Granted Patent B2

US 12,572,073 · App. 17/946,428 · Granted Mar 10, 2026

Inventors: Anton Chavez (West Newton, MA); Iou-Sheng Ke (Andover, MA); Shintaro Yamada (Shrewsbury, MA)

Assignee: DUPONT ELECTRONIC MATERIALS INTERNATIONAL, LLC

G03F7/094G03F7/0392G03F7/162G03F7/168G03F7/322

Abstract

Claims (113)

1 . A method of forming a pattern, the method comprising:

providing a photoresist underlayer over a substrate;

forming a photoresist layer over the photoresist underlayer;

patterning the photoresist layer; and

transferring a pattern from the patterned photoresist layer to the photoresist underlayer;

wherein the photoresist underlayer is formed from a composition comprising a solvent and a compound represented by Formula 1

or

a polymer having a repeating unit represented by Formula 2,

wherein Ar1 and Ar2 independently represent an aromatic group,

in Formula 1, each Y 1 and each Y 2 are independently —OH, —SH, —R A , —OR A , and in Formula 2, each Y 1 and each Y 2 are independently —OH, —SH, —C(O)OH, —NH 2 , —R A , —OR A , —C(O)OR A , —SR A , or —NHR A , and y 1 and y 2 are independently an integer from 0 to 6;

X 1 and X 2 are independently a single bond or a divalent linker;

X 3 is a divalent linker;

Z 1 and Z 2 are independently —OR A , —C(O)OR A , —SR A , —NHR A , —OC(O)CR B ═CH 2 , a substituted or unsubstituted C 1-18 alkyl group, a substituted or unsubstituted C 1-18 alkoxy group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 3-12 heterocycloalkyl group, a substituted or unsubstituted C 3-12 glycidyl group, a substituted or unsubstituted C 2-18 alkenyl group, a substituted or unsubstituted C 5-12 cycloalkenyl group, a substituted or unsubstituted C 3-18 alkynyl group, a substituted or unsubstituted C 6-14 aryl group, or a substituted or unsubstituted C 3-44 heteroaryl,

R A is independently a substituted or unsubstituted C 1 -C 18 alkyl, a substituted or unsubstituted C 3 -C 12 cycloalkyl, a substituted or unsubstituted C 3 -C 12 heterocycloalkyl, a substituted or unsubstituted C 2-18 alkenyl, a substituted or unsubstituted C 3-8 alkyne, a substituted or unsubstituted C 6 -C 14 aryl, or a substituted or unsubstituted C 6 -C 14 heteroaryl;

R B is hydrogen, fluorine, or a substituted or unsubstituted C 1-5 alkyl;

T 1 and T 2 are independently a divalent linker;

z 1 and z 2 are independently an integer from 0 to 6, and for the compound of Formula 1,

z 1 +y 1 is at least 1 and z 2 +y 2 is at least 1; and

t 1 and t 2 are independently an integer from 0 to 6.

2 . The method of claim 1 , wherein Ar1 and Ar2 are independently a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted quinolinyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted fluorenyl, or a substituted or unsubstituted carbazoyl.

3 . The method of claim 1 , wherein the divalent linker X 3 , T 1 , and T 2 of Formula 2 are independently —O—, —S—, —C(O)—, or a group moiety of

wherein

R D is a single bond, or —C(O)—, —S(O) 2 —, a substituted or unsubstituted C 1-6 alkylene, a substituted or unsubstituted C 3-14 cycloalkylene, a substituted or unsubstituted C 1-22 heteroalkylene, a substituted or unsubstituted C 6-24 arylene, or a substituted or unsubstituted C 3-24 heteroarylene,

R E is a substituted or unsubstituted C 1-6 alkylene, a substituted or unsubstituted C 3-14 cycloalkylene, a substituted or unsubstituted C 1-22 heteroalkylene, a substituted or unsubstituted C 6-24 arylene, or a substituted or unsubstituted C 3-24 heteroarylene,

W and W 1 are independently a substituted or unsubstituted C 1-4 alkylene, —O—, or a combination thereof;

Ar 4 and Ar 5 are independently a substituted or unsubstituted C 6-14 arylene, or a substituted or unsubstituted C 3-14 heteroarylene;

Z is absent, O, —S—, —C(O)—, a substituted or unsubstituted C 1-4 alkylene;

m is 0, 1, or 2; n is 0 or 1; and

* represents a point of attachment for the divalent linker.

4 . The method of claim 1 , wherein the photoresist underlayer composition further comprises a compound including an epoxy group or a polymer comprising an epoxy group.

5 . The method of claim 1 , wherein the photoresist underlayer composition further comprises:

a polymer derived from a monomer of Formula 4

wherein

L 2 is a divalent linking group;

J is a substituted or unsubstituted C 1 -C 10 alkyl group with a hydroxy group or a glycidyl group, a substituted or unsubstituted C 3 -C 10 cycloalkyl group with a hydroxy group or a glycidyl group, a substituted or unsubstituted C 6-24 aryl group with a hydroxy group or a glycidyl group, or a substituted or unsubstituted C 3-24 heteroaryl group with a hydroxy group or glycidyl group; and

R P is hydrogen, fluorine, or an optionally substituted C 1-5 alkyl; or

a polymer including a repeating unit represented by Formula 5;

wherein in Formula 5

Ring A represents an aromatic group,

Y is a divalent linking group, and

o is an integer from 1 to 8.

