JPH0288788A - Gold plating solution - Google Patents
Gold plating solutionInfo
- Publication number
- JPH0288788A JPH0288788A JP23871688A JP23871688A JPH0288788A JP H0288788 A JPH0288788 A JP H0288788A JP 23871688 A JP23871688 A JP 23871688A JP 23871688 A JP23871688 A JP 23871688A JP H0288788 A JPH0288788 A JP H0288788A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- ions
- gold plating
- plating solution
- plating soln
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010931 gold Substances 0.000 title claims abstract description 46
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 46
- 238000007747 plating Methods 0.000 title claims abstract description 46
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- -1 gold (I) ions Chemical class 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 3
- KAQBNBSMMVTKRN-UHFFFAOYSA-N 2,4,6-trinitrobenzoic acid Chemical compound OC(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O KAQBNBSMMVTKRN-UHFFFAOYSA-N 0.000 abstract description 2
- WDMUXYQIMRDWRC-UHFFFAOYSA-N 2-hydroxy-3,4-dinitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1O WDMUXYQIMRDWRC-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- JCMBWDZBURXGMC-UHFFFAOYSA-N 1,3,6-trinitronaphthalene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC2=CC([N+](=O)[O-])=CC=C21 JCMBWDZBURXGMC-UHFFFAOYSA-N 0.000 description 1
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UCHORLBOJMYECF-UHFFFAOYSA-N n-(2-hydroxyphenyl)-n-nitronitramide Chemical compound OC1=CC=CC=C1N([N+]([O-])=O)[N+]([O-])=O UCHORLBOJMYECF-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- IXHMHWIBCIYOAZ-UHFFFAOYSA-N styphnic acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(O)=C1[N+]([O-])=O IXHMHWIBCIYOAZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229950002929 trinitrophenol Drugs 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は有害なシアンイオンを含まない金めつき液に係
り、特に安定性に優れた金めつき液とこれを用いて製造
する電子部品に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a gold plating solution that does not contain harmful cyanide ions, and in particular to a gold plating solution with excellent stability and electronic components manufactured using the same. It is related to.
従来、金めつき液に関しては、金イオンの錯化剤として
有害なシアンイオンを用いる場合がほとんどであった。Conventionally, most gold plating solutions have used harmful cyanide ions as a complexing agent for gold ions.
かかる金めつき液の重大な欠点の一つは、錯化剤として
用いるシアンイオンが極めて毒性が強く、有害であるこ
とであり、この欠点を除くために、錯化剤を亜硫酸、チ
オ硫酸イオン等のイオウの酸素酸イオンとする金めつき
液が用いられて来たことも周知である。このような非シ
アン系の金めつき液の例はエレクトロケミカルバプリケ
ージ日ン社発行のゴールド ブレーティング テクノロ
ジー 第５２頁〜第５７頁（Ｄ、Ｇ、Ｆｏｕｌｋｅ、Ｇ
ｏｌｄ Ｐｒａｔｉｎｇ Ｔｅｃｈｎｏｌｏｇｙ、ｐ５
２−５７゜Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｐｕｂｌ
ｉｃａｔｉｏｎ （１９７４） ）に多く示されている
。One of the major drawbacks of such gold plating solutions is that the cyanide ions used as complexing agents are extremely toxic and harmful. It is also well known that gold plating solutions containing sulfur oxygen acid ions have been used. An example of such a non-cyanide gold plating solution is found in Gold Blating Technology, published by Electrochemical Bapricage Nikko, pp. 52-57 (D, G, Foulke, G.
old plating technology, p5
2-57゜Electrochemical Publ
(1974)).
しかし、イオウの酸素酸イオンな錯化剤とする金めつき
液では、錯化剤の熱力学的不安定性に起因する金イオン
の還元分解の対策がなされておらず、シアンイオンを錯
化剤とする金めつき液に比較して、液安定性が著しく劣
る問題があった。However, in gold plating solutions that use sulfur oxygen acid ions as a complexing agent, no measures have been taken to prevent the reductive decomposition of gold ions due to the thermodynamic instability of the complexing agent, and cyanide ions are used as the complexing agent. There was a problem in that the liquid stability was significantly inferior to that of the gold plating liquid.
本発明の目的は、イオウの酸素酸イオンを錯化剤とする
金めつき液において、液安定性を著しく向上する新規な
金めつき液を提供するにある。An object of the present invention is to provide a novel gold plating solution that uses sulfur oxygen acid ions as a complexing agent and has significantly improved solution stability.
