TWI674633B - Method for manufacturing flip chip mounted article, flip chip mounted article and resin composition for pre-applied underfill - Google Patents

Abstract

An object of the present invention is to provide a method for manufacturing a flip-chip mounting body, which can suppress generation of voids in a resin composition for underfill during a first-feed flip-chip bonding process.

The solution to the above-mentioned problem is a method for manufacturing a flip-chip package including the following steps: (1) providing solder to at least one of a copper bump electrode provided on a semiconductor element and a connection electrode provided on a circuit board; Layer steps; (2) pre-supply underfill containing (A) epoxy resin, (B) aromatic amine hardener, (C) inorganic filler, (D) silane coupling agent, and (E) flux A step of supplying the resin composition for the agent onto the circuit board; (3) thermocompression bonding the semiconductor element and the circuit board, heating the copper bump electrode for connection and the connection electrode for 1 second or more at a temperature higher than the melting point of the solder; A step of performing a solder connection when the reaction rate of the material is within a specific range; and (4) a step of hardening the resin composition under a specific pressure.

Description

Method for manufacturing flip chip mounting body, flip chip mounting body, and resin composition for first-supply underfill

The present invention relates to a method for manufacturing a flip-chip mounted body, a flip-chip mounted body manufactured by the manufacturing method, and a resin composition for a first-supply underfill used in the manufacturing method.

In recent years, flip chip bonding has been used as a mounting method for semiconductor wafers that can be used to further increase the density and frequency of electronic equipment wiring. Generally speaking, flip-chip bonding uses a material called an underfill to seal the gap between a semiconductor wafer and a substrate.

Generally, in flip-chip bonding, after the semiconductor wafer and the substrate are joined by soldering or the like, the gap between the semiconductor wafer and the substrate is filled with a thermosetting semiconductor resin sealing composition underfill (hereinafter referred to as "post-feed type"). "). However, in recent years, a first-supply flip-chip bonding process system has attracted much attention. It firstly applies an underfill to a substrate, and then mounts a semiconductor wafer, and simultaneously performs hardening and half-filling of the underfill. The connection between the conductor wafer and the substrate can shorten the steps and shorten the curing time. As a result, the manufacturing process can be performed at a low cost and low energy consumption. The sealing material resin composition (hereinafter referred to as "first-supply-type underfill") for this process The requirements for the resin composition "" for the agent are high.

In recent years, since the bump density of flip-chips has been further increased, there is a problem that voids (air bubbles) remain in the pre-feed type underfill resin composition in the pre-feed type flip-chip bonding process. In order to solve this problem, Patent Document 1 discloses a method for manufacturing a semiconductor device including an alignment step of aligning a semiconductor wafer on which a protruding electrode having a tip portion made of solder is formed on a substrate via a bonding material; An electrode bonding step of heating to a temperature above the melting point of the solder so that the hardening rate of the bonding material becomes 40% or less, and fusion-bonding the protruding electrode of the semiconductor wafer with the electrode portion of the substrate; and a hardening rate of 40% or less The above-mentioned bonding material is heated in a pressurized environment to remove voids.

However, since the bonding agent used in the above-mentioned method of manufacturing a semiconductor device essentially uses an acid anhydride as a hardener and an imidazole compound as a hardening accelerator (paragraphs 0052, 0055, and 0060 of Patent Document 1), it is likely to be bonded. The problem of gelation of the material and the occurrence of voids cannot be sufficiently suppressed. Furthermore, since the bonding material lacks stability, there is a problem that the pressure-curing oven has to be operated with a complicated procedure in the cavity removal step (Patent Document 1, paragraph 0054). Among them, it is described that the bonding material can achieve desired viscosity characteristics by containing a shake modifier (paragraph 0026 of Patent Document 1). When the shake modifier is 20% by weight or more, The rejection of the bonding material is low (Paragraph 0028 of Patent Document 1). On the other hand, it is described in Example 1 and Example 2 that it contains 40.6% shake modifier (Parameters 0052, 0055, 0060 of Patent Document 1). . As mentioned, it can be inferred that the bonding material of the conventional technology cannot pass the test of the hardening rate and reliability after the electrode bonding unless it has a very unstable exclusion composition, and the pressure will have to be operated with complicated procedures. Problems with hardening oven.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-123033

An object of the present invention is to provide a method for manufacturing a flip-chip mounted body and a resin composition for a first-supply underfill used in the method for manufacturing a flip-chip mounted body. The occurrence of voids in the first-feed type underfill resin composition during the first-feed type flip chip bonding process is suppressed.

