CN102074493A - Thermosetting die bonding film - Google Patents

Thermosetting die bonding film Download PDF

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Publication number
CN102074493A
CN102074493A CN2010105103449A CN201010510344A CN102074493A CN 102074493 A CN102074493 A CN 102074493A CN 2010105103449 A CN2010105103449 A CN 2010105103449A CN 201010510344 A CN201010510344 A CN 201010510344A CN 102074493 A CN102074493 A CN 102074493A
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China
Prior art keywords
die bonding
bonding film
weight
thermosetting
film
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CN2010105103449A
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Chinese (zh)
Inventor
宍户雄一郎
高本尚英
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN102074493A publication Critical patent/CN102074493A/en
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  • Engineering & Computer Science (AREA)
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  • Die Bonding (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a thermosetting die bonding film inhibiting curing shrinkage after die bonding and therefore preventing generation of warping in an adhered object and a cutting/die bonding film and a semiconductor device manufactured using the film. The thermosetting die bonding film in the invention is used for fixedly gluing a semiconductor element to an adhered object, wherein, via 120 degree and an hour thermal treatment and thermosetting, gel fraction of organic components is in the range of being below than 20 weight%, and via 175 degree and an hour thermal treatment and thermosetting, gel fraction of organic components is in the range of 10 to 30 weight%.

Description

Thermosetting die bonding film
Technical field
The thermosetting die bonding film that uses when the present invention relates to for example semiconductor elements such as semiconductor chip are affixed on the adherends such as substrate or lead frame.In addition, the present invention relates to this thermosetting die bonding film and cut the dicing/die bonding film that pellicular cascade forms.
Background technology
In the past, in the manufacture process of semiconductor device, the dicing/die bonding film (with reference to following patent documentation 1) that uses in cutting action gluing maintenance semiconductor wafer and also provide the needed chip set of installation procedure to stick with glue the agent layer.This dicing/die bonding film has the structure that stacks gradually adhesive phase and adhesive layer on support base material.That is, under the maintenance of adhesive layer with after the semiconductor wafer cutting, the stretching support base material picks up semiconductor chip with die bonding film.Again semiconductor chip is passed through the die bonding film chip join to the chip bonding pad of lead frame.
But in recent years, along with the maximization and the slimming of semiconductor wafer, semiconductor chip is slimming also.Such semiconductor chip is affixed on the adherend such as substrate by die bonding film and when making its hot curing (chip join), because the hot curing of die bonding film and cure shrinkage.As a result, produce the problem of adherend warpage.
The prior art document
Patent documentation 1: Japanese kokai publication sho 60-57342 communique
Summary of the invention
The present invention carries out in view of the above problems, and its purpose is to provide the thermosetting die bonding film and the dicing/die bonding film that can suppress the cure shrinkage after the chip join and can prevent to produce with respect to adherend warpage thus.
The inventor studies thermosetting die bonding film and dicing/die bonding film in order to solve above-mentioned existing problem.Found that,, when the gel fraction of its organic principle is in certain number range, can reduce its cure shrinkage, thereby finish the present invention for the thermosetting die bonding film after the heat treatment.
Promptly, thermosetting die bonding film of the present invention, be used for the gluing adherend that is fixed to of semiconductor element, it is characterized in that, by 120 ℃, 1 hour heat treatment after the hot curing in the scope of the gel fraction of organic principle below 20 weight %, and the heat treatment by 175 ℃, 1 hour and after the hot curing gel fraction of organic principle in the scope of 10～30 weight %.
When using thermosetting die bonding film to join to semiconductor element chip on the adherend, consider, preferably make thermosetting die bonding film hot curing fully from the gluing fixing reliable viewpoint that makes semiconductor element and adherend.But when the hot curing overreact was carried out, cure shrinkage took place in thermosetting die bonding film self sometimes.Among the present invention, as described in above-mentioned formation, since the heat treatment by 120 ℃, 1 hour and after the hot curing gel fraction of organic principle below 20 weight %, and the heat treatment by 175 ℃, 1 hour and after the hot curing gel fraction of organic principle in the scope of 10～30 weight %, therefore for example when joining to semiconductor element chip on the adherend, perhaps in the heat treatment of carrying out during wire bond, suppress the complete hot curing of film.Thus, can reduce the cure shrinkage of thermosetting die bonding film.As a result, can suppress on adherend, to produce warpage, thereby in the manufacturing of semiconductor device, can improve output owing to this cure shrinkage.
The thermosetting die bonding film of above-mentioned formation, preferably its acid number is in the scope of 4～10mgKOH/g.Thus, for example suppressing to produce warpage on the adherend by the heat treatment under 120 ℃, 1 hour condition when, can improve the clipping viscous force.
The thermosetting die bonding film of above-mentioned formation, preferably the thermoplastic resin in 10～40mgKOH/g scope forms by thermosetting resin and acid number.Thus, in the heat treatment of when chip join, thermosetting die bonding film being carried out, can suppress the hot curing of thermosetting die bonding film and excessively carry out.
Preferably be added with thermal curing catalyst in the thermosetting die bonding film of above-mentioned formation.For example, preferably by sealing resin will be on adherend the semiconductor element encapsulation of chip join, and when carrying out the back curing process, make the abundant hot curing of thermosetting die bonding film.Among the present invention, as described in above-mentioned formation, pass through to add thermal curing catalyst, when semiconductor element chip joined on the adherend, hot curing can make the hot curing of thermosetting die bonding film fully carry out to the degree that does not produce cure shrinkage when the curing process of described back.As a result, can make and be fixed on the adherend and semiconductor device that semiconductor element is not peeled off from adherend with semiconductor element is gluing reliably.
In the described formation, be preferably more than the 0.2MPa by the clipping viscous force after 120 ℃, 1 hour the heat treatment hot curing.Thus, even for example carry out the wire bond operation, can on the gluing surface of thermosetting die bonding film and semiconductor element or adherend, not produce detrusion owing to ultrasonic vibration or heating in this operation yet.That is, the ultrasonic vibration when semiconductor element can be because of wire bond is movable, can suppress the wire bond success rate thus and descend.
In addition, in the described formation, the melt viscosity under 120 ℃ before the hot curing is preferably in the scope of 50～1000Pas.By the melt viscosity before the hot curing that makes thermosetting die bonding film is more than the 50Pas, can make the adaptation of adherend good.As a result, with the gluing surface of adherend on, can reduce the generation in space.In addition, be below the 1000Pas by making described melt viscosity, can suppress adhesive component etc. and from thermosetting die bonding film, ooze out.As a result, can prevent to be adhesively fixed on adherend or the adherend pollution of fixed semiconductor element.
In the described formation, the energy storage modulus of elasticity under 260 ℃ by heat treatment in 175 ℃, 1 hour after the hot curing is preferably more than the 1MPa.Thus, for example,, can make the good semiconductor device of moisture-proof backflow even reliability is also high in moisture-proof reflow soldering test etc.
In addition, dicing/die bonding film of the present invention in order to address the above problem, is characterized in that, has the stacked structure of stating thermosetting die bonding film to some extent on the cutting film.
In addition, semiconductor device of the present invention in order to address the above problem, is characterized in that, uses above-mentioned thermosetting die bonding film or above-mentioned dicing/die bonding film and makes.
The present invention realizes following effect by the method for above-mentioned explanation.
Promptly, according to thermosetting die bonding film of the present invention, the gel fraction of organic principle was below the 20 weight % after the hot curing by 120 ℃, 1 hour heat treatment, and the heat treatment by 175 ℃, 1 hour and after the hot curing gel fraction of organic principle in the scope of 10～30 weight %, therefore, for example in the heat treatment of carrying out when joining to semiconductor element chip on the adherend or during wire bond, film is hot curing fully not.As a result, can reduce the cure shrinkage of thermosetting die bonding film, prevent to produce on the adherend warpage, thus the raising of output in the manufacturing of realization semiconductor device.
Description of drawings
Fig. 1 is the constructed profile of the dicing/die bonding film of expression an embodiment of the invention.
Fig. 2 is the constructed profile of the dicing/die bonding film of expression another embodiment of the present invention.
Fig. 3 is the example of semiconductor chip is installed in expression by the die bonding film of an embodiment of the invention a constructed profile.
Fig. 4 is that expression is by the three-dimensional constructed profile that the example of semiconductor chip is installed of described die bonding film.
Fig. 5 is that expression is used the said chip bonding film, passed through the three-dimensional constructed profile that the example of two semiconductor chips is installed of partition.
Fig. 6 is expression for having semiconductor chip on the resin substrates of soldering-resistance layer, be used to illustrate the key diagram of the assay method of its amount of warpage by the thermosetting die bonding film chip join.
Label declaration
1 base material
2 adhesive phases
3,13,21 die bonding films
The 3a die bonding film
The 3a part
The 3b part
5 semiconductor chips
6 adherends
7 bonding wires
8 sealing resins
9 pads
10,11 dicing/die bonding films
15 semiconductor chips
Embodiment
For the thermosetting die bonding film of present embodiment (below, be called " die bonding film "), the mode with as shown in Figure 1 the dicing/die bonding film that is laminated on the cutting film that is laminated with adhesive phase 2 on the base material 1 is that example describes below.
