CN104910825A

CN104910825A - Adhesive sheet and use thereof

Info

Publication number: CN104910825A
Application number: CN201510225030.7A
Authority: CN
Inventors: 木村雄大; 菅生悠树; 宇圆田大介
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2011-07-25
Filing date: 2012-07-25
Publication date: 2015-09-16
Also published as: CN102898966A; TW201305306A

Abstract

The invention provides an adhesive sheet for manufacturing a semiconductor device. The adhesive sheet inhibits cracking or chipping of a semiconductor wafer etc. and, at the same time, has chemical stability and controls physical property easily. The adhesive sheet for manufacturing the semiconductor device includes: a thermoplastic resin having a carboxyl group and not having an epoxy group; a thermosetting resin; and a complex forming organic compound which includes a benzene ring having two or more phenolic hydroxyl groups and forms a complex with cation.

Description

Sheet adhesive and uses thereof

The divisional application that the application is the applying date is on July 25th, 2012, application number is the Chinese patent application of 201210260856.3.

Technical field

The present invention relates to sheet adhesive and uses thereof.

Background technology

In recent years, by the memory unit chip (メモリパッケージチップ) of mobile phone, portable audio device, multistage is stacked and the stacking MCP (Multi Chip Package: multi-chip package) obtained is popularized.In addition, along with the multifunction of image processing techniques, mobile phone etc., advancing the densification of encapsulation, highly integrated and slimming.As the method be fixed to by semi-conductor chip on substrate etc., propose the method using thermosetting paste resin, the method using sheet adhesive thermoplasticity and thermosetting resin combinationally used.

On the other hand, there are the following problems: externally to being mixed into positively charged ion (such as, cupric ion, iron ion) in the crystalline substrate of wafer in the operation of semiconductor manufacturing, when this positively charged ion arrives the circuit forming surface formed on wafer, and electrical characteristic decline.In addition, exist and produce positively charged ion from circuit or metal wire in goods use, thus the problem that electrical characteristic decline.

For the problems referred to above, attempted processing the back side of wafer and forming crushable layer (strain) in the past, and to be caught by this crushable layer and the outside of decationize is gone defect method (hereinafter also referred to " EG ") or in the crystalline substrate of wafer, formed oxygen precipitation induced defects (acid element is separated out and owed Xian), and to be caught by this oxygen precipitation induced defects and defect method (hereinafter also referred to " IG ") is gone in the inside of decationize.

But along with the slimming of wafer in recent years, the effect of IG reduces, and cause wafer break or the back side strain of warpage is also removed, thus the effect of EG also can not get, thus there is the problem of going defect effect insufficient.

Therefore, propose various for supplementing the scheme of defect effect of going.In patent documentation 1, describe the film like tackiness agent possessing copper absorption layer, described copper absorption layer can form the resin of the skeleton of complex compound with cupric ion containing having.In addition, describe the resin inside that cupric ion can be made to be chemically adsorbed to copper absorption layer, significantly can reduce the impact of the cupric ion produced from the component taking copper as material than ever.In addition, in patent documentation 2,3, describe the adhesive glue adhesive composition containing ion capturing agent, disclose this ion capturing agent and there is the effect catching chlorion etc.In addition, in patent documentation 4, describe the film like tackiness agent containing ion trap agent, and describe this ion trap agent seizure haloid element.In addition, in patent documentation 5, describe the sheet adhesive containing anion ion exchange body.In addition, in patent documentation 6, describe containing chelate modified epoxy resin, the Web-form adhesive of inner ionic impurity can be caught.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2011-52109 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2009-203337 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2009-203338 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2010-116453 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2009-256630 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2011-105875 publication

Summary of the invention

But, even if use the above-mentioned supplementary technology of going defect effect, also can following point be produced.

First problem is, catches cationic technology not open for the film like tackiness agent by patent documentation 2 ~ 5 etc.Therefore, if catch chlorion, be then difficult to prevent from declining based on cationic electrical characteristic.In addition, ion capturing agent disclosed in patent documentation 2 ~ 5, ion trap agent, anion ion exchange body are mineral compound.Therefore, there are the following problems: in seizure property, produce deviation due to the dispersion state in the resin of film like tackiness agent etc., or when pasting on wafer, and mineral compound and contact wafers thus produce wafer breakage or defect.Especially, there is the requirement of the slimming of sheet adhesive in recent years, be therefore necessary breaking or defect of the wafer suppressing mineral compound to cause.

In addition, according to the film like tackiness agent of patent documentation 1 or the Web-form adhesive of patent documentation 6, cupric ion can be caught.In addition, the skeleton of complex compound can be formed with cupric ion owing to having in resin, therefore be difficult to produce mineral compound and contact wafers thus wafer produces and breaks or the problem of defect.But, in resin, the skeleton of complex compound can be formed with cupric ion, likely with other resin reaction forming film like tackiness agent etc.Therefore, there are the following problems: the chemical stability of film like tackiness agent etc. declines, or the physical property of film like tackiness agent etc. is difficult to control, thus can not get required characteristic.

Therefore, seeking suppress semiconductor wafer etc. break or while defect, there is chemical stability and physical property hold manageable semiconductor device manufacture sheet adhesive, there is the semiconductor device of the sheet adhesive of this semiconductor device manufacture and use the manufacture method of semiconductor device of sheet adhesive of this semiconductor device manufacture.

Second Problem is, in order to realize above-mentioned semiconductor device high capacity and by semiconductor packages size normalised time, not only need the slimming of wafer, and also need slimming for the film like tackiness agent of fixing semi-conductor chip.Generally speaking, containing during for guaranteeing the filler of the Young's modulus under high temperature in film like tackiness agent, film like tackiness agent is thinner, then the defect of the semi-conductor chip that contained in film like tackiness agent thick filler causes or the frequency of breaking more can rise.Along with slimming in recent years, the intensity of semi-conductor chip self also declines, and the generation of the defect or such physical abuse of breaking therefore with semi-conductor chip becomes obvious tendency.In addition, even such as film like tackiness agent contains the situation of the material of trap ions, in the propelling of the slimming of film like tackiness agent, the ion trapping efficiency of film like tackiness agent entirety also can decline, and therefore requires more effective ion trapping.In above-mentioned prior art (such as patent documentation 1), although trap ions in a way can be carried out, but because the skeleton part that can form complex compound exists only in resinous terminal, therefore decline with the contact frequency of cupric ion, complex compound is formed also insufficient, the leeway be therefore still improved.

Therefore, seeking to prevent the electrical characteristic of manufactured semiconductor device from declining thus improving goods reliability, even and if carry out the film like tackiness agent that slimming also can prevent the physical abuse to wafer or semi-conductor chip.

3rd problem is, using when having the sheet adhesive of ion-catching and cut film combinations and use as dicing/die bonding film, when finding that there is, the ion-catching of sheet adhesive declines.

Therefore, even if seeking to use the sheet adhesive of ion-catching also can prevent the ion-catching of sheet adhesive from declining, and the metal ion that is mixed into semi-conductor chip in the manufacturing process of semiconductor device can be caught thus the dicing/die bonding film that the electrical characteristic of semiconductor device decline can be prevented.

Present inventor has carried out research extensively and profoundly, found that, by adopting following formation, can solve above-mentioned existing issue, thus completing the present invention.

That is, the sheet adhesive of semiconductor device manufacture of the present invention, is characterized in that, contain: thermoplastic resin, and described thermoplastic resin has carboxyl and do not have epoxy group(ing); Thermosetting resin; With complex compound formative organic compound, described complex compound formative organic compound contains the phenyl ring with two or more phenolic hydroxyl group, and can form complex compound with positively charged ion.

According to described formation, containing the complex compound formative organic compound of complex compound can be formed with positively charged ion, the positively charged ion be mixed into from outside in the various operations of the manufacture of semiconductor device therefore can be caught.As a result, the positively charged ion be mixed into from outside is difficult to arrive the circuit forming surface formed at wafer, and electrical characteristic can be suppressed to decline, thus improves goods reliability.In addition, owing to being complex compound formative organic compound, even if therefore contact with semiconductor wafer etc. when gluing, wafer also can be suppressed to produce and to break or defect.

In addition, when semiconductor wafer being glued on adherend by sheet adhesive, generally speaking existing concavo-convex on adherend, therefore can be mixed into bubble.This bubble is diffused in sealing resin etc. by pressure etc. when resin seal usually, thus its impact weakens.But, when to use containing the compound of phenyl ring with two or more phenolic hydroxyl group as complex compound formative organic compound, when there is epoxy group(ing) in thermoplastic resin, by the thermal history in the operations such as the wire bond before resin seal, reaction can be cured tempestuously, thus bubble can not be made in resin seal operation to be diffused in sealing resin.As a result, the stripping caused by bubble is produced in gluing interface.Especially, when semi-conductor chip is multilayer laminated, thermal history increases, and bubble is remarkable on the impact of peeling off.According to the present invention, thermoplastic resin does not have epoxy group(ing), therefore can suppress with containing the reaction of complex compound formative organic compound of phenyl ring with two or more phenolic hydroxyl group.Therefore, the chemical stability of sheet adhesive can be improved.In addition, owing to being suppressed with the reaction of complex compound formative organic compound containing the phenyl ring with two or more phenolic hydroxyl group, therefore be cured reaction tempestuously before can suppressing forming process, thus the bubble at gluing interface can be made to be diffused in sealing resin etc.Thus, the stripping of gluing interface can be prevented.

In addition, according to aforementioned formation, thermoplastic resin has carboxyl, and therefore such as by the after fixing operation after resin seal, it is crosslinked that thermoplastic resin carries out to a certain degree, can prevent the stripping of gluing interface.

That is, according to aforementioned formation, contain: thermoplastic resin, described thermoplastic resin has carboxyl and does not have epoxy group(ing); Thermosetting resin; With complex compound formative organic compound, described complex compound formative organic compound contains the phenyl ring with two or more phenolic hydroxyl group, and complex compound can be formed with positively charged ion, therefore can improve the goods reliability of the semiconductor device using the sheet adhesive of this semiconductor device manufacture to manufacture.

In aforementioned formation, preferred: relative to total amount 100 weight part of the sheet adhesive of semiconductor device manufacture, containing complex compound formative organic compound described in thermosetting resin, 0 ~ 60 parts of filler material by weight and 0.1 ~ 5 weight part described in thermoplastic resin, 5 ~ 50 weight parts described in 5 ~ 95 weight parts.By described each composition is set in described numerical range, breaking or defect of semiconductor wafer etc. can be suppressed further, and chemical stability can be improved further, and more easily can control physical property.

In aforementioned formation, preferably: the sheet adhesive of the semiconductor device manufacture of weight 2.5g to be impregnated in the 50ml aqueous solution containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, the copper ion concentration in the described aqueous solution is 0 ~ 9.9ppm.According to aforementioned formation, the cupric ion be mixed into from outside in the various operations of the manufacture of semiconductor device can be caught further.As a result, the cupric ion be mixed into from outside is more difficult to reach the circuit forming surface formed at wafer.

In addition, semiconductor device of the present invention, is characterized in that, has the sheet adhesive of the semiconductor device manufacture recorded above.According to aforementioned formation, there is the sheet adhesive of the semiconductor device manufacture recorded above, therefore can obtain the semiconductor device that goods reliability improves.

In addition, the manufacture method of semiconductor device of the present invention, is characterized in that, semi-conductor chip is pasted the operation on adherend by the sheet adhesive comprising the semiconductor device manufacture by recording above.According to aforementioned formation, the semiconductor device of the sheet adhesive with the semiconductor device manufacture recorded can be manufactured above, therefore can obtain the semiconductor device that goods reliability improves.

In the present invention, as an embodiment, also comprise a kind of film like tackiness agent, it contains: the ion-catching organic compound dissociated from resin matrix, the mineral filler of below median size 500nm and tackiness resin.

In this film like tackiness agent, due to the median size of mineral filler is set as below 500nm, the ratio of median size relative to the thickness of film like tackiness agent of mineral filler therefore can be reduced.As a result, even if carry out the slimming of this film like tackiness agent in order to the high capacity of tackling semiconductor device, the physical abuse to semi-conductor chip etc. can also be prevented.In addition, ion-catching organic compound is in the free state (state be not combined with resin matrix) of all resins skeleton (comprising above-mentioned tackiness resin) that contains from this adhesive foil, therefore degree of freedom is high, also high with the contact frequency of metal ion, thus can ion-catching be improved.In addition, ion-catching organic compound self is organism, therefore with the consistency of resinous principle or affinity also good.Thus, balancedly can exist in this film like tackiness agent entirety, even if therefore carry out slimming, also can improve ion-catching efficiency.In addition, in this specification sheets, " resin matrix " is explained with resin or the normally used implication of field of polymer technology, such as, when forming resin by one or more repeating units, refers to that these repeating units connect and the structure of formation.The measuring method of the median size of mineral filler is based on the record of embodiment.

The thickness of this film like tackiness agent can suitably slimming to 3 ~ 15 μm.

More than one specifically for being selected from the group that is made up of acrylic resin, epoxy resin and resol of described tackiness resin.

Described in this film like tackiness agent, the content of mineral filler is preferably 1 ~ 30 % by weight.Thus, the Young's modulus of (such as 175 ~ 260 DEG C) under can high temperature being guaranteed, and mineral filler can be prevented the physical abuse of semi-conductor chip.

When stretching store elastic modulus after this film like tackiness agent solidifies 1 hour at 175 DEG C at 175 DEG C is 0.5 ~ 500MPa, even if also can suitably prevent this film like tackiness agent from peeling off from semi-conductor chip through pyroprocessing such as sealing process.

When this film like tackiness agent clipping viscous force solidified after 1 hour at 175 DEG C at 175 DEG C is 0.01 ~ 50MPa, the shearing strain caused due to the ultrasonic vibration in wire bond operation can be prevented while the tackiness that maintenance is good, thus can fabrication yield be improved.

In this film like tackiness agent, relative to described tackiness resin 100 weight part, preferably containing 1 ~ 10 weight part ion-catching organic compound.By the content of ion-catching organic compound is set as above-mentioned scope, effectively can catches metal ion and can prevent excessive ion-catching organic compound from causing the change of adhesive property.

