problem]
本發明之半導體裝置之特徵在於:具備半導體晶片、覆蓋上述半導體晶片之密封材、及俯視時面積大於上述半導體晶片之再配線層,並且上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為5~95重量%。 又,於另一態樣中,本發明之半導體裝置之特徵在於:具備半導體晶片、覆蓋上述半導體晶片之密封材、及俯視時面積大於上述半導體晶片之再配線層,並且將上述再配線層之層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.2×10-6 ~2.5×10-6 Pa。 又,於又一態樣中,本發明之半導體裝置之特徵在於:具備半導體晶片、覆蓋上述半導體晶片之密封材、及俯視時面積大於上述半導體晶片之再配線層,並且將上述再配線層之層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.4×10-6 ~1.8×10-6 Pa。The semiconductor device of the present invention is characterized in that it includes a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than the semiconductor wafer when viewed from above, and the interlayer insulating film of the rewiring layer is exposed to 10 The weight loss rate after heating up to 700°C at °C/min is 5-95% by weight. In another aspect, the semiconductor device of the present invention is characterized in that it includes a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than the semiconductor wafer when viewed from above, and the rewiring layer When the interlayer insulating film is kept at 100°C for 60 minutes, the volatile gas per 1 cm 2 is 0.2×10 -6 to 2.5×10 -6 Pa. In yet another aspect, the semiconductor device of the present invention is characterized by comprising a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than the semiconductor wafer when viewed from above, and the rewiring layer When the interlayer insulating film is kept at 100°C for 60 minutes, the volatile gas per 1 cm 2 is 0.4×10 -6 to 1.8×10 -6 Pa.
於本發明中,較佳為上述密封材與上述層間絕緣膜直接相接。In the present invention, it is preferable that the sealing material and the interlayer insulating film are directly in contact with each other.
於本發明中,較佳為上述密封材含有環氧樹脂。In this invention, it is preferable that the said sealing material contains an epoxy resin.
於本發明中,較佳為上述層間絕緣膜含有選自聚醯亞胺、聚苯并㗁唑及具有酚性羥基之聚合物中之至少一種。In the present invention, it is preferable that the interlayer insulating film contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.
於本發明中,較佳為上述層間絕緣膜含有包含以下通式(1)之結構之聚醯亞胺。 [化1] (通式(1)中,X1 為4價有機基,Y1 為2價有機基,m為1以上之整數)In the present invention, it is preferable that the interlayer insulating film contains polyimide having a structure of the following general formula (1). [化1] (In the general formula (1), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and m is an integer of 1 or more)
於本發明中,較佳為上述通式(1)中之X1 為含有芳香族環之4價有機基,上述通式(1)中之Y1 為含有芳香族環之2價有機基。In the present invention, it is preferable that X 1 in the above general formula (1) is a tetravalent organic group containing an aromatic ring, and Y 1 in the above general formula (1) is a divalent organic group containing an aromatic ring.
於本發明中,較佳為上述通式(1)中之X1 含有下述通式(2)~通式(4)所表示之至少一種結構。 [化2] [化3] [化4] (通式(4)中,R9 為氧原子、硫原子或2價有機基)In the present invention, it is preferable that X 1 in the above general formula (1) contains at least one structure represented by the following general formula (2) to (4). [化2] [化3] [化4] (In the general formula (4), R 9 is an oxygen atom, a sulfur atom or a divalent organic group)
較佳為上述通式(1)中之X1 含有下述通式(5)所表示之結構。 [化5] It is preferable that X 1 in the above general formula (1) contains a structure represented by the following general formula (5). [化5]
較佳為上述通式(1)中之Y1 含有下述通式(6)~通式(8)所表示之至少一種結構。 [化6] (R10 、R11 、R12 及R13 為氫原子、碳數1~5之1價脂肪族基或羥基,可相同亦可不同) [化7] (R14 ~R21 為氫原子、鹵素原子、碳數1~5之1價有機基或羥基,相互可不同,亦可相同) [化8] (R22 為2價基,R23 ~R30 為氫原子、鹵素原子、碳數1~5之1價脂肪族基或羥基,可相同亦可不同)It is preferable that Y 1 in the above general formula (1) contains at least one structure represented by the following general formulas (6) to (8). [化6] (R 10 , R 11 , R 12 and R 13 are hydrogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms or hydroxyl groups, which may be the same or different) [Chemical Formula 7] (R 14 to R 21 are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be different from each other or the same) [Chemical Formula 8] (R 22 is a divalent group, R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different)
於本發明中,較佳為上述通式(1)中之Y1 含有下述通式(9)所表示之結構。 [化9] In the present invention, it is preferable that Y 1 in the above general formula (1) contains a structure represented by the following general formula (9). [化9]
於本發明中,較佳為上述聚苯并㗁唑含有包含以下通式(10)之結構之聚苯并㗁唑。 [化10] (通式(10)中,Y2 與Y3 為2價有機基)In the present invention, it is preferable that the above-mentioned polybenzoxazole contains a polybenzoxazole having a structure of the following general formula (10). [化10] (In the general formula (10), Y 2 and Y 3 are divalent organic groups)
於本發明中,較佳為上述通式(10)之Y2 為碳數1~30之2價有機基。In the present invention, it is preferable that Y 2 of the general formula (10) is a divalent organic group with 1-30 carbon atoms.
於本發明中,較佳為上述通式(10)之Y2 為碳數1~8且氫原子之一部分或全部被取代為氟原子之鏈狀伸烷基。In the present invention, it is preferable that Y 2 of the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and part or all of the hydrogen atoms are substituted with fluorine atoms.
於本發明中,較佳為上述通式(10)之Y3 為含有芳香族基之2價有機基。In the present invention, it is preferable that Y 3 of the general formula (10) is a divalent organic group containing an aromatic group.
於本發明中,較佳為上述通式(10)之Y3 含有下述通式(6)~(8)所表示之至少一種結構。 [化11] (R10 、R11 、R12 及R13 為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [化12] (R14 ~R21 為氫原子、鹵素原子、碳數1~5之1價有機基,相互可不同,亦可相同) [化13] (R22 為2價基,R23 ~R30 為氫原子、鹵素原子、碳數1~5之1價脂肪族基,可相同亦可不同)In the present invention, it is preferable that Y 3 of the above general formula (10) contains at least one structure represented by the following general formulas (6) to (8). [化11] (R 10 , R 11 , R 12 and R 13 are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [化12] (R 14 to R 21 are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same) [Chemical 13] (R 22 is a divalent group, R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different)
較佳為上述通式(10)之Y3 含有下述通式(9)所表示之結構。 [化14] It is preferable that Y 3 of the above general formula (10) contains a structure represented by the following general formula (9). [化14]
於本發明中,較佳為上述通式(10)之Y3 為碳數1~40之2價有機基。In the present invention, it is preferable that Y 3 of the general formula (10) is a divalent organic group having 1-40 carbon atoms.
於本發明中,較佳為上述通式(10)之Y3 為碳數1~20之2價鏈狀脂肪族基。In the present invention, it is preferable that Y 3 of the above general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms.
於本發明中,較佳為上述具有酚性羥基之聚合物含有酚醛清漆型酚樹脂。In this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains a novolak type phenol resin.
於本發明中,較佳為上述具有酚性羥基之聚合物含有不具有不飽和烴基之酚樹脂與具有不飽和烴基之改性酚樹脂。In the present invention, it is preferable that the polymer having a phenolic hydroxyl group contains a phenol resin having no unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.
於本發明中,較佳為上述層間絕緣膜含有填料。In the present invention, it is preferable that the interlayer insulating film contains a filler.
於本發明中,較佳為上述填料為無機填料。In the present invention, it is preferable that the above-mentioned filler is an inorganic filler.
於本發明中,較佳為上述填料之形狀為粒子狀。In the present invention, it is preferable that the shape of the aforementioned filler is particulate.
於本發明中,較佳為上述填料之形狀為球狀。In the present invention, it is preferable that the shape of the filler is spherical.
於本發明中,較佳為上述填料之一次粒徑為5 nm~1 μm。In the present invention, it is preferable that the primary particle size of the above-mentioned filler is 5 nm to 1 μm.
於本發明中,較佳為關於上述再配線層,對上述再配線層進行剖面觀察時,含有第1層間絕緣膜層、第2層間絕緣膜層、及與上述第1層間絕緣膜層及上述第2層間絕緣膜層不同且設置於上述第1層間絕緣膜層與上述第2層間絕緣膜層之間之中間層。In the present invention, it is preferable that the rewiring layer includes a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the The second interlayer insulating film layer is different and is provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer.
於本發明中,較佳為上述第1層間絕緣膜層與上述密封材相接,上述第1層間絕緣膜層於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為5~95重量%。In the present invention, it is preferable that the first interlayer insulating film layer is in contact with the sealing material, and the weight reduction rate of the first interlayer insulating film layer is 5 when the temperature is raised to 700°C at 10°C/min in an air environment ~95% by weight.
於本發明中,較佳為上述第2層間絕緣膜層為與上述第1層間絕緣膜層不同之組成。In the present invention, it is preferable that the second interlayer insulating film layer has a different composition from the first interlayer insulating film layer.
於本發明中,較佳為上述第2層間絕緣膜層於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率與上述第1層間絕緣膜層於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率不同。In the present invention, it is preferable that the weight reduction rate of the second interlayer insulating film layer in an air environment at a temperature of 10°C/min to 700°C is the same as that of the first interlayer insulating film layer in an air environment at 10°C. The weight loss rate after heating up to 700°C per minute is different.
於本發明中,較佳為上述半導體裝置為扇出型之晶圓級晶片尺寸封裝型之半導體裝置。In the present invention, it is preferable that the above-mentioned semiconductor device is a fan-out wafer-level chip size package type semiconductor device.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為10~95重量%。In the present invention, it is preferable that the interlayer insulating film of the rewiring layer has a weight reduction rate of 10 to 95% by weight after the temperature is raised to 700°C at 10°C/min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為20~95重量%。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 20 to 95% by weight after the temperature is raised to 700°C at 10°C/min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為30~90重量%。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 30 to 90% by weight after being heated to 700°C at 10°C/min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為40~90重量%。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 40 to 90% by weight after the temperature is raised to 700°C at 10°C/min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為40~85重量%。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 40 to 85% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為40~80重量%。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 40 to 80% by weight after being heated to 700°C at 10°C/min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為40~75重量%。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 40 to 75% by weight after the temperature is raised to 700°C at 10°C/min in an air environment.
於本發明中,較佳為上述再配線層之層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為40~70重量%。 又,於本發明之另一態樣中,下述內容較佳。In the present invention, it is preferable that the weight loss rate of the interlayer insulating film of the rewiring layer is 40 to 70% by weight after the temperature is raised to 700°C at 10°C/min in an air environment. Furthermore, in another aspect of the present invention, the following content is preferable.
於本發明中,較佳為上述密封材與上述層間絕緣膜直接相接。In the present invention, it is preferable that the sealing material and the interlayer insulating film are directly in contact with each other.
於本發明中,較佳為上述密封材含有環氧樹脂。In this invention, it is preferable that the said sealing material contains an epoxy resin.
於本發明中,較佳為上述層間絕緣膜含有選自聚醯亞胺、聚苯并㗁唑及具有酚性羥基之聚合物中之至少一種。In the present invention, it is preferable that the interlayer insulating film contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.
於本發明中,較佳為上述層間絕緣膜含有包含以下通式(1)之結構之聚醯亞胺。 [化15] (通式(1)中,X1 為4價有機基,Y1 為2價有機基,m為1以上之整數)In the present invention, it is preferable that the interlayer insulating film contains polyimide having a structure of the following general formula (1). [化15] (In the general formula (1), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and m is an integer of 1 or more)
於本發明中,較佳為上述通式(1)中之X1 為含有芳香族環之4價有機基,上述通式(1)中之Y1 為含有芳香族環之2價有機基。In the present invention, it is preferable that X 1 in the above general formula (1) is a tetravalent organic group containing an aromatic ring, and Y 1 in the above general formula (1) is a divalent organic group containing an aromatic ring.
於本發明中,較佳為上述通式(1)中之X1 含有下述通式(2)~通式(4)所表示之至少一種結構。 [化16] [化17] [化18] (通式(4)中,R9 為氧原子、硫原子或2價有機基)In the present invention, it is preferable that X 1 in the above general formula (1) contains at least one structure represented by the following general formula (2) to (4). [化16] [化17] [化18] (In the general formula (4), R 9 is an oxygen atom, a sulfur atom or a divalent organic group)
較佳為上述通式(1)中之X1 含有下述通式(5)所表示之結構。 [化19] It is preferable that X 1 in the above general formula (1) contains a structure represented by the following general formula (5). [化19]
較佳為上述通式(1)中之Y1 含有下述通式(6)~通式(8)所表示之至少一種結構。 [化20] (R10 、R11 、R12 及R13 為氫原子、碳數1~5之1價脂肪族基或羥基,可相同亦可不同) [化21] (R14 ~R21 為氫原子、鹵素原子、碳數1~5之1價有機基或羥基,相互可不同,亦可相同) [化22] (R22 為2價基,R23 ~R30 為氫原子、鹵素原子、碳數1~5之1價脂肪族基或羥基,可相同亦可不同)It is preferable that Y 1 in the above general formula (1) contains at least one structure represented by the following general formulas (6) to (8). [化20] (R 10 , R 11 , R 12 and R 13 are hydrogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms or hydroxyl groups, which may be the same or different) [Chemical Formula 21] (R 14 to R 21 are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbons, or a hydroxyl group, which may be different from each other or the same) [Chemical Formula 22] (R 22 is a divalent group, R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different)
於本發明中,較佳為上述通式(1)中之Y1 含有下述通式(9)所表示之結構。 [化23] In the present invention, it is preferable that Y 1 in the above general formula (1) contains a structure represented by the following general formula (9). [化23]
於本發明中,較佳為上述聚苯并㗁唑含有包含以下通式(10)之結構之聚苯并㗁唑。 [化24] (通式(10)中,Y2 與Y3 為2價有機基)In the present invention, it is preferable that the above-mentioned polybenzoxazole contains a polybenzoxazole having a structure of the following general formula (10). [化24] (In the general formula (10), Y 2 and Y 3 are divalent organic groups)
於本發明中,較佳為上述通式(10)之Y2 為碳數1~30之2價有機基。In the present invention, it is preferable that Y 2 of the general formula (10) is a divalent organic group with 1-30 carbon atoms.
於本發明中,較佳為上述通式(10)之Y2 為碳數1~8且氫原子之一部分或全部被取代為氟原子之鏈狀伸烷基。In the present invention, it is preferable that Y 2 of the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and part or all of the hydrogen atoms are substituted with fluorine atoms.
於本發明中,較佳為上述通式(10)之Y3 為含有芳香族基之2價有機基。In the present invention, it is preferable that Y 3 of the general formula (10) is a divalent organic group containing an aromatic group.
於本發明中,較佳為上述通式(10)之Y3 含有下述通式(6)~(8)所表示之至少一種結構。 [化25] (R10 、R11 、R12 及R13 為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [化26] (R14 ~R21 為氫原子、鹵素原子、碳數1~5之1價有機基,相互可不同,亦可相同) [化27] (R22 為2價基,R23 ~R30 為氫原子、鹵素原子、碳數1~5之1價脂肪族基,可相同亦可不同)In the present invention, it is preferable that Y 3 of the above general formula (10) contains at least one structure represented by the following general formulas (6) to (8). [化25] (R 10 , R 11 , R 12 and R 13 are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [化26] (R 14 to R 21 are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same) [Chemical Formula 27] (R 22 is a divalent group, R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different)
較佳為上述通式(10)之Y3 含有下述通式(9)所表示之結構。 [化28] It is preferable that Y 3 of the above general formula (10) contains a structure represented by the following general formula (9). [化28]
於本發明中,較佳為上述通式(10)之Y3 為碳數1~40之2價有機基。In the present invention, it is preferable that Y 3 of the general formula (10) is a divalent organic group having 1-40 carbon atoms.
於本發明中,較佳為上述通式(10)之Y3 為碳數1~20之2價鏈狀脂肪族基。In the present invention, it is preferable that Y 3 of the above general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms.
於本發明中,較佳為上述具有酚性羥基之聚合物含有酚醛清漆型酚樹脂。In this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains a novolak type phenol resin.
於本發明中,較佳為上述具有酚性羥基之聚合物含有不具有不飽和烴基之酚樹脂與具有不飽和烴基之改性酚樹脂。In the present invention, it is preferable that the polymer having a phenolic hydroxyl group contains a phenol resin having no unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.
