TW202248391A - Adhesive for semiconductor, adhesive sheet for semiconductor, and method for manufacturing semiconductor device - Google Patents

Abstract

According to the present invention, in a semiconductor device in which a plurality of connection portions of a semiconductor chip and a plurality of connection portions of a wiring circuit board are electrically connected to each other or a semiconductor device in which a plurality of connection portions of each of a plurality of semiconductor chips are electrically connected to each other, an adhesive for a semiconductor used for sealing at least a part of the connection portions electrically connected to each other is disclosed. The adhesive for a semiconductor contains an epoxy resin, a curing agent, a thermoplastic resin, and an inorganic filler. The inorganic filler contains an inorganic filler having an average particle diameter of 100-400 nm, or exhibits at least one peak at the position of the particle diameter of 100-400nm in the particle size distribution obtained when the particle size distribution of the inorganic filler is measured by dynamic light scattering.

Description

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

The disclosure relates to an adhesive for semiconductors, an adhesive sheet for semiconductors, and a method for manufacturing a semiconductor device.

In order to manufacture a semiconductor device, a flip chip connection method in which a semiconductor wafer having a bump as a connection portion is directly connected to a connection portion (electrode) of a printed circuit board via a bump may be used. In the flip-chip connection method, an underfill that fills the gap between the semiconductor chip and the printed circuit board and seals the connection is usually formed by an adhesive.

As a method of forming an underfill, there is known a method of injecting a liquid resin into the gap between the semiconductor chip and the printed circuit board after connecting the semiconductor chip and the printed circuit board (see Patent Document 1). An underfill is also sometimes formed using an adhesive film such as an anisotropic conductive adhesive film (ACF) or a non-conductive adhesive film (NCF) (see Patent Document 2).

For high functionality and high-speed operation, through-silicon via (TSV: Through Silicon Via) is attracting attention as a three-dimensional mounting technology that connects semiconductor chips with the shortest distance (see Non-Patent Document 1). Therefore, it is required to make the semiconductor wafer as thin as possible while maintaining the mechanical strength. In order to make a semiconductor wafer thinner, what is called back grinding which grinds the back surface of a semiconductor wafer may be performed. In order to simplify the back grinding process, a resin having both the function of holding the semiconductor wafer and the function of an underfill material has been proposed (see Patent Documents 3 and 4).

[Patent Document 1] Japanese Patent Laid-Open No. 2000-100862 [Patent Document 2] Japanese Unexamined Patent Publication No. 2003-142529 [Patent Document 3] Japanese Patent Laid-Open No. 2001-332520 [Patent Document 4] Japanese Patent Laid-Open No. 2005-028734

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

In recent years, since the amount of heat generated by semiconductor packages has increased along with higher volume and higher capacity, many dummy bumps for heat dissipation have been arranged in semiconductor packages. When such dummy bumps are used, conventional adhesives for semiconductors have insufficient fluidity during mounting, so sometimes the adhesives for semiconductors cannot be completely eliminated, which may lead to insufficient contact of the connection part. poor connection.

Therefore, the main object of the present disclosure is to provide an adhesive for semiconductors that has good fluidity during mounting and can suppress warpage of a semiconductor wafer.

One aspect of the present disclosure relates to an adhesive for semiconductors, which is a semiconductor device in which a plurality of connection parts of a semiconductor wafer and a plurality of connection parts of a printed circuit board are electrically connected to each other, or a plurality of connection parts of a plurality of semiconductor chips are mutually connected. In an electrically connected semiconductor device, it is used to seal at least a part of the connecting parts that are electrically connected to each other.

One aspect of the adhesive for semiconductors contains an epoxy resin, a curing agent, a thermoplastic resin, and an inorganic filler. The inorganic filler contains an inorganic filler with an average particle diameter of 100-400 nm.

Another aspect of the adhesive for semiconductors contains an epoxy resin, a curing agent, a thermoplastic resin, and an inorganic filler. Inorganic filler When the particle size distribution of the inorganic filler is measured by the dynamic light scattering method, in the obtained particle size distribution, at least one maximum value is displayed at the position of the particle diameter of 100-400 nm.

According to these adhesives for semiconductors, while having favorable fluidity at the time of mounting, warpage of a semiconductor wafer can be suppressed.

Based on the total amount of the adhesive for semiconductors, the content of the inorganic filler may be 20 to 60% by mass.

The inorganic filler may be at least one selected from the group consisting of silicon dioxide, aluminum oxide and silicon nitride.

The weight average molecular weight of the thermoplastic resin may be 20,000-200,000.

The curing agent may be an imidazole-based curing agent.

The adhesive agent for semiconductors may contain an organic acid further.

Another aspect of this disclosure relates to the adhesive sheet for semiconductors. This adhesive agent sheet for semiconductors is equipped with the adhesive agent layer provided on a support base material and the support base material, and containing the said adhesive agent for semiconductors. The supporting substrate may have a plastic film and an adhesive layer disposed on the plastic film. In this case, the adhesive layer is provided on the adhesive layer.

Another aspect of the present disclosure relates to a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device includes at least one step selected from the following steps: while an adhesive is interposed between a semiconductor chip having a plurality of connection parts and a wiring circuit board having a plurality of connection parts, the semiconductor chip, wiring A step of forming a bonded body by heating and pressing the circuit board and the adhesive, wherein the connection portion of the bonding system semiconductor wafer and the connection portion of the printed circuit board are electrically connected to each other, and at least a part of the connection portions are electrically connected to each other A bonded body sealed by a cured adhesive; while the adhesive is interposed between a plurality of semiconductor chips having a plurality of connection parts, the semiconductor chip and the adhesive are heated and pressurized to form the following bonded body In the bonding system, the connecting parts of the plurality of semiconductor wafers are electrically connected to each other, and at least a part of the connecting parts that are electrically connected to each other is sealed with a cured adhesive; and the adhesive is interposed between the semiconductor wafers having the plurality of connecting parts Simultaneously with the semiconductor wafer having a plurality of connecting parts, the semiconductor wafer, the semiconductor wafer and the adhesive are heated, thereby forming the following step of the joint body, the connecting part of the aforementioned bonding system semiconductor wafer and the semiconductor wafer The connecting parts are electrically connected to each other, and at least a part of the connecting parts electrically connected to each other is sealed with a cured adhesive. The adhesive is the above-mentioned adhesive for semiconductors.

