CN101903437A - Film-like resin composition for encapsulation filling, method for manufacturing semiconductor package or semiconductor device using the same, and semiconductor device - Google Patents

Film-like resin composition for encapsulation filling, method for manufacturing semiconductor package or semiconductor device using the same, and semiconductor device Download PDF

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Publication number
CN101903437A
CN101903437A CN2008801210902A CN200880121090A CN101903437A CN 101903437 A CN101903437 A CN 101903437A CN 2008801210902 A CN2008801210902 A CN 2008801210902A CN 200880121090 A CN200880121090 A CN 200880121090A CN 101903437 A CN101903437 A CN 101903437A
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China
Prior art keywords
resin combination
resin
sealing
compound
membranaceous
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CN2008801210902A
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CN101903437B (en
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榎本哲也
永井朗
本田一尊
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/3121—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation
    • H01L23/3128—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation the substrate having spherical bumps for external connection
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • 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
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Abstract

Disclosed is a film-like resin composition for encapsulation filling, which contains (a) a thermoplastic resin, (b) an epoxy resin, (c) a curing agent and (d) a compound having two or more phenolic hydroxy groups.

Description

Manufacture method and the semiconductor device with membranaceous resin combination, the semiconductor package body of using this resin combination and semiconductor device filled in sealing
Technical field
The present invention relates to a kind of manufacture method and semiconductor device of filling that seal with membranaceous resin combination, the semiconductor package body of using this resin combination and semiconductor device.
Background technology
In recent years, progress along with e-machine miniaturization, multifunction, for semiconductor device, constantly require the raising (at the equity of answering of high frequency transmission) of miniaturization, slimming and electrical specification, and beginning was by being installed in mode on the substrate by wire-bonded with semi-conductor chip in the past, to forming the electroconductibility projection that is called projection and change with the direct-connected flip-chip mode of connection of electrode of substrate on semi-conductor chip.
As the flip-chip mode of connection, known have use scolding tin or tin etc. carry out metallic joint method, apply ultrasonic vibration and carry out the method for metallic joint, utilize the convergent force of resin and keep the method etc. of mechanical contact, wherein, consider from the viewpoint of productivity and connection reliability, extensively adopt and use scolding tin or tin etc. to carry out the method for metallic joint, particularly use the method for scolding tin, because it has demonstrated high connecting reliability, therefore be applicable to the installation of MPU (Micro Processing Unit) etc.
In the flip-chip mode of connection, have the thermal stresses that the coefficient of thermal expansion differences of semi-conductor chip and substrate causes and concentrate on connection section, thereby the risk that connection section is damaged, therefore, in order to disperse this thermal stresses, improve connection reliability, need seal filling to the space between semi-conductor chip and substrate with resin.As the sealing filling mode of resin, after general employing use scolding tin etc. connects semi-conductor chip and substrate, utilize capillary phenomenon again, in the space, inject the mode of aqueous sealing resin.
In this mode, when connecting chip and substrate, make metallic joint become easy in order to reduce lip-deep oxide films such as removing scolding tin, use is by formed solder flux such as rosin or organic acids, and if flux residue is residual, then when injecting aqueous resin, can become the reason that produces the bubble that is called as emptying aperture, perhaps produce the corrosion of distribution owing to sour composition, connection reliability descends, and therefore, needs the operation of washing residue.
Yet in recent years, along with the thin spaceization that connects spacing, the space between semi-conductor chip and substrate becomes narrow, therefore can produce the situation that is difficult to clean flux residue.Further, inject aqueous resin in the narrow gap between semi-conductor chip and substrate, need for a long time, so productivity reduces.
Therefore, need a kind of demonstrating to reduce the sealing resin of character (below, note is made flux activity) of existing oxide film on the metallic surfaces such as removing scolding tin.By using this sealing resin, can think after sealing resin is supplied to substrate, when connecting semi-conductor chip and substrate, can seal filling to the space between semi-conductor chip and substrate by this resin, and can omit the washing of flux residue.In addition, as the content relevant with flux activity, known have a following open communique.
[patent documentation 1] TOHKEMY 2001-223227 communique
[patent documentation 2] TOHKEMY 2005-272547 communique
[patent documentation 3] TOHKEMY 2006-169407 communique
Disclosure of the Invention
The problem that invention will solve
As the sealing resin that demonstrates flux activity, studying organic acid materials such as being combined with carboxylic acid, but because organic acid can be as the curing agent for epoxy resin that is widely used in sealing resin, therefore be difficult to the control reactivity and guarantee its storage stability, perhaps have the corrosion that produces distribution owing to sour composition, the situation that causes insulating reliability to descend.In addition, under sealing resin is aqueous situation, using the divider etc. will be resin-coated on substrate the time and since resin viscosity through the time variation, and have the situation that is difficult to stably control feed rate.
The object of the invention is to provide a kind of good storage stability and flux activity of demonstrating, and can make the membranaceous resin combination of sealing filling of the semiconductor article (semiconductor package body and semiconductor device etc.) of connection reliability excellence.The present invention also aims to provide a kind of semiconductor article and manufacture method thereof of using this resin combination.
The method that is used to deal with problems
The invention provides the membranaceous resin combination of sealing filling of (a) thermoplastic resin of a kind of containing, (b) bad epoxy resins, (c) solidifying agent and the compound that (d) has 2 above phenolic hydroxyl groups.
Sealing of the present invention is filled and is used membranaceous resin combination, demonstrates good storage stability and flux activity, by using said composition, can make the semiconductor article (semiconductor package body and semiconductor device etc.) of connection reliability excellence.In addition, because above-mentioned composition is membranaceous, therefore, compare with aqueous sealing resin, its property handled, operability are especially excellent.In addition, the present inventor is not confined to particular theory, and thinks and can improve flux activity and prevent the connection reliability main reasons for decrease, is to contain the compound with 2 above phenolic hydroxyl groups because sealing of the present invention is filled with membranaceous resin combination.
In addition, sealing of the present invention is filled and is used membranaceous resin combination, it is also understood that to containing (a) thermoplastic resin, (b) Resins, epoxy, (c) solidifying agent and the membranaceous sealed filling material (membranaceous sealing material or membranaceous packing material) that (d) has the compound of 2 above phenolic hydroxyl groups.
