Photoresist layer surface treatment, cap layer, and method of forming photoresist pattern

1. A method of forming a pattern in a photoresist layer,

comprising:

forming a photoresist layer over a substrate,

wherein the photoresist layer comprises a metal-containing photoresist composition;

reducing moisture or oxygen absorption characteristics of the photoresist layer,

wherein the reducing moisture or oxygen absorption characteristics of the photoresist layer comprises performing a surface treatment to a surface of the photoresist layer, wherein the surface treatment comprises changing the surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface;

selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and

developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern.

2. The method according to claim 1 , wherein the surface treatment comprises reacting end groups of ligands in the photoresist layer with ammonia, a silane, an alkyl halide, a silicon halide, an amino alkyl, or a carboxyl alkyl.

3. The method according to claim 1 , wherein the surface treatment comprises replacing end groups of ligands in the photoresist layer with a non-polar organic group.

4. The method according to claim 1 , wherein the surface treatment comprises converting hydrophilic end groups on ligands in the photoresist layer to hydrophobic end groups.

5. The method according to claim 1 , wherein the photoresist layer is formed over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

6. The method according to claim 1 , further comprising after selectively exposing the photoresist layer to form a latent pattern, heating the photoresist layer at a temperature ranging from 100° C. to 500° C.

7. The method according to claim 1 , wherein the surface treatment is performed in a same processing chamber as the forming a photoresist layer.

8. The method according to claim 1 , further comprising heating the photoresist layer at a temperature ranging from 40° C. to 150° C. after the surface treatment and before the selectively exposing the photoresist layer.

9. A method of manufacturing a semiconductor device,

comprising:

forming a photoresist layer over a substrate, comprising:

combining a first precursor and a second precursor in a vapor state to form a photoresist material, and

depositing the photoresist material over the substrate;

reducing moisture or oxygen absorption characteristics of the photoresist layer,

wherein the reducing moisture or oxygen absorption characteristics of the photoresist layer comprises changing a surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface;

selectively exposing the photoresist layer to actinic radiation to form a latent pattern in the photoresist layer;

developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer; and

extending the pattern in the photoresist layer into the substrate.

10. The method according to claim 9 , wherein the first precursor is an organometallic having a formula:

M a R b X c

where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu,

R is a substituted or unsubstituted alkyl, alkenyl, or carboxylate group,

X is a halide or sulfonate group, and

1≤a≤2, b≥1, c≥1, and b+c≤5; and

the second precursor is at least one of an amine, a borane, a phosphine, or water.

11. The method according to claim 9 , wherein the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

12. The method according to claim 9 , wherein the changing a surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface comprises reacting end groups of ligands in the photoresist layer with ammonia, a silane, an alkyl halide, a silicon halide, an amino alkyl, or a carboxyl alkyl.

13. The method according to claim 9 , wherein the changing a surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface comprises replacing end groups of ligands in the photoresist layer with a non-polar organic group.

14. The method according to claim 9 , wherein the changing a surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface comprises converting hydrophilic end groups on ligands in the photoresist layer to hydrophobic end groups.

15. The method according to claim 9 , wherein the changing a surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface is performed in a same processing chamber as the forming a photoresist layer.

16. The method according to claim 9 , further comprising heating the photoresist layer at a temperature ranging from 40° C. to 150° C. after the changing a surface of the photoresist layer from a hydrophilic surface to a hydrophobic surface and before the selectively exposing the photoresist layer.

17. A method of manufacturing a semiconductor device,

comprising:

depositing a photoresist composition comprising a first organometallic compound and a second compound over a substrate surface via atomic layer deposition (ALD) or chemical vapor deposition (CVD) to form a photoresist layer;

reducing moisture or oxygen absorption characteristics of the photoresist layer,

wherein the reducing moisture or oxygen absorption characteristics of the photoresist layer comprises reacting end groups of ligands in the photoresist layer with ammonia, a silane, a silylamine, an alkyl halide, an aryl halide, a silicon halide, an alkyl amine, a carboxy alkyl, or a carboxy aryl;

selectively exposing the photoresist layer to actinic radiation to form a latent pattern;

developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern exposing a portion of the substrate surface; and

removing a portion of the substrate surface exposed by the developing.

18. The method according to claim 17 , wherein the removing a portion of the substrate surface by the developing includes etching the substrate surface.

19. The method according to claim 17 , further comprising after selectively exposing the photoresist layer to form a latent pattern, heating the photoresist layer at a temperature ranging from 100° C. to 500° C.

20. The method according to claim 17 , further comprising heating the photoresist layer at a temperature ranging from 40° C. to 150° C. after the reducing moisture or oxygen absorption characteristics of the photoresist layer and before the selectively exposing the photoresist layer.