TWI818743B - Semiconductor device and manufacturing method thereof - Google Patents
Semiconductor device and manufacturing method thereof Download PDFInfo
- Publication number
- TWI818743B TWI818743B TW111136306A TW111136306A TWI818743B TW I818743 B TWI818743 B TW I818743B TW 111136306 A TW111136306 A TW 111136306A TW 111136306 A TW111136306 A TW 111136306A TW I818743 B TWI818743 B TW I818743B
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- Prior art keywords
- semiconductor device
- layer
- general formula
- protective layer
- insulating layer
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 253
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000010410 layer Substances 0.000 claims abstract description 167
- 239000011241 protective layer Substances 0.000 claims abstract description 105
- 239000003566 sealing material Substances 0.000 claims abstract description 47
- 239000011229 interlayer Substances 0.000 claims description 83
- 235000012431 wafers Nutrition 0.000 claims description 82
- 229920000642 polymer Polymers 0.000 claims description 60
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 48
- 239000004642 Polyimide Substances 0.000 claims description 47
- 229920001721 polyimide Polymers 0.000 claims description 47
- 125000000962 organic group Chemical group 0.000 claims description 46
- 239000000126 substance Substances 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 239000011342 resin composition Substances 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 39
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 37
- -1 polybenzoethazole Polymers 0.000 claims description 36
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 30
- 239000005011 phenolic resin Substances 0.000 claims description 29
- 229920001568 phenolic resin Polymers 0.000 claims description 27
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 23
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 22
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 150000002989 phenols Chemical class 0.000 claims description 15
- 150000004985 diamines Chemical class 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 10
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- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000002329 infrared spectrum Methods 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 5
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
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- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
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- 150000008065 acid anhydrides Chemical class 0.000 description 13
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
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- 238000011161 development Methods 0.000 description 6
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- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 5
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- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 5
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- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 4
- CSLFOBYNSUXTRU-UHFFFAOYSA-N 1,4-dioxonaphthalene-2-diazonium Chemical class C1=CC=C2C(=O)C=C([N+]#N)C(=O)C2=C1 CSLFOBYNSUXTRU-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
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Abstract
本發明之目的在於提供一種能保護半導體晶片及提高保護層側、及再配線層中之絕緣層側之間之密接性的半導體裝置。 本發明之半導體裝置具備:半導體晶片2、與半導體晶片2相接之密封材3、俯視下面積大於半導體晶片2之再配線層4、及用以保護半導體晶片2之保護層8,保護層8配置於半導體晶片2與再配線層4之絕緣層6之間,保護層8之楊氏模數與絕緣層6之楊氏模數之差為0.8~5.0 GPa。 An object of the present invention is to provide a semiconductor device that can protect a semiconductor chip and improve the adhesion between the protective layer side and the insulating layer side in the rewiring layer. The semiconductor device of the present invention includes: a semiconductor wafer 2, a sealing material 3 in contact with the semiconductor wafer 2, a rewiring layer 4 with an area larger than that of the semiconductor wafer 2 in plan view, and a protective layer 8 for protecting the semiconductor wafer 2. The protective layer 8 Disposed between the semiconductor chip 2 and the insulating layer 6 of the rewiring layer 4, the difference between the Young's modulus of the protective layer 8 and the Young's modulus of the insulating layer 6 is 0.8 to 5.0 GPa.
Description
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手法有各種方法。作為半導體封裝手法,例如有如下封裝手法:利用密封材覆蓋半導體晶片而形成元件密封材,進而,形成與半導體晶片電性連接之再配線層。半導體封裝手法中,近年來稱為扇出(Fan-Out)之半導體封裝手法成為主流。There are various methods for semiconductor packaging in semiconductor devices. As a semiconductor packaging method, for example, there is a packaging method in which a semiconductor wafer is covered with a sealing material to form an element sealing material, and then a rewiring layer electrically connected to the semiconductor wafer is formed. Among semiconductor packaging methods, a semiconductor packaging method called fan-out has become mainstream in recent years.
於扇出型半導體封裝中,形成大於半導體晶片之晶片尺寸之晶片密封體。進而,形成及至半導體晶片及密封材之區域為止之再配線層。再配線層係以較薄之膜厚形成。又,由於再配線層形成至密封材之區域為止,故可使外部連接端子之數量較多。In the fan-out semiconductor package, a chip sealing body larger than the chip size of the semiconductor chip is formed. Furthermore, a rewiring layer is formed up to the area of the semiconductor chip and the sealing material. The rewiring layer is formed with a thin film thickness. In addition, since the rewiring layer is formed up to the area of the sealing material, the number of external connection terminals can be increased.
例如,作為扇出型半導體裝置,已知有下述專利文獻1。 [先前技術文獻] [專利文獻] For example, the following Patent Document 1 is known as a fan-out semiconductor device. [Prior technical literature] [Patent Document]
[專利文獻1]日本專利特開2011-129767號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 2011-129767
[發明所欲解決之問題][Problem to be solved by the invention]
對於扇出型半導體裝置,不僅要求保護半導體晶片不受其後之製程中產生之熱歷程之影響,亦要求保護層側與再配線層中之絕緣層側之間之較高之密接性。然而,先前之扇出型半導體裝置之保護層側與再配線層中之絕緣層側之間之密接性並不充分。For fan-out semiconductor devices, it is not only required to protect the semiconductor chip from the thermal history generated in subsequent processes, but also requires high adhesion between the protective layer side and the insulating layer side in the rewiring layer. However, the adhesion between the protective layer side and the insulating layer side in the rewiring layer of the previous fan-out semiconductor device is insufficient.
本發明係鑒於該點而完成者,其目的在於提供一種能保護半導體晶片及能提高保護層側、及再配線層中之絕緣層側之間之密接性的半導體裝置,及其製造方法。 [解決問題之技術手段] The present invention was made in view of this point, and its object is to provide a semiconductor device that can protect a semiconductor chip and improve the adhesion between the protective layer side and the insulating layer side in the rewiring layer, and a manufacturing method thereof. [Technical means to solve problems]
本發明者發現可藉由以下技術手段解決上述課題。 [1] 一種半導體裝置,其具備: 半導體晶片、 與上述半導體晶片相接之密封材、 俯視下面積大於上述半導體晶片之再配線層、及 用於保護上述半導體晶片之保護層; 上述保護層配置於上述半導體晶片與上述再配線層之絕緣層之間, 上述保護層之楊氏模數與上述絕緣層之楊氏模數之差為0.8~5.0 GPa。 [2] 如項目1之半導體裝置,其中上述楊氏模數之差為1.0~5.0 GPa。 [3] 如項目1或2之半導體裝置,其中上述楊氏模數之差為2.0~4.5 GPa。 [4] 如項目1~3中任一項之半導體裝置,其中上述半導體晶片中供上述保護層配置一側之面以外之面由上述密封材覆蓋。 [5] 如項目1~4中任一項之半導體裝置,其中上述保護層與上述半導體晶片及上述絕緣層之至少一者相接。 [6] 如項目1~5中任一項之半導體裝置,其中上述再配線層具有電性連接於上述半導體晶片之中間層、及覆蓋上述中間層之上述絕緣層。 [7] 如項目6之半導體裝置,其於上述保護層形成有孔,且 通過上述孔將上述半導體晶片與上述中間層電性連接。 [8] 如項目7之半導體裝置,其中上述保護層中之上述半導體晶片側之面中源自上述孔之開口面積之比率未達一半。 [9] 如項目1~8中任一項之半導體裝置,其中上述密封材與上述絕緣層相接。 [10] 如項目1~9中任一項之半導體裝置,其中上述密封材包含環氧樹脂。 [11] 如項目1~10任一項之半導體裝置,其中上述保護層包含選自聚醯亞胺、聚苯并㗁唑、及具有酚性羥基之聚合物中之至少1種。 [12] 如項目1~11中任一項之半導體裝置,其中上述絕緣層包含選自聚醯亞胺、聚苯并㗁唑、及具有酚性羥基之聚合物中之至少1種。 [13] 如項目1~12中任一項之半導體裝置,其中上述保護層包含聚醯亞胺,利用全反射測定法(ATR法)進行IR(infrared radiation,紅外線)光譜測定之情形時之1380 cm -1附近之波峰高度與1500 cm -1附近之波峰高度之波峰比(1380 cm -1附近波峰高度/1500 cm -1附近波峰高度)為1.2~2.5。 [14] 如項目1~13中任一項之半導體裝置,其中上述絕緣層包含聚醯亞胺,利用全反射測定法(ATR法)進行IR光譜測定之情形時之1380 cm -1附近之波峰高度與1500 cm -1附近之波峰高度之波峰比(1380 cm -1附近波峰高度/1500 cm -1附近波峰高度)為0.2~0.9。 [15] 如項目1~14中任一項之半導體裝置,其中上述保護層及上述絕緣層之至少一者包含聚醯亞胺,該聚醯亞胺包含以下通式(1)之結構, [化1] (式中,X 1係源自四羧酸二酐之四價有機基,Y 1係源自二胺之二價有機基,m係1以上之整數)。 [16] 如項目15之半導體裝置,其中上述通式(1)中之X 1係包含芳香族環之四價有機基,上述通式(1)中之Y 1係包含芳香族環之二價有機基。 [17] 如項目15或16之半導體裝置,其中上述通式(1)中之X 1包含下述通式(2)~通式(4)所表示之至少1種結構: [化2] [化3] [化4] (通式(4)中,R 9係氧原子、硫原子、或二價有機基)。 [18] 如項目17之半導體裝置,其中上述通式(1)中之X 1包含下述通式(5)所表示之結構, [化5] 。 [19] 如項目15至18中任一項之半導體裝置,其中上述通式(1)中之Y 1包含下述通式(6)~通式(8)所表示之至少1種結構: [化6] (式中,R 10、R 11、R 12及R 13分別獨立地為氫原子、碳數為1~5之一價脂肪族基或羥基,可相同,亦可不同) [化7] (式中,R 14~R 21分別獨立地為氫原子、鹵素原子、碳數為1~5之一價有機基或羥基,可互不相同,亦可相同) [化8] (式中,R 22係二價基或氧原子,R 23~R 30分別獨立地為氫原子、鹵素原子、碳數為1~5之一價脂肪族基或羥基,可相同,亦可不同)。 [20] 如項目15至19中任一項之半導體裝置,其中上述通式(1)中之Y 1包含下述通式(9)所表示之結構, [化9] 。 [21] 如項目12之半導體裝置,其中上述絕緣層包含聚苯并㗁唑,該聚苯并㗁唑包含以下通式(10)之結構, [化10] (通式(10)中,U與V係二價有機基)。 [22] 如項目21之半導體裝置,其中上述通式(10)之U係碳數1~30之二價有機基。 [23] 如項目22之半導體裝置,其中上述通式(10)之U係碳數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。 [24] 如項目21至24中任一項之半導體裝置,其中上述通式(10)之V係包含芳香族基之二價有機基。 [25] 如項目24之半導體裝置,其中上述通式(10)之V包含下述通式(6)~通式(8)所表示之至少1種結構: [化11] (式中,R 10、R 11、R 12及R 13分別獨立地為氫原子、碳數為1~5之一價脂肪族基,可相同,亦可不同) [化12] (式中,R 14~R 21分別獨立地為氫原子、鹵素原子、碳數為1~5之一價有機基,可互不相同,亦可相同) [化13] (式中,R 22係二價基或氧原子,R 23~R 30分別獨立地為氫原子、鹵素原子、碳數為1~5之一價脂肪族基,可相同,亦可不同)。 [26] 如項目25之半導體裝置,其中上述通式(10)之V包含下述通式(9)所表示之結構, [化14] 。 [27] 如項目21至26中任一項之半導體裝置,其中上述通式(10)之V係碳數1~40之二價有機基。 [28] 如項目27之半導體裝置,其中上述通式(10)之V係碳數1~20之二價鏈狀脂肪族基。 [29] 如項目11之半導體裝置,其中上述具有酚性羥基之聚合物包含酚醛清漆型酚系樹脂。 [30] 如項目11之半導體裝置,其中上述具有酚性羥基之聚合物包含不具有不飽和烴基之酚系樹脂、及具有不飽和烴基之改性酚系樹脂。 [31] 如項目1至30中任一項之半導體裝置,其中在對上述再配線層進行剖面觀察時,上述再配線層包含: 第1絕緣層、 第2絕緣層、及 中間層,該中間層係與上述第1絕緣層及上述第2絕緣層不同層,設置於上述第1絕緣層與上述第2絕緣層之間; 上述保護層之楊氏模數與上述第1絕緣層及上述第2絕緣層之至少一者之楊氏模數之差為0.8~5.0 GPa。 [32] 如項目31之半導體裝置,其中上述第1絕緣層與上述密封材相接,上述楊氏模數之差為0.8~5.0 GPa以上。 [33] 如項目31或32之半導體裝置,其中上述第2絕緣層係與上述第1絕緣層不同之組成。 [34] 如項目1至33中任一項之半導體裝置,其中上述半導體裝置係扇出型之晶圓級晶片尺寸封裝型之半導體裝置。 [35] 一種半導體裝置之製造方法,其包括: 於半導體晶片形成保護層之步驟; 以該保護層之至少一部分露出之方式,利用密封材覆蓋形成有上述保護層之上述半導體晶片之步驟;及 於上述保護層側形成俯視下面積大於上述半導體晶片且包含絕緣層之再配線層之步驟;且 上述保護層與上述絕緣層之楊氏模數之差為0.8~5.0 GPa。 [36] 如項目35之半導體裝置之製造方法,其包括:保護層形成步驟,其利用可形成聚醯亞胺、聚苯并㗁唑、及具有酚性羥基之聚合物中之至少1種化合物的感光性樹脂組合物形成上述保護層。 [37] 如項目36或37之半導體裝置之製造方法,其包括:層間絕緣膜形成步驟,其利用可形成聚醯亞胺、聚苯并㗁唑、及具有酚性羥基之聚合物中之至少1種化合物的感光性樹脂組合物形成上述絕緣層。 [38] 一種再配線層,其配置於具備半導體晶片、密封材及保護層的半導體裝置中之上述半導體晶片及上述密封材之至少一面側,上述密封材與上述半導體晶片相接,上述保護層用於保護上述半導體晶片, 上述再配線層包含電性連接於上述半導體晶片之中間層、及與上述中間層相接之絕緣層,上述絕緣層與上述保護層之楊氏模數之差為0.8~5.0 GPa。 [發明之效果] The inventor found that the above problems can be solved by the following technical means. [1] A semiconductor device comprising: a semiconductor wafer, a sealing material in contact with the semiconductor wafer, a rewiring layer having an area larger than that of the semiconductor wafer in plan view, and a protective layer for protecting the semiconductor wafer; the above protective layer configuration Between the semiconductor chip and the insulating layer of the rewiring layer, the difference between the Young's modulus of the protective layer and the Young's modulus of the insulating layer is 0.8 to 5.0 GPa. [2] For example, the semiconductor device of item 1, wherein the difference in Young's modulus is 1.0 to 5.0 GPa. [3] Such as the semiconductor device of item 1 or 2, wherein the difference in the above-mentioned Young's modulus is 2.0~4.5 GPa. [4] The semiconductor device according to any one of items 1 to 3, wherein surfaces of the semiconductor wafer other than the side on which the protective layer is disposed are covered with the sealing material. [5] The semiconductor device according to any one of items 1 to 4, wherein the protective layer is in contact with at least one of the semiconductor chip and the insulating layer. [6] The semiconductor device according to any one of items 1 to 5, wherein the rewiring layer has an intermediate layer electrically connected to the semiconductor chip, and the insulating layer covering the intermediate layer. [7] The semiconductor device of Item 6, wherein a hole is formed in the protective layer, and the semiconductor chip and the intermediate layer are electrically connected through the hole. [8] The semiconductor device of Item 7, wherein the ratio of the opening area originating from the hole in the surface of the semiconductor chip side of the protective layer is less than half. [9] The semiconductor device according to any one of items 1 to 8, wherein the sealing material is in contact with the insulating layer. [10] The semiconductor device according to any one of items 1 to 9, wherein the sealing material contains epoxy resin. [11] The semiconductor device according to any one of items 1 to 10, wherein the protective layer contains at least one selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. [12] The semiconductor device according to any one of items 1 to 11, wherein the insulating layer contains at least one selected from the group consisting of polyimide, polybenzozoazole, and a polymer having a phenolic hydroxyl group. [13] The semiconductor device according to any one of items 1 to 12, wherein the protective layer contains polyimide, and the IR (infrared radiation, infrared) spectrum is measured using the total reflection measurement method (ATR method) 1380 The crest ratio between the crest height near cm -1 and the crest height near 1500 cm -1 (crest height near 1380 cm -1 /crest height near 1500 cm -1 ) is 1.2 to 2.5. [14] The semiconductor device according to any one of items 1 to 13, wherein the insulating layer contains polyimide, and the peak near 1380 cm -1 when the IR spectrum is measured using the total reflection measurement