TW201631674A - Conductive film-like adhesive, dicing tape attached with film-like adhesive, and manufacturing method of semiconductor device - Google Patents

Abstract

The present invention provides a conductive film-like adhesive with better heat-dissipation after hardening, and dicing tape attached with film-like adhesive. The present invention relates to a conductive film-like adhesive, which is heated and hardened to obtain a hardened object. The ratio of first thermal conductivity of the hardened object to the second thermal conductivity before hardening (the first thermal conductivity/ the second thermal conductivity) is more than 2.0. (claim 2) The first thermal conductivity is more than 1.7W/m*K. (claim 3) The conductive film-like adhesive contains conductive particles, said conductive particles contain sheet-like metal particles and sintering metal particles which, at least one portion of them, will be sintered at 200 DEG C.

Description

Conductive film-like adhesive, etched tape with film-like adhesive, and method of manufacturing semiconductor device

The present invention relates to a conductive film-like adhesive, a dicing tape with a film-like adhesive, and a method of manufacturing a semiconductor device.

In the manufacture of a semiconductor device, a method in which a semiconductor element is subsequently bonded to a substrate such as a metal lead frame (so-called wafer bonding method) is gradually transitioned from a conventional gold-germanium eutectic to a method using solder or a resin paste. Nowadays, a conductive resin paste is sometimes used.

However, in the method of using a resin paste, there is a problem that pores cause a decrease in conductivity, or a thickness of a resin paste is uneven, or a resin paste overflows to cause contamination of a pad. In order to solve such problems, a film-like adhesive containing a polyimide resin is sometimes used instead of the resin paste (for example, see Patent Document 1).

A film-like adhesive containing an acrylic resin is also known. For example, Patent Document 2 describes a technique for improving flexibility and reducing thermal damage of a lead frame by using an acrylic copolymer having a glass transition temperature of -10 ° C to 50 ° C.

In recent years, power semiconductor devices that control and supply power have become widespread. Since the current flows in the power semiconductor device, the amount of heat generation is large. Therefore, it is desirable that the conductive adhesive used in the power semiconductor device has high heat dissipation and low resistivity.

Regarding the wafer bonding method using a film-like adhesive, it is known to include a wafer having a film-like adhesive 503 and a semiconductor wafer 505, followed by crimping the wafer 541 to a bonding body of about 100 ° C to about 150 ° C as shown in FIG. The method of step 506.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-145639

[Patent Document 2] Japanese Patent No. 4137827

However, as a result of intensive studies, the present inventors have found that if the heat dissipation property of the film-like adhesive 503 is high, it may be difficult to soften the film-like adhesive 503 to the extent that it can be adhered to the adherend 506.

An object of the present invention is to solve the above problems and to provide a conductive film-like adhesive agent having heat dissipation properties after curing which is higher than heat dissipation before curing and a dicing tape having a film-like adhesive.

The present invention relates to a conductive film-like adhesive in which the ratio of the first thermal conductivity to the second thermal conductivity (the first thermal conductivity / the second thermal conductivity) is 2.0 or more. The first thermal conductivity is a thermal conductivity of the cured product obtained by curing the conductive film-like adhesive of the present invention by heating. The second thermal conductivity is the thermal conductivity before heating.

The first thermal conductivity is preferably 1.7 W/m‧K or more.

The conductive film-like adhesive of the present invention preferably contains conductive particles. The conductive particles preferably include flaky metal particles and sinter metal particles which are sintered at least at 200 ° C. Therefore, by curing the film-like adhesive of the present invention, the heat conduction path can be widened, and heat dissipation can be improved. The content of the sinter metal particles in 100% by weight of the conductive particles is preferably 5% by weight to 50% by weight.

The conductive film-like adhesive of the present invention contains a resin component. The resin component preferably contains a thermoplastic resin or a thermosetting resin. The conductive film-like adhesive of the present invention preferably further contains a curing agent.

The use of the conductive film-like adhesive of the present invention is preferably a wafer for subsequent use.

The present invention also relates to a dicing tape having a film-like adhesive provided with a dicing tape and a conductive film-like adhesive disposed on the dicing tape. The dicing tape has a substrate and an adhesive layer disposed on the substrate.

Further, the present invention relates to a method of manufacturing a semiconductor device, which comprises the step of pressure-bonding a wafer including a conductive film-like adhesive and a semiconductor wafer disposed on a conductive film-like adhesive to a member to be bonded.

1‧‧‧Cutting Tape

3‧‧‧membranous adhesive

3a

3b

4‧‧‧Semiconductor wafer

5‧‧‧Semiconductor wafer

6‧‧‧Exposed body

7‧‧‧bonding line

8‧‧‧ Sealing resin

10‧‧‧Cutting tape with film-like adhesive

11‧‧‧Substrate

12‧‧‧Adhesive layer

12a‧‧‧Parts corresponding to the attachment part of the workpiece of the adhesive layer 12

12b‧‧‧Other parts of the adhesive layer 12

41‧‧‧ wafer followed by wafer

61‧‧‧ Attached body with semiconductor wafer

100‧‧‧ Evaluation substrate

101‧‧‧Substrate

102a‧‧‧ copper wiring

102b‧‧‧ copper wiring

102c‧‧‧ copper wiring

102d‧‧‧ copper wiring

200‧‧‧ test film

300‧‧‧Test substrate

503‧‧‧membranous adhesive

505‧‧‧Semiconductor wafer

506‧‧‧Exposed body

541‧‧‧ wafer followed by wafer

Fig. 1 is a schematic cross-sectional view of a film-like adhesive.

Fig. 2 is a schematic cross-sectional view showing a dicing tape with a film-like adhesive.

Fig. 3 is a schematic cross-sectional view showing a dicing tape with a film-like adhesive attached to a modification.

4 is a cross-sectional view schematically showing a state in which a semiconductor wafer is placed on a dicing tape to which a film-like adhesive is attached.

Fig. 5 is a schematic cross-sectional view showing a wafer followed by a wafer or the like.

Fig. 6 is a schematic cross-sectional view of a member to which a semiconductor wafer is attached.

Fig. 7 is a schematic cross-sectional view showing a semiconductor device.

Fig. 8 is a plan view of the evaluation substrate.