In this film like tackiness agent, the content of described mineral filler is that benchmark is set as 1.1 ~ 80 relative to the ratio of the content of described ion-catching organic compound in weight, mineral filler can be utilized thus to prevent ion-catching organic compound from causing Young's modulus or adhesive power to decline, and mineral filler can be prevented the physical abuse of semi-conductor chip.

In the present invention, alternatively, also comprise a kind of dicing/die bonding film, it has: cutting film, and described cutting film has base material and stacked binder layer on the substrate; With the sheet adhesive be layered on described binder layer, described sheet adhesive contains the ion capturing agent that can catch metal ion, and the store elastic modulus of described binder layer at 26 DEG C is 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷below Pa.

In this dicing/die bonding film, binder layer has 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷the store elastic modulus of below Pa, therefore forms the crosslinking structure of appropriateness in this binder layer.Thus, ion capturing agent can be limited from sheet adhesive to the transfer etc. of binder layer, result, the decline of the ion-catching of sheet adhesive can be suppressed.In addition, sheet adhesive contains the ion capturing agent (below sometimes referred to as " ion capturing agent ") that can catch metal ion, therefore can effectively catch the metal ion being mixed into semi-conductor chip in semiconductor fabrication sequence, thus the deterioration of the electrical characteristic of obtained semiconductor device can be prevented.In addition, owing to can be kept the ion-catching of sheet adhesive to the transfer of binder layer etc. from sheet adhesive by restriction ion capturing agent, the further slimming of the sheet adhesive accompanied with the high capacity of semiconductor device can therefore also be tackled.

According to this dicing/die bonding film, described ion capturing agent is can form the organic compound of complex compound with metal ion, even if thus when the constituent material with binder layer has affinity, the transfer etc. of ion capturing agent also suitably can be suppressed.

About this dicing/die bonding film, preferably the sample of the weight 2.5g got from described sheet adhesive to be impregnated in the 50ml aqueous solution containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, the copper ion concentration in the described aqueous solution is 0 ~ 9.8ppm.By making sheet adhesive have such cupric ion seizure property, the metal ion being mixed into semi-conductor chip etc. in semiconductor device manufacturing process can be caught.As a result, the metal ion be mixed into from outside is difficult to arrive the circuit forming surface formed at wafer, thus can suppress the decline of electrical characteristic, improves goods reliability.

In this dicing/die bonding film, the acrylic resin of described binder layer preferably containing weight-average molecular weight more than 300,000.In addition, described acrylic resin is preferably using hydroxy acryl acid class monomer as being formed monomer.In addition, described binder layer preferably containing isocyanates linking agent, and contains 1 ~ 5 weight part isocyanates linking agent relative to described acrylic resin 100 weight part.By being used alone or in combination such formation, the crosslinking structure of the transfer that can limit ion capturing agent etc. suitably can be formed within the adhesive layer.

In this dicing/die bonding film, described binder layer can be radiation curable.Now, the store elastic modulus of binder layer before irradiation with radiation at 26 DEG C needs to be 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷below Pa.

This dicing/die bonding film, as mentioned above, can prevent the deterioration of the ion-catching of sheet adhesive, therefore can by the reduced thickness of described sheet adhesive to more than 3 μm and less than 150 μm.

Accompanying drawing explanation

Fig. 1 is the cross-sectional schematic of the dicing/die bonding film representing an embodiment of the invention.

Fig. 2 is the cross-sectional schematic of the example represented by the die bonding film mounting semiconductor chip in described dicing/die bonding film.

Fig. 3 is the cross-sectional schematic of the example represented by the three-dimensional mounting semiconductor chip of the die bonding film in described dicing/die bonding film.

Fig. 4 is the cross-sectional schematic of the dicing/die bonding film representing another embodiment of the present invention.

Embodiment

< first embodiment >

The sheet adhesive (hereinafter also referred to as " sheet adhesive ") of the semiconductor device manufacture of present embodiment, contain: thermoplastic resin, described thermoplastic resin has carboxyl and does not have epoxy group(ing); Thermosetting resin; With complex compound formative organic compound, described complex compound formative organic compound contains the phenyl ring with two or more phenolic hydroxyl group, and can form complex compound with positively charged ion.

Described sheet adhesive contains and can form the complex compound formative organic compound of complex compound with positively charged ion, therefore can catch the positively charged ion be mixed into from outside in the various operations of the manufacture of semiconductor device.As a result, the positively charged ion be mixed into from outside is difficult to arrive the circuit forming surface formed at wafer, can suppress the decline of electrical characteristic, thus improves goods reliability.In addition, owing to being complex compound formative organic compound, even if therefore contact with semiconductor wafer etc. when gluing, also can suppress to break or defect.

In addition, thermoplastic resin does not have epoxy group(ing), therefore can suppress with containing the reaction of compound of phenyl ring with two or more phenolic hydroxyl group.Therefore, the chemical stability of sheet adhesive can be improved.In addition, owing to being suppressed with the reaction of compound containing the phenyl ring with two or more phenolic hydroxyl group, being cured reaction tempestuously before therefore can suppressing forming process, thus the bubble at gluing interface can be made to be diffused in sealing resin etc.Thus, the stripping of gluing interface can be prevented.

In addition, thermoplastic resin has carboxyl base, and therefore such as by the after fixing operation after resin seal, it is crosslinked that thermoplastic resin carries out to a certain degree, can prevent the stripping of gluing interface.

That is, according to described sheet adhesive, contain: thermoplastic resin, described thermoplastic resin has carboxyl and does not have epoxy group(ing); Thermosetting resin; With complex compound formative organic compound, described complex compound formative organic compound contains the phenyl ring with two or more phenolic hydroxyl group, and complex compound can be formed with positively charged ion, therefore can improve the goods reliability of the semiconductor device using the sheet adhesive of this semiconductor device manufacture to manufacture.

Described complex compound formative organic compound preferably dissolves in organic solvent.When complex compound formative organic compound dissolves in organic solvent, can easily and suitably be distributed in resin.In addition, in the present invention, complex compound formative organic compound dissolves in organic solvent and refers to, such as, relative to methylethylketone 100 weight part as organic solvent, 1 weight part complex compound formative organic compound does not produce and to be suspended etc. and can to dissolve.

In the present invention, the positively charged ion of complex compound is formed with described complex compound formative organic compound, as long as positively charged ion is then not particularly limited, can enumerate such as: the ion of Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, V etc.

(complex compound formative organic compound)

As long as described complex compound formative organic compound is containing having the phenyl ring of phenolic hydroxyl group on two and the compound that can form complex compound with positively charged ion is then not particularly limited, from the viewpoint of suitably positively charged ion can be caught and suppress the reaction of the carboxyl had with described thermoplastic resin, tannin, rhodanine derivative (gallic acid, methyl gallate, pyrogallol) etc. can be enumerated.These compounds may be used singly or two or more in combination.As described complex compound formative organic compound, be preferably micro mist shape, be soluble in organic solvent or the organic compound of liquid state.

Described sheet adhesive contains and has carboxyl and thermoplastic resin and the thermosetting resin without epoxy group(ing).As described thermosetting resin, resol, aminoresin, unsaturated polyester resin, epoxy resin, urethane resin, polyorganosiloxane resin or thermoset polyimide resin etc. can be enumerated.These resins may be used singly or two or more in combination, especially, preferably use in epoxy resin and resol at least any one.Especially, when using epoxy resin, the high adhesive power under high temperature (such as 175 ~ 260 DEG C) can be obtained.Therefore, by complex compound formative organic compound and epoxy composite being used, the sheet adhesive that adhesive power under high temperature is high can be obtained.

Described epoxy resin, as long as the epoxy resin used usually used as adhesive compound is then not particularly limited, can use such as: bifunctional epoxy resin or the epoxy resin such as polyfunctional epoxy resin or glycolylurea type, triglycidyl isocyanurate type or glycidic amine type such as bisphenol A-type, bisphenol-f type, bisphenol S type, bmminated bisphenol-A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, phenol novolak type, ortho cresol novolak type, three (hydroxyphenyl) methane type, four (hydroxyphenyl) ethane type.These epoxy resin may be used singly or two or more in combination.In these epoxy resin, particularly preferably phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, three (hydroxyphenyl) methane type epoxy resin or four (hydroxyphenyl) ethane type epoxy resin.This is because: these epoxy resin are good with the reactivity as the resol of solidifying agent, and thermotolerance etc. are excellent.

In addition, described resol works as the solidifying agent of described epoxy resin, can enumerate such as: the novolak phenolics such as phenol resol resins, phenol aralkyl resin, cresol novolac resin, t-butylphenol novolac resin, nonylphenol novolac resin, resole (レゾー Le) polycarboxylated styrene etc. such as type resol, poly(4-hydroxystyrene).These resol may be used singly or two or more in combination.Particularly preferably phenol resol resins, phenol aralkyl resin in these resol.This is because the connection reliability of semiconductor device can be improved.

The mixing ratio of described epoxy resin and resol, such as, it is suitable for carrying out coordinating in the mode that is 0.5 ~ 2.0 equivalent relative to the hydroxyl in the epoxy group(ing) 1 equivalent resol in described epoxy resin ingredient.In addition, be more suitably 0.8 ~ 1.2 equivalent.That is, this is because: when both mixing ratios are beyond described scope, can not sufficient curing reaction be carried out, thus the characteristic of epoxy resin cured product is easily deteriorated.

As described thermoplastic resin, as long as there is carboxyl and the thermoplastic resin without epoxy group(ing) is then not particularly limited, can enumerate: the saturated polyester resins such as isoprene-isobutylene rubber, synthetic polyisoprene, chloroprene rubber, vinyl-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene, polycarbonate resin, thermoplastic polyimide resin, polyamide resin, phenoxy resin, acrylic resin, PET and PBT, polyamide-imide resin or fluorine resin etc.These thermoplastic resins may be used singly or two or more in combination.In these thermoplastic resins, hot other preferred ion impurity is few, thermotolerance is high and can guarantee the acrylic resin of the reliability of semiconductor element.

As described acrylic resin, as long as there is carboxyl and the acrylic resin without epoxy group(ing) is then not particularly limited, can enumerate such as: there is the ester of the acrylic or methacrylic acid of the straight or branched alkyl of carbonatoms less than 30, particularly carbonatoms 4 ~ 18 and the multipolymer of the monomer containing carboxyl.As described alkyl, can enumerate such as: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, amyl group, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, stearyl, octadecyl or eicosyl etc.In addition, as the monomer containing carboxyl, vinyl carboxylates, vinyl-acetic ester etc. can be enumerated.

In described sheet adhesive, relative to total amount 100 weight part of sheet adhesive, preferably containing 5 ~ 95 weight parts (more preferably 10 ~ 90 weight parts) described thermoplastic resin, 5 ~ 55 weight parts (more preferably 10 ~ 50 weight parts) described thermosetting resin, 0 ~ 60 weight part (more preferably 0 ~ 50 weight part) filler, and the described complex compound formative organic compound of 0.1 ~ 5 weight part (more preferably 0.5 ~ 3 weight part).By described each composition is set in described numerical range, breaking or defect of semiconductor wafer etc. can be suppressed further, and chemical stability can be improved further, and more easily can control physical property.

About described sheet adhesive, the sheet adhesive of weight 2.5g to be impregnated in the 50ml aqueous solution containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, copper ion concentration in the described aqueous solution is preferably 0 ~ 9.9ppm, more preferably 0 ~ 9.5ppm, further preferred 0 ~ 8ppm.About described sheet adhesive, the sheet adhesive of weight 2.5g to be impregnated in the 50ml aqueous solution containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, when copper ion concentration in the aqueous solution is 0 ~ 9.9ppm, more easily catch the positively charged ion be mixed into from outside in the various operations of the manufacture of semiconductor device.As a result, the positively charged ion be mixed into from outside is difficult to arrive the circuit forming surface formed at wafer, and electrical characteristic can be suppressed to decline, thus improves goods reliability.

Make described sheet adhesive carry out to a certain degree in advance crosslinked time, the polyfunctional compound that reacts with the functional group etc. of the molecule chain end of polymkeric substance can be added as linking agent.Thus, the adhesive property under high temperature can be improved, thus improve thermotolerance.

As described linking agent, existing known linking agent can be adopted.The particularly polyisocyanate compound such as affixture of more preferably tolylene diisocyanate, diphenylmethanediisocyanate, PPDI, 1,5-naphthalene diisocyanate, polyvalent alcohol and vulcabond.The addition of linking agent is preferably set to 0.05 ~ 7 weight part usually relative to described polymkeric substance 100 weight part.When the amount of linking agent is more than 7 weight part, adhesive power declines, therefore not preferred.On the other hand, during lower than 0.05 weight part, cohesive force is not enough, therefore not preferred.In addition, while containing such polyisocyanate compound, as required can together containing other polyfunctional compounds such as epoxy resin.

In addition, in described sheet adhesive, suitably can coordinate filler according to its purposes.The cooperation of filler can be given electroconductibility to described sheet adhesive or improve thermal conductivity, adjustable elastic modulus etc.As described filler, mineral filler and organic filler can be enumerated, from the viewpoint of raising operability, improve the characteristics such as pyro-conductivity, adjustment melt viscosity, imparting thixotropy, preferred mineral filler.As described mineral filler, be not particularly limited, can enumerate such as: aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium oxide, magnesium oxide, aluminum oxide, aluminium nitride, aluminium borate whisker, boron nitride, crystalline silica, amorphous silica etc.These fillers may be used singly or two or more in combination.From the viewpoint of raising pyro-conductivity, preferential oxidation aluminium, aluminium nitride, boron nitride, crystalline silica, amorphous silica.In addition, good from the viewpoint of above-mentioned each balance of properties, preferred crystalline silica or amorphous silica.In addition, from imparting electroconductibility, improve the object considerations such as pyro-conductivity, conductive material (conductive filler material) also can be used as mineral filler.As conductive filler material, can enumerate and silver, aluminium, gold, copper, nickel, electrical conductivity alloy etc. are formed as spherical, needle-like, flake and the metal oxide such as metal powder, aluminum oxide obtained, amorphous carbon black, graphite etc.

The median size of described filler can be set as 0.001 ~ 1 μm.By the median size of described filler is set as more than 0.001 μm, the wettability to adherend and tackiness can be improved.In addition, by being set as less than 1 μm, the effect in order to give the filler that above-mentioned each characteristic is added can being given full play to, can thermotolerance be guaranteed simultaneously.In addition, the median size of filler is such as the value obtained by luminosity formula size-grade distribution meter (HORIBA system, device name: LA-910).