method (ATR method) The crest ratio between the height and the crest height near 1500 cm -1 (crest height near 1380 cm -1 /crest height near 1500 cm -1 ) is 0.2 to 0.9. [15] The semiconductor device according to any one of items 1 to 14, wherein at least one of the above-mentioned protective layer and the above-mentioned insulating layer includes polyimide, and the polyimide includes the structure of the following general formula (1), [ chemical 1] (In the formula, X 1 is a tetravalent organic group derived from tetracarboxylic dianhydride, Y 1 is a divalent organic group derived from diamine, and m is an integer greater than 1). [16] The semiconductor device of item 15 , wherein Organic based. [17] The semiconductor device of item 15 or 16, 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): [Chemical 2] [Chemical 3] [Chemical 4] (In the general formula (4), R 9 is an oxygen atom, a sulfur atom, or a divalent organic group). [18] The semiconductor device of item 17, wherein X 1 in the above general formula (1) includes a structure represented by the following general formula (5), [Chemical 5] . [19] The semiconductor device according to any one of items 15 to 18, wherein Y 1 in the above general formula (1) contains at least one structure represented by the following general formula (6) to general formula (8): [ chemical 6] (In the formula, R 10 , R 11 , R 12 and R 13 are each independently a hydrogen atom, a monovalent aliphatic group with a carbon number of 1 to 5, or a hydroxyl group, and may be the same or different) [Chemical 7] (In the formula, R 14 to R 21 are each independently a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be different from each other or the same) [Chemical 8] (In the formula, R 22 is a divalent radical or an oxygen atom, and R 23 to R 30 are independently a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different. ). [20] The semiconductor device according to any one of items 15 to 19, wherein Y 1 in the above general formula (1) contains a structure represented by the following general formula (9), [Chemical 9] . [21] The semiconductor device of item 12, wherein the insulating layer includes polybenzoethazole, and the polybenzoethazole includes the structure of the following general formula (10), [Chemical 10] (In the general formula (10), U and V are divalent organic groups). [22] The semiconductor device of item 21, wherein U in the above general formula (10) is a divalent organic group having 1 to 30 carbon atoms. [23] The semiconductor device of item 22, wherein U in the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and a part or all of the hydrogen atoms are substituted with fluorine atoms. [24] The semiconductor device according to any one of items 21 to 24, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. [25] The semiconductor device of item 24, wherein V in the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8): [Chemical 11] (In the formula, R 10 , R 11 , R 12 and R 13 are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different) [Chemical 12] (In the formula, R 14 to R 21 are each independently a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, and may be different from each other or the same) [Chemical 13] (In the formula, R 22 is a divalent group or an oxygen atom, and R 23 to R 30 are independently a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different). [26] The semiconductor device of item 25, wherein V in the above general formula (10) includes a structure represented by the following general formula (9), [Chemical 14] . [27] The semiconductor device according to any one of items 21 to 26, wherein V in the above general formula (10) is a divalent organic group having 1 to 40 carbon atoms. [28] The semiconductor device of item 27, wherein V in the above general formula (10) is a bivalent chain aliphatic group having 1 to 20 carbon atoms. [29] The semiconductor device of item 11, wherein the polymer having a phenolic hydroxyl group includes a novolac-type phenolic resin. [30] The semiconductor device of item 11, wherein the polymer having a phenolic hydroxyl group includes a phenolic resin that does not have an unsaturated hydrocarbon group, and a modified phenolic resin that has an unsaturated hydrocarbon group. [31] The semiconductor device according to any one of items 1 to 30, wherein when the above-mentioned rewiring layer is observed in cross-section, the above-mentioned rewiring layer includes: a first insulating layer, a second insulating layer, and an intermediate layer, and the intermediate layer The layer system is different from the above-mentioned first insulating layer and the above-mentioned second insulating layer, and is arranged between the above-mentioned first insulating layer and the above-mentioned second insulating layer; the Young’s modulus of the above-mentioned protective layer is different from that of the above-mentioned first insulating layer and the above-mentioned second insulating layer. 2. The difference in Young’s modulus of at least one of the insulating layers is 0.8 to 5.0 GPa. [32] The semiconductor device of Item 31, wherein the first insulating layer is in contact with the sealing material, and the difference in Young’s modulus is 0.8 to 5.0 GPa or more. [33] The semiconductor device of item 31 or 32, wherein the above-mentioned second insulating layer has a different composition from the above-mentioned first insulating layer. [34] The semiconductor device according to any one of items 1 to 33, wherein the semiconductor device is a fan-out wafer-level chip size packaging type semiconductor device. [35] A method of manufacturing a semiconductor device, which includes: the step of forming a protective layer on a semiconductor wafer; the step of covering the above-mentioned semiconductor wafer on which the above-mentioned protective layer is formed with a sealing material in such a manner that at least part of the protective layer is exposed; and The step of forming a rewiring layer on the side of the protective layer that has an area larger than the semiconductor chip in plan view and includes an insulating layer; and the difference in Young's modulus of the protective layer and the insulating layer is 0.8 to 5.0 GPa. [36] The manufacturing method of a semiconductor device as in item 35, which includes: a protective layer forming step using at least one compound that can form polyimide, polybenzoethazole, and a polymer with a phenolic hydroxyl group The photosensitive resin composition forms the above protective layer. [37] The manufacturing method of a semiconductor device as in item 36 or 37, which includes: an interlayer insulating film forming step using at least one of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. A photosensitive resin composition of one compound forms the above-mentioned insulating layer. [38] A rewiring layer disposed on at least one side of the semiconductor wafer and the sealing material in a semiconductor device including a semiconductor wafer, a sealing material, and a protective layer, the sealing material being in contact with the semiconductor wafer, and the protective layer For protecting the above-mentioned semiconductor chip, the above-mentioned rewiring layer includes an intermediate layer electrically connected to the above-mentioned semiconductor chip and an insulating layer connected to the above-mentioned intermediate layer. The difference in Young's modulus of the above-mentioned insulating layer and the above-mentioned protective layer is 0.8. ~5.0 GPa. [Effects of the invention]
根據本發明,可提供一種能保護半導體晶片及能提高保護層側、及再配線層中之絕緣層側之密接性的半導體裝置,及其製造方法。According to the present invention, it is possible to provide a semiconductor device that can protect a semiconductor chip and improve the adhesion between the protective layer side and the insulating layer side in the rewiring layer, and a manufacturing method thereof.
以下,參照圖式對本發明之半導體裝置之一實施方式(以下,簡記為「實施方式」)進行說明。再者,本發明並不限定於以下實施方式,可於其主旨之範圍內進行各種變化後實施。於本實施方式中,使用「~」而記載之數值範圍將記載於「~」之前後之數值包含於其範圍內。又,於本實施方式中,於階段性記載之數值範圍內,於某一數值範圍內記載之上限值或下限值可替換成其他階段性記載之數值範圍之上限值或下限值。進而,於本實施方式中,於某一數值範圍內記載之上限值或下限值亦可替換成實施例所示之值。Hereinafter, one embodiment (hereinafter, abbreviated as "embodiment") of the semiconductor device of the present invention will be described 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 spirit. In this embodiment, the numerical range described using "~" includes the numerical values written before and after "~" within the range. Furthermore, in this embodiment, within the numerical range described in stages, the upper limit or lower limit value described in a certain numerical range may be replaced by the upper limit or lower limit of another numerical range described in stages. . Furthermore, in this embodiment, the upper limit value or the lower limit value described within a certain numerical range may be replaced with the value shown in the embodiment.
(半導體裝置) 圖1係本實施方式之半導體裝置之剖面模式圖。如圖1所示,半導體裝置(半導體IC)1具備: 半導體晶片2、 與半導體晶片2相接之密封材3、 俯視下面積大於半導體晶片2之再配線層4、及 用於保護半導體晶片2之保護層8; 保護層8配置於半導體晶片2與再配線層4之絕緣層(以下,有時稱為「層間絕緣膜」)6之間, 保護層8之楊氏模數與絕緣層6之楊氏模數之差為0.8~5.0 GPa。 (semiconductor device) FIG. 1 is a schematic cross-sectional view of the semiconductor device according to this embodiment. As shown in FIG. 1 , a semiconductor device (semiconductor IC) 1 includes: Semiconductor wafer 2. Sealing material 3 connected to semiconductor chip 2, The rewiring layer 4 has an area larger than that of the semiconductor chip 2 when viewed from above, and Protective layer 8 for protecting the semiconductor chip 2; The protective layer 8 is disposed between the semiconductor chip 2 and the insulating layer (hereinafter, sometimes referred to as "interlayer insulating film") 6 of the rewiring layer 4, The difference between the Young's modulus of the protective layer 8 and the Young's modulus of the insulating layer 6 is 0.8 to 5.0 GPa.
如圖1所示,密封材3與半導體晶片2相接,並且以於俯視(沿箭頭A之方向觀察)下大於半導體晶片2之區域之面積形成。As shown in FIG. 1 , the sealing material 3 is in contact with the semiconductor wafer 2 and is formed with 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構成為具有:複數個配線5,其等電性連接於設置於半導體晶片2之複數個端子2a;及層間絕緣膜6,其將配線5之間填埋。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之一端連接於端子2a,另一端連接於外部連接端子7。端子2a與外部連接端子7之間之配線5整個面由層間絕緣膜6覆蓋。The rewiring layer 4 is configured to include a plurality of wirings 5 that are electrically connected to a plurality of terminals 2 a provided on the semiconductor wafer 2 , and an interlayer insulating film 6 that fills spaces between the wirings 5 . A plurality of terminals 2 a provided on the semiconductor chip 2 are electrically connected to the wiring 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,於俯視(沿箭頭A之方向觀察)下,再配線層4形成為大於半導體晶片2。圖1所示之半導體裝置1係扇出(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係由矽等半導體構成,內部形成有電路。As shown in FIG. 1 , in a plan view (viewed in the direction of arrow A), the rewiring layer 4 is formed to be larger than the semiconductor wafer 2 . 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 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 is made of a semiconductor such as silicon, and has a circuit formed inside it.
(再配線層) 本實施方式之一態樣係一種半導體裝置2中之配置於半導體晶片2及密封材3之至少一面側之再配線層4,上述半導體裝置2具備: 半導體晶片2、 與半導體晶片2相接之密封材3、及 用於保護半導體晶片2之保護層8。 該再配線層4包含電性連接於半導體晶片2之中間層、及與中間層相接之絕緣層6,絕緣層6與保護層8之楊氏模數之差為0.8~5.0 GPa。藉由使用此種再配線層4,可提供一種能保護半導體晶片2且能提高保護層8側、及再配線層4中之絕緣層6側之間之密接性的半導體裝置2。 再配線層4主要是由中間層(例如配線5)、及覆蓋配線5周圍之層間絕緣膜6構成。就防止與配線5之意外導通之觀點而言,層間絕緣膜6較佳為絕緣性較高之構件。 (Rewiring layer) One aspect of this embodiment is a rewiring layer 4 disposed on at least one side of the semiconductor chip 2 and the sealing material 3 in a semiconductor device 2, the semiconductor device 2 having: Semiconductor wafer 2. sealing material 3 connected to the semiconductor chip 2, and The protective layer 8 is used to protect the semiconductor chip 2 . The rewiring layer 4 includes an intermediate layer electrically connected to the semiconductor chip 2 and an insulating layer 6 connected to the intermediate layer. The difference in Young's modulus of the insulating layer 6 and the protective layer 8 is 0.8 to 5.0 GPa. By using such a rewiring layer 4, it is possible to provide a semiconductor device 2 that can protect the semiconductor chip 2 and improve the adhesion between the protective layer 8 side and the insulating layer 6 side in the rewiring layer 4. The rewiring layer 4 is mainly composed of an intermediate layer (for example, the wiring 5 ) and an interlayer insulating film 6 covering the periphery of the wiring 5 . From the viewpoint of preventing accidental conduction with the wiring 5 , the interlayer insulating film 6 is preferably a member with high insulation properties.
此處,本實施方式中之「再配線層4」如上所述,係具有配線5與層間絕緣膜6之薄膜之層,不包含中介層或印刷配線板。Here, the "rewiring layer 4" in this embodiment is a thin film layer having the wiring 5 and the interlayer insulating film 6 as described above, and does not include an interposer or a printed wiring board.
於本實施方式中,可將再配線層4之膜厚設為3~30 μm左右。再配線層4之膜厚亦可為1 μm以上,亦可為5 μm以上,亦可為10 μm以上。又,再配線層4之膜厚亦可為40 μm以下,亦可為30 μm以下,亦可為20 μm以下。In this embodiment, the film thickness of the rewiring layer 4 can be set to approximately 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. In addition, the film thickness of the rewiring layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less.