Figure 9 is a plan view of the test substrate.

Figure 10 is a schematic cross-sectional view showing the next step of the wafer.

The present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the embodiments.

[membrane adhesive 3]

As shown in Fig. 1, the film-like adhesive 3 has a film shape. The film-like adhesive 3 has electrical conductivity and thermosetting properties.

The film-like adhesive 3 further has the following properties. That is, the ratio of the first thermal conductivity of the cured product obtained by curing by heating to the second thermal conductivity before heating (first thermal conductivity) / 2nd thermal conductivity) is 2.0 or more. It is preferably 2.5 or more. The upper limit of the value of the ratio of the first thermal conductivity to the second thermal conductivity is not particularly limited, and is, for example, 5.0 or the like.

The first thermal conductivity is preferably 1.7 W/m‧K or more, more preferably 2.0 W/m ‧ K or more, further preferably 2.5 W/m ‧ K or more, and particularly preferably 3.0 W/m ‧ K or more The upper limit of the first thermal conductivity is, for example, 20 W/m‧K, 30 W/m‧K, or the like.

The second thermal conductivity is preferably 0.3 W/m‧K or more, more preferably 0.5 W/m‧K or more. On the other hand, the second thermal conductivity is preferably 15 W/m‧K or less, more preferably 10 W/m‧K or less.

The first thermal conductivity and the second thermal conductivity were measured by the method described in the examples.

Preferably, the film-like adhesive 3 further has the following properties. In other words, the ratio of the first resistivity of the cured product obtained by curing by heating to the second resistivity before heating (first resistivity/second resistivity) is preferably 0.01 or more, more preferably 0.015 or more. The upper limit of the value of the ratio of the first resistivity to the second resistivity is, for example, 0.95, 0.9, or the like.

The first electrical resistivity is preferably 5 × 10 ^-5 Ω ‧ m or less, more preferably 3 × 10 ^-5 Ω ‧ m or less. The lower limit of the first electrical resistivity is, for example, 1 × 10 ^-7 Ω ‧ m or the like.

The second electrical resistivity is preferably 5 × 10 ^-5 Ω ‧ m or less, more preferably 4 × 10 ^-5 Ω ‧ m or less. The lower limit of the second electrical resistivity is, for example, 3 × 10 ^-7 Ω ‧ m or the like.

The first resistivity and the second resistivity were measured by the method described in the examples.

Preferably, the film-like adhesive 3 further has the following properties. That is, the storage modulus of the cured product at 175 ° C is preferably 50 MPa or more. On the other hand, the storage modulus of the cured product at 175 ° C is preferably 1,500 MPa or less.

Preferably, the film-like adhesive 3 further has the following properties. After attaching the film-like adhesive 3 to the mirror-finished wafer at 40 ° C, the adhesion measured at 25 ° C is preferably 1 N/10 mm or more, and more preferably 4 N/10 mm or more. When it is 1 N/10 mm or more, the film-like adhesive 3 can be attached to a semiconductor wafer at a low temperature of about 40 °C. The upper limit of the adhesion is not particularly limited and is, for example, 10 N/10 mm.

In the present specification, the adhesion force refers to the peeling force when the film-like adhesive 3 is peeled off from the mirror-finished wafer, and is measured by the following method.

A mirrored wafer of 40 ° C was attached to the film-like adhesive 3 using a 2 kg roller, and left at 40 ° C for 2 minutes. Thereafter, the film was allowed to stand at room temperature (25 ° C) for 20 minutes to obtain a sample having a film-like adhesive 3 and a mirror-finished wafer attached to the film-like adhesive 3. For the sample, a tensile tester (AGS-J manufactured by Shimadzu Corporation) was used to measure the peeling film-like adhesive from the mirror-finished wafer at a peeling angle of 180 degrees, a peeling temperature of 25 ° C, and a peeling speed of 300 mm/min. 3 o'clock peeling force.

The film-like adhesive 3 contains a resin component. Examples of the resin component include a thermoplastic resin and a thermosetting resin.

Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Polyene resin, polycarbonate resin, thermoplastic polyimide resin; 6-nylon, 6,6-nylon and other polyamide resin; phenoxy resin, acrylic resin; saturated polyester resin such as PET, PBT; An amine imine resin, or a fluororesin or the like. Among these thermoplastic resins, an acrylic resin having less ionic impurities, high heat resistance, and reliability of a semiconductor element can be preferably used.

The acrylic resin is not particularly limited, and one or two kinds of esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having a carbon number of 30 or less, particularly a carbon number of 4 to 18, may be mentioned. The above-mentioned polymer (acrylic copolymer) as a component. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl, or dodecyl, and the like.

Further, the other monomer forming the polymer (acrylic copolymer) is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, and acrylic acid carboxylate. Various carboxyl group-containing monomers such as pentamethyl ester, itaconic acid, maleic acid, fumaric acid or crotonic acid; various acid anhydride monomers such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meth) acrylate 10 - Various hydroxyl group-containing monomers such as hydroxydecyl ester, 12-hydroxylauryl (meth)acrylate or (4-hydroxymethylcyclohexyl)methyl acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl a variety of sulfonic acid groups such as acrylamide-2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryloxynaphthalenesulfonic acid a monomer; or a various phosphate group-containing monomer such as 2-hydroxyethyl acryloyl phosphate.

Among the acrylic resins, those having a weight average molecular weight of 100,000 or more, more preferably a weight average molecular weight of 300,000 to 3,000,000, more preferably a weight average molecular weight of 500,000 to 2,000,000 are preferable. The reason for this is that when it is in the above numerical range, it is excellent in adhesiveness and heat resistance. Further, the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated based on polystyrene.

The acrylic resin preferably contains a functional group reactive with an epoxy group. Thereby, the acrylic resin can be crosslinked with the epoxy resin.

Examples of the functional group reactive with the epoxy group include a carboxyl group, a hydroxyl group and the like. Among them, a carboxyl group is preferred because of its high reactivity with an epoxy group.

The acid value of the acrylic resin is preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more. If it is 1 mgKOH/g or more, good cohesive force can be obtained. On the other hand, the acid value of the acrylic resin is preferably 20 mgKOH/g or less, more preferably 10 mgKOH/g or less.

