CN101292006A - Adhesive composition, circuit connecting material, circuit member connection structure, and semiconductor device - Google Patents
Adhesive composition, circuit connecting material, circuit member connection structure, and semiconductor device Download PDFInfo
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- CN101292006A CN101292006A CN 200680038502 CN200680038502A CN101292006A CN 101292006 A CN101292006 A CN 101292006A CN 200680038502 CN200680038502 CN 200680038502 CN 200680038502 A CN200680038502 A CN 200680038502A CN 101292006 A CN101292006 A CN 101292006A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/06—Polymers
- H01L2924/078—Adhesive characteristics other than chemical
- H01L2924/0781—Adhesive characteristics other than chemical being an ohmic electrical conductor
- H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
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Abstract
The present invention provides an adhesive composition containing an adhesive component containing a thermoplastic resin, a radical polymerizable compound and a radical polymerization initiator, wherein the adhesive component has a signal in an ESR measurement at 25 ℃.
Description
Technical field
The invention relates to the connection structure and the semiconductor device of adhesive composite, circuit connection material, circuit member.
Background technology
In semiconductor element and liquid crystal display device, for the various members in the binding member, all use various bonding caking agents, the characteristic that requires caking agent to possess all the time, based on cementability, also relate generally to the many-sides such as reliability of thermotolerance, humid tropical condition.
In the prior art, as semiconductor element and the employed caking agent of liquid crystal display device, use excellent in adhesion, even particularly under hot conditions, also demonstrate the thermosetting resin (for example, referring to Patent Document 1) of the Resins, epoxy etc. of excellent cementability.The composition of above-mentioned caking agent generally use Resins, epoxy, with Resins, epoxy have reactive resol etc. stiffening agent, promote the latent heat catalyzer that Resins, epoxy and stiffening agent react.The latent heat catalyzer is the decision stiffening temperature of caking agent and the important factor of setting rate, by the viewpoint of the setting rate when the storage stability of room temperature and the heating, uses various compounds.Related caking agent generally hardened by the temperature heating at 170～250 ℃, thereby obtains cementability in 1～3 hour.
In recent years, along with the Gao Jitiization of semiconductor element, high-accuracyization of liquid crystal cell, between interelement and the wiring closet every towards narrow and smallization development.When so semiconductor element uses above-mentioned caking agent, because Heating temperature height and setting rate when making its sclerosis are slow, be not only desirable connecting portion, periphery material is superheated all, has the tendency of the major cause of the damage that becomes periphery material.And, must improve turnout for cost degradation, so require low temperature (100～170 ℃), short period of time (in 1 hour), in other words, require the bonding of " low temperature snap cure ".In order to realize this low temperature snap cure, must use the latent heat catalyzer of active-energy, still, active latent heat catalyzer that can be low is difficult to have simultaneously near the storage stability room temperature.
Recently, with acrylate derivative or methacrylate derivative (abbreviating (methyl) acrylate later on as) with as the superoxide of radical polymerization initiator mutually and the free radical sclerotic type caking agent of usefulness gazed at, the free radical sclerosis, because the free radical as the reactive behavior kind is rich in reactivity, but so short period of time sclerosis (for example, referring to Patent Document 2,3).
Patent documentation 1: the spy opens flat 01-113480 communique
Patent documentation 2: the spy opens the 2002-203427 communique
Patent documentation 3: the international brochure that discloses No. 98/044067
Summary of the invention
But, because free radical sclerotic type caking agent has hyperergy, so have the tendency that the process time domain (process margin) when carrying out hardening treatment narrows down, when for example using the caking agent of above-mentioned free radical sclerotic type for semiconductor element and liquid crystal display device are electrically connected, the process condition of the temperature and time when obtaining this hardening thing etc. will have the tendency of the characteristic that can't obtain stable bonding strength, connection resistance etc. as long as change a little.
Therefore, in view of the above problems, the purpose of this invention is to provide at low temperature and can carry out hardening treatment fully fast, and the adhesive composite that the process time domain when carrying out hardening treatment is wide, have abundant stable properties (bonding strength and connect resistance), and use its circuit connection material, the connection structure and the semiconductor device of circuit member.
The invention provides a kind of contain have thermoplastic resin, the adhesive composite of the caking agent composition of free-radical polymerised compound and radical polymerization initiator, above-mentioned caking agent composition is the adhesive composite that has signal under 25 ℃ during the ESR that carries out measures.
This adhesive composite can carry out hardening treatment fully apace at low temperature, and the process time domain when carrying out hardening treatment wide, can obtain fully stable bonding strength and connect the characteristic of resistance etc.Though caking agent group thing of the present invention is realized the major cause of above-mentioned relevant effect, still unclear till now, present inventor etc. think that its major cause is as follows, but major cause is not limited to this.
Promptly, but short period of time hardened major cause when low temperature, mainly be because adhesive composite of the present invention contains the caking agent composition of being made up of thermoplastic resin, free-radical polymerised compound and radical polymerization initiator, that is, owing to be so-called free radical sclerotic type adhesive composite.Process time domain when carrying out hardening treatment is wide, can obtain the major cause of fully stable characteristic, mainly is because adhesive composite of the present invention contains the caking agent composition that the ESR that carries out has signal in measuring under 25 ℃.That is, there is free radical in caking agent ingredient stability of the present invention ground.Suppositions such as present inventor are owing to possess whole inseparable above-mentioned formation, so can realize the sclerosis of low temperature short period of time, the process time domain when carrying out hardening treatment simultaneously extensively, fully promotes stable properties to high level.
As mentioned above, use adhesive composite of the present invention, then can carry out hardening treatment in short time, but and expansion process time domain.Therefore, even adhesive composite of the present invention be between the interelement of semiconductor element and liquid crystal cell etc. and the wiring closet every narrow and smallization, not only desirable connecting portion is even periphery material also heats, still can suppress the influence of the damage etc. of surrounding member, can improve turnout.
In addition, adhesive composition of the present invention, the g value of caking agent composition in ESR measures is preferably 2.0000～2.0100, because have so g value, resulting adhesive composite can more enlarge the process time domain when carrying out hardening treatment.
Adhesive composite of the present invention, preferably above-mentioned caking agent composition contains stable free radical compound again, " stable free radical compound " herein is meant that spin density under the equilibrium state measured in ESR measures is the state more than the 1016spin/g, at 25 ℃ of compounds that continue more than 10 minutes.By this, in the adhesive composite,, can more enlarge the process time domain when carrying out hardening treatment because free radical more stably exists.
And above-mentioned stable free radical compound is preferably nitrogenize oxygen (nitroxide) compound, because contain so compound, adhesive composite can more enlarge the process time domain when carrying out hardening treatment.
Adhesive composite of the present invention with respect to the thermoplastic resin of 100 mass parts, preferably contains the free-radical polymerised compound of 50～250 mass parts, the radical polymerization initiator and 0.01～10 mass parts stable free radical compound of 0.05～30 mass parts.Adhesive composition of the present invention by making the blending ratio of its constituent material according to above-mentioned scope, can be brought into play effect of the present invention more significantly.
Adhesive composite of the present invention preferably also contains electroconductive particle, and so adhesive composite can have autoconduction easily, therefore, this adhesive composite in the field of the electrical industry of circuit electrode and semi-conductor etc. and electronic industry, can be used as conductive adhesive to use; And, in this situation, because adhesive composite has electroconductibility, so can more reduce connection resistance after the sclerosis.
In addition, adhesive composite of the present invention with respect to the thermoplastic resin of 100 mass parts, preferably contains the electroconductive particle of 0.5～30 mass parts.Be set in above-mentioned scope by blending ratio, so the adhesive composition effect that can more bring into play electroconductive particle and produced with electroconductive particle.For example, when being used in the connection of circuit electrode, can possess anisotropic conductive, prevent from not conduct electricity between the circuit electrode of subtend or prevent short circuit between adjacent circuit electrode.And, comply with the adhesive composite that above-mentioned blending ratio contains electroconductive particle, can more demonstrate the anisotropy of electrical connection, can be used as the anisotropic conductive adhesive composite and use.
