Method of monitoring trace constituents in plating baths

• US 4,631,116 A
• Filed: 06/05/1985
• Issued: 12/23/1986
• Est. Priority Date: 06/05/1985
• Status: Expired due to Term

• Current Assignee: Technic, Inc.
• Original Assignee: Hughes Aircraft Company (Rtx Corporation)
• Inventors: Ludwig, Frank A.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/741,492
• Time in Patent Office: 566 Days
• Field of Search: 204/1 T, 204/400, 204/434
• US Class Current: 205/789.5
• CPC Class Codes: G01N 27/42 Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte

Abstract

A method for monitoring the minor constituents present in a plating bath solution which affect plating deposit properties. The method involves applying a predetermined dc potential to a working electrode positioned within the plating bath solution. A constant ac signal is superimposed on the dc potential. The dc potential is varied at a predetermined rate over a predetermined range, which includes potentials which plate and strip the plating deposit. The ac current of the applied ac signal is measured between the working electrode and a counter electrode positioned within the plating bath solution as the dc potential is varied over the predetermined range. The measurement of the ac current in relation to varying dc potential is expressed as an ac current spectra or fingerprint. By optimizing all ac and dc measurement variables, spectra are obtained which contain fine structure and which enable the monitoring of minor plating bath constituents which affect plating deposit properties.

Claims

1. A method for monitoring the minor constituents present in a solution used in a plating process wherein said minor constituents affect plating deposit properties, said method comprising the steps of:

(a) applying a selected dc potential to a working electrode which has been subjected to pretreatment and is positioned with said solution containing said minor constituents;

(b) superimposing a constant ac signal on said dc potential applied to said working electrode, said ac signal having a peak to peak potential and a frequency and producing an ac current;

(c) varying said dc potential at a chosen sweep rate over a chosen range; and

(d) measuring said ac current at one or more phase angles with respect to said constant ac signal between said working electrode and a counter electrode positioned within said solution as said dc potential is varied over said range, said measurement of ac current in relation to varying dc potential being expressed as an ac current spectra wherein the improvement comprises varying in combination each parameter comprising said peak to peak potential of said ac signal, said frequency of said ac signal, said sweep rate of said dc potential, said range of dc potential, said one or more phase angles, and said pretreatment of said working electrode, to determine the specific value of each said parameter which, when taken in combination with the remaining said parameters, provides maximum spectra detail in said ac current spectra to determine and monitor said minor constituents in said solution which affect said plating deposit properties.

2. A method according to claim 1 wherein said plating bath solution includes a metal for plating a deposit and wherein said range over which said dc potential is varied includes a plating potential range in which said metal is plated onto said working electrode and a stripping potential range in which metal present on said working electrode is stripped therefrom.

3. A method according to claim 2 wherein said dc potential is varied from said stripping range to said plating range and then back to said stripping range.

4. A method according to claim 2 wherein said working electrode is subjected to said pretreatment prior to said applying of said dc potential to said working electrode, and said pretreatment comprises establishing equilibrium conditions surrounding said working electrode by stirring said plating bath solution for a first selected period of time and then allowing said plating bath solution to be quiescent for a second selected period of time, and subsequently anodically preconditioning and stabilizing said working electrode at a selected voltage or set of voltages positive to or within said sripping potential range for one or more selected periods of time to thereby maximize the reproducibility of said spectra detail of said ac current spectra.

5. A method according to claim 4 wherein the working electrode is anodically preconditioned at a voltage equal to or more positive than said selected voltage to maximize halide ion interaction or at a voltage less positive than said selected voltage to minimize halide interactions.

6. A method according to claim 1 wherein said range of said dc potential is extended to a negative voltage limit at which the ac current or the subsequent ac stripping current rises to approximately 50 to 100 times the current of the smallest peaks in said ac current spectra.

7. A method according to claim 1 wherein measurement of said ac current is made at the second harmonic frequency relative to the frequency of said ac signal to further maximize said spectra detail.

8. A method according to claim 7 wherein said range of said dc potential is extended to a negative limit at which the ac current or the subsequent ac stripping current rises to approximately 50 to 100 times the current of the smallest peaks in said ac current spectra.