於俯視(沿箭頭A之方向觀察)半導體裝置1之情形時,成為以下圖2。圖2係本實施方式之半導體裝置之平面模式圖。再者,省略密封材3。When the semiconductor device 1 is viewed from above (viewed in the direction of arrow A), the following figure is shown in FIG. 2 . FIG. 2 is a schematic plan view of the semiconductor device according to this embodiment. Furthermore, the sealing material 3 is omitted.
圖2所示之半導體裝置1(參照圖1)構成為再配線層4之面積S1大於半導體晶片2之面積S2。再配線層4之面積S1雖未特別限定,就使外部連接端子之數量較多之觀點而言,再配線層4之面積S1較佳為半導體晶片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。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,由半導體晶片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 (see FIG. 1 ) is configured such that the area S1 of the rewiring layer 4 is larger than the area S2 of the semiconductor wafer 2 . Although the area S1 of the rewiring layer 4 is not particularly limited, from the viewpoint of increasing the number of external connection terminals, the area S1 of the rewiring layer 4 is preferably at least 1.05 times the area S2 of the semiconductor chip 2, and preferably 1.1 times or more, more preferably 1.2 times or more, especially 1.3 times or more. The upper limit is not particularly limited. 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 the area S2 of the semiconductor chip 2 . Furthermore, in FIG. 2 , the area of the portion of the rewiring layer 4 covered by the semiconductor chip 2 is also included in the area S1 of the rewiring 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 outer shapes of the semiconductor chip 2 and the rewiring layer 4 may be the same or different. In FIG. 2 , the semiconductor chip 2 and the rewiring layer 4 have similar external shapes to a rectangle, and the shapes may also be shapes other than a rectangular shape.
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之間填埋之層間絕緣膜6,亦可於再配線層4中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 a plurality of two or more layers. The rewiring layer 4 includes the wiring 5 and the interlayer insulating film 6 filling the spaces between the wirings 5. The rewiring layer 4 may also include a layer composed only of the interlayer insulating film 6 or a layer composed only of the wiring 5.
配線5並無特別限定,只要為導電性較高之構件即可,一般使用銅。The wiring 5 is not particularly limited as long as it is a member with high conductivity, and copper is generally 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 adhesion to the interlayer insulating film, epoxy resin is preferred.
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,可有效地提高半導體晶片2之表面至再配線層4之表面之密封性。 又,較佳為半導體晶片2中供保護層8配置一側之面以外之面由密封材3覆蓋。藉此,容易提高半導體晶片2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. Moreover, it is preferable that the surface of the semiconductor wafer 2 other than the surface on which the protective layer 8 is disposed is covered with the sealing material 3 . Thereby, the sealing property of the semiconductor wafer 2 can be easily 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 have a plurality of layers laminated. When the sealing material 3 has a laminated structure, it may be a laminated structure of the same material or a laminated structure of different materials.
(保護層)(protective layer)
於本實施方式中,層間絕緣膜6之楊氏模數與保護層8之楊氏模數之差為0.8~5.0 GPa。此處,楊氏模數可利用下述實施例所記載之方法等公知之方法進行測定。 關於上述情況,於測定楊氏模數時,優先使用實施例所記載之方法。另一方面,假定會產生根據樣品之形態或種類等而無法藉由實施例所記載之方法進行測定或藉由實施例所記載之方法進行測定並不現實等情況。僅於該情形時,可藉由其他方法導出楊氏模數。作為其他方法,採用公知並且基於業者通常想到之條件及手法之方法,作為一例,可例舉根據藉由奈米壓痕試驗所得之壓痕彈性模數導出楊氏模數之方法。 In this embodiment, the difference between the Young's modulus of the interlayer insulating film 6 and the Young's modulus of the protective layer 8 is 0.8 to 5.0 GPa. Here, the Young's modulus can be measured by a known method such as the method described in the following Examples. Regarding the above situation, when measuring Young's modulus, the method described in the Examples is preferably used. On the other hand, it is assumed that depending on the form or type of the sample, measurement by the method described in the Examples cannot be performed or that measurement by the method described in the Examples is impractical. In this case only, Young's modulus can be derived by other methods. As other methods, well-known methods based on conditions and techniques commonly thought of by those in the field are used. An example is a method of deriving Young's modulus from the indentation elastic modulus obtained by a nanoindentation test.
若楊氏模數之差為0.8~5.0 GPa,則半導體晶片2之保護性能良好,再配線層4中之層間絕緣膜6與配線5之密接性良好,並且層間絕緣膜6與保護層8之密接性優異。該等之原因雖不確定,但本發明者等人推測如下。 隨著微細化,對半導體晶片要求低介電常數。為此,提高半導體晶片中之空隙率係有效策略之一。然而,若空隙率提高,則半導體晶片對於來自外部之衝擊等容易變弱。因此,當製造具有提高了空隙率之半導體晶片之半導體裝置時,必須藉由保護層保護該半導體晶片免受物理衝擊傷害。為了保護半導體晶片免受物理衝擊傷害,較佳為變形量相對較小之保護層。 另一方面,存在因用於形成層間絕緣膜之曝光、顯影、硬化而於配線與層間絕緣膜之界面等產生殘留應力之情形。層間絕緣膜大多成為多層,於該情形時,會重複進行曝光、顯影、硬化,故於配線與層間絕緣膜之界面等產生殘留應力之可能性進一步提高。因此,就緩和該殘留應力之觀點而言,可較佳地使用變形量較大之保護層。 此處,於半導體晶片2中,將保護層8與層間絕緣膜6之楊氏模數之差調整為5.0 GPa以下,藉此,可抑制分子變形之程度之差,從而可抑制保護層8與層間絕緣膜6之界面之剝離。並且,藉由調整為0.8 GPa以上,可將變形量較大之層與變形量較小之層各自之保護半導體晶片2之功能組合發揮,故可進一步保護半導體晶片2免受物理衝擊傷害。 If the difference in Young's modulus is 0.8 to 5.0 GPa, the protective performance of the semiconductor chip 2 is good, the adhesion between the interlayer insulating film 6 and the wiring 5 in the wiring layer 4 is good, and the interlayer insulating film 6 and the protective layer 8 have good adhesion. Excellent adhesion. Although the reasons for these are not certain, the present inventors speculate as follows. Along with miniaturization, semiconductor wafers are required to have a low dielectric constant. To this end, increasing the void ratio in semiconductor wafers is one of the effective strategies. However, if the porosity is increased, the semiconductor wafer is likely to be weakened against external impact or the like. Therefore, when manufacturing a semiconductor device having a semiconductor wafer with increased porosity, the semiconductor wafer must be protected from physical impact by a protective layer. In order to protect the semiconductor chip from physical impact damage, a protective layer with a relatively small deformation is preferred. On the other hand, exposure, development, and hardening for forming the interlayer insulating film may cause residual stress at the interface between the wiring and the interlayer insulating film. Interlayer insulating films are often multi-layered. In this case, exposure, development, and hardening are repeated, so the possibility of generating residual stress at the interface between the wiring and the interlayer insulating film is further increased. Therefore, from the viewpoint of alleviating the residual stress, it is preferable to use a protective layer with a large deformation amount. Here, in the semiconductor wafer 2 , the difference in the Young's modulus of the protective layer 8 and the interlayer insulating film 6 is adjusted to 5.0 GPa or less. This can suppress the difference in the degree of molecular deformation, thereby suppressing the difference between the protective layer 8 and the interlayer insulating film 6 . The interface of the interlayer insulating film 6 is peeled off. Furthermore, by adjusting to 0.8 GPa or above, the layers with larger deformation and the layers with smaller deformation can combine their respective functions of protecting the semiconductor chip 2, so the semiconductor chip 2 can be further protected from physical impact damage.
上述楊氏模數之差較佳為4.5 GPa以下,更佳為4.0 GPa以下,尤佳為3.5 GPa以下。又,只要為0.8 GPa以上即可,並無限定,較佳為1.0 GPa以上,更佳為1.5 GPa以上,進而較佳為2.0 GPa以上,尤佳為2.5 GPa以上。藉此,容易獲得本發明之效果。The difference in Young's modulus is preferably 4.5 GPa or less, more preferably 4.0 GPa or less, and particularly preferably 3.5 GPa or less. Moreover, it is not limited as long as it is 0.8 GPa or more, but it is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, further preferably 2.0 GPa or more, particularly preferably 2.5 GPa or more. Thereby, the effect of the present invention can be easily obtained.
就保護半導體晶片2免受物理衝擊傷害之觀點而言,保護層8之楊氏模數較佳為4.0 GPa以上,更佳為4.5 GPa以上,尤佳為5 GPa以上。又,就顯影性之觀點而言,較佳為9.0 GPa以下,更佳為8.5 GPa以下,尤佳為8.0 GPa以下。 就吸收所產生之殘留應力之觀點而言,層間絕緣膜6之楊氏模數較佳為5.0 GPa以下,更佳為4.5 GPa以下,尤佳為4.0 GPa以下。又,就形成層間絕緣膜6時之耐化學品性之觀點而言,較佳為2.0 GPa以上,更佳為2.5 GPa以上,尤佳為3.0 GPa以上。 From the viewpoint of protecting the semiconductor chip 2 from physical impact damage, the Young's modulus of the protective layer 8 is preferably 4.0 GPa or more, more preferably 4.5 GPa or more, and particularly preferably 5 GPa or more. Moreover, from the viewpoint of developability, it is preferably 9.0 GPa or less, more preferably 8.5 GPa or less, even more preferably 8.0 GPa or less. From the viewpoint of absorbing the generated residual stress, the Young's modulus of the interlayer insulating film 6 is preferably 5.0 GPa or less, more preferably 4.5 GPa or less, and particularly preferably 4.0 GPa or less. Furthermore, from the viewpoint of chemical resistance when forming the interlayer insulating film 6, it is preferably 2.0 GPa or more, more preferably 2.5 GPa or more, and particularly preferably 3.0 GPa or more.
保護層8設置於半導體晶片2中未經密封材3覆蓋之面。於假定自經密封材3覆蓋之側俯視(沿圖1中A之箭頭方向觀察)半導體晶片2之情形時,保護層8成為半導體晶片2之背影而未被觀察到。The protective layer 8 is provided on the surface of the semiconductor wafer 2 that is not covered by the sealing material 3 . When the semiconductor wafer 2 is viewed from above (viewed in the direction of arrow A in FIG. 1 ) from the side covered by the sealing material 3 , the protective layer 8 becomes the back of the semiconductor wafer 2 and is not observed.
保護層8與半導體晶片2及層間絕緣膜6之至少一者相接。藉此,容易較佳地保護半導體晶片2。又,此種構成係容易期待提高保護層8側及層間絕緣膜6側之密接性之態樣,於半導體裝置1具有此種態樣之情形時,亦可提高保護層8側及層間絕緣膜6側之密接性。尤其是於半導體裝置1中,就上述觀點而言,保護層8與半導體晶片2及層間絕緣膜6之兩者相接為更佳態樣。再者,雖於半導體裝置1中省略,但只要可獲得本發明之效果,則亦可於半導體晶片2與層間絕緣膜6之間介存其他構件。The protective layer 8 is in contact with at least one of the semiconductor wafer 2 and the interlayer insulating film 6 . This makes it easy to better protect the semiconductor wafer 2 . In addition, this structure is an aspect that can easily be expected to improve the adhesion between the protective layer 8 side and the interlayer insulating film 6 side. When the semiconductor device 1 has such an aspect, it is also possible to improve the adhesiveness between the protective layer 8 side and the interlayer insulating film. 6 sides of tightness. Especially in the semiconductor device 1 , from the above point of view, it is more preferable that the protective layer 8 is in contact with both the semiconductor chip 2 and the interlayer insulating film 6 . Furthermore, although it is omitted from the semiconductor device 1 , other members may be interposed between the semiconductor chip 2 and the interlayer insulating film 6 as long as the effects of the present invention can be obtained.
於保護層8形成有孔8a,並通過孔8a將半導體晶片2側與配線5側電性連接。藉此,容易確保半導體晶片2側與配線5側之電性連接,且更容易保護半導體晶片2。保護層8之孔8a對應於半導體晶片2之端子2a設置有複數個,於複數之孔8a分別插設有端子2a。A hole 8a is formed in the protective layer 8, and the semiconductor chip 2 side and the wiring 5 side are electrically connected through the hole 8a. Thereby, it is easy to ensure the electrical connection between the semiconductor chip 2 side and the wiring 5 side, and it is easier to protect the semiconductor chip 2 . A plurality of holes 8a in the protective layer 8 are provided corresponding to the terminals 2a of the semiconductor chip 2, and the terminals 2a are respectively inserted into the plurality of holes 8a.
於半導體裝置1中,保護層8中之半導體晶片2側之面中源自孔8a之開口面積之比率未達一半。藉此,可確保用於保護半導體晶片2之保護面積,從而可進一步保護半導體晶片2。此處,「開口面積」係指半導體晶片2側之面的開口入口之合計面積。In the semiconductor device 1, the ratio of the opening area originating from the hole 8a in the surface of the semiconductor chip 2 side in the protective layer 8 is less than half. Thereby, the protection area for protecting the semiconductor wafer 2 can be ensured, so that the semiconductor wafer 2 can be further protected. Here, the "opening area" refers to the total area of the opening entrances on the 2-side surface of the semiconductor wafer.
保護層8之楊氏模數與層間絕緣膜6之楊氏模數例如係保護層8之楊氏模數較大。藉此,容易將變形量較大之層(於該情形時為保護層8)與變形量較小之層(於該情形時為層間絕緣膜6)各自之保護半導體晶片2之功能組合而發揮,從而更容易保護半導體晶片2。再者,關於保護層之楊氏模數與層間絕緣膜之楊氏模數的楊氏模數之關係,可使層間絕緣膜之楊氏模數較大。The Young's modulus of the protective layer 8 and the Young's modulus of the interlayer insulating film 6 are, for example, the Young's modulus of the protective layer 8 is larger. This makes it easy to combine the respective functions of the layer with a large deformation amount (in this case, the protective layer 8 ) and the layer with a small deformation amount (in this case, the interlayer insulating film 6 ) to protect the semiconductor chip 2 . , thereby making it easier to protect the semiconductor wafer 2 . Furthermore, regarding the relationship between the Young's modulus of the protective layer and the Young's modulus of the interlayer insulating film, the Young's modulus of the interlayer insulating film can be made larger.
又,再配線層4中之層間絕緣膜6可為多層。即,於剖面觀察再配線層4時,再配線層4亦可包含第1層間絕緣膜、第2層間絕緣膜、及與第1層間絕緣膜及第2層間絕緣膜不同且設置於第1層間絕緣膜與第2層間絕緣膜之間之中間層。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, when the rewiring layer 4 is viewed in cross section, the rewiring layer 4 may also include a first interlayer insulating film, a second interlayer insulating film, and a film that is different from the first interlayer insulating film and the second interlayer insulating film and is provided between the first layers. An intermediate layer between the insulating film and the second interlayer insulating film. The intermediate layer is the wiring 5, for example.
