JPS5980766A - Electroless ruthenium plating bath - Google Patents
Electroless ruthenium plating bathInfo
- Publication number
- JPS5980766A JPS5980766A JP19148682A JP19148682A JPS5980766A JP S5980766 A JPS5980766 A JP S5980766A JP 19148682 A JP19148682 A JP 19148682A JP 19148682 A JP19148682 A JP 19148682A JP S5980766 A JPS5980766 A JP S5980766A
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- solution
- bath
- plating bath
- salt
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
Description
【発明の詳細な説明】
本発明は、金属又は非金属材料の表面にルテニウムを無
電解メツ十するためのしドラジシ型メツ士浴に関し、そ
の目的とするところは、浴液の安定性が極めて優れ、ル
テニウムの利用率が高く、且つ操作温度が低い新規なメ
ツ中温を提供することにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a methane bath for electroless deposition of ruthenium onto the surface of metal or non-metallic materials, and an object of the present invention is to provide an extremely stable bath solution. It is an object of the present invention to provide a novel intermediate temperature device which is excellent, has a high utilization rate of ruthenium, and has a low operating temperature.
ルテニウムの被覆法はこれまで熱分解法によるものが主
流を占めていたために、金属、セラミックス等の耐熱材
料への処理に限られ、工業材料として汎用性の大きい高
分子材料、例えばイオン交換膜、合成樹脂等のプラスチ
ック材料には適用できなかった。Until now, the mainstream coating method for ruthenium has been thermal decomposition, which has limited its application to heat-resistant materials such as metals and ceramics. It could not be applied to plastic materials such as synthetic resins.
従って、上記プラスチック材料にも適用可能なルテニウ
ムの被覆法、特に化学メツ中法の開発が要望されている
が、現在までのところ、それに関する報告は非常に少な
い。Therefore, there is a demand for the development of a ruthenium coating method that can be applied to the above-mentioned plastic materials, especially a chemical coating method, but there have been very few reports regarding this to date.
また、ルテニウム以外の白金族金属の化学メツ中法には
、そのままルテニウムに応用できる方法は見当らない。Furthermore, there is no chemical method for platinum group metals other than ruthenium that can be directly applied to ruthenium.
本発明者は、先にルテニウムのアン三ン錯塩とシアル牛
ルアミシボランからなる浴液が使用し得ることを示した
（特開昭５７−１３４５８６号）。The present inventor has previously shown that a bath solution consisting of a ruthenium anthrine complex salt and sialoxalamisiborane can be used (Japanese Patent Application Laid-Open No. 134586/1986).
しかしながら、上記シアル＋ルアミンボラン型の浴液は
、好適なルテニウムメツ十が得られるが、メツ＋温度が
比較的高い（６０〜９０℃）ため適用可能なプラスチッ
クの範囲が狭くなる傾向があり、またルテニウムのアン
ミシ錯イオシの安定性が必ずしも良好ではないため浴液
中のルテニウムの利用率が充分でないという点で不満足
であった。However, although the above-mentioned sial + amine borane type bath liquid can obtain a suitable ruthenium metal, the range of applicable plastics tends to be narrowed because the metal + temperature is relatively high (60 to 90°C). Furthermore, the stability of the ruthenium amici complex iodine is not necessarily good, so the utilization rate of ruthenium in the bath liquid is unsatisfactory.
本発明者は、上記現状に鑑み、金属及び非金属双方の広
い範囲に適用出来、且つ浴液の安定性が高いルテニウム
の無電解メツ生温を開発する目的で特にヒドラジン型浴
液について研究したが、ルテニウムのア、：／ミシ錯塩
としドラ、；シの浴液はメツ＋が不完全で、浴液の自己
分解（沈殿等）が早く安定性が悪いため実用性に乏しい
ことが解った。In view of the above-mentioned current situation, the present inventor conducted research on hydrazine-type bath liquids in particular for the purpose of developing a ruthenium electroless wet bath that can be applied to a wide range of both metals and non-metals and has high bath liquid stability. However, it was found that the bath solution of the ruthenium A, :/Mish complex salt, Toshidora, ;C is not practical because the meth+ is incomplete and the bath solution undergoes rapid self-decomposition (precipitation, etc.) and poor stability. .
