JP2005054267A - Electroless gold plating method - Google Patents
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- 238000007747 plating Methods 0.000 title claims abstract description 169
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 118
- 239000010931 gold Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 166
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 83
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 31
- 239000004020 conductor Substances 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 19
- 230000002829 reductive effect Effects 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims description 23
- 229910000679 solder Inorganic materials 0.000 abstract description 69
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005476 soldering Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 21
- 238000001994 activation Methods 0.000 description 17
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 13
- 229910001096 P alloy Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000006073 displacement reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 239000002344 surface layer Substances 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- -1 Organic acid salt Chemical class 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910000521 B alloy Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- PQIJHIWFHSVPMH-UHFFFAOYSA-N [Cu].[Ag].[Sn] Chemical compound [Cu].[Ag].[Sn] PQIJHIWFHSVPMH-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/11—Manufacturing methods
Abstract
Description
本発明は、無電解金めっき処理方法に関し、特に、導体回路へ形成したニッケル系下地めっき上に無電解金めっき処理を行い、該ニッケル系下地めっき及び金めっきと、半田との接合をして導体回路と半田との電気的な接続を確保した場合における、半田の剥離現象を有効に防止することが可能となる無電解金めっき処理方法に関する。 The present invention relates to an electroless gold plating method, in particular, an electroless gold plating process is performed on a nickel-based undercoat formed on a conductor circuit, and the nickel-based undercoat and gold plating are joined to solder. The present invention relates to an electroless gold plating method capable of effectively preventing a solder peeling phenomenon when electrical connection between a conductor circuit and solder is ensured.
近年、超高集積回路素子のパッケージとして、超小型で且つ超多ピン化に対応したＣＳＰ（Chip Scale Package）やＢＧＡ（Ball Grid Array）等の超小型半導体パッケージの開発が盛んに行われている。 In recent years, development of ultra-small semiconductor packages such as CSP (Chip Scale Package) and BGA (Ball Grid Array), which are ultra-small and compatible with ultra-high pin count, has been actively conducted as ultra-high integrated circuit device packages. .
この超小型半導体パッケージの一つであるＢＧＡでは、プリント配線基板等のパッドとパッケージとを接続するために、ＢＧＡの搭載面に半田ボールと呼ばれる面格子端子が形成される。そして、この半田ボールを接続対象のパッドとに対向配置してリフロー処理をすることで、プリント配線基板等へ表面実装するのである。このＢＧＡのような超小型半導体パッケージは、近年の高密度、高信頼性の要求に対応できるものであり、広く普及している。 In the BGA, which is one of the ultra-small semiconductor packages, surface lattice terminals called solder balls are formed on the BGA mounting surface in order to connect a pad such as a printed wiring board and the package. Then, the solder balls are disposed opposite to the pads to be connected and subjected to a reflow process to be surface-mounted on a printed wiring board or the like. An ultra-small semiconductor package such as BGA can meet the recent demands for high density and high reliability, and is widely used.
ところで、このＢＧＡの半田ボールは、ＢＧＡの搭載面側に露出した金めっき部分へ接合されるのが一般的である。ＢＧＡは、半導体素子と接続された導体回路、例えば、銅などの金属で形成された導体回路を備えており、それに半田ボールを接続する必要がある。そして、この半田ボールを接合する部分の金めっき処理としては、通常、無電解金めっき処理が採用されている。 By the way, this BGA solder ball is generally joined to a gold-plated portion exposed on the BGA mounting surface side. The BGA includes a conductor circuit connected to a semiconductor element, for example, a conductor circuit formed of a metal such as copper, and a solder ball needs to be connected thereto. And as a gold plating process of the part which joins this solder ball, the electroless gold plating process is normally employ | adopted.
ここで、ＢＧＡの半田ボールについての形成工程を、図１に示すＢＧＡの搭載面側の一部分を拡大した概略断面図を参照しながら説明する。まず、ＢＧＡの導体回路１表面の一部には、厚み３〜１０μｍのニッケル系下地めっき２が無電解めっき処理される。また、その周囲はレジスト３により被覆されている。そして、このニッケル系下地めっき２上に、０．０１〜０．２０μｍ厚みの金めっき４を形成する無電解金めっき処理が行われる。ＢＧＡの半田ボール５は、この金めっき４及びニッケル下地めっき２の部分へ接合される。このようにして、ＢＧＡの搭載面側に複数の面格子端子としての半田ボール５を備えたものが製造される（例えば特許文献１参照）。
Here, a process of forming a BGA solder ball will be described with reference to an enlarged schematic cross-sectional view of a part of the BGA mounting surface shown in FIG. First, a nickel-based
このＢＧＡは、高密度、高信頼性を実現できる表面実装に好適なものとして広く普及しているものであるが、更なる小型、多ピン化に対応したパッケージとしての開発が進行しており、その特性要求も従来にまして非常に高いレベルのものとなっている。また、最近は環境問題の配慮から、半田材料として鉛フリー半田を用いることが多くなっており、錫−銀系、錫−亜鉛系等の種々の鉛フリー半田が使用されている。そのため、ＢＧＡの製造の際に鉛フリー半田を使用する場合にあっては、従来の錫−鉛系半田材料と同様な特性を実現することが必要となる。 This BGA is widely used as a surface mountable one that can achieve high density and high reliability, but development as a package that supports further miniaturization and increased pin count is in progress. The characteristic requirements are also at a very high level than before. Recently, in consideration of environmental problems, lead-free solder is often used as a solder material, and various lead-free solders such as tin-silver and tin-zinc are used. Therefore, when lead-free solder is used in the manufacture of BGA, it is necessary to realize the same characteristics as those of conventional tin-lead solder materials.
