WO2015045877A1 - 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
WO2015045877A1
WO2015045877A1 PCT/JP2014/073965 JP2014073965W WO2015045877A1 WO 2015045877 A1 WO2015045877 A1 WO 2015045877A1 JP 2014073965 W JP2014073965 W JP 2014073965W WO 2015045877 A1 WO2015045877 A1 WO 2015045877A1
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Prior art keywords
underfill material
reaction rate
underfill
semiconductor chip
reach
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PCT/JP2014/073965
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English (en)
French (fr)
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浩伸 森山
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デクセリアルズ株式会社
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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 US14/423,881 priority Critical patent/US9653371B2/en
Priority to KR1020157003774A priority patent/KR102321668B1/ko
Priority to CN201480002243.7A priority patent/CN104956471B/zh
Priority to EP14848144.3A priority patent/EP3051580B1/en
Publication of WO2015045877A1 publication Critical patent/WO2015045877A1/ja
Priority to US15/486,663 priority patent/US10062625B2/en

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    • H01L23/293—Organic, e.g. plastic
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    • H01L2225/00—Details relating to assemblies covered by the group H01L25/00 but not provided for in its subgroups
    • H01L2225/03—All the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/648 and H10K99/00
    • H01L2225/04—All the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/648 and H10K99/00 the devices not having separate containers
    • H01L2225/065—All the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/648 and H10K99/00 the devices not having separate containers the devices being of a type provided for in group H01L27/00
    • H01L2225/06503—Stacked arrangements of devices
    • H01L2225/06541—Conductive via connections through the device, e.g. vertical interconnects, through silicon via [TSV]
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L24/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/73—Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/74—Apparatus for manufacturing arrangements for connecting or disconnecting semiconductor or solid-state bodies
    • H01L24/75—Apparatus for connecting with bump connectors or layer connectors
    • H—ELECTRICITY
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2924/06—Polymers
    • H01L2924/0635—Acrylic polymer
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H01L2924/186—Material
    • H—ELECTRICITY
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    • H01L2924/20—Parameters
    • H01L2924/201—Temperature ranges
    • H01L2924/20102—Temperature range 0 C=<T<60 C, 273.15 K =<T< 333.15K
    • H—ELECTRICITY
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    • H01L2924/20103—Temperature range 60 C=<T<100 C, 333.15 K =< T< 373.15K
    • H—ELECTRICITY
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/201—Temperature ranges
    • H01L2924/20104—Temperature range 100 C=<T<150 C, 373.15 K =< T < 423.15K

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.
  • thermosetting adhesive using an epoxy resin as an adhesive for joining solder bumps has been devised.
  • a compounding composition using various curing agents such as phenol, acid anhydride, and amine curing agent as an epoxy resin curing agent has been devised (see, for example, Patent Document 2).
  • the present invention has been proposed in view of such conventional circumstances, and provides an underfill material that realizes voidless mounting and good solderability, and a method of manufacturing a semiconductor device using the underfill material.
  • the present inventor has found that the time until the first reaction rate is reached for a predetermined time or less, and the time until the second reaction rate higher than the first reaction rate is the predetermined time. As a result of the above, it has been found that voidless mounting and good solderability can be obtained, and the present invention has been completed.
  • the present invention is an underfill material that is preliminarily bonded to a semiconductor chip before mounting the semiconductor chip on which the soldered electrode is formed on an electronic component on which the counter electrode facing the soldered electrode is formed.
  • the time to reach 20% of the reaction rate at 240 ° C. calculated by the Ozawa method using a differential scanning calorimeter containing an epoxy resin and a curing agent is 2.0 sec or less, and the reaction rate The time to reach 60% is 3.0 sec or more.
  • 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. And a thermocompression bonding process for thermocompression bonding the semiconductor chip and the electronic component.
  • the underfill material contains an epoxy resin and a curing agent, and uses a differential scanning calorimeter. The time to reach 20% of the reaction rate at 240 ° C. calculated by the Ozawa method is 2.0 sec or less, and the time to reach 60% of the reaction rate is 3.0 sec or more.
  • the time to reach 20% of the reaction rate at 240 ° C. is 2.0 sec or less, and the time to reach 60% of the reaction rate is 3.0 sec or more. Can achieve excellent 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 flowchart showing a method for manufacturing a semiconductor device in the present embodiment.
  • FIG. 5 is a perspective view schematically showing a process of attaching an underfill film on the wafer.
