CN1923939B - Semiconductor device, adhesive, and adhesive film - Google Patents

Semiconductor device, adhesive, and adhesive film Download PDF

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Publication number
CN1923939B
CN1923939B CN2006100998102A CN200610099810A CN1923939B CN 1923939 B CN1923939 B CN 1923939B CN 2006100998102 A CN2006100998102 A CN 2006100998102A CN 200610099810 A CN200610099810 A CN 200610099810A CN 1923939 B CN1923939 B CN 1923939B
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China
Prior art keywords
tackiness agent
weight
film
mentioned
epoxy resin
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Expired - Fee Related
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CN2006100998102A
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CN1923939A (en
Inventor
山本和德
岛田靖
神代恭
稻田祯一
栗谷弘之
金田爱三
富山健男
野村好弘
细川羊一
桐原博
景山晃
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Publication of CN1923939A publication Critical patent/CN1923939A/en
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  • Engineering & Computer Science (AREA)
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  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention aims at improving the temperature resisting cycle characteristics after mounting and moisture absorption resiting reflow characteristics of a chip-mounted semiconductor, and provides an adhesive which functions as a bonding member (3) to be used when a semiconductor chip (6) is mounted on an organic supporting substrate (4) and which has storage moduli at 25 DEG C and at 260 DEG C as measured with a dynamic visco-elasticity measuring instrument of 10-2000 MPa and 3-50 MPa, respectively, a double-coated adhesive film produced therewith, a semiconductor device, an semiconductor chip mounting substrate, and methods of manufacturing these products.

Description

Semiconductor device, tackiness agent and bonding film
The application be Hitachi Chemical Co., Ltd. on October 8th, 1997 apply for, application number is 200410062123.4, denomination of invention is divided an application for the application for a patent for invention of " semiconductor device, tackiness agent and bonding film ".
Technical field
The present invention relates to semiconductor device and the tackiness agent and the bonding film that are suitable in the manufacturing of above-mentioned semiconductor device, using.
Background technology
In the last few years; Miniaturized and work high frequencyization along with e-machine; Load their semiconductor packages; Requirement is assembled on substrate with high-density, and along with the progress of miniaturized and lightness, people develop the compact package bottom, that be referred to as miniature BGA (BGA) and CSP (chip size packages) that an outside terminal area array (area array) is configured to encapsulation shape.
Following structure is adopted in these encapsulation: be loaded into chip on organic substrate of glass fiber reinforced epoxy resin substrate with 2 layers of wire structures or the polyimide substrate with 1 layer of wire structures etc. through the insulativity tackiness agent earlier; Couple together the terminal of the terminal of chip one side and running board one side with wire bonds or TAB inner bonding modes such as (band carry automated bonding) again; With epoxy be sealing material or epoxy to be liquid sealing material with connection portion and chip surface partly reach to end face part seals, be configured on the circuit board back side with making metal terminal area array shapes such as solder ball.And e-machine then adopts the mode with solder reflow, with high-density, encapsulates the fit on the substrate that total ground surface mounts e-machine to a plurality of these.
But; An example as the insulativity tackiness agent that in these encapsulation, uses; Usefulness with the dynamic viscoelastic device measure, at the liquid-state epoxy resin tube core tackiness agent of 25 ℃ storage elastic moduluss greater than 3000Mpa; After being assembled to encapsulation on the substrate, the connection reliability of solder ball connection portion (2 times one sides) is poor, and heatproof degree circulation safety degenerates.
In addition; In other instance, as the insulativity tackiness agent, the someone has proposed storage elastic modulus in the time of 25 ℃ less than the liquid state silicon series elastomerics of 10MPa; Though this elastomerics is fine aspect above-mentioned heatproof degree cyclicity; But it is poor to the cementability on circuit board surface but to exist when high temperature, and the also bad problem of anti-moisture absorption backflow property.
Particularly concerning anti-backflow property; In these two instances, be coated to a liquid insulativity tackiness agent in the process on organic substrate, also observed and be easy to be involved in bubble and be starting point with the bubble;, moisture absorption develops into the crack when refluxing, the bad pattern that the organic radical small drum for marking time is got up.
In addition, along with the progress of e-machine, the loading density of electronic unit uprises, and can expect that the assembling of semiconductor bare chip on printed wiring board of low price also obtained progress.
Substrate is used in assembling as semi-conductor chip, the ceramic substrate of always many employing aluminum oxide etc.Its reason is: because the thermal expansivity of semi-conductor chip is little of about 4ppm/ ℃; In order to ensure connection reliability; Will seek to use the less assembling of thermal expansivity to use substrate; Simultaneously, be easy to also will seek to use the higher assembling of thermal conductivity ratio to use substrate for the heat that semi-conductor chip is produced to the outside heat radiation.When semi-conductor chip being assembled on such ceramic substrate, use with the fluid binder of silver paste as representative.
In addition, film adhesive is used in flexible printed circuit board etc., and uses mostly with acrylonitrile-butadiene rubber and as the tackiness agent of staple be.
In research as the printed circuit board associated material; Material as the solder heat resistance property after the raising moisture absorption; Have the spy and open the disclosed tackiness agent that contains acrylic resin, epoxy resin, polymeric polyisocyanate and mineral filler in the clear 60-243180 communique; Also have in addition and open the spy that disclosed two ends that have urethane bond in acrylic resin, epoxy resin and the molecule that contain are the compound of primary amine and the tackiness agent of mineral filler in the clear 61-138680 communique, still, under the stringent condition of PCT (pressure cooking test) processing etc.; It is big to carry out under the situation of wet fastness experiment deterioration, is inappropriate.
If when assembling semiconductor chips on ceramic substrate, use the silver paste tackiness agent; Then exist owing to the sedimentation of silver fillers is arranged thereby disperse heterogeneity, the storage stability that must be careful silver paste, the operation property of semi-conductor chip assembling and the problem of the LOC relatively poor grades of relatively getting up such as (lead on chip, LOCs).
In addition, although film adhesive use with the adhesive composition of acrylonitrile-butadiene rubber mostly as staple,, but exist the descend shortcoming of big, electrocorrosion-resisting property difference etc. of bonding force after the long time treatment at high temperature.Under the stringent condition of the PCT processing of particularly in semi-conductor connection part reliability is estimated, using etc., the deterioration when carrying out anti-moisture test is big.
If with the spy open clear 60-243180 communique, the spy opens disclosed tackiness agent in the clear 61-138680 communique, when under the stringent condition that PCT handles etc., carrying out anti-moisture test, deterioration is greatly inappropriate.
Be assembled to semi-conductor chip under the situation on the printed circuit board with these tackiness agents as printed circuit board connection material, the difference of the thermal expansivity between semi-conductor chip and the printed circuit board is big, when refluxing, will produce the crack, so can not use.In addition, the deterioration when under the stringent condition that carries out that temperature cycling test or PCT handle etc., carrying out anti-moisture test is big, thereby can not use.
Summary of the invention
The present invention provides the semiconductor device of bonding semi-conductor chip of this bonding film of a kind of tackiness agent, bonding film and use and running board.Above-mentioned tackiness agent and bonding film; Have necessary thermotolerance, electrocorrosion-resisting property and wet fastness when the semi-conductor chip that the difference of thermal expansivity is big is assembled on the printed circuit board of glass fiber reinforced epoxy resin substrate or flexible substrate etc.; When particularly under the stringent condition that PCT handles etc., carrying out anti-moisture test, its deterioration is little.
In addition, the present invention also provides a kind of semiconductor device, its method of manufacture and is applicable to substrate for mounting semiconductor chip, its method of manufacture, tackiness agent and the double-sided adhesive film of making above-mentioned semiconductor device.Through tackiness agent mounting semiconductor chip to the organic system support substrate; And outside terminal is arranged in the semiconductor device of area array shape on substrate back; The characteristic of above-mentioned semiconductor device is: the circulative while of heatproof degree after improving assembling, also improve anti-moisture absorption backflow property.
Semiconductor device of the present invention be a kind of through adhesive member the semiconductor device of mounting semiconductor chip to the organic system support substrate; It is characterized in that: form the wiring of regulation in the mounting semiconductor chip side of above-mentioned organic system support substrate; Opposition side area array shape ground with the mounting semiconductor chip side of above-mentioned organic system support substrate forms outside terminal for connecting; The cloth bundle of lines semi-conductor chip terminal and the said external terminal for connecting of afore mentioned rules couple together; At least be to carry out resin-sealed to the connection portion between the wiring of above-mentioned semi-conductor chip terminal and regulation; And above-mentioned adhesive member possesses binder layer, and 25 ℃ the storage elastic modulus that the use Measurement of Dynamic Viscoelasticity device of above-mentioned tackiness agent is measured is 10～2000MPa, and 260 ℃ storage elastic modulus is 3～50MPa.
Substrate for mounting semiconductor chip of the present invention; It is a kind of substrate for mounting semiconductor chip that loads the organic system substrate of semi-conductor chip through adhesive member; It is characterized in that: form the wiring of regulation in any at least side of the opposition side of the mounting semiconductor chip side of above-mentioned organic system substrate and mounting semiconductor chip side; With the opposition side of the mounting semiconductor chip side of above-mentioned organic system substrate; Area array shape ground forms outside terminal for connecting, and above-mentioned adhesive member possesses binder layer, and 25 ℃ the storage elastic modulus that the cured article of above-mentioned tackiness agent uses the Measurement of Dynamic Viscoelasticity device to measure is 10～2000MPa; At 260 ℃ storage elastic moduluss is 3～50MPa, and above-mentioned adhesive member forms on the position of the regulation on the above-mentioned organic system substrate with the size of regulation.
The method of manufacture of substrate for mounting semiconductor chip of the present invention is characterized in that, comprises the size that the adhesive member film is cut into regulation, is hot-pressed onto on the organic system substrate.Above-mentioned organic system substrate forms the wiring of regulation in any at least side of the opposition side of mounting semiconductor chip side and mounting semiconductor chip side, at the outside terminal for connecting of the opposition side area array shape ground of mounting semiconductor chip side formation.Above-mentioned adhesive member film is the adhesive member that possesses binder layer; 25 ℃ the storage elastic modulus that the cured article of tackiness agent uses the Measurement of Dynamic Viscoelasticity device to measure is 10-2000MPa; And 260 ℃ storage elastic modulus is 3-50MPa, and above-mentioned tackiness agent is in the semi-cured state that thermal discharge reaches the sort of degree of 10-40% of total curing exotherm amount when measuring with DSC (differential calorimeter).
The method of manufacture of semiconductor device of the present invention; It is characterized in that, comprise following operation: bondingly on the substrate for mounting semiconductor of organic system substrate possessing the operation of the adhesive member of binder layer, load semi-conductive operation through adhesive member, make operation that the wiring of afore mentioned rules is connected with semi-conductor chip terminal and said external terminal for connecting, at least resin-sealed operation carried out in the connection portion between the wiring of above-mentioned semi-conductor chip terminal and regulation; Wherein, Above-mentioned organic system substrate; Form the wiring of regulation in any at least side of the opposition side of mounting semiconductor chip side and mounting semiconductor chip side; Opposition side area array shape ground in the mounting semiconductor chip side forms outside terminal for connecting, and 25 ℃ the storage elastic modulus that the cured article of above-mentioned tackiness agent uses the Measurement of Dynamic Viscoelasticity device to measure is 10-2000MPa, and 260 ℃ storage elastic modulus is 3-50MPa.
Tackiness agent of the present invention is made up of following A～D component:
E, a kind of tackiness agent; For (1) epoxy resin and solidifying agent 100 weight parts thereof; Contain: (2) contain (methyl) glycidyl acrylate; Be glycidyl acrylate and/or SY-Monomer G 2～6 weight %, Tg (second-order transition temperature) more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (3) curing catalyst 0.1～5 weight part more than 800,000.
