CN106661412B - 用于半导体的粘合膜 - Google Patents
用于半导体的粘合膜 Download PDFInfo
- Publication number
- CN106661412B CN106661412B CN201680002140.XA CN201680002140A CN106661412B CN 106661412 B CN106661412 B CN 106661412B CN 201680002140 A CN201680002140 A CN 201680002140A CN 106661412 B CN106661412 B CN 106661412B
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- Prior art keywords
- adhesive film
- epoxy resin
- resin
- semiconductor
- adhesive
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 317
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- 239000007787 solid Substances 0.000 claims description 68
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- 238000000034 method Methods 0.000 abstract description 77
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- 230000001070 adhesive effect Effects 0.000 description 90
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- 238000004519 manufacturing process Methods 0.000 description 19
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
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- 239000003054 catalyst Substances 0.000 description 7
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 229930003836 cresol Natural products 0.000 description 6
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- 239000011800 void material Substances 0.000 description 6
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- 239000004842 bisphenol F epoxy resin Substances 0.000 description 4
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
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- 239000004840 adhesive resin Substances 0.000 description 3
- 229920006223 adhesive resin Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
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- 230000035882 stress Effects 0.000 description 3
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- 229910052726 zirconium Inorganic materials 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical class [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
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- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
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- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCCSVJRERUIAGJ-UHFFFAOYSA-N [Mg].[Sb] Chemical compound [Mg].[Sb] HCCSVJRERUIAGJ-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- LEHUDBPYSAPFFO-UHFFFAOYSA-N alumane;bismuth Chemical compound [AlH3].[Bi] LEHUDBPYSAPFFO-UHFFFAOYSA-N 0.000 description 1
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 1
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- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- SKKNACBBJGLYJD-UHFFFAOYSA-N bismuth magnesium Chemical compound [Mg].[Bi] SKKNACBBJGLYJD-UHFFFAOYSA-N 0.000 description 1
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- 150000001639 boron compounds Chemical class 0.000 description 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
本发明涉及用于半导体的粘合膜,其可以更容易地掩埋不平坦,例如由于半导体基板的配线或连接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率。
Description
技术领域
相关申请的交叉引用
本申请要求在2015年4月29日向韩国知识产权局提交的韩国专利申请第10-2015-0060690号的权益,其公开内容通过引用全文并入本文。
本发明涉及用于半导体的粘合膜,其可以更容易地掩埋不平坦,例如来自半导体基板的配线、附接至半导体芯片的配线等的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率。
背景技术
近来,随着电子装置日益趋向小型化、高性能和大容量,对高密度且高度集成的半导体封装的需求快速增加,因此半导体芯片的尺寸正在逐渐变大,并且为了提高集成程度,越来越多地使用多级堆叠芯片的堆叠封装方法。
在这种多级堆叠结构中,为了确保其中设置有电连接下部芯片与基板的下部接合线的空间,在下部芯片与上部芯片之间的界面处引入间隔件。在引入这种用于确保空间的间隔件的情况下,封装的总厚度变厚并且增加了附接间隔件的单独过程。
为了克服该问题,近来使用在高温下具有低粘度的粘合剂代替间隔件来填充例如来自配线等的不平坦的方法。然而,存在这样的限制:具有低粘度的粘合剂可能无法确保高弹性并且具有高断裂伸长率。此外,如果粘合剂自身的弹性减小,则由于切割晶片时产生的热,粘合剂可软化以致部分产生毛刺,并因此其可污染晶片,或者可通过与下部支撑膜的粘合剂混合来使用,从而降低后续拾取效率。
此外,近来,由于半导体芯片变得更薄,所以存在在现有的刀片切割工艺中芯片受损从而降低产率的问题,为了克服这一问题,提出了首先用刀片切割半导体芯片然后抛光的制备工艺。粘合剂应该能够在低温下通过扩展工艺切割以应用于这样的制备工艺。
然而,具有低延展性的粘合剂在室温下不易切割,并且当在切割之后将其在室温下静置时,由于低延展性而发生再粘合,从而降低了半导体芯片的产率。
发明内容
技术问题
本发明的一个目的是提供用于半导体的粘合膜,其可以更容易地掩埋不平坦,例如由于半导体基板的配线、附接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率。
技术方案
本文中提供了用于半导体的粘合膜,其在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且在室温下在5%至10%伸长率下产生的模量为50MPa或更高。
