KR20150075387A - Resin film for semiconductor device, and method for producing semiconductor device - Google Patents

Abstract

The purpose of the present invention is to provide a resin film for a semiconductor device having enough ion capture properties after a heat history, and a manufacturing method of a semiconductor device using the resin film for the semiconductor device. The present invention relates to the resin film for the semiconductor device wherein a ratio B/A of a copper ion capture rate A before heat curing and a copper ion capture rate B after heat curing is more than or equal to 1.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin film for a semiconductor device, and a manufacturing method of the semiconductor device. [0002]

The present invention relates to a resin film for a semiconductor device, and a method of manufacturing a semiconductor device.

Conventionally, in a semiconductor device, metal ions (for example, copper ions) are generated from wirings (for example, copper wirings) formed on a substrate or wires (for example, copper wires) It is known that there is a case where a malfunction occurs.

In recent years, it has been studied to prevent malfunction of a semiconductor device by adding an additive that captures metal ions to a resin for bonding a semiconductor chip to a substrate such as a lead frame (see, for example, Patent Document 1) .

Japanese Patent Application Laid-Open No. 2005-333085

However, in the production of a semiconductor device, there is a problem that the additive may be pyrolyzed or the like because it undergoes various heating steps, and sufficient ion trapping property can not be exhibited.

An object of the present invention is to provide a resin film for a semiconductor device having sufficient ion trapping property even after a thermal history and a method of manufacturing a semiconductor device using the resin film for semiconductor devices .

The present inventors have made intensive studies on the resin film for semiconductor devices. As a result, it has been surprisingly found that, in a specific resin film for a semiconductor device, the ion trapping property after thermal curing and before thermal curing is equal to each other, or that after thermal curing, the ion capturing property is higher than that before thermal curing. It came to the following.

That is, the resin film for a semiconductor device according to the present invention is obtained by immersing a resin film for a semiconductor device having a weight of 2.5 g before thermosetting in 50 ml of an aqueous solution having 10 ppm of copper ions and leaving the resin film for 20 hours at 120 ° C, After immersing a resin film for a semiconductor device having a copper ion concentration (ppm) in a 50 ml aqueous solution having copper ions of 10 ppm and having a weight of 2.5 g after thermosetting at 175 캜 for 5 hours and leaving it at 120 캜 for 20 hours, (B / A) of the copper ion trapping rate A calculated by the following equation (1) and the copper ion trapping rate B calculated by the following equation (2) when the copper ion concentration (ppm) in the aqueous solution is represented by Y .

(1): [(10-X) / 10] x 100 (%)

(2): [(10-Y) / 10] x 100 (%)

According to the above constitution, the ratio B / A of the copper ion capture ratio A before thermosetting to the copper ion capturing ratio B after thermosetting is 1 or more, so that the cation capturing property is not lowered even after thermosetting compared with before thermosetting. Therefore, in the production of a semiconductor device, it has sufficient ion trapping property even after a thermal history.

In the above configuration, the 5% weight reduction temperature is preferably 200 DEG C or higher.

If the 5% weight reduction temperature is 200 占 폚 or more, the heat resistance of the entire resin film for semiconductor devices is excellent.

In the above-described constitution, it is preferable to contain an inorganic ion capturing agent for capturing a cation.

The inorganic ion capturing agent is relatively difficult to pyrolyze. Therefore, when an inorganic ion trapping agent is contained, it has a sufficient ion trapping property even after a thermal history.

In the above constitution, the content of the inorganic ion capturing agent is preferably 1 to 30% by weight.

By setting the content of the inorganic ion capturing agent to 1 wt% or more, the cation can be efficiently captured, and when it is 30 wt% or less, good film formability can be obtained.

In the above constitution, the resin film for a semiconductor device having a weight of 2.5 g after heat curing at 175 ° C for 5 hours was immersed in 50 ml of an aqueous solution having 10 ppm of copper ion, and the pH of the aqueous solution after being left at 120 ° C for 20 hours , Preferably in the range of 4 to 6.

The inorganic ion capturing agent generally captures cations by ion exchange. For this reason, the cation trapping property is affected by the pH. Specifically, when the pH becomes excessively acidic, the capturing property of the cation may be lowered. Therefore, by setting the pH within the range of 4 to 6, the cation capturing property can be improved.

Further, in the method of manufacturing a semiconductor device according to the present invention,

A step of preparing the resin film for a semiconductor device,

And a die bonding step of die-bonding the semiconductor chip onto the adherend with the resin film for semiconductor device interposed therebetween.

According to the above constitution, the ratio B / A of the copper ion capture ratio A before thermosetting and the copper ion capturing rate B after thermosetting of the resin film for semiconductor device is 1 or more, so that the cation capturing properties It does not. Therefore, in the production of a semiconductor device, it has sufficient ion trapping property even after a thermal history. As a result, defective operation of the semiconductor device to be manufactured can be suppressed.

1 is a schematic cross-sectional view showing a die-bonding film with a dicing sheet according to an embodiment of the present invention.
2 is a schematic cross-sectional view showing a die bonding film with a dicing sheet according to another embodiment of the present invention.
3 is a schematic cross-sectional view for explaining one manufacturing method of the semiconductor device according to the present embodiment.

Hereinafter, as a preferred embodiment of the present invention, a case where the resin film for a semiconductor device of the present invention is a die bonding film will be described below. The die-bonding film according to the present embodiment is a die-bonding film with a dicing sheet described below, in which the dicing sheet is not bonded. Therefore, in the following, a die bonding film with a dicing sheet will be described, and a die bonding film will be described.

1 is a schematic cross-sectional view showing a die-bonding film with a dicing sheet according to an embodiment of the present invention. 2 is a schematic cross-sectional view showing another die-bonding film with a dicing sheet according to another embodiment of the present invention.

As shown in Fig. 1, a die bonding film 10 with a dicing sheet has a structure in which a die bonding film 3 is laminated on a dicing sheet 11. As shown in Fig. The dicing sheet 11 is constituted by laminating a pressure-sensitive adhesive layer 2 on a substrate 1 and the die bonding film 3 is provided on the pressure-sensitive adhesive layer 2. [ On the other hand, the die-bonding film with a dicing sheet may have a structure in which a die bonding film 3 'is formed only on a work-attaching portion like the die bonding film 12 with a dicing sheet shown in Fig. The die bonding film 3 'differs only in shape from the die bonding film 3 and various resins, additives, fillers and the like constituting the film can be the same as the die bonding film 3.

Hereinafter, each configuration of the die bonding film 10 with a dicing sheet shown in Fig. 1 will be mainly described.

(Die bonding film)

The die bonding film 3 was prepared by immersing a die bonding film 3 having a weight of 2.5 g before heat curing in 50 ml of an aqueous solution having 10 ppm of copper ions and measuring the copper ion concentration ppm) was immersed in 50 ml of an aqueous solution having copper ions of X and 10 ppm for 5 hours at 175 캜 for 5 hours and then immersed in a die bonding film 3 having a weight of 2.5 g and allowed to stand at 120 캜 for 20 hours. The ratio B / A of the copper ion trapping rate A calculated by the following equation (1) to the copper ion trapping rate B calculated by the following equation (2) when the ion concentration (ppm) is Y is 1 or more.

(1): [(10-X) / 10] x 100 (%)

(2): [(10-Y) / 10] x 100 (%)

The ratio B / A is preferably 1 or more, and more preferably 1.1 or more. Further, the ratio B / A is preferably large but is, for example, 10 or less. In the die-bonding film 3, the ratio B / A is not less than 1, so that the cation capturing property is not lowered even after heat curing as compared with before heat curing. Therefore, in the production of a semiconductor device, it has sufficient ion trapping property even after a thermal history.

