WO2019093119A1 - Composition de pâte, dispositif à semi-conducteur et composant électrique/électronique - Google Patents

Composition de pâte, dispositif à semi-conducteur et composant électrique/électronique Download PDF

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Publication number
WO2019093119A1
WO2019093119A1 PCT/JP2018/039344 JP2018039344W WO2019093119A1 WO 2019093119 A1 WO2019093119 A1 WO 2019093119A1 JP 2018039344 W JP2018039344 W JP 2018039344W WO 2019093119 A1 WO2019093119 A1 WO 2019093119A1
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Prior art keywords
copper
paste composition
fine particles
copper fine
compound
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PCT/JP2018/039344
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English (en)
Japanese (ja)
Inventor
藤原　正和
勇哉 似内
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京セラ株式会社
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Publication of WO2019093119A1 publication Critical patent/WO2019093119A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/40—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers

Definitions

  • the present embodiment relates to a paste composition and a semiconductor device and an electric / electronic component manufactured using the paste composition.
  • a method of bonding a heat spreader to the die pad portion of the semiconductor element itself or a lead frame to which the semiconductor element is bonded or A method (for example, refer to Patent Document 1) or the like is adopted which has a function as a heat sink by exposing it.
  • the semiconductor element may be bonded to an organic substrate or the like having a heat dissipation mechanism such as a thermal via. Also in this case, high thermal conductivity is required of the material for bonding the semiconductor element.
  • the adhesive for bonding the light emitting element and the substrate may be discolored by heat or light, or the electric resistance value may change with time due to the high current input due to the high output of the light emitting element. .
  • the bonding material loses its adhesive force at the solder melting temperature and peels off when the electronic component or electronic device is soldered.
  • the enhancement of the performance of the white light emitting LED leads to an increase in the calorific value of the light emitting element chip, and along with this, the structure of the LED and the members used therefor are also required to improve the heat dissipation.
  • a copper particle-containing paste composition and a paste composition which are capable of sintering at low temperatures even in a non-reducing atmosphere, have excellent thermal conductivity, have excellent adhesive properties, and have reflow resistance are desired. It is done.
  • the paste composition of the present embodiment contains (A) copper fine particles having a thickness or short diameter of 10 to 500 nm, and (B) a sintering aid containing an acid anhydride structure, and the (A) copper fine particles described above.
  • the (B) sintering aid is blended in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass.
  • the paste composition of the present embodiment includes (A) copper fine particles having a thickness or short diameter of 10 to 500 nm, and (B) a sintering aid including an acid anhydride structure.
  • the (A) copper fine particle used in the present embodiment is not particularly limited as long as its thickness or short diameter is 10 to 500 nm.
  • the shape of the (A) copper fine particle for example, a spherical shape, a plate shape, a flake shape, a scaly shape, a dendritic shape, a rod shape, a wire shape or the like can be used.
  • the thickness may be plate-like, flake-like or scaly, and the shortest diameter in the dendritic or rod-like or wire-like or spherical shape may satisfy the above range.
  • the “diameter” means, for example, in the dendritic, rod-like or wire-like shape, the length of the diameter in the cross section perpendicular to the long axis of those, or in the spherical shape, the cross section passing through the center.
  • the calculation method of this diameter does not necessarily need to confirm a cross section, and may be calculated by the method using an electron micrograph as mentioned later.
  • the copper fine particles have the above-described thickness or short diameter that satisfies the above range, so that the sintering temperature is lowered, so that the sintering operation can be easily performed.
  • the (A) copper fine particles may be fine particles that self-sinter at 100 ° C. to 250 ° C.
  • self-sintering refers to a phenomenon in which copper fine particles in a dispersed state aggregate under specific temperature conditions and then form a metal bond between the copper fine particles.
  • the (A) copper fine particles may be coated with a compound that suppresses oxidation of the surface, and examples of such a compound include an amine compound, a carboxylic acid compound, and the like.
  • coating means that the compound which suppresses the said oxidation has adhered to all or one part of the surface of copper particulates.
