CN103250235A - Semiconductor wafer with adhesive layer, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Semiconductor wafer with adhesive layer, method for manufacturing semiconductor device, and semiconductor device Download PDF

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Publication number
CN103250235A
CN103250235A CN2011800578872A CN201180057887A CN103250235A CN 103250235 A CN103250235 A CN 103250235A CN 2011800578872 A CN2011800578872 A CN 2011800578872A CN 201180057887 A CN201180057887 A CN 201180057887A CN 103250235 A CN103250235 A CN 103250235A
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China
Prior art keywords
bond layer
resin
semiconductor wafer
bonding agent
methyl
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Pending
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CN2011800578872A
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Chinese (zh)
Inventor
森修一
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Publication of CN103250235A publication Critical patent/CN103250235A/en
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    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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Abstract

The present invention relates to a semiconductor wafer and a semiconductor wafer with an adhesive layer provided with an adhesive layer formed on one surface of the semiconductor wafer and wherein the adhesive layer is formed inside of the peripheral part of the semiconductor wafer. The present invention also relates to a method for manufacturing a semiconductor device comprising a step for forming the adhesive layer, formed from an adhesive, on the inside of the peripheral edge on one surface of the semiconductor wafer and a step for bringing the adhesive to a B stage.

Description

The semiconductor wafer of band bond layer, manufacture method and the semiconductor device of semiconductor device
Technical field
The present invention relates to the semiconductor wafer with bond layer, manufacture method and the semiconductor device of semiconductor device.More specifically, relate to chip join that the grafting material (Die bonding material) when being laminated to each other as semiconductor element such as stacked IC, LSI and lead frame, insulating properties supporting substrate supporting member or with semiconductor chip uses with the semiconductor wafer of being with bond layer, use manufacture method and the semiconductor device of its semiconductor device.
Background technology
Grafting material when being laminated to each other as the grafting material of semiconductor element such as IC, LSI and support component or with semiconductor chip, adds the bonding film of chip join of electroconductive stuffing or inorganic filler at the bonding film of the specific polyimide resin of known use in specific polyimide resin.
In recent years, for realizing that by the assembly process that on semiconductor wafer, carries out semiconductor device as described above in the lump the scheme of high efficiency studies.In addition, follow the stacked of semiconductor chip, there is the tendency of filming in the thickness of semiconductor wafer.Generally speaking, use the operation of using bonding film and the operation of utilizing spin-coating method coating chip join with bonding agent.
As the operation of using bonding film, can enumerate following method: press bonding film at the whole surface layer of semiconductor wafer, support membrane is used in the lamination cutting again, utilizes cutting action to carry out singualtion, and the semiconductor chip that is coated with bonding film is attached at semiconductor substrate or semiconductor chip.
As the method at whole coating adhesive of semiconductor wafer, common having by rotating at a high speed coated whole spin-coating method with the aqueous bonding agent on the semiconductor wafer.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-98213 communique
Patent documentation 2: the special fair 5-54262 communique of Japan
Summary of the invention
Invent problem to be solved
But, under the situation of using bonding film, the waste that in the operation of the bonding film of lamination, produces bonding film in wafer part in addition easily.In addition, adopting spin-coating method that aqueous bonding agent is coated under the situation of whole of semiconductor wafer, aqueous bonding agent can expand to the end of semiconductor wafer, because capillary effect, bond layer is easily in end bosses.Diminish the uniformity of bond layer thus, when the lamination of cutting film, be involved in bubble easily, problem such as therefore in cutting action, cause that chip disperses sometimes.In addition, when bond layer in uneven thickness, the loading that is carried on semiconductor wafer in the lamination operation of cutting film becomes inhomogeneous, especially can produce damaged at the semiconductor wafer of film sometimes.
The present invention In view of the foregoing finishes, and its purpose is, provide with uniform thickness semiconductor wafer be formed with the band bond layer of bond layer semiconductor wafer, use manufacture method and the semiconductor device of its semiconductor device.
For the means of dealing with problems
The invention provides a kind of semiconductor wafer with bond layer, it possesses semiconductor wafer and is formed at bond layer on the face of this semiconductor wafer, and this adhesive layer is formed on than the more close inboard place of the circumference of semiconductor wafer.
Above-mentioned bond layer is preferably by being that aqueous bonding agent forms under 15～35 ℃ of conditions.
The present invention also provides a kind of manufacture method of semiconductor device, and it comprises: the operation that forms the bond layer that is formed by bonding agent at the more close inboard place of the ratio circumference of a face of semiconductor wafer; With the operation of this bond layer being carried out the B rankization.According to this method, can on semiconductor wafer, form the bond layer with regulation shape with uniform thickness.
In the manufacture method of above-mentioned semiconductor device, bond layer can utilize silk screen print method, ink jet printing method, spin-coating method or gap rubbing method to form.
Above-mentioned bonding agent is aqueous bonding agent at 15～35 ℃ preferably.
The present invention also provides the semiconductor device that can utilize said method to make.
The invention effect
According to the present invention, can provide with uniform thickness semiconductor wafer be formed with the band bond layer of bond layer semiconductor wafer, use manufacture method and the semiconductor device of its semiconductor device.
Description of drawings
Fig. 1 is the schematic cross sectional view of execution mode of the semiconductor wafer of expression band bond layer.
Fig. 2 is the schematic diagram of an execution mode of the manufacture method of expression semiconductor device.
Fig. 3 is the schematic diagram of an execution mode of the manufacture method of expression semiconductor device.
Fig. 4 is the schematic diagram of an execution mode of the manufacture method of expression semiconductor device.
Fig. 5 is the schematic diagram of an execution mode of the manufacture method of expression semiconductor device.
Fig. 6 is the schematic cross sectional view of an execution mode of expression semiconductor device.
Embodiment
Below, with reference to accompanying drawing the semiconductor wafer of band bond layer of the present invention, the manufacture method of semiconductor device and a preferred execution mode of semiconductor device are elaborated.But the present invention is not subjected to the restriction of following execution mode.
The semiconductor wafer of＜band bond layer 〉
The semiconductor wafer of the described band bond layer of present embodiment possesses semiconductor wafer and is formed at bond layer on the face of this semiconductor wafer, and bond layer is formed on than the more close inboard place of the circumference of semiconductor wafer.
Fig. 1 is the schematic cross sectional view of execution mode of the semiconductor wafer of expression band bond layer.As shown in Figure 1, form the bond layer 7 of uniform thickness at semiconductor wafer 6.Semiconductor wafer 6 is used to form semiconductor chip 13a built-in in the semiconductor packages (with reference to Fig. 6) and 13b (with reference to Fig. 6).Typical semiconductor wafer 6 is silicon wafer.On semiconductor wafer 6, can utilize existing before continuous operation form circuit.
Bond layer 7 is preferred by being that aqueous bonding agent forms under 15～35 ℃ of conditions, can use Thermocurable or photosensitive bonding agent to form.
The described Thermocurable bonding agent of present embodiment preferably contain (A) heat-curing resin (below, according to circumstances be called " (A) composition "), (B) solvent (below, according to circumstances be called " (B) composition ") and (C) thermoplastic resin (below, according to circumstances be called " (C) composition ").
(A) heat-curing resin is so long as comprise the composition that utilizes heating to cause the reactive compounds of cross-linking reaction, and then there is no particular limitation.As (A) composition, can enumerate for example epoxy resin, cyanate ester resin, maleimide resin, pi-allyl Na Dike imide resin, phenolic resins, Lauxite, melmac, alkyd resins, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furane resins, polyurethane resin, ketone resin, the triallylcyanurate resin, polyisocyanate resin, the resin that contains three (2-hydroxyethyl) isocyanuric acid ester, the resin that contains the trimellitic acid triallyl, the heat-curing resin synthetic by cyclopentadiene reaches the heat-curing resin that is got by the tripolymerization of aromatic series cdicynanmide.Wherein, with the combined situation of polyimide resin under can have excellent bonding force under the high temperature aspect consider, as (A) composition, preferred epoxy, maleimide resin and pi-allyl Na Dike imide resin.In addition, these heat-curing resins may be used singly or in combin more than 2 kinds.
As epoxy resin, preferred molecule contains the epoxy resin of at least 2 above epoxy radicals, considers from the aspect of thermo-compressed, curing property, solidfied material characteristic, more preferably the epoxy resin of the glycidol ether type of phenol.As such resin, can enumerate for example bisphenol A-type (or AD type, the S type, the F type) glycidol ether, the glycidol ether of hydrogenated bisphenol A type, the glycidol ether of ethylene oxide adduct bisphenol A-type, the glycidol ether of propylene oxide adduct bisphenol A-type, the glycidol ether of phenol linear phenolic resin, the glycidol ether of cresols linear phenolic resin, the glycidol ether of bisphenol-A linear phenolic resin, the glycidol ether of naphthalene resin, the glycidol ether of 3 functional-type (or 4 functional-type), the glycidol ether of bicyclopentadiene phenolic resins, the glycidyl esters of dimeric dibasic acid, the glycidyl group amine of 3 functional-type (or 4 functional-type) and the glycidyl group amine of naphthalene resin.These resins may be used singly or in combin more than 2 kinds.
In addition, from preventing electromigration, preventing the viewpoint of the corrosion of metallic conductor circuit, as epoxy resin, preferred use will be reduced in high-purity product below the 300ppm as the alkali metal ion of foreign ion, alkaline-earth metal ions, halide ion especially chloride ion, water-disintegrable chlorine etc.
The amount of epoxy resin is 10～80 quality % with respect to the bonding agent total amount preferably, from the viewpoint of the reliability of bonding agent, more preferably 20～60 quality %.When this amount surpasses 80 quality %, the tendency that exist the viscosity of bonding agent to uprise, printing reduces.On the other hand, when the amount of epoxy resin during less than 10 quality %, there is the tendency that is difficult to obtain sufficient thermo-compressed and high temperature bonding.
(A) 5% quality of heat-curing resin minimizing temperature is preferably more than 150 ℃, more preferably more than 180 ℃, further is preferably more than 200 ℃.At this, 5% quality reduces temperature and refers to heat-curing resin is used differential thermogravimetric amount determinator (SII Technology system: the 5% quality minimizing temperature when TG/DTA6300) measuring simultaneously under 10 ℃/minute of programming rates, nitrogen stream (400mL/ minute).Reduce the high heat-curing resin of temperature by using 5% quality, thereby when thermo-compressed or hot curing, can suppress its volatilization.As so stable on heating heat-curing resin that has, can enumerate and have aromatic epoxy resin in the molecule, from cementability, stable on heating viewpoint, especially preferably use the glycidol ether of the glycidyl group amine, bisphenol A-type (or AD type, S type, F type) of 3 functional-type (or 4 functional-type).
