KR101082448B1

KR101082448B1 - Adheisive resin composition and dicing die bonding film using the same

Info

Publication number: KR101082448B1
Application number: KR1020070042017A
Authority: KR
Inventors: 박효순; 홍종완; 유현지; 김장순; 주효숙; 장석기
Original assignee: 주식회사 엘지화학
Priority date: 2007-04-30
Filing date: 2007-04-30
Publication date: 2011-11-11
Also published as: KR20080096991A; CN104745131A; CN101675137A; WO2008133472A1

Abstract

The present invention relates to an adhesive resin composition applied to the manufacture of a semiconductor package, an adhesive film using the same, a method for manufacturing the same, a dicing die bonding film, and a semiconductor device, wherein the adhesive resin composition according to the present invention comprises: a) a polyfunctional epoxy resin; b) a phenol resin having a moisture absorption of 2.0 wt% or less upon treatment for 48 hours at 121 ° C, 2 atmospheres and 100% RH; And c) a thermoplastic resin, and in the semi-cured state, the adhesion and embedding properties of the wafer are good to reduce the defect rate of the process, and in the hardened state, heat resistance, hygroscopic resistance, and downflow crack resistance are The semiconductor device which is excellent and excellent in reliability can be manufactured.

Adhesive resin composition, adhesive film, dicing die bonding film, wafer, semiconductor device, epoxy resin, thermoplastic resin, phenol resin

Description

Adhesive resin composition and dicing die bonding film using the same {ADHEISIVE RESIN COMPOSITION AND DICING DIE BONDING FILM USING THE SAME}

1 is a cross-sectional view of an adhesive film according to an embodiment of the present invention.

2 is a cross-sectional view of a dicing die bonding film according to an embodiment of the present invention.

3 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention.

&Lt; Description of reference numerals &

1 semiconductor chip

10 base film

20 adhesive layer

30 adhesive layer

40 description

50 wiring board

The present invention relates to an adhesive resin composition applied to the manufacture of a semiconductor package, an adhesive film using the same, a method for manufacturing the same, a dicing die bonding film, and a semiconductor device, wherein the adhesive resin composition according to the present invention comprises: a) a polyfunctional epoxy resin; b) a phenol resin having a moisture absorption of 2.0 wt% or less upon treatment for 48 hours at 121 ° C, 2 atmospheres and 100% RH; And c) a thermoplastic resin.

Recently, MCP (Multi Chip Package) method of stacking a plurality of semiconductor chips on a semiconductor substrate has been adopted, starting with a flash memory mounted in a mobile phone or a mobile terminal. In the MCP method, a film-like adhesive is used instead of a conventional liquid epoxy paste in bonding a semiconductor chip and a semiconductor substrate (Japanese Patent Laid-Open No. 3-192178 and Japanese Patent Laid-Open No. 4-234472).

On the other hand, the method of using the said film adhesive is a film single piece adhesion method and a wafer back surface adhesion method.

The film one-piece adhesive method is a post-process wire bonding method by cutting or punching an adhesive on a film, processing it into a single piece to fit a chip, adhering it to a semiconductor substrate, and picking a chip from a wafer and die-bonding it on the wafer. And a molding step to obtain a semiconductor device (Japanese Patent Laid-Open No. 9-17810).

In the wafer backside bonding method, a film-like adhesive is attached to the backside of the wafer, and a dicing tape having an adhesive layer is further attached to the backside not adhered to the backside of the wafer, and the wafer is diced and separated into individual chips. The chips are picked up and die-bonded to the semiconductor substrate, followed by a wire bonding and molding process to obtain a semiconductor device. However, the wafer backside bonding method has problems such as difficulty in transferring thinned wafers, increasing processes, difficulty in adapting to various chip thicknesses and sizes, difficulty in thinning films, and lack of reliability of high-performance semiconductor devices.

In order to solve the above problem, a method of adhering a film having an adhesive and an adhesive as a single layer to the back surface of a wafer has been proposed (Japanese Patent Laid-Open No. 2-32181, Japanese Patent Laid-Open No. 8-53655 and Japanese Patent Laid-Open No. 10-8001). ). The method is possible at one time without going through the lamination process twice, and since there is a wafer ring for supporting the wafer, there is no problem in transferring the wafer. Moreover, in the dicing die-bonding integrated film which consists of the point, adhesive agent and base material which consist of the composition of the said patent document, the ultraviolet curable adhesive and the thermosetting adhesive are mixed. Therefore, the pressure-sensitive adhesive serves to support the wafer in the dicing process, and loses the adhesive force after the ultraviolet curing process to facilitate the pickup of the chip from the wafer. Meanwhile, the adhesive may be hardened in the die bonding process to firmly bond the chip to the semiconductor substrate. However, in the dicing die-bonding integrated film, the pressure-sensitive adhesive layer and the adhesive layer in the film react with each other from manufacture to use, so that the substrate and the chip are not easily peeled off during the process of picking up the semiconductor chip after dicing. .

In order to solve the problems of the integrated film as described above, a dicing die-bonding-separable film having a pressure-sensitive adhesive and an adhesive separated from each other so as to be used as a dicing tape in a dicing process and used as an adhesive in a die bonding process has been proposed. . The dicing die-bonding separated film is easily separated from the adhesive and the adhesive by applying UV curing or heat after the dicing process, so that no problem occurs during the semiconductor chip pickup process, and the film thickness can be reduced during the die bonding process. It offers convenience. However, in the process of laminating the adhesive on the back side of the semiconductor wafer, a process of applying heat is added, unlike in the conventional method of attaching the adhesive at room temperature, and voids are also generated. In addition, there was a problem of warpage of the wafer due to the high temperature during heating, a problem of chip flying in the dicing process due to the difficulty of the progress of the post-process and the adhesive strength of the adhesive, ultimately had a problem in the reliability of the semiconductor package. Therefore, when semi-cured with an adhesive resin composition applied to semiconductor packaging, it is excellent in adhesive strength and embedding resistance, thereby reducing the process defect rate, and after the semiconductor package is manufactured in a cured state, heat resistance, hygroscopic resistance, and reflow crack resistance (reflow) There is an urgent need for development of an adhesive resin composition for semiconductors having excellent reliability such as crack resistance).