The method of manufacturing a semiconductor device may further include the following steps: a step of preparing a semiconductor wafer, the aforementioned semiconductor wafer having a wafer body having two main surfaces and a plurality of connecting parts provided on one main surface of the wafer body; a step of providing an adhesive layer containing an adhesive on the main surface of the wafer body on the connection portion side; a step of thinning the wafer body by grinding the main surface of the wafer body opposite to the connection portion; and The step of forming an adhesive-coated semiconductor wafer having a semiconductor wafer and an adhesive layer by dicing the thinned wafer body and adhesive layer. [Invention effect]

According to the present disclosure, it is possible to provide an adhesive for semiconductors that has good fluidity at the time of mounting and can suppress warpage of a semiconductor wafer. Several types of adhesives for semiconductors have excellent visible light transmittance, so they are easy to align and have excellent sensor visibility. Moreover, according to this disclosure, the adhesive sheet for semiconductors using the adhesive agent for semiconductors, and the manufacturing method of a semiconductor device can be provided.

Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. However, this indication is not limited to the following embodiment.

In this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. Within the numerical ranges described step by step in this specification, the upper limit or lower limit of the numerical range of a certain stage may be replaced with the upper limit or lower limit of the numerical range of other stages. Moreover, within the numerical range described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in an Example. In addition, the upper limit and lower limit described individually can be combined arbitrarily. Moreover, in this specification, "(meth)acrylate" means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryl" and "(meth)acryl". In addition, "(poly)" refers to both the case where there is a prefix of "poly" and the case where it does not. Moreover, "A or B" should just include any one of A and B, and may include both. Moreover, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content of each component in the composition refers to the total amount of the plurality of substances present in the composition.

Fig. 1 is a schematic sectional view showing an embodiment of an adhesive tablet. The adhesive sheet 10 shown in FIG. 1 is an adhesive sheet for semiconductors, and the adhesive sheet for semiconductors includes a support base 3, an adhesive layer 2 provided on the support base 3, and a protective film 1 covering the adhesive layer 2. .

The adhesive layer 2 is a layer formed of a thermosetting adhesive. The adhesive forming the adhesive layer 2 contains an epoxy resin (hereinafter, sometimes referred to as "component (A)"), a curing agent (hereinafter, sometimes referred to as "component (B)"), a thermoplastic resin ( Hereinafter, it may be referred to as "component (C)".), Inorganic filler (hereinafter, it may be referred to as "component (D)") Adhesive for semiconductors. Adhesives for semiconductors are semi-cured (B-stage) and can be fully cured (C-stage) after curing.

(A) Component: epoxy resin The (A) component is not particularly limited as long as it is an epoxy resin that is cured and has an adhesive effect. epoxy resin. Examples of the component (A) include bifunctional epoxy resins such as bisphenol A epoxy resins, novolac epoxy resins such as phenol novolak epoxy resins, and cresol novolak epoxy resins, triphenol methane Type epoxy resin, etc. As the component (A), generally known resins such as polyfunctional epoxy resins, glycidylamine epoxy resins, heterocyclic ring-containing epoxy resins, and alicyclic epoxy resins can be used.

From the viewpoint of suppressing the generation of volatile components due to decomposition at the time of connection at high temperature, when the temperature at the time of connection is 250°C, use an epoxy whose thermal weight loss rate at 250°C is 5% or less for component (A) Resin is preferred. When the temperature at the time of connection is 300°C, it is preferable to use an epoxy resin whose thermal weight loss rate at 300°C is 5% or less.

From the viewpoint of maintaining the heat resistance and adhesiveness of the adhesive after formation, and exhibiting high reliability, the content of the component (A) may be 40-95 parts by mass, 50-90 parts by mass, 60-85 parts by mass, or 70-80 parts by mass. When content of (A) component is 40 mass parts or more, it exists in the tendency which becomes easy to obtain higher connection reliability. When content of (A) component is 95 mass parts or less, there exists a tendency for an adhesive agent layer to maintain a shape easily.

(B) Component: curing agent Examples of the component (B) include imidazole-based curing agents, phenolic resin-based curing agents, acid anhydride-based curing agents, amine-based curing agents, and phosphine-based curing agents. Among them, the component (B) may be an imidazole-based curing agent.

Content of (B) component can be 0.1-40 mass parts with respect to 100 mass parts of (A) components. When content of (A) component is 0.1 mass part or more, it exists in the tendency which becomes easy to obtain sufficient curing reaction rate. When content of (A) component is 40 mass parts or less, it exists in the tendency which maintains favorable heat resistance and adhesiveness easily. Content of a curing agent may be 1-30 mass parts, 3-20 mass parts, or 5-10 mass parts with respect to 100 mass parts of (A) components.

Examples of imidazole-based curing agents include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetrical triammonium, 2,4-diamine Base-6-[2'-Undecylimidazolyl-(1')]-Ethyl-Symmetrical Tris, 2,4-Diamino-6-[2'-Ethyl-4'-Methylimidazole Base-(1')]-Ethyl-Symmetrical Trisyl, 2,4-Diamino-6-[2'-Methylimidazolyl-(1')]-Ethyl-Symmetrical Trisaluron Acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole , Adducts of epoxy resins and imidazoles, etc. Among them, from the viewpoint of excellent curability, the imidazole-based curing agent may be 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetrical trisisocyanate Cyanuric acid adduct. The content of the imidazole-based curing agent may be the same as the content of the above-mentioned (B) component.

Examples of the phenolic resin-based curing agent include various polyfunctional novolac resins such as phenol novolac resins, cresol novolac resins, phenol aralkyl resins, cresol naphthol formaldehyde condensation polymers, and triphenylmethane type polyfunctional phenolic resins. resin etc. The equivalent ratio of the phenolic resin curing agent to (A) component (phenolic hydroxyl group of the phenolic resin curing agent/epoxy group of (A) component (mole)) can be 0.3 to 1.5, 0.4 to 1.0 or 0.5 to 1.0 .

Examples of acid anhydride curing agents include methylcyclohexanetetracarboxylic dianhydride, 1,2,4-benzenetricarboxylic anhydride, pyromelite, benzophenone tetracarboxylic dianhydride, ethylene glycol bis (Dehydration 1,2,4-benzene tricarboxylate) (ethylene glycol bis (anhydro trimellitate)) etc. The equivalent ratio of the acid anhydride curing agent to the component (A) (acid anhydride group of the acid anhydride curing agent/epoxy group (mole) of the component (A)) may be 0.3 to 1.5, 0.4 to 1.0, or 0.5 to 1.0.

As an amine hardening agent, dicyandiamine etc. are mentioned, for example. The equivalent ratio of the amine-based curing agent to the component (A) (amine group of the amine-based curing agent/epoxy group (mole) of the component (A)) may be 0.3-1.5, 0.4-1.0, or 0.5-1.0.

Examples of the phosphine-based curing agent include triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis(4-methylphenyl)borate, and tetraphenylphosphonium tetrakis(4-fluorophenyl)borate. The content of the phosphine curing agent may be 0.1 to 10 parts by mass or 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (A).

