KR101023844B1 - Adhesive resin composition, adhesive film, dicing die bonding film and semiconductor device using the same - Google Patents

Abstract

The present invention relates to an adhesive resin composition, an adhesive film and a manufacturing method thereof, a dicing die bonding film, and a semiconductor device using the same, which are applied to a semiconductor package process. A flexible epoxy resin comprising an aliphatic structure, b) a rigid epoxy resin comprising a repeating unit of an aromatic structure in the main chain, c) a curing agent and d) at least two curing accelerators, wherein the adhesive resin composition in the A-stage state is 130 The storage modulus at 0.degree. C. is 0.5 to 10 MPa, and the peak of the curing reaction exothermic curve is 200 to 240.degree. C., reducing the occurrence of burr in the dicing process, and different reaction active temperatures. Two types of curing accelerators are used to induce two stages of curing reaction, followed by wire bonding process, and voids during molding process. The problem does not occur in the zone.

Epoxy resin, 2 or more types of curing accelerators, A-stage, storage modulus, adhesive resin, adhesive film, dicing die bonding film, wafer, semiconductor device

Description

Adhesive resin composition, adhesive film, dicing die bonding film and semiconductor device using the same}

The present invention relates to an adhesive resin composition, an adhesive film for a semiconductor formed therefrom, a method for manufacturing the same, a dicing die bonding film, and a semiconductor device, and more particularly, a flexible epoxy resin, a rigid epoxy resin, a curing agent, and two or more kinds of curing. An adhesive resin composition comprising an accelerator, wherein the adhesive resin composition in the A-stage state has a storage modulus of 0.5 to 10 MPa at 130 ° C., and a peak of the curing reaction heating curve is 200 ° C. to 240 ° C. The present invention relates to an adhesive film, a method of manufacturing the same, a dicing die bonding film, and a semiconductor device using the same.

In the semiconductor industry, since the advent of ceramic packages in the 1960s, plastic packages using lead frames and molding compounds have been recognized as the most effective way to reduce costs, and more than 40 years later have been used in a large part of the semiconductor market. . With the development of semiconductors, such as miniaturization of devices and high integration of ICs, semiconductor packages are becoming smaller and have higher pin counts. In addition, with the recent rapid development of microelectronic technology and the development of electronic components, the development of new packages with high reliability is being accelerated as the demand for various integrated and high performance semiconductor packages rapidly increases.

The chip scale package (CSP) has been developed as a new generation in accordance with the miniaturization and high integration of semiconductor chip sizes. According to CSP, the chip is almost the same size as the package. As part of this current package trend, one of the more advanced packages is MCP (Multi Chip Package). The MCP is a technology that mounts one more chip on a chip and can mount much more capacity than before in a package of the same chip size.

Recently, the demand for the MCP is rapidly increasing in accordance with the high integration and high functionality of the semiconductor memory, starting with the flash memory mounted in a mobile phone or a mobile terminal. In addition, in the case of stacking chips in multiple stages, the size and thickness of stacked chips are rapidly progressed, and it has become a standard to stack ultra-thin chips having a thickness of 100 µm or less. In this MCP method, a film-like adhesive is used in place of a conventional liquid epoxy paste for bonding a semiconductor chip and a semiconductor substrate (Japanese Patent Laid-Open No. 3-192178, and Japanese Patent Laid-Open No. 4-234472). Liquid epoxy paste is inexpensive, but can not solve the warpage of the chip in the die bonding process, it is difficult to control the flowability, defects in the wire bonding process, difficult to control the thickness of the adhesive layer, or void of the adhesive layer There were various problems such as occurrence.

On the other hand, the method of using the conventional film adhesive is a film single piece adhesion method and a wafer back surface adhesion method. The film single-piece adhesive method is a post-process wire that cuts or punches a film-like adhesive into a single piece to fit the chip, adheres it to a semiconductor substrate, picks up the chip from the wafer, and die-bonds it onto the wafer. A semiconductor device is obtained through a bonding and molding process (Japanese Patent Laid-Open No. 9-17810).

On the other hand, the wafer backside bonding method attaches a film adhesive to the backside of the wafer, and further attaches a dicing tape with an adhesive layer on the opposite side to the backside of the wafer, thereby dicing the wafer and dividing the wafer into individual chips. do. The separated chips are picked up and die-bonded to a semiconductor substrate, followed by a wire bonding and molding process to obtain a semiconductor device. The wafer backside bonding method has difficulty in transferring thin wafers, increasing the number of processes, adaptability to various chip thicknesses and sizes, thinning films, and securing reliability of high-performance semiconductor devices.

In order to solve the above problem, a method of adhering a film having a single layer of an adhesive and an adhesive to a wafer back surface has been proposed (Japanese Patent Laid-Open Nos. 2-32181, 8-53655, and 10-8001). . This method can be performed in one step without going through the lamination process twice, and there is no problem in transferring the wafer because there is a wafer ring for supporting the wafer. According to the said patent document, the dicing die-bonding integrated film which consists of a point adhesive agent and a base material which consist of a specific composition mixes an ultraviolet curable adhesive and a thermosetting adhesive. The adhesive serves as an adhesive in the dicing process, and then loses adhesive strength through an ultraviolet curing process to facilitate pick-up of the chip from the wafer, and in the die bonding process, the adhesive is thermally cured as an adhesive to firmly fix the chip to a semiconductor substrate. Can be bonded. However, such a dicing die-bonded film has a problem that the adhesive force is not sufficiently lowered after the ultraviolet curing, so that the substrate and the chip are not easily peeled off during the step of picking up the semiconductor chip after dicing, thereby causing a defect.

