Methods for forming a metallic film on a substrate by cyclical deposition and related semiconductor device structures
Methods for forming a metallic film on a substrate by cyclical deposition are provided. In some embodiments methods may include contacting the substrate with a first reactant comprising a non-halogen containing metal precursor comprising at least one of copper, nickel or cobalt and contacting the substrate with a second reactant comprising a hydrocarbon substituted hydrazine. In some embodiments related semiconductor device structures may include at least a portion of a metallic interconnect formed by cyclical deposition processes.
1. A method for forming a metallic film on a substrate by cyclical deposition, the method comprising:
contacting the substrate with a first reactant comprising a non-halogen containing metal precursor comprising at least one bidentate ligand and at least one of copper, nickel or cobalt to form metal-containing molecules on a surface of the substrate, wherein the non-halogen containing metal precursor comprises at least one ligand bonded to a metal atom through at least one oxygen atom and at least one nitrogen atom; and
contacting the substrate with a second reactant comprising a hydrocarbon substituted hydrazine precursor to thereby form the metallic film,
wherein the step of contacting the substrate with a second reactant immediately follows the step of contacting the substrate with a first reactant or immediately follows an intervening purge following the step of contacting the substrate with the first reactant, and
wherein the hydrocarbon substituted hydrazine precursor comprises a branch-chained allyl group or sec- or tert-isomer of alkyl group of at least four carbon atoms.
2. The method of claim 1 , wherein the cyclical deposition comprises atomic layer deposition.
3. The method of claim 1 , wherein the cyclical deposition comprises cyclical chemical vapor deposition.
4. The method of claim 1 , further comprising selecting the substituted hydrocarbon hydrazine precursor to comprise a C4-C8 hydrocarbon group.
5. The method of claim 1 , further comprising selecting the substituted hydrocarbon hydrazine precursor to comprise an aromatic hydrocarbon group.
6. The method of claim 1 , further comprising selecting the substituted hydrocarbon hydrazine precursor to comprise a tertbutyl alkyl group.
7. The method of claim 6 , further comprising selecting the alkyl group to comprise at least one of a methyl, an ethyl or a tertbutyl alkyl group.
8. The method of claim 1 , wherein the non-halogen containing metal precursor comprises at least one additional ligand which is bonded to the metal atom through at least one nitrogen atom.
9. The method of claim 1 , further comprising selecting the non-halogen containing metal precursor to comprise at least two non-halogen containing ligands.
10. The method of claim 1 , wherein the method comprises at least one deposition cycle in which the substrate is alternately and sequentially contacted with the first reactant and the second reactant.
11. The method of claim 7 , wherein the deposition cycle is repeated two or more times.
12. The method of claim 1 , further comprising forming the metallic film to have an electrical resistivity of less than 10 μΩ-cm.
13. The method of claim 1 , further comprising forming the metallic film to have an electrical resistivity of less than 10 μΩ-cm at a film thickness of less than 50 nm.
14. The method of claim 1 , further comprising heating the substrate to a temperature of less than about 500° C.
15. The method of claim 8 , further comprising heating the substrate to a temperature of more than about 50° C.
16. The method of claim 1 , further comprising selecting the first reactant and the second reactant to comprise non-plasma reactants.
17. The method of claim 1 , further comprising selecting the metallic film to comprise at least one of copper, cobalt or nickel.
18. A reaction system configured to perform the method of claim 1 .
19. A semiconductor device structure comprising at least a portion of a metallic interconnect formed by the method of claim 1 .
20. A method for forming a metallic film on a substrate by cyclical deposition, the method comprising:
contacting the substrate with a first reactant comprising a non-halogen containing metal precursor comprising at least one of Cu(dmap) 2 , Ni(dmap) 2 or Co(dmap) 2 ; and
contacting the substrate with a second reactant comprising a hydrocarbon substituted hydrazine precursor to thereby form the metallic film,
wherein the step of contacting the substrate with a second reactant immediately follows the step of contacting the substrate with a first reactant or immediately follows an intervening purge following the step of contacting the substrate with the first reactant, and
wherein the hydrocarbon substituted hydrazine precursor comprises a branch-chained allyl group or sec- or tert-isomer of alkyl group of at least four carbon atoms.