Granted Patent B2

US 12,656,682 · App. 17/231,413 · Granted Jun 16, 2026

Inventor: Chien-Chih Chen (Taipei City, TW)

Assignee: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.

G03F7/0382C08L101/02G03F7/0045G03F7/38G03F7/40

Abstract

Claims (54)

1 . A method of manufacturing a semiconductor device, comprising:

forming a photoresist layer over a substrate,

wherein the photoresist layer comprises a photoresist composition comprising a polymer,

wherein the polymer comprises:

a monomer unit having a pendant sensitizer selected from the group consisting of phenyl group, a naphthalenyl group, a phenanthrenyl group, an anthracenyl group, and a phenalenyl group, and a crosslinking group bonded to the sensitizer, wherein the crosslinking group is one or more of a C2-C30 aromatic group having a functional group selected from the group consisting of an azo group, an alkyl halide group, and a peroxide group;

a monomer unit having a pendant acid labile group; and

a monomer unit having a pendant organic group, wherein the pendant organic group is a C1-C30 group substituted with one or more of —I, —Br, —Cl, —NH 2 , —SH, —N 3 , —S(═O)—, an alkene group, an alkyne group, an imine group, an ether group, an aldehyde group, an amide group, a sulfone group, or a cyanide group;

selectively exposing the photoresist layer with the polymer comprising the monomer unit having the pendant sensitizer and crosslinking group and the monomer unit having the pendant acid labile group to actinic radiation, thereby causing the polymer to crosslink through the crosslinking group; and

developing the selectively exposed photoresist layer.

2 . The method according to claim 1 , wherein the photoresist composition further comprises a photoacid generator.

3 . The method according to claim 2 , wherein the photoacid generator releases an acid and the sensitizer generates secondary electrons upon exposure to radiation.

4 . The method according to claim 1 , wherein the polymer has a weight average molecular weight of 1000 to 200,000.

5 . The method according to claim 1 , wherein portions of the photoresist layer not exposed to actinic radiation are removed during the developing the selectively exposed photoresist layer.

6 . The method according to claim 1 , wherein the polymer undergoes an acid labile group deprotection reaction upon the exposure to actinic radiation.

7 . The method according to claim 1 , wherein the photoresist layer is a top layer of a trilayer resist.

8 . A method of manufacturing a semiconductor device, comprising:

forming a photoresist layer over a substrate,

wherein the photoresist layer comprises a photoresist composition comprising a polymer and a photoacid generator,

wherein the polymer comprises:

a monomer unit having a crosslinking group bonded to a pendant sensitizer,

wherein the pendant sensitizer is selected from the group consisting of a substituted or unsubstituted aromatic group and a substituted or unsubstituted heterocyclic group, and

the crosslinking group is selected from the group consisting of one or more of a C2-C30 aromatic group having a functional group selected from the group consisting of an azo group, an alkyl halide group and a peroxide group;

a monomer unit having a pendant acid labile group; and

a monomer unit having a pendant organic group, wherein the pendant organic group is a C1-C30 group substituted with one or more of —I, —Br, —Cl, —NH 2 , —SH, —N 3 , —S(═O)—, an alkene group, an alkyne group, an imine group, an ether group, an aldehyde group, an amide group, a sulfone group, or a cyanide group;

releasing an acid from the photoacid generator and generating a secondary electron and a radical from the sensitizer in a first portion of the photoresist layer;

deprotecting the acid labile group by the acid released from the photoacid generator;

activating the crosslinking group by the radical causing the polymer to crosslink; and

removing a second portion of the photoresist layer where the acid was not released and the secondary electron and radical were not generated,

wherein the releasing an acid from the photoacid generator and generating a secondary electron and a radical from the sensitizer in a first portion of the photoresist layer comprises exposing the first portion of the photoresist layer to actinic radiation.

9 . The method according to claim 8 , wherein the actinic radiation is extreme ultraviolet radiation.

10 . The method according to claim 8 , further comprising:

forming an organic bottom layer over the substrate; and

forming an inorganic middle layer over the organic bottom layer,

wherein the photoresist layer is formed over the middle layer.

11 . The method according to claim 8 , further comprising heating the photoresist layer after the releasing an acid from the photoacid generator and generating a secondary electron and a radical from the sensitizer in a first portion of the photoresist layer.

12 . The method according to claim 1 , wherein the pendant organic group is substituted with —I.

13 . The method according to claim 8 , wherein the pendant organic group is substituted with —I.

14 . A method of manufacturing a semiconductor device, comprising:

forming an organic bottom layer over a substrate;

forming a middle layer over the organic bottom layer;

forming a photoresist layer over the middle layer,

wherein the photoresist layer comprises a photoresist composition comprising a polymer,

wherein the polymer comprises:

a monomer unit having a pendant sensitizer selected from the group consisting of phenyl group, a naphthalenyl group, a phenanthrenyl group, an anthracenyl group, and a phenalenyl group, and a crosslinking group bonded to the sensitizer, wherein the crosslinking group is one or more of a C2-C30 aromatic group having a functional group selected from the group consisting of an azo group, an alkyl halide group, and a peroxide group;

a monomer unit having a pendant acid labile group; and

a monomer unit having a pendant organic group, wherein the pendant organic group is a C1-C30 group substituted with one or more of —I, —Br, —Cl, —NH 2 , —SH, —N 3 , —S(═O)—, an alkene group, an alkyne group, an imine group, an ether group, an aldehyde group, an amide group, a sulfone group, or a cyanide group;

selectively exposing the photoresist layer with the polymer comprising the monomer unit having the pendant sensitizer and crosslinking group and the monomer unit having the pendant acid labile group to actinic radiation, thereby causing the polymer to crosslink through the crosslinking group; and

developing the selectively exposed photoresist layer.

15 . The method according to claim 14 , wherein the actinic radiation is extreme ultraviolet radiation.

16 . The method according to claim 14 , further comprising heating the selectively exposed photoresist layer before the developing.

17 . The method according to claim 14 , further comprising removing a portion of the substrate exposed by the developing.

18 . The method according to claim 14 , wherein the photoresist composition further comprises a photoacid generator.

19 . The method according to claim 18 , wherein the photoacid generator releases an acid and the pendant sensitizer generates secondary electrons upon exposure to actinic radiation.

20 . The method according to claim 14 , wherein the polymer has a weight average molecular weight of 1000 to 200,000.

Assignments (1)

Continuity (2)

References Cited (25)