  • the copper particulate surface may be coated with an amine compound, or may be coated with an amino alcohol represented by the following chemical formula (1).
  • the copper fine particles whose surface is coated with an amine compound are easy to be removed because the coating layer is coordinate bonded, and they are sintered at a low temperature.
  • the copper fine particles are appropriately dispersed by combining with a sintering aid containing an acid anhydride structure (B) described later, and sintering is performed at a low temperature.
  • R 1 may be the same or different, and independently of each other represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxy group or a methoxy group, and n and m are integers of 0 to 10) And m + n is 10 or less.
  • the copper fine particles coated with such an amine compound are prepared by mixing the copper-containing compound, the amine compound and the reducing compound in an organic solvent to form a mixture, and heating the mixture to a temperature at which the copper-containing compound is thermally decomposed. It is obtained by doing.
  • the copper microparticles thus obtained are coated with an organic compound ion derived from a copper-containing compound and an amine compound, which are generated by decomposing the copper-containing compound.
  • the copper particles coated on the surface with these components are excellent in low-temperature sinterability.
  • the raw material used for manufacture of the copper fine particle of this embodiment is demonstrated below.
  • the copper-containing compound used here is a material for depositing metallic copper to form fine copper particles.
  • the copper-containing compound is decomposed by heating to release copper ions.
  • the copper ions are reduced to metal copper.
  • the copper-containing compound may be decomposed by heating to release copper ions and organic ions derived from the copper-containing compound.
  • Such copper-containing compounds include, for example, copper carboxylate, cuprous oxide, copper nitrate, copper sulfate and the like in which a carboxylic acid such as formic acid, oxalic acid, malonic acid, benzoic acid and phthalic acid is combined with copper. .
  • the amine compound used here may have an amino group as long as it forms a complex (copper-containing compound-amine complex) with the copper-containing compound.
  • amino alcohol, alkyl amine, alkoxy amine etc. are mentioned.
  • the amine compound can be appropriately selected and used according to the conditions of the thermal decomposition of the copper-containing compound to be used, the characteristics expected of the copper fine particles to be produced, and the like. These amine compounds adhere to the surface of copper microparticles obtained by thermally decomposing a copper-containing compound, and have the function of suppressing the oxidation of copper microparticles.
  • the amino compound may be an amino alcohol.
  • the amino alcohol may be an alcohol having an amino group represented by the above chemical formula (1). Specifically as this amino alcohol, aminoethanol, heptaminol, propanolamine, 1-amino-2-propanol, 2-aminodibutanol, 2-diethylaminoethanol, 3-diethylamino-1,2-propanediol, 3 And -dimethylamino-1,2-propanediol, 3-methylamino-1,2-propanediol, 3-amino-1,2-propanediol and the like.
  • the amino alcohol may have a boiling point of 70 to 300 ° C. from the viewpoint of sinterability.
  • the amino alcohol may be liquid at normal temperature from the viewpoint of workability.
  • the structure of the alkylamine is not particularly limited as long as it is an amine compound in which an aliphatic hydrocarbon group such as an alkyl group is bonded to an amino group.
  • Examples of the amine compound include alkyl monoamines having one amino group and alkyl diamines having two amino groups.
  • the above alkyl group may further have a substituent.
  • alkyl monoamines dipropylamine, butylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, 3-aminopropyltriethoxysilane, dodecylamine, oleylamine etc. It can be mentioned.
  • alkyldiamine ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-diethylethylenediamine, 1,3-propanediamine, 2,2-dimethyl- 1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, 1,4 -Diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N'-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane and the like , Is mentioned.
  • the alkyl monoamine is an alkyl monoamine such as a primary amine (R 2 NH 2 ) or a secondary amine (R 3 R 4 NH). May be.
  • the alkylamine does not include the alkoxyamine described below.
  • the alkoxyamine is not particularly limited as long as it is an amine compound having an alkoxyl group, and examples thereof include an alkoxy monoamine having one amino group and an alkoxy diamine having two amino groups.
