JP5569121B2 - Adhesive composition, circuit member connecting adhesive sheet, and method for manufacturing semiconductor device - Google Patents

Description

  The present invention relates to an adhesive composition, an adhesive sheet for connecting circuit members, 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, a method is generally known 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, through silicon vias (TSV: Through Silicon Via), which is a three-dimensional mounting technology for connecting chips at the shortest distance, has recently attracted attention as enabling higher functionality and higher speed operation (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 addition, with the demand for further thinning of semiconductor devices, so-called back grinding, in which the back surface of the wafer is ground, is performed 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

OKI Technical Review October 2007 / No. 211 VOL. 74 No. 3

  However, with the thinning of the semiconductor device, the gaps between the connection portions and the pitch between the terminals are becoming narrower. For this reason, insufficient filling between the pitches of the film-like resin due to insufficient wetting at the interface due to insufficient flow of the film-like resin at the time of connection or generation of voids due to foaming of the film-like resin, lowering the connection reliability There are things to do. 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.

  Also, in the face-down bonding method in which solder bumps are formed on the electrode part of the semiconductor chip and the semiconductor chip is directly connected to the circuit board by solder bonding, the solder surface and the metal surface of the connection terminal part are obtained in order to obtain good electrical bonding. It is required to remove the oxide film formed on the surface. However, with conventional adhesives, when solder bonding is performed by heating in a short time, flux activity for removing the oxide film on the solder surface and the metal surface of the connection terminal portion cannot be obtained, and solder wetting becomes insufficient. Connection reliability may be reduced.

  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 circuit member connecting 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. (F) a powder compound that is solid at room temperature and has a maximum particle size of 25 μm or less, and the component (F) is at least one selected from a compound having a carboxyl group, a compound having a methylol group, and a hydrazide compound. An adhesive composition that is a seed compound 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 with improved solder wettability, which can be sufficiently reduced, and by adding the component (F), the oxide film formed on the solder surface and the metal surface of the connection terminal portion can be removed. Can be formed.

  Moreover, in the adhesive composition of this invention, it is preferable that (B) component contains an epoxy resin from a viewpoint of improving heat resistance and adhesiveness.

  The adhesive composition of the present invention can be used for adhering circuit members by interposing them between circuit members having circuit electrodes that are opposed to each other and soldered. In this case, the circuit members can be bonded together with a sufficient adhesive force while suppressing the generation of voids by thermocompression bonding, and the circuit electrodes can be soldered well. Thereby, the connection body excellent in connection reliability can be obtained.

  The adhesive sheet for circuit member connection of this invention is equipped with a support base material and the adhesive bond layer which is provided on this support base material and consists of the adhesive composition of the said invention, It is characterized by the above-mentioned.

  It is preferable that the support substrate 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. Thereby, the adhesive sheet for circuit member connection of this invention can hold | maintain a semiconductor wafer stably at the time of back grinding of a semiconductor wafer.

  Moreover, the adhesive sheet for circuit member connection of this invention can be used between the circuit members which have the circuit electrode mutually opposed and solder-joined, and to adhere circuit members. In this case, the circuit members can be bonded together with a sufficient adhesive force while suppressing the generation of voids by thermocompression bonding, and the circuit electrodes can be soldered well. 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 thinning the semiconductor wafer by grinding the side of the semiconductor wafer opposite to the side where the circuit electrodes are provided, and a semiconductor with a film adhesive by dicing the thinned semiconductor wafer and the adhesive layer Provided is a method for manufacturing a semiconductor device, comprising a step of dividing into elements and a step of solder-bonding circuit electrodes of a semiconductor element with a film adhesive to a circuit electrode of a support member for mounting a semiconductor element.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the embedding property when it is made into a film form, the adhesive composition which enables preparation of the semiconductor device which is excellent in connection reliability, and the adhesive sheet for circuit member connection using the same Can be provided. 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.

  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 of the present invention constituting 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) organic fine particles, F) a powder compound that is solid at room temperature and has a maximum particle size of 25 μm or less.

