ALD of metal-containing films using cyclopentadienyl compounds
Atomic layer deposition (ALD) type processes for producing metal containing thin films comprise feeding into a reaction space vapor phase pulses of metal containing cyclopentadienyl precursors as a metal source material. In preferred embodiments the metal containing cyclopentadienyl reactant comprises a metal atom that is not directly bonded to an oxygen or halide atom. In other embodiments the metal atom is bonded to a cyclopentadienyl compound and separately bonded to at least one ligand via a nitrogen atom. In still other embodiments the metal containing cyclopentadienyl compound comprises a nitrogen-bridged ligand.
1. A process for depositing a thin film on a substrate in a reactor comprising:
contacting the substrate with a vapor phase first precursor comprising a first zirconium compound comprising at least one cyclopentadienyl ligand and at least one ligand comprising bidentate bonding that is bonded to the metal through nitrogen;
contacting the substrate with an inert purge gas; and
contacting the substrate with a vapor phase first reactant, wherein the first reactant is a plasma reactant.
2. The process of claim 1 , wherein an inert gas serves as a carrier gas for the first precursor.
3. The process of claim 1 , wherein the first reactant comprises N, C or O.
4. The process of claim 1 , wherein the thin film is an elemental metal thin film.
5. The process of claim 1 , wherein the thin film is a metal carbide thin film.
6. The process of claim 5 , wherein the first reactant comprises a hydrocarbon.
7. The process of claim 1 , wherein the thin film is a metal nitride thin film.
8. The process of claim 1 , wherein the thin film is a multicomponent thin film.
9. The process of claim 8 , wherein the process comprises contacting the substrate with a second precursor.
10. The process of claim 9 , wherein the second precursor comprises a second metal compound having a metal that is different from the metal of the first metal precursor.
11. The process of claim 1 , wherein the zirconium compound comprises a modified cyclopentadienyl group.
12. The process of claim 11 , wherein the modified cyclopentadienyl group is selected from the group consisting of Me 5 Cp, MeCp, EtCp, and Me 3 SiCp.
13. The process of claim 1 , wherein the substrate temperature is 200° C. to 400° C.
14. The process of claim 1 , wherein the thin film is an insulating thin film.
15. The process of claim 1 , wherein the first zirconium compound comprises a chelating ligand.
16. The process of claim 1 , wherein the first zirconium compound comprises a nitrogen bridged ligand.
17. The process of claim 1 , wherein the first zirconium compound has the formula (R 1 R 2 R 3 R 4 R 5 Cp) x -ZrR 0 z —(NR 1 NR 2 R) y ,
wherein each of the two R 1 groups, each of the two R 2 groups, and each of the R 3 , R 4 , R 5 , and R 0 groups is independently selected from hydrogen; linear and branched C 1 -C 20 alkyl, alkenyl and alkynyl groups which are independently substituted or unsubstituted; carbocylic groups; and heterocyclic groups,
wherein R can be any linear or branched C1-C20 alkyl, alkenyl and alkynl groups which are independently substituted or unsubstituted, wherein R is bonded to two nitrogen bridging atoms at any point of the alkyl, alkenyl or alkynl groups, and
wherein x≥1, y≥1 and z≥0.
18. The process of claim 17 , wherein the carbocyclic groups are selected from phenyl, cyclopentadienyl, alkylaryl and halogenated carbocyclic groups.
19. The process of claim 1 , wherein the first zirconium compound does not contain halide or oxygen atoms.