第1層間絕緣膜與第2層間絕緣膜可為相同組成,亦可為不同組成。第1層間絕緣膜與第2層間絕緣膜可為相同楊氏模數,亦可為不同楊氏模數。第1層間絕緣膜與第2層間絕緣膜可為相同膜厚,亦可為不同膜厚。若第1層間絕緣膜與第2層間絕緣膜具有不同組成、不同楊氏模數、及/或不同膜厚,則可使各層間絕緣膜具有不同性質,從而較佳。The first interlayer insulating film and the second interlayer insulating film may have the same composition or different compositions. The first interlayer insulating film and the second interlayer insulating film may have the same Young's modulus, or may have different Young's modulus. The first interlayer insulating film and the second interlayer insulating film may have the same film thickness, or may have different film thicknesses. It is preferable if the first interlayer insulating film and the second interlayer insulating film have different compositions, different Young's modulus, and/or different film thicknesses, so that each interlayer insulating film can have different properties.
(保護層之組成) 保護層之組成並無特別限定,例如較佳為包含選自聚醯亞胺、聚苯并㗁唑、及具有酚性羥基之聚合物中之至少1種化合物之膜。 (Composition of protective layer) The composition of the protective layer is not particularly limited, but for example, a film containing at least one compound selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group is preferred.
(形成保護層之樹脂組合物) 用於形成保護層之樹脂組合物並無特別限定,只要為感光性樹脂組合物即可,較佳為包含選自聚醯亞胺前驅物、聚苯并㗁唑前驅物、及具有酚性羥基之聚合物中之至少1種化合物之感光性樹脂組合物。用於形成保護層之樹脂組合物可為液體狀,亦可為膜狀。又,用於形成保護層之樹脂組合物可為負型感光性樹脂組合物,亦可為正型感光性樹脂組合物。 (Resin composition forming protective layer) The resin composition used to form the protective layer is not particularly limited as long as it is a photosensitive resin composition. Preferably, the resin composition is selected from the group consisting of polyimide precursors, polybenzoethazole precursors, and phenolic hydroxyl groups. A photosensitive resin composition containing at least one compound among the polymers. The resin composition used to form the protective layer may be in liquid form or film form. Moreover, the resin composition used for forming a protective layer may be a negative photosensitive resin composition, or it may be a positive photosensitive resin composition.
(層間絕緣膜之組成) 層間絕緣膜6之組成並無特別限定,例如較佳為包含選自聚醯亞胺、聚苯并㗁唑、及具有酚性羥基之聚合物中之至少1種化合物之膜。 (Composition of interlayer insulating film) The composition of the interlayer insulating film 6 is not particularly limited, but for example, a film containing at least one compound selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group is preferred.
(形成層間絕緣膜之樹脂組合物) 用於形成層間絕緣膜6之樹脂組合物並無特別限定,只要為感光性之樹脂組合物即可,較佳為包含選自聚醯亞胺前驅物、聚苯并㗁唑前驅物、及具有酚性羥基之聚合物中之至少1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感光性樹脂組合物,亦可為正型感光性樹脂組合物。 (Resin composition for forming interlayer insulating film) The resin composition used to form the interlayer insulating film 6 is not particularly limited, as long as it is a photosensitive resin composition, and is preferably selected from the group consisting of polyimide precursors, polybenzoethazole precursors, and A photosensitive resin composition containing at least one compound of a phenolic hydroxyl group polymer. The resin composition used to form the interlayer insulating film 6 may be in a liquid form or in a film form. In addition, the resin composition used to form the interlayer insulating film 6 may be a negative photosensitive resin composition or a positive photosensitive resin composition.
於本實施方式中,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所得者稱為硬化凸紋圖案。該硬化凸紋圖案成為保護層8、層間絕緣膜6。In the present embodiment, the pattern obtained by exposing and developing the photosensitive resin composition is called a relief pattern, and what is obtained by heating and hardening the relief pattern is called a cured relief pattern. This hardened relief pattern becomes the protective layer 8 and the interlayer insulating film 6 .
<聚醯亞胺前驅物組合物> (A)感光性樹脂 作為聚醯亞胺前驅物組合物所使用之感光性樹脂,可例舉聚醯胺、聚醯胺酸酯等。例如,作為聚醯胺酸酯,可使用包含下述通式(11)所表示之重複單元之聚醯胺酸酯。 <Polyimide precursor composition> (A)Photosensitive resin Examples of the photosensitive resin used in the polyamide precursor composition include polyamide, polyamide ester, and the like. 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15] R 1及R 2分別獨立地為氫原子、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係源自四羧酸二酐之四價有機基,Y 1係源自二胺之二價有機基,m為1以上之整數。m較佳為2以上,更佳為5以上。 [Chemical 15] R 1 and R 2 are each independently a hydrogen atom, a saturated aliphatic group with 1 to 30 carbon atoms, an aromatic group, a monovalent organic group with a carbon-carbon unsaturated double bond, or one of the carbon-carbon unsaturated double bonds. Valence ions. X 1 is a tetravalent organic group derived from tetracarboxylic dianhydride, Y 1 is a divalent organic group derived from diamine, and m is an integer greater than 1. m is preferably 2 or more, more preferably 5 or more.
於上述通式(11)之R 1及R 2係以一價陽離子之形式存在時,O帶負電荷(以-O -之形式存在)。又,X 1與Y 1亦可包含羥基。 When R 1 and R 2 in the above general formula (11) exist in the form of monovalent cations, O is negatively charged (existing in the form of -O - ). Moreover, X 1 and Y 1 may contain a hydroxyl group.
通式(11)中之R 1及R 2更佳為於下述通式(12)所表示之一價有機基、或下述通式(13)所表示之一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) more preferably have ammonium at the end of a monovalent organic group represented by the following general formula (12) or a monovalent organic group represented by the following general formula (13) The structure of ions.
[化16] (通式(12)中,R 3、R 4及R 5分別獨立地為氫原子或碳數1~5之有機基,並且m1為1~20之整數)。 [Chemical 16] (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 m1 is an integer from 1 to 20).
[化17] (通式(13)中,R 6、R 7及R 8分別獨立地為氫原子或碳數1~5之有機基,並且m 2為1~20之整數)。 [Chemical 17] (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).
亦可將複數種通式(11)所表示之聚醯胺酸酯進行混合。又,亦可使用時通式(11)所表示之聚醯胺酸酯彼此共聚而成之聚醯胺酸酯。A plurality of polyamide esters represented by the general formula (11) may be mixed. In addition, a polyamide ester obtained by copolymerizing polyamide esters represented by the general formula (11) may also be used.
X 1並無特別限定,就楊氏模數及耐化學品性之觀點而言,X 1較佳為包含芳香族基之四價有機基。具體而言,X 1較佳為包含下述通式(2)~通式(4)所表示之至少1種結構之四價有機基。 X 1 is not particularly limited, but from the viewpoint of Young's modulus and chemical resistance, X 1 is preferably a tetravalent organic group including an aromatic group. Specifically, X 1 is preferably a tetravalent organic group containing at least one structure represented by the following general formulas (2) to (4).
[化18] [Chemical 18]
[化19] [Chemical 19]
[化20] (通式(4)中,R 9係氧原子、硫原子、二價有機基之任一者)。 [Chemistry 20] (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例如係碳數1~40之二價有機基。R 9亦可包含羥基。 R 9 in the general formula (4) is, for example, a divalent organic group having 1 to 40 carbon atoms. R 9 may also contain a hydroxyl group.
就顯影性之觀點而言,X 1尤佳為包含下述通式(5)所表示之結構之四價有機基。 From the viewpoint of developability, X 1 is particularly preferably a tetravalent organic group containing a structure represented by the following general formula (5).
[化21] [Chemistry 21]
Y 1並無特別限定,就楊氏模數及耐化學品性之觀點而言,Y 1較佳為包含芳香族基之二價有機基。具體而言,Y 1較佳為包含下述通式(6)~通式(8)所表示之至少1種結構之二價有機基。 Y 1 is not particularly limited, but from the viewpoint of Young's modulus and chemical resistance, Y 1 is preferably a divalent organic group including an aromatic group. Specifically, Y 1 is preferably a divalent organic group containing at least one structure represented by the following general formulas (6) to (8).
[化22] (式中,R 10、R 11、R 12及R 13分別獨立地為氫原子、碳數為1~5之一價脂肪族基,可相同,亦可不同)。 [Chemistry 22] (In the formula, R 10 , R 11 , R 12 and R 13 are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).
[化23] (式中,R 14~R 21分別獨立地為氫原子、鹵素原子、碳數為1~5之一價有機基,可互不相同,亦可相同)。 [Chemistry 23] (In the formula, R 14 to R 21 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms, and may be different from each other or the same).
[化24] (式中,R 22係二價基或氧原子,R 23~R 30分別獨立地為氫原子、鹵素原子、碳數為1~5之一價脂肪族基,可相同,亦可不同)。 [Chemistry 24] (In the formula, R 22 is a divalent group or an oxygen atom, and R 23 to R 30 are independently a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).
通式(8)中之R 22例如係碳數1~40之二價有機基。 R 22 in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms.
就顯影性之觀點而言,Y 1尤佳為包含下述通式(9)所表示之結構之二價有機基。 From the viewpoint of developability, Y 1 is particularly preferably a bivalent organic group containing a structure represented by the following general formula (9).
[化25] [Chemical 25]
於上述聚醯胺酸酯中,其重複單元中之X 1源自用作原料之四羧酸二酐,Y 1源自用作原料之二胺。 In the above-mentioned polyamide ester, X 1 in its repeating unit is derived from the tetracarboxylic dianhydride used as the raw material, and Y 1 is derived from the diamine used as the raw material.
作為用作原料之四羧酸二酐,例如可例舉:均苯四甲酸二酐(PMDA)、二苯基醚-3,3',4,4'-四羧酸二酐(4,4-氧二鄰苯二甲酸二酐:ODPA)、二苯甲酮-3,3',4,4'-四羧酸二酐、聯苯基-3,3',4,4'-四羧酸二酐、二苯基碸-3,3',4,4'-四羧酸二酐、二苯甲烷-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,亦可將2種以上混合使用。Examples of the tetracarboxylic dianhydride used as a raw material include: pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (4,4 -Oxydiphthalic dianhydride: ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic Acid dianhydride, diphenyltrine-3,3',4,4'-tetracarboxylic dianhydride, 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. Moreover, these may be used individually or in mixture of 2 or more types.
作為用作原料之二胺,例如可例舉:對苯二胺(PPD)、間苯二胺、4,4'-二胺基二苯基醚(DADPE)、3,4'-二胺基二苯基醚、3,3'-二胺基二苯基醚、4,4'-二胺基-2,2'-二甲基聯苯基(m-TB)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'-二胺基二苯基碸、3,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、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'-二胺基二苯甲烷、3,4'-二胺基二苯甲烷、3,3'-二胺基二苯甲烷、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、鄰-聯甲苯胺碸、9,9-雙(4-胺基苯基)茀等。又,該等苯環上之氫原子之一部分亦可被取代。又,該等可單獨使用,亦可將2種以上混合使用。Examples of diamines used as raw materials include p-phenylenediamine (PPD), m-phenylenediamine, 4,4'-diaminodiphenyl ether (DADPE), and 3,4'-diaminodiphenyl ether. Diphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB) 4,4'-diamine diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'- Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamine Biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diamine diphenylmethane, 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-aminophenoxy)phenyl]benzene, bis[4-( 3-Aminophenoxy)phenyl]terine, 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)benzene base) hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-bistoluidine, 9,9-bis(4-aminophenyl)benzene, etc. In addition, part of the hydrogen atoms on the benzene ring may also be substituted. Moreover, these may be used individually or in mixture of 2 or more types.
於聚醯胺酸酯(A)之合成中,通常較佳地使用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交付至與二胺之縮合反應之方法。In the synthesis of the polyamide ester (A), it is generally preferred to use a method in which the tetracarboxylic acid diester obtained by performing the esterification reaction of the following tetracarboxylic dianhydride is directly subjected to a condensation reaction with a diamine. .
用於上述四羧酸二酐之酯化反應之醇類係具有烯烴性雙鍵之醇。具體而言,可例舉甲基丙烯酸2-羥基乙酯、2-甲基丙烯醯氧基乙基醇、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。該等醇類可單獨或將2種以上混合使用。The alcohols used in the esterification reaction of the above-mentioned tetracarboxylic dianhydride are alcohols having olefinic double bonds. Specific examples include, but are not limited to, 2-hydroxyethyl methacrylate, 2-methacryloxyethyl alcohol, glyceryl diacrylate, and glyceryl dimethacrylate. These alcohols can be used individually or in mixture of 2 or more types.
關於本實施方式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,例如可例舉國際公開第00/43439號手冊中所示之方法。即,可例舉如下方法:將四羧酸二酯暫時轉化成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交付至縮合反應,來製造聚醯胺酸酯(A)。又,亦可例舉如下方法:藉由將四羧酸二酯與二胺於有機脫水劑之存在下交付至縮合反應之方法來製造聚醯胺酸酯(A)。Regarding the specific synthesis method of the polyamide ester (A) used in this embodiment, a previously known method can be used. An example of the synthesis method is the method shown in International Publication No. 00/43439. That is, the method of temporarily converting the tetracarboxylic acid diester into the tetracarboxylic acid diester dichloride and the diamine in the presence of a basic compound can be exemplified. Condensation reaction to produce polyamide ester (A). Furthermore, a method of producing polyamide ester (A) by subjecting a tetracarboxylic acid diester and a diamine to a condensation reaction in the presence of an organic dehydrating agent can also be exemplified.
作為有機脫水劑之例,可例舉: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-(3-二甲基胺基丙基)碳二醯亞胺、1-環己基-3-(3-二甲基胺基丙基)碳二醯亞胺鹽酸鹽等。Examples of the organic dehydrating agent include dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, and ethylcyclohexylcarbodiimide. Amine, diphenylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-cyclohexyl-3-(3-dimethylamino) Propyl) carbodiimide hydrochloride, etc.
本實施方式所使用之聚醯胺酸酯(A)之重量平均分子量較佳為6000~150000,更佳為7000~50000,更佳為7000~20000。The weight average molecular weight of the polyamide ester (A) used in this embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, even more preferably 7,000 to 20,000.