The present invention relates to a method for manufacturing a flip-chip mounted body, a flip-chip mounted body, and a resin composition for a first-supply underfill by solving the above problems by having the following configurations.

[1] A method for manufacturing a flip-chip mounted body in which a copper bump electrode for connection provided on a semiconductor element and The connection electrodes of the circuit substrate are opposed to each other, and are connected by a solder connection between a copper bump electrode provided on the semiconductor element and a connection electrode provided on the circuit substrate, so that the semiconductor element is mounted on the circuit substrate, and the circuit substrate and The gap of the semiconductor element is sealed with a resin, and the method for manufacturing the flip-chip package includes the following steps in order: (1) providing at least one of a copper bump electrode for connection of a semiconductor element and a connection electrode for a circuit board; A step of a high melting point solder layer having a melting point of 210 to 250 ° C; (2) will include (A) an epoxy resin, (B) an aromatic amine hardener, (C) an inorganic filler, (D) a silane coupling agent, and ( E) The step of supplying the flux-required underfill resin composition to the circuit board; (3) thermocompression bonding the semiconductor element and the circuit board, and connecting the copper bump electrode for connection of the semiconductor element to the circuit board The step of performing solder connection when the reaction rate of the first-supply underfill resin composition is 0.1 to 25% after the electrode is heated at a temperature higher than the melting point of the solder for 1 second or more; and (4) under pressure : A step of hardening the supplied first-supply underfill resin composition under a pressure of 0.6 MPa or more.

[2] The method for producing a flip-chip mounted body according to the above [1], wherein the component (B) is selected from an aromatic amine hardener represented by chemical formula (7) and an aromatic represented by chemical formula (8) At least one group of amine hardeners:

[3] The method for producing a flip-chip mounted body according to the above [1] or [2], wherein the component (A) is selected from the group consisting of a bisphenol F-type epoxy resin, a bisphenol A-type epoxy resin, and an amine group. At least one of a group consisting of a phenol type epoxy resin and a naphthalene type epoxy resin.

[4] A flip-chip mounted body, which is a flip-chip mounted body manufactured by the method for manufacturing a flip-chip mounted body according to any one of [1] to [3] above.

[5] A resin composition for a first-supply underfill, comprising (A) an epoxy resin, (B) an aromatic amine hardener, (C) an inorganic filler, (D) a silane coupling agent, and (E ) Flux; viscosity at 25 ° C. is 10 to 100 Pa · s; it is used in the method for manufacturing a flip-chip mounted body as described in any one of [1] to [3] above.

[6] The resin composition for a first-supply underfill as described in the above [5], wherein the component (E) is 8-quinolinol, and 100 parts by mass of the resin composition for a first-supply type underfill, and the component (E) is 0.5 to 3 parts by mass.

[7] A first-feed type flip chip mounting body, which is a hardened product having the first-feed type underfill resin composition described in [5] or [6] above.

According to the present invention [1], it is possible to provide a method for manufacturing a flip-chip mounted body, which can suppress generation of voids in the resin composition for a first-feed underfill in a first-feed flip-chip bonding process.

According to the present inventions [4] and [7], it is possible to provide a flip-chip mounting body, which is a resin composition for an underfill manufactured by a first-feed flip-chip bonding process, in which generation of voids is suppressed.

According to the present invention [5], it is possible to provide a resin composition for a first-supply underfill, which can suppress the occurrence of voids in the resin composition for a first-supply underfill in a first-supply flip chip bonding process. .

FIG. 1 is a diagram showing a temperature curve of a Thermal-Compression-Bonding (TCB) curve A. FIG.

FIG. 2 is a diagram showing a temperature curve of the TCB curve B. FIG.

FIG. 3 is a diagram showing a temperature curve of the TCB curve C.

FIG. 4 is a diagram showing a temperature curve of the TCB curve D. FIG.

Fig. 5 is a diagram showing a temperature curve of the TCB curve E.

FIG. 6 is a diagram showing a temperature curve of the TCB curve F. FIG.

Fig. 7 is a photograph of a sample having an alloy layer formed on a cross section.

Fig. 8 is an example of a schematic diagram for explaining step (1).

Fig. 9 is an example of a schematic diagram for explaining steps (1) to (4).

Fig. 10 is an example of a schematic diagram for explaining the steps (1) to (4).

Fig. 11 is an example of a schematic diagram for explaining the steps (1) to (4).

