JP6827851B2 - Manufacturing method of circuit member connection sheet and semiconductor device - Google Patents

Description

The present invention relates to a circuit member connecting sheet and a method for manufacturing a semiconductor device using the sheet.

In recent years, a flip chip mounting method has been adopted from the viewpoints of high integration of semiconductor integrated circuits (ICs) and miniaturization of semiconductor devices (IC packages). This flip chip mounting method is a kind of wireless bonding method. A bump made of solder or the like is formed on an electrode on the surface of a semiconductor chip, and the semiconductor chip is turned upside down on a printed circuit board, a ceramic substrate, or the like. After mounting and aligning the bump and the electrode of the substrate, the bump is heated and melted to join the electrode of the semiconductor chip and the electrode of the substrate.

Further, from the viewpoint of increasing the capacity and high functionality of electronic circuits, the development of three-dimensional integrated laminated circuits (hereinafter, sometimes referred to as "laminated circuits") in which a plurality of semiconductor chips are three-dimensionally laminated is also in progress. Even in such a laminated circuit, due to the need for miniaturization and high functionality, a TSV chip having a through electrode (TSV) penetrating from the circuit forming surface to the opposite surface is manufactured, and direct conduction between the upper and lower TSV chips is performed. The method of connecting has been developed as an effective method.

In a semiconductor device manufactured by such a flip chip mounting method or a stack of semiconductor chips, in order to ensure electrical connection reliability and mechanical connection strength, generally, between the semiconductor chip and the substrate. Alternatively, a resin called an underfill material is interposed between the semiconductor chips. As a method of using the underfill material, a method is known in which after solder-bonding between the semiconductor chip and the substrate or between the semiconductor chips, an underfill material made of a liquid resin composition is injected into the gap between the two and the underfill material is cured. Has been done.

However, in recent years, with the increase in the number of electrodes, the narrowing of the pitch of electrodes, and the thinning of semiconductor devices due to the high integration of semiconductor integrated circuits, the distance between the bumps or through electrodes described above has become extremely narrow, and the distance between the bumps or through electrodes has become extremely narrow. The distance between the substrate and the semiconductor chip is becoming extremely small. Therefore, the above method using the liquid resin composition as the underfill material has a problem that it is difficult to completely fill the gap between the semiconductor chips and the substrate or the gap between the semiconductor chips.

To solve this problem, a method of adhering circuit members to each other by using an adhesive film called NCF (Non-Conductive Film) has been proposed (see, for example, Patent Document 1). The adhesive film described in Patent Document 1 includes a thermosetting adhesive layer, and by curing the adhesive layer by heating, circuit members can be firmly adhered to each other.

Patent No. 5569121

However, the conventional adhesive film as described in Patent Document 1 has a problem that the storage stability with respect to thermosetting is poor. That is, there is a problem that the adhesive layer is unintentionally cured before the adhesive layer is heated in order to cure the adhesive layer. For example, when the adhesive film is stored, the adhesive layer is cured due to an increase in ambient temperature or the like, the adhesive layer is cured by the heat generated when the adhesive film is laminated on a circuit member, or a semiconductor chip is formed. There is a problem that the adhesive layer is cured by the heat generated due to the high accumulation.

Further, in the conventional adhesive film as described in Patent Document 1, it takes a relatively long time from the start to the completion of curing of the adhesive layer, and as a result, there is a problem that the productivity of the semiconductor device is lowered. It was.

The present invention has been made in view of such an actual situation, and an object of the present invention is to provide a circuit member connecting sheet which is excellent in storage stability with respect to thermosetting and can cure an adhesive layer in a short time. And. The present invention also provides a highly productive method for manufacturing a semiconductor device using such a circuit member connecting sheet.

In order to achieve the above object, first, the present invention is a circuit member connecting sheet interposed between the opposing electrodes and used for electrically connecting the facing electrodes, and the circuit. The member connecting sheet includes at least a curable adhesive layer, and the adhesive layer includes a thermosetting resin, a thermoplastic resin, an imidazole-based curing catalyst, and the following formula (1).

Provided is a circuit member connecting sheet, which is formed from an adhesive composition containing a composite compound formed from a compound having the above structure, a flux component, and an inorganic filler (Invention 1).

In the circuit member connecting sheet according to the above invention (Invention 1), since the adhesive layer is formed from the adhesive composition containing the above composite compound, curing of the adhesive layer at an unintended stage is suppressed. Therefore, it is excellent in storage stability regarding thermosetting. Further, when the curing is started by heating the adhesive layer, the curing reaction proceeds rapidly and the curing reaction is completed in a short time, so that the circuit members can be bonded to each other in a short time. ..

In the above invention (Invention 1), it is preferable that the reaction rising temperature of the adhesive layer measured by the differential scanning calorimetry method is 140 ° C. or higher and 250 ° C. or lower (Invention 2).

In the above inventions (Inventions 1 and 2), the difference between the reaction rising temperature and the reaction peak temperature measured by the differential scanning calorimetry is preferably 1 ° C. or higher and 20 ° C. or lower in the adhesive layer (invention 1 and 2). Invention 3).

In the above inventions (Inventions 1 to 3), the imidazole-based curing catalyst is a compound having the structure of the following formula (2).

[In the formula (2), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent. , A phenyl group which may have a substituent, a benzyl group which may have a substituent or a cyanoethyl group. R ^{2 to} R ⁴ independently have a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 3 carbon atoms which may have a substituent. Shows a cycloalkyl group of ~ 20, a phenyl group which may have a substituent, a benzyl group which may have a substituent, or an acyl group having 1 to 20 carbon atoms which may have a substituent. .. ]
(Invention 4).

In the above inventions (Inventions 1 to 4), the content of the imidazole-based curing catalyst in the composite compound is 1.0 mol or more and 2.0 mol or more with respect to 1 mol of the compound having the structure of the formula (1). It is preferably less than a molar amount (Invention 5).

In the above inventions (Inventions 1 to 5), the thermosetting resin is an epoxy resin, or is a group consisting of an epoxy resin, a phenol resin, a melamine resin, a urea resin, an amine compound, and an acid anhydride compound. It is preferably a mixture with at least one selected from (Invention 6).

In the above inventions (Inventions 1 to 6), the flux component preferably contains a carboxyl group (Invention 7).

Secondly, in the present invention, one surface of the adhesive layer in the circuit member connecting sheet (Invention 1 to 7) and the surface of one circuit member provided with the electrode where the electrode is present are bonded together. The step, the step of bonding the other surface of the adhesive layer in the circuit member connecting sheet and the surface of the other circuit member having the electrode where the electrode exists, and the step of curing the adhesive layer. It is characterized by including a step of adhering the one circuit member and the other circuit member and electrically connecting the electrode of the one circuit member and the electrode of the other circuit member. Provided is a method for manufacturing a semiconductor device (invention 8).

The circuit member connecting sheet of the present invention is excellent in storage stability with respect to thermosetting, and can cure the adhesive layer in a short time. Further, according to the manufacturing method of the present invention, a semiconductor device can be manufactured with high productivity by using such a circuit member connecting sheet.

