WO2014046089A1 - 接続構造体の製造方法及び異方性導電接着剤 - Google Patents

接続構造体の製造方法及び異方性導電接着剤 Download PDF

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Publication number
WO2014046089A1
WO2014046089A1 PCT/JP2013/075039 JP2013075039W WO2014046089A1 WO 2014046089 A1 WO2014046089 A1 WO 2014046089A1 JP 2013075039 W JP2013075039 W JP 2013075039W WO 2014046089 A1 WO2014046089 A1 WO 2014046089A1
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Prior art keywords
solder particles
anisotropic conductive
conductive adhesive
electronic component
terminal
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PCT/JP2013/075039
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English (en)
French (fr)
Inventor
秀次 波木
士行 蟹澤
明 石神
青木　正治
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デクセリアルズ株式会社
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Publication of WO2014046089A1 publication Critical patent/WO2014046089A1/ja

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    • H—ELECTRICITY
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    • H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
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    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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    • 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
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    • H01L2924/07811—Extrinsic, i.e. with electrical conductive fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0224—Conductive particles having an insulating coating
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    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10106—Light emitting diode [LED]

Definitions

  • the present technology relates to an anisotropic conductive adhesive in which conductive particles are dispersed, and a method of manufacturing a connection structure using the same.
  • a chip such as a driver IC (Integrated Circuit) or LED (Light Emitting Diode) (
  • the present invention relates to an anisotropic conductive adhesive capable of dissipating heat generated by an element, and a method for manufacturing a connection structure using the same.
  • the wire bond method is used as a method for mounting the LED element on the substrate.
  • a method using a conductive paste has been proposed as a method without using wire bonds
  • a method using an anisotropic conductive adhesive has been proposed as a method without using a conductive paste.
  • LED elements for flip-chip (FC) mounting have been developed, and gold-tin eutectic bonding is used as a method of mounting the FC mounting LED elements on a substrate.
  • a solder connection method using a solder paste is proposed as a method without using a gold-tin eutectic, and a method using an anisotropic conductive adhesive is proposed as a method without using a solder paste.
  • the thermal conductivity of the cured anisotropic conductive adhesive is about 0.2 W / (m ⁇ K)
  • the heat generated from the LED element cannot be sufficiently released to the substrate side.
  • FC mounting using an anisotropic conductive adhesive only the conductive particles in the electrical connection portion serve as a heat radiation path, so the heat dissipation is poor.
  • the above-described object can be achieved by using solder particles as the conductive particles and heating and pressing at a temperature lower than the melting point of the solder particles using an anisotropic conductive adhesive.
  • the manufacturing method of the connection structure in an embodiment of the present technology includes a thermosetting adhesive composition containing an epoxy resin and an acid anhydride, and solder particles dispersed in the thermosetting adhesive composition.
  • a step of disposing an anisotropic conductive adhesive including a terminal between the terminal of the first electronic component and the terminal of the second electronic component, and the terminal of the first electronic component and the terminal of the second electronic component Using either of these, the anisotropic conductive adhesive is pressed at a temperature lower than the melting point of the solder particles, and the solder particles are placed between the terminals of the first electronic component and the terminals of the second electronic component.
  • An anisotropic conductive adhesive includes a thermosetting adhesive composition containing an epoxy resin and an acid anhydride, and solder particles dispersed in the thermosetting adhesive composition.
  • the thermosetting adhesive composition in which the solder particles are dispersed is heated at a temperature lower than the melting point of the solder particles.
  • the surface of the solder particles is wet because the anisotropic conductive adhesive is pressed at a temperature lower than the melting point of the solder particles.
  • the whole solder particles do not melt. Therefore, although the metal bond can be secured between the solder particles and the terminal surface, the contact area does not increase more than necessary, and the occurrence of cracks and the like due to the thermal cycle test can be prevented. Further, the contact formed by the metal bond serves as a heat dissipation path. Therefore, it is possible to provide a method for manufacturing a connection structure having high connection reliability and high heat dissipation, and particularly useful for connecting LED elements.
  • Anisotropic conductive adhesive and method for producing the same> An anisotropic conductive adhesive according to an embodiment of the present technology is obtained by dispersing solder particles in a binder (thermosetting adhesive composition that is an adhesive component) containing an epoxy resin and an acid anhydride.
  • the shape is a paste, a film, or the like, and can be appropriately selected according to the purpose.
  • the solder particles are heated and pressed at a temperature lower than the melting point at the time of pressure bonding, so that the surface of the solder particles is wet.
  • the entire solder particle does not melt.
  • the contact area does not become larger than necessary, and the occurrence of cracks and the like due to the thermal cycle test can be prevented.
  • the contact formed by the metal bond serves as a heat dissipation path. Therefore, it is possible to provide a method for manufacturing a connection structure having high connection reliability and high heat dissipation, and particularly useful for connecting LED elements.
  • solder particles are specified in, for example, JIS Z 3282-1999.
  • the constituent materials of the solder particles are Sn—Pb, Pb—Sn—Sb, Sn—Sb, Sn—Pb—Bi, Bi—Sn, Sn—Cu, Sn—Pb—Cu, Sn It can be appropriately selected from —In system, Sn—Ag system, Sn—Pb—Ag system, Pb—Ag system, etc. according to the electrode material and connection conditions. Further, the shape of the solder particles can be appropriately selected from granular, flake shaped, and the like. Note that the solder particles may be covered with an insulating layer in order to improve anisotropy.
  • the heating temperature at the time of heating and pressing is set lower than the melting point of the solder particles, the heating temperature at the time of this heating and pressing is the reaction start temperature of the thermosetting adhesive composition Preferably they are equal or greater.
  • the reaction temperature of the thermosetting resin adhesive composition is a general 140 ° C. to 220 ° C.
  • solder particles there are solder particles having a so-called solid phase point and a liquid phase point, and eutectic solder particles in which the solid phase point and the liquid phase point are substantially matched and grasped as one melting point.
  • any of the solder particles can be used, but when the former solder particles are used, they are heated and pressed below the solid phase point, and in the latter case, the eutectic melting point. If it is less than, it will heat-press. That is, in the present specification, the melting point of solder particles refers to a solidus temperature at which a solid phase (solid) solder starts to melt in an atmospheric pressure atmosphere.
  • the average particle size (D50) of the solder particles is preferably 1 ⁇ m to 20 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m.
  • the blending amount of the solder particles is preferably in the range of 1% by volume to 50% by volume with respect to the total amount of the anisotropic conductive adhesive from the viewpoint of connection reliability and insulation reliability. A range of 25% by volume is preferred. When the blending amount of the solder particles is 3% by volume or more, connection reliability and heat dissipation are reliably ensured, and when it is 25% by volume or less, short-circuiting due to contact between adjacent solder particles can be avoided. .
  • a conductive particle in addition to solder particles, epoxy resin, phenol resin, acrylic resin, acrylonitrile / styrene (AS) resin, benzoguanamine resin, divinylbenzene resin, Metal-coated resin particles obtained by coating the surface of resin particles such as styrene resin with a metal such as Au, Ni, and Zn can be used in combination.
  • white inorganic particles are dispersed in the anisotropic conductive adhesive (thermosetting adhesive composition) according to an embodiment of the present technology.
  • the white inorganic particles are blended for the purpose of imparting light reflectivity to the anisotropic conductive adhesive and increasing some thermal conductivity in the anisotropic conductive adhesive.
  • the white inorganic particles inorganic fine particles such as metal oxides, metal nitrides, and metal sulfides are used, and the particles are preferably gray to white under natural light.
  • specific white inorganic particles it is preferable to select and use various materials from titanium oxide, boron nitride, zinc oxide, aluminum oxide, and the like.
  • the thermal conductivity of the white inorganic particles is preferably 10 W / (m ⁇ K) or more.
  • the thermal conductivity of the white inorganic particles is 10 W / (m ⁇ K) or more, the heat dissipation of the connection structure can be improved.
  • the shape of the white inorganic particles may be spherical, scaly, indeterminate, acicular, etc., but considering reflectance, it is preferably spherical or scaly.
  • the average particle diameter (D50) of the white inorganic particles is larger than the solder particles, it becomes an obstacle in connection between the terminals, and therefore it is preferable that the white inorganic particles are smaller than the solder particles.
  • the specific average particle diameter (D50) is 0.02 ⁇ m to 20 ⁇ m, more preferably 0.2 ⁇ m to 10 ⁇ m, still more preferably 0.2 ⁇ m to 1.0 ⁇ m when the white inorganic particles are spherical.
  • the total amount of anisotropic conductive adhesive is 1 to 50% by volume. %, More preferably 2% to 25% by volume.
  • thermosetting adhesive composition an adhesive composition used in a conventional anisotropic conductive adhesive or anisotropic conductive film can be used.
  • Preferred examples of the main component of the thermosetting adhesive composition include an epoxy curable adhesive mainly composed of an alicyclic epoxy compound, a heterocyclic epoxy compound, a hydrogenated epoxy compound, or the like.
  • Preferred examples of the alicyclic epoxy compound include those having two or more epoxy groups in the molecule. These may be liquid or solid. Specific examples include glycidyl hexahydrobisphenol A, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, and the like. Among them, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate is preferred because it can ensure light transmission suitable for mounting LED elements on the cured product and is excellent in rapid curing. Can be preferably used.
  • heterocyclic epoxy compound examples include an epoxy compound having a triazine ring, and particularly preferably 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4, Mention may be made of 6- (1H, 3H, 5H) -trione.
  • hydrogenated epoxy compound hydrogenated products of the above-described alicyclic epoxy compounds and heterocyclic epoxy compounds, and other known hydrogenated epoxy resins can be used.
  • the alicyclic epoxy compound, heterocyclic epoxy compound and hydrogenated epoxy compound may be used alone, but two or more kinds may be used in combination.
  • other epoxy compounds may be used in combination as long as the effects of the present technology are not impaired.
  • the curing agent with which the main agent is reacted examples include an acid anhydride, an imidazole compound, and dicyan.
  • acid anhydrides that are difficult to discolor the cured product particularly alicyclic acid anhydride-based curing agents, can be preferably used.
