TW201414795A - Adhesive composition, method for manufacturing semiconductor device, and semiconductor device - Google Patents

Abstract

The present invention relates to an adhesive composition for encapsulating connection parts in a semiconductor device in which respective connection parts of a semiconductor chip and a wiring circuit board are electrically connected with each other or alternatively in a semiconductor device in which respective connection parts of a plurality of semiconductor chips are electrically connected with each other. The adhesive composition contains an epoxy resin, a curing agent and an acrylic surface-treated filler.

Description

Substrate composition, method of manufacturing semiconductor device, and semiconductor device

The present invention relates to an adhesive composition, a method of manufacturing a semiconductor device, and a semiconductor device.

In recent years, wire bonding methods using metal thin wires such as gold wires have been widely used to mount and connect semiconductor wafers to substrates. On the other hand, in order to cope with the demands of miniaturization, thinning, high performance, high integration, and high speed of semiconductor devices, it is gradually adopted to form conductive bumps called bumps between a semiconductor wafer and a substrate. A flip chip connection method (FC connection method) for connecting a semiconductor wafer to a substrate.

For example, COB (Chip On Board) is widely used in BGA (Ball Grid Array), CSP (Chip Size Package), and the like for connection between a semiconductor wafer and a substrate. The connection method of the type is also applicable to the FC connection method. In addition, the FC connection method is also widely used in a COC (Chip On Chip) type connection method in which a connection portion (bump or wiring) is formed on a semiconductor wafer to connect semiconductor wafers (see, for example, Patent Document 1) .

However, in order to meet the requirements of miniaturization, thinning, and high performance, the above-mentioned connection method is laminated and multi-stage wafer-stacked package and POP are required. (Package On Package, package stacking), and TSV (Through-Silicon Via) have also become widespread. Since such a multilayer multi-stage technique is configured by three-dimensionally arranging a semiconductor wafer or the like, the package can be reduced in comparison with the method of two-dimensional arrangement. In particular, TSV technology is also effective in improving semiconductor performance, noise reduction, reduction in mounting area, and power saving, and has attracted attention as the next generation of semiconductor wiring technology.

The main metal used in the connection portion (bump or wiring) may be solder, tin, gold, silver, copper, nickel, or the like, and a conductive material containing a plurality of such metals may be used. The metal used in the connection portion is oxidized on the surface to form an oxide film, or an impurity such as an oxide adheres to the surface, so that impurities may be generated on the connection surface of the connection portion. When such an impurity is present, there is a concern that the connectivity between the semiconductor wafer and the substrate or between the two semiconductor wafers and the insulation reliability are lowered, and the above-described connection method is impaired.

As a method for suppressing the generation of such impurities and improving the connectivity, for example, there is a method of pretreating the surface of the substrate or the semiconductor wafer before the connection, for example, treatment by OSP (Organic Solderbility Preservatives) A method of pre-flux or rust-preventing agent used in the process. However, there is also a case where the pre-flux or the anti-rust treatment agent remains and deteriorates after the pretreatment, and the connectivity is lowered.

On the other hand, in accordance with a method of sealing a connection portion between a semiconductor wafer and a substrate by a semiconductor sealing material (a semiconductor sealing adhesive), the connection portion can be sealed while the semiconductor wafer and the substrate or the semiconductor wafer are connected to each other. Therefore, it is possible to suppress the oxidation of the metal used in the joint portion or suppress the adhesion of the impurities to the joint portion, and protect the joint portion from the external environment. because This can effectively improve the connectivity, insulation reliability, workability, and productivity.

Further, in the semiconductor device manufactured by the flip chip connection method, the thermal stress caused by the difference in thermal expansion coefficient between the semiconductor wafer and the substrate or the difference in thermal expansion coefficient between the semiconductor wafers is not concentrated on the connection portion, thereby causing connection failure. The gap between the semiconductor wafer and the substrate must be sealed with a semiconductor sealing material. In particular, semiconductor wafers and substrates are often made of components having different coefficients of thermal expansion, and thus it is necessary to seal with a semiconductor packaging material to improve thermal shock resistance.

The sealing method using the above semiconductor sealing material can be roughly classified into a capillary flow method and a pre-applied method (for example, refer to Patent Documents 2 to 6). The capillary flow method is a method in which a liquid semiconductor sealing material is injected into a gap between a semiconductor wafer and a substrate by a capillary phenomenon after the semiconductor wafer and the substrate are connected. The precoating method is a method in which a semiconductor wafer or a substrate is supplied with a paste or a film-shaped semiconductor sealing material before the semiconductor wafer and the substrate are connected, and the semiconductor wafer is connected to the substrate. With regard to these sealing methods, as the size of the semiconductor device has progressed in recent years, the gap between the semiconductor wafer and the substrate has become narrow, and if it is injected by capillary flow, it takes a long time to lower the productivity, or In the case where it is impossible to inject, and even if it can be injected, there is a case where there is an unfilled portion and it is a cause of a hole. Therefore, by workability. productivity. From the point of view of reliability, the pre-coating method has achieved high performance. High accumulation. The high-speed sealing production method has become the mainstream.

[Previous Technical Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-294382

Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-223227

Patent Document 3: Japanese Laid-Open Patent Publication No. 2002-283098

Patent Document 4: Japanese Laid-Open Patent Publication No. 2005-272547

Patent Document 5: Japanese Laid-Open Patent Publication No. 2006-169407

Patent Document 6: Japanese Laid-Open Patent Publication No. 2006-188573

In the precoating method described above, in order to seal the gap between the semiconductor wafer and the substrate with a semiconductor sealing material while being joined by heating and pressurization, it is necessary to select a component of the semiconductor sealing material in consideration of connection conditions. When the connections are connected to each other, the connectivity is fully ensured. From the viewpoint of insulation reliability, metal bonding is generally used. Since the metal joining is a connection method using a high temperature (for example, 200 ° C or higher), the semiconductor is sealed by a volatile component remaining in the semiconductor sealing material or a volatile component newly formed by decomposition of a component of the semiconductor sealing material. The condition in which the material produces bubbles. Therefore, a bubble called a hole is generated to peel the semiconductor sealing material from the semiconductor wafer or the substrate. Further, when the springback of the hole or the semiconductor wafer or the like occurs during the pressurization heating/pressure release, the connection of the connection bumps to which the connection portions are connected may cause a connection failure such as breakage of the connection portion. . For these reasons, the past semiconductor sealing materials will have connectivity. The concern of reduced insulation reliability.

Moreover, when the semiconductor sealing material does not have sufficient flux activity (the effect of removing the oxide film or impurities on the metal surface), the oxide film or impurities on the metal surface cannot be removed, and a good metal-metal bonding cannot be formed, and thus There is no way to ensure continuity. Further, when the insulation reliability of the semiconductor sealing material is low, it is difficult to cause insulation failure in accordance with the narrow pitch of the connection portion. For these reasons, the past semiconductor sealing materials will have connectivity. The concern of reduced insulation reliability.

A semiconductor device fabricated using a semiconductor sealing material needs to be sufficiently graded in terms of reliability, more specifically, heat resistance, moisture resistance, and reflow resistance. In order to ensure reflow resistance, it is necessary to maintain a high adhesion strength which can suppress peeling or destruction of the adhesion layer (adhesive layer) at a reflow temperature of about 260 °C.

The present invention has been made in view of the above problems, and an object thereof is to provide an adhesive composition for a semiconductor device which is excellent in reflow resistance, connection reliability, and insulation reliability, and a semiconductor device using the same. Manufacturing method and semiconductor device.

The present invention provides an adhesive composition in which a semiconductor device in which a connection portion of a semiconductor wafer and a printed circuit board are electrically connected to each other or a connection portion in which a plurality of semiconductor wafers are electrically connected to each other is sealed in a semiconductor device. A composition comprising an epoxy resin, a hardener, and an acrylic surface-treated filler surface-treated with a compound having a group represented by the following formula (1).

In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ² represents an alkylene group having 1 to 30 carbon atoms.

Further, the present invention provides an adhesive composition for sealing a connection portion in a semiconductor device in which a connection portion of each of a semiconductor wafer and a printed circuit board is electrically connected to each other, or a connection portion in which a plurality of semiconductor wafers are electrically connected to each other A composition of the following, wherein the composition contains an epoxy resin, a hardener, and a filler having a group represented by the following formula (1):

In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ² represents an alkylene group having 1 to 30 carbon atoms.

