CN104221171A - 半导体装置、芯片粘合材料和半导体装置的制造方法 - Google Patents
半导体装置、芯片粘合材料和半导体装置的制造方法 Download PDFInfo
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- CN104221171A CN104221171A CN201380019303.1A CN201380019303A CN104221171A CN 104221171 A CN104221171 A CN 104221171A CN 201380019303 A CN201380019303 A CN 201380019303A CN 104221171 A CN104221171 A CN 104221171A
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- aromatic rings
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
一种半导体装置(10),其包括基板(1)、粘接层(2)和发光二极管芯片(3),粘接层(2)为芯片粘合材料的固化物,该芯片粘合材料含有树脂成分(A)、硅烷偶联剂(B)和无机填料(C),其中,树脂成分(A)为选自下述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种(式中,X表示氧原子或氮原子;m和n为0或1;R1、R2、R3、R4表示氢原子或不具有芳香环的有机基团,其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基的有机基团)。
Description
技术领域
本发明涉及半导体装置、芯片粘合(die attach)材料和半导体装置的制造方法。
背景技术
近年来,发光二极管(LED)作为手机的背光灯、喷水池的灯、聚光灯、台式计算机和电视的液晶显示器的背光灯等的低功率LED(低于0.3W/mK)或中功率LED(0.3~0.5W/mK)在各领域中使用。并且,今后期待着作为汽车的头灯等大功率LED(超过0.5W/mK)使用等的应用领域的更进一步的扩大。
LED通常利用芯片粘合膏将LED芯片粘接于基板或引线框上,以LED封装体的形态使用。
作为用于半导体装置的芯片粘合膏,目前已知有各种材料(例如参照专利文献1~3)。但是,作为用于LED的芯片粘合膏,为了最大限度地发挥LED的特征,要求兼备如下所述的特性。
(1)高光反射性
为了最大限度地利用从LED朝基板侧发射的光、使LED的光输出达到最大限度,要求高光反射性。
(2)高耐变色性
为了维持LED的最大光输出,要求高耐变色性。
(3)高弹性模量
由于在较小LED芯片的情况下,在低弹性模量时不能实现引线接合,所以要求高弹性模量。
(4)高密合强度
为了使LED芯片在引线接合中不会掉落,要求高密合强度。
作为现在的LED用芯片粘合膏,已知含有有机硅树脂、环氧树脂、丙烯酸树脂等的粘合膏(例如,参照专利文献4~9)。
含有有机硅树脂的芯片粘合膏,虽然在无色且高耐变色方面优异,但存在密合性差的缺点。含有环氧树脂的芯片粘合膏,虽然密合性优异,但存在容易着色、耐变色性低的缺点。含有丙烯酸树脂的芯片粘合膏,虽然光反射性优异,但存在密合性差、弹性模量低的缺点。
在先技术文献
专利文献
专利文献1:日本特开2001-019912号公报
专利文献2:日本特开2001-019722号公报
专利文献3:日本特开2001-019821号公报
专利文献4:日本特开2005-113059号公报
专利文献5:日本特开2009-242587号公报
专利文献6:日本特开2009-256400号公报
专利文献7:日本特开2010-248349号公报
专利文献8:日本特开2011-100927号公报
专利文献9:日本特开2011-088947号公报
发明内容
发明所要解决的课题
本发明的发明人进行了研究,结果发现:将现有的半导体装置用芯片粘合膏直接应用于LED,从高光反射性的方面考虑并不适合。
另外,利用现有的LED用芯片粘合膏,存在虽然在无色且高耐变色性方面优异,但密合性差;虽然密合性优异但容易着色、耐变色性低;虽然光反射性优异但密合性差、弹性模量低等的缺点,所以尚未得到能够满足上述背景技术中所述的(1)~(4)的各特征的LED用芯片粘合膏。
本发明是鉴于上述情况而完成的,提供一种具有高光反射性、高耐变色性、高弹性模量和高密合强度的平衡性优异的特性的半导体装置、和半导体装置的制造方法。
用于解决课题的技术方案
为了解决上述课题,本发明采用以下的构成。
即,本发明的第一方面提供一种半导体装置,其包括基板、粘接层和发光二极管芯片,
上述粘接层为含有树脂成分(A)、硅烷偶联剂(B)和无机填料(C)的芯片粘合材料的固化物,
其中,树脂成分(A)为选自下述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种,
硅烷偶联剂(B)为选自下述通式(b-1)所示的化合物(B1)和下述通式(b-2)所示的化合物(B2)中的至少1种。
(式中,X表示氧原子或氮原子,m和n各自独立地为0或1,当X为氧原子时m+n=1,当X为氮原子时m+n=2;R1、R2、R3、R4各自独立地表示氢原子或不具有芳香环的有机基团,其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R1、R2、R3、R4中的至少2个取代基可以形成环。)
Y-(CH2)m-SiR5R6R7 (b-1)
(S)n-((CH2)p-SiR5R6R7)2 (b-2)
(式中,R5、R6、R7各自独立地表示碳原子数1~10的烷基或碳原子数1~10的烷氧基,其中,R5、R6、R7中的至少一个为碳原子数1~10的烷氧基;Y为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中的任一种;m和p各自独立地为1~10的整数;n为1以上的整数。)
另外,本发明的第二方面提供一种用于将基板与发光二极管芯片粘接的芯片粘合材料,该芯片粘合材料含有:选自上述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种的树脂成分(A);选自下述通式(b-1)所示的化合物(B1)和下述通式(b-2)所示的化合物(B2)中的至少1种的硅烷偶联剂(B);和无机填料(C)。