It is sectional drawing of the circuit member connection sheet which concerns on 1st Embodiment of this invention. It is sectional drawing of the circuit member connection sheet which concerns on 2nd Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
[Sheet for connecting circuit members]
FIG. 1 shows a cross-sectional view of the circuit member connecting sheet 1 according to the first embodiment. As shown in FIG. 1, the circuit member connecting sheet 1 (hereinafter, may be referred to as “connecting sheet 1”) according to the present embodiment has an adhesive layer 11 and at least one surface of the adhesive layer 11. A release sheet 12 laminated to the above is provided. In addition, another release sheet may be further laminated on the surface of the adhesive layer 11 opposite to the release sheet 12. However, the release sheet 12 and another release sheet may be omitted.

Further, FIG. 2 shows a cross-sectional view of the circuit member connecting sheet 2 according to the second embodiment. As shown in FIG. 2, the circuit member connecting sheet 2 according to the present embodiment (hereinafter, may be referred to as “connecting sheet 2”) is laminated on the base material 14 and at least one surface side of the base material 14. The pressure-sensitive adhesive layer 13 and the adhesive layer 11 laminated on the surface side of the pressure-sensitive adhesive layer 13 opposite to the base material 14 are provided. A release sheet may be further laminated on the surface of the adhesive layer 11 opposite to the pressure-sensitive adhesive layer 13. However, the base material 14, the pressure-sensitive adhesive layer 13, and the release sheet may be omitted.

The circuit member connecting sheets 1 and 2 according to the present embodiment are used to electrically connect the electrodes facing each other. In this case, the adhesive layers 11 of the connecting sheets 1 and 2 are interposed between the electrodes facing each other. The circuit member is not particularly limited as long as it is a member in which electrodes are formed in the circuit. For example, in addition to semiconductor chips and semiconductor wafers, inorganic circuit boards such as lead frames, ceramic circuit boards, and glass circuit boards, and organic rigid circuits. Examples thereof include organic circuit boards such as substrates and flexible circuit boards. The electrode may be a through electrode. Further, in the present specification, the electrode also includes a bump made of solder or the like formed on the electrode.

In the circuit member connecting sheets 1 and 2 according to the present embodiment, the adhesive layer 11 has curability. Here, having curability means that the adhesive layer 11 can be cured by heating or the like. That is, the adhesive layer 11 is uncured in the state of forming the connecting sheets 1 and 2. The adhesive layer 11 is preferably thermosetting. As a result, even when the adhesive layer 11 is laminated between circuit members having no energy ray transmittance, the adhesive layer 11 can be satisfactorily cured.

In the circuit member connecting sheets 1 and 2 according to the present embodiment, the adhesive layer 11 is a thermosetting resin, a thermoplastic resin, an imidazole-based curing catalyst, and the following formula (1).

It is formed from an adhesive composition containing a composite compound formed from a compound having the above structure, a flux component, and an inorganic filler.

As will be described later, in the above composite compound, the compound of the above formula (1) does not dissociate from the imidazole-based curing catalyst until it is heated to a predetermined temperature. Further, the imidazole-based curing catalyst cannot function as a catalyst in a state where a composite compound is formed with the compound of the above formula (1). Therefore, the adhesive layer 11 does not start the curing reaction until it is heated to a predetermined temperature. As a result, in the circuit member connecting sheets 1 and 2 according to the present embodiment, such as when the connecting sheets 1 and 2 are stored and before heating for curing the adhesive layer 11 in the method of manufacturing a semiconductor device. Curing of the adhesive layer 11 at an unintended stage can be suppressed, and storage stability with respect to thermosetting is excellent.

On the other hand, when the composite compound is heated to a predetermined temperature, the compound of the above formula (1) is dissociated from the imidazole-based curing catalyst at once, and accordingly, the curing reaction is started at once in the pressure-sensitive adhesive layer 13. In addition, the reaction rate increases rapidly, and the curing reaction is completed in a short time. Therefore, when the connecting sheets 1 and 2 are used, the circuit members can be bonded to each other in a short time by heating to a predetermined temperature. Generally, when a semiconductor device is manufactured using an adhesive such as NCF, it takes time to cure the adhesive. Therefore, the takt time in manufacturing a semiconductor device may be determined by the curing time of the adhesive. There are many. On the other hand, according to the circuit member connecting sheets 1 and 2 according to the present embodiment, the curing reaction of the adhesive layer 11 is completed in a short time as described above, so that the tact time can be effectively shortened. Become. Therefore, by using the circuit member connecting sheets 1 and 2 according to the present embodiment, the productivity of the method for manufacturing the semiconductor device can be improved.

The compound of the above formula (1) is dissociated from the imidazole-based curing catalyst and then reacted with the thermosetting resin to be incorporated into the structure formed by the resin. Therefore, after the adhesive layer 11 is cured, the compound does not adversely affect the circuit members and the like.

1. 1. Adhesive layer (1) Composite compound The above composite compound is an imidazole-based curing catalyst and the following formula (1).

It is formed from a compound having the structure of. The compound of the formula (1) is also called 5-hydroxyisophthalic acid or 5-hydroxy-1,3-benzenedicarboxylic acid.

In the above-mentioned composite compound, it is preferable that the site necessary for exerting the function as a catalyst in the imidazole-based curing catalyst and the compound of the above formula (1) are bonded by a bond other than a covalent bond. As a result, in the state where the composite compound is formed, the catalytic function of the imidazole-based curing catalyst is effectively inhibited, and the curing reaction at an unintended stage is effectively suppressed, resulting in better storage stability. be able to.

An example of the above bond other than the covalent bond is a hydrogen bond. In this case, for example, at least one of the carboxyl groups of the compound of the above formula (1) and nitrogen constituting the imidazole ring structure in the imidazole-based curing catalyst. (in later-described formula (2), a hydrogen atom at the position of R ¹⁾ a hydrogen atom that is covalently bonded to an atom of hydrogen bond occurs between the.

The composite compound preferably has a structure in which two imidazole-based curing catalysts are linked by one compound of the above formula (1). In this case, each of the two carboxyl groups of the compound of the above formula (1) forms a hydrogen bond with the hydrogen atom in the imidazole-based curing catalyst. The composite is preferable from the viewpoint of excellent storage stability regarding thermosetting and easy achievement of a curing reaction in a short time. In the composite compound, the ratio of the compound of the above formula (1) to the imidazole-based curing catalyst is 1: 2.

Further, the composite compound may have a structure in which a plurality of compounds of the above formula (1) are linked to form a molecular chain, and imidazole-based curing catalysts are present at both ends thereof. In this case, the plurality of compounds of the above formula (1) have hydrogen bonds between the carboxyl groups, and the compound of the above formula (1) and the imidazole-based curing catalyst have the carboxyl groups and the above hydrogen, respectively. A hydrogen bond is formed with the atom. In such a composite compound, when the number of the compound of the above formula (1) is X, the ratio of the compound of the above formula (1) to the imidazole-based curing catalyst is X: 2. In particular, the composite compound preferably has a structure in which X is 2, from the viewpoint of excellent storage stability regarding thermosetting and easy achievement of a curing reaction in a short time.

