JP5252698B2 - Resin bump composition - Google Patents

Description

The present invention relates to a resin bump composition used in a flip chip mounting method. Specifically, it contains predetermined thermoplastic resin particles and a silicone-modified resin, and has a good printability and forms a stable B-stage state. And a resin composition that gives a cured product having a low elastic modulus.

The flip chip mounting method is a method in which a semiconductor chip is connected to an electrode on a substrate via a solder bump formed on an electrode pad on the chip, and is often used for miniaturizing a circuit. . By filling an underfill in the gap between the connected semiconductor chip and the wiring board, it is possible to improve the connection reliability between the solder bump and the electrode pad provided on the wiring board (Patent Document 1). .

Instead of solder bumps, it is known to use a conductive resin bump printed on a circuit and temporarily cured (Patent Document 2). As conductive resin, what mixed metal particles, such as Ag powder with an average particle diameter of 10 micrometers or less, in binders, such as an epoxy resin, is used.
JP 2005-353672 A JP 2004-95832 A

However, it is not easy to control the degree of temporary curing of the epoxy resin composition. If curing proceeds too much, a flip chip connection cannot be formed. In addition, the cured epoxy resin is generally less susceptible to thermal shock than the solder bump, and is likely to be cracked by heat from the circuit, wire bonding, resin sealing process, or the like. In particular, when the semiconductor chip has an interlayer low dielectric constant film (hereinafter referred to as “Low-k film”), it is possible to form a reliable connection to both the semiconductor chip and the electrode pad on the substrate. Have difficulty. By filling the underfill agent between the bumps, cracks and the like can be suppressed to some extent, but it is not sufficient. Therefore, an object of the present invention is to provide a composition for forming a resin bump that can easily form a B-stage and can form a bump excellent in thermal shock resistance.

That is, the present invention is as follows.
A method for producing a semiconductor device using a resin bump composition, comprising the following steps (i) to (v):
(I) a step of printing the resin bump composition on an electrode pad of a silicon wafer to form a bump;
(Ii) B-stage the bump by heating at 60 to 200 ° C. for 3 to 1 minute;
(Iii) cutting the silicon wafer provided with the bumps into a plurality of pieces;
(Iv) flip chip connecting the pieces through the bumps; and
(V) a step of thermosetting the bumps;
The resin bump composition is
(A) Epoxy resin 100 parts by mass (B) Curing agent The amount of the epoxy group and reactive group in the component (B) relative to 1 equivalent of the epoxy group in the component (A) is 0.8 to 1.25 equivalents. (C) Curing Accelerator 0.1 to 10 parts by mass (D) conductive filler with respect to 100 parts by mass in total of component (A) and component (B) Total of component (A) and component (B) 400 to 2000 parts by mass with respect to 100 parts by mass, and (E) particles of thermoplastic resin solid at 25 ° C. 5 to 50 parts by mass with respect to a total of 100 parts by mass of component (A) and component (B),
And at least one of component (A) and component (B) contains a silicone-modified resin, and the thermoplastic resin particles have a maximum particle size of 10 μm or less and an average particle size of 0.1 to 5 μm .
Furthermore, the present invention is as follows.
A method for producing a semiconductor device using a resin bump composition, comprising the following steps (1) to (4):
(1) A step of printing the resin bump composition on an electrode pad on a substrate to form a bump;
(2) Bumping the bumps by heating at 60 to 200 ° C. for 3 to 1 minute;
(3) a step of flip-chip connecting a silicon chip on the substrate provided with the bump via the bump; and
(4) a step of thermosetting the bumps;
The resin bump composition is
(A) Epoxy resin 100 parts by mass
(B) Curing agent The amount of the epoxy group and reactive group in the component (B) relative to 1 equivalent of the epoxy group in the component (A) is 0.8 to 1.25 equivalents.
(C) Curing accelerator 0.1 to 10 parts by mass with respect to 100 parts by mass in total of component (A) and component (B)
(D) Conductive filler 400 to 2000 parts by mass with respect to 100 parts by mass in total of component (A) and component (B), and
(E) particles of thermoplastic resin solid at 25 ° C. 5 to 50 parts by mass with respect to 100 parts by mass in total of component (A) and component (B),
And at least one of component (A) and component (B) contains a silicone-modified resin, and the thermoplastic resin particles have a maximum particle size of 10 μm or less and an average particle size of 0.1 to 5 μm.

