JP2014188561A - Joint method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a joint method by which a joint layer having a conductivity and a high shear strength can be formed.SOLUTION: A joint method joins members to be joined to each other by interposing a joint material containing metallic fine particles among the members and burns the material. The metallic fine particles are pre-disintegrated in an organic solvent by use of a wet type disintegrator, and burning thereof is carried out by heating the particles to a temperature within a range of 320 to 480°C under a reductive atmosphere containing hydrogen gas. The metallic fine particles contain metal elements of 90 weight percent or more and a metal hydroxide within a range of 1 to 35 weight percent, and further contain a nickel element of 50 weight parts or more per whole metal elements of 100 weight parts.

Description

  The present invention relates to a joining method that can be used for manufacturing electronic components and the like.

  Metal fine particles have physical and chemical properties different from those of bulk metals, and are therefore used in various industrial materials. In recent years, with the downsizing and thinning of electronic devices, the particle diameter of industrial metal fine particles has been reduced to about several tens to several hundreds of nanometers. For example, Patent Document 1 proposes a bonding material for electronic components using a nickel material that is relatively inexpensive and can be used at high temperatures. The bonding material of Patent Document 1 uses metal nanoparticles that include metal fine particles composed of nickel or a nickel alloy and an oxygen-containing film that covers the metal fine particles, and have an average particle diameter of 100 nm or less. .

  When metal fine particles are used for the bonding material, a baking process is required in which a bonding material containing metal fine particles is disposed between the members to be bonded and heated at a temperature of, for example, 300 ° C. or higher. The behavior of the metal fine particles in the firing step (hereinafter, sometimes referred to as “sinterability”) greatly affects the conductivity and shear strength of the bonding layer. For example, if the bonding layer after the firing step is in a state where the particle interface of many metal fine particles is confirmed, the conductivity and shear strength of the bonding layer are not sufficiently increased. On the other hand, when the bonding layer after the firing step is in a fused state in which the particle interface of the metal fine particles is not confirmed at all, it has conductivity and high shear strength.

  In Patent Document 2, a metal porous body having fine pores of nanometer order is obtained by heating a molded body of nickel particles and silver particles at 350 ° C. for 3 hours in an atmosphere of nitrogen gas (containing 3% hydrogen gas). A method for manufacturing a mass has been proposed. However, the metal porous body of Patent Document 2 is not supposed to be used as a bonding material.

International Publication WO2012 / 173187 Pamphlet JP 2012-224885 A

  When nickel fine particles are used as a bonding material, it is necessary that the nickel fine particles are fused to become conductive by firing and have electrical conductivity, and the bonding layer needs to have a sufficiently high shear strength. Factors that affect the conductivity and shear strength of the bonding layer include the average particle size of the metal fine particles used as a raw material, the particle size distribution, the dispersion / aggregation state, the surface modification state, and the firing conditions of the firing step. However, these factors are related to each other. For example, the optimum firing conditions vary depending on other factors, that is, the type and average particle size of the raw metal fine particles, the particle size distribution, the dispersion / aggregation state, the surface modification state, and the like. Therefore, there has been a demand for a bonding method that can form a bonding layer having conductivity and high shear strength with high reproducibility on an industrial scale.

  An object of the present invention is to provide a bonding method capable of forming a bonding layer having electrical conductivity and high shear strength.

  The joining method of this invention is a joining method which joins to-be-joined members by interposing a joining material containing metal microparticles between to-be-joined members, and baking. In the joining method of the present invention, the metal fine particles are preliminarily crushed in an organic solvent using a wet pulverizer, and the firing is performed in a reducing atmosphere containing hydrogen gas at 320 to 480. By heating to a temperature in the range of ° C.

  In the joining method of the present invention, the metal fine particles contain 90% by weight or more of a metal element and 1 to 35% by weight of a metal hydroxide, and nickel element is added to 100 parts by weight of all metal elements. It may contain 50 parts by weight or more.

  In the joining method of the present invention, the average particle size of the primary particles of the metal fine particles may be within a range of 50 to 150 nm, and the coefficient of variation (standard deviation / average particle size) of the particle size of the metal fine particles is It may be 0.3 or less.

  In the bonding method of the present invention, the metal fine particles may be coated with an ester compound having a molecular weight in the range of 100 to 500 after the crushing treatment.

  According to the joining method of the present invention, the metal fine particles previously pulverized in an organic solvent using a wet pulverizer are brought to a temperature in the range of 320 to 480 ° C. in a reducing atmosphere containing hydrogen gas. By heating and firing, a bonding layer having electrical conductivity and high shear strength can be formed.

2 is an FE-SEM photograph at a magnification of 250,000 times of a sample after firing in Example 1. FIG. 2 is an FE-SEM photograph of 500,000 times magnification of a sample after firing in Example 1. FIG. 3 is an FE-SEM photograph at a magnification of 250,000 times of a sample after firing in Example 2. FIG. 4 is an FE-SEM photograph of 500,000 times magnification of a sample after firing in Example 2. FIG. 4 is an FE-SEM photograph at a magnification of 250,000 times of a sample after firing in Example 3. FIG. 4 is an FE-SEM photograph of 500,000 times magnification of a sample after firing in Example 3. FIG. 4 is an FE-SEM photograph of a sample after firing in Example 4 at a magnification of 250,000. 4 is an FE-SEM photograph of 500,000 times magnification of a sample after firing in Example 4. FIG. It is a FE-SEM photograph of the magnification after 250,000 times of the sample after baking in Example 16. It is a FE-SEM photograph of magnification 500,000 times of the sample after baking in Example 16. 3 is an FE-SEM photograph of a sample after firing in Reference Example 1 at a magnification of 250,000. 4 is an FE-SEM photograph at a magnification of 500,000 times for a sample after firing in Reference Example 1. 5 is an FE-SEM photograph of a sample after firing in Reference Example 2 at a magnification of 250,000. 4 is an FE-SEM photograph of 500,000 times magnification of a sample after firing in Reference Example 2. 4 is an FE-SEM photograph of a sample after firing in Reference Example 3 at a magnification of 250,000 times. It is a FE-SEM photograph of magnification 500,000 times of the sample after firing in Reference Example 3. 4 is an FE-SEM photograph of a sample after firing in Reference Example 4 at a magnification of 250,000. It is a FE-SEM photograph of magnification 500,000 times of the sample after firing in Reference Example 4.

  Embodiments of the present invention will be described below. The joining method of the present embodiment is a joining method for joining members to be joined together by firing a joining material containing metal fine particles interposed between the members to be joined.

<Bonding material>
(Metal fine particles)
The bonding material used in the bonding method of the present embodiment contains metal fine particles. The metal fine particles preferably contain 90% by weight or more of a metal element. Examples of the metal fine particles include base metals such as nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, vanadium, gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, Metal fine particles containing single or two or more metal elements such as noble metals such as rhenium can be used. Among these metal fine particles, it is preferable to use nickel fine particles or an alloy of nickel fine particles and the above metal species. The nickel fine particles preferably contain 50 parts by weight or more of nickel element with respect to 100 parts by weight of all metal elements.

  Moreover, it is preferable that a metal microparticle contains a metal hydroxide within the range of 1-35 weight%. The metal hydroxide is an effective factor for improving the shear strength of the joining layer, but when the content of the metal hydroxide is more than 35% by weight, the shear strength of the joining layer tends to decrease. The content of the metal hydroxide is more preferably in the range of 3 to 15% by weight, further preferably in the range of 5 to 15% by weight, and most preferably in the range of 9 to 15% by weight.

  Moreover, it is preferable that the average particle diameter of the primary particle of a metal fine particle exists in the range of 50-150 nm. By setting the lower limit of the average particle size of the primary particles of the metal fine particles to 50 nm or more, it is possible to suppress the shrinkage change during sintering and to improve the sinterability by suppressing the total amount of the oxide layer of the metal fine particles. . Moreover, when the average particle diameter of the primary particles of the metal fine particles exceeds 150 nm, the low-temperature sinterability of the metal fine particles may deteriorate.

  The metal fine particles preferably have a narrow particle size distribution in order to obtain sufficient dispersibility. For example, the particle size variation particle size (standard deviation / average particle size) is 0.3 or less. Preferably, it is 0.2 or less.

  The metal fine particles used in the joining method of the present embodiment are preliminarily crushed in an organic solvent using a wet pulverizer. By the crushing treatment, the aggregated particles (secondary particles) of the metal fine particles are separated, and a substantially homogeneous aggregate of primary particles can be obtained. As a result, the fine particles uniformly contact each other, so that fusion between particles is promoted, the sinterability of the metal fine particles is improved, and the shear strength of the bonding layer can be increased. Further, it is considered that the sinterability of the metal fine particles is improved by making the hydroxide or oxide present on the surface of the metal fine particles or the organic film more nearly uniform by the crushing treatment.

  As the wet crusher used for the crushing treatment, for example, a high-pressure homogenizer, a wet jet mill or the like can be used. As the high-pressure homogenizer, for example, Starburst (trade name; manufactured by Sugino Machine Co., Ltd.) can be used.

  As an organic solvent used for the crushing treatment, an ether organic solvent having 4 to 30 carbon atoms, a saturated or unsaturated hydrocarbon organic solvent having 7 to 30 carbon atoms, an alcohol solvent having 3 to 18 carbon atoms, or the like is used. be able to. Specific examples include toluene, xylene, hexane, cyclohexane, octane, dencan, limonene, methanol, ethanol, propanol, isopropanol, butanol and the like.

  As conditions for the crushing treatment, for example, the pressure is preferably in the range of 70 MPa to 245 MPa, and more preferably in the range of 100 to 200 MPa. When the pressure is less than 70 MPa, the metal fine particles are not sufficiently crushed and it is difficult to obtain a sufficient shear strength. On the other hand, when the pressure exceeds 245 MPa, hydroxides or oxides present on the surface of the metal fine particles and organic substances are peeled more than necessary, and the metal fine particles tend to re-aggregate. From such a viewpoint, the metal fine particles are preferably obtained by reducing a metal salt that is a precursor of the metal fine particles in an organic solvent.