而して、本発明者は更に鋭意研究を続けた結果、ルテニ
ウムのイオン形態として特に従来使用されたことのない
ニド０ジルアン三シ錯イオシを選択し、還元剤としてヒ
ドラ、ｌ；シを組み合わせるときにはｐ ＩＩ Ｉ Ｑ
〜１３において極めて安定な浴液が得られること、更に
しドロ士シルアミシ塩を加えたときにはより一層安定性
を増すこと、これらのメツ生温は操作温度が低いため金
属は勿論広い範囲の非金属材料に好適に使用出来ること
、浴液が安定であるためヒト０士ジルアミン塩を加えな
いもので数週間以上、ヒト０士シルア″−シ塩を加えた
ものはその２〜３倍の期間自己分解することなく室温で
保存出来ること、及びルテニウムの利用率は９０％以上
と非常に高いことを見出し、本発明を完成するに至った
。Therefore, as a result of further intensive research, the present inventors selected the nido-0-ziluane trisiocomplex, which has never been used as an ionic form of ruthenium, and combined it with hydra, l; as a reducing agent. Sometimes p II I Q
-13, an extremely stable bath solution can be obtained, and furthermore, when Doroshicilamici salt is added, the stability is further increased, and since the operating temperature is low, it can be used not only for metals but also for a wide range of non-metals. Because the bath solution is stable, it can be used for several weeks or more without adding human oxysilamine salt, and for two to three times as long when adding human oxysilamine salt. They discovered that it can be stored at room temperature without decomposing, and that the utilization rate of ruthenium is extremely high at over 90%, leading to the completion of the present invention.
即ち本発明は、ルテニウムのニド０シルアシミシ錯塩及
びヒドラジンを含有し、ｐＨ１０〜１３であることを特
徴とするルテニウムの無電解メツ生温、並びにルテニウ
ムのニド０シルアンミシ錯塩、ヒドラジン及びヒドロ士
シルアミシ塩を含有し、ｐＨ１０〜１３であることを特
徴とするルテニウムの無電解メツ生温に係る。That is, the present invention provides an electroless raw temperature of ruthenium, which contains a ruthenium nido-0-cylamici complex salt and hydrazine, and has a pH of 10 to 13, and a ruthenium nido-0-cylamic acid complex salt, hydrazine, and a hydrazine salt. It relates to the electroless raw temperature of ruthenium, which contains ruthenium and has a pH of 10 to 13.
本発明において使用するルテニウムのニド０ジルアン、
：′Ｊ錯塩としては、（Ｒｕ （ＮＯ） （ＮＨ３）、
）Ｎ３（Ｘはハロゲン原子を表わす。以下同じ。）、
ＣＲｕ（ＮＯ）Ｃ０１１）ＣＮＩＩ、）４〕Ｘ２等のニ
ド０ジルアンミン錯塩を用いるか、或いはＮ２〔ＲｌＬ
（ＮＯ）Ｃｔ５〕（ＭはＮα、Ｋ、 Ｎ１１４等を表わ
す。以下同じ。）、ＭＣＲｔｔ（ＮＯ）Ｃｌ３（Ｎ２０
）〕、ＮＮ２ＲｌＬ（ＮＯ）（α０Ｃｔ４〕、〔ＲｔＬ
（＃０）Ｃ１３（Ｎ２０）２ 〕等のニド０シルハロゲ
ノ錯塩、Ｎ２〔Ｒｗ（ＮＯ）（０１１）（ＮＯ２）４〕
、〔ＲＬＬ（ＮＯ）（ＮＯ３）３（Ｎ２の、〕、〔Ｒｔ
Ｌ（ＮＯ）（Ｎ０２）（Ｎ０３）２（Ｎ２０）２〕等の
ニドＯシルニド０又はニド０シル硝酸錯塩、［Ｒｔｔ（
ＮＯ） （ＣＨ３ＣＯＯ）２）、Ｍ ［Ｒｕ、（ＮＯ）
（Ｃ１１３ＣＯＯ） ３（Ｎ２０）２］ 、Ｍ、 〔
Ｒｔｔ（ＮＯ） （０Ｈ）（Ｃ２０４）２〕、Ｎ２〔Ｒ
ｕ、（ＮＯ）（Ｃ２０４）２〕等のニド０シル有機酸錯
塩等をアン七ニア水中で加熱乃至煮沸してニド０シルア
シミシ錯塩を調製して用いる。Ruthenium nitride used in the present invention,
:'J complex salts include (Ru (NO) (NH3),
) N3 (X represents a halogen atom. The same applies hereinafter),
CRu(NO)C011)CNII, )4]X2 or the like, or use N2[RlL
(NO)Ct5] (M represents Nα, K, N114, etc. The same applies hereinafter), MCRtt(NO)Cl3 (N20
)], NN2RlL(NO)(α0Ct4), [RtL
(#0)C13(N20)2], etc. Nido-0-sylhalogeno complex salts, N2[Rw(NO)(011)(NO2)4]
, [RLL(NO)(NO3)3(N2's,], [Rt
L(NO)(N02)(N03)2(N20)2], nido-O-syl nido-0 or nido-0-syl nitrate complex salts, [Rtt(
NO) (CH3COO)2), M [Ru, (NO)
(C113COO) 3(N20)2] , M, [
Rtt(NO) (0H)(C204)2], N2[R
A nido-0-syl organic acid complex salt such as (NO) (C204)2] is heated or boiled in anhydrous water to prepare a nido-0-syl acid complex salt and used.
