JP7066350B2 - Highly productive underfill insulation film for gang bonding processes - Google Patents

Description

The present invention relates to an underfill insulating film (NCF) used for flip-chip mounting a semiconductor chip, chip / chip-to-chip or chip / circuit board-to-chip filling, and more specifically, such. The present invention relates to an underfill insulating film having properties suitable for a gang bonding process, which is an effective method for improving productivity (shortening tact time) in a various mounting process, and its use.

In mounting semiconductor chips such as flip chip (FC) mounting, it is more widely used than before to fill the space between the semiconductor chip and the circuit board with a liquid underfill material after connecting the semiconductor chip and the circuit board. (See, for example, Patent Document 1). Specifically, for example, in a flip chip BGA, a chip with a solder bump was FC-connected to a packaging substrate, and a liquid underfill was injected and cured.
However, in recent years, in order to increase the amount of signals between semiconductor chips, the number of bumps tends to increase, and the chip area is limited, so that the pitch of bumps is becoming narrower. For example, in the advanced fields of processors and memory, chips with ultra-multi-pin bumps are mounted close to each other on a silicon interposer, and memory chips with a large number of bumps formed on both sides by through silicon vias (TSVs) are stacked. It is expected that it will be put into practical use and that it will be widely used due to cost reduction.
In addition, the height of the bump was large in consideration of relaxation of thermal stress between the chip and the substrate and underfill filling property, but in the case of silicon interposers compatible with high-density bumps and cases where silicon chips are laminated. Since the same silicon material is used, it is not necessary to consider thermal stress, and the gap is becoming narrower due to the trend of heat conduction (heat dissipation) and the trend of lowering the height of IC packages.
In the filling method using a liquid underfill material, it has become difficult to fill without leaving air bubbles between the chips having such a narrow pitch and a narrow gap. Underfill is required to have functions such as ensuring insulation between bumps and supporting stress generated in the bump portion, but if the filling property is poor, the reliability is lowered in such a respect.
In addition, when a large chip is FC-connected to a resin substrate, the bump connection near the outer periphery may break due to heat stress such as during reflow, and the yield may decrease. In such a case, instead of post-injection of underfill, There has been a demand for a paste or film-like pre-injection material that forms an underfill that supports bumps at the same time as FC connection.
On the other hand, a method of flip-chip connection via an anisotropic conductive film (ACF) has also been put into practical use in the liquid crystal driver IC field. However, since this method adds conductive particles to the film, there is a concern that short circuits between bumps may be induced in the trend of narrowing the pitch of bumps. In addition, it is difficult to apply it in a general-purpose IC package because it cannot withstand the reflow temperature because it has been developed to be mounted on a display having no heat resistance. Due to its reliability and cost, it is difficult to connect with solder bumps, which are the mainstream in recent years, and to adapt to the process. Further, since the light transmittance is poor due to the addition of conductive particles, the alignment mark cannot be visually recognized when the ACF is attached to the bump surface of the chip, so that the alignment between the chip and the substrate cannot be performed. Therefore, there is also a problem that the bonding film cannot be attached to the bump surface at the wafer level and individualized to be used as a chip with a bonding material.
Also, in the method of arranging the paste-like underfill material (NCP) between the chips and the substrate before joining, it is difficult to control the protrusion of the resin, and when the chips are laminated or the chips are arranged close to each other. In addition, it becomes difficult to apply.

In this way, NCF is regarded as a promising bonding material in IC packages for FC mounting of bump chips with narrow pitch and narrow gap, FC mounting of large chips on resin substrates, and FC mounting of chips in close proximity. .. Specifically, a resin film is used as an underfill insulating film, and after being placed between the semiconductor chip and the substrate, the resin flows when the semiconductor chip and the substrate are FC-bonded by heating and weighting. Has proposed a technique for filling the space between a semiconductor chip and a substrate.
However, in the normal NCF method, since it is necessary to raise and cool the head of the flip chip bonder for each chip, there is a problem in productivity (tact time), and it has not been fully spread. In recent years, crimping using NCF is performed in two stages, temporary crimping and main crimping, and by adopting so-called gang bonding, in which multiple chips are collectively crimped, the need for temperature rise and cooling of the head and the number of times are reduced. Attempts have been made to improve productivity.
In the gang bonding process, the electrode on the chip side and the electrode on the substrate side are aligned and temporarily crimped in the temporary crimping process, and the solder is melted and soldered between the electrodes in the main crimping process. For example, Patent Document 2 describes a step 1 of supplying an adhesive film for semiconductor bonding to a surface of a semiconductor chip with a solder electrode having a solder electrode, and the semiconductor chip with a solder electrode via the semiconductor bonding adhesive film. Step 2 of temporary bonding (corresponding to the above-mentioned temporary crimping) on a semiconductor chip or circuit board having a counter electrode or electrode pad at a temperature lower than the solder melting temperature is brought into contact with a bonding head heated to a temperature higher than the solder melting temperature. This is an adhesive film for semiconductor bonding used in a method for manufacturing a semiconductor device having the step 3 of solder bonding (corresponding to the above-mentioned main crimping), and contains at least a thermosetting resin, a thermosetting agent, and a high molecular weight compound. A semiconductor bonding adhesive film having a specific minimum melt viscosity in a specific temperature range and having a specific relationship between the melt viscosity and the minimum melt viscosity at a temperature 10 ° C. higher than the temperature at which the minimum melt viscosity is reached is described. ing.
However, when a conventional adhesive film for semiconductor bonding is used, voids and poor continuity may occur in temporary crimping, and a solution thereof has been desired.

Japanese Unexamined Patent Publication No. 10-158366 Japanese Unexamined Patent Publication No. 2016-201418

The problem to be solved by the present invention is an underfill insulating film suitable for a gang bonding process, which can solve problems such as poor continuity and generation of voids in a so-called gang bonding process using NCF in view of the above background technique. This is to significantly improve productivity and cost in the semiconductor chip mounting process.

As a result of diligent studies to solve the above problems, the present inventors have made an underfill insulating film for a gang bonding process having a specific composition, that is, (a) a phenoxy resin, a polyimide resin, a polyamide imide resin, and a polyamide resin. , And at least one resin component selected from acrylic resin, (b) a heat radical polymerizable substance, optionally (c) an epoxy resin, and (d) a heat radical generator, each containing a predetermined amount of a gang bonding process. We have found that the above-mentioned problems can be effectively solved by the underfill insulating film for plastic use, and have completed the present invention.
That is, the present invention and each embodiment thereof are as described in the following [1] to [15].

[1]
Underfill insulating film for gang bonding process containing the following components (a) to (d):
(A) At least one resin component selected from phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin: 10 to 40 parts by mass (b) Thermal radically polymerizable substance: 20 to 85 parts by mass (c) ) Epoxy resin: 0 to 65 parts by mass (d) Thermal radical generator: 0.1 to 5 parts by mass (Here, the contents of (a), (b), (c) and (d) are (a). (B) and (c) are parts by mass with respect to a total of 100 parts by mass).
[2]
The content of the (b) thermal radically polymerizable substance is 20 to 65 parts by mass, the content of the (c) epoxy resin is 20 to 65 parts by mass, and the (f) epoxy curing agent is (a). The underfill insulating film for a gang bonding process according to [1], which contains 0.5 to 10 parts by mass with respect to 100 parts by mass in total of (b) and (c).
[3]
Further, the undercoat for the gang bonding process according to [1] or [2], which contains (e) a polymerization inhibitor in an amount of 600 to 10000 mass ppm with respect to the amount (mass) of the thermal radically polymerizable substance (b). Fill insulating film.
[4]
Further, any one of [1] to [3], which contains (g) a flux agent in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of (a), (b) and (c). The underfill insulating film for the gang bonding process described in.
[5]
In the measurement using the dynamic viscous elasticity measuring device, the melt viscosity η ^* ₁ at 120 ° C. when the temperature was raised from 60 ° C. to 10 ° C./min was 2 × 10 ² × 10 ⁴ Pa · s. The underfill insulating film for a gang bonding process according to any one of [1] to [4], wherein the melt viscosity η ^* ₂ at 140 ° C. is 3 × 10 ² to 3 × 10 ⁵ Pa · s. ..
[6]
In the measurement using the dynamic viscous elasticity measuring device, the minimum melt viscosity η ^* ₃ when the temperature is raised from 60 ° C to 10 ° C / min to 160 ° C is 2 × 10 ² to 5 × 10 ³ Pa · s. The underfill insulating film for a gang bonding process according to any one of [1] to [5], wherein the temperature at which the minimum melt viscosity is given is 100 ° C to 140 ° C.
[7]
In the measurement using the dynamic viscoelasticity measuring device, the temperature was raised from 60 ° C. to 160 ° C. at 10 ° C./min, then cooled to 60 ° C., and then raised again at 10 ° C./min. The underfill insulating film for a gang bonding process according to any one of [1] to [6], wherein the melt viscosity η ^* ₄ at ° C. is 1 × 10 ⁴ to 1 × 10 ⁸ Pa · s.
[8]
The underfill insulating film for a gang bonding process according to any one of [1] to [7], wherein the content of the conductive particles is 5% by mass or less.
[9]
The underfill insulating film for a gang bonding process according to any one of [1] to [8], wherein the 1-minute half-life temperature of the (d) thermal radical generator is 140 to 200 ° C.
[10]
The underfill insulating film for a gang bonding process according to any one of [3] to [9], wherein the ( e) polymerization inhibitor is a quinone-based polymerization inhibitor.
[11]
The underfill insulating film for a gang bonding process according to any one of [2] to [9], wherein the (f) epoxy curing agent is a latent curing agent.
[12]
The latent curing agents are 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2,4-diamino-6- [2'-methylimidazole- (2'-methylimidazolyl-). 1')]-The underfill insulating film for a gang bonding process according to [11], which is at least one selected from the ethyl-s-triazine isocyanuric acid adduct.
[13]
The underfill for a gang bonding process according to any one of [1] to [12], wherein the semiconductor chip on which the soldered electrode is formed and the circuit board on which the counter electrode facing the soldered electrode is formed are formed. It is a method of manufacturing a semiconductor device that is bonded via an insulating film.
α) The process of attaching the underfill insulating film for the gang bonding process on a wafer having a soldered electrode under vacuum, and
β) A step of dividing the wafer into semiconductor chips with an underfill insulating film for individual gang bonding processes, and
γ) A step of temporarily crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
δ) A plurality of thermocompression-bonded semiconductor chips and circuit boards that were thermocompression-bonded under temperature conditions where the maximum temperature was equal to or higher than the melting point temperature of the solder mounted on the chips. A method for manufacturing a semiconductor device, comprising a thermocompression bonding step, which is a step in which the semiconductor chip is simultaneously heated to a temperature condition equal to or higher than the melting point temperature of solder.
[14]
The underfill for a gang bonding process according to any one of [1] to [12], wherein the semiconductor chip on which the soldered electrode is formed and the circuit board on which the counter electrode facing the soldered electrode is formed are formed. It is a method of manufacturing a semiconductor device that is bonded via an insulating film.
α') The process of attaching the underfill insulating film for the gang bonding process on the circuit board, and
γ) A step of temporarily crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
δ) A plurality of thermocompression-bonded semiconductor chips and circuit boards that were thermocompression-bonded under temperature conditions where the maximum temperature was equal to or higher than the melting point temperature of the solder mounted on the chips. A method for manufacturing a semiconductor device, comprising a thermocompression bonding step, which is a step in which the semiconductor chip is simultaneously heated to a temperature condition equal to or higher than the melting point temperature of solder.
[15]
A method for manufacturing an electrical / electronic device using the method according to [13] or [14].