[Manufacturing Method of Flip Chip Mount]

In the method for manufacturing a flip-chip mounted body of the present invention, a copper bump electrode for connection provided on a semiconductor element and a connection-use electrode system provided on a circuit board are opposed to each other, and The copper bump electrode for connection of the semiconductor element is soldered with the connection electrode provided on the circuit substrate, so that the semiconductor element is mounted on the circuit substrate, and the gap between the circuit substrate and the semiconductor element is sealed with resin. The manufacturing method includes the following steps in order: (1) a step of providing a solder layer having a melting point of 210 to 250 ° C. on at least one of the copper bump electrodes for connection of a semiconductor element and a connection electrode for a circuit board; (2) applying A resin composition for first-supply underfill containing (A) an epoxy resin, (B) an aromatic amine hardener, (C) an inorganic filler, (D) a silane coupling agent, and (E) a flux is supplied to a circuit Steps on the substrate; (3) Thermocompression bonding the semiconductor element and the circuit substrate, and heating the copper bump electrode for connection of the semiconductor element and the connection electrode for the circuit substrate for 1 second or more at a temperature higher than the melting point of the solder. Later, the first-supply type of underfill tree The step of performing solder connection when the reaction rate of the fat composition is 0.1 or more and 25% or less; and (4) curing the supplied resin composition for the first-supply underfill under a pressure of 0.6 MPa or more step.

In the present invention, a copper bump electrode for connection provided on a semiconductor element is opposed to a connection electrode provided on a circuit substrate, and the copper bump electrode for connection provided on the semiconductor element and the connection electrode provided on the circuit substrate are opposed to each other. Semiconductor chip mounted on a circuit board by solder connection, and a method of manufacturing a flip-chip mounting body in which the gap between the circuit board and the semiconductor element is sealed with a resin, especially the first-supply type that uses copper bump electrodes for connection of semiconductor elements Manufacturing method used in flip chip bonding process.

(1) In the step of providing a solder layer having a melting point of 210 to 250 ° C in at least one of the copper bump electrode for connection of a semiconductor element and a connection electrode for a circuit board, when the melting point of the solder is too low, the component may be damaged due to the component. The heat generated during the operation causes the solder to melt and cause malfunctions. Therefore, the use environment is likely to be restricted. Moreover, when the temperature is too high, the thermal load on the parts during installation increases, and the usable components become restricted. Therefore, as long as it has a melting point of 210 to 250 ° C, there is no particular limitation, but from the standpoint of lead-free (Pb free), it is preferably a Sn-Ag system, a Sn-Cu system, or a Sn-Ag-Cu system. Furthermore, the substrate includes, but is not limited to, epoxy resin, glass-epoxy resin, and polyimide resin.

(2) Supply of (A) epoxy resin, (B) aromatic amine hardener, (C) inorganic filler, (D) silane coupling agent, and (E) flux The first-supply type underfill resin composition used in the step of supplying the resin composition for underfill type (hereinafter referred to as the underfill resin composition) to the circuit board will be described later.

Examples of a method for supplying the first-supply-type underfill resin composition to the circuit board include a dispenser, screen printing, and the like.

(3) The semiconductor element and the circuit board are thermocompression-bonded, and the copper bump electrode for connection of the semiconductor element and the connection electrode for the circuit board are heated at a temperature higher than the melting point of the solder for more than 1 second, and then used for the first-supply underfill. When the reaction rate of the resin composition is 0.1 to 25%, the thermocompression bonding in the step of soldering is performed. From the viewpoint of temperature and pressure controllability and mass productivity, it is preferable to use a flip chip bonding machine. . Furthermore, from the viewpoint of good solder bonding properties, it is preferable that the "temperature above the melting point of the solder" is higher than the melting point by 20 to 50 ° C. The reaction rate of the first-supply underfill resin composition was measured by differential scanning thermal analysis (DSC) using a resin composition for underfill before and after TCB (temperature increase rate: 10 ° C / minute). The peak area of the exothermic spectrum can be obtained according to the following formula: Formula: {1- (exothermic amount after TCB) / (exothermic amount before TCB)} × 100 (%).

For example, when the heat generation amount of the resin composition for underfill before TCB is 100 J / g and the heat generation amount after TCB is 80 J / g, the reaction rate becomes (1-80 / 100) × 100 = 20%. The analysis software (for example, the software name attached to DSC manufactured by NETZSCH Corporation: Proteus series) can simply indicate the amount of heat generation.