  • FIG. 6 is a perspective view schematically showing a process of dicing the wafer.
  • FIG. 7 is a perspective view schematically showing a process of picking up a semiconductor chip.
  • FIG. 8 is a graph showing the reaction rate of the underfill film with respect to the reaction time calculated by the DSC-Ozawa method.
  • 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, and an acid anhydride.
  • 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.
  • a phenoxy resin and an acrylic rubber polymer having a glycidyl group are preferably used.
  • 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.
  • the epoxy resin examples include dicyclopentadiene type epoxy resin, glycidyl ether type epoxy resin, glycidyl amine 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 type epoxy resin, tetrabromobisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, ⁇ -naphthol novolak type epoxy resin, brominated phenol novolak type epoxy resin And so on.
  • 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 dicyclopentadiene type epoxy resin from the point of high adhesiveness and heat resistance.
  • a known curing agent for epoxy compounds can be used, and it may be latent.
  • an acid anhydride curing agent, an imidazole curing agent, an amine curing agent and the like can be used.
  • 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 aliphatic acid anhydrides such as tetrapropenyl succinic anhydride and dodecenyl succinic anhydride, alicyclic acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, phthalic anhydride, and anhydride.
  • aromatic acid anhydrides such as trimellitic 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 an aliphatic acid anhydride from the viewpoint of solder connectivity.
  • curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 salt (DBU salt), tertiary amines such as 2- (dimethylaminomethyl) phenol, phosphines such as triphenylphosphine, and metal compounds such as tin octylate.
  • imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 salt (DBU salt)
  • tertiary amines such as 2- (dimethylaminomethyl) phenol
  • phosphines such as triphenylphosphine
  • metal compounds such as tin octylate.
  • the underfill material 20 further contains an epoxy resin and an acid anhydride.
  • the acrylic resin monofunctional (meth) acrylate, bifunctional or higher (meth) acrylate can be used.
  • monofunctional (meth) acrylate 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 bisphenol F-EO modified di (meth) acrylate, bisphenol A-EO modified di (meth) acrylate, trimethylolpropane PO modified (meth) acrylate, and polyfunctional urethane (meth) acrylate. Etc. These acrylic resins may be used alone or in combination of two or more. Among these, in this Embodiment, bifunctional (meth) acrylate is used suitably.
  • organic peroxides examples include peroxyesters, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, and peroxydicarbonates. These organic peroxides may be used alone or in combination of two or more. Among these, in this Embodiment, peroxyester is used suitably.
  • 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 20 having such a structure takes 2.0 seconds to reach 20% of the reaction rate at 240 ° C. calculated by the Ozawa method using a differential scanning calorimeter (DSC).
  • the time to reach 60% of the reaction rate is 3.0 sec or more.
  • voids are generated, and when the time to reach 60% of the reaction rate is less than 3.0 sec, good solder bonding cannot be obtained.
  • the viscosity when the reaction rate is 20% is 0.2 ⁇ 10 4 Pa ⁇ s or more, and the viscosity when the reaction rate is 60% is preferably 500 ⁇ 10 4 Pa ⁇ s or less.
  • the viscosity when the reaction rate is 20% is less than 0.2 ⁇ 10 4 Pa ⁇ s, boil remains, and when the viscosity when the reaction rate is 60% exceeds 500 ⁇ 10 4 Pa ⁇ s, Good solder joints cannot be obtained.
  • the reaction rate calculation method by DSC-Ozawa method is as follows. First, the calorific value of the entire peak, the peak temperature, and the rate of change to the peak top are calculated from the uniform temperature rise data for the sample. Next, an Ozawa plot is created by taking the common logarithmic value of the heating rate on the vertical axis and the inverse value of the peak temperature on the horizontal axis, and the activation energy, frequency factor, and reaction order for the sample are obtained. Then, by creating a reaction prediction diagram from the active energy, the frequency factor, and the reaction order, it is possible to calculate the time to reach a predetermined reaction rate at a predetermined temperature.
  • 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), and the like. 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), and the like. 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. 4 is a flowchart showing a method for manufacturing a semiconductor device in 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. 5 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. 6 is a perspective view schematically showing a process of dicing the wafer. As shown in FIG. 6, 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. 7 is a perspective view schematically showing a process of picking up a semiconductor chip. As shown in FIG. 7, 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 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.
  • the temperature raising 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.