According to the underfill insulating film for a gang bonding process having a specific composition of the present invention, problems such as poor continuity and generation of voids are effectively suppressed in a so-called gang bonding process having a temporary crimping process and a main crimping process. An underfill insulating film that can be used and is particularly preferably used in a gang bonding process is provided.
The method for manufacturing a semiconductor device using the underfill insulating film for a gang bonding process of the present invention is excellent in productivity and the performance of the manufactured semiconductor device.
By using the underfill insulating film for a gang bonding process having a specific composition of the present invention, a semiconductor device having excellent performance and its intermediate products and applied products can be manufactured with high productivity.

It is a schematic diagram which shows the method of flip-chip mounting a semiconductor chip using the underfill insulating film (NCF) of the prior art. It is a schematic diagram which shows the process using the underfill insulating film (NCF) for a gang bonding process which is one Embodiment of this invention. It is a schematic diagram which shows the TSV process using the underfill insulating film (NCF) for a gang bonding process which is another embodiment of this invention.

(Gang bonding process)
In the present invention, the "gang bonding process" is a semiconductor in which a semiconductor chip on which a soldered electrode is formed and a circuit board on which a counter electrode facing the soldered electrode is formed are bonded via an underfill insulating film. It ’s a method of manufacturing equipment.
A temporary crimping step of heating and pressurizing the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
The semiconductor device comprising a main crimping step of heating and pressurizing a plurality of temporarily crimped semiconductor chips and a circuit board under temperature conditions where the maximum temperature is equal to or higher than the melting point temperature of the solder mounted on the chips. The manufacturing method of.
Here, the underfill insulating film may be attached to a semiconductor chip on which a soldered electrode is formed, or is attached to a circuit board on which a counter electrode is formed, prior to the temporary crimping step. May be good.
(Underfill insulation film for gang bonding process)
The underfill insulating film for a gang bonding process of the present invention has a specific composition, and is more specifically selected from (a) a phenoxy resin, a polyimide resin, a polyamide imide resin, a polyamide resin, and an acrylic resin. An underfill insulating film for a gang bonding process containing at least one resin component, (b) a heat radical polymerizable substance, optionally (c) an epoxy resin, and (d) a heat radical generator in predetermined amounts. ..
Hereinafter, each component constituting the underfill insulating film of the present invention will be described.

((A) At least one resin component selected from phenoxy resin, polyimide resin, polyamide-imide resin, polyamide resin, and acrylic resin)
The underfill insulating film for a gang bonding process of the present invention contains at least one resin component selected from (a) a phenoxy resin, a polyimide resin, a polyamide-imide resin, a polyamide resin, and an acrylic resin.
(A) At least one resin component selected from a phenoxy resin, a polyimide resin, a polyamide-imide resin, a polyamide resin, and an acrylic resin is added for the purpose of functioning as a resin for forming a film. Among the resin components (a), a phenoxy resin, a polyimide resin, and a polyamide-imide resin are preferable from the viewpoint of the glass transition point after curing, and a resin that can be dissolved in an organic solvent is preferable from the viewpoint of film production. The preferred solvent is preferably soluble in ethyl acetate, toluene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), at low temperatures. From the viewpoint of drying, it is more preferable that it can be dissolved in a solvent having a boiling point of 150 ° C. or lower.
As the resin component (a), one type may be used alone, or two or more types may be used in combination.
Further, when the resin component (a) is modified with a functional group that reacts with a thermosetting resin such as (b) a resin derived from a thermoradical polymerizable substance described later and (c) an epoxy resin, physical properties after curing, for example, Tg And the thermal expansion rate is improved. On the other hand, since it is necessary to maintain the latent curability before crimping, it is often better to avoid functional groups that are too active.
It is preferable that the compatibility with (b) a resin derived from a thermally radically polymerizable substance, which will be described later, and (c) a thermosetting resin such as an epoxy resin is high. This is because if the NCF resin is phase-separated and becomes turbid, the mark visibility on the chip surface deteriorates when it is attached to the bump surface.
Further, as the physical properties of the mounting material after curing, it is required that the glass transition point is high and the coefficient of thermal expansion is low, as in the case of liquid underfill. Resins that are more preferable in that respect will be described in detail below.

The content of at least one resin component selected from (a) phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin in the insulating film for underfill of the present invention is (a) phenoxy resin, polyimide resin. With respect to a total of 100 parts by mass of at least one resin component selected from polyamideimide resin, polyamide resin, and acrylic resin, and (b) a thermally radically polymerizable substance, and (c) an epoxy resin if present. It is 10 to 40 parts by mass.
When the content of the resin component (a) is 10 parts by mass or more, appropriate strength is easily developed in producing or using the film in the uncured stage. The content of the resin component (a) is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
On the other hand, when the content of the resin component (a) is 40 parts by mass or less, problems such as deterioration of fluidity and insufficient curing of the thermosetting resin component can be effectively suppressed. The resin content of the resin component (a) is preferably 35 parts by mass or less, and more preferably 30 parts by mass or less.

(Phenoxy resin)
As the resin component (a), a phenoxy resin is particularly preferable from the viewpoint of solvent solubility, compatibility with a thermosetting resin, film forming ability, insulating property, and the like from the viewpoint of glass transition point.
Preferred phenoxy resins include bisphenol skeletons (bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, bisphenol acetophenone skeleton, etc.) Examples include, but are not limited to, phenoxy resins having one or more skeletons selected from the group consisting of adamantan skeletons, terpen skeletons and trimethylcyclohexane skeletons.

Of these, in the present invention, a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol skeleton, a biphenyl skeleton, and a fluorene skeleton is preferable, and a group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a fluorene skeleton. A phenoxy resin having one or more skeletons selected from the above is more preferable.

Among them, a phenoxy resin having a structure represented by the following general formula (P1) is preferable.

Here, Rx and Ry each independently represent a hydrogen atom or a glycidyl group. L represents a single bond, or -C (Ra) (Rb)-, -O-, -S- or -SO _2- . Here, Ra and Rb each independently represent a hydrogen atom or an alkyl group.
R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. The alkyl group in R ¹ is preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1. Examples thereof include methyl, ethyl, isopropyl, t-butyl, t-pentyl, 2-ethylhexyl, t-octyl and n-nonyl. The alkoxy group in R ¹ is preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1. Examples thereof include methoxy, ethoxy, isopropoxy, n-butoxy, 2-ethylhexyloxy, n-octyloxy and n-nonyloxy. Examples of the halogen atom in R ¹ include a fluorine atom, a chlorine atom and a bromine atom. A hydrogen atom is particularly preferable for ^R1 .
m1 is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.

As the phenoxy resin having a fluorene skeleton, a phenoxy resin obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with diglycidyl ether of bisphenol and / or diglycidyl ether of biphenol is preferable. Of these, the phenoxy resin obtained by reacting biphenol with diglycidyl ether is preferable, and the phenoxy resin obtained by reacting with 2,2', 6,6'-tetramethyl-4,4'-biphenol diglycidyl ether is preferable. Especially preferable.

The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or a glycidyl group, but a glycidyl group is preferable from the viewpoint of reactivity with other components. The phenoxy resin may be used alone or in combination of two or more.

Examples of commercially available phenoxy resins include, for example, trade names manufactured by Toto Kasei Co., Ltd., FX280, FX293, FX293S (fluorene skeleton-containing phenoxy resin), trade names manufactured by Mitsubishi Chemical Corporation, jER 1256, jER 4250, and the like. Product name YP-50, YP-50S (both bisphenol A skeleton-containing phenoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., product name YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , YX6954 (bisphenol acetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, trade names manufactured by Mitsubishi Chemical Corporation, YX7200, YL7553, YL6794, YL7213, YL7282, YL7482 and the like.

In the present invention, the molecular weight of the phenoxy resin that can be preferably used as the resin component (a) is not particularly limited, but from the viewpoint of film forming ability and the like, it is possible to use a phenoxy resin having a number average molecular weight of more than 5000 in terms of polystyrene. preferable. The number average molecular weight of the phenoxy resin is more preferably 7,000 or more, and particularly preferably 9000 or more. On the other hand, the upper limit of the number average molecular weight of the phenoxy resin is not particularly limited, but is preferably 15,000 or less, more preferably 12,000 or less. When the number average molecular weight is 15,000 or less, the solubility in an organic solvent is improved, and the productivity can be improved.
The epoxy equivalent of the phenoxy resin is preferably in the range of 3000 to 20000, more preferably 5000 to 10000.
Further, the glass transition temperature measured by the differential scanning calorimeter is preferably 80 ° C. or higher, more preferably 130 ° C. or higher. When the glass transition temperature is in this range, the glass transition temperature of the entire cured insulating film for underfilm becomes high, and the reliability of the mounted product is improved. There is no particular upper limit to the glass transition temperature, but 250 ° C. or lower is preferable from the viewpoint of solvent solubility.

When the phenoxy resin is used as the resin component (a) in the present invention, the content of the phenoxy resin is not particularly limited, but the resin component (a), the heat radically polymerizable substance (b), and when present are present. Is 10 to 40 parts by mass with respect to a total of 100 parts by mass of the epoxy resin (c).
When the content of the phenoxy resin is 10 parts by mass or more, appropriate strength is easily developed in producing or using the film in the uncured stage. The content of the phenoxy resin is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
On the other hand, when the content of the phenoxy resin is 40 parts by mass or less, problems such as deterioration of fluidity and insufficient curing of the thermosetting resin component can be effectively suppressed. (A) The content of the resin for forming a film is preferably 35 parts by mass or less, and more preferably 30 parts by mass or less.