(Low molecular dispersant)
The metal fine particles used in the bonding method of the present embodiment are coated with an ester compound having a molecular weight in the range of 100 to 500 (hereinafter sometimes referred to as “low molecular dispersant”) after being crushed. It is preferred that Examples of the low molecular weight dispersant include ester compounds containing two functional groups represented by the following general formula (1) or (2). These functional groups contribute to improving the dispersibility of the metal fine particles. The metal fine particles may form a complex with the ester compound. Here, the composite is a state in which the ester compound is adsorbed or adhered around the metal fine particles due to the interaction between the functional groups in the ester compound and the surface of the metal fine particles or the functional groups (for example, hydroxyl groups) present on the surface. Or a chemically bonded state. By taking such a complex form, the ester compound is in a state of being close to the metal fine particles, so that it is presumed that the dispersion effect by the ester compound is effectively exhibited.

[In formula (1) or (2), each group R independently represents an alkyl group having 1 to 6 carbon atoms, an optionally substituted phenyl group or a benzyl group. ]

  Here, as the alkyl group having 1 to 6, preferably 2 to 6 carbon atoms, for example, a linear or branched alkyl group is preferable. Moreover, as a phenyl group which may be substituted, any of a phenyl group, a tolyl group, or an anisoyl group is preferable, for example. The molecular weight of the ester compound is preferably in the range of 100 to 500, more preferably in the range of 150 to 450.

  Examples of the ester compound include an ester compound derived from tartaric acid, an ester compound derived from malonic acid, an ester compound derived from citric acid, and an ester compound derived from trimethylpentanediol. Specific examples of such ester compounds include, for example, dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D-tartaric acid, di-o-4- Toluoyl-L-tartaric acid, di-o-4-toluoyl-D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, di-m-4-toluoyl-D-tartaric acid, di-p-anisoyl-L- Tartaric acid, di-p-anisoyl-D-tartaric acid, di-o-anisoyl-L-tartaric acid, di-o-anisoyl-D-tartaric acid, di-m-anisoyl-L-tartaric acid, di-m-anisoyl-D- Tartaric acid, diacetyl-L-tartaric acid, diacetyl-D-tartaric acid, dipivaloyl-L-tartaric acid, dipivaloyl-D-tartaric acid, L-diisopropyl tartrate, D-diisopropyl tartrate, L-di-tartaric acid -Butyl, D-di-n-butyl tartrate, L-dimethyl tartrate, D-dimethyl tartrate, diethyl L-tartrate, diethyl D-tartrate, dibenzyl L-tartrate, dibenzyl tartrate, 2,3-O-isopropylidene Ester compounds derived from tartaric acid such as -L-dimethyl tartrate, 2,3-O-isopropylidene-D-dimethyl tartrate, diisopropyl malonate, di-t-butyl malonate, dibenzyl malonate, benzylmethyl malonate, Ester compounds derived from malonic acid such as dibutyl malonate, dihexyl malonate, diethyl isobutyl malonate, diethyl malonate, dimethyl malonate, trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate, O- Trimethyl acetyl citrate, O-acetyl chloride Ester compounds derived from citric acid such as triethyl acid, tripropyl O-acetylcitrate, tributyl O-acetylcitrate, and trimethylpentane such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate And ester compounds derived from diols.

  The ester compound derived from tartaric acid is preferably a tartaric acid derivative represented by the following general formula (I).

[In the formula (I), the group R ₁₁ and the group R ₁₂ each independently represent an optionally substituted phenyl group. ]

In the general formula (I), examples of the optionally substituted phenyl group represented by the group R ₁₁ and the group R ₁₂ include a phenyl group, an optionally substituted phenyl group, and an alkoxy group. The phenyl group etc. which may be mentioned can be mentioned. Here, as the alkyl group, for example, a lower alkyl group having 1 to 4 carbon atoms is preferable because it has an excellent dispersion effect, and a methyl group is more preferable. Moreover, as an alkoxy group, since a C1-C4 lower alkoxy group has the outstanding dispersion | distribution effect, a methoxy group is more preferable. Accordingly, specific examples of the optionally substituted phenyl group include a phenyl group, o-, m- or p-tolyl group, or o-, m- or p-anisoyl group. Among these, o- Most preferred are m, or p-tolyl groups.

  Preferred examples of the tartaric acid derivative represented by the general formula (I) include dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, and di-p-toluoyl-D-tartaric acid. Di-o-4-toluoyl-L-tartaric acid, di-o-4-toluoyl-D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, di-m-4-toluoyl-D-tartaric acid, di- -P-anisoyl-L-tartaric acid, di-p-anisoyl-D-tartaric acid, di-o-anisoyl-L-tartaric acid, di-o-anisoyl-D-tartaric acid, di-m-anisoyl-L-tartaric acid, di- -M-anisoyl-D-tartaric acid and the like can be mentioned. Among these, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D-tartaric acid, di-o-4-toluoyl-L-tartaric acid, and di-o-4-toluoyl- having excellent dispersing effect Most preferred are D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, and di-m-4-toluoyl-D-tartaric acid.

  The reason why the tartaric acid derivative represented by the general formula (I) has an excellent dispersing action on the metal fine particles is not yet clear, but between the metal fine particles and the tartaric acid derivative represented by the general formula (I). It is speculated that some kind of interaction has occurred. For example, the tartaric acid derivative represented by the general formula (I) has two ester structures derived from a carboxylic acid in the molecule and two bulky or hydrophobic aromatic rings respectively involved in the formation of these ester structures. have. These ester structures-aromatic rings may be involved in the dispersing action. That is, the interaction between the two ester structures-the aromatic ring and the metal fine particles causes the tartaric acid derivative to be present in the vicinity of the metal fine particles, thereby changing the electrical properties of the surface of the metal fine particles. Alternatively, it is considered that the aggregation of metal fine particles is suppressed by steric hindrance and further dispersibility is imparted by affinity with a solvent. Here, as the interaction, for example, an ionic bond, a covalent bond, an electrostatic bond, a coordination bond, a hydrogen bond, and the like can be considered.

  Moreover, the ester compound derived from tartaric acid is preferably a tartaric acid derivative represented by the following general formula (II).

[In formula (II), group R < ₂₁ >, group R < ₂₂ > shows a C3-C6 alkyl group each independently. ]

In the general formula (II), examples of the alkyl group having 3 to 6 carbon atoms represented by the group R ₂₁ and the group R ₂₂ include a propyl group, a butyl group, a pentyl group, and a hexyl group. Among these, a branched alkyl group having 3 to 6 carbon atoms is preferable because it has an excellent dispersion effect, and among them, an isopropyl group is more preferable.

  Preferable specific examples of the tartaric acid derivative represented by the general formula (II) include diisopropyl L-tartrate, diisopropyl D-tartrate, di-n-butyl L-tartrate, and di-n-butyl tartrate. Can do. Among these, L-isopropyl tartrate and D-isopropyl tartrate having the excellent dispersion effect are most preferable.

  The reason why the tartaric acid derivative represented by the general formula (II) has an excellent dispersing action on the metal fine particles is not yet clear, but between the metal fine particles and the tartaric acid derivative represented by the general formula (II). It is speculated that some kind of interaction has occurred. For example, a tartaric acid derivative represented by the general formula (II) has two ester structures derived from a carboxylic acid in the molecule and two alkyl groups (preferably branched alkyl groups) each involved in the formation of these ester structures. Group). These ester structures-alkyl groups may be involved in the dispersing action. That is, the two ester structures-alkyl groups cause an interaction between the metal fine particles, and the tartaric acid derivative is present in the vicinity of the metal fine particles, thereby changing the electrical properties of the surface of the metal fine particles. It is considered that the aggregation of metal fine particles is suppressed, and further, dispersibility is imparted by affinity with a solvent. Here, as the interaction, for example, an ionic bond, a covalent bond, an electrostatic bond, a coordination bond, a hydrogen bond, and the like can be considered.

  The ester compound derived from malonic acid is preferably a malonic acid derivative represented by the following general formula (III).

[In the formula (III), the group _{X 1} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or benzyl group, group _{R 31,} groups _{R 32} are each independently C 1 -C -6 alkyl group, a phenyl group, or a benzyl group is shown. ]

In the general formula (III), the group X ₁ is preferably a hydrogen atom, and the group R ₃₁ and the group R ₃₂ are each independently preferably an alkyl group having 3 to 6 carbon atoms or a benzyl group. Here, as a C3-C6 alkyl group, a propyl group, a butyl group, a pentyl group, a hexyl group etc. can be mentioned, for example. Among these, a branched alkyl group having 3 to 6 carbon atoms is preferable because it has an excellent dispersion effect. Among them, a branched propyl group or a branched butyl group is more preferable, and an isopropyl group and a t-butyl group are most preferable.

  Preferable specific examples of the malonic acid derivative represented by the general formula (III) include diisopropyl malonate, di-t-butyl malonate, dibenzyl malonate, benzylmethyl malonate, dibutyl malonate, dihexyl malonate and the like. Can be mentioned. Among these, di-t-butyl malonate and dibenzyl malonate having an excellent dispersion effect are most preferable.

  The reason why the malonic acid derivative represented by the general formula (III) has an excellent dispersing action on the metal fine particles is not yet clear, but the metal fine particles and the malonic acid derivative represented by the general formula (III) It is presumed that some kind of interaction has occurred between them. For example, the malonic acid derivative represented by the general formula (III) has two ester structures derived from carboxylic acid in the molecule, and a bulky or hydrophobic aromatic ring or alkyl involved in the formation of these ester structures. It has a group (preferably a branched alkyl group). Such a structure may be involved in the dispersion action. That is, interaction occurs between the metal ester by two ester structures and a bulky or hydrophobic aromatic ring or alkyl group (preferably a branched alkyl group), and the malonic acid derivative is in the vicinity of the metal microparticle. In this state, the electrical properties of the surface of the metal fine particles are changed, or the steric hindrance suppresses aggregation of the metal fine particles, and further imparts dispersibility by affinity with the solvent. It is thought that there is. Here, as the interaction, for example, an ionic bond, a covalent bond, an electrostatic bond, a coordination bond, a hydrogen bond, and the like can be considered.

  The ester compound derived from citric acid is preferably a citric acid derivative represented by the following general formula (IV).