  • examples of the alkoxy monoamine include methoxyethylamine, 2-ethoxyethylamine, 3-butoxypropylamine and the like
  • examples of the alkoxydiamine include N-methoxy-1,3-propanediamine and N-methoxy-1,4- A butane diamine etc. are mentioned.
  • the alkoxyamine may be an alkoxymonoamine such as a primary amine (R 2 ONH 2 ) or a secondary amine (R 3 (R 4 O) NH), in consideration of the coordination power to copper formed by reduction.
  • the substituent R 2 of the primary amine described in the above alkylamine and alkoxyamine represents an alkyl group and may be an alkyl group having 4 to 18 carbon atoms.
  • the substituents R 3 and R 4 of the secondary amine each represent an alkyl group, and may be an alkyl group having 4 to 18 carbon atoms.
  • the substituents R 3 and R 4 may be identical or different.
  • these alkyl groups may have a substituent such as silyl group or glycidyl group.
  • the boiling point of the amine compound may be 70 ° C. or more and 200 ° C. or less, and may be 120 ° C. or more and 200 ° C. or less. If the boiling point of the amine compound is 70 ° C. or more, there is no possibility that the amine is volatilized in the heating step, and if it is 200 ° C. or less, it is removed at the time of sintering the copper fine particles and it becomes easy to sinter at low temperature. Furthermore, the boiling point of the amino compound may be higher than the heating temperature in the heating step, or lower than the sintering temperature in use. Moreover, as this amine compound, it can also be used individually by 1 type or in combination of 2 or more.
  • the reducing compound used here is not particularly limited as long as it has a reducing power to reduce copper ions generated by the decomposition of the copper-containing compound and release metallic copper.
  • the boiling point of the reducing compound may be 70 ° C. or higher, or may be higher than the heating temperature in the heating step.
  • the reducing compound may be a compound soluble in an organic solvent (C) described later, which is composed of carbon, hydrogen and oxygen.
  • Such reducing compounds typically include hydrazine derivatives.
  • this hydrazine derivative include hydrazine monohydrate, methylhydrazine, ethylhydrazine, n-propylhydrazine, i-propylhydrazine, n-butylhydrazine, i-butylhydrazine, sec-butylhydrazine, t-butylhydrazine, n-pentylhydrazine, i-pentylhydrazine, neo-pentylhydrazine, t-pentylhydrazine, n-hexylhydrazine, i-hexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-d
  • the above-mentioned copper-containing compound, amine compound and reducing compound may be mixed in an organic solvent.
  • the organic solvent used here can be used without particular limitation as long as it can be used as a reaction solvent which does not inhibit the properties of the complex and the like generated from the mixture obtained by the above mixing.
  • the organic solvent may be an alcohol which is compatible with the above-described reducing compound.
  • the reduction reaction of copper ions by the reducing compound since the reduction reaction of copper ions by the reducing compound is an exothermic reaction, it may be an organic solvent which does not volatilize during the reduction reaction. Therefore, the boiling point of the organic solvent is 70 ° C. or higher, and may be composed of carbon, hydrogen and oxygen. When the boiling point of the organic solvent is 70 ° C. or more, the formation of copper ions by the decomposition of the copper-containing compound-alcoholamine compound complex and the control of the deposition of metallic copper by the reduction of the formed copper ions become easy, become stable.
  • alcohol used as an organic solvent 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, butyl carbitol, Examples include butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, diethylene glycol diethyl ether, butyl cellosolve and the like.
  • the above-mentioned amino alcohol and reducing compound are not included in this organic solvent.
  • Copper fine particles can be produced as follows using the above-described copper-containing compound, amine compound, reducing compound, and an organic solvent which is optionally added.
  • the mixture is formed by first storing the organic solvent in the reaction vessel and then mixing the copper-containing compound, the amine compound, and the reducing compound. The order of this mixing may mix the said compound in what kind of order.
  • the copper-containing compound and the amine compound are first mixed, and mixed for about 5 to 30 minutes at 0 to 50 ° C. May be added and mixed.
  • the amount of each compound used may be 0.5 to 10 mol of the amine compound amino alcohol and 0.5 to 5 mol of the reducing compound with respect to 1 mol of the copper-containing compound.