Contain under the situation of epoxy resin at (A) composition, bonding agent preferably further contains curing accelerator.As curing accelerator, so long as utilize heating to promote the curing/polymeric compounds of epoxy radicals, then have no particular limits, can enumerate for example phenol system compound, aliphatic amine, cycloaliphatic amines, aromatic polyamine, polyamide, aliphatic anhydride, alicyclic acid anhydrides, aromatic anhydride, dicyandiamide, organic acid dihydrazide, the boron trifluoride amine complex, imidazoles, cyanoguanidine derivative, the dicarboxyl acid dihydrazide, triphenylphosphine, the tetraphenylphosphoniphenolate tetraphenyl borate salts, 2-ethyl-4-methylimidazole-tetraphenyl borate salts, 2-[(3,5-dimethyl pyrazole base) carbonylamino] the ethyl-methyl acrylate, methacrylic acid 2-(0-[1 ' methyl propylidene amino] carboxyamino) ethyl ester, 1,8-diazabicyclo [5,4,0] hendecene-7-tetraphenyl borate salts and tertiary amine.Wherein, from the viewpoint of dissolubility, dispersiveness, preferably use imidazoles.In addition, from the viewpoint of cementability, thermal endurance, storage stability, as curing accelerator, especially preferably contain imidazoles.The amount of curing accelerator is 0.01～50 mass parts with respect to epoxy resin 100 mass parts preferably.
As imidazoles, reaction initiation temperature is preferably more than 50 ℃, more preferably more than 80 ℃, most preferably is more than 100 ℃.When reaction initiation temperature during less than 50 ℃, storage stability reduces, and the viscosity that therefore has a bonding agent rises and is difficult to control the tendency of thickness.
In addition, as imidazoles, preferably use following, more preferably following, the following compound of 5 μ m most preferably of 8 μ m of average grain diameter 10 μ m.By using the imidazoles of this kind particle diameter, thereby the viscosity that can suppress bonding agent changes, and can suppress the sedimentation of imidazoles.In addition, when forming film, can obtain uniform film by reducing concave-convex surface.And then, when solidifying, bonding agent is cured equably, therefore can reduce exhaust.In addition, by the deliquescent imidazoles of use shortage to epoxy resin, thereby can obtain good storage stability.
As imidazoles, also can use the imidazoles that is dissolved in epoxy resin.By using such imidazoles, thus the concave-convex surface can further reduce film and form the time.As such imidazoles, there is no particular limitation, can enumerate for example 2-ethyl-4-methylimidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-ethyl-4-methylimidazole, 1-cyano ethyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole and 1-benzyl-2-phenylimidazole.
In addition, above-mentioned bonding agent can contain the phenol system compound as curing agent.As phenol system compound, more preferably has the phenol system compound of at least 2 above phenol hydroxyls in the molecule.As such compound, can enumerate for example linear phenolic aldehyde of phenol, the linear phenolic aldehyde of cresols, the linear phenolic aldehyde of tert-butyl phenol, the linear phenolic aldehyde of bicyclopentadiene cresols, the linear phenolic aldehyde of bicyclopentadiene phenol, the linear phenolic aldehyde of xylylene modified phenol, naphthols based compound, three phenol system compounds, the linear phenolic aldehyde of four phenol, the linear phenolic aldehyde of bisphenol-A, poly-to vinylphenol and phenol aralkyl resin.Wherein, the phenol system compound of preferred number average molecular weight in 400～4000 scopes.Thus, during heating in the assembling process of semiconductor device, can suppress to cause exhaust pollution, during heating of semiconductor element or device etc.The amount of phenol system compound is 10～100 mass parts with respect to heat-curing resin 100 mass parts preferably, more preferably 10～70 mass parts.
Consider and prevent that bond layer described later from forming the volatilization of the solvent in the operation, as the solvent of (B) composition, preferably selects the solvent of boiling point more than 100 ℃.Utilize (B) solvent can adjust the viscosity of bonding agent.In addition, the higher limit of the boiling point of solvent is about 300 ℃.
As above-mentioned solvent, can enumerate for example N-N-methyl-2-2-pyrrolidone N-, diethylene glycol dimethyl ether (being also referred to as diethylene glycol dimethyl ether), triethylene glycol dimethyl ether (being also referred to as triglyme), diethylene glycol diethyl ether, 2-(2-methoxy ethoxy) ethanol, gamma-butyrolacton, isophorone, carbitol, the carbitol acetic acid esters, 1,3-dimethyl-2-imidazolidinone, acetic acid 2-(2-butoxy ethyoxyl) ethyl ester, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve diox, cyclohexanone, methyl phenyl ethers anisole, and with the petroleum distillate that uses with the solvent of black liquid as the printing solvent as main body.These solvents can use a kind or be mixed with two or more separately.
(B) solvent preferably cooperates according to the mode that the solid constituent that makes bonding agent reaches 20～90 quality %, more preferably 25～75 quality %, further preferred 30～60 quality %.When above-mentioned solid constituent is that 30 quality % are when above, be preferred from the viewpoint that suppresses dried volume based on the bond layer change of shape due to reducing, when above-mentioned solid constituent is 90 quality % when following, be preferred from the flowability that improves bonding agent and the viewpoint of operability.
Tg as the thermoplastic resin of (C) composition is preferably below 150 ℃, more preferably below 120 ℃, more preferably below 100 ℃, is preferably especially below 80 ℃.Surpass under 150 ℃ the situation at this Tg, have the tendency of the viscosity rising of bonding agent.In addition, when adherend is carried out thermo-compressed, need the high temperature more than 150 ℃, have the tendency that makes semiconductor wafer generation warpage easily sometimes.In addition, the lower limit of the Tg of thermoplastic resin is about-100 ℃.In addition, the viewpoint of the viscosity after the B rankization, (C) composition is solid-state material in room temperature (15 ℃～35 ℃) preferably.
At this, " Tg " refers to the main peak temperature that disperses when composition becomes membranization with (C).Use the viscoelastic analyzer " RSA-2 " (trade name) of RHEO Metrics corporate system, at thickness 100 μ m, 5 ℃/minute of programming rates, frequency 1Hz, measure under the condition of temperature-150～300 ℃ and measure, serve as the main peak temperature that disperses with near the tan δ peak temperature the Tg.
(C) weight average molecular weight of composition is preferably controlled in 5000～500000 scope, can highly take into account thermo-compressed and high temperature bonding aspect, more preferably 10000～300000.At this, " weight average molecular weight " refers to use the high performance liquid chromatograph " C-R4A " (trade name) of Shimadzu Seisakusho Ltd.'s corporate system and is converted into the weight average molecular weight of polystyrene when measuring.
As (C) composition, can enumerate for example mylar, polyether resin, polyamide, polyamide-imide resin, polyimide resin, polyetherimide resin, the siloxanes polyimide resin, polyesterimide resin, polyurethane resin, the imide-urethane resin, polyurethane amide imide resin, their copolymer, their precursor (polyamic acid etc.), polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide, polycarbonate resin, polyether ketone resin, weight average molecular weight is (methyl) acrylic copolymer of 10,000～1,000,000, linear phenolic resin and phenol resin.These materials can use a kind or be used in combination more than 2 kinds separately.In addition, (C) composition also can be to give material behind glycol-based, carboxyl and/or the hydroxyls such as ethylene glycol, propylene glycol to the main chain of these resins and/or side chain.
Wherein, from high temperature bonding, stable on heating viewpoint, (C) composition is preferably the resin with imide.As the resin with imide, can enumerate for example polyimide resin, polyamide-imide resin, polyetherimide resin, imide-urethane resin, polyurethane amide imide resin, siloxanes polyimide resin, polyesterimide resin and their copolymer.
Polyimide resin can utilize known method to make tetracarboxylic dianhydride and diamines generation polycondensation reaction and obtain.Namely, in organic solvent, in reaction temperature below 80 ℃, under preferred 0～60 ℃ of condition, make tetracarboxylic dianhydride and diamines with etc. mole carry out addition reaction, perhaps as required according to the total amount 1.0mol with respect to the tetracarboxylic dianhydride, the summation of diamines is preferably 0.5～2.0mol, more preferably the scope of 0.8～1.0mol is adjusted ratio of components (interpolation of each composition is in proper order for arbitrarily), makes tetracarboxylic dianhydride and diamines carry out addition reaction.Along with the carrying out of reaction, the viscosity of reactant liquor rises gradually, and the precursor that generates polyimide resin is polyamic acid.In addition, for the reduction of all characteristics of suppressing bonding agent, above-mentioned tetracarboxylic dianhydride is preferably with acetic anhydride and carries out tetracarboxylic dianhydride after recrystallizing and refining is handled.
Ratio of components about the tetracarboxylic dianhydride in the above-mentioned polycondensation reaction and diamines, when the total amount of diamines with respect to tetracarboxylic dianhydride's total amount 1.0mol when surpassing 2.0mol, the amount of the polyimide oligomers of amine end exist to become many tendencies in the polyimide resin of gained, and has the weight average molecular weight step-down of polyimide resin, the various characteristics that comprises the thermal endurance of the bonding agent inadequate tendency that becomes.On the other hand, when the total amount of diamines is during less than 0.5mol with respect to tetracarboxylic dianhydride's total amount 1.0mol, there is the tendency that becomes many in the amount of the polyimide resin oligomer that acid is terminal, and has the weight average molecular weight step-down of polyimide resin, the various characteristics that comprises the thermal endurance of the bonding agent inadequate tendency that becomes.
Polyimide resin can obtain by making above-mentioned reactant (polyamic acid) dehydration ring closure.Dehydration ring closure can utilize the heat pass of carrying out heat treated around-France grade the in chemistry pass around-France, that use dehydrating agent to carry out.
