Methods and apparatuses for monitoring organic additives in electrochemical deposition solutions

• US 7,435,320 B2
• Filed: 04/30/2004
• Issued: 10/14/2008
• Est. Priority Date: 04/30/2004
• Status: Active Grant

• Current Assignee: Ancosys GmbH (Nova Ltd.)
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Jung, Jay, Han, Jianwen, King, Mackenzie E., Wang, Weihua, Tom, Glenn
• Primary Examiner(s): Olsen, Kaj K
• Application Number:
  US10/836,546
• Publication Number:
  US 20050241948A1
• Time in Patent Office: 1,628 Days
• Field of Search: 204/409, 204/412, 204/434, 204/400, 204/411
• US Class Current: 204/409
• CPC Class Codes: C25D 1/00 Electroforming
• CPC Class Codes: C25D 21/12 Process control or regulation controlling or regulating in general G05
• CPC Class Codes: C25D 21/14 Controlled addition of electrolyte components
• CPC Class Codes: C25D 3/38 of copper
• CPC Class Codes: C25D 5/18 Electroplating using modulated, pulsed or reversing current
• 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
• CPC Class Codes: H05K 2203/163 Monitoring a manufacturing process
• CPC Class Codes: H05K 3/188 by direct electroplating

Abstract

The present invention relates in general to real-time analysis of electrochemical deposition (ECD) metal plating solutions, for the purpose of reducing plating defects and achieving high quality metal deposition. The present invention provides various new electrochemical analytical cell designs for reducing cross-contamination and increasing analytical signal strength. The present invention also provides improved plating protocols for increasing potential signal strength and reducing the time required for each measurement cycle. Further, the present invention provides new methods and algorithms for simultaneously determining concentrations of suppressor, accelerator, and leveler in a sample ECD solution within three experimental runs. A particularly preferred embodiment of the present invention provides a method for simultaneously determining concentrations of all three organic additives within a single experimental run by using a single analytical cell, while interactions between such additives are properly accounted for.

Claims

1. An electrochemical cell for analyzing a sample electrochemical deposition solution, comprising (1) a single measurement chamber for receiving the sample electrochemical deposition solution, said measurement chamber being in fluid communication with at least one liquid inlet and at least one liquid outlet, (2) a test electrode, a counter electrode, and a reference electrode positioned in said measurement chamber for contacting the sample electrochemical deposition solution, wherein said test electrode has a longitudinal axis and is characterized by an average transverse dimension of from about 1 μ

m to about 250 μ

m, as measured along a direction that is perpendicular to said longitudinal axis, wherein said test electrode does not extend into said measurement chamber, but terminates at a flat end surface that is flush with an inner surface of the measurement chamber so that the test electrode contacts said solution when present in said measurement chamber only at said flat end surface of the test electrode, wherein the counter electrode comprises a tubular element having an inner surface and an outer surface and whose hollow center serves as a liquid pathway for the electrochemical deposition solution, wherein the tubular counter electrode forms a part of the liquid outlet and serves as the liquid pathway for the sample electrochemical deposition solution to pass therethrough, wherein said inner surface of the counter electrode constitutes the only liquid contacting surface of said counter electrode, and wherein said counter electrode maintains contact with sample electrochemical deposition solution at its inner surface and connects to external electrical connectors at its outer surface.

2. The electrochemical cell of claim 1, wherein said test electrode has a cross-sectional diameter within a range of from about 1 μ

m to about 125 μ

m.

3. The electrochemical cell of claim 1, wherein said test electrode comprises platinum or platinum alloy.

4. The electrochemical cell of claim 1, wherein the liquid inlet, the liquid outlet, and said measurement chamber define a liquid pathway therethrough, wherein each of the test electrode, the counter electrode, and the reference electrode comprises one or more liquid-contacting surfaces, and wherein the test electrode, the counter electrode, and the reference electrode are arranged and constructed so that all of the liquid-contacting surfaces of said electrodes are flush with one or more inner surfaces of the liquid inlet, the liquid outlet, and/or the measurement chamber, such that the liquid pathway is free of blockage by the electrodes.

5. The electrochemical cell of claim 1, wherein said test electrode is embedded in a wall of said measurement chamber, and comprises electrical connectors extending outside of said measurement chamber.

