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