WO2010137442A1

WO2010137442A1 - Adhesive composition, adhesive sheet, and process for manufacture of semiconductor device

Info

Publication number: WO2010137442A1
Application number: PCT/JP2010/057594
Authority: WO
Inventors: 永井　朗; 大久保　恵介
Original assignee: 日立化成工業株式会社
Priority date: 2009-05-29
Filing date: 2010-04-28
Publication date: 2010-12-02
Also published as: JP5569126B2; JP2011080033A; KR20120036879A

Abstract

An adhesive composition comprising (A) a thermoplastic resin, (B) a heat-curable resin, (C) a latent curing agent, (D) an inorganic filler, and (E) organic microparticles.

Description

Adhesive composition, adhesive sheet, and method for manufacturing semiconductor device

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

In recent years, with the miniaturization and thinning of electronic devices, the density of circuits formed on circuit members has increased, and the distance between adjacent electrodes and the width of electrodes tend to be very narrow. Along with this, there is an increasing demand for thinner and smaller semiconductor packages. Therefore, as a semiconductor chip mounting method, instead of the conventional wire bonding method that uses metal wires to connect, protruding electrodes called bumps are formed on the chip electrodes, and the substrate electrodes and chip electrodes are directly connected via the bumps. The flip chip connection method is attracting attention.

Known flip-chip connection methods include a method using solder bumps, a method using gold bumps and a conductive adhesive, a thermocompression bonding method, and an ultrasonic method. In these systems, there is a problem that the connection reliability is lowered because thermal stress derived from the difference in thermal expansion coefficient between the chip and the substrate is concentrated on the connection portion. In order to prevent such a decrease in connection reliability, an underfill that fills the gap between the chip and the substrate is generally formed of a resin. Since thermal stress is alleviated by dispersion in the underfill, connection reliability can be improved.

As a method for forming an underfill, there is generally known a method in which a liquid resin is injected into a gap between a chip and a substrate after the chip and the substrate are connected (see Patent Document 1). In addition, underfill formation is completed in the process of connecting the chip and the substrate using a film-like resin such as an anisotropic conductive adhesive film (hereinafter referred to as ACF) or a non-conductive adhesive film (hereinafter referred to as NCF). The method of making it known is also known (refer patent document 2).

On the other hand, in recent years, through silicon vias (TSV: Through Silicon Via), which is a three-dimensional mounting technology for connecting chips with the shortest distance to enable higher functionality and higher speed operation, has been attracting attention (non-patent literature). 1). As a result, it has been demanded that the thickness of the semiconductor wafer be as thin as possible and the mechanical strength not be lowered.

In accordance with the demand for further thinning of the semiconductor device, so-called back grinding is performed to grind the back surface of the wafer in order to make the semiconductor wafer thinner, and the manufacturing process of the semiconductor device is complicated. . Therefore, as a method suitable for simplifying the process, a resin having a function of holding a semiconductor wafer during back grinding and an underfill function has been proposed (see Patent Documents 3 and 4).

Japanese Patent Laid-Open No. 2000-10082 JP 2003-142529 A JP 2001-332520 A JP 2005-028734 A

However, with the thinning of the semiconductor device, the gaps between the connection portions and the pitch between the terminals are becoming even narrower, resulting in insufficient wetting at the interface due to insufficient flow of the film-like resin at the time of connection and foaming of the film-like resin. Due to the generation of voids, etc., the filling of the film-like resin between the pitches becomes insufficient, and the connection reliability may be lowered. Therefore, the film-like adhesive used for connecting circuit members has excellent embedding properties, in which voids are unlikely to occur during crimping, and adhesive strength after curing, in order to ensure connection reliability. Is required to be high enough.

The present invention has been made in view of the above circumstances, and is sufficiently excellent in embedding property when formed into a film, and an adhesive composition that enables production of a semiconductor device excellent in connection reliability, It is an object of the present invention to provide a used adhesive sheet and a method for manufacturing a semiconductor device.

In order to solve the above problems, the present invention provides (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) an inorganic filler, and (E) an organic fine particle. An adhesive composition is provided.

According to the adhesive composition of the present invention, by including the above components (A), (B), (C), (D) and (E), it is excellent in embedding at the time of connection and generation of voids. A film adhesive that can be sufficiently reduced and has excellent connection reliability can be formed.

In the adhesive composition of the present invention, when the total content of the (A) thermoplastic resin, the (B) thermosetting resin, and the (C) latent curing agent is 100 parts by mass, D) The content of the inorganic filler is 50 to 150 parts by mass, the content of the (E) organic fine particles is 5 to 30 parts by mass, and the (D) inorganic filler and the (E) organic fine particles The total content is preferably 65 to 165 parts by mass. Such an adhesive composition can form a film-like adhesive that is more excellent in embedding property and connection reliability.

The adhesive composition of the present invention can be used for interposing between circuit members facing each other and bonding the circuit members to each other. In this case, the circuit members can be bonded with a sufficient adhesive force while suppressing generation of voids by thermocompression bonding. Thereby, the connection body excellent in connection reliability can be obtained. As the circuit member, a circuit member having a densified circuit can be used. For example, the adhesive composition of the present invention can be used to connect a circuit member having a through silicon via.

The adhesive sheet of the present invention comprises a support base material and an adhesive layer provided on the support base material and made of the adhesive composition of the present invention.

The support substrate preferably includes a plastic film and a pressure-sensitive adhesive layer provided on the plastic film, and the adhesive layer is preferably provided on the pressure-sensitive adhesive layer. Thereby, the adhesive sheet of this invention can hold | maintain a semiconductor wafer stably at the time of back grinding of a semiconductor wafer.

Further, the adhesive sheet of the present invention can be used for interposing between the circuit members facing each other and bonding the circuit members to each other. In this case, the circuit members can be bonded with a sufficient adhesive force while suppressing generation of voids by thermocompression bonding. Thereby, the connection body excellent in connection reliability can be obtained.

The present invention also provides a semiconductor wafer having a plurality of circuit electrodes on one of its main surfaces, and an adhesive layer made of the adhesive composition of the present invention is provided on the side of the semiconductor wafer on which the circuit electrodes are provided. A step of providing, a step of grinding the opposite side of the semiconductor wafer from the side on which the circuit electrodes are provided, thinning the semiconductor wafer, and dicing the thinned semiconductor wafer and the adhesive layer. Manufacturing of a semiconductor device comprising: a step of dividing into a semiconductor element with a film adhesive and a step of soldering the circuit electrode of the semiconductor element with a film adhesive to a circuit electrode of a support member for mounting a semiconductor element Provide a method.

According to the present invention, it is possible to provide an adhesive composition capable of producing a semiconductor device that is sufficiently excellent in embedding property when formed into a film and has excellent connection reliability, and an adhesive sheet using the same. Can do. Moreover, according to the method for manufacturing a semiconductor device of the present invention, a semiconductor device having excellent connection reliability can be provided.