  (A) As a thermoplastic resin, polyester resin, polyether resin, polyamide resin, polyamideimide resin, polyimide resin, polyvinyl butyral resin, polyvinyl formal resin, phenoxy resin, polyhydroxy polyether resin, acrylic resin, polystyrene resin, butadiene Examples thereof include 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.

  The component (A) can improve the film forming property of the adhesive composition. Film forming property indicates mechanical properties that are not easily torn, broken, or sticky when the adhesive composition is formed into 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 blending amount of the component (A) is preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C), which are resin components. It is more preferable that it is 20-35 mass parts. When the blending amount of the component (A) is within this range, the film forming property of the adhesive composition is improved, the fluidity is exhibited during thermocompression bonding, and the resin exclusion property between the bump and the circuit electrode can be improved. When the blending amount of the component (A) is less than 10 parts by mass, the film formability tends to decrease or the support base and the protective film protrude from the sides. On the other hand, when the blending amount of the component (A) exceeds 50 parts by mass, the fluidity at the time of thermocompression bonding is lowered, and the exclusion from the bump and the electrode tends to be lowered.

  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 35,000 to 100,000, and 40,000 to 8 It is particularly preferable that the number is 10,000. 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.

  Moreover, it is preferable that the glass transition temperature of (A) component is 20-170 degreeC from a viewpoint which provides adhesiveness to the adhesive bond layer 2 before hardening, maintaining film formation. 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.

  (B) Examples of thermosetting resins include epoxy resins, unsaturated polyester resins, melamine resins, urea resins, diallyl phthalate resins, bismaleimide resins, triazine resins, polyurethane resins, phenol resins, cyanoacrylate resins, and polyisocyanate resins. , Furan resin, resorcinol resin, xylene resin, benzoguanamine resin, silicone resin, siloxane-modified epoxy resin, and siloxane-modified polyamideimide resin. 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, bifunctional epoxy resins such as bisphenol A type epoxy, novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, and 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 blending amount of the component (B) is the sum of the components (A), (B) and (C) which are resin components in order to maintain the heat resistance and adhesiveness of the adhesive after curing and to exhibit high reliability. The amount is preferably 5 to 88 parts by mass, more preferably 20 to 50 parts by mass, and still more preferably 20 to 40 parts by mass with respect to 100 parts by mass. When the blending 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 easily lowered. On the other hand, when the compounding quantity of (B) component exceeds 88 mass parts, it will become difficult to hold | maintain a film-form body because there are too many low molecular weight components in the film state before hardening.

  (C) Examples of latent curing agents include phenolic, imidazole, hydrazide, thiol, benzoxazine, boron trifluoride-amine complexes, sulfonium salts, amine imides, polyamine salts, dicyandiamide and organic peroxides. Mention may be made of system curing agents. By the way, the adhesive sheet 10 for connecting circuit members is used for semiconductor devices such as sticking to a semiconductor wafer, protection of circuit electrodes during grinding of the semiconductor wafer, dicing of the semiconductor wafer, and bonding of the obtained semiconductor elements to the circuit electrodes. When it is applied to a series of manufacturing processes, it is exposed to a long-term room temperature environment and has characteristics that can be used when bonding to circuit electrodes without being affected by heat, humidity, light, etc. in the manufacturing process. Need to hold. In addition to this point, from the viewpoint of extending the usable period, it is preferable that the latent curing agent (C) is a microcapsule type latent curing agent.

  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.

  The average particle size of the microcapsule-type latent curing agent is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint of uniform dispersion of reaction starting points and ensuring flatness of the film. Moreover, it is preferable that the lower limit of an average particle diameter is 1 micrometer or more from a viewpoint of ensuring the solvent resistance with respect to the solvent used for the varnish at the time of film formation.

  The amount of component (C) is preferably 2 to 45 parts by mass, and 10 to 40 parts by mass with respect to 100 parts by mass as a total of the components (A), (B) and (C). It is more preferable that it is 22-40 mass parts. When the amount of component (C) is less than 2 parts by mass, the curing reaction tends to be difficult to proceed. On the other hand, when the blending amount of component (C) exceeds 45 parts by mass, the ratio of the curing agent in the adhesive composition is excessively increased. It tends to deteriorate the characteristics such as.