In the said chip bonding film 3, by 120 ℃, 1 hour heat treatment after the hot curing gel fraction of organic principle be below the 20 weight %, be preferably 0～15 weight %, more preferably in the scope of 0～10 weight %.Described gel fraction is 20 weight % when following, and for example, in the heat treatment when chip join, die bonding film 3 complete hot curings can suppress cure shrinkage thus.In addition, the heat treatment by 175 ℃, 1 hour and after the hot curing gel fraction of organic principle at 10～30 weight %, preferred 10～25 weight %, more preferably in the scope of 10～20 weight %.When described gel fraction was 10～30 weight %, even for example in the heat treatment when wire bond, die bonding film 3 is hot curing fully also, can suppress cure shrinkage thus.
The acid number of described die bonding film 3 is preferably in the scope of 4～10mgKOH/g, more preferably in the scope of 6～8mgKOH/g.Acid number is 4mgKOH/g when above, for example, when suppressing to produce warpage on the adherend by the heat treatment under 120 ℃, 1 hour condition, can improve the clipping viscous force.On the other hand, acid number is 10mgKOH/g when following, and the viscosity of the die bonding film 3 in the time of can suppressing normal temperature and preserve rises.
As the constituent material of described die bonding film 3, preferably form by thermosetting resin and thermoplastic resin.In addition, in the described thermoplastic resin, preferably comprise acid number and be preferably 10～40mgKOH/g, more preferably 20～40mgKOH/g, the further thermoplastic resin of preferred 25～35mgKOH/g.When acid number was lower than 10mgKOH/g, the clipping viscous force after 120 ℃ sometimes, 1 hour the heat treatment was insufficient.On the other hand, when acid number surpasses 40mgKOH/g, keeping quality variation sometimes.
As described thermoplastic resin, can enumerate: natural rubber, butyl rubber, isoprene rubber, neoprene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, polybutadiene, polycarbonate resin, thermoplastic polyimide resin, nylon 6 or saturated polyester resin, polyamide-imide resin or fluorine resins etc. such as nylon 6,6 polyamides such as grade, phenoxy resin, acrylic resin, PET or PBT.These thermoplastic resins may be used singly or two or more in combination.In these thermoplastic resins, special preferred ion impurity is few, thermal endurance is high, can guarantee the acrylic resin of the reliability of semiconductor element.
As described acrylic resin, be not particularly limited, can enumerate: have carbon number below 30, the particularly acrylate of the straight or branched alkyl of carbon number 4～18 or the polymer that methacrylate is composition etc. with one or more.As described alkyl, for example can enumerate: methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, isobutyl group, amyl group, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl, different nonyl, decyl, isodecyl, undecyl, lauryl, tridecyl, myristyl, stearyl, octadecyl or dodecyl etc.
In addition, other monomer as forming described polymer is not particularly limited, and for example can enumerate: acrylic acid, methacrylic acid, acrylic acid carboxylic ethyl ester, acrylic acid carboxylic pentyl ester, itaconic acid, maleic acid, fumaric acid or crotonic acid etc. contain carboxylic monomer; Anhydride monomers such as maleic anhydride or itaconic anhydride; Hydroxyl monomers such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-own ester of 6-hydroxyl, (methyl) acrylic acid-8-hydroxyl monooctyl ester, (methyl) acrylic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid-12-hydroxyl lauryl or acrylic acid (4-methylol cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamido-2-methyl propane sulfonic acid, (methyl) acrylamido propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester or (methyl) acryloxy naphthalene sulfonic acids etc. contain the sulfonic group monomer; Perhaps acryloyl phosphoric acid-phosphorous acidic group monomers such as 2-hydroxy methacrylate.In addition, (methyl) 2-Hydroxy ethyl acrylate is meant 2-Hydroxy ethyl acrylate and/or methacrylic acid-2-hydroxy methacrylate, and (methyl) of the present invention all has same implication.
As described thermosetting resin, can enumerate: phenolic resins, amino resins, unsaturated polyester resin, epoxy resin, polyurethane resin, polyorganosiloxane resin or thermoset polyimide resin etc.These resins may be used singly or two or more in combination.Especially preferably make the poor epoxy resin of the ionic impurity etc. of semiconductor element corrosion.In addition, as curing agent for epoxy resin, preferred phenolic resins.
Described epoxy resin, so long as then be not particularly limited, for example can use: bifunctional epoxy resin or polyfunctional epoxy resin or epoxy resin such as hydantoins type, triglycidyl isocyanurate type or glycidic amine type such as bisphenol A-type, Bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, phenol phenolic varnish type, orthoresol phenolic varnish type, three hydroxyphenyl methane types, four phenylol ethane types as the normally used epoxy resin of adhesive compound.These epoxy resin may be used singly or two or more in combination.In these epoxy resin, preferred especially phenolic resin varnish type epoxy resin, biphenyl type epoxy resin, three hydroxyphenyl methane type epoxy resin or four phenylol ethane type epoxy resin.This be because: these epoxy resin reactive good with as the phenolic resins of curing agent, and thermal endurance etc. is good.In addition, the content of the ionic impurity etc. of corrosion semiconductor element is few in the epoxy resin.
In addition, described phenolic resins works as described curing agent for epoxy resin, for example can enumerate: polycarboxylated styrenes such as phenolic varnish type phenol resin such as phenol novolac resin, phenol aralkyl resin, cresols novolac resin, tert-butyl phenol novolac resin, nonyl phenol novolac resin, resol (レ ゾ-Le) type phenol resin, poly(4-hydroxystyrene) etc.These phenolic resins may be used singly or two or more in combination.Preferred biphenyl type phenol novolac resin, phenol aralkyl resin in these phenolic resins by following chemical formulation.This is because can improve the connection reliability of semiconductor device.
Figure BSA00000310666800081
(described n is 0～10 natural number).
In addition, described n is preferably 0～10 natural number, more preferably 0～5 natural number.By in described number range, can guarantee the flowability of die bonding film 3.
Described epoxy resin and phenolic resins are that the mode in 1.5～6 the scope cooperates with respect to the ratio of the molal quantity of the phenolic hydroxyl group in the thermosetting resin composition with the molal quantity of the epoxy radicals in the described thermosetting composition.In addition, described ratio is preferably 1.5～4, and more preferably 2～3.By making described ratio is more than 1.3, can reduce the tensile modulus of elasticity of thermosetting die bonding film self, can reduce cure shrinkage.In addition, be below 6 by making described ratio, can prevent that the hot curing reaction of epoxy resin is insufficient.
In addition, the die bonding film 3 of present embodiment if formed by epoxy resin and the phenolic resins as the thermosetting composition, then also can contain other thermosetting composition.As other such thermosetting composition, for example can enumerate: amino resins, unsaturated polyester resin, polyurethane resin, organic siliconresin or thermoset polyimide resin etc.The thermosetting resin of precipitation thinner in addition,, sheetization, B rankization is fit to.These resins may be used singly or two or more in combination.The cooperation ratio of described other thermosetting composition with respect to 100 weight portion thermosetting compositions, is preferably in the scope of 0.1～10 weight portion, more preferably in the scope of 0.4～5 weight portion.
At this, when using acrylic resin as thermoplastic resin, with the ratio that cooperates of epoxy resin and phenolic resins be: with respect to 100 parts by weight of acrylic acid resinoids, the combined amount of epoxy resin and phenolic resins is preferably in the scope of 10～700 weight portions, more preferably in the scope of 20～600 weight portions.In addition, epoxy resin, phenolic resins and acrylic resin are because ionic impurity is few, and the thermal endurance height it is hereby ensured the reliability of semiconductor element.
The molal quantity of the epoxy radicals in the described thermosetting resin composition is under 1.5～6 the situation, can use the constituent material of thermal curing catalyst as die bonding film 3 with respect to the ratio of the molal quantity of the phenolic hydroxyl group in the thermosetting resin composition.As its cooperation ratio, with respect to 100 weight portion organic principles, preferably in the scope of 0.01～3.5 weight portion, more preferably in the scope of 0.01～1 weight portion, in the scope of preferred especially 0.01～0.5 weight portion.By making the cooperation ratio is more than 0.01 weight portion, during chip join between the unreacted epoxy groups polymerization until for example the back curing process, can reduce or eliminate this unreacted epoxy groups.As a result, can make and make that semiconductor element is gluing reliably to be fixed to that adherend (details as described later) is gone up and do not have the semiconductor device of peeling off.On the other hand, by the cooperation ratio is set at below 3.5 weight portions, can prevent to produce the curing obstacle.
As described thermal curing catalyst, be not particularly limited, for example can enumerate: glyoxaline compound, triphenylphosphine compounds, aminated compounds, triphenyl borine alkyl compound, three halo boranes compounds etc.These materials may be used singly or two or more in combination.
