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WO2015037634A1 - アンダーフィル材、及びこれを用いた半導体装置の製造方法 - Google Patents

アンダーフィル材、及びこれを用いた半導体装置の製造方法 Download PDF

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Publication number
WO2015037634A1
WO2015037634A1 PCT/JP2014/073967 JP2014073967W WO2015037634A1 WO 2015037634 A1 WO2015037634 A1 WO 2015037634A1 JP 2014073967 W JP2014073967 W JP 2014073967W WO 2015037634 A1 WO2015037634 A1 WO 2015037634A1
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WIPO (PCT)
Prior art keywords
underfill material
epoxy resin
semiconductor chip
underfill
inflection point
Prior art date
Application number
PCT/JP2014/073967
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English (en)
French (fr)
Inventor
太一 小山
Original Assignee
デクセリアルズ株式会社
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Filing date
Publication date
Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to CN201480002131.1A priority Critical patent/CN105283948B/zh
Priority to KR1020157003773A priority patent/KR102333581B1/ko
Priority to US14/423,966 priority patent/US9840645B2/en
Publication of WO2015037634A1 publication Critical patent/WO2015037634A1/ja

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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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Definitions

  • the present invention relates to an underfill material used for mounting a semiconductor chip and a method for manufacturing a semiconductor device using the same.
  • the mounting method using this pre-feed type underfill film is performed, for example, as follows (see, for example, Patent Document 1).
  • Step A An underfill film is attached to a wafer and diced to obtain a semiconductor chip.
  • Process B A semiconductor chip is aligned and mounted in a state where the underfill film is bonded.
  • Process C The semiconductor chip is thermocompression-bonded to ensure conduction by metal bonding of the solder bumps and to adhere by curing the underfill film.
  • the melt viscosity is set low in order to achieve good solder connectivity with respect to mounting on a substrate.
  • the storage elastic modulus G ′ is set to 10E + 04 Pa or less
  • the loss elastic modulus G ′′ is set to about 10E + 03 Pa
  • the molten fluidity does not indicate non-Bingham fluidity. This was insufficient, and the mounting body had voids.
  • the present invention has been proposed in view of such a conventional situation, and provides an underfill material capable of realizing voidless mounting and good solderability, and a method of manufacturing a semiconductor device using the underfill material.
  • the present invention preliminarily bonds a semiconductor chip on which a soldered electrode is formed to a semiconductor chip before mounting the semiconductor chip on an electronic component on which a counter electrode facing the soldered electrode is formed.
  • An underfill material comprising an epoxy resin, an acid anhydride, an acrylic resin, and an organic peroxide, and exhibiting non-Bingham fluidity at any temperature of 60 ° C. or more and 100 ° C.
  • the storage elastic modulus G ′ in the dynamic viscoelasticity measurement has an inflection point in an angular frequency region of 10E + 02 rad / s or less, and the storage elastic modulus G ′ at an angular frequency below the inflection point is 10E + 05 Pa or more and 10E + 06 Pa or less. It is characterized by being.
  • a method of manufacturing a semiconductor device wherein a soldered electrode is formed, and a semiconductor chip in which an underfill material is bonded to the electrode surface is formed on an electronic component having a counter electrode facing the soldered electrode.
  • a mounting step of mounting on the semiconductor chip, and a thermocompression bonding step of thermocompression bonding the semiconductor chip and the electronic component, and the underfill material includes an epoxy resin, an acid anhydride, an acrylic resin, and an organic peroxide. And exhibits non-Bingham fluidity at any temperature between 60 ° C.
  • the storage elastic modulus G ′ in dynamic viscoelasticity measurement is an inflection point in an angular frequency region of 10E + 02 rad / s or less.
  • the storage elastic modulus G ′ at the angular frequency below the inflection point is 10E + 05 Pa or more and 10E + 06 Pa or less.
  • the present invention since it exhibits non-Bingham fluidity when melted and has a predetermined storage elastic modulus G ', it is possible to achieve voidless mounting and good solderability.
  • FIG. 1 is a cross-sectional view schematically showing a semiconductor chip and a circuit board before mounting.
  • FIG. 2 is a cross-sectional view schematically showing a semiconductor chip and a circuit board when mounted.
  • FIG. 3 is a cross-sectional view schematically showing the semiconductor chip and the circuit board after thermocompression bonding.
  • FIG. 4 is a graph showing an example of a master curve in a molten state.
  • FIG. 5 is a flowchart showing a method for manufacturing a semiconductor device in the present embodiment.
  • FIG. 6 is a perspective view schematically showing a process of attaching an underfill film on the wafer.
  • FIG. 7 is a perspective view schematically showing a process of dicing the wafer.
  • FIG. 8 is a perspective view schematically showing a process of picking up a semiconductor chip.
  • Underfill material> The underfill material according to this embodiment is pre-bonded to a semiconductor chip before mounting the semiconductor chip on which the soldered electrode is formed on the electronic component on which the counter electrode facing the soldered electrode is formed. It is.
  • FIG. 1 is a cross-sectional view schematically showing a semiconductor chip and a circuit board before mounting
  • FIG. 2 is a cross-sectional view schematically showing the semiconductor chip and the circuit board at the time of mounting
  • FIG. 3 is a thermocompression bonding. It is sectional drawing which shows a back semiconductor chip and a circuit board typically.
  • the underfill material 20 in the present embodiment is used by being bonded in advance to the electrode surface of the semiconductor chip 10 on which the soldered electrode is formed, and the underfill material 20 is cured.
  • the layer 21 joins the semiconductor chip 10 and the circuit board 30 on which the counter electrode facing the soldered electrode is formed.
  • the semiconductor chip 10 has an integrated circuit formed on the surface of a semiconductor 11 such as silicon, and has soldered electrodes for connection called bumps.
  • the soldered electrode is obtained by joining the solder 13 on the electrode 12 made of copper or the like, and has a total thickness of the electrode 12 and the solder 13.
  • solder As the solder, Sn-37Pb eutectic solder (melting point 183 ° C), Sn-Bi solder (melting point 139 ° C), Sn-3.5Ag (melting point 221 ° C), Sn-3.0Ag-0.5Cu (melting point 217 ° C) ), Sn-5.0Sb (melting point: 240 ° C.), etc. can be used.
  • the circuit board 30 has a circuit formed on a base material 31 such as a rigid board or a flexible board.
  • a counter electrode 32 having a predetermined thickness is formed at a position facing the soldered electrode of the semiconductor chip 10 in the mounting portion where the semiconductor chip 10 is mounted.
  • the underfill material 20 contains a film-forming resin, an epoxy resin, an acid anhydride, an acrylic resin, and an organic peroxide.
  • the film-forming resin corresponds to a high-molecular weight resin having a weight average molecular weight of 10 ⁇ 10 4 or more, and preferably has a weight average molecular weight of 10 ⁇ 10 4 to 100 ⁇ 10 4 from the viewpoint of film formation.
