JP2009525404A - 基板表面をコーティングする方法および装置 - Google Patents
基板表面をコーティングする方法および装置 Download PDFInfo
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- JP2009525404A JP2009525404A JP2008552727A JP2008552727A JP2009525404A JP 2009525404 A JP2009525404 A JP 2009525404A JP 2008552727 A JP2008552727 A JP 2008552727A JP 2008552727 A JP2008552727 A JP 2008552727A JP 2009525404 A JP2009525404 A JP 2009525404A
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- 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
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1617—Purification and regeneration of coating baths
-
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Automation & Control Theory (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
【選択図】図2
Description
さらに本発明による方法によって、層は、安定したままの電解液により析出され、この事実は、安定したコーティング結果、また、例えば電解液の使用の全期間にわたる常に高い残留圧縮応力といった被膜の特性をもたらす。
有利には、硫黄を含む複素環が、触媒として電解液に添加される。硫黄を含む複素環として、好ましくはサッカリン、その塩および/または誘導体、最も好ましくはサッカリン・ナトリウムが使用される。先行技術から知られ、従来使用されているS2−ベースの触媒とは逆に、サッカリン塩の添加は、より高い濃度であっても、析出された金属層の腐食耐性にいかなる悪影響も及ぼさない。
4乃至6g/l ニッケル・イオン
25乃至60g/l 還元剤
25−70g/l 錯体形成剤
1乃至25g/l 触媒
0.1乃至2mg/l 安定化剤
0乃至3g/l 追加の成分
当該ベース電解液のpH範囲は、4.0乃至5.0である。既に上述したように、金属受容体として、好ましくは金属塩が使用され、その陰イオンは揮発性である。金属塩(その陰イオンは揮発性である)として、好ましくは、金属酢酸塩、金属ギ酸塩、金属硝酸塩、金属シュウ酸塩、金属プロピオン酸塩、金属クエン酸塩および金属アスコルビン酸塩からなる群からの一または複数の塩、最も好ましくは金属酢酸塩のみが使用される。反応の間、pHはH*−イオンの連続生成により減少し、水酸化物、炭酸塩などのアルカリ性媒質、または通常選択されるアンモニアによって複雑な方法でpHを目標範囲に維持しなければならないため、特別の利点は、陰イオンが揮発性であり、好ましくは酢酸塩、ギ酸塩、硝酸塩、シュウ酸塩、プロピオン酸塩、クエン酸塩およびアスコルビン酸塩の群に由来する金属塩の単独の使用に存在する。その理由は、金属−リン層の析出において、酢酸塩、ギ酸塩、硝酸塩、シュウ酸塩、プロピオン酸塩、クエン酸塩およびアスコルビン酸塩の陰イオンがナトリウム次亜リン酸塩からのナトリウムと反応して、酸ナトリウム塩を形成するからである。従って、析出処理の全体にわたって、電解液は、より多量のアルカリ性媒体を加える必要なしに、4.0乃至5.2、好ましくは4.3乃至4.8のpH範囲で作用する。この非常に有利なpH自己制御によって、処理の間、アルカリ性添加物はもちろん、連続pH制御も不要とすることができる。
500乃至580g/l 還元剤
5乃至15g/l 錯体形成剤
50乃至150g/l アルカリ性緩衝剤
11乃至20g/l 触媒
0乃至3g/l 追加の成分
10乃至50g/l 錯体形成剤
0.68乃至2.283mol/l 金属受容体
1乃至25g/l 触媒
40乃至80mg/l 安定化剤
図1においては、電解液の処理時間および電解液の除去された量に応じた、異なる電解液組成物の密度特徴が示される。グラフ1は、先行技術から知られているニッケル層の析出に関する電解液の密度特徴を示す。グラフ2は、3.3%の電解液除去の設定量におけるニッケル層の析出に関する先行技術の電解液の密度特徴を示す。グラフ3は、欧州特許出願EP1413646から知られている種類の電解液の密度特徴を示し、その電解液において、金属塩(その陰イオンは揮発性である)は、電解液組成物の金属ベースの塩として使用される。グラフ4は、3.3%の電解液除去の設定量でグラフ3に関連して記載された電解液を示す。グラフ5は、10%の電解液除去の設定量でグラフ3に関連して記載された電解液を示す。
2 電解槽
3 制御モジュール
4 センサ
5 任意の熱回収
6 充填水準センサ
7 除去された電解液のための収容容器
Claims (12)
- コーティング溶液において金属または酸化物の層で基板表面をコーティングする方法であって、ここで、溶液が少なくとも1つの成分を含み、その濃度がコーティング処理の経過で変化し、その結果、溶液の品質を維持するためにそれを補充または除去されなければならないものであって、
成分の補充および/または除去が溶液の組成物の密度に応じて行われることを特徴とするもの。 - コーティング溶液の測定された密度値が基準密度値と比較され、変化する成分の補充および/または除去が、測定された密度値の基準密度値からの偏差に応じて行われることを特徴とする、請求項1に記載の方法。