In order to solve the problem of the integrated film, a dicing die-bonding separated film composed of two layers, a pressure-sensitive adhesive layer and an adhesive layer, is used as a dicing tape in a dicing process and used as an adhesive in a die bonding process. Proposed. The dicing die-bonding type film can be easily separated from the pressure-sensitive adhesive layer and the adhesive layer 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, such a detachable film also has a thinner adhesive film, and the A-stage elastic modulus of the adhesive film is used to completely fill the curved surface when the adhesive film is adhered to the organic wiring board having the circuit line on the surface to be attached to the chip. Development has been in progress toward lowering. However, the low modulus of the film can not withstand the heat generated during dicing, causing burr generation. In addition, a slight curing process may be performed to prevent the die from being pushed or lifted during the wire bonding process after the die attach. In this process, the degree of crosslinking of the film is increased and voids are generated during the molding process. Problem, and ultimately, semiconductor package reliability.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is to reduce the occurrence of burrs during dicing, even when applied to a packaging process with a semi-curing process before wire bonding, It is to provide an adhesive resin composition excellent in embedding properties, there is no void generation, high adhesive strength and ultimately excellent semiconductor package reliability.

It is another object of the present invention to provide an adhesive film including the adhesive resin composition, a method for manufacturing the same, and a dicing die bonding film.

Still another object of the present invention is to provide a semiconductor wafer and a semiconductor device using the adhesive film or the dicing die-bonding film.

The present invention comprises a) a flexible epoxy resin comprising a long chain aliphatic structure in the main chain; b) a rigid epoxy resin comprising repeating units of an aromatic structure in the main chain; c) hardeners; And d) two or more kinds of curing accelerators, wherein the resin composition in the A-stage state has a storage elastic modulus of 0.5 to 10 MPa at 130 ° C., and has a highest peak of the curing reaction exothermic curve at 200 ° C. to 240 ° C. It relates to a resin composition.

When the adhesive resin composition satisfying the above properties is applied to the adhesive film of the dicing die-bonding film used in the packaging process for manufacturing a semiconductor device, defects caused by the dicing die are not generated, and the semi-curing process is performed before wire bonding. Even when passing through, the bending of the substrate to be attached is easily filled so as not to cause void defects.

The die adhesive film in the package must satisfy both the deflection and stress relaxation properties between the chip and the substrate. The coefficient of thermal expansion (CTE) of the chip is 4 ppm / ℃, and in the case of the substrate, 10 to 15 ppm / ℃, the tear may occur due to the bending and high temperature reliability due to the difference in the CTE. Therefore, in the present invention, the rigid epoxy resin reduces CTE to minimize warpage, realizes adhesion and heat resistance properties, and gives a stress relaxation effect at high and low temperatures by using a flexible epoxy resin. In other words, by applying a polymer alloy technique to mix and use two kinds of epoxy having different elasticity, both soft and hard segments can coexist to satisfy both characteristics.

As used herein, the term "A-stage" refers to the degree of curing of the thermosetting resin. Thermosetting resins, such as epoxy resins, can be classified into A-, B-, and C-stages depending on the degree of curing. In the case of A-stages, the uncured state is typically unchanged, and the conversion rate of the epoxy group by curing reaction is measured by FT-IR. When it is about 0 to 20% of the progress state, the B-stage shows the conversion rate of about 20 to 60%, the C-stage shows the conversion rate of about 60 to 100%.

The resin composition of the A-stage state used in the present invention is a state in which only an organic solvent is removed without a hardening reaction in the process of undergoing a drying step in the manufacture of an adhesive film.

In general, the temperature rises due to friction between the rotary blade and the wafer during the dicing process, which is a process of remodeling a semiconductor wafer on which a pattern is formed. At this time, the heat generated may cause flowability to the adhesive film in the A-stage state attached to the back side of the wafer, which may cause burr generation. However, when the high temperature (130 ° C.) storage elastic modulus of the adhesive film in the A-stage state before curing is present in a range of 0.5 to 10 MPa, burr occurrence defects due to the above factors can be reduced. When the storage modulus of 130 ° C. or less is 0.5 MPa, burrs are severely generated during the remodeling angle process. If the storage elastic modulus of 130 ° C. or more is 10 MPa or more, the hardness of the A-stage adhesive film may be too hard, and thus the backing force with the wafer may be reduced.

On the other hand, the peak of the curing reaction heating curve used in the present invention means the highest temperature of the heating curve formed by the progress of the curing reaction by the elevated temperature, more specifically 5 ~ 10 ℃ / min speed to 280 ℃ using DSC It can be measured by raising the temperature.

When the highest point on the DSC heating curve of the adhesive film in the A-stage state is 200 ° C to 240 ° C, and the two conditions of the storage modulus at 130 ° C are 0.5 MPa to 10 MPa or less are minimized, burr generation during the remodeling process is minimized. At the same time, even when used during the semiconductor packaging process undergoes a semi-hardening process, it has excellent buriedness to eliminate the defect rate due to voids.