The composition of the present invention is excellent in screen printability, and can form bumps on a wafer or a substrate. Printed bumps can be B-staged with good reproducibility. Furthermore, after heat-curing, a connection having excellent thermal shock resistance is formed between the semiconductor chip having excellent conductivity and a low-k film.

Hereinafter, the composition of this invention is demonstrated for every component.

(A) Epoxy resin In the present invention, examples of the (A) epoxy resin include novolak type, bisphenol type, biphenyl type, phenol aralkyl type, dicyclopentadiene type, naphthalene type, amino group-containing type, which will be described later. Examples include silicone-modified epoxy resins and mixtures thereof. Of these, bisphenol A type, bisphenol F type, novolac type epoxy resin and silicone-modified epoxy resin are preferable. The silicone-modified epoxy resin is described in the section (B) Curing Agent below together with the silicone-modified phenol resin.

(B) Curing agent As the curing agent, known curing agents for epoxy resins can be used, such as phenol resins (including silicone-modified phenol resins described later), acid anhydrides, and amines. Kind. Of these, phenol resins and silicone-modified phenol resins are preferred in consideration of the balance between curability and stability in the B-stage state. Examples of the phenol resin include novolak type, bisphenol type, trishydroxyphenylmethane type, naphthalene type, cyclopentadiene type, phenol aralkyl type and the like, and these may be used alone or in combination of two or more. Of these, the novolac type and the bisphenol type are preferable.

但し、Ｒ¹は水素原子であり、Ｒ²は水素原子又はメチル基であり、Xは水素原子又は臭素原子であり、ｎは０以上の整数、好ましくは０〜５０、より好ましくは１〜２０の整数である。 Examples of the silicone-modified phenol resin include a copolymer obtained by reacting an aromatic polymer with an organopolysiloxane. Examples of the aromatic polymer include compounds represented by the following formula (3) or (4).

However, R ¹ is hydrogen atom, R ² is a hydrogen atom or a methyl group, X is hydrogen atom or a bromine atom, n represents an integer of 0 or more, preferably 0-50, more preferably 1 to 20 Is an integer.

但し、Ｒ¹、Ｒ²、Ｘ及びｎについては上で述べた通りであり、ｍは０以上の整数、好ましくは０〜５の整数、より好ましくは０又は１である。 Examples of other aromatic polymers include alkenyl group-containing compounds represented by the following formulas (5) to (8).

However, R ¹ , R ² , X and n are as described above, and m is an integer of 0 or more, preferably an integer of 0 to 5, more preferably 0 or 1.

The silicone-modified epoxy resin already exemplified in (A) the epoxy resin is obtained by reacting an organopolysiloxane with one having an oxirane group-containing group in which R ¹¹ is represented by the following formula in the above formulas (3) to (8). The copolymer obtained by making it contain is mentioned.

The organopolysiloxane to be reacted with the aromatic polymer is represented by the formula (9).
(R ³ ) _a (R ⁴ ) _b SiO _{(4-ab) / 2} (9)
R ³ is a hydrogen atom, an organic group containing an amino group, an epoxy group, a hydroxy group or a carboxy group, or an alkoxy group, and R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group or hydroxy group. , An alkoxy group or an alkenyloxy group, and a and b are numbers satisfying 0.001 ≦ a ≦ 1, 1 ≦ b ≦ 3, and 1 ≦ a + b ≦ 4. The number of silicon atoms in one molecule is 1-1000, and 1 or more of R ³ directly bonded to the silicon atom in one molecule is included.

Here, examples of the amino group-containing organic group represented by R ³ include the following, wherein c is 1, 2, or 3.

Examples of the epoxy group-containing organic group include the following, where c is 1, 2, or 3.

