Selective deposition on metal or metallic surfaces relative to dielectric surfaces
Methods are provided for selectively depositing a material on a first metal or metallic surface of a substrate relative to a second, dielectric surface of the substrate, or for selectively depositing metal oxides on a first metal oxide surface of a substrate relative to a second silicon oxide surface. The selectively deposited material can be, for example, a metal, metal oxide, metal nitride, metal silicide, metal carbide and/or dielectric material. In some embodiments a substrate comprising a first metal or metallic surface and a second dielectric surface is alternately and sequentially contacted with a first vapor-phase metal halide reactant and a second reactant. In some embodiments a substrate comprising a first metal oxide surface and a second silicon oxide surface is alternately and sequentially contacted with a first vapor phase metal fluoride or chloride reactant and water.
1. A method for selectively depositing a metal oxide film on a first metal oxide surface of a substrate relative to a second dielectric surface of the substrate, the method comprising one or more deposition cycles comprising alternately and sequentially contacting the substrate with a vapor phase first reactant comprising a metal halide and a vapor phase second reactant comprising OH bonds,
wherein the substrate is contacted with the first reactant at a temperature equal to or above about 225° C., and
wherein the metal oxide film is deposited on the first metal oxide relative to the second dielectric surface with a selectivity of above about 50%.
2. The method of claim 1 , wherein the vapor phase second reactant comprises water.
3. The method of claim 1 , wherein the vapor phase second reactant comprises H 2 O 2 .
4. The method of claim 1 , wherein the second dielectric surface comprises Si—O bonds.
5. The method of claim 1 , wherein the second dielectric surface comprises SiO 2 .
6. The method of claim 5 , wherein the metal oxide is deposited on the first metal oxide surface relative to the second dielectric surface comprising SiO 2 with a selectivity of above about 95%.
7. The method of claim 1 , wherein the second dielectric surface comprises —OH group surface terminations.
8. The method of claim 1 , wherein the second dielectric surface comprises GeO 2 .
9. The method of claim 1 , wherein the first metal oxide surface is an oxidized surface of a metallic material.
10. The method of claim 1 , wherein the first metal oxide surface is created by oxidizing at least the surface of a metallic material using an oxygen compound.
11. The method of claim 1 , wherein the first metal oxide surface comprises tungsten oxide, hafnium oxide, titanium oxide, aluminum oxide, or zirconium oxide.
12. The method of claim 1 , wherein the deposited metal oxide film comprises NbO x .
13. The method of claim 1 , wherein the metal halide is selected from fluorides or chlorides of Nb, Ta, Mo, W, V, or Cr.
14. The method of claim 1 , wherein the metal halide is selected from NbCl 5 , NbF 5 , TaCl 5 , TaF 5 , MoF x , MoCl x , VF x , VCl x , and CrF x .
15. The method of claim 1 , wherein the metal halide is selected from NbCl 5 , NbF 5 , TaCl 5 , and TaF 5 .
16. The method of claim 1 , wherein the metal halide does not comprise tungsten.
17. The method of claim 1 , wherein there is no measurable deposition of metal oxide on the second dielectric surface of the substrate after 100 deposition cycles.
18. The method of claim 1 , wherein the metal oxide film is deposited on the first metal oxide surface relative to the second dielectric surface with a selectivity of above about 95%.
19. The method of claim 1 , wherein the substrate is contacted with the first vapor-phase reactant comprising a metal halide at a temperature equal to or above about 300° C.
20. The method of claim 1 , wherein the substrate is contacted with the first vapor-phase reactant comprising a metal halide at a temperature equal to or above about 250° C. and the metal oxide film is deposited on the first metal oxide surface relative to the second dielectric surface with a selectivity of above about 95%.