粘合膜可用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。
用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
本文中还提供了用于半导体的粘合膜,其在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且在室温下的伸长率为500%或更低。
粘合膜可用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。
用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
本文中还提供了用于半导体的粘合膜,其在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且在室温下的伸长率为500%或更低。
粘合膜可用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。
用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
本文中还提供了用于半导体的粘合膜,其在110℃的温度下在5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且在室温下的伸长率为500%或更低。
用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
包含在用于半导体的粘合膜中的液体环氧树脂在25℃下的粘度可为500mPa·s至20,000mPa·s。
液体环氧树脂的环氧当量重量可为100至1,000。
酚树脂的羟基当量重量可为80g/eq至400g/eq并且软化点可为70℃至160℃。
酚树脂的羟基当量重量可为100g/eq至178g/eq。
酚树脂的软化点可为高于100℃且160℃或更低、或者105℃至150℃。
在用于半导体树脂的粘合膜中,液体环氧树脂相对酚树脂的重量比可为0.5至1.5。
包含在用于半导体树脂的粘合膜中的固体环氧树脂可包括选自以下的一种或更多种树脂:联苯类环氧树脂、双酚A环氧树脂、双酚F环氧树脂、甲酚酚醛清漆环氧树脂、苯酚酚醛清漆环氧树脂、四官能环氧树脂、三酚甲烷型环氧树脂、经烷基改性的三酚甲烷型环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂和经二环戊二烯改性的酚型环氧树脂。
固体环氧树脂的平均环氧当量重量可为100至1,000。
固体环氧树脂的软化点可为50℃至120℃。
包含在用于半导体的粘合膜中的热塑性树脂可包括选自以下的一种或更多种聚合物树脂:聚酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚酰胺、聚醚砜、聚醚酮、聚烯烃、聚氯乙烯、苯氧基树脂、反应性丁二烯-丙烯腈共聚物橡胶和(甲基)丙烯酸酯类树脂。
(甲基)丙烯酸酯类树脂可为包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂。
(甲基)丙烯酸酯类树脂可包含0.1重量%至10重量%的含有环氧类官能团的(甲基)丙烯酸酯类重复单元。
包含在用于半导体的粘合膜中的固化剂还可包括选自胺类固化剂和酸酐类固化剂的一种或更多种化合物。
用于半导体的粘合膜还可包含离子清除剂,所述离子清除剂包括含有选自锆、锑、铋、镁和铝的一种或更多种金属的金属氧化物;多孔硅酸盐;多孔铝硅酸盐;或者沸石。
用于半导体的粘合膜还可包含选自磷化合物、磷-硼化合物和咪唑类化合物的一种或更多种固化催化剂。
用于半导体的粘合膜还可包含选自偶联剂和无机填料的一种或更多种添加剂。
此外,用于半导体的粘合膜可为管芯粘结膜。
此外,本文中提供了切割管芯粘结膜,其包含:基础膜;形成在所述基础膜上的粘性层;和形成在所述粘性层上的粘合剂层,所述粘合剂层包含上述用于半导体的粘合膜。
基础膜的厚度可为10μm至200μm,粘性层的厚度可为1μm至600μm、3μm至500μm或5μm至300μm,并且粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
本文中还提供了用于切割半导体晶片的方法,包括以下步骤:对包含切割管芯粘结膜的半导体晶片进行部分预处理;将晶片层合在切割管芯粘结膜的至少一侧上以使其被完全切割或可切割;以及将UV照射至经预处理的半导体晶片的基础膜,并且拾取通过切割半导体所分离的单独芯片。
有益效果
根据本发明,提供了用于半导体的粘合膜,其可以更容易地掩埋不平坦,例如半导体基板的配线、附接至半导体芯片的配线等的不平坦,并且还可以实现高耐热性和粘合强度以及改善的机械特性,并且可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率。
用于半导体的粘合膜因其独特特性而可以应用于非接触型粘合剂切割例如DBG(Dicing Before Grinding,研磨前切割)以及使用刀片的晶片切割,并且即使在相对低的温度下也具有优异的可切割性,并且因此即使将其在室温下静置,再粘合的可能性也变低,从而提高了半导体制造工艺中的可靠性和效率。
此外,用于半导体的粘合膜可以应用于各种半导体封装制造工艺,使得能够确保半导体末端与支撑构件(例如,下层的芯片或基板)的粘合过程中的高可靠性,并且可以实现优异的可加工性,同时确保在将半导体末端安装在半导体封装中时所需的耐热性、耐湿性和绝缘性。
此外,用于半导体的粘合膜可以确保提高的弹性和高机械特性,从而防止包含其的切割管芯粘结膜和使用所述切割管芯粘结膜切割半导体晶片的方法中的毛刺产生,进而提高切割过程中的拾取效率,并且确保低温和高温下的高可切割性。
具体实施方式
现在将详细说明根据本发明的具体实施方案的用于半导体的粘合膜。
根据本发明的一个实施方案,提供了用于半导体的粘合膜,其在110℃的温度在5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且在室温下在5%至10%伸长率下产生的模量为50MPa或更高。
此前,考虑到用于半导体的粘合膜的可掩埋性等,提出了添加具有低软化点的组分以降低熔体粘度的方法,但是该方法存在这样的限制:难以确保高弹性和断裂伸长率。
因此,本发明人通过实验确定:具有上述特定特性的用于半导体的粘合膜可以更容易地掩埋不平坦,例如由于半导体基板的配线、附接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率,并且完成了本发明。
特别地,由于用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量为50MPa或更高、或者50MPa至300MPa,所以该实施方案的粘合膜可以容易地应用于非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法,并且因此即使在低温下也具有优异的可切割性。
如果用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量低于50MPa,则即使在低温下进行扩展,可切割性也可能不足;如果将其在室温下静置,则可发生再粘合;并且由于在切割粘合膜所接合的晶片时产生的热,粘合剂可软化以致在粘合膜中产生毛刺,从而污染半导体芯片的电路侧。
此外,用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s。由于粘合膜在约110℃的温度下具有相对低的粘度,所以其可具有优异的粘合强度和对于半导体最佳化的流动性,这可有利于初始阶段固化的界面处和管芯连接过程中的空隙去除,并且在管芯连接之后,可顺利地实现接合线向周围空间的渗入而不显著影响粘合膜的形状和特性。
此外,由于用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,因此即使长时间暴露于在半导体制造过程中施加的高温条件,也基本上不会产生空隙,并且当应用于切割管芯粘结膜等时,可以确保足够的高温剪切力,从而确保优异的可切割性。
粘合膜可以用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。因此,粘合膜可加工成管芯粘结膜、切割管芯粘结膜等形式。
如上所述,如果用于半导体的粘合膜满足如下要求:在110℃的温度下在5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,以及在室温下在5%至10%伸长率下产生的模量为50MPa或更高,则可实现上述效果,并且具体组分没有显著限制。
例如,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
环氧树脂可与玻璃化转变温度为-10℃至20℃的热塑性树脂和含有软化点为70℃或更高的酚树脂的固化剂一起形成粘合剂组分的基体(或基质),并且其使得用于半导体的粘合膜在具有低粘度的同时具有高断裂强度和低断裂伸长率。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
由于用于半导体的粘合膜包含上述范围的相对于热塑性树脂的固体环氧树脂和液体环氧树脂,所以用于半导体的粘合膜可在高温下具有低粘度,并且还可实现高弹性、优异的机械特性和高粘合强度。由于环氧树脂的含量相对于热塑性树脂相对较低等原因,此前已知的用于半导体的粘合膜不能实现上述实施方案的用于半导体的粘合膜的独特特性。
