CN101058709A - Epoxy resin molding material for sealing use and semiconductor device - Google Patents

Epoxy resin molding material for sealing use and semiconductor device Download PDF

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Publication number
CN101058709A
CN101058709A CNA2007101047005A CN200710104700A CN101058709A CN 101058709 A CN101058709 A CN 101058709A CN A2007101047005 A CNA2007101047005 A CN A2007101047005A CN 200710104700 A CN200710104700 A CN 200710104700A CN 101058709 A CN101058709 A CN 101058709A
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epoxy resin
molding material
resin molding
following
encapsulation
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CN101058709B (en
Inventor
池泽良一
奈良直纪
茶木秀幸
水上义裕
远藤由则
柏原隆贵
古泽文夫
吉井正树
萩原伸介
片寄光雄
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Priority claimed from JP2003103357A external-priority patent/JP2004307646A/en
Priority claimed from JP2003103438A external-priority patent/JP2004307649A/en
Priority claimed from JP2003103435A external-priority patent/JP4418165B2/en
Priority claimed from JP2003103443A external-priority patent/JP2004307650A/en
Application filed by Hitachi Chemical Co Ltd filed Critical Hitachi Chemical Co Ltd
Publication of CN101058709A publication Critical patent/CN101058709A/en
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Publication of CN101058709B publication Critical patent/CN101058709B/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301—Thyristor
    • 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
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1301—Thyristor
    • H01L2924/13034—Silicon Controlled Rectifier [SCR]

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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides an epoxy resin forming material used for sealing, which contains (A) an epoxy resin, (B) a firming agent and (C) an inorganic filler, and is characterized in that the epoxy resin forming material used for sealing conforms to one of the conditions which are that: the glass transition temperature based on a TMA method is 150 DEG C or above 150 DEG C; the bending elasticity modulus based on JIS-K6911 is 19GPa or below 19GPa; the forming shrinkage factor based on JIS-K6911 is 0.2 percent or below 0.2 percent. The invention also provides a sealed semiconductor device of the epoxy resin forming material used for sealing.

Description

Epoxy resin molding material for encapsulation and semiconductor device
The application is to be on April 7th, 2004 applying date of original application, and application number is 200480008859.1, and denomination of invention is divided an application for the Chinese patent application of " epoxy resin molding material for encapsulation and semiconductor device ".
The application is that foundation is with the previous Japanese patent application that proposes of applicant, promptly specially be willing to 2003-103346 number (April 7 2003 applying date), specially be willing to 2003-103357 number (April 7 2003 applying date), specially be willing to 2003-103435 number (April 7 2003 applying date), specially be willing to 2003-103438 number (April 7 2003 applying date) and special claim of priority of being willing to 2003-103443 number (April 7 2003 applying date), quote its specification sheets here with as a reference.
Technical field
The present invention relates to epoxy resin molding material for encapsulation and semiconductor device.
In more detail, the present invention relates to have the epoxy resin molding material for encapsulation of the good fillibility that is applicable to flip-chip installation usefulness bottom filling.In addition, the present invention relates to use sealing with the epoxy resin molding material sealing, shaping unfavorable conditions such as space are few, and the good flip-chip mounted semiconductor device of the anti-reliability of fluidity, wet fastness etc. again.
Background technology
For the consideration of aspects such as productivity and cost, in the element field of sealing technology of electronic part apparatus such as transistor, IC be is main flow with resin-sealed in the past, is extensive use of epoxy resin molding material.This be because, the electrical specification of Resins, epoxy, wet fastness, thermotolerance, mechanical characteristics, good with the balance of many characteristics such as cementability of inset.
Along with the development of electronic unit in the high-density installationization of printed circuit board (PCB), it is main flow that semiconductor device has been transformed into the surface installing type package from previous pin type package in recent years.In addition, surface installing type IC, LSI etc. are in order to improve packing density and to reduce mounting height and become slim, compact package body, so element increases for the occupied area of package, and package thickness becomes extremely thin.In addition,, promoted the increase and the spininessization of chip area, and, impelled the downsizing of weld pad spacing and the downsizing of weld pad size, promptly so-called weld pad spacing stricturization because of weld pad (electrode) number increases along with the multifunction and the high capacity of element.In addition, for corresponding to further miniaturization and, packaged type also from QFP (small-sized square planar package), SOP (small size encapsulation) etc. to can and realizing more CSP of high-density installation (chip size packages) and BGA (BGA Package) more easily corresponding to spininessization.These encapsulation technologies have been developed novel textures such as flip chip type, lamination (accumulation) type, flip chip type, wafer level type in order to realize high speed, multifunction in recent years.
It is the interconnection technique that replaces lead-in wire connection method in the past that flip-chip is installed, and adheres to soldering projection on the weld pad of semi-conductor chip, utilizes this projection to be connected with pad on the circuit card.In addition, the chip that is attached with projection utilizes again that stream makes melt solder behind aligned position on the circuit card, forms electric property through the automatic fine tuning step, mechanicalness connects.For the various reliabilities of the device that improves installation like this, bottom filling is injected the slit of the chip/circuit card that connects through soldering projection.And do not produce space etc. for completely filled has disposed the narrow gap of soldering projection, bottom filling needs high fillibility.
In order to solve this problem, be to adopt to use to be the solvent of principal constituent or the liquid-type epoxy resin molding material for encapsulation of solvent-free system with bisphenol-type epoxy resin in the past, utilize capillary phenomenon to soak in the slit of chip/circuit card, again the solidified mode.
But the cost of liquid-type epoxy resin molding material for encapsulation is higher, therefore for the consideration of the aspect that reduces cost, has developed the novel forming technique of using the vacuum mode of solid type epoxy resin molding material for encapsulation, and fill the bottom that is used for flip-chip.But the fillibility of solid type shaped material in the past is lower, therefore is difficult to be sealed to unfavorable conditions such as the space does not take place.For example, possess in the process of flip-chip semiconductor device of future generation of soldering projection etc. of minuteness space in manufacturing, if use solid type encapsulating epoxy resin sealing in the past, will produce the space of size about the about 0.1mm of diameter, and can't fully be filled into the bottom filling part.In addition, from becoming more meticulous of flip-chip mounted semiconductor device, promptly bump height and bump pitch reduce, follow the input and output number to increase and number of lugs and flip-chip area increase this trend, will require higher fillibility from now on.
Therefore demand is applicable to the epoxy resin molding material for encapsulation with good fillibility of flip-chip installation with bottom filling.In addition, demand does not have the shaping unfavorable condition and has the flip-chip semiconductor device good anti-reliability of fluidity and wet fastness etc. again, that possess minuteness space soldering projection etc.
But, replace being used as the lead frame of inset in the past, the front end field semiconductor device of establishing is changed at present, and several element mountings on organic substrate or ceramic substrate etc., are used MAP (module array encapsulation) forming mode that cuts behind the epoxy resin molding material once-forming.This method is because of reducing material cost and improving the main flow that productivity becomes forming mode gradually.Replace the Au line be used for connect elements and distribution for the high speed of element and the viewpoint of multifunction this moment, developed soldered ball is installed on element, utilizes soldered ball to be connected this method that is called the flip-chip installation with pad on the circuit card.The chip that has adhered to soldered ball utilizes stream to make the soldered ball fusion behind aligned position on the circuit card again, forms electric property, mechanicalness connection through the automatic fine tuning step.
But flip-chip is installed owing to element surface and soldered ball part ingress of air, and reliability obviously descends.Therefore, inquired into and how to have made up, improved reliability, realized semi-conductive miniaturization and high speed, and improve productivity with described MAP forming mode.
With regard to installation of combination flip-chip and MAP forming mode, have problems such as shaping back substrate warpage and monolithic cutting back package warpage.In addition, substrate warpage cuts into the operation of monolithic semiconductor chip and the operation that soldering projection is installed after can obviously hindering and being shaped, and the package warpage then owing to lack flatness, can produce bad connection when being installed on circuit card in addition.
In order to address this problem the technology that is used for sealing element surface and soldered ball portion so far of having inquired into, promptly fill the method for the aqueous resin that is called bottom filling.But the cost of aqueous resin is higher than epoxy resin molding material, and easily makes substrate warpage behind the resin solidification.Therefore can't therefore begin to inquire into the suitability of the epoxy resin molding material of low cost and dimensional stability excellence corresponding to being the sealing of the large-sized substrate of purpose to improve productivity.
Developed and be used for flip-chip bottom novel forming technique that fill, that use the vacuum mode of solid type epoxy resin molding material for encapsulation.But the solid type shaped material adopted filling dose to be less than the method for SMD with epoxy resin molding material in order to improve fillibility in the past, therefore will make substrate and package warpage easily because of contraction after epoxy resin molding material solidifies.
Therefore demand is a kind of can keep suitable fillibility when installing with bottom filling as flip-chip, and can reduce the epoxy resin molding material for encapsulation of sealing back substrate and package warpage, and with shaping unfavorable conditions such as its sealing back tights, and the good flip-chip mounted semiconductor device of the anti-reliability of fluidity, wet fastness etc. again.
The present invention the 1st aspect provides, and is applicable to that sealing has the epoxy resin molding material for encapsulation of the more flip-chip mounted semiconductor device of minuteness space projection and input and output number (number of lugs).In addition, also provide with epoxy resin molding material for encapsulation of the present invention sealing, have minuteness space projection and a more flip-chip mounted semiconductor device of input and output number (number of lugs).
The present invention the 2nd aspect provides, can reduce sealing flip-chip mounted semiconductor device after, because of substrate warpage causes the unfavorable condition in the production and is installed to the epoxy resin molding material for encapsulation of problem such as circuit card because of the package warpage is bad.In addition, also provide with epoxy resin molding material for encapsulation of the present invention sealing, can reduce the unfavorable condition in the production that causes because of substrate warpage and be installed to the flip-chip mounted semiconductor device of problem such as circuit card because of the package warpage is bad.
Summary of the invention
The present invention relates to following item.
1. epoxy resin molding material for encapsulation contains (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, and the median size of described inorganic filler (C) is that 12 μ m or following its specific surface area are 3.0m 2/ g or more than.
2. epoxy resin molding material for encapsulation, contain (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, described inorganic filler (C) is, maximum particle diameter is at 63 μ m or following, and contains 5wt% or above particle diameter at 20 μ m or above inorganic filler.
3. epoxy resin molding material for encapsulation contains (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, and described inorganic median size of filling out agent (C) is that 15 μ m or following and specific surface area are 3.0～6.0m 2/ g is used for possessing (a1)～(d1) constitute one or more semiconductor device,
(a1) bump height of flip-chip is 150 μ m or following;
(b1) bump pitch of flip-chip is 500 μ m or following;
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following.
4. epoxy resin molding material for encapsulation contains (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, and the specific surface area of described inorganic filler (C) is 3.0～6.0m 2/ g further contains (D) coupler.
5. epoxy resin molding material for encapsulation, contain (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, described epoxy resin molding material for encapsulation satisfy second-order transition temperature based on the TMA method be 150 ℃ or above, based on the bending elastic modulus of JIS-K6911 be 19GPa or following, based on the shaping shrinkage rate of JIS-K6911 be 0.2% or following these conditions at least one condition.
Description of drawings
Fig. 1 is to use the sectional view of the flip chip type BGA (bottom filled-type) of epoxy resin molding material for encapsulation (sealing material) sealing.
Fig. 2 is to use the sectional view of the flip chip type BGA (pressing mold forming) of epoxy resin molding material for encapsulation (sealing material) sealing.
Fig. 3 is at the vertical view (part skeleton view) during across soldering projection 2 configuring semiconductor chips 3 on the circuit card 1.
Fig. 4 is that (x) sectional view after the pressing mold shaping one sealing (MAP shapings) of semiconductor device (flip-chip BGA) reaches (y) vertical view.
Among the figure, the 1st, circuit card; The 2nd, soldering projection; The 3rd, semi-conductor chip; The 4th, sealing material; The 5th, the bottom filling part; A is a bump height; B is a bump pitch; C is the area of semi-conductor chip; D is the total thickness of sealing material; The 11st, circuit card; The 12nd, soldering projection; The 13rd, semi-conductor chip; The 14th, sealing material.
Embodiment
The inventor etc. are the wholwe-hearted result who inquires in order to solve above-mentioned problem, discovery can by with specific inorganic filler serve as must composition specific semiconductor device with epoxy resin molding material for encapsulation and the semiconductor device that uses sealing to seal with epoxy resin molding material, achieve the above object, so that finished the present invention.
(Resins, epoxy)
(A) Resins, epoxy that uses among the present invention can be the employed material of general epoxy resin molding material for encapsulation, is not particularly limited, and for example can enumerate phenol novolak type epoxy resin; O-cresol phenolic epoxy varnish; With aphthols such as phenol such as the condensation under an acidic catalyst headed by the Resins, epoxy with tritane skeleton or polycondensation phenol, cresols, xylenol, Resorcinol, catechol, dihydroxyphenyl propane, Bisphenol F and/or naphthyl alcohol, 2-Naphthol, dihydroxy naphthlene and formaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, salicylic aldehyde etc. have the compound of aldehyde radical and the epoxide of the phenolic varnish type resin that obtains; The diglycidylether of the bis-phenol of dihydroxyphenyl propane, Bisphenol F, bisphenol S, alkyl replacement or non-replacement; Stilbene type Resins, epoxy; Hydroquinone type Resins, epoxy; The reaction of polyprotonic acid such as phthalic acid, dimeracid and Epicholorohydrin and the glycidyl ester type epoxy resin that obtains; The reaction of polyamines such as diaminodiphenyl-methane, cyamelide and Epicholorohydrin and the sweet amine type Resins, epoxy that contracts of shrink that obtains; The epoxide of the condensation resin of Dicyclopentadiene (DCPD) and phenol; Resins, epoxy with naphthalene nucleus; The epoxide of phenol-aralkyl resin, naphthols-aralkyl-type phenol resin such as aralkyl resin; Trimethylolpropane type Resins, epoxy; Terpene modified Resins, epoxy; With peracid olefin oxide keys such as peracetic acid and the linear aliphatic epoxy resin that obtains; Cycloaliphatic epoxy resin; Sulfur atom-containing Resins, epoxy etc., these can use separately or two kinds or above being used in combination.
Wherein, from the viewpoint of fillibility and anti-fluidity again, preferred biphenyl type epoxy resin, bisphenol f type epoxy resin, stilbene type Resins, epoxy and sulfur atom-containing Resins, epoxy; From the solidified nature viewpoint, preferred phenolic resin varnish type epoxy resin; From the agent of low hygroscopicity viewpoint, preferred dicyclopentadiene-type epoxy resin; From thermotolerance and low warpage properties viewpoint, preferred naphthalene type Resins, epoxy, tritane type Resins, epoxy preferably contain a kind of aforementioned epoxy resins at least.
Biphenyl type epoxy resin can be enumerated the Resins, epoxy shown in following general formula (IV) etc., bisphenol f type epoxy resin can be enumerated the Resins, epoxy shown in following general formula (V), stilbene type Resins, epoxy can be enumerated following to the Resins, epoxy shown in the general formula (VI), and sulfur atom-containing Resins, epoxy can be enumerated the Resins, epoxy shown in following general formula (VII) etc.
Figure A20071010470000111
(in the formula, R 1～R 8Be the monovalence alkyl that is selected from the replacement or the non-replacement of hydrogen atom and carbonatoms 1～10, can be all identical or different.N is 0～3 integer.)
Figure A20071010470000112
(in the formula, R 1～R 8Be the alkyl that is selected from hydrogen atom, carbonatoms 1～10, the alkoxyl group of carbonatoms 1～10, the aryl of carbonatoms 6～10, the aralkyl of carbonatoms 6～10, can be all identical or different.N is 0～3 integer.)
Figure A20071010470000113
(in the formula, R 1～R 8Be the monovalence alkyl that is selected from the replacement or the non-replacement of hydrogen atom and carbonatoms 1～5, can be all identical or different.N is 0～10 integer.)
Figure A20071010470000121
(in the formula, R 1～R 8Be the alkoxyl group of carbonatoms 1～10 of alkyl, replacement or non-replacement that is selected from the carbonatoms 1～10 of hydrogen atom, replacement or non-replacement, can be all identical or different.N is 0～3 integer.)
As the biphenyl type epoxy resin shown in the above-mentioned general formula (IV), can enumerate as with 4,4 '-two (2, the 3-glycidoxy) biphenyl or 4,4 '-two (2, the 3-glycidoxy)-3,3 ', 5,5 '-tetramethyl biphenyl be principal constituent Resins, epoxy, Epicholorohydrin and 4,4 '-bis-phenol or 4,4 '-(3,3 ', 5,5 '-tetramethyl-) bis-phenol reaction and the Resins, epoxy that obtains etc.Wherein preferred, with 4,4 '-two (2, the 3-glycidoxy)-3,3 ', 5,5 '-tetramethyl biphenyl is the Resins, epoxy of principal constituent.
As the bisphenol f type epoxy resin shown in the above-mentioned logical formula V, obtainable commercially available product is just like with R 1, R 3, R 6And R 8Be methyl, R 2, R 4, R 5And R 7Be hydrogen atom, n=0 is the YSLV-80XY (Nippon Steel Chemical Co., Ltd's system trade(brand)name) of principal constituent.
Stilbene type Resins, epoxy shown in the above-mentioned general formula (VI) can react stilbene as raw material in the presence of alkaline matter be phenol and Epicholorohydrin and obtain.This stilbene as raw material be phenol can enumerate as the 3-tertiary butyl-4,4 '-dihydroxyl-3 ', 5,5 '-trimethylammonium stilbene, the 3-tertiary butyl-4,4 '-dihydroxyl-3 ', 5 ', 6-trimethylammonium stilbene, 4,4 '-dihydroxyl-3,3 ', 5,5 '-trimethylammonium stilbene, 4,4 '-dihydroxyl-3 ', 3-di-t-butyl-5,5 '-dimethyl stilbene, 4,4 '-dihydroxyl-3 ', 3-di-t-butyl-6,6 '-the dimethyl stilbene etc., the wherein preferred 3-tertiary butyl-4,4 '-dihydroxyl-3 ', 5,5 '-trimethylammonium stilbene and 4,4 '-dihydroxyl-3 ', 3,5,5 '-the tetramethyl-stilbene.These stilbene type phenol can be used separately or two kinds or above being used in combination.
In the sulfur atom-containing Resins, epoxy shown in the above-mentioned general formula (VII), preferred R 2, R 3, R 6And R 7Be hydrogen atom and R 1, R 4, R 5And R 8Resins, epoxy for alkyl; More preferably R 2, R 3, R 6And R 7Be hydrogen atom, R 1And R 8Be the tertiary butyl, and R 4And R 5Resins, epoxy for methyl.As the obtainable commercially available product of this compound YSLV-120TE (chemical company of Nippon Steel system) etc. is arranged.
Above-mentioned Resins, epoxy can use any separately or two kinds or above being used in combination, but in order to bring into play its performance, with respect to the preferred 20 weight % of the combined amount of Resins, epoxy full dose or more than, more preferably 30 weight % or more than, especially preferred 50 weight % or more than.
Phenolic resin varnish type epoxy resin can be enumerated the Resins, epoxy shown in following general formula (VIII) etc.
Figure A20071010470000131
(in the formula, R is the monovalence alkyl that is selected from the replacement or the non-replacement of hydrogen atom, carbonatoms 1～10, and n is 0～10 integer.)