(4) Under pressure: 0.6MPa or more, The pressure in the step of hardening the pre-supply-type underfill resin composition is preferably 0.6 mPa or more from the viewpoint of reducing voids in the underfill resin composition, and from the viewpoint of structural safety From the viewpoint, it is preferably 1.0 MPa or less.

An example of a schematic diagram for explaining the manufacturing method of the flip-chip mounted body of this invention is shown to FIGS. 8-11. An example of a schematic diagram for explaining the step (1) is shown in FIG. 8. The upper diagram of FIG. 8 is a step of providing a solder layer on a copper bump electrode for connection of a semiconductor element (Die). The lower diagram of FIG. 8 is for connection of a circuit board (Substrate). The step of providing an electrode with a solder layer.

An example of a schematic diagram for explaining the steps (1) to (4) is shown in FIG. 9. FIG. 9 is an example in which a solder layer is provided on a copper bump electrode for connection of a semiconductor element (Die). First, as shown in FIG. 9 (1), a copper bump for connection to a semiconductor element (Die) is provided with a solder layer (Solder). Then, as indicated by 2 in FIG. 9, a pre-applied underfill resin composition (pre-applied underfill) is supplied onto a circuit board (Substrate). After that, as shown in FIG. 9 (3), the semiconductor element (Die) and the circuit substrate (Substrate) are thermocompression-bonded using a flip chip bonder to connect the semiconductor element (Die). After the copper bump electrode (Electrode) for connection to the circuit board (Substrate) is heated at a temperature higher than the melting point of the solder for more than 1 second, the reaction rate of the resin composition for the first-supply underfill is 0.1. Connect solder at 25% or more. At this time, a void is generated. Finally, as shown in Figure 4 (4), the pressure (Pressure) above 0.6 MPa Next, the supplied pre-applied underfill resin composition (Pre-applied underfill) is cured. By this pressurization, even if a cavity is generated in the step (C), the cavity can be discharged from the pre-applied underfill of the pre-applied underfill.

An example of a schematic diagram for explaining the steps (1) to (4) is shown in FIG. 10. FIG. 10 shows an example in which a solder layer is provided on a connection electrode (Electrode) of a circuit substrate. Otherwise, it is the same as that in FIG. 9.

An example of a schematic diagram for explaining the steps (1) to (4) is shown in FIG. 11. FIG. 11 shows that a solder layer is provided on a copper bump electrode for connection of a semiconductor element (Die), and a solder layer is provided on the connection electrode (Electrode) of a circuit substrate (Substrate). example. Otherwise, it is the same as that in FIG. 9.

[Resin composition for first supply type underfill]

The resin composition for underfill according to the present invention comprises (A) an epoxy resin, (B) an aromatic amine hardener, (C) an inorganic filler, (D) a silane coupling agent, and (E) a flux at a temperature of : The viscosity at 25 ° C. is 10 to 100 Pa · s, which is a method for manufacturing the above-mentioned flip chip mounting body.

The component (A) is used to impart adhesiveness to the resin composition for underfill and durability after curing. Examples of the component (A) include bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, and novolac. Type epoxy resin, alicyclic epoxy resin, ether-based or polyether-based epoxy resin, containing oxetan From the viewpoint of the viscosity of the resin composition for an underfill, the alkane compound and the like are selected from bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, aminophenol-type epoxy resin, and naphthalene-type. It is preferred that at least one of the groups of the epoxy resin is grouped.

As the bisphenol F-type epoxy resin, the one represented by formula (1) is preferred: In the formula, n represents an average value, preferably from 0 to 10, and particularly preferably from 0 to 4. The epoxy equivalent is preferably 160 to 900 g / eq.

As the bisphenol A type epoxy resin, the one represented by formula (2) is preferred: In the formula, m represents an average value, preferably from 0 to 10, and particularly preferably from 0 to 4. The epoxy equivalent is preferably 165 to 900 g / eq.

The aminophenol type epoxy resin is preferably one represented by formula (3): Examples of commercially available components of (A) include bisphenol F-type epoxy resin (product name: EXA-830CRP) made by DIC, bisphenol A-type epoxy resin (product name: EXA-850CRP) made by DIC, and naphthalene made by DIC. Type epoxy resin (product name: HP-4032D), amine-based phenol epoxy resin (product name: JER630) manufactured by Mitsubishi Chemical. (A) component can be used individually or in combination of 2 or more types.