(C) Component: thermoplastic resin Examples of the component (C) include polyester resin, polyether resin, polyamide resin, polyamideimide resin, polyimide resin, polyvinyl butyral resin, polyvinyl formal resin, phenoxy resin, polyhydroxypolyether resin, acrylic resin, polystyrene resin, butadiene resin, acrylonitrile/butadiene copolymer, acrylonitrile/butadiene/styrene resin, styrene/butadiene Diene Copolymer, Acrylic Copolymer.

When the adhesive agent for semiconductors contains (C)component, the film formability of an adhesive agent can be made favorable. The film formability refers to the mechanical property that the adhesive layer is not easily torn, cracked, or sticky when the adhesive layer is formed into a film by an adhesive. If it is easy to handle as a film in a normal state (eg, normal temperature (25° C.)), it can be said that the film formability is good. Among these, since it is excellent in heat resistance and mechanical strength, (C) component may contain a polyimide resin or a phenoxy resin.

(C) The weight average molecular weight of a component may be 10,000-800,000, 15,000-500,000, or 20,000-200,000. When the weight average molecular weight is in such a range, it is easy to make the strength and flexibility of the sheet-like or film-like adhesive layer 2 well balanced, and the fluidity of the adhesive layer 2 becomes good, so it is possible to sufficiently ensure the stability of the wiring. Circuit filling (embedding). In the present specification, the weight average molecular weight refers to a value converted using a standard polystyrene calibration curve measured by gel permeation chromatography.

The glass transition temperature of (C)component may be 20-170 degreeC or 25-120 degreeC from a viewpoint of maintaining film formability and providing adhesiveness to the adhesive layer before hardening. When the glass transition temperature of the component (C) is 20°C or higher, the film formability at room temperature (25°C) can be maintained, and the adhesive layer 2 tends to be less likely to be deformed during the processing of the semiconductor wafer in the back grinding step . When the glass transition temperature of the component (C) is 170° C. or lower, the effect of improving the connection reliability by the adhesive after the thermal history tends to be exhibited more remarkably.

Content of (C)component can be 5-60 mass parts, 10-50 mass parts, 15-40 mass parts, or 20-30 mass parts with respect to 100 mass parts of total amounts of (A) component and (C)component. When the content of the component (C) is within such a range, the film formability of the adhesive can be improved, fluidity can be exhibited during thermocompression bonding, and the resin repellency between the bump and the circuit electrode can be improved. tendency.

(D) Component: Inorganic filler Examples of the component (D) include glass, silica, alumina, titanium oxide, carbon black, mica, and boron nitride. Among them, it may be at least one selected from the group consisting of silicon dioxide, aluminum oxide, titanium oxide and boron nitride, or at least one selected from the group consisting of silicon dioxide, aluminum oxide and silicon nitride. A sort of.

When the adhesive for semiconductors contains the component (D), the linear expansion coefficient and elastic modulus of the adhesive can be maintained, and warping of the semiconductor wafer tends to be suppressed.

(D) Component can be surface-treated with a surface treatment agent from the viewpoint of compatibility with the surface, an organic solvent, other components, etc., and adhesive strength. As a surface treatment agent, a silane coupling agent etc. are mentioned, for example. As a functional group of a silane coupling agent, a vinyl group, a (meth)acryl group, an epoxy group, a mercapto group, an amine group, a diamine group, an alkoxy group, an ethoxy group etc. are mentioned, for example.

(D) The component satisfies either one of the following condition (a) or condition (b), and it is preferable to satisfy both condition (a) and condition (b). ・Condition (a): Component (D) contains an inorganic filler with an average particle diameter of 100 to 400 nm (hereinafter, sometimes referred to as "component (D1)"). ・Condition (b): When the particle size distribution of component (D) is measured by the dynamic light scattering method, in the obtained particle size distribution, at least one maximum value is shown at the particle diameter of 100 to 400 nm.

In the condition (a), the average particle diameter of the (D1) component is 100 to 400 nm, for example, 130 to 350 nm or 150 to 300 nm. When the average particle size of the component (D1) is 100nm or more, the specific surface area of the particles does not become too large, the viscosity (fluidity) can be maintained moderately, the embedding property in the protruding electrodes is improved, and the residue with voids is difficult to occur. tendency. When the average particle diameter of the component (D1) is 400 nm or less, it tends to be possible to prevent a decrease in visible light transmittance due to scattering of visible light. In addition, in condition (a), the average particle diameter means the average particle diameter calculated|required by the dynamic light scattering method.

In the condition (a), based on the total amount of the component (D), the content of the component (D1) may be 50% by mass or more, 55% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more. Mass % or more, 90 mass % or more, or 95 mass % or more may be 100 mass %.

In condition (a), in addition to (D1) component, (D) component may contain an inorganic filler with an average particle Inorganic fillers with a diameter exceeding 400 nm (hereinafter, sometimes referred to as "(D3) component"). (D)component, for example, may contain (D3)component. (D3) The average particle diameter of a component can be 1000 nm or less, 800 nm or less, or 600 nm or less, for example. Based on the total amount of component (D), the total content of component (D2) and component (D3) may be 0 to 50% by mass, 0 to 45% by mass, 0 to 40% by mass, 0 to 30% by mass, or 0% by mass. ～20 mass %, 0～10 mass %, or 0～5 mass %.

In condition (b), the particle size distribution of (D) component can be measured by the following method using the adhesive agent for semiconductors, for example. First, an adhesive for a semiconductor is prepared, the adhesive for a semiconductor is mixed with acetone, and the mixture is irradiated with ultrasonic waves to dissolve components other than the component (D) (operation (a)). Next, the mixed solution is centrifuged using a centrifuge, and the supernatant is removed (operation (b)). Such operation (a) and operation (b) were repeated three times, and (D) component was obtained as a residue. Next, the component (D) which is a residue is re-dispersed in the solvent for measurement, this is used as a measurement sample, and the particle size distribution is measured by the dynamic light scattering method.

In the condition (b), the component (D) exhibits at least one maximum value at a particle diameter of 100 to 400 nm in the obtained particle size distribution. (D) As long as the component exhibits at least one maximum value at a position of 100 to 400 nm in particle diameter, it may also exhibit a maximum value at a position less than 100 nm in particle diameter or at a position exceeding 400 nm in particle diameter. (D) It is preferable that the component shows at least one maximum value only at the particle diameter of 100 to 400 nm.