  • 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 bonder head is kept at a certain height by the elastic modulus of the resin up to the melting start temperature of the underfill film after being mounted, and then lowered at a stroke by the resin melting accompanying the temperature rise, Reach the lowest point.
  • This lowest point is determined by the relationship between the head lowering speed and the resin curing speed.
  • the height of the head gradually increases due to the thermal expansion of the resin and the head.
  • the manufacturing method of the semiconductor device in the present embodiment reaches 20% of the reaction rate at 240 ° C. calculated by the Ozawa method using the differential scanning calorimeter, containing the epoxy resin and the curing agent.
  • an underfill material having a time of 2.0 sec or less and a time to reach 60% of the reaction rate of 3.0 sec or more to a semiconductor chip on which a soldered electrode is formed, Mounting and good solderability can be realized.
  • 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, the time to reach a predetermined reaction rate was calculated by the DSC-Ozawa method, and the viscosity at the predetermined reaction rate was calculated.
  • the first IC chip having the soldered electrode and the second IC chip having the electrode facing the first IC chip are connected to produce a mounting body, and evaluation of voids and solder bonding properties is performed. did.
  • the present invention is not limited to these examples.
  • the fabrication of the mounting body, the time for reaching the predetermined reaction rate, the viscosity calculation for the predetermined reaction rate, the evaluation of voids, and the evaluation of solder bonding were performed as follows.
  • the underfill film was bonded on the wafer with a press machine at 50 ° C. to 0.5 MPa, and dancing was performed to obtain a first IC chip having a soldered electrode.
  • the first IC chip has a size of 7 mm ⁇ , a thickness of 200 ⁇ m, and a peripheral arrangement in which solder (Sn-3.5Ag, melting point 221 ° C.) having a thickness of 10 ⁇ m is formed at the tip of an electrode made of Cu having a thickness of 10 ⁇ m.
  • solder Sn-3.5Ag, melting point 221 ° C.
  • bumps ⁇ 30 ⁇ m, 85 ⁇ m pitch, 280 pins).
  • the second IC chip opposite to this has a size of 8 mm ⁇ and a thickness of 100 ⁇ m, and a 10 ⁇ m thick solder (Sn-3.5Ag, melting point) at the tip of an electrode made of 10 ⁇ m thick Cu. 221 ° C.) having peripherally arranged bumps ( ⁇ 30 ⁇ m, 85 ⁇ m pitch, 280 pins).
  • the first IC chip was mounted on the second IC chip under the conditions of 60 ° C. ⁇ 0.5 seconds ⁇ 30N.
  • the temperature was increased from 60 ° C. to 250 ° C. for 10 seconds and thermocompression bonded (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.
  • melt viscosity was measured on conditions of 5 degree-C / min and 1 Hz using the rheometer (ARES made from TA company). Further, using a differential scanning calorimeter (DSC), the calorific value of the entire peak, the peak temperature, and the rate of change to the peak top were obtained under the condition of 5 ° C./min. The rate of change is a value obtained by dividing the amount of heat up to the peak temperature by the amount of heat of the entire peak.
  • DSC differential scanning calorimeter
  • the temperature corresponding to the 20% reaction rate and the temperature corresponding to the 60% reaction rate are obtained from the DSC data, the melt viscosity corresponding to the temperature is obtained from the rheometer data, and the melt viscosity corresponding to the reaction rate of 20% and 60% is obtained. Asked.
  • Example 1 As shown in Table 1, 5.0 parts by mass of acrylic rubber polymer (product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX) and 10.0 parts by mass of phenoxy resin (product name: PKHH, manufactured by Union Carbide) 15.0 parts by mass of epoxy resin (product name: HP7200H, manufactured by Dainippon Ink Chemical Co., Ltd.), 9.0 parts by mass of acid anhydride (product name: MH-700, manufactured by Shin Nippon Chemical Co., Ltd.), and imidazole (product name: 2MZ) -A, 0.3 parts by mass of Shikoku Kasei Kogyo Co., Ltd., 24.0 parts by mass of acrylic resin (product name: DCP, Shin-Nakamura Chemical Co., Ltd.), initiator (product name: Perbutyl Z, manufactured by NOF Corporation) 0.3 parts by mass, 31.5 parts by mass of filler A (product name: SO-E5, manufactured by Admatex) and 5.0
  • peeled PET Polyethylene terephthalate
  • underfill film having a thickness of 40 ⁇ m (cover peeled PET (25 ⁇ m) / underfill).
