Photoacid generator for chemically amplified photoresists for deep ultra violet and extreme ultraviolet lithography

Patent metadata

Field	Value
Publication number	US-12306535-B2
Application number	US-202217648495-A
Country	US
Kind code	B2
Filing date	Jan 20, 2022
Priority date	Jan 20, 2022
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

A photoacid generator (PAG) anion, a photoresist composition, and a method are disclosed. The PAG anion includes a moiety, selected from an alkyl group, a monocyclic aromatic group, and a bicyclic aromatic group, that includes a carbon atom with a negative elementary charge. The PAG anion also includes an electron acceptor atom, selected from boron(III), aluminum(III), and phosphorus(V), which is covalently bonded to the carbon atom. The PAG anion also has at least one electron-withdrawing R group. The photoresist composition has a PAG that includes the PAG anion and a cation selected from triphenylsulfonium, diphenyliodonium, phenylthiolanium, and derivatives thereof. The method includes forming a layer of the photoresist composition over a material surface on a substrate, irradiating the layer to form a pattern of radiation-exposed regions, selectively removing portions of the irradiated layer to form exposed portions of the material surface, and etching or ion implanting the exposed portions.

First claim

What is claimed is:

1. A composition, comprising:
a photoacid generator (PAG) anion, comprising:
a first moiety selected from the group consisting of an alkyl group, a monocyclic aromatic group, and a bicyclic aromatic group, wherein the first moiety comprises a carbon atom with a negative elementary charge;
an electron acceptor atom selected from the group consisting of boron(III), aluminum(III), and phosphorus(V), wherein the electron acceptor atom is covalently bonded to the carbon atom; and
R groups comprising at least one electron-withdrawing R group.

2. The composition of claim 1 , wherein the PAG anion has the general formula (I):

wherein:
X represents the electron acceptor atom; and
R1, R2, R3, and R4 represent the R groups.

3. The composition of claim 1 , wherein the PAG anion has the general formula (II):

wherein:
X represents the electron acceptor atom;
R1, R2, R3, R4, and R5 represent the R groups;
Y represents a methylene group; and
n is 0 or an integer in a range from 1 to 3.

4. The composition of claim 3 , wherein at least two adjacent groups of the R groups are linked with each other to form a five-, six-, or seven-membered aromatic ring that includes at least one electron-withdrawing group.

5. The composition of claim 1 , wherein the PAG anion has the general formula (III):

wherein:
X represents the electron acceptor atom;
R1, R2, R3, R4, R5, and R6 represent the R groups;
Y and Z each represent a methylene group;
n is 0 or an integer in a range from 1 to 3; and
m is 0 or an integer in a range from 1 to 3.

6. The composition of claim 5 , wherein at least two adjacent groups of the R groups are linked with each other to form a five-, six-, or seven-membered aromatic ring that includes at least one electron-withdrawing group.

7. The composition of claim 1 , wherein the at least one electron-withdrawing R group is selected from the group consisting of cyano, cyanoimino, linear or branched C 1 to C 4 cyanoalkyl, linear or branched C 1 to C 4 cyanoalkenyl, linear or branched C 1 to C 4 cyanoalkylene, C 1 to C 4 alkylsulfonyl, (C 1 to C 4 alkylsulfonyl) imino, linear or branched C 1 to C 4 (C 1 to C 4 alkylsulfonyl) alkyl, linear or branched C 1 to C 4 (C 1 to C 4 alkylsulfonyl) alkenyl, linear or branched C 1 to C 4 (C 1 to C 4 alkylsulfonyl) alkylene, fluoro, fluoroimino, linear or branched C 1 to C 8 fluoroalkyl, (linear or branched C 1 to C 8 fluoroalkyl) imino, linear or branched C 1 to C 8 fluoroalkenyl, linear or branched C 1 to C 8 fluoroalkylene, (C 1 to C 4 fluoroalkyl) sulfonyl, (C 1 to C 4 fluoroalkyl) sulfonylimino, linear or branched C 1 to C 4 (C 1 to C 4 fluoroalkyl) sulfonylalkyl, linear or branched C 1 to C 4 (C 1 to C 4 fluoroalkyl) sulfonylalkenyl, linear or branched C 1 to C 4 (C 1 to C 4 fluoroalkyl) sulfonylalkylene, C 3 to C 7 fluorocycloalkyl, (C 3 to C 7 fluorocycloalkyl) imino, C 5 to C 7 fluoroaryl, (C 5 to C 7 fluoroaryl) imino, and derivatives thereof.

8. The composition of claim 1 , wherein the R groups further comprise at least one non-electron-withdrawing R group.

9. The composition of claim 8 , wherein the at least one non-electron-withdrawing R group is selected from the group consisting of H, optionally substituted linear or branched alkyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted saturated or unsaturated heterocyclic group, and derivatives thereof.