ＢＧＡにおいては、図１で説明したようにその搭載面側に半田ボールを形成する場合、ＢＧＡの導体回路表面にニッケル系下地めっきをし、その上に置換による金めっき処理を行うことが、一般的に行われている。しかしながら、近年、このような無電解金めっき処理方法により製造したＢＧＡにリフロー処理を行うと、半田／ニッケル界面の剥離現象を生じることが指摘され始めたのである。特に、近年の過酷なリフロー処理条件に曝される場合や鉛フリー半田を使用している場合では、半田／ニッケル界面の剥離現象が顕著になる傾向が指摘され、その改善を強く求められているのが現状である。 In the case of BGA, when solder balls are formed on the mounting surface side as described in FIG. 1, it is common to perform nickel-based base plating on the conductor circuit surface of BGA and to perform gold plating treatment on the surface thereof. Has been done. However, in recent years, it has begun to be pointed out that when a reflow treatment is performed on a BGA manufactured by such an electroless gold plating method, a peeling phenomenon of the solder / nickel interface occurs. In particular, when exposed to harsh reflow conditions in recent years or when using lead-free solder, the tendency of the solder / nickel interface delamination to be prominent has been pointed out, and there is a strong need for improvement. is the current situation.
本発明は、以上のような事情を背景になされたものであり、導体回路に形成したニッケル系下地めっきに無電解により金めっき処理を行う場合、該金めっき及びニッケル系下地めっきと半田との接合を行っても、半田／ニッケル界面の剥離現象を有効に防止できる無電解金めっき処理技術を提供することを目的とする。 The present invention has been made in the background as described above, and in the case of performing electroless gold plating on the nickel-based base plating formed on the conductor circuit, the gold plating, the nickel-based base plating, and the solder It is an object of the present invention to provide an electroless gold plating technique that can effectively prevent the peeling phenomenon of the solder / nickel interface even when bonding is performed.
本発明者らは、上記したＢＧＡの半田剥離現象について検討したところ、従来から行われている無電解金めっき処理方法では、ニッケル系下地めっきの組成が変化し、その結果、半田の接合特性を低下させているのではないかとの推測をした。このニッケル系下地めっきは、導体回路のバリアーとして形成されるものであるとともに、良好な半田／ニッケル接合が出来るように施されるものである。そして、この半田／ニッケル接合が良好になるように半田濡れ性を向上させるためにニッケル系下地めっき表面には、無電解金めっきとして置換金めっきが施される。 The present inventors examined the solder peeling phenomenon of the above-mentioned BGA. In the conventional electroless gold plating method, the composition of the nickel-based undercoating was changed, and as a result, the solder bonding characteristics were improved. I guessed that it was decreasing. This nickel base plating is formed as a barrier for the conductor circuit, and is applied so as to achieve good solder / nickel bonding. Then, in order to improve the solder wettability so that the solder / nickel bonding is good, the nickel base plating surface is subjected to substitution gold plating as electroless gold plating.
