Photoresist composition and method of manufacturing a semiconductor device

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, —NH2, —SH, —N3, —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.

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, —NH2, —SH, —N3, —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.