如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比低于上述范围,则用于半导体的粘合膜可在高温下表现出高粘度,或者表现出低断裂强度和高断裂伸长率,并且高温剪切力也可减小,因此不能充分确保可切割性。
此外,如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,则用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量可变得显著较高,或者粘合膜在室温下的伸长率可显著降低,从而极大地抑制可加工性。
此外,如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,则在固化过程中,用于半导体的粘合膜的粘度增加速率可显著增加,并因此可能难以除去所述膜内的空隙,这可能妨碍半导体封装的可靠性。
同时,在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
酚树脂可与液体环氧树脂和玻璃化转变温度为-10℃至30℃的热塑性树脂一起形成粘合剂组分的基体(或基质),其中所述酚树脂优选地以高于一定水平的含量包含在所述粘合剂组分的基体中。
特别地,如果在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比小于0.280,则不能向用于半导体的粘合膜提供足够的固化程度,从而降低耐热性,粘合膜在室温下在5%至10%伸长率下产生的模量可显著降低,并且粘合膜在室温下的伸长率可显著增加,并且在使用粘合膜制造的切割管芯粘结膜中,通过切割过程可过度产生毛刺,并且高温剪切力也可减小,并因此不能充分确保可切割性。
同时,包含在用于半导体的粘合膜中的固化剂可包含软化点为70℃或更高的酚树脂。所述酚树脂的软化点可为70℃或更高、80℃或更高、70℃至160℃、高于100℃且160℃或更低、或者105℃至150℃。
上述实施方案的用于半导体的粘合膜可包含软化点相对高的酚树脂,并且软化点为70℃或更高、80℃或更高、70℃至160℃、高于100℃且160℃或更低、或者105℃至150℃的酚树脂可与液体环氧树脂和玻璃化转变温度为-10℃至30℃的热塑性树脂一起形成粘合剂组分的基体(或基质),并且向用于半导体的粘合膜提供在室温下较高的拉伸模量和优异的粘合强度以及对于半导体最佳化的流动特性。
反之,如果酚树脂的软化点低于上述范围,则用于半导体的粘合膜在室温下的拉伸模量可降低,或者在室温下的伸长率可显著增加,并且用于半导体的粘合膜的熔体粘度可减小或者模量可降低,并因此可由在切割过程中产生的热产生更多毛刺,或者可切割性或拾取效率可降低。此外,如果接合粘合膜的过程或粘合膜长时间暴露于高温条件,则可能发生大量渗出。
此外,酚树脂的羟基当量重量可为80g/eq至400g/eq、90g/eq至250g/eq、100g/eq至178g/eq、或210至240g/eq。由于酚树脂具有上述的羟基当量重量范围,所以固化程度即使在短固化时间下也可增加,从而向用于半导体的粘合膜提供在室温下更高的拉伸模量和优异的粘合强度。
在上述实施方案的用于半导体的粘合膜中,液体环氧树脂相对酚树脂的重量比可为0.5至1.5。
如果液体环氧树脂相对酚树脂的重量比太高,则用于半导体的粘合膜的断裂强度可显著增加,在室温下的拉伸模量可降低,并且在低温切割过程中的可切割性或效率可降低。
此外,如果液体环氧树脂相对酚树脂的重量比太低,则在室温下在伸长率下产生的模量可变得太高,或者在室温下的伸长率可显著降低,从而显著降低最终产品的产率,并且用于半导体的粘合膜不能与晶片充分粘合,从而在制造过程中发生晶片与粘合膜之间的剥离。
液体环氧树脂的具体种类和性质没有显著限制,但是例如,液体环氧树脂在25℃下的粘度可为500mPa·s至20,000mPa·s。此外,液体环氧树脂的环氧当量重量可为100至1,000。
同时,液体环氧树脂可与玻璃化转变温度为-10℃至30℃的热塑性树脂和含有酚树脂的固化剂一起形成粘合剂组分的基体(或基质),并使粘合膜具有相对低的粘度,并且还具有优异的粘合强度和对于半导体最佳化的流动特性,并因此可有利于初始阶段固化中的界面处和管芯连接过程中的空隙去除。
同时,如上所述,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂。
热塑性树脂的实例没有特别限制,但是例如可包括:聚酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚酰胺、聚醚砜、聚醚酮、聚烯烃、聚氯乙烯、苯氧基树脂、反应性丁二烯-丙烯腈共聚物橡胶、(甲基)丙烯酸酯类树脂、其中两种或更多种的混合物、或者其中两种或更多种的共聚物。
特别地,(甲基)丙烯酸酯类树脂可为包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂。
通过使用包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂,在将用于半导体的粘合膜用于超薄晶片多级堆叠的情况下,可以确保高抗冲击性并且可改善半导体制造后的电特性。
环氧类官能团可在构成(甲基)丙烯酸酯类树脂主链的重复单元处被取代一次或更多次。
环氧类官能团可包含环氧基或缩水甘油基。
包含含量为0.1重量%至10重量%的含有环氧类官能团的(甲基)丙烯酸酯类重复单元的(甲基)丙烯酸酯类树脂的玻璃化转变温度可为-10℃至20℃或-5℃至15℃。通过使用具有上述玻璃化转变温度的(甲基)丙烯酸酯类树脂,用于半导体的粘合膜可具有足够的流动性并且最终制备的粘合膜可确保高粘合强度,并且易于制备薄膜等形式的用于半导体的粘合膜。
为了控制用于半导体的粘合膜的固化程度或提高粘合性能等,粘合膜可包含固体环氧树脂。
固体环氧树脂的具体实例可包括选自以下的一种或更多种聚合物树脂:联苯类环氧树脂、双酚A环氧树脂、双酚F环氧树脂、甲酚酚醛清漆环氧树脂、苯酚酚醛清漆环氧树脂、四官能环氧树脂、三酚甲烷型环氧树脂、经烷基改性的三酚甲烷型环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂和经二环戊二烯改性的酚型环氧树脂。
固体环氧树脂的软化点可为50℃至120℃。如果固体环氧树脂的软化点太低,则用于半导体的粘合膜的粘合强度可增加,从而减少切割后芯片的拾取;而如果固体环氧树脂的软化点太高,则用于半导体的粘合膜的流动性可降低,并且粘合强度可降低。
固体环氧树脂的环氧当量重量可为100至1,000。
如果在用于半导体的粘合膜中,热塑性树脂的含量太低,则树脂组合物在固化之后的模量可快速增加,并因此难以预期基板与晶片之间的应力松弛效应。此外,如果热塑性树脂的含量太高,则在B阶段的组合物的粘度可增加,并因此在管芯连接过程中与基板的粘合力可降低,并且在固化过程期间的空隙去除可变得困难,从而降低所述过程和最终产品的可靠性。
如果含有酚树脂的固化剂的含量太低,则可能难以确保足够的耐热性。如果含有酚树脂的固化剂的含量太高,则即使固化完全,未反应的酚基仍可存在,从而增加吸湿性,并因此在半导体封装过程中水分吸收后的回流过程中,可引起基板和粘合剂之间的分层。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
根据本发明的另一个实施方案,提供了用于半导体的粘合膜,其在110℃的温度下在5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且在室温下的伸长率为500%或更低。
此前,考虑到用于半导体的粘合膜的可掩埋性等,提出了添加具有低软化点的组分以降低熔体粘度的方法,但该方法存在这样的限制:难以确保高弹性,并且断裂伸长率高。
因此,本发明人通过实验确定:具有上述特定特性的用于半导体的粘合膜可以更容易地掩埋不平坦,例如由于半导体基板的配线或附接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率,并且完成了本发明。
特别地,用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s。由于粘合膜在约110℃的温度下具有相对低的粘度,所以其可具有优异的粘合强度和对于半导体最佳化的流动性,这可有利于初始阶段固化的界面处和管芯连接过程中的空隙去除,并且在管芯连接之后,可顺利地实现接合线向周围空间的渗入,而不显著影响粘合膜的形状和特性。
此外,由于用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,因此即使长时间暴露于在半导体制造过程中施加的高温条件,也基本上不会产生空隙,并且当应用于切割管芯粘结膜等时,可以确保足够的高温剪切力,从而确保优异的可切割性。
此外,用于半导体的粘合膜在室温下的伸长率可为500%或更低、50%至500%、或者100%至400%。由于用于半导体的粘合膜具有相对高的弹性,并且还表现出低伸长率和低断裂伸长率,因此其即使在低温下也可具有优异的可切割性,并且即使在应用非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法时也可确保优异的可切割性。
同时,如果用于半导体的粘合膜在室温下表现出高于500%的伸长率,则即使在低温下进行扩展,可切割性也可能不足;如果将其在室温下静置,则可发生再粘合;并且由于在切割接合有粘合膜的晶片时所产生的热,粘合剂可软化以致在粘合膜中产生毛刺,从而污染半导体芯片的电路侧。