このようにニッケル系下地めっきに対して置換金めっき処理を行うと、ニッケルと金とが置換反応することによりニッケル系下地めっき表面に金が析出することになるが、この置換現象の結果、ニッケル系下地めっき表層では、ニッケルの酸化溶出が起こる。また、無電解ニッケル−リン合金めっき或いはニッケル−ホウ素合金めっきなどの場合は、ニッケルが溶出することにより、ニッケルに対するリンやホウ素の濃度が相対的に高くなる状態が生じるものと考えられる。このことを図１の拡大図である図２を参照して説明すると、置換金めっき処理を行った結果、ニッケル−リン合金めっき或いはニッケル−ホウ素合金めっき等のニッケル系下地めっき２の断面で見ると、ニッケル系下地めっき２の表層側にリンやホウ素等が相対的に高濃度となった部分２１が形成され、その下方側ではニッケルに対するリンやホウ素等の相対濃度が低い部分２２が形成されるのである。
When the substitutional gold plating treatment is performed on the nickel-based undercoating as described above, gold is deposited on the surface of the nickel-based underplating due to a substitution reaction between nickel and gold. In the surface layer of the system base plating, oxidation elution of nickel occurs. Further, in the case of electroless nickel-phosphorus alloy plating or nickel-boron alloy plating, it is considered that a state in which the concentration of phosphorus or boron relative to nickel becomes relatively high due to elution of nickel. This will be described with reference to FIG. 2 which is an enlarged view of FIG. 1. As a result of the substitution gold plating treatment, it is seen in a cross section of a nickel-based
そして、このような状態となったニッケル系下地めっき上の置換金めっきの表面に、半田を接合し、その後リフロー処理による熱履歴がＢＧＡに加えられると、リンやホウ素が相対的に高濃度となったニッケル系下地めっきの表層部分において剥離現象が生じ、半田の接合不良を生じさせると考えられるのである。特に、熱履歴の条件が厳しい場合には、このリンやホウ素が相対的に高濃度となったニッケル系下地めっきの表層部分の存在やニッケル系下地めっき表層部の酸化が、半田の剥離現象の大きな要因と本発明者らは推測した。 And when solder is joined to the surface of the displacement gold plating on the nickel-based undercoating that has been in such a state, and then a thermal history due to the reflow treatment is added to the BGA, phosphorus and boron have a relatively high concentration. It is thought that a peeling phenomenon occurs in the surface layer portion of the nickel-based base plating thus formed, resulting in poor solder joints. In particular, when the conditions of the thermal history are severe, the presence of the surface layer portion of the nickel-based undercoating with a relatively high concentration of phosphorus and boron and the oxidation of the nickel-based undercoating surface layer cause solder delamination. The present inventors speculated that this was a major factor.
このような考察の結果、本発明者らは、ＢＧＡを製造する際に、ニッケル系下地めっきの組成変化が生じない金めっき処理方法、即ち、ニッケル系下地めっきに、置換反応によるニッケル系下地めっき表層の酸化溶出を極力抑制し、リンやホウ素等が相対的に高濃度となる状態及びニッケル系下地めっき表面層部の酸化を生じさせない無電解金めっき方法について検討した。 As a result of such considerations, the inventors of the present invention have proposed a gold plating method that does not cause a change in composition of the nickel-based undercoating when manufacturing the BGA, that is, a nickel-based undercoating by a substitution reaction in the nickel-based undercoating. An electroless gold plating method that suppresses oxidation elution of the surface layer as much as possible, and does not cause oxidation of the surface layer portion of the nickel-based undercoating and a state in which phosphorus, boron, and the like are at a relatively high concentration was studied.
そこで、まず、このニッケル系下地めっきに、置換反応によるニッケルの酸化溶出を抑え、リンやホウ素等が相対的に高濃度となる部分を形成しない手法の一つとして、本発明者らは置換金めっき処理を行わないで金めっき処理することを考えた。つまり、ニッケル系下地めっき表面に電解金めっき処理をすることにより金めっきを形成するのである。この電解金めっき処理を採用したＢＧＡについて、半田の剥離現象を確認したところ、従来の無電解金めっき処理方法で生じた剥離現象は全く見られなかった。しかしながら、現在行われているＢＧＡの製造工程においては、電解金めっき処理を採用することが全く不可能ではないにしても、そのために必要となる製造設備の大幅な変更、或いはＢＧＡ自体の設計変更を伴うことになり、現状においては電解金めっき処理方法を採用し得ないという結論に至った。 Therefore, first, as one of the methods for suppressing the nickel elution due to the substitution reaction and not forming a portion with a relatively high concentration of phosphorus, boron, etc., in the nickel-based undercoating, the present inventors have used substitution gold. The gold plating process was considered without performing the plating process. That is, gold plating is formed by performing electrolytic gold plating treatment on the nickel base plating surface. When the peeling phenomenon of the solder was confirmed for the BGA adopting this electrolytic gold plating treatment, no peeling phenomenon caused by the conventional electroless gold plating treatment method was found. However, in the current manufacturing process of BGA, even if it is not impossible to adopt electrolytic gold plating, it is possible to make a major change in manufacturing equipment or design change of BGA itself. Therefore, the present inventors have concluded that the electrolytic gold plating method cannot be adopted in the present situation.