(d) have the compound of 2 above phenolic hydroxyl groups, be preferably compound and be selected from the polycondensate of the compound more than at least a kind in the group of forming by the aromatics with 2 halogenated methyls, alkoxy methyl or hydroxymethyls, Vinylstyrene and aldehyde cpd with 1 above phenolic hydroxyl group.As polycondensate, for example be phenol novolac resin, cresols novolac resin, naphthol novolac varnish resin, phenol aralkyl resin etc.
(d) compound with 2 above phenolic hydroxyl groups is preferably and is aqueous compound when 120～300 ℃ (preferred 120～220 ℃, more preferably 180～220 ℃).That is to say, this compound be preferably corresponding to 120 ℃ of low melting point scolding tin melt temperature to 300 ℃ scope corresponding to high-melting-point scolding tin melt temperature, the compound that exists with liquid form (also can be below the temperature range) for aqueous at this.By this formation, can remove the oxide film on scolding tin surface more equably.
(c) solidifying agent is preferably imidazolium compounds.By using imidazolium compounds, can improve simultaneously as the thermotolerance of sealing filling with the storage stability and the cured article of membranaceous resin combination as solidifying agent.
Sealing of the present invention is filled and is preferably further contained mineral filler with membranaceous resin combination.By containing mineral filler, for example, the viscosity adjustment that sealing is filled with membranaceous resin combination becomes easily, can also control the curing rerum natura.
The present invention also provides a kind of the filling by above-mentioned sealing to use membranaceous resin combination, semi-conductor chip and substrate is carried out the manufacture method of the semiconductor package body that flip-chip is connected.
The present invention further provides a kind of manufacture method that connects the semiconductor device of semiconductor package body and substrate with membranaceous resin combination of filling by sealing.
These manufacture method are compared with using the manufacture method in the past of injecting aqueous sealing resin mode, and metallic joint becomes easily, can access the semiconductor package body and the semiconductor device of connection reliability excellence.
The present invention also provides a kind of semiconductor device that the substrate that connects with membranaceous resin combination is filled in the above-mentioned sealing of use that has.
Have and use above-mentioned sealing to fill the semiconductor device of the substrate that connects with membranaceous resin combination, compare with using the semiconductor device that injects the manufacturing of aqueous sealing resin mode, its connection reliability is especially excellent.
The invention effect
According to the present invention, a kind of good storage stability and flux activity of demonstrating can be provided, can make the membranaceous resin combination of sealing filling of the semiconductor article (semiconductor package body and semiconductor device etc.) of connection reliability excellence.In addition, also provide a kind of used this resin combination, especially excellent semiconductor article and the manufacture method thereof of connection reliability.
The simple declaration of accompanying drawing
[Fig. 1] is that the sectional view of sealing filling with a kind of embodiment of the semiconductor package body of membranaceous resin combination used in expression.
[Fig. 2] is that the sectional view of sealing filling with a kind of embodiment of the semiconductor device of membranaceous resin combination used in expression.
[Fig. 3] is that the sectional view of sealing filling with a kind of embodiment of the manufacture method of the semiconductor package body of membranaceous resin combination used in expression.
Nomenclature
1... soldered ball, 2... electrode pad, 3,19... projection, 4,11,14... distribution, 5,18... semi-conductor chip, 6,12, the 16... sealing is filled with membranaceous resin combination, 7,15... substrate, 8... female plug plate, 9... internal layer distribution, 10... passage, 13... through hole, 17... connecting joint, 20... platen, 100... semiconductor package body, 200... semiconductor device.
The best mode that is used to carry out an invention
Below, describe the present invention in detail by preferred implementation.
Sealing of the present invention is filled with membranaceous resin combination and is contained (a) thermoplastic resin, (b) Resins, epoxy, (c) solidifying agent and the compound that (d) has 2 above phenolic hydroxyl groups.Below, each composition is described.
(a) thermoplastic resin
Used (a) thermoplastic resin is to be solid when storage temperature (below 25 ℃) with membranaceous resin combination is filled in sealing among the present invention, is the resin of molten state in the sealing filling during with the Applicable temperature (more than 100 ℃) of membranaceous resin combination at least.
As (a) thermoplastic resin, can enumerate phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, vibrin, polyvinyl resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, acrylic rubber etc., the phenoxy resin of wherein preferred thermotolerance and film-forming properties excellence, polyimide resin, cyanate ester resin, polycarbodiimide resin etc., more preferably phenoxy resin, polyimide resin.Preferred especially intramolecularly has the phenoxy resin of fluorene skeleton.The second-order transition temperature of this phenoxy resin is about 90 ℃, and than other phenoxy resin that does not have fluorene skeleton (being about 60 ℃) height, therefore, when forming membranaceous resin composition for encapsulating, can improve second-order transition temperature, improves thermotolerance.
(a) weight-average molecular weight of thermoplastic resin is preferably more than 5000, more preferably more than 10000, more preferably more than 20000.When weight-average molecular weight is 5000 when following, have the situation that film forming ability descends.In addition, weight-average molecular weight is to use GPC (Gel Permeation Chromatography), and the value of being measured by polystyrene conversion.In addition, these thermoplastic resins can use separately, or use as mixture more than 2 kinds or multipolymer.
(b) Resins, epoxy
Used (b) Resins, epoxy is to have 2 above epoxy group(ing) (oxyethane ring, oxirane) compound of (more than 2 official's energy) among the present invention.
As (b) Resins, epoxy, for example, can use bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, Resorcinol type Resins, epoxy, the Resins, epoxy that contains the diphenyl sulfide skeleton, phenol aralkyl-type polyfunctional epoxy resin, the polyfunctional epoxy resin that contains the naphthalene skeleton, the polyfunctional epoxy resin that contains the Dicyclopentadiene (DCPD) skeleton, the polyfunctional epoxy resin that contains the tritane skeleton, the amino-benzene phenol-type epoxy resin, diaminodiphenyl-methane type Resins, epoxy, other various polyfunctional epoxy resins etc.
Wherein, consider from the viewpoint of lowering viscousity, low water absorption, high heat resistance, preferably use bisphenol A type epoxy resin, bisphenol f type epoxy resin, contain the naphthalene skeleton polyfunctional epoxy resin, contain the Dicyclopentadiene (DCPD) skeleton polyfunctional epoxy resin, contain the polyfunctional epoxy resin of tritane skeleton etc.In addition, as the proterties of these Resins, epoxy, in the time of 25 ℃, be aqueous or solid can, and, when connecting, preferably use its fusing point or the softening temperature resin lower than scolding tin fusing point at for example heating and melting scolding tin for solid Resins, epoxy.In addition, these Resins, epoxy can use separately, or use mixing more than 2 kinds.