(B) A component system gives hardening ability to the resin composition for underfills. Examples of the component (B) include phenol-based hardeners, acid anhydride hardeners, and imidazole-based hardeners. In terms of reaction control, an amine-based hardener is preferred. An aromatic amine-based hardener is particularly preferred in terms of suppression of solder connectivity and voiding during thermal compression bonding in the solder connection step and subsequent thermal compression bonding. In addition, as the aromatic amine-based hardener, in terms of adhesion and reliability, it is preferable to have a primary or secondary amine group in the molecular structure. The aromatic amine compound is preferably an aromatic amine compound having one aromatic ring and / or an aromatic amine compound having a plurality of aromatic rings.

Examples of the aromatic amine compound having one aromatic ring include m-phenylenediamine.

Examples of the aromatic amine compound having a plurality of aromatic rings include diaminodiphenylmethane, diaminodiphenylphosphonium, and the like, and it is preferably one represented by formula (4) or formula (5):

(In the formula, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.) More preferably, it is an alkyl group having 2 carbon atoms of R represented by formula (4) or formula (5).

The component (B) contains an aromatic amine compound having one aromatic ring and / or an aromatic amine compound having a plurality of aromatic rings. From a viewpoint, it is more preferable that the aromatic amine compound having a plurality of benzene rings is 20 to 100 parts by mass with respect to 100 parts by mass of the total amount of the aromatic amine compound. Still more preferably, the component (B) is selected from 4,4'-methylenebis (2-ethylaniline) represented by chemical formula (7) and diethyltoluenediamine represented by chemical formula (8). At least one species of group:

Examples of commercially available products of the component (B) include aromatic amine hardeners (4,4'-methylenebis (2-ethylaniline), product name: KAYAHARD AA), manufactured by Nippon Kayaku Co., Ltd. Ethyltoluenediamine hardener (product name: ETHACURE100), etc. (B) component can be used alone or in combination of two or more kinds.

The component (C) reduces the thermal expansion coefficient of the resin composition for underfill. Examples of the component (C) include silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, mica, white carbon, and the like. From the viewpoint of reduction in the thermal expansion coefficient of the resin composition for underfill after hardening and cost, Look, silicon oxide is better. Various types of silicon oxide used in this technical field, such as amorphous silicon oxide, crystalline silicon oxide, fused silicon oxide, and pulverized silicon oxide, can be used to reduce the thermal expansion coefficient of the resin composition for underfill after hardening. In point of view, amorphous silicon oxide is preferred. From the viewpoint of filling properties of the gap between the semiconductor wafer and the substrate, the particle diameter of the component (C) is preferably an average particle diameter: 0.1 to 2.0 μm, and more preferably 0.1 to 1.0 μm. The shape of the component (C) is not particularly limited, and examples thereof include a spherical shape, a scaly shape, and an irregular shape. From the viewpoint of the fluidity of the resin composition for an underfill, a spherical shape is preferred. (C) As a commercially available component, the silica particle (product name: SOE2) by Admatechs etc. are mentioned. (C) A component can be used individually or in combination of 2 or more types.

(D) component improves the adhesiveness of the resin composition for underfills. Examples of the component (D) include 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, p-styryltrimethoxysilane, and 3-methacrylic acid. Propylmethyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxy Silylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, etc., from the standpoint of adhesion, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane is preferred. (D) Commercially available products include KBM403, KBE903, and KBE9103 manufactured by Shin-Etsu Chemical Industry. (D) A component can be used individually or in combination of 2 or more types.

(E) The component system improves the solder wettability of the resin composition for underfills. Examples of the (E) component include 8-hydroxyquinoline represented by formula (6)

And 6-hydroxyquinoline, 4-hydroxyquinoline and the like, 8-hydroxyquinoline is preferred. (E) A component can be used individually or in combination of 2 or more types.

The resin composition for underfills of the present invention includes, from the viewpoint of adhesiveness of the resin composition for underfills and durability after curing, 100 parts by mass of the resin composition for underfills. The content of (A) component is preferably 10 to 35 parts by mass.

The resin composition for an underfill contains the component (B) in an amount of 30 to 120 based on 100 parts by mass of the component (A) from the viewpoints of the controllability of the reaction rate at the time of TCB and the high effect of suppressing voids during heating and pressing Mass parts are preferred.

The resin composition for an underfill is contained in an amount of 100 parts by mass with respect to the component (A) from the viewpoints of the fluidity of the resin composition for an underfill and the thermal expansion coefficient of the resin composition for an underfill after curing. The component (C) is preferably 160 to 400 parts by mass.

From the viewpoint of the adhesiveness of the resin composition for underfill, the resin composition for underfill preferably contains the component (D) in an amount of 0.05 to 2 parts by mass based on 100 parts by mass of the component (A).