Tetracarboxylic dianhydride as the raw material that is used as polyimide resin has no particular limits, and can enumerate for example pyromellitic acid dianhydride, 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-xenyl tetracarboxylic acid dianhydride, 2,2-two (3,4-dicarboxyl phenyl) propane dianhydride, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2,2-, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, benzene-1,2,3, the 4-tetracarboxylic acid dianhydride, 3,4,3 ', 4 '-benzophenone tetracarboxylic acid dianhydride, 2,3,2 ', 3 '-benzophenone tetracarboxylic acid dianhydride, 3,3,3 ', 4 '-benzophenone tetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride, 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 1,2,4,5-naphthalenetetracarbacidic acidic dianhydride, 2,6-dichloronaphtalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphtalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,7,8-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,6,7-tetracarboxylic acid dianhydride, luxuriant and rich with fragrance-1,2,9, the 10-tetracarboxylic acid dianhydride, pyrazine-2,3,5, the 6-tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) dimethylsilane dianhydride, two (3,4-dicarboxyl phenyl) aminomethyl phenyl silane dianhydride, two (3,4-dicarboxyl phenyl) diphenyl silane dianhydride, 1,4-two (3,4-dicarboxyl phenyl dimetylsilyl) benzene dianhydride, two (3, the 4-dicarboxyl phenyl)-1 of 1,3-, 1,3,3-tetramethyl bicyclohexane dianhydride, TOPOT 2,2 (trimellitic anhydride), the ethylene-tetracarboxylic acid dianhydride, 1,2,3,4-ethylene-dimalonic acid dianhydride, decahydronaphthalene-1,4,5, the 8-tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro naphthalene-1,2,5, the 6-tetracarboxylic acid dianhydride, pentamethylene-1,2,3, the 4-tetracarboxylic acid dianhydride, pyrrolidines-2,3,4,5-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, two (external form-dicyclos [2,2,1] heptane-2, the 3-dicarboxylic acid dianhydride, dicyclo-[2,2,2]-Xin-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] the propane dianhydride, 2, two (3, the 4-dicarboxyl phenyl) hexafluoropropane dianhydrides of 2-, 2,2-is two, and [4-(3, the 4-di carboxyl phenyloxy) phenyl] hexafluoropropane dianhydride, 4,4 '-two (3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride, two (2-hydroxyl hexafluoro isopropyl) benzene of 1,4-two (trimellitic anhydride), 1, two (2-hydroxyl hexafluoro isopropyl) benzene of 3-two (trimellitic anhydride), 5-(2,5-dioxy tetrahydrofuran base)-and 3-methyl-3-cyclohexene-1, the 2-dicarboxylic acid dianhydride, oxolane-2,3, tetracarboxylic dianhydride shown in 4,5-tetracarboxylic dianhydride and the following general formula (7).In the following formula (7), a represents 2～20 integer.
[changing 1]
Figure BDA00003281053100091
Tetracarboxylic dianhydride shown in the above-mentioned general formula (7) can be synthesized by for example trimellitic anhydride list chloride and corresponding glycol, particularly, can enumerate 1,2-(ethylidene) two (trimellitic anhydrides), 1,3-(trimethylene) two (trimellitic anhydrides), 1,4-(tetramethylene) two (trimellitic anhydrides), 1,5-(pentamethylene) two (trimellitic anhydrides), 1,6-(hexa-methylene) two (trimellitic anhydrides), 1,7-(heptamethylene) two (trimellitic anhydrides), 1,8-(eight methylene) two (trimellitic anhydrides), 1,9-(nine methylene) two (trimellitic anhydrides), 1,10-(decamethylene) two (trimellitic anhydrides), 1,12-(ten dimethylenes) two (trimellitic anhydrides), 1,16-(ten hexa-methylenes) two (trimellitic anhydrides) and 1,18-(18 methylene) two (trimellitic anhydrides).
In addition, as the tetracarboxylic dianhydride, from giving to the fine solubility of solvent and moisture-proof, to the viewpoint of the transparency of 365nm light, the tetracarboxylic dianhydride shown in preferred following formula (8) or (9).
[changing 2]
Above-described tetracarboxylic dianhydride can use a kind or be used in combination more than 2 kinds separately.
And then aspect the raising adhesive strength, (C) composition can use the polyimide resin that contains carboxyl and/or phenol hydroxyl.As the raw material of the above-mentioned polyimide resin that contains carboxyl and/or hydroxyl and the diamines that uses preferably contains the aromatic diamine shown in following formula (10), (11), (12) or (13).
[changing 3]
Other diamines as the raw material that is used as above-mentioned polyimide resin, have no particular limits, can enumerate for example o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine (PPD), 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, two (4-amino-3, the 5-3,5-dimethylphenyl) methane, two (4-amino-3, the 5-diisopropyl phenyl) methane, 3,3 '-diamino-diphenyl difluoromethane, 3,4 '-diamino-diphenyl difluoromethane, 4,4 '-diamino-diphenyl difluoromethane, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino-diphenyl thioether, 3,4 '-diamino-diphenyl thioether, 4,4 '-diamino-diphenyl thioether, 3,3 '-diamino-diphenyl ketone, 3,4 '-diamino-diphenyl ketone, 4,4 '-diamino-diphenyl ketone, 2, two (3-aminophenyl) propane of 2-, 2,2 '-(3,4 '-diamino-diphenyl) propane, 2, two (4-aminophenyl) propane of 2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2,2-(3,4 '-diamino-diphenyl) HFC-236fa, 2, two (4-aminophenyl) HFC-236fa of 2-, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, 3,3 '-(1,4-phenylene two (1-methyl ethidine)) dianil, 3,4 '-(1,4-phenylene two (1-methyl ethidine)) dianil, 4,4 '-(1,4-phenylene two (1-methyl ethidine)) dianil, 2, two (4-(3-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-(3-amino-benzene oxygen) phenyl) HFC-236fa of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of 2-, two (4-(3-amino ethoxy) phenyl) thioether, two (4-(4-amino ethoxy) phenyl) thioether, two (4-(3-amino ethoxy) phenyl) sulfone, two (4-(4-amino ethoxy) phenyl) sulfone, 3,3 '-dihydroxy-4,4 '-benzidine, and 3, aromatic diamines such as 5-diaminourea benzoic acid, 1, two (amino methyl) cyclohexanes of 3-, two (the 4-amino-benzene oxygen phenyl) propane of 2,2-, fatty ether diamines shown in the following general formula (14), and the siloxane diamine shown in the following general formula (15).
In the above-mentioned diamines, consider giving aspect the intermiscibility of other compositions, the fatty ether diamines shown in the preferred following general formula (14), more preferably ethylene glycol and/or propylene glycol are diamines.In the following general formula (14), R 1, R 2And R 3The alkylidene of representing carbon number 1～10 independently of one another, b are represented 2～80 integer.
[changing 4]
Figure BDA00003281053100111
As such fatty ether diamines, particularly, can enumerate the aliphatic diamines such as polyoxyalkylene diamines such as polyetheramine D-230, D-400, D-2000 of JEFFAMINE D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2000, EDR-148, the BASF (system) of Sun techno chemical (strain) system.These diamines are preferably 20 moles of whole diamines more than the %, with the intermiscibility of other gradation compositions such as (A) heat-curing resin and can highly take into account thermo-compressed and high temperature bonding aspect, more preferably 50 moles more than the %.
In addition, as above-mentioned diamines, give adaptation under the room temperature, cementability aspect, the siloxane diamine shown in the preferred following general formula (15).In the following general formula (15), R 4And R 9The alkylidene of representing carbon number 1～5 independently of one another maybe can have substituent phenylene, R 5, R 6, R 7And R 8Represent alkyl, phenyl or the phenoxy group of carbon number 1～5 independently of one another, d represents 1～5 integer.
[changing 5]
Figure BDA00003281053100121
These diamines are preferably 0.5～80 mole of % of whole diamines, can highly take into account thermo-compressed and high temperature bonding aspect, 1～50 mole of % more preferably.When being lower than 0.5 mole of %, the effect of adding siloxane diamine diminishes, and when being higher than 80 moles of %, exists and the intermiscibility of other compositions, the tendency of high temperature bonding reduction.
Siloxane diamine shown in the relevant above-mentioned general formula (15) particularly, is 1 siloxane diamine as the d in the formula (15), can enumerate 1,1,3,3-tetramethyl-1, two (4-aminophenyl) disiloxane of 3-, 1,1,3,3-, four phenoxy groups-1, two (4-amino-ethyl) disiloxane of 3-, 1,1,3,3-tetraphenyl-1, two (2-amino-ethyl) disiloxane of 3-, 1,1,3,3-tetraphenyl-1, two (3-aminopropyl) disiloxane of 3-, 1,1,3,3-tetramethyl-1, two (2-amino-ethyl) disiloxane of 3-, 1,1,3,3-tetramethyl-1, two (3-aminopropyl) disiloxane of 3-, 1,1,3,3-tetramethyl-1,3-two (the amino butyl of 3-) disiloxane and 1,3-dimethyl-1,3-dimethoxy-1,3-two (the amino butyl of 4-) disiloxane etc.Be 2 siloxane diamine as d, can enumerate 1,1,3,3,5,5-vegolysen, two (4-aminophenyl) trisiloxanes of 5-, 1,1,5,5-tetraphenyl-3,3-dimethyl-1, two (3-aminopropyl) trisiloxanes of 5-, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-two (the amino butyl of 4-) trisiloxanes, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-two (the amino amyl group of 5-) trisiloxanes, 1,1,5,5-tetramethyl-3,3-dimethoxy-1, two (2-amino-ethyl) trisiloxanes of 5-, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-two (the amino butyl of 4-) trisiloxanes, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-two (the amino amyl group of 5-) trisiloxanes, 1,1,3,3,5,5-vegolysen, two (3-aminopropyl) trisiloxanes of 5-, 1,1,3,3,5,5-Hexaethyl-1, two (3-aminopropyl) trisiloxanes and 1,1 of 5-, 3,3,5,5-, six propyl group-1, two (3-aminopropyl) trisiloxanes of 5-.
Above-mentioned diamines can use a kind or be used in combination more than 2 kinds separately.
In addition, above-mentioned polyimide resin can use a kind or mix (blending) use as required more than 2 kinds separately.
In addition, as mentioned above, when determining the composition of polyimide resin, preferably the mode that reaches below 150 ℃ according to this Tg designs, and as the diamines of the raw material of polyimide resin, preferably especially uses the fatty ether diamines shown in the above-mentioned general formula (14).
When above-mentioned polyimide resin synthetic, by will be shown in following formula (16), (17) or (18) such simple function acid anhydrides and/or the monofunctional amines of compound drop in the polycondensation reaction liquid, thereby functional group that can be beyond polymer ends import acid anhydrides or diamines.In addition, can reduce the molecular weight of polymer, the viscosity that reduces adhesive resin, raising thermo-compressed thus.
[changing 6]
Figure BDA00003281053100131
In addition, can have at the main chain of (C) composition and/or side chain and have the functional group of function that imidazoles etc. promotes the curing of epoxy resin.Polyimides with imidazoles skeleton can be by for example and with the diamines with the imidazoles skeleton shown in following formula (19) and (20) obtaining as two amine components.
[changing 7]
Figure BDA00003281053100141
As the imide-urethane resin, can use the resin shown in the following general formula (I).In the formula (I), R 1Expression contains the divalent organic group of aromatic ring or aliphat ring, R 2The divalent organic group of expression molecular weight 100～10000, R 3Expression contains 4 valency organic groups of 4 above carbon, and n and m are respectively 1～100 integer independently.