1 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members according to the present invention. 1 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members according to the present invention. It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device concerning the present invention. It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device concerning the present invention. It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device concerning the present invention. It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device concerning the present invention. It is a schematic cross section for explaining one embodiment of a manufacturing method of a semiconductor device concerning the present invention.

Preferred embodiments of an adhesive composition, an adhesive sheet, and a method for manufacturing a semiconductor device according to the present invention will be described below.

The adhesive sheet according to the present invention can be used for connecting circuit members. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members according to the present invention. An adhesive sheet 10 for connecting circuit members shown in FIG. 1 includes a support base 3, an adhesive layer 2 provided on the support base 3 and made of the adhesive composition of the present invention, and an adhesive layer 2. And a protective film 1 to be coated.

First, the adhesive composition constituting the adhesive layer 2 according to this embodiment will be described.

The adhesive composition according to this embodiment includes (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) an inorganic filler, and (E) organic fine particles. ,including.

(A) As a thermoplastic resin (hereinafter referred to as “component (A)”), polyester resin, polyether resin, polyamide resin, polyamideimide resin, polyimide resin, polyvinyl butyral resin, polyvinyl formal resin, phenoxy resin, Examples include polyhydroxy polyether resins, acrylic resins, polystyrene resins, butadiene resins, acrylonitrile / butadiene copolymers, acrylonitrile / butadiene / styrene resins, styrene / butadiene copolymers, and acrylic acid copolymers. These can be used alone or in admixture of two or more.

(A) component can make the film forming property of an adhesive composition favorable. Film-forming property indicates mechanical properties that do not easily tear, break, or stick when a liquid adhesive composition is solidified to form a film. If the film is easy to handle in a normal state (for example, room temperature), it can be said that the film formability is good. Among the thermoplastic resins described above, it is preferable to use a polyimide resin or a phenoxy resin because of excellent heat resistance and mechanical strength.

The weight average molecular weight of the component (A) is preferably 20,000 to 800,000, more preferably 30,000 to 500,000, still more preferably 40,000 to 100,000, and 40,000 to 80,000. It is particularly preferred. When the weight average molecular weight is within this range, it becomes easy to satisfactorily balance the strength and flexibility of the adhesive layer 2 in the form of a sheet or film, and the flowability of the adhesive layer 2 becomes good. The circuit filling property (embedding property) of the wiring can be sufficiently secured. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Further, from the viewpoint of imparting adhesiveness to the adhesive layer 2 before curing while maintaining the film formability, the glass transition temperature of the component (A) is preferably 20 to 170 ° C. 120 ° C. is more preferable. When the glass transition temperature of the component (A) is less than 20 ° C., the film formability at room temperature is lowered, and the adhesive layer 2 tends to be deformed during the processing of the semiconductor wafer in the back grinding process. If it exceeds, the adhesive temperature when the adhesive layer 2 is applied to the semiconductor wafer needs to be higher than 170 ° C., so that the thermosetting reaction of the component (B) proceeds and the fluidity of the adhesive layer 2 decreases. As a result, poor connection tends to occur.

The content of the component (A) is preferably 10 to 50 parts by weight, and preferably 15 to 50 parts by weight with respect to 100 parts by weight as a total of the components (A), (B) and (C). More preferably, it is 20 to 40 parts by mass, still more preferably 25 to 35 parts by mass. (A) By making content of a component into the said range, the film formation property of an adhesive composition becomes much better, and comes to show moderate fluidity at the time of thermocompression bonding, and between a bump and a circuit electrode. The resin rejection is further improved. Specifically, when the content of the component (A) is 10 parts by mass or more, the film formability is further improved, and the occurrence of a defect in which the adhesive composition protrudes from the side of the support substrate and the protective film occurs. , More reliably prevented. Further, when the content of the component (A) is 50 parts by mass or less, it has appropriate fluidity at the time of thermocompression bonding, the exclusion property between the bump and the circuit electrode becomes good, and the occurrence of poor connection occurs. More reliably prevented.

(B) As the thermosetting resin (hereinafter referred to as “component (B)”), for example, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, diallyl phthalate resin, bismaleimide resin, triazine resin, Examples include polyurethane resins, phenol resins, cyanoacrylate resins, polyisocyanate resins, furan resins, resorcinol resins, xylene resins, benzoguanamine resins, silicone resins, siloxane-modified epoxy resins, and siloxane-modified polyamideimide resins. These can be used alone or in admixture of two or more. From the viewpoint of improving heat resistance and adhesiveness, it is preferable to contain an epoxy resin as the component (B).

The epoxy resin is not particularly limited as long as it is cured and has an adhesive action. For example, a wide range of epoxy resins described in the epoxy resin handbook (edited by Masaki Shinbo, Nikkan Kogyo Shimbun) can be used. it can. Specifically, for example, a bifunctional epoxy resin such as bisphenol A type epoxy, a novolac type epoxy resin such as a phenol novolac type epoxy resin or a cresol novolac type epoxy resin, or a trisphenolmethane type epoxy resin can be used. Moreover, what is generally known, such as a polyfunctional epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin, can be applied.

The content of the component (B) is preferably 5 to 88 parts by mass and preferably 20 to 50 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C). More preferred is 20 to 40 parts by mass. By making content of (B) component into the said range, the heat resistance of the adhesive after hardening and adhesiveness will become excellent, and high reliability will be expressed. Specifically, when the content of the component (B) is 5 parts by mass or more, the cohesive force of the cured product is improved and the connection reliability is further improved. Further, when the content of the component (B) is 88 parts by mass or less, the film-like shape is easily held in the film state before curing, and the handleability is excellent.

(C) As the latent curing agent, for example, phenol, imidazole, hydrazide, thiol, benzoxazine, boron trifluoride-amine complex, sulfonium salt, amine imide, polyamine salt, dicyandiamide and organic peroxide Mention may be made of system curing agents. From the viewpoint of extending the visible time, it is preferable to use, as the component (C), those encapsulated with a polymer substance, an inorganic substance, a metal thin film, or the like using these curing agents as a core and microencapsulated.

The microcapsule-type latent curing agent comprises the above curing agent by coating with a polymer material such as polyurethane, polystyrene, gelatin and polyisocyanate, an inorganic material such as calcium silicate or zeolite, or a metal thin film such as nickel or copper. One whose core is substantially covered is mentioned.

When the adhesive composition is applied to a series of semiconductor device manufacturing processes including application to a semiconductor wafer, protection during grinding, dicing and connection to a circuit board, exposure to a long-term ambient temperature environment, It may be affected by external factors such as heat, humidity and light. Therefore, it is preferable that the adhesive composition has excellent resistance to the influence of external factors in the above-described semiconductor device manufacturing process and can maintain sufficiently usable characteristics over a series of processes.