F, a kind of tackiness agent; For (1) epoxy resin and solidifying agent 100 weight parts thereof; Contain: (2) and epoxy resin have intermiscibility and weight-average molecular weight at 10～40 weight parts of the high molecular weight resin more than 30,000; (3) contain (methyl) glycidyl acrylate 2～6 weight %, Tg (second-order transition temperature) more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (4) curing catalyst 0.1～5 weight part more than 800,000.
G, a kind of tackiness agent; For (1) epoxy resin and resol 100 weight parts; Contain: (2) contain (methyl) glycidyl acrylate 2～6 weight %, Tg more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (3) curing catalyst 0.1～5 weight part more than 800,000.
H, a kind of tackiness agent; For (1) epoxy resin and resol 100 weight parts; Contain: (2) phenoxy resin 10～40 weight parts; (3) contain (methyl) glycidyl acrylate 2～6 weight %, Tg more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (4) curing catalyst 0.1～5 weight part more than 800,000.
Double-sided adhesive film of the present invention has the 3-tier architecture of following E～H:
The double-sided adhesive film of E, a kind of 3-tier architecture; It is to use the thermotolerance thermoplastic film to be core; Has a kind of like this tackiness agent on the two sides of core: for (1) epoxy resin and solidifying agent 100 weight parts thereof; Contain: (2) contain (methyl) glycidyl acrylate 2～6 weight %, Tg (second-order transition temperature) more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 1 00～300 weight parts and (3) curing catalyst 0.1～5 weight part more than 800,000.
The double-sided adhesive film of F, a kind of 3-tier architecture; It is to use the thermotolerance thermoplastic film to be core; Has a kind of like this tackiness agent on the two sides of core: for (1) epoxy resin and solidifying agent 100 weight parts thereof; Contain: (2) and epoxy resin have intermiscibility and weight-average molecular weight at 10～40 weight parts of the high molecular weight resin more than 30,000; (3) contain (methyl) glycidyl acrylate 2～6 weight %, Tg (second-order transition temperature) more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (4) curing catalyst 0.1～5 weight part more than 800,000.
The double-sided adhesive film of G, a kind of 3-tier architecture; It is to use the thermotolerance thermoplastic film to be core; Has a kind of like this tackiness agent on the two sides of core: for (1) epoxy resin and resol 100 weight parts; Contain: (2) contain (methyl) glycidyl acrylate 2～6 weight %, Tg more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (3) curing catalyst 0.1～5 weight part more than 800,000.
The double-sided adhesive film of H, a kind of 3-tier architecture; It is to use the thermotolerance thermoplastic film to be core; Has a kind of like this tackiness agent on the two sides of core: for (1) epoxy resin and resol 100 weight parts; Contain: (2) phenoxy resin 10～40 weight parts; (3) contain (methyl) glycidyl acrylate 2～6 weight %, Tg more than-10 ℃ and weight-average molecular weight containing epoxy group(ing) acrylic copolymer 100～300 weight parts and (4) curing catalyst 0.1～5 weight part more than 800,000.
In semiconductor device of the present invention, the wiring of regulation can directly link to each other with the semi-conductor chip terminal with inside bonding mode of wire bonds or TAB (tape automated bonding) etc.
In semiconductor device of the present invention; Adhesive member is preferably film like; Adhesive member possesses binder layer, as the resinous principle of tackiness agent, can use contain epoxy resin, contain the epoxy group(ing) PEMULEN TR2, the material of epoxy curing agent and epoxy resin cure promotor.
Adhesive member preferably has a kind of like this structure: use second-order transition temperatures such as polyimide, polyethersulfone, polyamide-imide or polyetherimde films at the thermotolerance thermoplastic film more than 200 ℃ as core, on the two sides of this core, form binder layer.Also can use liquid crystalline polymer film as the thermotolerance thermoplastic film.Remaining quantity of solvent in the binder layer is preferably below 5 weight %.
In substrate for mounting semiconductor chip of the present invention; Adhesive member is preferably film like; Adhesive member possesses binder layer; As the resinous principle of tackiness agent, can use contain epoxy resin, contain the epoxy group(ing) PEMULEN TR2, the material of epoxy curing agent and epoxy resin cure promotor.
Adhesive member preferably has a kind of like this structure: use second-order transition temperatures such as polyimide, polyethersulfone, polyamide-imide or polyetherimde films at the thermotolerance thermoplastic film more than 200 ℃ as core, on the two sides of this core, form binder layer.As the thermotolerance thermoplastic film, also can use liquid crystalline polymer film.Remaining quantity of solvent in the binder layer is preferably below 5 weight %.
The adhesive member that on the regulation position on the organic system substrate, forms; Can use the film that becomes prescribed level with punching press with die stamping; The adhesive member that on the regulation position on the organic system substrate, forms; Be that above-mentioned tackiness agent is in the adhesive member film that thermal discharge reaches the semi-cured state of 10～40% the sort of degree of total curing exotherm amount when measuring with DSC, it is cut into after the size of regulation, be hot-pressed onto on the above-mentioned organic system substrate.
In the method for manufacture of substrate for mounting semiconductor chip of the present invention; Can be with after the precision positioning of the difference of the adhesive member film after cutting off; Carry out bonding temporarily with thermocompressor; After carrying a plurality of adhesive member films on the organic system substrate of putting in groups, handle mould with already heated release surface and push, carry out bonding totally.Release surface is handled the surperficial release materials of mould, at least a in preferably polytetrafluoroethylene and the siloxanes.Before the adhesive member film cuts off operation, can also increase by one at least and remove the electrostatic eliminostatic operation that the adhesive member film takes place in carrying.
In the method for manufacture of semiconductor device of the present invention, can be below substrate for mounting semiconductor chip a side and this two sides of semi-conductor chip one side heat, and make the temperature of chip one side higher at least.
Tackiness agent of the present invention preferably uses with the state that thermal discharge reaches 10～40% the sort of degree of total curing exotherm amount when measuring with DSC; When measuring with the Measurement of Dynamic Viscoelasticity device; The storage elastic modulus of tackiness agent cured article; Being 10～2000MPa at 25 ℃ preferably, is 3～50MPa at 260 ℃.
For adhesive resin composition 100 parts by volume, 2～20 parts by volume, the preferred aluminum oxide of mineral filler, silicon-dioxide are used in mineral filler.
On basement membrane, form tackiness agent and process bonding film, semi-conductor chip is connected with running board, just can obtain semiconductor device with this bonding film.
Double-sided adhesive film of the present invention preferably makes tackiness agent be in the state that thermal discharge reaches 10～40% the sort of degree of total curing exotherm amount when measuring with DSC and uses; When measuring with the Measurement of Dynamic Viscoelasticity device; The storage elastic modulus of tackiness agent cured article; Being 10～2000MPa at 25 ℃ preferably, is 3～50MPa at 260 ℃.For adhesive resin composition 100 parts by volume, 2～20 parts by volume, the preferred aluminum oxide of mineral filler, silicon-dioxide are used in mineral filler.
The thermotolerance thermoplastic film that in core, uses; Its second-order transition temperature is preferably more than 200 ℃; As second-order transition temperature at this thermotolerance thermoplastic film more than 200 ℃, preferred polyimide, polyethersulfone, polyamide-imide or polyetherimde films.Thermotolerance thermoplastic film as used in the core also can use liquid crystalline polymer film.
In order to solve said in the prior art problem; At first; Through the insulativity tackiness agent mounting semiconductor chip to organic circuit board; Couple together chip one side terminal and running board one side terminal with the gold wire bonding technology then; Solder ball outside terminal area array shape ground on substrate back is arranged,, resolved gimmick with the FEM elastoplasticity and investigate the physical properties of use therein insulativity tackiness agent and the relation between the heatproof degree cyclicity after the motherboard assembling for the semiconductor packages of such formation.
Consequently: the elastic modulus E of insulativity tackiness agent descends greatly more; Then by the CTE of chip (thermal linear expansion coefficient: 3.5ppm) with the CTE of motherboard (14～18ppm) difference produced, substrate solder ball external terminal portions divides suffered stress more little; If the elastic modulus E of measuring with the Measurement of Dynamic Viscoelasticity device is below the 2000MPa, preferably below 1000MPa; Then the equivalent deformation of the solder ball terminal of most peripheral part is very little; Even if can know and apply mechanically the Coffin-Manson rule, also there is 1000 times the fatigue lifetime more than the circulation in-55 ℃～125 ℃ temperature cycle.
Otherwise, common epoxy be the elastic modulus E of die bonding agent more than 3000MPa, can know existing problem aspect the heatproof degree circulation safety of solder ball.
On the other hand; If the elastic modulus E of insulativity tackiness agent is dropped to below the 10MPa of the sort of degree of silicone elastomer; Then 260 ℃ of the ceiling temperatures of reflux temperature; Elastic modulus E will become that surpass to measure the sort of degree of boundary ground little, becomes to losing the zone as the function of strength member, just can not expectation can also keep bonding between substrate surface and the silicon.The temperature dependency of shear adhesive strength has the tendency identical with the temperature dependency of Young's modulus, and the high more then intensity of temperature is more little.In other words, if the elastic modulus E under 260 ℃ of reflux temperatures is not more than 3MPa at least, then can not the expectation shear adhesive strength.If 260 ℃ of reflux temperatures and chip or substrate between the interface on produced and peeled off, then will after cause in the temperature cycling test implemented the spun gold broken string defective or in anti-moisture test, cause the corrosion broken string defective.
Therefore; Be loaded into the insulativity tackiness agent (tackiness agent cured article) on organic circuit board to chip as being used for; Young's modulus during its normal temperature is in the scope of 10～2000MPa, and is preferably in the scope of 50～1500MPa, preferred in the scope of 100～1000MPa; What use as the Young's modulus under 260 ℃ of reflux temperatures is the Young's modulus in this scope of 3～50MPa, can know that this is in order to make it to satisfy the condition of heatproof degree cyclicity and anti-moisture absorption backflow property.
Learn that from the result that the temperature dependent various thermosetting resins with above-mentioned Young's modulus are explored containing the epoxy group(ing) PEMULEN TR2 is the appropriate tackiness agent that can embody the rerum natura of this scope.
In addition, as the important factor that makes anti-moisture absorption backflow deterioration, be the bubble that on the interface between organic circuit board and the insulativity tackiness agent, takes place.Under the common mode that the liquid thermosetting adhesive that drips on a small quantity applies, be easy to be involved in bubble, become the reason that when moisture absorption refluxes, produces crack and substrate protuberance.
Therefore; Be processed into film like to the above-mentioned epoxy group(ing) PEMULEN TR2 that contains; Make remaining quantity of solvent be lower than 5% carrying out drying, when preferably being lower than 2%, being in the size that the bonding film that reaches the B stage solidification state of total curing exotherm amount 10～40% when measuring with DSC (differential calorimeter) cuts into regulation; Paste on organic circuit board with thermocompressor, obtain substrate for mounting semiconductor.
Then, process chip loading and hot pressing, wire bonds operation, sealing process obtain encapsulating finished product.
The encapsulation that obtains like this is difficult to take place gap and bubble, still on the interface between chip and the substrate; The inventor finds, when chip hot pressing, not only from substrate for mounting semiconductor one side; Under the situation about also heating from the two sides of chip one side; On the interface between chip and the tackiness agent, just be difficult to take place the gap, between the wiring portion of substrate, could imbed resin fully, just can improve anti-moisture absorption backflow property.In addition, be lower than 5% if be controlled to be the remaining quantity of solvent of above-mentioned bonding film, preferably be lower than 2%, then finding in the solidification process of bonding film not can bubbling, can not make the reduction of anti-moisture absorption backflow property.
