JP6507120B2 - Semiconductor in which the bonding surface with a substrate is surface-treated, and bonding method using copper powder paste - Google Patents
Semiconductor in which the bonding surface with a substrate is surface-treated, and bonding method using copper powder paste Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 38
- 239000000758 substrate Substances 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 21
- 239000010949 copper Substances 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 19
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 229910052758 niobium Inorganic materials 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 229910052715 tantalum Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000011651 chromium Substances 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 14
- 239000010955 niobium Substances 0.000 description 13
- 239000012535 impurity Substances 0.000 description 9
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000002335 surface treatment layer Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910003336 CuNi Inorganic materials 0.000 description 2
- 229910002535 CuZn Inorganic materials 0.000 description 2
- 229910003322 NiCu Inorganic materials 0.000 description 2
- 229910006164 NiV Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910017980 Ag—Sn Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Die Bonding (AREA)
Description
本発明は、基材との接合面が表面処理された半導体、および銅粉ペーストによる接合方法に関する。 The present invention relates to a semiconductor whose bonding surface with a substrate is surface-treated, and a bonding method using a copper powder paste.
パワーデバイスは電力変換用の素子として、エアコン用インバータや送変電など幅広い分野で使用されている。従来はＳｉチップのデバイスで対応できたが、高耐圧、大電流用途、高速動作が求められる分野では、Ｓｉよりもバンドギャップが大きいＳｉＣ、ＧａＮ等が近年注目を浴びている。 Power devices are used as elements for power conversion in a wide range of fields such as inverters for air conditioners, transmission and transformation, and the like. Conventionally, it has been possible to cope with Si chip devices, but in fields requiring high withstand voltage, large current applications, and high-speed operation, SiC, GaN, etc. having a larger band gap than Si have recently attracted attention.
従来のパワーモジュールでは動作温度がせいぜい１７０℃程度であったが、次世代型のＳｉＣ、ＧａＮ等では２００℃を超える可能性がある。これに伴い、これらチップを搭載したモジュールに使用される各材料には耐熱性、放熱性が求められている。 The operating temperature is at most about 170 ° C. in the conventional power module, but may exceed 200 ° C. in the next generation SiC, GaN and the like. Along with this, heat resistance and heat dissipation are required for each material used for a module mounted with these chips.
接合材料に関して、Ｐｂフリーの観点でＣｕ−Ａｇ−Ｓｎはんだが好ましいが、次世代型モジュールでは動作温度が２００℃を超える可能性があるので、融点が２１０〜２２０℃であるこのはんだは溶融してしまう可能性がある。Ｐｂはんだであれば次世代型モジュールの動作温度には対応しうるが、環境規制の観点から好ましくない。また、はんだは使用環境の温度によって、被接合材との間で金属拡散が進行する。はんだに含まれる金属成分によっては、拡散速度に差が生じ、接合界面にカーケンダルボイドが発生する。これは接合強度の劣化、すなわちパワーモジュールの信頼性低下につながる。 As for the bonding material, Cu-Ag-Sn solder is preferable from the viewpoint of Pb-free, but in the next-generation module, the operating temperature may exceed 200 ° C, so this solder having a melting point of 210-220 ° C melts There is a possibility of The Pb solder can cope with the operating temperature of the next generation module, but is not preferable from the viewpoint of environmental regulation. Moreover, metal diffusion proceeds between the solder and the material to be joined depending on the temperature of the use environment. Depending on the metal component contained in the solder, a difference in diffusion rate occurs, and a Kirkendall void is generated at the bonding interface. This leads to the deterioration of the joint strength, that is, the reduction of the reliability of the power module.
そこで、近年次世代型モジュールの接合材料として金属粉ペーストが注目されている。金属粉のサイズが小さいので、表面エネルギーが高く、これを利用してその金属の融点よりも低い温度で焼結が始まる。そして、はんだとは異なり、いったん焼結すれば、その金属の融点近くまで昇温しないと再溶融しない。このような特性を生かし、銀粉ペーストの開発が進んでいる（特許文献１）。 Therefore, metal powder paste has recently attracted attention as a bonding material for next-generation modules. Due to the small size of the metal powder, the surface energy is high and it is used to initiate sintering at a temperature below the melting point of the metal. And unlike solder, once sintered, it does not remelt unless the temperature is raised close to the melting point of the metal. Development of silver powder paste is in progress by making use of such characteristics (Patent Document 1).
銀粉ペーストは優れた接合材料となるが、材料コストの観点で不利である。一方、銅粉ペーストは材料コストの観点から有利である。したがって、本発明の目的は、銅粉ペーストによって半導体と基材とを接合する手段を提供することにある。 Silver powder paste is an excellent bonding material, but is disadvantageous in terms of material cost. On the other hand, copper powder paste is advantageous from the viewpoint of material cost. Therefore, an object of the present invention is to provide a means for bonding a semiconductor and a substrate by a copper powder paste.
