TW202212422A - Semiconductor device and manufacturing method thereof - Google Patents

Semiconductor device and manufacturing method thereof Download PDF

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TW202212422A
TW202212422A TW110147342A TW110147342A TW202212422A TW 202212422 A TW202212422 A TW 202212422A TW 110147342 A TW110147342 A TW 110147342A TW 110147342 A TW110147342 A TW 110147342A TW 202212422 A TW202212422 A TW 202212422A
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insulating film
interlayer insulating
semiconductor device
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TWI816256B (en
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平田竜也
坂田勇男
清水建樹
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日商旭化成股份有限公司
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488Arrangements 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
    • H01L23/498Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/48Manufacture 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
    • H01L21/4814Conductive parts
    • H01L21/4846Leads on or in insulating or insulated substrates, e.g. metallisation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/04Manufacture 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
    • H01L21/48Manufacture 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
    • H01L21/4814Conductive parts
    • H01L21/4846Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4853Connection or disconnection of other leads to or from a metallisation, e.g. pins, wires, bumps
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    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/48Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488Arrangements 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
    • H01L23/498Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
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    • H01L23/00Details of semiconductor or other solid state devices
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    • H01L23/488Arrangements 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
    • H01L23/498Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
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    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/18High density interconnect [HDI] connectors; Manufacturing methods related thereto
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181Encapsulation

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Abstract

The object of the present invention is to provide a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a packaging material and excellent electrical characteristics, and a manufacturing method thereof. The semiconductor device (1) of the present invention is characterized in that: the device is provided with a semiconductor chip (2), a packaging material (3) covering the semiconductor chip, and a rewiring layer (4) having an area larger than the aforementioned semiconductor chip when viewed from above; and the weight loss rate of the interlayer insulating film (6) of the rewiring layer, after heated to 700 DEG C in a speed of 10 DEG C/min in an air atmosphere is 5-95% by weight. According to the present invention, the semiconductor device having excellent adhesion between the interlayer insulating film in the rewiring layer and the packaging material and excellent electrical characteristics, and the manufacturing method thereof can be provided.

Description

半導體裝置及其製造方法Semiconductor device and method of manufacturing the same

本發明係關於一種半導體裝置及其製造方法。The present 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 of semiconductor packaging methods 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 further 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 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 a fan-out type semiconductor package, by covering the semiconductor chip with a sealing material, a chip seal body larger than the chip size of the semiconductor chip is formed. Furthermore, the rewiring layer which reaches the area|region of a semiconductor wafer and a sealing material is formed. The rewiring layer is formed with a relatively thin film thickness. In addition, since the rewiring layer can be formed up to the region of the sealing material, 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 Art 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][Problems to be Solved by 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。The fan-out type semiconductor device is required to have high adhesion between the interlayer insulating film in the rewiring layer and the sealing material. However, in the conventional fan-out type semiconductor device, the adhesion between the interlayer insulating film in the rewiring layer and the sealing material is insufficient. In addition, in the antenna-integrated module or the like, the electrical characteristics tend to be lowered.

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 has been made in view of this point, and an object of the present invention is to provide a semiconductor device having excellent adhesion between an interlayer insulating film and a sealing material in a rewiring layer, and excellent electrical properties, and a method for producing the same. [Technical means to solve problems]

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 cm 2中為0.2×10 -6~2.5×10 -6Pa。 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 cm 2中為0.4×10 -6~1.8×10 -6Pa。 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 that of the semiconductor chip in plan view, and the interlayer insulating film between the rewiring layers is in an air environment with a thickness of 10 The weight reduction rate after the temperature was raised to 700°C per minute was 5 to 95% by weight. In 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 that of the semiconductor chip in plan view, and the rewiring layer is 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 that of the semiconductor chip in plan view, and the rewiring layer is 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 this invention, it is preferable that the said sealing material and the said interlayer insulating film are in direct 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, the interlayer insulating film preferably 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]

Figure 02_image001
(通式(1)中,X 1為4價有機基,Y 1為2價有機基,m為1以上之整數) In this invention, it is preferable that the said interlayer insulating film contains the polyimide containing the structure of following general formula (1). [hua 1]
Figure 02_image001
(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X 1為含有芳香族環之4價有機基,上述通式(1)中之Y 1為含有芳香族環之2價有機基。 In the present invention, X 1 in the general formula (1) is preferably a tetravalent organic group containing an aromatic ring, and Y 1 in the 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X 1含有下述通式(2)~通式(4)所表示之至少一種結構。 [化2]

Figure 02_image003
[化3]
Figure 02_image005
[化4]
Figure 02_image007
(通式(4)中,R 9為氧原子、硫原子或2價有機基) In the present invention, X 1 in the above-mentioned general formula (1) preferably contains at least one structure represented by the following general formulae (2) to (4). [hua 2]
Figure 02_image003
[hua 3]
Figure 02_image005
[hua 4]
Figure 02_image007
(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X 1含有下述通式(5)所表示之結構。 [化5]

Figure 02_image009
Preferably, X 1 in the above general formula (1) contains a structure represented by the following general formula (5). [hua 5]
Figure 02_image009

較佳為上述通式(1)中之Y 1含有下述通式(6)~通式(8)所表示之至少一種結構。 [化6]

Figure 02_image011
(R 10、R 11、R 12及R 13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]
Figure 02_image013
(R 14~R 21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]
Figure 02_image015
(R 22為2價基,R 23~R 30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 said general formula (1) contains at least 1 type of structure represented by following general formula (6) - general formula (8). [hua 6]
Figure 02_image011
(R 10 , R 11 , R 12 and R 13 are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different) [Chemical 7]
Figure 02_image013
(R 14 to R 21 are a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be different from each other or the same) [Chem. 8]
Figure 02_image015
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 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Y 1含有下述通式(9)所表示之結構。 [化9]

Figure 02_image017
In the present invention, Y 1 in the above general formula (1) preferably has a structure represented by the following general formula (9). [Chemical 9]
Figure 02_image017

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]

Figure 02_image019
(通式(10)中,Y 2與Y 3為2價有機基) In this invention, it is preferable that the said polybenzoxazole contains the polybenzoxazole of the structure containing the following general formula (10). [Chemical 10]
Figure 02_image019
(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Y 2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 having 1 to 30 carbon atoms.

於本發明中,較佳為上述通式(10)之Y 2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, Y 2 of the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted with fluorine atoms.

於本發明中,較佳為上述通式(10)之Y 3為含有芳香族基之2價有機基。 In this invention, it is preferable that Y 3 of the said 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Y 3含有下述通式(6)~(8)所表示之至少一種結構。 [化11]

Figure 02_image021
(R 10、R 11、R 12及R 13為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [化12]
Figure 02_image023
(R 14~R 21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]
Figure 02_image025
(R 22為2價基,R 23~R 30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 formulae (6) to (8). [Chemical 11]
Figure 02_image021
(R 10 , R 11 , R 12 and R 13 are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different) [Chemical 12]
Figure 02_image023
(R 14 to R 21 are a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, which may be different from each other or the same.) [Chemical 13]
Figure 02_image025
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different)

較佳為上述通式(10)之Y 3含有下述通式(9)所表示之結構。 [化14]

Figure 02_image027
It is preferable that Y 3 of the above-mentioned general formula (10) contains a structure represented by the following general formula (9). [Chemical 14]
Figure 02_image027

於本發明中,較佳為上述通式(10)之Y 3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 to 40 carbon atoms.

於本發明中,較佳為上述通式(10)之Y 3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-mentioned 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 novolac-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 this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains the phenol resin which does not have an unsaturated hydrocarbon group, and the modified phenol resin which has an unsaturated hydrocarbon group.

於本發明中,較佳為上述層間絕緣膜含有填料。In this invention, it is preferable that the said interlayer insulating film contains a filler.

於本發明中,較佳為上述填料為無機填料。In this invention, it is preferable that the said 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 this invention, it is preferable that the shape of the said filler is a particle shape.

於本發明中,較佳為上述填料之形狀為球狀。In this invention, it is preferable that the shape of the said 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, the rewiring layer preferably contains a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the above-mentioned rewiring layer when viewed in cross-section. 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 in an air environment at 10°C/min to 700°C is 5. ~95 wt%.

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 this invention, it is preferable that the said 2nd interlayer insulating film layer is a composition different from the said 1st 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 above-mentioned 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 above-mentioned first interlayer insulating film layer in an air environment at a temperature of 10° C. The weight loss rate after the temperature was raised to 700°C per minute was 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 type wafer-level chip-scale 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, the interlayer insulating film of the rewiring layer preferably 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, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 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, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 30 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40~90重量%。In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 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, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 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, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 80 wt % 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40~75重量%。In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 75 wt % 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, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 70 wt % 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 contents are preferred.

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 this invention, it is preferable that the said sealing material and the said interlayer insulating film are in direct 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, the interlayer insulating film preferably 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]

Figure 02_image029
(通式(1)中,X 1為4價有機基,Y 1為2價有機基,m為1以上之整數) In this invention, it is preferable that the said interlayer insulating film contains the polyimide containing the structure of following general formula (1). [Chemical 15]
Figure 02_image029
(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X 1為含有芳香族環之4價有機基,上述通式(1)中之Y 1為含有芳香族環之2價有機基。 In the present invention, X 1 in the general formula (1) is preferably a tetravalent organic group containing an aromatic ring, and Y 1 in the 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X 1含有下述通式(2)~通式(4)所表示之至少一種結構。 [化16]

Figure 02_image031
[化17]
Figure 02_image033
[化18]
Figure 02_image035
(通式(4)中,R 9為氧原子、硫原子或2價有機基) In the present invention, X 1 in the above-mentioned general formula (1) preferably contains at least one structure represented by the following general formulae (2) to (4). [Chemical 16]
Figure 02_image031
[Chemical 17]
Figure 02_image033
[Chemical 18]
Figure 02_image035
(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X 1含有下述通式(5)所表示之結構。 [化19]

Figure 02_image037
Preferably, X 1 in the above general formula (1) contains a structure represented by the following general formula (5). [Chemical 19]
Figure 02_image037

較佳為上述通式(1)中之Y 1含有下述通式(6)~通式(8)所表示之至少一種結構。 [化20]

Figure 02_image039
(R 10、R 11、R 12及R 13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]
Figure 02_image041
(R 14~R 21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]
Figure 02_image043
(R 22為2價基,R 23~R 30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 said general formula (1) contains at least 1 type of structure represented by following general formula (6) - general formula (8). [hua 20]
Figure 02_image039
(R 10 , R 11 , R 12 and R 13 are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different) [Chemical 21]
Figure 02_image041
(R 14 to R 21 are a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be different from each other or the same) [Chemical 22]
Figure 02_image043
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 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Y 1含有下述通式(9)所表示之結構。 [化23]

Figure 02_image045
In the present invention, Y 1 in the above general formula (1) preferably has a structure represented by the following general formula (9). [Chemical 23]
Figure 02_image045

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]

Figure 02_image047
(通式(10)中,Y 2與Y 3為2價有機基) In this invention, it is preferable that the said polybenzoxazole contains the polybenzoxazole of the structure containing the following general formula (10). [Chemical 24]
Figure 02_image047
(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Y 2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 having 1 to 30 carbon atoms.

