TWI626292B - Composition for non-conductive adhesive film and non-conductive adhesive film including the same - Google Patents

Abstract

The present invention relates to a composition for a non-conductive adhesive film and a non-conductive adhesive film including the same, and more particularly to a composition for a non-conductive adhesive film and a non-conductive adhesive film including the same, that is, by curing Speed has been further improved to minimize soldering between wafers and resin flow during wafer-to-substrate soldering, improve productivity, improve bump filling properties and adhesion to semiconductor wafers, and have excellent room temperature stability. , Reflecting the heat resistance required for semiconductor products.

Description

Composition for non-conductive adhesive film and non-conductive adhesive film containing same

The present invention relates to a composition for a non-conductive adhesive film and a non-conductive adhesive film including the same, and more particularly to a composition for a non-conductive adhesive film and a non-conductive adhesive film including the same, that is, by curing The speed is increased to minimize the welding between the wafers, the resin flow during the wafer and substrate welding process, improve productivity, and at the same time improve the bump fillability and adhesion to the semiconductor wafer, with excellent room temperature stability, Reflects the heat resistance required for semiconductor products.

Recently, electronic devices including mobile devices have gradually become smaller and thinner. For this reason, the semiconductor industry has also become increasingly high-capacity and ultra-high-speed. At the same time, it has become extremely small and thin. In order to meet the needs of the semiconductor industry as described above, research and development of new-generation integrated circuit (IC) substrates, printed circuit boards (PCBs), flexible display substrates, and the like are being conducted for semiconductor devices. A method of high integration, high miniaturization, and high performance. With this trend, Korean Patent No. 1030497 also discloses a flexible display substrate. In the method for manufacturing a semiconductor device described above, an adhesive sheet (dicing sheet) is bonded to a semiconductor wafer formed of silicon, gallium, arsenic, or the like, and is separated (recombined) into individual semiconductor elements by dicing, cutting, and then carried out. Expanding, picking up the reorganized semiconductor element, and then transferring the semiconductor element to an assembly process of a semiconductor device that is wafer-bonded to a metal lead frame, a tape substrate, an organic hard substrate, or the like.

On the other hand, the technological innovations for reducing the thickness, thickness, and shortening of semiconductor devices have made remarkable progress. Therefore, they have been manufactured by making a variety of package structures. One example is the development of a multi-chip package product in which a plurality of semiconductor chips are mounted in a vertical structure. In the lamination, dozens or hundreds of fine holes are punched in the stacked semiconductor wafers, and the upper end wafer is electrically connected to the lower end wafer by filling with a conductor. The multi-chip package product having the structure described above has a shorter signal transmission distance between chips than conventional wire-bonded multi-chip package products, and therefore increases processing speed and reduces power consumption. This makes it easier to realize low-power products with high density, high capacity, and high performance. Therefore, it has recently attracted attention as a semiconductor package structure.

Specifically, FIG. 1b shows a multi-chip package in which a plurality of semiconductor wafers 300 are prepared, and the bumps of adjacent semiconductor wafers 100/200 and 200/300 are electrically connected to each other by lamination and thermal compression bonding. The wafer 300 is formed with a plurality of holes (FIG. 1 a), and the holes are formed with a bump 301 and a shoulder 302. As shown in FIG. 1b, the structure described above has the advantage that the distance between the semiconductor wafers is short, which can greatly increase the connection density between the wafers, and therefore, the processing speed can be further increased.

On the other hand, as shown in FIG. 1b, since the bumps are provided, an idle space S is formed between the upper and lower wafers. The bumps can be oxidized when exposed to the air existing in the idle space S, and because only the bumps between the wafers pass through the bumps. In order to prevent the above problems and strengthen the bump bonding part or improve the reliability, the resin composition is usually used to bond between the semiconductor wafer and the wafer and / or the lower part of the multi-wafer and the substrate in order to prevent the problem. The gap between them is sealed.

Specifically, the above-mentioned sealing work is performed by a method in which, after connecting the wafer to the wafer, an underfill liquid resin is injected between the wafer and the wafer and / or into a gap between a lower portion of the plurality of wafers and the substrate. To fix the connection part between the chip and the chip. However, when the underfill liquid resin injection step is performed, there is a problem that, due to capillary phenomenon, even if the liquid underfill resin flows between the semiconductor wafer and the bumps of the wafer, the resin cannot be sufficiently diffused. The unfilled portion or the liquid underfill resin is excessively extruded, thereby contaminating a substrate or a multi-wafer. In addition, an additional cleaning step is required, which causes environmental problems such as a long process step and a problem in the treatment of cleaning waste liquid. Since the sealing is performed by a capillary phenomenon, the sealing time is prolonged, resulting in poor productivity. Furthermore, when a semiconductor wafer is stacked three-dimensionally on a substrate in a vertical direction, in each element stacking process, a liquid resin is applied to an upper portion of the element or a space between the elements is applied. Injected, however, the above steps also have problems that are both complicated and difficult.

In order to improve the problems as described above, the use of non-conductivity is being developed recently A method of connecting a wafer to a substrate by bonding a film-like resin of a non-conductive film (NCF, Non Conductive Film).

The film-like resin material can be simply cut to the same size as the reconstituted wafer by laminating on a semiconductor wafer or an upper portion of the wafer by applying a lamination method, and then by a dicing step. In addition, in the case of an element in which elements are stacked three-dimensionally on a substrate in a vertical direction, compared with a case where a liquid resin material is used, there are advantages in that the process is simple and easy to stack.

In the case of using the above-mentioned non-conductive adhesive film, although many problems occurred in the conventional process of sealing with a liquid underfill resin have been improved, the non-conductive adhesive film currently developed has a film shape and a bump filling property. Insufficient adhesion, etc., often cause bump bonding failure. In order to solve the above problems, when a non-conductive adhesive film is connected to a semiconductor wafer including bumps by applying excessive pressure, Induced bump damage. In addition, when the curing speed of the thermosetting adhesive film is delayed, the melted adhesive component leaks from the wafer and the wafer or between the wafer and the substrate, thereby contaminating the multi-chip package. Furthermore, the slow curing speed significantly reduces the productivity as the soldering time between wafers is extended. At the same time, as the light-cured or low-temperature heat-curable non-conductive adhesive film undergoes bump bonding in a low-temperature environment, poor bonding between the bumps occurs. Also, when thermal curing is performed at a low temperature, the stability of the adhesive film is significantly reduced.

Therefore, there is an urgent need to develop a non-conductive adhesive film that adjusts the curing speed so that resin flow is properly generated, prevents contamination of multiple wafers and / or substrates, improves productivity, and increases voids by increasing adhesion. Minimized, has excellent room temperature stability, and can guarantee heat resistance.

The present invention has been made to solve the problems described above, and an object of the present invention is to provide a semiconductor laminate including a composition for a non-conductive adhesive film, and a non-conductive adhesive film using the same. And a non-conductive adhesive film, the above-mentioned composition for a non-conductive adhesive film has an improved curing speed, and in particular has an increased curing speed at high temperatures, so that the soldering between wafers or the soldering between a wafer and a substrate can be appropriately adjusted. process The flow of resin in the resin improves productivity, and at the same time improves bump filling properties and adhesion to semiconductor wafers. It has excellent room temperature stability and reflects the heat resistance required by semiconductor products.

In order to solve the above problems, the present invention provides a composition for a non-conductive adhesive film, that is, the composition for a non-conductive adhesive film includes a thermosetting portion including a first thermosetting portion including an epoxy component and an acrylic component. A second thermosetting portion; and a thermoplastic portion.

According to a preferred embodiment of the present invention, the epoxy component may include a glycidyl ether type epoxy component, a glycidyl amine type epoxy component, a glycidyl ester type epoxy component, a naphthalene type epoxy component, and an alicyclic ring. One or more of the oxygen components.

According to another preferred embodiment of the present invention, the acrylic component may include a polyfunctional acrylic monomer, and the polyfunctional acrylic monomer may include two or more vinyl groups.