於本發明中,較佳為關於上述再配線層,對上述再配線層進行剖面觀察時,含有第1層間絕緣膜層、第2層間絕緣膜層、及與上述第1層間絕緣膜層及上述第2層間絕緣膜層不同且設置於上述第1層間絕緣膜層與上述第2層間絕緣膜層之間之中間層。In the present invention, it is preferable that the rewiring layer includes a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the The second interlayer insulating film layer is different and is provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer.
於本發明中,較佳為上述第1層間絕緣膜層與上述密封材相接,上述第1層間絕緣膜層於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.2×10-6 ~2.5×10-6 Pa。 於本發明中,更佳為上述第1層間絕緣膜層與上述密封材相接,上述第1層間絕緣膜層於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.4×10-6 ~1.8×10-6 Pa。In the present invention, it is preferable that the first interlayer insulating film layer is in contact with the sealing material, and the volatile gas when the first interlayer insulating film layer is kept at 100°C for 60 minutes is 0.2×10 per cm 2 -6 ~2.5×10 -6 Pa. In the present invention, it is more preferable that the first interlayer insulating film layer is in contact with the sealing material, and the volatile gas when the first interlayer insulating film layer is kept at 100°C for 60 minutes is 0.4×10 per cm 2 -6 ~1.8×10 -6 Pa.
於本發明中,較佳為上述第2層間絕緣膜層為與上述第1層間絕緣膜層不同之組成。In the present invention, it is preferable that the second interlayer insulating film layer has a different composition from the first interlayer insulating film layer.
於本發明中,較佳為上述第2層間絕緣膜層於100℃下保持60分鐘時之揮發氣體與上述第1層間絕緣膜層於100℃下保持60分鐘時之揮發氣體不同。In the present invention, it is preferable that the volatile gas when the second interlayer insulating film layer is kept at 100°C for 60 minutes is different from the volatile gas when the first interlayer insulating film layer is kept at 100°C for 60 minutes.
於本發明中,較佳為上述半導體裝置為扇出型之晶圓級晶片尺寸封裝型之半導體裝置。In the present invention, it is preferable that the above-mentioned semiconductor device is a fan-out wafer-level chip size package type semiconductor device.
於本發明中,較佳為上述再配線層之層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.2×10-6 ~2.5×10-6 Pa。 於本發明中,更佳為上述再配線層之層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.6×10-6 ~1.8×10-6 Pa。In the present invention, it is preferable that the volatile gas when the interlayer insulating film of the rewiring layer is kept at 100° C. for 60 minutes is 0.2×10 -6 to 2.5×10 -6 Pa per 1 cm 2 . In the present invention, it is more preferable that the volatile gas when the interlayer insulating film of the rewiring layer is kept at 100°C for 60 minutes is 0.6×10 -6 to 1.8×10 -6 Pa per 1 cm 2 .
於本發明中,進而較佳為上述再配線層之層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.6×10-6 ~1.6×10-6 Pa。In the present invention, it is more preferred that the volatile gas of the interlayer insulating film of the rewiring layer is 0.6×10 -6 to 1.6×10 -6 Pa per 1 cm 2 when kept at 100° C. for 60 minutes.
於本發明中,進而更佳為上述再配線層之層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.6×10-6 ~1.4×10-6 Pa。In the present invention, it is more preferable that the volatile gas when the interlayer insulating film of the rewiring layer is kept at 100°C for 60 minutes is 0.6×10 -6 to 1.4×10 -6 Pa per 1 cm 2 .
於本發明中,較佳為上述層間絕緣膜含有熱交聯劑。In the present invention, it is preferable that the interlayer insulating film contains a thermal crosslinking agent.
於本發明中,較佳為上述層間絕緣膜含有揮發調整劑。In the present invention, it is preferable that the interlayer insulating film contains a volatilization regulator.
於本發明中,較佳為上述層間絕緣膜含有熱交聯劑及揮發調整劑。In the present invention, it is preferable that the interlayer insulating film contains a thermal crosslinking agent and a volatilization regulator.
於本發明中,較佳為上述再配線層含有與上述層間絕緣膜相接之無機膜。In the present invention, it is preferable that the rewiring layer includes an inorganic film in contact with the interlayer insulating film.
於本發明中,較佳為上述無機膜具有上述層間絕緣膜中所含之揮發氣體與上述無機膜之成分進行反應之反應層。In the present invention, it is preferable that the inorganic film has a reaction layer in which the volatile gas contained in the interlayer insulating film reacts with the components of the inorganic film.
本發明之半導體裝置之製造方法之特徵在於:具備以密封材覆蓋半導體晶片之步驟、及形成俯視時面積大於上述半導體晶片且含有層間絕緣膜之再配線層之步驟,並且上述層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為5~95重量%。 本發明之半導體裝置之製造方法之特徵在於:具備以密封材覆蓋半導體晶片之步驟、及形成俯視時面積大於上述半導體晶片且含有層間絕緣膜之再配線層之步驟,並且上述層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.2×10-6 ~2.5×10-6 Pa。 較佳為本發明之半導體裝置之製造方法之特徵在於:具備以密封材覆蓋半導體晶片之步驟、及形成俯視時面積大於上述半導體晶片且含有層間絕緣膜之再配線層之步驟,並且上述層間絕緣膜於100℃下保持60分鐘時之揮發氣體於每1 cm2 中為0.4×10-6 ~1.8×10-6 Pa。The method of manufacturing a semiconductor device of the present invention is characterized in that it includes a step of covering a semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and containing an interlayer insulating film, and the interlayer insulating film is exposed to air Under the environment, the weight loss rate after heating up to 700°C at 10°C/min is 5-95% by weight. The method of manufacturing a semiconductor device of the present invention is characterized in that it includes a step of covering a semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and containing an interlayer insulating film, and the interlayer insulating film is 100 The volatile gas when kept at ℃ for 60 minutes is 0.2×10 -6 ~2.5×10 -6 Pa per 1 cm 2 . Preferably, the method of manufacturing a semiconductor device of the present invention is characterized in that it includes a step of covering a semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer and containing an interlayer insulating film when viewed from above, and the interlayer insulation The volatile gas when the film is kept at 100°C for 60 minutes is 0.4×10 -6 to 1.8×10 -6 Pa per 1 cm 2 .
於本發明中,較佳為包含如下之層間絕緣膜形成步驟:利用可形成聚醯亞胺、聚苯并㗁唑、具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物形成上述層間絕緣膜。In the present invention, it is preferable to include the step of forming an interlayer insulating film: using a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and polymer having phenolic hydroxyl group. Interlayer insulating film.
於本發明中,較佳為上述層間絕緣膜形成步驟包含如下步驟:利用以上述層間絕緣膜於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率成為5~95重量%之方式經填料調整之上述感光性樹脂組合物,形成上述層間絕緣膜。 於本發明中,較佳為包含如下之層間絕緣膜形成步驟:利用可形成聚醯亞胺、聚苯并㗁唑、具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物形成上述層間絕緣膜。In the present invention, it is preferable that the step of forming the interlayer insulating film includes the following steps: using the interlayer insulating film in an air environment, the weight reduction rate after the temperature is raised to 700°C at 10°C/min to be 5 to 95% by weight The photosensitive resin composition adjusted by the filler forms the interlayer insulating film. In the present invention, it is preferable to include the step of forming an interlayer insulating film: using a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and polymer having phenolic hydroxyl group. Interlayer insulating film.
於本發明中,較佳為上述層間絕緣膜形成步驟包含如下步驟:利用以上述層間絕緣膜於100℃下保持60分鐘時之揮發氣體成為0.2×10-6 ~2.5×10-6 Pa之方式經調整之上述感光性樹脂組合物,形成上述層間絕緣膜。 於本發明中,更佳為上述層間絕緣膜形成步驟包含如下步驟:利用以上述層間絕緣膜於100℃下保持60分鐘時之揮發氣體成為0.4×10-6 ~1.8×10-6 Pa之方式經調整之上述感光性樹脂組合物,形成上述層間絕緣膜。In the present invention, it is preferable that the step of forming the interlayer insulating film includes the following steps: using the method in which the volatile gas becomes 0.2×10 -6 to 2.5×10 -6 Pa when the interlayer insulating film is kept at 100° C. for 60 minutes The adjusted photosensitive resin composition forms the interlayer insulating film. In the present invention, it is more preferable that the step of forming the interlayer insulating film includes the following steps: using the method in which the volatile gas becomes 0.4×10 -6 to 1.8×10 -6 Pa when the interlayer insulating film is kept at 100°C for 60 minutes The adjusted photosensitive resin composition forms the interlayer insulating film.
於本發明中,較佳為上述層間絕緣膜形成步驟包含如下步驟:利用以上述層間絕緣膜於100℃下保持60分鐘時之揮發氣體成為0.2×10-6 ~2.5×10-6 Pa之方式經熱交聯劑及/或揮發調整劑調整之上述感光性樹脂組合物,形成上述層間絕緣膜。 於本發明中,更佳為上述層間絕緣膜形成步驟包含如下步驟:利用以上述層間絕緣膜於100℃下保持60分鐘時之揮發氣體成為0.4×10-6 ~1.8×10-6 Pa之方式經熱交聯劑及/或揮發調整劑調整之上述感光性樹脂組合物,形成上述層間絕緣膜。 [發明之效果]In the present invention, it is preferable that the step of forming the interlayer insulating film includes the following steps: using the method in which the volatile gas becomes 0.2×10 -6 to 2.5×10 -6 Pa when the interlayer insulating film is kept at 100° C. for 60 minutes The photosensitive resin composition adjusted with a thermal crosslinking agent and/or a volatilization regulator forms the interlayer insulating film. In the present invention, it is more preferable that the step of forming the interlayer insulating film includes the following steps: using the method in which the volatile gas becomes 0.4×10 -6 to 1.8×10 -6 Pa when the interlayer insulating film is kept at 100°C for 60 minutes The photosensitive resin composition adjusted with a thermal crosslinking agent and/or a volatilization regulator forms the interlayer insulating film. [Effects of Invention]
根據本發明,可提供一種再配線層中之層間絕緣膜與密封材之密接性優異、電測定優異之半導體裝置及其製造方法。According to the present invention, it is possible to provide a semiconductor device with excellent adhesion between the interlayer insulating film in the rewiring layer and the sealing material and excellent electrical measurement, and a manufacturing method thereof.
以下,參考圖式詳細說明本發明之半導體裝置之一實施形態(以下,簡稱為「實施形態」)。再者,本發明不受以下實施形態限定,可於其主旨之範圍內進行各種變化而實施。Hereinafter, one embodiment of the semiconductor device of the present invention (hereinafter referred to simply as "embodiment") will be described in detail with reference to the drawings. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist.
(半導體裝置)
如圖1所示,半導體裝置(半導體IC(Integrated Circuit,積體電路))1具有半導體晶片2、覆蓋半導體晶片2之密封材(塑模樹脂)3、及與半導體晶片2及密封材3密接之再配線層4而構成。(Semiconductor device)
As shown in FIG. 1, a semiconductor device (semiconductor IC (Integrated Circuit)) 1 has a
如圖1所示,密封材3覆蓋半導體晶片2之表面,並且以俯視(沿箭頭A方向觀察)上大於半導體晶片2之區域之面積而形成。As shown in FIG. 1, the sealing
再配線層4具有與設置於半導體晶片2之複數個端子2a電性連接之複數個配線5、及將配線5間埋覆之層間絕緣膜6而構成。設置於半導體晶片2之複數個端子2a與再配線層4內之配線5電性連接。配線5之一端與端子2a連接,另一端與外部連接端子7連接。端子2a與外部連接端子7之間之配線5之整個面被層間絕緣膜6覆蓋。The
如圖1所示,俯視(沿箭頭A方向觀察)上再配線層4以大於半導體晶片2之方式形成。圖1所示之半導體裝置1為扇出(Fan-Out)型之晶圓級晶片尺寸封裝(WLCSP)型之半導體裝置。於扇出型之半導體裝置中,再配線層4中之層間絕緣膜6不僅與半導體晶片2密接,亦與密封材3密接。半導體晶片2包含矽等半導體,於內部形成電路。As shown in FIG. 1, the
(再配線層)
再配線層4主要包含配線5與覆蓋配線5之周圍之層間絕緣膜6。就防止與配線5之未意料之導通之觀點而言,層間絕緣膜6較佳為絕緣性較高之構件。(Rewiring layer)
The
此處,本實施形態中之所謂「再配線層4」係指如上所述具有配線5與層間絕緣膜6之薄膜之層,不含中介層(Interposer)或印刷配線板。半導體裝置(半導體IC)1使用再配線層4,故而如圖4所示,與覆晶BGA等使用中介層之半導體裝置相比較更薄。Here, the "
於本實施形態中,可將再配線層4之膜厚設為3~30 μm左右。再配線層4之膜厚可為1 μm以上,亦可為5 μm以上,亦可為10 μm以上。又,再配線層4之膜厚可為40 μm以下,亦可為30 μm以下,亦可為20 μm以下。
於俯視(沿箭頭A方向觀察)半導體裝置1之情形時,成為以下之圖2。再者,省略密封材3。In this embodiment, the film thickness of the
圖2所示之半導體裝置1係以再配線層4之面積S1大於半導體晶片2之面積S2之方式構成。再配線層4之面積S1並無特別限定,就增多外部連接端子之數目之觀點而言,較佳為再配線層4之面積S1為半導體晶片2之面積S2之1.05倍以上,較佳為1.1倍以上,更佳為1.2倍以上,尤佳為1.3倍以上。關於上限並無特別限定,再配線層4之面積S1可為半導體晶片2之面積S2之50倍以下,亦可為25倍以下,亦可為10倍以下,亦可為5倍以下。再者,於圖2中,被半導體晶片2覆蓋之再配線層4之部分之面積亦包含於再配線層4之面積S1中。The semiconductor device 1 shown in FIG. 2 is constructed such that the area S1 of the
