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WO2000002975A1 - Produit d'encapsulage a base de polymere en cristaux liquides - Google Patents

Produit d'encapsulage a base de polymere en cristaux liquides Download PDF

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Publication number
WO2000002975A1
WO2000002975A1 PCT/US1999/015095 US9915095W WO0002975A1 WO 2000002975 A1 WO2000002975 A1 WO 2000002975A1 US 9915095 W US9915095 W US 9915095W WO 0002975 A1 WO0002975 A1 WO 0002975A1
Authority
WO
WIPO (PCT)
Prior art keywords
molding compound
mole percent
filler
weight percent
liquid crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1999/015095
Other languages
English (en)
Inventor
Paul A. Koning
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
COOKSON SEMICONDUCTOR PACKAGING MATERIALS
BP Corp North America Inc
Original Assignee
COOKSON SEMICONDUCTOR PACKAGING MATERIALS
BP Corp North America Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by COOKSON SEMICONDUCTOR PACKAGING MATERIALS, BP Corp North America Inc filed Critical COOKSON SEMICONDUCTOR PACKAGING MATERIALS
Priority to AU48574/99A priority Critical patent/AU4857499A/en
Publication of WO2000002975A1 publication Critical patent/WO2000002975A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention relates to molding compounds useful for encapsulating electrical and electronic components. More particularly, the invention relates to thermoplastic molding compounds capable of carrying relatively high fractions of filler material.
  • thermosetting Materials used to encapsulated electrical and electronic components such as semiconductors typically have been thermosetting in nature.
  • these compounds are comprised of one or more epoxy thermosetting resins, a substantial weight fraction of an inert filler material such as silica, and a variety of additives such as catalysts, hardeners, coupling agents, and release agents.
  • Such compounds generally are well- suited for use as encapsulants as the compounds have relatively low melt viscosities that allow heated, uncured compound to flow around a device's connecting wires such as the 1 to 3 micron wires used in semiconductor leadframes prior to completion of the thermosetting process, and because the relatively high weight fraction of inert filler provides for a low coefficient of thermal expansion of the molded device.
  • Liquid crystalline polymers possess very low melt viscosities when compared to thermoplastics, and therefore are thought to be useful in molding compounds. LCP compounds are characterized by their ability to be processed in an anisotropic melt phase. Unfortunately, LCP encapsulants require relatively high amounts of filler to provide acceptable moisture uptake and thermal expansion performance. When inert filler materials are added to
  • LCPs for use in encapsulation applications, the low viscosity of the LCP deteriorates with increasing filler loading. At loadings as low as about 30 weight percent, the viscosity of the compound increases to the point where the compound shifts or displaces connecting wires for the device, resulting in the phenomena known as "wire sweep.” Because LCP encapsulants generally are believed to require greater than 30 weight percent of filler to obtain adequate thermal and moisture uptake performance, and because such filler loadings result in viscosity increases and unacceptable wire sweep performance, LCPs are not typically used in electronic molding compounds.
  • the wire sweep performance of certain LCP-based encapsulant compounds can be enhanced by coating fillers used in the compounds with certain silane coupling agents.
  • the viscosity can be reduced by factors of 10 to 25 by using appropriate non-polar silane coupling agents.
  • a polyester-based liquid crystal polymer resin was used as the base resin for the encapsulants of the following Examples.
  • the polymer used comprised approximately 7 mole percent hydroquinone, 10 mole percent purified isophthalic acid, 10 mole percent purified terephthalic acid, 60 mole percent parahydroxybenzoic acid, and 13 mole percent 4, 4' biphenyldiol.
  • the polymer exhibited a melting point of approximately 300 degrees Centigrade.
  • Coupling agents used to coat fillers were pre-reacted to the fillers and dried prior to compounding at a loading of 0.5 weight percent coupling agent calculated on the basis of filler weight. Molding formulations were then prepared by compounding on a 25 millimeter Berstorff co-rotating, meshing twin screw extruder. Compounded formulations were dried in a 100 degree Centigrade forced air drying prior to molding, and molding of samples was accomplished on a 55 ton Toyo injection molding machine using a three plate mold having two fill gates, one located top dead center on the die, and the other located bottom dead center on the die.