Further, the acid value can be measured by the titration method specified in JIS K 0070-1992.

The glass transition temperature of the thermoplastic resin is preferably -40 ° C or higher, more preferably -35 ° C or higher, and still more preferably -25 ° C or higher. If it is less than -40 ° C, the film-like adhesive 3 tends to become sticky and the pick-up property tends to be deteriorated. Further, the glass transition temperature of the thermoplastic resin is preferably -5 ° C or lower, more preferably -10 ° C or lower, further preferably -11 ° C or lower.

The content of the thermoplastic resin in 100% by weight of the resin component is preferably 5% by weight or more, more preferably 10% by weight or more. Further, the content of the thermoplastic resin in 100% by weight of the resin component is preferably 70% by weight or less, more preferably 50% by weight or less, still more preferably 25% by weight or less.

Examples of the thermosetting resin include a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a polyoxyxylene resin, or a thermosetting polyimide resin. In particular, an epoxy resin having a small content of ionic impurities or the like which causes corrosion of the semiconductor element is preferable. Further, as the curing agent for the epoxy resin, a phenol resin is preferred.

The epoxy resin is not particularly limited, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol AF type, biphenyl type, or the like can be used. Naphthalene type, bismuth type, phenol novolak type, o-cresol novolak type, trihydroxyphenylmethane type, tetraphenol ethane type and other difunctional epoxy resin or polyfunctional epoxy resin; or beta uregua form An epoxy resin such as a triglycidyl isocyanurate type or a glycidylamine type. Among these epoxy resins, a novolac type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetraphenol ethane type epoxy resin is particularly preferable. The reason for this is that these epoxy resins are rich in reactivity with a phenol resin as a curing agent, and are excellent in heat resistance and the like.

As the epoxy resin, an epoxy resin which is solid at 25 ° C and an epoxy resin which is liquid at 25 ° C can be used.

In the present specification, the liquid state at 25 ° C means that the viscosity is less than 5000 Pa ‧ at 25 ° C. On the other hand, a solid at 25 ° C means a viscosity of 5,000 Pa s or more at 25 ° C. The viscosity can be measured using a model HAAKE Roto VISCO1 manufactured by Thermo Scientific.

The content of the epoxy resin which is solid at 25 ° C in 100% by weight of the epoxy resin is preferably 10% by weight or more, and more preferably 30% by weight or more. If it is less than 10% by weight, the film-like adhesive 3 tends to become sticky and the pick-up property tends to be deteriorated. The content of the epoxy resin which is solid at 25 ° C in 100% by weight of the epoxy resin is preferably 80% by weight or less, more preferably 70% by weight or less. under.

The epoxy equivalent of the epoxy resin which is solid at 25 ° C is preferably 100 g / eq. or more, more preferably 110 g / eq. or more. On the other hand, the epoxy equivalent of the epoxy resin which is solid at 25 ° C is preferably 2000 g / eq. or less, more preferably 1500 g / eq. or less.

The epoxy equivalent of the epoxy resin can be measured by the method specified in JIS K 7236-2009.

The epoxy equivalent of the epoxy resin which is liquid at 25 ° C is preferably 100 g / eq. or more, more preferably 110 g / eq. or more. On the other hand, the epoxy equivalent of the epoxy resin which is liquid at 25 ° C is preferably 2,000 g/eq. or less, more preferably 1,500 g/eq. or less.

The phenol resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, and a nonylphenol novolak resin. Such as a novolac type phenol resin, a resol type phenol resin, polyhydroxy styrene such as polyhydroxy styrene, and the like. Among these phenol resins, a phenol novolak resin and a phenol aralkyl resin are particularly preferable. The reason for this is that the connection reliability of the semiconductor device can be improved.

The hydroxyl equivalent of the phenol resin is preferably 80 g/eq. or more, more preferably 85 g/eq. or more. On the other hand, the hydroxyl equivalent of the phenol resin is preferably 1000 g/eq. or less, more preferably 900 g/eq. or less.

The blending ratio of the epoxy resin and the phenol resin is, for example, suitably adjusted so that the hydroxyl group in the phenol resin is 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component. More suitable for 0.8~1.2 equivalents. That is, the reason is that if the blending ratio of the two is out of the above range, a sufficient curing reaction cannot be performed, and the properties of the cured product are likely to deteriorate.

The content of the thermosetting resin in 100% by weight of the resin component is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 75% by weight or more. The content of the thermosetting resin in 100% by weight of the resin component is preferably 95% by weight or less, more preferably 90% by weight or less.

The film-like adhesive 3 contains conductive particles.

As the conductive particles, sinter metal particles, flaky metal particles, or the like can be suitably used.

The sinter metal particles have a property of being sintered at least in part at 200 °C. Therefore, the sinter metal particles are sintered under standard hardening conditions. Therefore, by curing the film-like adhesive 3, the heat conduction path can be widened, and heat dissipation can be improved. Also, the resistivity can be lowered.

As the sinter metal particles, an aggregate of metal fine particles can be suitably used. Examples of the metal fine particles include fine particles containing metal, coated fine particles, and the like. The coated fine particles include a core fine particle and a coating film covering the core fine particles. Examples of the material of the core fine particles include glass. As a material of a coating film, a metal is mentioned. Examples of the metal include gold, silver, copper, and the like.

The average particle diameter of the sinter metal particles is preferably 0.005 μm or more, and more preferably 0.01 μm or more. The lower limit of the average particle diameter is also exemplified by 0.1 μm, 0.5 μm, and 1 μm. On the other hand, the average particle diameter of the sinter metal particles is preferably 30 μm or less, and more preferably 25 μm or less. The upper limit of the average particle diameter is also exemplified by 20 μm, 15 μm, 10 μm, and 5 μm.

The average particle diameter of the sinter metal particles was measured by the following method. That is, the measurement was performed in a standard mode using a particle size distribution measuring apparatus (MICROTRAC HRA manufactured by Nikkiso), and the D50 data thus obtained was used as the particle diameter.

The shape of the sinter metal particles is not particularly limited and is, for example, amorphous.