[changing 8]
Figure BDA00003281053100142
R in the formula (I) 1The shown divalent organic group that contains aromatic ring or aliphat ring is preferably the vulcabond residue and contains the structure shown in the following formula (II) of 10～100mol%.
[changing 9]
In addition, as remaining vulcabond residue, can enumerate following formula etc.These residues can use a kind or be used in combination more than 2 kinds separately.
[changing 10]
Figure BDA00003281053100151
R in the formula (I) 2The divalent organic group of shown molecular weight 100～10000 is diol residue.The diol residue group that glycol such as polybutadiene diol, polyisoprene glycol, PCDL, polybutadiene diol, PTMEG, polyester-diol, polycaprolactone glycol, silicone glycol for example derive of serving as reasons.R 2Preferably contain the structure that the repetitive by shown in the following formula (III) of 10～100mol% forms as diol residue.
[changing 11]
-(CH 2-CH 2-CH 2-CH 2-O)- (III)
In addition, as remaining diol residue, can enumerate the diol residue of the repetitive with following formula etc.These diol residue can be used a kind or be used in combination more than 2 kinds.The mean molecule quantity of these diol residue is preferably 100～10000, and more preferably 500～5000.
[changing 12]
-(CH 2-CH(CH 3)-O)-、
-(CH 2-CH 2-O)-、
-(CH 2-CH 2-CH 2-CH 2-O)-、
-(CH 2-CH (CH 3The a-of)-O) (CH 2-CH 2-O) b-(copolymer of a/b=9～1/1～9mol%)
-[CO-(CH 2) 4-CO-O-(CH 2) 2-O]-、
-[CO-(CH 2) 4-CO-O-(CH 2) 2-O-(CH 2) 2-O]-、
-[CO-(CH 2) 4-CO-O-CH 2-CH(CH 3)-O]-、
-[CO-(CH 2) 4-CO-O-(CH 2) 4-O]-、
-[CO-(CH 2) 4-CO-O-(CH 2) 6-O]-、
-[CO-(CH 2) 4-CO-O-CH 2-C(CH 3) 2-CH 2-O]-、
-[CO-(CH 2) 8-CO-O-(CH 2) 6-O]-、
-[CO-(CH 2) 5-O]-、
-[CO-O-(CH 2) 6-O]-、
-R 4-(Si (CH 3) 2-O)-R 4-(R 4Organic group for carbon number 1～10)
R in the formula (I) 3The shown 4 valency organic groups that contain 4 above carbon are the tetracarboxylic anhydride residue, can enumerate following formula etc.These tetracarboxylic anhydride residues can use a kind or be used in combination more than 2 kinds.
[changing 13]
Figure BDA00003281053100171
N in the formula (I) and m are respectively 1～100 integer, more preferably 1～50 integer independently.
The imide-urethane resin can synthesize by usual ways such as solution polymerization process.Under the situation of solution polymerization process, after in the solvent that dissolves the imide-urethane resin that generates, for example N-N-methyl-2-2-pyrrolidone N-(NMP), dissolving vulcabond composition and diol component, it was reacted 1～5 hour under 70～180 ℃ of conditions, the synthesis of carbamates oligomer, add tetracarboxylic acid dianhydride again, it was reacted 1～10 hour under 70～180 ℃ of conditions, obtain the nmp solution of imide-urethane resin.According to circumstances, can also further add monohydric alcohol, oxime, amine, isocyanates, acid anhydrides etc., continue reaction, the end of imide-urethane resin is modified.In addition, when imide-urethane resin synthetic, also can make water, alcohol, tertiary amine etc. as catalyst.
The imide-urethane resin solution of gained can also adopt the reprecipitation method of water to wait to separate the imide-urethane resin according to the purpose utilization.About the vulcabond composition of formation oligourethane and the ratio of components of diol component, preferably making diol component is 0.1～1.0mol with respect to vulcabond composition 1.0mol.About the urethane oligomer of formation imide-urethane resin and the ratio of components of tetracarboxylic acid dianhydride, preferably making tetracarboxylic acid dianhydride is 0.1～2.0mol with respect to urethane oligomer 1.0mol.
Utilization is that the mean molecule quantity that is converted into polystyrene that launches the imide-urethane resin that the gel permeation chromatography of solvent records is preferably 5000～500000 with the oxolane, more preferably 10000～200000.Less than 5000 o'clock, the intensity of resin was low at mean molecule quantity, surpassed at 500000 o'clock at mean molecule quantity, had the tendency of dissolving resin variation.
(C) use level of thermoplastic resin preferably with respect to the composition total amount behind removing in the bonding agent (B) composition, namely be 10～95 quality % with respect to nonvolatile component, the viewpoint of the operability after the B rankization, more preferably 10～70 quality %.During less than 10 quality %, that the toughness of the solidfied material after the bonding agent hot curing is insufficient at (C) composition, when (C) composition surpasses 95 quality, there is the tendency of the viscous force rising after the B rankization.
The described photosensitive adhesive of present embodiment preferably contain above-mentioned (A) heat-curing resin ((A) composition), (D) radiation polymerizable compound (below, according to circumstances be called " (D) composition ") and (E) Photoepolymerizationinitiater initiater (below, according to circumstances be called " (E) composition ").
As (D) radiation polymerizable compound; can enumerate the compound with ethylenic unsaturated group; as the ethylenic unsaturated group; particularly, can enumerate vinyl, pi-allyl, propargyl, cyclobutenyl, acetenyl, phenylacetylene base, dimaleoyl imino, Na Dike imide and (methyl) acryloyl group.From reactive viewpoint, the ethylenic unsaturated group is preferably (methyl) acryloyl group, as (D) composition, preferably contains (D1) simple function (methyl) acrylate.By adding simple function (methyl) acrylate, especially when being used for the exposure of B rankization, can reduce the crosslink density of bonding agent, can make thermo-compressed, low stress and cementability after the exposure be in good state.
As simple function (methyl) acrylate, its 5% quality reduces temperature and is preferably more than 100 ℃, more preferably more than 120 ℃, further more preferably more than 150 ℃, most preferably is more than 180 ℃.At this, 5% quality reduces temperature and refers to the radiation polymerizable compound is used differential thermogravimetric amount determinator (SII Technology system: the 5% quality minimizing temperature when TG/DTA6300) measuring simultaneously under 10 ℃/minute of programming rates, nitrogen stream (400mL/ minute).Reduce high simple function (methyl) acrylate of temperature by using 5% quality, utilize exposure to carry out the remaining volatilization of unreacted simple function (methyl) acrylate when thermo-compressed or hot curing in B rankization back thereby can be suppressed at.
So long as such simple function (methyl) acrylate, then there is no particular limitation, can enumerate (methyl) acrylate that for example contains glycidyl, phenol EO modification (methyl) acrylate, phenol PO modification (methyl) acrylate, nonyl phenol EO modification (methyl) acrylate, nonyl phenol PO modification (methyl) acrylate, (methyl) acrylate that contains the phenol hydroxyl, (methyl) acrylate that contains hydroxyl, fragrant family (methyl) acrylate such as phenylphenol glycidol ether (methyl) acrylate and phenoxy group ethyl (methyl) acrylate, (methyl) acrylate that contains imide, (methyl) acrylate that contains carboxyl, (methyl) acrylate that contains the isophorone base, (methyl) acrylate and isophorone base (methyl) acrylate that contain dicyclopentadienyl.
As simple function (methyl) acrylate, from with the B rankization after the adaptation, cementability, the stable on heating viewpoint after solidifying of adherend, preferably have carbamate groups, isocyanuric acid base, imide, hydroxyl, particularly preferably in the simple function that has imide in the molecule (methyl) acrylate.
In addition, also can preferably use simple function (methyl) acrylate with epoxy radicals.As the simple function with epoxy radicals (methyl) acrylate, viewpoint from storage stability, cementability, low venting quality, heat-resisting and moisture-proof reliability, 5% quality reduces temperature and is preferably more than 150 ℃, more preferably more than 180 ℃, most preferably is more than 200 ℃.As the such simple function with epoxy radicals (methyl) acrylate, there is no particular limitation, can be that polyfunctional epoxy resin more than 150 ℃ satisfies above-mentioned thermal endurance as raw material by using 5% quality to reduce temperature.
As the simple function with epoxy radicals (methyl) acrylate, there is no particular limitation, can enumerate for example glycidyl methacrylate, glycidyl acrylate, acrylic acid 4-hydroxyl butyl ester glycidol ether, methacrylic acid 4-hydroxyl butyl ester glycidol ether and make have with the compound of the functional group of epoxy reaction and ethylenic unsaturated group and polyfunctional epoxy resin reaction and compound.As above-mentioned and functional group epoxy reaction, there is no particular limitation, can enumerate for example NCO, carboxyl, phenol hydroxyl, hydroxyl, acid anhydrides, amino, mercapto and amide groups.These compounds can use a kind or be used in combination more than 2 kinds separately.
Simple function (methyl) acrylate with epoxy radicals is for example by making the polyfunctional epoxy resin that has at least 2 above epoxy radicals in 1 molecule and (methyl) acrylic acid reaction that with respect to epoxy radicals 1 equivalent is 0.1～0.9 equivalent obtain in the presence of triphenylphosphine, TBAB.In addition, in the presence of dibutyl tin laurate, make the epoxy compounds reaction of (methyl) acrylate and the hydroxyl of polyfunctional isocyanate's compound and hydroxyl, perhaps make polyfunctional epoxy resin and (methyl) acrylate reactions that contains NCO, can obtain containing carbamate (methyl) acrylate of glycidyl thus.
Relevant simple function (methyl) acrylate with epoxy radicals, from storage stability, cementability, assemble when heating and the low venting quality of the encapsulation after the assembling, viewpoint heat-resisting and moisture-proof is set out, 5% quality reduces temperature, being preferably more than 150 ℃ by the volatilization due to the heat drying or aspect the segregation on surface in the time can suppressing film and form, hole due to the exhaust in the time can suppressing by hot curing and peeling off, the aspect that cementability reduces is more preferably more than 180 ℃, further be preferably more than 200 ℃, the hole in the time can suppressing owing to reflux due to the unreacted component volatilization and peel off aspect most preferably be more than 260 ℃.As the such simple function with epoxy radicals (methyl) acrylate, has the compound of aromatic rings in the preferred molecule.