[In Formula (IV), group _{X 2} represents a hydrogen atom or an acetyl group, a group _{R 41,} group _{R 42,} groups _{R 43} are independently an alkyl group having 1 to 6 carbon atoms. ]

In the general formula (IV), examples of the alkyl group having 1 to 6 carbon atoms represented by the group R ₄₁ , the group R ₄₂ , and the group R ₄₃ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A xyl group can be mentioned. Further, in the citric acid derivative, a dispersion in which the group X ₂ is a hydrogen atom and the groups R ₄₁ , R ₄₂ , and R ₄₃ are alkyl groups having 3 to 6 carbon atoms in the general formula (IV) is excellent. Among these, a linear alkyl group having 3 to 6 carbon atoms is more preferable, and among them, a butyl group is most preferable.

  Preferable specific examples of the citric acid derivative represented by the general formula (IV) include trimethyl citrate, triethyl citrate, tripropyl citrate, tributyl citrate, trimethyl O-acetylcitrate, and triethyl O-acetylcitrate. , Tripropyl O-acetylcitrate, tributyl O-acetylcitrate and the like. Among these, tributyl citrate and O-acetyl tributyl citrate are most preferable because they have an excellent dispersion effect.

  The reason why the citric acid derivative represented by the general formula (IV) has an excellent dispersing action on the metal fine particles is not yet clear, but the metal fine particles and the citric acid derivative represented by the general formula (IV) It is presumed that some kind of interaction has occurred between them. For example, the citric acid derivative represented by the general formula (IV) has three ester structures derived from carboxylic acid in the molecule and three alkyl groups that are respectively involved in the formation of these ester structures. . These ester structures-alkyl groups may be involved in the dispersing action. That is, the interaction between the ester structure and the metal fine particles is caused by three ester structures and the electrical properties of the surface of the metal fine particles are changed by the presence of the citric acid derivative in the vicinity of the metal fine particles. Thus, it is considered that the aggregation of the metal fine particles is suppressed, and further, the dispersibility is imparted by the affinity with the solvent. Here, as the interaction, for example, an ionic bond, a covalent bond, an electrostatic bond, a coordination bond, a hydrogen bond, and the like can be considered.

  Moreover, as the ester compound derived from trimethylpentanediol, a trimethylpentanediol derivative represented by the following general formula (V) is preferable.

[In the formula (V), the group R ₅₁ and the group R ₅₂ each independently represent an acyl group having 4 to 6 carbon atoms. ]

In the general formula (V), the group R ₅₁ and the group R ₅₂ are preferably branched acyl groups having 4 to 6 carbon atoms because they have an excellent dispersion effect, and the group R ₅₁ and the group R ₅₂ are preferable. Are more preferably isobutanoyl groups.

  As the trimethylpentanediol derivative represented by the general formula (V), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate having an excellent dispersion effect is most preferable.

  The reason why the trimethylpentanediol derivative represented by the general formula (V) has an excellent dispersing action on the fine metal particles is not yet clear, but the trimethylpentanediol derivative represented by the fine metal particles and the general formula (V) is not yet clear. It is presumed that some interaction has occurred between For example, the trimethylpentanediol derivative represented by the general formula (V) has two ester structures in the molecule and a bulky or hydrophobic acyl group (preferably a branched acyl group) involved in the formation of the ester structure. have. Such a structure may be involved in the dispersion action. That is, two ester structures and a bulky or hydrophobic acyl group (preferably a branched acyl group) cause an interaction between the metal fine particles, and the trimethylpentanediol derivative comes close to the metal fine particles. By being present in a state, the electrical properties of the surface of the metal fine particles are changed, or the steric hindrance suppresses aggregation of the metal fine particles, and further imparts dispersibility by affinity with the solvent. It is considered a thing. Here, as the interaction, for example, an ionic bond, a covalent bond, an electrostatic bond, a coordination bond, a hydrogen bond, and the like can be considered.

  Among the ester compounds represented by the general formulas (I) to (V), the ester compound represented by the general formula (I) is particularly preferable.

  Said ester compound can also be used individually or in combination of 2 or more types. Moreover, it can also be used in combination with the dispersing agent which consists of another compound in the range which does not impair the effect of invention.

  The coating treatment with the low molecular dispersant is performed by adding the low molecular dispersant to a slurry containing the pulverized metal fine particles and the organic solvent. Thereby, the ester compound is coated on the surface of the metal fine particles. The method for adding the low molecular dispersant is not particularly limited, and may be added to the metal fine particles as they are, or may be added to the metal fine particles in a state dissolved in an arbitrary solvent.

  Since the low molecular dispersant has a strong aggregation suppressing action, an excellent dispersion effect can be expected even in a small amount. Therefore, the amount of the low molecular dispersant used is preferably in the range of 0.1 to 5 parts by weight, and in the range of 0.5 to 2 parts by weight with respect to 100 parts by weight of the metal fine particles. The inside is more preferable. When the amount of the low molecular dispersant used is less than 0.1 parts by weight based on 100 parts by weight of the metal fine particles, there is a tendency that a sufficient dispersion effect cannot be obtained. Tend to occur. Further, if the low molecular dispersant is excessively used exceeding the above upper limit, the product may be affected by the low molecular dispersant remaining in the finally obtained fine metal particles. Therefore, after applying a low molecular dispersant to the metal fine particles, it is preferable to remove the excess ester compound by washing. The washing can be performed using, for example, an alcohol solvent such as isopropanol.

  In the present embodiment, by using the ester compound, the fine metal fine particles having a particle diameter of 50 nm to 150 nm are suppressed in aggregation, and the metal fine particles having a sharp particle size distribution in which single particles are dispersed are used. Can be obtained. Further, since the ester compound has a strong aggregation suppressing action, an excellent dispersion effect can be expected even in a small amount. Furthermore, the effect which can reduce the volatile matter which generate | occur | produces by a baking process etc. is acquired by removing an excess ester compound.

  The bonding material used in the bonding method of the present embodiment can contain, for example, an organic solvent, a flux component, a viscosity modifier, a thixotropic agent, a reducing agent, a surfactant, a polymer dispersing agent and the like in addition to the metal fine particles. . The bonding material can be in the form of, for example, a slurry, a paste, a grease, or a wax.

<Paste>
It is preferable to add a high boiling point solvent to the metal fine particles coated with the low molecular dispersant and then concentrate and paste it. As the high boiling point solvent used in the pasting step, those having a boiling point of 150 ° C. or higher are preferable. Specific examples thereof include 1-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1- 7 or more aliphatic alcohols such as nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1, Examples include polyhydric alcohols such as 3-butanediol, 1,4-butanediol, tetramethylene glycol, and methyltriglycol, and terpineols such as α-terpineol, β-terpineol, and γ-terpineol. In order to prevent excessive water molecules from adhering to the surface of the metal fine particles, it is preferable to use a high boiling point solvent having a water content in the range of 0.01 to 0.1% by weight, for example.

  In order to maintain the form of the paste, the content of the metal fine particles is preferably within the range of 70 to 90% by weight of the total amount of the bonding material. If the content of the metal fine particles is less than 70% by weight, for example, it may be necessary to repeat coating several times, which may cause unevenness, and sufficient bonding strength may not be obtained. May decrease and usability as a bonding material may decrease. Further, in the bonding material application, the weight ratio of metal fine particles to solvent (metal fine particles / solvent) is preferably in the range of 1 to 19 in order to maintain a paste-like form.

[Baking process]
In this step, a joining material containing metal fine particles is interposed between the members to be joined, and heated to a temperature in the range of 320 to 480 ° C. in a reducing gas atmosphere containing a reducing gas. The metal fine particles are sintered to join the members to be joined together.

  This step is, for example, a step of applying a paste-like bonding material containing metal fine particles to one or both of the surfaces to be bonded (application step), bonding the surfaces to be bonded together, for example, a temperature of 320 ° C. By heating to a temperature in the range of 480 ° C. or lower, preferably 350 ° C. or higher and 450 ° C. or lower, the step of sintering the bonding material (firing step), and solidifying the sintered bonding material by cooling, A step of forming a bonding layer (solidification step).

  In the coating process for coating the bonding material, for example, methods such as spray coating, inkjet coating, and printing can be employed. The bonding material can be applied in an arbitrary shape such as a pattern shape, an island shape, a mesh shape, a lattice shape, or a stripe shape according to the purpose. In the applying step, it is preferable to apply the bonding material so that the thickness of the solidified bonding portion (metal bonding layer) after bonding is 120 nm or more. By applying with such a thickness, defects in the joint portion can be reduced, so that an increase in electrical resistance and a decrease in joint strength can be prevented.

  In the firing step, the metal fine particles are sintered, and a metal bonding layer having a uniform and strong adhesive force can be formed. Moreover, since the metal hydroxide film and the ester compound are reduced, oxygen is prevented from entering the metal bonding layer, and the conductivity of the metal bonding layer is ensured. The heating temperature for bonding is preferably 320 ° C. or higher, and more preferably 350 ° C. or higher in order to obtain sufficient bonding strength. In addition, when the heating temperature exceeds 480 ° C., there is a concern about damage to peripheral circuits or electrodes. Therefore, the upper limit of the heating temperature is preferably 450 ° C. or less.

The formation of the bonding layer with the metal fine particles is preferably performed in an atmosphere in which a reducing gas such as H ₂ is present. Further, by reducing the pressure, an effect of suppressing the generation of voids can be obtained. For example, the effect is confirmed at a pressure of 95% or less of the atmospheric pressure. Moreover, when bonding a joint surface, it can be pressurized as needed.

  The thickness of the joining portion (metal joining layer) formed by sintering the metal fine particles is preferably 120 nm or more, for example. When the thickness of the joint portion is thinner than this, defects in the joint portion increase, which causes an increase in electrical resistance and a decrease in strength. In addition, a joint part (metal joining layer) may have a void, when applying to the use which requires thermal stress relaxation.

  The bonding method according to the present embodiment can be used for bonding, for example, Si and SiC semiconductor materials as well as metal materials. In particular, when the base material deteriorates in the heat-affected zone in joining by wax material or welding, it is preferable to join at a low temperature. For example, the metal fine particles used in the bonding method of the present embodiment are hardened steel, stainless steel, and metal strengthened by work hardening, whose strength decreases due to recovery, recrystallization, etc. by heating at 450 ° C. or higher or 800 ° C. or higher. Suitable for joining materials, inorganic materials and metal materials that deteriorate due to thermal oxidation and thermal strain. Examples of the joined body include, but are not limited to, a pipe, a plate, a joint, a rod, a wire, and a bolt.

