JP2009256587A - Adhesive for sealing semiconductor, film-like adhesive for sealing semiconductor, manufacturing method for semiconductor apparatus, and semiconductor apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive for sealing a semiconductor capable suppressing generation of a void even when connection is performed at a high temperature of 300°C or higher in which a manufactured semiconductor has excellent connection reliability, and to provide a film-like adhesive for sealing a semiconductor using it, a manufacturing method for a semiconductor apparatus, and a semiconductor apparatus. <P>SOLUTION: The adhesive for sealing the semiconductor contains a compound formed by an epoxy resin (a), an organic acid (b) capable of reacting with the epoxy resin and a curing promoter. The adhesive further contains a polymer component (c) having a weight average molecular weight of 10,000 or more. The polymer component further contains a polyimide (d). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a semiconductor sealing adhesive, a semiconductor sealing film adhesive, a semiconductor device manufacturing method, and a semiconductor device.

  Up to now, as a method for manufacturing a semiconductor device, a wire bonding method using a fine metal wire such as a gold wire has been widely applied to connect a semiconductor chip and a substrate. On the other hand, in recent years, in order to meet the demands for miniaturization, thinning, and high functionality of semiconductor devices, flip chip connection methods in which conductive protrusions called bumps are formed on a semiconductor chip and directly connected to a substrate electrode are becoming widespread.

  Known flip-chip connection methods include metal bonding using solder, tin, etc., metal bonding by applying ultrasonic vibration, and method of maintaining mechanical contact by the shrinkage force of the resin. From the viewpoint of the reliability of the connecting portion, a method of metal joining using solder or tin is common.

  In particular, in liquid crystal display modules, which have been especially miniaturized and highly functional in recent years, a semiconductor chip for driving a liquid crystal in which gold bumps are formed on a polyimide substrate on which tin-plated wiring is formed is bonded to a metal by gold-tin eutectic. A semiconductor device called COF (Chip On Film) is used.

  In the case of COF, in order to form a gold-tin eutectic, it is necessary to set the connecting portion to 278 ° C. or higher which is the eutectic temperature. Furthermore, from the viewpoint of improving productivity, the connection time is required to be short, for example, 5 seconds or less. Therefore, in order to heat to the eutectic temperature or higher in a short time, the set temperature of the manufacturing apparatus needs to be a high temperature of 300 to 450 ° C.

  In COF, the gap between the semiconductor chip and the substrate is sealed with a resin in order to protect the connection from the external environment, prevent external stress from concentrating on the connection, and ensure insulation reliability between narrow pitch wiring. It is necessary to fill (see Patent Document 1). As a current sealing and filling method, a method in which a liquid resin is injected and hardened by capillary action after connecting a semiconductor chip and a substrate is generally used, but a reduction in the gap between the chip and the substrate due to narrow pitch connection. Therefore, it takes a long time for the injection, and there is a concern that productivity is lowered.

  As a method of solving this concern, a method of connecting the chip and the substrate after supplying an adhesive to the chip or the substrate can be considered.

JP 2006-188573 A

  However, when COF is connected by this method, the volatile component of the adhesive foams due to the high temperature of 300 ° C. or higher at the time of connection, and bubbles called voids tend to be generated. Since voids cause a decrease in insulation reliability between narrow pitch wirings, suppression of voids has been an issue.

  Therefore, in order to solve the above problems, the present invention can suppress the generation of voids even when connection is performed at a high temperature of 300 ° C. or higher, and the manufactured semiconductor has excellent connection reliability (low connection resistance). An object of the present invention is to provide a semiconductor sealing adhesive having high insulation reliability), a semiconductor sealing film adhesive using the same, a semiconductor device manufacturing method, and a semiconductor device.

  In view of the above circumstances, the present invention provides an adhesive for semiconductor encapsulation containing a compound formed from (a) an epoxy resin, and (b) an organic acid that reacts with the epoxy resin and a curing accelerator.

  According to such a semiconductor sealing adhesive, the generation of voids can be suppressed even when the connection is performed at a high temperature of 300 ° C. or higher, and the manufactured semiconductor has excellent connection reliability. The reason why such an effect can be obtained by the semiconductor sealing adhesive of the present invention is not necessarily clear, but the present inventors consider as follows.