And then, as the simple function with epoxy radicals (methyl) acrylate, from preventing electromigration, prevent the viewpoint of the corrosion of metallic conductor circuit, preferred use will be reduced in high-purity product below the 1000ppm as the alkali metal ion of foreign ion, alkaline-earth metal ions, halide ion especially chloride ion, water-disintegrable chlorine.For example, the polyfunctional epoxy resin that has reduced alkali metal ion, alkaline-earth metal ions, halide ion etc. by use can satisfy above-mentioned concentration impurity ion as raw material.Chloride content can be measured according to JIS K7243-3.
As the above-mentioned simple function with epoxy radicals (methyl) the acrylate composition that satisfies thermal endurance and purity, there is no particular limitation, can enumerate for example with bisphenol A-type (or AD type, the S type, the F type) glycidol ether, the glycidol ether of hydrogenated bisphenol A type, the glycidol ether of ethylene oxide adduct bisphenol-A and/or F type, the glycidol ether of propylene oxide adduct bisphenol-A and/or F type, the glycidol ether of phenol linear phenolic resin, the glycidol ether of cresols linear phenolic resin, the glycidol ether of bisphenol-A linear phenolic resin, the glycidol ether of naphthalene resin, the glycidol ether of 3 functional-type (or 4 functional-type), the glycidol ether of bicyclopentadiene phenolic resin, the glycidyl esters of dimeric dibasic acid, the glycidyl group amine of 3 functional-type (or 4 functional-type), the glycidyl group amine of naphthalene resin is the composition of raw material.
Especially in order to improve thermo-compressed, low stress and cementability, the number of epoxy radicals and ethylenic unsaturated group is preferably respectively below 3, and the number that especially preferably makes the ethylenic unsaturated group is below 2.As such compound, there is no particular limitation, preferably uses the compound shown in following general formula (1), (2), (3), (4) or (5).In following general formula (1)～(5), R 12And R 16Expression hydrogen atom or methyl, R 10, R 11, R 13And R 14Expression divalent organic group, R 15～R 18Expression has the organic group of epoxy radicals or ethylenic unsaturated group.
[changing 14]
Figure BDA00003281053100211
The amount of above-mentioned (D1) simple function (methyl) acrylate is 20～100 quality % with respect to (D) radiation polymerizable compound preferably, and more preferably 40～100 quality % most preferably are 50～100 quality %.Be above-mentioned amount by making simple function (methyl) acrylate, thereby can improve after the B rankization and adaptation and thermo-compressed adherend.
As (D) radiation polymerizable compound, can contain 2 officials can above (methyl) acrylate.As such acrylate, have no particular limits, can enumerate for example diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, the diethylene glycol dimethylacrylate, the triethylene glycol dimethylacrylate, the TEG dimethylacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, the trimethylolpropane dimethylacrylate, trimethylol-propane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexane diol diacrylate, 1,4-butanediol dimethylacrylate, 1,6-hexane diol dimethylacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, styrene, divinylbenzene, the 4-vinyltoluene, 4-vinylpridine, the N-vinyl pyrrolidone, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, 1,3-acryloxy-2-hydroxy propane, 1,2-methacryloxy-2-hydroxy propane, methylene-bisacrylamide, N,N-DMAA, N hydroxymethyl acrylamide, the triacrylate of three (beta-hydroxy ethyl) isocyanuric acid ester, compound shown in the following general formula (6), urethane acrylate, carbamate methacrylate and urea acrylate.
[changing 15]
Figure BDA00003281053100221
In the formula (6), R 19And R 20Represent hydrogen atom or methyl independently of one another, g and h represent 1～20 integer independently of one another.
These radiation polymerizable compounds can use a kind or be used in combination more than 2 kinds separately.Wherein, the radiation polymerizable compound with two ol skeletons shown in the above-mentioned general formula (6) can give the solvent resistance after the sufficient curing and have low viscosity, higher 5% quality reduces temperature, is preferred in these areas.
In addition, by using the high radiation polymerizable compound of functional group's equivalent, can realize low stressization, low warpageization.Polymer functional group's equivalent of the radiation polymerizable compound that functional group's equivalent is high is preferably more than the 200eq/g, more preferably more than the 300eq/g, most preferably is more than the 400eq/g.By use polymer functional group's equivalent as more than the 200eq/g, have the radiation polymerizable compound of ether skeleton, carbamate groups and/or isocyanuric acid base, thereby can improve the cementability of bonding agent and realize low stressization, low warpageization.In addition, can also and be that radiation polymerizable compound more than the 200eq/g and polymer functional group's equivalent are less than the radiation polymerizable compound of 200eq/g with polymer functional group's equivalent.
(D) amount of radiation polymerizable compound is 10～95 quality % with respect to the bonding agent total amount preferably, the viewpoint of the wetting autgmentability during from the chip crimping, 20～90 quality % more preferably from keeping the viewpoint of the shape after the B rankization, most preferably are 40～90 quality %.At (D) composition during less than 10 quality %, exist the viscous force after the B rankization to become big tendency, when (D) composition surpasses 95 quality %, the tendency that exists the adhesive strength after the hot curing to reduce.
(D) the radiation polymerizable compound is aqueous radiation polymerizable compound in room temperature (15 ℃～35 ℃) preferably, when considering paste from the detachment of netted galley, viscosity is preferably below the 5000mPas, further consider by the printing after flow to realize planarization certainly the time, more preferably below the 3000mPas.When viscosity surpasses 5000mPas, there is the tendency that viscosity rises, printing reduces of bonding agent.In addition, (D) lower limit of the viscosity of radiation polymerizable compound is about 0.1mPas.
As (D) radiation polymerizable compound, 5% quality reduces temperature and is preferably more than 120 ℃, more preferably more than 150 ℃, further more preferably more than 180 ℃.At this, 5% quality reduces temperature and refers to the radiation polymerizable compound is used differential thermogravimetric amount determinator (SII Technology system: the 5% quality minimizing temperature when TG/DTA6300) measuring simultaneously under 10 ℃/minute of programming rates, nitrogen stream (400mL/ branch).Reduce the high radiation polymerizable compound of temperature by using 5% quality, thereby can suppress the volatilization of unreacted radiation polymerizable compound when thermo-compressed or hot curing.
As (E) Photoepolymerizationinitiater initiater (light trigger), consider from the aspect that improves photosensitivity, be Photoepolymerizationinitiater initiater more than the 100mL/gcm to the molecule absorptivity of the light of wavelength 365nm preferably, the more preferably above Photoepolymerizationinitiater initiater of 200mL/gcm.In addition, the molecule absorptivity is following tries to achieve: 0.001 quality % acetonitrile solution of preparation sample, and use spectrophotometer (high and new technology company of Hitachi system, " U-3310 " (trade name)) to measure absorbance to this solution, try to achieve thus.
As such (E) composition; can enumerate for example 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone; 1-hydroxyl-cyclohexyl-phenyl-ketone; 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl acetone-1; 2; the 4-diethyl thioxanthone; aromatic ketones such as 2-EAQ and phenanthrenequione; benzil derivatives such as benzil dimethyl ketal; 2-(Chloro-O-Phenyl)-4; 5-diphenyl-imidazole dimer; 2-(Chloro-O-Phenyl)-4; 5-two (m-methoxyphenyl) imidazole dimer; 2-(adjacent fluorophenyl)-4; 5-phenylimidazole dimer; 2-(o-methoxyphenyl)-4; 5-diphenyl-imidazole dimer; 2-(p-methoxyphenyl)-4; 5-diphenyl-imidazole dimer; 2; 4-two (p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2; the 4-Dimethoxyphenyl)-4; 5-diphenyl-imidazole dimer etc. 2; 4; 5-triarylimidazoles dimer; 9-phenylacridine and 7-two (9; 9 '-acridinyl) acridine derivatives such as heptane; two (2; 6-dimethoxy benzoyl)-2; 4; 4-trimethyl-amyl group phosphine oxide and two (2,4,6;-trimethylbenzene formyl)-two acylphosphine oxides such as phenyl phosphine oxide, and the compound with maleimide.These materials may be used singly or in combin more than 2 kinds.
Deliquescent aspect in the never solvent-laden bonding agent is considered, as above-mentioned Photoepolymerizationinitiater initiater, preferred use 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl propane-1-ketone.In addition, even from air atmosphere, also can utilize the exposure carry out the B rankization aspect the consideration, preferred 2-benzyl-2-dimethylamino-1-(4-morpholinyl the phenyl)-butanone-1,2 that uses, 2-dimethoxy-1,2-diphenylethane-1-ketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl propane-1-ketone.
(E) composition can contain the light trigger that the irradiation that utilizes radiation embodies the function of the polymerization that promotes epoxy resin and/or reaction.As such light trigger, can enumerate the Photobase generator that for example utilizes irradiation with radiation to produce alkali, utilize the acidic photoacid generator of irradiation with radiation etc., special preferred light generated base alkaline agent.
By using Photobase generator, can further improve bonding agent to high temperature bonding and the moisture-proof of adherend.As its reason, think because: play a role effectively as the curing catalysts of epoxy resin by making the alkali that generated by Photobase generator, thereby can further improve crosslink density, and the situation of the curing catalysts corrosion substrate etc. of generation is tailed off.In addition, contain Photobase generator by making bonding agent, thereby can improve crosslink density, the exhaust in the time of can further reducing the high temperature placement.And then, can make curing process temperature low temperatureization, realize short timeization.
Photobase generator then can use with no particular limitation so long as produce the compound of alkali when irradiation with radiation.As the alkali that produces, consider preferred strongly alkaline compound from aspect reactive, curing rate.
As such alkali that produces when the irradiation with radiation, can enumerate for example imidazoles, 2, imdazole derivatives such as 4-methylimidazole and 1-methylimidazole, piperazine and 2, bridged piperazine derivatives such as 5-lupetazin, piperidines and 1, piperidine derivatives such as 2-lupetidine, proline derivative, trimethylamine, trialkylamine such as triethylamine and triethanolamine derivative, the pyridine derivate that 4 of 4-methylamino pyridine and 4-dimethylaminopyridines etc. are replaced by amino or alkylamino, pyrrolidin derivatives such as pyrrolidines and N-crassitude, dihydrogen pyridine derivative, triethylenediamine and 1,8-diazabicyclo (5,4,0) hendecene-1 ester ring type amine derivatives such as (DBU), and benzyl methylamine, benzyl amine derivatives such as benzyl dimethylamine and benzyl diethylamine.
As utilizing irradiation with radiation to produce the Photobase generator of alkali as described above, the quaternary ammonium salt derivative that can use for example Journal ofPhotopolymer Science and Technology12 volume, 313～314 (1999) or Chemistry ofMaterials11 volume, 170～176 (1999) to put down in writing in waiting.These quaternary ammonium salt derivatives utilize the irradiation of active ray to generate overbasic trialkylamine, therefore are suitable for most the curing of epoxy resin.