Circuit connection material of the present invention is to be used to make the circuit connection material that is electrically connected between the subtend circuit electrode, thereby circuit connection material preferably contains above-mentioned adhesive composite.
Circuit connection material so, even low temperature carries out bonding between the subtend circuit electrode in the also available abundant short period of time, but expansion process time domain also.And, by resulting hardening thing of circuit connection material so,, also can make bonding strength stable even change process temperature and time when obtaining this hardening thing.In addition, also circuit capable of inhibiting connect material hardening thing through the time the reduction of bonding strength, and, this circuit connection material is if contain electroconductive particle according to above-mentioned blending ratio, can more demonstrate the anisotropy of electrical connection, can be used as the anisotropic conductive circuit connection material that circuit electrode uses and use.
The invention provides above-mentioned adhesive composite is formed the film like caking agent that film like became, in addition, the invention provides and foregoing circuit is connected material form the film-shaped circuit connection material that film like became.The adhesive composite of formation film like and circuit connection material are because the operability excellence can more improve turnout.
The invention provides a kind of connection structure of circuit member, it possesses: between the interarea that be formed with the second circuit member that is formed with the second circuit electrode on the interarea of first circuit member, second circuit substrate of first circuit electrode on the interarea of first circuit substrate, is set at first circuit substrate and the interarea of second circuit substrate and the circuit transom that first circuit electrode and second circuit electrode are electrically connected under the subtend configuration status; The circuit transom is the hardening thing that foregoing circuit connects material.
So the connection of circuit member is constructed, can effectively utilize the circuit electrode that has been electrically connected, that is, because use above-mentioned circuit connection material to make first circuit electrode can be electrically connected, make that the circuit member mass deviation with connection structure of the present invention is few, can demonstrate abundant stable properties with the second circuit electrode.And, when the hardening thing that circuit connects material contains electroconductive particle, can reduce and connect resistance by mixing this electroconductive particle, can realize the optionally electrical connection between desirable member easily.In addition,, demonstrate the anisotropy of electrical connection, also can become the anisotropic conductive circuit connection material if contain electroconductive particle according to above-mentioned blending ratio.
In addition, the invention provides a kind of semiconductor device, it is to possess: the substrate of semiconductor element, semiconductor element mounted thereon and be set between semiconductor element and the substrate and the semiconductor element transom that semiconductor element is electrically connected with substrate; The semiconductor element transom is the hardening thing or the film like caking agent of above-mentioned adhesive composite.
Semiconductor device so is the hardening thing of above-mentioned adhesive composite because make the hardening thing of the adhesive composite that semiconductor element is electrically connected with substrate, so mass deviation is few, can demonstrate abundant stable properties.And, when the hardening thing of adhesive composite contains electroconductive particle, can reduce connection resistance, by mixing this electroconductive particle, can guarantee the electroconductibility between subtend semiconductor element and substrate fully.
According to the present invention, can be provided in low temperature can carry out very fast hardening treatment, the process time domain when carrying out hardening treatment wide, have the adhesive composite of abundant stable properties (bonding strength and connect resistance), and use its circuit connection material, the connection structure and the semiconductor device of circuit member.
Description of drawings
Fig. 1 represents the part sectional view of the embodiment that the connection of circuit member of the present invention is constructed.
The a series of block diagram of Fig. 2 junction circuit member.
Fig. 3 represents the part sectional view of one of them embodiment of semiconductor device of the present invention.
Nomenclature
1: the connection structure of circuit member, 2: semiconductor device, 5: the caking agent composition, 7: electroconductive particle, 10: the circuit transom, 11: the insulativity material, 20: the first circuit members, 21: the first circuit substrates, 22: the first circuit electrodes, 30: the second circuit member, 31: the second circuit substrate, 32: the second circuit electrode, 40: the film-shaped circuit transom, 50: semiconductor element, 60: substrate, 61: circuit pattern, 70: closed material, 80: the semiconductor element transom.
Embodiment
Below, in case of necessity with reference to the accompanying drawings, describe in detail, moreover in the accompanying drawing, same key element is with prosign about the suitableeest embodiment of the present invention, the repetitive description thereof will be omitted.In addition, the position relation that waits up and down, short of special requirement is just based on position relation represented on the accompanying drawing.And the dimension scale of accompanying drawing also is regardless of and is limited to illustrated ratio.In addition, " (methyl) acrylate " in the specification sheets of the present invention means " acrylate " and " methacrylic ester " corresponding with it; " (methyl) vinylformic acid " means " vinylformic acid " and " methacrylic acid " corresponding with it; " (methyl) acryl " means " acryl " and " methacryloyl " corresponding with it.
Adhesive composite
Adhesive composite of the present invention, contain have thermoplastic resin, the caking agent composition of free-radical polymerised compound, radical polymerization initiator, the ESR that above-mentioned caking agent composition carries out under 25 ℃ has signal in measuring.
Herein, the thermoplastic resin that the present invention is correlated with is used for bonding firm between the adhering object thing (following also only be called " by sticky object ").
Thermoplastic resin used in the present invention, not special restriction, can use known resin, particularly, can use for example polyamide-based, phenoxy resin class, poly-(methyl) esters of acrylic acid, polyimide, polyurethanes, polyester, polyvinylbutyral class etc., can be used alone or mix more than 2 kinds and use.And these resins also can contain siloxane bond or fluoro substituents at intramolecularly.These resins can be dissolved between institute's blended resin fully mutually, and perhaps to form the gonorrhoea state also applicable so long as produce microphase-separated.
In addition, to the restriction especially of the molecular weight of above-mentioned thermoplastic resin, the molecular weight of thermoplastic resin more can be healed greatly and be formed film described later easily, the melt viscosity that influences as the flowability of caking agent can be set in wide in range scope.If melt viscosity is set in wide in range scope, when being used for semiconductor element and liquid crystal cell etc. bonding, even between interelement and the wiring closet every narrow and smallization, can prevent further that caking agent is attached to surrounding member, can improve turnout.General weight-average molecular weight is preferably 5000～150000, is preferably 10000～80000 especially.Weight-average molecular weight is less than 5000, when then using as film described later, has film and forms the insufficient tendency of property, and weight-average molecular weight surpasses 150000, then has the tendency of intermiscibility variation of composition with other.
Moreover the weight-average molecular weight in this specification sheets is to abide by following condition to analyze via gel permeation chromatography (GPC), measures with following condition, uses the inspection amount line of polystyrene standard to calculate via converting.
The GPC condition
Use machine: the L-6000 of Hitachi type ((strain) Hitachi system, trade(brand)name)
Detector: L-3300RI ((strain) Hitachi system, trade(brand)name)
Tubing string: gelpack GL-R420+gelpack GL-R430+gelpack GL-R440 (adding up to 3) (Hitachi changes into industry (strain) system, trade(brand)name)
Eluat: tetrahydrofuran (THF)
Measure temperature: 40 ℃
Flow: 1.75ml/min
Free-radical polymerised compound used in the present invention, be have because granted certain energy produce free radical, polymerization forms the function of polymkeric substance by the chain reaction of this free radical compound, this Raolical polymerizable is generally speaking than cationoid polymerisation or anionoid polymerization is quicker reacts, therefore, use the present invention of free-radical polymerised compound, can in the relatively shorter time, carry out polymerization.
Free-radical polymerised compound used in the present invention; so long as having the compound of carbon-to-carbon double bond, the intramolecularly of (methyl) acrylic, (methyl) acryl or vinyl etc. gets final product; not special restriction; can use known compound, serve as preferred with the free-radical polymerised compound with (methyl) acryl again wherein.
The object lesson of free-radical polymerised compound, can enumerate for example epoxy (methyl) origoester acrylate, Padil (methyl) origoester acrylate, polyethers (methyl) origoester acrylate, the oligopolymer of polyester (methyl) origoester acrylate etc., trimethylolpropane tris (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, poly-alkane glycol two (methyl) acrylate, dicyclopentenyl (methyl) acrylate, two cyclopentenes oxygen base ethyl (methyl) acrylate, neopentyl glycol two (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, cyamelide modification 2 officials energy (methyl) acrylate, cyamelide modification 3 officials energy (methyl) acrylate, 2,2 '-two (methyl) acryloxy diethyl phosphoric acid ester, multifunctional (methyl) acrylic compound of 2-(methyl) acryloxy ethyl acid phosphoric acid ester etc. can use separately or mix in case of necessity more than 2 kinds and use.