  • methylhexahydrophthalic anhydride etc. can be mentioned preferably.
  • the acid anhydride can function as a flux for the solder particles, and the acid anhydride may be blended in excess of the equivalent of the main epoxy resin. Specifically, from the viewpoint of reaction, 0.7 equivalent to 1.0 equivalent of acid anhydride is sufficient for 1.0 equivalent of epoxy resin. It is preferable to blend between 0.0 equivalents and 1.3 equivalents. For this reason, the acid anhydride is preferably blended in the range of 0.7 equivalents to 1.3 equivalents with respect to 1.0 equivalent of the epoxy resin. An acid anhydride may be mix
  • the anisotropic conductive adhesive having such a configuration can obtain high heat dissipation and high connection reliability while maintaining a certain contact area between the terminals in combination with a manufacturing method described later.
  • connection structure and manufacturing method thereof> Next, a connection structure using the above-described anisotropic conductive adhesive will be described.
  • the terminal of the first electronic component and the terminal of the second electronic component are connected via the conductive particles in which the conductive metal layer is formed on the surface of the resin particles. Electrically connected. Solder particles are captured (held) between the terminal of the first electronic component and the terminal of the second electronic component.
  • a chip such as a driver IC (Integrated Circuit) or LED (Light Emitting Diode) that generates heat is suitable.
  • FIG. 1 is a cross-sectional view showing a configuration example of an LED mounting body.
  • an LED element (first electronic component) and a substrate (second electronic component) on which the LED element is mounted have anisotropy in which the above-described solder particles are dispersed in an adhesive component. They are connected using a conductive adhesive.
  • the LED element includes, for example, a first conductive clad layer 12 made of, for example, n-GaN, an active layer 13 made of, for example, an In x Al y Ga 1-xy N layer, on an element substrate 11 made of, for example, sapphire, and a second conductivity type cladding layer 14 made of p-GaN, and has a so-called double heterostructure. Further, a first conductivity type electrode 12 a is provided on a part of the first conductivity type cladding layer 12, and a second conductivity type electrode 14 a is provided on a part of the second conductivity type cladding layer 14. When a voltage is applied between the first conductivity type electrode 12a and the second conductivity type electrode 14a of the LED element, carriers are concentrated on the active layer 13 and recombination causes light emission.
  • the substrate includes a circuit pattern 22 for the first conductivity type and a circuit pattern 23 for the second conductivity type on the base material 21, and positions corresponding to the first conductivity type electrode 12a and the second conductivity type electrode 14a of the LED element. Each have an electrode 22a and an electrode 23a.
  • the anisotropic conductive adhesive is one in which solder particles 31 and white inorganic particles 32 are dispersed in a binder 33 as described above.
  • the terminals (electrodes 12 a and 14 a) of the LED element and the terminals (electrodes 22 a and 23 a) of the substrate are electrically connected via solder particles 31. Further, white inorganic particles 32 are dispersed between the LED element and the substrate.
  • the heat generated in the active layer 13 of the LED element can be efficiently released to the substrate side through the solder particles 31, and the LED mounted body can be extended in life while preventing the light emission efficiency from being lowered. Further, since the white inorganic particles 32 are white or gray achromatic, the light from the active layer 13 can be reflected and high luminance can be obtained.
  • the LED element for flip-chip mounting is designed such that the terminals (electrodes 12a and 14a) of the LED element are large due to the passivation 15, so that the terminals (electrodes 12a and 14a) of the LED element are designed. ) And the terminals (circuit patterns 22 and 23) of the substrate, more solder particles 31 are captured. Thereby, the heat generated in the active layer 13 of the LED element can be released to the substrate side more efficiently.
  • the materials of the LED element terminals (12a, 14a) and the substrate terminals (22, 23) are gold (Au) or gold-tin alloy (AuSn) for eutectic bonding with the solder particles.
  • Au gold
  • AuSn gold-tin alloy
  • the terminals (12a, 14a) of the LED element and the terminals (22, 23) of the substrate both contain gold.
  • the terminal (12a, 14a) of the LED element is a gold-tin alloy and the terminal (22, 23) of the substrate is gold.
  • a mounting body manufacturing method in which an anisotropic conductive adhesive in which the above-described solder particles are dispersed in a thermosetting adhesive composition containing an epoxy resin and an acid anhydride is first.
  • a placement step of placing between the terminal of the electronic component and the terminal of the second electronic component, and using one of the terminal of the first electronic component and the terminal of the second electronic component,
  • the first electronic component and the second electronic component are used, and the anisotropic conductive adhesive is heated and pressed using a heating tool such as a heating head.
  • the heating temperature is set to be lower than the melting point of the solder particles, thereby Contact each terminal without melting.
  • a more specific heating temperature is preferably a temperature equal to or higher than the reaction start temperature of the thermosetting adhesive composition, and is preferably 15 ° C. or lower than the melting point of the solder particles.
  • the heating temperature at the time of heating press can be approximated by the temperature of the heating tool when only the heating tool is used.
  • the temperature given to the anisotropic conductive adhesive may be higher than the heating tool, so the heating tool is heated rather than based on the temperature. It is desirable to actually measure the anisotropic conductive adhesive itself using a measuring device such as a thermocouple.
  • connection structure in the above-described embodiment of the present technology, the method not using the anisotropic conductive adhesive, the problems thereof, and the like are as follows.
  • a wire bonding (WB) method As a method for mounting LED elements on a substrate, a wire bonding (WB) method is used.
  • WB method as shown in FIG. 3, the electrodes (first conductivity type electrode 104a and second conductivity type electrode 102a) of the LED element are faced up (face up), and the LED element and the substrate are electrically joined.
  • Wire bonding (WB) 301a and 301b is performed, and a die bonding material 302 is used for bonding the LED element and the substrate.
  • the LED element electrodes face toward the substrate side (face down, flip chip) as shown in FIG.
  • a conductive baset 303 (303a, 303b) represented by silver paste for electrical connection between the element and the substrate.
  • the conductive paste 303 (303a, 303b) has a weak adhesive force, reinforcement with the sealing resin 304 is necessary. Furthermore, since the curing process of the sealing resin 304 is performed by oven curing, production takes time.
  • the electrode surface of the LED element is directed to the substrate side (face down, flip chip), and the electrical connection and adhesion between the LED element and the substrate are insulative.
  • an anisotropic conductive adhesive in which conductive particles 306 are dispersed in an adhesive binder 305. Since the anisotropic conductive adhesive has a short bonding process, the production efficiency is good.
  • An anisotropic conductive adhesive is inexpensive and excellent in transparency, adhesiveness, heat resistance, mechanical strength, electrical insulation, and the like.
  • FC mounting LED element can be designed to have a large electrode area by the passivation 105, bumpless mounting is possible. Further, the light extraction efficiency is improved by providing a reflective film under the light emitting layer.
  • Gold-tin eutectic bonding is a method in which a chip electrode is formed of an alloy 307 of gold and tin, a flux is applied to a substrate, the chip is mounted and heated, and eutectic bonding is performed with the substrate electrode.
  • solder connection method has a bad yield because there is an adverse effect on reliability due to chip displacement during heating or flux that could not be cleaned.
  • advanced mounting technology is required.
  • solder connection method As a method not using gold-tin eutectic, there is a solder connection method using a solder paste for electrical connection between the electrode surface of the LED element and the substrate, as shown in FIG.
  • solder connection method since the paste has isotropic conductivity, the pn electrodes are short-circuited and the yield is poor.
  • an ACF Anisotropic conductive film in which conductive particles are dispersed in an insulating binder is used for the electrical connection and adhesion between the LED element and the substrate as shown in FIG.
  • an anisotropic conductive adhesive such as film
  • the anisotropic conductive adhesive is filled with an insulating binder between the pn electrodes. Accordingly, the yield is good because short-circuiting hardly occurs. Moreover, since the bonding process is short, the production efficiency is good.
  • the active layer 103 is located on the substrate side, so that heat is efficiently transferred to the substrate side.
  • the electrodes are joined with the conductive paste 303 (303a, 303b)
  • heat can be radiated with high efficiency, but the connection with the conductive paste 303 (303a, 303b)
  • connection reliability is poor.
  • the connection reliability is poor as described above.
  • the active paste 303 (303a, 303b) can be activated by flip chip mounting with an anisotropic conductive adhesive such as ACF or ACP (Anisotropic Conductive Paste) without using the conductive paste 303 (303a, 303b).
  • the layer 103 is disposed near the substrate side, and heat is efficiently transferred to the substrate side. Moreover, since the adhesive force is high, high connection reliability can be obtained.
  • solder particles as conductive particles in an anisotropic conductive adhesive.
  • the light is reflected by reflecting the light by including white inorganic particles. It is conceivable to increase the total luminous flux.
  • solder particles are used for the anisotropic conductive adhesive, it is possible to ensure heat dissipation as well as connection reliability. However, if the entire solder particles are melted, the contact area between the solder particles and the terminals becomes higher than necessary, and if a thermal cycle test is performed in that state, defects such as cracks occur.
  • the anisotropic conductive adhesive contains white inorganic particles
  • the anisotropic conductive adhesive containing the white inorganic particles has a thermal conductivity of 10 W / (m ⁇ k) and is somewhat thermally conductive. Since the rate is high, heat dissipation can be expected.
  • the particle diameter of the white inorganic particles is the same as or larger than that of the conductive particles, it causes connection failure between the LED element and the terminal of the substrate.
  • the white inorganic particles have a small particle size, they do not come into contact with each other between the terminals, so that they cannot serve as heat dissipation paths. After all, when trying to ensure connection reliability, it is the reality that white inorganic particles cannot contribute to heat dissipation.
  • the solder particle component is Sn-3.0Ag-0.5Cu, and its melting point (solid phase point) is 217 ° C.
  • the refractive index of the white inorganic particles is 2.71.
  • the epoxy resin curing adhesives are alicyclic epoxy resin (trade name: CEL2021P, manufactured by Daicel Chemical Industries, Ltd.) and acid anhydride (MH700, manufactured by Shin Nippon Rika Co., Ltd.), each having an equivalent of 1.0. : It is mix
  • Example 4 produced an anisotropic conductive adhesive in the same manner as in Example 1 except that the solder particles (M10, manufactured by Senju Metal Co., Ltd.) were used.