更に、実用的な処決として、上記化合物を使用せず、例
えば三塩化ルテニウム等のハロゲン化物、硝酸塩等のル
テニウム塩（ルテニウムが三価又は四価のもの。）と亜
硝酸塩（アルカリ金属塩等）とをアシ七ニア水中で加熱
乃至煮沸してニド０ジルアシ三シ錯塩を調製して用いて
も良い。この場合には、亜硝酸塩の使用量をルテニウム
塩１モルに対して通常２〜５′ｆニル程度とするのが良
い。亜硝酸塩が上記範囲より少ない場合にはニトロシル
アシ三シ錯塩が充分に生成しないので好ましくない。ま
た、上記範囲より多い場合には浴液中にＮＯ２イオシが
過剰に存在することになるが、過剰のＮＯイオンはルテ
ニウムの還元速度を遅らせ、また浴液中のルテニウムの
利用率を低下させるので好ましくない。Furthermore, as a practical solution, instead of using the above compounds, for example, halides such as ruthenium trichloride, ruthenium salts such as nitrates (ruthenium is trivalent or tetravalent), nitrites (alkali metal salts, etc.) ) may be heated or boiled in acetic acid water to prepare a nido-o-di-a-ci-tri-di-complex salt and use it. In this case, the amount of nitrite to be used is usually about 2 to 5'fnyl per mole of ruthenium salt. If the amount of nitrite is less than the above range, the nitrosyl acyl tricyclocomplex will not be sufficiently produced, which is not preferable. Furthermore, if the amount exceeds the above range, NO2 ions will be present in excess in the bath solution, but excessive NO ions will slow down the reduction rate of ruthenium and reduce the utilization rate of ruthenium in the bath solution. Undesirable.
本発明におけるルテニウムのニド０ジルアン三シ錯塩は
、上記のいずれの方法によって調製した場合においても
、浴液中の有効イオシ種は（−１？ｗ（ＮＯ）（ＯＨ）
（ＮＨ３）４〕２＋、（Ｒｕ（ＮＯ）（Ａ＃Ｊ３）、）
” 等ノニト０シルアンミシ錯イオシであるが、通常は
純粋組成ではなくこれらの混合液を成している。In the present invention, the ruthenium nido-0-diane trisulfide complex salt is prepared by any of the above methods, and the effective iodine species in the bath liquid is (-1?w(NO)(OH)).
(NH3)4]2+, (Ru(NO)(A#J3),)
Although it is a non-nito-ocyl-amicyl complex, it usually does not have a pure composition but is a mixture of these.
これらのニド０ジルアン三シ錯イオシはｐＨ１Ｏ〜１３
の液性でしドラジンと共存しても自己分解することはな
い。These nido-0-ziluane trisulfide complexes have a pH of 10 to 13.
It is a liquid and will not self-decompose even if it coexists with drazine.
本発明におけるしドラ、；シとしては、水溶液の状態で
しドラジシとなるもの、例えばヒドラジンの水和物、塩
酸塩、硫酸塩等が好適に使用できる。As hydrazine in the present invention, those which form hydrazine in an aqueous solution state, such as hydrazine hydrate, hydrochloride, sulfate, etc., can be suitably used.
また、本発明において、浴液をよシ一層安定化させるた
めに使用するしドロ士シルアミシ塩としては、水溶−性
の塩例えば塩酸塩、硫酸塩、硝酸塩等が好ましい。Further, in the present invention, as the dorothysylamide salt used to further stabilize the bath liquid, water-soluble salts such as hydrochloride, sulfate, nitrate, etc. are preferable.
