Photoacid generator for chemically amplified photoresists for deep ultra violet and extreme ultraviolet lithography
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.
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)borane anion, bis(diphenylantimonyldicyanoethen-1-yl)-(1,1,2,4,5,5-hexacyanopent-1,4-dien-3-yl)borane anion, bis(diphenylbismuthyldicyanoethen-1-yl)-(1,1,2,4,5,5-hexacyanopent-1,4-dien-3-yl)borane anion, pentacyano-(trimethylstannyl)borinine anion, pentacyano-(dimethylantimonyl)borinine anion, pentacyano-(dimethylbismuthyl)borinine anion, pentacyano-(triphenylstannyl)borinine anion, pentacyano-(diphenylantimonyl)borinine anion, pentacyano-(diphenylbismuthyl)borinine anion, hexacyano-bis(trimethylstannyl)benzo[a]borinine anion, hexacyano-bis(dimethylantimonyl)benzo[a]borinine anion, hexacyano-bis(dimethylbismuthyl)benzo[a]borinine anion, hexacyano-bis(triphenylstannyl)benzo[a]borinine anion, hexacyano-bis(diphenylantimonyl)benzo[a]borinine anion, and hexacyano-bis(diphenylbismuthyl)benzo[a]borinine anion.
14. The composition of claim 1 , wherein a conjugate acid of the PAG anion has a proton dissociation energy smaller than 255 kcal/mol.
15. A photoresist composition comprising a photoacid generator (PAG), wherein the PAG comprises:
a PAG anion, the 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; and
a cation selected from the group consisting of triphenylsulfonium, diphenyliodonium, phenylthiolanium, and derivatives thereof.
16. The photoresist composition of claim 15 , wherein the PAG is in an amount of 5 to 95% by weight.
17. The composition of claim 15 , wherein a conjugate acid of the PAG anion has a proton dissociation energy smaller than 255 kcal/mol.
18. A method of forming a patterned material feature on a substrate, comprising:
providing a material surface on the substrate;
forming a layer of a photoresist composition over the material surface, wherein the photoresist composition comprises a photoacid generator (PAG), comprising:
a 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, wherein at least one of the R groups comprises an electron withdrawing group; and
a cation selected from the group consisting of triphenylsulfonium, diphenyliodonium, phenylthiolanium, and derivatives thereof;
irradiating the photoresist layer with an energy ray to form a pattern of radiation-exposed regions in the photoresist layer;
selectively removing portions of the irradiated photoresist layer to form exposed portions of the material surface; and
etching or ion implanting the exposed portions of the material surface, thereby forming the patterned material feature.
19. The method of claim 18 , wherein the energy ray is a deep ultraviolet (DUV) irradiation or an extreme ultraviolet (EUV) irradiation.
20. The method of claim 18 , wherein the PAG is in an amount of 5 to 95% by weight.