In addition, used scolding tin in sealing suitable of the present invention is filled with the semiconductor article (semiconductor package body and semiconductor device etc.) of membranaceous resin combination, can be leaded scolding tin, also can be Pb-free solder (for example, SnAgCu system, SnZnBi system, SnCu system).In addition, can be low melting point scolding tin (fusing point: about 120～150 ℃), also can be high-melting-point scolding tin (fusing point: about 180～300 ℃).
(c) solidifying agent
(c) solidifying agent that uses among the present invention is meant curing (b) curing agent for epoxy resin, and it also can be also to make (b) Resins, epoxy composition (compound that for example, has 2 above phenolic hydroxyl groups) in addition produce the material of curing reaction.
As (c) solidifying agent, can use imidazolium compounds, anhydrides, amine, hydrazides class, polythiol class, Lewis acid-amine coordination compound etc.Wherein, the imidazolium compounds of the excellent heat resistance of storage stability and cured article preferably.When solidifying agent is imidazolium compounds, for example, can enumerate 2MZ, C11Z, 2PZ, 2E4MZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CN, 2PZ-CNS, C11Z-CNS, 2MZ-A, C11Z-A, 2E4MZ-A, 2P4MHZ, 2PHZ, 2MA-OK, 2PZ-OK (Shikoku Chem's system, and the compound that makes these imidazolium compoundss and Resins, epoxy addition gained ProductName) etc..In addition, be that polymer substance etc. coats these solidifying agent and the material of micro encapsulation with polyurethane series, polyester, owing to prolonged working life, therefore preferred.These materials can use separately, or use mixing more than 2 kinds.
(d) has the compound of 2 above phenolic hydroxyl groups
Used (d) has the compound of (meaning is that per 1 molecule has more than 2) phenolic hydroxyl group more than 2 among the present invention, is the compound with hydroxyl that 2 above phenolic hydroxyl groups promptly are connected with phenyl ring.That is to say (d) to have the compound of 2 above phenolic hydroxyl groups, is to have at least 1 phenyl ring, and has the compound of at least 2 hydroxyls that are connected with phenyl ring (also can form condensed ring).
As this compound, for example, can enumerate pyrocatechol, Resorcinol, Resorcinol, '-biphenyl diphenol, dihydroxy naphthlene, hydroxyl Resorcinol, pyrogallol, methylene bis-phenol (Bisphenol F), isopropylidene bis-phenol (dihydroxyphenyl propane), ethylidene bis-phenol (dihydroxyphenyl propane D), 1,1,1-three (4-hydroxy phenyl) ethane, trihydroxybenzophenone, trihydroxy-acetophenone, poly-to vinylphenol, contain the multifunctional phenolic compound of tris-phenol skeleton etc.
Further, as compound, can also use the polycondensate of the compound more than at least a kind in compound with 1 above phenolic hydroxyl group and the group that is selected from aromatics, Vinylstyrene and aldehyde cpd composition with 2 halogenated methyls, alkoxy methyl or hydroxymethyls with 2 above phenolic hydroxyl groups.
As compound with 1 above phenolic hydroxyl group, for example, can enumerate phenol, alkylphenol, naphthols, cresols, pyrocatechol, Resorcinol, Resorcinol, '-biphenyl diphenol, dihydroxy naphthlene, hydroxyl Resorcinol, pyrogallol, methylene bis-phenol (Bisphenol F), isopropylidene bis-phenol (dihydroxyphenyl propane), ethylidene bis-phenol (dihydroxyphenyl propane D), 1,1,1-three (4-hydroxy phenyl) ethane, trihydroxybenzophenone, trihydroxy-acetophenone, poly-to vinylphenol etc.
As aromatics with 2 halogenated methyls, alkoxy methyl or hydroxymethyls, for example, can enumerate 1,2-two (chloromethyl) benzene, 1,3-two (chloromethyl) benzene, 1,4-two (chloromethyl) benzene, 1,2-two (methoxymethyl) benzene, 1,3-two (methoxymethyl) benzene, 1,4-two (methoxymethyl) benzene, 1,2-two (hydroxymethyl) benzene, 1,3-two (hydroxymethyl) benzene, 1,4-two (hydroxymethyl) benzene, two (chloromethyl) biphenyl, two (methoxymethyl) biphenyl etc.By make aromatics with 2 halogenated methyls, alkoxy methyl or hydroxymethyls and in the Vinylstyrene any and have the compound reaction of 1 above phenolic hydroxyl group, also can form compound, and show the effect same that flux activity improves with 2 above phenolic hydroxyl groups.
As aldehyde cpd, can enumerate formaldehyde (as the formalin of its aqueous solution), Paraformaldehyde 96, trioxane, vulkacit H etc.
As above-mentioned polycondensate, for example, can enumerate phenol novolac resin as the polycondensate of phenol and formaldehyde, cresols novolac resin as the polycondensate of cresols and formaldehyde, naphthol novolac varnish resin as the polycondensate of aphthols and formaldehyde, as phenol and 1, the phenol aralkyl resin of the polycondensate of 4-two (methoxymethyl) benzene, the polycondensate of dihydroxyphenyl propane and formaldehyde, the polycondensate of phenol and Vinylstyrene, cresols, the polycondensate of naphthols and formaldehyde etc., can also be these polycondensates modified rubber compound or in molecular skeleton, imported the material of aminotriazine skeleton or Dicyclopentadiene (DCPD) skeleton.
In addition, proterties as these compounds, at room temperature be solid state or aqueous can, but remove the oxide film of metallic surface in order to reduce equably, and do not damage the wettability of scolding tin, preferably use aqueous material, for example, form aqueous material as carrying out allylation, can enumerate allylation phenol novolac resin, diallyl bisphenol, diallyl Bisphenol F, diallyl '-biphenyl diphenol etc. by the compound that these is had phenolic hydroxyl group.These compounds can use separately, or will be used in combination more than 2 kinds.
Further, for example, when connecting by heating and melting scolding tin, the compound that adds in order to give flux activity must not decompose when heating and volatilize, and remains in the caking agent (sealing is filled and used membranaceous resin combination).That is to say, the compound that adds in order to give flux activity, its hot weight rate of measuring by TGA (Thermal Gravimetory Analysis) method is the minimum temperature of 0% (remaining weight is 0), preferably than the melt temperature height of scolding tin.In addition, as the compound that adds in order to give flux activity, when using under the normal temperature material as solid state, the melt temperature of preferred this compound is lower than the melt temperature of scolding tin, that is to say, in order to remove the oxide film on scolding tin surface equably, under the melt temperature of scolding tin, compound preferably has flowability, promptly exists with liquid form or molten state.