As described glyoxaline compound, can enumerate: glyoxal ethyline (trade name: 2MZ), 2-undecyl imidazole (trade name: C11Z), 2-heptadecyl imidazoles (trade name: C17Z), 1,2-methylimidazole (trade name: 1.2DMZ), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), 2-phenylimidazole (trade name: 2PZ), 2-phenyl-4-methylimidazole (trade name: 2P4MZ), 1 benzyl 2 methyl imidazole (trade name: 1B2MZ), 1-benzyl-2-phenylimidazole (trade name: 1B2PZ), 1-cyano ethyl-glyoxal ethyline (trade name: 2MZ-CN), 1-cyano ethyl-2-undecyl imidazole (trade name: C11Z-CN), 1-cyano ethyl-2-phenylimidazole trimellitic acid salt (trade name: 2PZCNS-PW), 2,4-diaminourea-6-[2 '-methylimidazolyl (1) '] ethyl-s-triazine (trade name: 2MZ-A), 2,4-diaminourea-6-[2 '-undecyl imidazole base (1) '] ethyl-s-triazine (trade name: C11Z-A), 2,4-diaminourea-6-[2 '-ethyl-4 '-methylimidazolyl (1) '] ethyl-s-triazine (trade name: 2E4MZ-A), 2,4-diaminourea-6-[2 '-methylimidazolyl (1) '] ethyl-s-triazine isocyanuric acid addition product (trade name: 2MA-OK), 2-phenyl-4,5-dihydroxy methylimidazole (trade name: 2PHZ-PW), 2 phenyl 4 methyl 5 hydroxy methylimidazole (trade name: 2P4MHZ-PW) etc. (be four countries and change into Co., Ltd.'s system).
As described triphenylphosphine compounds, be not particularly limited, for example can enumerate: three organic phosphines, tetraphenylphosphonibromide bromide such as triphenylphosphine, tributylphosphine, three (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine, diphenylmethyl Phenylphosphine (trade name: TPP-PB), methyl triphenyl
Figure BSA00000310666800102
(trade name: TPP-MB), the methyl triphenyl chlorination
Figure BSA00000310666800103
(trade name: TPP-MC), the methoxy triphenyl (trade name: TPP-MOC), benzyl triphenyl phosphonium chloride (trade name: TPP-ZC) etc. (be northern Xinghua and learn corporate system).In addition, as described triphenylphosphine compounds, preferably epoxy resin is shown the compound of non-solubility in fact.When epoxy resin is non-solubility, can suppresses hot curing and excessively carry out.As having the triphenylphosphine structure and epoxy resin being shown the thermal curing catalyst of non-solubility in fact, for example can enumerate: methyl triphenyl
Figure BSA00000310666800106
(trade name: TPP-MB) etc.In addition, described " non-solubility " is meant that the thermal curing catalyst that comprises the triphenylphosphine compounds is insoluble, more specifically, is meant in 10～40 ℃ of scopes of temperature and does not dissolve more than the 10 weight % in comprising the solvent of epoxy resin.
As described triphenyl borine alkyl compound, be not particularly limited, can enumerate for example three (p-methylphenyl) phosphine etc.In addition, as the triphenyl borine alkyl compound, also comprise compound with triphenylphosphine structure.As this compound with triphenylphosphine structure and triphenyl borine alkyl structure, be not particularly limited, for example can enumerate: tetraphenyl
Figure BSA00000310666800107
Tetraphenyl borate salts (trade name: TPP-K), tetraphenyl
Figure BSA00000310666800108
Four pairs three borates (trade name: TPP-MK), the benzyl triphenyl
Figure BSA00000310666800109
Tetraphenyl borate salts (trade name: TPP-ZK), triphenylphosphine triphenylborane (trade name: TPP-S) etc. (be northern Xinghua learn corporate system).
As described aminated compounds, be not particularly limited, for example can enumerate: monoethanolamine three borofluorides (ス テ ラ ケ ミ Off ア Co., Ltd. system), dicyandiamide (Na カ ラ イ テ ス Network Co., Ltd. system) etc.
As described three halo boranes compounds, be not particularly limited, can enumerate for example three chloroboranes etc.
Die bonding film 3 of the present invention is carried out under to a certain degree the crosslinked situation in advance, when making, can add polyfunctional compound with the reactions such as functional group of the molecule chain end of polymer as crosslinking agent.Thus, can improve the adhesive property under the high temperature, improve thermal endurance.
As described crosslinking agent, can use existing known crosslinking agent.Particularly more preferably toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, PPDI, 1, the polyisocyanate compounds such as addition product of 5-naphthalene diisocyanate, polyalcohol and vulcabond.As the addition of crosslinking agent, be preferably set to 0.05～7 weight portion usually with respect to described polymer 100 weight portions.When the amount of crosslinking agent surpassed 7 weight portions, adhesive tension descended, and is therefore not preferred.On the other hand, when being lower than 0.05 weight portion, the cohesiveness deficiency, therefore not preferred.In addition, as required, can together contain other polyfunctional compounds such as epoxy resin with such polyisocyanate compound.
In addition, in the die bonding film 3, can suitably cooperate inorganic filler (inorganic constituents) according to its purposes.The cooperation of inorganic filler can be given conductivity or be improved thermal conductivity, adjusting modulus of elasticity etc.As described inorganic filler, for example can enumerate: the various inorganic powders that comprise metals such as ceramic-like such as silicon dioxide, clay, gypsum, calcium carbonate, barium sulfate, aluminium oxide, beryllium oxide, carborundum, silicon nitride, aluminium, copper, silver, gold, nickel, chromium, lead, tin, zinc, palladium, scolding tin or alloy type and carbon etc.These fillers may be used singly or two or more in combination.Wherein, preferably use silicon dioxide, especially preferably use fused silica.In addition, the average grain diameter of inorganic filler is preferably in the scope of 0.1～80 μ m.The use level of described inorganic filler is preferably set to 0～80 weight portion with respect to organic resin composition 100 weight portions.Preferred especially 0～70 weight portion.
In addition, in the die bonding film 3, except described inorganic filler, can suitably cooperate other additive as required.As other additive, for example can enumerate: fire retardant, silane coupler or ion trap agent etc.As described fire retardant, for example can enumerate: antimony trioxide, antimony pentaoxide, brominated epoxy resin etc.These fire retardants may be used singly or two or more in combination.As described silane coupler, for example can enumerate: β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane etc.These compounds may be used singly or two or more in combination.As described ion trap agent, for example can enumerate: hydrotalcite, bismuth hydroxide etc.These ion trap agent may be used singly or two or more in combination.
The die bonding film 3 of described dicing/die bonding film 10,11 is preferably by partition protection (not shown).Partition has the function of the protective material of conduct protection die bonding film 3 before using for reality.In addition, partition can also use by the support base material when being transferred to die bonding film 3 on the adhesive phase 2.Partition is peeled off when pasting workpiece on the die bonding film 3 of dicing/die bonding film.As partition, can use PETG (PET), polyethylene, polypropylene or utilize removers such as fluorine-containing remover, chain alkyl esters of acrylic acid remover to carry out plastic film after the surface coated or paper etc.
In addition, the melt viscosity under 120 ℃ before the hot curing of described die bonding film 3 is preferably 50～1000Pas, more preferably 100～800Pas, preferred especially 200～600Pas.By described melt viscosity is set at more than the 50Pas, can make adaptation become good to adherends such as substrates.As a result, with the gluing surface of adherend on, can reduce the generation in space.On the other hand, by described melt viscosity is set at below the 1000Pas, can suppresses adhesive component etc. and from thermosetting die bonding film, ooze out.As a result, can prevent adherend or be adhesively fixed and fix on the pollution of the semiconductor element on the adherend.In addition, described melt viscosity is measured and is calculated by following assay method.That is, can use flow graph (HAAKE corporate system, trade name: RS-1), measure by parallel plate method.That is,, place and take from the 0.1g sample of die bonding film 3, and begin to measure being heated on 100 ℃ the plate.To measure the mean value of the melt viscosity of beginning after 120 seconds as melt viscosity.In addition, the gap between plate is 0.1mm.
Energy storage modulus of elasticity after the hot curing of described die bonding film 3 under 260 ℃ is preferably more than the 1MPa, more preferably 5～100MPa, preferred especially 10～100MPa.Thus, for example, can prevent that in sealing process semiconductor element from tilting, in addition, when the reflow soldering operation, can prevent to produce between die bonding film and the adherend and peel off.In addition, in the hot curing of this said die bonding film 3, be meant 140 ℃ carry out heat treatment in 2 hours after, the state when under 175 ℃, carrying out heat treatment in 1 hour again.In addition, the energy storage Determination of Modulus for example can be used solid determination of viscoelasticity device (Rheometric Scientific corporate system, model: RSA-III).Promptly, specimen size is set at long 400mm * wide 10mm * thick 200 μ m, to measure sample and be installed in film stretching mensuration with on the anchor clamps, at stretching energy storage modulus of elasticity and the loss elastic modulus measured under the condition of 10 ℃/minute of frequency 1Hz, programming rate under-50～300 ℃ of temperature ranges, obtain by reading energy storage modulus of elasticity under 260 ℃ (E ').
