CN1082067C - 光半导体元件包封用环氧树脂组合物 - Google Patents
光半导体元件包封用环氧树脂组合物 Download PDFInfo
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- CN1082067C CN1082067C CN95191178A CN95191178A CN1082067C CN 1082067 C CN1082067 C CN 1082067C CN 95191178 A CN95191178 A CN 95191178A CN 95191178 A CN95191178 A CN 95191178A CN 1082067 C CN1082067 C CN 1082067C
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0203—Containers; Encapsulations, e.g. encapsulation of photodiodes
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- 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
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Medicinal Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种光半导体元件包封用环氧树脂组成物,系由下述(A)~(C)成份组成:(A)环氧树脂;(B)硬化剂;及(C)下式(1)及(2)所示之化合物之至少一种:式中,Y1代表-H、-RCOOH、-COR’(其中R为2价有机基,R’为含碳数30以下之烷基);X代表8~200之整数(但X为化合物(1)中之X部分之平均值);n为重复部分,其重量比例设定为化合物全体之25~95重量%。式中,R代表2价有机基;Y2代表1价或2价以上之金属原子;m为对应Y2之价数之整数,X代表8~200之整数(但X为化合物(2)中之X部分之平均值);n:重复部分n之重量比例设定为化合物全体之25~95重量%。
Description
本发明系关于一种可供作具有优异之脱模性及透明性之包封料之光半导体元件包封用环氧树脂组成物。
有鉴于受光元件及发光元件等光半导体元件之包封料必须具备良好之耐湿性及耐热性,因此以往均使用环氧树脂组成物。
然而,习用之环氧树脂组成物虽具有良好之透明性,但在成形模具中对光半导体元件及环氧树脂组成物实行转送模制而制造光半导体装置时,因脱模性显著的变坏以致不易由成型模具取出光半导体装置。因此,常遭遇诸如因脱模时之应力引起光半导体装置之变形,封装体(package)发生裂痕,光半导体与包封树脂脱开以及金线松脱等各种问题。此等问题之发生虽可借由光半导体装置之各种寿命试验轻易的确认,但一般系于寿命试验前被判断为光半导体装置功能之不良品而被剔除。
为此,长久以来对于包封料的环氧树脂组成物预先添加脱模剂的问题已被探讨。此种添加有脱模剂之环氧树脂组成物,虽依使用的脱模剂之种类有些可增进光半导体元件包封用树脂组成物之重要特性之透明性,但其脱模性不尽理想。反之,借添加脱膜剂制造脱模性良好之包封用树脂组成物,却有透明性不良之问题发生。因此,兼备优良之透明性及脱模性之光半导体元件包封用环氧树脂迄今尚未被开发成功。
本发明系鉴于上述之问题研发一种在转送模制(transfer molding)时具有良好之脱模性且又具有优异之透明性之新颖光半导体元件包封用环氧树脂组成物。
为达成上述之目的,本发明提供一种由下述(A)~(C)成份组成为特征之光半导体元件包封用环氧树脂组成物:
(A)环氧树脂;
(B)硬化剂;及
(C)下式(1)及(2)所示之化合物之至少一种:
CH3CH2CH2-CH2XCH2-CH2-OCH2-CH2-OnY1 …(1)式中,Y1代表-H、-RCOOH、-COR’(其中R为2价有机基,
R’为含碳数30以下之烷基〕;
X代表8~200之整数(但X为化合物(1)中之X部分之平均值);
Y2代表1价或2价以上之金属原子;
m为对应Y2之价数之整数,
X代表8~200之整数(但X为化合物(2)中之X部分之平均值);
n:重复部分n之重量比例设定为化合物全体之25~95重量%。
即,本发明人等为了获得兼备有优异之透明性及脱模性之光半导体元件包封用环氧树脂组成物,经潜心研究结果发现,以前述式(1)及(2)之至少一种化合物作为(C)成份使用时,既可不损害包封用组成物之透明性且又可发挥优异之脱模性,从而完成本发明。
尤其对组成物之全体重量使用0.01~15重量%之上述(C)成份时,可确实防止玻璃转变温度及耐湿性之下降而发挥满意之脱模性。