The above-mentioned adhesive composition of the present invention further contains an acrylic-based surface-treated filler or a filler having a group represented by the above formula (1), even if it contains an epoxy resin and a hardener. When used as a semiconductor sealing adhesive in a flip chip bonding method in which metal bonding is performed at a high temperature (for example, 200 ° C or higher), high reflow resistance, connection reliability, and insulation reliability can be achieved.

In order to improve the reflow resistance of the adhesive composition, it is necessary to increase the moisture absorption after the high temperature. However, the fillers used in the past can reduce the moisture absorption rate and the thermal expansion rate, thereby effectively improving the connectivity. Insulation reliability, but the filler itself often lacks adhesion.

Here, it is known that if a decane coupling agent is contained in a resin together with a non-surface-treated filler, the surface of the synthetic filler can be treated with a decane coupling agent and A filler which exhibits various surface states depending on the substituent of the decane coupling agent. However, the decane coupling agent has a high volatility, and may cause voids in a semiconductor device manufacturing step having a high-temperature process such as metal bonding which is required to be joined at a high temperature. Similarly, when the conventionally used filler is subjected to surface treatment, an organic substance having high volatility such as methanol may be generated, which may cause pores to occur.

Generally, an insulating film called a solder resist is formed on a semiconductor substrate, and a solder resist mostly contains an acrylic material. Here, the present inventors have found that by containing the above-mentioned acrylic surface-treated filler or a filler having the group represented by the above formula (1), the elastic modulus of the adhesive composition at a high temperature and the moisture absorption can be improved. The force is applied and the reflow resistance is achieved. The present inventors have speculated that in the adhesive composition of the present invention, high-volatileness can be suppressed by using a surface-treated acrylic surface-treated filler or a filler having a group represented by the above formula (1). Since the substance is produced and the adhesion between the acrylic compound and the solder resist is excellent, the connectivity to the substrate can be improved. Moreover, the inventors of the present invention have estimated that the acrylic surface-treated filler or the filler having the group represented by the above formula (1) is difficult to reduce the insulation reliability of the joint portion, and it is difficult to harden the adhesive composition. The thermal expansion rate and the elastic modulus are lowered, so that the connection reliability can be improved.

The acrylic surface-treated filler or the filler having the group represented by the above formula (1) is excellent in dispersibility to the resin component, and can improve the sealing in the semiconductor device produced by using the adhesive composition of the present invention (substrate- The strength of the end portion of the wafer, wafer-wafer, etc.).

The above-mentioned adhesion improvement is not limited to solder resists, but also Between semiconductor wafers (SiO, SiN, etc.).

The compound having a group represented by the above formula (1) is preferably a compound represented by the following formula (2).

In the formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R ² represents an alkylene group having 1 to 30 carbon atoms, and R ³ represents an alkyl group having 1 to 30 carbon atoms.

The adhesive composition of the present invention can further improve the reflow resistance, the connection reliability, and the insulation reliability by containing a filler surface-treated with the compound represented by the above formula (2).

The adhesive composition of the present invention may further contain a polymer component having a weight average molecular weight of 10,000 or more from the viewpoint of improving heat resistance and film formability of the adhesive composition.

From the viewpoint of further improving the adhesion of the adhesive composition or the film formability, the polymer component preferably has a weight average molecular weight of 30,000 or more and a glass transition temperature of 100 ° C or lower.

The adhesive composition of the present invention can further improve the fluxing activity by further containing a fluxing active agent, and remove the oxide film or impurities on the metal surface of the joint portion to form a good metal-metal joint.

The workability of the adhesive composition of the present invention is preferably a film shape in order to improve the workability of sealing the gap between the semiconductor wafer and the printed circuit board or the gap between the plurality of semiconductor wafers by precoating.

Further, the present invention provides a method of manufacturing a semiconductor device, which is a method of manufacturing a semiconductor device in which a connection portion of each of a semiconductor wafer and a printed circuit board is electrically connected to each other, or a connection portion of each of a plurality of semiconductor wafers is electrically connected to each other. There is a step of sealing the joint using the above-described adhesive composition.

According to the method of manufacturing a semiconductor device of the present invention, by using the above-described adhesive composition, the reflow resistance, connection reliability, and insulation reliability of the semiconductor device can be improved.

When the connection portion contains at least one metal selected from the group consisting of gold, silver, copper, nickel, tin, and lead, the conductivity, thermal conductivity, and connection reliability of the connection portion can be further improved.

The present invention further provides a semiconductor device fabricated by the above-described method of fabricating a semiconductor device.

Since the semiconductor device of the present invention is produced by using the above-described method for manufacturing a semiconductor device, it is excellent in solder reflow resistance, connection reliability, and insulation reliability.

According to the present invention, it is possible to provide an adhesive composition excellent in reflow resistance, connection reliability, and insulation reliability, a method of manufacturing a semiconductor device using the adhesive composition, and a semiconductor device.

10‧‧‧Semiconductor wafer

15‧‧‧Wiring (connection)

20‧‧‧Substrate (wiring circuit board)

30‧‧‧Connecting bumps

32‧‧‧Bumps (connections)

34‧‧‧through electrode

40‧‧‧Binder composition (film-like adhesive)

50‧‧‧Intermediary

60‧‧‧Anti-flux

90‧‧‧ comb electrode

100, 200, 300, 400, 500, 600‧‧‧ semiconductor devices

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention.

Fig. 2 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

Figure 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention.

Fig. 4 is a cross-sectional view showing the steps of an embodiment of a method of manufacturing a semiconductor device of the present invention.

Fig. 5 is a view showing the appearance of a sample for insulation reliability test.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are given the same reference numerals, and the repeated description is omitted. Further, the positional relationship of up, down, left, and the like is based on the positional relationship shown in the drawing unless otherwise specified. In addition, the dimensional ratio of the drawings is not limited to the scale shown.

<Binder composition>

The adhesive composition (semiconductor sealing adhesive) of the present embodiment is a semiconductor device or a plurality of semiconductor wafers that are electrically connected to each other at a connection portion between a semiconductor wafer and a printed circuit board (hereinafter, simply referred to as "substrate"). In the semiconductor device in which the respective connection portions are electrically connected to each other, the adhesive composition of the connection portion is sealed, and the composition contains an epoxy resin (hereinafter also referred to as "(a) component") and a hardener (hereinafter also referred to as a case) The "(b) component"), the acrylic surface-treated filler or the filler having a group represented by the following general formula (1) (hereinafter also referred to as "(c) component"). Further, the adhesive composition may optionally contain a polymer having a weight average molecular weight of 10,000 or more. The component (hereinafter also referred to as "(d) component") or the fluxing active agent (hereinafter also referred to as "(e) component"). Hereinafter, each component constituting the adhesive composition of the present embodiment will be described.

(a) Composition: Epoxy resin

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in the molecule. Specific examples of the component (a) include bisphenol A type, bisphenol F type, naphthalene type, phenol novolak type, cresol novolac type, phenol aralkyl type, biphenyl type, and triphenylmethane. Dicyclopentadiene type and various polyfunctional epoxy resins. These resins may be used singly or in combination of two or more.

The component (a) suppresses the generation of volatile components due to decomposition at the time of connection at a high temperature. When the temperature at the time of connection is 250 ° C, it is preferred to use a thermal weight loss rate of 5% or less at 250 ° C. When the epoxy resin is 300 ° C, it is preferred to use an epoxy resin having a thermal weight loss rate of 5% or less at 300 ° C.

(b) Ingredients: Hardener

Examples of the component (b) include a phenol resin-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, an imidazole-based curing agent, and a phosphine-based curing agent. When the component (b) contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, it exhibits a weld activity which can suppress the formation of an oxide film at the joint portion, and can improve the connection reliability. Insulation reliability. Hereinafter, each curing agent will be described.

(i) phenol resin curing agent

The phenol resin-based curing agent is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule, and for example, a phenol novolak resin or a cresol novolac can be used. A varnish resin, a phenol aralkyl resin, a cresol naphthalene formaldehyde polycondensate, a triphenylmethane type polyfunctional phenol, and various polyfunctional phenol resins. These resins may be used singly or in combination of two or more.

