WO2010110069A1 - ダイボンディング用樹脂ペースト、それを用いた半導体装置の製造方法、及び半導体装置 - Google Patents

ダイボンディング用樹脂ペースト、それを用いた半導体装置の製造方法、及び半導体装置 Download PDF

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WO2010110069A1
WO2010110069A1 PCT/JP2010/054027 JP2010054027W WO2010110069A1 WO 2010110069 A1 WO2010110069 A1 WO 2010110069A1 JP 2010054027 W JP2010054027 W JP 2010054027W WO 2010110069 A1 WO2010110069 A1 WO 2010110069A1
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Prior art keywords
resin paste
resin
die bonding
semiconductor device
chip
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PCT/JP2010/054027
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English (en)
French (fr)
Japanese (ja)
Inventor
良史 杉浦
精吾 横地
修一 森
片山　陽二
隆史 堂々
哲 江花
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日立化成工業株式会社
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Priority to JP2011505970A priority Critical patent/JPWO2010110069A1/ja
Priority to KR1020117015583A priority patent/KR20120010220A/ko
Priority to CN2010800041529A priority patent/CN102272908A/zh
Publication of WO2010110069A1 publication Critical patent/WO2010110069A1/ja

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    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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    • C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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Definitions

  • the present invention is used as a bonding material (hereinafter referred to as a die bonding material) between a semiconductor chip (hereinafter also referred to as a chip) such as an IC or LSI and a support member of a lead frame or an insulating support substrate (hereinafter referred to as a substrate).
  • a bonding material hereinafter referred to as a die bonding material
  • a semiconductor chip hereinafter also referred to as a chip
  • a support member of a lead frame or an insulating support substrate hereinafter referred to as a substrate.
  • the present invention relates to a resin paste for die bonding, a semiconductor device manufacturing method using the same, and a semiconductor device.
  • Au—Si eutectic alloy, solder, silver paste, and the like are known as bonding materials between semiconductor elements such as IC and LSI and supporting members such as lead frames and insulating support substrates, that is, die bonding materials.
  • the Au—Si eutectic alloy has high heat resistance and moisture resistance, since it has a large elastic modulus, it tends to be easily broken when applied to a large chip. Further, the Au—Si eutectic alloy has a drawback that it is expensive.
  • solder is inexpensive, it is inferior in heat resistance, and its elastic modulus is as high as that of an Au—Si eutectic alloy, making it difficult to apply to a large chip.
  • silver paste (see, for example, Patent Document 1) is inexpensive, has high moisture resistance, has a lower elastic modulus than Au—Si eutectic alloy and solder, and has a thermocompression bonding wire bonder at 350 ° C. It has heat resistance that can be applied. Therefore, at present, silver paste is widely used among the above-described die bonding materials. However, it is difficult and efficient to spread the silver paste over the entire surface of the chip in response to the progress of high integration of ICs and LSIs and the accompanying increase in size of the chip. Absent.
  • a film-shaped die such as an adhesive film using a specific polyimide resin and an adhesive film for die bonding in which a conductive filler or an inorganic filler is added to a specific polyimide resin Bonding materials are known (see Patent Documents 2 to 4).
  • JP 2002-179769 A Japanese Patent Application Laid-Open No. 07-228697 Japanese Patent Laid-Open No. 06-145639 Japanese Patent Laid-Open No. 06-264035
  • the adhesive film type die bonding material can easily form a die bonding layer on a support substrate.
  • the adhesive film as disclosed in Patent Documents 2 to 4 can be suitably used for a support substrate such as 42 alloy lead frame (iron-nickel alloy), and has a good hot die shear strength. Are better.
  • a support substrate such as 42 alloy lead frame (iron-nickel alloy)
  • an adhesive device for cutting or punching the adhesive film into a chip size in advance and then attaching the adhesive film to the support substrate is required.
  • the method of punching the adhesive film and pasting a plurality of chips together tends to cause waste of the adhesive film.
  • the surface to which the adhesive film is applied has many irregularities, and voids are created when the adhesive film is applied, reducing the reliability of the semiconductor device. It tends to be easy.