The average long diameter of the flaky metal particles is preferably 0.5 μm or more, and more preferably 1.0 μm or more. When it is 0.5 μm or more, the electrical resistivity can be effectively lowered. On the other hand, the average long diameter of the flaky metal particles is preferably 50 μm or less, more preferably 30 μm or less.

The aspect ratio of the flaky metal particles is preferably 5 or more, preferably 8 or more, more preferably 10 or more. If it is 5 or more, the electrical resistivity can be effectively reduced. On the other hand, the aspect ratio of the flaky metal particles is preferably 10,000 or less, more preferably 100 or less, still more preferably 70 or less. Next, especially good is 50 or less.

The aspect ratio of the flaky metal particles is a ratio (average long diameter/average thickness) of the ratio of the average major axis to the average thickness. In the present specification, the average long diameter of the flaky particles is an average value obtained by observing the cross section of the film-like adhesive 3 by a scanning electron microscope (SEM) and measuring the long diameter of 100 randomly selected flaky metal particles. The average thickness of the flaky metal particles was observed by a scanning electron microscope (SEM) to observe the cross section of the film-like adhesive 3, and the average thickness of 100 randomly selected flaky metal particles was measured.

Examples of the material of the flaky metal particles include gold, silver, copper, and the like. Examples of the flaky metal particles include flaky particles of a metal, coated particles of a flaky shape, and the like. The coated particles include a coating film of core particles and coated core particles. Examples of the material of the core particles include glass and the like. As a material of a coating film, a metal is mentioned. Examples of the metal include gold, silver, copper, and the like.

The content of the sinter metal particles in 100% by weight of the conductive particles is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight or more. The content of the sinter metal particles in 100% by weight of the conductive particles is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 35% by weight or less. If it exceeds 50% by weight, there is a tendency that it is not easily formed into a film.

The content of the conductive particles in the film-like adhesive 3 is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 75% by weight or more. The content of the conductive particles in the film-like adhesive 3 is preferably 95% by weight or less, more preferably 90% by weight or less. If it exceeds 95% by weight, there is a tendency that it is not easily formed into a film.

The film-like adhesive 3 may contain, in addition to the above components, a preparation agent generally used for film production, for example, a crosslinking agent.

The film-like adhesive 3 can be produced by a usual method. For example, a solution of an adhesive composition containing the above respective components is produced, and a solution of the adhesive composition is applied onto a substrate separator to form a coating film, and then the coating film is dried, whereby the coating film can be dried. Membrane connection Agent 3.

The solvent used for the adhesive composition solution is not particularly limited, and an organic solvent which can uniformly dissolve, knead or disperse the above components is preferable. For example, a ketone solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone or cyclohexanone; toluene, xylene or the like can be mentioned. The coating method is not particularly limited. Examples of the method of solvent coating include a die coater, a gravure coater, a roll coater, a reverse coater, a riprap coater, a tube knife coater, and screen printing. Among them, a die coater is preferred in terms of high uniformity of coating thickness.

As the substrate separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a release agent such as a fluorine-based release agent or an acrylic long-chain alkyl ester release agent can be used for surface coating. Get plastic film or paper. Examples of the coating method of the adhesive composition solution include roll coating, screen coating, gravure coating, and the like. Further, the drying conditions of the coating film are not particularly limited, and for example, it can be carried out under the conditions of a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes.

For example, a method of producing the film-like adhesive 3 is preferably a method in which the above components are mixed by a stirrer, and the obtained mixture is press-molded to produce a film-like adhesive 3. As a stirrer, a planetary mixer etc. are mentioned.

The thickness of the film-like adhesive 3 is not particularly limited, but is preferably 5 μm or more, and more preferably 15 μm or more. If it is less than 5 μm, the area in contact with the semiconductor wafer or the semiconductor wafer may be unstable. Further, the thickness of the film-like adhesive 3 is preferably 100 μm or less, and more preferably 50 μm or less. When it exceeds 100 μm, there is a possibility that the film-like adhesive 3 excessively overflows due to the load of the wafer adhesion.

The film-like adhesive 3 is used to manufacture a semiconductor device. Among them, it can be suitably used for manufacturing a power semiconductor device. Specifically, it is used as a wafer adhesive film in which a substrate such as a lead frame is bonded to a semiconductor wafer (attached to the wafer). Examples of the adherend include a lead frame, an interposer, and a semiconductor wafer.

The film-like adhesive 3 is preferably used in the form of a dicing tape with a film-like adhesive. [Cutting tape 10 with film-like adhesive]

As shown in FIG. 2, the dicing tape 10 with a film-like adhesive agent has the dicing tape 1, and the film-form adhesive 3 arrange|positioned on the dicing tape 1. The dicing tape 1 includes a substrate 11 and an adhesive layer 12 disposed on the substrate 11. The film-like adhesive 3 is disposed on the adhesive layer 12.

As shown in FIG. 3, the dicing tape 10 with a film-like adhesive may be formed by forming a film-like adhesive 3 only on a workpiece (semiconductor wafer 4 or the like).

The base material 11 is a strength matrix of the dicing tape 10 to which a film-like adhesive is attached, and is preferably one having ultraviolet ray transmittance. Examples of the substrate 11 include low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, and homopolymerization. Polyolefins such as propylene, polybutene, polymethylpentene; ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, Alternate) polyesters such as copolymers, ethylene-butene copolymers, ethylene-hexene copolymers, polyurethanes, polyethylene terephthalate, polyethylene naphthalate, etc.; polycarbonate, Polyimine, polyetheretherketone, polyimine, polyetherimide, polyamine, wholly aromatic polyamine, polyphenylene sulfide, aromatic polyamide (paper), glass, glass cloth , fluororesin, polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyxylene resin, metal (foil), paper, and the like.

In order to improve adhesion to adjacent layers, retention, etc., the surface of the substrate 11 can be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage shock exposure, ionizing radiation treatment, etc. Or physical treatment, coating treatment using a primer (for example, an adhesive substance described later).

The thickness of the substrate 11 is not particularly limited and can be appropriately determined, and is generally about 5 to 200 μm.

The adhesive for forming the adhesive layer 12 is not particularly limited, and a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. Semiconductor In the case of an electronic component such as a wafer or glass, which is contaminated with impurities, such as an ultra-pure water or an organic solvent such as an alcohol, the pressure-sensitive adhesive is preferably an acrylic polymer based on an acrylic polymer. Adhesive.