Free-radical polymerised compound of the present invention so long as have (methyl) acryl as reactive base, needn't be selected by the material of sticky object, can be bonding securely., can be enumerated headed by the organic substrate of printed circuit board (PCB) and polyimide etc. by sticky object as this, and contain the metal of copper, aluminium etc. and ITO (indium tin oxide, indium tin oxide target), silicon nitride (SiN), silicon-dioxide (SiO
2) base material that constitutes of the material that waits.
The blending ratio of the free-radical polymerised compound in the adhesive composite of the present invention with respect to the thermoplastic resin of 100 mass parts, is preferably 50～250 mass parts, more preferably 60～150 mass parts.If the blending ratio of free-radical polymerised compound does not reach 50 mass parts, then have the tendency that the thermotolerance of the hardening thing of adhesive composite reduces, if surpass 250 mass parts, when then using adhesive composite, have the insufficient tendency of film shaped property as film described later.
In addition, adhesive composite of the present invention contains radical polymerization initiator.Free-radical polymerised compound, Once you begin Raolical polymerizable then carries out chain reaction, can harden securely, but produce relatively difficulty of free radical at first.Therefore, the present invention makes the radical polymerization initiator that containing the generation free radical of can low weightly changing places in the adhesive composite.
The radical polymerization initiator that the present invention is correlated with can use the known compound of the superoxide both known from previous technology and azo-compound etc.Particularly; can enumerate for example cumenyl new decanoate ester peroxide; 1; 1; 3; 3-tetramethyl butyl new decanoate ester peroxide; 1-cyclohexyl-1-methylethyl new decanoate ester peroxide; t-hexyl new decanoate ester peroxide; t-butyl peroxy neodecanoic acid ester; t-butyl peroxy trimethylacetic acid ester; 1; 1; 3; 3-tetramethyl butyl peroxidation-2-ethylhexanoate; 2; 5-dimethyl-2; 5-two (peroxidation of 2-ethyl hexanoyl base) hexane; t-hexyl peroxidation-2-ethylhexanoate; t-butyl peroxyization-2-ethylhexanoate; the new heptanoate of t-butyl peroxyization; t-amyl peroxyization-2-ethylhexanoate; two-t-butyl peroxyization, six hydrogen terephthalate; t-amyl peroxyization-3; 5; 5-tri-methyl hexanoic acid ester; 3-hydroxyl-1; 1-dimethylbutyl new decanoate ester peroxide; 1; 1; 3; 3-tetramethyl butyl peroxidation-2-ethylhexanoate; t-amyl peroxy neodecanoic acid ester; t-amyl peroxyization-2-ethylhexanoate; 2; 2 '-azo-group two-2; the 4-methyl pentane nitrile; 1; 1 '-azo-group two (1-acetoxyl group-1-diphenylphosphino ethane); 2; the two isopropyl cyanides of 2 '-azo-group; 2; 2 '-azo-group two (2-methylbutyronitrile); dimethyl-2; the two isopropyl cyanides of 2 '-azo-group; 4; 4 '-azo-group two (4-cyano group valeric acid); 1; 1 '-azo-group two (1-cyclohexane nitrile); t-hexyl peroxidation sec.-propyl monocarbonate; t-butyl peroxy toxilic acid; t-butyl peroxyization-3; 5; 5-tri-methyl hexanoic acid ester; t-butyl peroxy laurate; 2; 5-dimethyl-2; 5-two (peroxidation of 3-methyl benzoyl) hexane; t-butyl peroxyization-2-ethylhexyl monocarbonate; t-hexyl peroxide benzoate; 2; 5-dimethyl-2; 5-two (benzoyl peroxidation) hexane; t-butyl peroxy benzoic ether; dibutyl peroxidation trimethyladipic acid ester; t-amyl peroxy n-caprylic acid ester; the different pelargonate of t-amyl peroxyization; t-amyl peroxy benzoic ether etc.; these compounds can use separately, also can mix more than 2 kinds.
Wherein, preferably 1 minute half life temperature is 90～175 ℃, and weight-average molecular weight is 180～1000 peroxyester derivative or diacyl peroxide.Herein, " 1 minute half life temperature " is meant that the transformation period becomes 1 minute temperature, and " transformation period " is meant that compound concentrations reduces to the time of a half of initial value.1 minute half life temperature of radical polymerization initiator is 90～175 ℃, and is relatively more following with prior art then by the resulting hardening thing of adhesive composite of the present invention, can possess excellent connection resistance.
The blending ratio of the radical polymerization initiator in the adhesive composite of the present invention in addition is the thermoplastic resin with respect to 100 mass parts, is preferably 0.05～30 mass parts, more preferably 0.1～20 mass parts.During blending ratio less than 0.05 mass parts of radical polymerization initiator, then have the tendency of the polymerization velocity reduction of radical polymerization, the tendency of the hardening thing under-ageing of adhesive composite, if radical polymerization initiator surpasses 30 mass parts, then have the tendency of the storage stability reduction of adhesive composite.
Moreover the energy form of being granted among the present invention is not particularly limited, but can enumerate heat, electron beam, γ line, ultraviolet ray, infrared rays, visible light, microwave etc.
The caking agent composition that the present invention was correlated with contains above-mentioned thermoplastic resin, free-radical polymerised compound and radical polymerization initiator, and has signal in the measurement of the ESR under 25 ℃ of conditions.
ESR is the abbreviation of spectrum (Electron Spin Resonance), can detect existing free radical kind in the test portion by this measurement.
" ESR has signal in measuring " among the present invention is meant that having spin density is 1.0 * 10
16The signal strength that spins/g is above.Spin density can by with the known 4-hydroxyl-2,2,6 of concentration, the signal strength of 6-tetramethyl piperidine-when 1-oxygen base is the standard test portion obtains after relatively.
The signal of ESR in this specification sheets can be by being calculated with following conditioned measurement.
Use machine: ESP350 (BRUKER corporate system, trade(brand)name)
Microwave frequency is counted gauge: HP5351B (HEWLETT PACKARD corporate system, trade(brand)name)
Magnetometer: ER035M (BRUKER corporate system, trade(brand)name)
Near central magnetic field: the 3490G
Magnetic field scanning scope: 200G
Modulation: 100kHz, 1G
Microwave: 9.8GHz, 1mW
Sweep time: 83.886s * 4 time
Time constant: 327.68ms
Cavity: TM100, round tube type
During ESR measures, test portion is not subjected to shape and phase state (solid, liquid, gas) restriction, can carry out ESR under the state of film like yet and measure, still, the test portion of film like then wherein radical pair shows anisotropy in magnetic field, shows the asymmetrical signal of wide scope.Herein, the present invention carries out ESR with the solution that test portion is dissolved in solvent to measure, employed solvent, so long as solubilized test portion person get final product, and not special restriction, but preferred chloroform, the present invention uses chloroform.
In addition, test portion is through dissolved solution, but insolubles such as filtered particles and stopping composition in case of necessity also can only be measured filtered liquid, measures temperature and can be normal temperature, but when measuring ESR with film like, in order to resolve also available low-temperature measurement easily, the present invention then measures ESR at 25 ℃.
Adhesive composite is except the caking agent composition, and when also containing electroconductive particle, caking agent composition itself has signal in the ESR measurement, so it is preferred, based on the metal ingredient that uses in the electroconductive particle, thus signal had in the ESR measurement, but be difficult to obtain effect of the present invention in such cases.
Contain and have so adhesive composite of the caking agent composition of the signal of ESR, the free radical that demonstrates wherein to be contained surely exists.Generally speaking, radical polymerization is because the growth free radical has high reactivity, so be difficult to controlled polymerization speed, but, when adhesive composite contains the free radical (hereinafter referred to as " stabilized radical ") of stable existence, may command radical polymerization carry out speed.The stabilized free compound, because can be described as stable free radical compounds, so have very high reactivity with initial free radical kind or the terminal free radical of polymerization, therefore, stabilized radical almost can be held back the free radical that produces from radical polymerization initiator fully, by this, when stabilized radical is residual, can suppress beginning and carrying out of radical polymerization fully, after stabilized radical is consumed fully, carry out radical polymerization.Its result can guarantee to begin to the adhesive composite mobile time between the sclerosis beginning from adding thermocompression bonded, but the expansion process time domain at present for the effect that stabilized radical produced, and is regardless of the above-mentioned effect of inferring that is limited to.