  • the chip bonding method using the die bonding resin paste is, for example, that the die bonding resin paste applied to the substrate is B-staged, and then the chip is heated and pressure-bonded thereto to temporarily bond the chip and the substrate. In order to fix completely, it is common to post-cure at 180 degreeC for about 1 hour. Usually, if post-curing of the resin paste for die bonding is omitted, the adhesion between the chip and the substrate becomes insufficient, and there is a possibility that the chip vibrates and causes a defect in the wire bonding process. In the sealing process, if the adhesion between the chip and the substrate is insufficient, the chip may be peeled off due to the flow of the sealing material from the side surface of the chip.
  • a gap (hereinafter referred to as a void) may be generated between the layer of the die-bonding resin paste in a B-staged state and the chip when the chip is attached, and it is also desired that the void can be reduced.
  • the void is large, cracks are likely to occur in the die bonding material in the solder reflow process, which may reduce the reliability of the semiconductor device.
  • the resin paste for die bonding is excellent in die share strength during heating at 250 ° C. to 260 ° C. It is also required.
  • the present invention has been made in view of such circumstances, and in the B-stage, it has good adhesive strength with the chip in a wide temperature range, and can also reduce voids between the chip and solder reflow. It is an object of the present invention to provide a resin bonding for die bonding having a sufficient die shear strength during heating in the process. Another object of the present invention is to provide a method for manufacturing a semiconductor device using the die bonding resin paste. Furthermore, an object of the present invention is to provide a semiconductor device excellent in reliability using the die bonding resin paste.
  • the present invention adopts the following configuration. That is, in one embodiment of the present invention, a polymer (A) obtained by reacting a carboxyl group-containing butadiene polymer (a1) and an epoxy group-containing compound (a2), a thermosetting resin (B) and a filler ( C) containing resin paste for die bonding.
  • Another embodiment of the present invention relates to a method of manufacturing a semiconductor device using the die bonding resin paste, (1) a step of applying the die bonding resin paste on a substrate, and (2) drying the resin paste. And (3) a step of mounting a semiconductor chip on the B-staged resin paste, and a method of manufacturing a semiconductor device.
  • Another embodiment of the present invention relates to a method of manufacturing a semiconductor device using the die bonding resin paste, (1) a step of applying the die bonding resin paste on a substrate, and (2) drying the resin paste. And (3) a step of mounting a semiconductor chip on the B-staged resin paste.
  • Another embodiment of the present invention includes (1) a step of applying the die bonding resin paste on a substrate, (2) a step of mounting a semiconductor chip on the applied resin paste, and (3) sealing the semiconductor chip. And a step of sealing with an agent.
  • the disclosure of this specification relates to the subject matter included in Japanese Patent Application No. 2009-070531 (filed on Mar. 23, 2009), and is incorporated herein in its entirety with reference to these application specifications. .
  • the adhesive strength with the chip in the B-staging, can be reduced in a wide temperature range, the void between the chips can be reduced, and sufficient heat can be obtained in the solder reflow process. It is possible to provide a resin bonding for die bonding having a high die shear strength.
  • the post-curing after the chip is attached is omitted, there is no problem in the wire bonding and sealing process, so the manufacturing process can be shortened. is there.
  • the resin paste for die bonding according to an embodiment of the present invention is excellent in low-temperature adhesiveness, it is suitable for an insulating support substrate such as an organic substrate as a die bonding material. Moreover, according to one embodiment of the present invention, a method of manufacturing a semiconductor device having excellent workability can be provided by using the die bonding resin paste of the present invention. Furthermore, according to one embodiment of the present invention, a semiconductor device having excellent reliability can be provided by using the die bonding resin paste of the present invention.
  • FIG. 1 is a diagram showing an example of a manufacturing process of a semiconductor device of the present invention.
  • FIG. 2 is a cross-sectional view of a BOC which is an example of the semiconductor device of the present invention.
  • FIG. 3 is a cross-sectional view of an embodiment of a lead frame type semiconductor device which is an example of the semiconductor device of the present invention.
  • B-stage is to heat-treat the die bonding resin paste and volatilize the solvent (D), and to dry the applied die bonding resin paste. This means that the die bonding resin paste is not completely cured. Complete curing is defined as a state where there is no endothermic peak in the range of 80 to 180 ° C (temperature increase rate: 10 ° C / min) in DSC (Differential Scanning Calorimetry) measurement. is there.
  • the resin paste for die bonding according to the present invention (hereinafter sometimes simply referred to as “resin paste”) is obtained by reacting a butadiene polymer (a1) having a carboxyl group with a compound (a2) having an epoxy group.
