IP Library Granted Patent US 11,312,730
Granted Patent B2
US 11,312,730 · App. 16/347,028 · Granted Apr 26, 2022

Metal complexes containing cyclopentadienyl ligands

Inventors: Ming Fang (Somerville, NJ); Joby Eldo (Somerville, NJ); Charles Dezelah (Somerville, NJ); Daniel Moser (Somerville, NJ); Ravi Kanjolia (Somerville, NJ)
Assignee: MERCK PATENT GMBH
C07F5/00C23C14/12C23C16/18C23C16/45553H01L21/0228H01L21/02192H01L21/02274
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Quick Facts
Patent No.
US 11,312,730
App. No.
16/347,028
Granted
Apr 26, 2022
Kind
B2
Abstract

Metal complexes including cyclopentadienyl ligands and methods of using such metal complexes to prepare metal-containing films are provided.

Claims (49)

1. A metal complex corresponding in structure to Formula I:

[(R 1 ) n Cp] 2 M 1 L 1   (I)

wherein

M 1 is scandium;

each R 1 is independently C 1 -C 5 -alkyl or silyl;

n is 1, 2, 3, 4, or 5;

Cp is cyclopentadienyl ring; and

L 1 is selected from the group consisting of: N(SiR 4 R 5 R 6 ) 2 ; 3,5-R 7 R 8 —C 3 HN 2 ; 1-(R 32 )C 3 H 4 ; 1-R 33 -3-R 34 —C 3 H 3 ; and R 35 , R 36 —C 3 HO 2 ; wherein R 4 , R 5 , R 6 , R 7 , and R 8 are each independently C 1 -C 5 -alkyl; R 33 , R 34 , R 35 , and R 36 are each independently alkyl or silyl; and R 32 is silyl.

2. The metal complex of claim 1 , wherein each R 1 is independently methyl, ethyl, propyl or silyl; R 4 , R 5 , R 6 , R 7 and R 8 are each independently methyl, ethyl or propyl; and R 33 , R 34 , R 35 , and R 36 are each independently C 1 -C 4 -alkyl or silyl.

3. The metal complex of claim 1 , wherein each R 1 is independently methyl or ethyl; R 4 , R 5 , R 6 , R 7 , and R 8 are each independently methyl, or ethyl; and R 33 , R 34 , R 35 , and R 36 are each independently methyl, ethyl, propyl or silyl.

4. The metal complex of claim 1 , wherein each R 1 is methyl; R 4 , R 5 , R 6 , R 7 , and R 8 are each independently methyl; and R 32 , R 33 , R 34 , R 35 , and R 36 are each SiMe 3 .

5. The metal complex of claim 1 , wherein each R 1 is independently hydrogen, C 1 -C 4 -alkyl or silyl; and L 1 is 1-(SiMe 3 )C 3 H 4 or L 1 is 1,3-bis-(SiMe 3 ) 2 C 3 H 3 .

6. The metal complex of claim 1 , wherein the complex is:

Sc(MeCp) 2 [1-(SiMe 3 )C 3 H 4 ];

Sc(MeCp) 2 [1,3-bis-(SiMe 3 ) 2 C 3 H 3 ];

Sc(MeCp) 2 [N(SiMe 3 ) 2 ]; or

Sc(MeCp) 2 (3,5-Me 2 —C 3 HN 2 ).

7. A metal complex corresponding in structure to Formula II:

[((R 9 ) n Cp) 2 M 2 L 2 ] 2   (II)

wherein

M 2 is scandium;

each R 9 is independently C 1 -C 5 -alkyl;

n is 1, 2, 3, 4 or 5;

Cp is cyclopentadienyl ring; and

L 2 is selected from the group consisting of: Cl, F, Br, I, and 3,5-R 10 R 11 —C 3 HN 2 ; wherein

R 10 and R 11 are each independently hydrogen or C 1 -C 5 -alkyl;

wherein when L 2 is Cl, then R 9 is C 1 -C 5 -alkyl.

