EP0180090A2 - Système et procédé pour la surveillance et la maintenance automatique des concentrations désirées dans les bains métalliques de plaquage - Google Patents

Système et procédé pour la surveillance et la maintenance automatique des concentrations désirées dans les bains métalliques de plaquage Download PDF

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Publication number
EP0180090A2
EP0180090A2 EP85113091A EP85113091A EP0180090A2 EP 0180090 A2 EP0180090 A2 EP 0180090A2 EP 85113091 A EP85113091 A EP 85113091A EP 85113091 A EP85113091 A EP 85113091A EP 0180090 A2 EP0180090 A2 EP 0180090A2
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EP
European Patent Office
Prior art keywords
bath
plating
additive
concentration
plating bath
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.)
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Application number
EP85113091A
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German (de)
English (en)
Other versions
EP0180090A3 (fr
Inventor
Gary Vincent Arbach
Perminder Singh Bindra
David Noel Light
David Lee Rath
Judith Marie Roldan
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International Business Machines Corp
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International Business Machines Corp
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Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0180090A2 publication Critical patent/EP0180090A2/fr
Publication of EP0180090A3 publication Critical patent/EP0180090A3/fr
Withdrawn legal-status Critical Current

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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
    • C23C18/1617—Purification and regeneration of coating baths
    • 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

