Selectively lateral growth of silicon oxide thin film
Implementations disclosed herein generally relate to methods of forming silicon oxide films. The methods can include performing silylation on the surface of the substrate having terminal hydroxyl groups. The hydroxyl groups on the surface of the substrate are then regenerated using a plasma and H 2 O soak in order to perform an additional silylation. Further methods include catalyzing the exposed surfaces using a Lewis acid, directionally inactivating the exposed first and second surfaces and deposition of a silicon containing layer on the sidewall surfaces. Multiple plasma treatments may be performed to deposit a layer having a desired thickness.
1. A method of depositing a silicon oxide film, sequentially comprising:
positioning a substrate in a process chamber, the substrate having:
a first layer; and
a second layer disposed over the first layer, the second layer having an exposed second surface and one or more features formed therein, the features creating one or more sidewall surfaces and an exposed first surface;
treating the substrate with a catalyst, the catalyst comprising a Lewis acid, the catalyst forming terminal reactive groups on the exposed first surface, the one or more sidewall surfaces and the exposed second surface;
delivering a catalyst deactivator to the substrate, the catalyst deactivator being activated by a plasma, the substrate being biased such that the catalyst deactivator is received by the exposed first surface and the exposed second surface, the terminal reactive groups being maintained on the one or more sidewall surfaces; and
delivering a silanol to the substrate, the silanol depositing a silicon-containing layer on the one or more sidewall surfaces.
2. The method of claim 1 , wherein the terminal reactive group is CH3.
3. The method of claim 1 , wherein the silanol is a compound having the general formula Si(OR)3OH, the R group being a hydrocarbon.
4. The method of claim 1 , wherein the silanol is tris-(tert-butoxy)silanol, tris-(tert-pentoxy)silanol, or derivatives thereof.
5. The method of claim 1 , wherein the Lewis acid is an organoaluminum compound, an organoiron compound, an organotitanium compound, an organozinc compound, or combinations thereof.
6. The method of claim 1 , wherein the Lewis acid is trimethylaluminum (TMA).
7. The method of claim 1 , wherein the Lewis acid is AlCl3, FeCl3, TiCl4, ZnCl4 or combinations thereof.
8. The method of claim 1 , wherein the catalyst deactivator comprises O2, N2, NH3, H2, H2O, He, Ar, or combinations thereof.
9. The method of claim 1 , wherein the treating the substrate with the catalyst, the delivering of the catalyst deactivator to the substrate and the delivering of the silanol to the substrate are sequentially repeated one or more times.
10. A method of depositing a silicon oxide film, sequentially comprising:
positioning a substrate in a process chamber, the substrate having:
a metal layer comprising copper; and
a dielectric layer disposed over the metal layer, the dielectric layer having an exposed dielectric surface and one or more features formed therein, the features creating one or more sidewall surfaces and an exposed metal surface;
treating the substrate with a catalyst, the catalyst comprising a tetramethyl aluminum, the catalyst forming a terminal CH3 group on the exposed metal surface, the one or more sidewall surfaces and the exposed dielectric surface;
forming a capacitively coupled plasma comprising a catalyst deactivator;
delivering the capacitively coupled plasma to the substrate, the substrate being biased such that the catalyst deactivator is received by the exposed metal surface and the exposed dielectric surface, the terminal CH3 groups being maintained on the one or more sidewall surfaces; and
delivering a silanol to the substrate, the silanol depositing a silicon oxide layer on the one or more sidewall surfaces.
11. The method of claim 10 , wherein the silanol is tris-(tert-butoxy)silanol, tris-(tert-pentoxy)silanol, or derivatives thereof.
12. The method of claim 11 , wherein the catalyst deactivator comprises O2, N2, NH3, H2, H2O, He, Ar, or combinations thereof.