さらに精密な配線や電極の形成が必須なエレクトロニク
ス分野においては、金めつき液が高価であることに加え
、従来の不安定な金めつき液を用いると著しく歩留りが
低下して製品価格を上昇する問題があった。このため、
本発明の他の目的は、液安定性を著しく向上した新規な
金めつき液を用いることにより、安価でかつ精度良い配
線板や半導体等の電子部品を提供するにある。Furthermore, in the electronics field, where the formation of precise wiring and electrodes is essential, gold plating solutions are expensive, and using conventional unstable gold plating solutions significantly reduces yields and increases product prices. There was a problem. For this reason,
Another object of the present invention is to provide electronic components such as wiring boards and semiconductors at low cost and with high precision by using a new gold plating solution with significantly improved liquid stability.
上記目的を達成するために、次のような金めつき液の組
成とする。すなわち、金（Ｉ）イオンの錯化剤として、
イオウの酸素酸イオンを用いる金めつき液において、芳
香族ニトロ化合物を安定剤として加えるものである。In order to achieve the above object, the composition of the gold plating solution is as follows. That is, as a complexing agent for gold (I) ions,
An aromatic nitro compound is added as a stabilizer to a gold plating solution that uses sulfur oxygen acid ions.
通常、金めつき液として用いる場合には、金（Ｉ）イオ
ンを１乃至２０ ｔ／ｌに対し、錯化剤を金イオンに対
し、２当量以上加える。ここに錯化剤として用いるイオ
ウの酸素酸イオンは、亜硫酸イオンおよび／又はチオ硫
酸イオンが好んで用いられる。Usually, when used as a gold plating solution, 1 to 20 t/l of gold (I) ions are added and a complexing agent is added in an amount of 2 or more equivalents to the gold ions. As the sulfur oxygen acid ion used as a complexing agent here, sulfite ion and/or thiosulfate ion are preferably used.
本発明に係る安定剤としての芳香族ニトロ化合物とは、
モノ、ジ、トリニトロ安息香酸、モノ。The aromatic nitro compound as a stabilizer according to the present invention is
Mono, di, trinitrobenzoic acid, mono.
ジニトロサリチル酸、ニトロフタル酸、モノ、ジ。Dinitrosalicylic acid, nitrophthalic acid, mono, di.
トリニトロフェノール、ジニトロアミノフェノール、モ
ノ、ジ、トリニトロベンゼン、モノシ、トリニトロナフ
タレン、モノ、ジオトリニトロナフトール、モノ、ジ、
トリニトロレゾルシノール等を代表とするニトロ化合物
もしくはその誘導体を示す、かかるニトロ化合物は、金
めつき液に溶解するため水溶性であることが好ましく、
その配合量は、金めつき液１を当り１ミリモル以上溶解
限度以内とすることが望ましい。trinitrophenol, dinitroaminophenol, mono, di, trinitrobenzene, monocy, trinitronaphthalene, mono, ditrinitronaphthol, mono, di,
The nitro compound represented by trinitroresorcinol or its derivatives is preferably water-soluble because it dissolves in the gold plating solution.
The blending amount is desirably 1 mmol or more per gold plating solution and within the solubility limit.
ただし、本発明のニトロ化合物は上記に限定されるもの
ではないことは強調されるべきである。However, it should be emphasized that the nitro compounds of the invention are not limited to the above.
さらに、本発明の金めつき液には、その用途に応じて、
金（Ｉ）イオン、金（Ｉ）イオンの錯化剤、芳香族ニト
ロ化合物の他に、他の成分を含む場合があり、これらも
本発明を何ら制限するものでないことはもちろんである
。Furthermore, the gold plating solution of the present invention may include, depending on its use,
In addition to the gold (I) ion, the gold (I) ion complexing agent, and the aromatic nitro compound, other components may be included, and it goes without saying that these do not limit the present invention in any way.
かかる他の成分の例としては、ＰＨ調整剤、ＰＨ援衝剤
、重金属イオンのマスキング剤、電位調整剤、イオン強
度調整剤等を挙げることができ、これらの使用に関して
は当該業者に周知である。Examples of such other components include PH adjusting agents, PH buffering agents, heavy metal ion masking agents, potential adjusting agents, ionic strength adjusting agents, etc., the use of which is well known to those skilled in the art. .