本発明者は、この銅粉ペーストを接合材料として使用して、半導体と基材とを接合する手段を鋭意研究してきた。しかし、銀粉ペーストに使用するために提案されてきた従来の半導体構造のチップに対して、単に銀粉ペーストに代えて銅粉ペーストを使用しただけでは、接合強度は不十分であった。これは銅粉ペーストの組成を変更しても同様であった。そこで、むしろ半導体の接合面に表面処理を行って、銅粉ペーストによって十分な接合強度を達成するという着想に至った。すなわち、チップの接合のように非常に弱い拡散条件でも十分な接合強度を得るために、チップ側の接合面にＣｕ層を設ける着想に至った。 The inventors of the present invention have intensively studied means for bonding a semiconductor and a substrate using this copper powder paste as a bonding material. However, for the chip of the conventional semiconductor structure that has been proposed for use in silver powder paste, simply using copper powder paste instead of silver powder paste has insufficient bonding strength. This was the same even if the composition of the copper powder paste was changed. Therefore, the idea was that surface treatment was performed on the bonding surface of the semiconductor to achieve sufficient bonding strength by the copper powder paste. That is, in order to obtain sufficient bonding strength even under very weak diffusion conditions like bonding of chips, the idea of providing a Cu layer on the bonding surface on the chip side was reached.
しかし、本発明者の洞察によれば、従来の銀粉ペーストのために提案されてきたＡｇ層に代替して、単にＣｕ層を設けただけでは、Ｃｕ層とチップとの間にＮｉ層を設けてあっても、チップ側にＣｕが拡散し、チップの機能を低下させる可能性が生じる。 However, according to the inventor's insight, the Ni layer is provided between the Cu layer and the chip simply by providing the Cu layer instead of the Ag layer proposed for the conventional silver powder paste. However, there is a possibility that Cu diffuses to the chip side and degrades the function of the chip.
本発明者は、半導体のチップ側に適切な表面処理を行うことによって、銅粉ペーストによっても十分な接合強度が得られ、チップ側へのＣｕ拡散の可能性を回避でき、繰り返し高温にさらされる条件下でも接合強度が維持される（熱劣化耐性を有する）ことを見いだして、本発明に到達した。 By performing appropriate surface treatment on the chip side of the semiconductor, the inventors of the present invention can obtain sufficient bonding strength even with copper powder paste, avoid the possibility of Cu diffusion to the chip side, and are repeatedly exposed to high temperatures. The present invention has been reached by finding that the bonding strength is maintained even under conditions (having thermal degradation resistance).
したがって、本発明は以下の（１）以下を含む。
（１）
接合材との接合面側に、最表層から順に、Ｃｕ又はＣｕ合金の層、Ｎｉ又はＮｉ合金の層、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層を有する、半導体。
（２）
Ｃｕ又はＣｕ合金の層が厚み換算で１μｍ以下、Ｎｉ又はＮｉ合金の層が厚み換算で１μｍ以下、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層が厚み換算で１μｍ以下である、（１）に記載の半導体。
（３）
半導体が、ワイドギャップ半導体である、（１）〜（２）のいずれかに記載の半導体。
（４）
半導体の接合面側に、乾式成膜法で、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層、Ｎｉ又はＮｉ合金の層、Ｃｕ又はＣｕ合金の層を順に形成して、半導体の接合面を調製する工程、
を含む、（１）〜（３）のいずれかに記載の半導体を製造する方法。
（５）
半導体の接合面側に、乾式成膜法で、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層、Ｎｉ又はＮｉ合金の層、Ｃｕ又はＣｕ合金の層を順に形成して、（１）〜（３）のいずれかに記載の半導体を調製する工程、
調製された半導体の接合面を、銅粉ペーストによって基材に接合する工程、
を含む、半導体実装品を製造する方法。
（６）
調製された半導体の接合面を、銅粉ペーストによって基材に接合する工程が、
調製された半導体の接合面を、基材上に塗工された銅粉ペーストと接触させて焼成して、基材に接合する工程、又は
調製された半導体の接合面上に塗工された銅粉ペーストを、基材と接触させて焼成して、基材に接合する工程、
である、（５）に記載の方法。
（７）
半導体実装品が、パワーモジュールである、（５）〜（６）のいずれかに記載の方法。
（８）
（１）〜（３）のいずれかに記載の半導体、
基材、及び
半導体の接合面と基材とを接合する接合層、
を含んでなる、半導体実装品。
（９）
接合層が焼成された銅粉ペーストからなる接合層である、（８）に記載の半導体実装品。
（１０）
半導体実装品が、パワーモジュールである、（８）〜（９）のいずれかに記載の半導体実装品。
Therefore, the present invention includes the following (1):
(1)
A layer of Cu or Cu alloy, a layer of Ni or Ni alloy, and a layer of one kind of metal selected from Cr, Ti, Nb, Ta and Co on the bonding surface side with the bonding material, from the outermost layer, semiconductor.
