WO2015087971A1 - Composition adhésive et dispositif à semi-conducteurs utilisant cette composition - Google Patents

Composition adhésive et dispositif à semi-conducteurs utilisant cette composition Download PDF

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Publication number
WO2015087971A1
WO2015087971A1 PCT/JP2014/082839 JP2014082839W WO2015087971A1 WO 2015087971 A1 WO2015087971 A1 WO 2015087971A1 JP 2014082839 W JP2014082839 W JP 2014082839W WO 2015087971 A1 WO2015087971 A1 WO 2015087971A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
mass
particles
zinc
composition according
Prior art date
Application number
PCT/JP2014/082839
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English (en)
Japanese (ja)
Inventor
名取　美智子
田中　俊明
偉夫 中子
石川　大
山田　和彦
賢 藤田
千秋 岡田
Original Assignee
日立化成株式会社
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Publication of WO2015087971A1 publication Critical patent/WO2015087971A1/fr

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Classifications

    • 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
    • H01L33/64—Heat extraction or cooling elements
    • H01L33/641—Heat extraction or cooling elements characterized by the materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29339—Silver [Ag] as principal constituent

Definitions

  • the present invention relates to an adhesive composition and a semiconductor device using the same. More specifically, the present invention relates to an adhesive composition suitable for bonding an LED semiconductor element to a substrate such as a lead frame, a ceramic wiring board, a glass epoxy wiring board, a polyimide wiring board, and a semiconductor device using the same. About.
  • an adhesive in which a filler such as silver powder is dispersed in a resin such as an epoxy resin or a polyimide resin there is a method of using (for example, silver paste).
  • a paste adhesive is applied to a die pad of a lead frame using a dispenser, a printing machine, a stamping machine, etc., and then a semiconductor element is die-bonded and bonded by heat curing to obtain a semiconductor device.
  • an adhesive composition (Patent Documents 1 to 3) filled with high thermal conductivity silver particles and solder particles are used.
  • an adhesive composition Patent Document 4
  • an adhesive composition Patent Document 5
  • an adhesive composition Patent Document 5
  • an adhesive composition Patent Document 6
  • silver particles are sintered by heating at 100 ° C. or more and 400 ° C. or less by using micro-sized silver particles subjected to a special surface treatment.
  • JP 2006-73811 A JP 2006-302834 A Japanese Patent Laid-Open No. 11-66953 JP 2005-93996 A JP 2006-83377 A Japanese Patent No. 4353380
  • gold-tin alloy plating is applied to many of the adherend surfaces of the LED elements. This is due to the property that the gold-tin alloy plating has high thermal conductivity (that is, high heat dissipation) and is difficult to absorb LED light. Further, gold having higher thermal conductivity than gold-tin alloy plating is applied to the high-power LED element.
  • the silver particles proposed in Patent Document 6 are sintered with each other, so that the thermal conductivity and the connection reliability at a high temperature are higher than those of other methods. It is considered that the property is excellent.
  • the present inventors apply the adhesive composition proposed in Patent Document 6 to the mounting of an LED element having a deposition surface formed by gold-tin alloy plating, the present invention is sufficient for gold-tin alloy plating. It was found that the adhesive strength could not be obtained.
  • the present inventors have found that when the adhesive composition proposed in Patent Document 6 is applied to the mounting of an LED element having a deposition surface made of gold, the adhesive strength is remarkably reduced.
  • the present invention forms a cured product having a sufficiently high adhesive force and high thermal conductivity even when applied to the mounting of an LED element having a deposition surface made of gold-tin alloy or gold. It is an object to provide an adhesive composition that can be used and a semiconductor device using the same.
  • the present invention provides an adhesive composition containing silver particles containing silver atoms, zinc particles containing metallic zinc, and a thermosetting resin.
  • the content of silver atoms is 90% by mass or more based on the total amount of transition metal atoms, and the content of zinc atoms is 0.01% by mass based on the total amount of transition metal atoms. It is preferable that the content of the thermosetting resin is 0.1% by mass or more and 10% by mass or less based on the total amount of the adhesive composition.
  • the zinc particles preferably have an average primary particle size of 50 nm to 150,000 nm.
  • the zinc particles are preferably in the form of flakes.
  • piece shape is a concept including shapes, such as plate shape, dish shape, and scale shape.
  • the silver particles preferably have an average primary particle size of 0.1 ⁇ m to 50 ⁇ m.