Definitions

  • This invention relates to a system and method for monitoring metal plating bath concentrations, and more particularly to a system or method for electrolytically measuring the concentration of a metal plating bath and automatically replenishing the bath.
  • U.S. Patent 4,331,699 of Suzuki et al for "Method for Evaluating Electroless Plating” shows in FIG. 1, the use of the coulistatic method of measuring an electroless plating bath using a metallic working electrode 2, a reference electrode 8 of Pt, Cu, Ni, Pd, Cr, Rh, Ir or the like, and a counterelectrode 6.
  • a pulse generator produces pulses which test the solution from the electroless plating bath which is in the cell 4. This is relevant in that an electroless plating bath is being measured electrolytically.
  • the patent describes use of copper sulfate and EDTA in the Examples.
  • the Suzuki patent teaches the use of charge pulses applied to the working electrode.
  • the present invention does not apply any charge to the working electrode.
  • U.S. Patent 4,336,111 of Graunke for a "Method for Determining the Strength of a Metal Processing Solution” describes an in situ method for measuring the strength of an electroless plating solution or an etching solution. This arrangement involves only two electrodes, neither of which rotates.
  • U.S. Patent 4,350,717 of Araki et al for "Controlling Electroless Plating Bath” describes an automatic system for controlling the composition of the bath by measuring a constituent which is consumed and operating a controller to add the constituent being consumed to the required degree.
  • the concentration of the element in the bath is measured by a spectrophotometer 3 which senses the transmittance at the frequency of the metal complex in the bath which varies as a function of the concentration of the constituent being depleted.
  • the solution is enriched by controlling the valves 22 and 32 in response to the values measured.
  • a voltage is generated in response to the output of the spectrophotometer and it is compared with a fixed voltage to provide the control signals to the devices being controlled.
  • the present invention does not employ a spectrophotometer.
  • Araki teaches the measurement of a metal complex and not the measurement of any organic additives.
  • U.S. Patent 4,353,933 is similar to '717 above but it also includes a sensor 4 comprising a specific gravimeter for making measurements of the fluids in the bath. It differs from the present invention in the same ways as the above Araki patent.
  • An object of the present invention is to provide a system and a method of automatically monitoring and controlling, through replenishment, the concentration level of an additive employed in a metal plating bath by means of an automatic monitor and control system.
  • Another object of the present invention is to provide a system and method for measuring the presence of the additive in an electroless or electrolytic plating bath by taking a sample of the bath and measuring it in situ.
  • a further object of the present invention is to provide an automatic system for controlling the concentration of an additive to a plating bath in real time including means for measuring the mixed potential of the bath at zero net current applied to the bath, means for interpreting the mixed potential as a function of the velocity of the bath with respect to the measuring means, and means for refurbishing the bath as a function of the interpreted value.
  • the schematic drawing illustrates an embodiment of a system for the automatic, on-line analysis and control of chemical processing solutions. Monitoring and control of such solutions in manufacturing processes is particularly critical in order to maintain high standards of quality, throughput and efficiency of plating solutions used in printed circuit board plating and magnetic disk and head plating.
  • the automatic control system embodiment is shown in the block diagram in FIG. 2 and includes a sensing system such as measuring cell 10 which is illustrated in detail in FIG. 1.
  • the system of FIG. 2 also represents an embodiment for carrying out the process control method of the present invention.
  • the sensing system 10 consists of one or more sensing cells in which appropriate sensors are located.
  • a three electrode system 10 as shown in FIG. 1 with a rotating disk sensor 12 is employed to control agitation of the sample solution.
  • Other sensors 30 and 32 on electrodes 14 and 16 are used to measure pH and a thermometer is provided to monitor temperature.
  • the sensing process like the sampling process, is automatically controlled by the controller.
  • a number of techniques of the sensing subsystem have been successfully performed, including the galvanostatic pulse method, the potentiostatic pulse method, linear sweep methods, the polarization resistance method, the mixed potential method, and a number of spectrophotometric techniques.
  • the system of FIG. 2, in addition to the sensing means 10, further includes a controller 18, a plating tank 20, a mixing tank 22, a pump or control valve 24 and a reservoir 26.
  • the measuring cell 10 may be disposed in the bath in a standard plating tank 20 shown in FIG. 1, in which the plating bath solution is contained. Alternatively, a flow through tank may be used as shown in FIG. 1 which the plating solution may flow into and from as desired.
  • a replenishment bath from reservoir 26 can be pumped into mixing tank 22 by means of pump or control valve means 24 under the command of signals from controller 18 which in turn receives output signals from the measuring cell 10.
  • FIG. 2 illustrates an automatic plating bath replenishment system wherein in situ measurement devices sense the condition of the bath in the plating tank (or in a flow through tank), then feedback such measurements to a controller which in turn controls a pump or valve which introduces replenishment bath as needed for mixing with the sensed bath.
  • a controller which in turn controls a pump or valve which introduces replenishment bath as needed for mixing with the sensed bath.
  • This technique utilizes the concept of the mixed potential to determine the organic additive concentration in an electroless plating bath.
  • Organic additives generally participate in the plating process via a surface interaction and as such play a major role in determining the value of the mixed potential.
  • the mixed potential is best defined by considering two or more reactions occurring simultaneously. For example, in an electroless plating bath, the anodic reaction is the decomposition of the reducing agent. and the cathodic reaction the reduction of the metal complex
  • a necessary condition for electroless plating to occur is that the equilibrium potential for the reducing agent, E O R , is more cathodic than the corresponding potential E O M , for the metal deposition reaction.
  • the plating rate, i plating is given by: where i R and i M are the anodic and cathodic partial currents respectively.
  • the potential associated with this steady-state condition is referred to and hereinafter defined as the mixed potential E MP .
  • the value of the mixed potential lies between E O R and E O M and depends on parameters such as exchange current densities i O R and i O M , Tafel slopes b R and b M , temperature, etc.
  • Organic addition agents which directly participate in the mechanism for the deposition of the reducing agent or the deposition of the metal, or both, affect these parameters thereby altering the mixed potential. Changes in the value of the mixed potential resulting from different concentrations of a particular organic additive (such as thiodiglycolic acid in the Ni/B bath) can then be used to monitor the concentration of the organic additive in the electroless plating bath. This is illustrated in the examples which follow.
  • EXAMPLE 3 Additive monitoring in electrolytic copper plating baths.
  • An organic brightening agent used commonly in copper plating baths is thiourea, H 2 NCSNH 2 .
  • the mixed potential technique was applied to an electrolytic copper bath containing this additive.
  • the complete composition of the plating bath was as follows:
  • 2-Benzothiazolethiol is often a preferred organic additive in both electrolytic and electroless copper plating baths.
  • the technique described in this disclosure was applied to monitor 2-benzothiazolethiol in such a bath.
  • the calibration curve obtained is displayed in FIG. 6.
  • the plating bath had the following composition:
  • Electroless copper baths frequently contain thiourea as a brightener.
  • concentration of the brightener drifts unpredictably as it gets incorporated into the film or undergoes chemical reactions.
  • the mixed potential technique was applied to the bath with the following composition:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Automation & Control Theory (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Control Of Non-Electrical Variables (AREA)
EP85113091A 1984-10-30 1985-10-15 Système et procédé pour la surveillance et la maintenance automatique des concentrations désirées dans les bains métalliques de plaquage Withdrawn EP0180090A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66651284A 1984-10-30 1984-10-30
US666512 1984-10-30

Publications (2)

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EP0180090A2 true EP0180090A2 (fr) 1986-05-07
EP0180090A3 EP0180090A3 (fr) 1987-03-18