Since the adhesive composition according to the present embodiment is excellent in resistance to the influence of the external factors as described above, it can retain sufficiently usable characteristics over a series of steps in manufacturing a semiconductor device. And the said adhesive composition comes to be further excellent in the tolerance with respect to the influence of the above external factors by using a microcapsule-type latent hardening | curing agent as (C) component.

The average particle size of the microcapsule-type latent curing agent is preferably 10 μm or less, more preferably 5 μm or less. Such a microcapsule-type latent curing agent has a more uniform reaction start temperature, and the microcapsule-type latent curing agent The curing start temperature of the adhesive composition containing the latent curing agent is also uniform. Moreover, when average particle diameter becomes larger than 10 micrometers, the surface flatness at the time of hardening | curing an adhesive composition and shape | molding into a film form may not fully be obtained. If the surface flatness is not sufficient, there is a possibility that the gap between the pitches cannot be sufficiently sealed when used for connecting circuit members. Moreover, it is preferable that the lower limit of an average particle diameter is 1 micrometer or more. Such a microcapsule-type latent curing agent has high solvent resistance to the solvent used for the varnish during film formation, and can maintain the fluidity of the adhesive composition before heating and pressing for a long time. These microcapsule-type latent curing agents may be used alone or in combination of two or more.

The content of the component (C) in the adhesive composition according to this embodiment is preferably 2 to 45 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C). The amount is more preferably 10 to 40 parts by mass, and still more preferably 20 to 40 parts by mass. When the content of the component (C) is less than 2 parts by mass, the curing reaction tends to be difficult to proceed. When the content exceeds 45 parts by mass, the proportion of the curing agent in the total amount of the adhesive composition is excessively increased. The proportion of the thermosetting resin decreases, and the characteristics such as heat resistance and adhesiveness tend to be deteriorated.

The adhesive composition according to the present embodiment includes (D) an inorganic filler, so that the moisture absorption rate and the linear expansion coefficient of the cured adhesive layer 2 can be reduced and the elastic modulus can be increased. The connection reliability of the semiconductor device can be improved. As the component (D), an inorganic filler that does not reduce visible light transmittance can be selected in order to prevent visible light scattering in the adhesive layer 2 and improve visible light transmittance. As the component (D) capable of suppressing a decrease in visible light transmittance, an inorganic filler having a particle diameter finer than the wavelength of visible light is selected, or resin components (A), (B) and (C) It is preferable to select an inorganic filler having a refractive index close to the refractive index of a resin composition comprising the component (hereinafter sometimes referred to as “resin composition”).

The inorganic filler having a particle diameter finer than the wavelength of visible light is not particularly limited as long as it is a transparent filler, and the average particle diameter is preferably less than 0.3 μm, preferably 0.1 μm or less. It is more preferable that The refractive index of the inorganic filler is preferably 1.46 to 1.7.

As an inorganic filler having a refractive index approximate to the refractive index of the resin composition, after preparing a resin composition comprising the components (A), (B) and (C) and measuring the refractive index, approximate the refractive index. An inorganic filler having a refractive index of 5 can be selected. As the inorganic filler, it is preferable to use a fine filler from the viewpoint of filling the gap between the semiconductor chip of the adhesive layer 2 and the circuit board and suppressing the generation of voids in the connecting step. The average particle diameter of such an inorganic filler is preferably 0.01 to 5 μm, more preferably 0.1 to 2 μm, and still more preferably 0.3 to 1 μm. When the average particle size is less than 0.01 μm, the surface area of the particles increases, the viscosity of the adhesive composition increases, and it tends to be difficult to fill the inorganic filler.

The refractive index of the inorganic filler having a refractive index approximate to the refractive index of the resin composition is preferably in the range of the refractive index ± 0.06 of the resin composition. For example, when the refractive index of the resin composition is 1.60, an inorganic filler having a refractive index of 1.54 to 1.66 can be preferably used. The refractive index can be measured using an Abbe refractometer with sodium D line (589 nm) as a light source. Examples of such inorganic fillers include composite oxide fillers, composite hydroxide fillers, barium sulfate and viscosity minerals. Specifically, cordierite, falselite, mullite, barium sulfate, magnesium hydroxide, boric acid Aluminum, barium or silica titania can be used. Silica, calcium silicate, alumina, calcium carbonate and the like can also be used.

In addition, the two types of inorganic fillers described above may be used in combination, or two or more types of inorganic fillers in the same type may be used in combination. However, in order not to hinder the increase in viscosity of the adhesive composition, the addition amount of the inorganic filler having a particle diameter finer than the wavelength of visible light is composed of (A) component, (B) component and (C) component. It is preferable to make it less than 10 mass% on the basis of the total amount of the resin composition.

The component (D) preferably has a linear expansion coefficient of 7 × 10 ⁻⁶ / ° C. or less in the temperature range of 0 to 700 ° C. from the viewpoint of improving the elastic modulus of the adhesive layer 2. ^{-6 /} ° C. or less and more preferably.

Component (D) is preferably blended in an amount of 25 to 200 parts by weight, preferably 50 to 150 parts by weight, based on a total of 100 parts by weight of components (A), (B) and (C). More preferred is 75 to 125 parts by mass. If the blending amount of the component (D) is less than 25 parts by mass, the linear expansion coefficient of the adhesive layer formed from the adhesive composition is increased and the elastic modulus is decreased. It is difficult to obtain a void suppressing effect at the time of connection. On the other hand, when the blending amount of component (D) exceeds 200 parts by mass, the melt viscosity of the adhesive composition increases, and the wettability of the interface between the semiconductor chip and the adhesive layer or the interface between the circuit board and the adhesive layer. As a result of the decrease, voids remain due to peeling or insufficient embedding.

(E) Organic fine particles include, for example, acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR, SBR, silicone-modified resin and the like as components. A copolymer is mentioned. As the organic fine particles, organic fine particles having a molecular weight of 1 million or more or organic fine particles having a three-dimensional crosslinked structure are preferable. Such organic fine particles have high dispersibility in the adhesive composition. Moreover, the adhesive composition containing such organic fine particles is further excellent in adhesiveness and stress relaxation property after curing. Here, “having a three-dimensional crosslinked structure” means that the polymer chain has a three-dimensional network structure, and the organic fine particles having such a structure include, for example, a polymer having a plurality of reaction points. It can be obtained by treating with a crosslinking agent having two or more functional groups capable of binding to the reaction site. It is preferable that both organic fine particles having a molecular weight of 1 million or more and organic fine particles having a three-dimensional crosslinked structure have low solubility in a solvent. These organic fine particles having low solubility in a solvent can obtain the above-described effects more remarkably. Further, from the viewpoint of obtaining the above-described effect more remarkably, organic fine particles having a molecular weight of 1 million or more and organic fine particles having a three-dimensional cross-linked structure are (meth) acrylate alkyl-silicone copolymer, silicone- (meth). Organic fine particles made of an acrylic copolymer or a composite thereof are preferable. Further, organic fine particles such as polyamic acid particles and polyimide particles as described in JP-A-2008-150573 can also be used.