In addition, in described sheet adhesive, except described complex compound formative organic compound, can suitably coordinate other additive as required.As other additive, anion catching agent, dispersion agent, antioxidant, silane coupling agent, curing catalyst etc. can be enumerated.These additives may be used singly or two or more in combination.

As the manufacture method of the adhesive compound for the formation of described sheet adhesive, be not particularly limited, such as, described thermosetting resin, described thermoplastic resin and described complex compound formative organic compound and other additive are as required put in container, it is made to be dissolved in organic solvent, and be stirred to evenly, can obtain with the form of adhesive compound solution thus.

As described organic solvent, as long as the organic solvent dissolving, mediate or disperse with forming the uniform composition of sheet adhesive then can be not particularly limited, existing known organic solvent can be used.As such solvent, can enumerate such as: the ketones solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, acetone, methylethylketone, pimelinketone, toluene, dimethylbenzene etc.Obtain fast from the viewpoint of rate of drying, marked downly, preferably use methylethylketone, pimelinketone etc.Wherein, the methylethylketone of described complex compound formative organic compound can more preferably be dissolved.

The sheet adhesive of present embodiment, such as, can make in the following way.First, described adhesive compound solution is made.Then, film is formed, then in predefined conditions by this dried coating film by adhesive compound solution coat to base material partition reaches pre-determined thickness.As base material partition, polyethylene terephthalate (PET), polyethylene, polypropylene can be used or carry out the plastics film after surface coated or paper etc. by strippers such as fluorine-containing stripper, chain alkyl esters of acrylic acid strippers.In addition, as coating process, be not particularly limited, can enumerate such as: the coating of roller coat, silk screen, intaglio plate coating etc.In addition, as drying conditions, such as, can carry out in drying temperature 70 ~ 160 DEG C, the scope of 1 ~ 5 minute time of drying.Thus, the sheet adhesive of present embodiment can be obtained.

(manufacture method of semiconductor device)

Below, the embodiment using described sheet adhesive as the manufacture method of semiconductor device during die bonding film is described.Below, the manufacture method of semiconductor device of the dicing/die bonding film 10 being used in the sheet adhesive 3 (hereinafter also referred to die bonding film 3) existing known cutting film being laminated with present embodiment is described.The cutting film of present embodiment has the structure being laminated with binder layer 2 on base material 1.Fig. 1 is the cross-sectional schematic of the dicing/die bonding film representing present embodiment.Fig. 2 is the cross-sectional schematic of the example represented by the die bonding film mounting semiconductor chip in described dicing/die bonding film.

First, as shown in Figure 1, semiconductor wafer 4 is crimped on the semiconductor wafer adhesive portion 3a of the die bonding film 3 in dicing/die bonding film 10, and its gluing maintenance is fixed (installation procedure).This operation utilizes the extruding means extruding such as crimping roller to carry out.

Then, the cutting of semiconductor wafer 4 is carried out.Thus, semiconductor wafer 4 is cut into predetermined size and panelization, makes semi-conductor chip 5.Cutting is such as conventionally carried out from the circuit face side of semiconductor wafer 4.In addition, in this operation, such as, cutting mode etc. that be cut into dicing/die bonding film 10, that be called full cutting can be adopted.The cutting unit used in this operation is not particularly limited, and can adopt existing known cutting unit.In addition, semiconductor wafer is gluing fixing by dicing/die bonding film 10, chip defect or chip therefore can be suppressed to disperse, and can suppress the breakage of semiconductor wafer 4.

In order to peel off by the gluing fixing semi-conductor chip of dicing/die bonding film 10, carry out the pickup of semi-conductor chip 5.Pick-up method is not particularly limited, and can adopt existing known various method.Can enumerate such as: with pin, each semi-conductor chip 5 is pushed away from dicing/die bonding film 10 side, utilize pickup device to pick up the method etc. of the semi-conductor chip 5 above pushed away.

At this, when binder layer 2 is ultraviolet hardening, pick up after to this binder layer 2 irradiation ultraviolet radiation.Thus, the bounding force of binder layer 2 pairs of die bonding films 3 declines, and semi-conductor chip 5 is easily peeled off.As a result, can pick up when not damaging semi-conductor chip 5.

Then, as shown in Figure 2, semi-conductor chip 5 chip join of cutting formation will be passed through on adherend 6 by die bonding film 3.Chip join is undertaken by crimping.As the condition of chip join, be not particularly limited, can suitably set as required.Specifically, such as can carry out in chip join temperature 80 ~ 160 DEG C, chip join pressure 5N ~ 15N, the scope of 1 ~ 10 second chip join time.

Then, the wire bond operation utilizing bonding wire 7 to be electrically connected with the electrode pad (not shown) on semi-conductor chip 5 front end of the portion of terminal (inner lead) of adherend 6 is carried out.As described bonding wire 7, can use such as: gold thread, aluminum steel or copper cash etc.Temperature when carrying out wire bond is carried out in the scope of 80 ~ 250 DEG C, preferably 80 ~ 220 DEG C.In addition, several seconds ~ several minutes can be carried out its heat-up time.Wiring is being heated under the state in described temperature range, and the crimping by combinationally using ultrasonic vibration and applying pressure and produce can be carried out.

In addition, wire bond operation can when not making to carry out when die bonding film 3 thermofixation by heat treated.Now, die bonding film 3 is preferably more than 0.2MPa to the clipping viscous force of adherend at 25 DEG C, more preferably 0.2 ~ 10MPa.By described clipping viscous force is adjusted to more than 0.2MPa, even if carry out wire bond operation when not making die bonding film 3 thermofixation, also shearing strain can not be produced due to the ultrasonic vibration in this operation or heating on the gluing surface of die bonding film 3 and semi-conductor chip 5 or adherend 6.That is, semiconductor element can not be movable due to ultrasonic vibration during wire bond, thus, can prevent wire bond success ratio from declining.

Die bonding film 3 contains: there is carboxyl and do not have the thermoplastic resin of epoxy group(ing), thermosetting resin and containing have two or more phenolic hydroxyl group phenyl ring compound and the complex compound formative organic compound of complex compound can be formed with positively charged ion.Therefore, even if be subject to the thermal history of wire bond operation, the described thermoplastic resin without epoxy group(ing) also hardly with described complex compound formative organic compound reaction.As a result, die bonding film 3 can be suppressed to be cured reaction tempestuously.

Then, the sealing process sealed by semi-conductor chip 5 with sealing resin 8 is carried out.This operation is mounted in semi-conductor chip 5 on adherend 6 or bonding wire 7 carries out to protect.This operation is by carrying out with the ester moulding of mould by sealing.As sealing resin 8, such as, redix can be used.Heating temperature during resin seal is generally 175 DEG C, and carries out 60 ~ 90 seconds, but present embodiment is not limited thereto, and such as, also can solidify several minutes at 165 ~ 185 DEG C.Even if when not making die bonding film 3 thermofixation in after fixing operation afterwards, in this operation, also can make die bonding film 3 thermofixation and gluing fixing while sealing resin 8 solidifies.

In described installation procedure, generally speaking exist fine concavo-convex on semiconductor wafer 4, therefore bubble is mixed in the interface of semiconductor wafer 4 and die bonding film 3 etc.In this sealing process, pressure when this bubble is subject to resin seal and be diffused in sealing resin 8 grade, thus its impact weakens.In addition, as previously mentioned, being subject to the thermal history in wire bond operation of the die bonding film 3 and violent curing reaction caused is suppressed.As a result, bubble can be made in sealing process easily to spread, thus the stripping of the gluing interface of causing due to bubble can be prevented.

Then, in after fixing operation, make in aforementioned seal operation, solidify not enough sealing resin 8 and solidify completely.Even if when not making die bonding film 3 thermofixation in sealing process, in this operation, also can make die bonding film 3 thermofixation and gluing fixing while sealing resin 8 solidifies.Heating temperature in this operation is different because of the kind of sealing resin, and such as, in the scope of 165 ~ 185 DEG C, heat-up time is about 0.5 hour ~ about 8 hours.

In addition, sheet adhesive (die bonding film), also can suitably for as shown in Figure 3 carry out three-dimensional situation of installing by stacked for multiple semi-conductor chip.Fig. 3 is the cross-sectional schematic of the example represented by the three-dimensional mounting semiconductor chip of die bonding film.When three-dimensional shown in Fig. 3 is installed, first, by being cut into at least one die bonding film 3 chip attach of semi-conductor chip same size on adherend 6, then, by die bonding film 3, semi-conductor chip 5 is pasted in the mode that its wire bond face is upside.Then, die bonding film 13 is pasted by the electrode pad portion avoiding semi-conductor chip 5.And then, by another semi-conductor chip 15 with its wire bond face mode chip join that is upside on die bonding film 13.

Then, wire bond operation is carried out.Thus, with bonding wire 7, electrode pad respective in semi-conductor chip 5 and second half conductor chip 15 is electrically connected with adherend 6.In addition, this operation can when implementing without when the heating process of die bonding film 3,13.

Then, utilize sealing resin 8 to carry out sealing process semi-conductor chip 5 grade sealed, and sealing resin is solidified.Then, in after fixing operation, make in described sealing process, solidify insufficient sealing resin 8 and solidify completely.

When semi-conductor chip is multilayer laminated, the thermal history of wire bond operation etc. is many, and the bubble that the interface of die bonding film and semi-conductor chip exists is large on the impact of peeling off.But the described thermoplastic resin without epoxy group(ing) reacts with described complex compound formative organic compound hardly.As a result, die bonding film 3,13 can be suppressed to be cured reaction tempestuously.Therefore, can easily make bubble spread in sealing process, thus the stripping of the gluing interface caused by bubble can be prevented.

In the above-described embodiment, the situation that described sheet adhesive is die bonding film is illustrated, but, as long as the sheet adhesive that described sheet adhesive may be used for the manufacture of semiconductor device is then not particularly limited.Also can be the protective film at the back side of the semi-conductor chip for the protection of flip-chip semiconductor device, diaphragm seal for sealing between the front of the semi-conductor chip by flip-chip semiconductor device and adherend.Described sheet adhesive may be used for the manufacture method comprising the semiconductor device by described sheet adhesive, semi-conductor chip being pasted the operation on adherend.By described sheet adhesive, by semi-conductor chip, the operation pasted on adherend can adopt existing known adhering processes.In addition, the semiconductor device manufactured by the manufacture method of described semiconductor device, for having the semiconductor device of described sheet adhesive.

< second embodiment >

Below, about present embodiment, the difference with the first embodiment is described.The sheet adhesive of present embodiment, as the characteristic except illustrating in the project of present embodiment especially, can play the characteristic same with the sheet adhesive of the first embodiment.

[film like tackiness agent]

Described film like tackiness agent contains: the ion-catching organic compound dissociated from resin matrix, the mineral filler of below median size 500nm and tackiness resin.

In described film like tackiness agent, the median size of mineral filler is below 500nm, therefore can reduce the ratio of size relative to the thickness of film like tackiness agent of mineral filler.As a result, even if carry out the slimming of described film like tackiness agent in order to the high capacity of tackling semiconductor device, the physical abuse to semi-conductor chip etc. can also be prevented.In addition, ion-catching organic compound is in the free state of all resins skeleton that contains from described adhesive foil, and therefore degree of freedom is high, also high with the contact frequency of metal ion, thus can improve ion-catching.In addition, owing to being used as organic ion-catching organic compound, therefore can play the consistency good with resinous principle or affinity, and balancedly can exist in described film like tackiness agent entirety, even if therefore carry out slimming also can improve ion-catching efficiency.

The thickness of described sheet adhesive is not particularly limited, and because the median size of mineral filler contained in described sheet adhesive is below 500nm, therefore in order to tackle the high capacity of semiconductor device, easily can realize slimming.The thickness of sheet adhesive preferably can slimming to 3 ~ 15 μm, more preferably 3.5 ~ 13 μm, preferably carry out slimming to 3 further ~ and 10 μm.

Described film like tackiness agent 85 DEG C, place 120 little water-intake rates constantly in the atmosphere of 85%RH and be preferably less than 3 % by weight, more preferably less than 2 % by weight, further preferably less than 1 % by weight.When described water-intake rate is below 3 % by weight, in semiconductor packages, in film like tackiness agent, the motion of metal ion is suppressed, thus more suitably can catch positively charged ion.

The thermofixation at 175 DEG C of described film like tackiness agent was preferably more than 0.01MPa and below 50MPa to the clipping viscous force of silicon wafer after 1 hour under the condition of 175 DEG C, more preferably more than 0.02MPa and below 30MPa, further preferably more than 0.05MPa and below 25MPa.When described clipping viscous force is more than 0.01MPa under the condition of 175 DEG C, in semiconductor packages, metal ion easily spreads from bracing member (such as wafer etc.) to film like tackiness agent, thus more suitably can catch metal ion.In addition, the shearing strain because ultrasonic vibration during wire bond causes can be prevented, thus the success ratio of wire bond can be improved.

For described film like tackiness agent, the film like tackiness agent of weight 2.5g to be impregnated in the aqueous solution 50mL containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, copper ion concentration in the described aqueous solution is preferably 0 ~ 9.9ppm, more preferably 0 ~ 9.5ppm, further preferred 0 ~ 9.0ppm.By film like tackiness agent, there is such cupric ion catching, the metal ion being mixed into semi-conductor chip etc. in the manufacturing process of semiconductor device can be caught.As a result, the metal ion be mixed into from outside is difficult to arrive the circuit forming surface formed at wafer, can suppress the decline of electrical characteristic, thus can improve goods reliability.In the present invention, copper ion concentration after catching as making cupric ion is the method for 0 ~ 9.9ppm, as mentioned above, can adopt and make the method containing ion-catching organic compound in film like tackiness agent and in the resinous principle for using, introduce the method etc. that carboxylic acid group etc. can catch the method for the functional group of metal ion, boron ion implantation or n-type dopant.

(ion-catching organic compound)

Containing when can catch the ion-catching organic compound of metal ion in described film like tackiness agent, the metal ion being mixed into or can being mixed into semiconductor wafer or semi-conductor chip in the various operations of the manufacture of semiconductor device from outside more suitably can be caught.Ion-catching organic compound with from comprise tackiness resin skeleton described film like tackiness agent in the free state of resin matrix exist, therefore the degree of freedom of diffusion or migration is high, thus effectively can catch metal ion.