The equivalent ratio of the phenol resin-based curing agent to the component (a) (phenolic hydroxyl group/epoxy group, molar ratio) is preferably 0.3 to the viewpoint of good curability, adhesion, and storage stability. 1.5, more preferably 0.4 to 1.0, and even more preferably 0.5 to 1.0. When the equivalent ratio is 0.3 or more, the curability is improved and the adhesion is increased. When the ratio is 1.5 or less, the unreacted phenolic hydroxyl group does not remain excessively, and the water absorption rate is suppressed to be low, and the insulation reliability tends to be improved.

(ii) an acid anhydride hardener

As the acid anhydride-based curing agent, for example, methylcyclohexanetetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and ethylene glycol double dehydration can be used. Trimellitic acid ester. These compounds may be used singly or in combination of two or more.

The equivalent ratio (anhydride group/epoxy group, molar ratio) of the acid anhydride-based curing agent to the component (a) is preferably from 0.3 to 1.5 in terms of good curability, adhesion, and storage stability. More preferably, it is 0.4 to 1.0, and more preferably 0.5 to 1.0. When the equivalent ratio is 0.3 or more, the curability is improved and the adhesion is increased. When the ratio is 1.5 or less, the unreacted acid anhydride group does not remain excessively, and the water absorption rate is suppressed to be low, and the insulation reliability tends to be improved.

(iii) amine hardener

As the amine-based curing agent, for example, dicyanodiamine can be used.

The equivalent ratio (amine/epoxy group, molar ratio) of the amine-based curing agent to the above component (a) is excellent in hardenability, adhesion, and storage stability. From the viewpoint, it is preferably from 0.3 to 1.5, more preferably from 0.4 to 1.0, still more preferably from 0.5 to 1.0. When the equivalent ratio is 0.3 or more, the curability is improved and the adhesion is increased. When the ratio is 1.5 or less, the unreacted amine does not remain excessively, and the insulation reliability tends to be improved.

(iv) imidazole hardener

Examples of the imidazole-based curing agent include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1- Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2- Phenyl imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazoline-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-undecyl imidazoline-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazoline-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazoline-(1')]-ethyl-s-triazine Cyanuric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, And an adduct of an epoxy resin and an imidazole. Among these compounds, 1-cyanoethyl-2-undecylimidazole and 1-cyano-2-phenylimidazole are preferred from the viewpoints of excellent hardenability, storage stability, and connection reliability. , 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2 '-Methylimidazoline-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazoline-(1') ]-Ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazoline-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2 a phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. These compounds may be used singly or in combination of two or more. Alternatively, the compounds can be microencapsulated. Potential hardener.

The content of the imidazole-based curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the component (a). When the content of the imidazole-based curing agent is 0.1 part by mass or more, the curability tends to be improved. When the content is 20 parts by mass or less, the adhesive composition does not harden before the metal bonding is formed, and the connection failure tends to be less likely to occur.

(v) phosphine-based hardener

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

The content of the phosphine-based curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (a). When the content of the phosphine-based curing agent is 0.1 part by mass or more, the curing property tends to be improved. When the content is 10 parts by mass or less, the adhesive composition does not harden before the metal bonding is formed, and the connection failure tends to be less likely to occur.

The phenol resin-based curing agent, the acid anhydride-based curing agent, and the amine-based curing agent may be used alone or in combination of two or more. The imidazole-based curing agent and the phosphine-based curing agent may be used singly or in combination with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.

When the adhesive composition contains a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent as the component (b), the fluxing activity of the cured film can be removed, and the connection reliability can be further improved.

(c) component: an acrylic surface-treated filler or a filler having a group represented by the above formula (1)

The component (c) is not particularly limited as long as it is a surface-treated filler having a group represented by the above formula (1), and for example, an insulating inorganic filler, whiskers, and a resin filler may be used. Processor. That is, a filler having a group represented by the above formula (1) can be used as the component (c).

Here, in the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group. The larger the carbon number of R ¹ is, the larger the volume is. When the carbon number exceeds 2, the reactivity tends to decrease. R ² represents an alkylene group having 1 to 30 carbon atoms, preferably an alkylene group having 1 to 15 carbon atoms. When the carbon number of R ² exceeds 30, there is a tendency that it is difficult to surface-treat the filler.

Whether or not the component (c) has a group represented by the above formula (1) on the surface of the filler can be confirmed, for example, by the following method.

The adhesive composition of the present embodiment is heated, and the produced methanol is measured using a gas chromatograph (for example, manufactured by Shimadzu Corporation, product name "GC-17A"). From the amount of the methanol, it was confirmed that the group represented by the above formula (1) was present on the surface of the filler. In this case, the amount of methanol of the adhesive composition containing no component (C) was measured in the same manner as a reference.

Examples of the insulating inorganic filler include glass, cerium oxide, aluminum oxide, titanium oxide, carbon black, mica, and boron nitride, preferably cerium oxide, aluminum oxide, titanium oxide, and boron nitride. It is cerium oxide, aluminum oxide and boron nitride. Examples of the whisker include aluminum borate, aluminum titanate, zinc oxide, calcium citrate, magnesium sulfate, and boron nitride. Examples of the resin filler include polyurethanes and polyimines. These fillers and whiskers may be used singly or in combination of two or more. The shape, particle size and blending amount of the filler are not particularly limited. also Fine nano cerium oxide can be used. Among these fillers, the cerium oxide filler is preferred because of its ease of surface treatment and compatibility with a resin component.

As the component (c), a filler surface-treated with the compound represented by the above formula (2) can be used. Specifically, a cerium oxide filler surface-treated with an acrylic compound in which R ¹ is a hydrogen atom in the formula (2), and a surface treatment of a methacrylic compound in which R ¹ is a methyl group in the formula (2) can be used. The cerium oxide filler and the cerium oxide filler surface-treated with an ethyl acrylate compound in which R ¹ is an ethyl group in the formula (2). From the viewpoint of reactivity or formation of a bond with a resin component or a surface of a semiconductor substrate contained in the semiconductor adhesive, in the above formula (2), R ^{1 is} preferably a group having a small volume, and R ¹ is a hydrogen atom. Or an alkyl group having 1 or 2 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group. The larger the carbon number of R ¹ is, the larger the volume is. When the carbon number exceeds 2, the reactivity tends to decrease. That is, a ceria filler surface-treated with an acrylic compound, a methacrylic compound or an ethacrylic compound can be used as the component (c).

In the above formula (1) or (2), R ² represents an alkylene group having 1 to 30 carbon atoms, and is preferably an alkylene group having 1 to 15 carbon atoms from the viewpoint of a small amount of a volatile component. In the formula (2), R ³ represents an alkyl group having 1 to 30 carbon atoms, and can be appropriately selected depending on the easiness of surface treatment. When the carbon number of R ³ is 30 or less, there is a tendency that the filler is easily surface-treated.

The shape and particle diameter of the component (c) are not particularly limited as long as they are appropriately set depending on the use of the adhesive composition.

When the average particle diameter of the component (c) is spherical, the average particle diameter is preferably 2 μm or less, and the package has a narrower pitch and a narrower gap. In order to avoid a decrease in reliability due to trapping, it is preferably 1.5 μm or less, and particularly preferably 1.0 μm or less. Moreover, the lower limit is preferably 0.005 μm or more, and particularly preferably 0.01 μm or less from the viewpoint of workability.

The amount of the component (c) is preferably from 5 to 80% by mass, and more preferably from 10 to 70% by mass based on the total of the solid content of the adhesive composition. When the amount is 5% by mass or more, the adhesion tends to be increased. When the content is 80% by mass or less, the viscosity is easily adjusted, and the fluidity of the adhesive composition is not easily lowered or the filler is bitten toward the joint (overprint). There is a tendency to improve the reliability of the connection.

Further, when the decane coupling agent is not surface-treated with the filler in advance, it is added as a constituent component of the adhesive composition, and when surface treatment is performed in the system, methanol or the like is generated, which causes bubbles to be generated during the high-temperature process.

By improving the adhesion of the adhesive composition after moisture absorption at around 260 ° C and increasing the elastic modulus at around 260 ° C, the reflow resistance can be improved, and peeling or poor connection after reflow can be prevented.

(d) component: a polymer component having a weight average molecular weight of 10,000 or more

Examples of the component (d) include a phenoxy resin, a polyimide resin, a polyamide resin, a polycarbodiimide resin, a cyanate resin, an acrylic resin, a polyester resin, a polyethylene resin, and a polyether. Anthracene resin, polyether quinone imide resin, polyvinyl acetal resin, urethane resin and acrylic rubber. Among these, from the viewpoint of excellent heat resistance and film formability, a phenoxy resin, a polyimide resin, an acrylic rubber, a cyanate resin, and a polycarbodiimide resin are preferable. Phenoxy resin, polyimide resin and acrylic rubber. Such The component (d) may be used singly or in combination of two or more. However, the component (d) does not contain an epoxy resin as the component (a).