The thickness of die bonding film 3 (being gross thickness under the situation of duplexer) is not particularly limited, and for example, is about 5 μ m～about 100 μ m, preferred about 5 μ m～about 50 μ m.
In addition, die bonding film 3 for example can only be made of the adhesive layer individual layer.In addition, by the thermoplastic resin that glass transition temperature is different, the different thermosetting resin appropriate combination of heat curing temperature, can form two-layer above sandwich construction.Use cutting water in the cutting action of semiconductor wafer, therefore, die bonding film 3 moisture absorptions sometimes, moisture content reaches more than the normality.If be adhesive under the state of such high-moisture percentage on the substrate etc., then, produce perk sometimes at the gluing occluded water at the interface of back cure stage steam.Therefore, as die bonding film 3,, spread at back cure stage steam permeable film, thereby can avoid described problem by forming the structure of clamping high poisture-penetrability core by adhesive layer.Consider that from this viewpoint die bonding film 3 can adopt the sandwich construction that is formed with adhesive layer on the single or double of core.
As described core, can enumerate: film (for example polyimide film, polyester film, pet film, PEN film, polycarbonate film etc.), resin substrates, minute surface silicon wafer, silicon substrate or the glass substrate etc. that strengthen with glass fibre or plastics system non-woven fibre.
In addition, die bonding film 3 is preferably protected by partition (not shown).Partition has the function of the protective material of conduct protection die bonding film before using for reality.In addition, partition can also use by the support base material when die bonding film 3 being transferred on the cutting film.Partition is peeled off when pasting workpiece on die bonding film 3.As partition, can use PETG (PET), polyethylene, polypropylene or utilize removers such as fluorine-containing remover, chain alkyl esters of acrylic acid remover to carry out plastic film after the surface coated or paper etc.
As described cutting film, for example, can be set forth in the cutting film that is laminated with adhesive phase 2 on the substrate 1.Die bonding film 3 is layered on the adhesive phase 2.In addition, as shown in Figure 2, can be the structure that only forms die bonding film 3 ' in the semiconductor wafer adhesive portion.
Described base material 1 is as the intensity parent of dicing/die bonding film 10,11.For example can enumerate: low density polyethylene (LDPE), linear polyethylene, medium density polyethylene, high density polyethylene (HDPE), ultra-low density polyethylene, atactic copolymerized polypropene, block copolymerization polypropylene, homo-polypropylene, polybutene, polyolefin such as polymethylpentene, vinyl-vinyl acetate copolymer, ionomer resin, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate is (random, alternately) copolymer, ethylene-butene copolymer, ethene-hexene copolymer, polyurethane, PETG, polyester such as PEN, Merlon, polyimides, polyether-ether-ketone, polyimides, Polyetherimide, polyamide, Wholly aromatic polyamide, polyphenylene sulfide, aromatic polyamides (paper), glass, glass cloth, fluorine resin, polyvinyl chloride, polyvinylidene chloride, cellulosic resin, polyorganosiloxane resin, metal (paper tinsel), paper etc.When adhesive phase 2 was ultraviolet hardening, 1 pair of ultraviolet ray of preferred substrates had transmittance.
In addition, as the material of base material 1, can enumerate the polymer such as crosslinked body of above-mentioned resin.Described plastic film can not stretch and uses, and can carry out as required using after single shaft or the biaxial stretch-formed processing yet.Utilization has been given the resin sheet of heat-shrinkable by stretch processing etc., by making this base material 1 thermal contraction, can reduce the gluing area of adhesive phase 2 and die bonding film 3, thereby can easily reclaim semiconductor chip after cutting.
In order to improve and the adaptation of adjoining course, retentivity etc., the surface treatment that the surface of base material 1 can implement to habitually practise, utilizes the coating of silane coupling agent (adhesion substance for example described later) to handle at chemistry or physical treatments such as for example chromic acid processing, ozone exposure, fire exposure, high-voltage electric shock exposure, ionizing radiation processing.
Described base material 1 can suitably select to use of the same race or kinds of materials, also can use the material after the multiple material blend as required.In addition, in order to give base material 1 antistatic performance, can on described base material 1, be provided with and comprise metal, alloy, their thickness of oxide etc. for approximately
Figure BSA00000310666800151
～approximately
Figure BSA00000310666800152
The evaporation layer of conductive materials.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 μ m～about 200 μ m.
In addition, in the scope of not damaging effect of the present invention etc., can contain various additives (for example, colouring agent, filler, plasticizer, age resister, antioxidant, surfactant, fire retardant etc.) in the base material 1.
The adhesive that uses in the formation of adhesive phase 2 is as long as strippingly 3 of control chip bonding films are not particularly limited.For example, can use general pressure-sensitive adhesives such as acrylic adhesives, rubber adhesive.As described pressure-sensitive adhesive, the electronic unit that pollutes from taboos such as semiconductor wafer or glass utilizes the viewpoints such as cleaning washing performance of organic solvents such as ultra-pure water or alcohol to consider, preferably is the acrylic adhesives of base polymer with the acrylic polymer.
As described acrylic polymer, can enumerate and use the polymer of acrylate as the main monomer composition.As described acrylate, for example can enumerate: (for example use (methyl) alkyl acrylate, 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, the 2-Octyl Nitrite, different monooctyl ester, the ninth of the ten Heavenly Stems ester, the last of the ten Heavenly stems ester, the isodecyl ester, the hendecane ester, the dodecane ester, the tridecane ester, tetradecane ester, the hexadecane ester, the octadecane ester, the carbon number 1～30 of alkyl such as eicosane ester, the straight or branched Arrcostab of carbon number 4～18 etc. particularly) and (methyl) acrylic acid cycloalkanes ester (for example, ring pentyl ester, cyclohexyl etc.) one or more are as acrylic polymer of monomer component etc.In addition, (methyl) acrylate is represented acrylate and/or methacrylate, and (methyl) of the present invention all represents identical implication.
Described acrylic polymer, in order to improve cohesiveness, thermal endurance etc., can contain as required with can with the corresponding unit of other monomer component of described (methyl) alkyl acrylate or the copolymerization of cycloalkanes ester.As such monomer component, for example can enumerate: acrylic acid, methacrylic acid, (methyl) acrylic acid carboxylic ethyl ester, (methyl) acrylic acid carboxylic pentyl ester, itaconic acid, maleic acid, fumaric acid, crotonic acid etc. contain carboxylic monomer; Anhydride monomers such as maleic anhydride, itaconic anhydride; Hydroxyl monomers such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) acrylic acid-2-hydroxy propyl ester, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-own ester of 6-hydroxyl, (methyl) acrylic acid-8-hydroxyl monooctyl ester, (methyl) acrylic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid-12-hydroxyl lauryl, (methyl) acrylic acid (4-methylol cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester, (methyl) acryloxy naphthalene sulfonic acids etc. contain the sulfonic group monomer; Acryloyl phosphoric acid-phosphorous acidic group monomers such as 2-hydroxy methacrylate; Acrylamide, acrylonitrile etc.These copolymerisable monomer compositions can use one or more.The use amount of these copolymerisable monomers is preferably below the 40 weight % of whole monomer components.
In addition, described acrylic polymer is in order to carry out the crosslinked polyfunctional monomer etc. that also can contain as required as the comonomer composition.As such polyfunctional monomer, for example can enumerate: hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, carbamate (methyl) acrylate etc.These polyfunctional monomers can use one or more.The use amount of polyfunctional monomer is considered from viewpoints such as adhesion characteristics, is preferably below the 30 weight % of whole monomer components.
Described acrylic polymer can be by obtaining single monomer or two or more monomer mixture polymerization.Polymerization can be undertaken by any-modes such as polymerisation in solution, emulsion polymerisation, polymerisation in bulk, suspension polymerisations.From preventing that the content of preferred low molecular weight substance is few to viewpoints such as the pollution consideration of the adherend of cleaning.Consider that from this viewpoint the number-average molecular weight of acrylic polymer is preferably about more than 300,000, more preferably from about 400,000～about 3,000,000.
In addition, in order to improve the number-average molecular weight of acrylic polymer as base polymer etc., also can suitably adopt outside crosslinking agent in the described adhesive.As the concrete grammar of outside cross-linking method, can enumerate: add so-called crosslinking agent such as polyisocyanate compound, epoxy compounds, aziridine cpd, melamine class crosslinking agent and make the method for its reaction.When using outside crosslinking agent, its use amount is by suitably determining with the balance of the crosslinked base polymer of desire and according to the use as adhesive.Generally speaking,, be preferably below 5 weight portions, more preferably cooperate 0.1～5 weight portion with respect to described base polymer 100 weight portions.In addition, as required, in adhesive, except that mentioned component, also can use additives such as known in the past various tackifier, age resister.