(2)
The Cu or Cu alloy layer is 1 μm or less in thickness conversion, the Ni or Ni alloy layer is 1 μm or less in thickness conversion, 1 metal layer selected from Cr, Ti, Nb, Ta and Co is 1 μm in thickness conversion The semiconductor according to (1), which is the following.
(3)
The semiconductor according to any one of (1) to (2), wherein the semiconductor is a wide gap semiconductor.
(4)
A layer of one metal selected from Cr, Ti, Nb, Ta and Co, a layer of Ni or Ni alloy, a layer of Cu or Cu alloy are sequentially formed on the bonding surface side of the semiconductor by a dry film formation method. Preparing the bonding surface of the semiconductor,
A method of manufacturing the semiconductor according to any one of (1) to (3), including
(5)
A layer of one metal selected from Cr, Ti, Nb, Ta and Co, a layer of Ni or Ni alloy, a layer of Cu or Cu alloy are sequentially formed on the bonding surface side of the semiconductor by a dry film formation method. Preparing a semiconductor according to any one of (1) to (3),
Bonding the prepared semiconductor bonding surface to a substrate with a copper powder paste,
A method of manufacturing a semiconductor package including:
(6)
The step of bonding the prepared bonding surface of the semiconductor to a substrate with a copper powder paste,
A step of contacting the prepared semiconductor bonding surface with a copper powder paste coated on a substrate, baking it, and bonding it to the substrate, or copper coated on the prepared semiconductor bonding surface Baking the powder paste in contact with the substrate and bonding it to the substrate,
The method according to (5).
(7)
The method in any one of (5)-(6) whose semiconductor mounting goods are power modules.
(8)
The semiconductor according to any one of (1) to (3),
A substrate, and a bonding layer for bonding a bonding surface of a semiconductor to the substrate,
Semiconductor mounted products.
(9)
The semiconductor mounted product according to (8), wherein the bonding layer is a bonding layer made of a fired copper powder paste.
(10)
The semiconductor mounted article in any one of (8)-(9) whose semiconductor mounted article is a power module.
本発明による表面処理層を接合面に備えた半導体は、銅粉ペーストによって基材と接合することができて、十分な接合強度が得られ、繰り返し高温にさらされる条件下でも接合強度が維持できる。本発明によって得られた半導体実装品は、接合強度と熱劣化耐性を備えており、例えばパワーモジュールとして好適に使用できる。 The semiconductor provided with the surface treatment layer according to the present invention on the bonding surface can be bonded to the base material by copper powder paste, sufficient bonding strength can be obtained, and bonding strength can be maintained even under repeated exposure to high temperature . The semiconductor mounted product obtained by the present invention has bonding strength and resistance to thermal degradation, and can be suitably used, for example, as a power module.
以下に本発明を実施の態様をあげて詳細に説明する。本発明は以下にあげる具体的な実施の態様に限定されるものではない。 Hereinafter, the present invention will be described in detail by way of embodiments. The present invention is not limited to the specific embodiments described below.
［表面処理層を有する半導体］
本発明による半導体は、接合材との接合面側に、最表層から順に、Ｃｕ又はＣｕ合金の層、Ｎｉ又はＮｉ合金の層、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層を、表面処理層として有する。
[Semiconductor having a surface treatment layer]
The semiconductor according to the present invention is one selected from the layer of Cu or Cu alloy, the layer of Ni or Ni alloy, Cr, Ti, Nb, Ta and Co on the bonding surface side with the bonding material in order from the outermost layer. A metal layer is provided as a surface treatment layer.
［Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ又はＣｏの層］
Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層は、それぞれクロム及び不可避不純物、チタン及び不可避不純物、ニオブ及び不可避不純物、タンタル及び不可避不純物、コバルト及び不可避不純物を含有することができる。好適にはＣｒ、Ｔｉ及びＣｏから選択された１種の金属を使用できる。好適な実施の態様において、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ又はＣｏの層は、例えば接合面側の半導体上に直接に形成することができる。形成には公知の手段を使用することができ、例えば乾式成膜法、湿式成膜法を使用することができる。好ましくは乾式成膜法が使用され、例えば蒸着、スパッタリングをあげることができる。スパッタリングは公知の手段によって行うことができ、安定したスパッタリングのために、例えばＣｏに対して、Ｖ、Ｓｎ、Ｍｏ、Ｚｎ、Ｃｕ等を１〜１０ｗｔ％の含有量で含有させたターゲット材を使用することもできる。Ｃｒ、Ｔｉ、Ｎｂ及びＣｏから選択された１種の金属の層は、厚み換算で例えば１μｍ以下、０．１０μｍ以下、例えば０．５ｎｍ以上、１ｎｍ以上、例えば１〜２０ｎｍとすることができる。厚み換算とは、表面処理面を酸に浸漬させ、その酸溶液中の金属濃度をＩＣＰ発光分光分析で測定することで、処理面の単位面積当たりのその金属の付着量を求め、それをその金属の比重で割り返すことによって求めることができる。
[Layer of Cr, Ti, Nb, Ta or Co]
The layer of one metal selected from Cr, Ti, Nb, Ta and Co contains chromium and an unavoidable impurity, titanium and an unavoidable impurity, niobium and an unavoidable impurity, tantalum and an unavoidable impurity, cobalt and an unavoidable impurity, respectively. Can. Preferably, one metal selected from Cr, Ti and Co can be used. In a preferred embodiment, a layer of Cr, Ti, Nb, Ta or Co can, for example, be formed directly on the semiconductor on the junction side. A publicly known means can be used for formation, for example, a dry film formation method and a wet film formation method can be used. Preferably, a dry film formation method is used, and for example, vapor deposition and sputtering can be mentioned. Sputtering can be performed by a known means, and for stable sputtering, for example, a target material containing V, Sn, Mo, Zn, Cu, etc. at a content of 1 to 10 wt% with respect to Co is used You can also The thickness of one metal layer selected from Cr, Ti, Nb and Co can be, for example, 1 μm or less, 0.10 μm or less, for example, 0.5 nm or more, 1 nm or more, for example, 1 to 20 nm. With the thickness conversion, the surface-treated surface is immersed in an acid, and the metal concentration in the acid solution is measured by ICP emission spectral analysis to determine the amount of attached metal per unit area of the treated surface, and It can be determined by dividing by the specific gravity of metal.
［Ｎｉ又はＮｉ合金の層］
Ｎｉ又はＮｉ合金の層は、ニッケル及び不可避不純物を含有することができる。Ｎｉ合金層のＮｉ合金は、Ｎｉ合金及び不可避不純物を含有することができる。Ｎｉ合金としては、例えばＮｉＶ、ＮｉＣｕ、ＮｉＺｎをあげることができ、好ましくはＮｉＶ、ＮｉＣｕである。Ｎｉ又はＮｉ合金の層は、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層の上に形成することができる。形成には公知の手段を使用することができ、例えば乾式成膜法、湿式成膜法を使用することができる。好ましくは乾式成膜法が使用され、例えば蒸着、スパッタリングをあげることができる。スパッタリングは公知の手段によって行うことができ、安定したスパッタリングのために、例えばＮｉに対して、Ｖ、Ｓｎ、Ｍｏ、Ｚｎ、Ｃｕ等を１〜１０ｗｔ％の含有量で含有させたターゲット材を使用することもできる。例えば、Ｎｉ合金の層を、Ｖ、Ｃｕ、Ｓｎ、Ｍｏ、Ｗによるスパッタリング層として、形成することができる。Ｎｉ又はＮｉ合金の層は、厚み換算で例えば１μｍ以下、０．１０μｍ以下、例えば０．５ｎｍ以上、１ｎｍ以上、例えば１〜２０ｎｍとすることができる。厚み換算とは、表面処理面を酸に浸漬させ、その酸溶液中の金属濃度をＩＣＰ発光分光分析で測定することで、処理面の単位面積当たりのその金属の付着量を求め、それをその金属の比重で割り返すことによって求めることができる。
[Ni or Ni alloy layer]
The layer of Ni or Ni alloy can contain nickel and unavoidable impurities. The Ni alloy of the Ni alloy layer can contain a Ni alloy and unavoidable impurities. Examples of the Ni alloy include NiV, NiCu, and NiZn, and preferably NiV and NiCu. The layer of Ni or Ni alloy can be formed on the layer of one metal selected from Cr, Ti, Nb, Ta and Co. A publicly known means can be used for formation, for example, a dry film formation method and a wet film formation method can be used. Preferably, a dry film formation method is used, and for example, vapor deposition and sputtering can be mentioned. Sputtering can be performed by a known means, and for stable sputtering, for example, a target material containing V, Sn, Mo, Zn, Cu, etc. at a content of 1 to 10 wt% with respect to Ni is used You can also For example, a layer of Ni alloy can be formed as a sputtering layer of V, Cu, Sn, Mo, W. The thickness of the layer of Ni or Ni alloy can be, for example, 1 μm or less, 0.10 μm or less, for example, 0.5 nm or more, 1 nm or more, for example, 1 to 20 nm. With the thickness conversion, the surface-treated surface is immersed in an acid, and the metal concentration in the acid solution is measured by ICP emission spectral analysis to determine the amount of attached metal per unit area of the treated surface, and It can be determined by dividing by the specific gravity of metal.