According to another preferred embodiment of the present invention, the thermoplastic portion may include an acrylic copolymer, and the acrylic copolymer may be copolymerized by including an acrylic monomer containing an epoxy group.

According to another preferred embodiment of the present invention, the second thermal curing unit may include a second curing component having a half-life temperature of 100 ° C. or higher for 10 hours. Preferably, the 10-hour half-life temperature of the second curing component may be 100 to 160 ° C, and more preferably, 110 to 150 ° C.

According to another preferred embodiment of the present invention, the thermoplastic resin may contain 30 to 100 parts by weight based on 100 parts by weight of the total weight of the epoxy component and the acrylic component of the thermosetting portion.

According to another preferred embodiment of the present invention, the acrylic component may be contained in an amount of 70 to 120 parts by weight based on 100 parts by weight of the epoxy component.

According to another preferred embodiment of the present invention, the epoxy component may include an epoxy component having a solid phase at a temperature of 25 ° C.

According to still another preferred embodiment of the present invention, the first thermal curing part may further include a first curing component having a solid state at a temperature of 25 ° C.

According to another preferred embodiment of the present invention, the epoxy component does not include an epoxy component whose properties are in a liquid phase at a temperature of 25 ° C.

According to another preferred embodiment of the present invention, the above composition further includes an inorganic filler. Fillers, organic particles and silane coupling agents. At this time, the inorganic filler is contained in the composition in an amount of 50 to 150 parts by weight based on 100 parts by weight of the total weight of the epoxy component of the first thermally cured portion and the acrylic component of the second cured portion.

On the other hand, in order to solve the above-mentioned problems, the present invention provides a non-conductive adhesive film comprising the composition for a non-conductive adhesive film of the present invention.

In addition, the present invention provides a non-conductive adhesive film including the adhesive layer formed by drying the non-conductive adhesive film composition of the present invention, and a release member formed on the above. At least one side of the adhesive layer.

According to an embodiment of the present invention, in the adhesive layer, a melting interval according to the following mathematical formula 1 may be 90 ° C. or lower, and more preferably, 50 to 90 ° C.

Mathematical formula 1 Melting interval (△ T) = TA (℃) -TB (℃)

The above TA has a melt viscosity of 80,000 Pa. The temperature (° C) at S, the above TB has a melt viscosity of 20,000 Pa. Temperature at S (° C).

Moreover, this invention provides the semiconductor laminated body which hardened | cured by including the non-conductive adhesive film of this invention.

Hereinafter, terms used in the present invention will be described.

The composition for a non-conductive adhesive film of the present invention has an increased curing speed so that the resin flow during the soldering between wafers and the soldering process between the wafer and the substrate can be appropriately adjusted and productivity can be improved. In addition, since the bump filling property of the bonding film and the adhesion to the semiconductor wafer are improved, and the heat resistance required for a semiconductor product is expressed by having a high glass transition temperature, it is suitable for use in a semiconductor product. ) The voids between the bumps are minimized, and the wafer is prevented from delamination by improving the film adhesion on the wafer, so that it is widely used in various semiconductors and electrical and electronic products including the same.

1‧‧‧ sheet substrate

10‧‧‧ non-conductive adhesive film

11‧‧‧ release layer

100‧‧‧ semiconductor wafer

2‧‧‧ adhesive layer

21‧‧‧ peeling substrate

200‧‧‧Semiconductor wafer

30‧‧‧Semiconductor wafer

30a‧‧‧Function surface

300‧‧‧Semiconductor wafer

301‧‧‧ bump

302‧‧‧Shoulder

S‧‧‧Free space

1a and 1b are obtained by laminating and bonding a plurality of semiconductor wafers vertically. Partial cross-sectional view of the manufactured multi-chip module.

2 is a schematic cross-sectional view of a non-conductive adhesive film according to a preferred example of the present invention.

3 is a schematic cross-sectional view of a non-conductive adhesive film according to a preferred example of the present invention.

4 is a schematic cross-sectional view of a non-conductive adhesive film according to a preferred example of the present invention.

FIG. 5 is a schematic diagram of a non-conductive adhesive film according to a preferred example of the present invention.

FIG. 6 is a schematic diagram of a non-conductive adhesive film according to a preferred example of the present invention.

FIG. 7 is a schematic cross-sectional view of a semiconductor laminate according to a preferred example of the present invention.

Hereinafter, the present invention will be described in more detail.

The composition for a non-conductive adhesive film of the present invention includes a thermosetting portion and a thermoplastic portion.

The thermosetting portion functions to ensure heat resistance of the non-conductive adhesive film, bonding reliability between the wafers, adhesiveness, and the like. In addition, the thermoplastic portion improves the film formability, increases the adhesion force by elasticity, and ensures the reliability of bonding between wafers.

The thermosetting portion includes a first thermosetting portion including an epoxy component and a second thermosetting portion including an acrylic component.

First, the first thermosetting portion will be described.

The first heat-cured portion may include an epoxy component, and may further include a first curing component that cures the epoxy component.

When the said epoxy component is a well-known epoxy component required for preparation of a non-conductive adhesive film, it can be used without limitation. As a non-limiting example, the epoxy component includes a glycidyl ether epoxy resin, a glycidylamine epoxy resin, a glycidyl ester epoxy resin, a linear aliphatic epoxy resin, and a resin. Cycloaliphatic epoxy resins, heterocyclic epoxy resins, substituted epoxy resins, naphthalene-based epoxy resins, and their derivatives can be bifunctional or polyfunctional resins, which can be used alone or Mixed use.

More specifically, the glycidyl ether type epoxy resin includes phenolic glycidyl ether and alcoholic glycidyl ether, and the phenolic glycidyl ether includes, for example, bisphenol A type, bisphenol B type, bisphenol AD type, Bisphenol type epoxy such as bisphenol S, bisphenol F and resorcinol, such as phenol Aldehyde (Phenol novolac) epoxy, aralkylphenol novolac, terpene phenol novolac phenolic novolac and o-cresol novolac epoxy such as Cresol novolac epoxy can be used alone or Use 2 or more types together. Preferably, the first epoxy resin may be a bisphenol-based epoxy resin, and more preferably, it may be a bisphenol F-type epoxy resin. In this case, compared to the case where other types of epoxy resins are included, Can obtain more excellent physical properties.

The glycidylamine type epoxy resin includes diglycidylaniline, tetraglycidyldiaminodiphenylmethane, N, N, N ', N'-tetraglycidyl metaxylylenediamine, 1,3- Bis (diglycidylamine methyl) cyclohexane, triglycidyl-m-aminophenol and triglycidyl-aminophenol, which have both structures of glycidyl ether and glycidylamine, can be used alone or in two types Combine the above.

The above glycidyl ester type epoxy resin may be an epoxy resin by means of a hydroxy hydrocarbon acid such as p-hydroxybenzoic acid, β-hydroxynaphthoic acid, and a polycarbonate such as phthalic acid, terephthalic acid, or the like, and may be used alone or Use 2 or more types together. The linear aliphatic epoxy resin may be, for example, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolethane, or trimethylol. Glycidyl ethers such as propane, pentaerythritol, hydrogenated bisphenol A, decane hydrogen bisphenol F, ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol can be used alone or in combination of two or more.

The above alicyclic epoxy resin may include epoxy cyclohexane or 1,2-epoxycyclopentane, but is not limited thereto. The above cyclohexene oxide or 1,2-epoxycyclopentane may have at least Polyglycidyl ethers of an alicyclic ring polyol or a plurality of compounds containing a cyclohexene ring or a cyclopentene ring are epoxidized by an oxidizing agent. As an example, the alicyclic epoxy resin may be 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylformate, 3,4-epoxy-1-methylcyclohexyl-3 , 4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl- 3,4-epoxy-5-methylcyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, methyl-bis (3,4-epoxycyclohexane) , 2,2-bis (3,4-epoxycyclohexyl) propane, dicyclopentadiene dioxide, ethylene-bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxy Hexahydrophthalic acid and di-2-ethylhexyl epoxy hexahydrophthalic acid are used alone or in combination of two or more.