The present invention is to meet the needs as described above, the object of the present invention is an adhesive resin composition applied to semiconductor packaging is excellent in adhesive strength and embedding resistance when semi-cured, heat resistance, moisture absorption and downflow during curing It is to provide an adhesive resin composition having excellent reliability such as reflow crack resistance.

Another object of the present invention is to provide an adhesive film including the adhesive resin composition as an adhesive layer and a method of manufacturing the same.

Still another object of the present invention is to provide a dicing die bonding film comprising the adhesive film and the dicing tape.

Another object of the present invention is to provide a semiconductor wafer using a dicing die bonding film.

Still another object of the present invention is to provide a semiconductor device using the adhesive film.

The adhesive resin composition, the adhesive film, the dicing die bonding film, the semiconductor wafer, and the semiconductor device according to the present invention will be described in detail in sequence.

Adhesive resin composition

The present invention

a) polyfunctional epoxy resin;

b) a phenol resin having a moisture absorption of 2.0 wt% or less upon treatment for 48 hours at 121 ° C, 2 atmospheres and 100% RH; And

c) thermoplastic resin

It relates to an adhesive resin composition comprising a.

Hereinafter, each structural component of the resin composition of this invention is demonstrated in detail.

The a) polyfunctional epoxy resin used in the present invention is not particularly limited as long as it is cured to exhibit adhesive properties. Examples of a) polyfunctional epoxy resins used in the present invention include epoxy resins having three or more functional groups, preferably epoxy resins having an average epoxy equivalent of 180 to 1,000, more preferably cresol novolac epoxy resins and bisphenol A furnaces. Volac epoxy resin, phenol novolac epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin or The dicyclopentadiene modified phenol type epoxy resin is mentioned individually or in mixture of 2 or more types of the above. In the present invention, if the average epoxy equivalent of the a) polyfunctional epoxy resin is less than 180, the crosslinking density may be too high after curing to exhibit hard properties, and if the average epoxy equivalent exceeds 1,000, the glass transition temperature ( Tg) may be lowered.

In the present invention, in view of moisture resistance at a high temperature, the moisture absorption rate is 2.0% by weight or less upon treatment for 48 hours under pressure cooker test (PCT), specifically 121 ° C, 2 atmospheres and 100% RH. b) use phenolic resins; Moreover, when manufacturing a film using said b) phenol resin, it is preferable that the moisture absorption of a film is 1.5 weight% or less.

In the present invention, when the b) phenol resin is measured by thermogravimetric analysis (TGA), it is preferable that the weight loss ratio is less than 10% by weight when the temperature is raised from 50 ° C to 260 ° C at a rate of 10 ° C / min under a nitrogen atmosphere. . When the phenol resin has a weight loss ratio within the above range, since there are few volatile components in the process, reliability such as heat resistance and moisture resistance can be improved.

In the present invention, from the viewpoint of flowability, the viscosity of the b) phenol resin is preferably 200 cps or less when measured at 150 ° C., and when the phenol resin having the viscosity in the above range is used, the flowability is maintained well during the process. Since the embedding performance is improved, and the moisture resistance at high temperature is also good, the reliability of the semiconductor package can be improved. Although the minimum of the said viscosity is not specifically limited, 80 cps is preferable.

In the present invention, a polyfunctional phenol resin having three or more functional phenol hydroxy groups is used as the phenol resin in view of heat resistance, preferably a phenol resin having an average hydroxyl group equivalent of 100 to 500. If the average hydroxyl equivalent weight is less than 100, the hardness of the cured product is low, and there is a fear that the adhesive strength is lowered. If the equivalent weight exceeds 500, the glass transition temperature (Tg) is lowered and the heat resistance may be weak.

More preferable examples of the phenol resin used in the present invention include those represented by the following general formula (1).

[Formula 1]

(Where n is an integer of 0 to 50)

Preferred examples of the phenol resin represented by Formula 1 include dicyclopentadiene phenol novolac (hereinafter referred to as "DPP"), and the group consisting of DPP-6085, DPP-6095 and DPP-6115. At least one selected from is preferred.

In the adhesive resin composition of the present invention, the content of the phenol resin is preferably 0.5 to 1.2 equivalents relative to the epoxy resin, and the weight ratio is preferably included in the range of 60 to 150 parts by weight based on 100 parts by weight of the epoxy resin. Do. If the amount of the phenol resin is less than 60 parts by weight, the unreacted epoxy group remains, the glass transition temperature (Tg) is lowered, the remaining epoxy group is volatilized during the high temperature reliability test, there is a fear that the reliability of the semiconductor package. In addition, when the amount of the phenol resin exceeds 150 parts by weight, the crosslinking density increases, but there is a concern that the moisture absorption rate may increase or storage stability may deteriorate due to the unreacted hydroxyl group (OH).

