EP0016415B1 - Verfahren zum Messen und Regeln der Konzentration von Kupfer, Formaldehyd und Natronlauge in einem Bad zum stromlosen Abscheiden von Kupfer, sowie Probennahmevorrichtung zur Verwendung bei diesem Verfahren - Google Patents

Verfahren zum Messen und Regeln der Konzentration von Kupfer, Formaldehyd und Natronlauge in einem Bad zum stromlosen Abscheiden von Kupfer, sowie Probennahmevorrichtung zur Verwendung bei diesem Verfahren Download PDF

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Publication number
EP0016415B1
EP0016415B1 EP80101281A EP80101281A EP0016415B1 EP 0016415 B1 EP0016415 B1 EP 0016415B1 EP 80101281 A EP80101281 A EP 80101281A EP 80101281 A EP80101281 A EP 80101281A EP 0016415 B1 EP0016415 B1 EP 0016415B1
Authority
EP
European Patent Office
Prior art keywords
titration
determined
concentration
copper
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.)
Expired
Application number
EP80101281A
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German (de)
English (en)
French (fr)
Other versions
EP0016415A1 (de
Inventor
Jacky Dr. Vanhumbeeck
Hubert De Steur
Guido Heyneman
Chris Dipl.-Chem. Vandenbossche
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
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Siemens AG
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Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP0016415A1 publication Critical patent/EP0016415A1/de
Application granted granted Critical
Publication of EP0016415B1 publication Critical patent/EP0016415B1/de
Expired 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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/12—Condition responsive control