於本發明中,較佳為上述通式(10)之Y 2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, Y 2 of the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted with fluorine atoms.

於本發明中,較佳為上述通式(10)之Y 3為含有芳香族基之2價有機基。 In this invention, it is preferable that Y 3 of the said 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Y 3含有下述通式(6)~(8)所表示之至少一種結構。 [化25]

Figure 02_image049
(R 10、R 11、R 12及R 13為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [化26]
Figure 02_image051
(R 14~R 21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]
Figure 02_image053
(R 22為2價基,R 23~R 30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 formulae (6) to (8). [Chemical 25]
Figure 02_image049
(R 10 , R 11 , R 12 and R 13 are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different) [Chem. 26]
Figure 02_image051
(R 14 to R 21 are a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, which may be different from each other or the same.) [Chemical 27]
Figure 02_image053
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different)

較佳為上述通式(10)之Y 3含有下述通式(9)所表示之結構。 [化28]

Figure 02_image055
It is preferable that Y 3 of the above-mentioned general formula (10) contains a structure represented by the following general formula (9). [Chemical 28]
Figure 02_image055

於本發明中,較佳為上述通式(10)之Y 3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 to 40 carbon atoms.

於本發明中,較佳為上述通式(10)之Y 3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-mentioned 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 novolac-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 this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains the phenol resin which does not have an unsaturated hydrocarbon group, and the modified phenol resin which has 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, the rewiring layer preferably contains a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the above-mentioned rewiring layer when viewed in cross-section. 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 cm 2中為0.2×10 -6~2.5×10 -6Pa。 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 cm 2中為0.4×10 -6~1.8×10 -6Pa。 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 of the first interlayer insulating film layer when kept at 100° C. for 60 minutes is 0.2×10 per 1 cm 2 . -6 to 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 of the first interlayer insulating film layer when kept at 100° C. for 60 minutes is 0.4×10 per 1 cm 2 . -6 to 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 this invention, it is preferable that the said 2nd interlayer insulating film layer is a composition different from the said 1st 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, the volatile gas when the second interlayer insulating film is kept at 100°C for 60 minutes is preferably different from the volatile gas when the first interlayer insulating film 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 type wafer-level chip-scale 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 cm 2中為0.2×10 -6~2.5×10 -6Pa。 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 cm 2中為0.6×10 -6~1.8×10 -6Pa。 In the present invention, when the interlayer insulating film of the rewiring layer is kept at 100° C. for 60 minutes, the volatile gas is preferably 0.2×10 -6 to 2.5×10 -6 Pa per 1 cm 2 . In the present invention, more preferably, the volatile gas per 1 cm 2 is 0.6×10 -6 to 1.8×10 -6 Pa when the interlayer insulating film of the rewiring layer is kept at 100° C. for 60 minutes.

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 cm 2中為0.6×10 -6~1.6×10 -6Pa。 In the present invention, it is further 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 1.6×10 −6 Pa per 1 cm 2 .

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 cm 2中為0.6×10 -6~1.4×10 -6Pa。 In the present invention, more preferably, the volatile gas per 1 cm 2 of the interlayer insulating film of the rewiring layer is 0.6×10 -6 to 1.4×10 -6 Pa when kept at 100° C. for 60 minutes.

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, the interlayer insulating film preferably 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, the interlayer insulating film preferably contains a volatilization modifier.

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, the interlayer insulating film preferably contains a thermal crosslinking agent and a volatilization modifier.

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 this invention, it is preferable that the said rewiring layer contains the inorganic film in contact with the said 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 this invention, it is preferable that the said inorganic film has the reaction layer which the volatile gas contained in the said interlayer insulating film and the component of the said inorganic film react with.

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 cm 2中為0.2×10 -6~2.5×10 -6Pa。 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 cm 2中為0.4×10 -6~1.8×10 -6Pa。 The method of manufacturing a semiconductor device of the present invention is characterized by comprising 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 including an interlayer insulating film, and the interlayer insulating film is in the air. The weight reduction rate after raising the temperature to 700°C at 10°C/min under the environment is 5 to 95% by weight. The method of manufacturing a semiconductor device of the present invention is characterized by comprising the steps of covering a semiconductor wafer with a sealing material, and forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and the interlayer insulating film is formed at 100°C. The volatile gas when kept at ℃ for 60 minutes is 0.2×10 -6 to 2.5×10 -6 Pa per 1 cm 2 . Preferably, the method for manufacturing a semiconductor device of the present invention is characterized by comprising 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 including an interlayer insulating film, and the interlayer insulating layer When the film was kept at 100°C for 60 minutes, the volatile gas per 1 cm 2 was 0.4×10 -6 to 1.8×10 -6 Pa.

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 following step of forming an interlayer insulating film: forming the above-mentioned photosensitive resin composition using a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a 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 above-mentioned interlayer insulating film forming step includes the following steps: using the above-mentioned interlayer insulating film in an air environment, the weight reduction rate after the temperature is raised to 700° C. at 10° C./min becomes 5 to 95% by weight. The said photosensitive resin composition adjusted with the filler forms the said interlayer insulating film. In the present invention, it is preferable to include the following step of forming an interlayer insulating film: forming the above-mentioned photosensitive resin composition using a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a 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 -6Pa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 -6Pa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 that the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.2×10 −6 to 2.5×10 −6 Pa The adjusted said photosensitive resin composition forms the said interlayer insulating film. In the present invention, it is more preferable that the above-mentioned interlayer insulating film forming step includes the following step: using the method that the volatile gas when the above-mentioned interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.4×10 −6 to 1.8×10 −6 Pa The adjusted said photosensitive resin composition forms the said 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 -6Pa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 -6Pa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 that the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.2×10 −6 to 2.5×10 −6 Pa The above-mentioned photosensitive resin composition adjusted with a thermal crosslinking agent and/or a volatilization modifier forms the above-mentioned interlayer insulating film. In the present invention, it is more preferable that the above-mentioned interlayer insulating film forming step includes the following step: using the method that the volatile gas when the above-mentioned interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.4×10 −6 to 1.8×10 −6 Pa The above-mentioned photosensitive resin composition adjusted with a thermal crosslinking agent and/or a volatilization modifier forms the above-mentioned interlayer insulating film. [Effect 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。ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of the interlayer insulating film in the rewiring layer and the sealing material is excellent, and the semiconductor device which is excellent in electrical measurement, and its manufacturing method can be provided.

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, simply referred to 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 includes a semiconductor chip 2 , a sealing material (molding resin) 3 covering the semiconductor chip 2 , and the semiconductor chip 2 and the sealing material 3 in close contact with the semiconductor chip 2 and the sealing material 3 The rewiring layer 4 is formed.

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 material 3 covers the surface of the semiconductor wafer 2 and is formed to have an area larger than the area of the semiconductor wafer 2 in plan view (viewed in the direction of arrow A).

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 rewiring layer 4 includes a plurality of wirings 5 electrically connected to a plurality of terminals 2 a provided on the semiconductor wafer 2 , and an interlayer insulating film 6 for burying the wirings 5 . The plurality of terminals 2 a provided on the semiconductor chip 2 are electrically connected to the wirings 5 in the rewiring layer 4 . One end of the wiring 5 is connected to the terminal 2 a, and the other end is connected to the external connection terminal 7 . The entire surface of the wiring 5 between the terminal 2 a and the external connection terminal 7 is covered with the interlayer insulating film 6 .

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 rewiring layer 4 is formed to be larger than the semiconductor wafer 2 in plan view (viewed in the direction of arrow A). The semiconductor device 1 shown in FIG. 1 is a fan-out type wafer level chip scale package (WLCSP) type semiconductor device. In the fan-out type semiconductor device, the interlayer insulating film 6 in the rewiring layer 4 is in close contact with not only the semiconductor chip 2 but also the sealing material 3 . The semiconductor wafer 2 includes a semiconductor such as silicon, and forms a circuit therein.

(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 rewiring layer 4 mainly includes the wiring 5 and an interlayer insulating film 6 covering the periphery of the wiring 5 . From the viewpoint of preventing unexpected conduction with the wiring 5, the interlayer insulating film 6 is preferably a member having high insulating properties.

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 "rewiring layer 4" in this embodiment refers to a layer having a thin film of the wiring 5 and the interlayer insulating film 6 as described above, and does not include an interposer or a printed wiring board. Since the semiconductor device (semiconductor IC) 1 uses the rewiring layer 4, as shown in FIG. 4, it is thinner than a semiconductor device using an interposer such as a flip chip BGA.

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 rewiring layer 4 can be set to about 3 to 30 μm. The film thickness of the rewiring layer 4 may be 1 μm or more, 5 μm or more, or 10 μm or more. Moreover, the film thickness of the rewiring layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less. When the semiconductor device 1 is viewed in plan (viewed in the direction of arrow A), it becomes the following FIG. 2 . In addition, the sealing material 3 is abbreviate|omitted.

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 configured such that the area S1 of the rewiring layer 4 is larger than the area S2 of the semiconductor wafer 2 . The area S1 of the redistribution layer 4 is not particularly limited, but from the viewpoint of increasing the number of external connection terminals, the area S1 of the redistribution layer 4 is preferably 1.05 times or more the area S2 of the semiconductor chip 2, preferably 1.1 times or more, more preferably 1.2 times or more, particularly preferably 1.3 times or more. The upper limit is not particularly limited, and the area S1 of the rewiring layer 4 may be 50 times or less, 25 times or less, 10 times or less, or 5 times or less of the area S2 of the semiconductor wafer 2 . Furthermore, in FIG. 2 , the area of the portion of the redistribution layer 4 covered by the semiconductor wafer 2 is also included in the area S1 of the redistribution layer 4 .

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 external shapes of the semiconductor wafer 2 and the rewiring layer 4 may be the same or different. In FIG. 2 , the external shapes of the semiconductor chip 2 and the redistribution layer 4 are similar in shape to a rectangle, and the shape may also be a shape other than a rectangle.

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 rewiring layer 4 may be one layer, or may be a multilayer of two or more layers. The rewiring layer 4 includes the wirings 5 and the interlayer insulating film 6 burying the wirings 5 .

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 wiring 5 is not particularly limited as long as it is a member with high conductivity, and copper is usually used.

(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 material 3 is not particularly limited, but from the viewpoint of heat resistance and adhesiveness with the interlayer insulating film, epoxy resin is preferable.

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 material 3 is preferably in direct contact with the semiconductor wafer 2 and the rewiring layer 4 . Thereby, the sealing property from the surface of the semiconductor chip 2 to the surface of the rewiring layer 4 can be effectively improved.

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 material 3 may be a single layer, or may be a structure in which a plurality of layers are laminated. When the sealing material 3 has a laminated structure, it can be a laminated structure of the same material or a laminated structure of different materials.

(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) The present embodiment is characterized in that the weight reduction rate of the interlayer insulating film 6 is 5 to 95 wt % after the temperature is raised to 700° C. at 10° C./min in an air environment. Hereinafter, the weight reduction rate after the temperature is raised to 700° C. at 10° C./min in an air environment is simply referred to as “weight reduction rate”.

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 ratio is 5 to 95% by weight, the interlayer insulating film 6 and the sealing material 3 have excellent adhesion during high temperature treatment. The reason for this is not certain, but the inventors of the present invention speculate as follows.

