WO2015005372A1 - Dispositif à semi-conducteur à nanoparticules d'argent et son procédé de fabrication - Google Patents

Dispositif à semi-conducteur à nanoparticules d'argent et son procédé de fabrication Download PDF

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Publication number
WO2015005372A1
WO2015005372A1 PCT/JP2014/068270 JP2014068270W WO2015005372A1 WO 2015005372 A1 WO2015005372 A1 WO 2015005372A1 JP 2014068270 W JP2014068270 W JP 2014068270W WO 2015005372 A1 WO2015005372 A1 WO 2015005372A1
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Prior art keywords
silver
monoamine
semiconductor device
silver nanoparticles
aliphatic hydrocarbon
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PCT/JP2014/068270
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English (en)
Japanese (ja)
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岡本和樹
小妻宏禎
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株式会社ダイセル
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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Definitions

  • the present invention relates to a semiconductor device using silver nanoparticles and a manufacturing method thereof.
  • This application claims the priority of Japanese Patent Application No. 2013-143478 for which it applied to Japan on July 9, 2013, and uses the content here.
  • a method for joining a semiconductor element and a substrate in a semiconductor device a method using metal particles such as Au, Ag, and Cu can be given.
  • the particle size of the metal particles is very small, it can be sintered at a low temperature of about 150 to 350 ° C.
  • this method is suitable for a semiconductor device used for an application requiring heat resistance.
  • Patent Document 1 discloses a mounting structure using metal nanoparticles as a bonding material.
  • metal nanoparticles are interposed between a bump provided on a terminal of a semiconductor element and an electrode of the substrate, and the metal nanoparticle is sintered to sinter the terminal of the semiconductor element and the substrate.
  • the electrode is joined.
  • Patent Document 2 a sintered body obtained by sintering metal particles is arranged around a bump made of a bulk metal material, and the bump and the sintered body are each independently connected to a terminal of the semiconductor element.
  • a mounting structure that electrically connects the electrodes of the substrate is disclosed. This structure achieves high heat dissipation from the semiconductor element to the substrate and strong bondability while suppressing damage to the semiconductor element when the semiconductor element is bonded to the substrate.
  • each invention disclosed in the above-mentioned prior art documents has the following problems.
  • the joining portion (joining portion) obtained by sintering the metal nanoparticles has a low thermal conductivity, and thus efficiently dissipates heat generated by the semiconductor element to the substrate. This may cause problems such as unstable operation of the semiconductor device.
  • the semiconductor element is an LED (light emitting diode) element, there is a possibility that problems such as a decrease in light emission efficiency may occur.
  • Patent Document 2 it is necessary to prepare the bump and the sintered body separately, and it is necessary to adjust the thickness and arrangement of the sintered body with respect to the bump. There may be problems with manufacturing efficiency and accuracy.
  • the sintering temperature of the metal particles is not yet satisfactory for suppressing damage to the semiconductor element, and there is no disclosure of specific embodiments and conductivity of the metal particles.
  • a silver nanoparticle is mentioned as a typical example of the metal particle with a small particle diameter.
  • Silver nanoparticles are usually stabilized by being mixed with an organic stabilizer and used in the form of a silver coating composition (silver ink, silver paste).
  • a silver coating composition silver ink, silver paste.
  • sintering is possible at as low a temperature as possible.
  • removal of the organic stabilizer is insufficient.
  • the organic stabilizer present on the surface of the silver nanoparticles contributes to the stabilization of the silver nanoparticles, but on the other hand, tends to hinder the sintering of the silver nanoparticles.
  • the stabilization of the silver nanoparticles and the development of electrical conductivity particularly when sintering at a low temperature.
  • an object of the present invention is to suppress damage to the semiconductor element when the semiconductor element is bonded to the substrate, to have high heat dissipation from the semiconductor element to the substrate, and to be strong in bonding between the semiconductor element and the substrate.
  • An object of the present invention is to provide a highly accurate semiconductor device having high conductivity between a terminal of an element and an electrode of a substrate, high manufacturing efficiency, and a manufacturing method thereof.
  • the inventors of the present invention have found a method of joining a terminal of a semiconductor element and an electrode of a substrate using silver nanoparticles that can be sintered at a low temperature and in a short time and have excellent conductivity and thermal conductivity. Further, in the semiconductor device obtained using the silver nanoparticles, damage to the semiconductor element during bonding of the semiconductor element and the substrate is suppressed, heat dissipation from the semiconductor element to the substrate is high, and the semiconductor element and the substrate It has been found that the semiconductor device is a highly accurate semiconductor device with strong bonding, high conductivity between the terminal of the semiconductor element and the electrode of the substrate, high manufacturing efficiency. The present invention has been completed based on these findings.
  • the present invention is a semiconductor device including a semiconductor element and a substrate, wherein the terminal of the semiconductor element and the electrode of the substrate are opposed to each other, and the terminal and the electrode are joined by one or more joining portions.
  • At least one of the joints is a sintered body obtained by sintering silver nanoparticles
  • the silver nanoparticles are silver nanoparticles obtained by thermally decomposing a mixture containing an amine (A) having an aliphatic hydrocarbon group and an amino group and a silver compound (B). To do.
  • the mixture is an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms composed of an aliphatic hydrocarbon group and one amino group, the aliphatic hydrocarbon group and one amino group as the amine (A).
  • the aliphatic hydrocarbon monoamine (A2) having 5 or less carbon atoms and the aliphatic hydrocarbon diamine (A3) having 8 or less carbon atoms consisting of an aliphatic hydrocarbon group and two amino groups.
  • the mixture may include, as the amine (A), an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms composed of an aliphatic hydrocarbon group and one amino group, and an aliphatic hydrocarbon group and one amino group.
  • An aliphatic hydrocarbon monoamine (A2) having 5 or less carbon atoms and a group Based on the total of the monoamine (A1) and the monoamine (A2), the monoamine (A1) is 5 mol% or more and less than 20 mol%, and the monoamine (A2) is more than 80 mol% and 95 mol% or less.
  • a semiconductor device comprising the above-mentioned ratio.
  • the semiconductor device is provided, wherein the mixture includes, as the amine (A), a branched aliphatic hydrocarbon monoamine (A4) composed of a branched aliphatic hydrocarbon group having 4 or more carbon atoms and one amino group. .
  • the semiconductor device is provided in which the silver compound (B) is silver oxalate.
  • the semiconductor device is provided in which the silver nanoparticles are silver nanoparticles having an average particle diameter of 0.5 nm to 100 nm.
  • the semiconductor device is provided in which the joint portions are formed so as to form a plurality of rows arranged in parallel with each other at a predetermined interval.
  • the semiconductor device is provided in which the semiconductor element is an optical semiconductor element.
  • the present invention also provides a method for manufacturing the semiconductor device described above, A step of supplying a composition containing silver nanoparticles to at least one of a terminal of the semiconductor element and an electrode of the substrate, a step of allowing the terminal of the semiconductor element and the electrode of the substrate to face each other (b), and the semiconductor element A step (c) of forming a bonded portion by bonding the terminal of the substrate and the electrode of the substrate with the composition containing the silver nanoparticles, and heating the composition containing the silver nanoparticles to Provided is a method of manufacturing a semiconductor device including a step (d) of forming a sintered body.
  • the semiconductor device manufacturing method is provided in which the step (a) is a step (a1) of supplying the composition containing the silver nanoparticles to both the terminal of the semiconductor element and the electrode of the substrate.