The naphthalene-based epoxy resin may be 1,2-diglycidyl naphthalene, 1,5-diglycidyl Naphthalene, 1,6-diglycidyl naphthalene, 1,7-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, triglycidyl naphthalene, 1,2,5,6-tetraglycidyl naphthalene, etc. The bone epoxy resin can be used alone or in combination of two or more.

In addition to the above examples, it may be triglycidyl isocyanurate, and may be a ring having an epoxy cyclohexane ring in the molecule formed by oxidizing a compound having multiple double bonds in the molecule. Oxygen resin and so on.

On the other hand, in order to prevent the viscosity of the adhesive film from increasing due to the acrylic component of the second heat-cured portion described later, the epoxy component may be an epoxy component having a solid phase at a temperature of 25 ° C. More preferably, the epoxy component The epoxy component does not need to contain the epoxy component which has a liquid phase at a temperature of 25 ° C. In the case where a component having a liquid phase property is included, as the viscosity of the adhesive film increases, voids generated between the wafer and the adhesive film increase, thereby reducing the reliability of bonding between the wafers. In addition, the curing speed is lower than that in the case where a solid epoxy component is used, regardless of the second heat-curing portion described later. However, when an epoxy component having a liquid phase property is contained, the content thereof is preferably 5 weight percent or less of the entire epoxy component weight.

Moreover, when the 1st hardening component also contained in the said 1st thermosetting part is a well-known hardening component which hardens the said epoxy component, it can be used without limitation. Specific examples include aliphatic amines such as diethylenetriamine, triethylenetetramine, and aromatic amines such as m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylhydrazone, and azomethylphenol. Polyhydric hydroxy compounds such as phenol novolac resin, o-cresol novolac resin, naphthol novolac resin, aralkylphenol resin, and their modified products, anhydrous phthalic acid, anhydrous maleic anhydride, anhydrous hexahydrophthalic acid Acidic anhydrous curing agents such as dicarboxylic acid, anhydrous pyromellitic acid, and latent curing agents such as dicyandiamine, imidazole, BF3-amino modifier, and guanidine derivatives. These can be used alone or in combination of two or more.

In addition, it is preferable that the first curing component may include a curing component having a solid state at a temperature of 25 ° C. In the case of using a liquid-phase curing component, the viscosity of the adhesive film is increased together with the acrylic component in the second heat-curing section described later, and the voids generated between the wafer and the adhesive film are increased. The reliability of the intermeshing is reduced. In addition, the liquid first curing component cannot increase the curing speed to a desired level. Therefore, it is further preferred that the first curing component uses a component whose solid state is at a temperature of 25 ° C., and when a component whose liquid state is contained is contained, its content is preferably included in the entire weight of the first curing component. Account for 5 Below weight percent.

The first curing component is contained in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the epoxy component, but the invention is not limited to this, and can be changed according to the type of the selected epoxy component and curing component.

Then, the first heat-cured portion may further include a curing accelerator. The above-mentioned curing accelerator plays a role of adjusting the curing speed or the physical properties of the cured product. The above-mentioned curing accelerator can be used without limitation as a curing accelerator for a conventional non-conductive adhesive film containing an epoxy component, but it is not limited Examples of the property include an imidazole-based curing accelerator, a tertiary amine-based curing accelerator, and the like. Among them, an imidazole-based curing accelerator that is easy to adjust a curing speed or physical properties of a cured product is preferably used. The said hardening accelerator can be used individually or in combination of 2 or more types.

Although the imidazole-based curing accelerator is not particularly limited, the 1-cyanoethyl-2-phenylimidazole, which protects the 1-position of imidazole with cyanoethyl, or the basic name "2MA-," which is protected with isocyanuric acid, may be mentioned. "KK" (manufactured by Shikoku). These imidazole-based curing accelerators can be used alone or in combination of two or more.

When an acid anhydrous curing agent is used in combination with a curing accelerator such as an imidazole curing accelerator, it is preferable that the addition amount of the acid anhydrous curing agent is less than the theoretically equivalent equivalent to the epoxy group. . When the amount of the acid-anhydrous solidifying agent added is more than necessary, it is easy to dissolve chloride ions from the cured product of the composition of the present invention by means of water. For example, when the eluted component is extracted from the cured product of the composition of the present invention by heating water, the pH value of the extracted water is lowered to 4 to 5, and a large amount of chloride ions released from the epoxy resin may be dissolved.

In addition, when an amine-based curing agent is used in combination with a curing accelerator such as an imidazole-based curing accelerator, it is preferable that the addition amount of the amine-based curing agent is less than the theoretically equivalent equivalent to the epoxy group. When the addition amount of the amine water-based curing agent is more than necessary, it is easy to dissolve chloride ions from the cured product of the composition of the present invention via moisture. For example, when the eluted component is extracted from the cured product of the composition of the present invention by heating water, the pH of the extracted water is alkaline, and a large amount of chloride ions released from the epoxy resin may be eluted.

The curing accelerator may be contained in an amount of 10 to 50 parts by weight based on 100 parts by weight of the epoxy component, but is not limited thereto, and may be changed according to the type of the selected epoxy component, curing component, and curing accelerator. .

Hereinafter, the second thermosetting section will be described.

The second heat-cured portion contains an acrylic component, which is cured at a high temperature faster than the first heat-cured portion, and by increasing the curing speed of the first heat-cured portion together, the adhesive film is further improved at high temperatures. The solidification speed significantly prevents excessive generation of resin flow due to a short melting interval.

In the case of a non-conductive adhesive film containing only an epoxy component in the thermosetting portion, the curing speed at a high temperature is too low, and there is a problem that productivity is reduced. In addition, as the heat treatment is performed at a high temperature for a long time, the duration of the molten state increases, and at the same time, the adhesive film composition melted by the pressure applied during curing is separated from the wafers, thereby contaminating the side surfaces of the semiconductor element and the substrate. However, when the non-conductive adhesive film composition contains an acrylic component as the second heat-cured portion, the curing speed is further increased, the melting interval is shortened, and the resin flow is significantly reduced, thereby realizing a semiconductor device having excellent quality.

As the acrylic component, a known acrylic monomer can be used. Preferably, the acrylic monomer may use a polyfunctional (meth) acrylate containing two or more of the above-mentioned vinyl groups in order to express a faster curing speed at a high temperature and increase the curing speed of the first curing portion. In this case, the kind of the polyfunctional acrylate used is particularly limited. The present invention can use, for example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol Alcohol di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxypivalate dipentyl dimethacrylate (hydroxyl puivalic acid), bicyclic Dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified di (meth) acrylate, di (methyl) ) Acrylic acid oxyethyl isocyanate, allyl cyclohexyl di (meth) acrylate, tricyclosebacate (meth) acrylate, dimethylol dicyclopentane bis (methyl) Acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, neopentyl glycol modified trimethylpropane di (meth) acrylate, adamantane di (methyl) ) Acrylate or 9,9-bis [4- (2-propenyloxyethoxy) phenyl] fluorine and other bifunctional acrylates, trimethylolpropane tri (meth) acrylate, Dipentaerythritol (Meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth Acrylate), trifunctional urethane (meth) acrylate, tri (meth) acryloxyethyl isocyanurate, and other trifunctional acrylates, diglycerol tetra (meth) acrylate Or tetrafunctional acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol-modified dipentaerythritol penta (meth) acrylate, and other pentafunctional acrylates, and dipentaerythritol hexa (meth) acrylate, caprolactone Hexafunctional acrylates such as modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (e.g., reactants of isocyanate monomer and trimethylolpropane tri (meth) acrylate) Etc., but not limited to this.

However, it is preferable to use one or two or more kinds of tricyclodecanedimethanol diacrylate, tripropenyloxyethyl isocyanurate, and caprolactone-modified dipentaerythritol hexaacrylate.