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 rewiring layer 4 , the photosensitive resin composition is coated on the chip sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light. Then, the photosensitive resin composition is developed and hardened, thereby selectively forming a portion having a cured product of the photosensitive resin composition and a portion having no cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. In general, the rewiring layer 4 is often multi-layered. That is, the photosensitive resin composition is further coated, exposed, developed, and cured on the interlayer insulating film 6 and the wiring 5 .

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 interlayer insulating film 6 and the wiring 5, depending on the manufacturing method, a reflow step may be included. On the other hand, since the interlayer insulating film 6 needs to be patterned as described above, it usually contains a polar resin or an additive in many cases, and tends to contain moisture. It is presumed that the insulating film undergoes a temporary high temperature thermal history such as reflow, so that volatilized water is generated at the interface between the sealing material and the insulating film, and thus the adhesiveness is degraded. When the resin content of the interlayer insulating film 6 is low, that is, when the weight reduction rate of the interlayer insulating film 6 is within a certain range, the volatilization of moisture tends to be suppressed, so it exists between the sealing material 3 and the interlayer insulating film 6 . The interface is less likely to accumulate gas, and the sealing material 3 and the interlayer insulating film 6 tend not to be easily peeled off. Moreover, in the case where the weight reduction rate of the interlayer insulating film 6 falls within a specific range, the resin content rate is sufficiently high, so that the adhesiveness with the sealing material can be sufficiently secured.

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 interlayer insulating film 6 of the present embodiment preferably has a weight reduction rate of 5 to 95% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment. Therefore, in this embodiment, the adhesion between the interlayer insulating film 6 and the sealing material 3 is good, and the amount of water volatilized from the interlayer insulating film 6 during the thermal history is small, so the adhesion after the thermal history is also good.

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 material 3, the weight loss rate of the interlayer insulating film 6 is preferably 95% by weight or less, more preferably 90% by weight or less, and more preferably 85% by weight or less. , more preferably 80% by weight or less, particularly preferably 75% by weight or less.

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 interlayer insulating film 6 may be 70 wt % or less, 65 wt % or less, 60 wt % or less, 55 wt % or less, 50 wt % or less, or 45 wt % or less, 40 wt % or less, 35 wt % or less, 30 wt % or less, 25 wt % or less, or 20 wt % or less.

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 adhesiveness after the thermal history between the interlayer insulating film and the sealing material 3, the weight loss rate of the interlayer insulating film 6 is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 15% by weight % or more, more preferably 20 wt % or more, particularly preferably 25 wt % or more, particularly preferably 30 wt % or more, still more preferably 35 wt % or more, and most preferably 40 wt % or more.

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 interlayer insulating film 6 may be 45 wt % or more, 50 wt % or more, 55 wt % or more, 60 wt % or more, 65 wt % or more, or 70% by weight or more, 75% by weight or more, or 80% by weight or more.

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 interlayer insulating film 6 of the present embodiment is within a specific range, for example, when it is made into an antenna-integrated module, the electrical characteristics become favorable. The reason has not been identified, but the inventors of the present invention consider it as follows.

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 a material that is not easily reduced in weight, such as a large amount of inorganic fillers, and these tend to have a low dielectric loss tangent. Therefore, for example, compared with the antenna alone, 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 components such as resin, so the uniformity of the components contained in the interlayer insulating film is good, and the ripples of the signal sent to the antenna or sent from the antenna ( The disorder of the waveform) tends to be suppressed. In the case where the weight reduction rate of the interlayer insulating film 6 is in a specific range, these tendencies can be combined, and the electrical characteristics can be improved.

(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 cm 2中為0.2×10 -6~2.5×10 -6Pa。 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 cm 2中為0.4×10 -6~1.8×10 -6Pa。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 aspect of the present embodiment, the interlayer insulating film 6 is characterized in that the volatile gas per 1 cm 2 is 0.2×10 −6 to 2.5×10 when the interlayer insulating film 6 is kept at 100° C. for 60 minutes. 6 Pa. In yet another aspect of the present embodiment, the volatile gas when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is 0.4×10 −6 to 1.8×10 −6 Pa per 1 cm 2 . Hereinafter, the volatile gas at the time of holding at 100° C. for 60 minutes is simply referred to as “volatile gas pressure”.

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 volatile gas when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is in the above range, the adhesion between the interlayer insulating film 6 and the inorganic film 8 is excellent. The reason for this is not certain, but the inventors of the present invention speculate as follows.

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 rewiring layer 4 , the photosensitive resin composition is coated on the chip sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light. Then, the photosensitive resin composition is developed and hardened, thereby selectively forming a portion having a cured product of the photosensitive resin composition and a portion having no cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. In general, the rewiring layer 4 is often multi-layered. That is, on the interlayer insulating film 6 and the wiring 5, the photosensitive resin composition is further coated, exposed, developed, and cured.

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, in the step of forming the interlayer insulating film 6 and the wiring 5, depending on the manufacturing method, there is a case where a step of sputtering an inorganic film such as titanium is included. On the other hand, since the interlayer insulating film 6 needs to be patterned as described above, it usually contains a polar resin or an additive in many cases, and tends to contain moisture. The contained moisture or components that are easily volatilized in vacuum volatilize a certain amount during sputtering, thereby forming a layer between the interlayer insulating film 6 and the inorganic film 8 in which the inorganic film reacts with the volatile components. When the inorganic film 8 is titanium, a layer containing titanium oxide is formed. By this reaction layer, the adhesion between the interlayer insulating film 6 and the inorganic film 8 can be improved. However, when there are too many volatile components, there is a possibility that the adhesion between the interlayer insulating film 6 and the inorganic film 8 may decrease due to the volatile components.

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 cm 2中為0.4×10 -6~1.8×10 -6Pa。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 interlayer insulating film 6 of the present embodiment preferably has a volatile gas of 0.4×10 -6 to 1.8×10 -6 Pa per 1 cm 2 when kept at 100° C. for 60 minutes. Therefore, in this embodiment, the adhesion between the interlayer insulating film 6 and the inorganic film is good.

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 -6Pa以上,更佳為0.6×10 -6Pa以上,進而較佳為0.8×10 -6Pa以上,進而更佳為1.0×10 -6Pa以上。 From the viewpoint of the adhesion between the interlayer insulating film and the inorganic film, the volatile gas pressure when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is preferably 0.4×10 -6 Pa or more, more preferably 0.6×10 -6 Pa or more, more preferably 0.8×10 -6 Pa or more, still more preferably 1.0×10 -6 Pa or more.

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 cm 2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 volatile gas pressure when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is not limited as long as it is 1.8×10 −6 or less per 1 cm 2 . It is preferably 1.8×10 -6 or less, more preferably 1.6×10 -6 or less, particularly preferably 1.4×10 -6 or less.

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。When the volatile gas pressure when the interlayer insulating film 6 of the present embodiment is kept at 100° C. for 60 minutes is within a specific range, for example, when an antenna-integrated module is produced, the electrical characteristics become favorable. The reason is not certain, but the inventors of the present invention consider it as follows.

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 non-volatile materials such as polymers, and these tend to have a low dielectric loss tangent. Therefore, for example, compared with the antenna alone, when the antenna-integrated module is manufactured, the deviation tends to be smaller.

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。In addition, the interlayer insulating film 6 in the rewiring layer 4 may be multi-layered. That is, the rewiring layer 4 may include a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the above-mentioned second interlayer insulating film layer when the rewiring layer 4 is observed in cross-section. It is different and is provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer. The so-called intermediate layer is, for example, the wiring 5 .

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 may have different volatile gas pressures. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness, or may have different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different volatile 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 cm 2中為0.2×10 -6~2.5×10 -6Pa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 cm 2中為0.4×10 -6~1.8×10 -6Pa即可。 When the interlayer insulating film 6 is multi-layered, the volatile gas pressure of at least one layer of the interlayer insulating film 6 when kept at 100° C. for 60 minutes is 0.2×10 −6 per 1 cm 2 of the plurality of layers present. ~2.5×10 -6 Pa is sufficient. Preferably, when the interlayer insulating film 6 is multi-layered, among the multiple layers present, at least one layer of the interlayer insulating film 6 is kept at 100° C. for 60 minutes when the volatile gas pressure is 0.4× per 1 cm 2 . 10 -6 to 1.8×10 -6 Pa is sufficient.

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。In addition, the interlayer insulating film 6 in the rewiring layer 4 may be multi-layered. That is, the rewiring layer 4 may include a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the above-mentioned second interlayer insulating film layer when the rewiring layer 4 is observed in cross-section. It is different and is provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer. The so-called intermediate layer is, for example, the wiring 5 .

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 may have different weight reduction rates. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness, or may have different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different weight reduction rates, 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。In the case where the interlayer insulating film 6 is multi-layered, the weight reduction rate of the interlayer insulating film 6 in at least one of the multiple layers may be 5 to 95% by weight, but between the sealing material 3 and the interlayer insulating film layer Since it is easy to be peeled off by gas, the weight reduction rate of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is preferably 10 to 95% by weight. When the weight reduction rate of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is 10 to 95% by weight, the adhesiveness between the sealing material 3 and the interlayer insulating film 6 is excellent.

(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 interlayer insulating film 6 is not particularly limited. For example, it is preferably a film containing at least one compound selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

(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 for forming the interlayer insulating film 6 is not particularly limited as long as it is a photosensitive resin composition, and preferably contains a polyimide precursor, a polybenzoxazole precursor, or a phenolic one. A photosensitive resin composition of at least one compound in a polymer of hydroxyl groups. The resin composition for forming the interlayer insulating film 6 may be liquid or film. In addition, the resin composition for forming the interlayer insulating film 6 may be a negative-type photosensitive resin composition or a positive-type photosensitive resin composition.

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 the relief pattern is called a cured relief pattern. This hardened relief pattern becomes the interlayer insulating film 6 .

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, it is preferable that the photosensitive resin composition of the interlayer insulating film 6 contains a filler. The filler in the present embodiment is not limited as long as it is an inert substance added for the purpose of improving strength and various properties.

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。The filler is preferably in the form of particles from the viewpoint of suppressing an increase in viscosity when it is prepared as a resin composition. Examples of the particle shape include needle shape, plate shape, spherical shape, and the like, and the filler is preferably spherical from the viewpoint of suppressing an increase in viscosity at the time of preparing the resin composition.

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。As acicular fillers, wollastonite, potassium titanate, wollastonite, aluminum borate, acicular calcium carbonate, etc. are mentioned.

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。As a plate-like filler, talc, mica, sericite, glass flakes, montmorillonite, boron nitride, plate-like calcium carbonate, etc. are mentioned.

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。As spherical fillers, calcium carbonate, silicon oxide, aluminum oxide, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, barium titanate, etc. are mentioned. Among these, silicon oxide, aluminum oxide, titanium oxide, and barium titanate are preferable, and silicon oxide and aluminum oxide are more preferable from the viewpoint of electrical properties and storage stability when used as a resin composition.