Moreover, the said complex compound may be a clathrate compound. In this case, for example, it has a structure in which an imidazole-based curing catalyst as a guest is incorporated into a space formed by a plurality of compounds of the above formula (1) as a host. In the structure, the host compounds of the above formula (1) are bonded to each other by a bond other than a covalent bond (for example, a hydrogen bond) to form a space, and the guest imidazole-based curing catalyst is the above formula (1). It is preferable that a bond other than a covalent bond (for example, a hydrogen bond) is formed with the compound of the above and fixed in the space. Here, the hydrogen bond between the compound of the above formula (1) and the imidazole-based curing catalyst is preferably a hydrogen bond between the carboxyl group and the hydrogen atom as described above. The shape of the space formed by the host is not particularly limited, and examples thereof include a tunnel shape, a layered shape, and a net shape. The complex compound which is a clathrate compound can also be said to be a salt or a molecular complex formed from the compound of the above formula (1) and an imidazole-based curing catalyst.

When the compound compound is a clathrate compound, the host compound of the above formula (1) need only form the above space with at least a part of the complex compound, and the above formula (1) which does not form the above space. The compound of 1) may be contained in the composite compound. Further, the composite compound may contain an imidazole-based curing catalyst that is not incorporated into the above space.

A curing catalyst encapsulated by a conventional inclusion agent (host) (for example, an inclusion curing catalyst encapsulated by a tetrakisphenol-based compound) often loses its inclusion when dissolved in an organic solvent. Therefore, it is often used without using a solvent (so-called dry blend). When such a curing catalyst is used for the connecting sheet, the inclusion is removed when the adhesive composition is diluted with a solvent, so that unintended curing is performed as in the case of using an unencapsulated curing catalyst. The reaction is easy to proceed. On the other hand, when the composite compound is a clathrate compound using the compound of the above formula (1) as a host, the clathrate does not easily come off even when the composite compound is dissolved in an organic solvent. The curing reaction does not proceed easily, and the storage stability related to thermosetting becomes better.

The imidazole-based curing catalyst is a compound having the structure of the following formula (2).

Is preferable. Since the imidazole-based curing catalyst having the structure can proceed the curing reaction satisfactorily, when the curing reaction is started, the reaction can be advanced more rapidly and completed in a shorter time.

In the above formula (2), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent. , A phenyl group which may have a substituent, a benzyl group which may have a substituent or a cyanoethyl group is preferable.

Examples of alkyl groups having 1 to 10 carbon atoms in R ¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, and isopentyl group. , 2-Methylbutyl group, Neopentyl group, 1-Ethylpropyl group, Hexyl group, Isohexyl group, 4-Methylpentyl group, 3-Methylpentyl group, 2-Methylpentyl group, 1-methylpentyl group, 3,3-dimethyl Butyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2- Examples thereof include ethyl butyl group, heptyl group, octyl group, nonyl group and decyl group. Examples of the cycloalkyl group having 3 to 10 carbon atoms in R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopropylmethyl group and the like.

Further, in the above formula (2), R ^{2 to} R ⁴ independently have a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms and a substituent which may have a substituent. It may have a cycloalkyl group having 3 to 20 carbon atoms, a phenyl group which may have a substituent, a benzyl group which may have a substituent, or a carbon which may have a substituent. It is preferably an acyl group having a number of 1 to 20.

In R ^{2 to} R ⁴ , the number of carbon atoms of the alkyl group is preferably 17 or less, and particularly preferably 10 or less. The carbon number of the cycloalkyl group is preferably 17 or less, and particularly preferably 10 or less. Further, the number of carbon atoms of the acyl group is preferably 17 or less, and particularly preferably 10 or less.

As an example of the alkyl group having 1 to 20 carbon atoms in R ^{2 to} R ⁴ , those mentioned as an example of the alkyl group having 1 to 10 carbon atoms in R ¹ can be used. In the above R ² to R ^4, examples of the cycloalkyl group having 3 to 20 carbon atoms, a cyclopropyl group, cyclobutyl group, cyclopropylmethyl group and the like. Further, in the above-mentioned R ² to R ^4, examples of the acyl group having 1 to 20 carbon atoms, a formyl group, an acetyl group, a propionyl group, a butyryl group, valeryl group, benzoyl group and the like.

Specific examples of the imidazole-based curing catalyst represented by the above formula (2) include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2. -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl -4-Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di (hydroxy) Examples thereof include methyl) imidazole, and from the viewpoint of reactivity, it is preferable to use 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-ethyl-4-methylimidazole. As the imidazole-based curing catalyst, one type may be used alone, or two or more types may be used in combination.

In the above composite compound, the temperature at which the compound of the above formula (1) dissociates from the imidazole-based curing catalyst is preferably 180 ° C. or higher, particularly preferably 190 ° C. or higher, and further 200 ° C. or higher. Is preferable. Further, the temperature is preferably 300 ° C. or lower, particularly preferably 250 ° C. or lower, and further preferably 220 ° C. or lower. When the dissociation temperature is 180 ° C. or higher, the start of the curing reaction of the pressure-sensitive adhesive layer 13 at an unintended stage can be effectively suppressed, and more excellent storage stability can be achieved. Further, when the temperature is 300 ° C. or lower, dissociation can be caused without requiring excessive heating.

The content of the imidazole-based curing catalyst in the composite compound is preferably 1.0 mol or more, particularly 1.5 mol or more, with respect to 1 mol of the compound having the structure of the above formula (1). Is preferable. The content is preferably 2.0 mol or less with respect to 1 mol of the compound having the structure of the above formula (1). When the content is 1.0 mol or more, the content of the imidazole-based curing catalyst in the adhesive layer 11 becomes sufficient, and the curing failure of the adhesive layer 11 can be effectively suppressed and more quickly. Can be cured to. Further, when the content is 2.0 mol or less, the content of the compound of the above formula (1) in the composite compound becomes relatively large, and the compound of the above formula (1) becomes an imidazole-based curing catalyst. On the other hand, the complex compound is formed without deficiency, whereby the curing reaction at an unintended stage can be effectively suppressed.

The content of the composite compound in the adhesive composition is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. Is preferable. Further, the content is preferably 2.0% by mass or less, particularly preferably 1.6% by mass or less, and further preferably 1.5% by mass or less. When the content is in the above range, more excellent storage stability can be achieved, and the time from the start to the completion of curing can be further shortened.

(2) Thermosetting Resin In the circuit member connecting sheets 1 and 2 according to the present embodiment, since the pressure-sensitive adhesive composition contains the thermosetting resin, the circuit members can be firmly adhered to each other. .. The thermosetting resin is not particularly limited as long as it can cure the adhesive layer 11, and for example, a resin usually contained in an adhesive for connecting circuit members can be used. Specific examples thereof include epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, benzoxazine resin, phenoxy resin, amine-based compound, and acid anhydride-based compound. These can be used alone or in combination of two or more. Among these, epoxy resins, phenol resins, melamine resins, urea resins, amine compounds and acid anhydride compounds are preferably used from the viewpoint of being suitable for curing using an imidazole-based curing catalyst, and are particularly excellent. From the viewpoint of exhibiting adhesiveness, at least one selected from the group consisting of epoxy resins, phenol resins, mixtures thereof, or epoxy resins and phenol resins, melamine resins, urea resins, amine compounds and acid anhydride compounds. It is preferable to use a mixture with the seed.