  • various resins such as an acrylic rubber polymer, a phenoxy resin, an epoxy resin, a modified epoxy resin, and a urethane resin can be used. These film forming resins may be used alone or in combination of two or more.
  • an acrylic rubber polymer having a glycidyl group is suitably used from the viewpoint of film strength and adhesiveness.
  • the glass transition temperature Tg of the acrylic rubber polymer is preferably ⁇ 30 ° C. or higher and 20 ° C. or lower. Thereby, the flexibility of the underfill material 20 can be improved.
  • epoxy resin examples include glycidyl such as tetrakis (glycidyloxyphenyl) ethane, tetrakis (glycidyloxymethylphenyl) ethane, tetrakis (glycidyloxyphenyl) methane, trikis (glycidyloxyphenyl) ethane, and trikis (glycidyloxyphenyl) methane.
  • glycidyl such as tetrakis (glycidyloxyphenyl) ethane, tetrakis (glycidyloxymethylphenyl) ethane, tetrakis (glycidyloxyphenyl) methane, trikis (glycidyloxyphenyl) ethane, and trikis (glycidyloxyphenyl) methane.
  • Ether type epoxy resin dicyclopentadiene type epoxy resin, glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy Resin, terpene epoxy resin, tetrabromobisphenol A epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy Carboxymethyl resins, alpha-naphthol novolak type epoxy resin, and the like brominated phenol novolak type epoxy resin.
  • These epoxy resins may be used alone or in combination of two or more. Among these, in this Embodiment, it is preferable to use a glycidyl ether type epoxy resin from the point of high adhesiveness and heat resistance.
  • the acid anhydride has a flux function to remove the oxide film on the solder surface, excellent connection reliability can be obtained.
  • the acid anhydride include alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, aliphatic acid anhydrides such as tetrapropenyl succinic anhydride and dodecenyl succinic anhydride, phthalic anhydride, and trihydric anhydride. Examples thereof include aromatic acid anhydrides such as merit acid and pyromellitic anhydride.
  • These epoxy curing agents may be used alone or in combination of two or more. Among these epoxy curing agents, it is preferable to use alicyclic acid anhydrides from the viewpoint of solder connectivity.
  • a curing accelerator examples include 1,8-diazabicyclo (5,4,0) undecene-7 salt (DBU salt), 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, etc.
  • DBU salt 1,8-diazabicyclo (5,4,0) undecene-7 salt
  • 2-methylimidazole 2-ethylimidazole
  • 2-ethyl-4-methylimidazole examples thereof include imidazoles, tertiary amines such as 2- (dimethylaminomethyl) phenol, phosphines such as triphenylphosphine, and metal compounds such as tin octylate.
  • acrylic resin monofunctional (meth) acrylate, bifunctional or higher (meth) acrylate
  • monofunctional (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth) acrylate.
  • Bifunctional or higher (meth) acrylates include fluorene acrylate, bisphenol F-EO modified di (meth) acrylate, bisphenol A-EO modified di (meth) acrylate, trimethylolpropane PO modified (meth) acrylate, polyfunctional urethane A (meth) acrylate etc. can be mentioned.
  • These acrylic resins may be used alone or in combination of two or more. Among these, in the present embodiment, fluorene acrylate is preferably used.
  • organic peroxides examples include peroxyketals, peroxyesters, hydroperoxides, dialkyl peroxides, diacyl peroxides, and peroxydicarbonates. These organic peroxides may be used alone or in combination of two or more. Among these, peroxyketal is preferably used in the present embodiment.
  • an inorganic filler as another additive composition.
  • the fluidity of the resin layer at the time of pressure bonding can be adjusted.
  • the inorganic filler silica, talc, titanium oxide, calcium carbonate, magnesium oxide, or the like can be used.
  • silane coupling agents such as epoxy, amino, mercapto / sulfide, and ureido may be added.
  • the underfill material exhibits non-bingham fluidity that exhibits a behavior that does not cause flow unless a certain stress (yield stress) is applied at any temperature of 60 ° C. or higher and 100 ° C. or lower.
  • the non-Bingham fluidity can be known, for example, from the relationship in which the dynamic viscosity ⁇ ′ in the dynamic viscoelasticity measurement is inversely proportional to the angular frequency with a slope of 10 1.
  • FIG. 4 is a graph showing an example of a master curve in a molten state by dynamic viscoelasticity measurement.
  • the underfill material has an inflection point in the angular frequency region where the storage elastic modulus G ′ is 10E + 02 rad / s or less, and the storage elastic modulus G ′ at the angular frequency below the inflection point is It becomes a constant value in the range of 10E + 05 Pa to 10E + 06 Pa.
  • the underfill material has an inflection point in the angular frequency region where the storage elastic modulus G ′ is 10E + 02 rad / s or less, and the storage elastic modulus G ′ at the angular frequency below the inflection point is It becomes a constant value in the range of 10E + 05 Pa to 10E + 06 Pa.
  • the ratio of the total mass of the acrylic resin and the organic peroxide and the total mass of the epoxy resin and the acid anhydride is preferably 7: 3 to 4: 6.
  • an adhesive composition containing a film-forming resin, an epoxy resin, an acid anhydride, an acrylic resin, and an organic peroxide is dissolved in a solvent.
  • a solvent toluene, ethyl acetate or the like, or a mixed solvent thereof can be used.
  • the resin composition After preparing the resin composition, it is applied onto the release substrate using a bar coater, a coating device or the like.
  • the release substrate has, for example, a laminated structure in which a release agent such as silicone is applied to PET (Poly Ethylene Terephthalate), OPP (Oriented Polypropylene), PMP (Poly-4-methylpentene-1), PTFE (Polytetrafluoroethylene), etc. While preventing drying of a composition, the shape of a composition is maintained.
  • a release agent such as silicone is applied to PET (Poly Ethylene Terephthalate), OPP (Oriented Polypropylene), PMP (Poly-4-methylpentene-1), PTFE (Polytetrafluoroethylene), etc. While preventing drying of a composition, the shape of a composition is maintained.
  • the resin composition applied on the release substrate is dried by a heat oven, a heat drying apparatus or the like. Thereby, a pre-feed type underfill film having a predetermined thickness can be obtained.
  • FIG. 5 is a flowchart showing a method for manufacturing a semiconductor device according to the present embodiment.
  • the manufacturing method of the semiconductor device in the present embodiment includes an underfill film sticking step S1, a dicing step S2, a semiconductor chip mounting step S3, and a thermocompression bonding step S4.
  • FIG. 6 is a perspective view schematically showing a process of attaching an underfill film on a wafer.
  • the wafer 1 is fixed by a jig 3 having a ring-shaped or frame-shaped frame having a diameter larger than the diameter of the wafer 1, and the underfill is formed on the wafer 1.
  • the underfill film 2 functions as a dicing tape that protects and fixes the wafer 1 when the wafer 1 is diced and holds the wafer 1 during pick-up.