- コーティング溶液の密度が記憶された基準値に合致することを条件として、コンピュータ・ユニットが除去および/または補充のデバイスを制御することを特徴とする、請求項2に記載の方法。
- コーティング溶液の少なくとも1つの除去された成分が回収されリサイクリングに供給されることを特徴とする、請求項1乃至3の一に記載の方法。
- 処理の開始から、コーティング溶液組成物が、目標密度値に一致する密度で使用されることを特徴とする、請求項1乃至4の一に記載の方法。
- 処理において、基板上のニッケルまたはニッケル合金の層の析出のための電解液が使用されることを特徴とする、請求項1乃至5の一または複数に記載の方法。
- 処理において、酸化物層がアルミニウム基板の表面上に形成されることを特徴とする、請求項1乃至5の一または複数に記載の方法。
- 金属または酸化物の層で基板表面をコーティングするための電解液の少なくとも1つの電解液成分の連続的な除去および/または添加のための装置であって、前記装置が少なくとも1つの電解液成分の除去および/または添加のためのデバイス、電解液の密度を測定するためのデバイス、およびコンピュータ・ユニットを含み、ここで、少なくとも1つの電解液成分の除去および/または添加のためのデバイスが、密度を測定するためのデバイスによって測定される密度値に応じてコンピュータ・ユニットによって制御され、ここで、コンピュータ・ユニットが、記憶された基準密度値と電解液の密度を測定するためのデバイスによって測定された密度値とを比較するものであって、電解液の密度が、少なくとも1つの電解液成分の添加および/または除去によって、記憶された目標密度値に合致することを条件とするもの。
- 密度を測定するためのデバイスが比重瓶、屈折計、比重計、密度天秤または曲げ共振器であることを特徴とする、請求項8に記載の装置。
- 装置が溶液特性の測定のための追加のデバイスを含むことを特徴とする、請求項8または9の一または複数に記載の装置。
- 装置を既存のコーティングシステムに組み込むことができることを特徴とする、請求項8乃至10の一または複数に記載の装置。
- 請求項1乃至7の一または複数に記載の方法を実行するための請求項8乃至11の一または複数に記載の装置の使用。
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EP06002099A EP1816237A1 (de) | 2006-02-02 | 2006-02-02 | Verfahren und Vorrichtung zur Beschichtung von Substratoberflächen |
PCT/EP2007/000658 WO2007088008A2 (de) | 2006-02-02 | 2007-01-26 | Verfahren und vorrichtung zur beschichtung von substratoberflächen |
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EP2449148B1 (en) * | 2009-07-03 | 2019-01-02 | MacDermid Enthone Inc. | Beta-amino acid comprising electrolyte and method for the deposition of a metal layer |
US20130087463A1 (en) * | 2011-10-05 | 2013-04-11 | Globalfoundries Inc. | Method and System for Metal Deposition in Semiconductor Processing |
KR101502795B1 (ko) * | 2012-03-15 | 2015-03-13 | 김종호 | 포물선의 전체 또는 일부의 굴절경로를 갖는 진주광택 안료 입자 및 이의 제조방법 |
DE102018008312A1 (de) | 2018-10-22 | 2020-04-23 | RIAG Oberflächentechnik AG | Verfahren zur Beschichtung von Substratoberflächen, Vorrichtung mit Beschichtungsbad, Dichtemesseinrichtung, Entnahmeeinrichtung, Zugabeeinrichtungen und Steuerung |
CN113755937B (zh) * | 2021-09-09 | 2022-12-09 | 中国航发南方工业有限公司 | 电镀铂槽液的维护方法 |
CN114351231B (zh) * | 2022-01-04 | 2022-11-25 | 深圳技术大学 | 电解液中金属离子浓度的测量和监控的设备和方法 |
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CN101437986B (zh) | 2013-12-11 |
EP1979511B1 (de) | 2018-10-31 |
ES2706874T3 (es) | 2019-04-01 |
WO2007088008A2 (de) | 2007-08-09 |
US20090324804A1 (en) | 2009-12-31 |
WO2007088008A3 (de) | 2008-04-17 |
JP5695295B2 (ja) | 2015-04-01 |
CN101437986A (zh) | 2009-05-20 |
KR101466995B1 (ko) | 2014-12-01 |
EP1816237A1 (de) | 2007-08-08 |
PL1979511T3 (pl) | 2019-05-31 |
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