Epoxy resins generally have the property of forming a three-dimensional network when heated to form a strong cured product. As such an epoxy resin, various known epoxy resins can be used, and specifically, glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenylnovolac, and cresolnovolac; butanediol and polyethylene. Epoxy glycidyl ethers of alcohols such as glycols and polypropylene glycols; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; glycidyl type in which active hydrogen bonded to a nitrogen atom such as aniline isocyanurate is replaced with a glycidyl group or Alkylglycidyl type epoxy resin; vinylcyclohexanediepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-) Epoxy) Examples include so-called alicyclic epoxides in which epoxy is introduced by oxidizing carbon-carbon double bonds in the molecule, such as cyclohexane-m-dioxane. In addition, an epoxy resin having a biphenyl skeleton, a triphenylmethane skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, or the like can also be used. These epoxy resins may be used alone or in combination of two or more. Among the above-mentioned epoxy resins, it is preferable to use glycidyl ether of bisphenol A (bisphenol A type epoxy resin) or an epoxy resin having a triphenylmethane skeleton (triphenylmethane type epoxy resin).

Examples of the phenol resin include bisphenol A, tetramethylbisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane type phenol, tetrakisphenol, novolak type phenol, cresol novolac resin and the like. Among them, it is preferable to use novolak type phenol. These phenol resins can be used alone or in combination of two or more. When an epoxy resin is used as the curable resin, it is preferable to use a phenol resin in combination from the viewpoint of reactivity with the epoxy resin.

The content of the thermosetting resin in the adhesive composition is preferably 10% by mass or more, particularly preferably 15% by mass or more, and further preferably 20% by mass or more. Further, the content is preferably 80% by mass or less, particularly preferably 70% by mass or less, and further preferably 60% by mass or less. When the content is 10% by mass or more, the adhesive layer 11 is more sufficiently cured, and the circuit members can be more firmly bonded to each other. Further, when the content is 80% by mass or less, the curing of the adhesive layer 11 at an unintended stage can be further suppressed, and the storage stability becomes more excellent.

(3) Thermoplastic Resin In the circuit member connecting sheets 1 and 2 according to the present embodiment, since the pressure-sensitive adhesive composition contains the thermoplastic resin, it becomes easy to form the adhesive layer 11 in the form of a sheet. .. Therefore, the thermoplastic resin is not particularly limited as long as it enables the adhesive layer to be formed in a sheet shape. For example, a resin usually contained in an adhesive for connecting circuit members is used. can do. Examples of thermoplastic resins include phenoxy resins, olefin resins, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins, silane resins, rubber resins and the like. These can be used alone or in combination of two or more.

The phenoxy resin is not particularly limited, but for example, bisphenol A type, bisphenol F type, bisphenol A / bisphenol F copolymer type, bisphenol S type, bisphenol acetophenone type, novolak type, fluorene type, dicyclopentadiene type, norbornene. Examples include type, naphthalene type, anthracene type, adamantan type, terpen type, trimethylcyclohexane type, biphenol type, biphenyl type and the like, and among these, bisphenol A type phenoxy resin is preferably used.

The content of the thermoplastic resin in the adhesive composition is preferably 1.0% by mass or more, and particularly preferably 5.0% by mass or more. The content is preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the content is in the above range, it becomes easier to form the adhesive layer 11 in the form of a sheet.

(4) Flux component The flux component has a function of removing a metal oxide film formed on the electrode surface (hereinafter, may be referred to as a “flux function”). Therefore, by forming the adhesive layer 11 with the adhesive composition containing the flux component, the electrical connection between the electrodes can be made more reliable. The flux component is not particularly limited as long as it has a flux function, but is preferably a component having a phenolic hydroxyl group and / or a carboxyl group, and particularly preferably a component having a carboxyl group. The component having a carboxyl group has a flux function and also has an action as a curing agent when an epoxy resin is used as a thermosetting resin. Therefore, the component having a carboxyl group reacts and is consumed as a curing agent after the connection between the electrodes is completed, so that a defect caused by an excess flux component can be suppressed.

Specific examples of the flux component include glutaric acid, 2-methylglutaric acid, orthoanisic acid, dihydric acid, adipic acid, acetylsalicylic acid, benzoic acid, benzylic acid, azelaic acid, benzyl benzoic acid, malonic acid, 2,2-. Bis (hydroxymethyl) propionic acid, salicylic acid, o-methoxybenzoic acid, m-hydroxybenzoic acid, succinic acid, 2,6-dimethoxymethylparacresol, benzoic acid hydrazide, carbohydrazide, malonic acid dihydrazide, succinate dihydrazide, glutaric Acid dihydrazide, salicylate hydrazide, iminodiacetate dihydrazide, itaconic acid dihydrazide, citrate trihydrazide, thiocarbohydrazide, benzophenone hydrazide, 4,4'-oxybisbenzenesulfonyl hydrazide, adipic acid dihydrazide, rosin derivatives and the like Examples of the derivative include gum rosin, tall rosin, wood rosin, polymerized rosin, hydrogenated rosin, formylated rosin, rosin ester, rosin-modified maleic acid resin, rosin-modified phenol resin, and rosin-modified alkyd resin. Among these, it is preferable to use diphenolic acid from the viewpoint of exhibiting an excellent flux function. As the flux component, one type can be used alone or two or more types can be used in combination.

Since the compound of the above formula (1) also has a carboxyl group, the compound may be used as a flux component. In this case, the pressure-sensitive adhesive composition preferably contains the compound of the above formula (1) in the form of the above-mentioned composite compound.

At least one of the melting point and the softening point of the flux component is preferably 80 ° C. or higher, particularly preferably 110 ° C. or higher, and further preferably 130 ° C. or higher. When at least one of the melting point and the softening point of the flux component is within the above range, a more excellent flux function can be obtained, and the generation of outgas can be reduced. The upper limits of the melting point and the softening point of the flux component are not particularly limited, but may be, for example, equal to or lower than the melting point of the solder.

The content of the flux component in the adhesive composition is preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. Is preferable. Further, the content is preferably 20% by mass or less, particularly preferably 15% by mass or less, and further preferably 10% by mass or less. When the content is 0.1% by mass or more, the electrical connection between the electrodes can be made more reliable. Further, when the content is 20% by mass or less, it is possible to prevent problems such as ion migration due to an excess flux component.

(5) Inorganic Filler In the circuit member connecting sheets 1 and 2 according to the present embodiment, since the pressure-sensitive adhesive composition contains the inorganic filler, the cured adhesive layer 11 has excellent mechanical strength. , The reliability of the obtained semiconductor device is improved. The inorganic filler is not particularly limited, but silica, alumina, glass, titanium oxide, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, and oxidation. Examples of composite oxides such as aluminum, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica, mulite, cordierite, montmorillonite, smectite, etc. can be exemplified, and these may be used alone. Alternatively, two or more types can be used in combination. Among these, it is preferable to use a silica filler. The shape of the silica filler is preferably spherical.