Caking agent composition in the adhesive composite, the g value in ESR measures is preferably 2.0000～2.0100, and this g value is resultant by following formula (A).
g＝hν/βH (A)
Herein, in the formula (A), h represents quantum of action (6.6261 * 10
-34Js), ν represents microwave frequency number (Hz), and β represents Bohr magnetron (9.2740 * 10
-24J/T), H represents resonant field (T).
Moreover, the signal of ESR is based on the interaction between nuclear rotation or free radical, can give the splitted signal, make that the heart is a resonant field among the splitted signal this moment, in addition, when giving the signal of wide scope and complicated signal, the heart among between the signal of the signal of minimum magnetic field side and upfield side as the heart among the signal, is resonant field.
In ESR measured, the g value was 2.0000～2.0100, represented that then the πDian Zi that generally speaking the caking agent composition contains organic compound is the free radical kind.Adhesive composite of the present invention is by having so free radical kind, effect that can more effective performance expansion process time domain, and the g value is 2.0040～2.0090, then can more resultful expansion process time domain, so preferred.
For the caking agent composition is had as above-mentioned g value, can enumerate the method for the free radical kind of adding transition metal and ferromagnetism body, stable organic compound, but adhesive composite of the present invention most preferably adds stable free radical compound.
Stable free radical compound used in the present invention is that the organic compound of free radical kind gets final product so long as have πDian Zi, and not special restriction can not used known compound.Stable free radical compound can enumerate and have nitrogen oxygen (aminoxyl) base that (＞N-O) oxynitrides, its object lesson can be enumerated the represented oxynitrides of following general expression (B).
[changing 1]
Herein, in the formula (B), R
1Alkoxyl group, ester group or the acyloxy of the alkyl of expression hydrogen atom, hydroxyl, amido, carboxyl, cyano group, isothiocyanic acid ester group, carbon number 1～10, aryl, carbon number 1～20, X
1, X
2, X
3And X
4The alkyl of representing hydrogen atom or carbon number 1～5 independently of one another.
More specifically, oxynitrides can be enumerated following formula (1)～(16) represented compound, can enumerate again on the side chain of polyamine, polyester, polyacrylic ester etc., imports from the represented compound of above-mentioned general expression (B) to break away from R
1Or X
4The 1 valency base that is become is as substituent polymkeric substance.
[changing 2]
The aforementioned stable free radical compounds can use a kind separately, or makes up more than 2 kinds and use.
The blending ratio of stable free radical compound is the thermoplastic resin with respect to 100 mass parts, is preferably 0.01～10 mass parts, more preferably 0.02～0.5 mass parts.If this blending ratio is less than 0.01 mass parts, and the above-mentioned effect that then is difficult to oxynitrides is produced is proved effective, if surpass 10 mass parts, then has the tendency of the hardening reduction of adhesive composite.
Adhesive composite of the present invention preferably contains electroconductive particle, by containing electroconductive particle, can give this adhesive composite electroconductibility, therefore, adhesive composite of the present invention can be used as in the electrician's industry of circuit electrode and semi-conductor etc. and the conductive adhesive of electronics industry and uses.
Electroconductive particle used in the present invention gets final product so long as have the electroconductibility that can be electrically connected, not special restriction, and electroconductive particle can be enumerated metal or the carbon that for example contains Au, Ag, Ni, Cu and scolder etc.In addition, also can be with dielectric glass, pottery, plastics etc. is nuclear, goes up the material of above-mentioned metallics of lining and carbon in this nuclear, this metal of preferable alloy wherein as hot melt property, or when being nuclear with plastics, coated metal or carbon.These situations, because make its distortion easier by the hardening thing of heating and pressurization adhesive composite, with between the electrode electrically connected time, the contact area of increase electrode and adhesive composite can improve interelectrode electroconductibility.
And adhesive composite of the present invention also can contain the booklike particle of the surface of above-mentioned electroconductive particle with linings such as macromolecule resins.The electroconductive particle of the state of booklike particle is made an addition in the adhesive composite, even then increase the combined amount of electroconductive particle, because use resin-coated,, also can improve the insulativity between telegraph circuit so can more suppress to result from short circuit that contact produces between electroconductive particle.Moreover, can use a kind or mix such electroconductive particle and the booklike particle of use more than 2 kinds separately.
The median size of electroconductive particle, by the viewpoint of dispersiveness and electroconductibility, preferred 1～18 μ m.The blending ratio of electroconductive particle in addition, with respect to the thermoplastic resin of 100 mass parts, preferred 0.5～30 mass parts.And the blending ratio of this electroconductive particle, with respect to the adhesive composite of 100 volume %, be preferably 0.1～30 volume %, more preferably 0.1～10 volume %.The blending ratio of electroconductive particle then has the tendency that can't obtain sufficient electroconductibility during less than 0.1 volume %, surpasses 30 volume %, has the tendency that causes short circuit.In addition, the blending ratio of electroconductive particle (volume %) makes the volume of presclerotic each composition of adhesive composite decide when being based on 23 ℃.The volume of each composition can utilize proportion and is converted into volume by weight, in addition, in putting the container of the appropriate solvent of moistening this composition (water, ethanol class etc.) fully into, knocks down this composition, can calculate by the method for coming out from the volume calculation that is increased.
In addition, adhesive composite of the present invention, the caking agent auxiliary of interpolation coupler that also can be suitable and adaptation rising agent, flow agent etc., by this, and can more significant performance effect of the present invention, can give better adaptation and operability.Particularly, can enumerate alkoxyl silicone alkane derivatives and silicon amine alkane derivatives, wherein, preferably add the represented compound of following formula (C).
[changing 3]
Herein, in the formula (C), R
6, R
7And R
8Represent the alkyl of hydrogen atom, carbon number 1～5, the alkoxyl group of carbon number 1～5, the alkoxy carbonyl or the aryl of carbon number 1～5 independently of one another, R
9Expression hydrogen atom or methyl, p represents 1～10 integer.
And, in this general expression (C), work as R
6Be the alkyl or aryl of carbon number 1～5, R
7And R
8The alkoxyl group of representing carbon number 1～3 independently of one another, p are 2～4 o'clock, because cementability and connection resistance are more excellent, so preferred.Moreover the represented compound of general expression (C) can use a kind separately, also can mix more than 2 kinds.
In addition, bonding auxiliary can be phosphate derivative, this phosphate derivative, particularly, the represented compound of preferred following general expression (D).
[changing 4]
Herein, in the formula (D), R
2Expression hydrogen atom or methyl, n represents 1～10 integer, m represents 1 or 2 integers.These bonding auxilliary rib agent can be used a kind separately, or the compound that mixes more than 2 kinds uses.
In addition adhesive composite of the present invention can add other material in case of necessity, for example can and use the cementability rising agent of the crosslinking rate that improves caking agent, can more improve bonding strength by this.Promptly; except free-radical polymerised compound with (methyl) acryl; also can add have allyl group, the functional group's of free redical polymerization that maleic anhydride contracts imido grpup, vinyl etc. compound; particularly; can enumerate N-ethene imidazoles, N-vinylpyridine, N-V-Pyrol RC, N-ethylene carboxamide, N-ethene hexanolactam, 4; two (the N of 4 '-vinylidene; accelerine), N-ethene ethanamide, N; N-DMAA, N-N-isopropylacrylamide, N, N-diethyl acrylamide etc.Moreover these cementability rising agents can use a kind or mix more than 2 kinds separately.
