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

Patent metadata

Field	Value
Publication number	US-10620534-B2
Application number	US-201816104182-A
Country	US
Kind code	B2
Filing date	Aug 17, 2018
Priority date	Mar 31, 2006
Publication date	Apr 14, 2020
Grant date	Apr 14, 2020

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 consisting of: at least one first repeating unit represented by formula (1); and at least one second repeating unit represented by formula (2);
an acid-unstable resin having an acid-unstable group, comprising a third repeating unit represented by formula (2);
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 single bond, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, an amide group, a sulfonylamide group, or a urethane group; and
R 2 represents a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms or a monovalent partially or fully fluorinated alicyclic hydrocarbon group having 4 to 20 carbon atoms,

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 an amount of the third repeating unit in the acid-unstable resin is from 53.8 to 69.6 mol % with respect to an amount of all repeating units in the acid-unstable resin.

2. The radiation-sensitive resin composition according to claim 1 , wherein the acid-unstable resin further 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 acid-unstable resin.

10. The radiation-sensitive resin composition according to claim 1 , wherein a content of the fluorine-containing polymer in the radiation-sensitive resin composition is 0.1% or more by weight based on 100% by weight of the radiation-sensitive resin composition.

11. The radiation-sensitive resin composition according to claim 1 , 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.

12. 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.

13. 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.

14. The radiation-sensitive resin composition according to claim 1 , wherein an amount of the radiation-sensitive acid generator is from 7 to 9.5 parts by weight based on 100 parts by weight of the acid-unstable resin.

Assignees

• Jsr Corp

Inventors

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

Classifications

• G03F7/0046 Primary

  with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence) · CPC title

• C08F220/24

  containing perhaloalkyl radicals · CPC title

• G03F7/0397

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

• G03F7/039

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title

• G03F7/40

  Treatment after imagewise removal, e.g. baking · CPC title