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, in the case of spherical shape, the primary particle size is defined as the size, and in the case of plate shape or needle shape, the length of the long side is defined as the size, preferably 5 nm to 1000 nm, more preferably 10 nm nm~1000 nm. When it is 10 nm or more, there exists a tendency for it to become fully uniform when used as a resin composition, and when it is 1000 nm or less, photosensitivity can be provided. From the viewpoint of imparting photosensitivity, it is preferably 800 nm or less, more preferably 600 nm or less, and still more preferably 300 nm or less. From the viewpoint of adhesiveness or uniformity of the resin composition, it is preferably 15 nm or more, more preferably 30 nm or more, and still more 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, it is preferable that the photosensitive resin composition of the interlayer insulating film 6 contains a thermal crosslinking agent or a volatilization regulator. The photosensitive resin composition is not particularly limited, and may be a photosensitive resin composition containing at least one compound selected from a polyimide precursor, a polybenzoxazole precursor, or a polymer having a phenolic hydroxyl group. As the thermal crosslinking accelerator, for example, epoxy compounds, oxetane compounds, oxazoline compounds, aldehydes, aldehyde-modified compounds, isocyanate compounds, unsaturated bond-containing compounds, polyol compounds, polyol compounds can be preferably used. Amine compounds, melamine compounds, metal chelating agents, C-methylol compounds, N-methylol compounds, and the like.

作為揮發調整劑,可列舉:聚乙二醇、聚丙二醇等。As a volatility modifier, 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。 <Polyimide precursor composition> (A) Photosensitive resin As a photosensitive resin used for a polyimide precursor composition, a polyamide, a polyamide, etc. are mentioned. For example, as the polyamic acid ester, a polyamic acid ester containing a repeating unit represented by the following general formula (11) can be used.

[化29]

Figure 02_image057
R 1及R 2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。X 1為4價有機基,Y 1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。 [Chemical 29]
Figure 02_image057
R 1 and R 2 are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a valent organic group having a carbon-carbon unsaturated double bond, or a valence having 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R 1及R 2作為一價陽離子存在時,O帶負之電荷(作為-O -而存在)。又,X 1與Y 1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- ). Moreover, X 1 and Y 1 may contain a hydroxyl group.

通式(11)中之R 1及R 2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 a monovalent organic group represented by the following general formula (12) or a monovalent organic group represented by the following general formula (13) having an ammonium ion at the terminal the structure.

[化30]

Figure 02_image059
(通式(12)中,R 3、R 4及R 5分別獨立為氫原子或碳數1~5之有機基,並且m 1為1~20之整數) [Chemical 30]
Figure 02_image059
(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]

Figure 02_image061
(通式(13)中,R 6、R 7及R 8分別獨立為氫原子或碳數1~5之有機基,並且m 2為1~20之整數)。 [Chemical 31]
Figure 02_image061
(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。Polyurethanes represented by a plurality of general formula (11) may be mixed. Moreover, the polyamic acid ester which copolymerized the polyamic acid ester represented by General formula (11) can be used.

X 1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,X 1較佳為含有芳香族基之4價有機基。具體而言,X 1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。 X1 is not particularly limited, but from the viewpoint of the adhesiveness between the interlayer insulating film 6 and the sealing material 3 , X1 is preferably a tetravalent organic group containing an aromatic group. Specifically, X 1 is preferably a tetravalent organic group containing at least one structure represented by the following general formula (2) to (4).

[化32]

Figure 02_image063
[Chemical 32]
Figure 02_image063

[化33]

Figure 02_image065
[Chemical 33]
Figure 02_image065

[化34]

Figure 02_image067
(通式(4)中,R 9為氧原子、硫原子、2價有機基之任一者) [Chemical 34]
Figure 02_image067
(In the general formula (4), R 9 is any one of an oxygen atom, a sulfur atom, and a divalent organic group)

通式(4)中之R 9例如為碳數1~40之2價有機基或鹵素原子。R 9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 hydroxyl groups.

就層間絕緣膜6與密封材3之密接性之觀點而言,X 1尤佳為含有下述通式(5)所表示之結構之4價有機基。 From the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, X 1 is particularly preferably a tetravalent organic group containing a structure represented by the following general formula (5).

[化35]

Figure 02_image069
[Chemical 35]
Figure 02_image069

Y 1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,Y 1較佳為含有芳香族基之2價有機基。具體而言,Y 1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, but Y 1 is preferably a divalent organic group containing an aromatic group from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 . Specifically, Y 1 is preferably a divalent organic group containing at least one structure represented by the following general formula (6) to (8).

[化36]

Figure 02_image071
(R 10、R 11、R 12及R 13為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [Chemical 36]
Figure 02_image071
(R 10 , R 11 , R 12 and R 13 are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different)

[化37]

Figure 02_image073
(R 14~R 21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) [Chemical 37]
Figure 02_image073
(R 14 to R 21 are hydrogen atoms, halogen atoms, and monovalent organic groups having 1 to 5 carbon atoms, which may be different from each other or the same)

[化38]

Figure 02_image075
(R 22為2價基,R 23~R 30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) [Chemical 38]
Figure 02_image075
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different)

通式(8)中之R 22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,Y 1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 film 6 and the sealing material 3, Y 1 is particularly preferably a divalent organic group containing a structure represented by the following general formula (9).

[化39]

Figure 02_image077
[Chemical 39]
Figure 02_image077

於上述聚醯胺酸酯中,其重複單元中之X 1係源自用作原料之四羧酸二酐,Y 1係源自用作原料之二胺。 In the above-mentioned polyamic acid 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。Examples of the tetracarboxylic dianhydride used as a raw material include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, and benzophenone-3,3 ',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl-3,3',4,4'-tetracarboxylic acid 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 not limited to these. In addition, these may 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。Examples of diamines used as raw materials include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diamine -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, 4,4'-diaminobiphenyl, 3,4'-diphenyl Aminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone 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) phenoxy) phenyl] bismuth, bis[4-(3-aminophenoxy)phenyl] bismuth, 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, bi-o-toluidine, 9,9 -Bis(4-aminophenyl) fluoride etc. Moreover, a part of hydrogen atoms on these benzene rings may be substituted. In addition, these may 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 the polyamic acid ester (A), the following method can be preferably used: the tetracarboxylic acid diester obtained by performing the esterification reaction of the following tetracarboxylic dianhydride is directly subjected to 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 for the esterification reaction of the said tetracarboxylic dianhydride is the alcohol which has an olefinic double bond. Specific examples thereof include, but are not limited to, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethanol, glycerin diacrylate, and glycerol dimethacrylate. These alcohols may 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)。As for the specific synthesis method of the polyamic acid ester (A) used in this embodiment, a conventionally known method can be adopted. As a synthesis method, the method shown in the specification of International Publication No. 00/43439 can be mentioned, for example. That is, a method of temporarily converting a tetracarboxylic acid diester into a tetracarboxylic acid diester diacid chloride, and subjecting the tetracarboxylic acid diester diacid chloride and a diamine to condensation in the presence of a basic compound can be used. The reaction is carried out to produce a polyamic acid ester (A). Moreover, the method of producing a polyamic acid ester (A) by the method of subjecting a tetracarboxylic-acid diester and a diamine to a condensation reaction in presence of an organic dehydrating agent is mentioned.

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 the organic dehydrating agent 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 polyamic acid ester (A) used in the present embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and 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

Figure 110147342-0000-3
、2-甲基-9-氧硫𠮿
Figure 110147342-0000-3
、2-異丙基-9-氧硫𠮿
Figure 110147342-0000-3
及二乙基-9-氧硫𠮿
Figure 110147342-0000-3
等9-氧硫𠮿
Figure 110147342-0000-3
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) Photoinitiator When the resin composition used for formation of the interlayer insulating film 6 is a negative-type photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, dibenzophenone, methyl o-benzoic acid benzoate, 4-benzyl-4'-methylbenzophenone, dibenzyl ketone, and fenone can be used. Acetophenone derivatives, acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 9-oxythiophenone
Figure 110147342-0000-3
, 2-methyl-9-oxothio
Figure 110147342-0000-3
, 2-isopropyl-9-oxothio
Figure 110147342-0000-3
and diethyl-9-oxothioate
Figure 110147342-0000-3
Wait for 9-oxysulfur 𠮿
Figure 110147342-0000-3
Derivatives, benzil derivatives such as benzil, benzil dimethyl ketal and benzil-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-bis( Azides such as 4'-diazidebenzylidene)-4-methylcyclohexanone and 2,6'-bis(4'-diazidebenzylidene)cyclohexanone, 1-phenyl -1,2-Butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2 -(O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2-(O-benzyl) oxime, 1,3-diphenylglycerol-2-(O-ethoxy Carbonyl) oximes, oximes such as 1-phenyl-3-ethoxyglycerol-2-(O-benzyl) oxime, N-arylglycines such as N-phenylglycine, Peroxides such as benzyl oxide, aromatic biimidazoles, and titanocenes, etc. Among them, the above-mentioned oximes are preferred in terms of photosensitivity.

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 amount of these photoinitiators added is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the polyurethane (A). It is excellent in photosensitivity by adding 1 mass part or more of photoinitiators with respect to 100 mass parts of polyamic acid esters (A). Moreover, by adding 40 mass parts or less, it is excellent in thick-film curability.

(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 for the formation of the interlayer insulating film 6 is a positive-type photosensitive resin, a photoacid generator is added. By containing a photoacid generator, an acid is generated in an ultraviolet-ray exposure part, and the solubility with respect to an alkaline aqueous solution of an exposure part increases. Thereby, it can be used as a positive photosensitive resin composition.

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。As a photoacid generator, a quinonediazide compound, a pernium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned. Among them, a quinonediazide compound is preferably used in terms of exhibiting an excellent dissolution inhibitory effect and obtaining a high-sensitivity positive photosensitive resin composition. Moreover, two or more types of 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 for formation of the interlayer insulating film 6, the weight reduction rate can be adjusted. As the inorganic filler, the above-mentioned fillers can be used. <How to adjust the amount of volatilized gas> If a thermal crosslinking agent or a volatilization modifier is added to the resin composition used for the formation of the interlayer insulating film 6 , the amount of volatilized gas when kept at 100° C. for 60 minutes can be adjusted. As the thermal cross-linking agent, the polymer forming the interlayer insulating film 6 reacts with the thermal cross-linking agent to cross-link, or the thermal cross-linking agent is cross-linked with each other. The thermal cross-linking agent is not limited. A compound of a functional group above the functional group (epoxy group, methacryloyl group, acryl group, etc.).

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 the volatilization temperature and the volatilization pressure can be adjusted. Among them, polyethylene glycol, polypropylene glycol, etc. are exemplified from the viewpoint of having a site capable of hydrogen bonding with the polar functional group of the polymer and having no adverse effect during development.

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 which 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 mentioned.

(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 There is no particular limitation as long as it is a solvent in which each component can be dissolved or dispersed. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, etc. are mentioned. These solvents can be used within a range of 30 to 1500 parts by mass with respect to 100 parts by mass of the (A) photosensitive resin, depending on 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 the (A) photosensitive resin when the polyimide precursor composition is exposed to light and heat-hardened after development, 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, a sensitizer for enhancing photosensitivity, an adhesive adjuvant for enhancing adhesion to a substrate, and the like may be contained.

(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 to light, the unneeded portion is rinsed with a developer. The developer to be used is not particularly limited, and in the case of a polyimide precursor composition for development with a solvent, N,N-dimethylformamide, dimethylsulfoxide, N ,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates and other good solvents, these good solvents and lower alcohols, water, aromatic Mixed solvents of poor solvents such as hydrocarbons, etc. After development, rinse with a 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, ethylene glycol Aqueous solutions of compounds showing basicity such as amine and hexamethylenediamine.

