Freeze-less methods for self-aligned double patterning

1. A method of patterning a substrate, the method comprising:

forming a relief pattern on a substrate, the relief pattern comprising a first photoacid generator, wherein forming the relief pattern comprises forming the relief pattern from a layer of photoresist by exposing the layer of photoresist to actinic radiation to activate the first photoacid generator;

depositing an overcoat in openings of the relief pattern supported by the substrate, the relief pattern further comprising a solubility-shifting agent different from the first photoacid generator, and a first deprotectable monomer sensitive to the solubility-shifting agent, the overcoat comprising a second deprotectable monomer sensitive to the solubility-shifting agent, wherein the relief pattern comprises a first solubility threshold relative to a predetermined developer and the overcoat comprises a second solubility threshold relative to the predetermined developer lower than the first solubility threshold;

activating the solubility-shifting agent to at least reach the second solubility threshold of the overcoat without reaching the first solubility threshold of the relief pattern;

diffusing the solubility-shifting agent a predetermined distance from structures of the relief pattern into the overcoat to form soluble regions in the overcoat, the soluble regions being soluble in the predetermined developer while the relief pattern remains insoluble in the predetermined developer; and

developing the substrate with the predetermined developer to remove the soluble regions of the overcoat.

2. The method of claim 1 , wherein the solubility-shifting agent is a thermal acid generator, and wherein activating the solubility-shifting agent comprises applying heat to the substrate to activate the solubility-shifting agent.

3. The method of claim 1 , wherein

the first photoacid generator is activated at a first wavelength,

the solubility-shifting agent is a second photoacid generator activated at a second wavelength different from the first wavelength, and

activating the solubility-shifting agent comprises exposing the second photoacid generator to actinic radiation comprising the second wavelength to activate the second photoacid generator.

4. The method of claim 1 , wherein the solubility-shifting agent comprises a photodestroyable quencher.

5. The method of claim 4 , wherein the photodestroyable quencher is camphorsulfonic acid.

6. The method of claim 1 , wherein the overcoat comprises a developable bottom anti-reflective coating.

7. The method of claim 1 , wherein the first deprotectable monomer comprises methyl-adamantyl methacrylate, isoadamantyl methacrylate, or tert-Butyl acrylate.

8. The method of claim 1 , wherein the second deprotectable monomer comprises acetal or ester functionality.

9. The method of claim 1 , wherein the predetermined developer comprises tetramethylammonium hydroxide.

10. A method of patterning a substrate, the method comprising:

forming a relief pattern on a substrate, the relief pattern comprising a first photoacid generator, wherein forming the relief pattern comprises forming the relief pattern from a layer of photoresist by exposing the layer of photoresist to actinic radiation to activate the first photoacid generator;

depositing an overcoat in openings of the relief pattern supported by the substrate, the relief pattern further comprising a solubility-shifting agent different from the first photoacid generator, and a first deprotectable monomer having a first activation energy, and the overcoat comprising a second deprotectable monomer having a second activation energy, the first activation energy being higher than the second activation energy;

deprotecting the second deprotectable monomer without deprotecting the first deprotectable monomer to form soluble regions in the overcoat by activating the solubility-shifting agent and diffusing the solubility-shifting agent a predetermined distance from structures of the relief pattern into the overcoat, the soluble regions being soluble in a predetermined developer while the relief pattern remains insoluble in the predetermined developer; and

developing the substrate with the predetermined developer to remove the soluble regions of the overcoat.

11. The method of claim 10 , wherein the solubility-shifting agent is a thermal acid generator, and wherein activating the solubility-shifting agent comprises applying heat to the substrate to activate the solubility-shifting agent.

12. The method of claim 10 , wherein the solubility-shifting agent is a second photoacid generator, and wherein activating the solubility-shifting agent comprises exposing the second photoacid generator to actinic radiation to activate the second photoacid generator.

13. The method of claim 10 , wherein the solubility-shifting agent comprises a photodestroyable quencher.

14. A method of patterning a substrate, the method comprising:

forming a relief pattern on a substrate from a layer of photoresist by exposing the photoresist to actinic radiation comprising a first wavelength to activate a first photoacid generator, the photoresist comprising the first photoacid generator and a solubility-shifting agent;

depositing a deprotectable resin in openings of the relief pattern;

activating the solubility-shifting agent;

diffusing the solubility-shifting agent a predetermined distance from structures of the relief pattern into the deprotectable resin to form soluble regions in the deprotectable resin by deprotecting the deprotectable resin, the soluble regions being soluble in a predetermined developer while the relief pattern remains insoluble in the predetermined developer; and

developing the substrate with the predetermined developer to remove the soluble regions of the deprotectable resin.

15. The method of claim 14 , wherein the solubility-shifting agent is a thermal acid generator, and wherein activating the solubility-shifting agent comprises applying heat to the substrate to activate the solubility-shifting agent.

16. The method of claim 14 , wherein

the first photoacid generator is activated at the first wavelength,

the solubility-shifting agent is a second photoacid generator activated at a second wavelength, and

activating the solubility-shifting agent comprises exposing the second photoacid generator to actinic radiation comprising the second wavelength to activate the second photoacid generator.

17. The method of claim 14 , wherein the solubility-shifting agent comprises a photodestroyable quencher.

18. The method of claim 14 , wherein the photoresist comprises a higher contrast than the deprotectable resin relative to the predetermined developer.

19. A method of patterning a substrate, the method comprising:

depositing an overcoat in openings of a relief pattern supported by a substrate, the relief pattern comprising a solubility-shifting agent and a first deprotectable monomer sensitive to the solubility-shifting agent, the overcoat comprising a second deprotectable monomer sensitive to the solubility-shifting agent, wherein the relief pattern comprises a first solubility threshold relative to a predetermined developer and the overcoat comprises a second solubility threshold relative to the predetermined developer lower than the first solubility threshold;

activating the solubility-shifting agent to at least reach the second solubility threshold of the overcoat without reaching the first solubility threshold of the relief pattern;

diffusing the solubility-shifting agent a predetermined distance from structures of the relief pattern into the overcoat to form soluble regions in the overcoat, the soluble regions being soluble in the predetermined developer while the relief pattern remains insoluble in the predetermined developer; and

developing the substrate with the predetermined developer to remove the soluble regions of the overcoat, wherein

the solubility-shifting agent is a first photoacid generator activated at a first wavelength,

the relief pattern further comprises a second photoacid generator activated at a second wavelength different from the first wavelength, and

activating the solubility-shifting agent comprises exposing the first photoacid generator to actinic radiation comprising the first wavelength to activate the first photoacid generator.

20. The method of claim 19 , the overcoat comprises a developable bottom anti-reflective coating.