Application with bonding film of above-mentioned rerum natura; Not only for gold wire bonding technology chip one side terminal with running board one side terminal couples together and make outside terminal on substrate back, be arranged in the semiconductor packages of area array shape; And also have same effect and effect to the encapsulation (encapsulation of chip one side terminal and the direct-connected mode of running board one side terminal) that chip one side terminal and running board one side terminal couple together, and satisfiedly simultaneously have whole heatproof degree cyclicity and an anti-moisture absorption backflow property that bonds to semi-conductor chip through tackiness agent this area array package of the structure on organic circuit board for inside bonding mode with TAB (band carry an automated bonding).Outside terminal for connecting area array shape ground promptly disposes on whole of substrate back latticedly or is configured to one at peripheral part and is listed as or ordered series of numbers.
As organic circuit board, can be FR-4 substrates such as BT (bismaleimides) substrate, glass fiber reinforced epoxy resin substrate, also can be the polyimide film substrate, to not restriction of substrate material.In addition, above-mentioned bonding film also can form with the thermosetting adhesive with above-mentioned rerum natura, but in order to ensure the rigidity when rolling or transmitting as carrier band, also can be formed on the 3-tier architecture that the two sides of polyimide film applies.The contriver finds that this structure has effect identical with said structure and effect.
The method of bonding bonding film is on organic circuit board, cuts into bonding film the shape of regulation earlier, and then, the correct position of film alignment with after cutting off is hot-pressed onto on organic circuit board.
The cutting-off method of bonding film; So long as correctly cut into the method for the shape of regulation to film, how all right, but if consider operation property and adhibit quality; Then preferably cut off bonding film, be pressed onto on organic circuit board then temporarily or formally with press tool.
The hot pressing of bonding film after the cut-out on organic circuit board; Have after cutting off bonding film; After attractive material is adsorbed onto on the hot pressing member and has carried out correctly position alignment, be pressed onto on organic circuit board earlier temporarily, carry out formal hot pressed method with thermocompressor then; With earlier add press fit after with the die stamping bonding film with punching press temporarily, carry out formal hot pressed method with thermocompressor then.In addition, under situation, go back handlebar do not carry out hot pressed method with not adding any change with the good self adhesive tape of press tool punching press with press tool.
Bond on organic circuit board as long as add the self adhesive tape that it is good that press fit makes punching press temporarily, do not have what special qualifications.
When carrying out formal hot pressing, preferred 30～250 ℃ of the hot pressing temperature of bonding film, more preferred 70～150 ℃.Hot pressing temperature is lower than 30 ℃, and not only the Young's modulus of bonding film is high, and the pressurization bed knife is low, and when pressurization was fixed to the wiring top of organic circuit board, the imbedibility of tackiness agent around wiring was bad, is undesirable.If hot pressing temperature is more than 250 ℃, then wiring can be oxidized, and organic circuit board meeting deliquescing, aspect operation property, is unfavorable.
Preferred 1～the 20kg/cm of formal hot pressed pressure 2, more preferred 3～10kg/cm 2If hot pressing pressure is less than 1kg/cm 2, then the pressurization bed knife of bonding film is bad with the imbedibility around the wiring, if greater than 20kg/cm 2, then tackiness agent can spill into outside the position of regulation, and the dimensional precision of tackiness agent is degenerated.
Formal hot pressing time so long as it is just passable to carry out the bonding time with above-mentioned hot pressing temperature and hot pressing pressure, but is considered operation property, preferred 0.3～60 second, and more preferred 0.5～10 second.
Thermocompressor is used in formal hot pressing, preferably the releasing agent processing is carried out on the surface and is made tackiness agent not bond to the lip-deep thermocompressor of thermocompressor, and particularly using the thermocompressor of tetrafluoroethylene, siloxanes is being preferred aspect release property and the operation property.
The epoxy resin that uses among the present invention gets final product so long as after curing, present the resin of bonding effect.Use the above epoxy resin of 2 functional groups, preferred molecular weight is less than 5000, and more preferred molecular weight is less than 3000.If particularly use molecular weight to be lower than 500 bisphenol A-type or Bisphenol F type liquid resin, because the flowability can improve lamination the time, so be ideal.Molecular weight is lower than 500 bisphenol A-type or Bisphenol F type liquid resin, is sold with the trade(brand)name of EPIKOTE 807, EPIKOTE 827, EPIKOTE 828 by Yuka ShellEpoxy Co., Ltd..In addition, Dow chemistry Amada Co., Ltd. also sells with the trade(brand)name of D.E.R.330, D.E.R.331, D.E.R.361.Toto Kasei KK is also selling with the trade(brand)name of YD128, YDF170 in addition.
As epoxy resin, turn to purpose with high Tg (second-order transition temperature) and can add polyfunctional epoxy resin, as polyfunctional epoxy resin, can enumerate solvable fusible phenol aldehyde type epoxy resin, the solvable phenol aldehyde type epoxy resin of cresols etc.
Solvable fusible phenol aldehyde type epoxy resin, Nippon Kayaku K. K sells with the trade(brand)name of EPPN-201.And the solvable phenol aldehyde type epoxy resin of cresols is just by the trade(brand)name of Sumitomo Chemical Company Ltd with ESCN-001, ESCN-195, and sold with the trade(brand)name of EOCN1012, EOCN1025, EOCN1027 by above-mentioned Nippon Kayaku K. K.As epoxy resin; (for example can also use brominated epoxy resin, brominated bisphenol a type epoxy resin; Sumitomo Chemical Company Ltd makes; Commodity are called ESB-400), the solvable fusible phenol aldehyde type epoxy resin of bromination (for example, Nippon Kayaku K. K produces, and commodity are called BREN-105, BREN-S) etc.
As curing agent for epoxy resin; Normally used solidifying agent can be used, amine, polymeric amide, acid anhydrides, polysulphide, boron trifluoride and this example can be enumerated as the bisphenols A that contains the compound of 2 above phenol property hydroxyls at an intramolecularly, bisphenols F, bisphenols S etc.Electrocorrosion-resisting property during particularly owing to moisture absorption is outstanding, preferably uses this solvable fusible phenol aldehyde type epoxy resin as resol, bis-phenol phenolic resin varnish type epoxy resin, the solvable phenol aldehyde type epoxy resin of cresols etc.
This preferred solidifying agent is sold with the trade(brand)name of PHENORITE LF2882, PHENORITE LF2822, PHENORITE TD-2090, PHENORITE TD-2149, PHENORITE VH4150, PHENORITEVH4170 by Dainippon Ink. & Chemicals Inc.In addition, as solidifying agent, can use this tetrabromobisphenol class A (Teijin Chemicals, Ltd. produces, and commodity are called FIREGUARD FG-2000) etc. as the bromination oxybenzene compound.
It is preferred using curing catalyst with solidifying agent.As curing catalyst, preferably use various imidazoles.As imidazoles, can enumerate glyoxal ethyline, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenyl trimellitic acid imidazoles etc.
Imidazoles changes into Co., Ltd. by four countries and sells with the trade(brand)name of 2E4MZ, 2PZ-CN, 2PZ-CNS at present.
As having intermiscibility and weight-average molecular weight at the high molecular weight resin more than 30,000, can enumerate phenoxy resin, high molecular expoxy resin, ultra-high molecular weight epoxy resin, contain strong polar functional group rubber, contain reactive rubber of strong polar functional group or the like with epoxy resin.Flexibility when solidifying with improvement for the crease that reduces the tackiness agent of B in the stage, can make weight-average molecular weight is more than 30,000.The above-mentioned reactive rubber that contains strong polar functional group can be enumerated the rubber of the strong polar functional group that in acrylic rubber, has added carboxyl and so on.Here, so-called have intermiscibility with epoxy resin, refers to forming homogenizing mixture after the curing not to separate into 2 this character more than mutually with epoxy resin.
Phenoxy resin is sold with the trade(brand)name of PHENOTOHTO YP-40, PHENOTOHTO YP-50, PHENOTOHTO YP-60 etc. by Toto Kasei KK.High molecular expoxy resin; Molecular weight is arranged is 30,000～80,000 high molecular expoxy resin, also have molecular weight to surpass 80,000 ultra-high molecular weight epoxy resin (please referring to the fair 7-59617 of spy number, special fair 7-59618 number, special fair 7-59619 number, special fair 7-59620 number, special fair 7-64911 number, special fair 7-68327 communique), all changes into Co., Ltd. by Hitachi and makes.As the reactive rubber that contains strong polar functional group, contain carboxy acrylic rubber and sell with the trade(brand)name of HTR-860P by Teikoku Chemical Industries Co., Ltd.
Has intermiscibility and weight-average molecular weight addition with above-mentioned epoxy resin at the high molecular weight resin more than 30,000; For prevent with epoxy resin be staple phase (below; Be called the epoxy resin phase) reduction and the reduction of the insulativity that causes because of crack etc. of not enough, the tackiness of flexibility; Be decided to be more than 10 weight parts, the reduction for the Tg that prevents epoxy resin is decided to be below 40 weight parts.
This as contain (methyl) glycidyl acrylate 2～6 weight %, Tg more than-10 ℃ and weight-average molecular weight containing the epoxy group(ing) acrylic copolymer 800,000 or more, can use the commodity of selling by Teikoku Chemical Industries Co., Ltd to be called the product of HTR-860P-3.The monomer is if use the vinylformic acid of carboxylic-acid or (methyl) vinylformic acid hydroxyl methyl esters of hydroxy kind; Then be easy to carry out crosslinking reaction and exist because of in the gelation under the varnish state, the problem of reduction etc. of the caused bonding force of rising of degree of cure under the B stage condition, so be not preferred.Be used as the amount of (methyl) glycidyl acrylate of monomer in addition, be decided to be 2～6 weight % of multipolymer.For obtaining bonding force, can be decided to be more than the 2 weight %, for preventing the gelation of rubber, can be decided to be below the 6 weight %.Remaining part can be used (methyl) ethyl propenoate or (methyl) Bing Xisuandingzhi or both mixtures, but mixture ratio will determine behind the Tg that considers multipolymer.If Tg is less than-10 ℃, then because the tackiness of the bonding film under the B stage condition becomes big, operability degenerates, so be decided to be more than-10 ℃.Polymerization method can be enumerated pearl polymerization, solution polymerization etc., can obtain polymkeric substance by these methods.
The weight-average molecular weight that contains the epoxy group(ing) acrylic copolymer is decided to be more than 800,000, because in this scope, sheet, membranaceous intensity and the reduction of flexibility, the increase of tackiness etc. are lacked.
The above-mentioned addition that contains the epoxy group(ing) acrylic copolymer; For the intensity that prevents film reduces and the tackiness increase, be decided to be more than 100 weight parts, contain the addition of epoxy group(ing) acrylic rubber like increase; Then rubber constituent increases mutually; Epoxy resin reduces mutually, reduces owing to can cause the operability under the high temperature, so be decided to be below 300 weight parts.
For tackiness agent,, can also cooperate coupler for the interface of improving between foreign material combines.As coupler, the preferred silane coupler.
As silane coupling agent, can enumerate γ-glycidoxypropyltrime,hoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan, γ-urea groups propyl-triethoxysilicane, N-β-aminoethyl-gamma-amino propyl trimethoxy silicane etc.
Above-mentioned silane coupling agent; γ-glycidoxypropyltrime,hoxysilane is with NUC A-187, and γ-Qiu Jibingjisanjiayangjiguiwan is with NUC A-189, and γ-An Jibingjisanyiyangjiguiwan is with NUC A-1100; γ-urea groups propyl-triethoxysilicane is with NUC A-1160; N-β-aminoethyl-gamma-amino propyl trimethoxy silicane is sold by Japan Unicar Co., Ltd. with the trade(brand)name of NUC A-1120, can use very suitably.
The use level of coupler from because of adding effect, thermotolerance and the price that is produced, preferably for resin 100 weight parts, is added 0.1～10 weight part.