本発明の浴液組成としては、ルテニウムのニドＤシルア
ンミシ錯塩をルテニウム濃度としてｌＯ〜３〜２ｘ１０
−”Ｍ／ｌ（０，１〜２０ｔ／ｌ）好ｉＬ＜ ｔｊ、
ｔＯ−３〜１０−”ｘ／ｌ （０，１〜ｔｏ ｔ／ｌ）
、 及ヒヒドラ、、；シを０．００３〜１．５Ｍ／ｌ
ｃ−水和物の場合、０．１５〜７５ ？／ｌ ）好まし
くは０．００３〜０．３ Ｍ／ｌ（−水和物の場合、０
．１５〜１５ ｆ／ｌ ）である。また、しドロ士シル
ア三ン塩を用いる場合の濃度は、ヒトＤ＋シルアＥｕト
Ｌ、テ０．００１４〜０．７ Ｍ／Ｌ（塩酸塩の場合、
０．１〜５０ ｆ／ｌ ）好ましくは０．００１４〜０
．０１４Ｍ／ｌ （塩酸塩の場合、０．１〜ｉｆ／４）
である。The bath solution composition of the present invention is such that the ruthenium concentration is 1O~3~2x10
-"M/l (0,1~20t/l) good iL<tj,
tO-3~10-"x/l (0,1~to t/l)
, and hydra, 0.003 to 1.5 M/l
For c-hydrates, 0.15-75? /l) Preferably 0.003 to 0.3 M/l (-in the case of hydrates, 0
．． 15-15 f/l). In addition, when using Shidoroshi Silua Triphosphate, the concentration is human D + Silua Eu to L, Te 0.0014 to 0.7 M/L (in the case of hydrochloride,
0.1-50 f/l) preferably 0.0014-0
．． 014M/l (0.1-if/4 in case of hydrochloride)
It is.
本発明においては上記組成の浴液を、アシ七ニア水又は
アルカリ性ｐＨ緩衝液によシ、ｐＨ１０〜１３好ましく
は！１〜１２の範囲に調製して使用する。In the present invention, the bath solution having the above composition is replaced with acetic acid water or an alkaline pH buffer solution, preferably with a pH of 10 to 13! The number is adjusted to a range of 1 to 12 before use.
ｐＨが１３以上になると還元速度が速くなり自己分解し
易くなる。またｐＨがｌＯよシ低いと還元速度が小さく
なりメツ牛時間が長くなる。しドロ十ジルアミンが５０
ｆ／を以上になるとメツ中層の成長を極端に抑えるの
で好ましくない。When the pH is 13 or higher, the reduction rate becomes faster and self-decomposition becomes easier. Furthermore, if the pH is lower than 1O, the reduction rate will be lower and the time required for feeding will be longer. Shidrodecadylamine is 50
If f/ is more than that, it is not preferable because the growth of the middle layer of the mets is extremely suppressed.
斯くして調製された本発明メツ牛浴に、予め活性化処理
を経た被メツ牛体を浸漬すると、室温〜６０℃程度好ま
しくは３５〜５０℃の温度で、接触的に還元反応が進行
し、ルテニウムのメツ牛層が成長する。メツ＋温度が室
温より低いとメツ＋は進行しにくくなる。またメツ＋温
度が６０℃を越えると自己分解が起こり始めると同時に
、析出したルテニウムの金属光沢はなくなシ水素を吸蔵
して黒色状（ルテニウム黒）になってメツ＋が進みにく
くなシ、又得られたメツ中層の導電性が悪くなる。When the body of a cow to be fed that has been previously subjected to an activation treatment is immersed in the thus prepared bath of the present invention, a reduction reaction proceeds catalytically at a temperature of about room temperature to 60°C, preferably 35 to 50°C. , the ruthenium metal layer grows. If the temperature is lower than room temperature, Met+ will be less likely to progress. Furthermore, when the temperature exceeds 60°C, self-decomposition begins to occur, and at the same time, the precipitated ruthenium loses its metallic luster and absorbs hydrogen, becoming black (ruthenium black), making it difficult for ruthenium to proceed. Furthermore, the conductivity of the resulting metsu middle layer becomes poor.
上記温度範囲内では、ルテニウム黒を生成することなく
、メツ中は良好に進行し、浴液中のルテニウムが９０チ
以上という高率に消費されるまで継続する。従って、本
発明メツ中温から析出するルテニウムの状態は他の錯イ
オン型温からの析出物に比べて、極めて良好な金属光沢
と導電性を示す。Within the above temperature range, the bathing process proceeds smoothly without producing ruthenium black and continues until the ruthenium in the bath liquid is consumed at a high rate of 90 or more. Therefore, the state of ruthenium precipitated from medium temperatures according to the present invention exhibits extremely good metallic luster and conductivity compared to other complex ion type precipitates from temperatures.
メツ中中にはルテニウムの析出と、窒素及び夕刊゛のア
シ七ニア、水素が副生ずる。ルテニウムの析出は被メツ
十体表面に選択的に起シ、器壁等への沈着はない。メツ
士時間は被メツ牛体の形状にもよるので一定ではないが
、例えば約３μｍのルテニウムメツ中層を得る場合の例
を述べれば２〜４時間という短時間である。Ruthenium is precipitated in the meth, and nitrogen, ash, and hydrogen are produced as by-products. Ruthenium precipitation occurs selectively on the surface of the body to be treated, and there is no deposition on the vessel walls. The time required for the treatment is not constant because it depends on the shape of the cow to be treated, but for example, in the case of obtaining a ruthenium meat layer of about 3 μm, it is a short time of 2 to 4 hours.