6 . The method of claim 1 , wherein the compounds of Formula 1 are represented by the following:

and

the polymers with the repeating unit of Formula 2 are represented as follows;

or

y 1 and y 2 are independently 0, 1, 2, or 3 and y 1 +y 2 is at least 1, each Y 1 and each Y 2 are independently —OH, —SH, —C(O)OH, 13 NH 2 , R A , —OR A , —C(O)OR A , —SR A , or —NHR A , and R A is independently a substituted or unsubstituted C 1 -C 6 alkyl, a substituted or unsubstituted C 3 -C 6 heterocycloalkyl, or a substituted or unsubstituted C 6 -C 14 aryl; and

X 3 , T 1 , and T 2 independently comprise an aromatic group with one to three aromatic rings, and/or

W and W 1 are independently a substituted or unsubstituted C 1-4 alkylene, —O—, or a combination thereof;

Ar 4 and Ar 5 are independently a substituted or unsubstituted C 6-14 arylene, or a substituted or unsubstituted C 3-14 heteroarylene;

Z is absent, O, —S—, —C(O)—, a substituted or unsubstituted C 1-4 alkylene;

m is 0, 1, or 2; n is 0 or 1; and

* represents a point of attachment for the divalent linker

t 1 and t 2 are independently 0, 1, or 2.

7 . A method of forming a pattern, the method comprising:

providing a photoresist underlayer over a substrate;

forming a photoresist layer over the photoresist underlayer;

patterning the photoresist layer; and

transferring a pattern from the patterned photoresist layer to the photoresist underlayer;

wherein the photoresist underlayer is formed from a composition comprising a solvent and a compound represented by Formula 1

or

a polymer having a repeating unit represented by Formula 2,

wherein Ar1 and Ar2 independently represent an aromatic group,

in Formula 1, each Y 1 and each Y 2 are independently —OH, —SH, —NH 2 , —R A , —OR A , and in Formula 2, each Y 1 and each Y 2 are independently —OH, —SH, —C(O)OH, —NH 2 , —R A , —OR A , —C(O)OR A , —SR A , or —NHR A , and y 1 and y 2 are independently an integer from 0 to 6;

X 1 and X 2 are independently a single bond or a divalent linker;

X 3 is a divalent linker;

Z 1 and Z 2 of Formula 1 are independently, represented by the following:

wherein in Formula 1,

* represents a point of attachment to X 1 or X 2, or if X 1 or X 2 is a single bond then a point of connection to a ring carbon of Ar1 or Ar2, respectively, and

R is hydrogen, substituted or unsubstituted C 1-22 alkyl, substituted or unsubstituted C 3-14 cycloalkyl, substituted or unsubstituted C 1-22 heteroalkyl, substituted or unsubstituted C 2-14 heterocycloalkyl, substituted or unsubstituted C 6-24 aryl, or substituted or unsubstituted C 3-24 heteroaryl, and Z 1 and Z 2 in Formula 2 are independently —OR A , —C(O)OR A , —SR A , —NHR A , —OC(O)CR B ═CH 2 , a substituted or unsubstituted C 1-18 alkyl group, a substituted or unsubstituted C 1-18 alkoxy group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 3-12 heterocycloalkyl group, a substituted or unsubstituted C 3-12 glycidyl group, a substituted or unsubstituted C 2-18 alkenyl group, a substituted or unsubstituted C 5-12 cycloalkenyl group, a substituted or unsubstituted C 3-18 alkynyl group, a substituted or unsubstituted C 6-14 aryl group, or a substituted or unsubstituted C 3-44 heteroaryl, where R A is independently a substituted or unsubstituted C 1 -C 18 alkyl, a substituted or unsubstituted C 3 -C 12 cycloalkyl, a substituted or unsubstituted C 3 -C 12 heterocycloalkyl, a substituted or unsubstituted C 2-18 alkenyl, a substituted or unsubstituted C 3-8 alkyne, a substituted or unsubstituted C 6 -C 14 aryl, or a substituted or unsubstituted C 6 -C 14 heteroaryl; and

where R B is hydrogen, fluorine, or a substituted or unsubstituted C 1-5 alkyl;

T 1 and T 2 are independently a divalent linker;

z 1 and z 2 are independently an integer from 0 to 6, and for the compound of Formula 1, z 1 +y 1 is at least 1 and z 2 +y 2 is at least 1; and

t 1 and t 2 are independently an integer from 0 to 6.