As the component (E), organic fine particles having a core-shell structure and having different compositions between the core layer and the shell layer can also be used. Specific examples of the core-shell type organic fine particles include particles obtained by grafting an acrylic resin with a silicone-acrylic rubber core, and particles obtained by grafting an acrylic resin with an acrylic copolymer as a core. Further, core-shell type silicone fine particles as described in WO2009 / 051067, (meth) acrylic acid alkyl ester-butadiene-styrene copolymer or composite as described in WO2009 / 020005, (meth) acrylic Organic fine particles such as acid alkyl ester-silicone copolymer or composite, silicone- (meth) acrylic acid copolymer or composite, core-shell structure polymer particles as described in JP-A-2002-256037, Rubber particles having a core-shell structure as described in JP-A-2004-18803 can also be used. These core-shell type organic fine particles may be used alone or in combination of two or more.

In the case where the component (E) is an organic fine particle having a molecular weight of 1 million or more or an organic fine particle having a three-dimensional cross-linked structure, the solubility in an organic solvent is low. Can be blended. Therefore, the organic fine particles are dispersed in an island shape in the adhesive layer 2 after curing, and the strength of the connection body is improved. In addition, (E) component has a function as an impact-resistant relaxation agent which has stress relaxation property.

The component (E) preferably has an average particle size of 0.1 to 2 μm. More preferably, it is 0.1 to 0.9 μm. When the average particle size of the component (E) is less than 0.1 μm, the melt viscosity of the adhesive composition increases, and when solder is used when connecting circuit members, the solder wettability tends to be hindered. The effect of reducing the viscosity is reduced, and a void suppressing effect tends to be hardly obtained at the time of connection.

(E) component, in order to impart void suppression at the time of connection and stress relaxation effect after connection to the adhesive layer 2, for a total of 100 parts by mass of (A), (B) and (C) components, The amount is preferably 5 to 30 parts by mass. When the blending amount of the component (E) is less than 5 parts by mass, the effect of suppressing voids at the time of connection tends to be difficult and the stress relaxation effect tends to be hardly exhibited, and when it exceeds 30 parts by mass, the fluidity decreases. Solder wettability decreases and causes residual voids, and the elastic modulus of the cured product tends to be too low, leading to a decrease in connection reliability.

From the viewpoints of sufficiently suppressing voids, excellent stress relaxation effect after connection, and reducing the moisture absorption rate and linear expansion coefficient to increase the elastic modulus, the components (A), (B) and (C) The content of the component (D) is 50 to 150 parts by mass, the content of the component (E) is 5 to 30 parts by mass, and the component (D) and ( The total content of component E) is preferably 65 to 165 parts by mass. The content of the component (D) is 50 to 130 parts by mass, the content of the component (E) is 7 to 20 parts by mass, and the total content of the components (D) and (E) Is more preferably 65 to 132 parts by mass, the content of component (D) is 50 to 110 parts by mass, the content of component (E) is 10 to 20 parts by mass, and (D) More preferably, the total content of the component and the component (E) is 65 to 110 parts by mass.

When the blending amount of the component (D) is less than 50 parts by mass, the bulk strength of the adhesive layer formed from the adhesive composition is low, and the connection reliability in the heat resistance test tends to decrease, and the blending of the component (D) When the amount is more than 150 parts by mass, the thixotropy of the adhesive composition becomes too high, and the peeling failure tends to increase. Moreover, since the suppression effect of a void improves further that the sum total of content of (D) component and (E) component is 65 mass parts or more, an adhesive composition is circuit member connection as it is 165 mass parts or less. It is preferable because the fluidity suitable for use is maintained, the wettability of the interface is improved, and the effect of suppressing separation failure is further improved. Moreover, when there is more sum total of content of (D) component and (E) component than 165 mass parts, there exists a tendency for connection resistance to deteriorate.

Further, the content of the component (E) is preferably 5 to 100 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the component (D), and 10 to 30 parts by mass. And more preferred. When the content of the component (E) is 5 parts by mass or more with respect to 100 parts by mass of the component (D), the deformability of the adhesive composition is improved, and the effect of suppressing peeling failure at the adherend interface is excellent. . On the other hand, if the amount is more than 100 parts by mass, the thermal expansion suppressing effect by the inorganic filler cannot be obtained, and the connection reliability is deteriorated. On the other hand, when the component (D) is excessively present, the thixotropy becomes too high, so that wetting on the adherend interface becomes insufficient and the connectivity is lowered.

In the adhesive composition according to this embodiment, various coupling agents can be added in order to modify the surface of the inorganic filler to improve the interfacial bond between different materials and increase the adhesive strength. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based coupling agents. Among them, a silane-based coupling agent is preferable because it is highly effective.

Examples of silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldisilane. Examples include ethoxysilane, 3-ureidopropyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. These can be used alone or in combination of two or more.

In the adhesive composition according to the present embodiment, an ion scavenger may be added in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. There are no particular restrictions on such ion scavengers, for example, triazine thiol compounds, bisphenol reducing agents, etc., compounds known as copper damage inhibitors to prevent ionization and dissolution, zirconium-based, antimony, etc. Examples include inorganic ion adsorbents such as bismuth-based magnesium aluminum compounds.

The adhesive composition suppresses the temperature change after the semiconductor chip and the circuit board are connected, expansion due to heat absorption, etc., and achieves high connection reliability. preferably the linear expansion coefficient at ° C. is 60 × ^{10 -6} / ℃ or less, more preferably 55 × ^{10 -6} / ℃ or less, and more preferably 50 × ^{10 -6} / ℃ or less. When the linear expansion coefficient of the adhesive layer 2 after curing exceeds 60 × 10 ⁻⁶ / ° C., the electric current between the connection terminals of the semiconductor chip and the wiring of the circuit board is caused by the temperature change after mounting and the expansion due to heat absorption. Connection may not be maintained. Moreover, although the electroconductive particle can be made to contain in the adhesive composition of this invention and it can be set as an anisotropic conductive adhesive film (ACF), it is set as a nonelectroconductive adhesive film (NCF) without containing electroconductive particle. Is preferred.

The adhesive layer 2 formed from the adhesive composition according to the present embodiment has a reaction rate of 60% or more measured by differential scanning calorimetry (hereinafter referred to as “DSC”) after heating at 250 ° C. for 10 seconds. It is preferable that it is 70% or more. Moreover, it is preferable that the reaction rate of the adhesive layer 2 measured by DSC is less than 10% after storing the circuit composition connecting composition sheet for 14 days at room temperature. Thereby, by using the adhesive composition according to the present embodiment, it is possible to obtain a film adhesive that is sufficiently excellent in reactivity at the time of connection and excellent in storage stability.

The adhesive layer 2 preferably has an uncured visible light transmittance of 5% or more, more preferably a visible light transmittance of 8% or more, and a visible light transmittance of 10% or more. Is more preferable. If the visible light transmittance is less than 5%, the recognition mark cannot be identified by the flip chip bonder, and the alignment work tends to be impossible. On the other hand, there is no particular limitation on the upper limit of the visible light transmittance.