The content of the component (D) may be 10 to 80% by mass, 15 to 70% by mass, or 20 to 60% by mass based on the total amount of the adhesive for semiconductors. When the content of the component (D) is 10% by mass or more, the increase in the coefficient of linear expansion and the decrease in the elastic modulus of the adhesive layer 2 are prevented, and the connection reliability between the semiconductor wafer and the substrate after pressure bonding tends to be easily maintained. . When the content of the component (D) is 80% by mass or less, it is easy to maintain the melt viscosity of the adhesive, by preventing the decrease in the wettability of the interface between the semiconductor wafer and the adhesive layer 2 or the interface between the circuit board and the adhesive layer 2 , there is a tendency to prevent the occurrence of remaining voids caused by peeling or insufficient embedding.

The adhesive agent for semiconductors may also contain an organic acid (Hereinafter, it may be referred to as "(E) component."). (E) The component functions as a flux. That is, the component (E) has a melting point at a temperature lower than that of the solder, and can improve the solder wettability of the adhesive layer by removing oxides on the surface of the solder and metal surfaces such as circuit electrodes after melting. (E) The component may be an organic acid having a carboxyl group.

(E) The component is preferably dissolved in an organic solvent used for preparing the resin varnish. Then, in the film forming step, the organic solvent is vaporized by heating, whereby the dissolved component (E) is precipitated again, and is uniformly present in the film as a fine powder. Therefore, the specific surface area of the flux increases, and the number of contact points with the oxide film increases, so that the oxide film is easily removed, and solder connectivity is improved.

The melting point of the component (E) may be 50 to 200° C. from the viewpoint of melting and liquefying the fine powder flux during thermocompression bonding to improve flux properties. When the melting point of the component (E) is within such a range, higher connection reliability tends to be easily obtained.

(E) The melting point of the component can be measured using a usual melting point measuring device. For the sample for measuring the melting point, it is required to reduce the temperature deviation in the sample by pulverizing into fine powder and using a small amount. As a sample container, capillary tubes with one end closed are often used, but depending on the measuring device, there are also containers sandwiched between two microscope coverslips as containers. In addition, if the temperature is raised rapidly, a temperature gradient will be generated between the sample and the thermometer to cause a measurement error. Therefore, it is preferable to measure the heating of the point at the time of measuring the melting point at a rate of increase of 1° C. per minute or less.

The content of the component (E) may be 0.1 to 20% by mass or 0.5 to 10% by mass based on the total amount of the adhesive for semiconductors. When the content of the component (E) is within this range, it is easy to ensure good solder wettability.

The adhesive agent for semiconductors may contain an organic filler (Hereinafter, it may be called "(F) component."). When the adhesive agent for semiconductors contains (F) component, the adhesiveness etc. of an adhesive agent can be controlled. Since the component (F) is generally insoluble in an organic solvent, it can be formulated into an adhesive while maintaining the particle shape. Therefore, the component (F) can be dispersed in the form of islands in the adhesive layer 2 after curing, and the strength of the connected body can be kept high. Thereby, a function as an impact-resistant mitigating agent having stress relieving properties can be imparted to the adhesive.

Examples of the component (F) include acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, Copolymer with polystyrene, NBR, SBR, polysiloxane modified resin, etc. as ingredients.

The component (F) may be an organic filler having a molecular weight of 1,000,000 or more or an organic filler having a three-dimensional crosslinked structure from the viewpoint of improving dispersibility to the adhesive, stress relaxation, and adhesiveness. Examples of such organic fillers include alkyl (meth)acrylate-butadiene-styrene copolymers; alkyl (meth)acrylate-polysiloxane copolymers; polysiloxane-(methyl) ) acrylic acid copolymers; such complexes, etc. Here, "an organic filler with a molecular weight of 1 million or more or an organic filler with a three-dimensional cross-linked structure" refers to an organic filler that has poor solubility in solvents due to its ultra-high molecular weight, or an organic filler that has a three-dimensional network structure, so Organic fillers with poor solubility in solvents. (F) The component has a core-shell structure, and organic fillers having different compositions in the core layer and the shell layer can also be used. Examples of the core-shell type organic filler include particles obtained by grafting acrylic resin with polysiloxane-acrylic rubber as a core, and particles obtained by grafting acrylic resin to acrylic copolymer.

(F) The average particle diameter of a component can be 0.1-2 micrometers, for example. When the average particle diameter is 0.1 μm or more, the effect of suppressing voids tends to be easily obtained.

The content of the component (F) may be 5 to 20% by mass based on the total amount of the adhesive for semiconductors in order to impart void suppression during connection and stress relaxation after connection to the adhesive layer.

Various coupling agents can also be added to the adhesive for semiconductors in order to modify the surface of the filler to improve the interfacial bonding between different materials, thereby increasing the bonding strength. As a coupling agent, coupling agents, such as a silane type, a titanium type, and an aluminum type, are mentioned, for example. In terms of high effect, the coupling agent may be a silane-based coupling agent.

Examples of silane-based coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureapropyltriethoxysilane, 3-ureapropyltrimethoxysilane, etc.

In order to adsorb ionic impurities and improve insulation reliability during moisture absorption, an ion-scavenging agent can also be added to the adhesive for semiconductors. Examples of ion trapping agents include tristhiol compounds; compounds known as copper inhibitors such as bisphenol-based reducing agents to prevent ionized elution of copper; zirconium-based compounds; antimony-bismuth-based compounds; magnesium-aluminum-based compounds and other inorganic ion adsorbents.

The adhesive tablet 10 may be an anisotropic conductive adhesive film (ACF) in which the adhesive layer 2 contains conductive particles, or a non-conductive adhesive film (NCF) in which the adhesive layer 2 does not contain conductive particles.

Regarding the adhesive layer 2 formed of the adhesive for semiconductors, the reaction rate measured by DSC after heating at 250° C. for 10 seconds may be 60% or more or 70% or more. After storing the adhesive tablet at room temperature for 14 days, the reaction rate of the adhesive layer 2 measured by DSC may not reach 10%.

The visible light transmittance of the adhesive layer 2 formed of the adhesive for semiconductors may be 5% or more, 8% or more, or 10% or more. When the visible light transmittance is 5% or more, alignment tends to be difficult. On the other hand, the upper limit of the visible light transmittance is not particularly limited.

The adhesive layer 2 can be formed by dissolving or dispersing an adhesive for semiconductors in an organic solvent to form a resin varnish, applying the resin varnish on the protective film 1, and removing the organic solvent by heating. Then, the adhesive sheet 10 of this embodiment can be obtained by laminating the support base material 3 on the adhesive layer 2 at normal temperature (25 degreeC) - 80 degreeC. The adhesive layer 2 can also be formed by applying the above-mentioned resin varnish on the support substrate 3 and removing the organic solvent by heating.