本発明のメツ生温においては、ルテニウムのニド０シル
アンミシ錯塩自体が浴液中で極めて安定であるため、被
メツ牛体が浸漬されない場合には、室温で数週間以上保
存しても自己分解することなく極めて優れた安定性を示
す。また、ヒドロ中ジルアミン塩が加わるとよシ一層安
定性を増して、上記条件で上記の２〜３倍の期間自己分
解することがない。In the wet temperature of the present invention, the nido-0-silamicium complex salt of ruthenium itself is extremely stable in the bath solution, so if the body of the meat to be treated is not immersed, it will self-decompose even if stored at room temperature for several weeks or more. It shows extremely excellent stability without any problems. Furthermore, when a hydrolyzed diylamine salt is added, the stability is further increased, and self-decomposition does not occur under the above conditions for a period of 2 to 3 times the above period.
本発明メツ中温が適用できる対象としては、金属、例え
ば銅、ニッケル、鉄、それらの合金、チタシ、タン、タ
ル等の電子部品あるいは電極材料等の工業材料等が挙げ
られる。また、アクリロニトリル−づタジエシースチレ
ン共重合体（ＡＢＳ）樹脂、ボリア三ド樹脂、カーボネ
ート樹脂等の合成樹脂、ガラス、セラミックス等、通常
の無電解メツ中が可能な材質に対して適用できる。さら
に本発明メツ平俗は、イオン交換膜等の高分子膜の膜面
にルテニウムを接合する浴液として特に好適である。こ
の様な接合体は、固体高分子電解質電解法に利用される
。Examples of objects to which the present invention can be applied include metals such as copper, nickel, iron, alloys thereof, electronic parts such as titanium, tan, and tar, and industrial materials such as electrode materials. Further, it can be applied to materials that can be processed in ordinary electroless metals, such as synthetic resins such as acrylonitrile-buttadiene styrene copolymer (ABS) resin, tri-borea resin, and carbonate resin, glass, and ceramics. Further, the present invention is particularly suitable as a bath liquid for bonding ruthenium to the membrane surface of a polymer membrane such as an ion exchange membrane. Such a conjugate is used in solid polymer electrolyte electrolysis.
いずれの場合も、被メツ士体については予め活性化処理
を行っておくのが好ましい。In either case, it is preferable to perform activation processing on the body to be treated in advance.
金属の場合は、表面清浄後、パラジウム、白金、０、；
ラム、ルテニウム、金、銀等の塩類水溶液に浸漬し、必
要ならば引続き水素化ホウ素塩水溶液等に浸漬還元処理
して活性化した後、本発明メツ生温に浸漬する。In the case of metals, after surface cleaning, palladium, platinum, 0;
The meat of the present invention is immersed in an aqueous salt solution of rum, ruthenium, gold, silver, etc., and if necessary, is subsequently activated by immersion reduction treatment in an aqueous boron hydride salt solution, etc., and then immersed in the raw temperature of the meat of the present invention.
高分子材料、ガラス、セラミックスの場合にも、通常、
これらの表面に銅、ニッケル等の化学メツ士を行なう場
合に利用されている表面親水化、増感処理、上記金属の
場合と同様の活性化処理を行った後、本°発明メツ生温
に浸漬する。Also in the case of polymeric materials, glasses, and ceramics, usually
After performing surface hydrophilic treatment, sensitization treatment, and activation treatment similar to those used for the above metals, which are used when chemical metals such as copper and nickel are applied to these surfaces, the present invention can be heated to lukewarm temperature. Soak.
また、高分子膜例えばイオン交換膜の場合は、表面粗化
した後まず金属塩（例えば、ルテニウムの塩）溶液を吸
着させ、ついで水素化ホウ素ナト以下、参考例及び実施
例を挙げて本発明を更に具体的に説明する。In addition, in the case of a polymer membrane, such as an ion exchange membrane, after roughening the surface, a metal salt (for example, ruthenium salt) solution is first adsorbed, and then a solution of borohydride is introduced. will be explained more specifically.
参考例 ｌ
ルテニウムのニトロシルアシミン錯塩溶液をっぎの方法
において作成した。Reference Example 1 A nitrosylacimine complex salt solution of ruthenium was prepared by the method described above.
Ａ。A.