Visible light transmittance can be measured using a Hitachi U-3310 spectrophotometer. For example, after a baseline correction measurement was performed using a Teijin DuPont PET film (Purex, 555 nm transmittance: 86.03%) having a thickness of 50 μm as a reference material, an adhesive layer 2 having a thickness of 25 μm was formed on the PET film. Thereafter, the transmittance in the visible light region of 400 to 800 nm is measured. Since the wavelength relative intensity of the halogen light source and light guide used in the flip chip bonder is the strongest at 550 to 600 nm, in this specification, the transmittance of the adhesive layer 2 is compared using the transmittance at 555 nm. Yes.

The adhesive layer 2 is obtained by dissolving or dispersing the above-described adhesive composition according to the present invention in a solvent to form a varnish, and applying the varnish on a protective film (hereinafter, sometimes referred to as “first film”) 1. It can be formed by removing the solvent by heating. Thereafter, the supporting substrate 3 is laminated on the adhesive layer 2 at room temperature to 60 ° C. to obtain the adhesive sheet for connecting circuit members of the present invention. Alternatively, the adhesive layer 2 can be formed by applying the varnish on the support substrate 3 and removing the solvent by heating.

The solvent to be used is not particularly limited, but it is preferable to determine the volatility when forming the adhesive layer in consideration of the boiling point. Specifically, for example, a solvent having a relatively low boiling point such as methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, and xylene forms an adhesive layer. It is preferable in that the curing of the adhesive layer is difficult to proceed. These solvents can be used alone or in combination of two or more.

As the protective film 1, for example, a plastic film such as polyethylene terephthalate, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, or the like can be used. From the viewpoint of peelability, it is also preferable to use a film having a low surface energy made of a fluororesin such as a polytetrafluoroethylene film as the protective film 1.

In order to improve the peelability of the protective film 1, the surface of the protective film 1 on which the adhesive layer 2 is formed is treated with a release agent such as a silicone-based release agent, a fluorine-based release agent, or a long-chain alkyl acrylate-based release agent. It is preferable. As commercially available products, for example, “A-63” (mold release treatment: modified silicone type) and “A-31” (mold release treatment: Pt type silicone) manufactured by Teijin DuPont Films Ltd. are available. Can do.

The protective film 1 preferably has a thickness of 10 to 100 μm, more preferably 10 to 75 μm, and particularly preferably 25 to 50 μm. If the thickness is less than 10 μm, the protective film tends to be broken during coating, and if it exceeds 100 μm, the cost tends to be inferior.

As a method of applying the varnish on the protective film 1 (or the supporting substrate 3), generally known methods such as knife coating, roll coating, spray coating, gravure coating, bar coating, curtain coating, and the like are used. Is mentioned.

The thickness of the adhesive layer 2 is not particularly limited, but is preferably 5 to 200 μm, more preferably 7 to 150 μm, and still more preferably 10 to 100 μm. If the thickness is less than 5 μm, it will be difficult to ensure sufficient adhesion, and the convex electrodes of the circuit board will not be filled. If it is thicker than 200 μm, it will not be economical, and there will be a demand for miniaturization of the semiconductor device. It becomes difficult to respond to.

Examples of the supporting substrate 3 include plastic films such as a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polymethylpentene film, a polyvinyl acetate film, a polyvinyl chloride film, and a polyimide film. Further, the support base 3 may be a mixture of two or more selected from the above materials, or a multilayer of the above film.

The thickness of the support substrate 3 is not particularly limited, but is preferably 5 to 250 μm. If the thickness is less than 5 μm, the support substrate may be cut during grinding (back grinding) of the semiconductor wafer, and if it is more than 250 μm, it is not economical, which is not preferable.

The support substrate 3 preferably has high light transmittance, and specifically, the minimum light transmittance in the wavelength region of 500 to 800 nm is preferably 10% or more.

In addition, as the support base 3, one obtained by laminating an adhesive layer on the plastic film (hereinafter sometimes referred to as “second film”) can be used.

FIG. 2 is a schematic cross-sectional view showing a preferred embodiment of the adhesive sheet for connecting circuit members according to the present invention. The adhesive sheet 11 for connecting a circuit member shown in FIG. 2 is provided on a support substrate 3 having a plastic film 3b and an adhesive layer 3a provided on the plastic film 3b, and on the adhesive layer 3a. An adhesive layer 2 made of the adhesive composition of the present invention and a protective film 1 covering the adhesive layer 2 are provided.

In order to improve the adhesion between the second film 3b and the pressure-sensitive adhesive layer 3a, the surface of the second film is subjected to chemical treatment such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc. Or you may give a physical process.

The pressure-sensitive adhesive layer 3a has an adhesive force at room temperature, preferably has a necessary adhesion to an adherend, and is cured by high energy rays such as radiation or heat (that is, reduces the adhesive force). The thing provided with is preferable. The pressure-sensitive adhesive layer 3a can be formed using, for example, acrylic resin, various synthetic rubbers, natural rubber, or polyimide resin. The thickness of the pressure-sensitive adhesive layer 3a is usually about 5 to 25 μm.

The circuit member connecting

adhesive sheets

10 and 11 described above are interposed between a circuit member and a semiconductor element having circuit electrodes to be opposed to each other or between semiconductor elements, and the circuit member and the semiconductor element or semiconductor element. It can be used to bond them together. In this case, by thermocompression bonding the circuit member and the semiconductor element or the semiconductor elements, it is possible to bond with sufficient adhesive force while suppressing the generation of voids, and it is possible to bond the circuit electrodes satisfactorily. Thereby, the connection body excellent in connection reliability can be obtained. Moreover, the

adhesive sheet

10 and 11 for circuit member connection can also be used as an adhesive sheet in the lamination | stacking technique using a silicon penetration electrode.

Next, a method for manufacturing a semiconductor device using the adhesive sheet 10 for connecting circuit members will be described.

3 to 7 are schematic cross-sectional views for explaining a preferred embodiment of a method for manufacturing a semiconductor device according to the present invention. The manufacturing method of the semiconductor device according to this embodiment is as follows:
(A) A semiconductor wafer having a plurality of circuit electrodes on one main surface is prepared, and an adhesive layer made of the adhesive composition according to the present embodiment is provided on the side of the semiconductor wafer on which the circuit electrodes are provided. Process,
(B) a step of grinding the opposite side of the semiconductor wafer to the side where the circuit electrodes are provided to thin the semiconductor wafer;
(C) a step of dicing the thinned semiconductor wafer and the adhesive layer into individual semiconductor elements with a film adhesive;
(D) bonding the circuit electrode of the semiconductor element with a film adhesive to the circuit electrode of the semiconductor element mounting support member;
Is provided.