The average particle size of the inorganic filler is preferably 10 nm or more, particularly preferably 20 nm or more, and further preferably 30 nm or more. The average particle size of the inorganic filler is preferably 200 nm or less, particularly preferably 150 nm or less, and further preferably 100 nm or less. When the average particle size of the inorganic filler is in the above range, it is possible to form the adhesive layer 11 having excellent transparency. The average particle size of the inorganic filler in the present specification is a value measured by a dynamic light scattering method using a particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name “Nanotrack Wave-UT151”).

The maximum particle size of the inorganic filler is preferably 1000 nm or less, and particularly preferably 500 nm or less. When the maximum particle size of the inorganic filler is 1000 nm or less, it becomes easy to electrically connect the electrodes of the circuit board to each other.

The content of the inorganic filler in the adhesive composition is preferably 35% by mass or more, particularly preferably 40% by mass or more, and further preferably 43% by mass or more. Further, the content is preferably 64% by mass or less, particularly preferably 60% by mass or less, and further preferably 56% by mass or less. When the content is 35% by mass or more, the adhesive layer 11 has better mechanical strength. Further, when the content is 64% by mass or less, the content of the thermosetting resin, the composite compound, etc. in the adhesive composition becomes relatively high, and the storage stability is better and the storage time is shorter. It becomes easier to achieve curing.

(6) Other Ingredients The pressure-sensitive adhesive composition may further contain a plasticizer, a stabilizer, a tackifier, a colorant, a coupling agent, an antistatic agent, an antioxidant, conductive particles, and the like.

The conductive particles can impart anisotropic conductivity to the circuit member connecting sheets 1 and 2, and electrically attach the circuit members to each other in a manner that complements the solder bonding or in a mode different from the solder bonding. Can be joined to.

(7) Physical Properties, etc. In the circuit member connecting sheets 1 and 2 according to the present embodiment, the reaction rising temperature of the adhesive layer 11 before curing, which is measured by the differential scanning calorimetry, is 140 ° C. or higher. It is preferable, particularly preferably 150 ° C. or higher, and further preferably 160 ° C. or higher. Further, the reaction rising temperature is preferably 250 ° C. or lower, particularly preferably 230 ° C. or lower, and further preferably 200 ° C. or lower. Here, the reaction rising temperature is defined as the peak caused by the curing reaction of the adhesive layer 11 in the DSC curve acquired by the differential scanning calorimetry, when the slope of the tangent line in contact with the peak becomes maximum. It shall refer to the temperature (° C). That is, the reaction rising temperature means the temperature at which the reaction rate is maximized in the curing reaction of the adhesive layer 11. When the reaction rising temperature is 140 ° C. or higher, the progress of the curing reaction of the adhesive layer 11 at an unintended stage can be effectively suppressed, and more excellent storage stability can be achieved. Further, when the reaction rising temperature is 250 ° C. or lower, it is possible to proceed the curing reaction without requiring excessive heating.

In the circuit member connecting sheets 1 and 2 according to the present embodiment, the difference between the reaction rising temperature and the reaction peak temperature measured by the differential scanning calorimetry of the adhesive layer 11 before curing is 20 ° C. or less. The temperature is preferably 15 ° C. or lower. Here, the reaction peak temperature refers to the temperature (° C.) that brings about the peak of the peak generated by the curing reaction of the adhesive layer 11 in the DSC curve obtained by the differential scanning calorimetry. To do. When the difference between the reaction rising temperature and the reaction peak temperature is 20 ° C. or less, the time from the start to the completion of curing of the adhesive layer 11 is effectively shortened, whereby the connecting sheets 1 and 2 are used. When the semiconductor device is manufactured, the productivity can be effectively improved. Although the lower limit of the difference between the reaction rising temperature and the reaction peak temperature is not particularly limited, for example, the difference may be 1.0 ° C. or higher, and may be 5.0 ° C. or higher.

In the circuit member connecting sheets 1 and 2 according to the present embodiment, the reaction start temperature of the adhesive layer 11 before curing, which is measured by the differential scanning calorimetry, is preferably 110 ° C. or higher, particularly 120 ° C. The above is preferable. The reaction start temperature is preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower. Here, the reaction start temperature refers to the temperature (° C.) at which the peak that occurs due to the curing reaction of the adhesive layer 11 in the DSC curve acquired by the differential scanning calorimetry starts to occur. It shall be. When the reaction start temperature is 110 ° C. or higher, the start of the curing reaction of the adhesive layer 11 at an unintended stage can be effectively suppressed, and more excellent storage stability can be achieved. Further, when the reaction start temperature is 200 ° C. or lower, the curing reaction can be started without requiring excessive heating.

The reaction rise temperature, reaction peak temperature, and reaction start temperature described above can be measured using a differential scanning calorimeter. For example, the adhesive layer 11 having a thickness of 15 mm is heated from 50 ° C. to 300 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (manufactured by TA Instruments, product name “Q2000”). , Can be obtained from the DSC curve obtained thereby.

The thickness of the adhesive layer 11 is preferably 2 μm or more, particularly preferably 5 μm or more, and further preferably 10 μm or more. Further, the thickness is preferably 500 μm or less, particularly preferably 300 μm or less, and further preferably 100 μm or less. When the thickness of the adhesive layer 11 is 2 μm or more, the electrodes existing in the circuit member can be satisfactorily embedded in the adhesive layer 11. Further, since the thickness of the adhesive layer 11 is 500 μm or less, the adhesive layer 11 does not exude too much to the side surface when the circuit members are bonded to each other via the adhesive layer 11, and the reliability is high. It is possible to manufacture expensive semiconductor devices.

2. 2. Release sheet The circuit member connection sheets 1 and 2 according to the present embodiment may include a release sheet 12. The structure of the release sheet 12 is arbitrary, and examples thereof include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and plastic films such as polyolefin films such as polypropylene and polyethylene. It is preferable that these peeled surfaces (surfaces of the connecting sheets 1 and 2 in contact with the adhesive layer 11) are subjected to a peeling treatment. Examples of the release agent used in the release treatment include silicone-based, fluorine-based, and long-chain alkyl-based release agents.

The thickness of the release sheet 12 is not particularly limited, but is usually 20 μm or more and 250 μm or less.

3. 3. Adhesive Layer In the circuit member connecting sheet 2 according to the second embodiment, the adhesive layer 13 may be composed of a non-curable pressure-sensitive adhesive or a curable pressure-sensitive adhesive. As will be described later, when the circuit member connecting sheet 2 according to the present embodiment is used in the method for manufacturing a semiconductor device, the adhesive layer 11 may be peeled off from the laminate of the base material 14 and the pressure-sensitive adhesive layer 13. .. In this case, from the viewpoint of facilitating the peeling, it is preferable that the pressure-sensitive adhesive layer 13 is composed of a curable pressure-sensitive adhesive and the adhesive strength is reduced by curing.