  • a large number of integrated circuits (ICs) are formed on the wafer 1, and soldered electrodes are provided on the bonding surface of the wafer 1 for each semiconductor chip 10 divided by scribe lines as shown in FIG. 1. Yes.
  • ICs integrated circuits
  • FIG. 7 is a perspective view schematically showing a process of dicing the wafer. As shown in FIG. 7, in the dicing step S2, the blade 4 is pressed along the scribe line to cut the wafer 1 and divide it into individual semiconductor chips.
  • FIG. 8 is a perspective view schematically showing a process of picking up a semiconductor chip. As shown in FIG. 8, each semiconductor chip 10 with an underfill film is held and picked up by the underfill film.
  • the semiconductor chip 10 with the underfill film and the circuit board 30 are arranged via the underfill film. Further, the semiconductor chip 10 with the underfill film is aligned and disposed so that the soldered electrode and the counter electrode 32 face each other. Then, by the heat bonder, fluidity is generated in the underfill film, but the film is heated and pressed under conditions of a predetermined temperature, pressure, and time that do not cause main curing.
  • the temperature condition at the time of mounting is preferably 30 ° C. or higher and 155 ° C. or lower.
  • the pressure condition is preferably 50 N or less, more preferably 40 N or less.
  • time conditions are 0.1 second or more and 10 seconds or less, More preferably, they are 0.1 second or more and 1.0 second or less.
  • thermocompression bonding step S4 for example, under a bonding condition in which the temperature is increased from a first temperature to a second temperature at a predetermined temperature increase rate, the solder of the soldered electrode is melted to form a metal bond, and underfill Allow the film to cure completely.
  • the bonder head is kept at a certain height by the elastic modulus of the resin until the melting temperature of the underfill film after mounting, and then descends at a stretch by the resin melting accompanying the temperature rise and reaches the lowest point of the head .
  • This lowest point is determined by the relationship between the head lowering speed and the resin curing speed. After the resin curing further proceeds, the height of the head gradually increases due to the thermal expansion of the resin and the head.
  • the first temperature is preferably substantially the same as the minimum melt viscosity attainment temperature of the underfill material, and is preferably 50 ° C. or higher and 150 ° C. or lower. Thereby, the hardening behavior of the underfill material can be matched with the bonding conditions, and the generation of voids can be suppressed. Further, the temperature rising rate is preferably 50 ° C./sec or more and 150 ° C./sec or less.
  • the second temperature is preferably 200 ° C. or higher and 280 ° C. or lower, more preferably 220 ° C. or higher and 260 ° C. or lower, although it depends on the type of solder. Thus, the soldered electrode and the substrate electrode can be metal-bonded, the underfill film can be completely cured, and the electrode of the semiconductor chip 10 and the electrode of the circuit board 30 can be electrically and mechanically connected.
  • the method for manufacturing a semiconductor device in the present embodiment includes an epoxy resin, an acid anhydride, an acrylic resin, and an organic peroxide, and at any temperature of 60 ° C. or higher and 100 ° C. or lower.
  • Non-Bingham fluidity, storage elastic modulus G ′ in dynamic viscoelasticity measurement has an inflection point in an angular frequency region of 10E + 02 rad / s or less, and storage elastic modulus G ′ at an angular frequency below the inflection point
  • the underfill material 20 of 10E + 05 Pa or more and 10E + 06 Pa or less in advance to the semiconductor chip 10 on which the soldered electrode is formed, it is possible to realize voidless mounting and good solderability.
  • the underfill film is allowed to function as a dicing tape.
  • the present invention is not limited to this, and dicing tape is used separately, and flip chip mounting is performed using the underfill film after dicing. You may go.
  • the present technology can also be applied to a TSV (Through Silicon Via) technology in which a plurality of chip substrates stacked in a sandwich shape are electrically connected by filling a small hole provided in a semiconductor chip with metal.
  • TSV Three Silicon Via
  • a semiconductor device in which a plurality of chip substrates having a first surface on which a soldered electrode is formed and a second surface on which a counter electrode facing the soldered electrode is formed on the opposite side of the first surface are stacked. This method can also be applied.
  • the first chip substrate is mounted on the second surface of the second chip substrate with the underfill film attached to the first surface side. Thereafter, a semiconductor in which a plurality of chip substrates are stacked by thermocompression bonding the first surface of the first chip substrate and the second surface of the second chip substrate at a temperature equal to or higher than the melting point of the solder of the soldered electrode. A device can be obtained.
  • Example> Examples of the present invention will be described below.
  • a pre-feed type underfill film was prepared, and dynamic viscoelasticity measurement was performed.
  • an IC chip which has an electrode with solder using an underfill film, and an IC substrate which has an electrode which counters this were produced, a mounting object was produced, and a void and a solder joint state were evaluated.
  • the present invention is not limited to these examples.
  • the underfill film was bonded onto the wafer with a press machine at 50 ° C. to 0.5 MPa, and dancing was performed to obtain an IC chip having a soldered electrode.
  • the IC chip has a size of 7 mm ⁇ and a thickness of 200 ⁇ m, and a peripherally arranged bump (16 ⁇ m thick solder (Sn-3.5Ag, melting point 221 ° C.) formed on the tip of an electrode made of Cu having a thickness of 20 ⁇ m. ⁇ 30 ⁇ m, 85 ⁇ m pitch, 280 pins).
  • a peripherally arranged bump (16 ⁇ m thick solder (Sn-3.5Ag, melting point 221 ° C.) formed on the tip of an electrode made of Cu having a thickness of 20 ⁇ m. ⁇ 30 ⁇ m, 85 ⁇ m pitch, 280 pins).
  • the IC substrate opposite to this has a size of 7 mm ⁇ , a thickness of 200 ⁇ m, and a peripheral arrangement bump ( ⁇ 30 ⁇ m, 85 ⁇ m pitch, 280 pins) on which an electrode made of Cu of 20 ⁇ m is formed. I had it.
  • an IC chip was mounted on the IC substrate using a flip chip bonder under the conditions of 80 ° C. ⁇ 0.5 seconds ⁇ 30N.
  • thermocompression bonding was performed from 80 ° C. to 250 ° C. at a temperature rising rate of 50 ° C./sec using a flip chip bonder. Further, the bonder head was lowered to the lowest point within the time to raise the temperature from 80 ° C. to 250 ° C. (30 N). Further, it was cured at 150 ° C. for 2 hours to obtain a mounting body. The temperature at the time of using the flip chip bonder is obtained by measuring the actual temperature of the sample with a thermocouple.
  • Example 1 40 parts by mass of acrylic rubber polymer (product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX Corporation) as a film-forming resin, 30 parts by mass of epoxy resin (product name: JER1031S, manufactured by Mitsubishi Chemical Corporation), acid anhydride (product name) : 20 parts by mass of Jamaicacid HNA-100 (manufactured by Shin Nippon Rika Co., Ltd.), 1 part by mass of imidazole (product name: U-CAT-5002, manufactured by San Apro) as a curing accelerator, and acrylic resin (product name: Oxol EA-0200) 49 parts by mass of Osaka Organic Chemical Co., Ltd., 1 part by mass of organic peroxide (product name: Perhexa V, manufactured by NOF Corporation), and 15 parts by mass of filler (product name: Aerosil R202, manufactured by Nippon Aerosil Co., Ltd.) A resin composition having an acrylic / epoxy ratio of 50/50 was prepared.
