TW201925338A - Film-shaped semiconductor-sealing material - Google Patents

Abstract

The present invention has been made in an effort to provide a film-shaped semiconductor sealing material that satisfies the required characteristics of NCF. By (A) a compound having a benzoxazine structure, (B) an epoxy resin which is liquid at room temperature, (C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more, and (D) average A film-shaped semiconductor sealing material having a particle diameter of 1 μm or less and (E) a compound having an acid group and having a heating loss of 30% or less at 200 ° C solves this problem.

Description

Film-like semiconductor sealing material

The present invention relates to a film-like semiconductor sealing material used as NCF (Non Conductive Film) at the time of semiconductor mounting.

In the past, for the semiconductor mounting, the surface of the electrode (bump) that will form the IC (Integrated Circuit) wafer is faced, and the electrode of the substrate (electrode pad) is faced, and the bump of the IC wafer and the electrode of the substrate are performed. A flip chip method in which pads are electrically connected.
In the flip chip method, the connection portions of the electrodes are externally protected, and the stress caused by the difference in the coefficient of linear expansion between the IC wafer and the substrate is moderated. Usually, after the electrodes are connected, a liquid called an underfill agent is used. The thermosetting adhesive is cast between the semiconductor wafer and the substrate to be cured.

In recent years, the miniaturization of IC chips has been rapidly progressing. Accordingly, the distance between adjacent electrodes or the gap between the semiconductor wafer and the substrate tends to be gradually narrowed. Therefore, when the underfill agent is caused to flow between the IC wafer and the substrate by capillary action, there is a problem that voids are generated or a longer time is required for casting of the underfill agent.
Therefore, a liquid adhesive called NCP (Non Conductive Paste) or a film-like adhesive called NCF (Non Conductive Film) is applied or bonded to the substrate in advance, and then flip-chip bonded (Flip chip) In the case of a so-called first-in method in which the resin is cured by thermal compression bonding (TCB) and the electrode pad of the IC chip is connected (see Patent Document 1).

As a property required for NCF, it is void free, and it is required to have excellent electrical connectivity and its reliability. Further, in a device such as a laminate or between devices, it is necessary to carry it in a tape shape, and it is required to ensure handling property and resistance to bending. Moreover, when the resistance to bending is insufficient, in the cutting step performed after the TCB step, there is a fear that the NCF may cause mounting defects of cutting and burrs.
When the position at the start of the work is installed, the NCF attached to the wafer is required to have an excellent transparency when it is necessary to confirm the mark of the mark of the wafer or the wafer.

In the flip chip method, there are many cases in which electrical connection is performed using solder. There are many cases where lead-free solder is used in the solder material, and the melting point tends to be higher than that of the lead solder in the past. As a result, the temperature at which the flip chip is mounted using the NCF tends to become higher.
With the increase in temperature, defects such as voids tend to occur due to side reactions or volatilization of components, and it is difficult to prevent defects such as voids and connectivity.

A compound having a benzoxazine structure is subjected to a hardening reaction at a high temperature, so that it is stable at room temperature treatment, and it is difficult to start the reaction at a temperature at which the melting point of the solder is reached, and it is possible to suppress the outgas generation caused by side effects, and is similar to the use of epoxy resin. The ring-opening polymerization of the dihydrooxazine ring is characterized by the fact that it hardly causes outgassing under the hardening mechanism. Patent Document 2 proposes an adhesive composition for a semiconductor device containing a compound having a benzoxazine structure.
However, when the compound having a benzoxazine structure is used as a film, its characteristics are brittle and easily collapse. Therefore, when used as a component of NCF, it is seen that the resistance to bending is insufficient.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] Patent No. 4752107
[Patent Document 2] JP-A-2008-231287

[Problems solved by the invention]

The present invention is intended to solve the above problems in the prior art, and to provide a film-shaped semiconductor sealing material which satisfies the required characteristics of the above NCF.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a film-like semiconductor sealing material which contains
(A) a compound having a benzoxazine structure,
(B) epoxy resin which is liquid at room temperature,
(C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more,
(D) a filler having an average particle diameter of 1 μm or less and
(E) A compound having an acid group at a heating loss of 200 ° C of 30% or less.

In the film-form semiconductor sealing material of the present invention, the compound having a benzoxazine structure of the component (A) is preferably a compound represented by the following formula (1) or (2).

In the film-form semiconductor sealing material of the present invention, the epoxy resin having a liquid phase at room temperature (B) preferably contains any of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.

In the film-form semiconductor sealing material of the present invention, the compound of the above (E) component is preferably a carboxylic acid.

