EP0246494A1 - Dosage polarographique d'additifs pour bains d'électrodéposition - Google Patents

Dosage polarographique d'additifs pour bains d'électrodéposition Download PDF

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Publication number
EP0246494A1
EP0246494A1 EP87106582A EP87106582A EP0246494A1 EP 0246494 A1 EP0246494 A1 EP 0246494A1 EP 87106582 A EP87106582 A EP 87106582A EP 87106582 A EP87106582 A EP 87106582A EP 0246494 A1 EP0246494 A1 EP 0246494A1
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EP
European Patent Office
Prior art keywords
electrode
polarographic
peak
additives
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.)
Granted
Application number
EP87106582A
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German (de)
English (en)
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EP0246494B1 (fr
Inventor
Rudy Dipl.-Chem. De Doncker
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
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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Publication date
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Priority to AT87106582T priority Critical patent/ATE49613T1/de
Publication of EP0246494A1 publication Critical patent/EP0246494A1/fr
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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
    • C25D21/14—Controlled addition of electrolyte components

Definitions

  • the invention relates to a method for the polarographic determination of organic additives in galvanic baths, in particular gloss additives and wetting agents in galvanic copper baths.
  • the galvanic deposition of a metal ion on a workpiece connected as a cathode is possible from an aqueous solution of the corresponding metal salt.
  • technical baths used in electroplating consistently contain several salts and other additives.
  • conductive salts increase the conductivity of the bath and influence the dissociation of the metal salts.
  • Buffers have the task of keeping the pH of a bath constant.
  • Additives influence the properties of the metal deposits. For example, gloss additives allow the deposition of shiny precipitates, while wetting agents suppress the pore formation in the precipitates.
  • the invention has for its object to provide a method for determining gloss additives and wetting agents in galvanic copper baths, which provides information about whether and in what effective concentration these additives are contained in the copper bath with little effort.
  • This object is achieved in that the current-voltage relationship of the bath solution to be examined is determined on the electrodes of a polarographic analyzer with a mercury drop electrode with a hanging mercury drop and with an applied direct voltage and that in the event of a sudden increase in the current intensity in the form of a polarographic spade each peak voltage is evaluated as a characteristic variable for the type of additive contained in the bath solution and the peak height as a characteristic variable for the effective concentration of this additive.
  • Conventional polarography is an electrometric method of chemical analysis based on the current-voltage relationship on a specific type of electrode.
  • the solution to be examined is located between two electrodes and is exposed to a constantly increasing voltage. As soon as the reduction potential of one of the ion types in the solution is reached, the current strength increases suddenly. If there is a further reduction in the ions concerned at a higher voltage, a new increase in the current intensity is obtained. If you plot the voltage in a diagram, the so-called polarogram, against the respective current strength, you get a step-shaped curve that z. B. shows in the reduction of the divalent copper ion Cu2+ two such polarographic steps. The position of the steps can then be used to infer the type of the respective ions, while the height of the steps provides information about the concentration of the respective ions.
  • the corresponding polarogram shows the polarographic steps typical for the reduction of the divalent copper ion Cu2+.
  • the polarogram is now modified in a characteristic manner by the presence of gloss additives and wetting agents, ie at certain voltages associated with the gloss additive or the wetting agent, there is a sudden increase in the current intensity in the form of a polarographic peak. This is due to adsorption processes on the polarized electrode, due to which gloss additive and wetting agent act as an activator or inhibitor for copper reduction.
  • the effectiveness of the additives in the bath and not the absolute concentration can be determined from this effect.
  • the effect of additives described above can then also provide information about the type and concentration of the additives with other additives and with other galvanic baths.
  • the prerequisite for such a determination of the efficiency of additives is the use of a mercury drop electrode with a hanging mercury drop and with a DC voltage designed.
  • the additives are neither reduced nor oxidized.
  • the use of the otherwise usual dripping cross silver drip electrode or the differential pulse polarography or the alternating current polarography would not allow such a determination of the efficiency of an additive.
  • FIG. 1 shows a highly simplified schematic representation of a polarographic analyzer for determining gloss additives in galvanic copper baths.