The die bonding film 3 preferably has a 5% weight reduction temperature of 200 ° C or higher, more preferably 250 ° C or higher, and still more preferably 300 ° C or higher. If the 5% weight reduction temperature of the die bonding film 3 is 200 占 폚 or more, the die bonding film 3 has excellent heat resistance as a whole. The method of measuring the 5% weight reduction temperature is based on the method described in the examples. The 5% weight reduction temperature of the die bonding film 3 can be selected by selecting the resin, additive, filler or the like constituting the die bonding film 3 or the manufacturing conditions (for example, The drying temperature after the film formation and the drying time).

The die-bonding film 3 preferably contains an additive that captures cations. When an additive for capturing a cation is contained in the die bonding film 3, ion capture property can be easily expected.

Examples of the cation that can be captured by the additive that captures the cation include Na, K, Ni, Cu, Cr, Co, Hf, Pt, Ca, Ba, Sr, Fe, Al, Ti, Zn, And the like (cation). The additive for capturing the cation is preferably at least a Cu ion (copper ion). Copper ions are more likely to occur in large quantities than other ions, and there is a high possibility that copper ions will greatly affect the operation failure of the semiconductor device.

Examples of the additive for capturing the cation include an inorganic ion capturing agent and a complex forming compound that forms a complex with a cation. Among them, an inorganic ion capturing agent is preferable. The inorganic ion capturing agent is relatively difficult to pyrolyze, and therefore has sufficient ion capture property even after the thermal history.

(Inorganic ion capturing agent)

The inorganic ion capturing agent is an inorganic ion exchanger that captures cations by ion exchange. The inorganic ion capturing agent is preferably an inorganic ion trapping agent capable of trapping not only cations but also anions. If the inorganic ion trapping agent is both an ion trapping agent, the change in pH is small. As a result, deterioration of ion trapping property due to aging can be suppressed. Concretely, ions (for example, hydrogen ions) released as counter ions are neutralized when ions are captured (for example, hydroxide ions) as counter ions when anions are trapped. Since the ion trapping is performed by the equilibrium reaction (ion exchange), the concentration of the counter ions is decreased, and ion exchange of the target ions is promoted.

In the present specification, both of the ion trapping agents refer to both inorganic and inorganic ion exchangers capable of capturing at least a certain amount of both copper ions and chloride ions. Specifically, examples of the both inorganic ion exchangers include a copper (II) ion distribution coefficient (Kd) determined according to the following method of measuring the copper (II) ion distribution coefficient of 10 or more, (Meq / g) of 0.5 or more.

≪ Measurement method of copper (II) ion partition coefficient >

5.0 g of inorganic ion exchanger and 50 ml of a test solution containing 0.01 N of copper (II) ion are put into a 100 ml plastic container, tightly closed and shaken at 25 ° C for 24 hours. After shaking, the solution was filtered with a membrane filter having a pore size of 0.1 mu m to measure the concentration of copper (II) ion in the filtrate with lCP-AES (SPS-1700HVR, manufactured by SIII Nanotechnology Co., Ltd.) The distribution coefficient Kd is obtained. Kd (ml / g) is (C ₀ -C) × V / represents the (m × C), C ₀ is the initial ion concentration, C is the concentration of test liquid ion, V is the volume of the test solution (ml), m is both inorganic ion The weight (g) of the exchanger.

≪ Measurement method of ion exchange capacity >

1.0 g of both inorganic ion exchangers were immersed in 50 ml of a saturated aqueous solution of NaCl and left at room temperature for 20 hours. The amount of hydroxide ions generated by both ion exchangers is quantified by titration with a 0.1N HCl aqueous solution to determine the ion exchange capacity (meq./g).

The die bonding film 3 was prepared by immersing a die bonding film 3 having a weight of 2.5 g after heat curing at 175 캜 for 5 hours in 50 ml of an aqueous solution having 10 ppm of copper ions and leaving the die bonding film 3 at 120 캜 for 20 hours The pH of the aqueous solution is preferably in the range of 4 to 6, more preferably in the range of 4.2 to 5.8, and still more preferably in the range of 4.4 to 5.5. The inorganic ion capturing agent generally captures cations by ion exchange. For this reason, the cation trapping property is affected by the pH. Specifically, when the pH becomes excessively acidic, the capturing property of the cation may be lowered. Therefore, by setting the pH within the range of 4 to 6, the cation capturing property can be improved. As a method for bringing the pH within the range of 4 to 6, there is a method using the following inorganic ion trapping agent. The use of both of the ionic and ionic capturing agents can prevent the pH from becoming excessively acidic and maintain high ion trapping properties.

The inorganic ion scavenger is not particularly limited and various inorganic ion scavengers may be used. For example, oxidized hydrides of elements selected from the group consisting of antimony, bismuth, zirconium, titanium, tin, . These may be used alone or in combination of two or more. Among them, a three-component oxide hydrate of magnesium, aluminum and zirconium is preferable. In the three-component system of magnesium, aluminum and zirconium, since both ions of a cation and anion are captured by ion exchange, the pH is maintained near neutral even when ions are captured. Therefore, better ion trapping property can be obtained. Further, the three-component system of magnesium, aluminum and zirconium is particularly suitable for semiconductor applications in which antimony free (free) is required.

Commercially available products of the inorganic ion capturing agent include trade names IXEPLAS-A1 and IXEPLAS-A2 manufactured by Toa Gosei Co., Ltd. These are both inorganic ion scavengers.

The average particle diameter of the inorganic ion capturing agent is preferably 0.1 to 1 占 퐉, more preferably 0.2 to 0.6 占 퐉. By setting the average particle diameter of the inorganic ion trapping agent to 1 m or less, the specific surface area can be increased. As a result, the ion trapping property can be further improved. Further, by setting the average particle diameter of the inorganic ion capturing agent to 1 m or less, the thickness of the die bonding film 3 can be reduced. In addition, dispersibility can be improved by setting the average particle diameter of the inorganic ion trapping agent to 0.1 탆 or more.

The inorganic ion capturing agent is preferably treated (pre-treated) with a silane coupling agent. When the silane coupling treatment is carried out, the dispersibility of the inorganic ion capturing agent becomes good, and the film-forming property of the die-bonding film 3 is excellent. Particularly, the smaller the particle diameter of the inorganic ion trapping agent, the more easily aggregation occurs. However, when the silane coupling treatment is carried out, the dispersibility becomes better. As a result, it becomes possible to suitably produce the thin die-bonding film 3 containing the inorganic ion capturing agent. On the other hand, the present inventors have confirmed that even when the inorganic ion capturing agent is subjected to the silane coupling treatment, the cation trapping property is not equal to or significantly lower than that in the untreated state.

The silane coupling agent preferably includes a silicon atom, a hydrolyzable group and an organic functional group.

Hydrolyzable groups are bonded to silicon atoms.

Examples of the hydrolyzable group include a methoxy group and an ethoxy group. Among them, a methoxy group is preferred because of its fast hydrolysis rate and easiness of processing.

The number of hydrolysable groups in the silane coupling agent can be crosslinked between the silane coupling agents while being crosslinked with the inorganic ion scavenger and even if the surface of the inorganic ion scavenger has a small crosslinking point, Preferably 2 to 3, and more preferably 3 in terms of being capable of surface treatment with a ring agent.

The organic functional group is bonded to a silicon atom.

Examples of the organic functional group include an acryl group, a methacryl group, an epoxy group, a phenylamino group and the like. Among them, an acrylic group is preferable because it has no reactivity with an epoxy resin and has good storage stability of an inorganic ion capturing agent treated.