Phenolic resin varnish type epoxy resin shown in the above-mentioned general formula (VIII) can easily obtain by reaction table chloropharin in phenolic varnish type resol, wherein, R in the general formula (VIII) is preferably the alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the alkoxyl group of carbonatomss 1～10 such as methoxyl group, oxyethyl group, propoxy-, butoxy, more preferably hydrogen atom or methyl.The integer of n preferred 0～3.In the phenolic resin varnish type epoxy resin shown in the above-mentioned general formula (VIII), preferred again o-cresol phenolic epoxy varnish.
When using phenolic resin varnish type epoxy resin, in order to bring into play its performance, with respect to the preferred 20 weight % of the combined amount of Resins, epoxy full dose or more than, more preferably 30 weight % or more than.
Dicyclopentadiene-type epoxy resin can be enumerated the Resins, epoxy shown in following general formula (IX) etc.
Figure A20071010470000132
(in the formula, R 1And R 2Be the replacement that is selected from hydrogen atom, carbonatoms 1～10 respectively or the monovalence alkyl of non-replacement, n is 0～10 integer, and m is 0～6 integer.)
R in the above-mentioned formula (IX) 1Can enumerate as hydrogen atom; Methyl, ethyl, propyl group, butyl, alkyl such as sec.-propyl, the tertiary butyl; Alkenyls such as vinyl, allyl group, butenyl; Replacement or the monovalence alkyl of non-replacement, wherein alkyl such as preferable methyl, ethyl and hydrogen atom, the more preferably methyl and the hydrogen atom of carbonatomss 1～5 such as haloalkyl, amino substituted alkyl, sulfydryl substituted alkyl.R 2Can enumerate as hydrogen atom; Alkyl such as methyl, ethyl, propyl group, butyl, sec.-propyl, the tertiary butyl; Alkenyls such as vinyl, allyl group, butenyl; The replacement of carbonatomss 1～5 such as haloalkyl, amino substituted alkyl, sulfydryl substituted alkyl or the monovalence alkyl of non-replacement, wherein preferred hydrogen atom.
When using dicyclopentadiene-type epoxy resin, in order to bring into play its performance, with respect to the preferred 20 weight % of the combined amount of Resins, epoxy full dose or more than, more preferably 30 weight % or more than.
Naphthalene type Resins, epoxy can be enumerated the Resins, epoxy shown in following general formula (X) etc., and tritane type Resins, epoxy can be enumerated the Resins, epoxy shown in following general formula (X1) etc.
Figure A20071010470000141
(in the formula, R 1～R 3Be the monovalence alkyl of the carbonatoms 1～12 that is selected from hydrogen atom, replacement or non-replacement respectively, can be all identical or different.P is 1 or 0, respectively do for oneself 0～11 integer of l and m, and (l+m) be 1～11 integer, (l+p) be 1～12 integer.I is 0～3 integer, and j is 0～2 integer, and k is 0～4 integer.)
Naphthalene type Resins, epoxy shown in the above-mentioned general formula (X) can enumerate as containing l disorderly constitute unit and m unitary random copolymers of formation, the alternating copolymer that alternately contains, the multipolymer that contains regularly, with the segmented copolymer that block-wise contains, can use any separately or two kinds or above being used in combination.
(in the formula, R is the monovalence alkyl that is selected from the replacement or the non-replacement of hydrogen atom, carbonatoms 1～10, and n is 1～10 integer.)
These Resins, epoxy can use any separately or both are used in combination, but in order to bring into play its performance, with respect to the preferred 20 weight % of the combined amount of Resins, epoxy full dose or more than, more preferably 30 weight % or more than, especially preferred 50 weight % or more than.
Above-mentioned biphenyl type epoxy resin, stilbene type Resins, epoxy, sulfur atom-containing Resins, epoxy, phenolic resin varnish type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type Resins, epoxy and tritane type Resins, epoxy, can use any separately or two kinds or above being used in combination, but its combined amount with respect to the preferred 50 weight % of Resins, epoxy full dose or more than, more preferably 60 weight % or more than, especially preferred 80 weight % or more than.
With regard to the fillibility viewpoint, (A) used in the present invention Resins, epoxy 150 ℃ melt viscosity preferred 2 the pool or below, more preferably 1 the pool or below, especially preferred 0.5 the pool or below.Here, melt viscosity is meant, with the viscosity of ICI cone-and-plate viscometer mensuration.
(solidifying agent)
(B) used in the present invention solidifying agent can be the employed material of general epoxy resin molding material for encapsulation, there is no particular restriction, for example, aphthols such as phenol such as condensation or polycondensation phenol, cresols, Resorcinol, catechol, dihydroxyphenyl propane, Bisphenol F, phenylphenol, amino-phenol and/or naphthyl alcohol, 2-Naphthol, dihydroxy naphthlene and formaldehyde, phenyl aldehyde, salicylic aldehyde etc. have the compound of aldehyde radical and the phenolic varnish type resol that obtains in the presence of an acidic catalyst; Synthesizing phenol class and/or aphthols and dimethoxy p-Xylol or two (methoxymethyl) biphenyl and the phenol-aralkyl resin, the naphthols-aralkyl-type phenol resin such as aralkyl resin that obtain; Phenol and/or aphthols and cyclopentadiene copolymerization and dicyclopentadiene-type resol such as the dicyclopentadiene-type phenol phenolic varnish type resin that obtains, naphthol novolak varnish type resin; Terpene modified resol etc., these can use separately or two kinds or above being used in combination.
Wherein, from the flame retardant resistance viewpoint, preferred biphenyl type resol; From anti-fluidity again and solidified nature viewpoint, preferred aralkyl-type phenol resin; From the agent of low hygroscopicity viewpoint, preferred dicyclopentadiene-type resol; From thermotolerance, low thermal expansion and low warpage properties viewpoint, preferred tritane type resol; From the solidified nature viewpoint, preferred phenolic varnish type resol preferably contains a kind of these resol at least.
Biphenyl type resol can be enumerated the resol shown in following general formula (XII) etc.
Figure A20071010470000151
R in the above-mentioned formula (XII) 1～R 9Can be all identical or different, be to be selected from hydrogen atom, the alkyl of carbonatomss 1～10 such as methyl, ethyl, propyl group, butyl, sec.-propyl, isobutyl-, the alkoxyl group of carbonatomss 1～10 such as oxyethyl group, propoxy-, butoxy, the aralkyl of carbonatomss 6～10 such as the aryl of carbon atoms such as phenyl, tolyl, xylyl 6～10 and benzyl, styroyl, wherein preferred hydrogen atom and methyl.N is 0～10 integer.
Biphenyl type resol shown in the above-mentioned general formula (XII) can be enumerated as R 1～R 9All be compound of hydrogen atom etc.,, preferably contain 50 weight % or above n and be 1 or the condenses mixture of above condenses wherein from the melt viscosity viewpoint.As the obtainable commercially available product of this compound just like MEH-7851 (bright and change into Co., Ltd. system trade(brand)name).
When using biphenyl type resol, in order to bring into play its performance, with respect to the preferred 30 weight % of the combined amount of solidifying agent full dose or more than, more preferably 50 weight % or more than, especially preferred 60 weight % or more than.
Aralkyl-type phenol resin can be enumerated as phenol-aralkyl resin, naphthols-aralkyl resin etc., phenol shown in the preferred following general formula (XIII)-aralkyl resin, more preferably the R in the general formula (XIII) is that the mean value of hydrogen atom and n is phenol-aralkyl resin of 0～8.Concrete example can be enumerated as p-Xylol type phenol-aralkyl resin, m-xylene type phenol-aralkyl resin etc.When using these aralkyl-type phenol resin, in order to bring into play its performance, with respect to the preferred 30 weight % of the combined amount of solidifying agent full dose or more than, more preferably 50 weight % or more than.
Figure A20071010470000161
(in the formula, R is the monovalence alkyl of the replacement or the non-replacement of hydrogen atom, carbonatoms 1～10, and n is 0～10 integer.)
Dicyclopentadiene-type resol can be enumerated the resol shown in following general formula (XIV) etc.
Figure A20071010470000162
(in the formula, R 1And R 2Be the replacement that is selected from hydrogen atom, carbonatoms 1～10 independently of one another or the monovalence alkyl of non-replacement, n is 0～10 integer, and m is 0～6 integer.)
When using dicyclopentadiene-type resol, in order to bring into play its performance, with respect to the preferred 30 weight % of the combined amount of solidifying agent full dose or more than, more preferably 50 weight % or more than.
Tritane type resol can be enumerated the resol shown in following general formula (XV).
Figure A20071010470000171
(in the formula, R is selected from the monovalence alkyl of the replacement or the non-replacement of hydrogen atom, carbonatoms 1～10, and n is 1～10 integer.)
When using tritane type resol, in order to bring into play its performance, with respect to the preferred 30 weight % of the combined amount of solidifying agent full dose or more than, more preferably 50 weight % or more than.
Phenolic varnish type resol can be enumerated as phenol novolac resin, cresols novolac resin, naphthol novolac varnish resin etc., wherein preferred phenol novolac resin.When using phenolic varnish type resol, in order to bring into play its performance, with respect to the preferred 30 weight % of the combined amount of solidifying agent full dose or more than, more preferably 50 weight % or more than.
Above-mentioned biphenyl type resol, aralkyl-type phenol resin, dicyclopentadiene-type resol, tritane type resol and phenolic varnish type resol can use any separately or be used in combination two kinds or more than, its add up to combined amount with respect to the preferred 60 weight % of solidifying agent full dose or more than, more preferably 80 weight % or more than.
From the fillibility viewpoint, (B) used in the present invention solidifying agent 150 ℃ melt viscosity preferred 2 the pool or below, more preferably 1 the pool or below.Here, melt viscosity is represented ICI viscosity.
(A) Resins, epoxy and (B) equivalence ratio of solidifying agent, promptly, there is no particular restriction to the ratio of epoxy radix in the Resins, epoxy (in the solidifying agent in hydroxyl value/Resins, epoxy epoxy radix) for hydroxyl value in the solidifying agent, but in order to suppress unreacted components separately, preferred settings is in 0.5～2 scope, and more preferably 0.6～1.3.In order to obtain having the epoxy resin molding material for encapsulation of good plasticity and anti-fluidity again, further preferably set scope 0.8～1.2.
(inorganic filler)
(C) used in the present invention inorganic filler is for water absorbability, reduce linear expansivity, improve heat conductivity, improve intensity and add in the epoxy resin molding material for encapsulation, can enumerate as fused silica, crystalline silica, aluminum oxide, zircon, Calucium Silicate powder, lime carbonate, potassium titanate, silicon carbide, silicon nitride, aluminium nitride, boron nitride, beryllium oxide, zirconium white, zircon, forsterite, steatite, spinel, the powder of mullite, titanium dioxide etc. or be made into spheric pearl, glass fibre etc.In addition, the inorganic filler with flame retardant effect can be enumerated as aluminium hydroxide, magnesium hydroxide, zinc borate, zinc molybdate etc.
These inorganic fillers can use separately or two kinds or above being used in combination.Wherein, preferred molten silica from fillibility and reduction linear expansivity viewpoint, preferred aluminum oxide from the high thermal conductivity viewpoint, the shape of inorganic filler is considered then preferred spherical from fillibility and mould abrasion aspect.
The preferred median size of (C) used in the present invention inorganic filler is that 15 μ m or following and specific surface area are 3.0～6.0m 2/ g so just can satisfy the flip-chip with minuteness space projection the fillibility of filling purposes with the bottom is installed.Median size is 10 μ m or following more preferably, especially preferred 8 μ m or following.Just be difficult to epoxy resin molding material is injected into the gap of the chip/circuit card that connects with projection when surpassing 15 μ m, fillibility descends.In addition, more preferably 3.5～5.5m of specific surface area 2/ g, especially preferred 4.0～5.0m 2/ g.Be lower than 3.0m 2/ g reaches and surpasses 6.0m 2During/g, be easy to generate the space in the gap of the chip/circuit card that connects with projection, and can reduce fillibility.
From the fillibility viewpoint, can remove the coarse particle component of (C) inorganic filler with mesh screen.This moment, preferred 53 μ m or above (C) composition be at 0.5 weight % or following, and more preferably 30 μ m or above (C) composition be at 0.5 weight % or following, and especially preferred 20 μ m or above (C) composition are at 0.5 weight % or following.
From fillibility and viewpoint of reliability, (C) inorganic filler is with respect to preferred 60～95 weight % of the combined amount of epoxy resin molding material for encapsulation, more preferably 70～90 weight %, especially preferred 75～85 weight %.Can tend to reduce anti-fluidity again when being lower than 60 weight %, then can tend to reduce fillibility when surpassing 95 weight %.
(coupler)
In order to improve the cementability of resinous principle and weighting agent, epoxy resin molding material for encapsulation of the present invention preferably adds coupler.Can be in reaching the scope of effect of the present invention as required and use coupler.Coupler can be the employed material of general epoxy resin molding material for encapsulation, there is no particular restriction, for example can enumerate silane compound, epoxy silane with primary amino, secondary amino group or uncle's amino, various silane compounds such as hydrosulphonyl silane, alkyl silane, phenyl silane, urea groups silane, vinyl silanes, titanium compound, aluminum chelate class, aluminium/zirconium compounds etc.These can use separately or two kinds or above being used in combination.
The total combined amount of coupler is with respect to preferred 0.037～4.75 weight % of epoxy resin molding material for encapsulation, more preferably 0.088～2.3 weight %.Can tend to reduce the cementability with circuit card when being lower than 0.037 weight %, in addition, can increase volatile component when surpassing 4.75 weight %, and easily produce the shaping unfavorable condition of relevant fillibilities such as space, and tend to reduce the plasticity of package.
(silane coupling agent) with secondary amino group
Above-mentioned coupler preferred (D2) has the silane coupling agent of secondary amino group, but can also use other coupler in the scope that can reach effect of the present invention as required.
The silane coupling agent that (D2) used in the present invention has secondary amino group can be the silane compound that intramolecularly has secondary amino group, there is no particular restriction, for example, γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, γ-anilino propyl group methyl dimethoxysilane, γ-anilino propyl group methyldiethoxysilane, γ-anilino propyl group ethyl diethoxy silane, γ-anilino propyl group ethyl dimethoxy silane, γ-anilino methyltrimethoxy silane, γ-anilino Union carbide A-162, γ-anilino methyl dimethoxy silane, γ-anilino methyl diethoxy silane, γ-anilino methylethyl diethoxy silane, γ-anilino methylethyl dimethoxy silane, N-(p-methoxyphenyl)-gamma-amino propyl trimethoxy silicane, N-(p-methoxyphenyl)-γ-An Jibingjisanyiyangjiguiwan, N-(p-methoxyphenyl)-gamma-amino propyl group methyl dimethoxysilane, N-(p-methoxyphenyl)-gamma-amino propyl group methyldiethoxysilane, N-(p-methoxyphenyl)-gamma-amino propyl group ethyl diethoxy silane, N-(p-methoxyphenyl)-gamma-amino propyl group ethyl dimethoxy silane, γ-(N-methyl) TSL 8330, γ-(N-ethyl) TSL 8330, γ-(N-butyl) TSL 8330, γ-(N-benzyl) TSL 8330, γ-(N-methyl) aminopropyltriethoxywerene werene, γ-(N-ethyl) aminopropyltriethoxywerene werene, γ-(N-butyl) aminopropyltriethoxywerene werene, γ-(N-benzyl) aminopropyltriethoxywerene werene, γ-(N-methyl) aminopropyl methyl dimethoxysilane, γ-(N-ethyl) aminopropyl methyl dimethoxysilane, γ-(N-butyl) aminopropyl methyl dimethoxysilane, γ-(N-benzyl) aminopropyl methyl dimethoxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, γ-(beta-aminoethyl) TSL 8330, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane etc.
Wherein from the fillibility viewpoint, the aminosilane coupling agent shown in the preferred following general formula (I).
(in the formula, R 1Be the alkyl that is selected from hydrogen atom, carbonatoms 1～6 and the alkoxyl group of carbonatoms 1～2, R 2Be alkyl and the phenyl that is selected from carbonatoms 1～6, R 3Be methyl or ethyl, n is 1～6 integer, and m is 1～3 integer.)
Aminosilane coupling agent shown in the above-mentioned general formula (I) can be enumerated as γ-anilino propyl trimethoxy silicane, γ-anilino propyl-triethoxysilicane, γ-anilino propyl group methyl dimethoxysilane, γ-anilino propyl group methyldiethoxysilane, γ-anilino propyl group ethyl diethoxy silane, γ-anilino propyl group ethyl dimethoxy silane, γ-anilino methyltrimethoxy silane, γ-anilino Union carbide A-162, γ-anilino methyl dimethoxy silane, γ-anilino methyl diethoxy silane, γ-anilino methylethyl diethoxy silane, γ-anilino methylethyl dimethoxy silane, N-(p-methoxyphenyl)-gamma-amino propyl trimethoxy silicane, N-(p-methoxyphenyl)-γ-An Jibingjisanyiyangjiguiwan, N-(p-methoxyphenyl)-gamma-amino propyl group methyl dimethoxysilane, N-(p-methoxyphenyl)-gamma-amino propyl group methyldiethoxysilane, N-(p-methoxyphenyl)-gamma-amino propyl group ethyl diethoxy silane, N-(p-methoxyphenyl)-gamma-amino propyl group ethyl dimethoxy silane etc.Especially preferred γ-anilino propyl trimethoxy silicane.
(D2) has the silane coupling agent of secondary amino group with respect to preferred 0.037～4.75 weight % of the combined amount of epoxy resin molding material for encapsulation, more preferably 0.088～2.3 weight %.Can reduce flowability when being lower than 0.037 weight %, be easy to generate the tendency about the cementability of the shaping unfavorable condition of fillibility and reduction and circuit card such as space and exist.Can increase volatile component when surpassing 4.75 weight %, and have the shaping unfavorable condition that is easy to generate relevant fillibilities such as space and the tendency of reduction package plasticity.