Adhesive composite of the present invention, can and with the fluidity improving agent of simple function (methyl) acrylate etc., by this, can more improve the flowability of the adhesive composite when connecting.Particularly; can enumerate tetramethylolmethane (methyl) acrylate; 2-cyano ethyl (methyl) acrylate; cyclohexyl (methyl) acrylate; two cyclopentenes (methyl) acrylate; two cyclopentenes oxygen base ethyl (methyl) acrylate; 2-(2-ethoxy ethoxy) ethyl (methyl) acrylate; 2-ethoxyethyl group (methyl) acrylate; 2-ethylhexyl (methyl) acrylate; n-hexyl (methyl) acrylate; 2-hydroxyethyl (methyl) acrylate; hydroxypropyl (methyl) acrylate; isobornyl (methyl) acrylate; isodecyl (methyl) acrylate; iso-octyl (methyl) acrylate; n-lauryl (methyl) acrylate; 2-methoxy ethyl (methyl) acrylate; 2-phenoxy group ethyl (methyl) acrylate; tetrahydrofurfuryl (methyl) acrylate; 2-(methyl) propionyloxy ethyl phosphonic acid ester; N; N-dimethyl amido ethyl (methyl) acrylate; N, N-dimethyl amido propyl group (methyl) acrylate; (methyl) acryloyl morpholine.Moreover these fluidity improving agents can use a kind or mix more than 2 kinds and to use separately.
And; adhesive composite of the present invention also can and be used the rubber based material that improves stress mitigation and cementability; particularly; can enumerate polyisoprene; polyhutadiene; the C-terminal polyhutadiene; the C-terminal polyhutadiene; 1; the 2-polyhutadiene; C-terminal 1; the 2-polyhutadiene; C-terminal 1, the 2-polyhutadiene; acrylic rubber; styrene butadiene rubbers; the C-terminal styrene butadiene rubbers; acrylonitrile-butadiene rubber; polymer ends contains carboxyl; hydroxyl; the acrylonitrile-butadiene rubber of (methyl) acryl or morpholinyl; carboxylated nitrile rubber; C-terminal gathers (oxygen base propylene); alkoxysilane group terminal poly-(oxygen base propylene); poly-(oxygen base four is stretched methyl) glycol; the polyolefine glycol; poly--6-caprolactone.
Above-mentioned rubber based material, the viewpoint by cementability improves preferably contains the high functional group's of polarity cyano group, the glue rubber of carboxyl at side chain or end, by the viewpoint that flowability more improves, preferred liquid.Particularly, can enumerate aqueous acrylonitrile-butadiene rubber, polymer ends contains the aqueous acrylonitrile-butadiene rubber of carboxyl, hydroxyl, (methyl) acryl or morpholinyl, aqueous carboxylated nitrile rubber.The acrylonitrile content of polar group is preferably 10～60 quality % of these rubber based material integral body, moreover these rubber based materials can use a kind or mix more than 2 kinds and use separately.
And adhesive composite of the present invention can and be forbidden the additive of agent etc. therefore, can more improving the adhesive composite storage stability with the polymerization of representatives such as t-butyl-catechol, t-butylphenol, p-methoxyphenol.
When adhesive composite of the present invention is aqueous at normal temperature, can use by the thickener shape, when normal temperature is solid down, heating back pasty stateization, or use solvent that its pasty stateization also can.Spendable solvent, so long as with adhesive composite reaction, and demonstrate sufficient solvability and get final product, do not limit especially, preferably its boiling point is 50～150 ℃ under normal pressure.If boiling point is less than 50 ℃, then solvent volatilizees easily in room temperature, has the tendency of operability variation when making the aftermentioned film; Boiling point surpasses 150 ℃ in addition, and then solvent is difficult to volatilization, has the tendency that can't obtain competent bonding strength after bonding.
Adhesive composite of the present invention, use after can forming film like, this film like caking agent, can be by will in bonding composition, adding the mixed solution of solvent etc., coat on the separability base material of fluorine resin film, polyethylene terephthalate, release paper etc., or make to be placed on after the above-mentioned mixed solution of impregnation such as tNonwovens and peel off on the base material, remove and make after desolvating etc.So adhesive composition makes film like, and operability is more convenient.
In addition, make film behind the interpolation electroconductive particle in the adhesive composite of the present invention, then can be made into the anisotropic conductive film, this anisotropic conductive film, for example be placed on the base material relatively to electrode between, can the person's of gluing two electrodes by heating and pressurizing, be electrically connected simultaneously., form the substrate of electrode herein, can be fit to use each combination of compound of the organism, glass/epoxy etc. of the inanimate matter, polyimide, polycarbonate etc. of semi-conductor, glass, pottery etc.
And, adhesive composite of the present invention can and carry out bonding with heating and pressurization, the not special restriction of Heating temperature, but the temperature with 50～190 ℃ is preferred, pressure so long as do not damage by the scope of sticky object gets final product, generally be preferably 0.1～10MPa, such heating and pressurization are preferably carried out in 0.5 second～120 seconds scope.
By the present invention, low temperature can be provided at and hardening treatment can be carried out fully apace, the process time domain when carrying out hardening treatment is wide, have abundant stable properties (bonding strength and connect resistance), and the fully excellent adhesive composite of storage stability.
And, adhesive composite of the present invention, because can carry out hardening treatment fully apace at low temperature, the process time domain when carrying out hardening treatment is wide, have abundant stable properties (bonding strength and connect resistance), so applicable to using as circuit connection material.When the circuit electrode of first circuit member is electrically connected with the circuit electrode of second circuit member, make under these the state of circuit member subtend configuration, grant a wherein side circuit electrode with adhesive composite of the present invention, can be electrically connected by Raolical polymerizable with the opposing party's circuit electrode.Use so adhesive composite as circuit connection material, then can be electrically connected at short notice, even process temperature when connecting and time change, also can become the connection material of the stability of characteristics of bonding strength and connection resistance etc., in addition, also circuit capable of inhibiting connect material hardening thing through the time characteristic reduce.And this circuit connection material can demonstrate the anisotropy of electrical connection if contain electroconductive particle, can be used as the anisotropic conductive circuit connection material that circuit electrode uses and uses.
Above-mentioned circuit connection material, the circuit connection material by sticky object that can be used as the different different kind of thermal expansivity uses, particularly, circuit connection material, the CSP that can be used as representatives such as anisotropically conducting adhesive, silver-colored thickener, silver-colored film uses with the semiconductor element adhesives of representatives such as bottom filler material, LOC patch with elastomerics, CSP.
The connection structure of circuit member
Then, the better suited embodiment of constructing about the connection of using circuit member of the present invention is described.Fig. 1 represents one of them the summary sectional view of embodiment of the connection structure of circuit member of the present invention, as shown in Figure 1, the connection structure 1 of the circuit member of present embodiment, first circuit member 20 and the second circuit member 30 that possess mutual subtend, between first circuit member 20 and the second circuit member 30, the circuit transom 10 that is used for being electrically connected these is set.First circuit member 20 possesses first circuit substrate 21 and is formed at first circuit electrode 22 on the interarea 21a of circuit substrate 21.Moreover, on the interarea 21a of circuit substrate 21, can form insulation layer (not shown) according to situation.
On the other hand, second circuit member 30 possesses second circuit substrate 31 and is formed at second circuit electrode 32 on the interarea 31a of second circuit substrate 31.In addition, on the interarea 31a of circuit substrate 31, can form insulation layer (not shown) according to situation.
Moreover, when circuit transom 10 does not contain electroconductive particle 7, by making first circuit electrode 22 and second circuit electrode 32 directly contact or close electrical connection the very, make the electric current of the desirable amount that flows between first circuit electrode 22 and the second circuit electrode 32.
The manufacture method of the connection structure of circuit member
Then, about the manufacture method of the connection of foregoing circuit member structure, describe with reference to Fig. 2 of block diagram.
At first, prepare above-mentioned first circuit member 20 and film-shaped circuit connection material 40 (with reference to figure 2 (a)).Film-shaped circuit connection material 40 is circuit connection material to be configured as film like become.Circuit connection material herein contains caking agent composition 5, electroconductive particle 7, and caking agent composition 5 herein uses the relevant caking agent composition of the invention described above.Moreover even circuit connection material does not contain electroconductive particle 7, this circuit connection material still can be used as the insulativity caking agent, and to be used in anisotropic conductive bonding, is called NCP (Non-Conductive Paste, non-conductive paste) sometimes especially.In addition, when circuit connection material contained electroconductive particle 7, this circuit connection material was ACP (Anisotropic Conductive Paste, anisotropic conductive is stuck with paste) sometimes.
