KR102351843B1 - Film adhesive for semiconductor, semiconductor device manufacturing method and semiconductor device - Google Patents

Abstract

The film adhesive for semiconductors of this invention is provided on the 1st layer containing the 1st adhesive agent containing a flux compound, and the 2nd adhesive agent which is provided on the 1st layer and does not contain a flux compound substantially provide a layer

Description

Film adhesive for semiconductor, semiconductor device manufacturing method and semiconductor device

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

Conventionally, in order to connect a semiconductor chip and a board|substrate, the wire bonding method using metal thin wires, such as a gold wire, is widely applied. On the other hand, in order to meet the demands for high functionality, high integration, and high speed of semiconductor devices, a flip chip connection method (FC connection method) in which conductive projections called bumps are formed on a semiconductor chip or substrate to directly connect the semiconductor chip to the substrate (FC connection method) This is spreading.

For example, in connection between a semiconductor chip and a substrate, a COB (Chip On Board) type connection method that is actively used in a Ball Grid Array (BGA), a Chip Size Package (CSP), etc. corresponds to the FC connection method. The FC connection method is also widely used in a COC (Chip On Chip) type connection method in which a connection portion (eg, a bump and a wiring) is formed on a semiconductor chip to connect the semiconductor chips.

Further, in a package that is strongly required for further miniaturization, thickness reduction and high functionality, a chip stack type package, POP (Package On Package), TSV (Through -Silicon Via) is also beginning to be widely used. In this stacking/multilayering technique, since semiconductor chips and the like are arranged three-dimensionally, the package can be made small compared to a two-dimensional arrangement method. In addition, since it is effective for improving semiconductor performance, reducing noise, reducing mounting area, and saving power, it is attracting attention as a next-generation semiconductor wiring technology.

By the way, generally, metal bonding is used for the connection of connection parts from a viewpoint of ensuring sufficient connection reliability (for example, insulation reliability). As a main metal used for the said connection part (for example, bump and wiring), there exist solder, tin, gold|metal|money, silver, copper, nickel, etc., and the electrically-conductive material containing these multiple types is also used. In the metal used for the connection part, impurities may be generated on the connection surface of the connection part because the surface is oxidized to form an oxide film and impurities such as oxide adhere to the surface. When such impurities remain, there is a concern that the connection reliability (eg, insulation reliability) between the semiconductor chip and the substrate or between the two semiconductor chips will decrease, and the merit of employing the above-described connection method will be impaired.

In addition, as a method of suppressing the generation of these impurities, there is a method of coating the connection part with an antioxidant film, which is known in OSP (Organic Solderbility Preservatives) treatment, etc. It may be the cause.

Then, as a method of removing the above-mentioned oxide film and impurities, a method using a single-layer film containing a flux agent as a semiconductor material has been proposed (see, for example, Patent Document 1).

Patent Document 1: International Publication No. 2013/125086

By the way, in flip-chip packages, high functionality and high integration are progressing further in recent years. As the function and integration are increased, the pitch between wirings becomes narrower, so that the connection reliability tends to decrease.

Moreover, from a viewpoint of improving productivity, it is calculated|required to shorten the crimping|compression-bonding time at the time of assembling a flip-chip package in recent years. When crimping|compression-bonding time is shortened and the film adhesive for semiconductors does not fully harden|cure during crimping|bonding, a connection part cannot fully be protected and when the pressure at the time of crimping|compression-bonding is released, poor connection arises. Moreover, when solder is used for a connection part, if the film adhesive for semiconductors does not fully harden|cure during crimping|compression-bonding in the temperature range lower than the solder melting temperature, when the temperature at the time of crimping|compression-bonding reaches the solder melting temperature, the solder scattering and flow occurs, resulting in poor connection. On the other hand, when the film adhesive for semiconductors hardens|cures before connecting parts contact by crimping|bonding, it will be in the state which the adhesive agent interposed between connecting parts, and poor connection arises.

Then, an object of this invention is to provide the film adhesive for semiconductors which can acquire the outstanding connection reliability even when crimping|compression-bonding time is shortened. Moreover, this invention aims at providing the semiconductor device using such a film adhesive for semiconductors, and its manufacturing method.

The film adhesive for semiconductors of this invention is provided on the 1st layer containing the 1st adhesive agent containing a flux compound, and the 2nd adhesive agent which is provided on the 1st layer and does not contain a flux compound substantially provide a layer

According to the film adhesive for semiconductors of the present invention, since the second layer is less susceptible to the influence of the flux compound, the second layer can exhibit properties of curing quickly and sufficiently after contacting the connecting parts with each other. Even when crimping is performed at a high temperature or for a short time, excellent connection reliability (eg, insulation reliability) can be obtained. Moreover, according to the film adhesive for semiconductors of this invention, since shortening of crimping|compression-bonding time is possible, productivity can be improved. Moreover, according to the film adhesive for semiconductors of this invention, a flip-chip package can be made highly functional and highly integrated easily.

However, in the conventional adhesive for semiconductors, when the adhesive for semiconductors is hot-bonded in an uncured state, voids may occur. On the other hand, according to the film adhesive for semiconductors of this invention, since hardening is fully possible in a short time, generation|occurrence|production of a void can be suppressed easily.

In recent years, as the metal of the connection portion, solder, copper, or the like tends to be used in place of gold, which is difficult to corrode, for the purpose of reducing the cost. Also, regarding the surface treatment of wirings and bumps, for the purpose of reducing the cost, there is a tendency to use solder, copper, etc. instead of gold which is difficult to corrode, and there is a tendency to perform processing such as OSP (Organic Solderability Preservative) treatment. In a flip chip package, since such a cost reduction is progressing in addition to narrow pitch and multi-pin formation, the metal which corrodes and tends to reduce insulation tends to be used, and insulation reliability falls easily. On the other hand, according to the film adhesive for semiconductors of this invention, it can suppress that the insulation reliability with respect to the said metal falls.

It is preferable that the hardening reaction rate when a 2nd adhesive agent is hold|maintained at 200 degreeC for 5 second is 80 % or more. In this case, even when crimping is performed at a high temperature and in a short time, more excellent connection reliability can be obtained.

The second adhesive preferably contains a radical polymerizable compound and a thermal radical generator. In this case, since the curing rate is very excellent, it is difficult to generate voids even when compression is performed at a high temperature and for a short time, and more excellent connection reliability can be obtained.

The thermal radical generator is preferably a peroxide. In this case, since the further excellent handleability and storage stability can be acquired, the further outstanding connection reliability is easy to be acquired.

It is preferable that a radically polymerizable compound is a (meth)acrylic compound. In this case, it is easy to obtain the further excellent connection reliability.

The (meth)acrylic compound preferably has a fluorene-type skeleton. In this case, it is easy to obtain the further excellent connection reliability.

It is preferable that the flux compound has a carboxyl group, and it is more preferable that it has two or more carboxyl groups. In this case, it is easy to obtain the further excellent connection reliability.

The flux compound is preferably a compound represented by the following formula (2). In this case, it is easy to obtain the further excellent connection reliability.

[In formula (2), R ¹ and R ² each independently represent a hydrogen atom or an electron-donating group, and n represents 0 or an integer of 1 or more.]

It is preferable that the melting point of the flux compound is 150° C. or less. In this case, since the flux is melted before the adhesive is cured during thermocompression bonding and the oxide film such as solder is removed by reduction, further excellent connection reliability can be easily obtained.

A method for manufacturing a semiconductor device of the present invention is a method for manufacturing a semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other, wherein the connection portion The process of sealing at least one part using the film adhesive for semiconductors mentioned above is provided. According to the method for manufacturing a semiconductor device of the present invention, a semiconductor device having excellent connection reliability (eg, insulation reliability) can be obtained even when crimping is performed at a high temperature and for a short time. That is, according to the manufacturing method of this invention, the semiconductor device excellent in connection reliability (for example, insulation reliability) can be manufactured in a short time.

The semiconductor device of the present invention is a semiconductor device in which the respective connecting portions of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a semiconductor device in which respective connecting portions of a plurality of semiconductor chips are electrically connected to each other, wherein at least a portion of the connecting portions are It is sealed with the hardened|cured material of the film adhesive for semiconductors. This semiconductor device is excellent in connection reliability (eg, insulation reliability).

ADVANTAGE OF THE INVENTION According to this invention, even when crimping|compression-bonding time is shortened, the film adhesive for semiconductors which can obtain the outstanding connection reliability can be provided. Moreover, according to this invention, the semiconductor device using such a film adhesive for semiconductors, and its manufacturing method can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows one Embodiment of the semiconductor device of this invention.
Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.
4 is a process cross-sectional view schematically showing an embodiment of a method for manufacturing a semiconductor device of the present invention.

In this specification, "(meth)acrylate" means at least one of an acrylate and the methacrylate corresponding to it. The same applies to other similar expressions such as “(meth)acryloyl” and “(meth)acrylic acid”. In addition, the numerical range shown using "-" represents a range including the numerical value described before and after "-" as a minimum value and a maximum value, respectively.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.

In addition, the same code|symbol is attached|subjected to the same or corresponding part in drawing, and overlapping description is abbreviate|omitted. In addition, the positional relationship, such as up, down, left and right, shall be based on the positional relationship shown in drawing, unless it specifically asks for understanding.

In addition, the dimension ratio of a drawing is not limited to the ratio shown.