  • thermosetting resin preferably contains one or more resins selected from the group consisting of epoxy-phenol resins, acrylic resins, and bismaleimide resins.
  • the adhesive composition according to the present invention preferably further contains a dispersion medium.
  • the dispersion medium preferably contains at least one dispersion medium having a boiling point of 300 ° C. or higher selected from the group consisting of alcohol, carboxylic acid and ester.
  • the boiling point in this invention means the boiling point under 1 atmosphere.
  • the volume resistivity of a cured product obtained by thermosetting the adhesive composition is 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and the thermal conductivity is 30 W / m ⁇ K or more. Preferably there is.
  • the adhesive composition according to the present invention is preferably 100 to 300 ° C. for 5 seconds to 10 hours, more preferably 150 to 300 ° C. for 30 minutes to 5 hours, still more preferably 150 to 250 ° C. for 1 to 2 hours, particularly preferably. Is preferably cured at 200 ° C. for 1 hour.
  • the adhesive composition according to the present invention is preferably used for an adherend surface having a gold-tin alloy.
  • the present invention also provides a semiconductor device having a structure in which an LED element and an LED element mounting support member are bonded via the above-described adhesive composition.
  • the deposition surface of the LED element has a gold-tin alloy.
  • a cured product having a sufficiently high adhesive force and a high thermal conductivity even when applied to the mounting of an LED element having a deposition surface made of gold-tin alloy or gold.
  • An adhesive composition that can be formed and an LED device using the same can be provided.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition in the present specification when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. Means the total amount of substances.
  • the adhesive composition of this embodiment contains silver particles, zinc particles, and a thermosetting resin. According to the adhesive composition of the present embodiment, a high adhesive force can be expressed even on a gold-tin alloy or gold-coated surface, and a cured product having a high thermal conductivity can be formed.
  • the adhesive composition of this embodiment may further contain a dispersion medium.
  • the silver particles are particles containing silver atoms, preferably particles containing silver atoms as a main component (for example, the silver content in the solid content is 90% by mass or more, the same applies hereinafter).
  • the composition mainly composed of silver atoms include metallic silver and silver oxide, with metallic silver being preferred.
  • Examples of the shape of the silver particles include a spherical shape, a lump shape, a needle shape, and a flake shape.
  • the silver particles preferably have an average primary particle size of 0.001 ⁇ m to 500 ⁇ m, more preferably 0.01 ⁇ m to 100 ⁇ m, and still more preferably 0.1 ⁇ m to 50 ⁇ m.
  • the average particle size (volume average particle size) of primary particles of silver particles can be measured with a laser scattering particle size distribution analyzer. An example of the measurement method is shown below.
  • distilled water is introduced into the liquid module by the Rinse command of the measurement program, and De-bubble, Measurement Offset, Align, and Measurement Background are performed in the measurement program. Subsequently, measurement loading is performed in the measurement program, and when the aqueous dispersion is shaken and homogenized, the aqueous dispersion is added to the liquid module using a dropper until the sample amount becomes low to OK in the measurement program. Thereafter, Measurement is performed in the measurement program to obtain a particle size distribution.
  • the zinc particles are particles containing metallic zinc, and are preferably particles containing metallic zinc as a main component (for example, the zinc content in the solid content is 90% by mass or more).
  • Zinc particles include, for example, metallic zinc particles, zinc particles whose particle nuclei are metallic zinc and having a zinc oxide layer on the surface, zinc particles whose particle nuclei are metallic zinc and having an organic protective coating, and whose particle nuclei are metallic zinc Zinc particles having a metallic silver layer on the surface can be used.
  • the zinc particles preferably have an average primary particle size of 150,000 nm or less, more preferably 50,000 nm or less, from the viewpoint of obtaining a contact area with an inorganic material such as a conductor layer or a substrate. More preferably, it is 1,000 nm or less.
  • the average particle size of primary particles of zinc particles is preferably 50 nm or more.
  • Examples of the shape of the zinc particles include a spherical shape, a lump shape, a needle shape, and a flake shape. Among these, flaky particles are preferable from the viewpoint of reducing the influence of the oxidation described above.
  • the content of silver atoms is preferably 90% by mass or more, more preferably 95% by mass or more based on the total amount of transition metal atoms.
  • the adhesive composition can express sufficiently high adhesive force and thermal conductivity.