  • the time to reach 20% reaction rate of the underfill film of Example 1 was 0.04 sec, and the time to reach 60% reaction rate was 4.83 sec.
  • the melt viscosity with a reaction rate of 20% was 5.5E + 04 Pa ⁇ s, and the melt viscosity with a reaction rate of 60% was 1.8E + 06 Pa ⁇ s.
  • the evaluation of a void was (circle) and evaluation of solder joint property was (circle).
  • Example 2 As shown in Table 1, 5.0 parts by mass of acrylic rubber polymer (product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX) and 10.0 parts by mass of phenoxy resin (product name: PKHH, manufactured by Union Carbide) 47.5 parts by mass of epoxy resin (product name: HP7200H, manufactured by Dainippon Ink Chemical Co., Ltd.), 1.0 part by mass of imidazole (product name: 2MZ-A, manufactured by Shikoku Kasei Kogyo Co., Ltd.), filler A (product name: SO- 31.5 parts by mass of E5 (manufactured by Admatechs) and 5.0 parts by mass of filler B (product name: Aerosil RY200, Nippon Aerosil Co., Ltd.) were blended to prepare a resin composition of an underfill film.
  • acrylic rubber polymer product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX
  • phenoxy resin product name:
  • peeled PET Polyethylene terephthalate
  • underfill film having a thickness of 40 ⁇ m (cover peeled PET (25 ⁇ m) / underfill).
  • the time to reach 20% reaction rate of the underfill film of Example 2 was 0.58 sec, and the time to reach 60% reaction rate was 4.80 sec.
  • the melt viscosity at a reaction rate of 20% was 5.6E + 04 Pa ⁇ s, and the melt viscosity at a reaction rate of 60% was 1.4E + 06 Pa ⁇ s.
  • the evaluation of a void was (circle) and evaluation of solder joint property was (circle).
  • Example 3> As shown in Table 1, 5.0 parts by mass of acrylic rubber polymer (product name: Teisan Resin SG-P3, manufactured by Nagase ChemteX) and 10.0 parts by mass of phenoxy resin (product name: PKHH, manufactured by Union Carbide) , 27.0 parts by mass of epoxy resin (product name: HP7200H, manufactured by Dainippon Ink Chemical Co., Ltd.), 16.2 parts by mass of acid anhydride (product name: MH-700, manufactured by Shin Nippon Chemical Co., Ltd.), imidazole (product name: 2MZ) -A, 0.5 parts by mass of Shikoku Kasei Kogyo Co., Ltd., 4.8 parts by mass of acrylic resin (product name: DCP, Shin-Nakamura Chemical Co., Ltd.), initiator (product name: Perbutyl Z, manufactured by NOF Corporation) 0.1 part by mass, 31.5 parts by mass of filler A (product name: SO-E5, manufactured by Admatex), and
  • peeled PET Polyethylene terephthalate
  • underfill film having a thickness of 40 ⁇ m (cover peeled PET (25 ⁇ m) / underfill).
  • the time to reach the reaction rate of 20% of the underfill film of Example 3 was 1.71 sec, and the time to reach the reaction rate of 60% was 8.18 sec.
  • the melt viscosity with a reaction rate of 20% was 6.3E + 04 Pa ⁇ s, and the melt viscosity with a reaction rate of 60% was 1.6E + 06 Pa ⁇ s.
  • the evaluation of a void was (circle) and evaluation of solder joint property was (circle).
  • peeled PET Polyethylene terephthalate
  • underfill film having a thickness of 40 ⁇ m (cover peeled PET (25 ⁇ m) / underfill).
  • the time to reach 20% reaction rate of the underfill film of Comparative Example 1 was 2.45 sec, and the time to reach 60% reaction rate was 6.48 sec.
  • the melt viscosity at a reaction rate of 20% was 1.0E + 03 Pa ⁇ s, and the melt viscosity at a reaction rate of 60% was 2.3E + 05 Pa ⁇ s.
  • the evaluation of a void was x and the evaluation of solder joint property was o.
  • peeled PET Polyethylene terephthalate
  • underfill film having a thickness of 40 ⁇ m (cover peeled PET (25 ⁇ m) / underfill).
  • the time to reach 20% reaction rate of the underfill film of Comparative Example 2 was 0.02 sec, and the time to reach 60% reaction rate was 0.07 sec.