  • a semiconductor device including a semiconductor element and a substrate, wherein a terminal of the semiconductor element and an electrode of the substrate are opposed to each other, and the terminal and the electrode are bonded by one or more bonding portions. At least one of the parts is a sintered body formed by sintering silver nanoparticles, A semiconductor device, wherein the silver nanoparticles are silver nanoparticles obtained by thermally decomposing a mixture containing an amine (A) having an aliphatic hydrocarbon group and an amino group and a silver compound (B).
  • the mixture is an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms composed of an aliphatic hydrocarbon group and one amino group, an aliphatic hydrocarbon group and one amino as the amine (A). And an aliphatic hydrocarbon monoamine (A2) having 5 or less carbon atoms composed of a group and an aliphatic hydrocarbon diamine (A3) having 8 or less carbon atoms composed of an aliphatic hydrocarbon group and two amino groups [1] ]
  • the semiconductor device as described in. [3]
  • the content of the monoamine (A1) in the mixture is 10 mol% to 65 mol% based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3). 2].
  • the content of the monoamine (A2) in the mixture is 5 mol% to 50 mol% based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3). [2] or [3].
  • the content of the diamine (A3) in the mixture is 15 mol% to 50 mol% based on the total of the monoamine (A1), the monoamine (A2), and the diamine (A3).
  • the semiconductor device according to any one of [2] to [4].
  • the total amount of the monoamine (A1), the monoamine (A2), and the diamine (A3) is 1 to 20 moles with respect to 1 mole of silver atoms in the silver compound (B).
  • the semiconductor device includes, as the amine (A), an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms composed of an aliphatic hydrocarbon group and one amino group, and an aliphatic hydrocarbon group and one amine.
  • An aliphatic hydrocarbon monoamine (A2) composed of an amino group and having 5 or less carbon atoms, Based on the total of the monoamine (A1) and the monoamine (A2), the monoamine (A1) is 5 mol% or more and less than 20 mol%, and the monoamine (A2) is more than 80 mol% and 95 mol% or less.
  • a method for manufacturing a semiconductor device according to any one of [1] to [17], A step of supplying a composition containing silver nanoparticles to at least one of a terminal of the semiconductor element and an electrode of the substrate, a step of allowing the terminal of the semiconductor element and the electrode of the substrate to face each other (b), and the semiconductor element A step (c) of forming a bonded portion by bonding the terminal of the substrate and the electrode of the substrate with the composition containing the silver nanoparticles, and heating the composition containing the silver nanoparticles to A method for manufacturing a semiconductor device, comprising a step (d) of forming a sintered body.
  • the step (a) is a step (a1) of supplying a composition containing the silver nanoparticles to both a terminal of a semiconductor element and an electrode of a substrate.
  • the semiconductor device of the present invention can be sintered at a low temperature in a short time, and is obtained by bonding the terminals of a semiconductor element and the electrodes of a substrate using a composition containing silver nanoparticles having excellent conductivity and thermal conductivity. Therefore, damage to the semiconductor element at the time of bonding the semiconductor element and the substrate is suppressed, heat dissipation from the semiconductor element to the substrate is high, the bonding between the semiconductor element and the substrate is strong, and the terminal of the semiconductor element is The semiconductor device has high conductivity with the electrode of the substrate, high manufacturing efficiency, and high accuracy.
  • the semiconductor device of the present invention includes at least a semiconductor element and a substrate, the terminal of the semiconductor element and the electrode of the substrate are opposed (arranged so as to be opposed), and the terminal and the electrode are one or more. It has the structure joined by the junction part.
  • An example of the semiconductor device of the present invention is shown in the cross-sectional view of FIG. 1, but the present invention is not limited to this.
  • the semiconductor device 1 of FIG. 1 includes a semiconductor element 4, a terminal 5 formed on the semiconductor element 4, a substrate 2, an electrode 3 formed on the substrate 2, and a junction 6.
  • the terminal 5 and the electrode 3 are disposed so as to face each other, and the terminal 5 and the electrode 3 are joined by a joint portion 6. In this way, the semiconductor element 4 is mounted on the substrate 2.
  • the semiconductor device of the present invention may further include a member other than the semiconductor element and the substrate (for example, a sealing material for the semiconductor element).
  • At least one of the above-described joint portions is a sintered body obtained by sintering silver nanoparticles, and the silver nanoparticles are amines having an aliphatic hydrocarbon group and an amino group (A ) And a silver nanoparticle obtained by thermally decomposing a mixture containing the silver compound (B) as an essential component (sometimes referred to as “silver nanoparticle of the present invention”).
  • the semiconductor element (4 in FIGS. 1 to 5) in the semiconductor device of the present invention is not particularly limited.
  • a power semiconductor element or an optical semiconductor element such as an LED (Light Emitting Diode) element can be used.
  • the semiconductor element is bonded to an electrode on the substrate through the bonding portion by a terminal.
  • the substrate (2 in FIGS. 1 to 5) in the semiconductor device of the present invention is not particularly limited, but is preferably made of a material excellent in heat dissipation or thermal conductivity, such as alumina or aluminum nitride. Alternatively, a substrate with high heat dissipation such as a metal core substrate or a metal base substrate is preferable.
  • the silver nanoparticles of the present invention used in the semiconductor device of the present invention can be sintered at a low temperature and in a short time, as will be described later.
  • a heat-resistant plastic substrate such as a polyimide film, a polyester film such as a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film, a polypropylene film, etc.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • a general-purpose plastic substrate having low heat resistance such as a polyolefin film can also be suitably used.
  • the substrate in the semiconductor device of the present invention has an electrode for energizing the semiconductor element.
  • the material for forming the terminal of the semiconductor element (5 in FIGS. 1 to 5) and the electrode of the substrate (3 in FIGS. 1 to 5) is not particularly limited.
  • the shape and the like of the terminal and the electrode are not particularly limited, and are appropriately selected from well-known and usual modes.
  • the bonding portion in the semiconductor device of the present invention is a portion that physically bonds the terminal of the semiconductor element and the electrode of the substrate.
  • the bonding portion plays a role of electrically and / or thermally bonding the terminal of the semiconductor element and the electrode of the substrate.
  • the semiconductor device of the present invention may have only one junction or may have two or more. Especially, it is preferable that the semiconductor device of this invention has 2 or more of the said junction parts from a viewpoint of electroconductivity and thermal conductivity.
  • the semiconductor device of the present invention is a semiconductor device in which at least one of the joints is a sintered body formed by sintering the silver nanoparticles of the present invention. Therefore, in the semiconductor device of the present invention, damage to the semiconductor element at the time of manufacture is suppressed, heat dissipation from the semiconductor element to the substrate is high, the bonding between the semiconductor element and the substrate is strong, and the terminal of the semiconductor element And a substrate with high conductivity, high manufacturing efficiency, and high accuracy.
  • the semiconductor device of the present invention has two or more of the junctions, at least one of them may be a sintered body formed by sintering the silver nanoparticles of the present invention.
  • 50% or more (for example, 50 to 100%) of the total number (100%) of the joined bodies is a sintered body obtained by sintering the silver nanoparticles of the present invention.
  • a part of the joined body may be a joined body formed of a material other than a sintered body obtained by sintering the silver nanoparticles of the present invention.
  • a general-purpose metal material for example, gold , Silver, copper, aluminum, or an alloy thereof).
  • the arrangement of the junctions is not particularly limited, and a well-known and commonly used arrangement of junctions in the semiconductor device can be applied.