When the pressure-sensitive adhesive layer 13 is composed of a curable pressure-sensitive adhesive, the pressure-sensitive adhesive may be an energy ray-curable pressure-sensitive adhesive or a thermosetting pressure-sensitive adhesive. Here, the adhesive layer 11 is preferably thermosetting, and the adhesive layer 13 and the adhesive layer 11 are preferably cured at different stages. Therefore, the adhesive layer 13 is energy ray curable. It is preferably composed of a pressure-sensitive adhesive.

The non-curable pressure-sensitive adhesive preferably has desired adhesive strength and removability. For example, acrylic pressure-sensitive adhesive, rubber-based pressure-sensitive adhesive, silicone-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, and the like. A polyvinyl ether adhesive or the like can be used. Among these, it is preferable to use an acrylic pressure-sensitive adhesive from the viewpoint of effectively suppressing unintended peeling at the interface between the pressure-sensitive adhesive layer 13 and the adhesive layer 11.

The energy ray-curable pressure-sensitive adhesive may be mainly composed of a polymer having energy ray curability, or at least one non-energy ray-curable polymer (polymer having no energy ray curability). The main component may be a mixture of the above-mentioned monomer and / or oligomer having an energy ray-curable group. It may also be a mixture of an energy ray-curable polymer and a non-energy ray-curable polymer, a monomer having an energy ray-curable polymer and at least one energy ray-curable group, and / or It may be a mixture with an oligomer or a mixture of three kinds thereof.

The energy ray-curable polymer is preferably a (meth) acrylic acid ester (co) polymer in which a functional group (energy ray-curable group) having energy ray curability is introduced into a side chain. This polymer is preferably obtained by reacting an acrylic copolymer having a functional group-containing monomer unit with an unsaturated group-containing compound having a functional group bonded to the functional group. In addition, in this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.

As the monomer and / or oligomer having at least one or more energy ray-curable groups, for example, an ester of a polyhydric alcohol and (meth) acrylic acid can be used.

As the non-energy ray-curable polymer component, for example, an acrylic copolymer having the above-mentioned functional group-containing monomer unit can be used.

The thickness of the pressure-sensitive adhesive layer 13 is not particularly limited, but is preferably 1 μm or more, and particularly preferably 10 μm or more. The thickness is preferably 100 μm or less, and particularly preferably 50 μm or less.

4. Base material In the circuit member connecting sheet 2 according to the second embodiment, the material constituting the base material 14 is not particularly limited. However, when the connection sheet 2 is a dicing sheet integrated connection sheet (dicing / die bonding sheet) as described later, the material constituting the base material 14 is generally the base material constituting the dicing sheet. It is preferably the material used. For example, a plastic film can be used as such a base material 14, specifically, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, and a vinyl chloride co-weight. Combined film, polyethylene terephthalate film, polyvinyl terephthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film , Polystyrene film, vinyl polyisoprene film, polycarbonate film, polyolefin film, or laminated film thereof and the like can be used.

Further, when the connection sheet 2 is a back grind sheet integrated connection sheet as described later, the material constituting the base material 14 is a material generally used for the base material constituting the back grind sheet. It is preferable to have. For example, a plastic film can be used as the material of such a base material 14, and specifically, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, an ethylene / vinyl acetate copolymer film, or a laminate thereof. A film or the like can be used.

The surface of the base material 14 on the pressure-sensitive adhesive layer 13 side may be subjected to surface treatment such as primer treatment, corona treatment, and plasma treatment in order to enhance the adhesion to the pressure-sensitive adhesive layer 13.

The thickness of the base material 14 is not particularly limited, but is preferably, for example, 10 μm or more, and particularly preferably 15 μm or more. Further, the thickness is preferably, for example, 500 μm or less, and particularly preferably 100 μm or less.

5. Method for Manufacturing Circuit Member Connecting Sheet The circuit member connecting sheet 1 according to the first embodiment can be manufactured in the same manner as the conventional circuit member connecting sheet. For example, in the case of producing a circuit member connecting sheet 1 including the release sheet 12, an adhesive composition and, if desired, a coating liquid containing a solvent or a dispersion medium are prepared and placed on the release surface of the release sheet 12. The connecting sheet 1 can be manufactured by applying the coating liquid with a die coater, a curtain coater, a spray coater, a slit coater, a knife coater, or the like to form a coating film, and drying the coating film. The properties of the coating liquid are not particularly limited as long as it can be applied, and the coating liquid may contain a component for forming the adhesive layer 11 as a solute or a dispersoid. .. The release sheet 12 may be peeled off as a process material, or the adhesive layer 11 may be protected until it is attached to the circuit member.

Further, as a method for manufacturing a laminated body in which the release sheets 12 are laminated on both sides of the circuit member connecting sheet 1, a coating liquid is applied on the release surfaces of the release sheet 12 to form a coating film. This is dried to form a laminate composed of the adhesive layer 11 and the release sheet 12, and the surface of the adhesive layer 11 of the laminate opposite to the release sheet 12 is attached to the release surface of the other release sheet 12. Then, a laminate composed of the release sheet 12 / adhesive layer 11 / release sheet 12 can be obtained. At least one of the release sheets 12 in this laminate may be peeled off as a process material, or the adhesive layer 11 may be protected until it is attached to a circuit member. Examples of the solvent include organic solvents such as toluene, ethyl acetate, and methyl ethyl ketone.

The circuit member connecting sheet 2 according to the second embodiment can also be manufactured in the same manner as the conventional circuit member connecting sheet. For example, a laminate of the adhesive layer 11 and the release sheet and a laminate of the adhesive layer 13 and the base material 14 are prepared, respectively, and these laminates are in contact with the adhesive layer 11 and the adhesive layer 13. The connection sheet 2 can be obtained by sticking the above.

For the laminate of the adhesive layer 11 and the release sheet, the above-mentioned coating liquid for forming the adhesive layer 11 is prepared, and the coating film is applied onto the release surface of the release sheet by the above-mentioned coating method. It can be obtained by forming and drying the coating film.

For the laminate of the pressure-sensitive adhesive layer 13 and the base material 14, a coating liquid containing a material constituting the pressure-sensitive adhesive layer 13 and, if desired, a solvent or a dispersion medium is prepared, and the base material 14 is prepared by the above-mentioned coating method. It can be obtained by applying it to one side of the above to form a coating film and drying the coating film. Further, as another method for producing a laminate of the pressure-sensitive adhesive layer 13 and the base material 14, the pressure-sensitive adhesive layer 13 is formed on the peeling surface of the process release sheet, and then the pressure-sensitive adhesive layer 13 is applied to the base material 14. A laminate of the pressure-sensitive adhesive layer 13 and the base material 14 may be obtained by transferring to one side and peeling off the process release sheet from the pressure-sensitive adhesive layer 13.

[Manufacturing method of semiconductor devices]
A semiconductor device can be manufactured by using the circuit member connecting sheets 1 and 2 according to the present embodiment. In particular, this manufacturing method includes a step of adhering circuit members to each other using the circuit member connecting sheets 1 and 2.