Examples of the acrylic polymer include alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, second butyl ester, and third butyl ester, Amyl, isoamyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, decyl, isodecyl, undecyl, dodecyl, ten The alkyl group such as a trialkyl ester, a tetradecyl ester, a hexadecyl ester, an octadecyl ester or an eicosyl ester has a carbon number of 1 to 30, particularly a linear chain having a carbon number of 4 to 18. One or more of a cycloalkyl (meth) acrylate or the like (for example, a cyclopentyl ester or a cyclohexyl ester), and an acrylic polymer used as a monomer component Wait. In addition, the (meth)acrylate means an acrylate and/or a methacrylate, and what is called (meth) in this invention is the same.

For the purpose of improving the cohesive force, the heat resistance, and the like, the acrylic polymer may contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester, if necessary. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like. Carboxyl group-containing monomer; anhydride monomer such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid a hydroxyl group-containing monomer such as (4-hydroxymethylcyclohexyl)methyl ester; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methylpropanesulfonic acid, (methyl a sulfonic acid group-containing monomer such as acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; Base monomer; acrylamide, acrylonitrile, and the like. One or two or more kinds of these copolymerizable monomer components can be used. The amount of the copolymerizable monomers used is preferably 40% by weight or less based on the total of the monomer components.

Further, in order to cause crosslinking, the acrylic polymer may contain a polyfunctional monomer or the like as a monomer component for copolymerization as needed. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol di(meth)acrylate. Neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyurethane (meth) acrylate, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 30% by weight or less based on the total of the monomer components in terms of adhesion characteristics and the like.

The acrylic polymer is obtained by polymerizing a single monomer or a mixture of two or more kinds of monomers. The polymerization can be carried out by any one of 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 terms of prevention of contamination of the cleaned adherend or the like. In this regard, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, and more preferably about 400,000 to 3,000,000.

Moreover, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used as the above-mentioned adhesive. Specific examples of the external crosslinking method include a method of adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine crosslinking agent. In the case of using an external crosslinking agent, the amount thereof can be appropriately determined depending on the balance with the base polymer to be crosslinked, and the use as the adhesive. Usually, the external crosslinking agent is preferably formulated in an amount of 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. Further, in addition to the above components, additives such as various conventionally known adhesion-imparting agents and anti-aging agents may be used as needed.

The adhesive layer 12 can be formed using a radiation hardening type adhesive. The radiation-curable adhesive can be irradiated with radiation such as ultraviolet rays to increase the degree of crosslinking and easily reduce the adhesion.

The radiation adhesion to the other portion 12b can be set by irradiating only the portion 12a corresponding to the workpiece attachment portion of the adhesive layer 12 shown in Fig. 2 . In this case, the portion 12b formed of the unhardened radiation-curable adhesive adheres to the film-like adhesive 3, and the holding force at the time of cutting can be ensured.

Moreover, the radiation-curable adhesive layer 12 is cured in accordance with the film-like adhesive 3 shown in FIG. 3, whereby the portion 12a in which the adhesive force is remarkably lowered can be formed. In this case, the wafer ring can be fixed to the above-described portion 12b formed of an uncured radiation-curable adhesive.

In other words, when the adhesive layer 12 is formed by the radiation-curable adhesive, it is preferable that the portion 12a is irradiated with radiation so that the adhesive force of the portion 12a in the adhesive layer 12 is <the adhesion of the other portion 12b.

The radiation-curable adhesive can be a material having a radiation curable functional group such as a carbon-carbon double bond and exhibiting adhesiveness without any particular limitation. The radiation-curable adhesive agent may, for example, be a radiation-curable type in which a radiation-curable monomer component or an oligomer component is blended in a usual pressure-sensitive adhesive such as the above-described acrylic pressure-sensitive adhesive or rubber-based pressure-sensitive adhesive. Adhesive.

Examples of the radiation curable monomer component to be blended include a urethane oligomer, a (meth) acrylate urethane, a trimethylolpropane tri(meth) acrylate, and the like. Methyl hydroxymethane tetra(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxy penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Ester, 1,4-butanediol di(meth)acrylate, and the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the molecular weight thereof is about 100 to 30,000. The range of oligomers is more appropriate. The blending amount of the radiation-hardening monomer component or the oligomer component can be appropriately determined according to the kind of the above-mentioned adhesive layer to reduce the adhesive strength of the adhesive layer. Usually, it is based on a basic polymer such as an acrylic polymer constituting an adhesive. The compound is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the compound.

Further, as the radiation-curable adhesive, in addition to the above-described additive-type radiation-curable adhesive, a base polymer having a carbon-carbon double bond in a polymer side chain or a main chain or a main chain terminal may be mentioned. An intrinsic type radiation hardening adhesive. Since the intrinsic type radiation curable adhesive does not need to contain an oligomer component as a low molecular component or does not contain a large amount of an oligomer component as a low molecular component, the oligomer component or the like does not change over time. It is preferred that the adhesive layer moves in the adhesive layer to form a stable layer structure of the adhesive layer.

The base polymer having a carbon-carbon double bond described above can be used without any particular limitation, and has a carbon-carbon double bond and has adhesiveness. As such a base polymer, an acrylic polymer is preferably used as a basic skeleton. The basic skeleton of the acrylic polymer may, for example, be an acrylic polymer exemplified above.

The introduction method for introducing the carbon-carbon double bond into the above acrylic polymer is not particularly limited, and various methods can be employed. However, when a carbon-carbon double bond is introduced into the polymer side chain, molecular design is easily performed. For example, a method in which an acrylic polymer and a monomer having a functional group are copolymerized in advance, and a functional group capable of reacting with the functional group and carbon is maintained while maintaining the radiation curability of the carbon-carbon double bond The compound of the carbon double bond is subjected to a condensation or addition reaction.