  • the bonding portion is a bonding surface of the terminal of the semiconductor element (surface bonded to the electrode via the bonding portion) and / or a bonding surface of the electrode of the substrate (surface bonded to the terminal via the bonding portion).
  • Is formed so as to form a plurality of rows arranged in parallel with each other at a predetermined interval specifically, two or more rows formed by arranging a plurality of joint portions at a predetermined interval ( Preferably, two or more rows are arranged in parallel with each other at a predetermined interval.
  • the semiconductor device shown in FIG. 1 is a schematic diagram (cross-sectional view) showing an example of a semiconductor device (semiconductor device of the present invention) in which all of the joints are sintered bodies obtained by sintering the silver nanoparticles of the present invention.
  • It is. 1 is a sintered body formed by sintering a composition containing silver nanoparticles (specifically, a sintered body formed by sintering silver nanoparticles in the composition by heating).
  • the joining part 6 is a conductor having high conductivity and thermal conductivity by sintering silver nanoparticles, and as a result of being in contact with the terminal 5 and the electrode 3, the terminal 5 and the electrode 3 are joined.
  • the part 6 is in a state of being electrically and thermally well connected.
  • composition containing silver nanoparticles used in the semiconductor device of the present invention include, for example, a large number of silver nanoparticles (silver nanoparticles of the present invention) that are components that exhibit conductivity and thermal conductivity, and the silver.
  • maintaining a nanoparticle in the dispersed state is mentioned.
  • the composition is not particularly limited and can take various forms.
  • a silver coating composition called a so-called silver ink can be prepared by dispersing the silver nanoparticles of the present invention in a suspended state in a suitable organic solvent (dispersion medium).
  • a silver coating composition called a so-called silver paste can be produced by dispersing the silver nanoparticles of the present invention in a state of being kneaded in an organic solvent.
  • the organic solvent for obtaining the coating composition is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane; toluene, xylene, Aromatic hydrocarbon solvents such as mesitylene; alcohol solvents such as methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, terpineol, etc. Is mentioned.
  • the average particle diameter of the silver nanoparticles of the present invention is not particularly limited, but is preferably 0.5 nm to 100 nm, more preferably 0.5 nm to 50 nm, and further preferably 0.5 nm to 25 nm. It is preferably 0.5 nm to 10 nm.
  • the silver nanoparticles of the present invention comprise an amine (A) having an aliphatic hydrocarbon group and an amino group (sometimes referred to simply as “amine (A)”), and a mixture containing a silver compound (B) (simply “a mixture”).
  • amine (A) having an aliphatic hydrocarbon group and an amino group
  • B a mixture containing a silver compound
  • the silver nanoparticles of the present invention are in a state where the surface is coated with a protective agent containing an amine (A), have excellent stability, and have a low temperature of less than 200 ° C. (eg, 150 ° C. or less, preferably 120 ° C. or less).
  • the composition containing the silver nanoparticles can be obtained by a well-known and conventional method using silver nanoparticles (silver nanoparticles of the present invention) obtained by pyrolyzing the mixture, and is not particularly limited.
  • the silver nanoparticles obtained above can be obtained by suspending, dispersing or the like in an organic solvent by a conventional method after washing or the like as necessary.
  • Amine (A) As the amine (A) used in forming the silver nanoparticles of the present invention, any known and commonly used amine (amine compound) can be used as long as it has an aliphatic hydrocarbon group and an amino group.
  • the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. Each aliphatic hydrocarbon group includes a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group.
  • the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group.
  • specific embodiments of the amine (A) used in forming the silver nanoparticles of the present invention will be exemplified as amine embodiments 1 to 3, but the amine (A) is not limited to these embodiments. Absent.
  • Examples of the amine (A) include aliphatic hydrocarbon monoamines (A1) having 6 or more carbon atoms composed of an aliphatic hydrocarbon group and one amino group (sometimes simply referred to as “monoamine (A1)”), fatty acid An aliphatic hydrocarbon monoamine (A2) having 5 or less carbon atoms composed of an aromatic hydrocarbon group and one amino group (sometimes simply referred to as “monoamine (A2)”), and an aliphatic hydrocarbon group and two
  • the aspect using at least C8 or less aliphatic hydrocarbon diamine (A3) (it may only be called "diamine (A3)" which consists of an amino group is mentioned. That is, as one aspect of the above mixture, a mixture containing at least a monoamine (A1), a monoamine (A2), and a diamine (A3) as the amine (A) can be mentioned.
  • amine other than the said monoamine (A1), the said monoamine (A2), the said diamine (A3), etc. may be used. it can.
  • the monoamine (A1) is a monoamine in which the total number of carbon atoms (carbon number) constituting the monoamine (A1) is 6 or more.
  • the monoamine (A1) has a high function as a protective agent (stabilizer) on the surface of the silver nanoparticles produced by the hydrocarbon chain.
  • the monoamine (A1) is preferably an alkyl monoamine having 6 to 12 carbon atoms.
  • the monoamine (A1) includes a primary amine, a secondary amine, and a tertiary amine.
  • Examples of the primary amine monoamine (A1) include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine. , Saturated aliphatic hydrocarbon monoamines (that is, alkyl monoamines) such as heptadecylamine and octadecylamine.
  • saturated aliphatic hydrocarbon monoamine in addition to the above linear aliphatic hydrocarbon monoamine, for example, branched (branched) aliphatic hydrocarbon monoamines such as isohexylamine, 2-ethylhexylamine, tert-octylamine and the like Can be mentioned. Also included are cycloalkyl monoamines such as cyclohexylamine. Furthermore, unsaturated aliphatic hydrocarbon monoamines (that is, alkenyl monoamines) such as oleylamine can be mentioned.
  • Examples of the secondary amine monoamine (A1) include N, N-dipropylamine, N, N-dibutylamine, N, N-dipentylamine, N, N-dihexylamine, N, N-dipeptylamine, Examples thereof include dialkyl monoamines such as N, N-dioctylamine, N, N-dinonylamine, N, N-didecylamine, N, N-diundecylamine, N, N-didodecylamine, and N-propyl-N-butylamine.
  • Examples of the monoamine (A1) that is a tertiary amine include tributylamine and trihexylamine.
  • the monoamine (A1) a saturated aliphatic hydrocarbon monoamine having 6 or more carbon atoms is preferable.
  • the number of carbon atoms is not particularly defined, but saturated aliphatic hydrocarbon monoamines having up to 18 carbon atoms are usually preferred in consideration of availability, ease of removal during sintering, and the like.
  • alkyl monoamines having 6 to 12 carbon atoms such as hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, and dodecylamine are preferably used.
  • the monoamine (A1) may be used alone or in combination of two or more.
  • the monoamine (A1) is not particularly limited, but is 10 mol% to 65 mol based on the total (100 mol%) of the monoamine (A1), the monoamine (A2) and the diamine (A3). % Is preferably included.
  • the monoamine (A2) is an aliphatic hydrocarbon monoamine having 5 or less carbon atoms composed of an aliphatic hydrocarbon group and one amino group. That is, the monoamine (A2) is a monoamine having a total number of carbon atoms (carbon number) constituting the monoamine (A2) of 5 or less. Since the carbon chain length is shorter than that of the monoamine (A1), the function as a protective agent (stabilizer) itself is considered to be low. However, since the polarity is higher than that of the monoamine (A1), the silver compound ( It is considered that B) has a high coordination ability to silver and is effective in promoting complex formation.