In addition, for adsorbed ion property impurity, the insulating reliability when improving moisture absorption can also cooperate the ion trap agent.The use level of ion trap agent, from effect, thermotolerance and the price that is produced because of interpolation, preferred 5-10 weight part.As the ion trap agent, form stripping behind the ion in order to prevent copper, also can cooperate to prevent the compound that agent is widely known by the people as the copper evil, for example triazine thiol compound, bis-phenol are reductive agent.As bis-phenol is reductive agent, can enumerate 2,2 '-methylene radical-two-(4-methyl-6-tert butyl phenol) and 4,4 '-sulphur-two-(3 methy 6 tert butyl phenol) etc.
With the triazine thiol compound is that the copper evil of composition prevents that agent from being sold with the trade(brand)name of ZISNET DB by three Pharmaceutical Co., Ltd of association.In addition, be that reductive agent is that the copper evil of composition prevents that agent from being sold with the trade(brand)name of YOSHINOX BB by Yoshitomi Pharmaceutical Industries Co., Ltd with bis-phenol.
In addition, with operability or the thermal conductivity of improving tackiness agent, to give flame retardant resistance, adjust melt viscosity, give thixotropy, improve surface hardness be purpose, for adhesive resin composition 100 parts by volume, preferably cooperates the mineral filler of 2～20 parts by volume.From the effect that cooperates, when use level is more than 2 parts by volume, cooperate quantitative change for a long time because can cause that the storage elastic modulus of tackiness agent rises, cementability reduces, because of the remaining problems such as electrical specification reduction that cause of bubble, so be decided to be below 20 parts by volume.
As mineral filler, can enumerate white lake, Marinco H, lime carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, quicklime, Natural manganese dioxide, alumina powder, aluminium nitride powder, aluminium borate whisker, boron nitride powder, crystallinity silicon-dioxide, amorphism silicon-dioxide etc.
In order to improve thermal conductivity, preferred aluminum oxide, aluminium nitride AlN, SP 1, crystallinity silicon-dioxide, amorphism silicon-dioxide etc.
Wherein, aluminum oxide is good at thermal diffusivity, is suitable on thermotolerance, the good this point of insulativity.In addition, crystallinity silicon-dioxide or amorphism silicon-dioxide, though ratio aluminum oxide is poor on the thermal diffusivity this point,,,, be suitable on this point less to the corrosion of Copper Foil, aluminum steel, aluminium sheet etc. so the insulativity when PCT handles is high because ionic impurity is few.
For giving flame retardant resistance, preferred white lake, Marinco H and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.
In order to adjust melt viscosity and to give thixotropic purpose, preferred white lake, Marinco H, lime carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, quicklime, Natural manganese dioxide, aluminum oxide, crystallinity silicon-dioxide, amorphism silicon-dioxide etc.
For the raising of surface hardness, preferred alumina short fibre, aluminium borate whisker etc.
Bonding film of the present invention obtains like this: with the various compositions dissolving of tackiness agent or be distributed to and process varnish in the solvent, it is coated on the basement membrane, heating is desolvated to remove, and on basement membrane, forms binder layer thus.As basement membrane, can use the plastics film of polytetrafluoroethylene film, pet film, pet film, polyvinylidene film, PP SHEET FOR OPP TAPE, poly-methyl pentene film, Kapton etc. through demoulding processing.Basement membrane both can strip down in use and only use bonding film, also can use with basement membrane, and then remove it.
As the plastics film that uses in the present invention; For example can use the Kapton of KAPTON (trade(brand)name that Dong Li-Dupont Kabushiki Kaisha produces), APIKAL (trade(brand)name that Kanegafuchi Chemical Industry Co., Ltd produces) etc., the pet film of LUMIRROR-(trade(brand)name that Dong Li-Dupont Kabushiki Kaisha produces), PUREX (trade(brand)name that Teijin Ltd produces) etc. etc.
The solvent of varnishization preferably uses the lower methyl ethyl ketone of boiling point, acetone, MIBK, cellosolvo, toluene, ethylene glycol butyl ether, methyl alcohol, ethanol, 2-methyl cellosolve etc.In addition, the purpose from improving filming property etc. can also add high boiling solvent.As high boiling solvent, can enumerate N,N-DIMETHYLACETAMIDE, N, SL 1332, pimelinketone etc.
The manufacturing of varnish is being considered under the dispersive situation of mineral filler, can use sand mill, 3 rollers mill and ball mill etc., perhaps combines them and carries out.Can also adopt in advance mix filler and lower molecular weight thing after, cooperate the way of HMW thing to shorten again and mix the needed time.In addition, after processing varnish, preferably remove the bubble in the varnish by means of vacuum outgas.
Above-mentioned tackiness agent can adopt and be coated onto tackiness agent varnish on the basement membrane of above-mentioned plastics film etc., and heat drying removes the way of desolvating and makes, and makes the tackiness agent that obtains like this be in the state that thermal discharge reaches total curing exotherm amount 10～40% of measuring with DSC.Though remove heating when desolvating, at this moment carry out the curing reaction of binder compsn, the beginning gelation.At this moment solid state has influence on the flowability of tackiness agent, makes cementability and operability optimization.DSC (differential scanning calorimetry) is measuring principle with the zero-method, can use commercially available determinator.The zero-method measuring principle is to supply with or remove heat, make in measuring TR, constantly offset and the standard model of not heat release or heat absorption between temperature head.The reaction of resin combination is thermopositive reaction, if with the constant heat-up rate sample is heated up, then sample reacts, and emits heat.This thermal discharge is outputed on the recording paper, is benchmark with the baseline, obtains the area that is surrounded by exotherm and baseline, assigns this area as thermal discharge.℃ measure from room temperature to 250, obtain above-mentioned thermal discharge with 5～10 ℃/minute heat-up rate.The device that can automatically measure is also arranged, use full-automatic device easily to measure.Then, obtain with following method and be coated onto on the above-mentioned basement membrane and the thermal discharge of the tackiness agent that after drying, obtains.At first, under 25 ℃, make solvent seasoning, measure total thermal discharge of uncured sample with vacuum drier, with it as A (J/g).Secondly, measure apply, the thermal discharge of dried sample, with it as B.The degree of cure C (%) of sample (making the state after heat release finishes through heating, drying) is provided by following formula (1).
C(％)＝(A-B)×100/A ...(1)
The storage elastic modulus that tackiness agent of the present invention is measured with the Measurement of Dynamic Viscoelasticity device must be to be 20～2000MPa at 25 ℃, is the so-called low elastic modulus of 3～50MPa at 260 ℃.The mensuration of storage elastic modulus; Carry out with the temperature dependency mode determination; This pattern is following: tackiness agent cured article (95～100% of total curing exotherm amount tackiness agent when thermal discharge reaches and measures with DSC) is applied the stretching loading; Under frequency 10Hz,, rise to 300 ℃ from-50 ℃ and measure with 5～10 ℃/minute of heat-up rates.Storage elastic modulus under 25 ℃ surpasses the tackiness agent of 2000MPa, because the stress demulcent effect that when refluxing, takes place that the difference by semi-conductor chip and the thermal expansivity of printing circuit board is caused reduces, so can make it to take place the crack.On the other hand, during less than 20MPa, the operability of tackiness agent will degenerate at storage elastic modulus.Be preferably 50～1000MPa.
Characteristic of the present invention is, contains the epoxy group(ing) acrylic copolymer and near the Young's modulus of epoxy resin tackiness agent room temperature is low.Contain the epoxy group(ing) acrylic copolymer; In order to be reduced near the Young's modulus the room temperature; Adopt the way that increases the ratio of mixture that contains the epoxy group(ing) acrylic copolymer; To relax the stress that takes place in the difference heating process of cooling that cause, when refluxing by semi-conductor chip and the thermal expansivity of printing circuit board, just can suppress the crack by means of this effect.In addition owing to contain reactive good between epoxy group(ing) acrylic copolymer and the epoxy resin, the tackiness agent cured article since chemically, physically stablize and in the anti-moisture test that is treated to representative with PCT, demonstrate good performance.In addition, solve the problem that existing bonding film intensity reduces, flexibility reduces, the tackiness increase waits the operability aspect with following method.
1) use stipulate among the present invention contain the epoxy group(ing) acrylic copolymer, the crack takes place in the time of can suppressing to reflux.
2) use the big acrylic copolymer of molecular weight,, also can guarantee the film strength and the flexibility of bonding film even under the few situation of the addition of multipolymer.
3) add with epoxy resin and have intermiscibility and weight-average molecular weight, can reduce tackiness at the high molecular weight resin more than 30,000.
In addition; If use tackiness agent of the present invention, then because epoxy resin and the high molecular weight resin intermiscibility is good and homogeneous, partly react the epoxy group(ing) and they that are contained in the acrylic copolymer; Comprise all the carrying out crosslinked of unreacted epoxy resin and gelation takes place; This has just suppressed flowability, even if under the situation that contains many epoxy resin etc., also can not damage operability.In addition, owing to remaining in gel many unreacted epoxy resin are arranged, under the situation of exerting pressure, unreacted component oozes out from gel, even if all under the situation of gelation, the reduction of cementability also seldom.
When tackiness agent dry; Though the epoxy group(ing) and the epoxy resin that are contained in the epoxy group(ing) acrylic copolymer all react; But; The molecular weight that contains the epoxy group(ing) acrylic copolymer is big, in a molecular chain, contains a plurality of epoxy group(ing), so even if gelation takes place also under the situation that reaction is carried out.Usually, reach 10～40% the state of measuring the curing exotherm amount with DSC, in preceding half stage in A stage or B stage gelation takes place in other words at thermal discharge.Therefore, gelation takes place under the state of the unreacted component that contains many epoxy resin etc., with the situation ratio that gelation does not take place, melt viscosity increases significantly, and can not damage operability.In addition, under the situation of exerting pressure, owing to unreacted component oozes out from gel, so even if under the situation of gelation, cementability reduces seldom.In addition, tackiness agent can form film under the state of the unreacted component that contains many epoxy resin etc., so have long advantage of bonding film life-span (effective life).
If with existing epoxy resin tackiness agent; Because begin just to produce gelation under the state at the beginning of the C stage from second half section in B stage, in the stage that gelation takes place, the unreacted component of epoxy resin etc. is few; So it is mobile low; Even if under the situation of exerting pressure, the unreacted component that from gel, oozes out is also few, so cementability reduces.
Should explain; Though the easy degree of reaction about the epoxy group(ing) of the epoxy group(ing) that contains in the acrylic copolymer and low-molecular-weight epoxy resin is not come to understand as yet; But; As long as have the reactivity of equal extent at least, there is no need be the sort of only optionally with acrylic copolymer in the material that reacts of the epoxy group(ing) that contains.
Also have, in this case, A, B, C stage are represented tackiness agent solidified degree.The A stage is almost uncured and the state of gelation not, is 0～20% the state that thermal discharge reaches total curing exotherm amount when measuring with DSC.The B stage is the state that has carried out some curing, gelation, is 20～60% the state that thermal discharge reaches total curing exotherm amount.The C stage be quite solidify, the state of gelation, be 60～100% the state that thermal discharge reaches total curing exotherm amount.
About the judgement of gelation, in big solvent such as the impregnability that is dipped into tackiness agent THF (THF) etc., 25 ℃ of held after 20 hours, not dissolving fully but the tackiness agent that is in solvent swelling state is judged to be gelation.Should explain, judge with following method experimentally.
Be dipped into tackiness agent (weight W 1) among the THF, after 20 hours, filter not solvent components, measure its dried weight (W2) with 200 purpose nylon cloths 25 ℃ of placements.Calculate the percentage extraction (%) of THF with following formula (2).The tackiness agent that surpasses the THF percentage extraction 80 weight % is judged to be not gelation, is judged to be gelation to the tackiness agent below the 80 weight %.
THF percentage extraction (weight %)=(weight W 1-weight W 2) * 100/ weight W 1... (2)
In the present invention, owing to can adopt the way of adding filler to increase melt viscosity, thixotropy can also appear, so can further increase above-mentioned effect.