A commercially available product may be used as the polymer component such as the phenoxy resin or the polyimide resin, and a synthesizer may be used.

The polyimine resin can be obtained, for example, by a condensation reaction of a tetracarboxylic dianhydride with a diamine by a conventional method. More specifically, it is preferable to mix a molar or substantially equimolar tetracarboxylic dianhydride and a diamine in an organic solvent (the order of addition of each component is arbitrary), and the reaction temperature is set to 80 ° C or lower, preferably. It is 0 to 60 ° C for the addition reaction. Further, in order to suppress the deterioration of the properties of the adhesive composition, it is preferred to subject the above tetracarboxylic dianhydride to recrystallization purification treatment with acetic anhydride.

As the above addition reaction progresses, the viscosity of the reaction liquid gradually rises to form polyglycine which is a precursor of polyimine. The polyimine resin can be obtained by dehydrating and ring-closing the above polyamic acid. The dehydration ring closure can be carried out by a thermal closed loop process by heat treatment or a chemical ring closure process using a dehydrating agent. The above polylysine can be adjusted in molecular weight by depolymerization by heating at 50 to 80 °C.

The tetracarboxylic dianhydride used as a raw material of the polyimide resin is not particularly limited, and examples thereof include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2 , 2',3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, double (2,3) -dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 3,4,9,10-anthracene Carboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'- Benzophenone tetracarboxylic dianhydride, 2,3,2',3'-benzophenonetetracarboxylic dianhydride, 3,3,3',4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4 , 5-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Acid dianhydride, 2,3,6,7-tetrachloronaphthalene di-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine- 2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3, 4,3',4'-biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethyl decane II Anhydride, bis(3,4-dicarboxyphenyl)methylphenyldecane dianhydride, bis(3,4-dicarboxyphenyl)diphenyldecane dianhydride, 1,4-bis(3,4-di Carboxyphenyl dimethyl decyl benzene phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p-extension Phenyl bis(trimellitic anhydride), ethyltetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, decalin-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7 - hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylate Acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, bis(exo-bicyclo[2,2,1]heptane-2,3-dicarboxylic dianhydride, bicyclo-[2 , 2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-double [4-(3,4-Dicarboxyphenyl)phenyl]propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-( 3,4-Dicarboxyphenyl)phenyl]hexapropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 1,4-bis(2- Hydroxy hexafluoroisopropyl) benzene bis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 5-(2,5-dionetetrahydrofuranyl)-3- Methyl-3-cyclohexane-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, represented by the following formula (I) The tetracarboxylic dianhydride and the tetracarboxylic dianhydride represented by the following formula (II).

In the formula (I), a represents an integer of 2-20.

The tetracarboxylic dianhydride represented by the above formula (I) can be synthesized from trimellitic anhydride monochloride and a corresponding diol, and specific examples thereof include 1,2-(extended ethyl)bis(trimellitic anhydride) and 1, 3-(trimethylene)bis(trimellitic anhydride), 1,4-(tetramethylene)bis(trimellitic anhydride), 1,5-(pentamethylene)bis(trimellitic anhydride), 1,6-(hexamethylene Bis(trimellitic anhydride), 1,7-(heptylene)bis(trimellitic anhydride), 1,8-(octamethylene)bis(trimellitic anhydride), 1,9-(nonamethylene)bis (trimellitic anhydride) , 1,10-(decamethylene)bis(trimellitic anhydride), 1,12-(dodecyl)bis(trimellitic anhydride), 1,16-(hexamethylene)bis(trimellitic anhydride) and 1 , 18-(octadecyl) bis (trimellitic anhydride).

The tetracarboxylic dianhydride represented by the above formula (II) is preferred from the viewpoint of imparting excellent moisture resistance reliability to the tetracarboxylic dianhydride. Above four The carboxylic acid dianhydride may be used singly or in combination of two or more.

The content of the tetracarboxylic dianhydride represented by the above formula (II) is preferably 40 mol% or more, more preferably 50 mol% or more, and still more preferably 70 mol% based on the total tetracarboxylic dianhydride. the above. When the content is 40% by mole or more, the moisture resistance reliability effect obtained by using the carboxylic acid dianhydride represented by the above formula (II) tends to be sufficiently ensured.

The diamine used as a raw material of the above polyimine resin is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and 3,3'-diaminodiphenyl. Ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, 4,4'-diaminodiphenyl ether methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-di Isopropylphenyl)methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldi Fluoromethane, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenylanthracene, 3,3'-diamino Diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4 '-Diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-di Aminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,4'- Diamine Diphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-amine Benzophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 3,3'-(1,4-phenylphenylbis(1-methylethylidene))diphenylamine, 3,4'-(1,4-phenylenebis(1-methylethylidene))diphenylamine, 4,4'-(1,4-phenylenebis(1-methylethylidene) Diphenylamine, 2,2-bis(4-(3- Aminophenoxy)phenyl)propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-aminophenoxy) Phenyl) hexafluoropropane, bis(4-(3-aminophenoxy)phenyl) sulfide, bis(4-(4-aminophenoxy)phenyl) sulfide, bis (4) An aromatic diamine such as -(3-aminophenoxy)phenyl)anthracene, bis(4-(4-aminophenoxy)phenyl)anthracene or 3,5-diaminobenzoic acid; 3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, an aliphatic ether diamine represented by the following formula (III) or (IV) An aliphatic diamine represented by the following general formula (V) and a nonoxyalkylene diamine represented by the following general formula (VI).

In the formula (III), Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 1 to 80.

In the formula (IV), Q ⁴ , Q ⁵ , Q ⁶ and Q ⁷ each independently represent an alkylene group having 1 to 10 carbon atoms, and c, d and e each independently represent an integer of 1 to 50.

In the formula (V), f represents an integer of 5-20.

In the formula (VI), Q ⁸ and Q ¹³ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenyl group which may have a substituent, and Q ⁹ , Q ¹⁰ , Q ¹¹ and Q ¹² each independently represent a carbon number of 1 ~5 alkyl, phenyl or phenoxy, g represents an integer from 1 to 5.

Among these compounds, a diamine represented by the above formula (III), (IV) or (V) is preferred from the viewpoint of imparting low stress, low-temperature lamination property and low-temperature adhesion. From the viewpoint of imparting low water absorbability and low hygroscopicity, a diamine represented by the above formula (VI) is preferred. These diamines may be used singly or in combination of two or more.

The content of the aliphatic ether diamine represented by the above formula (III) or (IV) is preferably from 1 to 50 mol% of the total diamine, and the aliphatic diamine represented by the above formula (V) The content is preferably from 20 to 80 mol% of the total diamine, and the content of the nonoxyldiamine represented by the above formula (VI) is preferably from 20 to 80 mol% of the total diamine. When it is in the above content range, the effect of imparting low-temperature lamination property and low water absorption property tends to be large.

Further, specific examples of the aliphatic ether diamine represented by the above formula (III) include aliphatic ether diamines of the following formulas (III-1) to (III-5). Further, in the general formulae (III-4) and (III-5), n represents an integer of 1 or more.

The weight average molecular weight of the aliphatic ether diamine represented by the above formula (III-4) is preferably, for example, 350, 750, 1100 or 2100. Further, the weight average molecular weight of the aliphatic ether diamine represented by the above formula (III-5) is preferably, for example, 230, 400 or 2,000.

In the above aliphatic ether diamine, from the viewpoint of ensuring low-temperature lamination property and good adhesion to a substrate having an organic barrier, it is preferred to respectively use the above formula (IV) and the following formula ( An aliphatic ether diamine represented by VII), (VIII) or (IX).

In the formula (VII), h represents an integer of 2 to 80, preferably 2 to 70.

In the formula (VIII), c, d and e represent an integer of from 1 to 50, preferably from 2 to 40.

In the formula (IX), j and k each independently represent an integer of 1 to 70.

