Cure method for cross-linking Si-hydroxyl bonds
Embodiments described herein provide a method of forming a silicon-and-oxygen-containing layer having covalent Si—O—Si bonds by cross-linking terminal silanol groups. The method includes positioning a substrate in a chamber. The substrate has one or more trenches including a width of 10 nanometers (nm) or less, and an aspect ratio of 2:1 or greater. The aspect ratio is defined by a ratio of a depth to the width of the one or more trenches. A silicon-and-oxygen-containing layer is disposed over the one or more trenches. The silicon-and-oxygen-containing layer has terminal silanol groups. The substrate is heated, and the silicon-and-oxygen-containing layer is exposed to an ammonia or amine group-containing precursor distributed across a process volume.
1. A method, comprising:
disposing a silicon-and-oxygen-containing layer in one or more trenches on a substrate, the silicon-and-oxygen-containing layer having terminal silanol groups and the trench having:
a width of 10 nanometers (nm) or less; and
an aspect ratio of 2:1 or greater, the aspect ratio defined by a ratio of a depth to the width of the one or more trenches;
transferring the substrate having the silicon-and-oxygen-containing layer thereon into a chamber;
heating the substrate in the chamber; and
exposing the silicon-and-oxygen-containing layer to an ammonia or amine group-containing catalyst distributed across a process volume of the chamber.
2. The method of claim 1 , wherein positioning the substrate comprises:
transferring the substrate to a substrate support of the chamber; and
elevating the substrate support an elevated processing position to a process distance of about 0.25 inches to about 5 inches between the substrate support and a showerhead of the chamber.
3. The method of claim 1 , wherein a pressure in the chamber is about 0.5 Torr to about 600 Torr.
4. The method of claim 1 , wherein the ammonia or amine group-containing catalyst is introduced to the process volume at a flow rate of about 0.1 SLM to about 25 SLM.
5. The method of claim 1 , wherein inert gas is introduced to the process volume at a flow rate of about 1 SLM to about 10 SLM.
6. The method of claim 1 , wherein the ammonia or amine group-containing catalyst comprises ammonia.
7. The method of claim 1 , further comprising transferring the substrate to an ultraviolet (UV) curing chamber and UV curing the silicon-and-oxygen-containing layer after exposing the silicon-and-oxygen-containing layer to the ammonia or amine group-containing catalyst.
8. A method, comprising:
positioning a substrate on a substrate support in a chamber, the substrate having:
one or more trenches comprising:
a width of 10 nanometers (nm) or less; and
an aspect ratio of 2:1 or greater, the aspect ratio defined by a ratio of a depth to the width of the one or more trenches;
depositing a silicon-and-oxygen-containing layer in the one or more trenches, the silicon-and-oxygen-containing layer having terminal silanol groups;
heating the substrate support with the substrate thereon to a temperature of about 10° C. to about 1000° C.; and
exposing the silicon-and-oxygen-containing layer to an ammonia or amine group-containing catalyst distributed across a process volume, the exposing comprising cross-linking adjacent terminal silanol groups to form a polymerized silicon-and-oxygen-containing layer.
9. The method of claim 8 , wherein the depositing the silicon-and-oxygen-containing layer comprises:
introducing oxygen radicals and a silicon-containing precursor to the process volume of the chamber, the oxygen radicals polymerizing the silicon-containing precursor to deposit the silicon-and-oxygen-containing layer in the one or more trenches with the terminal silanol groups.
10. The method of claim 9 , further comprising:
prior to the introducing the oxygen radicals and the silicon-containing precursor, elevating the substrate support a first process distance of about 0.5 inches to about 5 inches between the substrate support and a showerhead of the chamber; and
prior to the exposing the silicon-and-oxygen-containing layer to the ammonia or amine group-containing catalyst, elevating the substrate support a second process distance of about 0.25 inches to about 5 inches between the substrate support and the showerhead.
11. The method of claim 10 , wherein the silicon-containing precursor comprises one or more of siloxanes, carbo-silanes, octamethylcyclotetrasiloxane (OMCTS), tetramethylcyclotetrasiloxane (TMCTS), octadecyltrichlorosilane (OTS), hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), tetraethoxysilane (TEOS), bis(trimethylsilyl)methane (BTMSM), methylenebis(dimethylsilane), methylenebis(methylsilane), methylenedisilane, silane, disilane, trisilylamine, or any combination thereof.
12. The method of claim 8 , wherein a pressure in the chamber during the exposing the silicon-and-oxygen-containing layer to the ammonia or amine group-containing catalyst is about 0.5 Torr to about 50 Torr.
13. The method of claim 8 , wherein the ammonia or amine group-containing catalyst is introduced to the process volume at a flow rate of about 0.1 SLM to about 25 SLM.
14. The method of claim 8 , wherein inert gas is provided to the process volume at a flow rate of about 1 SLM to about 10 SLM.
15. The method of claim 8 , wherein the ammonia or amine group-containing catalyst comprises one or more of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, or any combination thereof.
16. The method of claim 8 , wherein the one or more trenches comprise a silicon nitride layer and a titanium layer disposed therein, and wherein the silicon-and-oxygen-containing layer is formed over the silicon nitride layer and the titanium layer.
17. The method of claim 8 , further comprising transferring the substrate to an ultraviolet (UV) curing chamber and UV curing the silicon-and-oxygen-containing layer after exposing the silicon-and-oxygen-containing layer to the ammonia or amine group-containing catalyst.
18. A method, comprising:
positioning a substrate on a substrate support in a first chamber, the substrate having:
one or more trenches comprising:
a width of 10 nanometers (nm) or less; and
an aspect ratio of 2:1 or more, the aspect ratio defined by a ratio of a height to the width of the one or more trenches;
depositing a silicon-and-oxygen-containing layer, the depositing the silicon-and-oxygen-containing layer comprising:
introducing oxygen radicals and a silicon-containing precursor to a process volume of the first chamber, wherein the oxygen radicals and the silicon-containing precursor deposit the silicon-and-oxygen-containing layer over the one or more trenches with terminal silanol groups;
removing the substrate from the first chamber and positioning the substrate in a second chamber;
heating the substrate support with the substrate thereon to a temperature of about 10° C. to about 1000° C.;
exposing the silicon-and-oxygen-containing layer to an ammonia or amine group-containing catalyst distributed across a process volume, the exposing comprising cross-linking adjacent terminal silanol groups to form a polymerized silicon-and-oxygen-containing layer, the forming the polymerized silicon-and-oxygen-containing layer generating H 2 O; and
exhausting the H 2 O from the chamber.
19. The method of claim 18 , wherein the ammonia or amine group-containing catalyst comprises one or more of ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, or any combination thereof.
20. The method of claim 18 , further comprising transferring the substrate to an ultraviolet (UV) curing chamber and UV curing the silicon-and-oxygen-containing layer after exposing the silicon-and-oxygen-containing layer to the ammonia or amine group-containing catalyst.
21. The method of claim 1 , wherein the exposing comprises cross-linking adjacent terminal silanol groups to form a polymerized silicon-and-oxygen-containing layer.