  • the carbon chain length since the carbon chain length is short, it can be removed from the surface of the silver nanoparticles in a short time of 30 minutes or less or 20 minutes or less even when sintering at a low temperature of 120 ° C. or lower, or about 100 ° C. or lower. This is effective for low-temperature sintering of the obtained silver nanoparticles.
  • the monoamine (A2) includes a primary amine, a secondary amine, and a tertiary amine.
  • Examples of the monoamine (A2) include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, isopentylamine, tert-pentylamine and the like.
  • Examples thereof include saturated aliphatic hydrocarbon monoamines having 2 to 5 carbon atoms (that is, alkyl monoamines).
  • dialkyl monoamines such as N, N-dimethylamine, N, N-diethylamine, N-methyl-N-propylamine, N-ethyl-N-propylamine and the like can be mentioned.
  • n-butylamine isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, isopentylamine, tert-pentylamine and the like are preferable, and the above butylamines are particularly preferable.
  • the monoamine (A2) may be used alone or in combination of two or more.
  • the monoamine (A2) is not particularly limited, but is 5 mol% to 50 mol based on the total (100 mol%) of the monoamine (A1), the monoamine (A2), and the diamine (A3). It is preferable that it is contained in mol%.
  • the diamine (A3) is a diamine having a total number (carbon number) of carbon atoms constituting the diamine (A3) of 8 or less.
  • the diamine (A3) has a high coordination ability to the silver of the silver compound (B), and is effective in promoting complex formation.
  • the aliphatic hydrocarbon diamine generally has a higher polarity than the aliphatic hydrocarbon monoamine, and the coordination ability of the silver compound (B) to silver is high. Further, the diamine (A3) has an effect of promoting thermal decomposition at a lower temperature and in a shorter time in the thermal decomposition step of the complex compound, and silver nanoparticles can be produced more efficiently.
  • the protective film of the silver nanoparticles containing the diamine (A3) has a high polarity, the dispersion stability of the silver nanoparticles in a dispersion medium containing a highly polar solvent is improved. Furthermore, since the diamine (A3) has a short carbon chain length, even in sintering at a low temperature of, for example, 120 ° C. or less, or about 100 ° C. or less, the silver nanoparticle can be obtained in a short time of 30 minutes or less or 20 minutes or less. Since it can be removed from the particle surface, it is effective in sintering the obtained silver nanoparticles at a low temperature in a short time.
  • the diamine (A3) is preferably an alkyl diamine having 2 to 8 carbon atoms. More specifically, the diamine (A3) is, for example, ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1, 3-propanediamine, 2,2-dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, N, N-diethyl -1,3-propanediamine, N, N′-diethyl-1,3-propanediamine, 1,4-butanediamine, N, N-dimethyl-1,4-butanediamine, N, N′-dimethyl-1 , 4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N′-diethyl-1
  • alkylenediamines having 8 or less carbon atoms (total number of carbon atoms) in which at least one of the two amino groups is a primary amino group or a secondary amino group, and the silver of the silver compound (B) Is highly effective in promoting complex formation.
  • N N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propane
  • diamine (A3) N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propane
  • One of two amino groups such as diamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dimethyl-1,6-hexanediamine, etc.
  • R 1 and R 2 may be the same or different and each represents an alkyl group. However, the total number of carbon atoms of R, R 1 and R 2 is 8 or less.
  • the alkylene group does not contain a hetero atom such as an oxygen atom or a nitrogen atom.
  • the alkyl group does not contain a hetero atom such as an oxygen atom or a nitrogen atom.
  • a diamine having 6 or less carbon atoms is preferable, and a diamine having 5 or less carbon atoms (total number of carbon atoms) is more preferable from the viewpoint of being able to be removed from the silver nanoparticle surface in a short time even in low-temperature sintering.
  • the diamine (A3) may be used alone or in combination of two or more.
  • the diamine (A3) is not particularly limited, but 15 mol% to 50 mol based on the total (100 mol%) of the monoamine (A1), the monoamine (A2) and the diamine (A3). % Is preferably included.
  • the total amount of the monoamine (A1), the monoamine (A2), and the diamine (A3) used in this aspect (amine embodiment 1) in the present invention is not particularly limited.
  • the total amount of these amine components [(A1) + (A2) + (A3)] per mole of silver atom B) is preferably about 1 to 20 moles.
  • the total amount of the amine component is less than 1 mole relative to 1 mole of the silver atom, a silver compound that is not converted into a complex compound in the step of producing a complex compound of the amine (A) and the silver compound (B) ( B) may remain.
  • the uniformity of the silver nanoparticles may be impaired, and the particles may be enlarged, or the silver compound (B) may remain without being thermally decomposed.
  • the total amount of the amine component is preferably about 2 mol or more, for example.
  • the complex compound generation step and the thermal decomposition step can be performed satisfactorily.
  • About the minimum of the total amount of the said amine component, 2 mol or more is preferable with respect to 1 mol of silver atoms of the said silver compound (B), and 6 mol or more is more preferable.
  • an aliphatic hydrocarbon monoamine (A1) having 6 or more carbon atoms composed of an aliphatic hydrocarbon group and one amino group, an aliphatic hydrocarbon group and one amino group At least an aliphatic hydrocarbon monoamine (A2) having 5 or less carbon atoms and 5 mol of the monoamine (A1) based on the total (100 mol%) of the monoamine (A1) and the monoamine (A2). % To less than 20 mol% (for example, 5 mol% to 19 mol%), and the monoamine (A2) in a proportion of more than 80 mol% to 95 mol% (for example, 81 mol% to 95 mol%) The aspect used by is mentioned.
  • the amine (A) includes the monoamine (A1) and the monoamine (A2), and the monoamine (A1) and the monoamine (A2) are based on the total (100 mol%) of the monoamine. And a mixture containing (A1) in a proportion of 5 mol% or more and less than 20 mol% and monoamine (A2) in a proportion of more than 80 mol% and 95 mol% or less.
  • the use ratio of the monoamine (A1) and the monoamine (A2) is based on the total (100 mol%) of the monoamine (A1) and the monoamine (A2). Less than mol% (for example, 5 mol% or more and 19 mol% or less), and the monoamine (A2): more than 80 mol% and 95 mol% or less (for example, 81 mol% or more and 95 mol% or less).
  • amine other than the said monoamine (A1) and the said monoamine (A2) etc. can be used in the range which does not inhibit the effect by this invention.
  • a protective and stabilizing function of the surface of the silver nanoparticles to be produced can be obtained by the carbon chain of the monoamine (A1).
  • the expression of the protective stabilization function may be weak.
  • the content of the monoamine (A1) is 20 mol% or more, the protective stabilization function is sufficient, but the monoamine (A1) is formed by low-temperature sintering when forming a relatively thick sintered film. Is difficult to remove.
  • About the minimum of content of the said monoamine (A1), 10 mol% or more, for example, 13 mol% or more is preferable.
  • About the upper limit of content of the said monoamine (A1), 19 mol% or less, for example, 17 mol% or less is preferable.
  • the content of the monoamine (A2) is more than 80 mol% and 95 mol% or less, a complex formation accelerating effect can be easily obtained, and itself can contribute to low temperature and short time sintering.
  • the content of the monoamine (A2) is 80 mol% or less, the effect of promoting complex formation is weak, or the monoamine (A1) contains silver nano-particles during sintering when forming a relatively thick sintered film. It may be difficult to remove from the particle surface.