8. The metal complex of claim 7 , wherein each R 9 is independently C 1 -C 4 -alkyl.

9. The metal complex of claim 7 , wherein L 2 is Cl and each R 9 is independently methyl, ethyl or propyl.

10. The metal complex of claim 7 , wherein the complex is: [Sc(MeCp) 2 ]Cl] 2 .

11. A method of forming a metal-containing film by a vapor deposition process, the method comprising vaporizing at least one metal complex corresponding in structure to Formula I:

(R 1 Cp) 2 M 1 L 1   (I)

wherein

M 1 is scandium;

each R 1 is independently C 1 -C 5 -alkyl or silyl;

Cp is cyclopentadienyl ring; and

L 1 is selected from the group consisting of: N(SiR 4 R 5 R 6 ) 2 ; 3,5-R 7 R 8 —C 3 HN 2 ; 1-(R 32 )C 3 H 4 ; 1-R 33 -3-R 34 —C 3 H 3 ; and R 35 , R 36 —C 3 HO 2 ; wherein R 4 , R 5 , R 6 , R 7 , and R 8 are each independently C 1 -C 5 -alkyl; R 33 , R 34 , R 35 , and R 36 are each independently alkyl or silyl; and R 32 is silyl.

12. The method of claim 11 , wherein each R 1 is independently methyl, ethyl, propyl, or silyl; R 4 , R 5 , R 6 , R 7 , and R 8 are each independently methyl, ethyl or propyl; and R 33 , R 34 , R 35 , and R 36 are each independently C 1 -C 4 -alkyl or silyl.

13. The method of claim 11 , wherein each R 1 is independently methyl, or ethyl; and R 4 , R 5 , R 6 , R 7 , R 8 are each independently methyl, or ethyl; and R 33 , R 34 , R 35 , and R 36 are each independently methyl, ethyl, propyl or silyl.

14. The method of claim 11 , wherein each R 1 is methyl; R 4 , R 5 , R 6 , R 7 , and R 8 are each independently methyl; and R 32 , R 33 , R 34 , R 35 , and R 36 are each SiMe 3 .

15. The method of claim 11 , wherein each R 1 is independently C 1 -C 4 -alkyl or silyl; and L 1 is 1-(SiMe 3 )C 3 H 4 or L 1 is 1,3-bis-(SiMe 3 ) 2 C 3 H 3 .

16. The method of claim 11 , wherein the complex is:

Sc(MeCp) 2 [1-(SiMe 3 )C 3 H 4 ];

Sc(MeCp) 2 [1,3-bis-(SiMe 3 ) 2 C 3 H 3 ];

Sc(MeCp) 2 [N(SiMe 3 ) 2 ]; and/or

Sc(MeCp) 2 (3,5-Me 2 —C 3 HN 2 ).

17. The method of claim 11 , wherein the vapor deposition process is chemical vapor deposition or atomic layer deposition, wherein the chemical vapor deposition is pulsed chemical vapor deposition, continuous flow chemical vapor deposition, or liquid injection chemical vapor deposition, and wherein the atomic layer deposition is liquid injection atomic layer deposition or plasma-enhanced atomic layer deposition.

18. The method of claim 11 , wherein the metal complex is delivered to a substrate in pulses alternating with pulses of an oxygen source, wherein the oxygen source is selected from the group consisting of H 2 O, H 2 O 2 , O 2 , ozone, air, i-PrOH, t-BuOH, and N 2 O.

19. The method of claim 11 , further comprising vaporizing at least one co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, a hydrazine, a borane, a silane, ozone, and a combination of any two or more thereof, wherein the hydrazine is hydrazine (N 2 H 4 ) or N,N-dimethylhydrazine.

Continuity (2)
Provisional Application 62418981 · Nov 8, 2016
Related Publication 20190276477A1 · Sep 12, 2019
Cited By (2)
US 12,286,449 US 12,565,714