On the other hand, if a functional group having a high reactivity with an epoxy group is present, it will react with the epoxy resin, resulting in deterioration of storage stability and fluidity. From the standpoint of suppressing the deterioration of fluidity, it is preferable that the organic functional group does not include a primary amino group, a mercapto group or an isocyanate group.

The number of organic functional groups in the silane coupling agent is preferably one. Since silicon atoms make four bonds, the number of hydrolysis groups is insufficient when the number of organic functional groups is large.

The silane coupling agent may further contain an alkyl group bonded to the silicon atom. Since the silane coupling agent contains an alkyl group, the reactivity can be made lower than that of the methacrylic group, and deviation of the surface treatment due to abrupt reaction can be prevented. Examples of the alkyl group include a methyl group and a dimethyl group. Among them, a methyl group is preferable.

Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane But are not limited to, trimethylolpropane, trimethylolpropane trimethoxy silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane , Methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like can be given.

The method of treating the inorganic ion capturing agent with a silane coupling agent is not particularly limited, and a wet method in which an inorganic ion capturing agent and a silane coupling agent are mixed in a solvent, an inorganic ion trap agent and a silane coupling agent in a gas phase Dry method, and the like.

The throughput of the silane coupling agent is not particularly limited, but it is preferable to treat the silane coupling agent in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the inorganic ion trap agent.

The content of the additive for capturing the cation is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, and still more preferably 3 to 20% by weight. By setting the content of the additive for capturing the cation to 1 wt%, it is possible to efficiently capture the cation, and when the content is 30 wt% or less, good film formability can be obtained.

The die bonding film 3 preferably contains either or both of a thermoplastic resin and a thermosetting resin. Examples of the thermosetting resin include a phenol resin, an amino resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a silicone resin, and a thermosetting polyimide resin. These resins can be used alone or in combination of two or more kinds, and it is particularly preferable to use at least one of an epoxy resin and a phenol resin. Among them, it is preferable to use an epoxy resin. When the epoxy resin is contained, a high adhesive force between the die bonding film 3 and the wafer can be obtained at a high temperature. As a result, water hardly enters the bonding interface between the die bonding film 3 and the wafer, making it difficult for the ions to move. This improves the reliability.

The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition and examples thereof include epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, A bifunctional epoxy resin or a polyfunctional epoxy resin such as a fluorene type, a phenol novolac type, an orthocresol novolac type, a tris hydroxyphenyl methane type and a tetraphenyl ether type, An epoxy resin such as an isocyanurate type or glycidyl amine type is used. These may be used alone or in combination of two or more. Of these epoxy resins, novolak type epoxy resins, biphenyl type epoxy resins, trishydroxyphenylmethane type resins and tetraphenylether type epoxy resins are particularly preferable. These epoxy resins are rich in reactivity with a phenol resin as a curing agent and have excellent heat resistance.

The phenol resin acts as a curing agent for the epoxy resin. Examples of the phenol resin include phenol novolak resin, phenol aralkyl resin, cresol novolak resin, tert-butyl phenol novolac resin, and nonyl phenol novolak resin Phenol resins such as phenol resin, phenol resin, phenol resin, phenol resin, phenol resin, phenol resin, phenol resin, phenol resin, These may be used alone or in combination of two or more. Of these phenolic resins, phenol novolac resins and phenol aralkyl resins are particularly preferable. This is because connection reliability of the semiconductor device can be improved.

The mixing ratio of the epoxy resin to the phenol resin is preferably such that the hydroxyl group in the phenol resin is equivalent to 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitable is 0.8 to 1.2 equivalents. That is, if the mixing ratio of the two is out of the above range, sufficient curing reaction does not proceed and the properties of the epoxy resin cured product tend to deteriorate.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene resin, polycarbonate resin, A polyamide resin such as 6-nylon or 6,6-nylon, a phenoxy resin, an acrylic resin, a saturated polyester resin such as PET or PBT, a polyamideimide resin, or a fluororesin. These thermoplastic resins may be used alone or in combination of two or more. Among these thermoplastic resins, an acrylic resin which is low in ionic impurities and high in heat resistance and can secure the reliability of a semiconductor element is particularly preferable.

The acrylic resin is not particularly limited and is preferably a polymer having one or more kinds of ester of acrylic acid or methacrylic acid having a linear or branched alkyl group having 30 or less carbon atoms, particularly 4 to 18 carbon atoms as a monomer component Copolymer), and the like. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, cyclohexyl group, An alkenyl group, an isoamyl group, an isoamyl group, an isoamyl group, an isoamyl group, a hexyl group, an octyl group, an isooctyl group, a nonyl group, And the like.

The other monomer forming the polymer is not particularly limited and includes, for example, a monomer containing a carboxyl group such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid or crotonic acid (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylic acid such as 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (Meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide-based monomer, With methanesulfonic acid, sulfopropyl (meth) acrylate or (meth) sulfonic acid group-containing monomers, such as one oxy-naphthalene-sulfonic acid with acrylic or 2-hydroxyethyl acrylate may be mentioned phosphoric acid group-containing monomers such as phosphate. These may be used alone or in combination of two or more.

The compounding ratio of the thermosetting resin is not particularly limited as long as the die bonding film 3 exhibits a function as a thermosetting type when heated under a predetermined condition, but it is preferably in a range of 5 to 60 wt%, more preferably in a range of 10 to 50 wt% %. ≪ / RTI >

The die-bonding film 3 preferably contains an epoxy resin, a phenolic resin, and an acrylic resin, and the total amount of the epoxy resin and the phenolic resin with respect to 100 parts by weight of the acrylic resin is preferably 10 to 2000 parts by weight, More preferably from 10 to 1000 parts by weight. By setting the total amount of the epoxy resin and the phenol resin to 10 parts by weight or more with respect to 100 parts by weight of the acrylic resin, the adhesion effect by curing can be obtained and the peeling can be suppressed. By setting the amount to 2000 parts by weight or less, So that deterioration in workability can be suppressed.

When the die bonding film 3 is previously crosslinked to some extent, a polyfunctional compound which reacts with the functional group at the molecular chain terminal of the polymer is preferably added as a crosslinking agent. This makes it possible to improve the adhesive property under high temperature and to improve the heat resistance.

As the crosslinking agent, conventionally known ones can be employed. Particularly, it is possible to use a polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, polyhydric alcohol and diisocyanate And polyisocyanate compounds such as adducts are more preferable. The amount of the crosslinking agent to be added is preferably 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. By reducing the amount of the cross-linking agent to 7 parts by weight or less, deterioration of the adhesive strength can be suppressed. When the amount is 0.05 part by weight or more, the cohesive force can be improved. If necessary, other polyfunctional compounds such as an epoxy resin may be included together with such a polyisocyanate compound.

In the die bonding film 3, a filler can be appropriately added depending on the application. The compounding of the filler makes it possible to improve the thermal conductivity and control the elastic modulus of the die bonding film 3. Examples of the filler include an inorganic filler and an organic filler. An inorganic filler is preferable from the viewpoints of improving handling properties, improving heat conductivity, adjusting melt viscosity, imparting thixotropic properties, and the like. The inorganic filler is not particularly limited and includes, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, Silica, and amorphous silica. These may be used alone or in combination of two or more. From the viewpoint of improving the thermal conductivity, aluminum oxide, aluminum nitride, boron nitride, crystalline silica and amorphous silica are preferable. In addition, from the viewpoint that the balance of the above characteristics is good, crystalline silica or amorphous silica is preferable.