  • the content of the monoamine (A2) exceeds 95 mol%, the effect of promoting complex formation is obtained, but the content of the monoamine (A1) is relatively reduced, and the surface of the silver nanoparticles to be produced It is difficult to achieve stable protection.
  • the monoamine (A2) having a high coordination ability to the silver of the silver compound (B) is used in the above proportion, so that the silver nanoparticles of the monoamine (A1) are used. Less adhesion on the surface. Therefore, even in the case of sintering at a low temperature and a short time, these amines are easily removed from the surface of the silver nanoparticles, and the silver nanoparticles are sufficiently sintered.
  • the total amount of the monoamine (A1) and the monoamine (A2) used in this aspect of the present invention is not particularly limited, but is 1 mol of silver atom of the silver compound (B).
  • the amount of the amine [(A1) + (A2)] is preferably about 1 to 72 mol.
  • the silver compound (B) that is not converted into the complex compound remains in the complex compound formation step. In the subsequent pyrolysis step, the uniformity of the silver nanoparticles may be impaired and the particles may be enlarged, or the silver compound (B) may remain without being pyrolyzed.
  • the amount of the amine [(A1) + (A2)] exceeds about 72 mol with respect to 1 mol of the silver atom.
  • the amount of the amine [(A1) + (A2)] is preferably about 2 mol or more, for example.
  • the diamine (A3) can also be used.
  • a branched aliphatic hydrocarbon monoamine (A4) composed of a branched aliphatic hydrocarbon group having 4 or more carbon atoms and one amino group (simply referred to as “monoamine (A4)”)
  • monoamine (A4) a branched aliphatic hydrocarbon group having 4 or more carbon atoms and one amino group
  • A4 a branched aliphatic hydrocarbon group having 4 or more carbon atoms and one amino group
  • the steric factor of the branched aliphatic hydrocarbon group reduces the amount on the surface of the silver nanoparticle.
  • a larger area of the surface of the silver nanoparticle can be covered with the amount of adhesion. Therefore, moderate stabilization of the silver nanoparticles can be obtained with a smaller amount of adhesion on the surface of the silver nanoparticles. Since the amount of the protective agent (organic stabilizer) to be removed at the time of sintering is small, the organic stabilizer can be efficiently removed even when sintering at a low temperature of 200 ° C. or less, and the silver nanoparticles are sintered. Proceed sufficiently.
  • the number of carbon atoms of the branched aliphatic hydrocarbon group in the monoamine (A4) is 4 or more, for example, 4 to 16. In order to obtain the steric factor of the branched aliphatic hydrocarbon group, 4 or more carbon atoms are required.
  • the monoamine (A4) include 4 to 16 carbon atoms such as isobutylamine, sec-butylamine, tert-butylamine, isopentylamine, tert-pentylamine, isohexylamine, 2-ethylhexylamine, tert-octylamine and the like.
  • Preferred examples include primary amines having 4 to 8 carbon atoms.
  • Examples of the monoamine (A4) include N, N-diisobutylamine, N, N-diisopentylamine, N, N-diisohexylamine, and N, N-di (2-ethylhexyl) amine. Secondary amines are mentioned. Further, for example, tertiary amines such as triisobutylamine, triisopentylamine, triisohexylamine, tri (2-ethylhexyl) amine and the like can be mentioned.
  • N N-di (2-ethylhexyl) amine
  • the carbon number of the 2-ethylhexyl group is 8, but the total number of carbons contained in the monoamine (A4) is 16.
  • the total number of carbons contained in the monoamine (A4) is 24.
  • the monoamine (A4) is preferably a branched alkyl monoamine compound having 4 to 6 carbon atoms in the main chain, such as isopentylamine, isohexylamine, 2-ethylhexylamine and the like.
  • the “main chain” means a chain (chain composed of carbon-carbon bonds) having the longest length in the branched aliphatic hydrocarbon group. When the carbon number of the main chain is 4 to 6, moderate stabilization of the silver nanoparticles can be easily obtained. From the viewpoint of the steric factor of the branched aliphatic hydrocarbon group, it is effective that the second carbon atom is branched from the N atom side.
  • the monoamine (A4) may be used alone or in combination of two or more.
  • the amount of the monoamine (A4) used in the embodiment (amine embodiment 3) in the present invention is not particularly limited, but is 1 mol with respect to 1 mol of silver atoms of the starting silver compound (B). About 15 mol is preferable.
  • the amount of the monoamine (A4) is less than 1 mole relative to 1 mole of the silver atom, a silver compound (not converted into a complex compound) in the complex compound production step of the amine (A) and the silver compound (B) ( B) may remain. Further, in the subsequent pyrolysis step, the uniformity of the silver nanoparticles may be impaired, the particles may be enlarged, or the silver compound (B) may remain without being pyrolyzed.
  • the amount of the monoamine (A4) is preferably about 2 mol or more, for example.
  • the amount of the monoamine (A4) is preferably about 2 mol or more, for example.
  • the complex compound generation step and the thermal decomposition step can be performed satisfactorily.
  • About the minimum of the quantity of the said monoamine (A4), 2 mol or more is preferable with respect to 1 mol of silver atoms of the said silver compound (B), and 6 mol or more is more preferable.
  • the ratio of the monoamine (A4) to the total amount (100 mol%) of the amine (A) used in this aspect (amine embodiment 3) of the present invention is not particularly limited, but is 80 mol to 100 mol%. Preferably, it is 90 to 100 mol% (for example, 90 to 98 mol%). By controlling the ratio within such a numerical range, it is possible to efficiently produce silver nanoparticles having excellent dispersion stability in a dispersion medium, and to efficiently sinter silver nanoparticles. There is a tendency to be able to.
  • the monoamine (A4) in addition to the monoamine (A4), the monoamine ( An aliphatic hydrocarbon amine compound selected from A1), the monoamine (A2), and the diamine (A3) can be used independently.
  • the monoamine (A2) and the diamine (A3) are effective in promoting complex formation.
  • Silver compound (B) As the silver compound (B), a silver compound that is easily decomposed by heating to form metallic silver is used. Examples of such silver compounds include silver formate, silver acetate, silver oxalate, silver malonate, silver benzoate, silver phthalate and the like; silver fluoride, silver chloride, silver bromide, silver iodide, etc. Silver sulfate; silver sulfate, silver nitrate, silver carbonate and the like can be used, but silver oxalate is preferably used from the viewpoint that metal silver is easily generated by decomposition and impurities other than silver are hardly generated. Silver oxalate is advantageous in that it has a high silver content and does not require a reducing agent, so that metallic silver can be obtained by thermal decomposition as it is, and impurities derived from the reducing agent do not easily remain.
  • the composition containing the silver nanoparticles includes nanoparticles of metals other than silver (sometimes referred to as “other metals”), composites of silver and other metals.
  • Other nanoparticles such as nanoparticles may be included.
  • other metal compounds metal compounds
  • metal compounds may be used in place of the silver compound (B) in the method for producing silver nanoparticles of the present invention, or other compounds may be used together with the silver compound (B). It can manufacture by using a metal compound together.
  • a metal compound that is easily decomposed by heating to produce the other metal is used instead of the silver compound (B).
  • metal compounds include metal salts corresponding to the above silver compound (B), such as metal carboxylates; metal halides; metal salts such as metal sulfates, metal nitrates, and metal carbonates. Compounds can be used. Of these, metal oxalate is preferably used from the viewpoint of easily generating metal by decomposition and hardly generating impurities other than metal.