又,半導體晶片2及再配線層4之外形可相同,亦可不同。於圖2中,半導體晶片2及再配線層4之外形均為矩形之相似形狀,形狀亦可為矩形以外之形狀。In addition, the outer shape of the
再配線層4可為1層,亦可為2層以上之多層。再配線層4包含配線5及將配線5間埋覆之層間絕緣膜6,但再配線層4中亦包含僅由層間絕緣膜6構成之層或僅由配線5構成之層。The
配線5只要為導電性較高之構件,則並無特別限定,通常使用銅。The
(密封材)
密封材3之材料並無特別限定,就耐熱性、與層間絕緣膜之密接性之觀點而言,較佳為環氧樹脂。(Sealing material)
The material of the sealing
如圖1所示,密封材3較佳為與半導體晶片2及再配線層4直接相接。藉此,可有效地提高自半導體晶片2之表面至再配線層4之表面之密封性。As shown in FIG. 1, the sealing
密封材3可為單層,亦可為積層有複數層之構成。於密封材3為積層結構之情形時,可為同種材料之積層結構,亦可為不同材料之積層結構。The sealing
(層間絕緣膜)
於本實施形態中,有如下特徵:層間絕緣膜6於空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為5~95重量%。以下,將空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率簡稱為「重量減少率」。(Interlayer insulating film)
In this embodiment, it has the following characteristics: the interlayer insulating
若重量減少率為5~95重量%,則層間絕緣膜6與密封材3之高溫處理時之密接性優異。其理由並不確定,但本發明者等人推測如下。If the weight reduction rate is 5 to 95% by weight, the
於扇出型之半導體裝置之製造過程中,為形成再配線層4,於包含半導體晶片2及密封材3之晶片密封體上塗佈感光性樹脂組合物。繼而,將感光性樹脂組合物曝光。其後,將感光性樹脂組合物進行顯影、硬化,藉此選擇性地形成具有光性樹脂組合物之硬化物之部分與不具有光性樹脂組合物之硬化物之部分。感光性樹脂組合物之硬化物成為層間絕緣膜6。又,於不具有感光性樹脂組合物之硬化物之部分形成配線5。通常,再配線層4成為多層之情形較多。即,於層間絕緣膜6與配線5上進而將感光性樹脂組合物塗佈、曝光、顯影、硬化。In the manufacturing process of the fan-out type semiconductor device, in order to form the
另外,於形成層間絕緣膜6與配線5之步驟中,根據製造方法,存在包含回焊步驟之情形。另一方面,層間絕緣膜6如上所述需要進行圖案化,故而通常含有具有極性之樹脂或添加劑之情形較多,存在易於含有水分之傾向。推測由於該絕緣膜經過回焊等暫時高溫度之熱歷程,從而導致揮發之水分產生於密封材與絕緣膜之界面,故而密接性下降。於層間絕緣膜6之樹脂含有率較低,即,層間絕緣膜6之重量減少率為特定範圍之情形時,存在水分之揮發得以抑制之傾向,故而存在於密封材3與層間絕緣膜6之界面不易蓄積氣體,不易剝離密封材3與層間絕緣膜6之傾向。又,於層間絕緣膜6之重量減少率為特定範圍之情形時,樹脂含有率充分高,故而可充分確保與密封材之密接性。In addition, in the step of forming the
本實施形態之層間絕緣膜6較佳為空氣環境下、以10℃/分鐘升溫至700℃後之重量減少率為5~95重量%。故而,於本實施形態中,層間絕緣膜6與密封材3之密接性良好,且熱歷程中自層間絕緣膜6揮發之水分較少,故而熱歷程後之密接性亦良好。The
就層間絕緣膜與密封材3之初始之密接性之觀點而言,層間絕緣膜6之重量減量率較佳為95重量%以下,更佳為90重量%以下,進而較佳為85重量%以下,進而更佳為80重量%以下,尤佳為75重量%以下。From the viewpoint of the initial adhesion between the interlayer insulating film and the sealing
層間絕緣膜6之重量減量率可為70重量%以下,亦可為65重量%以下,亦可為60重量%以下,亦可為55重量%以下,亦可為50重量%以下,亦可為45重量%以下,亦可為40重量%以下,亦可為35重量%以下,亦可為30重量%以下,亦可為25重量%以下,亦可為20重量%以下。The weight loss rate of the
就層間絕緣膜與密封材3之熱歷程後之密接性之觀點而言,層間絕緣膜6之重量減量率較佳為5重量%以上,更佳為10重量%以上,進而較佳為15重量%以上,進而更佳為20重量%以上,尤佳為25重量%以上,尤其更佳為30重量%以上,進一步較佳為35重量%以上,最佳為40重量%以上。From the viewpoint of the adhesion between the interlayer insulating film and the sealing
層間絕緣膜6之重量減量率可為45重量%以上,亦可為50重量%以上,亦可為55重量%以上,亦可為60重量%以上,亦可為65重量%以上,亦可為70重量%以上,亦可為75重量%以上,亦可為80重量%以上。The weight loss rate of the
於本實施之形態之層間絕緣膜6之重量減少率為特定範圍之情形時,例如製為天線一體型模組時之電特性變得良好。理由並未確定,但本發明者等人認為如下。In the case where the weight reduction rate of the
即,於重量減少率較小之情形時,成為含有較多無機填料等重量不易減少之材料之層間絕緣膜,該等存在介電損耗正切較低之傾向。故而存在例如與天線單獨體相比較,製為天線一體型模組時之偏移較小之傾向。於重量減少率較大之情形時,於層間絕緣膜中含有較多樹脂等成分,故而存在層間絕緣膜中所含之成分之均勻性良好,送至天線或自天線送出之信號之漣波(波形之混亂)得以抑制之傾向。推測於層間絕緣膜6之重量減少率為特定範圍之情形時,可兼具該等傾向,可使電特性變得良好。That is, when the weight reduction rate is small, it becomes an interlayer insulating film containing more inorganic fillers and other materials that are not easily reduced in weight, and these tend to have a low dielectric loss tangent. Therefore, for example, compared with a single antenna body, the deviation tends to be smaller when the antenna integrated module is manufactured. When the weight reduction rate is large, the interlayer insulating film contains more resin and other components, so there is a good uniformity of the components contained in the interlayer insulating film, and the ripple of the signal sent to or from the antenna ( The chaos of the waveform) can be suppressed. It is estimated that when the weight reduction rate of the
(層間絕緣膜)
於本實施之另一形態中,有如下特徵:層間絕緣膜6於100℃下保持60分鐘時之揮發氣體於每1 cm2
中為0.2×10-6
~2.5×10-6
Pa。
於本實施之又一形態中,有如下特徵:層間絕緣膜6於100℃下保持60分鐘時之揮發氣體於每1 cm2
中為0.4×10-6
~1.8×10-6
Pa。以下,將100℃下保持60分鐘時之揮發氣體簡稱為「揮發氣體壓力」。(Interlayer insulating film) In another form of this embodiment, it has the following characteristics: the volatile gas of the
若層間絕緣膜6於100℃下保持60分鐘時之揮發氣體為上述範圍,則層間絕緣膜6與無機膜8之密接性優異。其理由並不確定,但本發明者等人推測如下。If the volatilized gas when the
於扇出型之半導體裝置之製造過程中,為形成再配線層4,於包含半導體晶片2及密封材3之晶片密封體上塗佈感光性樹脂組合物。繼而,將感光性樹脂組合物曝光。其後,將感光性樹脂組合物進行顯影、硬化,藉此選擇性地形成具有光性樹脂組合物之硬化物之部分與不具有光性樹脂組合物之硬化物之部分。感光性樹脂組合物之硬化物成為層間絕緣膜6。又,於不具有感光性樹脂組合物之硬化物之部分形成配線5。通常,再配線層4成為多層之情形較多。即,於層間絕緣膜6與配線5上進而塗佈感光性樹脂組合物並曝光、顯影、硬化。In the manufacturing process of the fan-out type semiconductor device, in order to form the
另外,於形成層間絕緣膜6與配線5之步驟中,根據製造方法,有包含濺鍍鈦等無機膜之步驟之情形。另一方面,層間絕緣膜6如上所述需要進行圖案化,故而通常含有具有極性之樹脂或添加劑之情形較多,存在易於含有水分之傾向。含有之水分或易於在真空中揮發之成分於濺鍍中揮發一定量,由此於層間絕緣膜6與無機膜8之間形成無機膜與揮發成分進行反應之層。若無機膜8為鈦之情形,則形成含有氧化鈦之層。藉由該反應層,可提高層間絕緣膜6與無機膜8之密接性。但若揮發成分過多,則存在因揮發成分而導致層間絕緣膜6與無機膜8之密接性下降之虞。In addition, the step of forming the
本實施形態之層間絕緣膜6較佳為於100℃下保持60分鐘時之揮發氣體於每1 cm2
中為0.4×10-6
~1.8×10-6
Pa。故而,於本實施形態中,層間絕緣膜6與無機膜之密接性良好。The
就層間絕緣膜與無機膜之密接性之觀點而言,層間絕緣膜6於100℃下保持60分鐘時之揮發氣體壓力較佳為0.4×10-6
Pa以上,更佳為0.6×10-6
Pa以上,進而較佳為0.8×10-6
Pa以上,進而更佳為1.0×10-6
Pa以上。From the viewpoint of the adhesion between the interlayer insulating film and the inorganic film, the volatile gas pressure of the
層間絕緣膜6於100℃下保持60分鐘時之揮發氣體壓力只要於每1 cm2
中為1.8×10-6
以下則並無限定。較佳為1.8×10-6
以下,更佳為1.6×10-6
以下,尤佳為1.4×10-6
以下。The pressure of the volatile gas when the
於本實施之形態之層間絕緣膜6於100℃下保持60分鐘時之揮發氣體壓力為特定範圍之情形時,例如製為天線一體型模組時之電特性變得良好。理由並不確定,但本發明者等人考慮如下。In the case where the volatile gas pressure of the
即,在於100℃下保持60分鐘時之揮發氣體壓力較低之情形時,成為含有較多聚合物等不易揮發之材料之層間絕緣膜,該等存在介電損耗正切較低之傾向。故而,存在例如與天線單獨體相比較,製為天線一體型模組時之偏移較小之傾向。That is, when the volatile gas pressure is low when kept at 100°C for 60 minutes, it becomes an interlayer insulating film containing more polymers and other non-volatile materials, and these tend to have a low dielectric loss tangent. Therefore, there is a tendency that the deviation when manufactured as an antenna integrated module is smaller than that of a single antenna.
又,再配線層4中之層間絕緣膜6可為多層。即,關於再配線層4,對再配線層4進行剖面觀察時,可含有第1層間絕緣膜層、第2層間絕緣膜層、及與第1層間絕緣膜層及上述第2層間絕緣膜層不同且設置於第1層間絕緣膜層與第2層間絕緣膜層之間之中間層。所謂中間層例如為配線5。Moreover, the
第1層間絕緣膜層與第2層間絕緣膜層可為相同組成,亦可為不同組成。第1層間絕緣膜層與第2層間絕緣膜層可為相同揮發氣體壓力,亦可為不同揮發氣體壓力。第1層間絕緣膜層與第2層間絕緣膜層可為相同膜厚,亦可為不同膜厚。若第1層間絕緣膜層與第2層間絕緣膜層為不同組成或不同揮發氣體壓力或不同膜厚,則各層間絕緣膜層可具有不同性質,故較佳。The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same volatile gas pressure or different volatile gas pressures. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions or different volatilized gas pressures or different film thicknesses, each interlayer insulating film layer can have different properties, which is preferable.
於層間絕緣膜6為多層之情形時,存在之複數個層中,至少1層之層間絕緣膜6於100℃下保持60分鐘時之揮發氣體壓力於每1 cm2
中為0.2×10-6
~2.5×10-6
Pa即可。
較佳為於層間絕緣膜6為多層之情形時,存在之複數個層中,至少1層之層間絕緣膜6於100℃下保持60分鐘時之揮發氣體壓力於每1 cm2
中為0.4×10-6
~1.8×10-6
Pa即可。In the case where the
又,再配線層4中之層間絕緣膜6可為多層。即,關於再配線層4,對再配線層4進行剖面觀察時,可含有第1層間絕緣膜層、第2層間絕緣膜層、及與第1層間絕緣膜層及上述第2層間絕緣膜層不同且設置於第1層間絕緣膜層與第2層間絕緣膜層之間之中間層。所謂中間層例如為配線5。Moreover, the
第1層間絕緣膜層與第2層間絕緣膜層可為相同組成,亦可為不同組成。第1層間絕緣膜層與第2層間絕緣膜層可為相同重量減少率,亦可為不同重量減少率。第1層間絕緣膜層與第2層間絕緣膜層可為相同膜厚,亦可為不同膜厚。若第1層間絕緣膜層與第2層間絕緣膜層為不同組成或不同重量減少率或不同膜厚,則各層間絕緣膜層可具有不同性質,故較佳。The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same weight reduction rate or different weight reduction rates. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions or different weight reduction rates or different film thicknesses, each interlayer insulating film layer may have different properties, which is preferable.
於層間絕緣膜6為多層之情形時,存在之複數個層中,至少1層之層間絕緣膜6之重量減少率為5~95重量%即可,但密封材3與層間絕緣膜層之間易於因氣體而剝離,故而較佳為與密封材3相接之層間絕緣膜層之層間絕緣膜6之重量減少率為10~95重量%。若與密封材3相接之層間絕緣膜層之層間絕緣膜6之重量減少率為10~95重量%,則密封材3與層間絕緣膜6之密接性優異。When the
(層間絕緣膜之組成)
層間絕緣膜6之組成並無特別限定,例如較佳為含有選自聚醯亞胺、聚苯并㗁唑或具有酚性羥基之聚合物中之至少一種化合物之膜。(Composition of interlayer insulating film)
The composition of the
(形成層間絕緣膜之樹脂組合物)
用於形成層間絕緣膜6之樹脂組合物只要為感光性之樹脂組合物,則並無特別限定,較佳為含有選自聚醯亞胺前驅物、聚苯并㗁唑前驅物或具有酚性羥基之聚合物中之至少一種化合物之感光性樹脂組合物。用於形成層間絕緣膜6之樹脂組合物可為液體狀亦可為膜狀。又,用於形成層間絕緣膜6之樹脂組合物可為負型之感光性樹脂組合物,亦可為正型之感光性樹脂組合物。(Resin composition for forming interlayer insulating film)
The resin composition used to form the
於本實施形態中,將對感光性樹脂組合物進行曝光及顯影後之圖案稱為凸紋圖案,將對凸紋圖案進行加熱硬化後之圖案稱為硬化凸紋圖案。該硬化凸紋圖案成為層間絕緣膜6。In this embodiment, the pattern after exposing and developing the photosensitive resin composition is called a relief pattern, and the pattern after heat-hardening a relief pattern is called a hardened relief pattern. This hardened relief pattern becomes the interlayer insulating
於本實施形態中,層間絕緣膜6之感光性樹脂組合物較佳為含有填料。所謂本實施形態中之填料,只要為以改良強度或各種性質為目的而添加之惰性物質,則並無限定。In this embodiment, the photosensitive resin composition of the
就抑制製為樹脂組合物時之黏度上升之觀點而言,填料較佳為粒子狀。作為粒子狀之例,有針狀、板狀、球狀等,就抑制製為樹脂組合物時之黏度上升之觀點而言,填料較佳為球狀。From the viewpoint of suppressing the increase in viscosity when the resin composition is prepared, the filler is preferably in the form of particles. Examples of the particle shape include needle shape, plate shape, spherical shape, and the like. From the viewpoint of suppressing the increase in viscosity when the resin composition is prepared, the filler is preferably spherical.
作為針狀填料,可列舉:矽灰石、鈦酸鉀、硬矽鈣石、硼酸鋁、針狀碳酸鈣等。Examples of needle-shaped fillers include wollastonite, potassium titanate, xonotlite, aluminum borate, and needle-shaped calcium carbonate.
作為板狀填料,可列舉:滑石、雲母、絹雲母、玻璃鱗片、蒙脫石、氮化硼、板狀碳酸鈣等。Examples of the plate-like filler include talc, mica, sericite, glass flakes, montmorillonite, boron nitride, and plate-like calcium carbonate.
作為球狀填料,可列舉:碳酸鈣、氧化矽、氧化鋁、氧化鈦、黏土、水滑石(hydrotalcite)、氫氧化鎂、氧化鋅、鈦酸鋇等。該等之中,就電特性或製為樹脂組合物時之保存穩定性之觀點而言,較佳為氧化矽、氧化鋁、氧化鈦、鈦酸鋇,更佳為氧化矽、氧化鋁。Examples of spherical fillers include calcium carbonate, silica, alumina, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, and barium titanate. Among them, from the viewpoint of electrical properties or storage stability when the resin composition is prepared, silica, alumina, titanium oxide, and barium titanate are preferred, and silica and alumina are more preferred.
作為填料之大小,於球狀之情形時將一次粒徑定義為大小,於板狀或針狀之情形時將長邊之長度定義為大小,較佳為5 nm~1000 nm,更佳為10 nm~1000 nm。若為10 nm以上,則存在製為樹脂組合物時變得充分均勻之傾向,若為1000 nm以下,則可賦予感光性。就感光性賦予之觀點而言,較佳為800 nm以下,更佳為600 nm以下,尤佳為300 nm以下。就密接性或樹脂組合物均勻性之觀點而言,較佳為15 nm以上,更佳為30 nm以上,尤佳為50 nm以上。As the size of the filler, the primary particle size is defined as the size in the case of a spherical shape, and the length of the long side is defined as the size in the case of a plate or needle shape, preferably 5 nm to 1000 nm, more preferably 10 nm~1000 nm. If it is 10 nm or more, it tends to become sufficiently uniform when used as a resin composition, and if it is 1000 nm or less, photosensitivity can be imparted. From the viewpoint of imparting photosensitivity, it is preferably 800 nm or less, more preferably 600 nm or less, and particularly preferably 300 nm or less. From the viewpoint of adhesion or resin composition uniformity, it is preferably 15 nm or more, more preferably 30 nm or more, and particularly preferably 50 nm or more.
於本實施之另一形態中,層間絕緣膜6之感光性樹脂組合物較佳為含有熱交聯劑或揮發調整劑。對感光性樹脂組合物並無特別限定,可為含有選自聚醯亞胺前驅物、聚苯并㗁唑前驅物或具有酚性羥基之聚合物中之至少一種化合物之感光性樹脂組合物。作為熱交聯促進劑,例如可較佳使用:環氧化合物、氧環丁烷化合物、㗁唑啉化合物、醛、醛改性物、異氰酸酯化合物、含不飽和鍵之化合物、多元醇化合物、多胺化合物、三聚氰胺化合物、金屬螯合劑、C-羥甲基系化合物、N-羥甲基系化合物等。In another aspect of this embodiment, the photosensitive resin composition of the
作為揮發調整劑,可列舉:聚乙二醇、聚丙二醇等。As a volatilization adjusting agent, polyethylene glycol, polypropylene glycol, etc. are mentioned.