Have again, except that above-mentioned effect, can also improve tackiness agent thermal diffusivity, give tackiness agent and make it to have appropriate viscosity with flame retardant resistance, under bonding temp, can also give the characteristic of improving surface hardness etc.With bonding film of the present invention semiconductor device that semi-conductor chip and running board is bonding in anti-backflow property, temperature cycling test, electrocorrosion-resisting property, wet fastness aspect excellent propertys such as (anti-PCT property).
In the present invention; The thermotolerance thermoplastic film that in core, uses; Preferred glass transition temperature T g is polymkeric substance or the film of liquid crystalline polymers more than 200 ℃, preferably uses polyimide, polyethersulfone, polyamidoimide, polyetherimide or Wholly aromatic polyester etc.The thickness of film preferably uses in 5～200 microns scope, but is not to be defined in this scope.Be Tg thermoplastic film below 200 ℃ when the core, the high temperature of solder reflow etc. often regular meeting cause viscous deformation, be unfavorable.
In the present invention; The tackiness agent that on the two sides of core, forms; Can adopt to dissolve each composition of tackiness agent or be distributed to earlier and process varnish in the solvent, be coated onto on the thermotolerance thermoplastic film that constitutes core, the way that adds the heat extraction solvent is made; Also can be employed in the way that forms binder layer on the thermotolerance thermoplastic film that becomes core, obtain the double-sided adhesive film of 3-tier architecture.The thickness of tackiness agent can use in 2～150 microns scope, and as thinner than this, then cementability and thermal stresses buffering effect are poor, and be then uneconomical as thicker than this, but be not limited thereto.
In addition; Can also adopt each composition dissolving of tackiness agent or be distributed to and process varnish in the solvent; Be coated onto this varnish on the basement membrane again, add the way of heat extraction solvent, make the bonding film that only constitutes by binder constituents; Be attached to the way on the two sides of the thermotolerance thermoplastic film that constitutes core to the bonding film that only constitutes again, obtain the double-sided adhesive film of 3-tier architecture by binder constituents.Here; As the basement membrane that only is used to make the bonding film that constitutes by binder constituents, the plastics film of the polyethylene terephthalate film that can use poly tetrafluoroethylene, polyethylene terephthalate film, handle through the demoulding, polyethylene film, polypropylene screen, polymethylpentene film, polyimide film etc.As plastics film; For example can use the Kapton of KAPTON (trade(brand)name that Dong Li-Dupont Kabushiki Kaisha produces), APIKAL (trade(brand)name that Kanegafuchi Chemical Industry Co., Ltd produces) etc., the pet film of LUMIRROR-(trade(brand)name that Dong Li-Dupont Kabushiki Kaisha produces), PUREX (trade(brand)name that Teijin Ltd produces) etc. etc.
The solvent of varnishization is preferably with the lower methyl ethyl ketone of boiling point, acetone, MIBK, cellosolvo, toluene, ethylene glycol butyl ether, methyl alcohol, ethanol, 2-methyl cellosolve etc.In addition, the purpose from improving filming property etc. can also add high boiling solvent.As high boiling solvent, can enumerate N,N-DIMETHYLACETAMIDE, N, SL 1332, pimelinketone etc.
The manufacturing of varnish is being considered under the dispersive situation of mineral filler, can use sand mill, 3 rollers mill and ball mill etc., perhaps combines them and carries out.Can also be employed in advance mix filler and lower molecular weight thing after, cooperate the way of HMW thing, shorten and mix the needed time.In addition, after processing varnish, preferably remove the bubble in the varnish by means of vacuum outgas.
Above-mentioned tackiness agent can adopt and be coated onto tackiness agent varnish on the basement membrane of the thermotolerance thermoplastic film that constitutes core or above-mentioned plastics film etc.; Heat drying removes the way of desolvating and makes, and the tackiness agent that obtains so preferably is in the state that thermal discharge reaches total curing exotherm amount 10～40% of measuring with DSC.Heat the curing reaction of binder compsn generation at this moment, beginning gelation when desolvating removing.At this moment solid state has influence on the flowability of tackiness agent, makes cementability and operability.DSC (differential scanning calorimetry) is measuring principle with the zero-method, can use commercially available determinator.The zero-method measuring principle is to supply with or remove heat, make in measuring TR, constantly offset and the standard model of not heat release or heat absorption between temperature head.The reaction of resin combination is thermopositive reaction, if with the constant heat-up rate sample is heated up, then sample reacts, and emits heat.This thermal discharge is outputed on the recording paper, is benchmark with the baseline, obtains the area that is surrounded by exotherm and baseline, this area as thermal discharge.℃ measure from room temperature to 250, ask above-mentioned thermal discharge with 5～10 ℃/minute heat-up rate.The device that can automatically carry out these mensuration is also arranged, if use full-automatic device then can easily measure.
Obtain with following method and to be coated onto on the thermotolerance thermoplastic film that constitutes core or the basement membrane and the thermal discharge of the tackiness agent that after drying, obtains.At first, only take out binder constituents, under 25 ℃, make solvent seasoning, measure total thermal discharge of uncured sample with vacuum drier, with it as A (J/g).Secondly, measure apply, the thermal discharge of dried sample, with it as B.The degree of cure C (%) of sample (making the state after heat release finishes through heating, drying) is provided by following formula.
C(％)＝(A-B)×100/A ...(1)
Binder constituents of the present invention, it is 20～2000MPa at 25 ℃ preferably with the storage elastic modulus that the Measurement of Dynamic Viscoelasticity device is measured, and is the so-called low elastic modulus of 3～50MPa at 260 ℃.The mensuration of storage elastic modulus is carried out with the temperature dependency mode determination, and this pattern is following: the tackiness agent cured article is applied the stretching loading, under frequency 10Hz, with 5～10 ℃/minute of heat-up rates, be warming up to 300 ℃ from-50 ℃ and measure.Storage elastic modulus under 25 ℃ surpasses the tackiness agent of 2000MPa, because the stress demulcent effect that when refluxing, takes place that the difference by semi-conductor chip and the thermal expansivity of printing circuit board is caused reduces, so can make it to take place the crack.On the other hand, during less than 20MPa, the operability of tackiness agent degenerates at storage elastic modulus.
Characteristic of the present invention is, is employed in the three-decker of using the thermotolerance thermoplastic film in the core, contains epoxy group(ing) acrylic copolymer and near the Young's modulus of epoxy resin tackiness agent room temperature and hangs down the problem of having improved the bonding film poor operability.In other words, by means of three-decker of the present invention, near the operation of the position alignment of the no inflexible bonding film room temperature etc. can realize robotization easily, and, can also realize the slow effect of closing of good thermal stresses of this tackiness agent system.In the present invention, solve the problem that waits the operability aspect that causes because of existing low elastic modulus bonding film rigidity is low with following method.
3) employing is configured to the three-decker on the core to the thermotolerance thermoplastic film, can easily use the tackiness agent of low elastic modulus with film like.
The thermotolerance thermoplastic film of the formation core of 4) stipulating among use the present invention can be suppressed at the viscous deformation of bonding film when refluxing.
In addition; In the present invention, because the good and homogeneous of intermiscibility of epoxy resin and high molecular weight resin, partly react the epoxy group(ing) and they that are contained in the acrylic copolymer; Comprise that unreacted epoxy resin all carries out crosslinked generation gelation; So this will suppress mobile, even if, also can not damage operability containing under the situation of many epoxy resin etc.In addition, owing to remaining in gel many unreacted epoxy resin are arranged, so under the situation of exerting pressure, unreacted component oozes out from gel, so even if all under the situation of gelation, the reduction of cementability is also little.
When tackiness agent dry; Though the epoxy group(ing) and the epoxy resin that are contained in the epoxy group(ing) acrylic copolymer all react; But; The molecular weight that contains the epoxy group(ing) acrylic copolymer is big, in a molecular chain, contains a plurality of epoxy group(ing), so even if proceed in reaction gelation takes place also under the situation to a certain degree.Usually, reach 10～40% state of total curing exotherm amount when measuring, in preceding half stage in A stage or B stage gelation takes place in other words with DSC at thermal discharge.Therefore, gelation takes place under the state of the unreacted component that contains many epoxy resin etc., with the situation ratio that gelation does not take place, melt viscosity increases significantly, and can not damage operability.In addition, under the situation of exerting pressure, owing to unreacted component oozes out from gel, so even if under the situation of gelation, cementability reduces seldom.In addition, tackiness agent can form film under the state of the unreacted component that contains many epoxy resin etc., so have long advantage of bonding film life-span (effective life).
If with existing epoxy resin tackiness agent; Because begin just to produce gelation under the state at the beginning of the C stage from second half section in B stage, in the stage that gelation takes place, the unreacted component of epoxy resin etc. is few; So it is mobile low; Even if under the situation of exerting pressure, the unreacted component that from gel, oozes out is also few, so cementability reduces.
Should explain; Though the easy degree of reaction about the epoxy group(ing) of the epoxy group(ing) that contains in the acrylic copolymer and low-molecular-weight epoxy resin is not come to understand as yet; But; As long as have the reactivity of equal extent at least, there is no need be the sort of only optionally with acrylic copolymer in the material that reacts of the epoxy group(ing) that contains.
Also have, in this case, A, B, C stage are represented tackiness agent solidified degree.The A stage is almost uncured and the state of gelation not, is 0～20% the state that thermal discharge reaches total curing exotherm amount when measuring with DSC.The B stage is the state that has carried out some curing gelizations, is 20～60% the state that thermal discharge reaches total curing exotherm amount.The C stage be quite solidify, the state of gelation, be 60～100% the state that thermal discharge reaches total curing exotherm amount.
About the judgement of gelation, in big solvent such as the impregnability that is dipped into tackiness agent THF (THF) etc., 25 ℃ of held after 20 hours, not dissolving fully but the tackiness agent that is in solvent swelling state is judged to be gelation.Should explain, judge with following method experimentally.
Be dipped into tackiness agent (weight W 1) among the THF, after 20 hours, filter not solvent components, measure its dried weight (W2) with 200 purpose nylon cloths 25 ℃ of placements.Calculate the percentage extraction (%) of THF with following formula (2).The tackiness agent that surpasses the THF percentage extraction 80 weight % is judged to be not gelation, is judged to be gelation to the tackiness agent below the 80 weight %.
THF percentage extraction (weight %)=(weight W 1-weight W 2) * 100/ weight W 1... (2)
In the present invention, owing to can adopt the way of adding filler to increase melt viscosity, thixotropy can also appear, so can further increase above-mentioned effect.
Have again, except that above-mentioned effect, can also improve tackiness agent thermal diffusivity, give tackiness agent and make it to have appropriate viscosity with flame retardant resistance, under bonding temp, can also give the characteristic of improving surface hardness etc.
Description of drawings
Fig. 1 (a) is the sectional view of individual layer hot setting binding film of the present invention, and Fig. 1 (b) is the sectional view of three layers of bonding film of the present invention.
Fig. 2 is the sectional view that is hot-pressed onto adhesive member the substrate for mounting semiconductor that forms on organic circuit board.
Fig. 3 is the sectional view that is hot-pressed onto adhesive member the substrate for mounting semiconductor that forms on organic circuit board.
Fig. 4 is the sectional view of semiconductor device of the present invention.
Fig. 5 is the sectional view of another example of semiconductor device of the present invention.
Fig. 6 is the sectional view of manufacturing process of an embodiment of explanation substrate for mounting semiconductor and semiconductor device.
Fig. 7 is the sectional view of manufacturing process of another embodiment of explanation substrate for mounting semiconductor and semiconductor device.
Fig. 8 is the sectional view of another example of semiconductor device of the present invention.
Embodiment
Below, according to accompanying drawing various embodiment of the present invention are described.