On the other hand, when the above-mentioned acrylic component is charged in an oligomer state other than a monomer, the melt viscosity becomes very high, the bump filling property is reduced, and a problem occurs in fluidity. Therefore, it is preferable that the acrylic component Should be included as a monomer.

The acrylic component of the said 2nd thermosetting part may be contained with respect to 100 weight part of epoxy resins of a 1st thermosetting part. When the above-mentioned acrylic component is contained in an amount of less than 70 parts by weight, it is difficult to increase the curing speed to a desired level, and as a result, the curing time is lengthened and the productivity is reduced. Therefore, with a shortened curing time, void generation will increase significantly. In addition, curing at a high temperature of 280 ° C. or higher is required, and as curing is performed at a high temperature for a long period of time, there is a problem that excessive resin flow occurs, and components and / or substrates are contaminated. In addition, when the acrylic component is contained in an amount of more than 120 parts by weight, curing proceeds faster, and there is a problem in stability, and the tack at room temperature is increased. Therefore, delamination may occur after bonding to a wafer. At this time, voids are generated due to false bonding, and the generated voids cannot be discharged to the outside due to the viscosity at room temperature. In addition, as the curing speed of the adhesive film becomes excessively fast, the curing reaction of the adhesive film ends before the bump bonding is performed. Therefore, in order to perform the bump bonding, it is necessary to increase the welding pressure, thereby increasing the problem of bump damage.

In addition, the second heat curing unit may further include a second curing component for curing the acrylic component, and the second curing component may use a known component for curing an acrylic monomer without limitation. As a non-limiting example, one or more kinds of peroxides, azos, and the like may be used in combination.

Specifically, the above-mentioned peroxide-based component may be tert-butylperoxylaurate, 1,1,3,3-t-methylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl -2,5-bis (2-ethylhexylperoxy) hexane, 1-cyclohexyl-1-methylethyl peroxide-2-ethylhexanoate, 2,5-dimethyl -2,5-di (m-toluene peroxide) hexane, tert-butyl peroxy isopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoic acid, Tert-butyl peracetate, dicumyl peroxide, 2,5, -dimethyl-2,5-di (tert-butyl peroxy) hexane, tert-butyl cumene peroxide, tert-hexyl Peroxyneodecanoic acid, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-2-ethylhexanoate, tert-butylperoxyisobutyric acid, 1,1-bis ( Tert-butyl peroxy) cyclohexane, tert-hexyl peroxy isopropyl monocarbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate zinc, tert-butyl peroxypivalate, iso Propylbenzene neodecanoic acid, diisopropylbenzene hydrogen peroxide, cumene hydrogen peroxide, isobutyl peroxide, 2,4-dichlorobenzene peroxide Formamidine, 3,5,5-trimethylhexamethylene peroxide, octyl peroxide, lauryl peroxide, lauryl peroxide, stearyl peroxide, amber peroxide, benzyl Terbium peroxide, 3,5,5-trimethylhexamethane peroxide, benzamidine benzoylperoxide toluene, 1,1,3,3-tetramethylbutylperoxyneodecanoic acid, 1 -Cyclohexyl-1-methylethylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxycarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate Ester, di-2-ethoxymethoxyperoxydicarbonate, bis (2-ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, bis (3-methyl -3-methoxybutylperoxy) dicarbonate, 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) ) Cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (tert-butylperoxy) cyclododecane, 2,2 -Bis (tert-butylperoxy) decane, tert-butyltrimethylsilyl peroxide, bis (tert-butyl) dimethylsilyl peroxide, Butyl triallyl silicon alkyl peroxides, bis (t-butyl) and diallyl dialkyl peroxide silicon tri (t-butyl) peroxide aryl silicon group used alone or two or more kinds.

In addition, as the azo-based component, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methyl Methyl propionate), 2,2'-azobis (n-cyclohexyl-2-methylpropionamine), 2,2-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), 2,2'-azobis [n- (2-propenyl) -2-form Propylpropylamine], 2,2'-azobis (n-butyl-2-methylpropylamidamine), 2,2'-azobis [n- (2-propenyl) -2-methylpropyl Fluorene], 1,1'-azobis (cyclohexane-1-carbonitrile), 1-[(cyano-1-methylethyl) azo] formamide, etc., alone or two or more And use.

Preferably, the above-mentioned second curing component having a half-life temperature of 100 ° C. or higher for 10 hours can be used. When the above-mentioned second curing component having a half-life temperature of less than 100 ° C. for 10 hours is used, the adhesive film is cured only by a drying process. However, in order to prevent an increase in curing initiation temperature and a decrease in curing speed caused by a high 10-hour half-life temperature, the 10-hour half-life temperature of the second curing component may be 110 to 150 ° C.

Preferably, the aforementioned second curing component may be contained in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the aforementioned acrylic component. In the case where the second curing component is less than 1 part by weight, the curing degree of the acrylic component is insufficient, or the acrylic component is cured only by a single molecule with a small molecular weight. Therefore, when applied to a wafer, voids are generated, thereby making the semiconductor reliable. When it exceeds 20 parts by weight, an excessive curing reaction is caused to cause a significant increase in the shrinkage of the adhesive layer, thereby causing the wafer to bend.

Hereinafter, the said thermoplastic part is demonstrated.

The thermoplastic part has a function of having a good film forming property, and the film forming property is a mechanical property that is difficult to tear, chip, and adhere when the adhesive composition is embodied in a film form. In a normal state (for example, normal temperature), if it is easy to handle into a film, it can be considered to have good film formation. The thermoplastic portion has a function of improving the physical properties of the non-conductive adhesive film, such as flexibility of the non-conductive adhesive film, mechanical strength or heat resistance of a cured product, and reliability with a semiconductor element.

For this reason, it is preferable that the thermoplastic portion may include an acrylic copolymer to be subjected to a copolymerization reaction by including an acrylic monomer including an epoxy group. The acrylic copolymer has an epoxy group at a terminal and / or a branch (a pendant position), and the epoxy group-containing acrylic monomer included in the acrylic copolymer can be used without limitation, and a conventional monomer known in the art is preferably used. It may be one or more monomers of 2,3-epoxypropyl acrylate and 2,3-epoxypropyl methacrylate, More preferably, it can be 2,3-epoxypropyl methacrylate, which can further improve the physical properties of the non-conductive adhesive film.

According to a preferred embodiment of the present invention, the copolymer contains 1 to 10% by weight of the acrylic monomer containing the epoxy group. In the case where the above monomers exceed 10% by weight, only the lower molecular weight (less than 10,000) propylene resin can be obtained through the cohesive force of the epoxy group, which reduces the film formability, and the flexibility of the cured product cannot be sufficiently improved, which is difficult to reflect. Physical properties aiming at a non-conductive adhesive film such as reduction in bump bonding reliability. In addition, when the monomer is less than 1% by weight, although a high-molecular-weight propylene resin can be obtained, there is a concern that the ultimate viscosity may be increased and / or gelation may occur. Therefore, the strength or heat resistance of the cured product may be increased. Insufficient problems such as insufficient bump bonding reliability such as bump cavities, and difficulty in expressing the physical properties of the intended non-conductive adhesive film.