Definitions

  • the invention relates to a method for measuring and regulating the concentration of copper, formaldehyde and sodium hydroxide solution in a bath for electroless deposition of copper, the copper ion concentration colorimetrically detecting the sodium hydroxide concentration by potentiometric titration and the formaldehyde concentration by amperometric titration and compared with adjustable target values, as well as on a drug-taking device for use in this method.
  • the main components of a chemical copper bath are to be analyzed and regulated with such a process so that the deposition conditions remain constant and perfect copper layers are achieved.
  • a method of the type mentioned at the outset has become known from US Pat. No. 4,096,301.
  • a bath sample is continuously taken from the copper bath.
  • a standardized acid of such a concentration and amount is also continuously added to this bath sample that a potentially predetermined final value can be achieved.
  • the bath sample passes through a pH value measuring station, in which the actual pH value is measured and compared with a predetermined target value.
  • sodium hydroxide solution is then metered into the copper bath in accordance with this deviation.
  • the bath sample then passes through a colorimeter station, in which the copper ion concentration is checked and, in the event of a deviation from the nominal value, an amount of copper solution corresponding to this deviation is metered into the copper bath.
  • a colorimeter station After passing through the colorimeter station, sodium sulfide is continuously added to the bath sample and, after appropriate mixing, is fed to another pH value station, where the pH value of the bath sample is measured again and the difference is formed using the previously determined pH value. This difference is a measure of the formaldehyde concentration. If there is a deviation from the specified setpoint, a corresponding amount of formaldehyde is added to the bath.
  • a method of the same type is known from DE-A-2 751 104.
  • a bath sample is also continuously taken from the chemical copper bath and passed into a chamber where a deposition electrode is located. Adjacent to this chamber is a further chamber with a comparison electrode, which together with the deposition electrode serves to measure a mixed potential. After the so-called “mixed potential" has been recorded, the bath sample is fed to a pH value station and a colorimeter station via a heat exchanger. The individual bath components are then regulated as a function of this mixed potential.
  • GB-A-1 168370 has also disclosed a process of the type mentioned at the outset, in which the pH is kept at a constant value with the aid of alkali hydroxide in order to stabilize the bath, and the copper ions at the specified pH Concentration is measured colorimetrically. Depending on this measurement, a mixture of formaldehyde and copper salt is added in a certain molar ratio.
  • the invention has for its object to improve a method of the type mentioned so that the content of the main components can be analyzed, displayed and controlled more precisely.
  • This object is achieved in that a sample is taken discontinuously for each of the components mentioned and this is diluted with a certain amount of water, that the copper ion concentration by colorimetry, the sodium hydroxide solution concentration by potentiometric titration and the formaldehyde concentration are then independent of one another be determined by amperometric titration and that in the amperometric titration of the formaldehyde concentration as the titrant hydroxylammonium hydrochloride and as the working electrode a gold electrode operated with a constant polarization voltage of 0-200 mV against a silver-silver chloride reference electrode are used, the current between the working electrode and a counter electrode is measured.
  • the titration end point is preferably made from the three by an approximation method known per se largest potential steps with constant addition of titrant are calculated, the supply of the titrant being added with the aid of a motor piston burette in constant volume units by appropriate step-by-step control of the buret motor and after each addition of titrant for stabilization a constant rest time is inserted before the measurement signal is detected. In this way an extremely precise determination of the sodium hydroxide concentration is achieved.
  • the end point of the amperometric titration is determined by the intersection of two straight lines, one of which runs parallel to the abscissa and the minimum of the titration curve and the other through several measuring points of the quasi-linear range of the rising part following the minimum the titration curve is determined. It has been found to be particularly favorable that the minimum of the titration curve is determined and stored in order to determine the one straight line, and that five measuring points of the quasi-linear region of the ascending part of the titration curve are used to determine the other straight line, and that this straight line is calculated using a regression method and determining the intersection of the two straight lines with the aid of a computer.
