CN111033640A - Paste composition, semiconductor device, and electrical/electronic component - Google Patents

Paste composition, semiconductor device, and electrical/electronic component Download PDF

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CN111033640A
CN111033640A CN201880052559.5A CN201880052559A CN111033640A CN 111033640 A CN111033640 A CN 111033640A CN 201880052559 A CN201880052559 A CN 201880052559A CN 111033640 A CN111033640 A CN 111033640A
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paste composition
silver
meth
acrylate
anhydride
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荒川阳辅
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Kyocera Corp
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Kyocera Corp
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    • 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
    • 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 potential barriers, e.g. a 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)
  • Led Device Packages (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

The invention provides a paste composition for bonding a semiconductor and a paste composition for a light-emitting device, which have high thermal conductivity and excellent heat dissipation and can well bond a semiconductor element and a light-emitting element to a substrate in a non-pressure manner. The present invention provides a paste composition, a semiconductor device using the paste composition as a die bonding paste, and an electric and electronic component using the paste composition as a material for bonding a heat dissipating member, the paste composition comprising: (A) silver particles having a thickness or a short diameter of 1nm to 200 nm; silver powder (B) having an average particle diameter of more than 0.2 μm and not more than 30 μm, excluding the silver fine particles (A); and (C) a sintering aid having an anhydride structure, wherein 0.01 to 1 part by mass of the sintering aid (C) is added to 100 parts by mass of the total amount of the silver particles (A) and the silver powder (B).

Description

Paste composition, semiconductor device, and electrical/electronic component
Technical Field
The present invention relates to a paste composition, a semiconductor device and an electric/electronic component manufactured using the same.
Background
As semiconductor products have been increased in capacity, high-speed processing, and fine-circuit, the amount of heat generated during operation of the semiconductor products has increased, and so-called thermal management for releasing heat from the semiconductor products has been demanded. Therefore, a method of mounting a heat dissipating member such as a heat sink or a heat sink on a semiconductor product is generally used, and a material having higher thermal conductivity is desired for bonding the heat dissipating member.
In order to further improve the heat management efficiency according to the form of the semiconductor product, a method of bonding a heat spreader to the semiconductor element itself or to a lower pad portion (ダイパッド portion) of a lead frame to which the semiconductor element is bonded, a method of exposing the lower pad portion to the package surface to provide a function as a heat sink, or the like is employed (for example, see patent document 1).
In addition, a semiconductor element may be bonded to an organic substrate or the like having a heat dissipation mechanism such as a thermal via. In this case, the material used for bonding the semiconductor element is also required to have high thermal conductivity. In recent years, white light-emitting LEDs have been widely used for backlights of full-color liquid crystal displays, lighting devices such as ceiling lamps and ceiling lamps, because of their high luminance. Further, due to high current input caused by the increase in output power of the light-emitting element, the adhesive for bonding the light-emitting element and the substrate may be discolored by heat, light, or the like, or the resistance value may change with time. In particular, in the method of bonding completely depending on the adhesive force of the adhesive, when soldering and packaging electronic components, the bonding material may lose the adhesive force at the solder melting temperature and peel off, and may be extinguished. Further, the high performance of the white light emitting LED increases the amount of heat radiation of the light emitting element chip, and accordingly, the structure of the LED and the heat dissipation of the member used therein are required to be improved.
In particular, in recent years, a power semiconductor device using a wide band gap semiconductor such as silicon carbide (SiC) or gallium nitride having a small power loss has been actively developed, and since the element itself has high heat resistance, it can operate at a high temperature of 250 ℃. However, in order to exhibit the characteristics thereof, a bonding material is required which needs to efficiently release operating heat and which has excellent heat resistance at high temperatures for a long period of time in addition to electrical conductivity and heat conductivity.
In this way, materials (such as die-attach paste and materials for bonding heat dissipation members) used for bonding components of semiconductor devices and electrical/electronic components are required to have high thermal conductivity. These materials are also required to withstand reflow soldering during mounting of a product on a substrate, and are often required to be bonded over a large area, and also required to have low stress properties in order to reduce warpage and the like caused by differences in thermal expansion coefficients between constituent members.
Here, in order to obtain a binder having high thermal conductivity, it is generally necessary to disperse a metal filler such as silver powder or copper powder, or a ceramic filler such as aluminum nitride or boron nitride as a filler in an organic binder at a high content (for example, see patent document 2). However, as a result, the elastic modulus of the cured product becomes high, and it is difficult to achieve both good thermal conductivity and good reflow soldering property (i.e., a property that peeling is difficult to occur after the reflow soldering process).
However, in recent years, as a candidate for a bonding method capable of withstanding such a demand, a bonding method based on silver nanoparticles capable of bonding under a condition of a lower temperature than bulk silver has been focused (for example, see patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2006 and 086273
Patent document 2: japanese patent laid-open publication No. 2005-113059
Patent document 3: japanese patent laid-open publication No. 2011-240406
Disclosure of Invention
Problems to be solved by the invention
However, bonding based on silver nanoparticles generally requires applying pressure while heating at the time of bonding. Therefore, the element may be damaged by the pressurization.
In addition, the environment in the case of using silver nanoparticles to form a junction body requires an oxidizing environment similar to that in the air in order to remove the organic substance coating the surfaces of the silver nanoparticles by oxidative decomposition. Therefore, when a base material such as copper is used, there is a possibility that the adhesion of the sealing material is poor due to oxidation of the copper surface as the base material. In particular, the finer the joined body, the more required is the adhesion. Therefore, if a bonding material that exhibits a sufficient bonding force in an inert environment such as nitrogen can be provided, oxidation of the base material and the like can be reduced, and the field of use and the application possibility of the bonding agent can be significantly expanded.
Accordingly, the present invention provides a paste composition having excellent thermal conductivity, good adhesive properties, and reflow soldering peeling resistance, and a semiconductor device and an electric/electronic component having excellent reliability obtained by using the paste composition as an adhesive material.
Technical scheme for solving problems
The paste composition of the present invention comprises: (A) silver particles having a thickness or a short diameter of 1nm to 200 nm; silver powder (B) having an average particle diameter of more than 0.2 μm and not more than 30 μm, excluding the silver fine particles (A); and (C) a sintering aid having an anhydride structure, wherein 0.01 to 1 part by mass of the (C) sintering aid is added to 100 parts by mass of the total amount of the (A) silver particles and the (B) silver powder.
In the paste composition, the silver particles (A) include at least one of (A1) plate-type silver particles having a center particle diameter of 0.3 to 15 μm and a thickness of 10 to 200nm and (A2) spherical silver particles having an average particle diameter of 10 to 200nm, and may be self-sintered at 100 to 250 ℃. In addition, the sintering aid (C) containing the anhydride structure can be anhydride with the melting point of 40-150 ℃ and the boiling point of 100-300 ℃. The mass ratio of the silver particles (A) to the silver powder (B) is 10:90 to 90: 10.
The semiconductor device of the present invention includes: a substrate; and a semiconductor element bonded and fixed to the substrate via a die bonding material, the die bonding material including the paste composition of the present invention.
Further, an electrical/electronic component of the present invention includes: a heat-radiating member; and a heat-dissipating member bonded and fixed to the heat-dissipating member via a heat-dissipating member bonding material, the heat-dissipating member bonding material including the paste composition of the present invention.
