Metal heterocyclic compounds for deposition of thin films

Inventors: Julien Gatineau (Tsuchiura, JP); Kazutaka Yanagita (Tsukuba, JP); Shingo Okubo (Tsukuba, JP)

Assignee: L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude

C23C16/18 C01G23/00 C01G25/02 C23C16/34 C23C16/405 Y10T117/10

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Quick Facts

Patent No.: US 9,109,281
App. No.: 14/147,168
Granted: Aug 18, 2015
Kind: B2

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Abstract

Methods and compositions for depositing a metal containing film on a substrate are disclosed. A reactor and at least one substrate disposed in the reactor are provided. A metal containing precursor is provided and introduced into the reactor, which is maintained at a temperature of at least 100° C. A metal is deposited on to the substrate through a deposition process to form a thin film on the substrate.

Claims (29)

1. A method of forming a metal containing film on a substrate, comprising:

a) providing a reactor and at least one substrate disposed therein;

b) introducing a metal precursor into the reactor, wherein the metal precursor is selected from the group consisting of: Te(CH 3 NCHCHNCH 3 ); Te(C 2 H 5 NCHCHNC 2 H 5 ); Te(NCH(CH 3 )CHCHNCH(CH 3 ) 2 ); Te(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 ); Te(NC(CH 3 ) 3 C(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Ti(CH 3 NCHCHNCH 3 ); Ti(C 2 H 5 NCHCHNC 2 H); Ti(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Ti(NC(CH 3 ) 3 NCHCHNC(CH 3 ) 3 ); Ti(NC(CH 3 ) 3 NC(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Si(CH 3 NCHCHNCH 3 ); Si(C 2 H 5 NCHCHNC 2 H 5 ); Si(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Si(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 ); Si(NC(CH 3 ) 3 NC(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Sn(NCH 3 NCHCHNCH 3 ); Sn(C 2 H 5 NCHCHNC 2 H 5 ); Sn(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Sn(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 ); Sn(NC(CH 3 ) 3 C(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Sb(N(CH 3 )CHCHN(CH 3 ))(N(CH 3 ) 2 ); Sb(N(CH 3 )CHCHN(CH 3 ))(CH 3 ); Sb(N(CH 3 )CHCHN(CH 3 )(C 2 H 5 ); Sb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ); Sb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(CH 3 ); Sb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(C 2 H 5 ); Ru(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(C 5 H 5 ); Ti(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Si(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Sn(NC(CH 3 ) 3 CHCHN(C(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Ti(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(CH 3 ) 2 ; Si(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(CH 3 ) 2 ; Ti(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(C 2 H 5 ) 2 ; Si(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(C 2 H 5 ) 2 ; Si(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(C 2 H 5 ) 2 ; Ru(NC(CH 3 ) 3 CHCHN(C(CH 3 ) 3 )(iPrNC(CH 3 )NiPr) 2 ; Fe(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(iPrNC(CH 3 )NiPr) 2 ; Os(N(C(CH 3 ) 3 )CHCHN(C(CH 3 ) 3 )(iPrNC(CH 3 )NiPr) 2 ; Ta(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(NMe 2 ) 3 ; Ta(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(CH 3 ) 3 ; Ta(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(C 2 H 5 ) 3 ; Nb(NC(CH 3 ) 3 CHCHCNC(CH 3 ) 3 )(NMe 2 ) 3 ; Nb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(CH 3 ) 3 ; and Nb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(C 2 H 5 ) 3 ;

c) maintaining the reactor at a temperature of at least about 100° C.; and

d) decomposing the metal precursor onto the substrate to form a metal containing film.

2. The method of claim 1 , wherein the metal precursor comprises an imido bond; the total number of R groups is greater than or equal to 2; and two R groups are substituted by one imido ligand.

