Radiation-sensitive resin composition, method for forming resist pattern, polymer and polymerizable compound

Patent metadata

Field	Value
Publication number	US-10048586-B2
Application number	US-201615056264-A
Country	US
Kind code	B2
Filing date	Feb 29, 2016
Priority date	Sep 18, 2009
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

A radiation-sensitive resin composition includes a first polymer including an acid-labile group, an acid generator to generate an acid upon exposure to radiation, and a second polymer including a fluorine atom and a functional group shown by a general formula (x). The second polymer has a fluorine atom content higher than a fluorine atom content of the first polymer. R 1 represents an alkali-labile group. A represents an oxygen atom, —NR′—, —CO—O— # or —SO 2 —O— ## , wherein the oxygen atom represented by A is not an oxygen atom bonded directly to an aromatic ring, a carbonyl group, or a sulfoxyl group, R′ represents a hydrogen atom or an alkali-labile group, and “#” and “##” each indicate a bonding hand bonded to R 1 .

-A-R 1   (x).

First claim

The invention claimed is:

1. A composition comprising:
a first polymer comprising an acid-labile group; and
a second polymer comprising a first repeating unit represented by formula (c0) and a second repeating unit represented by formula (c4), wherein the second polymer comprises a fluorine atom and has a fluorine atom content higher than a fluorine atom content of the first polymer:

wherein:
n is an integer from 1 to 3;
R 1 represents an alkali-labile group, wherein each R 1 is a same as or different from each other when n is 2 or 3;
A represents an oxygen atom, —NR′—, —CO—O—* or —SO 2 —O—*, wherein R′ represents a hydrogen atom or alkali-liable group, the oxygen atom represented by A is not an oxygen atom bonded directly to an aromatic ring, a carbonyl group, or a sulfoxyl group, and * indicates a bonding hand bonded to R 1 , wherein each A is a same as or different from each other when n is 2 or 3;
R 2 represents a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, wherein each R 2 is a same as or different from each other when n is 2 or 3;
X 0 represents a single bond or a divalent chain hydrocarbon group having 1 to 20 carbon atoms in which some or all of hydrogen atoms are substituted with a fluorine atom, wherein each X 0 is a same as or different from each other when n is 2 or 3;
R 3 represents an (n+1)-valent hydrocarbon group having 1 to 20 carbon atoms, wherein, optionally, an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O—, or —CO—NH— is bonded to an end of R 3 which is bonded to R 2 ;
E represents an oxygen atom, —CO—O—*, or —CO—NH—*, wherein * indicates a bonding hand bonded to R 3 ; and
R represents a hydrogen atom, a methyl group, or a trifluoromethyl group,

wherein:
m is an integer from 1 to 3;
R is as defined in formula (c0);
A is as defined in formula (c0), and * indicates a bonding hand bonded to R 7 , wherein each A is either a same as or different from each other when m is 2 or 3;
R 7 represents a hydrogen atom;
R 6 represents a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, wherein each R 6 is either a same as or different from each other when m is 2 or 3;
R 5 represents an (m+1)-valent hydrocarbon group having 1 to 20 carbon atoms, wherein, optionally, an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O—, or —CO—NH— is bonded to an end of R 5 which is bonded to R 6 ; and
X 2 represents a single bond, a difluoromethylene group, or a linear or branched perfluoroalkylene group having 2 to 20 carbon atoms, wherein each X 2 is either a same as or different from each other when m is 2 or 3.

2. The composition according to claim 1 , wherein the first repeating unit is represented by formula (c1):

wherein each of E, n, R, R 1 , R 2 , R 3 , and A is as defined in formula (c0), and X 1 represents a single bond, a difluoromethylene group, or a linear or branched perfluoroalkylene group having 2 to 20 carbon atoms.

3. The composition according to claim 2 , wherein the first repeating unit is represented by formula (c2):

wherein each of n, R, R 1 , R 2 , R 3 , X 1 , and A is as defined in formula (c1).

4. The composition according to claim 2 , wherein the first repeating unit is represented by formula (c2-1):

wherein each of n, R, R 2 , R 3 , and X 1 is as defined in formula (c1), and R 8 represents a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

5. The composition according to claim 2 , wherein the first repeating unit is represented by formula (c2-2):

wherein
each of R, R 2 , and X 1 is as defined in formula (c1),
R 31 represents a divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent cyclic hydrocarbon group having 4 to 20 carbon atoms, wherein, optionally, an oxygen atom, a sulfur atom, an imino group, a carbonyl group, —CO—O—, or —CO—NH— is bonded to an end of R 31 which is bonded to R 2 , and
R 9 represents a group shown by formula (1), formula (2) or formula (3):

wherein R 10 represents a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, or an acyloxy group having 1 to 10 carbon atoms, wherein each R 10 is either a same as or different from each other when a plurality of R 10 are present,
m 1 is an integer from 0 to 5,
m 2 is an integer from 0 to 4, and
each of R 11 and R 12 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or R 11 and R 12 bond to each other to form an alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom bonded to R 11 and R 12 .

6. The composition according to claim 2 , wherein the second polymer further comprises a repeating unit shown by formula (c3),

wherein
R is as defined in formula (c1),
G represents a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO 2 —O—NH—, —CO—NH—, or —O—CO—NH—, and
R 4 represents a fluorine-substituted chain hydrocarbon group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, or a fluorine-substituted cyclic hydrocarbon group having 4 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom.

7. The composition according to claim 1 , wherein an amount of the second polymer is 0.1 to 20 parts by mass based on 100 parts by mass of the first polymer.

8. The composition according to claim 1 , further comprising an acid generator.

9. A method comprising:
applying a composition directly or indirectly on a substrate to form a resist film;
exposing the resist film by applying radiation to the resist film via a mask pattern; and developing the exposed resist film to form a resist pattern,
wherein the composition comprises:
a first polymer comprising an acid-labile group; and
a second polymer comprising a first repeating unit represented by formula (c0) and a second repeating unit represented by formula (c4), wherein the second polymer comprises a fluorine atom and has a fluorine atom content higher than a fluorine atom content of the first polymer:

wherein:
n is an integer from 1 to 3;
R 1 represents an alkali-labile group, wherein each R 1 is a same as or different from each other when n is 2 or 3;
A represents

Assignees

• Jsr Corp

Inventors

• Asano Yuusuke
• Sato Mitsuo
• Nakashima Hiromitsu
• Kasahara Kazuki
• Oizumi Yoshifumi
• Hori Masafumi
• Kawakami Takanori
• Matsuda Yasuhiko
• Nakahara Kazuo

Classifications

• G03F7/2041

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

• C08F20/22 Primary

  Esters containing halogen · CPC title

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title

• C08F20/26

  Esters containing oxygen in addition to the carboxy oxygen · CPC title

• G03F7/0046

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