粘合膜可以用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。因此,粘合膜可加工成管芯粘结膜、切割管芯粘结膜等形式。
如上所述,如果用于半导体的粘合膜满足如下要求:在110℃的温度下在5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且在室温下的伸长率为500%或更低,则可实现上述效果,并且具体组分没有显著限制。
例如,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
环氧树脂可与玻璃化转变温度为-10℃至20℃的热塑性树脂和含有软化点为70℃或更高的酚树脂的固化剂一起形成粘合剂组分的基体(或基质),并且其使得用于半导体的粘合膜具有低粘度,并且还具有高断裂强度和低断裂伸长率。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
由于用于半导体的粘合膜包含上述范围的相对于热塑性树脂的固体环氧树脂和液体环氧树脂,所以用于半导体的粘合膜可在高温下具有低粘度,并且还可实现高弹性、优异的机械特性和高粘合强度。由于环氧树脂的含量相对于热塑性树脂相对较低等原因,此前已知的用于半导体的粘合膜不能实现上述实施方案的用于半导体的粘合膜的独特特性。
如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比低于上述范围,则用于半导体的粘合膜可在高温下表现出高粘度,或者表现出低断裂强度和高断裂伸长率,并且高温剪切力也可减小,因此不能充分确保可切割性。
此外,如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,则用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量可变得显著较高,或者粘合膜在室温下的伸长率可显著降低,从而极大地抑制可加工性。
此外,如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,则在固化过程中,用于半导体的粘合膜的粘度增加速率可显著增加,并因此可能难以除去所述膜内的空隙,这可能妨碍半导体封装的可靠性。
同时,在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
酚树脂可与液体环氧树脂和玻璃化转变温度为-10℃至30℃的热塑性树脂一起形成粘合剂组分的基体(或基质),其中所述酚树脂优选地以高于一定水平的含量包含在所述粘合剂组分的基体中。
特别地,如果在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比小于0.280,则不能向用于半导体的粘合膜提供足够的固化程度,从而降低耐热性;用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量可显著降低,并且粘合膜在室温下的伸长率可显著增加;并且在使用粘合膜制造的切割管芯粘结膜中,通过切割过程可过度产生毛刺,并且高温剪切力也可减小,并因此不能充分确保可切割性。
同时,包含在用于半导体的粘合膜中的固化剂可包含软化点为70℃或更高的酚树脂。所述酚树脂的软化点可为70℃或更高、80℃或更高、70℃至160℃、高于100℃且160℃或更低、或者105℃至150℃。
上述实施方案的用于半导体的粘合膜可包含软化点相对高的酚树脂,并且软化点为70℃或更高、80℃或更高、70℃至160℃、高于100℃且160℃或更低、或者105℃至150℃的酚树脂可与液体环氧树脂和玻璃化转变温度为-10℃至30℃的热塑性树脂一起形成粘合剂组分的基体(或基质),并且向用于半导体的粘合膜提供在室温下较高的拉伸模量和优异的粘合强度以及对于半导体最佳化的流动特性。
反之,如果酚树脂的软化点低于上述范围,则用于半导体的粘合膜在室温下的拉伸模量可降低,或者在室温下的伸长率可显著增加,并且用于半导体的粘合膜的熔体粘度可减小或者模量可降低,并因此可由在切割过程中产生的热产生更多毛刺,或者可切割性或拾取效率可降低。此外,如果接合粘合膜的过程或粘合膜长时间暴露于高温条件,则可能发生大量渗出。
此外,酚树脂的羟基当量重量可为80g/eq至400g/eq、或100g/eq至200g/eq。由于酚树脂具有上述的羟基当量重量范围,所以固化程度即使在短固化时间下也可增加,从而向用于半导体的粘合膜提供在室温下更高的拉伸模量和优异的粘合强度。
在上述实施方案的用于半导体的粘合膜中,液体环氧树脂相对酚树脂的重量比可为0.5至1.5。
如果液体环氧树脂相对酚树脂的重量比太高,则用于半导体的粘合膜的断裂强度可显著增加,在室温下的拉伸模量可降低,并且在低温切割过程中的可切割性或效率可降低。
此外,如果液体环氧树脂相对酚树脂的重量比太低,则在室温下在伸长率下产生的模量可变得太高,或者在室温下的伸长率可显著降低,从而显著降低最终产品的产率,并且用于半导体的粘合膜不能与晶片充分粘合,从而在制造过程中发生晶片与粘合膜之间的剥离。
液体环氧树脂的具体种类和性质没有显著限制,但是例如,液体环氧树脂在25℃下的粘度可为500mPa·s至20,000mPa·s。此外,液体环氧树脂的环氧当量重量可为100至1,000。
同时,液体环氧树脂可与玻璃化转变温度为-10℃至30℃的热塑性树脂和含有酚树脂的固化剂一起形成粘合剂组分的基体(或基质),并使粘合膜具有相对低的粘度,并且还具有优异的粘合强度和对于半导体最佳化的流动特性,并因此可有利于初始阶段固化中的界面处和管芯连接过程中的空隙去除。
如上所述,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂。
热塑性树脂的实例没有特别限制,但是例如可包括:聚酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚酰胺、聚醚砜、聚醚酮、聚烯烃、聚氯乙烯、苯氧基树脂、反应性丁二烯-丙烯腈共聚物橡胶、(甲基)丙烯酸酯类树脂、其中两种或更多种的混合物、或者其中两种或更多种的共聚物。
特别地,(甲基)丙烯酸酯类树脂可为包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂。
通过使用包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂,在将用于半导体的粘合膜用于超薄晶片多级堆叠的情况下,可确保高抗冲击性并可改善半导体制造后的电特性。
环氧类官能团可在构成(甲基)丙烯酸酯类树脂主链的重复单元处被取代一次或更多次。
环氧类官能团可包含环氧基或缩水甘油基。
包含含量为0.1重量%至10重量%的含有环氧类官能团的(甲基)丙烯酸酯类重复单元的(甲基)丙烯酸酯类树脂的玻璃化转变温度可为-10℃至20℃或-5℃至15℃。通过使用具有上述玻璃化转变温度的(甲基)丙烯酸酯类树脂,用于半导体的粘合膜可具有足够的流动性并且最终制备的粘合膜可确保高粘合强度,并且易于制备薄膜等形式的用于半导体的粘合膜。
为了控制用于半导体的粘合膜的固化程度或提高粘合性能等,粘合膜可包含固体环氧树脂。
固体环氧树脂的具体实例可包括选自以下的一种或更多种聚合物树脂:联苯类环氧树脂、双酚A环氧树脂、双酚F环氧树脂、甲酚酚醛清漆环氧树脂、苯酚酚醛清漆环氧树脂、四官能环氧树脂、三酚甲烷型环氧树脂、经烷基改性的三酚甲烷型环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂和经二环戊二烯改性的酚型环氧树脂。
固体环氧树脂的软化点可为50℃至120℃。如果固体环氧树脂的软化点太低,则用于半导体的粘合膜的粘合强度可增加,从而减少切割后芯片的拾取;而如果固体环氧树脂的软化点太高,则用于半导体的粘合膜的流动性可降低,并且粘合强度可降低。
固体环氧树脂的环氧当量重量可为100至1,000。
如果在用于半导体的粘合膜中,热塑性树脂的含量太低,则树脂组合物在固化之后的模量可快速增加,并因此难以预期基板与晶片之间的应力松弛效应。此外,如果热塑性树脂的含量太高,则在B阶段的组合物的粘度可增加,并因此在管芯连接过程中与基板的粘合力可降低,并且在固化过程期间的空隙去除可变得困难,从而降低所述过程和最终产品的可靠性。
如果含有酚树脂的固化剂的含量太低,则可能难以确保足够的耐热性。如果含有酚树脂的固化剂的含量太高,则即使固化完全,未反应的酚基仍可存在,从而增加吸湿性,并因此在半导体封装过程中水分吸收后的回流过程中,可引起基板和粘合剂之间的分层。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
根据本发明的另一个实施方案,提供了用于半导体的粘合膜,其在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且在室温下的伸长率为500%或更低。
此前已知的用于半导体的粘合膜不能确保低断裂伸长率和高弹性,并因此不能实现足够的可掩埋性和可切割性。
因此,本发明人通过实验确定:具有上述特定特性的用于半导体的粘合膜可以更容易地掩埋不平坦,例如由于半导体基板的配线或附接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率,并且完成了本发明。