The average particle diameter of the filler may be 0.005 to 10 mu m. By setting the average particle diameter of the filler to 0.005 탆 or more, it is possible to improve the wettability and adhesive property of the adherend. In addition, by setting the thickness to 10 탆 or less, the effect of the filler added for imparting the respective characteristics can be made sufficient, and the heat resistance can be ensured. On the other hand, the average particle diameter of the filler is, for example, a value obtained by a photometric type particle size distribution meter (manufactured by HORIBA, device name: LA-910).

On the other hand, in addition to the additive for capturing the cation, the die bonding film 3 may contain other additives if necessary. Examples of other additives include an anion capturing agent, a dispersant, an antioxidant, a silane coupling agent, and a curing accelerator. These may be used alone or in combination of two or more.

The thickness of the die-bonding film 3 is not particularly limited, but is preferably 1 to 40 m, more preferably 3 to 35 m, further preferably 5 to 30 m. If the thickness is 40 mu m or less and the thickness is relatively small, the thickness of the entire semiconductor device using the die bonding film 3 can be reduced. In addition, when the thickness is 1 m or more, good ion trapping property can be exhibited.

(Dicing sheet)

The dicing sheet 11 has a constitution in which a pressure-sensitive adhesive layer 2 is laminated on a base material 1.

The base material 1 serves as the strength base of the die bonding film 10 with a dicing sheet. It is preferable that the base material 1 has ultraviolet transmittance. Examples of the base material 1 include polyolefins such as low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymerized polypropylene, homopolypropylene, polybutene, , Ethylene-vinyl acetate copolymers, ionomer resins, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester (random, alternating) copolymers, ethylene-butene copolymers, , Polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyimide, polyetherketone, polyimide, polyetherimide, polyamide, all aromatic polyamide, polyphenylsulfide, , Glass, glass cloth, fluororesin, polyvinyl chloride, polyvinylidene chloride, cell There may be mentioned Ross-based resin, a silicone resin, metal (foil), paper or the like.

As the material of the base material 1, a polymer such as a crosslinked product of the resin may be mentioned. The above-mentioned plastic film may be used in a non-stretched state, or may be one obtained by one-axis or two-axis stretching processing, if necessary. According to the resin sheet to which heat-shrinkability is imparted by stretching treatment or the like, the adhesive area of the pressure-sensitive adhesive layer 2 and the die-bonding film 3 is reduced by thermally shrinking the base material 1 after dicing, Thereby facilitating the operation.

The surface of the base material 1 may be chemically or physically treated such as an ordinary surface treatment such as chromium acid treatment, ozone exposure, flame exposure, high voltage exposure, and ionizing radiation treatment, in order to improve adhesion with the adjacent layer, Treatment, and coating treatment with a primer (for example, an adhesive material described later). As the base material (1), homogeneous or heterogeneous materials can be appropriately selected and used, and if necessary, several kinds of materials may be blended.

The thickness of the base material 1 is not particularly limited and can be appropriately determined, but is generally about 5 to 200 mu m.

The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer (2) is not particularly limited, and for example, general pressure-sensitive pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives and rubber pressure-sensitive adhesives can be used. As the above pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive using an acrylic polymer as a base polymer is preferable from the viewpoints of ultrapure water of an electronic component that is not susceptible to contamination of a semiconductor wafer or glass, or clean cleaning property by an organic solvent such as alcohol.

Examples of the acrylic polymer include (meth) acrylic acid alkyl esters such as methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, Hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, tridecyl ester, (Meth) acrylic acid cycloalkyl ester (for example, cyclopentyl ester, cyclopentyl ester, cyclopentyl ester, cyclopentyl ester, cyclopentyl ester, and cyclopentyl ester) Cyclohexyl ester, and the like) as the monomer component, and the like Can. On the other hand, (meth) acrylic acid ester refers to acrylic acid ester and / or methacrylic acid ester, and (meth)

The acrylic polymer may contain units corresponding to other monomer components copolymerizable with the (meth) acrylic acid alkyl ester or the cycloalkyl ester, if necessary, for the purpose of modifying the cohesive force, heat resistance and the like. Examples of such a monomer component include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Acid anhydride monomers such as maleic anhydride and itaconic anhydride; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyl group-containing monomers such as (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; (Meth) acrylamide sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene, (meth) acrylamide, Sulfonic acid group-containing monomers such as sulfonic acid; Phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; Acrylamide, acrylonitrile, and the like. These copolymerizable monomer components may be used alone or in combination of two or more. The amount of these copolymerizable monomers to be used is preferably 40% by weight or less based on the total monomer components.

In order to crosslink the acrylic polymer, the polyfunctional monomer and the like may be included as a monomer component for copolymerization, if necessary. Examples of such a polyfunctional monomer include hexane diol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, ) Acrylate, polyester (meth) acrylate, and urethane (meth) acrylate. These multifunctional monomers may be used alone or in combination of two or more. The amount of the multifunctional monomer to be used is preferably 30% by weight or less based on the total amount of the monomer components from the viewpoint of adhesion properties and the like.

The acrylic polymer is obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization may be carried out by any method such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. It is preferable that the content of the low molecular weight substance is small in view of prevention of contamination to a clean adherend. In this respect, the number average molecular weight of the acrylic polymer is preferably 100,000 or more, more preferably about 200,000 to 3,000,000, and particularly preferably about 300,000 to 1,000,000.

To the pressure-sensitive adhesive, an external crosslinking agent may be suitably employed in order to increase the number-average molecular weight of the acryl-based polymer as the base polymer. Specific examples of the external crosslinking method include a method in which a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound, or a melamine crosslinking agent is added and reacted. When an external crosslinking agent is used, its amount to be used is appropriately determined depending on the balance with the base polymer to be crosslinked and also in accordance with the intended use as a pressure-sensitive adhesive. Generally, about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer is preferably blended. In addition to the above components, various conventionally known additives such as a tackifier and an antioxidant may be used for the pressure-sensitive adhesive, if necessary.

The pressure-sensitive adhesive layer (2) can be formed by a radiation-curable pressure-sensitive adhesive. The radiation-curing pressure-sensitive adhesive can increase the degree of crosslinking by irradiation with radiation such as ultraviolet rays to easily lower the adhesive force, and only the portion 2a corresponding to the work-attaching portion of the pressure-sensitive adhesive layer 2 shown in Fig. It is possible to provide a difference in adhesive force with the other portion 2b.

In addition, by curing the radiation-curable pressure-sensitive adhesive layer 2 in combination with the die bonding film 3 'shown in Fig. 2, it is possible to easily form the portion 2a in which the adhesive force is remarkably decreased. The interface between the portion 2a of the pressure-sensitive adhesive layer 2 and the die-bonding film 3 'is set at the time of picking-up, because the die bonding film 3' is adhered to the portion 2a, And easily peeled off. On the other hand, the portion not irradiated with radiation has sufficient adhesive force to form the portion 2b. On the other hand, irradiation of the pressure sensitive adhesive layer with radiation may be performed before dicing and before picking up.

As described above, in the pressure-sensitive adhesive layer 2 of the die-bonding film 10 with a dicing sheet shown in Fig. 1, the portion 2b formed by the uncured radiation-curable pressure- So that the holding force at the time of dicing can be ensured. The radiation-curing pressure-sensitive adhesive in this way can support the die bonding film 3 for fixing the chipped work (semiconductor chip or the like) to an adherend such as a substrate in a good balance of adhesion and peeling. In the pressure-sensitive adhesive layer 2 of the die bonding film 11 with the dicing sheet shown in Fig. 2, the portion 2b can fix the wafer ring.

