TWI425066B - Preparation method of adhesive composition, circuit board for connecting circuit member, and manufacturing method of semiconductor device - Google Patents

Description

Substrate composition, adhesive sheet for connecting circuit member, and method for manufacturing semiconductor device

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

In recent years, with the miniaturization and thinning of electronic devices, the density of circuits formed in circuit members has progressed, and the interval between adjacent electrodes or the width of electrodes has become extremely narrow. Along with this, it is also highly demanded to be thinner or smaller in size in accordance with the semiconductor package. Therefore, as a mounting method of the semiconductor wafer, instead of using a conventional wire-bonding method using a metal wire connection, a bump electrode called a bump is formed on the wafer electrode, and the substrate electrode and the wafer electrode are directly transmitted through the bump. The connected flip chip connection method has attracted attention.

As a flip chip connection method, a method of using a solder bump, a method of using a gold bump and a conductive adhesive, a hot press method, an ultrasonic method, and the like are known. In these methods, the thermal stress caused by the difference in thermal expansion coefficient between the wafer and the substrate is concentrated on the connection portion, which causes a problem of reduced connection reliability. In order to prevent such a decrease in reliability, a resin is generally used to form an underfill filled in a gap between the wafer and the substrate. Since the thermal stress is alleviated by the dispersion to the bottom filling, the connection reliability can be improved.

In the method of forming the underfill, a method is generally known in which a liquid resin is injected into a gap between a wafer and a substrate after the wafer is connected to the substrate (see Patent Document 1). Also, a method is known which is used In the step of connecting the wafer and the substrate with a film-like resin such as an anisotropic conductive film (hereinafter referred to as ACF) or a non-conductive adhesive film (hereinafter referred to as NCF), the underfill is also formed (see Patent Document 2). .

On the other hand, in recent years, a TSV (Through Silicon Via) which is a three-dimensional mounting technique for connecting the wafers at the shortest distance as a further high-performance and high-speed actor has been attracting attention (see Non-Patent Document 1). As a result, the thickness of the semiconductor wafer is required to be as thin as possible without deteriorating the mechanical strength.

Further, in order to further reduce the thickness of the semiconductor device, in order to make the semiconductor wafer thinner, the so-called back grinding of the wafer back surface is performed, and the manufacturing steps of the semiconductor device are complicated. Therefore, there has been proposed a method for simplifying the steps as a method for maintaining the function of the semiconductor wafer and the function of the underfill at the time of back surface polishing (see Patent Documents 3 and 4).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2000-100862

[Patent Document 2] JP-A-2003-142529

[Patent Document 3] JP-A-2001-332520

[Patent Document 4] JP-A-2005-028734

[Non-patent literature]

[Non-Patent Document 1] OKI Technology October 2007 / No. 211 Vol.74 No.3

However, as the semiconductor device is thinned, the gap between the terminals or the distance between the terminals becomes narrower. Therefore, the insufficient wettability of the interface due to insufficient flow of the film-like resin at the time of connection or voiding due to foaming of the film-like resin causes insufficient filling of the film-like resin between the pitches, and the connection reliability is lowered. . Therefore, from the viewpoint of ensuring the connection reliability, the film-like adhesive used for the connection of the circuit members needs to have excellent embedding property in which voids are hard to be formed at the time of pressing, or a sufficiently high adhesive force after curing.

Further, a solder bump is formed on the electrode portion of the semiconductor wafer, and a face down bonding method in which the semiconductor wafer is directly connected to the circuit substrate by solder bonding is required to be removed in order to obtain a good electrical joint. An oxide film formed on the surface of the solder and the metal surface of the connection terminal portion. However, when the past adhesive is soldered for a short time, the flux activity of the oxide film for removing the solder surface and the metal surface of the connection terminal portion cannot be obtained, and the solder wettability is insufficient to cause the connection. The situation of reduced reliability.

The present invention has been made in view of the above problems, and an object of the invention is to provide an adhesive composition, an adhesive sheet for connecting a circuit member using the same, and a method for producing a semiconductor device, which are buried in a film form. The semiconductor device is excellent in connection quality and can be fabricated with excellent connection reliability.

In order to solve the above problems, the present invention provides an adhesive composition comprising (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) an inorganic filler, and (E) an organic fine particle. And (F) a powder compound having a solid maximum particle diameter of 25 μm or less at room temperature, and the component (F) is at least one compound selected from the group consisting of a compound having a carboxyl group, a compound having a methylol group, and an anthracene compound.

According to the adhesive composition of the present invention, by containing the above components (A), (B), (C), (D) and (E), a film-like adhesive can be formed, which is excellent in embedding property when joined. The hole can be sufficiently reduced, and by further blending the component (F), the oxide film formed on the surface of the solder and the metal surface of the connection terminal portion can be removed, and the solder wettability can be improved.

Further, in the adhesive composition of the present invention, the component (B) preferably contains an epoxy resin from the viewpoint of improving heat resistance and adhesion.

The adhesive composition of the present invention can be used between circuit components to cause circuit components to follow each other, the circuit components having opposing and solder-bonded circuit electrodes. In this case, by heating the circuit members to each other, it is possible to suppress the occurrence of voids and to sufficiently follow the force, and the circuit electrodes can be welded to each other favorably. Therefore, a connector excellent in connection reliability can be obtained.

The adhesive sheet for connecting circuit members of the present invention is characterized in that it has a support base material and an adhesive layer which is provided on the base material and is composed of the above-described adhesive composition of the present invention.

Preferably, the support substrate is provided with a plastic film and is disposed on the plastic The adhesive layer on the film, and the adhesive layer is disposed on the adhesive layer. According to this, when the adhesive sheet for connecting the circuit member of the present invention is polished on the back surface of the semiconductor wafer, the semiconductor wafer can be stably held.

Further, the circuit member connecting adhesive sheet of the present invention can be used between circuit members to cause circuit members to be connected to each other, the circuit members having opposite and solder-bonded circuit electrodes. In this case, by heating the circuit members to each other, it is possible to suppress the occurrence of voids and to sufficiently follow the force, and the circuit electrodes can be welded to each other favorably. According to this, a connector excellent in connection reliability can be obtained.

The present invention further provides a method of fabricating a semiconductor device, the method comprising the steps of: preparing a semiconductor wafer having a plurality of circuit electrodes on one side of a main surface, and providing the present invention on a side of the semiconductor wafer provided with circuit electrodes a step of forming an adhesive layer formed by the composition of the adhesive; a step of thinning the semiconductor wafer by grinding the opposite side of the semiconductor wafer on the side of the circuit electrode; dicing the thinned semiconductor wafer and And a step of singulating the semiconductor layer of the semiconductor element with the film-like adhesive; and soldering and bonding the circuit electrode of the semiconductor element with the film-like adhesive; The steps of the circuit electrode.