That is, (b) an adhesive including a compound formed from an organic acid that reacts with an epoxy resin and a curing accelerator has a lower viscosity than an adhesive including a normal curing accelerator (organic acid and curing Compounds formed from accelerators have a higher melting point than curing accelerators that do not contain organic acids). Therefore, good results can be obtained with respect to ensuring initial conduction of the semiconductor device, embedding between narrow pitch wirings, and the like.
In addition, (b) the compound formed from the organic acid that reacts with the epoxy resin and the curing accelerator reaches the active region in a short time when the bump and the wiring are connected, and thus exhibits immediate curing. Increases viscosity and eliminates the cause of voids such as springback.
Furthermore, at the time of connection, (b) the organic acid is liberated from the compound formed from the organic acid that reacts with the epoxy resin and the curing accelerator, so that the metal (wiring, bump, etc.) is dissolved, or the conductive material is removed. If formed or decomposed by heat, the HAST resistance may be reduced. On the other hand, when an organic acid that reacts with an epoxy resin is used, the organic acid reacts with the epoxy resin in the system and is taken into the reaction system, so that the problem of reduced HAST resistance can be solved. The present inventors are thinking.

  It is preferable that the adhesive for semiconductor encapsulation of the present invention further contains (c) a polymer component having a weight average molecular weight of 10,000 or more.

  (C) The polymer component having a weight average molecular weight of 10,000 or more preferably includes (d) a polyimide resin, and the (d) polyimide resin has a weight average molecular weight of 30,000 or more and a glass transition temperature of 100 ° C. or less. preferable.

  (A) The epoxy resin is preferably solid at 1 atm and 25 ° C. (room temperature). When an epoxy resin that is solid at room temperature is used, generation of volatile components (voids) due to decomposition of the epoxy resin during high-temperature heating can be prevented. For the same reason, the compound formed from (b) the organic acid that reacts with the epoxy resin and the curing accelerator is preferably solid at 1 atm and 25 ° C.

  (B) The melting point of the compound formed from the organic acid that reacts with the epoxy resin and the curing accelerator is preferably 120 ° C. or higher.

Moreover, it is preferable that the active region of the compound formed from (b) the organic acid that reacts with the epoxy resin and the curing accelerator is 120 ° C. or higher.
The “active region” refers to the exothermic peak temperature when the temperature is raised by mixing an epoxy resin and a curing accelerator (the temperature with the highest calorific value). For example, a differential scanning calorimeter (manufactured by PERKIN-ELMER, DSC7, heating rate: 10 ° C./min).

  The organic acid is preferably an acid having a carboxyl group, and more preferably trimellitic acid.

  The curing accelerator is preferably an imidazole.

  The adhesive for semiconductor sealing of the present invention preferably has a melt viscosity at 350 ° C. or higher of 250 Pa · s or lower and a void generation rate of 5% or lower when pressed at 350 ° C. for 5 seconds or longer.

  The film-like adhesive for semiconductor sealing of the present invention is formed by forming the adhesive for semiconductor sealing of the present invention into a film. According to such a film-like adhesive for semiconductor sealing, since the adhesive for semiconductor sealing of the present invention is used, generation of voids can be suppressed even when connection is performed at a high temperature of 300 ° C. or higher, In addition, the manufactured semiconductor has excellent connection reliability.

The method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device comprising a semiconductor chip having bumps and a substrate having metal wiring, wherein the semiconductor chip and the substrate are bonded to the semiconductor sealing adhesive of the present invention. Or it arrange | positions so that a bump and metal wiring may mutually oppose through the film-form adhesive for semiconductor sealing, and it pressurizes and heats a semiconductor chip and a board | substrate and opposes a semiconductor sealing adhesive or semiconductor A sealing film-like adhesive is cured, and a connecting step for electrically connecting the bump and the metal wiring is provided. In the connecting step, the semiconductor chip and the substrate are pressed in the opposing direction and heated to 300 ° C. or more to form a gold-tin eutectic between the bump containing gold and the metal wiring having the tin plating layer. In addition, it is preferable to electrically connect the bump and the metal wiring.
According to this method for manufacturing a semiconductor device, since the film-like adhesive for sealing a semiconductor of the present invention is used, a semiconductor device having excellent connection reliability can be manufactured.

  The semiconductor device of the present invention is manufactured by the manufacturing method of the present invention. Since this semiconductor device is manufactured by the manufacturing method of the present invention, it has excellent connection reliability.

  ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it connects at the high temperature of 300 degreeC or more, generation | occurrence | production of a void can be suppressed, and the semiconductor sealing adhesive with which the manufactured semiconductor has the outstanding connection reliability, and it It is possible to provide a film-like adhesive for sealing a semiconductor using the above, a method for manufacturing a semiconductor device, and a semiconductor device.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

  The adhesive for semiconductor encapsulation of the present invention contains a compound formed from (a) an epoxy resin, and (b) an organic acid that reacts with the epoxy resin and a curing accelerator. Further, the semiconductor sealing adhesive of the present invention preferably contains (c) a polymer component having a weight average molecular weight of 10,000 or more, more preferably (d) a polyimide resin. Hereinafter, each component will be described.