  • the component of the solder particles is Sn-5.0Sb, and its melting point (solid phase point) is 240 ° C.
  • Example 5 produced an anisotropic conductive adhesive in the same manner as in Example 1 except that no white inorganic particles were blended.
  • Comparative Example 1 is the same method as Example 1 except that conductive particles (particles obtained by electroless gold plating of 0.2 ⁇ m on acrylic resin particles, manufactured by Nippon Chemical Industry Co., Ltd.) were used instead of solder particles. An anisotropic conductive adhesive was prepared.
  • Comparative Example 3 is an anisotropic conductive adhesive similar to Example 1, except that the temperature at the time of heating and pressing is higher than the melting point of the solder, as will be described later.
  • the LED chip is aligned and mounted, and the temperature of the heating head is changed (180 ° C., 200 ° C., 220 ° C., 260 ° C.) for 60 seconds to 1 kg / kg Thermocompression bonding was performed under the conditions of chip.
  • the actual anisotropic conductive adhesive based on the temperature of the heating head was measured using a thermocouple measuring device (product name: Data Logger, manufactured by Graphtec).
  • Table 1 shows heat dissipation characteristics, optical characteristics, adhesiveness, and electrical characteristics of the obtained LED mounting body.
  • each measuring method is as follows.
  • Example 3 an LED chip having AuSn bumps was mounted on the Au electrode substrate.
  • die shear strength The die shear strength of the chip / anisotropic conductive adhesive / substrate was measured. The die shear strength is measured by scratching the mounted LED chip in the horizontal direction and measuring the strength when the chip is detached. The measurement was performed at a measurement speed of 20 ⁇ m / sec in a measurement environment of 25 ° C. As a measuring device, Bond Tester PTR-1100 (manufactured by Reska) was used.
  • Table 1 shows the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 3.
  • Example 1 solder particles (particle size: 10 ⁇ m, mp 217 ° C.) and white inorganic particles are mixed in a binder mainly composed of an epoxy resin (CEL2021P) and an acid anhydride (MH700), and the reflectance is 450 nm. Of 65% anisotropic conductive adhesive was obtained. Using this anisotropic conductive adhesive, the LED chip having the LED chip-side electrode plated with Au and the substrate having the substrate-side electrode plated with Au were heat-pressed at 200 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • the total luminous flux of this LED module was 9 lm, the thermal resistance value of the electrical connection portion was 15 K / W, and the die shear strength was 50 N / 1 mm ⁇ .
  • the LED chip side electrode and the solder particles, and the substrate side electrode and the solder particles are Au—Su eutectic bonded, and the solder particles are not crushed and spread. It was confirmed that the thickness was maintained. Further, the initial conduction characteristics and initial insulation characteristics of the LED module were good, and stable conduction characteristics were obtained even in the TCT test ( ⁇ 40 ⁇ 100).
  • Example 2 solder particles (particle size 10 ⁇ m, mp 217 ° C.) and white inorganic particles were mixed in a binder mainly composed of epoxy resin (CEL2021P) and acid anhydride (MH700), and the reflectance was 450 nm. Of 65% anisotropic conductive adhesive was obtained. Using this anisotropic conductive adhesive, an LED chip with an Au plating on the LED chip side electrode and a substrate with an Au plating on the substrate side electrode were hot-pressed at 180 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • the total luminous flux of this LED module was 9 lm, the thermal resistance value of the electrical connection portion was 15 K / W, and the die shear strength was 50 N / 1 mm ⁇ .
  • the LED chip side electrode and the solder particles, and the substrate side electrode and the solder particles are Au—Su eutectic bonded, and the solder particles are not crushed and spread. It was confirmed that the thickness was maintained. Further, the initial conduction characteristics and initial insulation characteristics of the LED module were good, and stable conduction characteristics were obtained even in the TCT test ( ⁇ 40 ⁇ 100).
  • Example 3 solder particles (particle size 10 ⁇ m, mp 217 ° C.) and white inorganic particles were mixed in a binder mainly composed of an epoxy resin (CEL2021P) and an acid anhydride (MH700), and the reflectance was 450 nm. Of 65% anisotropic conductive adhesive was obtained. Using this anisotropic conductive adhesive, the LED chip with the AuSn plating applied to the LED chip side electrode and the substrate with the Au plating applied to the substrate side electrode were subjected to thermocompression bonding at 180 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • the total luminous flux of this LED module was 9 lm, the thermal resistance value of the electrical connection portion was 15 K / W, and the die shear strength was 45 N / 1 mm ⁇ .
  • the LED chip side electrode and the solder particles, and the substrate side electrode and the solder particles are Au—Su eutectic bonded, and the solder particles are not crushed and spread. It was confirmed that the thickness was maintained. Further, the initial conduction characteristics and initial insulation characteristics of the LED module were good, and stable conduction characteristics were obtained even in the TCT test ( ⁇ 40 ⁇ 100).
  • Example 4 solder particles (particle size 10 ⁇ m, mp 240 ° C.) and white inorganic particles were mixed in a binder mainly composed of an epoxy resin (CEL2021P) and an acid anhydride (MH700), and the reflectance was 450 nm. Of 60% anisotropic conductive adhesive was obtained. Using this anisotropic conductive adhesive, the LED chip with the Au electrode plated on the LED chip and the substrate with the Au electrode plated on the substrate were heat-pressed at 220 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • This LED module had a total luminous flux of 8.5 lm, a thermal resistance value of the electrical connection portion of 14 K / W, and a die shear strength of 40 N / 1 mm ⁇ .
  • the LED chip side electrode and the solder particles, and the substrate side electrode and the solder particles are Au—Su eutectic bonded, and the solder particles are not crushed and spread. It was confirmed that the thickness was maintained. Further, the initial conduction characteristics and initial insulation characteristics of the LED module were good, and stable conduction characteristics were obtained even in the TCT test ( ⁇ 40 ⁇ 100).
  • Example 5 solder particles (particle size: 10 ⁇ m, mp 240 ° C.) were mixed in a binder mainly composed of epoxy resin (CEL2021P) and acid anhydride (MH700), and the reflectance was 8% with 450 nm light. An isotropic conductive adhesive was obtained. Using this anisotropic conductive adhesive, an LED chip with an Au plating on the LED chip side electrode and a substrate with an Au plating on the substrate side electrode were hot-pressed at 180 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • the thermal resistance value of the electrical connection portion was 15 K / W and the die shear strength was 50 N / 1 mm ⁇ .
  • the LED chip side electrode and the solder particles, and the substrate side electrode and the solder particles are Au—Su eutectic bonded, and the solder particles are not crushed and spread. It was confirmed that the thickness was maintained. Further, the initial conduction characteristics and initial insulation characteristics of the LED module were good, and stable conduction characteristics were obtained even in the TCT test ( ⁇ 40 ⁇ 100).
  • Comparative Example 1 conductive particles (particle size: 10 ⁇ m, resin core Au plating particles) and white inorganic particles were mixed in a binder mainly composed of epoxy resin (CEL2021P) and acid anhydride (MH700), and 450 nm An anisotropic conductive adhesive having a reflectance of 55% with light was obtained. Using this anisotropic conductive adhesive, an LED chip with an Au plating on the LED chip side electrode and a substrate with an Au plating on the substrate side electrode were hot-pressed at 180 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • the total luminous flux of this LED module was 7 lm, but the thermal resistance value of the electrical connection portion was as high as 30 K / W, and the die shear strength was as low as 20 N / 1 mm ⁇ . Further, the initial conduction characteristics and initial insulation characteristics of the LED module were good, and stable conduction characteristics were obtained even in the TCT test ( ⁇ 40 ⁇ 100).
  • solder particles particle size 10 ⁇ m, mp 217 ° C.
  • white inorganic particles are mixed in a binder mainly composed of an epoxy resin (CEL2021P) and an amine-based curing agent, and the reflectance is 65 with light of 450 nm.
  • Anisotropic conductive adhesive was obtained. Using this anisotropic conductive adhesive, an LED chip with an Au plating on the LED chip side electrode and a substrate with an Au plating on the substrate side electrode were hot-pressed at 180 ° C., which is lower than the melting point of the solder particles. Electrical connection was made to obtain an LED module.
  • the total luminous flux of this LED module was 9 lm, but the thermal resistance value of the electrical connection portion was as high as 25 K / W, and the die shear strength was as low as 20 N / 1 mm ⁇ .
  • the LED chip-side electrode and the solder particles, and the substrate-side electrode and the solder particles were not Au—Su eutectic bonded.
  • the initial conduction characteristics and initial insulation characteristics of the LED module were good, but in the TCT test ( ⁇ 40 ⁇ 100), conduction OPEN occurred after 1000 cycles.
  • solder particles particles (particle size 10 ⁇ m, mp 217 ° C.) and white inorganic particles were mixed in a binder mainly composed of an epoxy resin (CEL2021P) and an acid anhydride (MH700), and the reflectance was 450 nm.
  • anisotropic conductive adhesive was obtained.
  • the LED chip with the Au electrode plated on the LED chip and the substrate with the Au electrode plated on the substrate were heat-pressed at 260 ° C., which is higher than the melting point of the solder particles. Electrical connection was made to obtain an LED module. As a result, a short circuit occurred in the initial conduction characteristics of the LED module. Further, as a result of cross-sectional observation of the electrical connection portion of the LED module, it was confirmed that the solder particles were melted and spread between the PN electrodes.
  • an anisotropic conductive adhesive containing solder particles is used, and heat bonding is performed at a temperature lower than the solder melting point. It has been found that an LED module having heat dissipation characteristics and high adhesion characteristics can be manufactured. Further, the heating temperature and the melting point of the solder particles have a difference of 17 ° C., 20 ° C., and 37 ° C. in Examples 1 to 4, ie, the difference between the melting point of the solder particles and 15 ° C. or more is sufficient. I understood.
  • Examples 1 to 4 had high reflectivity due to the blending of the white inorganic particles, and thus the optical characteristics were improved.
