Vapor phase deposition of organic films
Methods and apparatus for vapor deposition of an organic film are configured to vaporize an organic reactant at a first temperature, transport the vapor to a reaction chamber housing a substrate, and maintain the substrate at a lower temperature than the vaporization temperature. Alternating contact of the substrate with the organic reactant and a second reactant in a sequential deposition sequence can result in bottom-up filling of voids and trenches with organic film in a manner otherwise difficult to achieve. Deposition reactors conducive to depositing organic films are provided.
1. A method for reducing the aspect ratio of three-dimensional structures on a semiconductor substrate, comprising:
vaporizing a first reactant to form a first reactant vapor;
exposing a semiconductor substrate in a reaction space to the first reactant vapor, the semiconductor substrate comprising a topography with a three-dimensional structure; and
depositing an organic film over the semiconductor substrate preferentially over lower features of the topography compared to higher features of the topography such that the organic film reduces an aspect ratio of the three-dimensional structure on the semiconductor substrate as it deposits, wherein depositing includes exposing the semiconductor substrate to the first reactant vapor.
2. The method of claim 1 , wherein vaporizing is conducted at a temperature A and the semiconductor substrate is at a temperature B during depositing, and a ratio of temperature A to temperature B in Kelvin is between about 1 and about 1.15.
3. The method of claim 2 , wherein the temperature B is between about 5° C and about 50° C lower than the temperature A.
4. The method of claim 1 wherein depositing further comprises:
exposing the semiconductor substrate to a second reactant vapor to react with species of the first reactant vapor on the semiconductor substrate.
5. The method of claim 4 , wherein exposing the semiconductor substrate to the first reactant vapor and exposing the semiconductor substrate to the second reactant vapor comprise alternately and sequentially repeatedly exposing the semiconductor substrate to the first reactant vapor and the second reactant vapor.
6. The method of claim 4 , wherein the second reactant vapor comprises a diamine.
7. The method of claim 6 , wherein the diamine comprises 1,6-diaminohexane (DAH).
8. The method of claim 1 , further comprising controlling a vaporization temperature A and a semiconductor substrate temperature B, such that B<A.
9. The method of claim 8 , further comprising in situ cleaning the gas line and/or reaction space with an oxygen-containing reactant.
10. The method of claim 8 , wherein depositing the organic film comprises depositing a polyamic acid film.
11. The method of claim 10 , further comprising converting the polyamic acid film to a polyimide film.
12. The method of claim 10 , wherein the polyamic acid film mostly comprises polyamic acid.
13. The method of claim 8 , wherein depositing the organic film comprises depositing a polymer film.
14. The method of claim 1 , wherein the first reactant is an organic reactant, and exposing comprises feeding the first reactant vapor though a heated gas line extending through a side of a reactor defining the reaction space, to a gas distribution block overlying the semiconductor substrate within the reaction space.
15. The method of claim 14 , further comprising controlling a vaporization temperature A, a semiconductor substrate temperature B, a gas line temperature C and a gas distribution block temperature D, such that B<A<C<D.
16. The method of claim 15 , wherein the gas distribution block maintains separate flow paths for the first reactant vapor and a second reactant vapor until reaching the reaction space.
17. The method of claim 15 , wherein the gas distribution block comprises a common plenum through which the first reactant vapor and a second reactant vapor are fed.
18. The method of claim 14 , wherein the gas distribution block comprises an outlet to an exhaust and a valve for controlling exhaust from the gas distribution block for purging.
19. The method of claim 1 , wherein the first reactant comprises a dianhydride.
20. The method of claim 19 , wherein the dianhydride comprises pyromellitic dianhydride (PMDA).
21. The method of claim 1 , wherein exposing the semiconductor substrate to the first reactant vapor comprises maintaining the semiconductor substrate at a temperature below 130° C.
22. The method of claim 1 , wherein exposing the semiconductor substrate to the first reactant vapor comprises maintaining the semiconductor substrate at a temperature between about 100° C and about 150° C.