In the present invention, as the metal ion caught by described ion-catching organic compound, as long as metal ion is then not particularly limited, can enumerate such as: the ion of Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, Mo, Mn, V etc.

Described ion-catching organic compound, as long as the organic compound of complex compound can be formed with metal ion, then be not particularly limited, from the viewpoint of suitably metal ion can be caught, be preferably selected from more than one in the group be made up of nitrogenous compound, hydroxy-containing compounds and carboxylated compound.

(nitrogenous compound)

As described nitrogenous compound, preferred micro mist shape, be soluble in organic solvent or the nitrogenous compound of liquid state.As such nitrogenous compound, from the viewpoint of more suitably metal ion can be caught, preferably there is the heterogeneous ring compound of tertiary N atom, triazole compounds, tetrazole compound or Bipyridine compound can be enumerated.From the viewpoint of the stability of the complex compound formed between cupric ion, more preferably triazole compounds.These materials may be used singly or two or more in combination.

As described triazole compounds, be not particularly limited, can enumerate: 1,2,3-benzotriazole, two (2-ethylhexyl) amino methyl of 1-{N, N-} benzotriazole, carboxyl benzotriazole, 2-{2 '-hydroxyl-5 '-aminomethyl phenyl } benzotriazole, 2-{2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl }-5-chlorobenzotriazole, 2-{2 '-hydroxyl-3 '-the tertiary butyl-5 '-aminomethyl phenyl }-5-chlorobenzotriazole, 2-{2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl } benzotriazole, 2-{2 '-hydroxyl-5 '-tertiary octyl phenyl } benzotriazole, the tertiary octyl group-6 of 6-(2 benzotriazole base)-4-'-the tertiary butyl-4 '-methyl-2,2 '-methylene radical bis-phenol, 1-(2 ', 3 '-hydroxypropyl) benzotriazole, 1-(1 ', 2 '-dicarboxyl diethyl) benzotriazole, 1-(2-ethylhexylamino methyl) benzotriazole, 2,4-bis-tert-pentyl-6-{ (H-benzotriazole-1-base) methyl } phenol, 2-(2-hydroxyl-5-tert-butyl-phenyl)-2H-benzotriazole, 3-(2H-benzotriazole-2-base)-5-(1,1-dimethyl ethyl)-4-hydroxyl, octyl group-3-[3-tertiary butyl-4-hydroxy-5-(the chloro-2H-benzotriazole of 5--2-base) phenyl] propionic ester, 2-ethylhexyl-3-[3-tertiary butyl-4-hydroxy-5-(the chloro-2H-benzotriazole of 5--2-base) phenyl] propionic ester, 2-(2H-benzotriazole-2-base)-6-(1-methyl isophthalic acid-phenylethyl)-4-(1,1,3,3-tetramethyl butyl) phenol, 2-(2H-benzotriazole-2-base)-4-TBP, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tertiary octyl phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-{2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl } benzotriazole, 2-{2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl }-5-chlorobenzotriazole, 2-[2 '-hydroxyl-3,5-bis-(1,1-dimethyl benzyl) phenyl]-2H-benzotriazole, 2,2 '-methylene-bis [6-(2H-benzotriazole-2-base)-4-(1,1,3,3-tetramethyl butyl) phenol], (2-[two (alpha, alpha-dimethylbenzyl) phenyl of 2-hydroxyl-3,5-]-2H-benzotriazole, 3-(3-(2H-benzotriazole-2-base)-5-tert-butyl-hydroxy phenyl) methyl propionate etc.

As the commercially available product of described triazole compounds, be not particularly limited, can enumerate: the trade(brand)name that north of the city KCC manufactures: BT-120, BT-LX, CBT-1, JF-77, JF-78, JF-79, JF-80, JF83, JAST-500, BT-GL, BT-M, BT-260, BT-365; The trade(brand)name that BASF AG manufactures: TINUVIN PS, TINUVIN P, TINUVIN P FL, TINUVIN 99-2, TINUVIN 109, TINUVIN 900, TINUVIN 928, TINUVIN234, TINUVIN 329, TINUVIN 329FL, TINUVIN 326, TINUVIN 326FL, TINUVIN 571, TINUVIN 213; The trade(brand)name of Taiwan Optical Chemical Company's manufacture forever: EVERSORB 81, EVERSORB 109, EVERSORB 70, EVERSORB 71, EVERSORB 72, EVERSORB 73, EVERSORB 74, EVERSORB 75, EVERSORB 76, EVERSORB 78, EVERSORB 80 etc.Triazole compounds also can use as rust-preventive agent.

As described tetrazole compound, be not particularly limited, 5-amino-1H-TETRAZOLE etc. can be enumerated.

As described Bipyridine compound, be not particularly limited, can 2 be enumerated, 2 '-dipyridyl, 1,10-phenanthroline etc.

(hydroxy-containing compounds)

As described hydroxy-containing compounds, be not particularly limited, preferred micro mist shape, be soluble in organic solvent or the hydroxy-containing compounds of liquid state.As such hydroxy-containing compounds, from the viewpoint of more suitably catching metal ion, preferably an aromatic nucleus has the compound of two or more hydroxyl, diphenol compounds, hydroxyanthraquinone compound or polyphenolic substance can be enumerated particularly, from the viewpoint of the stability of the complex compound formed between cupric ion, more preferably polyphenolic substance.These materials may be used singly or two or more in combination.In addition, aromatic nucleus refers to the conjugate ring structure of π-electron system non-localized, not only comprise the aromatic nucleus (such as phenyl ring) of non-condensation, also comprise the aromatic nucleus (such as, naphthalene nucleus, anthracene nucleus, phenanthrene ring, tetracene ring, pentacene ring, pyrene ring etc.), anthraquinone ring etc. of condensation.

As described diphenol compounds, be not particularly limited, 1,2-dihydroxy-benzene etc. can be enumerated.

As described hydroxyanthraquinone compound, be not particularly limited, alizarin, 1,5-dihydroxyanthraquinone etc.

As described polyphenolic substance, be not particularly limited, tannin, rhodanine derivative (gallic acid, alkyl gallates (as alkyl, such as methyl, ethyl, propyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc. can be enumerated), pyrogallol) etc. can be enumerated.

(carboxylated compound)

As described carboxylated compound, be not particularly limited, can enumerate containing carboxyl aromatics, containing carboxylic fatty compounds of group etc.

As described containing carboxyl aromatics, be not particularly limited, phthalic acid, pyridine carboxylic acid, pyrroles-2-formic acid etc. can be enumerated.

As described containing carboxylic fatty compounds of group, be not particularly limited, higher fatty acid, carboxylic acid type chelating reagent etc. can be enumerated.

As the commercially available product of described carboxylic acid type chelating reagent, be not particularly limited, the trade(brand)name that キレスト Co., Ltd. manufactures can be enumerated: キレスト A, キレスト 110, キレスト B, キレスト 200, キレスト C, キレスト D, キレスト 400, キレスト 40, キレスト 0D, キレスト NTA, キレスト 700, キレスト PA, キレスト HA, キレスト MZ-2, キレスト MZ-4A, キレスト MZ-8 etc.

The content of described ion-catching organic compound is preferably 1 ~ 10 weight part, more preferably 2 ~ 8 weight parts relative to resinous principle 100 weight part forming described sheet adhesive, further preferred 3 ~ 5 weight parts.By being set as more than 1 weight part, effectively can catch positively charged ion (particularly cupric ion), by being set as below 10 weight parts, the decline of thermotolerance or the increase of cost can be suppressed, and the change of the adhesive property that can prevent excessive ion-catching organic compound from causing.

(mineral filler)

In described film like tackiness agent, the mineral filler containing below median size 500nm.The median size of mineral filler is below 500nm, is not particularly limited, preferred 500nm ~ 1nm, more preferably 450nm ~ 2nm, further preferred 400nm ~ 5nm.By the median size of mineral filler is set as below 500nm, the physical abuse to semi-conductor chip can be prevented, and the decline of Young's modulus under high temperature or adhesive power can be prevented.

As described mineral filler, the mineral filler in the first embodiment suitably can be adopted.

Described mineral filler have special restriction, can be any one shape such as spherical, elliposoidal, tabular, bar-shaped, column, stratiform, chain, flakey, circular (De ー Na Star shape), indefinite shape.In addition, although be any one shape, median size is obtained when the mineral filler of object is assumed to spherical based on the diameter of this ball.

The content of mineral filler described in described film like tackiness agent, as long as can prevent from being then not particularly limited the physical abuse of semi-conductor chip, preferably 1 ~ 50 % by weight, more preferably 3 ~ 45 % by weight, further preferably 5 ~ 40 % by weight.Thus, the Young's modulus under high temperature can be guaranteed while preventing mineral filler to the physical abuse of semi-conductor chip.

In described film like tackiness agent, take weight as the ratio of content relative to the content of described ion-catching organic compound of the described mineral filler of benchmark, can consider that the damage of ion-catching, chip preventive, adhesive power etc. are suitably selected, preferably 1.1 ~ 80, more preferably 1.5 ~ 70, further preferably 2.0 ~ 60.By described weight ratio is set in described scope, the Young's modulus that mineral filler can be utilized to prevent ion-catching organic compound from causing or the decline of adhesive power, and mineral filler can be prevented the physical abuse of semi-conductor chip.

(tackiness resin)

In described film like tackiness agent, containing tackiness resin.As tackiness resin, the existing known resin with tackiness can be used, can suitably use thermoplastic resin or thermosetting resin.

(thermoplastic resin)

Described film like tackiness agent is preferably containing thermoplastic resin.As described thermoplastic resin, resin cited in natural rubber and the first embodiment suitably can be used.But, with the first embodiment unlike, the restriction not containing epoxy group(ing) and carboxyl, both containing wherein a kind of, also containing wherein two kinds, also can can not contain.

In described film like tackiness agent, preferred described thermoplastic composition and thermosetting component described later can be cross-linked with each other.Be cross-linked by thermoplastic composition and thermosetting component, the adhesive power under high temperature (such as 175 ~ 260 DEG C) is higher, and can prevent the stripping etc. in reflow soldering operation etc., result, can improve the yield rate of the manufacture of semiconductor device.As the means making described thermoplastic composition and described thermosetting component be cross-linked with each other, can enumerate such as: in two-component, introduce the functional group that can be cross-linked with each other; Deng.As the combination of the functional group that can be cross-linked with each other, can enumerate such as: epoxy group(ing) and hydroxyl, epoxy group(ing) and carboxyl, epoxy group(ing) and amino etc.By the side in the combination of these functional groups is incorporated in described thermoplastic composition, and the opposing party functional group is incorporated in described thermosetting component, described thermoplastic composition and described thermosetting component can be made to be cross-linked with each other.

In order to make described thermoplastic composition and described thermosetting component be cross-linked with each other, when described thermoplastic composition has epoxy group(ing) or carboxyl particularly, suitably can carry out crosslinking reaction with thermosetting component.When thermoplastic composition has epoxy group(ing), described sheet adhesive preferably contains resol as thermosetting component.In addition, when thermoplastic composition has carboxyl, described sheet adhesive preferably contains epoxy resin as thermosetting component.Suitably crosslinking reaction can be carried out between the hydroxyl of the epoxy group(ing) of thermoplastic composition and the resol of thermosetting component or between the epoxy group(ing) of the hydroxyl of thermoplastic composition and the epoxy resin of thermosetting component.In order to introduce epoxy group(ing) in described thermoplastic composition, the monomer containing epoxy group(ing) can be adopted as the formation monomer of described acrylic copolymer.As the monomer containing epoxy group(ing), be then not particularly limited as long as have epoxy group(ing), can enumerate such as: glycidyl acrylate, glycidyl methacrylate etc.In addition, in order to introduce carboxyl in described thermoplastic composition, the monomer containing carboxyl can be adopted as the formation monomer of described acrylic copolymer.As the monomer containing carboxyl, be then not particularly limited as long as have carboxyl, can enumerate such as: vinylformic acid, methacrylic acid, carboxy ethyl acrylate, carboxypentyl acrylate, methylene-succinic acid, toxilic acid, fumaric acid and β-crotonic acid etc.

In described acrylic resin, preferred acid number is the acrylic resin of 5 ~ 150, and more preferably acid number is the acrylic resin of 10 ~ 145, and further preferred acid number is the acrylic resin of 20 ~ 140, and particularly preferably acid number is the acrylic resin of 20 ~ 40.When being the acrylic resin of 5 ~ 150 containing acid number in described film like tackiness agent, the carboxyl of acrylic resin is contributed being formed of complex compound and promoting the seizure effect of ion-catching organic compound, by such synergy, metal ion can be caught more well.The acid number of acrylic resin in the present invention, refers to the mg number of the potassium hydroxide needed for free fatty acids, resinous acid etc. contained in the every 1g sample of neutralization.

In addition, as other monomer forming described polymkeric substance, be not particularly limited, can enumerate such as: anhydride monomers, as maleic anhydride or itaconic anhydride etc.; Hydroxyl monomer, as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxylauric ester, (methyl) vinylformic acid (4-hydroxymethylcyclohexyl) methyl esters etc.; Containing sulfonic group monomer, as styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulphur propyl ester or (methyl) acryloyl-oxy naphthene sulfonic acid etc.; Or phosphorous acid-based monomers, as acryloyl phosphoric acid-2-hydroxy methacrylate etc.; Deng.These monomers may be used singly or two or more in combination.

(thermosetting resin)

In addition, described film like tackiness agent preferably contains thermosetting resin while containing described thermoplastic resin.As described thermosetting resin, can suitably use the thermosetting resin illustrated in the first embodiment.

As the mixing ratio of described thermosetting resin, as long as the degree played as the function of heat curing-type film like tackiness agent is then not particularly limited when heating film like tackiness agent in predefined conditions, 0 ~ 90 % by weight is preferably, more preferably 5 ~ 85 % by weight relative to the weight of film like tackiness agent.