  • the amount of the organic solvent may be such that each component can sufficiently react. For example, about 50 to 2000 mL may be used.
  • the mixture obtained by mixing above is sufficiently heated to allow the thermal decomposition reaction of the copper-containing compound to proceed.
  • the copper-containing compound forming a complex is decomposed into the organic ion derived from the copper-containing compound and the copper ion.
  • the copper ion is reduced by the reducing compound, and metallic copper precipitates and grows into copper fine particles.
  • the metal ion derived from the copper-containing compound at the same time as the metal copper precipitates tends to be coordinated to the specific crystal plane of the metal copper that has been precipitated. For this reason, it is possible to control the growth direction of the copper particulates to be generated, and to obtain plate-like copper particulates efficiently.
  • the amine compound adheres to the surface of the copper fine particles, and has an effect of preventing the particles from becoming coarse by reducing the growth.
  • the heating temperature in the heating step of this mixture is a temperature at which the copper-containing compound is thermally decomposed and reduced to form plate-like copper fine particles.
  • the heating temperature may be, for example, 70 ° C. to 150 ° C., or may be 80 to 120 ° C. Furthermore, at this time, the heating temperature may be lower than the boiling point of the raw material component and the organic solvent.
  • the heating temperature is 70 ° C. or more, the thermal decomposition reaction of the copper-containing compound proceeds stably, so copper microparticles can be efficiently generated.
  • the heating temperature is 150 ° C. or less, the volatilization amount of the amine compound is reduced, so the uniformity in the system is maintained, and the thermal decomposition of the copper-containing compound proceeds stably, thereby efficiently forming copper fine particles. it can.
  • the solid precipitated here may be separated from the organic solvent or the like by centrifugation or the like, and then the solid may be dried under reduced pressure.
  • the copper microparticles of the present embodiment can be obtained by such an operation.
  • the complex formed from the copper-containing compound and the reducing agent is thermally decomposed in the amine compound, and the amine compound forms a coordination bond with the copper atom generated. It is surmised that aggregation of these copper atoms results in the formation of copper microparticles coated with an amine compound.
  • the obtained copper fine particles are composed of an amine compound and an organic ion derived from copper carboxylate which is generated by thermally decomposing the copper carboxylate in addition thereto. It is presumed that the surface is coated.
  • Such copper particulates have specific properties and shapes derived from molecules that coat the surface.
  • the copper fine particles can have any shape and size by appropriately selecting the kind of copper-containing compound, amine compound, reducing agent and reaction temperature to be used. Further, by adding an amino alcohol and another amine compound as an amine compound to the mixture of the copper-containing compound and the reducing agent, the copper fine particles generated by the above thermal decomposition are also coated with the other amine compound. Thereby, the oxidation of copper particulates is reduced and the growth direction of copper particulates is controlled. Thus, when the growth direction of the metallic copper is controlled, the obtained copper fine particles have a plate shape.
  • the copper particles obtained by the above-described method for producing copper particles can be fired at a low temperature.
  • the paste composition using the copper fine particles can be fired even in a non-reducing atmosphere.
  • the resistance can be reduced, and the amount of outgassing that can cause generation of voids is small, so a dense sintered film can be obtained.
  • the shape of the obtained copper fine particles can be confirmed by observation with a scanning electron microscope (manufactured by JEOL Ltd., trade name: JSM-7600F; SEM).
  • an average value is an arithmetic average value, and it is good also as ten or more copper microparticles
  • the sintering aid containing the acid anhydride structure (B) used in the present embodiment is a substance that promotes the sintering of the (A) copper fine particles or a substance that densifies a sintered body obtained by sintering. If it is, it will not be limited in particular.
  • the (B) sintering aid has a structure in which two molecules of oxo acid are dehydrated and condensed.
  • the sintering aid may have a structure in which the carboxyl groups of the compound having a plurality of carboxyl groups are dehydrated and condensed in the molecule.
  • the carboxylic acid anhydride since the carboxylic acid anhydride has a high ability to coordinate to the surface of the copper fine particle, it is substituted with a protective group on the surface of the copper fine particle, and the carboxylic acid anhydride is coordinated to the surface of the copper fine particle.