(A) Epoxy resin (a) The epoxy resin is not particularly limited as long as it has two or more epoxy groups in the molecule. For example, bisphenol A type, bisphenol F type, naphthalene type, phenol novolac type, cresol A novolac type, a phenol aralkyl type, a biphenyl type, a triphenylmethane type, a dicyclopentadiene type, various polyfunctional epoxy resins, and the like can be used. These can be used individually by 1 type or in mixture of 2 or more types.
For example, bisphenol A type and bisphenol F type liquid epoxy resins have a 1% thermogravimetric temperature reduction temperature of 250 ° C. or less, and may decompose during high temperature heating to generate volatile components. It is desirable to use an epoxy resin.

(B) Compound formed from organic acid that reacts with epoxy resin and curing accelerator (b) Compound formed from organic acid that reacts with epoxy resin and curing accelerator, for example, reacts with epoxy resin Examples thereof include a salt of an organic acid and a curing accelerator, and an adduct of an organic acid that reacts with an epoxy resin and a curing accelerator. (B) The compound formed from the organic acid that reacts with the epoxy resin and the curing accelerator has a melt viscosity at 350 ° C. or higher and 250 Pa · s or lower, depending on the composition of the semiconductor sealing adhesive, and 350 It is more desirable to select the void generation rate to be 5% or less when pressed at 5 ° C. for 5 seconds or more.

  Any organic acid may be used as long as it reacts with the epoxy resin. For example, an acid having a carboxyl group, phenol, enol, alcohol, thiol, sulfonic acid, or the like can be used. Among them, an acid having a carboxyl group is preferable, an acid having a plurality of carboxyl groups is more preferable, and trimellitic acid is particularly preferable in that it easily reacts with an epoxy resin and has a low influence on HAST resistance reduction.

Any curing accelerator may be used as long as it forms a salt or an adduct with an organic acid. For example, phosphines, imidazoles, and triazines can be used.
Examples of imidazoles include 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, and 2-methylimidazole.

(B) Specific examples of compounds formed from an organic acid that reacts with an epoxy resin and a curing accelerator include 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. Salt. Moreover, the salt and adduct of the adduct of an epoxy resin and imidazoles, and an organic acid can also be used. Among these, 1-cyanoethyl-2-undecylimidazolium trimellitate, which is a salt of imidazoles and trimellitic acid, from the viewpoint of curability, storage stability, and organic acid easily react with epoxy resin. -Cyanoethyl-2-phenylimidazolium trimellitate is preferred. These can be used individually by 1 type or in mixture of 2 or more types.
Moreover, you may use what microencapsulated these and raised the potential.

  The compounding amount of the compound formed from (b) the organic acid that reacts with the epoxy resin and the curing accelerator in the semiconductor sealing adhesive is preferably 0.1 to 100 parts by weight of the (a) epoxy resin. 10 parts by weight, more preferably 0.1 to 7 parts by weight, still more preferably 0.1 to 5 parts by weight. When the blending amount of the component (b) is less than 0.1 parts by weight, the curability may be lowered, and when it exceeds 10 parts by weight, it hardens before the connection part by the gold-tin eutectic is formed. May result in poor connection.

(C) Polymer component having a weight average molecular weight of 10,000 or more (c) Examples of the polymer component having a weight average molecular weight of 10,000 or more include epoxy resin, phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, phenol resin, and cyanate ester. Examples thereof include resins, acrylic resins, polyester resins, polyethylene resins, polyethersulfone resins, polyetherimide resins, polyvinyl acetal resins, urethane resins, and acrylic rubbers. Among these, epoxy resin, phenoxy resin, polyimide resin, cyanate ester resin, polycarbodiimide resin, acrylic rubber and the like are preferable from the viewpoint of excellent heat resistance and film formability, epoxy resin, phenoxy resin, polyimide resin, acrylic rubber Is more preferable. A phenol resin is also preferable from the viewpoint of highly controlling the viscosity and physical properties of the cured product. These polymer components can be used alone or in combination of two or more.

(D) Polyimide resin (d) A polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, tetracarboxylic dianhydride and diamine are used in an organic solvent in an equimolar or almost equimolar amount (the order of addition of each component is arbitrary), and the addition reaction is carried out at a reaction temperature of 80 ° C. or less, preferably 0 to 60 ° C. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The acid dianhydride is preferably recrystallized and purified with acetic anhydride in order to suppress deterioration of various properties of the film adhesive.

  The molecular weight of the polyamic acid can be adjusted by heating and depolymerizing at a temperature of 50 to 80 ° C.

  The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed and a chemical ring closure method using a dehydrating agent.

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2 , 3,4-Butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2 , 2]-Oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2, -bis [4- (3 , 4-Dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2, -bis [4- (3,4-di Carboxyphenyl) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (tri Merit acid anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid anhydride), 5- (2,5-dioxotetrahydride) Furyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following general formula (I) Acid dianhydride (in the general formula (I), n represents an integer of 2 to 20),

  Examples thereof include tetracarboxylic dianhydrides represented by the following formula (II).