According to the present invention, it is possible to provide an adhesive composition and an adhesive sheet for connecting a circuit member using the same, which is excellent in embedding property in a film form, and can produce a semiconductor excellent in connection reliability. Device. Moreover, according to the method of manufacturing a semiconductor device of the present invention, it is possible to provide a semiconductor device having excellent connection reliability.

Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members of the present invention. The circuit member connection adhesive sheet 10 shown in FIG. 1 includes a support substrate 3, an adhesive layer 2 provided on the support substrate 3 and composed of the adhesive composition of the present invention, and a cover adhesive layer 2 Protective film 1.

First, the adhesive composition of the present invention which constitutes the adhesive layer 2 will be described.

The adhesive composition of the present invention comprises (A) a thermoplastic resin, (B) a thermosetting resin, (C) a latent curing agent, (D) an inorganic filler, (E) an organic fine particle, and (F) at room temperature It is a powder compound having a maximum particle diameter of 25 μm or less.

As the (A) thermoplastic resin, it is exemplified by a polyester resin, a polyether resin, a polyamide resin, a polyamidimide resin, a polyimide resin, a polyvinyl butyral resin, a polyvinyl formal resin, Phenoxy resin, polyhydroxy polyether resin, acrylic resin, polystyrene resin, butadiene resin, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene resin, styrene-butadiene copolymerization , acrylic copolymer. These may be used alone or in combination of two or more.

The component (A) can improve the film formability of the adhesive composition. The film formability means that when the adhesive composition is in the form of a film, it is not acceptable. A mechanical property that is easily broken, broken, and sticky. When the film is easily handled in a normal state (for example, normal temperature), it is said that the film formability is good. Among the above thermoplastic resins, a polyimide resin or a phenoxy resin is preferably used because of its excellent heat resistance and mechanical strength.

The amount of the component (A) is preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C) of the resin component. More preferably 20 to 35 parts by mass. When the amount of the component (A) is within this range, the film formation property of the adhesive composition is improved, and the fluidity is exhibited at the time of hot pressing, and the resin-removing property between the bump and the circuit electrode can be improved. When the amount of the component (A) is less than 10 parts by mass, the film formability is lowered, and the self-supporting substrate and the protective film tend to bleed out. On the other hand, when the amount of the component (A) is more than 50 parts by mass, the fluidity at the time of hot pressing is lowered, and the exclusion property between the bump and the electrode tends to be lowered.

The weight average molecular weight of the component (A) is preferably from 20,000 to 800,000, more preferably from 30,000 to 500,000, still more preferably from 35,000 to 100,000, and most preferably from 40,000 to 80,000. When the weight average molecular weight is in this range, the strength and flexibility of the adhesive layer 2 which is formed into a sheet or a film form are easily balanced, and the fluidity of the adhesive layer 2 is good, so that the circuit filling property of the wiring can be sufficiently ensured. (buried). In the present specification, the weight average molecular weight means a value measured by a gel permeation chromatograph and converted using a standard polystyrene calibration line.

Further, in view of maintaining the film formability on the one hand and imparting adhesion to the adhesive layer 2 before curing, the glass transition of the component (A) The shift temperature is preferably from 20 to 170 ° C, more preferably from 25 to 120 ° C. When the glass transition temperature of the component (A) is less than 20 ° C, the film formation property at room temperature is low, and the adhesive layer 2 tends to be easily deformed during the processing of the semiconductor wafer in the back grinding step, and the adhesive layer 2 is more than 170 ° C. When the bonding temperature to be bonded to the semiconductor wafer needs to be higher than 170 ° C, the thermal curing reaction of the component (B) continues, and the fluidity of the adhesive layer 2 decreases, which tends to cause connection failure. .

(B) The thermosetting resin is exemplified by, for example, an epoxy resin, an unsaturated polyester resin, a melamine resin, a urea formaldehyde resin, a diallyl phthalate resin, a bismaleimide resin, a triazine resin, a polyamine. Carbamate resin, phenol resin, cyanoacrylate resin, polyisocyanate resin, furan resin, resorcinol resin, xylene resin, benzoguanamine resin, oxime resin, decyl oxide modified epoxy Resin and alkane-modified polyamidoximine resin. These may be used alone or in combination of two or more. From the viewpoint of improving heat resistance and adhesion, an epoxy resin is preferably contained as the component (B).

The epoxy resin is not particularly limited as long as it is used after being cured, and for example, an epoxy resin described in the epoxy resin manual (New Masaaki, Nikkan Kogyo Shimbun) can be widely used. Specifically, for example, a difunctional epoxy resin such as a bisphenol A epoxy resin, a phenol novolak epoxy resin, or a novolak epoxy resin of a cresol novolak epoxy resin, a phenol methane can be used. Type epoxy resin. Further, as the polyfunctional epoxy resin, a glycidylamine type epoxy resin, a hetero ring-containing epoxy resin or an alicyclic epoxy resin can be generally used.

In order to maintain the heat resistance and adhesion of the adhesive after curing, and to exhibit high reliability, the blending amount of the component (B) is 100 parts by mass based on the total of the components (A), (B) and (C) of the resin component. It is preferably from 5 to 88 parts by mass, more preferably from 20 to 50 parts by mass, even more preferably from 20 to 40 parts by mass. When the amount of the component (B) is less than 5 parts by mass, the cohesive force of the cured product is lowered, and the connection reliability is liable to be lowered. On the other hand, when the amount of the component (B) is more than 88 parts by mass, the low molecular weight component in the film state before curing becomes too large, so that it is difficult to maintain the film-like body.

Examples of the (C) latent curing agent include, for example, a phenol type, an imidazole type, an anthraquinone type, a thiol type, a benzoxazine, a boron trifluoride-amine complex, an onium salt, an amine imide, A polyamine salt, a dicyandiamide and an organic peroxide-based hardener. However, the circuit member connection adhesive sheet 10 is used for bonding a semiconductor wafer, protecting a circuit electrode during semiconductor wafer grinding, cutting a semiconductor wafer, and bonding a circuit electrode of the obtained semiconductor element. When manufacturing a semiconductor device in a series of steps, it is necessary to maintain the following characteristics: it can be used for bonding the circuit electrodes without being affected by heat, temperature, light, or the like in the manufacturing step while being exposed to a normal temperature environment for a long period of time. In addition to this aspect, the latent curing agent of (C) is preferably a microcapsule-type latent curing agent from the viewpoint of extending the usable period.

The microcapsule-type latent curing agent is exemplified by a core material composed of the above-mentioned curing agent by a coating film: a polymer material such as polyurethane, polystyrene, gelatin or polyisocyanate; An inorganic substance such as calcium acid or zeolite; or a metal film such as nickel or copper.