  • the copper fine particle which the carboxylic anhydride coordinated to the surface improves the dispersibility.
  • the carboxylic anhydride since the carboxylic anhydride is excellent in volatility, low temperature sinterability is improved.
  • the melting point of the sintering aid (B) used in the present embodiment may be in the range of 40 to 150.degree. When the melting point of the sintering aid is in this range, the sintering promoting property of the paste composition is improved and the workability such as the stability of the life of the paste composition is improved.
  • the boiling point of the sintering aid (B) used in the present embodiment may be 100 to 300 ° C., or may be 100 to 275 ° C. If the boiling point is in this range, there is no risk of void formation.
  • By blending such an acid anhydride as a sintering aid it is possible to obtain a paste composition having improved adhesion properties, thermal conductivity and reflow peel resistance.
  • the amount of the sintering additive (B) may be 0.01 to 1 part by mass, based on 100 parts by mass of the (A) copper fine particles. Adhesive property improves that the compounding quantity of a sintering aid is 0.01 mass part or more, and since there is no possibility of void generation
  • the paste composition of the present embodiment may use (C) an organic solvent.
  • the organic solvent (C) used here any known solvent can be used as long as it functions as a reducing agent.
  • alcohol may be sufficient and, for example, aliphatic polyhydric alcohol can be mentioned.
  • aliphatic polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, diprylene glycol, 1,4-butanediol, glycerin, glycols such as polyethylene glycol, and the like. These organic solvents can be used alone or in combination of two or more.
  • the paste composition of the present embodiment a dense sintered structure is obtained by using alcohol as the organic solvent (C), so the conductivity is high, and the adhesion with a substrate such as a lead frame is high. It becomes a thing.
  • This mechanism is presumed as follows. Since the bonding portion is sandwiched between the semiconductor element and the substrate, the alcohol is partially refluxed by heating at the time of sintering. Because of this, the alcohol stays at the joint for a while without volatilizing immediately. At this time, the copper oxide partially present in the copper particles of the paste composition and the metal oxide (for example, copper oxide) present on the substrate surface to be bonded are reduced to a metal (for example, copper) by alcohol. . Thereafter, the copper particles sinter with the reduced metal (eg, copper). As a result, the paste composition at the bonding portion forms a metal bond having high conductivity and high adhesion to the substrate.
  • alcohol organic solvent
  • the boiling point of the organic solvent (C) may be 100 to 300 ° C., or may be 150 to 290 ° C.
  • the volatility does not become too high even at normal temperature, the reduction ability by the volatilization of the dispersion medium can be maintained, and stable adhesive strength can be obtained.
  • the boiling point is 300 ° C. or less, sintering of the cured film (conductive film) is easily caused, and a film excellent in compactness can be formed.
  • the organic solvent is not volatilized and the remaining of the organic solvent in the film can be reduced.
  • the blending amount may be 7 to 20 parts by mass based on 100 parts by mass of copper particles. If it is 7 parts by mass or more, the viscosity is not too high and the workability can be improved, and if it is 20 parts by mass or less, the viscosity is not too low, and the copper settling in the paste is reduced, and the reliability is improved. It can be enhanced.
  • the paste composition of the present embodiment may use (D) a thermosetting resin.
  • the thermosetting resin (D) used in the present embodiment is not particularly limited as long as it is a thermosetting resin generally used as an adhesive application.
  • the thermosetting resin may be a liquid resin or a resin which is liquid at room temperature (25 ° C.).
  • Examples of the (D) thermosetting resin include cyanate resin, epoxy resin, radical polymerizable acrylic resin, maleimide resin and the like. These may be used alone or in combination of two or more.
  • an adhesive material (paste) having an appropriate viscosity can be obtained.
  • the paste composition of the present embodiment includes a thermosetting resin, the temperature of the paste composition is increased by the reaction heat at the time of curing thereof, and the sinterability of the copper particles is promoted.
  • thermosetting resin (D) when blended, it is blended so as to be 1 to 20 parts by mass when the above (A) copper fine particles are 100 parts by mass.