Specifically, the manufacturing method is a step of bonding one surface of the adhesive layer 11 of the connecting sheets 1 and 2 to the surface of one circuit member provided with the electrode where the electrode exists (hereinafter, , "First bonding step"), the other surface of the adhesive layer 11 in the connecting sheets 1 and 2 and the surface of the other circuit member provided with the electrode where the electrode exists are bonded. The joining step (hereinafter, may be referred to as "second bonding step") and the adhesive layer 11 are cured to bond one circuit member and another circuit member, and in one circuit member. It includes a step of electrically connecting an electrode and an electrode in another circuit member (hereinafter, may be referred to as an “adhesive step”).

In the first bonding step and the second bonding step, bonding can be performed by a general method. For example, when the circuit member connecting sheet 1 according to the first embodiment is used, in the first bonding step, the surface of the adhesive layer 11 opposite to the release sheet 12 and the electrode in one circuit member are After bonding the existing surfaces, the release sheet 12 is peeled from the adhesive layer 11, and as a second bonding step, the exposed surface of the adhesive layer 11 and the surface on which the electrodes are present in other circuit members are bonded to each other. Stick them together. Further, when the circuit member connecting sheet 2 according to the second embodiment is used, in the first bonding step, the surface of the adhesive layer 11 opposite to the adhesive layer 13 and the electrode in one circuit member are used. After bonding the surface on which the adhesive layer is present, the laminate of the pressure-sensitive adhesive layer 13 and the base material 14 is separated from the adhesive layer 11, and as a second bonding step, the exposed surface of the adhesive layer 11 and others It is bonded to the surface of the circuit member where the electrodes are present. When separating the laminated body from the adhesive layer 11, if the pressure-sensitive adhesive layer 13 is composed of a curable pressure-sensitive adhesive, the pressure-sensitive adhesive layer 13 is cured to cure the adhesive layer 11 of the laminated body. It is preferable to reduce the adhesive force against the material and separate it. In the second bonding step, the electrodes of one circuit member and the electrodes of the other circuit member may be bonded while being aligned so that they can be electrically connected well in the subsequent bonding process. preferable.

In the above bonding step, circuit members can be bonded to each other and electrodes can be electrically connected to each other by a general method. For example, a laminate obtained by laminating one circuit member, an adhesive layer 11, and another circuit member in this order, which is obtained by the second bonding step, is pressurized and heated. The pressurization brings the electrodes of one circuit member into contact with the electrodes of the other circuit member to form an electrical connection, and the heating cures the adhesive layer 11 so that the circuit members are brought together. It will be glued. The heating is preferably to a temperature sufficient to initiate the curing reaction of the adhesive layer 11, and in particular, in the composite compound, the compound of the above formula (1) is dissociated from the imidazole-based curing catalyst. It is preferable to heat to a sufficient temperature.

In the above manufacturing method, at least one of the back grind step and the dicing step may be performed between the first bonding step and the second bonding step. Further, when the dicing step is performed, a pickup step may be further performed between the dicing step and the second bonding step. It is preferable to use the circuit member connecting sheet 2 according to the second embodiment in the manufacturing method including these additional steps. In particular, when performing the back grind step, it is preferable to use a material suitable for back grind as the base material 14 and use the connecting sheet 2 as the back grind sheet integrated adhesive sheet. Further, when performing the dicing step, it is preferable to use a material suitable for dicing as the base material 14 and use the connecting sheet 2 as a dicing sheet integrated connection sheet (dicing / dicing sheet).

When the backgrinding step is performed, the circuit member preferably has electrodes on only one surface, and specifically, it is preferably a semiconductor wafer having electrodes on only one surface. In this case, for example, in the first bonding step, the surface of the semiconductor wafer provided with the electrodes is bonded to the circuit member connecting sheet 2 according to the second embodiment. Subsequently, as a backgrinding step, the surface of the semiconductor wafer not provided with electrodes is polished on the connection sheet 2 to thin the semiconductor wafer. If necessary, back surface processing other than the back grind process may be performed.

When the dicing step is performed, the circuit member is preferably a semiconductor wafer. In this case, for example, in the first bonding step, the circuit member connecting sheet 2 and the semiconductor wafer according to the second embodiment are bonded. Subsequently, as a dicing step, the semiconductor wafer is cut on the connection sheet 2 and separated into semiconductor chips. At this time, the adhesive layer 11 is also cut to be individualized together with the semiconductor wafer. The cutting method of the semiconductor wafer is not particularly limited, and is performed by various conventionally known dicing methods. For example, a method of cutting a semiconductor wafer using a dicing blade can be mentioned. Further, another dicing method such as laser dicing may be adopted.

When the pick-up step is performed following the dicing step, the obtained semiconductor chip can be picked up by a general method. When the semiconductor chip is picked up, the semiconductor chip with the adhesive layer 11 can be obtained by picking up the semiconductor chip with the individualized adhesive layer 11 attached. Following this, in the second bonding step, the surface of the obtained semiconductor chip with the adhesive layer 11 on the adhesive layer 11 side is placed on the surface of the other circuit member where the electrodes are present. If necessary, the distance between the semiconductor chips may be increased by expanding the connection sheet 2 before the pickup.

In the circuit member connecting sheets 1 and 2 according to the present embodiment, since the adhesive layer 11 is formed from the adhesive composition containing the above-mentioned composite compound, the adhesive layer 11 is heated to a predetermined temperature. The curing reaction is not started until it is done. Therefore, it is possible to suppress the curing of the adhesive layer 11 at an unintended stage, and it is possible to achieve excellent storage stability with respect to thermosetting. Further, when the curing reaction is started by heating the adhesive layer 11 to a predetermined temperature, the curing reaction proceeds rapidly, and the circuit members can be bonded to each other in a short time. As a result, the time of the entire semiconductor device manufacturing method can be shortened, and the productivity of the semiconductor device manufacturing method can be improved.

The embodiments described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

Hereinafter, the present invention will be described in more detail by showing Examples and Test Examples, but the present invention is not limited to the following Test Examples and the like.

[Examples 1 and 2 and Comparative Examples 1 and 2]
The adhesive composition containing the constituents shown in Table 1 was diluted with methyl ethyl ketone so that the solid content concentration was 40% by mass to obtain a coating liquid. The coating liquid is applied onto a silicone-treated release film (manufactured by Lintec Corporation, product name "SP-PET38131"), and the obtained coating film is dried in an oven at 100 ° C. for 1 minute to increase the thickness. A circuit member connecting sheet composed of an adhesive layer having a size of 45 μm and a release film was obtained.

[Test Example 1] (Differential scanning calorimetry)
Using the circuit member connecting sheets prepared in Examples and Comparative Examples, a plurality of adhesive layers were laminated to prepare a measurement sample having a thickness of 15 mm. The obtained measurement sample was heated from 50 ° C. to 300 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter (manufactured by TA Instruments, product name “Q2000”). As a result, the DSC curve is acquired, and for the peak generated due to the curing reaction of the adhesive layer, the temperature that brings about the peak (reaction peak temperature) (° C.) and the slope of the tangent line in contact with the peak become maximum. The temperature at the time (reaction rising temperature) (° C) was obtained. Further, the difference (° C.) was calculated by subtracting the value of the reaction rising temperature from the value of the reaction peak temperature. These results are shown in Table 2.