The average particle diameter of the microcapsule-type latent curing agent is preferably 10 μm or less, more preferably 5 μm or less from the viewpoint of ensuring uniform dispersion of the reaction starting point and film flatness. In addition, the lower limit of the average particle diameter is preferably 1 μm or more from the viewpoint of solvent resistance of the solvent used for the paint at the time of film formation.

The amount of the component (C) is preferably from 2 to 45 parts by mass, more preferably from 10 to 40 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C) of the resin component. Good for 22~40 parts by mass. When the amount of the component (C) is less than 2 parts by mass, the curing reaction tends to be difficult to proceed. On the other hand, when the amount of the component (C) is more than 45 parts by mass, the ratio of the curing agent to the adhesive composition is too large, and the ratio of the thermosetting resin is small, and the properties such as heat resistance and adhesion are deteriorated. tendency.

By including the (D) inorganic filler in the adhesive composition, since the moisture absorption rate and the linear expansion coefficient of the adhesive layer 2 after hardening can be lowered, and the elastic modulus is increased, the connection reliability of the fabricated semiconductor device can be improved. . Further, in order to prevent scattering of visible light in the adhesive layer 2 and to improve visible light transmittance, the (D) component may be selected from inorganic fillers which do not lower the visible light transmittance. It is preferable to select an inorganic filler having a particle diameter smaller than the wavelength of visible light as the component (D) capable of suppressing a decrease in visible light transmittance, or preferably (A) or (B) having a refractive index similar to that of a resin component. An inorganic filler having a refractive index of a resin composition (hereinafter sometimes referred to as "resin composition") composed of the component (C).

The inorganic filler having a particle diameter smaller than the wavelength of visible light is not particularly limited as long as it is a filler having transparency, and is preferably an average particle. The diameter is less than 0.3 μm, more preferably 0.1 μm or less. Moreover, the inorganic filler preferably has a refractive index of 1.46 to 1.7.

An inorganic filler having a refractive index close to a refractive index of a resin composition may be selected to have a refractive index after the refractive index is determined by preparing a resin composition composed of (A), (B), and (C) An inorganic filler having a refractive index. As for the inorganic filler, it is preferable to use a fine filler from the viewpoint of the filling property of the adhesive layer 2 on the gap between the semiconductor wafer and the circuit substrate, and from the viewpoint of suppressing the occurrence of voids in the joining step. The average particle diameter of the inorganic filler is preferably from 0.01 to 5 μm, more preferably from 0.1 to 2 μm, still more preferably from 0.3 to 1 μm. When the average particle diameter is less than 0.01 μm, the specific surface area of the particles is increased to increase the viscosity of the adhesive composition, and the inorganic filler tends to be difficult to be filled.

The inorganic filler having a refractive index close to the refractive index of the resin composition preferably has a refractive index in the range of ±0.06 of the refractive index 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 used. The refractive index can be measured using an Abbe refractometer using sodium D line (589 nm) as a light source. As for the inorganic filler, it is exemplified by a composite oxide filler, a composite hydroxide filler, barium sulfate, and a clay mineral, and specifically, cordierite, forsterite, mullite, barium sulfate, magnesium hydroxide can be used. , aluminum borate, barium or titanium dioxide dioxide.

Further, the above two types of inorganic fillers may be used in combination. However, in order not to affect the viscosity increase of the adhesive composition, the addition amount of the inorganic filler having a particle diameter smaller than the wavelength of visible light is based on the component (D). Fortunately, it is less than 10% by mass.

Further, in the component (D), from the viewpoint of improving the elastic modulus of the adhesive layer 2, the linear expansion coefficient is preferably in the range of from 0 to 700 ° C in the range of 7 × 10 ^-6 / ° C or less, more preferably 3 ×. 10 ^-6 / °C or less.

The amount of the component (D) is preferably from 25 to 200 parts by mass, more preferably from 50 to 150 parts by mass, based on 100 parts by mass of the total of the components (A), (B) and (C) of the resin component. More preferably 75 to 125 parts by mass. When the amount of the component (D) is less than 25 parts by mass, the linear expansion coefficient of the adhesive layer 2 formed of the adhesive composition is likely to increase and the elastic modulus is lowered. As a result, it is easy to reduce the connection reliability between the semiconductor wafer after pressing and the substrate, and it is also difficult to obtain a hole suppressing effect at the time of connection. On the other hand, when the content of the component (D) exceeds 200 parts by mass, the melt viscosity of the adhesive composition is increased, and the interface between the semiconductor wafer and the adhesive layer 2 or the interface between the circuit substrate and the adhesive layer 2 is wetted. The sex is degraded, and it is easy to cause peeling or residual pores caused by insufficient burying.

(E) organic fine particles, which are listed, for example, containing acrylic resin, oxime resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic acid A copolymer of a rubber, a polystyrene, an NBR, an SBR, a decane-modified resin, or the like as a component. The organic fine particles are preferably organic fine particles having a molecular weight of 1,000,000 or more or organic fine particles having a three-dimensional crosslinked structure from the viewpoint of dispersibility, stress relaxation, and adhesion of the adhesive composition. The organic fine particles are exemplified by an alkyl (meth)acrylate-butadiene-styrene copolymer, an alkyl (meth)acrylate-oxime copolymer, and an oxygen-(methyl group). One or more of an acrylic copolymer or a composite. Here, the "organic fine particles having a molecular weight of 1,000,000 or more or the organic fine particles having a three-dimensional crosslinked structure" are poor in solubility to a solvent due to an ultrahigh molecular weight, or have a solubility in a solvent due to a three-dimensional network structure. By. Further, as the component (E), an organic fine particle having a core-shell type structure and a composition different from the core layer and the shell layer may be used. Specific examples of the core-shell type organic fine particles include particles obtained by using a ruthenium-acrylic rubber as a core and an acrylic resin as a shell, and grafting an acrylic resin onto an acrylic copolymer.

Since the component (E) has a crosslinked structure or an ultrahigh molecular weight resin, it is not dissolved in the organic solvent, and thus the particle shape can be maintained in the adhesive composition. Therefore, the component (E) can be dispersed in an island shape in the cured adhesive layer 2, and the strength of the bonded body can be maintained at a high level. The component (E) is a function as an impact-relieving agent containing stress relaxation properties.

The average particle diameter of the component (E) is preferably from 0.1 to 2 μm. When the average particle diameter of the component (E) is less than 0.1 μm, the melt viscosity of the adhesive composition increases, and the solder wettability at the time of joining is hindered. When the thickness exceeds 2 μm, the effect of reducing the melt viscosity is reduced, and when it is connected, It is difficult to obtain a tendency to suppress the hole.

