JP7394257B1 - metal particles - Google Patents
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- 239000002923 metal particle Substances 0.000 title claims abstract description 81
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 229910020888 Sn-Cu Inorganic materials 0.000 claims description 7
- 229910019204 Sn—Cu Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 43
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 34
- 238000007747 plating Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 17
- 238000009713 electroplating Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- -1 brighteners Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 239000007791 liquid phase Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
【課題】極高温ないし極低温環境の過酷な温度変動に対しても、金属間化合物の脆さを克服して優れた接合強度および機械的強度を維持できる金属粒子を提供する。【解決手段】Ｓｎと、Ｓｎ－Ｃｕ合金と、を含む母相中に、Ｓｎ、Ｃｕ、Ｎｉ、ＡｌおよびＣｒを含む金属間化合物結晶を有し、前記金属粒子の組成が、Ｃｕ ０．７～１５質量％、Ｎｉ 1～０.０２質量％、Ａｌ ３～０.０２質量％、Ｃｒ ２～０.０２質量％、残部がＳｎであり、前記母相の組成が、Ｓｎ ９２～９９．９質量％、Ｃｕ ５質量％以下、Ｎｉ １質量％以下、Ａｌ ３質量％以下であり、前記金属間化合物の組成が、Ｃｕ ５～５０質量％、Ｎｉ ６.５～０.１質量％、Ａｌ ２０～０．５質量％、Ｃｒ ０．００１～０．１質量％、残部がＳｎである金属粒子によって上記課題を解決した。【選択図】図４ＢThe present invention provides metal particles that can overcome the brittleness of intermetallic compounds and maintain excellent bonding strength and mechanical strength even under severe temperature fluctuations in extremely high-temperature or extremely low-temperature environments. The present invention has an intermetallic compound crystal containing Sn, Cu, Ni, Al, and Cr in a matrix containing Sn and a Sn--Cu alloy, and the composition of the metal particles is Cu 0.7. -15% by mass, Ni 1-0.02% by mass, Al 3-0.02% by mass, Cr 2-0.02% by mass, the balance being Sn, and the composition of the parent phase is Sn 92-99. 9% by mass, Cu 5% by mass or less, Ni 1% by mass or less, Al 3% by mass or less, and the composition of the intermetallic compound is Cu 5-50% by mass, Ni 6.5-0.1% by mass, The above problem was solved by metal particles containing 20 to 0.5% by mass of Al, 0.001 to 0.1% by mass of Cr, and the balance being Sn. [Selection diagram] Figure 4B
Description
本発明は、金属粒子に関する。 The present invention relates to metal particles.
ＩｏＴ（Internet of Things）の進展や、一層の省エネルギーが求められる中で、その技術の核心を担うパワー半導体の重要性が益々高まっている。しかしながら、その活用には多くの課題がある。パワー半導体は、高電圧、大電流の大きな電力を扱うことと超高速伝送から、多くの熱を発して高温となる。現行のＳｉパワー半導体に求められる耐熱性は約１７５℃程度への対応であるが、約２００℃の温度に耐えるＳｉパワー半導体の開発が進められており、また、ＳｉＣやＧａＮのような次世代のパワー半導体は高速通信伝送にはデバイスの表裏面に金を使用し伝送特性を維持し、極高温耐熱性２５０～５００℃に耐えることが要求される。 With the advancement of the Internet of Things (IoT) and the need for further energy conservation, the importance of power semiconductors, which play the core of this technology, is increasing. However, there are many challenges to its utilization. Power semiconductors generate a lot of heat and reach high temperatures because they handle large amounts of power at high voltages and currents, and because of ultra-high-speed transmission. The heat resistance required for current Si power semiconductors is about 175°C, but the development of Si power semiconductors that can withstand temperatures of about 200°C is progressing, and next-generation Si power semiconductors such as SiC and GaN are being developed. For high-speed communication transmission, power semiconductors are required to use gold on the front and back surfaces of the device to maintain transmission characteristics, and to withstand extremely high temperatures of 250 to 500 degrees Celsius.
一方、接合材に関して言えば、上述のようなＳｉＣやＧａＮのような次世代のパワー半導体に求められる高い耐熱性を有する接合材は存在しない。
例えば、特許文献１に開示されているＳｎＡｇＣｕ系接合材（粉末はんだ材料）では、約１２５℃程度に対応したパワー半導体に適用可能であるに過ぎず、次世代のパワー半導体に適用することができない。
また従来のハンダ接合材では、アルミニウムに対し接合することができないという課題がある。
On the other hand, with regard to bonding materials, there is no bonding material that has the high heat resistance required for next-generation power semiconductors such as SiC and GaN as described above.
For example, the SnAgCu-based bonding material (powder solder material) disclosed in Patent Document 1 is only applicable to power semiconductors that can handle temperatures of about 125°C, and cannot be applied to next-generation power semiconductors. .
Another problem with conventional solder bonding materials is that they cannot be bonded to aluminum.
一方、本出願人は特許文献２において、外殻と、コア部とからなり、前記コア部は、金属又は合金を含み、前記外殻は、金属間化合物の網目状から成り、前記コア部を覆っており、前記コア部は、Ｓｎ又はＳｎ合金を含み、前記外殻は、ＳｎとＣｕとの金属間化合物を含む、金属粒子を提案している。この金属粒子により形成された接合部は、長時間にわたって高温動作状態が継続した場合でも、また、高温動作状態から低温停止状態へと大きな温度変動を伴うなど、過酷な環境下で使用された場合でも、長期にわたって高い耐熱性、接合強度及び機械的強度を維持することができる。
しかし、金属間化合物は脆いという弱点があり、この問題点を解決すれば、更に高い耐熱性、接合強度及び機械的強度を有する接合材を提供できることになる。
On the other hand, in Patent Document 2, the present applicant has disclosed that the core part is composed of an outer shell and a core part, the core part contains a metal or an alloy, the outer shell is made of a mesh of an intermetallic compound, and the core part is Metal particles are proposed, the core portion comprising Sn or a Sn alloy, and the outer shell comprising an intermetallic compound of Sn and Cu. The joints formed by these metal particles can be used in harsh environments, such as when high-temperature operation continues for a long period of time, or when there are large temperature fluctuations from high-temperature operation to low-temperature shutdown. However, high heat resistance, bonding strength, and mechanical strength can be maintained over a long period of time.
However, intermetallic compounds have the disadvantage of being brittle, and if this problem is solved, it will be possible to provide a bonding material with even higher heat resistance, bonding strength, and mechanical strength.
そこで本出願人はさらに特許文献３において、ＳｎおよびＳｎ－Ｃｕ合金を含む母相中に、Ｓｎ、ＣｕおよびＮｉからなる金属間化合物を有し、前記母相におけるＳｎ－Ｃｕ合金および前記金属間化合物の少なくとも１部が、エンドタキシャル接合してなる金属粒子を提案した。しかし、２６０℃加熱雰囲気以上では、金属間化合物を囲っている母相が収縮し、エンドタキシャル接合の崩壊が起きボイドの発生を助長することが判明した。したがって、高温下での過酷な環境下で使用された場合、長期にわたって高い耐熱性、接合強度及び機械的強度を維持することができなくなる恐れがある。 Therefore, the present applicant has further disclosed in Patent Document 3 that an intermetallic compound consisting of Sn, Cu, and Ni is contained in a matrix containing Sn and a Sn-Cu alloy, and the Sn-Cu alloy in the matrix and the intermetallic compound are We have proposed metal particles in which at least a portion of the compound is endotaxially bonded. However, it has been found that in a heating atmosphere of 260° C. or higher, the matrix surrounding the intermetallic compound contracts, causing collapse of the endotaxial bond and promoting the generation of voids. Therefore, when used in a harsh environment at high temperatures, there is a risk that high heat resistance, bonding strength, and mechanical strength may not be maintained over a long period of time.