そのため、本発明者らは、既存のＢＧＡ製造設備でも対応可能な方法をさらに検討した結果、本発明を想到するに至った。まず、第一の本発明として、導体回路上にニッケル系下地めっき処理をし、該ニッケル系下地めっき上に無電解金めっきをする無電解金めっき処理方法において、前記ニッケル系下地めっき処理後、該ニッケル系下地めっき表面を金触媒活性化処理又はパラジウム触媒活性化処理をし、還元金めっき処理を行うものとした。 For this reason, the present inventors have come up with the present invention as a result of further studying a method that can be handled by existing BGA manufacturing facilities. First, as the first aspect of the present invention, in the electroless gold plating method in which a nickel-based undercoating treatment is performed on a conductor circuit and electroless gold plating is performed on the nickel-based undercoating, after the nickel-based undercoating treatment, The nickel-based base plating surface was subjected to a gold catalyst activation treatment or a palladium catalyst activation treatment to perform a reduced gold plating treatment.
この第一の本発明に係る無電解金めっき処理方法は、ニッケル系下地めっき表面を金又はパラジウムの触媒活性化処理することにより、半田の剥離現象が効果的に防止できることが判明したことによるものである。第一の本発明の無電解金めっき処理方法における金触媒活性化処理又はパラジウム触媒活性化処理は、従来の置換金めっきのように０．０１〜０．２０μｍ厚みの金めっきを析出させるものではなく、極薄い触媒金属の析出、即ち極薄い金又はパラジウムの析出を行う。本発明者らの研究によると、ニッケル系下地めっき表面への置換金めっきの厚みが０．０１μｍ以上になると、わずかに金色の表面を呈するようになり半田／ニッケル界面の剥離現象を生じ始めるのであるが、本発明の金又はパラジウムの触媒活性化処理での極薄い触媒金属の析出であれば、半田／ニッケル界面の剥離現象が生じなくなるのである。現在までの本発明者の研究によると、この金又はパラジウムの触媒活性化処理で析出させる金又はパラジウムの厚みは０．０１μｍ未満の薄い厚みの析出であれば、その後の還元金めっき処理も良好に行え、半田／ニッケル界面の剥離現象も生じないことを確認している。この第一の本発明に係る無電解金めっき処理方法では、金又はパラジウムの触媒活性化処理を行うことで、ニッケル系下地めっきの表層に従来のようなめっき厚みで金を置換析出させないので、ニッケル系下地めっき表層の酸化を抑制し、ニッケルに対するリンやホウ素等の濃度が相対的に高くなる部分を形成しないことが可能となる。 The electroless gold plating method according to the first aspect of the present invention is based on the fact that it has been found that the solder peeling phenomenon can be effectively prevented by subjecting the nickel base plating surface to a catalyst activation treatment of gold or palladium. It is. The gold catalyst activation treatment or palladium catalyst activation treatment in the electroless gold plating treatment method of the first aspect of the present invention does not deposit 0.01 to 0.20 μm thick gold plating as in the case of conventional displacement gold plating. And very thin catalytic metal deposition, i.e. very thin gold or palladium deposition. According to the study by the present inventors, when the thickness of the displacement gold plating on the nickel-based base plating surface becomes 0.01 μm or more, the gold surface slightly appears and the peeling phenomenon of the solder / nickel interface starts to occur. However, if the ultra-thin catalytic metal is deposited by the catalyst activation treatment of gold or palladium according to the present invention, the peeling phenomenon of the solder / nickel interface does not occur. According to the present inventors' research so far, if the thickness of gold or palladium deposited by the catalyst activation treatment of gold or palladium is a thin deposit of less than 0.01 μm, the subsequent reduction gold plating treatment is also good. It has been confirmed that there is no peeling phenomenon at the solder / nickel interface. In the electroless gold plating method according to the first present invention, by performing a catalyst activation treatment of gold or palladium, the surface layer of the nickel-based base plating does not cause substitution deposition of gold with a conventional plating thickness. It is possible to suppress oxidation of the nickel-based base plating surface layer and not to form a portion where the concentration of phosphorus, boron, or the like with respect to nickel is relatively high.
第一の本発明に係る無電解金めっき処理方法における金又はパラジウムの触媒活性化処理は、液の種類や処理条件等に特に制限はなく、要はニッケル系下地めっき表面に、極力、ニッケルの酸化溶出反応を抑制した状態で、還元金めっきの析出ができるように、金又はパラジウムの触媒金属を種付けすればよいものである。 The catalyst activation treatment of gold or palladium in the electroless gold plating method according to the first aspect of the present invention is not particularly limited with respect to the type of liquid and the treatment conditions. A catalytic metal such as gold or palladium may be seeded so that reduced gold plating can be deposited in a state where the oxidation elution reaction is suppressed.