（１１三塩化Ｊｌ／ テ： ’） ム（ＲｕＣ１ｙ、
・３ Ｈ２Ｃ） ２．６９（２） 亜硝酸ナトリ
ウム（ＮａＮＯ２）２．５ｆｆ３１ ：Ｐ ン’ｅ
： ７水 （２８％、以下同じ） ２０．０ｍ（
４）水 全ｉｔ ５００ ｍ１ｆｉ＋
を５０ｍ１の水に溶解し、塩酸数滴を加えた後、（２）
を少量づつ加えて煮沸し、さらにアシ七ニア水を加えて
煮沸まで加熱した後冷却し水で５００ｍＡ’とした。こ
の溶液１（１＋＋／は２ｏ■のルテニウムを含む。(11 Jl trichloride/ Te: ') Mu (RuC1y,
・3 H2C) 2.69 (2) Sodium nitrite (NaNO2) 2.5ff31 :P n'e
: 7 water (28%, same below) 20.0m (
4) Water total 500 m1fi+
After dissolving in 50ml of water and adding a few drops of hydrochloric acid, (2)
was added little by little and boiled, and then Acinannia water was added and heated to boiling, then cooled and adjusted to 500 mA' with water. This solution 1 (1++/) contains 2o■ of ruthenium.
Ｂ。B.
＋１１ 三塩化ルテニウム
２．６２（２） 亜硝酸ナトリウム
２．５ｆ（３） アン七ニア水
２０．Ｏｍ（４） しドロ＋シルア三
シ塩酸塩 １．０ｆ（５）水
全量 ５００１ｎＩ！（１）を５０ｍＡ’の水
に溶解し、塩酸数滴を加えた後、（２）を少量づつ加え
て煮沸させる。ついで（３）及び（４）を加えて再び加
熱して煮沸させた後、冷却し、水で５００ｍＡ！とした
。この溶液ＩＱｍは２０１ｒｐｙのルテニウムを含む。+11 Ruthenium trichloride
2.62(2) Sodium nitrite
2.5f (3) Annunia water
20. Om(4) Shidoro + Silua trishydrochloride 1.0f(5) Water
Total amount 5001nI! Dissolve (1) in 50 mA' water, add a few drops of hydrochloric acid, then add (2) little by little and boil. Next, (3) and (4) were added and heated again to boil, then cooled and heated to 500mA with water! And so. This solution IQm contains 201 rpy of ruthenium.
Ｃ２
ｆｌ ペクタクロ０ニド０シルルテニウムカリウム（
Ｋ２ＣＲｕ、（ＮＯ）Ｃｔ５’３ ） ３．
８ Ｆ（２） アシ七ニア水
２０ｍ１（３）シト０＋シルアミシ塩酸塩
１．Ｏｆ（４）水 全量 ５
００ｄｆｌ）及び（２）を加熱し煮沸させた後、（３）
を加え水で５００ｍ１とした。この溶液ＩＱｍ／は２０
■のルテニウムを含む。C2 fl pectachloronideosilruthenium potassium (
K2CRu, (NO)Ct5'3) 3.
8 F (2) Ashishania water
20ml (3) Cyto0+ Shilamishi Hydrochloride
1. Of(4) Water Total amount 5
After heating and boiling (00dfl) and (2), (3)
was added and the volume was made up to 500ml with water. This solution IQm/ is 20
■Contains ruthenium.
（３）シト０＋シルアミシ塩酸塩 １．
５１（４）水 全量 ５００ｄ（１１を
（２）に加え加熱溶解させた後、（３）を加え、水で５
００１Ｌｌとした。この溶液１０ｄは２０ＷＰｙのルテ
ニウムを含む。(3) Cyto0+silamici hydrochloride 1.
51 (4) Water Total amount 500 d (Add 11 to (2) and heat to dissolve, then add (3) and dissolve with water.
It was set as 001Ll. This solution 10d contains 20 WPy of ruthenium.
実施例 ｌ
銅板試料（２ｘ４ｃｒｒＩ）を脱脂、清浄化処理後、５
％塩化パラジウムを含む２ Ｎ −１１ｃｔ溶液に室温
３０秒浸漬した後水洗して活性化した。Example 1 After degreasing and cleaning a copper plate sample (2x4crrI), 5
It was activated by immersing it in a 2N-11ct solution containing % palladium chloride for 30 seconds at room temperature and then washing with water.