  The tetracarboxylic dianhydride represented by the general formula (I) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, specifically 1,2- (ethylene) bis. (Trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- ( Nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dode ) Bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like. Especially, the tetracarboxylic dianhydride represented by the said Formula (II) is preferable at the point which can provide the outstanding moisture-proof reliability. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  Further, the content of the tetracarboxylic dianhydride represented by the above formula (II) is preferably 40 mol% or more, more preferably 50 mol% or more based on the total tetracarboxylic dianhydride. 70 mol% or more is extremely preferable. When it is less than 40 mol%, it is not possible to sufficiently ensure the effect of moisture resistance reliability due to the use of the tetracarboxylic dianhydride represented by the above formula (II).

There is no restriction | limiting in particular as diamine used as a raw material of the said polyimide resin, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'- diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4 , 4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4- Amino-3,5-diisopropylphenyl) methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenylsulfone, 3,4'-diamino Phenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3, 4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-amino) Enoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis) (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2, 2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) Sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, Aromatic diamines such as bis (4- (4-aminophenoxy) phenyl) sulfone, 3,5-diaminobenzoic acid, 1,3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) Propane, aliphatic ether diamine represented by the following general formula (III) (in general formula (III), Q ¹ , Q ² and Q ³ each independently represents an alkylene group having 1 to 10 carbon atoms, 80 represents an integer),

  An aliphatic diamine represented by the following general formula (IV) (wherein n represents an integer of 5 to 20),

Siloxane diamine represented by the following general formula (V) (wherein Q ⁴ and Q ⁹ each independently represents an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and p represents an integer of 1 to 5)

Etc. Among them, the diamine represented by the above general formula (III) or (IV) is preferable in that low stress property, laminating property, and adhesiveness can be imparted. Moreover, the diamine represented by the said general formula (V) is preferable at the point which can provide low water absorption and low hygroscopicity. These diamines can be used alone or in combination of two or more. In this case, the aliphatic ether diamine represented by the general formula (III) is 1 to 50 mol% of the total diamine, the aliphatic diamine represented by the general formula (IV) is 20 to 80 mol% of the total diamine, And it is preferable that the siloxane diamine represented by the said general formula (V) is 20-80 mol% of all the diamines. When the content is outside the above range of mol%, the effect of imparting laminating properties and low water absorption tends to be reduced.

  Further, as the aliphatic ether diamine represented by the general formula (III), specifically,

Etc. Among them, aliphatic ether diamines represented by the following general formula (VI) (wherein m represents an integer of 2 to 80) are those that can ensure low-temperature laminating properties and good adhesion to a substrate with an organic resist. Particularly preferred.

  Examples of the aliphatic ether diamine represented by the general formula (VI) include, for example, Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-900 manufactured by Sun Techno Chemical Co., Ltd. , ED-2001, EDR-148, aliphatic ether diamines such as polyoxyalkylene diamines such as polyether amines D-230, D-400, D-2000 manufactured by BAS can be used.

  Examples of the aliphatic diamine represented by the general formula (IV) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2- Diaminocyclohexane and the like can be mentioned, among which 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane are preferable.

Examples of the siloxane diamine represented by the general formula (V) include, for example, in the general formula (V), <when p is 1,> 1,1,3,3-tetramethyl-1,3- Bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3- Bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3- Bis (2-aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3- Bis (3-aminobutyl) disiloxane, 1,3-dimethyl -1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane and the like, and when <p is 2,> 1,1,3,3,5,5-hexamethyl-1,5- Bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetra Phenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) Trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy -1,5-bis (4-aminobutyl) Lisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5, Examples include 5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.
The above polyimide resins can be used alone or in combination (blend) of two or more as required.

(D) The glass transition temperature (Tg) of the polyimide resin is preferably 100 ° C. or lower, more preferably 75 ° C. or lower, from the viewpoint of sticking to a substrate or a chip. When the temperature is higher than 100 ° C., bumps formed on the semiconductor chip, unevenness such as electrodes and wiring patterns formed on the substrate cannot be embedded, and bubbles remain, causing voids.
The above Tg is measured using DSC (differential scanning thermal analysis, DSC-7 manufactured by Perkin Elmer Co.) under the conditions of a sample amount of 10 mg, a heating rate of 5 ° C./min, and a measurement atmosphere: air. Of Tg.

  (D) The weight average molecular weight of the polyimide is preferably 30000 or more, more preferably 40000 or more, and further preferably 50000 or more in terms of polystyrene in order to exhibit good film-formability independently. (D) When the weight average molecular weight of the polyimide is smaller than 30000, the film formability may be lowered. In addition, said weight average molecular weight shows a weight average molecular weight when measured in polystyrene conversion using a high performance liquid chromatography (Shimadzu Corporation C-R4A).