The thickness of film-shaped circuit connection material 40 is preferably 10～50 μ m, if the thickness deficiency of film-shaped circuit connection material 40 10 μ m, then have the tendency of 22,32 circuit connection material lack of fills of circuit electrode, in addition, if surpass 50 μ m, the adhesive composite that then has 22,32 of circuit electrodes can't be got rid of fully, the tendency of guaranteeing to become difficulty of the conducting that circuit electrode is 22,32.
Then, with film-shaped circuit connection material 40, be positioned on the face of formation circuit electrode 22 of first circuit member 20, moreover, when film-shaped circuit connection material 40 is gone up attached to support (not shown), make film-shaped circuit connection material 40 sides, under the situation of first circuit member 20, be placed on first circuit member 20.At this moment, because film-shaped circuit connection material 40 is a film like, thus processing ease, therefore, can make film-shaped circuit connection material 40 easily between first circuit member 20 and second circuit member 30, and can carry out the attended operation of first circuit member 20 and second circuit member 30 easily.
Then, pressurization film-shaped circuit connection material 40 on the arrow A of Fig. 2 (a) and B direction, film-shaped circuit connection material 40 vacations are connected (with reference to Fig. 2 (b)) in first circuit member 20, at this moment, can pressurize while heating, but Heating temperature is the adhesive composite hardened temperature that does not make in the film-shaped circuit connection material 40, promptly produces the low temperature of temperature of free radical than radical polymerization initiator.
Then, shown in Fig. 2 (c),, make the second circuit circuit face under the situation of first circuit member 20, be placed on film with on the circuit connection material 40 with second circuit member 30.Moreover, when film-shaped circuit connection material 40 is gone up attached to support (not shown), after Zhi Teti peeled off second circuit member 30 is placed on the film-shaped circuit connection material 40.
Then, heat film-shaped circuit connection material 40 on one side, on the arrow A of Fig. 2 (c) and B direction, pressurize on one side across first and second circuit member 20,30, the Heating temperature of this moment, can produce the temperature of free radical for radical polymerization initiator, by this, produce free radical in the radical polymerization initiator, make free-radical polymerised compound begin polymerization, like this, make film-shaped circuit connection material 40 carry out hardening treatment, carry out real connection, obtain the connection structure of circuit member as shown in Figure 1.
For example, Heating temperature is 90～200 ℃, and for example 1 second～10 minutes tie-time, such condition can suitably be selected according to use, adhesive composite, circuit member, can carry out post-hardening in case of necessity.
As the above-mentioned practice, make the connection structure of circuit member, in the connection structure of resulting circuit member, electroconductive particle 7 is contacted with circuit electrode 22,32 both sides of mutual subtend, can reduce the connection resistance of 22,32 of circuit electrodes fully.
In addition, heating by film-shaped circuit connection material 40, under the state that the distance between circuit electrode 22 and the circuit electrode 32 fully diminishes, becoming insulativity material 11, the first circuit members 20 after 5 sclerosis of caking agent composition is connected across circuit transom 10 securely with second circuit member 30.Promptly, in the connection structure of resulting circuit member, circuit transom 10 is made of the hardening thing of the circuit connection material that contains above-mentioned adhesive composite, so improve the bonding strength of the circuit transom 10 of circuit member 20 or 30 fully, and can reduce by 22,32 connections of circuit electrode resistance fully.In addition, the connection of this circuit member structure can continue this state between long-term.So, the connection of resulting circuit member structure, prevent fully 22,32 of circuit electrodes distance through the time change the long-term reliability excellence of the electrical characteristic that circuit electrode is 22,32.
Moreover caking agent composition 5 can contain at least by adding the radical polymerization initiator of thermogenesis free radical, only also can use the radical polymerization initiator that produces free radical with rayed to replace this radical polymerization initiator.At this moment, during the hardening treatment of film-shaped circuit connection material 40, also the available light irradiation replaces heating.Other can use the radical polymerization initiator that produces free radical by ultrasound, hertzian wave etc. in case of necessity.In addition, also available epoxy and potentiality stiffening agent as the hardening composition in the caking agent composition 5.
In addition, above-mentioned embodiment, use film-shaped circuit connection material 40 to make the connection structure of circuit member, but also can use the circuit connection material that does not form film like to replace film-shaped circuit connection material 40, make circuit connection material be dissolved in solvent this moment, with wherein the after drying of this solution coat, can make 20,30 of first and second circuit members across circuit connection material in first circuit member 20 or second circuit member 30.
In addition, can use other electro-conductive material to replace electroconductive particle 7,, can enumerate the metal wire of the carbon of particle shape or staple fibre shape, the Ni line of plating Au etc. etc. as other electro-conductive material.
Semiconductor device
Then, embodiment about semiconductor device of the present invention is described.Fig. 3 is the summary sectional view of one of them embodiment of this semiconductor device of expression, as shown in Figure 3, the semiconductor device 2 of present embodiment possesses semiconductor element 50 and the substrate 60 that becomes semi-conductive support member, between semiconductor element 50 and the substrate 60, the semiconductor element transom 80 that these are electrically connected is set.In addition, semiconductor element transom 80 is laminated on the interarea 60a of substrate 60, and semiconductor element 50 more is laminated on this semiconductor element transom 80.
The not special restriction of the material of semiconductor element 50, but can use the semiconductor element of 4 families of silicon, germanium, the III-V compound semiconductor element of GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, InAs, GaInP, AlInP, AlGaInP, GaNAs, GaNP, GaInNAs, GaInNP, GaSb, InSb, GaN, AlN, InGaN, InNAsP etc., the II-VI compound semiconductor element of HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, ZeTe etc., and CuInSe various semiconductor elements such as (ClS).
Semiconductor element transom 80 contains insulativity material 11 and electroconductive particle 7.Electroconductive particle 7 not only is disposed between semiconductor element 50 and the circuit pattern 61, also is disposed between semiconductor element 50 and the interarea 60a.In the semiconductor device 2 of present embodiment, semiconductor element 50 and circuit pattern 61, be electrically connected across electroconductive particle 7, therefore the connection resistance of semiconductor element 50 and circuit pattern 61 is reduced fully, so flowing of the electric current that semiconductor element 50 and circuit pattern are 61 can be carried out smoothly, the function that can bring into play semi-conductor fully and had.In addition, be above-mentioned blending ratio, can demonstrate the anisotropy of electrical connection by making this electroconductive particle 7.
Moreover, when semiconductor element transom 80 does not contain electroconductive particle 7,, can make its directly contact or very closely be electrically connected in order to make the flow electric current of desirable amounts of semiconductor element 50 and circuit pattern 61.
Semiconductor element transom 80, because constituted by the hardening thing that contains above-mentioned caking agent composition, so improve the bonding strength of the semiconductor element transom 40 of semiconductor element 50 and substrate 60 fully, and can reduce the resistance that is connected of semiconductor element 50 and 61 of circuit patterns fully, in addition, this state can continue between long-term, so, can improve the long-term reliability of the electrical characteristic of 60 of semiconductor element 50 and substrates fully.
The manufacture method of semiconductor device
Then explanation is about the manufacture method of above-mentioned semiconductor device.
At first, prepare to form circuit pattern 61 substrate 60, be connected material with the film like semiconductor element.Film like semiconductor element connection material connects material forming with semiconductor element and is formed by film like.Semiconductor element herein connects material and contains caking agent composition 5, electroconductive particle 7, and caking agent composition 5 herein uses the relevant caking agent composition of the invention described above.Moreover when semiconductor element connected material and do not contain electroconductive particle 7, this semiconductor element connected material and can be used as the insulativity caking agent to be used in anisotropic conductive bonding, is called NCP (Non-Conductive Paste) sometimes especially.In addition, when semiconductor element connection material contained electroconductive particle 7, this semiconductor element connection material was ACP (AnisotropicConductive Paste) sometimes.