In addition, so-called flux activity among the present invention, be meant and reduce the oxide film of removing the metallic surface, thereby make the easy fusion of metal, and can not hinder the wetting expansion of molten metal, can obtain to form the performance of the state of metallic joint portion, for example, be meant heating and melting soldered ball on copper coin etc. and when connecting, size of solder ball becomes big than the initial stage diameter, wetting expansion on the copper surface, and when the soldered ball after the fusion is carried out shearing test, can obtain to produce fracture on the interface of scolding tin and copper, and the soldered ball big damaged state that rises.
In addition, when the soldered ball after the fusion was defined as the wetting rate of spread of scolding tin described later with respect to its initial stage diameter variation rate, in order to realize good flux activity, the wetting rate of spread of scolding tin was preferably more than 20%, more preferably more than 30%, and more preferably more than 40%.
(a) use level of thermoplastic resin with respect to (a) thermoplastic resin and (b) total amount 100 weight parts of Resins, epoxy, is preferably 5～50 weight parts, and more preferably 5～40 weight parts are preferably 10～35 weight parts especially.When this use level during less than 5 weight parts, have and be difficult to film forming tendency, when it surpasses 50 weight parts, have viscosity and uprise, produce the risk of bad connection.
(b) use level of Resins, epoxy with respect to (a) thermoplastic resin and (b) total amount 100 weight parts of Resins, epoxy, is preferably 10～90 weight parts, 15～90 weight parts more preferably, and 20～80 weight parts more preferably.When this use level during, have the tendency that the thermotolerance of cured article descends, and when it surpasses 90 weight parts, have the risk of film-forming properties decline less than 10 weight parts.
(c) use level of solidifying agent is according to the kind of solidifying agent and in general difference, with respect to (b) Resins, epoxy 100 weight parts, is 0.05～30 weight part.When solidifying agent is imidazolium compounds, with respect to (b) Resins, epoxy 100 weight parts, be preferably 0.1～20 weight part, and 1～10 weight part more preferably.When this use level during, solidify insufficient less than 0.1 weight part.In addition, when its during more than 20 weight parts, have the situation that the thermotolerance of cured article descends.
(d) have the use level of the compound of 2 above phenolic hydroxyl groups,, be preferably 0.5～20 weight part with respect to (a) thermoplastic resin and (b) total amount 100 weight parts of Resins, epoxy, and 1～15 weight part more preferably.When this use level during less than 0.5 weight part, have the insufficient situation of flux activity, and when it surpasses 20 weight parts, it then is not the independent curing system of Resins, epoxy, but formed the curing system (in the network of cured article, having inserted phenols) of Resins, epoxy and phenols, therefore have owing to used compound, cause fully to show the characteristic of Resins, epoxy, the risk that the thermotolerance of cured article descends with phenolic hydroxyl group.
In addition, (d) have the kind and the optimal use level of the compound of 2 above phenolic hydroxyl groups, not only consider to have or not flux activity, and consider film-forming properties, the operability (the viscosity variation of varnish etc.) when film is made, the processing (processibilities such as viscosity, stamping-out or cutting etc.) of film etc., set.
Sealing of the present invention is filled and is used membranaceous resin combination, preferably also contains mineral filler.By containing mineral filler, for example, the viscosity adjustment that sealing is filled with membranaceous resin combination becomes easily, can also control the curing rerum natura.In addition, can also be suppressed at generation space and inhibition rate of moisture absorption when connecting semi-conductor chip and substrate.
As mineral filler, be not particularly limited, for example, can enumerate glass, silicon-dioxide (silica), aluminum oxide (alumina), titanium oxide (titania), magnesium oxide (magnesia), carbon black, mica, barium sulfate etc.These fillers can use separately, perhaps use mixing more than 2 kinds.In addition, can also be that the composite oxides that contain metal oxide more than 2 kinds (are not the formed materials of the simple mixing of metal oxide more than 2 kinds, but metal oxide each other Chemical bond and form can't separate stage material), for example, can enumerate formed composite oxides such as silicon-dioxide and titanium oxide, silicon-dioxide and aluminum oxide, boron oxide and aluminum oxide, silicon-dioxide and aluminum oxide and magnesium oxide etc.In addition, with regard to the particle diameter of filler, be electrically connected in order to prevent that the filler portion of being connected catches and hinders when carrying out the flip-chip connection, preferably its median size is below the 10 μ m.Further, in order to adjust viscosity and cured article rerum natura, filler combination that can also particle diameter more than 2 kinds is different is used.
The use level of filler among the present invention with respect to (a) thermoplastic resin and (b) total amount 100 weight parts of Resins, epoxy, is preferably below 200 weight parts, more preferably below 150 weight parts.When this use level during more than 200 weight parts, the viscosity that has caking agent uprises, and the risk of bad connection takes place, and in addition, also has the flexible decline of film and the tendency that becomes fragile.
In addition, roughly the same by the specific refractory power that makes mineral filler and resin when containing mineral filler, can realize to wavelength being the light of 555nm, the transmitance more than at least 10%.By having this transmitance, carry out in the method for singualtion after affixing to substrate or semi-conductor chip with membranaceous resin combination will sealing to fill, be easy to see through the sealing filling and discern with membranaceous resin combination and be used to carry out the position registration mark that the singualtion position overlaps with the position of substrate and semi-conductor chip.
When using Resins, epoxy as resin, the specific refractory power of mineral filler is preferably 1.53～1.65 with respect to the specific refractory power of about 1.6 Resins, epoxy.As the mineral filler that demonstrates this specific refractory power, can enumerate the formed composite oxides of barium sulfate, magnesium oxide, silicon-dioxide and titanium oxide, silicon-dioxide and the formed composite oxides of aluminum oxide, boron oxide and the formed composite oxides of aluminum oxide, silicon-dioxide and aluminum oxide and the formed composite oxides of magnesium oxide etc.