Specific examples of the aliphatic ether diamine represented by the above formula (VII) include Jeffamine D-230, D-400, D-2000 and D-4000 manufactured by Suntechno Chemical Co., Ltd., manufactured by BASF. The polyetheramines D-230, D-400, and D-2000, as the aliphatic ether diamine represented by the above formula (VIII), specifically, Jeffamine ED-600 manufactured by Suntechno Chemical Co., Ltd. ED-900 and ED-2001, as the aliphatic ether diamine represented by the above formula (IX), Jeffamine EDR-148 manufactured by Suntechno Chemical Co., Ltd. may be mentioned.

Examples of the aliphatic diamine represented by the above formula (V) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, and 1, 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1, 10-Diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and 1,2-diaminocyclohexane. Among these compounds, preferred are 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. .

The dioxane diamine represented by the above formula (VI), when g in the formula (VI) is 1, may be exemplified by 1,1,3,3-tetramethyl-1,3-bis ( 4-aminophenyl)dioxane, 1,1,3,3-tetraphenoxy-1,3-bis(4-aminoethyl) Dioxane, 1,1,3,3-tetraphenyl-1,3-bis(2-aminoethyl)dioxane, 1,1,3,3-tetraphenyl-1,3 - bis(3-aminopropyl)dioxane, 1,1,3,3-tetramethyl-1,3-bis(2-aminoethyl)dioxane, 1,1,3 ,3-tetramethyl-1,3-bis(3-aminopropyl)dioxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminobutyl) Dioxane, and 1,3-dimethyl-1,3-dimethoxy-1,3-bis(4-aminobutyl)dioxane. When g is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)trioxane, 1,1,5,5- may be mentioned. Tetraphenyl-3,3-dimethyl-1,5-bis(3-aminopropyl)trioxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy -1,5-bis(4-aminobutyl)trioxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-amino group Pentyl)trioxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(2-aminoethyl)trioxane, 1,1 ,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trioxane, 1,1,5,5-tetramethyl-3, 3-dimethoxy-1,5-bis(5-aminopentyl)trioxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-amine Propyl)trioxane, 1,1,3,3,5,5-hexaethyl-1,5-bis(3-aminopropyl)trioxane, and 1,1,3, 3,5,5-hexapropyl-1,5-bis(3-aminopropyl)trioxane.

The above polyimine resin may be used singly or in combination of two or more.

The glass transition temperature (Tg) of the component (d) is preferably 100 ° C or less, and more preferably 85 ° C or less from the viewpoint of excellent adhesion of the adhesive composition to the substrate or the wafer. When the Tg is 100 ° C or less, the bump formed on the semiconductor wafer or the uneven portion such as the electrode or the wiring pattern formed on the substrate can be easily buried in the adhesive composition, and the bubble does not remain easily. The tendency to create holes. Further, the above Tg system was DSC (DSC-7 type manufactured by Perkin Elmer Co., Ltd.), and the sample amount was 10 mg, and the temperature increase rate was 10 ° C/min. Determination of atmosphere: Tg as determined by air conditions.

The weight average molecular weight of the component (d) is 10,000 or more in terms of polystyrene, but it is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 50,000 or more, in order to exhibit good film formability. When the weight average molecular weight is 10,000 or more, film formability and heat resistance tend to be improved. In the description of the present invention, the weight average molecular weight means a weight average molecular weight measured in terms of polystyrene using a high-speed liquid chromatography (for example, manufactured by Shimadzu Corporation, product name "C-R4A").

The content of the component (d) is not particularly limited, but is preferably in the form of a film, and is preferably from 1 to 500 parts by mass, more preferably from 5 to 300 parts by mass, more preferably from 100 to 300 parts by mass, per 100 parts by mass of the component (a). 10 to 200 parts by mass. When the content of the component (d) is 1 part by mass or more, the effect of improving the film formability tends to be easily obtained, and when it is 500 parts by mass or less, the curability of the adhesive composition is improved, and the adhesion is improved. tendency.

(e) Ingredients: fluxing active agent

The adhesive composition of the present invention may contain a component (e), that is, a flux active agent which exhibits a fluxing activity (activity of removing oxides or impurities). Examples of the flux activator include nitrogen-containing compounds having an unshared electron pair such as imidazoles or amines, carboxylic acids, phenols, and alcohols.

Among these compounds, since the carboxylic acid has a strong fluxing activity, it can react with the epoxy resin of the component (a) without being present in a free state in the cured product of the adhesive composition, thereby preventing insulation reliability. The decline.

Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, dodecanoic acid, myristic acid, and ten. An aliphatic saturated carboxylic acid such as hexaic acid, heptadecanoic acid or octadecanoic acid; oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, etc. Aliphatic unsaturated carboxylic acid; aliphatic dicarboxylic acid such as maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid; benzoic acid, phthalic acid, isophthalic acid , aromatic carboxylic acid such as terephthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, pentanecarboxylic acid, and mellitic acid acid. Further, examples of the carboxylic acid having a hydroxyl group include lactic acid, malic acid, citric acid, and salicylic acid.

Further, an aromatic carboxylic acid having an electron withdrawing or electron-donating substituent on the aromatic carboxylic acid and changing the acidity of the aromatic carboxylic acid by a substituent may be used. Although the higher the acidity of the carboxylic acid, the higher the tendency of the fluxing activity is, the lower the acidity, the lower the insulation reliability. Examples of the electron-donating substituent which can increase the acidity of the carboxylic acid include a nitro group, a cyano group, a trifluoromethyl group, a halogen group, and a phenyl group. Examples of the electron-donating substituent which can weaken the acidity of the carboxylic acid include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a dimethylamino group, and a trimethylamino group. Further, the number or position of the above substituents is not particularly limited as long as the fluxing activity or the insulation reliability is not lowered.

(other ingredients)

In addition to the component (c), the adhesive composition of the present embodiment may be formulated with other fillers to control the viscosity or the physical properties of the cured product, and to suppress the occurrence of voids or the moisture absorption rate when the semiconductor wafer and the substrate are joined.

As the filler, an insulating inorganic filler, whiskers or a resin filler can be used. As the insulating inorganic filler, the whisker or the resin filler, the same ones as the above component (c) can be used. The fillers, whiskers and resin fillers can be used alone Use one or a mixture of two or more. The shape, average particle diameter and content of the filler are not particularly limited.

Further, an additive such as an antioxidant, a decane coupling agent, a titanium coupling agent, a leveling agent, or an ion trapping agent may be formulated in the adhesive composition of the present embodiment. These additives may be used alone or in combination of two or more. The amount of the additives to be added may be appropriately adjusted so as to exhibit the effect of each additive.

The adhesive composition of this embodiment can be formed into a film shape. Hereinafter, a method of producing a film-form adhesive using the adhesive composition of the present embodiment will be described. First, the component (a), the component (b), the component (c), and the component (d) or the component (e) to be added as needed are added to an organic solvent, and are dissolved or dispersed by stirring, mixing, or the like. To modulate the resin paint. Subsequently, the resin paint is applied onto the substrate film subjected to the release treatment using a knife coater, a roll coater or an applicator, and then the organic solvent is removed by heating, thereby obtaining on the substrate film. Film-like adhesive.

The organic solvent used for the preparation of the resin paint preferably has a property of uniformly dissolving or dispersing each component, and examples thereof include dimethylformamide, dimethylacetamide, and N-methyl- 2-pyrrolidone, dimethyl hydrazine, diethylene glycol dimethyl ether, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl solution Fiber, dioxane, cyclohexanone, and ethyl acetate. These organic solvents may be used singly or in combination of two or more. The stirring or kneading at the time of preparation of the resin paint can be carried out using, for example, a stirrer, a kneader, a triaxial roll, a ball mill, a bead mill, and a homogenizer.

The base film is not particularly limited as long as it has heat resistance to the heating conditions in which the organic solvent is volatilized, and examples thereof include a polyolefin film such as a polypropylene film or a polymethylpentene film, and polyethylene terephthalate. A polyester film such as an ester film or a polyethylene naphthalate film, a polyimide film, and a polyether quinone film. The base film is not limited to a single layer formed of the films, and may be a multilayer film composed of two or more materials.

The drying condition in which the organic solvent is volatilized from the resin paint applied to the base film is preferably a condition in which the organic solvent is sufficiently volatilized, and specifically, it is preferably heated at 50 to 200 ° C for 0.1 to 90 minutes.

Further, the adhesive composition of the present embodiment can be directly applied by spin coating on a wafer, and dried, and then diced the wafer, from the viewpoint of improving workability.