  • the melt viscosity with a reaction rate of 20% was 1.1E + 06 Pa ⁇ s, and the melt viscosity with a reaction rate of 60% was 1.0E + 07 Pa ⁇ s or more.
  • the evaluation of a void was (circle) and evaluation of solder joint property was x.
  • Comparative Example 1 voids occurred because the time to reach 20% of the reaction rate was over 2.0 sec. In Comparative Example 1, since the viscosity when the reaction rate was 20% was less than 0.2 ⁇ 10 4 Pa ⁇ s, the boil remained.
  • Comparative Example 2 since the time to reach 60% of the reaction rate was less than 3.0 seconds, good solder joint could not be obtained. Further, in Comparative Example 2, since the viscosity when the reaction rate is 60% is more than 500 ⁇ 10 4 Pa ⁇ s, good solder bonding cannot be obtained.
  • the time to reach 20% of the reaction rate at 240 ° C. is 2.0 sec or less, and the time to reach 60% of the reaction rate is 3.0 sec or more. Boydless mounting and good solderability were achieved.

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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す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を提供する。エポキシ樹脂と、硬化剤とを含有し、示差走査熱量計を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、該反応率の６０％に到達する時間が、３．０ｓｅｃ以上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２７日に出願された日本特許出願番号特願２０１３－２０１６１３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。
　このような実装方法において、ハンダバンプを接合する接着剤としてエポキシ樹脂を用いた熱硬化接着剤が考案されている。この接着剤において、エポキシ樹脂の硬化剤としてフェノール、酸無水物、アミン系硬化剤等の様々な硬化剤を用いた配合組成が考案されている（例えば、特許文献２参照。）。
　高温圧着のボイド対策として、硬化剤として過酸化物等を用い、硬化速度を速くすることで、ボイドレスが可能であるものの、ハンダ接合性が悪化してしまう。
特開２００５－２８７３４号公報 特開２０１０－１０６６９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す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を提供する。
　本件発明者は、鋭意検討を行った結果、第１の反応率に至るまでの時間が所定時間以下であり、第１の反応率よりも高い第２の反応率に至るまでの時間が所定時間以上であることにより、ボイドレス実装及び良好なハンダ接合性が得られることを見出し、本発明を完成させるに至った。
　すなわち、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、硬化剤とを含有し、示差走査熱量計を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、該反応率の６０％に到達する時間が、３．０ｓｅｃ以上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、硬化剤とを含有し、示差走査熱量計を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、該反応率の６０％に到達する時間が、３．０ｓｅｃ以上であることを特徴とする。
　本発明によれば、２４０℃での反応率の２０％に到達する時間が２．０ｓｅｃ以下であり、反応率の６０％に到達する時間が３．０ｓｅｃ以上であることにより、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。
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、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は、ＤＳＣ－小沢法により算出された反応時間に対するアンダーフィルフィルムの反応率を示すグラフである。
　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、フェノキシ樹脂、及び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、ジシクロペンタジエン型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、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、ジシクロペンタジエン型エポキシ樹脂を用いることが好ましい。