  The content of (d) the polyimide resin in the semiconductor sealing adhesive is not particularly limited, but (d) the content of the epoxy resin is 1 to 400 parts by weight with respect to 100 parts by weight of the polyimide resin. Preferably, it is 10 to 400 parts by weight, more preferably 10 to 300 parts by weight. (A) When content of an epoxy resin is less than 1 weight part, sclerosis | hardenability falls and there exists a possibility that adhesive force may fall, and when it exceeds 400 weight part, there exists a possibility that film forming property may fall.

  The semiconductor sealing adhesive of the present invention may contain a phenol resin as a curing agent from the viewpoint of highly controlling viscosity and physical properties of a cured product. The phenol resin is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule. For example, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type A polyfunctional phenol resin, various polyfunctional phenol resins, etc. can be used. These can be used individually by 1 type or in mixture of 2 or more types.

  The equivalent ratio (phenol resin / epoxy resin) between the phenol resin and the (a) epoxy resin when the phenol resin is blended is 0.3 to 1.5 from the viewpoints of curability, adhesiveness, storage stability, and the like. Preferably, it is 0.4 to 1.2, more preferably 0.5 to 1.0. If the equivalence ratio is less than 0.3, the curability may be lowered and the adhesive force may be lowered. If the equivalent ratio is more than 1.5, an unreacted phenolic hydroxyl group remains excessively, and the water absorption increases. Insulation reliability may be reduced.

  In the semiconductor sealing adhesive of this embodiment, a filler may be blended in order to control the viscosity and the physical properties of the cured product. As the filler, an insulating inorganic filler, whisker, or resin filler can be used. Examples of the insulating inorganic filler include glass, silica, alumina, titanium oxide, carbon black, mica, boron nitride and the like. Among them, silica, alumina, titanium oxide, boron nitride and the like are preferable, silica, alumina, Boron nitride is more preferred. Examples of whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride. A polyurethane resin, a polyimide resin, or the like can be used as the resin filler. These fillers and whiskers can be used alone or in combination of two or more. There is no particular limitation on the shape, particle size, and blending amount of the filler.

  Furthermore, you may mix | blend a silane coupling agent, a titanium coupling agent, a leveling agent, antioxidant, and an ion trap agent with the semiconductor sealing adhesive of this embodiment. These can be used individually by 1 type or in mixture of 2 or more types. What is necessary is just to adjust about a compounding quantity so that the effect of each additive may express.

  The void generation rate in the semiconductor sealing adhesive of the present embodiment is preferably 5% or less, more preferably 3%, and further desirably 1% or less. If the void generation rate exceeds 5%, voids remain between narrow pitch wirings, and insulation reliability may be reduced. The void generation rate can be measured by the method described in the examples.

  The above-mentioned adhesive for semiconductor sealing can be suitably used for the production of COF.

A method for producing a semiconductor sealing adhesive (semiconductor sealing film adhesive) of this embodiment will be described below.
The above-mentioned components are added to an organic solvent, and dissolved or dispersed by stirring, mixing, kneading, or the like to prepare a resin varnish. Then, after applying the resin varnish using a knife coater, roll coater or applicator on the base film subjected to the release treatment, the organic solvent is removed by heating, and a film adhesive is applied on the base film. Form.
In preparing the resin varnish, (d) the organic solvent used in the synthesis of the polyimide resin may be used without being removed, and another component may be added thereto to prepare the resin varnish.

  As the organic solvent used for preparing the resin varnish, those having properties capable of uniformly dissolving or dispersing each component are preferable. For example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, Examples include toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, and ethyl acetate. These organic solvents can be used individually by 1 type or in mixture of 2 or more types. Mixing, kneading, and the like in preparing the resin varnish can be performed using a stirrer, a raking machine, a three roll, a ball mill, a homodisper, or the like.

  In addition, the base film is not particularly limited as long as it has heat resistance that can withstand the heating conditions when the organic solvent is volatilized, and a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film. Polyether naphthalate film, methylpentene film and the like can be exemplified. The base film is not limited to a single layer made of these films, and may be a multilayer film made of two or more materials.

  Furthermore, it is preferable that the conditions for volatilizing the organic solvent from the resin varnish after coating are such that the organic solvent is sufficiently volatilized, specifically, heating at 50 to 200 ° C. for 0.1 to 90 minutes. It is preferable to carry out.

A method for manufacturing the semiconductor device of this embodiment will be described below.
The manufacturing method of the semiconductor device of this embodiment has a connection process which connects a semiconductor chip and the board | substrate which has metal wiring at the temperature of 300 degreeC or more via the above-mentioned film-form adhesive for semiconductor sealing.

  Examples of the material of the bump formed on the semiconductor chip include gold, low melting point solder, high melting point solder, nickel, tin and the like. Among them, gold is suitable when applied to COF.