  • Example 1 The formulation tested was unfilled LCP as described above. The measured melt viscosity was 0.2 Pascal-seconds.
  • Example 2 The formulation tested was LCP filled with 50 weight percent of Denka FB-74 spherical silica filler having an average particle size of about 35 microns. The filler was uncoated. The measured melt viscosity was about 48 Pascal-seconds.
  • Example 3 The formulation tested was LCP filled with 50 weight percent of Denka FB-74 spherical silica filler having an average particle size of about 35 microns.
  • the silica filler was coated and dried as described above using a tri(2-methoxyethoxy) vinylsilane coupling agent available as Silquest A-172 from the Whitco Corporation of Tarrytown, New York.
  • the measured melt viscosity was about 1 Pascal-second.
  • Example 4 The formulation tested was LCP filled with 50 weight percent of Denka FB-74 spherical silica filler having an average particle size of about 35 microns.
  • the silica filler was coated and dried as described above using a 3- glycidyloxypropyltrimethoxysilane coupling agent available as Silquest A-187 from the Whitco Corporation of Tarrytown, New York.
  • the measured melt viscosity was about 14 Pascal-second.
  • Example 5 The formulation tested was LCP filled with 50 weight percent of Denka FB-74 spherical silica filler having an average particle size of about 35 microns.
  • the silica filler was coated and dried as described above using a 3- aminopropyltriethoxysilane coupling agent available as Silquest A-1100 from the Whitco Corporation of Tarrytown, New York.
  • the measured melt viscosity was about 6 Pascal-second.
  • the formulation tested was LCP filled with 50 weight percent of Denka FB-74 spherical silica filler having an average particle size of about 35 microns.
  • the silica filler was coated and dried as described above using a trimethoxymethylsilane coupling agent available as Silquest A-1630 from the Whitco Corporation of Tarrytown, New York.
  • the measured melt viscosity was about 2 Pascal-seconds.
  • An LCP formulation was prepared from 47.5 weight percent of the resin used in Example 3, 50 weight percent of a 35 micron spherical silica filler equivalent to the filler used in Example 3, and 2.5 weight percent of a polysulfone adhesion promoter.
  • the adhesion promoter was a polysulfone compound available from Amoco Chemical Company as Polysulfone P-1700
  • the adhesion of the molded formulation to a copper 194 alloy was measured by preparing lap shear strength test specimens. The test specimens with a one inch overlap. A 15 mil thick film of the LCP formulation was placed in the overlap within a metal fixture. The fixture was placed in a 330 degree Centigrade compression mold, allowed to heat, and pressurized to cause the melted formulation to flow slightly. The resulting 10 mil thick bond was allowed to cool to room temperature and tested in an Instron/MTS model 1122 tensile machine at a crosshead speed of 0.05 inches per minute. The lap shear strength measure in this manner was approximately 469 psi. The 469 psi value corresponds favorably to current low stress epoxy mold compounds which typically exhibit a lap shear strength to the same copper alloy of about 400 psi.
  • a thin quad flat pack (TQFP) integrated circuit was prepared by molding an LCP formulation consisting of 45 weight percent of the resin used in Example 7, 50 weight percent of a 35 micron spherical silica filler equivalent to the filler used in Example 3, and 5 weight percent of the polysulfone adhesion promoter used in Example 7, around a TQFP die and leadframe assembly at about 300 degrees Centigrade.
  • the TQFP wires connecting the die to the leadframe were 144, 100 mil long, 1.3 mil diameter gold lead wires.
  • the molded device was examined by x-ray micrograph using a Nicolet NXR-300, and showed that the average wire sweep of the four worst wires was only about 5 percent.
  • Example 9 The experiment of Example 8 was repeated with a filler loading of approximately 70 weight percent. The x-ray micrograph showed severe wire sweep and in some cases, wire debonding from the die.
  • Example 8 demonstrates that complex devices such as a 144 lead