在本发明的第一方面和第二方面中,优选上述芯片粘合材料为芯片粘合膏。
在本发明的第一方面和第二方面中,优选上述化合物(A1)含有选自下述通式(a1-1)所示的化合物和下述通式(a1-2)所示的化合物中的至少1种。
(式中,R1、R2、R3各自独立地为氢原子或不具有芳香环的有机基团,R1、R2、R3中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团。)
(式中,R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团。)
在本发明的第一方面和第二方面中,优选上述化合物(A1)为分子内至少具有3个以上的丙烯酰基或(甲基)丙烯酰基的化合物。
在本发明的第一方面和第二方面中,优选上述丙烯酸酯化合物(A2)含有下述通式(a2-1)所示的化合物,
(R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R11、R12各自独立地为直链状的亚烷基或单键,Z表示亚环烷基。)
在本发明的第一方面和第二方面中,优选上述树脂成分(A)含有上述通式(a1-1)所示的化合物。
在本发明的第一发明和第二方面中,优选上述硅烷偶联剂(B)含有上述通式(b-1)所示的化合物。
在本发明的第一方面和第二方面中,优选上述通式(b-1)中Y为环氧丙氧基或(甲基)丙烯酰氧基。
本发明的第三方面提供一种半导体装置的制造方法,其包括:
将树脂成分(A)、硅烷偶联剂(B)和无机填料(C)混合制造芯片粘合材料的工序,上述树脂成分(A)为选自下述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种,硅烷偶联剂(B)为选自下述通式(b-1)所示的化合物(B1)和下述通式(b-2)所示的化合物(B2)中的至少1种;
将上述芯片粘合材料涂布在基板或发光二极管芯片上的工序;和
将上述发光二极管芯片粘接在上述基板上的工序。
在本发明的第三方面中,优选上述芯片粘合材料为芯片粘合膏。
在本发明的第三方面中,优选上述化合物(A1)含有选自上述通式(a1-1)所示的化合物和上述通式(a1-2)所示的化合物中的至少1种。
在本发明的第三方面中,优选上述化合物(A1)为分子中至少具有3个以上的丙烯酰基或(甲基)丙烯酰基的化合物。
在本发明的第三方面中,优选上述丙烯酸酯化合物(A2)含有上述通式(a2-1)所示的化合物。
在本发明的第三方面中,优选上述树脂成分(A)含有上述通式(a1-1)所示的化合物。
在本发明的第三方面中,优选上述硅烷偶联剂(B)含有上述通式(b-1)所示的化合物。
在本发明的第三方面中,优选上述通式(b-1)中Y为环氧丙氧基或(甲基)丙烯酰氧基。
发明效果
根据本发明,能够提供一种具有高光反射性、高耐变色性、高弹性模量和高密合强度的平衡性优异的特性的半导体装置、以及半导体装置的制造方法。
附图说明
图1是表示本实施方式的半导体装置的一个示例的截面图。
具体实施方式
下面,使用附图对本发明的实施方式进行说明。其中,在所有的附图中,对相同的构成要素标注相同的符号,适当地省略说明。
本实施方式的半导体装置包括基板、粘接层和发光二极管芯片。
作为基板,没有特别限制,可以使用一直以来在LED半导体装置中所使用的基板。
具体而言,作为基板可以列举:在铜、铜合金、陶瓷、有机基板等的表面上,以提高光反射性为目的而实施了银、金、银合金等的电镀而形成的框等。其中,通常为实施了镀银的铜框,也更为优选。
图1是表示本实施方式的半导体装置的一个示例的截面图。
作为本实施方式的半导体装置10,例如如图1所示,包括基板1、搭载于上述基板1上的发光二极管芯片3、和设置于上述基板1与上述发光二极管芯片3之间的粘接层2。另外,在本实施方式的半导体装置10中,上述基板1和上述发光二极管芯片3通过接合线20而电连接。而且,发光二极管芯片3和接合线20被透明的封装树脂21封装。
在本实施方式的半导体装置中,粘接层具备含有以下成分的芯片粘合材料的固化物:
选自上述通式(1)所示的化合物(A1)(以下,称为“(A1)成分”)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)(以下,称为“(A2)成分”)中的至少1种的树脂成分(A)(以下,称为“(A)成分”);
选自上述通式(b-1)所示的化合物(B1)(以下,称为“(B1)成分”)和上述通式(b-2)所示的化合物(B2)(以下,称为“(B2)成分”)中的至少1种的硅烷偶联剂(B)(以下,称为“(B)成分”);和
无机填料(C)(以下,称为“(C)成分”)。
下面,对芯片粘合材料的各成分进行说明。
本实施方式中的芯片粘合材料可以是芯片粘合膜,也可以是芯片粘合膏。并且,本实施方式中的芯片粘合材料优选为芯片粘合膏。
下面,关于本实施方式中的芯片粘合材料,以芯片粘合膏为例进行说明。
<(A)成分>
(A)成分是含有(A1)成分和/或(A2)成分的树脂成分。
(A1)成分是下述通式(1)所示的化合物。
(式中,X表示氧原子或氮原子,m和n各自独立地为0或1,当X为氧原子时m+n=1,当X为氮原子时m+n=2;R1、R2、R3、R4各自独立地表示氢原子或不具有芳香环的有机基团,其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R1、R2、R3、R4中的至少2个取代基可以形成环。)
在上述通式(1)中,X表示氧原子或氮原子,m和n各自独立地为0或1。其中,当X为氧时m+n=1,当X为氮时m+n=2。X优选为氮原子。
在上述通式(1)中,R1、R2、R3、R4各自独立地表示氢原子或不具有芳香环的有机基团。其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团。
作为R1、R2、R3、R4的有机基团,例如可以例示源自下列物质的有机基团:不含芳香环的多异氰酸酯、与不含芳香环且分子中具有1个羟基和1个以上的(甲基)丙烯酰基的化合物的反应物;不含芳香环且分子中具有1个异氰酸酯基和1个以上的(甲基)丙烯酰基的化合物、与不含芳香环的多元醇的反应物;不含芳香环的多异氰酸酯、与不含芳香环且分子中具有1个氨基和1个以上的(甲基)丙烯酰基的化合物的反应物;不含芳香环且分子中具有1个异氰酸酯基和1个以上的(甲基)丙烯酰基的化合物、与不含芳香环的多胺的反应物;异氰脲酸酯环的氮上的取代基具有(甲基)丙烯酰基的化合物等。