  Since the adhesive composition contains (D) an inorganic filler, 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. Reliability 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 composed of the components (A), (B) and (C) and measuring the refractive index, An inorganic filler having an approximate refractive index 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 suitably 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 clay minerals. Specifically, cordierite, forsudite, mullite, barium sulfate, magnesium hydroxide, aluminum borate Barium or silica titania can be used.

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

The component (D) is preferably 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, and 3 × 10. More preferably, it is ⁻⁶ / ° C. or lower.

  The blending amount of the component (D) is preferably 25 to 200 parts by weight, and 50 to 150 parts by weight with respect to a total of 100 parts by weight of the components (A), (B) and (C). It is more preferable that it is 75-125 mass parts. When the blending amount of the component (D) is less than 25 parts by mass, an increase in the linear expansion coefficient and a decrease in the elastic modulus of the adhesive layer 2 formed from the adhesive composition are likely to occur. For this reason, the connection reliability between the semiconductor chip and the substrate after pressure bonding is likely to be lowered, and further, it is difficult to obtain a void suppressing effect at the time of connection. On the other hand, when the content of component (D) exceeds 200 parts by mass, the melt viscosity of the adhesive composition increases, and the interface between the semiconductor chip and the adhesive layer 2 or the interface between the circuit board and the adhesive layer 2 is increased. By reducing the wettability, voids are likely to 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 1,000,000 or more or organic fine particles having a three-dimensional cross-linked structure are preferable from the viewpoints of dispersibility in the adhesive composition, stress relaxation properties, and adhesion improvement. As such organic fine particles, 1 selected from alkyl (meth) acrylate-butadiene-styrene copolymer, alkyl (meth) acrylate-silicone copolymer, silicone- (meth) acrylic copolymer or composite. More than types. Here, “organic fine particles having a molecular weight of 1 million or more or organic fine particles having a three-dimensional cross-linked structure” are those having a high molecular weight and poor solubility in a solvent, or having a three-dimensional network structure. Therefore, the solubility in a solvent is poor. Further, as the component (E), organic fine particles having a core-shell structure and having different compositions in the core layer and the shell layer can be used. As core-shell type organic fine particles, specifically, the silicone - particles grayed raft acrylic resin as a core of acrylic rubber include particles of acrylic resin and graft acrylic copolymer.

  Since the component (E) has a cross-linked structure or is an ultrahigh molecular weight resin, it does not dissolve in an organic solvent, so that it can be blended in the adhesive composition while maintaining the particle shape. For this reason, (E) component can be disperse | distributed to island shape in the adhesive bond layer 2 after hardening, and the intensity | strength of a connection body can be kept high. The component (E) has a function as an anti-shock agent having stress relaxation properties.

  (E) It is preferable that an average particle diameter is 0.1-2 micrometers. When the average particle size of the component (E) is less than 0.1 μm, the melt viscosity of the adhesive composition increases, and there is a tendency to prevent solder wettability at the time of connection, and when it exceeds 2 μm, the effect of reducing the melt viscosity decreases. It tends to be difficult to obtain a void suppression effect at the time of connection.

  The amount of component (E) is such that the void suppression at the time of connection and the stress relaxation effect after connection are imparted to the adhesive layer 2, so that the total amount of components (A), (B) and (C) is 100 parts by mass. The amount is preferably 5 to 20 parts by mass. If 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 difficult to be exhibited. 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.