  • other metals include Al, Au, Pt, Pd, Cu, Co, Cr, In, and Ni.
  • the above silver compound (B) and other than the above silver A metal compound may be used in combination.
  • other metals include Al, Au, Pt, Pd, Cu, Co, Cr, In, and Ni.
  • the silver composite is composed of silver and one or more other metals, and examples thereof include Au—Ag, Ag—Cu, Au—Ag—Cu, and Au—Ag—Pd.
  • the silver composite is not particularly limited, but based on the total metal, silver is at least 20% by weight (ie, 20% by weight or more), usually 50% by weight (ie, 50% by weight or more), for example, 80% by weight. % (That is, 80% by weight or more).
  • the silver nanoparticles used in the semiconductor device of the present invention are obtained by heating the above mixture (a mixture containing at least the amine (A) and the silver compound (B)) (specifically, thermally decomposing the silver compound (B) by heating). Can be generated).
  • the preparation method of the said mixture is not specifically limited, For example, when using 2 or more types of amines (A), these mixtures (amine mixture liquid) are prepared, and silver compound (B) is added here after that.
  • the said mixture can be prepared by adding and mixing.
  • the addition of the silver compound (B) can be performed all at once or sequentially. When adding silver compound (B) sequentially, you may carry out continuously and can also carry out intermittently. Although it is not clear, it is presumed that complex formation of both proceeds at the stage of mixing the amine (A) and the silver compound (B).
  • the heating temperature (thermal decomposition temperature) of the above mixture for producing silver nanoparticles is not particularly limited, but can be appropriately set within a range of 60 to 150 ° C., for example.
  • the thermal decomposition can be efficiently advanced by heating at 80 to 120 ° C., so that silver nanoparticles are produced with high productivity. be able to.
  • the heating temperature can be constant, or can be controlled so as to change continuously or intermittently.
  • the time for heating the mixture (heating time) is not particularly limited, and can be appropriately set within a range of, for example, 5 to 360 minutes. Thereby, the composition containing silver nanoparticles is obtained.
  • Aliphatic carboxylic acid (C) when preparing silver nanoparticles, an aliphatic carboxylic acid (C) may be further used as a stabilizer in order to further improve the dispersibility of the silver nanoparticles in the dispersion medium.
  • the aliphatic carboxylic acid (C) can be used by being included in the amine mixed solution.
  • aliphatic carboxylic acid (C) a saturated or unsaturated aliphatic carboxylic acid is used.
  • aliphatic carboxylic acid a saturated or unsaturated aliphatic carboxylic acid is used.
  • saturated aliphatic monocarboxylic acids having 4 or more carbon atoms such as icosanoic acid and eicosenoic acid
  • unsaturated aliphatic monocarboxylic acids having 8 or more carbon atoms such as oleic acid
  • the aliphatic carboxylic acid (C) is preferably a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 18 carbon atoms.
  • the number of carbon atoms By setting the number of carbon atoms to 8 or more, an interval between the silver nanoparticles can be secured when the carboxylic acid group is adsorbed on the surface of the silver nanoparticles, thereby improving the effect of preventing aggregation of the silver nanoparticles.
  • saturated or unsaturated aliphatic monocarboxylic acids having up to 18 carbon atoms are usually preferred.
  • octanoic acid, oleic acid and the like are preferably used.
  • the aliphatic carboxylic acid (C) may be used alone or in combination of two or more.
  • the amount of the aliphatic carboxylic acid (C) used is not particularly limited, but is preferably 0.05 mol to 10 mol, for example, 0.1 mol with respect to 1 mol of silver atoms of the starting silver compound (B). ⁇ 5 mol is more preferable, and 0.5 mol to 2 mol is more preferable.
  • the amount of the aliphatic carboxylic acid (C) is less than 0.05 mol with respect to 1 mol of the silver atom, the stability improving effect in the dispersed state by the addition of the aliphatic carboxylic acid (C) is weak.
  • At least one of the joints in the semiconductor device of the present invention is a sintered body obtained by sintering the silver nanoparticles of the present invention.
  • the method for sintering the silver nanoparticles include well-known and commonly used methods for forming metal structures (sintered bodies) by sintering metal nanoparticles, and are not particularly limited.
  • a composition containing silver nanoparticles is supplied to the terminal and / or the electrode (either or both of the terminal and the electrode) by a desired thickness, shape, etc., by printing, etc.
  • the method of heating, after joining a terminal and the said electrode with the said composition is mentioned.
  • the heating conditions are not particularly limited, but by using the silver nanoparticles of the present invention, a low temperature of less than 200 ° C.
  • the joint part which is a sintered body obtained by sintering the silver nanoparticles of the present invention, is obtained. More specifically, the junction can be formed by a method in a semiconductor device manufacturing method described below.
  • the method for manufacturing a semiconductor device of the present invention is not particularly limited, and can be performed according to a well-known and commonly used method for manufacturing a semiconductor device. Specifically, as the manufacturing method, for example, the following steps (a) to (d) (step (a), step (b), step (c), and step (d)) are essential steps. The method of including is mentioned.
  • the method for performing each of the above-described steps (a) to (d) is not particularly limited, and can be performed according to a well-known and commonly used method. Further, the order in which the above-described steps (a) to (d) are performed is not particularly limited. For example, the steps (a), (b), (c), and (d) are performed in this order. Can do. Specifically, for example, it can be performed according to the method of performing each step in the description of the manufacturing method of the semiconductor device shown in FIGS. In particular, from the viewpoint of electrical conductivity and thermal conductivity between the terminal of the semiconductor element and the electrode of the substrate, the step (a) includes both the terminal of the semiconductor element and the electrode of the substrate according to the present invention. A step of supplying a composition containing silver nanoparticles (sometimes referred to as “step (a1)”) is preferable. Although it does not specifically limit as an aspect which supplies the said composition, For example, application
  • each step can be performed only once or twice or more.
  • the above-described steps (a) to (d) can be performed sequentially, or two or more steps can be performed simultaneously.
  • the semiconductor device manufacturing method of the present invention may include other steps in addition to the above-described steps (a) to (d).
  • FIGS. 2 to 4 show an example of a method of manufacturing a semiconductor device (semiconductor device of the present invention) in which all of the joints are sintered bodies obtained by sintering the silver nanoparticles of the present invention.
  • FIGS. 2 (a), 3 (a), and 4 (a) show an LED element as an example of the semiconductor element 4.
  • a semiconductor element 4 having terminals 5 is prepared.
  • a junction 6a may be formed on the terminal 5 of the semiconductor element 4 by a composition containing silver nanoparticles, as shown in FIG. As shown in a), the joint 6a may not be formed.
  • the joint 6a can be formed by applying or printing a composition containing silver nanoparticles on the terminal 5.
  • coating or printing For example, spin coating, inkjet printing, screen printing, dispenser printing, relief printing (flexographic printing), sublimation printing, offset printing, laser printer printing (toner printing), intaglio Examples thereof include printing (gravure printing), contact printing, and micro contact printing.
  • coating or printing For example, spin coating, inkjet printing, screen printing, dispenser printing, relief printing (flexographic printing), sublimation printing, offset printing, laser printer printing (toner printing), intaglio Examples thereof include printing (gravure printing), contact printing, and micro contact printing.