The amount of the component (E) is preferably 100 parts by mass based on the total of the components (A), (B), and (C) in order to impart a stress relaxation effect to the adhesion of the adhesive layer 2 at the time of connection. It is 5 to 20 parts by mass. When the amount of the component (E) is less than 5 parts by mass, it is difficult to achieve suppression. The effect of the hole at the time of the connection is also difficult to exhibit the stress relaxation effect. When the amount is more than 20% by mass, the fluidity is low, so that the wettability of the solder is lowered to cause the residual hole, and the elastic modulus of the cured product is too low. The tendency for connection reliability to decrease.

(F) The powder compound having a maximum particle diameter of 25 μm or less at room temperature is a compound containing at least one selected from the group consisting of a compound having a carboxyl group, a compound having a methylol group, and a hydrazine compound. The component (F) has a function as a solder wettability modifier (hereinafter, the component (F) is a "solder wettability modifier"). That is, the component (F) has a melting point lower than the melting point of the solder, and the solder wettability of the adhesive layer 2 can be improved by removing the oxide of the metal surface such as the solder surface and the circuit electrode after the melting. The component (F) is exemplified by, for example, acetyl salicylic acid, benzoic acid, benzilic acid, adipic acid, sebacic acid, benzyl benzoic acid, malonic acid, 2,2-dual ( Hydroxymethyl)propionic acid, salicylic acid, m-hydroxybenzoic acid, succinic acid, 2,6-dihydroxymethyl-p-cresol, bismuth benzoate, carbonium, diammonium malonate, succinic acid Diterpenoid, diammonium glutarate, bismuth salicylate, diammonium diamine diacetate, diterpene itaconate, triterpenoid citrate, thiocarbonate, benzophenone oxime, 4,4'-oxybisbenzenesulfonate and diammonium adipate. However, as long as it is a solid at room temperature, a compound having a carboxyl group, a compound having a methylol group or a hydrazine compound, it is not limited thereto. From the viewpoint of improving the dispersibility of the adhesive layer 2, it is preferred to pulverize the compounds in a mortar, and after micronizing, the particles having a large particle size are removed by a filter of at least 25 μm. The maximum particle diameter of the component (F) is preferably 20 μm or less. Further, the minimum particle diameter of the component (F) is about 0.01 μm.

The melting point of the component (F) is preferably 100 ° C or more, more preferably 130 to 200 ° C, and still more preferably 140 to 180 ° C. When the melting point of the component (F) is less than 100 ° C, the powder is dissolved at the drying temperature at the time of film formation, and reacts with the thermosetting component to impair the preservability.

The blending amount of the component (F) is preferably from 1 to 20 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the adhesive composition. When the amount of the component (F) is less than 1 part by mass, the effect of improving the wettability is insufficient, and even if the amount is more than 20 parts by mass, the effect of improving the solder wettability is saturated, so that the component becomes excessive.

In the subsequent composition, in order to modify the surface of the inorganic filler to improve the interfacial bonding between the dissimilar materials and increase the bonding strength, various coupling agents may be added. The coupling agent is exemplified by, for example, a decane-based, titanium-based or aluminum-based coupling agent. Among them, a decane-based coupling agent is preferred in terms of high effect.

The decane coupling agent is exemplified by, for example, γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-Mercaptopropyltriethoxydecane, 3-aminopropylmethyldiethoxydecane, 3-ureidopropyltriethoxydecane, 3-ureidopropyltrimethoxydecane. These may be used alone or in combination of two or more.

In the subsequent composition, an ion trapping agent may be added in order to adsorb ionic impurities and improve insulation reliability at the time of moisture absorption. The ion trapping agent is not particularly limited. For example, a compound known as a copper damage preventive agent for preventing copper from being ionized and eluted, such as a triazine thiol compound or a bisphenol-based reducing agent, and inorganic ion adsorption such as a zirconium-based or lanthanide-based magnesium-aluminum compound are exemplified. Agent .

In order to suppress the temperature change or the expansion due to heat absorption and the like after the connection of the semiconductor wafer and the circuit board, and to achieve high connection reliability, the adhesive composition layer 2 is cured at 40 to 100 ° C. The coefficient of linear expansion is preferably 60 × 10 ^-6 / ° C or less, more preferably 55 × 10 ^-6 / ° C or less, more preferably 50 × 10 ^-6 / ° C or less, and the line of the adhesive layer 2 after hardening. When the expansion coefficient exceeds 60 × 10 ^-6 /°C, there is a case where the temperature connection after the mounting or the expansion due to heating and moisture absorption cannot maintain the electrical connection between the connection terminal of the semiconductor wafer and the wiring of the circuit board. In addition, the adhesive sheet 10 for connecting the circuit member may contain conductive particles in the adhesive composition constituting the adhesive layer 2 to form an anisotropic conductive adhesive film (ACF), but preferably contains no conductive particles. Become a non-conductive adhesive film (NCF).

After the adhesive layer 2 formed of the adhesive composition is heated at 250 ° C for 10 seconds, the reaction rate measured by differential scanning calorimetry (hereinafter referred to as "DSC") is preferably 60% or more, more preferably 70% or more. Further, after the substrate member-connecting composition sheet was allowed to stand at room temperature for 14 days, the reaction rate of the adhesive layer 2 measured by DSC was preferably less than 10%. According to this, by using the adhesive composition of the present invention, a film-like adhesive which is excellent in reactivity at the time of connection and excellent in storage stability can be obtained.

When the agent layer 2 is not cured, the visible light transmittance is preferably 5% or more, more preferably the visible light transmittance is 8% or more, and the visible light transmittance is more than 10%. When the visible light transmittance is less than 5%, it is impossible to identify by the identification of the flip-chip solid crystal, and there is a tendency that the position alignment operation cannot be performed. On the other hand, the upper limit of the visible light transmittance is not particularly limited.

The visible light transmittance can be measured using a U-3310 spectrophotometer manufactured by Hitachi. For example, after performing a baseline correction measurement on a PET film (Purex, light transmittance of 86.03% at 555 nm) manufactured by Teijin DuPont having a film thickness of 50 μm, the adhesive layer 2 is formed on the PET film at a thickness of 25 μm, and then measured. Light transmittance in the visible light region of 400 to 800 nm. Since the relative intensity of the wavelength of the halogen light source and the light guide used for the flip chip solid crystal is 550 to 600 nm, the light transmittance of the adhesive layer 2 is compared using the light transmittance of 555 nm in the present specification.