Examples of the combination of such functional groups include a carboxylic acid group and an epoxy group, a carboxylic acid group and an aziridine group, a hydroxyl group and an isocyanate group. In the combination of such functional groups, a combination of a hydroxyl group and an isocyanate group is preferred in terms of ease of reaction tracking. Further, as long as a combination of the above-mentioned functional groups is used to form the above-mentioned acrylic polymer having a carbon-carbon double bond, the functional group may be located on either of the acrylic polymer and the above compound, but In a preferred combination, it is preferred that the acrylic polymer has a hydroxyl group and the above compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate and 2-methyl propylene oxime. Ethyl ethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, as the acrylic polymer, an ether group copolymerized with the above-described hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether can be used. Compounds, etc.

The above-mentioned intrinsic type radiation-curable adhesive can be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, or can be blended with the radiation curable monomer to the extent that the properties are not deteriorated. Ingredients or oligomer components. The radiation curable oligomer component or the like is 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.

When the radiation curable adhesive is cured by ultraviolet rays or the like, it contains a photopolymerization initiator. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one or α-hydroxy-α,α'-dimethylacetophenone. , an α-keto alcohol compound such as 2-methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylbenzene Ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinylpropane-1 and other acetophenone-based compounds; benzoin a benzoin ether compound such as diethyl ether, benzoin isopropyl ether, fennel aceton methyl ether; a ketal compound such as benzoin dimethyl ketal; an aromatic sulfonium chloride compound such as 2-naphthalene sulfonium chloride; Photoactive lanthanide compounds such as benzophenone-1,1-propanedione-2-(O-ethoxycarbonyl)anthracene; benzophenone, benzamidine benzoic acid, 3,3'-dimethyl-4 a benzophenone compound such as methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthiophene a thioxanthone compound such as ketone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone or 2,4-diisopropylthioxanthone; camphorquinone; halogenated ketone; Phosphine oxide Ester and the like. The amount of the photopolymerization initiator to be added is, for example, about 0.05 to 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

In addition, as the radiation-curable adhesive, an addition polymerization property having two or more unsaturated bonds as disclosed in JP-A-60-196956, for example, is mentioned. A photopolymerizable compound such as an alkoxysilane having an epoxy group; and a rubber-based adhesive or acrylic adhesive which is a photopolymerization initiator such as a carbonyl compound, an organic sulfur compound, a peroxide, an amine or a phosphonium salt compound; Agents, etc.

The radiation-curable adhesive layer 12 may contain a compound which is colored by radiation irradiation, if necessary. By including the compound colored by radiation irradiation in the adhesive layer 12, it is possible to color only the portion irradiated with radiation. The compound which is colored by radiation irradiation is a colorless or pale color before irradiation with radiation, and a compound which becomes colored by radiation irradiation, and examples thereof include a leuco dye. The ratio of use of the compound which is colored by radiation irradiation can be appropriately set.

The thickness of the adhesive layer 12 is not particularly limited, and is preferably about 1 to 50 μm in terms of prevention of the chip cut surface notch and fixing of the film-like adhesive 3. It is preferably 2 to 30 μm, and more preferably 5 to 25 μm.

The film-like adhesive 3 of the dicing tape 10 with a film-like adhesive is preferably protected by a separator (not shown). The separator has a function as a protective material for protecting the film-like adhesive 3 before being put to practical use. The separator is peeled off when the workpiece is attached to the film-like adhesive 3. As the separator, polyethylene terephthalate (PET), polyethylene, polypropylene, or a surface release coating using a release agent such as a fluorine-based release agent or a long-chain alkyl acrylate release agent may be used. Plastic film or paper.

The dicing tape 10 with a film-like adhesive can be produced by a usual method. For example, by bonding the adhesive layer 12 of the dicing tape 1 to the film-like adhesive 3, a dicing tape 10 with a film-like adhesive can be produced.

The peeling force of the film-like adhesive 3 from the dicing tape 1 at a peeling temperature of 25 ° C and a peeling speed of 300 mm/min is preferably 0.01 to 3.00 N / 20 mm. If it is less than 0.01 N/20 mm, there is a problem that the wafer scatters during dicing. On the other hand, when it exceeds 3.00 N/20 mm, picking becomes difficult.

[Method of Manufacturing Semiconductor Device]

A method of manufacturing a semiconductor device will be described.

As shown in FIG. 4, the dicing tape 10 with a film-like adhesive is pressure-bonded to the semiconductor wafer 4. Examples of the semiconductor wafer 4 include a germanium wafer, a tantalum carbide wafer, and a compound semiconductor wafer. As the compound semiconductor wafer, a gallium nitride wafer or the like can be cited.

Examples of the pressure bonding method include a method of pressing by a pressing device such as a pressure roller, and the like.

The crimping temperature (attachment temperature) is preferably 35 ° C or higher, more preferably 37 ° C or higher. The upper limit of the crimping temperature is preferably low, preferably 50 ° C or lower, more preferably 45 ° C or lower. The warpage of the semiconductor wafer 4 can be suppressed by crimping at a low temperature.

Further, the pressure is preferably from 1 × 10 ⁵ Pa to 1 × 10 ⁷ Pa, more preferably from 2 × 10 ⁵ Pa to 8 × 10 ⁶ Pa.

As shown in FIG. 5, a wafer subsequent wafer 41 is formed by dicing the semiconductor wafer 4. The wafer subsequent wafer 41 includes a film-like adhesive 3 and a semiconductor wafer 5 disposed on the film-like adhesive 3. In this step, for example, a cutting method called a full cut which cuts into the dicing tape 10 with a film-like adhesive can be used. The cutting device used in this step is not particularly limited, and a conventionally known device can be used. Further, since the semiconductor wafer 4 is subsequently fixed by the dicing tape 10 with the film-like adhesive, the wafer notch or the wafer scattering can be suppressed, and the semiconductor wafer 4 can be prevented from being damaged.

The wafer is then picked up with wafer 41. The method of picking up is not particularly limited, and various methods known in the prior art can be employed. For example, the following method or the like is used: the wafer subsequent wafer 41 is lifted from the side of the dicing tape 1 by the needle, and the wafer to be lifted is then picked up by the wafer 41 by the pick-up device.

When the adhesive layer 12 is an ultraviolet curing type, it is picked up after ultraviolet irradiation of the adhesive layer 12. Thereby, the adhesion of the adhesive layer 12 to the wafer following the wafer 41 is lowered, so that the wafer can be easily picked up by the wafer 41. The conditions such as the irradiation intensity and the irradiation time at the time of ultraviolet irradiation are not particularly limited, and may be appropriately set as necessary.