In the step (a) in the present embodiment, the adhesive layer is provided by sticking the adhesive layer 2 of the adhesive sheet 10 to the side of the semiconductor wafer where the circuit electrodes are provided. In the step (d) in the present embodiment, the solder bonding is performed by heating, and the film adhesive interposed between the semiconductor element and the semiconductor element mounting support member is also cured. Hereinafter, each process will be described with reference to the drawings.

(A) Process First, the adhesive sheet 10 is arrange | positioned to a predetermined apparatus, and the protective film 1 is peeled off. Subsequently, a semiconductor wafer A having a plurality of circuit electrodes 20 on one of the main surfaces is prepared, the adhesive layer 2 is pasted on the side of the semiconductor wafer A on which the circuit electrodes are provided, and the support substrate 3 / adhesive layer 2 / A laminated body in which the semiconductor wafers A are laminated is obtained (see FIG. 3). The circuit electrode 20 may be provided with bumps coated with solder for soldering. Note that solder can also be provided on the circuit electrode of the conductor element mounting support member.

Examples of the circuit electrode 20 include gold bumps, copper bumps, and nickel bumps formed using plating, vapor deposition, or metal wires. Further, a conductive resin bump formed of a resin or a resin core bump having a resin as a core and a metal deposited on the surface thereof may be used. The protruding circuit electrode does not need to be composed of a single metal, and may contain a plurality of metal components such as gold, silver, copper, nickel, indium, palladium, tin, and bismuth. May be laminated.

In the above step (a), a commercially available film sticking apparatus or laminator can be used as a method for obtaining a laminate in which the support substrate 3 / adhesive layer 2 / semiconductor wafer A is laminated. In order to attach the adhesive layer 2 to the semiconductor wafer A without involving any voids, it is preferable that the attaching device is provided with a heating mechanism and a pressurizing mechanism, and more preferably a vacuum suction mechanism. Further, the shape of the adhesive sheet 10 may be a shape that can be worked by the sticking device, may be a roll shape or a sheet shape, and may be processed according to the outer shape of the semiconductor wafer A.

The lamination of the semiconductor wafer A and the adhesive layer 2 is preferably performed at a temperature at which the adhesive layer 2 is softened. The lamination temperature is preferably 40 to 80 ° C., more preferably 50 to 80 ° C., and 60 to 80 ° C. Further preferred. When laminating at a temperature lower than the temperature at which the adhesive layer 2 is softened, insufficient embedding of the semiconductor wafer A around the protruding circuit electrode 20 occurs, a void is involved, and the adhesive layer is peeled off during dicing. Deformation of the adhesive layer at the time of pickup, recognition mark identification failure at the time of alignment, and further reduction in connection reliability due to voids are likely to occur.

(B) Process Next, as shown in FIG. 4, the side opposite to the side where the circuit electrode 20 of the semiconductor wafer A is provided is ground by the grinder 4 to thin the semiconductor wafer. The thickness of the semiconductor wafer can be, for example, 10 to 300 μm. From the viewpoint of miniaturization and thinning of the semiconductor device, the thickness of the semiconductor wafer is preferably 20 to 100 μm.

In the step (b), the semiconductor wafer A can be ground using a general back grind (B / G) apparatus. In order to uniformly grind the semiconductor wafer A without thickness unevenness in the B / G step, it is preferable that the adhesive layer 2 is evenly attached in the step (a) without involving voids.

(C) Process Next, as FIG. 5A shows, the dicing tape 5 is affixed on the semiconductor wafer A of a laminated body, this is arrange | positioned to a predetermined apparatus, and the support base material 3 is peeled off. At this time, when the support substrate 3 includes the pressure-sensitive adhesive layer 3a and the pressure-sensitive adhesive layer 3a is radiation curable, the pressure-sensitive adhesive layer 3a is cured by irradiating radiation from the support substrate 3 side. The adhesive force between the adhesive layer 2 and the support base 3 can be reduced. Here, examples of the radiation used include ultraviolet rays, electron beams, and infrared rays. Thereby, the support base material 3 can be easily peeled off. After the support substrate 3 is peeled off, the semiconductor wafer A and the adhesive layer 2 are diced by a dicing saw 6 as shown in FIG. Thus, the semiconductor wafer A is divided into a plurality of semiconductor elements A ′, and the adhesive layer 2 is divided into a plurality of film adhesives 2a.

Next, as shown in FIG. 6, the dicing tape 5 was expanded (expanded), and the semiconductor elements A ′ obtained by the dicing were separated from each other and pushed up by the needle from the dicing tape 5 side. The semiconductor element 12 with a film adhesive comprising the semiconductor element A ′ and the film adhesive 2 a is sucked and picked up by the suction collet 7. The film-like adhesive-attached semiconductor element 12 may be collected by tray packing, or may be directly mounted on a circuit board with a flip chip bonder.

(C) In the step (c), the work of attaching the dicing tape 5 to the ground semiconductor wafer A can be performed in the same step as the fixing to the dicing frame using a general wafer mounter. A commercially available dicing tape can be applied to the dicing tape 5, which may be a UV curable type or a pressure sensitive type.

(D) Step Next, as shown in FIG. 7, the circuit electrode 20 of the semiconductor element A ′ to which the film adhesive 2 a is attached and the circuit electrode 22 of the semiconductor element mounting support member 8 are aligned, The semiconductor element with film adhesive 12 and the semiconductor element mounting support member 8 are thermocompression bonded. By this thermocompression bonding, the circuit electrode 20 and the circuit electrode 22 are joined and electrically and mechanically connected, and the film adhesive 2a is cured between the semiconductor element A ′ and the semiconductor element mounting support member 8. Things are formed.

The temperature during thermocompression bonding is preferably 200 ° C. or higher, more preferably 220 to 260 ° C. from the viewpoint of solder bonding. The thermocompression bonding time can be 1 to 20 seconds. The pressure for thermocompression bonding can be 0.1 to 5 MPa.

In mounting on a circuit board using a flip chip bonder, the alignment mark formed on the circuit surface of the semiconductor chip is confirmed through the adhesive layer 2a formed on the circuit surface of the semiconductor chip, and mounted on the circuit board. The position can be confirmed and implemented.

The semiconductor device 30 is obtained through the above steps. The film adhesive comprising the adhesive composition according to this embodiment is excellent in embedding property and adhesive strength after curing. Therefore, in the semiconductor device 30, the generation of voids is sufficiently suppressed, the circuit electrodes are satisfactorily bonded, and the semiconductor element A ′ and the semiconductor element mounting support member are bonded with sufficient adhesive strength. And can be excellent in connection reliability.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, although the above embodiment has been described as an adhesive sheet for connecting circuit members, the adhesive sheet of the present invention may be an underfill forming adhesive sheet.