Effects of the invention
According to the paste composition of the present invention, since the cured product has excellent thermal conductivity, good adhesive properties, and excellent reflow soldering peel resistance, the paste composition can be used as a paste composition for bonding a semiconductor and a paste composition for a light-emitting device.
In addition, by using the paste composition as a binder, a semiconductor device and an electric/electronic component excellent in reliability can be provided.
Detailed Description
As mentioned above, the paste composition of the present invention comprises: (A) silver particles having a thickness or a short diameter of 1nm to 200 nm; silver powder (B) having an average particle diameter of more than 0.2 μm and not more than 30 μm, excluding the silver fine particles (A); and (C) a sintering aid containing an anhydride structure.
With such a configuration, a paste composition with little change in viscosity and excellent storage stability can be obtained. Further, the paste composition of the present invention can be bonded without applying pressure, and is also excellent in adhesiveness. Therefore, a semiconductor device and an electric/electronic component manufactured by using the paste composition as a die bonding paste or a material for bonding a heat dissipating member have excellent reflow soldering resistance.
The present invention will be described in detail below.
The silver fine particles (A) used in the present invention are not particularly limited as long as the thickness or the minor axis thereof is 1nm to 200 nm. As the shape of the silver fine particles, spheres, plates, flakes, scales, dendrites, rods, wires, and the like can be used. Here, the thickness of the plate, flake or scale shape, or the shortest diameter of the dendrite, rod, line or sphere may satisfy the above range. In addition, among these, (a) the silver particles may be contained in at least one of (a1) plate-type silver particles and (a2) spherical silver particles.
The plate-like silver fine particles (a1) used in the present invention are plate-like flaky particles having a uniform thickness obtained by growing one metal crystal plane largely, unlike spherical nanoparticles, and known plate-like silver fine particles which can be blended in a resin composition can be mentioned. In general, the plate has a size of the order of micrometers and a thickness of about several nanometers, and has a shape of a triangular plate, a hexagonal plate, a truncated triangular plate, or the like. In addition, the upper surface can be widely covered by [111 ].
Since the (a1) plate-type silver nanoparticles are sintered mainly in the thickness direction, the internal stress is small as compared with the use of spherical silver nanoparticles. Further, the plate-shaped silver fine particles are highly oriented, and thus a bonding material having excellent reflectance is obtained. In addition, since the plate-type silver fine particles are less susceptible to the presence or absence of oxygen unlike ordinary silver fine particles (silver nanoparticles), the plate-type silver fine particles can be sintered in an inert gas atmosphere such as nitrogen.
Further, by containing the plate-type silver microparticles in the paste composition, the thermal conductivity becomes higher than that of a paste composition that is normally filled with only silver powder.
The plate-type silver fine particles (A1) may have a center particle diameter of 0.3 to 15 μm. By setting the center particle diameter in this range, the dispersibility of the silver microparticles in the resin component can be improved.
Further, the paste composition containing such silver fine particles can suppress clogging of a nozzle, deformation of a chip at the time of assembling a semiconductor element, and the like. Here, the central particle diameter refers to a 50% integrated value (50% particle diameter) in a volume-based particle size distribution curve obtained by measurement using a laser diffraction particle size distribution measuring apparatus. In addition, the thickness may be 10 to 200 nm.
This thickness is a value measured by data processing of an observation picture obtained by a Transmission Electron Microscope (TEM) or a Scanning Electron Microscope (SEM). Further, as long as the average thickness of this thickness is within the range. This average thickness is calculated as a number average thickness as described below.
First, a thickness range (maximum thickness: x1, minimum thickness: xn +1) measured from 50 to 100 plate-shaped silver fine particle observation pictures is divided into n parts, and each thickness interval is referred to as [ xj, xj +1] (j is 1,2, · · · · · · n). The division in this case is an aliquot on a logarithmic scale. The representative thickness in each thickness section based on the logarithmic coordinates is represented by the following formula.
[ mathematical formula 1]
Figure BDA0002383441910000051
In addition, r isj(j ═ 1,2,. cndot. cndot., n) is defined as an AND interval [ xj、xj+1]The corresponding relative amount (% difference) can be calculated by the following equation when the total of all the intervals is 100%.
[ mathematical formula 2]
Figure BDA0002383441910000052
Since μ is a numerical value on a logarithmic coordinate and does not have a unit of thickness, 10 is calculated to return the unit of thicknessμI.e. to the power of μ of 10. Will be 10 ofμThe number average thickness is noted.
The length of the long side in the direction perpendicular to the thickness direction may be in the range of 8 to 150 times the thickness, and may be 10 to 50 times. The thickness of the short side perpendicular to the thickness direction may be in the range of 1 to 100 times the thickness, and may be 3 to 50 times.
The silver particles of (A1) plate type can be self-sintered at 100 to 250 ℃. Thus, the inclusion of silver particles that self-sinter at 100 to 250 ℃ improves the fluidity of the silver particles during thermal curing. As a result, the contact points of the silver particles with each other become more numerous.
Further, by increasing the number of contact points of the silver microparticles with each other, the area of the contact points is increased, and the conductivity is significantly improved.
Accordingly, the sintering temperature of the plate-type silver particles may be 100 to 200 ℃.
Here, the self-sinterable means that sintering is performed by heating at a temperature lower than the melting point without applying pressure or adding an additive or the like.
(A1) The plate-type silver particles may be single crystals. The paste composition can ensure good conductivity even when solidified at low temperature by containing the plate-shaped silver fine particles of single crystal.
(A1) The plate-type silver particles are oriented in the horizontal direction in the coating film, having more contact points, so that the conductivity can be improved. This is because the compression by the self weight of the chip at the time of thermal curing, the volume phenomenon due to vaporization of the low boiling point component contained in the paste composition, and the volume shrinkage due to thermal curing of the paste composition have such an effect of excluding the volume, and the like, and the coating film is naturally oriented so as to be stacked in the thickness direction, and a large contact point between the silver microparticles can be secured.
The surface of the silver particles of the (a1) plate form may be surface-treated as necessary, and examples thereof include stearic acid, palmitic acid, caproic acid, and oleic acid for improving compatibility.
Examples of the plate-type silver fine particles (A1) include M612 (product name: center particle diameter: 6 to 12 μ M, particle thickness: 60 to 100nm, melting point: 250 ℃) manufactured by TOKUSEN industries, Inc. (トクセン industries, Co., Ltd.), M27 (product name: center particle diameter: 2 to 7 μ M, particle thickness: 60 to 100nm, melting point: 200 ℃), M13 (product name: center particle diameter: 1 to 3 μ M, particle thickness: 40 to 60nm, melting point: 200 ℃), N300 (product name: center particle diameter: 0.3 to 0.6 μ M, particle thickness: 50nm or less, melting point: 150 ℃). These plate-type silver particles may be used alone or in combination. In particular, in order to increase the filling rate, for example, in the plate-shaped silver fine particles, silver fine particles having a small particle diameter such as N300 may be combined with relatively large silver fine particles such as M27 and M13.
The spherical silver fine particles (A2) used in the present invention have a particle diameter of 10 to 200 nm. The spherical silver fine particles (a2) are generally fine particles having a coating layer of an organic compound provided on the metal surface of the silver fine particles or fine particles having the silver fine particles dispersed in an organic compound. In such a configuration, the metal surfaces of the silver fine particles can be prevented from coming into direct contact with each other, so that the formation of aggregated lumps of silver fine particles can be reduced, and the state in which the silver fine particles are dispersed can be maintained. The particle size is a value measured by data processing of an observation picture obtained by a Transmission Electron Microscope (TEM) or a Scanning Electron Microscope (SEM). The average particle diameter of the (a2) spherical silver fine particles may be within the above range. The average particle diameter is calculated as a number average particle diameter of particle diameters measured from 50 to 100 observation pictures of the spherical silver fine particles. The number average particle diameter may be calculated in the same manner as the average thickness.