Examples of the hydroxy group-containing organic group include the following, wherein d is 0, 1, 2, or 3, and e is 1, 2, or 3.

またアルコキシ基としては、メトキシ基、エトキシ基、ｎ-プロポキシ基等の炭素数１〜４のものが挙げられる。 Examples of the carboxy group-containing organic group include the following, where f is an integer of 1 to 10.

Moreover, as an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, and n-propoxy group, are mentioned.

The substituted or unsubstituted monovalent hydrocarbon group for R ⁴ is preferably one having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. Tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group and other alkyl groups, vinyl group, allyl group, propenyl group, butenyl group and other alkenyl groups, phenyl group, tolyl group and the like Aralkyl groups such as aryl groups, benzyl groups and phenylethyl groups, and halogen-substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms or the like.

但し、Ｒ⁶はアミノ基、エポキシ基、ヒドロキシ基、又はカルボキシ基含有の1価炭化水素基であり、Ｒ⁵は置換、或いは非置換の１価炭化水素基、好ましくはメチル基或いはフェニル基であり、ｐは０〜１０００の整数、好ましくは３〜４００の整数であり、ｑは０〜２０の整数、好ましくは０〜５の整数である。 Further, a and b are the values described above, but preferably 0.01 ≦ a ≦ 0.1, 1.8 ≦ b ≦ 2, 1.85 ≦ a + b ≦ 2.1, and the number of silicon atoms is 2 to 400. It is desirable that it is, and it is particularly desirable that it be 5 to 200. Examples of the organopolysiloxane include compounds of the formula (10) or (11).

R ⁶ is an amino group, epoxy group, hydroxy group, or carboxy group-containing monovalent hydrocarbon group, and R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group, preferably a methyl group or a phenyl group. And p is an integer of 0 to 1000, preferably an integer of 3 to 400, and q is an integer of 0 to 20, preferably an integer of 0 to 5.

The following can be mentioned as an example of such an organopolysiloxane.

The molecular weight of the organopolysiloxane of formula (10) is preferably 100 to 100,000. When the molecular weight of the organopolysiloxane is within the above range, the homogeneous structure in which the organopolysiloxane is uniformly dispersed in the matrix or the organopolysiloxane is included in the matrix depending on the structure or molecular weight of the aromatic polymer to be reacted with the organopolysiloxane. Sea-island structures that form fine layer separation appear.

When the molecular weight of the organopolysiloxane is relatively small, in particular when it is 100 to 10,000, it has a uniform structure, whereas when the molecular weight of the organopolysiloxane is relatively large, especially when it is 10,000 to 100,000, sea islands. A structure is formed. Whether a uniform structure or a sea-island structure is selected is selected according to the application. Here, if the molecular weight of the organopolysiloxane is less than 100, the cured product becomes rigid and brittle. On the other hand, if the molecular weight is greater than 100,000, the sea islands become large and local stress is generated. This is not in line with the main point of introducing the epoxy resin or the curing agent into the molecule.

A known method can be used as a method for reacting the aromatic polymer with the organopolysiloxane. For example, the aromatic polymer and the organopolysiloxane are subjected to an addition reaction in the presence of a platinum-based catalyst. To do.

In the composition of the present invention, the compounding ratio of the component (A) and the component (B) is the equivalent ratio of the epoxy group and the epoxy group in the curing agent to the reactive group, (epoxy group) / (in the curing agent). Is preferably 0.8 to 1.25, more preferably 0.9 to 1.1. When the equivalence ratio is not within this range, the reaction is partially unreacted, which may hinder the performance of the cured product and the performance of the semiconductor device using the cured product.

  In addition, when a component (B) does not contain a silicone modified phenol resin, a component (A) is a silicone modified epoxy resin. That is, at least one of the component (A) and the component (B) contains a silicone-modified resin.