  • a polymer (A), a thermosetting resin (B), and a filler (C) are included.
  • the butadiene polymer having a carboxyl group (hereinafter sometimes abbreviated as component (a1)) is not particularly limited as long as it has a polybutadiene structure and a carboxyl group.
  • component (a1)) a copolymer of a polybutadiene structure derived from butadiene and a compound having a carboxyl group may be used.
  • the main chain may be a copolymer of butadiene and another polymerizable compound such as acrylonitrile, and at least one of its terminals may have a carboxyl group.
  • the number average molecular weight of component (a1) is preferably 500 to 10,000, and more preferably 1000 to 7000.
  • the component (a1) is more preferably a butadiene-acrylonitrile copolymer having a carboxyl group represented by the following general formula (1).
  • x / y is 95/5 to 50/50, and n is an integer of 5 to 50.
  • the compound represented by the general formula (1) can also be obtained as a commercial product.
  • Examples of the butadiene-acrylonitrile copolymer having a carboxyl group represented by the general formula (1) include Hycar CTBN-2009 ⁇ 162, CTBN-1300 ⁇ 31, CTBN-1300 ⁇ 8, CTBN-1300 ⁇ 13, CTBNX-1300 ⁇ 9 (all manufactured by Ube Industries, Ltd.) is available as a commercial product.
  • a low molecular weight liquid polybutadiene having a carboxyl group NISSO-PB-C-2000 (manufactured by Nippon Soda Co., Ltd., trade name) (manufactured by Nippon Soda Co., Ltd.) , Product name) and the like.
  • Compound having epoxy group (a2) Although it does not specifically limit as a compound (henceforth abbreviated as component (a2)) which has an epoxy group,
  • component (a2) ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol di
  • Glycidyl ether type epoxy compounds such as glycidyl ether and glycerin triglycidyl ether
  • Glycidyl ester type epoxy compounds using polyvalent carboxylic acids such as dimer acid and anhydrides as raw materials
  • Glycidyl amine type epoxy compounds using aliphatic amines as raw materials, etc.
  • Aliphatic epoxy compounds hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, resorcinol, methylresorcinol, catechol, methylcateco , Biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3 , 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxy Phenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4
  • a phenol glycidyl ether type epoxy resin can also be used.
  • resins include bisphenol A, bisphenol AD, bisphenol S, bisphenol F, or a condensate of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, and bisphenol A novolac resin.
  • a glycidyl ether etc. are mentioned. These can be used alone or in combination of two or more.
  • an epoxy compound represented by the following general formula (2) is particularly preferable from the viewpoint of the strength of the resin.
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m and n each independently represents an integer of 1 to 4.
  • n is 2 or more
  • a plurality of R 1 may be the same or different
  • m is 2 or more
  • a plurality of R 2 may be the same or different.
  • the polymer (A) is obtained by reacting the component (a1) and the component (a2).
  • the compounding ratio is 0.01 or more with respect to 1 carboxylic acid equivalent of the component (a1)
  • the epoxy equivalent of the component (a2) is 0.01 or more considering the adhesive strength, and the difficulty of peeling due to outgas generation is considered. It is preferably 10 or less, more preferably 0.1 to 2, and particularly preferably 0.25 to 1.
  • the viscosity of the polymer (A) can be adjusted by the reaction temperature and reaction time during synthesis, and the viscosity tends to increase by increasing the reaction temperature or increasing the reaction time.
  • a suitable viscosity of the polymer (A) is 150 Pa ⁇ s or more, more preferably 300 to 900 Pa ⁇ s, and particularly preferably 500 to 700 Pa ⁇ s from the viewpoint of improving the adhesive strength.
  • the adhesive strength when the resin paste is obtained is further improved. It is preferable from the viewpoint of improvement, and when it is 900 Pa ⁇ s or less, workability is improved when a resin paste is used.
  • the weight average molecular weight of the polymer (A) is preferably 5000 or more, more preferably 15000 to 70000, and particularly preferably 17000 to 40000.
  • the weight average molecular weight is 5000 or more, the adhesive strength is excellent, and when it is less than 70000, the workability when the resin paste is obtained can be further improved.
  • a weight average molecular weight (Mw) and a number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC) (converted with a calibration curve using standard polystyrene).