  • an acid anhydride is used as a curing agent, and the acid anhydride functions as a flux in addition to curing of the main epoxy resin, so that Comparative Example 2 in which no acid anhydride is blended is used. It was found that higher adhesive properties can be obtained than
  • An anisotropic conductive adhesive comprising a thermosetting adhesive composition containing an epoxy resin and an acid anhydride and solder particles dispersed in the thermosetting adhesive composition, a terminal of the first electronic component, Placing between the terminals of the second electronic component; Using one of the terminals of the first electronic component and the terminal of the second electronic component, pressing the anisotropic conductive adhesive at a temperature that is less than the melting point of the solder particles, By holding the solder particles between the terminals of the first electronic component and the terminals of the second electronic component, the terminals of the first electronic component and the second electronic component are interposed via the solder particles. And a step of electrically connecting the terminal to the manufacturing method of the connection structure.
  • connection structure according to (1) The method for manufacturing a connection structure according to (1), wherein the temperature is a temperature lower by about 15 ° C. or more than a melting point of the solder particles.
  • white inorganic particles are dispersed in the thermosetting adhesive composition.
  • the first electronic component is an LED element; The method for manufacturing a connection structure according to any one of (1) to (6), wherein the second electronic component is a substrate on which the LED element is mounted.
  • the terminal of the LED element includes gold, The method for manufacturing a connection structure according to (7), wherein the terminal of the substrate includes gold. (9)
  • the terminal of the LED element is a gold-tin alloy, The method for manufacturing a connection structure according to (8), wherein the terminal of the substrate is gold.
  • thermosetting adhesive composition containing an epoxy resin and an acid anhydride; Solder particles dispersed in the thermosetting adhesive composition, The thermosetting adhesive composition in which the solder particles are dispersed is heated at a temperature below the melting point of the solder particles.
  • Anisotropic conductive adhesive (1) The anisotropic conductive adhesive according to (10), wherein white inorganic particles are dispersed in the thermosetting adhesive composition.
  • the white inorganic particles have an average particle size of about 0.2 ⁇ m to 10 ⁇ m, and the white inorganic particles are contained in a range of about 1% by volume to 50% by volume with respect to the total amount of the anisotropic conductive adhesive
  • the solder particles have an average particle diameter of about 1 ⁇ m to 20 ⁇ m, and the solder particles are contained in a range of about 1% by volume to 50% by volume with respect to the total amount of the anisotropic conductive adhesive

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Abstract

　接続構造体の製造方法は、エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物とその熱硬化性接着剤組成物に分散されたはんだ粒子とを含む異方性導電接着剤を、第１の電子部品の端子と第２の電子部品の端子との間に配置する工程と、第１の電子部品の端子及び第２の電子部品の端子のうちのいずれか一方を用いて、はんだ粒子の融点未満である温度で異方性導電接着剤を押圧して、第１の電子部品の端子と第２の電子部品の端子との間にはんだ粒子を保持させることにより、はんだ粒子を介して第１の電子部品の端子と第２の電子部品の端子とを電気的に接続させる工程とを含む。

Description

接続構造体の製造方法及び異方性導電接着剤
　本技術は、導電性粒子が分散された異方性導電接着剤、及びそれを用いた接続構造体の製造方法に関し、特に、ドライバーＩＣ（Integrated Circuit）、ＬＥＤ（Light Emitting Diode）等のチップ（素子）が発する熱を放熱することが可能な異方性導電接着剤、及びそれを用いた接続構造体の製造方法に関する。
　ＬＥＤ素子を基板に実装する工法として、ワイヤーボンド工法が用いられている。この他、ワイヤーボンドを用いない工法として、導電性ペーストを用いる工法が提案されていると共に、導電性ペーストを用いない工法として、異方性導電接着剤を用いる工法が提案されている。
　また、フリップチップ（ＦＣ：Flip-Chip）実装するためのＬＥＤ素子が開発されており、そのＦＣ実装用ＬＥＤ素子を基板に実装する工法として、金スズ共晶接合が用いられている。この他、金スズ共晶を用いない工法として、はんだペーストを用いるはんだ接続工法が提案されていると共に、はんだペーストを用いない工法として、異方性導電接着剤を用いる工法が提案されている。
特開平１１－４０６４号公報 特開昭６０－１７８６９０号公報 特開平１１－１７６８７９号公報 特開平８－１８６１５６号公報 特開２０１１－０５７９１７号公報
　しかしながら、異方性導電接着剤の硬化物の熱伝導率は、０．２Ｗ／（ｍ・Ｋ）程度であるため、ＬＥＤ素子から発生する熱を基板側に十分に逃がすことができない。また、異方性導電接着剤を用いたＦＣ実装では、電気接続部分の導電性粒子のみが放熱路となるため、放熱性が悪い。
　したがって、接続信頼性が高く、しかも高い放熱性が得られる異方性導電接着剤及び接続構造体の製造方法を提供することが望ましい。
　本技術では、導電性粒子としてはんだ粒子を使用すると共に、異方性導電接着剤を用いて、はんだ粒子の融点未満の温度で加熱押圧することで、上述の目的を達成できることを見出した。
　すなわち、本技術の一実施形態における接続構造体の製造方法は、エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物とその熱硬化性接着剤組成物に分散されたはんだ粒子とを含む異方性導電接着剤を、第１の電子部品の端子と第２の電子部品の端子との間に配置する工程と、第１の電子部品の端子及び第２の電子部品の端子のうちのいずれか一方を用いて、はんだ粒子の融点未満である温度で異方性導電接着剤を押圧して、第１の電子部品の端子と第２の電子部品の端子との間にはんだ粒子を保持させることにより、はんだ粒子を介して第１の電子部品の端子と第２の電子部品の端子とを電気的に接続させる工程とを含むようにしたものである。
　また、本技術の一実施形態における異方性導電接着剤は、エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物と、その熱硬化性接着剤組成物に分散されたはんだ粒子とを含み、はんだ粒子が分散された熱硬化性接着剤組成物は、そのはんだ粒子の融点未満の温度で加熱されるものである。