(B1)光起始劑 於用於形成保護層、及層間絕緣膜之樹脂組合物為負型感光性樹脂之情形時,添加光起始劑。作為光起始劑,例如使用:二苯甲酮、鄰苯甲醯苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基酮、二苄基酮、及茀酮等二苯甲酮衍生物;2,2'-二乙氧基苯乙酮、及2-羥基-2-甲基苯丙酮等苯乙酮衍生物;1-羥基環己基苯基酮、9-氧硫𠮿、2-甲基9-氧硫𠮿、2-異丙基9-氧硫𠮿、及二乙基9-氧硫𠮿等9-氧硫𠮿衍生物;本偶醯、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)環己酮等二疊氮類;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,就感光度之方面而言,較佳為上述肟類。 (B1) Photoinitiator When the resin composition used to form the protective layer and the interlayer insulating film is a negative photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and benzyl ketone can be used. Benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and other acetophenone derivatives; 1-hydroxycyclohexyl phenyl ketone, 9-oxosulfide 𠮿 , 2-Methyl 9-oxosulfide𠮿 , 2-isopropyl 9-oxosulfide𠮿 , and diethyl 9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 Derivatives; benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal and benzoyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-bis( Diazides such as 4'-benzylidenediazide)-4-methylcyclohexanone and 2,6'-bis(4'-benzylidenediazide)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-benzoyl)oxime, 1,3-diphenylglycerol-2-(O-ethyl Oximes such as oxycarbonyl) oxime, 1-phenyl-3-ethoxyglycerone-2-(O-benzoyl) oxime; N-arylglycines such as N-phenylglycine ; Peroxides such as benzoyl peroxide; aromatic biimidazole, and titanocene, etc. Among these, the above-mentioned oximes are preferred in terms of sensitivity.
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。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,藉此感光度優異。又,藉由添加40質量份以下,厚膜硬化性優異。The added amount of these photoinitiators is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass relative to 100 parts by mass of polyamide ester (A). The photoinitiator is excellent in sensitivity by adding 1 part by mass or more of a photoinitiator based on 100 parts by mass of polyamide ester (A). In addition, by adding 40 parts by mass or less, thick film curability is excellent.
(B2)光酸產生劑 於用於形成保護層、及層間絕緣膜之樹脂組合物為正型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,可用作正型感光性樹脂組合物。 (B2) Photoacid generator When the resin composition used to form the protective layer and the interlayer insulating film is a positive photosensitive resin, a photoacid generator is added. By containing a photoacid generator, an acid is generated in the ultraviolet-exposed part, and the solubility of the exposed part in an alkaline aqueous solution is increased. Thereby, it can be used as a positive photosensitive resin composition.
作為光酸產生劑,可例舉醌二疊氮化合物、鋶鹽、鏻鹽、重氮鎓鹽、錪鹽等。其中,就表現出優異之溶解抑制效果,從而獲得高感度之正型感光性樹脂組合物之方面而言,可較佳地使用醌二疊氮化合物。又,亦可包含2種以上之光酸產生劑。Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and phosphonium salts. Among them, a quinonediazide compound can be preferably used in terms of exhibiting an excellent dissolution-inhibiting effect and obtaining a highly sensitive positive-type photosensitive resin composition. Moreover, two or more types of photoacid generators may be included.
(C)添加劑 保護層、及層間絕緣膜之楊氏模數之差可藉由聚合物結構進行調整,亦可利用添加劑之種類及量進行調節。若使用與聚合物分子鏈具有相互作用且具有平面性較高之結構之添加劑,則可使楊氏模數增加。作為增大楊氏模數之添加劑,例如可使用N-(4-溴苯基)鄰苯二甲醯亞胺、N-(4-氯苯基)鄰苯二甲醯亞胺、聯苯等。又,亦可藉由添加具有2個以上之交聯部位之化合物並使其交聯來增加楊氏模數。交聯部位之數量較佳為2以上,更佳為3以上。交聯部位可例示(甲基)丙烯酸基、烷氧基甲基或環氧部位、氧雜環丁烷部位或苯并㗁𠯤部位。又,作為使楊氏模數降低之添加劑,可例舉具有如環氧乙烷鏈及環氧丙烷鏈之可撓性結構之化合物。關於添加劑之量,根據目標楊氏模數差適當調整即可。 (C)Additives The difference in Young's modulus of the protective layer and the interlayer insulating film can be adjusted by the polymer structure, and can also be adjusted by the type and amount of additives. If additives are used that interact with the polymer molecular chain and have a relatively planar structure, the Young's modulus can be increased. As additives for increasing Young's modulus, for example, N-(4-bromophenyl)phthalimide, N-(4-chlorophenyl)phthalimide, biphenyl, etc. can be used . In addition, the Young's modulus can also be increased by adding a compound having two or more cross-linking sites and cross-linking the compound. The number of cross-linked sites is preferably 2 or more, more preferably 3 or more. Examples of the cross-linking site include (meth)acrylic acid groups, alkoxymethyl groups, epoxy sites, oxetane sites, and benzodiazepine sites. Examples of additives that reduce Young's modulus include compounds having flexible structures such as ethylene oxide chains and propylene oxide chains. Regarding the amount of additives, it can be adjusted appropriately according to the target Young's modulus difference.
(D)溶劑 只要為可使各成分溶解或分散之溶劑即可,並無特別限定。例如可例舉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,於相對於(A)感光性樹脂100質量份為30~1500質量份之範圍內使用。 (D)Solvent It is not particularly limited as long as it is a solvent that can dissolve or disperse each component. Examples thereof include N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl styrene, and the like. These solvents can be used in the range of 30 to 1500 parts by mass based on 100 parts by mass of the (A) photosensitive resin, depending on the thickness and viscosity of the coating film.
(E)其他 亦可使聚醯亞胺前驅物組合物含有交聯劑。作為交聯劑,可使用於對聚醯亞胺前驅物組合物進行曝光、顯影後,進行加熱硬化時,可使(A)感光性樹脂交聯或交聯劑本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)Others The polyimide precursor composition may also contain a cross-linking agent. As a cross-linking agent, it can be used to cross-link (A) the photosensitive resin or the cross-linking agent itself can form a cross-linked network structure when the polyimide precursor composition is exposed and developed and then heated and hardened. Cross-linking agent. By using a cross-linking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further enhanced.
此外,亦可包含用於提高感光度之增感劑、用於提高與基材之接著性之接著助劑等。In addition, it may also contain a sensitizer for increasing the sensitivity, an adhesive agent for improving the adhesion with the base material, etc.
(顯影) 於對聚醯亞胺前驅物組合物進行曝光後,利用顯影液對無用部分進行沖洗。作為所使用之顯影液,並無特別限制,於利用溶劑進行顯影之聚醯亞胺前驅物組合物之情形時,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,視需要利用不良溶劑等進行沖洗洗淨。 (Develop) After the polyimide precursor composition is exposed, the useless parts are rinsed with a developer. There is no particular limitation on the developer used. In the case of a polyimide precursor composition that is developed using a solvent, N,N-dimethylformamide, dimethylsterine, N, Good solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidinone, cyclopentanone, γ-butyrolactone, acetate esters, etc. These good solvents are compatible with lower alcohols, water, and aromatic hydrocarbons. Mixed solvents such as poor solvents, etc. After development, rinse and clean with a poor solvent if necessary.
於利用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、二乙基胺基乙醇、氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、三乙基胺、二乙基胺、甲基胺、二甲基胺、乙酸二甲基胺基乙酯、二甲基胺基乙醇、甲基丙烯酸二甲基胺基乙酯、環己基胺、乙二胺、六亞甲基二胺等表現出鹼性之化合物之水溶液。In the case of a polyimide precursor composition for development using an alkaline aqueous solution, an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate Aqueous solutions of alkaline compounds such as ester, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc.
(熱硬化) 對顯影後、曝光後之聚醯亞胺前驅物組合物進行加熱,藉此使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。 (heat hardening) The developed and exposed polyimide precursor composition is heated to close the ring of the polyimide precursor to form polyimide. This polyimide becomes a hardened relief pattern, that is, an interlayer insulating film.
用於使聚醯亞胺前驅物組合物熱硬化之加熱溫度並無特別限定,通常有熱硬化溫度越高楊氏模數越大之傾向。就使本實施方式之保護層之楊氏模數成為所需值之觀點而言,較佳為250℃以上,更佳為280℃以上,尤佳為300℃以上。又,就使本實施方式之層間絕緣膜之楊氏模數成為所需值之觀點而言,該加熱溫度較佳為160℃以上,更佳為180℃以上,尤佳為200℃以上。就對其他構件之影響之觀點而言,較佳為400℃以下。The heating temperature for thermosetting the polyimide precursor composition is not particularly limited. Generally, the higher the thermosetting temperature, the greater the Young's modulus. From the viewpoint of making the Young's modulus of the protective layer of this embodiment a desired value, it is preferably 250°C or higher, more preferably 280°C or higher, and particularly preferably 300°C or higher. Moreover, from the viewpoint of making the Young's modulus of the interlayer insulating film of this embodiment a desired value, the heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and particularly preferably 200°C or higher. From the viewpoint of the influence on other members, the temperature is preferably 400°C or lower.
<聚醯亞胺> 由上述聚醯亞胺前驅物組合物形成之硬化凸紋圖案之結構成為下述通式(1)。即,保護層及層間絕緣膜之至少一者包含聚醯亞胺,上述聚醯亞胺包含以下通式(1)之結構。 <Polyimide> The structure of the hardened relief pattern formed from the above polyimide precursor composition is the following general formula (1). That is, at least one of the protective layer and the interlayer insulating film contains polyimide, and the polyimide has a structure of the following general formula (1).
[化26] [Chemical 26]
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係四價有機基,Y 1係二價有機基,m係1以上之整數。通式(11)中之較佳之X 1、Y 1、m因相同原因,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 integer above. The preferred X 1 , Y 1 and m in the general formula (11) are also preferred in the polyimide of the general formula (1) for the same reason.
於鹼可溶性聚醯亞胺之情形時,亦可將聚醯亞胺之末端設為羥基。 於本實施方式之保護層包含聚醯亞胺之情形時,利用全反射測定法(Attenuated Total Reflection;ATR法)進行IR光譜測定之情形時之1380 cm -1附近之波峰高度與1500 cm -1附近之波峰高度之波峰比(1380 cm -1附近波峰高度/1500 cm -1附近波峰高度)較佳為1.2~2.5。就耐化學品性之觀點而言,較佳為1.3以上,更佳為1.4以上,尤佳為1.5以上。就顯影性之觀點而言,較佳為2.4以下,更佳為2.3以下,尤佳為2.2以下。 此處所言之「1380 cm -1附近之波峰高度」例如係1330~1430 cm -1之範圍內之最大波峰高度,此處所言之「1500 cm -1附近之波峰高度」例如係1450~1550 cm -1之範圍內之最大波峰高度。 In the case of alkali-soluble polyimide, the terminal of the polyimide can also be set to a hydroxyl group. When the protective layer of this embodiment contains polyimide, when the IR spectrum is measured using the Attenuated Total Reflection (ATR method), the peak height near 1380 cm -1 and 1500 cm -1 The crest ratio of nearby crest heights (crest height near 1380 cm -1 /crest height near 1500 cm -1 ) is preferably 1.2 to 2.5. From the viewpoint of chemical resistance, it is preferably 1.3 or more, more preferably 1.4 or more, and particularly preferably 1.5 or more. From the viewpoint of developability, it is preferably 2.4 or less, more preferably 2.3 or less, and particularly preferably 2.2 or less. The "wave crest height near 1380 cm -1 " mentioned here is, for example, the maximum wave crest height in the range of 1330 to 1430 cm -1 . The "wave crest height near 1500 cm -1 " mentioned here is, for example, 1450 to 1550 cm. The maximum wave crest height within the range of -1 .
於本實施方式之層間絕緣膜包含聚醯亞胺之情形時,利用全反射測定法(Attenuated Total Reflection;ATR法)進行IR光譜測定之情形時之1380 cm -1附近之波峰高度與1500 cm -1附近之波峰高度之波峰比(1380 cm -1附近波峰高度/1500 cm -1附近波峰高度)較佳為0.2~0.9。就耐化學品性之觀點而言,較佳為0.3以上,更佳為0.4以上,尤佳為0.5以上。就顯影性之觀點而言,較佳為0.8以下,更佳為0.7以下,尤佳為0.6以下。 此處所言之「1380 cm -1附近之波峰高度」例如係1330~1430 cm -1之範圍內之最大波峰高度,此處所言之「1500 cm -1附近之波峰高度」例如係1450~1550 cm -1之範圍內之最大波峰高度。 When the interlayer insulating film of this embodiment contains polyimide, when the IR spectrum is measured using the Attenuated Total Reflection (ATR method), the peak height near 1380 cm -1 and 1500 cm - The crest ratio of the crest height near 1 (crest height near 1380 cm -1 /crest height near 1500 cm -1 ) is preferably 0.2 to 0.9. From the viewpoint of chemical resistance, it is preferably 0.3 or more, more preferably 0.4 or more, and particularly preferably 0.5 or more. From the viewpoint of developability, 0.8 or less is preferred, 0.7 or less is more preferred, and 0.6 or less is particularly preferred. The "wave crest height near 1380 cm -1 " mentioned here is, for example, the maximum wave crest height in the range of 1330 to 1430 cm -1 . The "wave crest height near 1500 cm -1 " mentioned here is, for example, 1450 to 1550 cm. The maximum wave crest height within the range of -1 .
<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,可使用包含下述通式(14)所表示之重複單元之聚(鄰羥基醯胺)。 <Polybenzoethazole precursor composition> (A)Photosensitive resin As the photosensitive resin used in the polybenzoethazole precursor composition, poly(o-hydroxyamide) containing a repeating unit represented by the following general formula (14) can be used.
[化27] (通式(14)中,Y 2與Y 3係二價有機基)。 [Chemical 27] (In the general formula (14), Y 2 and Y 3 are divalent organic groups).
就層間絕緣膜與密封材之密接性之觀點而言,Y 2較佳為碳數1~30之二價有機基,更佳為碳數1~15之鏈狀伸烷基(其中,鏈狀伸烷基之氫原子亦可被取代為鹵素原子),尤佳為碳數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。 From the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y 2 is preferably a divalent organic group having 1 to 30 carbon atoms, and more preferably a chain alkylene group having 1 to 15 carbon atoms (wherein, chain The hydrogen atom of the alkylene group may be substituted with a halogen atom), and a chain alkylene group having 1 to 8 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferred.
又,就層間絕緣膜與密封材之密接性之觀點而言,Y 3較佳為包含芳香族基之二價有機基,更佳為包含下述通式(6)~通式(8)所表示之至少1種結構之二價有機基。 In addition, from the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y 3 is preferably a divalent organic group including an aromatic group, and more preferably includes the following general formula (6) to general formula (8). It represents a divalent organic radical of at least one structure.
[化28] (式中,R 10、R 11、R 12及R 13分別獨立地為氫原子、碳數為1~5之一價脂肪族基,可相同,亦可不同)。 [Chemical 28] (In the formula, R 10 , R 11 , R 12 and R 13 are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).
[化29] (式中,R 14~R 21分別獨立地為氫原子、鹵素原子、碳數為1~5之一價有機基,可互不相同,亦可相同)。 [Chemical 29] (In the formula, R 14 to R 21 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms, and may be different from each other or the same).