(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。 (heat hardening) After development, the polyimide precursor is ring-closed by heating to form polyimide. This polyimide becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

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, but generally, the lower the heat curing temperature, the smaller the refractive index difference tends to be. 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 above polyimide precursor composition is the following general formula (1).

[化40]

Figure 02_image079
[Chemical 40]
Figure 02_image079

通式(1)中之X 1、Y 1、m與通式(11)中之X 1、Y 1、m相同,X 1為4價有機基,Y 1為2價有機基,m為1以上之整數。通式(11)中之較佳X 1、Y 1、m因相同理由,於通式(1)之聚醯亞胺中亦較佳。 X 1 , Y 1 , and m in the general formula (1) are the same as X 1 , Y 1 , and m in the general formula (11), X 1 is a tetravalent organic group, Y 1 is a divalent organic group, and m is 1 the above integers. 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 terminal of the polyimide can be made into 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, a poly(o-hydroxyamide) containing a repeating unit represented by the following general formula (14) can be used.

[化41]

Figure 02_image081
(通式(14)中,Y 2與Y 3為2價有機基) [Chemical 41]
Figure 02_image081
(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,Y 2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 film 6 and the sealing material 3, Y 2 is preferably a divalent organic group having 1 to 30 carbon atoms, more preferably a chain alkylene group having 1 to 15 carbon atoms (wherein, The hydrogen atom of the chain alkylene may be substituted with a halogen atom), particularly preferably a chain alkylene having 1 to 8 carbon atoms and a hydrogen atom substituted with a fluorine atom.

又,就層間絕緣膜6與密封材3之密接性之觀點而言,Y 3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。 In addition, from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, Y 3 preferably contains a divalent organic group containing an aromatic group, and more preferably contains the following general formulas (6) to (8) A divalent organic group representing at least one structure.

[化42]

Figure 02_image083
(R 10、R 11、R 12及R 13為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [Chemical 42]
Figure 02_image083
(R 10 , R 11 , R 12 and R 13 are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different)

[化43]

Figure 02_image085
(R 14~R 21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) [Chemical 43]
Figure 02_image085
(R 14 to R 21 are hydrogen atoms, halogen atoms, and monovalent organic groups having 1 to 5 carbon atoms, which may be different from each other or the same)

[化44]

Figure 02_image087
(R 22為2價基,R 23~R 30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) [Chemical 44]
Figure 02_image087
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different)

通式(8)中之R 22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,Y 3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 film 6 and the sealing material 3, Y 3 is particularly preferably a divalent organic group containing a structure represented by the following general formula (9).

[化45]

Figure 02_image089
[Chemical 45]
Figure 02_image089

就層間絕緣膜6與密封材3之密接性之觀點而言,Y 3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 film 6 and the sealing material 3, Y 3 is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, Particularly preferred is a divalent chain aliphatic group having 1 to 20 carbon atoms.

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 generally be synthesized from dicarboxylic acid derivatives and hydroxyl-containing diamines. Specifically, after converting a dicarboxylic acid derivative into a dihalide derivative, it can be synthesized by reacting with diamines. As the dihalide derivative, a dichloride derivative is preferred.

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 a halogenating agent with a dicarboxylic acid derivative. As the halogenating agent, thionyl chloride, phosphonium chloride, phosphorus oxychloride, phosphorus pentachloride and the like used in the chlorination reaction of common 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 of synthesizing a dichloride derivative, a method of reacting a dicarboxylic acid derivative with the above-mentioned halogenating agent in a solvent, a method of reacting with an excess halogenating agent, and then distilling off the excess part can be used. 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。As the dicarboxylic acid used for the dicarboxylic acid derivative, for example, 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) bismuth, 2 ,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6 - Naphthalene dicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic 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, dodecafluorooctanedioic 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, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid, tetracosanedioic acid, Pentacosanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Hecosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Thirty Dioxanedioic acid, oxydiacetic acid, etc. These may be used in combination.

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。As the hydroxyl group-containing diamine, for example, 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)propane, bis(4-amino) -3-Hydroxyphenyl) bismuth, 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, etc. These may be used in combination.

(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 of the light-irradiated part. As a photoacid generator, a naphthoquinone diazonium compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl perionium salt, etc. are mentioned. Among them, the diazonaphthoquinone compound is preferred because of its higher sensitivity.

(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 It will not be specifically limited if it is a solvent which can dissolve or disperse each component.

(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 adjuvant, 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 to light, the unnecessary parts are rinsed with a developer. The developer to be used is not particularly limited, and examples thereof include alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. Aqueous 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 has been centered on the positive-type polybenzoxazole precursor composition, but a negative-type polybenzoxazole precursor composition may also be used.

(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。 (heat hardening) After development, the polybenzoxazole precursor is ring-closed by heating to form polybenzoxazole. This polybenzoxazole becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

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 influence on other members, the heating temperature is preferably lower. It is preferably 250 degrees or less, more preferably 230 degrees or less, more preferably 200 degrees or less, and still more 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 above polybenzoxazole precursor composition is the following general formula (10).

[化46]

Figure 02_image091
[Chemical 46]
Figure 02_image091

通式(10)中之Y 2、Y 3與通式(14)中之Y 2、Y 3相同。通式(14)中之較佳Y 2、Y 3因相同理由,於通式(10)之聚苯并㗁唑中亦較佳。 Y 2 and Y 3 in the general formula (10) are the same as Y 2 and Y 3 in the general formula (14). 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 thereof include vinyl polymers containing monomeric units having phenolic hydroxyl groups such as poly(hydroxystyrene), phenol resins, poly(hydroxyamides), poly(hydroxyphenylene) ethers, poly(hydroxyphenylene) ethers, and poly(hydroxyphenylene) ethers. 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, a phenol resin is preferable, and a novolak-type phenol resin is particularly preferable in terms of low cost and small volume shrinkage at the time of hardening.

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 is a polycondensation product of phenol or its derivatives and aldehydes. The polycondensation is carried out in the presence of a catalyst such as an acid or a base. The phenol resin obtained when an acid catalyst is used is specifically referred to as a novolac-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, adamantanephenol, benzyloxyphenol, xylenol, and phthalate. Phenol, resorcinol, ethyl resorcinol, hexyl resorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rosin acid, 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)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxyl) -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 the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, triacetaldehyde, glyoxal, cyclohexanal, diphenylacetaldehyde, Ethyl butyraldehyde, benzaldehyde, glyoxylic acid, 5-nor alkene-2-carbaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salialdehyde, naphthalene formaldehyde, 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 component (A) preferably contains (a) a phenol resin not having an unsaturated hydrocarbon group and (b) a modified phenol resin having an unsaturated hydrocarbon group. It is more preferable that the said (b) component is modified|denatured 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 the component (b), it is preferable to use a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms to further improve the mechanical properties (elongation at break, elastic modulus and residual stress). Sexual phenolic 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 having unsaturated hydrocarbon groups are usually phenol or derivatives thereof and compounds having unsaturated hydrocarbon groups (preferably those having 4 to 100 carbon atoms) (hereinafter, sometimes simply referred to as "unsaturated hydrocarbon group-containing resins") A polycondensation product of a reaction product (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and an aldehyde, or a reaction product of a phenol resin and an unsaturated hydrocarbon group-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 is the same as the phenol derivative described above about 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。The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups from the viewpoint of the adhesion and thermal shock resistance of the photoresist pattern. Moreover, the unsaturated hydrocarbon group-containing compound is preferably one having 8 to 80 carbon atoms, more preferably one having 10 to 60 carbon atoms, from the viewpoints of compatibility when it is used as a resin composition and flexibility of the cured film.

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 the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, 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, oleic acid, codoleic acid, sinapic acid, tetracosenoic acid, and linseed oil acid, alpha-linolenic acid, eleric acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among them, esters of unsaturated fatty acids having 8 to 30 carbon atoms and monohydric to trihydric alcohols having 1 to 10 carbon atoms are particularly preferred, and unsaturated fatty acids having 8 to 30 carbon atoms and trihydric alcohols are particularly preferred. of glycerol esters.

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。Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerol are commercially available as vegetable oils. Vegetable oils include non-drying oils with an iodine value of less than 100, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of more than 130. 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 drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. Moreover, the processed vegetable oil 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 vegetable oils, non-drying oils are preferably used from the viewpoint of preventing gelation accompanying excessive reaction in the reaction between phenol or its derivatives or phenol resin and vegetable oil and improving 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 drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferable, and tung oil and linseed oil are more preferable in that the effects of the present invention can be more effectively and surely exhibited.

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 may 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 above-mentioned phenol derivative and the above-mentioned unsaturated hydrocarbon group-containing compound are reacted to prepare 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, the unsaturated hydrocarbon group-containing compound is preferable with respect to 100 parts by mass of the phenol derivative from the viewpoint of improving the flexibility of the cured film (resist pattern). It is 1-100 mass parts, More preferably, it is 5-50 mass parts. When the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and when 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。A phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced by polycondensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes. The aldehydes can be used 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 of the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and the synthesis conditions of previously known phenol resins 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 may 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-mentioned 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 and amount of the catalyst used, but 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 phenolic resin modified with an unsaturated hydrocarbon group-containing compound. In addition, solvents, such as toluene, xylene, and methanol, can be used for 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 the compound containing an unsaturated hydrocarbon group can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative together with a compound other than a phenol such as meta-xylene, and an aldehyde. In this case, the molar ratio of the compound other than the 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) above 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 to be reacted 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. Moreover, regarding 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 (resist pattern), the unsaturated hydrocarbon group-containing compound is preferable with respect to 100 parts by mass of the phenol resin. It is 1-100 mass parts, More preferably, it is 2-70 mass parts, More preferably, it is 5-50 mass parts. When the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and when it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the Tendency to decrease heat resistance. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like can be used as a catalyst as needed. In addition, solvents, such as toluene, xylene, methanol, and tetrahydrofuran, can be used for 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 phenolic resin modified with the unsaturated hydrocarbon group-containing compound produced by the above method. Thereby, the acid-modified phenol resin can also be used as (b) component. By carrying out acid modification with a polybasic acid anhydride and introducing a carboxyl group, the solubility of the component (b) in an alkaline aqueous solution (developing solution) 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 condensation of the carboxyl group of a polybasic acid having a plurality of carboxyl groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Hydrogen phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, terrestrial anhydride, 3,6-endomethylene tetrahydro phthalic anhydride, methyl endo Dibasic acid anhydrides such as methylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aromatic tetrabasic acid dianhydrides such as anhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. These can be used alone or in combination of two or more. Among these, 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, there is an advantage that a photoresist pattern having 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。Moreover, (A) the alkali-soluble resin which has a phenolic hydroxyl group may contain the phenol resin which made the polybasic acid anhydride react and acid-modified. The solubility of the (A) component to an alkaline aqueous solution (developing solution) is further improved by containing the phenol resin acid-modified with the polybasic acid anhydride in the (A) component.