本发明之光半导体元件包封用环氧树脂组成物系由环氧树脂(A成份)、硬化剂(B成份)及特定之化合物(C成份)以及视需要添加硬化促进剂所组合而成者,其通常呈粉末状,亦可将粉末打锭成为颗粒或锭状。
在本发明中使用之环氧树脂(A成份),只要透明性无问题,不特别限定,可使用习知之环氧树脂,包括:双酚A型环氧树脂、双酚F型环氧树脂、酚线型酚醛环氧树脂、甲酚线型酚醛树脂、脂环或环氧树脂、三缩水甘油异三聚氰酸酯、乙内醋脲系环氧树脂等含氮环氧树脂,加水双酚A型环氧树脂、脂肪族系环氧树脂、缩水甘油醚型环氧树脂以及双酚S型环氧树脂等。此等树脂可单独或混合使用。上述各种环氧树脂中,为在光半导体元件包封后防止包封树脂不变色,最好使用双酚A型环氧树脂、双酚F型环氧树脂、脂环或环氧树脂及三缩水甘油异三聚氰酸酯。
至于与上述环氧树脂(A成份)连用之硬化剂(B成份),只要在透明性方面无问题,则无特别限制,可选用对包封树脂之变色影响极小之各种酸酐,例如酞酸酐、马来酸酐、苯偏三酸酐、苯均四酸酐、六氢酞酸酐、四氢酞酸酐、甲基拿吉酸酐(methyl nadic anhydride)、拿吉酸酐、戊二酸酐、甲基六氢酞酸酐、甲基四氢酞酸酐等。此等硬化剂可单独或混合使用。较可取者为酞酸酐。六氢酞酸酐、四氢酞酸酐及甲基六氢酞酸酐。除上述之酸酐系硬化剂之外亦可单独或混合使用习知之胺类、酚类、或六氢酞酸、四氢酞酸及甲基六氢酞等羧酸类之硬化剂。
上述环氧树脂(A成份)及硬化剂(B成份)之用量比例为,例如以酸酐作为硬化剂时,对环氧树脂中之环氧基1当量使用酸酐0.5~1.5当量,尤其0.7~1.2当量更为可取。即,在上述用量比例中,如酸酐当量为0.5当量以下时,所得之环氧树脂组成物之硬化后之色相变恶,反之超过1.5当量时耐湿性有低降之倾向。又,如以酸酐以外之上述胺类、酚类、羧酸类等硬化剂作为硬化剂单独或混合使用时,其用量比例亦准用上述使用酸酐之用量比例(当量比)。
与上述A成份及B成份连用之特定化合物(C成份)可选自式(1)及(2)之任一种化合物。使用此等化合物时,可防止包封树脂之透明性之下降,同时又可于转送模制时,使半导体装置容易脱模。使用此等化合物为本发明之重要特征。
CH3CH2CH2-CH2xCH2-CH2-OCH2-CH2-OnY1…(1)
上式中Y1代表氢原子、-RCOOH(R为2价有机基)、-COR’或R’(R’为碳原子30以下之烷基)。最好Y1为氢原子,-RCOOH(R为碳原子30以下之亚烃基)、-COR’或-R’(R’为C1-C30烷基)。
上式中Y2为金属原子,例如锌、钙、钡、铝、镁、铅、钾、钠等。特别考虑透明性时,Y2为钙、钠及锌较佳。
在上式(1)及(2)中,重复部分X之数为8~200而且重复部分n之重量比例须设定为式(1)及(2)各化合物全体之25~95%范围。较可取为式(1)及(2)之重复部分X各为13~28而且重复部分n之重量比例为各化合物全体之35~85%,更可取为式(1)及(2)之重复部分X为17~23而且重复部分n之重量比例为45~70%。若上述式(1)及(2)之化合物各有数种时,其重复数X为各化合物之重复数X之平均值,同时上述重复部分n之重量比例(%)为依下式算出之值。
根据上述,式(1)及(2)所代表之化合物须使用平均分子量300~30万范围,较可取为平均分子量600~12,000,尤其平均分子量900~5,000之化合物。
上述式(1)之化合物可借例如令乙烯氧附加于高级醇而制得。
上述式(1)及(2)之至少一种化合物(C成份)之用量应为环氧树脂组成物全体重量之0.01~15%范围,0.1~5%较可取,尤其0.5~3%更为可取。即,C成份之用量比过低时,难使半导体装置自成形模脱离(即脱模性不佳),反之过高时有减低玻璃转变温度及耐湿性之虞。
本发明之光半导体元件包封用环氧树脂组成物,除上述之A~C成份之外,在不损害其透明性之范围内,可视需要适当添加习用之诸如硬化促进剂、染颜料、改性剂、抗氧化剂、螯合剂及脱模剂等。
可用之硬化促进剂并无特别的限制,习用之例如叔胺类、咪唑类、季铵及有机金属盐类、磷化合物。1,8-重氮-二环(5,4,0)十一碳烯-7及彼等衍生物。此等硬化促进剂可单独或混合使用。较可取者为叔胺、咪唑类。硬化促进剂之用量为对上述环氧树脂(A成份)100重量份设定于0.01~8重量份范围,更可取为0.1~3%重量份。硬化剂用量低于0.01重量份时,无法发挥充分之硬化促进效果,超过8重量份时会引起包封树脂(硬化物)之变色。
上述改性剂可选自习知之二醇类或硅酮类。
上述抗氧化剂可选自习知之酚系化合物,胺系化合物、有机硫磺系化合物、膦系化合物等。
上述抗螯合剂可选自习知之硅烷系、钛酸盐系化合物。
上述脱模剂可选自习知之例如十八烷酸、二十烷酸、二十九烷酸等长链羧酸及其金属盐,十八烷醇等高级醇类、十八烷基二酰胺等酰胺类、卡诺巴腊(carnaubawax)、磷酸酯等酯类,及烷烃系石腊等。此等脱模剂之用量通常为树脂组成物全体之3重量%,但只要不损害透明性,使用量不受此限定。