Hereinafter, each composition component of the adhesive film composition of this invention is demonstrated more concretely.

a) Flexible  Epoxy resin

The a) flexible epoxy resin used in the present invention means an epoxy resin having a glass transition temperature of 50 ° C. or less after curing. The flexible epoxy resin may be used without limitation as long as it contains two or more epoxy groups in the main chain and has a glass transition temperature of 50 ° C. or less. For example, a long-chain aliphatic repeating unit may be included or aliphatic in the main chain constituting the skeleton of the epoxy. The epoxy resin which consists only of a main chain can be used. The long chain aliphatic repeating unit includes a long chain alkyl structure such as polyethylene, polypropylene, or polybutadiene; Long chain alkyl glycols; Acrylic ester structures such as ethyl hexyl acrylate, butyl acrylate, n-octyl acrylate, or n-dodecyl methacrylate; And vinyl acetate; Or a polymer structure in which vinyl compounds such as styrene are appropriately mixed. Such an epoxy resin does not occur at room temperature or low temperature even after curing. Therefore, the flexible epoxy resin can be maintained in a film form without breaking before curing at high molecular weight, forms a crosslinked structure during the curing process, and has a viscoelasticity even after it becomes a crosslinked product.

The glass transition temperature of the flexible epoxy resin before curing is preferably -30 to 50 ° C, more preferably -20 to 40 ° C, and most preferably 0 to 30 ° C. If the glass transition temperature is less than -30 ℃, there is a problem that the flowability during the film formation, the deterioration of handling properties, and if the glass transition temperature is higher than 50 ℃, the adhesion strength with the wafer at low temperature is lowered, the chip is scattered during the dicing process or the adhesive and chip There is a problem that the wash water penetrates in between.

The weight average molecular weight of the flexible epoxy resin is preferably 100,000 to 1 million, more preferably 100,000 to 800,000, and most preferably 100,000 to 300,000. If the weight average molecular weight is less than 100,000, the film is inferior in handleability and heat resistance, and flowability during circuit filling of the semiconductor substrate cannot be controlled. When the weight average molecular weight exceeds 1 million, the elastic modulus is increased, and the flow inhibiting effect during die bonding is large, thereby reducing the circuit filling and reliability of the adhesive film.

The high molecular weight flexible epoxy resin having a glass transition temperature of less than −30 to 50 ° C. and a weight average molecular weight of 100,000 to 1 million may use a high molecular weight aliphatic epoxy, a rubber modified epoxy, or a mixture thereof, and has an ether group in the main chain. It is preferable that the structure excellent in its elasticity.

b) Rigid  Epoxy resin

B) Rigid epoxy resin used in the present invention means an epoxy resin having a glass transition temperature of more than 50 ° C. after curing. The rigid epoxy resin may be used without limitation as long as the resin contains two or more epoxy groups in the main chain and the glass transition temperature exceeds 50 ° C., for example, an epoxy including a repeating unit having an aromatic structure in the main chain forming the skeleton of the epoxy Resin can be used. Such an epoxy resin is hardened by forming a crosslinked structure through a curing process and has excellent mechanical strength such as excellent adhesion and heat resistance.

It is preferable that the said rigid epoxy resin uses the polyfunctional epoxy resin whose average epoxy equivalent is 180-1000. When the epoxy equivalent is less than 180, the crosslinking density is too high, and thus the entire adhesive film is easily exhibited a hard property. When the epoxy equivalent exceeds 1000, the glass transition temperature may be lowered as opposed to the property of the present invention, which requires high heat resistance. . Examples of the epoxy resins include cresol novolac epoxy resins, bisphenol A novolac epoxy resins, phenol novolac epoxy resins, tetrafunctional epoxy resins, biphenyl type epoxy resins, triphenol methane type epoxy resins and alkyl modified triphenols. Methane epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene modified phenol type epoxy resins, and the like, and these may be used alone or in combination of two or more thereof.

It is preferable that the self-softening point before hardening of the said rigid epoxy resin is 50-100 degreeC. If the softening point is less than 50 ° C, the A-stage modulus of the adhesive film is dropped and the tack becomes large, and the handleability is deteriorated. Cause problems.

The content of the rigid epoxy resin is preferably 10 to 200 parts by weight, more preferably 20 to 100 parts by weight based on 100 parts by weight of the flexible epoxy resin. If it is less than 10 weight part, heat resistance and handleability will fall, and if it exceeds 200 weight part, the rigidity of a film will become strong and workability and reliability will fall.

c) curing agent

The c) hardener used in the present invention is not particularly limited as long as it is a resin that forms a crosslinked structure by reacting with the a) flexible epoxy resin and / or the b) rigid epoxy resin, but the a) flexible epoxy resin and the b) more preferably, a resin that reacts with both rigid epoxy resins to form a crosslinked structure. These resins each form a crosslinked structure with a) flexible epoxy resin, which forms a soft segment, and b) a rigid epoxy resin, which forms a hard segment, thereby improving the heat resistance of the cured adhesive, and at the same time, a) the interface between the flexible epoxy resin and b) a rigid epoxy resin. It is advantageous in terms of improving the reliability of semiconductor package by acting as a link between two resins.