(Polyimide resin)
In the present invention, a polyimide resin can also be preferably used as the resin component (a).
For example, a solvent-soluble polyimide obtained by dehydrating and condensing a commercially available tetracarboxylic acid and a diamine in a solvent to polymerize is also suitable as a film-forming polymer preferably used in the present invention. A solvent-soluble polyimide can be polymerized with a combination of known monomers.
As a reaction point with the thermosetting resin, one having a reactive group in the side chain is more preferable in terms of increasing the Tg after curing and decreasing the coefficient of thermal expansion. A Tg of about 50 to 200 ° C. is preferable for developing melting characteristics when combined with a thermosetting resin.
Polyamide-imide resin, polyamide resin, and acrylic resin can also be applied to the present invention with the same index as the above-mentioned polyimide resin.

In the underfill insulating film for the gang bonding process of the present invention, it is preferable that the specific melt viscosities η ^* ₁ and η ^* ₂ at specific temperatures and conditions are within specific ranges, respectively, as described later, and further specific. In particular, the minimum melt viscosity η ^* ₃ obtained under the temperature and conditions, and the temperature that gives it, and the melt viscosity η ^* ₄ obtained under different specific temperatures and conditions, are each within a specific range. preferable. From this point of view, the underfill insulating film for the gang bonding process of the present invention is in the form of a solid film at room temperature, and is once melted by heating to reduce its viscosity so that it can adhere and penetrate bumps, and is cured by further heating. It is preferable to have a so-called thermosetting property, which increases the viscosity and makes it possible to suppress voids. For this purpose, in addition to at least one resin component selected from the above-mentioned (a) phenoxy resin, polyimide resin, polyamide-imide resin, polyamide resin, and acrylic resin, (b) a heat radical polymerizable substance, and (d). Use a thermal radical generator.
By using a resin derived from a system in which (b) a thermal radical polymerizable substance and (d) a thermal radical generator are combined, the resin film for underfill of the present invention can be obtained with an appropriate degree of design freedom. The curing start temperature, curing rate, potential, etc. can be imparted.
In the underfill insulating film for the gang bonding process of the present invention, from the viewpoint of further improving the degree of freedom in design and further improving the adhesiveness to the adherend, (b) a heat radically polymerizable substance and (b) It is particularly preferable to use (c) an epoxy resin in addition to d) a thermal radical generator.

((B) Thermal radically polymerizable substance)
The underfill insulating film for a gang bonding process of the present invention contains (b) a predetermined amount of a heat radically polymerizable substance for the purpose of suppressing voids during curing. The thermal radical reaction system is excellent for exhibiting rapid curing in a temperature range in which voids are suppressed in NCF applications because of its potential effect.
Here, the (b) thermally radically polymerizable substance is a substance having a functional group polymerized by a thermal radical, and examples thereof include (meth) acrylate and a maleimide compound. The thermally radically polymerizable substance can be used in either a monomer or an oligomer state, and a monomer and an oligomer can be used in combination.
As the (b) thermal radically polymerizable substance, (meth) acrylate is particularly preferable. As the (meth) acrylate, a monofunctional (meth) acrylate and a bifunctional or higher (meth) acrylate can be used. Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) acrylate. Examples of the bifunctional or higher (meth) acrylate include bisphenol F-EO modified di (meth) acrylate, bisphenol A-EO modified di (meth) acrylate, bisphenol F epoxy (meth) acrylate, bisphenol A epoxy (meth) acrylate, and tri. Examples thereof include methylol propanetri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, and polyfunctional urethane (meth) acrylate. These (b) thermally radically polymerizable substances may be used alone or in combination of two or more.
Among these, bifunctional (meth) acrylate is preferably used because it is easy to control the characteristics at the time of curing. Among them, epoxy (meth) acrylate and the like are particularly preferably used from the viewpoint of compatibility and heat resistance.
It is also preferable to use a polyfunctional (meth) acrylate in combination to introduce a crosslinked structure. As the polyfunctional (meth) acrylate, trimethylolpropane tri (meth) acrylate or the like is particularly preferably used.
In the present invention, (meth) acrylate means acrylate or methacrylate.

The content of (b) the heat radically polymerizable substance is (a) at least one resin component selected from phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin, and (b) heat radically polymerizable substance. It is 20 to 85 parts by mass with respect to 100 parts by mass of the total amount of the substance and (c) epoxy resin if present.
(B) The content of the heat radically polymerizable substance is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more. Since it is 20 parts by mass or more, it becomes easy to suppress voids at the time of curing. On the other hand, the content of (b) the heat radically polymerizable substance is preferably 65 parts by mass or less, and more preferably 55 parts by mass or less. When it is 85 parts by mass or less, the stickiness of the underfill insulating film for the gang bonding process can be suppressed. The less sticky, the easier it is to handle wafers and chips with NCF. Transport troubles that stick to jigs that come into contact with the NCF surface can also be suppressed. Adhesion of dust can also be suppressed.
Further, in order not to deteriorate the visibility when attached to the chip, it is preferable to select a structure that does not phase-separate from other resins.

((C) Epoxy resin)
The underfill insulating film for a gang bonding process of the present invention may contain a predetermined amount of (c) epoxy resin from the viewpoint of imparting adhesiveness to an adherend.
(C) Examples of the epoxy resin include bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type and phenol novolac type. , Bifunctional epoxy resins such as cresol novolak type, trishydroxyphenylmethane type, tetraphenylol ethane type and polyfunctional epoxy resins, or epoxy resins such as hydantin type, trisglycidyl isocyanurate type or glycidylamine type can be used. However, it is not limited to these. The epoxy resin can be used alone or in combination of two or more. From the viewpoint of alignment mark visibility, it is preferable that the resin has good compatibility with the film-forming resin and other thermosetting resins and does not phase-separate from them.
From the viewpoint of reducing stickiness at room temperature, a solid epoxy resin is preferable, and from the viewpoint of improving the glass transition point and elastic modulus after curing, a polyfunctional epoxy resin having two or more functionalities is more preferable. For these reasons, a cresol novolac type epoxy resin can be particularly preferably used.

The cresol novolak type epoxy resin may be any of o-cresol novolak type epoxy resin, m-cresol novolak type epoxy resin, and p-cresol novolak type epoxy resin, and in particular, o- represented by the following formula. Cresol novolac type epoxy resin is preferable. Further, as the glycidyl group in these resins, it is preferable that the phenolic hydroxyl group in the corresponding cresol novolak resin is replaced with a glycidyl group.
The molecular weight of the cresol novolak type epoxy resin is preferably 800 to 1300, more preferably 900 to 1300. The softening point is preferably 60 ° C. or higher, more preferably 80 ° C. or higher.

In the present invention, for example, when (c) an epoxy resin is used for the purpose of imparting adhesiveness, adjusting the curing speed, etc., the content of (c) epoxy resin is (a) phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin. , And at least one resin component selected from the acrylic resin, (b) a thermally radically polymerizable substance, and (c) an epoxy resin, which is 0 to 65 parts by mass with respect to 100 parts by mass in total. (C) The content of the epoxy resin is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more. (C) When the epoxy resin is contained, the adhesiveness and the curing rate of the entire film can be controlled more appropriately. On the other hand, the content of (c) epoxy resin is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less. (C) When the content of the epoxy resin is 65 parts by mass or less, the detrimental effect on the film formation can be further suppressed, and the blending amount of the radical curing system for suppressing voids can be secured.

((F) Epoxy curing agent)
When (c) an epoxy resin is used as the resin for imparting adhesiveness and adjusting the curing speed in the present invention, it is preferable to appropriately use (f) an epoxy curing agent. Since potential, migration resistance, and an appropriate curing rate are required for this application, it is desirable to appropriately select an applicable curing agent. Of these, the thermal radical curing system is responsible for the rapid curing required for void suppression, so latent curability is particularly important. That is, it is preferable to use a latent curing agent as the (f) epoxy curing agent.
The known curing agents, whether amine-based or acid anhydride-based, do not always have sufficient potential, and it is preferable to select a known curing agent that is suitable for this purpose to some extent from a part of phenol curing and imidazole curing.
Among them, a solid imidazole-based curing agent having good potential can be preferably used. More specifically, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1'). )]-Ethyl-s-triazine isocyanuric acid adduct and the like can be particularly preferably used.

The content of (f) epoxy curing agent is 0.5 to 10 parts by mass with respect to 100 parts by mass in total of (a) resin component, (b) thermal radically polymerizable substance, and (c) epoxy resin. It is preferably, more preferably 1 to 5 parts by mass. When it is 0.5 parts by mass or more, the curing time by heat treatment is shortened and it becomes easy to improve the productivity. Further, when the content of (f) the epoxy curing agent is 10 parts by mass or less, it becomes easy to secure long-term storage stability, which is also preferable from the viewpoint of suppressing outgas during crimping.

((D) Thermal radical generator)
In the underfill insulating film for the gang bonding process of the present invention, (d) thermal radical generation of organic peroxides, azo compounds, etc. is performed in order to promote the polymerization of (b) thermally radically polymerizable substances such as acrylic compounds. Use a predetermined amount of the agent together.
As the organic peroxide, for example, peroxyester, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate and the like can be preferably used. These organic peroxides may be used alone or in combination of two or more.
Among these (d) thermal radical generators, those having a one-minute half-life temperature of 140 ° C. or higher are preferable, and more preferably 160 ° C. or higher. When the 1-minute half-life temperature is 140 ° C or higher, the fluidity of the resin during crimping is appropriate, so the resin bites between the electrodes between the chip and the substrate (curing progresses before the electrodes come into contact, and the electrodes It is preferably used from the viewpoint of suppressing the phenomenon that the resin bites in between). On the other hand, one having a one-minute half-life temperature of 200 ° C. or lower is preferable, and more preferably 190 ° C. or lower. When the half-life temperature for 1 minute is 200 ° C. or lower, curing at the time of crimping is appropriate, and the effect of suppressing voids is high.
Further, from the viewpoint of suppressing peroxide volatilization in the solvent drying step during film production, the molecular weight of (d) the thermal radical generator is preferably 200 or more, more preferably 250 or more.
Among these, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane (manufactured by NOF CORPORATION, Pertetra A), n-butyl-4,4-di (t-). Butyl Peroxy) Valerate (NOF Corporation, Perhexa V), 2,5-dimethyl-2,5-bis (t-Butyl Peroxy) Hexane (NOF Corporation, Perhexa 25B), 2,5- Dimethyl-2,5-di (t-butylperoxy) -3-hexin (manufactured by NOF CORPORATION, perhexin 25B) and the like are preferably used.
The amount of (d) thermal radical generator added such as organic peroxide is (a) at least one resin component selected from phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin, and (b). ) The thermal radical polymerizable substance, and if present, (c) 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of the epoxy resin, and it is preferable to add 0.3 to 3 parts by mass. Since it is 0.1 part by mass or more, the curing of acrylate or the like is sufficient, and since it is 5 parts by mass or less, the storage stability of the underfill insulating film for the gang bonding process is good, and the outgas during crimping is good. Since it is suppressed, it is also preferable from the viewpoint of void suppression.