  • the acid value of the polymer (A) is preferably 10 to 25 mgKOH / g, and more preferably 15 to 23 mgKOH / g. When the acid value is 10 to 25 mg KOH / g, the workability when the resin paste is obtained can be further improved.
  • the acid value of the polymer (A) can be measured by the following method. First, about 1 g of the resin solution of polymer (A) is precisely weighed, 30 g of acetone is added to the resin solution, and the resin solution is uniformly dissolved.
  • the content of the component (A) is preferably 50 to 99% by weight in the total amount of the component (A) and the component (B) from the viewpoint of stress relaxation between the substrate and the chip and the adhesive strength. More preferably, it is ⁇ 97 wt%, particularly preferably 80 to 95 wt%.
  • thermosetting resin (B) Although it does not specifically limit as a thermosetting resin (B), for example, the imide compound etc. which have an epoxy resin, a phenol resin, and at least 2 thermosetting imide group in 1 molecule are mentioned. These are used singly or in combination of two or more.
  • the epoxy resin contains at least two epoxy groups in the molecule, and phenol glycidyl ether type epoxy resin is preferred from the viewpoint of hot die shear strength.
  • phenol glycidyl ether type epoxy resin is preferred from the viewpoint of hot die shear strength.
  • resins include bisphenol A, bisphenol AD, bisphenol S, bisphenol F, or a condensate of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, and bisphenol A novolac resin.
  • a glycidyl ether etc. are mentioned. These are used singly or in combination of two or more.
  • the content is preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight with respect to 100 parts by weight of the polymer (A), from the viewpoint of die shear strength during heating. 3 to 20 parts by mass is particularly preferable.
  • the phenol resin has at least two phenolic hydroxyl groups in the molecule, and examples thereof include phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, poly-p-vinylphenol, phenol aralkyl resin and the like. It is done. These are used singly or in combination of two or more.
  • the content in the case of using the phenol resin is preferably 0.5 to 100 parts by mass with respect to 100 parts by weight of the polymer (A) in consideration of hot die shear strength and semiconductor package reliability.
  • the amount is more preferably 50 parts by mass, and particularly preferably 2 to 20 parts by mass.
  • thermosetting imide groups in one molecule examples include orthobismaleimide benzene, metabismaleimide benzene, parabismaleimide benzene, and 1,4-bis (p-maleimide cumyl). Examples thereof include benzene and 1,4-bis (m-maleimidocumyl) benzene. These are used singly or in combination of two or more.
  • X ′ and Y represent O, CH 2 , CF 2 , SO 2 , S, CO, C (CH 3 ) 2 or C (CF 3 ) 2 ;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine;
  • D is a dicarboxylic acid having an ethylenically unsaturated double bond Represents a residue;
  • m ′ represents an integer of 0 to 4;
  • the content when the imide compound is used is more preferably less than 100 parts by weight with respect to 100 parts by weight of the polymer (A).
  • Examples of the imide compound of formula (I) include 4,4-bismaleimide diphenyl ether, 4,4-bismaleimide diphenylmethane, 4,4-bismaleimide-3,3′-dimethyl-diphenylmethane, and 4,4-bismaleimide.
  • Examples of the imide compound of the formula (II) include bis [4- (4-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] methane, and bis [4- (4-maleimidophenoxy).
  • Phenyl] fluoromethane bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4 -(4-maleimidophenoxy) phenyl] ketone, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [ 4- (4-maleimidophenoxy) phenyl] propane and the like.
  • a radical polymerization agent may be used.
  • the radical polymerization agent include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like.
  • the content is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the imide compound.
  • the content of the thermosetting resin as the component (B) is the above component (A) from the viewpoint of improving the wetting and spreading of the die bonding layer at the time of chip thermocompression bonding when the B-staging is performed at a relatively high temperature.
  • It is preferably 1 to 100 parts by weight, more preferably 3 to 30 parts by weight, and particularly preferably 5 to 20 parts by weight with respect to 100 parts by weight.
  • Filler (C) examples include, but are not limited to, conductive fillers such as silver powder, gold powder, and copper powder; inorganic fillers such as silica, alumina, titania, glass, iron oxide, and ceramic; Can be mentioned. These are used singly or in combination of two or more.
  • conductive fillers such as silver powder, gold powder, and copper powder can improve the conductivity and heat conductivity of the die bonding material and the thixotropy of the resin paste.