　本技術の一実施形態における接続構造体の製造方法又は異方性導電接着剤によれば、はんだ粒子の融点未満の温度で異方性導電接着剤を押圧するため、はんだ粒子の表面は濡れるものの、はんだ粒子全体は溶融しない。そのために、はんだ粒子と端子表面とは金属結合を確保できるものの、接触面積が必要以上に大きくならない効果を有し、熱サイクル試験によるクラックなどの発生を防止することができる。また、金属結合により形成された接触は、放熱路としての役割を果たす。したがって、接続信頼性が高く、放熱性の高い、特に、ＬＥＤ素子の接続に有用な接続構造体の製造方法を提供することができる。
本技術の一実施形態におけるＬＥＤ実装体の一例を示す断面図である。 本技術の他の一実施形態におけるＬＥＤ実装体の一例を示す断面図である。 ワイヤーボンド工法によるＬＥＤ実装体の一例を示す断面図である。 導電性ペーストを用いたＬＥＤ実装体の一例を示す断面図である。 異方性導電接着剤を用いたＬＥＤ実装体の一例を示す断面図である。 ＦＣ実装用ＬＥＤを金スズ共晶接合により実装したＬＥＤ実装体の一例を示す断面図である。 ＦＣ実装用ＬＥＤを導電性ペーストにより実装したＬＥＤ実装体の一例を示す断面図である。 ＦＣ実装用ＬＥＤを異方性導電接着剤により実装したＬＥＤ実装体の一例を示す断面図である。
　以下、本技術の一実施形態について、図面を参照しながら下記順序にて詳細に説明する。
 
　１．異方性導電接着剤及びその製造方法
　２．接続構造体及びその製造方法
　３．実施例
 
＜１．異方性導電接着剤及びその製造方法＞
　本技術の一実施形態における異方性導電接着剤は、エポキシ樹脂と酸無水物とを含有するバインダー（接着剤成分である熱硬化性接着剤組成物）中にはんだ粒子が分散されたものであり、その形状は、ペースト、フィルムなどであり、目的に応じて適宜選択することができる。
　本技術の一実施形態では、異方性導電接着剤を後述する構成とすることにより、圧着時に、はんだ粒子がその融点未満の温度で加熱加圧されるため、はんだ粒子の表面は濡れるものの、はんだ粒子全体は溶融しない。このため、はんだ粒子と端子表面とは金属結合を確保できるものの、接触面積が必要以上に大きくならず、熱サイクル試験によるクラックなどの発生を防止することができる。また、金属結合により形成された接触は、放熱路としての役割を果たす。したがって、接続信頼性が高く、放熱性の高い、特に、ＬＥＤ素子の接続に有用な接続構造体の製造方法を提供することができる。
　はんだ粒子の組成及び形状などに関しては、例えばＪＩＳ Ｚ ３２８２－１９９９に規定されている。はんだ粒子の構成材料としては、Ｓｎ－Ｐｂ系、Ｐｂ－Ｓｎ－Ｓｂ系、Ｓｎ－Ｓｂ系、Ｓｎ－Ｐｂ－Ｂｉ系、Ｂｉ－Ｓｎ系、Ｓｎ－Ｃｕ系、Ｓｎ－Ｐｂ－Ｃｕ系、Ｓｎ－Ｉｎ系、Ｓｎ－Ａｇ系、Ｓｎ－Ｐｂ－Ａｇ系、Ｐｂ－Ａｇ系などから、電極材料や接続条件などに応じて適宜選択することができる。また、はんだ粒子の形状としては、粒状、燐片状などから適宜選択することができる。なお、はんだ粒子は、異方性を向上させるために絶縁層で被覆されていても構わない。
　本技術の一実施形態では、加熱押圧する際の加熱温度がはんだ粒子の融点よりも低く設定されるが、この加熱押圧の際の加熱温度は、熱硬化性接着剤組成物の反応開始温度と等しい又はそれ以上であることが好ましい。具体的には、熱硬化性樹接着剤組成物の反応温度が、一般的な１４０℃～２２０℃である場合、はんだ粒子の融点が２１０℃～２５０℃の範囲のものを選択することが好ましく、２１０℃～２４０℃の範囲のものを選択することがより好ましい。
　はんだ粒子の中には、いわゆる固相点及び液相点を有するはんだ粒子と、固相点と液相点が実質的に合致して一つの融点として把握される共晶はんだ粒子がある。本技術の一実施形態においては、そのいずれのはんだ粒子も使用が可能であるが、前者のはんだ粒子を使用する場合には、固相点未満で加熱押圧し、後者の場合には共晶融点未満で加熱押圧することになる。すなわち、本明細書において、はんだ粒子の融点は、大気圧雰囲気で固相（固体）のはんだが溶け始める固相線温度を云う。
　はんだ粒子の平均粒径（Ｄ５０）は、１μｍ～２０μｍであることが好ましく、より好ましくは２μｍ～１０μｍである。また、はんだ粒子の配合量は、接続信頼性及び絶縁信頼性の観点から異方性導電接着剤全量に対して１体積％～５０体積％の範囲であることが好ましく、特に、３体積％～２５体積％の範囲であることが好ましい。はんだ粒子の配合量が、３体積％以上であると、接続信頼性と放熱性を確実に確保され、２５体積％以下であると、隣接するはんだ粒子の接触に伴うショート等を避けることができる。
　なお、導電性粒子として、はんだ粒子以外にも、本技術の効果に影響を与えない範囲において、エポキシ樹脂、フェノール樹脂、アクリル樹脂、アクリロニトリル・スチレン（ＡＳ）樹脂、ベンゾグアナミン樹脂、ジビニルベンゼン系樹脂、スチレン系樹脂等の樹脂粒子の表面をＡｕ、Ｎｉ、Ｚｎ等の金属で被覆した金属被覆樹脂粒子を併用することができる。
　また、本技術の一実施形態における異方性導電接着剤（熱硬化性接着剤組成物）中に白色無機粒子が分散されていることが好ましい。白色無機粒子は、異方性導電接着剤に光反射性を与えるとともに、異方性導電接着剤に多少の熱伝導性を高める目的で配合される。
　白色無機粒子としては、金属酸化物、金属窒素化物、金属硫化物等の無機微粒子が用いられ、自然光の下で灰色から白色を呈する粒子であることが好ましい。具体的な白色無機粒子としては、酸化チタン、窒化ホウ素、酸化亜鉛、及び酸化アルミニウム等の中から種々選択して使用することが好ましい。
　また、白色無機粒子の熱伝導率は、１０Ｗ／（ｍ・Ｋ）以上であることが好ましい。白色無機粒子の熱伝導率が１０Ｗ／（ｍ・Ｋ）以上であることにより、接続構造体の放熱性を向上させることができる。
　白色無機粒子の形状は、球状、鱗片状、不定形状、針状等で良いが、反射率を考慮すると、球状又は鱗片状であることが好ましい。白色無機粒子の平均粒径（Ｄ５０）は、はんだ粒子よりも大きいと端子間接続の際の障害となるため、はんだ粒子よりも小さいことが好ましい。具体的な平均粒径（Ｄ５０）は、白色無機粒子が球状の場合、０．０２μｍ～２０μｍ、より好ましくは０．２μｍ～１０μｍ、さらに好ましくは０．２μｍ～１．０μｍである。
　また、白色無機粒子の配合量は、少なすぎると光反射性の実現の効果がなく、また多すぎるとはんだ粒子の接続の障害となるため、異方導電接着剤全量において１体積％～５０体積％、より好ましくは２体積％～２５体積％である。
　熱硬化性接着剤組成物としては、従来の異方性導電接着剤や異方性導電フィルムにおいて使用されている接着剤組成物を利用することができる。熱硬化性接着剤組成物の主剤としては、脂環式エポキシ化合物や複素環系エポキシ化合物や水素添加エポキシ化合物等を主成分としたエポキシ硬化系接着剤が好ましく挙げられる。
　脂環式エポキシ化合物としては、分子内に２つ以上のエポキシ基を有するものが好ましく挙げられる。これらは、液状であっても固体状であってもよい。具体的には、グリシジルヘキサヒドロビスフェノールＡ、３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレート等を挙げることができる。中でも、硬化物にＬＥＤ素子の実装等に適した光透過性を確保でき、速硬化性にも優れている点から、３，４－エポキシシクロヘキセニルメチル－３’，４’－エポキシシクロヘキセンカルボキシレートを好ましく使用することができる。
　複素環状エポキシ化合物としては、トリアジン環を有するエポキシ化合物を挙げることができ、特に好ましくは１，３，５－トリス（２，３－エポキシプロピル）－１，３，５－トリアジン－２，４，６－（１Ｈ，３Ｈ，５Ｈ）－トリオンを挙げることができる。
　水素添加エポキシ化合物としては、先述の脂環式エポキシ化合物や複素環系エポキシ化合物の水素添加物や、その他公知の水素添加エポキシ樹脂を使用することができる。
　脂環式エポキシ化合物や複素環系エポキシ化合物や水素添加エポキシ化合物は、単独で使用してもよいが、２種以上を併用することができる。また、これらのエポキシ化合物に加えて本技術の効果を損なわない限り、他のエポキシ化合物を併用してもよい。例えば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ジアリールビスフェノールＡ、ハイドロキノン、カテコール、レゾルシン、クレゾール、テトラブロモビスフェノールＡ、トリヒドロキシビフェニル、ベンゾフェノン、ビスレゾルシノール、ビスフェノールヘキサフルオロアセトン、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、トリス（ヒドロキシフェニル）メタン、ビキシレノール、フェノールノボラック、クレゾールノボラック等の多価フェノールとエピクロルヒドリンとを反応させて得られるグリシジルエーテル；グリセリン、ネオペンチルグリコール、エチレングリコール、プロピレングリコール、ヘキシレングリコール、ポリエチレングリコール、ポリプロピレングリコール等の脂肪族多価アルコールとエピクロルヒドリンとを反応させて得られるポリグリシジルエーテル；ｐ－オキシ安息香酸、β－オキシナフトエ酸のようなヒドロキシカルボン酸とエピクロルヒドリンとを反応させて得られるグリシジルエーテルエステル；フタル酸、メチルフタル酸、イソフタル酸、テレフタル酸、テトラハイドロフタル酸、エンドメチレンテトラハイドロフタル酸、エンドメチレンヘキサハイドロフタル酸、トリメット酸、重合脂肪酸のようなポリカルボン酸から得られるポリグリシジルエステル；アミノフェノール、アミノアルキルフェノールから得られるグリシジルアミノグリシジルエーテル；アミノ安息香酸から得られるグリシジルアミノグリシジルエステル；アニリン、トルイジン、トリブロムアニリン、キシリレンジアミン、ジアミノシクロヘキサン、ビスアミノメチルシクロヘキサン、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルスルホン等から得られるグリシジルアミン；エポキシ化ポリオレフィン等の公知のエポキシ樹脂類が挙げられる。
　主剤を反応させる硬化剤としては、酸無水物、イミダゾール化合物、ジシアン等を挙げることができる。中でも、硬化物を変色させ難い酸無水物、特に脂環式酸無水物系硬化剤を好ましく使用できる。具体的には、メチルヘキサヒドロフタル酸無水物等を好ましく挙げることができる。
　また、酸無水物は、はんだ粒子に対するフラックスとして機能することができ、主剤のエポキシ樹脂の当量を超えて、酸無水物を配合することも差し支えない。具体的には、反応の観点からは、エポキシ樹脂の１．０当量に対して酸無水物が０．７当量～１．０当量で十分であるが、さらに、フラックスとして機能させるために、１．０当量～１．３当量の間で配合することが好ましい。このため、酸無水物は、エポキシ樹脂の１．０当量に対して０．７当量～１．３当量の範囲で配合されていることが好ましい。酸無水物は、エポキシ樹脂の１．０当量に対して１．０当量を超えて配合されてもよい。
　このような構成からなる異方性導電接着剤は、後述の製造方法と相まって、端子間のある程度の接触面積を維持しながら、高い放熱性及び高い接続信頼性を得ることができる。