  • epoxy resin product name:
  • peeled PET Polyethylene terephthalate
  • bar coater This was applied to peeled PET (Polyethylene terephthalate) using a bar coater and dried in an oven at 80 ° C. for 3 minutes to produce a 50 ⁇ m thick underfill film (cover peeled PET (25 ⁇ m) / underfill). Film (50 ⁇ m) / base release PET (50 ⁇ m)).
  • Table 1 shows the results of dynamic viscoelasticity measurement of the underfill film and the evaluation results of the mounted body.
  • the inflection point was 10E + 1.9 rad / s
  • the storage modulus G ′ was 10E + 5.3 Pa
  • the slope of ⁇ ′ was a power of 10
  • the underfill film exhibited non-Bingham fluidity.
  • the evaluation of the void of the mounting body produced using this underfill film was ⁇
  • the evaluation of solder bonding was ⁇ .
  • ⁇ Comparative Example 1 40 parts by mass of acrylic rubber polymer (product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX Corporation) as a film-forming resin, 55 parts by mass of epoxy resin (product name: JER1031S, manufactured by Mitsubishi Chemical Corporation), acid anhydride (product name) : 44 parts by mass of Jamaicacid HNA-100 (manufactured by Shin Nippon Rika Co., Ltd.), 2 parts by mass of imidazole (product name: U-CAT-5002, manufactured by San Apro) as a curing accelerator, filler (product name: Aerosil R202, Nippon Aerosil) 15 parts by mass) was prepared, and a resin composition having an acrylic / epoxy ratio of 50/50 was prepared.
  • acrylic rubber polymer product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX Corporation
  • epoxy resin product name: JER1031S, manufactured by Mitsubishi Chemical Corporation
  • acid anhydride product name
  • peeled PET Polyethylene terephthalate
  • bar coater This was applied to peeled PET (Polyethylene terephthalate) using a bar coater and dried in an oven at 80 ° C. for 3 minutes to produce a 50 ⁇ m thick underfill film (cover peeled PET (25 ⁇ m) / underfill). Film (50 ⁇ m) / base release PET (50 ⁇ m)).
  • Table 1 shows the results of dynamic viscoelasticity measurement of the underfill film and the evaluation results of the mounted body.
  • the inflection point was 10E + 4.0 rad / s
  • the storage elastic modulus G ′ was 10E + 4.3 Pa
  • the slope of ⁇ ′ was less than 10 1
  • the underfill film did not exhibit non-Bingham fluidity.
  • the evaluation of the void of the mounting body produced using this underfill film was ⁇
  • the evaluation of solder bonding was ⁇ .
  • peeled PET Polyethylene terephthalate
  • bar coater This was applied to peeled PET (Polyethylene terephthalate) using a bar coater and dried in an oven at 80 ° C. for 3 minutes to produce a 50 ⁇ m thick underfill film (cover peeled PET (25 ⁇ m) / underfill). Film (50 ⁇ m) / base release PET (50 ⁇ m)).
  • Table 1 shows the results of dynamic viscoelasticity measurement of the underfill film and the evaluation results of the mounted body.
  • the inflection point is not clear, the storage elastic modulus G ′ of 10E + 02 rad / s or less is 10E + 6.5 Pa, the slope of ⁇ ′ of 10E + 02 rad / s or less is more than 10 1, and the underfill film is non-Bingham fluidity Did not show.
  • the evaluation of the void of the mounting body produced using this underfill film was x, and the evaluation of solder bonding was x.

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Abstract

　ボイドレス実装及び良好なハンダ接合性を実現可能なアンダーフィル材、及びこれを用いた半導体装置の製造方法を提供する。エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有し、６０℃以上１００℃以下のいずれかの温度で、非ビンガム流動性を示し、動的粘弾性測定における貯蔵弾性率Ｇ'が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、該変曲点以下の角周波数における貯蔵弾性率Ｇ'が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下であるアンダーフィル材を用いる。これにより、ボイドレス実装及び良好なハンダ接合性を実現することができる。