また、第二の本発明に係る無電解金めっき処理方法は、還元パラジウムめっき処理をニッケル系下地めっきの表面に行い、その後無電解金めっき処理を行うものである。この方法によりＢＧＡを製造した場合、半田の剥離現象を効果的に防止できることが判明したのである。 In addition, the electroless gold plating method according to the second aspect of the present invention performs a reduction palladium plating process on the surface of the nickel base plating, and then performs an electroless gold plating process. It has been found that when a BGA is manufactured by this method, the solder peeling phenomenon can be effectively prevented.
第二の本発明の無電解金めっき処理方法における還元パラジウムめっき処理は、ニッケル系下地めっき表面を酸化溶出させないで、ニッケル系下地めっき表面に還元によりパラジウム金属を析出させ、その後無電解で金めっきを析出可能とするものである。本発明者らの研究によると、還元パラジウムめっき処理を行うと、従来の置換金めっき処理に比べて、半田／ニッケル界面の剥離現象が確実に防止されることを確認している。また、本発明において還元パラジウムめっき処理のパラジウムの被覆量は極わずかであることが好ましいことも確認している。その還元パラジウムめっき厚みは、０．０１〜０．５０μｍが望ましい。０．０１μｍ未満であると、無電解金めっき処理が良好に行えず、０．５０μｍを超えると、半田／ニッケル界面の剥離現象が生じやすくなる傾向となるからである。実用的には、０．０３〜０．１μｍが望ましい。 In the reduced palladium plating process in the electroless gold plating method of the second invention, the nickel-based undercoating surface is not oxidized and eluted, but palladium metal is deposited on the nickel-based undercoating surface by reduction, and then electrolessly gold-plated. Can be deposited. According to the study by the present inventors, it has been confirmed that when the reduced palladium plating process is performed, the peeling phenomenon of the solder / nickel interface is surely prevented as compared with the conventional displacement gold plating process. In the present invention, it is also confirmed that the amount of palladium covered by the reduced palladium plating treatment is preferably extremely small. The reduced palladium plating thickness is desirably 0.01 to 0.50 μm. If the thickness is less than 0.01 μm, the electroless gold plating process cannot be performed satisfactorily, and if it exceeds 0.50 μm, a peeling phenomenon at the solder / nickel interface tends to occur. Practically, 0.03-0.1 μm is desirable.
また、この第二の本発明における無電解金めっき処理方法では、還元パラジウムめっき処理後に行う無電解金めっきは、置換金めっき処理或いは還元金めっき処理のいずれを採用してもよいものである。本発明者等の研究によると、ニッケル系下地めっきの表面に還元パラジウムめっき処理をしておけば、その後の無電解金めっきが置換型或いは還元型であることに関わらず、半田／ニッケル界面の剥離現象を有効に防止できることを確認したからである。 In the electroless gold plating method according to the second aspect of the present invention, the electroless gold plating performed after the reduction palladium plating treatment may employ either a displacement gold plating treatment or a reduction gold plating treatment. According to the study by the present inventors, if the surface of the nickel-based base plating is subjected to reduction palladium plating, the solder / nickel interface can be obtained regardless of whether the subsequent electroless gold plating is a substitution type or a reduction type. This is because it has been confirmed that the peeling phenomenon can be effectively prevented.
本発明に係る無電解金めっき処理方法によれば、導体回路に形成したニッケル系下地めっきに無電解により金めっき処理を行っても、該金めっき及びニッケル系下地めっきと半田との接合はリフロー処理などの熱履歴を加えられても、半田／ニッケル界面での剥離現象を有効に防止することができる。特に、近年における過酷なリフロー処理条件が適用されるＢＧＡを製造する際に好適な無電解金めっき処理方法である。 According to the electroless gold plating method of the present invention, even if the nickel-based undercoating formed on the conductor circuit is subjected to electroless gold plating, the gold plating and the bonding between the nickel-based undercoating and the solder are reflowed. Even if a thermal history such as treatment is applied, the peeling phenomenon at the solder / nickel interface can be effectively prevented. In particular, it is an electroless gold plating method suitable for manufacturing a BGA to which recent severe reflow processing conditions are applied.
以下に、本発明の好ましい実施形態について説明する。 Hereinafter, preferred embodiments of the present invention will be described.