As the coating layer on the surface of the silver fine particles or the organic compound for dispersing the silver fine particles, an organic compound having a molecular weight of 20000 or less and having nitrogen, carbon, and oxygen as components, specifically, an organic compound having a functional group such as an amino group or a carboxyl group can be used.
Examples of the organic compound having a carboxyl group used herein include at least one organic compound selected from organic carboxylic acids having a molecular weight of 110 to 20000.
Examples thereof include carboxylic acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, eicosanoic acid, behenic acid, 2-ethylhexanoic acid, oleic acid, linoleic acid, linolenic acid, and dipropionic acid-terminated polyethylene oxide. Further, as the organic compound, a carboxylic acid derivative of the carboxylic acid may also be used.
Examples of the amino group-containing organic compound used herein include alkylamines.
Primary amines such as butylamine, methoxyethylamine, 2-ethoxyethylamine, hexylamine, octylamine, 3-butoxypropylamine, nonylamine, dodecylamine, hexadecylamine, octadecylamine, cocoamine, tallowamine, hydroxytallowamine, oleylamine, laurylamine, stearylamine, and 3-aminopropyltriethoxysilane; secondary amines such as coco-amine, dihydrotallow amine, and distearyl amine; and tertiary amines such as dodecyldimethylamine, didodecylmonomethylamine, tetradecyldimethylamine, octadecyldimethylamine, cocoyldimethylamine, dodecyltetradecyldimethylamine, trioctylamine and the like; in addition, diamines such as naphthalenediamine, stearylpropylenediamine, octamethylenediamine, nonanediamine, diamine-terminated polyethylene oxide, triamine-terminated polypropylene oxide, and diamine-terminated polypropylene oxide.
When the molecular weight of the organic compound coating or dispersing (a2) the spherical silver fine particles is smaller than 20000, the organic compound is easily released from the surface of the metal particles. Therefore, after the paste is fired, the remaining amount of the organic compound in the cured product decreases. As a result, good conductivity was obtained.
Further, if the molecular weight of the organic compound coating or dispersing (a2) the spherical silver fine particles is 50 or more, aggregation of the silver fine particles is reduced in the paste form, and therefore, good storage stability can be obtained.
The mass ratio of the silver fine particles to the organic compound that coats or disperses the silver fine particles in the spherical silver fine particles (a2) may be 90:10 to 99.5: 0.5. When the mass ratio is within this range, aggregation of silver particles can be reduced in the paste, and low-temperature sinterability can be imparted to the paste composition. In addition, the residue of organic compounds in the cured product is reduced after the paste is fired.
This can increase the filling ratio of the paste composition with silver particles including silver powder (B) described later.
Further, by combining the silver fine particles (a1) plate type silver fine particles and the silver fine particles (a2) sphere as the silver fine particles (a), the paste composition can be made to be a paste composition having better characteristics such as filling rate of silver particles and low-temperature sinterability.
The silver powder (B) used in the present invention is a silver powder having an average particle diameter of more than 0.2 μm and not more than 30 μm, and it is usually only necessary to add a silver powder as an inorganic filler for imparting conductivity to the resin binder. When the obtained paste composition is used for bonding an element such as a semiconductor element and a supporting substrate, the bonding strength can be further improved by adding the silver particles of the (B) silver powder of micron order to the silver fine particles of the (a) silver. The shape of the silver particles used herein includes, for example, flake, scaly, dendritic, rod, linear, spherical, and the like. The silver powder (B) does not contain the silver particles (a).
Here, the average particle diameter refers to a 50% integrated value (50% particle diameter) in a volume-based particle size distribution curve obtained by measurement using a laser diffraction particle size distribution measuring apparatus.
The ratio of the silver particles (A) to the silver powder (B) may be 10:90 to 90:10, or 10:90 to 50:50, where the total amount of the silver particles (A) and the silver powder (B) is 100. When the ratio of the silver microparticles (A) to the silver powder (B) is in this range, voids are not generated in the cured product, and a stringiness phenomenon is not generated during mounting, so that good workability can be obtained.
The sintering aid (C) having an anhydride structure used in the present invention is not particularly limited as long as it promotes sintering of the silver fine particles (a) or densifies a sintered body obtained by sintering. The sintering aid (C) has a structure in which two molecules of an oxyacid are subjected to dehydration condensation, and for example, it is sufficient that the sintering aid has a structure in which a carboxyl group of a compound having a plurality of carboxyl groups is subjected to dehydration condensation in a molecule.
In particular, since the carboxylic anhydride has high coordination energy with respect to the surface of the silver fine particles, the carboxylic anhydride is coordinated to the surface of the silver fine particles instead of the protective group on the surface of the silver fine particles. The silver fine particles coordinated to the carboxylic anhydride on the surface exhibit good dispersibility. Further, since the carboxylic anhydride is excellent in volatility, it exhibits good low-temperature sinterability.
As the sintering aid (C), specifically, examples of the acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, iso-butyric anhydride, valeric anhydride, trimethyl acetic anhydride, hexanoic anhydride, heptanoic anhydride, decanoic anhydride, lauric anhydride, myristic anhydride, palmitic anhydride, stearic anhydride, behenic anhydride, crotonic anhydride, methacrylic anhydride, oleic anhydride, linoleic anhydride, chloroacetic anhydride, iodoacetic anhydride, dichloroacetic anhydride, trifluoroacetic anhydride, chlorodifluoroacetic anhydride, trichloroacetic anhydride, pentafluoropropionic anhydride, heptafluorobutyric anhydride, succinic anhydride, methylsuccinic anhydride, 2-dimethylsuccinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, diethanol anhydride, benzoic anhydride, phenylsuccinic anhydride, phenylmaleic anhydride, homophthalic anhydride, isatoic anhydride, phthalic anhydride, tetrafluorophthalic anhydride, tetrabromophthalic anhydride, and the like.
Among them, the aromatic-free compound does not generate voids and is excellent in low-temperature sinterability.
The melting point of the sintering aid (C) used in the present invention may be in the range of 40 to 150 ℃. When the melting point is within this range, the storage stability of the paste composition, the workability in applying the paste, and the sinterability during heating the paste are good.
The boiling point of the sintering aid (C) used in the invention can be 100-300 ℃ or 100-275 ℃. If the boiling point is in this range, voids are not generated. By blending such an acid anhydride as a sintering aid, a paste composition excellent in adhesiveness, thermal conductivity, and reflow soldering peel resistance can be obtained.
In the present invention, the paste composition may also use (D) a thermosetting resin. The thermosetting resin (D) used in the present invention is not particularly limited as long as it is a thermosetting resin generally used for adhesive applications. (D) The thermosetting resin may be a resin that is liquid at room temperature (25 ℃). Examples of the thermosetting resin (D) include cyanate ester resins, epoxy resins, radical polymerizable acrylic resins, and maleimide resins. By containing (D) the thermosetting resin, an adhesive material (paste) having an appropriate viscosity can be obtained. In addition, by containing (D) a thermosetting resin, the temperature of the paste composition is increased by the reaction heat at the time of curing, and the sintering property of the silver fine particles is promoted.