The subsequent layer 2 can be applied to a protective film (hereinafter sometimes referred to as "first film") 1 by dissolving or dispersing the above-described adhesive composition of the present invention in a solvent to form a paint. It is formed by removing the solvent by heating. Subsequently, the support substrate 3 is laminated on the adhesive layer 2 at a normal temperature to 60 ° C to obtain the adhesive member sheet 10 for connection of circuit members of the present invention. Further, the adhesive layer 2 can also be formed by applying the above-mentioned paint to the support substrate 3 and removing the solvent by heating.

The solvent to be used is not particularly limited, but is preferably determined by considering the volatility at the time of formation of the adhesive layer from the boiling point. Specifically, in terms of difficulty in promoting hardening of the adhesive layer at the time of formation of the adhesive layer, for example, methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, methyl A solvent having a relatively low boiling point such as ethyl ketone, acetone, methyl isobutyl ketone, toluene or xylene is preferred. These solvents may be used alone or in combination of two or more.

As the protective film 1, for example, polyethylene terephthalate or polytetrafluoroethylene can be used. Plastic film such as vinyl film, polyethylene film, polypropylene film, polymethylpentene film. From the viewpoint of the releasability, a film having a low surface energy composed of a fluororesin such as a polytetrafluoroethylene film is preferably used as the protective film 1.

In order to improve the releasability of the protective film 1, the surface of the protective film 1 on which the adhesive layer 2 is formed is preferably treated with a release agent such as a ruthenium-based release agent, a fluorine-based release agent, or a long-chain alkyl acrylate release agent. As for the marketer, "A-63" (release agent: modified oxime system) and "A-31" (release agent: Pt system 矽 oxygen system) manufactured by Teijin DuPont Film Co., Ltd. can be purchased.

The thickness of the protective film 1 is preferably from 10 to 100 μm, more preferably from 10 to 75 μm, still more preferably from 25 to 50 μm. When the thickness is less than 10 μm, the protective film tends to be broken during coating, and when it exceeds 100 μm, the inexpensiveness tends to be deteriorated.

The method of applying the above paint to the protective film 1 (or the support substrate 3) is exemplified by a doctor blade coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, and a curtain coating method. A commonly known method such as cloth method.

The thickness of the layer 2 is not particularly limited, but is preferably 5 to 200 μm, more preferably 7 to 150 μm, still more preferably 10 to 100 μm. When the thickness is less than 5 μm, it is difficult to secure a sufficient adhesion force, and the convex electrode of the circuit board cannot be buried. When it is thicker than 200 μm, it is not uneconomical and it is difficult to meet the requirements for miniaturization of the semiconductor device.

The support substrate 3 is exemplified by, for example, 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 poly Bismuth imide film Plastic film. Further, the support base material 3 may be one obtained by mixing two or more kinds selected from the above materials, or may be a multilayered film as described above.

The thickness of the support substrate 3 is not particularly limited, but is preferably 5 to 250 μm. When the thickness is thinner than 5 μm, the semiconductor wafer may be cut to the support substrate when it is ground (back-grinded), and it is uneconomical when the thickness exceeds 250 m.

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

Further, the adhesive film layer may be laminated on the plastic film (hereinafter sometimes referred to as "second film") as the support substrate 3.

Fig. 2 is a schematic cross-sectional view showing a preferred embodiment of the adhesive sheet for connecting circuit members of the present invention. The circuit member connecting adhesive sheet 11 shown in FIG. 2 includes: a supporting substrate 3 having a plastic film 3b and an adhesive layer 3a provided on the plastic film 3b; and a protective member layer 3a provided on the adhesive layer 3a. The adhesive layer 2 composed of the adhesive composition of the invention and the protective film 1 covering the adhesive layer 2 are provided.

In order to improve the adhesion between the second film 3b and the adhesive layer 3a, the surface of the second film may also be subjected to chemical or physical treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, or the like.

The adhesive layer 3a preferably has an adhesive force at room temperature and has a necessary adhesion to the adherend, and preferably has a high energy line or heat by radiation or the like (i.e., reduces adhesion). By. The adhesive layer 3a can be formed using, for example, an acrylic resin, various synthetic rubbers, natural rubber, or a polyimide resin. The thickness of the adhesive layer 3a is usually 5 to 20 μm. about.

The above-described circuit member connecting adhesive sheets 10 and 11 may be used between the circuit member and the semiconductor element or between the semiconductor elements such that the circuit member and the semiconductor element are followed by or the semiconductor elements are connected to each other, the circuit member A circuit electrode having opposing and solder joints. In this case, by thermally pressing the circuit member and the semiconductor element or by heat-pressing the semiconductor elements, it is possible to suppress the occurrence of voids and to sufficiently adhere the force, and the circuit electrodes can be welded to each other favorably. According to this, a connector excellent in connection reliability can be obtained. Further, the circuit member connecting adhesive sheets 10 and 11 can also be used as an adhesive in a lamination technique using a tantalum through electrode.

Hereinafter, a method of manufacturing a semiconductor device using the adhesive sheet 10 for circuit member connection will be described.

3 to 7 are schematic cross-sectional views illustrating an embodiment of a method of manufacturing a semiconductor device according to the present invention. The method for fabricating a semiconductor device according to the present embodiment includes the steps of: (a) preparing a semiconductor wafer having a plurality of circuit electrodes on one side of a main surface, and providing a side of the semiconductor wafer on which a circuit electrode is provided a step of forming an adhesive layer composed of a composition of the second component, (b) a step of thinning the semiconductor wafer by grinding the opposite side of the semiconductor wafer on the side of the circuit electrode, and (c) cutting the thinned semiconductor crystal a step of singulating a round and an adhesive layer into a semiconductor element with a film-like adhesive, and (d) a circuit electrode of a semiconductor element with a film-like adhesive The step of soldering the circuit electrode to the support member for mounting the semiconductor element.

In the step (a) of the present embodiment, an adhesive layer is provided by bonding the adhesive layer 2 of the above-mentioned circuit member connecting adhesive sheet 10 to the circuit electrode side of the semiconductor wafer. Further, in the step (d) of the present embodiment, the bonding is performed by heating, and the film-like adhesive interposed between the semiconductor element and the supporting member for mounting the semiconductor element is also cured. The steps will be described below with reference to the drawings.

(a) steps

First, the circuit member connecting adhesive sheet 10 is placed on a specific device, and the protective film 1 is peeled off. Next, a semiconductor wafer A having a plurality of circuit electrodes 20 on one side of the main surface is prepared, and an adhesive layer 2 is bonded to the side of the semiconductor wafer A on which the circuit electrodes are provided to obtain a support substrate 3/adhesive Layer 2 / Semiconductor Wafer A laminated laminate (see Figure 3). A bump to which solder for solder bonding is applied is provided on the circuit electrode 20. Further, solder may be provided on the circuit electrode of the support member for mounting the semiconductor element.