  • a particularly simply constructed sampling device for use in the method according to the invention is characterized in that the individual bath samples can be removed from the bath by means of slide-controlled sampling valves with the aid of measuring loops, the individual measuring loops being connected in series when the samples are taken and this series connection of the measuring loop being controlled by a controllable valve in parallel is switched.
  • the content of the measuring loops can be transferred into the vessels with the aid of metering syringes which add distilled water.
  • FIG. 1 denotes a galvanic bath which is said to have a specific composition, the main components being copper, sodium hydroxide solution and formaldehyde. The concentrations of these components should be regulated to constant values.
  • This chemical copper bath works, for example, at a temperature above 50 ° C. A certain proportion of the sample is taken from the chemical copper bath via a line 2. This portion passes through a cooling device 3 and is cooled there to at least 30 ° C. This portion is fed to the individual stations via a line 4.
  • the upper part of FIG. 1 shows the process sequence for determining the copper ion concentration by colorimetry. We are looking for the concentration in grams of copper per liter, as indicated by a symbol 5.
  • a discontinuous sampling takes place, namely of 1 ml.
  • This sample is diluted in a mixing vessel 8 with twice 20 ml of water, as indicated by an arrow 9.
  • the two measuring cells 10 and 11 of a colorimeter 12 are filled from the mixing vessel 8, the measuring cell 11 having a thickness of 10 mm and the measuring cell 10 having a thickness of 20 mm.
  • the measurement in the colorimeter 12 takes place at 690 nm.
  • An alternating light colorimeter is preferably used, since this only requires a photo element for light measurement, onto which the measuring beam and the comparison beam alternately fall. Signals proportional to the light intensity can then be taken from an output line 13 and fed to a corresponding evaluation circuit 14, where the copper concentration C cu is calculated from the product kA, k being a calibration factor and A being the measurement signal proportional to the copper concentration.
  • the process sequence for the titration of the sodium hydroxide solution is shown in the middle of FIG.
  • the concentration of the sodium hydroxide solution in grams per liter is sought, as indicated by symbol 15.
  • a sample amount of 2 ml is preferably taken and mixed in a mixing vessel 18 with twice 20 ml of water, as indicated by an arrow 19.
  • the sodium hydroxide solution is titrated with dilute hydrochloric acid (HCl) in the same mixing vessel 18.
  • a pH electrode is indicated at 22.
  • the signals are fed to an evaluation circuit 24 via a line 23, the alkali concentration C NaoH being determined from the product K'. ⁇ , where K 'is a calibration factor and ⁇ the calculated volumes in the titration end point.
  • FIG. 1 In the lower part of FIG. 1, the chemical procedure for the amperometric titration of formaldehyde is shown.
  • the concentration of formaldehyde in grams per liter should be determined, as symbol 25 shows.
  • a symbol 30 illustrates that 15 ml of 1 M NaOH diluted with 45 ml of H 2 O are fed to the titration vessel 29 before the actual titration.
  • the two substances are mixed intimately with the aid of a stirring device 31.
  • a gold electrode 32 as the working electrode, a platinum electrode 33 as the counter electrode and a silver / silver chloride electrode 34 as the reference electrode are immersed in the titration vessel 29.
  • a titrant is added via a line 36, specifically hydroxylammonium hydrochloride (NH 2 0H. HCl).
  • the voltage between the working electrode 32 and the counter electrode 33 is regulated so that the voltage of the working electrode 32 always remains constant with respect to the reference electrode 34. If a silver / silver chloride electrode is used as the reference electrode, it is advantageous that a polarization voltage of +50 mV is selected.
  • the current flowing between counter electrode 33 and working electrode 32 is measured and results in a specific titration curve depending on the amount of titrant added.
  • the titration end point can then be determined by methods known per se using the titration curve according to FIG. Preferably, such a method is chosen that the titration end point can be determined fully automatically.
  • the use of a gold electrode as the working electrode has the advantage that no copper can settle there because the gold electrode always has a positive potential. It has proven to be particularly favorable if the titrant NH Z OH. HCl has a concentration of 0.5 g / l.
  • K are a calibration factor and ⁇ the calculated volume at the titration end point.
  • Figure 3 shows the typical course of a titration curve K in an amperometric titration of formaldehyde under the aforementioned conditions.
  • V [ml] the amount of the continuously added titrant
  • NH 2 0H the amount of the continuously added titrant
  • HCI the current I [mA] plotted.
  • the end point Ep of the amperometric titration is preferably determined by the intersection A of two straight lines G1, G2, one of which runs parallel to the abscissa axis and goes through the minimum of the titration curve and the other through several measuring points P1 ... P5 of the quasi-linear range of the the minimum following ascending part of the titration curve is determined.
  • the concentration of copper, sodium hydroxide solution and formaldehyde are therefore determined completely independently of one another.