Description

アンダーフィル材、及びこれを用いた半導体装置の製造方法
　本発明は、半導体チップの実装に用いられるアンダーフィル材、及びこれを用いた半導体装置の製造方法に関する。本出願は、日本国において２０１３年９月１１日に出願された日本特許出願番号特願２０１３－１８７９８０を基礎として優先権を主張するものであり、この出願は参照されることにより、本出願に援用される。
　近年、半導体チップの実装方法において、工程短縮を目的に、半導体ＩＣ（Integrated Circuit）電極上にアンダーフィルフィルムを貼り付ける「先供給型アンダーフィルフィルム（ＰＵＦ：Pre-applied Underfill Film）」の使用が検討されている。
　この先供給型アンダーフィルフィルムを使用した実装方法は、例えば、以下のように行われる（例えば、特許文献１参照。）。
　工程Ａ：ウエハにアンダーフィルフィルムを貼り付け、ダイシングして半導体チップを得る。
　工程Ｂ：アンダーフィルフィルムが貼り合わされた状態で、半導体チップを位置合わせして搭載する。
　工程Ｃ：半導体チップを熱圧着し、ハンダバンプの金属結合による導通確保、及びアンダーフィルフィルムの硬化による接着を行う。
　先供給型アンダーフィルフィルムは、予めウエハにラミネートされた状態で使用されるため、基板への実装に対して、良好なハンダ接続性を実現するために溶融粘度が低く設定されている。例えば、貯蔵弾性率Ｇ’が１０Ｅ＋０４Ｐａ以下、損失弾性率Ｇ’’が１０Ｅ＋０３Ｐａ程度に設定されているものが多く、さらに溶融状態の流動性が非ビンガム流動性を示していないため、実装時のエアーの排除が不十分となり、ボイドを内在した実装体となっていた。
特開２００５－２８７３４号公報
　本発明は、このような従来の実情に鑑みて提案されたものであり、ボイドレス実装及び良好なハンダ接合性を実現可能なアンダーフィル材、及びこれを用いた半導体装置の製造方法を提供する。
　前述した課題を解決するために、本発明は、ハンダ付き電極が形成された半導体チップを、ハンダ付き電極と対向する対向電極が形成された電子部品に搭載する前に、半導体チップに予め貼り合わされるアンダーフィル材であって、エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有し、６０℃以上１００℃以下のいずれかの温度で、非ビンガム流動性を示し、動的粘弾性測定における貯蔵弾性率Ｇ’が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、該変曲点以下の角周波数における貯蔵弾性率Ｇ’が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下であることを特徴とする。
　また、本発明に係る半導体装置の製造方法は、ハンダ付き電極が形成され、該電極面にアンダーフィル材が貼り合わされた半導体チップを、前記ハンダ付き電極と対向する対向電極が形成された電子部品に搭載する搭載工程と、前記半導体チップと前記電子部品とを熱圧着する熱圧着工程とを有し、前記アンダーフィル材は、エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有し、６０℃以上１００℃以下のいずれかの温度で、非ビンガム流動性を示し、動的粘弾性測定における貯蔵弾性率Ｇ’が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、該変曲点以下の角周波数における貯蔵弾性率Ｇ’が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下であることを特徴とする。
　本発明によれば、溶融時に非ビンガム流動性を示し、所定の貯蔵弾性率Ｇ’を有しているため、ボイドレス実装及び良好なハンダ接合性を実現することができる。
図１は、搭載前の半導体チップと回路基板とを模式的に示す断面図である。 図２は、搭載時の半導体チップと回路基板とを模式的に示す断面図である。 図３は、熱圧着後の半導体チップと回路基板とを模式的に示す断面図である。 図４は、溶融状態のマスターカーブの一例を示すグラフである。 図５は、本実施の形態における半導体装置の製造方法を示すフローチャートである。 図６は、ウエハ上にアンダーフィルフィルムを貼り付ける工程を模式的に示す斜視図である。 図７は、ウエハをダイシングする工程を模式的に示す斜視図である。 図８は、半導体チップをピックアップする工程を模式的に示す斜視図である。
　以下、本発明の実施の形態について、下記順序にて詳細に説明する。
１．アンダーフィル材
２．半導体装置の製造方法
３．実施例
　＜１．アンダーフィル材＞
　本実施の形態に係るアンダーフィル材は、ハンダ付き電極が形成された半導体チップを、ハンダ付き電極と対向する対向電極が形成された電子部品に搭載する前に、半導体チップに予め貼り合わされるものである。
　図１は、搭載前の半導体チップと回路基板とを模式的に示す断面図、図２は、搭載時の半導体チップと回路基板とを模式的に示す断面図、及び、図３は、熱圧着後の半導体チップと回路基板とを模式的に示す断面図である。
　図１～図３に示すように、本実施の形態におけるアンダーフィル材２０は、ハンダ付き電極が形成された半導体チップ１０の電極面に予め貼り合わされて使用され、アンダーフィル材２０が硬化した接着層２１により半導体チップ１０と、ハンダ付き電極と対向する対向電極が形成された回路基板３０とを接合する。
　半導体チップ１０は、シリコンなどの半導体１１表面に集積回路が形成され、バンプと呼ばれる接続用のハンダ付き電極を有する。ハンダ付き電極は、銅などからなる電極１２上にハンダ１３を接合したものであり、電極１２の厚みとハンダ１３の厚みとを合計した厚みを有する。
　ハンダとしては、Ｓｎ－３７Ｐｂ共晶ハンダ（融点１８３℃）、Ｓｎ－Ｂｉハンダ（融点１３９℃）、Ｓｎ－３．５Ａｇ（融点２２１℃）、Ｓｎ－３．０Ａｇ－０．５Ｃｕ（融点２１７℃）、Ｓｎ－５．０Ｓｂ（融点２４０℃）などを用いることができる。
　回路基板３０は、例えばリジット基板、フレキシブル基板などの基材３１に回路が形成されている。また、半導体チップ１０が搭載される実装部には、半導体チップ１０のハンダ付き電極と対向する位置に所定の厚みを有する対向電極３２が形成されている。
　アンダーフィル材２０は、膜形成樹脂と、エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有する。
　膜形成樹脂は、重量平均分子量が１０×１０４以上の高分子量樹脂に相当し、フィルム形成性の観点から、１０×１０４～１００×１０４の重量平均分子量であることが好ましい。膜形成樹脂としては、アクリルゴムポリマー、フェノキシ樹脂、エポキシ樹脂、変性エポキシ樹脂、ウレタン樹脂等の種々の樹脂を用いることができる。これらの膜形成樹脂は、１種を単独で用いても、２種類以上を組み合わせて用いても良い。これらの中でも、本実施の形態では、膜強度及び接着性の観点から、グリシジル基を有するアクリルゴムポリマーが好適に用いられる。また、アクリルゴムポリマーのガラス転移温度Ｔｇは、－３０℃以上２０℃以下であることが好ましい。これにより、アンダーフィル材２０の可撓性を向上させることができる。