<Film-type adhesive for semiconductor>

The film adhesive for semiconductors of this embodiment is provided on the 1st layer (flux containing layer) containing the 1st adhesive agent containing a flux compound, and the 1st layer, The 2nd adhesive agent which does not contain a flux compound substantially and a second layer (flux-free layer) comprising:

The film adhesive for semiconductors of the present embodiment is, for example, a semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other. It is used for sealing at least a part of the connection part.

According to the film adhesive for semiconductors of this embodiment, in manufacture of the said semiconductor device, when the crimping|compression-bonding time (for example, the crimping|compression-bonding time in the process of crimping|bonding in order to bond a semiconductor chip and a wiring circuit board together) is shortened (for example, Even when the crimping time is set to 5 seconds or less), excellent connection reliability can be obtained.

(first adhesive)

The first adhesive contains, for example, a thermosetting component and a flux compound. As a thermosetting component, a thermosetting resin, a hardening|curing agent, etc. are mentioned. Examples of the thermosetting resin include an epoxy resin, a phenol resin (except when contained as a curing agent), and a polyimide resin. Among these, it is preferable that a thermosetting resin is an epoxy resin. Moreover, the film adhesive for semiconductors of this embodiment may contain the polymer component and filler whose weight average molecular weight is 10000 or more as needed.

Hereinafter, the first adhesive includes an epoxy resin (hereinafter, sometimes referred to as “component (a)”), a curing agent (hereinafter referred to as “component (b)” in some cases), and a flux compound (hereinafter, referred to as “component (b)” in some cases). , sometimes referred to as “component (c)”) and, if necessary, a polymer component having a weight average molecular weight of 10000 or more (hereinafter referred to as “component (d)” in some cases) and fillers (hereinafter, in the case An embodiment containing "(e) component" will be described.

[(a) component: epoxy resin]

As an epoxy resin, if it has two or more epoxy groups in a molecule|numerator, it can use without restriction|limiting in particular. (a) As a component, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, A triphenylmethane type epoxy resin, a dicyclopentadiene type epoxy resin, and various polyfunctional epoxy resins can be used. These can be used individually or as a mixture of 2 or more types.

(a) component, from the viewpoint of suppressing the generation of volatile components by decomposition at the time of connection at high temperature, when the temperature at the time of connection is 250 ° C., the thermogravimetric decrease ratio at 250 ° C. is 5% or less epoxy It is preferable to use a resin, and when the temperature at the time of connection is 300 degreeC, it is preferable to use the epoxy resin whose thermogravimetric reduction amount ratio in 300 degreeC is 5 % or less.

The content of the component (a) is, for example, 5 to 75 mass%, preferably 10 to 50 mass%, and more preferably 15 to 35 mass%, based on the total amount of the first adhesive.

[(b) component: curing agent]

Examples of the component (b) include a phenol resin curing agent, an acid anhydride curing agent, an amine curing agent, an imidazole curing agent, and a phosphine curing agent. When the component (b) contains a phenolic hydroxyl group, an acid anhydride, an amine, or an imidazole, flux activity for suppressing the formation of an oxide film on the connection portion is exhibited, and connection reliability and insulation reliability can be improved. Hereinafter, each hardening|curing agent is demonstrated.

(i) phenolic resin curing agent

The phenol resin curing agent 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, cresolnaphthol formaldehyde polycondensate, triphenylmethane type polyfunctional A phenol resin and various polyfunctional phenol resins can be used. These can be used individually or as a mixture of 2 or more types.

The equivalent ratio of the phenolic resin curing agent to the component (a) (the number of moles of phenolic hydroxyl groups in the phenolic resin curing agent / the number of moles of epoxy groups in the component (a)) is 0.3 to 1.5 is preferable, 0.4-1.0 are more preferable, and 0.5-1.0 are still more preferable. When the equivalence ratio is 0.3 or more, curability is improved and adhesive strength tends to be improved, and when it is 1.5 or less, unreacted phenolic hydroxyl groups do not remain excessively, water absorption is suppressed low, and insulation reliability tends to be improved. .

(ii) an acid anhydride curing agent

As the acid anhydride curing agent, for example, methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride and ethylene glycol bisanhydrotrimellitate can be used. These can be used individually or as a mixture of 2 or more types.

The equivalent ratio of the acid anhydride curing agent to the component (a) (the number of moles of the acid anhydride groups of the acid anhydride curing agent / the number of moles of the epoxy groups of the component (a)) is, from the viewpoint of good curability, adhesiveness and storage stability, 0.3-1.5 are preferable, 0.4-1.0 are more preferable, and 0.5-1.0 are still more preferable. When the equivalence ratio is 0.3 or more, curability tends to improve and adhesive strength tends to improve, and when it is 1.5 or less, unreacted acid anhydride does not remain excessively, water absorption is suppressed low, and insulation reliability tends to be improved.

(iii) amine-based curing agent

As the amine curing agent, for example, dicyandiamide can be used.

The equivalent ratio of the amine-based curing agent to the component (a) (the number of moles of active hydrogen groups in the amine-based curing agent / the number of moles of epoxy groups in the component (a)) is 0.3 to 1.5 from the viewpoint of good curability, adhesion and storage stability. is preferable, 0.4 to 1.0 are more preferable, and 0.5 to 1.0 are still more preferable. When the equivalence ratio is 0.3 or more, curability improves and adhesive force tends to improve, and when it is 1.5 or less, unreacted amine does not remain excessively and insulation reliability tends to improve.

(iv) imidazole-based curing agent

Examples of the imidazole-based curing agent include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-cya. Noethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenyl Midazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'- Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl- s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and imidazoles are mentioned. . Among these, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-unde from a viewpoint of the outstanding sclerosis|hardenability, storage stability, and connection reliability. Silimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl- s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazolisocyanuric acid adduct, 2-phenyl-4,5-dihydr Preference is given to hydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. These can be used individually or in combination of 2 or more types. Moreover, it is good also as a latent hardening|curing agent which microencapsulated these.

0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for content of an imidazole type hardening|curing agent, 0.1-10 mass parts is more preferable. It exists in the tendency for sclerosis|hardenability to improve that content of an imidazole type hardening|curing agent is 0.1 mass part or more. Moreover, when content of an imidazole type hardening|curing agent is 20 mass parts or less, the fluidity|liquidity of the 1st adhesive agent at the time of crimping|compression-bonding can be ensured and the 1st adhesive agent between connection parts can fully be excluded. As a result, since curing of the first adhesive in the state interposed between the solder and the connecting portion is suppressed, there is a tendency that poor connection is unlikely to occur.

(v) phosphine-based curing agent

Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphoniumtetraphenylborate, tetraphenylphosphoniumtetra(4-methylphenyl)borate, and tetraphenylphosphonium(4-fluorophenyl)borate.

0.1-10 mass parts is preferable with respect to 100 mass parts of (a) component, and, as for content of a phosphine-type hardening|curing agent, 0.1-5 mass parts is more preferable. If the content of the phosphine-based curing agent is 0.1 parts by mass or more, curability tends to be improved, and if it is 10 parts by mass or less, the first adhesive does not cure before metal bonding is formed, and there is a tendency that poor connection is unlikely to occur. have.

Each of the phenol resin curing agent, the acid anhydride curing agent and the amine curing agent may be used alone or as a mixture of two or more thereof. The imidazole-based curing agent and the phosphine-based curing agent may be used alone, or may be used together with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.

When the first adhesive includes a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent as the component (b), it exhibits flux activity for removing the oxide film, thereby further improving connection reliability.

[(c) component: flux compound]

Component (c) is a compound having flux activity, and functions as a flux agent in the first adhesive. As the component (c), a known component can be used without particular limitation, as long as it facilitates metal bonding by reducing and removing the oxide film on the surface of solder or the like. (c) As a component, 1 type of flux compound may be used independently, and 2 or more types of flux compound may be used together. However, (c) component does not contain the hardening|curing agent which is (b) component.

The flux compound preferably has a carboxyl group, and more preferably has two or more carboxyl groups, from the viewpoint that sufficient flux activity can be obtained and superior connection reliability can be obtained. Among these, the compound which has two carboxyl groups is preferable. Compared with the compound (monocarboxylic acid) which has one carboxyl group, the compound which has two carboxyl groups is hard to volatilize also by the high temperature at the time of connection, and can suppress generation|occurrence|production of a void further. Moreover, when the compound which has two carboxyl groups is used, compared with the case where the compound which has three or more carboxyl groups is used, the increase in the viscosity of the film adhesive for semiconductors at the time of storage and connection work, etc. can be suppressed further, , the connection reliability of the semiconductor device can be further improved.

As the flux compound having a carboxyl group, a compound having a group represented by the following formula (1) is preferably used.

In Formula (1), R<^1> represents a hydrogen atom or an electron-donating group.

From the viewpoint of being excellent in reflow resistance and further excellent in connection reliability, it is preferable that ^{R 1 is an electron donor.} In this embodiment, after the 1st adhesive contains an epoxy resin and a hardening|curing agent, among the compounds which have a group represented by Formula (1), R<^1> is an electron-donating group and also contains a compound, whereby metal bonding is carried out. Even when it applies as a film adhesive for semiconductors in a chip connection system, manufacture of the semiconductor device excellent in reflow resistance and connection reliability is attained.

It is necessary to suppress the adhesive force fall after moisture absorption in high temperature for the improvement of reflow property. Although carboxylic acid is conventionally used as a flux compound, the present inventors consider that the fall of adhesive force arises in the conventional flux compound for the following reasons.