<聚醯亞胺前驅物組合物> (A)感光性樹脂 作為用於聚醯亞胺前驅物組合物之感光性樹脂,可列舉:聚醯胺、聚醯胺酸酯等。例如,作為聚醯胺酸酯,可使用含有下述通式(11)所表示之重複單元之聚醯胺酸酯。<Polyimine precursor composition> (A) Photosensitive resin Examples of the photosensitive resin used for the polyimide precursor composition include polyamide, polyamide ester, and the like. For example, as the polyamide, a polyamide containing a repeating unit represented by the following general formula (11) can be used.
[化29] R1 及R2 分別獨立為氫原子、碳數1~30之飽和脂肪族基、芳香族基、具有碳碳不飽和雙鍵之一價有機基、或具有碳碳不飽和雙鍵之一價離子。X1 為4價有機基,Y1 為2價有機基,m為1以上之整數。m較佳為2以上,更佳為5以上。[化29] R 1 and R 2 are each independently a hydrogen atom, a saturated aliphatic group with 1 to 30 carbons, an aromatic group, a monovalent organic group with a carbon-carbon unsaturated double bond, or a monovalent organic group with a carbon-carbon unsaturated double bond ion. X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and m is an integer of 1 or more. m is preferably 2 or more, more preferably 5 or more.
上述通式(11)之R1 及R2 作為一價陽離子存在時,O帶負之電荷(作為-O- 而存在)。又,X1 與Y1 可含有羥基。When R 1 and R 2 of the above general formula (11) exist as monovalent cations, O has a negative charge (exists as -O - ). In addition, X 1 and Y 1 may contain a hydroxyl group.
通式(11)中之R1 及R2 更佳為下述通式(12)所表示之1價有機基、或下述通式(13)所表示之1價有機基之末端具有銨離子之結構。R 1 and R 2 in the general formula (11) are more preferably the monovalent organic group represented by the following general formula (12), or the monovalent organic group represented by the following general formula (13) has an ammonium ion at the end The structure.
[化30] (通式(12)中,R3 、R4 及R5 分別獨立為氫原子或碳數1~5之有機基,並且m1 為1~20之整數)[化30] (In the general formula (12), R 3 , R 4 and R 5 are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m 1 is an integer of 1 to 20)
[化31] (通式(13)中,R6 、R7 及R8 分別獨立為氫原子或碳數1~5之有機基,並且m2 為1~20之整數)。[化31] (In the general formula (13), R 6 , R 7 and R 8 are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m 2 is an integer of 1 to 20).
可混合複數種通式(11)所表示之聚醯胺酸酯。又,可使用使通式(11)所表示之聚醯胺酸酯彼此共聚而成之聚醯胺酸酯。A plurality of polyamide esters represented by the general formula (11) can be mixed. In addition, a polyamide obtained by copolymerizing polyamides represented by the general formula (11) with each other can be used.
X1
並無特別限定,就層間絕緣膜6與密封材3之密接性之觀點而言,X1
較佳為含有芳香族基之4價有機基。具體而言,X1
較佳為含有下述通式(2)~通式(4)所表示之至少一種結構之4價有機基。X 1 is not particularly limited. From the viewpoint of the adhesion between the interlayer insulating
[化32] [化32]
[化33] [化33]
[化34] (通式(4)中,R9 為氧原子、硫原子、2價有機基之任一者)[化34] (In the general formula (4), R 9 is any one of an oxygen atom, a sulfur atom, or a divalent organic group)
通式(4)中之R9 例如為碳數1~40之2價有機基或鹵素原子。R9 可含有羥基。R 9 in the general formula (4) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom. R 9 may contain a hydroxyl group.
就層間絕緣膜6與密封材3之密接性之觀點而言,X1
尤佳為含有下述通式(5)所表示之結構之4價有機基。Tetravalent
[化35] [化35]
Y1
並無特別限定,就層間絕緣膜6與密封材3之密接性之觀點而言,Y1
較佳為含有芳香族基之2價有機基。具體而言,Y1
較佳為含有下述通式(6)~通式(8)所表示之至少一種結構之2價有機基。Y 1 is not particularly limited. From the viewpoint of the adhesion between the interlayer insulating
[化36] (R10 、R11 、R12 及R13 為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同)[化36] (R 10 , R 11 , R 12 and R 13 are hydrogen atoms and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)
[化37] (R14 ~R21 為氫原子、鹵素原子、碳數1~5之1價有機基,相互可不同,亦可相同)[化37] (R 14 to R 21 are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)
[化38] (R22 為2價基,R23 ~R30 為氫原子、鹵素原子、碳數1~5之1價脂肪族基,可相同亦可不同)[化38] (R 22 is a divalent group, R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different)
通式(8)中之R22 例如為碳數1~40之2價有機基或鹵素原子。R 22 in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.
就層間絕緣膜6與密封材3之密接性之觀點而言,Y1
尤佳為含有下述通式(9)所表示之結構之2價有機基。From the viewpoint of the adhesion between the interlayer insulating
[化39] [化39]
於上述聚醯胺酸酯中,其重複單元中之X1 係源自用作原料之四羧酸二酐,Y1 係源自用作原料之二胺。In the above-mentioned polyamide ester, X 1 in the repeating unit is derived from tetracarboxylic dianhydride used as a raw material, and Y 1 is derived from diamine used as a raw material.
作為用作原料之四羧酸二酐,例如可列舉:均苯四甲酸二酐、二苯醚-3,3',4,4'-四羧酸二酐、二苯甲酮-3,3',4,4'-四羧酸二酐、聯苯-3,3',4,4'-四羧酸二酐、二苯碸-3,3',4,4'-四羧酸二酐、二苯基甲烷-3,3',4,4'-四羧酸二酐、2,2-雙(3,4-鄰苯二甲酸酐)丙烷、2,2-雙(3,4-鄰苯二甲酸酐)-1,1,1,3,3,3-六氟丙烷等,但並不限定於該等。又,該等可單獨使用,亦可混合兩種以上使用。As the tetracarboxylic dianhydride used as a raw material, for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, and benzophenone-3,3 can be mentioned. ',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl sulfide-3,3',4,4'-tetracarboxylic dianhydride Anhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4 -Phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., but it is not limited to these. Moreover, these can be used individually or in mixture of 2 or more types.
作為用作原料之二胺,例如可列舉:對苯二胺、間苯二胺、4,4'-二胺基二苯醚、3,4'-二胺基二苯醚、3,3'-二胺基二苯醚、4,4'-二胺基二苯硫醚、3,4'-二胺基二苯硫醚、3,3'-二胺基二苯硫醚、4,4'-二胺基二苯碸、3,4'-二胺基二苯碸、3,3'-二胺基二苯碸、4,4'-二胺基聯苯、3,4'-二胺基聯苯、3,3'-二胺基聯苯、4,4'-二胺基二苯甲酮、3,4'-二胺基二苯甲酮、3,3'-二胺基二苯甲酮、4,4'-二胺基二苯基甲烷、3,4'-二胺基二苯基甲烷、3,3'-二胺基二苯基甲烷、1,4-雙(4-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、4,4-雙(4-胺基苯氧基)聯苯、4,4-雙(3-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]醚、雙[4-(3-胺基苯氧基)苯基]醚、1,4-雙(4-胺基苯基)苯、1,3-雙(4-胺基苯基)苯、9,10-雙(4-胺基苯基)蒽、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基)丙烷、2,2-雙[4-(4-胺基苯氧基)苯基)六氟丙烷、1,4-雙(3-胺基丙基二甲基矽烷基)苯、聯鄰甲苯胺碸、9,9-雙(4-胺基苯基)茀等。又,亦可為該等之苯環上之氫原子之一部分被取代者。又,該等可單獨使用,亦可混合兩種以上使用。As the diamine used as a raw material, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3' -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl sulfide, 3,4'-Diaminodiphenyl sulfide, 3,3'-Diaminodiphenyl sulfide, 4,4'-Diaminodiphenyl, 3,4'-di Amino biphenyl, 3,3'-diamino biphenyl, 4,4'-diamino benzophenone, 3,4'-diamino benzophenone, 3,3'-diamino Benzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis( 4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-amine Phenyloxy)phenyl]sulphur, bis[4-(3-aminophenoxy)phenyl]sulphur, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis (3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1, 4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4 -Aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2 -Bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, di-o-toluidine, 9,9 -Bis(4-aminophenyl) pyridium and the like. In addition, part of the hydrogen atoms on the benzene ring may be substituted. Moreover, these can be used individually or in mixture of 2 or more types.
於聚醯胺酸酯(A)之合成中,通常可較佳使用如下方法:將進行下述四羧酸二酐之酯化反應而獲得之四羧酸二酯直接供至與二胺之縮合反應。In the synthesis of polyamide (A), the following method can usually be preferably used: the tetracarboxylic acid diester obtained by the following esterification reaction of tetracarboxylic dianhydride is directly supplied to the condensation with diamine reaction.
上述四羧酸二酐之酯化反應中所使用之醇類係具有烯烴性雙鍵之醇。具體可列舉:甲基丙烯酸2-羥基乙酯、2-甲基丙烯醯氧基乙醇、甘油二丙烯酸酯、甘油二甲基丙烯酸酯等,但並不限定於該等。該等醇類可單獨使用或混合兩種以上使用。The alcohol used in the esterification reaction of the tetracarboxylic dianhydride is an alcohol having an olefinic double bond. Specific examples include 2-hydroxyethyl methacrylate, 2-methacryloxyethanol, glycerol diacrylate, glycerol dimethacrylate, and the like, but are not limited to these. These alcohols can be used alone or in combination of two or more.
關於本實施形態中所使用之聚醯胺酸酯(A)之具體合成方法,可採用先前公知之方法。關於合成方法,例如可列舉國際公開第00/43439號說明書中所示之方法。即,可列舉如下方法:將四羧酸二酯暫時轉換為四羧酸二酯二醯氯化物,將該四羧酸二酯二醯氯化物與二胺於鹼性化合物之存在下供至縮合反應,從而製造聚醯胺酸酯(A)。又,可列舉如下方法:藉由將四羧酸二酯與二胺於有機脫水劑之存在下供至縮合反應之方法而製造聚醯胺酸酯(A)。Regarding the specific synthesis method of the polyamide (A) used in this embodiment, a previously known method can be used. As for the synthesis method, for example, the method described in the specification of International Publication No. 00/43439 can be cited. That is, the following method can be cited: the tetracarboxylic acid diester is temporarily converted into the tetracarboxylic acid diester diacyl chloride, and the tetracarboxylic acid diester diacyl chloride and diamine are supplied to condensation in the presence of a basic compound It reacts to produce polyamide (A). In addition, the following method can be cited: a method in which a tetracarboxylic acid diester and a diamine are subjected to a condensation reaction in the presence of an organic dehydrating agent to produce a polyamide (A).
作為有機脫水劑之例,可列舉:二環己基碳二醯亞胺(DCC)、二乙基碳二醯亞胺、二異丙基碳二醯亞胺、乙基環己基碳二醯亞胺、二苯基碳二醯亞胺、1-乙基-3-(3-二甲胺基丙基)碳二醯亞胺、1-環己基-3-(3-二甲胺基丙基)碳二醯亞胺鹽酸鹽等。Examples of organic dehydrating agents include: dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, and ethylcyclohexylcarbodiimide , Diphenylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-cyclohexyl-3-(3-dimethylaminopropyl) Carbodiimide hydrochloride, etc.
本實施形態中所使用之聚醯胺酸酯(A)之重量平均分子量較佳為6000~150000,更佳為7000~50000,更佳為7000~20000。The weight average molecular weight of the polyamide (A) used in this embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and even more preferably 7,000 to 20,000.
(B1)光起始劑
於層間絕緣膜6之形成中所使用之樹脂組合物為負型之感光性樹脂之情形時,添加光起始劑。作為光起始劑,例如可使用:二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基酮、二苄基酮及茀酮等二苯甲酮衍生物、2,2'-二乙氧基苯乙酮及2-羥基-2-甲基苯丙酮等苯乙酮衍生物、1-羥基環己基苯基酮、9-氧硫𠮿、2-甲基-9-氧硫𠮿、2-異丙基-9-氧硫𠮿及二乙基-9-氧硫𠮿等9-氧硫𠮿衍生物、苯偶醯、苯偶醯二甲基縮酮及苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物、安息香甲醚等安息香衍生物、2,6-二(4'-二疊氮苯亞甲基)-4-甲基環己酮及2,6'-二(4'-二疊氮苯亞甲基)環己酮等疊氮類、1-苯基-1,2-丁二酮-2-(O-甲氧基羰基)肟、1-苯基丙二酮-2-(O-甲氧基羰基)肟、1-苯基丙二酮-2-(O-乙氧基羰基)肟、1-苯基丙二酮-2-(O-苯甲醯基)肟、1,3-二苯基丙三酮-2-(O-乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(O-苯甲醯基)肟等肟類、N-苯基甘胺酸等N-芳基甘胺酸類、過氧化苯甲醯等過氧化物類、芳香族聯咪唑類、以及二茂鈦類等。該等之中,就光敏度之方面而言,較佳為上述肟類。(B1) A photoinitiator is added when the resin composition used in the formation of the
該等光起始劑之添加量相對於聚醯胺酸酯(A)100質量份,較佳為1~40質量份,更佳為2~20質量份。藉由相對於聚醯胺酸酯(A)100質量份添加1質量份以上之光起始劑,光敏度優異。又,藉由添加40質量份以下,厚膜硬化性優異。The addition amount of these photoinitiators is preferably 1-40 parts by mass, more preferably 2-20 parts by mass relative to 100 parts by mass of the polyamide (A). By adding 1 part by mass or more of the photoinitiator to 100 parts by mass of the polyamide (A), the photosensitivity is excellent. In addition, by adding 40 parts by mass or less, thick film curability is excellent.
(B2)光酸產生劑
於層間絕緣膜6之形成中所使用之樹脂組合物為正型之感光性樹脂之情形時,添加光酸產生劑。藉由含有光酸產生劑,於紫外線曝光部產生酸,曝光部對鹼性水溶液之溶解性增大。藉此,可作為正型感光性樹脂組合物而使用。(B2) Photoacid generator
When the resin composition used in the formation of the
作為光酸產生劑,可列舉:醌二疊氮化合物、鋶鹽、鏻鹽、重氮鎓鹽、錪鹽等。其中,就表現優異之溶解抑止效果,獲得高感度之正型感光性樹脂組合物之方面而言,較佳使用醌二疊氮化合物。又,可含有兩種以上之光酸產生劑。Examples of photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, it is preferable to use a quinonediazide compound in terms of exhibiting an excellent dissolution suppression effect and obtaining a high-sensitivity positive photosensitive resin composition. In addition, two or more photoacid generators may be contained.
<重量減少率之調整方法>
若於層間絕緣膜6之形成中所使用之樹脂組合物中添加無機填料,則可調整重量減少率。作為無機填料,可使用上述填料。
<揮發氣體量之調整方法>
若於層間絕緣膜6之形成中所使用之樹脂組合物中添加熱交聯劑或揮發調整劑,則可調整於100℃下保持60分鐘時之揮發氣體量。作為熱交聯劑,係形成層間絕緣膜6之聚合物與熱交聯劑反應而交聯者,或熱交聯劑彼此交聯者,並不限定熱交聯劑,可較佳使用具有3官能以上之官能基(環氧基、甲基丙烯醯基、丙烯醯基等)之化合物。<How to adjust the weight reduction rate>
If an inorganic filler is added to the resin composition used in the formation of the
作為揮發調整劑,只要為可調整揮發溫度或揮發壓力者,則並無限定。其中,就具有可與聚合物之極性官能基進行氫鍵結之部位,顯影時不會帶來不良影響之觀點而言,可列舉聚乙二醇或聚丙二醇等。The volatilization modifier is not limited as long as it can adjust volatilization temperature or volatilization pressure. Among them, from the viewpoint that it has a site capable of hydrogen bonding with the polar functional group of the polymer and does not cause adverse effects during development, polyethylene glycol or polypropylene glycol may be mentioned.
藉由以合適之量組合使用該等化合物,可適宜調整揮發氣體量。By using these compounds in combination in an appropriate amount, the amount of volatile gas can be appropriately adjusted.
作為可與上述熱交聯劑或揮發調整劑較佳組合之聚合物,例如可列舉:聚醯亞胺前驅物、聚苯并㗁唑前驅物或具有酚性羥基之聚合物等。As a polymer that can be preferably combined with the above-mentioned thermal crosslinking agent or volatilization regulator, for example, a polyimide precursor, a polybenzoxazole precursor, or a polymer having a phenolic hydroxyl group can be cited.