In addition, when using sealing filling of the present invention to connect semi-conductor chip and substrate with membranaceous resin combination, the sealing that is cut into monolithic can be filled and stick on the substrate with membranaceous resin combination, also can stick on semi-conductor chip formation on the face of projection.In addition, also can be before with the substrate singualtion, under the state that a plurality of substrates connect together, will seal to fill and stick on substrate on the whole with membranaceous resin combination, behind the connection semi-conductor chip, carry out singualtion.In addition, sealing can also be filled with membranaceous resin combination and stick on the semiconductor wafer before monolithic turns to semi-conductor chip, its monolithic be turned to semi-conductor chip by cutting.
Further, sealing of the present invention is filled with in the membranaceous resin combination, can also cooperate additives such as curing catalyst, silane coupling agent, titanium coupling agent, oxidation inhibitor, flow agent, ion capturing agent.These additives may be used alone, or two or more kinds may be used in combination.For use level, be adjusted to the effect that can show each additive and get final product.
The viscosity with membranaceous resin combination is filled in sealing of the present invention, is below the 50Pas in the time of 150 ℃ preferably, more preferably below the 40Pas, more preferably below the 30Pas.When viscosity is higher than 50Pas, have the situation that produces bad connection.The measuring method of viscosity can use shear viscoelasticity determinator (for example, TA instrument company system ARES), film is clipped between the parallel cylinder that diameter is 8～25mm, and under the temperature of regulation, be to measure under the condition of 1～10Hz in frequency, and measure and automatically to carry out.
In addition, can also calculate by the following method: stamping-out is clipped between the sheet glass with membranaceous resin combination for circular sealing filling, and the specific time that under the pressure of the temperature of stipulating, regulation, pressurizes, calculate by the variation of resin thickness before and after the pressurization.That is to say, can calculate by following formula (1) (relating to uncommon thunder (the ヒ one リ one) formula of uniaxial compression mobile between parallel plate).
η＝8πFtZ 4Z 0 4/3V 2(Z 0 4-Z 4)...(1)
η: viscosity (Pas)
F: loading (N)
T: clamping time (s)
Z: the resin thickness after the pressurization (m)
Z 0: the resin thickness (m) before the pressurization
V: the volume (m of resin 3)
Sealing of the present invention is filled with the gelation time of membranaceous resin combination 260 ℃ the time, is preferably 1～60s, 3～40s more preferably, and 5～30s more preferably.When it was shorter than 1s, scolding tin etc. had just solidified before fusion, had the risk that produces bad connection, and when its during more than 60s, have productivity to descend, or curing becomes insufficient and causes the risk of reliability decrease.In addition, gelation time is meant sealing of the present invention filled to be placed on the hot plate that is set at 260 ℃ with membranaceous resin combination, and stirs with scraper etc., up to the time that can't stir.
Sealing of the present invention is filled and is used membranaceous resin combination, for example, can followingly make.That is to say, in organic solvents such as toluene, ethyl acetate, methyl ethyl ketone, mixing (a) thermoplastic resin, (b) Resins, epoxy, (c) solidifying agent, (d) have compound, mineral filler and other additive of 2 above phenolic hydroxyl groups, make varnish, use Scraper applicator or roller coating machine this varnish to be coated on the film base materials such as pet resin of having implemented demoulding processing, drying is removed organic solvent then, thereby makes.
Fig. 1 is that expression uses sealing of the present invention to fill the sectional view of a kind of embodiment of the semiconductor package body made from membranaceous resin combination.Semiconductor package body 100 shown in Figure 1 has following structure: have on the one side on the semi-conductor chip 5 of projection 3 (solder bump etc.) and the one side and have the substrate 7 that has the electrode pad 2 that is formed with soldered ball 1 on distribution 4, the another side, fill with membranaceous resin combination 6 joints by sealing, make that projection 3 and distribution 4 are electrically connected.In semiconductor package body 100, seal or fill with membranaceous resin combination 6 by the sealing filling around gap between semi-conductor chip 5 and the substrate 7 and the semi-conductor chip 5.
As semi-conductor chip 5, be not particularly limited, can use various semi-conductors such as compound semiconductor such as elemental semiconductors such as silicon, germanium, gallium arsenide, indium phosphide.
As substrate 7, can be common circuit substrate, perhaps also can be semi-conductor chip.The occasion of circuit substrate, can use unwanted position etching in the metal levels such as copper that will on insulated substrate surfaces such as glass epoxy resin, polyimide, polyester, pottery, form to remove and formed the substrate of Wiring pattern, by copper facing at the substrate that has formed Wiring pattern on the insulated substrate surface, the printing conductive material has formed the substrate of Wiring pattern etc. on the insulated substrate surface.On the surface of Wiring pattern (distribution 4), can form the metal level that is constituted by low melting point scolding tin, high-melting-point scolding tin, tin, indium, gold, nickel, silver, copper, palladium etc., this metal level can only be made of single composition, also can be made of multiple composition.In addition, can also form the structure that a plurality of metal level laminations form.
As the material of the electroconductibility projection that is called projection 3, can use the material that is constituted by low melting point scolding tin, high-melting-point scolding tin, tin, indium, gold and silver, copper etc., it can only be made of single composition, also can be made of multiple composition.In addition, can also form these metal laminated structures that forms.Projection can form on semi-conductor chip 5, also can form on substrate 7, and can form on the two at semi-conductor chip 5 and substrate 7.
As semiconductor package body, be on the substrate that is known as built-in inserted plate (interposer), to carry semi-conductor chip, and carry out resin-sealed formed package, for example, can enumerate CSP (chip size packages) or BGA (ball grid array) etc.In addition, thus as by need not built-in inserted plate and just can be equipped on semiconductor package body on the substrate on the semiconductor chip surface electrode part of semi-conductor chip being carried out distribution again, for example, can enumerate the package that is called as wafer-class encapsulation.As the substrate that carries semiconductor package body, can be common circuit substrate, with respect to built-in inserted plate, can be called the female plug plate.
Fig. 2 is that expression uses sealing of the present invention to fill the sectional view of a kind of embodiment of the semiconductor device made from membranaceous resin combination.Semiconductor device 200 shown in Figure 2 has following structure: female plug plate 8 and semiconductor package body 100 (referring to Fig. 1) are filled by sealing and are engaged with membranaceous resin combination 12, make that soldered ball 1 and distribution 11 are electrically connected, described female plug plate 8 is formed with internal layer distribution 9, path 10 and through hole 13 and has distribution 11 on one side.In semiconductor device 200, seal or fill with membranaceous resin combination 12 by the sealing filling around gap between substrate 7 and the female plug plate 8 and the semiconductor package body 100.