Examples of organic solvents include aromatic hydrocarbons such as toluene, xylene, p-cymene, cumene, and p-cymene; aliphatic hydrocarbons such as hexane and heptane; and cyclic alkanes such as methylcyclohexane; Tetrahydrofuran, 1,4-dioxane and other cyclic ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and other ketones; methyl acetate Esters, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone and other esters; ethyl carbonate, propylene carbonate and other carbonates; N,N-dimethylformamide, N , Amides such as N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.

As the protective film 1, plastic films, such as a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polymethylpentene film, etc. are mentioned, for example. From the viewpoint of releasability, as the protective film 1 , a film made of a fluororesin such as a polytetrafluoroethylene film and having a low surface energy may be used.

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 may be 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. As a commercially available protective film treated with a release agent, for example, "A-63" (release treatment agent: modified silicone system) and "A-31" (release agent) manufactured by TOYOBO FILM SOLUTIONS LIMITED. Mold treatment agent: Pt-based polysiloxane).

The thickness of the protective film 1 may be 10-100 μm, 10-75 μm or 25-50 μm. When the thickness of the protective film 1 is 10 μm or more, the protective film tends to be less likely to be broken during coating, and when the thickness of the protective film 1 is 100 μm or less, it tends to be easily purchased at a low price.

Examples of the method of coating the above resin varnish on the protective film 1 (or the supporting substrate 3) include knife coating, roll coating, spray coating, gravure coating, bar coating, and curtain coating. known methods such as law.

The thickness of the adhesive layer 2 is not particularly limited, and may be 5-200 μm, 7-150 μm, or 10-100 μm. When the thickness of the adhesive layer 2 is 5 μm or more, it tends to be easy to ensure sufficient adhesive force, and to easily bury the protruding electrodes of the circuit board. When the thickness of the adhesive layer 2 is 200 μm or less, it is economically advantageous and tends to easily meet the demand for miniaturization of semiconductor devices.

As the supporting substrate 3, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polymethylpentene film, polyvinyl acetate film, polyvinyl chloride film , Polyimide film and other plastic films. The support substrate 3 may be a substrate obtained by mixing two or more materials selected from the above-mentioned materials, or a substrate obtained by multilayering the above-mentioned films.

The thickness of the supporting substrate 3 may be, for example, 5 to 250 μm. When the thickness of the supporting base material 3 is 5 μm or more, it tends to be possible to prevent breakage of the supporting base material during grinding (back grinding) of the semiconductor wafer. When the thickness of the supporting base material 3 is 250 μm or less, it tends to be economically advantageous.

The minimum light transmittance in the wavelength region of 500 to 800 nm of the supporting base material 3 may be 10% or more.

As the support base material 3, a base material in which an adhesive layer is laminated on the above-mentioned plastic film can be used.

Fig. 2 is a schematic sectional view showing another embodiment of the adhesive tablet. The adhesive sheet 11 shown in Fig. 2 is equipped with: a supporting base material 3 having a plastic film 3b and an adhesive layer 3a disposed on the plastic film 3b; an adhesive layer 2 disposed on the adhesive layer 3a and formed by the present embodiment The semiconductor is formed with an adhesive; and the protective film 1 covers the adhesive layer 2 .

In order to improve the adhesion between the plastic film 3b and the adhesive layer 3a, chemical or physical treatments such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, and ionizing radiation treatment can also be performed on the surface of the plastic film 3b.

The adhesive layer 3 a has adhesive force at room temperature (25° C.), and may have the required adhesion force to the adherend. The adhesive layer 3a may also have the property of being cured by high-energy rays such as radiation or heat (that is, the adhesive force is lowered). The adhesive layer 3 a can be formed using, for example, acrylic resin, various synthetic rubbers, natural rubber, and polyimide resin. The thickness of the adhesive layer 3 a may be, for example, 5 to 20 μm.

The adhesive tablets 10 and 11 can be used in a semiconductor device in which a plurality of connection parts of a semiconductor chip and a plurality of connection parts of a printed circuit board are electrically connected to each other, or in a semiconductor device in which a plurality of connection parts of a plurality of semiconductor chips are electrically connected to each other, Used to seal at least a part of the connection portions electrically connected to each other. The adhesive sheets 10 and 11 can also be used as an adhesive in a build-up technique using through-silicon electrodes.

Hereinafter, an example of a method of manufacturing a semiconductor device using the adhesive sheet 10 or 11 will be described. 3, 4, 5, 6 and 7 are schematic cross-sectional views showing an embodiment of a method of manufacturing a semiconductor device. The method shown in FIGS. 3 to 7 consists of the steps of preparing a semiconductor wafer with a wafer body A having two main surfaces and a plurality of connecting portions 20 provided on one main surface of the wafer body A. The step of 30; the step of setting the adhesive layer 2 containing the adhesive on the main surface of the connection part 20 side of the wafer body A; Grinding, the step of thinning the wafer body A; by cutting the thinned wafer body A and the adhesive layer 2, forming a semiconductor wafer 30' with a wafer body A' and a plurality of connecting parts 20 and an adhesive layer 2. The step of the semiconductor wafer 35 with adhesive; and the step of forming the bonding body 50, that is, the adhesive layer 2 is interposed between the semiconductor chip 30' having a plurality of connecting parts 20 and the wiring circuit having a plurality of connecting parts 22 Simultaneously between the substrates 40, the semiconductor wafer 30', the printed circuit board 40, and the adhesive layer 2 are heated, whereby the connection portion 20 of the semiconductor wafer 30' and the connection portion 22 of the printed circuit board 40 are electrically connected to each other, and are connected to each other. The connection portions 20, 22 for electrical connection are sealed by the cured adhesive layer 2a.

As shown in FIG. 3 , the adhesive layer 2 on the support substrate 3 is pasted on the main surface of the wafer body A on one side where the connection portion 20 is provided, to obtain a laminated support substrate 3/adhesive layer 2/semiconductor A laminated body made of wafer 30 . Part or all of the plurality of connection portions 20 provided on the wafer body A may be solder bumps for solder bonding. A part or all of the connecting portion 22 of the printed circuit board 40 may be a solder bump.

In order to obtain a laminate in which the supporting base material 3/adhesive layer 2/semiconductor wafer 30 are laminated, a commercially available film attaching device or laminator can be used. In order to stick the adhesive layer 2 on the semiconductor wafer 30 without getting involved in voids, the sticking device may include a heating mechanism and a pressurizing mechanism, and may also include a vacuum suction mechanism. The adhesive layer 2 can also be pasted on the semiconductor wafer 30 using a roll-shaped or sheet-shaped adhesive sheet 10 processed according to the shape of the semiconductor wafer 30 .

It is desirable to attach the adhesive layer 2 on the semiconductor wafer 30 at a temperature at which the adhesive layer 2 softens. The temperature for attaching may be 40-80°C, 50-80°C or 60-80°C.