特别地,由于用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量为50MPa或更高、或者50MPa至300MPa,所以该实施方案的粘合膜可以容易地应用于非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法,并因此即使在低温下也具有优异的可切割性。
如果用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量低于50MPa,则即使在低温下进行扩展,可切割性也可能不足;如果将其在室温下静置,则可发生再粘合;并且由于在切割粘合膜所接合的晶片时产生的热,粘合剂可软化以致在粘合膜中产生毛刺,从而污染半导体芯片的电路侧。
此外,用于半导体的粘合膜在室温下的伸长率可为500%或更低、50%至500%、或者100%至400%。由于用于半导体的粘合膜具有相对高的弹性,并且还表现出低伸长率和低断裂伸长率,因此其即使在低温下也可具有优异的可切割性,并且即使在应用非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法时也可确保优异的可切割性。
同时,如果用于半导体的粘合膜表现出在室温下高于500%的伸长率,则即使在低温下进行扩展,可切割性也可能不足;如果将其在室温下静置,则可发生再粘合;并且由于在切割接合有粘合膜的晶片时所产生的热,粘合剂可软化以致在粘合膜中产生毛刺,从而污染半导体芯片的电路侧。
粘合膜可以用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。因此,粘合膜可加工成管芯粘结膜、切割管芯粘结膜等形式。
如上所述,如果用于半导体的粘合膜满足如下要求:在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且在室温下的伸长率为500%或更低,则可实现上述效果,并且具体组分没有显著限制。
例如,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
更特别地,用于半导体的粘合膜可包含:连续相基体,包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、和液体环氧树脂;以及分散在所述连续相基体中的固体环氧树脂。
环氧树脂可与玻璃化转变温度为-10℃至20℃的热塑性树脂和含有软化点为70℃或更高的酚树脂的固化剂一起形成粘合剂组分的基体(或基质),并且其使得用于半导体的粘合膜在具有低粘度的同时具有高断裂强度和低断裂伸长率。
在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比可为1.6至2.6、1.7至2.5、1.75至2.4、或1.8至2.3。
由于用于半导体的粘合膜包含上述范围的相对于热塑性树脂的固体环氧树脂和液体环氧树脂,所以用于半导体的粘合膜可在高温下具有低粘度,并且还可实现高弹性、优异的机械特性和高粘合强度。由于环氧树脂的含量相对于热塑性树脂相对较低等原因,此前已知的用于半导体的粘合膜不能实现上述实施方案的用于半导体的粘合膜的独特特性。
如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比低于上述范围,则用于半导体的粘合膜可在高温下表现出高粘度,或者表现出低断裂强度和高断裂伸长率,并且高温剪切力也可减小,因此不能充分确保可切割性。
此外,如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,则用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量可变得显著较高,或者粘合膜在室温下的伸长率可显著降低,从而极大地抑制可加工性。
此外,如果在用于半导体的粘合膜中,固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,则在固化过程中,用于半导体的粘合膜的粘度增加速率可显著增加,并因此可能难以除去所述膜内的空隙,这可能妨碍半导体封装的可靠性。
同时,在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比可为0.280或更大、或者0.300至0.600。
酚树脂可与液体环氧树脂和玻璃化转变温度为-10℃至30℃的热塑性树脂一起形成粘合剂组分的基体(或基质),其中所述酚树脂优选地以高于一定水平的含量包含在所述粘合剂组分的基体中。
特别地,如果在用于半导体的粘合膜中,酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比小于0.280,则不能向用于半导体的粘合膜提供足够的固化程度,从而降低耐热性;粘合膜在室温下在5%至10%伸长率下产生的模量可显著降低,并且粘合膜在室温下的伸长率可显著增加;并且在使用粘合膜制造的切割管芯粘结膜中,通过切割过程可过度产生毛刺,并且高温剪切力也可减小,并因此不能充分确保可切割性。
同时,包含在用于半导体的粘合膜中的固化剂可包含软化点为70℃或更高的酚树脂。所述酚树脂的软化点可为70℃或更高、80℃或更高、70℃至160℃、高于100℃且160℃或更低、或者105℃至150℃。
上述实施方案的用于半导体的粘合膜可包含软化点相对高的酚树脂,并且软化点为70℃或更高、80℃或更高、70℃至160℃、高于100℃且160℃或更低、或者105℃至150℃的酚树脂可与液体环氧树脂和玻璃化转变温度为-10℃至30℃的热塑性树脂一起形成粘合剂组分的基体(或基质),并且向用于半导体的粘合膜提供在室温下较高的拉伸模量和优异的粘合强度以及对于半导体最佳化的流动特性。
反之,如果酚树脂的软化点低于上述范围,则用于半导体的粘合膜在室温下的拉伸模量可降低,或者在室温下的伸长率可显著增加,并且用于半导体的粘合膜的熔体粘度可减小或者模量可降低,并因此可由在切割过程中产生的热产生更多毛刺,或者可切割性或拾取效率可降低。此外,如果接合粘合膜的过程或粘合膜长时间暴露于高温条件,则可能发生大量渗出。
此外,酚树脂的羟基当量重量可为80g/eq至400g/eq、或100g/eq至200g/eq。由于酚树脂具有上述的羟基当量重量范围,所以固化程度即使在短固化时间下也可增加,从而向用于半导体的粘合膜提供在室温下更高的拉伸模量和优异的粘合强度。
在上述实施方案的用于半导体的粘合膜中,液体环氧树脂相对酚树脂的重量比可为0.5至1.5。
如果液体环氧树脂相对酚树脂的重量比太高,则用于半导体的粘合膜的断裂强度可显著增加,在室温下的拉伸模量可降低,并且在低温切割过程中的可切割性或效率可降低。
此外,如果液体环氧树脂相对酚树脂的重量比太低,则在室温下在伸长率下产生的模量可变得太高,或者在室温下的伸长率可显著降低,从而显著降低最终产品的产率,并且用于半导体的粘合膜不能与晶片充分粘合,从而在制造过程中发生晶片与粘合膜之间的剥离。
液体环氧树脂的具体种类和性质没有显著限制,但是例如,液体环氧树脂在25℃下的粘度可为500mPa·s至20,000mPa·s。此外,液体环氧树脂的环氧当量重量可为100至1,000。
同时,液体环氧树脂可与玻璃化转变温度为-10℃至30℃的热塑性树脂和含有酚树脂的固化剂一起形成粘合剂组分的基体(或基质),并使粘合膜具有相对低的粘度,并且还具有优异的粘合强度和对于半导体最佳化的流动特性,并因此可有利于初始阶段固化中的界面处和管芯连接过程中的空隙去除。
如上所述,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂。
热塑性树脂的实例没有特别限制,但是例如可包括:聚酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚酰胺、聚醚砜、聚醚酮、聚烯烃、聚氯乙烯、苯氧基树脂、反应性丁二烯-丙烯腈共聚物橡胶、(甲基)丙烯酸酯类树脂、其中两种或更多种的混合物、或者其中两种或更多种的共聚物。
特别地,(甲基)丙烯酸酯类树脂可为包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂。
通过使用包含含有环氧类官能团的(甲基)丙烯酸酯类重复单元并且玻璃化转变温度为-10℃至20℃的(甲基)丙烯酸酯类树脂,在将用于半导体的粘合膜用于超薄晶片多级堆叠的情况下,可确保高抗冲击性并可改善半导体制造后的电特性。
环氧类官能团可在构成(甲基)丙烯酸酯类树脂主链的重复单元处被取代一次或更多次。
环氧类官能团可包含环氧基或缩水甘油基。
包含含量为0.1重量%至10重量%的含有环氧类官能团的(甲基)丙烯酸酯类重复单元的(甲基)丙烯酸酯类树脂的玻璃化转变温度可为-10℃至20℃或-5℃至15℃。通过使用具有上述玻璃化转变温度的(甲基)丙烯酸酯类树脂,用于半导体的粘合膜可具有足够的流动性并且最终制备的粘合膜可确保高粘合强度,并且易于制备薄膜等形式的用于半导体的粘合膜。
为了控制用于半导体的粘合膜的固化程度或提高粘合性能等,粘合膜可包含固体环氧树脂。
固体环氧树脂的具体实例可包括选自以下的一种或更多种聚合物树脂:联苯类环氧树脂、双酚A环氧树脂、双酚F环氧树脂、甲酚酚醛清漆环氧树脂、苯酚酚醛清漆环氧树脂、四官能环氧树脂、三酚甲烷型环氧树脂、经烷基改性的三酚甲烷型环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂和经二环戊二烯改性的酚型环氧树脂。