The cyanate ester resin is a compound having an-NCO group in a molecule, and is a resin which is cured by reacting the-NCO group by heating to form a three-dimensional network structure. Specific examples thereof include 1, 3-dicyanobenzene, 1, 4-dicyanobenzene, 1,3, 5-tricyanobenzene, 1, 3-dicyanonaphthalene, 1, 4-dicyanonaphthalene, 1, 6-dicyanonaphthalene, 1, 8-dicyanonaphthalene, 2, 6-dicyanonaphthalene, 2, 7-dicyanonaphthalene, 1,3, 6-tricyanonaphthalene, 4' -dicyanobenzene, bis (4-cyanophenyl) methane, bis (3, 5-dimethyl-4-cyanophenyl) methane, 2-bis (4-cyanophenyl) propane, 2-bis (3, 5-dibromo-4-cyanophenyl) propane, bis (4-cyanophenyl) ether, bis (4-cyanophenyl) sulfide, and mixtures thereof, Bis (4-cyanophenyl) sulfone, tris (4-cyanophenyl) phosphite, tris (4-cyanophenyl) phosphate, and cyanate esters obtained by reacting a novolak resin with a cyanogen halide. In addition, a prepolymer having a triazine ring formed by trimerizing the cyanate group of the polyfunctional cyanate ester resin can be used as the cyanate ester resin. The prepolymer can be obtained by polymerizing the polyfunctional cyanate ester resin monomer with an acid such as an inorganic acid or a lewis acid, a base such as sodium alkoxide or tertiary amine, or a salt such as sodium carbonate as a catalyst.
As the curing accelerator for the cyanate ester resin, generally known ones can be used. Examples thereof include, but are not limited to, organic metal complexes such as zinc octoate, tin octoate, cobalt naphthenate, zinc naphthenate, and iron acetylacetonate, metal salts such as aluminum chloride, tin chloride, and zinc chloride, and amines such as triethylamine and dimethylbenzylamine. These curing accelerators may be used alone or in combination of two or more. In addition, the cyanate ester resin can be used in combination with other resins such as epoxy resin, acrylic resin, maleimide resin, and the like.
The epoxy resin is a compound having one or more glycidyl groups in a molecule, and is a resin which is cured by reacting glycidyl groups by heating to form a three-dimensional network structure.
The compound containing two or more glycidyl groups in one molecule can be obtained by epoxidizing a compound having two or more hydroxyl groups. Examples of such a compound include, but are not limited to, a bifunctional substance obtained by epoxidizing a diol having an alicyclic structure such as bisphenol a, bisphenol F, hydrogenated bisphenol, cyclohexanediol, cyclohexanedimethanol, and cyclohexanediol, or a derivative thereof, a bifunctional substance obtained by epoxidizing an aliphatic diol such as butanediol, hexanediol, octanediol, nonanediol, and decanediol, or a derivative thereof, a trifunctional substance obtained by epoxidizing a compound having a trihydroxyphenylmethane skeleton or an aminophenol skeleton, and a polyfunctional substance obtained by epoxidizing a phenol novolac resin, a cresol novolac resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a naphthol aralkyl resin, and the like. Since the epoxy resin is in the form of a paste or a liquid at room temperature as a resin composition, it may be in the form of a liquid at room temperature alone or as a mixture. Commonly used reactive diluents may also be used. Examples of the reactive diluent include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and tolyl glycidyl ether, and aliphatic glycidyl ethers.
In this case, a curing agent is used for the purpose of curing the epoxy resin, and examples of the curing agent for the epoxy resin include aliphatic amines, aromatic amines, dicyandiamide, dihydrazide compounds, acid anhydrides, phenol resins, and the like. The dihydrazide compound may include a carboxylic acid dihydrazide such as adipic acid dihydrazide, dodecane acid dihydrazide, isophthalic acid dihydrazide, or paraoxybenzoic acid dihydrazide, and the acid anhydride may include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, a reaction product of maleic anhydride and polybutadiene, or a copolymer of maleic anhydride and styrene.
The phenolic resin used as a curing agent for an epoxy resin is a compound having two or more phenolic hydroxyl groups in one molecule, and a crosslinked structure cannot be formed in the case of a compound having one phenolic hydroxyl group in one molecule, and therefore, the cured product characteristics are deteriorated and cannot be used.
The number of phenolic hydroxyl groups in one molecule may be two or more, but the number of phenolic hydroxyl groups may be 2 to 5, or two or three. When the number of phenolic hydroxyl groups is within this range, a viscosity having an appropriate molecular weight and good handleability can be obtained.
Examples of such compounds include bisphenols such as bisphenol F, bisphenol a, bisphenol S, tetramethylbisphenol a, tetramethylbisphenol F, tetramethylbisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, tetramethylbisphenol, ethylenebisphenol, methylethylenebis (methylphenol), cyclohexylenediphenol, and bisphenol, and derivatives thereof, trifunctional phenols such as tris (hydroxyphenyl) methane and tris (hydroxyphenyl) ethane, and derivatives thereof, and dinuclear or trinuclear compounds obtained by reacting phenols such as phenol novolak and cresol novolak with formaldehyde, and derivatives thereof.
In addition, the paste composition of the present invention may contain a curing accelerator for accelerating curing. Examples of the curing accelerator for epoxy resins include imidazoles, triphenylphosphine, tetraphenylphosphine, and salts thereof, amine compounds such as diazacycloundecene, and salts thereof. As the curing accelerator for the epoxy resin, for example, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-C11H23Imidazole compounds such as addition products of imidazole and 2, 4-diamino-6-vinyltriazine. The imidazole compound may have a melting point of 180 ℃ or higher. In addition, epoxy resins can be used in combination with cyanate ester resins, acrylic resins, maleimide resins.
The radical polymerizable acrylic resin is a compound having one or more (meth) acryloyl groups in a molecule, and is a resin which forms a three-dimensional network structure by reacting with a (meth) acryloyl group and is cured.
Examples of the acrylic resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, 2-cyclohexanediol mono (meth) acrylate, 1, 3-cyclohexanediol mono (meth) acrylate, 1, 4-cyclohexanediol mono (meth) acrylate, 1, 2-cyclohexanedimethanol mono (meth) acrylate, 1, 3-cyclohexanedimethanol mono (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, 1, 2-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-cyclohexanediol (meth) acrylate, 1, 3-cyclohexanedimethanol mono (meth) acrylate, 1, 4-cyclohexanedimethanol mono (meth) acrylate, hydroxyl group-containing (meth) acrylates such as 1, 3-cyclohexanediol mono (meth) acrylate, 1, 4-cyclohexanediol mono (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, and carboxyl group-containing (meth) acrylates obtained by reacting these hydroxyl group-containing (meth) acrylates with dicarboxylic acids or derivatives thereof. Examples of the dicarboxylic acid that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and derivatives thereof.
Furthermore, methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isopentyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylates, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, 2,3,3, 3-bis (meth) acrylamide, N-octyloxy) methacrylate, N-bis (meth) acrylamide, N-octyloxyethyl (meth) acrylate, N-octyleneglycol (meth) acrylate, N-acrylamide, N-2, N-octyleneglycol (meth) acrylate, N-acrylamide, N-2, N-octyleneglycol (meth) acrylate, N-N-octyleneglycol (meth) acrylate, N-acrylamide, N-octyleneglycol (meth) acrylate, N-2, N-acrylamide, N-2, N-acrylamide, N-2, N-octyleneacrylamide, N-2-acrylamide, N-N-octyleneglycol (meth).