  • the individual control processes and the measurement value processing are carried out with the aid of a control circuit 39 containing a microprocessor.
  • the concentration of the main components copper, sodium hydroxide solution and formaldehyde are therefore analyzed independently and the analysis results are recorded, as indicated at 40.
  • a signal that is proportional to the deviation is formed for each component.
  • These signals can be used to control appropriate dosing groups to refresh the bath.
  • the bath temperature can also be measured and logged.
  • FIG. 2 shows the mechanical construction of the bath guiding device in principle, with the same parts having the same reference numerals as in FIG. 1.
  • a measuring line 42 always receives the actual bath composition
  • part of the bath 1 is pumped in the circuit via a line 41 in the secondary flow.
  • This flow can be controlled by means of a valve 43. If the valve 43 is closed, the liquid is pressed through the measuring line 42.
  • the measuring line 42 can also be connected via a valve 44, which can be a slide valve, for example, to a line 46 which is connected to a container which contains a calibration solution for the purpose of calibrating the individual devices. With the help of a slide 45, the measurement can then Line 42 can either be connected to line 4 or to a line 46.
  • a compressed air-controlled valve 7 is used for discontinuous sampling.
  • the individual connection bores of the valve are designated by a to f and can be connected to one another or to one another by corresponding grooves 7a, 7b and 7c in the slide.
  • a measuring loop 47 is connected between the connection bores b and c and is calibrated to 1 ml. In the slide position shown in FIG. 2, the line 4 is thus connected via the bores a and b of the valve 44 to the connection bore a in the valve 7.
  • the sample passes through the connection bore b into the measuring loop 47 and from there via the connection bore c, the longitudinal groove 7c and the connection bore d into the measuring line 42, where it continues in a corresponding manner through the valves 17 and 27 and finally can flow back to the bathroom via the measuring line 4.
  • the smaller diameter piston 7d of the valve 7 is constantly pressurized with compressed air from a compressed air supply system 48. If a valve 49 is activated for taking a sample, the compressed air of the compressed air system 48 now also reaches a piston 7a with a larger diameter than that of the piston 7d. Accordingly, the slide is moved to the right in relation to FIG.
  • the longitudinal grooves 7b and 7c of the slide now connect the connection bores b and e or c and f; with the help of a dosing syringe 50, a precisely dosed amount of water, namely 20 ml, is taken from a line 51, which is fed via a line 52 to the connection bore f, so that the content of the measuring loop 47 is transferred to the line 9, which ends in the mixing vessel 8 .
  • the mixing vessel 8 is provided with a drain valve 53 and a stirring motor 54.
  • a valve 59 indicates that the sample raised in the measuring cuvettes 10 and 11 1 can either be returned to the vessel 8 or can be passed into a collecting container; the sample can also be lifted several times.
  • the valve 17 is constructed in the same way as the valve 7, except that a measuring loop 60 is inserted into the connection bores b and c, which is calibrated to 2 ml in the special case. With the aid of a dosing syringe 61, the content of this measuring loop can be transferred into the mixing vessel 18 by sucking in distilled water via a line 62, namely with a 20 ml stroke, as can be seen from FIG.
  • the pH electrode 22 is immersed in the mixing vessel 18, so that it also serves as a titration vessel.
  • 63 is a drain valve and 64 an agitator.
  • the engine piston burette, designated 20, takes HCI via a line 65 and is supplied to the vessel 18 via line 21, the engine feeding the engine piston burette to the bath sample intermittently in each case 0.2 ml until the titration end point is recognized.
  • the valve 27 corresponds in structure and operation to the valves 7 and 17, except that a measuring loop 66 is connected between the connection bores b and c, which is calibrated to 0.1 ml.
  • the valve 27 is activated via a valve 67 in the same way as the valve 49.
  • the bath sample taken with the help of the measuring loop 66 is mixed with 45 ml of water and fed to the titration vessel 29 via a line 28.
  • a certain quantity of sodium hydroxide solution NaOH
  • the titration is then carried out with NH 2 0H. HCI via a line 36.
  • the motor piston burette 35 is driven step by step until the titration end point is reached.
  • amperometric titration is used for the determination of formaldehyde, since it is much more precise than the known other titration methods.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Chemically Coating (AREA)
EP80101281A 1979-03-21 1980-03-12 Verfahren zum Messen und Regeln der Konzentration von Kupfer, Formaldehyd und Natronlauge in einem Bad zum stromlosen Abscheiden von Kupfer, sowie Probennahmevorrichtung zur Verwendung bei diesem Verfahren Expired EP0016415B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2911073A DE2911073C2 (de) 1979-03-21 1979-03-21 Verfahren und Vorrichtung zum automatischen Messen und Regeln der Konzentration der Hauptkomponenten eines Bades zum stromlosen Abscheiden von Kupfer
DE2911073 1979-03-21