具体而言,作为上述不含芳香环的多异氰酸酯,例如可以列举亚丙基二异氰酸酯、亚丁基二异氰酸酯、亚己基二异氰酸酯、亚戊基二异氰酸酯、1,2-亚丙基二异氰酸酯、2,3-亚丁基二异氰酸酯、1,3-亚丁基二异氰酸酯、亚十二烷基二异氰酸酯、2,4,4-三甲基亚己基二异氰酸酯等的脂肪族二异氰酸酯;3-异氰酸酯基甲基-3,5,5-三甲基环己基异氰酸酯[别名:异佛尔酮二异氰酸酯]、1,3-环戊烷二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、甲基-2,4-环己烷二异氰酸酯、甲基-2,6-环己烷二异氰酸酯、4,4′-亚甲基双(环己基异氰酸酯)、1,3-双(异氰酸酯甲基)环己烷、1,4-双(异氰酸酯基甲基)环己烷、氢化苯二甲基二异氰酸酯、氢化二苯甲烷二异氰酸酯等的脂环族二异氰酸酯。
作为不含芳香环且分子中具有1个羟基和1个以上的(甲基)丙烯酰基的化合物,例如可以例示:2-羟乙基(甲基)丙烯酸酯、2-羟丙基(甲基)丙烯酸酯、2-羟丁基(甲基)丙烯酸酯、4-羟丁基(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯等在分子中具有1个羟基的脂肪族(甲基)丙烯酸酯;聚乙二醇一(甲基)丙烯酸酯、聚(己内酯)二醇一(甲基)丙烯酸酯等在分子中具有1个羟基的聚亚烷基醚一(甲基)丙烯酸酯、聚酯一(甲基)丙烯酸酯等。
另外,作为不含芳香环且分子中具有1个异氰酸酯基和1个以上的(甲基)丙烯酰基的化合物,可以例示:2-(甲基)丙烯酰氧乙基异氰酸酯、1,1-(双丙烯酰氧甲基)乙基异氰酸酯等在分子中具有1个异氰酸酯基和1个以上的(甲基)丙烯酰基的脂肪族丙烯酸酯。
作为不含芳香环的多元醇,可以例示:乙二醇、丙二醇、二乙二醇、二丙二醇、丁二醇、1,6-已二醇、3-甲基-1,5-戊二醇、新戊二醇、己三醇等脂肪族二元醇;三羟甲基丙烷、季戊四醇等脂肪族多元醇;聚乙二醇等聚亚烷基醚二元醇;聚(己内酯)二元醇等聚酯二元醇;三(2-羟乙基)异氰脲酸酯等异氰脲酸酯环的氮上的取代基具有羟烷基的化合物。
作为不含芳香环的多胺,可以例示:亚丙基二胺、亚丁基二胺、亚己基二胺、亚戊基二胺、1,2-丙二胺、2,3-丁二胺、1,3-丁二胺、亚十二烷基二胺、2,4,4-三甲基亚己基二胺等脂肪族二胺;3-氨甲基-3,5,5-三甲基环己胺[别名:异佛尔酮二胺]、1,3-环戊烷二胺、1,3-环己烷二胺、1,4-环己烷二胺、甲基-2,4-环己烷二胺、甲基-2,6-环己烷二胺、4,4′-亚甲基双(环己胺)、1,3-双(氨甲基)环己烷、1,4-双(氨甲基)环己烷等脂环族二胺;精胺、亚精胺等脂肪族多胺等。
作为异氰脲酸酯环的氮上的取代基具有(甲基)丙烯酰基的化合物,可以例示:(三(2-羟乙基)异氰脲酸酯三丙烯酸酯、二(2-丙烯酰氧乙基)异氰脲酸酯、ε-己内酯改性三(2-丙烯酰氧乙基)异氰脲酸酯等,但不限定于此,通过2-羟乙基异氰脲酸酯或异氰脲酸与(甲基)丙烯酸或(甲基)丙烯酰卤的缩合反应而导入(甲基)丙烯酰基的化合物;在使2-羟乙基异氰脲酸酯的羟基与聚亚烷基二元醇、聚酯二元醇反应而得到的化合物的末端,通过(甲基)丙烯酸或(甲基)丙烯酰卤的缩合反应而导入(甲基)丙烯酰基的化合物也包括在本发明中。
其中,优选三(2-羟乙基)异氰脲酸酯三丙烯酸酯(SartomerCompany,Inc.,SR-368)、季戊四醇三丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物、季戊四醇三丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物(共荣社化学社,UA-306H)、季戊四醇三丙烯酸酯异佛尔酮二异氰酸酯聚氨酯预聚物(共荣社化学社,UA-306I)、二季戊四醇五丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物(共荣社化学社,UA-510H)、ε-己内酯改性三(2-丙烯酰氧乙基)异氰脲酸酯(新中村化学工业社,A-9300-1CL)、三(2-丙烯酰氧乙基)异氰脲酸酯、二(2-丙烯酰氧乙基)异氰脲酸酯。
在上述通式(1)中,R1、R2、R3、R4中的至少2个取代基可以形成环。此时,X优选为氮原子。
作为(A1)成分,优选含有选自下述通式(a1-1)所示的化合物和下述通式(a1-2)所示的化合物中的至少1种,特别优选下述通式(a1-1)所示的化合物。
(式中,R1、R2、R3各自独立地为氢原子或不具有芳香环的有机基团,R1、R2、R3中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团。)
(式中,R1′、R2′各自独立为具有(甲基)丙烯酰基而不具有芳香环的有机基团。)
在上述通式(a1-1)中,R1、R2、R3各自独立地为氢原子或不具有芳香环的有机基团,与上述通式(1)相同。作为R1、R2、R3的有机基团,优选(甲基)丙烯酰基、内酯改性(甲基)丙烯酰基、聚亚烷基二元醇(甲基)丙烯酰基,更优选为(甲基)丙烯酰基、内酯改性(甲基)丙烯酰基,特别优选为(甲基)丙烯酰基。
优选R1、R2、R3中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R1、R2、R3中的任一个为具有(甲基)丙烯酰基而不具有芳香环的有机基团。
在上述通式(a1-2)中,R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团,与上述R1、R2、R3的有机基团相同。在上述通式(a1-2)中,作为R1′、R2′的有机基团,优选源自季戊四醇三丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物、季戊四醇三丙烯酸酯甲苯二异氰酸酯聚氨酯预聚物、季戊四醇三丙烯酸酯异佛尔酮二异氰酸酯聚氨酯预聚物、二季戊四醇五丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物等的有机基团,更优选源自季戊四醇三丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物、季戊四醇三丙烯酸酯异佛尔酮二异氰酸酯聚氨酯预聚物的有机基团,特别优选源自季戊四醇三丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物的有机基团。