  • the total amount of transition metal atoms means the total amount of transition metal atoms in the solid content of the adhesive composition.
  • the content of zinc atoms is preferably 0.01% by mass or more, more preferably 0.05% by mass or more based on the total amount of transition metal atoms, The content is more preferably 0.08% by mass or more, and particularly preferably 0.09% by mass or more.
  • the zinc atom content is preferably 0.6% by mass or less, more preferably 0.5% by mass or less, based on the total amount of transition metal atoms. More preferably, it is 0.2 mass% or less.
  • the content of silver atoms and zinc atoms in the adhesive composition can be measured by XRD, SEM-EDX, fluorescent X-ray measurement or the like.
  • An example of a technique for measuring the content of silver atoms and zinc atoms by SEM-EDX is shown below.
  • the adhesive composition is stretched in a petri dish so as to have a thickness of 1 mm or less, and dried in a vacuum dryer at 70 ° C., 100 Pa or less, for 40 hours or more to obtain a dry adhesive composition.
  • the dry adhesive composition is molded on a SEM sample stage so as to be flat with a thickness of 2 ⁇ m or more to obtain a sample for SEM.
  • the ratio of each transition metal atom in the adhesive composition can be obtained by quantitatively analyzing the SEM sample according to an example of a quantitative method using SEM-EDX described later.
  • the content of silver atoms and zinc atoms in the adhesive composition after curing can be measured, and this can be used as the content of silver atoms and zinc atoms in the adhesive composition. This is because silver atoms and zinc atoms do not volatilize in the adhesive composition after curing, and their contents do not substantially change.
  • the adhesive composition is uniformly applied to a glass plate with a thickness of 0.1 to 0.5 mm, and subjected to curing treatment at 200 to 300 ° C. for 1 hour in the air. obtain. About this hardened
  • the adhesive composition of this embodiment may contain transition metal atoms other than silver atoms and zinc atoms in the solid content.
  • the content of transition metal atoms other than silver atoms and zinc atoms is, for example, preferably less than 10% by mass and more preferably less than 5% by mass based on the total amount of transition metal atoms.
  • thermosetting resin In the adhesive composition of this embodiment, the content of the thermosetting resin is preferably 0.1% by mass or more and 10% by mass or less based on the total amount of the adhesive composition.
  • the thermosetting resin is preferably one or more resins selected from the group consisting of epoxy-phenol resins, acrylic resins, and bismaleimide resins. Further, from the viewpoint of increasing the efficiency of the mounting process, the shorter the reaction end time of the thermosetting resin, the better.
  • the dispersion medium may be either organic or inorganic, but preferably has a boiling point of 200 ° C. or higher, and more preferably has a boiling point of 300 ° C. or higher, from the viewpoint of preventing drying in the coating process. preferable. Moreover, it is preferable that it has a boiling point of 400 degrees C or less so that a dispersion medium does not remain after sintering.
  • the dispersion medium it is preferable to use one or more dispersion mediums having a boiling point of 300 ° C. or higher selected from the group consisting of alcohol, carboxylic acid and ester. Further, as the dispersion medium, one or more kinds of dispersion medium having a boiling point of 300 ° C. or more and 400 ° C. or less selected from the group consisting of alcohol, carboxylic acid and ester, and a volatile component having a boiling point of 100 ° C. or more and less than 300 ° C. It is more preferable to use together.
  • alcohols, carboxylic acids or esters having a boiling point of 300 ° C. or higher include aliphatic carboxylic acids such as palmitic acid, stearic acid, arachidic acid, terephthalic acid, oleic acid, pyromellitic acid, o-phenoxybenzoic acid and the like.
  • Aromatic carboxylic acid cetyl alcohol, isobornyl cyclohexanol, aliphatic alcohol such as tetraethylene glycol, aromatic alcohol such as p-phenylphenol, octyl octoate, ethyl myristate, methyl linoleate, tributyl citrate, benzoic acid And esters such as benzyl acid.
  • aromatic alcohols or carboxylic acids having 6 to 20 carbon atoms are preferred.
  • volatile components having a boiling point of 100 ° C. or higher and lower than 300 ° C. include monovalent and polyvalent compounds such as pentanol, hexanol, heptanol, octanol, decanol, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, ⁇ -terpineol, and the like.