As such a resin, a polyfunctional phenol resin is preferable in terms of heat resistance, and the phenol resin preferably has a hydroxyl equivalent of 100 to 1000. When the hydroxyl equivalent is less than 100, depending on the type of phenolic resin, the cured product with the epoxy is generally hardened, which may reduce the buffering effect in the semiconductor package of the adhesive film, and when the hydroxyl equivalent exceeds 1000, Crosslinking density of hardened | cured material falls, and heat resistance can be inhibited.

Such polyfunctional phenol resins include bisphenol A resins, phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, phenol aralkyl resins, polyfunctional novolac resins, dicyclopentadiene phenol novolac resins, amino Any triazine phenol novolak resin, polybutadiene phenol novolak resin, biphenyl type resin, or other polyfunctional resin can be used, and these may be used alone or in combination of two or more thereof.

In addition, the curing agent is preferably a softening point of 50 ~ 100 ℃. If the softening point is less than 50 ℃, the handleability and heat resistance may be deteriorated due to the increase in tack properties.If the softening point exceeds 100 ℃, the adhesive strength between the adhesive film and the wafer may be reduced by increasing the hardness of the adhesive film. This may cause defects such as chip scattering.

The content of the curing agent is preferably 0.4 to 2 equivalents, more preferably 0.8 to 1.2 equivalents, relative to the epoxy integrated equivalents of a) flexible epoxy resin and b) rigid epoxy resin. If the ratio of a) flexible epoxy resin and b) rigid epoxy resin is less than 0.4 equivalent ratio of epoxy equivalent, many unreacted epoxy remains and glass transition temperature is low, resulting in low heat resistance, and high temperature or long-term heat must be supplied for reaction of unreacted epoxy group. If the ratio exceeds 2 equivalents, the crosslinking density is increased, but there may be disadvantages such as a decrease in storage stability and an increase in moisture absorption / dielectric property due to unreacted hydroxyl groups.

d) two or more curing accelerators

In the present invention, two or more curing accelerators are used to adjust the storage modulus on the A-stage of the adhesive film, and to control the rate and degree of curing reaction, and may be used in combination of two or more in search of suitable types experimentally. It is preferable to use 2 or more types of hardening accelerators in which hardening reaction start temperature differs.

In the case of using two kinds of curing accelerators, a small amount of mesophilic active curing accelerator preferentially induces a curing reaction during the semi-curing process to ensure working stability during the wire bonding process, and a high temperature active curing accelerator is a curing reaction during the post-curing process. It is possible to fully realize the physical properties of the adhesive film without impairing the physical properties such as heat resistance due to uncured.

In addition, even after the semi-curing process, the voids completely fall out during the post-curing process, thereby minimizing defects due to the voids.

The type of the curing accelerator is not particularly limited, and imidazoles, triphenylphosphine (TPP) s, tertiary amines or mixtures thereof may be used. In particular, imidazole-based curing accelerators 2-methyl imidazole (2MZ), 2-ethyl-4-methyl imidazole (2E4MZ), 2-phenyl imidazole (2PZ), 1-cyanoethyl-2-phenylmidazole (2PZ-CN), 2-undecyl imidazole (C11Z), 2-heptadecyl imidazole (C17Z), 1-cyanoethyl-2phenylimidazole trimetalate (2PZ-CNS) or mixtures thereof Can be mentioned.

The content of the two or more curing accelerators is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight based on 100 parts by weight of the weight of the flexible epoxy resin and the rigid epoxy resin. When the content of the curing accelerator is less than 0.01 parts by weight, the reaction rate is lowered, the crosslinking of the epoxy resin is insufficient, and the heat resistance is lowered. When the content of the curing accelerator is more than 5 parts by weight, the curing reaction occurs rapidly and an adhesive film in the A-stage state can be obtained. The storage stability of the missing or prepared A-stage state adhesive film is lowered.

e) Filling

The adhesive resin composition of the present invention may further include a filler. By including the said filler, handleability improvement, heat resistance improvement, and melt viscosity adjustment are possible. Examples of the filler include organic fillers and inorganic fillers, and inorganic fillers are more preferable in view of characteristics. The inorganic filler is not particularly limited, but silica, aluminum hydroxide, calcium carbonate, magnesium hydroxide, aluminum oxide, talc, aluminum nitride and mixtures thereof are preferable.

Although the content of the said filler is not specifically limited, 0.5-100 weight part is preferable with respect to 100 weight part of resin except a filler, and 5 weight part-50 weight part are more preferable. If the content is less than 0.5 parts by weight, the effect of improving the heat resistance and handleability due to the addition of the filler is not sufficient. If the content is more than 100 parts by weight, the workability and the substrate adhesion deteriorate.

0.001-10 micrometers is preferable and, as for the average particle diameter of a filler, 0.005-1 micrometer is more preferable. When the average particle diameter is less than 0.001 µm, fillers tend to aggregate in the adhesive film and appearance defects occur. When the average particle diameter exceeds 10 µm, the filler easily protrudes to the surface in the adhesive film, which may damage the chip during the wafer and thermocompression bonding, and the effect of improving the adhesiveness may be lowered.

The present invention also provides a base film; And

It is related with the adhesive film formed on the said base film, and containing the adhesive layer containing the adhesive resin composition which concerns on this invention.

As the base film, a plastic film such as polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyimide film, or the like may be used. In addition, the surface of the base film is preferably a release treatment. Alkyl-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based, or wax-based may be used as the release agent used in the release treatment, and in particular, alkylated, silicone-based, or fluorine-based may be preferable.