As Photobase generator, can also use Journal of American ChemicalSociety118 to roll up the carbamic acid derivative of record in 12925 pages (1996) or the Polymer Journal28 volume 795 pages (1996) etc.
Produce the Photobase generator of alkali as the irradiation that utilizes active ray, can use 2,4-dimethoxy-1,2-diphenylethane-1-ketone, 1,2-octane diketone, 1-[4-(thiophenyl)-2-(o-benzoyl oxime)], ethyl ketone and 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-9 oxime derivates such as (adjacent acetyl oximes), produce commercially available 2-benzyl-2-dimethylamino-1-(4-morpholinyl the phenyl)-1-butanone of agent as optical free radical, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, (phenyl can be by halogen for the hexa-aryl bi-imidazole derivative, alkoxyl, nitro, substituting groups such as cyano group replace), and benzoisoxazole ketone derivatives.
As Photobase generator, can use the compound at the group of high molecular main chain and/or side chain importing generation alkali.As the molecular weight of this moment, from cementability, flowability and stable on heating viewpoint as bonding agent, weight average molecular weight is preferably 1000～100000, and more preferably 5000～30000.
Above-mentioned Photobase generator can not demonstrate the reactivity with epoxy resin under non-exposure status, so the storage-stable under the room temperature is very excellent.
Utilize exposure carry out under the situation of operation of B rankization, the described bonding agent of present embodiment can as required and use sensitizer.As this sensitizer, can enumerate for example camphorquinone (camphorquinone), benzil, biacetyl, the benzil dimethyl ketal, benzil diethyl ketal, benzil two (2-methoxy ethyl) ketal, 4,4 '-dimethyl benzil-dimethyl ketal, anthraquinone, the 1-chloroanthraquinone, the 2-chloroanthraquinone, 1,2-benzo anthraquinone, the 1-hydroxy-anthraquione, the 1-methylanthracene quinone, the 2-EAQ, the 1-bromo anthraquinone, thioxanthones, the 2-isopropyl thioxanthone, 2-nitro thioxanthones, 2-methyl thioxanthones, 2,4-dimethyl thioxanthones, 2, the 4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones, 2-chloro-7-trifluoromethyl thioxanthones, thioxanthones-10, the 10-dioxide, thioxanthones-10-oxide, benzoin methyl ether, the benzoin ethylether, isopropyl ether, the benzoin isobutyl ether, benzophenone, two (4-dimethylaminophenyl) ketone, 4,4 '-two diethylamino benzophenone and contain the compound of azido.These sensitizers can use separately or and with more than 2 kinds.
Utilize exposure carry out under the situation of operation of B rankization, in the described bonding agent of present embodiment, the raising low stress, and the adaptation of adherend, thermo-compressed aspect, can contain above-mentioned (C) thermoplastic resin.
Utilize exposure carry out under the situation of operation of B rankization, the described bonding agent of present embodiment can use hot radical generation agent as required.Produce agent as hot radical, be preferably organic peroxide.As organic peroxide, preferred 1 minute half life temperature is the organic peroxide more than 80 ℃, and more preferably 1 minute half life temperature is the organic peroxide more than 100 ℃, and most preferably 1 minute half life temperature is the organic peroxide more than 120 ℃.The modulation condition of organic peroxide consideration bonding agent, film temperature processed, curing (applying) condition, process conditions, storage-stable etc. are selected.As the peroxide that can use, there is no particular limitation, for example can enumerate 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide hexane), dicumyl peroxide, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, uncle's hexyl peroxidating-2 ethyl hexanoic acid ester, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (peroxidating of uncle's hexyl)-3 of 1-, 3,5-trimethyl-cyclohexane and two (4-tert-butylcyclohexyl) peroxy dicarbonate.These peroxide can use a kind or be mixed with two or more separately.By containing organic peroxide, thereby unreacted radiation polymerization compound remaining in exposure is reacted, and can realize low exhaustization, high bondingization.
With respect to the total amount of radiation polymerization compound, the amount that hot radical produces agent is preferably 0.01～20 quality %, more preferably 0.1～10 quality %, more preferably 0.5～5 quality %.The amount that produces agent when hot radical is during less than 0.01 quality %, the reduction of curing property, and additive effect diminishes, and when the amount that produces agent when hot radical surpasses 5 quality %, exists to demonstrate the tendency that air displacement increases, storage stability reduces.
Produce agent as hot radical, so long as half life temperature is the compound more than 80 ℃, then there is no particular limitation, can enumerate for example PERHEXA25B (day oily corporate system), 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide hexane) (1 minute half life temperature: 180 ℃), PERCUMYL D (day oily corporate system), and dicumyl peroxide (1 minute half life temperature: 175 ℃).
In addition, when the formation at bond layer, under the significant situation of generation of bubble, hole, effectively add additives such as defoamer, foamicide, foam inhibitor at above-mentioned (B) solvent or (D) in the radiation polymerizable compound.The addition of these additives, press down the viewpoint of bubble effect from performance, with (B) solvent or (D) total amount of radiation polymerizable compound and additive be benchmark, be preferably more than the 0.01 quality %, viewpoint from the viscosity stability of cementability, paste is preferably below the 10 quality %.
In this specification, " lowest melt viscosity " is illustrated in the baking oven the following 4 hours heating process of 80 ℃ of conditions or utilizes light quantity 1000mJ/cm 2The exposure process of light in the bond layer after the B rankization is used the minimum of the melt viscosity under 20～300 ℃ of conditions of determination of viscoelasticity device ARES (RHEOMETRICS Scientific FE (strain) system) when measuring.In addition, assay plate is the parallel-plate of diameter 8mm, and condition determination is for heating up 5 ℃/minute, and measuring temperature and be 20 ℃～300 ℃, frequency is 1Hz.
Lowest melt viscosity after the above-mentioned B rankization is preferably below the 20000Pas, more preferably below the 18000Pas, further more preferably below the 15000Pas.By having the lowest melt viscosity in the above-mentioned scope, thereby can guarantee sufficient connecing property of low temperature and pressure, even also can give good adaptation for having concavo-convex substrate etc.The lower limit of above-mentioned lowest melt viscosity has no particular limits, and aspect operability, is preferably more than the 10Pas.
In order to give storage stability, Technological adaptability or non-oxidizability to the described bonding agent of present embodiment, can in the scope of not damaging curing property, further add polymerization inhibitor or the antioxidant of quinones, polyatomic phenol, phenols, phosphorous acid esters and sulphur class etc.
And then the described bonding agent of present embodiment also can suitably contain filler.As filler, can enumerate for example metallic stuffings such as silver powder, bronze, copper powder and nickel powder, inorganic fillers such as aluminium oxide, aluminium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicates, magnesium silicate, calcium oxide, magnesium oxide, aluminium oxide, aluminium nitride, crystallinity silicon dioxide, amorphous silicon di-oxide, boron nitride, titanium dioxide, glass, iron oxide and pottery, and carbon and rubber are organic fillers such as filler.Above-mentioned filler all can use with no particular limitation regardless of kind and shape.
Above-mentioned filler can corresponding required function and use respectively.For example, metallic stuffing is added to give bonding agent conductivity, heat conductivity and thixotropic purpose, nonmetal inorganic filler is added with the purpose of giving bond layer heat conductivity, low heat expansion and agent of low hygroscopicity, and organic filler is added with the purpose of giving bond layer toughness.
These metallic stuffings, inorganic filler or organic filler can be used a kind or be used in combination more than 2 kinds separately.Wherein, giving aspects such as the desired conductivity of bonding agent that semiconductor device fabrication uses, heat conductivity, low moisture-absorption characteristics, insulating properties, the filler of preferable alloy filler, inorganic filler or insulating properties, in inorganic filler or insulating properties filler, to the favorable dispersibility of resin varnish and can give high bonding force when hot aspect consider more preferably silica filler.
It is below the 10 μ m that above-mentioned filler preferably makes average grain diameter and maximum particle diameter is below the 30 μ m, and more preferably making average grain diameter is below the 5 μ m and maximum particle diameter is below the 20 μ m.When average grain diameter surpasses 10 μ m and maximum particle diameter and surpasses 30 μ m, there is the tendency that is difficult to be improved fully the effect of destroying toughness.In addition, the lower limit of average grain diameter and maximum particle diameter has no particular limits, and both are more than the 0.001 μ m usually.
The amount of above-mentioned filler decides according to the characteristic of giving or function, with respect to the summation of resinous principle and filler, is preferably 0～50 quality %, more preferably 1～40 quality %, more preferably 3～30 quality %.By increasing the amount of filler, thereby can realize low αization, low moisture absorptionization, high elastic modulusization, and can effectively improve cutting (based on the cuttability of cutting edge), wire bond (ultrasonic wave efficient), follow intensity when hot.
When the amount with filler increases to requiredly when above, exist viscosity to rise or the impaired tendency of thermo-compressed, therefore, the amount of filler is preferably controlled in above-mentioned scope.In order to obtain the balance of desirable characteristics, determine the amount of best filler.Mixing when using filler and mixing can the common mixer of appropriate combination, dispersion machines such as mixing and kneading machine, three roller mixing rolls, ball mill carry out.
In order to make the interface combination well between foreign material, in the described bonding agent of present embodiment, also can add various coupling agents.As coupling agent, for example can enumerating, silane system, titanium system and aluminium are coupling agent.Wherein, additive effect high aspect consider that preferred silane is coupling agent, more preferably have the compound of functional group of functional group, methacrylate and/or the acrylate israds polymerism of Thermocurables such as epoxy radicals.In addition, the boiling point of above-mentioned silane series coupling agent and/or decomposition temperature are preferably more than 150 ℃, more preferably more than 180 ℃, further more preferably more than 200 ℃.That is, most preferably use boiling point and/or the decomposition temperature more than 200 ℃ and have the silane series coupling agent of functional group of functional group, methacrylate and/or the acrylate israds polymerism of Thermocurables such as epoxy radicals.The amount of relevant above-mentioned coupling agent is considered from effect, thermal endurance and the cost aspect brought by its interpolation, with respect to employed bonding agent 100 mass parts, is preferably 0.01～20 mass parts.