9. A method according to claim 8 wherein said range of said dc potential is extended beyond said negative limit in order to avoid interferences between plating bath constituents or to develop extra peaks for analysis of all said minor constituents.

10. A method according to claim 9 wherein the negative limit is extended until the signal/noise ratio decreases to an undesirable level.

11. A method acccording to claim 10 wherein quantitative analyses of said minor constituents in said plating bath are obtained by determining two or more spectra for said minor constituents and wherein interferences are eliminated by varying the phase angle and ac frequency.

12. A method according to claim 1 wherein said plating bath solution includes a metal selected from the group consisting of copper, iron, nickel, chromium, zinc, tin, gold, silver, lead, platinum, cadmium, palladium, rhodium, indium, cobalt and mixtures thereof.

13. A method according to claim 12 wherein the dc potential is varied from about 1 millivolt/second to about 500 millivolts/second.

14. A method according to claim 13 wherein said metal is copper and said plating bath solution is acidic, and wherein the dc potential is varied at a rate of about 20 millivolts/second.

15. A method according to claim 12 wherein said ac signal has a peak to peak potential of between about 5 millivolts and 100 millivolts and a frequency of between about 10 hertz and 10,000 hertz.

16. A method according to claim 15 wherein said metal is copper and said plating bath solution is acidic, and wherein the peak to peak potential is about 25 millivolts and the frequency is about 50 hertz.

17. A method according to claim 12 wherein said metal is copper and said plating bath solution is acidic, and the range over which said dc potential is varied is between about +1.1 volts and -0.2 volt versus a standard calomel electrode.

18. A method for monitoring the change in minor constituents present in a plating bath solution which affect plating deposit properties, said method comprising the steps of:

using the method of claim 1 to make a first determination of one or more ac current spectra for a plating bath solution having known desirable plating properties;

using the method of claim 1 to make a second determination of one or more ac current spectra for said plating bath solution at a time after said first determination; and

comparing said second spectra to said first spectra to monitor changes in the minor constituents present in the plating bath solution.

19. A method according to claim 1 wherein the following steps are performed in turn:

(a) the value of each of said parameters is set at a predetermined level;

(b) the value of a first said parameter is varied in order to determine and set a specific value of said first parameter which optimizes the detail in said ac current spectra;

(c) the value of a second said parameter is varied in order to determine and set a specific value of said second parameter which optimizes the detail in said ac current spectra; and

(d) the value of each remaining said parameter, in turn, is varied in order to determine and set the specific value of each said remaining parameters which optimizes the detail in said ac current spectra wherein said specific values of said parameters, when taken in combination, provide said miximum spectra detail.

20. In a cyclic voltammetric stripping method for monitoring the presence of minor constituents in a metal plating bath solution wherein:

(a) a dc potential is applied to a pretreated working electrode immersed in said plating bath solution and said dc potential is cycled at a constant sweep rate over a chosen range so that a small amount of said metal is alternately deposited on the surface of said working electrode by electrodeposition and stripped off by anodic dissolution;

(b) a constant ac signal is superimposed on said dc potential applied to working electrode, said ac signal having a chosen peak to peak potential and a chosen frequency and producing an ac current;

(c) measuring said ac current at one or more phase angles with respect to said constant ac signal between said working electrdoe and a counter electrode positioned within said plating bath solution as said dc potential is cycled, said measurement of said ac current in relation to said cycled dc potential being expressed as an ac current spectra of said plating bath solution wherein the improvement comprises varying in combination each parameter comprising said peak to peak potential of said ac signal said frequency of said ac signal, said sweep rate of said dc potential, said range of said dc potential, said one or more phase angles, and said pretreatment of said working electrode to determine the specific value of each said parameter which, when taken in combination with the remaining said parameters, provides maximum spectra detail in said ac current spectra to determine and monitor said minor constituents present in said plating bath solution.

21. An improved method according to claim 20 wherein measurement of said ac current is made at the second harmonic frequency of said ac signal.