As shown in FIG. 6, the wafer is bonded to the adherend 6 by the wafer 41, whereby the adherend 61 to which the semiconductor wafer is attached is obtained. The adherend 61 to which the semiconductor wafer is attached includes the adherend 6 , the film-like adhesive 3 disposed on the adherend 6 , and the semiconductor wafer 5 disposed on the film-like adhesive 3 .

The temperature at which the wafer is subsequently pressed against the adherend 6 by the wafer 41 (hereinafter referred to as "wafer adhesion temperature") is preferably 80 ° C or higher, more preferably 90 ° C or higher. Further, the wafer adhesion temperature is preferably 150 ° C or lower, more preferably 130 ° C or lower.

The film-like adhesive 3 is cured by heating the adherend 61 with the semiconductor wafer under pressure. By thermally curing the film-like adhesive 3 under pressure, the pores existing between the film-like adhesive 3 and the adherend 6 can be eliminated, and the area in which the film-like adhesive 3 is in contact with the adherend 6 can be ensured.

The method of heating under pressure may, for example, be a method of heating the adherend 61 with a semiconductor wafer placed in a chamber filled with an inert gas. The pressure in the pressurized atmosphere is preferably 0.5 kg/cm ² (4.9 × 10 ^-2 MPa) or more, more preferably 1 kg/cm ² (9.8 × 10 ^-2 MPa) or more, and still more preferably 5 kg/cm ² (4.9). ×10 ^-1 MPa) or more. When it is 0.5 kg/cm ² or more, the pores existing between the film-like adhesive 3 and the adherend 6 can be easily eliminated. The pressure of the pressurized atmosphere is preferably 20kg / cm ² (1.96MPa) or less, more preferably 18kg / cm (1.77MPa) ² or less, and further preferably 15kg / cm ² (1.47MPa) or less. When it is 20 kg/cm ² or less, the overflow of the film-like adhesive 3 due to excessive pressurization can be suppressed.

The heating temperature is preferably 80 ° C or higher, more preferably 100 ° C or higher, further preferably 120 ° C or higher, and particularly preferably 170 ° C or higher. When it is 80 ° C or more, the film-like adhesive 3 can be made to have a moderate hardness, and the pores can be effectively eliminated by press hardening. The heating temperature is preferably 260 ° C or lower, more preferably 220 ° C or lower, further preferably 200 ° C or lower, and particularly preferably 180 ° C or lower. When it is 260 ° C or less, decomposition of the film-like adhesive 3 before hardening can be prevented.

The heating time is preferably 0.1 hour or longer, more preferably 0.2 hour or longer, and further preferably More than 0.5 hours. When it is 0.1 hour or more, the effect of pressurization can fully be obtained. The heating time is preferably 24 hours or shorter, more preferably 3 hours or shorter, and still more preferably 1 hour or shorter.

As shown in FIG. 7, a wire bonding step of electrically connecting the front end of the terminal portion (internal lead) of the adherend 6 to the electrode pad (not shown) on the semiconductor wafer 5 by the bonding wire 7 is performed. As the bonding wire 7, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The temperature at the time of wire bonding is preferably 80 ° C or higher, more preferably 120 ° C or higher, and the temperature is preferably 250 ° C or lower, more preferably 175 ° C or lower. Further, the heating time is carried out under the conditions of several seconds to several minutes (for example, one second to one minute). The wiring is performed by using the vibration energy of the ultrasonic wave and the pressure of the pressure applied by the pressure in a state where the heating reaches the above temperature range.

Then, a sealing step of sealing the semiconductor wafer 5 with the sealing resin 8 is performed. This step is performed to protect the semiconductor wafer 5 and the bonding wires 7 mounted on the adherend 6 . This step is carried out by molding the sealing resin with a mold. As the sealing resin 8, for example, an epoxy resin is used. The heating temperature at the time of resin sealing is preferably 165 ° C or higher, more preferably 170 ° C or higher, and the heating temperature is preferably 185 ° C or lower, more preferably 180 ° C or lower.

The seal can be further heated as needed (post-hardening step). Thereby, the sealing resin 8 which is insufficiently hardened in the sealing step can be completely cured. The heating temperature can be set as appropriate.

As described above, the semiconductor device can be manufactured by a method including a step of crimping the wafer including the film-like adhesive 3 and the semiconductor wafer 5 disposed on the film-like adhesive 3 to the substrate 6 by the wafer 41. The method further includes the step of heating the adherend 61 with the semiconductor wafer obtained by the step of crimping the wafer to the adherend 6 with the wafer 41, whereby the film-like adhesive 3 is cured.

More specifically, the method of the first embodiment includes the steps of: preparing a dicing tape 10 with a film-like adhesive; crimping the semiconductor wafer 4 to the film-like adhesive 3; and disposing the film in a film form. The semiconductor wafer 4 on the third agent 3 is diced to form a wafer followed by the wafer 41; the wafer is subsequently bonded to the adherend 6 by the wafer 41; The sheet is then subjected to a step of curing the film-like adhesive 3 by heating the adherend 61 with the semiconductor wafer obtained by the step of pressing the wafer 41 to the adherend 6 to be cured.

[Examples]

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.

The components used in the examples will be described.

Thermoplastic resin: Teisan Resin SG-70L manufactured by Nagase Chemtex Co., Ltd. (acrylic copolymer having carboxyl group and hydroxyl group, Mw: 900,000, acid value: 5 mgKOH/g, glass transition temperature: -13 ° C)

Epoxy Resin 1: EOCN-1020-4, manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 198 g/eq., epoxy resin at 25 ° C)

Epoxy Resin 2: JER828 manufactured by Mitsubishi Chemical Corporation (epoxy resin having a bisphenol type skeleton at 25 ° C, epoxy equivalent of 184 g / eq. ~ 194 g / eq.)

Epoxy Resin 3: EPICLON EXA-4816 manufactured by DIC Corporation (epoxy equivalent: 403 g/eq., epoxy resin at 25 ° C)

Phenol Resin 1: MEH-8000H (hydroxyl equivalent of 139 g/eq. to 143 g/eq. of phenol resin) manufactured by Minghe Chemical Co., Ltd.