10-500 micrometers is preferable and, as for the thickness of the said base film, More preferably, it is 20-200 micrometers. If the thickness is less than 10 μm, deformation of the base film easily occurs during the drying process, resulting in uneven appearance of the adhesive layer, and it is not economical if it exceeds 500 μm.

Although the thickness of the said adhesive layer is not specifically limited, Although the thickness of the adhesive layer heat-hardened after application | coating is not specifically limited, 1-200 micrometers is preferable and 5-100 micrometers is more preferable. If the thickness is less than 1 μm, the stress relaxation effect and embedding property may be insufficient at a high temperature, and if it is more than 200 μm, it is not economical.

The present invention also comprises the steps of dissolving or dispersing the adhesive resin composition in a solvent to produce a resin varnish; Applying the resin varnish to a base film; And it relates to a method for producing an adhesive film comprising the step of removing the solvent by heating the base film.

The adhesive resin composition is as described above, the solvent for varnishing to prepare the adhesive film is typically methyl ethyl ketone (MEK), acetone (Acetone), toluene (Toluene), dimethylformamide (DMF), methyl cell Rosolve (MCS), tetrahydrofuran (THF), N-methylpyrrolidone (NMP) or mixtures thereof and the like can be used. Since the heat resistance of a base film is not good, it is preferable to use a low boiling point solvent, but in order to improve the uniformity of a coating film, a high boiling point solvent may be used, and these solvents may be used in mixture of 2 or more types.

A well-known method can be used as a method of apply | coating a resin varnish to the said base film. For example, the knife coat method, the roll coat method, the spray coat method, the gravure coat method, the curtain coat method, the comma coat method, or the lip coat method etc. are mentioned.

In order to improve the dispersibility in the adhesive film when the filler is included in the adhesive resin composition, a ball mill, bead mill, three rolls, or a grinder may be used alone, It can also be used in combination. Examples of the material of the ball and the beads include glass, alumina, zirconium, and the like. In view of dispersibility of the particles, zirconium balls or beads are preferable.

In the present invention, after mixing the solvent and the filler with a ball mill or bead mill for a predetermined time, a low viscosity rigid epoxy resin and a curing agent are added and mixed, and finally a high viscosity flexible epoxy resin and two or more curing accelerators are mixed. It is easy to shorten the mixing time and the dispersibility is improved.

In addition, in the step of removing the solvent by heating the base film, the heating conditions are preferably about 1 to 10 minutes at 70 ~ 250 ℃.

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 tape is a base film; And an adhesive layer formed on the base film.

The base film of the dicing tape is polyethylene film, polypropylene film, polytetrafluoroethylene film, polyethylene terephthalate film, polyurethane film, ethylene vinyl acetone film, ethylene-propylene copolymer film, ethylene-ethyl acrylate copolymer film Or an ethylene-methyl acrylate copolymer film etc. can be used and surface treatment, such as a primer application | coating, a corona treatment, an etching process, or a UV treatment, may be performed as needed. Moreover, when hardening an adhesive by ultraviolet irradiation, the thing with good light transmittance can be selected. Although the thickness of a dicing tape base material is not specifically limited, 60-160 micrometers is suitable and 80-120 micrometers is preferable in consideration of handleability and the process of a packaging company.

As an adhesive layer of a dicing tape, a normal ultraviolet curable adhesive or a thermosetting adhesive can be used. In the case of an ultraviolet curable pressure sensitive adhesive, ultraviolet rays are irradiated from the substrate side to raise the cohesive force and the glass transition temperature of the pressure sensitive adhesive to lower the adhesive force, and in the case of the thermosetting adhesive, the adhesive force is lowered by applying a temperature.

As a method of manufacturing a dicing die-bonding film according to the present invention as described above, a method of hot roll laminating and pressing of a dicing tape and an adhesive film may be used, and in view of the possibility and efficiency of a continuous process, desirable. Hot roll lamination conditions are preferably from 0.1 to 10kgf / cm ² at 10 ~ 100 ℃.

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. It can manufacture.

Also,

Wiring board;

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

A semiconductor device comprising a semiconductor chip 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 described above, the pressure-sensitive adhesive cured by ultraviolet rays or heat decreases the adhesive strength with the adhesive, so that the pick-up of the chip becomes easy in a later step. At this time, a dicing die bonding film can be stretched as needed. When the expansion process is performed, the gap between the chips is extended 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 is peeled from the adhesive layer of the dicing die bonding film, and the chip | tip with only an adhesive bond layer can be obtained. 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> . When using a curved organic wiring board during this process, embedding is required.

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 adhesive layer curing-dicing-expanding process or may proceed to a dicing-expanding-adhesive layer curing process. The chip attach process may further include a heating or cooling process.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

Preparation of Adhesive Film Example  1-4, Comparative example  1 ~ 3)

Example 1

75 parts by weight of high molecular weight aliphatic epoxy resin (SA-34, LG Chemical, Tg = 20 ° C, weight average molecular weight of 300,000), 25 parts by weight of aromatic epoxy resin (novolak type epoxy resin, softening point of 80 ° C), epoxy resin 19 parts by weight of a phenol resin (phenol novolak resin, softening point 90 ° C.), 0.1 part by weight of a medium temperature onset curing accelerator (2-methyl imidazole (2MZ)), a high temperature onset curing accelerator (2-phenyl-4-methyl already Varnish was prepared by stirring and mixing methyl ethyl ketone to a composition consisting of 0.5 parts by weight of dozol (2P4MZ)) and 5 parts by weight of silica (fused silica, average particle diameter: 75 nm) as a filler.