Usually, the curing reaction proceeds by reacting the epoxy resin with the curing agent. At this time, the carboxylic acid as a flux compound is collected in the curing reaction. That is, an ester bond may be formed when the epoxy group of an epoxy resin reacts with the carboxyl group of a flux compound. This ester bond easily causes hydrolysis etc. by moisture absorption etc., and decomposition|disassembly of this ester bond is considered to be one cause of the fall of the adhesive force after moisture absorption.

On the other hand, among the compounds having a group represented by the formula (1), when a compound having a group in which R ¹ is an electron-donating group, that is, a compound having a carboxyl group having an electron-donating group in its vicinity, is contained, the flux activity is reduced by the carboxyl group. While sufficiently obtained, even when the above-described ester bond is formed, the electron density of the ester bond portion increases due to the electron-donating group, and decomposition of the ester bond is suppressed. Moreover, since a substituent (electron-donating group) exists in the vicinity of a carboxyl group, reaction of a carboxyl group and an epoxy resin is suppressed by steric hindrance, and it is thought that it becomes difficult to produce|generate an ester bond.

For these reasons, among the compounds having a group represented by Formula (1), ^{when using the first adhesive further containing a compound in which R 1} is an electron-donating group, composition changes due to moisture absorption or the like hardly occur, and excellent adhesive strength is maintained do. In addition, it can be said that the above-described action is difficult to inhibit the curing reaction of the epoxy resin and the curing agent by the flux compound. can

When the electron-donating group of the electron-donating group becomes strong, the effect of suppressing the decomposition of the above-described ester bond tends to be easily obtained. Moreover, when the steric hindrance of an electron-donating group is large, it will become easy to acquire the effect of suppressing reaction of the above-mentioned carboxyl group and an epoxy resin. The electron-donating group preferably has a good balance between electron donating and steric hindrance.

Examples of the electron-donating group include an alkyl group, a hydroxyl group, an amino group, an alkoxy group, and an alkylamino group. As the electron-donating group, a group that does not readily react with other components (eg, the epoxy resin of component (a)) is preferable, and specifically, an alkyl group, a hydroxyl group or an alkoxy group is preferable, and an alkyl group is more preferable.

As an alkyl group, a C1-C10 alkyl group is preferable, and a C1-C5 alkyl group is more preferable. As the number of carbon atoms in the alkyl group increases, electron donating and steric hindrance tend to increase. Since the alkyl group having the carbon number within the above range is excellent in the balance between electron donating and steric hindrance, the effect of the present invention is further remarkably exhibited according to the above alkyl group.

Moreover, linear or branched form may be sufficient as an alkyl group, and it is preferable that it is linear. When the alkyl group is linear, it is preferable that the number of carbon atoms in the alkyl group is equal to or less than the number of carbon atoms in the main chain of the flux compound from the viewpoint of the balance of electron donating and steric hindrance. For example, when the flux compound is a compound represented by the following formula (2) and the electron-donating group is a linear alkyl group, the number of carbon atoms in the alkyl group is preferably not more than (n+1) carbon atoms in the main chain of the flux compound.

As an alkoxy group, a C1-C10 alkoxy group is preferable and a C1-C5 alkoxy group is more preferable. As the number of carbon atoms in the alkoxy group increases, electron donating and steric hindrance tend to increase. Since the alkoxy group having the carbon number within the above range is excellent in the balance between electron donating and steric hindrance, the effect of the present invention is further remarkably exhibited according to the above alkoxy group.

Moreover, linear or branched form may be sufficient as the alkyl group part of an alkoxy group, and it is preferable that it is linear. When the alkoxy group is linear, the carbon number of the alkoxy group is preferably equal to or less than the carbon number of the main chain of the flux compound from the viewpoint of the balance of electron donating and steric hindrance. For example, when the flux compound is a compound represented by the following formula (2) and the electron-donating group is a straight-chain alkoxy group, it is preferable that the carbon number of the alkoxy group is not more than (n+1) carbon atoms in the main chain of the flux compound.

Examples of the alkylamino group include a monoalkylamino group and a dialkylamino group. As a monoalkylamino group, a C1-C10 monoalkylamino group is preferable, and a C1-C5 monoalkylamino group is more preferable. The alkyl group part of the monoalkylamino group may be linear or branched, and it is preferable that it is linear.

As a dialkylamino group, a C2-C20 dialkylamino group is preferable, and a C2-C10 dialkylamino group is more preferable. The alkyl group part of the dialkylamino group may be linear or branched, and it is preferable that it is linear.

As the flux compound having two carboxyl groups, a compound represented by the following formula (2) can be suitably used. According to the compound represented by following formula (2), the reflow resistance and connection reliability of a semiconductor device can be improved further.

In formula (2), R ¹ and R ² each independently represent a hydrogen atom or an electron-donating group, and n represents 0 or an integer of 1 or more. A plurality of R ^{2 s} may be the same or different from each other.

R ¹ is synonymous with Formula (1). In addition, the electron donor represented by R ² are the same as examples of the above-described electron-donating group described as R ^1. For the same reason as explained in formula (1), ^{it is preferable that R 1} in formula (2) is an electron-donating group.

It is preferable that n in Formula (2) is 1 or more. When n is 1 or more, compared with the case where n is 0, the flux compound is less likely to volatilize even at a high temperature during connection, and generation of voids can be further suppressed. Moreover, as for n in Formula (2), it is preferable that it is 15 or less, It is more preferable that it is 11 or less, 6 or less or 4 or less may be sufficient. When n is 15 or less, further excellent connection reliability can be obtained.

Moreover, as a flux compound, the compound represented by following formula (3) is more suitable. According to the compound represented by following formula (3), the reflow resistance and connection reliability of a semiconductor device can be improved further.

In formula (3), R ¹ and R ² each independently represent a hydrogen atom or an electron-donating group, and m represents 0 or an integer of 1 or more.

It is preferable that m in Formula (3) is 10 or less, It is more preferable that it is 5 or less, It is still more preferable that it is 3 or less. When m is 10 or less, further excellent connection reliability can be obtained.

In Formula (3), R<^1> and R<^2> may be a hydrogen atom or an electron-donating group may be sufficient as it. It is preferable that at least one of ^R<1> and R<^2> is an electron-donating group from a viewpoint of being able to acquire the further outstanding connection reliability. When R ¹ is an electron-donating group and R ² is a hydrogen atom, the melting point tends to be low, and the connection reliability of the semiconductor device can be further improved in some cases. In addition, when R ¹ and R ² are different electron-donating groups, ^{compared to the case where R 1} and R ² are the same electron-donating groups, the melting point tends to be lowered, which can further improve the connection reliability of the semiconductor device. There are cases.

Moreover, in Formula (3), when R<^1> and R<^2> are the same electron-donating group, it becomes a symmetric structure and there exists a tendency for melting|fusing point to become high. Even in this case, the effect of this invention is fully acquired. In particular, when the melting point is sufficiently low at 150° C. or less, even when R ¹ and R ² are the same group, the same level of connection reliability as in the case where ^{R 1} and R ^{2 are different groups can be obtained.}

Examples of the flux compound include dicarboxylic acids selected from succinic acid, glutaric acid, adipic acid, pimelinic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid and dodecanedioic acid, and these dicarboxylic acids. A compound in which an electron-donating group is substituted at the 2-position of the acid may be used.

150 degrees C or less is preferable, as for melting|fusing point of a flux compound, 140 degrees C or less is more preferable, and 130 degrees C or less is still more preferable. Such a flux compound tends to sufficiently exhibit flux activity before the curing reaction between the epoxy resin and the curing agent occurs. Therefore, according to the film adhesive for semiconductors using the 1st adhesive agent containing such a flux compound, the semiconductor device further excellent in connection reliability can be implement|achieved. Moreover, 25 degreeC or more is preferable and, as for melting|fusing point of a flux compound, 50 degreeC or more is more preferable. In addition, it is preferable that the flux compound is solid at room temperature (25°C).

The melting point of the flux compound can be measured using a general melting point measuring device. The sample for measuring the melting point is pulverized into a fine powder, and it is required to reduce the temperature variation in the sample by using a trace amount. A capillary tube closed at one end is often used as a container for a sample, but depending on the measuring device, it is used as a container by sandwiching two pieces of cover glass for a microscope. In addition, when the temperature is rapidly increased, a temperature gradient is generated between the sample and the thermometer, which causes measurement errors. Therefore, the heating at the time of measuring the melting point is preferably measured at a rate of increase of 1° C. or less per minute.

As described above, since the material for measuring the melting point is prepared as a fine powder, the sample before melting is opaque due to diffuse reflection from the surface. It is common that the temperature at which the appearance of the sample begins to become transparent is the lower limit of the melting point, and the temperature at which the sample has been melted is the upper limit. Although various types of measuring devices exist, the most classic device is a device that heats the sample with a hot bath by attaching a capillary filled with a sample to a double-tube thermometer. For the purpose of bonding the capillary to the double tube thermometer, a liquid with high viscosity is used as the liquid of the warm bath, and concentrated sulfuric acid or silicone oil is often used. Moreover, as a melting|fusing point measuring apparatus, while heating using a metal heat block, while measuring the light transmittance, it can also use what determines melting|fusing point automatically while adjusting heating.