  The joining method of this embodiment can also be used in the manufacturing process of electronic components. Here, examples of the electronic component mainly include a semiconductor device and an energy conversion module component. When the electronic component is a semiconductor device, for example, between the back surface of the semiconductor element and the substrate, between the semiconductor electrode and the substrate electrode, between the semiconductor electrode and the semiconductor electrode, between the power device or the power module and the heat dissipation member. It can be applied to joining.

  When bonding electronic components, in order to increase the bonding strength, for example, a contact metal layer made of a material such as Au, Cu, Pd, Ni, Ag, Cr, Ti or an alloy thereof is previously formed on one or both of the surfaces to be bonded. Is preferably provided. When the material of the surface to be joined is SiC or Si or an oxide film on the surface thereof, a contact metal layer made of a material such as Ti, TiW, TiN, Cr, Ni, Pd, V or an alloy thereof is used. It is preferable to provide it. The thickness of each contact metal layer is preferably in the range of, for example, 50 nm or more and 2 μm or less. If the thickness of the contact metal layer is less than 50 nm, defects are likely to occur, and if it exceeds 2 μm, the vapor deposition process becomes long, and the production efficiency may be reduced.

[Nickel fine particles]
Next, nickel fine particles, which are the most preferable aspect of the metal fine particles used in the bonding material of the present embodiment, and a manufacturing method thereof will be described in detail.

The nickel fine particles preferably have a nickel hydroxide (Ni (OH) ₂ ) coating on the surface thereof. By having a nickel hydroxide coating, it is so hard that it will not be crushed even if pressure is applied to the coating film when it is applied as a bonding material to the bonded members, and the coating film itself will be sticky. The shear strength of the bonding layer can be increased. In addition, the hydroxide coating suppresses the surface activity of the nickel fine particles, and can suppress low-temperature combustion or rapid gasification that occurs during the out-of-system release of the carbon element in the firing step.

  The nickel hydroxide coating may be a coating partially present on the surface of the nickel fine particles, or a coating covering the entire surface of the particles. The nickel hydroxide coating may contain adsorbed water present on the surface of the nickel fine particles. The nickel hydroxide film is preferably grown by dipping in an alcoholic organic solvent. Nickel fine particles in which a nickel hydroxide film is grown by immersion in an alcohol-based organic solvent tend to exhibit a high shear strength when a bonding layer is formed.

  The nickel fine particles used in the bonding material of the present embodiment has a nickel hydroxide content of 1 to 35% by weight, preferably 3 to 15% by weight, more preferably 5 to 15% by weight. Of these, more preferably in the range of 9 to 15% by weight. When the content of nickel hydroxide is less than 1% by weight, the effect of improving the shear strength of the bonding layer cannot be obtained. On the other hand, when the content of nickel hydroxide is more than 35% by weight, the shear strength of the bonding layer tends to decrease.

  The fine nickel particles used in the bonding material of the present embodiment have a carbon element content of 0.3 to 2.5% by weight, preferably 0.5 to 2.0% by weight. The carbon element is derived from an organic compound present on the surface of the nickel fine particles, and contributes to an improvement in the dispersibility of the nickel fine particles. Therefore, when the carbon element content is less than 0.3% by weight, sufficient dispersibility may not be obtained. When the carbon element content exceeds 2.5% by weight, carbonization is performed after firing to form residual charcoal. There is a possibility of reducing the conductivity.

  The nickel fine particles used for the bonding material of the present embodiment has an oxygen element content of 0.9 to 9.0% by weight, preferably 2.0 to 6.5% by weight. The oxygen element is mainly derived from the nickel hydroxide coating, and when the nickel hydroxide coating is reduced and no longer exists, the sintering of the nickel fine particles is started. When the oxygen element content exceeds 9.0% by weight, the nickel fine particles are likely to be aggregated, the paste state cannot be maintained, and the powder tends to become powdery.

  The nickel fine particles used for the bonding material of the present embodiment have a carbon element content ratio (carbon element content / oxygen element content; C / O ratio) to oxygen element of more than 0.1 and not more than 0.35. Within the range, preferably more than 0.1 and not more than 0.25, more preferably more than 0.1 and not more than 0.2. The C / O ratio takes into consideration both the dispersibility and the reducibility of the nickel fine particles. When the C / O ratio is 0.1 or less, the nickel fine particles are likely to aggregate, and the nickel fine particles are sintered. In addition to the large shrinkage change during ligation, the continuity may be reduced. Moreover, when C / O ratio exceeds 0.35, the tendency for an organic compound to carbonize at the time of baking and to become a residual carbon becomes strong. By setting the C / O ratio within the above range, it is particularly advantageous when sintering is performed in a reducing gas atmosphere containing hydrogen gas.

  The nickel fine particles used for the bonding material of the present embodiment preferably have a chlorine element content of less than 900 ppm by weight from the viewpoint of oxidation resistance in the firing step and prevention of corrosion after firing. In particular, when nickel chloride is used as a raw material for the nickel fine particles, it is preferable to reduce the amount of chlorine by performing a chlorine removal treatment after the formation of the nickel fine particles. The chlorine removal process will be described later.

  The nickel fine particles used in the bonding material of the present embodiment are fine particles mainly composed of nickel, and the content of nickel element is preferably 50 parts by weight or more with respect to 100 parts by weight of all metal elements. The amount is preferably 70 parts by weight or more, more preferably 75 parts by weight or more. Nickel fine particles include, for example, base metals such as nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, vanadium, gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium. These may contain one or more metal elements such as noble metals.

  The thickness of the nickel hydroxide coating is preferably in the range of 1 to 8 nm, for example, from the viewpoint of effectively suppressing aggregation of nickel fine particles. In the present specification, the thickness of the nickel hydroxide film means that the surface of the nickel fine particles extracted at random 200 is observed with a transmission electron microscope with an acceleration voltage of 300 KV, and from the lattice spacing with a high contrast. The length from the end that can be identified as a fine particle to the end of the portion with a low contrast is measured, and the average of the measurement results of 10 nickel fine particles is taken as the thickness of the coating.

  The average particle diameter of the primary particles of the nickel fine particles used for the bonding material of the present embodiment is preferably in the range of 50 to 150 nm, for example. The thickness of the nickel hydroxide coating is almost the same regardless of the average particle diameter of the nickel particles, but the nickel hydroxide content tends to increase as the average particle diameter of the nickel fine particles decreases. By setting the lower limit to 50 nm or more, it is possible to improve the sinterability by suppressing the change in shrinkage during sintering and suppressing the total amount of the oxidized layer of nickel fine particles. Moreover, when the average particle diameter of the primary particles of the nickel fine particles exceeds 150 nm, the low-temperature sinterability of the nickel fine particles may deteriorate. In addition, in this specification, the average particle diameter of the primary particles of the nickel fine particles, including the values used in the examples, is a photograph of a sample by a field emission scanning electron microscope (FE-SEM). Is a value calculated based on the number of particles, which is obtained by randomly extracting 200 images from each of the images, obtaining the respective areas, and converting them into true spheres.

  The nickel fine particles used in the bonding material of the present embodiment preferably have a narrow particle size distribution, for example, a CV value of 0.3 or less, in order to sufficiently exhibit the dispersion effect of the ester compound.

  The nickel fine particles used in the bonding material of the present embodiment have a nickel hydroxide coating, so that the nickel fine particles are hard enough not to be crushed even when pressure is applied to the coating film when applied to the bonded member as a bonding material. Since the film itself has adhesiveness, the shear strength of the bonding layer after firing can be increased. In addition, the hydroxide coating suppresses the surface activity of the nickel fine particles, and can suppress low-temperature combustion or rapid gasification that occurs during the out-of-system release of the carbon element in the firing step. As described above, nickel fine particles having few aggregated particles and having a sharp particle size distribution can be suitably used as a bonding material, for example.

[Production method of nickel fine particles]
Next, a preferred method for producing nickel fine particles used for the bonding material of the present embodiment will be described. The method for producing nickel fine particles can include the following first and second steps.
First step:
A step of depositing raw material nickel fine particles having a nickel hydroxide coating by reducing nickel ions from a mixture containing a nickel salt and an organic amine by a wet reduction method.
Second step:
A step of crushing raw material nickel fine particles in an organic solvent using a wet crusher.

<First step>
In the first step, nickel ions are reduced by a wet reduction method from a mixture containing a nickel salt and an organic amine to deposit raw material nickel fine particles having a nickel hydroxide coating. In this step, first, a mixture containing a nickel salt and an organic amine is prepared.

(Nickel salt)
Examples of the nickel salt include inorganic salts such as nickel carboxylate (nickel carboxylate), nickel chloride, nickel nitrate, nickel sulfate, nickel carbonate, nickel hydroxide, Ni (acac) ₂ (β-diketonato complex), A nickel salt composed of an organic ligand such as nickel stearate can be used. Among these, it is preferable to use nickel carboxylate, which has a relatively low dissociation temperature (decomposition temperature) in the reduction process and does not cause the concern of residual chlorine element.

(Organic amine)
As the organic amine, a primary amine can be preferably used. The primary amine can form a complex with nickel ions, and effectively exhibits a reducing ability for nickel complexes (or nickel ions). On the other hand, secondary amines have great steric hindrance and may hinder the good formation of nickel complexes. Since tertiary amines do not have the ability to reduce nickel ions, none can be used alone. When these are used, these may be used in combination as long as the shape of the nickel fine particles to be produced is not hindered. The primary amine is not particularly limited as long as it can form a complex with nickel ions, and can be a solid or liquid at room temperature. Here, room temperature means 20 ° C. ± 15 ° C. The primary amine that is liquid at room temperature also functions as an organic solvent for forming the nickel complex. In addition, even if it is a primary amine solid at normal temperature, there is no particular problem as long as it is liquid by heating at 100 ° C. or higher, or can be dissolved using an organic solvent.