(F) The powder compound that is solid at room temperature and has a maximum particle size of 25 μm or less is a compound containing at least one selected from a compound having a carboxyl group, a compound having a methylol group, and a hydrazide compound. The component (F) has a function as a solder wettability modifier (hereinafter, the component (F) is referred to as “solder wettability modifier”). That is, the component (F) has a melting point at a temperature lower than the melting point of the solder, and removes oxides on the metal surface such as the solder surface and the circuit electrode after melting, thereby improving the solder wettability of the adhesive layer 2. Can be improved. Examples of the component (F) include acetylsalicylic acid, benzoic acid, benzylic acid, adipic acid, azelaic acid, benzylbenzoic acid, malonic acid, 2,2-bis (hydroxymethyl) propionic acid, salicylic acid, m-hydroxybenzoic acid, succinic acid, 2,6-di hydro carboxymethyl p-cresol, hydrazide benzoic acid, carbohydrazide, dihydrazide malonate, dihydrazide succinate, glutaric acid dihydrazide, salicylic acid hydrazide, iminodiacetic acid dihydrazide, itaconic acid dihydrazide, trihydrazide citrate, thio Carbohydrazide, benzophenone hydrazone, 4,4′-oxybisbenzenesulfonyl hydrazide and adipic acid dihydrazide. However, it is not limited to these compounds as long as they are solid at room temperature and have a carboxyl group, a methylol group or a hydrazide compound. From the viewpoint of improving the dispersibility in the adhesive layer 2, it is preferable to use these compounds after pulverizing them with a mortar and pulverizing them, and then removing those having a large particle size with a filter of at least 25 μm. The maximum particle size of the component (F) is more preferably 20 μm or less. In addition, the minimum particle diameter of (F) component is about 0.01 micrometer.

  (F) It is preferable that melting | fusing point of a component is 100 degreeC or more, It is more preferable that it is 130-200 degreeC, It is still more preferable that it is 140-180 degreeC. When the melting point of the component (F) is less than 100 ° C., the powder dissolves at the drying temperature during film formation, reacts with the thermosetting component, and the storage stability tends to be impaired.

  The compounding amount of the component (F) is preferably 1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the adhesive composition. If the blending amount of the component (F) is less than 1 part by mass, the effect of improving the solder wettability is not sufficient, and even if blended in excess of 20 parts by mass, the effect of improving the solder wettability is saturated, so that it becomes an excess component.

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

  An ion scavenger can be added to the adhesive composition in order to adsorb ionic impurities and improve insulation reliability when absorbing moisture. There is no restriction | limiting in particular as such an ion trapping agent. For example, compounds such as triazine thiol compounds, bisphenol reducing agents, etc., which are known as copper damage inhibitors to prevent ionization and dissolution, inorganic ions adsorbents such as zirconium-based and antimony bismuth-based magnesium aluminum compounds, etc. It is done.

The adhesive composition suppresses temperature change after connecting the semiconductor chip and the circuit board, expansion due to heat absorption, etc., and achieves high connection reliability. The linear expansion coefficient at 60 ° C. is preferably 60 × 10 ⁻⁶ / ° C. or less, more preferably 55 × 10 ⁻⁶ / ° C. or less, and further preferably 50 × 10 ⁻⁶ / ° C. or less. When the linear expansion coefficient of the adhesive layer 2 after curing exceeds 60 × 10 ⁻⁶ / ° C., electricity between the connection terminals of the semiconductor chip and the wiring of the circuit board is caused by temperature change after mounting or expansion due to heat absorption. Connection may not be maintained. Moreover, the adhesive sheet 10 for circuit member connection can make an anisotropic conductive adhesive film (ACF) by making an adhesive composition which comprises the adhesive bond layer 2 contain conductive particles, but contains conductive particles. A non-conductive adhesive film (NCF) is preferably used.

  The adhesive layer 2 formed from the adhesive composition preferably has a reaction rate measured by differential scanning calorimetry (hereinafter referred to as “DSC”) of 60% or more after heating at 250 ° C. for 10 seconds. More preferably, 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 of this invention, the film adhesive which is fully excellent in the reactivity at the time of a connection, and is excellent also in storage stability can be obtained.

  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.

  The visible light transmittance can be measured using a Hitachi U-3310 spectrophotometer. For example, after performing baseline correction measurement using a Teijin DuPont PET film having a film thickness of 50 μm (Purex, transmittance of 86.03% at 555 nm) as a reference material, the adhesive layer 2 having a thickness of 25 μm is applied to the PET film. After the formation, 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, the transmittance of the adhesive layer 2 is compared using the transmittance at 555 nm in this specification. 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. Then, the support base material 3 is laminated | stacked at normal temperature-60 degreeC on the adhesive bond layer 2, and the adhesive sheet 10 for circuit member connection of this invention can be obtained. 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 is preferably determined in consideration of the volatility at the time of forming the adhesive layer from 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, plastic films, such as a polyethylene terephthalate, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polymethylpentene film, can be used, for example. 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” (release treatment agent: modified silicone type) or “A-31” (release treatment agent: Pt silicone type) manufactured by Teijin DuPont Films Ltd. 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.