(D)溶劑 只要為各成分可溶解或分散之溶劑,則並無特別限定。例如可列舉:N-甲基-2-吡咯啶酮、γ-丁內酯、丙酮、甲基乙基酮、二甲基亞碸等。該等溶劑可根據塗佈膜厚、黏度,相對於(A)感光性樹脂100質量份於30~1500質量份之範圍內使用。(D) Solvent As long as it is a solvent in which each component can be dissolved or dispersed, it is not particularly limited. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide and the like can be mentioned. These solvents can be used within the range of 30 to 1500 parts by mass with respect to 100 parts by mass of the photosensitive resin (A) according to the coating film thickness and viscosity.
(E)其他 可於聚醯亞胺前驅物組合物中含有交聯劑。作為交聯劑,可使用將聚醯亞胺前驅物組合物曝光、顯影後進行加熱硬化時可將(A)感光性樹脂交聯之交聯劑、或交聯劑自身可形成交聯網狀結構之交聯劑。藉由使用交聯劑,可進一步強化硬化膜(層間絕緣膜)之耐熱性及耐化學品性。(E) Other A crosslinking agent may be included in the polyimide precursor composition. As the cross-linking agent, a cross-linking agent that can cross-link (A) the photosensitive resin when the polyimide precursor composition is exposed and developed is heat-cured, or the cross-linking agent itself can form a cross-linked network structure The crosslinking agent. By using a crosslinking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further strengthened.
另外,可含有用以提高光敏度之增感劑、用以提高與基材之接著性之接著助劑等。In addition, it may contain a sensitizer to improve the photosensitivity, an adhesive assistant to improve the adhesion to the substrate, etc.
(顯影) 將聚醯亞胺前驅物組合物曝光後,將不需要之部分以顯影液沖洗。作為使用之顯影液,並無特別限制,於以溶劑進行顯影之聚醯亞胺前驅物組合物之情形時,可使用:N,N-二甲基甲醯胺、二甲基亞碸、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、環戊酮、γ-丁內酯、乙酸酯類等良溶劑、該等良溶劑與低級醇、水、芳香族烴等不良溶劑之混合溶劑等。顯影後視需要以不良溶劑等進行沖洗。(development) After exposing the polyimide precursor composition, the unnecessary parts are rinsed with a developer. The developer used is not particularly limited. In the case of a polyimide precursor composition developed with a solvent, it can be used: N,N-dimethylformamide, dimethyl sulfide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetate and other good solvents, such good solvents and lower alcohols, water, aromatics Mixed solvents of poor solvents such as hydrocarbons. After development, rinse with poor solvent or the like as necessary.
於以鹼性水溶液進行顯影之聚醯亞胺前驅物組合物之情形時,較佳為氫氧化四甲基銨之水溶液、二乙醇胺、二乙胺基乙醇、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙胺、二乙胺、甲胺、二甲胺、乙酸二甲胺基乙酯、二甲胺基乙醇、甲基丙烯酸二甲胺基乙酯、環己胺、乙二胺、己二胺等顯示鹼性之化合物之水溶液。In the case of a polyimide precursor composition developed with an alkaline aqueous solution, it is preferably an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, carbonic acid Sodium, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenedi Aqueous solutions of amines, hexamethylene diamine and other compounds showing basicity.
(熱硬化)
顯影後,藉由加熱而將聚醯亞胺前驅物閉環,形成聚醯亞胺。該聚醯亞胺成為硬化凸紋圖案,即層間絕緣膜6。(Thermal hardening)
After development, the polyimide precursor is ring-closed by heating to form polyimide. The polyimide becomes a hardened relief pattern, that is, the
加熱溫度並無特別限定,通常存在加熱硬化溫度越低,折射率差變得越小之傾向。就表現為未達作為本實施形態之折射率差之0.0150之觀點而言,較佳為200℃以下,較佳為180℃以下,較佳為160℃以下。The heating temperature is not particularly limited. Generally, the lower the heating and curing temperature, the smaller the refractive index difference becomes. From the viewpoint of showing less than 0.0150, which is the refractive index difference of the present embodiment, it is preferably 200°C or lower, preferably 180°C or lower, and more preferably 160°C or lower.
<聚醯亞胺> 自上述聚醯亞胺前驅物組合物形成之硬化凸紋圖案之結構為下述通式(1)。<Polyimide> The structure of the hardened relief pattern formed from the polyimide precursor composition is the following general formula (1).
[化40] [化40]
通式(1)中之X1 、Y1 、m與通式(11)中之X1 、Y1 、m相同,X1 為4價有機基,Y1 為2價有機基,m為1以上之整數。通式(11)中之較佳X1 、Y1 、m因相同理由,於通式(1)之聚醯亞胺中亦較佳。Formula (1) in the X-1, Y 1, m in the general formula (11) in the X 1, Y 1, the same m, X 1 is a tetravalent organic group, Y 1 is a divalent organic group, m is 1 The above integer. The preferred X 1 , Y 1 , and m in the general formula (11) are also preferred in the polyimide of the general formula (1) for the same reason.
於鹼可溶性聚醯亞胺之情形時,可使聚醯亞胺之末端成為羥基。In the case of alkali-soluble polyimide, the end of the polyimide can be made a hydroxyl group.
<聚苯并㗁唑前驅物組合物> (A)感光性樹脂 作為用於聚苯并㗁唑前驅物組合物之感光性樹脂,可使用含有下述通式(14)所表示之重複單元之聚(鄰羥基醯胺)。<Polybenzoxazole precursor composition> (A) Photosensitive resin As the photosensitive resin used for the polybenzoxazole precursor composition, poly(o-hydroxyamide) containing a repeating unit represented by the following general formula (14) can be used.
[化41] (通式(14)中,Y2 與Y3 為2價有機基)[化41] (In the general formula (14), Y 2 and Y 3 are divalent organic groups)
就層間絕緣膜6與密封材3之密接性之觀點而言,Y2
較佳為碳數1~30之2價有機基,更佳為碳數1~15之鏈狀伸烷基(其中,鏈狀伸烷基之氫原子可被取代為鹵素原子),尤佳為碳數1~8且氫原子被取代為氟原子之鏈狀伸烷基。From the viewpoint of the adhesion between the interlayer insulating
又,就層間絕緣膜6與密封材3之密接性之觀點而言,Y3
較佳為含有芳香族基之2價有機基,更佳為含有下述通式(6)~(8)所表示之至少一種結構之2價有機基。Also, from the viewpoint of the adhesion between the interlayer insulating
[化42] (R10 、R11 、R12 及R13 為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同)[化42] (R 10 , R 11 , R 12 and R 13 are hydrogen atoms and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)
[化43] (R14 ~R21 為氫原子、鹵素原子、碳數1~5之1價有機基,相互可不同,亦可相同)[化43] (R 14 to R 21 are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)
[化44] (R22 為2價基,R23 ~R30 為氫原子、鹵素原子、碳數1~5之1價脂肪族基,可相同亦可不同)[化44] (R 22 is a divalent group, R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different)
通式(8)中之R22 例如為碳數1~40之2價有機基或鹵素原子。R 22 in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.
就層間絕緣膜6與密封材3之密接性之觀點而言,Y3
尤佳為含有下述通式(9)所表示之結構之2價有機基。From the viewpoint of the adhesion between the interlayer insulating
[化45] [化45]
就層間絕緣膜6與密封材3之密接性之觀點而言,Y3
較佳為碳數1~40之2價有機基,更佳為碳數1~40之2價鏈狀脂肪族基,尤佳為碳數1~20之2價鏈狀脂肪族基。From the viewpoint of the adhesion between the interlayer insulating
聚苯并㗁唑前驅物通常可自二羧酸衍生物與含羥基之二胺類而合成。具體而言,可藉由將二羧酸衍生物轉換為二鹵化物衍生物後,進行與二胺類之反應而合成。作為二鹵化物衍生物,較佳為二氯化物衍生物。Polybenzoxazole precursors can usually be synthesized from dicarboxylic acid derivatives and hydroxyl-containing diamines. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with diamines. The dihalide derivative is preferably a dichloride derivative.
二氯化物衍生物可使鹵化劑與二羧酸衍生物產生作用而合成。作為鹵化劑,可使用通常之羧酸之醯氯化反應中所使用之亞硫醯氯、磷醯氯、氧氯化磷、五氯化磷等。Dichloride derivatives can be synthesized by reacting halogenating agents with dicarboxylic acid derivatives. As the halogenating agent, thiochloride, phosphonium chloride, phosphorus oxychloride, phosphorus pentachloride, etc. used in the chlorination reaction of ordinary carboxylic acids can be used.
作為合成二氯化物衍生物之方法,可藉由使二羧酸衍生物與上述鹵化劑於溶劑中反應之方法、於過剩之鹵化劑中進行反應後,將過剩之部分蒸餾去除之方法等而合成。As a method for synthesizing dichloride derivatives, the method of reacting the dicarboxylic acid derivative with the above-mentioned halogenating agent in a solvent, the method of reacting in excess halogenating agent and then distilling off the excess part, etc. synthesis.
作為用於二羧酸衍生物之二羧酸,例如可列舉:間苯二甲酸、對苯二甲酸、2,2-雙(4-羧基苯基)-1,1,1,3,3,3-六氟丙烷、4,4'-二羧基聯苯、4,4'-二羧基二苯醚、4,4'-二羧基四苯基矽烷、雙(4-羧基苯基)碸、2,2-雙(對羧基苯基)丙烷、5-第三丁基間苯二甲酸、5-溴間苯二甲酸、5-氟間苯二甲酸、5-氯間苯二甲酸、2,6-萘二羧酸、丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二-正丁基丙二酸、琥珀酸、四氟琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、2,3-二甲基琥珀酸、二甲基甲基琥珀酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、八氟己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、氧二乙酸等。可將該等混合使用。Examples of dicarboxylic acids used for dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3, 3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl) sulfide, 2 , 2-bis(p-carboxyphenyl)propane, 5-tertiary butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6 -Naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methyl succinic acid Acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3- Methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid , 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoro suberic acid, azelaic acid, decane Diacid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid Alkanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, Pentadecanedioic acid, hexadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonacrylic acid, triaconanedioic acid, hexadecanedioic acid, thirty Dioxanedioic acid, oxydiacetic acid, etc. These can be mixed and used.
作為含羥基之二胺,例如可列舉:3,3'-二胺基-4,4'-二羥基聯苯、4,4'-二胺基-3,3'-二羥基聯苯、雙(3-胺基-4-羥基苯基)丙烷、雙(4-胺基-3-羥基苯基)丙烷、雙(3-胺基-4-羥基苯基)碸、雙(4-胺基-3-羥基苯基)碸、2,2-雙(3-胺基-4-羥基苯基)-1,1,1,3,3,3-六氟丙烷、2,2-雙(4-胺基-3-羥基苯基)-1,1,1,3,3,3-六氟丙烷等。可將該等混合使用。Examples of hydroxyl-containing diamines include: 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-Amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl) ash, bis(4-amino -3-Hydroxyphenyl) sulfide, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4 -Amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the like. These can be mixed and used.
(B2)光酸產生劑 光酸產生劑係具有增大光照射部之鹼性水溶液可溶性之功能者。作為光酸產生劑,可列舉:重氮萘醌化合物、芳基重氮鎓鹽、二芳基錪鹽、三芳基鋶鹽等。其中,重氮萘醌化合物之感度較高,故較佳。(B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the alkaline aqueous solution in the light-irradiated part. As a photoacid generator, a diazonaphthoquinone compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl sulfonium salt, etc. are mentioned. Among them, the diazonaphthoquinone compound has a higher sensitivity and is therefore preferred.
(D)溶劑 只要為可溶解或分散各成分之溶劑,則並無特別限定。(D) Solvent As long as it is a solvent which can dissolve or disperse each component, it will not specifically limit.
(E)其他 聚苯并㗁唑前驅物組合物可含有交聯劑、增感劑、接著助劑、熱酸產生劑等。(E) Other The polybenzoxazole precursor composition may contain a crosslinking agent, a sensitizer, an adhesive agent, a thermal acid generator, and the like.
(顯影) 將聚苯并㗁唑前驅物組合物曝光後,將不需要之部分以顯影液沖洗。作為使用之顯影液,並無特別限制,例如可列舉氫氧化鈉、氫氧化鉀、矽酸鈉、氨、乙胺、二乙胺、三乙胺、三乙醇胺、氫氧化四甲基銨等鹼性水溶液作為較佳者。(development) After exposing the polybenzoxazole precursor composition, the unnecessary parts are rinsed with developer. The developer used is not particularly limited. Examples include alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. Sexual aqueous solution is preferred.
上述中,以正型之聚苯并㗁唑前驅物組合物為中心進行了說明,但亦可為負型之聚苯并㗁唑前驅物組合物。In the above, the description is centered on the positive polybenzoxazole precursor composition, but it may also be the negative polybenzoxazole precursor composition.
(熱硬化)
顯影後,藉由加熱而將聚苯并㗁唑前驅物閉環,形成聚苯并㗁唑。該聚苯并㗁唑成為硬化凸紋圖案,即層間絕緣膜6。(Thermal hardening)
After development, the polybenzoxazole precursor is ring-closed by heating to form polybenzoxazole. This polybenzoxazole becomes a hardened relief pattern, that is, the
加熱溫度並無特別限定,就對其他構件之影響之觀點而言,加熱溫度較佳為較低溫度。較佳為250度以下,更佳為230度以下,更佳為200度以下,尤佳為180度以下。The heating temperature is not particularly limited, but from the viewpoint of the influence on other components, the heating temperature is preferably a lower temperature. It is preferably 250 degrees or less, more preferably 230 degrees or less, more preferably 200 degrees or less, and particularly preferably 180 degrees or less.
<聚苯并㗁唑> 自上述聚苯并㗁唑前驅物組合物形成之硬化凸紋圖案之結構為下述通式(10)。<Polybenzoxazole> The structure of the hardened relief pattern formed from the aforementioned polybenzoxazole precursor composition is the following general formula (10).
[化46] [化46]
通式(10)中之Y2 、Y3 與通式(14)中之Y2 、Y3 相同。通式(14)中之較佳Y2 、Y3 因相同理由,於通式(10)之聚苯并㗁唑中亦較佳。 2, 2, Y 3 Y 3 same general formula Y (14) in the general formula (10) in the Y. The preferred Y 2 and Y 3 in the general formula (14) are also preferred in the polybenzoxazole of the general formula (10) for the same reason.
<具有酚性羥基之聚合物> (A)感光性樹脂 係於分子中具有酚性羥基之樹脂,對鹼為可溶。作為其具體例,可列舉:聚(羥基苯乙烯)等含有具有酚性羥基之單體單元之乙烯系聚合物、酚樹脂、聚(羥基醯胺)、聚(羥基伸苯基)醚、聚萘酚。<Polymer with phenolic hydroxyl group> (A) Photosensitive resin It is a resin with a phenolic hydroxyl group in the molecule and is soluble in alkali. Specific examples include: vinyl polymers containing monomer units having phenolic hydroxyl groups such as poly(hydroxystyrene), phenol resins, poly(hydroxyamide), poly(hydroxyphenylene) ether, poly Naphthol.
該等之中,就成本便宜或硬化時之體積收縮較小之方面而言,較佳為酚樹脂,尤佳為酚醛清漆型酚樹脂。Among them, in terms of low cost or small volume shrinkage during curing, phenol resin is preferred, and novolak type phenol resin is particularly preferred.
酚樹脂係酚或其衍生物與醛類之縮聚產物。縮聚係於酸或鹼等觸媒存在下進行。將使用酸觸媒之情形時所獲得之酚樹脂特稱為酚醛清漆型酚樹脂。Phenolic resin series phenol or its derivatives and aldehydes condensation products. The polycondensation is carried out in the presence of a catalyst such as acid or alkali. The phenol resin obtained when an acid catalyst is used is specifically called a novolak type phenol resin.
作為酚衍生物,例如可列舉:苯酚、甲酚、乙基苯酚、丙基苯酚、丁基苯酚、戊基苯酚、苄基苯酚、金剛烷苯酚、苄氧基苯酚、二甲苯酚、鄰苯二酚、間苯二酚、乙基間苯二酚、己基間苯二酚、對苯二酚、鄰苯三酚、間苯三酚、1,2,4-三羥基苯、玫紅酸、聯苯酚、雙酚A、雙酚AF、雙酚B、雙酚F、雙酚S、二羥基二苯基甲烷、1,1-雙(4-羥基苯基)環己烷、1,4-雙(3-羥基苯氧基苯)、2,2-雙(4-羥基-3-甲基苯基)丙烷、α,α'-雙(4-羥基苯基)-1,4-二異丙基苯、9,9-雙(4-羥基-3-甲基苯基)茀、2,2-雙(3-環己基-4-羥基苯基)丙烷、2,2-雙(2-羥基-5-聯苯基)丙烷、二羥基苯甲酸等。Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantylphenol, benzyloxyphenol, xylenol, and catechol Phenol, resorcinol, ethyl resorcinol, hexyl resorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rosolic acid, biphenyl Phenol, bisphenol A, bisphenol AF, bisphenol B, bisphenol F, bisphenol S, dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,4-bis (3-hydroxyphenoxybenzene), 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropyl Benzene, 9,9-bis(4-hydroxy-3-methylphenyl) pyrene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy -5-Biphenyl) propane, dihydroxybenzoic acid, etc.