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 said 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, terresin, 3,6-endomethylenetetrahydrophthalic anhydride, methyl Dibasic acid anhydrides such as endomethylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aliphatic and aromatic tetrabasic acid dianhydrides such as dianhydrides, butane tetracarboxylic dianhydrides, cyclopentane tetracarboxylic dianhydrides, pyromellitic dianhydrides, benzophenone tetracarboxylic dianhydrides, and the like. These can be used alone or in combination of two or more. Among these, 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 naphthoquinone diazonium compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl perionium salt, etc. are mentioned. Among them, the nitrogen naphthoquinone compound is preferred because of its higher sensitivity.

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, aldehyde-modified compounds, isocyanate compounds, unsaturated bond-containing compounds, polyol compounds, polyol compounds can be preferably used. Amine compounds, melamine compounds, metal chelating agents, C-methylol compounds, N-methylol compounds, and the like.

(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 It will not be specifically limited if it is a solvent which can dissolve or disperse each component.

(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 A thermal crosslinking agent, a sensitizer, an adjuvant, a dye, a surfactant, a dissolution accelerator, a crosslinking accelerator, etc. may be contained. However, when the photosensitive resin film after pattern formation is heat-hardened by containing a thermal crosslinking agent, a thermal crosslinking agent component and (A) component react to form a crosslinked structure. Thereby, it can be hardened at low temperature, and the embrittlement of a film or the melting of a film can be prevented. As the thermal crosslinking agent component, specifically, a compound having a phenolic hydroxyl group, a compound having a methylolamine group, and a compound having an epoxy group can be 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 having a phenolic hydroxyl group, the unnecessary part is rinsed with a developer. The developer to be used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and 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。 (heat hardening) After the development, the polymers having phenolic hydroxyl groups are thermally cross-linked by heating. The cross-linked polymer becomes a hardened relief pattern, that is, the interlayer insulating film 6 .

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 influence on other members, the heating temperature is preferably lower. It is preferably 250 degrees or less, more preferably 230 degrees or less, more preferably 200 degrees or less, and still more 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。 (Manufacturing method of semiconductor device) The manufacturing method of the semiconductor device of this embodiment is demonstrated using FIG. 3. FIG. In FIG. 3A, the wafer 10 after the previous steps are prepared. In addition, in FIG. 3B , the wafer 10 after the previous step is diced to form a plurality of semiconductor chips 2 . The semiconductor wafer 2 may also be a purchased item. The semiconductor wafer 2 thus prepared is attached to the support 11 at predetermined intervals as shown in FIG. 3C .

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)。Next, the molding resin 12 is applied all over the semiconductor wafer 2 to the support 11, and molding sealing is performed as shown in FIG. 3D. Next, the support body 11 is peeled off, and the mold resin 12 is turned over (see FIG. 3E ). As shown in FIG. 3E , the semiconductor wafer 2 and the molding resin 12 are present on substantially the same plane. Then, in the step shown in FIG. 3F , the photosensitive resin composition 13 is coated on the semiconductor wafer 2 and the molding resin 12 . At this time, the photosensitive resin composition 13 is preferably adjusted with a filler. Then, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). In addition, the photosensitive resin composition 13 may be either positive type or negative type. Furthermore, the relief pattern is heated to form a hardened relief pattern (interlayer insulating film forming step). Furthermore, wiring is formed in the site|part where the hardened relief pattern is not formed (wiring formation process).

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-described 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 semiconductor wafer 2 .

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 multi-layered. 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。Then, in FIG. 3G , a plurality of external connection terminals 7 corresponding to the semiconductor wafers 2 are formed (bump formation), and dicing is performed between the semiconductor wafers 2 . Thereby, as shown in FIG. 3H, a semiconductor device (semiconductor IC) 1 can be obtained. In this embodiment, a plurality of fan-out semiconductor devices 1 can be obtained by the manufacturing method shown in FIG. 3 .

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 cm 2中可為0.2×10 -6~2.5×10 -6Pa。 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 cm 2中可為0.4×10 -6~1.8×10 -6Pa。 In this embodiment, the weight reduction rate of the hardened relief pattern (interlayer insulating film) formed through the above steps may be 5 to 95% by weight. In another aspect of this embodiment, the volatile gas per 1 cm 2 of the hardened relief pattern (interlayer insulating film) formed by the above steps may be 0.2×10 -6 to 2.5 when kept at 100° C. for 60 minutes. ×10 -6 Pa. In yet another form of this embodiment, the volatile gas per 1 cm 2 of the hardened relief pattern (interlayer insulating film) formed by the above steps may be 0.4×10 -6 to 1.8 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 the present embodiment, in the above-mentioned interlayer insulating film formation step, it is preferable to form the photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a 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, the Example performed in order to clarify the effect of this invention is demonstrated. In the examples, the following materials and assay 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, the Example performed in order to clarify the effect of this invention is demonstrated.

(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) as a tetracarboxylic dianhydride was added to a 2-liter separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were added and stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the heat generation caused by the reaction was completed, it was cooled to room temperature and left to stand 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。Next, under ice-cooling, a solution of dicyclohexylcarbodiimide (DCC) dissolved in γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Then, it added over 60 minutes, stirring and suspending the 4,4'- diamine diphenyl ether (DADPE) which is a diamine in (gamma)-butyrolactone. Furthermore, after stirring at room temperature for 2 hours, 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 solution.

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 a crude polymer. The resulting crude polymer was separated by filtration and dissolved in tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to water to precipitate the polymer, and the obtained precipitate was separated by filtration and then 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) A polyimide precursor (polymer A-2) was obtained by reacting in the same manner as the method described in the above-mentioned polymer A-1 except that tetracarboxylic dianhydride and diamine were changed as shown in Table 1 below. .

(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'-diphenylether dicarboxylic acid as dicarboxylic acid and N-methylpyrrolidone were added. After cooling the flask to 5°C, thionium chloride was added dropwise, and it was allowed to react 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 and 2.18 g of m-aminophenol as bisaminophenol, pyridine was added. Furthermore, after the solution of dimethyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was recovered, washed three times with pure water, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer B-1)). The mass of the compound used in the polymer B-1 is 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) A polybenzoxazole precursor (polymer B-2) was obtained by reacting in the same manner as the method described in the above-mentioned polymer B-1 except that the dicarboxylic acid was changed as shown in Table 1 below.

(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 Phenolic Resin) A phenol resin containing 85 g of the C1 resin shown below and 15 g of the C2 resin shown below was prepared as the polymer C-1. C1: cresol novolak resin (cresol/formaldehyde novolak resin, m-cresol/p-cresol (molar ratio) = 60/40, weight average molecular weight in terms of polystyrene = 12,000, manufactured by Asahi Organic Materials Co., Ltd., Trade 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: The C2 line was synthesized as follows. <C2: Synthesis of a phenolic resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms> 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 the mixture was stirred at 120° C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). Next, 130 g of vegetable oil-modified phenol derivative (a), 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed, and the mixture was stirred at 90° C. for 3 hours. Then, the temperature was raised to 120° C., and the mixture was stirred under reduced pressure for 3 hours. Then, 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. under atmospheric pressure for 1 hour. The reaction liquid was cooled to room temperature to obtain a phenolic resin (hereinafter referred to as "C2 resin") modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (acid value: 120 mgKOH/g) 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]    聚合物 四羧酸二酐(A) A之質量 (g) 二胺(B) B之質量 (g) 聚醯亞胺前驅物 聚合物A-1 4,4'-氧二鄰苯二甲酸二酐 (ODPA) 147.11 4,4'-二胺基二苯醚 (DADPE) 92.9 聚合物A-2 4,4'-氧二鄰苯二甲酸二酐 (ODPA) 147.11 2,2'-雙二甲基-4,4'-二胺基聯苯 (m-TB) 98.5       聚合物 二羧酸(C) C之質量 (g) 雙胺基苯酚(D) D之質量 (g) 聚苯并㗁唑前驅物 聚合物B-1 4,4'-二苯醚二羧酸 15.48 2,2-雙(3-胺基-4-羥基苯基)-六氟丙烷 18.3 聚合物B-2 癸二酸 12.13 2,2-雙(3-胺基-4-羥基苯基)-六氟丙烷 18.3       聚合物 甲酚酚醛清漆樹脂(E) E之質量 (g) 改性之酚樹脂(F) F之質量 (g) 酚樹脂 聚合物C-1 C1樹脂 85 C2樹脂 15 聚合物C-2 C1樹脂 100 C2樹脂 0 [Table 1] polymer Tetracarboxylic dianhydride (A) Mass of A (g) Diamine (B) Mass of B (g) Polyimide precursor Polymer A-1 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diaminodiphenyl ether (DADPE) 92.9 Polymer A-2 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 2,2'-bisdimethyl-4,4'-diaminobiphenyl (m-TB) 98.5 polymer Dicarboxylic acid (C) Mass of C (g) Diaminophenol (D) Mass of D (g) Polybenzoxazole precursor Polymer B-1 4,4'-Diphenyl ether dicarboxylic acid 15.48 2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer B-2 sebacic acid 12.13 2,2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 polymer Cresol Novolak Resin (E) Mass of E (g) Modified Phenolic Resin (F) Mass of F (g) Phenolic resin Polymer C-1 C1 resin 85 C2 resin 15 Polymer C-2 C1 resin 100 C2 resin 0

[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 prepared as shown in following Table 2, and obtained the solution of the photosensitive resin composition.

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 of the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2 was prepared by using the compounds described in Table 2 below and the compounding amounts described in Table 3 below. In addition, the unit of Table 3 is mass part.

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 produced photosensitive resin composition was subjected to (1) measurement of the weight reduction rate in an air environment, and (2) an adhesion test with a sealing material. In addition, (3) the electrical characteristics after the antenna-type module was fabricated were evaluated. 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) Measurement of weight loss rate Using the photosensitive resin compositions prepared in Examples and Comparative Examples, a fan-out type wafer-level chip-scale package type semiconductor device was produced. The self-fabricated semiconductor device is taken out as complete as possible with a thickness of 10 μm of the interlayer insulating film. About 10 mg of the interlayer insulating film taken out was put into a platinum pan, and the weight reduction rate after the temperature was raised to 700° C. at a heating rate of 10° C./min under an air flow rate of 50 ml/min was measured.

(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/cm 2,實施例6、7及比較例1、2為500 mJ/cm 2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 R4000 series manufactured by Nagase ChemteX was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated on the silicon wafer of aluminum sputtering so that the thickness would be about 150 μm, and thermal curing was performed at 130° C. to harden the epoxy-based sealing material. The photosensitive resin composition produced in the Example and the comparative example was apply|coated on the said epoxy-type cured film so that a final film thickness might become 10 micrometers. The coated photosensitive resin composition was exposed to the entire surface under the exposure conditions of 200 mJ/cm 2 in Examples 1 to 5, and 500 mJ/cm 2 in Examples 6 and 7 and Comparative Examples 1 and 2. , at 230 ℃ for 2 hours for thermal curing, to produce a first layer of cured film 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 for the formation of the cured film of the first layer was applied on the cured film of the first layer, and the entire surface was exposed under the same conditions as in the preparation of the cured film of the first layer. Thermal 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 calcining furnace (manufactured by Koyo Thermo Systems, model name 6841-20AMC-36), under simulated reflow conditions, the test piece after the formation of the cured film of the second layer was heated to The peak temperature is 260℃. The so-called simulated reflow conditions refer to the reflow conditions described in IPC/JEDEC J-STD-020A, Item 7.6, which is the standard specification of the American semiconductor industry group related to the evaluation method of semiconductor devices. It is normalized by assuming a high temperature of 220°C.