  • TQFP can be successfully molded using LCP encapsulants in accordance with the present device at filler loadings of at least 50 weight percent. While the TQFP failed to mold successfully at 70 weight percent filler loading, it is believed that packages having fewer leads and or thicker wires, such as dual in line packages (DIPs), can be successfully molded at filler loadings exceeding 50 weight percent.
  • DIPs dual in line packages
  • Example 10 The moisture resistance of the TQFP molded in Example 8 was measured in Example 10, below.
  • Example 10 The 144 lead TQFP of Example 8 was preconditioned at JEDEC Level
  • Example 11 The physical robustness of the TQFP's of the type molded in Example 8 is demonstrated by Example 11 , below.
  • Example 11 144 lead TQFP's of the type molded in Example 8 were decapped using nitric acid and microscopically examined at 400x magnification.
  • the decapped devices showed no evidence of cracking in the passivation layer, no line/metalization shift, and no cracking of the wire bonds.
  • polyester liquid crystal polymer resins having a number average molecular weight between about 1000 and 25,000 and melting points between about 230 and 500 degrees Centigrade. Those resins having number average molecular weights between about 1000 and 5000 and melting points between 250 and 350 degrees Centigrade are preferred. Most preferred are those resins containing three or more components selected from the group consisting of hydroquinone, isophthalic acid, purified terephthalic acid, parahydroxybenzoic acid, and 4, 4' biphenyldiol.
  • Preferred ranges for the foregoing components are 0-40 mole percent hydroquinone, 0-20 mole percent purified isophthalic acid, 0-40 mole percent purified terephthalic acid, 40-80 mole percent parahydroxybenzoic acid, and 0-40 mole percent 4, 4' biphenyldiol.
  • Most preferred is a base resin containing between 5 and 10 mole percent hydroquinone, 5 and 15 mole percent purified isophthalic acid, 5 and 15 mole percent purified terephthalic acid, 50 and 70 mole percent parahydroxybenzoic acid, and 8 and 18 mole percent 4, 4' biphenyldiol.
  • silane coupling agents useful in the invention include any non-polar silane coupling agent.
  • silane coupling agent refers to a silicone molecule substituted with a plurality of (typically 3) alkoxy groups and an additional non-alkoxy group.
  • non-alkoxy group contains a heteroatom-substituted group such as an amine or a mercapto group, or contains a functional group such as a glycydal ether group
  • that coupling agent is called a "polar" silane coupling agent, including for example 3-aminopropyltriethoxysilane and 3- glycidyloxypropyltrimethoxysiiane
  • the non-alkoxy group is alkyl, alkenyl, aryl or combinations thereof, that coupling agent is called a "non- polar" silane coupling agent.
  • the coupling agents can be used in any amount that can be carried successfully by the filler, typically from 0.1 to 2.0 weight percent, based on filler weight, and most preferably 0.25 to 0.75 weight percent.
  • Fillers useful in the invention include any particulate inorganic material, and can be present in loadings of 10 to 80 weight percent, more preferably 30 to 70 weight percent, and most preferably 40 to 60 weight percent. While the fillers used typically will be angular or spherical silicon dioxide, other fillers may be used. For example, where improved filler heat transfer is desired, fillers such as boron nitride, silica coated aluminum nitride, or carbon fiber may be used.
  • spherical silica fillers is preferred for use in LCP-based encapsulants according to the invention as the spherical shape maximizes the volume to surface area ratio of the filler and results in smaller increases in viscosity than result from similarly sized angular fillers at equivalent filler loadings.
  • Additives useful in the LCP formulations of the invention include any of those known to those skilled in the art. These include, for example, silicon rubbers, dyes, mold release agents, pigments, antioxidants, adhesion promoters, flow promoters, impact modifiers and heat stabilizers. Where adhesion promoters such as those used in Example 7 are employed they may be added in an amount between about 0.05 and 10 weight percent of the formulation, with the preferred range being from 0.25 to 5 weight percent. Other adhesion promoters thought to be particularly useful in the invention in addition to polysulfone materials include poly(bisphenol-A-co- epichlorohydrins) having average molecular weights between about 1000 and 70,000. Additional details of LCP resins useful in the invention can be found in