The thickness that the film like semiconductor element connects material is preferably 10～50 μ m, when the film like semiconductor element connects the thickness less than 10 μ m of material, then have the tendency that 50 semiconductor elements of circuit pattern 61 and semiconductor element are connected the material lack of fill, in addition, surpass 50 μ m, then the adhesive composite of 50 of circuit pattern 61 and semiconductor elements can't be got rid of fully, the tendency that the guaranteeing of the conducting that circuit pattern 61 and semiconductor element are 50 becomes difficult.
Then, the film like semiconductor element is connected material, be positioned on the face of formation circuit pattern 61 of substrate 60, moreover, when film like semiconductor element connection material is gone up attached to support (not shown), make the film like semiconductor element connect the material side, under the situation of substrate 60, be placed on the substrate 60.At this moment, because it is film like that the film like semiconductor element connects material, thus processing ease, therefore, can make the film like semiconductor element connect material between substrate 60 and semiconductor element 50 easily, and can carry out the attended operation of substrate 60 and semiconductor element 50 easily.
Then, pressurization film like semiconductor element connects material, the film like semiconductor element is connected the material vacation be fixed in substrate 60, at this moment, can pressurize while heating, but Heating temperature is the adhesive composite hardened temperature that does not make in the film like semiconductor element connection material, promptly produces the low temperature of temperature of free radical than radical polymerization initiator.
Then, semiconductor element 50 is placed on the film like semiconductor element to be connected on the material, moreover the film like semiconductor element connects material when going up attached to support (not shown), makes semiconductor element 50 be placed on the film like semiconductor element after Zhi Teti is peeled off and connects on the material.
Then, heat the film like semiconductor element on one side and connect material, pressurize across substrate 60 and semiconductor element 50 on one side, the Heating temperature of this moment can produce the temperature of free radical for radical polymerization initiator, by this, produce free radical in the radical polymerization initiator, make free-radical polymerised compound begin polymerization, like this, make the film like semiconductor element connect material and carry out hardening treatment, carry out real connection.
Heating temperature for example is 90～200 ℃, and for example 1 second～10 minutes tie-time, these conditions can suitably be selected according to use, adhesive composite, substrate, can carry out post-hardening in case of necessity.
Then, carry out the resin-encapsulated semiconductor element in case of necessity, at this moment, resin-sealing material is formed at the surface of substrate, but also can with the face of the surface opposite side of substrate on form resin-blocked material, can obtain semiconductor device as shown in Figure 3.
As the above-mentioned practice, make semiconductor device, in the resulting semiconductor device, electroconductive particle 7 is contacted with semiconductor element 50 both sides with the circuit pattern 61 of mutual subtend, can reduce the resistance that is connected of circuit pattern 61 and 50 of semiconductor elements fully.
In addition, connect material heating by the film like semiconductor element, under the state that the distance between circuit pattern 61 and the semiconductor element 50 fully diminishes, become insulativity material 11 after 5 sclerosis of caking agent composition, substrate 60 is connected across semiconductor element transom 80 securely with semiconductor element 50.Promptly, in the resulting semiconductor device, semiconductor element transom 80 is made of the hardening thing that the semiconductor element that contains above-mentioned adhesive composite connects material, so improve the bonding strength of substrate 50 or semiconductor element 50 and semiconductor element transom 80 fully, and can reduce the connection resistance of 61 of semiconductor element 50 and circuit patterns fully.In addition, this semiconductor device can continue this state between long-term.So, resulting semiconductor device prevent fully 50 of circuit patterns 61, semiconductor element distance through the time change the long-term reliability excellence of the electrical characteristic that circuit pattern 61, semiconductor element are 50.
Moreover in the above-mentioned embodiment, caking agent composition 5 can use the material that contains at least by the radical polymerization initiator that adds the thermogenesis free radical, only also can use the radical polymerization initiator that produces free radical by rayed to replace this radical polymerization initiator.At this moment, when the film like semiconductor element connected the hardening treatment of material, also the available light irradiation replaced heating.Other can use the radical polymerization initiator that produces free radical by ultrasound, hertzian wave etc. in case of necessity, and in addition, also available epoxy and potentiality stiffening agent are as the hardening composition in the caking agent composition 5.
In addition, in the above-mentioned embodiment, use the film like semiconductor element to connect material and make semiconductor device, but also can use the semiconductor element that does not form film like to connect material and replace film like semiconductor element connection material, this moment, semiconductor element connected material dissolves in solvent, after one of them of substrate 60 or semiconductor element 50, drying can make 50 of substrate 60 or semiconductor elements connect material across semiconductor element with this solution coat.
In addition, can use other electro-conductive material to replace electroconductive particle 7,, can enumerate the metal wire of the carbon of particle shape or staple fibre shape, the Ni line of plating Au etc. etc. as other electro-conductive material.
More than, illustrate about better suited embodiment of the present invention, but the present invention and be regardless of and be limited to these embodiments.
Embodiment
Below, by the present invention of embodiment more detailed description, but the present invention and be regardless of and be limited to these embodiment.
The modulation of phenoxy resin solution
Phenoxy resin (Union Carbide corporate system with 40 mass parts, trade(brand)name: PKHC, weight-average molecular weight 45000), the methyl ethyl ketone that is dissolved in 60 mass parts of putting into Glass Containers is (with the pure pharmaceutical worker's industry of light corporate system, trade(brand)name: 2-butanone, purity 99%) in, the phenoxy resin solution of modulation solid composition 40 quality %.
Synthesizing of Padil resin
Poly adipate succinic acid ester (polybuthylene adipate diol) (Aldrich corporate system with 450 mass parts, weight-average molecular weight 2000), polyoxy tetramethylene glycol (polyoxytetramethyleneglycol) (the Aldrich corporate system of 450 mass parts, weight average molecular weight 2000), 1 of 100 mass parts, 4-butyleneglycol (Aldrich corporate system), the methyl ethyl ketone that is dissolved in 4000 mass parts is (with the pure pharmaceutical worker's industry of light (thigh) system, trade(brand)name: 2-butanone, purity 99%) in, obtain reaction solution after adding the diphenylmethanediisocyanate (Aldrich corporate system) of 390 mass parts this moment, then, make this reaction with 70 ℃ of reactions 60 minutes, obtain the Padil resin.Moreover oil bath is used in the temperature control of this moment, and (Ah taste's outer (thigh) system, trade(brand)name: HOB-50D) carry out, the weight average molecular weight of resulting Padil resin is 350,000 via the gpc measurement result.
The preparation of free-radical polymerised compound
Prepare isocyanuric acid ester EO modification diacrylate (East Asia synthetic (thigh) system, trade(brand)name: M-215), Padil acrylate (common prosperity society chemistry (thigh) system, trade(brand)name: AT-600) and 2-(methyl) acryloxy ethyl phosphonic acid ester (common prosperity society chemistry (thigh) system, trade(brand)name: P-2M).
The preparation of radical polymerization initiator
T-hexyl peroxidation-2-ethylhexanoate (Japanese grease (thigh) system, trade(brand)name: perhexyl O).
The preparation of stable free radical compound
Prepare 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (TEMPOL, rising sun electrochemical industry (thigh) system, trade(brand)name: LA7-RD), 4-ethanamide-2,2,6,6,-tetramethyl piperidine-1-oxygen base (TEMPOL-NHAc, Tokyo changes into industry (thigh) system), 2,2,6,6 ,-tetramethyl piperidine-1-oxygen base (the pure pharmaceutical worker's industry of TEMPO and light (thigh) system).
The making of electroconductive particle
On the surface of polystyrene particle, be provided with thickness reach 0.2 μ m by nickel became layer, more on this surface by the layer that nickel became, the layer by Jin Suocheng that thickness reaches 0.02 μ m is set, so the practice is made the electroconductive particle of median size 4 μ m and proportion 2.5.
In the phenoxy resin solution (phenoxy resin that contains 25 mass parts) of above-mentioned 62.5 mass parts, mix the Padil resin of the solid composition of 25 mass parts, as the perhexyl O of 3 mass parts of the P-2M of the AT-600 of the M-215 of 25 mass parts of free-radical polymerised compound, 25 mass parts, 5 mass parts, radical polymerization initiator and as the TEMPOL of 0.2 mass parts of stable free radical compound.Obtain adhesive composite behind the above-mentioned electroconductive particle of dispersing and mixing in the resulting solution, the blending ratio of electroconductive particle is 1.5 volume % for the total amount of adhesive composite.