本発明の目的は、極高温ないし極低温環境の過酷な温度変動に対しても、金属間化合物の脆さを克服して優れた接合強度および機械的強度を維持できるとともに、アルミニウムに対し接合が可能な金属粒子を提供することにある。 The object of the present invention is to overcome the brittleness of intermetallic compounds and maintain excellent bonding strength and mechanical strength even under severe temperature fluctuations in extremely high-temperature or extremely low-temperature environments. The objective is to provide possible metal particles.
本発明は、Ｓｎと、Ｓｎ－Ｃｕ合金と、を含む母相中に、Ｓｎ、Ｃｕ、Ｎｉ、ＡｌおよびＣｒを含む金属間化合物結晶を有する、金属粒子であって、
前記金属粒子の組成が、
Ｃｕ ０．７～１５質量％、
Ｎｉ １～０.０２質量％、
Ａｌ ３～０.０２質量％、
Ｃｒ ２～０.０２質量％、
残部がＳｎであり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記母相の組成が、
Ｓｎ ９２～９９．９質量％、
Ｃｕ ５質量％以下、
Ｎｉ １質量％以下、
Ａｌ ３質量％以下であり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記金属間化合物の組成が、
Ｃｕ ５～５０質量％、
Ｎｉ ６.５～０.１質量％、
Ａｌ ２０～０．５質量％、
Ｃｒ ０．００１～０．１質量％、
残部がＳｎであり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記母相中に前記金属間化合物結晶が包含されて存在する、
ことを特徴とする金属粒子を提供するものである。
また本発明は、前記１に記載の金属粒子からなる固結体を提供するものである。
The present invention provides metal particles having intermetallic compound crystals containing Sn, Cu, Ni, Al, and Cr in a matrix containing Sn and a Sn-Cu alloy,
The composition of the metal particles is
Cu 0.7-15% by mass,
Ni 1-0.02% by mass,
Al 3-0.02% by mass,
Cr 2-0.02% by mass,
The remainder is Sn (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The composition of the matrix is
Sn 92-99.9% by mass,
Cu 5% by mass or less,
Ni 1% by mass or less,
Al is 3% by mass or less (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The composition of the intermetallic compound is
Cu 5-50% by mass,
Ni 6.5-0.1% by mass,
Al 20-0.5% by mass,
Cr 0.001-0.1% by mass,
The remainder is Sn (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The intermetallic compound crystal is included in the matrix,
The present invention provides metal particles characterized by the following.
The present invention also provides a solidified body made of the metal particles described in 1 above.
本発明によれば、極高温ないし極低温環境の過酷な温度変動に対しても、金属間化合物の脆さを克服して優れた接合強度および機械的強度を維持できるとともに、アルミニウムに対し接合が可能な金属粒子及び固結体を提供することができる。
本発明者らは鋭意検討を行ったところ、本発明の金属粒子は、Ｃｕ、Ｎｉ、Ａｌ、Ｃｒおよび残部がＳｎからなる組成の原材料を下記条件の製造方法に基づき製造することにより、ＳｎとＳｎ－Ｃｕ合金とを含む母相中に、Ｓｎ、Ｃｕ、Ｎｉ、ＡｌおよびＣｒを含む金属間化合物結晶を包含するという特徴的な構造を有することになる。この金属粒子およびこれを固結してなる固結体は、金属の固相、液相温度の調整が可能になり、また金属間化合物結晶にＡｌが存在することによって、従来は不可とされていたＡｌおよび他の金属間の接合を可能にするとともに、上述の金属間化合物は脆さに起因する課題を解決でき、優れた接合強度および機械的強度を維持できる。
According to the present invention, it is possible to overcome the brittleness of intermetallic compounds and maintain excellent bonding strength and mechanical strength even under severe temperature fluctuations in extremely high-temperature or extremely low-temperature environments. Possible metal particles and concretions can be provided.
The present inventors conducted extensive studies and found that the metal particles of the present invention can be produced by manufacturing raw materials having a composition consisting of Cu, Ni, Al, Cr, and the remainder Sn according to the manufacturing method under the following conditions. It has a characteristic structure in which intermetallic compound crystals containing Sn, Cu, Ni, Al, and Cr are included in a parent phase containing Sn--Cu alloy. These metal particles and the solidified bodies formed by solidifying them enable adjustment of the solid phase and liquid phase temperatures of the metal, and the presence of Al in the intermetallic compound crystals makes it possible to adjust the solid phase and liquid phase temperatures of the metal, which was previously considered impossible. In addition to enabling bonding between Al and other metals, the above-mentioned intermetallic compounds can solve problems caused by brittleness and maintain excellent bonding strength and mechanical strength.
以下、本発明をさらに詳しく説明する。
先に、本明細書における用語法は、特に説明がない場合であっても、以下による。
（１）金属というときは、金属元素単体のみならず、複数の金属元素を含む合金、金属間化合物を含むことがある。
（２）ある単体の金属元素に言及する場合、完全に純粋に当該金属元素のみからなる物質だけを意味するものではなく、微かな他の物質を含む場合もあわせて意味する。すなわち、当該金属元素の性質にほとんど影響を与えない微量の不純物を含むものを除外する意味ではないことは勿論、たとえば、母相という場合、Ｓｎの結晶中の原子の一部が他の元素（たとえば、Ｃｕ）に置き換わっているものを除外する意味ではない。例えば、前記他の物質または他の元素は、金属粒子中、０～０．１質量％含まれる場合がある。
The present invention will be explained in more detail below.
First, the terminology used in this specification is as follows even if there is no particular explanation.
(1) The term metal may include not only a single metal element, but also an alloy containing multiple metal elements and an intermetallic compound.
(2) When we refer to a single metal element, we do not mean only a substance that is completely pure only of the metal element, but also mean a substance that contains trace amounts of other substances. That is, of course, this does not mean to exclude those containing minute amounts of impurities that have little effect on the properties of the metal element. For example, when we say the parent phase, some of the atoms in the Sn crystal are mixed with other elements ( For example, this does not mean excluding those replaced with Cu). For example, the other substance or other element may be contained in the metal particles in an amount of 0 to 0.1% by mass.
本発明の金属粒子およびこれを用いた固結体は、Ｓｎと、Ｓｎ－Ｃｕ合金と、を含む母相中に、Ｓｎ、Ｃｕ、Ｎｉ、ＡｌおよびＣｒを含む金属間化合物結晶を有することを特徴とする。 The metal particles of the present invention and the solidified bodies using the same have intermetallic compound crystals containing Sn, Cu, Ni, Al, and Cr in a matrix containing Sn and a Sn-Cu alloy. Features.