若要求光分散性,则除上述成份之外尚可添加诸如石英玻璃粉末、滑石、硅氧粉末、铝氧粉末、碳酸钙等习知之无机填充剂。
使用上述成份构成之光半导体元件包封用环氧树脂组成物中,其为获得优异之透明性及脱模性,较可取之成份组合,为以双酚A型环氧树脂、三缩水甘油异三聚氰酸酯、酚线型酚醛环氧树脂、脂环或环氧树脂作为环氧树脂(A成份),以四氢酞酸酐、酞酸酐作为硬化剂(B成份),以叔胺类、咪唑类等添加剂作为硬化促进剂,而令该等成份与上述式(1)及(2)之任意一种化合物(C成份)相组合。此时所使用之式(1)或式(2)化合物中,其重复数X宜为13~28范围之整数,而重复部分n之重量比例宜为化合物全体之35~85%范围。
在上述之可取组合中,从防止包封树脂硬化物之变色观点看,最好之组合为以双酚A型环氧树脂、三缩甘油异三聚氰酸酯作为环氧树脂(A成份),以四氢酞酸酐作为硬化剂(B成份),以咪唑类作为硬化促进剂,令此等成份与上述式(1)或(2)中其重复数X为17~23,重复部分n之重量比例为化合物全体之45~70%之化合物(成份C)相组合。
本发明之光半导体元件包封用环氧树脂组成物例如可依下法制备。即对上述A~C成份,视需要添加所定比例之硬化促进剂、染料、颜料、改性剂、抗氧化剂、螯合剂、脱模剂、填充剂等添加剂,依干混法或融混法等一般常用法予以混合、混捏,然后冷却、粉碎。进而视需要将所得之粉末体予以打锭制取目的之环氧树脂组成物。
使用此种环氧树脂组成物实施光半导体元件之包封时,其方法虽无特别限制,但宜用转送模制法等一般习用之成型法。
由此制得之半导体装置,因其包封树脂具有优异之透明性及脱模性,故可避免起因于脱模性不良而产生之种种问题。
本发明之包封树脂硬化物经分光光度计测定结果,厚度1mm之硬化物对波长600nm之光显示70%以上之透过率,较可取者达80%以上透过率。
<本发明最可取之实施例:>
兹将本发明实施例配合比较例说明于下。
在实施本发明之实施例前,预先准备表1所示之化合物a~1。其中化合物a~i为上述式(1)之化合物,且末端之Y1为氢原子之化合物。
表1
另准备表2所示化合物m~o,此等化合物为上述式(1)所示之化合物。
式(1)所示之化合物 | 结构式 | 平均分子量 | 重复数n | ||
重复数-X | 反复数部分n的重量比例(%)* | ||||
a | 10 | 50.4 | CH3CHCG2-CH2xCH2-CH2-CH2-OCH2-CH2-OnH | 742 | 8.5 |
b | 14 | 49.8 | 928 | 10.5 | |
c | 14 | 79.9 | 2314 | 42.0 | |
d | 17 | 50.0 | 1100 | 12.5 | |
e | 22 | 50.5 | 1394 | 16.0 | |
r | 69 | 50.0 | 4008 | 45.5 | |
g | 14 | 19.1 | 576 | 2.5 | |
h | 17 | 19.4 | 682 | 3.0 | |
i | 22 | 20.3 | 866 | 4.0 | |
j | 二十二烷酸 | ||||
k | 卡诺巴腊 | ||||
l | 十八酸锌 |
同时又准备下述之环氧树脂A~D,硬化剂E~G,硬化促进剂H、I及抗氧化剂J~L:
〔环氧树脂A〕
双酚A型环氧树脂(环氧当量650,融点83℃)
〔环氧树脂B〕
三(2,3-环氧丙基)异三聚氰酸酯(还氧当量100,融点110℃)
〔环氧树脂C〕
甲酚线型酚醛树脂(环氧当量215,软化点92℃)
〔环氧树脂D〕
如下式(3)所示之脂环式环氧树脂(环氧当量187,软化点73℃)式(3)中,R1为三羟甲基丙烷残基,而A为〔硬化剂E〕:四氢酞酸酐〔硬化剂F〕:二氨基二苯甲烷〔硬化剂G〕:酚线型酚醛树脂(羟基当量105,软化点72℃)〔硬化促进剂H〕:2-乙基-4-甲基咪唑〔硬化促进剂I〕:二甲基苯甲胺〔抗氧化剂J〕:如下结构式(4)所示之2,6-二-叔丁基氢化甲苯〔抗氧化剂K〕:如下结构式(5)所示之三苯基亚磷酸酯
〔抗氧化剂L〕:9,10-二氢-9-氧-10-磷菲-10-氧化物
实施例1~27及比较例1~6
将下面表4~表8所示之各成份以同表中所示之比例掺合,而在混合辊机中在80-130℃下实行熔融混捏,待熟成后在室温下冷却,然后予以粉碎获得目的之粉末状环氧树脂组成物。〔表4〕 (份)
[表5]
实 施 例 | ||||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
环氧树脂 | A | 725 | 725 | 725 | 725 | 80 | 80 | 80 |
B | 27.5 | 27.5 | 27.5 | 27.5 | 20 | 20 | 20 | |