Can have the silane coupling agent of secondary amino group and other coupler of usefulness with (D2), it can be the employed material of general epoxy resin molding material for encapsulation, there is no particular restriction, for example can enumerate silane compound, various silane compounds such as epoxy silane, hydrosulphonyl silane, alkyl silane, phenyl silane, urea groups silane, vinyl silanes, titanium compound, aluminum chelate class, aluminium/zirconium compounds etc. with primary amino and/or uncle's amino.Concrete example can be enumerated as vinyl trichloro silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, vinyl nitrilotriacetic base silane, γ-Qiu Jibingjisanjiayangjiguiwan, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group methyldiethoxysilane, γ-(N, the N-dimethyl) TSL 8330, γ-(N, the N-diethyl) TSL 8330, γ-(N, the N-dibutyl) TSL 8330, γ-(N-methyl) anilino propyl trimethoxy silicane, γ-(N-ethyl) anilino propyl trimethoxy silicane, γ-(N, the N-dimethyl) aminopropyltriethoxywerene werene, γ-(N, the N-diethyl) aminopropyltriethoxywerene werene, γ-(N, the N-dibutyl) aminopropyltriethoxywerene werene, γ-(N-methyl) anilino propyl-triethoxysilicane, γ-(N-ethyl) anilino propyl-triethoxysilicane, γ-(N, the N-dimethyl) aminopropyl methyl dimethoxysilane, γ-(N, the N-diethyl) aminopropyl methyl dimethoxysilane, γ-(N, the N-dibutyl) aminopropyl methyl dimethoxysilane, γ-(N-methyl) anilino propyl group methyl dimethoxysilane, γ-(N-ethyl) anilino propyl group methyl dimethoxysilane, N-(Trimethoxy silane base propyl group) ethylene diamine, N-(dimethoxy-methyl silylation sec.-propyl) ethylene diamine, methyltrimethoxy silane, dimethyldimethoxysil,ne, Union carbide A-162, γ-r-chloropropyl trimethoxyl silane, hexamethyldisilane, vinyltrimethoxy silane, γ-silicane couplers such as sulfydryl propyl group methyl dimethoxysilane; Sec.-propyl three isostearoyl titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, sec.-propyl three (N-amino-ethyl-amino-ethyl) titanic acid ester, two (double tridecyl phosphorous acid ester) titanic acid ester of four octyl groups, four (2,2-two allyloxy methyl isophthalic acid-butyl) two (double tridecyl) phosphorous acid ester titanic acid ester, two (dioctylphyrophosphoric acid ester) ethoxyacetic acid ester titanic acid ester, two (dioctylphyrophosphoric acid ester) ethylidene titanic acid ester, sec.-propyl three decoyl titanic acid ester, sec.-propyl dimethyl propylene thiazolinyl isostearoyl titanic acid ester, sec.-propyl three lauryl benzene sulfonyl titanic acid ester, isopropyl stearyl diallyl titanic acid ester, sec.-propyl three (dioctyl phosphorous acid ester) titanic acid ester, sec.-propyl three cumyl phenyl titanium acid esters, titanate ester couplers such as two (dioctyl phosphorous acid ester) titanic acid ester of tetra isopropyl etc., these can use separately or two kinds or above being used in combination.
When using this other coupler, in order to bring into play performance, the silane coupling agent that (D) has a secondary amino group with respect to the preferred 30 weight % of the combined amount of coupler full dose or more than, more preferably 50 weight % or more than.Contain the whole combined amount of coupler that above-mentioned (D2) has the silane coupling agent of secondary amino group, with respect to preferred 0.037～4.75 weight % of epoxy resin molding material for encapsulation, more preferably 0.088～2.3 weight %.Can tend to reduce the cementability with circuit card when being lower than 0.037 weight %, can increase volatile component when surpassing 4.75 weight %, and easily tend to produce the shaping unfavorable condition of relevant fillibilities such as space, and tend to reduce the plasticity of package.In addition, above-mentioned coupler is with respect to preferred 0.05～5 weight % of the combined amount of (C) inorganic filler, more preferably 0.1～2.5 weight %.The reason of regulation combined amount is with above-mentioned.
(coupler fraction of coverage)
When the present invention used coupler, coupler was preferred 0.3～1.0 to the fraction of coverage of inorganic filler, and more preferably 0.4～0.9, further preferred 0.5～0.8 scope.The fraction of coverage of coupler was greater than 1.0 o'clock, and the volatile component that is produced when understanding because of shaping increases bubble, so tend to easily make thinner wall section to produce the space.In addition, the fraction of coverage of coupler can reduce the bonding force of resin and weighting material less than 0.3 o'clock, and tended to reduce molding intensity.
The coupler fraction of coverage X of epoxy resin molding material is defined as the formula as (xxx).
X(％)＝S c/S f (xxx)
In the formula, S cAnd S fRespectively do for oneself total minimum area coverage and the whole total surface areas of fillers of whole couplers of epoxy resin molding material is with (yyy) formula and (zzz) formula definition.
S c=A 1* M 1+ A 2* M 2+ A n* M n(n for use coupler kind quantity) (yyy)
S f=B 1* W 1+ B 2* W 2+ B 1* W 1(1 for use packing material kind quantity) (zzz)
In the formula, A and M respectively the do for oneself minimum area coverage and the usage quantity thereof of each coupler, B and W respectively the do for oneself specific surface area and the usage quantity thereof of each filler.
(method of control coupler fraction of coverage)
If employed each coupler of known epoxy resin molding material and inorganic filler minimum area coverage and specific surface area separately, just can by (xxx) formula, (yyy) formula and (zzz) formula calculate the coupler that becomes purpose coupler fraction of coverage and the usage quantity of packing material.
(phosphorus compound)
From fillibility and flame retardant resistance viewpoint, the present invention preferably further contains (E) phosphorus compound.There is no particular restriction for (E) used in the present invention phosphorus compound, for example, covers or do not have covering red phosphorus; Phosphorous and nitrogen compounds such as ring phosphine piperazine; Nitrilo trimethylene phosphonic tricalcium, methane-1-hydroxyl-1, phosphonates such as 1-di 2 ethylhexyl phosphonic acid two calcium salts; Triphenylphosphine oxidation thing, 2-(two phenenyl phosphinyl) quinhydrones, 2,2-[(2-(two phenenyl phosphinyl)-1,4-phenylene) two (oxygen methylenes)] phosphine compound such as two-oxyethane, tri-n-octyl phosphine oxide compound; Have the phosphorous and nitrogen compound of the ester cpds, ring phosphine piperazine etc. of phosphorus atom etc., these can use separately or two kinds or above being used in combination.Wherein, from the moisture-proof viewpoint of reliability, preferably phosphoric acid ester, phosphine oxide.
Because of red phosphorus has the fire retardant effect, so as long as can obtain effect of the present invention just is not particularly limited, but the red phosphorus that preferably covers with thermosetting resin, the red phosphorus that covers with mineral compound and organic compound etc. cover red phosphorus.
There is no particular restriction for the thermosetting resin that the red phosphorus that covers with thermosetting resin uses, for example can enumerate Resins, epoxy, resol, melamine resin, urethane resin, cyanate ester resin, urea-formaldehyde resin, aniline one formaldehyde resin, furane resin, polyamide resin, polyamide-imide resin, polyimide resin etc., these can use separately or two kinds or above being used in combination.In addition, also can use the monomer of these resins or oligopolymer to cover simultaneously and polymerization, cover the thermosetting resin that obtains by polymerization, solidify again after perhaps thermosetting resin also can cover earlier.Wherein, from the intermiscibility viewpoint of the matrix resin that is mixed into epoxy resin molding material for encapsulation, preferred epoxy, resol and melamine resin.
There is no particular restriction for the mineral compound that the red phosphorus that covers with mineral compound and organic compound uses, for example can enumerate aluminium hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, zirconium hydroxide, oxidizing aqueous zirconium, bismuth hydroxide, barium carbonate, lime carbonate, zinc oxide, titanium oxide, nickel oxide, ferric oxide etc., these can use separately or two kinds or above being used in combination.Wherein, the zirconium hydroxide that preferably phosphoric acid ion supplementary result is good, oxidizing aqueous zirconium, aluminium hydroxide and zinc oxide.
In addition, the organic compound that the red phosphorus that covers with mineral compound and organic compound uses there is no special limit, for example can enumerate the low-molecular weight compound that coupler and chelating etc. use in surface treatment, thermoplastic resin, thermosetting resin equimolecular quantity are than higher compound etc., and these can use separately or two kinds or above being used in combination.Wherein, from the viewpoint of coverage effect, preferred thermosetting resin, from the intermiscibility viewpoint of the matrix resin that is mixed into epoxy resin molding material for encapsulation, more preferably Resins, epoxy, resol and melamine resin.
When covering red phosphorus with mineral compound and organic compound, it covers the order of handling, and there is no particular restriction, can after covering mineral compound, be coated with organic compounds, or cover mineral compound after being coated with organic compounds, or use both mixtures to cover simultaneously.In addition, there is no particular restriction to cover form, can be physical property absorption, chemical combination or other form.In addition, cover state or both the part or all of bonded states that back mineral compound and organic compound can be existence out of the ordinary.
As long as can obtain effect of the present invention, there is no particular restriction for the amount of mineral compound and organic compound, the weight ratio of mineral compound and organic compound (mineral compound/organic compound) preferred 1/99～99/1, more preferably 10/90～95/5, especially preferred 30/70～90/10, preferred adjustment mineral compound and organic compound or its raw material are the usage quantity of monomer, oligopolymer, to become this weight ratio.
Red phosphorus that covers with thermosetting resin or the red phosphorus that covers with mineral compound and organic compound etc. cover the manufacture method of red phosphorus there is no particular restriction, for example can use the spy to open the known covering method that clear 62-21704 communique, spy are opened record in the clear 52-131695 communique etc.In addition, so long as can obtain effect of the present invention, there is no particular restriction for the thickness of mulch film, can be evenly during covering or cover the red phosphorus surface unevenly.
So long as can obtain effect of the present invention, the particle diameter of red phosphorus just is not particularly limited, but preferred 1～100 μ m of median size (being accumulated as the particle diameter of 50 weight % with size-grade distribution), more preferably 5～50 μ m.When median size is lower than 1 μ m, the phosphate ion concentration of molding just increases, and has the tendency of wet fastness variation, if surpass 100 μ m, when then being used for the narrow high integrated densification halfbody device of weld pad spacing, there is the tendency that is easy to generate unfavorable conditions such as electric wire distortion, short circuit, fracture.
Phosphorous and nitrogen compound has the fire retardant effect, therefore so long as can obtain effect of the present invention and just be not particularly limited, for example can enumerate the cyclic phosphines piperazine compound that contains repeating unit shown in following formula (XXV) and/or the following formula (XXVI) in the main chain backbone, perhaps contain compound to repeating unit shown in different following formula (XXVII) of the position of substitution of phosphorus atom in the phosphine piperazine ring and/or the following formula (XXVIII) etc.
Figure A20071010470000241
During this formula (XXV) reached (XXVII), m was 1～10 integer; R 1～R 4For being selected from the alkyl and the aryl that can have substituent carbonatoms 1～12, can be all identical or different; A is the alkylidene group or the arylidene of carbonatoms 1～4.In formula (XXVI) and the formula (XXVIII), n is 1～10 integer; R 5～R 8For being selected from the alkyl or aryl that can have substituent carbonatoms 1～12, can be all identical or different; A is the alkylidene group or the arylidene of carbonatoms 1～4.In addition, m R in the formula 1, R 2, R 3, R 4But m all identical or different, n R 5, R 6, R 7, R 8But n all identical or different.In above-mentioned formula (XXV)～formula (XXVIII), R 1～R 8There is no particular restriction for the shown alkyl or aryl with substituent carbonatoms 1～12, for example can enumerate methyl, ethyl, propyl group, sec.-propyl, alkyl such as butyl, isobutyl-, sec-butyl, the tertiary butyl; Aryl such as phenyl, 1-naphthyl, 2-naphthyl; O-tolyl, a tolyl, p-methylphenyl, 2,3-xylyl, 2,4-xylyl, adjacent cumenyl, a cumenyl, to alkyl substituting aromatic bases such as cumenyl, Lay bases; Aryl such as benzyl, styroyl substituted alkyls etc., in addition, the substituting group that is replaced can be enumerated as alkyl, alkoxyl group, aryl, hydroxyl, amino, epoxy group(ing), vinyl, hydroxyalkyl, alkylamino etc.
In the above-mentioned substance, from thermotolerance, the wet fastness viewpoint of epoxy resin molding material, preferred aryl groups, more preferably phenyl or hydroxy phenyl.Wherein, preferred R 1～R 4In at least one be hydroxy phenyl, R 1～R 8Can all be hydroxy phenyl, but more preferably R 1～R 4In one be hydroxy phenyl.R 1～R 8Epoxy resin cured product is become fragile, in addition, R 1～R 8Can't enter the crosslinking structure of Resins, epoxy when all being phenyl, and easily reduce the thermotolerance of epoxy resin cured product.
In above-mentioned formula (XXV)～formula (XXVIII), there is no particular restriction for the alkylidene group of carbonatoms shown in the A 1～4 or arylidene, for example can enumerate methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, phenylene, methylene phenyl, xylylene, naphthylidene etc., wherein, from the thermotolerance and the wet fastness viewpoint of epoxy resin molding material, preferred arylidene, more preferably phenylene.
Cyclic phosphines piperazine compound can be any polymkeric substance in above-mentioned formula (XXV)～formula (XXVIII), above-mentioned formula (XXV) and the multipolymer of above-mentioned formula (XXVI) or the multipolymer of above-mentioned formula (XXVII) and above-mentioned formula (XXVIII), in addition, during multipolymer can be random copolymers, segmented copolymer or mutual multipolymer.There is no particular restriction for its copolymerization mol ratio m/n, but from the thermotolerance that improves epoxy resin cured product and the viewpoint of intensity, be preferably 1/0～1/4, and more preferably 1/0～1/1.5.In addition, polymerization degree m+n is 1～20, and is preferred 2～8, more preferably 3～6.
Preferred cyclic phosphines piperazine compound can be enumerated the polymkeric substance of following formula (XXIX) and the multipolymer of following formula (XXX) etc.
(here, in formula (XXIX), m is 0～9 integer, R 1～R 4Independent separately is hydrogen or hydroxyl.)
Figure A20071010470000262
In the formula (XXX), m and n are 0～9 integer, R 1～R 4Be selected from hydrogen or hydroxyl independently of one another, R 5～R 8Be selected from hydrogen or hydroxyl independently of one another.In addition, cyclic phosphines piperazine compound can be shown in the above-mentioned formula (XXX), mutual shape, block-wise or random shape contain following shown in the material of m repeating unit (a) and n repeating unit (b), but preferably contain with random shape.
Figure A20071010470000271
Wherein, preferably with R in the above-mentioned formula (XXIX) 1～R 4In one be that 3～6 polymkeric substance is the material of principal constituent for hydroxyl and m; Perhaps with R in the above-mentioned formula (XXX) 1～R 4In one be hydroxyl, R 5～R 8All be that hydrogen or one are hydroxyl, m/n is 1/2～1/3, and m+n is that 3～6 multipolymer is the material of principal constituent.In addition, obtainable commercially available phosphine piperazine compound is then just like SPE-100 (Da mound chemistry system trade(brand)name).
Phosphoric acid ester can be the ester cpds of phosphoric acid and alkylol cpd or oxybenzene compound, there is no particular restriction, for example can enumerate trimethyl phosphate, triethyl phosphate, triphenyl, tricresyl alkaliine, three xylyl phosphoric acid ester, cresols diphenyl phosphoester, xylyl diphenyl phosphoester, three (2, the 6-3,5-dimethylphenyl) phosphoric acid ester and aromatic condensation phosphoric acid ester etc.Wherein, from the viewpoint of hydrolytic resistance, the aromatic condensation phosphoric acid ester shown in the preferred following general formula (II).
Figure A20071010470000272
(in the formula, 8 R are the alkyl of carbonatoms 1～4, can be all identical or different.Ar is an aromatic ring).
The example of the phosphoric acid ester of above-mentioned formula (II) can be enumerated the phosphoric acid ester shown in the following array structure formula (XVI)～(XX) etc.
Figure A20071010470000281
The addition of this phosphoric acid ester is preferably with respect to the whole added ingredientss except weighting agent, in the scope of phosphorus atom amount at 0.2～3.0 weight %.Can reduce fillibility when being less than 0.2 weight %, and easily produce shaping unfavorable conditions such as space, and tend to reduce flame retardant effect.Can reduce plasticity and wet fastness when surpassing 3.0 weight %, and can ooze out phosphoric acid ester when being shaped and hinder outward appearance.
Compound shown in the preferred following general formula of phosphine oxide (III).
Figure A20071010470000291
(in the formula, R 1, R 2And R 3Be alkyl, aryl, aralkyl and the hydrogen atom of the replacement or the non-replacement of carbonatoms 1～10, can be all identical or different.But getting rid of all is the situation of hydrogen atom).
In the phosphorus compound shown in the above-mentioned general formula (I), from the hydrolytic resistance viewpoint, preferred R 1～R 3Be the aryl of replacement or non-replacement, especially preferred phenyl.
Phosphine oxide is preferably with respect to the combined amount of epoxy resin molding material for encapsulation, and the amount of phosphorus atom is 0.01～0.2 weight %, more preferably 0.02～0.1 weight %, especially preferred 0.03～0.08 weight %.Flame retardant resistance can be reduced when being lower than 0.01 weight %, plasticity and wet fastness can be reduced when surpassing 0.2 weight %.
(curing catalyst)
From the viewpoint of solidified nature, preferred (F) curing catalyst that further adds among the present invention.(F) used in the present invention curing catalyst can be the employed material of general epoxy resin molding material for encapsulation, there is no particular restriction, for example can enumerate 1,8-diaza-two ring (5,4,0) hendecene-7,1,5-diaza-two ring (4,3,0) nonene, 5,6-dibutylamino-1, cyclic amidine compounds such as 8-diaza-two ring (5,4,0) hendecene-7 grade and in this compound addition maleic anhydride, 1, the 4-benzoquinones, 2, the 5-toluquinone, 1, the 4-naphthoquinones, 2,2, the 6-phlorone, 2,3-dimethoxy-5-methyl isophthalic acid, the 4-benzoquinones, 2,3-dimethoxy-1, the 4-benzoquinones, phenyl-1, naphtoquinone compounds such as 4-benzoquinones, two azobenzene methane, resol etc. have the compound of π key and obtain have an intramolecularly polar compound; Tertiary amines and derivatives thereof such as benzyldimethylamine, trolamine, dimethylaminoethanol, three (dimethylaminomethyl) phenol; Imidazoles and derivatives thereof such as glyoxal ethyline, 2-phenylimidazole, 2-phenyl-4-methylimidazole; Organic phosphine classes such as tributylphosphine, methyldiphenyl base phosphine, triphenylphosphine, three (4-aminomethyl phenyl) phosphine, diphenylphosphine, Phenylphosphine and in this phosphine class addition maleic anhydride, above-mentioned naphtoquinone compounds, two azobenzene methane, resol etc. have the compound of π key and obtain have an intramolecularly polar compound; Tetraphenyl boron salt such as tetraphenylphosphoniphenolate tetraphenyl boric acid ester, triphenylphosphine tetraphenyl boric acid ester, 2-ethyl-4-methylimidazole tetraphenyl boric acid ester, N-methylmorpholine tetraphenyl boric acid ester and derivative thereof etc., these can use separately or two kinds or above being used in combination.Wherein, from fillibility and the anti-viewpoint of fluidity again, the affixture of preferred organic phosphine and naphtoquinone compounds.
The combined amount of curing catalyst then is not particularly limited, but is 0.005～2 weight % with respect to epoxy resin molding material for encapsulation preferably, more preferably 0.01～0.5 weight % so long as can reach the amount of solidifying facilitation effect.Have the tendency of short period of time solidified nature variation when being lower than 0.005 weight %, then can be difficult to obtain good molding too soon when surpassing 2 weight % because of curing speed.
(fire retardant)
From the viewpoint of flame retardant resistance, the present invention can further add various fire retardants.This fire retardant can be the employed material of general epoxy resin molding material for encapsulation, and there is no particular restriction, for example can enumerate brominated epoxy resins such as the 2-glycidyl ether compound of tetrabromo-bisphenol or bromination phenol phenolic resin varnish.In addition, as nitrogenous compounds such as phosphorus compounds such as weisspiessglanz, red phosphorus and above-mentioned phosphoric acid ester, trimeric cyanamide, melamine cyanurate, cyanurotriamide modified resol and guanamine modified phenolic resinss; Phosphorous/nitrogen compounds such as ring phosphine piperazine; Metallic compounds such as zinc oxide, ferric oxide, molybdenum oxide, ferrocene, above-mentioned aluminium hydroxide, magnesium hydroxide and complex metal hydroxide etc.