As described in the above embodiment as an adhesive sheet for connecting circuit members, the adhesive sheet of the present invention has excellent embeddability in which voids hardly occur during pressure bonding. Therefore, for example, when the adhesive sheet of the present invention is used in the connection between the substrate and the chip, an underfill that sufficiently fills the gap between the chip and the substrate is formed. According to such an underfill, the thermal stress derived from the difference in thermal expansion coefficient between the chip and the substrate is dispersed, so that it is possible to prevent a decrease in connection reliability due to the thermal stress. As an adhesive sheet for underfill formation of this invention, the form similar to suitable embodiment of the above-mentioned adhesive sheet for circuit member connection is employable.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

(Preparation of support substrate)
First, an acrylic copolymer was synthesized by a solution polymerization method using 2-ethylhexyl acrylate and methyl methacrylate as main monomers and hydroxyethyl acrylate and acrylic acid as functional group monomers. The resulting acrylic copolymer had a weight average molecular weight of 400,000 and a glass transition point of −38 ° C. A pressure-sensitive adhesive composition solution was prepared by blending 10 parts by mass of a polyfunctional isocyanate cross-linking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Industry Co., Ltd.) with respect to 100 parts by mass of this acrylic copolymer.

The obtained pressure-sensitive adhesive composition solution was applied onto a polyolefin film (thickness: 100 μm) so that the thickness of the pressure-sensitive adhesive layer when dried was 10 μm and dried. Furthermore, a biaxially stretched polyester film (Teijin DuPont, trade name: A3170, thickness: 25 μm) surface-treated with a silicone release agent was laminated on the pressure-sensitive adhesive layer surface. The laminate with the pressure-sensitive adhesive layer was allowed to stand at room temperature for 1 week and sufficiently aged, and then the polyolefin film was used as a support substrate.

Example 1
<Preparation of adhesive composition>
“ZX1356-2” (trade name, phenoxy resin manufactured by Toto Kasei Co., Ltd.) 25 parts by mass, “1032H60” (trade name, epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) 25 parts by mass, “Epicoat 828” (Japan Epoxy Resin Co., Ltd.) Product name, liquid epoxy resin) 15 parts by mass and “HX3941HP” (Asahi Kasei Electronics Co., Ltd., product name, microcapsule type latent curing agent) 35 parts by mass were dissolved in a mixed solvent of toluene and ethyl acetate. To this solution, 10 parts by weight of “KW-4426” (trade name, core-shell type organic fine particles manufactured by Mitsubishi Rayon Co., Ltd.), 5 μm classification treatment, average particle size of 1 μm cordierite particles (2MgO · 2Al ₂ O _3. 5 SiO ₂ , specific gravity 2.4, linear expansion coefficient: 1.5 × 10 ⁻⁶ / ° C., refractive index: 1.57) and 100 parts by mass were dispersed to obtain an adhesive varnish.

<Preparation of adhesive sheet for connecting circuit members>
The obtained adhesive varnish was applied onto a polyethylene terephthalate (PET) film (manufactured by Teijin DuPont Films, trade name “AH-3”, thickness: 50 μm) using a roll coater, and 10% in an oven at 70 ° C. It was dried for minutes to form an adhesive layer having a thickness of 25 μm. Next, the adhesive layer and the pressure-sensitive adhesive layer surface of the support substrate were bonded together at room temperature to obtain an adhesive sheet for connecting circuit members.

(Example 2)
An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1 except that the amount of “KW-4426” in adjusting the adhesive varnish was 20 parts by mass and the amount of cordierite particles was 50 parts by mass. It was.

(Example 3)
An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1 except that the amount of “KW-4426” in adjusting the adhesive varnish was 7 parts by mass and the amount of cordierite particles was 125 parts by mass. It was.

Example 4
Instead of “KW-4426” in adjusting the adhesive varnish, “EXL-2655” (trade name, core-shell type organic fine particles manufactured by Rohm and Haas Japan Co., Ltd.) 30 parts by mass is replaced by “SE2050” instead of cordierite particles. An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1 except that 50 parts by mass (trade name manufactured by Admatechs Co., Ltd., silica filler having an average particle size of 0.5 μm) were blended.

(Example 5)
Except for blending 15 parts by mass of “EXL-2655” instead of “KW-4426” and 50 parts by mass of “SE2050” instead of cordierite particles in the adjustment of the adhesive varnish, the same procedure as in Example 1 was performed. Then, an adhesive sheet for connecting circuit members was obtained.

(Example 6)
Except for blending 15 parts by mass of “EXL-2655” instead of “KW-4426” and 150 parts by mass of “SE2050” instead of cordierite particles in the adjustment of the adhesive varnish, the same procedure as in Example 1 was performed. Then, an adhesive sheet for connecting circuit members was obtained.

(Comparative Example 1)
An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1 except that “KW-4426” in adjusting the adhesive varnish was not blended.

(Comparative Example 2)
An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 2 except that the cordierite particles in the adjustment of the adhesive varnish were not blended.

(Comparative Example 3)
Adhesive sheet for connecting circuit members in the same manner as in Example 1, except that cordierite particles in the adjustment of the adhesive varnish were not blended and 35 parts by mass of “EXL-2655” was blended in place of “KW-4426” Got.

(Comparative Example 4)
An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1 except that cordierite particles and “KW-4426” were not blended in the adjustment of the adhesive varnish.

[Evaluation of adhesive layer]
(Measurement of linear expansion coefficient)
The adhesive sheets for connecting circuit members obtained in the examples and comparative examples were left in an oven set at 180 ° C. for 3 hours to perform heat curing treatment. The adhesive layer after heat curing was peeled off from the support substrate to prepare a test piece having a size of 30 mm × 2 mm. Using “TMA / SS6100” (trade name) manufactured by Seiko Instruments Inc., the above test piece is mounted in the apparatus so that the distance between chucks is 20 mm, measurement temperature range: 20 to 300 ° C., temperature increase rate: 5 ° C./min, load Conditions: Thermomechanical analysis was performed in the tensile test mode under the condition that the pressure was 0.5 MPa with respect to the cross-sectional area of the test piece, and the linear expansion coefficient was measured. After the measurement, the linear expansion difference between 100 ° C. and 40 ° C. was obtained, and the value divided by the temperature difference was calculated, and this was used as the average linear expansion coefficient for comparison.

(Reaction rate measurement)
2-10 mg of the adhesive layer in the adhesive sheet for connecting circuit members obtained in Examples and Comparative Examples was weighed into an aluminum measuring container, and DSC (Differential Scanning Calorimeter) “Pyris1” (trade name) manufactured by PerkinElmer Co., Ltd. was used. The heating value was raised to 30 to 300 ° C. at a heating rate of 20 ° C./min, and the calorific value was measured. Next, the temperature was confirmed with a thermocouple that sandwiched the heating head of the thermocompression bonding apparatus, and the temperature reached 250 ° C. after 10 seconds. With this heating head setting, the adhesive sheet for connecting the circuit members was sandwiched between the separators and heated for 20 seconds to obtain an adhesive layer that had been subjected to the same heat treatment as in thermocompression bonding. The heat generation amount of the adhesive layer after the heat treatment was measured in the same manner, and this was used as the heat generation amount after the heating. Further, the calorific value was similarly measured for the adhesive layer after the adhesive sheet for circuit member connection was stored at room temperature (25 ° C.) for 14 days, and this was defined as the calorific value after storage. The reaction rate (%) was calculated from the obtained calorific value by the following formula.
Reaction rate (%) = (initial calorific value−calorific value after heating or calorific value after storage) / (initial calorific value) × 100

<Fabrication and evaluation of semiconductor devices>
Using the adhesive sheet for connecting circuit members obtained above, a semiconductor device was prepared and evaluated according to the following procedure. The results are shown in Tables 1 and 2.