((E) Polymerization inhibitor)
The underfill insulating film for a gang bonding process of the present invention comprises at least one resin component selected from the above (a) phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin, and (b) thermal radical polymerization. It is preferable to contain (e) a polymerization inhibitor in addition to the substance and (d) the thermal radical generator. By containing (e) a polymerization inhibitor, (b) unnecessary polymerization of the heat radically polymerizable substance can be suppressed during storage, so that storage stability is improved. Further, in the case of a thermal radical curing system, the curing start temperature and the curing rate can be adjusted.
The content (mass) of the (e) polymerization inhibitor is preferably 600 to 10000 ppm, more preferably 800 to 5000 ppm with respect to the amount (mass) of the (b) thermally radically polymerizable substance. (E) Since the content of the polymerization inhibitor is 600 ppm or more, it is easy to realize sufficient storage stability, and since it is 100,000 ppm or less, (b) polymerization of the thermally radical polymerizable substance is necessary at the time of curing. It is possible to effectively suppress voids and the like without inhibiting the above. In particular, when the NCF is attached to a semiconductor wafer and used, the chip with the NCF is FC-connected after undergoing the dicing and pick-up steps. It may take some time from the wafer laminating to the flip chip connection, and particularly high storage stability is required. Therefore, it is preferable to contain (e) a polymerization inhibitor in the above range.

The type of (e) polymerization inhibitor is not particularly limited, and (e) a polymerization inhibitor suitable for (b) the type of the thermally radical polymerizable substance, the polymerization mechanism, and the like can be appropriately used. For example, quinones such as hydroquinone, methyl ether hydroquinone, p-benzoquinone, t-butylparabenzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, tetrachloro-p-benzoquinone; o -Nitro compounds such as dinitrobenzene, m-dinitrobenzene, 2,4-dinitrotoluene, 1,3,5-trinitrobenzene, 1,3,5-trinitrotoluene; o-nitrophenol, m-nitrophenol, p- Nitrophenols such as nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol; nitroso and nitron compounds such as methyl-α-nitrosoisopropylketone and phenyl-t-butylnitron; iron chloride (III) ) And the like, phenothiazine and the like can be appropriately used, but the present invention is not limited thereto.
Above all, it is preferable to use quinones because the polymerization inhibitory effect can be effectively exhibited even in the step of attaching NCF to the bump forming surface of the wafer, and p-benzoquinone (also referred to as PBQ), methyl-p-benzoquinone. , T-Butylparabenzoquinone (also referred to as TBQ), 2,5-diphenyl-p-benzoquinone is particularly preferred.

((G) Flux agent)
Further, in addition to / instead of the above (f) epoxy curing agent, (g) a flux agent, preferably an acid (anhydride) having a flux function can also be used. Such an acid (anhydrous) can cure the epoxy resin (c) and also has a flux function to remove the oxide film on the solder surface and the electrode surface, so that it is a semiconductor chip. It is preferable because the electric junction between the circuit board and the circuit board can be made easier and more reliable.
Examples of the acid (anhydride) having a flux function include aliphatic dicarboxylic acids such as adipic acid, aliphatic acid anhydrides such as tetrapropenyl anhydride succinic acid and dodecenyl anhydride succinic acid, hexahydroanhydride phthalic acid, and methyltetrahydrohydride phthalic acid. Examples thereof include alicyclic acid anhydrides such as acids, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride. As the acids (anhydrides) having these flux functions, one type may be used alone or two or more types may be used in combination. If these fluxes can be solidly dispersed in NCF, the potential becomes advantageous in terms of reaction with the epoxy resin. In order to disperse in solid form, those having poor solubility in the solvent used in the compounding solution described later are preferable. It is advisable to grind it into a size sufficiently smaller than the thickness of the NCF film and mix it. On the other hand, it is preferable that the melting point is reached at a temperature lower than the solder melting temperature and the flux activity is exhibited. Among these acids (anhydrides), succinic acid, adipic acid and the like are particularly preferable in view of the above-mentioned characteristics, solder connectivity and epoxy curing action, and industrial availability.

The blending amount of the (g) flux agent including the acid (anhydrous) having a flux function is at least one resin selected from (a) phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin. It is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of the components, (b) the heat radical polymerizable substance, and (c) the epoxy resin if present, more preferably. It is 0.5 parts by mass or more and 3 parts by mass or less. When the amount of (g) flux agent such as acid (anhydride) having a flux function is 0.1 parts by mass or more, solder wetting is promoted and electrical connection between the semiconductor chip and the substrate is established. It can be effectively promoted. When the blending amount of the (g) flux agent such as acid (anhydride) having a flux function is 10 parts by mass or less, it is preferable from the viewpoint of ensuring storage stability and suppressing outgas during a crimping test.

(Filler)
By adding the filler, the coefficient of thermal expansion of the underfill insulating film for the gang bonding process is lowered, the dimensional stability and the like are improved, the thermal stress on the chip and the substrate is lowered, and the reliability is also improved. On the other hand, as the filling amount increases, the flow characteristics deteriorate. In terms of mark visibility, in the case of a filler having a refractive index difference from that of the resin, if the size is larger from the vicinity of the wavelength of light, scattering will occur and the visibility will be deteriorated. Further, if a filler having a larger size intervenes in the chip / substrate gap, it causes defects such as chip cracking. If a large filler gets caught between the bump and the electrode, conduction failure will occur.
As the inorganic filler, silica (molten silica, crystalline silica, fumed silica, etc.), alumina, aluminum nitride, silicon nitride, boron nitride powder, etc. may be used as long as they satisfy the above conditions. In terms of fluidity, fumed silica and fused silica are particularly preferable.

The average particle size of the inorganic filler is preferably 0.01 μm or more. When it is 0.01 μm or more, it is possible to suppress an increase in melt viscosity due to the interaction between the filler and the resin. The average particle size of the inorganic filler is preferably 3 μm or less, more preferably 3 μm or less, from the viewpoint of suppressing the biting of the filler between the semiconductor element and the electrode of the substrate and the transparency of the underfill insulating film for the gang bonding process. It is 1 μm or less, more preferably 0.1 μm or less. The average particle size can be determined by observation with a photometric particle size distribution meter (for example, manufactured by HORIBA, device name; LA-910) or a microscope. However, in these fine particles, if the dispersion treatment is not performed well, the secondary particle size will be measured.
The particle size of the filler is preferably top-cut by the classification operation, and it is preferable to cut the coarse particles with a filter also in the process of compounding, dispersing and coating.

The content of the inorganic filler in the underfill insulating film for the gang bonding process is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more. When it is 5% by mass or more, the coefficient of thermal expansion after curing becomes better than that without addition. The content of the inorganic filler in the underfill insulating film for the gang bonding process is preferably 60% by mass or less, more preferably 40% by mass or less. When it is 60% by mass or less, fluidity can be ensured, good transparency can be obtained, and biting of the filler can be satisfactorily suppressed when the semiconductor chip is mounted on the substrate via NCF.

(Other additives)
In the underfill insulating film for the gang bonding process of the present invention, components other than the above can be appropriately blended as long as it does not contradict the object of the present invention. Examples of other components include flame retardants, silane coupling agents, ion trapping agents, organic fillers and the like.
As the flame retardant, for example, a phosphorus compound, a metal hydroxide, an antimony trioxide, an antimony pentoxide, a brominated epoxy resin and the like can be used, but the flame retardant is not limited thereto.
By adding a silane coupling agent, it is possible to improve the adhesiveness between the filler and the resin interface, the semiconductor chip used in the process, the circuit board and the like, and the underfill insulating film for the gang bonding process. Examples of the silane coupling agent include an epoxy group such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. Those having a reactive double bond, etc. can be used, but are not limited thereto.
By adding an ion trap agent, ionic impurities such as cations and anions from other materials that make up the electrode wiring and the underfill insulating film for the gang bonding process are captured, and migration and corrosion of the wiring are prevented. can do. As the ion trapping agent, for example, hydrotalcites, bismuth hydroxide, chelates and the like can be used, but the ion trapping agent is not limited thereto.

(Physical characteristics of underfill insulating film for gang bonding process)
The underfill insulating film for a gang bonding process of the present invention comprises at least one resin component selected from (a) a phenoxy resin, a polyimide resin, a polyamide imide resin, a polyamide resin, and an acrylic resin, and (b) a thermally radical polymerizable substance. If desired, (c) an epoxy resin and (d) a thermal radical generator may be contained in a predetermined amount, and the physical properties of the film itself are not particularly limited, but various physical properties such as melt viscosity. However, it is preferable to satisfy the conditions described below.
That is, the underfill insulating film for a gang bonding process of the present invention is an underfill insulating film for a gang bonding process having the above-mentioned specific composition, and is measured using a dynamic viscoelasticity measuring device in relation to its use. It is preferable that the melt viscosity under each specific condition satisfies any or all of the following conditions.
The melt viscosity η ^* ₁ at 120 ° C. when the temperature is raised from 60 ° C. to 10 ° C./min is 2 × 10 ² to 2 × 10 ⁴ Pa · s.
Similarly, the melt viscosity η ^* ₂ at 140 ° C. is 3 × 10 ² to 3 × 10 ⁵ Pa · s.

The melt viscosity η ^* can be measured by using a rheometer (dynamic viscous elasticity measuring device (shear)) and raising the temperature at 10 ° C./min under the condition of a frequency of 1 Hz under nitrogen.
When the melt viscosity η ^* ₁ at 120 ° C. is 2 × 10 ² Pa · s or more, it is preferable from the viewpoint of preventing excessive protrusion and creeping up of the resin. The melt viscosity η ^* ₁ at 120 ° C. is more preferably 5 × 10 ² Pa · s or more.
Further, when the melt viscosity η ^* ₁ at 120 ° C. is 2 × 10 ⁴ Pa · s or less, air is entrained from the viewpoint of achieving an appropriate viscosity in the temporary crimping process of the gang bonding process and due to insufficient fluidity. , It is preferable from the viewpoint of suppressing defects such as poor penetration of bumps. In the early stages of the process of joining a semiconductor chip and a circuit board, the resin constituting the underfill insulating film for the gang bonding process of the present invention exhibits appropriate fluidity, and a narrow space between the semiconductor chip and the substrate is exhibited. It becomes easy to fill the resin without a gap, and it becomes difficult for the resin to get caught between the electrode on the semiconductor chip side and the electrode on the substrate side, and it becomes easy to secure good conduction between the two. The melt viscosity η ^* ₁ at 120 ° C. is more preferably 5 × 10 ³ Pa · s or less, and further preferably 2 × 10 ³ Pa · s or less.