さらに、金を電気的に析出させる電解めっき液として用
いる場合のみに止まらず、無電的に析出させる無電解め
っき液として用いる場合にも、本発明はさらに有効であ
ることは強調されるべきである。かかる場合には、他の
成分として金（Ｉ）イオンの還元剤を必須成分として含
む必要があり、これに関しても当該業者に周知の還元剤
を用いることができる。Furthermore, it should be emphasized that the present invention is more effective not only when used as an electrolytic plating solution that deposits gold electrically, but also when used as an electroless plating solution that deposits gold electrolessly. . In such a case, it is necessary to include a reducing agent for gold (I) ions as an essential component, and in this regard, reducing agents well known to those skilled in the art can be used.
本発明の芳香族ニトロ化合物は、イオウの酸素酸イオン
が分解して生じる、金（Ｉ）イオンを還元する活性な中
間体に作用し、これを不活性化することで、めっき液が
自然に分解するのを防止するものである。かかる作用を
有するため、有害なシアンイオンを含まない金めつき液
で、液安定性を著しく向上することが可能になったので
ある。The aromatic nitro compound of the present invention acts on an active intermediate that reduces gold (I) ions, which is produced by the decomposition of sulfur oxygen acid ions, and inactivates it, so that the plating solution naturally changes. This prevents it from decomposing. Because of this effect, it has become possible to significantly improve the stability of a gold plating solution that does not contain harmful cyanide ions.
さらに、本発明の金めつき液を用いて半導体等の電子部
品に金めつきを施すと、作業の歩留りが著しく向上する
ため、かかる部品の製造を著しく容易にする。Further, when electronic parts such as semiconductors are plated with gold using the gold plating solution of the present invention, the production yield of the work is significantly improved, so that the manufacture of such parts is significantly facilitated.
以下に本発明の一実施例を説明する。 An embodiment of the present invention will be described below.
実施例１
次の組成の金めつき液をｖＩ４堅し、めっき液の安定性
を調べた。Example 1 A gold plating solution having the following composition was hardened to vI4, and the stability of the plating solution was investigated.
かかるめっき液はおよそ電流密度０．２乃至１、ＯｍＡ
／−で金を還元析出させることができる。作業温度は５
０乃至７０℃が好ましい。めっき液の不安定性は、めっ
き液が自己分解し、液中で金を還元析出する現象に顕著
に表れる。そこで、本発明に係る芳香族ニトロ化合物の
効果を調べるために、めっき液を６０℃で１００時間加
熱して、液中の金の沈澱の有無を判定した。Such a plating solution has a current density of approximately 0.2 to 1, OmA.
/- can reduce and precipitate gold. Working temperature is 5
0 to 70°C is preferred. The instability of a plating solution is clearly manifested in the phenomenon that the plating solution self-decomposes and gold is reduced and precipitated in the solution. Therefore, in order to investigate the effect of the aromatic nitro compound according to the present invention, the plating solution was heated at 60° C. for 100 hours, and the presence or absence of gold precipitation in the solution was determined.
この結果、第１図に示すように、芳香族ニトロ化合物を
含まない場合には、１００時間の放置で金めつき液が分
解し、金の沈澱を生じてしまうのに対し、本発明に係る
芳香族ニトロ化合物を含んだめっき液では沈澱を生じる
ことが全くなかった。As a result, as shown in FIG. 1, when the gold plating solution does not contain an aromatic nitro compound, the gold plating solution decomposes after being left for 100 hours and gold precipitates. The plating solution containing the aromatic nitro compound did not cause any precipitation.
かかる結果より、芳香族ニトロ化合物の分解抑制効果が
著しいものであることがわかった。These results revealed that the effect of inhibiting the decomposition of aromatic nitro compounds was remarkable.
さらに、亜硫酸イオンな錯化剤とする金めつき液に止ま
らず、他のイオウの酸素酸イオンとしてチオ硫酸イオン
もしくは亜硫酸イオンとチオ硫酸イオンの混合物などを
錯化剤として用いる場合においても、芳香族ニトロ化合
物の顕著な効果は、全くかわらないこともわかった。Furthermore, in addition to gold plating solutions that use sulfite ions as a complexing agent, aromatic It was also found that the significant effects of group nitro compounds were not changed at all.
