Polymer, resist composition containing polymer, and method for manufacturing device using same

1. A polymer, comprising:

a unit A; and

a unit B,

wherein: the unit A has an onium salt structure and generates a first radical by irradiation with a particle beam or an electromagnetic wave;

the unit B has a radical generating structure containing at least one multiple bond selected from the group consisting of: a multiple bond between a carbon atom and a carbon atom; and a multiple bond between a carbon atom and a heteroatom;

the unit B generates a second radical by irradiation with a particle beam or an electromagnetic wave;

the multiple bond in the radical generating structure is not a multiple bond contained in a benzenoid aromatic;

the polymer does not comprise a unit having an acid dissociable group whose solubility in a water-soluble developer is enhanced by an acid; and

the unit B is represented by at least one of following general formulas (III) to (V),

wherein, in the general formulas (III) to (V),

R 1 is any one selected from the group consisting of:

a hydrogen atom;

a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and

a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms, and

where at least one hydrogen atom in the alkyl group and the alkenyl group in R 1 may be substituted with a fluorine atom;

L is any one selected from the group consisting of: a carbonyloxy group, a phenylenediyl group, a naphthalenediyl group, a phenylenediyloxy group, a naphthalenediyloxy group, a phenylenediylcarbonyloxy group, a naphthalenediylcarbonyloxy group, a phenylenediyloxycarbonyl group and a naphthalenediyloxycarbonyl group;

Sp is any one selected from the group consisting of:

a direct bond;

a linear, branched or cyclic alkylene group which may have a substituent, the alkylene group having 1 to 6 carbon atoms; and

a linear, branched or cyclic alkenylene group which may have a substituent, the alkenylene group having 1 to 6 carbon atoms, and

where at least one methylene group in the Sp may be substituted with a divalent heteroatom-containing group;

each R 3 is independently any one selected from the group consisting of:

a hydrogen atom;

a hydroxy group;

—R a , where R a is a linear, branched or cyclic alkyl group which may have a substituent, the alkyl group having 1 to 12 carbon atoms, and at least one methylene group in R a may be substituted with a divalent heteroatom-containing group;

—OR a ;

a group where at least one carbon-carbon single bond in R a is substituted with a carbon-carbon double bond; and

—R b , where R b is an aryl group which may have a substituent, the aryl group having 6 to 14 carbon atoms, or R b is a heteroaryl group which may have a substituent, the heteroaryl group having 4 to 12 carbon atoms,

where two of R 3 may form a ring structure with each other through a direct single bond, or any one selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group;

R 4 is any one selected from the group consisting of: —R a ; —R b ; —OR a ; —SR a ; —OR b ; —SR b ; —OC(═O)R a ; —OC(═O)R b ; —C(═O)OR a ; —C(═O)OR b ; —OC(═O)OR a ; —OC(═O)OR b ; —NHC(═O)R a ; —NR a C(═O)R a ; —NHC(═O)R b ; —NR b C(═O)R b ; —NR a C(═O)R b ; —NR b C(═O)R a ; —N(R a ) 2 ; —N(R b ) 2 ; —N(R a )(R b ); —SO 3 R a ; —SO 3 R b ; —SO 2 R a ; —SO 2 R b ; a group where at least one carbon-carbon single bond in R a is substituted with a carbon-carbon double bond; and a nitro group,

n 1 is an integer of 1 to 3, m 1 is an integer of 0 to 4 when n 1 is 1, m 1 is an integer of 0 to 6 when n 1 is 2, and m 1 is 0 to 8 when n 1 is 3; and

R 5 is any one selected from the group consisting of:

a linear, branched or cyclic alkylene group which may have a substituent, the alkylene group having 1 to 12 carbon atoms;

a linear, branched or cyclic alkyleneoxy group which may have a substituent, the alkyleneoxy group having 1 to 12 carbon atoms;

a linear, branched or cyclic alkenylene group which may have a substituent, the alkenylene group having 1 to 12 carbon atoms;

a linear, branched or cyclic alkenyleneoxy group which may have a substituent, the alkenyleneoxy group having 1 to 12 carbon atoms;

an arylene group which may have a substituent, the arylene group having 6 to 14 carbon atoms; and

a heteroarylene group which may have a substituent, the heteroarylene group having 4 to 12 carbon atoms, and

where at least one methylene group in R 5 may be substituted with a divalent heteroatom-containing group.

