Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same

Patent metadata

Field	Value
Publication number	US-10465289-B2
Application number	US-201615396183-A
Country	US
Kind code	B2
Filing date	Dec 30, 2016
Priority date	Dec 30, 2016
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

Group 4 transition metal-containing film forming compositions comprising Group 4 transition metal precursors having the formula:

wherein M is Ti, Zr, or Hf; each E is independently C, Si, B or P; m and n is independently 0, 1 or 2; m+n>1; o and p is independently 0, 1 or 2; o+p>1; each R is independently hydrogen or or a C 1 -C 4 hydrocarbon group; each L is independently a −1 anionic ligand selected from the group consisting of NR′ 2 , OR′, Cp, amidinate, β-diketonate or keto-iminate, wherein R′ is a H or a C 1 -C 4 hydrocarbon group; and each L′ is independently NR″ or O, wherein R″ is a H or a C 1 -C 4 hydrocarbon group. Also disclosed are methods of synthesizing and using the disclosed precursors to deposit Group 4 transition metal-containing films on one or more substrates via vapor deposition processes.

First claim

We claim:

1. A method of depositing of a Group 4 transition metal-containing film on a substrate, comprising the steps of:
introducing a vapor of a Group 4 transition metal-containing film forming composition into a reactor having a substrate disposed therein and depositing at least part of the Group 4 transition metal-containing precursor onto the substrate, wherein the Group 4 transition metal-containing film forming composition comprises a Group 4 transition metal precursor having the formula selected from the group consisting of:
L-M-C 5 R 3 -1-[(ER 2 ) m -(ER 2 ) n -L′]-2-[(ER 2 ) o -(ER 2 ) p -L′]- and
L-M-C 5 R 3 -1-[(ER 2 ) n -(ER 2 ) m )-L′]-3-[(ER 2 ) o -(ER 2 ) p -L′]-,

referring to the following structure formula, respectively:

and combinations thereof, wherein M is Ti, Zr, or Hf bonded in an η 5 bonding mode to the Cp group; each E is independently C, Si, B or P; m and n is independently 0, 1 or 2; m+n>1; o and p is independently 0, 1 or 2; o+p>1; each R is independently hydrogen or a C 1 -C 4 hydrocarbon group; each L is independently a −1 anionic ligand; and each L′ is independently NR″ or O, wherein R″ is a H or a C 1 -C 4 hydrocarbon group.

2. The method of claim 1 , further comprising introducing at least one reactant into the reactor.

3. The method of claim 2 , wherein the reactant is selected from the group consisting of: O 2 , O 3 , H 2 O, H 2 O 2 , NO, N 2 O, NO 2 , oxygen radicals thereof, and mixtures thereof.

4. The method of claim 2 , wherein the reactant is a M′-containing precursor and the Group 4 transition metal-containing film is MM′ i O x , wherein i ranges from 0 to 1; x ranges from 1 to 6; and M′ is selected from a Group 3 element, a different Group 4 element, a Group 5 element, a lanthanide, Si, Al, B, P or Ge.

5. The method of claim 2 , wherein the Group 4 transition metal-containing film forming composition and the reactant are introduced into the reactor simultaneously and the reactor is configured for chemical vapor deposition.

6. The method of claim 5 , wherein the chemical vapor deposition is plasma enhanced.

7. The method of claim 2 , wherein the Group 4 transition metal-containing film forming composition and the reactant are introduced into the chamber sequentially and the reactor is configured for atomic layer deposition.

8. The method of claim 7 , wherein the atomic layer deposition is plasma enhanced.

9. The method of claim 2 , wherein the Group 4 transition metal-containing film forming composition is used to form a DRAM capacitor.

Assignees

• Air Liquide
• Lair Liquide Sa Pour Letude At Lexploitation Des Procedes Georges Claude

Inventors

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

Classifications

• C23C16/45536

  Use of plasma, radiation or electromagnetic fields · CPC title

• C23C16/448

  characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials · CPC title

• C07F7/003

  without C-Metal linkages · CPC title

• C23C16/405

  of refractory metals or yttrium · CPC title

• C23C16/45553

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