  • a sample of the bath solution Bl to be examined in a container Bh there is a storage vessel Vg with mercury Hg, from which a glass capillary Gk extends below the level of the bath solution B1.
  • a drop of mercury which acts as a so-called mercury drop electrode with a hanging drop of mercury.
  • a counter electrode labeled Ge and a reference electrode labeled Re are also immersed in the bath solution B1.
  • the current-voltage relationship of the bath solution Bl to be examined is now determined by applying a time-variable DC potential E between the mercury drip electrode Qe and the reference electrode Re and measuring the current i between the mercury drip electrode Qe and the counter electrode Ge.
  • FIG. 2 shows a highly simplified schematic representation of the polarogram recorded by the analyzer according to FIG. 1, in which the ordinate indicates the current intensity i while on Tears the potential E is plotted.
  • the dash-dotted curve shows the polarogram of a pure galvanic copper bath that contains neither a gloss additive nor a wetting agent.
  • the solid curve shows the polarogram of a galvanic copper bath, which contains a gloss additive and a wetting agent.
  • the first polarographic peak PN is caused by the wetting agent in the copper bath, while the second polarographic peak PG is caused by the addition of gloss in the copper bath.
  • the peak voltage PNS ie the potential E at which the polarographic peak PN occurs
  • the peak voltage PGS ie the potential E at which the polarographic peak PG occurs
  • the peak height PNH which corresponds to the highest current i of the polarographic peak PN, is a characteristic variable for the effective concentration of the wetting agent contained in the copper bath.
  • the peak height PGH which corresponds to the highest current i of the polarographic peak PG, is a characteristic variable for the effective concentration of the gloss additive contained in the copper bath.
  • the peak heights do not indicate the absolute amounts of the additives contained in the galvanic bath, but rather the effective amounts or the Efficiency of these additives. This is a considerable advantage for bath monitoring, since the effective amounts always allow a comparison with the fresh bath batch and the corresponding separation conditions.
  • the gloss additive labeled "Glänzer 67 liquid” and the wetting agent labeled "Netzstoff 67 M” are products from Henkel & Cie. GmbH, Düsseldorf (DE).
  • the measurements are carried out separately for the wetting agent and the gloss additive, since a higher sensitivity can be achieved with separate measurements.
  • FIG. 3 shows an example of a polarographic peak PN caused by wetting agents.
  • the potential E between the mercury drop electrode Qe and a reference electrode Re designed as a silver / silver chloride electrode was determined starting from an initial potential E of + 0.1 V at a rate of 20 mV / sec to a final potential E of - 0.5 V changed, in which area the polarographic peak PN occurred.
  • the corresponding current intensity i was measured between the mercury drip electrode Qe and the counter electrode Ge designed as a platinum electrode. The measurement was carried out with direct current in a large drop of mercury (drop size: large).
  • the peak height is given as the current in ⁇ A; however, it can also be measured in mm.
  • FIG. 4 shows an example of a polarographic peak PG caused by the addition of gloss, in which case the measurement was carried out on an undiluted bath solution B1.
  • the potential E was changed with direct current in the case of a large drop of mercury from an initial potential E of + 0.200 V at a rate of 20 mV / sec to an end potential of - 0.450 V, the polarographic peak in this area PG occurred.
  • the current strength i or peak height is given in ⁇ A; however, it can also be measured in mm.
  • FIG. 5 shows the determination of polarographic spades PN1, PN2, PN3, PN4, PN5 and PN6 with the corresponding con concentrations of the wetting agent of 4, 6, 7, 8, 9 and 10 ml per l bath solution. The measurements were carried out on a fresh bath.
  • FIG. 6 shows the determination of polarographic spades PG1, PG2, PG3, PG4, PG5, PG6 PG7 and PG8 with corresponding concentrations GK of the gloss addition of 20, 30, 40, 50, 60, 70, 80 and 100 ⁇ l per l bath solution. The measurements were also carried out on a fresh bath. The potential was changed from + 0.2 V to - 0.45 V for each of the spades PG1 to PG8 measured.
  • FIGS. 7 and 8 show the calibration curves obtained from the measurements corresponding to FIGS. 5 and 6.
  • 7 shows the effective concentration of the wetting agent in ml / l above the peak height PNH given in mm.
  • 8 shows the effective concentration of the gloss additive in ⁇ l / l above the peak height PGH given in mm.
  • the peak height PNH of the peak PN shown in FIG. 3 is approximately 120 mm, this corresponds to an effective concentration of the wetting agent of 7.5 ml / l according to FIG. 7.
  • the peak height PGH of the peak PG shown in FIG. 4 is approximately 75 mm, this corresponds to an effective concentration of the added gloss of 45 ⁇ l / l according to FIG. 8.
  • the measurements described above can be carried out both in a standing and in a stirred bath solution.
  • the measuring sensitivity is increased and there is a better correlation between the effective amount of the added gloss and the properties of the electrodeposited layers, especially when analyzing a loaded bath.