[化30] (式中,R 22係二價基或氧原子,R 23~R 30分別獨立地為氫原子、鹵素原子、碳數為1~5之一價脂肪族基,可相同,亦可不同)。 [Chemical 30] (In the formula, R 22 is a divalent group or an oxygen atom, and R 23 to R 30 are independently a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).
通式(8)中之R 22例如係碳數1~40之二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.
就層間絕緣膜與密封材之密接性之觀點而言,Y 3尤佳為包含下述通式(9)所表示之結構之二價有機基。 From the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y 3 is particularly preferably a divalent organic group containing a structure represented by the following general formula (9).
[化31] [Chemical 31]
就層間絕緣膜與密封材之密接性之觀點而言,Y 3較佳為碳數1~40之二價有機基,更佳為碳數1~40之二價鏈狀脂肪族基,尤佳為碳數1~20之二價鏈狀脂肪族基。 From the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y 3 is preferably a divalent organic group with a carbon number of 1 to 40, more preferably a divalent chain aliphatic group with a carbon number of 1 to 40, and particularly preferably It is a bivalent chain aliphatic group with 1 to 20 carbon atoms.
聚苯并㗁唑前驅物通常可由二羧酸衍生物與含羥基之二胺類合成。具體而言,可將二羧酸衍生物轉化成二鹵化物衍生物後,與二胺類進行反應,藉此合成。作為二鹵化物衍生物,較佳為二氯化物衍生物。Polybenzoethazole precursors can usually be synthesized from dicarboxylic acid derivatives and hydroxyl-containing diamines. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and reacting it with diamines. As the dihalide derivative, a dichloride derivative is preferred.
二氯化物衍生物可使鹵化劑作用於二羧酸衍生物來合成。作為鹵化劑,可使用通常之羧酸之醯氯化反應所使用之亞硫醯氯、磷醯氯、氧氯化磷、五氯化磷等。Dichloride derivatives can be synthesized by acting on dicarboxylic acid derivatives with a halogenating agent. As the halogenating agent, thionite chloride, phosphorus chloride, phosphorus oxychloride, phosphorus pentachloride, etc. used in the general chloride reaction of carboxylic acids can be used.
作為合成二氯化物衍生物之方法,可利用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多餘部分蒸餾去除之方法等合成。As a method of synthesizing the dichloride derivative, a method of reacting a dicarboxylic acid derivative with the above-mentioned halogenating agent in a solvent, a method of reacting an excess halogenating agent and then distilling off the excess can be used.
作為二羧酸衍生物所使用之二羧酸,例如可例舉: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'-二羧基二苯基醚、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、間苯二甲5-第三丁酸、5-溴間苯二甲酸、5-氟間苯二甲酸、5-氯間苯二甲酸、2,6-萘二甲酸、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、丁二酸、四氟丁二酸、甲基丁二酸、2,2-二甲基丁二酸、2,3-二甲基丁二酸、二甲基甲基丁二酸、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、二甘醇酸、二環戊二烯羧酸等。亦可將該等混合使用。Examples of dicarboxylic acids used as dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, and 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)sine , 2,2-bis(p-carboxyphenyl)propane, isophthalic 5-tertiary butyric acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2 ,6-Naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, Methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, dimethyl methyl succinic acid, glutaric acid, hexafluoroglutaric acid, 2-methyl succinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanediamine Acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid Acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, decacanedioic acid Hexacanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, behenedioic acid, tricosanedioic acid, Tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hexadecanedioic acid Monoalkanedioic acid, triacontanedioic acid, diglycolic acid, dicyclopentadiene carboxylic acid, etc. These can also be used in combination.
作為含羥基之二胺,例如可例舉: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。亦可將該等混合使用。Examples of the hydroxyl-containing diamine include: 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amine hydroxy-3-hydroxyphenyl)trine, 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 can also be used in combination.
(B2)光酸產生劑 光酸產生劑具有使光照射部之鹼性水溶液可溶性增大之功能。作為光酸產生劑,可例舉: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,重氮萘醌化合物因感度較高而較佳。 (B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the alkaline aqueous solution in the light-irradiated part. Examples of the photoacid generator include naphthoquinone diazonium compounds, aryl diazonium salts, diaryl ionium salts, triarylsulfonium salts, and the like. Among them, naphthoquinone diazonium compounds are preferred because of their high sensitivity.
(C)添加劑 較佳之添加劑之種類及量與聚醯亞胺前驅物組合物之項目中所記載之內容相同。 (C)Additives The preferred types and amounts of additives are the same as those described in the item of the polyimide precursor composition.
(D)溶劑 只要為可使各成分溶解或分散之溶劑即可,並無特別限定。 (D)Solvent It is not particularly limited as long as it is a solvent that can dissolve or disperse each component.
(E)其他 聚苯并㗁唑前驅物組合物可包含交聯劑、增感劑、接著助劑、熱酸產生劑等。 (E)Others The polybenzoethazole precursor composition may include cross-linking agents, sensitizers, adhesion auxiliaries, thermal acid generators, etc.
(顯影) 對聚苯并㗁唑前驅物組合物進行曝光後,利用顯影液沖洗無用部分。作為所使用之顯影液,並無特別限制,例如可例舉氫氧化鈉、氫氧化鉀、矽酸鈉、氨、乙基胺、二乙基胺、三乙基胺、三乙醇胺、四甲基氯化銨等鹼性水溶液作為較佳者。 (Develop) After exposing the polybenzoethazole precursor composition, the useless portions are rinsed with a developer. The developer used is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylamine. Alkaline aqueous solutions such as ammonium chloride are preferred.
上述中,以正型聚苯并㗁唑前驅物組合物為中心進行了說明,亦可為負型聚苯并㗁唑前驅物組合物。In the above description, the positive polybenzoethazole precursor composition has been mainly described, but a negative polybenzoethazole precursor composition may also be used.
(熱硬化) 顯影後,對聚苯并㗁唑前驅物組合物進行加熱,藉此使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 polybenzoethazole precursor composition is heated, thereby closing the ring of the polybenzoethazole precursor to form polybenzoethazole. This polybenzoconazole becomes the hardened relief pattern, that is, the interlayer insulating film 6 .
用以使聚苯并㗁唑前驅物組合物熱硬化之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之溫度。該加熱溫度較佳為250℃以下,更佳為230℃以下,更佳為200℃以下,尤佳為180℃以下。The heating temperature used to thermally harden the polybenzoethazole precursor composition is not particularly limited. From the viewpoint of the influence on other components, the heating temperature is preferably a lower temperature. The heating temperature is preferably 250°C or lower, more preferably 230°C or lower, more preferably 200°C or lower, especially 180°C or lower.
<聚苯并㗁唑> 由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成為下述通式(10)。 <Polybenzoethazole> The structure of the hardened relief pattern formed from the above-mentioned polybenzoethazole precursor composition is the following general formula (10).
[化32] [Chemical 32]
通式(10)中之U與通式(14)中之Y 2相同,通式(10)中之V與通式(14)中之Y 3相同。通式(14)中之較佳之Y 2、Y 3因相同原因,於通式(10)之聚苯并㗁唑中亦較佳。 U in the general formula (10) is the same as Y 2 in the general formula (14), and V in the general formula (10) is the same as Y 3 in the general formula (14). Y 2 and Y 3 which are preferred in the general formula (14) are also preferred in the polybenzoethazole 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 感光性樹脂係分子中具有酚性羥基之樹脂,可溶於鹼中。作為其具體例,可例舉:聚(羥基苯乙烯)等包含具有酚性羥基之單體單元之乙烯基聚合物、酚系樹脂、聚(羥基醯胺)、聚(羥基伸苯基)醚、聚萘酚。 <Polymer with phenolic hydroxyl group> (A)Photosensitive resin Photosensitive resin is a resin with phenolic hydroxyl groups in its molecules and is soluble in alkali. Specific examples thereof include vinyl polymers containing a monomer unit having a phenolic hydroxyl group such as poly(hydroxystyrene), phenolic resins, poly(hydroxyamide), and poly(hydroxyphenylene) ether. , polynaphthol.
該等之中,就成本廉價及硬化時之體積收縮較小之方面而言,較佳為酚系樹脂,尤佳為酚醛清漆型酚系樹脂。Among these, phenol-based resins are preferred in terms of low cost and small volume shrinkage during hardening, and novolac-type phenolic resins are particularly preferred.
酚系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之存在下進行。將使用酸觸媒之情形時所獲得之酚系樹脂特別稱為酚醛清漆型酚系樹脂。Phenolic resin is a condensation product of phenol or its derivatives and aldehydes. Polycondensation is carried out in the presence of catalysts such as acid or alkali. The phenolic resin obtained when an acid catalyst is used is particularly called a novolak type phenolic resin.
作為酚衍生物,例如可例舉: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、苄基氧基苯酚、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, o- Hydroquinone, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rose acid , bisphenol, 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-diiso Propylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)benzene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2- Hydroxy-5-biphenyl)propane, dihydroxybenzoic acid, etc.
作為醛化合物,可例舉: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、乙基丁基醛、苯甲醛、乙醛酸、5-降𦯉烯-2-羧基醛、丙二醛、丁二醛、戊二醛、水楊醛、萘醛、對苯二甲醛等。Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexanal, and diphenyl acetaldehyde. , ethyl butyl aldehyde, benzaldehyde, glyoxylic acid, 5-norphenyl-2-carboxylic aldehyde, malondialdehyde, succinic aldehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, etc.
(A)成分較佳為包含(a)不具有不飽和烴基之酚系樹脂及(b)具有不飽和烴基之改性酚系樹脂者。上述(b)成分更佳為藉由酚性羥基與多元酸酐之反應而進一步被改性而成者。The component (A) preferably contains (a) a phenolic resin that does not have an unsaturated hydrocarbon group and (b) a modified phenolic resin that has an unsaturated hydrocarbon group. It is more preferable that the said (b) component is further modified by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride.
又,作為(b)成分,就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,較佳為使用經碳數4~100之具有不飽和烴基之化合物改性之酚系樹脂。Furthermore, from the viewpoint of further improving the mechanical properties (elongation at break, elastic modulus and residual stress), component (b) is preferably modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. Phenolic resin.
(b)具有不飽和烴基之改性酚系樹脂通常係酚或其衍生物與具有不飽和烴基之化合物(較佳為碳數為4~100者)(以下,視情形而有時簡稱為「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」)與醛類之縮聚產物、或酚系樹脂與含不飽和烴基之化合物之反應產物。(b) Modified phenolic resin having an unsaturated hydrocarbon group is usually phenol or a derivative thereof and a compound having an unsaturated hydrocarbon group (preferably one with a carbon number of 4 to 100) (hereinafter, sometimes abbreviated to " The reaction product of "unsaturated hydrocarbon group-containing compound" (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and aldehydes, or the reaction product of phenolic resin and unsaturated hydrocarbon group-containing compound.
此處所言之酚衍生物可使用與作為(A)成分之酚系樹脂之原料而於上文中說明之酚衍生物相同者。As the phenol derivative here, the same thing as the phenol derivative described above as a raw material of the phenol-based resin of the component (A) can be used.
就抗蝕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包含2個以上之不飽和基。又,就製成樹脂組合物時之相溶性及硬化膜之可撓性之觀點而言,含不飽和烴基之化合物較佳為碳數8~80者,更佳為碳數10~60者。From the viewpoint of the adhesion of the resist pattern and the thermal shock resistance, the unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated groups. Moreover, from the viewpoint of compatibility when forming a resin composition and flexibility of a cured film, the unsaturated hydrocarbon group-containing compound is preferably one having 8 to 80 carbon atoms, and more preferably one having 10 to 60 carbon atoms.
作為含不飽和烴基之化合物,例如為碳數4~100之不飽和烴、具有羧基之聚丁二烯、環氧化聚丁二烯、亞麻醇、油醇、不飽和脂肪酸及不飽和脂肪酸酯。作為較佳之不飽和脂肪酸,可例舉:丁烯酸、肉豆蔻油酸、棕櫚油酸、油酸、反油酸、異油酸酸、鱈油酸、芥酸、二十四烯酸、亞麻油酸、α-次亞麻油酸、桐酸、十八碳四烯酸、花生四烯酸、二十碳五烯酸、鯡魚酸及二十二碳六烯酸。該等之中,尤其是碳數8~30之不飽和脂肪酸與碳數1~10之一元醇至三元醇之酯更佳,尤佳為碳數8~30之不飽和脂肪酸與作為三元醇之甘油之酯。Examples of compounds containing unsaturated hydrocarbon groups include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having carboxyl groups, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids and unsaturated fatty acid esters. . Preferable unsaturated fatty acids include: crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, codoleic acid, erucic acid, tetracosyl acid, and nylonic acid. Sesoleic acid, alpha-linolenic acid, eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among these, esters of unsaturated fatty acids with 8 to 30 carbon atoms and monohydric to trihydric alcohols with 1 to 10 carbon atoms are particularly preferred, and particularly preferred are esters of unsaturated fatty acids with 8 to 30 carbon atoms and trihydric alcohols with 1 to 10 carbon atoms. Glycerol ester of alcohol.
碳數8~30之不飽和脂肪酸與甘油之酯可以植物油自商業上獲取。植物油有碘值為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,例如可例舉:橄欖油、牽牛花種子油、何首烏籽油、山茶花油、山茶油、蓖麻油及花生油。作為半乾性油,例如可例舉玉米油、棉籽油及芝麻油。作為乾性油,例如可例舉桐油、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,亦可使用對該等植物油進行加工而獲得之加工植物油。Esters of unsaturated fatty acids with 8 to 30 carbon atoms and glycerin can be obtained commercially from 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 but 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 the semi-drying oil include corn oil, cottonseed oil and sesame oil. Examples of the drying oil include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil, and mustard oil. Moreover, processed vegetable oil obtained by processing these vegetable oils can also be used.
於上述植物油之中,就於酚或其衍生物或酚系樹脂與植物油之反應中,防止反應過度進行所伴隨之凝膠化,從而提高良率之觀點而言,較佳為使用非乾性油。另一方面,就提高抗蝕圖案之密接性、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本發明所帶來之效果之方面而言,較佳為桐油、亞麻仁油、大豆油、胡桃油及紅花油,更佳為桐油及亞麻仁油。Among the above-mentioned vegetable oils, in the reaction between phenol or its derivatives or phenolic resin and vegetable oil, it is preferable to use a non-drying oil from the viewpoint of preventing gelation associated with excessive reaction and thereby improving the yield. . On the other hand, from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the resist pattern, it is preferable to use dry oil. Among dry oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferred, and tung oil and linseed are more preferred in terms of more effectively and reliably exerting the effects of the present invention. Oil.