Wherein, from the viewpoint of having the tackiness under low temperature and the Young's modulus under high temperature concurrently, tackiness resin be preferably selected from the group be made up of acrylic resin, epoxy resin and resol more than one.Especially, as tackiness resin, containing epoxy resin, resol and acrylic resin, relative to acrylic resin 100 weight part, the total amount of epoxy resin and resol is preferably 10 ~ 2000 weight parts, more preferably 10 ~ 1500 weight parts, further preferred 10 ~ 1000 weight parts.By being set as more than 10 weight parts by relative to the epoxy resin of acrylic resin 100 weight part and the total amount of resol, plybonding effect can be obtained by solidification, can suppress to peel off, by being set as below 2000 weight parts, film can be suppressed to become fragile and the situation of workability decline.

(linking agent)

When to be carried out by described film like tackiness agent to a certain degree in advance crosslinked, the polyfunctional compound that reacts with the functional group etc. of the molecule chain end of polymkeric substance can be added as linking agent.Thus, the adhesive property under high temperature can be improved, improve thermotolerance.As described linking agent, can suitably use the linking agent illustrated in the first embodiment.

(other additive)

In addition, in described film like tackiness agent, except mentioned component, can suitably coordinate other additive as required.As other additive, can suitably use the additive illustrated in the first embodiment.

In above-mentioned embodiment, the situation being used as the thermosetting resin of tackiness resin, thermoplastic resin as tackiness agent principal constituent contained in film like tackiness agent is illustrated, but, in the present invention, as tackiness agent principal constituent contained in film like tackiness agent, the inorganic componentss such as ceramic-like, cement class, solder can be contained on the basis of above-mentioned thermosetting resin, thermoplastic resin.

[manufacture method of film like tackiness agent]

The film like tackiness agent of present embodiment, such as, make in the following manner.First, the adhesive compound of the precursor as film like tackiness agent is prepared.As preparation method, be not particularly limited, such as, ion-catching organic compound and thermosetting resin as required, thermoplastic resin, other additive put in container, dissolve in organic solvent, and be stirred to evenly, can the form of adhesive compound solution obtain thus.Later program suitably can adopt the program in the first embodiment.

Purposes as described film like tackiness agent is not particularly limited; suitably for the manufacture of semiconductor device, can be able to enumerate such as: can as semi-conductor chip being fixed to die bonding film on the adherends such as lead frame, using for the protection of the protective film at the back side of the semi-conductor chip of flip-chip semiconductor device, the diaphragm seal that is used for sealing semiconductor chips.

The stretching store elastic modulus of described film like tackiness agent before thermofixation at 60 DEG C is preferably more than 0.01MPa and below 1000MPa, more preferably more than 0.05MPa and below 100MPa, further preferably more than 0.1MPa and below 50MPa.By the stretching store elastic modulus before thermofixation at 60 DEG C is adjusted to more than 0.01MPa, the shape as film can be kept, good workability can be given.In addition, by the stretching store elastic modulus before thermofixation at 60 DEG C is adjusted to below 1000MPa, the good wettability to adherend can be given.

[semiconductor device]

Semiconductor device with reference to figure 2 pairs of present embodiments is described.Semiconductor device has: adherend 6, the described film like tackiness agent 3 be layered on described adherend 6, the semi-conductor chip 5 be configured on described film like tackiness agent 3.As adherend 6, can be substrate, also can be other semi-conductor chip.Use substrate as adherend in Fig. 2.In semiconductor device shown in Fig. 2, the mode be connected with the electrode pad (not shown) on semi-conductor chip 5 with the front end of the portion of terminal (inner lead) by adherend 6 further arranges the bonding wire 7 be electrically connected with adherend 6 by semi-conductor chip 5, comprise bonding wire 7, semi-conductor chip 5 is covered by sealing resin 8.

In the semiconductor device of present embodiment, this film like tackiness agent is used when fixing semi-conductor chip on adherend, even if the pyroprocessing therefore through sealing process or reflow soldering operation etc. also can effectively catch the metal ion be mixed in its manufacturing process keeping film like tackiness agent and semi-conductor chip adhering while, as a result, excellent goods reliability can be guaranteed.

[manufacture method of semiconductor device]

Below, the embodiment using above-mentioned film like tackiness agent as the manufacture method of semiconductor device in the situation of die bonding film is described.

(dicing/die bonding film)

Below, the manufacture method of semiconductor device for the dicing/die bonding film 10 being used in the film like tackiness agent 3 (hereinafter also referred to die bonding film 3) existing known cutting film being laminated with present embodiment is described.In addition, the cutting film of present embodiment is the structure being laminated with binder layer 2 on base material 1.

(manufacture method of semiconductor device)

As the manufacture method of the semiconductor device of present embodiment, can suitably adopt the manufacture method illustrated in the first embodiment.

< the 3rd embodiment >

The dicing/die bonding film of present embodiment, has the formation being laminated with sheet adhesive 3 on the cutting film that binder layer 2 is laminated in base material 1 as shown in Figure 1.Sheet adhesive 3 is layered on binder layer 2.In addition, as the generation type of sheet adhesive, as shown in Figure 4, can be the formation being only formed with sheet adhesive 3 ' at semiconductor wafer adhesive portion 3a (with reference to figure 1).

[cutting film]

As described cutting film, can enumerate such as: the cutting film being laminated with binder layer 2 on base material 1.

(base material)

Described base material 1 is as the intensity parent of dicing/die bonding film 10,11.Can enumerate such as: Low Density Polyethylene, linear polyethylene, medium-density polyethylene, high density polyethylene(HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, homo-polypropylene, polybutene, the polyolefine such as polymethylpentene, vinyl-vinyl acetate copolymer, ionomer resin, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate is (random, alternately) multipolymer, ethylene-butene copolymer, ethylene-hexene co-polymers, urethane, polyethylene terephthalate, the polyester such as PEN, polycarbonate, polyimide, polyether-ether-ketone, polyimide, polyetherimide, polymeric amide, Wholly aromatic polyamide, polyphenylene sulfide, aromatic poly amide (paper), glass, woven fiber glass, fluorine resin, polyvinyl chloride, polyvinylidene dichloride, cellulosic resin, polyorganosiloxane resin, metal (paper tinsel), paper etc.When binder layer 2 is ultraviolet hardening, preferred substrates 1 pair of ultraviolet has transmissivity.

In addition, as the material of base material 1, the polymkeric substance such as the crosslinked of aforementioned resin can be enumerated.Described plastics film can not stretch and use, and uses after can carrying out single shaft or biaxial stretch-formed process as required yet.Utilize the resin sheet being imparted heat-shrinkable by stretch processing etc., by making this base material 1 thermal contraction after dicing, the gluing area of binder layer 2 and sheet adhesive 3 can be reduced, thus easily can reclaim semi-conductor chip.

In order to improve and the adhesivity of adjoining course, retentivity etc., usual surface treatment can be implemented in the surface of base material 1, such as, the chemistry such as chromic acid process, ozone exposure, fire exposure, high-voltage electric shock exposure, ionizing ray process or physical treatment, the coating process of silane coupling agent (such as adhesive substance described later) is utilized.

Described base material 1 can the suitably of the same race or different types of material of choice for use, also can use as required several materials is blended after material.In addition, in order to give base material 1 antistatic performance, can arrange on described base material 1 and comprising metal, alloy, their thickness of oxide compound etc. for about the evaporation layer of conductive material.Base material 1 can be individual layer or two or more multilayers.

The thickness of base material 1 is not particularly limited, and can suitably determine, is generally about 5 μm ~ about 200 μm.

In addition, in base material 1, in the scope of effect not damaging present embodiment, various additive (such as, tinting material, weighting agent, softening agent, antiaging agent, antioxidant, tensio-active agent, fire retardant etc.) can be contained.

(binder layer)

The store elastic modulus of binder layer 2 at 26 DEG C is 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷below Pa.Be there is by binder layer 2 the store elastic modulus of such scope, the crosslinking structure of appropriateness can be formed in this binder layer.Thus, ion capturing agent can be limited from sheet adhesive to the transfer etc. of binder layer, result, the decline of the ion-catching of sheet adhesive can be suppressed.

The tackiness agent used in the formation of binder layer 2, as long as show predetermined store elastic modulus after binder layer is formed, and the tackiness agent that can control sheet adhesive 3 in a releasable manner is then not particularly limited.Such as, the pressure-sensitive adhesive that acrylic adhesives, rubber adhesive etc. are general can be used.As described pressure-sensitive adhesive, the viewpoint such as the clean detergency of the organic solvent such as ultrapure water or alcohols that utilizes of the electronic unit polluted from the taboo such as semiconductor wafer or glass is considered, preferably the acrylic adhesives of polymkeric substance based on acrylic polymers.

As described acrylic polymers, the acrylic polymers using acrylate as main monomer component can be enumerated.As described acrylate, can enumerate such as: use (methyl) alkyl acrylate (such as, methyl esters, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, secondary butyl ester, the tert-butyl ester, pentyl ester, isopentyl ester, own ester, heptyl ester, monooctyl ester, 2-ethylhexyl, different monooctyl ester, the ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems ester, isodecyl ester, undecane ester, dodecane ester, tridecane ester, tetradecane ester, n-Hexadecane ester, octadecane ester, the carbonatoms 1 ~ 30 of the alkyl such as eicosane ester, the particularly straight or branched alkyl ester etc. of carbonatoms 4 ~ 18) and (methyl) acrylate ester is (such as, ring pentyl ester, cyclohexyl etc.) one or more acrylic polymerss etc. as monomer component.In addition, (methyl) acrylate represents acrylate and/or methacrylic ester, and (methyl) of the present invention all represents identical implication.

In order to improve cohesive force, thermotolerance etc., described acrylic polymers as required can containing with can with unit corresponding to other monomer component of described (methyl) alkyl acrylate or the copolymerization of cycloalkanes ester.As such monomer component, can enumerate such as: carboxyl group-containing monomer, as vinylformic acid, methacrylic acid, (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxyl pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid etc.; Anhydride monomers, as maleic anhydride, itaconic anhydride etc.; Hydroxyl monomer, as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxybutyl, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxylauric ester, (methyl) vinylformic acid (4-hydroxymethylcyclohexyl) methyl esters etc.; Containing sulfonic group monomer, as styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid, (methyl) acryamidopropanesulfonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) acryloyl-oxy naphthene sulfonic acid etc.; Phosphorous acid-based monomers is as acryloyl phosphoric acid-2-hydroxy methacrylate etc.; Acrylamide, vinyl cyanide etc.These copolymerisable monomer compositions can use one or more.The usage quantity of these copolymerisable monomers is preferably less than 40 % by weight of whole monomer component.

In addition, described acrylic polymers in order to carry out crosslinked as required also can containing polyfunctional monomer etc. as comonomer composition.As such polyfunctional monomer, can enumerate such as: hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, carbamate (methyl) acrylate etc.These polyfunctional monomers also can use one or more.The usage quantity of polyfunctional monomer is considered to be preferably less than 30 % by weight of whole monomer component from viewpoints such as adhesion characteristics.

Described acrylic polymers can by obtaining the polymerization of mixtures of single monomer or two or more monomer.Polymerization can be undertaken by any-modes such as solution polymerization, letex polymerization, mass polymerization, suspension polymerizations.From preventing from considering viewpoints such as the pollutions of clean adherend, the content of preferred low molecular weight substance is few, in addition, shows predetermined store elastic modulus from the viewpoint of binder layer, the weight-average molecular weight of acrylic polymers is preferably about more than 300,000, and further preferred about 400,000 ~ about 3,000,000.

The second-order transition temperature (Tg) of acrylic polymers, from the viewpoint of peel adhesion, preferably more than-70 DEG C.More preferably more than-60 DEG C.In addition, second-order transition temperature is preferably-40 ~ 15 DEG C.Therefore, for the principal monomer for the formation of acrylic polymers, the second-order transition temperature of homopolymer is more than-70 DEG C is suitable.The measuring method of the second-order transition temperature (Tg) of acrylic polymers is based on the record of embodiment.

The iodine number of acrylic polymers preferably in the scope of 5 ~ 10, more preferably 5.5 ~ 9 scope in.When described iodine number is less than 5, the bounding force decline effect after irradiation with radiation when binder layer 2 is radiation curable is sometimes insufficient.On the other hand, when described iodine number is more than 10, cutting film improves the bounding force of sheet adhesive, is sometimes difficult to pickup.In addition, the numerical range of described iodine number is the value measured based on JIS K 0070-1992, measures the record of detailed content based on embodiment of program.

The hydroxyl value of acrylic polymers preferably in the scope of 7 ~ 30, more preferably 10 ~ 25 scope in.When described hydroxyl value is less than 7, the bounding force decline effect after irradiation with radiation when binder layer 2 is radiation curable is sometimes insufficient.On the other hand, when described hydroxyl value is more than 30, cutting film improves the bounding force of die bonding film, is sometimes difficult to pickup.In addition, the numerical range of described hydroxyl value is the value by measuring based on the acetylation method of JIS K 0070-1992, measures the record of detailed content based on embodiment of program.

In addition, in order to the weight-average molecular weight of the acrylic polymers etc. of polymkeric substance based on improving, in described tackiness agent, also suitably external crosslinker can be adopted.The concrete means of outside cross-linking method can be enumerated: add the so-called linking agents such as polyisocyanate compound, epoxy compounds, aziridine cpd, melamine class linking agent and the method making it react.When using external crosslinker, its usage quantity is according to the balance with the base polymer that should be cross-linked and suitably determine as the use of tackiness agent.Generally speaking, preferably coordinate below about 5 weight parts relative to described base polymer 100 weight part, preferably coordinate 0.1 ~ 5 weight part further.In addition, from the viewpoint of binder layer being given to predetermined store elastic modulus, relative to described acrylic resin 100 weight part, preferably containing 1 ~ 5 weight part isocyanates linking agent.In addition, as required, in tackiness agent, the additives such as known various tackifier, antiaging agent can also be used except aforesaid ingredients.

Binder layer 2 can be formed by radiation curable tackiness agent.Now, the store elastic modulus of binder layer before irradiation with radiation at 26 DEG C needs to be 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷below Pa.Radiation curable tackiness agent increases degree of crosslinking by utilizing the irradiation of ultraviolet israds thus can easily make its bounding force decline.Such as, in binder layer 2 shown in Fig. 1, by only to the part 2a illumination radiation line corresponding with semiconductor wafer adhesive portion 3a, can arrange with this part 2a beyond the poor adhesion of part 2b.

