Method of selective deposition for forming fully self-aligned vias

1. A substrate processing method, comprising:

providing a substrate containing a dielectric material, a metal layer, and an oxidized metal layer on the metal layer;

exposing the substrate to a reactant gas containing a molecule that forms self-assembled monolayers (SAMs) on the substrate;

selectively depositing a metal oxide film on the dielectric material relative to the oxidized metal layer by exposing the substrate to a deposition gas; and

exposing the substrate to a process gas containing a silanol gas for a time period that selectively deposits a SiO 2 film on the metal oxide film.

2. The method of claim 1 , wherein the metal layer contains Cu, Ru, Co, or W, and the oxidized metal layer contains oxidized Cu, oxidized Ru, oxidized Co, or oxidized W.

3. The method of claim 1 , wherein the molecule includes a head group, a tail group, and a functional end group, and wherein the head group includes a thiol, a silane, or a phosphonate.

4. The method of claim 1 , wherein the molecule includes perfluorodecyltrichlorosilane (CF 3 (CF 2 ) 7 CH 2 CH 2 SiCl 3 ), perfluorodecanethiol (CF 3 (CF 2 ) 7 CH 2 CH 2 SH), chlorodecyldimethylsilane (CH 3 (CH 2 ) 8 CH 2 Si(CH 3 ) 2 Cl), or tertbutyl(chloro)dimethylsilane ((CH 3 ) 3 CSi(Cl)(CH 3 ) 2 )).

5. The method of claim 1 , wherein the metal oxide film contains HfO 2 , ZrO 2 , or Al 2 O 3 .

6. The method of claim 1 , wherein the exposing the substrate to the process gas containing the silanol gas is performed in the absence of any oxidizing and hydrolyzing agent at a substrate temperature of approximately 150° C., or less.

7. The method of claim 1 , wherein the silanol gas is selected from the group consisting of tris(tert-pentoxy) silanol, tris(tert-butoxy) silanol, and bis(tert-butoxy)(isopropoxy) silanol.

8. The method of claim 1 , further comprising:

repeating the exposing the substrate to a reactant gas, selectively depositing a metal oxide film, and exposing the substrate to a process gas containing a silanol gas at least once in order to increase a thickness of the metal oxide film and the SiO 2 film on the dielectric material.

9. The method of claim 1 , wherein the dielectric material surrounds the metal layer.

10. A substrate processing method, comprising:

providing a substrate containing a dielectric material and a metal layer, the metal layer having an oxidized metal layer thereon, wherein the metal layer contains Cu, Ru, Co, or W, and the oxidized metal layer contains oxidized Cu, oxidized Ru, oxidized Co, or oxidized W;

exposing the substrate to a reactant gas containing a molecule that forms self-assembled monolayers (SAMs) on the substrate, wherein the molecule includes a head group, a tail group, and a functional end group, and wherein the head group includes a thiol, a silane, or a phosphonate;

selectively depositing a metal oxide film on the dielectric material relative to the oxidized metal layer by exposing the substrate to a deposition gas;

exposing the substrate to a process gas containing a silanol gas for a time period that selectively deposits a SiO 2 film on the metal oxide film; and

repeating the exposing the substrate to a reactant gas, selectively depositing a metal oxide film, and exposing the substrate to a process gas containing a silanol gas at least once in order to increase a thickness of the metal oxide film and the SiO 2 film on the dielectric material.

11. A substrate processing method, comprising:

providing a substrate containing a dielectric material and a metal layer, the metal layer having an oxidized metal layer thereon;

exposing the substrate to hydrogen (H 2 ) gas excited by a plasma source;

selectively depositing a metal oxide film on the dielectric material relative to the oxidized metal layer by exposing the substrate to a deposition gas; and

exposing the substrate to a process gas containing a silanol gas for a time period that selectively deposits a SiO 2 film on the metal oxide film.

12. The method of claim 11 , wherein the metal layer contains Cu, Ru, Co, or W, and the oxidized metal layer contains oxidized Cu, oxidized Ru, oxidized Co, or oxidized W.

13. The method of claim 11 , wherein the exposing the substrate to the hydrogen gas excited by the plasma source forms a hydrogen-termination on the oxidized metal layer.

14. The method of claim 11 , further comprising:

removing the oxidized metal layer from the metal layer; and

selectively depositing the metal oxide film on the dielectric material relative to the metal layer by exposing the substrate to a deposition gas.

15. The method of claim 11 , wherein the removing includes a chemical oxide removal (COR) process.

16. The method of claim 11 , wherein the metal oxide film contains HfO 2 , ZrO 2 , or Al 2 O 3 .

17. The method of claim 11 , wherein the exposing the substrate to the process gas containing the silanol gas is performed in the absence of any oxidizing and hydrolyzing agent at a substrate temperature of approximately 150° C., or less.

18. The method of claim 11 , wherein the silanol gas is selected from the group consisting of tris(tert-pentoxy) silanol, tris(tert-butoxy) silanol, and bis(tert-butoxy)(isopropoxy) silanol.

19. The method of claim 11 , further comprising:

repeating the exposing the substrate to hydrogen (H 2 ) gas excited by a plasma source, selectively depositing a metal oxide film, and exposing the substrate to a process gas containing a silanol gas at least once in order to increase a thickness of the metal oxide film and the SiO 2 film on the dielectric material.

20. The method of claim 11 , wherein the dielectric material surrounds the metal layer.