(C) Curing accelerator (C) Examples of the curing accelerator include basic organic compounds such as organic phosphorus, imidazole, and tertiary amine. Examples of organic phosphorus include triphenylphosphine, tributylphosphine, tri (p-toluyl) phosphine, tri (p-methoxyphenyl) phosphine, tri (p-ethoxyphenyl) phosphine, triphenylphosphine / triphenylborate derivatives, tetra Examples thereof include phenylphosphine and tetraphenylborate derivatives. Examples of imidazole include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy Examples thereof include triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo (5,4,0). ) Undecene-7 and the like.

但し、Ｒ^７〜Ｒ^１４は夫々独立に水素原子又は或いは炭素数１〜１０の炭化水素基、或いはハロゲン原子である。

但し、Ｒ^１５はメチル基或いはメチロール基であり、Ｒ^１６は炭素数１〜１０の炭化水素基である。 Among these, a tetraphenylphosphine / tetraphenylborate derivative represented by the following formula (1) or a methylolimidazole derivative represented by the following formula (2) is preferable, and a curing agent (B) described later is more preferable. These phenol resins or silicone-modified phenol resins are used in combination.

However, R < ⁷ > -R < ¹⁴ > is a hydrogen atom or a C1-C10 hydrocarbon group, or a halogen atom each independently.

^{However, R 15} is a methyl group or a methylol ^{group, R 16} is a hydrocarbon group having 1 to 10 carbon atoms.

The addition amount of the (C) curing accelerator is desirably 0.1 to 10 parts by mass, particularly 0.2 with respect to 100 parts by mass in total of the (A) epoxy resin and the (B) curing agent. It is desirable that it is -5 mass parts. If the curing accelerator is less than the lower limit, the adhesive composition may be insufficiently cured, and if it is greater than the upper limit, the storage stability of the adhesive composition or the stability of the B stage state May cause trouble.

(D) Conductive filler Examples of the conductive filler include various metals such as gold, silver, copper, tin, zinc, nickel, cobalt, iron, manganese, aluminum, molybdenum, tungsten, and alloys thereof. Examples of the shape include a spherical shape, a granular shape, a scale shape, and a needle shape. Moreover, you may use the powder which vapor-deposited or plated the surface of insulating powders, such as a silica, an alumina, organic resin, and silicone rubber, with said various metals. The average particle size is preferably from 0.1 to 30 μm, particularly preferably from 0.5 to 10 μm.

(D) The addition amount of the conductive filler is preferably 300 to 2000 parts by mass, particularly 600 to 1500 parts by mass with respect to 100 parts by mass of the total of (A) epoxy resin and (B) curing agent. . When it is less than the lower limit, the conductivity is insufficient, and when it exceeds the upper limit, the cured product becomes rigid, which may impair flexibility and thermal shock resistance. The volume resistivity of the cured product is desirably 10 ⁻² Ω · cm or less, particularly 10 ⁻³ Ω · cm or less at room temperature.

(E) Thermoplastic resin particles that are solid at 25 ° C. The thermoplastic resin particles that are solid at 25 ° C. may be known resin particles, for example, AAS resin, AES resin, AS resin, ABS resin, MBS. Resin, vinyl chloride resin, vinyl acetate resin, methacrylic resin, phenoxy resin, polybutadiene resin, various fluororesins, various silicone resins, polyacetal, various polyamides, polyamideimide, polyimide, polyetherimide, polyetheretherketone, polyethylene , Polyethylene oxide, polyethylene terephthalate, polycarbonate, polystyrene, polysulfone, polyethersulfone, polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl formal, poniphenylene ether, polyphenylene Two sulfide, polybutylene terephthalate, polypropylene, polymethylpentene and the like. Among these, methacrylic resin, phenoxy resin, butadiene resin, polystyrene resin or a copolymer thereof is desirable. Alternatively, a core / shell structure in which the resin is different between the inner core (core) portion and the outer shell (shell) portion of the particle may be used. In that case, it is desirable that the core is rubber particles made of silicone resin, fluororesin, butadiene resin or the like, and the shell is the above-mentioned various thermoplastic resins made of linear molecular chains.