実施例１では、ニッケル系下地めっきに対して電解金めっき処理を行い、ＢＧＡを製造した場合の半田の剥離現象を調査した結果を示す。まず、実施例１−１として、図１で示すＢＧＡ基板のＣｕ（銅）の導体回路１上に、無電解によるニッケル−リン合金めっき２（厚み６μｍ）を施し、続いて電解金メッキ処理により約０．０５μｍの金めっき４を施した。そして、このニッケル−リン合金めっき２及び金めっき４の部分に、鉛フリー半田（錫−銀−銅の三元合金半田）を用いて半田ボール５を形成してＢＧＡを製造した。
Example 1 shows the result of investigating the solder peeling phenomenon when a BGA is manufactured by performing an electrolytic gold plating process on a nickel-based base plating. First, as Example 1-1, the electroless nickel-phosphorus alloy plating 2 (thickness 6 μm) is applied on the Cu (copper)
実施例１−２として、上記実施例１−１の無電解によるニッケル−リン合金めっきの代わりに電解により無光沢ニッケルめっき（厚み６μｍ）を下地として施し、その後の金めっき処理及び半田ボールの形成は実施例１−１と同様にしてＢＧＡを製造した。 As Example 1-2, instead of the electroless nickel-phosphorus alloy plating of Example 1-1 above, matte nickel plating (thickness 6 μm) is applied by electrolysis as a base, followed by gold plating treatment and formation of solder balls Produced BGA in the same manner as in Example 1-1.
さらに、従来例１としてＣｕ（銅）の導体回路１上に無電解によるニッケル−リン合金めっき２（厚み６μｍ）を施し、続いて置換金メッキ処理により約０．０５μｍの金めっき４を施した。その後、実施例１−１と同じ鉛フリー半田を用いて半田ボールを形成してＢＧＡを製造した。上述した各めっき処理の具体的な条件を以下に纏めて示す。
Further, as a conventional example 1, electroless nickel-phosphorus alloy plating 2 (thickness 6 μm) was applied on a Cu (copper)
・ 無電解ニッケル−リン合金めっき処理（実施例１−１、従来例１）
Ｎｉ ６ｇ／Ｌ
次亜リン酸Ｎａ ３０ｇ／Ｌ
ｐＨ ４．５〜５．０
液温 ９０℃
浸漬時間 １８ｍｉｎ
Electroless nickel-phosphorus alloy plating treatment (Example 1-1, conventional example 1)
Ni 6g / L
Hypophosphite Na 30g / L
pH 4.5-5.0
Liquid temperature 90 ℃
Immersion time 18min
・ 無光沢の電解ニッケルめっき処理（実施例１−２）
スルファミン酸Ｎｉ ７５ｇ／Ｌ（Ｎｉメタルとして）
ホウ酸 ３０ｇ／Ｌ
塩化ニッケル ６ｇ／Ｌ
ｐＨ ３．０〜４．５
液温 ５５℃
電流密度 ３Ａ／ｄｍ２
Matte electrolytic nickel plating treatment (Example 1-2)
Sulfamic acid Ni 75g / L (as Ni metal)
Boric acid 30g / L
Nickel chloride 6g / L
pH 3.0-4.5
Liquid temperature 55 ℃
Current density 3A / dm 2
・ 電解金めっき処理（実施例１−１〜２）
シアン化金カリウム ２ｇ／Ｌ
有機酸塩 ２００ｇ／Ｌ
ｐＨ ３．５〜４．０
液温 ５０℃
電流密度 ３Ａ／ｄｍ２
Electrolytic gold plating treatment (Examples 1-1 and 2)
Potassium cyanide 2g / L
Organic acid salt 200g / L
pH 3.5-4.0
Liquid temperature 50 ℃
Current density 3A / dm 2
・ 置換金めっき処理（従来例１）
シアン化金カリウム ４ｇ／Ｌ
キレート剤 ５０ｇ／Ｌ
有機酸塩 ２０ｇ／Ｌ
ｐＨ ４．０〜５．０
液温 ９０℃
・ Replacement gold plating treatment (conventional example 1)
Potassium cyanide 4g / L
Chelating agent 50g / L
Organic acid salt 20g / L
pH 4.0-5.0
Liquid temperature 90 ℃
以上のようにして得られた各ＢＧＡについて、リフロー処理の熱履歴を加え、半田ボールの半田プル強度測定を行った。 For each BGA obtained as described above, the heat history of the reflow process was added, and the solder pull strength of the solder ball was measured.
上述したリフロー処理条件の熱履歴を加えた各ＢＧＡについて、半田プル強度を測定することで、接合強度とその破壊モードを調査した。その結果を表１に示す。半田プル強度測定は、半田プル強度測定器（Ｄａｇｅ Ｂｏｎｄ ｔｅｓｔｅｒ ４０００、Ｄａｇｅ社製）を用いて半田ボールの接合強度を測定した。表１に示す破壊モード値は、半田プル強度測定後のサンプルを確認することで、全測定サンプル数に占める、界面剥がれ（ニッケル系下地めっき部分と半田ボールとの接合界面で剥がれたもの）が生じていたサンプル数の割合を算出した値である。 About each BGA which added the thermal history of the reflow processing conditions mentioned above, the joint strength and its failure mode were investigated by measuring solder pull strength. The results are shown in Table 1. The solder pull strength measurement was performed by measuring the solder ball bonding strength using a solder pull strength measuring device (Dage Bond tester 4000, manufactured by Dage). The failure mode values shown in Table 1 show that after peeling the solder pull strength measurement, the interface peeling (those peeled off at the bonding interface between the nickel-based base plating portion and the solder ball) occupying the total number of measurement samples. It is a value obtained by calculating the ratio of the number of samples that occurred.