In the film-form semiconductor sealing material of the present invention, the compound of the above (E) component is preferably at least one selected from the group consisting of oleic acid, stearic acid, citric acid, and maleic acid resin.

The film-form semiconductor sealing material of the present invention preferably further contains (F) a decane coupling agent.

In the film-form semiconductor sealing material of the present invention, the decane coupling agent of the component (F) is preferably a compound containing any one of the following formula (3) or formula (4).

It is preferable that the film-form semiconductor sealing material of the present invention further contains (G) an elastomer.

In the film-form semiconductor sealing material of the present invention, the elastomer of the component (G) is preferably a polybutadiene skeleton.

Further, the present invention provides a semiconductor device using the film-shaped semiconductor sealing material of the present invention.

[Effects of the Invention]

The film-form semiconductor sealing material of the present invention has excellent bending resistance, and is excellent in handleability in conveyance of a device such as a laminate or between devices or attachment to a device. Moreover, when used as an NCF, there is no concern that cutting and burrs are generated in the cutting step performed after the TCB step.
The film-shaped semiconductor sealing material of the present invention has excellent visibility, and when used as an NCF, it can be confirmed that the mark of the wafer or the wafer is recognized by the NCF attached to the wafer.
When the film-form semiconductor sealing material of the present invention is used as NCF, it has excellent mountability in the TCB step.
When the film-form semiconductor sealing material of the present invention is used as NCF, it has good moisture absorption reflow resistance.

[Type of implementation of the invention]

The invention will be described in detail below.
The film-form semiconductor sealing material of the present invention contains the following components (A) to (E) as essential components.

(A) a compound having a benzoxazine structure
The compound having a benzoxazine structure of the component (A) is subjected to a curing reaction at a high temperature, so that it is stable at room temperature treatment, and it is difficult to initiate a reaction at a temperature at which the melting point of the solder is reached, and it is possible to suppress outgassing caused by side effects. When a ring-opening polymerization reaction using a dihydrocarbazine ring similar to an epoxy resin is characterized by hardly causing outgassing under a hardening mechanism, when the film-form semiconductor sealing material of the present invention is used as NCF, It is a component that imparts preservation stability and hardening properties to the film.

In the film-form semiconductor sealing material of the present invention, the compound having a benzoxazine structure of the component (A) is preferably a compound represented by the following formula (1) or (2).


From the viewpoint of film properties, the compound having a benzoxazine structure of the component (A) is preferably a compound represented by the formula (2).

(B) Epoxy resin which is liquid at room temperature
(B) An epoxy resin which is liquid at room temperature (hereinafter referred to as "liquid epoxy resin") is a component which imparts handleability to a film when the film-form semiconductor sealing material of the present invention is used as NCF.
The compound having a benzoxazine structure of the component (A) has a preferable feature for the above NCF, but when it is a film, its characteristics are brittle and easily collapse. Further, the liquid epoxy resin as the component (B) can be treated as a film by imparting moderate flexibility.

The liquid epoxy resin in the present invention is preferably one having a viscosity at room temperature (25 ° C) of 100,000 mPa·s or less.

The liquid epoxy resin in the present invention may, for example, be a bisphenol A type epoxy resin having an average molecular weight of about 400 or less; for example, p-glycidyloxyphenyldimethyl bisphenol A diglycidyl group Branched polyfunctional bisphenol A type epoxy resin of ether; bisphenol F type epoxy resin; phenol novolak type epoxy resin having an average molecular weight of about 570 or less; such as vinyl (3,4-cyclohexene) Dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl)methyl, adipic acid bis(3,4-epoxy-6-methylcyclohexylmethyl), 2 An alicyclic epoxy resin of -(3,4-epoxycyclohexyl)5,1-spiro(3,4-epoxycyclohexyl)-m-dioxane such as 3,3',5,5'- a biphenyl type epoxy resin of tetramethyl-4,4'-diglycidyloxybiphenyl; such as hexahydrophthalic acid diglycidyl, 3-methylhexahydrophthalic acid Glycidyl-based, hexahydroterephthalic acid diglycidyl glycidyl ester type epoxy resin; such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, four Glycidyl-m-xylenediamine, tetraglycidyl bis(aminomethyl)cyclohexane a glycidylamine type epoxy resin; and an intramethylene quinone type epoxy resin such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; an epoxy resin containing a naphthalene ring . Further, an epoxy resin having a polyfluorene skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldioxane may also be used. Further, for example, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane a diepoxide of methanol diglycidyl ether; such as trimethylolpropane triglycidyl ether, a tricyclic oxide of glycerol triglycidyl ether, and the like.
Among them, a bisphenol type epoxy resin, an aminophenol type epoxy resin, and a polyoxymethylene modified epoxy resin are preferable. More preferably, it is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
The liquid epoxy resin as the component (B) may be used alone or in combination of two or more.