［Ｃｕ又はＣｕ合金の層］
Ｃｕ又はＣｕ合金の層は、半導体の接合面側の表面処理層の最表面（最外面）に位置しており、接合材と接して、接合される。Ｃｕ層のＣｕは、銅及び不可避不純物を含有することができる。Ｃｕ合金層のＣｕ合金は、Ｃｕ合金及び不可避不純物を含有することができる。Ｃｕ合金としては、例えばＣｕＺｎ、ＣｕＮｉ、チタン銅をあげることができ、好ましくはＣｕＺｎ、ＣｕＮｉである。Ｃｕ又はＣｕ合金の層は、Ｎｉ又はＮｉ合金の層の上に形成することができる。形成には公知の手段を使用することができ、例えば乾式成膜法、湿式成膜法を使用することができる。好ましくは乾式成膜法が使用され、例えば蒸着、スパッタリングをあげることができる。Ｃｕ又はＣｕ合金の層は、厚み換算で例えば５μｍ以下、１μｍ以下、０．１０μｍ以下、例えば５ｎｍ以上、１０ｎｍ以上、例えば５ｎｍ〜５μｍとすることができる。厚み換算とは、表面処理面を酸に浸漬させ、その酸溶液中の金属濃度をＩＣＰ発光分光分析で測定することで、処理面の単位面積当たりのその金属の付着量を求め、それをその金属の比重で割り返すことによって求めることができる。
[Layer of Cu or Cu alloy]
The layer of Cu or Cu alloy is located on the outermost surface (outermost surface) of the surface treatment layer on the bonding surface side of the semiconductor, and is bonded in contact with the bonding material. The Cu of the Cu layer can contain copper and unavoidable impurities. The Cu alloy of the Cu alloy layer can contain a Cu alloy and unavoidable impurities. As a Cu alloy, CuZn, CuNi, titanium copper can be mentioned, for example, Preferably it is CuZn, CuNi. The layer of Cu or Cu alloy can be formed on the layer of Ni or Ni alloy. A publicly known means can be used for formation, for example, a dry film formation method and a wet film formation method can be used. Preferably, a dry film formation method is used, and for example, vapor deposition and sputtering can be mentioned. The layer of Cu or Cu alloy can be, for example, 5 μm or less, 1 μm or less, 0.10 μm or less, for example 5 nm or more, 10 nm or more, for example 5 nm to 5 μm in thickness conversion. With the thickness conversion, the surface-treated surface is immersed in an acid, and the metal concentration in the acid solution is measured by ICP emission spectral analysis to determine the amount of attached metal per unit area of the treated surface, and It can be determined by dividing by the specific gravity of metal.
［半導体］
表面処理層を付与される半導体としては、銅粉ペーストによって基材との接着される半導体であれば、特に制限は無い。好適な実施の態様において、接合強度と熱劣化耐性が求められる半導体が使用される。このような半導体として、例えばワイドギャップ半導体、をあげることができる。ワイドギャップ半導体とは、Ｓｉのバンドギャップが１．１２ｅＶであるので、これに対してその約２倍、すなわち２．２ｅＶ以上のバンドギャップをもつ半導体をいう。代表的な例として、ＩＩＩ−Ｖ族半導体をあげることができ、例えばＧａＮ（３．３９ｅＶ）、ＳｉＣ（２．２〜３．０ｅＶ）、ダイヤモンド（５．４７ｅＶ）をあげることができる。
[semiconductor]
The semiconductor to which the surface treatment layer is to be applied is not particularly limited as long as it is a semiconductor to be adhered to a substrate by a copper powder paste. In a preferred embodiment, semiconductors are used which require bonding strength and resistance to thermal degradation. As such a semiconductor, for example, a wide gap semiconductor can be mentioned. The wide gap semiconductor refers to a semiconductor having a band gap about twice that of Si, that is, 2.2 eV or more, since the band gap of Si is 1.12 eV. As a representative example, a III-V group semiconductor can be mentioned, for example, GaN (3.39 eV), SiC (2.2 to 3.0 eV) and diamond (5.47 eV) can be mentioned.
［基材］
接合される基材としては、公知の基材をあげることができる。好適な実施の態様において、接合強度と熱劣化耐性が求められる基材が使用される。このような基材として、例えばＳｉ3Ｎ4（窒化ケイ素）、ＡｌＮ（窒化アルミニウム）、銅または銅合金のリードフレームをあげることができる。基材がＳｉＮ、ＡｌＮまたは銅合金である場合、上記半導体の接合面側の表面に行った表面処理を、基材の接合面側の表面に行って、同様の表面処理層を設けてもよく、すなわち、基材の最表層から順に、Ｃｕ又はＣｕ合金の層、Ｎｉ又はＮｉ合金の層、Ｃｒ、Ｔｉ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層を、表面処理層として設けてもよい。
[Base material]
A well-known base material can be mentioned as a base material joined. In a preferred embodiment, a substrate for which bonding strength and resistance to thermal degradation are required is used. As such a substrate, for example, a lead frame of Si 3 N 4 (silicon nitride), AlN (aluminum nitride), copper or a copper alloy can be mentioned. When the base material is SiN, AlN or a copper alloy, the surface treatment performed on the bonding surface side of the semiconductor may be performed on the bonding surface side of the base material to provide a similar surface treatment layer. That is, a layer of Cu or Cu alloy, a layer of Ni or Ni alloy, a layer of one kind of metal selected from Cr, Ti, Nb, Ta and Co, in order from the outermost layer of the substrate, as the surface treatment layer You may provide.