固体环氧树脂的软化点可为50℃至120℃。如果固体环氧树脂的软化点太低,则用于半导体的粘合膜的粘合强度可增加,从而减少切割后芯片的拾取;而如果固体环氧树脂的软化点太高,则用于半导体的粘合膜的流动性可降低,并且粘合强度可降低。
固体环氧树脂的环氧当量重量可为100至1,000。
如果在用于半导体的粘合膜中,热塑性树脂的含量太低,则树脂组合物在固化之后的模量可快速增加,并因此难以预期基板与晶片之间的应力松弛效应。此外,如果热塑性树脂的含量太高,则在B阶段的组合物的粘度可增加,并因此在管芯连接过程中与基板的粘合力可降低,并且在固化过程期间的空隙去除可变得困难,从而降低所述过程和最终产品的可靠性。
如果含有酚树脂的固化剂的含量太低,则可能难以确保足够的耐热性。如果含有酚树脂的固化剂的含量太高,则即使固化完全,未反应的酚基仍可存在,从而使吸湿性增加,并因此在半导体封装过程中水分吸收后的回流过程中,可引起基板和粘合剂之间的分层。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
根据本发明的另一个实施方案,提供了用于半导体的粘合膜,其在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且在室温下的伸长率为500%或更低。
此前已知的用于半导体的粘合膜不能确保低断裂伸长率和高弹性,并因此不能实现足够的可掩埋性和可切割性。
此外,此前,考虑到用于半导体的粘合膜的可掩埋性等,提出了添加具有低软化点的组分以降低熔体粘度的方法,但是该方法存在这样的限制:难以确保高弹性,并且断裂伸长率高。
因此,本发明人通过实验确定:具有上述特定特性的用于半导体的粘合膜可以更容易地掩埋不平坦,例如由于半导体基板的配线、附接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率,并且完成了本发明。
特别地,由于用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量为50MPa或更高、或者50MPa至300MPa,所以该实施方案的粘合膜可以容易地应用于非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法,并因此即使在低温下也具有优异的可切割性。
如果用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量低于50MPa,则即使在低温下进行扩展,可切割性也可能不足;如果将其在室温下静置,则可发生再粘合;并且由于在切割粘合膜所接合的晶片时产生的热,粘合剂可软化以致在粘合膜中产生毛刺,从而污染半导体芯片的电路侧。
此外,用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s。由于粘合膜在约110℃的温度下具有相对低的粘度,所以其可具有优异的粘合强度和对于半导体最佳化的流动性,这可有利于初始阶段固化的界面处和管芯连接过程中的空隙去除,并且在管芯连接之后,可顺利地实现接合线向周围空间的渗入,而不显著影响粘合膜的形状和特性。
此外,由于用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,因此即使长时间暴露于在半导体制造过程中施加的高温条件,也基本上不会产生空隙,并且当应用于切割管芯粘结膜等时,可确保足够的高温剪切力,从而确保优异的可切割性。
此外,用于半导体的粘合膜在室温下的伸长率可为500%或更低、50%至500%、或者100%至400%。由于用于半导体的粘合膜具有相对高的弹性并且还表现出低伸长率和低断裂伸长率,因此其即使在低温下也可具有优异的可切割性,并且即使在应用非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法时也可确保优异的可切割性。
同时,如果用于半导体的粘合膜表现出高于500%的伸长率,则即使在低温下进行扩展,可切割性也可能不足;如果将其在室温下静置,则可发生再粘合;并且由于在切割接合有粘合膜的晶片时所产生的热,粘合剂可软化以致在粘合膜中产生毛刺,从而污染半导体芯片的电路侧。
粘合膜可以用作管芯粘附膜(DAF)以用于连接引线框或基板与管芯或者连接管芯与管芯。因此,粘合膜可加工成管芯粘结膜、切割管芯粘结膜等形式。
如上所述,如果用于半导体的粘合膜满足如下要求:在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且在室温下的伸长率为500%或更低,则可实现上述效果,并且具体组分没有显著限制。
例如,用于半导体的粘合膜可包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂。
玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为70℃或更高的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂的详情包括以上关于以上实施方案的用于半导体的粘合膜所说明的内容。
用于半导体的粘合膜的厚度可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
包含在上述实施方案的各用于半导体的粘合膜中的固化剂还可包括选自胺类固化剂和酸酐类固化剂的一种或更多种化合物。
考虑到最终所制备的粘合膜的特性等,可适当选择所使用的固化剂的量,并且例如,基于100重量份的环氧树脂,其可以以10重量份至700重量份或30重量份至300重量份的量使用。
用于半导体的粘合膜还可包含固化催化剂。
固化催化剂的功能是促进固化剂的作用或者促进用于半导体的粘合膜的固化,并且可以没有显著限制地使用已知用于制造用于半导体的粘合膜等的任何固化催化剂。例如,作为固化催化剂,可使用选自以下的一种或更多种:磷化合物、硼化合物、磷-硼化合物和咪唑类化合物。考虑到粘合膜的特性等,可适当选择所使用的固化催化剂的量,并且例如,基于100重量份的液体环氧树脂、固体环氧树脂、(甲基)丙烯酸酯类树脂和酚树脂,固化催化剂可以以0.5重量份至10重量份的量使用。
用于半导体的粘合膜还可包含离子清除剂,所述离子清除剂包括含有选自锆、锑、铋、镁和铝的一种或更多种金属的金属氧化物;多孔硅酸盐;多孔铝硅酸盐;或者沸石。
含有选自锆、锑、铋、镁和铝的一种或更多种金属的金属氧化物的实例可包括氧化锆、氧化锑、氧化铋、氧化镁、氧化铝、基于锑铋的氧化物、基于锆铋的氧化物、基于锆镁的氧化物、基于镁铝的氧化物、基于锑镁的氧化物、基于锑铝的氧化物、基于锑锆的氧化物、基于锆铝的氧化物、基于铋镁的氧化物、基于铋铝的氧化物、或者其中两种或更多种的混合物。
离子清除剂可用于吸附存在于用于半导体的粘合膜内的金属离子或卤素离子等,并因此可提高与粘合膜接触的配线的电可靠性。
用于半导体的粘合膜中的离子清除剂的含量没有显著限制,但是考虑到与过渡金属离子的反应性、可加工性和由树脂组合物制造的粘合膜的特性,基于用于半导体的粘合膜的重量,离子清除剂可以以0.01重量%至20重量%,优选0.01重量%至10重量%的含量包含在内。
用于半导体的粘合膜还可包含选自偶联剂和无机填料的一种或更多种添加剂。偶联剂和无机填料的实例没有特别限制,并且可没有显著限制地使用已知可在用于半导体封装的粘合剂中使用的组分。
根据本发明的又一个实施方案,提供了切割管芯粘结膜,其包含:基础膜;形成在所述基础膜上的粘性层;以及形成在所述粘性层上的粘合剂层,所述粘合剂层包含根据上述实施方案中任一个的用于半导体的粘合膜。
由于切割管芯粘结膜的粘合剂层包含根据上述实施方案中任一个的用于半导体的粘合膜,因此切割管芯粘结膜可具有优异的机械特性(例如,耐热性和抗冲击性等)和高粘合强度,并且表现出低吸湿性,从而防止水分蒸发、基板和管芯粘结膜之间的分层或者由于蒸发所产生的回流裂纹等。
此外,由于切割管芯粘结膜的粘合剂层包含根据上述实施方案中任一个的用于半导体的粘合膜,因此具有上述特定特性的用于半导体的粘合膜可以更容易地掩埋不平坦,例如由于半导体基板的配线或附接至半导体芯片的配线等引起的不平坦,并且还可以没有特别限制地应用于各种切割方法以实现优异的可切割性,从而提高半导体封装工艺的可靠性和效率。
此外,如上所述,由于切割管芯粘结膜包含具有上述特定特性的用于半导体的粘合膜,因此其可以容易地应用于非接触型切割方法例如DBG(研磨前切割)和使用刀片的晶片切割方法,并且粘合剂层即使在低温下也可具有优异的可切割性。
根据上述实施方案中任一个的用于半导体的粘合膜的详情如上所述。
特别地,用于半导体的粘合膜在110℃的温度和5rad/s的剪切速率下的熔体粘度可为1,000Pa·s至4,000Pa·s。
此外,用于半导体的粘合膜在室温下在5%至10%伸长率下产生的模量可为50MPa或更高。
此外,用于半导体的粘合膜的伸长率可为500%或更低。
包含在切割管芯粘结膜中的基础膜的种类没有特别限制,并且例如,可使用本领域中已知的塑料膜或金属箔等。
例如,基础膜可包括低密度聚乙烯、线性聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、聚丙烯的无规共聚物、聚丙烯的嵌段共聚物、均聚聚丙烯、聚甲基戊烯、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-离聚物共聚物、乙烯-乙烯醇共聚物、聚丁烯、苯乙烯共聚物、或者其中两者或更多者的混合物。
包含两种或更多种聚合物的混合物的基础膜包括多层膜和单层膜二者,所述多层膜的每个膜层包含上述聚合物,所述单层膜包含两种或更多种上述聚合物。