作為醛化合物,可列舉:甲醛、多聚甲醛、乙醛、丙醛、新戊醛、丁醛、戊醛、己醛、三㗁烷、乙二醛、環己醛、二苯基乙醛、乙基丁醛、苯甲醛、乙醛酸、5-降𦯉烯-2-甲醛、丙二醛、丁二醛、戊二醛、柳醛、萘甲醛、對苯二甲醛等。Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexanal, diphenylacetaldehyde, Ethyl butyraldehyde, benzaldehyde, glyoxylic acid, 5-nor ene-2-carboxaldehyde, malondialdehyde, succinic aldehyde, glutaraldehyde, salicaldehyde, naphthaldehyde, terephthalaldehyde, etc.
(A)成分較佳為含有(a)不具有不飽和烴基之酚樹脂與(b)具有不飽和烴基之改性酚樹脂者。上述(b)成分更佳為藉由酚性羥基與多元酸酐之反應而進而改性者。The (A) component is preferably one containing (a) a phenol resin that does not have an unsaturated hydrocarbon group and (b) a modified phenol resin that has an unsaturated hydrocarbon group. The above-mentioned component (b) is more preferably modified by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride.
又,作為(b)成分,就可進一步提高機械特性(斷裂伸長率、彈性模數及殘留應力)之觀點而言,較佳為使用以具有碳數4~100之不飽和烴基之化合物進行改性之酚樹脂。In addition, as component (b), from the viewpoint of further improving mechanical properties (elongation at break, modulus of elasticity, and residual stress), it is preferable to use a compound having an unsaturated hydrocarbon group with 4 to 100 carbon atoms. Sexual phenol resin.
(b)具有不飽和烴基之改性酚樹脂通常係酚或其衍生物和具有不飽和烴基之化合物(較佳為碳數4~100者)(以下,有時簡稱為「含不飽和烴基之化合物」)之反應產物(以下稱為「不飽和烴基改性酚衍生物」)與醛類的縮聚產物、或酚樹脂與含不飽和烴基之化合物之反應產物。(b) Modified phenol resins with unsaturated hydrocarbon groups are usually phenols or their derivatives and compounds with unsaturated hydrocarbon groups (preferably those with 4 to 100 carbons) (hereinafter, sometimes referred to as "unsaturated hydrocarbon group-containing Compound ") (hereinafter referred to as "unsaturated hydrocarbyl-modified phenol derivative") is a condensation product of aldehydes, or a reaction product of a phenol resin and an unsaturated hydrocarbyl-containing compound.
此處之酚衍生物可使用與關於作為(A)成分之酚樹脂之原料而於上文敍述之酚衍生物相同者。The phenol derivative here can be the same as the phenol derivative described above regarding the raw material of the phenol resin as the component (A).
就光阻圖案之密接性及耐熱衝擊性之觀點而言,含不飽和烴基之化合物之不飽和烴基較佳為含有2個以上之不飽和基。又,就製為樹脂組合物時之相溶性及硬化膜之可撓性之觀點而言,含不飽和烴基之化合物較佳為碳數8~80者,更佳為碳數10~60者。From the viewpoint of the adhesiveness and thermal shock resistance of the photoresist pattern, the unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups. In addition, from the viewpoint of compatibility when preparing the resin composition and flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, and more preferably has 10 to 60 carbon atoms.
作為含不飽和烴基之化合物,例如為:碳數4~100之不飽和烴、具有羧基之聚丁二烯、環氧化聚丁二烯、亞麻醇、油醇、不飽和脂肪酸及不飽和脂肪酸酯。作為較佳之不飽和脂肪酸,可列舉:丁烯酸、肉豆蔻油酸、棕櫚油酸、油酸、反油酸、異油酸、鱈油酸、芥子酸、二十四碳烯酸、亞麻油酸、α-次亞麻油酸、桐酸、十八碳四烯酸、花生油酸、二十碳五烯酸、鯡魚酸及二十二碳六烯酸。該等之中,尤其更佳為碳數8~30之不飽和脂肪酸與碳數1~10之一元至三元醇之酯,尤佳為碳數8~30之不飽和脂肪酸與作為三元醇之甘油之酯。Examples of compounds containing unsaturated hydrocarbon groups include: unsaturated hydrocarbons with 4 to 100 carbon atoms, polybutadiene with carboxyl groups, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acids ester. Preferred unsaturated fatty acids include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, isoleic acid, codoleic acid, erucic acid, arachidonic acid, linseed oil Acid, α-linolenic acid, eleostearic acid, stearidonic acid, arachidic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among them, particularly preferred are esters of unsaturated fatty acids with 8 to 30 carbons and monohydric to trihydric alcohols with 1 to 10 carbons, and particularly preferred are unsaturated fatty acids with 8 to 30 carbons and trihydric alcohols. The esters of glycerol.
碳數8~30之不飽和脂肪酸與甘油之酯可作為植物油而於商業上獲取。植物油有碘值100以下之非乾性油、超過100且未達130之半乾性油或130以上之乾性油。作為非乾性油,例如可列舉:橄欖油、牽牛花籽油、何首烏籽油、茶梅油、山茶油、蓖麻油及花生油。作為半乾性油,例如可列舉:玉米油、棉籽油及芝麻油。作為乾性油,例如可列舉:桐油、亞麻仁油、大豆油、胡桃油、紅花油、葵花籽油、紫蘇油及芥子油。又,可使用將該等植物油進行加工所獲得之加工植物油。The ester of unsaturated fatty acid and glycerin with carbon number of 8-30 can be obtained commercially as vegetable oil. Vegetable oils include non-drying oils with an iodine value below 100, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, Polygonum multiflorum seed oil, camellia oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. In addition, processed vegetable oils obtained by processing these vegetable oils can be used.
上述植物油之中,就於酚或其衍生物或酚樹脂與植物油之反應中,防止伴隨過度反應之進行之凝膠化,提高良率之觀點而言,較佳為使用非乾性油。另一方面,就提高光阻圖案之密接性、機械特性及耐熱衝擊性之觀點而言,較佳為使用乾性油。乾性油之中,就可更有效且確實地發揮藉由本發明之效果之方面而言,較佳為桐油、亞麻仁油、大豆油、胡桃油及紅花油,更佳為桐油及亞麻仁油。Among the above-mentioned vegetable oils, it is preferable to use non-drying oils from the viewpoint of preventing gelation accompanying the progress of excessive reaction in the reaction of phenol or its derivatives or phenol resin with vegetable oils and improving the yield. On the other hand, from the viewpoint of improving the adhesion, mechanical properties, and thermal shock resistance of the photoresist pattern, it is preferable to use a drying oil. Among the dry oils, in terms of more effectively and reliably exerting the effects of the present invention, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferable, and tung oil and linseed oil are more preferable.
該等含不飽和烴基之化合物可單獨使用一種或組合使用兩種以上。These unsaturated hydrocarbon group-containing compounds can be used alone or in combination of two or more.
製備(b)成分時,首先使上述酚衍生物與上述含不飽和烴基之化合物進行反應,製作不飽和烴基改性酚衍生物。上述反應較佳為於50~130℃下進行。關於酚衍生物與含不飽和烴基之化合物之反應比率,就提高硬化膜(光阻圖案)之可撓性之觀點而言,相對於酚衍生物100質量份,含不飽和烴基之化合物較佳為1~100質量份,更佳為5~50質量份。若含不飽和烴基之化合物未達1質量份,則存在硬化膜之可撓性下降之傾向,若超過100質量份,則存在硬化膜之耐熱性下降之傾向。於上述反應中,視需要可使用對甲苯磺酸、三氟甲磺酸等作為觸媒。When preparing the component (b), first, the phenol derivative and the unsaturated hydrocarbon group-containing compound are reacted to produce an unsaturated hydrocarbon group-modified phenol derivative. The above reaction is preferably carried out at 50 to 130°C. Regarding the reaction ratio of the phenol derivative and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (photoresist pattern), the unsaturated hydrocarbon group-containing compound is preferable to 100 parts by mass of the phenol derivative It is 1-100 parts by mass, more preferably 5-50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. can be used as a catalyst as necessary.
藉由使利用上述反應而生成之不飽和烴基改性酚衍生物與醛類進行縮聚,生成藉由含不飽和烴基之化合物而改性之酚樹脂。醛類可使用與作為用以獲得酚樹脂之醛類而於上文敍述者相同者。By polycondensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes, a phenol resin modified by an unsaturated hydrocarbon group-containing compound is produced. The aldehydes can be the same as those described above as the aldehydes used to obtain the phenol resin.
上述醛類與上述不飽和烴基改性酚衍生物之反應係縮聚反應,可使用先前公知之酚樹脂之合成條件。反應較佳為於酸或鹼等觸媒之存在下進行,更佳為使用酸觸媒。作為酸觸媒,例如可列舉:鹽酸、硫酸、甲酸、乙酸、對甲苯磺酸及草酸。該等酸觸媒可單獨使用一種或組合使用兩種以上。The reaction between the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon-modified phenol derivative is a polycondensation reaction, and the previously known synthesis conditions of phenol resin can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, and more preferably an acid catalyst is used. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.
上述反應通常較佳為於反應溫度100~120℃下進行。又,反應時間根據所使用之觸媒之種類或量而有所不同,通常為1~50小時。反應結束後,將反應產物於200℃以下之溫度下進行減壓脫水,藉此獲得藉由含不飽和烴基之化合物而改性之酚樹脂。再者,反應中可使用甲苯、二甲苯、甲醇等溶劑。The above reaction is usually preferably carried out at a reaction temperature of 100 to 120°C. In addition, the reaction time varies depending on the type or amount of the catalyst used, and is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature below 200° C., thereby obtaining a phenol resin modified by an unsaturated hydrocarbon group-containing compound. In addition, solvents such as toluene, xylene, and methanol can be used in the reaction.
藉由含不飽和烴基之化合物而改性之酚樹脂亦可藉由使上述不飽和烴基改性酚衍生物同如間二甲苯之酚以外之化合物一起,與醛類進行縮聚而獲得。於該情形時,酚以外之化合物相對於使酚衍生物與含不飽和烴基之化合物反應而獲得之化合物之莫耳比較佳為未達0.5。The phenol resin modified by an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative with compounds other than phenol such as meta-xylene with aldehydes. In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative with the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.
(b)成分亦可使上述(a)成分之酚樹脂與含不飽和烴基之化合物反應而獲得。The component (b) can also be obtained by reacting the phenol resin of the component (a) with an unsaturated hydrocarbon group-containing compound.
與酚樹脂反應之含不飽和烴基之化合物可使用與上述含不飽和烴基之化合物相同者。The unsaturated hydrocarbon group-containing compound that reacts with the phenol resin can be the same as the above-mentioned unsaturated hydrocarbon group-containing compound.
酚樹脂與含不飽和烴基之化合物之反應通常較佳為於50~130℃下進行。又,關於酚樹脂與含不飽和烴基之化合物之反應比率,就提高硬化膜(光阻圖案)之可撓性之觀點而言,相對於酚樹脂100質量份,含不飽和烴基之化合物較佳為1~100質量份,更佳為2~70質量份,進而較佳為5~50質量份。若含不飽和烴基之化合物未達1質量份,則存在硬化膜之可撓性下降之傾向,若超過100質量份,則存在反應中凝膠化之可能性變高之傾向、及硬化膜之耐熱性下降之傾向。此時,視需要可使用對甲苯磺酸、三氟甲磺酸等作為觸媒。再者,可於反應中使用甲苯、二甲苯、甲醇、四氫呋喃等溶劑。The reaction of the phenol resin with the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130°C. In addition, with regard to the reaction ratio of the phenol resin and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (photoresist pattern), the unsaturated hydrocarbon group-containing compound is preferable to 100 parts by mass of the phenol resin It is from 1 to 100 parts by mass, more preferably from 2 to 70 parts by mass, and still more preferably from 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease. If it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the cured film tends to become more flexible. The tendency of heat resistance to decline. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. can be used as a catalyst as needed. Furthermore, solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used in the reaction.
進而使多元酸酐與利用如以上之方法生成之藉由含不飽和烴基之化合物而改性之酚樹脂中殘存之酚性羥基進行反應。藉此,亦可將酸改性之酚樹脂用作(b)成分。藉由以多元酸酐進行酸改性,導入羧基,(b)成分對鹼性水溶液(顯影液)之溶解性更進一步提高。Furthermore, the polybasic acid anhydride is reacted with the phenolic hydroxyl group remaining in the phenol resin modified by the unsaturated hydrocarbon group-containing compound produced by the above method. Thereby, acid-modified phenol resin can also be used as (b) component. By acid modification with polybasic acid anhydride and introduction of carboxyl groups, the solubility of component (b) in alkaline aqueous solution (developer) is further improved.
多元酸酐只要具備具有複數個羧基之多元酸之羧基進行脫水縮合所形成之酸酐基,則並無特別限定。作為多元酸酐,例如可列舉:鄰苯二甲酸酐、琥珀酸酐、辛烯基琥珀酸酐、十五碳烯基琥珀酸酐、順丁烯二酸酐、伊康酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、耐地酸酐、3,6-內亞甲基四氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、四溴鄰苯二甲酸酐及偏苯三甲酸酐等二元酸酐、聯苯四羧酸二酐、萘四羧酸二酐、二苯醚四羧酸二酐、丁烷四羧酸二酐、環戊烷四羧酸二酐、均苯四甲酸二酐及二苯甲酮四羧酸二酐等芳香族四元酸二酐。該等可單獨使用一種或組合使用兩種以上。該等之中,多元酸酐較佳為二元酸酐,更佳為選自由四氫鄰苯二甲酸酐、琥珀酸酐及六氫鄰苯二甲酸酐所組成之群中之一種以上。於該情形時,具有可形成具有更良好之形狀之光阻圖案之優點。The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration and condensation of the carboxyl group of a polybasic acid having a plurality of carboxy groups. Examples of polybasic acid anhydrides include: phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexa Hydrogen phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, tertiary acid anhydride, 3,6-endomethylene tetrahydro phthalic anhydride, methyl Dibasic acid anhydrides such as methylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aromatic tetrabasic acid dianhydrides such as anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride. These can be used individually by 1 type or in combination of 2 or more types. Among them, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, it has the advantage that a photoresist pattern with a better shape can be formed.
又,(A)具有酚性羥基之鹼可溶性樹脂可含有進而使多元酸酐反應而酸改性之酚樹脂。藉由使(A)成分含有以多元酸酐進行酸改性之酚樹脂,(A)成分對鹼性水溶液(顯影液)之溶解性更進一步提高。In addition, (A) the alkali-soluble resin having a phenolic hydroxyl group may contain a phenol resin that is further acid-modified by reacting a polybasic acid anhydride. When the component (A) contains a phenol resin acid-modified with a polybasic acid anhydride, the solubility of the component (A) in an alkaline aqueous solution (developer) is further improved.
作為上述多元酸酐,例如可列舉:鄰苯二甲酸酐、琥珀酸酐、辛烯基琥珀酸酐、十五碳烯基琥珀酸酐、順丁烯二酸酐、伊康酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、耐地酸酐、3,6-內亞甲基四氫鄰苯二甲酸酐、甲基內亞甲基四氫鄰苯二甲酸酐、四溴鄰苯二甲酸酐、偏苯三甲酸酐等二元酸酐、聯苯四羧酸二酐、萘四羧酸二酐、二苯醚四羧酸二酐、丁烷四羧酸二酐、環戊烷四羧酸二酐、均苯四甲酸二酐、二苯甲酮四羧酸二酐等脂肪族、芳香族四元酸二酐等。該等可單獨使用一種或組合使用兩種以上。該等之中,多元酸酐較佳為二元酸酐,例如更佳為選自由四氫鄰苯二甲酸酐、琥珀酸酐及六氫鄰苯二甲酸酐所組成之群中之一種以上。As the above-mentioned polybasic acid anhydride, for example, phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tertiary acid anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl Endomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride and other dibasic anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aliphatic and aromatic tetrabasic acid dianhydrides such as dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, etc. These can be used individually by 1 type or in combination of 2 or more types. Among them, the polybasic acid anhydride is preferably a dibasic acid anhydride, for example, more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride.