When the melt viscosity η ^* ₂ at 140 ° C. is 3 × 10 ² Pa · s or more, the resin constituting NCF is appropriately cured during the temperature rise, so that the generation of voids during crimping can be suppressed. .. The melt viscosity η ^* ₂ at 140 ° C. is more preferably 1 × 10 ³ Pa · s or more, and further preferably 5 × 10 ³ Pa · s or more.
In addition, since the melt viscosity η ^* ₂ at 140 ° C. is ³ × 105 Pa · s or less, stable conduction is ensured at the initial stage of the process of joining the semiconductor chip and the circuit board. Is possible. The melt viscosity η ^* ₂ at 140 ° C. is more preferably ¹ × 105 Pa · s or less. This is because if the curing progresses too rapidly, the bump penetration may be poor and the continuity may be poor.
The melt viscosity η ^* ₁ and η ^* ₂ at 120 ° C. and 140 ° C. are, for example, at least one selected from fillers in films and (a) phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin. It can be adjusted by appropriately increasing or decreasing the content of the resin component of (b) the resin derived from the thermoradical polymerizable substance, (c) the curing start temperature of the thermosetting resin such as epoxy resin, and the curing rate. can. The curing start temperature and curing rate of the heat-curable resin are (b) the decomposition temperature of the heat radical generator if the heat radical curing system (mainly (b) when the curing behavior is defined by the heat radical polymerizable substance). The curing start temperature can be adjusted by changing. If it is an epoxy curing system (mainly (c) when the curing behavior is defined by the epoxy resin), it can be adjusted by changing (f) the epoxy curing agent.

In the underfill insulating film for the gang bonding process of the present invention, the minimum melt viscosity η ^* ₃ when the temperature is raised from 60 ° C. to 160 ° C. at 10 ° C./min in the dynamic viscoelasticity measuring device is 2 × 10. It is preferably ² to 5 × 10 ³ Pa · s, and the temperature at which the minimum melt viscosity is given is preferably 100 ° C. to 140 ° C.
Having a minimum melt viscosity η ^* ₃ within the above range in the temperature range of 100 ° C to 140 ° C, the underfill insulating film for the gang bonding process of the present embodiment is particularly suitable for the temporary pressure bonding step of the gang bonding process. Will have a good viscosity.
The minimum melt viscosity η ^* ₃ is more preferably 4 × 10 ² to 2 × 10 ³ Pa · s.
The temperature at which the minimum melt viscosity is given is more preferably 105 to 135 ° C, still more preferably 110 to 130 ° C.
The minimum melt viscosity η ^* ₃ and the temperature at which the minimum melt viscosity is given are, for example, a filler in a film and at least one resin component selected from (a) a phenoxy resin, a polyimide resin, a polyamideimide resin, a polyamide resin, and an acrylic resin. It can be adjusted by appropriately increasing or decreasing the content of (b) a resin derived from a thermoradical polymerizable substance, (c) a curing start temperature of a thermosetting resin such as an epoxy resin, and a curing rate. The curing start temperature and curing rate of the heat-curable resin are (b) the decomposition temperature of the heat radical generator if the heat radical curing system (mainly (b) when the curing behavior is defined by the heat radical polymerizable substance). The curing start temperature can be adjusted by changing. If it is an epoxy curing system (mainly (c) when the curing behavior is defined by the epoxy resin), it can be adjusted by changing (f) the epoxy curing agent.

In the underfill insulating film for the gang bonding process of the present invention, in the dynamic viscoelasticity measuring device, the temperature is raised from 60 ° C. to 160 ° C. at 10 ° C./min, cooled to 60 ° C., and then 10 again. It is preferable that the melt viscosity η ^* ₄ at 150 ° C. when the temperature is raised at ° C./min is 1 × 10 ⁴ to 1 × 10 ⁸ Pa · s. When the melt viscosity η ^* ₄ is in the above range, the underfill insulating film that has been heated by temporary crimping and then cooled can exhibit appropriate fluidity in this crimping, and the semiconductor chip and circuit board can be exhibited. Good bonding with and can be achieved.
The melt viscosity η ^* ₄ at 150 ° C. when the temperature was raised from 60 ° C. to 160 ° C. at 10 ° C./min, then cooled to 60 ° C., and then raised again at 10 ° C./min, was 1 ×. It is more preferably 10 ⁵ to 5 × 10 ⁷ Pa · s, and more preferably 1 × 10 ⁶ to 2 × 10 ⁷ Pa · s.
The melt viscosity η ^* ₄ at 150 ° C. when the temperature is raised from 60 ° C. to 160 ° C. at 10 ° C./min, then cooled to 60 ° C., and then raised again at 10 ° C./min, is, for example, It can be adjusted by appropriately increasing or decreasing the curing start temperature, curing rate, or the like of (b) a resin derived from a heat radical polymerizable substance, or (c) a heat-curing resin such as an epoxy resin. If the heat-curing resin has a curing start temperature and a curing rate of a thermal radical curing system (mainly (b) when the curing behavior is defined by a thermal radical polymerizable substance), (b) the decomposition temperature of the thermal radical generator is used. The curing start temperature can be adjusted by changing it. If it is an epoxy curing system (mainly (c) when the curing behavior is defined by the epoxy resin), it can be adjusted by changing (f) the epoxy curing agent.

In the process using the underfill insulating film for the gang bonding process of the present invention, the soldered electrode formed on the semiconductor chip is typically in direct contact with or bonded to the counter electrode formed on the circuit board. Ensures continuity. In this respect, the underfill insulating film for a gang bonding process of the present invention is also used for bonding a semiconductor chip and a substrate, but the so-called anisotropic method in which conduction between the semiconductor chip and the circuit can be obtained via conductive particles. Distinguished from conductive film (ACF).
Regarding the characteristics of the resin, since the anisotropic conductive film is usually used when mounting the driver chip of the display, it is required to be cured at a maximum temperature of 200 ° C. or less and about 180 ° C. for a non-heat resistant display. .. In addition, since it is a premise that conductive particles are bitten, the required level for bump penetration is low. The inventors have found that when the resin formulation used in the anisotropic conductive film is applied to the resin formulation of the underfill insulating film, it cures quickly, resulting in poor bonding due to poor fluidity during pressure bonding. rice field. As described above, it is difficult to directly apply the resin formulation of the anisotropic conductive film to the underfill insulating film.

The conductive particles contained in the anisotropic conductive film are fine with a diameter of several μm to several tens of μm, but with the recent further miniaturization of semiconductor devices and further increase in the density of mounting, such a situation is observed. Even with the use of fine conductive particles, it is difficult to completely eliminate the risk of unintended short circuits between electrodes. From this point of view, underfill insulating films for gang bonding processes are anisotropically conductive. It is an underfill film that is more suitable for mounting semiconductor devices that are finer than sex films at high density, and its superiority is expected to become even more remarkable in the future.

As described above, the underfill insulating film for the gang bonding process of the present invention preferably does not have conductivity in the thickness direction in order to prevent an unintended short circuit between the electrodes. From the standpoint of preventing short circuits, the underfill insulating film for the gang bonding process of the present invention has a low content of conductive particles or substantially no conductive particles unless there is a special technical need. Is desirable. That is, the content of the conductive particles in the underfill insulating film for the gang bonding process of the present invention is preferably 5% by mass or less, and particularly preferably 2% by mass or less.
From the viewpoint of preventing short circuits, it is desirable that the underfill insulating film for the gang bonding process of the present invention has a low metal content or substantially no metal content unless there is a special technical need. That is, the metal content of the underfill insulating film for the gang bonding process of the present invention is preferably 5% by mass or less, and particularly preferably 2% by mass or less.

(Manufacturing method of underfill insulating film for gang bonding process)
The underfill insulating film for the gang bonding process of the present invention is produced, for example, as follows. First, each of the above-mentioned components, which is a material for forming an underfill insulating film for a gang bonding process, is blended and dissolved or dispersed in a solvent (for example, methyl ethyl ketone, ethyl acetate, toluene, etc.) to prepare a coating liquid. When the filler is dispersed, it is dispersed by using a dispersion device such as a bead mill, if necessary. Next, the prepared coating liquid is applied on a substrate separator with a general-purpose coater to a predetermined thickness, and then the solvent is dried using a heat oven or the like to obtain an underfill insulating film for a gang bonding process. Form. As the drying conditions, if the residual solvent remains extremely, it becomes a factor of generating voids at the time of FC connection, so it is preferable to adjust the drying conditions to at least 1% or less. It is preferable to adjust the drying temperature and the drying time to such an extent that the curing reaction does not start significantly in the drying step. Adjust at 100 ° C for a few minutes as a guide.
Since there is a limit to the thickness that can be applied under the above conditions, if an excessively thick NCF is required, a predetermined thickness can be obtained by laminating a plurality of NCFs having a thickness satisfying the residual solvent condition.
The base material separator is preferably, for example, PET (polyethylene terephthalate), OPP (stretched polypropylene), CPP, poly-4-methylpentene-1, PTFE or the like coated with a release agent such as silicone as needed. Can be used.
Considering the adhesion of foreign matter, it is better not to handle NCF barely. In such a surface, after drying with the above coater, a slightly adhesive film may be laminated on the NCF surface, or a separator may be heat-laminated. If there is a difference in the ease of peeling of the easily peelable material on both sides of the NCF, the subsequent handling of the NCF becomes easy. By first peeling off the easily peelable material on the side that can be easily peeled off, NCF can be stably left on the heavier peelable easy-release material.

The thickness of the underfill insulating film for the gang bonding process of the present invention is not particularly limited, and should be appropriately set in consideration of the gap between the semiconductor chip and the circuit board and the height of connecting members such as electrodes and solder. Just do it. Assuming the current ordinary process, a thickness of about 1 to 250 μm is preferable, and a thickness of about 5 to 25 μm is more preferable. In the case of flip-chip connection between silicon materials, the thermal stress is small and the necessity of taking a large gap is small, so it is expected that the gap will be small in the future. On the other hand, when the resin substrate and the chip are connected, the bump height is increased so that the thermal stress can be alleviated according to the chip size and the characteristics of the resin substrate material. It is advisable to prepare a film thickness corresponding to each.
In the space under the chip filled with the underfill insulating film, there is a volume of protrusions such as bumps, and there is an appropriate gap in which the bumps are appropriately crushed. To form such an appropriate gap, subtract the bump volume from the volume calculated by the product of the gap and the chip area, add the volume of the good protrusion formation, and divide the volume by the chip area. , Appropriate film thickness can be estimated. Since the fluidity of the underfill insulating film changes depending on the bump layout, it is more preferable to test with a real chip.