＜２．接続構造体及びその製造方法＞
　次に、前述した異方性導電接着剤を用いた接続構造体について説明する。本技術の一実施形態における接続構造体では、第１の電子部品の端子と、第２の電子部品の端子とが、樹脂粒子の表面に導電性金属層が形成された導電性粒子を介して電気的に接続されている。第１の電子部品の端子と第２の電子部品の端子との間には、はんだ粒子が捕捉（保持）されている。
　本技術の一実施形態における電子部品としては、熱を発するドライバーＩＣ（Integrated Circuit）、ＬＥＤ（Light Emitting Diode）等のチップ（素子）が好適である。
　図１は、ＬＥＤ実装体の構成例を示す断面図である。このＬＥＤ実装体は、ＬＥＤ素子（第１の電子部品）と、そのＬＥＤ素子を搭載する基板（第２の電子部品）とを、前述したはんだ粒子が接着剤成分中に分散された異方性導電接着剤を用いて接続したものである。
　ＬＥＤ素子は、例えばサファイヤからなる素子基板１１上に、例えばｎ－ＧａＮからなる第１導電型クラッド層１２と、例えばＩｎｘ　Ａｌｙ　Ｇａ１－ｘ－ｙ　Ｎ層からなる活性層１３と、例えばｐ－ＧａＮからなる第２導電型クラッド層１４とを備え、いわゆるダブルヘテロ構造を有する。また、第１導電型クラッド層１２上の一部に第１導電型電極１２ａを備え、第２導電型クラッド層１４上の一部に第２導電型電極１４ａを備える。ＬＥＤ素子の第１導電型電極１２ａと第２導電型電極１４ａとの間に電圧を印加すると、活性層１３にキャリアが集中し、再結合することにより発光が生じる。
　基板は、基材２１上に第１導電型用回路パターン２２と、第２導電型用回路パターン２３とを備え、ＬＥＤ素子の第１導電型電極１２ａ及び第２導電型電極１４ａに対応する位置にそれぞれ電極２２ａ及び電極２３ａを有する。
　異方性導電接着剤は、前述と同様、はんだ粒子３１と、白色無機粒子３２とがバインダー３３に分散されたものである。
　図１に示すように、ＬＥＤ実装体では、ＬＥＤ素子の端子（電極１２ａ、１４ａ）と、基板の端子（電極２２ａ、２３ａ）とが、はんだ粒子３１を介して電気的に接続される。また、ＬＥＤ素子と基板との間に白色無機粒子３２が分散されている。
　これにより、ＬＥＤ素子の活性層１３で発生した熱をはんだ粒子３１を介して効率良く基板側に逃がすことができ、発光効率の低下を防ぐとともにＬＥＤ実装体を長寿命化させることができる。また、白色無機粒子３２が、白又は灰色の無彩色であることにより、活性層１３からの光を反射し、高い輝度を得ることができる。
　また、フリップチップ実装するためのＬＥＤ素子は、図２に示すように、パッシベーション１５により、ＬＥＤ素子の端子（電極１２ａ、１４ａ）が大きく設計されているため、ＬＥＤ素子の端子（電極１２ａ、１４ａ）と基板の端子（回路パターン２２、２３）との間にはんだ粒子３１がより多く捕捉される。これにより、ＬＥＤ素子の活性層１３で発生した熱をさらに効率良く基板側に逃がすことができる。
　また、ＬＥＤ素子の端子（１２ａ、１４ａ）及び基板の端子（２２、２３）のそれぞれの材質は、はんだ粒子との共晶結合のために、金（Ａｕ）又は金－錫合金（ＡｕＳｎ）であることが好ましい。詳細には、ＬＥＤ素子の端子（１２ａ、１４ａ）及び基板の端子（２２、２３）は、いずれも金を含んでいることが好ましい。中でも、ＬＥＤ素子の端子（１２ａ、１４ａ）は金－錫合金であると共に、基板の端子（２２、２３）は金であることがより好ましい。
　次に、上述した接続構造体の製造方法について説明する。本技術の一実施形態における実装体の製造方法は、エポキシ樹脂と酸無水物とを含有する熱硬化性接着剤組成物に前述したはんだ粒子が分散された異方性導電接着剤を、第１の電子部品の端子と第２の電子部品の端子との間に配置する配置工程と、第１の電子部品の端子及び第２の電子部品の端子のうちのいずれか一方を用いて、所定の加熱温度で異方性導電接着剤を押圧して、第１の電子部品の端子と第２の電子部品の端子との間にはんだ粒子を捕捉させる押圧工程を有する。押圧工程では、第１の電子部品と第２の電子部品とを用いると共に、加熱ヘッド等の加熱ツールを使って、異方性導電接着剤を加熱押圧する。
　この加熱押圧により、はんだ粒子を第１の電子部品の端子と第２の電子部品の端子との間に捕捉させる際、その加熱温度は、はんだ粒子の融点未満とすることで、はんだ粒子全体を溶融させずに各端子に接触させる。より具体的な加熱温度としては、熱硬化性接着剤組成物の反応開始温度以上の温度であることが好ましいと共に、はんだ粒子の融点よりも１５℃以上低い温度であることが好ましい。これにより、はんだ粒子と端子との接触面積が必要以上に大きくならず、熱サイクル試験におけるクラック等の発生を防止することができる。
　なお、加熱押圧の際の加熱温度は、加熱ツールのみを使用する場合は、加熱ツールの温度で近似することができる。また、接続構造体を配置するステージが加熱される場合、加熱ツールよりも異方性導電接着剤に与えられる温度が高いことがあるため、加熱ツールの温度を基準とするのではなく、加熱される異方性導電接着剤自体を熱電対等の測定機器を使って、実測を行うことが望ましい。
　なお、上記した本技術の一実施形態における接続構造体の製造方法及び異方性導電接着剤を用いない方法及びその問題点等は、以下の通りである。
　ＬＥＤ素子を基板に実装する工法として、ワイヤーボンド（ＷＢ：Wire Bonding）工法が用いられている。ＷＢ工法は、図３に示すように、ＬＥＤ素子の電極（第１導電型電極１０４ａ及び第２導電型電極１０２ａ）面を上に向け（フェイスアップ）、そのＬＥＤ素子と基板の電気的接合をワイヤーボンド（ＷＢ）３０１ａ、３０１ｂで行い、ＬＥＤ素子と基板との接着には、ダイボンド材３０２を用いる。
　しかし、このようなワイヤーボンドで電気的接続を得る方法では、電極（第１導電型電極１０４ａ及び第２導電型電極１０２ａ）からのワイヤーボンドの物理的破断・剥離のリスクがあるため、より信頼性の高い技術が求められている。さらに、ダイボンド材３０２の硬化プロセスは、オーブン硬化で行われるため、生産に時間が掛かる。
　ワイヤーボンドを用いない工法として、図４に示すように、ＬＥＤ素子の電極（第１導電型電極１０４ａ及び第２導電型電極１０２ａ）面を基板側に向け(フェイスダウン、フリップチップ)、そのＬＥＤ素子と基板との電気的接続に、銀ペーストに代表される導電性ベースト３０３（３０３ａ、３０３ｂ）を用いる方法がある。
　しかし、導電性ペースト３０３（３０３ａ、３０３ｂ）は、接着力が弱いため、封止樹脂３０４による補強が必要である。さらに、封止樹脂３０４の硬化プロセスは、オーブン硬化で行われるため、生産に時間が掛かる。
　導電性ペーストを用いない工法として、図５に示すように、ＬＥＤ素子の電極面を基板側に向け(フェイスダウン、フリップチップ)、そのＬＥＤ素子と基板との電気的接続及び接着に、絶縁性の接着剤バインダー３０５中に導電性粒子３０６を分散させた異方性導電接着剤を用いる方法がある。異方性導電接着剤は、接着プロセスが短いため、生産効率が良い。また、異方性導電接着剤は、安価であり、透明性、接着性、耐熱性、機械的強度、電気絶縁性等に優れている。
　また、フリップチップ（ＦＣ：Flip-Chip ）実装するためのＬＥＤ素子が開発されている。このＦＣ実装用ＬＥＤ素子は、パッシベーション１０５により、電極面積を大きく取る設計が可能であるため、バンプレス実装が可能となる。また、発光層の下に反射膜を設けることによって光取り出し効率が良くなる。
　ＦＣ実装用ＬＥＤ素子を基板に実装する工法としては、図６に示すように、金スズ共晶接合が用いられている。金スズ共晶接合は、チップ電極を金とスズの合金３０７で形成し、フラックスを基板に塗布し、チップを搭載、加熱することで基板電極と、共晶接合させる工法である。しかし、このようなはんだ接続工法は、加熱中のチップズレや洗浄しきれなかったフラックスによる信頼性への悪影響があるため歩留まりが悪い。また、高度な実装技術が必要である。
　金スズ共晶を用いない工法として、図７に示すように、ＬＥＤ素子の電極面と基板との電気的接続に、はんだペーストを用いるはんだ接続工法がある。しかし、このようなはんだ接続工法は、ペーストが等方性の導電性を有するため、ｐｎ電極間がショートしてしまい歩留まりが悪い。
　はんだペーストを用いない工法として、図８に示すように、ＬＥＤ素子と基板との電気的接続及び接着に、図５と同様、絶縁性のバインダー中に導電性粒子を分散させたＡＣＦ（Anisotropic conductive film）などの異方性導電接着剤を用いる方法がある。異方性導電接着剤は、ｐｎ電極間に絶縁性のバインダーが充填される。よって、ショートが発生しにくいため歩留まりが良い。また、接着プロセスが短いため、生産効率が良い。
　ところで、ＬＥＤ素子の活性層（ジャンクション）１０３は、光の他に多くの熱を発生し、発光層温度（Ｔｊ＝ジャンクション温度）が１００℃以上になると、ＬＥＤの発光効率が低下し、ＬＥＤの寿命が短くなる。このため、活性層１０３の熱を効率良く逃がすための構造が必要である。
　図３に示すようなＷＢ実装では、活性層１０３がＬＥＤ素子の上側に位置するため、発生した熱が基板側に効率良く伝わらないため放熱性が悪い。
　また、図４、図６及び図７に示すようなフリップチップ実装を行うと、活性層１０３が基板側に位置するため、熱が基板側に効率良く伝わる。図４及び図７に示すように、電極間を導電性ペースト３０３（３０３ａ、３０３ｂ）で接合した場合、高効率で放熱することができるが、導電性ペースト３０３（３０３ａ、３０３ｂ）による接続は、上記で述べたように接続信頼性が悪い。また、図６に示すように、金スズ共晶接合を行った場合も、上記で述べたのと同様に接続信頼性が悪い。
　また、図５及び図８に示すように、導電性ペースト３０３（３０３ａ、３０３ｂ）を用いずにＡＣＦやＡＣＰ（Anisotropic Conductive Paste）等の異方性導電接着剤でフリップチップ実装することで、活性層１０３が基板側近くに配置され、熱が基板側に効率良く伝わる。また、接着力が高いため、高い接続信頼性が得られる。
　また、はんだペーストに類似する技術として、異方性導電接着剤に、導電性粒子としてはんだ粒子を配合することが考えられる。
　また、ＬＥＤ素子に使用される異方性導電接着剤に、接着層内部に入射する光を効率的に利用するために、白色無機粒子を含有させることにより、当該光を反射させてＬＥＤ素子の全光束量を高めることが考えられる。
　異方性導電接着剤にはんだ粒子を用いれば、接続信頼性の確保はもとより、放熱性の確保も期待できる。しかしながら、はんだ粒子全体を溶融させてしまうと、必要以上にはんだ粒子と端子との接触面積が高くなり、その状態で熱サイクル試験を行うと、クラックなどの不良が発生してしまう。
　また、異方性導電接着剤に白色無機粒子を含有させる場合には、その白色無機粒子を含有する異方性導電接着剤の熱伝導率が１０Ｗ／（ｍ・ｋ）であり、多少熱伝導率が高いため、放熱性が期待できる。しかし、白色無機粒子の粒子径が導電性粒子と同じ又は大きい場合、ＬＥＤ素子と基板の端子間に対して接続不良の原因となる。また、白色無機粒子の粒径が小さい場合、端子間同士で接触しないため放熱路となりえない。結局、接続信頼性を確保しようとすると、白色無機粒子は放熱性に寄与させることができないのが現実である。