  Although there is no restriction | limiting in particular in the thickness of the adhesive bond layer 2, 5-200 micrometers is preferable, It is more preferable that it is 7-150 micrometers, It is still more preferable that it is 10-100 micrometers. 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.

  Although the thickness of the support base material 3 does not have a restriction | limiting in particular, 5-250 micrometers is preferable. 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 base material 3 preferably has high light transmittance. Specifically, the minimum light transmittance in a wavelength region of 500 to 800 nm is preferably 10% or more.

  In addition, as the support base 3, a substrate in which an adhesive layer is laminated 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 20 μm.

  The above-mentioned adhesive sheets 10 and 11 for connecting a circuit member are interposed between a circuit member and a semiconductor element having circuit electrodes which are opposed to each other and soldered, or between semiconductor elements, and the circuit member and the semiconductor element or semiconductor. It can be used for bonding elements together. In this case, the circuit member and the semiconductor element or the semiconductor elements can be bonded together with sufficient adhesive force while suppressing generation of voids, and the circuit electrodes can be soldered well. Thereby, the connection body excellent in connection reliability can be obtained. Moreover, the adhesive sheets 10 and 11 for circuit member connection can also be used as an adhesive in a lamination technique using silicon through electrodes.

  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 of this embodiment is as follows:
(A) preparing a semiconductor wafer having a plurality of circuit electrodes on one of the main surfaces, and providing an adhesive layer made of the adhesive composition of the present invention on the side of the semiconductor wafer on which the circuit electrodes are provided; (B) grinding the opposite side of the semiconductor wafer from the side on which 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) solder bonding the circuit electrode of the semiconductor element with a film adhesive to the circuit electrode of the supporting member for mounting the semiconductor element;
Is provided.

  In the step (a) in this 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 for circuit member connection 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 is provided with bumps coated with solder for soldering. Note that solder may be provided on the circuit electrode of the semiconductor element mounting support member.

  In the 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 laminating temperature is preferably 40 to 80 ° C, more preferably 50 to 80 ° C, and still more preferably 60 to 80 ° C. 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, resulting in a state where a void is involved. In this case, peeling of the adhesive layer at the time of dicing, deformation of the adhesive layer at the time of pick-up, recognition mark identification failure at the time of alignment, and a decrease 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 semiconductor element 12 with a film adhesive may be collected by tray packing, or may be mounted on a circuit board as it is with a flip chip bonder.

  In the step (c), the operation 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 electrically and mechanically connected by solder bonding, and the film adhesive 2a is interposed between the semiconductor element A ′ and the semiconductor element mounting support member 8. A cured product is formed.

  The temperature during thermocompression bonding is preferably 200 ° C. or higher, and 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 the present invention is excellent in embedding property and adhesive strength after curing, and can remove an oxide film formed on the solder surface even in a short time solder joint. And solder wettability can be improved. Therefore, in the semiconductor device 30, generation of voids is sufficiently suppressed, the circuit electrodes are well soldered, and the semiconductor element A ′ and the semiconductor element mounting support member are bonded with a sufficient adhesive force, thereby being resistant to reflow cracking. And can be excellent in connection reliability.

  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 (trade name “WNH-2110”, thickness: 100 μm, manufactured by Okamoto Co., Ltd.) so that the thickness of the pressure-sensitive adhesive layer upon drying was 10 μm and dried. did. Further, a biaxially stretched polyester film (trade name “A3170, thickness: 25 μm” manufactured by Teijin DuPont Films, Ltd.) surface-treated with a silicone release agent as the second film was laminated on the pressure-sensitive adhesive layer. The layered laminate was allowed to stand at room temperature for 1 week and sufficiently aged, and then the polyolefin film was used as a supporting substrate.