(Product form of underfill insulating film for gang bonding process)
The underfill insulating film for the gang bonding process of the present invention is preferably protected by a releasable film. The release film has a function as a protective material for protecting the underfill insulating film for the gang bonding process until it is used in the actual process. The release film is peeled off, for example, when the semiconductor element is attached onto the underfill insulating film for a gang bonding process. As the release film, an easily peelable film such as a separator or a slightly adhesive film used in the above-mentioned manufacturing process may be used as it is.
Further, the underfill insulating film for the gang bonding process may be laminated with the back grind (BG) tape. As a method of using the underfill insulating film, as an adhesive tape for protecting the circuit surface at the time of back grind (BG), it is used by attaching it to the bump surface of the wafer with an easily peelable film / underfill insulating film configuration, and the easy peeling film layer. Disclosed is a method of dicing the underfill insulating film and the wafer after peeling off the underfill insulating film to obtain a chip with the underfill insulating film. The underfill insulating film for the gang bonding process of the present invention may be used in such a form.
Further, the underfill insulating film for the gang bonding process may be laminated with the dicing (DC) tape. As a method of using the underfill insulating film, a method of integrally using the dicing tape and the underfill insulating film is also disclosed, and the underfill insulating film for the gang bonding process of the present invention is used in such a form. You may.

(Manufacturing method of semiconductor device)
Using the underfill insulating film for the gang bonding process of the present invention, for example, by filling the space between the semiconductor chip and the circuit board, a soldered electrode formed on the semiconducting chip and provided on the circuit board. The joint with the counter electrode can be protected.
As the material of the solder, tin-lead metal material, tin-silver metal material, tin-silver-copper metal material, tin-zinc metal material, tin-zinc-bismuth metal material and the like are preferably used. can. It also includes a structure in which the solder is formed at the tip of the copper pillar. The material of the electrode and the counter electrode is not particularly limited as long as it is conductive, and examples thereof include gold / nickel and copper.

As one embodiment of the present invention, a semiconductor chip on which a soldered electrode is formed and a circuit board on which a counter electrode facing the soldered electrode is formed are connected via an underfill insulating film for a gang bonding process of the present invention. It is a manufacturing method of semiconductor devices that are joined together.
α) The process of attaching the underfill insulating film for the gang bonding process on a wafer having a soldered electrode under vacuum, and
β) A step of dividing the wafer into semiconductor chips with an underfill insulating film for individual gang bonding processes, and
γ) A step of temporarily crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
δ) A plurality of temporarily crimped semiconductor chips and the circuit board are subjected to thermal crimping under temperature conditions where the maximum temperature is equal to or higher than the melting point temperature of the solder mounted on the chip. Examples of the method for manufacturing a semiconductor device include a thermal pressure bonding step, which is a step in which the semiconductor chip is simultaneously heated to a temperature condition equal to or higher than the melting point temperature of solder.

Further, the underfill insulating film for the gang bonding process may be first attached to the substrate side instead of the wafer, and as an embodiment in such a case, the semiconductor chip on which the soldered electrode is formed faces the soldered electrode. A method for manufacturing a semiconductor device, in which a circuit board on which a counter electrode is formed is bonded via an underfill insulating film for a gang bonding process of the present invention.
α') The process of attaching the underfill insulating film for the gang bonding process on the circuit board, and
γ) A step of temporarily crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
δ) A plurality of temporarily crimped semiconductor chips and the circuit board are subjected to thermal crimping under temperature conditions where the maximum temperature is equal to or higher than the melting point temperature of the solder mounted on the chip. Examples of the method for manufacturing a semiconductor device include a thermal pressure bonding step, which is a step in which the semiconductor chip is simultaneously heated to a temperature condition equal to or higher than the melting point temperature of solder.

In the above embodiment, the underfill insulating film for a gang bonding process of the present invention, which exhibits appropriate plasticity and fluidity in temporary crimping and does not generate voids during solder melting in the main crimping for joining a semiconductor chip and a substrate, is used. Since it is used, the conduction between the soldered electrode formed on the semiconductor chip and the counter electrode provided on the circuit board is ensured, and the space between the semiconductor chip and the circuit board is filled without voids. Moreover, it is possible to provide high reliability of the semiconductor chip mounted on the circuit board after curing. Furthermore, by adopting a gang bonding process, multiple temporarily crimped semiconductor chips are heated to a temperature condition that is equal to or higher than the melting point temperature of the solder at the same time, which requires a long tact time for raising and cooling the head. It is possible to manufacture semiconductor devices with high productivity.

Hereinafter, a method for manufacturing a semiconductor device according to the above embodiment will be described with reference to the drawings.
First, a method of flip-chip mounting a semiconductor chip using an underfill insulating film (NCF) according to the prior art will be described with reference to FIG. 1.
FIG. 1A shows a step of attaching an underfill insulating film on a wafer having a soldered electrode under vacuum, and a step of dividing the wafer into individual semiconductor chips with an underfill insulating film. The semiconductor chip (1) and the circuit board (5) before the step of crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines. , And the cross-sectional view schematically showing the underfill insulating film (4). The semiconductor chip (1) has an integrated circuit formed on the surface of a semiconductor such as silicon, and has a soldered electrode for connection called a bump. The soldered electrode is formed by forming solder (3) on an electrode (2a) made of copper or the like via a diffusion-preventing metal film of a bump material.
These solder surfaces oxidize over time. If the oxide film is removed by plasma treatment or the like before applying the NCF, a more stable bond can be obtained.

In the circuit board (5), a circuit is formed on a substrate such as a rigid substrate, a flexible substrate, a silicon substrate, or a glass substrate. Further, in the mounting portion on which the semiconductor chip (1) is mounted, a counter electrode (2b) having a predetermined thickness is formed at a position facing the soldered electrode of the semiconductor chip (1).

Here, the underfill insulating film (4) is attached to the bumped semiconductor chip (1) in a process (not shown). The pasting is performed under vacuum at a temperature of, for example, 60 to 120 ° C. The underfill insulating film (4) exhibits fluidity, embeds irregularities due to the electrodes (2a) and solder (3) formed on the semiconductor chip (1), and adheres to the semiconductor chip (1).
Subsequently, the wafer with the underfill insulating film is separated into individual pieces to produce individual chips with the underfilm.

First, the plurality of electrodes (2a) and the plurality of counter electrodes (2b) are aligned after mark recognition so as to be in contact with each other on the substantially center line of each. The mark recognition is performed by recognizing the mark formed in the vicinity of the chip mounting portion of the substrate and the mark formed on the chip surface with the camera by the flip chip bonder. At this time, if the edge of the mark cannot be clearly identified through the NCF, the mounting position accuracy deteriorates. On the device side as well, devise ways to make it easier to recognize mark edges by using coaxial / diffuse lighting. Then, as shown in FIG. 1 (A), the head or the stage is moved based on the coordinates registered in advance, and the alignment is performed.

Next, as shown in FIG. 1 (B), the head (6) pressurizes and raises the temperature of the semiconductor chip to which the underfill insulating film (4) is attached, and the semiconductor chip is heated to the circuit board (5). ) Thermocompression bonding on top.
At this time, the stage side is set to about 80 ° C. to 180 ° C. in the setting with the constant heater. In the case of a resin substrate, warpage occurs, so that the temperature is preferably about 60 to 100 ° C. In the case where a silicon chip or silicon wafer is placed on the stage, the heat transfer is good, so the heating of the head escapes to the stage side and the actual temperature of the chip is significantly lower than the setting of the head, so the stage temperature is raised. It is good to set to.
The chip with NCF is held on the head side, but the temperature here is such that the underfill insulating film has fluidity at the initial stage of applying a load, but does not start curing significantly, for example, 60 ° C to 150 ° C. Is preferably in the range of 80 ° C to 130 ° C. Since the time during which sufficient bump contact can be achieved on the entire surface of the chip varies depending on the chip size and bump layout, it is preferable to adjust the time within a few seconds.
Next, the temperature of the head side is raised so that the actual temperature of the chip becomes the solder melting temperature. Since there is often a discrepancy between the set temperature of the head (6) and the actual temperature of the bump portion due to the effect of heat escape to the stage, a simulated chip with a thermocouple sandwiched under the chip is used. It is preferable to investigate the correspondence between the actual temperature and the set temperature.
The duration at the solder melting temperature is preferably in the range of 0.1 seconds to 20 seconds, more preferably in the range of 0.5 seconds to 5 seconds, from the viewpoint of reliably joining the electrodes. Further, if necessary, the semiconductor device may be cooled from the solder melting temperature and then released. Further, the duration of heat and pressure is preferably in the range of 30 seconds, more preferably in the range of 1 to 20 seconds, from the viewpoint of productivity.

Next, with reference to FIG. 2, a process using an underfill insulating film (NCF) for a gang bonding process, which is an embodiment of the present invention, will be described.
FIG. 2A schematically shows a step of temporarily crimping the semiconductor chip onto the circuit board so that the electrode of the semiconductor chip and the counter electrode of the circuit board are in contact with each other on substantially the center lines of each. It is a cross-sectional view which shows.
It should be noted that, α) the step of attaching the underfill insulating film for the gang bonding process under vacuum on the wafer having the soldered electrode, and β) the individual gang bonding process of the wafer, which is carried out prior to the step γ). The steps of dividing into a semiconductor chip with an underfill insulating film for use are the steps of attaching the underfill insulating film on a wafer having a soldered electrode under vacuum and the steps of attaching the wafers individually, respectively, as described in the above-mentioned prior art method. It is a process similar to the process of dividing into a semiconductor chip with an underfill insulating film, and differs only in that the underfill insulating film is for a gang bonding process.
In FIG. 2A, the left and center semiconductor chips (1), the circuit board (5), and the underfill insulating film (4) have been temporarily crimped, and the right semiconductor chip (1) and the circuit. The substrate (5) and the underfill insulating film (4) are intended to be temporarily crimped. Mark recognition and alignment are performed in the same manner as in the prior art.
The conditions for temporary crimping are not particularly limited, but for example, the stage side is set to about 80 ° C to 180 ° C. In the case of a resin substrate, about 60 to 100 ° C. is preferable in order to prevent warpage from occurring. In the case where a silicon chip or silicon wafer is placed on the stage, the heat transfer is good, so the heating of the head escapes to the stage side and the actual temperature of the chip is significantly lower than the setting of the head, so the stage temperature is raised. It is good to set to.
As the temporary crimping head, a ceramic heater similar to that of the prior art or an inexpensive constant heater can be used. The temperature on the head side is preferably in the range of, for example, 100 ° C. to 180 ° C. because the underfill insulating film causes fluidity in the initial stage of applying the load and the electrode on the chip side and the electrode on the substrate side are brought into contact with each other. The load varies depending on the chip size and the bump layout, but is preferably about 10 to 500 N. Although the time during which sufficient bump contact can be achieved on the entire surface of the chip varies, it is preferable to adjust the time within a few seconds in consideration of productivity.
In the process shown in FIG. 2A, the combination of the semiconductor chip (1), the circuit board (5), and the underfill insulating film (4) is sequentially temporarily crimped.