From in recent years the environmental problem and the viewpoint of high-temperature standing properties, the fire retardant of preferred non-halogen, non-antimony system.Wherein, from the viewpoint of fillibility, the preferably phosphoric acid ester, from the viewpoint of security and wet fastness, preferred complex metal hydroxide.
Compound shown in the preferred following composition formula of complex metal hydroxide (XXI).
p(M 1aOb)·q(M 2cOd)·r(M 3cOd)·mH 2O (XXI)
(in the formula, M 1, M 2And M 3Be different metallic element mutually, a, b, c, d, p, q and m are positive number, r be 0 or positive number).
Wherein, further the r in the preferred group accepted way of doing sth (XXI) is 0 compound, the compound shown in the promptly following composition formula (XXIa).
m(M 1aOb)·n(M 2cOd)·l(H 2O) (XXIa)
(in the formula, M 1And M 2Be mutual different metallic element, a, b, c, d, m, n and l are positive number).
M during above-mentioned composition formula (XXI) reaches (XXIa) 1And M 2Be different metallic element mutually, there is no particular restriction, but from the viewpoint of flame retardant resistance, preferred M 1And M 2Be difference, and M 1Be the metallic element that was selected from for the 3rd cycle, IIA family the alkaline-earth metal element, belong to the metallic element of IVB family, IVB family, VIII family, IB family, IIIA family and IVA family, and M 2Be the transition metal that is selected from IIIB～IIB family, more preferably M 1Be to be selected from magnesium, calcium, aluminium, tin, titanium, iron, cobalt, nickel, copper and zinc, M 2Be chosen from Fe, cobalt, nickel, copper and zinc.From mobile viewpoint, preferred M 1Be magnesium and M 2Be zinc or nickel, more preferably M 1Be magnesium and M 2Be zinc.
So long as can obtain effect of the present invention, p, the q in the above-mentioned composition formula (XXI), there is no particular restriction for the mol ratio of r, but preferred r=0, the mol ratio p/q of p and q is 99/1～50/50.That is the mol ratio m/n preferred 99/1～50/50 of m in the composition formula (XXIa) and n.
In addition, the classification of metallic element is a foundation, with the typical element for the A subtribe and be B ferrous long period type periodictable (publish: upright altogether publish the 30th printing of Co., Ltd.'s distribution minimo in " chemical voluminous dictionary 4 " on February 15th, 1987) with the transition element.
There is no particular restriction for the shape of complex metal hydroxide, but from the viewpoint of flowability and fillibility, preferably have the polyhedron-shaped of suitable thickness.In addition, complex metal hydroxide is than the easy crystallization that obtains polyhedral of metal hydroxides.
There is no particular restriction for the combined amount of complex metal hydroxide, but be 0.5～20 weight % with respect to epoxy resin molding material for encapsulation preferably, more preferably 0.7～15 weight %, especially preferred 1.4～12 weight %.Have the inadequate tendency of flame retardant resistance when being lower than 0.5 weight %, then have the tendency that fillibility and anti-fluidity again reduce when surpassing 20 weight %.
(other composition)
In addition, from the wet fastness of semiconductor elements such as raising IC and the viewpoint of high-temperature standing properties, epoxy resin molding material for encapsulation of the present invention can also add anion ion exchange body.There is no particular restriction for this anion ion exchange body, can be known material, hydrotalcite or be selected from hydrous oxide of elements such as magnesium, aluminium, titanium, zirconium, bismuth etc. for example, and these can use separately or two kinds or above being used in combination.Wherein, the hydrotalcite shown in the preferred following composition formula (XXI).
Mg 1-XAl X(OH) 2(CO 3) X/2·mH 2O…(XXI)
(0＜X≤0.5, m is a positive number.)
And then, epoxy resin molding material for encapsulation of the present invention in case of necessity can add other additive, for example tinting materials such as releasing agent, carbon black such as higher fatty acid, higher fatty acid metal-salt, ester type waxes, polyolefin-wax, polyethylene, oxidic polyethylene, silicone oil or silicone rubber powder equal stress negative catalyst etc.
(weight loss on heating rate)
The weight loss on heating rate of epoxy resin molding material is necessary for 0.25 weight % or following, preferred 0.22 weight % or following, more preferably 0.20 weight % or following.When the weight loss on heating rate surpassed 0.25 quality %, the volatile component that is produced when understanding because of shaping increased bubble, so easily make thin part produce the space.
(definition of weight loss on heating rate)
Be determined at the weight W that adds in the heat resistance container of weight A behind the resin combination 0It is positioned over 200 ℃ of atmosphere after following 1 hour, measures the total weight W of container and resin combination.Obtain the weight loss on heating rate Y of this moment by following formula.
Y＝100×(W 0-W)/(W 0-A)
(control method of weight loss on heating rate)
The volatile component that is produced when measuring the weight loss on heating rate is mainly moisture and alcohols.Therefore, effective ways comprise reduce to be shaped before the water ratio of epoxy resin molding material, make the minimum of coupler must measure optimizing, use the coupler that is difficult to generate volatile component etc.
(rerum natura after epoxy resin molding material solidifies)
The preferred epoxy resin molding material for encapsulation that meets at least one condition in the following condition that uses: based on the second-order transition temperature of TMA method be 150 ℃ or above, based on the bending elastic modulus of JIS-K6911 as 19GPa or following, based on the shaping shrinkage rate of JIS-K6911 be 0.2% or below.More preferably meet two or more above-mentioned conditions, especially preferred three all meet.From the viewpoint of warpage, this second-order transition temperature preferred 160 ℃ or more than, more preferably 170 ℃ or more than.Can tend to increase warpage when being lower than 150 ℃.From the viewpoint of warpage, the preferred 18.5GPa of bending elastic modulus or following, more preferably 18GPa or following.Can tend to increase warpage when surpassing 19GPa.In addition, from the viewpoint of warpage, shaping shrinkage rate preferred 0.18% or below, more preferably 0.15% or below.Surpass at 0.2% o'clock and can tend to increase warpage.
(modulation and using method)
Epoxy resin molding material for encapsulation of the present invention, so long as various raw materials of dispersing and mixing equably, then can use any method modulation, can enumerate as behind the raw material that utilizes the given combined amount of thorough mixing such as agitator as general method, after utilizing mixing such as mixing roll, extrusion machine, shredder, planetary stirrer or fusion to mix, cool off, and the method for deaeration as required, pulverizing etc.In addition, can make tablet according to size that meets molding condition and weight in case of necessity.
With epoxy resin molding material for encapsulation of the present invention is in the method for sealing material sealed semiconductor device, and prevailing is the low-pressure transfer moulding method, and other also has injection molding method, compression forming method etc.Also can use distribution means, casting mode, mode of printing etc.From the viewpoint of fillibility, the preferred moulding method that can under decompression state, be shaped.
Enumerate several embodiments below epoxy resin molding material for encapsulation of the present invention is described.
(the 1st embodiment)
The 1st embodiment of relevant epoxy resin molding material for encapsulation of the present invention, can enumerate as contain (A) Resins, epoxy, (B) solidifying agent and (C) median size be that 12 μ m or following and specific surface area are 3.0m 2The epoxy resin molding material for encapsulation of/g or above inorganic filler.At this moment, inorganic filler (C) preferably meets at least one condition in the following condition: particle diameter 12 μ m or following have 50wt% or above, particle diameter 24 μ m following have 70wt% or above, particle diameter 32 μ m or following have 80wt%, particle diameter 48 μ m following have 90wt% or more than.In addition, (C) median size of inorganic filler is preferably 10 μ m or following.(C) specific surface area of inorganic filler is preferably 3.5～5.5m 2/ g.
Preferably reach (C) inorganic filler according to selected (A) Resins, epoxy of following viewpoint, (B) solidifying agent.
During selected (A) Resins, epoxy preferably the melt viscosity at 150 ℃ be 2 pool or following materials, more preferably 1 pool or following material.This selection is effective in the high situation of blending ratio of (C) inorganic filler especially.Wherein, from the viewpoint of fillibility and reliability, it is at least a that preferred use is selected from biphenyl type epoxy resin, bisphenol f type epoxy resin, stilbene type Resins, epoxy and sulfur atom-containing Resins, epoxy.In addition, from the viewpoint of the warpage that reduces flip-chip mount type package, preferably use from naphthalene type Resins, epoxy and tritane type Resins, epoxy, select at least a.In order to take into account fillibility and warpage properties, preferred and use from biphenyl type epoxy resin, bisphenol f type epoxy resin, stilbene type Resins, epoxy and sulfur atom-containing Resins, epoxy, select at least a with from naphthalene type Resins, epoxy, tritane type Resins, epoxy, select at least a.
During selected (B) solidifying agent preferably the melt viscosity at 150 ℃ be 2 pool or following materials, more preferably 1 pool or following material.This selection is effective in the high situation of blending ratio of (C) inorganic filler especially.And be effective in the situation selecting the situation of at least a conduct (A) Resins, epoxy of from phenolic resin varnish type epoxy resin, selecting with regard to the plasticity viewpoint for use, select dicyclopentadiene-type epoxy resin with regard to the agent of low hygroscopicity viewpoint for use, with regard to thermotolerance and low warpage properties viewpoint and select at least a situation of from naphthalene type Resins, epoxy and tritane type Resins, epoxy, selecting for use.
Selected (C) median size is that 15 μ m or following and specific surface area are 3.0～6.0m 2During the inorganic filler of/g, preferably in median size is 15 μ m or following scope, getting final product of the size that consider to be fit to the bump height of flip-chip mounted semiconductor device of the present invention and bump pitch and to select to inject, if but selected material for use less than required size, flowability and fillibility will be reduced.For fear of this situation, preferably select for use specific surface area at 3.0～6.0m 2The material of/g scope.In order to make median size and specific surface area meet above-mentioned scope, effectively way is that two kinds of combinations or above commercially available inorganic filler are regulated.
In addition, in case of necessity can be with mesh screen except that the coarse particle component in (C) inorganic filler.Preferred 53 μ m or above (C) composition are 0.5 weight % or following, and more preferably 30 μ m or above (C) composition are 0.5 weight % or following, and especially preferred 20 μ m or above (C) composition are 0.5 weight % or following.
Selecting (C) median size is that 12 μ m or following and specific surface area are 3.0m 2When/g or above inorganic filler, preferably in median size 12 μ m or following scope, getting final product of the size that consider to be fit to the bump height of flip-chip mounted semiconductor device of the present invention and bump pitch and to select to inject, but, therefore should avoid if select for use material can reduce flowability less than required size.In addition, preferably at specific surface area 3.0m 2In/g or the above scope, be chosen in the median size that the to inject little material of trying one's best.In order to make median size and specific surface area both sides meet above-mentioned scope, effective means is combination two kinds or an above commercially available inorganic filler.In addition, can screen out coarse particle component in (C) inorganic filler in case of necessity.Preferred 53 μ m or above (C) composition are 0.5 weight % or following, and more preferably 30 μ m or above (C) composition are 0.5 weight % or following, and especially preferred 20 μ m or above (C) composition are 0.5 weight % or following.
Except mentioned component, also can add silane coupling agent that (D2) have secondary amino group, (E) phosphorus compound and (F) any in the curing catalyst as required.Can obtain flip-chip mount type bottom filling epoxy resin molding material for encapsulation by adjusting the array mode and the combined amount of each composition.Can obtain flip-chip mount type bottom filling epoxy resin molding material for encapsulation by adjusting the array mode and the combined amount of each composition.
(the 2nd embodiment)
The 2nd embodiment of relevant epoxy resin molding material for encapsulation of the present invention, can enumerate contain (A) Resins, epoxy, (B) solidifying agent and (C) maximum particle diameter be that 63 μ m or following and particle diameter are 20 μ m or the above epoxy resin molding material for encapsulation that 5wt% or above inorganic filler are arranged.At this moment, (C) preferred 10 μ m or following of the median size of inorganic filler.In addition, (C) preferred 3.5～5.5m of the specific surface area of inorganic filler 2/ g.In addition, can select for use (A) Resins, epoxy, (B) solidifying agent to reach (C) inorganic filler according to the viewpoint identical with the 1st embodiment.
Except mentioned component, also can add silane coupling agent that (D2) have secondary amino group, (E) phosphorus compound and (F) any in the curing catalyst as required.Can obtain flip-chip mount type bottom filling epoxy resin molding material for encapsulation by adjusting the array mode and the combined amount of each composition.
When manufacturing possesses the flip-chip semiconductor device of future generation of the soldering projection of fine pitch etc., use the situation of solid type encapsulating epoxy resin in the past, can't fill the bottom filling part owing to produce the big a little space about diameter 0.1mm.But be used as sealing material by epoxy resin molding material for encapsulation of the present invention, can eliminate described problem with the 1st, 2 embodiments.
(the 3rd embodiment)
The 3rd embodiment of relevant epoxy resin molding material for encapsulation of the present invention, can enumerate contained must composition for (A) Resins, epoxy, (B) solidifying agent and (C) median size be that 15 μ m or following and specific surface area are 3.0～6.0m 2The epoxy resin molding material for encapsulation of the inorganic filler of/g.Can select for use (A) Resins, epoxy, (B) solidifying agent to reach (C) inorganic filler according to the viewpoint identical with the 1st embodiment.
Except mentioned component, also can add silane coupling agent that (D2) have secondary amino group, (E) phosphorus compound and (F) any in the curing catalyst as required.Can obtain flip-chip mount type bottom filling epoxy resin molding material for encapsulation by adjusting the array mode and the combined amount of each composition.The semiconductor device of one or more formations in following in particular for possessing (a1)～(d1):
(a1) bump height of flip-chip is 150 μ m or following;
(b1) bump pitch of flip-chip is 500 μ m or following;
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following.
(the 4th embodiment)
The 4th embodiment of relevant epoxy resin molding material for encapsulation of the present invention, can enumerate and contain (A) Resins, epoxy, (B) solidifying agent, (C) inorganic filler and (D) epoxy resin molding material for encapsulation of coupler, wherein, (C) specific surface area of inorganic filler is 3.0～6.0m 2/ g.Can select for use (A) Resins, epoxy, (B) solidifying agent to reach (C) inorganic filler according to the viewpoint identical with the 1st embodiment.
(D) the weighting material fraction of coverage preferred 0.3～1.0 of coupler.In addition, the preferred 0.25 weight % or following of weight loss on heating rate after the 200 ℃/1hr heating.Also can add mentioned component other additive in addition as required.Can obtain flip-chip mount type bottom filling epoxy resin molding material for encapsulation by adjusting the array mode and the combined amount of each composition.
(the 5th embodiment)
The 5th embodiment of relevant epoxy resin molding material for encapsulation of the present invention, can enumerate at least and contain (A) Resins, epoxy, (B) solidifying agent and (C) in the epoxy resin molding material for encapsulation of inorganic filler, meet the epoxy resin molding material for encapsulation of at least one condition in the following condition: based on the second-order transition temperature of TMA method be 150 ℃ or more than; Bending elastic modulus based on JIS-K6911 is 19GPa or following; Based on the shaping shrinkage rate of JIS-K6911 be 0.2% or below.Can select for use (A) Resins, epoxy, (B) solidifying agent to reach (C) inorganic filler according to the viewpoint identical with the 1st embodiment.
Can be used for possessing following (c1) this moment, (d1) and one or more the semiconductor device that (g1) constitutes:
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following;
(g1) the sealing material shaping area of once-forming mode is 3000mm 2Or more than.
In addition, can be used for possessing following (c2), (d2) and one or more the semiconductor device that (g2) constitutes:
(c2) area of semi-conductor chip is 50mm 2Or more than;
(d2) total thickness of sealing material is 1.5mm or following;
(g2) the sealing material shaping area of once-forming mode is 5000mm 2Or more than.
The warpage of the semiconductor device of the 5th embodiment gained is 5.0mm or following, and the warpage of preferred semiconductor device is 2.0mm or following.
When manufacturing possesses the flip-chip semiconductor device of future generation of soldering projection of fine pitch etc., use the situation of solid type encapsulating epoxy resin sealing in the past, can't fully fill the bottom filling part owing to produce the big a little space about diameter 0.1 μ m.But be used as sealing material by the encapsulating epoxy resin of the present invention that is representative in order to above-mentioned the 1st～the 5th embodiment, can eliminate described problem.That is, epoxy resin molding material for encapsulation of the present invention is applicable to and makes the semiconductor device of giving fixed structure that possesses explanation in the following semiconductor device part.
In addition,, can install as flip-chip with bottom filling and in the suitable fillibility keeping, reduce the substrate warpage after the sealing and the warpage of package according to the 5th embodiment.
(embodiment 1 of semiconductor device)
The embodiment of semiconductor device of the present invention is described below with reference to Fig. 1～Fig. 4.But semiconductor device of the present invention is not limited to this.
Fig. 1 is the sectional view of the flip chip type BGA of bottom filled-type, and Fig. 2 is the sectional view of the flip chip type BGA of pressing mold forming.Fig. 3 is at the vertical view (part skeleton view) during across soldering projection 2 configuring semiconductor chips 3 on the circuit card 1 of flip chip type BGA.
The semiconductor device 10 of the flip chip type BGA of bottom shown in Figure 1 filled-type is following obtaining: dispose soldering projection 2 with given bump pitch b as shown in Figure 3 on circuit card 1; Semi-conductor chip 3 is connected and fixed on the circuit card 1 with bump height a across this soldering projection 2; Use epoxy resin molding material for encapsulation (sealing material) 4 to seal the bottom filling part 5 that is formed between circuit card 1 and the semi-conductor chip 3.The semiconductor device 20 of the flip chip type BGA of pressing mold forming shown in Figure 2, then except sealed bottom filling part 5 in seal process and cover the semi-conductor chip 3 comprehensively, other is then similarly made with aforementioned.
Here, make in the embodiment of semiconductor device of the present invention, be preferably as follows bump height a, the bump pitch b, the area c of semi-conductor chip and the total thickness d of sealing material that set semiconductor device.
The preferred 150 μ m or following of the height a of soldering projection 2, more preferably 100 μ m or following, especially preferred 80 μ m or following.The spacing b of soldering projection 2, i.e. preferred 500 μ m or following of the centre compartment of soldering projection, more preferably 400 μ m or following, especially preferred 300 μ m or following.
The number of soldering projection 2 preferred 100 or more than, more preferably 150 or more than, especially preferred 200 or more than.
The preferred 25mm of the area of semi-conductor chip 3 2Or more than, more preferably 50mm 2Or more than, especially preferred 80mm 2Or more than.
The preferred 2mm of the total thickness d of sealing material 4 or following, more preferably 1.5mm or following, especially preferably 1.0mm or following.
In addition, the total thickness of bottom filled-type is identical value with bump height a.
(embodiment 2 of semiconductor device)
Fig. 4 is for after utilizing soldering projection 2 to be connected and fixed semi-conductor chip 3 on the circuit card 1, utilize the flip chip type BGA of epoxy resin molding material for encapsulation (sealing material) 4 sealings, wherein Fig. 4 (x) is sectional view (pressing mold forming), (y) is vertical view (part skeleton view).
In the semiconductor device of the present invention shown in Figure 4, the preferred 25mm of area c of semi-conductor chip 3 2Or more than, more preferably 50mm 2Or more than, especially preferred 70mm 2Or more than.