  • Alcohols ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol isobutyl ether, diethylene glycol hexyl ether, triethylene glycol methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether Ter, diethylene glycol butyl methyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol Ethers such as butyl ether, dipropylene glycol dimethyl ether, tripropylene glycol methyl ether, trip
  • Examples of mercaptans having an alkyl group having 1 to 18 carbon atoms include ethyl mercaptan, n-propyl mercaptan, i-propyl mercaptan, n-butyl mercaptan, i-butyl mercaptan, t-butyl mercaptan, pentyl mercaptan, hexyl mercaptan, and the like.
  • Examples of mercaptans having a cycloalkyl group having 5 to 7 carbon atoms include mercaptans such as cyclopentyl mercaptan, cyclohexyl mercaptan, and cycloheptyl mercaptan.
  • mercaptans having a boiling point of 100 ° C. or higher and lower than 300 ° C. a volatile component having a boiling point of 150 ° C. or higher is preferable, and alcohols, esters and ethers having 4 to 12 carbon atoms are more preferable.
  • the above-mentioned dispersion media can be used alone or in combination of two or more.
  • the content of the dispersion medium is preferably 0.1 to 20 parts by mass when the total amount of the adhesive composition is 100 parts by mass.
  • the total content of the silver particles, the zinc particles and the dispersion medium is preferably 90 parts by mass or more and more preferably 95 parts by mass or more when the total amount of the adhesive composition is 100 parts by mass. More preferably, it is 98 parts by mass or more.
  • the adhesive composition of the present embodiment may include one or more of a sintering aid, a wettability improver, and an antifoaming agent. Note that the adhesive composition of the present embodiment may contain components other than those listed here.
  • the adhesive composition of the present embodiment further includes a moisture absorbent such as calcium oxide and magnesium oxide, a wetting improver such as a nonionic surfactant and a fluorine surfactant, and a defoaming agent such as silicone oil.
  • a moisture absorbent such as calcium oxide and magnesium oxide
  • a wetting improver such as a nonionic surfactant and a fluorine surfactant
  • a defoaming agent such as silicone oil.
  • Agents, ion trapping agents such as inorganic ion exchangers, polymerization inhibitors, curing accelerators, silane coupling agents, and the like can be added as appropriate.
  • the above-mentioned adhesive composition is a combination of dispersing or dissolving devices such as a stirrer, raky machine, three rolls, planetary mixer, etc., by mixing or dividing the above components all together, heating and mixing as necessary, It can be used as a uniform paste by dissolving, pulverizing and kneading or dispersing.
  • the adhesive composition preferably has a viscosity suitable for each printing and coating method when it is molded.
  • the viscosity of the adhesive composition for example, the Casson viscosity at 25 ° C. is preferably 0.05 Pa ⁇ s to 2.0 Pa ⁇ s, more preferably 0.06 Pa ⁇ s to 1.0 Pa ⁇ s. preferable.
  • the Casson viscosity of the adhesive composition can be measured with a viscoelasticity measuring device (Physica MCR-501, manufactured by Anton Paar).
  • a cone-type measuring jig (CP50-1) having an angle of 1 ° and a diameter of 50 mm is mounted, and an adhesive composition is introduced into the measuring apparatus so that the adhesive composition overflows from the measuring jig at the measurement position. Thereafter, the measurement jig is lowered to the measurement position, and the adhesive composition overflowing at that time is scraped off to perform measurement.
  • the measurement is performed at 25 ° C., and the following two steps are continuously performed, and the shear rate and the shear stress are recorded in the second step.
  • Shear rate 0 to 100 s ⁇ 1 shear rate increase rate 100/60 s ⁇ 1 / step, measurement interval 1 second, number of measurement points 60 points.
  • the Casson viscosity is calculated by the method described in -46). Specifically, the square root of each obtained shear rate and shear stress is calculated and approximated by the least square method from (shear stress) ⁇ (1/2) to (shear rate) ⁇ (1/2). Calculate the slope of the straight line. The square of this slope is the Casson viscosity.
  • the above-mentioned adhesive composition can be cured, for example, by heating at 100 to 300 ° C. for 5 seconds to 10 hours.
  • the content of silver atoms and zinc atoms does not substantially change before and after heating.
  • the content of silver atoms and zinc atoms in the total transition metal atoms in the cured adhesive composition can be determined by methods such as SEM-EDX, TEM-EDX, and Auger electron spectroscopy using the cured adhesive composition. Can be quantified.