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention porte sur des composés moulables d'encapsulage de composants électroniques, à base de résine de polymère en cristaux liquides chargée, revêtue d'un agent de couplage de silane non polaire qui en réduit la viscosité.
PCT/US1999/015095 1998-07-10 1999-07-02 Produit d'encapsulage a base de polymere en cristaux liquides Ceased WO2000002975A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU48574/99A AU4857499A (en) 1998-07-10 1999-07-02 Liquid crystal polymer encapsulant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9234798P 1998-07-10 1998-07-10
US60/092,347 1998-07-10
US34274699A 1999-06-29 1999-06-29
US09/342,746 1999-06-29

Publications (1)

Publication Number Publication Date
WO2000002975A1 true WO2000002975A1 (fr) 2000-01-20

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ID=26785561

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/015095 Ceased WO2000002975A1 (fr) 1998-07-10 1999-07-02 Produit d'encapsulage a base de polymere en cristaux liquides

Country Status (2)

Country Link
AU (1) AU4857499A (fr)
WO (1) WO2000002975A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004026009A1 (fr) * 2002-09-16 2004-03-25 World Properties, Inc. Composites polymeres cristallins liquides, leur procede de fabrication et articles constitues desdits composites
CN103360729A (zh) * 2012-03-28 2013-10-23 住友化学株式会社 液晶高分子的注射成型体及其制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273646A2 (fr) * 1986-12-26 1988-07-06 Polyplastics Co. Ltd. Composition de polyester
EP0353933A2 (fr) * 1988-08-04 1990-02-07 Polyplastics Co. Ltd. Composition d'étanchéité pour composants électroniques et ses composants électroniques
JPH05287177A (ja) * 1992-04-06 1993-11-02 Polyplastics Co 液晶性ポリエステル樹脂組成物
EP0779338A2 (fr) * 1995-12-15 1997-06-18 Toray Industries, Inc. Composition de résine cristallin liquide et compositions à mouler

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0273646A2 (fr) * 1986-12-26 1988-07-06 Polyplastics Co. Ltd. Composition de polyester
EP0353933A2 (fr) * 1988-08-04 1990-02-07 Polyplastics Co. Ltd. Composition d'étanchéité pour composants électroniques et ses composants électroniques
JPH05287177A (ja) * 1992-04-06 1993-11-02 Polyplastics Co 液晶性ポリエステル樹脂組成物
EP0779338A2 (fr) * 1995-12-15 1997-06-18 Toray Industries, Inc. Composition de résine cristallin liquide et compositions à mouler

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199348, Derwent World Patents Index; Class A23, AN 1993-383233, XP002119965 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004026009A1 (fr) * 2002-09-16 2004-03-25 World Properties, Inc. Composites polymeres cristallins liquides, leur procede de fabrication et articles constitues desdits composites
GB2410620A (en) * 2002-09-16 2005-08-03 World Properties Inc Liquid crystalline polymer composites, method of manufacture thereof, and articles formed therefrom
US6994896B2 (en) 2002-09-16 2006-02-07 World Properties, Inc. Liquid crystalline polymer composites, method of manufacture thereof, and articles formed therefrom
GB2410620B (en) * 2002-09-16 2006-06-21 World Properties Inc Liquid crystalline polymer composites, method of manufacture thereof, and articles formed therefrom
CN103360729A (zh) * 2012-03-28 2013-10-23 住友化学株式会社 液晶高分子的注射成型体及其制造方法

Also Published As

Publication number Publication date
AU4857499A (en) 2000-02-01

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