Further, a polyether having a molecular weight of 100 to 10000, a polyester, a polycarbonate, a compound having a (meth) acrylic group in a poly (meth) acrylate, a (meth) acrylate having a hydroxyl group, a (meth) acrylamide having a hydroxyl group, or the like can be used.
The polyether skeleton may be one in which organic groups having 1 to 6 carbon atoms are repeated via an ether bond. In addition, the polyether backbone may be free of aromatic rings. The compound having a (meth) acrylic group in the polyether can be obtained by reacting a polyether polyol with (meth) acrylic acid or a derivative thereof.
The polyester skeleton may be one in which organic groups having 1 to 6 carbon atoms are repeated via ester bonds. In addition, the polyester backbone may not contain aromatic rings. The compound having a (meth) acrylic group in the polyester can be obtained by reacting a polyester polyol with (meth) acrylic acid or a derivative thereof.
The polycarbonate skeleton may be one in which organic groups having 1 to 6 carbon atoms are repeated via a carbonate bond. In addition, the polycarbonate backbone may be free of aromatic rings. The compound having a (meth) acrylic group in the polycarbonate can be obtained by reacting a polycarbonate polyol with (meth) acrylic acid or a derivative thereof.
As the poly (meth) acrylate skeleton, a copolymer of (meth) acrylic acid and (meth) acrylate; copolymers of (meth) acrylates having hydroxyl groups and (meth) acrylates having no polar groups such as carboxyl groups and hydroxyl groups; and copolymers of (meth) acrylates having glycidyl groups and (meth) acrylates having no polar group.
As for the copolymers, each can be obtained by reacting a carboxyl group with a (meth) acrylate having a hydroxyl group or a (meth) acrylate having a glycidyl group, or by reacting a hydroxyl group with a (meth) acrylic acid having no polar group and derivatives thereof.
Further, the compound having a (meth) acrylic group in the poly (meth) acrylate can be obtained by reacting a poly (meth) acrylate polyol with (meth) acrylic acid or a derivative thereof.
The hydroxyl group-containing (meth) acrylate or (meth) acrylamide is a hydroxyl group-containing (meth) acrylate or (meth) acrylamide having one or more (meth) acrylic groups in each molecule.
The (meth) acrylate having a hydroxyl group can be obtained by reacting a polyol compound with (meth) acrylic acid and a derivative thereof. The reaction can be carried out by a known reaction, and usually 0.5 to 5 times by mol of an acrylic acid ester or acrylic acid is used for the polyol compound.
The (meth) acrylamide having a hydroxyl group can be obtained by reacting an amine compound having a hydroxyl group with (meth) acrylic acid or a derivative thereof. In the method for producing (meth) acrylamides by reacting a (meth) acrylate with an amine compound, usually, an amine, cyclopentadiene, alcohol, or the like is added to a double bond as a protecting group in advance, and after completion of amidation, the protecting group is released by heating to produce the desired product. This is to enrich the double bond of the (meth) acrylate with stability.
In this way, the hydroxyl group is contained, whereby the sintering property by the reduction effect is promoted and the adhesion is improved.
The hydroxyl group as referred to herein is an alcoholic group in which a hydrogen atom of an aliphatic hydrocarbon group is substituted, and if the content of the hydroxyl group is in the range of 1 to 50 in one molecule, the curing is excessive and the sinterability is not inhibited.
Examples of the acrylic resin compound having such a hydroxyl group include compounds represented by the following general formulae (I) to (IV).
[ chemical formula 1]
Figure BDA0002383441910000141
(in the formula, R1Represents a hydrogen atom or a methyl group, R2Represents a divalent aliphatic hydrocarbon group having 1 to 100 carbon atoms or an aliphatic hydrocarbon group having a cyclic structure. )
[ chemical formula 2]
Figure BDA0002383441910000142
(in the formula, R1And R2Each represents the same group as described above. )
[ chemical formula 3]
Figure BDA0002383441910000143
(in the formula, R1The same groups as above, and n represents an integer of 1 to 50. )
[ chemical formula 4]
Figure BDA0002383441910000144
(in the formula, R1And n represents the same groups as described above, respectively. )
As the (meth) acrylate or the (meth) acrylamide, the compounds may be used alone or in combination of two or more.
R in the general formulae (I) and (II)2The number of carbon atoms of (A) is 1 to 100, and may be 1 to 36. If R is2The carbon number of (2) is in the range of 1 to 36, the curing is excessive, and the sinterability is not impaired.
Here, when the thermosetting resin (D) is an acrylic resin, a polymerization initiator is generally used in the polymerization, but a thermal radical polymerization initiator may be used as the polymerization initiator, and a known thermal radical polymerization initiator may be used.
As the thermal radical polymerization initiator, an initiator having a decomposition temperature of 40 ℃ to 140 ℃ in a rapid heating test (decomposition starting temperature at 4 ℃/min when a sample (1 g) is placed on a hot plate) was used. When the decomposition temperature is 40 ℃ or higher, the normal temperature storage stability of the conductive paste is good, and when the decomposition temperature is 140 ℃ or lower, an appropriate curing time can be obtained.
Specific examples of the thermal radical polymerization initiator satisfying such characteristics include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1-bis (t-butylperoxy) 3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-hexylperoxy) 3,3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (4, 4-di-t-butylperoxycyclohexyl) propane, 1-bis (t-butylperoxy) cyclododecane, n-butyl-4, 4-bis (t-butylperoxy) valerate, 2-bis (t-butylperoxy) butane, 1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, t-hexylhydroperoxide, dicumyl peroxide, 2, 5-dimethyl-2-butylperoxy) isopropyl carbonate, 3, 5-di (t-butylperoxy) isopropyl carbonate, 3, 5-butyl peroxy ethyl peroxy) methyl butyrate, 3, 5-butyl peroxy ethyl peroxy benzoate, 5-butyl peroxy ethyl peroxy isobutyrate, di (t-butyl) methyl peroxy) methyl hexanoate, di (t-butyl) hexanoate, di (t-butyl peroxy) peroxy ethyl peroxy benzoate, di (t-butyl) peroxy ethyl peroxy) isobutyrate, di (t-butyl) peroxy benzoate, di (t-butyl) peroxy ethyl peroxy benzoate, di (t-butyl) peroxy ethyl peroxy benzoate, di (t-butyl) peroxy benzoate, di (t-butyl) peroxy benzoate, di-butyl peroxy benzoate, di (t-butyl peroxy) peroxy benzoate, di-butyl peroxy) peroxy benzoate, di (t-butyl peroxy benzoate, di (t-butyl peroxy) peroxy benzoate, di (t-butyl peroxy) peroxy benzoate, di (t-butyl peroxy) peroxy benzoate, di-butyl peroxy) peroxy benzoate, di-butyl peroxy benzoate, di (t-butyl peroxy benzoate, di-butyl peroxy) peroxy benzoate, di (t-butyl peroxy benzoate, di-butyl peroxy.
These polymerization initiators may be used alone or in combination of two or more for curability control. In addition, various polymerization inhibitors may be added in advance in order to improve the storage stability of the die-bonding paste.
The amount of the thermal radical initiator may be 0.1 to 10 parts by mass per 100 parts by mass of the radical polymerizable acrylic resin component.
If the amount is 0.1 parts by mass or more, a die bonding paste having good curability can be obtained, and if the amount is 10 parts by mass or less, storage stability is excellent and good workability can be obtained.