Next, as shown in FIGS. 2B and 2C, a combination of a plurality of semiconductor chips (1), a circuit board (5), and an underfill insulating film (4) after temporary crimping is combined with the main crimping head. Using (8), heat and pressurize under a temperature condition where the maximum temperature is equal to or higher than the melting point temperature of the solder (3), and the main crimping is performed. Here, a plurality of temporarily crimped semiconductor chips (1) are simultaneously pressurized under temperature conditions that are equal to or higher than the melting point temperature of the solder.
The conditions for the main crimping are not particularly limited, but for example, the stage side is set in the same manner as the above-mentioned temporary crimping. An inexpensive constant heater can be used for the main crimping head. Since there is often a discrepancy between the set temperature of the crimping head (8) and the actual temperature of the bump portion due to the effect of heat escape to the stage, it is simulated that a thermocouple is sandwiched under the chip. It is preferable to check the correspondence between the actual temperature and the set temperature on the chip.
The load varies depending on the chip size and the bump layout, but is preferably about 10 to 500 N. The duration at the solder melting temperature is preferably in the range of 0.5 seconds to 30 seconds from the viewpoint of reliably joining the electrodes, and more preferably in the range of 1 second to 20 seconds from the viewpoint of productivity. Particularly preferably, it is in the range of 2 to 10 seconds. Further, if necessary, the semiconductor device may be cooled from the solder melting temperature and then released.
In the embodiment shown in FIG. 2, since the temporary crimping and the main crimping are performed using separate heads set to different temperatures suitable for each process, the head temperature rises and falls are reduced or eliminated. By saving the time required for raising and lowering the head temperature, it is possible to significantly shorten the tact time and greatly improve the productivity. Further, since the main crimping is performed on a plurality of semiconductor chips at the same time, the productivity can be significantly improved in this respect as well. Further, since the main crimping does not require high-precision alignment, the main crimping can be performed with an inexpensive press device, and the cost can be significantly reduced.

The semiconductor chip (1) on which the soldered electrode (2a) is formed by the above process, the underfill insulating film (4) for the gang bonding process of the present invention, and the counter electrode facing the soldered electrode. The circuit board (5) on which (2b) is formed is a laminated body bonded in this order, and at least a part, preferably all of the soldered electrode (2a) is the counter electrode. It is possible to produce a laminate that is in electrical contact with at least a part, preferably all of (2b).

In the laminated body, the electrode (2a) with solder (3) and the counter electrode (2a) are located at a position where the electrode (2a) with solder (3) is in electrical contact with the counter electrode (2b). It is preferable that there is no underfill insulating film (5) for the gang bonding process between the 2b) and the solder (3), whereby a sufficient bonding area between the soldered electrode (2a) and the counter electrode (2b) is provided. Is ensured (solder is sufficiently wet and a solder joint is formed), and sufficient conduction is obtained.
Further, in the laminated body, at a position where the electrode (2a) with solder (3) is in electrical contact with the counter electrode (2b), the underfill insulating film (5) for a gang bonding process is contained. It is preferable that a through hole is formed, whereby a sufficient bonding area between the electrode (2a) with solder (3) and the counter electrode (2b) is secured (soldering is sufficient and solder bonding is sufficient). Is formed), and sufficient conduction is obtained.

FIG. 3 is a schematic view showing a process using an underfill insulating film (NCF) for a gang bonding process, which is another embodiment of the present invention.
In the embodiment shown in FIG. 3, a memory chip (TSV chip) in which a large number of bumps are formed on both sides by a through silicon via (TSV) is laminated in the vertical direction (thickness direction).
FIG. 3A shows a temporary crimping step corresponding to FIG. 2A in the embodiment described above, and the lower one of the two TSV chips (9) shown is FIG. 2. The left and center semiconductor chips (1) in (A) have been temporarily crimped, and the upper one has been temporarily crimped in the same manner as the right semiconductor chip (1) in FIG. 2 (A). It is something to try.
Next, as shown in FIGS. 3B and 3C, the semiconductor chip (1) after the temporary crimping, the plurality of TSV chips (9), the circuit board (5), and the underfill insulating film (4) are attached. Using the main crimping head (10), the main crimping is performed by heating and pressurizing under temperature conditions where the maximum temperature is equal to or higher than the melting point temperature of the solder (3). Here, the plurality of temporarily crimped TSV chips (9) are simultaneously heated to a temperature condition that is equal to or higher than the melting point temperature of the solder.
The conditions for the temporary crimping and the main crimping in this embodiment are basically the same as those described above with reference to FIG. 2, but the thermal conductivity is lowered by laminating a plurality of chips in the vertical direction. It is desirable to adjust the settings as appropriate in consideration of.

The laminate of the above two embodiments is a circuit board on which a semiconductor chip is mounted, and can be used as a semiconductor device through a necessary process. In the above laminated body, the underfill insulating film for the gang bonding process of the present invention after curing fills the space between the semiconductor chip and the circuit board with substantially no voids or voids, and has excellent performance as a semiconductor device. It has. That is, by using the underfill insulating film for the gang bonding process of the present invention, a semiconductor device having excellent performance can be manufactured with high productivity.
Such semiconductor devices can be suitably mounted on electrical and electronic devices used in information processing devices, displays, communication devices, transportation devices, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

In the following Examples / Comparative Examples, the evaluation of physical properties / characteristics was performed by the following method.
(Melting viscosity)
It was determined by measuring the temperature dispersion of molten viscoelasticity using a rheometer (manufactured by Anton Pearl, model number: MCR302). For the measurement, an underfill insulating film laminated to a thickness of 1.0 mm was used, and the film was previously brought into close contact with a jig at 80 ° C. for 3 minutes, and then measured under the following conditions. The second measurement was carried out again after the temperature was lowered to 60 ° C. over about 30 minutes after the first measurement was completed.
Environment: Nitrogen atmosphere Measuring jig: Parallel plate 8 mmφ
Deformation mode: Slip frequency: 1Hz
Temperature rise rate: 10 ° C / min Temperature range: 60 to 160 ° C (first time), 60 to 200 ° C (second time)
(Crimping test)
For test chips (G03 manufactured by Global Net Co., Ltd., vacuum diameter: 20 μm, vacuum pitch: 40 μm, bump height: 19 μm (copper pillar with tin / silver solder), size: 5 mm × 5 mm, daisy chain structure), Underfill insulating film for gang bonding process (20 μm) / Detachable PET film (Purex A54, 38 μm manufactured by Teijin DuPont Film Co., Ltd.) so that the underfill insulating film for gang bonding process is on the test chip side. , Laminated under vacuum using a vacuum laminator (manufactured by Takatori Co., Ltd.) (vacuum degree: 80 ° C. for 1 minute after reaching 13 Pa). An unnecessary chip peripheral portion was removed from the obtained laminated product with a design knife, and then the release film was removed to obtain a chip with an insulating film for an under film.
Next, using a bonder (manufactured by Shibuya Kogyo Co., Ltd., DB250), the chip with an insulating film for underfilm is appropriately positioned with respect to a test substrate (manufactured by Global Net Co., Ltd., G03, silicon substrate). After that, it was crimped under the following conditions.
Stage temperature: 160 ° C
Temporary crimping process Chip temperature: 160 ° C, load: 45N (4s)
Main crimping process Chip temperature: 260 ° C, load: 45N (10s)
The chip temperature was measured by separately creating a jig in which a thermocouple was inserted between the chip / substrate and crimping under the same conditions.
Voids were evaluated by observing the obtained laminated product of the chip / underfill insulating film / substrate for the gang bonding process from the chip side with an infrared microscope. Those with almost no voids were marked with "○", and those with significant voids were marked with "x". In addition, those with electrical connection were marked with "○", and those with poor continuity were marked with "x".

[Example 1]
As the resin component (a) for forming a film, 30 parts by mass of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX7200B35 (number average molecular weight of about 10,000, glass transition temperature by DSC, glass transition temperature of 149 ° C., epoxy equivalent of 8000)), (c) epoxy resin. 30 parts by mass of epoxy resin (manufactured by DIC Co., Ltd., N-695 (cresol novolac type, softening point 90 to 100 ° C.), prepared in advance using a methyl ethyl ketone solution having a solid content of 70%), (b) thermal radical As a polymerizable substance, a mixture of acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-130, bisphenol A-based epoxy acrylate 55-60%, acrylate monomer 40-45%, average molecular weight (Mw) 500, (e) polymerization prohibited. 40 parts by mass of hydroquinone monomethyl ether (conventional name: methquinone) 400 ppm as agent 1, and imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MAOK-PW (2,4-diamino-6- [2)) as an epoxy curing agent. '-Methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct)) 3 parts by mass, (d) Organic peroxide as a thermal radical generator (Perhexa 25B (manufactured by Nichiyu Co., Ltd., 1) Minute half-life temperature 180 ° C., molecular weight 290.45) 1 part by mass, (g) 1 part by mass of adipic acid as a flux agent, silica as a filler (OX50 (Japan Aerodil Co., Ltd., hydrophilic fumed silica, BET specific surface area) 50 m ² / g, average particle size about 0.05 μm)) 25 parts by mass, (e) TBQ (t-butylparabenzoquinone) as the polymerization inhibitor 2 (b) Thermal radically polymerizable substance (organic peroxide) A resin composition having a solid content concentration of 50% was prepared by blending 1000 ppm and methyl ethyl ketone. This was applied to the peeled PET using an applicator and dried in an oven at 90 ° C. for 5 minutes. , A plurality of underfill insulating films were prepared.
For at least one of the obtained films, the melt viscosity η ^* ₁ at 120 ° C., the melt viscosity η ^* ₂ at 140 ° C., and the minimum melt viscosity η ^* ₃ at the first temperature rise were evaluated, and the minimum melting was performed. The temperature at which the viscosity was given was specified. After cooling to 60 ° C. for about 30 minutes, the melt viscosity η ^* ₄ at 150 ° C. was evaluated at the second temperature rise. In addition, a crimping test was performed using a film prepared under the same conditions to evaluate voids and continuity. The results are shown in Table 1.