The thermoplastic resin used in the present invention preferably has a glass transition temperature (Tg) of −60 to 30 ° C. and a weight average molecular weight of 100,000 to 1000,000 from the viewpoint of adhesion and heat resistance. By including the thermoplastic resin as described above it is possible to control the flowability during film molding, it is possible to secure the flexibility of the finished film by reducing the elastic modulus. If the glass transition temperature (Tg) is less than -60 ℃ in the above, the adhesive force is too large, there is a fear that the handleability and workability rather deteriorate, if it exceeds 30 ℃ there is a fear that the adhesive strength at low temperature. If the weight average molecular weight of the thermoplastic resin used in the present invention is less than 100,000, the flexibility and strength of the adhesive film may be lowered, resulting in poor handleability, and the flow may be increased during circuit filling of the semiconductor substrate, making it impossible to control the flowability. There is. In addition, when the weight average molecular weight exceeds 1000,000, the effect of suppressing flowability during die bonding is increased, and when the surface of the substrate has irregularities, the embedding property is lowered, thereby reducing the reliability and the circuit filling property of the adhesive film. .

The thermoplastic resin to be used in the present invention can be appropriately selected by those skilled in the art to which the present invention pertains, and is not particularly limited, but polyimide, polyether imide, polyester imide, polyamide, polyether sulfone, At least one selected from polyether ketone, polyolefin, polyvinyl chloride, phenoxy, reactive butadiene acrylonitrile copolymer rubber and acrylic resin is preferred, and acrylic resin is more preferred.

The acrylic resin is preferably an acrylic copolymer containing acrylic acid and derivatives thereof. Examples of the acrylic acid and its derivatives include acrylic acid; Methacrylic acid; Acrylic acid alkyl esters having 1 to 12 carbon atoms such as methyl acrylate or ethyl acrylate; Methacrylic acid alkyl esters having 1 to 12 carbon atoms such as methyl methacrylate or ethyl methacrylate; Monomers such as acrylonitrile or acrylamide and other copolymerizable monomers. In addition, the acrylic copolymer preferably includes at least one functional group selected from glycidyl group, hydroxyl group, carboxyl group and nitrile group. Preferable examples of the monomer having the above functional group include glycidyl (meth) acrylate as the case having a glycidyl group; Hydroxy (meth) acrylate or hydroxy ethyl (meth) acrylate in the case of having hydroxy; Or carboxyl (meth) acrylate etc. are mentioned as a case of having a carboxyl group.

Although the content of the functional group of the said acrylic copolymer is not specifically limited, It is preferable that it is the range of 0.5-10 weight part with respect to 100 weight part of acrylic resin. If the amount of the functional group is less than 0.5 parts by weight, it is difficult to secure the desired adhesive strength, and if it exceeds 10 parts by weight, the adhesive strength becomes excessively strong, resulting in poor workability and gelation.

It is preferable that the thermoplastic resin contained in the adhesive resin composition which concerns on this invention is contained in 100-400 weight part with respect to 100 weight part of epoxy resins. If the amount of the thermoplastic resin is less than 100 parts by weight, the elastic modulus increases, making it difficult to mold the resin composition into a film shape in the manufacturing process, and the flow tends to increase during molding, and if it exceeds 400 parts by weight, the flow inhibiting effect is increased. There exists a tendency for it to become so large that embedding property falls and the handleability in high temperature deteriorates.

The manufacturing method of the said thermoplastic resin can be suitably selected by those skilled in the art of this invention, It does not restrict | limit, For example, methods, such as solution polymerization, emulsion polymerization, or suspension polymerization, can be used.

The adhesive resin composition according to the present invention may further include a coupling agent, and the coupling agent may be included in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total resin component. In the present invention, by including the coupling agent, the adhesion to the interface of the semiconductor wafer or the silica filler can be improved, and at the time of the curing reaction, the organic functional group of the coupling agent reacts with the resin component, thereby adhering without damaging the heat resistance of the cured product. Performance and adhesion can be improved, and heat and moisture resistance is also improved. If the coupling agent is included in less than 0.01 parts by weight, the adhesive effect of the adhesive film is not sufficient, if included in more than 10 parts by weight may cause voids (void) or heat resistance due to the unreacted coupling agent may be lowered.

Although the coupling agent which can be used by this invention will not be specifically limited if it exhibits the above-mentioned effect, A silane coupling agent, a titanium coupling agent, an aluminum coupling agent, or a combination of 2 or more types of the above is preferable, and it is cost The silane coupling agent is more preferable in that the contrast effect is high. As a preferable example of the said silane coupling agent, one or more selected from amino silane, epoxy silane, mercapto silane, ureido silane, methacryloxy silane, vinyl silane, glycidoxy silane and sulfido silane is preferable.

Preferred examples of the amino silane include N-β- (aminoethyl) -γ-aminopropyl trimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane and γ-aminopropyl triethoxy Silane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyl trimethoxy cysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyl trimethoxy Silane, triaminopropyl-trimethoxysilane, or N-phenyl-γ-aminopropyl trimethoxysilane; Preferred examples of the epoxy silanes include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; Preferred examples of mercapto silanes include γ-mercaptopropyl trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, or γ-mercaptopropyl triethoxysilane; Preferred examples of ureido silanes include 3-ureidopropyl triethoxysilane, or 3-ureidopropyl trimethoxysilane; Preferred examples of the methacryloxy silane include γ-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, or γ-methacryloxypropylmethyl dimethoxysilane; Preferred examples of the vinyl silane include vinyl methyl dimethoxy silane, vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane and the like; Preferred examples of glycidoxy silanes include, but are not limited to, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropylmethyl dimethoxysilane, or γ-glycidoxypropylmethyl diethoxysilane. no.

The adhesive resin composition according to the present invention may further include a curing accelerator in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the epoxy resin, and the curing accelerator may be included to thereby The curing reaction can be promoted. When the amount of the curing accelerator is less than 0.1 part by weight, the crosslinking of the epoxy resin is insufficient, and heat resistance tends to be lowered. When the amount of the curing accelerator is more than 10 parts by weight, the curing reaction proceeds rapidly and the storage stability may be lowered.