　エポキシ樹脂としては、例えば、テトラキス(グリシジルオキシフェニル)エタン、テトラキス（グリシジルオキシメチルフェニル）エタン、テトラキス（グリシジルオキシフェニル）メタン、トリキス（グリシジルオキシフェニル）エタン、トリキス（グリシジルオキシフェニル）メタン等のグリシジルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、スピロ環型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テルペン型エポキシ樹脂、テトラブロムビスフェノールＡ型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、α－ナフトールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂などを挙げることができる。これらのエポキシ樹脂は、１種を単独で用いても、２種類以上を組み合わせて用いても良い。これらの中でも、本実施の形態では、高接着性、耐熱性の点から、グリシジルエーテル型エポキシ樹脂を用いることが好ましい。
　酸無水物は、ハンダ表面の酸化膜を除去するフラックス機能を有するため、優れた接続信頼性を得ることができる。酸無水物としては、例えばヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸などの脂環式酸無水物、テトラプロペニル無水コハク酸、ドデセニル無水コハク酸などの脂肪族酸無水物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸などの芳香族酸無水物などを挙げることができる。これらのエポキシ硬化剤は、１種を単独で用いても、２種類以上を組み合わせて用いても良い。これらのエポキシ硬化剤の中でもこれらのうちハンダ接続性の点から、脂環式酸無水物を用いることが好ましい。
　また、硬化促進剤を添加することが好ましい。硬化促進剤の具体例としては、１，８－ジアザビシクロ（５，４，０）ウンデセン－７塩（ＤＢＵ塩）、２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾールなどのイミダゾ－ル類、２－（ジメチルアミノメチル）フェノールなどの第３級アミン類、トリフェニルホスフィンなどのホスフィン類、オクチル酸スズなどの金属化合物などが挙げられる。
　アクリル樹脂としては、単官能（メタ）アクリレート、２官能以上の（メタ）アクリレートを使用可能である。単官能（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート等が挙げられる。２官能以上の（メタ）アクリレートとしては、フルオレン系アクリレート、ビスフェノールＦ―ＥＯ変性ジ（メタ）アクリレート、ビスフェノールＡ―ＥＯ変性ジ（メタ）アクリレート、トリメチロールプロパンＰＯ変性（メタ）アクリレート、多官能ウレタン（メタ）アクリレート等を挙げることができる。これらのアクリル樹脂は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。これらの中でも、本実施の形態では、フルオレン系アクリレートが好適に用いられる。
　有機過酸化物としては、例えば、パーオキシケタール、パーオキシエステル、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート等を挙げることができる。これらの有機過酸化物は、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。これらの中でも、本実施の形態では、パーオキシケタールが好適に用いられる。
　また、その他の添加組成物として、無機フィラーを含有することが好ましい。無機フィラーを含有することにより、圧着時における樹脂層の流動性を調整することができる。無機フィラーとしては、シリカ、タルク、酸化チタン、炭酸カルシウム、酸化マグネシウム等を用いることができる。
　さらに、必要に応じて、エポキシ系、アミノ系、メルカプト・スルフィド系、ウレイド系などのシランカップリング剤を添加してもよい。
　このように硬化反応の比較的遅いエポキシ系と、硬化反応の比較的速いアクリル系とを併用することにより、ボイドレス実装及び良好なハンダ接合性を実現することができる。
　また、アンダーフィル材は、６０℃以上１００℃以下のいずれかの温度において、ある一定以上の応力（降伏応力）を与えないと流動を起こさないという挙動を示す非ビンガム流動性を示す。非ビンガム流動性は、例えば、動的粘弾性測定における動的粘性率η’が角周波数に対して１０の１乗の傾きで反比例する関係から知ることができる。
　図４は、動的粘弾性測定による溶融状態のマスターカーブの一例を示すグラフである。アンダーフィル材は、図４に示すマスターカーブにおいて、貯蔵弾性率Ｇ’が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、変曲点以下の角周波数における貯蔵弾性率Ｇ’が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下の範囲で一定値となる。これにより、ボイドレス実装及び良好なハンダ接合性を実現することができる。
　また、アクリル樹脂と有機過酸化物との合計質量と、エポキシ樹脂と酸無水物との合計質量との比は、７：３～４：６であることが好ましい。これにより、ボイドレス実装及び良好なハンダ接合性を実現するアンダーフィル材を得ることができる。
　次に、前述したアンダーフィル材が膜状に形成された先供給型アンダーフィルフィルムの製造方法について説明する。先ず、膜形成樹脂と、エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有する接着剤組成物を溶剤に溶解させる。溶剤としては、トルエン、酢酸エチルなど、又はこれらの混合溶剤を用いることができる。樹脂組成物を調整後、バーコーター、塗布装置などを用いて剥離基材上に塗布する。
　剥離基材は、例えば、シリコーンなどの剥離剤をＰＥＴ（Poly Ethylene Terephthalate）、ＯＰＰ（Oriented Polypropylene）、ＰＭＰ（Poly-4-methylpentene－1）、ＰＴＦＥ（Polytetrafluoroethylene）などに塗布した積層構造からなり、組成物の乾燥を防ぐとともに、組成物の形状を維持するものである。
　次に、剥離基材上に塗布された樹脂組成物を熱オーブン、加熱乾燥装置などにより乾燥させる。これにより、所定の厚さの先供給型アンダーフィルフィルムを得ることができる。
　＜２．半導体装置の製造方法＞
　次に、前述した先供給型アンダーフィルフィルムを用いた半導体装置の製造方法について説明する。
　図５は、本実施の形態における半導体装置の製造方法を示すフローチャートである。図５に示すように、本実施の形態における半導体装置の製造方法は、アンダーフィルフィルム貼付工程Ｓ１と、ダイシング工程Ｓ２と、半導体チップ搭載工程Ｓ３と、熱圧着工程Ｓ４とを有する。
　図６は、ウエハ上にアンダーフィルフィルムを貼り付ける工程を模式的に示す斜視図である。図６に示すように、アンダーフィルフィルム貼付工程Ｓ１では、ウエハ１の直径よりも大きな直径を有するリング状又は枠状のフレームを有する治具３によりウエハ１を固定し、ウエハ１上にアンダーフィルフィルム２を貼り付ける。アンダーフィルフィルム２は、ウエハ１のダイシング時にウエハ１を保護・固定し、ピックアップ時に保持するダイシングテープとして機能する。なお、ウエハ１には多数のＩＣ（Integrated Circuit）が作り込まれ、ウエハ１の接着面には、図１に示すようにスクライブラインによって区分される半導体チップ１０毎にハンダ付き電極が設けられている。
　図７は、ウエハをダイシングする工程を模式的に示す斜視図である。図７に示すように、ダイシング工程Ｓ２では、ブレード４をスクライブラインに沿って押圧してウエハ１を切削し、個々の半導体チップに分割する。
　図８は、半導体チップをピックアップする工程を模式的に示す斜視図である。図８に示すように、各アンダーフィルフィルム付き半導体チップ１０は、アンダーフィルフィルムに保持されてピックアップされる。
　半導体チップ搭載工程Ｓ３では、図２に示すように、アンダーフィルフィルム付き半導体チップ１０と回路基板３０とをアンダーフィルフィルムを介して配置する。また、アンダーフィルフィルム付き半導体チップ１０をハンダ付き電極と対向電極３２とが対向するように位置合わせして配置する。そして、加熱ボンダーによって、アンダーフィルフィルムに流動性は生じるが、本硬化は生じない程度の所定の温度、圧力、時間の条件で加熱押圧し、搭載する。