另外,通式(1)所示的化合物(A1)优选在分子内至少具有3个以上的丙烯酰基或(甲基)丙烯酰基的化合物。由此,能够实现具有高光反射性、高耐变色性、高弹性模量和高密合强度的平衡性更优异的特性的半导体装置。
(A2)成分是1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物。
作为(A2)成分,优选下述通式(a2-1)所示的化合物。
(R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R11、R12各自独立地为直链状的亚烷基或单键,Z表示亚环烷基。)
在上述通式(a2-1)中,R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团,同上。在上述通式(a2-1)中,作为R1′、R2′的有机基团,优选为(甲基)丙烯酰氧基、烷基(甲基)丙烯酰氧基、聚亚烷基二元醇(甲基)丙烯酰氧基,更优选为(甲基)丙烯酰氧基、烷基(甲基)丙烯酰氧基,特别优选为(甲基)丙烯酰氧基。
在上述通式(a2-1)中,R11、R12各自独立地表示直链状的亚烷基或单键。作为R11、R12的直链状的亚烷基,可以例举亚甲基、亚乙基、亚丙基等。
作为R11、R12,优选为直链状的亚烷基,特别优选R11、R12均为亚甲基。
在上述通式(a2-1)中,Z表示亚环烷基。亚环烷基可以为单环,也可以为多环,优选为多环。亚环烷基的碳原子数优选为6以上,更优选为8以上,特别优选为10以上。
作为亚环烷基的具体例,可以列举:亚环戊基、亚环己基、三环亚癸基(tricyclodecylene group)等。其中,优选亚环己基、三环亚癸基,特别优选为三环亚癸基。
作为这样的化合物,例如有三环癸烷二甲醇二丙烯酸酯(新中村化学工业社,A-DCP)。
在本实施方式中,芯片粘合膏中所含的优选的树脂成分(A)的含量为3重量%以上20重量%以下,更优选的范围为5重量%以上16重量%以下,进一步优选的范围为7重量%以上12重量%以下。其理由是,当树脂成分(A)的含量在上述范围内时,可兼具良好的密合强度和高弹性模量,并且在引线接合时不易发生不良。
<(B)成分>
(B)成分是含有选自下述通式(b-1)所示的(B1)成分和/或下述通式(b-2)所示的(B2)成分中的至少1种的硅烷偶联剂。
Y-(CH2)m-SiR5R6R7 (b-1)
(S)n-((CH2)p-SiR5R6R7)2(b-2)
(式中,R5、R6、R7各自独立地表示碳原子数1~10的烷基或碳原子数1~10的烷氧基,其中,R5、R6、R7中的至少一个为碳原子数1~10的烷氧基;Y为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中的任一种;m和p各自独立地为1~10的整数;n为1以上的整数。)
在上述通式(b-1)和(b-2)中,R5、R6、R7各自独立地表示碳原子数1~10的烷基或碳原子数1~10的烷氧基。其中,R5、R6、R7中的至少一个为碳原子数1~10的烷氧基。
R5、R6、R7的烷基优选碳原子数为1~8,更优选为1~5,进一步优选为1~3。作为R5、R6、R7的烷基的具体例,可以列举甲基、乙基、丙基。其中,优选为甲基、乙基,特别优选为甲基。
R5、R6、R7的烷氧基优选碳原子数为1~8,更优选为1~5,进一步优选为1~3。作为R5、R6、R7的烷氧基的具体例,可以列举甲氧基、乙氧基、丙氧基、丁氧基。其中,优选为甲氧基、乙氧基、丙氧基,特别优选为甲氧基或乙氧基。
R5、R6、R7中的至少一个为碳原子数1~10的烷氧基,优选至少2个为碳原子数1~10的烷氧基,特别优选R5、R6、R7全部为碳原子数1~10的烷氧基。
在上述通式(b-1)中,Y为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中的任一种。其中,Y优选为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基,特别优选为环氧丙氧基或(甲基)丙烯酰氧基。
在上述通式(b-1)和(b-2)中,m和p各自独立地为1~10的整数,优选为1~6的整数,更优选为1~3的整数。
在上述通式(b-2)中,n为1以上的整数,优选为2以上10以下的整数,更优选为2以上4以下的整数。
在本实施方式中,作为(B)成分,从密合强度和反射率的观点来看,优选为(B1)成分。
在本实施方式中,芯片粘合膏中所含的优选的硅烷偶联剂(B)的含量为0.1重量%以上10重量%以下,更优选的范围为0.5重量%以上8重量%以下,进一步优选的范围为1重量%以上5重量%以下。其理由是,在上述范围内时,能够得到良好的密合强度,并且不易对空隙(voids)或渗出(bleeding)造成不良影响。
<(C)成分>
(C)成分是无机填料。作为无机填料,没有特别限制,可以使用以往公知的材料,具体而言,可以列举银粉、金粉、镍粉、铜粉等的导电性填料,氮化铝、碳酸钙、二氧化硅、氧化铝等的绝缘填料。这些无机填料可以1种单独使用,也可以组合2种以上使用。其中,为了用于大功率的LED,需要导热性,优选使用20W/m·K以上的导热性填料。另外,在同时要求绝缘性的情况下,更优选使用氧化铝、氧化镁、氮化硼、氮化铝,特别优选氧化铝。
在本发明中,芯片粘合膏中所含的优选的无机填料(C)的含量为60重量%以上90重量%以下,更优选的范围为65重量%以上85重量%以下,进一步优选的范围为70重量%以上80重量%以下。其理由是,在上述范围内时,能够得到良好的操作性、导热率。
<任选成分>
在本实施方式中,芯片粘合膏除了上述(A)成分、(B)成分和(C)成分以外,还可以根据需要添加现有公知的任选成分。具体而言,例如可以列举:(A)成分以外的丙烯酸酯树脂(以下,称为“(D)成分”)、有机过氧化物(以下,称为“(E)成分”)等。
<(D)成分>