The curing accelerator usable in the present invention is not particularly limited as long as it is commonly used in the technical field of the present invention, but at least one selected from an imidazole compound, triphenylphosphine (TTP), and a tertiary amine can be used. More preferably, an imidazole compound is used. Preferred examples of the imidazole compound include 2-methyl imidazole (2MZ), 2-ethyl-4-methyl imidazole (2E4MZ), 2-phenyl imidazole (2PZ), and 1-cyanoethyl-2-phenyl imidazole. (2PZ-CN), 2-undecyl imidazole (C11Z), 2-heptadecyl imidazole (C17Z) and 1-cyanoethyl-2-phenyl imidazole trimetalate (2PZ-CNS) One or more may be mentioned, but is not limited thereto.

The resin composition of the present invention may further include 5 to 100 parts by weight of a filler with respect to 100 parts by weight of the solid resin, in view of improving handleability and heat resistance and adjusting melt viscosity. If the amount of the filler is less than 5 parts by weight, the effect of improving the heat resistance and handleability due to the addition of the filler is insufficient, and if it exceeds 100 parts by weight, the effect of improving the workability and adhesion may be reduced.

Examples of the filler include organic fillers and inorganic fillers, and inorganic fillers are preferable in view of characteristics. The inorganic fillers include at least one selected from silica, talc, aluminum hydroxide, calcium carbonate, magnesium hydroxide, alumina and aluminum nitride, and have good dispersibility in the resin composition and uniform adhesion in the film. In terms of spherical silica is more preferred.

Although the average particle diameter of the said filler is not specifically limited, 10-1,000 nm is preferable, When the said particle diameter is less than 10 nm, there exists a possibility that a filler may aggregate easily in an adhesive film and a poor appearance may arise, and when it exceeds 1,000 nm, There is a fear that the filler in the film may protrude to the surface, and there is a risk of damaging the chip or impairing the adhesive improvement effect when thermocompression bonding with the wafer.

Adhesive film

The present invention also provides a base film; And

The adhesive layer formed on the said base film and containing the adhesive resin composition which concerns on this invention.

It relates to an adhesive film comprising a. The adhesive film of the present invention contains the adhesive resin composition according to the present invention, wherein the composition includes a low moisture absorption rate b) a phenol resin, thereby having excellent adhesion and embedding properties in a semi-cured state, and c) a thermoplastic resin and By using the filler, it is excellent in heat resistance, hygroscopic resistance and downflow crack resistance.

Referring to Figure 1 describes the adhesive film according to the present invention.

The base film 10 of the adhesive film according to the present invention is a polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film or polyimide film and the like. Plastic film can be used. Moreover, it is preferable to perform a mold release process on the surface of the said base film. Examples of the release agent used for the surface release treatment include alkyd, silicone, fluorine, unsaturated ester, polyolefin, or wax based, and in particular, alkyd, silicone or fluorine are particularly preferred.

10-500 micrometers is preferable and, as for the thickness of a base film, 20-200 micrometers is more preferable. When the thickness is less than 10 μm, the stretching is large when the substrate is coated and cured.

The adhesive layer 20 of the adhesive film contains the adhesive resin composition according to the present invention to minimize the generation of voids when bonding with the semiconductor wafer at low temperatures, and to maintain high adhesion with the wafer to prevent scattering of chips in the dicing process Can be.

Although the thickness of the said contact bonding layer is not specifically limited, It is preferable that the thickness of the heat-hardened contact bonding layer is 5-200 micrometers, and it is more preferable that it is about 10-100 micrometers. If the thickness is less than 5 mu m, the stress relaxation effect is insufficient at a high temperature, and if the thickness exceeds 200 mu m, it is not economical.

In addition, the adhesive layer 20 may be formed on one surface of the base film 10 to form a two-layer structure of the base film / adhesive layer, or to form a three-layer structure of the adhesive layer / base film / adhesive layer or the base film / adhesive layer / base film. It may be.

The invention also relates to a process for producing the adhesive film of the invention.

The method of manufacturing the adhesive film may include a first step of preparing a resin varnish by dissolving or dispersing an adhesive resin composition in a solvent;

A second step of applying the resin varnish to the base film; And

And a third step of removing the solvent by heating the base film coated with the resin varnish.

The first step of the production method of the present invention is to prepare a resin varnish using the adhesive resin composition according to the present invention.

The varnish is typically methyl ethyl ketone (MEK), acetone (Acetone), toluene (Toluene), dimethylformamide (DMF), methyl cellosolve (MCS), tetrahydrofuran (THF), N-methyl Pyridone (NMP) or a mixture of two or more of the above may be used. Although it is preferable to use a low boiling point solvent in consideration of the heat resistance of a base film, you may use a high boiling point solvent in order to improve coating property.

In addition, in the first step, a filler may be used to shorten the process time or improve the dispersibility in the adhesive film. When the filler is used, the first step may include:

(a) mixing a solvent, a filler and a coupling agent;

(b) adding and mixing an epoxy resin and a phenol resin to the mixture of step (a); And

(c) may include mixing the thermoplastic resin and the curing accelerator in the mixture of step (b).

Examples of the filler include a ball mill, a bead mill, three rolls, or a high speed disperser alone or a combination of two or more of the above. Examples of the material of the ball and the beads include glass, alumina, zirconium, and the like, and in terms of dispersibility of the particles, a ball or bead of a zirconium material is preferable.

The second step of the manufacturing method of the adhesive film according to the present invention is a step of applying the resin varnish to the base film.

The method of applying the resin varnish to the base film is not particularly limited, and conventional methods in the technical field of the present invention can be used. For example, a knife coat method, a roll coat method, a spray coat method, a gravure coat method , Curtain coat method, comma coat method or lip coat method can be used.