(Attaching to semiconductor wafer)
A semiconductor wafer (6 inch diameter, thickness 725 μm) on which gold-plated bumps were formed was placed on the suction stay heated to 80 ° C. of a die attach film mounter manufactured by JCMM with the bump side facing up. The adhesive sheet for connecting circuit members is cut to 200 mm × 200 mm and the adhesive layer excluding the first film as the protective film is directed to the bump side of the semiconductor wafer, and die attach from the end of the semiconductor wafer so as not to entrain air. The laminate was pressed with the mounting roller of the mounter. After lamination, the protruding portion of the adhesive was cut along the outer shape of the wafer.

(Back grinding of the backside of the semiconductor wafer and peeling of the support substrate)
After the back surface of the semiconductor wafer is back-ground to a thickness of 150 μm with the back grinder manufactured by DISCO Corporation, the laminated body of the circuit sheet connecting adhesive sheet and the semiconductor wafer (thickness: 625 μm), and then back-ground semiconductor The wafer was placed on the suction stage of a die attach film mounter manufactured by JCM Co., Ltd., and ADEKA dicing tape “AD80H” was attached at the same time as the dicing frame at room temperature. Next, a back grind tape peeling tape made by Nitto Denko was pasted on the supporting substrate, and only the supporting substrate was peeled off by peeling off 180 degrees.

(Dicing)
The semiconductor wafer with the adhesive layer fixed to the above-mentioned dicing frame was diced to 10 mm × 10 mm with a disco-made fully automatic dicing saw “DFD6361”. After dicing, washing, removing water, and UV irradiation from the dicing tape side, the separated semiconductor chip with adhesive was picked up.

(Crimping)
After aligning the semiconductor chip with adhesive on a glass epoxy substrate having a circuit in which solder containing SnAgCu as a constituent component is formed at a position facing the bump, using a flip chip bonder “FCB3” manufactured by Matsushita Electric Industrial Co., Ltd., 250 A semiconductor device was obtained by thermocompression bonding at 0 ° C. and 0.5 MPa for 10 seconds.

The embedding property and connection resistance of the film adhesive in the semiconductor device manufactured as described above were evaluated. Next, the produced semiconductor device was left to stand in a constant temperature and humidity chamber of 85 ° C. and 60% RH for 168 hours to absorb moisture, and exposed to a reflow furnace set at 260 ° C. three times. After the exposure, the connection resistance and the interface state of the connection part were confirmed.

<Connection resistance>
About the produced semiconductor device, the connection resistance after pressure bonding and the connection resistance after reflow were measured using a digital multimeter (manufactured by Advantest Co., Ltd., product name) and evaluated based on the following criteria. The results are shown in Tables 1 and 2.
a: Connection resistance at all terminal connections of the mounting TEG applied to the test is obtained.
b: A disconnection defective terminal exists.

<Embedment after crimping>
The adhesion state of the adhesive layer was observed with an ultrasonic flaw detector (SAT) manufactured by Hitachi Construction Machinery and evaluated based on the following criteria. The results are shown in Tables 1 and 2.
a: Peeling and voids are not observed.
b: Peeling and voids are observed.

<Connectivity after reflow>
The connection state after reflow of the adhesive layer was observed with an ultrasonic flaw detector (SAT) manufactured by Hitachi Construction Machinery, and evaluated based on the following criteria. The results are shown in Tables 1 and 2.
a: No peeling is observed.
b: Peeling is observed.

As shown in Tables 1 and 2, when the adhesive sheets for connecting circuit members obtained in Examples 1 to 6 were used, the connection resistance was excellent, no void was generated, and good connectivity was achieved after reflow. Indicated. On the other hand, when the adhesive sheets for connecting circuit members obtained in Comparative Examples 1 to 4 were used, voids were generated and peeled off after reflowing, confirming poor connection reliability.

DESCRIPTION OF SYMBOLS 1 ... Protective film, 2 ... Adhesive layer, 3 ... Support base material, 3a ... Adhesive layer, 3b ... Plastic film, 4 ... Grinder, 5 ... Dicing tape, 6 ... Dicing saw, 7 ... Suction collet, 8 ... Semiconductor Support member for mounting elements, 10 ... adhesive sheet for connecting circuit members, 11 ... adhesive sheet for connecting circuit members, 12 ... semiconductor element with film adhesive, 20 ... circuit electrode, 30 ... semiconductor device, A ... semiconductor wafer .

Claims

(A) a thermoplastic resin;
(B) a thermosetting resin;
(C) a latent curing agent;
(D) an inorganic filler;
(E) organic fine particles;
An adhesive composition comprising:
With respect to 100 parts by mass of the total content of the (A) thermoplastic resin, the (B) thermosetting resin, and the (C) latent curing agent,
The content of the (D) inorganic filler is 50 to 150 parts by mass,
(E) the content of the organic fine particles is 5 to 30 parts by mass, and
The adhesive composition according to claim 1, wherein the total content of the (D) inorganic filler and the (E) organic fine particles is 65 to 165 parts by mass.
The adhesive composition according to claim 1 or 2, wherein the adhesive composition is used for adhering the circuit members by interposing them between the circuit members facing each other.
An adhesive sheet comprising: a support base material; and an adhesive layer provided on the support base material and made of the adhesive composition according to any one of claims 1 to 3.
The adhesive sheet according to claim 4, wherein the supporting base material includes a plastic film and a pressure-sensitive adhesive layer provided on the plastic film, and the adhesive layer is provided on the pressure-sensitive adhesive layer.
The adhesive sheet according to claim 4 or 5, which is used for adhering the circuit members by interposing between the circuit members facing each other.
A semiconductor wafer having a plurality of circuit electrodes on one of the main surfaces is prepared, and the adhesive composition according to any one of claims 1 to 3 is provided on the side of the semiconductor wafer on which the circuit electrodes are provided. Providing an adhesive layer comprising:
Grinding the opposite side of the semiconductor wafer from the side where the circuit electrodes are provided to thin the semiconductor wafer;
Dicing the thinned semiconductor wafer and the adhesive layer into individual semiconductor elements with a film adhesive; and
Bonding the circuit electrode of the semiconductor element with a film adhesive to the circuit electrode of the semiconductor element mounting support member;
A method for manufacturing a semiconductor device.