作为(D)成分的丙烯酸酯树脂,例如可以列举:三羟甲基丙烷三甲基丙烯酸酯、2-(甲基)丙烯酰氧乙基丁二酸、2-(甲基)丙烯酰氧丙基丁二酸、2-(甲基)丙烯酰氧乙基六氢化邻苯二甲酸、2-(甲基)丙烯酰氧丙基六氢化邻苯二甲酸、2-(甲基)丙烯酰氧乙基甲基六氢化邻苯二甲酸、2-(甲基)丙烯酰氧丙基甲基六氢化邻苯二甲酸、2-(甲基)丙烯酰氧乙基邻苯二甲酸、2-(甲基)丙烯酰氧丙基邻苯二甲酸、2-(甲基)丙烯酰氧乙基四氢化邻苯二甲酸、2-(甲基)丙烯酰氧丙基四氢化邻苯二甲酸、2-(甲基)丙烯酰氧乙基甲基四氢化邻苯二甲酸、2-(甲基)丙烯酰氧丙基甲基四氢化邻苯二甲酸、2-羟基-1,3二(甲基)丙烯酰氧基丙烷、四羟甲基甲烷三(甲基)丙烯酸酯、2-羟乙基(甲基)丙烯酸酯、2-羟丙基(甲基)丙烯酸酯、2-羟丁基(甲基)丙烯酸酯、丙三醇二(甲基)丙烯酸酯、2-羟基-3-(甲基)丙烯酰氧丙基(甲基)丙烯酸酯、1,4-环己烷二甲醇一(甲基)丙烯酸酯、乙基-α-(羟甲基)(甲基)丙烯酸酯、4-羟丁基(甲基)丙烯酸酯、甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、正丁基(甲基)丙烯酸酯、异丁基(甲基)丙烯酸酯、叔丁基(甲基)丙烯酸酯、异癸基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、十三烷基(甲基)丙烯酸酯、十六烷基(甲基)丙烯酸酯、硬酯酰(甲基)丙烯酸酯、异戊基(甲基)丙烯酸酯、异硬酯酰(甲基)丙烯酸酯、山嵛基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、其它的烷基(甲基)丙烯酸酯、环己基(甲基)丙烯酸酯、叔丁基环己基(甲基)丙烯酸酯、四氢糠基(甲基)丙烯酸酯、苯甲基(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯、异冰片基(甲基)丙烯酸酯、环氧丙基(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、一(甲基)丙烯酸锌(zinc mono(meth)acrylate)、二(甲基)丙烯酸锌、二甲基氨基乙基(甲基)丙烯酸酯、二乙基氨基乙基(甲基)丙烯酸酯、新戊二醇(甲基)丙烯酸酯、三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、2,2,3,3,4,4-六氟丁基(甲基)丙烯酸酯、全氟辛基(甲基)丙烯酸酯、全氟辛基乙基(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、甲氧基乙基(甲基)丙烯酸酯、丁氧基乙基(甲基)丙烯酸酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚亚烷基二醇一(甲基)丙烯酸酯、辛氧基聚亚烷基二醇一(甲基)丙烯酸酯、月桂氧基聚亚烷基二醇一(甲基)丙烯酸酯、硬脂酰氧基聚亚烷基二醇一(甲基)丙烯酸酯、烯丙氧基聚亚烷基二醇一(甲基)丙烯酸酯、壬基苯氧基聚亚烷基二醇一(甲基)丙烯酸酯、N,N′-亚甲基双(甲基)丙烯酰胺、N,N′-亚乙基双(甲基)丙烯酰胺、1,2-二(甲基)丙烯酰胺乙二醇、二(甲基)丙烯酰氧甲基三环癸烷、2-(甲基)丙烯酰氧乙基、N-(甲基)丙烯酰氧乙基马来酰亚胺、N-(甲基)丙烯酰氧乙基六氢化邻苯二甲酰亚胺、N-(甲基)丙烯酰氧乙基邻苯二甲酰亚胺、N-乙烯基-2-吡咯烷酮、乙氧基化双酚A(甲基)丙烯酸酯、丙氧基化双酚A(甲基)丙烯酸酯、苯乙烯衍生物、α-甲基苯乙烯衍生物等,但没有特别限制。另外,这些丙烯酸酯树脂从固化性、操作性、粘接性等观点来看,也可以并用2种以上。
芯片粘合膏中所含的优选的丙烯酸酯树脂(D)不是必须成分,但在调节粘度或固化性等需要的情况下,其含量为0.1重量%以上20重量%以下,更优选的范围为0.5重量%以上15重量%以下,进一步优选的范围为1重量%以上10重量%以下。
<(E)成分>
作为(E)成分的有机过氧化物,例如可以列举:1,1-二(叔丁基过氧化)环己烷、甲乙酮过氧化物、甲基环己酮过氧化物、甲基乙酰乙酸酯过氧化物、乙酰丙酮过氧化物、1,1-双(叔丁基过氧化)3,3,5-三甲基环己烷、1,1-双(叔己基过氧化)环己烷、1,1-双(叔己基过氧化)3,3,5-三甲基环己烷、1,1-双(叔丁基过氧化)环己烷、2,2-双(4,4-二-叔丁基过氧化环己基)丙烷、1,1-双(叔丁基过氧化)环十二烷、正丁基4,4-双(叔丁基过氧化)戊酸酯、2,2-双(叔丁基过氧化)丁烷、1,1-双(叔丁基过氧化)-2-甲基环己烷、叔丁基过氧化氢、对薄荷烷过氧化氢、1,1,3,3-四甲基丁基过氧化氢、叔己基过氧化氢、二异丙苯过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、α,α′-双(叔丁基过氧化)二异丙基苯、叔丁基异丙苯基过氧化物、二-叔丁基过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化)己炔-3、异丁酰过氧化物、3,5,5-三甲基己酰过氧化物、辛酰过氧化物、月桂酰过氧化物、桂皮酸过氧化物、间甲苯酰过氧化物、苯甲酰过氧化物、二异丙基过氧化二碳酸酯、双(4-叔丁基环己基)过氧化二碳酸酯、二-3-甲氧基丁基过氧化二碳酸酯、二-2-乙基己基过氧化二碳酸酯、二-仲丁基过氧化二碳酸酯、二(3-甲基-3-甲氧基丁基)过氧化二碳酸酯、二(4-叔丁基环己基)过氧化二碳酸酯、α,α′-双(新癸酰基过氧化)二异丙基苯、异丙苯基过氧化新癸酸酯、1,1,3,3-四甲基丁基过氧化新癸酸酯、1-环己基-1-甲基乙基过氧化新癸酸酯、叔己基过氧化新癸酸酯、叔丁基过氧化新癸酸酯、叔己基过氧化新戊酸酯、叔丁基过氧化新戊酸酯、2,5-二甲基-2,5-双(2-乙基己酰过氧化)己烷、1,1,3,3-四甲基丁基过氧化-2-乙基己酸酯、1-环己基-1-甲基乙基过氧化-2-乙基己酸酯、叔己基过氧化-2-乙基己酸酯、叔丁基过氧化-2-乙基己酸酯、叔丁基过氧化异丁酸酯、叔丁基过氧化马来酸、叔丁基过氧化月桂酸酯、叔丁基过氧化-3,5,5-三甲基已酸酯、叔丁基过氧化异丙基一碳酸酯、叔丁基过氧化-2-乙基己基一碳酸酯、2,5-二甲基-2,5-双(苯甲酰过氧化)己烷、叔丁基过氧化乙酸酯、叔己基过氧化苯甲酸酯、叔丁基过氧化-间甲苯酰基苯甲酸酯、叔丁基过氧化苯甲酸酯、双(叔丁基过氧化)间苯二甲酸酯、叔丁基过氧化烯丙基一碳酸酯、3,3′,4,4′-四(叔丁基过氧化羰基)二苯甲酮等,它们可以单独使用,或者为了控制固化性而并用2种以上。
芯片粘合膏中所含的优选的有机过氧化物(E)的含量为0重量%以上0.15重量%以下,更优选的范围为0重量%以上0.1重量%以下,进一步优选的范围为0重量%以上0.05重量%以下。
另外,在本实施方式的芯片粘合膏中,可以根据需要使用固化剂、有机溶剂、消泡剂、表面活性剂、弹性体等添加剂。
在本实施方式中,芯片粘合膏例如可以如下所述制造:将各成分预混合,之后,使用3辊机进行混练,然后在真空下进行脱泡。并且,固态成分优选在预混合之前预先溶解于有机溶剂中后使用。