表１を見ると判るように、ニッケル系下地めっきに電解金めっき処理を行うと、半田の剥離現象を防止できることが明確に判明した。このことより、半田の剥離現象がニッケル系下地めっきに置換金めっき処理を行うことが大きな要因であるということが推定された。 As can be seen from Table 1, it was clearly found that the solder peeling phenomenon can be prevented by performing electrolytic gold plating on the nickel base plating. From this, it was presumed that the solder peeling phenomenon was a major factor in performing the displacement gold plating treatment on the nickel base plating.
この実施例２では、ニッケル系下地めっきとして無電解によるニッケル−リン合金めっき（厚み６μｍ）を施したものに、本発明に係る無電解金めっき処理方法における金又はパラジウムの触媒活性化処理を施して還元金めっき処理（約０．０５μｍ）を行った場合、及び還元パラジウムめっき処理を施して還元金めっき処理（約０．０５μｍ）を行った場合によりＢＧＡを製造した場合の半田の剥離現象を調査した結果を示す。 In Example 2, the nickel-phosphorus alloy plating (thickness: 6 μm) that was electrolessly plated as the nickel-based base plating was subjected to a catalyst activation treatment of gold or palladium in the electroless gold plating method according to the present invention. When the reduced gold plating process (about 0.05 μm) is performed and when the reduced palladium plating process is performed and the reduced gold plating process (about 0.05 μm) is performed, the solder peeling phenomenon when the BGA is manufactured The survey results are shown.
まず、実施例２−１として、図１で示したＢＧＡのＣｕ（銅）の導体回路１上に無電解によるニッケル−リン合金めっき２（厚み６μｍ）を施し、続いて、金触媒液をニッケル−リン合金めっき表面に接触させることで触媒活性化処理を行った。その後、還元金めっき処理をすることにより、０．０５μｍの金めっき４を施した。そして、実施例１と同様な半田ボールを形成してＢＧＡを製造した。尚、この際の還元金めっきの処理条件は実施例１と同様である。
First, as Example 2-1, electroless nickel-phosphorus alloy plating 2 (thickness 6 μm) was applied on the BGA Cu (copper)
実施例２−２として、上記実施例２−１の金触媒液による触媒活性化処理の代わりに、パラジウム触媒液を接触することで触媒活性化処理した。その後の還元金めっき処理及び半田ボールの形成は実施例２−１と同様にしてＢＧＡを製造した。 As Example 2-2, instead of the catalyst activation treatment with the gold catalyst solution of Example 2-1 above, the catalyst activation treatment was performed by contacting the palladium catalyst solution. Subsequent reduction gold plating treatment and solder ball formation were carried out in the same manner as in Example 2-1, to produce BGA.
実施例２−３として、図１で示したＢＧＡのＣｕ（銅）の導体回路１上に無電解によるニッケル−リン合金めっき２（厚み６μｍ）を施し、続いて、還元パラジウムめっきをニッケル−リン合金めっき表面に施した。その後、還元金めっき処理をすることにより、０．０５μｍの金めっき４を施した。そして、実施例１と同様な半田ボールを形成してＢＧＡを製造した。尚、この際の還元金めっきの処理条件は実施例２と同様である。
As Example 2-3, electroless nickel-phosphorus alloy plating 2 (thickness 6 μm) was applied on the BGA Cu (copper)
実施例２−４として、図１で示したＢＧＡのＣｕ（銅）の導体回路１上に無電解によるニッケル−リン合金めっき２（厚み６μｍ）を施し、続いて、還元パラジウムめっきをニッケル−リン合金めっき表面に施した。その後、置換金めっき処理をすることにより、０．０５μｍの金めっき４を施した。そして、実施例１と同様な半田ボールを形成してＢＧＡを製造した。尚、この際の置換金金めっきの処理条件は上記従来例１と同様である。
As Example 2-4, electroless nickel-phosphorus alloy plating 2 (thickness 6 μm) was applied on the BGA Cu (copper)
・ 金触媒液による触媒活性化処理（実施例２−１）
シアン化金カリウム ４ｇ／Ｌ
キレート剤 ７０ｇ／Ｌ
還元剤 １ｇ／Ｌ
ｐＨ ４．０
液温 ５５℃
浸漬時間 １ｍｉｎ
-Catalyst activation treatment with gold catalyst solution (Example 2-1)
Potassium cyanide 4g / L
Chelating agent 70g / L
Reducing agent 1g / L
pH 4.0
Liquid temperature 55 ℃
・ パラジウム触媒液による触媒活性化処理（実施例２−１）
ジニトロジアミンパラジウム ２５ ｍｇ／Ｌ（Ｐｄメタルとして）
ｐＨ ７．０
液温 ３０℃
浸漬時間 １ｍｉｎ
Catalyst activation treatment with palladium catalyst solution (Example 2-1)
Dinitrodiamine palladium 25 mg / L (as Pd metal)
pH 7.0
Liquid temperature 30 ℃