The acrylic copolymer may include a monomer having the following components in addition to the acrylic monomer having an epoxy group, that is, a linear or branched alkyl group having a carbon number of 30 or less, in particular, a carbon number of 4 to 18 One or more types of acrylic or methacrylic esters. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethyl Hexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, stearyl, or decyl Dialkyl, etc. In addition, the acrylic copolymer may include, as a monomer, a carboxyl group-containing monomer such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic anhydride, fumaric acid, or butenoic acid. Monomers such as anhydrous maleic anhydride or anhydrous itaconic acid monomers, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, or (4- Carboxyl group-containing monomers such as methylolcyclohexyl) -methacrylate, such as styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, ( Sulfonic acid group-containing monomers such as (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, or (meth) acrylamido naphthalenesulfonic acid, or 2-hydroxyethylpropene Phosphoric acid group-containing monomers such as oxyphosphoric acid. The rubber-based monomer may include monomers such as butadiene, styrene, and acrylonitrile. According to a preferred embodiment of the present invention, the acrylic copolymer may be a straight chain or a chain having 1,000 to 4000 parts by weight of the carbon number of 4 to 18 with respect to 100 parts by weight of the epoxy group-containing acrylic monomer. Branched alkyl acrylic ester monomers and / or straight or branched alkyl groups having 4 to 18 carbon atoms A copolymer prepared by copolymerizing an methacrylic acid ester monomer, 100 to 1,000 parts by weight of the aforementioned rubber-based monomer, and 0 to 200 parts by weight of an acrylic or methacrylic monomer containing the above-mentioned hydroxyl group. In addition to epoxy-based acrylic monomers, at least four monomers among methyl methacrylate, ethyl acrylate, butyl acrylate, acrylonitrile, and 2-hydroxyethyl (meth) acrylate are copolymerized for copolymerization. Copolymer.

The weight average molecular weight of the acrylic copolymer containing the epoxy group may be 100,000 to 1.2 million, preferably, the weight average molecular weight may be 300,000 to 800,000, and more preferably, 400,000 to 750,000. In the case where the above range is satisfied, it is expected that the physical properties of the non-conductive adhesive film of the following target can be expressed, that is, the flexibility and the lightness and flexibility of the cured product can be balanced while improving the flexibility, and the fluidity of the cured product becomes good , The filling property becomes better, which improves the reliability of bump bonding and the like. The weight average molecular weight is a value measured by gel permeation chromatography and displayed by a standard polystyrene calibration curve. When the molecular weight is less than 100,000, the film formability is lowered, the cured product flexibility cannot be sufficiently improved, and it is difficult to reflect a non-conductive adhesive film intended to improve the reliability of bump bonding. In addition, when the molecular weight exceeds 1.2 million, there is a problem that the resin fluidity decreases.

In addition, the glass transition temperature of the acrylic copolymer may be -30 to 80 ° C. More preferably, the glass transition temperature may be -10 to 50 ° C, and even more preferably, it may be 0 to 30 ° C. In the case where the glass transition temperature is lower than -30 ° C, the film formation property at room temperature is reduced. Since the tacky is strong, the adhesiveness is displayed. When the wafer is bonded, voids are generated due to false bonding. When the temperature exceeds 80 ° C., it hardens at room temperature and significantly reduces flexibility. Therefore, bump damage is likely to occur when a non-conductive film is pasted on a semiconductor wafer, and bump filling properties are significantly reduced.

In addition, the viscosity of the above acrylic copolymer at a temperature of 150 ° C may be 1,000 to 50000 Pa. s. However, in order to reflect more improved physical properties, preferably, the viscosity at a temperature of 150 ° C. may be 3000 to 30,000 Pa. s, more preferably, may be 5000 ~ 15000Pa. s. The viscosity at 150 ℃ is lower than 1000Pa. In the case of s, the film formability at low temperature is reduced, and the tacky is strong, and voids are generated due to home bonding during wafer bonding. Moreover, the viscosity at a temperature of 150 ° C is greater than 50,000 Pa. In the case of s, there is a problem that the reliability of the bump bonding is significantly reduced, that is, as the fluidity is significantly reduced, the bump filling property is significantly reduced, and bump damage is caused.

The thermoplastic resin may contain 30 to 100 weight percent of the above-mentioned epoxy group-containing acrylic copolymer. When the acrylic copolymer containing an epoxy group is less than 30% by weight, when it is used together with the above-mentioned thermosetting portion, the flexibility of the non-conductive adhesive film, the mechanical strength or heat resistance of the cured product, and the The effect of improving the physical properties of a non-conductive adhesive film such as reliability is negligible.

In addition, the thermoplastic part may be a polyester resin, a polyether resin, a polyimide resin, a polyimide resin, a polyimide resin, a polyvinyl butyral resin, a polyvinyl formal resin, or phenoxy. Base resin, polyhydroxy polyether resin, polystyrene resin, butadiene resin, acrylonitrile butadiene copolymer, acrylonitrile butadiene styrene resin, styrene butadiene copolymer alone or two or more And used to include. However, preferably, it may further include a phenoxy group, and more preferably, the weight-average molecular weight of the phenoxy group may be 10,000 to 100,000, and more preferably, 20,000 to 60,000. In this case, the physical properties of the target non-conductive adhesive film can be more favorably expressed.

The thermoplastic resin containing an acrylic copolymer may be contained in an amount of 30 to 100 parts by weight based on 100 parts by weight of the total weight of the epoxy component and the acrylic component of the thermosetting portion. body. Preferably, it may include 40 to 80 parts by weight, and more preferably 50 to 70 parts by weight, with respect to 100 parts by weight of the post-curing thermosetting resin. When the thermoplastic resin contains less than 30 parts by weight of thermoplastic resin, the desired non-conductive adhesive film cannot be reflected as the reliability of the bump bonding decreases significantly, that is, the film forming property is reduced or The film composition leaks out to the side of the supporting base material, and if it exceeds 100 parts by weight, the fluidity at the time of thermocompression bonding decreases, and the filling property between the bumps and the motor decreases.

On the other hand, according to a preferred embodiment of the present invention, the non-conductive adhesive film composition of the present invention may further include an inorganic filler, organic fine particles, and a silane coupling agent in addition to the above-mentioned thermosetting portion and thermoplastic portion.

The inorganic filler may improve thermal conductivity and adjust storage elasticity. The inorganic filler may generally be an inorganic filler contained in a non-conductive adhesive film composition. As a non-limiting example, the inorganic filler may include Various inorganic powders such as ceramics such as silicon dioxide, clay, gypsum, calcium carbonate, barium sulfate, aluminum oxide, barium oxide, silicon carbide, and silicon nitride. These can be used alone or in combination of two or more. Among them, it is preferable to use silicon dioxide. None of the above Although the shape of the organic filler is not particularly limited, preferably, spherical particles can be used. Preferably, the average particle diameter of the inorganic filler is in a range of 0.01 μm to 0.5 μm, and more preferably, in a range of 0.01 μm to 0.3 μm. When the average particle diameter is less than 0.01 μm, the strength of the inorganic filler is likely to be reduced as a result of aggregation. When the average particle diameter is more than 0.5 μm, the transparency of the cured product is reduced, and it is difficult to mark the position of the surface of the semiconductor element. Identification, which significantly reduces operability. In the present invention, inorganic fillers having different average particle diameters can be used in combination with each other.

On the other hand, in order to reduce the occurrence of stickiness of the adhesive film caused by the inclusion of the acrylic component in the heat-cured portion, it may be preferable to include 100 parts by weight of the total weight of the epoxy component and the acrylic component of the heat-cured portion. 50 to 150 parts by weight of the above-mentioned inorganic filler may more preferably include 90 to 130 parts by weight. When the content of the inorganic filler is less than 10 parts by weight, the viscosity of the adhesive film increases, and the reliability of bonding between the wafers decreases. In addition, when the content of the inorganic filler exceeds 150 parts by weight, the content of the thermosetting portion is relatively reduced, and the thermosetting performance is suppressed.