< embodiment 1 >
Fig. 1 (a) is the sectional view of individual layer hot setting binding film, and it is to be made up of thermosetting adhesive 1.The Young's modulus under 25 ℃ that its cured article is measured with the Measurement of Dynamic Viscoelasticity device is defined as the scope of 10～2000MPa; And; Young's modulus under 260 ℃ is defined as the scope of 3～50MPa, is in the semi-cured state that thermal discharge reaches 10～40% the sort of degree of total curing exotherm amount when measuring with DSC (differential calorimeter).Use to be dried to quantity of solvent remaining in the hot setting binding film and contain epoxy group(ing) PEMULEN TR2 film below 2%.
Fig. 1 (b) illustrates the sectional view that is coated onto thermosetting adhesive 1 three layers of bonding film on the two sides of polyimide film 2.In this example, as polyimide film, use the UPILEX (trade(brand)name) of 50 micron thick of the emerging generation product of space portion.
Fig. 2 be suitable for partly coupling together semi-conductor terminal part and circuit board one side terminal with the wire bonds mode, be hot-pressed onto the sectional view of the substrate for mounting semiconductor that forms on organic circuit board 4 to adhesive member 3, Fig. 3 is suitable for that inside bonding mode with TAB partly couples together semi-conductor terminal part and circuit board one side terminal, as to be hot-pressed onto adhesive member 3 substrate for mounting semiconductor of formation on the tape type wiring substrate 5 sectional view.Fig. 4 faces up chip 6 to bond on the substrate for mounting semiconductor of Fig. 2; Get up semi-conductor terminal part and running board one side terminal bonding with wire 7; The sectional view of the semiconductor device that seals with sealing material again and constitute; Fig. 5 be face down chip 6 on the substrate for mounting semiconductor that bonds to Fig. 3 after; With the inside bonding mode of TAB, partly couple together semi-conductor terminal part and substrate one side terminal, again the sectional view of the end face of chip 6 with the semiconductor device of liquid sealing material 8 sealing back formations.In addition, as shown in Figure 8, also can be formed at the opposition side with mounting semiconductor chip one side of substrate to wiring 9.In this case, external connection terminals 12 is formed on the surface of the wiring 9 that the opposition side with mounting semiconductor chip one side forms.In addition, the exposed portions serve of wiring 9 is covered by photoresist material 11.
Fig. 6 shows the manufacturing process of substrate for mounting semiconductor and semiconductor device.
The thermosetting adhesive band (adhesive member) 3 that constitutes by thermosetting adhesive 1, cut into the size (Fig. 6 (a)) of regulation with stamping machine.The cured article of thermosetting adhesive 1; The Young's modulus of measuring with the Measurement of Dynamic Viscoelasticity device at 25 ℃ is defined as 10～2000MPa; And 260 ℃ Young's modulus is defined as 3～50MPa, is in the semi-cured state that thermal discharge reaches 10～40% the sort of degree of total curing exotherm amount when measuring with DSC.
Implementing 1 layer of Cu wiring and forming on the surface of outside scolder terminal with the polyimide film substrate (organic circuit board) 4 of through hole; The thermosetting adhesive band 3 that cuts off is critically carried out after the position alignment; Carry out hot pressing with thermocompressor, obtain substrate for mounting semiconductor (Fig. 6 (b)).
In this example; Carry out the cut-out of hot setting binding film respectively, precision positioning loading and working fastening on polyimide substrate, afterwards; With thermocompressor the hot setting binding film of loaded is carried out formal hot pressing totally, obtain the frame-like substrate for mounting semiconductor of 7 polyphones.In addition in this example, before cutting off the operation of hot setting binding film 3, also implement to be blown into the static of charged air and remove operation, when cutting off operation, be attached on the anchor clamps to prevent charged insulativity film.This is external carry out bonding and totally temporarily formal bonding when, also to the mold enforcement tetrafluoroethylene of the thermocompressor that contact with hot setting binding film 3 or the release surface processing of siloxanes be adhered on the mold to prevent the thermoset film.Semi-conductor chip 6 faceup precision positioning be loaded into the mounting semiconductor in groups that obtains like this with on the frame base, carry out with the bonding chip attachment operation (Fig. 6 (c)) of thermocompressor pressurization.In this example, be set at the Heating temperature of semi-conductor chip one side and be higher than substrate for mounting semiconductor one side at least, heat from the two sides and add press fit.
Afterwards; Through the terminal part of the terminal part of semi-conductor chip one side and substrate one side being carried out the wire bonds operation (Fig. 6 (d)) of bonding with spun gold; With the sealing process that seals with the moulding of epoxy resin sealing material transfer mould (Fig. 6 (e)); Then load solder ball and after reflow process, form operation through the solder ball that forms outside terminal 9 again, obtain semiconductor device of the present invention (Fig. 6 (f)).As sealing material 8, the biphenyl that uses Hitachi to change into production is epoxy sealing material C EL-9200 (trade(brand)name).
Comparative example 1
Implementing 1 layer of Cu wiring and forming above the polyimide film circuit board (identical) of outside scolder terminal with through hole with the substrate that in embodiment 1, uses; Drip and apply the insulativity fluid binder with the die bonding device, and critically locate and load semi-conductor chip.
Said tackiness agent is staple with epoxy resin, and its cured article is 3000MPa with 25 ℃ the Young's modulus that DMA (Measurement of Dynamic Viscoelasticity device) measures.Then, the same after the set time through regulation in clean baking oven with embodiment 1, form operation through wire bonds operation, sealing process and solder ball, obtain semiconductor device.
Comparative example 2
With embodiment 1 on the identical polyimide circuit board of the substrate that uses, drip and apply the insulativity fluid binder with the die bonding device, load semi-conductor chip.Said tackiness agent is staple with epoxy resin, and its cured article is 10MPa at 25 ℃ Young's modulus, and 260 ℃ Young's modulus is little of not measurable the sort of degree.Then, through obtaining semiconductor device with embodiment 1 identical operation.
< embodiment 2 >
Fig. 7 shows the manufacturing process of substrate for mounting semiconductor and semiconductor device.
The thermosetting adhesive band (adhesive member) 3 that constitutes by thermosetting adhesive 1, cut into the size (Fig. 7 (a)) of regulation with stamping machine.The cured article of thermosetting adhesive 1; The Young's modulus of measuring with the Measurement of Dynamic Viscoelasticity device at 25 ℃ is defined as 10～2000MPa; And 260 ℃ Young's modulus is defined as 3～50MPa, is in the semi-cured state that thermal discharge reaches 10～40% the sort of degree of total curing exotherm amount when measuring with DSC.
Implement 1 layer of Cu wiring and formation and TAB with same inner lead portion and the surface of outside scolder terminal with the polyimide film substrate 5 of through hole on; The thermosetting adhesive band 3 that cuts off is critically carried out after the position alignment; Carry out hot pressing with thermocompressor, obtain substrate for mounting semiconductor (Fig. 7 (b)).
In this example, through removing operation with the static before the cut-out operation described in the embodiment 1 and on thermocompressor mold face, implementing the identical operation that release surface is handled, the mounting semiconductor that obtains is in groups used frame base.
Then, semi-conductor chip 6 is faced down carry out being loaded into mounting semiconductor successively with on the frame base after precision positions is aimed at, carry out hot pressing (Fig. 7 (c)) with thermocompressor.Afterwards; Through (in this example with TAB leading wire bonding machine; Be single-point bonding machine) be connected to the leading wire bonding (Fig. 7 (d)) on chip one side terminal to this Cu inner lead portion 10 respectively as substrate one side terminal; With divider is epoxy that liquid sealing material 8 is layed onto on the surface of chip end face and polyimide film substrate 5 (Fig. 7 (e)), again through predetermined heating with after set time, obtains semiconductor device (Fig. 7 (f)).In this example, inner lead portion is used the lead-in wire of the plating Sn in the Cu top, and the semi-conductor terminal part is used and formed the protruding terminal of plating Au, engages with Au/Sn to connect.
Comparative example 3
On the inner lead portion of implementing 1 layer of Cu wiring and forming the TAB band and outside scolder terminal surface with the polyimide film substrate identical of through hole with embodiment 2; Drip and apply the insulativity fluid binder with the die bonding device, and critically locate and load semi-conductor chip.Said tackiness agent is staple with epoxy resin, and 25 ℃ the Young's modulus that its cured article uses DMA to measure is 3000MPa.But resin trickles to inner bonding part always, though inside bonding afterwards can't carry out; But keeping this appearance the same with embodiment 2 unchangeably, is the liquid sealing material of main body in order to epoxy resin, and the chip end face is sealed; Form solder ball, relatively article.
Comparative example 4
On the inner lead portion of implementing 1 layer of Cu wiring and forming the TAB band and outside scolder terminal the polyimide film substrate identical with embodiment 2 with through hole; Drip and apply the insulativity fluid binder with the die bonding device, and likewise load semi-conductor chip with embodiment 2.Said tackiness agent is staple with the silicone resin, and its cured article is 10MPa at 25 ℃ Young's modulus, and little of not measurable the sort of degree at 260 ℃ Young's modulus.But resin trickles to inner bonding part always, though inside bonding afterwards can't carry out; But keeping this appearance the same with embodiment 2 unchangeably, is the liquid sealing material of main body in order to epoxy resin, and the chip end face is sealed; Form solder ball, relatively article.
Comparative example 5
Annotating with the silicone resin to the polyfluortetraethylene plate patrix is staple; Its cured article is 10MPa at 25 ℃ Young's modulus; And at the little insulativity tackiness agent of 260 ℃ Young's modulus to not measurable the sort of degree; Afterwards, after making it to solidify with the predetermined heating temperature and time, obtain the film of low elasticity.On the two sides of this film, being coated in said in the comparative example 3 is the thermosetting adhesive of main body with epoxy resin, identical with embodiment 2 with through hole of the inner lead portion of implementing 1 layer of Cu wiring and forming the TAB band and outside scolder terminal; On the surface of polyimide film substrate, use thermocompressor hot pressing, then; After ground that semi-conductor chip is faced down is bonding; Through behind the leading wire bonding operation described in the embodiment 2, sealing process, form solder ball, relatively article.
When the semiconductor device of embodiment 1, embodiment 2, comparative example 1～5 was implemented the backflow test of anti-the moisture absorption, each semiconductor device that also is assembled to refluxing on the FR-4 circuit board was implemented the round-robin test of heatproof degree.Test-results is shown in table 1.For the moisture absorption backflow test; Before moisture absorption and under the condition of 85 ℃ and 85%RH, make it after the moisture absorption 24 hours and 48 hours; Implement IR down 240 ℃ of top temperatures and reflux, investigate peeling off and the crack in the experiment product, its result has been shown in table 1 with SAT (ultrasonic fault detection failure detector).In addition; It is softening to implement IR down 240 ℃ of top temperatures, investigates peeling off and the crack in the experiment with SAT (ultrasonic fault detection failure detector), and the heatproof degree round-robin test of each sample is-25 ℃ of substrate assembling back enforcements (30 minutes; In the air)～150 ℃ (30 minutes; In the air) temperature cycle, connect resistance with the solder ball that 4 terminal methods are measured the outside terminal of encapsulation then, be used as the sample of resistance more than 50m Ω defective.
[table 1]
(notes)
Anti-backflow property
Zero: on the interface between chip 6 and organic circuit board 4,5 and the thermosetting adhesive 3, peel off seldom, can not use SAT (ultrasonic fault detection failure detector) to detect with bubble.
In A:10 the sample 2～3 imbedding between the wiring of organic circuit board is insufficient, has observed bubble when applying thermosetting adhesive 3, and this position is being developed into and is being peeled off.
*: in 10 samples 10 the above-mentioned outside that arrives encapsulation of peeling off is arranged, the backflow after extends in the encapsulation, and observes the crack.Also observe the sample that makes wire bonds part and inner lead portion that broken string takes place after peeling off.
Heatproof degree cyclicity
Zero: the connection resistance of solder ball connection portion does not change.
