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 plasma enhanced atomic layer deposition process for producing a metal containing thin film on a substrate comprising alternately and sequentially contacting the substrate with a first vapor phase reactant, and a second reactant, wherein the first vapor phase reactant comprises a volatile metal containing cyclopentadienyl compound comprising at least one cyclopentadienyl bonded to zirconium and at least one other ligand that is separately bonded to the zirconium atom via nitrogen, and wherein the zirconium is not directly bonded to a halide or oxygen atom.
2. The process of claim 1 , wherein the metal containing cyclopentadienyl compound has the formula: (R 1 R 2 R 3 R 4 R 5 Cp) x -MR 0 z -(NR 1 R 2 ) y
wherein M is zirconium;
wherein each of the R 1 groups, each of the R 2 groups, and each of the R 3 , R 4 , R 5 , and R 0 groups is independently selected from:
(i) hydrogen;
(ii) linear and branched C 1 -C 20 alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted;
(iii) carbocyclic groups, such as aryl, phenyl, cyclopentadienyl, alkylaryl, and halogenated carbocyclic groups; and
(iv) heterocyclic groups; and
wherein x≧1, y≧1 and z≧0.
3. The process of claim 2 , wherein each of the R 1 groups and each of the R 2 groups is independently selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-amyl, isoamyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 2,3-dimethyl-2-butyl.
4. The process of claim 2 wherein each of the R 1 groups and each of the R 2 groups is independently selected from linear and branched C 1 -C 4 alkyl, alkenyl, and alkynyl groups, which are independently substituted or unsubstituted.
5. The process of claim 4 , wherein each of the R 1 groups and each of the R 2 groups is independently selected from linear and branched C 1 -C 4 alkyl, which are independently substituted or unsubstituted.
6. The process of claim 2 , wherein z is 0.
7. The process of claim 6 , wherein y is 3.
8. The process of claim 1 , wherein the metal containing cyclopentadienyl compound does not comprise halide or oxygen atoms.
9. The process of claim 1 , wherein the metal containing thin film comprises an insulator material.
10. The process of claim 1 , wherein the temperature is 200° C. to 400° C.
11. An atomic layer deposition process for producing a metal containing thin film on a substrate comprising alternately and sequentially
contacting the substrate with a vapor phase first reactant comprising a volatile cyclopentadienyl compound having the formula (R 1 R 2 R 3 R 4 R 5 Cp) x -MR 0 z -(NR 1 R 2 ) y and a second reactant
wherein in the formula of the cyclopentadienyl compound M is zirconium;
each of the R 1 groups, each of the R 2 groups, and each of the R 3 , R 4 , R 5 , and R 0 groups is independently selected from:
hydrogen, and
linear and branched C 1 -C 20 alkyl, alkenyl and alkynyl groups, which are independently substituted or unsubstituted, and
x≧1, y≧1 and z≧0.
12. The process of claim 11 , wherein an inert gas serves as a carrier gas for the first reactant.
13. The process of claim 11 , wherein the atomic layer deposition process comprises a plasma enhanced atomic layer deposition process.
14. The process of claim 11 , wherein each of the R 1 groups and each of the R 2 groups is independently selected from linear and branched C 1 -C 4 alkyl, alkenyl, and alkynyl groups, which are independently substituted or unsubstituted.
15. The process of claim 14 , wherein each of the R 1 groups and each of the R 2 groups is independently selected from linear and branched C 1 -C 4 alkyl, which are independently substituted or unsubstituted.
16. The process of claim 15 , wherein each of the R 1 groups and each of the R 2 groups is independently selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.
17. The process of claim 11 , wherein z is 0.
18. The process of claim 17 , wherein y is 3.
19. The process of claim 11 , wherein the metal containing cyclopentadienyl compound does not comprise halide or oxygen atoms.
20. The process of claim 11 , wherein the metal containing cyclopentadienyl compound comprises a modified cyclopentadienyl group.
21. The process of claim 20 , wherein the modified cyclopentadienyl group is selected from the group consisting of Me 5 Cp, MeCp, EtCp, and Me 3 SiCp.
22. The process of claim 11 , wherein the metal containing thin film comprises an insulating thin film.