The third step of the manufacturing method of the adhesive film according to the present invention is a step of removing the solvent by heating the base film coated with the resin varnish. In this case, the heating is preferably performed at 70 to 250 ° C. for about 5 to 20 minutes, and the thickness of the heated and cured adhesive layer after applying varnish is preferably 5 to 200 μm, more preferably 10 to 100 μm.

Dicing die Bonding film

The invention also provides a dicing tape; And

It relates to a dicing die bonding film comprising the adhesive film according to the present invention laminated on the dicing tape.

The dicing die bonding film according to the present invention will be described with reference to FIG. 2.

The dicing tape is

Base film 40; And

It is preferable to include the adhesion layer 30 formed on the said base film.

Examples of the base film 40 of the dicing tape include polyethylene film, polypropylene film, polytetrafluoroethylene film, polyethylene terephthalate film, polyurethane film, ethylene vinyl acetone film, ethylene-propylene copolymer film, and ethylene-ethyl acrylate. A copolymer film, an ethylene-methyl acrylate copolymer film, etc. can be used, You may surface-treat, such as a primer application | coating, a corona treatment, an etching process, or UV treatment as needed. Moreover, when hardening an adhesive by ultraviolet irradiation, the thing with good light transmittance can be selected.

Although the thickness of the said dicing tape base material is not specifically limited, Considering handleability and a packaging process, it is preferable that it is 60-160 micrometers, and 80-120 micrometers is more preferable.

As the adhesive layer 30 of a dicing tape, a conventional ultraviolet curing adhesive or a thermosetting adhesive can be used. In the case of an ultraviolet curable adhesive, ultraviolet-ray is irradiated from the base material side, the cohesion force of an adhesive is raised and adhesive force is reduced, In the case of a thermosetting adhesive, temperature is added and a adhesive force is reduced.

As a method of manufacturing a dicing die bonding film according to the present invention as described above, a method of hot roll laminating a dicing tape and an adhesive film, a method of laminating press, etc. may be mentioned. Lamination methods are preferred. In addition, the hot roll laminate is preferably carried out at a pressure of 0.1 to 10kgf / cm ² at 10 to 100 ℃.

When the dicing die bonding film according to the present invention is bonded to a semiconductor wafer and diced, the dicing die bonding film has excellent adhesion to prevent chip scattering, and the adhesive film is easily peeled off at the time of pick-up so that the embedding property is excellent when bonding to the semiconductor substrate. It is possible to impart good package reliability to the semiconductor package.

Semiconductor wafer

The present invention also relates to a semiconductor wafer in which the adhesive film of the dicing die bonding film according to the present invention is attached to one side of the wafer, and the dicing tape of the dicing die bonding film is fixed to the wafer ring frame. .

In the semiconductor wafer as described above, the adhesive film of the dicing die bonding film is attached to the back surface of the wafer at a lamination temperature of 0 to 180 ° C., and the dicing tape of the dicing die bonding film is fixed to the wafer ring frame. Can be prepared.

Semiconductor devices

Also,

Wiring board 50;

An adhesive layer 20 comprising an adhesive composition according to the present invention attached to a chip mounting surface of the wiring board; And

A semiconductor device comprising a semiconductor chip 1 mounted on the adhesive layer.

The manufacturing process of the semiconductor device will be described below.

The semiconductor wafer with the dicing die bonding film mentioned above is cut | disconnected completely using a dicing apparatus, and it divides into individual chips.

Subsequently, if the dicing tape is an ultraviolet curing adhesive, the substrate side is irradiated with ultraviolet rays to cure, and if it is a thermosetting adhesive, the temperature is raised to cure the adhesive. As mentioned above, the adhesive hardened | cured by ultraviolet-ray or heat falls, and the adhesive force of an adhesive falls and it becomes easy to pick up a chip in a post process. At this time, as needed, a dicing die bonding film can be stretched. When such an expanding process is performed, the spacing between chips is determined to facilitate pick-up, and a misalignment occurs between the adhesive layer and the pressure-sensitive adhesive layer, thereby improving pickup performance.

Then, chip pick-up is performed. At this time, the adhesive layer of the semiconductor wafer and the dicing die bonding film may be peeled off from the pressure-sensitive adhesive layer of the dicing die bonding film to obtain a chip having only the adhesive layer attached thereto. The obtained chip | tip with the said adhesive bond layer is affixed on the board | substrate for semiconductors. The adhesion temperature of a chip is 100-180 degreeC normally, an adhesion time is 0.5-3 second, and an adhesion pressure is 0.5-2 kg _f / cm <^2> .

After the above process, a semiconductor device is obtained through a wire bonding and molding process.

The manufacturing method of a semiconductor device is not limited to the said process, Arbitrary process may be included and the order of a process may be changed. For example, the process may proceed to an ultraviolet curing-dicing-expanding process or a dicing-expanding-ultraviolet curing process. The chip attach process may further include a heating or cooling process.

Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited to the examples given below.

Example One

Production of Acrylic Resin

150 g butyl acrylate, 200 g ethyl acrylate, 140 g acrylonitrile, 16 g glycidyl methacrylate and 1500 g deionized distilled water were placed in a four-necked 3L reactor equipped with a stirrer, nitrogen substituent and thermometer. 4 g of polyvinyl alcohol (trade name: NH-17, manufactured by Nippon ghosei Co., Ltd.) diluted with 4% of water with a suspending agent, and 0.3 g of dodecyl mercaptan as a molecular weight regulator. To prepare a mixture. The mixture was subjected to nitrogen substitution for about 1 hour, and the temperature was raised to 55 ° C., and diethylhexyl peroxy dicarbonate diluted with 2% ethyl acetate as an initiator when the temperature was reached to the set temperature (trade names: Trigonox EHP, Akzo Nobel Co., Ltd. ( 4)) 4 g was added to initiate the polymerization reaction. At 4 hours after the start of the reaction, the reaction was terminated, washed with deionized distilled water several times, and dried using a centrifuge and a vacuum oven to obtain a polymer bead. The yield was 90%, the weight average molecular weight measured by gel permeation chromatography was 700,000, the molecular weight distribution was 3.0, and the glass transition temperature (Tg) measured by DSC (Differential Scanning Calorimeter) was 5 ℃. The obtained polymer beads were dissolved in methyl ethyl ketone and used for coating.