In addition, by making radiation-curable adhesive layer 2 solidify according to sheet adhesive 3 ', the part 2a that bounding force significantly declines can easily be formed.Due to sheet adhesive 3 ' be pasted onto solidification and bounding force decline part 2a on, therefore the interface of part 2a and sheet adhesive 3 ' has the character easily peeled off when picking up.On the other hand, the part of non-illumination radiation line has sufficient bounding force, forming section 2b.

As mentioned above, in the binder layer 2 of the dicing/die bonding film 10 shown in Fig. 1, the described part 2b formed by uncured radiation curable tackiness agent and sheet adhesive 3 bond, and can guarantee confining force when cutting.Like this, radiation curable tackiness agent can with good gluing-peel off balanced support for semi-conductor chip being fixed to the sheet adhesive 3 on the adherends such as substrate.In the binder layer 2 of the dicing/die bonding film 11 shown in Fig. 4, paster ring (wafer ring) can be fixed by described part 2b.

Described radiation curable tackiness agent can use without particular limitation has carbon-to-carbon double bond israds solidified nature functional group, and shows fusible radiation curable tackiness agent.As radiation curable tackiness agent, can illustrate such as: the addition type radiation curable tackiness agent being combined with radiation curing monomer component or oligopolymer composition in the pressure sensitive adhesive that acrylic adhesives, rubber adhesive etc. are general.

As the radiation curing monomer component for coordinating, can enumerate such as: oligourethane, carbamate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, BDO two (methyl) acrylate etc.In addition, radiation curing oligopolymer composition can enumerate the various oligopolymer such as amino formate, polyethers, polyester, polycarbonate-based, polybutadiene, and its weight-average molecular weight is suitable in the scope of about 100 ~ about 30000.The use level of radiation curing monomer component or oligopolymer composition suitably can determine the amount of the bounding force that can reduce binder layer according to the kind of described binder layer.Generally speaking, relative to base polymer 100 weight part such as acrylic polymers forming tackiness agent, such as, be about 5 weight parts ~ about 500 weight parts, preferably about 40 weight parts ~ about 150 weight parts.

In addition, as radiation curable tackiness agent, except the addition type radiation curable tackiness agent illustrated above, can also enumerate and be used in polymer lateral chain or main chain or the inherent type radiation curable tackiness agent of polymkeric substance based on polymkeric substance that main chain terminal has a carbon-carbon double bond.Inherent type radiation curable tackiness agent is without the need to containing or not containing the oligopolymer composition etc. as low molecular weight compositions in a large number, therefore oligopolymer composition etc. can not be passed in time and move in tackiness agent, the binder layer of stable Rotating fields can be formed, therefore preferably.

The described base polymer with carbon-carbon double bond, can use without particular limitation and have carbon-carbon double bond and have fusible polymkeric substance.As such base polymer, preferably using acrylic polymers as the polymkeric substance of basic framework.As the basic framework of acrylic polymers, the acrylic polymers that foregoing illustrative is crossed can be enumerated.

The method introducing carbon-carbon double bond in described acrylic polymers is not particularly limited, and can adopt various method, but, carbon-carbon double bond is introduced polymer lateral chain in molecular designing than being easier to.Can enumerate such as: first will there is the monomer copolymerization of functional group in acrylic polymers, then, make to have and can carry out the method for condensation or addition reaction when keeping the radiation curing of carbon-carbon double bond with the compound of the functional group of this functional group reactions and carbon-carbon double bond.

As the combination example of these functional groups, can enumerate such as: carboxyl and epoxy group(ing), carboxyl and '-aziridino, hydroxyl and isocyanate group etc.From the viewpoint of the easiness of reactive tracing in the combination of these functional groups, the combination of preferred hydroxyl and isocyanate group.In addition, if have the combination of the acrylic polymers of carbon-carbon double bond described in being generated by the combination of these functional groups, then functional group can in any one party of acrylic polymers and described compound, in described preferably combination, the situation that preferred acrylic polymers has hydroxyl, described compound has isocyanate group.Now, as the isocyanate compound with carbon-carbon double bond, can enumerate such as: methacryloyl isocyanic ester, 2-methylacryoyloxyethyl isocyanic ester, a pseudoallyl-α, alpha-alpha-dimethyl dibenzoyl isocyanic ester etc.In addition, as acrylic polymers, copolymerization can be used to have the polymkeric substance of ether compound etc. of the hydroxyl monomer of foregoing illustrative or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl base ether.

There is described in described inherent type radiation curable tackiness agent can be used alone the base polymer (particularly acrylic polymers) of carbon-carbon double bond, also can coordinate described radiation curing monomer component or oligopolymer composition in the scope not damaging characteristic.Radiation curing oligopolymer composition etc. relative to base polymer 100 weight part usually in the scope of 30 weight parts, the preferably scope of 0 ~ 10 weight part.

Described radiation curable tackiness agent can contain Photoepolymerizationinitiater initiater when being solidified by ultraviolet etc.As Photoepolymerizationinitiater initiater, can enumerate such as: α-one alcohol compound, as 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2-methyl-2-hydroxypropiophenonepreparation, 1-hydroxycyclohexylphenylketone etc.; Acetophenone compounds, as methoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenones, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropane-1-ketone etc.; Benzoin ether compounds, as ethoxybenzoin, benzoin iso-propylether, anisoin methyl ether etc.; Ketal compounds, as dibenzoyl dimethyl ketal etc.; Aromatic sulfonyl compounds, as 2-naphthalic sulfonic chloride etc.; Photolytic activity oxime compounds, as 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl) oxime etc.; Benzophenone compound, as benzophenone, benzoylbenzoic acid, 3,3 '-dimethyl-4-methoxy benzophenone etc.; Thioxanthone compounds, as thioxanthone, CTX, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-bis-clopenthixal ketones, 2,4-diethyl thioxanthones, 2,4-diisopropylthioxanthone etc.; Camphorquinone; Halogenated ketone; Acylphosphine oxide; Acyl phosphonate etc.The use level of Photoepolymerizationinitiater initiater relative to base polymer 100 weight part such as acrylic polymers forming tackiness agent, such as, is about 0.05 weight part ~ about 20 weight parts.

When forming binder layer 2 by radiation curable tackiness agent, preferably the bounding force that irradiation with radiation makes the bounding force < part 2b of part 2a is carried out to a part for binder layer 2.Such as, in the dicing/die bonding film of Fig. 1, for the relation of the SUS304 plate (#2000 grinding) as adherend, be the bounding force of the bounding force < part 2b of part 2a.

As the method forming described part 2a in described binder layer 2, can enumerate: form radiation-curable adhesive layer 2 on base material 1 after, to the described part 2a illumination radiation line method that makes it solidify partly.The irradiation with radiation of local can be undertaken by the photomask being formed with the pattern corresponding with the part 3b beyond semiconductor wafer adhesive portion 3a etc.In addition, the method etc. that point-like irradiation ultraviolet radiation is cured can be enumerated.The formation of radiation-curable adhesive layer 2 can be undertaken by the radiation-curable adhesive layer be arranged on partition being transferred on base material 1.The irradiation with radiation of local also can carry out the radiation-curable adhesive layer 2 be arranged on partition.

In addition, when forming binder layer 2 by radiation curable tackiness agent, the whole of the part beyond to the part corresponding with semiconductor wafer adhesive portion 3a of at least one side of base material 1 or local can be used to carry out the base material of shading, irradiation with radiation is carried out after forming radiation-curable adhesive layer 2 on the substrate, make corresponding with semiconductor wafer adhesive portion 3a partially cured, thus form the described part 2a that bounding force declines.As light screening material, the material that can become photomask by printing or evaporation in support film makes.By described manufacture method, the dicing/die bonding film 10 of present embodiment effectively can be manufactured.

In addition, when producing solidification obstacle during irradiation with radiation because of oxygen, preferably utilize any means from the surperficial isolating oxygen (air) of radiation-curable adhesive layer 2.Can enumerate such as: with partition by the method for the surface coverage of described binder layer 2 or the method etc. of irradiation of carrying out ultraviolet israds in nitrogen atmosphere.

The thickness of binder layer 2 is not particularly limited, and from realizing preventing the viewpoint such as the defect in chip cutting face and the fixing maintenance of adhesive layer from considering simultaneously, is preferably about 1 μm to about 50 μm.Preferably 2 μm ~ 30 μm, more preferably 5 μm ~ 25 μm.

In addition, in binder layer 2, in the scope of effect not damaging present embodiment, various additive (such as, tinting material, thickening material, extender, weighting agent, tackifier, softening agent, antiaging agent, antioxidant, tensio-active agent, linking agent etc.) can be contained.

[sheet adhesive]

Sheet adhesive 3,3 ' (sometimes both merging being called " sheet adhesive 3 " below) containing the ion capturing agent that can catch metal ion, and suitably containing thermoplastic resin and thermosetting resin, also can contain other composition further.As sheet adhesive 3,3 ', the sheet adhesive of above-mentioned embodiment suitably can be adopted.

The thickness of sheet adhesive 3 is not particularly limited, and owing to can suppress ion capturing agent from sheet adhesive 3 to the transfer etc. of binder layer, therefore in order to tackle the high capacity of semiconductor device, easily can realize slimming.The thickness of sheet adhesive preferably can slimming until more than 3 μm and the scope of less than 150 μm, more preferably can slimming until more than 4 μm and the scope of less than 120 μm, preferably more than 5 μm and the scope of less than 100 μm further.

For sheet adhesive 3, the sheet adhesive of weight 2.5g to be impregnated in the aqueous solution 50mL containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, copper ion concentration in the described aqueous solution is preferably 0 ~ 9.8ppm, is more preferably 0 ~ 9.5ppm, further preferred 0 ~ 9.0ppm.By sheet adhesive, there is such cupric ion catching, the metal ion being mixed into semi-conductor chip etc. in the manufacturing process of semiconductor device from outside can be caught.As a result, the metal ion be mixed into from outside is difficult to arrive the circuit forming surface formed at wafer, can suppress the decline of electrical characteristic, thus can improve goods reliability.In present embodiment, copper ion concentration after catching as making cupric ion is the method for 0 ~ 9.8ppm, except making in sheet adhesive, containing except the method for ion capturing agent, can also to adopt and introduce the method etc. that carboxylic acid group etc. can catch the method for the functional group of metal ion, boron ion implantation or n-type dopant in the resinous principle for using as mentioned above.

The stretching store elastic modulus of described sheet adhesive before thermofixation at 60 DEG C is preferably more than 0.01MPa and below 1000MPa, more preferably more than 0.05MPa and below 100MPa, further preferably more than 0.1MPa and below 50MPa.By the stretching store elastic modulus before thermofixation at 60 DEG C is adjusted to more than 0.01MPa, the shape as film can be kept, good workability can be given.In addition, by the stretching store elastic modulus before thermofixation at 60 DEG C is adjusted to below 1000MPa, the good wettability to adherend can be given.

[manufacture method of dicing/die bonding film]

The dicing/die bonding film 10,11 of present embodiment, such as, by making cutting film and sheet adhesive respectively, finally can paste them and making.Specifically, can make according to following program.

First, base material 1 can by existing known film-forming method masking.As this film-forming method, can illustrate such as: the casting in calendering masking method, organic solvent, blowing extrusion molding, T-shaped extrusion, coetrusion, dry lamination method etc. in enclosed system.

Then, the binder composition that binder layer is formed is prepared.The resin, additive etc. that illustrated in binder layer project is combined with in binder composition.The binder composition that base material 1 is coated with preparation forms film, then makes this dried coating film (as required heat cross-linking) in predefined conditions and forms binder layer 2.Be not particularly limited as coating process, can enumerate such as: the coating of roller coat, silk screen, intaglio plate coating etc.In addition, as drying conditions, such as, carry out in drying temperature 80 ~ 150 DEG C, the scope of 0.5 ~ 5 minute time of drying.In addition, also can be formed after film by coating adhesive composition on partition, dry coating under aforementioned drying condition and form binder layer 2.Afterwards, binder layer 2 is pasted on base material 1 together with partition.Thus, the cutting film with base material 1 and binder layer 2 is made.In addition, as cutting film, at least there is base material and binder layer, when having other key elements such as partition also referred to as cutting film.

The sheet adhesive of present embodiment, such as, make in the following manner.First, such as, ion capturing agent and thermosetting resin as required, thermoplastic resin, other additive are put in container, dissolve in organic solvent, and be stirred to evenly, can the form of adhesive compound solution obtain thus.

As described organic solvent, as long as the organic solvent dissolving, mediate or disperse with forming the uniform composition of sheet adhesive then can not limited, existing known organic solvent can be used.As such solvent, can enumerate such as: the ketones solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, acetone, methylethylketone, pimelinketone, toluene, dimethylbenzene etc.Obtain fast from the viewpoint of rate of drying, marked downly, preferably use methylethylketone, pimelinketone etc.

Film is formed, then in predefined conditions by this dried coating film by the adhesive compound solution coat as above prepared to base material partition reaches pre-determined thickness.As base material partition, polyethylene terephthalate (PET), polyethylene, polypropylene can be used or carry out the plastics film after surface coated or paper etc. by strippers such as fluorine-containing stripper, chain alkyl esters of acrylic acid strippers.In addition, as coating process, be not particularly limited, can enumerate such as: the coating of roller coat, silk screen, intaglio plate coating etc.In addition, as drying conditions, such as, carry out in drying temperature 70 ~ 160 DEG C, the scope of 1 ~ 5 minute time of drying.Thus, the sheet adhesive of present embodiment can be obtained.

Then, peel off partition from cutting film, the mode being sticking veneer with sheet adhesive and binder layer is by sheet adhesive and cutting film applying.Paste and such as can be undertaken by crimping.Now, laminating temperature is not particularly limited, such as preferably 30 ~ 50 DEG C, more preferably 35 ~ 45 DEG C.In addition, line pressure is also not particularly limited, such as preferably 0.1 ~ 20kgf/cm, more preferably 1 ~ 10kgf/cm.Then, the base material partition on adhesive foil is peeled off, the dicing/die bonding film of present embodiment can be obtained.

[semiconductor device and manufacture method thereof]

As semiconductor device and the manufacture method thereof of present embodiment, the semiconductor device and manufacture method that illustrated in the first embodiment suitably can be adopted.