［銅粉ペーストによる基材との接合］
本発明の半導体の接合面を、銅粉ペーストによって基材に接合する工程、を行って、半導体実装品を製造することができる。銅粉ペーストによって基材に接合する工程は、半導体の接合面を、基材上に塗工された銅粉ペーストと接触させて焼成して、基材に接合する工程、又は、半導体の接合面上に塗工された銅粉ペーストを、基材と接触させて焼成して、基材に接合する工程、とすることができる。
Bonding to a substrate with copper powder paste
The step of bonding the bonding surface of the semiconductor of the present invention to a base material with a copper powder paste can be performed to manufacture a semiconductor mounted product. In the step of bonding to the substrate with the copper powder paste, the bonding surface of the semiconductor is brought into contact with the copper powder paste coated on the substrate and fired to bond to the substrate, or the bonding surface of the semiconductor The copper powder paste coated on top can be contacted with a base material, it can be baked, and it can be set as the process of joining to a base material.
［塗工］
銅粉ペーストの塗工は、公知の手段によって行うことができ、例えばスクリーン印刷、インクジェット印刷、メタルマスク印刷、マイクロコンタクト法、パッド印刷等によって行うことができる。塗工されて形成される塗膜の膜厚は、例えば１０〜５００μｍ、２０〜２００μｍの範囲とすることができる。塗膜は、所望により適宜乾燥して、その後の焼成を行うことができる。
[Coating]
The coating of the copper powder paste can be performed by a known means, for example, screen printing, ink jet printing, metal mask printing, microcontact method, pad printing and the like. The film thickness of the coating film formed by being coated can be made into the range of 10-500 micrometers and 20-200 micrometers, for example. The coating can be dried as appropriate, if desired, and then fired.
［焼成］
焼成は、銅粉ペーストの焼成の条件として公知の条件を使用することができる。焼成の温度は、例えば２２０℃〜３００℃の範囲とすることができる。好適な実施の態様において、十分に接合するように、焼成は、接合する面を加圧する加圧焼成によって行うことができる。加圧の圧力は、例えば０〜１ＭＰａの範囲とすることができる。
[Firing]
Firing can use conditions well-known as conditions of baking of a copper powder paste. The firing temperature can be, for example, in the range of 220 ° C to 300 ° C. In a preferred embodiment, the firing can be performed by pressure firing, in which the surfaces to be joined are pressurized, in order to achieve sufficient bonding. The pressure of pressurization can be, for example, in the range of 0 to 1 MPa.
［雰囲気］
焼成は、例えば非酸化性雰囲気下又は還元性雰囲気下で行うことができる。非酸化性雰囲気下とは、酸化性気体が含まれない又は低減された雰囲気をいう。還元性雰囲気は、雰囲気中にＣＯ、Ｈ2Ｓ、ＳＯ2、Ｈ2、ＨＣＨＯ、ＨＣＯＯＨ、Ｈ2Ｏ等の還元性気体が、０．５ｖｏｌ％以上、好ましくは１．０ｖｏｌ％以上で含まれる雰囲気をいう。還元性雰囲気としては、例えば大気圧の気体窒素及び気体水素を含む雰囲気を挙げることができる。
[atmosphere]
The firing can be performed, for example, in a non-oxidizing atmosphere or a reducing atmosphere. The non-oxidizing atmosphere refers to an atmosphere containing no or reduced oxidizing gas. The reducing atmosphere contains a reducing gas such as CO, H 2 S, SO 2 , H 2 , HCHO, HCOOH, H 2 O, etc. at 0.5 vol% or more, preferably 1.0 vol% or more. I say the atmosphere. As a reducing atmosphere, for example, an atmosphere containing gaseous nitrogen and gaseous hydrogen at atmospheric pressure can be mentioned.