The preferred 2mm of the total thickness d of sealing material 4 or following, more preferably 1.5mm or following, especially preferably 1.0mm or following.
The preferred 3000mm of sealing material shaping area g of once-forming mode 2Or more than, more preferably 5000mm 2Or more than.
(other embodiment of semiconductor device)
Other embodiment of semiconductor device of the present invention, can enumerate and finish the winding of wiring, circuit card, glass supporting member and installing on the substrate, after carrying elements such as passive element such as active component, electrical condenser, resistor, coil such as semi-conductor chip, transistor, diode, thyristor, utilize the flip-chip mounted semiconductor device of epoxy resin molding material for encapsulation sealing etc.
Here, as the epoxy resin molding material for encapsulation that constitutes described semiconductor device, can use the epoxy resin molding material for encapsulation of embodiment of the present invention.For example use the inorganic filler that contains (A) Resins, epoxy, (B) solidifying agent and (C) meet any one condition in following (1) and (2) at least:
(1) median size is 12 μ m or following, and specific surface area is 3.0m 2/ g or more than;
(2) maximum particle diameter is 63 μ m or following, and particle diameter be 20 μ m or above inorganic filler content be 5wt% or more than;
And, contain the silane coupling agent and (E) epoxy resin molding material for encapsulation of curing catalyst that (D2) has secondary amino group as required.
From improving the viewpoint of fillibility, (C) inorganic filler of inorganic filler preferably eligible (1) is from improving the viewpoint of flash, the then preferred inorganic filler that uses eligible (2), but from these two viewpoints, the weighting agent of more preferably eligible (1) and (2).
There is no particular restriction as substrate is installed, for example can enumerate interpolation substrates such as organic substrate, organic film, ceramic substrate, glass substrate, liquid crystal with glass substrate, MCM (multi-chip module) with substrate, mix IC with substrate etc.
As the embodiment of semiconductor device of the present invention, preferably possess the following formation that one or more are defined as set-point separately: (a) number of lugs of the total thickness of the area of the bump pitch of the bump height of flip-chip, (b) flip-chip, (c) semi-conductor chip, (d) sealing material, (e) flip-chip reaches the ventage thickness when (f) being shaped.Particularly, preferably possess one or more formation in following (a1)～(f1):
Bump height when (a1) flip-chip is installed is 150 μ m or following;
(b1) bump pitch of flip-chip is 500 μ m or following;
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following;
(e1) number of lugs of flip-chip be 100 or more than;
Ventage thickness when (f1) being shaped is 40 μ m or following.
More preferably possess one or more the semiconductor device of formation in following (a2)～(f2):
Bump height when (a2) flip-chip is installed is 100 μ m or following;
(b2) bump pitch of flip-chip is 400 μ m or following;
(c2) area of semi-conductor chip is 50mm 2Or more than;
(d2) total thickness of sealing material is 1.5mm or following;
(e2) number of lugs of flip-chip be 150 or more than;
Ventage thickness when (f2) being shaped is 30 μ m or following.
Especially preferably possess one or more the semiconductor device of formation in following (a3)～(f3):
Bump height when (a3) flip-chip is installed is 150 μ m or following;
(b3) bump pitch of flip-chip is 300 μ m or following;
(c3) area of semi-conductor chip is 80mm 2Or more than;
(d2) total thickness of sealing material is 1.0mm or following;
(e3) number of lugs of flip-chip be 200 or more than;
Ventage thickness when (f3) being shaped is 20 μ m or following.
To enumerate below semiconductor device preferred embodiment will be described, wherein, preferably possess the semiconductor device that (a)～(f) constitutes with following combination.
From the fillibility viewpoint, preferably possesses the semiconductor device of the either party in formation (a) and the formation (b) at least.More specifically, preferably possess formation (a1) and semiconductor device (b1), possess formation (a1) and semiconductor device (d1), possess formation (a1) and semiconductor device (c1), possess formation (b1) and semiconductor device (d1), possess formation (b1) and semiconductor device (c1).More preferably possess formation (a2) and semiconductor device (b2), possess formation (a2) and semiconductor device (d2), possess formation (a2) and semiconductor device (c2), possess formation (b2) and semiconductor device (d2), possess formation (b2) and semiconductor device (c2).Further preferably possess formation (a3) and semiconductor device (b3), possess formation (a3) and semiconductor device (d3), possess formation (a3) and semiconductor device (c3), possess formation (b3) and semiconductor device (d3), possess formation (b3) and semiconductor device (c3).
As such semiconductor device can enumerate as, with the flip-chip binding material with semi-conductor chip be connected to be formed at circuit card or distribution on glass after, COB (Chip On Board), the semiconductor device such as installation such as COG (the Chip On Glass) nude film of etc.ing that obtains with epoxy resin molding material for encapsulation sealing of the present invention again; With the flip-chip binding material passive elements such as active component such as semi-conductor chip, transistor, diode, thyristor and/or electrical condenser, resistor, coil are connected to and are formed on circuit card or the distribution on glass, again the mixing IC that obtains with epoxy resin molding material for encapsulation sealing of the present invention; With semiconductor-chip-mounting on the interpolation substrate that forms MCM (multi-chip module) motherboard terminal for connecting, after connecting semi-conductor chip and the distribution that is formed on the interpolation substrate with projection again, carry side and the BGA (BGA Package), CSP (chip size packages), the MCP (encapsulation of multicore sheet) etc. that obtain with epoxy resin molding material for encapsulation sealing semiconductor chips of the present invention.In addition, this semiconductor device can be to carry stacked (lamination) type package of two or more elements with overlap mode on the installation substrate, or seals the once-forming type package of two or more elements together with epoxy resin molding material for encapsulation.
(embodiment 2 of semiconductor device)
The preferred epoxy resin molding material for encapsulation of the present invention of employed epoxy resin molding material for encapsulation.Promptly, at least contain (A) Resins, epoxy, (B) solidifying agent and (C) in the epoxy resin molding material for encapsulation of inorganic filler, preferred employed epoxy resin molding material for encapsulation meets at least one condition in the following condition: epoxy resin molding material for encapsulation based on the second-order transition temperature of TMA method be 150 ℃ or more than, bending elastic modulus based on JIS-K6911 is 19GPa or following, based on the shaping shrinkage rate of JIS-K6911 be 0.2% or below.More preferably meet two or more conditions, especially preferred three conditions all meet.From the viewpoint of angularity, second-order transition temperature preferred 160 ℃ or more than, more preferably 170 ℃ or more than.The tendency that exists angularity to increase when being lower than 150 ℃.From the viewpoint of angularity, the preferred 18.5GPa of bending elastic modulus or following, more preferably 18GPa or following.The tendency that exists angularity to increase when surpassing 19GPa.In addition, from the viewpoint of angularity, shaping shrinkage rate preferred 0.18% or below, more preferably 0.15% or below.Surpass the tendency that had the angularity increase at 0.2% o'clock.
Use the preferred 5.0mm of angularity of semiconductor device of above-mentioned epoxy resin molding material for encapsulation sealing or following, more preferably 2.0mm or following, especially preferred 1.5mm or following.When surpassing 5.0mm, for the semiconductor device of once-forming mode, in the time of can impairing cutting semiconductor device monolithic and the operation during mounting circuit boards.
There is no particular restriction as substrate is installed, for example can enumerate interpolation substrates such as organic substrate, organic film, ceramic substrate, glass substrate, liquid crystal with glass substrate, MCM (multi-chip module) with substrate, mix IC with substrate etc.
As semiconductor device of the present invention, preferably possesses the following formation that one or more are defined as set-point separately: (a) number of lugs of the total thickness of the area of the bump pitch of the bump height of flip-chip, (b) flip-chip, (c) semi-conductor chip, (d) sealing material, (e) flip-chip and (g) the sealing material shaping area of once-forming mode.
Particularly, the formation that preferably possesses one or more following (a1)～(g1).
Here, " total thickness of sealing material " of the present invention is meant bump height for the filled-type of bottom.
(a1) bump height of flip-chip is 150 μ m or following;
(b1) bump pitch of flip-chip is 500 μ m or following;
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following;
(e1) number of lugs of flip-chip be 100 or more than;
(g1) the sealing material shaping area of once-forming mode is 3000mm 2Or more than.
The formation that more preferably possesses one or more following (a2)～(g2).
(a2) bump height of flip-chip is 100 μ m or following;
(b2) bump pitch of flip-chip is 400 μ m or following;
(c2) area of semi-conductor chip is 50mm 2Or more than;
(d2) total thickness of sealing material is 1.5mm or following;
(e2) number of lugs of flip-chip be 150 or more than;
(g2) the sealing material shaping area of once-forming mode is 5000mm 2Or more than.
Especially preferably the formation that possesses one or more following (a3)～(g3).
(a3) bump height of flip-chip is 80 μ m or following;
(b3) bump pitch of flip-chip is 300 μ m or following;
(c3) area of semi-conductor chip is 80mm 2Or more than;
(d3) total thickness of sealing material is 1.0mm or following;
(e3) number of lugs of flip-chip be 200 or more than;
(g3) the sealing material shaping area of once-forming mode is 7000mm 2Or more than.
To enumerate below semiconductor device preferred embodiment will be described, but especially preferably possess the semiconductor device that following (a)～(g) constitutes with following combination.
From the viewpoint of fillibility, preferably possesses the semiconductor device of at least one side in formation (a) and the formation (b).More specifically, preferably possess formation (a1) and (b1) semiconductor device, possess formations (a1) and semiconductor device (d1), possess formations (a1) and semiconductor device (c1), possess formation (b1) and reach (d1) semiconductor device, possess formation (b1) and reach (c1) semiconductor device.More preferably possess formation (a2) and semiconductor device (b2), possess formation (a2) and semiconductor device (d2), possess formation (a2) and semiconductor device (c2), possess formation (b2) and semiconductor device (d2), possess formation (b2) and semiconductor device (c2).Especially preferably possess formation (a3) and semiconductor device (c3), possess formation (a3) and semiconductor device (d3), possess formation (a3) and semiconductor device (c3), possess formation (b3) and semiconductor device (d3), possess formation (b3) and semiconductor device (c3).
In addition, from the viewpoint of angularity, preferably possess formation (c), constitute (d) and constitute at least one semiconductor device in (g).More specifically, preferably possess formation (c1) and (g1) semiconductor device, possess formations (c1) and semiconductor device (d1), possess formation (d1) and reach (g1) semiconductor device.More preferably possess formation (c2) and semiconductor device (g2), possess formation (c2) and semiconductor device (d2), possess formation (d2) and semiconductor device (g2).Especially preferably possess formation (c3) and (g3) semiconductor device, possess formations (c3) and (d3) structure semiconductor device, possess formation (d3) and reach (g3) semiconductor device.
Embodiment
Represent embodiments of the invention below, but scope of the present invention is not limited to these embodiment.In addition, do not having under the situation about specifying, the evaluation of each epoxy resin molding material for encapsulation and semiconductor device is based on the described evaluation method in back and carries out.
Embodiment A
(embodiment A 1～A7, Comparative examples A 1～A6)
After mixing each material of composition premix (do and mix) shown in table 1～table 3, mixed 10 minutes with the about 80 ℃ twin shaft roller mill of roll surface temperature, then cooling is pulverized, and obtains each epoxy resin molding material for encapsulation A1～A13 of embodiment A 1～A7 and Comparative examples A 1～A6.Here, consist of weight part in the table.
(A) Resins, epoxy
Employed biphenyl type epoxy resin is the goods エ ピ コ one ト YH-4000H (epoxy equivalent (weight) 196 by name that ジ ヤ パ Application エ Port キ シ レ ジ Application society makes, 106 ℃ of fusing points) material, brominated epoxy resin is the goods ESB-400 (epoxy equivalent (weight) 400 by name that sumitomo chemical company is made, the table dimorphism of bromine content 49% (エ ピ PVC ス type) Resins, epoxy, 2,2 '-two (4-hydroxyl-3,5-dibromo phenyl) propane is by the 2-glycidyl etherificate modifier of Epicholorohydrin) material.
(B) solidifying agent
Employed (B) solidifying agent is, 73 ℃ of hydroxyl equivalents 156, softening temperature by the phenol-phenyl aldehyde shown in the following structural (XXII)-xylylene diformazan alkoxide polycondensate (living in golden ケ ミ カ Le corporate system name of an article HE510-05), and 83 ℃ of hydroxyl equivalents 100, softening temperature by the phenol-hydroxy benzaldehyde resin shown in the following structural (XXIII) (bright and change into corporate system name of an article MEH-7500-3S).
Figure A20071010470000431
(in the formula, n is 0～8 positive number.)
Figure A20071010470000441
(in the formula, n is 0～8 positive number.)
Utilize and shift forming mill, add up to 13 kinds shaped material to be shaped separately gained with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times, again with helicoidal flow, gel time test evaluation.
[making semiconductor device A1 (flip-chip BGA)]
Then, use epoxy resin molding material for encapsulation A1～A13 to make the semiconductor device of embodiment A 1～A7 and Comparative examples A 1～A6.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment A 1～A7 (table): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of semiconductor-chip-mounting side and reverse side; be that the mounting semiconductor element of indulging 22mm * horizontal 14mm * thick 0.3mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 9mm * horizontal 8mm * thick 0.4mm (area 72mm 2), the semiconductor element of 160 of projection footpath 145 μ m, bump pitch 200 μ m, number of lugs flows to handle again and installs.Bump height after the installation is 100 μ m.Then use epoxy resin molding material for encapsulation 1～7, the mounting semiconductor element face is carried out vacuum transfer with the size of vertical 22mm * horizontal 14mm * thick 0.7mm with above-mentioned condition be shaped, obtain the flip-chip BGA device of embodiment 1～7.
Comparative examples A 1～A6 (table): except using epoxy resin molding material for encapsulation A8～A13, other and embodiment A 1～A7 similarly carry out, and make the semiconductor device of Comparative examples A 1～A6.
[making semiconductor device A2 (flip-chip BGA)]
Then, use epoxy resin molding material for encapsulation A1～A13, make the semiconductor device of embodiment A 1～A7 and Comparative examples A 1～A6.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment A 1～A7 (table): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 22mm * horizontal 14mm * thick 0.3mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 6mm * horizontal 5mm * thick 0.4mm (area 30mm 2), projection footpath 300 μ m, bump pitch 490 μ m, the semiconductor element that number of lugs is 120 flows to handle again to be installed.Bump height after the installation is 260 μ m.Then use epoxy resin molding material for encapsulation 1～7, the size of mounting semiconductor element face with vertical 22mm * horizontal 14mm * thick 1.2mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of embodiment.
Comparative examples A 1～A6 (table): except using epoxy resin molding material for encapsulation A8～A13, other and embodiment A 1～A7 carry out in the same manner, make the semiconductor device of Comparative examples A 1～A6.
[making semiconductor device A3 (flip-chip BGA)]
Then, use epoxy resin molding material for encapsulation A1～A13, make the semiconductor device of embodiment A 1～A7 and Comparative examples A 1～A6.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment A 1～A7 (table): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 22mm * horizontal 14mm * thick 0.3mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 5mm * horizontal 4mm * thick 0.4mm (area 20mm 2), the semiconductor element of 40 of projection footpath 390 μ m, bump pitch 700 μ m, number of lugs flows to handle again and installs.Bump height after the installation is 350 μ m.Then, use epoxy resin molding material for encapsulation 1～7, the size of mounting semiconductor element face with vertical 22mm * horizontal 14mm * thick 2.5mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of embodiment 1～7.
Comparative examples A 1～A6 (table): except using epoxy resin molding material for encapsulation 8～13, other and embodiment A 1～A7 similarly carry out, and make the semiconductor device of Comparative examples A 1～A6.
Semiconductor device by following test evaluation gained embodiment A 1～A7 and Comparative examples A 1～A6.The result is shown in table 2～table 3.
Table 1
Project Weighting agent A Weighting agent B Weighting agent C Weighting agent D Weighting agent E Weighting agent F Weighting agent G
Size-grade distribution (accumulating weight %) ～1gm 11 11 27 27 10 10 11
～2μm 20 20 38 42 20 21 25
～4μm 30 30 45 54 29 31 41
～6μm 37 36 50 63 34 37 52
～12μm 50 53 73 86 45 48 82
～24μm 71 75 87 96 61 68 100
～32μm 81 83 93 100 72 80 100
～48μm 95 96 98 100 86 94 100
～64μm 100 100 100 100 92 97 100
～96μm 100 100 100 100 98 100 100
Median size μm 12 11 6 3 18 15 6
Specific surface area m 2/g 3.5 3.3 4.0 3.5 3.5 3.8 2.7
Maximum particle diameter μm 63 53 53 30 105 75 30
20 μ m or above packing material amount wt％ 33 30 15 5 43 37 4
Table 2
Project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
Resin No. 1 2 3 4 5 6 7
Resins, epoxy YX-4000H 85 85 85 85 85 85 85
*1 15 15 15 15 15 15 15
Solidifying agent Structural formula (XXII) 75 75 75 75 - - -
Structural formula (XXIII) - - - - 50 50 50
Curing catalyst *2 3.5 3.5 3.5 3.5 2.5 2.5 2.5
Coupler *3 5 5 5 5 5 5 5
ANTIMONY TRIOXIDE SB 203 99.8 PCT Sb 2O 3 5 5 5 5 5 5 5
Releasing agent Carnauba wax 2 2 2 2 2 2 2
Tinting material Carbon black 3 3 3 3 3 3 3
Weighting agent A 1850 - - - - - -
B - 1850 - - 1320 - -
C - - 1850 - - 1320 -
D - - - 1400 - - 1179
E - - - - - - -
F - - - - - - -
G - - - - - - -
Helicoidal flow cm 105 115 95 100 160 145 130
Gel time sec 38 43 42 45 50 50 52
Flash - Well Well Well Well Well Well Well
The space generation Semiconductor device 1 0/20 0/20 0/20 0/20 0/20 0/20 0/20
Semiconductor device 2 0/20 0/20 0/20 0/20 0/20 0/20 0/20
Semiconductor device 3 0/20 0/20 0/20 0/20 0/20 0/20 0/20
*1:2, the ether modifier of the Epicholorohydrin of two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-
*2: the affixture of triphenylphosphine and benzoquinones
*3: γ-glycidoxypropyltrime,hoxysilane
Table 3
Project Comparative examples A 1 Comparative examples A 2 Comparative examples A 3 Comparative examples A 4 Comparative examples A 5 Comparative examples A 6
Resin No. 8 9 10 11 12 13
Resins, epoxy YX-4000H 85 85 85 85 85 85
*1 15 15 15 15 15 15
Solidifying agent Structural formula (XXII) 75 75 75 - - -
Structural formula (XXIII) - - - 50 50 50
Curing catalyst *2 3.5 3.5 3.5 2.5 2.5 2.5
Coupler *3 5 5 5 5 5 5
Tellurium dioxide Sb 2O 3 5 5 5 5 5 5
Releasing agent Carnauba wax 2 2 2 2 2 2
Tinting material Carbon black 3 3 3 3 3 3
Weighting agent A - - - - - -
B - - - - - -
C - - - - - -
D - - - - - -
E 1850 - - 1320 - -
F - 1850 - - 1320 -
G - - 1400 - - 1179
Helicoidal flow cm 95 100 75 150 160 105
Gel time sec 37 38 42 49 50 50
Flash - Well Well NG Well Well NG
The space generation Semiconductor device 1 20/20 10/20 15/20 20/20 8/20 11/20
Semiconductor device 2 15/20 0/20 0/20 13/20 0/20 0/20
Semiconductor device 3 0/20 0/20 0/20 0/20 0/20 0/20
*1:2, the ether modifier by Epicholorohydrin of two (4-hydroxyl-3, the 5-dibromo phenyl) propane of 2-
*2: the affixture of triphenylphosphine and benzoquinones
*3: γ-glycidoxypropyltrime,hoxysilane
[evaluation method]
(1) helicoidal flow (fluidity index)
Utilization is measured with behind the die forming according to the helicoidal flow of EMMI-1-66, obtains mobile distance.