　硬化剤としては、エポキシ化合物の硬化剤として公知のものを使用でき、潜在性であってもよい。例えば、酸無水物系硬化剤、イミダゾール系硬化剤、アミン系硬化剤などを使用できる。
　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、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、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、脂肪族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、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、１，８－ジアザビシクロ（５，４，０）ウンデセン－７塩（ＤＢＵ塩）、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。
　また、アンダーフィル材２０は、エポキシ樹脂と、酸無水物とをさらに含有する。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、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、２官能（メタ）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、パーオキシエステル、パーオキシケタール、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、パーオキシエステ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。
　このような構成からなるアンダーフィル材２０は、示差走査熱量計（ＤＳＣ：Differential Scanning Calorimeter）を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、反応率の６０％に到達する時間が、３．０ｓｅｃ以上である。反応率の２０％に到達する時間が２．０ｓｅｃ超の場合、ボイドが発生し、反応率の６０％に到達する時間が３．０ｓｅｃ未満の場合、良好なハンダ接合が得られない。
　また、反応率が２０％のときの粘度は、０．２×１０４Ｐａ・ｓ以上であり、反応率が６０％のときの粘度は、５００×１０４Ｐａ・ｓ以下であることが好ましい。反応率が２０％のときの粘度が０．２×１０４Ｐａ・ｓ未満の場合、ボイルが残ってしまい、反応率が６０％のときの粘度が５００×１０４Ｐａ・ｓ超の場合、良好なハンダ接合が得られない。
　ＤＳＣ－小沢法による反応率の算出方法は、次の通りである。先ず、サンプルについての等速昇温データよりピーク全体の熱量、ピーク温度及びピークトップまでの変化率を算出する。次に、昇温スピードの常用対数値を縦軸にとり、ピーク温度の逆数値を横軸にとることにより小沢プロットを作成し、サンプルについての活性化エネルギー、頻度因子、及び反応次数を求める。そして、活性エネルギー、頻度因子及び反応次数より反応予測図を作成することにより、所定温度での所定反応率に到達する時間を算出することができる。
　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４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４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５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６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６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７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７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。
　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。
　また、熱圧着工程Ｓ４において、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。
　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、硬化剤とを含有し、示差走査熱量計を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、反応率の６０％に到達する時間が、３．０ｓｅｃ以上であるアンダーフィル材を、ハンダ付き電極が形成された半導体チップ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、ＤＳＣ－小沢法により所定反応率に到達する時間を算出し、所定反応率の粘度を算出した。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第１のＩＣチップと、これに対向する電極を有する第２のＩＣチップとを接続させて実装体を作製し、ボイド及びハンダ接合性について評価した。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。
　実装体の作製、所定反応率に到達する時間を算出、所定反応率の粘度算出、ボイドの評価及びハンダ接合性の評価は、次のように行った。
　［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第１のＩＣチップを得た。
　第１のＩＣチップは、その大きさが７ｍｍ□、厚み２００μｍであり、厚み１０μｍのＣｕからなる電極の先端に厚み１０μｍ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、これに対向する第２のＩＣチップは、同様に、その大きさは８ｍｍ□、厚み１００μｍであり、厚み１０μｍのＣｕからなる電極の先端に厚み１０μｍ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。
