Method of slimming radiation-sensitive material lines in lithographic applications

1. A method of patterning a substrate comprising:

forming a layer of radiation-sensitive material on a substrate;

exposing said layer of radiation-sensitive material to a pattern of radiation, wherein said pattern includes:

a first region having a high radiation exposure,

a second region having a low radiation exposure, and

a third region having an exposure gradient ranging from about said high radiation exposure to about said low radiation exposure;

performing a post-exposure bake following said exposing;

performing positive-tone developing by contacting said layer of radiation-sensitive material with a first organic solvent-based composition to remove said first region from said substrate to provide a developed layer of radiation-sensitive material;

removing said exposure gradient of said third region by transforming said second region and said third region to a fourth region having a substantially uniform level of radiation exposure, polarity, or de-protection, or a combination thereof; and

slimming said fourth region.

2. The method of claim 1 , wherein said layer of radiation-sensitive material comprises:

a hydrophilic polymer that decreases in polarity upon performing

said exposing and said post-exposure bake following said exposing of said layer of radiation-sensitive material,

an acid wash and a post-acid wash bake of said layer of radiation-sensitive material,

a heating of said layer of radiation-sensitive material to a temperature equal to or greater than a thermal decomposition temperature of said radiation-sensitive material, or

any combination of two or more thereof; or

an acid generator that provides acid-catalyzed rearrangement of the hydrophilic polymer to a more hydrophobic polymer upon performing

said exposing and said post-exposure bake following said exposing of said layer of radiation-sensitive material;

said acid wash and said post-acid wash bake of said layer of radiation-sensitive material;

said heating of said layer of radiation-sensitive material to said temperature equal to or greater than said thermal decomposition temperature of said radiation-sensitive material, or

any combination of two or more thereof.

3. The method of claim 1 , wherein said removing said exposure gradient comprises:

performing a flood exposure and a post-flood exposure bake of said developed layer of radiation-sensitive material;

performing an acid wash and a post-acid wash bake of said developed layer of radiation-sensitive material; or

heating said developed layer of radiation-sensitive material to a temperature equal to or greater than a thermal decomposition temperature of said radiation-sensitive material.

4. The method of claim 3 , wherein said slimming said fourth region comprises

contacting said fourth region with a second organic solvent-based composition at an ultra-cold temperature to remove a portion of said fourth region, wherein said ultra-cold temperature is less than 25° C. and greater than a freezing point of said second organic solvent-based composition.

5. The method of claim 3 , wherein said slimming said fourth region comprises contacting said fourth region with a second organic solvent-based composition to remove a portion of said fourth region, wherein said second organic solvent-based composition achieves a rate of a dissolution ranging from about 0.1 nm/sec to about 5 nm/sec.

6. The method of claim 3 , wherein said slimming said fourth region comprises contacting said fourth region with an aqueous base solution to remove a portion of said fourth region.

7. The method of claim 3 , wherein said slimming said fourth region comprises contacting said fourth region with an aqueous solution comprising a promoting agent to remove a portion of said fourth region.

8. The method of claim 7 , wherein the promoting agent is a salt comprising an alkali metal.

9. The method of claim 3 , wherein said slimming said fourth region comprises contacting said fourth region with an aqueous base solution at a temperature ranging from about 30° C. to about the boiling point of the aqueous base solution.

10. A method of patterning a substrate comprising:

forming a layer of radiation-sensitive material on a substrate;

exposing said layer of radiation-sensitive material to a pattern of radiation, wherein said pattern includes:

a first region having a high radiation exposure,

a second region having a low radiation exposure, and

a third region having an exposure gradient ranging from about said high radiation exposure to about said low radiation exposure;

performing a post-exposure bake following said exposing;

performing negative-tone developing of said layer of radiation-sensitive material by contacting said layer of radiation-sensitive material with a first organic solvent-based composition to remove said second region from said substrate to provide a developed layer of radiation-sensitive material;

removing said exposure gradient of said third region by transforming said third region, and optionally said first region, to a fourth region formed from said first and said third regions having a substantially uniform level of radiation exposure, polarity, or de-protection, or a combination thereof, wherein said removing said exposure gradient comprises:

performing a flood exposure and a post-flood exposure bake of said developed layer of radiation-sensitive material;

performing an acid wash and a post-acid wash bake of said developed layer of radiation-sensitive material; or