  • a sample having a layer of the cured adhesive composition having a thickness of 3 ⁇ m or more is hardened with an epoxy casting resin.
  • a polishing apparatus Using a polishing apparatus, a cross section perpendicular to the layer of the cured adhesive composition is cut out, and the cross section is finished smoothly.
  • a noble metal antistatic layer having a thickness of about 10 nm is formed on the finished cross section using a sputtering apparatus or a vapor deposition apparatus to produce a sample for SEM.
  • the sample for SEM is set in a SEM-EDX (for example, ESEM XL, manufactured by Philips) apparatus and observed at a magnification of about 5,000 to 10,000 times.
  • the EDX point analysis was performed around the center of the cured adhesive composition, sample tilt angle: 0 °, acceleration voltage 25 kV, Ev / Chan: 10, Amp. Accumulated under the conditions of Time: 50 ⁇ S, Choose Preset: Live Time 300 secs, and the analysis conditions are Matrix: ZAF, SEC (Standardless element Coefficient): EDAX, quantitative method: None, and cured adhesive composition
  • the proportion of each transition metal atom in the product is obtained.
  • the cured adhesive composition preferably has a volume resistivity of 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less, and a thermal conductivity of 30 W / m ⁇ K or more. It is preferable.
  • the volume resistivity of the cured adhesive composition is preferably as low as possible. The higher the thermal conductivity of the cured adhesive composition, the more preferable it is from the viewpoint of suppressing the device temperature rise.
  • the semiconductor device of this embodiment includes a semiconductor element and a semiconductor element mounting support member, and has a structure in which the semiconductor element and the semiconductor element mounting support member are bonded via the adhesive composition of the present embodiment. .
  • semiconductor elements and supporting members for mounting semiconductor elements As a semiconductor element used in the present embodiment, an LED element having a gold-tin alloy or gold on a deposition surface can be given. In addition, in this embodiment, the LED element whose deposition surface is silver can also be used. Examples of the semiconductor element mounting support member used in the present embodiment include an LED element mounting support member. Examples of the LED element mounting support member include a support member having gold or silver on the surface of the adherend. In addition, the LED element mounting support member may be formed by patterning a plurality of materials of gold, silver, and gold-tin alloy on the base material.
  • the manufacturing method of the semiconductor device of this embodiment using the adhesive composition of this embodiment can have at least the following steps.
  • (A) A process of applying an adhesive composition to an LED element or an LED element mounting support member, and bonding the LED element and the LED element mounting support member (hereinafter referred to as “process (A)”),
  • (B) A step of curing the adhesive composition and bonding the LED element and the LED element mounting support member (hereinafter referred to as “step (B)”).
  • step (A) after applying the adhesive composition, it may have a drying step.
  • the adhesive composition can be prepared by mixing the above-described silver particles, zinc particles, thermosetting resin, and optional components in a dispersion medium.
  • the adhesive composition may be stirred after mixing.
  • the adhesive composition may adjust the maximum particle size of the dispersion by filtration.
  • the stirring treatment can be performed using a stirrer.
  • a stirrer examples include a rotation / revolution stirrer, a lycra machine, a twin-screw kneader, a triple roll, a planetary mixer, and a thin layer shear disperser.
  • Filtration can be performed using a filtration device.
  • the filter for filtration include a metal mesh, a metal filter, and a nylon mesh.
  • the adhesive composition layer is formed by applying the adhesive composition onto the LED element mounting support member or the LED element. Examples of the application method include coating or printing.
  • the adhesive composition for example, pin transfer, dipping, spray coating, bar coating, die coating, comma coating, slit coating, and applicator can be used.
  • a printing method for printing the adhesive composition for example, a dispenser, stencil printing, intaglio printing, screen printing, needle dispenser, or jet dispenser method can be used.
  • the adhesive composition layer formed by the application of the adhesive composition can be appropriately dried from the viewpoint of suppressing flow and void generation during curing.
  • drying at room temperature drying by heating, or drying under reduced pressure
  • hot plate warm air dryer, warm air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic heating device
  • a heater heating device, a steam heating furnace, a hot plate press device, or the like can be used.
  • the temperature and time for drying are preferably adjusted as appropriate according to the type and amount of the dispersion medium used, and are preferably dried at 50 to 120 ° C. for 1 to 120 minutes, for example. However, the temperature for drying is preferably set to a temperature that avoids the reaction of the thermosetting resin.
