Metal complexes containing cyclopentadienyl ligands

Patent metadata

Field	Value
Publication number	US-12286449-B2
Application number	US-202217692998-A
Country	US
Kind code	B2
Filing date	Mar 11, 2022
Priority date	Nov 8, 2016
Publication date	Apr 29, 2025
Grant date	Apr 29, 2025

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 C p] 2 M 1 L 1   (I)

wherein
when M 1 is lanthanum;
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: 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 and R 8 are each independently hydrogen or C 1 -C 5 -alkyl; R 32 is ethyl, butyl, pentyl, or silyl; and R 33 , R 34 , R 35 , and R 36 are each independently alkyl or silyl; or

when M 1 is yttrium;
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: 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 7 and R 8 are each independently hydrogen or C 1 -C 5 -alkyl; R 32 is methyl, propyl, butyl, pentyl, or silyl; and R 33 , R 34 , and R 35 are each independently alkyl or silyl; and R 36 is C 2 -C 8 -alkyl or silyl.

2. The metal complex of claim 1 , wherein each R 1 is independently C 1 -C 4 -alkyl or silyl, and R 8 are each independently hydrogen or C 1 -C 5 -alkyl, R 33 , R 34 , and R 35 are each independently C 1 -C 4 -alkyl or silyl, and R 36 is C 1 -C 4 -alkyl or silyl when M 1 is lanthanum, and R 36 is C 2 -C 4 -alkyl or silyl when M 1 is yttrium.

3. The metal complex of claim 1 , wherein each R 1 is independently C 1 -C 4 -alkyl or silyl; and L 1 is 3,5-R 7 R 8 -C 3 HN 2 or R 35 ,R 36 -C 3 HO 2 .

4. The metal complex of claim 1 , wherein the complex is:
Y(MeCp) 2 (3-methyl-5-pentyl-pyrazolate) or
Y(MeCp) 2 (6-methyl-2,4-heptanedionate).

5. 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 ) n C p] 2 M 1 L 1   (I)

wherein
M 1 is yttrium or lanthanum;
each R 1 is independently C 1 -C 5 -alkyl or silyl;
Cp is cyclopentadienyl ring; and
when M 1 is lanthanum:
n is 1, 2, 3, 4, or 5; and
L 1 is selected from the group consisting of: 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 and R 8 are each independently hydrogen or C 1 -C 5 -alkyl; and R 32 , R 33 , R 34 , R 35 , and R 36 are each independently alkyl or silyl; and

when M 1 is yttrium:
n is 1, 2, 3, 4, or 5; and
L 1 is selected from the group consisting of: 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 7 and R 8 are each independently hydrogen or C 1 -C 5 -alkyl; R 32 , R 33 , R 34 , and R 35 are each independently alkyl or silyl; and R 36 is C 2 -C 8 -alkyl or silyl; or
n is 1, 2, 3, or 4; and
L 1 is R 35 ,R 36 -C 3 HO 2 , wherein R 35 and R 36 are each independently alkyl or silyl.

6. The method of claim 5 , wherein each R 1 is independently C 1 -C 4 -alkyl or silyl; and R 8 are each independently hydrogen or C 1 -C 5 -alkyl; and R 32 , R 33 , R 34 , and R 35 are each independently C 1 -C 4 -alkyl or silyl, and R 36 is C 1 -C 4 -alkyl or silyl when M 1 is lanthanum, and R 36 is C 2 -C 4 -alkyl or silyl when M 1 is yttrium.

7. The method of claim 5 , wherein each R 1 is independently C 1 -C 4 -alkyl or silyl; and L 1 is 3,5-R 7 R 8 -C 3 HN 2 or R 35 ,R 36 -C 3 HO 2 .

8. The method of claim 5 , wherein the complex is:
Y(MeCp) 2 (3,5-methyl-5-pentyl-pyrazolate) or
Y(MeCp) 2 (6-methyl-2,4-heptanedionate).

9. The method of claim 5 , wherein the vapor deposition process is chemical vapor deposition or the vapor deposition process is atomic layer deposition.

10. The method of claim 5 , 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.

11. The method of claim 5 , 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.

12. A metal complex corresponding in structure to Formula I:
[(R 1 ) n C p] 2 M 1 L 1   (I)

wherein
M 1 is yttrium or lanthanum;
each R 1 is independently C 1 -C 5 -alkyl or silyl;
n is 1, 2, 3, or 4;
Cp is cyclopentadienyl ring; and
L 1 is R 35 ,R 36 -C 3 HO 2 ; wherein R 35 and R 36 are each independently alkyl or silyl.

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

• C23C14/12

  Organic material · CPC title

• C23C16/45553

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