The content of the liquid epoxy resin of the component (B) is preferably 0.5 to 70 parts by mass, more preferably 1 to 67 parts by mass, per 100 parts by mass of the compound of the component (A).

(C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more
The polymer compound (hereinafter referred to as "polymer compound") having a mass average molecular weight (Mw) of (C) component of 10,000 or more is a component which imparts a film forming ability, and can help prevent detachment, depression, and the like at the time of film formation. In the film forming step, the film end portion gradually shrinks toward the center portion, and the recessed portion refers to a case where crater-like irregularities are formed on the film surface in the film forming step.
When the mass average molecular weight (Mw) of the component (C) is less than 10,000, sufficient film formation energy cannot be obtained, and it is not possible to prevent detachment, depression, and the like at the time of film formation.
The upper limit of the mass average molecular weight (Mw) of the component (C) is not particularly limited, and when it is used at 500,000 or less, it is preferably from the viewpoint of solubility in the paint, and it is preferably used in the case of 200,000 or less.

As the polymer compound of the component (C), a phenoxy resin having a mass average molecular weight (Mw) of 10,000 or more or an acrylic copolymer having a mass average molecular weight (Mw) of 10,000 or more can be used.
The phenoxy resin as the component (C) is not particularly limited as long as the mass average molecular weight (Mw) is 10,000 or more, and is preferably a bisphenol A type phenoxy resin, a bisphenol F type phenoxy resin, or a double A phenol A-bisphenol F copolymerized phenoxy resin is preferred.
The acrylic copolymer as the component (C) is not particularly limited as long as the mass average molecular weight (Mw) is 10,000 or more, and it is preferred to have a copolymer having a soft block segment and a hard block segment, and a polybutene as a soft block segment. The acrylate structure and the polymethacrylate structure as a hard block are preferred.

The content of the polymer compound of the component (C) is preferably from 15 to 450 parts by mass, more preferably from 20 to 400 parts by mass, per 100 parts by mass of the compound of the component (A).

(D) a filler having an average particle diameter of 1 μm or less
In the filler of the component (D), when the film-form semiconductor sealing material of the present invention is used as NCF, it is added for the purpose of improving the reliability of the mounted semiconductor package.
As the filler of the component (D), those having an average particle diameter of 1 μm or less are used. This reason is due to the excellent visibility of the film and the fluidity of a narrow gap of about 5 to 80 μm. When the average particle diameter exceeds 1 μm as the filler, the visibility of the film is lowered. When the NCF is used, the identification mark of the mark of the wafer or the wafer cannot be confirmed by the NCF attached to the wafer. .
The filler of the component (D) is preferably one having an average particle diameter of 0.7 μm or less.

The filler of the component (D) is not particularly limited as long as the average particle diameter is 1 μm or less, and an inorganic filler can be used. Specific examples thereof include amorphous ceria, crystalline ceria, alumina, boron nitride, aluminum nitride, niobium carbide, and hafnium nitride.
Among these, it is preferable that the cerium oxide, particularly the amorphous spherical cerium oxide, is chemically stable, easy to adjust the particle size, and disperse to the resin component.
Further, the so-called cerium oxide is an organic group derived from a raw material for production, and may have, for example, an alkyl group such as a methyl group or an ethyl group. The amorphous spherical cerium oxide can be obtained by a known production method such as a melting method, a combustion method, or a sol-gel method, and can be suitably selected in accordance with characteristics such as desired particle size, impurity content, and surface state. method.
Further, as the cerium oxide used as the filler, a cerium oxide-containing composition obtained by the production method described in JP-A-2007-197655 can also be used.

Further, the shape of the filler is not particularly limited, and may be any of a spherical shape, an amorphous shape, and a scaly shape. Further, when the shape of the filler is spherical, the average particle diameter of the filler means the average maximum diameter of the filler.

Further, as the filler, a surface treatment can be carried out by using a decane coupling agent or the like. When a filler to be surface-treated is used, an effect of preventing aggregation of the filler can be expected.

The content of the filler of the component (D) is preferably from 5 to 75% by mass in terms of the total mass of each component of the film-form semiconductor sealing material of the present invention, and preferably from 10 to 70% by mass.

(E) a compound having an acid group at a heating loss of 200% or less at 200 ° C
The compound having an acid group of the component (E) is a component of the flux when the film-form semiconductor sealing material of the present invention is used as NCF.
When the film-form semiconductor sealing material of the present invention contains (E) component and is used as NCF, electrical connectivity and reliability can be improved.

