US 6,309,796 B1Granted

High molecular weight silicone compounds resist compositions, and patterning method

AssigneeShin-Etsu Chemical Co., Ltd.

InventorsMutsuo Nakashima, Ichiro Kaneko, Toshinobu Ishihara, Junji Tsuchiya, Jun Hatakeyama, Shigehiro Nagura

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Abstract

The invention provides a high molecular weight silicone compound comprising recurring units of formula (1) and having a weight average molecular weight of 1,000-50,000. Some or all of the hydrogen atoms of carboxyl groups or carboxyl and hydroxyl groups in the silicone compound may be replaced by acid labile groups. Z is di- to hexavalent, non-aromatic, monocyclic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group; Z′ is a di- to hexavalent, normal or branched hydrocarbon group or non-aromatic, monocyclic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group; x, y and z are integers of 1-5 corresponding to the valence of Z and Z′; R1 is —OCHR—R′ —OH or —NHCHR—R′ —OH; R2 is alkyl or alkenyl or a monovalent, non-aromatic, polycyclic hydrocarbon or bridged cyclic hydrocarbon group; p1, p2, p3 and p4 are 0 or positive numbers. A resist composition comprising the high molecular weight silicone compound as a base resin is sensitive to actinic radiation and has a high sensitivity and resolution so that it is suitable for microfabrication with electron beams or deep UV. Since the composition has low absorption at the exposure wavelength of an ArF or KrF excimer laser, a finely defined pattern having walls perpendicular to the substrate can be readily formed.

Claims23

Dependent claims

A high molecular weight silicone compound comprising recurring units represented by formula (1), said silicone compound having a weight average molcular weight of 1,000 to 50,000,

wherein Z is a divalent to hexavalent, non-aromatic, monocyclic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 5 to 12 carbon atoms;
Z′ is a divalent to hexavalent, normal or branched hydrocarbon group having 1 to 20 carbon atoms or non-aromatic, monocyclic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 3 to 20 carbon atoms;
Z or Z′ may have a nitrogen, oxygen or sulfur atom interposed in a carbon-to-carbon bond, the hydrogen atom on a carbon atom may be replaced by a halogen, alkoxy, nitro, cyano or acetyl group, and a methylene group in the carbon skeleton may be replaced by a carbonyl group;
x, y and z are independently integers of 1 to 5 corresponding to the valence of Z and Z′;
R1 is a group represented by formula (2a) or (2b);
R2 is a normal, branched or cyclic, substituted or unsubstituted, alkyl or alkenyl group having 1 to 8 carbon atoms or a monovalent, non-aromatic, polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 5 to 12 carbon atoms;
wherein R is hydrogen, hydroxyl group or a normal, branched or cyclic alkyl group having 1 to 20 carbon atoms, R′ is a normal, branched or cyclic alkenylene group having 1 to 20 carbon atoms, an alkyl R or an alkylene R′ group may have an oxygen atom interposed in a carbon-to-carbon bond, some of the hydrogen atoms attached to carbon atoms may be replaced by hydroxyl groups;
or R and R′, taken together, may form a ring, and each of R and R′ is a normal or branched alkylene group of 1 to 8 carbon atoms when they form a ring;
and
p1 is a positive number and p2, p3 and p4 are 0 or positive numbers and satisfy:
p1+p2+p3+p4=1,
0<p1/(p1+p2+p3+p4)≦0.9,
0≦p2/(p1+p2+p3+p4)≦0.8,
0≦p3/(p1+p2+p3+p4)≦0.7,
0≦p4/(p1+p2+p3+p4)≦0.9.

