IP Library Granted Patent US 9,714,464
Granted Patent B2
US 9,714,464 · App. 14/407,238 · Granted Jul 25, 2017

Precursors for atomic layer deposition

Inventors: Charles H. Winter (Bloomfield Hills, MI); Lakmal C. Kalutarage (Detroit, MI)
Assignee: Wayne State University
C23C16/45553C01B13/14C01B21/06C07C251/12C07C251/76C07F13/00C07F15/025C22B15/00C22B23/00C23C16/18
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Quick Facts
Patent No.
US 9,714,464
App. No.
14/407,238
Granted
Jul 25, 2017
Kind
B2
Abstract

Atomic layer deposition (ALD) and chemical vapor deposition (CVD) precursors that are useful for forming metal-containing films are provided. These compounds include triazapentadienyl, α-imino enolate compounds and α-imino ketone compounds having formulae 1, 2, and 3, respectively. An ALD method using the precursors is also provided.

Claims (52)

1. A compound having formula (I):

wherein:

M is a metal selected from groups 2 to 12 of the Periodic Table;

R 1 is C 1-8 alkyl, C 5-12 aryl, or NR 5 R 6 ;

R 2 is C 1-8 alkyl;

R 3 , R 4 are each independently hydrogen or C 1-8 alkyl; and

R 5 , R 6 are each independently C 1-8 alkyl with the proviso that when M is Cr, R 5 is C 2-8 alkyl.

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

3. The compound of claim 1 wherein R 2 is t-butyl.

4. The compound of claim 1 wherein when R 1 is C 1-8 alkyl, M is Zn, Mg, Cr, Mn, Fe, Co, or Ni, and when R 1 is NR 5 R 6 , M is Zn, Mg, Mn, Fe, Co, or Ni.

5. The compound of claim 1 wherein R 1 is C 1-8 alkyl and M is Zn, Mg, Cr, Mn, Fe, Co, or Ni.

6. The compound of claim 1 wherein R 1 is NR 5 R 6 and M is Zn, Mg, Mn, Fe, Co, or Ni.

7. The compound of claim 1 wherein R 1 is C 1-8 alkyl.

8. The compound of claim 1 wherein R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, or phenyl.

9. The compound of claim 1 wherein R 1 is t-butyl or N(CH 3 ) 2 .

10. A compound having formula 2:

wherein:

M is a metal selected from groups 2 to 12 of the Periodic Table;

R 7 , R 8 , R 9 are each independently hydrogen, C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl; and

R 10 is C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl.

11. The compound of claim 10 wherein M is Zn, Mg, Cr, Mn, Fe, Co, Ni, or Cu.

12. The compound of claim 10 wherein R 7 , R 8 , R 9 , R 10 are each independently C 1-8 alkyl.

13. The compound of claim 10 wherein R 10 is t-butyl.

14. A compound having formula (3):

M is a metal selected from groups 2 to 12 of the Periodic Table;

R 11 is C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl; and

R 12 , R 13 are each independently hydrogen, C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl.

15. The compound of claim 14 wherein M is Zn, Mg, Cr, Mn, Fe, Co, Ni, or Cu.

16. A method comprising:

a) reacting a compound having bidentate ligands with an reactive compound to form a first product, the compound having bidentate ligands being selected from the group consisting of:

wherein:

M is a metal selected from groups 2 to 12 of the Periodic Table;

R 1 is C 1-8 alkyl, C 5-12 aryl, or NR 5 R 6 ;

R 2 is C 1-8 alkyl;

R 3 , R 4 are each independently hydrogen or C 1-8 alkyl;

R 5 , R 6 are each independently C 1-8 alkyl with the proviso that when M is Zn, Mg, Cr, R 5 is C 2-8 alkyl;

R 7 , R 8 , R 9 are each independently hydrogen, C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl; and

R 10 is C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl;

R 11 is C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl; and

R 12 , R 13 are each independently hydrogen, C 1-8 alkyl, C 5-12 aryl, or C 5-12 heteroaryl.

17. The method of claim 16 wherein M is Zn, Mg, Cr, Mn, Fe, Co, or Ni.

18. The method of claim 16 wherein the reactive compound is an oxidizing agent and the first product includes a metal oxide.

19. The method of claim 16 wherein the reactive compound is a reducing agent and the first product includes a metal in the zero oxidation state.

20. The method of claim 16 wherein the activating reactive compound is a nitriding agent and the first product includes a metal nitride.

21. The method of claim 16 comprising a deposition cycle including:

a) contacting a substrate with a vapor of the compound having bidentate ligands form a first modified surface; and

c) contacting the substrate with the reactive compound.

22. The method of claim 21 wherein a metal-containing layer is deposited on the substrate.

23. The method of claim 22 wherein the metal-containing layer includes a component selected from the group consisting of metals in the zero oxidation state, metal nitrides, metal oxides, and combinations thereof.

24. The method of claim 21 further comprising contacting the first modified surface with an acid.

25. The method of claim 16 wherein the compound having bidentate ligands has formula 1:

26. The method of claim 25 wherein M is Zn, Mg, Cr, Mn, Fe, Co, or Ni.

Assignments (2)
CONFIRMATORY LICENSE Recorded Jan 5, 2017
From: WAYNE STATE UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 041260/0237 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 20, 2015
From: WINTER, CHARLES H.; KALUTARAGE, LAKMAL C.
To: WAYNE STATE UNIVERSITY
Reel/Frame 034993/0844 →
Continuity (2)
Provisional Application 61658064 · Jun 11, 2012
Related Publication 20150159273A1 · Jun 11, 2015