Next, as shown in FIG. 4 , the surface of the wafer body A opposite to the side on which the connection portion 20 is provided is ground by the grinder 4 to make the wafer body A thinner. The thickness of the thinned wafer body A may be, for example, 10-300 μm or 20-100 μm.

Grinding of the wafer body A can be performed using a common back grinding (B/G) apparatus. In order to grind the wafer body A uniformly without thickness unevenness in the B/G step, the adhesive layer 2 can also be uniformly attached to the semiconductor wafer 30 without being involved in voids.

As shown in FIG. 5( a ), the dicing tape 5 is attached to the semiconductor wafer 30 of the laminate, which is placed on a predetermined device, and the supporting base material 3 is peeled off. At this time, as in the adhesive sheet 11 shown in FIG. The adhesive layer 3a can be hardened, and the adhesive force between the adhesive layer 2 and the support base material 3 can be reduced. Among these, examples of radiation to be used include ultraviolet rays, electron beams, infrared rays, and the like. Thereby, the support base material 3 can be peeled off easily. After the supporting substrate 3 is peeled off, as shown in FIG. 5( b ), the wafer body A and the adhesive layer 2 of the semiconductor wafer 30 are cut by the dicing saw 6 . In this way, the wafer body A is divided into a plurality of wafer bodies A', and the adhesive layer 2 is divided into a plurality of parts on the wafer body A'. By dicing, a singulated semiconductor wafer 30' having a wafer body A' and a plurality of connecting portions 20 is formed.

Next, as shown in FIG. 6, by expanding (expanding) the dicing tape 5, the semiconductor wafers 30' are separated from each other, and the wafers 30' are picked up by suction from the dicing tape 5 side upwards with a needle using a suction collet 7. Semiconductor wafer 30 ′ and semiconductor wafer 35 with adhesive formed by adhesive layer 2 . The semiconductor chip 35 with the adhesive can be reeled and recovered, or it can be directly mounted on the printed circuit board 40 by using a flip chip bonder.

The operation of attaching the dicing tape 5 to the ground wafer body A can be carried out in the same step as the step of fixing to the dicing frame using a normal wafer mounter. The dicing tape 5 can be a commercially available dicing tape, which can be UV curable or pressure sensitive.

As shown in FIG. 7 , the semiconductor chip 35 and the printed circuit board 40 are thermocompression-bonded by aligning the connecting portion 20 of the semiconductor chip 30' and the connecting portion 22 of the printed circuit board 40 . By this thermocompression bonding, a bonded body 50 composed of the printed circuit board 40, the semiconductor chip 30', and the cured adhesive layer 2a is formed. The printed circuit board 40 has a base material 8 and a plurality of connecting portions 22 provided on the base material 8 . The connection portion 20 and the connection portion 22 are electrically and mechanically connected by solder bonding or the like. Between the semiconductor wafer 30' and the printed circuit board 40, a cured adhesive layer 2a is formed to seal the connection portions 20, 22. The step of forming the bonded body 50 may also include: a step of forming a temporary crimped body by thermocompression-bonding the semiconductor wafer 35 with an adhesive agent and the wiring circuit board 40 at a temperature lower than the melting point of the connection portions 20, 22; and A step of forming the bonded body 50 by heating and pressurizing the temporarily crimped body at a temperature at which at least one of the connection portions 20 or 22 melts.

From the viewpoint of solder bonding, the temperature at the time of thermocompression bonding may be 200°C or higher or 220 to 260°C. The thermocompression bonding time may be 1 to 20 seconds. The pressure of thermocompression bonding can be 0.1-5 MPa.

When mounting on the printed circuit board 40 using a flip chip bonder, the connection portions 20, 22 can be aligned by referring to the alignment marks formed on the circuit surface of the chip body A'.

Through the above-mentioned steps, a semiconductor device including a bonded body 50 having a printed circuit board 40 , a semiconductor chip 30 ′ mounted on the printed circuit board 40 , and sealed connection portions 20 and 22 interposed therebetween is obtained. The adhesive layer 2a.

Fig. 8 is a schematic cross-sectional view showing another embodiment of a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device shown in FIG. 8 includes the step of forming the bonding body 50 as follows, that is, the adhesive layer 2 formed by the adhesive is interposed between the semiconductor wafer 30 ′ having a plurality of connection portions 20 and the semiconductor wafer 30 ′ having a plurality of connection portions 23 Simultaneously between the semiconductor wafers 30, the semiconductor wafer 30', the semiconductor wafer 30 and the adhesive layer 2 are heated, whereby the connection portion 20 of the semiconductor wafer 30' and the connection portion 23 of the semiconductor wafer A are electrically connected to each other , and the connection portions 22 and 23 that are electrically connected to each other are sealed by the adhesive layer 2a, and the adhesive layer 2a is formed of a cured adhesive. More specifically, the step of forming the bonding body 50 includes: a step of disposing the semiconductor wafer 30 on the workbench 60 as shown in FIG. 8( a ); 1. The step of the laminated body composed of the adhesive layer 2 and the semiconductor wafer 30', that is, the temporary crimped body 55; as shown in FIG. Next, heat and pressurize the temporary crimping body 55 to form the bonding body 50 in which the connecting portion 20 and the connecting portion 23 are electrically connected as shown in FIG. 8( d ); A step of further heating and pressurizing the bonded body 50 in the pressure oven 90 .

The connection portion 20 of the semiconductor chip 30' has a post or bump 20a provided on the chip body A' and a solder 20b provided on the post or bump 20a. The semiconductor wafer 30 has a wafer body A, wiring 15 disposed on the wafer body A, connection portions 24 disposed on the wiring 15 , and a passivation film 16 disposed on the wafer body A and covering the wiring 15 .

The temporary press-bonded body 55 is formed by thermocompression-bonding the semiconductor wafer 35 with the adhesive on the semiconductor wafer 30 using the crimping tool 70 on the heated workbench 60 . The heating temperature of the table 60 is lower than the melting point of the connection part 20 (especially the solder 20 b ) and the melting point of the connection part 23 , for example, may be 60-150° C. or 70-100° C. The temperature of the crimping tool 70 may be, for example, 80-350°C or 100-170°C. The time for thermocompression bonding to form the temporarily crimped body 55 may be, for example, 5 seconds or less, 3 seconds or less, or 2 seconds or less.

The bonded body 50 is heated to a temperature above at least one of the melting point of the connecting portion 20 (especially the solder 20 b ) or the melting point of the connecting portion 23 by using the crimping tool 80 to heat the temporary crimped body 55 on the heated workbench 60 . formed under pressure. The temperature of the crimping tool 80 may be, for example, 180°C or higher, 220°C or higher, or 250°C or higher, and may be 350°C or lower, 320°C or lower, or 300°C or lower. The heating temperature of the workbench 60 during the thermocompression bonding for forming the bonded body 50 may be 60-150°C or 70-100°C. The time for thermocompression bonding by the crimping tool 80 to form the bonded body 50 may be, for example, 5 seconds or less, 3 seconds or less, or 2 seconds or less.