作为有机溶剂,例如可以列举:苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、γ-丁内酯、草酸二丁酯、马来酸二甲酯、马来酸二乙酯、乙二醇一丁酸酯、碳酸丙烯酯、N-甲基吡咯烷酮、2-(己氧基)乙醇、二乙二醇、二乙二醇一乙醚、二乙二醇一丁醚、三乙二醇一甲醚、二丙二醇、三丙二醇一甲醚、水杨酸甲酯、二乙二醇一乙醚乙酸酯、二乙二醇一丁醚乙酸酯。其中,优选为苯甲酸乙酯、苯甲酸丙酯、苯甲酸丁酯、γ-丁内酯、草酸二丁基、马来酸二乙基、乙二醇一丁酸酯、碳酸丙烯酯、二乙二醇、二乙二醇一丁醚、三乙二醇一甲醚、二丙二醇、三丙二醇一甲醚、水杨酸甲酯、二乙二醇一乙基醚乙酸酯、二乙二醇一丁醚乙酸酯,更优选为γ-丁内酯。
将如上所述制备的芯片粘合膏涂布在基板和发光二极管芯片上,将该发光二极管芯片粘接在该基板上,由此制造本实施方式的半导体装置。其中,在本实施方式的芯片粘合材料是芯片粘合膜的情况下,将芯片粘合材料设置在基板与发光二极管芯片之间,将该发光二极管芯片粘接在基板上,由此制造本实施方式的半导体装置。
本实施方式的半导体装置具有粘接层,该粘接层具备具有高光反射性、高耐变色性、高弹性模量、高密合强度等的平衡性优异的特性的芯片粘合膏的固化物。因此,本实施方式的半导体装置能够使光输出达到最大限度,并且能够维持最大光输出。另外,本实施方式的半导体装置即使LED芯片非常小,在引线接合时也能够粘接在基板等上而不会发生LED芯片的脱落。
能够获得上述效果的理由尚不明确,但可以推测如下。
即,本实施方式的半导体装置的粘接层中使用的芯片粘合膏,作为树脂成分(A),具有(A1)成分和/或(A2)成分。
(A1)成分的结构中具有高极性的NC(=O)骨架。因此,推测能够实现高密合强度。
另外,(A2)成分由于不具有芳香环,所以光吸收较小,能够实现高光反射率。因此,推测即使是发光二极管芯片朝基板侧发射的光也能够最大限度地利用,能够使LED的光输出达到最大限度。另外,推测由于具有作为刚性更强的骨架的亚环烷基,因而能够实现固化后的高弹性模量。
特别是在树脂成分(A)为上述通式(a1-1)所示的化合物时,由于兼备(A1)成分的特征和(A2)成分的特征,所以能够得到具有具备芯片粘合膏的固化物的粘接层的半导体装置,该芯片粘合膏的固化物具有高光反射性、高耐变色性、高弹性模量、高密合强度等的平衡性更优异的特性。
另外,本实施方式的半导体装置的粘接层中使用的芯片粘合膏含有特定的硅烷偶联剂(B1)成分和/或(B2)成分。
(B1)成分是具有氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中任一种的硅烷偶联剂,(B2)成分是具有硫键(sulfidebond)的硅烷偶联剂。特别是通过含有具有环氧丙氧基、(甲基)丙烯酰氧基的硅烷偶联剂,能够赋予良好的密合性,并且芯片粘合膏的清漆成分不易着色,能够实现高光反射率,因而优选。其中,在不损害密合性、光反射性等特性的范围内,硅烷偶联剂可以并用2种以上。
实施例
下面,通过实施例来具体地说明本发明,但本发明不限于这些实施例。
<实施例1~5、比较例1~3>
配合表1所示的各成分,使用3辊机进行混炼,在脱泡后得到芯片粘合膏。
[表1]
表1中的各简写符号具有以下的含义。另外,各成分的配合量为重量%。另外,实施例和比较例所使用的各成分如下所示。
(A)-1:三(2-羟乙基)异氰脲酸酯三丙烯酸酯(商品名:SR-368,Sartomer Company,Inc.生产)。
(A)-2:季戊四醇三丙烯酸酯亚己基二异氰酸酯聚氨酯预聚物(商品名:UA-306H,共荣社化学株式会社生产)。
(A)-3:三环癸烷二甲醇二丙烯酸酯(商品名:A-DCP,新中村化学工业株式会社生产)。
(A)-4:双酚F型环氧树脂(商品名:SB-403S,日本化药工业社生产)
(A)-5:间对甲酚缩水甘油醚(商品名:m,p-CGE、阪本药品工业株式会社生产)。
(B)-1:3-环氧丙氧基丙基三甲氧基硅烷(商品名KBM-403E,信越化学工业株式会社生产)
(B)-2:3-甲基丙烯酰氧丙基三甲氧基硅烷(商品名KBM-503P,信越化学工业株式会社生产)。
(B)-3:2-(3,4-环氧环已基)乙基三甲氧基硅烷(商品名:KBM-303,信越化学工业株式会社生产)。
(C)-1:氧化铝(AX3-15R,Nippon Steel Sumikin Materials Co.,Ltd.生产,平均粒径3μm)
(C)-2:甲硅烷化二氧化硅(商品名:AEROSIL R805,NipponAerosil Co.,Ltd.)。
(D)-1:三羟甲基丙烷三甲基丙烯酸酯(商品名:TMP,共荣社化学株式会社生产)
(D)-2:以四乙二醇二甲基丙烯酸酯为主成分的化合物(商品名:LIGHTESTER 4EG,共荣社化学株式会社生产)。
(E)-1:1,1-二(叔丁基过氧化)环己烷(商品名:PERHEXA C(S)、日本油脂株式会社生产)。
(F)-1:苯酚线型酚醛树脂(商品名:PR-51470,住友电木株式会社生产)
(F)-2:双氰胺(商品名:EH3636AS、ADEKA Corporation生产)。
(S)-1:γ-丁内酯
(G)-1:四苯基鏻四苯基硼酸酯(商品名:TPP-K,北兴化学工业株式会社生产)。
用以下的方法对各实施例、比较例中得到的芯片粘合膏进行评价。
<光反射性>
制作6×3×0.1mm的膜状的试验片(固化条件:以30分钟从25℃升温至175℃、在175℃30分钟),使用分光测色计(商品名:X-rite 8200,S.D.G.K.K.生产)测定波长450nm时的光反射率。
将反射率为60%以上的评价为“A”、反射率低于60%的评价为“B”。将结果示于表2。
<耐紫外线性>
用分光光度计U-4100(Hitachi High-Technologies Corporation生产)测定1mm厚的片状固化物(固化条件:以30分钟从25℃升温至175℃、在175℃30分钟)的波长450nm时的透光率(T0)。同样测定用装备有365nm通带滤波器的UV照射装置(照度100mW/cm2)照射该固化物24小时后的透光率(T1),求得T1/T0(%)。
将T1/T0为90%以上的评价为“A”、T1/T0低于90%的评价为“B”。将结果示于表2。
<粘接强度>
将0.5×0.5mm的硅芯片安装于镀Ag的铜框上,固化条件为以30分钟从25℃升温至175℃、175℃30分钟,在烘箱中使其固化。固化后使用自动粘接力测定装置测定260℃时的热时晶片剪切强度。将260℃热时芯片剪切强度为5N以上的评价为“A”、3N以上且低于5N的评价为“B”、低于3N的评价为“C”。将结果示于表2。
