Metal complexes containing cyclopentadienyl ligands

Patent metadata

Field	Value
Publication number	US-11312730-B2
Application number	US-201716347028-A
Country	US
Kind code	B2
Filing date	Nov 3, 2017
Priority date	Nov 8, 2016
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

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

First claim

What is claimed is:

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.

Assignees

• Merck Patent Gmbh

Inventors

• Fang Ming
• Eldo Joby
• Dezelah Charles
• Moser Daniel
• Kanjolia Ravi

Classifications

• H10P14/69396

  the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium · CPC title

• H10P14/6339

  deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD · CPC title

• H10P14/6336

  in the presence of a plasma [PECVD] · CPC title

• C23C16/45553

  characterized by the use of precursors specially adapted for ALD · CPC title

• C23C16/18

  from metallo-organic compounds · CPC title