Adhesive resin composition, adhesive film and Dicing die Bonding Manufacture of film

Cresol novolac epoxy resin (EOCN-1020-55, manufactured by Nippon Chemical Co., Ltd .; epoxy equivalent: 199, softening point: 55 ° C) as an epoxy resin, 100 parts by weight of DPP-6115 (Kolon emulsifier (manufacturer); hydroxyl group Equivalence: 180, Softening point: 115%, 121 ° C, Moisture absorption rate at the time of 48 hours treatment at 2 atmospheres and 100% RH: 1.0% by weight) 90 parts by weight, 150 parts by weight of the thermoplastic resin prepared by the above method, curing 0.5 parts by weight of 2-phenyl-4-methyl-5-dihydroxymethyl imidazole (2P4MHZ, Shikoku Kasei) as a promoter, γ-glycidoxy propyl trimethoxy silane (KBM-403, Shin-Etsu) as a coupling agent 2 parts by weight of chemistry (agent) and 30 parts by weight of UFP-80 (denka, spherical silica, average particle diameter: 75 nm) were put into methyl ethyl ketone and stirred and mixed to prepare a varnish.

The varnish was applied to a base film having a thickness of 38 μm (release polyester film, RS-21G, SKC), dried at 160 ° C. for 3 minutes to prepare an adhesive film having a thickness of 20 μm, and then The adhesive film was laminated on the dicing tape (Srion Tech 6360-50) at 5 degreeC at 5 kgf / cm <^2> using the laminator (made by Fujishoko company), and the dicing die bonding film was obtained.

Example 2

Except that 100 parts by weight of dicyclopentadiene-modified epoxy (XD-1000L, Nippon Chemical Co., Ltd .; epoxy equivalent: 253, softening point: 74 ° C.) and 70 parts by weight of DPP-6115 were used as the phenol resin. A film was prepared in the same manner as in Example 1.

Example 3

Example except that 100 parts by weight of naphthol novolac epoxy (NC-7300L, Nippon Chemical Co., Ltd .; epoxy equivalent: 215, softening point: 62 ° C.) and 85 parts by weight of DPP-6115 as the phenol resin were used. The film was manufactured by the same method as 1.

Example 4

85 weights of DPP-6085 (Kolon emulsification (product); hydroxyl equivalent: 168, softening point: 87 degreeC, 121 degreeC, moisture absorption at the time of 2 atmospheres and 100% RH for 48 hours) as a phenol resin: A film was prepared in the same manner as in Example 1, except that part was used as a negative part.

Comparative example One

The film was prepared in the same manner as in Example 1, except that 100 parts by weight of bisphenol A epoxy (YD-128, Kukdo Chemical Co., Ltd .; epoxy equivalent: 187) was used as the epoxy resin and 100 parts by weight of DPP-6115 was used as the phenol resin. Prepared.

Comparative example 2

Phenolic novolak resin (KPH-F2001, Kolon Emulsifier (manufacturer); hydroxyl equivalent: 106, softening point: 84 ° C, 121 ° C, moisture absorption rate during 48 hours treatment under conditions of 2 atm and 100% RH as phenolic resin: 4.5 weight %) A film was prepared in the same manner as in Example 1, except that 50 parts by weight was used.

Comparative example 3

Bisphenol A novolac resin (Phenolite VH-4170, Gangnam Chemical Co., Ltd.) as a phenolic resin; hydroxyl equivalent: 118, softening point: hygroscopicity at 48 hours under conditions of 105 ° C, 121 ° C, 2 atmospheres and 100% RH: 5.2 wt%) A film was prepared in the same manner as in Example 1, except that 60 parts by weight was used.

Comparative example 4

Xylloc resin (KPH-F3075, Kolon Emulsifier) as a phenolic resin; hydroxyl equivalent: 175, softening point: 75%, 121 ° C, moisture absorption rate during 48 hours treatment at 2 atmospheres and 100% RH: 3.2% by weight A film was prepared in the same manner as in Example 1, except that 90 parts by weight was used.

The composition of the Example and Comparative Example and the moisture absorption rate and weight loss rate of the phenol resin used above are shown in Tables 1 and 2, respectively.

Furtherance ( Parts by weight ) Epoxy resin phenol
Suzy Thermoplastic resin Hardening
Accelerators (2 P4MHZ ) Coupling agent ( KBM -403) Filler ( UFP -80) Example One 100 90 150 0.5 2 30 Example 2 100 70 150 0.5 2 30 Example 3 100 85 150 0.5 2 30 Example 4 100 85 150 0.5 2 30 Comparative example One 100 100 150 0.5 2 30 Comparative example 2 100 50 150 0.5 2 30 Comparative example 3 100 60 150 0.5 2 30 Comparative example 4 100 90 150 0.5 2 30

Example Comparative example One 2 3 4 One 2 3 4 Of phenolic resin Moisture absorption rate ^* (weight%) 1.0 1.0 1.0 1.5 1.0 4.5 5.2 3.2 Weight loss rate of phenolic resin ^** (weight%) 7.5 7.5 7.5 7.8 7.5 17.4 25.2 8.0

* 121 ℃, 2 atmospheres and 100% RH At the time of 48 hours of processing Moisture absorption rate

** from 50 ° C to 260 ° C at a rate of 10 ° C / min under a nitrogen atmosphere Heated up Weight loss rate of city

Physical properties of the Examples 1 to 4 and Comparative Examples 1 to 4 were measured by the following methods, and the results are summarized in Table 3.