8 . A photoresist underlayer composition comprising a solvent and a compound represented by Formula 1

or a polymer having a repeating unit represented by Formula 2,

wherein:

Ar1 and Ar2 independently represent an aromatic group,

in Formula 1, each Y 1 and each Y 2 are independently —SH, —R A , —OR A , and in Formula 2, each Y 1 and each Y 2 are independently —OH, —SH, —C(O)OH, —NH 2 , —R A , —OR A , —C(O)OR A , —SR A , or —NHR A , and y 1 and y 2 are independently an integer from 0 to 6;

X 1 and X 2 are independently a single bond or a divalent linker;

X 3 is a divalent linker;

Z 1 and Z 2 are independently —OR A , —C(O)OR A , —SR A , —NHR A , —OC(O)CR B ═CH 2 , a substituted or unsubstituted C 1-18 alkyl group, a substituted or unsubstituted C 1-18 alkoxy group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 3-12 heterocycloalkyl group, a substituted or unsubstituted C 3-12 glycidyl group, a substituted or unsubstituted C 2-18 alkenyl group, a substituted or unsubstituted C 5-12 cycloalkenyl group, a substituted or unsubstituted C 3-18 alkynyl group, a substituted or unsubstituted C 6-14 aryl group, or a substituted or unsubstituted C 3-44 heteroaryl,

where R A is independently a substituted or unsubstituted C 1 -C 18 alkyl, a substituted or unsubstituted C 3 -C 12 cycloalkyl, a substituted or unsubstituted C 3 -C 12 heterocycloalkyl, a substituted or unsubstituted C 2-18 alkenyl, a substituted or unsubstituted C 3-8 alkyne, a substituted or unsubstituted C 6 -C 14 aryl, or a substituted or unsubstituted C 6 -C 14 heteroaryl;

where R B is hydrogen, fluorine, or a substituted or unsubstituted C 1-5 alkyl;

T 1 and T 2 are independently a divalent linker;

z 1 and z 2 are independently an integer from 0 to 6, and for the compound of Formula 1,

z 1 +y 1 is at least 1 and z 2 +y 2 is at least 1; and

t 1 and t 2 are independently an integer from 0 to 6,

wherein the photoresist underlayer is free of photoacid generators.

9 . The photoresist underlayer composition of claim 8 , further comprising:

a polymer derived from a monomer of Formula 4

wherein

L 2 is a divalent linking group;

J is a substituted or unsubstituted C 1 -C 10 alkyl group with a hydroxy group or a glycidyl group, a substituted or unsubstituted C 3 -C 10 cycloalkyl group with a hydroxy group or a glycidyl group, a substituted or unsubstituted C 6-24 aryl group with a hydroxy group or a glycidyl group, or a substituted or unsubstituted C 3-24 heteroaryl group with a hydroxy group or glycidyl group; and

R P is hydrogen, fluorine, or an optionally substituted C 1-5 alkyl; or

a polymer including a repeating unit represented by Formula 5;

wherein in Formula 5

Ring A represents an aromatic group,

Y is a divalent linking group, and

o is an integer from 1 to 8.

10 . A photoresist underlayer composition comprising a solvent, a compound including an epoxy group or a polymer comprising an epoxy group, and a compound represented by Formula 1

or a polymer having a repeating unit represented by Formula 2,

wherein:

Ar1 and Ar2 independently represent an aromatic group,

in Formula 1, each Y 1 and each Y 2 are independently —SH, —R A , —OR A , and in Formula 2, each Y 1 and each Y 2 are independently —OH, —SH, —C(O)OH, —NH 2 , —R A , —OR A , —C(O)OR A , —SR A , or —NHR A , and y 1 and y 2 are independently an integer from 0 to 6;

X 1 and X 2 are independently a single bond or a divalent linker;

X 3 is a divalent linker;

Z 1 and Z 2 are independently —OR A , —C(O)OR A , —SR A , —NHR A , —OC(O)CR B ═CH 2 , a substituted or unsubstituted C 1-18 alkyl group, a substituted or unsubstituted C 1-18 alkoxy group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 3-12 heterocycloalkyl group, a substituted or unsubstituted C 3-12 glycidyl group, a substituted or unsubstituted C 2-18 alkenyl group, a substituted or unsubstituted C 5-12 cycloalkenyl group, a substituted or unsubstituted C 3-18 alkynyl group, a substituted or unsubstituted C 6-14 aryl group, or a substituted or unsubstituted C 3-44 heteroaryl,

where R A is independently a substituted or unsubstituted C 1 -C 18 alkyl, a substituted or unsubstituted C 3 -C 12 cycloalkyl, a substituted or unsubstituted C 3 -C 12 heterocycloalkyl, a substituted or unsubstituted C 2-18 alkenyl, a substituted or unsubstituted C 3-8 alkyne, a substituted or unsubstituted C 6 -C 14 aryl, or a substituted or unsubstituted C 6 -C 14 heteroaryl;

where R B is hydrogen, fluorine, or a substituted or unsubstituted C 1-5 alkyl;

T 1 and T 2 are independently a divalent linker;

z 1 and z 2 are independently an integer from 0 to 6, and for the compound of Formula 1,

z 1 +y 1 is at least 1 and z 2 +y 2 is at least 1; and

t 1 and t 2 are independently an integer from 0 to 6.

Assignments (4)

Continuity (1)

References Cited (17)