The compound having an acid group as the component (E) can be prevented from being generated in the TCB step by using a compound having a heating loss of 30% or less at 200 ° C when used as NCF.
The heating reduction at 200 ° C can be measured as follows.
The constant temperature increase (for example, 10 ° C /min) from a low temperature to a high temperature using a thermogravimetric analyzer can be determined by measuring the heating loss per temperature unit in the temperature rise.
As the compound having an acid group which has a heating loss of 200% or less at 200 ° C, oleic acid or stearic acid can be used.

The compound having an acid group of the component (E) is preferably a carboxylic acid.
The compound having an acid group of the component (E) is preferably at least one selected from the group consisting of oleic acid, stearic acid, citric acid, and maleic acid resin. As the maleic acid resin, a commercially available product can be used. An example of this is the Maltese No. 32 (product name, manufactured by Arakawa Chemical Industries Co., Ltd.).

The content of the compound having an acid group in the component (E) is preferably 0.5 to 35 parts by mass, more preferably 1 to 32 parts by mass, per 100 parts by mass of the compound of the component (A).

The film-form semiconductor sealing material of the present invention may further contain any of the following components.

(F) decane coupling agent
When the film-form semiconductor sealing material of the present invention is used as NCF, the decane coupling agent of the component (F) is added for the purpose of improving the adhesion to the IC wafer or the substrate.
As the decane coupling agent of the component (F), various decane coupling agents such as an epoxy-based, an amine-based, a vinyl-based, a methacrylic-based, an acrylic-based, or a fluorenyl-based compound can be used. Among these, when a compound of any one of the following formula (3) or formula (4) is contained, it is preferable because of the high adhesion.

When the decane coupling agent is contained as the component (F), the content of the decane coupling agent is preferably 0.1 to 3.5% by mass based on the total mass of each component of the film-form semiconductor sealing material of the present invention. 0.2 to 3.0% by mass is preferred.

(G) Elastomer
When the film-form semiconductor sealing material of the present invention is used as NCF, the elastomer of the component (G) is added for the purpose of adjusting the modulus of elasticity or stress.
The elastomer containing the (G) component preferably contains a polybutadiene skeleton from the viewpoints of flexibility, handleability, and compatibility. As the elastomer containing a polybutadiene skeleton, epoxy-modified polybutadiene or carboxyl terminal acrylonitrile-butadiene can be used.

When the elastomer is contained in the component (G), the content of the elastomer is preferably 0.1 to 25 parts by mass, and preferably 0.2 to 20 parts by mass, based on 100 parts by mass of the compound of the component (A).

(other compounding agents)
The film-form semiconductor sealing material of the present invention may further contain components other than the above components (A) to (G) as needed. Specific examples of such a component include a curing accelerator, a rheology modifier, a dispersant, a precipitation inhibitor, an antifoaming agent, a colorant, and a surface conditioner. Further, other solid resins may be contained for the purpose of adjusting the viscosity, toughness, and the like of the film-form semiconductor sealing material of the present invention. As the above solid resin, a solid epoxy resin can be used. Further, for the thermosetting resin other than the component (A) or the component (B), for example, a phenol resin, a bismaleimide resin, a cyanate resin, an amine resin, a quinone imine resin, or an unsaturated polyester may be added. Resin, (meth) acrylate resin, urethane resin. The type and amount of each compounding agent can be based on the usual method.

(Manufacture of film-like semiconductor sealing material)
The film-form semiconductor sealing material of the present invention can be produced by a conventional method. For example, in the presence or absence of a solvent, the above components (A) to (E), and the above-mentioned (F) component, (G) component and other compounding agents which are further blended are subjected to a heating vacuum kneading machine. After mixing, the resin composition was prepared.
The components (A) to (E) and the components (G) and other complexing agents required for further blending are dissolved in a predetermined solvent concentration at a desired content ratio, and these are heated to 10%. At 80 ° C, the amount was measured in a reaction vessel, and the mixture was rotated at a number of revolutions of 100 to 1000 rpm, and the mixture was stirred at normal pressure for 3 hours, and then further mixed for 3 to 60 minutes under vacuum (maximum 1 Torr).
The resin composition prepared by the above procedure is diluted with a solvent to form a lacquer, and this is applied to at least one surface of the support, and after drying, it can be provided as a film-like semiconductor sealing material attached to the support or by the support. Peeled film-like semiconductor sealing material.

