IP Library › Granted Patent US 10,982,336
Granted Patent B2
US 10,982,336 · App. 16/090,307 · Granted Apr 20, 2021

Method for etching a metal surface

Inventor: Charles H. Winter (Bloomfield Hills, MI)
Assignee: WAYNE STATE UNIVERSITY
C23F4/00C23C16/45553C23C16/56C23F1/00C23F1/12
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Quick Facts
Patent No.
US 10,982,336
App. No.
16/090,307
Granted
Apr 20, 2021
Kind
B2
Abstract

A method for etching a metal surface includes a step of contacting a metal surface with a protic compound for a first time period to produce a first modified surface. The first modified surface is contacted with a protic ligand-forming compound that reacts with the first modified surface to form a volatile metal-containing compound including a metal atom and the protic ligand-forming compound. The volatile metal-containing compound is removed from the vicinity of the metal surface.

Claims (49)

1. A method for etching a metal surface comprising:

a) contacting the metal surface having metal atoms M with a protic compound for a first time period to produce a first modified surface, the protic compound having labile H + ;

b) contacting the first modified surface with a vapor of a protic ligand-forming compound for a second time period that reacts with the first modified surface to form a volatile metal-containing compound including a metal atom and the protic ligand-forming compound, wherein the protic ligand-forming compound is selected from the group consisting of:

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 R 9 , R 10 are each independently H, C 1-12 alkyl or N(R 11 ) 2 and R 11 is H or C 1-12 alkyl; and

c) removing the volatile metal-containing compound, wherein the pressure during etching is 10 −6 Torr to about 760 Torr.

2. The method of claim 1 wherein protic compound is selected from the group consisting of C 1-6 carboxylic acids, C 1-6 primary alcohols, C 2-8 secondary alcohols, C 6-10 phenols, C 1-6 primary amines, C 2-8 secondary amines, and combinations thereof.

3. The method of claim 1 wherein the protic compound is formic acid.

4. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

5. The method of claim 4 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 are each independently H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl.

6. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

7. The method of claim 6 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 are each independently H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl.

8. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

and tautomers thereof;

where R 5 , R 7 are each independently H, C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

9. The method of claim 8 wherein R 5 , R 7 , R 11 are each independently H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl.

10. The method of claim 1 wherein the first time period and the second time period are each independently from 0.0001 to 200 seconds.

11. The method of claim 1 wherein M is a transition metal.

12. The method of claim 1 wherein M is a metal selected from Groups 2 to 12 of the Periodic Table.

13. The method of claim 1 wherein M is Zn, Mg, Cr, Mn, Fe, Co, Ni, or Cu.

14. The method of claim 1 wherein steps a, b, and c are repeated from 1 to 10,000 times.

15. The method of claim 1 wherein steps a, b, and c are performed at a temperature from 50° C. to 300° C.

16. The method of claim 1 wherein the protic ligand-forming compound is a compound selected from the group consisting of diketones, imino ketones, and diketimines.

17. A method for etching a surface comprising:

a) contacting an element surface having atoms therein with a protic compound for a first time period to produce a first modified surface, the protic compound having labile H + ;

b) contacting the first modified surface with a vapor of a protic ligand-forming compound for a second time period that reacts with the first modified surface to form a volatile element-containing compound including a metal atom and the protic ligand-forming compound, wherein the protic ligand-forming compound is selected from the group consisting of:

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 R 9 , R 10 are each independently H, C 1-12 alkyl or N(R 11 ) 2 and R 11 is H or C 1-12 alkyl; and

c) removing the volatile element-containing compound, wherein the pressure during etching is 10 −6 Torr to about 760 Torr.

18. The method of claim 17 wherein protic compound is selected from the group consisting of C 1-6 carboxylic acids, C 1-6 primary alcohols, C 2-8 secondary alcohols, C 6-10 phenols, C 1-6 primary amines, C 2-8 secondary amines, and combinations thereof.

19. The method of claim 17 wherein the protic compound is formic acid.

20. The method of claim 17 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

21. The method of claim 20 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 are each independently H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl.

22. The method of claim 17 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

23. The method of claim 22 wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 are each independently H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, or tert-butyl.

24. The method of claim 17 wherein the first time period and the second time period are each independently from 0.0001 to 200 seconds.

25. The method of claim 17 wherein steps a, b, and c are performed at a temperature from 50° C. to 300° C. and wherein the pressure during etching is 0.1 millitorr to 10 Torr.

26. The method of claim 1 wherein the pressure during etching is 0.1 millitorr to 10 Torr.

27. The method of claim 1 wherein steps a), b), and c) are carried out in an atomic layer deposition reactor.

28. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 1 , R 2 , R 3 , R 6 , R 7 , R 8 , R 9 , R 10 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

29. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

30. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 6 , R 7 , R 8 , R 9 , R 10 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

31. The method of claim 1 wherein the protic ligand-forming compound is selected from the group consisting of:

wherein R 6 , R 7 , R 8 , R 9 are each independently H or C 1-12 alkyl or N(R 11 ) 2 and R 11 is C 1-12 alkyl.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 11, 2019
From: WINTER, CHARLES H.
To: WAYNE STATE UNIVERSITY
Reel/Frame 048560/0226 →
Continuity (2)
Provisional Application 62316903 · Apr 1, 2016
Related Publication 20190112716A1 · Apr 18, 2019