In addition, in this specification, melting|fusing point 150 degreeC or less means that the upper limit of melting|fusing point is 150 degrees C or less, and melting|fusing point 25 degreeC or more means that the lower limit of melting|fusing point is 25 degreeC or more.

(c) It is preferable that it is 0.5-10 mass % based on the whole quantity of a 1st adhesive agent, and, as for content of component, it is more preferable that it is 0.5-5 mass %.

[Component (d): polymer component having a weight average molecular weight of 10000 or more]

The 1st adhesive agent may contain the polymer component ((d) component) whose weight average molecular weight is 10000 or more as needed. The first adhesive containing the component (d) is further excellent in heat resistance and film formability.

(d) As the component, for example, phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, and acrylic rubber are mentioned. Among these, phenoxy resins, polyimide resins, acrylic rubbers, cyanate ester resins and polycarbodiimide resins are preferable from the viewpoint of excellent heat resistance and film formability, and phenoxy resins, polyimide resins and acrylic rubbers are more desirable. These (d) components may be used individually or as a mixture or copolymer of 2 or more types. However, the compound corresponding to the component (a) and the compound corresponding to the component (e) are not included in (d) component.

(d) The weight average molecular weight of the component is, for example, 10000 or more, preferably 20000 or more, and more preferably 30000 or more. According to such component (d), the heat resistance and film formability of a 1st adhesive agent can be improved further.

Moreover, it is preferable that it is 1000000 or less, and, as for the weight average molecular weight of (d) component, it is more preferable that it is 500000 or less. According to such component (d), the heat resistance of a 1st adhesive agent can be improved further.

In addition, in this specification, a weight average molecular weight means a weight average molecular weight when it measures in polystyrene conversion using high performance liquid chromatography (The Shimadzu Corporation make, brand name: C-R4A). For the measurement, for example, the following conditions can be used.

Detector: LV4000 UV Detector (manufactured by Hitachi, Ltd., trade name)

Pump: L6000 Pump (manufactured by Hitachi, Ltd., trade name)

Column: Gelpack GL-S300MDT-5 (two copies in total) (manufactured by Hitachi Chemical Co., Ltd., trade name)

Eluent: THF/DMF=1/1 (volume ratio)+LiBr (0.03 mol/L)+H3PO4 (0.06 mol/L)

Flow: 1 mL/min

When the first adhesive contains the component (d), the ratio C _a /C _{d (mass ratio) of the content C a} of the component (a) to _{the content C d} of the component (d) is preferably 0.01 to 5, and , It is more preferable that it is 0.05-3, and it is still more preferable that it is 0.1-2. When the ratio (C _a /C _d ) is 0.01 or more, better curability and adhesive force can be obtained, and when the ratio (C _a /C _d ) is 5 or less, better film formability can be obtained.

[(e) component: filler]

The 1st adhesive agent may contain the filler ((e) component) as needed. (e) The component can control the viscosity of the first adhesive, the physical properties of the cured product of the first adhesive, and the like. Specifically, according to the component (e), it is possible to achieve, for example, suppression of generation of voids during connection, reduction of the moisture absorption rate of the cured product of the first adhesive, and the like.

(e) As a component, an inorganic filler (inorganic particle), an organic filler (organic particle), etc. are mentioned. Examples of the inorganic filler include insulating inorganic fillers such as glass, silica, alumina, titanium oxide, mica, and boron nitride, and among them, at least one selected from the group consisting of silica, alumina, titanium oxide and boron nitride is preferable; At least one selected from the group consisting of silica, alumina and boron nitride is more preferable. A whisker may be sufficient as an insulating inorganic filler. Examples of the whisker include aluminum borate, aluminum titanate, zinc oxide, calcium silicate, and boron nitride. As an organic filler, a resin filler (resin particle) is mentioned, for example. Polyurethane, polyimide, etc. are mentioned as a resin filler. Since a resin filler can provide flexibility at high temperature, such as 260 degreeC, compared with an inorganic filler, since it is suitable for improving reflow resistance, and since softness|flexibility provision is possible, it is effective also in film formability improvement.

From the viewpoint of further excellent insulation reliability, the component (e) is preferably insulating. It is preferable that the 1st adhesive agent does not contain electroconductive metal fillers (metal particles), such as a silver filler and a solder filler, and electroconductive inorganic fillers, such as carbon black.

(e) The physical properties of the component may be appropriately adjusted by surface treatment. It is preferable that (e) component is the filler which surface-treated from a viewpoint that dispersibility or adhesive force improves. As a surface treatment agent, the compound of a glycidyl type (epoxy type), an amine type, a phenyl type, a phenylamino type, a (meth)acrylic type, a vinyl type, etc. are mentioned.

As the surface treatment, silane treatment with a silane compound such as an epoxysilane type, an aminosilane type or an acrylsilane type is preferable from the viewpoint of the easiness of the surface treatment. The surface treatment agent is preferably at least one selected from the group consisting of a glycidyl compound, a phenylamino compound and a (meth)acrylic compound from the viewpoint of excellent dispersibility, fluidity and adhesion. As a surface treating agent, at least 1 sort(s) selected from the group which consists of a phenyl-type compound and a (meth)acrylic-type compound from a viewpoint of being excellent in storage stability is preferable.

(e) The average particle diameter of the component is preferably 1.5 µm or less from the viewpoint of preventing meshing during flip-chip connection, and more preferably 1.0 µm or less from the viewpoint of excellent visibility (transparency).

(e) The content of the component is 30% by mass or more based on the total amount of the first adhesive from the viewpoint of suppressing the lowering of the heat dissipation property and the tendency to easily suppress the occurrence of voids, increase in moisture absorption, etc. This is preferable, and 40 mass % or more is more preferable. The content of the component (e) tends to suppress the decrease in the fluidity of the first adhesive due to the increase in viscosity and the occurrence of entrapment (trapping) of the filler in the connection portion, and tends to easily suppress the decrease in connection reliability. From a viewpoint, 90 mass % or less is preferable based on the whole quantity of a 1st adhesive agent, and 80 mass % or less is more preferable. From these viewpoints, 30-90 mass % is preferable on the basis of the whole quantity of the 1st adhesive agent, and, as for content of (e) component, 40-80 mass % is more preferable.

[Other Ingredients]

Additives, such as antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion trap agent, may be mix|blended with the 1st adhesive agent. These can be used individually by 1 type or in combination of 2 or more type. About these compounding quantities, what is necessary is just to adjust suitably so that the effect of each additive may be expressed.

(Second Adhesive)

The second adhesive is substantially free of flux compounds. "It does not contain substantially" means that the content of the flux compound in the second adhesive is less than 0.5 mass% based on the total amount of the second adhesive.

It is preferable that the hardening reaction rate of a 2nd adhesive agent when hold|maintained for 5 second at 200 degreeC from a viewpoint that the effect of this invention can be acquired remarkably is 80 % or more. Examples of the second adhesive include a radical curing adhesive. Although the reason why the effect of this invention can be acquired remarkably by such an adhesive agent is not clear, the present inventors guess as follows.

That is, in the conventional film adhesive containing a flux compound, since a flux component deactivates radicals, a radical curing system could not be applied, but the cationic curing system using an epoxy etc. was applied in many cases. In this curing system (reaction system), since curing proceeds by nucleophilic addition reaction, the curing rate is slow, and voids may be generated after crimping. In the conventional film adhesive, it is guessed that the trouble (for example, peeling of the semiconductor material in reflow temperature around 260 degreeC, connection defect of a connection part, etc.) had generate|occur|produced by the void at the time of this mounting. On the other hand, since the above-described second adhesive does not contain a flux compound substantially, the curing system can be set as a radical curing system, and a sufficient curing rate can be obtained. Therefore, by using the 2nd adhesive agent mentioned above for a 2nd layer, even when crimping|compression-bonding is performed at high temperature and a short time, it becomes difficult to generate|occur|produce a void, and it is guessed that the effect of this invention becomes remarkable. Moreover, since sufficient hardening rate can be obtained in this embodiment, for example, even when solder is used for a connection part, a film adhesive can be hardened in the temperature range lower than the solder melting temperature. Therefore, it is possible to sufficiently suppress the occurrence of solder scattering and flow, resulting in poor connection.

Hereinafter, the second adhesive is a radically polymerizable compound (hereinafter referred to as "component (A)" in some cases), a thermal radical generator (hereinafter referred to as "component (B)" in some cases) and , if necessary, a polymer component (hereinafter, sometimes referred to as “(C) component”) and a filler (hereinafter referred to as “(D) component” in some cases.) will be described. do.

[Component (A): radically polymerizable compound]

The component (A) is a compound capable of a radical polymerization reaction by generating radicals by heat, light, radiation, electrochemical action, or the like. (A) As a component, a (meth)acrylic compound, a vinyl compound, etc. are mentioned. (A) As a component, a (meth)acrylic compound is preferable from a viewpoint of being excellent in durability, electrical insulation, and heat resistance. The (meth)acrylic compound is not particularly limited as long as it is a compound having one or more (meth)acryl group ((meth)acryloyl group) in the molecule, for example, bisphenol A type, bisphenol F type, naphthalene type, phenol novolac type , cresol novolak type, phenol aralkyl type, biphenyl type, triphenylmethane type, dicyclopentadiene type, fluorene type, adamantane type or isocyanuric acid type skeleton containing (meth)acrylic compound; Various polyfunctional (meth)acrylic compounds (except the (meth)acrylic compound containing the said skeleton) etc. can be used. Examples of the polyfunctional (meth)acrylic compound include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and trimethylolpropane di(meth)acrylate. (A) A component can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of excellent heat resistance, the component (A) preferably has a bisphenol A skeleton, a bisphenol F skeleton, a naphthalene skeleton, a fluorene skeleton, an adamantane skeleton or an isocyanuric acid skeleton, fluorene It is more preferable to have a type skeleton. (A) As for component, it is more preferable that it is (meth)acrylate which has any frame|skeleton mentioned above.

