Methods of atomic layer deposition using titanium-based precursors
View Patent ↗Methods of forming titanium-containing films by atomic layer deposition are provided. The methods comprise delivering at least one precursor to a substrate, wherein the at least one precursor corresponds in structure to Formula I: wherein: R is C 1 -C 6 -alkyl; n is zero, 1, 2, 3, 4 or 5; L is C 1 -C 6 -alkoxy or amino, wherein the amino is optionally independently substituted 1 or 2 times with C 1 -C 6 -alkyl.
1. A method of forming a titanium-containing film by atomic layer deposition, the method comprising delivering at least one precursor to a substrate, wherein the at least one precursor corresponds in structure to Formula I II:
wherein:
R is C 1 -C 6 -alkyl;
n is 1, 2, 3, or 4 or 5; and
L is C 1 -C 6 -alkoxy or amino, wherein the amino is optionally independently substituted 1 or 2 times with C 1 -C 6 -alkyl.
2. The method of claim 1 , wherein
R is methyl, ethyl or propyl;
n is 1 or 2; and
L is selected from the group consisting of methoxy, ethoxy, propoxy, and butoxy, dimethylamino, ethylmethylamino, and diethylamino.
3. The method of claim 1 , wherein
R is methyl or ethyl;
n is 1 or 2; and
L is selected from the group consisting of methoxy, ethoxy, propoxy, and butoxy.
4. The method of claim 1 , wherein
R is methyl or ethyl;
n is 1; and
L is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.
5. The method of claim 1 , wherein
R is methyl or ethyl;
n is 1 or 2; and
L is selected from the group consisting of dimethylamino, ethylmethylamino, and diethylamino.
6. The method of claim 1 , wherein the compound of Formula (I) II is selected from the group consisting of:
(methylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(ethylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(propylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(methylcyclopentadienyl)Ti(NEt 2 ) 3 ;
(ethylcyclopentadienyl)Ti(NEt 2 ) 3 ;
(propylcyclopentadienyl)Ti(NEt 2 ) 3 ;
(methylcyclopentadienyl)Ti(NMeEt) 3 ;
(ethylcyclopentadienyl)Ti(NMeEt) 3 ;
(propylcyclopentadienyl)Ti(NMeEt) 3 ;
(methylcyclopentadienyl)Ti(OMe) 3 ;
(ethylcyclopentadienyl)Ti(OMe) 3 ;
(propylcyclopentadienyl)Ti(OMe) 3 ;
(methylcyclopentadienyl)Ti(OEt) 3 ;
(ethylcyclopentadienyl)Ti(OEt) 3 ;
(propylcyclopentadienyl)Ti(OEt) 3 ;
(methylcyclopentadienyl)Ti(OiPr) 3 ;
(ethylcyclopentadienyl)Ti(OiPr) 3 ;
(propylcyclopentadienyl)Ti(OiPr) 3 ;
(methylcyclopentadienyl)Ti(OtBu) 3 ;
(ethylcyclopentadienyl)Ti(OtBu) 3 ; and
(propylcyclopentadienyl)Ti(OtBu) 3 .
7. The method of claim 1 , wherein the compound of Formula (I) II is selected from the group consisting of:
(methylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(methylcyclopentadienyl)Ti(OMe) 3 ;
(methylcyclopentadienyl)Ti(OiPr) 3 ; and
(methylcyclopentadienyl)Ti(OtBu) 3 .
8. The method of claim 1 , wherein the atomic layer deposition comprises photo-assisted atomic layer deposition.
9. The method of claim 1 , wherein the atomic layer deposition comprises liquid injection atomic layer deposition.
10. The method of claim 1 , wherein the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source.
11. The method of claim 10 , wherein the oxygen source is selected from H 2 O, O 2 or ozone.
12. The method of claim 1 , further comprising delivering to the substrate at least one co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazines, alkylhydrazines, boranes, silanes, ozone and a combination thereof.
13. The method of claim 1 , wherein at least two precursors corresponding in structure to Formula I II are delivered to the substrate to form a titanium-containing film by atomic layer deposition.
14. The method of claim 1 , further comprising delivering to the substrate at least one non-titanium precursor to form a mixed metal film by atomic layer deposition.
15. The method of claim 14 , wherein the mixed metal film formed is selected from the group consisting of strontium titanate, barium titanate, hafnium titanate, zirconium titanate and lead zirconate titanate.
16. The method of claim 1 , wherein the titanium-containing film is used for a memory and/or logic application.
17. The method of claim 1, wherein the substrate is silicon, silicon oxide, silicon nitride, tantalum, tantalum nitride, or copper.
18. A method of forming a titanium-containing film by atomic layer deposition, the method comprising delivering at least one precursor to a substrate, wherein the at least one precursor corresponds in structure to Formula III:
wherein:
R is C 1 -C 6 -alkyl;
n is 1, 2, 3, 4 or 5; and
L is amino, wherein the amino is optionally independently substituted 1 or 2 times with C 1 -C 6 -alkyl.
19. The method of claim 18, wherein
R is methyl, ethyl or propyl;
n is 1 or 2; and
L is selected from the group consisting of dimethylamino, ethylmethylamino, and diethylamino.
20. The method of claim 18, wherein
R is methyl or ethyl;
n is 1 or 2; and
L is selected from the group consisting of dimethylamino, ethylmethylamino, and diethylamino.
21. The method of claim 18, wherein the compound of Formula III is selected from the group consisting of:
(methylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(ethylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(propylcyclopentadienyl)Ti(NMe 2 ) 3 ;
(methylcyclopentadienyl)Ti(NEt 2 ) 3 ;
(ethylcyclopentadienyl)Ti(NEt 2 ) 3 ;
(propylcyclopentadienyl)Ti(NEt 2 ) 3 ;
(methylcyclopentadienyl)Ti(NMeEt) 3 ;
(ethylcyclopentadienyl)Ti(NMeEt) 3 ; and
(propylcyclopentadienyl)Ti(NMeEt) 3 .
22. The method of claim 18, wherein the compound of Formula III is methylcyclopentadienyl)Ti(NMe 2 ) 3 .
23. The method of claim 18, wherein the atomic layer deposition comprises photo-assisted atomic layer deposition.
24. The method of claim 18, wherein the atomic layer deposition comprises liquid injection atomic layer deposition.
25. The method of claim 18, wherein the at least one precursor is delivered to the substrate in pulses alternating with pulses of an oxygen source.
26. The method of claim 25, wherein the oxygen source is selected from H 2 O, O 2 or ozone.
27. The method of claim 18, further comprising delivering to the substrate at least one co-reactant selected from the group consisting of hydrogen, hydrogen plasma, oxygen, air, water, ammonia, hydrazines, alkylhydrazines, boranes, silanes, ozone and a combination thereof.
28. The method of claim 18, wherein at least two precursors corresponding in structure to Formula III are delivered to the substrate to form a titanium-containing film by atomic layer deposition.
29. The method of claim 18, further comprising delivering to the substrate at least one non-titanium precursor to form a mixed metal film by atomic layer deposition.
30. The method of claim 29, wherein the mixed metal film formed is selected from the group consisting of strontium titanate, barium titanate, hafnium titanate, zirconium titanate and lead zirconate titanate.
31. The method of claim 18, wherein the titanium-containing film is used for a memory and/or logic application.
32. The method of claim 18, wherein the substrate is silicon, silicon oxide, silicon nitride, tantalum, tantalum nitride, or copper.