In the above step (a), as a method of obtaining a laminate in which the support substrate 3 / the adhesive layer 2 / the semiconductor wafer A is laminated, a commercially available film bonding apparatus or laminator can be used. In order to bond the adhesive layer 2 without entanglement of the hole in the semiconductor wafer A, it is preferable to provide a heating mechanism and a pressurizing mechanism to the bonding apparatus, and it is preferable to provide a vacuum suction mechanism. Further, the shape of the adhesive member sheet 10 for circuit member connection is a shape that can be operated by a bonding device. Alternatively, it may be in the form of a roll or a sheet, or may be processed in conformity with the shape of the semiconductor wafer A.

The lamination of the semiconductor wafer A and the adhesive layer 2 is preferably carried out at a temperature at which the adhesive layer 2 is softened. The lamination temperature is preferably from 40 to 80 ° C, more preferably from 50 to 80 ° C, and even more preferably from 60 to 80 ° C. When lamination is performed at a temperature at which the adhesive layer 2 is not softened, insufficient embedding occurs in the periphery of the circuit electrode 20 protruding from the semiconductor wafer A, and the hole is wound. In this case, peeling of the adhesive layer at the time of dicing, deformation of the adhesive layer at the time of picking, identification of the identification mark at the time of positioning, and deterioration of connection reliability due to the hole are likely to occur.

(b) steps

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

In the step (b), the grinding of the semiconductor wafer A can be performed using a general back grinding (B/G) device. In the B/G step, the semiconductor wafer A can be uniformly ground in order not to have uneven thickness, and the adhesive layer 2 in the step (a) is preferably uniformly bonded so as not to be entangled in the holes.

(c) steps

Next, as shown in FIG. 5( a ), the dicing tape 5 is attached to the laminate. On the semiconductor wafer A, it is placed on a specific device and the support substrate 3 is peeled off. At this time, the support base material 3 is provided with the adhesive layer 3a, and when the adhesive layer 3a is radiation-curable, the adhesive layer 3a can be hardened by the irradiation of the radiation from the support substrate 3 side to lower the adhesive layer. The adhesion between 2 and the support substrate 3. Here, the radiation used is exemplified by ultraviolet rays, electron beams, infrared rays, and the like. According to this, the support substrate 3 can be easily peeled off. After the support substrate 3 is peeled off, as shown in FIG. 5(b), the semiconductor wafer A and the adhesive layer 2 are cut by the dicing saw 6. Thus, the semiconductor wafer A can be divided into a plurality of semiconductor elements A', and the adhesive layer 2 can be cut into a plurality of film-like adhesives 2a.

Next, as shown in FIG. 6, while the dicing tape 5 is expanded, the semiconductor elements A' obtained by the dicing are separated from each other, and the absorbing tape 7 is detachably picked up from the side of the dicing tape 5 by the absorbing tape 7 to be attached by the needle. The semiconductor element 12 of the film-like adhesive is composed of the semiconductor element A' and the film-like adhesive 2a. The semiconductor element 12 to which the film-like adhesive is attached may be placed in a tray for recycling, or may be directly mounted on the circuit board by flip chip bonding.

In the step (c), the operation of bonding the dicing tape 5 to the ground semiconductor wafer A is performed by using a general wafer mounter, and can be performed in the same manner as the fixing of the cut lead frame. As the dicing tape 5, a commercially available dicing tape can be used, and a UV curing type or a pressure sensitive type can be used.

(d) steps

Next, as shown in FIG. 7, the semiconductive of the film-like adhesive 2a is adhered. The circuit electrode 20 of the body element A' is aligned with the circuit electrode 22 of the semiconductor element mounting support member 8, and the semiconductor element 12 to which the film-like adhesive is attached and the semiconductor element mounting support member 8 are heat-pressed. By the hot pressing, the circuit electrode 20 and the circuit electrode 22 can be electrically and mechanically connected by solder bonding, and the film-like adhesive 2a can be hardened between the semiconductor element A' and the semiconductor element mounting support member 8. Things.

The temperature at the time of hot pressing is preferably 200 ° C or higher, more preferably 220 to 260 ° C from the viewpoint of solder joint. The hot pressing time can be 1 to 20 seconds. The pressure of hot pressing can be 0.1~5MPa.

By mounting the circuit board with a flip chip, the alignment mark formed on the circuit surface of the semiconductor wafer can be confirmed by the film-like adhesive layer 2a formed on the circuit surface of the semiconductor wafer, and the mounting position of the circuit board can be confirmed. Implementation.

Through the above steps, the semiconductor device 30 is obtained. The film-like adhesive composed of the adhesive composition of the present invention is excellent in embedding property and adhesion after hardening, and at the same time, the oxide film formed on the surface of the solder can be removed even by soldering for a short time, and the wettability of the solder can be improved. . According to this, the semiconductor device 30 can sufficiently suppress the occurrence of voids, and the circuit electrodes can be soldered to each other favorably, and the semiconductor element A' and the semiconductor element mounting supporting member can be adhered to with sufficient adhesion, and the reflow-resistant cracking property and the connection can be reliably ensured. Excellent sex.

[Examples]

The present invention will be more specifically described below by way of examples and comparative examples. But this The invention is not limited to the embodiments.

(Preparation of supporting substrate)

First, an acrylic copolymer was synthesized by a solution polymerization method using 2-ethylhexyl acrylate and methyl methacrylate as main monomers, using hydroxyethyl acrylate and acrylic acid as functional monomers. The obtained acrylic copolymer had a weight average molecular weight of 400,000 and a glass transition temperature of -38 °C. To 100 parts by mass of the acrylic copolymer, 10 parts by mass of a polyfunctional isocyanate crosslinking agent (manufactured by Polyurethan Industrial Co., Ltd., trade name "Coronate HL") was prepared to prepare an adhesive composition solution.

The obtained adhesive composition solution was applied to a polyolefin film (manufactured by Okamoto Co., Ltd., trade name "WNH-2110", thickness: 100 μm) and dried, and the thickness of the adhesive layer was 10 μm. Next, a second film, that is, a biaxially stretched polyester film (manufactured by Teijin DuPont Film Co., Ltd., trade name "A3170", thickness: 25 μm) which was surface-treated with a silicone-based release agent, was laminated on the adhesive layer. The laminate to which the adhesive layer was applied was allowed to stand at room temperature for one week and then cured for a sufficient period of time, and then a release polyolefin film was used as a support substrate.