From the viewpoint of solder wettability of the resin composition for underfill, the resin composition for underfill is contained in an amount of 0.5 to 3 parts by mass relative to 100 parts by mass of the resin composition for underfill. Better.

In the resin composition for underfills of the present invention, pigments such as carbon black, dyes, defoamers, antioxidants, other additives, and the like may be further blended as needed, as long as the object of the present invention is not impaired. Solvents, etc. However, from the viewpoint of suppressing foaming of the resin composition for underfill during coating in a heated environment, in the present invention, an organic solvent having a low boiling point is preferably not included.

The resin composition for an underfill of the present invention can be divided into components (A) to (E), other additives, etc. simultaneously or separately. It is obtained by applying heat treatment separately as needed, while stirring, melting, mixing, and dispersing. In particular, when the component (B) is solid, the viscosity of the resin will be increased and the handleability will be significantly deteriorated if it is directly blended. Therefore, it is preferable to liquefy by heating before mixing with the component (A). These mixing, stirring, and dispersing devices are not particularly limited, and a masher, a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like having a stirring and heating device can be used. Furthermore, these devices can be used in appropriate combination.

The resin composition for underfill of the present invention has a viscosity at a temperature of 25 ° C. of 10 to 100 Pa · s. Among them, the viscosity was measured using a Toki Sangyo viscosity meter (model: TV-20).

The resin composition for underfill of the present invention is preferably heat-cured at a pressure of 0.6 MPa or more and at 150 to 200 ° C. for 30 to 240 minutes.

[Flip-Chip Mount]

The flip-chip mounted body of the present invention is manufactured by the above-mentioned method for manufacturing a flip-chip mounted body. In addition, the flip-chip mounted body of the present invention includes the hardened product of the above-mentioned resin composition for an underfill.

[Example]

Although the present invention is described by way of examples, the present invention is not limited to these examples. In the following examples, unless otherwise specified, parts and% represent parts by weight and% by weight.

[Examples 1 to 28, Comparative Examples 1 to 24]

The formulations shown in Tables 1 to 4 were used to prepare a resin composition for underfill using a 3-roll mill.

[Evaluation of viscosity]

The viscosity of the prepared resin composition for underfill was measured at 25 ° C using a viscosity meter (model: TV-20) manufactured by Toki Sangyo. The results are shown in Tables 1 to 4.

[Sample production conditions]

A test wafer was prepared to evaluate the prepared resin composition for underfill. First, on the test wafer [Si size: 7.3 mm (width) x 7.3 mm (length) x 0.125 mm (thickness)]], a copper bump electrode for connection [for bumps: 30 μm (width) x 30 μm (length)] A solder layer was formed on a Cu pillar of 30 μm (height), the number of bumps: 1048, configured as an area matrix], and an organic resin substrate for loading a test wafer [substrate size: 187.5 mm (width) × 64.0 mm (length) × 0.36 mm (thickness), connection electrode: Cu / OSP (organic solderability protector) treatment). The solder formed on the Cu pillar was an Sn-Ag-based solder (melting point: about 223 ° C).

Using a dispenser (model: Super Σ CM II V5) made by Musashi Engineering Co., Ltd., the prepared resin composition for underfill was coated on an organic resin substrate into an X pattern with a 23G needle.

Then, using a flip-chip bonding machine (model: FCB3) manufactured by Panasonic Factory Solutions, a thermal-compression-bonding (TCB: Thermal-Compression-Bonding) test wafer and an organic resin substrate were used to perform copper bump electrodes for connection of the test wafer. Connection to an electrode for connection with an organic resin substrate. At this time, the table temperature of the flip chip bonding machine was set to 60 ° C, and the TCB temperature curve was set to six conditions of A, B, C, D, E, and F. Figures 1 to 6 show the TCB temperature curves for these six conditions. The TCB curve is obtained by placing a thermocouple (50 μm) between the test wafer and the organic resin substrate. ). The highest temperature of curves A to E is 262 ° C, and the highest temperature of curve F is 155 ° C. In curve A, the temperature is above the melting point of the solder for 1.2 seconds; in curve B, the temperature is above the melting point of the solder for 3.8 seconds; It was heated at a temperature of 10.9 seconds, and was heated at a temperature above the melting point of the solder for 15.8 seconds on the curve E, and it was not reached a temperature above the melting point of the solder on the curve F. The pressure of the TCB temperature curve for these six conditions was 40N.