The curing of the adhesive layer 2 is sufficiently advanced by heating and pressurizing in the pressurized oven 90 . However, in the process of heating and pressing for forming the bonded body 50, curing of the adhesive layer 2 may also be partially performed. The heating temperature of the pressurized oven 90 may be a temperature at which the curing of the adhesive layer 2 does not reach the melting point of the connecting portions 20 and 24 , and may be, for example, 170 to 200° C.

It is also possible to sequentially mount a plurality of semiconductor wafers 30 ′ on a semiconductor wafer 30 with an adhesive layer 2 interposed therebetween to form a bonded body 50 with a plurality of semiconductor wafers 30 ′, and then heat and add heat in a pressurized oven 90 . Compression body 50 . At this time, the adhesive layer 2 between the semiconductor wafer 30' initially placed on the semiconductor wafer 30 and the semiconductor wafer 30 continues to experience the thermal history of the stage 60 until all the semiconductor wafers 30' are loaded. . The adhesive layer 2 containing the adhesive of the above embodiment can provide the bonded body 50 with high reliability even after a long time heat history.

The manufacturing method of the semiconductor device of this embodiment may also include the following steps: while interposing an adhesive layer containing an adhesive between a plurality of semiconductor wafers having a plurality of connection parts, the connection part of the semiconductor wafer and the adhesive layer Heating is performed to electrically connect the connection portions of the plurality of semiconductor chips to each other, and at least a part of the connection portions electrically connected to each other is sealed by the cured adhesive.

The adhesive for semiconductors of this embodiment and the adhesive layer formed from the adhesive are excellent in embedment and adhesive force after curing, and can remove the oxide film formed on the surface of the solder even in a short-term solder joint, Can improve solder wettability. Therefore, the bonded body 50 can sufficiently suppress the generation of voids, the connection parts can be well bonded to each other, the semiconductor chip 30' and the printed circuit board 40, the semiconductor chip 30 or other semiconductor chips can be bonded with sufficient adhesive force, and the reflow resistance (reflow resistance) can be achieved. ) Joints with excellent breakability and connection reliability. [Example]

Hereinafter, an Example and a comparative example are given and this indication is demonstrated more concretely. However, the present disclosure is not limited to these Examples.

The compounds used in each Example and Comparative Example are as follows. (A) Component: epoxy resin ・A-1: Multifunctional solid epoxy resin containing a trisphenolmethane skeleton (manufactured by Mitsubishi Chemical Corporation., trade name "EP1032H60") ・A-2: Bisphenol F type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YL983U") ・A-3: Flexible epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "YX7110B80") (B) Component: curing agent ・B-1: 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-symmetric tris-isocyanuric acid adduct (manufactured by SHIKOKU CHEMICALS CORPORATION. , trade name "2MAOK-PW") (C) Component: thermoplastic resin ・C-1: Phenoxy resin (manufactured by NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD., trade name "FX293") (D) Component: Inorganic filler ・D1-1: Silica filler treated with methacrylate silane (average particle size: 180nm) (manufactured by Admatechs Corporation, trade name "KG180G-HLA") ・D1-2: Silica filler treated with methacrylate silane (average particle diameter: 300nm) (manufactured by Admatechs Corporation, trade name "3SM-EH1") ・D2-1: Silica methacrylate surface-treated filler (average particle size 50nm) (manufactured by Admatechs Corporation, trade name "YA050C-SE1") ・D3-1: Silica filler (average particle diameter 500nm) (manufactured by Admatechs Corporation, trade name "SE2050") ・D3-2: Epoxysilane-treated silica filler (average particle size 500nm) (manufactured by Admatechs Corporation, trade name "SE2050-SEJ")

＜Production of adhesives for semiconductors＞ (A) component, (B) component, (C) component, and (D) component (A) component, (B) component, (C) component, and (D) component in the compounding quantity (unit: mass part) shown in Table 1 were added so that NV value (solid content amount) might become 50 mass % Organic solvent (cyclohexanone). Then, Φ1.0mm beads and Φ2.0mm zirconia beads having the same mass as the solid content were added to the same container, and stirred with a ball mill (Fritsch Japan Co., Ltd., planetary fine pulverizer P-7) 30 minutes. After stirring, the zirconia beads were removed by filtration to prepare a resin varnish.

The obtained resin varnish was coated on a substrate film (manufactured by Teijin Dupont Films Japan Ltd., trade name "Purex A55") with a small precision coating device (Yasui Seiki Inc.), and was dried in a clean oven (manufactured by ESPEC CORP) By drying under the condition of 100 degreeC/5 minutes, the adhesive agent for semiconductors of Examples 1-4 and the adhesive agent for comparative example 1 of the film form of 20 micrometers in thickness were obtained.

＜Evaluation of Adhesives for Semiconductors＞ (measurement of melt viscosity) Using the adhesives for semiconductors of Examples and Comparative Examples, the melt viscosity (130° C. shear viscosity) at 130° C. was measured using a rotational rheometer (manufactured by TA Instruments, trade name: ARES-G2). The results are shown in Table 1.

(Measurement of Coefficient of Linear Expansion (CTE)) Evaluation samples were prepared by curing the adhesives for semiconductors of Examples and Comparative Examples on the conditions of 170° C. and 2 hours. For the obtained evaluation samples, the coefficient of linear expansion (CTE) was measured using a thermomechanical analysis apparatus (trade name "TMA/SS7100", manufactured by Hitachi High-Tech Science Corporation). The measurement mode is tensile mode, the measurement load is 20-49mN, the measurement environment is atmospheric environment, the heating rate is 10°C/min for the 1st operation, 5°C/min for the 2nd operation, and the measurement results at 50-70°C for the 2nd operation are set to is α ₁ (ppm/°C). The results are shown in Table 1.