Then, the manufacture method to semiconductor package body of the present invention describes.Fig. 3 is that the sectional view of sealing filling of the present invention with a kind of embodiment of the manufacturing method for semiconductor chips of membranaceous resin combination used in expression.
(1) at first, the substrate that be formed with distribution 14 15 of preparation shown in Fig. 3 (a).Then, shown in Fig. 3 (b), make it cover distribution 14 with membranaceous resin combination 16 at substrate 15 superimposed layers and stickup sealing filling.Stickup can be undertaken by thermocompressor, roll-type laminating machine, vacuum laminator etc.Sealing is filled and is set according to bonding area and film thickness with the feed rate of membranaceous resin combination 16, and the size by semi-conductor chip 18, bump height (projection 19 is from the height on semi-conductor chip 18 surfaces) etc. are stipulated, even viscosity etc. produce through the time change, also can control feed rate at an easy rate.
In addition, sealing can be filled and stick on the semi-conductor chip 18 with membranaceous resin combination 16, cut after perhaps also can stick on the semiconductor wafer with membranaceous resin combination 16 the sealing filling, its monolithic is turned to semi-conductor chip 18, be pasted with the semi-conductor chip 18 of sealing filling with membranaceous resin combination 16 thereby can make.
(2) then, shown in Fig. 3 (c), the semi-conductor chip 18 that will have projection 19 (solder bump) is installed on the connecting joint 17 of coupling devices such as flip-chip bond device, on the other hand, fill with membranaceous resin combination 16 and the substrate 15 that has a distribution 14 and be installed on the platen 20 of same coupling device being pasted with sealing, carry out aligned in position, heat semi-conductor chip 18 and substrate 15 with the temperature more than projection 19 fusing points on one side then, Yi Bian push.Then, shown in Fig. 3 (d),, semi-conductor chip 18 and substrate 15 is electrically connected, simultaneously, fills the space that seals 15 of filling semiconductor chips 18 and substrates with membranaceous resin combination 16 by the fused sealing by engagement protrusion 19 and distribution 14.At this moment, because the flux activity with membranaceous resin combination 16 is filled in sealing, the oxide film on projection 19 surfaces is reduced to be removed, and projection 19 fusions form connection section by metallic joint.
In addition, though not record among Fig. 3, but also can be by making the alignment of semi-conductor chip and substrate position, on one side with projection (solder bump) not the fused temperature heat, push on one side, sealing is filled with membranaceous resin combination fusion, remove the projection of semi-conductor chip and the resin between electrode of substrate, and seal space between filling semiconductor chip and substrate simultaneously, working fastening semi-conductor chip and substrate by carry out heat treated in reflow ovens, make the projection fusion then, connect semi-conductor chip and substrate, make semiconductor package body thus.
(3) further, in order to improve connection reliability, can also in heated oven etc., carry out heat treated to above-mentioned semiconductor package body, further seal the curing of filling with membranaceous resin combination.
Use the manufacture method of sealing filling of the present invention, can roughly similarly implement with the manufacture method of above-mentioned semi-conductor chip with the semiconductor device of membranaceous resin combination.That is to say, the semi-conductor chip with projection 19 18 that the semiconductor package body 100 of use Fig. 1 replaces among Fig. 3, use being formed with internal layer distribution 9, path 10 and through hole 13 and on one side, having the substrate that is formed with distribution 14 15 that the female plug plate 8 of distribution 11 replaces among Fig. 3 among Fig. 2, and the sealing filling is fallen between with membranaceous resin combination 16, on one side semiconductor package body 100 and female plug plate 8 are heated to more than the fusing point of soldered ball 1, on one side pressurization engage the two.
Embodiment
Below, by reference example, embodiment and comparative example explanation the present invention, but scope of the present invention does not limit thus.
(reference example)
Will be as 25 weight part phenoxy resin FX293 (Toto Kasei KK's systems of (a) thermoplastic resin, the goods name), as solid shape polyfunctional epoxy resin EP1032H60 (the japan epoxy resin corporate system of 30 weight parts of (b) Resins, epoxy, the goods name) and aqueous bisphenol A type epoxy resin EP828 (the japan epoxy resin corporate system of 45 weight parts, the goods name), has the compound shown in the 5 weight part tables 1 of compound of 2 above phenolic hydroxyl groups as (d), 100 weight part SE6050 (Admatechs corporate systems as the spherical silicon dioxide filler, the goods name, median size 2 μ m) dissolving mixes in toluene-ethyl acetate solvent, making solid component concentration is 60～70%, makes varnish.Use Scraper applicator that this varnish is coated on the barrier film (PET film), in 70 ℃ baking oven dry 10 minutes then, making thickness thus was the membranaceous resin combination of the reference example 1～7 of 40～45 μ m.In use, its 2 are superimposed together, and adjustment thickness is that 80～90 μ m use by the hot-roll lamination machine.
(flux activity evaluation method)
According to following program, the flux activity of evaluation reference example.
Post glass epoxy substrate (Hitachi Chemical Co., Ltd.'s system of Copper Foil being cut into the square two sides of 25mm, goods name: MCL-E-679F, thickness is 0.3mm, passed through degreasing and cleanup acid treatment) the copper surface on, adhesion is cut into the square membranaceous resin combination of 10mm, peel off barrier film, on membranaceous resin combination, dispose 5 soldered ball (Senju Metal Industry Co., Ltd's systems then, goods name: M705 (Sn-3Ag-0.5Cu), spherical diameter is 0.4mm, fusing point is 217～220 ℃), and cover glass (it is square to be of a size of 18mm, and thickness is 0.17mm) further is set, make to estimate and use sample, and,, use 2 evaluations to estimate with sample for various membranaceous resin combinations.
This evaluation was placed for 30 seconds being heated on 160 ℃ the hot plate with sample, and continue to place for 30 seconds being heated on 260 ℃ the hot plate, be back to room temperature again, to estimate with sample then and be immersed in the methyl ethyl ketone, membranaceous resin combination is removed in dissolving, measures to remain in lip-deep soldered ball quantity of glass epoxy substrate and diameter.The wetting rate of spread of scolding tin is calculated according to following formula (2).
The wetting rate of spread of scolding tin (%)=(remaining in the soldered ball diameter-initial stage soldered ball diameter on the substrate surface)/initial stage soldered ball diameter * 100... (2)
Further, the soldered ball of glass epoxy substrate remained on surface is implemented shearing test, the result, the situation note that will produce fracture on the interface of soldered ball and Copper Foil is made " B ", and the situation of soldered ball main body destruction breakage is that flux activity is abundant, and note is made " A ".In addition, shearing test use to engage tester series 4000 (DAGE society system, goods names), and at room temperature, shear height is 50 μ m, and velocity of shear is to carry out under the condition of 100 μ m/s.