The radiation-curable pressure-sensitive adhesive can be used without any particular limitation, which has a radiation-curable functional group such as a carbon-carbon double bond and exhibits adhesiveness. As the radiation-curing pressure-sensitive adhesive, for example, an addition-type radiation-curing pressure-sensitive adhesive in which a radiation-curable monomer component or an oligomer component is blended with a common pressure-sensitive adhesive such as the acrylic pressure-sensitive adhesive and the rubber pressure-

Examples of the radiation curable monomer component to be blended include urethane oligomer, urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,4-butanediol di Methacrylate, and the like. Examples of the radiation-curable oligomer component include urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based oligomers. The molecular weight of the oligomer is suitably in the range of about 100 to 30000. The amount of the radiation-curable monomer component or the oligomer component can be appropriately determined depending on the type of the pressure-sensitive adhesive layer so that the adhesive force of the pressure-sensitive adhesive layer can be lowered. Generally, it is about 5 to 500 parts by weight, preferably about 40 to 150 parts by weight, based on 100 parts by weight of the base polymer such as acrylic polymer constituting the pressure-sensitive adhesive.

As the radiation-curable pressure-sensitive adhesive, there can be enumerated the radiation-curing pressure-sensitive adhesive of the internal type using the one having the carbon-carbon double bond at the polymer side chain, the main chain or the main chain end as the base polymer, in addition to the addition type radiation- The radiation-curing pressure-sensitive adhesive of the internal type does not need or need to contain an oligomer component which is a low-molecular component, so that the oligomer component or the like does not migrate with time in the pressure- Can be formed.

The above-mentioned base polymer having a carbon-carbon double bond may have a carbon-carbon double bond and a sticky property without particular limitation. As such a base polymer, an acrylic polymer is preferably used as a basic skeleton. Examples of the basic skeleton of the acrylic polymer include the acrylic polymer exemplified above.

There are no particular restrictions on the method for introducing the carbon-carbon double bond into the acryl-based polymer, and various methods can be employed, but introduction of the carbon-carbon double bond into the side chain of the polymer is easy in terms of molecular design. For example, after a monomer having a functional group is copolymerized with an acrylic polymer in advance, a compound having a functional group capable of reacting with the functional group and a carbon-carbon double bond is condensed or adhered while maintaining the radiation curability of the carbon- And the like.

Examples of combinations of these functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridyl group, and a hydroxyl group and an isocyanate group. Of these combinations of functional groups, a combination of a hydroxyl group and an isocyanate group is suitable for easy reaction tracking. In the combination of these functional groups, the functional group may be either an acrylic polymer or the above compound, provided that the acrylic polymer having the carbon-carbon double bond is produced. In the preferred combination, the acryl polymer is a hydroxyl group , And the compound having an isocyanate group is suitable. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, m-isopropenyl-alpha, alpha - dimethylbenzyl isocyanate, and the like. As the acryl-based polymer, there can be used, for example, a copolymer obtained by copolymerizing the above-mentioned hydroxyl group-containing monomer, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, do.

The radiation-curable pressure-sensitive adhesive of the internal type may use the above-mentioned base polymer having a carbon-carbon double bond (in particular acrylic polymer) alone, but it is also possible to mix the radiation curable monomer component or oligomer component have. The radiation-curable oligomer component and the like are usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, based on 100 parts by weight of the base polymer.

The radiation-curable pressure-sensitive adhesive contains a photo-polymerization initiator when it is cured by ultraviolet rays or the like. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone,? -Hydroxy- ?,? '- dimethylacetophenone, -? - ketol compounds such as hydroxypropiophenone and 1-hydroxycyclohexyl phenyl ketone; Methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) An acetophenone-based compound such as polynaphropene-1; Benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether; Ketal compounds such as benzyl dimethyl ketal; Aromatic sulfonyl chloride-based compounds such as 2-naphthalenesulfonyl chloride; Optically active oxime compounds such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime; Benzophenone compounds such as benzophenone, benzoylbenzoic acid and 3,3'-dimethyl-4-methoxybenzophenone; 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethyl Thioxanthone compounds such as thioxanthone and 2,4-diisopropylthioxanthone; Campquinone; Halogenated ketones; Acylphosphine oxides; Acylphosphonates, and the like. The blending amount of the photopolymerization initiator is, for example, about 0.05 to 20 parts by weight relative to 100 parts by weight of the base polymer such as acrylic polymer constituting the pressure-sensitive adhesive.

Examples of radiation-curable pressure-sensitive adhesives include those described in JP 60-196956 A, an addition polymerizable compound having two or more unsaturated bonds, a photopolymerizable compound such as an alkoxysilane having an epoxy group, Based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, and the like containing a photopolymerization initiator such as a compound, an organic sulfur compound, a peroxide, an amine, and an onium salt compound.

The radiation-curable pressure-sensitive adhesive layer (2) may contain a compound that is colored by radiation if necessary. By incorporating a compound that is colored by irradiation with radiation in the pressure-sensitive adhesive layer (2), only the irradiated portion can be colored. That is, the portion 2a corresponding to the work attaching portion 3a shown in Fig. 1 can be colored. Therefore, whether or not the pressure-sensitive adhesive layer 2 is irradiated with radiation can be immediately determined by the naked eye, the work-attaching portion 3a can be easily recognized, and the work can be easily attached. Further, when the semiconductor chip is detected by an optical sensor or the like, its detection precision is increased, and malfunctions are not caused at the time of picking up the semiconductor chip.

The compound that is colored by irradiation with light is a colorless or pale color before irradiation but becomes a color by irradiation. Preferable specific examples of such compounds include leuco dyes. As the leuco dyes, triphenylmethane-based, fluororan-based, phenothiazine-based, aramine-based, and spiropyran-based ones are preferably used. Specific examples include 3- [N- (p-tolylamino)] - 7-anilinofluoran, 3- [N- (p- tolyl) 7-anilinofluoran, crystal violet lactone, 4,4 ', 4 "- (2-methylphenyl) Trisdimethylaminotriphenylmethanol, 4,4 ', 4 "-trisdimethylaminotriphenylmethane, and the like.

Examples of a developer that is preferably used together with these leuco dyes include electron acceptors such as an early polymer, an aromatic carboxylic acid derivative, and an activated clay of phenol-form aline resin conventionally used. When changing the coloring agent, various known coloring agents may be used in combination.

Such a compound that is colored by irradiation with radiation may be contained in the radiation curable adhesive once dissolved in an organic solvent or the like, or may be incorporated into the pressure sensitive adhesive in the form of a fine powder. The use ratio of the compound is preferably 10% by weight or less, preferably 0.01 to 10% by weight, more preferably 0.5 to 5% by weight in the pressure-sensitive adhesive layer (2). If the proportion of the compound exceeds 10% by weight, the radiation irradiated onto the pressure-sensitive adhesive layer 2 is excessively absorbed by the compound, so that the curing of the portion 2a of the pressure-sensitive adhesive layer 2 becomes insufficient, May not be lowered. On the other hand, in order to sufficiently color, the proportion of the compound is preferably 0.01% by weight or more.

In the case where the pressure-sensitive adhesive layer 2 is formed by a radiation-curing pressure-sensitive adhesive, a part of the pressure-sensitive adhesive layer 2 is applied so that the pressure-sensitive adhesive layer 2 has an adhesive force of the portion 2a and an adhesive force of the other portion 2b Radiation may also be used.