Adhesive phase 2 can be formed by radiation curing type adhesive.Radiation curing type adhesive increases the degree of cross linking, thereby can easily reduce its bonding force by the irradiation of ultraviolet israds.For example, by only to the part 2a illumination radiation line of adhesive phase shown in Figure 22, can be provided with and part 2b between poor adhesion.
In addition, by radiation curing type adhesive phase 2 being solidified, can easily form the part 2a that bonding force significantly descends with die bonding film 3 '.Owing on the part 2a of curing and bonding force decline, paste die bonding film 3 ', so the interface of part 2a and die bonding film 3 ' has the character of peeling off easily when picking up.On the other hand, the part of illumination radiation line does not have sufficient adhesive, forms part 2b.
As previously mentioned, bonding in the adhesive phase 2 of dicing/die bonding film 10 shown in Figure 1 by described part 2b and die bonding film 3 that uncured radiation curing type adhesive forms, the confining force in the time of can guaranteeing to cut.Like this, radiation curing type adhesive can with good gluing-peel off balanced support and be used for semiconductor chip (semiconductor chip etc.) is affixed to die bonding film 3 on the adherends such as substrate.In the adhesive phase 2 of dicing/die bonding film 11 shown in Figure 2, described part 2b is wafer central (wafer ring) fixedly.
Radiation curing type adhesive can use with being not particularly limited to have carbon-to-carbon double bond israds curable functional group and shows fusible radiation curing type adhesive.As radiation curing type adhesive, can illustration for example: in general contact adhesive such as described acrylic adhesives, rubber adhesive, be combined with the monomer component of radiation curing or the addition type radiation curing type adhesive of oligomer composition.
As the described radiation curing monomer component that cooperates, for example can enumerate: oligourethane, carbamate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,4-butanediol two (methyl) acrylate etc.In addition, radiation curing oligomers composition, can enumerate: various oligomer such as carbamates, polyethers, polyesters, polycarbonate-based, polybutadiene, its weight average molecular weight is suitable in about scope of 100～about 30000.The use level of radiation curing monomer component or oligomer composition can be according to the suitably definite amount that can reduce the bonding force of adhesive phase of the kind of described adhesive phase.Generally speaking, with respect to base polymers such as acrylic polymer 100 weight portions that constitute adhesive, for example be about 5 weight portions～about 500 weight portions, preferred about 40 weight portions～about 150 weight portions.
In addition, as radiation curing type adhesive, except the radiation curing type adhesive of the addition type that illustrates previously, can also enumerate use in polymer lateral chain or main chain or the main chain end have the interior radiation curing type adhesive in type of the polymer of carbon-to-carbon double bond as base polymer.The oligomer that the radiation curing type adhesive of inherent type need not to contain or do not contain in a large number as low molecular weight compositions becomes to grade, therefore oligomer becomes to grade can not pass in time in adhesive and moves, can form the adhesive phase of stable layer structure, therefore preferred.
Described base polymer with carbon-to-carbon double bond can use to have carbon-to-carbon double bond and have fusible polymer with being not particularly limited.As such base polymer, preferably with the polymer of acrylic polymer as basic framework.As the basic framework of acrylic polymer, can enumerate the acrylic polymer that the front illustration is crossed.
The introduction method of carbon-to-carbon double bond is not particularly limited in the described acrylic polymer, can adopt the whole bag of tricks, and with carbon-to-carbon double bond import polymer lateral chain on MOLECULE DESIGN than being easier to.Can enumerate for example following method: the monomer copolymerization of functional group will be had in advance in acrylic polymer after, make to have and under the state of the radiation curing that keeps carbon-to-carbon double bond, to carry out condensation or addition reaction with the functional group of this functional group reactions and the compound of carbon-to-carbon double bond.
As the combination example of these functional groups, can enumerate: carboxyl and epoxy radicals, carboxyl and '-aziridino, hydroxyl and NCO etc.In the combination of these functional groups, consider the easiness that reaction is followed the trail of, the combination of preferred hydroxyl and NCO.In addition, if generate described combination with acrylic polymer of carbon-to-carbon double bond by the combination of these functional groups, then functional group can be in any side of acrylic polymer and described compound, in described preferred compositions, preferred acrylic polymer has hydroxyl, described compound has the situation of NCO.At this moment,, for example can enumerate: methacryl isocyanates, 2-methylacryoyloxyethyl isocyanates, isopropenyl-α, alpha-alpha-dimethyl dibenzoyl isocyanates etc. as isocyanate compound with carbon-to-carbon double bond.In addition, as acrylic polymer, can use copolymerization such as ether compound and the polymer that obtains with the illustrative hydroxyl monomer in front or 2-hydroxyethyl vinyl ethers, 4-hydroxybutyl vinyl ethers, diethylene glycol mono vinyl ether.
The radiation curing type adhesive of described inherent type can use described base polymer (particularly acrylic polymer) with carbon-to-carbon double bond separately, also can cooperate described radiation curing monomer component or oligomer composition in the scope of not damaging characteristic.The radiation curing oligomers becomes to grade, with respect to base polymer 100 weight portions usually in the scope of 30 weight portions, the scope of preferred 0～10 weight portion.
Described radiation curing type adhesive preferably contains Photoepolymerizationinitiater initiater by curing such as ultraviolet rays the time.As Photoepolymerizationinitiater initiater, for example can enumerate: 4-(2-hydroxyl-oxethyl) phenyl (2-hydroxyl-2-propyl group) ketone, Alpha-hydroxy-α, α-ketols compounds such as α '-dimethyl acetophenone, 2-methyl-2-hydroxypropiophenonepreparation, 1-hydroxycyclohexylphenylketone; Methoxyacetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 2-methyl isophthalic acid-[4-(methyl mercapto)-phenyl]-2-morpholinyl propane-acetophenone compounds such as 1-ketone; Benzoin ether compounds such as benzoin ethyl ether, benzoin iso-propylether, anisoin methyl ether; Ketal compounds such as benzil dimethyl ketal; Aromatic sulfonyl compounds such as 2-naphthalene sulfonyl chloride; 1-phenyl-1, photolytic activity oxime compounds such as 2-propanedione-2-(O-ethoxy carbonyl) oxime; Benzophenone, benzoyl benzoic acid, 3,3 '-dimethyl-benzophenone compounds such as 4-methoxy benzophenone; Thioxanthones, 2-clopenthixal ketone, 2-methyl thioxanthones, 2,4-dimethyl thioxanthones, isopropyl thioxanthone, 2,4-two clopenthixal ketones, 2,4-diethyl thioxanthone, 2, thioxanthones compounds such as 4-diisopropyl thioxanthones; Camphorquinone; Halogenated ketone; Acylphosphine oxide; Acyl phosphonate etc.The use level of Photoepolymerizationinitiater initiater with respect to base polymers such as acrylic polymer 100 weight portions that constitute adhesive, for example is about 0.05 weight portion～about 20 weight portions.
Form by radiation curing type adhesive under the situation of adhesive 2, preferably the part of adhesive phase 2 is carried out irradiation with radiation and make the bonding force of bonding force＜part 2b of part 2a.In the dicing/die bonding film of Fig. 2, for example,, be the bonding force of bonding force＜part 2b of part 2a for relation as the SUS304 plate (#2000 polishing) of adherend.
As the method that in described adhesive phase 2, forms described part 2a, can enumerate: on base material 1, form radiation curing type adhesive phase 2 backs to described part 2a partly the illumination radiation line make the method for its curing.Local irradiation with radiation can carry out across the photomask that is formed with the pattern corresponding with part 3b etc. beyond the semiconductor wafer adhesive portion 3a.In addition, can enumerate method that the point-like irradiation ultraviolet radiation is cured etc.The formation of radiation curing type adhesive phase 2 can be transferred on the base material 1 and carries out by being arranged on radiation curing type adhesive phase on the partition.Local radiation curing also can carry out the radiation curing type adhesive phase 2 that is arranged on the partition.
In addition, form by radiation curing type adhesive under the situation of adhesive phase 2, can use the whole or local base material that carries out shading to the part beyond part single face at least, corresponding with semiconductor wafer adhesive portion 3a of base material 1, after forming radiation curing type adhesive phase 2 on this base material, carry out irradiation with radiation, make corresponding with semiconductor wafer adhesive portion 3a partly solidified, thereby form the described part 2a that bonding force descends.As light screening material, can make by the material that printing or evaporation etc. on support film can become photomask.By described manufacture method, can make dicing/die bonding film 10 of the present invention effectively.
In addition, because of oxygen produces under the situation of solidifying obstacle, preferably utilize the surface blocking-up oxygen (air) of any means during irradiation with radiation from radiation curing type adhesive phase 2.For example can enumerate: coat the method on surface of described adhesive phase 2 or the method etc. of in nitrogen atmosphere, carrying out the irradiation of ultraviolet israds with partition.
