Fluorine-containing polymer, purification method, and radiation-sensitive resin composition

Patent metadata

Field	Value
Publication number	US-10082733-B2
Application number	US-201615299871-A
Country	US
Kind code	B2
Filing date	Oct 21, 2016
Priority date	Mar 31, 2006
Publication date	Sep 25, 2018
Grant date	Sep 25, 2018

Abstract

An object of the present invention is to provide a novel fluorine-containing polymer, a radiation-sensitive resin composition for liquid immersion lithography which contains the fluorine-containing polymer, which leads to a pattern having an excellent shape and excellent depth of focus, wherein the amount of an eluted component in a liquid for liquid immersion lithography such as water that comes in contact with the resist during exposure in liquid immersion lithography is little, and which provides a larger receding contact angle between the resist film and the liquid for liquid immersion lithography such as water, and a method for purifying the fluorine-containing polymer. The present resin composition comprises a novel fluorine-containing polymer (A) containing repeating units represented by the general formulae (1) and (2) and having Mw of 1,000-50,000, a resin (B) having an acid-unstable group, a radiation-sensitive acid generator (C), a nitrogen-containing compound (D) and a solvent (E).

First claim

The invention claimed is:

1. A radiation-sensitive resin composition comprising:
a fluorine-containing polymer comprising a first repeating unit represented by formula (1) and a repeating unit represented by formula (2);
at least one acid-unstable resin having an acid-unstable group, comprising at least two second repeating units each represented by formula (2) and at least one third repeating unit represented by formula (5);
a radiation-sensitive acid generator;
a nitrogen-containing compound; and
a solvent,

wherein:
R 1 represents a hydrogen atom, a methyl group or a trifluoromethyl group;
A represents a connecting group; and
R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, the linear or branched alkyl group and the monovalent alicyclic hydrocarbon group represented by R 2 comprising at least one fluorine atom, or a derivative thereof,

wherein:
R 3 represents a hydrogen atom, a methyl group or a trifluoromethyl group; and
each R 4 individually represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and optionally two of R 4 s taken together represent a divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atom to which the two of R 4 s bond,

wherein:
R 9 represents hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group or a hydroxymethyl group; and R 10 represents a bridged cyclic hydrocarbon group,
wherein the at least two second repeating units comprises a repeating units comprising a monocyclic structure, and a repeating units comprising a polycyclic structure, and
wherein a content of the fluorine-containing polymer in the radiation-sensitive resin composition is from 0.5% to 35% by weight based on 100% by weight of the radiation-sensitive resin composition.

2. The radiation-sensitive resin composition according to claim 1 , wherein the at least one acid-unstable resin comprises a repeating unit comprising a lactone structure.

3. The radiation-sensitive resin composition according to claim 1 , wherein the radiation-sensitive acid generator comprises an onium ion, the onium ion comprising:
a cation; and
an anion represented by R 17 C n F 2n SO 3 − , an anion represented by R 17 SO 3 − , or both thereof, wherein R 17 represents a fluorine atom, a cycloalkyl group, or a bridge alicyclic hydrocarbon group, the cycloalkyl group and the bridge alicyclic hydrocarbon group having no more than 12 carbon atoms and optionally being substituted, and n is an integer of 1 to 10.

4. The radiation-sensitive resin composition according to claim 3 , wherein the anion is represented by R 17 C n F 2n SO 3 − .

5. The radiation-sensitive resin composition according to claim 3 , wherein R 17 is the bridge alicyclic hydrocarbon group.

6. The radiation-sensitive resin composition according to claim 3 , wherein the anion is represented by R 17 C n F 2n SO 3 − , and R 17 is the bridge alicyclic hydrocarbon group.

7. The radiation-sensitive resin composition according to claim 3 , wherein the cation is represented by formula (7-1),

wherein
R 14 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms;
R 15 represents a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxyl group;
R 16 individually represents a linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, or two R 16 s taken together represent a substituted or unsubstituted divalent group which comprises 2 to 10 carbon atoms;
k is an integer of 0 to 2; and
r is an integer of 0 to 10.

8. The radiation-sensitive resin composition according to claim 7 , wherein R 16 individually represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

9. The radiation-sensitive resin composition according to claim 1 , wherein an amount of the radiation-sensitive acid generator is from 0.5 to 10 parts by weight based on 100 parts by weight of a total of the fluorine-containing polymer and the resin.

10. The radiation-sensitive resin composition according to claim 1 , wherein the fluorine-containing polymer has a weight average molecular weight determined by gel permeation chromatography in a range from 1,000 to 50,000.

11. The radiation-sensitive resin composition according to claim 1 , wherein in the formula (1), A represents a single bond, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, an amide group, a sulfonylamide group, or a urethane group.

12. The radiation-sensitive resin composition according to claim 1 , wherein the nitrogen-containing compound comprises at least one of an amine compound, an amide group-containing compound, a urea compound, or a nitrogen-containing heterocyclic compound.

13. The radiation-sensitive resin composition according to claim 1 , wherein a molar ratio of the repeating unit comprising a monocyclic structure to the repeating unit comprising a polycyclic structure is from 12/88 to 49/51.

14. The radiation-sensitive resin composition according to claim 1 ,
wherein in formula (1), A is —COO—, R 1 represents a methyl group, and R 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms which comprises at least one fluorine atom, and
wherein in the repeating unit represented by formula (2) included in the fluorine-containing polymer, R 3 represents a methyl group, and each R 4 individually represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms,
wherein at least one R 4 represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or
wherein two of R 4 s taken together represent a divalent alicyclic hydrocarbon group together with the carbon atom to which the two of R 4 s bond.

Assignees

• Jsr Corp

Inventors

• Nakagawa Hiroki
• Nakashima Hiromitsu
• Wakamatsu Gouji
• Gotou Kentarou
• Nishimura Yukio
• Shioya Takeo

Classifications

• G03F7/2006

  using coherent light; using polarised light · CPC title

• G03F7/162

  Coating on a rotating support, e.g. using a whirler or a spinner · CPC title

• G03F7/2041

  in the presence of a fluid, e.g. immersion; using fluid cooling means · CPC title

• G03F7/168

  Finishing the coated layer, e.g. drying, baking, soaking · CPC title

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title