該等含不飽和烴基之化合物可單獨使用1種或將2種以上組合使用。These unsaturated hydrocarbon group-containing compounds may be used individually by 1 type or in combination of 2 or more types.
於製備(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。就提高硬化膜(抗蝕圖案)之可撓性之觀點而言,酚衍生物與含不飽和烴基之化合物之反應比率較佳為相對於酚衍生物100質量份,含不飽和烴基之化合物為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,則有硬化膜之可撓性降低之傾向,若超過100質量份,則有硬化膜之耐熱性降低之傾向。於上述反應中,亦可視需要將對甲苯磺酸、三氟甲磺酸等用作觸媒。When preparing 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. From the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenol derivative and the unsaturated hydrocarbon group-containing compound is preferably 100 parts by mass of the phenol derivative, and the unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may also be used as a catalyst if necessary.
藉由使藉由上述反應而生成之不飽和烴基改性酚衍生物與醛類縮聚,生成經含不飽和烴基之化合物改性之酚系樹脂。醛類可使用與作為用於獲得酚系樹脂之醛類而於上文中說明者相同者。By condensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes, a phenol-based resin modified with an unsaturated hydrocarbon group-containing compound is produced. The aldehydes that can be used are the same ones described above as the aldehydes used to obtain the phenolic 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系樹脂之合成條件。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,例如可例舉鹽酸、硫酸、甲酸、乙酸、對甲苯磺酸及草酸。該等酸觸媒可單獨使用1種或將2種以上組合使用。The reaction between the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon-modified phenol derivative is a condensation polymerization reaction, and previously known synthesis conditions of phenolic resins can be used. The reaction is preferably carried out in the presence of a catalyst such as acid or alkali, and more preferably an acid catalyst is used. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used individually by 1 type or in combination of 2 or more types.
上述反應通常較佳為於反應溫度100~120℃下進行。又,反應時間視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,藉此獲得經含不飽和烴基之化合物改性之酚系樹脂。再者,反應亦可使用甲苯、二甲苯、甲醇等溶劑。The above reaction is usually preferably carried out at a reaction temperature of 100 to 120°C. In addition, the reaction time varies depending on the type or amount of 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 a compound containing an unsaturated hydrocarbon group. Furthermore, solvents such as toluene, xylene, and methanol can also be used in the reaction.
經含不飽和烴基之化合物改性之酚系樹脂,亦可藉由使上述不飽和烴基改性酚衍生物與間二甲苯之類之酚以外之化合物以及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。A phenol resin modified with an unsaturated hydrocarbon group-containing compound can also be obtained by polycondensing the unsaturated hydrocarbon group-modified phenol derivative with a compound other than phenol such as m-xylene and aldehydes. In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting a phenol derivative and an unsaturated hydrocarbon group-containing compound is preferably less than 0.5.
(b)成分亦可使上述(a)成分之酚系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 phenolic resin of the component (a) above with an unsaturated hydrocarbon group-containing compound.
與酚系樹脂反應之含不飽和烴基之化合物可使用與上述含不飽和烴基之化合物相同者。The unsaturated hydrocarbon group-containing compound that reacts with the phenolic resin can be the same as the above-mentioned unsaturated hydrocarbon group-containing compound.
酚系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,作為酚系樹脂與含不飽和烴基之化合物之反應比率,就提高硬化膜(抗蝕圖案)之可撓性之觀點而言,較佳為相對於酚系樹脂100質量份,含不飽和烴基之化合物為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,則有硬化膜之可撓性降低之傾向,若超過100質量份,則有於反應中凝膠化之可能性變高之傾向、及有硬化膜之耐熱性降低之傾向。此時,亦可視需要將對甲苯磺酸、三氟甲磺酸等用作觸媒。再者,反應亦可使用甲苯、二甲苯、甲醇、四氫呋喃等溶劑。The reaction between the phenolic resin and the compound containing unsaturated hydrocarbon groups is usually preferably carried out at 50 to 130°C. In addition, as the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (resist pattern), it is preferable that the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound is 100 parts by mass of the phenolic resin. The amount of the hydrocarbon group compound is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, and still more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film will tend to decrease. If it exceeds 100 parts by mass, the possibility of gelation during the reaction will tend to increase, and hardening will occur. The film's heat resistance tends to decrease. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may also be used as catalysts if necessary. Furthermore, solvents such as toluene, xylene, methanol, and tetrahydrofuran can also be used in the reaction.
使多元酸酐進而與殘留於藉由如以上之方法而生成之經含不飽和烴基之化合物改性之酚系樹脂中的酚性羥基反應。藉此,亦可將經酸改性之酚系樹脂用作(b)成分。利用多元酸酐進行酸改性,藉此導入羧基,使(b)成分於鹼性水溶液(顯影液)中之溶解性更進一步提高。The polybasic acid anhydride is further 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, an acid-modified phenolic resin can also be used as the component (b). Acid modification is performed using polybasic acid anhydride to introduce carboxyl groups, thereby further improving the solubility of component (b) in an alkaline aqueous solution (developer).
多元酸酐並無特別限定,只要具有含有複數個羧基之多元酸之羧基脫水縮合而形成之酸酐基即可。作為多元酸酐,例如可例舉:鄰苯二甲酸酐、琥珀酸酐、辛烯基琥珀酸酐、十五烯基琥珀酸酐、順丁烯二酸酐、依康酸酐、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、二苯基醚四羧酸二酐、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1種或將2種以上組合使用。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1種以上。於該情形時,具有可形成具有更良好之形狀之抗蝕圖案之優勢。The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of carboxyl groups of a polybasic acid containing a plurality of carboxyl groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenylsuccinic anhydride, pentadecenylsuccinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Hydrophthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride Dibasic acid anhydrides such as methylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic acid dianhydride and benzophenone tetracarboxylic dianhydride. These can be used individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern with a better shape can be formed.
又,(A)具有酚性羥基之鹼可溶性樹脂可進而含有使多元酸酐反應從而進行酸改性而成之酚系樹脂。藉由使(A)成分含有經多元酸酐酸改性之酚系樹脂,(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 further contain the phenolic resin which acid-modified it by reacting a polybasic acid anhydride. By making component (A) contain a phenolic resin modified with a polybasic acid anhydride acid, the solubility of component (A) in an alkaline aqueous solution (developer) is further improved.
作為上述多元酸酐,例如可例舉:鄰苯二甲酸酐、琥珀酸酐、辛烯基琥珀酸酐、十五烯基琥珀酸酐、順丁烯二酸酐、依康酸酐、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、二苯基醚四羧酸二酐、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1種或將2種以上組合使用。該等之中,多元酸酐較佳為二元酸酐,更佳為選自由例如四氫鄰苯二甲酸酐、琥珀酸酐及六氫鄰苯二甲酸酐所組成之群中之1種以上。Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenylsuccinic anhydride, pentadecenylsuccinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydropthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl Endomethylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride and other dianhydrides, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride and other aliphatic and aromatic tetracarboxylic acid dianhydrides. These can be used individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more types selected from the group consisting of, for example, tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride.
(B2)光酸產生劑 作為光酸產生劑,可例舉: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,重氮萘醌化合物因感度較高而較佳。 (B2) Photoacid generator Examples of the photoacid generator include naphthoquinone diazonium compounds, aryl diazonium salts, diaryl ionium salts, triarylsulfonium salts, and the like. Among them, naphthoquinone diazonium compounds are preferred because of their high sensitivity.
(C)添加劑 較佳之添加劑之種類及量與聚醯亞胺前驅物組合物之項目中所記載之內容相同。 (C)Additives The preferred types and amounts of additives are the same as those described in the item of the polyimide precursor composition.
(D)溶劑 只要為可使各成分溶解或分散之溶劑即可,並無特別限定。 (D)Solvent It is not particularly limited as long as it is a solvent that can dissolve or disperse each component.
(E)其他 可包含熱交聯劑、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,於對圖案形成後之感光性樹脂膜進行加熱而使其硬化時,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,可防止膜之脆弱及膜之熔融。作為熱交聯劑成分,具體而言,可將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用作較佳者。 (E)Others It can include thermal cross-linking agents, sensitizers, adhesion assistants, dyes, surfactants, dissolution accelerators, cross-linking accelerators, etc. Among them, by containing a thermal crosslinking agent, when the photosensitive resin film after pattern formation is heated and hardened, the thermal crosslinking agent component reacts with the component (A) to form a crosslinked structure. Thereby, it can be hardened at low temperature, and the film can be prevented from being fragile and melting. As the thermal crosslinking agent component, specifically, compounds having a phenolic hydroxyl group, a compound having a hydroxymethylamine group, and a compound having an epoxy group can be used as preferred ones.
(顯影) 對具有酚性羥基之聚合物進行曝光後,利用顯影液對無用部分進行沖洗。作為所使用之顯影液,並無特別限制,例如可較佳地使用氫氧化鈉、氫氧化鉀、矽酸鈉、氨、乙基胺、二乙基胺、三乙基胺、三乙醇胺、氫氧化四甲基銨(TMAH)等鹼性水溶液。 (Develop) After exposing the polymer having phenolic hydroxyl groups, the useless parts are rinsed with a developer. The developer used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, hydrogen Tetramethylammonium oxide (TMAH) and other alkaline aqueous solutions.
(熱硬化) 顯影後,對具有酚性羥基之聚合物進行加熱,藉此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 development, the polymers having phenolic hydroxyl groups are heated, whereby the polymers having phenolic hydroxyl groups are thermally cross-linked with each other. The cross-linked polymer becomes the hardened relief pattern, that is, the interlayer insulating film 6 .
用以使具有酚性羥基之聚合物熱硬化之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之溫度。該加熱溫度較佳為250℃以下,更佳為230℃以下,更佳為200℃以下,尤佳為180℃以下。The heating temperature for thermally hardening the polymer having a phenolic hydroxyl group is not particularly limited. From the viewpoint of the influence on other members, the heating temperature is preferably a lower temperature. The heating temperature is preferably 250°C or lower, more preferably 230°C or lower, more preferably 200°C or lower, especially 180°C or lower.
(半導體裝置之製造方法) 本實施方式之半導體裝置之製造方法包括: (保護層形成步驟),其係於半導體晶片形成保護層之步驟; (密封材形成步驟),其係以該保護層之至少一部分露出之方式利用密封材覆蓋形成有保護層之半導體晶片之步驟;及 (再配線層形成步驟),其係於保護層側形成俯視下面積大於半導體晶片且包含層間絕緣膜之再配線層之步驟; 保護層與層間絕緣膜之楊氏模數之差為1.0~5.0 GPa。 使用圖3對本實施方式中之半導體裝置之製造方法進行說明。圖3係本實施方式之半導體裝置之製造步驟之一例。於圖3A中,準備完成了前步驟之晶圓10。其後,塗佈感光性樹脂組合物(保護層形成用之感光性組合物),並進行曝光顯影而形成凸紋圖案(保護層形成步驟)。接下來,於圖3B中,對上述晶圓進行切割,形成複數個半導體晶片2。將以如上方式而準備之半導體晶片2如圖3C所示般以特定間隔貼附於支持體11上。 (Method for manufacturing semiconductor device) The manufacturing method of the semiconductor device of this embodiment includes: (Protective layer forming step), which is a step of forming a protective layer on a semiconductor wafer; (Sealing material forming step), which is a step of covering the semiconductor wafer on which the protective layer is formed with a sealing material in such a manner that at least a portion of the protective layer is exposed; and (Rewiring layer forming step), which is a step of forming a rewiring layer on the side of the protective layer that has an area larger than the semiconductor wafer in plan view and includes an interlayer insulating film; The difference in Young's modulus of the protective layer and the interlayer insulating film is 1.0 to 5.0 GPa. The manufacturing method of the semiconductor device in this embodiment will be described using FIG. 3 . FIG. 3 shows an example of manufacturing steps of the semiconductor device according to this embodiment. In FIG. 3A , the wafer 10 having completed the previous steps is prepared. Thereafter, a photosensitive resin composition (photosensitive composition for forming a protective layer) is applied and exposed and developed to form a relief pattern (protective layer forming step). Next, as shown in FIG. 3B , the above-mentioned wafer is cut to form a plurality of semiconductor wafers 2 . The semiconductor wafer 2 prepared in the above manner is attached to the support 11 at specific intervals as shown in FIG. 3C .
繼而,自半導體晶片2上至支持體11上塗佈塑模樹脂12,如圖3D所示進行塑模密封(密封材形成步驟)。繼而,將支持體11剝離,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出現於大致相同平面內。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。接下來,對經塗佈之感光性樹脂組合物13進行曝光顯影,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,對凸紋圖案進行加熱,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 mold resin 12 is applied from the semiconductor wafer 2 to the support 11, and mold sealing is performed as shown in FIG. 3D (sealing material forming step). Next, the support 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 appear in substantially the same plane. Next, in the step shown in FIG. 3F , the photosensitive resin composition 13 is coated on the semiconductor wafer 2 and the molding resin 12 . Next, 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 a positive type or a 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 portion where the hardened relief pattern is not formed (wiring forming step).
再者,於本實施方式中,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一併設為形成連接於半導體晶片2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 collectively regarded as 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亦可為多層。因此,再配線層形成步驟亦可包含複數次凸紋圖案形成步驟、複數次層間絕緣膜形成步驟及複數次配線形成步驟。The interlayer insulating film in the rewiring layer may be multi-layered. Therefore, the rewiring layer forming step may also include a plurality of relief pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.
接下來,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),並將各半導體晶片2間切斷。藉此,如圖3H所示,可獲得半導體裝置(半導體IC)1。於本實施方式中,可藉由圖3所示之製造方法獲得複數個扇出型半導體裝置1。Next, in FIG. 3G , a plurality of external connection terminals 7 corresponding to each semiconductor wafer 2 are formed (bump formation), and each semiconductor wafer 2 is cut off. 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 through the manufacturing method shown in FIG. 3 .
於本實施方式中,於上述層間絕緣膜形成步驟中,較佳為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1種化合物之感光性樹脂組合物形成層間絕緣膜。 [實施例] In this embodiment, in the interlayer insulating film forming step, it is preferable to use a photosensitive resin composition that can form at least one compound that can form polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. Form an interlayer insulating film. [Example]
以下,對為了明確本發明之效果而進行之實施例進行說明。於實施例中,使用以下材料及測定方法。Hereinafter, Examples performed in order to clarify the effects of the present invention will be described. In the examples, the following materials and measurement methods were used.
以下,對為了明確本發明之效果而進行之實施例進行說明。Hereinafter, Examples performed in order to clarify the effects of the present invention will be described.