C | - | - | - | - | - | - | - | |
D | - | - | - | - | - | - | - | |
硬化剂 | E | 55.2 | 55.2 | 55.2 | 55.2 | 44.2 | 44.2 | 44.2 |
F | - | - | - | - | - | - | - | |
G | - | - | - | - | - | - | - | |
硬化促进剂 | H | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
I | - | - | - | - | - | - | - | |
抗氧化剂 | J | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
K | 1.0 | 1.0 | 1.0 | 1.0 | 1.5 | 1.5 | 1.5 | |
L | - | - | - | - | - | - | - | |
化合物 | a | 1.6 | - | - | - | - | - | - |
b | - | 1.6 | - | - | - | - | - | |
c | - | - | 8.3 | - | - | - | - | |
d | - | - | - | 1.6 | 4.5 | - | - | |
e | - | - | - | - | - | 0.44 | 0.74 | |
化合物含量(%) | 1.0 | 1.0 | 5.0 | 1.0 | 3.0 | 0.3 | 0.5 |
(份)
实 施 例 | |||||||||
8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | ||
环氧树脂 | A | 80 | 80 | 100 | - | 55 | 60 | 80 | 80 |
B | 20 | 20 | - | - | - | - | 20 | 20 | |
C | - | - | - | 100# | 45 | - | - | - | |
D | - | - | - | - | - | 40 | - | - | |
硬化剂 | E | 44.2 | 44.2 | - | - | 46.2 | 37.2 | 44.2 | 44.2 |
F | - | - | 7.6 | - | - | - | - | - | |
G | - | - | - | 50 | - | - | - | - | |
硬化促进剂 | H | 0.4 | 0.4 | - | 0.4 | - | - | 0.4 | 0.4 |
I | - | - | - | - | 0.8 | 0.8 | - | - | |
抗氧化剂 | J | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
K | 1.5 | 1.5 | - | - | - | - | 1.5 | 1.5 | |
L | - | - | 1.0 | 1.0 | 1.0 | 1.0 | - | - | |
化合物 | a | - | - | - | - | - | - | - | - |
b | - | - | - | - | - | - | - | - | |
c | - | - | - | - | - | - | - | - | |
d | - | - | - | - | - | - | - | - | |
e | 4.5 | 7.7 | 3.4 | 4.7 | 4.6 | 4.3 | 16.4 | - | |
f | - | - | - | - | - | - | - | 0.15 | |
化合物含量(%) | 3.0 | 5.0 | 3.0 | 3.0 | 3.0 | 3.0 | 10.0 | 0.1 |
*实施例11,使用甲酚线型酚醛环氧树脂(环氧当量215,软化点71℃)[表6]
(份)
[表7]
实 施 例 | |||||||||
16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | ||
环氧树脂 | A | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
B | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | |
C | - | - | - | - | - | - | - | - | |
D | - | - | - | - | - | - | - | - | |
硬化剂 | E | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 |