　搭載時の温度条件は、３０℃以上１５５℃以下であることが好ましい。また、圧力条件は５０Ｎ以下であることが好ましく、より好ましくは４０Ｎ以下である。また、時間条件は０．１秒以上１０秒以下であることが好ましく、より好ましくは０．１秒以上１．０秒以下である。これにより、ハンダ付き電極が溶融せずに回路基板３０側の電極と接している状態とすることができ、アンダーフィルフィルムが完全硬化していない状態とすることができる。また、低い温度で固定するため、ボイドの発生を抑制し、半導体チップ１０へのダメージを低減することができる。
　次の熱圧着工程Ｓ４では、例えば第１の温度から第２の温度まで所定の昇温速度で昇温させるボンディング条件で、ハンダ付き電極のハンダを溶融させて金属結合を形成させるとともに、アンダーフィルフィルムを完全硬化させる。
　また、ボンダーヘッドは、搭載後のアンダーフィルフィルムの溶融開始温度まで樹脂の弾性率により一定の高さに保たれた後、昇温に伴う樹脂溶融により一気に下降し、ヘッドの最下点に達する。この最下点は、ヘッドの下降速度と樹脂の硬化速度との関係により決まる。樹脂硬化がさらに進行した後、ヘッドの高さは、樹脂とヘッドの熱膨張により徐々に上昇する。このように、第１の温度から第２の温度に昇温する時間内にボンダーヘッドを最下点まで下降させることにより、樹脂溶融に伴うボイドの発生を抑制することができる。
　第１の温度は、アンダーフィル材の最低溶融粘度到達温度と略同一であることが好ましく、５０℃以上１５０℃以下であることが好ましい。これによりアンダーフィル材の硬化挙動をボンディング条件に合致させることができ、ボイドの発生を抑制することができる。また、昇温速度は、５０℃／ｓｅｃ以上１５０℃／ｓｅｃ以下であることが好ましい。また、第２の温度は、ハンダの種類にもよるが、２００℃以上２８０℃以下であることが好ましく、より好ましくは２２０℃以上２６０℃以下である。これにより、ハンダ付き電極と基板電極とを金属結合させるとともに、アンダーフィルフィルムを完全硬化させ、半導体チップ１０の電極と回路基板３０の電極とを電気的、機械的に接続させることができる。
　このように本実施の形態における半導体装置の製造方法は、エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有し、６０℃以上１００℃以下のいずれかの温度で、非ビンガム流動性を示し、動的粘弾性測定における貯蔵弾性率Ｇ’が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、該変曲点以下の角周波数における貯蔵弾性率Ｇ’が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下であるアンダーフィル材２０を、ハンダ付き電極が形成された半導体チップ１０に予め貼り合わせることにより、ボイドレス実装及び良好なハンダ接合性を実現することができる。
　なお、前述の実施の形態では、アンダーフィルフィルムをダイシングテープとして機能させることとしたが、これに限られるものではなく、ダイシングテープを別に用い、ダイシング後にアンダーフィルフィルムを使用してフリップチップ実装を行ってもよい。
　［他の実施の形態］
　また、本技術は、半導体チップに設けた小さな孔に金属を充填することによって、サンドイッチ状に積み重ねた複数のチップ基板を電気的に接続するＴＳＶ（Through Silicon Via）技術にも適用可能である。
　すなわち、ハンダ付き電極が形成された第１の面と、第１の面の反対側にハンダ付き電極と対向する対向電極が形成された第２の面を有する複数のチップ基板を積層する半導体装置の製造方法にも適用可能である。
　この場合、第１のチップ基板の第１の面側にアンダーフィルフィルムを貼り付けた状態で、第２のチップ基板の第２の面に搭載する。その後、第１のチップ基板の第１の面と第２のチップ基板の第２の面とをハンダ付き電極のハンダの融点以上の温度で熱圧着することにより、複数のチップ基板を積層した半導体装置を得ることができる。
　＜３．実施例＞
　以下、本発明の実施例について説明する。本実施例では、先供給型のアンダーフィルフィルムを作製し、動的粘弾性測定を行った。そして、アンダーフィルフィルムを用いてハンダ付き電極を有するＩＣチップと、これに対向する電極を有するＩＣ基板とを接続させて実装体を作製し、ボイド及びハンダ接合状態を評価した。なお、本発明はこれらの実施例に限定されるものではない。
　動的粘弾性測定、実装体の作製、ボイドの評価、及びハンダ接合の評価は、次のように行った。
　［動的粘弾性測定］
　各アンダーフィルフィルムについて、レオメータ（ＴＡ社製ＡＲＥＳ）を用いて、設定温度を８０℃として、角周波数に対する動的粘性率η’、及び角周波数に対する貯蔵弾性率Ｇ’のマスターカーブを作成し、変曲点（塑性降伏点）、変曲点以下の角周波数における貯蔵弾性率Ｇ’、及び変曲点以下の角周波数に対する動的粘性率η’の傾きを求めた。
　［実装体の作製］
　アンダーフィルフィルムをウエハ上にプレス機にて、５０℃－０．５ＭＰａの条件で貼り合わせ、ダンシングしてハンダ付き電極を有するＩＣチップを得た。
　ＩＣチップは、その大きさが７ｍｍ□、厚み２００μｍであり、厚み２０μｍのＣｕからなる電極の先端に厚み１６μｍのハンダ（Ｓｎ－３．５Ａｇ、融点２２１℃）が形成されたペリフェラル配置のバンプ（φ３０μｍ、８５μｍピッチ、２８０ピン）を有するものであった。
　また、これに対向するＩＣ基板は、同様に、その大きさは７ｍｍ□、厚み２００μｍであり、厚み２０μｍのＣｕからなる電極が形成されたペリフェラル配置のバンプ（φ３０μｍ、８５μｍピッチ、２８０ピン）を有するものであった。
　次に、フリップチップボンダーを用いて、８０℃－０．５秒－３０Ｎの条件でＩＣ基板上にＩＣチップを搭載した。
　その後、フリップチップボンダーを用いて、８０℃から２５０℃まで５０℃／ｓｅｃの昇温速度で熱圧着した。また、８０℃から２５０℃に昇温する時間内にボンダーヘッドを最下点まで下降させた（３０Ｎ）。さらに、１５０℃－２時間の条件でキュアし、実装体を得た。なお、フリップチップボンダー使用時における温度は、熱電対によりサンプルの実温を測定したものである。
　［ボイドの評価］
　実装体をＳＡＴ（Scanning Acoustic Tomograph, 超音波映像装置）を用いて観察した。ボイドが発生していない場合を「○」と評価し、実装体にボイドが発生している場合を「×」と評価した。一般的に、ボイドが生じると、長期信頼性に悪影響を及ぼす可能性が高くなる。
　［ハンダ接合の評価］
　実装体のサンプルを切断し、断面研磨を行い、ＩＣチップの電極とＩＣ基板の電極との間のハンダの状態をＳＥＭ（Scanning Electron Microscope）観察した。ハンダ接続、ハンダ濡れ共に良好な状態を「○」と評価し、実装体のハンダ接続、又はハンダ濡れが不十分な状態を「×」と評価した。
　＜実施例１＞
　膜形成樹脂としてのアクリルゴムポリマー（品名：テイサンレジンＳＧ－Ｐ３、ナガセケムテックス社製）を４０質量部、エポキシ樹脂（品名：ＪＥＲ１０３１Ｓ、三菱化学社製）を３０質量部、酸無水物（品名：リカシッドＨＮＡ－１００、新日本理化社製)を２０質量部、硬化促進剤としてのイミダゾール（品名：Ｕ－ＣＡＴ－５００２、サンアプロ社製）を１質量部、アクリル樹脂（品名：オクゾールＥＡ－０２００、大阪有機化学社製）を４９質量部、有機過酸化物（品名：パーヘキサＶ、日油社製）を１質量部、フィラー（品名：アエロジルＲ２０２、日本アエロジル社製）を１５質量部配合し、アクリル／エポキシが５０／５０の樹脂組成物を調製した。これを、剥離処理されたＰＥＴ（Polyethylene terephthalate）にバーコーターを用いて塗布し、８０℃のオーブンで３分間乾燥させ、厚み５０μｍのアンダーフィルフィルムを作製した（カバー剥離ＰＥＴ（２５μｍ）／アンダーフィルフィルム（５０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　表１に、アンダーフィルフィルムの動的粘弾性測定の結果、及び実装体の評価結果を示す。変曲点は１０Ｅ＋１．９ｒａｄ／ｓ、貯蔵弾性率Ｇ’は１０Ｅ＋５．３Ｐａ、η’の傾きは１０の１乗であり、アンダーフィルフィルムは、非ビンガム流動性を示した。このアンダーフィルフィルムを用いて作製した実装体のボイドの評価は○、ハンダ接合の評価は○であった。