Example 1
<Preparation of adhesive composition>
“ZX1356-2” (trade name, manufactured by Tohto Kasei Co., Ltd., phenoxy resin) 100 parts by mass, “1032H60” (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), 100 parts by mass, “Epicoat 828” (Japan Epoxy Resin Co., Ltd.) Product name, liquid epoxy resin) 60 parts by mass and "HX3941HP" (Asahi Kasei Electronics Co., Ltd., product name, microcapsule type latent curing agent) 140 parts by mass were dissolved in a mixed solvent of toluene and ethyl acetate. To this solution, 40 parts by mass of “KW-4426” (trade name, core-shell type organic fine particles manufactured by Mitsubishi Rayon Co., Ltd.) and an average particle size of 1 μm cordierite particles (2MgO · 2Al ₂ O _3. “ADH” (product of Otsuka Chemical Co., Ltd.) subjected to classification treatment of 400 parts by mass and 10 μm, 5SiO ₂ , specific gravity 2.4, linear expansion coefficient: 1.5 × 10 ⁻⁶ / ° C., refractive index: 1.57 40 parts by weight of adipic acid dihydrazide) was 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 (trade name “AH-3”, thickness: 50 μm, manufactured by Teijin DuPont Films Ltd.), which is the first film, using a roll coater. It was dried in an oven at 0 ° C. for 10 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 “EXL2655” (trade name, manufactured by Rohm and Haas) was used instead of “KW-4426” in the preparation of the adhesive varnish. .

(Example 3)
The same as Example 1 except that it was mixed with “2,2-bis (hydroxymethyl) propionic acid” (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter abbreviated as “BHPA”) instead of “ADH” in the preparation of the adhesive varnish. Thus, an adhesive sheet for connecting circuit members was obtained.

(Example 4)
An adhesive sheet for connecting circuit members was prepared in the same manner as in Example 1 except that “EXL2655” was substituted for “KW-4426” and “BHPA” was substituted for “ADH” in the preparation of the adhesive varnish. Obtained.

(Example 5)
Instead of the "ADH" in the preparation of adhesive varnish "2,6-hydro carboxymethyl p-cresol" (Asahi Organic material trade name, "26DMPC") except formulated into in the same manner as in Example 1, An adhesive sheet for connecting circuit members was obtained.

(Example 6)
An adhesive sheet for connecting circuit members in the same manner as in Example 1 except that “EXL2655” was blended in place of “KW-4426” and “26DMPC” was blended in place of “ADH” in the preparation of the adhesive varnish. Got.

(Comparative Example 1)
An adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1 except that “ADH” in the preparation of the adhesive varnish was not blended.

(Comparative Example 2)
In place of “KW-4426” in the preparation of the adhesive varnish, “EXL2655” was blended and “ADH” was not blended, and an adhesive sheet for connecting circuit members was obtained in the same manner as in Example 1.

[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.

(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) “Pylis1” (trade name) manufactured by PerkinElmer Co. 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 of the adhesive layer after the circuit member connecting adhesive sheet was stored at room temperature (20 to 25 ° C.) for 14 days was similarly measured, 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 circuit member connection obtained above, a semiconductor device was produced and evaluated according to the following procedure. The results are shown in Table 1.

(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)
The back surface of the semiconductor wafer was back-ground with the back grinder manufactured by DISCO Corporation using a laminate of the above-mentioned adhesive sheet for connecting circuit members and a semiconductor wafer (thickness: 625 μm) until the thickness reached 150 μm. Thereafter, the back-ground semiconductor wafer was placed on the suction stage of a die attach film mounter manufactured by JCM, 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 moisture, and performing 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 bumps, a flip chip bonder “FCB3” manufactured by Matsushita Electric Industrial Co., Ltd. is used. 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.

<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.
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.
A: No peeling is observed.
B: Peeling is observed.