  • the LED element and the LED element mounting support member are bonded together via the adhesive composition layer.
  • it may be performed at any stage before or after the bonding process.
  • a curing process is performed on the adhesive composition layer.
  • the curing process may be performed by heat treatment or by heat and pressure treatment.
  • heat treatment hot plate, hot air dryer, hot air heating furnace, nitrogen dryer, infrared dryer, infrared heating furnace, far infrared heating furnace, microwave heating device, laser heating device, electromagnetic heating device, heater heating An apparatus, a steam heating furnace, or the like can be used.
  • a hot plate press apparatus etc. may be used for a heat pressurizing process, and the above-mentioned heat processing may be performed, putting a weight and pressurizing.
  • the LED element and the LED element mounting support member are made of a cured product of the adhesive composition of the present embodiment excellent in adhesiveness, high thermal conductivity, and high heat resistance.
  • a bonded semiconductor device can be manufactured.
  • the LED module thus obtained is an adhesive member (cured product of an adhesive composition layer) having high adhesion, high thermal conductivity, high conductivity and high heat resistance between the LED element and the LED element mounting support member. ).
  • Examples of the semiconductor device of this embodiment include an LED module.
  • Average particle diameter of primary particles 0.01 g of zinc particles or silver particles, 0.1 g of sodium dodecylbenzenesulfonate (manufactured by Wako Pure Chemical Industries), 9.99 g of distilled water (manufactured by Wako Pure Chemical Industries), Were mixed and treated with an ultrasonic cleaner for 5 minutes to obtain an aqueous dispersion.
  • a laser scattering particle size distribution analyzer LS13 320 manufactured by Beckman Coulter
  • the main body was turned on and left for 30 minutes to stabilize the light source.
  • distilled water was introduced into the liquid module by the Rinse command of the measurement program, and De-bubble, Measurement Offset, Align, and Measurement Background were performed in the measurement program. Subsequently, measurement loading was performed in the measurement program, and when the aqueous dispersion was shaken and homogenized, the aqueous dispersion was added to the liquid module using a dropper until the sample amount became low to OK in the measurement program. Thereafter, measurement was performed using a measurement program to obtain a particle size distribution.
  • the adhesive strength of the cured adhesive composition was evaluated by die shear strength. Using an all-purpose bond tester (4000 series, manufactured by DAGE) equipped with a 50N load cell, the LED chip with a measurement speed of 500 ⁇ m / s, a measurement height of 50 ⁇ m and a gold-tin alloy surface is pressed in the horizontal direction. The die shear strength of the cured composition was measured. The average of the measured values of five samples was taken as the die shear strength.
  • the adhesive strength of the cured adhesive composition was evaluated by die shear strength. Using a universal bond tester (4000 series, manufactured by DAGE) equipped with a 50N load cell, a silicon chip with a measurement speed of 500 ⁇ m / s, a measurement height of 100 ⁇ m, and a gold-plated surface is pressed in the horizontal direction, and the adhesive composition The die shear strength of the cured product was measured. The average of the measured values of 12 samples was defined as the die shear strength.
  • Example 1 (Preparation of adhesive composition) 5 parts by mass of isobornylcyclohexanol (Telsolve MTPH, manufactured by Nippon Terpene) and 5 parts by mass of dipropylene glycol methyl ether acetate (DPMA, manufactured by Daicel Chemical) as a dispersion medium, and stearic acid (New Nippon Rika) as a particle surface treatment agent 0.79 parts by mass was mixed and sealed in a plastic bottle. This solution was warmed in a water bath at 50 ° C. to obtain a transparent and uniform solution with occasional shaking.
  • Telsolve MTPH dipropylene glycol methyl ether acetate
  • stearic acid New Nippon Rika
  • the plastic bottle was sealed, and the mixture was stirred at 2000 rpm for 1 minute using a rotation / revolution type stirring device (Planetary Vacuum Mixer ARV-310, manufactured by Sinky) to obtain an adhesive composition.
  • the average particle size of the primary particles of the scaly zinc particles was 23 ⁇ m
  • the average particle size of the primary particles of the scaly silver particles was 5.42 ⁇ m
  • the average particle size of the primary particles of the spherical silver particles was 1.64 ⁇ m.