<Semiconductor device>

The semiconductor device of the present embodiment will be described below with reference to Figs. 1 and 2 . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. As shown in FIG. 1(a), the semiconductor device 100 has semiconductor wafers 10 and substrates (circuit wiring boards) 20 opposed to each other, and wirings 15 disposed on opposite surfaces of the semiconductor wafer 10 and the substrate 20, respectively. The connection bumps 30 of the semiconductor wafer 10 and the wiring 15 of the substrate 20 are connected to each other, and the adhesive composition 40 which fills the gap between the semiconductor wafer 10 and the substrate 20 without a gap. The semiconductor wafer 10 and the substrate 20 are connected in a flip chip manner by the wiring 15 and the connection bumps 30. The wiring 15 and the connection bumps 30 are sealed by the adhesive composition 40 to be isolated from the external environment.

As shown in FIG. 1(b), the semiconductor device 200 has mutual orientation The semiconductor wafer 10 and the substrate 20 are respectively disposed on the bumps 32 on the surfaces of the semiconductor wafer 10 and the substrate 20 facing each other, and the adhesive composition 40 which is filled in the gap between the semiconductor wafer 10 and the substrate 20 without gaps. The semiconductor wafer 10 and the substrate 20 are connected in a flip chip manner by connecting the opposing bumps 32 to each other. The bump 32 is sealed from the external environment by the seal of the adhesive composition 40.

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

The semiconductor wafer 10 is not particularly limited, and an elemental semiconductor composed of the same element such as ruthenium or osmium or a compound semiconductor such as gallium arsenide or indium phosphide can be used.

The substrate 20 is not particularly limited as long as it is a circuit board, and can be used as an insulating material containing glass epoxy resin, polyimide, polyester, ceramic, epoxy resin, bismaleimide triazine or the like as a main component. a circuit board having a wiring (wiring pattern) 15 formed by etching unnecessary portions of the metal film on the surface of the substrate, a circuit board on which the wiring 15 is formed by metal plating or the like on the surface of the insulating substrate, or A circuit board on which the conductive material is printed on the surface of the insulating substrate to form the wiring 15 is formed.

The connection portion of the wiring 15 or the bump 32 or the like contains gold, silver, copper, and solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), Nickel, tin, lead, etc. are used as a main component, and may also contain a plurality of metals.

Among the above metals, it becomes the conductivity of the joint. From the viewpoint of sealing having excellent thermal conductivity, gold, silver and copper are preferred, and silver and copper are more preferred. From the viewpoint of being a cost-effective seal, it is preferably inexpensive, preferably silver, copper, and solder, more preferably copper and solder, and more preferably solder. Since the productivity is lowered or the cost is increased when an oxide film is formed on the surface of the metal at room temperature, gold, silver, copper, and solder are preferable from the viewpoint of suppressing the formation of the oxide film, and more preferably gold or silver. , solder, and more preferably gold, silver.

The surface of the wiring 15 and the bump 32 may be formed of, for example, gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper), tin, or the like by plating. A metal layer containing nickel or the like as a main component. The metal layer may be composed of only a single component or a plurality of components. Further, the metal layer may have a structure in which a single layer or a plurality of metal layers are laminated.

Further, the semiconductor device of the present embodiment may have a plurality of structures (sealing) as shown in the semiconductor devices 100 to 400. In this case, the semiconductor devices 100-400 may also contain gold, silver, copper, solder (main components such as tin-silver, tin-lead, tin-bismuth, tin-copper, tin-silver-copper), tin, The bumps or wires of nickel or the like are electrically connected to each other.

As a method of a plurality of laminated semiconductor devices, as shown in FIG. 3, for example, a TSV (through-hole via) technique can be cited. Fig. 3 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention, which is a semiconductor device using TSV technology. In the semiconductor device 500 shown in FIG. 3, the semiconductor wafer 10 and the interposer are connected by connecting the wiring 15 formed on the interposer 50 to the wiring 15 of the semiconductor wafer 10 via the connection bump 30. 50 is connected by flip chip. The subsequent composition 40 is filled in the gap between the semiconductor wafer 10 and the interposer 50 without a gap. The semiconductor wafer 10 is repeatedly laminated on the surface of the semiconductor wafer 10 opposite to the interposer 50 so as to sandwich the wiring 15 and the bumps 30 and the adhesive composition 40. The wirings 15 of the pattern surface on the front and back sides of the semiconductor wafer 10 are connected to each other through the through electrodes 34 filled in the holes penetrating the inside of the semiconductor wafer 10. Further, copper, aluminum, or the like can be used as the material of the through electrode 34.

With such TSV technology, signals can also be obtained from the reverse side of a semiconductor wafer that is not normally used. Further, since the through electrodes 34 in the semiconductor wafer 10 pass vertically, the distance between the opposite semiconductor wafers 10 or between the semiconductor wafer 10 and the interposer 50 is shortened, and the connection can be made soft. The adhesive composition of the present embodiment can be used as a semiconductor sealing adhesive between the semiconductor wafers 10 or between the semiconductor wafer 10 and the interposer 50 in the TSV technology.

Further, by the bump forming method having a high degree of freedom such as the area bump wafer technique, the semiconductor wafer can be directly mounted on the motherboard without the interposer. The adhesive composition of this embodiment can also be used in the case where the semiconductor wafer is directly mounted on a motherboard. Further, in the case where two wiring circuit substrates are laminated, the adhesive composition of the present embodiment can also be used to seal the gaps between the substrates.

<Method of Manufacturing Semiconductor Device>

The method of manufacturing the semiconductor device of the present embodiment will be described below with reference to Fig. 4 . Fig. 4 is a cross-sectional view showing the steps of an embodiment of a method of manufacturing a semiconductor device of the present invention.

First, as shown in FIG. 4(a), a solder resist 60 having an opening is formed on the substrate 20 having the wiring 15 at a position where the connection bumps 30 are formed. The solder resist 60 does not necessarily need to be provided. However, by providing a solder resist on the substrate 20, bridging between the wires 15 can be suppressed, and the connection reliability is improved. Insulation reliability. The solder resist 60 can be formed using, for example, a commercially available ink for soldering for sealing. Specific examples of the commercially available ink for sealing flux are SR series (manufactured by Hitachi Chemical Co., Ltd., trade name) and PSR4000-AUS series (manufactured by Sun Ink Manufacturing Co., Ltd., trade name).

Next, as shown in FIG. 4(a), the connection bumps 30 are formed in the openings of the solder resist 60. Then, as shown in FIG. 4(b), a film-form adhesive composition (hereinafter, referred to as "film-like adhesive" as appropriate) is attached to the substrate 20 on which the connection bumps 30 and the solder resist 60 are formed. . The attachment of the film-like adhesive 40 can be carried out by heat pressing, roll lamination, vacuum lamination, or the like. The supply area or thickness of the film-like adhesive 40 is appropriately set depending on the size of the semiconductor wafer 10 and the substrate 20 or the height of the connection bumps 30.

After the film-like adhesive 40 is attached to the substrate 20 as described above, the wiring 15 of the semiconductor wafer 10 is aligned with the connection bump 30 by using a bonding device such as a flip chip bonder. Next, the semiconductor wafer 10 and the substrate 20 are heated and pressed at a temperature higher than the melting point of the connection bump 30, as shown in FIG. 4(c), while the semiconductor wafer 10 and the substrate 20 are joined, a film-like adhesive 40 is used. The gap between the semiconductor wafer 10 and the substrate 20 is sealed and filled. According to the above method, the semiconductor device 600 is fabricated.

In the method of fabricating the semiconductor device of the present embodiment, it is also possible to temporarily fix (the state in which the semiconductor adhesive is interposed) after the alignment position, and then The reflow furnace is subjected to heat treatment, whereby the connection bumps 30 are melted to connect the semiconductor wafer 10 and the substrate 20. Since it is not necessary to form a metal joint at the temporary fixing stage, it can be pressed by a low load, a short time, and a low temperature as compared with the above-described method of pressing while heating, thereby improving productivity and suppressing deterioration of the joint portion. .

Further, after the semiconductor wafer 10 is connected to the substrate 20, heat treatment may be performed in an oven or the like to further improve connection reliability and insulation reliability. The heating temperature is preferably a temperature at which the film-like adhesive is hardened, more preferably a temperature at which the curing is complete. The heating temperature and heating time are set as appropriate.