The thermoplastic resin particles may be substantially spherical, cylindrical or prismatic, indeterminate, crushed, and flake-like, and are preferably substantially spherical and indeterminate with no sharp corners for die bond applications.
The average particle size of the thermoplastic resin particles is appropriately selected depending on the application, but it is usually desirable that the maximum particle size is 10 μm or less, particularly 5 μm or less, and the average particle size is 0.1 to 5 μm, particularly It is desirable that it is 0.1-2 micrometers. When the maximum particle size is larger than the above upper limit value or the average particle size is larger than 5 μm, a part of the particle thermoplastic resin remains not sufficiently swollen or dissolved in the B-stage stage or the curing stage, and after the curing The properties of the composition may be impaired. On the other hand, when the average particle size is smaller than the lower limit, the viscosity of the composition is increased, and workability may be significantly deteriorated. The particle size can be measured by observation with an electron microscope.

The thermoplastic resin particles may have a crosslinked structure. However, since it is considered preferable to form a structure in which the thermoplastic resin (C) is uniformly dispersed in the epoxy resin network structure, the degree of crosslinking is preferably low, and more preferably linear molecular chains without crosslinking. It is.

The molecular weight of the thermoplastic resin particles is appropriately selected depending on the type of resin. Typically, the polystyrene-equivalent number average molecular weight is 1,000 to 10,000,000, preferably 10,000 to 100,000, and the weight average molecular weight is 10,000 to 100,000,000, preferably 100,000. 000 to 1,000,000. If the number average molecular weight is smaller than the lower limit value or the weight average molecular weight is smaller than the lower limit value, the swelling temperature becomes too low, and the B stage appears early, so the A stage state may become unstable. There is. In addition, sufficient B-stage hardness cannot be obtained, and there is a risk that defects such as voids, outflow, or die shift may occur, particularly in die bond material applications. On the other hand, when the number average molecular weight is larger than the above upper limit value or the weight average molecular weight is larger than the above upper limit value, the swelling temperature becomes high, the difference from the appearance temperature of the C stage becomes small, and the B stage state is unstable. There is a risk of becoming. Moreover, there is a possibility that a part of the particle thermoplastic resin may inhibit the formation of the epoxy resin network structure after the B-stage or the C-stage.

The content of the thermoplastic resin particles is preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B) in order to obtain a stable B stage state. Preferably it is 10-30 mass parts. When the content is less than the lower limit, sufficient B-stage hardness cannot be obtained, and the resin may flow out to the outside of the semiconductor chip, which may generate fillets. On the other hand, when the content is larger than the upper limit, the B stage state becomes too hard, and there is a possibility that defects such as insufficient adhesion may occur.

(F) Diluent A diluent may be added for the purpose of adjusting the viscosity of the resin composition of the present invention. The type of the diluent is not particularly limited, but the component (A) epoxy resin (B) curing agent is soluble in the diluent, while the component (C) curing accelerator is insoluble. desirable. For example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone, cyclohexanone, isophorone, diacetone alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol Glycol ethers such as methyl cellosolve acetate, ethyl cellosolve acetate, carbitol acetate, and the like. Further, in order to obtain a viscosity with good workability in the printing step (step (i) or step (1)) in the method of the present invention described later, the diluent has a certain high boiling point, for example, 180 ° C to 230 ° C. Among the above-mentioned diluents, isophorone, methyl carbitol, ethyl carbitol, butyl carbitol, carbitol acetate and the like having a boiling point in this range are particularly preferable.

The content of the diluent is not particularly limited, but is preferably 40 parts by mass or less with respect to a total of 100 parts by mass of the (A) epoxy resin (B) curing agent. Here, when there is more content of a diluent than 40 mass parts, there exists a possibility that a resin composition may become low viscosity too much and (D) electroconductive filler mentioned later may settle during long-term storage.

In addition to the above components, the composition of the present invention has an insulating filler, such as silica, alumina, talc, mica, silicon nitride, boron nitride, etc., silane coupling agent, flame retardant, ion trap agent, Waxes, colorants, adhesion aids, and the like can be added in amounts that do not impair the purpose of the present invention.

  Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N-β (aminoethyl) ) Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino Propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, γ-isocyanatopropyltriethoxysilane, etc. Is mentioned. These can be used singly or in combination of two or more. Among these, it is preferable to use γ-glycidoxypropyltrimethoxysilane. When using the said coupling agent, the usage-amount is 0.1-5.0 mass parts normally with respect to 100 mass parts of said (A)-(F) component, Preferably 0.3-3. 0 parts by mass.

Method for preparing composition The composition of the present invention can be prepared by mixing the above-described components using a known mixing method, for example, a mixer, a roll, or the like.

Method of using the composition The resin bump composition of the present invention comprises the following steps (i) to (v):
(I) a step of printing the resin bump composition on an electrode pad of a silicon wafer to form a bump;
(Ii) B-stage the bump by heating at 60 to 200 ° C. for 3 to 1 minute;
(Iii) cutting the silicon wafer provided with the bumps into a plurality of pieces;
(Iv) a step of flip-chip connecting the individual pieces via the bumps, and (v) a step of thermosetting the bumps;
Or the following steps (1) to (4):
(1) A step of printing the resin bump composition on an electrode pad on a substrate to form a bump;
(2) Bumping the bumps by heating at 60 to 200 ° C. for 3 to 1 minute;
(3) a step of flip-chip connecting a silicon chip via the bump on the substrate provided with the bump, and (4) a step of thermosetting the bump.
Used to manufacture a semiconductor device.

In the step (1) or (i), bumps having a diameter of several hundred μm to several mm can be formed by screen printing.
In step (2) or (ii), it is heated in an open / closed or continuous oven to make it a B stage, that is, in a non-fluid state, in step (iii), a dicer is used, and in step (3) or (iv) A chip is mounted via a resin bump with a die bonder, and in step (4) or (v), the adhesive composition is cured in an open / close or continuous oven. Hereinafter, each step will be described in detail.

Separation method Wafer cutting (dicing) usually includes dicing for cutting a wafer by rotating a diamond blade at high speed and laser dicing using a laser, and is appropriately selected according to the application.

Flip chip connection conditions Flip chip connection conditions include preheat temperature and time, chip and substrate temperature, time, and pressure during flip chip connection. The purpose of the preheating is to improve the adhesion between the flip chip or the resin composition applied to the substrate and the semiconductor chip. The preheating temperature is desirably 50 ° C. to 150 ° C. for 10 minutes to 2 seconds. The flip-chip connection temperature is preferably 25 ° C. to 250 ° C. for the semiconductor chip, 25 ° C. to 200 ° C. for the substrate, 0.1 seconds to 10 seconds for the time, and 0.01 MPa to 10 MPa for the pressure.

Curing conditions Typical curing conditions for the resin composition are 8 hours to 1 hour at a temperature of 100C to 200C. In the subsequent step of sealing the semiconductor device, curing may be performed simultaneously.

Examples Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples.
Examples 1-5, Comparative Examples 1 and 2
Each component shown in Table 1 was mixed with a planetary mixer at 25 ° C., passed through three rolls at 25 ° C., and then mixed again at 25 ° C. with a planetary mixer to prepare each composition. Each composition was subjected to the following tests (a) to (d). The results are shown in Table 1. In the tests (b) to (d), each composition was heated at 125 ° C. for 1 hour and then heated at 165 ° C. for 2 hours to be cured.

Resin used, etc. (A) Epoxy resin Epoxy resin (bisphenol A type epoxy resin, epoxy equivalent 180, Nippon Kayaku Co., Ltd. RE310S)
Silicone-modified epoxy resin (Synthesis example 1)
(B) Curing agent curing agent (phenol novolak, equivalent 110, Meiwa Kasei DL92)
Silicone-modified phenolic resin curing agent (Synthesis Example 2)
(C) Curing accelerator Curing accelerator (tetraphenylphosphine / tetraphenylborate, TPP-K manufactured by Hokuko Chemical)
(D) Conductive filler silver powder f (flake powder, average particle size 2.5 μm, maximum particle size 14 μm, Fukuda Metal Foil Powder Industry Ag C-239)
(E) Thermoplastic resin particulate thermoplastic resin (manufactured by polymethyl methacrylate, number average molecular weight 50,000, weight average molecular weight 150,000, average particle size 1 micron, maximum particle size 3 microns)
(F) Diluent carbitol acetate adhesion aid KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

