Selective metal oxide deposition using a self-assembled monolayer surface pretreatment
Embodiments of the invention provide methods for selective film deposition using a surface pretreatment. According to one embodiment, the method includes providing a substrate containing a dielectric layer and a metal layer, exposing the substrate to a reactant gas containing a molecule that forms self-assembled monolayers (SAMs) on the substrate, and thereafter, selectively depositing a metal oxide film on a surface of the dielectric layer relative to a surface of the metal layer by exposing the substrate to a deposition gas.
1. A method of processing a substrate, comprising:
providing a substrate containing a dielectric layer and a metal layer;
exposing the substrate to a reactant gas containing a molecule that forms self-assembled monolayers (SAMs) on the substrate; and
thereafter, selectively depositing a metal oxide film on a surface of the dielectric layer relative to a surface of the metal layer by exposing the substrate to a deposition gas.
2. The method of claim 1 , wherein the metal layer contains Cu, Al, Ta, Ti, W, Ru, Co, Ni, or Mo.
3. The method of claim 1 , further comprising oxidizing the surface of the metal layer prior to or during the exposing of the substrate to the reactant gas.
4. 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.
5. 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 )).
6. The method of claim 1 , wherein the metal oxide film contains HfO 2 , ZrO 2 , or Al 2 O 3 .
7. The method of claim 1 , wherein a density of the SAMs is greater on the surface of the metal layer than on the surface of the dielectric layer.
8. The method of claim 1 , wherein the exposing the substrate to the deposition gas forms metal oxide nuclei on the surface of the metal layer, the method further comprising
removing, by etching, the metal oxide nuclei from the surface of the metal layer.
9. The method of claim 1 , further comprising:
in the absence of any oxidizing and hydrolyzing agent, at a substrate temperature of approximately 150° C., or less, exposing the substrate to a process gas containing a silanol gas to selectively deposit a conformal SiO 2 film on the metal oxide film relative to the metal layer.
10. The method of claim 9 , 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.
11. A method of processing a substrate, comprising:
providing a substrate containing a dielectric layer and a metal layer;
exposing the substrate to a reactant gas containing a molecule that forms self-assembled monolayers (SAMs) on the substrate;
thereafter, selectively forming a metal-containing catalyst layer on a surface of the dielectric layer relative to a surface of the metal layer by exposing the substrate to a gas containing a metal-containing precursor; and
in the absence of any oxidizing and hydrolyzing agent, at a substrate temperature of approximately 150° C., or less, exposing the substrate to a process gas containing a silanol gas to selectively deposit a SiO 2 film on the metal-containing catalyst layer relative to the metal layer.
12. The method of claim 11 , wherein the metal layer contains Cu, Al, Ta, Ti, W, Ru, Co, Ni, or Mo.
13. The method of claim 11 , further comprising oxidizing the surface of the metal layer prior to or during the exposing of the substrate to the reactant gas.
14. The method of claim 11 , wherein the molecule includes a head group, a tail group, and a functional end group, wherein the head group includes a thiol, a silane, or a phosphonate.
15. The method of claim 11 , 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 )).
16. The method of claim 11 , wherein the metal-containing precursor includes aluminum (Al) or titanium (Ti).
17. The method of claim 11 , wherein the metal-containing precursor includes AlMe 3 .
18. The method of claim 11 , wherein a density of the SAMs is greater on the surface of the metal layer than on the surface of the dielectric layer.
19. The method of claim 11 , wherein the exposing the substrate to the gas containing the metal-containing precursor forms metal-containing nuclei on the surface of the metal layer, the method further comprising
removing, by etching, the metal-containing nuclei from the surface of the metal layer.
20. 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.