3. The method of claim 1 , wherein the precursor comprises at least one member selected from the group consisting of: Te(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Te(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 ); Te(NC(CH 3 ) 3 C(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Ti(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Ti(NC(CH 3 ) 3 NCHCHNC(CH 3 ) 3 ); Ti(NC(CH 3 ) 3 NC(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Si(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Si(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 ); Si(NC(CH 3 ) 3 NC(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Sn(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ); Sn(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 ); Sn(NC(CH 3 ) 3 C(CH 3 )C(CH 3 )NC(CH 3 ) 3 ); Sb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ); Sb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(CH 3 ); Sb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(C 2 H 5 ); Ti(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Si(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Ge(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Sn(NC(CH 3 ) 3 CHCHN(C(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 ; Ru(NC(CH 3 ) 3 CHCHN(C(CH 3 ) 3 )(iPrNC(CH 3 )NiPr) 2 ; Ta(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(NMe 2 ) 3 ; and Nb(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(NMe 2 ) 3 .

4. The method of claim 3 , wherein the precursor is Ti(NCH(CH 3 ) 2 CHCHNCH(CH 3 ) 2 ).

5. A method of forming a metal containing film on a substrate, comprising:

a) providing a reactor and at least one substrate disposed therein;

b) introducing a metal precursor into the reactor, wherein the metal precursor is selected from the group consisting of:

Ti(N(tBu)CH 2 CH 2 N(tBu))(NMe 2 ) 2 ; Zr(N(tBu)CH 2 CH 2 N(tBu))(NMe 2 ) 2 ; and Ni(SiNC(CH 3 ) 3 CH 2 CH 2 NC(CH 3 ) 3 ) 4 ;

c) maintaining the reactor at a temperature of at least about 100° C.; and

d) decomposing the metal precursor onto the substrate to form a metal containing film.

6. The method of claim 5 , wherein the precursor is Ti(N(tBu)CH 2 CH 2 N(tBu))(NMe 2 ) 2 .

7. The method of claim 1 , further comprising maintaining the reactor at a temperature between about 100° C. and about 500° C.

8. The method of claim 7 , further comprising maintaining the reactor at a temperature between about 200° C. and about 350° C.

9. The method of claim 1 , further comprising maintaining the reactor at a pressure between about 1 Pa and about 10 5 Pa.

10. The method of claim 9 , further comprising maintaining the reactor at a pressure between about 25 Pa and about 10 3 Pa.

11. The method of claim 1 , further comprising introducing at least one reducing gas into the reactor, wherein the reducing gas comprises at least one member selected from the group consisting of: H 2 ; NH 3 ; SiH 4 ; Si 2 H 6 ; Si 3 H 8 ; hydrogen radicals; and mixtures thereof.

12. The method of claim 11 , wherein the metal precursor and the reducing gas are introduced into the chamber either substantially simultaneously, or sequentially.

13. The method of claim 12 , wherein the reducing gas and the metal precursor are introduced into the chamber substantially simultaneously, and the chamber is configured for chemical vapor deposition.

14. The method of claim 12 , the reducing gas, and the metal precursor are introduced into the chamber sequentially, and the chamber is configured for atomic layer deposition.

15. The method of claim 1 , further comprising introducing at least one oxidizing gas into the reactor, wherein the oxidizing gas comprises at least one member selected from the group consisting of: O 2 ; O 3 ; H 2 O; H 2 O 2 ; NO; N 2 O, oxygen radicals; and mixtures thereof.

16. The method of claim 15 , wherein the metal containing precursor and the oxidizing gas are introduced into the chamber either substantially simultaneously, or sequentially.

17. The method of claim 15 , wherein the metal containing precursor and the oxidizing gas are introduced into the chamber substantially simultaneously, and the chamber is configured for chemical vapor deposition.

18. The method of claim 15 , wherein the metal containing precursor and the oxidizing gas are introduced into the chamber sequentially, and the chamber is configured for atomic layer deposition.

19. A metal containing thin film coated substrate comprising the product of the method of claim 1 .

20. The method of claim 3 , wherein the precursor is Ti(NC(CH 3 ) 3 CHCHNC(CH 3 ) 3 )(N(CH 3 ) 2 ) 2 .

Continuity (3)

Division 12492000 · Jun 25, 2009

Provisional Application 61075664 · Jun 25, 2008

Related Publication 20140119977A1 · May 1, 2014