[Evaluation method of film]

(1) adhesive force ( Peel strength )

The 8-inch silicon wafer was laminated for 10 seconds with a die bonding film in a tape mounter (Hongle Electronics) set at 60 ° C. The die bonding film was measured using a TA.XT Plus tester (Stable Micro System) under conditions of 5 mm / sec peel rate and 180 ° peel angle.

(2) Landfill

PCBs with a height difference of 10 μm were used as the substrate. The die bonding film (20 μm) was cut into 25 mm × 25 mm and laminated at 60 ° C. with the chip in a tape mounter (Hongel Electronics). The chip attached to the PCB and the die bonding was pressed for 1 second at a pressure of 1.5 Kg at 130 ° C. The embedding rate was calculated by calculating the amount of the film flowing between the circuit patterns of the PCB, and the method of evaluating embedding was as follows.

◎: Purchase rate is 60% or more

○: purchase rate is 30-60%

X: Purchase rate is 30% or less

(3) of film Moisture absorption rate

The mass (A) of the film cured in an oven at 190 ° C. for 2 hours was measured, and the film was treated with a PCT instrument (Hyrayama) for 48 hours under conditions of 121 ° C./100% RH / 2 atm. Moisture was removed and the mass (B) was measured. The measured value was substituted into the following equation (1) to calculate the moisture absorption rate.

Equation (1)-Hygroscopicity (wt%) = ([B-A] × 100) / A

(4) moisture resistance ( moisture resistance )

The wafer and the film adhered to each other were observed for 72 hours after treatment using a PCT apparatus at 121 ° C., 100% humidity, and 2 atmospheres for 72 hours. The evaluation method was as follows.

○: no peeling occurs

×: peeling occurs

(5) IR Reflow ( reflow ) exam

After bonding the chip and the PCB to the die bonding film and cured for 2 hours at 180 ℃ to produce a semiconductor package sample. The sample was left to stand at -65 ° C. for 15 minutes using a thermal shock tester (Dimostec), followed by five steps of 15 minutes in an atmosphere of 150 ° C., and 72 hours in a constant temperature and humidity chamber at 85 ° C. and 85%. After standing, the sample was passed through an IR reflow apparatus whose temperature was set so that the maximum temperature of the sample surface was maintained at 260 ° C. for 30 seconds, and the treatment of standing at room temperature and cooling was repeated three times. Thereafter, cracks in the sample were observed by an ultrasonic microscope (SAT), and the evaluation method was as follows.

○: no peeling or cracking occurs

×: peeling or cracking occurs

Film evaluation items Adhesion (g / in ) Landfill Moisture absorption rate (weight%) Moisture resistance Downflow room
city
Yes One 50 ◎ 1.01 ○ ○ 2 58 ◎ 0.96 ○ ○ 3 51 ○ 0.84 ○ ○ 4 62 ◎ 1.08 ○ ○ ratio
School
Yes One 50 ○ 1.62 × × 2 53 × 3.10 × × 3 65 ○ 3.21 × × 4 45 ○ 1.85 × ○

As shown in Table 2, it can be confirmed that the adhesive films of Examples 1 to 4 according to the present invention have excellent physical properties in the semi-cured state and physical properties in the cured state compared to Comparative Examples 1 to 4.

In addition, in the film using the phenol resin contained in the formula (1) of the present invention, there was a slight difference in adhesion and embedding properties according to the type of epoxy resin, but the level was not enough to cause a problem in the process progress, low moisture absorption Excellent results were found in performance downflow. On the other hand, in Comparative Example 1 using a bifunctional epoxy resin without using a polyfunctional epoxy resin, although adhesion and embedding properties were secured to some extent, there was a problem in terms of reliability due to low heat resistance, and a comparison using a phenol resin having a high moisture absorption rate. Example 2 and 3 also confirmed that there is a problem in reliability. In the case of Comparative Example 4 using a phenol resin having a low weight loss rate but a high moisture absorption rate, the reflow resistance was good, but a problem occurred in terms of moisture resistance.

The adhesive film for semiconductors according to the present invention can reduce the defect rate of the process by good adhesion and embedding with the wafer in the semi-cured state, heat resistance, hygroscopicity or downflow crack after being manufactured in the semiconductor package in the hardened state It is possible to manufacture a semiconductor device with excellent reliability and excellent reliability.

Claims

a) polyfunctional epoxy resin;

b) a phenol resin having a moisture absorption of 2.0 wt% or less upon treatment for 48 hours at 121 ° C., 2 atmospheres, and 100% RH; And

c) thermoplastic resin

Adhesive resin composition comprising:

[Formula 1]

Wherein n is an integer from 0 to 50.

The method of claim 1,

Adhesive resin composition, characterized in that the average epoxy equivalent of the polyfunctional epoxy resin is 180 to 1,000.

The method of claim 1,

Multifunctional epoxy resin is cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, tetrafunctional epoxy resin, biphenyl type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane epoxy Adhesive resin composition, characterized in that at least one selected from the group consisting of a resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin and dicyclopentadiene modified phenol type epoxy resin.

The method of claim 1,

Adhesive resin composition, characterized in that the weight loss rate when the phenol resin is raised from 50 ℃ to 260 ℃ at a rate of 10 ℃ / min at a nitrogen atmosphere of less than 10% by weight.

The method of claim 1,

Adhesive resin composition, characterized in that the viscosity of the phenol resin is 200 cps or less at 150 ℃.