図１は、下記実施例１で得られた本発明の金属粒子を用いて形成した固結体をFIB（集束イオンビーム）で薄くカッティングした断面のSTEM像である。図１の金属粒子からなる固結体を参照すると、該金属粒子は、ＳｎとＳｎ－Ｃｕ合金とを含む母相（淡色部分）に、Ｓｎ、Ｃｕ、Ｎｉ、ＡｌおよびＣｒを含む金属間化合物結晶（濃色部分）を有している。本発明の金属粒子の粒子径は、例えば好適には１μｍ～５０μｍの範囲であり、本発明の金属粒子からなる固結体は厚さが10mm以下である。 FIG. 1 is a STEM image of a cross section obtained by cutting a solid body formed using the metal particles of the present invention obtained in Example 1 below into a thin layer using a focused ion beam (FIB). Referring to the solid body made of metal particles in FIG. 1, the metal particles have an intermetallic compound containing Sn, Cu, Ni, Al, and Cr in a matrix (light colored part) containing Sn and a Sn-Cu alloy. It has crystals (dark colored parts). The particle diameter of the metal particles of the present invention is, for example, preferably in the range of 1 μm to 50 μm, and the thickness of the solid body made of the metal particles of the present invention is 10 mm or less.
本発明の金属粒子は、例えばその組成が、
Ｃｕ ０．７～１５質量％、
Ｎｉ １～０.０２質量％、
Ａｌ ３～０.０２質量％、
Ｃｒ ２～０.０２質量％、
残部がＳｎである。ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である。
The metal particles of the present invention have, for example, a composition of
Cu 0.7-15% by mass,
Ni 1-0.02% by mass,
Al 3-0.02% by mass,
Cr 2-0.02% by mass,
The remainder is Sn. However, when unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less.
本発明の金属粒子は、例えばＣｕ８質量％、Ｎｉ１質量％、Ａｌ１質量％、Ｃｒ１質量％および残部がＳｎからなる組成の原材料から製造することができる。例えば、該原材料を溶融し、これを窒素ガス雰囲気中で高速回転する皿形ディスク上に供給し、遠心力により該溶融金属を小滴として飛散させ、減圧下で冷却固化させることにより得られる。
また本発明の固結体（以下、バルクと言うことがある）は、本発明の金属粒子を１００℃～１９０℃に加熱された圧延回転ロールに直接挿入し加工することにより得ることができ、バルクの形状は例えばシート状であり、これを複数枚積層してもよい。
なお、バルク化を行っても、本発明の金属粒子の構造が維持されることを本発明者らは確認している。
The metal particles of the present invention can be manufactured from a raw material having a composition of, for example, 8% by mass of Cu, 1% by mass of Ni, 1% by mass of Al, 1% by mass of Cr, and the balance is Sn. For example, it can be obtained by melting the raw material, feeding it onto a dish-shaped disk rotating at high speed in a nitrogen gas atmosphere, scattering the molten metal as small droplets by centrifugal force, and cooling and solidifying it under reduced pressure.
Further, the solidified body of the present invention (hereinafter sometimes referred to as bulk) can be obtained by directly inserting the metal particles of the present invention into a rotating rolling roll heated to 100 ° C. to 190 ° C., and processing it. The shape of the bulk is, for example, a sheet, and a plurality of sheets may be stacked.
Note that the present inventors have confirmed that the structure of the metal particles of the present invention is maintained even when bulking is performed.
本発明の金属粒子の製造に好適な製造装置の一例を図２を参照して説明する。粒状化室１は上部が円筒状、下部がコーン状になっており、上部に蓋２を有する。蓋２の中心部には垂直にノズル３が挿入され、ノズル３の直下には皿形回転ディスク４が設けられている。符号５は皿形回転ディスク４を上下に移動可能に支持する機構である。また粒状化室１のコーン部分の下端には生成した粒子の排出管６が接続されている。ノズル３の上部は粒状化する金属を溶融する電気炉（高周波炉：従来はセラミックるつぼを使用したが、本発明ではカーボンるつぼを使用している）７に接続されている。混合ガスタンク８で所定の成分に調整された雰囲気ガスは配管９及び配管１０により粒状化室１内部及び電気炉７上部にそれぞれ供給される。粒状化室１内の圧力は弁１１及び排気装置１２、電気炉７内の圧力は弁１３及び排気装置１４によりそれぞれ制御される。ノズル３から皿形回転ディスク４上に供給された溶融金属は皿形回転ディスク４による遠心力で微細な液滴状になって飛散し、減圧下で冷却されて固体粒子になる。生成した固体粒子は排出管６から自動フィルター１５に供給され分別される。符号１６は微粒子回収装置である。 An example of a manufacturing apparatus suitable for manufacturing the metal particles of the present invention will be described with reference to FIG. 2. The granulation chamber 1 has a cylindrical upper part, a cone-shaped lower part, and a lid 2 on the upper part. A nozzle 3 is vertically inserted into the center of the lid 2, and a dish-shaped rotating disk 4 is provided directly below the nozzle 3. Reference numeral 5 denotes a mechanism that supports the dish-shaped rotating disk 4 so as to be movable up and down. Further, a discharge pipe 6 for the generated particles is connected to the lower end of the cone portion of the granulation chamber 1. The upper part of the nozzle 3 is connected to an electric furnace (high frequency furnace: conventionally a ceramic crucible was used, but in the present invention a carbon crucible is used) 7 for melting the metal to be granulated. The atmospheric gas adjusted to a predetermined composition in the mixed gas tank 8 is supplied to the inside of the granulation chamber 1 and the upper part of the electric furnace 7 through piping 9 and piping 10, respectively. The pressure inside the granulation chamber 1 is controlled by a valve 11 and an exhaust device 12, and the pressure inside the electric furnace 7 is controlled by a valve 13 and an exhaust device 14, respectively. The molten metal supplied from the nozzle 3 onto the dish-shaped rotating disk 4 is dispersed in the form of fine droplets due to the centrifugal force of the dish-shaped rotating disk 4, and is cooled under reduced pressure to become solid particles. The generated solid particles are supplied from the discharge pipe 6 to the automatic filter 15 and separated. Reference numeral 16 is a particle collection device.
溶融金属を高温溶解から冷却固化させる過程は、本発明の金属粒子を形成するために重要である。
例えば次のような条件が挙げられる。
溶解炉７における金属の溶融温度を６００℃～８００℃に設定し、その温度を保持したまま、ノズル３から皿型回転ディスク４上に溶融金属を供給する。
皿形回転ディスク４として、内径３５ｍｍ、回転体厚さ５ｍｍの皿形ディスクを用い、毎分８万～１０万回転とする。
粒状化室１として、９×１０-２Ｐａ程度まで減圧する性能を有する真空槽を使用して減圧した上で、１５～５０℃の窒素ガスを供給しつつ排気を同時に行って、粒状化室１内の気圧を１×１０－１Ｐａ以下とする。
The process of cooling and solidifying the molten metal from high-temperature melting is important for forming the metal particles of the present invention.
For example, the following conditions may be mentioned.
The melting temperature of the metal in the melting furnace 7 is set at 600° C. to 800° C., and the molten metal is supplied from the nozzle 3 onto the dish-shaped rotating disk 4 while maintaining that temperature.
As the dish-shaped rotating disc 4, a dish-shaped disc with an inner diameter of 35 mm and a rotating body thickness of 5 mm is used, and the rotation rate is 80,000 to 100,000 per minute.