In the method of manufacturing a semiconductor device of the present embodiment, the substrate 20 may be connected after the film-like adhesive 40 is attached to the semiconductor wafer 10. Further, after the semiconductor wafer 10 and the substrate 20 are connected via the wiring 15 and the connection bumps 30, a paste-like adhesive composition may be filled in the gap between the semiconductor wafer 10 and the substrate 20.

From the viewpoint of improving productivity, the adhesive composition may be supplied to a semiconductor wafer obtained by bonding a plurality of semiconductor wafers 10, and then an adhesive composition may be supplied onto the semiconductor wafer 10 by dicing dicing. The structure. Further, when the adhesive composition is in the form of a paste, it is not particularly limited, but the wiring or the bumps on the semiconductor wafer 10 may be buried by a coating method such as spin coating to uniformize the thickness. In this case, since the supply amount of the resin is fixed, the productivity can be improved, and the occurrence of voids due to insufficient filling and the decrease in the cutting property can be suppressed. On the other hand, in the case where the adhesive composition is in the form of a film, it is not particularly limited, but the wiring or the bump on the semiconductor wafer 10 is buried by a bonding method such as heat pressing, roll lamination, and vacuum lamination. Into The film-like resin composition may be supplied in a manner. In this case, since the supply amount of the resin is fixed, the productivity can be improved, and the occurrence of voids due to insufficient filling and the decrease in the cutting property can be suppressed.

The connection load is set in consideration of the variation in the number or height of the connection bumps 30, the connection bump 30 due to pressurization, or the amount of deformation of the wiring that receives the bump of the connection portion. The connection temperature is preferably such that the temperature of the connection portion is equal to or higher than the melting point of the connection bump 30, but it is a temperature at which metal bonding of individual connection portions (bumps or wiring) can be formed. When the connection bump 30 is a solder bump, it is preferably about 240 ° C or higher.

The connection time at the time of connection varies depending on the constituent metal of the connection portion, but from the viewpoint of improving productivity, the shorter the time, the better. When the connection bump 30 is a solder bump, the connection time is preferably 20 seconds or less, more preferably 10 seconds or less, still more preferably 5 seconds or less. When it is a copper-copper or copper-gold metal connection, the connection time is preferably 60 seconds or less.

In the flip chip joint of the above various sealing structures, the adhesive composition of the present invention also exhibits excellent reflow resistance, connection reliability, and insulation reliability.

[Examples]

Hereinafter, the present invention will be described using examples and comparative examples, but the present invention is not limited to the examples below.

(Synthesis of Polyimine)

Into a 300 mL flask equipped with a thermometer, a stirrer, and a calcium chloride tube, 2.10 g (0.035 mol) of 1,12-diaminododecane, polyether diamine (manufactured by BASF, trade name "ED2000"), molecular weight :1923)17.31g (0.03 m), 1,3-bis(3-aminopropyl)tetramethyldioxane (manufactured by Shin-Etsu Chemical Co., trade name "LP-7100") 2.61 g (0.035 mol), and N-methyl-2-pyrrolidone 150 g (manufactured by Kanto Chemical Co., hereinafter referred to as "NMP") was stirred. After the above diamine was dissolved, the flask was cooled in an ice bath while a small amount of 4,4'-(4,4'-isopropylidenediphenoxy)bis(benzene) purified by recrystallization from acetic anhydride was added in small portions. Dicarboxylic anhydride) (manufactured by ALDRICH, trade name "BPADA") 15.62 g (0.10 mol). After reacting for 8 hours at room temperature, 100 g of xylene was added and nitrogen gas was blown while heating at 180 ° C, and xylene was azeotropically removed together with water to obtain a polyimide resin. The obtained polyimine resin removal solvent (NMP) was dissolved in methyl ethyl ketone (MEK) so as to have a solid content of 50% by mass, and it was referred to as "polyimine A". Polyethylenimine A had a Tg of 30 ° C, a weight average molecular weight of 50,000, and an SP value (solubility parameter) of 10.2.

The compounds used in the respective examples and comparative examples are as follows.

(a) Epoxy resin

. A polyfunctional solid epoxy resin containing a trisphenol methane skeleton (manufactured by Nippon Epoxy Resin Co., Ltd., trade name "EP1032H60", hereinafter referred to as "EP1032").

. Bisphenol F type liquid epoxy resin (manufactured by Nippon Epoxy Resin Co., Ltd., trade name "YL983U", hereinafter referred to as "YL983").

. Soft epoxy resin (manufactured by Nippon Epoxy Resin Co., Ltd., trade name "YL7175", hereinafter referred to as "YL7175").

(b) hardener

. 2-Phenyl-4.5-dihydroxymethylimidazole (manufactured by Shikoku Chemicals Co., Ltd., The product name is "2PHZ-PW", hereinafter referred to as "2PHZ").

. 2,4-Diamino-6-[2'-methylimidazoline-(1')]-ethyl-s-triazine isocyanuric acid adduct (manufactured by Shikoku Kasei Co., Ltd., trade name " 2MAOK-PW", hereinafter referred to as "2MAOK").

(c) an acrylic surface-treated filler or a filler having a group represented by the above formula (1)

. A methacrylic acid surface-treated cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "SE2050-SMJ", an average particle diameter of 0.5 μm, hereinafter referred to as "SM cerium oxide").

. A methacrylic acid surface-treated nano cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "YA050C-SM", hereinafter referred to as "SM nano cerium oxide").

(c') other fillers

. Untreated cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "SE2050", average particle diameter 0.5 μm, hereinafter referred to as "untreated cerium oxide").

. Amino decane-treated cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "SE2050-SXJ", average particle diameter: 0.5 μm, hereinafter referred to as "SX cerium oxide").

. An epoxy decane-treated cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "SE2050-SEJ", an average particle diameter of 0.5 μm, hereinafter referred to as "SE cerium oxide").

. Phenyl decane-treated cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "SE2050-SPJ", average particle diameter 0.5 μm, hereinafter referred to as "SP" Ceria").

. A phenyl surface-treated nano cerium oxide filler (manufactured by Admatech Co., Ltd., trade name "YA050C-SP", an average particle diameter of 50 nm, hereinafter referred to as "SP nano cerium oxide").

. Organic filler (1) (manufactured by Mitsubishi Ray, trade name "W5500", hereinafter referred to as "W5500").

. Organic filler (2) (manufactured by ROHM & HASS Co., Ltd., trade name "EXL-2655", core-shell type organic fine particles, hereinafter referred to as "EXL2655").

(d) a polymer component having a molecular weight of 10,000 or more

. Phenoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name "ZX1356", Tg: about 71 ° C, Mw: about 63,000, hereinafter referred to as "ZX1356").

. Polyimine A synthesized as described above

(e) fluxing active agent (flux)

. Diphenolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

. Adipic acid (made by Wako Pure Chemical Industries Co., Ltd.)

<Preparation of film-like adhesive for semiconductor sealing>

(Example 1)

100 parts by mass of the epoxy resin (EP1032), 7.5 parts by mass of the curing agent (2PHZ), 175 parts by mass of the filler (SM cerium oxide), and the flux active agent (diphenolic acid) were fed so as to have a solid content of 60% by mass. 25 parts by mass, and a MEK solvent, a bead having a diameter of 0.8 mm and a bead having a diameter of 2.0 mm, which are equal to the solid content, are used as a bead mill (Japan FRITSCH Co., Ltd., planetary micropulverizer "P- 7") Stir for 30 minutes. Next, 100 parts by mass (converted solid content) of polyimine A was added, and the mixture was again stirred by a bead mill. After mixing for 30 minutes, the beads used for the stirring were removed by filtration to obtain a resin paint.

The obtained resin paint was applied to a base film (manufactured by Teijin DuPont Film Co., Ltd., trade name "PUREX A53") in a small precision coating device (manufactured by Lianjing Seiki), and in a clean oven (ESPEC shares) The product was manufactured by drying at 70 ° C for 10 minutes to prepare a film-like adhesive.

(Examples 2 to 3 and Comparative Examples 1 to 6)

The film-form adhesives of Examples 2 to 3 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1 except that the composition of the raw materials used was changed in accordance with Table 1 below.

The evaluation methods of the film-form adhesives obtained in the examples and the comparative examples are described below.