(measurement of visible light transmittance) Visible light transmittance was measured for the adhesives for semiconductors of Examples 1 to 4 excellent in melt viscosity and coefficient of linear expansion (CTE). Visible light transmittance was measured using a U-3310 model spectrophotometer (manufactured by Hitachi, Ltd.). The measurement procedure is to measure the transmittance of the film adhesive of the example in the visible light region of 400 to 800 nm after performing baseline correction measurement using the base film (manufactured by Teijin Dupont Films Japan Ltd., trade name "Purex A55") as a reference substance rate, and the transmittance at 550 nm was taken as the visible light transmittance. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 (A) A-1 45 45 45 45 45 A-2 15 15 15 15 15 A-3 5 5 5 5 5 (B) B-1 5 5 5 5 5 (C) C-1 20 20 20 20 20 (D) D2-1 - - - - 40 D1-1 70 35 - 40 - D1-2 - 35 70 - - D3-1 - - - 15 15 D3-2 - - - 15 15 Melt viscosity@130℃（Pa・s） 1700 1300 950 1500 3500 Linear expansion coefficient α ₁ (ppm/℃) 34 35 35 41 41 Visible light transmittance @550nm (%) 30 twenty two 15 5 -

As shown in Table 1, compared with the adhesive for semiconductors of Comparative Example 1, the adhesives for semiconductors of Examples 1 to 4 tended to have a lower melt viscosity at 130° C. and the same or lower linear expansion coefficients. From these results, it was confirmed that the adhesive agent for semiconductors of this disclosure has favorable fluidity at the time of mounting, and can suppress the warpage of a semiconductor wafer.

1: Protective film 2: Adhesive layer 2a: Cured adhesive layer 3: Support base material 3a: Adhesive layer 3b: plastic film 4: Grinder 5: Cutting tape 6: Chopping saw 7: Suction collet 8: Substrate 10,11: Follower tablets 20: Connecting part 22: Connecting part 30: Semiconductor wafer 30': Semiconductor wafer 35: Semiconductor wafer with adhesive 40: Wiring circuit board 50:Joint body

Fig. 1 is a schematic sectional view showing another embodiment of an adhesive tablet. Fig. 2 is a schematic sectional view showing another embodiment of the adhesive tablet. Fig. 3 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 4 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device. 5 is a schematic cross-sectional view showing one embodiment of a method for manufacturing a semiconductor device, and FIGS. 5( a ) and 5 ( b ) are schematic cross-sectional views showing each step. Fig. 6 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 7 is a schematic cross-sectional view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 8 is a schematic cross-sectional view showing another embodiment of a manufacturing method of a semiconductor device, and Fig. 8(a), Fig. 8(b), Fig. 8(c), Fig. 8(d) and Fig. 8(e) show Schematic sectional view of each step.

Claims (11)

An adhesive for semiconductors, which is used in a semiconductor device in which a plurality of connection parts of a semiconductor chip and a plurality of connection parts of a printed circuit board are electrically connected to each other, or in a semiconductor device in which a plurality of connection parts of a plurality of semiconductor chips are electrically connected to each other, For sealing at least a part of the aforementioned connecting portions electrically connected to each other, wherein The aforementioned semiconductor adhesive contains epoxy resin, curing agent, thermoplastic resin and inorganic filler, The aforementioned inorganic filler includes an inorganic filler with an average particle diameter of 100 to 400 nm. An adhesive for semiconductors, which is used in a semiconductor device in which a plurality of connection parts of a semiconductor chip and a plurality of connection parts of a printed circuit board are electrically connected to each other, or in a semiconductor device in which a plurality of connection parts of a plurality of semiconductor chips are electrically connected to each other, For sealing at least a part of the aforementioned connecting portions electrically connected to each other, wherein The aforementioned semiconductor adhesive contains epoxy resin, curing agent, thermoplastic resin and inorganic filler, When the particle size distribution of the inorganic filler is measured by the dynamic light scattering method, in the obtained particle size distribution, at least one maximum value is displayed at the position of the particle diameter of 100-400 nm. The adhesive for semiconductors as described in Claim 1 or Claim 2, wherein Based on the total amount of the adhesive for semiconductors, the content of the aforementioned inorganic filler is 20 to 60% by mass. The adhesive for semiconductor according to any one of claim 1 to claim 3, wherein The aforementioned inorganic filler is at least one selected from the group consisting of silicon dioxide, aluminum oxide and silicon nitride. The adhesive for semiconductors according to any one of claim 1 to claim 4, wherein The weight average molecular weight of the said thermoplastic resin is 20000-200000. The adhesive for semiconductor according to any one of claim 1 to claim 5, wherein The aforementioned curing agent is an imidazole-based curing agent. The adhesive for semiconductors according to any one of claim 1 to claim 6, which further contains an organic acid. An adhesive sheet for a semiconductor comprising a support substrate and an adhesive layer provided on the support substrate and containing the adhesive for a semiconductor according to any one of claim 1 to claim 7. The adhesive sheet for semiconductors according to claim 8, wherein The aforementioned supporting substrate has a plastic film and an adhesive layer disposed on the aforementioned plastic film, and the aforementioned adhesive layer is disposed on the aforementioned adhesive layer. A method of manufacturing a semiconductor device, comprising at least one step selected from the following steps: While interposing an adhesive agent between a semiconductor wafer having a plurality of connection portions and a wiring circuit board having a plurality of connection portions, heating and pressing the semiconductor wafer, the wiring circuit board, and the adhesive agent, thereby forming A step of the bonded body, wherein the bonding system is a joint in which the connection portion of the semiconductor wafer and the connection portion of the printed circuit board are electrically connected to each other, and at least a part of the connection portions electrically connected to each other is sealed with the cured adhesive body; A step of forming a junction body by heating and pressing the semiconductor wafer and the adhesive while interposing the adhesive between the plurality of semiconductor wafers having the plurality of connection parts, the junction system comprising the plurality of the aforementioned semiconductor The connection parts of the wafer are electrically connected to each other, and at least a part of the connection parts electrically connected to each other is sealed with the cured adhesive; and While interposing an adhesive agent between a semiconductor wafer having a plurality of connection portions and a semiconductor wafer having a plurality of connection portions, the semiconductor wafer, the semiconductor wafer, and the adhesive agent are heated to form the following bonded body The step of the bonding system is a bonded body in which the aforementioned connecting portion of the aforementioned semiconductor wafer and the aforementioned connecting portion of the aforementioned semiconductor wafer are electrically connected to each other, and at least a part of the aforementioned connecting portion that is electrically connected to each other is sealed by the cured adhesive, The aforementioned adhesive is the adhesive for semiconductors described in any one of claim 1 to claim 7. According to the method for manufacturing a semiconductor device as described in claim 10, the method for manufacturing a semiconductor device further includes the following steps: A step of preparing a semiconductor wafer, the aforementioned semiconductor wafer having a wafer body having two main surfaces and a plurality of the aforementioned connection portions provided on one main surface of the aforementioned wafer body; A step of providing an adhesive layer containing the adhesive on the main surface of the wafer body on the side of the connecting portion; a step of thinning the wafer body by grinding the main surface of the wafer body opposite to the connecting portion; and A step of forming an adhesive-attached semiconductor wafer having the aforementioned semiconductor wafer and the aforementioned adhesive layer by dicing the thinned aforementioned wafer body and the aforementioned adhesive layer.

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