As the granulation chamber 1, the pressure is reduced using a vacuum chamber capable of reducing the pressure to about 9×10 -2 Pa, and nitrogen gas at 15 to 50° C. is supplied and exhausted at the same time to complete the granulation chamber. The atmospheric pressure within the room shall be 1×10 −1 Pa or less.
また、本発明の金属粒子における母相の組成は、
Ｓｎ ９２～９９．９質量％、
Ｃｕ ５質量％以下（例えば０．０２～５質量％）、
Ｎｉ １質量％以下（例えば０．０２～１質量％）、
Ａｌ ３質量％以下（例えば０．０２～３質量％）であり、不可避不純物が存在する場合は、０．１質量％以下であることが好ましい。
Furthermore, the composition of the matrix in the metal particles of the present invention is as follows:
Sn 92-99.9% by mass,
Cu 5% by mass or less (for example, 0.02 to 5% by mass),
Ni 1% by mass or less (for example, 0.02 to 1% by mass),
Al is preferably 3% by mass or less (for example, 0.02 to 3% by mass), and if unavoidable impurities are present, it is preferably 0.1% by mass or less.
また、本発明の金属粒子における金属間化合物結晶の組成は、
Ｃｕ ５～５０質量％、
Ｎｉ ６.５～０.１質量％、
Ａｌ ２０～０．５質量％、
Ｃｒ ０．００１～０．１質量％、
残部がＳｎであることが好ましい。不可避不純物が存在する場合は、０．１質量％以下であることが好ましい。
また、本発明の金属粒子における金属間化合物の割合は、金属粒子全体に対し、例えば２０～６０質量％であり、３０～４０質量％が好ましい。
前記金属間化合物は、前記母相中に包含されて存在する。
Furthermore, the composition of the intermetallic compound crystal in the metal particles of the present invention is
Cu 5-50% by mass,
Ni 6.5-0.1% by mass,
Al 20-0.5% by mass,
Cr 0.001-0.1% by mass,
It is preferable that the remainder be Sn. When unavoidable impurities are present, the amount is preferably 0.1% by mass or less.
Further, the proportion of the intermetallic compound in the metal particles of the present invention is, for example, 20 to 60% by mass, preferably 30 to 40% by mass, based on the entire metal particle.
The intermetallic compound exists included in the parent phase.
前記母相および金属間化合物の組成および割合は、前記金属粒子の製造条件に従うことにより満たすことができる。 The composition and ratio of the matrix and the intermetallic compound can be satisfied by following the manufacturing conditions of the metal particles.
本発明の金属粒子を接合材として用い、Ａｌおよび他の金属間の接合を行う場合は、例えば次の方法（１）によって達成することができる。
（１）前記他の金属上に、本発明の金属粒子からなるめっき層を形成した後、Ａｌと前記めっき層との間を超音波印可する方法。
めっき層の形成方法は、例えば特許７３２３９７９号公報に記載の方法に従えばよいが、以下説明する。
前記他の金属（例えば銅、銅合金またはステンレス等）を基材とする。一方、本発明の金属粒子を用いて電解めっき用電極を作製し、前記基材の表面にめっき層を形成する。
前記電解めっき用電極は、可溶性電極であることができ、次の方法により製造することができる。
まず、本発明の金属粒子を製造する。続いて、得られた本発明の金属粒子を真空下、高周波誘導加熱することにより溶融させ、これを窒素ガス雰囲気中、大気圧下で鋳型鋳込みを行い、冷却固化させ、圧延シートとする。
前記高周波誘導加熱および冷却固化条件は、例えば次のような条件が挙げられる。
高周波誘導加熱：９×１０-２Ｐａ程度まで減圧可能な性能を有する真空槽内に高周波溶解用るつぼを設置し、該るつぼに本発明の金属粒子を導入し、前記減圧度程度まで減圧したまま本発明の金属粒子に対し高周波誘導加熱を行い、加熱温度を８００℃～１０００℃にして本発明の金属粒子を溶解させ、その温度を５分～１５分保持する。
冷却固化：続いて、１５～５０℃の窒素ガスを槽内に流しつつ、大気圧下で前記加熱温度を約４００℃以上に設定し、鋳型鋳込みを行い、３０℃以下で冷却固化させる。
電解めっき用電極の組成は、本発明の金属粒子と同じである。すなわち、上記のような前記電解めっき用電極の製造を行っても、本発明の金属粒子の構造および組成は同様に維持される。
続いて、前記電解めっき用電極を陽極とし、電解めっきを行うと、めっき浴中に電解めっき用電極に含まれる金属間化合物結晶がナノサイズ（１μｍ以下）で分散し、荷電を伴って母相とともに基材表面上にめっきされ、めっき層を形成する。形成されためっき層もまた、本発明の金属粒子と同じ構造および組成が維持される。
めっき浴には、本発明の金属粒子が含まれ、金属間化合物結晶がナノサイズ（１μｍ以下）で分散し、荷電を伴って母相とともに前記他の金属上にめっきされ、めっき層を形成する。形成されためっき層は、本発明の金属粒子と同じ組成を有する。
Bonding between Al and other metals using the metal particles of the present invention as a bonding material can be achieved, for example, by the following method (1).
(1) A method in which a plating layer made of the metal particles of the present invention is formed on the other metal, and then ultrasonic waves are applied between Al and the plating layer.
The method for forming the plating layer may be, for example, the method described in Japanese Patent No. 7323979, and will be explained below.
The other metal (for example, copper, copper alloy, stainless steel, etc.) is used as the base material. On the other hand, an electrode for electrolytic plating is produced using the metal particles of the present invention, and a plating layer is formed on the surface of the base material.
The electrolytic plating electrode can be a soluble electrode, and can be manufactured by the following method.
First, the metal particles of the present invention are manufactured. Subsequently, the obtained metal particles of the present invention are melted by high-frequency induction heating under vacuum, cast into a mold under atmospheric pressure in a nitrogen gas atmosphere, and cooled and solidified to form a rolled sheet.
Examples of the high frequency induction heating and cooling solidification conditions include the following conditions.
High-frequency induction heating: A crucible for high-frequency melting is installed in a vacuum chamber capable of reducing the pressure to about 9 × 10 -2 Pa, the metal particles of the present invention are introduced into the crucible, and the pressure is reduced to about the above degree of pressure reduction. The metal particles of the present invention are subjected to high-frequency induction heating to a heating temperature of 800° C. to 1000° C. to dissolve the metal particles of the present invention, and the temperature is maintained for 5 minutes to 15 minutes.
Cooling and solidification: Next, while flowing nitrogen gas at 15 to 50°C into the tank, the heating temperature is set to about 400°C or higher under atmospheric pressure, casting is performed, and the mixture is cooled and solidified at 30°C or lower.
The composition of the electrolytic plating electrode is the same as that of the metal particles of the present invention. That is, even if the electrode for electrolytic plating is manufactured as described above, the structure and composition of the metal particles of the present invention are maintained in the same manner.
Next, when electrolytic plating is performed using the electrolytic plating electrode as an anode, the intermetallic compound crystals contained in the electrolytic plating electrode are dispersed in the plating bath at nano-sized (1 μm or less), and are electrically charged into the matrix. It is also plated on the surface of the base material to form a plating layer. The formed plating layer also maintains the same structure and composition as the metal particles of the present invention.