[Test Example 2] (Evaluation of storage stability)
A measurement sample having a thickness of 15 mm was prepared by laminating a plurality of adhesive layers using the circuit member connecting sheets immediately after being prepared in Examples and Comparative Examples. Immediately after the measurement sample thus obtained, a differential scanning calorimeter (manufactured by TA Instruments, product name "Q2000") was used to raise the temperature from 50 ° C to 300 ° C at a heating rate of 10 ° C / min. It was heated. Thereby obtaining a DSC curve, calculate the heat of reaction from the peak area of that caused by the curing reaction of the adhesive layer, the calculated heat of reaction was H _0.

Furthermore, after the measurement sample obtained in the same manner as above and 1 months storage under 23 ° C. environment, the heat of reaction in the same manner as described above adhesive layer was measured, the calculated heat of reaction was H _1.

Using the obtained heats of reaction H ₀ and H ₁ , the following formula (3)
((H ₀ −H ₁ ) / H ₀ ) × 100 = H ₂ … (3)
H ₂ was calculated from the above, and the storage stability was evaluated by assigning a value of 10% or less as “◯” and a value of more than 10% as “x”. The results are shown in Table 2.

[Test Example 3] (Measurement of time until completion of curing)
Using the circuit member connecting sheets prepared in Examples and Comparative Examples, a plurality of adhesive layers were laminated to prepare a measurement sample having a thickness of 15 mm. The obtained measurement sample was heated at 200 ° C. for a predetermined time using a differential scanning calorimeter (manufactured by TA Instruments, product name “Q2000”). As a result, the DSC curve was obtained, and the time at which the peak caused by the curing reaction of the adhesive layer disappeared was measured, and this was taken as the time (minutes) until the curing was completed. The results are shown in Table 2.

Here, the details of the constituent components shown in Table 1 are as follows.
[Thermoplastic resin]
BisA type phenoxy resin: Bisphenol A type phenoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER1256")
[Thermosetting resin]
BisA type epoxy resin: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828")
Triphenylmethane type epoxy resin: Triphenylmethane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name "EPPN502H")
Novolac-type phenol: Novolac-type phenol (manufactured by Showa Denko, product name "BRG-556")
[Composite compound / curing catalyst]
Encapsulation catalyst 1: 2-Phenyl-4-methyl-5-hydroxymethylimidazole is a composite compound in which 5-hydroxyisophthalic acid is included (manufactured by Nippon Soda Co., Ltd., product name "HIPA-2P4MHZ", imidazole content: 1 mol per 1 mol of 5-hydroxyisophthalic acid)
Encapsulation catalyst 2: A composite compound in which 2-ethyl-4-methylimidazole is encapsulated with 5-hydroxyisophthalic acid (manufactured by Nippon Soda Co., Ltd., product name "HIPA-2E4MZ", imidazole content: 5-hydroxyisophthalic acid) 1.0 mol for 1 mol)
Inclusion catalyst 3: A compound in which 2-phenyl-4-methyl-5-hydroxymethylimidazole is encapsulated with 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (manufactured by Shikoku Kasei Co., Ltd., product name). "TEP-2P4MHZ", imidazole content: 1.0 mol per 1 mol of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane)
Imidazole-based thermosetting catalyst: 2,4-diamino-6- [2'-methylimidazolyl- (1')] -ethyl-s-triazine (manufactured by Shikoku Chemicals Corporation, product name "2MZA")
[Flux component]
Diphenolic acid: Diphenolic acid (manufactured by Kanto Chemical Co., Inc., product name "diphenolic acid")
[Inorganic filler]
Silica filler: Silica filler (manufactured by Admatex, product name "YA050C-MJE", average particle size: 50 nm)

As can be seen from Table 2, the circuit member connecting sheet obtained in the examples was excellent in storage stability regarding the curing reaction, and when the curing reaction started, the curing reaction was completed in a short time.

The circuit member connecting sheet according to the present invention is excellent in storage stability with respect to thermosetting and can cure the adhesive layer in a short time, so that it is suitable for manufacturing an excellent semiconductor device with high productivity. It can be used.

1,2 ... Circuit member connection sheet 11 ... Adhesive layer 12 ... Release sheet 13 ... Adhesive layer 14 ... Base material

Claims (7)

A circuit member connection sheet that is interposed between the opposing electrodes and is used to electrically connect the opposing electrodes.
The circuit member connecting sheet includes at least a curable adhesive layer and has a curable adhesive layer.
The adhesive layer includes a thermosetting resin, a thermoplastic resin, an imidazole-based curing catalyst, and the following formula (1).

Complex compound formed from a compound having the structure of state, and are not formed from the adhesive composition containing a flux component and an inorganic filler,
The adhesive layer is a circuit member connecting sheet characterized in that the reaction rising temperature measured by the differential scanning calorimetry is 140 ° C. or higher and 250 ° C. or lower . The circuit member connection according to claim 1, wherein the adhesive layer has a difference between the reaction rising temperature and the reaction peak temperature measured by the differential scanning calorimetry method of 1 ° C. or higher and 20 ° C. or lower. Sheet for. The imidazole-based curing catalyst is a compound having the structure of the following formula (2).

[In the formula (2), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent. , A phenyl group which may have a substituent, a benzyl group which may have a substituent or a cyanoethyl group. R ^{2 to} R ⁴ independently have a hydrogen atom, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 3 carbon atoms which may have a substituent. Shows a cycloalkyl group of ~ 20, a phenyl group which may have a substituent, a benzyl group which may have a substituent, or an acyl group having 1 to 20 carbon atoms which may have a substituent. .. ]
The circuit member connecting sheet according to claim 1 or 2 , wherein the sheet is characterized by the above. The content of the imidazole-based curing catalyst in the composite compound is 1.0 mol or more and 2.0 mol or less with respect to 1 mol of the compound having the structure of the formula (1). Item 6. The circuit member connecting sheet according to any one of Items 1 to 3 . The thermosetting resin is an epoxy resin or a mixture of an epoxy resin and at least one selected from the group consisting of a phenol resin, a melamine resin, a urea resin, an amine compound and an acid anhydride compound. The circuit member connecting sheet according to any one of claims 1 to 4 , wherein the sheet is characterized by the above. The circuit member connecting sheet according to any one of claims 1 to 5 , wherein the flux component contains a carboxyl group. A step of bonding one surface of the adhesive layer in the circuit member connecting sheet according to any one of claims 1 to 6 to the surface of one circuit member provided with an electrode in which the electrode is present. ,
The step of bonding the other surface of the adhesive layer in the circuit member connecting sheet to the surface of the other circuit member provided with the electrode where the electrode is present, and curing the adhesive layer to obtain the above. A semiconductor characterized by comprising a step of adhering one circuit member and the other circuit member and electrically connecting the electrode of the one circuit member and the electrode of the other circuit member. Manufacturing method of the device.