Then, with resultant adhesive composite, use apparatus for coating (the smart machine of Kang Jing (thigh) system, trade(brand)name: SNC-S3.0) filmed after coating the fluorine resin film of thickness 80 μ m, then the warm air drying by this is filmed and carries out 10 minutes with 70 ℃ obtains the film-shaped circuit connection material that thickness is 15 μ m.
Replace the TEMPOL of 0.2 mass parts except mixing TEMPOL-NHAc as 0.2 mass parts of stable free radical compound, all the other are the practice similarly to Example 1, obtains film-shaped circuit connection material.
Embodiment 3
Replace the TEMPOL of 0.2 mass parts except mixing TEMPO as 0.2 mass parts of stable free radical compound, all the other are the practice similarly to Example 1, obtains film-shaped circuit connection material.
Embodiment 4
Replace 0.2 mass parts except mixing 0.05 mass parts TEMPOL as stable free radical compound, all the other are the practice similarly to Example 1, obtains film-shaped circuit connection material.
Comparative example 1
Except not mixing the TEMPOL as stable free radical compound, all the other are the practice similarly to Example 1, obtains film-shaped circuit connection material.
The ratio of mixture of each composition of the foregoing description and the resulting adhesive composite of comparative example is shown in table 1.
Table 1
ESR measures
With resulting film-shaped circuit connection material, (the METLLER corporate system, trade(brand)name: UMX2) weighing 70mg makes an addition to the interior back of Glass Containers of having placed 1ml chloroform (with the pure pharmaceutical worker's industry of light (thigh) system, superfine reagent, purity 98%) and stirs with electronic balance.Like this practice obtains film-shaped circuit connection material is dissolved in the solution of chloroform, then this solution is filtered with filter paper (quantitative paper No.5C, ADVANTEC Japan corporate system), obtains containing the filtered liquid of caking agent composition.
Filtered liquid is bubbled after the degassing with nitrogen, put to the flat grid of ESR, use the ESR device to count gauge HP5351B (HEWLETT PACK ARD corporate system), magnetometer ER035M (BRUKER corporate system) and round tube type TM100 cavity with ESP350 (BRUKER corporate system), microwave frequency, measure the ESR of caking agent composition, obtain the g value, the ESR measuring condition of this moment is set near the central magnetic field 3490G, magnetic field scanning scope 200G, modulation 100kHz, 1G, microwave 9.8GH, 1mW, sweep time 83.886s * 4 times, time constant 327.68ms, 25 ℃.
In addition, by with the known 4-hydroxyl-2,2,6 of the concentration of reference material, the signal strength of 6-tetramethyl piperidine-1-oxygen base during as the standard test portion relatively carries out the measurement of spin density, resulting result is shown in table 2 through the above-mentioned practice.
Table 2
| |
|
Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| The g value | 2.0055 | 2.0053 | 2.0054 | 2.0055 | - |
| Spin density (spins/g) | 7.7×10 18 | 8.6×10 18 | 5.0×10 17 | 5.0×10 17 | 0 |
The caking agent composition of embodiment 1～3 is measured through ESR, obtains having the signal of 2.0000～2.0100 g value, and on the other hand, the caking agent composition of comparative example 1 can't be observed signal in the ESR measurement.
The making of the connection structure of circuit member
At first, preparation has glass substrate (ito substrate, thickness 1.1mm, surface resistivity 20 Ω/) of thin layer of flexible circuit board (FPC substrate), whole indium tin oxide target (ITO) that forms 0.2 μ m of copper circuit distribution of 500 live width 25 μ m, spacing 50 μ m, thickness 18 μ m, then, between these FPC substrates and ito substrate, dispose the resulting film-shaped circuit connection material of the above-mentioned practice.Then, use thermocompression bonded device (type of heating: the constant type of hot pressing temperature, Toray Engineering limited-liability company system), under the condition of fixed temperature, 3MPa, carry out 10 seconds heating and pressurizing at these stacked direction, the practice by this, the width that making is electrically connected FPC substrate and the ito substrate hardening thing by circuit connection material reach 2mm circuit member be connected structure, moreover above-mentioned fixed temperature is to adopt 3 patterns of 160 ℃, 180 ℃ and 200 ℃.
Connect the measurement of resistance
With the connection resistance between the circuit in the connection structure of resulting circuit member, (1) firm bonding back, and the hot and humid groove of (2) bonding back 80 ℃, 95%RH in carry out humidity test in 120 hours after, with volt ohm-milliammeter (ADVANTEST corporate system, trade(brand)name: TR6848) measure.Moreover resistance value is represented with average (the x+3 σ) of 150 of the resistance between adjacent circuit, and the result is shown in table 3.
The measurement of bonding strength
With the strength of joint between the circuit in the connection structure of resulting circuit member, (1) firm bonding back, and the hot and humid groove of (2) bonding back 80 ℃, 95%RH in carry out humidity test in 120 hours after, peeling off method according to 90 degree of JIS-Z0237 measures, assesses, herein, the measuring apparatus of bonding strength uses TENSILON UTM-4 (peeling rate 50mm/min, 25 ℃, Japan ボ one Le De ウ イ Application corporate system), and the result is shown in table 3.
Table 3
When using the film-shaped circuit connection material of embodiment 1～4, in each Heating temperature, the connection resistance after firm bonding back and the humidity test demonstrates the less value of deviation, demonstrates good electrical characteristic for the Heating temperature of wide scope.
With respect to this, when using the film-shaped circuit connection material of comparative example 1,, after the humidity test, connect resistance and further rise again along with Heating temperature uprises and connects resistance and significantly rise.
Utilizability on the industry
According to the present invention, low temperature can be provided at and cure process can be carried out fully fast, the adhesive composite that process time domain when carrying out cure process is wide, have fully stable characteristic (bonding intensity and contact resistance), and use its circuit connection material, connection structure and the semiconductor device of circuit member.
Claims (12)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP302944/2005 | 2005-10-18 | ||
| JP2005302944 | 2005-10-18 | ||
| JP182388/2006 | 2006-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101995600A Division CN102277091A (en) | 2005-10-18 | 2006-08-24 | Adhesive composition, circuit connecting material, connection structure of circuit connectors and semiconductor devices |
| CN2011101035061A Division CN102222649A (en) | 2005-10-18 | 2006-08-24 | Adhesive composition,circuit connecting material, connection structure of circuit connectors and semiconductor devices |
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| CN101292006A true CN101292006A (en) | 2008-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200680038502 Pending CN101292006A (en) | 2005-10-18 | 2006-08-24 | Adhesive composition, circuit connecting material, circuit member connection structure, and semiconductor device |
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| CN (1) | CN101292006A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103858217A (en) * | 2011-09-09 | 2014-06-11 | 汉高股份有限及两合公司 | Sealant composition for electronic device |
| CN105473674A (en) * | 2013-08-30 | 2016-04-06 | 迪睿合株式会社 | Radical polymerizable adhesive composition and method for producing electrical connector |
| CN110556344A (en) * | 2012-02-24 | 2019-12-10 | 日立化成株式会社 | Adhesive for semiconductor, method for manufacturing semiconductor device, and semiconductor device |
-
2006
- 2006-08-24 CN CN 200680038502 patent/CN101292006A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103858217A (en) * | 2011-09-09 | 2014-06-11 | 汉高股份有限及两合公司 | Sealant composition for electronic device |
| CN110556344A (en) * | 2012-02-24 | 2019-12-10 | 日立化成株式会社 | Adhesive for semiconductor, method for manufacturing semiconductor device, and semiconductor device |
| CN105473674A (en) * | 2013-08-30 | 2016-04-06 | 迪睿合株式会社 | Radical polymerizable adhesive composition and method for producing electrical connector |
| CN110591570A (en) * | 2013-08-30 | 2019-12-20 | 迪睿合株式会社 | Radical polymerization type adhesive composition and method for producing electric connection body |
| CN110591570B (en) * | 2013-08-30 | 2022-03-11 | 迪睿合株式会社 | Radical polymerization type adhesive composition and method for producing electric connection body |
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