＜３．実施例＞
　以下、本技術の実施例について詳細に説明するが、本技術はこれらの実施例に限定されるものではない。
［異方性導電接着剤の作製］
　実施例１～３、比較例２、３では、白色無機粒子として、その表面がＳｉ及びＡｌによりコートされた平均粒子径が０．５μｍ酸化チタン（品名：ＪＲ、テイカ（株）製）、及びはんだ粒子（Ｍ７０７、千住金属（株）製）をエポキシ樹脂硬化系接着剤に分散し、目的の異方性導電接着剤を作成した。
　なお、上記のはんだ粒子の成分は、Ｓｎ－３．０Ａｇ－０．５Ｃｕであり、その融点（固相点）は２１７℃である。また、白色無機粒子の屈折率は、２．７１である。また、エポキシ樹脂硬化系接着剤は、脂環式エポキシ樹脂（商品名：ＣＥＬ２０２１Ｐ、（株）ダイセル化学製）及び酸無水物（ＭＨ７００、新日本理化（株）製）が、夫々当量１．０：１．１の割合で配合されている。
　実施例４は、はんだ粒子（Ｍ１０、千住金属（株）製）に代えた以外は、実施例１と同様に異方性導電接着剤を作成した。ここで、はんだ粒子の成分は、Ｓｎ－５．０Ｓｂであり、その融点（固相点）は２４０℃である。
　実施例５は、白色無機粒子が配合されていない以外は、実施例１と同様の方法で異方性導電接着剤を作成した。
　比較例１は、はんだ粒子の代わりに、導電性粒子（アクリル樹脂粒子に０．２μｍの無電解金メッキを施した粒子、日本化学工業社製）を使用した以外は、実施例１と同様の方法で異方性導電接着剤を作成した。
　比較例２は、酸無水物を使用しないこと以外は、実施例１と同様の方法で異方性導電接着剤を作成した。
　比較例３は、実施例１と同様の異方性導電接着剤であるが、後述する通り、加熱押圧する際の温度がはんだの融点より高い点が相違する。
［異方性導電接着剤の光反射率の測定］
　上記の各異方性導電接着剤をセラミックス製の白色板に乾燥厚で１００μｍとなるように塗布し、２００℃で１分間加熱硬化させた。この硬化物について、分光光度計（Ｕ３３００、日立製作所（株））を用いて、波長４５０ｎｍの光に対する反射率（ＪＩＳ　Ｋ７１５０）を測定した。得られた結果を表１に示す。反射率は、実用上３０％以上であることが望まれる。
［ＬＥＤ実装体の作製］
　実施例１、２、４、５及び比較例１～３の異方性導電接着剤を用いてＡｕバンプを必要としないフリップチップ用ＬＥＤチップ（青色ＬＥＤ、Ｖｆ＝３．２Ｖ（Ｉｆ＝３５０ｍＡ））をＡｕ電極基板に搭載した。異方性導電接着剤をＡｕ電極基板に塗布した後、ＬＥＤチップをアライメントして搭載し、加熱ヘッドの温度を変えて（１８０℃、２００℃、２２０℃、２６０℃）、６０秒－１ｋｇ／ｃｈｉｐの条件で加熱圧着を行った。なお、加熱ヘッドの温度に基づく実際の異方性導電接着剤を熱電対測定器（品名：データロガー、グラフテック社製）を用いて測定した。
　また、Ａｕ電極基板は、バンプボンダーにてＡｕバンプを形成した後、フラットニング処理を行ったものを使用した（ガラスエポキシ基板、導体スペース＝１００μｍ、Ｎｉ／Ａｕメッキ＝５．０μｍ／０．３μｍ、金バンプ＝１５μｍ）。
　得られたＬＥＤ実装体について、放熱特性、光学特性、接着性、及び電気特性を表１に示す。なお、各測定方法は、下記の通りである。
　なお、実施例３においては、ＡｕＳｎバンプを有するＬＥＤチップを前記Ａｕ電極基板に搭載した。
［放熱性の評価］
　過渡熱抵抗測定装置（ＣＡＴＳ電子設計社製）を用いて、ＬＥＤ実装体の熱抵抗値（℃／Ｗ）を測定した。測定条件はＩｆ＝２００ｍＡ（定電流制御）で行った。
［光特性の評価］
　積分球による全光束測定装置（ＬＥ－２１００、大塚電子株式会社製）を用いて、ＬＥＤ実装体の全光束量（ｍｌｍ）を測定した。測定条件はＩｆ＝２００ｍＡ（定電流制御）で行った。
[接着特性の評価（ダイシェア強度）]
　チップ／異方性導電接着剤／基板のダイシェア強度を測定した。ダイシェア強度は、実装したＬＥＤチップを横方向に引っかき、チップが外れるときの強度を測定するものである。測定環境２５℃において、測定速度２０μｍ／ｓｅｃで測定した。測定装置は、ボンドテスターＰＴＲ－１１００（レスカ社製）を用いた。
［電気特性の評価］
（導通特性）
　初期Ｖｆ値として、Ｉｆ＝２０ｍＡ時のＶｆ値を測定した。また、－４０℃／３０ｍｉｎ～１００℃／３０ｍｉｎ、１０００サイクルの熱衝撃試験に投入し、Ｉｆ＝２０ｍＡ時のＶｆ値を測定した。熱衝撃試験の初期の評価は、導通の破断を確認した場合（ＯＰＥＮ）を「×」と評価し、それ以外を「○」と評価した。熱衝撃試験後の評価は、初期Ｖｆ値よりも５％以上上昇した場合を導通ＮＧとして「×」評価し、それ以外を「○」と評価した。なお、「○」は良、「×」は不良を意味している。
（絶縁特性）
　逆電圧５Ｖ印加時の初期Ｉｒ値を測定し、Ｉｒ＝１μＡ以上でリークＮＧとして「×」と評価し、それ以外を「○」と評価した。
　表１に、実施例１～５、及び比較例１～３の評価結果を示す。
Figure JPOXMLDOC01-appb-T000001
　実施例１では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２１７℃）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が６５％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い２００℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は９ｌｍ、電気接続部分の熱抵抗値は１５Ｋ／Ｗ、ダイシェア強度は５０Ｎ／１ｍｍ□であった。ＬＥＤモジュールの電気接続部分の断面観察の結果、ＬＥＤチップ側電極とはんだ粒子、及び基板側電極とはんだ粒子とがＡｕ－Ｓｕ共晶結合しており、はんだ粒子は潰れ広がることなく、接着層の厚みが保持されていることを確認した。また、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であり、ＴＣＴ試験（－４０＜＞１００）においても安定した導通特性が得られた。
　実施例２では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２１７℃）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が６５％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い１８０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は９ｌｍ、電気接続部分の熱抵抗値は１５Ｋ／Ｗ、ダイシェア強度は５０Ｎ／１ｍｍ□であった。ＬＥＤモジュールの電気接続部分の断面観察の結果、ＬＥＤチップ側電極とはんだ粒子、及び基板側電極とはんだ粒子とがＡｕ－Ｓｕ共晶結合しており、はんだ粒子は潰れ広がることなく、接着層の厚みが保持されていることを確認した。また、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であり、ＴＣＴ試験（－４０＜＞１００）においても安定した導通特性が得られた。
　実施例３では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２１７℃）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が６５％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕＳｎめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い１８０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は９ｌｍ、電気接続部分の熱抵抗値は１５Ｋ／Ｗ、ダイシェア強度は４５Ｎ／１ｍｍ□であった。ＬＥＤモジュールの電気接続部分の断面観察の結果、ＬＥＤチップ側電極とはんだ粒子、及び基板側電極とはんだ粒子とがＡｕ－Ｓｕ共晶結合しており、はんだ粒子は潰れ広がることなく、接着層の厚みが保持されていることを確認した。また、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であり、ＴＣＴ試験（－４０＜＞１００）においても安定した導通特性が得られた。
　実施例４では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２４０℃）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が６０％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い２２０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は８．５ｌｍ、電気接続部分の熱抵抗値は１４Ｋ／Ｗ、ダイシェア強度は４０Ｎ／１ｍｍ□であった。ＬＥＤモジュールの電気接続部分の断面観察の結果、ＬＥＤチップ側電極とはんだ粒子、及び基板側電極とはんだ粒子とがＡｕ－Ｓｕ共晶結合しており、はんだ粒子は潰れ広がることなく、接着層の厚みが保持されていることを確認した。また、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であり、ＴＣＴ試験（－４０＜＞１００）においても安定した導通特性が得られた。
　実施例５では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２４０℃）を混合し、４５０ｎｍの光で反射率が８％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い１８０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は５ｌｍと低いものの、電気接続部分の熱抵抗値は１５Ｋ／Ｗ、ダイシェア強度は５０Ｎ／１ｍｍ□であった。ＬＥＤモジュールの電気接続部分の断面観察の結果、ＬＥＤチップ側電極とはんだ粒子、及び基板側電極とはんだ粒子とがＡｕ－Ｓｕ共晶結合しており、はんだ粒子は潰れ広がることなく、接着層の厚みが保持されていることを確認した。また、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であり、ＴＣＴ試験（－４０＜＞１００）においても安定した導通特性が得られた。
　比較例１では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、導電性粒子（粒径１０μｍ、樹脂コアＡｕめっき粒子）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が５５％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い１８０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は７ｌｍであったが、電気接続部分の熱抵抗値は３０Ｋ／Ｗと高く、ダイシェア強度は２０Ｎ／１ｍｍ□と低かった。また、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であり、ＴＣＴ試験（－４０＜＞１００）においても安定した導通特性が得られた。