　次に、フリップチップボンダーを用いて、６０℃－０．５秒－３０Ｎの条件で第２のＩＣチップ上に第１の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、１０秒間に６０℃から２５０℃まで温度を上げて熱圧着した（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。
　［所定反応率に到達する時間の算出］
　所定反応率に到達する時間の算出は、以下の手順により算出した。
（１）示差走査熱量計（ＤＳＣ）を使用して、同装置に添付されているＤＳＣ小沢法ソフトウエアのマニュアルの記述に従い、各試料についての等速昇温データ（昇温スピード５℃／ｍｉｎ，１０℃／ｍｉｎ，２０℃／ｍｉｎ）よりピーク全体の熱量、ピーク温度、及びピークトップまでの変化率を求めた。変化率は、ピーク温度までの熱量をピーク全体の熱量で除した値である。
（２）昇温スピードの常用対数値を縦軸にとり、ピーク温度の逆数値を横軸にとることにより小沢プロットを作成後、各試料についての活性化エネルギー、頻度因子、反応次数を求めた。
（３）（２）で求めた活性エネルギー、頻度因子及び反応次数より反応予測図を作成し、この図より２４０℃での２０％の反応率、及び６０％の反応率に到達する時間を算出した。
　［所定反応率の粘度算出］
　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、５℃／ｍｉｎ、１Ｈｚの条件で溶融粘度を測定した。また示差走査熱量計（ＤＳＣ）を使用して、５℃／ｍｉｎの条件でピーク全体の熱量、ピーク温度、及びピークトップまでの変化率を求めた。変化率は、ピーク温度までの熱量をピーク全体の熱量で除した値である。ＤＳＣデータより２０％反応率に対応する温度、及び６０％反応率に対応する温度を求め、その温度に対応する溶融粘度をレオメータデータから求め、反応率２０％、６０％に対応する溶融粘度を求めた。
　［ボイドの評価］
　各実装体について、ＳＡＴ（Scanning Acoustic Tomograph, 超音波映像装置）を用いて観察し、ボイドがＩＣチップ面積の５％以下であるものを○、ボイドがＩＣチップ面積の５％超であるものを×とした。
　［ハンダ接合性の評価］
　各実装体を切断し、断面研磨を行い、電極間のハンダの接合界面をＳＥＭ（Scanning Electron Microscope）観察した。ハンダの接合界面がない場合を○、樹脂を挟み込んでしまい、ハンダの接合界面がある場合を×と評価した。
　＜実施例１＞
　表１に示すように、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５．０質量部、フェノキシ樹脂（品名：ＰＫＨＨ、ユニオンカーバイド社製）を１０．０質量部、エポキシ樹脂（品名：ＨＰ７２００Ｈ、大日本インキ化学社製）を１５．０質量部、酸無水物（品名：ＭＨ－７００、新日本理化社製)を９．０質量部、イミダゾール（品名：２ＭＺ－Ａ、四国化成工業社製）を０．３質量部、アクリル樹脂（品名：ＤＣＰ、新中村化学社製）を２４．０質量部、開始剤（品名：パーブチルＺ、日本油脂社製）を０．３質量部、フィラーＡ（品名：ＳＯ－Ｅ５、アドマテックス社製）を３１．５質量部、及びフィラーＢ（品名：アエロジルＲＹ２００、日本アエロジル社製）を５．０質量部配合し、アンダーフィルフィルム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４０μｍ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（４０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　図８に示すように、実施例１のアンダーフィルフィルムの２０％の反応率に到達する時間は０．０４ｓｅｃであり、６０％の反応率に到達する時間は４．８３ｓｅｃであった。また、２０％の反応率の溶融粘度は５．５Ｅ＋０４Ｐａ・ｓであり、６０％の反応率の溶融粘度は１．８Ｅ＋０６Ｐａ・ｓであった。また、ボイドの評価は○であり、ハンダ接合性の評価は○であった。
　＜実施例２＞
　表１に示すように、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５．０質量部、フェノキシ樹脂（品名：ＰＫＨＨ、ユニオンカーバイド社製）を１０．０質量部、エポキシ樹脂（品名：ＨＰ７２００Ｈ、大日本インキ化学社製）を４７．５質量部、イミダゾール（品名：２ＭＺ－Ａ、四国化成工業社製）を１．０質量部、フィラーＡ（品名：ＳＯ－Ｅ５、アドマテックス社製）を３１．５質量部、及びフィラーＢ（品名：アエロジルＲＹ２００、日本アエロジル社製）を５．０質量部配合し、アンダーフィルフィルム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４０μｍ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（４０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　図８に示すように、実施例２のアンダーフィルフィルムの２０％の反応率に到達する時間は０．５８ｓｅｃであり、６０％の反応率に到達する時間は４．８０ｓｅｃであった。また、２０％の反応率の溶融粘度は５．６Ｅ＋０４Ｐａ・ｓであり、６０％の反応率の溶融粘度は１．４Ｅ＋０６Ｐａ・ｓであった。また、ボイドの評価は○であり、ハンダ接合性の評価は○であった。
　＜実施例３＞
　表１に示すように、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５．０質量部、フェノキシ樹脂（品名：ＰＫＨＨ、ユニオンカーバイド社製）を１０．０質量部、エポキシ樹脂（品名：ＨＰ７２００Ｈ、大日本インキ化学社製）を２７．０質量部、酸無水物（品名：ＭＨ－７００、新日本理化社製)を１６．２質量部、イミダゾール（品名：２ＭＺ－Ａ、四国化成工業社製）を０．５質量部、アクリル樹脂（品名：ＤＣＰ、新中村化学社製）を４．８質量部、開始剤（品名：パーブチルＺ、日本油脂社製）を０．１質量部、フィラーＡ（品名：ＳＯ－Ｅ５、アドマテックス社製）を３１．５質量部、及びフィラーＢ（品名：アエロジルＲＹ２００、日本アエロジル社製）を５．０質量部配合し、アンダーフィルフィルム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４０μｍ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（４０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　図８に示すように、実施例３のアンダーフィルフィルムの２０％の反応率に到達する時間は１．７１ｓｅｃであり、６０％の反応率に到達する時間は８．１８ｓｅｃであった。また、２０％の反応率の溶融粘度は６．３Ｅ＋０４Ｐａ・ｓであり、６０％の反応率の溶融粘度は１．６Ｅ＋０６Ｐａ・ｓであった。また、ボイドの評価は○であり、ハンダ接合性の評価は○であった。