The plating bath contains the metal particles of the present invention, and the intermetallic compound crystals are dispersed in nano-size (1 μm or less) and plated on the other metal together with the parent phase while being electrically charged to form a plating layer. . The formed plating layer has the same composition as the metal particles of the present invention.
前記めっき層を設けるためのめっき浴は、前記電解めっき用電極を備えてなること以外に、例えば次の組成を有することができる。
硫酸銅 １８０～２５０ｇ／Ｌ
硫酸第一錫 ３０～ ５０ｇ／Ｌ
硫酸 ８０～１２０ｇ／Ｌ
各添加剤等（付着抑制材、界面錯形成作用材、皮膜形成材、電界拡散消耗形成材）
前記のめっき浴の成分例示に加え、必要に応じて公知の分散剤、光沢剤、酸化防止剤等を適宜添加できる。例えばポリオキシエチレンクミルフェニルエーテル、ポリオキシエチレンラウリルエーテルなどの分散剤、クレゾールスルホン酸、アセトアルデヒド、アセチルアセトンなどの光沢剤、ホルマリン、カテコール、ヒドロキノンなどの酸化防止剤等を挙げることができる。
めっき温度は、例えば３０℃以下であり、１５～２０℃が好適である。
電流密度は、例えば１～１０Ａ／ｄｍ２の範囲で適宜調整される。
The plating bath for providing the plating layer can have the following composition, for example, in addition to being equipped with the electrolytic plating electrode.
Copper sulfate 180-250g/L
Stannous sulfate 30-50g/L
Sulfuric acid 80-120g/L
Various additives, etc. (adhesion suppressing material, interfacial complex forming agent, film forming material, electric field diffusion consumable forming material)
In addition to the above-mentioned examples of components of the plating bath, known dispersants, brighteners, antioxidants, etc. can be added as appropriate. Examples include dispersants such as polyoxyethylene cumyl phenyl ether and polyoxyethylene lauryl ether, brightening agents such as cresol sulfonic acid, acetaldehyde, and acetylacetone, and antioxidants such as formalin, catechol, and hydroquinone.
The plating temperature is, for example, 30°C or lower, preferably 15 to 20°C.
The current density is appropriately adjusted, for example, in the range of 1 to 10 A/dm 2 .
めっき後の基材は、続いて加熱処理される。加熱処理条件としては、例えば温度１００～３００℃であり、加熱時間は例えば５～３０秒程度である。
以上の操作により、基材の表面上にめっき層が形成される。めっき層の厚さとしては、例えば２μｍ～１０μｍである。
The plated base material is then heat treated. The heat treatment conditions are, for example, a temperature of 100 to 300° C., and a heating time of, for example, about 5 to 30 seconds.
Through the above operations, a plating layer is formed on the surface of the base material. The thickness of the plating layer is, for example, 2 μm to 10 μm.
Ａｌと前記めっき層との間になされる超音波印可（超音波用溶着）の条件としては、公知の条件に適宜従えばよいが、例えば周波数：20～110ｋＨｚ、発振モード：20～500ms、荷重範囲：5N～1000N、発振範囲：X350mm × Y100mm等が挙げられる。 The conditions for applying ultrasonic waves (ultrasonic welding) between Al and the plating layer may be according to known conditions, for example, frequency: 20 to 110 kHz, oscillation mode: 20 to 500 ms, load. Range: 5N to 1000N, oscillation range: X350mm x Y100mm, etc.
なお、Ａｌ以外の金属と前記その他の金属との接合を行う場合、加熱などの接合条件は、常法に従えばよい。 Note that when bonding a metal other than Al and the other metal, the bonding conditions such as heating may be according to a conventional method.
本発明のバルクは、上述のように金属粒子を１００℃～１９０℃に加熱された圧延回転ロールに直接挿入し加工することにより得ることができ、バルクの形状は例えばシート状であり、これを複数枚積層してもよい。
本発明のバルクは、例えば、Ｓｎより導電性が高いＣｕ、Ｎｉ合金粒子、水素化Ti粉末と、本発明の金属粒子（IMC粒子）とを組み合わせると、導電性がよく、かつ、比較的幅広い温度領域で体積変化が抑制されることからセラミック等の異質接合材シートを作ることができ、放熱機能を有する接合材として機能する機材を得ることもできる。
The bulk of the present invention can be obtained by directly inserting metal particles into a rotating rolling roll heated to 100°C to 190°C and processing them as described above, and the shape of the bulk is, for example, a sheet. A plurality of sheets may be stacked.
For example, the bulk of the present invention has good conductivity and a relatively wide range by combining Cu, Ni alloy particles, hydrogenated Ti powder, which have higher conductivity than Sn, and the metal particles (IMC particles) of the present invention. Since the volume change is suppressed in the temperature range, it is possible to make sheets of different bonding materials such as ceramics, and it is also possible to obtain equipment that functions as a bonding material with a heat dissipation function.
また、本発明の金属粒子を有機ビヒクル中に混在させて、導電性ペーストを得ることもできる。 Moreover, a conductive paste can also be obtained by mixing the metal particles of the present invention in an organic vehicle.
なお、前記バルクまたは前記導電性ペーストは、ＳｎＡｇＣｕ系合金粒子、Ｃｕ、Ｃｕ合金粒子、Ｎｉ、Ｎｉ合金粒子またはこれらの混合物のような他の粒子を加え、金属粒子との混合物としてもよい。これら他の粒子は、必要に応じてＳｉのような金属でコートされていてもよい。
例えば、Ｓｎより導電性が高いＣｕやＮｉ合金粒子と金属粒子とを組み合わせると、導電性がよく、かつ、比較的幅広い温度領域で体積変化が抑制された金属接合層が得られる。
Note that the bulk or the conductive paste may be a mixture with metal particles by adding other particles such as SnAgCu alloy particles, Cu, Cu alloy particles, Ni, Ni alloy particles, or a mixture thereof. These other particles may be coated with a metal such as Si, if necessary.
For example, when Cu or Ni alloy particles, which have higher conductivity than Sn, are combined with metal particles, a metal bonding layer with good conductivity and suppressed volume change over a relatively wide temperature range can be obtained.
本発明の金属粒子を用いることにより、該金属粒子の効果をそのまま享受できる接合構造部を得ることができる。
図５は、本発明における接合構造部の構造を説明するための模式断面図である。
図５において、接合構造部は、対向配置された基板１００(例えばＣｕ）、５００（例えばチップ）に形成された金属/合金体１０１、５０１（図５では一方がＣｕ、他方がＡｌ）を接合する。本発明の金属粒子により、異種金属の拡散相３００が形成され、拡散相３００は接合構造部の主要の構成となっている。
By using the metal particles of the present invention, it is possible to obtain a bonded structure that can enjoy the effects of the metal particles as they are.
FIG. 5 is a schematic cross-sectional view for explaining the structure of the joining structure section in the present invention.
In FIG. 5, the bonding structure unit connects metal/alloy bodies 101, 501 (in FIG. 5, one is Cu and the other is Al) formed on substrates 100 (for example, Cu) and 500 (for example, a chip) that are arranged facing each other. do. A diffusion phase 300 of different metals is formed by the metal particles of the present invention, and the diffusion phase 300 is the main component of the bonding structure.