基础膜的厚度没有特别限制,并且通常,其形成的厚度为10μm至200μm,优选50μm至180μm。如果厚度小于10μm,则存在切割过程中切割深度的控制可能不稳定的问题;而如果厚度大于200μm,则在切割过程中可能产生大量毛刺或伸长率可能降低,并因此不能准确地完成扩展过程。
如有必要,基础膜可经历一般的物理或化学处理,例如哑光处理、电晕放电处理、底漆处理、交联等。
同时,粘性层可包含可UV固化的粘合剂或可热固化的粘合剂。在使用可UV固化的粘合剂的情况下,从基础膜侧照射UV以提高粘合剂的内聚性和玻璃化转变温度,从而降低粘合强度;而在使用可热固化的粘合剂的情况下,提高温度以降低粘合强度。
此外,可UV固化的粘合剂可包含(甲基)丙烯酸酯类树脂、可UV固化的化合物、光引发剂和交联剂。
(甲基)丙烯酸酯类树脂的重均分子量可为100,000至1,500,000,优选200,000至1,000,000。如果重均分子量小于100,000,则可涂覆性或内聚性可能降低,并因此在分层时残余物可能保留在粘合物中,或者可能出现粘合剂破裂。此外,如果重均分子量大于1,500,000,则基础树脂可能阻碍可UV固化的化合物反应,并因此存在不能有效地实现剥离强度降低的问题。
(甲基)丙烯酸酯类树脂的实例可包括(甲基)丙烯酸酯类单体和含可交联官能团单体的共聚物。其中,(甲基)丙烯酸酯类单体的实例可包括(甲基)丙烯酸烷基酯,特别是具有碳原子数为1至12的烷基的单体,例如(甲基)丙烯酸戊酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸癸酯或其混合物。随着单体的烷基的碳数变高,最终共聚物的玻璃化转变温度变低,因此可以根据期望的玻璃化转变温度选择合适的单体。
含可交联官能团单体的实例可包括含羟基单体、含羧基单体、含氮单体或其混合物。含羟基化合物的实例可包括(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯等;含羧基化合物的实例可包括(甲基)丙烯酸酯等;含氮单体的实例可包括(甲基)丙烯腈、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺等,但不限于此。
在(甲基)丙烯酸酯类树脂中,可额外地包含含碳-碳双键的低分子量化合物,例如乙酸乙烯酯、苯乙烯、丙烯腈等,以改善其他功能性如相容性等。
可UV固化的化合物的种类没有特别限制,并且例如,可使用重均分子量为500至300,000的多官能化合物(例如,多官能氨基甲酸酯丙烯酸酯、多官能丙烯酸酯单体或低聚物等)。本领域普通技术人员可根据期望用途容易地选择合适的化合物。
基于100重量份的上述基础树脂,可UV固化的化合物的含量可为5重量份至400重量份,优选10重量份至200重量份。如果可UV固化的化合物的含量小于5重量份,则固化后的粘合力降低可能不足,并因此存在降低拾取性的问题;而如果可UV固化的化合物的含量大于400重量份,则在UV照射之前粘合剂的内聚性可能不足,或者可能不易实现与离型膜等的分层。
光引发剂的种类没有特别限制,并且可使用本领域公知的那些,其中基于100重量份的可UV固化的化合物,其含量可为0.05重量份至20重量份。如果光引发剂的含量小于0.05重量份,则通过UV照射的固化反应可能变得不足而降低拾取性;而如果其含量大于20重量份,则在固化过程中可能与短单元发生交联反应,可产生未反应的可UV固化的化合物以在粘合表面上产生残余物,或者固化后的剥离强度可能过度降低而降低拾取性。
此外,包含在粘性部分中以提供粘合力和内聚性的交联剂的种类也没有特别限制,并且可使用常用的那些,例如异氰酸酯类化合物、氮丙啶类化合物、环氧类化合物、金属螯合物类化合物等。基于100重量份的基础树脂,交联剂可以以2重量份至40重量份,优选2重量份至20重量份的含量包含在内。如果其含量小于2重量份,则粘合剂的内聚性可能不足;而如果其含量大于20重量份,则UV照射前的粘合力可能不足,并因此存在芯片分散等问题。此外,在粘性层中还可包含增粘剂,例如松香树脂、萜烯树脂、酚树脂、苯乙烯树脂、脂肪族石油树脂、芳香族石油树脂、脂肪族芳香族共聚物石油树脂等。
用于在基础膜上形成包含上述组分的粘性层的方法没有特别限制,并且例如可使用将粘合剂组合物直接涂覆在基础膜上以形成粘性层的方法;或者先将粘合剂组合物涂覆在可剥离基底上以制备粘性层,然后使用可剥离基底将粘性层转移至基础膜的方法;等等。
在此,涂覆和干燥粘合剂组合物的方法没有特别限制,并且例如可使用以下方法:按原样涂覆含有上述组分的组合物,或者将其稀释在合适的有机溶剂中并通过已知工具(例如,缺角轮涂布机(comma coater)、凹版涂布机、模压涂布机、反向涂布机等)涂覆,然后在60℃至200℃的温度下干燥溶剂10秒至30分钟。此外,在上述过程中,还可进行老化过程以进行粘合剂的充分交联。
虽然粘性层的厚度没有特别限制,但是例如,其可为1μm至600μm、3μm至500μm、或5μm至300μm。
如上所述,粘合剂层在粘性层上形成,并且可包含上述实施方案的用于半导体的粘合膜。用于半导体的粘合膜的详情包括上述的那些。
虽然粘合剂层的厚度没有特别限制,但是例如,其可为1μm至300μm。此外,粘合膜的厚度可为1μm或更大、3μm或更大、5μm或更大、或者10μm或更大。此外,粘合膜的厚度可为300μm或更小、100μm或更小、90μm或更小、或者70μm或更小。
切割管芯粘结膜还可包含形成在粘合剂层上的离型膜。可以使用的离型膜的实例可包括一种或更多种塑料膜,例如聚对苯二甲酸乙二醇酯膜、聚四氟乙烯膜、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、氯乙烯共聚物膜、聚酰亚胺膜等。
离型膜的表面可用醇酸树脂类、硅类、氟类、不饱和酯类、聚烯烃类或蜡类离型剂中的一种或更多种进行处理,其中可优选耐热的醇酸树脂类、硅类或氟类离型剂。
离型膜可通常形成为10μm至500μm,优选约20μm至200μm的厚度,但不限于此。
用于制造上述切割管芯粘结膜的方法没有特别限制,并且例如可使用在基础膜上顺序形成粘性部分、粘合剂部分和离型膜的方法;或者单独制备切割膜(基础膜+粘性部分)和在其上形成有管芯粘结膜或粘合剂部分的离型膜然后将其层合的方法;等等。
层合方法没有特别限制,并且可使用热轧层合法或层合压制,其中就连续过程的可能性和效率而言,优选热轧层合法。热轧层合法可在10℃至100℃的温度和0.1kgf/cm2至10kgf/cm2的压力下进行,但不限于此。
根据本发明的另一个实施方案,提供了用于切割半导体晶片的方法,其包括以下步骤:对包含切割管芯粘结膜的半导体晶片进行部分预处理;将晶片层合在切割管芯粘结膜的至少一侧上以使其完全切割或可切割;以及将UV照射至经预处理的半导体晶片的基础膜,并且拾取通过切割半导体所分离的单独芯片。
切割管芯粘结膜的详情包括上述的那些。
除关于切割方法的步骤的细节以外,可没有特别限制地使用用于半导体晶片等的切割方法的公知设备和方法。
用于切割半导体晶片的方法还可包括在预处理之后扩展半导体晶片的步骤。在这种情况下,接着进行如下过程:将UV照射至经扩展的半导体晶片的基础膜并且拾取通过切割半导体晶片所分离的单独芯片。
通过使用包含切割膜的切割管芯粘结膜,可使在半导体晶片的切割过程期间产生的毛刺最小化,从而防止半导体芯片的污染并且提高半导体芯片的可靠性和寿命。
本发明的具体实施方案将在以下实施例中进行详细说明。然而,这些实施例仅用于举例说明本发明的具体实施方案,并且本发明的范围不限于此。
[实施例1至5和比较例1至3:用于半导体的粘合剂树脂组合物和用于半导体的粘合膜的制备]
实施例1
(1)用于半导体的粘合剂树脂组合物的溶液的制备
将40g酚树脂KH-6021(由DIC公司生产,双酚A酚醛清漆树脂,羟基当量重量121g/eq,软化点:125℃)(其为环氧树脂的固化剂)、38g环氧树脂EOCN-104S(由日本化药有限公司生产,甲酚酚醛清漆型环氧树脂,环氧当量重量214g/eq,软化点:83℃)、50g液体环氧树脂RE-310S(由日本化药有限公司生产,双酚A环氧树脂,环氧当量重量为180g/eq)、40g热塑性丙烯酸酯树脂KG-3015(Mw:900,000,玻璃化转变温度:10℃)、5g硅烷偶联剂A-187(GEToshiba Silicone,γ-缩水甘油氧基丙基三甲氧基硅烷)、0.1g固化促进剂2PZ(ShikokuChemicals公司,2-苯基咪唑)和100g填料SC-2050(Admatec公司,球形二氧化硅,平均粒径约400nm)在甲基乙基酮溶剂中混合以获得用于半导体的粘合剂组合物的溶液(固体含量20重量%)。
(2)管芯粘结膜的制备
将以上制备的用于半导体的粘合剂组合物的溶液涂覆在经离型处理的聚对苯二甲酸乙二醇酯膜(厚度38μm)上,然后在110℃下干燥3分钟以获得厚度为约60μm的用于半导体的粘合膜(管芯粘结膜)。
实施例2至5
通过与实施例1相同的方法获得用于半导体的粘合剂树脂组合物的溶液(固体含量20重量%)和用于半导体的粘合膜(管芯粘结膜),不同之处在于使用下表1中所述的组分和量。
比较例1和2
通过与实施例1相同的方法获得用于半导体的粘合膜(管芯粘结膜),不同之处在于使用下表1中的组分和含量制备用于半导体的粘合剂树脂组合物的溶液(在甲基乙基酮中的浓度为20重量%)。
[表1]
实施例和比较例的树脂组合物的组成[单位:g]
-KH-6021:双酚A酚醛清漆树脂(DIC公司,软化点:125℃)