  Hereinafter, the first step will be described by taking as an example the case of using a primary amine as the organic amine and nickel carboxylate as the nickel salt. The kind of carboxylic acid in nickel carboxylate is not particularly limited. For example, the carboxyl group may be one monocarboxylic acid, or the carboxyl group may be two or more carboxylic acids. Moreover, acyclic carboxylic acid may be sufficient and cyclic carboxylic acid may be sufficient. As such nickel carboxylate, nickel acyclic monocarboxylate can be preferably used, and among nickel acyclic monocarboxylate, nickel formate, nickel acetate, nickel propionate, nickel oxalate, benzoic acid It is more preferable to use nickel or the like. By using these nickel acyclic monocarboxylates, the resulting nickel fine particles are less likely to have a variation in shape and are easily formed in a uniform shape. The nickel carboxylate may be an anhydride or a hydrate.

  The primary amine may be an aromatic primary amine, but an aliphatic primary amine is preferred from the viewpoint of easy nickel complex formation in the reaction solution. Aliphatic primary amine can control the particle diameter of nickel fine particles produced by adjusting the length of the carbon chain, for example, and produces nickel fine particles having an average particle diameter in the range of 50 nm to 150 nm. This is advantageous. From the viewpoint of controlling the particle diameter of the nickel fine particles, the aliphatic primary amine is preferably selected from those having about 6 to 20 carbon atoms. The larger the carbon number, the smaller the particle size of the nickel fine particles obtained. Examples of such amines include octylamine, trioctylamine, dioctylamine, hexadecylamine, dodecylamine, tetradecylamine, stearylamine, oleylamine, myristylamine, and laurylamine. For example, oleylamine exists in a liquid state under the temperature conditions in the nickel fine particle production process, and therefore the reaction can proceed efficiently in a homogeneous solution.

Since the primary amine functions as a surface modifier during the production of the nickel fine particles, secondary aggregation can be suppressed even after removal of the primary amine. In addition, the primary amine is preferably liquid at room temperature from the viewpoint of ease of processing operation in the washing step of separating the solid component of the generated nickel fine particles and the solvent or unreacted primary amine after the reduction reaction. . Further, the primary amine is preferably one having a boiling point higher than the reduction temperature from the viewpoint of ease of reaction control when the nickel complex is reduced to obtain nickel fine particles. That is, the aliphatic primary amine preferably has a boiling point of 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably has 9 or more carbon atoms. Here, for example, the boiling point of aliphatic amine [C ₉ H ₂₁ N (nonylamine)] having 9 carbon atoms is 201 ° C. The amount of primary amine is preferably 2 mol or more, more preferably 2.2 mol or more, and more preferably 4 mol or more with respect to 1 mol of nickel. When the amount of primary amine is less than 2 mol, it is difficult to control the particle diameter of the obtained nickel fine particles, and the particle diameter tends to vary. The upper limit of the amount of primary amine is not particularly limited, but is preferably 20 mol or less from the viewpoint of productivity, for example.

(Organic solvent)
In the first step, an organic solvent other than the primary amine may be newly added in order to allow the reaction in the homogeneous solution to proceed more efficiently. When an organic solvent is used, the organic solvent may be mixed simultaneously with the nickel carboxylate and the primary amine. However, when the organic solvent is added after first mixing the nickel carboxylate and the primary amine to form a complex, It is more preferable because it efficiently coordinates to a nickel atom. The organic solvent that can be used is not particularly limited as long as it does not inhibit the complex formation between the primary amine and the nickel ion. For example, the organic solvent having 4 to 30 carbon atoms, 7 to 30 carbon atoms, and the like. A saturated or unsaturated hydrocarbon organic solvent, an alcohol organic solvent having 8 to 18 carbon atoms, or the like can be used. Moreover, from the viewpoint of enabling use even under heating conditions by microwave irradiation, it is preferable to select an organic solvent having a boiling point of 170 ° C. or higher, more preferably in the range of 200 to 300 ° C. It is better to choose one. Specific examples of such an organic solvent include tetraethylene glycol and n-octyl ether.

(Complex formation)
A divalent nickel ion is known as a ligand-substituted active species, and the ligand of the complex to be formed may easily change in complex formation by ligand exchange depending on temperature and concentration. For example, in the step of obtaining a reaction solution by heat-treating a mixture of nickel carboxylate and primary amine, considering steric hindrance such as the carbon chain length of the amine used, for example, carboxylate ions (R ₁ COO, R ₂ COO) There is a possibility of coordination by either bidentate coordination or monodentate coordination. Furthermore, when the amine concentration is in a large excess, there may be a structure in which carboxylate ions are present in the outer sphere. In order to obtain a homogeneous solution at the target reaction temperature (reduction temperature), at least one of the ligands must be coordinated with a primary amine. In order to take this state, it is necessary that the primary amine is excessively present in the reaction solution, and it is preferable that at least 2 mol per 1 mol of nickel ions is present, and 2.2 mol or more exist. It is more preferable that 4 mol or more is present.

  Although this complex formation reaction can proceed even at room temperature, the reaction is carried out by heating to a temperature in the range of 100 ° C. to 165 ° C. in order to perform a sufficient and more efficient complex formation reaction. This heating is particularly advantageous when nickel carboxylate hydrate such as nickel formate dihydrate or nickel acetate tetrahydrate is used as nickel carboxylate. The heating temperature is preferably a temperature exceeding 100 ° C., more preferably a temperature of 105 ° C. or more, so that the ligand substitution reaction between the coordinating water coordinated with nickel carboxylate and the primary amine is efficient. The water molecule as the complex ligand can be dissociated, and the water can be discharged out of the system, so that the complex with the amine can be efficiently formed. For example, nickel formate dihydrate has a complex structure in which two coordination waters and two formate ions as bidentate ligands exist at room temperature. In order to efficiently form a complex by substituting a ligand for a primary amine, it is preferable to dissociate the water molecule as the complex ligand by heating at a temperature higher than 100 ° C. In addition, the heat treatment in the complex formation reaction between nickel carboxylate and primary amine is surely separated from the subsequent heat reduction process by microwave irradiation of the nickel complex (or nickel ion) to complete the complex formation reaction. In view of the above, the temperature is set to the upper limit temperature or lower, preferably 160 ° C. or lower, more preferably 150 ° C. or lower.

  The heating time can be appropriately determined according to the heating temperature and the content of each raw material, but is preferably 10 minutes or more from the viewpoint of completing the complex formation reaction. There is no upper limit on the heating time, but heat treatment for a long time is useless from the viewpoint of saving energy consumption and process time. The heating method is not particularly limited, and may be heating by a heat medium such as an oil bath or heating by microwave irradiation.

  The complex formation reaction between nickel carboxylate and primary amine can be confirmed by a change in the color of the solution when a solution obtained by mixing nickel carboxylate and primary amine in an organic solvent is heated. . In addition, this complex formation reaction is carried out by measuring the absorption maximum wavelength of the absorption spectrum observed in the wavelength region of 300 nm to 750 nm using, for example, an ultraviolet / visible absorption spectrum measuring apparatus, and measuring the maximum absorption wavelength of the raw material (for example, nickel formate). In dihydrate, the maximum absorption wavelength is 710 nm, and in nickel acetate tetrahydrate, the maximum absorption wavelength is 710 nm.) The shift of the complexing reaction solution (the maximum absorption wavelength shifts to 600 nm) is observed. Can be confirmed.

  After the complex formation between nickel carboxylate and primary amine is performed, the resulting reaction solution is heated by microwave irradiation to reduce the nickel ions of the nickel complex as described below. At the same time, the carboxylate ions coordinated in the nuclei are decomposed, and finally nickel fine particles containing nickel having an oxidation number of 0 are generated. In general, nickel carboxylate is hardly soluble under conditions other than using water as a solvent, and a solution containing nickel carboxylate needs to be a homogeneous reaction solution as a pre-stage of the heat reduction reaction by microwave irradiation. On the other hand, the primary amine used in the present embodiment is liquid under the operating temperature conditions, and is considered to be liquefied by coordination with nickel ions to form a homogeneous reaction solution.

  Next, the complexing reaction solution obtained by the complex formation reaction between nickel carboxylate and primary amine is heated to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction solution. A raw material nickel fine particle slurry having a nickel hydroxide coating is obtained. The temperature for heating by microwave irradiation is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of suppressing variation in the shape of the obtained raw material nickel fine particles. The upper limit of the heating temperature is not particularly limited, but is preferably set to 270 ° C. or less, for example, from the viewpoint of efficiently performing the treatment. In addition, the use wavelength of a microwave is not specifically limited, For example, it is 2.45 GHz. The heating temperature can be appropriately adjusted depending on, for example, the type of nickel carboxylate and the use of an additive that promotes the nucleation of the raw material nickel fine particles.

  In this step, since microwaves penetrate into the reaction solution, uniform heating is performed, and energy can be directly applied to the medium, so that rapid heating can be performed. As a result, the entire reaction solution can be made uniform at a desired temperature, and the processes of reduction, nucleation, and nucleation of the nickel complex (or nickel ions) occur simultaneously in the entire solution. Narrow monodisperse particles can be easily produced in a short time.

  In order to produce raw material nickel fine particles having a uniform particle size, the nickel complex is uniformly and sufficiently produced in the complexing reaction liquid production step (step in which the nickel complex is produced), and the raw material nickel fine particle slurry is produced. In the step (step of heating and reducing by microwave irradiation), it is necessary to simultaneously generate and grow nickel (zero-valent) nuclei generated by reduction of the nickel complex (or nickel ion). That is, by adjusting the heating temperature of the complexing reaction liquid generation step within the above specific range and ensuring that it is lower than the heating temperature by the microwave in the raw material nickel fine particle slurry generation step, Easy to produce ordered particles. For example, if the heating temperature is too high in the complexing reaction liquid generation process, the formation of a nickel complex and the reduction reaction to nickel (zero valence) proceed at the same time to generate different types of metal species. It may be difficult to produce particles having a uniform particle shape. Moreover, if the heating temperature in the raw material nickel fine particle slurry generation process is too low, the reduction reaction rate to nickel (zero valence) is slowed and the generation of nuclei is reduced, so that not only the particles become larger but also the yield of the raw material nickel fine particles It is not preferable also from a point.

  The raw material nickel fine particle slurry obtained by heating by microwave irradiation is, for example, left and separated, and after removing the supernatant liquid, the raw material nickel fine particles are obtained by washing with an appropriate solvent and drying. In the raw material nickel fine particle slurry generating step, the organic solvent described above may be added as necessary. As described above, the primary amine used for the complex formation reaction is preferably used as it is as the organic solvent.