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 films of the samples before reflow and after reflow produced above, and an adhesion test was performed using a pull tester (manufactured by Quad Group, SEBASTIAN 5 type). Evaluation: Adhesion strength 70 MPa or more・・・Adhesion ◎ 50 MPa or more - less than 70 MPa・・・Adhesion ○ 30 MPa or more - less than 50 MPa・・・Adhesion △ Less than 30 MPa・・・Adhesion ×

(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 modules (electrical characteristics) Using the photosensitive resin compositions prepared in Examples and Comparative Examples, an antenna-integrated module in which a fan-out wafer-level chip-scale packaged semiconductor device and an antenna were integrated was fabricated. The photosensitive resin compositions prepared in Examples and Comparative Examples were used as interlayer insulating films for semiconductor devices. In addition, the photosensitive resin compositions produced in Examples and Comparative Examples were also used as an insulating member between an antenna and a ground (reference potential). The thickness of the insulating member affects the radiation rate of the antenna, so it is set to the 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。Also, 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。The reflection characteristics (electrical characteristics) were evaluated, and the deviation from 300 GHz of the antenna alone was less than 5 GHz as ○, 5 GHz or more and less than 10 GHz as △, and 10 GHz or more as ×. In addition, those with visible ripples were set as ×, and those with no visible ripples were set as ○. Furthermore, the so-called reflection characteristic here refers to the ratio of the electric power reflected by the antenna and returned to the input port to the input power of the input port opposite to the input power to the antenna.

[表2] 光起始劑 D-1

Figure 02_image093
光酸產生劑 D-2
Figure 02_image095
交聯劑 E-1
Figure 02_image097
填料 F-1 氧化矽填料(Admatechs公司製造,粒徑100 nm) 溶劑 G-1 γ-丁內酯 G-2 二甲基亞碸 G-3 丙二醇單甲醚乙酸酯 G-4 乳酸乙酯 [Table 2] photoinitiator D-1
Figure 02_image093
photoacid generator D-2
Figure 02_image095
cross-linking agent E-1
Figure 02_image097
filler F-1 Silica filler (manufactured by Admatechs, particle size 100 nm) solvent G-1 gamma-butyrolactone G-2 dimethyl sulfoxide G-3 Propylene Glycol Monomethyl Ether Acetate G-4 Ethyl lactate

[表3]       實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 比較例1 比較例2 聚合物 A-1 100 100                      A-2       100                   B-1          100                B-2             100             B-3                            C-1                100    100 100 C-2                   100       光起始劑 D-1 2 2 2                   光酸產生劑 D-2          10 10 15 15 15 15 交聯劑 E-1                15 15 15 15 填料 F-1 200 300 200 200 200 200 200 1 3000 溶劑 G-1 160 160 160 225 225             G-2 40 40 40                   G-3          25 25             G-4                120 120       硬化溫度    230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 重量減少率    33% 25% 33% 35% 35% 39% 39% 99% 4% 密接性(回焊前)    × 密接性(回焊後)    × × 電特性    × 漣波    × [table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 polymer A-1 100 100 A-2 100 B-1 100 B-2 100 B-3 C-1 100 100 100 C-2 100 photoinitiator D-1 2 2 2 photoacid generator D-2 10 10 15 15 15 15 cross-linking agent E-1 15 15 15 15 filler F-1 200 300 200 200 200 200 200 1 3000 solvent G-1 160 160 160 225 225 G-2 40 40 40 G-3 25 25 G-4 120 120 hardening temperature 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ Weight loss rate 33% 25% 33% 35% 35% 39% 39% 99% 4% Adhesion (before reflow) × Adhesion (after reflow) × × Electrical characteristics × Ripple ×

[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 to 14, Comparative Example 3] It prepared as shown in following Table 4, and obtained the solution of the photosensitive resin composition.

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, each of the photosensitive resin compositions of Examples 8 to 14 and Comparative Example 3 was prepared by using the compounds described in Table 4 below and in the compounding amounts described in Table 5 below. In addition, the unit of Table 5 is mass part.

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 produced photosensitive resin composition was subjected to (1) volatile gas measurement at 100° C. for 60 minutes, and (2) an adhesion test with an inorganic film. In addition, (3) the electrical characteristics after the antenna-type module was fabricated were evaluated. 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 cm 2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) Measurement of volatile gas at 100° C. for 60 minutes Using the photosensitive resin compositions prepared in Examples and Comparative Examples, a fan-out type wafer-level chip-scale package type semiconductor device was produced. The self-fabricated semiconductor device is taken out as complete as possible with a thickness of 10 μm of the interlayer insulating film. The taken out interlayer insulating film was cut out to a size of 1 cm 2 , and the measurement was performed using a temperature-increasing desorption measuring apparatus (manufactured by Electronic Science Co., Ltd., EMD-WA1000S). After the temperature was raised to 100°C at a temperature increase rate of 10°C/min, the pressure after holding at 100°C for 60 minutes was 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/cm 2,實施例13、14及比較例3為500 mJ/cm 2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 compositions prepared in Examples and Comparative Examples were applied on a silicon wafer so that the final film thickness would be 10 μm. For the coated photosensitive resin composition, under the exposure conditions of 200 mJ/cm 2 in Examples 8 to 12, and 500 mJ/cm 2 in Examples 13, 14 and Comparative Example 3, the entire surface was exposed to light. Thermal curing was performed at 230° C. for 2 hours to produce a cured film with a thickness of 10 μm.

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。Using a sputtering apparatus (L-440S-FHL manufactured by CANON ANELVA), a titanium layer of 2000 Å was sputtered on the obtained cured film, and then a copper layer of 4000 Å was sputtered.

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 type). Evaluation: Adhesion strength 70 MPa or more・・・Adhesion ◎ 50 MPa or more - less than 70 MPa・・・Adhesion ○ 30 MPa or more - less than 50 MPa・・・Adhesion △ Less than 30 MPa・・・Adhesion ×

(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 modules (electrical characteristics) Using the photosensitive resin compositions prepared in Examples and Comparative Examples, an antenna-integrated module in which a fan-out wafer-level chip-scale packaged semiconductor device and an antenna were integrated was fabricated. The photosensitive resin compositions prepared in Examples and Comparative Examples were used as interlayer insulating films for semiconductor devices. In addition, the photosensitive resin compositions produced in Examples and Comparative Examples were 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 the 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。Also, 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。The reflection characteristics (electrical characteristics) were evaluated, and the deviation from 300 GHz of the antenna alone was less than 5 GHz as ○, 5 GHz or more and less than 10 GHz as △, and 10 GHz or more as ×. Furthermore, the so-called reflection characteristic here refers to the ratio of the electric power reflected by the antenna and returned to the input port to the input power of the input port opposite to the input power to the antenna.

[表4] 光起始劑 D-1

Figure 02_image099
光酸產生劑 D-2
Figure 02_image101
交聯劑 E-1
Figure 02_image103
熱交聯劑、揮發調整劑 H-1 二季戊四醇四丙烯酸酯 H-2 異氰尿酸三縮水甘油酯 H-3 聚乙二醇900 溶劑 G-1 γ-丁內酯 G-2 二甲基亞碸 G-3 丙二醇單甲醚乙酸酯 G-4 乳酸乙酯 [Table 4] photoinitiator D-1
Figure 02_image099
photoacid generator D-2
Figure 02_image101
cross-linking agent E-1
Figure 02_image103
Thermal crosslinking agent, volatilization regulator H-1 dipentaerythritol tetraacrylate H-2 Triglycidyl isocyanurate H-3 polyethylene glycol 900 solvent G-1 gamma-butyrolactone G-2 dimethyl sulfoxide G-3 Propylene Glycol Monomethyl Ether Acetate G-4 Ethyl lactate

[表5]       實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 比較例3 聚合物 A-1 100 100                   A-2       100                B-1          100             B-2             100          B-3                         C-1                100    100 C-2                   100    光起始劑 D-1 2 2 2                光酸產生劑 D-2          10 10 15 15 15 交聯劑 E-1                15 15 15 熱交聯劑、揮發調整劑 H-1 10 10 10                H-2          10 10 5 5    H-3                      15 溶劑 G-1 160 160 160 225 225          G-2 40 40 40                G-3          25 25          G-4                120 120 120 硬化溫度    230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 揮發氣體壓力(Pa)    0.8×10 -6 0.7×10 -6 0.8×10 -6 1×10 -6 1.2×10 -6 1.4×10 -6 1.4×10 -6 3×10 -6 密接性    × 電特性    × [table 5] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 3 polymer A-1 100 100 A-2 100 B-1 100 B-2 100 B-3 C-1 100 100 C-2 100 photoinitiator D-1 2 2 2 photoacid generator D-2 10 10 15 15 15 cross-linking agent E-1 15 15 15 Thermal crosslinking agent, volatilization regulator H-1 10 10 10 H-2 10 10 5 5 H-3 15 solvent G-1 160 160 160 225 225 G-2 40 40 40 G-3 25 25 G-4 120 120 120 hardening temperature 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ Volatile gas pressure (Pa) 0.8× 10-6 0.7× 10-6 0.8× 10-6 10-6 1.2× 10-6 1.4× 10-6 1.4× 10-6 10-6 tightness × Electrical characteristics ×

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] Using the photosensitive resin compositions described in Examples 1 to 14, a fan-out type wafer-level chip-scale package type semiconductor device containing an epoxy resin in a mold resin can be operated 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 redistribution layer connected to the semiconductor chip, especially a fan-out type wafer-level chip-scale 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 21:焊球 22:焊料凸塊 23:密封樹脂 24:中介層 1: Semiconductor device 2: Semiconductor wafer 2a: Terminal 3: Sealing material 4: Rewiring layer 5: Wiring 6: Interlayer insulating film 7: External connection terminal 10: Wafer 11: Support body 12: Molding resin 13: Photosensitive resin composition 21: Solder Balls 22: Solder bumps 23: Sealing resin 24: Intermediary layer

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 the present embodiment. FIG. 2 is a schematic plan view of the semiconductor device of the present embodiment. 3A to 3H are examples of manufacturing steps of the semiconductor device of the present embodiment. FIG. 4 is a comparison diagram of a flip chip BGA (Ball Grid Array, ball grid array) and a fan-out (Fan-Out) type 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: Rewiring 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

Claims (38)