Embodiment

Below, the preferred embodiments of the present invention are illustrated illustratively.But the material recorded in this embodiment, use level etc., if the record of being not particularly limited property, be not then only only limitted to these by main idea of the present invention.In addition, hereinafter, weight part is referred to when to have part.

[the first embodiment]

Following each embodiment etc., corresponding with the described sheet adhesive of the first embodiment.

(embodiment 1)

Following (a) ~ (e) is dissolved in methylethylketone, obtains the adhesive compound solution of concentration 20 % by weight.

A () has carboxyl and the hydroxyl acrylic resin (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-708-6, weight-average molecular weight 700,000) 29.97 parts as functional group

(b) epoxy resin (Nippon Steel Chemical Co., Ltd manufactures, YDF-8170C) 4.995 parts

(c) resol (bright and change into Co., Ltd. and manufacture, MEH-7851H) 4.995 parts

(d) silica filler (Co., Ltd. ア De マテッ Network ス manufactures, SC-2050, median size 0.5 μm) 59.94 parts

(e) complex compound formative organic compound (Tokyo HuaCheng Industry Co., Ltd manufactures, gallate dodecyl) 0.1 part

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the embodiment 1 of thickness 20 μm is made.

(embodiment 2)

A () has carboxyl and the hydroxyl acrylic resin (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-708-6, weight-average molecular weight 700,000) 28.5 parts as functional group

(b) epoxy resin (Nippon Steel Chemical Co., Ltd manufactures, YDF-8170C) 4.75 parts

(c) resol (bright and change into Co., Ltd. and manufacture, MEH-7851H) 4.75 parts

(d) silica filler (Co., Ltd. ア De マテッ Network ス manufactures, SC-2050, median size 0.5 μm) 57 parts

(e) complex compound formative organic compound (Tokyo HuaCheng Industry Co., Ltd manufactures, gallate dodecyl) 5 parts

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the embodiment 2 of thickness 20 μm is made.

(embodiment 3)

A () has carboxyl and the hydroxyl acrylic resin (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-708-6, weight-average molecular weight 700,000) 27 parts as functional group

(b) epoxy resin (Nippon Steel Chemical Co., Ltd manufactures, YDF-8170C) 4.5 parts

(c) resol (bright and change into Co., Ltd. and manufacture, MEH-7851H) 4.5 parts

(d) silica filler (Co., Ltd. ア De マテッ Network ス manufactures, SC-2050, median size 0.5 μm) 54 parts

(e) complex compound formative organic compound (Tokyo HuaCheng Industry Co., Ltd manufactures, gallate dodecyl) 10 parts

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the embodiment 3 of thickness 20 μm is made.

(comparative example 1)

A () has the acrylic resin (Na ガセケ system テッ Network ス Co., Ltd. manufacture, SG-P3, weight-average molecular weight 85 ten thousand) 28.5 part of epoxy group(ing) as functional group

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the comparative example 1 of thickness 20 μm is made.

(comparative example 2)

A () has the acrylic resin (Na ガセケ system テッ Network ス Co., Ltd. manufacture, SG-600TEA, weight-average molecular weight 120 ten thousand) 28.5 part of hydroxyl as functional group

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the comparative example 2 of thickness 20 μm is made.

(comparative example 3)

(e) complex compound formative organic compound (north of the city KCC manufactures, TT-LX, triazole compounds) 5 parts

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the comparative example 3 of thickness 20 μm is made.

(comparative example 4)

Following (a) ~ (d) is dissolved in methylethylketone, obtains the adhesive compound solution of concentration 20 % by weight.

A () has carboxyl and the hydroxyl acrylic resin (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-708-6, weight-average molecular weight 700,000) 30 parts as functional group

(b) epoxy resin (Nippon Steel Chemical Co., Ltd manufactures, YDF-8170C) 5 parts

(c) resol (bright and change into Co., Ltd. and manufacture, MEH-7851H) 5 parts

(d) silica filler (Co., Ltd. ア De マテッ Network ス manufactures, SC-2050, median size 0.5 μm) 60 parts

After in described adhesive compound solution coat to the demoulding process film be made up of the pet film of the thickness after polysiloxane demoulding process 50 μm, 130 DEG C of dryings 2 minutes.Thus, the sheet adhesive of the comparative example 4 of thickness 20 μm is made.

(evaluation of cupric ion seizure property)

The sheet adhesive (thickness 20 μm) of embodiment and comparative example is cut into respectively the size (about 2.5g) of 240mm × 300mm, its five doublings are obtained the size of 37.5mm × 60mm, be placed in cylindric closed teflon (registered trademark) container of diameter 58mm, height 37mm, and added copper (II) the deionized water solution 50ml of 10ppm.Then, place 20 hours at 120 DEG C in freeze-day with constant temperature machine (エスペッ Network Co., Ltd. system, PV-231).After taking out film, use ICP-AES (エスアイアイ Na ノテ Network ノロジー Co., Ltd. system, SPS-1700HVR) measures the copper ion concentration in the aqueous solution.The concentration of the cupric ion in the aqueous solution is evaluated as zero when being 0 ~ 9.8ppm, be evaluated as when being greater than 9.8ppm ×.Result is as shown in table 1.

(space deorienting)

The sheet adhesive (thickness 20 μm) of embodiment and comparative example is pasted on the square semi-conductor chip of 10mm respectively under the condition of temperature 40 DEG C, then by each sheet adhesive, semi-conductor chip is installed on BGA substrate.Mounting condition be temperature 120 DEG C, pressure 0.1MPa, 1 second.Then, utilize drying machine at 175 DEG C to the BGA substrate heat process 30 minutes being provided with semi-conductor chip, then use sealing resin (Nitto Denko Corp manufactures, GE-100) to encapsulate.Air-proof condition is: Heating temperature 175 DEG C, 90 seconds.Then, the semiconductor device glass cutter after sealing is cut off, use ultrasonic microscope to observe its section, measure the void area in the sticking veneer of each sheet adhesive and BGA substrate.Void area relative to bonding area lower than 50% time be evaluated as zero, be evaluated as when being more than 50% ×.Result is as shown in table 1 below.

(moisture-proof reflow soldering)

The sheet adhesive (thickness 20 μm) of embodiment and comparative example is pasted on the square semi-conductor chip of 10mm respectively under the condition of temperature 40 DEG C, then by each sheet adhesive, semi-conductor chip is installed on BGA substrate.Mounting condition be temperature 120 DEG C, pressure 0.1MPa, 1 second.Then, utilize drying machine at 175 DEG C to the BGA substrate heat process 30 minutes being provided with semi-conductor chip, then use sealing resin (Nitto Denko Corp manufactures, GE-100) to encapsulate.Air-proof condition is: Heating temperature 175 DEG C, 90 seconds.Then, 85 DEG C, 60%RH, carry out moisture absorption under the condition of 168 hours time, then the BGA substrate-placing that will be provided with described semi-conductor chip is in the IR reflow ovens of carrying out setting in the mode kept 10 seconds more than 260 DEG C.Then, the semiconductor device glass cutter after sealing is cut off, use ultrasonic microscope to observe its section, confirm that the boundary of each thermosetting die bonding film and BGA substrate is with or without stripping.9 semi-conductor chips are confirmed, when the semi-conductor chip be peeling is below 3, is evaluated as zero, be evaluated as when being more than 4 ×.Result is as shown in table 1 below.

Table 1

Embodiment 1

Embodiment 2

Embodiment 3

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Copper ion concentration (ppm)

8.50

3.20

2.25

3.22

3.18

0.15

10.0

The evaluation of cupric ion seizure property

○

╳

Space deorienting

○

╳

○

╳

○

Moisture-proof reflow soldering

○

╳

○

(result)

In an embodiment, cupric ion seizure property, space deorienting, moisture-proof reflow soldering all show good result.On the other hand, in comparative example 1, the epoxy reaction that gallate dodecyl and acrylic resin have, is cured tempestuously, and space deorienting during shaping declines.In addition, in comparative example 2, acrylic resin not existing the functional group of reacting with curable resin or complex compound formative organic compound (the complex compound formative organic compound of phenyl ring containing having two or more phenolic hydroxyl group), it is hereby ensured space deorienting during shaping.But acrylic resin is uncrosslinked, therefore can not tolerates reflow soldering test, cause stripping in gluing interface, thus produce space.In addition, in comparative example 3, TT-LX does not have reactivity with the resin forming sheet adhesive, but works as basic catalyst, therefore promoted the reaction of epoxy group(ing) and carboxyl or epoxy group(ing) and phenolic group by thermal history, thus space deorienting when being shaped declines.In addition, in comparative example 4, containing the complex compound formative organic compound of complex compound can be formed with positively charged ion, therefore metal ion can not be caught.

[the second embodiment]

Following each embodiment etc., corresponding with the described sheet adhesive of the second embodiment.

(embodiment 1)

A acrylic polymer (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-70L) 80 parts that () is principal constituent with ethyl propenoate-methyl methacrylate

(b) epoxy resin (JER Co., Ltd. manufactures, エピコート 1004) 10 parts

10 parts, (c) resol (Mitsui Chemicals, Inc manufactures, ミレッ Network ス XLC-LL)

(d) silicon-dioxide (Japanese アエロジ Le Co., Ltd. manufactures, R972, median size 0.016 μm) 13 parts

(e) gallate dodecyl (Tokyo HuaCheng Industry Co., Ltd's manufacture) 1.5 parts

Using described adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the pet film of the thickness after polysiloxane demoulding process 50 μm after, 130 DEG C of dryings 2 minutes.Thus, the film like tackiness agent A of thickness 20 μm is made.

(embodiment 2)

(b) epoxy resin (JER Co., Ltd. manufactures, エピコート 1004) 10 parts

(d) silicon-dioxide (Japanese アエロジ Le Co., Ltd. manufactures, R972, median size 0.016 μm) 15 parts

(e) gallate dodecyl (Tokyo HuaCheng Industry Co., Ltd's manufacture) 10 parts

Using described adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the pet film of the thickness after polysiloxane demoulding process 50 μm after, 130 DEG C of dryings 2 minutes.Thus, the film like tackiness agent B of thickness 20 μm is made.

(embodiment 3)

(b) epoxy resin (JER Co., Ltd. manufactures, エピコート 1004) 10 parts

(d) silicon-dioxide (Sakai Chemical Industry Co., Ltd. manufactures, Sciqas, grade 0.4 μm (median size 0.4 μm)) 135 parts

(e) gallate dodecyl (Tokyo HuaCheng Industry Co., Ltd's manufacture) 3 parts

Using described adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the pet film of the thickness after polysiloxane demoulding process 50 μm after, 130 DEG C of dryings 2 minutes.Thus, the film like tackiness agent C of thickness 20 μm is made.

(embodiment 4)

(b) epoxy resin (JER Co., Ltd. manufactures, エピコート 1004) 10 parts

(e) gallate dodecyl (Tokyo HuaCheng Industry Co., Ltd's manufacture) 55 parts

Using described adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the pet film of the thickness after polysiloxane demoulding process 50 μm after, 130 DEG C of dryings 2 minutes.Thus, the film like tackiness agent D of thickness 20 μm is made.

(comparative example 1)

(b) epoxy resin (JER Co., Ltd. manufactures, エピコート 1004) 10 parts

Using described adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the pet film of the thickness after polysiloxane demoulding process 50 μm after, 130 DEG C of dryings 2 minutes.Thus, the film like tackiness agent E of thickness 20 μm is made.

(comparative example 2)

(b) epoxy resin (JER Co., Ltd. manufactures, エピコート 1004) 10 parts

(d) silicon-dioxide (Ube Nitto Kasei Co manufactures, Ha イプレシカ UF, median size 5.0 μm) 13 parts

(e) gallate dodecyl (Tokyo HuaCheng Industry Co., Ltd's manufacture) 1.5 parts

Using described adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the pet film of the thickness after polysiloxane demoulding process 50 μm after, 130 DEG C of dryings 2 minutes.Thus, the film like tackiness agent F of thickness 20 μm is made.

(median size of mineral filler measures)

The median size of filler is obtained by luminosity formula size-grade distribution meter (HORIBA system, device name: LA-910).Implement under following condition determination: laser 89.7%, distributional pattern is single dispersing, measures number of times (Qu り Write body and returns number) be 10 times.

(evaluation of cupric ion seizure property)

Each film like tackiness agent A ~ F of embodiment and comparative example is cut into weight and is about 2.5g, be laminated for the size of 30mm × 37.5mm × 0.32mm, by stacked and sample that is that obtain heats 5 hours at 175 DEG C.Sample after heating is placed in cylindric closed teflon (registered trademark) container of diameter 58mm, height 37mm, and adds copper (II) the deionized water solution 50ml of 10ppm.Then, place 20 hours at 120 DEG C in freeze-day with constant temperature machine (エスペッ Network Co., Ltd. system, PV-231).After taking out film, use ICP-AES (エスアイアイ Na ノテ Network ノロジー Co., Ltd. system, SPS-1700HVR) measures the copper ion concentration in the aqueous solution.The concentration of the cupric ion in the aqueous solution is evaluated as zero when being 0 ~ 9.8ppm, be evaluated as when being greater than 9.8ppm ×.Result is as shown in table 2.In the lump the copper ion concentration (ppm) measured after test is arranged in table 2.

(chip Damage Evaluation during chip join)

The film like tackiness agent A ~ F obtained in embodiment and comparative example and cutting film (Nitto Denko Corp manufactures, DU-300) are pasted, obtains the film like tackiness agent with cutting film.After the wafer being formed with the thickness 30 μm of circuit is pasted at 60 DEG C with the film like tackiness agent with the film like tackiness agent cutting film, carry out cutting (cutting unit: Co., Ltd. DISCO manufactures, DFD6361), the chip being pasted with the 10mm × 10mm of film like tackiness agent is made.The microarray biochip with film like tackiness agent made is joined on lead frame (Alloy42).Chip join under applying load (0.1MPa), the heating condition of 1 second, uses chip engagement machine (Arakawa Co., Ltd. SPA-300) to carry out at the temperature of 120 DEG C.The average evaluation all not producing damage in the chip 50 of chip join is zero, though the average evaluation having to produce defect or the equivalent damage that breaks for ×.Result is as shown in table 2.

