EP0045970B1 - Verfahren zur Bestimmung der Stromausbeute bei galvanischen Bädern - Google Patents

Verfahren zur Bestimmung der Stromausbeute bei galvanischen Bädern Download PDF

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Publication number
EP0045970B1
EP0045970B1 EP81106263A EP81106263A EP0045970B1 EP 0045970 B1 EP0045970 B1 EP 0045970B1 EP 81106263 A EP81106263 A EP 81106263A EP 81106263 A EP81106263 A EP 81106263A EP 0045970 B1 EP0045970 B1 EP 0045970B1
Authority
EP
European Patent Office
Prior art keywords
electrode
current
rotating disc
electro
time
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.)
Expired
Application number
EP81106263A
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German (de)
English (en)
French (fr)
Other versions
EP0045970A1 (de
Inventor
Frank Dr. Vangaever
Jacky Dr. Vanhumbeeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0045970A1 publication Critical patent/EP0045970A1/de
Application granted granted Critical
Publication of EP0045970B1 publication Critical patent/EP0045970B1/de
Expired legal-status Critical Current

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    • 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

  • the invention relates to a method for determining the current yield and possibly for determining the scatter in galvanic baths, according to the preamble of claim 1.
  • the invention has for its object to provide a method for determining the current efficiency in a galvanic bath.
  • the automatic determination of the current yield in conjunction with a corresponding control enables constant layer thicknesses to be maintained, in particular in the case of continuous galvanic systems.
  • the time for anodic removal of the deposited metal is preferably determined from the potential-time curve.
  • the potential between the rotating disk electrode and a reference electrode is recorded, which has a constant voltage.
  • the time for anodic removal is determined by at least two measurements with different distances between the rotating disk electrode and the counter electrode.
  • control of all components required for the automatic implementation of the method and / or the processing of measured values is preferably carried out by a process control circuit.
  • the method according to the invention is explained in more detail with reference to the drawing.
  • the drawing shows an arrangement for automatically measuring the current yield in principle.
  • I denotes a process part that contains a galvanic bath 1 as the most important part in which the process electrolyte is located. It is assumed that the galvanic bath is a continuous galvanic system.
  • the boxes denoted by 3 and 4 are intended to indicate that a defined current density (or current) and a specific belt speed can be specified in order to achieve a specific layer thickness, as indicated by a dashed arrow 5. Such systems are known per se and do not form the subject of this invention.
  • thermostatted measuring cell 6 which can be supplied with a defined amount of electrolyte solution from the galvanic bath 1 by means of a metering syringe 7 via a valve 8 and a line 9.
  • the measuring cell 7 has a rotating disk electrode 10, a counter electrode 11 opposite it and a reference electrode 12 as the working electrode.
  • the disk electrode 10 carries a metal disk 13 at the lower end, which faces the counter electrode 11.
  • the reference electrode 12 is conventional and can be, for example, a calomel, Ag or AgCL electrode.
  • the counterelectrode 11 can be, for example, a platinized titanium sheet, or it is adapted to the respective measurement problem, as is the metal disk 13 of the disk electrode 10.
  • the electromotive drive of the rotating disk electrode 10 is designated by 14, which is connected via lines 15 and 16 to an electronic part III is related, as will be described in more detail below.
  • a pipe 18 is connected, which leads, for example, to a waste container.
  • Another outlet of the three-way valve 18 is connected to the galvanic bath 1 via a pipeline 19, so that the bath sample located in the measuring cell 6 can be returned to the galvanic bath 1, which is particularly important when using a noble metal electrolyte.
  • a suitable electrolyte solution which can also be supplied to the measuring cell 6 by means of a metering syringe 21 via a pipeline 22. Furthermore, water or another liquid for rinsing and cleaning can be supplied to the measuring cell 6 via a pipe 23 and valve 24.
  • the electronic part III contains a control part 25 for the rotating disk electrode 10, the output Ant of which is connected to the connection of the line 15 which is identified by the same name.
  • the rotational speed of the disk electrode 10 can be specified via the control part 25.
  • a potentiograph is designated, which for recording the potential-time Curve serves.
  • the outputs of the potentiograph 26 labeled AE and BE are connected to the correspondingly labeled connections AE and BE of the working electrode 10 and the reference electrode 12, respectively.
  • the disk electrode 10 and the counter electrode 11 lie in a circuit which can be supplied with constant current by a current source 27.
  • the outputs AE and GE of the current source 27 are connected to the correspondingly designated connections of the disk electrode 10 and the counter electrode 11.