The thickness of adhesive phase 2 is not particularly limited, and from realizing preventing the defective of chip cutting face and viewpoints such as the fixedly maintenance consideration of adhesive layer simultaneously, is preferably about 1 μ m to about 50 μ m.Further preferred 2 μ m～30 μ m, more preferably 5 μ m～25 μ m.
In addition, in the scope of not damaging effect of the present invention etc., can contain various additives (for example, colouring agent, thickener, extender, filler, tackifier, plasticizer, age resister, antioxidant, surfactant, crosslinking agent etc.) in the adhesive phase 2.
The dicing/die bonding film of present embodiment can followingly be made.Below, be that example describes with dicing/die bonding film 10.At first, base material 1 can be by existing known film-forming method system film.As this film-forming method, can illustration for example: the The tape casting in calendering system embrane method, the organic solvent, the blowing extrusion molding in the enclosed system, T shape die head extrusion molding, coetrusion, dry lamination method etc.
Then, coating adhesive composition and dry (heat cross-linking as required) and form adhesive phase 2 on base material 1.As coating method, can enumerate: roller coat, silk screen coating, intaglio plate coating etc.In addition, coating can directly be carried out on base material 1, also can be applied to the surface and carry out being transferred to then on the base material 1 on the peeling paper etc. of lift-off processing.
On the other hand, the formation material that is used to form die bonding film 3 is applied to predetermined thickness on peeling paper, under predetermined condition, carries out drying again and form coating.By this coating being transferred on the above-mentioned adhesive phase 2, form die bonding film 3.In addition, after will forming material and being coated directly onto on the above-mentioned adhesive phase 2, under predetermined condition, carry out drying, also can form die bonding film 3 thus.By above method, can obtain dicing/die bonding film 10 of the present invention.
(manufacture method of semiconductor device)
Below, the method for the die bonding film that uses present embodiment being made semiconductor device describes.Fig. 3 is the example of semiconductor element is installed in expression by die bonding film a constructed profile.
The manufacture method of the semiconductor device of present embodiment has: the wafer adhesive portion 3a (hereinafter referred to as die bonding film 3a) by die bonding film 3 is affixed to set operation on the adherend 6 with semiconductor chip (semiconductor element) 5; With the wire bond operation of carrying out wire bond.In addition, have: use sealing resin 8 the resin-sealed operation of semiconductor chip 5 sealings and the back curing process that sealing resin 8 backs are solidified.
As described adherend 6, can enumerate the semiconductor chip of lead frame, TAB film, substrate or making in addition etc.Adherend 6 for example can be the deformation type adherend of easy deformation, also can be the non-deformation type adherend (semiconductor wafer etc.) that is difficult to be out of shape.As described substrate, can use known in the past substrate.In addition, as described lead frame, organic substrate that can use die-attach area such as Cu lead frame, 42 alloy lead wire frames or make by glass epoxide, BT (bismaleimides-triazine), polyimides etc.But, the invention is not restricted to these, be also included within semiconductor element be installed, be electrically connected the operable circuitry substrate in back with semiconductor element.
Described set operation as shown in Figure 1, is with the operation of semiconductor chip 5 chip join to the adherend 6 by die bonding film 3a.This operation makes die bonding film 3a hot curing by heat-treating under predetermined condition, and semiconductor chip 5 is glued on the adherend 6 fully.Temperature when heat-treating is preferably 100～200 ℃, more preferably in 120～180 ℃ scope.In addition, heat treatment time is preferably 0.25 hour～and 10 hours, more preferably 0.5 hour～8 hours.As the method that semiconductor chip 5 is affixed on the adherend 6, for example can enumerate: after being laminated to die bonding film 3a on the adherend 6, with semiconductor chip 5 is that upside stacks gradually the method for carrying out set on die bonding film 3a with the wire bond face.In addition, also set in advance can there be the semiconductor chip 5 of die bonding film 3a to be affixed on the adherend 6 also stacked.
Described wire bond operation is the operation that the front end of the portion of terminal (inner lead) of adherend 6 is electrically connected with electrode pad (not shown) on the semiconductor chip 5 with bonding wire 7.As described bonding wire 7, can use for example gold thread, aluminum steel or copper cash etc.Wire bond carries out in temperature is 80～250 ℃, preferred 80～220 ℃ scope.In addition, its heating time be the several seconds～several minutes.Under the state of connecting line in heating reaches described temperature range, can carry out by the crimping that is used in combination hyperacoustic vibrational energy and pressurization.
Described resin-sealed operation is to utilize the operation of sealing resin 8 with semiconductor chip 5 sealings.This operation is carried out in order to protect the semiconductor chip 5 and the bonding wire 7 of lift-launch on adherend 6.This operation is undertaken by with mould sealing resin being shaped.As sealing resin 8, for example can use epoxy resin.When resin-sealed, under 175 ℃ heating-up temperature, carried out 60～90 seconds usually, still, the invention is not restricted to this, for example also can under 165～185 ℃, carry out solidifying in several minutes.Thus, sealing resin is solidified.Among the present invention, in the chip join operation,, after the sealing resin operation, the space between die bonding film 3a and the adherend 6 is disappeared even under the situation of heat-treating in order to make die bonding film 3a hot curing.
In the curing process of described back, make and in described sealing process, solidify inadequate sealing resin 8 full solidification.Heating-up temperature in this operation is according to the kind of sealing resin and difference, and for example in 165～185 ℃ scope, be about 0.5 hour～about 8 hours heating time.In addition, in this operation, can make the complete hot curing of die bonding film 3a.At this moment, preferably in die bonding film 3a, cooperate described thermal curing catalyst.Thus, make and carry out polymerization reaction between the residual unreacted epoxy radicals mutually, carry out the hot curing of die bonding film 3a again.As a result, can semiconductor chip 5 be fixed on the adherend reliably by die bonding film 3a.
The semiconductor packages that more than obtains when for example carrying out moisture-proof reflow soldering test, also has the high reliability that can tolerate this test.Moisture-proof reflow soldering test is undertaken by known method in the past.
In addition, dicing/die bonding film of the present invention as shown in Figure 4, also goes for a plurality of semiconductor chips are stacked and situation that carry out three-dimensional installation.Fig. 4 is that expression is by the three-dimensional constructed profile that the example of semiconductor chip is installed of die bonding film.Under the situation that three-dimensional shown in Figure 4 is installed, at least one die bonding film 3a that at first will be cut into the same size of semiconductor chip is affixed on the adherend 6, and the mode that is upside with semiconductor chip 15 with its wire bond face by die bonding film 3a is carried out set then.Then, the electrode pad of avoiding semiconductor chip 5 partly comes set die bonding film 13.And then the mode that is upside with second half conductor chip 15 with its wire bond face on die bonding film 13 is carried out set.
Then, carry out the wire bond operation.Thus, with bonding wire 7 separately electrode pad in semiconductor chip 5 and second half conductor chip 15 is electrically connected with adherend 6.
Then, use the sealing process of sealing resin 8, sealing resin is solidified sealing such as semiconductor chip 5 grades.And utilize die bonding film 3a with set between adherend 6 and the semiconductor chip 5.In addition, utilize die bonding film 13 with also set between semiconductor chip 5 and second half conductor chip 15.In addition, behind the sealing process, can carry out the back curing process.
Even under the situation that the three-dimensional of semiconductor chip is installed,, therefore can simplify manufacturing process and improve rate of finished products owing to do not carry out die bonding film 3a, 13 heat treated.In addition, adherend 6 does not produce warpage, and semiconductor chip 5 and second half conductor chip 15 do not crack, and therefore can realize the further slimming of semiconductor element.
In addition, as shown in Figure 5, can between semiconductor chip, carry out three-dimensional and install by the stacked pad of die bonding film.Fig. 5 is that expression utilizes the constructed profile of die bonding film with the three-dimensional example of installing of two semiconductor chips across pad.
Under the situation that three-dimensional shown in Figure 5 is installed, at first on adherend 6, stack gradually die bonding film 3a, semiconductor chip 5 and die bonding film 21 and temporary transient set.And then, on die bonding film 21, stack gradually pad 9, die bonding film 21, die bonding film 3a and semiconductor chip 5 and set.
Then, as shown in Figure 5, carry out the wire bond operation.Thus, with bonding wire 7 electrode pad in the semiconductor chip 5 is electrically connected with adherend 6.
Then, utilize the sealing process of sealing resin 8, sealing resin 8 is solidified semiconductor chip 5 sealings.Thus, obtain semiconductor package body.The preferred disposable Sealing Method that only semiconductor chip 5 one side single faces is sealed of sealing process (one draws together envelope ends method).Sealing is carried out in order to protect the semiconductor chip of pasting on the bonding sheet 5, the method for its exemplary process for using sealing resin 8 to be shaped in mould.At this moment, the general mould that is made of the upper die and lower die with a plurality of chambers that uses carries out sealing process simultaneously.Heating-up temperature preference when resin-sealed is as in 170～180 ℃ scope.Behind the sealing process, also can carry out the back curing process.
