Extreme ultraviolet photoresist with high-efficiency electron transfer

Patent metadata

Field	Value
Publication number	US-10520813-B2
Application number	US-201715614032-A
Country	US
Kind code	B2
Filing date	Jun 5, 2017
Priority date	Dec 15, 2016
Publication date	Dec 31, 2019
Grant date	Dec 31, 2019

Abstract

A method includes forming a photoresist layer over a substrate, wherein the photoresist layer includes a polymer, a sensitizer, and a photo-acid generator (PAG), wherein the sensitizer includes a resonance ring that includes nitrogen and at least one double bond. The method further includes performing an exposing process to the photoresist layer. The method further includes developing the photoresist layer, thereby forming a patterned photoresist layer.

First claim

What is claimed is:

1. A method comprising:
forming a photoresist layer over a substrate, wherein the photoresist layer includes a polymer that exhibits a change in solubility in a developer, a sensitizer that emits electrons when exposed to EUV radiation, and a photo-acid generator (PAG), wherein a cation of the PAG has a chemical bond to a sulfur and an additional chemical bond, and wherein the sensitizer includes a material selected from the group consisting of

 and a combination thereof;
performing an exposing process to the photoresist layer, the exposing process having a dose that is less than 20 mJ/cm 2 ;
after the exposing process, performing a thermal treatment to the photoresist layer at a temperature from about 120° C. to about 160° C.; and
after the thermal treatment, developing the photoresist layer, thereby forming a patterned photoresist layer.

2. The method of claim 1 , wherein the sensitizer is chemically bonded to the PAG.

3. The method of claim 1 , wherein the PAG comprises an absorbing group that includes a structure with a plurality of rings, wherein at least one of the rings is heterocyclic and includes at least one double bond.

4. The method of claim 3 , wherein the structure includes one of: sulfur, iodine, or carbon.

5. The method of claim 1 , wherein the exposing process is an extreme ultraviolet (EUV) exposure.

6. The method of claim 1 , where in the sensitizer further includes an oligomer which includes a resonance ring that includes nitrogen and at least one double bond.

7. The method of claim 1 , where in the sensitizer further includes a polymer which includes a resonance ring that includes nitrogen and at least one double bond.

8. The method of claim 1 , wherein the cation of the PAG is a sulfonium cation.

9. The method of claim 8 , wherein the sulfonium cation is a triphenylsulfonium group.

10. The method of claim 1 , wherein an anion of the PAG is a triflate anion.

11. The method of claim 1 , wherein the polymer that exhibits the change in solubility includes a material selected from the group consisting of a poly(norbornene)-co-malaic anhydride (COMA) polymer, a polyhydroxystyrene (PHS) polymer, an acrylate-based polymer, and a combination thereof.

12. The method of claim 11 , wherein the acrylate-based polymer includes a poly (methyl methacrylate) (PMMA) polymer.

13. A method comprising:
forming a photoresist layer over a substrate, wherein the photoresist layer includes a polymer that becomes more soluble or less soluble in a developer, a sensitizer that emits electrons when exposed to EUV radiation, and a photo-acid generator (PAG), wherein the PAG comprises an absorbing group that includes a structure with a plurality of rings, in which one of the rings is a heterocyclic resonance ring with at least one double bond, wherein a cation of the PAG has a chemical bond to a sulfur and an additional chemical bond;
performing an exposing process to the photoresist layer, the exposing process having a dose less than 20 mJ/cm 2 ; and
developing the photoresist layer, thereby forming a patterned photoresist layer, wherein the sensitizer includes a material selected from the group consisting of

 and a combination thereof.

14. The method of claim 13 , wherein the heterocyclic resonance ring includes at least one carbon atom and at least one of: oxygen or nitrogen.

15. The method of claim 13 , further comprising performing a thermal treatment to the photoresist layer at a temperature from about 120° C. to about 160° C. after the exposing process and before the developing.

16. The method of claim 13 , wherein the cation of the PAG is a triphenylsulfonium group.

17. A method comprising:
forming a photoresist layer over a substrate, wherein the photoresist layer includes:
a polymer that changes solubility in a developer;
a sensitizer that emits electrons when exposed to EUV radiation and that includes a resonance ring that includes nitrogen and at least one double bond, wherein the sensitizer includes a material selected from the group consisting of

 and a combination thereof; and
a photo-acid generator (PAG), wherein the PAG comprises an absorbing group that includes a structure with a plurality of rings, in which one of the rings is a heterocyclic resonance ring with at least one double bond, wherein a cation of the PAG has a chemical bond to a sulfur and an additional chemical bond;

performing an extreme ultraviolet (EUV) exposure to the photoresist layer;
after the EUV exposure, performing a thermal treatment to the photoresist layer at a temperature from about 120° C. to about 160° C.; and
after the thermal treatment, developing the photoresist layer, thereby forming a patterned photoresist layer.

18. The method of claim 17 , wherein the PAG includes a heterocyclic ring with at least two double bonds and an oxygen atom.

19. The method of claim 17 , wherein the PAG includes a heterocyclic ring with at least two double bonds and a nitrogen atom.

Assignees

• Taiwan Semiconductor Mfg Co Ltd

Inventors

• Lai Wei-Han
• Lin Chin-Hsiang
• Wang Chien-Wei

Classifications

• G03F7/0045 Primary

  with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors · CPC title

• G03F7/0046

  with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence) · CPC title

• G03F7/0392

  the macromolecular compound being present in a chemically amplified positive photoresist composition · CPC title

• G03F7/0042

  with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence) · CPC title

• C07D273/00

  Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 · CPC title