<Second step>
In this step, the raw material nickel fine particles are pulverized in an organic solvent using a wet pulverizer. By crushing the raw material nickel fine particles having the nickel hydroxide coating obtained in the first step, a bonding layer having excellent shear strength can be formed when used as a bonding material. The conditions for the crushing treatment are as described above.

  Furthermore, in the manufacture of nickel fine particles, for example, a dispersion process, a pasting process, and a chlorine removing process can be performed as optional processes.

<Chlorine removal process>
When nickel chloride is used as the raw material nickel salt, the raw material nickel fine particles obtained in the first step are preferably subjected to acid treatment as the chlorine removal step. By the acid treatment, the chlorine element derived from nickel chloride, which is the nickel precursor, is removed, and the content of the chlorine element can be reduced to preferably less than 900 mass ppm, more preferably less than 100 mass ppm. The acid treatment also has an action of removing hydroxides such as nickel hydroxide present on the surface of the raw material nickel fine particles and fine particles adhering to the surface, so that the oxygen content can be adjusted. The acid that can be used for the acid treatment of the raw material nickel fine particles is preferably a weak acid, for example, an inorganic acid such as carbonic acid, or an organic acid such as acetic acid, propionic acid, tartaric acid, malonic acid, succinic acid, ascorbic acid, or citric acid. Can be used. The acid treatment can be performed by, for example, a method of washing the raw material nickel fine particles with an acid solution, a method of blowing a gasified acid (for example, carbon dioxide gas) into a slurry of the raw material nickel fine particles, and the like. In the method of washing the raw material nickel fine particles with an acid solution, the raw material nickel fine particles are preferably washed with, for example, an acid solution having a pH in the range of 3.5 to 6.5, preferably pH 4.5 to 6.0. When the acid solution has a pH of less than 3.5, oxidation and dissolution of the surface of the raw material nickel fine particles progress, and it becomes easy to sinter and it becomes difficult to make the particles spherical. When the acid solution exceeds pH 6.5, the effect of acid treatment cannot be sufficiently obtained.

  As described above, nickel fine particles can be prepared. Since the nickel fine particles thus obtained can maintain a uniform dispersion state, the flatness when applied in a paste state is high, and the shear strength of the bonding layer can be sufficiently increased. In addition, also when manufacturing a nickel alloy and the metal fine particle of another metal seed | species, it can carry out according to the said method.

  The features of the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.

[Measurement of average particle size]
The average particle diameter is measured by taking a picture of a sample with a field emission scanning electron microscope (FE-SEM), and randomly extracting 200 samples from each of the samples. The average particle size of the primary particles was calculated based on the number of particles obtained when converted to a true sphere. The CV value (coefficient of variation) was calculated by (standard deviation) / (average particle diameter). In addition, it shows that a particle diameter is so uniform that a CV value is small.

[Evaluation of dispersibility]
Evaluation of dispersibility was performed using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd., trade name: LA-950V2). A slurry solution in which metal fine particles are dispersed in isopropanol is diluted to a predetermined concentration, and dispersed in the particle size distribution measuring apparatus with ultrasonic waves for 5 minutes, and volume distribution is measured. A comparative evaluation of sex was performed.

[Quantitative determination of nickel hydroxide]
Determination of nickel hydroxide {Ni _{(OH) 2}} is Atsushi Nobori analyzer (Thermal Desorption Spectroscopy: TDS, manufactured by Electronic Science Co., trade name; WA1000S / W type) with a ^{10 -6} to At a measurement pressure of 10 ⁻³ Pa, the sample is heated at a rate of 10 ° C./min, and water desorbed from the surface of the sample is detected by mass spectrometry in a temperature range from 120 ° C. to 250 ° C., The absolute number was calculated from the correlation equation between the detection intensity and the number of molecules.

[Quantification of oxygen content]
The oxygen content was quantified by heating the sample in a carbon furnace at about 1800 ° C. using an inert gas melting-infrared absorption measuring device (manufactured by LECO, trade name: TC600) and measuring the carbon dioxide generated by the reduction reaction. Obtained from the amount of infrared absorption.

[Quantitative determination of nickel oxide]
When nickel hydroxide is heated in an inert atmosphere, it changes from the reaction of formula (1) to nickel oxide.
Ni (OH) ₂ → NiO + H ₂ O (1)
Therefore, the amount of nickel oxide (NiO) was calculated from a value obtained by subtracting the amount of oxygen calculated from the “quantitative determination of nickel hydroxide” from the amount of oxygen obtained by the “quantitative determination of oxygen content”.

[Quantification of organic substances present on the surface of nickel fine particles]
The organic substance present on the surface of the nickel fine particles was quantified using a differential thermothermal gravimetric simultaneous measurement apparatus (Thermogravimetry-Differential Thermal Analysis: TG-DTA, manufactured by SII Nanotechnology, Inc., trade name: TG / DTA6200). Under the measurement conditions of heating and heating at a rate of 10 ml / min with a nitrogen gas flow rate of 200 ml / min, the weight reduction amount of the sample is measured, and this weight and the desorption of water determined in the above-mentioned “determination of nickel hydroxide” The amount of organic matter was calculated from the difference from the amount.

[Evaluation of sinterability]
3 mg of the paste prepared in each example was sandwiched between glass substrates and fixed with a clip to obtain a sample for sinterability test (about 10 mmΦ). This sample was heated under predetermined conditions, and the periphery of the fired sample attached to the cooled glass substrate was observed with a field emission scanning electron microscope (FE-SEM). The evaluation of sinterability is "impossible" when all the nickel fine particles are confirmed to have all the particle interfaces confirmed, and "possible" when the nickel particle is partially visible at each nickel fine particle. In at least one of the cases, the state in which no particle interface was confirmed was defined as “good”, and the state in which no particle interface was confirmed in all nickel fine particles was defined as “best”.

[Measurement of oxygen content in sample after firing]
The paste produced in each example was applied on a glass substrate so that the film thickness was 200 μm or less, and fired under predetermined conditions. The amount of oxygen in 100 mg of the fired sample was determined as described above [quantitative determination of oxygen content]. Quantified in the same manner.

[Quantification of residual carbon content in the sample after firing]
The paste prepared in each example was applied on a glass substrate so that the film thickness was 200 μm or less, fired under predetermined conditions, and the carbon amount residue in 100 mg of the fired sample was burned-infrared absorbing device ( It was measured by the product made by LECO, brand name; CS-444).

[Baking method]
The sinterability test sample was fired as follows.
I) Firing in a mixed gas atmosphere of 3% hydrogen and 97% nitrogen uses a small inert gas oven (trade name: KLO-30NH, manufactured by Koyo Thermo Systems Co., Ltd.) at a temperature increase rate of 5 ° C./min. The temperature was raised from 1 to a predetermined temperature, and then kept at this predetermined temperature for 1 hour. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then left to room temperature.
II) For firing in a 100% nitrogen atmosphere, a small inert gas oven (manufactured by Koyo Thermo System Co., Ltd., trade name: KLO-30NH) was used, and the temperature was raised from room temperature to a predetermined temperature at a temperature rising rate of 5 ° C./min. Then, it was kept at this predetermined temperature for 1 hour. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then left to room temperature.
III) For firing in a mixed gas atmosphere of 3% formic acid and 97% nitrogen, a desktop small vacuum solder reflow apparatus (manufactured by UniTemp, trade name: RSS-350-160) is used, and the heating rate is 16 ° C. / In minutes, the temperature was raised from room temperature to 350 ° C., and then held at 350 ° C. for 1 hour. Next, the temperature was lowered to 50 ° C. over 60 minutes, and then left to room temperature.
IV) For firing in the air, a small inert gas oven (manufactured by Koyo Thermo Systems Co., Ltd., trade name: KLO-30NH) is used, and the temperature is raised from room temperature to a predetermined temperature at a heating rate of 5 ° C./min. It was kept at a predetermined temperature for 1 hour. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then left to room temperature.

[Evaluation of shear strength (shear strength)]
Method 1) Using a stainless steel mask (mask width: 1.0 mm × length; 1.0 mm × thickness: 0.05 to 0.1 mm), the sample was gold-plated copper substrate (width: 10 mm × length; A coating film is formed by coating on 10 mm × thickness: 1.0 mm), and then a silicon die (width: 1.0 mm × length: 1.0 mm × thickness: 0.75 mm) is formed on the coating film. ). Then, it was left to stand at room temperature for 30 minutes, and sandwiched and fired between clips (pressure strength; 2.5 MPa to 5 MPa). The shear strength of the obtained joining sample (thickness of the joining layer; about 10 to 30 μm) was measured with a joining strength tester (manufactured by Daisy Japan, trade name: Bond Tester 4000). A bond tester tool was pressed from the side of the die at a height of 50 μm from the substrate and a tool speed of 100 μm / second, and the load when the joint was sheared was determined as shear strength (shear strength). The gold-plated copper substrate is obtained by plating Ni / Au with a thickness of 4 μm / 40 to 50 nm on the surface of a Cu substrate (thickness: 1.0 mm), and the silicon die is a Si substrate (thickness). 0.75 mm), Au is deposited in a thickness of 15 to 20 nm on the joint surface.
Method 2) Same as Method 1 except that a silicon die is used instead of the gold-plated copper substrate in Method 1.

(Synthesis Example 1)
To 642 parts by weight of oleylamine, 100.1 parts by weight of nickel acetate tetrahydrate was added and heated at 150 ° C. for 20 minutes under a nitrogen flow to dissolve nickel acetate to obtain a complexing reaction solution. Next, 492 parts by weight of oleylamine was added to the complexing reaction solution, and the mixture was heated at 250 ° C. for 5 minutes using a microwave to obtain a nickel fine particle slurry.

  The nickel fine particle slurry was allowed to stand and separated, the supernatant was removed, washed with toluene and methanol, and then dried in a vacuum dryer maintained at 60 ° C. for 6 hours to obtain nickel fine particles (average particle size; 92 nm, CV value; 0.19) was obtained. As a result of elemental analysis of the nickel fine particles, C: 0.9, N <0.1, O: 1.4 (unit: mass%).