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EP (1) EP0180090A3 (fr)
JP (1) JPS61110799A (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2198750A (en) * 1986-10-31 1988-06-22 Kollmorgen Corp Controlling electroless deposition
US4908242A (en) * 1986-10-31 1990-03-13 Kollmorgen Corporation Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
EP0588323A2 (fr) * 1992-09-16 1994-03-23 Hughes Aircraft Company Capteur électrochimique placé dans une cuve
WO1999057340A3 (fr) * 1998-05-01 2000-02-03 Dj Parker Company Inc Melange chimique, regeneration et systeme de traitement des dechets
US6746579B2 (en) 2001-11-21 2004-06-08 Hitachi Kyowa Engineering Co., Ltd. Electrolytic gold plating method and apparatus therefor
EP1191128A3 (fr) * 2000-09-20 2004-08-25 Ebara Corporation Procédé de placage et dispositif de placage
US7851222B2 (en) 2005-07-26 2010-12-14 Applied Materials, Inc. System and methods for measuring chemical concentrations of a plating solution
ES2353706A1 (es) * 2008-11-21 2011-03-04 Universidad Politecnica De Valencia Celda electroquímica de generación de gases para el análisis de procesos electroquímicos.
CN102998353A (zh) * 2011-09-15 2013-03-27 上海宝钢工业检测公司 镀锡板镀层中铅测定样品处理自动试验装置
CN107227468A (zh) * 2017-07-31 2017-10-03 赣州市恒源科技股份有限公司 一种稀土金属自动电解设备
CN110863237A (zh) * 2019-11-06 2020-03-06 江门荣信电路板有限公司 一种电镀液自动添加的防呆系统及其使用方法
CN112030196A (zh) * 2020-08-20 2020-12-04 中南大学 一种精密电铸系统及控制方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5509120B2 (ja) * 2011-02-28 2014-06-04 メルテックス株式会社 無電解ニッケルめっき液の硫黄化合物濃度測定方法
JP5443409B2 (ja) * 2011-02-28 2014-03-19 トヨタ自動車株式会社 硫黄系化合物の管理方法及びその管理システム
JP6373157B2 (ja) * 2014-10-14 2018-08-15 日置電機株式会社 電気化学センサおよび電気化学測定装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2371522B1 (fr) * 1976-11-22 1980-02-15 Kollmorgen Tech Corp
DE2911073A1 (de) * 1979-03-21 1980-10-02 Siemens Ag Badfuehrungsgeraet fuer ein bad zum stromlosen abscheiden von kupfer
US4406249A (en) * 1979-11-14 1983-09-27 C. Uyemura & Co., Ltd. Apparatus for controlling electroless plating bath

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2371522B1 (fr) * 1976-11-22 1980-02-15 Kollmorgen Tech Corp
DE2911073A1 (de) * 1979-03-21 1980-10-02 Siemens Ag Badfuehrungsgeraet fuer ein bad zum stromlosen abscheiden von kupfer
US4406249A (en) * 1979-11-14 1983-09-27 C. Uyemura & Co., Ltd. Apparatus for controlling electroless plating bath

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF ELECTROCHEMICAL SOCIETY, vol. 127, no. 2, February 1980, pages 365-369; M. PAUNOVIC "An electrochemical control system for electroless copper bath" *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2198750A (en) * 1986-10-31 1988-06-22 Kollmorgen Corp Controlling electroless deposition
US4908242A (en) * 1986-10-31 1990-03-13 Kollmorgen Corporation Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
GB2198750B (en) * 1986-10-31 1991-01-02 Kollmorgen Corp Method for electrolessly depositing high quality copper
EP0588323A2 (fr) * 1992-09-16 1994-03-23 Hughes Aircraft Company Capteur électrochimique placé dans une cuve
EP0588323A3 (fr) * 1992-09-16 1995-05-24 Hughes Aircraft Co Capteur électrochimique placé dans une cuve.
WO1999057340A3 (fr) * 1998-05-01 2000-02-03 Dj Parker Company Inc Melange chimique, regeneration et systeme de traitement des dechets
EP1191128A3 (fr) * 2000-09-20 2004-08-25 Ebara Corporation Procédé de placage et dispositif de placage
US6746579B2 (en) 2001-11-21 2004-06-08 Hitachi Kyowa Engineering Co., Ltd. Electrolytic gold plating method and apparatus therefor
US7851222B2 (en) 2005-07-26 2010-12-14 Applied Materials, Inc. System and methods for measuring chemical concentrations of a plating solution
ES2353706A1 (es) * 2008-11-21 2011-03-04 Universidad Politecnica De Valencia Celda electroquímica de generación de gases para el análisis de procesos electroquímicos.
CN102998353A (zh) * 2011-09-15 2013-03-27 上海宝钢工业检测公司 镀锡板镀层中铅测定样品处理自动试验装置
CN102998353B (zh) * 2011-09-15 2016-08-10 上海宝钢工业技术服务有限公司 镀锡板镀层中铅测定样品处理自动试验装置
CN107227468A (zh) * 2017-07-31 2017-10-03 赣州市恒源科技股份有限公司 一种稀土金属自动电解设备
CN110863237A (zh) * 2019-11-06 2020-03-06 江门荣信电路板有限公司 一种电镀液自动添加的防呆系统及其使用方法
CN112030196A (zh) * 2020-08-20 2020-12-04 中南大学 一种精密电铸系统及控制方法
CN112030196B (zh) * 2020-08-20 2021-09-14 中南大学 一种精密电铸系统及控制方法

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Publication number Publication date
EP0180090A3 (fr) 1987-03-18
JPS61110799A (ja) 1986-05-29

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