Selective deposition of silicon oxide on metal surfaces
Methods for selective deposition of silicon oxide films on metal or metallic surfaces relative to dielectric surfaces are provided. A dielectric surface of a substrate may be selectively passivated relative to a metal or metallic surface, such as by exposing the substrate to a silylating agent. Silicon oxide is then selectively deposited on the metal or metallic surface relative to the passivated oxide surface by contacting the metal surface with a metal catalyst and a silicon precursor comprising a silanol.
1. A method of selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of the substrate, the method comprising, in order:
contacting the substrate with a passivation agent;
contacting the substrate with a metal catalyst; and
contacting the substrate with a silicon reactant comprising a silanol,
wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.
2. The method of claim 1 , wherein the dielectric surface comprises a silicon oxide.
3. The method of claim 1 , wherein contacting the substrate with the passivation agent results in selectively passivating the dielectric surface relative to the metal surface.
4. The method of claim 1 , wherein the passivation agent is a silylating agent.
5. The method of claim 4 , wherein the silylating agent comprises an alkylaminosilane.
6. The method of claim 4 , wherein the silylating agent comprises allyltrimethylsilane (TMS-A), chlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).
7. The method of claim 1 , wherein the metal catalyst comprises trimethylaluminum (TMA), dimethylaluminumchloride, aluminum trichloride (AlCl 3 ), dimethylaluminum isopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA).
8. The method of claim 1 , wherein the silicon reactant comprises tris(tert-butoxy)silanol (TBS), tris(isopropoxy)silanol (TIS), or tris(tert-pentoxy)silanol (TPS).
9. The method of claim 1 , additionally comprising forming a passivation blocking layer on the metal surface prior to contacting the substrate with the passivation agent.
10. The method of claim 9 , wherein the passivation blocking layer comprises a polymer or a self-assembled monolayer (SAM).
11. The method of claim 1 , wherein the selectivity of deposition of silicon oxide on the catalyzed metal surface relative to the passivated dielectric surface is greater than about 50%.
12. A method of selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of the substrate comprising a deposition super-cycle comprising:
contacting the substrate with a silylating agent, and
conducting one or more silicon oxide deposition sub-cycles comprising alternately and sequentially contacting the substrate with a metal catalyst and a silanol,
wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.
13. The method of claim 12 , wherein the silylating agent is N-(trimethylsilyl)dimethylamine.
14. The method of claim 12 , wherein the metal catalyst comprises trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl 3 ), dimethylaluminum isopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA).
15. The method of claim 12 , wherein the silanol is tris(tert-pentoxy)silanol.
16. The method of claim 12 , wherein the silicon oxide deposition sub-cycle is repeated two or more times in the deposition super-cycle.
17. The method of claim 16 , wherein the substrate is contacted with the silanol two or more times in at least one silicon oxide deposition sub-cycle.
18. The method of claim 12 , wherein the deposition super-cycle is repeated two or more times.
19. A method of selectively depositing silicon oxide on a metal surface of a substrate relative to a dielectric surface of the substrate comprising alternately and sequentially contacting the substrate with a silylating agent comprising allyltrimethylsilane (TMS-A), chlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA); trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl 3 ), dimethylaluminum isopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA); and tris(tert-pentoxy)silanol,
wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.