The adhesive resin composition was applied to a base film (SKC, RS-21G) having a thickness of 38 μm, dried to produce an adhesive film having a thickness of 20 μm, which is commonly used by packaging companies.

[Example 2]

A resin was prepared in the same manner as in Example 1 except that 0.2 part by weight of a medium temperature initiation cure accelerator (2-methyl imidazole (2MZ)) was used, and an adhesive film was prepared.

Example 3

75 parts by weight of high molecular weight aliphatic epoxy resin (SA-34, LG Chemical, Tg = 20 ° C, weight average molecular weight of 300,000), 25 parts by weight of aromatic epoxy resin (novolak type epoxy resin, softening point of 80 ° C), epoxy resin 19 parts by weight of phenol resin (phenol novolak resin, softening point 90 DEG C), 0.1 part by weight of medium temperature onset curing accelerator (triphenyl phosphine (TPP)), high temperature onset curing accelerator (2-phenyl-4-methyl imidazole) (2P4MZ)) 0.5 weight part and the composition which consists of 5 weight part of silicas (melted silica, average particle diameter 75nm) as a filler were stirred and mixed with methyl ethyl ketone, and the varnish was manufactured. An adhesive film was produced in the same manner as in Example 1.

Example 4

75 parts by weight of high molecular weight aliphatic epoxy resin (SA-34, LG Chemical, Tg = 20 ° C, weight average molecular weight of 300,000), 25 parts by weight of aromatic epoxy resin (novolak type epoxy resin, softening point of 50 ° C), epoxy resin 19 parts by weight of a phenol resin (phenol novolak resin, softening point 100 ° C.), 0.2 parts by weight of a medium temperature onset curing accelerator (2-methyl imidazole (2MZ)), a high temperature onset curing accelerator (2-phenyl-4-methyl Varnish was prepared by stirring and mixing methyl ethyl ketone to a composition consisting of 0.5 parts by weight of dozol (2P4MZ)) and 5 parts by weight of silica (fused silica, average particle diameter: 75 nm) as a filler. An adhesive film was prepared in the same manner as in Example 1.

Comparative Example 1

75 parts by weight of high molecular weight aliphatic epoxy resin (SA-34, LG Chemical, Tg = 20 ° C, weight average molecular weight of 300,000), 25 parts by weight of aromatic epoxy resin (novolak type epoxy resin, softening point of 80 ° C), epoxy resin 19 parts by weight of a phenol resin (phenol aralkyl resin, softening point 88 ° C.) as a curing agent, 0.7 parts by weight of a high temperature start-up curing accelerator (2-phenyl-4-methyl imidazole (2P4MZ)), silica as a filler (fused silica, average particle diameter) 75 nm) was mixed with methyl ethyl ketone in a composition consisting of 5 parts by weight to prepare a varnish. An adhesive film was produced in the same manner as in Example 1.

Comparative Example 2

A resin was prepared in the same manner as in Comparative Example 1 except that the curing accelerator was 0.7 parts by weight of a moderate temperature starting curing accelerator (2-methyl imidazole (2MZ)). An adhesive film was produced in the same manner as in Example 1.

Comparative Example 3

The same method as in Example 1, except that 0.5 parts by weight of the medium temperature onset curing accelerator (2-methyl imidazole (2MZ)) and 0.2 parts by weight of the high temperature onset curing accelerator (2-phenyl-4-methyl imidazole (2P4MZ)) were used. To prepare a resin and adhesive film.

<Property evaluation>

About the adhesive film which has the composition of Examples 1-4 and Comparative Examples 1-3, the physical property of the following item was measured.

(1) Measuring the peak temperature of the heating curve using DSC

The adhesive film in the A-stage state is measured using a DSC at a rate of 5 to 10 ° C / min up to 280 ° C. The highest point of the exothermic curve formed by the progress of the curing reaction by the elevated temperature was found, and the temperature at that time was measured.

(2) Measurement of the degree of gelation of the adhesive film in the A-stage state

The A-stage adhesive film was immersed in 100 mL of tetrahydrofuran, a strong solvent, and left at 25 ° C. for 20 hours, after which the solution was filtered through a 300 mesh wire mesh and dried to calculate the weight ratio. The weight ratio of undissolved fraction was called the degree of gelation of the adhesive film in the A-stage state.

(3) 130 ℃ storage modulus

The adhesive film is prepared by laminating 10 sheets in a predetermined direction. After taking in the longitudinal direction of the sample using a sampler of TMA (Thermo Mechanical Analysis), the temperature is raised from 40 ℃ to 150 ℃ 10 ℃ / min conditions, the load is 0.01g, using a TMA in N ₂ atmosphere Measure the variation with temperature.

The change of the specimen is measured at 130 ° C. and the elastic modulus is measured by the following equation.

Modulus of elasticity (MPa) = (F * L0) / (S * dL)

F: load, L0 = initial length, S = sectional area, dL = extended length

(4) back adhesion evaluation

The produced A-stage adhesive film was laminated over 10 seconds on an 8-inch silicon wafer using a tape mounter (DS hole) maintained at 50 ° C. Back adhesion was evaluated by the presence or absence of voids after lamination.