  • the electronics part 111 also contains a process control circuit 28 with a microprocessor 29 and an operating panel 30. Furthermore, the entire system is equipped with a controller 31. For example, the speed of rotation of the disc electrode 10 of the desired current density, i.e. be set and controlled by the microprocessor 29 to be examined electrolyte. Furthermore, the entire sequence of the measuring process and the regulation of the current density and the belt speed of the galvanic bath can be controlled by the same microprocessor 29.
  • the measuring cycle consists of the following steps: With the aid of the metering syringe 7, a defined amount of electrolyte solution is removed from the galvanic bath 1 and this bath sample is introduced into the thermostated measuring cell 6. Here, the temperature in the measuring cell during deposition is kept equal to the temperature in the galvanic bath 1.
  • the rotating working electrode 10 is used to increase and keep the mass transport constant.
  • the setting of the corresponding rotational speed of the disk electrode and the current density i k are controlled by the microprocessor 29.
  • the current is switched off and the bath sample from the measuring cell 6 is returned to the galvanic bath 1 via the three-way valve 17 and line 19.
  • the process control 28 then rinses the measuring cell 6 with water via valve 24 and drains it off via line 18.
  • a defined amount of electrolyte solution is then introduced from the electrolyte container 22 into the measuring cell 6 with the aid of the metering syringe 21.
  • This electrolyte solution is adapted to the metal precipitation; however, it should enable a constant, if possible 100% current yield when removing the metal deposited on the metal disk 13 of the disk electrode 10.
  • the potentials on the disk electrode 10 and on the counter electrode 11 are reversed, with the aid of the microprocessor 29 the anodic current i a and the optimum rotational speed of the disk electrode 10 being adjusted for removal.
  • the temperature is also kept constant during anodic removal. For procedural reasons, it can be kept lower, for example to avoid steam formation.
  • the potential-time data are continuously stored in the microprocessor 29 and the end point is determined therefrom.
  • the potential profile between the disk electrode 10 and the reference electrode 12 can be recorded during the removal.
  • the end point of the metal removal results in the time t a and is indicated in the potential-time curve by a strong change in potential.
  • the power supply to the electrodes is switched off; the measuring cell is then emptied and rinsed and prepared for a new measurement.
  • the disc electrode may need to be cleaned of any remaining deposits. A corresponding other liquid is used for this.
  • the amount of electricity required for removal is equal to i a ⁇ t a ⁇ ⁇ a , where ⁇ a is the anodic current yield.
  • the anodic current efficiency ⁇ a 1 can be kept by a suitable choice of the electrolyte solution.
  • the current yield can now be calculated using the microprocessor 29 in the following way:
  • the current density in the galvanic bath and / or the exposure time is preferably regulated as a function of the current yield (r lk ).
  • the evaluation of the potential-time curve for determining t a can be carried out in a manner known per se, for example by the intersection of straight lines through linear sections of the curve or a turning point in the case of an S-shaped curve.
  • the scattering of an electrolyte can also be determined with the method according to the invention.
  • Scattering means the fluctuating layer thickness that occurs on a part to be electroplated, if the distance between the surface of the part and the part ode is not the same.
  • at least two measurements with different distances between the rotating disk electrode 10 and the counter electrode 11 must be carried out to determine the scatter.
  • two mutually independent measuring cells with different distances between the rotating disk electrode (10) and the counter electrode (11) are used to determine the scatter. Two rik values are calculated from this; the ratio of these two values is a measure of the spread.
  • a rotating disk electrode which carries several suitable metal disks at the lower end, e.g. 2 for the ring-disc electrode and 3 for a split ring-disc electrode (i.e. the so-called split-ring-disc electrode).
  • Two or more llk values are calculated from this; the ratio of these values is a measure of the spread.
  • the measuring principle according to the invention is not limited to the direct voltage method, but can e.g. can also be used for pulse separation.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Automation & Control Theory (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
EP81106263A 1980-08-13 1981-08-11 Verfahren zur Bestimmung der Stromausbeute bei galvanischen Bädern Expired EP0045970B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3030664 1980-08-13
DE3030664A DE3030664C2 (de) 1980-08-13 1980-08-13 Verfahren zur Bestimmung der Stromausbeute bei galvanischen Bädern

Publications (2)

Publication Number Publication Date
EP0045970A1 EP0045970A1 (de) 1982-02-17
EP0045970B1 true EP0045970B1 (de) 1985-01-16

Family

ID=6109561

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81106263A Expired EP0045970B1 (de) 1980-08-13 1981-08-11 Verfahren zur Bestimmung der Stromausbeute bei galvanischen Bädern

Country Status (5)

Country Link
US (1) US4595462A (enrdf_load_stackoverflow)
EP (1) EP0045970B1 (enrdf_load_stackoverflow)
JP (1) JPS5754849A (enrdf_load_stackoverflow)
CA (1) CA1166187A (enrdf_load_stackoverflow)
DE (1) DE3030664C2 (enrdf_load_stackoverflow)