The above-mentioned organic fine particles play a role of imparting both flexibility and excellent stress relaxation properties to the cured product of the composition according to the present invention. The kind of the organic fine particles is particularly limited, and organic fine particles generally used for non-conductive adhesive films can be used without limitation. As a non-limiting example of the above-mentioned organic fine particles, organic fine particles having a core and shell structure may be used, and more specifically, rubber particles having a core and shell structure having different glass transition temperatures between the core (core material) and the shell (skin) may be used. By containing the rubber particles, the cured product has a phase separation structure in which the rubber component is stable compared with the epoxy resin of the matrix resin. The rubber particles may be particles of a core-shell structure including a multilayer structure of two or more layers, may include a multilayer structure of three or more layers, and in the case of particles of a core-shell structure including the multilayer structure of three or more layers, The outer shell refers to the outermost skin. In addition, it is preferable that the shell of the rubber particles is gelled by epoxy resin and standby or some cross-linking, and does not dissolve in the epoxy resin. As a resin component constituting the rubber particles, it is preferable that an allyl-based resin is usually used as the core. The said resin component can be used individually or in combination of 2 or more types. In addition, the shell of the rubber particles may have a functional group that reacts with an epoxy group in the epoxy resin. The functional group that reacts with an epoxy group is not particularly limited, and examples thereof include an amino group, a urethane group, an imine group, an alcoholic hydroxyl group, a carboxyl group, and an epoxy group. The functional group that reacts with the epoxy group can be used alone or in combination of two types. Combine the above. Although the rubber particles are not particularly limited, the average particle diameter is preferably 30 μm or less. When the average particle diameter of the rubber particles exceeds 30 μm, the stress relaxation properties of the cured product of the composition of the present invention may not be sufficiently improved.

The organic fine particles are preferably contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the total weight of the epoxy component and the acrylic component of the thermosetting portion, but are not limited thereto.

The silane coupling agent has a function of further improving the adhesion to the adherend, and a silane coupling agent generally used for a composition for a non-conductive adhesive film can be used without limitation. As a non-limiting example, an amino silane coupling agent, an epoxy silane coupling agent, a ureido silane coupling agent, an isocyanate silane coupling agent, a vinyl silane coupling agent, a propylene silane coupling agent, and a ketimine silane coupling agent may be mentioned. The agent and the like may preferably be an epoxy silane coupling agent. These silane coupling agents can be used alone or in combination of two or more. As the coupling agent for improving the adhesion to the adherend, in addition to the silane coupling agent, a titanium coupling agent, an aluminum coupling agent, or the like may be included. In addition, the silane coupling agent may be contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total weight of the epoxy component and the acrylic component of the thermosetting portion, but is not limited thereto.

In addition to the above-mentioned substances, a pH adjuster, an ion trapping agent, a viscosity adjuster, a thixotropy imparting agent, an oxidation inhibitor, a heat stabilizer, and a light may be added to the composition for a non-conductive adhesive film of the present invention as necessary. One or two or more kinds of various additives such as a stabilizer, an ultraviolet absorber, a colorant, a dehydrating agent, a flame retardant, an antistatic agent, a mold inhibitor, a preservative, and a solvent.

Although the pH adjusting agent is not particularly limited, examples thereof include acidic fillers such as silicon dioxide, and alkaline fillers such as calcium carbonate. These pH adjusting agents may be used alone or in combination of two or more.

Preferably, the ion trapping agent may be a trapping agent capable of reducing the amount of ionic impurities. Although not particularly limited, examples thereof include aluminosilicate, titanium hydroxide, bismuth hydroxide, zirconium phosphate, titanium phosphate, The above-mentioned ion trapping agents, such as hydrotalcite, molybdenum ammonium phosphate, zinc hexacyano, and organic ion exchange resins, can be used alone or in combination of two or more.

On the other hand, according to a preferred example of the present invention, the composition for a non-conductive adhesive film may further include a solvent. As the solvent, a solvent generally used for a composition for a non-conductive adhesive film can be used without limitation, and as a non-limiting example thereof, acetone and methyl ethyl ketone can be used. (MEK), ketones such as methyl isobutyl ketone (MIBK), cyclohexanone, and ethers such as methyl cellulose, ethylene glycol dibutyl ether, and butyl cellulose acetate. Although the amount of the solvent used is not particularly limited, it is preferably 10 to 500 parts by weight based on 100 parts by weight of the fir tree thermosetting resin.

The present application includes a non-conductive adhesive film for a semiconductor including the composition for a non-conductive adhesive film.

2 is a schematic cross-sectional view of a non-conductive adhesive film according to a preferred example of the present invention, which may include a sheet substrate 1 and an adhesive layer 2 containing the composition for a non-conductive adhesive film of the present invention.

The sheet substrate 1 may include a supporting substrate and an adhesive layer. As a non-limiting example of the supporting substrate, a resin film having excellent heat resistance or chemical resistance and a resin constituting the resin film may be used. A crosslinked film or a film subjected to a release treatment by applying a silicone resin or the like to the surface of the resin film.

In addition, although the resin constituting the resin film is not particularly limited, polyester, polyethylene, polypropyl, polybutene, polybutadiene, polyolefin, chlorinated vinyl, ethylene-methacrylic acid copolymer, and ethylene can be used. -Vinyl acetate copolymer, polyester, polyimide, polyethylene terephthalate, polyimide, polyurethane, etc.

In addition, although the thickness of the sheet substrate 1 is not particularly limited, it is preferably 3 μm or more and 500 μm or less, more preferably 3 μm or more and 100 μm or less, and still more preferably 10 μm or more and 75 μm or less.

On the other hand, although the thickness of the adhesive layer 2 is not particularly limited, it is preferably 3 μm or more and 100 μm or less, and more preferably 10 μm or more and 75 μm or less.

If the thicknesses of the sheet substrate 1 and the adhesive layer 2 are smaller than the lower limit, the effect of the semiconductor film 10 may be reduced. If the thickness exceeds the upper limit, the product may be difficult to prepare and the thickness accuracy may be reduced. Case.

Hereinafter, the manufacturing method of the non-conductive adhesive film 10 for semiconductors is demonstrated briefly. The method for preparing a non-conductive adhesive film to be described below is only an example, and the non-conductive adhesive film for semiconductors of the present invention is not limited thereto.

FIG. 3 is a schematic cross-sectional view of a non-conductive adhesive film according to a preferred example of the present invention. First, the method for preparing the adhesive film shown in FIG. 3 is described.

In FIG. 3, the adhesive layer 2 is obtained by applying the composition for a non-conductive adhesive film of the present invention to an upper part of a release substrate 21 such as a polyester sheet and drying the composition at a predetermined temperature. Only the adhesive layer 2 side of the adhesive layer 2 formed on the release substrate 21 is cut in half, so that the adhesive layer 2 is formed in a shape almost the same as that of the semiconductor wafer, for example, a circular shape. In this case, an adhesive film formed of the adhesive layer 2 and the release substrate 21 is obtained. The sheet substrate 1 is laminated on the above-mentioned adhesive layer 2 so that the adhesive layer of the sheet substrate 1 is in contact, so that a non-conductive adhesive film for a semiconductor as shown in FIG. 3 can be prepared.

As described above for the method of preparing the adhesive film of FIG. 3, the adhesive film is prepared by applying a composition for a non-conductive adhesive film on an upper part of a release substrate to dry the laminate substrate, and laminating the sheet substrate. By coating and drying a non-conductive adhesive film composition on the top of a sheet substrate that is not a release substrate, and laminating the release substrate, the adhesive film as shown in FIG. 2 can be prepared without laminating the release substrate. .

At this time, the melting zone of the adhesive layer in which the composition for an adhesive film is dried in the adhesive film may be 90 ° C or lower, more preferably 50 to 90 ° C.

Mathematical formula 1 Melting interval (△ T) = TA (℃) -TB (℃)

The above TA has a melt viscosity of 80,000 Pa. The temperature (° C) at S, the above TB has a melt viscosity of 20,000 Pa. Temperature at S (° C).

The long melting interval indicates that the time for applying heat for curing is prolonged in the step of preparing a semiconductor laminate described later using an adhesive film. If the extended time is too long, there is a concern that resin flow may occur. Therefore, the melting interval is preferably It is below 90 ° C. However, in the case where the melting range is lower than 50 ° C, it is difficult to adjust the curing speed, and it is difficult to achieve the desired physical properties such as bump damage.

