Lanthanide precursors and deposition of lanthanide-containing films using the same

Patent metadata

Field	Value
Publication number	US-11242597-B2
Application number	US-202016747129-A
Country	US
Kind code	B2
Filing date	Jan 20, 2020
Priority date	Dec 30, 2016
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

Lanthanide-containing film forming compositions comprising Lanthanide precursors having the general formulae:wherein Ln is a Lanthanide; A is independently N, Si, B, P or O; each E is independently C, Si, B or P; m and n are independently 0, 1 or 2; m+n>1; each R is independently an H or a C1-C4 hydrocarbyl group; L is a −1 anionic ligand selected from the group consisting of NR′2, OR′, Cp, amidinate, β-diketonate, or keto-iminate, wherein R′ is an H or a C1-C4 hydrocarbon group; and L′ is NR″ or O, wherein R″ is an H or a C1-C4 hydrocarbon group. Also disclosed are methods of synthesizing and using the disclosed precursors to deposit Lanthanide-containing films on one or more substrates via vapor deposition processes.

First claim

What is claimed is:

1. A method of forming a Lanthanide-containing film on a substrate, the method comprising the steps of:
introducing the Lanthanide precursor into a reactor having a substrate disposed therein; and

depositing at least part of the Lanthanide precursor onto the substrate to form the Lanthanide-containing film on the substrate using a vapor deposition process, wherein the Lanthanide precursor has the general formulae:
L-Ln-C 5 R 4 —[(ER 2 ) m -(ER 2 ) n -L′]-,

L-Ln-C 4 AR 3 -3-[(ER 2 ) m -(ER 2 ) n -L′]-,

L-Ln-C 3 (m-A 2 )R 2 -4-[(ER 2 ) m -(ER 2 ) n -L′]-,

referring to the following structure formula, respectively:

wherein Ln is selected from Lanthanide elements consisting of La, Y, Sc, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu bonded in an η 5 bonding mode to the aromatic group; A is independently N, Si, B, P or O; each E is independently C or Si; m and n are independently 0, 1 or 2; m+n>1; each R is independently an H or a C 1 -C 4 hydrocarbyl group; each L is independently a −1 anionic ligand, wherein the −1 anionic ligand is selected from the group consisting of NR′ 2 , OR′, Cp, Amidinate, β-diketonate, and keto-iminate, wherein R′ is an H or a C 1 -C 4 hydrocarbon group; each L′ is independently NR″, wherein R″ is an H or a C 1 -C 4 hydrocarbon group; and each of R 2 , R 3 and R 4 is an H or a C 1 -C 4 hydrocarbyl group.

2. The method of claim 1 , further comprising introducing a reactant species into the reactor.

3. The method of claim 2 , wherein the reactant species is selected from the group consisting of O 2 , O 3 , H 2 O, H 2 O 2 , acetic acid, formalin, para-formaldehyde, and combinations thereof.

4. The method of claim 3 , wherein the reactant species is ozone.

5. The method of claim 1 , wherein the Lanthanide precursor is selected from the group consisting of (Me 2 N)-La—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Y—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Sc—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Ce—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Pr—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Nd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Sm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Eu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Gd—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Tb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Dy—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Ho—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Er—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Tm—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Yb—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-, (Me 2 N)—Lu—C 5 H 3 -1-Me-3-(CH 2 —CH 2 —NMe)-.

6. The method of claim 5 , wherein the deposition process is an atomic layer deposition process.

7. The method of claim 1 , further comprising introducing a precursor into the reactor, wherein the precursor is different from the Lanthanide precursor, and depositing at least part of the precursor to form the Lanthanide-containing film on the substrate.

8. The method of claim 7 , wherein the precursor contains an element selected from the group consisting of Hf, Si, Al, Ga, Mn, Ti, Ta, Bi, Zr, Pb, Nb, Mg, Sr, Ba, Ca, and combinations thereof.

9. The method of claim 1 , wherein the deposition process is a chemical vapor deposition process.

10. The method of claim 1 , wherein the deposition process is an atomic layer deposition process.

Assignees

• Air Liquide

Inventors

• Gatineau Satoko
• Kim Daehyeon
• Noh Wontae
• Girard Jean-Marc

Classifications

• C23C16/40 Primary

  Oxides · CPC title

• C23C16/45553 Primary

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

• C23C16/18 Primary

  from metallo-organic compounds · CPC title

• C23C16/409

  of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide · CPC title

• C07F5/00

  Compounds containing elements of Groups 3 or 13 of the Periodic Table · CPC title