The maleimide resin is a compound containing one or more maleimide groups in one molecule, and is cured by heating to react the maleimide groups to form a three-dimensional network structure. For example, bismaleimide resins such as N, N '- (4, 4' -diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, and 2, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane may be mentioned.
The maleimide resin is a compound obtained by reacting dimer acid diamine with maleic anhydride, and is a compound obtained by reacting maleinized amino acid such as maleinimidoacetic acid or maleinimidocaproic acid with polyhydric alcohol.
As the maleimidoylated amino acid, it can be obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid. As the polyol, polyether polyol, polyester polyol, polycarbonate polyol, poly (meth) acrylate polyol can be used.
The maleimide resin may contain no aromatic ring.
The maleimide group can be used in combination with an allyl ester resin because it can react with an allyl group. The allyl ester resin may be aliphatic.
Further, the allyl ester resin may be a compound obtained by transesterification of cyclohexane diallyl ester with an aliphatic polyol. The number average molecular weight of the allyl ester compound is not particularly limited, and may be 500 to 10,000, or 500 to 8,000. When the number average molecular weight is within the above range, curing shrinkage can be particularly reduced, and a decrease in adhesion can be prevented. In addition, the resin can be used together with cyanate ester resin, epoxy resin and acrylic resin.
The maleimide resin is a bismaleimide resin having an aliphatic hydrocarbon group in the main chain, and the main chain connecting two maleimide groups may have one or more aliphatic hydrocarbon groups having carbon atoms.
The aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have 6 or more carbon atoms, 12 or more carbon atoms, or 24 or more carbon atoms. In addition, the aliphatic hydrocarbon group may be directly bonded to the maleimide group.
As the maleimide resin, for example, a compound represented by the following general formula (V) can be used.
[ chemical formula 5]
Figure BDA0002383441910000171
(wherein Q represents a divalent straight, branched or cyclic aliphatic hydrocarbon group having 6 or more carbon atoms, and P is a divalent atom or organic group and is selected from O, CO, COO and CH2、C(CH3)2、C(CF3)2、S、S2SO and SO2At least one divalent atom or organic group, and m represents an integer of 1 to 10. )
Here, the divalent atom represented by P includes O, S and the like, and the divalent organic group includes CO, COO, CH2、C(CH3)2、C(CF3)2、S2、SO、SO2And the like, and organic groups containing at least one of these atoms or organic groups. Examples of the organic group containing the above atom or organic group include a hydrocarbon group having 1 to 3 carbon atoms as a structure other than the above, and a benzene ringExamples of P in this case include a group represented by the following chemical formula.
[ chemical formula 6]
Figure BDA0002383441910000181
A thermosetting resin composition for semiconductor bonding which has excellent heat resistance, low stress, and good thermal bonding strength after moisture absorption can be obtained by using a bismaleimide resin having an aliphatic hydrocarbon group in the main chain.
Specific examples of such maleimide resins include BMI-1500 (product name: 1500, manufactured by Designer polymers Co., Ltd. (デジグナーモレキュールズ Co.)), BMI-1700 (product name: 1700, manufactured by Designer polymers Co., Ltd.), and the like.
In addition, the maleimide resin may be used in combination with a polymer of allylated bisphenol and epichlorohydrin, i.e., allylated epoxy resin or radical polymerizable acrylic resin containing the hydroxyl group.
The allylated epoxy resin, which is a polymer of allylated bisphenol and epichlorohydrin, can be obtained, for example, by dissolving a polyphenol compound in an alcohol such as methanol, isopropanol, or n-propanol, or a ketone such as acetone or methyl ethyl ketone, reacting a halogenated allyl group such as allyl chloride or allyl bromide with a base such as sodium hydroxide or potassium hydroxide to obtain an allyl ether of the polyphenol compound, and reacting the resultant with a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at 20 to 120 ℃ for 0.5 to 10 hours while adding the solid as a catalyst to a mixture of the allylated polyphenol compound and the epihalohydrin.
As the allylated epoxy resin, a compound represented by the following general formula (VI) can be used.
[ chemical formula 7]
Figure BDA0002383441910000191
(in the formula, R3～R10Each independently is a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group and a substituted or unsubstituted allyl group, at least one of which is a substituted or unsubstituted allyl group, and X is selected from SO, SO2、CH2、C(CH3)2、C(CF3)2O, CO and COO, k is 0 or 1).
When the maleimide resin and the allylated epoxy resin are used in combination, the compounding ratio thereof may be 50/50 to 95/5, or 65/35 to 90/10.
When the maleimide resin and the radical polymerizable acrylic resin are used in combination, the blending ratio thereof may be 5/95 to 95/5.
Here, when the thermosetting resin (D) is blended, the total amount of the silver particles (a) and the silver powder (B) is 1 to 20 parts by mass, based on 100 parts by mass of the total amount.
If the thermosetting resin (D) is 1 part by mass or more, the workability at the time of application of the paste composition becomes good, and if the thermosetting resin (D) is 20 parts by mass or less, the high thermal conductivity after firing of the paste composition can be ensured, and good heat dissipation can be obtained.
In addition, if (D) the thermosetting resin is in the above range, deterioration due to light and heat is reduced, and therefore, the life of the light-emitting device can be maintained without lowering the coloring and the intensity.
Within such a blending range, the adhesive performance of the acrylic resin can be utilized to prevent the silver particles from contacting each other, and the mechanical strength of the entire adhesive layer can be easily maintained.
Further, the paste composition of the present invention may also contain (E) a solvent. As the solvent (E), any known solvent can be used as long as it functions as a reducing agent. The solvent may be an alcohol, for example, an aliphatic polyol. Examples of the aliphatic polyhydric alcohol include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol, glycerin, and polyethylene glycol. These solvents may be used alone or in combination of two or more.
As the (E) solvent, an alcohol solvent functioning as a reducing agent is heated to a high temperature by heat treatment at the time of paste curing (firing) to increase the reducing power of the alcohol, and silver oxide partially present in silver powder and silver microparticles and metal oxide (for example, copper oxide) on the metal substrate are reduced to pure metal by the alcohol. As a result, it is considered that a more dense cured film having improved conductivity and high adhesion to the substrate can be formed. Further, by being interposed between the semiconductor element and the metal substrate, the alcohol is partially refluxed during the heat treatment at the time of curing the paste, and the alcohol as a solvent is not directly lost from the system by vaporization. Therefore, even if the paste curing temperature is not lower than the boiling point of the solvent, the metal oxide can be reduced more efficiently.
The boiling point of the solvent (E) may be, specifically, 100 to 300 ℃ or 150 to 290 ℃.
If the boiling point is 100 ℃ or higher, the amount of the solvent volatilized is reduced, thus maintaining the reducing power of the paste composition. Therefore, stable adhesive strength can be obtained.
Further, if the boiling point is 300 ℃ or lower, the amount of the solvent remaining in the paste after sintering is reduced, and a dense sintered body can be obtained.
The amount of the solvent (E) to be mixed may be 7 to 20 parts by mass, based on 100 parts by mass of the total amount of the silver particles (a) and the silver powder (B). When the solvent is contained in an amount of 7 parts by mass or more, the viscosity can be improved in workability in paste application. If the content of the solvent is 20 parts by mass or less, the silver fine particles and the silver powder do not settle in the paste composition. When the amount of the solvent is within this range, a paste composition having good reliability can be obtained.