In addition,, be not particularly limited, can use for example existing known silicon, polyimide film etc. as described pad 9.In addition, as described pad, also can use core.Be not particularly limited as core, can use existing known core.Particularly, the resin substrates, minute surface silicon wafer, silicon substrate or the glass substrate that can use film (for example polyimide film, polyester film, pet film, PEN film, polycarbonate film etc.), strengthen with glass fibre or plastics system non-woven fibre.
Then, on printed circuit board (PCB), above-mentioned semiconductor package body is carried out mounted on surface.As the method for mounted on surface, for example can enumerate: in advance after supplying with scolder on the printed circuit board (PCB), the reflow soldering of welding by heating and meltings such as hot blasts.As heating means, can enumerate hot air reflux, infrared ray backflow etc.In addition, can be the any-mode of whole heating, localized heating.Heating-up temperature is preferably 240～265 ℃, and heating time is preferably in 1 second～20 seconds scope.
(other item)
Three-dimensional when semiconductor element is installed on described substrate etc., form buffering in the one side of the circuit that forms semiconductor element and film.Film as this buffering, for example can enumerate: film by the buffering that heat stable resins such as silicon nitride film or polyimide resin form.
In addition, when the three-dimensional of semiconductor element was installed, the die bonding film that each stage uses was not limited to also can suitably change according to create conditions or purposes etc. by constituting same the composition.
In addition, in the above-mentioned execution mode, be illustrated, still, the invention is not restricted to this for last disposable modes of carrying out the wire bond operation later on such as a plurality of semiconductor elements being laminated to substrate.For example, all carry out the wire bond operation in the time of also can be on semiconductor element being laminated to substrate etc. at every turn.
Embodiment
Below, the preferred embodiments of the present invention are carried out illustration ground describe in detail, still, material of putting down in writing among this embodiment or use level etc., the record of short of special qualification, then the present invention is not limited to this.In addition, part is meant weight portion.
(embodiment 1)
To with ethyl acrylate-methyl methacrylate acrylic polymer (Na ガ セ ケ system テ Star Network ス Co., Ltd. system of principal component, WS-023, acid number 20mgKOH/g) 7.5 weight %, epoxy resin A (JER Co., Ltd. system, Epicoat 1004) 18.6 weight %, epoxy resin B (JER Co., Ltd. system, Epicoat 827) 12.0 weight %, phenolic resins (Mitsui Chemicals, Inc's system, ミ レ Star Network ス XLC-4L) 21.7 weight %, preparing spherical SiO 2 (ア De マ テ Star Network ス Co., Ltd. system, SO-25R) 39.9 weight %, silane coupler (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI system, KBM-303) (four countries change into Co., Ltd.'s system for 0.29 weight % and thermal curing catalyst, C11-Z) 0.01 weight % (is 0.017 weight portion with respect to 100 weight portions of the organic principle except that preparing spherical SiO 2) is dissolved in the methylethylketone, the adhesive compound (wherein, from above-mentioned organic principle, removing methylethylketone) of preparation concentration 23.6 weight %.In addition, (molal quantity of the epoxy radicals in the thermosetting composition of adhesive compound)/(molal quantity of the phenolic hydroxyl group in the thermosetting composition of adhesive compound) is 1.5.
The demoulding that the pet film of thickness 50 μ m after this adhesive compound solution coat handled to the polysiloxanes demoulding is made is handled on the film (release liner), then 130 ℃ of dryings 2 minutes.Thus, make the thermosetting die bonding film of thickness 25 μ m.
(embodiment 2)
To with ethyl acrylate-methyl methacrylate acrylic polymer (Na ガ セ ケ system テ Star Network ス Co., Ltd. system of principal component, SG-700AS, acid number 36mgKOH/g) 7.5 weight %, epoxy resin A (JER Co., Ltd. system, Epicoat 1004) 18.6 weight %, epoxy resin B (JER Co., Ltd. system, Epicoat 827) 12.0 weight %, phenolic resins (Mitsui Chemicals, Inc's system, ミ レ Star Network ス XLC-4L) 21.7 weight %, preparing spherical SiO 2 (ア De マ テ Star Network ス Co., Ltd. system, SO-25R) 39.9 weight %, silane coupler (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI system, KBM-303) (four countries change into Co., Ltd.'s system for 0.29 weight % and thermal curing catalyst, C11-Z) 0.01 weight % (is 0.017 weight portion with respect to 100 weight portions of the organic principle except that preparing spherical SiO 2) is dissolved in the methylethylketone, the adhesive compound (wherein, from above-mentioned organic principle, removing methylethylketone) of preparation concentration 23.6 weight %.In addition, (molal quantity of the epoxy radicals in the thermosetting composition of adhesive compound)/(molal quantity of the phenolic hydroxyl group in the thermosetting composition of adhesive compound) is 1.5.
The demoulding that the pet film of thickness 50 μ m after this adhesive compound solution coat handled to the polysiloxanes demoulding is made is handled on the film (release liner), then 130 ℃ of dryings 2 minutes.Thus, make the thermosetting die bonding film of thickness 25 μ m.
(embodiment 3)
To with ethyl acrylate-methyl methacrylate acrylic polymer (Na ガ セ ケ system テ Star Network ス Co., Ltd. system of principal component, SG-700AS changes, acid number 50mgKOH/g) 7.5 weight %, epoxy resin A (JER Co., Ltd. system, Epicoat 1004) 18.6 weight %, epoxy resin B (JER Co., Ltd. system, Epicoat 827) 12.0 weight %, phenolic resins (Mitsui Chemicals, Inc's system, ミ レ Star Network ス XLC-4L) 21.7 weight %, preparing spherical SiO 2 (ア De マ テ Star Network ス Co., Ltd. system, SO-25R) 39.9 weight %, silane coupler (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI system, KBM-303) (four countries change into Co., Ltd.'s system for 0.29 weight % and thermal curing catalyst, C11-Z) 0.01 weight % (is 0.017 weight portion with respect to 100 weight portions of the organic principle except that preparing spherical SiO 2) is dissolved in the methylethylketone, the adhesive compound (wherein, from above-mentioned organic principle, removing methylethylketone) of preparation concentration 23.6 weight %.In addition, (molal quantity of the epoxy radicals in the thermosetting composition of adhesive compound)/(molal quantity of the phenolic hydroxyl group in the thermosetting composition of adhesive compound) is 1.5.
The demoulding that the pet film of thickness 50 μ m after this adhesive compound solution coat handled to the polysiloxanes demoulding is made is handled on the film (release liner), then 130 ℃ of dryings 2 minutes.Thus, make the thermosetting die bonding film of thickness 25 μ m.
(comparative example 1)
To with ethyl acrylate-methyl methacrylate acrylic polymer (Na ガ セ ケ system テ Star Network ス Co., Ltd. system of principal component, SG-70L, acid number 4mgKOH/g) 7.5 weight %, epoxy resin A (JER Co., Ltd. system, Epicoat 1004) 18.6 weight %, epoxy resin B (JER Co., Ltd. system, Epicoat 827) 12.0 weight %, phenolic resins (Mitsui Chemicals, Inc's system, ミ レ Star Network ス XLC-4L) 21.7 weight %, preparing spherical SiO 2 (ア De マ テ Star Network ス Co., Ltd. system, SO-25R) 39.9 weight %, silane coupler (organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI system, KBM-303) (four countries change into Co., Ltd.'s system for 0.29 weight % and thermal curing catalyst, C11-Z) 0.01 weight % (is 0.017 weight portion with respect to 100 weight portions of the organic principle except that preparing spherical SiO 2) is dissolved in the methylethylketone, the adhesive compound (wherein, from above-mentioned organic principle, removing methylethylketone) of preparation concentration 23.6 weight %.In addition, (molal quantity of the epoxy radicals in the thermosetting composition of adhesive compound)/(molal quantity of the phenolic hydroxyl group in the thermosetting composition of adhesive compound) is 1.5.
The demoulding that the pet film of thickness 50 μ m after this adhesive compound solution coat handled to the polysiloxanes demoulding is made is handled on the film (release liner), then 130 ℃ of dryings 2 minutes.Thus, make the thermosetting die bonding film of thickness 25 μ m.
(mensuration of gel fraction)
For the thermosetting die bonding film of making in the foregoing description and the comparative example, mensuration gel fraction as described below.That is, get the sample of about 1g each thermosetting die bonding film before hot curing, they are burnt at 750 ℃ of skies that carried out 2 hours.Afterwards, cooling at room temperature.In addition, take by weighing in the crucible, with burner be fired to do not produce cigarette till.Then, 750 ℃ of calcinings 0.5 hour, make its ashing.Cooling at room temperature, the weight of residual ash content in the mensuration crucible.Obtain the weight % of ash content by the weight before and after the sample ashing.With the weight % of the ash content of this moment as the weight % of the inorganic constituents in the thermosetting die bonding film.