It is preferable that (A) component is solid at room temperature (25 degreeC). Compared with liquid, voids are less likely to occur in the solid one, and the viscosity (tack) of the second adhesive before curing (B stage) is small and thus excellent in handling properties. As component (A) which is solid at room temperature (25 degreeC), the (meth)acrylate etc. which have a bisphenol A-type skeleton, a fluorene-type skeleton, an adamantane-type skeleton, or an isocyanuric-acid-type skeleton are mentioned.

(A) As for the number of the functional groups of the (meth)acryl group in component, 3 or less are preferable. When the number of functional groups is large, the network of curing may proceed rapidly, and unreacted groups may remain. On the other hand, if the number of functional groups is 3 or less, since the number of functional groups does not increase too much and hardening by a short time fully advances easily, it is easy to suppress that hardening reaction rate falls.

(A) It is preferable that it is smaller than 2000, and, as for the molecular weight of a component, it is more preferable that it is 1000 or less. (A) Reaction advances easily, so that the molecular weight of a component is small, and hardening reaction rate becomes high.

The content of component (A) is preferably 10 mass % or more based on the total amount of the second adhesive, and 15 mass % or more, from the viewpoint of suppressing the decrease in the curing component and sufficiently easily controlling the flow of the resin after curing. % or more is more preferable. The content of component (A) is preferably 50% by mass or less based on the total amount of the second adhesive from the viewpoint that the cured product is suppressed from becoming too hard, and from the viewpoint that it tends to be easily suppressed from increasing the curvature of the package, , 40 mass% or less is more preferable. From these viewpoints, 10-50 mass % is preferable on the basis of the whole quantity of a 2nd adhesive agent, and, as for content of (A) component, 15-40 mass % is more preferable.

(A) As for content of component, 0.01 mass part or more is preferable with respect to 1 mass part of (C) component from a viewpoint that it is suppressed that sclerosis|hardenability falls and it is easy to suppress that adhesive force falls, and 0.05 mass part or more This is more preferable, and 0.1 mass part or more is still more preferable. (A) From a viewpoint that it is easy to suppress that film-formability falls, 10 mass parts or less are preferable with respect to 1 mass part of (C)component, and, as for content of (A) component, 5 mass parts or less are more preferable. From these viewpoints, 0.01-10 mass parts is preferable with respect to 1 mass part of (C)component, as for content of (A) component, 0.05-5 mass parts is more preferable, 0.1-5 mass parts is still more preferable.

[(B) component: thermal radical generator]

The component (B) is not particularly limited as long as it functions as a curing agent for the component (A), but from the viewpoint of excellent handleability, a thermal radical generator is preferable.

Examples of the thermal radical generating agent include azo compounds and peroxides (such as organic peroxides). As a thermal radical generating agent, a peroxide is preferable and an organic peroxide is more preferable. In this case, a radical reaction does not progress in the process of drying the solvent at the time of setting it as a film form, and it is excellent in handling property and storage stability. Therefore, when a peroxide is used as a thermal radical generating agent, further excellent connection reliability is easy to be acquired. Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, diacylperoxide, peroxydicarbonate, and peroxyester. The organic peroxide is preferably at least one selected from the group consisting of hydroperoxides, dialkyl peroxides and peroxyesters from the viewpoint of excellent storage stability. Moreover, as an organic peroxide, at least 1 sort(s) selected from the group which consists of a hydroperoxide and a dialkyl peroxide from a viewpoint of being excellent in heat resistance is preferable. Examples of the dialkyl peroxide include dicumyl peroxide and di-tert-butyl peroxide.

(B) From a viewpoint that hardening fully advances easily, 0.5 mass part or more is preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component, 1 mass part or more is more preferable. (B) 10 mass parts or less are preferable with respect to 100 mass parts of (A) component, and, as for content of component, 5 mass parts or less are more preferable. (B) When the upper limit of content of a component is the said range, hardening advances rapidly and it is suppressed that reaction points increase, and it is suppressed that a molecular chain becomes short and unreacted group remains. Therefore, there exists a tendency for reliability fall to be easy to suppress that the upper limit of content of (B) component is the said range. From these viewpoints, 0.5-10 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component, 1-5 mass parts is more preferable.

[(C) component: polymer component]

The second adhesive may further contain a polymer component. (C) component, epoxy resin, phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, (meth)acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, Polyetherimide resin, polyvinyl acetal resin, urethane resin, acrylic rubber, etc. are mentioned, Among them, from the viewpoint of excellent heat resistance and film formability, epoxy resin, phenoxy resin, polyimide resin, (meth)acrylic resin , preferably at least one selected from the group consisting of acrylic rubber, cyanate ester resin and polycarbodiimide resin, and selected from the group consisting of epoxy resin, phenoxy resin, polyimide resin, (meth)acrylic resin and acrylic rubber At least one of them is more preferable. (C) A component can also be used individually by 1 type or as a 2 or more types of mixture or a copolymer. However, (C)component does not contain the compound applicable to (A) component, and the compound applicable to (D)component.

(C) From a viewpoint that it is excellent in the stickability to the board|substrate or chip|tip of the film adhesive for semiconductors, as for the glass transition temperature (Tg) of component, 120 degrees C or less is preferable, 100 degrees C or less is more preferable, and 85 degrees C or less is more preferable. In the case of these ranges, it is possible to easily fill in unevenness|corrugation, such as a bump formed in a semiconductor chip, an electrode, or a wiring pattern formed in a board|substrate, with the film adhesive for semiconductors (it is easy to suppress that a hardening reaction starts), and a bubble It tends to be easy to suppress the occurrence of voids by remaining. Here, the Tg is Tg when measured using DSC (manufactured by Parkin-Elmar, trade name: DSC-7 type) under conditions of a sample amount of 10 mg, a temperature increase rate of 10° C./min, and a measurement atmosphere: air.

(C) As for the weight average molecular weight of component, 10000 or more are preferable in polystyrene conversion, and in order to independently show favorable film formability, 30000 or more are more preferable, 40000 or more are still more preferable, and 50000 or more are especially preferable. When a weight average molecular weight is 10000 or more, it exists in the tendency which is easy to suppress that film formability falls.

[(D) component: filler]

The second adhesive may further contain a filler for controlling the viscosity or physical properties of the cured product, and for further suppressing the generation of voids or moisture absorption when the semiconductor chip and the substrate or semiconductor chips are connected. . As (D) component, the same filler as the filler mentioned as (d) component in a 1st adhesive agent can be used. Examples of preferred fillers are also the same.

(D) The content of the component is 30% by mass or more based on the total amount of the second adhesive from the viewpoint of suppressing the lowering of the heat dissipation property and the tendency to easily suppress the occurrence of voids, increase in moisture absorption, etc. This is preferable, and 40 mass % or more is more preferable. The content of the component (D) tends to suppress the decrease in the fluidity of the second adhesive due to the increase in viscosity and the occurrence of entrapment (trapping) of the filler in the connection portion, and tends to easily suppress the decrease in connection reliability. From a viewpoint, 90 mass % or less is preferable based on the whole quantity of 2nd adhesive agent, and 80 mass % or less is more preferable. From these viewpoints, 30-90 mass % is preferable on the basis of the whole quantity of a 2nd adhesive agent, and, as for content of (D)component, 40-80 mass % is more preferable.

[Other Ingredients]

You may mix|blend polymeric compounds other than a radically polymerizable compound (for example, a cationically polymerizable compound and an anionically polymerizable compound) with a 2nd adhesive agent. In addition, you may mix|blend with the 2nd adhesive agent other components similar to the 1st adhesive agent. These can be used individually by 1 type or in combination of 2 or more type. What is necessary is just to adjust these compounding quantities suitably so that the effect of each additive may be expressed.

It is preferable that it is 80 % or more, and, as for the hardening reaction rate when hold|maintaining the 2nd adhesive agent at 200 degreeC for 5 second, it is more preferable that it is 90 % or more. When the curing reaction rate at 200°C (below the solder melting temperature)/5 seconds is 80% or more, it is easy to suppress that the solder scatters and flows during connection (above the solder melting temperature), thereby reducing the connection reliability. The curing reaction rate can be obtained by placing 10 mg of the second adhesive (uncured, flux-free layer) in an aluminum pan, and then measuring the calorific value using DSC (manufactured by Parkin-Elmar, trade name: DSC-7 type). Specifically, a measurement sample containing 10 mg of the second adhesive (uncured flux-free layer) placed in an aluminum pan is placed on a hot plate heated to 200° C., and the measurement sample is peeled off on the hot plate after 5 seconds. . The measurement sample after heat treatment and the measurement sample untreated are each measured by DSC. From the obtained calorific value, the curing reaction rate is calculated by the following formula.