F | - | - | - | - | - | - | - | - | |
G | - | - | - | - | - | - | - | - | |
硬化促进剂 | H | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
I | - | - | - | - | - | - | - | - | |
抗氧化剂 | J | 1.0. | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
K | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
L | - | - | - | - | - | - | - | - | |
化合物 | m | 3.0 | - | - | - | - | - | - | - |
n | - | 0.3 | - | - | - | - | - | - | |
o | - | - | 3.0 | - | - | - | 0.15 | 7.7 | |
p | - | - | - | 3.0 | - | - | - | - | |
q | - | - | - | - | 3.0 | - | - | - | |
r | - | - | - | - | - | 3.0 | - | - | |
化合物含量(%) | 20 | 0.2 | 20 | 20 | 20 | 20 | 0.1 | 5.0 |
(份)
〔表8〕
实 施 例 | |||||||
24 | 25 | 26 | 27 | 28 | 29 | ||
环氧树脂 | A | 80 | 80 | 80 | 80 | 80 | 80 |
B | 20 | 20 | 20 | 20 | 20 | 20 | |
C | - | - | - | - | - | - | |
D | - | - | - | - | - | - | |
硬化剂 | E | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 |
F | - | - | - | - | - | - | |
G | - | - | - | - | - | - | |
硬化促进剂 | H | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
I | - | - | - | - | - | - | |
抗氧化剂 | J | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
K | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
L | - | - | - | - | - | - | |
化合物 | e | - | - | - | - | 1.5 | 1.5 |
q | 0.15 | 7.7 | - | - | 1.5 | - | |
r | - | - | 0.15 | 7.7 | - | 1.5 | |
化合物含量(%) | 0.1 | 5.0 | 0.1 | 5.0 | 20 | 20 |
(份)
比 较 例 | |||||||
1 | 2 | 3 | 4 | 5 | 6 | ||
环氧树脂 | A | 80 | 80 | 80 | 80 | 80 | 80 |
B | 20 | 20 | 20 | 20 | 20 | 20 | |
C | - | - | - | - | - | - | |
D | - | - | - | - | - | - | |
硬化剂 | E | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 | 44.2 |
F | - | - | - | - | - | - | |
G | - | - | - | - | - | - | |
硬化促进剂 | H | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
I | - | - | - | - | - | - | |
抗氧化剂 | J | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
K | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
L | - | - | - | - | - | - | |
化合物 | g | 4.5 | - | - | - | - | - |
h | - | 4.5 | - | - | - | - | |
i | - | - | 4.5 | - | - | - | |
j | - | - | - | 3.0 | - | - | |