  • inorganic fillers such as silica, alumina, titania, glass, iron oxide, and ceramic can improve the low thermal expansion, low moisture absorption, and thixotropy of the die bonding material.
  • silica is generally preferred from the viewpoint of semiconductor package reliability.
  • the filler (C) preferably has an average particle size of 0.001 ⁇ m to 10 ⁇ m, more preferably 0.005 to 5 ⁇ m, and preferably 0.01 to 1 ⁇ m. Particularly preferred.
  • An inorganic ion exchanger may be added as a filler (C) that improves the electrical reliability of the semiconductor device.
  • the inorganic ion exchanger include ions extracted into an aqueous solution when the cured resin paste is extracted in hot water, for example, ions such as Na + , K + , Cl ⁇ , F ⁇ , RCOO ⁇ and Br ⁇ . Those having a capturing action are effective.
  • Examples of such ion exchangers include naturally produced zeolites, natural minerals such as zeolites, acid clay, dolomite, hydrotalcites, and artificially synthesized synthetic zeolites.
  • conductive fillers or inorganic fillers can be used in combination of two or more. As long as the physical properties are not impaired, one or more conductive fillers and one or more inorganic fillers may be mixed and used.
  • the content of the filler (C) is preferably 1 part by weight or more when considering the thixotropy index (1.5 or more) of the resin paste with respect to 100 parts by weight of the polymer (A), and the adhesive strength and the elasticity of the cured product.
  • it is preferably 100 parts by mass or less. More preferably, it is 2 to 50 parts by mass, and particularly preferably 3 to 30 parts by mass.
  • it is preferable that it is 10 mass parts or more from a viewpoint which can suppress the wetting spread of the die-bonding layer at the time of subsequent chip
  • the mixing and kneading of the filler (C) is carried out by appropriately combining dispersers such as a normal stirrer, raky machine, three rolls, and ball mill.
  • the resin paste of the present invention may contain a solvent (D).
  • the solvent (D) is preferably selected from organic solvents that can uniformly knead or disperse the filler. It is preferable to select an organic solvent having a boiling point (atmospheric pressure) of 100 ° C. or more and less than 250 ° C. in consideration of prevention of volatilization of the organic solvent at the time of printing and drying property in B-stage.
  • organic solvents examples include N-methyl-2-pyrrolidinone, diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), diethylene glycol diethyl ether, 2- (2-methoxyethoxy) ethanol, ⁇ -butyrolactone, isophorone, carbitol, carbitol acetate, 1,3-dimethyl-2-imidazolidinone, 2- (2-butoxyethoxy) ethyl acetate, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, anisole And solvents mainly composed of petroleum distillates. These are used singly or in combination of two or more.
  • carbitol acetate is particularly preferred because of its low water absorption.
  • the content in the case of using the solvent (D) is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of printability. It is preferably 30 to 80 parts by mass.
  • thermosetting resin (B) is liquid at room temperature from the viewpoint of printability.
  • the resin paste of the present invention preferably contains a curing accelerator (E).
  • the curing accelerator (E) can accelerate the curing of the thermosetting resin (B). This is particularly effective when an epoxy resin is used as the thermosetting resin (B).
  • curing accelerator (E) examples include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo. (5,4,0) undecene-7-tetraphenylborate and the like. You may use these individually by 1 type or in combination of 2 or more types.
  • the content is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the thermosetting resin (B), and is 20 parts by mass or less in consideration of storage stability of the resin paste.
  • the resin paste of the present invention includes an antifoaming agent, an antifoaming agent, an antifoaming agent, a silane coupling agent, a titanium coupling agent, a nonionic surfactant, and a fluorine surfactant as necessary.
  • Various additives such as a silicone plasticizer can also be added.
  • Each of the above components can be mixed and stirred for 10 minutes at a blade of 10 rpm using, for example, a kneading machine such as a Hibis Disper mix to obtain a resin paste.
  • the elastic modulus after curing of the resin paste (when cured at 180 ° C. for 1 hour at a thickness of 100 ⁇ m), that is, the elastic modulus of the resin paste cured product, is considered to be difficult to shift between the substrate and the chip and the assembly workability.
  • 1 MPa or more is preferable, and considering the stress relaxation property between the substrate and the chip and the temperature cycle resistance of the semiconductor package, 300 MPa or less is preferable.
