Methods for vapor deposition of group 4 transition metal-containing films using Group 4 transition metal-containing films forming compositions

Patent metadata

Field	Value
Publication number	US-11008351-B2
Application number	US-201716331204-A
Country	US
Kind code	B2
Filing date	Apr 10, 2017
Priority date	Sep 9, 2016
Publication date	May 18, 2021
Grant date	May 18, 2021

Abstract

Disclosed are methods of using Group 4 transition metal azatrane 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:
(a) introducing into a reactor, having a substrate disposed therein, a vapor of a Group 4 transition metal-containing film forming composition comprising a Group 4 transitional metal-containing azatrane precursor having the following formula:

wherein M is selected from Group 4 transition metals consisting of Ti, Zr, or Hf; R is a Cp, alkyl or silyl substituted Cp, amidinate, or DAD; each R 1 is independently H or a C1 to C6 hydrocarbyl group; and each R 2 is independently a C1 to C6 hydrocarbyl group, and
(b) depositing at least part of the Group 4 transition metal-containing azatrane precursor onto the substrate.

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 greater than 0 to 1; x ranges from 1 to 6; and M′ is selected from a Group 3 element, a different Group 4 element (i.e., M≠M′), a Group 5 element, a lanthanide, Si, Al, B, P or Ge.

5. The method of claim 4 , wherein the deposition is plasma enhanced.

6. The method of claim 4 , wherein R is Cp or alkyl- or silyl-substituted Cp.

7. The method of claim 4 , wherein the Group 4 transitional metal-containing azatrane precursor is Me 5 Cp-M((—N(Me)-CH 2 —CH 2 —) 3 N), Me 5 Cp-M((—N(iPr)—CH 2 —CH 2 —) 3 N), Cp-M((—N(Me)-CHMe—CH 2 —) 3 N), or Cp-M((—N(iPr)—CHMe—CH 2 —) 3 N).

8. 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.

9. The method of claim 8 , wherein the deposition is plasma enhanced.

10. 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.

11. The method of claim 2 , wherein the precursor is used to form a DRAM capacitor.

12. The method of claim 1 , wherein R is Cp or alkyl- or silyl-substituted Cp.

13. The method of claim 1 , wherein the Group 4 transitional metal-containing azatrane precursor is Me 5 Cp-M((—N(Me)-CH 2 —CH 2 —) 3 N), Me 5 Cp-M((—N(iPr)—CH 2 —CH 2 ) 3 N), Cp-M((—N(Me)-CHMe—CH 2 —) 3 N), or Cp-M((—N(iPr)—CHMe—CH 2 —) 3 N).

Assignees

• Air Liquide
• Wang Ziyun
• Wan Zhiwen
• Girard Jean Marc

Inventors

• Wang Ziyun
• Wan Zhiwen
• Girard Jean-Marc

Classifications

• C07F7/00

  Compounds containing elements of Groups 4 or 14 of the Periodic Table · CPC title

• C23C16/08

  from metal halides · CPC title

• C07F17/00

  Metallocenes · CPC title

• C23C16/40

  Oxides · CPC title

• C23C16/18

  from metallo-organic compounds · CPC title