<弹性模量>
制作4×20×0.1mm的膜状的试验片(固化条件:以30分钟从25℃升温至175℃、在175℃30分钟),用动态粘弹性测定机(DMA)在拉伸模式下进行测定。测定条件如下所述。
测定温度:-100~300℃
升温速度:5℃/分钟
频率:10Hz
负荷:100mN
将200℃时的贮存弹性模量作为弹性模量,将弹性模量为800MPa的评价为“A”、400MPa以上且低于800MPa的评价为“B”、低于400MPa的评价为“C”。将结果示于2。
<综合评价>
基于上述评价结果,将实用上能够适用于LED半导体装置的评价为“A”、不能适用的评价为“B”。将结果示于2。
[表2]
由表2的结果可确认:实施例1~5的芯片粘合膏,LED半导体装置的粘接层所要求的反射率即光反射性、耐紫外线性即高耐变色性、弹性模量和密合强度等各种特性均优异,能够制造可实用的LED半导体装置。另外,比较例的芯片粘合膏实用上均无法适用于LED半导体装置。
特别是使用上述通式(a1-1)所示的化合物作为树脂成分(A)的实施例1~3中,所有评价项目均优异。实施例4虽然在树脂成分的结构中具有高极性的NC(=O)骨架,但由于不具有刚性结构,所以虽然能够实现高密合强度,但从弹性模量的观点来看,其结果比实施例1~3稍差。另外,实施例5虽然在树脂成分的结构中具有刚性的环亚烷基骨架,但由于不具有高极性的官能团,所以虽然能够实现高弹性模量,且从密合强度的观点来看,其结果比实施例1~3稍差。
另一方面,在使用环氧树脂作为树脂成分的比较例1中,可以确认其反射率、耐紫外线性差。可以推测这是因为比较例1的树脂成分含有在可见光区域具有光吸收的芳香环,并且含有容易被氧化的官能团所导致的结果。
另外,在使用通式(b-3)所示的硅烷偶联剂的比较例2中,尽管使用上述通式(a1-1)所示的化合物作为树脂成分(A),但可以确认其粘接性较差。可以推测这是因为比较例2中所使用的硅烷偶联剂与实施例所使用的偶联剂相比,具有体积大的反应性官能团,因此,与树脂成分的反应性差,无法得到树脂成分与无机填料、或者树脂成分与被粘附体的良好的结合所导致的结果。
另外,在作为树脂成分不含树脂成分(A)的比较例3中,可以确认其粘接强度、弹性模量差。可以推测这是因为比较例3的树脂成分不具有高极性的官能团,且不含环亚烷基骨架等刚性结构所导致的结果。
以上说明了本发明的优选的实施例,但本发明并不限于这些实施例。在不脱离本发明要点的范围内,可以进行结构的附加、省略、置换及其它变更。本发明并不受上述说明的限制,而仅由权利要求限定。
Claims (17)
1.一种半导体装置,其包括基板、粘接层和发光二极管芯片,该半导体装置的特征在于:
所述粘接层为含有树脂成分(A)、硅烷偶联剂(B)和无机填料(C)的芯片粘合材料的固化物,
树脂成分(A)为选自下述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种,
硅烷偶联剂(B)为选自下述通式(b-1)所示的化合物(B1)和下述通式(b-2)所示的化合物(B2)中的至少1种,
式中,X表示氧原子或氮原子,m和n各自独立地为0或1,当X为氧原子时m+n=1,当X为氮原子时m+n=2;R1、R2、R3、R4各自独立地表示氢原子或不具有芳香环的有机基团,其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R1、R2、R3、R4中的至少2个取代基可以形成环,
Y-(CH2)m-SiR5R6R7 (b-1)
(S)n-((CH2)p-SiR5R6R7)2 (b-2)
式中,R5、R6、R7各自独立地表示碳原子数1~10的烷基或碳原子数1~10的烷氧基,其中,R5、R6、R7中的至少一个为碳原子数1~10的烷氧基;Y为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中的任一种;m和p各自独立地为1~10的整数;n为1以上的整数。
2.如权利要求1所述的半导体装置,其特征在于:
所述芯片粘合材料为芯片粘合膏。
3.如权利要求1或2所述的半导体装置,其特征在于:
所述化合物(A1)含有选自下述通式(a1-1)所示的化合物和下述通式(a1-2)所示的化合物中的至少1种,
式中,R1、R2、R3各自独立地为氢原子或不具有芳香环的有机基团,R1、R2、R3中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,
式中,R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团。
4.如权利要求1~3中任一项所述的半导体装置,其特征在于:
所述化合物(A1)为分子内至少具有3个以上的丙烯酰基或(甲基)丙烯酰基的化合物。
5.如权利要求1或2所述的半导体装置,其特征在于:
所述丙烯酸酯化合物(A2)含有下述通式(a2-1)所示的化合物,
R1′——R11——Z——R12——R2′ (a2-1)
R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R11、R12各自独立地为直链状的亚烷基或单键,Z表示亚环烷基。
6.如权利要求3所述的半导体装置,其特征在于:
所述树脂成分(A)含有所述通式(a1-1)所示的化合物。
7.如权利要求1~6中任一项所述的半导体装置,其特征在于:
所述硅烷偶联剂(B)含有所述通式(b-1)所示的化合物。
8.如权利要求1~7中任一项所述的半导体装置,其特征在于:
在所述通式(b-1)中,Y为环氧丙氧基或(甲基)丙烯酰氧基。
9.一种芯片粘合材料,用于将基板与发光二极管芯片粘接,所述芯片粘合材料的特征在于,含有:
选自下述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种的树脂成分(A);
选自下述通式(b-1)所示的化合物(B1)和下述通式(b-2)所示的化合物(B2)中的至少1种的硅烷偶联剂(B);和
无机填料(C),
式中,X表示氧原子或氮原子,m和n各自独立地为0或1,当X为氧原子时m+n=1,当X为氮原子时m+n=2;R1、R2、R3、R4各自独立地表示氢原子或不具有芳香环的有机基团,其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R1、R2、R3、R4中的至少2个取代基可以形成环,