For adion impurity and the insulating reliability when making moisture absorption good, in the described bonding agent of present embodiment, also can further add ion capturing agent.As such ion capturing agent, have no particular limits, can enumerate for example triazine thiol compound, phenol and be that conduct such as reducing agent is used for preventing copper ionization and the copper evil of stripping prevents agent and compound known, pulverous bismuth system, antimony system, magnesium system, aluminium system, zirconium system, calcium system, titanium system, tin are and the inorganic compound of their mixed stocker etc.As concrete example, there is no particular limitation, and inorganic ion scavenger, trade name, IXE-300 (antimony system), IXE-500 (bismuth system), IXE-600 (antimony, bismuth mixed stocker), IXE-700 (magnesium, aluminium mixed stocker), IXE-800 (zirconium system), the IXE-1100 (calcium system) etc. of East Asia synthetic (strain) system are arranged.These materials can use separately or be mixed with two or more.The amount of relevant above-mentioned ion capturing agent is considered from effect, thermal endurance and the cost aspect brought by its interpolation, with respect to bonding agent 100 mass parts, is preferably 0.01～10 mass parts.
From the viewpoint of when utilizing print process to form bond layer, when the peristome of the netted galley of printing forward direction is supplied with the paste of bonding agent, stably supplying with, the thixotropy index of bonding agent is preferably 1.0～8.0, paste when considering printing is from the disengaging of netted peristome, the thixotropy index of bonding agent more preferably 1.0～4.0, make the bubble of printing back bond layer, the viewpoint of netted vestige planarization from flow by aforesaid paste spontaneously, the thixotropy index of bonding agent is preferably 1.0～2.0 especially.When above-mentioned thixotropy index is 1.0 when above, have following trend: suppress to utilize print process supply with and the aforesaid paste of coating in the generation of collapsing etc., can keep printing shape well.And then, when this thixotropy index is 8.0 when following, have following trend: can suppress to utilize print process supply with and the aforesaid paste of coating in the generation of " disappearance ", the style of calligraphy characterized by hollow strokes etc.
The viscosity of bonding agent (25 ℃), from when operating, paste being supplied to the viewpoint of galley operability first-class, paste, be preferably 0.1～1000Pas, the viewpoint from netted peristome paste disengaging during from printing, 0.1～300Pas more preferably, make the bubble of printing back bond layer, the viewpoint of netted vestige planarization from flow by paste spontaneously, be preferably 0.1～100Pas especially.
Value when above-mentioned viscosity is to use E type rotation viscometer (TOKYO KEIKI INC. system) to measure under 3 ° of cones, 25 ℃, the condition of rotating speed 0.5rpm.The ratio of the value when measuring under the value when the thixotropy index is defined as and measures under 25 ℃, the condition of rotating speed 1rpm with E type rotation viscometer and 25 ℃, the condition of rotating speed 10rpm.
Viscosity under viscosity/10rpm under thixotropy index=1rpm
＜semiconductor device 〉
Fig. 2～5th, the schematic diagram of an execution mode of the manufacture method of expression semiconductor device of the present invention.The manufacture method of the described semiconductor device of present embodiment comprises: the operation (bond layer forms operation) that forms the bond layer 7 that is formed by above-mentioned bonding agent at a face of semiconductor wafer 6; Utilize heating or exposure bond layer 7 to be carried out the operation (B rank chemical industry order) of B rankization; With the operation (cutting action) that semiconductor wafer 6 is cut with B rank bond layer 8.
(bond layer formation operation)
Method as forming bond layer has no particular limits, for example, can be as shown in Figure 2, utilize silk screen print method printing bonding agent 5 at the face (back side) of a side opposite with the face of the circuit that is formed with semiconductor wafer 6.
The described bonding agent of present embodiment can be suitable as the above-mentioned bonding agent 5 in the manufacture method of above-mentioned semiconductor packages.
In addition, in utilizing the bonding agent painting process of silk screen print method, the preferred galley that for example is provided with the peristome 3 of netted galley than semiconductor wafer 6 of using with more dwindling.Thus, as shown in Figure 1, the bond layer 7 of uniform thickness is formed on the ratio circumference of the semiconductor wafer 6 on the back side of semiconductor wafer 6 with dwindling and locates more in the inner part.
Bond layer 7 is being formed under the ratio circumference situation more in the inner part of semiconductor wafer 6, bond layer 7 does not cover the end of semiconductor wafer 6, and the projection on the end of bond layer 7 is reduced, and can improve the uniformity of bond layer 7.By bond layer 7 is formed at the inboard of the circumference of semiconductor wafer 6, thereby the thickness of bond layer 7 is become evenly, in the lamination operation of aftermentioned cutting film, can make the pressure that is carried on wafer more even, can prevent the breakage of semiconductor wafer.In addition, when being formed uniformly the thickness of bond layer 7, lamination cuts film equably easily, therefore, after cutting action in, the problem that is called as " chip disperses " that the semiconductor chip that can prevent singualtion is flown by blowing from the cutting film, rate of finished products reduces.
Silk screen print method roughly is divided into two kinds usually.A kind of peristome, so-called process of using the operplate printing version for be provided with patterning at smooth metallic plate.In this process, at the object of wanting to print the operplate printing version is set, sweep with the metallic plate that is called as scraper plate (squeegee) 4 and scrape the black liquid that is equipped on the operplate printing version, be coated with black liquid thus.Utilize this operation, be coated with black liquid according to the shape of the patterns of openings that is arranged at the operplate printing version.
As another silk screen print method, have in the net of preparing by the silk of braiding stainless steel, nylon and polyester etc. with the process residual mode landfill resin of wanting the part that is coated with only etc., the netted galley of so-called use.In this process, sweep and scrape the black liquid that is equipped on the netted galley with being called as the resin system of scraper plate (scraper) or metal plate.Utilize this operation, black liquid is infiltrated into not by the peristome of the landfills such as resin of netted galley.Then, use the scraper plate of being made by polyurethane, silicon rubber etc. 4, scrape sweeping on the netted galley.Utilize this operation, the black liquid that permeates in peristome is transferred on the printing object, finish printing process.
In the present embodiment, any typography method all can be only in the desired position, regioselectivity ground coating adhesive, therefore, can reduce the waste of bonding agent, finished material rate excellence.
In the process of using the operplate printing version, when when wideer scope is printed, because peristome is without any parts, therefore can not produce at the stress from galley at the pressure of the scraper plate of peristome, pressure concentrates on the central authorities of scraper plate, the scraper plate central portion firmly pushes peristome, has the tendency of the thickness reduction of peristome central authorities.That is, peristome is more wide usually, and the central portion of scraper plate more firmly pushes, and exists the thickness of central authorities to get over the tendency that reduces.
On the other hand, in the process of using netted galley, owing at peristome twine is arranged also, therefore can produce the stress from netted galley at the pressure of scraper plate.That is, even at the scraper plate central portion, be positioned at the twine of peristome as support component performance function, therefore, scraper plate can be to the powerful extruding of peristome yet.Therefore, also can not reduce and uniform bond layer even can access at scraper plate central portion thickness.
In the silk screen print method of present embodiment, from the viewpoint of the bond layer of uniform film thickness is set in whole this wideer scope of semiconductor wafer, preferably use the process of netted galley.
In bond layer forms operation, can also use ink jet printing method except above-mentioned silk screen print method, spin-coating method, gap rubbing method etc. and bond layer 7 is formed at the desired zone of semiconductor wafer 6.
In ink jet printing method, the bonding agent of dropletization is ejected into required scope as the semiconductor wafer 6 of printing object from the pore that is called as nozzle, can form bond layer 7 in the target area thus.In addition, in spin-coating method, bonding agent is spun on the semiconductor wafer 6 that circumference is pasted with masking tape (masking tape), peels off masking tape then, can form bond layer 7 in the target area thus.And then, in the rubbing method of gap, the mounting circumference is pasted with the semiconductor wafer 6 of masking tape on smooth objective table, then, place bonding agent in the end of semiconductor wafer 6, make the parallel movement of spreader (applicator) that arranges in required interval height, coat bonding agent on the wafer after, peel off masking tape, can form bond layer 7 in the target area thus.
(B rank chemical industry order)
Above-mentioned bonding agent 7 is to utilize heating or exposure to carry out B rankization back has cementability to adherend bonding agent.For the bond layer that is coated with, utilize heater such as baking oven, exposure device that the bonding agent that constitutes bond layer 7 is carried out the B rankization.
Under the situation of Thermocurable bonding agent, utilize heating to make the solvent evaporates that contains in the bonding agent or in solvent evaporates, make Thermocurable bond layer after heat-curing resin reacts, carries out the B rankization, have suitable adhesiveness and cementability.Particularly, bond layer is fixed in semiconductor wafer.
On the other hand, under the situation of photosensitive adhesive, utilize exposure to make the Photoepolymerizationinitiater initiater and the radiation polymerizable compound that contain in the photosensitive adhesive carry out polymerization reaction, carry out the photosensitive adhesive layer after the B rankization, have suitable adhesiveness and cementability.Particularly, the photosensitive adhesive layer is fixed in semiconductor wafer.From avoiding hindering because of oxygen the viewpoint of photopolymerization reaction, exposure is preferred under nitrogen atmosphere or under the vacuum condition or photosensitive adhesive is pressed layer by layer under the state of transparent overlay film and carry out.
More specifically, the bond layer 8 that utilizes heating or exposure to carry out the B rankization has and suitablely carries out singualtion and can shell the suitable adhesiveness of From and to the cementability of adherends such as semiconductor chip and glass substrate from supporter when cutting by cutting.
Be 200gf/cm by making the bond layer after heating or the exposure at 30 ℃ surperficial viscous force 2Below, thereby demonstrate bond layer by the B rankization.
When the surperficial viscous force at 30 ℃ surpasses 200gf/cm 2The time, have the tendency that surface adhesion uprises, operability reduces under the room temperature of bond layer, and exist with cutting after the fissility reduction, the tendency of picking up property reduction of cutting film.In addition, when the surperficial viscous force at 30 ℃ be 1gf/cm 2The interface of when following, have the adhesiveness step-down of bonding agent, water infiltrating bonding agent and cutting film when cutting, the tendency that the generation chip disperses.
Bond layer after heating or the exposure is preferably 200gf/cm at 120 ℃ surperficial viscous force 2More than.Surperficial viscous force under 120 ℃ is less than 200gf/cm 2The time, have that thermo-compressed is impaired, produce the tendency of space, thermo-compressed temperature high temperatureization during thermo-compressed.In addition, when the surperficial viscous force at 120 ℃ be 500gf/cm 2Under the above situation, the tendency that wetting expansion is excessive when having thermo-compressed, bonding agent overflows in chip sides.
