# Patent

## Title
Methods for determining organic component concentrations in an electrolytic solution

## Abstract

The present invention relates to a method and apparatus for determining organic additive concentrations in a sample electrolytic solution, preferably a copper electroplating solution, by measuring the double layer capacitance of a measuring electrode in such sample solution. Specifically, the present invention utilizes the correlation between double layer capacitance and the organic additive concentration for concentration mapping, based on the double layer capacitance measured for the sample electrolytic solution.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional application of U.S. patent application Ser. No. 10/833,194, entitled “Methods For Determining Organic Component Concentrations In An Electrolytic Solution”, filed on Apr. 27, 2004, and issued as U.S. Pat. No. 6,984,299 on Jan. 10, 2006.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to methods and apparatuses for determining organic component concentrations in an electrolytic solution, and more specifically to determination of organic component concentrations in a copper electroplating solution.
2. Description of the Related Art
In electrochemical deposition (ECD) process, the rigorous control of the relative proportions of respective inorganic and organic ingredients in the ECD bath is critical to the achievement of satisfactory results in the rate of metal film formation and the quality of the film so formed. During the use of the plating bath solution, the plating process may be affected by depletion of inorganic components and organic additives as well as by organic byproduct formation. The ECD bath chemistry therefore must be maintained by periodic replacement of a part or the entire ECD bath. It is therefore important to continuously or periodically monitor the concentrations of inorganic and/or organic components in the ECD bath, and responsively add respective components to the bath to maintain the composition of the bath in an effective state for the electrochemical deposition operation.
It is therefore one object of the present invention to provide an improved method for measuring concentrations of one or more organic components in an ECD bath.
Other objects and advantages will be more fully apparent from the ensuring disclosure and appended claims.
SUMMARY OF THE INVENTION
The present invention in one aspect relates to a method for determining concentration of an organic component in a sample electrolytic solution. Such method comprises 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 the sample electrolytic solution under the applied potential step; and
        (c) determining the concentration of the organic component in the sample electrolytic solution, based on the double layer capacitance measured in step (b).
    
    


Another aspect of the present invention relates to an apparatus for measuring concentration of an organic component in a sample electrolytic solution, comprising:

    
    
        (a) a measuring chamber containing a working electrode and a reference electrode, for receiving at least a portion of the sample electrolytic solution;
        (b) an electrical source for applying a potential step to the sample electrolytic solution through the working and reference electrodes;
        (c) means for measuring double layer capacitance of the working electrode in said sample electrolytic solution under the applied potential step; and
        (d) computational means for determining the concentration of the organic component in said sample electrolytic solution, based on the double layer capacitance measured for the working electrode in the sample electrolytic solution.
    
    


Other aspects, features and embodiments of the present invention will be more fully apparent from the ensuing disclosure and appended claims.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the current response curves measured for four different electrolytic solutions over time under an initial potential step of about −0.208V.



DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF
The boundary between a measuring electrode and an electrolytic solution is called an interface. The electrolytic solution is a first phase in which charge is carried by the movement of ions, and the measuring electrode is a second phase in which charge is carried by the movements of electrons.
Two types of processes occur at the electrode-solution interface: (1) the faradaic process involves actual electron transfers between the measuring electrode and the electrolytic solution; and (2) the non-faradaic process involves adsorption and desorption of organic species onto and from the electrode surface where no charge actually cross the interface.
During non-faradaic process, although no charge actually cross the interface, external transient currents are present when the electrical potential, electrode surface area, or the composition of the electrolytic solution changes. These transient currents flow to charge or discharge the electrode-solution interfacial region, which is generally referred to as an electrical double layer.
The capacitance of such electrical double layer (Cd) is a function of the applied electrical potential (E), the composition and concentration of the electrolytic solution, and the active electrode surface area. When the applied electrical potential and the active electrode surface area are constant, the double layer capacitance is directly correlative to the composition and concentration of the electrolytic solution.
Therefore, the present invention in one aspect provides a method for measuring the organic additive (i.e., suppressors, accelerators, and levelers) concentrations in a metal electroplating solution, more preferably a copper electroplating solution, based on the double layer capacitance of a working electrode that is immersed in such metal electroplating solution.
Under a given initial electrical potential or potential step (E), the metal electroplating solution demonstrates a current response that is characterized by an initial current peak or maximum current (Imax) at initial time t0 and an exponentially decaying current (I) at subsequent time t, which are determined by:




  
    
      
        
          
            I
            max
          
          =
          
            E
            
              R
              s
            
          
        
        ;
      
    
    
      
        (
        I
        )
      
    
  
  
    
      
        I
        =
        
          
            I
            max
          
          ×
          
            e
            
              (
              
                t
                
                  
                    R
                    s
                  
                  ⁢
                  
                    C
                    d
                  
                
              
              )
            
          
        
      
    
    
      
        (
        II
        )
      
    
  




where Rs is the electrical resistance of the electrolytic solution, and e is the base for natural exponential.