・還元パラジウムめっき処理（実施例２−３、２−４）
Ｐｄ １ｇ／Ｌ
アンモニア水 ３０ｇ／Ｌ
ホウ酸 ４０ｇ／Ｌ
無機酸塩 １１０ｇ／Ｌ
ｐＨ ８．０
液温 ５３℃
Reduction palladium plating treatment (Examples 2-3 and 2-4)
Pd 1g / L
Ammonia water 30g / L
Boric acid 40g / L
Inorganic acid salt 110g / L
pH 8.0
Liquid temperature 53 ℃
・還元金めっき処理（実施例２−１〜３）
シアン化金カリウム ５ｇ／Ｌ
水酸化カリウム ９ｇ／Ｌ
水素化ホウ素ナトリウム １５ｇ／Ｌ
ｐＨ １３．０
液温 ７０℃
浸漬時間 １ｍｉｎ
-Reduction gold plating treatment (Examples 2-1 to 3)
Potassium cyanide 5g / L
Potassium hydroxide 9g / L
Sodium borohydride 15g / L
pH 13.0
Liquid temperature 70 ℃
以上のようにして得られた各ＢＧＡをについて、実施例１で説明したリフロー処理の熱履歴を加え、半田ボールの半田プル強度測定を行った。リフロー処理条件、半田プル強度測定については、実施例１と同じであるため説明を省略する。各実施例のＢＧＡにおける、接合強度とその破壊モードの測定結果を表２に示す。 For each BGA obtained as described above, the thermal history of the reflow processing described in Example 1 was added, and the solder pull strength measurement of the solder balls was performed. Since the reflow processing conditions and the solder pull strength measurement are the same as those in the first embodiment, the description thereof is omitted. Table 2 shows the measurement results of the bonding strength and the fracture mode in the BGA of each example.
表２を見ると判るように、ニッケル系下地めっきに対して、触媒活性化処理を行うと、半田の剥離現象を防止できることが判明した。また、本発明の無電解めっき処理方法における還元パラジウムめっき処理を行うと、その後の無電解金めっきの種類、即ち還元金めっき処理或いは置換金めっき処理に関わらず、触媒活性化処理の場合と同様に、半田の剥離現象を効果的に防止できることが判明した。 As can be seen from Table 2, it has been found that when the catalyst activation treatment is performed on the nickel base plating, the solder peeling phenomenon can be prevented. Further, when the reduced palladium plating treatment in the electroless plating treatment method of the present invention is performed, it is the same as in the case of the catalyst activation treatment regardless of the type of subsequent electroless gold plating, that is, the reduced gold plating treatment or the displacement gold plating treatment. In addition, it has been found that the solder peeling phenomenon can be effectively prevented.
１ 導体回路
２ ニッケル系下地めっき
３ レジスト
４ 金めっき
５ 半田ボール
1
Claims (2)
前記ニッケル系下地めっき処理後、該ニッケル系下地めっき表面を金触媒活性化処理又はパラジウム触媒活性化処理をし、還元金めっき処理を行うことを特徴とする無電解金めっき処理方法。 In the electroless gold plating method of performing nickel-based base plating on the conductor circuit and performing electroless gold plating on the nickel-based base plating,
An electroless gold plating method, wherein after the nickel-based undercoating treatment, the nickel-based undercoating surface is subjected to a gold catalyst activation treatment or a palladium catalyst activation treatment to perform a reduced gold plating treatment.
前記ニッケル系下地めっき処理後、ニッケル系下地めっき表面に還元パラジウムめっき処理を行い、その後無電解金めっき処理を行うことを特徴とする無電解金めっき処理方法。
In the electroless gold plating method of performing a nickel-based undercoating treatment on a conductor circuit and performing an electroless gold plating treatment on the nickel-based undercoating,
An electroless gold plating method, wherein after the nickel-based undercoating treatment, a reduced palladium plating treatment is performed on the nickel-based undercoating surface, and then an electroless gold plating treatment is performed.
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