As a method for forming the portion 2a on the pressure-sensitive adhesive layer 2, a radiation-curable pressure-sensitive adhesive layer 2 is formed on the supporting substrate 1, and then the portion 2a is irradiated with radiation partially, . The partial irradiation with radiation can be performed through a photomask having a pattern corresponding to the portion 3b or the like other than the work attaching portion 3a. In addition, a method of irradiating ultraviolet rays in a spot manner to cure them may be used. The radiation-curable pressure-sensitive adhesive layer 2 can be formed by transferring the pressure-sensitive adhesive layer 2 provided on the separator onto the supporting base material 1. The partial radiation curing may be performed on the radiation curable pressure sensitive adhesive layer 2 provided on the separator.

When the pressure-sensitive adhesive layer 2 is formed by a radiation-curing pressure-sensitive adhesive, it is preferable to use a product in which all or a part of at least one surface of the supporting substrate 1 other than the portion corresponding to the work- After the radiation-curable pressure-sensitive adhesive layer 2 is formed on the pressure-sensitive adhesive layer 2, the portion 2a corresponding to the work-attaching portion 3a is cured by irradiating it with radiation to lower the adhesive force. As the light-shielding material, what can be a photomask on the support film can be formed by printing, vapor deposition or the like. According to this manufacturing method, it is possible to efficiently manufacture the die bonding film 10 with a dicing sheet of the present invention.

On the other hand, when curing inhibition by oxygen occurs at the time of irradiation with radiation, it is preferable to block oxygen (air) from the surface of the radiation-curing pressure-sensitive adhesive layer 2 by any method. For example, a method of covering the surface of the pressure-sensitive adhesive layer 2 with a separator, a method of irradiating radiation such as ultraviolet rays in a nitrogen gas atmosphere, and the like can be given.

The thickness of the pressure-sensitive adhesive layer (2) is not particularly limited, but is preferably about 1 to 50 mu m in terms of prevention of breakage of the cut surface of the chip and compatibility of fixation and maintenance of the adhesive layer. Preferably 2 to 30 mu m, further preferably 5 to 25 mu m.

(Production method of die bonding film with dicing sheet)

The die bonding film with dicing sheet 10 is produced, for example, in the following manner.

First, the base material 1 can be formed by a conventionally known film-forming method. Examples of the film-forming method include a calendar film-forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, a dry lamination method and the like.

Next, a pressure-sensitive adhesive composition solution is applied on the substrate 1 to form a coating film, and then the coating film is dried under predetermined conditions (heating crosslinking if necessary) to form a pressure-sensitive adhesive layer 2. [ The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are, for example, within a range of a drying temperature of 80 to 150 DEG C and a drying time of 0.5 to 5 minutes. Further, the pressure-sensitive adhesive composition may be coated on the separator to form a coating film, and then the coating film may be dried under the above drying conditions to form the pressure-sensitive adhesive layer (2). Thereafter, the pressure-sensitive adhesive layer 2 is bonded to the substrate 1 together with the separator. Thus, the dicing sheet 11 is produced.

The die bonding film 3 is produced, for example, in the following manner.

First, a resin composition solution which is a material for forming the die bonding film 3 is prepared. The resin composition solution can be obtained by appropriately adding an additive for capturing a cation, a thermosetting resin, a thermoplastic resin, a filler or the like into a container as needed, dissolving in an organic solvent, and stirring the mixture uniformly.

The organic solvent is not limited as long as it can uniformly dissolve, knead or disperse the components constituting the die bonding film (3), and conventionally known ones can be used. Examples of such a solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone and cyclohexanone, toluene and xylene. It is preferable to use methyl ethyl ketone, cyclohexanone or the like because the drying speed is high and it can be obtained at low cost.

Next, the resin composition solution is applied on the substrate separator so as to have a predetermined thickness to form a coating film, and then the coating film is dried under predetermined conditions to form an adhesive layer (die bonding film 3). The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. The drying conditions are, for example, a drying temperature of 70 to 160 DEG C and a drying time of 1 to 5 minutes. Further, after the resin composition solution is applied on the separator to form a coating film, the coating film may be dried under the above drying conditions to form the die bonding film 3. Thereafter, the die bonding film 3 is bonded together with the separator on the substrate separator.

Subsequently, the separator is peeled from the dicing sheet 11 and the die bonding film 3, respectively, and the die bonding film 3 and the pressure sensitive adhesive layer 2 are bonded to each other so as to bond them together. The bonding can be performed, for example, by pressing. At this time, the temperature of the laminate is not particularly limited, but is preferably 30 to 50 占 폚, and more preferably 35 to 45 占 폚. The line pressure is not particularly limited, but is preferably 0.1 to 20 kgf / cm, more preferably 1 to 10 kgf / cm. Next, the substrate separator on the die bonding film 3 is peeled off to obtain the die bonding film 10 with the dicing sheet according to the present embodiment.

(Manufacturing Method of Semiconductor Device)

The method for manufacturing a semiconductor device according to the present embodiment includes the steps of preparing the thermosetting die-bonding film,

And a die bonding step of die bonding the semiconductor chip onto the adherend with the thermosetting die bonding film interposed therebetween (hereinafter, also referred to as the first embodiment).

The manufacturing method of the semiconductor device according to the present embodiment may further include a step of preparing the die bonding film with a dicing sheet described above,

A bonding step of bonding the thermosetting die bonding film of the die bonding film with the dicing sheet to the back surface of the semiconductor wafer,

A dicing step of dicing the semiconductor wafer together with the thermosetting die bonding film to form a semiconductor chip on the chip,

A pickup step of picking up the semiconductor chip together with the thermosetting die bonding film from the die bonding film with the dicing sheet,

And a die bonding step of die-bonding the semiconductor chip onto the adherend with the thermosetting die bonding film interposed therebetween (hereinafter, also referred to as the second embodiment).

The method for manufacturing a semiconductor device according to the first embodiment uses the die bonding film with a dicing sheet in the method for manufacturing a semiconductor device according to the second embodiment, while the method for manufacturing a semiconductor device according to the first embodiment Method is different in that the die bonding film is used as a single body, and is common in other respects. In the manufacturing method of the semiconductor device according to the first embodiment, after the die bonding film is prepared and the step of bonding the dicing film to the dicing sheet is performed, thereafter, the same process as in the semiconductor device manufacturing method according to the second embodiment . In the following, a method of manufacturing the semiconductor device according to the second embodiment will be described.

In the method of manufacturing a semiconductor device according to the present embodiment, first, a die bonding film with a dicing sheet is prepared (preparing step). The die bonding film with dicing sheet 10 is suitably used as follows by appropriately peeling a separator provided arbitrarily on the die bonding film 3. Hereinafter, a case in which the die bonding film 10 with a dicing sheet is used will be described with reference to Fig.

First, the semiconductor wafer 4 is pressed onto the semiconductor wafer attaching portion 3a of the die bonding film 3 in the die bonding film 10 with a dicing sheet, and the semiconductor wafer 4 is held by adhesion and fixed (bonding step) . This step is carried out while being pressed by a pressing means such as a press roll. The mounting temperature at the time of mounting is not particularly limited, and is preferably within a range of, for example, 40 to 90 캜.

Next, the semiconductor wafer 4 is diced (dicing step). As a result, the semiconductor wafer 4 is cut into a predetermined size and individualized to manufacture the semiconductor chip 5. The dicing method is not particularly limited, but is performed from the circuit surface side of the semiconductor wafer 4 according to a conventional method. In this step, for example, a cutting method called full cutting in which the die-bonding film 10 with a dicing sheet is cut is used. The dicing apparatus used in the present step is not particularly limited and conventionally known dicing apparatuses can be used. Further, since the semiconductor wafer is adhered and fixed by the die bonding film 10 with the dicing sheet, chip breakage and chip scattering can be suppressed, and breakage of the semiconductor wafer 4 can be suppressed.

