Organometallic photoresists for DUV or EUV lithography

Patent metadata

Field	Value
Publication number	US-12135503-B2
Application number	US-202117220412-A
Country	US
Kind code	B2
Filing date	Apr 1, 2021
Priority date	Apr 1, 2021
Publication date	Nov 5, 2024
Grant date	Nov 5, 2024

Abstract

Organometallic photoresists suitable for use in deep ultraviolet (DUV) or extreme ultraviolet (EUV) lithography are provided. The organometallic photoresists contain an organometallic molecule having least a metal element M selected from the group consisting of Bi, Sb, and mixtures thereof, and having an oxidation state of 3+, and at least one polymerizable group R. A method of forming a patterned materials feature on a substrate utilizing the organometallic photoresist compositions is also provided.

First claim

The invention claimed is:

1. An organometallic photoresist composition comprising:
a first organometallic molecule having at least Bi as a metal element, and having an oxidation state of 3+, and at least one first organometallic molecule polymerizable group R, wherein the first organometallic molecule is sensitive to DUV and EUV radiation;
a second organometallic molecule having at least Sb as a metal element, and having an oxidation state of 3+, and at least one second organometallic molecule polymerizable group R, wherein the second organometallic molecule is sensitive to DUV and EUV radiation;
a solvent that dissolves the first and second organometallic molecules.

2. The organometallic photoresist composition according to claim 1 , wherein both the first organometallic molecule and the second organometallic molecule have the general formula (I):

wherein
M represents the metal element;
at least one R group of R 1 , R 2 and R 3 represents the polymerizable group;
the remaining R group(s) of R 1 , R 2 and R 3 represent a non-polymerizable group; and
n is an integer in a range from 1 to the maximum number of hydrogen atoms of the R 3 group.

3. The organometallic photoresist composition according to claim 2 , wherein n is an integer in a range from 1 to 12.

4. The organometallic photoresist composition according to claim 1 , wherein the first organometallic molecule has one of the general formulae (a), (b), or (c), and the second organometallic molecule has one of the general formulae (d), (e), or (f):

wherein
at least one R group of R 1 , R 2 and R 3 represents the polymerizable group; and
the remaining R group(s) of R 1 , R 2 and R 3 represent a non-polymerizable group.

5. The organometallic photoresist composition according to claim 2 , wherein the polymerizable group is selected from the group consisting of a linear, a branched, a cyclic, or a heterocyclic unsaturated monomer having an alkenyl group or an alkynyl group.

6. The organometallic photoresist composition according to claim 2 , wherein the polymerizable group is selected from the group consisting of vinyl, isopropenyl, 1,3-butadienyl, styrene, alpha-methylstyrene, vinylstyrene, cyclopentenyl, cyclohexenyl, cycloheptenyl, acrylate, methacrylate, 2,4-pentadienoate, acrylamide, methacrylamide, 2,4-pentadienamide, phenylacrylate, phenylmethacrylate, phenyl-2,4-pentadienoate, phenylacrylamide, phenylmethacrylamide, phenyl-2,4-pentadienamide, vinylbenzoate, isopropenylbenzoate, butadienylbenzoate, N-vinylbenzamide, N-isopropenylbenzamide, N-butadienylbenzamide, and derivatives thereof; and/or the non-polymerizable group is selected from the group consisting of linear or branched or a cyclic unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted aryl group having 3 to 30 carbon atoms; an unsubstituted or an substituted unsaturated or a saturated heterocyclic group having a 3 to 30 membered ring; and derivatives thereof.

7. The organometallic photoresist composition according to claim 6 , wherein the linear or the branched alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosayl, and derivatives thereof; and/or the cyclic alkyl group is selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, cyclooctane, and derivatives thereof; and/or the aryl group is selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, and derivatives thereof; and/or 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.

8. The organometallic photoresist composition according to claim 2 , wherein the R groups are either separated from each other or at least two R groups are connected via a covalent bond, or a connecting atom, selected from the group consisting of —C—, —O—, —S—, or a connecting group, selected from the group consisting of —C(O)—, —S(O)—, and —S(O) 2 —, between any of two C atoms of the two R groups.

9. The organometallic photoresist composition according to 2, wherein all R groups are polymerizable groups.

10. The organometallic photoresist composition according to claim 2 , further comprising a linking atom or linking group between at least one R group and the metal element M.

11. The organometallic photoresist composition according to claim 10 , wherein the linking atom is selected from the group consisting of —O—, —S—, —Se—, —Te—, and/or the linking group is selected from the group consisting of —C(H) 2 —, —N(X)—, and —P(X)—, wherein X is selected from the group consisting linear or branched or a cyclic unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted aryl group having 3 to 30 carbon atoms; an unsubstituted or a substituted unsaturated or a saturated heterocyclic group having a 3 to 30 membered ring; and derivatives thereof.

12. The organometallic photoresist composition according to claim 1 , comprising from 10 to 80% by weight, based on the total weight of the photoresist composition, of the first organometallic molecule and the second organometallic molecule, and
the solvent is selected from the group consisting of a glycol ether, an aromatic hydrocarbon, an ester and mixtures thereof.

13. The organometallic photoresist composition according to claim 2 , wherein the smallest of the homolytic dissociation energies of the bond between the metal element M and a R group or of the bond between the metal element M and a linking atom or a linking group is larger than 40 kcal/mol and smaller than 60 kcal/mol.

14. The organometallic photoresist composition according to claim 12 , wherein the first organometallic molecule is an organobismuth(III) molecule and the second organometallic molecule is an organoantimony(III) molecule, wherein the organobismuth(III) and the organoantimony(III) molecules are selected from the group consisting of:
tris(ethenyl)bismuthane,
1,4-bis(di(ethenyl)bismuthanyl)benzene,
1,3,5-tris(di(ethenyl)bismuthanyl)benzene,
1,4-bis(di(ethenyl)stibanyl)benzene,
1,3,5-tris(di(ethenyl)stibanyl)benzene,
tris(propen-2-yl)bismuthane,
1,4-bis(di(propen-2-yl)bismuthanyl)benzene,
1,3,5-tris(di(propen-2-yl)bismuthanyl)benzene,
tris(propen-2-yl)stibane,
1,4-bis(di(propen-2-yl)stibanyl)benzene,
1,3,5-tris(di(propen-2-yl)stibanyl)benzene,
tris(buta-1,3-dien-1-yl)bismuthane,
1,4-bis(di(buta-1,3-dien-1-yl)bismuthanyl)benzene,
1,3,5-tris(di(buta-1,3-dien-1-yl)bismuthanyl)benzene,
tris(buta-1,3-dien-1-yl)stibane,
1,4-bis(di(buta-1,3-dien-1-yl)stibanyl)benzene,
1,3,5-tris(di(buta-1,3-dien-1-yl)stibanyl)benzene,
5-(4-ethenylphenyl)-2,8-diethenyl-dibenzobismole,
1,4-bis(2,8-diethenyl-dibenzobismol-5-yl)benzene,
1,3,5-tris(2,8-diethenyl-dibenzobismol-5-yl)benzene,
5-(4-ethenylphenyl)-

Assignees

• IBM

Inventors

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

Classifications

• G03F7/0042 Primary

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

• C07F9/90

  Antimony compounds · CPC title

• C07F9/902

  Compounds without antimony-carbon linkages · CPC title

• C07F9/92

  Aromatic compounds · CPC title

• C07F9/94

  Bismuth compounds · CPC title