  • coating or printing For example, spin coating, inkjet printing, screen printing, dispenser printing, relief printing (flexographic printing), sublimation printing, offset printing, laser printer printing (toner printing), intaglio Examples thereof include printing (gravure printing), contact printing, and micro contact printing.
  • the patterned joint 6a can be formed by coating or printing.
  • the area of the terminal 5 is relatively large, it is preferable to form a plurality of the joint portions 6 a on one terminal 5 of the semiconductor element 4. As a result, the heat generated by the semiconductor element 4 can be radiated to the substrate 2 more effectively via the terminal 5 and the joint 6. Even when the semiconductor element 4 is an LED element, it is possible to suppress a decrease in light emission efficiency of the LED element due to its effective heat dissipation.
  • junction part 6 sintered body
  • the junction part 6a which consists of a composition containing a silver nanoparticle. It is not necessary to sinter yet.
  • a substrate 2 provided with electrodes 3 is prepared.
  • the bonding portion 6 b may be formed on the electrode 3 with a composition containing silver nanoparticles. Formation of the joining part 6b by the composition containing silver nanoparticles can be performed by coating or printing, as in the formation of the joining part 6a described above.
  • the composition containing the silver nanoparticles may be sintered to form a sintered body, or may not be sintered at this stage.
  • the bonding portion 6 is not a composition containing silver nanoparticles but a general-purpose one. It can comprise only the bump which consists of metal materials. Thereby, the usage-amount of the composition containing a silver nanoparticle can be saved.
  • the terminal 5 of the semiconductor element 4 and the electrode 3 of the substrate 2 are opposed to each other.
  • the bonding part 6a or the bonding part 6b is a sintered body of silver nanoparticles (that is, when it is 6)
  • the semiconductor element 4 is placed on the substrate while applying ultrasonic vibration to the semiconductor element 4. You may press toward 2. Thereby, the terminal 5 of the semiconductor element 4 and the electrode 3 of the board
  • the bonded portion 6a or the bonded portion 6b made of the composition containing silver nanoparticles is heated by heating through the substrate 2.
  • Sintering is less than 200 ° C. (eg 150 ° C. or less, preferably 120 ° C. or less, more preferably 100 ° C. or less, more preferably 80 ° C. or less) and 2 hours or less (eg 1 hour or less, preferably 30 minutes or less, more It is preferably 15 minutes or less, more preferably 10 minutes or less.
  • the sintering of silver nanoparticles sufficiently proceeds even by sintering at a low temperature and in a short time as described above. As a result, a sintered body having excellent conductivity (low resistance value, for example, 15 ⁇ cm or less) is formed.
  • the sintering may be performed simultaneously when the terminal 5 and the electrode 3 are joined. Thereby, the number of processes can be reduced. Moreover, it is not restricted to the method of heating through the board
  • energy such as an ultrasonic wave and electromagnetic waves
  • the joint portion 6 when the joint portion 6 is provided in a dot shape, it is preferable that a predetermined interval is provided between the dots so that the rows of the dots are parallel to each other. Thereby, the gas generated at the time of sintering can be efficiently released to the outside, and voids inside the joint portion 6 (sintered body) can be reduced, so that heat dissipation is improved. Furthermore, the bonding between the semiconductor element 4 and the substrate 2 can be further stabilized by regularly providing the plurality of bonding portions 6.
  • composition containing silver nanoparticles is applied or printed on the terminals 5 of the semiconductor element 4, in addition to being applied or printed in a dot shape as shown in FIG. A joint portion 6 having a large area can be formed. In that case, coating or printing may be performed so that the bonding portion 6 is provided on almost the entire surface of the terminal 5 of the semiconductor element 4. As a result, the conductivity and heat dissipation can be further improved.
  • the composition containing silver nanoparticles may be supplied to only one of the terminal 5 and the electrode 3 (for example, coating, printing, etc.). You may supply.
  • terminals 5 of the semiconductor element 4 it is not necessary for all the terminals 5 of the semiconductor element 4 to face the electrode 3 of the substrate 2.
  • at least one of the plurality of terminals 5 is provided on the substrate 2. As long as it is facing.
  • the obtained silver sintered film was measured using a four-terminal method (Loresta GP MCP-T610).
  • the measuring range limit of this device is 10 7 ⁇ cm.
  • N N-dimethyl-1,3-propanediamine
  • 2-ethylhexylamine MW: 129.25
  • Wako Pure Chemical Industries, Ltd. n-butylamine (MW: 73. 14): Reagent n-hexylamine (MW: 101.19) manufactured by Tokyo Chemical Industry Co., Ltd.
  • Reagent n-octylamine MW: 129.25
  • Reagent oleic acid MW: 282.47 manufactured by Tokyo Chemical Industry Co., Ltd.
  • Methanol Reagents manufactured by Wako Pure Chemical Industries, Ltd. 1-Butanol: Reagents manufactured by Tokyo Chemical Industry Co., Ltd. Octanes: Reagents manufactured by Wako Pure Chemical Industries, Ltd. Dihydroxyterpineol: Silver oxalate manufactured by Nippon Terpene Co., Ltd. (MW: 303. 78): synthesized from silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and oxalic acid dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • Example 1 (Preparation of silver nanoparticles) In a 50 mL flask, 1.28 g (12.5 mmol) of N, N-dimethyl-1,3-propanediamine, 0.91 g (12.5 mmol) of n-butylamine, 3.24 g (32.0 mmol) of n-hexylamine, n-Octylamine 0.39 g (3.0 mmol) and oleic acid 0.09 g (0.33 mmol) were added and stirred at room temperature to prepare a uniform mixed solution (amine-carboxylic acid mixed solution).
  • reaction mixture was heated and stirred at 105 ° C. to 110 ° C.
  • the reaction with the generation of carbon dioxide started immediately after the start of stirring, and then the stirring was continued until the generation of carbon dioxide was completed.
  • a suspension in which silver nanoparticles exhibiting a blue luster were suspended was obtained. .
  • the coating film was formed, it was immediately sintered at 120 ° C. for 15 minutes in a blow drying furnace to form a silver sintered film having a thickness of about 1 ⁇ m.
  • the specific resistance value of the obtained silver sintered film was measured by a four-terminal method and found to be 8.4 ⁇ cm.
  • [1] initial stage dispersibility evaluation and [2] storage stability evaluation were performed as follows. [1] When the silver nanoparticle dispersion immediately after preparation was filtered through a 0.2 ⁇ m filter, the filter was not clogged. That is, the silver nanoparticle dispersion liquid maintained a good dispersion state. [2] The silver nanoparticle dispersion liquid immediately after preparation was put in a transparent glass sample bottle, sealed, and stored in the dark at 25 ° C. for 7 days. No silver mirror was observed. When the silver nanoparticle dispersion after storage was filtered with a 0.2 ⁇ m filter, the filter was not clogged. That is, the silver nanoparticle dispersion after storage maintained a good dispersion state.
  • the viscous white substance obtained during the preparation of the silver nanoparticles is a combination of silver oxalate and alkylamine, and is based on the silver atoms of silver oxalate. It was speculated that this was a silver oxalate-amine complex in which the amino group of the alkylamine was coordinated.