Next, in order to peel off the semiconductor chip adhered and fixed to the die bonding film with dicing sheet 10, the semiconductor chip 5 is picked up (pickup step). The pick-up method is not particularly limited, and various conventionally known methods can be employed. For example, there is a method in which individual semiconductor chips 5 are pushed up by needles from the side of the die bonding film with dicing sheet 10, and the picked-up semiconductor chips 5 are picked up by a pickup device.

As for the pickup condition, it is preferable to set the needle streak speed at 5 to 100 mm / sec, more preferably 5 to 10 mm / sec, from the standpoint of chipping prevention.

Here, the pick-up is performed after ultraviolet rays are applied to the pressure-sensitive adhesive layer 2 when the pressure-sensitive adhesive layer 2 is of the ultraviolet curing type. As a result, the adhesive force of the pressure-sensitive adhesive layer 2 to the die bonding film 3 is lowered, and the peeling of the semiconductor chip 5 is dissolved. As a result, the semiconductor chip 5 can be picked up without damaging it. The conditions such as the irradiation intensity at the time of ultraviolet irradiation, the irradiation time, and the like are not particularly limited and may be appropriately set according to necessity. As the light source used for ultraviolet irradiation, the above-described materials can be used. On the other hand, when the pressure-sensitive adhesive layer is cured by irradiating ultraviolet rays in advance, and the cured pressure-sensitive adhesive layer is bonded to the die-bonding film, ultraviolet irradiation here is unnecessary.

Next, the picked-up semiconductor chip 5 is bonded and fixed to the adherend 6 via the die bonding film 3 (die bonding step). Examples of the adherend 6 include a lead frame, a TAB film, a substrate, or a separately manufactured semiconductor chip. The adherend 6 may be, for example, a deformable adsorbent that is easily deformed, or a non-deformable adherend (semiconductor wafer or the like) that is not easily deformed.

As the substrate, conventionally known ones can be used. As the lead frame, a metal lead frame such as a Cu lead frame and a 42 Alloy lead frame, or an organic substrate made of glass epoxy, BT (bismaleimide-triazine), polyimide or the like can be used. However, the present invention is not limited to this, but includes a circuit board which can be used by being mounted on a semiconductor chip and electrically connected to the semiconductor chip.

Next, since the die bonding film 3 is of a thermosetting type, the semiconductor chip 5 is adhered and fixed to the adherend 6 by thermal curing to improve the heat resistance (heat curing step). The heating temperature may be 80 to 200 占 폚, preferably 100 to 175 占 폚, and more preferably 100 to 140 占 폚. The heating time may be 0.1 to 24 hours, preferably 0.1 to 3 hours, and more preferably 0.2 to 1 hour. The thermosetting may be performed under a pressurizing condition. As the pressing conditions, 1~20kg / cm ² range preferably of I and, 3~15kg / cm ² in the range I is more preferable. Thermal curing under pressure can be performed, for example, in a chamber filled with an inert gas. On the other hand, the semiconductor chip 5 bonded to the substrate or the like through the die bonding film 3 can be provided in the reflow process.

The shear adhesive force of the die bonding film 3 after heat curing is preferably 0.2 MPa or more, and more preferably 0.2 to 10 MPa with respect to the adherend 6. When the die bonding film 3 has a shear adhesive strength of at least 0.2 MPa or more, the die bonding film 3 and the semiconductor chip 5 or the adherend 6 The shear deformation does not occur at the bonding surface of the sheet. That is, the semiconductor chip does not move due to the ultrasonic vibration at the time of wire bonding, thereby preventing the success rate of the wire bonding from being lowered.

3, the tip of the terminal portion (inner lead) of the adherend 6 and the electrode pad (not shown) on the semiconductor chip 5 are electrically connected to each other by a bonding wire 7 (Wire bonding process). As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire, or the like is used. The temperature at which wire bonding is carried out is performed within a range of 80 to 250 캜, preferably 80 to 220 캜. Further, the heating time is performed for several seconds to several minutes. The connection is carried out by the combination of the vibration energy by the ultrasonic wave and the compression energy by the application of pressure while being heated to be within the above-mentioned temperature range. This step can be carried out without thermally curing the die bonding film 3. Further, in the process of the present step, the semiconductor chip 5 and the adherend 6 are not fixed by the die bonding film 3.

Next, as shown in Fig. 3, if necessary, the semiconductor chip 5 is sealed with the sealing resin 8 (sealing step). This step is performed in order to protect the semiconductor chip 5 and the bonding wire 7 mounted on the adherend 6. This step can be performed by molding a resin for encapsulation into a metal mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is usually 60 to 90 seconds at 175 DEG C, but the present invention is not limited to this, and curing can be performed at 165 to 185 DEG C for several minutes. As a result, the sealing resin is cured and the semiconductor chip 5 and the adherend 6 are fixed via the die bonding film 3. That is, in the present invention, even in the case where the post-curing step to be described later is not performed, it is possible to fix with the die bonding film 3 in the present step, to reduce the number of manufacturing steps and shorten the manufacturing period of the semiconductor device You can contribute. Further, in the present encapsulation step, a method of embedding the semiconductor chip 5 in a sheet for encapsulating a sheet (see, for example, JP-A-2013-7028) may be adopted.

Next, heating is carried out as occasion demands, so that the sealing resin 8 hardly cured in the sealing step is completely cured (post-curing step). Even in the case where the die bonding film 3 is not completely thermally cured in the sealing step, complete thermal curing of the die bonding film 3 together with the sealing resin 8 in this step becomes possible. The heating temperature in this step varies depending on the type of the encapsulating resin, but is in the range of 165 to 185 占 폚, for example, and the heating time is about 0.5 to 8 hours.

Thus, the semiconductor device shown in Fig. 3 is obtained. Since the semiconductor device thus manufactured has the die bonding film 3 having a ratio B / A of 1 or more and sufficient ion capture property even after passing through a thermal history, it is possible to suppress defective operation due to positive ions Lt; / RTI >

On the other hand, in the method of manufacturing the semiconductor device according to the present embodiment, the wire bonding is performed without going through the heat curing step by the heat treatment of the die bonding film 3 after the hardening by the die bonding step, (5) may be sealed with an encapsulating resin to cure (postcure) the encapsulating resin. In this case, the shear adhesive force at the time of hardening of the die-bonding film 3 is preferably 0.2 MPa or more, more preferably 0.2 to 10 MPa with respect to the adherend 6. When the die bonding film 3 has a shear adhesive strength of at least 0.2 MPa or more at the time of hardening, even if the wire bonding step is performed without the heating step, the die bonding film 3 ) And the bonding surface of the semiconductor chip 5 or the adherend 6. That is, the semiconductor chip does not move due to the ultrasonic vibration at the time of wire bonding, thereby preventing the success rate of the wire bonding from being lowered. On the other hand, the temporary bonding means that the die bonding film is hardened (semi-cured state) so that the curing reaction of the thermosetting die bonding film does not reach a fully advanced state, Is fixed. On the other hand, when the wire bonding is performed without the heat curing step by the heat treatment of the die bonding film, the step of post curing corresponds to the heat curing step in this specification.

On the other hand, the die bonding film with a dicing sheet of the present invention can be suitably used also in the case of stacking a plurality of semiconductor chips and performing three-dimensional mounting. At this time, the die bonding film and the spacer may be laminated between the semiconductor chips, or only the die bonding film may be laminated between the semiconductor chips without stacking the spacers, and may be appropriately changed according to the manufacturing conditions and applications.