*: exist the connection resistance of one solder ball connection portion to surpass 50m Ω at least.
-: inner bonding can not be carried out, connection resistance can not be measured.Can not estimate.
< embodiment 3 >
As epoxy resin, use bisphenol A type epoxy resin (epoxy equivalent (weight) 200, the EPIKOTE 828 that YukaShell Epoxy Co., Ltd. produces) 45 weight parts; The solvable phenol aldehyde type epoxy resin of cresols (epoxy equivalent (weight) 220, the ESCN001 that Sumitomo Chemical Company Ltd produces) 15 weight parts; As epoxy curing agent, use solvable fusible phenol aldehyde type epoxy resin (PLYOPHENLF2882 that Dainippon Ink. & Chemicals Inc produces) 40 weight parts; As intermiscibility and weight-average molecular weight being arranged at the high molecular weight resin more than 30,000, use phenoxy resin (molecular weight 50,000, the PHENOTOHTO YP-50 that Toto Kasei KK produces) 15 weight parts with epoxy resin; As containing the epoxy group(ing) acrylic rubber, use to contain epoxy group(ing) acrylic rubber (molecular weight 1,000,000, the HTR-860-P3 that Teikoku Chemical Industries Co., Ltd produces) 150 weight parts; As curing catalyst, use curing catalyst 1-cyanoethyl-2-phenylimidazole (CUREZOLE 2PZ-CN) 0.5 weight part; As silane coupling agent, use γ-glycidoxypropyltrime,hoxysilane (the NUC A-187 that Japan Unicar Co., Ltd. produces) 0.7 weight part, in the compsn of above-mentioned composition, add methyl ethyl ketone and mix stirring, carry out vacuum outgas.Being coated onto thickness to resulting varnish is 75 microns having carried out on the polyethylene terephthalate film that the demoulding handles, 140 ℃ of following heat dryings 5 minutes, forms thickness and be 80 microns the filming of B stage condition, and makes bonding film.
Under this state, the degree of cure of tackiness agent is measured the result of (10 ℃/minute of heat-up rates) with DSC (E.I.Du Pont Company produce 912 type DSC), is the state after 15% heat release of total curing exotherm amount finishes.In addition, be soaked in tackiness agent (weight W 1) among the THF, and 25 ℃ place 20 hours after; Do not dissolve part with the filtration of 200 purpose nylon cloths; Measure its dried weight (weight W 2), obtain the THF percentage extraction (=(W1-W2) * 100/W1), the THF percentage extraction is 35 weight %.In addition; (RHEOLOGY company produces with the Measurement of Dynamic Viscoelasticity device; DVE-V4) measure the result of the storage elastic modulus (80 microns of sample size: length 20mm, width 4mm, thickness, heat-up rate: 5 ℃/minute, stretch mode, dead weight automatically) of tackiness agent cured article; At 25 ℃ is 360MPa, is 4MPa at 260 ℃.
< embodiment 4 >
A phenoxy resin of removing handle use in embodiment 3 changes to and contains outside carboxylated acrylonitrile-divinyl rubber (molecular weight 400,000, the PNR-1 that uses Japan Synthetic Rubber Co. Ltd to produce), and warp is processed bonding film with embodiment 3 identical processing.Should explain that the degree of cure of the tackiness agent under this state with the result that DSC measures, is in 20% the state that thermal discharge reaches total curing exotherm amount.The THF percentage extraction is 35 weight %.Measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 300MPa at 25 ℃, is 3MPa at 260 ℃.
< embodiment 5 >
Tackiness agent for the tackiness agent varnish of embodiment 3 forms branch 100 parts by volume admittedly, to the silicon-dioxide that wherein adds 10 parts by volume, with ball mill mixing 60 minutes, processes bonding film with the varnish warp that forms like this with embodiment 3 same processing.With the result that DSC measures, be in 15% the state that thermal discharge reaches total curing exotherm amount.The THF percentage extraction is 30 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 1500MPa at 25 ℃, is 10MPa at 260 ℃.
< embodiment 6 >
Except that not using the phenoxy resin that in embodiment 3, uses, warp is processed bonding film with embodiment 3 same processing.With the result that DSC measures, be in 15% the state that thermal discharge reaches total curing exotherm amount.The THF percentage extraction is 35 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 350MPa at 25 ℃, is 4MPa at 260 ℃.
< comparative example 6 >
Except that the amount that contains the epoxy group(ing) acrylic rubber of embodiment 3 from 150 weight parts change 50 weight parts into, warp is processed bonding film with embodiment 3 same processing.With the result that DSC measures, be in 20% the state that thermal discharge reaches total curing exotherm amount.The THF percentage extraction is 40 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 3000MPa at 25 ℃, is 5MPa at 260 ℃.
< comparative example 7 >
Except that the amount that contains the epoxy group(ing) acrylic rubber of embodiment 3 from 150 weight parts change 400 weight parts into, warp is processed bonding film with embodiment 3 same processing.With the result that DSC measures, be in 20% the state that thermal discharge reaches total curing exotherm amount.The THF percentage extraction is 30 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 200MPa at 25 ℃, is 1MPa at 260 ℃.
< comparative example 8 >
Except that the amount that contains the epoxy group(ing) acrylic rubber of embodiment 3 from 150 weight parts change phenoxy resin (phenoxy resin 160 weight parts) into, warp is processed bonding film with embodiment 3 same processing.This bonding film is 20% of total curing exotherm amount, and the THF percentage extraction is 90 weight %.In addition, storage elastic modulus is 3400MPa at 25 ℃, is 3MPa at 260 ℃.
< comparative example 9 >
Except that the epoxy group(ing) acrylic rubber that contains embodiment 3 changes into the acrylonitrile-butadiene rubber, warp is processed bonding film with embodiment 3 same processing.This bonding film is 20% of total curing exotherm amount, and the THF percentage extraction is 90 weight %.In addition, storage elastic modulus is 500MPa at 25 ℃, is 2MPa at 260 ℃.
For the semiconductor device of processing with resulting bonding film, examine or check its thermotolerance, electrocorrosion-resisting property and wet fastness.In the stable on heating evaluation method, adopt the anti-backflow crack property and the temperature cycling test of the semiconductor device sample (on a face, forming solder ball) that the flexibility printed circuit board that uses 25 micron thick polyimide films to semi-conductor chip and base material forms with the bonding film stickup.The broken up evaluation of anti-backflow is performed such: earlier sample is sent in the IR of design temperature (infrared rays) reflow ovens; So that the top temperature of sample surfaces is 240 ℃ and kept this temperature 20 seconds; At room temperature place cooling, after carrying out repeatedly handling for 2 times, the crack in the observation sample.Fissured sample not taking place be decided to be well, fissured sample takes place be decided to be defective.Temperature cycling test is that sample was placed 30 minutes in-55 ℃ atmosphere, in 125 ℃ atmosphere, places 30 minutes then, is used as a circulation to this operation, is expressed as the cycle index till destroying.In addition; The evaluation of electrocorrosion-resisting property is performed such: the comb pattern that on the FR-4 substrate, forms lines/at interval=75/75 micron; Be attached to its top to bonding film then, apply at 85 ℃/85%RH/ and measure the insulating resistance value of sample after 1000 hours of processing like this under the condition of DC6V.Insulating resistance value is good more than 10 Ω, and less than 10 Ω is defective.In addition, the wet fastness evaluation is performed such: after being placed on the processing of carrying out in the pressure cooking tester 96 hours (PCT processing) to the semiconductor device sample, observe peeling off and variable color of bonding film.Do not find out bonding film peel off and variable color be regarded as good, have peel off have variable color as defective.Its result is shown in table 2.
No matter embodiment 3,4 and 5 which all be contain simultaneously epoxy resin and solidifying agent thereof, with epoxy resin have intermiscibility high molecular weight resin, contain the tackiness agent of epoxy group(ing) acrylic copolymer, curing catalyst; Embodiment 6 is the tackiness agents that contain epoxy resin and solidifying agent thereof simultaneously, contain epoxy group(ing) acrylic copolymer and curing catalyst, demonstrates the storage elastic modulus under 25 ℃ and 260 ℃ that stipulate among the present invention.Their anti-backflow crack property, temperature cycling test, electrocorrosion-resisting property, anti-PCT property are good.
Comparative example 6 so storage elastic modulus is high, can not relax stress because the amount that contains the epoxy group(ing) PEMULEN TR2 of regulation is few in the present invention, and the result of anti-backflow crack property, temperature cycling test is bad, and safety is bad.In addition, comparative example 7 is because the amount that contains the epoxy group(ing) acrylic copolymer of regulation is too much in the present invention, so though storage elastic modulus is low, be good, the operability of bonding film is bad.Comparative example 8 since its be not contained in forming stipulate among the present invention contain the epoxy group(ing) PEMULEN TR2, the same so storage elastic modulus is high with comparative example 6, can not relax stress, the result in anti-backflow crack property, temperature cycling test is bad.Comparative example 9 has provided following result: be not contained in stipulate among the present invention contain the epoxy group(ing) PEMULEN TR2, and contain rubber constituent in addition, though low at 25 ℃ storage elastic modulus, electrocorrosion-resisting property aspect is bad.
< embodiment 7 >
Use bisphenol A type epoxy resin (epoxy equivalent (weight) 200, the product of the commodity that Yuka ShellEpoxy Co., Ltd. produces EPIKOTE 828 by name) 45 weight parts as epoxy resin; The solvable phenol aldehyde type epoxy resin of cresols (epoxy equivalent (weight) 220, Sumitomo Chemical Company Ltd produces, commodity are called ESCN001) 15 weight parts; As curing agent for epoxy resin, use solvable fusible phenol aldehyde type epoxy resin (commodity that Dainippon Ink. & Chemicals Inc produces PLYOPHEN LF2882 by name) 40 weight parts; As intermiscibility and weight-average molecular weight being arranged at the high molecular weight resin more than 30,000, use phenoxy resin (molecular weight 50,000, the commodity that Toto Kasei KK produces PHENOTOHTO YP-50 by name) 15 weight parts with epoxy resin; As containing the epoxy group(ing) acrylic copolymer, use to contain epoxy group(ing) acrylic rubber (molecular weight 1,000,000, the commodity that Teikoku Chemical Industries Co., Ltd produces HTR-860P-3 by name) 150 weight parts; As curing catalyst, use curing catalyst 1-cyanoethyl-2-phenylimidazole (CUREZOLE 2PZ-CN) 0.5 weight part; As silane coupling agent; Use γ-glycidoxypropyltrime,hoxysilane (commodity that Japan Unicar Co., Ltd. produces NUC A-187 by name) 0.7 weight part; In the compsn of above-mentioned composition, add methyl ethyl ketone and mix stirring, carry out vacuum outgas.Being coated onto thickness to resulting varnish is 50 microns having carried out on the polyimide film of plasma treatment, 130 ℃ of following heat dryings 5 minutes, forms thickness and be 50 microns the filming of B stage condition, and makes the single face bonding film.Secondly, on that one side of the uncoated tackiness agent of the polyimide film of this single face bonding film, apply same varnish,, form thickness and be 50 microns the filming of B stage condition, be made into the double-sided adhesive film of three-decker 140 ℃ of following heat dryings 5 minutes.
Under this state, the degree of cure of the binder constituents of bonding film is measured the result of (heat-up rate is 10 ℃/minute) with DSC (DSC of the commodity that E.I.Du Pont Company produces 912 types by name), is in 15% the state that thermal discharge reaches total curing exotherm amount.In addition, be soaked in tackiness agent (weight W 1) among the THF, and 25 ℃ place 20 hours after; Do not dissolve part with the filtration of 200 purpose nylon cloths; Measure its dried weight (weight W 2), obtain the THF percentage extraction (=(W1-W2) * 100/W1), the THF percentage extraction is 35 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 360MPa at 25 ℃, is 4MPa at 260 ℃.