Phenol Resin 2: MEH-8005 (hydroxyl equivalent of 133 g/eq. to 138 g/eq. of phenol resin) manufactured by Minghe Chemical Co., Ltd.

Conductive particle 1: 1200YP (flaky copper powder, average particle size 3.5μm, aspect ratio: 10) manufactured by Mitsui Mining Co., Ltd.

Conductive particle 2: 1400YP manufactured by Mitsui Mining Co., Ltd. (flaky copper powder, average particle size 7.0 μm, aspect ratio: 25)

Conductive particle 3: SPH02J manufactured by Mitsui Mining Co., Ltd. (aggregate of silver fine particles, average particle size of aggregates of 1.8 μm, amorphous)

Catalyst: TPP-K (tetraphenylphosphonium tetraphenylborate) manufactured by Beixing Chemical Co., Ltd.

[Production of film-like adhesive]

The components and the solvent (methyl ethyl ketone) described in Table 1 were placed in a stirred tank of a hybrid stirrer (HM-500 manufactured by Keyence) according to the blending ratios shown in Table 1, and stirred and mixed for 3 minutes in a stirring mode. The obtained varnish was applied to a release-treated film (MRA50, manufactured by Mitsubishi Plastics Co., Ltd.) using a die coater, and then dried to prepare a film-like adhesive having a thickness of 30 μm.

[Production of hardened material]

The film-like adhesive was heated at 140 ° C for 1 hour using a dryer, followed by heating at 200 ° C for 2 hours, thereby obtaining a cured product.

[Evaluation 1]

The following film-like adhesive and cured product were evaluated as follows. The results are shown in Table 1.

(Thermal conductivity)

The thermal diffusivity α (m ² /s) was measured by a temperature wave thermal analysis method (TWA method) using Ai-Phase Mobile manufactured by Ai-phase Co., Ltd. Using DSC6220 manufactured by SII Nanotechnology Co., Ltd., the DSC measurement was carried out under the conditions of a temperature increase rate of 10 ° C / min and a temperature of 20 ° C to 300 ° C, and the specific heat capacity was determined by the method described in JIS Manual (specific heat capacity measurement method K-7123 1987). Cp (J/g‧°C). Determine the specific gravity. Then, the thermal conductivity was obtained by the following formula.

[Number 1]

λ=α×ρ×Cρ

λ: thermal conductivity (W/m‧K)

α: thermal diffusivity α (m ² /s)

ρ: density (kg/m ³ )

Cρ: specific heat capacity (kJ/(kg‧K))

(resistivity)

As shown in FIG. 8, the evaluation substrate 100 having the substrate 101 and the copper wirings 102a, 102b, 102c, and 102d having a wiring width of 2 mm and a wiring thickness of 10 μm disposed on the substrate 101 was prepared. The distance between the copper wiring 102a and the copper wiring 102b, the distance between the copper wiring 102b and the copper wiring 102c, and the interval between the copper wiring 102c and the copper wiring 102d are 15 mm. A test film 200 of 10 mm × 50 mm × 30 μm was cut out from the film-like adhesive. As shown in FIG. 9, the test film 200 was pressure-bonded to the copper wirings 102a, 102b, 102c, and 102d under conditions of 70 ° C, 0.5 MPa, and 10 mm/s to prepare a test substrate 300. The test substrate 300 was heated at 140 ° C for 1 hour in a nitrogen atmosphere, followed by heating at 200 ° C for 2 hours, whereby the test film 200 was cured. The resistance value between the copper wiring 102a and the copper wiring 102b, the resistance value between the copper wiring 102a and the copper wiring 102c, and the resistance value between the copper wiring 102a and the copper wiring 102d were measured using a milliohm meter. The volume resistance value between the copper wiring 102a and the copper wiring 102b, the bulk resistance value between the copper wiring 102b and the copper wiring 102c, and the bulk resistance value between the copper wiring 102c and the copper wiring 102d are calculated from the respective resistance values. Further, the average value of the three bulk resistance values was calculated. Then, the specific resistance was calculated by the following formula.

[Number 2]

ρ=R×A/L

ρ: resistivity

R: resistance

A: sectional area

L: conductor length

[Evaluation 2]

The following evaluations were performed on the conductive particles 1 to 3.

(sintering)

The conductive particles 1 to 3 placed on the glass plate were heated at 140 ° C for 1 hour, and then heated at 200 ° C for 2 hours. The conductive particles 1 to 3 were observed by a scanning electron microscope (SEM) before and after heating. In the conductive particles 3, sintering (fusion phenomenon) was not confirmed before heating, but sintering was confirmed after heating. On the other hand, for the conductive particles 1 to 2, No sintering was confirmed before and after heating.

3‧‧‧membranous adhesive

Claims (10)

A conductive film-like adhesive which has a ratio of a first thermal conductivity of a cured product obtained by curing by heating to a second thermal conductivity before heating (the first thermal conductivity / the second The thermal conductivity) is 2.0 or more. The conductive film-like adhesive according to claim 1, wherein the first thermal conductivity is 1.7 W/m‧K or more. The conductive film-like adhesive according to claim 1, which contains conductive particles, and the conductive particles contain flaky metal particles and sinter metal particles which are sintered at least at 200 ° C. The conductive film-like adhesive according to claim 3, wherein the content of the sinter metal particles in 100% by weight of the conductive particles is 5% by weight to 50% by weight. The conductive film-like adhesive of claim 1, which contains a resin component, and the resin component contains a thermoplastic resin or a thermosetting resin. The conductive film-like adhesive of claim 5, which further contains a curing agent. The conductive film-like adhesive of claim 1 is used in the following wafer. A dicing tape provided with a film-like adhesive comprising: a dicing tape; and a conductive film-like adhesive according to claim 1 disposed on the dicing tape. A zoning tape having a film-like adhesive agent as claimed in claim 8, wherein the dicing tape comprises a substrate and an adhesive layer disposed on the substrate. A method of manufacturing a semiconductor device, comprising the steps of: using a conductive film-like adhesive according to any one of claims 1 to 7 and a semiconductor wafer disposed on the conductive film-like adhesive The wafer is crimped to the adherend.