  • the elastic modulus is a value of 25 ° C. when the storage elastic modulus E ′ of the cured resin paste after drying and curing is measured with a dynamic viscoelasticity measuring device.
  • “After drying and curing” means after the resin component is completely cured, for example, by applying a resin paste, forming a B-stage, and then heating at 180 ° C. for 1 hour with a dryer or the like.
  • the solid content concentration of the resin paste is preferably 20 to 95% by weight, more preferably 40 to 90% by weight or more, and particularly preferably 60 to 80% by weight.
  • the solid content is 20% by weight or more, it is preferable from the viewpoint of shape change suppression based on volume reduction after drying the resin paste, and when it is 95% by weight or less, the fluidity and printing workability of the resin paste can be further improved.
  • the thixotropy index of the resin paste is preferably 1.5 to 10.0, more preferably 2.0 to 7.0, and particularly preferably 3.0 to 5.0.
  • the thixotropy index of the resin paste is 1.5 or more, it is preferable from the viewpoint of suppressing the occurrence of sagging or the like in the resin paste supplied and applied by the printing method and maintaining a good printed shape.
  • the thixotropy index is preferably 10.0 or less from the viewpoint of suppressing the occurrence of “chips” and / or scum in the resin paste supplied and applied by the printing method.
  • the viscosity (25 ° C.) of the resin paste is preferably 5 to 1000 Pa ⁇ s, more preferably 20 to 500, and particularly preferably 50 to 200 Pa ⁇ s.
  • the viscosity of the resin paste is preferably 5 to 1000 Pa ⁇ s from the viewpoint of printability.
  • the viscosity of the resin paste is preferably adjusted as appropriate according to the type of printing method. For example, when a mesh or the like is stretched on the mask opening, such as a screen mesh plate, the viscosity of the mesh paste is taken into consideration.
  • the range is preferably from 100 to 100 Pa ⁇ s. In the case of a stencil plate or the like, it is preferably adjusted to a range from 20 to 500 Pa ⁇ s.
  • the above viscosity is a value measured at 25 ° C. and a rotation speed of 0.5 rpm using an E-type viscometer.
  • FIG. 1 is a schematic view showing an example of a manufacturing process of a semiconductor device.
  • the resin paste of the present invention is printed on a substrate.
  • printed materials include lead frames such as 42 alloy lead frames and copper lead frames; or plastic films such as polyimide resins, epoxy resins and polyimide resins; and polyimide resins and epoxy resins on substrates such as glass nonwoven fabrics.
  • Insulating support substrate made of ceramics such as alumina, or impregnated / cured plastic such as polyimide resin.
  • the printing method include a screen printing method.
  • a resin paste 104 of the present invention may be applied to a substrate 101 through a metal mask 102 using a squeegee 103.
  • the applied resin paste is heat treated to dry the solvent (B-stage), and a B-staged die bonding layer is obtained (FIG. 1B).
  • a support substrate on which a layer of a resin paste in a B-stage state (hereinafter referred to as a die bonding layer) is obtained.
  • the temperature for forming the B stage is preferably 100 to 200 ° C, more preferably 120 to 180 ° C.
  • the time for forming the B stage is preferably 120 minutes or less from the viewpoint of work efficiency, and when the solvent (D) is used, it is preferably 5 minutes or more from the viewpoint of increasing the volatility.
  • a semiconductor element such as an IC or LSI is attached to the support substrate on which the die bonding layer is formed, and the chip is pressure-bonded to the support substrate by heating.
  • the die bonding layer side of the substrate may be attached to a chip 107 placed on the heat source 106.
  • the heating temperature is preferably 200 ° C. or less from the viewpoint of heat resistance of the organic substrate, and preferably from 100 to 200 ° C. from the viewpoint of adhesive strength.
  • a cured die bonding layer 108 is obtained, and the chip is mounted on the support substrate (FIG. 1 (d)).
  • the post-curing of the die bonding layer may be performed together with the post-curing process of the sealing material.
  • the problem in the mounting assembly process mentioned here is that the chip and the substrate are not sufficiently fixed, and the chip vibrates during the wire bonding process, causing problems in the wire bonding, or in the sealing process. It means that the chip is peeled off due to the flow of the sealing material from the side surface of the chip because the chip is insufficiently fixed on the substrate.