  • Example 2 (Preparation of adhesive composition) 5 parts by mass of isobornylcyclohexanol (Telsolve MTPH, manufactured by Nippon Terpene) and 5 parts by mass of dipropylene glycol methyl ether acetate (DPMA, manufactured by Daicel Chemical) as a dispersion medium, and stearic acid (New Nippon Rika) as a particle surface treatment agent 0.79 parts by mass was mixed and sealed in a plastic bottle. This solution was warmed in a water bath at 50 ° C. to obtain a transparent and uniform solution with occasional shaking.
  • Telsolve MTPH isobornylcyclohexanol
  • DPMA dipropylene glycol methyl ether acetate
  • stearic acid New Nippon Rika
  • the plastic bottle was sealed, and the mixture was stirred at 2000 rpm for 1 minute using a rotation / revolution type stirring device (Planetary Vacuum Mixer ARV-310, manufactured by Sinky) to obtain an adhesive composition.
  • the average particle size of the primary particles of the scaly zinc particles was 23 ⁇ m
  • the average particle size of the primary particles of the scaly silver particles was 5.42 ⁇ m
  • the average particle size of the primary particles of the spherical silver particles was 1.64 ⁇ m.
  • Example 3 (Preparation of adhesive composition) 5 parts by mass of isobornylcyclohexanol (Telsolve MTPH, manufactured by Nippon Terpene) and 5 parts by mass of dipropylene glycol methyl ether acetate (DPMA, manufactured by Daicel Chemical) as a dispersion medium, and stearic acid (New Nippon Rika) as a particle surface treatment agent 0.79 parts by mass was mixed and sealed in a plastic bottle. This solution was warmed in a 50 ° C. water bath, and was made into a transparent and uniform solution with occasional shaking.
  • Telsolve MTPH isobornylcyclohexanol
  • DPMA dipropylene glycol methyl ether acetate
  • stearic acid New Nippon Rika
  • the plastic bottle was sealed, and the mixture was stirred at 2000 rpm for 1 minute using a rotation / revolution type stirring device (Planetary Vacuum Mixer ARV-310, manufactured by Sinky) to obtain an adhesive composition.
  • the average particle size of the primary particles of the scaly zinc particles was 23 ⁇ m
  • the average particle size of the primary particles of the scaly silver particles was 5.42 ⁇ m
  • the average particle size of the primary particles of the spherical silver particles was 1.64 ⁇ m.
  • the average particle size of the primary particles of the scaly zinc particles was 23 ⁇ m
  • the average particle size of the primary particles of the scaly silver particles was 5.42 ⁇ m
  • the average particle size of the primary particles of the spherical silver particles was 1.64 ⁇ m.
  • Table 1 shows the amount of each component.
  • Table 2 shows the measurement results of die shear strength and thermal conductivity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)
  • Led Device Packages (AREA)

Abstract

　Cette composition adhésive comprend des particules d'argent contenant des atomes d'argent, des particules de zinc contenant du zinc métallique, et une résine thermodurcissable.
PCT/JP2014/082839 2013-12-13 2014-12-11 Composition adhésive et dispositif à semi-conducteurs utilisant cette composition WO2015087971A1 (fr)

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JP2017132877A (ja) * 2016-01-27 2017-08-03 京セラ株式会社 半導体接着用樹脂組成物及び半導体装置
US20210139746A1 (en) * 2019-11-08 2021-05-13 Nitto Denko Corporation Thermosetting sheet and dicing die bonding film
US20210139745A1 (en) * 2019-11-08 2021-05-13 Nitto Denko Corporation Thermosetting sheet and dicing die bonding film

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JP6903282B2 (ja) * 2017-02-14 2021-07-14 三菱瓦斯化学株式会社 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート及びプリント配線板
JP7099700B2 (ja) 2017-06-19 2022-07-12 ユニチカ株式会社 ビスマレイミド変性体およびその製造方法
CN113831865A (zh) * 2020-06-24 2021-12-24 日东电工株式会社 热固性片及切割芯片接合薄膜
JP2022069969A (ja) * 2020-10-26 2022-05-12 日東電工株式会社 熱硬化性シート、ダイシングダイボンドフィルム、及び、半導体装置

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US20210139746A1 (en) * 2019-11-08 2021-05-13 Nitto Denko Corporation Thermosetting sheet and dicing die bonding film
US20210139745A1 (en) * 2019-11-08 2021-05-13 Nitto Denko Corporation Thermosetting sheet and dicing die bonding film

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