  Examples of the material of the substrate include inorganic substances such as ceramics, and organic substances such as epoxy resins, bismaleimide triazine resins, and polyimide resins. Especially, when applying to COF, a polyimide resin is suitable.

  Examples of the material for forming the wiring on the substrate include copper, aluminum, silver, gold, and nickel. The wiring is formed by etching or pattern plating. The surface of the wiring may be plated with gold, nickel, tin or the like. Especially, when applying to COF, the copper wiring by which the surface was tin-plated is suitable.

The film-like adhesive for semiconductor sealing may be used after being cut into a predetermined size and then attached to a substrate, or after being attached to a bump forming surface of a semiconductor wafer and dicing into pieces. Thus, a semiconductor chip to which a film-like adhesive for semiconductor sealing is attached may be produced. The area and thickness of the film adhesive are appropriately set according to the semiconductor chip size, bump height, and the like.
After the film-like adhesive for semiconductor sealing is attached to the substrate or the semiconductor chip, the wiring pattern of the substrate and the bump of the semiconductor chip are aligned and pressed at a temperature of 300 to 450 ° C. for 0.5 to 5 seconds. Thus, the substrate and the semiconductor chip are connected, and the gap between the semiconductor chip and the substrate is sealed and filled with the adhesive.

  The connection load depends on the number of bumps and the like, but is set in consideration of absorption of bump height variations and control of the amount of bump deformation. After the semiconductor chip and the substrate are connected, heat treatment may be performed in an oven or the like.

  The semiconductor device manufactured by the above manufacturing method can be suitably used for, for example, a liquid crystal display module.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not restrict | limited by an Example.

(Synthesis of polyimide resin)
In a 300 ml flask equipped with a thermometer, a stirrer and a calcium chloride tube, 2.10 g (0.035 mol) of 1,12-diaminododecane, 17.31 g of polyetherdiamine (manufactured by BASF, ED2000 <weight average molecular weight: 1923>) (0.03 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., LP-7100) 2.61 g (0.035 mol) and N-methyl-2- Pyrrolidone (manufactured by Kanto Chemical Co., Inc.) 150 g was charged and stirred. After dissolution of the diamine, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic dianhydride) (made by ALDRICH, purified by recrystallization with acetic anhydride while cooling the flask in an ice bath, BPADA) 15.62 g (0.10 mol) was added in small portions. After reacting at room temperature (25 ° C.) for 8 hours, 100 g of xylene was added, heated at 180 ° C. while blowing nitrogen gas, and azeotropic removal of xylene with water was performed. Polyimide resin (Tg: 22 ° C., weight average molecular weight: 47000, SP value: 10.2, hereinafter, referred to as “synthetic polyimide”).

(Method for producing film adhesive)
Synthetic polyimide 1.62 g and epoxy resin YDCN-702; 0.18 g, VG3101L; 0.18 g, silica filler R972; 0.11 g, boron nitride HPP1-HJ; 0.70 g, cured to 20 ml of glass screw tube Accelerator 0.0036g and N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Inc.) 4.4g were charged and stirred with a stirring / defoaming device AR-250 (manufactured by Shinky Co., Ltd.). After defoaming, it is applied with a coating machine PI1210FILMCOATER (manufactured by Tester Sangyo Co., Ltd.), dried in a clean oven (manufactured by Espetsk Co., Ltd.) Obtained.

(Examples 1 and 2 and Comparative Examples 1 to 4)
A film-like adhesive was produced in the same manner as the above-described method for producing a film-like adhesive except that the composition of the used material was changed as shown in Table 1.

The compounds used in Examples and Comparative Examples are shown below.
(A) Epoxy resin / cresol novolak type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-702)
・ Multifunctional special epoxy resin (Printtech, VG3101L)
(B) Compound formed from an organic acid that reacts with an epoxy resin and a curing accelerator: 1-cyanoethyl-2-phenylimidazolium trimellitate (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2PZ-CNS)
1-cyanoethyl-2-undecylimidazolium trimellitate (Shikoku Kasei Kogyo Co., Ltd., C11Z-CNS)
(B ′) Curing accelerator 1-cyanoethyl-2-phenylimidazole (manufactured by Shikoku Chemicals Co., Ltd., 2PZ-CN)
2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine (manufactured by Shikoku Chemicals Co., Ltd., 2MZA-PW)
(B ″) Adduct of organic acid and curing accelerator, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct (Shikoku Chemicals Co., Ltd.) (2MAOK-PW made by company)
(D) Polyimide resin / the above-mentioned synthetic polyimide (e) Other component phenolic resin:
Cresol naphthol formaldehyde polycondensate (manufactured by Nippon Kayaku Co., Ltd., Kayahard NHN)
Filler:
Boron nitride (manufactured by Mizushima Alloy Iron Co., Ltd., HPP1-HJ <average particle size: 1.0 μm, maximum particle size: 5.1 μm>)
Silica filler (Nippon Aerosil Co., Ltd., R972 <average particle size 20 nm>)

(Evaluation of film adhesive)
For the film-like adhesives obtained in Examples 1 and 2 and Comparative Examples 1 to 4, the viscosity, void generation rate, connection resistance, and HAST resistance were measured by the methods described below. The results are shown in Table 1.