　比較例２では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）とアミン系硬化剤を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２１７℃）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が６５％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも低い１８０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。このＬＥＤモジュールの全光束量は９ｌｍであったが、電気接続部分の熱抵抗値は２５Ｋ／Ｗと高く、ダイシェア強度は２０Ｎ／１ｍｍ□と低かった。ＬＥＤモジュールの電気接続部分の断面観察の結果、ＬＥＤチップ側電極とはんだ粒子、及び基板側電極とはんだ粒子とがＡｕ－Ｓｕ共晶結合していないことを確認した。その結果、ＬＥＤモジュールの初期導通特性、初期絶縁特性は良好であったが、ＴＣＴ試験（－４０＜＞１００）においては１０００ｃｙｃｌｅ経過後に導通ＯＰＥＮが発生した。
　比較例３では、エポキシ樹脂（ＣＥＬ２０２１Ｐ）と酸無水物（ＭＨ７００）を主成分としたバインダーに、はんだ粒子（粒径１０μｍ、ｍｐ２１７℃）と、白色無機粒子を混合し、４５０ｎｍの光で反射率が６５％の異方性導電接着剤を得た。この異方性導電接着剤を用いてＬＥＤチップ側電極にＡｕめっきを施したＬＥＤチップと、基板側電極にＡｕめっきを施した基板とをはんだ粒子の融点よりも高い２６０℃で加熱圧着して電気接続し、ＬＥＤモジュールを得た。その結果、ＬＥＤモジュールの初期導通特性はショートが発生した。また、ＬＥＤモジュールの電気接続部分の断面観察の結果、はんだ粒子は溶融し、ＰＮ電極間に広がっていることを確認した。
　以上のように、ＬＥＤ素子の電極と基板電極とを電気的に接続する方法として、はんだ粒子を含む異方性導電接着剤を使用し、はんだ融点よりも低い温度で加熱圧着することにより、高い放熱特性及び高い接着特性を有するＬＥＤモジュールを製造することができることが分かった。また、加熱温度とはんだ粒子の融点とは、実施例１～４においては、１７℃、２０℃、３７℃の差異があり、すなわち、はんだ粒子の融点との差が１５℃以上あれば良いことがわかった。また、実施例１～４のＬＥＤチップの接続構造体は、白色無機粒子の配合により、反射率が高く、そのために光学特性が向上することが分かった。また、実施例１～５では、硬化剤として酸無水物を使用し、酸無水物が主剤のエポキシ樹脂の硬化に加え、フラックスとしても機能するため、酸無水物が配合されていない比較例２と比較して、高い接着特性が得られることが分かった。
　また、本技術は以下の構成を採用することもできる。
（１）
　エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物とその熱硬化性接着剤組成物に分散されたはんだ粒子とを含む異方性導電接着剤を、第１の電子部品の端子と第２の電子部品の端子との間に配置する工程と、
　前記第１の電子部品の端子及び前記第２の電子部品の端子のうちのいずれか一方を用いて、前記はんだ粒子の融点未満である温度で前記異方性導電接着剤を押圧して、前記第１の電子部品の端子と前記第２の電子部品の端子との間に前記はんだ粒子を保持させることにより、前記はんだ粒子を介して前記第１の電子部品の端子と前記第２の電子部品の端子とを電気的に接続させる工程と
　を含む、接続構造体の製造方法。
（２）
　前記温度が、前記はんだ粒子の融点よりも約１５℃以上低い温度である
　（１）に記載の接続構造体の製造方法。
（３）
　前記温度が、前記熱硬化性接着剤組成物の反応開始温度以上の温度である
　（１）又は（２）に記載の接続構造体の製造方法。
（４）
　前記はんだ粒子の融点が、約２１０℃～２５０℃の範囲である
　（１）乃至（３）のいずれか１項に記載の接続構造体の製造方法。
（５）
　前記熱硬化性接着剤組成物に白色無機粒子が分散されている
　（１）乃至（４）のいずれか１項に記載の接続構造体の製造方法。
（６）
　前記白色無機粒子の熱伝導率が、約１０Ｗ／（ｍ・Ｋ）以上である
　（５）に記載の接続構造体の製造方法。
（７）
　前記第１の電子部品が、ＬＥＤ素子であり、
　前記第２の電子部品が、前記ＬＥＤ素子を搭載する基板である
　（１）乃至（６）のいずれか１項に記載の接続構造体の製造方法。
（８）
　前記ＬＥＤ素子の端子が金を含み、
　前記基板の端子が金を含む
　（７）に記載の接続構造体の製造方法。
（９）
　前記ＬＥＤ素子の端子が金錫合金であり、
　前記基板の端子が金である
　（８）に記載の接続構造体の製造方法。
（１０）
　エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物と、
　その熱硬化性接着剤組成物に分散されたはんだ粒子と
　を含み、
　前記はんだ粒子が分散された前記熱硬化性接着剤組成物は、そのはんだ粒子の融点未満の温度で加熱される、
　異方性導電接着剤。
（１１）
　前記熱硬化性接着剤組成物に白色無機粒子が分散されている
　（１０）に記載の異方性導電接着剤。
（１２）
　前記白色無機粒子の平均粒径が約０．２μｍ～１０μｍであり、前記白色無機粒子が当該異方性導電接着剤全量に対して約１体積％～５０体積％の範囲で含有され、
　前記はんだ粒子の平均粒子径が約１μｍ～２０μｍであり、前記はんだ粒子が当該異方性導電接着剤全量に対して約１体積％～５０体積％の範囲で含有され、
　前記酸無水物が前記エポキシ樹脂１．０当量に対して約０．７当量～１．３当量の範囲で含有されている
　（１１）に記載の異方性導電接着剤。
（１３）
　前記酸無水物が前記エポキシ樹脂１．０当量に対して約１．０当量を超えて含有されている
　（１２）に記載の異方性導電接着剤。
　本出願は、日本国特許庁において２０１２年９月２４日に出願された日本特許出願番号第２０１２－２１０２２５号を基礎として優先権を主張するものであり、この出願のすべての内容を参照によって本出願に援用する。
　当業者であれば、設計上の要件や他の要因に応じて、種々の修正、コンビネーション、サブコンビネーション、及び変更を想到し得るが、それらは添付の請求の範囲の趣旨やその均等物の範囲に含まれるものであることが理解される。

Claims (13)

  1. 　エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物とその熱硬化性接着剤組成物に分散されたはんだ粒子とを含む異方性導電接着剤を、第１の電子部品の端子と第２の電子部品の端子との間に配置する工程と、
    　前記第１の電子部品の端子及び前記第２の電子部品の端子のうちのいずれか一方を用いて、前記はんだ粒子の融点未満である温度で前記異方性導電接着剤を押圧して、前記第１の電子部品の端子と前記第２の電子部品の端子との間に前記はんだ粒子を保持させることにより、前記はんだ粒子を介して前記第１の電子部品の端子と前記第２の電子部品の端子とを電気的に接続させる工程と
    　を含む、接続構造体の製造方法。
  2. 　前記温度が、前記はんだ粒子の融点よりも約１５℃以上低い温度である
    　請求項１に記載の接続構造体の製造方法。
  3. 　前記温度が、前記熱硬化性接着剤組成物の反応開始温度以上の温度である
    　請求項１又は２に記載の接続構造体の製造方法。
  4. 　前記はんだ粒子の融点が、約２１０℃～約２５０℃の範囲である
    　請求項１乃至３のいずれか１項に記載の接続構造体の製造方法。
  5. 　前記熱硬化性接着剤組成物に白色無機粒子が分散されている
    　請求項１乃至４のいずれか１項に記載の接続構造体の製造方法。
  6. 　前記白色無機粒子の熱伝導率が、約１０Ｗ／（ｍ・Ｋ）以上である
    　請求項５に記載の接続構造体の製造方法。
  7. 　前記第１の電子部品が、ＬＥＤ素子であり、
    　前記第２の電子部品が、前記ＬＥＤ素子を搭載する基板である
    　請求項１乃至６のいずれか１項に記載の接続構造体の製造方法。
  8. 　前記ＬＥＤ素子の端子が金を含み、
    　前記基板の端子が金を含む
    　請求項７に記載の接続構造体の製造方法。
  9. 　前記ＬＥＤ素子の端子が金錫合金であり、
    　前記基板の端子が金である
    　請求項８に記載の接続構造体の製造方法。
  10. 　エポキシ樹脂及び酸無水物を含有する熱硬化性接着剤組成物と、
    　その熱硬化性接着剤組成物に分散されたはんだ粒子と
    　を含み、
    　前記はんだ粒子が分散された前記熱硬化性接着剤組成物は、そのはんだ粒子の融点未満の温度で加熱される、
    　異方性導電接着剤。
  11. 　前記熱硬化性接着剤組成物に白色無機粒子が分散されている
    　請求項１０に記載の異方性導電接着剤。
  12. 　前記白色無機粒子の平均粒径が約０．２μｍ～約１０μｍであり、前記白色無機粒子が当該異方性導電接着剤全量に対して約１体積％～約５０体積％の範囲で含有され、
    　前記はんだ粒子の平均粒子径が約１μｍ～約２０μｍであり、前記はんだ粒子が当該異方性導電接着剤全量に対して約１体積％～約５０体積％の範囲で含有され、
    　前記酸無水物が前記エポキシ樹脂１．０当量に対して約０．７当量～約１．３当量の範囲で含有されている
    　請求項１１に記載の異方性導電接着剤。
  13. 　前記酸無水物が前記エポキシ樹脂１．０当量に対して約１．０当量を超えて含有されている
    　請求項１２記載の異方性導電接着剤。
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WO2015178482A1 (ja) * 2014-05-23 2015-11-26 デクセリアルズ株式会社 接着剤及び接続構造体
JP2015221876A (ja) * 2014-05-23 2015-12-10 デクセリアルズ株式会社 接着剤及び接続構造体
JP2015221875A (ja) * 2014-05-23 2015-12-10 デクセリアルズ株式会社 接着剤及び接続構造体
US10435601B2 (en) 2014-05-23 2019-10-08 Dexerials Corporation Adhesive agent and connection structure
JP2017045832A (ja) * 2015-08-26 2017-03-02 日亜化学工業株式会社 発光装置及び発光装置の製造方法
JP7469641B2 (ja) 2020-05-20 2024-04-17 日亜化学工業株式会社 発光装置の検査方法及び検査用治具

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