  • thermosetting resin is 1 part by mass or more, sufficient adhesiveness by the thermosetting resin can be obtained, and when the thermosetting resin is 20 parts by mass or less, high thermal conductivity can be sufficiently ensured. The heat dissipation can be improved.
  • the amount of the organic component is not too large, and deterioration due to light and heat can be suppressed, and as a result, the lifetime of the light-emitting device can be increased. By setting it as such a compounding range, it is easy to reduce the contact between copper particles and to maintain the mechanical strength of the entire adhesive layer by utilizing the adhesive performance of the thermosetting resin.
  • a curing accelerator in addition to the above-described components, a curing accelerator, a stress reducing agent such as rubber or silicone, a coupling agent, an antifoamer, and the like generally compounded in this type of composition.
  • Surfactants, colorants (pigments, dyes), various polymerization inhibitors, antioxidants, solvents, and other various additives can be blended as necessary. Any of these additives may be used alone or in combination of two or more.
  • the paste composition of the present embodiment includes each of the components (A) to (B) described above, optional components (C) and (D) blended if necessary, and other additives such as a coupling agent and the like, After sufficiently mixing the solvent and the like, the mixture can be further kneaded by a disperser, a kneader, a three-roll mill or the like, and then defoamed to prepare.
  • the paste composition also includes those with low viscosity such as a slurry or an ink.
  • the viscosity of the paste composition of the present embodiment may be, for example, 20 to 300 Pa ⁇ s, or 30 to 200 Pa ⁇ s.
  • the adhesive strength of the paste composition of the present embodiment may be 20 MPa or more, 25 MPa or more, or 30 MPa or more.
  • the said viscosity and adhesive strength can be measured by the method as described in an Example.
  • the paste composition of the present embodiment thus obtained is excellent in high thermal conductivity and heat dissipation. Therefore, when used as a bonding material of the element or the heat dissipation member to the substrate or the like, the heat dissipation inside the device can be improved and the product characteristics can be stabilized.
  • the semiconductor device of the present embodiment is formed by adhering a semiconductor element on a substrate serving as an element support member, using the above-described paste composition. That is, here, the paste composition is used as a die attach paste, and the semiconductor element and the substrate are adhered and fixed via this paste composition.
  • the semiconductor element may be a known semiconductor element, and examples thereof include a transistor, a diode, and the like.
  • a light emitting element such as an LED may be mentioned.
  • the type of the light emitting element is not particularly limited.
  • a light emitting layer in which a nitride semiconductor such as InN, AlN, GaN, InGaN, AlGaN, InGaAlN or the like is formed on a substrate by MOCVD method is also mentioned.
  • a support member formed of a material such as copper, copper-plated copper, PPF (precoating lead frame), glass epoxy, ceramics, etc. may be mentioned.
  • the paste composition of this embodiment can also adhere to a substrate that has not been metal plated.
  • the connection reliability with respect to the temperature cycle after mounting is dramatically improved as compared with the related art.
  • the electric resistance value is sufficiently small and the change with time is small, there is an advantage that the output does not decrease with time even when driven for a long time and the life is long.
  • the electric / electronic device of the present embodiment is formed by bonding a heat dissipation member to a heat generating member using the above-described paste composition. That is, here, the paste composition is used as a heat radiation member bonding material, and the heat radiation member and the heat generation member are bonded and fixed via the paste composition.
  • the heat generating member the above-described semiconductor element or a member having the semiconductor element may be used, or any other heat generating member may be used.
  • heat generating members other than semiconductor elements include optical pickups and power transistors.
  • a heat dissipation member a heat sink, a heat spreader, etc. are mentioned.
  • the heat radiating member to the heat generating member using the above-described paste composition
  • the heat generated by the heat generating member can be efficiently released to the outside by the heat radiating member, and the temperature rise of the heat generating member It can be suppressed.
  • the heat-generating member and the heat-radiating member may be bonded directly via the paste composition, or may be bonded indirectly by sandwiching another member having a high thermal conductivity.