参考例１のＡ液４０ｍ１に水ＩＱｍｌ及びヒドラジ：／
（Ｎ２Ｈ４・Ｈ２Ｏ）の４０％溶液０，５ゴを加えて
調製したｐＨ１１，８の浴液中に４０℃、３時間浸漬し
、約５μ展のメツ中層を得た。この間浴液の分解は起ら
なかった。ルテニウムの利用率は９５チであった。40 ml of solution A of Reference Example 1, IQ ml of water and hydrazide:/
It was immersed for 3 hours at 40° C. in a bath solution of pH 11.8 prepared by adding 0.5 μg of a 40% solution of (N2H4.H2O) to obtain a middle layer with a thickness of about 5 μm. During this time, no decomposition of the bath liquid occurred. The utilization rate of ruthenium was 95 cm.
実施例 ２
パーフルオロカーポジスルホン酸型のカチオシ交換膜〔
デュポン社製、「ナフイオシ１１７」、膜厚７．ｌニル
（約０．１７５關）〕の直径８０ｍの円型部分にルテニ
ウムを公知の方法、すなわち、表面粗化→清浄化→ルテ
ニウムのアン三シ錯塩溶液吸着→水素化ホウ素ナトリウ
ム溶液による還元→水洗の処理で接合し、約１μｍの接
合層をもつ接合体を得た。Example 2 Perfluorocarposisulfonic acid type cation exchange membrane [
Manufactured by DuPont, "NAFUIOSHI 117", film thickness 7. Ruthenium was applied to a circular part of 80 m in diameter (approximately 0.175 mm) using a known method: surface roughening → cleaning → adsorption of ruthenium in an trisic complex solution → reduction with a sodium borohydride solution → They were bonded by washing with water to obtain a bonded body with a bonding layer of about 1 μm.
この接合体をメツ士セルに挟み、参考例１のＢ液１３Ｑ
＋ｕｔ（ルテニウムとして約２６０ηを含む）にアシ上
ニア水１０ｍ１．ｔ、ドラジン−水和物の４０チ溶液５
ｍｌ及び水を全量で４００−になる量加えて調製した
ｐＨ１１，８の浴液を各メツ＋室に循環ポジづで送水循
環しながら、４０〜５０℃でメツ牛した。This conjugate was sandwiched between Metsushi cells, and B liquid 13Q of Reference Example 1 was prepared.
+ut (contains about 260η as ruthenium) and 10ml of reed water. t, 40% solution of drazine-hydrate 5
A bath solution with a pH of 11.8 prepared by adding a total amount of 400 ml of water was heated at 40 to 50° C. while circulating water to each bath chamber.
約３μｍのメツ牛層に成長させるのに３時間を要し、浴
液中のルテニウムの利用率は９５％であった。It took 3 hours to grow the ruthenium layer to about 3 μm, and the utilization rate of ruthenium in the bath solution was 95%.
実施例 ３
パーフルオロカーボンスルホシ酸及びカルボン酸の複合
膜（デュポン社製、［ナフイオ−７９０１Ｊ）のカルポ
ジ酸膜側に公知の接合法で約２μｍのルテニウムを接合
した接合体を試料に用いた。Example 3 A composite membrane of perfluorocarbon sulfosic acid and carboxylic acid (manufactured by DuPont, [NAFIO-7901J) with approximately 2 μm of ruthenium bonded to the carbodiic acid membrane side by a known bonding method was used as a sample.
接合膜をメツ十セルに組み、メツ＋する側には参考例１
のＣ液７０ｄ（ルテニウムとして約１４０■を含む）に
アン七ニア水５ｍＡ’、しドラ、；シー水和物の４０チ
溶液５ｄ及び水金量２００ｍ１を加えて調製したｐＨ１
１，５の浴液を、またスルホン酸膜側には水２００ｍを
循環ポジづで循環しながら４０〜５０℃でメツ＋し、３
時間で約３μｍのルテニウム層を成長させ、全接合ルテ
ニウム層５μｍの接合体を得た。浴液中のルテニウムの
分解は見られず、利用率は９２チであった。Assemble the bonding film into 10 cells, and use Reference Example 1 on the 1+ side.
pH 1 was prepared by adding 5 mA' of aqueous solution, 5 d of a 40% solution of Shidora, Sea hydrate, and 200 ml of water gold to 70 d of solution C (containing about 140 ml of ruthenium).
1 and 5, and 200 m of water on the sulfonic acid membrane side, were heated at 40 to 50°C while circulating in a circulation position.
A ruthenium layer of about 3 μm thick was grown in an hour, and a bonded body with a ruthenium layer of 5 μm thick was obtained. No decomposition of ruthenium in the bath liquid was observed, and the utilization rate was 92%.