k | - | - | - | - | 4.5 | - | |
l | - | - | - | - | - | 0.74 | |
化合物含量(%) | 3.0 | 3.0 | 3.0 | 2.0 | 3.0 | 0.5 |
使用上述实施例及比较例制备而得之粉末状环氧树脂,对光半导体元件实施转送模制(模制条件:150℃,4分钟),继后在150℃下实施3小时之后硬化处理而制取目的之光半导体装置。
对此光半导体装置评估其自转送模具脱离之脱模性。脱模性之评估方法为先使用三聚氰胺树脂(melamine resin,日本Carbite公司制,商品名Nicalet ECR,AA级)实施清扫成型后,连续实行转送模制(transfer molding),并对第4次模制所得之光半导体装置,只利用顶销(injectorpin)之操作自模具内腔顶出光半导体装置〔其封装之尺寸:19.8mm×13.9mm×2.8mm(厚度)〕。此时可以顺利顶出者评估为◎;需另配合吹气才能取出者评估为○;靠顶销及吹气仍无法取出而需以外加机械力才能取出致使封装发生变形及裂伤者评估为X,其结果显示于如下表9~表13。
另外,使用上述各环氧树脂组成物模制厚度1mm之硬化物(成型条件:150℃,4分钟,及后硬化处理:150℃,3小时)。对此制品借由分光光度计(岛津制作所制,UV-3101PC)测定波长600nm光之透过率,其结果一并示于表9~表13。
[表9]
[表10]
[表11]
[表12]
[表13]
实 施 例 | |||||||
1 | 2 | 3 | 4 | 5 | 6 | 7 | |
脱模性 | ○ | ○ | ○ | ○ | ◎ | ○ | ○ |
光透过率(%) | 82.4 | 84.6 | 81.0 | 88.3 | 72.3 | 92.9 | 94.4 |
实 施 例 | ||||||||
8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | |
脱模性 | ◎ | ◎ | ○ | ○ | ○ | ○ | ○ | ○ |
光透过率(%) | 95.2 | 95.6 | 78.0 | 91.3 | 94.0 | 94.8 | 96.0 | 73.0 |
实 施 例 | ||||||||
16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | |
脱模性 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
光透过率(%) | 90.0 | 70.0 | 91.0 | 88.0 | 78.0 | 81.2 | 93.0 | 79.0 |
实 施 例 | ||||||
24 | 25 | 26 | 27 | 28 | 29 | |
脱模性 | ○ | ◎ | ○ | ◎ | ◎ | ◎ |
光透过率(%) | 85.0 | 72.0 | 90.0 | 73.0 | 85.0 | 88.0 |
比 较 例 | ||||||
1 | 2 | 3 | 4 | 5 | 6 | |
脱模性 | ◎ | ◎ | ◎ | × | ◎ | × |
光透过率(%) | 1.0> | 1.0> | 1.0> | 98.8 | 1.0> | 91.0 |
由上表9~13之结果可知,本发明之实施例制品不但光透过性高而且具有良好脱模性,显示兼备要求之两特性。与此相比,比较例1~及比较例5之制品虽具良好之脱模性,但光透光率非常差。又,比较例4及6之光透过率虽高,但脱模性非常差, 显示比较例者并未兼备良好之光透过性及脱模性。
由上所述,本发明之光半导体包封环氧树脂组成物含有式(1)或式(2)之特定化合物至少一种(C成份),使得由其构成之树脂封装(package)兼备优异之透明性及脱模性,在产业上具有极高之利用性。尤其将上述之成份(C)之含有量设于环氧树脂组成物全体之0.01~15重量%之场合,更具有可防止玻璃转变温度及耐湿性之减低之功效。因此,利用此环氧树脂组成物包封光半导体元件时,可防止因脱模性之不良而引起之制品缺陷,制取品质及可靠性高之光半导体装置。
Claims (8)
1.一种光半导体元件包封用的环氧树脂组合物,该组合物包括:(A)环氧树脂;(B)硬化剂;及(C)下式(1)及(2)所示之化合物之至少一种,式(1)为:
CH3CH2CF2-CH2XCH2-CH2-OCH2-CH2-OnY1 …(1)式中,Y1代表-H、-RCOOH、-COR’,其中R为2价有机基,
R’为含碳原子数30以下之烷基;
X代表17~200之整数,但X为化合物(1)中之X部分之平均值;
n为重复部分,其重量比例设定为化合物全体之25~95重量%,式(2)为:
式中,R代表2价有机基;
Y2代表1价或2价以上之金属原子;
m为对应Y2之价数之整数,