実施例２
本発明の金めつき液を用いて、第２図に示すように半導
体に微細な突起電極１を形成した。かかる電極形成法は
当該業者には周知の方法であり、前工程を経たシリコン
ウェハ２の全面にバリア金属膜３を形成した後、所定部
を７オトレジスト（図示しない）でマスキングする。次
でこのウェハに、本発明の金めつき液を用いて２５μｍ
厚の金めつきを施した後、レジストを除去し、不要なバ
リア金属６を溶解して突起電極１を形成した。かかる突
起電極１は、パシベーション層４で保護されたアルミ配
線５の所定部に設けられ、外部回路との接続に利用され
ることも当該業者には周知である。Example 2 Using the gold plating solution of the present invention, fine protruding electrodes 1 were formed on a semiconductor as shown in FIG. Such an electrode forming method is well known to those skilled in the art, and after forming the barrier metal film 3 on the entire surface of the silicon wafer 2 which has undergone the previous step, predetermined portions are masked with a 7-photoresist (not shown). Next, this wafer was coated with a 25 μm layer using the gold plating solution of the present invention.
After applying thick gold plating, the resist was removed and unnecessary barrier metal 6 was dissolved to form protruding electrodes 1. It is well known to those skilled in the art that such a protruding electrode 1 is provided at a predetermined portion of an aluminum wiring 5 protected by a passivation layer 4 and is used for connection with an external circuit.
かかる突起電極形成においては、電極の寸法が小になれ
ばなるほど本発明の金めつき液はその著しい液安定性に
より、極めて良好な生産性を発揮することがわかった。In the formation of such protruding electrodes, it has been found that the smaller the size of the electrode, the more excellent the productivity of the gold plating solution of the present invention is due to its remarkable solution stability.
その最も好ましい電極寸法はおよそ８０μｍ以下である
。The most preferred electrode size is approximately 80 μm or less.
本発明によれば、無害でかつ安定性に優れた金めつき液
を工業的に利用できるようになり、その経済効果には測
り知れないものがある。According to the present invention, a gold plating solution that is harmless and has excellent stability can be used industrially, and its economic effects are immeasurable.
第１図は本発明の一実施例の効果を示す表示図、第２図
は本発明の金めつき液を用いて形成した、半導体装置の
突起電極部分の断面図である。
１・・・突起電極、２・・・シリコンウェハ、３・・・
ドリア金属層、４・・・パシベーション層、５・・・ア
ルミ配線。FIG. 1 is a diagram showing the effects of an embodiment of the present invention, and FIG. 2 is a sectional view of a protruding electrode portion of a semiconductor device formed using the gold plating solution of the present invention. 1... Projection electrode, 2... Silicon wafer, 3...
Doria metal layer, 4... passivation layer, 5... aluminum wiring.
Claims (1)
とする金めっき液において、芳香族ニトロ化合物を含ん
でなることを特徴とする金めっき液。1. A gold plating solution containing gold (I) ions and sulfur oxygen acid ions as essential components, which is characterized by containing an aromatic nitro compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23871688A JPH0288788A (en) | 1988-09-26 | 1988-09-26 | Gold plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23871688A JPH0288788A (en) | 1988-09-26 | 1988-09-26 | Gold plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0288788A true JPH0288788A (en) | 1990-03-28 |
Family
ID=17034206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23871688A Pending JPH0288788A (en) | 1988-09-26 | 1988-09-26 | Gold plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0288788A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010024099A1 (en) * | 2008-08-25 | 2010-03-04 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Hard gold plating liquid |
| JP2011012314A (en) * | 2009-07-02 | 2011-01-20 | Ne Chemcat Corp | Gold plating bath for forming electrode and method for forming electrode by using the same |
| JP2014139348A (en) * | 2008-08-25 | 2014-07-31 | Electroplating Eng Of Japan Co | Hard gold-based plating solution |
-
1988
- 1988-09-26 JP JP23871688A patent/JPH0288788A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010024099A1 (en) * | 2008-08-25 | 2010-03-04 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Hard gold plating liquid |
| JP2010077527A (en) * | 2008-08-25 | 2010-04-08 | Electroplating Eng Of Japan Co | Liquid for hard gold plating |
| JP2014139348A (en) * | 2008-08-25 | 2014-07-31 | Electroplating Eng Of Japan Co | Hard gold-based plating solution |
| JP2011012314A (en) * | 2009-07-02 | 2011-01-20 | Ne Chemcat Corp | Gold plating bath for forming electrode and method for forming electrode by using the same |
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