Methods for determining organic component concentrations in an electrolytic solution

1. A method for determining concentration of an organic component in a sample electrolytic solution, said method comprising the steps of:

(a) applying a potential step to the sample electrolytic solution by using at least a working electrode and a reference electrode;

(b) measuring double layer capacitance of the working electrode in said sample electrolytic solution under the applied potential step;

(c) determining the concentration of the organic component in said sample electrolytic solution, based on the double layer capacitance measured in step (b), and

(d) adding organic component when the concentration of organic component falls below effective electrolytic solution levels,

wherein the sample electrolytic solution comprises a copper electroplating solution comprising copper ions, and wherein the copper ions do not deposit onto the working electrode;

wherein the double layer capacitance of the working electrode is measured by monitoring current response of the sample electrolytic solution under the potential step over time; and

wherein the current response is measured using at least one measuring device selected from the group consisting of poteniometers, ammeters and ohmmeters.

2. The method of claim 1 , wherein the organic component comprises an organic additive selected from the group consisting of suppressors, accelerators, and levelers.

3. The method of claim 1 , wherein one or more calibration solutions containing said organic component at unique, known concentrations are provided, wherein the double layer capacitance of the working electrode in each of said calibration solutions under the potential step is measured, which is correlated to the concentration of the organic component in respective calibration solution, and wherein the concentration of the organic component in the sample electrolytic solution is determined based on the double layer capacitance measured for said sample electrolytic solution and the capacitance-concentration correlation obtained by measuring the calibration solutions.

4. The method of claim 3 , wherein said one or more calibration solutions are compositionally identical to said sample electrolytic solution but for the organic component concentration.

5. The method of claim 1 , wherein the double layer capacitance (C d ) of the working electrode is determined by:

C

d

=

t

c

×

I

max

E

wherein E is the applied potential step, I max is the current peak observed under said applied potential step E, and t c is a time constant, which is equal to the time required for the current to drop from I max to about 0.368×I max .

6. A method for determining concentration of an organic component in a sample electrolytic solution, said method comprising the steps of:

(a) applying a potential step to the sample electrolytic solution by using at least a working electrode and a reference electrode;

(b) measuring double layer capacitance of the working electrode in said sample electrolytic solution under the applied potential step;

(c) determining the concentration of the organic component in said sample electrolytic solution, based on the double layer capacitance measured in step (b), and

(d) adding organic component when the concentration of organic component falls below effective electrolytic solution levels,

wherein the sample electrolytic solution comprises a copper electroplating solution comprising copper ions, and wherein the copper ions do not deposit onto the working electrode;

wherein one or more calibration solutions containing said organic component at unique, known concentrations are provided, wherein the double layer capacitance of the working electrode in each of said calibration solutions under the potential step is measured, which is correlated to the concentration of the organic component in respective calibration solution, and wherein the concentration of the organic component in the sample electrolytic solution is determined based on the double layer capacitance measured for said sample electrolytic solution and the capacitance-concentration correlation obtained by measuring the calibration solutions; and

wherein the capacitance-concentration correlation data set is stored in a memory of a computational assembly.

7. The method of claim 6 , wherein said computation assembly comprises an assembly selected from the group consisting of computers, central processing units (CPUs), mirocprocessors, and integrated circuitry.

8. The method of claim 6 , wherein said computational assembly maps concentration of the organic component in said sample electrolytic solution based on the measured double layer capacitance and a correlative data set that empirically correlates double layer capacitance with concentration of the organic component.

9. The method of claim 6 , wherein the capacitance-concentration correlation data set is constructed in situ by said computational assembly according to a capacitance-concentration correlation protocol.

10. The method of claim 6 , wherein the organic component comprises an organic additive selected from the group consisting of suppressors, accelerators, and levelers.

11. The method of claim 6 , wherein said one or more calibration solutions are compositionally identical to said sample electrolytic solution but for the organic component concentration.

12. The method of claim 6 , wherein the double layer capacitance of the working electrode is measured by monitoring current response of the sample electrolytic solution under the potential step over time.

13. The method of claim 6 , wherein the double layer capacitance (C d ) of the working electrode is determined by:

C

d

=

t

c

×

I

max

E

wherein E is the applied potential step, I max is the current peak observed under said applied potential step E, and t c is a time constant, which is equal to the time required for the current to drop from I max to about 0.368×I max .

14. A method for determining concentration of an organic component in a sample electrolytic solution, said method comprising the steps of:

(a) applying a potential step to the sample electrolytic solution by using at least a working electrode and a reference electrode;

(b) measuring double layer capacitance of the working electrode in said sample electrolytic solution under the applied potential step;

(c) determining the concentration of the organic component in said sample electrolytic solution, based on the double layer capacitance measured in step (b), and

(d) adding organic component when the concentration of organic component falls below effective electrolytic solution levels,

wherein the sample electrolytic solution comprises a copper electroplating solution comprising copper ions, and wherein the copper ions do not deposit onto the working electrode; and

wherein the organic additives contained in the sample electrolytic solution are not consumed during the measurement of the double layer capacitance.

15. The method of claim 14 , wherein organic component comprises an organic additive selected from the group consisting of suppressors, accelerators, and levelers.

16. The method of claim 14 , wherein one or more calibration solutions containing said organic component at unique, known concentrations are provided, wherein the double layer capacitance of the working electrode in each of said calibration solutions under the potential step is measured, which is correlated to the concentration of the organic component in respective calibration solution, and wherein the concentration of the organic component in the sample electrolytic solution is determined based on the double layer capacitance measured for said sample electrolytic solution and the capacitance-concentration correlation obtained by measuring the calibration solutions.

17. The method of claim 16 , wherein said one or more calibration solutions are compositionally identical to said sample electrolytic solution but for the organic component concentration.

18. The method of claim 14 , wherein the double layer capacitance of the working electrode is measured by monitoring current response of the sample electrolytic solution under the potential step over time.

19. The method of claim 18 , wherein the current response is measured using at least one measuring device selected from the group consisting of poteniometers, ammeters and ohmmeters.

20. The method of claim 14 , wherein the double layer capacitance (C d ) of the working electrode is determined by:

C

d

=

t

c

×

I

max

E

wherein E is the applied potential step, I max is the current peak observed under said applied potential step E, and t c is a time constant, which is equal to the time required for the current to drop from I max to about 0.368×I max .