［接合強度・熱劣化耐性］
接合強度は、実施例に記載のように、測定することができる。本発明の接合強度は、−４０℃〜＋２５０℃の間で温度を変化させて、それぞれの両端で３０分保持するサイクル（すなわち−４０℃に３０分静置した後に＋２５０℃に３０分静置するというサイクル）を、５００サイクル、及び１０００サイクル行った後の接合強度である。それぞれの温度条件のサイクル後に維持される接合強度を示すので、すなわち、温度変化に対する耐久性
、熱劣化耐性を示すものである。好適な実施の態様において、例えば初期接合強度（温度変化サイクル前の強度）は、２０ＭＰａ以上、３０ＭＰａ以上、４０ＭＰａ以上とすることができ、例えば２０〜５０ＭＰａの範囲とすることができる。好適な実施の態様において、温度変化サイクル１０００回後に、例えば初期接合強度の５０％以上、６０％以上の接合強度とすることができ、例えば初期接合強度の７０％〜９５％の範囲の接合強度とすることができる。好適な実施の態様において、温度変化サイクル１０００回後に、例えば初期接合強度の６０％以上、７０％以上の接合強度とすることができ、例えば初期接合強度の７５％〜９５％の範囲の接合強度とすることができる。
[Joint strength and thermal degradation resistance]
Bonding strength can be measured as described in the examples. In the bonding strength of the present invention, the temperature is changed between −40 ° C. and + 250 ° C., and each cycle is held for 30 minutes (ie, left at −40 ° C. for 30 minutes and then left at + 250 ° C. for 30 minutes) Bond strength) after 500 cycles and 1000 cycles. As it shows the bonding strength maintained after each temperature condition cycle, it shows the durability against temperature change and the thermal degradation resistance. In a preferred embodiment, for example, the initial bonding strength (the strength before the temperature change cycle) can be 20 MPa or more, 30 MPa or more, 40 MPa or more, and can be, for example, in the range of 20 to 50 MPa. In a preferred embodiment, the bonding strength can be, for example, 50% or more and 60% or more of the initial bonding strength after 1000 temperature change cycles, for example, a bonding strength in the range of 70% to 95% of the initial bonding strength. It can be done. In a preferred embodiment, the joint strength can be, for example, 60% or more and 70% or more of the initial joint strength after 1000 temperature change cycles, for example, a joint strength in the range of 75% to 95% of the initial joint strength. It can be done.
［半導体実装品］
上記半導体を銅ペーストで基材に接合する方法、該接合方法を含む製造方法、該製造方法によって製造されてなる半導体実装品、パワーモジュールもまた本発明の範囲内にある。
[Semiconductor mounted products]
A method of bonding the above semiconductor to a substrate with a copper paste, a manufacturing method including the bonding method, a semiconductor mounted product manufactured by the manufacturing method, and a power module are also within the scope of the present invention.
以下に実施例をあげて、本発明をさらに詳細に説明する。本発明は、以下の実施例に限定されるものではない。 The present invention will be described in more detail by way of the following examples. The present invention is not limited to the following examples.
［銅粉の調製］
Ｌビーカー内に亜酸化銅粉５０ｇとアラビアゴム０．２５ｇを３５０ｍＬの純水に分散させ、そこに体積比率２５％の希硫酸１００ｍＬを添加した。このスラリーからデカンテーション、水洗を繰り返し、Ｄ５０ ０．２μｍの銅粉２０ｇを得た。この銅微粒子２０ｇと、水溶性３級アミン１ｇを含む水溶液１００ｍＬを３００ｒｐｍで１時間混合した後、銅粉を回収した。その後、窒素中で７０℃で１時間乾燥させた後、解砕し、表面処理された銅粉を得た。
[Preparation of copper powder]
50 g of cuprous oxide powder and 0.25 g of gum arabic were dispersed in 350 mL of pure water in an L beaker, and 100 mL of dilute sulfuric acid having a volume ratio of 25% was added thereto. Decantation and water washing were repeated from this slurry to obtain 20 g of a copper powder having a D50 of 0.2 μm. After 20 g of this copper fine particle and 100 mL of an aqueous solution containing 1 g of a water-soluble tertiary amine were mixed at 300 rpm for 1 hour, a copper powder was recovered. Thereafter, it was dried at 70 ° C. in nitrogen for 1 hour and then crushed to obtain a surface-treated copper powder.
［銅粉ペーストの調製］
前記銅粉、ターピネオール、アクリル樹脂を重量比率で８５％、１３．５％、１．５％となるように遊星ミキサーで混練した後、３本ロールに通して、試験に供するペーストを調整した。
[Preparation of copper powder paste]
The copper powder, terpineol, and acrylic resin were mixed by a planetary mixer so as to be 85%, 13.5%, and 1.5% by weight ratio, and then passed through three rolls to prepare a paste to be subjected to the test.