  • the substrate and the chip may be electrically connected by a wire 109 (FIG. 1 (e)).
  • the substrate on which the chip is mounted may be placed in the mold, and the mold 110 may be filled with the sealing material 112 by the extruder 111 and sealed (FIG. 1 (f)).
  • the method for manufacturing a semiconductor device according to the present invention may include the above steps, and the semiconductor device according to the present invention can be manufactured by a manufacturing method including the above steps.
  • FIG. 2 is a schematic cross-sectional view showing the structure of a BOC type semiconductor device which is an embodiment of the semiconductor device according to the present invention.
  • a semiconductor element 6 is mounted on one surface of a substrate 2 having a window at the center via a die bonding layer 4, and a wiring pattern 8 is formed on the opposite surface of the substrate 2 to the semiconductor element mounting surface.
  • An insulating layer 10 and solder balls 12 are formed, terminal portions (not shown) of the semiconductor element 2 and the wiring pattern 8 are connected by wires 14, and at least the connecting portions are sealed by a sealing material 16 such as resin.
  • a sealing material 16 such as resin
  • the resin paste according to the present invention is not limited to the manufacture of the BOC type semiconductor device, but can be suitably used in the manufacture of a semiconductor device having other configurations (for example, the lead frame type semiconductor device shown in FIG. 3). It is.
  • the silicon chip 201 is fixed to the lead frame 203 with a resin paste 202, and the Al pad 204 on the silicon chip and the Ag plating 205 on the lead frame are electrically connected by a gold wire 206. Connected to. These are sealed with a sealing resin 207, and external plating 208 is applied to the end of the lead frame protruding outward.
  • the resin paste contains a solvent, but when used in a method for manufacturing a semiconductor device, most of the solvent is volatilized by being B-staged in the drying process, so there are few voids in the die bonding layer. A semiconductor device having good mounting reliability can be assembled.
  • the semiconductor element is pasted without using the B stage, and then the chip is bonded to the support substrate by heating. You can also. Furthermore, it is possible to omit the curing step of the sealant. Furthermore, it is possible to omit both the B-stage and the sealing agent curing step.
  • another method for manufacturing a semiconductor device includes the steps of applying a predetermined amount of the resin paste on a substrate, mounting a chip on the resin paste, and curing the resin in the resin paste.
  • another semiconductor device according to the present invention is manufactured by a manufacturing method including the above steps.
  • the measuring method of viscosity is as follows.
  • the viscosity of the resin paste at 25 ° C. was measured using a 19.4 mm diameter, 3 ° cone with an E-type viscometer manufactured by Toki Sangyo Co., Ltd. (0.5 rpm).
  • the molecular weight was measured using GPC under the following conditions.
  • thermosetting resin (B) 4.7 parts by weight of an epoxy resin (trade name: YDCN-700-7, manufactured by Toto Kasei Co., Ltd.) and a phenol resin (trade name: TrisP-PA-MF, Honshu) are used as the thermosetting resin (B).
  • B thermosetting resin
  • Example 2 A resin paste was obtained in the same manner as in Example 1 except that the types and contents of the base resin, the curing accelerator, and the filler were changed as shown in Table 1.
  • Table 2 shows the solid content concentration, viscosity, and thixotropy index of the resin pastes obtained in Examples 2 to 7 and Comparative Example 1.
  • each of the resin pastes of Examples 1 to 7 and Comparative Example 1 was performed under the condition that the set temperature for the B stage was changed to 140 ° C., 145 ° C., 150 ° C., 155 ° C., 160 ° C., 165 ° C. and 170 ° C.
  • the shear strength (kgf / chip) at 180 ° C. was measured. The results are shown in Table 3.
  • the resin pastes of Examples 1 to 7 and Comparative Example 1 were printed on a 42 alloy lead frame at 3 mm ⁇ 10 mm and a thickness of 100 ⁇ m.
  • the B stage was set to 135 ° C. to make a B stage.
  • the B-stage condition is that the temperature is raised from 40 ° C. to 135 ° C. in 30 minutes with a hot air dryer, dried at 135 ° C. for 30 minutes, and then lowered from 135 ° C. to 40 ° C. in 30 minutes.
  • a coating film (die bonding layer) was formed. Thereafter, a transparent glass plate was pressure-bonded on the die bonding layer for 1 second on a 140 ° C. heating plate with a load of 5 kg. This was heat-pressed under conditions of 180 ° C. and 4 MPa for 90 seconds, and voids were visually evaluated according to the following criteria.