Above-mentioned surperficial viscous force is the value of measuring in such a way.Bonding agent is being utilized silk screen print method etc. coat on the silicon wafer and utilize under the situation of the operation that heating carries out the B rankization to filming of gained, in baking oven, in 80 ℃ of following heating processes of 4 hours, carrying out the B rankization; Carry out utilizing light quantity 1000mJ/cm under the situation of operation of B rankization utilizing exposure 2The exposure process that carries out of light in carry out the B rankization.Then, use the PROBE TUCKING testing machine of RHESCA corporate system, at probe diameter: 5.1mm, peeling rate: 10mm/s, contact loading: 100gf/cm 2, time of contact: under the condition in 1 second, the viscous force on bond layer 8 surfaces under measuring 30 ℃ and 120 ℃.
(cutting action)
Then, the above-mentioned semiconductor wafer 6 that is coated with bonding agent is cut from semiconductor wafer side, make the semiconductor chip of singualtion.That is, utilize cutting machine to cut off semiconductor wafer 6, thus semiconductor wafer 6 is cut into a plurality of semiconductor chip 13a and 13b.Before this cutting action, preferably attach the cutting film at the back side of the semiconductor wafer 6 that is coated with above-mentioned bonding agent.Attaching limit heating edge is as required carried out.For example, preferably utilizing cutting film 10 to make overall fixed under the state of framework (wafer ring) 9 (with reference to Fig. 3) use cutter to attach (with reference to Fig. 4).The semiconductor chip 11 of the band bond layer of singualtion uses the chip join device to wait to pick up (with reference to Fig. 5).
As shown in Figure 6, the semiconductor chip 13a that utilizes cutting action to obtain is disposed at separately on the support component of preparing 14 or with semiconductor chip 13b and is disposed on the semiconductor chip 13a that joins support component in advance to.At this moment, by thermo-compressed bond layer 16 and 17, thereby make the bonding and semiconductor chip 13b of semiconductor chip 13b and support component 14 and semiconductor chip 12a bonding, semiconductor chip is adhesively fixed in support component or semiconductor chip.
Then, utilize heating to carry out the hot curing of bond layer, utilize welding wire 18 to connect solder pad (bonding pad) and support component on the semiconductor chips, with sealing material 15 semiconductor chip is sealed with welding wire, finish semiconductor packages as shown in Figure 6 thus.
According to the manufacture method of the semiconductor packages of above explanation, for bonding semiconductor chip and support component or bonding agent that semiconductor chip is bonded to each other, can utilize only coating adhesive on semiconductor wafer of typography method.Thus, regardless of the composition of bonding agent, can be coated with required thickness by change galley.Therefore, can reduce the waste of the bonding agent in the manufacture method of semiconductor packages, and can be coated with multiple thickness with single bonding agent.
Embodiment
Below, enumerate the present invention of embodiment and be described more specifically.But the present invention is not subjected to the restriction of following examples.
(synthesizing of thermoplastic resin)
With diphenyl methane-4,4 '-vulcabond (1.0mol), diphenyl methane-2, the polytetramethylene glycol (0.8mol) of 4 '-vulcabond (1.0mol) and mean molecule quantity 2000 and 1-Methyl-2-Pyrrolidone mix, under nitrogen atmosphere, 100 ℃ the reaction 1 hour after, add 4,4 '-oxygen diphthalic anhydrides (1.0mol) and 1-Methyl-2-Pyrrolidone stirred 3 hours at 140 ℃ again.Then, to wherein further adding 2-diacetylmonoxime (0.2mol), stirred 1 hour at 100 ℃, obtain reactant liquor.The reactant liquor of gained is placed water after the vigorous stirring, the leaching sediment, in a vacuum 60 ℃ dry 48 hours down, obtain the imide-urethane resin.Use result that the molecular weight of the imide-urethane resin of the gained of GPC measures for the weight average molecular weight (Mw) with polystyrene conversion is 93700, number-average molecular weight (Mn) is 38800.In addition, the imide-urethane resin of gained at room temperature is semi-solid shape, and glass transition temperature (Tg) is-40 ℃.
(modulation of bonding agent)
(aqueous bonding agent 1)
With above-mentioned imide-urethane resin 5.0 mass parts, " YDCN700-7 " (the linear phenol aldehyde type epoxy resin of cresols, Dongdu change into (strain) system, trade name) 12.5 mass parts, " TrisP-PA " (4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethane-1,1-two bases] bis-phenol, Honshu chemical industry (strain) system, trade name) 5.0 mass parts and carbitol acetic acid esters (with the pure medicine of light (strain) system) 16.0 mass parts drop in the flask that is arranged in the oil bath, under nitrogen atmosphere, under 80 ℃, add thermal agitation, preparation solution.In the solution of gained, add " SO-C2 " (silica filler, ADMATECHS (strain) system, trade name) 10.0 mass parts and " TPPK " (tetraphenylphosphoniphenolate tetraphenyl borate salts, Tokyo change into industry (strain) system, trade name) 0.2 mass parts; place mixing and kneading machine; carry out mixing after, it is mixing to carry out deaeration in 1 hour again below 5Torr.Then, add carbitol acetic acid esters 5.0 mass parts as printing ink solvent, it is mixing to carry out deaeration, adjusts viscosity thus, and the viscosity that obtains under the rotating speed 0.5rpm is that 26Pas, thixotropy index are 1.1 aqueous aqueous bonding agent 1.
(aqueous bonding agent 2)
" YDCN700-7 " 30 mass parts and " ARONIX M-140 " (N-acryloxy ethyl hexahydrophthalic phthalimide, East Asia synthetic (strain) system, trade name) 40 mass parts are dropped in the flask that is arranged in the oil bath, under nitrogen atmosphere, under 60 ℃, add thermal agitation, make its dissolving.Then, in flask, add " I-379EG " (2-(dimethylamino)-2-(4-methyl-benzyl)-1-(4-morpholinyl phenyl) butane-1-ketone, CIBA JAPAN (strain) system, trade name) 0.4 mass parts and " 1B2PZ " (1-benzyl-2-phenylimidazole, four countries change into industry (strain) system, trade name) 0.2 mass parts, stir, the viscosity that obtains under the rotating speed 0.5rpm is that 13Pas, thixotropy index are 1.0 aqueous bonding agent 2.
(formation of bond layer)
Embodiment 1～4
Use is provided with the MK-838SV printing machine (MINAMI Co., Ltd. system) of the netted galley of V-screen V50 ((strain) NBC Meshtec Inc. system), with the aqueous bonding agent 1 of gained or 2 with the circumference of silicon wafer (below, being also referred to as " end ") mode that do not form bond layer coats with the circle printing on the back side of silicon wafer of 5 inches φ, thus produce the wafer of band bond layer respectively.By the state of the bonding agent after the Visual Confirmation printing, the result can not have ground such as the style of calligraphy characterized by hollow strokes bond layer is set uniformly.
Comparative example 1
Same with the formation of the bond layer of embodiment, use the MK-838SV printing machine that is provided with the netted galley of V-screen V50 to print coating, produce the wafer of band bond layer.But, the set positions of the silicon wafer of 5 inches φ of change, the mode that covers whole of silicon wafer according to the galley peristome is printed, and also has been coated with bonding agent in the silicon wafer end.
(the inhomogeneity evaluation of bond layer)
Wafer with the band bond layer of the embodiment 1～3 that makes as described above and comparative example 1 uses baking oven 80 ℃ of heating 4 hours, and bond layer is carried out the B rankization.In addition, use parallel exposure machine ((strain) LUMINOUS system, trade name " ML-210FM Mask Aligner "), under nitrogen atmosphere, 1000mJ/cm 2Condition under the wafer of the band bond layer of embodiment 4 is exposed, bond layer is carried out the B rankization.For the wafer of each band bond layer, use noncontact film thickness gauge (KEYENCE (strain) system, trade name " KS-1100 "), measure silicon wafer end and the distance of bond layer end, the thickness of bond layer, the projection of bond layer end.The projection of end is made as the difference of height of the peak of the par of bond layer and bossing.The table 1 that the results are shown in gained.
[table 1]
Figure BDA00003281053100361
As shown in table 1, in the described bond layer of embodiment, end bosses is compared with comparative example significantly with respect to the ratio of bond layer thickness and is reduced.Thus, locate to form adhesive linkage more in the inner part by the ratio circumference at semiconductor wafer, thereby even confirm the uniformity of also possessing bond layer in the bond layer end.
In addition, the silicon wafer upper strata crush-cutting of the band bond layer of making in embodiment and comparative example cuts film, carried out cutting action, result: in the silicon wafer of embodiment 1, the part of the periphery after printing produces collapsing of paste, but can not influence flatness, even cutting action also can be handled on no problem ground.Cutting action no problem ground is handled.Relative therewith, in the silicon wafer of comparative example 1, behind the lamination of cutting film, produce less crack at the silicon wafer circumference, cause the breakage of silicon wafer.In addition, when the silicon wafer after the observation cutting, mainly disperse at wafer circumference portion generation chip.
Utilizability on the industry
According to the present invention, can provide with uniform thickness semiconductor wafer be formed with the band bond layer of bond layer semiconductor wafer, use manufacture method and the semiconductor device of its semiconductor device.
Symbol description
1... galley housing, 2... the part of inserting with resin in the netted galley, 3... the peristome in the netted galley, 4... scraper plate, 5... bonding agent, 6... semiconductor wafer, 7... bond layer, 8...B the bond layer that rank have been changed, 9... framework, 10... cutting film, 11... the bonding agent semiconductor chip of the band bond layer of singualtion, 12... cutter, 13a... the 1st layer of semiconductor chip, 13b... the 2nd layer of semiconductor chip, 14... support component, 15... encapsulant, 16... the bond layer with the 1st layer of semiconductor chip and support component joint, 17... the bond layer with the 2nd layer of semiconductor chip and the 1st layer of semiconductor core chip bonding, 18... welding wire.

Claims (6)

1. semiconductor wafer with bond layer, it possesses semiconductor wafer and is formed at bond layer on the face of described semiconductor wafer,
Be formed with described bond layer than the more close inboard place of the circumference of described semiconductor wafer.
2. the semiconductor wafer of band bond layer according to claim 1, wherein, described bond layer is by being that aqueous bonding agent forms under 15～35 ℃ of conditions.
3. the manufacture method of a semiconductor device, it comprises:
Form the operation of the bond layer that is formed by bonding agent at the more close inboard place of the ratio circumference of a face of semiconductor wafer; With
Described bond layer is carried out the operation of B rankization.
4. the manufacture method of semiconductor device according to claim 3, wherein, described bond layer utilizes silk screen print method, ink jet printing method, spin-coating method or gap rubbing method to form.
5. according to the manufacture method of claim 3 or 4 described semiconductor devices, wherein, described bonding agent is aqueous under 15～35 ℃ of conditions.
6. semiconductor device, it can utilize in the claim 3～5 manufacture method of each described semiconductor device to be made.
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