In addition, from each thermosetting die bonding film before the hot curing of embodiment and comparative example making, get the sample of 0.3g (initial weight) respectively, with their Teflon (registered trade mark) sheet parcels, be impregnated into then among the THF of 40mL and placed 7 days with thickness 0.2 μ m.Afterwards, insoluble composition is washed secondary with 20mL THF again together with the Teflon sheet, be dried to solid then.Its weighing is obtained the dry weight of sample.In addition, by the front and back weight of sample, obtain gel fraction with following formula.To from the gained gel fraction, deduct the value of the weight % gained of described inorganic constituents, as the gel fraction of the organic principle of thermosetting die bonding film.The result is as shown in table 1 below.
Gel fraction (weight %)=(dry weight of sample (g)) ÷ (initial weight of sample (g)) * 100
(mensuration of melt viscosity)
For each thermosetting die bonding film before the hot curing of making in each embodiment and the comparative example, measure 120 ℃ melt viscosity respectively.That is (the HAAKE corporate system RS-1) is measured melt viscosity by parallel plate method, to use flow graph.Get the sample of 0.1g in the thermosetting die bonding film of from each embodiment or comparative example, making, put in advance on the plate of 100 ℃ of heating.Then, will measure the value of beginning after 300 seconds as melt viscosity.Gap between plate is set at 0.1mm.The result is as shown in table 1 below.
(mensuration of the melt viscosity all around)
For each thermosetting die bonding film before the hot curing of making in each embodiment and the comparative example, under 23 ℃ environment, placed 672 hours.Then, measure 120 ℃ melt viscosity respectively.That is (the HAAKE corporate system RS-1) is measured melt viscosity by parallel plate method, to use flow graph.Get the sample of 0.1g in the thermosetting die bonding film of from each embodiment or comparative example, making, put in advance on the plate of 100 ℃ of heating.Then, will measure the value of beginning after 300 seconds as melt viscosity.Gap between plate is set at 0.1mm.The result is as shown in table 1 below.
(mensuration of the acid number of thermosetting die bonding film)
The mensuration of the acid number of the thermosetting die bonding film of making in each embodiment and the comparative example is carried out according to the neutralization titration of JIS K 0070.
Particularly, at first each thermosetting die bonding film is cut into the square size of about 1cm, makes to measure and use sample.Then, the described mensuration sample of weighing joins its 1g in the conical flask of volume 200mL with methylethylketone 100mL exactly.Afterwards, carry out 20 minutes ultrasonic wave dissolving, make sample solution respectively.
Then, to described sample solution, use the potassium hydroxide-ethanol solution (indicator:, carry out the mensuration of acid number of 0.025mol/L 1% phenolphthalein) as titrating solution.That is, in each sample solution, add several phenolphthalein solutions, in water-bath, carry out jolting fully and be mixed to sample and dissolve fully.Carry out titration with potassium hydroxide-ethanol solution again, the pale red of indicator is continued moment of 30 seconds as terminal point.
(260 ℃ energy storage modulus of elasticity)
Each thermosetting die bonding film of making in each embodiment and the comparative example after 1 hour, 175 ℃ of heat treated of carrying out 1 hour, is made its hot curing 120 ℃ of heat treated again.Then, each thermosetting die bonding film after the hot curing is cut into the strip of thickness 200 μ m, length 400mm, width 10mm with cutter.Then, use solid determination of viscoelasticity device (RSAIII, Rheometric Scientific corporate system), under the condition of 10 ℃/minute of frequency 1Hz, programming rate, measure stretching energy storage modulus of elasticity and loss elastic modulus under-50～300 ℃ of these samples.260 ℃ the value of energy storage modulus of elasticity (E ') when reading this mensuration obtains.The result is as shown in table 1 below.
(clipping viscous force)
The following mensuration of clipping viscous force of the thermosetting die bonding film of making in the foregoing description and the comparative example.
At first, use laminating machine that each thermosetting die bonding film is pasted on the semiconductor element (long 5mm * wide 5mm * thick 0.5mm).The stickup condition is: 50 ℃ of temperature, laminating machine speed 10mm/ second, pressure 0.15MPa.In addition, upward paste above-mentioned semiconductor element at second half conductor element (long 10mm * wide 10mm * thick 0.5mm) by thermosetting die bonding film.The stickup condition is: 50 ℃ of temperature, laminating machine speed 10mm/ second, pressure 0.15MPa.Then, under 120 ℃, 1 hour condition, heat-treat, carry out the hot curing of thermosetting die bonding film.
After the hot curing, (the Dagy corporate system #4000), is measured 175 ℃ of platform temperature, head height 100 μ m, the clipping viscous force of speed 0.5mm/ under second to use the adhesive test machine.The result is as shown in table 1 below.
(amount of warpage)
With each thermosetting die bonding film of making in each embodiment and the comparative example respectively paste under the condition of 40 ℃ of temperature that 10mm is square, on the semiconductor chip of thickness 50 μ m.In addition, by each thermosetting die bonding film semiconductor chip is installed on the resin substrates (glass epoxide type substrate, substrate thickness 0.23mm) that has soldering-resistance layer.The condition of this moment is: 120 ℃ of temperature, pressure 0.2MPa, 2 seconds.In addition, the described resin substrates that semiconductor chip is installed is carried out heat treatment in 2 hours with drying machine at 140 ℃, make the thermosetting die bonding film hot curing.
Then, be that the mode of downside is arranged on the flat board with the gained material with described resin substrates, measure concavo-convex on the diagonal of semiconductor chip.Thus, measure the height of the semiconductor chip of perk from the flat board, i.e. amount of warpage (μ m).During mensuration, the both ends on the diagonal of semiconductor chip are proofreaied and correct to balance (being 0).In addition, (the Veeco corporate system DEKTAK8), is carried out under the condition of finding speed 1.5mm/ second, load 1g measure to use the surface roughness meter.Measurement result is to be evaluated as zero below the 50 μ m with amount of warpage, will be evaluated as above 50 μ m *.The result is as shown in table 1 below.
(result)
As the result of the embodiment in the following table 1 1～3 as can be known, the acid number of thermoplastic resin is 20, during 36mgKOH/g, and can make the clipping viscous force of the thermosetting die bonding film of hot curing under 120 ℃, 1 hour condition is more than the 0.5MPa.In addition, in embodiment 1 and 2, for around after 120 ℃ melt viscosity, also can suppress its increase, confirm that keeping quality is good.In addition, the amount of warpage that has the resin substrates of solder resist is below the 50 μ m, confirms that the cure shrinkage of thermosetting die bonding film is suppressed.
On the other hand, in comparative example 1, when the acid number of thermoplastic resin was 4mgKOH/g, 120 ℃ melt viscosity after around can suppressing increased, but the clipping viscous force after the hot curing rests on 0.1MPa under 120 ℃, 1 hour condition, confirms that adhesivity is poor.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
The acid number of thermoplastic resin (mgKOH/g) 20 36 50 4
Gel fraction under 120 ℃, 1 hour (weight %) 7.5 10.1 15.2 5.2
Gel fraction under 175 ℃, 1 hour (weight %) 15.6 18.8 26.7 8.1
Clipping viscous force (MPa) 0.6 1.1 1.7 0.1
Melt viscosity (Pas) 342 364 398 362
The acid number of thermosetting die bonding film (mgKOH/g) 4.4 8.0 11.1 1.0
Energy storage modulus of elasticity (MPa) ＞1.0 ＞1.0 ＞1.0 ＜1.0
Melt viscosity all around (Pas) 387 523 ＞1000 372
Amount of warpage (μ m) 10 20 25 5

Claims (9)

1. a thermosetting die bonding film is used for the gluing adherend that is fixed to of semiconductor element, wherein,
By 120 ℃, 1 hour heat treatment after the hot curing in the scope of the gel fraction of organic principle below 20 weight %, and the heat treatment by 175 ℃, 1 hour and after the hot curing gel fraction of organic principle in the scope of 10～30 weight %.
2. thermosetting die bonding film as claimed in claim 1, wherein,
Acid number is in the scope of 4～10mgKOH/g.
3. thermosetting die bonding film as claimed in claim 1 or 2, wherein,
Thermoplastic resin in 10～40mgKOH/g scope forms by thermosetting resin and acid number.
4. as each described thermosetting die bonding film in the claim 1 to 3, wherein,
Be added with thermal curing catalyst.
5. as each described thermosetting die bonding film in the claim 1 to 4, wherein,
The clipping viscous force was more than the 0.2MPa after the hot curing by 120 ℃, 1 hour heat treatment.
6. as each described thermosetting die bonding film in the claim 1 to 5, wherein,
Melt viscosity under 120 ℃ before the hot curing is in the scope of 50～1000Pas.
7. as each described thermosetting die bonding film in the claim 1 to 6, wherein,
Energy storage modulus of elasticity under 260 ℃ by 175 ℃, 1 hour heat treatment after the hot curing is more than the 1MPa.
8. dicing/die bonding film wherein, has on the cutting film structure of each described thermosetting die bonding film in the stacked requirement 1 to 7 of having the right.
9. a semiconductor device is made by each described thermosetting die bonding film or the described dicing/die bonding film of claim 8 in the use claim 1 to 7.
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