実施例 ４
ＡＢＳ樹脂（日本合成づム■製）の厚さ２ｍｓの板状試
料（５ｘ５ｃｒｒ１）を公知の方法に従って化学二゛シ
ケルメツ中し、この表面を実施例１と同様なパラジウム
活性化処理を行った後、参考例１のＤ液を用いてルテニ
ウムをメツ士した。Example 4 A plate-shaped sample (5 x 5 crr1) with a thickness of 2 ms of ABS resin (manufactured by Nippon Gosei Rubber Co., Ltd.) was placed in a chemical solution using a known method, and the surface was subjected to the same palladium activation treatment as in Example 1. After that, ruthenium was removed using Solution D of Reference Example 1.
Ｄ液７０ｍ１（ルテニウムとして約１４０■を含む）に
しドラジン−水和物の４０％溶液５−及び水金量１５０
ＴＬｌを加えて調製したｐＨ１２，０の浴液に浸漬し、
４０〜５０℃で３時間で約３μｍのルテニウム層を得た
。Add 70 ml of solution D (containing about 140 ml of ruthenium) to 5 ml of a 40% solution of drazine hydrate and 150 ml of water.
Immerse in a bath solution with pH 12.0 prepared by adding TLl,
A ruthenium layer of about 3 μm was obtained at 40-50° C. for 3 hours.
浴液中の分解はなく、ルテニウム利用率は９５チであっ
た。There was no decomposition in the bath liquid, and the ruthenium utilization rate was 95%.
（以 上）(that's all)
Claims (1)
ンを含有し、ｐＨ１０〜１３であることを特徴とするル
テニウムの無電解メツ生温。 ■ ルテニウムのニド０シルアシミシ錯塩、ヒドラジン
及びしドロ士シルアミシ塩を含有し、ｐＨ１０〜１３で
あることを特徴とするルテニウムの無電解メツ中浴。[Scope of Claims] (1) An electroless raw temperature of ruthenium, which contains a ruthenium nido-0-dylammine complex salt and a dorazine, and has a pH of 10 to 13. (2) An electroless bath of ruthenium, which contains a ruthenium nido-0-syl-achimic salt, hydrazine, and a ruthenium-nido-ocyl-achimic salt, and has a pH of 10 to 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19148682A JPS5934784B2 (en) | 1982-10-29 | 1982-10-29 | Ruthenium electroless plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19148682A JPS5934784B2 (en) | 1982-10-29 | 1982-10-29 | Ruthenium electroless plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5980766A true JPS5980766A (en) | 1984-05-10 |
| JPS5934784B2 JPS5934784B2 (en) | 1984-08-24 |
Family
ID=16275439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19148682A Expired JPS5934784B2 (en) | 1982-10-29 | 1982-10-29 | Ruthenium electroless plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5934784B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4959132A (en) * | 1988-05-18 | 1990-09-25 | North Carolina State University | Preparing in situ electrocatalytic films in solid polymer electrolyte membranes, composite microelectrode structures produced thereby and chloralkali process utilizing the same |
| WO2004042815A1 (en) * | 2002-10-31 | 2004-05-21 | Intel Corporation | Forming a copper diffusion barrier |
| JP2012508819A (en) * | 2008-11-12 | 2012-04-12 | ラム リサーチ コーポレーション | Plating solution for electroless deposition of ruthenium |
| CN110284128A (en) * | 2019-07-29 | 2019-09-27 | 合肥学院 | The method of chemical plating metal ruthenium |
| CN110952081A (en) * | 2018-09-27 | 2020-04-03 | Imec 非营利协会 | Method and solution for forming interconnects |
-
1982
- 1982-10-29 JP JP19148682A patent/JPS5934784B2/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4959132A (en) * | 1988-05-18 | 1990-09-25 | North Carolina State University | Preparing in situ electrocatalytic films in solid polymer electrolyte membranes, composite microelectrode structures produced thereby and chloralkali process utilizing the same |
| WO2004042815A1 (en) * | 2002-10-31 | 2004-05-21 | Intel Corporation | Forming a copper diffusion barrier |
| US7279423B2 (en) | 2002-10-31 | 2007-10-09 | Intel Corporation | Forming a copper diffusion barrier |
| JP2012508819A (en) * | 2008-11-12 | 2012-04-12 | ラム リサーチ コーポレーション | Plating solution for electroless deposition of ruthenium |
| TWI509104B (en) * | 2008-11-12 | 2015-11-21 | Lam Res Corp | Plating solutions for electroless deposition of ruthenium |
| CN110952081A (en) * | 2018-09-27 | 2020-04-03 | Imec 非营利协会 | Method and solution for forming interconnects |
| CN110284128A (en) * | 2019-07-29 | 2019-09-27 | 合肥学院 | The method of chemical plating metal ruthenium |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5934784B2 (en) | 1984-08-24 |
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