Synthesis Example 1: Synthesis of silicone-modified epoxy resin 42.0 g (0.10 mol) of epoxy resin of formula (12) and 168.0 g of toluene were placed in a flask equipped with a stirring blade, a dropping funnel, a thermometer, an ester adapter and a reflux tube. And azeotropic dehydration was performed at 130 ° C./2 hours. This was cooled to 100 ° C., 0.5 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (14) and 145.2 g of toluene. Was added dropwise in about 30 minutes and further aged at 100 ° C./6 hours. From this, toluene was removed to obtain a yellow transparent liquid (η = 5 Pa · s / 25 ° C., epoxy equivalent 400, organopolysiloxane content 46.4% by mass).

Synthesis Example 2: Synthesis of silicone modified phenolic resin 30.8 g (0.10 mol) of phenolic resin of formula (13) and 123.2 g of toluene in a flask equipped with a stirring blade, a dropping funnel, a thermometer, an ester adapter and a reflux tube. And azeotropic dehydration was performed at 130 ° C./2 hours. This was cooled to 100 ° C., 0.5 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (14) and 145.2 g of toluene. Was added dropwise in about 30 minutes and further aged at 100 ° C./6 hours. From this, toluene was removed to obtain a brown transparent liquid (η = 20 Pa · s / 25 ° C., phenol equivalent 340, organopolysiloxane content 54.1% by mass).

Test method
(A) Viscosity For each composition, according to JIS Z-8803, using an E-type viscometer (HBDV-III, manufactured by Brookfield), measurement temperature 25 ° C., shear rate 2.00 (sec ⁻¹ ), The viscosity at 2 minutes after the start of rotation was measured.

(B) Volume resistivity of cured product Based on the Japan Rubber Association Standard (SRIS) 2301, the volume resistivity at a measurement temperature of 25C was measured for the cured product of each composition.

(C) Tensile modulus of cured product Based on JIS K 7113, the cured product of each composition was measured for tensile modulus at a measurement temperature of 25 ° C.

(D) Tensile Breaking Elongation of Cured Product Based on JIS K 7113, the tensile breaking elongation at a measurement temperature of 25 ° C. was measured for the cured product of each composition.
(E) Temperature cycle test Using the composition of Example 1 and the composition of Comparative Example 1 respectively, 20 test pieces as shown in FIG. 1 were prepared. Observation (SAT) was performed, and the number of test pieces in which cracks or the like were observed was counted.
The method of making the specimen is as follows:
Each composition was screen printed on an electrode pad of a semiconductor wafer (200 mmφ, 200 μm thick) to form resin bumps. The bump was heated at 100 ° C. for 10 minutes to form a B-stage. Next, the semiconductor wafer was diced with a dicer to obtain a 15 mm × 15 mm semiconductor chip having 1600 bumps.
The obtained chip was bonded onto a BT substrate (thickness of 200 microns, 35 mm × 35 mm) at 150 ° C. (chip) / 100 ° C. (substrate) / 1 Mpa / 1 second. Next, an underfill agent (SMC378S (manufactured by Shin-Etsu Chemical Co., Ltd.)) was dispensed between the chip and the substrate, and heated at 150 ° C. for 2 hours to make the resin bump and the underfill agent C-staged.
20 chips obtained were each maintained at −55 ° C./30 minutes + (from −55 ° C. to 125 ° C.) / 5 minutes + 125 ° C./30 minutes maintained + (from 125 ° C. to −55 ° C.) in a temperature cycle tester ) / 5 minutes as one cycle, and subjected to a temperature test of 1000 cycles in total.