heating said developed layer of radiation-sensitive material to a temperature equal to or greater than a thermal decomposition temperature of said radiation-sensitive material; and

slimming said fourth region by contacting said fourth region with a second organic solvent-based composition,

wherein said layer of radiation-sensitive material comprises:

a material that increases in polarity upon performing

said exposing and said post-exposure bake following said exposing of said layer of radiation-sensitive material,

an acid wash and a post-acid wash bake of said layer of radiation-sensitive material,

a heating of said layer of radiation-sensitive material to said temperature equal to or greater than said thermal decomposition temperature of said radiation-sensitive material, or

any combination of two or more thereof; or

an acid generator that generates acid upon performing

said exposing and said post-exposure bake following said exposing of said layer of radiation-sensitive material;

said acid wash and said post-acid wash bake of said layer of radiation-sensitive material;

said heating of said layer of radiation-sensitive material to said temperature equal to or greater than said thermal decomposition temperature of said radiation-sensitive material, or

any combination of two or more thereof; or

a protected polymer that undergoes de-protection upon heating to a temperature equal to or greater than a thermal decomposition temperature of said protected polymer.

11. A method of patterning a substrate comprising:

forming a layer of radiation-sensitive material on a substrate;

exposing said layer of radiation-sensitive material to a pattern of radiation, wherein said pattern includes:

a first region having a high radiation exposure,

a second region having a low radiation exposure, and

a third region having an exposure gradient ranging from about said high radiation exposure to about said low radiation exposure;

performing a post-exposure bake following said exposing;

performing negative-tone developing of said layer of radiation-sensitive material by contacting said layer of radiation-sensitive material with a first aqueous base solution to remove said second region from said substrate to provide a developed layer of radiation-sensitive material;

removing said exposure gradient of said third region by transforming said third region, and optionally said first region, to a fourth region formed from said first and said third regions having a substantially uniform level of radiation exposure, polarity, or de-protection, or a combination thereof; and

slimming said fourth region,

wherein said layer of radiation-sensitive material comprises:

a material that decreases in polarity upon performing

said exposing and said post-exposure bake following said exposing of said layer of radiation-sensitive material,

an acid wash and a post-acid wash bake of said layer of radiation-sensitive material,

a heating of said layer of radiation-sensitive material to a temperature equal to or greater than a thermal decomposition temperature of said radiation-sensitive material, or

any combination of two or more thereof; or

an acid generator that generates acid upon performing

said exposing and said post-exposure bake following said exposing of said layer of radiation-sensitive material;

said acid wash and said post-acid wash bake of said layer of radiation-sensitive material;

said heating of said layer of radiation-sensitive material to said temperature equal to or greater than said thermal decomposition temperature of said radiation-sensitive material, or

any combination of two or more thereof; or

a protected polymer that undergoes de-protection upon heating to a temperature equal to or greater than a thermal decomposition temperature of said protected polymer.

12. The method of claim 11 , wherein said removing said exposure gradient comprises:

performing a flood exposure and a post-flood exposure bake of said developed layer of radiation-sensitive material;

performing an acid wash and a post-acid wash bake of said developed layer of radiation-sensitive material; or

heating said developed layer of radiation-sensitive material to a temperature equal to or greater than said thermal decomposition temperature of said radiation-sensitive material.

13. The method of claim 12 , wherein said slimming said fourth region comprises

contacting said fourth region with an organic solvent-based composition at an ultra-cold temperature to remove a portion of said fourth region, wherein said ultra-cold temperature is less than 25° C. and greater than a freezing point of said organic solvent-based composition.

14. The method of claim 12 , wherein said slimming said fourth region comprises contacting said fourth region with an organic solvent-based composition to remove a portion of said fourth region, wherein said organic solvent-based composition achieves a rate of a dissolution ranging from about 0.1 nm/sec to about 5 nm/sec.

15. The method of claim 12 , wherein said slimming said fourth region comprises contacting said fourth region with a second aqueous base solution to remove a portion of said fourth region.

16. The method of claim 12 , wherein said slimming said fourth region comprises contacting said fourth region with a second aqueous solution comprising a promoting agent to remove a portion of said fourth region.

17. The method of claim 16 , wherein the promoting agent is a salt comprising an alkali metal.

18. The method of claim 12 , wherein said slimming said fourth region comprises contacting said fourth region with a second aqueous basic solution at a temperature ranging from about 30° C. to about the boiling point of the aqueous base solution.