(mensuration of volatilization end temp)
The mensuration of the volatilization end temp of compound (hot weight rate is 0% o'clock a minimum temperature) is to use TG/DTA6300 (Seiko instrument company system, the goods name), at heat-up rate is 10 ℃/min, air flow quantity is 200ml/min, measuring temperature range is 30～300 ℃, and example weight is to carry out under the condition of 5～10mg.
The evaluation result of flux activity is shown in table 1.(in addition, " 〉=" expression in the table 1 " more than ", "＜" expression " less than ".)
[table 1]
Compound name Proterties Phenolic hydroxyl group quantity The volatilization end temp (℃) The soldered ball extant number The wetting rate of spread of scolding tin (%) The shearing test fracture mode Remarks (manufacturers)
Reference example 1 Do not have ?- - - 3/10 59 A and B mix and exist -
Reference example 2 Right-(α-cumyl) phenol Solid state (fusing point: 75 ℃) 1 258.7 4/10 50 A and B mix and exist Kanto Kagaku K. K.
Reference example 3 The phenol novolac resin Solid state (softening temperature: 80 ℃) ≥2 ＜300 8/10 65 A The HP-850 of Hitachi Chemical Co., Ltd. (goods name)
Reference example 4 Phenol aralkyl resin Solid state is (softening ≥2 ＜300 7/10 64 A Mitsui Chemicals Industrial Co., Ltd
Point: 70 ℃) XLC-3L (goods name)
Reference example 5 Allylation phenol novolac resin Aqueous ≥2 ＜300 9/10 71 A Bright and change into the MEH8000H of Industrial Co., Ltd (goods name)
Reference example 6 2,2 '-diallyl bisphenol Aqueous 2 ＜300 8/10 50 A Sigma aldrich company
Reference example 7 2, the 5-resorcylic acid Solid state (fusing point: 95 ℃) 2 ＜300 8/10 48 A Co., Ltd.'s gentisinic acid (goods name) is learned in greening
In reference example 1, though can observe the flux activity that is considered to result from existing alcoholic extract hydroxyl group in phenoxy resin and the Resins, epoxy, its effect is also insufficient, and in reference example 2, does not also demonstrate sufficient flux activity.Shown in reference example 3～6, the compound that has 2 above phenolic hydroxyl groups by use, compare with reference example 1,2, the wetting rate of spread of soldered ball survival rate or scolding tin improves, in shearing test, on the interface of soldered ball and Copper Foil, do not produce fracture, and it is big damaged to rise, demonstrated and as organic acid 2 the same flux activity of 5-resorcylic acid (reference example 7).
(embodiment 1～4 and comparative example 1,2)
Will be as 25 weight part phenoxy resin FX293 (Toto Kasei KK's systems of (a) thermoplastic resin, the goods name), as solid shape polyfunctional epoxy resin EP1032H60 (the japan epoxy resin corporate system of 30 weight parts of (b) Resins, epoxy, the goods name) and aqueous bisphenol A type epoxy resin EP828 (the japan epoxy resin corporate system of 45 weight parts, the goods name), 3 weight parts 2 as (c) solidifying agent, 4-dihydroxyl methyl-(four countries change into Co., Ltd.'s system to 5-phenylimidazole 2PHZ, the goods name), has the compound shown in the 5 weight part tables 2 of compound of 2 above phenolic hydroxyl groups as (d), and as 100 weight parts of mineral filler SE6050 (Admatechs corporate system as the spherical silicon dioxide filler, the goods name), dissolving mixes in toluene-ethyl acetate solvent, making solid component concentration is 60～70%, makes varnish.Use Scraper applicator that this varnish is coated on the barrier film (PET film), in 70 ℃ baking oven dry 10 minutes then, make thickness thus and be the embodiment 1～4 of 40～45 μ m and the sealing shown in the comparative example 1～3 and fill and use membranaceous resin combination.In use, its 2 are superimposed together, and adjustment thickness is that 80～90 μ m use by the hot-roll lamination machine.
(comparative example 3)
Except the use level that makes mineral filler is 220 weight parts and embodiment 1～4 and comparative example 1,2 similarly make.
The rerum natura with the cured article of membranaceous resin combination, following mensuration are filled in sealing.
(mensuration of average coefficient of linear expansion)
Preparation will carry out handling under the heating condition of 200 ℃/1h sample is cut into the material of 3.0mm * 25mm size, and use TMA/SS6000 (Seiko instrument company system, the goods name), be 15mm in the chuck spacing, to measure temperature range be that 20～300 ℃, heat-up rate are 5 ℃/min, are to measure under the condition of stretching loading of 0.5MPa with respect to the sectional area of film, calculates the average coefficient of linear expansion in 40～100 ℃ of temperature ranges.
(mensuration of Young's modulus and second-order transition temperature (Tg))
Preparation will carry out handling under the heating condition of 200 ℃/1h sample is cut into the material of 5.0mm * 45mm size, and use DMS6100 (Seiko instrument company system, the goods name), in the chuck spacing is that 20mm, frequency are 1Hz, to measure temperature range be that 20～300 ℃, heat-up rate are under the condition of 5.0 ℃/min, carry out the mensuration of storage modulus, out-of-phase modulus and tan δ, the storage modulus when reading 40 ℃ and as the peak temperature of the tan δ of second-order transition temperature (Tg).
(viscosimetric analysis)
The material that preparation is prepared as follows: with stamping-out is that diameter is that the sealing of 4mm circle is filled and to be sticked on the sheet glass of 15mm square (thickness is 0.7mm) with membranaceous resin combination, peel off barrier film, place cover glass (it is square to be of a size of 18mm, and thickness is 0.17mm) then to cover the membranaceous resin combination of sealing filling.(Panasonic produces scientific and technological corporate system at flip-chip bond device FCB3 with the material configuration of above-mentioned preparation, the goods name) on, and be that 185 ℃, platen temperature are that 50 ℃, loading are 12.6N, clamping time to be to heat, pressurize under the condition of 1s (to 150 ℃) at head temperature.When hypothesis resin given volume, the relation of following formula (3) is set up, therefore, and with the radius after the measurement microscope pressurization, and according to preceding formula (1), the viscosity when calculating 150 ℃.