The TCB-treated test piece was placed in a pressure oven (heating and pressing oven) having a combination of the following temperature curves A to C and pressure curves A to D to harden the resin composition for underfill.

Temperature curve A: The temperature was raised from room temperature to 165 ° C in 30 minutes, and the temperature was lowered to room temperature after being held at 165 ° C for 90 minutes.

Temperature curve B: The temperature was raised from room temperature to 165 ° C in 30 minutes, and the temperature was lowered to room temperature after being held at 165 ° C for 60 minutes.

Temperature curve C: The temperature was raised from room temperature to 165 ° C in 30 minutes, and the temperature was lowered to room temperature after being held at 165 ° C for 30 minutes.

Pressure curve A: At the same time when the temperature starts to rise, the pressure is increased from normal pressure, and the pressure of the oven is increased to 0.7 MPa in 5 minutes. At the same time, the pressure was reduced to bring the pressure down to normal pressure.

Pressure curve B: The pressure rises from normal pressure at the same time as the temperature starts to rise. The pressure of the oven is increased to 0.6 MPa in 5 minutes, and the pressure is reduced at the same time as the heating time ends to reduce the pressure to normal pressure.

Pressure curve C: The pressure rises from normal pressure at the same time as the temperature starts to rise. The pressure of the oven is increased to 0.5 MPa in 5 minutes, and the pressure is reduced at the same time as the heating time ends to reduce the pressure to normal pressure.

Pressure curve D: The pressure rises from normal pressure at the same time as the temperature rises. The pressure of the oven is increased to 0.3 MPa in 5 minutes, and the pressure is reduced at the same time as the heating time ends to reduce the pressure to normal pressure.

[Measurement of reaction rate]

The reaction rate (unit:%) of the resin composition for underfills was measured. Using differential scanning thermal analysis (DSC) measurement of the resin composition for underfill before and after TCB (temperature increase rate: 10 ° C / min), from the area of the exothermic peak before and after heating, according to the formula: {1- (the release after TCB) Heat) / (Exothermic heat before TCB)} × 100 (%).

[Initial evaluation]

For each example and comparative example, seven test pieces were produced.

"C-SAM Test"

In the test pieces produced in each of the examples and comparative examples, the state of occurrence of voids and interlayer peeling was confirmed by a reflection method using an ultrasonic flaw detection device. The determination It is implemented on all test pieces produced. Those who see a white shadow on the C-SAM image are defective.

"Flat grinding test"

From the 7 test pieces produced, 2 test pieces were taken out, and only the wafer portion was removed by grinding. Then, the wafer-removed portion of the organic resin substrate from which the wafer was removed was observed with an optical microscope (× 100, × 200) to confirm the existence of the cavity. Those who observed more than one cavity were considered to be defective. In addition, when two modes of good and bad were confirmed by the C-SAM test, the test pieces were observed as good and bad one by one.

"Solder Wetting Test"

Two test pieces were taken out of the seven test pieces produced, and cut to observe the joint portion between the wafer and the substrate, and then polished to expose the joint portion between the wafer and the substrate. Then, using a scanning electron microscope (SEM), the exposed joints were observed at 1000 times. At this time, it was considered that the alloy layer was not formed in the joint part as a defect. Furthermore, when two modes of good and defective products were confirmed by the C-SAM test, the good and defective products were observed one by one. FIG. 7 shows a photograph of a test piece having an alloy layer formed on a cross section. It can be seen from FIG. 7 that the alloy layer is formed in the solder, particularly near the interface between the copper bump electrode (the lower part in FIG. 7) and the solder, and the interface between the connection electrode (the upper part in FIG. 7) and the solder. nearby.

"Resistance Test"

The resistance values of the seven test pieces produced were measured, and the resistance values between the pads were measured. The test piece has a daisy chain structure, and a test piece with a resistance value of 28 to 32 Ω is acceptable.

"X-ray observation"

The X-ray inspection apparatus was used for the test pieces produced in each of the examples and comparative examples, and it was confirmed whether there was solder bridge between the terminals. This measurement is performed on all the test pieces produced. In the X-ray image, the solder connected between the terminals is defective.

[MRT Evaluation]

In the initial evaluation, the prepared test piece (n = 3) was placed in a constant temperature and humidity tank (30 ° C / 60% RH) for 192 hours, and then passed through a reflow furnace at 260 ° C three times.

The C-SAM test, resistance test, and X-ray observation were performed in the same manner as in the initial evaluation. In addition, test pieces with poor initial evaluation results were not evaluated by MRT.