  • the DSC measurement conditions were as follows. Apparatus: DSC 6220-ASD2 (manufactured by SII Nanotechnology) Sample container: 15 ⁇ L gold-plated sealed cell (manufactured by SII Nanotechnology) Temperature increase rate: 10 ° C / min (room temperature to 600 ° C) Atmospheric gas: Atmospheric pressure in the cell Air confinement Outside nitrogen flow
  • the white material with a viscous obtained during the preparation of the silver nanoparticles was subjected to IR spectrum measurement, absorption derived from the alkyl group of the alkyl amine (2900 cm around -1, around 1000 cm -1) was observed It was done. This also shows that the viscous white substance obtained during the preparation of the silver nanoparticles is formed by the combination of silver oxalate and alkylamine, and the silver oxalate has silver atoms. On the other hand, it was presumed to be a silver oxalate-amine complex in which the amino group was coordinated.
  • Example 2 In the preparation of silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 1.28 g (12.5 mmol) of N, N-dimethyl-1,3-propanediamine, 0.91 g (12.5 mmol) of n-butylamine, Example 1 was repeated except that n-hexylamine was changed to 3.24 g (32.0 mmol), n-octylamine 0.39 g (3.0 mmol), and oleic acid 0.13 g (0.45 mmol). Then, a silver nanoparticle dispersion was prepared, and a coating film was formed and sintered.
  • the obtained silver sintered film had a thickness of about 1 ⁇ m and a specific resistance value of 11.3 ⁇ cm.
  • Example 3 In the preparation of silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 1.53 g (15.0 mmol) of N, N-dimethyl-1,3-propanediamine, 0.73 g (10.0 mmol) of n-butylamine, Example 1 was repeated except that n-hexylamine was changed to 3.24 g (32.0 mmol), n-octylamine 0.39 g (3.0 mmol), and oleic acid 0.13 g (0.45 mmol). Then, a silver nanoparticle dispersion was prepared, and a coating film was formed and sintered.
  • the obtained silver sintered film had a thickness of about 1 ⁇ m and a specific resistance value of 14.2 ⁇ cm.
  • Example 4 In the preparation of silver nanoparticles, the composition of the amine-carboxylic acid mixed solution was changed to 1.02 g (10 mmol) of N, N-dimethyl-1,3-propanediamine, 1.10 g (15.0 mmol) of n-butylamine, n- Except for changing to 3.24 g (32.0 mmol) of hexylamine, 0.39 g (3.0 mmol) of n-octylamine, and 0.13 g (0.45 mmol) of oleic acid, the same as in Example 1, A silver nanoparticle dispersion was prepared, and a coating film was formed and sintered.
  • the obtained silver sintered film had a thickness of about 1 ⁇ m and a specific resistance value of 14.5 ⁇ cm.
  • Example 5 (Preparation of silver nanoparticles) To a 50 mL flask, 10.84 g (150 mmol) of n-butylamine and 3.00 g (30 mmol) of n-hexylamine were added and stirred at room temperature to prepare a uniform mixed solution (amine mixed solution).
  • reaction mixture was heated and stirred at 85 ° C. to 90 ° C.
  • the color gradually changed to brown, and by stirring for 2 hours, a suspension in which silver nanoparticles were suspended was obtained.
  • the coating film was sintered in a blow drying oven under the following conditions to form a silver sintered film of each thickness.
  • the specific resistance value of the obtained silver sintered film was measured by a four-terminal method.
  • Example 6 A silver nanoparticle-containing paste was prepared in the same manner as in Example 5 except that n-hexylamine 3.00 g (30 mmol) was changed to n-octylamine 3.88 g (30 mmol) in the composition of the amine mixed solution. The coating film was formed and sintered under the following conditions.
  • the thickness of the obtained silver sintered film was about 1 ⁇ m, and the specific resistance value was about 2.0E + 08 ⁇ cm.
  • the silver nanoparticles used in the semiconductor device of the present invention have good dispersibility and storage stability in the dispersion, and have a relatively thick film of, for example, 1 ⁇ m or more. Even when the silver sintered film is formed by sintering at a low temperature for a short time, good conductivity can be imparted. Moreover, since a dense silver sintered body with high purity can be obtained at a low temperature and in a short time, it is possible to impart both good heat dissipation and high strength.
  • the semiconductor device and the manufacturing method thereof according to the present invention are particularly useful as a semiconductor device including a power semiconductor having high heat generation, an optical semiconductor element, etc. and requiring heat dissipation, and a manufacturing method thereof.
  • the electrical conductivity of the junction is excellent, the energy efficiency is high, so that it is useful as a semiconductor device that contributes to energy saving and a manufacturing method thereof.

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Abstract

　La présente invention concerne un dispositif à semi-conducteur de haute précision dont le semi-conducteur est protégé contre les endommagements au moment de la liaison de l'élément semi-conducteur et le substrat, qui présente une haute performance de dissipation thermique de l'élément semi-conducteur vers le substrat, qui présente une liaison ferme entre l'élément semi-conducteur et le substrat, qui présente une haute conductivité électrique à partir de la borne de l'élément semi-conducteur et de l'électrode du substrat, et dont le rendement de production est élevé. L'invention concerne en outre un procédé de fabrication dudit dispositif à semi-conducteur. Le dispositif à semi-conducteur selon l'invention comprend : un élément semi-conducteur et un substrat, ledit dispositif à semi-conducteur étant caractérisé en ce que la borne de l'élément semi-conducteur et l'électrode du substrat sont orientées face à face, ladite borne et ladite électrode étant reliées par un ou plusieurs éléments de liaison, au moins un des éléments de liaison étant un corps fritté obtenu par frittage de nanoparticules d'argent, et lesdites nanoparticules d'argent étant obtenues par décomposition thermique d'un mélange contenant un amine (A) comprenant un groupe hydrocarboné aliphatique et un groupe aminé, et un composé d'argent (B). L'invention concerne en outre un procédé de fabrication dudit dispositif à semi-conducteur.
PCT/JP2014/068270 2013-07-09 2014-07-09 Dispositif à semi-conducteur à nanoparticules d'argent et son procédé de fabrication WO2015005372A1 (fr)

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TWI695389B (zh) * 2015-02-06 2020-06-01 國立大學法人北海道大學 複合微粒及分散液以及彼等之製造方法及用途
WO2021256040A1 (fr) * 2020-06-15 2021-12-23 ソニーセミコンダクタソリューションズ株式会社 Dispositif à semi-conducteurs et son procédé de production

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JPWO2022050353A1 (fr) * 2020-09-07 2022-03-10
US11652052B2 (en) 2021-03-29 2023-05-16 Tpk Advanced Solutions Inc. Contact structure and electronic device having the same

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JP2010140928A (ja) * 2008-12-09 2010-06-24 Shinkawa Ltd 半導体装置ならびに半導体ダイの実装方法
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JP2007332259A (ja) * 2006-06-14 2007-12-27 Nichia Chem Ind Ltd トランスファーモールド用タブレット、その製造方法、発光装置及びその製造方法
JP2010140928A (ja) * 2008-12-09 2010-06-24 Shinkawa Ltd 半導体装置ならびに半導体ダイの実装方法
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TWI695389B (zh) * 2015-02-06 2020-06-01 國立大學法人北海道大學 複合微粒及分散液以及彼等之製造方法及用途
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JP7002230B2 (ja) 2017-06-22 2022-01-20 スタンレー電気株式会社 電子デバイスの製造方法
WO2021256040A1 (fr) * 2020-06-15 2021-12-23 ソニーセミコンダクタソリューションズ株式会社 Dispositif à semi-conducteurs et son procédé de production
EP4167274A4 (fr) * 2020-06-15 2024-01-03 Sony Semiconductor Solutions Corporation Dispositif à semi-conducteurs et son procédé de production

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