Bottom-up gap-fill by surface poisoning treatment

1. A processing method comprising:

exposing a substrate surface having at least one feature thereon to a plasma comprising an organic-based poisoning agent to preferentially poison a top of the at least one feature relative to a bottom of the at least one feature, the organic-based poisoning agent selected from the group consisting of ethanolamine (ETA), hexane, and toluene, the plasma generated in an environment having a pressure in a range of from 0 Torr to 15 Torr via at least one source with a power in a range of from 50 W to 1000 W, the at least one feature having an aspect ratio greater than or equal to 10:1; and

depositing a film comprising silicon in the at least one feature in a bottom-up manner, such that growth on the top of the at least one feature is less than about 25% of the growth that occurs at the bottom of the feature after exposure to the organic-based poisoning agent and such that there are no voids or seams present in the at least one feature.

2. The method of claim 1 , wherein depositing the film in the at least one feature comprises sequentially exposing the substrate surface to a precursor and a reactant.

3. The method of claim 2 , wherein exposing the substrate surface to the poisoning agent occurs before each exposure to the precursor.

4. The method of claim 1 , wherein the substrate surface is exposed to the poisoning agent after depositing a film with a thickness in the range of about 10 Å to about 50 Å.

5. The method of claim 1 , wherein the plasma comprises one or more of NH 3 , N 2 , Ar, H 2 O, CO 2 , N 2 O, H 2 and/or hydrazine.

6. The method of claim 1 , wherein the poisoning agent is present in the plasma in a sub-saturative amount.

7. The method of claim 1 , wherein the organic-based poisoning agent thermally reacts with the surface.

8. The method of claim 7 , wherein the organic-based poisoning agent is introduced in a small amount to react preferentially with the top of the at least one feature.

9. The method of claim 1 , further comprising repeating the exposure to the organic-based poisoning agent and the film deposition to fill the at least one feature.

10. The method of claim 9 , wherein the film deposited in the at least one feature has a wet etch rate ratio less than 2.

11. A processing method comprising:

positioning a substrate surface in a processing chamber, the substrate surface having at least one feature thereon, the at least one feature creating a gap with a bottom, top and sidewalls, and having an aspect ratio greater than or equal to 10:1;

exposing the substrate surface to a plasma comprising an organic-based poisoning agent to preferentially inhibit film growth at the top of the at least one feature relative to a bottom of the at least one feature, the organic-based poisoning agent selected from the group consisting of ethanolamine (ETA), hexane, and toluene, the plasma generated in an environment having a pressure in a range of from 0 Torr to 15 Torr via at least one source with a power in a range of from 50 W to 1000 W;

sequentially exposing the substrate surface to a precursor and a reactant to deposit a layer in the gap; and

repeating exposure to the precursor and reactant to fill the gap of the at least one feature in a bottom-up manner, such that growth on the top of the at least one feature is less than about 25% of the growth that occurs at the bottom of the feature after exposure to the organic-based poisoning agent and such that there are no voids or seams present in the at least one feature.

12. The processing method of claim 11 , wherein the plasma is a directional plasma.

13. The processing method of claim 11 , wherein poisoning the substrate occurs after sequentially exposing the substrate to the precursor and the reactant in the range of two to about 10 times.

14. The processing method of claim 11 , wherein the substrate surface is exposed to the organic-based poisoning agent prior to each exposure to the precursor.

15. A processing method comprising:

placing a substrate having a substrate surface into a processing chamber comprising a plurality of sections, each section separated from adjacent sections by a gas curtain, the substrate surface having at least one feature with a top, bottom and sides and an aspect ratio greater than or equal to 10:1;

exposing at least a portion of the substrate surface to a first process condition in a first section of the processing chamber, the first process condition comprising a plasma comprising an organic-based poisoning agent to preferentially inhibit film growth at the top of the at least one feature relative to the bottom of the at least one feature, such that growth on the top of the at least one feature is less than about 25% of the growth that occurs at the bottom of the feature after exposure to the organic-based poisoning agent and such that there are no voids or seams present in the at least one feature, the organic-based poisoning agent selected from the group consisting of ethanolamine (ETA), hexane, and toluene, the plasma generated in an environment having a pressure in a range of from 0 Torr to 15 Torr via at least one source with a power in a range of from 50 W to 1000 W;

laterally moving the substrate surface through a gas curtain to a second section of the processing chamber;

exposing the substrate surface to a second process condition in the second section of the processing chamber, the second process condition comprising silicon precursor;

laterally moving the substrate surface through a gas curtain to a third section of the processing chamber;

exposing the substrate surface to a third process condition in the third section of the processing chamber, the third process condition comprising an oxygen-containing reactant to form a SiO 2 film; and

repeating exposure to the first section, second section and third section including lateral movement of the substrate surface to fill the at least one feature.