Curing reaction rate (%) = (1-[calorific value of measured sample after heat treatment]/[caloric value of untreated measured sample]) x 100

When the second resin contains an anionic polymerizable epoxy resin (especially an epoxy resin having a weight average molecular weight of 10000 or more), it may be difficult to adjust the curing reaction rate to 80% or more. It is preferable that it is 20 mass parts or less with respect to 80 mass parts of (A) component, and, as for content of an epoxy resin, it is more preferable that it does not contain an epoxy resin.

The second layer (flux-free layer) including the second adhesive can be compressed at a high temperature of 200° C. or higher. Further, in a flip-chip package in which a connection is formed by melting a metal such as solder, further excellent curability is expressed.

Regarding the thickness of the film adhesive for semiconductors of this embodiment, when the sum of the heights of the said connection part is made into x and the total thickness of the film adhesive for semiconductors is made into y, the relationship between x and y at the time of crimping|bonding From the viewpoints of connectivity and filling properties of the adhesive, it is preferable to satisfy 0.70 x ≤ y ≤ 1.3 x, more preferably 0.80 x ≤ y ≤ 1.2 x. The total thickness of the film adhesive for semiconductors may be 10-100 micrometers, for example, 10-80 micrometers may be sufficient, and 10-50 micrometers may be sufficient as it.

The thickness of the first layer may be, for example, 1 to 50 µm, 3 to 50 µm, 4 to 30 µm, or 5 to 20 µm.

The thickness of the second layer may be, for example, 7 to 50 µm, 8 to 45 µm, or 10 to 40 µm.

The ratio of the thickness of the second layer to the thickness of the first layer (thickness of the second layer/thickness of the first layer) may be, for example, 0.1 to 10.0, 0.5 to 6.0, or 1.0 to 4.0.

Although the film adhesive for semiconductors of this embodiment may be further equipped with layers other than a 1st layer and a 2nd layer, it is preferable that only a 1st layer and a 2nd layer are included. In addition, the film adhesive for semiconductors of this embodiment is a base material on the surface on the opposite side to the 2nd layer in a 1st layer, and/or on the surface on the opposite side to the 1st layer in a 2nd layer. A film and/or a protective film may be provided.

<The manufacturing method of the film adhesive for semiconductors>

The film adhesive for semiconductors of this embodiment prepares, for example, the 1st film adhesive with a 1st layer, and the 2nd film adhesive with a 2nd layer, The 1st film adhesive with a 1st layer, and a agent It can obtain by bonding together the 2nd film adhesive with two layers.

In the process of preparing a 1st film adhesive, for example, first, (a) component, (b) component, and (c) component, and other components, such as (d) component and (e) component, which are added as needed, are organic It is added in a solvent, it is made to melt|dissolve or disperse|distribute by stirring mixing, kneading|mixing, etc., and a resin varnish (coating varnish) is prepared. Then, on the base film subjected to the release treatment, the resin varnish is applied using a knife coater, roll coater, applicator, etc., and then the organic solvent is reduced by heating, and the agent containing the first adhesive on the base film One layer can be formed.

As an organic solvent used for preparation of a resin varnish, it is preferable to have the characteristic which can melt|dissolve or disperse|distribute each component uniformly, for example, dimethylformamide, dimethylacetamide, N-methyl-2- pyrrolidone, dimethyl sulfoxide. , diethylene glycol dimethyl ether, 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 or in combination of 2 or more types. Stirring mixing and kneading at the time of preparing the resin varnish can be performed using, for example, a stirrer, a rake machine, three rolls, a ball mill, a bead mill, or a homodisper.

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. Polyolefin films such as polypropylene films and polymethylpentene films, polyethylene terephthalate films, polyethylene naphthalate films A polyester film, a polyimide film, and a polyetherimide film can be illustrated. The base film is not limited to the single layer containing these films, and may be a multilayer film containing two or more types of materials.

It is preferable that the drying conditions at the time of volatilizing an organic solvent from the resin varnish apply|coated to the base film make it into conditions that an organic solvent fully volatilizes, Specifically, it is 50-200 degreeC, It is preferable to perform heating for 0.1-90 minutes. do. If there is no influence on the void or viscosity adjustment after mounting, it is preferable that an organic solvent is removed to 1.5 mass % or less with respect to 1st film adhesive whole quantity.

At the process of preparing a 2nd film adhesive, it is a base film by the method similar to a 1st layer except using other components, such as (A) component and (B) component, and (C)component added as needed. A second layer including a second adhesive may be formed thereon.

As a method of bonding a 1st film adhesive and a 2nd film adhesive, methods, such as a hot press, roll lamination, and vacuum lamination, are mentioned, for example. Lamination may be performed under heating conditions of 30-120 degreeC, for example.

After the film adhesive for semiconductors of this embodiment forms one of a 1st layer or a 2nd layer on a base film, for example, on the obtained 1st layer or 2nd layer, the other of a 1st layer or a 2nd layer It may be obtained by forming the side. You may form a 1st layer and a 2nd layer by the method similar to the formation method of the 1st layer and 2nd layer in manufacture of the film adhesive with a base material mentioned above.

<Semiconductor device>

The semiconductor device of this embodiment is demonstrated below using FIG.1 and FIG.2. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing which shows one Embodiment of the semiconductor device of this invention. As shown in FIG. 1A , the semiconductor device 100 includes a semiconductor chip 10 and a substrate (circuit wiring board) 20 that oppose each other, and the semiconductor chip 10 and the substrate 20 are mutually opposite each other. Between the wiring 15 arranged on opposite surfaces, the connection bump 30 which interconnects the wiring 15 of the semiconductor chip 10 and the board|substrate 20, respectively, and the semiconductor chip 10 and the board|substrate 20 has a sealing portion 40 containing a cured product of an adhesive (a first adhesive and a second adhesive) filled with no gaps in the pores of the ? The semiconductor chip 10 and the board|substrate 20 are flip-chip-connected by the wiring 15 and the connection bump 30. As shown in FIG. The wiring 15 and the connection bump 30 are sealed with a cured product of an adhesive, and are shielded from the external environment. The sealing part 40 has an upper part 40a containing the hardened|cured material of a 1st adhesive agent, and the lower part 40b containing the hardened|cured material of a 2nd adhesive agent.

As shown in FIG. 1B , the semiconductor device 200 includes a semiconductor chip 10 and a substrate 20 that are opposed to each other, and surfaces of the semiconductor chip 10 and the substrate 20 that are opposite to each other, respectively. It has bumps 32 arranged and a sealing portion 40 comprising a cured product of an adhesive (a first adhesive and a second adhesive) filled without a gap in the gap between the semiconductor chip 10 and the substrate 20. . The semiconductor chip 10 and the board|substrate 20 are flip-chip-connected by mutually connecting the bump 32 which opposes. The bumps 32 are sealed with a cured product of an adhesive, and are shielded from the external environment. The sealing part 40 has an upper part 40a containing the hardened|cured material of a 1st adhesive agent, and the lower part 40b containing the hardened|cured material of a 2nd adhesive agent.

Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. As shown in FIG. 2A , the semiconductor device 300 is a semiconductor device except that two semiconductor chips 10 are flip-chip connected by a wiring 15 and a connection bump 30 . Same as (100). As shown in FIG. 2B , the semiconductor device 400 is the same as the semiconductor device 200 except that two semiconductor chips 10 are flip-chip connected by bumps 32 .

The semiconductor chip 10 is not particularly limited, and an elemental semiconductor composed of the same type of element such as silicon or germanium, or a compound semiconductor such as gallium arsenide or indium phosphorus can be used.

The substrate 20 is not particularly limited as long as it is a circuit board, and unnecessary portions of the metal film are etched on the surface of the insulating substrate containing glass epoxy, polyimide, polyester, ceramic, epoxy, bismaleimide triazine, etc. as main components. A circuit board having a wiring (wiring pattern) 15 formed by removing, a circuit board having a wiring 15 formed on the surface of the insulating substrate by metal plating or the like, and a wiring 15 by printing a conductive material on the surface of the insulating substrate The formed circuit board or the like can be used.

The interconnection portion of the wiring 15 and the bump 32 and the like have gold, silver, copper, and solder as main components (the main components are, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.) ), nickel, tin, lead, and the like, and may contain a plurality of metals.

Among the above metals, gold, silver, and copper are preferable, and silver and copper are more preferable from the viewpoint of providing a package excellent in electrical conductivity and thermal conductivity of the connection portion. From the viewpoint of providing a package with reduced cost, silver, copper, and solder, which are inexpensive materials, are preferable, copper and solder are more preferable, and solder is still more preferable. When an oxide film is formed on the surface of a metal at room temperature, since productivity may fall and cost may increase, from a viewpoint of suppressing formation of an oxide film, gold, silver, copper and solder are preferable, and gold, silver , solder is more preferable, and gold and silver are still more preferable.

Gold, silver, copper, solder (the main component is, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, etc.), tin, nickel, etc. The metal layer used as a component may be formed by plating, for example. This metal layer may be comprised only by a single component, or may be comprised by several components. In addition, the said metal layer may have a single layer or the structure in which several metal layers were laminated|stacked.

In the semiconductor device of the present embodiment, a plurality of structures (packages) as shown in the semiconductor devices 100 to 400 may be stacked. In this case, the semiconductor devices 100 to 400 include gold, silver, copper, solder (the main component is, for example, tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper, etc.), tin, They may be electrically connected to each other by bumps, wirings, or the like containing nickel or the like.

