Group 6 transition metal-containing compounds for vapor deposition of group 6 transition metal-containing films
Disclosed are Group 6 film forming compositions comprising Group 6 transition metal-containing precursors selected from the group consisting of: M(=O)(NR 2 ) 4 Formula I, M(=O) 2 (NR 2 ) 2 Formula II, and M(=NR) 2 (OR) 2 Formula III, wherein M is Mo or W and each R is independently H, a C1 to C6 alkyl group, or SiR′ 3 , wherein R′ is H or a C1 to C6 alkyl group. Also disclosed are methods of synthesizing and using the disclosed compositions to deposit Group 6 transition metal-containing films on substrates via vapor deposition processes.
1. A Group 6 film forming composition comprising a Group 6 transition metal-containing precursor having the formula:
Mo(═O)(NR 2 ) 4
wherein each R is independently H, a C1 to C6 alkyl group, or SiR′ 3 ,
wherein R′ is H or a C1 to C6 alkyl group.
2. The Group 6 film forming composition of claim 1 , wherein each R is independently selected from the group consisting of H, Me, Et, nPr, iPr, nBu, iBu, sBu, tBu, tAmyl and SiMe 3 .
3. A method of depositing of a Group 6 transition metal-containing film on a substrate, comprising the steps of: introducing a vapor of the Group 6 film forming composition of claim 1 into a reactor having a substrate disposed therein and depositing at least part of the Group 6 transition metal-containing precursor onto the substrate.
4. The Group 6 film forming composition of claim 1 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NMe 2 ) 4 , Mo(═O)(NMeEt) 4 , Mo(═O)(Net 2 ) 4 , Mo(═O)(NiPr 2 ) 4 , Mo(═O)(NnPr 2 ) 4 , Mo(═O)(NiBu 2 ) 4 , Mo(═O)(NnBu 2 ) 4 , Mo(═O)(NtBu 2 ) 4 , Mo(═O)(NsBu 2 ) 4 , and Mo(═O)(NtAm 2 ) 4 .
5. The Group 6 film forming composition of claim 1 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(N(SiMe 3 ) 2 ) 4 , Mo(═O)(N(SiHMe 2 ) 2 ) 4 , and Mo(═O)(N(SiMeH 2 ) 2 ) 4 .
6. The Group 6 film forming composition of claim 1 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NHMe) 4 , Mo(═O)(NHEt) 4 , Mo(═O)(NHiPr) 4 , Mo(═O)(NHnPr) 4 , Mo(═O)(NHiBu) 4 , Mo(═O)(NHnBu) 4 , Mo(═O)(NHtBu) 4 , Mo(═O)(NHsBu) 4 , and Mo(═O)(NHtAm) 4 .
7. The Group 6 film forming composition of claim 1 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NMe 2 ) 2 (NtBu 2 ) 2 and Mo(═O)(NiPr 2 ) 2 (NtBu 2 ) 2 .
8. The Group 6 film forming composition of claim 1 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NHSiMe 3 ) 4 , Mo(═O)(NH(SiHMe 2 )) 4 , Mo(═O)(NH(SiMeH 2 )) 4 , Mo(═O)(NHiPr) 2 (N(SiMe 3 ) 2 ) 2 , and Mo(═O)(NiPr 2 ) 2 (N(SiMe 3 ) 2 ) 2 .
9. The method of claim 3 , wherein each R is independently selected from the group consisting of H, Me, Et, nPr, iPr, nBu, iBu, sBu, tBu, tAmyl and SiMe 3 .
10. The method of claim 3 , further comprising introducing at least one reactant into the reactor.
11. The method of claim 10 , wherein the reactant is selected from the group consisting of H 2 , H 2 CO N 2 H 4 , NH 3 , SiH 4 , Si 2 H 6 , Si 3 H 8 , SiH 2 Me 2 , SiH 2 Et 2 , N(SiH 3 ) 3 , hydrogen radicals thereof, and mixtures thereof.
12. The method of claim 10 , 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.
13. The method of claim 10 , wherein the Group 6 film forming composition and the reactant are introduced into the reactor simultaneously and the reactor is configured for chemical vapor deposition.
14. The method of claim 10 , wherein the Group 6 film forming composition and the reactant are introduced into the chamber sequentially and the reactor is configured for atomic layer deposition.
15. The method of claim 8 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NMe 2 ) 4 , Mo(═O)(NMeEt) 4 , Mo(═O)(Net 2 ) 4 , Mo(═O)(NiPr 2 ) 4 , Mo(═O)(NnPr 2 ) 4 , Mo(═O)(NiBu 2 ) 4 , Mo(═O)(NnBu 2 ) 4 , Mo(═O)(NtBu 2 ) 4 , Mo(═O)(NsBu 2 ) 4 , and Mo(═O)(NtAm 2 ) 4 .
16. The method of claim 3 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(N(SiMe 3 ) 2 ) 4 , Mo(═O)(N(SiHMe 2 ) 2 ) 4 , and Mo(═O)(N(SiMeH 2 ) 2 ) 4 .
17. The method of claim 3 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NHMe) 4 , Mo(═O)(NHEt) 4 , Mo(═O)(NHiPr) 4 , Mo(═O)(NHnPr) 4 , Mo(═O)(NHiBu) 4 , Mo(═O)(NHnBu) 4 , Mo(═O)(NHtBu) 4 , Mo(═O)(NHsBu) 4 , and Mo(═O)(NHtAm) 4 .
18. The method of claim 3 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NMe 2 ) 2 (NtBu 2 ) 2 and Mo(═O)(NiPr 2 ) 2 (NtBu 2 ) 2 .
19. The method of claim 3 , wherein the Group 6 transition metal-containing precursor is selected from the group consisting of Mo(═O)(NHSiMe 3 ) 4 , Mo(═O)(NH(SiHMe 2 )) 4 , Mo(═O)(NH(SiMeH 2 )) 4 , Mo(═O)(NHiPr) 2 (N(SiMe 3 ) 2 ) 2 , and Mo(═O)(NiPr 2 ) 2 (N(SiMe 3 ) 2 ) 2 .