<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.
(Connection resistance after crimping)
A: The resistance value when all terminals (176 terminals) of the mounting TEG applied to the test are connected is 7 to 10Ω.
B: Resistance at all terminal connection is not obtained, or resistance value at all terminal connection is larger than 10Ω (connection resistance after reflow)
A: Resistance increase within 20% of the connection resistance value after crimping B: Resistance increase exceeding 20% with respect to the connection resistance value after crimping

<Temperature cycle test>
The semiconductor device after the reflow was put into a temperature cycle test in which one cycle was −55 ° C. for 30 minutes and 125 ° C. for 30 minutes, and it was evaluated whether or not the connection resistance in the test machine was maintained. Table 1 shows the number of cycles that could be energized.

  As shown in Table 1, when the circuit sheet connecting adhesive sheets obtained in Examples 1 to 6 were used, no void was generated, and good connectivity was exhibited even after reflowing. It was possible to conduct for more than one cycle. On the other hand, when the adhesive sheet for circuit member connection obtained in Comparative Examples 1 and 2 was used, there was no void generation and good connectivity after reflow, but there was a connection failure in 300 cycles of the temperature cycle test. It was confirmed that since solder wettability was insufficient, solder bonding was insufficient and connection reliability was poor.

  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 (7)

It is interposed between circuit members having circuit electrodes that are opposite to each other and solder-bonded, and is an adhesive sheet for connecting circuit members used for bonding the circuit members,
A support substrate, and an adhesive layer provided on the support substrate and made of an adhesive composition,
The adhesive composition is
(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 size of 0.01 to 5 μm;
(E) Organic fine particles having an average particle diameter of 0.1 to 2 μm and a molecular weight of 1,000,000 or more, or organic fine particles having a three-dimensional crosslinked structure;
(F) a powder compound which is solid at room temperature and has a melting point of 100 to 200 ° C. and a maximum particle size of 25 μm or less;
Including
The component (C) is selected from the group consisting of phenolic, imidazole, thiol, benzoxazine, boron trifluoride-amine complexes, sulfonium salts, amine imides, polyamine salts, dicyandiamide, and organic peroxide curing agents. A latent curing agent containing at least one selected,
The component (F) includes acetylsalicylic acid, benzoic acid, benzylic acid, adipic acid, azelaic acid, benzylbenzoic acid, malonic acid, 2,2-bis (hydroxymethyl) propionic acid, salicylic acid, succinic acid, 2,6- Dihydroxymethyl paracresol, benzoic acid hydrazide, carbohydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, salicylic acid hydrazide, iminodiacetic acid dihydrazide, itaconic acid dihydrazide, citric acid trihydrazide, thiocarbohydroxide 4, An adhesive sheet for connecting circuit members, which is at least one compound selected from the group consisting of bisbenzenesulfonyl hydrazide and adipic acid dihydrazide .   The adhesive sheet for connecting circuit members according to claim 1, wherein the thermoplastic resin is a phenoxy resin. The component (C), microswitch is a capsule-type latent curing agent, the adhesive sheet for circuit member connection according to claim 1 or 2.   The inorganic filler is at least one selected from the group consisting of cordierite, forosite, mullite, barium sulfate, magnesium hydroxide, aluminum borate, barium, and silica titania. The adhesive sheet for circuit member connection as described.   The blending amount of the component (D) is 25 to 200 parts by weight with respect to a total of 100 parts by weight of the component (A), the component (B) and the component (C), and the blending amount of the component (F) is The adhesive sheet for circuit member connection according to any one of claims 1 to 4, wherein the adhesive sheet is 1 to 20 parts by mass with respect to 100 parts by mass of the adhesive composition.   The said support base material is provided with the adhesive layer provided on the plastic film and this plastic film, and the said adhesive layer is provided on the said adhesive layer, The any one of Claims 1-5. The adhesive sheet for circuit member connection as described in 2. A semiconductor wafer having a plurality of circuit electrodes on one of its main surfaces is prepared, and the circuit member connecting adhesive according to any one of claims 1 to 6 is provided on a side of the semiconductor wafer on which the circuit electrodes are provided. Providing the adhesive layer of the agent sheet;
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
Soldering the circuit electrode of the film-like adhesive-attached semiconductor element to the circuit electrode of the semiconductor element mounting support member; and
A method for manufacturing a semiconductor device.

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