[Example 2]
As the resin component (a) for film formation, 30 parts by mass of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, 1256B40 (bisphenol A skeleton, number average molecular weight about 10,000, glass transition temperature by DSC, glass transition temperature 98 ° C., epoxy equivalent 7800)), ( c) As the epoxy resin, 20 parts by mass of an epoxy resin (manufactured by DIC Co., Ltd., N-672-EXP (cresol novolac type, softening point 71 to 79 ° C.), prepared in advance using a methyl ethyl ketone solution having a solid content of 70%). (B) As a heat radical polymerizable substance, a mixture of acrylate (KAYARAD R-130 manufactured by Nippon Kayaku Co., Ltd., 55-60% bisphenol A epoxy acrylate, 40-45% acrylate monomer, average molecular weight (Mw) 500, (E) 50 parts by mass of hydroquinone monomethyl ether (conventional name: methquinone) 500 ppm as the polymerization inhibitor 1, and (f) imidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MAOK-PW (2,4-diamino)) as the epoxy curing agent. -6- [2'-methylimidazolyl- (1')] -ethyl-s-triazine isocyanuric acid adduct)) 3 parts by weight, (d) Organic peroxide as a thermal radical generator (manufactured by Nichiyu Co., Ltd.) , Perhexa V (n-butyl-4,4-di (t-butylperoxy) valerate), 1 minute half-life temperature 173 ° C., molecular weight 334.46) 0.7 parts by mass, (g) Adipine as a flux agent 1 part by mass of acid, 54 parts by mass of silica (manufactured by Denka Co., Ltd., SFP-20M (ultrafine spherical type molten silica, d50: 0.3 μm)) as a filler, (e) TBQ (t-) as a polymerization inhibitor 2. Butylparabenzoquinone) was added to (b) a thermally radically polymerizable substance (organic peroxide) at 800 ppm and a methyl ethyl ketone to prepare a resin composition having a solid content concentration of 55%. This was applied to the peeled PET using an applicator and dried in an oven at 90 ° C. for 5 minutes to prepare a plurality of underfill insulating films having a thickness of 20 μm.
For at least one of the obtained films, the melt viscosity η ^* ₁ at 120 ° C., the melt viscosity η ^* ₂ at 140 ° C., and the minimum melt viscosity η ^* ₃ at the first temperature rise were evaluated, and the minimum melting was performed. The temperature at which the viscosity was given was specified. After cooling, the melt viscosity η ^* ₄ at 150 ° C. was evaluated by raising the temperature a second time. In addition, a crimping test was performed using a film prepared under the same conditions to evaluate voids and continuity. The results are shown in Table 1.

[Comparative Example 1]
As the resin component (a) for forming a film, 30 parts by mass of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, YX7200B35 (number average molecular weight about 10,000, glass transition temperature by DSC, glass transition temperature 149 ° C., epoxy equivalent 8000)), (c) epoxy resin 35 parts by mass of epoxy resin (manufactured by Mitsubishi Chemical Corporation, YL983U (bisphenol F type epoxy resin, epoxy equivalent 165 to 175)), and epoxy resin (manufactured by DIC Co., Ltd., HP4710 (naphthalen type, softening point 85 to 105)). 35 parts by mass (f) as an epoxy curing agent (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2MAOK-PW (2,4-diamino-6-]) 2'-Methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct)) 0.2 parts by mass, (g) 1 part by mass of adipic acid as a flux agent, and silica (EMIX300 (EMIX300) as a filler. Tatsumori Co., Ltd., silica fine particles. Primary particle size 300 nm)) 25 parts by mass and methyl ethyl ketone were blended to prepare a resin composition having a solid content concentration of 50%. It was applied using an applicator and dried in an oven at 90 ° C. for 5 minutes to prepare a plurality of underfill insulating films for a gang bonding process having a thickness of 20 μm.
For at least one of the obtained films, the melt viscosity η ^* ₁ at 120 ° C., the melt viscosity η ^* ₂ at 140 ° C., and the minimum melt viscosity η ^* ₃ at the first temperature rise were evaluated, and the minimum melting was performed. The temperature at which the viscosity was given was specified. After cooling, the melt viscosity η ^* ₄ at 150 ° C. was evaluated by raising the temperature a second time. In addition, a crimping test was performed using a film prepared under the same conditions to evaluate voids and continuity. The results are shown in Table 1.

実施例１及び２では、仮圧着及び本圧着のいずれにおいても、ボイドが抑制されるとともに、良好な導通が得られ、これらの実施例のアンダーフィル絶縁フィルムが、ギャングボンディングプロセスにおいて好適に使用できるものであることがわかった。
比較例１では、ボイドを抑制することができず、更に仮圧着では導通を確保できず、ギャングボンディングプロセスでの使用に適さないフィルムであった。

In Examples 1 and 2, voids are suppressed and good conduction is obtained in both temporary crimping and main crimping, and the underfill insulating film of these examples can be suitably used in the gang bonding process. It turned out to be a thing.
In Comparative Example 1, the film could not suppress voids and could not secure continuity by temporary crimping, and was not suitable for use in the gang bonding process.

The underfill insulating film for a gang bonding process of the present invention can effectively suppress problems such as poor continuity and generation of voids in a so-called gang bonding process having a temporary crimping process and a main crimping process, and the underfill insulating film can be used. It has a technical effect of high practical value, that is, it is possible to manufacture semiconductor devices with excellent performance, intermediate products and applied products thereof with high productivity, and it has a technical effect of high practical value, and in particular, in each field of industry. It has high utility in the fields of the electrical and electronic industry, including the manufacture of semiconductor devices.

1: Semiconductor chip 2a: Electrode 2b: Opposite electrode 3: Solder 4: Underfill insulating film, Underfill insulating film for gang bonding process 5: Circuit board 6: Head 7: Temporary crimping head 8, 10: Main crimping head 9: TSV chip

Claims (13)

Underfill insulating film for gang bonding process containing the following components (a) to (d):
(A) At least one resin component selected from phenoxy resin, polyimide resin, polyamideimide resin, polyamide resin, and acrylic resin: 10 to 40 parts by mass (b) Thermal radically polymerizable substance: 20 to 65 parts by mass (c) ) Epoxy resin: 20 to 65 parts by mass (d) Thermal radical generator: 0.1 to 5 parts by mass (Here, the contents of (a), (b), (c) and (d) are (a). (B) and (c) are parts by mass with respect to a total of 100 parts by mass.)
Further, (f) an epoxy curing agent is contained in an amount of 0.5 to 10 parts by mass with respect to a total of 100 parts by mass of (a), (b) and (c), and (e) a polymerization inhibitor is contained. (B) The underfill insulating film for a gang bonding process containing 600 to 10000 mass ppm with respect to the amount (mass) of the heat radical polymerizable substance. The underfill for a gang bonding process according to claim 1, further comprising (g) a flux agent in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of (a), (b) and (c). Insulation film. In the measurement using the dynamic viscous elasticity measuring device, the melt viscosity η ^* ₁ at 120 ° C. when the temperature was raised from 60 ° C. to 10 ° C./min was 2 × 10 ² × 10 ⁴ Pa · s. The underfill insulating film for a gang bonding process according to claim 1 or 2, wherein the melt viscosity η ^* ₂ at 140 ° C. is 3 × 10 ² to 3 × 10 ⁵ Pa · s. In the measurement using the dynamic viscous elasticity measuring device, the minimum melt viscosity η ^* ₃ when the temperature is raised from 60 ° C to 10 ° C / min to 160 ° C is 2 × 10 ² to 5 × 10 ³ Pa · s. The underfill insulating film for a gang bonding process according to any one of claims 1 to 3, wherein the temperature at which the minimum melt viscosity is given is 100 ° C to 140 ° C. In the measurement using the dynamic viscoelasticity measuring device, the temperature was raised from 60 ° C. to 160 ° C. at 10 ° C./min, then cooled to 60 ° C., and then raised again at 10 ° C./min. The underfill insulating film for a gang bonding process according to any one of claims 1 to 4, wherein the melt viscosity η ^* ₄ at ° C. is 1 × 10 ⁴ to 1 × 10 ⁸ Pa · s. The underfill insulating film for a gang bonding process according to any one of claims 1 to 5, wherein the content of the conductive particles is 5% by mass or less. The underfill insulating film for a gang bonding process according to any one of claims 1 to 6, wherein the 1-minute half-life temperature of the (d) thermal radical generator is 140 to 200 ° C. The underfill insulating film for a gang bonding process according to any one of claims 1 to 7, wherein the ( e) polymerization inhibitor is a quinone-based polymerization inhibitor. The underfill insulating film for a gang bonding process according to any one of claims 1 to 7, wherein the (f) epoxy curing agent is a latent curing agent. The latent curing agents are 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2,4-diamino-6- [2'-methylimidazole- (2'-methylimidazolyl-). 1')]-The underfill insulating film for a gang bonding process according to claim 9, which is at least one selected from the ethyl-s-triazine isocyanuric acid adduct. The underfill insulating film for a gang bonding process according to any one of claims 1 to 10, wherein the semiconductor chip on which the soldered electrode is formed and the circuit board on which the counter electrode facing the soldered electrode is formed are formed. It is a manufacturing method of a semiconductor device that is joined via
α) The process of attaching the underfill insulating film for the gang bonding process on a wafer having a soldered electrode under vacuum, and
β) A step of dividing the wafer into semiconductor chips with an underfill insulating film for individual gang bonding processes, and
γ) A step of temporarily crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
δ) A plurality of thermocompression-bonded semiconductor chips and circuit boards that were thermocompression-bonded under temperature conditions where the maximum temperature was equal to or higher than the melting point temperature of the solder mounted on the chips. A method for manufacturing a semiconductor device, comprising a thermocompression bonding step, which is a step in which the semiconductor chip is simultaneously heated to a temperature condition equal to or higher than the melting point temperature of solder. The underfill insulating film for a gang bonding process according to any one of claims 1 to 10, wherein the semiconductor chip on which the soldered electrode is formed and the circuit board on which the counter electrode facing the soldered electrode is formed are formed. It is a manufacturing method of a semiconductor device that is joined via
α') The process of attaching the underfill insulating film for the gang bonding process on the circuit board, and
γ) A step of temporarily crimping the semiconductor chip onto the circuit board so that the electrodes of the semiconductor chip and the counter electrodes of the circuit board come into contact with each other on their respective substantially center lines.
δ) A plurality of thermocompression-bonded semiconductor chips and circuit boards that were thermocompression-bonded under temperature conditions where the maximum temperature was equal to or higher than the melting point temperature of the solder mounted on the chips. A method for manufacturing a semiconductor device, comprising a thermocompression bonding step, which is a step in which the semiconductor chip is simultaneously heated to a temperature condition equal to or higher than the melting point temperature of solder. A method for manufacturing an electrical / electronic device using the method according to claim 11 or 12.

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