In the above-described embodiments, the resin film for a semiconductor device of the present invention is a die bonding film. However, the resin film for a semiconductor device according to the present invention is not limited to this example as long as it is used in a semiconductor device, and may be a flip chip type semiconductor backside film for forming a back surface of a semiconductor element flip-chip bonded on an adherend , Or a sealing film for sealing semiconductor devices.

Example

Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in this embodiment are not intended to limit the gist of the present invention to them, unless otherwise specified.

The components used in the examples are described below.

Acrylic copolymer: TAYASA RESIN SG-P3 (weight average molecular weight: 850,000, glass transition temperature: 12 DEG C) manufactured by Nagase Chemtex Co.,

Phenol resin: MEH-7851SS (phenol resin having a biphenyl aralkyl skeleton, softening point: 67 ° C, hydroxyl group equivalent: 203 g / eq.) Manufactured by Meiwa Chemical Co.,

Epoxy resin: YDCN-700-2 (o-cresol novolak type epoxy resin, epoxy equivalence 200, softening point: 61 캜) manufactured by Shinnitetsu Chemical Co.,

Inorganic filler: SO-E2 (fumed spherical silica, average particle diameter 0.5 mu m) manufactured by Admatex Co.,

Additive for capturing cations: IXEPLAS-A1 (trivalent oxide hydrate of magnesium, aluminum and zirconium, average particle size 0.5 mu m)

Additive for capturing cations: BT-120 (1,2,3-benzotriazole) manufactured by JOHOKU CHEMICAL INDUSTRIES CO.

Additive for capturing cations: IXE-100 (zirconium oxide hydrate, average particle size 1.0 mu m)

On the other hand, IXEPLAS-A1 and IXE-100 as additives for capturing cations were subjected to surface treatment in advance. The surface treatment was carried out by a dry method and treated with a silane coupling agent of the amount shown in Table 1 (throughput of silane coupling agent). As the silane coupling agent, KBM503 (3-methacryloxypropyltriethoxysilane) of Shin-Etsu Chemical Co., Ltd. was used. Further, in the case of using BT-120 as an additive for capturing a cation, the silane coupling agent was dissolved in an organic solvent together with other components.

[Examples and Comparative Examples]

Each component was dissolved and dispersed in methyl ethyl ketone as an organic solvent according to the compounding ratio shown in Table 1 to obtain a resin composition solution having a concentration of 20% by weight. This resin composition solution was coated on a mold releasing film made of a polyethylene terephthalate film having a thickness of 38 占 퐉 which was subjected to a silicon release treatment and then dried at 110 占 폚 for 5 minutes. As a result, a resin film having a thickness of 25 mu m was obtained.

(Calculation of ratio B / A)

[One. Calculation of Copper Ion Capture Ratio A of the Resin Film Before Thermal Curing]

2.5 g each of the resin films (thickness: 25 탆) were cut out and folded into a vessel made of a cylindrical Teflon 占 cylinder having a diameter of 58 mm and a height of 37 mm to prepare a 10 ppm aqueous copper (II) ₂ aqueous solution). Thereafter, it was allowed to stand at 120 DEG C for 20 hours in a constant temperature drier (PV-231, manufactured by Espec Co., Ltd.). Thereafter, it was cooled to room temperature. After the film was taken out, the concentration of copper ion (copper ion concentration X) in the aqueous solution was measured using ICP-AES (SP-1700HVR, manufactured by SIII Nanotechnology Co., Ltd.).

Thereafter, the copper ion capture ratio A of the resin film before heat curing was calculated by the following formula (1). The results are shown in Table 1.

(1): [(10-X) / 10] x 100 (%)

[2. Calculation of Copper Ion Permeability B of the Resin Film After Thermal Curing]

Each of the resin films (thickness: 25 mu m) was cut out so as to have a weight of 2.5 g after peeling off the releasing film, bent, and thermally cured at 175 DEG C for 5 hours. Next, the releasing film was peeled off and placed in a cylindrical container made of Teflon (registered trademark) in the shape of a cylinder having a diameter of 58 mm and a height of 37 mm, and 50 ml of a copper (II) ion aqueous solution (CuCl ₂ aqueous solution) of 10 ppm was added. Thereafter, it was allowed to stand at 120 DEG C for 20 hours in a constant temperature drier (PV-231, manufactured by Espec Co., Ltd.). Thereafter, it was cooled to room temperature. After the film was taken out, the concentration of copper ion (copper ion concentration Y) in the aqueous solution was measured using ICP-AES (SP-1700HVR, manufactured by SII Ai Nanotechnology Co., Ltd.).

Thereafter, the copper ion capture ratio B of the resin film after thermosetting was calculated by the following formula (2). The results are shown in Table 1.

(2): [(10-Y) / 10] x 100 (%)

Based on the calculated copper ion capture ratio A and copper ion capture ratio B, the ratio B / A was calculated. The results are shown in Table 1.

(Measurement of 5% weight loss temperature)

A sample was weighed in an amount of 10 mg, and the measurement was carried out at a temperature raising rate of 10 占 폚 / min between 40 and 550 占 폚 in an air atmosphere with a differential thermal balance (TG-DTA, manufactured by Rigaku Corporation). The temperature at which the weight decreased by 5% was read.

(PH of aqueous solution after copper ion capture)

2 " (Aqueous solution when the copper ion concentration Y was measured) at the time of "calculation of the copper ion trapping rate B of the resin film after thermosetting" was measured using a Kastani ACT pH meter (D-51, manufactured by Horiba KK) did. The results are shown in Table 1.

On the other hand, the pH of the aqueous 10 ppm copper (II) ion solution before immersing the resin film was 5.6.

In Examples 1 and 2 using IXEPLASE-A1, the pH was between 4.5 and 5.5, and pH was inhibited from becoming acidic even after the copper ion was captured by ion exchange. Therefore, it is presumed that the ion trapping property is maintained high even after the thermal curing.

On the other hand, in Comparative Example 2 using IXE-100, the pH was about 3.5 and the acidity was strong. Therefore, it is presumed that the ion trapping property after the thermal curing is lowered.

Claims (6)

A resin film for a semiconductor device,
A resin film for a semiconductor device having a weight of 2.5 g before heat curing was immersed in 50 ml of an aqueous solution having 10 ppm of copper ions and the copper ion concentration (ppm) in the aqueous solution after being left at 120 캜 for 20 hours was changed to X, , The resin film for a semiconductor device having a weight of 2.5 g after heat curing at 175 ° C for 5 hours was immersed in the solution and the copper ion concentration (ppm) in the aqueous solution after being left at 120 ° C for 20 hours was defined as Y , And the ratio B / A of the copper ion trapping rate A calculated by the following formula (1) to the copper ion trapping rate B calculated by the following equation (2) is 1 or more.
(1): [(10-X) / 10] x 100 (%)
(2): [(10-Y) / 10] x 100 (%) The method according to claim 1,
And the 5% weight reduction temperature is 200 占 폚 or higher. The method according to claim 1,
And an inorganic ion capturing agent for capturing a cation. The method of claim 3,
Wherein the content of the inorganic ion-capturing agent is 1 to 30% by weight. The method of claim 3,
A resin film for a semiconductor device having a weight of 2.5 g after heat curing at 175 DEG C for 5 hours was immersed in 50 ml of an aqueous solution having 10 ppm of copper ions and the pH of the aqueous solution after being left at 120 DEG C for 20 hours was in the range of 4 to 6 Wherein the resin film is a resin film for a semiconductor device. A method for manufacturing a semiconductor device, comprising the steps of: preparing the resin film for a semiconductor device according to any one of claims 1 to 5;
And a die bonding step of die bonding the semiconductor chip onto an adherend with the resin film for semiconductor device interposed therebetween.

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