［基板への積層及びペーストによる接合］
厚み０．６ｍｍ、１５ｍｍ角のＳｉ3Ｎ4の両面に、厚み０．３ｍｍ、１３ｍｍ角のＣｕ板を共晶反応によって接合させたＤＣＢ基板を準備した。また、厚み０．１８ｍｍ、１．８５ｍｍ角のＳｉＣチップの接合面となる面にＣｕ、Ｃｒ、Ｔｉ、ＮｉＶ（Ｖ７ｗｔ％）、ＣｏＶ（（Ｖ７ｗｔ％））、Ｔａ、Ｎｂ、Ａｕ、Ａｇのターゲットを用いてスパッタリングにより各層を形成した。ＤＣＢ基板の片側銅板上に、前記手順で準備したペーストをスクリーン印刷で膜厚５０μｍ、５ｍｍ角となるように塗工し、大気中で１２０℃で１分乾燥させた。この塗膜上にスパッタリングで処理した面が向かい合うようにＳｉＣチップを載せ、２ｖｏｌ％Ｈ２を含むＮ２中で２５０℃、１０分間、０．４ＭＰａの圧力をかけて、ＳｉＣチップとＤＣＢ基板をペーストで接合させた。
[Lamination to substrate and bonding by paste]
A DCB substrate was prepared in which a 0.3 mm thick, 13 mm square Cu plate was bonded to both sides of a 0.6 mm thick, 15 mm square Si 3 N 4 by eutectic reaction. In addition, Cu, Cr, Ti, NiV (V 7 wt%), CoV ((V 7 wt%)), Ta, Nb, Au, Ag targets on the surface to be a bonding surface of a 0.18 mm thick, 1.85 mm square SiC chip The respective layers were formed by sputtering using The paste prepared in the above procedure was applied by screen printing to a film thickness of 50 μm, 5 mm square, on one side copper plate of the DCB substrate, and dried at 120 ° C. for 1 minute in the air. The SiC chip and the DCB substrate are pasted on this coating film by placing the SiC chip on opposite sides of the coated film and applying a pressure of 0.4 MPa for 10 minutes at 250 ° C. in N 2 containing 2 vol% H 2. It was made to join.
［接合強度試験］
接合した材料の接合強度の変化をサイクル試験で調査した。試料を、−４０℃に３０分静置した後に、＋２５０℃に３０分静置するというサイクルの試験を行った。サイクル試験前（表中では‘０回’と表記）、５００サイクル後、１０００サイクル後の接合強度を測定した。
[Joint strength test]
Changes in bonding strength of the bonded materials were investigated in a cycle test. The samples were subjected to a cycle test of leaving at −40 ° C. for 30 minutes and then leaving at + 250 ° C. for 30 minutes. Before cycle test (denoted as “0 times” in the table), after 500 cycles, bonding strength after 1000 cycles was measured.
［結果］
実施例１〜１０及び比較例１〜１０の処理の条件及び接合強度試験の結果を、表１にまとめて示す。
[result]
The conditions of the treatment of Examples 1 to 10 and Comparative Examples 1 to 10 and the results of the bonding strength test are summarized in Table 1.
実施例１〜１０は初期及び、１０００サイクル後の接合強度が十分に高い。一方、比較例１〜３、６〜１０では初期ですら十分な接合強度が得られなかった。比較例４、５では、初期の接合強度は高かったものの、５００サイクル後、１０００サイクル後の接合強度は大幅に低下した。 In Examples 1 to 10, the initial bonding strength and the bonding strength after 1000 cycles are sufficiently high. On the other hand, in Comparative Examples 1 to 3 and 6 to 10, sufficient bonding strength was not obtained even at the initial stage. In Comparative Examples 4 and 5, although the initial bonding strength was high, after 500 cycles, the bonding strength after 1000 cycles was significantly reduced.
本発明は、銅粉ペーストによって基材と接合することができて、十分な接合強度が得られ、繰り返し高温にさらされる条件下でも接合強度が維持できる半導体を提供する。本発明は産業上有用な発明である。 The present invention provides a semiconductor that can be bonded to a substrate by a copper powder paste, obtain sufficient bonding strength, and maintain bonding strength even under repeated exposure to high temperatures. The present invention is an industrially useful invention.
Claims (5)
接合材との接合面側に、最表層から順に、Ｃｕ又はＣｕ合金の層、Ｎｉ又はＮｉ合金の層、Ｃｒ、Ｎｂ、Ｔａ及びＣｏから選択された１種の金属の層を有する半導体を調製する工程、
調製された半導体の接合面を、銅粉ペーストによって基材に接合する工程、
を含む、半導体実装品を製造する方法。 A layer of one metal selected from Cr, Nb, Ta and Co, a layer of Ni or Ni alloy, a layer of Cu or Cu alloy are sequentially formed on the bonding surface side of the semiconductor by dry film formation method,
A semiconductor having a layer of Cu or Cu alloy, a layer of Ni or Ni alloy, and a layer of one kind of metal selected from Cr , Nb, Ta and Co on the bonding surface side with the bonding material in order from the outermost layer Preparing step,
Bonding the prepared semiconductor bonding surface to a substrate with a copper powder paste,
A method of manufacturing a semiconductor package including:
調製された半導体の接合面を、基材上に塗工された銅粉ペーストと接触させて焼成して、基材に接合する工程、又は
調製された半導体の接合面上に塗工された銅粉ペーストを、基材と接触させて焼成して、基材に接合する工程、
である、請求項１〜３のいずれかに記載の製造方法。 The step of bonding the prepared bonding surface of the semiconductor to a substrate with a copper powder paste,
A step of contacting the prepared semiconductor bonding surface with a copper powder paste coated on a substrate, baking it, and bonding it to the substrate, or copper coated on the prepared semiconductor bonding surface Baking the powder paste in contact with the substrate and bonding it to the substrate,
The manufacturing method according to any one of claims 1 to 3, wherein
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