(2) gel time
Utilize JSR system Curelasto meter to add the sulfur test machine, under sample 3g, 180 ℃ of conditions of temperature, measure torque curve to the time (s) of rising.
(3) space generation
Utilize ultrasonic investigation mapping device (Hitachi builds machine corporate system HYE-HOCUS type) fluoroscopic observation semiconductor device, observation has or not diameter 0.1mm or above space to produce, and estimates to produce space semiconductor device number/semiconductor test apparatus number again.
(4) flash
Utilization is obtained effusive flash length in the slit with vernier callipers after being provided with die forming than the slit of the also thick 10 μ m of still.In addition, set in the slit flash length and be lower than 10 μ m for well, 10 μ m or above be NG.
The epoxy resin molding material for encapsulation that flip-chip of the present invention is installed usefulness has as the desired high fillibility of bottom filling, and shaping unfavorable condition such as space is less, so its industrial value is very big.
Embodiment B
[making epoxy resin molding material for encapsulation]
Add following ingredients with the weight part shown in table 4, the table 5, carry out roller mill with 80 ℃ of the temperature of mixing, the condition of the 10 minutes time of mixing again and mix, obtain epoxy resin molding material for encapsulation B1～B19.
(Resins, epoxy)
Employed Resins, epoxy is, the biphenyl type epoxy resin (the system trade(brand)name エ ピ コ one ト YX-4000H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.) that epoxy equivalent (weight) 196, fusing point are 106 ℃; The bisphenol f type epoxy resin that epoxy equivalent (weight) 186, fusing point are 75 ℃ (the system trade(brand)name YSLV-80XY of Nippon Steel Chemical Co., Ltd); The stilbene type Resins, epoxy that epoxy equivalent (weight) 210, fusing point are 120 ℃ (the system trade(brand)name ESLV-210 of Sumitomo Chemical Company Ltd); The sulfur atom-containing Resins, epoxy that epoxy equivalent (weight) 245, fusing point are 110 ℃ (the system trade(brand)name YSLV-120TE of Nippon Steel Chemical Co., Ltd); The molten tris-phenol type Resins, epoxy 1 (the system trade(brand)name エ ピ コ one ト E1032H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.) that touches viscosity 2.4 pools that epoxy equivalent (weight) 170, softening temperature are 60 ℃, 150 ℃; The tris-phenol type Resins, epoxy 2 of fusion granularity 3.1 pools that epoxy equivalent (weight) 170, softening temperature are 70 ℃, 150 ℃ (the system trade(brand)name エ ピ コ one ト E1032H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.); The o-cresol phenolic epoxy varnish that epoxy equivalent (weight) 195, softening temperature are 65 ℃ (the system trade(brand)name ESCN-190 of Sumitomo Chemical Company Ltd).
(solidifying agent)
Employed solidifying agent is the phenol of 70 ℃ of softening temperatures, hydroxyl equivalent 175-aralkyl resin (the system trade(brand)name ミ レ of Mitsui Chemicals, Inc Star Network ス XL-225); The tris-phenol type Resins, epoxy 1 of melt viscosity 1.3 pools of 83 ℃ of softening temperatures of the biphenyl type resol of 80 ℃ of softening temperatures, hydroxyl equivalent 199 (bright and change into Co., Ltd. system trade(brand)name MEH-7851), 103,150 ℃ of hydroxyl equivalents (bright and change into system trade(brand)name MEH-7500-3S); The tris-phenol type Resins, epoxy 2 of melt viscosity 3.0 pool of 101 ℃ of softening temperatures, 101,150 ℃ of hydroxyl equivalents (bright and change into system trade(brand)name MEH-7500-SS); The phenol novolac resin of 80 ℃ of softening temperatures, hydroxyl equivalent 106 (bright and change into Co., Ltd. system trade(brand)name H-1).
(curing catalyst)
Employed curing catalyst is the affixture (curing catalyst) of triphenylphosphine and para benzoquinone, and coupler is silane coupling agent (γ-anilino propyl trimethoxy silicane (anilino silane)), the γ-glycidoxypropyltrime,hoxysilane (epoxy silane) that contains secondary amino group.
(fire retardant)
Employed fire retardant is aromatic condensation phosphoric acid ester (big eight chemistry system trade(brand)name PX-200); Triphenylphosphine oxidation thing; テ ホ chemistry system complex metal hydroxide エ コ one マ グ Z-10; ANTIMONY TRIOXIDE SB 203 99.8 PCT; The bisphenol A-type brominated epoxy resin of epoxy equivalent (weight) 375,80 ℃ of softening temperatures, bromine content 48 weight % (the system trade(brand)name ESB-400T of Sumitomo Chemical Company Ltd).
(inorganic filler)
Employed inorganic filler is median size 6.7 μ m, specific surface area 3.0m 2The spheroidal fused silica 1 of/g; Median size 8.8 μ m, specific surface area 4.6m 2The spheroidal fused silica 2 of/g; Median size 12.5 μ m, specific surface area 3.2m 2The spheroidal fused silica 3 of/g; Median size 6.0 μ m, specific surface area 2.7m 2The spheroidal fused silica 4 of/g; Median size 17 μ m, specific surface area 3.8m 2The spheroidal fused silica 5 of/g; Median size 0.8 μ m, specific surface area 6.3m 2The spheroidal fused silica 6 of/g.
(other additive)
Employed other additive is carnauba wax (Network ラ リ ア Application ト corporate system) and carbon black (the system trade(brand)name MA-100 of Mitsubishi chemical Co., Ltd).
The mixing of table 4 epoxy resin molding material for encapsulation forms 1
Mixing element Embodiment epoxy resin molding material for encapsulation B
1 2 3 4 5 6 7 8 9 10
Biphenyl type epoxy resin - - - - - - - - - 85
Bisphenol f type epoxy resin 10 10 10 10 10 10 10 10 10 -
Stilbene type Resins, epoxy - - - - - - - - - -
Sulfur atom-containing Resins, epoxy - - - - - - - - - -
Tris-phenol type Resins, epoxy 1 75 75 75 75 75 75 - 75 75 -
Tris-phenol type Resins, epoxy 2 - - - - - - 75 - - -
O-cresol phenolic epoxy varnish - - - - - - - - - -
Brominated epoxy resin 15 15 15 15 15 15 15 15 15 15
Phenol-aralkyl resin - - - - - - - - - -
Biphenyl type resol - - - - - - - - - -
Tris-phenol type resol 1 55 55 55 55 55 55 55 - 55 49
Tris-phenol type resol 2 - - - - - - - 55 - -
The phenol novolac resin - - - - - - - - - -
Curing catalyst 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 3.0
The aromatic condensation phosphoric acid ester - - - - - - - - - -
Triphenylphosphine oxidation thing - - - - - - - - - -
Complex metal hydroxide - - - - - - - - - -
ANTIMONY TRIOXIDE SB 203 99.8 PCT 15 15 15 15 15 15 15 15 15 15
Anilino silane 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 - 4.5
Epoxy silane - - - - - - - - 4.5 -
Spheroidal fused silica 1 868 - - - - - - - - -
Spheroidal fused silica 2 - 868 - - - - 868 868 868 933
Spheroidal fused silica 3 - - 868 - - - - - - -
Spheroidal fused silica 4 - - - 868 - - - - - -
Spheroidal fused silica 5 - - - - 868 - - - - -
Spheroidal fused silica 6 - - - - - 868 - - - -
Carnauba wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Carbon black 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0
Inorganic filler amount (weight %) 83 83 83 83 83 83 83 83 83 84
The mixing of table 5 epoxy resin molding material for encapsulation forms 2
Mixing element Embodiment epoxy resin molding material for encapsulation B
11 12 13 14 15 16 17 18 19
Biphenyl type epoxy resin - - - 85 - - - - -
Bisphenol f type epoxy resin 85 - - - - 100 10 10 10
Stilbene type Resins, epoxy - 85 - - - - - - -
Sulfur atom-containing Resins, epoxy - - 85 - - - - - -
Tris-phenol type Resins, epoxy 1 - - - - - - 90 90 90
Tris-phenol type Resins, epoxy 2 - - - - - - - - -
O-cresol phenolic epoxy varnish - - - - 85 - - - -
Brominated epoxy resin 15 15 15 15 15 - - - -
Phenol-aralkyl resin - - - 83 - - - - -
Biphenyl type resol - - - - - 107 - - -
Tris-phenol type resol 1 51 46 40 - - - 60 60 60
Tris-phenol type resol 2 - - - - - - - - -
The phenol novolac resin - - - - 50 - - - -
Curing catalyst 3.5 3.5 3.5 3.5 2.0 3.5 3.0 3.0 3.0
The aromatic condensation phosphoric acid ester - - - - - - 35 - -
Triphenylphosphine oxidation thing - - - - - - - 35 -
Complex metal hydroxide - - - - - - - - 150
ANTIMONY TRIOXIDE SB 203 99.8 PCT 15 15 15 15 15 15 15 15 15
Anilino silane 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5
Epoxy silane - - - - - - - - -
Spheroidal fused silica 1 - - - - - - - - -
Spheroidal fused silica 2 951 922 890 1121 613 1756 1076 1076 757
Spheroidal fused silica 3 - - - - - - - - -
Spheroidal fused silica 4 - - - - - - - - -
Spheroidal fused silica 5 - - - - - - - - -
Spheroidal fused silica 6 - - - - - - - - -
Carnauba wax 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Carbon black 3.5 3.5 3.5 3.5 3.5 3.5 3.0 3.0 3.0
Inorganic filler amount (weight %) 84 84 84 84 78 88 83 83 83
Estimate the characteristic of gained epoxy resin molding material for encapsulation B1～B19 with test subject shown in table 3, the table 4 (helicoidal flow, hardness, flame retardant resistance when plectane is mobile, hot).The result is shown in table 6, table 7.
The characteristic 1 of table 6 epoxy resin molding material for encapsulation
Characteristic Embodiment epoxy resin molding material for encapsulation B
1 2 3 4 5 6 7 8 9 10
Helicoidal flow (cm) 171 175 174 100 175 68 113 107 166 232
Moving plate current moving (mm) 121 130 127 76 127 56 88 81 102 125
Hardness when hot (Shore D) 77 77 78 77 78 76 82 83 76 82
The UL-94 test V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
The characteristic 2 of table 7 epoxy resin molding material for encapsulation
Characteristic Embodiment epoxy resin molding material for encapsulation B
11 12 13 14 15 16 17 18 19
Helicoidal flow (cm) 237 229 225 206 145 118 180 178 117
Plectane flow (mm) 127 115 113 110 100 95 133 132 92
Hardness when hot (Shore D) 80 83 79 73 83 75 70 71 78
The UL-94 test V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0
[making semiconductor device B1 (flip-chip BGA)]
Then, use epoxy resin molding material for encapsulation B1～B19, make the semiconductor device of Embodiment B 1～B16 and comparative example B1～B3.In addition, be, after being shaped with 165 ℃ of die temperatures, compacting pressure 9.8MPa, vacuum tightness 530Pa, the condition of 90 seconds set times, with 165 ℃ of after fixing 5 hours with the method for epoxy resin molding material for encapsulation sealing.
Embodiment B 1～B16 (table 8; table 9): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 40mm * horizontal 40mm * thick 1.3mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 9mm * horizontal 8mm * thick 0.4mm (area 72mm 2), the semiconductor element of projection footpath 145 μ m, bump pitch 200 μ m flows to handle again and installs.Bump height after the installation is 100 μ m.Then, use epoxy resin molding material for encapsulation B1～B3 and B7～B19, the size of mounting semiconductor element face with vertical 12mm * horizontal 12mm * thick 0.7mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of Embodiment B 1～B16.
Comparative example B1～B3 (table 12): except using epoxy resin molding material for encapsulation 4～6, other and Embodiment B 1～B16 similarly carry out, and make the semiconductor device of comparative example B1～B3.
[making semiconductor device B2 (flip-chip BGA)]
Then, use epoxy resin molding material for encapsulation B1～B19, make the semiconductor device of Embodiment B 17～B32 and comparative example B4～B6.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 165 ℃ of die temperatures, compacting pressure 9.8MPa, vacuum tightness 530Pa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment 17～32 (tables 10; table 11): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 40mm * horizontal 40mm * thick 1.3mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 6mm * horizontal 5mm * thick 0.4mm (area 30mm 2), the semiconductor element of projection footpath 175 μ m, bump pitch 400 μ m flows to handle again and installs.Bump height after the installation is 120 μ m.Then use epoxy resin molding material for encapsulation B1～B3 and B7～B19, the size of mounting semiconductor element face with vertical 12mm * horizontal 12mm * thick 1.2mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of Embodiment B 17～B32.
Comparative example B4～B6 (table 13): except using epoxy resin molding material for encapsulation 4～6, other and Embodiment B 17～B32 similarly carry out, and make the semiconductor device of comparative example B4～B6.
[making semiconductor device B3 (flip-chip BGA)]
Use epoxy resin molding material for encapsulation B1～B19, make the semiconductor device of comparative example B7～B25.In addition, be, utilize and shift forming mill, after vacuum tightness 530Pa, the condition of 90 seconds set times are shaped, with 180 ℃ of after fixing 5 hours with 165 ℃ of die temperatures, compacting pressure 9.8MPa with the method for epoxy resin molding material for encapsulation sealing.
Comparative example 7～25 (tables 14; table 15): at insulation base material (woven fiber glass-semiconductor device laminated board; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 40mm * horizontal 40mm * thick 1.3mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 5mm * horizontal 4mm * thick 0.4mm (area 20mm 2), the semiconductor element of projection footpath 250 μ m, bump pitch 700 μ m flows to handle again and installs.Bump height after the installation is 180 μ m.Then use epoxy resin molding material for encapsulation 1～19, the size of mounting semiconductor element face with vertical 12mm * horizontal 12mm * thick 2.5mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of comparative example B7～B25.
Carry out the space growing amount of the semiconductor device of gained Embodiment B 1～B32 and comparative example B1～B25 and test to estimate, evaluation result is shown in table 8～table 15.
The evaluation result 1 of table 8 semiconductor device (semiconductor device B1)
Characteristic Embodiment B
1 2 3 4 5 6 7 8 9
Epoxy resin molding material for encapsulation B 1 2 3 7 8 9 10 11 12
The space growing amount 2/20 0/20 2/20 3/20 4/20 3/20 0/20 0/20 1/20
The evaluation result 2 of table 9 semiconductor device (semiconductor device B1)
Characteristic Embodiment B
10 11 12 13 14 15 16
Epoxy resin molding material for encapsulation B 13 14 15 16 17 18 19
The space growing amount 0/20 0/20 2/20 2/20 0/20 0/20 3/20
The evaluation result 3 of table 10 semiconductor device (semiconductor device B2)
Characteristic Embodiment B
17 18 19 20 21 22 23 24 25
Epoxy resin molding material for encapsulation B 1 2 3 7 8 9 10 11 12
The space growing amount 1/20 0/20 1/20 3/20 3/20 2/20 0/20 0/20 0/20
The evaluation result 4 of table 11 semiconductor device (semiconductor device B2)
Characteristic Embodiment B
26 27 28 29 30 31 32
Epoxy resin molding material for encapsulation B 13 14 15 16 17 18 19
The space growing amount 0/20 0/20 1/20 1/20 0/20 0/20 2/20
The evaluation result 5 of table 12 semiconductor device (semiconductor device B1)
Characteristic Comparative example B
1 2 3
Epoxy resin molding material for encapsulation B 4 5 6
The space growing amount 11/20 Do not fill 18/20
The evaluation result 6 of table 13 semiconductor device (semiconductor device B2)
Characteristic Comparative example B
4 5 6
Epoxy resin molding material for encapsulation B 4 5 6
The space growing amount 8/20 Do not fill 10/20
The evaluation result 7 of table 14 semiconductor device (semiconductor device B3)
Characteristic Comparative example B
7 8 9 10 11 12 13 14 15 16
Epoxy resin molding material for encapsulation B 1 2 3 4 5 6 7 8 9 10
The space growing amount 0/20 0/20 0/20 2/20 3/20 2/20 0/20 0/20 0/20 0/20
The evaluation result 8 of table 15 semiconductor device (semiconductor device B3)
Characteristic Comparative example B
17 18 19 20 21 22 23 24 25
Epoxy resin molding material for encapsulation B 11 12 13 14 15 16 17 18 19
The space growing amount 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20 0/20
[evaluation reliability]
Embodiment B 33～B48 (table 16, table 17), comparative example B26～B28 (table 17):
Then, use epoxy resin molding material for encapsulation B1～B19 to estimate various reliabilities (anti-fluidity again, wet fastness, high-temperature standing properties).Evaluation result is shown in table 16, table 17.In addition, use semiconductor device 2 during evaluation by condition making same as described above.
Table 16 reliability 1 (semiconductor device B2)
Characteristic Embodiment B
33 34 35 36 37 38 39 40 41 42
Epoxy resin molding material for encapsulation B 1 2 3 7 8 9 10 11 12 13
The anti-72h of fluidity again 96h 168h 336h 0/5 0/5 1/5 3/5 0/5 0/5 2/5 3/5 0/5 0/5 1/5 4/5 0/5 1/5 3/5 5/5 0/5 1/5 5/5 5/5 0/5 0/5 0/5 3/5 0/5 0/5 0/5 2/5 0/5 0/5 0/5 2/5 0/5 0/5 0/5 2/5 0/5 0/5 0/5 0/5
Wet fastness 100h 300h 500h 1000h 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10
High-temperature standing properties 100h 300h 500h 1000h 0/10 0/10 2/10 10/10 0/10 0/10 2/10 10/10 0/10 0/10 3/10 10/10 0/10 0/10 1/10 7/10 0/10 0/10 2/10 7/10 0/10 0/10 8/10 10/10 0/10 0/10 5/10 10/10 0/10 0/10 6/10 10/10 0/10 0/10 3/10 8/10 0/10 0/10 5/10 10/10
Table 17 reliability 2 (semiconductor device B2)
Characteristic Embodiment B Comparative example B
43 44 45 46 47 48 26 27 28
Epoxy resin molding material for encapsulation B 14 15 16 17 18 19 4 5 6
The anti-72h of fluidity again 96h 168h 336h 0/5 0/5 0/5 0/5 3/5 5/5 5/5 5/5 0/5 0/5 0/5 0/5 0/5 0/5 0/5 1/5 0/5 0/5 0/5 2/5 0/5 0/5 3/5 5/5 0/5 2/5 4/5 5/5 5/5 5/5 5/5 5/5 0/5 4/5 5/5 5/5
Wet fastness 100h 300h 500h 1000h 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 2/10 5/10 0/10 0/10 0/10 2/10 0/10 0/10 0/10 0/10 3/10 5/10 8/10 10/10 10/10 10/10 10/10 10/10 5/10 8/10 10/10 10/10
High-temperature standing properties 100h 300h 500h 1000h 0/10 2/10 8/10 10/10 0/5 0/5 3/5 5/5 0/10 0/10 0/10 0/10 0/10 0/10 0/10 2/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 0/10 3/10 9/10 0/10 0/10 2/10 10/10 0/10 0/10 2/10 10/10
With not containing median size is that 15 μ m or following and specific surface area are 3.0～6.0m 2The semiconductor device of the comparative example B1～B6 of the epoxy resin molding material for encapsulation B4 of (C) inorganic filler of/g～B6 sealing can produce a large amount of spaces and not fill situation, and fillibility is poor.In addition, the semiconductor device of comparative example B26～B28 can reduce anti-fluidity again and wet fastness.