(Production Example 1)
The nickel fine particle slurry obtained in Synthesis Example 1 was allowed to stand and separated, the supernatant was removed, washed with toluene and isopropanol, and then used with a high-pressure homogenizer (trade name: Starburst manufactured by Sugino Machine Co., Ltd.). Thus, a slurry solution (solid content concentration 68.4 wt%) in which nickel fine particles were dispersed in isopropanol under a pressure of 200 MPa was prepared. As a result of measuring the particle size distribution of the slurry solution, the volume distribution was D50; 0.30, D90; 0.55, D99; 1.01 (unit: μm).

(Production Example 2)
The nickel fine particle slurry obtained in Synthesis Example 1 was allowed to stand and separated, the supernatant was removed, washed with toluene and isopropanol, and then used with a high-pressure homogenizer (trade name: Starburst manufactured by Sugino Machine Co., Ltd.). Thus, a slurry solution (solid content concentration: 72.3 wt%) in which nickel fine particles were dispersed in isopropanol under a pressure of 100 MPa was prepared. As a result of measuring the particle size distribution of the slurry solution, the volume distribution was D50; 0.55, D90; 1.00, D99; 2.27 (unit: μm).

(Production Example 3)
The nickel fine particle slurry obtained in Synthesis Example 1 was allowed to stand and separated, the supernatant was removed, washed with toluene and isopropanol, and then used with a high-pressure homogenizer (trade name: Starburst manufactured by Sugino Machine Co., Ltd.). Thus, a slurry solution (solid content concentration: 70.5 wt%) in which nickel fine particles were dispersed in isopropanol under a pressure of 150 MPa was prepared. As a result of measuring the particle size distribution of this slurry solution, the volume distribution was D50; 0.44, D90; 0.82, D99; 1.73 (unit: μm).

Example 1
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, and 2 parts by weight of di-p-toluoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and slurry solution 1 ( A solid content concentration of 76.8 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 1, the volume distribution was D50; 0.11, D90; 0.22, D99; 0.48 (unit: μm).

The slurry solution 1 was dried for 2 hours with a vacuum dryer maintained at 80 ° C. to obtain nickel fine particles 1 (average particle size: 92 nm, CV value: 0.19). The nickel content in the nickel fine particles 1 was 97.0 wt%. Further, from the chart obtained by X-ray photoelectron spectroscopy (XPS), the area ratios derived from the peaks of Ni, NiO, and Ni (OH) ₂ were 27.3%, 66.4%, and 6.3%, respectively. there were.

<Preparation of paste>
250 parts by weight of the slurry solution 1 is taken, 33.2 parts by weight of 1-octanol (boiling point: 195 ° C.) is mixed with the slurry solution, concentrated at 60 ° C. and 100 hPa in an evaporator, and 172 parts by weight of paste. 1 (solid content concentration 75.4 wt%) was prepared. With respect to 100 parts by weight of the nickel fine particles contained in paste 1, nickel hydroxide is 3.44 parts by weight, nickel oxide is 3.02 parts by weight, and di-p-toluoyl-L-tartaric acid is 0.72 parts by weight. there were.

<Baking process>
A sample for sinterability test was prepared using the paste 1 by the above method, and the sample was held at a heating temperature of 350 ° C. for 1 hour in a mixed gas atmosphere of 3% hydrogen and 97% nitrogen. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

An FE-SEM photograph of the sample after firing is shown in FIGS. 1A and 1B. 1A is an FE-SEM photograph at a magnification of 250,000, and FIG. 1B is an FE-SEM photograph at a magnification of 500,000. From FIG. 1A and FIG. 1B, it is confirmed that there are nickel fine particles in which no particle interface is confirmed, and that the sintering of the nickel fine particles proceeds well. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1 and the method 2, and the shear strength measured was 0.9 kgf / mm < ² > (method 1) and 2.5 kgf / mm < ² > (method 2), respectively. The results are shown in Table 1.

(Example 2)
<Preparation of paste>
Paste 1 (solid content concentration 75.4 wt%) prepared in Example 1 was collected and left in a sealed state at room temperature for 200 days to prepare paste 2 (solid content concentration 80.1 wt%). . With respect to 100 parts by weight of the nickel fine particles contained in Paste 2, 9.90 parts by weight of nickel hydroxide, 2.89 parts by weight of nickel oxide, and 0.69 parts by weight of di-p-toluoyl-L-tartaric acid there were.

<Baking process>
A sample for sinterability test was prepared using the paste 2 by the above method, and the sample was held at a heating temperature of 350 ° C. for 1 hour in a mixed gas atmosphere of 3% hydrogen and 97% nitrogen. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

The FE-SEM photograph of the sample after firing is shown in FIGS. 2A and 2B. 2A is an FE-SEM photograph at a magnification of 250,000, and FIG. 2B is an FE-SEM photograph at a magnification of 500,000. From FIG. 2A and FIG. 2B, it is confirmed that there are nickel fine particles in which the particle interface is not confirmed at all, and that the sintering of the nickel fine particles proceeds well. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. The calcined sample had an oxygen content of 0.93% by weight. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 1.9 kgf / mm < ² >. The results are shown in Table 1.

(Example 3)
A sample after firing was obtained in the same manner as in Example 2 except that the heating temperature in the firing step was 400 ° C. The FE-SEM photograph of the sample after firing is shown in FIGS. 3A and 3B. 3A is an FE-SEM photograph at a magnification of 250,000, and FIG. 3B is an FE-SEM photograph at a magnification of 500,000. From FIG. 3A and FIG. 3B, the particle interface is not confirmed at all in all of the nickel fine particles, and it is confirmed that the sintering of the nickel fine particles proceeds better than in Example 2. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. The oxygen content and carbon content of the sample after firing were 0.53% by weight and 0.30% by weight, respectively. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 2.1 kgf / mm < ² >. The results are shown in Table 1.

Example 4
A sample after firing was obtained in the same manner as in Example 2 except that the heating temperature was 450 ° C. The FE-SEM photograph of the sample after firing is shown in FIGS. 4A and 4B. 4A is an FE-SEM photograph at a magnification of 250,000, and FIG. 4B is an FE-SEM photograph at a magnification of 500,000. From FIG. 4A and FIG. 4B, in all the nickel fine particles, the particle interface was not confirmed at all, and it was confirmed that the sintering of the nickel fine particles proceeded best as compared with Example 2 and Example 3. The The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. The oxygen content and carbon content of the calcined sample were 0.10 wt% and 0.17 wt%, respectively. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 2.6 kgf / mm < ² >. The results are shown in Table 1.

(Example 5)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, 2 parts by weight of dibenzoyl-D-tartaric acid was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 2 (solid content concentration 77 .4 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 2, the volume distribution was D50; 0.15, D90; 0.29, D99; 0.58 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 2 was collected, and 33.2 parts by weight of 1-octanol was mixed therewith, and concentrated at 60 ° C. and 100 hPa in an evaporator to give 172 parts by weight of paste 3 (solid content concentration 75 .8 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 3 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.9 kgf / mm < ² >. The results are shown in Table 1.

(Example 6)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, and 2 parts by weight of di-p-anisoyl-D-tartaric acid was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 3 ( A solid content concentration of 78.0 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 3, the volume distribution was D50; 0.20, D90; 0.37, D99; 0.67 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 3 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa in an evaporator, and 172 parts by weight of paste 4 (solid content concentration 76 0.0 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 4 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.7 kgf / mm < ² >. The results are shown in Table 1.

(Example 7)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, 2 parts by weight of D-isopropyl D-tartrate was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 4 (solid content concentration 73. 6 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 4, the volume distribution was D50; 0.11, D90; 0.23, D99; 0.51 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 4 was collected, and 33.2 parts by weight of 1-octanol was mixed therewith, and concentrated at 60 ° C. and 100 hPa in an evaporator to give 172 parts by weight of paste 5 (solid content concentration 75 .9 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 5 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.9 kgf / mm < ² >. The results are shown in Table 1.

(Example 8)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, 2 parts by weight of di-t-butyl malonate was added thereto, stirred for 15 minutes, then washed with isopropanol, and the slurry solution 5 (solid content (Concentration 77.1 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 5, the volume distribution was D50; 0.14, D90; 0.25, D99; 0.51 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 5 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa in an evaporator, and 172 parts by weight of paste 6 (solid content concentration 75). .6 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 6 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.8 kgf / mm < ² >. The results are shown in Table 1.

Example 9
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, and 2 parts by weight of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TMPD) was added thereto and stirred for 15 minutes. Thereafter, it was washed with isopropanol to prepare slurry solution 6 (solid content concentration 76.8 wt%). As a result of measuring the particle size distribution of the slurry solution 6, the volume distribution was D50; 0.24, D90; 0.42, D99; 0.77 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 6 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa in an evaporator, and 172 parts by weight of paste 7 (solid content concentration 75). .8 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 7 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.6 kgf / mm < ² >. The results are shown in Table 1.

(Example 10)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, and 2 parts by weight of tributyl O-acetylcitrate was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 7 (solid content concentration). 76.1 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 7, the volume distribution was D50; 0.20, D90; 0.39, D99; 0.89 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 7 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa with an evaporator, and 172 parts by weight of paste 8 (solid content concentration 75). .4 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 8 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.8 kgf / mm < ² >. The results are shown in Table 1.

(Example 11)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 2 was collected, 2 parts by weight of phenylmalonic acid was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 8 (solid content concentration 78.7 wt. %) Was prepared. As a result of measuring the particle size distribution of the slurry solution 8, the volume distribution was D50; 0.19, D90; 0.38, D99; 0.88 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 8 was collected, 33.2 parts by weight of 1-octanol was mixed with the slurry solution, concentrated at 60 ° C. and 100 hPa in an evaporator, and 172 parts by weight of paste 9 (solid content concentration 75). 0.5 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 9 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.7 kgf / mm < ² >. The results are shown in Table 2.

(Example 12)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 2 was collected, 2 parts by weight of triethyl citrate was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 9 (solid content concentration: 77.2 wt. %) Was prepared. As a result of measuring the particle size distribution of the slurry solution 9, the volume distribution was D50; 0.23, D90; 0.46, D99; 1.01 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 9 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa in an evaporator to give 172 parts by weight of paste 10 (solid content concentration 76 0.0 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 10 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.6 kgf / mm < ² >. The results are shown in Table 2.