一種半導體裝置,其特徵在於: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 cm 2中為0.2×10 -6~2.5×10 -6Pa。 A semiconductor device comprising a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than the semiconductor wafer in plan view, and an interlayer insulating film between the rewiring layers is maintained at 100° C. for 60 minutes The volatilized gas is 0.2×10 -6 to 2.5×10 -6 Pa per 1 cm 2 . 一種半導體裝置,其特徵在於: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 cm 2中為0.4×10 -6~1.8×10 -6Pa。 A semiconductor device comprising a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than the semiconductor wafer in plan view, and an interlayer insulating film between the rewiring layers is maintained at 100° C. for 60 minutes The volatilized gas is 0.4×10 -6 to 1.8×10 -6 Pa per 1 cm 2 . 如請求項1或2之半導體裝置,其中上述密封材與上述層間絕緣膜直接相接。The semiconductor device according to claim 1 or 2, wherein the sealing material and the interlayer insulating film are in direct contact with each other. 如請求項1至3中任一項之半導體裝置,其中上述密封材含有環氧樹脂。The semiconductor device according to any one of claims 1 to 3, wherein the sealing material contains an epoxy resin. 如請求項1至4中任一項之半導體裝置,其中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。The semiconductor device according to any one of claims 1 to 4, wherein the interlayer insulating film contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. 如請求項5之半導體裝置,其中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]
Figure 03_image029
(通式(1)中,X 1為4價有機基,Y 1為2價有機基,m為1以上之整數)。
The semiconductor device of claim 5, wherein the interlayer insulating film contains a polyimide having a structure of the following general formula (1);
Figure 03_image029
(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).
如請求項6之半導體裝置,其中上述通式(1)中之X 1為含有芳香族環之4價有機基, 上述通式(1)中之Y 1為含有芳香族環之2價有機基。 The semiconductor device according to claim 6, wherein X 1 in the general formula (1) is a tetravalent organic group containing an aromatic ring, and Y 1 in the general formula (1) is a divalent organic group containing an aromatic ring . 如請求項6或7之半導體裝置,其中上述通式(1)中之X 1含有下述通式(2)~通式(4)所表示之至少一種結構; [化2]
Figure 03_image031
[化3]
Figure 03_image033
[化4]
Figure 03_image035
(通式(4)中,R 9為氧原子、硫原子或2價有機基)。
The semiconductor device according to claim 6 or 7, wherein X 1 in the above general formula (1) contains at least one structure represented by the following general formula (2) to general formula (4);
Figure 03_image031
[hua 3]
Figure 03_image033
[hua 4]
Figure 03_image035
(In the general formula (4), R 9 is an oxygen atom, a sulfur atom or a divalent organic group).
如請求項8之半導體裝置,其中上述通式(1)中之X 1含有下述通式(5)所表示之結構; [化5]
Figure 03_image037
The semiconductor device according to claim 8, wherein X 1 in the above general formula (1) contains a structure represented by the following general formula (5);
Figure 03_image037
.
如請求項6至9中任一項之半導體裝置,其中上述通式(1)中之Y 1含有下述通式(6)~通式(8)所表示之至少一種結構; [化6]
Figure 03_image039
(R 10、R 11、R 12及R 13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]
Figure 03_image041
(R 14~R 21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]
Figure 03_image043
(R 22為2價基,R 23~R 30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)。
The semiconductor device according to any one of claims 6 to 9, wherein Y 1 in the general formula (1) contains at least one structure represented by the following general formulas (6) to (8);
Figure 03_image039
(R 10 , R 11 , R 12 and R 13 are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different) [Chemical 7]
Figure 03_image041
(R 14 to R 21 are a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be different from each other or the same) [Chem. 8]
Figure 03_image043
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different).
如請求項10之半導體裝置,其中上述通式(1)中之Y 1含有下述通式(9)所表示之結構; [化9]
Figure 03_image045
The semiconductor device according to claim 10, wherein Y 1 in the above general formula (1) contains a structure represented by the following general formula (9);
Figure 03_image045
.
如請求項5之半導體裝置,其中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]
Figure 03_image047
(通式(10)中,Y 2與Y 3為2價有機基)。
The semiconductor device according to claim 5, wherein the above-mentioned polybenzoxazole contains a polybenzoxazole having the structure of the following general formula (10); [Chemical 10]
Figure 03_image047
(In the general formula (10), Y 2 and Y 3 are divalent organic groups).
如請求項12之半導體裝置,其中上述通式(10)之Y 2為碳數1~30之2價有機基。 The semiconductor device according to claim 12, wherein Y 2 of the general formula (10) is a divalent organic group having 1 to 30 carbon atoms. 如請求項13之半導體裝置,其中上述通式(10)之Y 2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。 The semiconductor device according to claim 13, wherein Y 2 in the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms are substituted with fluorine atoms. 如請求項12至14中任一項之半導體裝置,其中上述通式(10)之Y 3為含有芳香族基之2價有機基。 The semiconductor device according to any one of claims 12 to 14, wherein Y 3 of the above general formula (10) is a divalent organic group containing an aromatic group. 如請求項15之半導體裝置,其中上述通式(10)之Y 3含有下述通式(6)~(8)所表示之至少一種結構; [化11]
Figure 03_image049
(R 10、R 11、R 12及R 13為氫原子、碳數1~5之1價脂肪族基,可相同亦可不同) [化12]
Figure 03_image051
(R 14~R 21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]
Figure 03_image053
(R 22為2價基,R 23~R 30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)。
The semiconductor device of claim 15, wherein Y 3 of the general formula (10) contains at least one structure represented by the following general formulas (6) to (8);
Figure 03_image049
(R 10 , R 11 , R 12 and R 13 are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different) [Chemical 12]
Figure 03_image051
(R 14 to R 21 are a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, which may be different from each other or the same.) [Chemical 13]
Figure 03_image053
(R 22 is a divalent group, and R 23 to R 30 are a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different).
如請求項16之半導體裝置,其中上述通式(10)之Y 3含有下述通式(9)所表示之結構; [化14]
Figure 03_image055
The semiconductor device of claim 16, wherein Y 3 of the above general formula (10) contains a structure represented by the following general formula (9);
Figure 03_image055
.
如請求項12至14中任一項之半導體裝置,其中上述通式(10)之Y 3為碳數1~40之2價有機基。 The semiconductor device according to any one of claims 12 to 14, wherein Y 3 of the general formula (10) is a divalent organic group having 1 to 40 carbon atoms. 如請求項18之半導體裝置,其中上述通式(10)之Y 3為碳數1~20之2價鏈狀脂肪族基。 The semiconductor device according to claim 18, wherein Y 3 of the general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. 如請求項5之半導體裝置,其中上述具有酚性羥基之聚合物含有酚醛清漆型酚樹脂。The semiconductor device according to claim 5, wherein the polymer having a phenolic hydroxyl group contains a novolac-type phenol resin. 如請求項5之半導體裝置,其中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。The semiconductor device according to claim 5, wherein the polymer having a phenolic hydroxyl group contains a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. 如請求項1至21中任一項之半導體裝置,其中關於上述再配線層,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。The semiconductor device according to any one of claims 1 to 21, wherein the rewiring layer includes a first interlayer insulating film layer, a second interlayer insulating film layer, a The first interlayer insulating film layer and the second interlayer insulating film layer are different, and are provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer. 如請求項22之半導體裝置,其中上述第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 cm 2中為0.4×10 -6~1.8×10 -6Pa。 The semiconductor device of claim 22, wherein the first interlayer insulating film layer is in contact with the sealing material, and the volatile gas per 1 cm 2 of the first interlayer insulating film layer when kept at 100° C. for 60 minutes is 0.4× 10 -6 to 1.8×10 -6 Pa. 如請求項22或23之半導體裝置,其中上述第2層間絕緣膜層為與上述第1層間絕緣膜層不同之組成。The semiconductor device according to claim 22 or 23, wherein the second interlayer insulating film layer has a different composition from that of the first interlayer insulating film layer. 如請求項22至24中任一項之半導體裝置,其中上述第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。The semiconductor device according to any one of claims 22 to 24, wherein the volatile gas when the second interlayer insulating film is kept at 100°C for 60 minutes and the volatile gas when the first interlayer insulating film is kept at 100°C for 60 minutes Volatile gases are different. 如請求項1至25中任一項之半導體裝置,其中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。The semiconductor device according to any one of claims 1 to 25, wherein the semiconductor device is a fan-out type wafer-level chip-scale package type semiconductor device. 如請求項1至26中任一項之半導體裝置,其中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 cm 2中為0.6×10 -6~1.8×10 -6Pa。 The semiconductor device according to any one of claims 1 to 26, wherein the volatile gas per 1 cm 2 of the interlayer insulating film between the rewiring layers is 0.6×10 −6 to 1.8×10 when kept at 100° C. for 60 minutes. -6 Pa. 如請求項27之半導體裝置,其中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 cm 2中為0.6×10 -6~1.6×10 -6Pa。 The semiconductor device of claim 27, wherein the volatile gas per 1 cm 2 of the interlayer insulating film between the rewiring layers is 0.6×10 -6 to 1.6×10 -6 Pa per 100° C. for 60 minutes. 如請求項27之半導體裝置,其中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 cm 2中為0.6×10 -6~1.4×10 -6Pa。 The semiconductor device of claim 27, wherein the volatile gas per 1 cm 2 of the interlayer insulating film between the rewiring layers is 0.6×10 -6 to 1.4×10 -6 Pa when kept at 100° C. for 60 minutes. 如請求項1至29中任一項之半導體裝置,其中上述層間絕緣膜含有熱交聯劑。The semiconductor device according to any one of claims 1 to 29, wherein the above-mentioned interlayer insulating film contains a thermal crosslinking agent. 如請求項1至29中任一項之半導體裝置,其中上述層間絕緣膜含有揮發調整劑。The semiconductor device according to any one of claims 1 to 29, wherein the interlayer insulating film contains a volatilization modifier. 如請求項1至29中任一項之半導體裝置,其中上述層間絕緣膜含有熱交聯劑及揮發調整劑。The semiconductor device according to any one of claims 1 to 29, wherein the interlayer insulating film contains a thermal crosslinking agent and a volatilization modifier. 如請求項1至32中任一項之半導體裝置,其中上述再配線層含有與上述層間絕緣膜相接之無機膜。The semiconductor device according to any one of claims 1 to 32, wherein the rewiring layer includes an inorganic film in contact with the interlayer insulating film. 如請求項33之半導體裝置,其中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。The semiconductor device of claim 33, wherein the inorganic film has a reaction layer in which a volatile gas contained in the interlayer insulating film reacts with a component of the inorganic film. 一種半導體裝置之製造方法,其特徵在於包含: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 cm 2中為0.4×10 -6~1.8×10 -6Pa。 A method of manufacturing a semiconductor device, comprising: 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 heated at 100° C. The volatilized gas in 1 cm 2 is 0.4×10 -6 to 1.8×10 -6 Pa when it is kept at low temperature for 60 minutes. 如請求項35之半導體裝置之製造方法,其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。The method for manufacturing a semiconductor device according to claim 35, comprising the step of forming an interlayer insulating film: using a photosensitive resin that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group The composition forms the above-mentioned interlayer insulating film. 如請求項36之半導體裝置之製造方法,其中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 -6Pa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。 The method for manufacturing a semiconductor device according to claim 36, wherein the interlayer insulating film forming step comprises the step of: using the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes to become 0.4×10 −6 to 1.8×10 The above-mentioned photosensitive resin composition adjusted by the method of 6 Pa forms the above-mentioned interlayer insulating film. 如請求項37之半導體裝置之製造方法,其中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 -6Pa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。 The method for manufacturing a semiconductor device according to claim 37, wherein the step of forming the interlayer insulating film comprises the step of: using the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes to become 0.4×10 −6 to 1.8×10 The above-mentioned photosensitive resin composition adjusted by a thermal crosslinking agent and/or a volatilization modifier in the form of 6 Pa forms the above-mentioned interlayer insulating film.
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