When t=RsCd, the current I has decreased to about 37% of the initial current peak, as follows:

I=Imax×e(−1)=0.368×Imax  (III)

The value of RsCd is usually referred to as the time constant tc, which is characteristic to the given electrode-solution interface.
From equations (I)-(III), one can express the double layer capacitance Cd as:




  
    
      
        
          C
          d
        
        =
        
          
            
              t
              c
            
            ×
            
              I
              max
            
          
          E
        
      
    
    
      
        (
        IV
        )
      
    
  




Therefore, by measuring the current peak Imax, the time constant tc required for the current to decrease to about 37% of the current peak Imax, and the initial potential step E, the double layer capacitance Cd of the measuring electrode in the sample electroplating solution can be determined quantitatively.
The current response of an electrolytic solution can be monitored by using one or more measuring devices. For example, an ammeter can be used to directly measuring the current flow through the sample electrolytic solution over time; alternatively, a combination of one or more potentiometers and one or more ohmmeters can be used to measuring the real-time potential and electrical resistance of the sample electrolytic solution, from which the current flow can be calculated.
Preferably, one or more calibration solutions are provided for constructing a correlative data set, which empirically correlates the double layer capacitance with the concentration of an organic component of interest. Specifically, each calibration solution so provided is compositionally identical to the sample electroplating solution but for the concentration of the organic component of interest, and each calibration solution preferably contains said organic component of interest at a unique, known concentration. The double layer capacitance of each calibration solution is measured according to the method described hereinabove and used in conjunction with the respective known concentration of the organic component of interest in each calibration solution to form the correlative data set.
Such correlative data set can then be used for direct mapping of the concentration of the organic component of interest in the sample electroplating solution, based on the double layer capacitance measured for such sample electroplating solution.
Preferably, the present invention employs a computer-based quantitative analyzer, which may comprise a computer, central processor unit (CPU), microprocessor, integrated circuitry, operated and arranged to collect the current response data for determining the double layer capacitance of the sample solution and according to the method described hereinabove and for mapping the organic component concentration. More preferably, such quantitative analyzer has a correlative data set stored in its memory for direct concentration mapping based on the double layer capacitance measured for the sample solution. Alternatively, such quantitative analyzer comprises a capacitance-concentration correlation protocol for in situ construction of such a correlative data set based on current response data collected for various calibration solutions and the respective known organic component concentrations in such calibration solutions. The capacitance-concentration correlation protocol can be embodied in any suitable form, such as software operable in a general-purpose programmable digital computer. Alternatively, the protocol may be hard-wired in circuitry of a microelectronic computational module, embodied as firmware, or available on-line as an operational applet at an Internet site for concentration analysis.
Usage of double layer capacitance for determining organic component concentrations in the present invention is particularly advantageous for analysis of copper electroplating solutions. First, measurement of the double layer capacitance involves little or no reduction of the copper ions (Cu2+), because such measurement is carried out in a potential range that is lower than that required for Cu2+ reduction reaction, which protects the measuring electrode from being alloyed with the reduced copper and increases the useful life of the electrode. Further, since measurement of the double layer capacitance does not involve copper deposition, the organic additives contained in the sample electrolytic solution are not consumed, and the concentration of such organic additives in the electrolyte solution throughout the measurement cycles remains constant, therefore significantly increasing the reproducibility of the measurement results.
FIG. 1 shows the current response curves of four different electrolytic solutions, which include (1) a first electrolytic solution that contains cupper sulfate, sulfuric acid, and chloride and is additive-free, (2) a second electrolytic solution that is compositionally identical to the first electrolytic solution but for containing a suppressor at a concentration of about 2.0 mL/L; (3) a third electrolytic solution that is compositionally identical to the first electrolytic solution but for containing an accelerator at a concentration of about 6.0 mL/L; (4) a fourth electrolytic solution that is compositionally identical to the first electrolytic solution but for containing a leveler at a concentration of about 2.5 mL/L.
An initial potential step (E) of about −0.208V is applied to each of the above-listed electrolytic solutions, and the current response curves of the electrolytic solutions under such initial potential step are obtained.
The current peak (Imax) and the time constant (tc) required for the current (I) to drop from the peak value to about 37% of the peak value can be directly read from such current response curves, and from which the double layer capacitance (Cd) can be calculated, according to equation (IV) provided hereinabove.
Following is a table listing the measurements obtained from the current response curves shown in FIG. 1.
















Solution (1)
Solution (2)
Solution (3)
Solution (4)

























Potential Step (E)

−0.208
V
−0.208
V
−0.208
V
−0.208
V


Current Peak (Imax)
Ave.
−77.6
nA
−45.1
nA
−58.1
nA
−73.8
nA



RSD
−0.20%

−1.50%

−0.50%

−0.50%


Time Constant (tc)

0.065
sec.
0.0749
sec.
0.0586
sec.
0.0684
sec.


Double Layer Capacitance (Cd)

24.2
nF
16.2
nF
16.4
nF
24.3
nF


Capacitance Change Rate

0%

−33%

−32%

0.04%









Among the three organic additives tested, the suppressor as added into solution (2) has the greatest impact on the double layer capacitance, and the leveler as added into solution (4) has the least impact at the given concentration. Therefore, different organic additives have relatively different impact on the double layer capacitance, which can be used for distinguishing said organic components from one another.
While the invention has been described herein with reference to specific aspects, features and embodiments, it will be recognized that the invention is not thus limited, but rather extends to and encompasses other variations, modifications and alternative embodiments. Accordingly, the invention is intended to be broadly interpreted and construed to encompass all such other variations, modifications, and alternative embodiments, as being within the scope and spirit of the invention as hereinafter claimed.

## Claims

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 (Cd) of the working electrode is determined by:




  
    C
    d
  
  =
  
    
      
        t
        c
      
      ×
      
        I
        max
      
    
    E
  




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

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 (Cd) of the working electrode is determined by:




  
    C
    d
  
  =
  
    
      
        t
        c
      
      ×
      
        I
        max
      
    
    E
  




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

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 (Cd) of the working electrode is determined by:




  
    C
    d
  
  =
  
    
      
        t
        c
      
      ×
      
        I
        max
      
    
    E
  




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