The method of claim 1,

Adhesive resin composition, characterized in that the average hydroxyl group equivalent of the phenol resin is from 100 to 500.

delete

The method of claim 1,

A phenol resin is dicyclopentadiene phenol novolak resin, The adhesive resin composition characterized by the above-mentioned.

The method of claim 1,

Adhesive resin composition, characterized in that the phenol resin is included in the range of 60 to 150 parts by weight based on 100 parts by weight of the epoxy resin.

The method of claim 1,

Adhesive resin composition, characterized in that the glass transition temperature of the thermoplastic resin is -60 to 30 ℃, the weight average molecular weight is 100,000 to 1000,000.

11. The method of claim 10,

Thermoplastic resin is selected from the group consisting of polyimide, polyether imide, polyester imide, polyamide, polyether sulfone, polyether ketone, polyolefin, polyvinyl chloride, phenoxy, reactive butadiene acrylonitrile copolymer rubber and acrylic resin Adhesive resin composition, characterized in that at least one selected.

The method of claim 11,

Adhesive resin composition, characterized in that the acrylic resin is an acrylic copolymer comprising at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, acrylonitrile and acrylamide.

13. The method of claim 12,

Acrylic copolymer is an adhesive resin composition, characterized in that it comprises at least one functional group selected from the group consisting of glycidyl group, hydroxyl group, carboxyl group and nitrile group.

The method of claim 13,

The content of the functional group of the acrylic copolymer is an adhesive resin composition, characterized in that 0.5 to 10 parts by weight with respect to 100 parts by weight of the acrylic resin.

The method of claim 1,

Adhesive resin composition, characterized in that the thermoplastic resin is contained in 100 to 400 parts by weight based on 100 parts by weight of the epoxy resin.

The method of claim 1,

An adhesive resin composition further comprising 0.01 to 10 parts by weight of a coupling agent based on 100 parts by weight of the total resin component.

The method of claim 16,

The coupling agent is at least one selected from the group consisting of a silane coupling agent, a titanium coupling agent and an aluminum coupling agent.

The method of claim 17,

The adhesive resin composition, wherein the silane coupling agent is at least one selected from the group consisting of amino silane, epoxy silane, mercapto silane, ureido silane, methacryloxy silane, vinyl silane, glycidoxy silane and sulfido silane.

The method of claim 1,

The adhesive resin composition characterized by further including the hardening accelerator of the range of 0.1-10 weight part with respect to 100 weight part of epoxy resins.

The method of claim 19,

The curing accelerator is at least one selected from the group consisting of an imidazole compound, triphenylphosphine and tertiary amine.

The method of claim 20,

The imidazole compound is 2-methyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 2-undecyl imidazole, 2-heptadecyl imid An adhesive resin composition, characterized in that at least one selected from the group consisting of dazole, and 1-cyanoethyl-2-phenyl imidazole trimetalate.

The method of claim 1,

Adhesive resin composition, characterized in that it further comprises 5 to 100 parts by weight of the filler with respect to 100 parts by weight of the solid resin.

The method of claim 22,

Adhesive resin composition, characterized in that the filler is at least one selected from the group consisting of silica, talc, aluminum hydroxide, calcium carbonate, magnesium hydroxide, alumina and aluminum nitride.

The method of claim 22,

Adhesive resin composition, characterized in that the average particle diameter of the filler is 10 to 1,000 nm.

Base film; And

The adhesive film formed on the said base film and containing the adhesive layer containing the adhesive resin composition of any one of Claims 1-6 or 8-24.

The method of claim 25,

An adhesive film, wherein the base film is a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film or a polyimide film.

The method of claim 25,

The surface of the base film is an adhesive film, characterized in that the release treatment with at least one release agent selected from the group consisting of alkyd-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based and wax-based.

The method of claim 25,

The thickness of a base film is 10-500 micrometers, The adhesive film characterized by the above-mentioned.

The method of claim 25,

The adhesive film characterized by the thickness of the heat-hardened adhesive layer is 5-200 micrometers.

A first step of preparing a resin varnish by dissolving or dispersing the adhesive resin composition according to any one of claims 1 to 6 or 8 to 24 in a solvent;

A second step of applying the resin varnish to the base film; And

A third step of removing the solvent by heating the base film coated with the resin varnish

Method for producing an adhesive film comprising a.

31. The method of claim 30,

The first step is

(a) mixing a solvent, a filler and a coupling agent;

(c) mixing the thermoplastic resin and the curing accelerator into the mixture of step (b).

Method for producing an adhesive film comprising a.

Dicing tape; And

The adhesive film according to claim 25 laminated on the dicing tape

Dicing die bonding film comprising a.

33. The method of claim 32,

Dicing tape

Base film; And

Adhesion layer formed on the base film

Dicing die bonding film comprising a.

The method of claim 33, wherein

The base film is a polyethylene film, polypropylene film, polytetrafluoroethylene film, polyethylene terephthalate film, polyurethane film, ethylene vinyl acetone film, ethylene-propylene copolymer film, ethylene-acrylic acid ethyl copolymer film, or ethylene-acrylic acid A dicing die bonding film, which is a methyl copolymer film.

The method of claim 33, wherein

Dicing die bonding film, characterized in that the surface of the base film is surface-treated by at least one method selected from the group consisting of primer coating, corona treatment, etching treatment, and UV treatment.

The method of claim 33, wherein

The pressure-sensitive adhesive layer is an ultraviolet curing adhesive or a heat curing adhesive.

A semiconductor wafer, wherein an adhesive film of the dicing die bonding film according to claim 32 is attached to one side of the wafer, and the dicing tape of the dicing die bonding film is fixed to the wafer ring frame.

Wiring board;

The adhesive film according to claim 25 attached to the chip mounting surface of the wiring board; And

A semiconductor chip mounted on the adhesive film

A semiconductor device comprising a.