(Example 1) <Preparation of the composition of the adhesive>

100 parts by mass of "ZX1356-2" (trade name manufactured by Tohto Kasei Co., Ltd., phenoxy resin), and "1032H60" (trade name of epoxy resin company, epoxy resin) 100 parts by weight, " 60 parts by weight of Epikote 828 (trade name, liquid epoxy resin manufactured by Nippon Epoxy Co., Ltd.) and "HX3941HP" (trade name manufactured by Asahi Kasei Electronics Co., Ltd., microcapsule latent curing agent) dissolved in 140 parts by mass In a mixed solvent of toluene and ethyl acetate. 40 parts by mass of "KW-4426" (trade name manufactured by Mitsubishi Rayon Co., Ltd., core-shell type organic fine particles), and a 5 μm-graded cordierite particle having an average particle diameter of 1 μm (2MgO.2Al ₂ O ₃ .5SiO ₂ , specific gravity 2.4, linear expansion coefficient: 1.5 × 10 ^-6 / ° C, refractive index: 1.57) 400 parts by mass, "10H" classified "ADH" (trade name of Otsuka Chemical Co., Ltd., diammonium adipate) 40 parts by mass was dispersed in the solution to obtain an adhesive paint.

<Preparation of an adhesive sheet for connecting circuit members>

The obtained adhesive paint was applied to a first film, that is, a polyethylene terephthalate (PET) film (manufactured by Teijin DuPont Film Co., Ltd., trade name "AH-3", thickness: 50 μm) using a roll coater. It was dried in an oven at 70 ° C for 10 minutes to form an adhesive layer having a thickness of 25 μm . Next, the adhesive layer on the adhesive layer and the above-mentioned support base material is bonded to the normal temperature to obtain an adhesive sheet for connecting the circuit member.

(Example 2)

An adhesive sheet for connecting a circuit member was obtained in the same manner as in Example 1 except that "EXL2655" (trade name manufactured by Rohm and Haas Company) was used instead of "KW-4426" in the preparation of the adhesive paint.

(Example 3)

The same as in the first embodiment except that "2,2-bis(hydroxymethyl)propionic acid" (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter abbreviated as "BHPA") was used instead of "ADH" in the preparation of the adhesive paint. An adhesive sheet for connecting circuit members was obtained.

(Example 4)

In the same manner as in Example 1, except that "EXL2655" was used instead of "KW-4426" in the preparation of the adhesive paint, and the "BHA" was replaced with "ADH", the adhesive sheet for connecting the circuit member was obtained.

(Example 5)

The same as in the first embodiment, except that "2,6-dihydroxymethyl-p-cresol" (trade name "26DMPC" manufactured by Asahi Organic Materials Co., Ltd.) was used instead of "ADH" in the preparation of the adhesive paint. An adhesive sheet for connecting circuit members was obtained.

(Example 6)

In the same manner as in Example 1, except that "EXB2655" was used instead of "KW-4426" in the preparation of the adhesive paint, and the "ADH" was replaced by "260DMPC", the adhesive sheet for connecting the circuit member was obtained.

(Comparative Example 1)

An adhesive sheet for connecting a circuit member was obtained in the same manner as in Example 1 except that "ADH" in the preparation of the adhesive paint was not prepared.

(Comparative Example 2)

In the same manner as in Example 1, except that "EXB2655" was used instead of "KW-4426" in the preparation of the adhesive paint, the adhesive sheet for connecting the circuit member was obtained in the same manner as in Example 1.

[Evaluation of adhesive layer] (Measurement of linear expansion coefficient)

The adhesive sheet for connecting the circuit member obtained in the examples and the comparative examples was placed in an oven set at 180 ° C for 3 hours, and heat-hardened. The self-supporting substrate was peeled off from the adhesive layer after heat curing to prepare a test piece having a size of 30 mm × 2 mm. Using the "TMA/SS6100" (trade name) manufactured by Seiko Instruments, the test piece was placed in the apparatus at a jig pitch of 20 mm to measure the temperature range: 20 to 300 ° C, and the temperature increase rate was 5 ° C / min. Load condition: The pressure was applied to the test piece with a sectional area of 0.5 MPa, and the thermomechanical analysis was performed in a tensile test mode to determine the coefficient of linear expansion.

(reaction rate measurement)

The adhesive layer in the adhesive sheet for connecting circuit members obtained in the examples and the comparative examples obtained by weighing 2 to 10 mg in an aluminum measuring container was used, and a DSC (Differential Scanning Card) "Pylis 1" manufactured by Perkin Elmer Co., Ltd. was used. (trade name), the calorific value of the temperature rise from 30 ° C to 300 ° C at a temperature increase rate of 20 ° C /min was measured, and this was used as the initial calorific value. Next, to clamp on The thermocouple of the separator is subjected to temperature confirmation of the heating head of the hot pressing device, and is set to a temperature of 250 ° C after 10 seconds. With the heating head setting, the circuit member connecting adhesive sheet was sandwiched in a separator and heated for 20 seconds to obtain an adhesive layer in a state in which heat treatment was performed in the same manner as in the case of hot pressing. The calorific value was also measured for the adhesive layer after the heat treatment as the calorific value after heating. Further, the calorific value of the adhesive layer after storage of the adhesive sheet for circuit member connection at room temperature (20 to 25 ° C) for 14 days was measured in the same manner 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

<Production and evaluation of semiconductor devices>

Using the adhesive sheet for connecting circuit members obtained above, a semiconductor device was fabricated and evaluated in the following order. The results are shown in Table 1.

(Matching to semiconductor wafers)

A semiconductor wafer (6-inch diameter, 725 μm in thickness) in which gold-plated bumps were formed was mounted on a suction table heated to 80 ° C in a die-attached film mounter manufactured by JCM so that the bump side faces upward. on. The circuit member connecting adhesive sheet is cut into 200 mm × 200 mm, and the protective film, that is, the adhesive layer of the first film is removed toward the bump side of the semiconductor wafer, so that the air is not entangled from the semiconductor wafer end. Plaster mounting machine The attached roller is pressed and laminated. After lamination, the exposed portions of the adhesive are cut along the wafer.

(backside polishing of the back side of the semiconductor wafer and peeling of the supporting substrate)

The laminate of the above-mentioned circuit member connecting adhesive sheet and the semiconductor wafer (thickness: 625 μm) was subjected to back surface polishing of the back surface of the semiconductor wafer to a thickness of 150 μm by a back grinding apparatus manufactured by DISCO Co., Ltd. Subsequently, the back-grinded semiconductor wafer was placed on the adsorption stage of the paste film mounting machine manufactured by JCM, and the Adeka cutting tape "AD80H" was attached to the cut lead frame at room temperature. Next, the back grinding tape release tape manufactured by Nitto Denko was attached to the support substrate, and peeled off at 180 degrees, and only the support substrate was peeled off.