(1) Measurement of viscosity Sample A in which glass chip 1, film adhesive 2, and cover glass 3 shown in FIG. 1 were laminated in this order was prepared. Specifically, the produced film adhesive is cut out (diameter 6 mm, thickness about 0.1 mm), affixed on a glass chip (15 mm × 15 mm × thickness 0.7 mm), and a cover glass (18 mm × 18 mm × thickness 0). .12 to 0.17 mm) and a sample A was produced. This sample A was crimped with FCB3 (flip chip bonder, manufactured by Matsushita Electric Industrial Co., Ltd.) (crimping conditions: 350 ° C., 0.5 seconds, 1 MPa), and the volume change of the film adhesive before and after the crimping was measured. The viscosity was calculated from the volume change by the parallel plate plastometer method according to the following formula.

  In addition, about the film-form adhesive of Example 1 and Comparative Examples 2-4, the change of the viscosity at the time of changing crimping time into 0.5, 1 and 5 second was measured, respectively. The results are shown in Table 2.

(2) Measurement of Void Incidence Rate Sample B in which glass chip 1, film adhesive 2, and chip 4 with gold bump 5 shown in FIG. 2 were laminated in this order was prepared. Specifically, the produced film adhesive is cut out (5 mm × 5 mm × thickness 0.03 mm) and pasted on a glass chip (15 mm × 15 mm × thickness 0.7 mm), and the chip with gold bump (1) (4 .26 mm × 4.26 mm × thickness 0.27 mm, bump height 0.02 mm), and sample B was fabricated. Sample B was crimped with FCB3 (flip chip bonder) (crimping conditions: head temperature 350 ° C., stage temperature 100 ° C., 5 seconds, 1 MPa), and the void generation rate before and after the crimping was measured. The void generation rate was calculated by the ratio of the generated void area after pressurization per chip (1) area with the gold bump.

(3) Manufacture of semiconductor devices (evaluation of connection resistance)
Cut out the produced film adhesive (2.5 mm × 15.5 mm × 0.03 mm thickness), polyimide substrate (polyimide substrate: 38 μm thickness, copper wiring: 8 μm thickness, wiring tin plating: 0.2 μm thickness, Inc. A chip with gold bumps (2) (chip size 1.6 mm × 15.1 mm × thickness 0.4 mm, bump size: 20 μm × 100 μm × height 15 μm) pasted on Hitachi Super LSI Systems, JKIT COF TEG — 30-B) , Bump number 726, manufactured by Hitachi ULSI Systems Co., Ltd., JTEG PHASE6_30) was mounted on FCB3 (mounting conditions: head temperature 350 ° C., stage temperature 100 ° C., 1 second, 50 N).
FIG. 3 is a photograph showing the entire manufactured semiconductor device, and FIG. 4 is a photograph showing a cross section of the semiconductor device. In the drawing, reference numerals 6, 7, 8, and 9 denote a polyimide substrate, a chip (2), a tin-plated copper wiring, and a gold bump (2), respectively.
The semiconductor device (without film adhesive) in which the polyimide substrate and the chip with gold bump (2) (daisy chain connection) are mounted with FCB3 had a connection resistance value of around 160 (Ω). The case of less than 200 (Ω) was evaluated as “◯”, and the case of 200 (Ω) or more was evaluated as “x”.

(4) Insulation reliability test (HAST test: Highly Accelerated Storage Test)
A sample C in which a film adhesive was laminated on a polyimide substrate 11 on which a tin-plated copper wiring 10 was formed in a comb shape shown in FIG. 5 was produced. Specifically, the produced film adhesive (thickness: 30 μm) is attached to a comb-shaped electrode evaluation TEG (30 μm pitch) on which a tin-plated copper wiring is formed on a polyimide film, and a clean oven (manufactured by ESPEC CORPORATION) ) (180 ° C., 1 hour) to prepare Sample C. After curing, sample C was taken out and placed in an accelerated life test apparatus (Hirayama Seisakusho, PL-422R8, conditions: 110 ° C., 85%, 100 hours), and the insulation resistance was measured.
During the measurement, was evaluated when the insulation resistance is not less than 10 ⁷ Omega as "○", "×" a is equal to or less than 10 ⁷ Omega.