Z/Z 0＝(r 0/r) 2...(3)
Z 0: the resin thickness before the pressurization
Z: the resin thickness after the pressurization
r 0: the radius of the resin before the pressurization (, being 2mm therefore) owing to being that 4mm carries out stamping-out with the diameter
R: the radius of the resin after the pressurization
(storage stability)
Sealing filled with membranaceous resin combination be placed in 40 ℃ the thermostatic bath, the viscosity after 6 days is that the material of initial stage viscosity below 2 times has storage stability, is denoted by " A ", and does not have storage stability greater than 2 times material, is denoted by " B ".Viscosimetric analysis uses preceding method to measure.
(mensuration of gelation time)
The sealing of having peeled off dividing plate filled with membranaceous resin combination be configured on 260 ℃ the hot plate, will be stirred to the time that to stir as gelation time with scraper.
(connecting the making of sample)
On the copper wiring surface, be formed with printed base plate JKITTYPE III (super LSI system house of the Hitachi system of the support soldering-tin layer of Sn-3.0Ag-0.5Cu, the goods name) chip carries on the zone, be cut into after the square sealing of 10mm fills with membranaceous resin combination pasting under the condition of 80 ℃/50N/5s, peel off barrier film, (Panasonic produces scientific and technological corporate system to use flip-chip bond device FCB3, the goods name) is formed with chip Phase2E175 (super LSI system house of the Hitachi system of high-melting-point solder bump (95Pb-5Sn), the goods name, it is square to be of a size of 10mm, thickness is 550 μ m, number of lugs is 832, bump pitch is 175 μ m) and the aligned in position of printed base plate, pressurize with the loading of 5N on one side, on one side the temperature curve with 180 ℃/5～30s+230～280 ℃/5s heats, and connects chip and substrate.Then, in 165 ℃ baking oven, carry out 2 hours heat treated, make the connection sample.
(scolding tin connectivity)
The checking that connects sample, material note that can conducting is made " A ".Then, observe the cross section of connection section, projection is made " A " with supporting scolding tin material note evenly wetting and that engage, evenly not wetting material note is made " B ".
(moisture-proof reliability)
With after connecting sample and in the Thoughs that is set at 130 ℃/relative humidity of temperature 85%, placing 100 hours, carry out checking, compare with the resistance that is connected before placing, resistance change rate has the moisture-proof reliability for ± 10% with interior material, is denoted by " A ".
(insulating reliability)
Having wide with distribution is 20 μ m, wiring closet apart from being on the polyimide substrate of comb type pattern of the formed copper wiring of 40 μ m, under the condition of 80 ℃/100N/5s, paste the membranaceous resin combination of sealing filling, to cover comb type pattern, peel off barrier film, in 165 ℃ baking oven, carry out 2 hours heat treated then, make to estimate and use sample.Sample is placed in the Thoughs that is set to 130 ℃/relative humidity of temperature 85%, and sample is applied the volts DS of 5V, use the insulation resistance in migration tester MIG-8600 (IMV society system, goods name) the METHOD FOR CONTINUOUS DETERMINATION Thoughs.To in 100 hours mensuration, keep 10 6The material of the above insulation resistance of Ω note is made " A ", with insulation resistance less than 10 6The material note of Ω is made " B ".
(synthetic determination)
As comprehensive evaluation according to above-mentioned each evaluation index, will have as the sealing filling and make " A " with the material note of the connection reliability of membranaceous resin combination, the material note that does not have connection reliability is made " B ".
Evaluation result is shown in table 2.
Figure BPA00001159989900201
By result shown in the table 2 as can be known, in embodiment 1～4, good storage stability, scolding tin connectivity, moisture-proof reliability and insulating reliability have been demonstrated.On the other hand, in comparative example 1, in cross-section, projection and support scolding tin are evenly not wetting, the flux activity deficiency.In comparative example 2, though the scolding tin connectivity is good, storage stability is poor, in insulating reliability is estimated, produces bad after measuring 80 hours.In comparative example 3, can think that storage stability is poor, and projection and support scolding tin are evenly not wetting, therefore the viscosity height of membranaceous resin combination has hindered the wetting expansion of fusion scolding tin.
As mentioned above,, can obtain a kind ofly demonstrating good storage stability and flux activity, and the sealing of connection reliability excellence is filled and is used membranaceous resin combination according to the present invention.In addition, the sealing of the application of the invention is filled and is used membranaceous resin combination, carries out metallic joint easily, can make the semiconductor device of connection reliability excellence.Further, can realize good productivity.
Industrial applicibility
According to the present invention, can provide a kind of and demonstrate good storage stability and flux activity, and the membranaceous resin combination of the sealing of connection reliability excellence filling. In addition, the sealing of the application of the invention is filled and is used membranaceous resin combination, and a kind of metal bond, the manufacture method of connection reliability excellence and semiconductor device of carrying out easily can also be provided.

Claims (8)

1. a sealing is filled and is used membranaceous resin combination, the compound that it contains (a) thermoplastic resin, (b) Resins, epoxy, (c) solidifying agent and (d) has 2 above phenolic hydroxyl groups.
2. sealing as claimed in claim 1 is filled and is used membranaceous resin combination, wherein, the compound that (d) has 2 above phenolic hydroxyl groups is the polycondensate that has the compound of 1 above phenolic hydroxyl group and be selected from least a compound in the group of being made up of the aromatics with 2 halogenated methyls, alkoxy methyl or methylols, Vinylstyrene and aldehyde cpd.
3. sealing as claimed in claim 1 or 2 is filled and is used membranaceous resin combination, and wherein, (d) compound with 2 above phenolic hydroxyl groups is to be aqueous compound in the time of 120～300 ℃.
4. each described sealing is filled and is used membranaceous resin combination as claim 1～3, and wherein, (c) solidifying agent is an imidazolium compounds.
5. each described sealing is filled and is used membranaceous resin combination as claim 1～4, and it further contains mineral filler.
6. the manufacture method of a semiconductor package body, it is filled by each described sealing of claim 1～5 and with membranaceous resin combination semi-conductor chip and substrate is carried out flip-chip and be connected.
7. the manufacture method of a semiconductor device, it is filled by each described sealing of claim 1～5 and connects semiconductor package body and substrate with membranaceous resin combination.
8. semiconductor device, it has and uses each described sealing of claim 1～5 to fill substrate with membranaceous resin combination connection.
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