SIMULTANEOUS INORGANIC, ORGANIC AND BYPRODUCT ANALYSIS IN ELECTROCHEMICAL DEPOSITION SOLUTIONS
First Claim
1. A method for simultaneously determining concentrations of copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) thereof in a sample electrochemical deposition solution, comprising the steps of:
- (a) identifying one or more non-compositional variables that affect electropotential responses of electrochemical deposition solutions during electrochemical metal deposition;
(b) establishing a multiple regression model that expresses the electropotential responses of electrochemical deposition solutions as a function of (1) said one or more non-compositional variables, (2) organic additive concentrations in the solutions, (3) inorganic additive concentrations in the solutions, (4) byproduct concentrations in the solutions, and the corresponding coefficients;
(c) conducting multiple calibration runs, by measuring electropotential responses of multiple calibration solutions having unique, known organic additive, inorganic additive, and/or byproduct concentrations at unique, predetermined values of said one or more variables;
(d) determining the coefficients that correspond to said one or more variables and the organic additive, inorganic additive, and/or byproduct concentrations in the multiple regression model, based on information obtained from the calibration runs; and
(e) conducting N experimental runs, by measuring electropotential responses of the sample electrochemical deposition solution at unique, predetermined values of said one or more variables;
(f) establishing N number of equations based on the established multiple regression model, said equations containing the coefficients determined in step (d), the electropotential responses measured during the N experimental runs in step (e) and the corresponding predetermined values of said one or more variables, and the unknown concentrations of the copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) thereof in the sample electrochemical deposition solution; and
(g) calculating said copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct concentrations in the sample solution by solving the N equations provided in step (f).
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Abstract
Real-time analysis of electrochemical deposition (ECD) metal plating solutions is described, for the purpose of reducing plating defects and achieving high quality metal deposition. Improved plating protocols are utilized for increasing potential signal strength and reducing the time required for each measurement cycle. New methods and algorithms for simultaneously determining concentrations of organic additives, inorganic additives, and/or byproducts in a sample ECD solution are described. In one aspect, a method is provided for simultaneously determining concentrations of all organic additives, inorganic additives, and/or byproducts within a single experimental run by using a single analytical cell, while interactions between such additives are properly accounted for.
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Citations
20 Claims
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1. A method for simultaneously determining concentrations of copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) thereof in a sample electrochemical deposition solution, comprising the steps of:
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(a) identifying one or more non-compositional variables that affect electropotential responses of electrochemical deposition solutions during electrochemical metal deposition;
(b) establishing a multiple regression model that expresses the electropotential responses of electrochemical deposition solutions as a function of (1) said one or more non-compositional variables, (2) organic additive concentrations in the solutions, (3) inorganic additive concentrations in the solutions, (4) byproduct concentrations in the solutions, and the corresponding coefficients;
(c) conducting multiple calibration runs, by measuring electropotential responses of multiple calibration solutions having unique, known organic additive, inorganic additive, and/or byproduct concentrations at unique, predetermined values of said one or more variables;
(d) determining the coefficients that correspond to said one or more variables and the organic additive, inorganic additive, and/or byproduct concentrations in the multiple regression model, based on information obtained from the calibration runs; and
(e) conducting N experimental runs, by measuring electropotential responses of the sample electrochemical deposition solution at unique, predetermined values of said one or more variables;
(f) establishing N number of equations based on the established multiple regression model, said equations containing the coefficients determined in step (d), the electropotential responses measured during the N experimental runs in step (e) and the corresponding predetermined values of said one or more variables, and the unknown concentrations of the copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) thereof in the sample electrochemical deposition solution; and
(g) calculating said copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct concentrations in the sample solution by solving the N equations provided in step (f). - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9)
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10. A method for simultaneously determining concentrations of copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) thereof in a sample electrochemical deposition solution, by using a single electrochemical analytical cell and a single plating protocol, comprising the steps of:
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(a) selecting n compositional terms that include copper sulfate concentration, sulfuric acid concentration, chloride ion concentration, suppressor concentration, accelerator concentration, leveler concentration, byproduct(s) concentrations, and interactions between two or more of said concentrations, wherein n≧
3;
(b) establishing m multiple regression models that correspond to m time points during the electrochemical metal deposition process, wherein each model expresses electropotential responses of electrochemical deposition solutions as a function of the n selected compositional terms and their corresponding coefficients, wherein m≧
3;
(c) using said electrochemical analytical cell and said plating protocol for measuring electropotential responses of multiple calibration solutions at each of said m time points, wherein said calibration solutions contain copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) at unique, known concentrations;
(d) determining the coefficients of said n selected compositional terms for each of the m multiple regression models, based on information obtained in step (c);
(e) using said electrochemical analytical cell and said plating protocol for measuring electropotential responses of the sample electrochemical deposition solution at each of said m time points; and
(f) determining the n selected compositional terms based on the established multiple regression models, the coefficients determined in step (d), and the electropotential responses measured in step (e); and
(g) calculating concentrations of copper sulfate, sulfuric acid, chloride ion, suppressor, accelerator, leveler, and/or byproduct(s) in the sample electrochemical deposition solution from the compositional terms so determined. - View Dependent Claims (11, 12, 13, 14, 15)
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16. A method for simultaneously determining concentrations of inorganic additives, suppressor, accelerator, leveler, and/or byproduct(s) thereof in a sample electrochemical deposition solution, comprising the steps of:
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(a) identifying one or more non-compositional variables that affect electropotential responses of electrochemical deposition solutions during electrochemical metal deposition;
(b) establishing a multiple regression model that expresses the electropotential responses of electrochemical deposition solutions as a function of (1) said one or more non-compositional variables, (2) organic additive concentrations in the solutions, (3) inorganic additive concentrations in the solutions, (4) byproduct concentrations in the solutions, and the corresponding coefficients;
(c) conducting multiple calibration runs, by measuring electropotential responses of multiple calibration solutions having unique, known organic additive, inorganic additive, and/or byproduct concentrations at unique, predetermined values of said one or more variables;
(d) determining the coefficients that correspond to said one or more variables and the organic additive, inorganic additive, and/or byproduct concentrations in the multiple regression model, based on information obtained from the calibration runs; and
(e) conducting N experimental runs, by measuring electropotential responses of the sample electrochemical deposition solution at unique, predetermined values of said one or more variables;
(f) establishing N number of equations based on the established multiple regression model, said equations containing the coefficients determined in step (d), the electropotential responses measured during the N experimental runs in step (e) and the corresponding predetermined values of said one or more variables, and the unknown concentrations of the inorganic additives, suppressor, accelerator, leveler, and/or byproduct(s) thereof in the sample electrochemical deposition solution; and
(g) calculating said inorganic additives, suppressor, accelerator, leveler, and/or byproduct concentrations in the sample solution by solving the N equations provided in step (f). - View Dependent Claims (17, 18, 19, 20)
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Specification