(B2)光酸產生劑 作為光酸產生劑,可列舉:重氮萘醌化合物、芳基重氮鎓鹽、二芳基錪鹽、三芳基鋶鹽等。其中,氮萘醌化合物之感度較高,故較佳。(B2) Photoacid generator As a photoacid generator, a diazonaphthoquinone compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl sulfonium salt, etc. are mentioned. Among them, the azonaphthoquinone compound has higher sensitivity and is therefore preferred.
作為熱交聯促進劑,例如可較佳使用:環氧化合物、氧環丁烷化合物、㗁唑啉化合物、醛、醛改性物、異氰酸酯化合物、含不飽和鍵之化合物、多元醇化合物、多胺化合物、三聚氰胺化合物、金屬螯合劑、C-羥甲基系化合物、N-羥甲基系化合物等。As the thermal crosslinking accelerator, for example, epoxy compounds, oxetane compounds, oxazoline compounds, aldehydes, modified aldehydes, isocyanate compounds, unsaturated bond-containing compounds, polyol compounds, poly Amine compounds, melamine compounds, metal chelating agents, C-methylol compounds, N-methylol compounds, etc.
(D)溶劑 只要為可溶解或分散各成分之溶劑,則並無特別限定。(D) Solvent As long as it is a solvent which can dissolve or disperse each component, it will not specifically limit.
(E)其他 可含有熱交聯劑、增感劑、接著助劑、染料、界面活性劑、溶解促進劑、交聯促進劑等。其中,藉由含有熱交聯劑,將圖案形成後之感光性樹脂膜進行加熱硬化時,熱交聯劑成分與(A)成分反應而形成交聯結構。藉此,可於低溫下硬化,可防止膜之脆化或膜之熔融。作為熱交聯劑成分,具體而言,可使用具有酚性羥基之化合物、具有羥甲基胺基之化合物、具有環氧基之化合物作為較佳者。(E) Other It may contain thermal crosslinking agents, sensitizers, adhesives, dyes, surfactants, dissolution promoters, crosslinking promoters, etc. Among them, by containing a thermal crosslinking agent, when the photosensitive resin film after pattern formation is heat-cured, the thermal crosslinking agent component reacts with the (A) component to form a crosslinked structure. Thereby, it can be hardened at low temperature and can prevent the embrittlement of the film or the melting of the film. As the thermal crosslinking agent component, specifically, a compound having a phenolic hydroxyl group, a compound having a methylolamino group, and a compound having an epoxy group are preferably used.
(顯影) 將具有酚性羥基之聚合物曝光後,將不需要之部分以顯影液沖洗。作為使用之顯影液,並無特別限制,例如可較佳使用氫氧化鈉、氫氧化鉀、矽酸鈉、氨、乙胺、二乙胺、三乙胺、三乙醇胺、氫氧化四甲基銨(TMAH)等鹼性水溶液。(development) After exposing the polymer with phenolic hydroxyl group, the unnecessary part is washed with developer. The developer used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide can be preferably used. (TMAH) and other alkaline aqueous solutions.
(熱硬化)
顯影後,藉由加熱而使具有酚性羥基之聚合物彼此進行熱交聯。該交聯後之聚合物成為硬化凸紋圖案,即層間絕緣膜6。(Thermal hardening)
After development, the polymers having phenolic hydroxyl groups are thermally crosslinked by heating. The crosslinked polymer becomes a hardened relief pattern, that is, the
加熱溫度並無特別限定,就對其他構件之影響之觀點而言,加熱溫度較佳為較低溫度。較佳為250度以下,更佳為230度以下,更佳為200度以下,尤佳為180度以下。The heating temperature is not particularly limited, but from the viewpoint of the influence on other components, the heating temperature is preferably a lower temperature. It is preferably 250 degrees or less, more preferably 230 degrees or less, more preferably 200 degrees or less, and particularly preferably 180 degrees or less.
(半導體裝置之製造方法)
關於本實施形態之半導體裝置之製造方法,使用圖3進行說明。圖3A中,準備完成前步驟之晶圓10。並且,圖3B中,對完成前步驟之晶圓10進行切晶,形成複數個半導體晶片2。半導體晶片2亦可為購買品。將如此準備之半導體晶片2,如圖3C所示以所定間距貼附於支持體11上。(Method of manufacturing semiconductor device)
The manufacturing method of the semiconductor device of this embodiment will be described with reference to FIG. 3. In FIG. 3A, the
繼而,將塑模樹脂12遍塗於半導體晶片2上至支持體11上,如圖3D所示進行塑模密封。繼而,剝離支持體11,將塑模樹脂12翻轉(參照圖3E)。如圖3E所示,半導體晶片2與塑模樹脂12呈現於大致同一平面。繼而,於圖3F所示之步驟中,將感光性樹脂組合物13塗佈於半導體晶片2上及塑模樹脂12上。此時,感光性樹脂組合物13較佳為以填料進行調整。並且,將塗佈之感光性樹脂組合物13曝光顯影,形成凸紋圖案(凸紋圖案形成步驟)。再者,感光性樹脂組合物13可為正型或負型之任一者。進而,將凸紋圖案加熱而形成硬化凸紋圖案(層間絕緣膜形成步驟)。進而,於未形成硬化凸紋圖案之部位形成配線(配線形成步驟)。Then, the
再者,於本實施形態中,將上述凸紋圖案形成步驟、層間絕緣膜形成步驟及配線形成步驟合併為形成與半導體晶片2連接之再配線層之再配線層形成步驟。Furthermore, in this embodiment, the above-mentioned relief pattern forming step, interlayer insulating film forming step, and wiring forming step are combined into a rewiring layer forming step for forming a rewiring layer connected to the
再配線層中之層間絕緣膜可為多層。因此,再配線層形成步驟可包含複數次之凸紋圖案形成步驟、複數次之層間絕緣膜形成步驟及複數次之配線形成步驟。The interlayer insulating film in the rewiring layer may be multiple layers. Therefore, the rewiring layer forming step may include a plurality of relief pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.
並且,於圖3G中,形成與各半導體晶片2對應之複數個外部連接端子7(凸塊形成),將各半導體晶片2間進行切晶。藉此,如圖3H所示,可獲得半導體裝置(半導體IC)1。於本實施形態中,藉由圖3所示之製造方法,可獲得複數個扇出型之半導體裝置1。In addition, in FIG. 3G, a plurality of
於本實施形態中,經過上述步驟而形成之硬化凸紋圖案(層間絕緣膜)之重量減少率可為5~95重量%。 於本實施之另一形態中,經過上述步驟而形成之硬化凸紋圖案(層間絕緣膜)於100℃下保持60分鐘時之揮發氣體於每1 cm2 中可為0.2×10-6 ~2.5×10-6 Pa。 於本實施之又一形態中,經過上述步驟而形成之硬化凸紋圖案(層間絕緣膜)於100℃下保持60分鐘時之揮發氣體於每1 cm2 中可為0.4×10-6 ~1.8×10-6 Pa。In this embodiment, the weight reduction rate of the hardened relief pattern (interlayer insulating film) formed through the above steps can be 5-95% by weight. In another aspect of this embodiment, the hardened relief pattern (interlayer insulating film) formed by the above steps can have a volatile gas of 0.2×10 -6 ~2.5 per 1 cm 2 when kept at 100°C for 60 minutes ×10 -6 Pa. In another aspect of this implementation, the hardened relief pattern (interlayer insulating film) formed through the above steps can have a volatile gas of 0.4×10 -6 ~1.8 per 1 cm 2 when kept at 100°C for 60 minutes ×10 -6 Pa.
於本實施形態中,於上述層間絕緣膜形成步驟中,較佳為以可形成聚醯亞胺、聚苯并㗁唑、具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物形成層間絕緣膜。 [實施例]In this embodiment, in the above-mentioned interlayer insulating film forming step, it is preferable to form a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and polymer having phenolic hydroxyl group. Interlayer insulating film. [Example]
以下,對為明確本發明之效果而進行之實施例進行說明。於實施例中,使用以下材料及測定方法。Hereinafter, examples performed to clarify the effects of the present invention will be described. In the examples, the following materials and measurement methods were used.
以下,對為明確本發明之效果而進行之實施例進行說明。Hereinafter, examples performed to clarify the effects of the present invention will be described.
(聚合物A-1:聚醯亞胺前驅物之合成) 將作為四羧酸二酐之4,4'-氧二鄰苯二甲酸二酐(ODPA)添加至2升容量之可分離式燒瓶中。進而,添加甲基丙烯酸2-羥基乙酯(HEMA)與γ-丁內酯,於室溫下攪拌,一面攪拌一面添加吡啶,獲得反應混合物。由反應所引起之發熱結束後,冷卻至室溫,放置16小時。(Polymer A-1: Synthesis of polyimide precursor) 4,4'-oxydiphthalic dianhydride (ODPA), which is tetracarboxylic dianhydride, was added to a separable flask with a capacity of 2 liters. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were added, stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the exotherm caused by the reaction is over, it is cooled to room temperature and left for 16 hours.
其次,於冰浴冷卻下,一面攪拌將二環己基碳二醯亞胺(DCC)溶解於γ-丁內酯中之溶液,一面以40分鐘添加至反應混合物中。繼而,一面攪拌使作為二胺之4,4'-二胺基二苯醚(DADPE)懸浮於γ-丁內酯者,一面以60分鐘進行添加。進而,於室溫下攪拌2小時後,添加乙醇並攪拌1小時,其次添加γ-丁內酯。藉由過濾,去除於反應混合物中產生之沈澱物,獲得反應液。Secondly, under cooling in an ice bath, while stirring the solution of dicyclohexylcarbodiimide (DCC) dissolved in γ-butyrolactone, it was added to the reaction mixture in 40 minutes. Then, while stirring, 4,4'-diaminodiphenyl ether (DADPE) which is a diamine was suspended in γ-butyrolactone, it was added for 60 minutes. Furthermore, after stirring for 2 hours at room temperature, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.
將所得反應液添加至乙醇中,生成包含粗聚合物之沈澱物。將生成之粗聚合物過濾分離,溶解於四氫呋喃,獲得粗聚合物溶液。將所得粗聚合物溶液滴加至水中,使聚合物沈澱,將所得沈澱物過濾分離後進行真空乾燥,獲得粉末狀之聚合物(聚醯亞胺前驅物(聚合物A-1))。關於成分A-1中使用之化合物之質量,如下述表1所示。The obtained reaction solution was added to ethanol to generate a precipitate containing crude polymer. The produced crude polymer was separated by filtration and dissolved in tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (polyimide precursor (polymer A-1)). The mass of the compound used in component A-1 is shown in Table 1 below.
(聚合物A-2之合成) 除將四羧酸二酐與二胺如下述表1進行變更以外,以與上述聚合物A-1中記載之方法相同之方式進行反應,獲得聚醯亞胺前驅物(聚合物A-2)。(Synthesis of polymer A-2) Except that the tetracarboxylic dianhydride and diamine were changed as shown in Table 1 below, the reaction was carried out in the same manner as the method described in the above polymer A-1 to obtain a polyimide precursor (polymer A-2) .
(聚合物B-1:聚苯并㗁唑前驅物之合成) 於具備攪拌機、溫度計之0.5升之燒瓶中添加作為二羧酸之4,4'-二苯醚二羧酸15.48 g、N-甲基吡咯啶酮。將燒瓶冷卻至5℃後,滴加亞硫醯氯,使之反應30分鐘,獲得二甲醯氯之溶液。繼而,於具備攪拌機、溫度計之0.5升之燒瓶中添加N-甲基吡咯啶酮。將作為雙胺基苯酚之雙(3-胺基-4-羥基苯基)六氟丙烷18.30 g與間胺基苯酚2.18 g攪拌溶解後,添加吡啶。並且,一面將溫度保持為0~5℃,一面以30分鐘滴加二甲醯氯之溶液後,持續攪拌30分鐘。將溶液投入3升之水中,回收析出物,以純水洗淨3次後,進行減壓乾燥,獲得聚合物(聚苯并㗁唑前驅物(聚合物B-1))。關於聚合物B-1中使用之化合物之質量,如下述表1所示。(Polymer B-1: Synthesis of polybenzoxazole precursor) In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid as a dicarboxylic acid and N-methylpyrrolidone were added. After cooling the flask to 5°C, sulfite chloride was added dropwise and reacted for 30 minutes to obtain a solution of dimethyl chloride. Next, N-methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane which is a bisaminophenol and 2.18 g of m-aminophenol, pyridine was added. In addition, while maintaining the temperature at 0 to 5°C, the solution of dimethyl chloride was added dropwise for 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was recovered, washed with pure water three times, and dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer B-1)). The masses of the compounds used in the polymer B-1 are shown in Table 1 below.
(聚合物B-2之合成) 除將二羧酸如下述所示之表1進行變更以外,以與上述聚合物B-1中記載之方法相同之方式進行反應,獲得聚苯并㗁唑前驅物(聚合物B-2)。(Synthesis of polymer B-2) Except for changing the dicarboxylic acid as shown in Table 1 below, the reaction was carried out in the same manner as the method described in the above-mentioned polymer B-1 to obtain a polybenzoxazole precursor (polymer B-2).
(聚合物C-1:酚樹脂之合成) 準備含有下述所示之C1樹脂85 g與下述所示之C2樹脂15 g之酚樹脂作為聚合物C-1。 C1:甲酚酚醛清漆樹脂(甲酚/甲醛酚醛清漆樹脂,間甲酚/對甲酚(莫耳比)=60/40,聚苯乙烯換算重量平均分子量=12,000,旭有機材工業公司製造,商品名「EP4020G」)(Polymer C-1: Synthesis of phenol resin) A phenol resin containing 85 g of C1 resin shown below and 15 g of C2 resin shown below was prepared as polymer C-1. C1: Cresol novolac resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (mole ratio) = 60/40, polystyrene conversion weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Industry Co., Ltd., (Product name "EP4020G")
C2:C2係以如下方式合成。 <C2:以具有碳數4~100之不飽和烴基之化合物改性之酚樹脂之合成> 混合苯酚100質量份、亞麻仁油43質量份及三氟甲磺酸0.1質量份,於120℃下攪拌2小時,獲得植物油改性酚衍生物(a)。繼而,混合植物油改性酚衍生物(a)130 g、多聚甲醛16.3 g及草酸1.0 g,於90℃下攪拌3小時。繼而,升溫至120℃,於減壓下攪拌3小時後,於反應液中添加琥珀酸酐29 g及三乙胺0.3 g,於大氣壓下、100℃下攪拌1小時。將反應液冷卻至室溫,獲得作為反應產物之以具有碳數4~100之不飽和烴基之化合物改性之酚樹脂(以下,稱為「C2樹脂」)(酸值120 mgKOH/g)。C2: C2 is synthesized in the following manner. <C2: Synthesis of phenol resin modified with a compound having an unsaturated hydrocarbon group with carbon number of 4-100> 100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 part by mass of trifluoromethanesulfonic acid were mixed and stirred at 120°C for 2 hours to obtain a vegetable oil modified phenol derivative (a). Then, 130 g of vegetable oil modified phenol derivative (a), 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed, and stirred at 90°C for 3 hours. Then, the temperature was raised to 120°C, and after stirring for 3 hours under reduced pressure, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction solution, and the mixture was stirred at 100°C for 1 hour under atmospheric pressure. The reaction liquid was cooled to room temperature to obtain a phenol resin (hereinafter referred to as "C2 resin") (acid value 120 mgKOH/g) modified with a compound having an unsaturated hydrocarbon group with a carbon number of 4 to 100 as a reaction product.
(聚合物C-2之合成) 準備下述C1樹脂100 g作為聚合物C-2。(Synthesis of polymer C-2) 100 g of the following C1 resin was prepared as polymer C-2.
[表1]
[實施例1~7、比較例1~2] 如下述表2所示進行調配,獲得感光性樹脂組合物之溶液。[Examples 1 to 7, Comparative Examples 1 to 2] It was prepared as shown in Table 2 below to obtain a photosensitive resin composition solution.
即,使用下述表2中記載之化合物,以下述表3中記載之調配量,製作實施例1~7及比較例1~2之各感光性樹脂組合物。再者,表3之單位為質量份。That is, each photosensitive resin composition of Examples 1-7 and Comparative Examples 1-2 was produced using the compound described in the following Table 2 with the compounding quantity described in the following Table 3. Furthermore, the unit in Table 3 is parts by mass.