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  • 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)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
EP87106582A 1986-05-21 1987-05-07 Dosage polarographique d'additifs pour bains d'électrodéposition Expired - Lifetime EP0246494B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87106582T ATE49613T1 (de) 1986-05-21 1987-05-07 Verfahren zur polarographischen bestimmung von zusaetzen in galvanischen baedern.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3617046 1986-05-21
DE3617046 1986-05-21

Publications (2)

Publication Number Publication Date
EP0246494A1 true EP0246494A1 (fr) 1987-11-25
EP0246494B1 EP0246494B1 (fr) 1990-01-17

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EP87106582A Expired - Lifetime EP0246494B1 (fr) 1986-05-21 1987-05-07 Dosage polarographique d'additifs pour bains d'électrodéposition

Country Status (4)

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EP (1) EP0246494B1 (fr)
JP (1) JPS62285057A (fr)
AT (1) ATE49613T1 (fr)
DE (1) DE3761442D1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1932953A1 (fr) * 2006-12-11 2008-06-18 Atotech Deutschland Gmbh Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide
CN103014823A (zh) * 2013-01-05 2013-04-03 江苏物联网研究发展中心 改进铜电沉积的添加剂效果快速判定方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5509121B2 (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定量分析方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
METALLOBERFLÄCHE, Band 20, Nr. 7, Juli 1966, Seiten 320-321, DE; VON A.V. KRUSENSTJERN et al.: "Die polarographische Bestimmung von Saccharin in galvanischen Nickelbädern" *
PLATING AND SURFACE FINISHING, Juni 1981, Seiten 78-83, US; M.L. ROTHSTEIN et al.: "Polarographic methods of analyzing plating baths" *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1932953A1 (fr) * 2006-12-11 2008-06-18 Atotech Deutschland Gmbh Procédé galvanique avec analyse du bain electrolytique par extraction en phase solide
WO2008071371A3 (fr) * 2006-12-11 2009-02-26 Atotech Deutschland Gmbh Procédé galvanique avec analyse du bain électrolytique par extraction en phase solide
US9057145B2 (en) 2006-12-11 2015-06-16 Atotech Deutschland Gmbh Electrodeposition method with analysis of the electrolytic bath by solid phase extraction
CN103014823A (zh) * 2013-01-05 2013-04-03 江苏物联网研究发展中心 改进铜电沉积的添加剂效果快速判定方法
CN103014823B (zh) * 2013-01-05 2015-05-13 华进半导体封装先导技术研发中心有限公司 改进铜电沉积的添加剂效果快速判定方法

Also Published As

Publication number Publication date
DE3761442D1 (de) 1990-02-22
ATE49613T1 (de) 1990-02-15
JPS62285057A (ja) 1987-12-10
EP0246494B1 (fr) 1990-01-17

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