ALD of metal-containing films using cyclopentadienly 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. An atomic layer deposition process for depositing a metal containing thin film on a substrate in a reaction space comprising one or more deposition cycles comprising:
contacting the substrate with a pulse of a vapor phase first reactant comprising a volatile zirconium compound having the formula (R 1 R 2 R 3 R 4 R 5 Cp) x -ZrR 0 z —(NR 1 R 2 ) y ;
contacting the substrate with a pulse of a vapor phase second reactant; and
wherein in the first reactant 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 wherein x≧1, y≧1 and z≧0.
2. The process of claim 1 , wherein an inert gas serves as a carrier gas for the first reactant.
3. The process of claim 1 , wherein the atomic layer deposition process comprises a plasma enhanced atomic layer deposition process.
4. The process of claim 1 , wherein the one or more deposition cycles comprise purging the reaction space between the pulses of the first and second reactants.
5. The process of claim 1 , 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.
6. The process of claim 5 , 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 groups which are independently substituted or unsubstituted.
7. The process of claim 6 , 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.
8. The process of claim 1 , wherein z is 0.
9. The process of claim 8 , wherein y is 3.
10. The process of claim 1 , wherein the zirconium compound comprises a modified cyclopentadienyl group.
11. The process of claim 10 , wherein the modified cyclopentadienyl group is selected from the group consisting of Me 5 Cp, MeCp, EtCp, and Me 3 SiCp.
12. The process of claim 1 , wherein the temperature is 200° C. to 400° C.
13. The process of claim 1 , wherein the second reactant contributes nitrogen to the metal containing thin film.
14. The process of claim 1 , wherein the second reactant contributes carbon to the metal containing thin film.
15. The process of claim 1 , wherein the second reactant contributes oxygen to the metal containing thin film.
16. The process of claim 1 , wherein the metal containing thin film is an insulating thin film.
17. A plasma enhanced atomic layer deposition process for producing a multicomponent metal containing thin film on a substrate comprising:
a first deposition cycle comprising alternately and sequentially contacting the substrate with a first metal precursor comprising a volatile cyclopentadienyl compound and a first reactant comprising N, C or O,
wherein the first metal precursor 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;
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≧2 land z≧0.
18. The process of claim 17 , wherein the first reactant is a plasma reactant.
19. The process of claim 17 , wherein the first reactant contributes oxygen to the multicomponent metal containing thin film.
20. The process of claim 17 additionally comprising a second deposition cycle comprising contacting the substrate with a second metal precursor and a second reactant.
21. The process of claim 20 , wherein the second metal precursor is different from the first metal precursor.
22. The process of claim 20 , wherein the second reactant is different from the first reactant.
23. The process of claim 22 , wherein the second reactant contributes a different species to the multicomponent thin film from the first reactant.