(Example 13)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 2 was collected, 2 parts by weight of tributyl citrate was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 10 (solid content concentration: 73.9 wt. %) Was prepared. As a result of measuring the particle size distribution of the slurry solution 10, the volume distribution was D50; 0.15, D90; 0.31, D99; 0.77 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 10 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa in an evaporator, and 172 parts by weight of paste 11 (solid content concentration 75). 0.1 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 11 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.7 kgf / mm < ² >. The results are shown in Table 2.

(Example 14)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 3 was collected, and 2 parts by weight of monobenzyl phenylmalonate was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 11 (solid content concentration 76 0.5 wt%) was prepared. As a result of measuring the particle size distribution of the slurry solution 11, the volume distribution was D50; 0.21, D90; 0.44, D99; 1.01 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 11 is collected, 33.2 parts by weight of 1-octanol is mixed with this, and concentrated at 60 ° C. and 100 hPa with an evaporator, and 172 parts by weight of paste 12 (solid content concentration 75). .7 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 12 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.5 kgf / mm < ² >. The results are shown in Table 2.

(Example 15)
<Preparation of slurry solution>
100 parts by weight of the slurry solution prepared in Preparation Example 3 was collected, 2 parts by weight of dibenzyl malonate was added thereto, stirred for 15 minutes, and then washed with isopropanol to obtain slurry solution 12 (solid content concentration 76.9 wt. %) Was prepared. As a result of measuring the particle size distribution of the slurry solution 12, the volume distribution was D50; 0.20, D90; 0.57, D99; 1.01 (unit: μm).

<Preparation of paste>
250 parts by weight of the slurry solution 12 was collected, 33.2 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C. and 100 hPa with an evaporator, and 172 parts by weight of paste 13 (solid content concentration 75). .7 wt%) was prepared.

<Baking process>
A sample after firing was obtained in the same manner as in Example 1 except that the paste 13 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.6 kgf / mm < ² >. The results are shown in Table 2.

(Example 16)
<Preparation of paste>
In Production Example 1, 252 parts by weight of the slurry solution was fractionated, 35.9 parts by weight of 1-octanol was mixed with this, and concentrated at 60 ° C./100 hPa with an evaporator to obtain 241 parts by weight of paste 14 (solid A partial concentration of 86.3 wt%) was prepared.

<Baking process>
A sample for a sinterability test was prepared by the above method using the paste 14, and held at a heating temperature of 350 ° C. for 1 hour in a mixed gas atmosphere of 3% hydrogen and 97% nitrogen. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

The FE-SEM photograph of the sample after firing is shown in FIGS. 5A and 5B. 5A is an FE-SEM photograph at a magnification of 250,000, and FIG. 5B is an FE-SEM photograph at a magnification of 500,000. From FIG. 5A and FIG. 5B, it is confirmed that there are nickel fine particles in which the particle interface between the nickel fine particles is not completely confirmed, and that the sintering of the nickel fine particles proceeds well. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.4 kgf / mm < ² >. The results are shown in Table 2.

(Reference Example 1)
A sample for sinterability test was prepared by the above method using the paste 2 prepared in Example 2, and held at a heating temperature of 70 ° C. for 16 hours in a mixed gas atmosphere of 100% nitrogen. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

The FE-SEM photograph of the sample after firing is shown in FIGS. 6A and 6B. 6A is an FE-SEM photograph at a magnification of 250,000, and FIG. 6B is an FE-SEM photograph at a magnification of 500,000. From FIG. 6A and FIG. 6B, it is confirmed that the sintering of the nickel fine particles has hardly progressed. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. The oxygen content of the sample after firing was 1.24% by weight. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0 kgf / mm < ² >. The results are shown in Table 2.

(Reference Example 2)
A sample after firing was obtained in the same manner as in Reference Example 1 except that the heating temperature in the firing step was 400 ° C. The FE-SEM photograph of the sample after firing is shown in FIGS. 7A and 7B. 7A is an FE-SEM photograph at a magnification of 250,000, and FIG. 7B is an FE-SEM photograph at a magnification of 500,000. From FIG. 7A and FIG. 7B, it is confirmed that the sintering of the nickel fine particles has hardly progressed. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. The oxygen content and carbon content of the sample after firing were 0.95% by weight and 0.60% by weight, respectively. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0 kgf / mm < ² >. The results are shown in Table 2.

(Reference Example 3)
A sample for sinterability test was prepared by the above method using the paste 2 prepared in Example 2, and held at a heating temperature of 350 ° C. for 1 hour in a mixed gas atmosphere of 3% formic acid and 97% nitrogen. Next, the temperature was lowered to 50 ° C. over 60 minutes, and then allowed to stand at room temperature to obtain a baked sample.

The FE-SEM photograph of the sample after firing is shown in FIGS. 8A and 8B. 8A is an FE-SEM photograph at a magnification of 250,000, and FIG. 8B is an FE-SEM photograph at a magnification of 500,000. 8A and 8B, although the nickel fine particles are being sintered, the particle interface is partially confirmed in each nickel fine particle. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.2 kgf / mm < ² >. The results are shown in Table 2.

(Reference Example 4)
A sample for sinterability test was prepared by the above method using the paste 2 prepared in Example 2, and the sample was held at a heating temperature of 350 ° C. for 1 hour in the air. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

The FE-SEM photograph of the sample after firing is shown in FIGS. 9A and 9B. 9A is an FE-SEM photograph at a magnification of 250,000, and FIG. 9B is an FE-SEM photograph at a magnification of 500,000. 9A and 9B, although the nickel fine particles are being sintered, the particle interface is partially confirmed in each nickel fine particle.
When the presence or absence of electrical continuity in the sample after firing was examined with a two-terminal tester, continuity could not be confirmed. Moreover, the joining sample was produced by the said method 1, and the shear strength measured was 0.8 kgf / mm < ² >. The results are shown in Table 2.

  The above results are summarized in Table 1 and Table 2. In addition, the shear strength in Tables 1 and 2 is a value measured by Method 1.

(Example 17)
<Preparation of slurry solution>
5 parts by weight of the slurry solution prepared in Preparation Example 1 was collected, 25 parts by weight of a 25% aqueous ammonia solution was added thereto, subjected to 28 kHz ultrasonic treatment for 30 minutes, and then washed with isopropanol. Next, 25 parts by weight of propionic acid was added, and 28 kHz ultrasonic treatment was performed for 30 minutes, followed by washing with isopropanol to obtain a slurry solution 13 ′ (solid content concentration 61 wt%). Further, 2 parts by weight of di-p-toluoyl-L-tartaric acid was added to 100 parts by weight of the slurry solution 13 ′, stirred for 15 minutes, washed with isopropanol, and the slurry solution 13 (solid content concentration 78.78). 0 wt%) was obtained.

The slurry solution 13 was dried for 2 hours with a vacuum dryer maintained at 80 ° C. to obtain nickel fine particles 13. The nickel content in the nickel fine particles 13 was 97.3 wt%. From the chart obtained by X-ray photoelectron spectroscopy (XPS), the area ratios derived from the peaks of Ni, NiO, and Ni (OH) ₂ are 59.7%, 39.7%, and 0.6%, respectively. there were.

<Preparation of paste>
255 parts by weight of the slurry solution 13 was collected, 51.8 parts by weight of 1-octanol was mixed with this, and concentrated by an evaporator at 60 ° C. and 100 hPa, and 150 parts by weight of paste 15 (solid content concentration 78 0.5 wt%) was prepared.

<Baking process>

  A sample after firing was obtained in the same manner as in Example 1 except that the paste 15 was used.

In the sample after firing, it was confirmed by observation with FE-SEM that there were nickel fine particles in which no particle interface was confirmed, and that the nickel fine particles were satisfactorily sintered. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 2, and the shear strength measured was 2.4 kgf / mm < ² >.

(Reference Example 5)
A sample for a sinterability test was prepared by the above method using the paste 15 prepared in Example 17, and the sample was held at a heating temperature of 70 ° C. for 16 hours in a mixed gas atmosphere of 100% nitrogen. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

As for the sample after baking, it was confirmed by the observation by FE-SEM that the sintering of nickel fine particles has hardly progressed. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 2, and the shear strength measured was 0.7 kgf / mm < ² >.

(Reference Example 6)
A sample for sinterability test was prepared by the above method using the paste 1 prepared in Example 1, and the sample was held at a heating temperature of 70 ° C. for 16 hours in a mixed gas atmosphere of 100% nitrogen. Next, the temperature was lowered to 50 ° C. over 400 minutes, and then allowed to stand at room temperature to obtain a baked sample.

As for the sample after baking, it was confirmed by the observation by FE-SEM that the sintering of nickel fine particles has hardly progressed. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 2, and the shear strength measured was 2.5 kgf / mm < ² >.

(Reference Example 7)
100 parts by weight of the nickel fine particle slurry prepared in Synthesis Example 1 was collected, 2 parts by weight of di-p-toluoyl-L-tartaric acid was added thereto, and the mixture was stirred for 15 minutes and then washed with isopropanol. After the preparation, 1-octanol was mixed and concentrated by an evaporator at 60 ° C. and 100 hPa to prepare a paste 16.

  A sample after firing was obtained in the same manner as in Example 1 except that the paste 16 was used.

As for the sample after baking, it was confirmed by the observation by FE-SEM that the sintering of nickel fine particles has hardly progressed. The presence or absence of electrical conduction in the sample after firing was examined with a two-terminal tester, and conduction was confirmed. Moreover, the joining sample was produced by the said method 2, and the shear strength measured was 1.1 kgf / mm < ² >.

As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment.

Claims (4)

It is a joining method for joining members to be joined by firing a joining material containing metal fine particles interposed between the members to be joined,
The metal fine particles are preliminarily crushed in an organic solvent using a wet pulverizer,
A bonding method in which the firing is performed by heating to a temperature in the range of 320 to 480 ° C. in a reducing atmosphere containing hydrogen gas.   The metal fine particles contain 90% by weight or more of metal element and 1 to 35% by weight of metal hydroxide, and contain 50 parts by weight or more of nickel element with respect to 100 parts by weight of all metal elements. The joining method according to claim 1.   The average particle diameter of primary particles of the metal fine particles is in the range of 50 to 150 nm, and the coefficient of variation (standard deviation / average particle diameter) of the particle diameter of the metal fine particles is 0.3 or less. 2. The joining method according to 2. The joining method according to any one of claims 1 to 3, wherein the metal fine particles are coated with an ester compound having a molecular weight in the range of 100 to 500 after the crushing treatment.