(cutting)

The semiconductor wafer bonded to the adhesive layer fixed to the above-mentioned cutting lead frame was cut into 10 mm × 10 mm by a fully automatic cutting saw "DFD6361" manufactured by DISCO Corporation. After the dicing, after washing and rinsing the water, UV irradiation was performed from the side of the dicing tape, and the singulated semiconductor wafer to which the adhesive was attached was picked up.

(pressed)

The semiconductor wafer to which the adhesive was attached was subjected to positional alignment on a glass epoxy substrate by a flip chip bonding machine "FCB3" manufactured by Matsushita Electric Industrial Co., Ltd., and then heat-pressed at 250 ° C and 0.5 MPa for 10 seconds to obtain a semiconductor device. , The glass epoxy substrate is a circuit formed of a solder having SnAgCu as a constituent component at a position facing the bump.

The embedding property and connection resistance of the film-form adhesive in the semiconductor device produced as described above were evaluated. Next, the fabricated semiconductor device was placed in a thermo-hygrostat at 85 ° C and 60% RH for 168 hours to absorb moisture, and exposed to a reflow furnace set at 260 ° C three times. After exposure, confirm the connection resistance and the interface state of the connection part.

<buried after pressing>

The adhesion state of the adhesive layer was observed by the Hitachi Construction Mechanism Ultrasonic Flaw Detector (SAT), and evaluation was performed based on the following criteria.

A: No peeling or holes were observed.

B: Peeling, hole is observed

<Connectivity after reflow>

The connection state of the adhesive layer after reflow was observed by the Hitachi Construction Mechanism Ultrasonic Flaw Detector (SAT), and evaluation was performed based on the following criteria.

A: No peeling was observed

B: Observed peeling

<connection resistance>

For the fabricated semiconductor device, the connection resistance after pressing and the connection resistance after reflow were measured using a digital multifunction meter (manufactured by Advantest Co., Ltd.), and evaluated based on the following criteria.

(connection resistance after pressing)

A: The resistance value of all the terminals (176 terminals) of the TEG used for the test is 7~10Ω.

B: The resistance of all the terminals is not obtained, or the resistance value of all the terminals is greater than 10Ω.

(connection resistance after reflow)

A: The resistance rises within 20% with respect to the value of the connection resistance after pressing

B: The resistance rises by more than 20% with respect to the connection resistance after pressing

<temperature cycle test>

The reflowed semiconductor device was placed in a temperature cycle test in which a cycle was repeated at -55 ° C for 30 minutes and at 125 ° C for 30 minutes, and the presence or absence of connection resistance maintenance in the test machine was evaluated. The number of cycles that can be energized is shown in Table 1.

As shown in Table 1, when the adhesive sheets for connection of circuit members obtained in Examples 1 to 6 were used, no voids were formed, and good connectivity was exhibited after reflow, and it was possible to pass 1000 cycles or more in the temperature cycle test. Turn on. On the other hand, when the adhesive sheets for connection of circuit members obtained in Comparative Examples 1 and 2 were used, although no voids were formed and good connectivity was exhibited after reflow, the temperature cycle test caused connection failure at 300 cycles. Further, since the wettability of the bump was insufficient, it was confirmed that the solder joint was insufficient and the connection reliability was poor.

1‧‧‧Protective film

2‧‧‧ adhesive layer

3‧‧‧Support substrate

3a‧‧‧Adhesive layer

3b‧‧‧Plastic film

4‧‧‧ Grinder

5‧‧‧Cut Tape

6‧‧‧Cutting saw

7‧‧‧Adsorption gripper

8‧‧‧Supporting member for mounting semiconductor components

10‧‧‧Attachment sheet for connecting circuit components

11‧‧‧Attachment sheet for connecting circuit components

12‧‧‧Semiconductor components with film-like adhesives

20‧‧‧Circuit electrodes

30‧‧‧Semiconductor device

A‧‧‧Semiconductor Wafer

Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members of the present invention.

Fig. 2 is a schematic cross-sectional view showing a preferred embodiment of an adhesive sheet for connecting circuit members of the present invention.

Fig. 3 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device of the present invention.

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

Fig. 5 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device of the present invention.

Fig. 6 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device of the present invention.

Fig. 7 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device of the present invention.

Claims (3)

An adhesive sheet for connecting circuit members for interposing between circuit members for mutually connecting the circuit members, wherein the circuit members have opposite and soldered circuit electrodes, and the circuit member connection adhesive sheets are provided with support groups a material and an adhesive layer, wherein the adhesive layer is provided on the support substrate and is composed of an adhesive composition, and the adhesive composition comprises: (A) a thermoplastic resin having a weight average molecular weight of 20,000 to 800,000 (B) a thermosetting resin containing an epoxy resin, (C) a latent curing agent, (D) an inorganic filler having an average particle diameter of 0.01 to 5 μm , (E) an organic fine particle having a molecular weight of 1,000,000 or more or An organic fine particle having a three-dimensional crosslinked structure, and (F) a powder compound having a maximum particle diameter of 25 μm or less at room temperature, wherein the component (C) is selected from the group consisting of a phenol type, an imidazole type, and a thiol. a group of benzoxazines, boron trifluoride-amine complexes, phosphonium salts, amine imines, polyamine salts, dicyandiamides, and organic peroxide-based hardeners. At least one latent hardener, the aforementioned (F) component is selected from the group consisting of Salicylic acid, benzoic acid, diphenyl glycolic acid, adipic acid, sebacic acid, benzyl benzoic acid, malonic acid, 2,2-bis(hydroxymethyl)propionic acid, salicylic acid, succinic acid, 2,6-dihydroxymethyl-p-cresol, bismuth benzoate, carbonium, diammonium malonate, diterpene succinate, diammonium glutarate, bismuth salicylate, imine a group of diterpene acetate, itaconic acid diterpene, trihdral citrate, thiocarbonium, 4,4'-oxybisbenzenesulfonate and diammonium adipate At least one compound. The adhesive sheet for connecting circuit members of claim 1, wherein the support substrate comprises a plastic film and an adhesive layer provided on the plastic film, and the adhesive layer is provided on the adhesive layer. A method of manufacturing a semiconductor device, comprising the steps of: preparing a semiconductor wafer having a plurality of circuit electrodes on one side of a main surface, and providing a request item 1 on a side of the semiconductor wafer on which the circuit electrode is provided Or the step of connecting the adhesive layer in the adhesive sheet of the circuit member of 2; the step of grinding the opposite side of the semiconductor wafer on the side of the circuit electrode to thin the semiconductor wafer; dicing a step of singulating the thinned semiconductor wafer and the adhesive layer into a semiconductor element with a film-like adhesive; and the foregoing circuit of the semiconductor element with the film-like adhesive The electrode is soldered to the circuit electrode of the support member for mounting the semiconductor element.