Comparatively speaking, then all be that to produce the space few with the semiconductor device of the Embodiment B 1～B32 of the epoxy resin molding material for encapsulation B1～B3, the B7 that contain (A)～(C) composition～B19 sealing, fillibility is good.In addition, the semiconductor device of Embodiment B 33～B48 has good anti-fluidity again and wet fastness.
The present invention who does not possess one or more with regard to semiconductor device constitutes with regard to the semiconductor device of comparative example B7～B25 of (a)～(b), the space growing amount is also few, fillibility is good, and no advantage is poor between epoxy resin molding material for encapsulation B1～B3, B7～B19 and the epoxy resin molding material for encapsulation B4～B6.
In addition, the Embodiment B 45～B48 with the epoxy resin molding material for encapsulation B16 that do not contain fire retardant and epoxy resin molding material for encapsulation B17～B19 sealing of containing non-halogenated flame retardant then has the excellent high-temperature standing properties.
The epoxy resin molding material for encapsulation that usefulness is installed because of the flip-chip of embodiment A has as the desired high fillibility of bottom filling, and shaping unfavorable conditions such as space are few, and the anti-reliability of fluidity, wet fastness etc. again is also excellent, so its industrial value is very big.
[evaluation method]
(1) helicoidal flow
Use is measured based on the helicoidal flow of EMMI-1-66 and is used mould, utilizes and shifts forming mill with 180 ℃ of die temperatures, compacting pressure 6.9MPa, and the condition of 90 seconds set times is obtained the distance (cm) that flows after epoxy resin molding material for encapsulation is shaped.
(2) plectane flows
Use has the plectane flow assay flat plate mold of the counterdie of the patrix of 200mm (W) * 200mm (D) * 25mm (H) and 200mm (W) * 200mm (D) * 15mm (H), sample (epoxy resin molding material for encapsulation) 5g that is heated to 180 ℃ accurate weighing is placed the counterdie central part, the patrix that closes and be heated to 180 ℃ after 5 seconds, again with loading 78N, the condition compression molding of 90 seconds set times, with the major diameter (mm) and the minor axis (mm) of vernier callipers mensuration molding, set its mean value (mm) and flow for plectane.
Hardness when (3) hot
After making epoxy resin molding material for encapsulation be configured as the plectane of diameter 50mm * thick 3mm with above-mentioned condition, fixed with Shore D type hardness tester instrumentation at once.
(4) flame retardant resistance
Use the to be shaped mould of thick 1/16 inch test film, with above-mentioned condition epoxy resin molding material for encapsulation is shaped after, with 180 ℃ of after fixing 5 hours, estimate flame retardant resistance with the UL-94 test method(s) again.
(5) space growing amount
Utilize ultrasonic investigation mapping device (Hitachi builds machine corporate system HYE-HOCUS type) fluoroscopic observation semiconductor device, observe to have or not producing diameter 0.1mm or above space, estimate to produce space semiconductor device number/test conductor means number again.
(6) anti-fluidity again
With 85 ℃, the condition of 85%RH with various semiconductor device 3 humidifications after, flow processing again with 260 ℃, 10 seconds condition at regular intervals, and observe leakless is arranged, to estimate with respect to the generation crack package number of test package number (5).
(7) wet fastness
Various semiconductor devices 3 are carried out humidification after the pre-treatment, check the broken string unfavorable condition that causes because of the aluminum wiring corrosion at regular intervals, to estimate with respect to the bad package number of test package number (10).
Here, pre-treating process is, with 85 ℃, 85%RH, 72 hours condition with flat package body humidification after, the vapour phase of carrying out 215 ℃, 90 seconds flows processing again.Thereafter with 0.2MPa, 121 ℃ condition humidification.
(8) high-temperature standing properties
Various semiconductor device 3 keepings in 200 ℃ high temperature groove, are taken out at regular intervals and carried out conduction test, estimate high-temperature standing properties with poor flow package number with respect to test package number (10).
Embodiment C
[making epoxy resin molding material for encapsulation]
Behind following each composition of the mixing of weight part shown in the table 18, carry out roller mill with the temperature 80 of mixing, the condition of the 10 minutes time of mixing and mix, obtain the epoxy resin molding material for encapsulation of Embodiment C 1～C4 and comparative example C1～C4.
(Resins, epoxy)
Resins, epoxy A: epoxy equivalent (weight) 196, the biphenyl type epoxy resin that fusing point is 106 ℃ (the system trade(brand)name エ ピ コ one ト YX-4000H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.)
Resins, epoxy B: epoxy equivalent (weight) 176, the biphenyl type epoxy resin that fusing point is 125 ℃ (the system trade(brand)name エ ピ コ one ト YL-6121H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.)
Resins, epoxy C: 60 ℃ of softening temperatures, the tris-phenol type Resins, epoxy of 150 ℃ melt viscosity 2.4 pools (the system trade(brand)name エ ピ コ one ト E1032H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.)
Resins, epoxy D: epoxy equivalent (weight) 186, the bisphenol f type epoxy resin that fusing point is 75 ℃ (the system trade(brand)name YSLV-80XY of Nippon Steel Chemical Co., Ltd)
(solidifying agent)
Phenol-formaldehyde A: the tris-phenol type resol of melt viscosity that hydroxyl equivalent is 103,150 ℃ 1.3 pools (bright and change into system trade(brand)name MEH-7500-3S)
Bakelite B: 80 ℃ of softening temperatures, the phenol novolac resin of hydroxyl equivalent 106 (bright and change into Co., Ltd. system trade(brand)name H-1)
(curing catalyst)
Curing catalyst A: the affixture of triphenylphosphine and para benzoquinone
Curing catalyst B: the affixture of three (4-aminomethyl phenyl) phosphines and para benzoquinone
(releasing agent)
Release agent A: polyethylene wax (Network ラ リ ア Application ト corporate system)
Releasing agent B: montanate (Network ラ リ ア Application ト corporate system)
(fire retardant)
Fire retardant: epoxy equivalent (weight) 375,80 ℃ of softening temperatures, the bisphenol A-type brominated epoxy resin of bromine content 48 weight % (the system trade(brand)name ESB-400T of Sumitomo Chemical Company Ltd)
Flame retardant: ANTIMONY TRIOXIDE SB 203 99.8 PCT
(tinting material)
Carbon black: carbon black (the system trade(brand)name MA-100 of Mitsubishi chemical Co., Ltd)
(other additive)
Additive A: polyether modified silicon oil (the beautiful organosilicon corporate system in DOW CORNING east)
Additive B: epoxide modified silicone oil (the beautiful organosilicon corporate system in DOW CORNING east)
Addition of C: hydrotalcite
Additive D: bismuth hydroxide
(coupler)
Coupler A: γ-anilino propyl trimethoxy silicane (anilino silane)
Coupler B: methyltrimethoxy silane
Coupler C: γ-Qiu Jibingjisanjiayangjiguiwan
Coupler D: γ-glycidoxypropyltrime,hoxysilane (epoxy silane)
(inorganic filler)
Fused silica: all be the spheroidal fused silica
Table 18
Embodiment C
1 2 3 4 5 6 7 8
Resins, epoxy A 6.06 5.96 5.06
Resins, epoxy B 6.84 6.97 6.26
Resins, epoxy C 5.41 6.74
Resins, epoxy D 2.25 0.90
Resol 3.60 4.42 4.51 4.87 3.54 3.54 4.95 4.07
Curing catalyst 0.32 0.24 0.25 0.18 0.32 0.16 0.16 0.18
Releasing agent 0.32 0.14 0.33 0.15 0.32 0.06 0.15 0.12
Fire retardant 1.07 1.2 1.23 1.35 1.05 0.56 1.35 1.10
Fire-retardant rib agent 1.07 1.2 1.23 1.35 1.05 0.34 1.35 1.10
Carbon black 0.36 0.24 0.25 0.27 0.35 0.15 0.27 0.22
Additive 1.72 1.93 1.97 1.71 1.68 0.06 2.16 1.76
Coupler A *1 0.31 0.35 0.17 0.19 0.47 0.39 0.32
Coupler B *2 0.21 0.24 0.12 0.14 0.32 0.25 0.27 0.22
Coupler C *3 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01
Coupler D *4 0.37
Fused silica A *5 76.46 76.48 80.46
Fused silica B *6 66.52 66.50 65.35
Fused silica C *7 56.92
Fused silica D *8 76.00
Fused silica E *9 8.49 8.47 8.93 8.47
Fused silica F *10 16.65 16.65 16.31 24.37
Median size (μ m) 13.5 8.46 8.46 8.46 13.5 13.5 4.3 15.3
Specific surface area (m 2/g) 3.43 4.62 4.62 4.62 3.43 3.43 3.04 3.40
Coupler fraction of coverage (%) 0.77 0.65 0.34 0.375 1.13 0.86 1.14 0.79
Weight loss on heating rate (quality %) 0.185 0.223 0.142 0.142 0.279 0.254 0.216 0.191
Void area (mm 2) 0.103 0.124 0.115 0.110 0.181 0.146 0.149 0.175
Ellipsis in the formula has the following meaning.
*1: minimum area coverage 307.0m 2/ g;
*2: minimum area coverage 575.6m 2/ g;
*3: minimum area coverage 399.4m 2/ g;
*4: minimum area coverage 315.2m 2/ g;
*5: median size 11.7 μ m, specific surface area 3.2m 2/ g;
*6: median size 10.8 μ m, specific surface area 4.2m 2/ g;
*7: median size 9.3 μ m, specific surface area 1.6m 2/ g;
*8: median size 13.5 μ m, specific surface area 3.2m 2/ g;
*9: median size 0.6 μ m, specific surface area 5.5m 2/ g;
*10: median size 0.5 μ m, specific surface area 6.3m 2/ g.
(1) void area evaluation method
To indulge 9.1mm * horizontal 8.2mm * thick 0.4mm (area 74.6mm 2), the semiconductor element of projection footpath 200 μ m, the projection degree of depth 135 μ m, bump pitch 490 μ m is fixed in the die cavity middle position, again with the molding condition of 7.5 seconds filling times, 90 seconds set times in 165 ℃ of die temperatures, compacting pressure 4.4MPa, vacuum tightness 0.1MPa, the die cavity, be shaped with the epoxy resin molding material for encapsulation vacuum transfer, obtain the molding of vertical 14mm * horizontal 22mm * thick 0.7mm.
Take the space of the projection portion that comes across the gained molding with magnification X,, calculate actual void area SB according to (xx) formula again by void area SP on the photo and photo magnification.
SB＝SP/X (xx)
The epoxy resin molding material for encapsulation that usefulness is installed because of flip-chip of the present invention has as the desired high fillibility of bottom filling, and shaping unfavorable conditions such as space are few, and the anti-reliability of fluidity, wet fastness etc. again is also excellent, so its industrial value is very big.
Embodiment D
To the present invention be described with embodiment below, but scope of the present invention is not limited to these embodiment.In addition, the evaluation of each epoxy resin molding material for encapsulation and semiconductor device is based on the evaluation method that illustrates later and carries out under situation about not indicating especially.
[making epoxy resin molding material for encapsulation]
After adding following each composition with weight part shown in table 19, the table 20, knead with the condition of powder mix feed rate 200Kg/h and to mix, obtain epoxy resin molding material for encapsulation D1～13.
(Resins, epoxy)
Employed Resins, epoxy is, the biphenyl type epoxy resin (the system trade(brand)name エ ピ コ one ト YX-4000H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.) that epoxy equivalent (weight) 196, fusing point are 106 ℃; The bisphenol f type epoxy resin that epoxy equivalent (weight) 186, fusing point are 75 ℃ (the system trade(brand)name YSLV-80XY of Nippon Steel Chemical Co., Ltd); The sulfur atom-containing Resins, epoxy that epoxy equivalent (weight) 245, fusing point are 110 ℃ (the system trade(brand)name YSLV-120TE of Nippon Steel Chemical Co., Ltd); The tris-phenol type Resins, epoxy (polyfunctional group type Resins, epoxy) (the system trade(brand)name エ ピ コ one ト E1032H of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.) of melt viscosity 3.1 pools that o-cresol phenolic epoxy varnish that epoxy equivalent (weight) 195, softening temperature are 65 ℃ (the system trade(brand)name ESCN-190 of Sumitomo Chemical Company Ltd) and epoxy equivalent (weight) 170, softening temperature are 70 ℃, 150 ℃
(solidifying agent)
Employed solidifying agent is, the phenol of 70 ℃ of softening temperatures, hydroxyl equivalent 175-aralkyl resin (Mitsui Chemicals, Inc system trade(brand)name ミ レ Star Network ス XL-225), the phenol novolac resin of 80 ℃ of softening temperatures, hydroxyl equivalent 106 (bright and change into the system trade(brand)name H-1 of Co., Ltd.); The polyfunctional group type resol of 83 ℃ of softening temperatures, hydroxyl equivalent 103 (bright and change into Co., Ltd. system trade(brand)name MEH-7500-3S).
(curing catalyst)
Employed curing catalyst is the affixture (curing catalyst) of triphenylphosphine and para benzoquinone.
(coupler)
Employed coupler is, γ-glycidoxypropyltrime,hoxysilane (epoxy silane) contains the silane coupling agent (γ-anilino propyl trimethoxy silicane (anilino silane)) of secondary amino group.
(fire retardant)
Employed fire retardant is the bisphenol A-type brominated epoxy resin of 80 ℃ of ANTIMONY TRIOXIDE SB 203 99.8 PCT and softening temperatures, bromine content 4.8 weight % (the system trade(brand)name ESB-400T of Sumitomo Chemical Company Ltd).
(silicone resin)
Employed silicone resin is methyl phenyl silicone resin and silicon rubber.
(inorganic filler)
Employed inorganic filler is the spheroidal fused silica of median size 28 μ m, median size 20 μ m, median size 8 μ m, median size 0.5 μ m.
(other additive)
Employed other additive is higher fatty acid wax and carbon black.
Table 19
Project Epoxy resin molding material D
1 2 3 4 5 6 7
O-cresol phenolic epoxy varnish 7.4 6.7 4.6
Biphenyl type epoxy resin 6.9 7 1.4
Sulfur atom-containing Resins, epoxy
Polyfunctional group type Resins, epoxy 4 5.5
Bisphenol f type epoxy resin 3.6 2.3
The bisphenol A-type brominated epoxy resin 1.3 1.4 1.2 1.2 1.3 1.2 0.7
The phenol novolac resin 1.8
Phenol aralkyl resin 6.2 5.7 2.2
Polyfunctional group type resol 4.8 4.9 4.5 4.6
The affixture of triphenylphosphine and para benzoquinone 0.2 0.2 0.2 0.2 0.2 0.2 0.1
Epoxy silane 0.4 0.4
Anilino silane 0.4 0.2 0.4 0.2 0.3
Higher fatty acid wax 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Carbon black 0.3 0.3 0.2 0.2 0.2 0.2 0.1
ANTIMONY TRIOXIDE SB 203 99.8 PCT 1.3 1.4 1.2 1.2 0.5 0.5 0.4
Silicon rubber
Methyl phenyl silicone resin 1.3 1.4 1.2 1.2
The spheroidal fused silica of median size 28 μ m
The spheroidal fused silica of median size 20 μ m 75.3 76.5
The spheroidal fused silica of median size 8 μ m 66.1 65.9 67.3 67.3 79.4
The spheroidal fused silica of median size 0.5 μ m 16.6 16.4 16.8 16.8 8.4 8.5 8.9
Add up to 100 100 100 100 100 100 100
Table 20
Project Epoxy resin molding material D
8 9 10 11 12 13
O-cresol phenolic epoxy varnish
Biphenyl type epoxy resin 6.7 5.1 6.3 5.2
Sulfur atom-containing Resins, epoxy 5.1
Polyfunctional group type Resins, epoxy 7.6
Bisphenol f type epoxy resin
The bisphenol A-type brominated epoxy resin 1.2 0.6 0.9 1.3 1.1 0.9
The phenol novolac resin
Phenol aralkyl resin 6.6 4.9 2.9
Polyfunctional group type resol 4.9 1.9 1.5
The affixture of triphenylphosphine and para benzoquinone 0.3 0.2 0.2 0.1 0.2 0.2
Epoxy silane 0.4
Anilino silane 0.3 0.3 0.4 0.3 0.3
Higher fatty acid wax 0.1 0.1 0.1 0.1 0.1 0.1
Carbon black 0.1 0.1 0.2 0.3 0.2 0.2
ANTIMONY TRIOXIDE SB 203 99.8 PCT 0.5 0.3 0.4 1.3 1.1 0.9
Silicon rubber 3.3 2.7
Methyl phenyl silicone resin 1.3
The spheroidal fused silica of median size 28 μ m 50.5 61.9 67.5
The spheroidal fused silica of median size 20 μ m 74.4 77.0 79.3
The spheroidal fused silica of median size 8 μ m 25.2 17.7 17.9
The spheroidal fused silica of median size 0.5 μ m 8.4 8.9 4.5 8.3 8.5 8.7
Add up to 100 100.1 100 100 100 100
Estimate the characteristic of gained epoxy resin molding material for encapsulation D1～D13 with test subject shown in the table (helicoidal flow, hardness, bending elastic modulus, shaping shrinkage rate, second-order transition temperature when plectane is mobile, hot).The result is shown in table 21, table 22.
Table 21
Project Unit Epoxy resin molding material D
1 2 3 4 5 6 7
Helicoidal flow inch 90 73 92 93 53 52 45
Plectane flows mm 125 107 117 114 79 92 88
Hardness when Shore D is hot - 77 85 86 80 82 81 89
Bending elastic modulus GPa 17.8 18.3 18.5 18.5 21.6 22.3 23.8
Shaping shrinkage rate ％ 0.189 0.122 0.13 0.142 0.344 0.339 0.165
Second-order transition temperature ℃ 163 184 165 161 140 142 146
Table 22
Project Unit Epoxy resin molding material D
8 9 10 11 12 13
Helicoidal flow inch 58 54 47 77 75 57
Plectane flows mm 90 100 93 117 95 86
Hardness when Shore D is hot - 84 81 80 84 75 82
Bending elastic modulus GPa 20.8 23.4 25.6 17.1 19.7 22.2
Shaping shrinkage rate ％ 0.362 0.169 0.164 0.177 0.181 0.145
Second-order transition temperature ℃ 118 138 132 185 163 159
[making semiconductor device D1 (flip-chip BGA)]
Then, use epoxy resin molding material for encapsulation D1～D13 to make the semiconductor device of embodiment D1～D10 and Comparative Example D 1～D3.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment D1～D10 (table 23; 24): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into system trade(brand)name E-679) go up form fine interconnection pattern after; insulation protection resist (sun イ Application キ system trade(brand)name PSR4000AUS5) is coated on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 40mm * horizontal 80mm * thick 0.6mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 9mm * horizontal 8mm * thick 0.4mm (area 72mm 2), projection footpath 145 μ m, bump pitch 200 μ m, the semiconductor element that number of lugs is 160 flows to handle again to be installed.Bump height after the installation is 110 μ m.Then, use epoxy resin molding material for encapsulation D1～D4, D7 and D9～D13, the size of mounting semiconductor element face with vertical 30mm * horizontal 70mm * thick 0.8mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of embodiment D1～D10.