2. The polymer of claim 1 , wherein the unit A is represented by a following general formula (I),

wherein, in the general formula (I), M + is a sulfonium ion or an iodonium ion,

X − is a monovalent anion,

L is any one selected from the group consisting of: a carbonyloxy group, a phenylenediyl group, a naphthalenediyl group, a phenylenediyloxy group, a naphthalenediyloxy group, a phenylenediylcarbonyloxy group, a naphthalenediylcarbonyloxy group, a phenylenediyloxycarbonyl group and a naphthalenediyloxycarbonyl group,

Sp is any one selected from the group consisting of:

a direct bond;

a linear, branched or cyclic alkylene group which may have a substituent, the alkylene group having 1 to 6 carbon atoms; and

a linear, branched or cyclic alkenylene group which may have a substituent, the alkenylene group having 1 to 6 carbon atoms, and

where at least one methylene group in the Sp may be substituted with a divalent heteroatom-containing group, and

R 1 is any one selected from the group consisting of:

a hydrogen atom;

a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and

a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms, and

where at least one hydrogen atom in the alkyl group and the alkenyl group in R 1 may be substituted with a fluorine atom.

3. The polymer of claim 2 , wherein the unit A is represented by a following formula (II),

wherein, in the general formula (II), R 1 , L, Sp and X − are the same as those in the general formula (I),

R 2a is any one selected from the group consisting of:

a linear, branched or cyclic alkylene group which may have a substituent, the alkylene group having 1 to 6 carbon atoms;

a linear, branched or cyclic alkenylene group which may have a substituent, the alkenylene group having 1 to 6 carbon atoms;

an arylene group which may have a substituent, the arylene group having 6 to 14 carbon atoms;

a heteroarylene group which may have a substituent, the heteroarylene group having 4 to 12 carbon atoms; and

a direct bond, and

where at least one methylene group in R 2a may be substituted with a divalent heteroatom-containing group, and

each of R 2b is independently any one selected from the group consisting of:

a linear, branched or cyclic alkyl group which may have a substituent, the alkyl group having 1 to 6 carbon atoms;

a linear, branched or cyclic alkenyl group which may have a substituent, the alkenyl group having 1 to 6 carbon atoms;

an aryl group which may have a substituent, the aryl group having 6 to 14 carbon atoms; and

a heteroaryl group which may have a substituent, the heteroaryl group having 4 to 12 carbon atoms, and

where at least one methylene group in R 2b may be substituted with a divalent heteroatom-containing group, and two selected from R 2a and two of R 2b may form a ring structure with each other through a direct single bond, or any one selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group.

4. The polymer of claim 2 , wherein X − is any one selected from the group consisting of an anion A and an anion B;

where the anion A is any one selected from the group consisting of an alkyl sulfonate anion, an aryl sulfonate anion, an alkyl carboxylate anion, an aryl carboxylate anion, a tetrafluoroborate anion, a hexafluorophosphonate anion, a dialkylsulfonylimide anion, a trialkylsulfonatemethide anion, a tetrakisphenylborate anion, hexafluoroantimonate and a monovalent metal oxonium anion;

the anion B is a hydrogen acid anion containing the anion A; and

at least one hydrogen atom of the alkyl group and the aryl group in X − may be substituted with a fluorine atom.

5. The polymer of claim 1 , wherein the unit B is represented by at least one of the following general formulas (III) and (V).

6. The polymer of claim 1 , further comprising a unit C,

wherein the unit C includes a compound represented by following general formulas (VI) to (VIII) bonding to an Sp group of formula (1),

wherein, in the general formulas (VI) to (VIII),

each of R 6 , R 7 and R 8 is independently any one selected from the group consisting of:

a hydrogen atom; an electron donating group; and an electron withdrawing group, and

where at least one of R 6 and R 7 is the electron donating group, and at least one of R 8 is the electron donating group,