X代表8~200之整数,但X为化合物(2)中之X部分之平均值;
n为重复部分,其重量比例设定为化合物全体之25~95重量%;
其中(C)的含量为环氧树脂组合物的0.01-15重量%。
2.根据权利要求1的组合物,其中式(1)及式(2)之重复数X为17~28之整数,且重复部份n之重量比例为化合物全体之35~85重量%。
3.根据权利要求1的组合物,其中式(1)及式(2)之重复数X为-17~23之整数,且重复部份n之重量比例为化合物全体之45~70重量%。
4.根据权利要求1、2或3的组合物,其中成份(C)之含量为组成物全体之0.1~5重量%。
5.根据权利要求1、2或3的组合物,其中成份(C)之含量为组成物全体之0.5~3重量%。
6.根据权利要求1的组合物,其中成份(A)系选自双酚A型环氧树脂、三缩水甘油三聚氰酸酯、酚线型酚醛环氧树脂及脂环氧树脂之至少一种环氧树脂;成份(B)系选自四氢酞酸酐及酞酸酐之至少一种硬化剂;成份(C)系选自式(1)及式(2)之至少一种化合物,其中式(1)及(2)之重复数X为17~28之整数,重复部分n之重量比例为化合物全体之35~85重量%,且另掺合有选自叔胺类及咪唑类之至少一种硬化促进剂。
7.根据权利要求1的组合物,其中成份(A)系选自双酚A型环氧树脂及三缩水甘油异三聚氰酸酯之一种;成份(B)系四氢酞酸酐;成份(C)系式(1)及式(2)之至少一种化合物,其中式(1)及(2)之重复数X为17~23之整数,重复部分n之重量比例为化合物全体之45~70重量%;硬化促进剂咪唑类。
8.一种光半导体装置,该装置是由包括成分(A)~(C)的环氧树脂组合物包封所构成的,所说成分(A)~(C)为:
(A)环氧树脂;
(B)硬化剂;及
(C)下式(1)及(2)所示之化合物之至少一种,式(1)为:
CH3CHCH2-CHXCH2-CH2-OCH2-CH2-OnY1 …(1)
式中,Y1代表-H、-RCOOH、-COR’,其中R为2价有机基,
R’为含碳原子数30以下之烷基;
X代表17~200之整数,但X为化合物(1)中之X部分之平均值;
Y2代表1价或2价以上之金属原子;
m为对应Y2之价数正整数,
X代表8~200之整数,但X为化合物(2)中之X部分之平均值;
n为重复部分,其重量比例设定为化合物体之25~95重量%;其中成分(C)的含量为环氧树脂组合物的0.01-15重量%。
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JP20595695A JPH09208805A (ja) | 1994-11-09 | 1995-08-11 | 光半導体素子封止用エポキシ樹脂組成物 |
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US (1) | US6001483A (zh) |
EP (1) | EP0738759B1 (zh) |
JP (1) | JPH09208805A (zh) |
KR (1) | KR100343308B1 (zh) |
CN (1) | CN1082067C (zh) |
DE (1) | DE69531191T2 (zh) |
TW (1) | TW288186B (zh) |
WO (1) | WO1996015191A1 (zh) |
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JP3392068B2 (ja) * | 1999-01-26 | 2003-03-31 | 松下電工株式会社 | 光半導体封止用エポキシ樹脂組成物及び光半導体装置 |
JP3617386B2 (ja) * | 1999-09-27 | 2005-02-02 | 松下電工株式会社 | 光半導体用エポキシ樹脂組成物及び光半導体装置 |
JP3430150B2 (ja) | 2000-12-18 | 2003-07-28 | 日東電工株式会社 | 光半導体素子封止用エポキシ樹脂組成物の製造方法 |
JP2002201288A (ja) * | 2001-01-09 | 2002-07-19 | Nitto Denko Corp | 半導体封止用エポキシ樹脂組成物の製造方法 |
SG115811A1 (en) * | 2004-03-31 | 2005-10-28 | Nitto Denko Corp | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
JP4890872B2 (ja) * | 2006-01-30 | 2012-03-07 | ルネサスエレクトロニクス株式会社 | 光半導体封止用透明エポキシ樹脂組成物及びそれを用いた光半導体集積回路装置 |