Comparative Example D 1～D3 (table 25): use epoxy resin molding material for encapsulation D5, D6 and D8, similarly carry out, make the semiconductor device D of comparative example 1～3 with embodiment D1～D10.
Table 23
Project Embodiment D
1 2 3 4 5
Epoxy resin molding material D 1 2 3 4 7
Mounting semiconductor element substrate profile Vertical 40mm * horizontal 80mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 30mm * horizontal 70mm * thick 0.8mm
Table 24
Project Embodiment D
6 7 8 9 10
Epoxy resin molding material D 9 10 11 12 13
Mounting semiconductor element substrate profile Vertical 40mm * horizontal 80mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 30mm * horizontal 70mm * thick 0.8mm
Table 25
Project Comparative Example D
1 2 3
Epoxy resin molding material D 5 6 8
Mounting semiconductor element substrate profile Vertical 40mm * horizontal 80mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 30mm * horizontal 70mm * thick 0.8mm
[making semiconductor device D2 (flip-chip BGA)]
Use epoxy resin molding material for encapsulation D1～D13 to make embodiment D11～D20 and Comparative Example D 4～D6 semiconductor device.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment D11～D20 (table 26; table 27): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 50mm * horizontal 100mm * thick 0.6mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 9mm * horizontal 8mm * thick 0.4mm (area 72mm 2), projection footpath 145 μ m, bump pitch 200 μ m, the semiconductor element that number of lugs is 160 flows to handle again to be installed.Bump height after the installation is 110 μ m.Then use epoxy resin molding material for encapsulation D1～D4, D7 and D9～D13, the size of mounting semiconductor element face with vertical 40mm * horizontal 90mm * thick 0.8mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of embodiment D11～D20.
Comparative Example D 4～D6 (table 28): use epoxy resin molding material for encapsulation D5, D6 and D8, similarly carry out, make the semiconductor device of Comparative Example D 4～D6 with embodiment D11～D20.
Table 26
Project Embodiment D
11 12 13 14 15
Epoxy resin molding material D 1 2 3 4 7
Mounting semiconductor element substrate profile Vertical 50mm * horizontal 100mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 40mm * horizontal 90mm * thick 0.8mm
Table 27
Project Embodiment D
16 17 18 19 20
Epoxy resin molding material D 9 10 11 12 13
Mounting semiconductor element substrate profile Vertical 50mm * horizontal 100mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 40mm * horizontal 90mm * thick 0.8mm
Table 28
Project Comparative Example D
4 5 6
Epoxy resin molding material D 5 6 8
Mounting semiconductor element substrate profile Vertical 50mm * horizontal 100mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 40mm * horizontal 90mm * thick 0.8mm
[making semiconductor device 3 (flip-chip BGA)]
Use epoxy resin molding material for encapsulation D1～D13 to make the semiconductor device of embodiment D21～D30 and Comparative Example D 7～D9.In addition, be with the method for epoxy resin molding material for encapsulation sealing, utilize shift forming mill and be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times after, with 180 ℃ of after fixing 5 hours.
Embodiment D21～D30 (table 29; 30): at insulation base material (woven fiber glass-Resins, epoxy lamination plate; Hitachi changes into manufacturing; trade(brand)name E-679) after the last formation fine interconnection pattern; (sun イ Application キ makes with the insulation protection resist; trade(brand)name PSR4000AUS5) coats on the face except the external connection terminals of the gold-plated terminal of mounting semiconductor element side and reverse side; be that the mounting semiconductor element of indulging 60mm * horizontal 120mm * thick 0.6mm was used substrate dry 2 hours with 120 ℃ with the gained profile again, flow technology again with 260 ℃ according to IR thereafter; 10 seconds condition is to vertical 9mm * horizontal 8mm * thick 0.4mm (area 72mm 2), the semiconductor element of 160 of projection footpath 145 μ m, bump pitch 200 μ m, number of lugs flows to handle again and installs.Bump height after the installation is 110 μ m.Then use epoxy resin molding material for encapsulation 1～4,7 and 9～13, the size of mounting semiconductor element face with vertical 50mm * horizontal 110mm * thick 0.8mm is shaped with above-mentioned condition vacuum transfer, obtain the flip-chip BGA device of embodiment D21～D30.
Comparative Example D 7～D9 (table 31): use epoxy resin molding material for encapsulation D5, D6 and D8, similarly carry out, make the semiconductor device of Comparative Example D 7～D9 with embodiment D21～D30.
Table 29
Project Embodiment D
21 22 23 24 25
Epoxy resin molding material D 1 2 3 4 7
Mounting semiconductor element substrate profile Vertical 60mm * horizontal 120mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 50mm * horizontal 110mm * thick 0.8mm
Table 30
Project Embodiment D
26 27 28 29 30
Epoxy resin molding material D 9 10 11 12 13
Mounting semiconductor element substrate profile Vertical 60mm * horizontal 120mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 2001μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 50mm * horizontal 110mm * thick 0.8mm
Table 31
Project Comparative Example D
7 8 9
Epoxy resin molding material D 5 6 8
Mounting semiconductor element substrate profile Vertical 60mm * horizontal 120mm * thick 0.6mm
The semiconductor element profile Vertical 9mm * horizontal 8mm * thick 0.4mm
Semiconductor element projection footpath 145μm
The semiconductor element bump pitch 200μm
The semiconductor element number of lugs 160
The semiconductor element encapsulation profile Vertical 50mm * horizontal 110mm * thick 0.8mm
The substrate warpage amount of the semiconductor device by gained embodiment D1～D30 and Comparative Example D 1～D9 is tested and is estimated, relatively second-order transition temperature, bending elastic modulus, shaping shrinkage rate, the fillibility when semiconductor element is shaped.Evaluation result is shown in table 32～35.
Table 32
Project Unit Embodiment D
1 2 3 4 5 6 7 8 9 10
Epoxy resin molding material D - 1 2 3 4 7 9 10 11 12 13
Second-order transition temperature ℃ 163 184 165 161 146 138 132 185 163 159
Bending elastic modulus GPa 17.8 18.3 18.5 18.5 23.8 23.4 25.6 17.1 19.7 22.2
Shaping shrinkage rate ％ 0.189 0.122 0.130 0.142 0.165 0.169 0.164 0.177 0.181 0.145
Substrate warpage mm 0.9 1.1 1.1 1.0 4.5 3.8 4.2 1.1 2.4 1.8
The shaping filling ratio Area % 100 100 100 100 66 100 71 100 100 75
Table 33
Project Unit Embodiment D
11 12 13 14 15 16 17 18 19 20
Epoxy resin molding material D - 1 2 3 4 7 9 10 11 12 13
Second-order transition temperature ℃ 163 184 165 161 146 138 132 185 163 159
Bending elastic modulus GPa 17.8 18.3 18.5 18.5 23.8 23.4 25.6 17.1 19.7 22.2
Shaping shrinkage rate ％ 0.189 0.122 0.130 0.142 0.165 0.169 0.164 0.177 0.181 0.145
Substrate warpage mm 1.5 1.6 1.4 1.5 4.9 4.0 4.8 1.7 2.8 2.2
The shaping filling ratio Area % 100 100 100 100 54 90 71 98 94 71
Table 34
Project Unit Embodiment D
21 22 23 24 25 26 27 28 29 30
Epoxy resin molding material D - 1 2 3 4 7 9 10 11 12 13
Second-order transition temperature ℃ 163 184 165 161 146 138 132 185 163 159
Bending elastic modulus GPa 17.8 18.3 18.5 18.5 23.8 23.4 25.6 17.1 19.7 22.2
Shaping shrinkage rate ％ 0.189 0.122 0.130 0.142 0.165 0.169 0.164 0.177 0.181 0.145
Substrate warpage mm 1.8 2.0 1.9 1.9 5.0 4.3 5.0 2.0 3.1 2.5
The shaping filling ratio Area % 100 100 100 100 66 77 52 88 84 58
Table 35
Project Unit Comparative Example D
1 2 3 4 5 6 7 8 9
Epoxy resin molding material D - 5 6 8 5 6 8 5 6 8
Second-order transition temperature ℃ 140 142 118 140 142 118 140 142 118
Bending elastic modulus GPa 21.6 22.3 20.8 21.6 22.3 20.8 21.6 22.3 20.8
Shaping shrinkage rate ％ 0.344 0.339 0.362 0.344 0.339 0.362 0.344 0.339 0.362
Substrate warpage mm 10.5 12.8 8.8 13.6 15.1 10.2 15.5 18.0 12.7
Army shape filling ratio Area % 62 84 95 52 77 84 41 63 71
With do not meet second-order transition temperature based on TMA method (differential expansion fashion) be 150 ℃ or above, based on the bending elastic modulus of JIS K6911 be 19GPa or following, based on the shaping shrinkage rate of JIS K6911 be 0.2% or the Resins, epoxy of following any condition be shaped as the comparative examples 1～9 of material 5,6 and 8 sealings, the substrate warpage degree is all big, and the fillibility during shaping is also bad.
Comparatively speaking, little with 1～30 substrate warpage degree of embodiment of the epoxy resin molding material 1～4,7 that meets at least one condition in the above-mentioned condition and 9～10 sealings, and the fillibility when being shaped is also good.In addition, with the embodiment of the epoxy resin molding material 1～4 that meets full terms and 11 sealings then substrate warpage smaller or equal to 2.0mm, good especially, and the fillibility when being shaped also is not produce the space and good especially.
[evaluation method]
(1) helicoidal flow
Use is measured based on the helicoidal flow of EMMI-1-66 and is used mould, utilizes the transfer forming mill with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times epoxy resin molding material for encapsulation to be shaped, and obtains the distance (inch) that flows.
(2) plectane flows
Use has the plectane flow assay flat plate mold of the counterdie of the patrix of 200mm (w) * 200mm (D) * 25mm (H) and 200mm (w) * 200mm (D) * 15mm (H), sample (epoxy resin molding material for encapsulation) 5g of accurate weighing is placed the counterdie central part that is heated to 180 ℃, the patrix that closes and be heated to 180 ℃ after 5 seconds, with loading 78N, the condition compression molding of 90 seconds set times, major diameter (mm) and minor axis (mm) with vernier callipers mensuration molding flow its mean value (mm) as plectane.
Hardness when (3) hot
After with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times epoxy resin molding material for encapsulation being configured as the plectane of diameter 50mm * thick 3mm, fixed with Shore D type hardness tester instrumentation at once.
(4) bending elastic modulus
Use is based on the pliability test sheet molding die of JIS K6911, after utilizing the transfer forming mill to be shaped with 180 ℃ of die temperatures, compacting pressure 6.9GPa, the condition of 90 seconds set times, with 180 ℃ of after fixing 5 hours, the bend test method of being put down in writing according to JIS K6911 was measured bending elastic modulus again.
(5) shaping shrinkage rate
Use is measured according to the shaping shrinkage rate of JIS K6911 and is used mould, after utilizing the transfer forming mill to be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times, with 180 ℃ of after fixing 5 hours, the shaping shrinkage rate test method determination shaping shrinkage rate of being put down in writing according to JIS K6911 again.
(6) second-order transition temperature
Use can be made the mould of the test film of 20mm * 4mm * 4mm, after utilizing the transfer forming mill to be shaped with 180 ℃ of die temperatures, compacting pressure 6.9MPa, the condition of 90 seconds set times, with 180 ℃ of after fixing 5 hours, utilize (strain) マ Star Network サ イ エ Application ス system TMA device (TSC1000), measure second-order transition temperature and thermal expansivity according to TMA method (differential expansion fashion).
(7) substrate warpage amount
Flip-chip BGA substrate after placing ester moulding on level and the level and smooth face with an end of 50g counterweight stationary substrate length direction, utilizes carpenter's square to read size that the other end floats from even surface to 1/10mm.
Filling ratio when (8) being shaped
Utilize ultrasonic investigation mapping device (Hitachi builds machine corporate system HYE-HOCUS type) fluoroscopic observation semiconductor device, the filling area ratio of calculating with respect to sealing surface area (area %) is estimated.
Utilize possibility on the industry
Flip-chip of the present invention is installed the epoxy resin molding material for encapsulation of usefulness, have as the desired high fillibility of bottom filling, and shaping unfavorable condition such as space is few, so its industrial value is very big.In addition, flip-chip of the present invention is installed the epoxy resin molding material for encapsulation of usefulness, has as the desired low warpage properties of bottom filling, demonstrate good flow characteristics, so its industrial value is very big.
As mentioned above, under the condition that does not exceed aim of the present invention and scope, those skilled in the art can carry out many changes and correction to preferred implementation of the present invention.

Claims (27)

1. epoxy resin molding material for encapsulation, contain (A) Resins, epoxy, (B) solidifying agent and (C) inorganic filler, it is characterized by, described epoxy resin molding material for encapsulation meets at least one condition in the following condition: based on the second-order transition temperature of TMA method be 150 ℃ or more than; Bending elastic modulus based on JIS-K6911 is 19GPa or following; Based on the shaping shrinkage rate of JIS-K6911 be 0.2% or below.
2. epoxy resin molding material for encapsulation according to claim 1 is characterized by, (A) Resins, epoxy 150 ℃ melt viscosity be 2 pools or below.
3. epoxy resin molding material for encapsulation according to claim 1, it is characterized by, (A) Resins, epoxy contains in biphenyl type epoxy resin, bisphenol f type epoxy resin, stilbene type Resins, epoxy, sulfur atom-containing Resins, epoxy, phenolic resin varnish type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene type Resins, epoxy and the tritane type Resins, epoxy at least a kind.
4. epoxy resin molding material for encapsulation according to claim 1 is characterized by, (B) solidifying agent 150 ℃ melt viscosity be 2 pools or below.
5. epoxy resin molding material for encapsulation according to claim 1, it is characterized by, (B) solidifying agent contains at least a in biphenyl type resol, aralkyl-type phenol resin, dicyclopentadiene-type resol, tritane type resol and the phenolic varnish type resol.
6. epoxy resin molding material for encapsulation according to claim 1 is characterized by, and further contains (F) curing catalyst.
7. epoxy resin molding material for encapsulation according to claim 1 is characterized by, and further contains (D) coupler.
8. epoxy resin molding material for encapsulation according to claim 7 is characterized by, and (D) coupler has the silane coupling agent of secondary amino group for (D2).
9. epoxy resin molding material for encapsulation according to claim 8 is characterized by, and the silane coupling agent that (D2) has secondary amino group contains the compound shown in the following general formula (I),
Figure A2007101047000003C1
In the formula, R 1Be selected from the alkyl of hydrogen atom, carbonatoms 1～6, the alkoxyl group of carbonatoms 1～2; R 2Be selected from the alkyl and the phenyl of carbonatoms 1～6; R 3Expression methyl or ethyl; N represents 1～6 integer; M represents 1～3 integer.
10. epoxy resin molding material for encapsulation according to claim 1 is characterized by, and further contains (E) phosphorus compound.
11. epoxy resin molding material for encapsulation according to claim 10 is characterized by, (E) phosphorus compound contains phosphoric acid ester.
12. epoxy resin molding material for encapsulation according to claim 11 is characterized by, phosphoric acid ester contains the compound shown in the following general formula (II),
Figure A2007101047000003C2
In the formula, 8 R represent the alkyl of carbonatoms 1～4, can be all identical or different; Ar represents aromatic ring.
13. epoxy resin molding material for encapsulation according to claim 10 is characterized by, (E) phosphorus compound contains phosphine oxide.
14. epoxy resin molding material for encapsulation according to claim 13 is characterized by, phosphine oxide contains the compound shown in the following general formula (III),
Figure A2007101047000003C3
In the formula, R 1, R 2And R 3The replacement of expression carbonatoms 1～10 or alkyl, aryl, aralkyl and the hydrogen atom of non-replacement can be all identical or different, all are the situation of hydrogen atom but get rid of.
15. epoxy resin molding material for encapsulation according to claim 7 is characterized by, (D) the filler fraction of coverage of coupler is 0.3～1.0.
16. epoxy resin molding material for encapsulation according to claim 7 is characterized by, the weight loss on heating rate after the 200 ℃/lhr heating is 0.25 weight % or following.
17. epoxy resin molding material for encapsulation according to claim 15 is characterized by, the weight loss on heating rate after the 200 ℃/lhr heating is 0.25 weight % or following.
18. epoxy resin molding material for encapsulation according to claim 1 is characterized by, and is used for possessing following (c1), (d1) and one or more the semiconductor device that (g1) constitutes,
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following;
(g1) the sealing material shaping area of once-forming mode is 3000mm 2Or more than.
19. epoxy resin molding material for encapsulation according to claim 1 is characterized by, and is used for possessing following (c2), (d2) and one or more the semiconductor device that (g2) constitutes,
(c2) area of semi-conductor chip is 50mm 2Or more than;
(d2) total thickness of sealing material is 1.5mm or following;
(g2) the sealing material shaping area of once-forming mode is 5000mm 2Or more than.
20. according to claim 18 or 19 described epoxy resin molding material for encapsulation, it is characterized by, the warpage of semiconductor device is 5.0mm or following.
21. according to claim 18 or 19 described epoxy resin molding material for encapsulation, it is characterized by, the warpage of semiconductor device is 2.0mm or following.
22. epoxy resin molding material for encapsulation according to claim 1, wherein, (C) the inorganic filler containing ratio is 70～90wt% with respect to epoxy resin molding material.
23. a semiconductor device is characterized by, with the described epoxy resin molding material for encapsulation sealing of claim 1.
24. semiconductor device according to claim 23 is characterized by, and possesses in following (a1)～(f1) formation one or more,
(a1) bump height of flip-chip is 150 μ m or following;
(b1) bump pitch of flip-chip is 500 μ m or following;
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following;
(e1) number of lugs of flip-chip be 100 or more than;
Ventage thickness when (f1) being shaped is 40 μ m or following.
25. semiconductor device according to claim 23 is characterized by, and possesses in following (a2)～(f2) formation one or more,
(a2) bump height of flip-chip is 100 μ m or following;
(b2) bump pitch of flip-chip is 400 μ m or following;
(c2) area of semi-conductor chip is 50mm 2Or more than;
(d2) total thickness of sealing material is 1.5mm or following;
(e2) number of lugs of flip-chip be 150 or more than;
Ventage thickness when (f2) being shaped is 30 μ m or following.
26. semiconductor device according to claim 23 is characterized by, and possesses following (c1), (d1) and (g1) one or more in constituting,
(c1) area of semi-conductor chip is 25mm 2Or more than;
(d1) total thickness of sealing material is 2mm or following;
(g1) the sealing material shaping area of once-forming mode is 3000mm 2Or more than.
27. semiconductor device according to claim 23 is characterized by, and possesses following (c2), (d2) and (g2) one or more in constituting,
(c2) area of semi-conductor chip is 50mm 2Or more than;
(d2) total thickness of sealing material is 1.5mm or following;
(g2) the sealing material shaping area of once-forming mode is 5000mm 2Or more than.
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