6. The electrochemical cell of claim 1, wherein said reference electrode is embedded in a wall of said measurement chamber, said reference electrode comprising (1) electrical connectors extending outside of said measurement chamber, and (2) terminating at a flat end surface constituting a liquid-contacting surface that is flush with an inner surface of the measurement chamber for contacting sample electrochemical deposition solution therein, wherein said flat end surface of the reference electrode flush with the inner surface of the measurement chamber constitutes the only liquid-contacting surface of said reference electrode, such that the liquid pathway is free of blockage by the reference electrode.

7. The electrochemical cell of claim 1, wherein said measurement chamber further comprises one or more temperature sensors for monitoring liquid temperature therewithin.

8. The electrochemical cell of claim 1, wherein the measurement chamber comprises five leg portions, with the test electrode embedded in a first leg, the reference electrode embedded in a second leg, and the counter electrode is coupled with a third leg.

9. The electrochemical cell of claim 8, further comprising a temperature sensor in a fourth leg, and a liquid inlet coupled with a fifth leg.

10. An electrochemical cell for analyzing a sample electrochemical deposition solution, including a measurement chamber comprising an inner volume defined by a bottom surface, a top surface and a chamber wall therebetween, with a liquid inlet and a liquid outlet communicating with the inner volume of the measurement chamber, and a test electrode, a counter electrode and a reference electrode in the measurement chamber, wherein the test electrode, the counter electrode, and the reference electrode extend from the top surface downwardly into the inner volume of said measurement chamber in parallel side by side relationship to one another, each terminating at a lower end and having a substantially similar length measured from the top surface of the measurement chamber to its lower end, and wherein the liquid inlet comprises an opening on the bottom surface of said measurement chamber for introducing liquid from the bottom surface upwardly into the inner volume of the measurement chamber, wherein said measurement chamber comprises a first and a second liquid outlet, wherein said first liquid outlet comprises a first opening on the chamber wall, wherein said second liquid outlet comprises a second opening on the chamber wall positioned such that the distance between the first opening and the bottom surface is greater than the distance between the ends of the electrodes extending downwardly into the inner volume of the chamber and the bottom surface, and wherein the distance between said first opening and the bottom surface of the measurement chamber is less than the distance between said second opening and the bottom surface of the measurement chamber.

11. The electrochemical cell of claim 10, wherein the liquid outlet comprises an opening on the chamber wall wherein the distance between the opening on the chamber wall and the bottom surface of the chamber is greater than the distance between the ends of the electrodes extending downwardly into the inner volume of the chamber and the bottom surface.

12. The electrochemical cell of claim 11, wherein the liquid outlet further comprises a liquid passage in fluid communication with the opening, and said liquid passage is slanted in a downward direction so as to prevent liquid backflow into the inner volume of the measurement chamber.

13. An electrochemical cell for analyzing a sample electrochemical deposition solution, including a measurement chamber comprising an inner volume defined by a bottom surface, a top surface and a chamber wall therebetween, with a liquid inlet and a liquid outlet communicating with the inner volume of the measurement chamber, and a test electrode, a counter electrode and a reference electrode in the measurement chamber, wherein the test electrode, the counter electrode, and the reference electrode extend from the top surface downwardly into the inner volume of said measurement chamber in parallel side by side relationship to one another, each terminating at a lower end and having a substantially similar length measured from the top surface of the measurement chamber to its lower end, and wherein the liquid inlet comprises an opening on the bottom surface of said measurement chamber for introducing liquid from the bottom surface upwardly into the inner volume of the measurement chamber, wherein said measurement chamber comprises a first and a second liquid outlet, wherein said first liquid outlet comprises a first opening on the chamber wall, wherein said second liquid outlet comprises a second opening on the chamber wall positioned such that the distance between the first opening and the bottom surface is greater than the distance between the ends of the electrodes extending downwardly into the inner volume of the chamber and the bottom surface, and wherein the distance between said first opening and the bottom surface of the measurement chamber is less than the distance between said second opening and the bottom surface of the measurement chamber, wherein at least one of the first and the second liquid outlet comprises a liquid passage in fluid communication with the respective opening, wherein said liquid passage is slanted in a downward direction so as to prevent liquid backflow into the inner volume of the measurement chamber.