　＜比較例１＞
　表１に示すように、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５．０質量部、フェノキシ樹脂（品名：ＰＫＨＨ、ユニオンカーバイド社製）を１０．０質量部、エポキシ樹脂（品名：ＨＰ７２００Ｈ、大日本インキ化学社製）を３０．０質量部、酸無水物（品名：ＭＨ－７００、新日本理化社製)を１８．０質量部、イミダゾール（品名：２ＭＺ－Ａ、四国化成工業社製）を０．５質量部、フィラーＡ（品名：ＳＯ－Ｅ５、アドマテックス社製）を３１．５質量部、及びフィラーＢ（品名：アエロジルＲＹ２００、日本アエロジル社製）を５．０質量部配合し、アンダーフィルフィルム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４０μｍ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（４０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　図８に示すように、比較例１のアンダーフィルフィルムの２０％の反応率に到達する時間は２．４５ｓｅｃであり、６０％の反応率に到達する時間は６．４８ｓｅｃであった。また、２０％の反応率の溶融粘度は１．０Ｅ＋０３Ｐａ・ｓであり、６０％の反応率の溶融粘度は２．３Ｅ＋０５Ｐａ・ｓであった。また、ボイドの評価は×であり、ハンダ接合性の評価は○であった。
　＜比較例２＞
　表１に示すように、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５．０質量部、フェノキシ樹脂（品名：ＰＫＨＨ、ユニオンカーバイド社製）を１０．０質量部、アクリル樹脂（品名：ＤＣＰ、新中村化学社製）を４８．０質量部、開始剤（品名：パーブチルＺ、日本油脂社製）を０．５質量部、フィラーＡ（品名：ＳＯ－Ｅ５、アドマテックス社製）を３１．５質量部、及びフィラーＢ（品名：アエロジルＲＹ２００、日本アエロジル社製）を５．０質量部配合し、アンダーフィルフィルム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４０μｍ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（４０μｍ）／ベース剥離ＰＥＴ（５０μｍ））。
　図８に示すように、比較例２のアンダーフィルフィルムの２０％の反応率に到達する時間は０．０２ｓｅｃであり、６０％の反応率に到達する時間は０．０７ｓｅｃであった。また、２０％の反応率の溶融粘度は１．１Ｅ＋０６Ｐａ・ｓであり、６０％の反応率の溶融粘度は１．０Ｅ＋０７Ｐａ・ｓ以上であった。また、ボイドの評価は○であり、ハンダ接合性の評価は×であった。
Figure JPOXMLDOC01-appb-T000001
　比較例１は、反応率の２０％に到達する時間が２．０ｓｅｃ超であるため、ボイドが発生した。また、比較例１は、反応率が２０％のときの粘度が０．２×１０４Ｐａ・ｓ未満であるため、ボイルが残っていた。
　また、比較例２は、反応率の６０％に到達する時間が３．０ｓｅｃ未満であるため、良好なハンダ接合が得られなかった。また、比較例２は、反応率が６０％のときの粘度が５００×１０４Ｐａ・ｓ超であるため、良好なハンダ接合が得られなかった。
　一方、実施例１～３は、２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、反応率の６０％に到達する時間が、３．０ｓｅｃ以上であるため、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 (8)

  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、硬化剤とを含有し、
    　示差走査熱量計を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、該反応率の６０％に到達する時間が、３．０ｓｅｃ以上であるアンダーフィル材。
  2. 　前記反応率が２０％のときの粘度が、０．２×１０４Ｐａ・ｓ以上であり、前記反応率が６０％のときの粘度が、５００×１０４Ｐａ・ｓ以下である請求項１記載のアンダーフィル材。
  3. 　前記エポキシ樹脂が、ジシクロペンタジエン型エポキシ樹脂であり、
    　前記硬化剤が、脂肪族酸無水物又はイミダゾール系硬化剤である請求項１又は２記載のアンダーフィル材。
  4. 　アクリル樹脂と、有機過酸化物とをさらに含有する請求項１又は２記載のアンダーフィル材。
  5. 　アクリル樹脂と、有機過酸化物とをさらに含有する請求項３記載のアンダーフィル材。
  6. 　前記アクリル樹脂が、２官能（メタ）アクリレートであり、
    　前記有機過酸化物が、パーオキシエステルである請求項４に記載のアンダーフィル材。
  7. 　前記アクリル樹脂が、２官能（メタ）アクリレートであり、
    　前記有機過酸化物が、パーオキシエステルである請求項５に記載のアンダーフィル材。
  8. 　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、酸無水物とを含有し、示差走査熱量計を用いた小沢法により算出された２４０℃での反応率の２０％に到達する時間が、２．０ｓｅｃ以下であり、該反応率の６０％に到達する時間が、３．０ｓｅｃ以上である半導体装置の製造方法。
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