As a method of stacking a plurality of semiconductor devices, as shown in FIG. 3 , for example, a TSV (Through-Silicon Via) technique is used. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention, and is a semiconductor device using TSV technology. In the semiconductor device 500 shown in FIG. 3 , the wiring 15 formed on the interposer 50 is connected to the wiring 15 of the semiconductor chip 10 via the connection bump 30 , so that the semiconductor chip 10 is ) and the interposer 50 are flip-chip connected. The gap between the semiconductor chip 10 and the interposer 50 is filled with a cured product of an adhesive (the first adhesive and the second adhesive) without a gap, and constitutes the sealing part 40 . On the surface of the semiconductor chip 10 opposite to the interposer 50 , the semiconductor chip 10 is repeatedly laminated through the wiring 15 , the connection bump 30 , and the sealing portion 40 . The wirings 15 on the patterned surface on the front and back of the semiconductor chip 10 are interconnected by through electrodes 34 filled in holes penetrating the inside of the semiconductor chip 10 . In addition, as a material of the through electrode 34, copper, aluminum, etc. can be used.

With this TSV technology, it becomes possible to acquire a signal even from the back surface of a semiconductor chip that is not normally used. Furthermore, since the through electrode 34 is vertically passed through the semiconductor chip 10, the distance between the opposing semiconductor chips 10 and between the semiconductor chip 10 and the interposer 50 is shortened, so that flexible connection is possible. The film adhesive for semiconductors of this embodiment is such a TSV technique. WHEREIN: Between the semiconductor chips 10 which oppose, and between the semiconductor chip 10 and the interposer 50, it is applicable as a film adhesive for semiconductors. .

In addition, in a bump forming method with a high degree of freedom, such as an area bump chip technology, the semiconductor chip can be directly mounted on the motherboard without going through an interposer. The film adhesive for semiconductors of this embodiment is applicable also when mounting such a semiconductor chip directly on a motherboard. In addition, when laminating|stacking two wiring circuit boards, the film adhesive for semiconductors of this embodiment is applicable also, when sealing the space|gap between board|substrates.

<Method for manufacturing semiconductor device>

The manufacturing method of the semiconductor device of this embodiment is demonstrated below using FIG. Fig. 4 is a diagram schematically showing one embodiment of a method for manufacturing a semiconductor device of the present invention, and Figs. 4 (a), 4 (b) and 4 (c) showing each step are cross-sections of the semiconductor device. shows

First, as shown in FIG.4(a), on the board|substrate 20 which has wiring 15, the soldering resist 60 which has an opening in the position where the connection bump 30 is formed is formed. The solder resist 60 is not necessarily formed. However, by forming a soldering resist on the board|substrate 20, generation|occurrence|production of the bridge|bridging between wiring 15 can be suppressed and connection reliability and insulation reliability can be improved. The solder resist 60 can be formed using, for example, a commercially available ink for a solder resist for a package. Specific examples of commercially available ink for soldering resists for packages include SR series (manufactured by Hitachi Chemical Co., Ltd., trade name) and PSR4000-AUS series (manufactured by Taiyo Ink Seijo Co., Ltd., trade name).

Next, as shown to Fig.4 (a), the connection bump 30 is formed in the opening of the soldering resist 60. As shown in FIG. And as shown in FIG.4(b), on the board|substrate 20 on which the connection bump 30 and the soldering resist 60 were formed, the surface on the side of the 2nd layer 41b containing a 2nd adhesive agent is a board|substrate (20) The film adhesive for semiconductors of this embodiment (Hereinafter, it is called "film adhesive" in some cases.) 41 of this embodiment is attached so that it may become the side. The film adhesive 41 can be pasted by hot press, roll lamination, vacuum lamination, or the like. The supply area and thickness of the film adhesive 41 are suitably set according to the size of the semiconductor chip 10 and the board|substrate 20, the height of the connection bump 30, etc. In addition, you may perform sticking of the film adhesive 41 so that the surface by the side of the 1st layer 41a containing a 1st adhesive agent may become the board|substrate 20 side.

After attaching the film adhesive 41 to the substrate 20 as described above, the wiring 15 of the semiconductor chip 10 and the connection bump 30 are fixed by using a connection device such as a flip chip bonder. match Next, the semiconductor chip 10 and the substrate 20 are compressed while heating at a temperature equal to or higher than the melting point of the connection bump 30 , and as shown in FIG. 4C , the semiconductor chip 10 and the substrate 20 are bonded together. While connecting, the space|gap between the semiconductor chip 10 and the board|substrate 20 is sealingly filled with the sealing part 40 containing the hardened|cured material of the film adhesive 41. As described above, the semiconductor device 600 can be obtained.

The compression time may be, for example, 5 seconds or less. In this embodiment, since the film adhesive 41 of this embodiment mentioned above is used, even if crimping|compression-bonding time is 5 second or less, the semiconductor device which has the outstanding connection reliability can be obtained.

In the manufacturing method of the semiconductor device of this embodiment, after alignment, it temporarily fixes (state through the film adhesive for semiconductors) and heat-processes in a reflow furnace, the connection bump 30 is melted, and the semiconductor chip 10 ) and the substrate 20 may be connected. Since the formation of a metal joint is not necessarily required in the temporary fixing step, compared to the above-described method of pressing while heating, compression by low load, short time, and low temperature may be used, and the productivity can be improved and deterioration of the connection can be suppressed. have.

Moreover, after connecting the semiconductor chip 10 and the board|substrate 20, you may heat-process in an oven etc., and you may improve connection reliability and insulation reliability further. The temperature at which hardening of a film adhesive advances is preferable, and, as for heating temperature, the temperature to harden|cure completely is more preferable. The heating temperature and heating time are appropriately set.

In the manufacturing method of the semiconductor device of this embodiment, after attaching the film adhesive 41 to the semiconductor chip 10, you may connect the board|substrate 20.

After supplying the film adhesive for semiconductors to the semiconductor wafer to which the some semiconductor chip 10 was connected from a viewpoint that productivity improves, by dicing and dividing into pieces, on the semiconductor chip 10 for semiconductors You may obtain the structure to which the film adhesive was supplied. What is necessary is just to supply the film adhesive for semiconductors so that wiring, bumps, etc. on the semiconductor chip 10 may be embedded, for example by attaching methods, such as hot press, roll lamination, and vacuum lamination. In this case, since the supply amount of resin becomes constant, productivity is improved, and generation|occurrence|production of a void and the fall of dicing property by lack of embedding can be suppressed.

The connection load is set in consideration of variations in the number and height of the connection bumps 30 , the connection bumps 30 due to pressurization, or the amount of deformation of the wiring that receives the bumps in the connection part. As for the connection temperature, although it is preferable that the temperature of a connection part is more than melting|fusing point of the connection bump 30, it is sufficient as long as it is the temperature at which the metal junction of each connection part (bump and wiring) is formed. When the connection bump 30 is a solder bump, about 240 degreeC or more is preferable.

Although the connection time at the time of connection changes with the constituent metals of a connection part, from a viewpoint of improving productivity, the shorter time is preferable. When the connection bump 30 is a solder bump, 20 second or less is preferable, as for the connection time, 10 second or less is more preferable, and its 5 second or less is still more preferable. In the case of copper-copper or copper-gold metal connection, the connection time is preferably 60 seconds or less.

Also in the flip-chip connection part of the various package structure mentioned above, the film adhesive for semiconductors of this embodiment shows the outstanding reflow resistance and connection reliability.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to the said embodiment.

[Example]

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

<Production of single-layer film with flux-containing layer>

The compounds used for the preparation of the single-layer film with the flux-containing layer are shown below.

(a) Epoxy resin

・Multifunctional solid epoxy containing triphenolmethane skeleton (Japan Epoxy Resins Co., Ltd., trade name "EP1032H60")

・Bisphenol F-type liquid epoxy (manufactured by Japan Epoxy Resins, Ltd., trade name “YL983U”)

(b) hardener

- 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (Shikoku Chemical Co., Ltd. make, trade name "2MAOK-" PW”)

(c) flux agent

・Glutaric acid (manufactured by Tokyo Chemical Co., Ltd., melting point about 98°C)

·2-Methylglutaric acid (manufactured by Aldrich, melting point about 78°C)

·3-methylglutaric acid (Tokyo Chemical Co., Ltd., melting point about 87°C)

(d) polymer component

・Phenoxy resin (manufactured by Toto Chemical Co., Ltd., trade name "ZX1356-2", Tg: about 71°C, weight average molecular weight Mw: about 63000)

(e) filler

Silica filler (AdMatex Co., Ltd., SE2050, average particle size: 0.5 μm)

・Epoxysilane surface treatment filler (AdMatex, Ltd., SE2050-SEJ, average particle size: 0.5 μm)

・Methacryl surface treatment nano silica filler (AdMatex, Ltd., YA050C-MJE, average particle diameter: about 50 nm)

・Organic filler (resin filler, manufactured by Rohm & Haas Japan Co., Ltd., EXL-2655: core shell type organic fine particles)

Epoxy resin, curing agent, flux agent, inorganic filler, and organic filler in the compounding amounts (unit: parts by mass) shown in Table 1, the NV value ([mass of coating material after drying] / [mass of coating material before drying] × 100) was 60 % was added to an organic solvent (methyl ethyl ketone). Thereafter, the same mass as the solid content (epoxy resin, curing agent, flux agent, polymer component, inorganic filler and organic filler) was added to the Φ 1.0 mm bead and the Φ 2.0 mm bead, and a bead mill (Pritu Japan Co., Ltd., The mixture was stirred for 30 minutes with a planetary pulverizer P-7). After stirring, the beads were removed by filtration to prepare a coating varnish.