In the paste composition of the present invention, in addition to the above components, a curing accelerator, a rubber, a low-stress agent such as silicone, a coupling agent, an antifoaming agent, a surfactant, a colorant (pigment, dye), various polymerization inhibitors, an antioxidant, a solvent, and other various additives, which are generally blended in such a composition, may be blended as necessary within a range not to impair the effect of the present invention. These additives may be used alone or in combination of two or more.
Examples of such additives include silane coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and sulfide silane, coupling agents such as titanate coupling agents, aluminum coupling agents, and aluminum/zirconium coupling agents, colorants such as carbon black, solid stress-reducing components such as silicone oil and silicone rubber, and inorganic ion exchangers such as hydrotalcite.
The method for producing the paste composition of the present invention comprises sufficiently mixing the above-mentioned essential components (A) to (C), optional components (D) and (E) which may be blended as required, additives such as other coupling agents, and solvents. Subsequently, kneading treatment is performed by a disperser, kneader, three-roll mill, or the like. Further, it can be prepared by defoaming.
The paste composition of the present invention obtained in this manner has high thermal conductivity and excellent heat dissipation properties. Therefore, if the resin composition is used as a bonding material for a substrate or the like of an element or a heat dissipation member, the property of releasing heat from the inside of the device to the outside can be improved, and the product characteristics can be stabilized.
Next, the semiconductor device and the electric/electronic component of the present invention will be described.
The semiconductor device of the present invention is a device for bonding a semiconductor element to a substrate as an element support member by using the paste composition. That is, here, a paste composition is used as the die-bonding paste, and the semiconductor element and the substrate are bonded and fixed via this paste composition.
Here, the semiconductor element may be any known semiconductor element, and examples thereof include a transistor and a diode. Further, as the semiconductor element, a light emitting element such as an LED can be given. The type of the light-emitting element is not particularly limited, and examples thereof include a light-emitting element formed by forming a nitride semiconductor such as InN, AlN, GaN, InGaN, AlGaN, and InGaAlN as a light-emitting layer on a substrate by MOCVD or the like. Examples of the element support member include copper, silver-plated copper, PPF (pre-plated lead frame), glass epoxy, and ceramics.
The semiconductor device and the electric and electronic parts of the present invention can bond a semiconductor element to a base material which is not subjected to a metal plating treatment by using the above-mentioned paste composition. The semiconductor device obtained in this way has a significantly improved connection reliability with respect to a temperature cycle after mounting as compared with the conventional device. Further, since the resistance value is sufficiently small and the change with time is small, there is an advantage that the reduction with time of the output power is small and the life is long even if the driving is performed for a long time.
In addition, the electric/electronic component of the present invention is a device for bonding a heat-dissipating member to a heat-dissipating member using the paste composition. That is, here, the paste composition is used as a heat dissipation member bonding material, and the heat dissipation member are bonded and fixed via the paste composition.
Here, the heat radiating member may be the semiconductor element or a member having the semiconductor element, or may be another heat radiating member. Examples of the heat radiating member other than the semiconductor element include an optical pickup and a power transistor. Examples of the heat dissipation member include a heat sink and a heat sink.
In this manner, by bonding the heat radiating member to the heat radiating member using the paste composition, heat generated by the heat radiating member can be more effectively radiated to the outside through the heat radiating member, and a temperature increase of the heat radiating member can be suppressed. The heat-radiating member and the heat-radiating member may be directly bonded via the paste composition, or may be indirectly bonded with another member having high thermal conductivity interposed therebetween.
[ examples ]
The present invention will be further described with reference to examples, but the present invention is not limited to these examples at all.
Examples 1 to 12 and comparative examples 1 to 4
In the present invention, the components were mixed in the formulation shown in tables 1 and 2, and kneaded using rolls to obtain a paste composition. The obtained paste composition was evaluated using the following method. The results are shown in tables 1 and 2. As the materials used in the examples and comparative examples, commercially available products as described below can be used.
(A1) The method comprises the following steps Plate-type silver particles (manufactured by TOKUSEN industries, Ltd.) (トクセン industries, Ltd.) having a product name of M13, a center particle diameter of 2 μ M and a thickness of 50nm or less)
(A2) The method comprises the following steps Spherical silver particles (product name: MDot, manufactured by Sanzhiji ribbon (Ltd.); average particle diameter: 50nm)
(B) The method comprises the following steps Silver powder (manufactured by Futian Metal foil powder industry Co., Ltd.; product name: AgC-212D; average particle diameter: 5 μm)
(C1) The method comprises the following steps Sintering aid 1 (glutaric anhydride, Wako pure chemical industries, Ltd., melting point: 50 ℃ C., boiling point: 150 ℃ C.)
(C2) The method comprises the following steps Sintering aid 2 (succinic anhydride, manufactured by Wako pure chemical industries, Ltd., melting point: 118 ℃ C., boiling point: 261 ℃ C.)
(C3) The method comprises the following steps Sintering aid 3 (diethanol anhydride, manufactured by Wako pure chemical industries, Ltd., melting point: 92 ℃ C., boiling point: 240 ℃ C.)
(C4) The method comprises the following steps Sintering aid 4 (phthalic anhydride, manufactured by Wako pure chemical industries, Ltd., melting point: 130 ℃ C., boiling point: 284 ℃ C.)
(D1) The method comprises the following steps Hydroxyethyl acrylamide ((HEAA, Kabushiki Kaisha)
(D2) The method comprises the following steps imide-Expandable bismaleimide (product name: BMI-1500; number average molecular weight: 1500, manufactured by Designer polymers, Inc. (デジグナーモレキュールズ Co.))
(D3) The method comprises the following steps Diallyl bisphenol A diglycidyl ether type epoxy resin (product name: RE-810NM, manufactured by Nippon Kabushiki Kaisha, epoxy equivalent: 223, hydrolyzable chlorine: 150ppm (1N KOH-ethanol, dioxane solvent, reflux for 30 minutes)
(D4) The method comprises the following steps 4-hydroxybutylacrylate (product name: 4HBA, manufactured by Nippon Kabushiki Kaisha)
Polymerization initiator: dicumyl peroxide (product name: PERCUMYL D (パークミル D) manufactured by Nippon fat and oil Co., Ltd.; decomposition temperature in rapid heating test: 126 ℃ C.)
(E) The method comprises the following steps Diethylene glycol (manufactured by Tokyo chemical industry Co., Ltd.)
< evaluation method >
[ viscosity ]
The viscosity of the paste composition was measured at 25 ℃ and 5rpm using an E-type viscometer (3 ℃ cone).
[ pot life ]
Regarding the pot life of the paste composition, the number of days for which the viscosity increased to 1.5 times or more the initial viscosity when the paste composition was placed in a thermostatic bath at 25 ℃ was measured.
[ thermal conductivity ]
As to the thermal conductivity of the paste composition after curing, it was measured by the laser flash method in accordance with JIS R1611-1997.
[ resistance ]
For the sample, a conductive paste was applied to a glass substrate (thickness 1mm) in a thickness of 200 μm by a screen printing method, and cured at 200 ℃ for 60 minutes. The resistance of the cured paste composition was measured by a four-terminal method using the product name "MCP-T600" (manufactured by mitsubishi chemical corporation) for the obtained wiring.
[ Heat adhesion Strength ]
For the sample, a gold-backed chip provided with a gold vapor-deposited layer on a bonding surface of 4mm × 4mm was mounted on a pure copper frame and PPF (Ni — Pd/Au-plated copper frame) using a paste composition, and cured at 200 ℃ for 60 minutes. The sample with the chip mounted on the frame was subjected to moisture absorption treatment at 85 ℃ and a relative humidity of 85% for 72 hours.