(5) Landfillability before semi-hardening process

PCBs with a 10 μm height difference are used as substrate. An A-stage adhesive film (20 μm) was cut to 25 mm × 25 mm and laminated at 50 ° C. with the chip in a tape mounter (DS Precision). The chip on which the PCB and the adhesive film are attached is pressed at 130 ° C. and 1.5 kg for 1 second. The fill rate is calculated by calculating the amount of film flowing and flowing between the circuit patterns of the PCB. When the purchase rate was 60% or more,?

(6) Landfill after semi-hardening process

PCBs with a 10 μm height difference are used as substrate. The adhesive film (20 μm) in the A-stage state was subjected to a semi-curing process at 125 ° C. for 1 hour, and then cut into 25 mm × 25 mm and laminated at 50 ° C. with a chip in a tape mounter (DS Precision). The chip on which the PCB and the adhesive film are attached is pressed at 130 ° C. and 1.5 kg for 1 second. The fill rate is calculated by calculating the amount of film flowing and flowing between the circuit patterns of the PCB. If the purchase rate is 50% or more,?, If 50% to 30%,?, If 30 to 20%, and less than 20%, it was ×.

(7) package reliability

After bonding the chip to the PCB substrate with an adhesive film, five cycles of temperature cycle (with the process of leaving it for 15 minutes at -55 ° C and 15 minutes in a 125 ° C atmosphere as one cycle) were carried out, and the constant temperature and humidity chamber was 85 ° C. After standing for 72 hours at / 85% condition, the sample is passed through an IR reflow temperature set so that the maximum temperature of the sample surface is maintained at 260 ° C. for 20 seconds. Cracks were observed by ultrasonic microscopy. It was good that the destruction, such as peeling or a crack, did not generate | occur | produce, and the thing which generate | occur | produced one or more was made into defect.

The evaluation results for the evaluation items are shown in Table 1 below.

division Example Comparative example One 2 3 4 One 2 3 DSC heat generation maximum temperature (℃) 220 215 208 211 - 172 185 Gelation degree (%) 15 20 22 18 0.7 62 54 130 ℃ Storage modulus (MPa) 0.9 1.3 1.5 1.3 0.1 13.4 12 Backside adhesion Good Good Good Good Good Bad Bad Landfill Before semi-hardening process ◎ ○ ○ ○ ◎ △ ○ After semi-hardening process ○ ○ △ ○ ◎ × × Package reliability Good Good Good Good Bad Bad Bad

Looking at Table 1, it can be seen that the films of Examples 1 to 4 prepared according to the present invention are excellent in package reliability, including back adhesion and embedding properties, compared to films of Comparative Examples 1 to 3. That is, when the highest point on the DSC heating curve of the adhesive film in the A-stage state is 200 ° C. or more and 240 ° C. or less, and satisfies two conditions in which the storage modulus at 130 ° C. is 0.5 MPa or more and 10 MPa or less, burr generation during the remodeling process is prevented. At the same time, it can be confirmed that even when used during the semiconductor packaging process undergoing the semi-hardening process, it has an excellent embedding property and can eliminate the defect rate due to voids.

In addition, when the high temperature active curing accelerator alone is used as in Comparative Example 1, the curing reaction is significantly delayed, so that the buried property and the adhesion to the back surface of the wafer are excellent, but the physical properties are low, and the storage modulus at high temperature is low, thereby causing burr generation. Its reliability is lowered due to deterioration of heat resistance. When only the middle temperature active curing accelerator was used as in Comparative Example 2, or when the ratio of the middle temperature active curing accelerator and the high temperature active curing accelerator was reversed to the example as in Comparative Example 3, the mechanical properties of the adhesive film were increased to generate burr. However, the wafer backside adhesion characteristics and embedding properties after the semi-curing process are deteriorated, thereby deteriorating the reliability of the semiconductor package. However, it can be seen that in Examples 1 to 4 using two kinds of curing agents according to the present invention, even after the semi-curing process, voids completely fall out during the post-curing process, thereby minimizing defects due to the voids.

Adhesive film prepared from the adhesive resin composition of the present invention is attached to the back surface of the wafer to minimize the generation of burrs in the adhesive film in the process of converting each chip into a single chip, and undergoes a semi-hardening process when bonding the chip and the organic wiring board Even in the case of having an excellent embedding property with respect to the curved organic wiring board, it can be bonded without defects due to voids during the post-curing process, it is possible to manufacture a semiconductor device having excellent reliability.