As can be seen from Tables 1 to 6, the results of the void test, the connectivity test, the MRT-evaluated void test, and the connectivity test for all of Examples 1 to 28 were good. In contrast, Comparative Examples 1 to 4, 15 to 20 where the response rate at the end of the TCB curve was too high were observed in the initial evaluation. To the hollow. In Comparative Examples 5 to 14 in which the pressure of the heating and pressing oven was too low, voids were also observed in the initial evaluation. Comparative Example 21 not containing the (E) component had poor connectivity in the initial evaluation. In Comparative Example 22, where the temperature of the TCB curve was too low (maximum temperature: 155 ° C), the connectivity evaluated in the initial stage was also poor. In Comparative Example 23 not containing the (D) component, the resistance value evaluated at the initial stage and the result of X-ray observation were poor. In Comparative Example 24 which did not contain the (C) component, voids were observed in the initial evaluation.

As described above, it is possible to provide a method for manufacturing a flip-chip mounting body and a resin composition for a first-supply underfill used in the method for manufacturing the flip-chip mounting body. The first-feed type flip chip bonding process is very useful because it can suppress the occurrence of voids in the first-feed type underfill resin composition.

Claims (7)

A method for manufacturing a flip chip mounting body in which a copper bump electrode for connection provided on a semiconductor element is opposed to a connection electrode provided on a circuit board, and is provided by the semiconductor element The copper bump electrode for connection is connected to the solder of the connection electrode provided on the circuit board, so that the semiconductor element is mounted on the circuit board, and the gap between the circuit board and the semiconductor element is sealed with resin. This method of manufacturing a flip chip package The following steps are included in sequence: (1) a step of providing a solder layer with a melting point of 210 to 250°C on at least one of the copper bump electrode for connection of the semiconductor element and the connection electrode of the circuit board; (2) will include ( A) The pre-supplied underfill resin composition for epoxy resin, (B) aromatic amine hardener, (C) inorganic filler, (D) silane coupling agent, and (E) flux is supplied to the circuit board Steps; (3) Thermo-compression bonding the semiconductor element and the circuit board, heating the copper bump electrode for connection of the semiconductor element and the connection electrode for the circuit board at a temperature above the melting point of the solder for more than 1 second, and then feeding the bottom of the type The step of performing solder connection when the reaction rate of the resin composition for the filler is 0.1 or more and 25% or less; and (4) Under the pressure of 0.6 MPa or more, the resin composition for the under-filler supplied first is supplied The step of hardening the substance; the above reaction rate is measured using differential scanning thermal analysis (DSC) of the resin composition for underfill before and after TCB (heating rate: 10°C/min), by the peak area of the exothermic spectrum before and after heating, according to The following formula is obtained: Formula: {1-(heat release after TCB)/(heat release before TCB)}×100(%). The method for manufacturing a flip-chip mounted body as described in item 1 of the patent application, wherein the component (B) is selected from the group consisting of an aromatic amine hardener represented by the chemical formula (7) and an aromatic represented by the chemical formula (8) At least one group of amine hardeners:

The method for manufacturing a flip-chip mounted body as described in item 1 or 2 of the patent application, wherein (A) component is selected from bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type At least one kind of epoxy resin and naphthalene-type epoxy resin. A flip-chip mounted body manufactured by the method for manufacturing a flip-chip mounted body as described in any one of claims 1 to 3. A resin composition for first-feed underfill, which contains (A) epoxy resin, (B) aromatic amine hardener, (C) inorganic filler, (D) silane coupling agent and (E) flux ; At a temperature: 25°C, the viscosity is 10 to 100 Pa‧s; it is a method for manufacturing a flip-chip mounted body as described in any one of patent application items 1 to 3, wherein The reaction rate of the supply-type underfill resin composition after being heated at a temperature above the melting point of the solder for 1 second or more is 0.1 or more and 25% or less. Analysis (DSC) measurement (heating rate: 10°C/min), obtained by the peak area of the exothermic spectrum before and after heating, according to the following formula; formula: {1-(heat release after TCB)/(heat release before TCB Calories)}×100(%). The resin composition for pre-feeding underfill as described in item 5 of the scope of patent application, wherein (E) component is 8-hydroxyquinoline and is 100 parts by mass relative to the resin composition for pre-feeding underfill , (E) component is 0.5 to 3 parts by mass. A pre-fed flip chip mounted body having a cured product of a resin composition for a pre-fed underfill as described in item 5 or 6 of the patent application.