基板１００，５００は、半導体素子を備え、例えばパワーデバイスなどの電子・電気機器を構成する基板であり、金属/合金体１０１，５０１は、電極、バンプ、端子またはリード導体などとして、基板１００，５００に一体的に設けられている接続部材である。 The substrate 100, 500 is a substrate that includes a semiconductor element and constitutes an electronic/electrical device such as a power device, and the metal/alloy body 101, 501 is used as an electrode, bump, terminal, lead conductor, etc. 500 is a connecting member provided integrally with the connector.
本発明の金属粒子を用いて加熱後に得られる接合構造部は、該金属粒子の結晶構造と同様の結晶構造を有することが、本発明者らによって確認されている（ただし、金属/合金体１０１，５０１がＣｕを含む場合は接合構造部にＣｕがさらに加わる）。 The present inventors have confirmed that the bonded structure obtained after heating using the metal particles of the present invention has a crystal structure similar to that of the metal particles (however, the metal/alloy body 101 , 501, Cu is further added to the bonding structure).
本発明の接合構造部は、Ｓｎと、Ｓｎ－Ｃｕ合金と、を含む母相中に、Ｓｎ、Ｃｕ、Ｎｉ、ＡｌおよびＣｒを含む金属間化合物結晶を有し、
前記接合構造部の組成が、
Ｃｕ ０．７～１５質量％、
Ｎｉ １～０.０２質量％、
Ａｌ ３～０.０２質量％、
Ｃｒ ２～０.０２質量％、
残部がＳｎであり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記母相の組成が、
Ｓｎ ９２～９９．９質量％、
Ｃｕ ５質量％以下、
Ｎｉ １質量％以下、
Ａｌ ３質量％以下であり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記金属間化合物の組成が、
Ｃｕ ５～５０質量％、
Ｎｉ ６.５～０.１質量％、
Ａｌ ２０～０．５質量％、
Ｃｒ ０．００１～０．１質量％、
残部がＳｎである（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）。
なお接合構造部において、前記母相中に前記金属間化合物が包含されて存在する。
The joint structure of the present invention has an intermetallic compound crystal containing Sn, Cu, Ni, Al and Cr in a matrix containing Sn and a Sn-Cu alloy,
The composition of the joint structure is
Cu 0.7-15% by mass,
Ni 1-0.02% by mass,
Al 3-0.02% by mass,
Cr 2-0.02% by mass,
The remainder is Sn (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The composition of the matrix is
Sn 92-99.9% by mass,
Cu 5% by mass or less,
Ni 1% by mass or less,
Al is 3% by mass or less (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The composition of the intermetallic compound is
Cu 5-50% by mass,
Ni 6.5-0.1% by mass,
Al 20-0.5% by mass,
Cr 0.001-0.1% by mass,
The remainder is Sn (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less).
Note that in the bonding structure, the intermetallic compound is included in the parent phase.
また、本発明の接合構造部における金属間化合物の割合は、接合構造部に対し、例えば２０～６０質量％であり、３０～４０質量％が好ましい。 Further, the proportion of the intermetallic compound in the joint structure of the present invention is, for example, 20 to 60% by mass, preferably 30 to 40% by mass, based on the joint structure.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されない。 EXAMPLES The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
実施例１
原材料としてＣｕ８質量％、Ｎｉ１質量％、Ａｌ１質量％、Ｃｒ１質量％および残部がＳｎからなる組成の原材料を用い、図２に示す製造装置により、直径約３～１３μｍの金属粒子１を製造した。
その際、以下の条件を採用した。
溶解炉７に溶融るつぼを設置し、その中に上記原材料を入れ、６５０℃で溶融し、その温度を保持したまま、ノズル３から皿型回転ディスク４上に溶融金属を供給した。
皿形回転ディスク４として、直径３５ｍｍ、回転盤厚さ３～５ｍｍの皿形ディスクを用い、毎分８万～１０万回転とした。
粒状化室１として、９×１０-２Ｐａ程度まで減圧する性能を有する真空槽を使用して減圧した上で、１５～５０℃の窒素ガスを供給しつつ排気を同時に行って、粒状化室１内の気圧を１×１０－１Ｐａ以下とした。
Example 1
Metal particles 1 having a diameter of about 3 to 13 μm were produced using the production apparatus shown in FIG. 2 using a raw material having a composition of 8% by mass of Cu, 1% by mass of Ni, 1% by mass of Al, 1% by mass of Cr, and the balance being Sn.
At that time, the following conditions were adopted.
A melting crucible was installed in the melting furnace 7, and the above-mentioned raw materials were put therein and melted at 650° C., and while maintaining that temperature, the molten metal was supplied from the nozzle 3 onto the dish-shaped rotating disk 4.
As the dish-shaped rotating disk 4, a dish-shaped disk having a diameter of 35 mm and a rotary plate thickness of 3 to 5 mm was used, and the rotation speed was 80,000 to 100,000 per minute.
As the granulation chamber 1, the pressure is reduced using a vacuum chamber capable of reducing the pressure to about 9×10 -2 Pa, and nitrogen gas at 15 to 50° C. is supplied and exhausted at the same time to complete the granulation chamber. The atmospheric pressure inside the chamber was set to 1×10 −1 Pa or less.
得られた金属粒子１は、前記図１に示すような断面を有しており、金属粒子１断面のEDSによる元素マッピング分析を行ったところ（図３ＡおよびＢ参照）、金属粒子の組成は
Ｃｕ 8.08質量％、
Ｎｉ 2.42質量％、
Ａｌ 1.65質量％、
Ｃｒ 1.68質量％、
残部Ｓｎであることが判明した。
また、母相の組成は、
Ｓｎ 94.55質量％、
Ｃｕ 4.73質量％、
Ｎｉ 0.71質量％、
Ａｌ 0.11質量％、
であることが判明した。
また、金属間化合物結晶の組成は、
Ｃｕ 18.49質量％、
Ｎｉ 7.71質量％、
Ａｌ 19.58質量％、
Ｃｒ 0.98質量％、
残部Ｓｎであることが判明した。
The obtained metal particles 1 have a cross section as shown in FIG. 1, and elemental mapping analysis of the cross section of the metal particles 1 by EDS (see FIGS. 3A and B) revealed that the composition of the metal particles was Cu. 8.08% by mass,
Ni 2.42% by mass,
Al 1.65% by mass,
Cr 1.68% by mass,
The remainder was found to be Sn.
In addition, the composition of the matrix is
Sn 94.55% by mass,
Cu 4.73% by mass,
Ni 0.71% by mass,
Al 0.11% by mass,
It turned out to be.
In addition, the composition of the intermetallic compound crystal is
Cu 18.49% by mass,
Ni 7.71% by mass,
Al 19.58% by mass,
Cr 0.98% by mass,
The remainder was found to be Sn.
また、金属粒子１における金属間化合物は、金属粒子中、３０～３５質量％を占めていた。 Further, the intermetallic compound in Metal Particle 1 accounted for 30 to 35% by mass in the metal particles.
