Granted Patent B2

US 12,216,402 · App. 18/503,696 · Granted Feb 4, 2025

Inventors: Gerhard Ingmar Meijer (Zurich, CH); Valery Weber (Gattikon, CH); Peter Willem Jan Staar (Zurich, CH)

Assignee: International Business Machines Corporation

G03F7/0045C07C309/06C07C309/19C07C309/30C07C309/39C07C311/48C07D285/16C07F7/2208C07F9/92C07F9/94G03F7/26C07C381/12C07C2602/42G03F7/2004

Abstract

Claims (93)

1. A photoacid generator compound cation using

R n —X +

wherein X represents an element

(i) having for 92 eV photons (extreme ultraviolet (EUV)) an absorption cross section of at least 0.5×10 7 ·cm 2 /mol;

(ii) having at least two stable oxidation states; and

(iii) selected from the elements of group 1 to group 15 of the periodic table of the elements;

R represents a linear or branched or a cyclic unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted aryl group having 3 to 30 carbon atoms; or an unsubstituted or a substituted unsaturated or a saturated heterocyclic group having a 3 to 30 membered ring; or derivatives thereof;

wherein at least two R groups are linked via a covalent bond with each other; and

n is 2 to 5.

2. The photoacid generator compound cation according to claim 1 , wherein the at least two stable oxidation states are 1+ and 3+; 2+ and 4+; 3+ and 5+; or 4+ and 6+.

3. The photoacid generator compound cation according to claim 1 , wherein X is selected from the group consisting of the elements In, Sn, Sb, Tl, Pb, and Bi.

4. The photoacid generator compound cation according to claim 1 , wherein the linear or the branched alkyl group is selected from the group consisting of methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosayl and derivatives thereof;

the cyclic alkyl group is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane and derivatives thereof;

the aryl group is selected from the group consisting of phenyl, naphthyl and derivatives thereof; and

the saturated or unsaturated heterocyclic group having one or two heteroatoms is selected from the group consisting of pyrrolidine, pyrrole, tetrahydrofuran, furan, tetrahydrothiophene, thiophene, imidazolidine, imidazole, oxazolidine, oxyzole, thiazolidine, thiazole, dioxolane, dithiolane, piperidine, pyridine, tetrahydropyran, pyran, thiane, thiopyran, diazinane, diazine, in particular pyridazin (1,2-diazin), pyrimidine (1,3-diazin) and pyrazin (1,4-diazin), morpholine, oxazine, thiomorpholine, thiazine, dioxane, dioxine, dithiane, dithiin, quinolone, isoquinoline and derivatives thereof.

5. The photoacid generator compound cation according to claim 1 , wherein the alkyl group or aryl group or heterocyclic group include at least one substituent selected from the group consisting of halogen, hydroxyl, alkyl, alkoxy, aryl, aryloxy, nitro, and cyano.

6. The photoacid generator compound cation according claim 1 , wherein the at least two R groups are linked via a covalent bond between any of two C atoms of the two R groups or a linking atom or linking group, selected from the group consisting of —C—, —O—, —S—, —C(O)—, —S(O)—, and —S(O) 2 —.

7. The photoacid generator compound cation according to claim 1 , wherein the photoacid generator compound cation is selected from the group consisting of triphenyltin, 2,2′-biphenylylene-phenyltin, tetraphenylantimony, 2,2′-biphenylylene-diphenylantimony, tetraphenylbismuth, and 2,2′-biphenylylene-diphenylbismuth.

8. The photoacid generator comprising the photoacid generator compound cation according to claim 1 and an anion.

9. The photoacid generator according to claim 8 , wherein the anion is selected from the group consisting of camphorsulfonate, p-toluenesulfonate, trifluoromethanesulfonate, perfluoro-1-butanesulfonate, hexafluorophosphate, hexafluoroantimonate, tetrakis(pentafluorophenyl)borate, tris(trifluoromethanesulfonyl)methide, hexafluoropropane-1,3-disulfonimide, bis(trifluoromethenesulfonyl)amide, perfluorobutane-1,4-disulfonate, 2-(trifluoromethyl)benzenesulfonate and derivatives thereof.

10. The photoacid generator according to claim 9 , wherein the photoacid generator is selected from the group consisting of:

triphenyltin camphorsulfonate,

triphenyltin p-toluenesulfonate,

triphenyltin trifluoromethenesulfonate,

triphenyltin perfluoro-1-butanesulfonate,

triphenyltin hexafluorophosphate,

triphenyltin hexafluoroantimonate,

triphenyltin tetrakis(pentafluorphenyl)borate,

triphenyltin tris(trifluoromethanesulfonyl)methide,

triphenyltin hexafluoropropane-1,3-disulfonimide

triphenyltin bis(trifluoromethenesulfonyl)amide,

bis(triphenyltin) perfluorbutane-1,4-disulfonate,

triphenyltin 2-(trifluormethyl)benzenesulfonate,

2,2′-biphenylylene-phenyltin camphorsulfonate,

2,2′-biphenylylene-phenyltin p-toluenesulfonate,

2,2′-biphenylylene-phenyltin trifluoromethenesulfonate,

2,2′-biphenylylene-phenyltin perfluoro-1-butanesulfonate,

2,2′-biphenylylene-phenyltin hexafluorophosphate,

2,2′-biphenylylene-phenyltin hexafluoroantimonate,

2,2′-biphenylylene-phenyltin tetrakis(pentafluorphenyl)borate,

2,2′-biphenylylene-phenyltin tris(trifluoromethanesulfonyl)methide,

2,2′-biphenylylene-phenyltin hexafluoropropane-1,3-disulfonimide,

2,2′-biphenylylene-phenyltin bis(trifluoromethenesulfonyl)amide,

bis(2,2′-biphenylylene-phenyltin) perfluorbutane-1,4-disulfonate,

2,2′-biphenylylene-phenyltin 2-(trifluormethyl)benzenesulfonate,

tetraphenylantimony camphorsulfonate,

tetraphenylantimony p-toluenesulfonate,

tetraphenylantimony trifluoromethenesulfonate,

tetraphenylantimony perfluoro-1-butanesulfonate,

tetraphenylantimony hexafluorophosphate,

tetraphenylantimony hexafluoroantimonate,

tetraphenylantimony tetrakis(pentafluorphenyl)borate,

tetraphenylantimony tris(trifluoromethanesulfonyl)methide,

tetraphenylantimony hexafluoropropane-1,3-disulfonimide,

tetraphenylantimony bis(trifluoromethenesulfonyl)amide,

bis(tetraphenylantimony) perfluorbutane-1,4-disulfonate,

tetraphenylantimony 2-(trifluormethyl)benzenesulfonate,

2,2′-biphenylylene-diphenylantimony camphorsulfonate,

2,2′-biphenylylene-diphenylantimony p-toluenesulfonate,

2,2′-biphenylylene-diphenylantimony trifluoromethenesulfonate,

2,2′-biphenylylene-diphenylantimony perfluoro-1-butanesulfonate,

2,2′-biphenylylene-diphenylantimony hexafluorophosphate,

2,2′-biphenylylene-diphenylantimony hexafluoroantimonate,

2,2′-biphenylylene-diphenylantimony tetrakis(pentafluorphenyl)borate,

2,2′-biphenylylene-diphenylantimony tris(trifluoromethanesulfonyl)methide,

2,2′-biphenylylene-diphenylantimony hexafluoropropane-1,3-disulfonimide,

2,2′-biphenylylene-diphenylantimony bis(trifluoromethenesulfonyl)amide,

bis(2,2′-biphenylylene-diphenylantimony) perfluorbutane-1,4-disulfonate,

2,2′-biphenylylene-diphenylantimony 2-(trifluormethyl)benzenesulfonate,

tetraphenylbismuth camphorsulfonate,

tetraphenylbismuth p-toluenesulfonate,

tetraphenylbismuth trifluoromethenesulfonate,

tetraphenylbismuth perfluoro-1-butanesulfonate,

tetraphenylbismuth hexafluorophosphate,

tetraphenylbismuth hexafluoroantimonate,

tetraphenylbismuth tetrakis(pentafluorphenyl)borate,

tetraphenylbismuth tris(trifluoromethanesulfonyl)methide,

tetraphenylbismuth hexafluoropropane-1,3-disulfonimide,

tetraphenylbismuth bis(trifluoromethenesulfonyl)amide,

bis(tetraphenylbismuth) perfluorbutane-1,4-disulfonate,

tetraphenylbismuth 2-(trifluormethyl)benzenesulfonate,

2,2′-biphenylylene-diphenylbismuth camphorsulfonate,

2,2′-biphenylylene-diphenylbismuth p-toluenesulfonate,

2,2′-biphenylylene-diphenylbismuth trifluoromethenesulfonate,

2,2′-biphenylylene-diphenylbismuth perfluoro-1-butanesulfonate,

2,2′-biphenylylene-diphenylbismuth hexafluorophosphate,

2,2′-biphenylylene-diphenylbismuth hexafluoroantimonate,

2,2′-biphenylylene-diphenylbismuth tetrakis(pentafluorphenyl)borate,

2,2′-biphenylylene-diphenylbismuth tris(trifluoromethanesulfonyl)methide,

2,2′-biphenylylene-diphenylbismuth hexafluoropropane-1,3-disulfonimide,

2,2′-biphenylylene-diphenylbismuth bis(trifluoromethenesulfonyl)amide,

bis(2,2′-biphenylylene-diphenylbismuth) perfluorbutane-1,4-disulfonate, and

2,2′-biphenylylene-diphenylbismuth 2-(trifluormethyl)benzenesulfonate.

Assignments (1)

Continuity (2)

References Cited (41)