對製作之感光性樹脂組合物進行(1)空氣環境下之重量減少率測定、(2)與密封材之密接性試驗。又,(3)對天線型模組製成後之電特性進行評價。各試驗結果示於下述表3。The prepared photosensitive resin composition was subjected to (1) the weight reduction rate measurement in an air environment, and (2) the adhesion test with the sealing material. In addition, (3) Evaluate the electrical characteristics of the antenna module after it is manufactured. The results of each test are shown in Table 3 below.
(1)重量減少率測定 使用實施例、比較例中製成之感光性樹脂組合物,製作扇出型之晶圓級晶片尺寸封裝型之半導體裝置。自製作之半導體裝置儘可能完整地取出厚10 μm之層間絕緣膜。將取出之層間絕緣膜約10 mg放入鉑盤,測定於空氣流量50 ml/分鐘下以升溫速度10℃/分鐘升溫至700℃後之重量減少率。(1) Determination of weight loss rate Using the photosensitive resin composition prepared in the Examples and Comparative Examples, fan-out wafer-level chip size package type semiconductor devices were produced. Take out the 10 μm-thick interlayer insulating film as completely as possible from the manufactured semiconductor device. Put about 10 mg of the interlayer insulating film taken out into a platinum pan, and measure the weight loss rate after heating to 700°C at a heating rate of 10°C/min at an air flow rate of 50 ml/min.
(2)與密封材之密接性試驗 準備Nagase chemteX公司製造之R4000系列作為環氧系密封材。繼而,將密封材以厚度成為約150微米之方式旋轉塗佈於鋁濺鍍之矽晶圓上,於130℃下進行熱硬化,使環氧系密封材硬化。將實施例、比較例中製作之感光性樹脂組合物以最終膜厚成為10微米之方式塗佈於上述環氧系硬化膜上。對塗佈之感光性樹脂組合物,於實施例1~5為200 mJ/cm2 ,實施例6、7及比較例1、2為500 mJ/cm2 之曝光條件下進行整個面之曝光後,於230℃下以2小時進行熱硬化,製作厚度10微米之第1層之硬化膜。(2) Adhesion test with sealing material Prepare R4000 series manufactured by Nagase chemteX as epoxy sealing material. Then, the sealing material is spin-coated on the aluminum sputtered silicon wafer so that the thickness becomes about 150 microns, and the epoxy-based sealing material is cured by thermal curing at 130°C. The photosensitive resin composition produced in the Examples and Comparative Examples was applied on the epoxy-based cured film so that the final film thickness became 10 micrometers. For the coated photosensitive resin composition, the entire surface was exposed under the exposure conditions of 200 mJ/cm 2 in Examples 1 to 5, and 500 mJ/cm 2 in Examples 6, 7 and Comparative Examples 1 and 2 , Heat curing at 230°C for 2 hours to produce a cured film of the first layer with a thickness of 10 microns.
於上述第1層之硬化膜上塗佈第1層之硬化膜形成中所使用之感光性樹脂組合物,於與第1層之硬化膜製作時相同之條件下進行整個面之曝光後,進行熱硬化,製作厚度10微米之第2層之硬化膜。The photosensitive resin composition used in the formation of the cured film of the first layer is coated on the cured film of the first layer, and the entire surface is exposed under the same conditions as the cured film of the first layer. Heat curing to produce a second layer of cured film with a thickness of 10 microns.
使用網帶式連續煅燒爐(Koyo Thermo Systems公司製造,型號名6841-20AMC-36),於模擬之回焊條件下,於氮氣環境下,將第2層之硬化膜形成後之試驗片加熱至波峰溫度260℃。所謂模擬之回焊條件,係指以依據與半導體裝置之評價方法相關之美國半導體業界團體之標準規格即IPC/JEDEC J-STD-020A之7.6項中記載之回焊條件的形態,將焊料熔點假設為高溫之220℃從而規格化。Using a mesh belt continuous calcination furnace (manufactured by Koyo Thermo Systems, model name 6841-20AMC-36), under simulated reflow conditions, in a nitrogen environment, heat the test piece after the second layer of cured film is formed to The peak temperature is 260℃. The so-called simulated reflow conditions refer to the form of the reflow conditions described in IPC/JEDEC J-STD-020A, the standard specification of the American semiconductor industry group related to the evaluation method of semiconductor devices, and the melting point of the solder It is assumed to be 220°C at a high temperature and standardized.
於上述製作之回焊前及回焊後之樣品之感光性樹脂硬化膜上立設銷,使用拉取試驗機(pull tester)(Quad Group公司製造,SEBASTIAN 5型)進行密接性試驗。 評價:接著強度70 MPa以上・・・密接力◎ 50 MPa以上―未達70 MPa・・・密接力○ 30 MPa以上―未達50 MPa・・・密接力△ 未達30 MPa・・・密接力×Pins were erected on the photosensitive resin cured film of the samples before and after the reflow produced above, and the adhesion test was performed using a pull tester (manufactured by Quad Group, SEBASTIAN 5). Evaluation: Adhesive strength 70 MPa or more・・・Adhesive strength◎ 50 MPa or more-less than 70 MPa...adhesive force○ 30 MPa or more-less than 50 MPa...adhesive force△ Less than 30 MPa・・・Sealing force×
(3)天線一體型模組之評價(電特性) 使用實施例、比較例中製成之感光性樹脂組合物,製成將扇出型之晶圓級晶片尺寸封裝型之半導體裝置與天線一體化之天線一體型模組。實施例、比較例中製作之感光性樹脂組合物係用作半導體裝置之層間絕緣膜。又,實施例、比較例中製作之感光性樹脂組合物亦用作天線與地(ground)(基準電位)之間之絕緣構件。該絕緣構件之厚度對天線之放射光率產生影響,故而設為可獲得最大放射效果之厚度。(3) Evaluation of antenna integrated module (electrical characteristics) Using the photosensitive resin composition prepared in the Examples and Comparative Examples, a fan-out wafer-level chip size package type semiconductor device and an antenna were integrated into an antenna integrated module. The photosensitive resin compositions produced in the examples and comparative examples are used as interlayer insulating films of semiconductor devices. In addition, the photosensitive resin composition produced in the Examples and Comparative Examples is also used as an insulating member between the antenna and the ground (reference potential). The thickness of the insulating member affects the radiation rate of the antenna, so it is set to a thickness that can obtain the maximum radiation effect.
又,天線一體型模組係以於300 GHz下動作之方式設計。In addition, the antenna integrated module is designed to operate at 300 GHz.
評價反射特性(電特性),將與天線單獨之300 GHz之背離未達5 GHz者設為○,將5 GHz以上且未達10 GHz者設為△,將10 GHz以上者設為×。又,將可見漣波者設為×,將未見者設為○。再者,此處之所謂反射特性係指由天線反射而返回至輸入端口之電量相對於對向天線輸入電力之輸入端口之輸入電力的比率。To evaluate the reflection characteristics (electrical characteristics), the deviation from the 300 GHz of the antenna alone by less than 5 GHz is set to ○, the ones above 5 GHz and below 10 GHz are set to △, and those above 10 GHz are set to ×. Also, those with visible ripples are set to ×, and those not seen are set to ○. Furthermore, the so-called reflection characteristic here refers to the ratio of the amount of power reflected by the antenna and returned to the input port relative to the input power of the input port to the opposite antenna.
[表2]
[表3]
[實施例8~14、比較例3] 如下述表4所示進行調配,獲得感光性樹脂組合物之溶液。[Examples 8-14, Comparative Example 3] It was formulated as shown in Table 4 below to obtain a photosensitive resin composition solution.
即,使用下述表4中記載之化合物,以下述表5中記載之調配量,製作物實施例8~14及比較例3之各感光性樹脂組合物。再者,表5之單位為質量份。That is, the compounds described in Table 4 below were used to prepare the photosensitive resin compositions of Product Examples 8 to 14 and Comparative Example 3 at the compounding amounts described in Table 5 below. In addition, the unit in Table 5 is parts by mass.
對製作之感光性樹脂組合物進行(1)於100℃下保持60分鐘時之揮發氣體測定、(2)與無機膜之密接性試驗。又,(3)對天線型模組製成後之電特性進行評價。各試驗之結果示於下述表5。The prepared photosensitive resin composition was subjected to (1) volatile gas measurement when kept at 100°C for 60 minutes, and (2) adhesion test to inorganic film. In addition, (3) Evaluate the electrical characteristics of the antenna module after it is manufactured. The results of each test are shown in Table 5 below.
(1)於100℃下保持60分鐘時之揮發氣體測定 使用實施例、比較例中製成之感光性樹脂組合物,製作扇出型之晶圓級晶片尺寸封裝型之半導體裝置。自製作之半導體裝置儘可能完整地取出厚10 μm之層間絕緣膜。將取出之層間絕緣膜切出1 cm2 之大小,使用升溫脫附測定裝置(電子科學股份有限公司製造,EMD-WA1000S)進行測定。以升溫速度10℃/分鐘升溫至100℃後,將於100℃下保持60分鐘後之壓力作為揮發氣體壓力。(1) Volatile gas measurement when kept at 100°C for 60 minutes Using the photosensitive resin composition prepared in the Examples and Comparative Examples, fan-out wafer-level chip size package type semiconductor devices were produced. Take out the 10 μm-thick interlayer insulating film as completely as possible from the manufactured semiconductor device. The interlayer insulating film taken out was cut into a size of 1 cm 2 and measured using a temperature-rising desorption measuring device (manufactured by Electronic Science Co., Ltd., EMD-WA1000S). After heating up to 100°C at a heating rate of 10°C/min, the pressure after maintaining at 100°C for 60 minutes is used as the volatile gas pressure.
(2)與無機膜之密接性試驗 將實施例、比較例中製作之感光性樹脂組合物以最終膜厚成為10微米之方式塗佈於矽晶圓上。對塗佈之感光性樹脂組合物,於實施例8~12為200 mJ/cm2 ,實施例13、14及比較例3為500 mJ/cm2 之曝光條件下進行整個面之曝光後,於230℃下以2小時進行熱硬化,製作厚度10微米之硬化膜。(2) Adhesion test with inorganic film The photosensitive resin composition produced in the examples and comparative examples was applied on a silicon wafer so that the final film thickness became 10 microns. For the coated photosensitive resin composition, the entire surface was exposed under the exposure conditions of 200 mJ/cm 2 in Examples 8-12, and 500 mJ/cm 2 in Examples 13, 14 and Comparative Example 3. Heat curing at 230°C for 2 hours to produce a cured film with a thickness of 10 microns.
使用濺鍍裝置(CANON ANELVA公司製造L-440S-FHL),於所得硬化膜上濺鍍鈦層2000 Å,繼而濺鍍銅層4000 Å。A sputtering device (L-440S-FHL manufactured by CANON ANELVA) was used to sputter a titanium layer of 2000 Å and then a copper layer of 4000 Å on the obtained hardened film.
於上述製成之樣品之感光性樹脂硬化膜上立設銷,使用拉取試驗機(Quad Group公司製造,SEBASTIAN 5型)進行密接性試驗。 評價:接著強度70 MPa以上・・・密接力◎ 50 MPa以上―未達70 MPa・・・密接力○ 30 MPa以上―未達50 MPa・・・密接力△ 未達30 MPa・・・密接力×A pin was erected on the photosensitive resin cured film of the sample prepared above, and the adhesion test was performed using a pull tester (manufactured by Quad Group, SEBASTIAN 5). Evaluation: Adhesive strength 70 MPa or more・・・Adhesive strength◎ 50 MPa or more-less than 70 MPa...adhesive force○ 30 MPa or more-less than 50 MPa...adhesive force△ Less than 30 MPa・・・Sealing force×
(3)天線一體型模組之評價(電特性) 使用實施例、比較例中製成之感光性樹脂組合物,製成將扇出型之晶圓級晶片尺寸封裝型之半導體裝置與天線一體化之天線一體型模組。實施例、比較例中製作之感光性樹脂組合物係用作半導體裝置之層間絕緣膜。又,實施例、比較例中製作之感光性樹脂組合物亦用作天線與地(基準電位)之間之絕緣構件。該絕緣構件之厚度對天線之放射光率產生影響,故而設為可獲得最大放射效果之厚度。(3) Evaluation of antenna integrated module (electrical characteristics) Using the photosensitive resin composition prepared in the Examples and Comparative Examples, a fan-out wafer-level chip size package type semiconductor device and an antenna integrated antenna module were manufactured. The photosensitive resin compositions produced in the examples and comparative examples are used as interlayer insulating films of semiconductor devices. In addition, the photosensitive resin composition produced in the Examples and Comparative Examples is also used as an insulating member between the antenna and the ground (reference potential). The thickness of the insulating member affects the radiation rate of the antenna, so it is set to a thickness that can obtain the maximum radiation effect.
又,天線一體型模組係以於300 GHz下動作之方式設計。In addition, the antenna integrated module is designed to operate at 300 GHz.
評價反射特性(電特性),將與天線單獨之300 GHz之背離未達5 GHz者設為○,將5 GHz以上且未達10 GHz者設為△,將10 GHz以上者設為×。再者,此處之所謂反射特性係指由天線反射而返回至輸入端口之電量相對於對向天線輸入電力之輸入端口之輸入電力的比率。To evaluate the reflection characteristics (electrical characteristics), the deviation from the 300 GHz of the antenna alone by less than 5 GHz is set to ○, the ones above 5 GHz and below 10 GHz are set to △, and those above 10 GHz are set to ×. Furthermore, the so-called reflection characteristic here refers to the ratio of the amount of power reflected by the antenna and returned to the input port relative to the input power of the input port to the opposite antenna.
[表4]
[表5]
使用實施例1~14中記載之感光性樹脂組合物,製作於塑模樹脂中含有環氧樹脂之扇出型之晶圓級晶片尺寸封裝型之半導體裝置時,可無問題地動作。 [產業上之可利用性]When the photosensitive resin composition described in Examples 1 to 14 is used to produce a fan-out wafer-level chip size package type semiconductor device containing epoxy resin in the mold resin, it can operate without problems. [Industrial availability]
本發明可較佳地應用於具有半導體晶片及與半導體晶片連接之再配線層之半導體裝置,尤其扇出(Fan-Out)型之晶圓級晶片尺寸封裝型之半導體裝置。The present invention can be preferably applied to a semiconductor device having a semiconductor chip and a rewiring layer connected to the semiconductor chip, especially a fan-out (fan-out) wafer-level chip size package type semiconductor device.
1:半導體裝置
2:半導體晶片
2a:端子
3:密封材
4:再配線層
5:配線
6:層間絕緣膜
7:外部連接端子
10:晶圓
11:支持體
12:塑模樹 脂
13:感光性樹脂組合物
1: Semiconductor device
2:
圖1係本實施形態之半導體裝置之剖面模式圖。 圖2係本實施形態之半導體裝置之俯視模式圖。 圖3A~H係本實施形態之半導體裝置之製造步驟之一例。 圖4係覆晶BGA(Ball Grid Array,球柵陣列)與扇出(Fan-Out)型WLCSP之比較圖。FIG. 1 is a schematic cross-sectional view of the semiconductor device of this embodiment. FIG. 2 is a schematic plan view of the semiconductor device of this embodiment. 3A to H are examples of manufacturing steps of the semiconductor device of this embodiment. Figure 4 is a comparison diagram of flip chip BGA (Ball Grid Array) and Fan-Out WLCSP.
1:半導體裝置 1: Semiconductor device
2:半導體晶片 2: Semiconductor wafer
2a:端子 2a: terminal
3:密封材 3: Sealing material
4:再配線層 4: Redistribution layer
5:配線 5: Wiring
6:層間絕緣膜 6: Interlayer insulating film
7:外部連接端子 7: External connection terminal
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2019
- 2019-11-25 JP JP2019212170A patent/JP7370229B2/en active Active
- 2019-12-25 TW TW108147585A patent/TWI753339B/en active
- 2019-12-25 TW TW112131420A patent/TW202348688A/en unknown
- 2019-12-25 TW TW110147342A patent/TWI816256B/en active
- 2019-12-26 CN CN201911367935.2A patent/CN111384021B/en active Active
- 2019-12-26 CN CN202410525922.8A patent/CN118448385A/en active Pending
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JP7370229B2 (en) | 2023-10-27 |
CN118448386A (en) | 2024-08-06 |
TWI816256B (en) | 2023-09-21 |
CN111384021A (en) | 2020-07-07 |
TWI753339B (en) | 2022-01-21 |
CN111384021B (en) | 2024-04-16 |
TW202348688A (en) | 2023-12-16 |
CN118448385A (en) | 2024-08-06 |
JP2020113748A (en) | 2020-07-27 |
TW202212422A (en) | 2022-04-01 |
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