R 9 is any one selected from the group consisting of: a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent,

where at least one methylene group in R 9 may be substituted with a divalent heteroatom-containing group,

each of R 10 is independently any one selected from the group consisting of: a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent,

where two of R 10 may bond each other to form a ring structure,

E is any one selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom and a methylene group,

m 2 is an integer of 0 or 1,

n 4 and n 5 are each an integer of 0 to 2, where n 4 +n 5 is 2,

n 2 is an integer of 0 to 4 when n 4 is 1, and n 2 is an integer of 0 to 6 when n 4 is 2,

n 3 is an integer of 0 to 4 when n 5 is 1, and n 3 is an integer of 0 to 6 when n 5 is 2,

n 6 is an integer of 0 to 7, and

n 7 is 1 or 2, n 6 is an integer of 0 to 5 when n 7 is 1, and n 6 is an integer of 0 to 7 when n 7 is 2,

wherein formula (1) is:

wherein, R 1 is any one selected from the group consisting of:

a hydrogen atom;

a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and

a linear, branched or cyclic alkenyl group having 1 to 6 carbon atoms, and

where at least one hydrogen atom in the alkyl group and the alkenyl group in R 1 may be substituted with a fluorine atom,

L is any one selected from the group consisting of: a carbonyloxy group, a phenylenediyl group, a naphthalenediyl group, a phenylenediyloxy group, a naphthalenediyloxy group, a phenylenediylcarbonyloxy group, a naphthalenediylcarbonyloxy group, a phenylenediyloxycarbonyl group and a naphthalenediyloxycarbonyl group,

Sp is any one selected from the group consisting of:

a direct bond;

a linear, branched or cyclic alkylene group which may have a substituent, the alkylene group having 1 to 6 carbon atoms; and

a linear, branched or cyclic alkenylene group which may have a substituent, the alkenylene group having 1 to 6 carbon atoms, and

where at least one methylene group in the Sp may be substituted with a divalent heteroatom-containing group, and

* represents a bonding site with the compound represented by the general formulas (VI) to (VIII).

7. The polymer of claim 1 , further comprising a unit D having a radical scavenger structure.

8. The polymer of claim 1 , further comprising an organometallic compound-containing unit E having a metal atom selected from the group consisting of: Sn, Sb, Ge, Bi and Te.

9. A resist composition comprising the polymer of claim 1 .

10. The resist composition of claim 9 , further comprising a compound represented by any one of following general formulas (VI) to (VIII),

wherein, in the general formulas (VI) to (VIII),

m 2 is an integer of 0 or 1,

n 4 and n 5 are each an integer of 0 to 2, where n 4 +n 5 is 2,

n 2 is an integer of 0 to 4 when n 4 is 1, and n 2 is an integer of 0 to 6 when n 4 is 2,

n 3 is an integer of 0 to 4 when n 5 is 1, and n 3 is an integer of 0 to 6 when n 5 is 2,

n 6 is an integer of 0 to 7, and

n 7 is 1 or 2, n 6 is an integer of 0 to 5 when n 7 is 1, and n 6 is an integer of 0 to 7 when n 7 is 2,

when any of R 6 , R 7 and R 8 are present, each of R 6 , R 7 and R 8 is independently selected from the group consisting of: a hydrogen atom; an electron donating group; and an electron withdrawing group,

when more than one R 6 is present, at least one R 6 is the electron donating group, when more than one R 7 is present, at least one R 7 is the electron donating group, and when more than one R 8 is present, at least one of R 8 is the electron donating group,

R 9 is any one selected from the group consisting of: a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent, and at least one methylene group in R 9 may be substituted with a divalent heteroatom-containing group,

each of R 10 is independently any one selected from the group consisting of: a hydrogen atom; an alkyl group which may have a substituent; and an alkenyl group which may have a substituent, and two of R 10 may bond each other to form a ring structure, and

when E is present, E is any one selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom and a methylene group.

11. The resist composition of claim 9 , further comprising at least one of an organometallic compound or an organometallic complex,

wherein a metal of the organometallic compound and the organometallic complex is at least one selected from the group consisting of: Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn and Ra.

12. A method for manufacturing a device, comprising:

a resist film forming step of forming the resist film on a substrate using the resist composition of claim 9 ;

a photolithography step of exposing the resist film to a particle beam or an electromagnetic wave; and

a pattern forming step of developing the exposed resist film to obtain a photoresist pattern.

13. The method of claim 12 , wherein the particle beam is an electron beam, and the electromagnetic wave is an extreme ultraviolet radiation.