The obtained coating varnish was coated on a base film (manufactured by Teijin DuPont Film Co., Ltd., trade name "Purex A54") with a small precision coating device (Yasui Seiki), and dried in a clean oven (manufactured by ESPEC) (80 °C/10 min) to obtain single-layer films (A-1), (A-2) and (A-3) shown in Table 1.

<Production of single-layer film with flux-free layer>

The compounds used for the preparation of a single-layer film having a flux-free layer are shown below.

(A) (meth)acrylic compound

Acrylates having a fluorene-type backbone (Osaka Chemical Co., Ltd., EA-0200, 2 functional groups)

・Acrylate having a bisphenol A-type skeleton (Shin-Nakamura Chemical Industry Co., Ltd., EA1020)

・Ethoxyisocyanuric acid triacrylate (Shin-Nakamura Chemical Industry Co., Ltd., A-9300)

(B) Thermal radical generator

・Dicumyl peroxide (Nichi Oil Co., Ltd., Pacumyl (registered trademark) D)

・Di-tert-butyl peroxide (Nichi Oil Co., Ltd., Parbutyl (registered trademark) D)

· 1,4-bis-((tert-butylperoxy)diisopropyl)benzene (Nichi Oil Co., Ltd., Parbutyl (registered trademark) P)

(C) polymer component

・Acrylic resin (Hitachi Chemical Co., Ltd., KH-CT-865, weight average molecular weight Mw: 100000, Tg: 10°C)

(D) filler

The same filler (component (d)) used for preparation of the single-layer film with the flux-containing layer was used.

The (meth)acrylic compound, the polymer component, the inorganic filler, and the organic filler of the compounding quantity (unit: mass part) shown in Table 2 were added to the organic solvent (methyl ethyl ketone) so that the NV value might be 60%. Thereafter, the same mass as the solid content ((meth)acrylic compound, polymer component, inorganic filler and organic filler) was added to the Φ 1.0 mm bead and the Φ 2.0 mm bead, and a bead mill (Pritu Japan Co., Ltd., planetary mill) was added. It was stirred for 30 minutes with a grinder P-7). After stirring, the beads were removed by filtration. Next, a thermal radical generating agent was added to the obtained mixture, and it stirred and mixed, and the coating varnish was produced.

The obtained coating varnish was coated on a base film (manufactured by Teijin DuPont Film Co., Ltd., trade name "Purex A54") with a small precision coating device (Yasui Seiki), and dried in a clean oven (manufactured by ESPEC) (80 °C/10 min) to obtain single-layer films (B-1), (B-2), (B-3), (B-4) and (B-5) shown in Table 2.

<Production of two-layer film>

(Examples 1 and 2, and Comparative Examples 1 to 8)

Two of the single-layer films produced above (1st film and 2nd film) were laminated at 50 degreeC, and the film adhesive with a total thickness of 40 micrometers was produced. The single-layer film combinations were as shown in Table 3.

<Evaluation>

By the method shown below, initial stage connection evaluation of the film adhesive obtained by the Example and the comparative example, void evaluation, solder wettability evaluation, and insulation reliability evaluation were performed. A result is shown in Table 3.

(Evaluation of initial connectivity)

The film adhesive produced in the Example or the comparative example was cut out to predetermined size (8 mm long x 8 mm wide x 40 micrometers in thickness), and the sample for evaluation was produced. Next, a sample for evaluation was affixed on a glass epoxy substrate (glass epoxy substrate: 420 μm thick, copper wiring: 9 μm thick), and a semiconductor chip with solder bumps (chip size: 7.3 mm long × 7.3 mm wide × 0.15 mm thick) , bump height: about 40 µm in total copper pillar + solder, the number of bumps 328) was mounted with a flip mounting device “FCB3” (manufactured by Panasonic, trade name) (mounting conditions: crimping head temperature 350°C, crimping time 3 seconds, crimping pressure 0.5 MPa). Accordingly, a semiconductor device in which the glass epoxy substrate and the semiconductor chip with solder bumps were daisy-chained in the same manner as in FIG. 4 was produced. In addition, the evaluation samples of Examples 1 and 2 were affixed on a glass substrate so that a flux non-containing layer and a glass epoxy substrate might contact.

The initial conduction|electrical_connection after mounting was evaluated by measuring the connection resistance value of the obtained semiconductor device using the multimeter (The ADVANTEST make, brand name "R6871E"). When the connection resistance value is 10.0 Ω or more and 13.5 Ω or less, the connection resistance is “A” (good), and when the connection resistance is greater than 13.5 Ω and 20 Ω or less, the connection resistance is “B” (bad), and the connection resistance is 20 Ω When larger, the case where a connection resistance value was less than 10 ohms and the case where a resistance value was not displayed with connection defect were all evaluated as connection "C" (defect).

(Void evaluation)

For the semiconductor device manufactured by the above method, an external image was taken with an ultrasonic imaging device (trade name "Insight-300", manufactured by Insight), and the adhesive on the chip was taken with a scanner GT-9300 UF (manufactured by EPSON, trade name). Acquire the image of the layer (layer containing the cured product of film adhesive for semiconductor), use image processing software Adobe Photoshop (registered trademark) to identify void portions by color correction and 2nd gradation, and to the histogram The ratio occupied by the void portion was calculated by Let the area of the adhesive part on the chip be 100%, the case where the void generation rate is 5% or less is "A", the case where it is more than 5% and 10% or less is "B", and the case where it is more than 10% is "C" was evaluated as

(Solder wettability evaluation)

Regarding the semiconductor device fabricated by the method described above, by observing the cross section of the connection portion, “A” (good) indicates that the upper surface of the Cu wiring is wetted with solder by 90% or more, and “A” (good) indicates that the wetness of the solder is less than 90%. B" (lack of wetness) and evaluated.

(Insulation Reliability Test [HAST Test: Highly Accelerated Storage Test])

The film adhesive (thickness: 40 µm) produced in the Example or Comparative Example was attached to the comb-type electrode evaluation TEG (manufactured by Hitachi Chemical Co., Ltd., wiring pitch: 50 µm), and in a clean oven (manufactured by ESPEC). , and cured at 175°C for 2 hours. The cured sample was installed in an accelerated life tester (manufactured by HIRAYAMA, trade name "PL-422R8", conditions: 130°C/85% RH/100 hours, 5 V applied), and insulation resistance was measured. The case where the insulation resistance after 100 hours was 10 ⁸ Ω or more was evaluated as “A”, the case of 10 ⁷ Ω or more and ^{less than 10 8} Ω as “B”, and the ^{case of less than 10 7} Ω as “C” was evaluated. .

As for the film adhesive for semiconductors of Examples 1 and 2, void generation|occurrence|production was fully suppressed, solder wettability was favorable, and it was confirmed that it was excellent in HAST resistance.

10 semiconductor chip, 15 wiring (connection part), 20 board (wiring circuit board), 30 connection bump, 32 bump (connection part), 34 through electrode, 40 sealing part, 41 film adhesive for semiconductor , 50: interposer, 60: solder resist, 100, 200, 300, 400, 500, 600: semiconductor device.

Claims (12)

a first layer comprising a first adhesive comprising a thermosetting resin, a curing agent and a flux compound;
a second layer provided on said first layer and comprising a second adhesive substantially free of flux compound;
The second adhesive is a film adhesive for semiconductors containing a radical polymerizable compound and a thermal radical generator. The film adhesive for semiconductors of Claim 1 whose hardening reaction rate when hold|maintained for 5 second at 200 degreeC of said 2nd adhesive agent is 80 % or more. The film adhesive for semiconductors according to claim 1, wherein the thermal radical generator is a peroxide. The film adhesive for semiconductors of Claim 1 or 3 whose said radically polymerizable compound is a (meth)acrylic compound. The film adhesive for semiconductors according to claim 4, wherein the (meth)acrylic compound has a fluorene-type skeleton. The film adhesive for semiconductors according to any one of claims 1 to 3, wherein the flux compound has a carboxyl group. The film adhesive for semiconductors according to any one of claims 1 to 3, wherein the flux compound has two or more carboxyl groups. The film adhesive for semiconductors according to any one of claims 1 to 3, wherein the flux compound is a compound represented by the following formula (2).

[In formula (2), R ¹ and R ² each independently represent a hydrogen atom or an electron-donating group, and n represents 0 or an integer of 1 or more.] The film adhesive for semiconductors according to any one of claims 1 to 3, wherein the flux compound has a melting point of 150°C or less. A method of manufacturing a semiconductor device in which respective connecting portions of a semiconductor chip and a wiring circuit board are electrically connected to each other, or a semiconductor device in which respective connecting portions of a plurality of semiconductor chips are electrically connected to each other, comprising:
The manufacturing method of the semiconductor device provided with the process of sealing at least one part of the said connection part using the film adhesive for semiconductors in any one of Claims 1-3. A semiconductor device in which each connection portion of a semiconductor chip and a wiring circuit board is electrically connected to each other, or a semiconductor device in which each connection portion of a plurality of semiconductor chips is electrically connected to each other, the semiconductor device comprising:
The semiconductor device by which at least one part of the said connection part is sealed with the hardened|cured material of the film adhesive for semiconductors in any one of Claims 1-3. delete

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