Examples of the solvent which can be used for the lacquer include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; dioctyl phthalate and dibutyl. High boiling point solvents such as phthalates. The amount of the solvent to be used is not particularly limited, and may be used in the past, but it is preferably 20 to 90% by mass based on the respective components of the film-form semiconductor sealing material.

The support can be suitably selected from the form of the film-form semiconductor sealing material in the production method, and is not particularly limited, and examples thereof include a metal foil such as copper or aluminum, and a resin carrier film such as polyester or polyethylene. When the film-form semiconductor sealing material of the present invention is provided as a film form which is peeled off from the support, it is preferred that the support is subjected to release treatment by a release agent such as a polysiloxane.

The method of applying the lacquer is not particularly limited, and examples thereof include a slit die method, a concave plate method, and a blade coating method, and can be appropriately selected in accordance with the thickness of the desired film. The film is applied to the thickness of the film formed after drying to a desired thickness. Such a thickness can be estimated by the manufacturer by the solvent content.

The drying conditions can be appropriately selected in accordance with the kind or amount of the solvent to be used for painting, the amount of the paint to be used, the thickness of the coating, and the like, and are not particularly limited, and can be carried out, for example, at 60 to 150 ° C under atmospheric pressure.

Next, the characteristics of the film-form semiconductor sealing agent of the present invention will be described.

The film-form semiconductor sealing material of the present invention has excellent visibility, and the evaluation results of the visibility in the initial mounting state are good for the examples described later. Therefore, when used as an NCF, it is possible to confirm the identification mark of the mark of the wafer or the wafer via the NCF attached to the wafer.

The film-form semiconductor sealing material of the present invention has excellent bending resistance, and no cracking occurred in the evaluation of film properties in the examples described later. Therefore, it is preferable to carry out transportation in a device such as a laminate or between devices, or when attaching to a device. Moreover, when used as NCF, there was no concern of cutting and burrs in the cutting step performed after the TCB step.
When the film-form semiconductor sealing material of the present invention is used as NCF, the mountability in the TCB step is excellent, and in the examples described later, the evaluation of the voids in the initial mounting state and the evaluation of the connectivity are good.
When the film-form semiconductor sealing material of the present invention is used as NCF, the moisture absorption reflow resistance is good, and in the examples described later, the void/delamination at the time of moisture absorption and reflow is evaluated to be good.
The film-form semiconductor sealing material of the present invention can be mounted in a short period of time, so that productivity is high.
The film-form semiconductor sealing material of the present invention has a combined soldering effect and has excellent solder connectivity.

The film-form semiconductor sealing material of the present invention is suitable for NCF because of the above characteristics.

Next, the procedure for using the film-form semiconductor sealing material of the present invention is as follows.
When the semiconductor package is mounted by using the film-shaped semiconductor sealing material of the present invention, the film-shaped semiconductor sealing material is bonded to the desired shape by a laminate or the like in the desired position on the semiconductor wafer on the mounting substrate.
Further, on the wafer on which the semiconductor circuit is formed, after bonding with a laminate or the like, each wafer can be cut by a dicer or the like. The lamination conditions are not particularly limited, and conditions such as heating, pressurization, and reduced pressure can be appropriately combined. In particular, when fine defects are bonded to defects such as voids, the heating temperature is 40 to 120 ° C, the pressure reduction is 1 hPa or less, and the pressure is 0.1 MPa or more.
After bonding the film-shaped semiconductor sealing material by lamination or the like, the semiconductor wafer is mounted on the wafer mounting position on the substrate by thermocompression bonding (TCB) by a flip chip bonding machine or the like. The TCB condition is not particularly limited, and the TCB condition can be appropriately selected by the semiconductor wafer size, the projection material, the number of protrusions, and the like.
The heating temperature is 50 to 300 ° C, the time is 1 to 20 seconds, and the pressure is 5 to 450 N.

In the semiconductor device of the present invention, the film-shaped semiconductor sealing material of the present invention is used in the production of the semiconductor device, and is not particularly limited. A specific example of the semiconductor device of the present invention includes a semiconductor device having a flip chip structure. The flip chip has a projecting electrode called a bump, and is connected to an electrode such as a substrate via the electrode. Examples of the bump material include solder, gold, copper, and the like, and each of them may be exemplified separately, or a structure in which a solder layer is formed on copper may be exemplified. As the substrate to be connected to the flip chip, a single layer or a laminated organic substrate such as FR-4, an inorganic substrate such as ruthenium, glass, or ceramic, copper or copper plating or tin plating on copper, and OSP on copper are used. (Organic Solderability Preservative) processes to form an electrode such as a solder layer. The semiconductor device of the flip-chip structure includes a memory device such as a DRAM (Dynamic Random Access Memory), a processing device such as a CPU (Central Processing Unit) GPU (Graphics Processing Unit), and a light-emitting device such as an LED (Light Emitting Diode). Used in driver ICs such as LCD (Liquid Crystal Display).