< embodiment 8 >
Contain carboxylated acrylonitrile-divinyl rubber (molecular weight 400,000 except changing the phenoxy resin that in embodiment 7, uses into; Japan Synthetic Rubber Co. Ltd produces; Commodity are called PNR-1) outside, warp is made the double-sided adhesive film of three-decker with embodiment 7 identical processing.Should explain that the degree of cure of the binder constituents of the bonding film under this state with the result that DSC measures, is in 20% the state that thermal discharge reaches total curing exotherm amount.The THF percentage extraction is 35 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 300MPa at 25 ℃, is 3MPa at 260 ℃.
< embodiment 9 >
Being coated onto thickness to the tackiness agent varnish that in embodiment 7, uses is 50 microns gathering on this dioctyl phthalate glycol ester film; 140 ℃ of heat dryings 5 minutes; Form thickness and be 50 microns the filming of B stage condition, process and be used to be laminated to the bonding film on the thermotolerance thermoplastic film that constitutes core.80 ℃ of laminating machine roller temperatures; Feeding speed 0.2m/ branch; Under the lamination of line pressure 5kg, using vacuum laminator to be laminated to thickness to this bonding film is on 50 microns the two sides of the polyimide film of having implemented plasma treatment, makes the double-sided adhesive film of three-decker thus.Should explain, the degree of cure of the binder constituents of the bonding film under this state, with the result that DSC measures, the state after being in 20% heat release that thermal discharge reaches total curing exotherm amount and finishing.The THF percentage extraction is 35 weight %.In addition, measuring the result of the storage elastic modulus of tackiness agent cured article with the Measurement of Dynamic Viscoelasticity device, is 360MPa at 25 ℃, is 4MPa at 260 ℃.
< comparative example 10 >
Being coated onto thickness to the tackiness agent varnish that in embodiment 7, uses is on 50 microns the polyethylene terephthalate film, 140 ℃ of heat dryings 5 minutes, forms thickness and be 75 microns the filming of B stage condition, and processes bonding film.With 2 pieces of these bonding films, under the lamination identical, make it the synthetic bonding film of layer without core with embodiment 9.The binder constituents of resulting bonding film is 20% of total curing exotherm amount, and the THF percentage extraction is 35 weight %.In addition, storage elastic modulus is 360MPa at 25 ℃, is 4MPa at 260 ℃.
< comparative example 11 >
Except the polyimide film that uses the thermotolerance thermoplastic film as constituting core of embodiment 7 changes into to the polypropylene screen, the double-sided adhesive film of three-decker is processed in warp and embodiment 7 identical processing.The binder constituents of this bonding film is 20% of total curing exotherm amount, and the THF percentage extraction is 35 weight %.In addition, storage elastic modulus is 360MPa at 25 ℃, is 4MPa at 260 ℃.
< comparative example 12 >
Except the epoxy group(ing) acrylic copolymer that contains embodiment 7 changes (phenoxy resin 165 weight parts) the phenoxy resin into, the double-sided adhesive film of three-decker is processed in warp and embodiment 7 identical processing.The binder constituents of this bonding film is 20% of total curing exotherm amount, and the THF percentage extraction is 90 weight %.In addition, storage elastic modulus is 3400MPa at 25 ℃, is 3MPa at 260 ℃.
< comparative example 13 >
Except the epoxy group(ing) acrylic copolymer that contains embodiment 7 changes into the acrylonitrile-butadiene rubber, the double-sided adhesive film of three-decker is processed in warp and embodiment 7 identical processing.The binder constituents of this bonding film is 20% of total curing exotherm amount, and the THF percentage extraction is 90 weight %.In addition, storage elastic modulus is 500MPa at 25 ℃, is 2MPa at 260 ℃.
For resulting bonding film, investigate its thermotolerance, electrocorrosion-resisting property and wet fastness.In the stable on heating evaluation method, the anti-backflow crack property and the temperature cycling test of the sample that forms pasted semi-conductor chip and printed circuit board in employing with the double-sided adhesive film of three-decker.The broken up evaluation of anti-backflow is performed such: earlier sample is sent in the IR reflow ovens of design temperature; So that the top temperature of sample surfaces is 240 ℃ and kept this temperature 20 seconds; At room temperature place cooling, after carrying out repeatedly handling for 2 times, the crack in the observation sample.Fissured sample not taking place be decided to be well, fissured sample takes place be decided to be defective.Temperature cycling test is that sample was placed 30 minutes in-55 ℃ atmosphere, in 125 ℃ atmosphere, places 30 minutes then, is used as a circulation to this operation, is expressed as the cycle index till destroying.
The evaluation of electrocorrosion-resisting property is performed such: the comb pattern that on the FR-4 substrate, forms lines/at interval=75/75 micron; Be attached to its top to bonding film then, apply at 85 ℃/85%RH and measure the insulating resistance value of sample after 1000 hours of processing like this under the condition of DC6V.Insulating resistance value is good more than 10 Ω, and less than 10 Ω is defective.
The wet fastness evaluation is performed such: after being placed on the processing of carrying out in the pressure cooking tester 96 hours (PCT processing) to the semiconductor device sample, observe peeling off and variable color of bonding film.Do not find out bonding film peel off and variable color be regarded as good, peeling off arranged or have variable color as defective.Its result is shown in table 3.
Figure 2006100998102A00800031
No matter which all is the double-sided adhesive film that is used as the thermotolerance thermoplastic film three-decker of core for embodiment 7,8,9; In binder constituents, all contain epoxy resin and solidifying agent thereof, the high molecular weight resin of intermiscibility arranged and contain the epoxy group(ing) acrylic copolymer, demonstrate the storage elastic modulus under 25 ℃ and 260 ℃ that stipulate in the present invention with epoxy resin.Their operability is good, and anti-backflow crack property, temperature cycling test, electrocorrosion-resisting property and anti-PCT property are good.
Comparative example 10 is owing to being not the double-sided adhesive film that is used as the thermotolerance thermoplastic film three-decker of the core of stipulating among the present invention, so operability is bad.Comparative example 11 is owing to being used as core to the bad polypropylene screen of thermotolerance, so the result of anti-backflow property and temperature cycling test is bad.Comparative example 12 since its be not contained in forming stipulate among the present invention contain the epoxy group(ing) acrylic copolymer, so the storage elastic modulus that demonstrates under 25 ℃ has surpassed the numerical value of stipulating, the result of anti-backflow crack property and temperature cycling test is bad.Comparative example 13 since with 25 ℃ of regulation under storage elastic modulus consistent but do not contain stipulate among the present invention contain the epoxy group(ing) acrylic rubber, so show electrocorrosion-resisting property and the bad result of anti-PCT property.
The possibility of utilizing in the industry
Adopt the present invention, can make the good and good semiconductor packages of heatproof degree cyclicity under the state that is assembled on the motherboard of anti-moisture absorption backflow property.
Tackiness agent of the present invention and bonding film; Because near the Young's modulus room temperature is low; Be assembled to semi-conductor chip with the glass fiber reinforced epoxy resin substrate or with polyimide substrate be under the rigidity printed circuit board and the situation on the flexible printed circuit board of representative, the thermal stresses in the time of can relaxing the heating cooling that the difference because of thermal expansivity causes.Therefore, do not find during backflow that excellent heat resistance takes place in the crack.In addition, contain as the low elastic modulus composition contain the epoxy group(ing) acrylic copolymer, can provide a kind of electrocorrosion-resisting property, wet fastness good, the few jointing material of deterioration when particularly under the condition of strictnesses such as PCT processing, carrying out humidity test.
Be used as the thermotolerance thermoplastic film double-sided adhesive film of the three-decker of core of the present invention; Although near the Young's modulus of binder layer room temperature is low; But operability is good; And be under the rigidity printed circuit board and the situation on the flexible printed circuit board of representative being assembled to semi-conductor chip with glass fiber reinforced epoxy resin substrate and polyimide substrate, the thermal stresses in the time of can relaxing the heating cooling that the difference because of thermal expansivity causes.Therefore, do not find during backflow that excellent heat resistance takes place in the crack.In addition, contain as the low elastic modulus composition contain the epoxy group(ing) acrylic copolymer, can provide a kind of electrocorrosion-resisting property, wet fastness good, the few jointing material of deterioration when particularly under the condition of strictnesses such as PCT processing, carrying out humidity test.
Of the present invention, outside terminal by the area array shape be arranged in the semiconductor packages on the substrate back, be very suitable for being assembled on the miniature electric machine of portable machine particularly or PDA purposes.

Claims (14)

1. a tackiness agent is used in the manufacturing of semiconductor device, it is characterized in that:
Above-mentioned tackiness agent is the tackiness agent of Thermocurable; Wherein, With respect to more than 2 functional groups and the epoxy resin of molecular weight less than 5000 and epoxy curing agent 100 weight parts, contain: glycidyl acrylate or SY-Monomer G, the second-order transition temperature that contains 2～6 weight % for more than-10 ℃ and weight-average molecular weight be to contain epoxy group(ing) acrylic copolymer 100～300 weight parts more than 800,000; And epoxy resin cure promotor 0.1～5 weight part,
The storage elastic modulus that uses the Measurement of Dynamic Viscoelasticity device to survey periodic tackiness agent cured article is 10～2000MPa under 25 ℃, is 3～50Mpa under 260 ℃.
2. tackiness agent according to claim 1 is characterized in that:
Remaining quantity of solvent is below 5 weight %.
3. tackiness agent according to claim 1 is characterized in that:
State after 10～40% heat release of the total curing exotherm amount when said tackiness agent is in the differential calorimeter measurement finishes.
4. the described tackiness agent of claim 1, it is characterized in that: above-mentioned solidifying agent is a resol.
5. tackiness agent according to claim 1 is characterized in that:
Also contain with epoxy resin and have intermiscibility and weight-average molecular weight at the high molecular weight resin more than 30,000.
6. tackiness agent according to claim 5 is characterized in that:
In the above-mentioned tackiness agent, also contain above-mentioned high molecular weight resin 10～40 weight parts.
7. tackiness agent according to claim 6 is characterized in that:
Above-mentioned high molecular weight resin is a phenoxy resin,
Above-mentioned solidifying agent is a resol.
One kind through adhesive member the semiconductor device of mounting semiconductor chip to the organic system support substrate, it is characterized in that:
The mounting semiconductor chip side of above-mentioned organic system support substrate and with the opposition side that loads semi-conductor chip one side in any at least side, form the wiring of regulation,
Form outside terminal for connecting on opposition side area array shape above-mentioned organic system support substrate and the mounting semiconductor chip side ground, the cloth bundle of lines semi-conductor chip terminal and the said external terminal for connecting of afore mentioned rules couple together,
At least the connection portion between the wiring of above-mentioned semi-conductor chip terminal and regulation is carried out resin-sealed,
Above-mentioned adhesive member is to make the tackiness agent described in the claim 1 always solidify the member that the back is constituted.
9. semiconductor device according to claim 8 is characterized in that: the wiring that will stipulate is carried out wire bonds with the semi-conductor chip terminal or directly is connected.
10. semiconductor device according to claim 8 is characterized in that: above-mentioned adhesive member is a kind of structure that on the two sides of core, is formed with the layer of the described tackiness agent of claim 1.
11. a bonding film is characterized in that:
Film like ground forms the described tackiness agent of claim 1.
12. a bonding film is characterized in that:
It is the three-decker that possesses core and the layer of the described tackiness agent of claim 1 is set on the two sides of this core.
13. bonding film according to claim 12 is characterized in that:
The second-order transition temperature of above-mentioned core is more than 200 ℃.
14. bonding film according to claim 12 is characterized in that:
Above-mentioned core is selected among polyimide, polyethersulfone, polyamidoimide and polyetherimide.
CN2006100998102A 1996-10-08 1997-10-08 Semiconductor device, adhesive, and adhesive film Expired - Fee Related CN1923939B (en)

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