Y-(CH2)m-SiR5R6R7 (b-1)
(S)n-((CH2)p-SiR5R6R7)2 (b-2)
式中,R5、R6、R7各自独立地表示碳原子数1~10的烷基或碳原子数1~10的烷氧基,其中,R5、R6、R7中的至少一个为碳原子数1~10的烷氧基:Y为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中的任一种;m和p各自独立地为1~10的整数;n为1以上的整数。
10.一种半导体装置的制造方法,其特征在于,包括:
将树脂成分(A)、硅烷偶联剂(B)和无机填料(C)混合制造芯片粘合材料的工序,所述树脂成分(A)为选自下述通式(1)所示的化合物(A1)、和在1分子内具有亚环烷基和2个以上的(甲基)丙烯酰基而不具有芳香环的丙烯酸酯化合物(A2)中的至少1种,硅烷偶联剂(B)为选自下述通式(b-1)所示的化合物(B1)和下述通式(b-2)所示的化合物(B2)中的至少1种;
在基板与发光二极管芯片之间设置所述芯片粘合材料的工序;和
将所述发光二极管芯片粘接在所述基板上的工序,
式中,X表示氧原子或氮原子,m和n各自独立地为0或1,当X为氧原子时m+n=1,当X为氮原子时m+n=2;R1、R2、R3、R4各自独立地表示氢原子或不具有芳香环的有机基团,其中,R1、R2、R3、R4中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R1、R2、R3、R4中的至少2个取代基可以形成环,
Y-(CH2)m-SiR5R6R7 (b-1)
(S)n-((CH2)p-SiR5R6R7)2 (b-2)
式中,R5、R6、R7各自独立地表示碳原子数1~10的烷基或碳原子数1~10的烷氧基,其中,R5、R6、R7中的至少一个为碳原子数1~10的烷氧基;Y为氨基、环氧丙氧基、(甲基)丙烯酰氧基、巯基、异氰酸酯基中的任一种;m和p各自独立地为1~10的整数;n为1以上的整数。
11.如权利要求10所述的半导体装置的制造方法,其特征在于:
所述芯片粘合材料为芯片粘合膏,
在设置所述芯片粘合材料的所述工序中,将所述芯片粘合膏涂布在所述基板和所述发光二极管芯片上。
12.如权利要求10或11所述的半导体装置的制造方法,其特征在于:
所述化合物(A1)含有选自下述通式(a1-1)所示的化合物和下述通式(a1-2)所示的化合物中的至少1种,
式中,R1、R2、R3各自独立地为氢原子或不具有芳香环的有机基团,R1、R2、R3中的至少2个为具有(甲基)丙烯酰基而不具有芳香环的有机基团,
式中,R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团。
13.如权利要求10~12中任一项所述的半导体装置的制造方法,其特征在于:
所述化合物(A1)为分子内至少具有3个以上的丙烯酰基或(甲基)丙烯酰基的化合物。
14.如权利要求10或11所述的半导体装置的制造方法,其特征在于:
所述丙烯酸酯化合物(A2)含有下述通式(a2-1)所示的化合物,
R1′——R11——Z——R12——R2′ (a2-1)
R1′、R2′各自独立地为具有(甲基)丙烯酰基而不具有芳香环的有机基团,R11、R12各自独立地为直链状的亚烷基或单键,Z表示亚环烷基。
15.如权利要求12所述的半导体装置的制造方法,其特征在于:
所述树脂成分(A)含有所述通式(a1-1)所示的化合物。
16.如权利要求10~15中任一项所述的半导体装置的制造方法,其特征在于:
所述硅烷偶联剂(B)含有所述通式(b-1)所示的化合物。
17.如权利要求10~16中任一项所述的半导体装置的制造方法,其特征在于:
在所述通式(b-1)中,Y为环氧丙氧基或(甲基)丙烯酰氧基。
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- 2013-04-10 TW TW102112698A patent/TWI577767B/zh not_active IP Right Cessation
- 2013-04-10 KR KR20147031367A patent/KR20150003287A/ko active IP Right Grant
- 2013-04-10 SG SG11201405729QA patent/SG11201405729QA/en unknown
- 2013-04-10 JP JP2014510055A patent/JP6247204B2/ja active Active
- 2013-04-10 CN CN201380019303.1A patent/CN104221171B/zh not_active Expired - Fee Related
- 2013-04-10 US US14/391,591 patent/US20150060889A1/en not_active Abandoned
- 2013-04-10 EP EP13775725.8A patent/EP2838126A4/en not_active Withdrawn
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Also Published As
Publication number | Publication date |
---|---|
TWI577767B (zh) | 2017-04-11 |
JP6247204B2 (ja) | 2017-12-13 |
CN104221171B (zh) | 2017-11-24 |
KR20150003287A (ko) | 2015-01-08 |
SG11201405729QA (en) | 2014-11-27 |
EP2838126A4 (en) | 2015-10-28 |
WO2013153803A1 (ja) | 2013-10-17 |
EP2838126A1 (en) | 2015-02-18 |
US20150060889A1 (en) | 2015-03-05 |
TW201345994A (zh) | 2013-11-16 |
JPWO2013153803A1 (ja) | 2015-12-17 |
MY170959A (en) | 2019-09-20 |
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