The component (b) (curing accelerator) of Example 1 is a salt of the curing accelerator of Comparative Example 2 and an organic acid that reacts with the epoxy resin, and the curing accelerator of Comparative Example 3 is that of Comparative Example 4. An organic acid that does not react with the epoxy resin is added to the curing accelerator.
In Examples 1 and 2, the void generation rate is drastically reduced as compared with Comparative Example 1 by adding the component (b). Examples 1-2 and Comparative Example 3 using a compound formed from an organic acid and a curing accelerator, and Comparative Example 1 not using a curing accelerator have a viscosity of 250 Pa · s or less and a sufficient connection resistance. Low and secures continuity.

  From Table 2, when Example 1 and Comparative Example 2 are compared, the film-like adhesive of Example 1 has a sufficiently small increase in viscosity even after solvent drying (80 ° C./30 minutes and 120 ° C./30 minutes). It is clear. In addition, compared with the case where no curing accelerator is used (Comparative Example 1), in the film adhesives of Examples 1 and 2, the void generation rate is drastically reduced. It is clear that the component is active even at 120 ° C. or higher. Moreover, it is clear that the film adhesives of Examples 1 and 2 have better HAST resistance as compared with Comparative Example 3.

It is a schematic cross section of the sample A used for a viscosity measurement. It is a schematic cross section of the sample B used for the measurement of a void generation rate. It is a photograph which shows the whole semiconductor device manufactured by manufacture of a semiconductor device. It is a photograph which shows the cross section of the semiconductor device manufactured by manufacture of a semiconductor device. It is a photograph which shows the general view of the sample C used for an insulation reliability test.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Glass chip, 2 ... Film adhesive, 3 ... Cover glass, 4 ... Chip (1), 5 ... Gold bump (1), 6 ... Polyimide substrate, 7 ... Chip (2), 8 ... Tin plating copper wiring , 9 ... Gold bump (2), 10 ... Tin-plated copper wiring, 11 ... Polyimide substrate and film adhesive.

Claims (16)

  A semiconductor sealing adhesive comprising a compound formed from (a) an epoxy resin, and (b) an organic acid that reacts with the epoxy resin and a curing accelerator.   (C) The semiconductor sealing adhesive according to claim 1, further comprising a polymer component having a weight average molecular weight of 10,000 or more.   The adhesive for semiconductor encapsulation according to claim 2, wherein the polymer component (c) having a weight average molecular weight of 10,000 or more contains (d) a polyimide resin.   (D) The adhesive for semiconductor sealing of Claim 3 whose weight average molecular weights of a polyimide resin are 30000 or more, and whose glass transition temperature is 100 degrees C or less.   (A) Adhesive for semiconductor sealing as described in any one of Claims 1-4 whose epoxy resin is solid at 1 atmosphere and 25 degreeC.   (B) The semiconductor sealing adhesive according to any one of claims 1 to 5, wherein the compound formed from the organic acid that reacts with the epoxy resin and the curing accelerator is solid at 1 atm and 25 ° C. .   (B) Adhesive for semiconductor sealing as described in any one of Claims 1-6 whose melting | fusing point of the compound formed from the organic acid and the hardening accelerator which react with an epoxy resin is 120 degreeC or more.   (B) The semiconductor sealing adhesive according to claim 1, wherein an active region of a compound formed from an organic acid that reacts with an epoxy resin and a curing accelerator is 120 ° C. or higher.   The adhesive for semiconductor encapsulation according to claim 1, wherein the organic acid is an acid having a carboxyl group.   The adhesive for semiconductor encapsulation according to claim 1, wherein the curing accelerator is an imidazole.   The adhesive for semiconductor sealing as described in any one of Claims 1-10 whose said organic acid is trimellitic acid.   12. The semiconductor according to claim 1, wherein a melt viscosity at 350 ° C. or more is 250 Pa · s or less, and a void generation rate is 5% or less when pressed at 350 ° C. for 5 seconds or more. Sealing adhesive.   The film-form adhesive for semiconductor sealing formed by forming the adhesive for semiconductor sealing as described in any one of Claims 1-12 into a film form. A method for manufacturing a semiconductor device comprising a semiconductor chip having bumps and a substrate having metal wiring,
The semiconductor chip and the substrate are bonded to the bump and the metal via the semiconductor sealing adhesive according to any one of claims 1 to 12 or the semiconductor sealing film adhesive according to claim 13. Arrange the wiring so that they face each other,
The semiconductor chip and the substrate are pressed and heated in a facing direction to cure the semiconductor sealing adhesive or the semiconductor sealing film adhesive, and electrically connect the bump and the metal wiring. A manufacturing method having a connecting step of connecting.   In the connecting step, the semiconductor chip and the substrate are pressurized in a facing direction and heated to 300 ° C. or more, and gold-tin is formed between the bump containing gold and the metal wiring having the tin plating layer. The manufacturing method of Claim 14 which forms a eutectic and electrically connects the said bump and the said metal wiring.   A semiconductor device manufactured by the manufacturing method according to claim 14.