[Examples]

The present invention will be described in detail below by way of examples without limitation.

(Examples 1 to 26, Comparative Examples 1 to 7)
The raw materials to be mixed were mixed in the following table, and the mixture was dissolved and dispersed in a solvent at a concentration of 50% by weight to prepare a coating paint. The solvent was methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.).
The coated coating was applied to a PET (polyethylene terephthalate) film (35 μm thick) coated with a release agent to a dry thickness of about 20 μm or about 35 μm. Thereafter, the coating layer was coated with a paint release agent-treated PET (polyethylene terephthalate) film in a dryer at 80 ° C for 10 minutes, and then the solvent was removed to prepare a thickness of 20 μm and 35 μm. Two thick films. Further, the numerical values of the respective components in the table indicate the parts by mass.

The components used in the production of the film-form resin composition are as follows.

(A) a compound having a benzoxazine structure
(A1) A compound represented by the following formula (1) (product name Pd type, manufactured by Shikoku Chemical Industry Co., Ltd.)

(A2) A compound represented by the following formula (2) (product name Fa type, manufactured by Shikoku Chemical Industry Co., Ltd.)

(B) Liquid epoxy resin
(B1) bisphenol F liquid epoxy resin/bisphenol A liquid epoxy resin mixture (product name EXA835LV, manufactured by DIC Co., Ltd., viscosity: 2000 to 2500 mPa·s)
(B2) bisphenol A type liquid epoxy resin (product name EXA850CRP, manufactured by DIC Corporation, viscosity: 3500 to 5500 mPa·s)
(B3) bisphenol F type liquid epoxy resin (product name EXA830CRP, manufactured by DIC Corporation, viscosity: 1100 to 1500 mPa·s)
(B') bisphenol A type semi-solid epoxy resin (product name: EPICRON 860, manufactured by DIC Co., Ltd., viscosity: 1180 Pa·s)

(C) polymer compound
(C1) Acrylic Copolymer (product name: M52N, manufactured by Arkema Co., Ltd., Mw: about 80,000)
(C2) Acrylic Copolymer (product name LA4258, manufactured by Kuraray Co., Ltd., Mw: about 80,000)
(C3) bisphenol A/bisphenol F copolymerized phenoxy resin, product name jER4250, manufactured by Mitsubishi Chemical Corporation, Mw: 60000)

(D) cerium oxide filler
(D1) Product name Sciqas, average particle size 0.05 μm (manufactured by Dai Chemical Industry Co., Ltd.)
(D2) Product name Sciqas, average particle size 0.1 μm (manufactured by Dai Chemical Industry Co., Ltd.)
(D3) Product name Sciqas, average particle size 0.4 μm (manufactured by Dai Chemical Industry Co., Ltd.)
(D4) Product name Sciqas, average particle size 0.7 μm (manufactured by Dai Chemical Industry Co., Ltd.)
(D') product name SOE-5, average particle size 1.5μm (manufactured by Admatechs Co., Ltd.)

(E) a compound having an acid group
(E1) Oleic acid (made by Wako Pure Chemical Industries, Ltd.), heating reduction at 200 ° C: 1.7%
(E2) Stearic acid (manufactured by Wako Pure Chemical Industries, Ltd.), heating reduction at 200 ° C: 0.8%
(E3) tannic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), heating reduction at 200 ° C: 0.9%
(E4) Maleic acid resin (product name: Malachite No. 32, manufactured by Arakawa Chemical Industry Co., Ltd.), heating loss at 200 ° C: 0.8%
(E') p-benzoic acid (manufactured by Wako Pure Chemical Industries, Ltd.), heating loss at 200 ° C: 32.5%

(F) decane coupling agent
(F1) 3-glycidoxypropyltrimethoxydecane (formula (3)) (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.)

(F2) N-phenyl-3-aminopropyltrimethoxydecane (formula (4)) (product name: KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.)

(G) Elastomer
(G1) epoxy-denatured polybutadiene (product name: PB3600, manufactured by Toagosei Co., Ltd.)
(G2) carboxyl terminal acrylonitrile-butadiene (product name: CTBN, CVC Thermoset Specialties)

The following evaluation was carried out using the film produced in the above procedure.