  • each of the resin pastes of Examples 1 to 7 and Comparative Example 1 was performed under the condition that the set temperature for the B stage was changed to 140 ° C., 145 ° C., 150 ° C., 155 ° C., 160 ° C., 165 ° C. and 170 ° C. Similarly, the voids were visually evaluated. The results are shown in Table 3.
  • A Void area is less than 5% with respect to the bonding area between the die bonding layer and the glass substrate.
  • B Void area is 5% or more with respect to the bonding area between the die bonding layer and the glass substrate.
  • a B-staging temperature range in which the adhesive strength was 0.1 MPa or more and the void evaluation was “A” was defined as the B-staging temperature tolerance. The results are shown in Table 3. It means that it is excellent, so that B stage-izing temperature tolerance is large.
  • the adhesive strength is 0.1 MPa or more
  • the subsequent assembly process that is, wire bonding and sealing can be performed even if the post-curing process is omitted.
  • the package substrate for evaluation was prepared by applying for 1 second.
  • Each of the obtained package substrates for evaluation was sealed using a transfer molding machine (transfer press manufactured by Towa Seiki Co., Ltd.) (sealing agent; product name: CEL-9240HF-SI (manufactured by Hitachi Chemical Co., Ltd.)) Sealing conditions; mold temperature: 180 ° C., pressure: 6.9 MPa, molding time: 90 seconds).
  • the sealing material was heated and cured in a hot air dryer at 175 ° C. for 5 hours to obtain a BOC package for evaluation of 10.1 mm ⁇ 12.2 mm ⁇ 1.0 mmt.
  • the obtained evaluation BOC package was subjected to moisture absorption under the conditions of 85 ° C./85% RH / 168 hours and 85 ° C./60% RH / 168 hours, respectively, and then the maximum surface temperature of the evaluation BOC package was 260 ° C. And passed through an IR reflow furnace (made by TAMURA) set to reach 3 times.
  • SAT Scanning Automatic Tomography, HYE-FOCUS manufactured by Hitachi, Ltd.
  • the reflow resistance was evaluated. The results are shown in Table 3.
  • Level 1 No peeling of the die-bonding layer or bubbles in both conditions of 85 ° C./85% RH / 168 hours and 85 ° C./60% RH / 168 hours.
  • Level 1 means better reflow resistance than Level 2.
  • YDCN-700-7 Toto Kasei Co., Ltd., cresol novolac type epoxy resin (epoxy equivalent: 197-207 g / eq)
  • TrisP-PA Honshu Chemical Industry Co., Ltd. (4- [4- [1,1-bis (4-hydroxyphenyl) ethyl] - ⁇ , ⁇ -dimethylbenzyl] phenol)
  • TPPK Tokyo Chemical Industry Co., Ltd., Tetraphenylphosphonium Tetraphenylborate 2P4MHZ: Shikoku Chemical Industry Co., Ltd. (2-phenyl-4-methyl-5-hydroxymethylimidazole)
  • Aerosil # 50 Nippon Aerosil Co., Ltd. (silica fine powder, average particle size 0.03 ⁇ m)
  • CA carbitol acetate
  • the resin paste for die bonding of the present invention is excellent in adhesive strength with a chip in a wide temperature range in B-stage, and can reduce voids between the chips, and in the solder reflow process, Excellent reflow resistance.
  • the present invention it is possible to provide a die bonding resin paste that can be easily supplied and applied by a printing method to a substrate on which a semiconductor chip needs to be attached at a relatively low temperature.

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PCT/JP2010/054027 2009-03-23 2010-03-10 ダイボンディング用樹脂ペースト、それを用いた半導体装置の製造方法、及び半導体装置 WO2010110069A1 (ja)

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JP2018172695A (ja) * 2016-06-02 2018-11-08 日立化成株式会社 樹脂組成物及び積層体の製造方法
US11024598B2 (en) 2016-08-22 2021-06-01 Senju Metal Industry Co., Ltd. Metallic sintered bonding body and die bonding method

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WO2017002315A1 (ja) * 2015-06-29 2017-01-05 タツタ電線株式会社 放熱材料接着用組成物、接着剤付放熱材料、インレイ基板、及びその製造方法
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