Radiation-sensitive resin composition, method for forming resist pattern, polymer and polymerizable compound
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 .
1. A radiation-sensitive resin composition comprising:
a first polymer comprising an acid-labile group;
an acid generator to generate an acid upon exposure to radiation; and
a second polymer comprising a fluorine atom and a repeating unit shown by formula (c2-1),
the second polymer having a fluorine atom content higher than a fluorine atom content of the first polymer, and being in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the first polymer,
wherein
n is an integer from 1 to 3,
X 1 represents a single bond, a difluoromethylene group, or a linear or branched perfluoroalkylene group having 2 to 20 carbon atoms,
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,
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 ,
R represents a hydrogen atom, a methyl group, or a trifluoromethyl group,
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, wherein each R 8 is a same as or different from each other when n is 2 or 3, and
R 8 and the CO group bonded to R 8 taken together are an alkali-labile group, wherein the alkali-labile group is a group that is separable to form a polar functional group in a presence of an alkali.
2. The radiation-sensitive resin composition according to claim 1 , wherein the second polymer further comprises a repeating unit shown by formula (c3) or a repeating unit shown by formula (c4),
wherein
R is a same as defined for the formula (c2-1),
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, and
wherein
m is an integer from 1 to 3,
R is a same as defined for the formula (c2-1),
A represents an oxygen atom or —CO—O— # , wherein the oxygen atom represented by A is not bonded directly to an aromatic ring, a carbonyl group which is not included in R 7 , or a sulfoxyl group, “#” indicates a bonding hand bonded to R 7 , and each A is either a same as or different from each other when m is 2 or 3,
R 7 represents a hydrogen atom or an acid-labile group, wherein each R 7 is either a same as or different from each other when m is 2 or 3,
R 6 is a same as defined for R 2 in the formula (c2-1), wherein each R 6 is either a same as or different from each other when m is 2 or 3,
R 5 is a same as defined for R 3 in the formula (c2-1), and
X 2 is a same as defined for X 1 in the formula (c2-1), wherein each X 2 is either a same as or different from each other when m is 2 or 3.
3. A method for forming a resist pattern comprising:
applying the radiation-sensitive resin composition according to claim 1 on a substrate to provide a resist film on the substrate;
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.
4. The method according to claim 3 , wherein the resin film is exposed via an immersion liquid provided over the resist film.
5. The radiation-sensitive resin composition according to claim 1 , wherein the second polymer has the fluorine content higher than the fluorine content of the first polymer by 1 mass % or more.
6. The radiation-sensitive resin composition according to claim 1 , wherein the second polymer has the fluorine content higher than the fluorine content of the first polymer by 5 mass % or more.
7. A radiation-sensitive resin composition comprising:
a first polymer comprising an acid-labile group;
an acid generator to generate an acid upon exposure to radiation; and
a second polymer comprising a fluorine atom and a repeating unit shown by formula (c2-2),
the second polymer having a fluorine atom content higher than a fluorine atom content of the first polymer, and being in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the first polymer,
wherein
X l represents a single bond, a difluoromethylene group, or a linear or branched perfluoroalkylene group having 2 to 20 carbon atoms,
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,
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 ,
R represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and
R 9 is an alkali-labile group and represents a group shown by formula (1), formula (2) or formula (3), wherein the alkali-labile group is a group that is separable to form a polar functional group in a presence of an alkali,
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″ and R 12 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or R″ 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 .
8. The radiation-sensitive resin composition according to claim 7 , wherein the second polymer further comprises a repeating unit shown by formula (c3) or a repeating unit shown by formula (c4),
wherein
R is a same as defined for the formula (c2-2),
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, and
wherein
m is an integer from 1 to 3,
R is a same as defined for the formula (c2-2),
A represents an oxygen atom or —CO—O— # , wherein the oxygen atom represented by A is not bonded directly to an aromatic ring, a carbonyl group which is not included in R 7 , or a sulfoxyl group, “#” indicates a bonding hand bonded to R 7 , and each A is either a same as or different from each other when m is 2 or 3,
R 7 represents a hydrogen atom or an acid-labile group, wherein each R 7 is either a same as or different from each other when m is 2 or 3,
R 6 is a same as defined for R 2 in the formula (c2-2), wherein each R 6 is either a same as or different from each other when m is 2 or 3,
R 5 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 , and
X 2 is a same as defined for X 1 in the formula (c2-2), wherein each X 2 is either a same as or different from each other when m is 2 or 3.
9. A method for forming a resist pattern comprising:
applying the radiation-sensitive resin composition according to claim 7 on a substrate to provide a resist film on the substrate;
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.
10. The method according to claim 9 , wherein the resin film is exposed via an immersion liquid provided over the resist film.
11. The radiation-sensitive resin composition according to claim 7 , wherein the second polymer has the fluorine content higher than the fluorine content of the first polymer by 1 mass % or more.
12. The radiation-sensitive resin composition according to claim 7 , wherein the second polymer has the fluorine content higher than the fluorine content of the first polymer by 5 mass % or more.