The thermal adhesive strength of the paste composition was determined by measuring the thermal die shear strength between the chip and the frame at 260 ℃ using a mounting strength measuring apparatus.
[ Heat adhesion Strength after Heat treatment at high temperature ]
For the sample, a gold-backed chip having a gold vapor-deposited layer provided on a bonding surface of 4mm × 4mm was mounted on a PPF (Ni — Pd/Au-plated copper frame) using a paste composition for a semiconductor, and cured at 200 ℃ for 60 minutes.
Regarding the thermal adhesive strength after the high-temperature heat treatment of the paste composition, after the heat treatment at 250 ℃ for 100 hours and 1000 hours, the hot die shear strength at 260 ℃ was measured using a mounting strength measuring apparatus.
Regarding the thermal adhesive strength after the high-temperature heat treatment by the cold and hot cycle treatment of the paste composition, the operation of raising the temperature from-40 ℃ to 250 ℃ and then cooling to-40 ℃ was described as 1 cycle, and after the treatment of the above was performed for 100 cycles and 1000 cycles, the hot die shear strength at 260 ℃ was measured by using a mounting strength measuring apparatus.
[ thermal shock resistance ]
For the sample, a back gold silicon chip having a gold vapor-deposited layer provided on a 6mm × 6mm bonding surface was mounted on a copper frame and a PPF using a paste composition, and heat curing was performed at 200 ℃ for 60 seconds (HP curing) or at 200 ℃ for 60 minutes (OV curing) using an oven on a hot plate.
The thermal shock resistance was evaluated by subjecting a package molded under the following conditions to moisture absorption treatment under conditions of 85 ℃ and 85% relative humidity for 168 hours using an epoxy sealing material (product name: KE-G3000D) made of kyoto (ltr), IR reflow soldering treatment (260 ℃ for 10 seconds) and cold-heat cycle treatment (operation of raising the temperature from-55 ℃ to 150 ℃ and then cooling to-55 ℃ is referred to as 1 cycle, and this is performed for 1000 cycles), and observing the number of internal cracks generated in each package after each treatment by using an ultrasonic microscope. The evaluation results of the thermal shock resistance were expressed as the number of samples having cracks among 5 samples.
Sample and epoxy sealing Material curing conditions
The type of encapsulation: 80pQFP (14mm X20 mm X2 mm thickness)
Chip overview: silicon chip and back gold-plated chip
Lead frame: PPF and copper
Molding of epoxy-based sealing materials: 175 ℃ for 2 minutes
Post mold cure: 175 ℃ for 8 hours
[ energization test ]
The paste composition was applied to an alumina substrate for a light-emitting device having a concave reflector structure on the side surface by a stamping method, and a light-emitting element provided with a 600 μm square silver vapor deposition layer was further mounted thereon, followed by heat curing at 200 ℃ for 60 minutes.
Next, the electrodes of the light-emitting element and the electrodes of the substrate were wired using gold wires, and sealed with silicone resin (manufactured by shin-Etsu chemical Co., Ltd.).
In the energization test, the decrease in reflectance from the initial value after energization of 50mA at 25 ℃ for 500 hours, 1000 hours and 2000 hours was calculated from the following equation.
The reduction rate (%) of the reflectance with respect to the initial value is (reflectance after t hours) ÷ (initial reflectance) × 100
[ void fraction ]
The porosity of the paste composition was observed using a microfocus X-ray inspection apparatus (SMX-1000, manufactured by Shimadzu corporation), and the porosity was evaluated as "good" when it was less than 5%, as "good" when it was 5% or more and less than 8%, and as "failed" when it was 8% or more. The solder joint portion was observed from a direction perpendicular to the joint surface by an X-ray transmission device, the void area and the joint portion area were obtained, and the porosity was calculated from the following equation.
Void fraction (%) — void area ÷ (void area + junction area) × 100
[ deformation of the chip surface ]
For the deformation of the chip surface of the paste composition, the package warpage of a semiconductor package fabricated by mounting a gold-backed chip having a gold vapor-deposited layer provided on a bonding surface of 8mm × 8mm on a Ni — Pd/Au-plated Mo substrate using the paste composition and curing at 200 ℃ for 60 minutes was measured at room temperature. The measurement was carried out using a shadow waviness measurement apparatus (ThermoareAXP, manufactured by Akrometrix) according to JEITA ED-7306, a standard of the Association for the electronic information technology industry. Specifically, a virtual plane calculated by the least square method from all data on the substrate surface of the measurement area is taken as a reference plane, and when a maximum value and a minimum value in a vertical direction of the reference plane are denoted as a and B, a value of | a | + | B | is expressed as a package warp value, and evaluation is performed as follows.
Good: less than 5 μm, pass: 5 μm or more and less than 10 μm, fail: 10 μm or more
[ Table 1]
Figure BDA0002383441910000261
[ Table 2]
Figure BDA0002383441910000271
From the above results, it is understood that the paste composition of the present invention has excellent thermal conductivity, excellent low stress property, good adhesion property, and excellent reflow soldering peel resistance by containing the sintering aid containing an anhydride structure in addition to the predetermined silver particles.
In addition, the paste composition of the present invention is particularly excellent in thermal adhesive strength after high-temperature treatment. Therefore, by using the paste composition as a die bonding paste for bonding elements or a material for bonding heat dissipation members, a semiconductor device and an electric and electronic apparatus having excellent reliability can be obtained.

Claims (9)

1. A paste composition characterized in that,
comprises the following steps:
(A) silver particles having a thickness or a short diameter of 1nm to 200 nm;
silver powder (B) having an average particle diameter of more than 0.2 μm and not more than 30 μm, excluding the silver fine particles (A); and
(C) a sintering aid containing an anhydride structure,
the sintering aid (C) is added in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the total amount of the silver particles (A) and the silver powder (B).
2. The paste composition of claim 1,
the silver fine particles (A) include: (A1) the plate-type silver particles have a central particle diameter of 0.3 to 15 μm and a thickness of 10 to 200 nm.
3. The paste composition of claim 1 or 2,
the silver fine particles (A) include: (A2) spherical silver fine particles having an average particle diameter of 10 to 200 nm.
4. A paste composition according to any one of claims 1 to 3,
the silver particles (A) are self-sintered particles at 100 to 250 ℃.
5. The paste composition according to any one of claims 1 to 4,
the mass ratio of the silver particles (A) to the silver powder (B) is 10: 90-90: 10.
6. A paste composition according to any one of claims 1 to 5,
the sintering aid (C) is acid anhydride with the melting point of 40-150 ℃ and the boiling point of 100-300 ℃.
7. A semiconductor device is characterized in that a semiconductor element,
comprising: a substrate; and a semiconductor element bonded to the substrate via a die-bonding material, the die-bonding material comprising the paste composition according to any one of claims 1 to 6.
8. The semiconductor device according to claim 7,
the semiconductor element is a light emitting element.
9. An electric and electronic device characterized in that,
comprising: a heat-radiating member; and a heat-dissipating member bonded to the heat-dissipating member via a heat-dissipating member bonding material, the heat-dissipating member bonding material comprising the paste composition according to any one of claims 1 to 6.
CN201880052559.5A 2017-09-27 2018-09-11 Paste composition, semiconductor device, and electrical/electronic component Pending CN111033640A (en)

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