In addition, according to a preferred example of the present invention, a non-conductive adhesive film for semiconductor as shown in FIG. 4 can be prepared. FIG. 4 includes: a release substrate 21; a bonding agent layer 2 formed on the upper portion of the release substrate 21; A film, or an ultraviolet (UV) or non-ultraviolet (Non UV) release layer 11 is formed on the upper portion of the adhesive layer 2; and a sheet substrate 1. The release film is easy to peel between the sheet substrate 1 and the adhesive layer 2, so that the handleability of the semiconductor wafer is improved.

The above-mentioned method for preparing a non-conductive adhesive film firstly The composition for a non-conductive adhesive film of the present invention is applied to an upper part of a release film such as a polyethylene terephthalate film, and after drying at a predetermined temperature, 21 layers of a release substrate such as a polyester sheet Press the upper part of the dried adhesive layer 2 and cut only the release film and the adhesive layer 2 side by half so that the release film and the adhesive layer 2 have almost the same shape as the semiconductor wafer. For example, a circular shape. In this case, an adhesive film composed of a release film, an adhesive layer 2 and a release substrate 21 can be obtained, and a non-conductive adhesive film as shown in FIG. 3 can be prepared by laminating the sheet substrate 1 on the release film. .

On the other hand, the present invention includes a semiconductor laminate that is cured by including the non-conductive adhesive film for semiconductors of the present invention.

The semiconductor laminate includes a non-conductive adhesive film for semiconductors and a wafer for semiconductors, regardless of dicing or not.

Specifically, FIG. 6 is a schematic cross-sectional view of a semiconductor laminate according to a preferred example of the present invention. A non-conductive adhesive film 10 is laminated on the functional surface 30a of the semiconductor wafer 30 with a non- Conductive adhesive film 10. A functional bump 30 (not shown) may be formed on the functional surface 30 a of the semiconductor wafer 30.

The semiconductor laminated body as described above is cut and separated (recombined) with each semiconductor element by performing a dicing process, and then unrolled and picked up, and the semiconductor element reassembled is mounted on the upper portion of the substrate, and then the adhesive layer 2 is processed by The semiconductor device is heated and cured to prepare a semiconductor device in which a semiconductor element is laminated on an upper portion of a substrate.

Furthermore, as another example, another semiconductor laminated body (semiconductor element, second element) of the present invention may be stacked three-dimensionally on an upper portion of a semiconductor element (first element) stacked on the above substrate to embody a semiconductor device. The functional surfaces of the first element and the second element can be connected to the back surface by bonding wires to shorten the transmission distance of electrical signals. Therefore, in order to improve the response speed, a conductor portion can be formed that penetrates in the thickness direction of each element. Through which you can exchange electrical signals between the functional surface and the back of the component. In addition, the first element and the second element may be electrically connected by solder bumps, and a non-conductive adhesive film including one of the first element or the second element may be positioned between the first element and the second element. The amount of adhesive layer.

The present invention will be described in more detail through the following examples, but it should be understood that the following examples do not limit the scope of the present invention, but are used to easily understand the present invention.

Example 1

First, 100 parts by weight of the epoxy component (solid, cycloaliphatic, EHPE3150, DAICEL) of the first heat-cured portion is added to 100 parts by weight of the second heat-cured portion of the heat-cured portion. A difunctional acrylic component (M200, Miwon Specialty Chemical Co., Ltd.) containing a vinyl group as a functional group. Based on 100 parts by weight of the total weight of the above-mentioned epoxy component and acrylic component, 30 parts by weight of an acrylic copolymer (KW197CHM, negamikogyo company) of about 700,000 weight average molecular weight and 10 parts by weight were added to the thermoplastic part. As the solvent of methyl ethyl ketone, the above acrylic copolymer contains 2,3-epoxypropyl methacrylate, which is an acrylic monomer containing epoxy groups, in a weight percentage of 25%. In the copolymer, the methyl ethyl ketone as the solvent is based on 100 parts by weight of the total weight of the epoxy component and the acrylic component, and then mixed by using a stirrer. Based on 100 parts by weight of the aforementioned epoxy component, 60 parts by weight of an acid anhydride curing agent (B4500, Dainippon Ink Chemical Company (DIC)) as a curing agent, and 5.7 parts by weight of a curing accelerator were added to the mixture. Imidazoles (2PZ-CN, Shikoku). In addition, 2 parts by weight of a propylene curing agent (Perbutyl-Z, manufactured by the company) was added based on 100 parts by weight of the acrylic component described above. In addition, based on 100 parts by weight of the total weight of the epoxy component and the acrylic component, 123 parts by weight of spherical silica (SGSO100, Sukgyung AT Co., Ltd.) having a particle diameter of 100 nm was used as an inorganic filler. And 4.0 parts by weight of a silane coupling agent (KBM403, Shintsu Corporation), and stirred at room temperature for 2 hours to obtain a composition for a non-conductive adhesive film. After filtering the above composition using a capsule screening program with a pore diameter of 10 μm, the substrate film (SG31, SKC) with a thickness of 38 μm was coated with a comma coating agent, and the temperature was 100 ° C. for 5 minutes. Drying was performed to obtain a non-conductive adhesive film having a thickness of 20 μm from which methyl ethyl ketone was removed, as shown in Table 1 below.

Examples 2 to 12

It was prepared in the same manner as in Example 1. By changing the composition ratio of the composition for a non-conductive adhesive film to the following Tables 1 to 3, the non-conductive adhesive films of Tables 1 to 3 were obtained. .

Comparative Example 1 to Comparative Example 2

Prepared in the same manner as in Example 1, by bonding non-conductive The composition ratio and the like of the film composition were changed as shown in Table 3 below to obtain a non-conductive adhesive film shown in Table 3 below.

Experimental example 1

The physical properties of the non-conductive adhesive films prepared in Examples and Comparative Examples were measured and shown in Tables 1 to 4.

1. Glass transition temperature and △ T detection

A differential thermal analyzer (DSC) was used to detect the glass transition temperature and ΔT.

At this time, by using a differential thermal analyzer to detect (condition: 0 to 300 (10 ° C / min)) △ T, the value of the peak temperature (Peak Temperature) minus the onset temperature (Onset Temperature) is judged as the △ T value .

2. Melt viscosity test

The non-conductive adhesive film was sampled at a thickness of 600 μm, 2.0 cm and 2.0 cm, and tested at 50 to 200 (10 ° C./min) using a rheometer (Rheometer). On the other hand, the viscosity value having the lowest numerical value of the detected value is determined as the lowest melt viscosity.

3． Tack evaluation at room temperature

A non-conductive adhesive film was sampled at a size of 3 cm 3 cm, and the viscosity was measured using a probe tack detection device. At this time, the diameter of the probe was 5 mm, and the detection condition was load. 200g. After the force of f was maintained for 10 seconds, the adhesiveness was measured by pulling at 10 mm / sec.

At this time, if the viscosity is 10g. f or more, it is judged that there is a problem in the process due to excessive viscosity and marked with ×, if it is 10g. Below f, it is judged that there is no problem in the process and is marked with ○.

Experimental example 2

The non-conductive adhesive films prepared in the examples and comparative examples were brought into contact with the adhesive layer (2 in FIG. 1) in the non-conductive adhesive film on the first surface (the surface on which the substrate and the semiconductor element are connected) of the silicon wafer. Thereafter, a vacuum laminator was used for lamination at a thinning speed of 0.1 mm / min, a pressure of 0.3 Mpa, and a temperature of 70 ° C to prepare a semiconductor wafer with a non-conductive non-conductive adhesive film. The diameter of the silicon wafer It is 8 inches, has a thickness of 500 μm, and has bumps (height 60 μm, pitch 150 μm) made of tin (Sn) / silver (Ag) on both sides. Then, for the prepared The non-conductive adhesive film shown in Tables 1 to 4 shows the occurrence of voids in the bonded semiconductor wafer.

Whether a void is generated or not is specifically observed by means of an optical microscope. When no void is generated, it is marked with X, and when a void is generated, it is marked with ○.