-GPH-103:联苯酚醛清漆树脂(日本化药有限公司,软化点:103℃)
-HE200C-17:联苯酚醛清漆树脂(Air Water有限公司,软化点:75℃)
-KPH-3065:xyloc A酚醛清漆苯酚树脂(Kolon Chemical有限公司,羟基当量重量:180g/eq,软化点67℃)
-KG-3015P:丙烯酸酯类树脂(包含3重量%的缩水甘油基甲基丙烯酸酯类重复单元,玻璃化转变温度:10℃,重均分子量900,000)
-EOCN-104S:甲酚酚醛清漆环氧树脂(日本化药有限公司,环氧当量重量:180g/eq,软化点:90℃)
-RE-310S:双酚A环氧液体树脂(日本化药,环氧当量重量:约180g/eq,在25℃下的粘度:约13,000mPa·s至17,000mPa·s)
[实验例:用于半导体的粘合膜的特性评估]
实验例1:熔体粘度的测量
将实施例和比较例中分别获得的粘合膜堆叠至650μm的厚度,然后使用辊式层合机在60℃下层合。其后,使每个试样形成直径为10mm的圆形,然后使用TA公司的先进流变扩展系统(advanced rheometric expansion system,ARES)在40℃至160℃的温度范围内、1Hz且5rads的剪切速率和20℃/分钟的温度上升速率下测量根据温度而变化的熔体粘度。
实验例2:室温拉伸特性的评估
为了测量实施例和比较例中分别获得的粘合膜的拉伸特性,使用质构仪(TextureAnalyzer,Stable Micro System,Ltd.)。具体地,将实施例和比较例中分别获得的粘合膜切割成宽度为15mm且长度为100mm的尺寸以制备样品,并且两端均贴上胶带而留下50mm的样品中心部分。此外,将贴上胶带的样品的两端固定至该设备,并且在以0.3mm/秒的速率伸长时,绘制拉伸曲线。由拉伸曲线测量5%伸长率下的斜率值以确定模量,并且测量样品被完全切割时的时间以确定伸长率。
实验例3:毛刺产生的观察
(1)切割膜的制造
使75g丙烯酸2-乙基己酯、10g甲基丙烯酸2-乙基己酯和15g丙烯酸2-羟基乙酯在300g丙烯酸乙酯溶剂中共聚,以获得重均分子量为850,000的共聚物(玻璃化转变温度:10℃),然后向其中添加10g可光固化材料丙烯酸异氰酸酯化合物,从而获得反应物。其后,将10g多官能异氰酸酯低聚物和1g作为光引发剂的Darocur TPO混合以制备可UV固化的粘合剂组合物。
将可UV固化的粘合剂组合物涂覆在厚度为38μm的经离型处理的聚酯膜上,使得干燥后的厚度变成10μm,并在110℃下干燥3分钟。将经干燥的粘性层层合在厚度为100μm的聚烯烃膜上以制造切割膜。
(2)切割管芯粘结膜的制造
将在上述过程中获得的粘性层以及实施例和比较例中获得的各粘合膜(宽度:18mm,长度:10cm)层合以制造用于切割管芯接合的多层粘合膜。
(3)毛刺产生率的测量
使用100μm晶片和晶片环安装器在50℃下层合以上制备的各切割管芯粘结膜,并且使用切割设备以40K rpm和20mm/秒的速率将其切割成10mm*10mm的芯片尺寸,然后确定管芯上产生的毛刺数量以测量毛刺产生率。
实验例4:高温剪切力的评估
在60℃的条件下,在厚度为约600μm至700μm的晶片的镜面侧上层合实施例和比较例中分别获得的粘合膜,并将晶片分段为5mm*5mm的尺寸以制备具有该管芯尺寸的粘合膜。此外,将10mm*10mm尺寸的70μm晶片镜面置于130℃的热板上,然后在2kg且2秒的晶片管芯的条件下连接管芯粘结膜,在125℃下进行固化1小时,并在175℃下再进行固化2小时。
此外,在于250℃下以0.05mm/秒的速率按压晶片管芯的同时,使用管芯剪切测试仪DAGE 4000测量力,以测量高温剪切力。
实验例5:可切割性的评估
将实施例1至4和比较例1和2中获得的粘合剂层合至切割膜,由此制造切割管芯粘结膜。
使用预切成5mm*5mm尺寸的厚度为50μm的8英寸晶片和晶片环安装器,在60℃下层合以上制备的各切割管芯粘结膜,然后使其在室温下静置30分钟。其后,在低温室中安装层合有切割管芯粘结膜的晶片,并在-10℃下以100mm/秒的速率进行低温扩展至5mm的高度。此外,将晶片转移至热收缩装置,并以1mm/秒扩展至4mm,然后加热以使切割膜热收缩。其后,确定晶片在室温下的切割比。
[表2]
实验例的结果
如表2中所示,可确定,由于实施例1至5中制备的粘合膜在室温下在5%至10%伸长率下产生的模量为50MPa至150MPa,在110℃的温度和5rad/秒的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且在室温下的伸长率为500%或更低,因此即使在室温下进行扩展,也可确保100%的可切割性。
还可确定,在使用实施例1至5的粘合膜制造的切割管芯粘结膜中,通过切割过程基本上不产生毛刺,并且实施例1至5的粘合膜具有高的高温剪切力,并因此具有改善的耐热性和粘合强度。
制备比较例1的粘合膜使得固体环氧树脂和液体环氧树脂的总含量相对热塑性树脂的重量比大于2.6,并且酚树脂相对热塑性树脂、酚树脂和液体环氧树脂的总重量的重量比小于0.280。如表2中所示,可确定在比较例1的粘合膜的情况下,在室温下在5%至10%伸长率下产生的模量小于40MPa,并且在室温下的伸长率大于550%。
此外,还可确定,在其中使用具有低软化点的酚树脂的比较例2的情况下,在室温下在5%至10%伸长率下产生的模量小于30MPa,并且在室温下的伸长率达到750%。
可确定由于比较例1和2的粘合膜在室温下具有高伸长率,并且其在低温扩展过程中具有低可切割性,并因此难以确保充分的可切割性,如表2中所示。
此外,可确定在使用比较例1和2的粘合膜制造的切割管芯粘结膜中,通过切割过程产生20%或更多的毛刺,并且比较例1和2的粘合膜不具有足够的高温剪切力,并因此难以确保足够的粘合强度。
Claims (9)
1.一种用于半导体的粘合膜,在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且
在室温下在5%至10%伸长率下产生的模量为50MPa或更高,
其中所述用于半导体的粘合膜包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为105℃至160℃的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂,
其中所述固体环氧树脂和所述液体环氧树脂的总含量相对所述热塑性树脂的重量比为1.6至2.6,
所述酚树脂相对所述热塑性树脂、所述酚树脂和所述液体环氧树脂的总重量的重量比为59/149至0.600。
2.根据权利要求1所述的用于半导体的粘合膜,其中所述粘合膜用作管芯粘附膜以用于连接引线框或基板与管芯或者连接管芯与管芯。
3.一种用于半导体的粘合膜,在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,并且
在室温下的伸长率为500%或更低,
其中所述用于半导体的粘合膜包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为105℃至160℃的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂,
其中所述固体环氧树脂和所述液体环氧树脂的总含量相对所述热塑性树脂的重量比为1.6至2.6,
所述酚树脂相对所述热塑性树脂、所述酚树脂和所述液体环氧树脂的总重量的重量比为59/149至0.600。
4.根据权利要求3所述的用于半导体的粘合膜,其中所述粘合膜用作管芯粘附膜以用于连接引线框或基板与管芯或者连接管芯与管芯。
5.一种用于半导体的粘合膜,在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且
在室温下的伸长率为500%或更低,
其中所述用于半导体的粘合膜包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为105℃至160℃的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂,
其中所述固体环氧树脂和所述液体环氧树脂的总含量相对所述热塑性树脂的重量比为1.6至2.6,
所述酚树脂相对所述热塑性树脂、所述酚树脂和所述液体环氧树脂的总重量的重量比为59/149至0.600。
6.根据权利要求5所述的用于半导体的粘合膜,其中所述粘合膜用作管芯粘附膜以用于连接引线框或基板与管芯或者连接管芯与管芯。
7.一种用于半导体的粘合膜,在110℃的温度和5rad/s的剪切速率下的熔体粘度为1,000Pa·s至4,000Pa·s,
在室温下在5%至10%伸长率下产生的模量为50MPa或更高,并且
在室温下的伸长率为500%或更低,
其中所述用于半导体的粘合膜包含玻璃化转变温度为-10℃至20℃的热塑性树脂、含有软化点为105℃至160℃的酚树脂的固化剂、液体环氧树脂、和固体环氧树脂,
其中所述固体环氧树脂和所述液体环氧树脂的总含量相对所述热塑性树脂的重量比为1.6至2.6,
所述酚树脂相对所述热塑性树脂、所述酚树脂和所述液体环氧树脂的总重量的重量比为59/149至0.600。
8.根据权利要求7所述的用于半导体的粘合膜,其中所述粘合膜用作管芯粘附膜以用于连接引线框或基板与管芯或者连接管芯与管芯。
9.根据权利要求7所述的用于半导体的粘合膜,其中所述粘合膜的厚度为1μm至300μm。
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