(mensuration of the stretching store elastic modulus after thermofixation at 175 DEG C)

The film like tackiness agent of each embodiment and comparative example is placed 5 hours in the baking oven of 175 DEG C, then the stretching store elastic modulus after the thermofixation of use determination of viscoelasticity device (manufacture of RSA-II, レオメトリッ Network company) mensuration at 175 DEG C.In mensuration, use by the multi-disc sheet adhesive of making paste and to obtain the mensuration sample that length is 30mm, the mode of width 10mm, thickness 0.20mm is cut.Stretching store elastic modulus be determined at the temperature range of-40 ~ 300 DEG C under carry out under the condition of frequency 1Hz, dependent variable 0.1%, heat-up rate 10 DEG C/min.Stretching store elastic modulus is evaluated as zero when being more than 0.1MPa, be evaluated as lower than during 0.1MPa ×.Measured value at 175 DEG C and result arrange in table 2 in the lump.

(the clipping viscous force after thermofixation at 175 DEG C measures)

Sample after chip join in said chip Damage Evaluation is heated 1 hour at 175 DEG C, sheet adhesive is solidified.Use shear testing maschine (Dage company manufactures, Dage4000), measure the clipping viscous force of sheet adhesive and wafer chip.The condition of shearing test is: finding speed 500 μm/s, mensuration 100 μm, gap, platform temperature 175 DEG C.Clipping viscous force is the average evaluation of more than 0.01MPa is zero, the average evaluation lower than 0.01MPa is ×.Measured value at 175 DEG C and result arrange in table 2 in the lump.

Table 2

From the results shown in Table 2, the clipping viscous force after the store elastic modulus after damaging, the thermofixation of chip when the cupric ion of the film like tackiness agent of embodiment catches property, chip join at 175 DEG C and thermofixation at 175 DEG C is good result.On the other hand, although the film like tackiness agent of comparative example 1 does not produce chip damage, due to not containing ion-catching organic compound, therefore ion-catching is shown hardly.In addition, although the film like tackiness agent ion-catching of comparative example 2 is good, chip produces damage.This is considered to because the median size of mineral filler is up to 5.0 μm, thus mineral filler contacts with chip and causes when chip join.

[the 3rd embodiment]

Following each embodiment etc., corresponding with the described dicing/die bonding film of the 3rd embodiment.

(preparation of base material)

Prepare the pet film (PET film) of thickness 50 μm as base material.

(preparation of acrylic polymers A)

In the reaction vessel with prolong, nitrogen introducing tube, thermometer and whipping appts, drop into 4 parts of ethyl acrylates, 3 parts of butyl acrylates, 100 parts of 2-Hydroxy ethyl acrylates, 0.2 part of benzoyl peroxide and 20 parts of acetic acid, in nitrogen gas stream, carry out 6 hours aggregation processing at 61 DEG C, obtain acrylic polymers A.Be 300,000 about acrylic polymers A, weight-average molecular weight Mw, second-order transition temperature (Tg) is-16 DEG C, and iodine number is 2, and hydroxyl value (mgKOH/g) is 30.

(preparation of acrylic polymers B)

In the reaction vessel with prolong, nitrogen introducing tube, thermometer and whipping appts, drop into 80 parts of ethyl acrylates, 20 parts of 2-Hydroxy ethyl acrylates and 65 parts of toluene, in nitrogen gas stream, carry out 6 hours aggregation processing at 61 DEG C, obtain acrylic polymers B.Be 800,000 about acrylic polymers B, weight-average molecular weight Mw, second-order transition temperature (Tg) is-60 DEG C, and iodine number is 6, and hydroxyl value (mgKOH/g) is 30.

(preparation of acrylic polymers C)

In the reaction vessel with prolong, nitrogen introducing tube, thermometer and whipping appts, in the acrylic polymers 100 parts of the number-average molecular weight about 300,000 be made up of 100 parts of butyl acrylates, 5 parts of vinyl cyanide and 5 parts of vinylformic acid, coordinate 5 parts of polyisocyanates, 15 parts of pentaerythritol triacrylates and 1 part of Alpha-hydroxy cyclohexyl-phenyl ketone, obtain acrylic polymers C.Be 500,000 about acrylic polymers C, weight-average molecular weight Mw, second-order transition temperature (Tg) is 10 DEG C, and iodine number is 1, and hydroxyl value (mgKOH/g) is 30.In addition, the measuring method of each assessment item is as described below.

(mensuration of weight-average molecular weight Mw)

The mensuration of the weight-average molecular weight Mw of acrylic polymers A ~ C is undertaken by GPC (gel permeation chromatography).Condition determination is as described below.In addition, weight-average molecular weight is calculated by polystyrene conversion.

Determinator: HLC-8120GPC (goods name, Dong Cao Inc.)

Post: TSKgel GMH-H (S) × 2 (goods number, Dong Cao Inc.)

Flow: 0.5ml/ minute

Injection volume: 100 μ l

Column temperature: 40 DEG C

Elutriant: THF

Sample injection concentration: 0.1 % by weight

Detector: differential refractometer

(mensuration of second-order transition temperature (Tg))

The mensuration of second-order transition temperature (Tg) is by the Tg of the homopolymer of each monomer _1-nwith the weight fraction W of each monomer _1-n, utilize 1/Tg=W ₁/ Tg ₁+ ... + W _n/ Tg _nthe value measured.

(mensuration of hydroxyl value)

The hydroxyl value of acrylic polymers A ~ C, evaluates according to JIS K 0070-1992 (acetylation method).That is, each acrylic polymers is after the drying about in 3g and adds 10ml acetylation reagent, then the pyridine 30ml added as solvent and dimethyl formamide 30ml.This solution is carried out in the water-bath possessing condenser heating in 1.5 hours in (95 ~ 100 DEG C).Add water 3ml again, then carry out heating in 10 minutes.

Then, cool to room temperature, by the washing with alcohol of condenser 5ml, and adds this washings in above-mentioned solution.In this solution, put into stirrer, while by magnetic stirrer, use potential difference titration apparatus to carry out titration with the potassium hydroxide solution of 0.5mol/L.During by the acetylize of 1g sample, the mg number of the potassium hydroxide needed for acetic acid of neutralization and hydroxy combining is as hydroxyl value.

(mensuration of iodine number)

The iodine number of acrylic polymers A ~ C, evaluates according to JIS K 0070-1992.That is, each acrylic polymers is after the drying about in 3g and adds 30ml chloroform and make it dissolve.Add 25ml Webster liquid (ウィイス liquid) wherein and stir.Then, cover lid becomes air-tight state, at 23 DEG C, in the dark place 1 hour.In this solution, add liquor kalii iodide 20ml and water 100ml, stir.With the hypo solution of 0.1mol/L, titration is carried out to this solution, when solution becomes micro-yellow, add several starch solutions, carry out titration until blue disappearance.When making halogen and 100g specimen reaction, in conjunction with halogen quantity be scaled the g number of iodine and the value obtained is iodine number.

(preparation of binder composition solution A ~ C)

In each polymkeric substance of acrylic polymers A ~ C, adding 24.1 parts of 2-methylacryoyloxyethyl isocyanic ester, (Showa electrician company manufactures, hereinafter also referred to " MOI "), in air draught, carry out addition reaction process in 48 hours at 50 DEG C, obtain acrylic polymers A ' ~ C '.

Then, 3 parts of polyisocyanate compounds (trade(brand)name " コロネート L " is added in acrylic polymers A ' ~ C ' is each 100 parts, Japanese polyurethane Co., Ltd. manufactures) and 3 parts of Photoepolymerizationinitiater initiater (trade(brand)names " イ Le ガキュア 651 ", Ciba Specialty Chemicals manufactures), be dissolved in toluene, obtained the binder composition solution A ~ C of concentration 20 % by weight.

(preparation of cutting film A ~ C)

On the above-mentioned base material prepared, be coated with the binder composition solution A ~ C obtained respectively, and dry, form the binder layer of thickness 30 μm, obtain cutting film A ~ C thus.

(making of sheet adhesive A)

(a) acrylic rubber (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-708-6) 33 parts

(b) epoxy resin (Nippon Steel Chemical Co., Ltd manufactures, YDF-8170H) 4.5 parts

(d) silicon-dioxide (Co., Ltd. ア De マテッ Network ス manufactures, SC-2050) 55 parts

(e) ion capturing agent (large and change into Co., Ltd. and manufacture, VERZONE) 3 parts

Using this adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the 50 μm of pet films of the thickness after polysiloxane demoulding process, and 130 DEG C of dryings 2 minutes, thus, the sheet adhesive A of thickness 20 μm is made.

(making of sheet adhesive B)

(a) acrylic rubber (Na ガセケ system テッ Network ス Co., Ltd. manufactures, SG-708-6) 35 parts

(b) epoxy resin (Nippon Steel Chemical Co., Ltd manufactures, YDF-8170H) 5 parts

(c) resol (bright and change into Co., Ltd. and manufacture, MEH-7851H) 5 parts

(d) silicon-dioxide (Co., Ltd. ア De マテッ Network ス manufactures, SC-2050) 45 parts

(e) ion capturing agent (Toagosei Co., Ltd manufactures, IXE-100) 10 parts

Using this adhesive compound solution coat to as release liner, on the demoulding process film that is made up of the 50 μm of pet films of the thickness after polysiloxane demoulding process, and 130 DEG C of dryings 2 minutes, thus, the sheet adhesive B of thickness 20 μm is made.

(embodiment 1 ~ 4)

By cutting film A ~ C and sheet adhesive A ~ B separately with the combination shown in table 3, paste at normal temperatures, make the dicing/die bonding film of embodiment 1 ~ 4.

(mensuration of the store elastic modulus of binder layer)

Use binder composition solution A ~ C, release liner (polyester company of Mitsubishi Chemical manufactures, MRF38, thickness 38 μm) forms binder layer, this binder layer is prepared into thickness 3mm, diameter 8mm φ, and it can be used as test sample.Then, use the test for viscoelastic machine ARES that レオメトリッ Network ス company manufactures, test sample is sandwiched with the parallel plate of diameter 7.9mm (shearing test with), the shear strain of frequency 1Hz is provided, with at the determination of heating rate 26 DEG C of 5 DEG C/min store elastic modulus (G ': Pa).Result is as shown in table 3.

(evaluation of the velocity of variation of cupric ion seizure amount)

Sheet adhesive A and B is cut into weight respectively and is about 2.5g, the sample cut out is put into the container that diameter 58mm, the highly cylindric teflon (registered trademark) of 37mm are made, and add Cu (II) the deionized water solution 50mL of 10ppm.Then, place 20 hours at 120 DEG C in freeze-day with constant temperature machine (エスペッ Network Co., Ltd. system, PV-231).After taking out film, use ICP-AES (エスアイアイ Na ノテ Network ノロジー Co., Ltd. system, SPS-1700HVR) measures copper (II) ionic concn in the aqueous solution.Thus, obtain and each cupric ion seizure amount X cutting the sheet adhesive A before film applying and B (initial stage copper ion concentration 10ppm-test after copper ion concentration ppm).

In addition, after the dicing/die bonding film of preparation embodiment 1 ~ 4, place 30 days at normal temperatures.Then, uviolizing (400mJ/cm is carried out to dicing/die bonding film ²), from cutting film, the sheet adhesive A ' after gluing treatment and B ' is peeled off.Using these sheet adhesive A ' and B ' as sample, measure copper ion concentration in the same manner as said procedure.Thus, obtain with the gluing treatment cutting film after sheet adhesive A ' and each cupric ion seizure amount Y (initial stage copper ion concentration 10ppm-test after copper ion concentration ppm) of B '.

By following formula, calculate the velocity of variation (%) with the cupric ion seizure amount of cutting sheet adhesive before and after film applying.

{ (cupric ion seizure amount X-cupric ion seizure amount Y)/cupric ion seizure amount X} × 100 (%)

The velocity of variation of cupric ion seizure amount is evaluated as zero when being less than 5%, be evaluated as during more than 5% ×.Result is as shown in table 3.

Table 3

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					The kind of cutting film	A	B	C	A
The thickness [μm] of binder layer	30	30	30	30
					The kind of sheet adhesive	A	A	A	B
The thickness [μm] of sheet adhesive	20	20	20	20
					The store elastic modulus (26 DEG C) [Pa] of binder layer	3×10 ⁵	3×10 ⁴	4×10 ⁶	3×10 ⁵
The velocity of variation evaluation of cupric ion seizure amount	○	○	○	○

From the results shown in Table 3, the store elastic modulus of the dicing/die bonding film of embodiment 1 ~ 4 binder layer is separately all 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷in the scope of below Pa, therefore can suppress ion capturing agent from sheet adhesive to the transfer etc. of binder layer of cutting film, though with cutting film applying after also suitably can play the ion-catching of sheet adhesive.

Claims

1. a dicing/die bonding film, it has:

Cutting film, described cutting film has base material and stacked binder layer on the substrate, and

Be layered in the sheet adhesive on described binder layer;

Described sheet adhesive contains the ion capturing agent that can catch metal ion,

The store elastic modulus of described binder layer at 26 DEG C is 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷below Pa.

2. dicing/die bonding film as claimed in claim 1, wherein, described ion capturing agent is can form the organic compound of complex compound with metal ion.

3. dicing/die bonding film as claimed in claim 1, wherein, the sample of the weight 2.5g got from described sheet adhesive to be impregnated in the 50ml aqueous solution containing 10ppm cupric ion and after placing 20 hours at 120 DEG C, the copper ion concentration in the described aqueous solution is 0 ~ 9.8ppm.

4. dicing/die bonding film as claimed in claim 1, wherein, described binder layer contains the acrylic resin of weight-average molecular weight more than 300,000.

5. dicing/die bonding film as claimed in claim 4, wherein, described acrylic resin is using hydroxy acryl acid class monomer as being formed monomer.

6. dicing/die bonding film as claimed in claim 4, wherein, described binder layer contains isocyanates linking agent.

7. dicing/die bonding film as claimed in claim 6, wherein, described binder layer contains 1 ~ 5 weight part isocyanates linking agent relative to described acrylic resin 100 weight part.

8. dicing/die bonding film as claimed in claim 1, wherein, described binder layer is radiation curable, and the store elastic modulus before irradiation with radiation at 26 DEG C is 1.0 × 10 ⁴more than Pa and 1.0 × 10 ⁷below Pa.

9. dicing/die bonding film as claimed in claim 1, wherein, the thickness of described sheet adhesive is more than 3 μm and less than 150 μm.