12 more elements

A resist composition comprising

(A) an organic solvent,
(B) a base resin in the form of a high molecular weight silicone compound comprising recurring units represented by formula (1), some or all of the hydrogen atoms of carboxyl groups or carboxyl groups and hydroxyl groups in said silicone compound being replaced by at least one acid labile group, said silicone compound having a weight average molecular weight of 1,000 to 50,000,
wherein Z is a divalent to hexavalent, non-aromatic, monocylic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 5 to 12 carbon atoms;
Z′ is a divalent to hexavalent, normal or branched hydrocarbon group having 1 to 20 carbon atoms or non-aromatic, monocylic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 3 to 20 carbon atoms;
Z or Z′ may have a nitrogen, oxygen or sulfur atom interposed in a carbon-to-carbon bond, the hydrogen atom on a carbon atom may be replaced by a halogen, alkoxy, nitro, cyano or acetyl group, and a methylene group in the carbon skeleton may be replaced by a carbonyl group;
x, y and z are independently integers of 1 to 5 corresponding to the valence of Z and Z′;
R1 is a group represented by formula (2a) or (b);
R2 is a normal, branched or cyclic, substituted or unsubstituted, alkyl or alkenyl group having 1 to 8 carbon atoms or a monovalent, non-aromatic, polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 5 to 12 carbon atoms;
wherein R is hydrogen, hydroxyl group or a normal, branched or cyclic alkyl group having 1 to 20 carbon atoms, R′ is a normal, branced or cyclic alkylene group having 1 to 20 carbon atoms an alkyl R or an alkylene R′ group may have an oxygen atom interposed in a carbon-to-carbon bond, some of the hydrogen atoms attached to carbon atoms may be replaced by hydroxyl groups;
or R and R′, taken together, may form a ring, and each of R and R′ is a normal or branched alkylene group of 1 to 8 carbon atoms when they form a ring;
and
p1 is a positive number, and p2, p3 and p4 are 0 or positive numbers and satisfy:
p1+p2+p3+p4=1,
0<p1/(p1+p2+p3+p4)≦0.9,
0≦p2/(p1+p2+p3+p4)≦0.8,
0≦p3/(p1+p2+p3+p4)≦0.7,
0≦p4/(p1+p2+p3+p4)≦0.9,
and
(C) a photoacid generator.

16 more elements

A resist composition comprising

(A) an organic solvent,
(B) a base resin in the form of a high molecular weight silicone compound comprising recurring units represented by formula (1), or a high molecular weight silicone compound in which some of the hydrogen atoms of carboxyl groups or carboxyl groups and hydroxyl groups in the silicone compound of formula (1) are replaced by at least one acid labile group, said silicone compound having a weight average molecular weight of 1,000 to 50,000,
wherein Z is a divalent to hexavalent, non-aromatic, monocylic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 5 to 12 carbon atoms;
Z′ is a divalent to hexavalent, normal or branched hydrocarbon group having 1 to 20 carbon atoms or non-aromatic, monocyclic or polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 3 to 20 carbon atoms;
Z or Z′ may have a nitrogen, oxygen or sulfur atom interposed in a carbon-to-carbon bond, the hydrogen atom on a carbon atom may be replaced by a halogen, alkoxy, nitro, cyano or acetyl group, and a methylene group in the carbon skeleton may be replaced by a carbonyl group;
x, y and z are independently integers of 1 to 5 corresponding to the valence of Z and Z′;
R1 is a group represented by formula (2a) or (2b);
R2 is a normal, branched or cyclic, substituted or unsubstituted, alkyl or alkenyl group having 1 to 8 carbon atoms or a monovalent, non-aromatic, polycyclic hydrocarbon or bridged cyclic hydrocarbon group having 5 to 12 carbon atoms;
wherein R is hydrogen, hydroxyl group or a normal, branched or cyclic alkyl group having 1 to 20 carbon atoms, R′ is a normal, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyl R or an alkylene R′ group may have an oxygen atom interposed in a carbon-to-carbon bond, some of the hydrogen atoms attached to carbon atoms may be replaced by hydroxyl groups;
or R and R′, taken together, may form a ring, and each of R and R′ is a normal or branched alkylene group of 1 to 8 carbon atoms when they form a ring;
and
p1 is a positive number, and p2, p3 and p4 are 0 or positive numbers and satisfy:
p1+p2+p3+p4=1,
0<p1/(p1+p2+p3+p4)≦0.9,
0≦p2/(p1+p2+p3+p4)≦0.8,
0≦p3/(p1+p2+p3+p4)≦0.7,
0≦p4/(p1+p2+p3+p4)≦0.9,
(C) a photoacid generator, and
(H) a compound crosslinkable by the action of acid.

16 more elements

Dependencies are inferred from the claim text.