As shown in Table 1, the compositions of the examples of the present invention form connections with excellent electrical conductivity. In addition, since it has a low elastic modulus and sufficient elongation, it is highly resistant to thermal shock. In particular, by using an underfill agent in combination, an apparatus having excellent thermal shock resistance can be constructed. Since the composition of Comparative Example 1 lacks a silicone-modified resin, the cured product has a high elastic modulus and insufficient elongation. Further, Comparative Example 2 lacks thermoplastic resin particles, and the B-stage is performed by curing the epoxy resin to some extent, but it is difficult to control the degree of curing.

The composition of the present invention is suitable for the manufacture of a semiconductor device that is required to be miniaturized because it is easy to control the B-stage and can form a conductive connection excellent in thermal shock resistance.

It is sectional drawing of the apparatus created in the Example.

Explanation of symbols

1 Semiconductor chip 2 Resin bump 3 Underfill agent 4 Substrate

Claims (6)

Comprising the step of following (i) ~ (v), a method of manufacturing a semiconductor device using a tree fat bump composition,
(I) a step of printing the resin bump composition on an electrode pad of a silicon wafer to form a bump;
(Ii) B-stage the bump by heating at 60 to 200 ° C. for 3 to 1 minute;
(Iii) cutting the silicon wafer provided with the bumps into a plurality of pieces;
(Iv) a step of flip-chip connecting the individual pieces via the bumps, and (v) a step of thermosetting the bumps ;
The resin bump composition is
(A) Epoxy resin 100 parts by mass
(B) Curing agent The amount of the epoxy group and reactive group in the component (B) relative to 1 equivalent of the epoxy group in the component (A) is 0.8 to 1.25 equivalents.
(C) Curing accelerator 0.1 to 10 parts by mass with respect to 100 parts by mass in total of component (A) and component (B)
(D) Conductive filler 400 to 2000 parts by mass with respect to 100 parts by mass in total of component (A) and component (B), and
(E) particles of thermoplastic resin solid at 25 ° C. 5 to 50 parts by mass with respect to 100 parts by mass in total of component (A) and component (B),
And at least one of component (A) and component (B) contains a silicone-modified resin, and the thermoplastic resin particles have a maximum particle size of 10 μm or less and an average particle size of 0.1 to 5 μm. Comprising the following steps (1) to (4), a method of manufacturing a semiconductor device using a tree fat bump composition,
(1) A step of printing the resin bump composition on an electrode pad on a substrate to form a bump;
(2) Bumping the bumps by heating at 60 to 200 ° C. for 3 to 1 minute;
(3) a step of flip-chip connecting a silicon chip via the bump on the substrate provided with the bump, and (4) a step of thermosetting the bump .
The resin bump composition is
(A) Epoxy resin 100 parts by mass
(B) Curing agent The amount of the epoxy group and reactive group in the component (B) relative to 1 equivalent of the epoxy group in the component (A) is 0.8 to 1.25 equivalents.
(C) Curing accelerator 0.1 to 10 parts by mass with respect to 100 parts by mass in total of component (A) and component (B)
(D) Conductive filler 400 to 2000 parts by mass with respect to 100 parts by mass in total of component (A) and component (B), and
(E) particles of thermoplastic resin solid at 25 ° C. 5 to 50 parts by mass with respect to 100 parts by mass in total of component (A) and component (B),
And at least one of component (A) and component (B) contains a silicone-modified resin, and the thermoplastic resin particles have a maximum particle size of 10 μm or less and an average particle size of 0.1 to 5 μm. (E) Particles of a thermoplastic resin solid at 25 ° C. are particles of a thermoplastic resin selected from a methacrylic resin, a phenoxy resin, a butadiene resin, a polystyrene resin, or a copolymer thereof. The method described. (E) Particles of a thermoplastic resin solid at 25 ° C. have a polystyrene-equivalent number average molecular weight of 10,000 to 100,000 and a weight average molecular weight of 100,000 to 1,000,000. The method of any one of these. The method according to any one of claims 1 to 4, wherein the resin bump composition further comprises (F) a diluent selected from isophorone, methyl carbitol, ethyl carbitol, butyl carbitol, carbitol acetate. . A semiconductor device manufactured by the method according to claim 1 .

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