　＜比較例１＞
　膜形成樹脂としてのアクリルゴムポリマー（品名：テイサンレジンＳＧ－Ｐ３、ナガセケムテックス社製）を４０質量部、エポキシ樹脂（品名：ＪＥＲ１０３１Ｓ、三菱化学社製）を５５質量部、酸無水物（品名：リカシッドＨＮＡ－１００、新日本理化社製)を４４質量部、硬化促進剤としてのイミダゾール（品名：Ｕ－ＣＡＴ－５００２、サンアプロ社製）を２質量部、フィラー（品名：アエロジルＲ２０２、日本アエロジル社製）を１５質量部配合し、アクリル／エポキシが５０／５０の樹脂組成物を調製した。これを、剥離処理されたＰＥＴ（Polyethylene terephthalate）にバーコーターを用いて塗布し、８０℃のオーブンで３分間乾燥させ、厚み５０μｍのアンダーフィルフィルムを作製した（カバー剥離ＰＥＴ（２５μｍ）／アンダーフィルフィルム（５０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　表１に、アンダーフィルフィルムの動的粘弾性測定の結果、及び実装体の評価結果を示す。変曲点は１０Ｅ＋４．０ｒａｄ／ｓ、貯蔵弾性率Ｇ’は１０Ｅ＋４．３Ｐａ、η’の傾きは１０の１乗未満であり、アンダーフィルフィルムは、非ビンガム流動性を示さなかった。このアンダーフィルフィルムを用いて作製した実装体のボイドの評価は○、ハンダ接合の評価は×であった。
　＜比較例２＞
　膜形成樹脂としてのアクリルゴムポリマー（品名：テイサンレジンＳＧ－Ｐ３、ナガセケムテックス社製）を４０質量部、アクリル樹脂（品名：オクゾールＥＡ－０２００、大阪有機化学社製）を９６質量部、有機過酸化物（品名：パーヘキサＶ、日油社製）を５質量部、フィラー（品名：アエロジルＲ２０２、日本アエロジル社製）を１５質量部配合し、アクリル／エポキシが５０／５０の樹脂組成物を調製した。これを、剥離処理されたＰＥＴ（Polyethylene terephthalate）にバーコーターを用いて塗布し、８０℃のオーブンで３分間乾燥させ、厚み５０μｍのアンダーフィルフィルムを作製した（カバー剥離ＰＥＴ（２５μｍ）／アンダーフィルフィルム（５０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　表１に、アンダーフィルフィルムの動的粘弾性測定の結果、及び実装体の評価結果を示す。変曲点は明確ではなく、１０Ｅ＋０２ｒａｄ／ｓ以下の貯蔵弾性率Ｇ’は１０Ｅ＋６．５Ｐａ、１０Ｅ＋０２ｒａｄ／ｓ以下のη’の傾きは１０の１乗超であり、アンダーフィルフィルムは、非ビンガム流動性を示さなかった。このアンダーフィルフィルムを用いて作製した実装体のボイドの評価は×、ハンダ接合の評価は×であった。
Figure JPOXMLDOC01-appb-T000001
　実施例のように溶融時に非ビンガム流動性を示すアンダーフィルフィルムを用いることにより、ボイドレス実装及び良好なハンダ接合性を実現することができた。
　１　ウエハ、　２　アンダーフィルフィルム、　３　治具、　４　ブレード、　１０　半導体チップ、１１　半導体、１２　電極、１３　ハンダ、２０　アンダーフィル材、２１　第１の接着剤層、２２　第２の接着剤層、　３０　回路基板、３１　基材、３２　対向電極

Claims (9)

  1. 　ハンダ付き電極が形成された半導体チップを、ハンダ付き電極と対向する対向電極が形成された電子部品に搭載する前に、半導体チップに予め貼り合わされるアンダーフィル材であって、
    　エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有し、
    　６０℃以上１００℃以下のいずれかの温度で、非ビンガム流動性を示し、
    　動的粘弾性測定における貯蔵弾性率Ｇ’が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、該変曲点以下の角周波数における貯蔵弾性率Ｇ’が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下であるアンダーフィル材。
  2. 　前記動的粘弾性測定における動的粘性率η’が、前記変曲点以下の角周波数に対して１０の１乗の傾きで反比例する請求項１記載のアンダーフィル材。
  3. 　前記変曲点以下の角周波数における貯蔵弾性率Ｇ’が、一定値である請求項１又は２記載のアンダーフィル材。
  4. 　前記エポキシ樹脂が、グリシジルエーテル型エポキシ樹脂であり、
    　前記酸無水物が、脂環式酸無水物である請求項１又は２記載のアンダーフィル材。
  5. 　前記エポキシ樹脂が、グリシジルエーテル型エポキシ樹脂であり、
    　前記酸無水物が、脂環式酸無水物である請求項３記載のアンダーフィル材。
  6. 　前記アクリル樹脂が、フルオレン系アクリレートであり、
    　前記有機過酸化物が、パーオキシケタールである請求項１又は２記載のアンダーフィル材。
  7. 　前記アクリル樹脂が、フルオレン系アクリレートであり、
    　前記有機過酸化物が、パーオキシケタールである請求項３記載のアンダーフィル材。
  8. 　前記アクリル樹脂が、フルオレン系アクリレートであり、
    　前記有機過酸化物が、パーオキシケタールである請求項４記載のアンダーフィル材。
  9. 　ハンダ付き電極が形成され、該電極面にアンダーフィル材が貼り合わされた半導体チップを、前記ハンダ付き電極と対向する対向電極が形成された電子部品に搭載する搭載工程と、
    　前記半導体チップと前記電子部品とを熱圧着する熱圧着工程とを有し、
    　前記アンダーフィル材は、エポキシ樹脂と、酸無水物と、アクリル樹脂と、有機過酸化物とを含有し、６０℃以上１００℃以下のいずれかの温度で、非ビンガム流動性を示し、動的粘弾性測定における貯蔵弾性率Ｇ’が、１０Ｅ＋０２ｒａｄ／ｓ以下の角周波数領域に変曲点を有し、該変曲点以下の角波数における貯蔵弾性率Ｇ’が、１０Ｅ＋０５Ｐａ以上１０Ｅ＋０６Ｐａ以下である半導体装置の製造方法。
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CN108140732B (zh) * 2015-07-29 2021-12-21 汉高知识产权控股有限责任公司 含阻挡膜的制品及其用于3d tsv封装体用预施加底部填充膜的用途
US11203181B2 (en) 2015-07-29 2021-12-21 Henkel Ag & Co. Kgaa Barrier film-containing format and the use thereof for pre-applied underfill film for 3D TSV packages
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JP7413804B2 (ja) 2020-02-03 2024-01-16 三菱ケミカル株式会社 粘接着剤組成物、粘接着剤、粘接着シート、及び積層体

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US20160017191A1 (en) 2016-01-21
JP6069142B2 (ja) 2017-02-01
US9840645B2 (en) 2017-12-12
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TWI611526B (zh) 2018-01-11
CN105283948A (zh) 2016-01-27

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