<Measurement of elastic modulus at 260 ° C>

The film-like adhesive was cut into a specific size (length 37 mm × width 4 mm × thickness 0.13 mm), and was cured in a clean oven (manufactured by ESPEC Co., Ltd.) at 180 ° C for 3 hours. After the hardening, the modulus of elasticity at 260 ° C was measured using a viscoelasticity measuring device (manufactured by Rheometrics, trade name "RAS II"), and 260 ° C was the temperature at which the reflow furnace was reached during the evaluation of the reflow resistance. The measurement was carried out at a temperature range of -30 to 270 ° C, a temperature increase rate of 5 ° C / min, and a measurement wavelength of 10 Hz.

<Measurement of the adhesion force at 260 ° C after moisture absorption>

The film-like adhesive was cut into a specific size (length 5 mm × width 5 mm × thickness 0.025 mm), and attached to a ruthenium wafer (length 5 mm × width 5 mm × thickness 0.725 mm, oxide film coating) at 60 ° C, and then used Hot pressing test machine (Hitachi Chemical Division) (manufactured by TECH Co., Ltd.) pressed against a glass epoxy substrate (thickness: 0.02 mm) coated with a solder resist (manufactured by Sun Ink, trade name "AUS308") (compression conditions: film-like adhesive reaches temperature of 180 ° C /10 sec / 0.5 MPa; subsequently, the film-like adhesive reached a temperature of 245 ° C / 10 sec / 0.5 MPa). Next, post-hardening (180 ° C / 3 hours) was carried out in a clean oven (manufactured by ESPEC Co., Ltd.). Subsequently, it was placed in a thermo-hygrostat (manufactured by ESPEC Co., Ltd., trade name "PR-2KP") at 85 ° C and a relative humidity of 60% for 48 hours, and after taking out, a force measuring device was used on a hot plate at 260 ° C. (manufactured by DAGE, the universal type Bond Tester DAGE4000), measured at a tool height of 0.05 mm from the substrate and a tool speed of 0.05 mm/sec.

<Evaluation of initial connectivity>

The film-form adhesive prepared was cut into a specific size (length 8 mm × width 8 mm × thickness 0.025 mm) and attached to a glass epoxy substrate (glass epoxy substrate: 420 μm thick, copper wiring: 9 μm thick, 80 μm) On the pitch), a semiconductor wafer with solder bumps is mounted on the flip chip mounting device "FCB3" (manufactured by Panasonic, trade name) (wafer size: length 7 mm × width 7 mm × height 0.15 mm; bumps: copper pillars and solder 80 μm pitch) (Installation conditions: the film-like adhesive reaches a temperature of 180 ° C, 10 seconds, 0.5 MPa; subsequently, the film-like adhesive reaches a temperature of 245 ° C, 10 seconds, 0.5 MPa). Thereby, in the same manner as in FIG. 4, a semiconductor device in which the glass epoxy substrate and the semiconductor bump-attached semiconductor wafer are daisy-chained is obtained.

The connection resistance value of the obtained semiconductor device is measured by using a multimeter (manufactured by ADVANTEST, trade name "R6871E"). Evaluate whether it can be initially turned on after installation. When the connection resistance value is 11 to 14 Ω, it is evaluated as good "A", and if it is a connection resistance value other than the above or a connection failure (disconnection) and the resistance value cannot be expressed, it is evaluated as "B".

<Evaluation of reflow resistance>

The above semiconductor device was molded into a specific shape at 180 ° C, 6.75 MPa, and 90 seconds using a sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name "CEL9700HF10K"), and in a clean oven (ESPEC Co., Ltd.) In the manufacture, it was hardened at 175 ° C for 5 hours to obtain a package. Next, the seal was subjected to high-temperature moisture absorption under the conditions of JEDEC level 2, and then sealed by an IR reflow furnace (manufactured by FURUKAWA ELECTRIC, trade name "SALAMANDER"). The sealing property after the reflow was evaluated in the same manner as the evaluation of the initial connectivity described later, and was evaluated as the reflow resistance. The case where the peeling is not good and the connection is good is "A", and the case where the peeling or the connection failure occurs and the resistance value cannot be expressed is "B".

<Evaluation of connection reliability (TCT evaluation)>

The above semiconductor device was molded into a specific shape at 180 ° C, 6.75 MPa, and 90 seconds using a sealing material (manufactured by Hitachi Chemical Co., Ltd., trade name "CEL9700HF10K"), and in a clean oven (ESPEC Co., Ltd.) In the manufacture, it was hardened at 175 ° C for 5 hours to obtain a package. Next, the seal was placed in a thermal cycle tester (manufactured by ETAC, thermal shock chamber NT1200), and a current of 1 mA was applied thereto at 25 ° C for 2 minutes / -55 ° C for 15 minutes / 25 ° C for 2 minutes / 125 ° C 15 The connection resistance was measured as a cycle in minutes/25 ° C for 2 minutes, and the change in connection resistance after repeating 1000 cycles was evaluated. Compared with the initial resistance value waveform, there is no significant change after 1000 cycles. "A" is "B" when a difference of 1 Ω or more is generated.

<Evaluation of insulation reliability (HAST evaluation)>

The film-form adhesive prepared was cut into a specific size (length 10 mm × width 5 mm × thickness 25 μm), and attached to a polyimide electrode substrate on which a wiring copper wiring was formed (wiring pitch: 0.05 mm) As shown in FIG. 5, a sample of the film-like adhesive 40 is laminated on the substrate 20 on which the comb-shaped electrode 90 is formed. Further, in Fig. 5, the illustration of the film-like adhesive is omitted for the sake of convenience. Next, the sample was placed in a clean oven (manufactured by ESPEC Co., Ltd.) and hardened at 185 ° C for 3 hours. After hardening, each sample was taken out and placed in an accelerated life tester (manufactured by HIRAYAMA Co., Ltd., trade name "PL-422R8", condition: 130 ° C / relative humidity: 85% / 200 hours / applied voltage: 5 V), and the insulation resistance was measured. After 200 hours, the insulation resistance was 108 Ω or more, and it was evaluated as "A". When it is less than 108 Ω, it is evaluated as "B".

The raw material compositions (unit: parts by mass) of the adhesive compositions of the respective examples and comparative examples are shown in Table 1, and the results of the respective tests are shown in Table 2.

It has been confirmed that Examples 1 to 3 using an acrylic surface-treated filler have higher adhesion at 260 ° C after moisture absorption, and are resistant to reflow, TCT and HAST. Excellent for sex.

Claims (10)

An adhesive composition which is formed by sealing a semiconductor device in which a connection portion of a semiconductor wafer and a printed circuit board are electrically connected to each other, or a semiconductor device in which respective connection portions of a plurality of semiconductor wafers are electrically connected to each other And the adhesive composition comprising an epoxy resin, a hardener, and an acrylic surface-treated filler surface-treated with a compound having a group represented by the following formula (1); [In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ² represents an alkylene group having 1 to 30 carbon atoms]. The adhesive composition of claim 1, wherein the compound is a compound represented by the following formula (2); In the formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R ² represents an alkylene group having 1 to 30 carbon atoms, and R ³ represents an alkyl group having 1 to 30 carbon atoms. An adhesive composition which is formed by sealing a semiconductor device in which a connection portion of a semiconductor wafer and a printed circuit board are electrically connected to each other, or a semiconductor device in which respective connection portions of a plurality of semiconductor wafers are electrically connected to each other And the binder composition comprising an epoxy resin, a hardener, and a filler having a group represented by the following formula (1); [In the formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and R ² represents an alkylene group having 1 to 30 carbon atoms]. The adhesive composition according to any one of claims 1 to 3, further comprising a polymer component having a weight average molecular weight of 10,000 or more. The adhesive composition of claim 4, wherein the polymer component has a weight average molecular weight of 30,000 or more and a glass transition temperature of 100 ° C or less. The adhesive composition according to any one of claims 1 to 5, further comprising a fluxing active agent. The adhesive composition according to any one of claims 1 to 6, which is in the form of a film. A method of manufacturing a semiconductor device, which is a semiconductor wafer and wiring A method of manufacturing a semiconductor device in which a connection portion of each of the circuit boards is electrically connected to each other or a connection portion of each of the plurality of semiconductor wafers is electrically connected to each other, and the manufacturing method is provided as used in any one of claims 1 to 7 The adhesive composition is a step of sealing the connecting portion. The manufacturing method of claim 8, wherein the connecting portion contains at least one metal selected from the group consisting of gold, silver, copper, nickel, tin, and lead as a main component. A semiconductor device obtained by the manufacturing method of claim 8 or 9.