Selective deposition of silicon oxide on dielectric surfaces relative to metal surfaces

1. A method of selectively depositing silicon oxide on a dielectric surface of a substrate relative to a metal surface of the substrate, the method comprising, in order:

selectively passivating the dielectric surface relative to the metal surface;

selectively forming a polymer passivation layer on the metal surface;

contacting the dielectric surface with a metal catalyst; and

contacting the dielectric surface with a silicon reactant comprising a silanol.

2. The method of claim 1 , wherein the metal surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe, and Mo.

3. The method of claim 1 , wherein the dielectric surface comprises silicon oxide.

4. The method of claim 1 , wherein selectively passivating the dielectric surface comprises contacting the dielectric surface with 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 , additionally comprising treating the dielectric surface with plasma after selectively forming the polymer passivation layer on the metal surface and prior to contacting the dielectric surface with the metal catalyst.

8. The method of claim 1 , wherein the metal catalyst comprises trimethyl aluminum (TMA), dimethylaluminumchloride, aluminum trichloride (AlCl 3 ), dimethylaluminum isopropoxide (DMAI), tri s(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA).

9. The method of claim 1 , wherein the metal catalyst is a metal compound comprising Zn, Mg, Mn, La, Hf, Al, Zr, Ti, Sn, or Ga.

10. 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).

11. The method of claim 1 , wherein the polymer passivation layer formed on the metal surface comprises a self-assembled monolayer (SAM) or a polyimide layer.

12. The method of claim 1 , wherein the selectivity of deposition of silicon oxide on the catalyzed dielectric surface relative to the metal surface on which the polymer passivation layer has been formed is greater than about 50%.

13. A method of selectively depositing silicon oxide on a dielectric surface of a substrate relative to a metal surface of the substrate comprising:

selectively forming a polymer passivation layer on the metal surface, and

conducting one or more silicon oxide deposition cycles comprising alternately and sequentially contacting the substrate with a metal catalyst and a silanol.

14. The method of claim 13 , additionally comprising contacting the dielectric surface with a silylating agent prior to selectively forming the polymer passivation layer on the metal surface.

15. The method of claim 14 , wherein the silylating agent comprises alyltrimethylsilane (TMS-A), chlorotrimethylsilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS), or N-(trimethylsilyl)dimethylamine (TMSDMA).

16. The method of claim 13 , wherein the metal catalyst comprises trimethyl aluminum (TMA), dimethylaluminumchloride, aluminum trichloride (AlCl 3 ), dimethylaluminum isopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA) or triethyl aluminum (TEA).

17. The method of claim 13 , wherein the silanol is tris(tert-pentoxy)silanol (TPS).

18. The method of claim 13 , wherein the silicon oxide deposition cycle is repeated two or more times in a row.

19. The method of claim 13 , wherein the substrate is contacted with the silanol two or more times in at least one silicon oxide deposition cycle.

20. The method of claim 13 , wherein the polymer passivation layer comprises a polyimide layer or a thiol SAM.