次に、金属粒子１を乾粉圧接してシートを作成し、当該シートをＣｕ電極とＣｕ基板との接合に用い、接合構造部を形成して、２６０℃の高温保持試験（ＨＴＳ）を行ったところ、試験開始時から約１００時間までは、シェア強度が約５０ＭＰaから約６０ＭＰａまで上昇し、１００時間超の時間領域では、ほぼ６０ＭＰａで安定するという試験結果が得られた。
また、（-４０～２００℃）の冷熱サイクル試験（ＴＣＴ）では、全サイクル（１０００サイクル）に渡って、シェア強度が約５０ＭＰaで安定するという試験結果が得られた。
なお、前記シートは、前記図１に示すような断面を有しており、前記金属粒子１断面のEDSによる元素マッピング分析と同様の結果を示した。
Next, a sheet was created by dry-powder welding the metal particles 1, and the sheet was used to bond the Cu electrode and the Cu substrate to form a bonding structure, and a high temperature holding test (HTS) at 260° C. was conducted. However, the test results showed that the shear strength increased from about 50 MPa to about 60 MPa for about 100 hours from the start of the test, and stabilized at about 60 MPa for more than 100 hours.
In addition, in a thermal cycle test (TCT) at (-40 to 200°C), the test result was that the shear strength remained stable at about 50 MPa over the entire cycle (1000 cycles).
Note that the sheet had a cross section as shown in FIG. 1, and showed the same results as the elemental mapping analysis by EDS of the cross section of the metal particle 1.
実施例２
原材料としてＣｕ８質量％、Ｎｉ１質量％、Ａｌ１質量％、Ｃｒ１質量％および残部がＳｎからなる組成の原材料を用いて、実施例１と同じ条件で金属粒子１を製造した。続いて、得られた金属粒子１を用い、電解めっき用電極を作製した。
その際、以下の条件を採用した。
高周波誘導加熱：９×１０-２Ｐａ程度まで減圧可能な性能を有する真空槽内に高周波溶解用るつぼを設置し、該るつぼに上記本発明の金属粒子１を導入し、上記減圧度程度まで減圧したまま上記本発明の金属粒子１に対し高周波誘導加熱を行い、加熱温度を９００℃にして上記本発明の金属粒子を溶解させ、その温度を５分保持した。
冷却固化：続いて、１５～５０℃の窒素ガスを槽内に１０分間流しつつ、大気圧下で原材料の加熱温度を約４００℃に設定し、鋳型鋳込みを行い、室温で冷却固化させた。
得られた材料を用い、圧延シート化し、厚さ３００μｍの金属シート２を得て、これを実施例２の電解めっき用電極とし、下記のメッキ浴に設置した。
Example 2
Metal particles 1 were produced under the same conditions as in Example 1 using a raw material having a composition of 8% by mass of Cu, 1% by mass of Ni, 1% by mass of Al, 1% by mass of Cr, and the balance being Sn. Subsequently, an electrode for electrolytic plating was produced using the obtained metal particles 1.
At that time, the following conditions were adopted.
High-frequency induction heating: A crucible for high-frequency melting is installed in a vacuum chamber capable of reducing the pressure to about 9 × 10 -2 Pa, the metal particles 1 of the present invention are introduced into the crucible, and the pressure is reduced to about the above degree of pressure reduction. The metal particles 1 of the present invention were then subjected to high-frequency induction heating to a heating temperature of 900° C. to dissolve the metal particles of the present invention, and the temperature was maintained for 5 minutes.
Cooling and solidification: Next, while flowing nitrogen gas at 15 to 50°C into the tank for 10 minutes, the heating temperature of the raw material was set to about 400°C under atmospheric pressure, casting was carried out into a mold, and the material was cooled and solidified at room temperature.
The obtained material was rolled into a sheet to obtain a metal sheet 2 with a thickness of 300 μm, which was used as an electrode for electrolytic plating in Example 2 and placed in the following plating bath.
得られた実施例２の電解めっき用電極は、前記図１に示すような断面を有していた。また上記電解めっき用電極の１断面のＥＤＳによる元素マッピング分析を行ったところ、
Ｃｕ 8.08質量％、
Ｎｉ 2.42質量％、
Ａｌ 1.65質量％、
Ｃｒ 1.68質量％、
残部Ｓｎであることが判明した。
また、母相の組成は、
Ｓｎ 94.55質量％、
Ｃｕ 4.73質量％、
Ｎｉ 0.71質量％、
Ａｌ 0.11質量％、
であることが判明した。
また、金属間化合物結晶の組成は、
Ｃｕ 18.49質量％、
Ｎｉ 7.71質量％、
Ａｌ 19.58質量％、
Ｃｒ 0.98質量％、
残部Ｓｎであることが判明した。
また、上記電解めっき用電極における金属間化合物結晶は、３０～３５質量％を占めていた。
The obtained electrolytic plating electrode of Example 2 had a cross section as shown in FIG. 1 above. In addition, elemental mapping analysis by EDS of one cross section of the electrode for electrolytic plating was performed.
Cu 8.08% by mass,
Ni 2.42% by mass,
Al 1.65% by mass,
Cr 1.68% by mass,
The remainder was found to be Sn.
In addition, the composition of the matrix is
Sn 94.55% by mass,
Cu 4.73% by mass,
Ni 0.71% by mass,
Al 0.11% by mass,
It turned out to be.
In addition, the composition of the intermetallic compound crystal is
Cu 18.49% by mass,
Ni 7.71% by mass,
Al 19.58% by mass,
Cr 0.98% by mass,
The remainder was found to be Sn.
Furthermore, the intermetallic compound crystals in the electrolytic plating electrode accounted for 30 to 35% by mass.
基材（陰極）として、銅クリップ（銅板）を用いた。
次の条件で該基材に対し、前記電解めっき用電極を用い、電解めっきを行い、めっき板金を得た。
A copper clip (copper plate) was used as the base material (cathode).
Electrolytic plating was performed on the base material using the electrolytic plating electrode under the following conditions to obtain a plated sheet metal.
めっき浴組成組成（水１リットルに対する濃度）：
硫酸銅 １８０～２５０ｇ／Ｌ
硫酸第一錫 ３０～ ５０ｇ／Ｌ
硫酸 ８０～１２０ｇ／Ｌ
また、公知の参照電極を用い、添加剤を適量加えた。
めっき温度：７０℃
電流密度：３Ａ／ｄｍ２
めっき後の基材の加熱処理温度：２００℃
めっき後の基材の加熱処理時間：３００秒（窒素雰囲気下）
Plating bath composition (concentration per 1 liter of water):
Copper sulfate 180-250g/L
Stannous sulfate 30-50g/L
Sulfuric acid 80-120g/L
Further, an appropriate amount of additive was added using a known reference electrode.
Plating temperature: 70℃
Current density: 3A/ dm2
Heat treatment temperature of base material after plating: 200℃
Heat treatment time of base material after plating: 300 seconds (under nitrogen atmosphere)
得られためっき層の組成は、前記本発明の電解めっき用電極の組成と同じであった。 The composition of the obtained plating layer was the same as that of the electrolytic plating electrode of the present invention.