(thin film)
The film formed on the PET by the above procedure was cut into 10 mm × 100 mm to prepare a test piece. The test piece was bent 180 degrees to confirm whether cracks were generated. The above procedure was carried out for N=5 for each film thickness of 20 μm and 35 μm. In the case where all of the film thicknesses N=5 did not cause two film thickness cracks, it was ○, and the case where only one test piece was cracked was ×.

(initial installation status)
The 20 μm thick film produced in the above procedure was used as NCF, and the test wafer was mounted on the substrate by the following procedure.
The substrate used was a ruthenium substrate having a size of 10 mm × 10 mm × 0.725 mm (t), and was subjected to plating treatment of Ni and Au on Cu as an electrode material.
The test wafer was 7.3 mm × 7.3 mm × 0.125 mm (t) in size, and 1048 protrusions were formed on the copper pillar of 42 μm φ × 10 μm to form a solder layer (10 μm). On a tantalum wafer having a structure connected to the above-described size test wafer, a 20 μm-thick NCF was laminated using a vacuum pressure-bonded laminate (manufactured by Nago Seisakusho Co., Ltd., trade name: MLP500/600) under the following conditions.
Vacuum degree: below 1hPa Temperature: 70°C
Pressurization: 0.4MPa
Time: 180sec
After lamination, a dicer was used, and the tantalum wafer was bonded to each of the wafer test wafers of a predetermined size (7.3 mm × 7.3 mm) containing NCF. Then, using a flip chip bonding machine (trade name FCB3, manufactured by Panasonic Factory Solutions Co., Ltd.), the test wafer and the tantalum substrate were subjected to thermocompression bonding (TCB) at a temperature of 260 ° C to the NCF. The above procedure was implemented with N=5.
Identification: In the step of adjusting the position of the flip chip bonding machine, the case where no identification error occurs in all N=5 is ○, and even if only one test piece is generated, the case where the recognition error occurs is ×.
Cavity: The prepared test piece was observed by a reflection method using an ultrasonic flaw detection apparatus (Scanning Acoustic Tomography, SAT). The case where no shadow of the cavity was observed on all of the images of N=5 was ○, and even if only one test piece was observed, the case where the shadow was observed was ×.
Connection: In the prepared test piece, 1 test piece was pulled out, and a section of the peripheral device portion was observed through a cross section of the grinding and grinding connection section. Whether or not solder wettture was formed on the interface between the solder of the test wafer and the Pad of the Bottom wafer, and it was confirmed by a scanning electron microscope that the solder wet condition was ○, and the case where the solder wetness was not confirmed was ×.

(moisture reflow)
The test piece prepared in the above procedure was allowed to stand at 85 ° C / 60% RH for 168 hours (JEDEC level 2 moisture absorption condition). Thereafter, it was passed through a reflow furnace up to a temperature of 260 ° C for 3 times. The above procedure is implemented as N=4. After the implementation of the moisture absorption reflow, the test piece was observed by a reflection method using an ultrasonic flaw detection apparatus (Scanning Acoustic Tomography, SAT). The case where no shadow of the void/delamination was observed on all the images of N=4 was ○, and the case where the shadow was observed only for one test piece was ×.

(tightness strength)
An FR-4 substrate which was dried at 150 ° C for 20 minutes and an Si wafer which was a semiconductor wafer with a SiN film of 2 mm square length were prepared. A film-shaped semiconductor sealing agent of 1 mmφ was placed on the substrate, and a semiconductor wafer was mounted on the film-shaped semiconductor sealing agent. Thereafter, the film-like semiconductor blocking agent was cured at 175 ° C for 2.5 hours. The adhesion strength (unit: N/mm ² ) was measured in a shear mode using an Aiko-Engineering Strength Tester (Model: 1605HTP). When N=10 is performed, the average value of the adhesion strength is obtained.