Claims (37)

a) a flexible epoxy resin comprising a long chain aliphatic structure in the main chain; b) a rigid epoxy resin comprising repeating units of an aromatic structure in the main chain; c) curing agent; And d) two or more kinds of curing accelerators, The resin composition in the A-stage state has a storage modulus of 0.5 to 10 MPa at 130 ° C., Adhesive resin composition wherein the peak of the curing reaction heating curve is 200 ℃ to 240 ℃. The method of claim 1, Adhesive resin composition, characterized in that the glass transition temperature before curing of the flexible epoxy resin is -30 to 50 ℃. delete The method of claim 1, Adhesive resin composition, characterized in that the weight average molecular weight of the flexible epoxy resin is 100,000 to 1 million. The method of claim 1, Flexible epoxy resin is an adhesive resin composition, characterized in that selected from the group consisting of aliphatic epoxy resin, rubber modified epoxy resin and mixtures thereof. delete The method of claim 1, Rigid epoxy resin is an adhesive resin composition, characterized in that the polyfunctional epoxy resin having an average epoxy equivalent of 180 to 1000. The method of claim 6, The rigid 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 resin , An adhesive resin composition selected from the group consisting of naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, dicyclopentadiene modified phenol type epoxy resins, and mixtures of two or more thereof. The method of claim 1, Adhesive resin composition, characterized in that the softening point before curing of the rigid epoxy resin is 50 to 100 ℃. The method of claim 1, The content of the rigid epoxy resin is an adhesive resin composition, characterized in that 10 to 200 parts by weight based on 100 parts by weight of the flexible epoxy resin. The method of claim 1, The curing agent reacts with both the flexible epoxy resin and the rigid epoxy resin to form a crosslinked structure. The method of claim 11, The curing agent is an adhesive resin composition, characterized in that the polyfunctional phenol resin. 13. The method of claim 12, The polyfunctional phenol resin is an adhesive resin composition, characterized in that the hydroxyl equivalent of 100 to 1000. 13. The method of claim 12, Polyfunctional phenolic resins include bisphenol A resin, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, phenol aralkyl resin, polyfunctional novolak resin, dicyclopentadiene phenol novolak resin, amino triazine phenol Adhesive resin composition, characterized in that selected from the group consisting of a novolak resin, polybutadiene phenol novolak resin, a biphenyl type resin and a mixture selected from these. The method of claim 1, Hardening agent adhesive resin composition, characterized in that the softening point is 50 to 100 ℃. The method of claim 1, The curing agent is an adhesive resin composition, characterized in that the ratio of 0.4 to 2 equivalents to the epoxy integrated equivalent of the flexible epoxy resin and the rigid epoxy resin. The method of claim 1, 2 types The above curing accelerator is an adhesive resin composition, characterized in that two or more different curing start temperature. The method of claim 1, 2 types The above curing accelerator is selected from the group consisting of imidazoles, triphenylphosphine (TPP), tertiary amines and a mixture of two or more selected from them. The method of claim 18, The imidazole curing accelerators are 2-methyl imidazole (2MZ), 2-ethyl-4-methyl imidazole (2E4MZ), 2-phenyl imidazole (2PZ), and 1-cyanoethyl-2-phenylmidazole ( 2PZ-CN), 2-undecyl imidazole (C11Z), 2-heptadecyl imidazole (C17Z), 1-cyanoethyl-2-phenylimidazole trimetalate (2PZ-CNS) and 2 selected from these Adhesive resin composition, characterized in that selected from the group consisting of more than one species. The method of claim 1, The content of the at least two curing accelerators is 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the flexible epoxy resin and rigid epoxy resin. The method of claim 1, The adhesive resin composition further comprises a filler selected from the group consisting of silica, aluminum hydroxide, calcium carbonate, magnesium hydroxide, aluminum oxide, talc, aluminum nitride and a mixture of two or more selected from these. . The method of claim 21, The content of the filler is an adhesive resin composition, characterized in that 0.5 to 100 parts by weight based on 100 parts by weight of the adhesive resin composition. The method of claim 21, Adhesive resin composition, characterized in that the average particle diameter of the filler is 0.001 ~ 10㎛. Base film; And An adhesive film formed on a base film and comprising an adhesive layer containing the adhesive resin composition according to any one of claims 1, 2, 4, 5, and 7 to 23. The method of claim 24, The thickness of a base film is 10-500 micrometers, The adhesive film characterized by the above-mentioned. The method of claim 24, The adhesive film is 1-200 micrometers in thickness. A method of preparing a resin varnish by dissolving or dispersing the adhesive resin composition according to any one of claims 1, 2, 4, 5 and 7 to 23 in a solvent; Applying the resin varnish to a base film; And Method of manufacturing an adhesive film comprising the step of removing the solvent by heating the base film. 28. The method of claim 27, Solvents are methyl ethyl ketone (MEK), acetone, toluene, dimethylformamide (DMF), methyl cellosolve (MCS), tetrahydrofuran (THF), N-methylpyrrolidone (NMP) and Method for producing an adhesive film, characterized in that selected from a mixture of these. 28. The method of claim 27, The step of preparing a resin varnish by dissolving or dispersing the adhesive resin composition in a solvent is characterized in that after mixing the solvent and the filler to add a rigid epoxy resin and a curing agent, and mixed with the flexible epoxy resin and two or more curing accelerators Method of producing an adhesive film. 28. The method of claim 27, Heating conditions of the step of removing the solvent by heating the base film is a method for producing an adhesive film, characterized in that 1 to 10 minutes at 70 to 250 ℃. Dicing tape; And A dicing die bonding film comprising the adhesive film according to claim 24 laminated on the dicing tape. The method of claim 31, wherein The dicing tape includes a base film; And A dicing die bonding film comprising an adhesive layer formed on the base film. 33. The method of claim 32, The base film is 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. 33. The method of claim 32, 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. 33. The method of claim 32, The pressure-sensitive adhesive layer comprises 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 31 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 24 attached to the chip mounting surface of the wiring board; And And a semiconductor chip mounted on the adhesive film.