Experimental example 3

Using the non-conductive adhesive films prepared in the examples and comparative examples, the non-conductive attached semiconductor wafers prepared according to the procedure of Experimental Example 1 were subjected to a dicing process in the following order, and it was confirmed whether delamination occurred. And shown in Tables 1 to 3 below.

The above-mentioned delamination evaluation method is to evaluate the adhesion of the non-conductive adhesive film by using an optical microscope to observe the semiconductor wafer before the cutting process is completed and picked up. In the case, mark ○.

Experimental Example 4

Using the non-conductive adhesive films prepared in the examples and comparative examples, the non-conductive semiconductor wafers prepared according to the procedure of Experimental Example 2 were subjected to the dicing process in the order of Experimental Example 3, and the non-conductive that was cut was picked and bonded. After bonding the film to a semiconductor wafer and positioning it by inverted wafer welding on a 0.195mm thick epoxy-based circuit board on which solder made of tin / silver is formed, a 40N bond is applied at a bonding temperature of 250 ° C. The semiconductor device is prepared by thermal compression bonding at different soldering times of 3 seconds, 8 seconds, or 13 seconds under pressure. The following physical properties of the prepared semiconductor device were evaluated and shown in Tables 1 to 3.

Bump bonding

Cross-section of the prepared semiconductor device was used to confirm the bump bonding property. When there is no node defect every 10 bumps, mark x, and when the node defect is less than 2, mark △. If there are more than two node failures, mark ○.

2.Have voids been generated after wafer bonding?

When the semiconductor device was observed with an ultrasonic flaw detection device, when no void was generated, it was marked with X, and when a void was generated, it was marked with ○.

3. Whether bump damage occurs or not

During the soldering time of 3 seconds, the surface was observed with an optical microscope, and when bump damage did not occur, it was marked with X, and when bump damage was generated, it was marked with ○.

As confirmed from the above-mentioned Tables 1 to 3, in the case of Example 2 in which the acrylic component of the second heat-cured portion is included so as to be smaller than the preferred range of the present invention, the problem of viscosity at ordinary temperature is not respected, but, The curing speed is less than that in Example 1, and the bump bonding failure also occurs in the welding time of 8 seconds. It takes 8 to 13 seconds for the welding time to prevent the problems of bump bonding and void generation. It was confirmed that the welding time was significantly longer because it exceeded 8 seconds. In addition, it was confirmed that the melting interval was somewhat extended, and it was predicted that there was a concern that resin flow would occur.

In addition, in Example 5 in which the acrylic component of the second heat-cured portion was included so as to exceed the preferred range of the present invention, it was confirmed that the viscosity at room temperature significantly increased and bump damage occurred after welding. It can be predicted that the bumps will be damaged by the pressure applied when the curing reaction progresses with an excessively fast curing speed when the bumps are joined.

On the other hand, in the case of Examples 1, 3, and 4 which satisfy the preferable content of the acrylic component of the present invention, it was confirmed that all physical properties are superior to those of Examples 2 and 4.

On the other hand, in the case of Example 6, it was confirmed that the viscosity at room temperature was not good as the component having a liquid phase property was used as the epoxy component. It was also confirmed that bump damage occurred after welding. In addition, in the case of Example 7 where the epoxy was semi-solid, it was confirmed that the viscosity at room temperature was generated and the curing speed was reduced.

In addition, in the case of Example 8 where the homogeneous state of the epoxy and the first curing component was liquid, there was a problem in the process due to the occurrence of room temperature viscosity, and it was confirmed that bump voids were generated after the semiconductor wafers were bonded and cured. Speed is also significantly reduced.

In addition, when the epoxy property is a solid phase, it can be confirmed that, compared with Example 8, the curing speed of Example 9 in which the first curing component is mixed with a liquid is improved, but the problem of viscosity at room temperature and the curing speed are improved. The reduced problem is more significant than in Example 1.

In addition, in the case of Example 10 in which the number of functional groups of the acrylic component was one, it was confirmed that the curing speed was lower than that in Example 1.

In addition, in Example 11 where the half-life temperature of the second curing component was less than 100 ° C, it was confirmed that delamination occurred after the dicing step, and bump damage also occurred.

On the other hand, compared with Example 1, it can be confirmed that the solidification speed of the comparative example which does not include a 2nd hardening part is remarkably lowered, the silver melting interval is long, and there exists a possibility that resin flow may arise.

In addition, in the case of Comparative Example 2, since the first heat-curing portion was not included, although the curing speed was fast, but the degree was too fast, it was confirmed that as the curing adjustment was difficult, bump damage occurred, and Produced room temperature viscosity.

The above description is exemplary only, and not restrictive. Any equivalent modification or change made without departing from the spirit and scope of the present invention shall be included in the scope of the attached patent application.

Claims (14)

A non-conductive adhesive film comprising: a thermosetting portion including a first thermosetting portion including an epoxy component and a second thermosetting portion including an acrylic component; and a thermoplastic portion, and the thermosetting portion is added to 100 parts by weight of the thermosetting portion. The total weight of the epoxy component and the acrylic component of the part includes 30 to 100 parts by weight of the thermoplastic part. For example, the non-conductive adhesive film according to item 1 of the application, wherein the epoxy component includes a glycidyl ether type epoxy component, a glycidyl amine type epoxy component, a glycidyl ester type epoxy component, and a naphthalene type epoxy component. And one or more of alicyclic epoxy components. For example, the non-conductive adhesive film according to the first patent application range, wherein the acrylic component includes a polyfunctional acrylic monomer, and the polyfunctional acrylic monomer includes two or more vinyl groups. For example, the non-conductive adhesive film according to claim 1 is characterized in that the thermoplastic portion includes an acrylic copolymer, and the acrylic copolymer undergoes a copolymerization reaction by including an acrylic monomer containing an epoxy group. For example, the non-conductive adhesive film according to item 1 of the patent application range, wherein the second thermally cured portion contains a second curing component having a half-life temperature of 100 ° C. or higher for 10 hours. For example, the non-conductive adhesive film according to item 1 of the patent application range includes 70 to 120 parts by weight of the acrylic component with respect to 100 parts by weight of the epoxy component. For example, the non-conductive adhesive film according to the first patent application range, wherein the epoxy component includes an epoxy component having a solid phase property. For example, the non-conductive adhesive film according to item 1 of the patent application scope, wherein the first thermally cured portion includes a first cured component having a solid phase at a temperature of 25 ° C. For example, the non-conductive adhesive film according to item 7 of the patent application scope, wherein the epoxy component does not include an epoxy component having a liquid phase property at a temperature of 25 ° C. For example, the non-conductive adhesive film according to item 5 of the application, wherein the second heat-cured portion contains 1 to 20 parts by weight of the second curing component relative to 100 parts by weight of the acrylic component. For example, the non-conductive adhesive film according to the first patent application range, wherein the composition further contains 50 to 100 parts by weight of the total weight of the epoxy component of the first thermally cured portion and the acrylic component of the second cured portion. 150 parts by weight of an inorganic filler. A non-conductive adhesive film, comprising: an adhesive layer including: a thermosetting portion including a first thermosetting portion including an epoxy component and a second thermosetting portion including an acrylic component; and a thermoplastic portion. 100 parts by weight of the total weight of the epoxy component and the acrylic component of the thermosetting portion, the composition comprising 30 to 100 parts by weight of the thermoplastic portion is dried; and a release member is formed on at least one side of the adhesive layer. For example, the non-conductive adhesive film according to item 12 of the application, wherein in the above adhesive layer, the melting range according to the following mathematical formula 1 is 90 ° C or lower: Mathematical formula 1 Melting interval (△ T) = TA (° C) ) -TB (° C) The above TA has a melt viscosity of 80,000 Pa. The temperature (° C) at S, the above TB has a melt viscosity of 20,000 Pa. Temperature at S (° C). A semiconductor laminate comprising a non-conductive adhesive film according to any one of the scope of claims 1 to 12 of a patent application, which is thermally cured.