Process for etching mixed metal oxides

• US 5,356,516 A
• Filed: 02/26/1993
• Issued: 10/18/1994
• Est. Priority Date: 02/26/1993
• Status: Expired due to Fees

• Current Assignee: Sandia Corporation (Martin Marietta Corporation), United States Of America As Represented By The Department Of Energy
• Original Assignee: Sandia Corporation (Martin Marietta Corporation)
• Inventors: Ginley, David S., Ashby, Carol I. H.
• Primary Examiner(s): Breneman, R. Bruce
• Assistant Examiner(s): CHANG, JONI YUK YING
• Application Number:
  US08/023,286
• Time in Patent Office: 599 Days
• Field of Search: 156/633, 156/634, 156/637, 156/667, 156/664
• US Class Current: 216/101
• CPC Class Codes: C04B 41/5353 Wet etching, e.g. with etchants dissolved in organic solvents
• CPC Class Codes: H10N 60/0688 Etching

Abstract

An etching process using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstom range may be achieved by this method.

Claims

1. A process for controllably etching at least one of the metal oxides from a mixed metal oxide surface comprising contacting the surface with an aqueous solution of at least one chelating poly-carboxylic acid selected from the group consisting of bicarboxylic acids and tricarboxylic acids.

2. The process of claim 1 wherein the aqueous solution further contains a mineral acid in a concentration sufficient to act as an activating agent.

3. The process of claim 1 wherein the mixed metal oxide is a high temperature superconductor material.

4. The process of claim 1 wherein the mixed metal oxide is a ferroelectric material.

5. The process of claim 1 wherein the aqueous solution is treated with a deoxygenating agent.

6. The process of claim 5 wherein the agent is nitrogen gas.

7. The process of claim 1 wherein the at least one chelating carboxylic acid is selected from the group consisting of dicarboxylic acids, tricarboxylic acids, and combinations thereof.

8. The process of claim 1 wherein the at least one acid is selected from the group consisting of malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, maleic acid, phthalic acid, oxalic acid, citric acid, and combinations thereof.

9. The process of claim 4 wherein the ferroelectric material is selected from the group consisting of PZT and PLZT compounds.

10. The process of claim 9 wherein the at least one acid is selected from the group consisting of citric acid, adipic acid, and combinations thereof.

11. The process of claim 10 wherein the concentration of the at least one acid is greater than about 0.01M.

12. The process of claim 3 wherein the high temperature superconductor is selected from the group consisting of YBa₂ Cu₃ O₇ and Tl₂ Ca₂ Ba₂ Cu₃ O₁₀.

13. The process of claim 12 wherein the concentration of the at least one acid is greater than about 0.01M.

14. The process of claim 1 wherein the rate of the etching is controlled by adjusting the pH of the solution.

15. The process of claim 1 wherein the aqueous solution is treated with a decarbonating agent.

16. A process for controllably etching at least one of the metal oxides from a ferroelectric material selected from the group consisting of PZT and PLZT compounds comprising contacting the surface of the material with an aqueous solution of at least one chelating poly-carboxylic acid.

17. The process of claim 16 wherein the at least one acid is selected from the group consisting of citric acid, adipic acid, and combinations thereof.

18. The process of claim 17 wherein the concentration of the at least one acid is greater than about 0.01M.