10. The composition of claim 1 , wherein the PAG anion is selected from the group consisting of 2-(dicyanoboranyl)propanedinitrile anion, bis(methylsulfonyl)boranyl-bis(methylsulfonyl)methane anion, dicyanoboranyl-bis(methylsulfonyl)methane anion, 2-(bis(trifluoromethyl)boranyl)-1,1,1,3,3,3-hexafluoropropane anion, bis(trifluoromethylsulfonyl)boranyl-bis(trifluoromethylsulfonyl)methane anion, dicyanoboranyl-bis(trifluoromethylsulfonyl)methane anion, 2-(dicyanoaluminyl)propanedinitrile anion, bis(methylsulfonyl)aluminyl-bis(methylsulfonylmethane) anion, dicyanoaluminyl-bis(methylsulfonylmethane) anion, 2-(bis(trifluoromethyl)aluminyl)-1,1,1,3,3,3-hexafluoropropane anion, bis(trifluoromethylsulfonyl)aluminyl-bis(trifluoromethylsulfonyl)methane anion, dicyanoaluminyl-bis(trifluoromethylsulfonyl)methane anion, bis(cyanoimino)(dicyanomethyl)phosphorane anion, bis(methylsulfonylimino)-bis(methylsulfonyl)methylphosphorane anion, bis(trifluoromethylimino)(1,1,1,3,3,3-hexafluoroprop-2-yl)phosphorane anion, bis(trifluoromethylsulfonylimino)-bis(trifluoromethylsulfonyl)methylphosphorane anion, bis(dicyanomethylene)(dicyanomethyl)phosphorane anion, bis(bis(methylsulfonyl)methylene)-bis(methylsulfonyl)methylphosphorane anion, bis(bis(trifluoromethyl)methylene) (1,1,1,3,3,3-hexafluoroprop-2-yl)phosphorane anion, bis(bis(trifluoromethylsulfonyl)methylene)-bis(trifluoromethylsulfonyl)methylphosphorane anion, 1,2,3,4,5,6-hexacyanoborinine anion, 1,2,3,4,5,6-hexakis(methylsulfonyl)borinine anion, 1-cyano-2,3,4,5,6-pentakis(methylsulfonyl)borinine anion, 1,2,3,4,5,6-hexakis(trifluoromethyl)borinine anion, 1,2,3,4,5,6-hexakis(trifluoromethylsulfonyl)borinine anion, 1-cyano-2,3,4,5,6-pentakis(trifluoromethylsulfonyl)borinine anion, 1,2,3,4,5,6-hexacyanoaluminine anion, 1,2,3,4,5,6-hexakis(methylsulfonyl)aluminine anion, 1-cyano-2,3,4,5,6-pentakis(methylsulfonyl)aluminine anion, 1,2,3,4,5,6-hexakis(trifluoromethyl)aluminine anion, 1,2,3,4,5,6-hexakis(trifluoromethylsulfonyl)aluminine anion, 1-cyano-2,3,4,5,6-pentakis(trifluoromethylsulfonyl)aluminine anion, 1,2,3,4,5,6,7,8-octacyanobenzo[a]borinine anion, 1,8-(1,2,3,4-tetracyanobuta[1,3]dieno)-2,3,4,5,6,7-hexacyanobenzo[a]borinine anion, bis-[1,8:4,5]-(1,2,3,4-tetracyanobuta[1,3]dieno)-2,3,6,7-tetracyanobenzo[a]borinine anion, 1,2,3,4,5,6,7,8-octacyanobenzo[a]aluminine anion, 1,8-(1,2,3,4-tetracyanobuta[1,3]dieno)-2,3,4,5,6,7-hexacyanobenzo[a]aluminine anion, bis-[1,8:4,5]-(1,2,3,4-tetracyanobuta[1,3]dieno)-2,3,6, 7-tetracyanobenzo[a]aluminine anion, 1,2,3,4,5,6-hexakis(methylsulfonyl)borinine anion, 1-cyano-2,3,4,5,6-pentakis(methylsulfonyl)borinine anion, 1,2,3,4,5,6,7,8-octakis(methylsulfonyl)benzo[a]borinine anion, 1,2,3,4,5,6-hexakis(methylsulfonyl)aluminine anion, 1-cyano-2,3,4,5,6-pentakis(methylsulfonyl)aluminine anion, and 1,2,3,4,5,6,7,8-octakis(methylsulfonyl)benzo[a]aluminine anion.

11. The composition of claim 1 , wherein the at least one electron-withdrawing R group is selected from the group consisting of a trialkylstannyl-, a triarylstannyl-, a dialkylantimonyl-, a diarylantimonyl, a dialkylbismuthyl-, and a diarylbismuthyl group.

12. The composition of claim 1 , wherein the at least one electron-withdrawing R group is selected from the group consisting of cyanoethenyl, dicyanoethenyl, tricyanoethenyl, methylsulfonyl, methylsulfonylimino, cyanomethylene, dicyanomethylene, methylsulfonylmethylene, and bis(methylsulfonyl)methylene.

13. The composition of claim 1 , wherein the PAG anion is selected from the group consisting of bis(trimethylstannyldicyanoethen-1-yl)-(1,1,2,4,5,5-hexacyanopent-1,4-dien-3-yl)borane anion, bis(dimethylantimonyldicyanoethen-1-yl)-(1,1,2,4,5,5-hexacyanopent-1,4-dien-3-yl)borane anion, bis(dimethylbismuthyldicyanoethen-1-yl)-(1,1,2,4,5,5-hexacyanopent-1,4-dien-3-yl)borane anion, bis(triphenylstannyldicyanoethen-1-yl)-(1,1,2,4,5,5-hexacyanopent-1,4-dien-3-yl)bor

Assignees

• IBM

Inventors

• Meijer Gerhard Ingmar
• Weber Valery
• Staar Peter Willem Jan

Classifications

• G03F7/0382

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

• C07F5/027 Primary

  Organoboranes and organoborohydrides · CPC title

• C07C381/12

  Sulfonium compounds · CPC title

• G03F7/0392

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

• C07F9/5355

  Phosphoranes containing the structure P=N- · CPC title