次に、得られためっき層を表面に有する銅クリップと、Ｓｉチップ上のアルミニウム面とを超音波溶着した。超音波溶着の条件は、周波数:80ｋＨｚ、発振モード:80%(8段階、25～500ms)、とした。
得られた銅クリップのめっき層の面とＳｉチップ上のアルミニウム面との間の接着強度測定として、２６０℃の高温保持試験（ＨＴＳ）を行ったところ、試験開始時から約１００時間までは、シェア強度が約７０ＭＰaから約７５ＭＰａまで上昇し、１００時間超の時間領域では、ほぼ７５ＭＰａで安定するという試験結果が得られた。
また、（-４０～２００℃）の冷熱サイクル試験（ＴＣＴ）では、全サイクル（１０００サイクル）に渡って、シェア強度が約７０ＭＰaで安定するという試験結果が得られた。
図４Ａ（ａ）は、銅クリップのめっき層の面１２０とＳｉチップ上のアルミニウム面１４０の接合面断面のＳＥＭ像であり、図４Ａ(b)は拡大図である。接合部分Ｃのさらなる拡大図を図４Ｂに示す。図４Ｂから異種金属の拡散状況が行われている事が分かる。
Next, the copper clip having the obtained plating layer on its surface was ultrasonically welded to the aluminum surface on the Si chip. The conditions for ultrasonic welding were: frequency: 80 kHz, oscillation mode: 80% (8 steps, 25 to 500 ms).
A high temperature holding test (HTS) at 260°C was conducted to measure the adhesive strength between the surface of the plating layer of the obtained copper clip and the aluminum surface of the Si chip. The test results showed that the shear strength increased from about 70 MPa to about 75 MPa, and stabilized at about 75 MPa in a time range of more than 100 hours.
Furthermore, in a thermal cycle test (TCT) at (-40 to 200°C), the test result was that the shear strength remained stable at about 70 MPa over the entire cycle (1000 cycles).
FIG. 4A(a) is a SEM image of a cross section of the bonding surface between the surface 120 of the plating layer of the copper clip and the aluminum surface 140 on the Si chip, and FIG. 4A(b) is an enlarged view. A further enlarged view of junction C is shown in FIG. 4B. It can be seen from FIG. 4B that dissimilar metals are being diffused.
比較例１
なお、比較例として、従来のSnAgCu系接合材（粒径５μｍの粉末はんだ材料）を用い、実施例１の（-４０～２００℃）の冷熱サイクル試験（ＴＣＴ）を行ったところ、１００サイクルももたずに接合部崩壊してしまい、本発明の金属粒子のような耐熱性および強度を到底得ることができなかった。
本発明者らの検討により、従来のSnAgCu系接合材は、金属間化合物が存在せず、単一金属の元素が分散していることが確認された。
Comparative example 1
As a comparative example, a conventional SnAgCu-based bonding material (powdered solder material with a particle size of 5 μm) was subjected to the thermal cycle test (TCT) at (-40 to 200°C) as in Example 1. The joints collapsed without holding, and the heat resistance and strength of the metal particles of the present invention could not be obtained at all.
Through studies conducted by the present inventors, it has been confirmed that in the conventional SnAgCu-based bonding material, no intermetallic compound exists and a single metal element is dispersed.
以上、添付図面を参照して本発明を詳細に説明したが、本発明はこれらに限定されるものではなく、当業者であれば、その基本的技術思想および教示に基づき、種々の変形例を想到できることは自明である。 Although the present invention has been described above in detail with reference to the accompanying drawings, the present invention is not limited thereto, and those skilled in the art will be able to make various modifications based on the basic technical idea and teachings thereof. It is obvious that it can be imagined.
１ 粒状化室
２ 蓋
３ ノズル
４ 皿形回転ディスク
５ 回転ディスク支持機構
６ 粒子排出管
７ 電気炉
８ 混合ガスタンク
９ 配管
１０ 配管
１１ 弁
１２ 排気装置
１３ 弁
１４ 排気装置
１５ 自動フィルター
１６ 微粒子回収装置
１００ 基板
１０１ 金属/合金体
３００ 拡散相
５００ 基板
５０１ 金属/合金体
１２０ 銅クリップのめっき層の面
１４０ Ｓｉチップ上のアルミニウム面
1 Granulation chamber 2 Lid 3 Nozzle 4 Dish-shaped rotating disk 5 Rotating disk support mechanism 6 Particle discharge pipe 7 Electric furnace 8 Mixed gas tank 9 Piping 10 Piping 11 Valve 12 Exhaust device 13 Valve 14 Exhaust device 15 Automatic filter 16 Particulate recovery device 100 Substrate 101 Metal/alloy body 300 Diffused phase 500 Substrate 501 Metal/alloy body 120 Copper clip plating layer surface 140 Aluminum surface on Si chip
Claims (2)
前記金属粒子の組成が、
Ｃｕ ０．７～１５質量％、
Ｎｉ １～０.０２質量％、
Ａｌ ３～０.０２質量％、
Ｃｒ ２～０.０２質量％、
残部がＳｎであり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記母相の組成が、
Ｓｎ ９２～９９．９質量％、
Ｃｕ ５質量％以下、
Ｎｉ １質量％以下、
Ａｌ ３質量％以下であり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記金属間化合物の組成が、
Ｃｕ ５～５０質量％、
Ｎｉ ６.５～０.１質量％、
Ａｌ ２０～０．５質量％、
Ｃｒ ０．００１～０．１質量％、
残部がＳｎであり（ただし、不可避不純物が存在する場合、前記不可避不純物は０．１質量％以下である）、
前記母相中に前記金属間化合物結晶が包含されて存在し、
前記金属粒子における前記金属間化合物の割合は、前記金属粒子全体に対し、２０～６０質量％である、
ことを特徴とする金属粒子。 Metal particles having intermetallic compound crystals containing Sn, Cu, Ni, Al and Cr in a matrix containing Sn and a Sn-Cu alloy,
The composition of the metal particles is
Cu 0.7-15% by mass,
Ni 1-0.02% by mass,
Al 3-0.02% by mass,
Cr 2-0.02% by mass,
The remainder is Sn (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The composition of the matrix is
Sn 92-99.9% by mass,
Cu 5% by mass or less,
Ni 1% by mass or less,
Al is 3% by mass or less (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The composition of the intermetallic compound is
Cu 5-50% by mass,
Ni 6.5-0.1% by mass,
Al 20-0.5% by mass,
Cr 0.001-0.1% by mass,
The remainder is Sn (however, if unavoidable impurities are present, the unavoidable impurities are 0.1% by mass or less),
The intermetallic compound crystal is included and exists in the parent phase ,
The proportion of the intermetallic compound in the metal particles is 20 to 60% by mass with respect to the entire metal particles,
Metal particles characterized by:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010274326A (en) | 2009-05-29 | 2010-12-09 | Nihon Superior Co Ltd | Joined structure of solder joint |
| JP2018150614A (en) | 2017-03-10 | 2018-09-27 | 有限会社 ナプラ | Metal particle |
| JP6799649B1 (en) | 2019-08-27 | 2020-12-16 | 有限会社 ナプラ | Metal particles |
| US20210078112A1 (en) | 2019-09-18 | 2021-03-18 | Napra Co., Ltd. | Bonding structure |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010274326A (en) | 2009-05-29 | 2010-12-09 | Nihon Superior Co Ltd | Joined structure of solder joint |
| JP2018150614A (en) | 2017-03-10 | 2018-09-27 | 有限会社 ナプラ | Metal particle |
| JP6799649B1 (en) | 2019-08-27 | 2020-12-16 | 有限会社 ナプラ | Metal particles |
| US20210078112A1 (en) | 2019-09-18 | 2021-03-18 | Napra Co., Ltd. | Bonding structure |
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