Publications (2)

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EP0016415A1 EP0016415A1 (de) 1980-10-01
EP0016415B1 true EP0016415B1 (de) 1984-06-13

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EP80101281A Expired EP0016415B1 (de) 1979-03-21 1980-03-12 Verfahren zum Messen und Regeln der Konzentration von Kupfer, Formaldehyd und Natronlauge in einem Bad zum stromlosen Abscheiden von Kupfer, sowie Probennahmevorrichtung zur Verwendung bei diesem Verfahren

Country Status (4)

Country Link
US (1) US4286965A (enrdf_load_stackoverflow)
EP (1) EP0016415B1 (enrdf_load_stackoverflow)
JP (1) JPS55128572A (enrdf_load_stackoverflow)
DE (1) DE2911073C2 (enrdf_load_stackoverflow)

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JPS61110799A (ja) * 1984-10-30 1986-05-29 インタ−ナシヨナル　ビジネス　マシ−ンズ　コ−ポレ−シヨン 金属めつき槽の制御装置
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FR2575306B1 (fr) * 1984-12-21 1987-02-13 Elf Aquitaine Procede de regulation de la charge d'amine sur une colonne d'epuration du gaz naturel
JPS61199069A (ja) * 1985-02-28 1986-09-03 C Uyemura & Co Ltd めっき液濃度自動連続管理装置
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US4654126A (en) * 1985-10-07 1987-03-31 International Business Machines Corporation Process for determining the plating activity of an electroless plating bath
US4967690A (en) * 1986-02-10 1990-11-06 International Business Machines Corporation Electroless plating with bi-level control of dissolved oxygen, with specific location of chemical maintenance means
US4774101A (en) * 1986-12-10 1988-09-27 American Telephone And Telegraph Company, At&T Technologies, Inc. Automated method for the analysis and control of the electroless metal plating solution
DE3718584A1 (de) * 1987-06-03 1988-12-15 Norddeutsche Affinerie Verfahren zur messung der wirksamen inhibitorkonzentration waehrend der metallabscheidung aus waessrigen elektrolyten
US4908676A (en) * 1987-12-18 1990-03-13 Bio-Recovery Systems, Inc. Sensors for dissolved substances in fluids
US5117370A (en) * 1988-12-22 1992-05-26 Ford Motor Company Detection system for chemical analysis of zinc phosphate coating solutions
US5352350A (en) * 1992-02-14 1994-10-04 International Business Machines Corporation Method for controlling chemical species concentration
KR100201377B1 (ko) * 1995-10-27 1999-06-15 김무 다성분 도금용액의 농도조절장치
US6269533B2 (en) 1999-02-23 2001-08-07 Advanced Research Corporation Method of making a patterned magnetic recording head
US6419754B1 (en) 1999-08-18 2002-07-16 Chartered Semiconductor Manufacturting Ltd. Endpoint detection and novel chemicals in copper stripping
US6496328B1 (en) 1999-12-30 2002-12-17 Advanced Research Corporation Low inductance, ferrite sub-gap substrate structure for surface film magnetic recording heads
TWI240763B (en) * 2001-05-16 2005-10-01 Ind Tech Res Inst Liquid phase deposition production method and device
US6986835B2 (en) * 2002-11-04 2006-01-17 Applied Materials Inc. Apparatus for plating solution analysis
US7851222B2 (en) * 2005-07-26 2010-12-14 Applied Materials, Inc. System and methods for measuring chemical concentrations of a plating solution
KR20140066513A (ko) * 2012-11-23 2014-06-02 삼성전기주식회사 금속 도금액 중의 알데히드 화합물의 분석방법
CA3017667A1 (en) 2017-09-18 2019-03-18 Ecolab Usa Inc. Adaptive range titration systems and methods
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US11397170B2 (en) * 2018-04-16 2022-07-26 Ecolab Usa Inc. Repetition time interval adjustment in adaptive range titration systems and methods
CN108344700A (zh) * 2018-05-15 2018-07-31 珠海倍力高科科技有限公司 一种化学铜分析控制系统

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BE630787A (enrdf_load_stackoverflow) * 1962-04-10
NL301241A (enrdf_load_stackoverflow) * 1963-12-02
FR1551275A (enrdf_load_stackoverflow) * 1966-12-19 1968-12-27
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Publication number Publication date
DE2911073C2 (de) 1984-01-12
JPS55128572A (en) 1980-10-04
US4286965A (en) 1981-09-01
DE2911073A1 (de) 1980-10-02
EP0016415A1 (de) 1980-10-01
JPS6318664B2 (enrdf_load_stackoverflow) 1988-04-19

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