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GB8408113D0 (en) * 1984-03-29 1984-05-10 Quantel Ltd Video editing/viewing systems
US4917774A (en) * 1986-04-24 1990-04-17 Shipley Company Inc. Method for analyzing additive concentration
US4956610A (en) * 1988-02-12 1990-09-11 Pgm Diversified Industries, Inc. Current density measurement system by self-sustaining magnetic oscillation
US5059908A (en) * 1990-05-31 1991-10-22 Capital Controls Company, Inc. Amperimetric measurement with cell electrode deplating
CA2087801C (en) * 1993-01-21 1996-08-13 Noranda Ipco Inc. Method and apparatus for on-line monitoring the quality of a purified metal sulphate solution
US6269533B2 (en) * 1999-02-23 2001-08-07 Advanced Research Corporation Method of making a patterned magnetic recording head
US6496328B1 (en) 1999-12-30 2002-12-17 Advanced Research Corporation Low inductance, ferrite sub-gap substrate structure for surface film magnetic recording heads
US20040040842A1 (en) * 2002-09-03 2004-03-04 King Mackenzie E. Electrochemical analytical apparatus and method of using the same
US6986835B2 (en) * 2002-11-04 2006-01-17 Applied Materials Inc. Apparatus for plating solution analysis
US20050067304A1 (en) * 2003-09-26 2005-03-31 King Mackenzie E. Electrode assembly for analysis of metal electroplating solution, comprising self-cleaning mechanism, plating optimization mechanism, and/or voltage limiting mechanism
US20050109624A1 (en) * 2003-11-25 2005-05-26 Mackenzie King On-wafer electrochemical deposition plating metrology process and apparatus
US20050224370A1 (en) * 2004-04-07 2005-10-13 Jun Liu Electrochemical deposition analysis system including high-stability electrode
US6984299B2 (en) * 2004-04-27 2006-01-10 Advanced Technology Material, Inc. Methods for determining organic component concentrations in an electrolytic solution
US7435320B2 (en) 2004-04-30 2008-10-14 Advanced Technology Materials, Inc. Methods and apparatuses for monitoring organic additives in electrochemical deposition solutions
US7427346B2 (en) * 2004-05-04 2008-09-23 Advanced Technology Materials, Inc. Electrochemical drive circuitry and method
WO2005124335A1 (en) * 2004-06-11 2005-12-29 Carnegie Mellon University Apparatus and method for determining the zeta potential of surfaces and for the measurement of streaming metrics related thereto
US7851222B2 (en) * 2005-07-26 2010-12-14 Applied Materials, Inc. System and methods for measuring chemical concentrations of a plating solution
US20070261963A1 (en) * 2006-02-02 2007-11-15 Advanced Technology Materials, Inc. Simultaneous inorganic, organic and byproduct analysis in electrochemical deposition solutions
DE102008061877B3 (de) * 2008-12-11 2010-09-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Vorrichtung zur Bestimmung von Prozessbedingungen bei der elektrochemischen Beschichtung eines Profilkörpers und Verfahren
EP2495357B1 (de) 2010-11-25 2014-10-08 Somonic Solutions GmbH Einrichtung und Verfahren zur Messung der Geschwindigkeit oder der Stromausbeute bei der Abscheidung oder beim Abtrag von Oberflächen und zur darauf basierenden Prozesssteuerung
DE102015106432A1 (de) 2015-04-27 2016-10-27 Gramm Technik Gmbh Verfahren und Vorrichtung zur Herstellung eines Werkstücks
CN106199199B (zh) * 2016-09-30 2017-06-16 山东齐星新能源科技有限责任公司 一种软包装锂离子电池铝塑膜腐蚀的检测方法
US10329683B2 (en) * 2016-11-03 2019-06-25 Lam Research Corporation Process for optimizing cobalt electrofill using sacrificial oxidants

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US3215609A (en) * 1962-12-04 1965-11-02 Conversion Chem Corp Electroplating test cell and method
DE1935231C3 (de) * 1969-07-11 1979-04-05 Fernsteuergeraete Kurt Oelsch Kg, 1000 Berlin Verfahren zur Bestimmung der Stromansbeute elektrolytischer Bäder
US4132605A (en) * 1976-12-27 1979-01-02 Rockwell International Corporation Method for evaluating the quality of electroplating baths
US4102770A (en) * 1977-07-18 1978-07-25 American Chemical And Refining Company Incorporated Electroplating test cell
US4153521A (en) * 1977-08-05 1979-05-08 Litvak Rafael S Method of automatic control and optimization of electrodeposition conditions
US4229264A (en) * 1978-11-06 1980-10-21 The Boeing Company Method for measuring the relative etching or stripping rate of a solution
US4310389A (en) * 1980-06-16 1982-01-12 Chrysler Corporation Method for simultaneous determination of thickness and electrochemical potential in multilayer plated deposits

Also Published As

Publication number Publication date
JPS5754849A (en) 1982-04-01
DE3030664C2 (de) 1982-10-21
DE3030664A1 (de) 1982-03-18
CA1166187A (en) 1984-04-24
US4595462A (en) 1986-06-17
EP0045970A1 (de) 1982-02-17
JPH021262B2 (enrdf_load_stackoverflow) 1990-01-10

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