  • Synthesis Example 2 Similar to Synthesis Example 1 except that 1-amino-2-propanol of Example 1 was replaced with 60 mmol of octylamine, plate-shaped powdery copper microparticles 2 with a particle diameter of 0.10 ⁇ m were obtained. The surface of the copper fine particle 1 was coated with octylamine.
  • Examples 1 to 4 Comparative Example 1
  • Each component was mixed according to the composition (parts by mass) of Table 1 and kneaded with a roll to obtain a resin paste.
  • cured material was investigated, and the following method evaluated. The results are shown in Table 1 together.
  • the materials used in Examples 1 to 4 and Comparative Example 1 are as follows. Commercial products were used except for the copper fine particles obtained in Synthesis Examples 1 and 2.
  • A1 Commercially available copper fine particles (Mitsui Metals Co., Ltd., trade name: CH-0200; particle diameter: 0.16 ⁇ m)
  • A2 Copper fine particle 1 (polyhedron shape, particle diameter 0.22 ⁇ m)
  • A3 Copper fine particle 2 (plate shape, particle diameter 0.10 ⁇ m)
  • (B) sintering auxiliary material (B1): sintering aid 1 (glutaric anhydride, manufactured by Wako Pure Chemical Industries, Ltd., melting point 50 ° C., boiling point 150 ° C.)
  • (Other sintering aids] Malonic acid (manufactured by Wako Pure Chemical Industries, Ltd., melting point 135 ° C.)
  • thermosetting resin (D1): thermosetting resin 1 (diallyl bisphenol A diglycidyl ether type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., trade name: RD-810 NM; epoxy equivalent 223, hydrolyzable chlorine 150 ppm (1N KOH-ethanol, dioxane Solvent, reflux 30 minutes)
  • Polymerization initiator Dicumyl peroxide (manufactured by NOF Corp., trade name: Park Mill C; decomposition temperature in rapid heating test: 126 ° C.)
  • Thermal conductivity The thermal conductivity after curing of the paste composition was cured at 200 ° C. for 60 minutes, and then the thermal conductivity was measured by a laser flash method according to JIS R 1611-1997.
  • Heat bonding strength (die shear strength)
  • the sample for the measurement of adhesive strength at the time was a back surface gold chip provided with a gold deposited layer on the 4 mm ⁇ 4 mm adhesive surface, and using the obtained paste composition, solid copper frame and PPF (Ni-PC / Au plating) Copper frame) and cured at 200.degree. C. for 60 minutes.
  • the heat bond strength was measured after curing and moisture absorption treatment (85 ° C., relative humidity 85%, 72 hours) using a mount strength measuring apparatus at heat at 260 ° C.
  • Thermal bond strength (cold thermal cycle processing) after high temperature heat treatment is one cycle consisting of heating up from -40 ° C to 250 ° C and cooling down to -40 ° C as 100 cycles and 1000 cycles 2.) For each of the latter, the hot die shear strength at 260 ° C. was measured using a mount strength measurement device.
  • Thermal shock resistance is 85 ° C, relative humidity 85%, after absorbing moisture for 168 hours, IR reflow treatment (260 ° C, 10 seconds) and thermal cycle treatment (-55 ° C to 150 ° C), and -55
  • the operation of cooling to 0 C was regarded as one cycle, and this was performed 1000 cycles), and the number of internal cracks in each package after each treatment was observed with an acoustic microscope.
  • the evaluation results show the number of cracked samples for five samples.
  • Chip Silicon chip and backside gold plated chip
  • Lead frame PPF and copper Sealing material molding: 175 ° C, 2 minutes
  • Post mold cure 175 ° C, 8 hours
  • the paste composition of the present embodiment is excellent in thermal conductivity and excellent in low stress property by containing a sintering aid containing an acid anhydride structure in addition to predetermined copper particles. It was found that the characteristics were good and the reflow peeling resistance was excellent. Moreover, the paste composition of the present embodiment is particularly excellent in hot adhesive strength after high temperature treatment. Therefore, by using this paste composition as a die attach paste for element bonding or a heat radiation member bonding material, a semiconductor device and an electric / electronic device having excellent reliability can be obtained.