(聚合物A-1:聚醯亞胺前驅物之合成) 將作為四羧酸二酐之4,4'-氧二鄰苯二甲酸二酐(ODPA)添加至2升容量之可分離式燒瓶中。進而,添加甲基丙烯酸2-羥基乙酯(HEMA)與γ-丁內酯,並於室溫下進行攪拌,一面攪拌,一面添加吡啶,獲得反應混合物。於因反應而產生之發熱結束後,冷卻至室溫,並放置16小時。 (Polymer A-1: Synthesis of polyimide precursor) 4,4'-oxydiphthalic dianhydride (ODPA) as tetracarboxylic dianhydride was added to a 2 liter capacity separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were added and stirred at room temperature. While stirring, pyridine was added to obtain a reaction mixture. After the heat generated by the reaction ends, the mixture is cooled to room temperature and left to stand for 16 hours.
繼而,於冰冷下,一面對將二環己基碳二醯亞胺(DCC)溶解於γ-丁內酯中所得之溶液進行攪拌,一面歷時40分鐘將該溶液添加至反應混合物中。繼而,一面對將作為二胺之4,4'-二胺基二苯基醚(DADPE)懸浮於γ-丁內酯中所得者進行攪拌,一面歷時60分鐘添加。進而,於室溫下攪拌2小時後,添加乙醇並攪拌1小時,繼而添加γ-丁內酯。藉由過濾將反應混合物中所產生之沈澱物去除,獲得反應液。Then, a solution obtained by dissolving dicyclohexylcarbodiimide (DCC) in γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring the solution under ice cooling. Next, the suspension of 4,4'-diaminodiphenyl ether (DADPE) as a diamine in γ-butyrolactone was added over 60 minutes while stirring. 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 is removed by filtration to obtain a reaction liquid.
將所獲得之反應液添加至乙醇中,生成包含粗聚合物之沈澱物。對所生成之粗聚合物進行過濾分離,並將其溶解於四氫呋喃中,獲得粗聚合物溶液。將所獲得之粗聚合物溶液滴加至水中,使聚合物沈澱,並對所獲得之沈澱物進行過濾分離,然後進行真空乾燥,獲得粉末狀聚合物(聚醯亞胺前驅物(聚合物A-1))。關於成分A-1中所使用之化合物之質量,如下述所示之表1所示。The obtained reaction liquid was added to ethanol to generate a precipitate containing a crude polymer. The generated 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 filtered and separated, 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 shown below.
(聚合物A-2~A-5之合成) 將四羧酸二酐與二胺如下述表1所示般變更,除此以外,以與上述聚合物A-1所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~A-5)。 (Synthesis of polymers A-2 to A-5) Except for changing the tetracarboxylic dianhydride and the diamine as shown in Table 1 below, the reaction was carried out in the same manner as described for the above-mentioned polymer A-1 to obtain a polyimide precursor (polymer). A-2~A-5).
(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'-二苯基醚二羧酸15.48 g、N-甲基吡咯啶酮。將燒瓶冷卻至5℃後,滴加亞硫醯氯,並反應30分鐘,獲得二羧醯氯之溶液。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及間胺基苯酚2.18 g攪拌溶解後,添加吡啶。接下來,一面將溫度保持在0~5℃,一面歷時30分鐘滴加二羧醯氯之溶液,然後繼續攪拌30分鐘。將溶液投入3升之水中,回收析出物,並利用純水洗淨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中所使用之化合物之質量,如下述表1所示。 (Polymer B-1: Synthesis of polybenzoethazole precursor) To a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid as a dicarboxylic acid and N-methylpyrrolidone were added. After the flask was cooled to 5°C, thionyl chloride was added dropwise and the reaction was carried out for 30 minutes to obtain a solution of dicarboxylic acid 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, pyridine was added. Next, while maintaining the temperature at 0 to 5°C, a solution of dicarboxylic acid chloride was added dropwise over 30 minutes, and then 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 dried under reduced pressure to obtain a polymer (polybenzoconazole precursor (polymer B-1)). The mass of the compound used in polymer B-1 is shown in Table 1 below.
(聚合物B-2~B-3之合成) 將二羧酸與雙胺基苯酚如下述所示之表1般變更,除此以外,以與上述聚合物B-1所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~B-3)。 (Synthesis of polymers B-2~B-3) Except for changing the dicarboxylic acid and the bisaminophenol as shown in Table 1 below, the reaction was carried out in the same manner as described for the above-mentioned polymer B-1 to obtain a polybenzoethazole precursor ( Polymers B-2 to B-3).
(聚合物C-1:酚系樹脂之合成) 準備包含下述所示之C1樹脂85 g及下述所示之C2樹脂15 g之酚系樹脂作為聚合物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-based resin containing 85 g of the C1 resin shown below and 15 g of the C2 resin shown below was prepared as polymer C-1. C1: Cresol novolac resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene-converted weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Industry Co., Ltd. Product name "EP4020G")
C2:C2係如下所述半合成。 <C2:經碳數4~100之具有不飽和烴基之化合物改性之酚系樹脂之合成> 將苯酚100質量份、亞麻仁油43質量份及三氟甲磺酸0.1質量份進行混合,並於120℃下攪拌2小時,獲得植物油改性酚衍生物(a)。繼而,將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進行混合,並於90℃下攪拌3小時。繼而,升溫至120℃,並於減壓下攪拌3小時後,向反應液中添加琥珀酸酐29 g及三乙基胺0.3 g,並於大氣壓下且於100℃下攪拌1小時。將反應液冷卻至室溫為止,獲得作為反應產物之經碳數4~100之具有不飽和烴基之化合物改性之酚系樹脂(以下,稱為「C2樹脂」)(酸值120 mgKOH/g)。 C2: C2 is semi-synthesized as described below. <C2: Synthesis of phenolic resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms> Mix 100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 parts by mass of triflate, and stir 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 stirred at 90° C. for 3 hours. Then, the temperature was raised to 120°C and 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 for 1 hour under atmospheric pressure. The reaction liquid was cooled to room temperature to obtain a reaction product, a phenolic resin modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (hereinafter referred to as "C2 resin") (acid value: 120 mgKOH/g ).
(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) Prepare 100 g of the following C1 resin as polymer C-2.
[表1]
[調配例1~13] 如下述所示之表2所示般進行調配,獲得感光性樹脂組合物之溶液。再者,表2之單位為質量份。 關於表中所記載之楊氏模數,利用下述方法進行測定。 [Preparation examples 1 to 13] It was prepared as shown in Table 2 shown below, and a solution of the photosensitive resin composition was obtained. Furthermore, the units in Table 2 are parts by mass. The Young's modulus described in the table was measured using the following method.
針對所製作之感光性樹脂組合物,進行(1)楊氏模數測定、(2)基於ATR法之波峰比之算出、(3)封裝形成及龜裂、剝落評價。各試驗之結果示於下述表3、4中。Regarding the produced photosensitive resin composition, (1) Young's modulus measurement, (2) peak ratio calculation based on the ATR method, and (3) package formation, cracking, and peeling evaluation were performed. The results of each test are shown in Tables 3 and 4 below.
(1)楊氏模數測定 將調配例中所製備之樹脂組合物以硬化後膜厚成為10 μm之方式旋轉塗佈於表面設有鋁蒸鍍層之6英吋矽晶圓基板,並於110℃下預烘烤4分鐘。其後,使用縱型固化爐(Koyo Lindberg公司製造,型號名VF-2000B),以表中所記載之硬化溫度實施2小時加熱硬化處理,製作形成有樹脂膜之晶圓。使用晶圓切割機(DISCO股份有限公司製造 DAD 3350)於該晶圓之樹脂膜切出3 mm寬之切縫後,於稀鹽酸水溶液中浸漬一夜,將樹脂膜片剝離並進行乾燥。將其切成長度50 mm,製成樣品。 針對上述樣品,使用TENSILON(Orientec公司製造 UTM-II-20),以試驗速度40 mm/min、初始負荷0.5 fs測定楊氏模數。 (1)Measurement of Young’s modulus The resin composition prepared in the preparation example was spin-coated on a 6-inch silicon wafer substrate with an aluminum evaporation layer on the surface in such a way that the film thickness after curing became 10 μm, and pre-baked at 110°C for 4 minutes. Thereafter, a vertical curing oven (model name VF-2000B manufactured by Koyo Lindberg Co., Ltd.) was used to perform heat curing treatment for 2 hours at the curing temperature described in the table, thereby producing a wafer on which a resin film was formed. After cutting a 3 mm wide slit in the resin film of the wafer using a wafer cutting machine (DAD 3350 manufactured by DISCO Co., Ltd.), the wafer was immersed in a dilute hydrochloric acid aqueous solution overnight, and the resin film was peeled off and dried. Cut it into a length of 50 mm to make a sample. For the above sample, the Young's modulus was measured using TENSILON (UTM-II-20 manufactured by Orientec) at a test speed of 40 mm/min and an initial load of 0.5 fs.
(2)基於ATR法之波峰比之算出 針對以與上述(1)相同之方法而獲得之形成有樹脂膜之晶圓,使用Thermo Fisher Scientific公司製造之FT-IR,以測定範圍4000~400 cm -1、測定次數50次進行測定。藉由求出硬化膜之1380 cm -1附近之波峰高度與1500 cm -1附近之波峰高度而算出。 (2) Calculation of peak ratio based on ATR method Using FT-IR manufactured by Thermo Fisher Scientific, measuring range 4000 to 400 cm was used for the resin film-formed wafer obtained by the same method as (1) above. -1 . Measure the number of times 50 times. It is calculated by finding the peak height near 1380 cm -1 and the peak height near 1500 cm -1 of the cured film.
(3)封裝形成及龜裂、剝落評價 於已形成鋁墊、氧化矽之半導體晶片塗佈調配例中所調配之感光性樹脂組合物,並於表中之硬化溫度下進行硬化,藉此形成保護層。其後,形成銅柱,塗佈調配例中所調配之感光性樹脂組合物,並於表中之硬化溫度下進行硬化,藉此形成層間絕緣膜。其後,利用作為環氧系密封材之長瀨化成公司製造之R4000系列進行密封,並於130℃下進行熱硬化。 對上述環氧系密封樹脂進行研磨,使用形成上述層間絕緣膜之相同種類之感光性樹脂組合物形成2層再配線層。 進行對該封裝進行20次回焊後之晶片有無龜裂、保護層與層間絕緣膜之剝落之評價。 晶片龜裂評價; 將100個晶片中,產生龜裂之晶片為0個者評價為優,將1~9個者評價為良,將10~19個者評價為合格,將20個以上者評價為不合格。 剝落評價; 將100個封裝中,產生剝落之封裝為0個者評價為優,將1~9個者評價為良,將10~19個者評價為合格,將20個以上者評價為不合格。 再者,回焊係於使用網帶式連續焙燒爐(Koyo Thermo Systems公司製造,型號名6841-20AMC-36)之模擬性回焊條件下,於氮氣氛圍下加熱至波峰溫度260℃。所謂模擬性回焊條件,係依據與半導體裝置之評價方法相關之作為美國半導體業界團體之標準之IPC/JEDEC J-STD-020A之7.6項所記載之回焊條件之形態,將焊料熔點假定為高溫之220℃並標準化。 (3) Package formation, cracking, and peeling evaluation The photosensitive resin composition prepared in the preparation example is applied to the semiconductor wafer that has formed aluminum pad and silicon oxide, and is cured at the curing temperature in the table to form a protective layer. Thereafter, copper pillars are formed, the photosensitive resin composition prepared in the preparation example is applied, and cured at the curing temperature in the table, thereby forming an interlayer insulating film. Thereafter, R4000 series manufactured by Nagase Kasei Co., Ltd., which is an epoxy sealing material, was used for sealing and thermal hardening at 130°C. The above-mentioned epoxy-based sealing resin was polished, and two rewiring layers were formed using the same type of photosensitive resin composition used to form the above-mentioned interlayer insulating film. After the package was reflowed 20 times, the chip was evaluated for cracks and peeling of the protective layer and interlayer insulating film. Wafer crack evaluation; Among 100 wafers, 0 wafers with cracks were evaluated as excellent, 1 to 9 wafers were evaluated as good, 10 to 19 wafers were evaluated as pass, and 20 or more wafers were evaluated as failed. peeling evaluation; Out of 100 packages, 0 packages with peeling were evaluated as excellent, 1 to 9 packages as good, 10 to 19 packages as qualified, and 20 or more packages as failed. Furthermore, the reflow was performed under simulated reflow conditions using a mesh belt continuous baking furnace (manufactured by Koyo Thermo Systems, model name: 6841-20AMC-36), and was heated to a peak temperature of 260°C in a nitrogen atmosphere. The so-called simulated reflow conditions are based on the form of the reflow conditions described in Section 7.6 of IPC/JEDEC J-STD-020A, which is a standard for the U.S. semiconductor industry group regarding the evaluation method of semiconductor devices. The melting point of the solder is assumed to be High temperature of 220℃ and standardized.
[表2]
表2
[表3]
[表4]
根據表4明確,根據針對實施例1~10之感光性樹脂組合物而進行之結果,藉由將楊氏模數差設為固定範圍,可抑制晶片龜裂及剝落。As is clear from Table 4, according to the results of the photosensitive resin compositions of Examples 1 to 10, wafer cracking and peeling can be suppressed by setting the Young's modulus difference to a fixed range.
又,使用實施例1~10之感光性樹脂組合物製作塑模樹脂中包含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,結果無問題地運作。 [產業上之可利用性] Furthermore, the photosensitive resin compositions of Examples 1 to 10 were used to produce a fan-out wafer-level chip-size packaged semiconductor device containing an epoxy resin in the molding resin, and the result was that the device operated without any problem. [Industrial availability]
本發明可較佳地應用於具有半導體晶片、及連接於半導體晶片之再配線層之半導體裝置、尤其是扇出(Fan-Out)型之晶圓級晶片尺寸封裝型之半導體裝置。The present invention can be preferably applied to a semiconductor device having a semiconductor chip and a rewiring layer connected to the semiconductor chip, especially a fan-out type wafer-level chip size packaging 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(絕緣層) 7:外部連接端子 8:保護層 8a:孔 10:晶圓 11:支持體 12:塑模樹脂 13:感光性樹脂組合物 1:Semiconductor device 2:Semiconductor wafer 2a:Terminal 3:Sealing material 4:Rewiring layer 5: Wiring 6: Interlayer insulation film (insulation layer) 7:External connection terminal 8: Protective layer 8a:hole 10:wafer 11:Support 12:Molding resin 13: Photosensitive resin composition
圖1係本實施方式之半導體裝置之剖面模式圖。 圖2係本實施方式之半導體裝置之平面模式圖。 圖3A~H係本實施方式之半導體裝置之製造步驟之一例。 FIG. 1 is a schematic cross-sectional view of the semiconductor device according to this embodiment. FIG. 2 is a schematic plan view of the semiconductor device according to this embodiment. 3A to 3H are examples of manufacturing steps of the semiconductor device according to this embodiment.
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(絕緣層) 6: Interlayer insulation film (insulation layer)
7:外部連接端子 7:External connection terminal
8:保護層 8: Protective layer
8a:孔 8a:hole
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