In Examples 1 to 26, film properties (cracking), initial mounting state (void, connection, visibility), moisture absorption reflow (void/delamination) were all good. Further, Example 2 is an example in which Example 1 is a compound having a benzoxazine structure which changes the component (A). Examples 3 and 4 are examples of the polymer compound in which the component (C) is changed in the second embodiment. Examples 5 to 7 are examples in which Example 2 is a ceria filler having a different average particle diameter as the component (D). Examples 8 and 9 are examples of the liquid epoxy resin which changed the component (B) for Example 2. Example 10 is an example of the decane coupling agent which changes the component (F) for Example 2. Example 11 is an example in which the blending ratio of the liquid epoxy resin of the component (B) was changed without changing the decane coupling agent of the component (F). Example 12 is an example in which the blending ratio of the liquid epoxy resin of the component (B) and the polymer compound of the component (C) was changed to the semi-solid epoxy resin in which the component (B') was not added. Example 13 is an example in which the blending ratio of the ceria filler of the component (D) was changed for Example 2. In Example 14, Example 2 is an example in which the mixing ratio of the liquid epoxy resin of the component (B), the semi-solid epoxy resin of the component (B'), and the ceria filler of the component (D) was changed. Example 15 is an example in which the blending ratio of the liquid epoxy resin of the component (B) is changed by using the polymer compound of the two types (C) as the elastomer having no component (G) added thereto. Example 16 is an example in which the mixing ratio of the liquid epoxy resin of the component (B) and the decane coupling agent of the component (F) is changed in the second embodiment. Example 17 is an example in which the mixing ratio of the decane coupling agent of the component (F) and the elastomer of the component (G) is changed in the second embodiment. Example 18 is an example in which the mixing ratio of the compound of the component (E) and the elastomer of the component (G) is changed in the second embodiment. Example 19 is an example in which the mixing ratio of the semi-solid epoxy resin of the component (B') and the compound of the component (E) is changed. Examples 20, 25, and 26 are examples of compounds in which the compound of the component (E) is changed. In Example 21, Example 2 is an example in which the mixing ratio of the liquid epoxy resin of the component (B) and the compound of the component (E) was changed. Example 22 In the example 2, the semi-solid epoxy resin having no (B') component added thereto, and the polymer compound of the two types (C) component was used, and the mixing ratio of each component was changed. Example 23 is an example in which Example 2 is an elastomer which changes the polymer compound of the component (C) and the component (G). In Example 24, in Example 2, an elastomer having no (G) component added thereto was changed, and the liquid epoxy resin of the component (B), the semi-solid epoxy resin of the component (B'), the compound of the component (C), and ( An example of the blending ratio of the ceria filler of component D).
Comparative Example 1 is an example in which a ceria filler having an average particle diameter of more than 1 μm was used as the component (D'), and the visibility in the initial mounting state was ×. Therefore, other evaluations in the initial installation state and moisture absorption reflow evaluation were not performed. Comparative Example 2 is an example of a compound in which the component (E) was not added, and the connectivity in the initial mounting state was ×. Therefore, moisture absorption reflow evaluation was not performed. Comparative Example 3 is an example of a ceria filler to which no component (D) was added, and the moisture absorption reflow was evaluated as ×. Comparative Example 4 is an example in which a compound having a heating loss of more than 30% at 200 ° C was used as the component (E'), and the void in the initial mounting state was ×. Therefore, moisture absorption reflow evaluation was not performed. Comparative Examples 5 and 6 are examples of a liquid epoxy resin to which the component (B) was not added, and the film properties were evaluated as ×. Therefore, the evaluation in the initial installation state and the moisture absorption reflow evaluation were not performed. From the results of Comparative Examples 5 and 6, it was confirmed that even in the case of the elastomer containing the component (G), the liquid epoxy resin not containing the component (B) may deteriorate the film properties. Comparative Example 7 is an example of a compound in which the component (A) was not added, and the void in the initial mounting state was ×. Therefore, moisture absorption reflow evaluation was not performed.

Claims (10)

A film-like semiconductor sealing material characterized by containing (A) a compound having a benzoxazine structure, (B) epoxy resin which is liquid at room temperature, (C) a polymer compound having a mass average molecular weight (Mw) of 10,000 or more, (D) a filler having an average particle diameter of 1 μm or less and (E) A compound having a heating loss of an acid group at 200 ° C of 30% or less. The film-like semiconductor sealing material of claim 1, wherein the compound having the benzoxazine structure of the component (A) is a compound represented by the following formula (1) or (2); . The film-form semiconductor sealing material of claim 1, wherein the epoxy resin which is liquid at room temperature in the component (B) is any one of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. The film-form semiconductor sealing material of claim 1, wherein the compound of the component (E) is a carboxylic acid. The film-form semiconductor sealing material of claim 1, wherein the compound of the component (E) is at least one selected from the group consisting of oleic acid, stearic acid, citric acid, and maleic acid. The film-form semiconductor sealing material of claim 1, further comprising (F) a decane coupling agent. The film-like semiconductor sealing material of claim 6, wherein the decane coupling agent of the component (F) is a compound containing any one of the following formula (3) or formula (4); . The film-like semiconductor sealing material of claim 1, further comprising (G) an elastomer. The film-form semiconductor sealing material of claim 8, wherein the elastomer of the component (G) is a polybutadiene skeleton. A semiconductor device characterized by using the film-form semiconductor sealing material according to any one of claims 1 to 9.