Abstract

La présente invention concerne une composition de pâte qui présente des propriétés de conductivité thermique et de dissipation de chaleur exceptionnellement élevées et qui est capable de souder de manière satisfaisante un élément semi-conducteur et un élément électroluminescent à un substrat sans pression. Plus précisément, la présente invention concerne : une composition de pâte comprenant (A) des microparticules de cuivre dans lesquelles l'axe de l'épaisseur ou mineur va de 10 à 500 nm, et (B) un agent auxiliaire de frittage qui comprend une structure d'anhydride d'acide, 0,01 à 1 partie en masse de l'élément auxiliaire de frittage (B) étant ajoutée pour 100 parties en masse des microparticules de cuivre (A) ; un dispositif à semi-conducteur dans lequel ladite composition de pâte est utilisée en tant que pâte de fixation de puce ; et un composant électrique/électronique dans lequel ladite composition de pâte est utilisée en tant que matériau pour le soudage d'un élément de dissipation de chaleur.
PCT/JP2018/039344 2017-11-13 2018-10-23 Composition de pâte, dispositif à semi-conducteur et composant électrique/électronique WO2019093119A1 (fr)

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JP2002329945A (ja) * 2001-04-27 2002-11-15 Harima Chem Inc 異方性導電材料を利用する基板間導通の形成方法
JP2009074054A (ja) * 2007-09-21 2009-04-09 Samsung Electro Mech Co Ltd 非水系導電性ナノインク組成物
JP2011216475A (ja) * 2010-03-18 2011-10-27 Furukawa Electric Co Ltd:The 導電性ペースト、及びその製造方法、並びに導電接続部材
JP2012023014A (ja) * 2010-06-16 2012-02-02 National Institute For Materials Science 金属ナノ粒子ペースト、並びに金属ナノ粒子ペーストを用いた電子部品接合体、ｌｅｄモジュール及びプリント配線板の回路形成方法
WO2015129466A1 (fr) * 2014-02-27 2015-09-03 学校法人関西大学 Nanoparticules de cuivre et leurs procédé de production, dispersion fluide de nanoparticules de cuivre, nano-encre au cuivre, procédé de conservation de nanoparticules de cuivre et procédé de frittage de nanoparticules de cuivre
JP2016089146A (ja) * 2014-10-30 2016-05-23 日華化学株式会社 導電性インク組成物及びそれにより製造された導電性部材
JP2017206755A (ja) * 2016-05-20 2017-11-24 京セラ株式会社 銅微粒子の製造方法、銅微粒子、ペースト組成物、半導体装置及び電気・電子部品

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002329945A (ja) * 2001-04-27 2002-11-15 Harima Chem Inc 異方性導電材料を利用する基板間導通の形成方法
JP2009074054A (ja) * 2007-09-21 2009-04-09 Samsung Electro Mech Co Ltd 非水系導電性ナノインク組成物
JP2011216475A (ja) * 2010-03-18 2011-10-27 Furukawa Electric Co Ltd:The 導電性ペースト、及びその製造方法、並びに導電接続部材
JP2012023014A (ja) * 2010-06-16 2012-02-02 National Institute For Materials Science 金属ナノ粒子ペースト、並びに金属ナノ粒子ペーストを用いた電子部品接合体、ｌｅｄモジュール及びプリント配線板の回路形成方法
WO2015129466A1 (fr) * 2014-02-27 2015-09-03 学校法人関西大学 Nanoparticules de cuivre et leurs procédé de production, dispersion fluide de nanoparticules de cuivre, nano-encre au cuivre, procédé de conservation de nanoparticules de cuivre et procédé de frittage de nanoparticules de cuivre
JP2016089146A (ja) * 2014-10-30 2016-05-23 日華化学株式会社 導電性インク組成物及びそれにより製造された導電性部材
JP2017206755A (ja) * 2016-05-20 2017-11-24 京セラ株式会社 銅微粒子の製造方法、銅微粒子、ペースト組成物、半導体装置及び電気・電子部品

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