DE102006030038A1 (de) * | 2006-06-29 | 2008-01-03 | Qimonda Ag | Versiegelungsschicht zum Versiegeln gegenüber einer Umgebung |
JP2008031229A (ja) * | 2006-07-26 | 2008-02-14 | Matsushita Electric Works Ltd | 光半導体封止用エポキシ樹脂組成物及び光半導体装置 |
JP5072070B2 (ja) * | 2007-03-08 | 2012-11-14 | 日東電工株式会社 | 光半導体素子封止用エポキシ樹脂組成物およびそれを用いた光半導体装置 |
KR100898337B1 (ko) * | 2007-12-26 | 2009-05-20 | 제일모직주식회사 | 반도체 소자 밀봉용 에폭시 수지 조성물 및 이를 이용한 반도체 소자 |
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JP5410085B2 (ja) * | 2008-12-17 | 2014-02-05 | 日東電工株式会社 | 光半導体素子封止用エポキシ樹脂組成物およびそれを用いた光半導体装置 |
DE102009007392A1 (de) * | 2009-01-29 | 2010-08-05 | Siemens Aktiengesellschaft | Tränkharzsystem für Isolierstoffe in Schaltanlagen |
DE102009008464A1 (de) | 2009-02-10 | 2010-08-12 | Siemens Aktiengesellschaft | Gießharzsystem für Isolierstoffe in Schaltanlagen |
KR101332430B1 (ko) | 2009-12-31 | 2013-11-22 | 제일모직주식회사 | 반도체 소자 밀봉용 에폭시 수지 조성물 및 이를 이용한 반도체 소자 패키지 |
JP5699443B2 (ja) * | 2010-04-09 | 2015-04-08 | 日立化成株式会社 | 光反射用熱硬化性樹脂組成物、光半導体素子搭載用基板及びその製造方法、並びに光半導体装置 |
JP6524840B2 (ja) * | 2015-07-30 | 2019-06-05 | 新日本理化株式会社 | エポキシ樹脂組成物及びエポキシ硬化物 |
JP6989044B1 (ja) | 2021-03-31 | 2022-01-05 | 住友ベークライト株式会社 | 封止構造体の製造方法およびタブレット |
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- 1995-11-07 CN CN95191178A patent/CN1082067C/zh not_active Expired - Fee Related
- 1995-11-07 KR KR1019960703694A patent/KR100343308B1/ko not_active IP Right Cessation
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- 1995-11-07 US US08/669,317 patent/US6001483A/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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DE69531191T2 (de) | 2004-04-15 |
KR100343308B1 (ko) | 2002-11-23 |
US6001483A (en) | 1999-12-14 |
DE69531191D1 (de) | 2003-08-07 |
EP0738759A1 (en) | 1996-10-23 |
WO1996015191A1 (en) | 1996-05-23 |
EP0738759A4 (en) | 1998-09-09 |
EP0738759B1 (en) | 2003-07-02 |
CN1138343A (zh) | 1996-12-18 |
JPH09208805A (ja) | 1997-08-12 |
TW288186B (zh) | 1996-10-11 |
KR970700232A (ko) | 1997-01-08 |
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