JP2018199781A - Polymer, resist composition containing polymer, and method for manufacturing device using the same - Google Patents

Abstract

To provide a polymer used for a resist composition which has large absorption efficiency of a particle beam or an electromagnetic wave, and is excellent in characteristics of sensitivity, resolution and pattern performance, a resist composition containing the polymer, and a method for manufacturing a device using them.SOLUTION: A polymer used for a resist composition contains a unit A and a unit B, where the unit A is a unit which has an onium salt structure having an anion part and a cation part, and produces a state in which a polymer type conjugate base and a hydrogen cation are paired by irradiation with a particle beam or an electromagnetic wave, the onium salt structure is covalently bonded to a polymer chain directly or through a first spacer, the unit B has a structure containing metal atoms or semi-metal atoms, the structure of the unit B is covalently or coordinately bonded to the polymer main chain directly or through a second spacer, when the structure of the unit B is covalently bonded to the polymer chain, the polymer type conjugate base is subjected to an additional or substitution reaction to the metal atoms or the semi-metal atoms to form an acid ester structure or an ion pair, or when the structure of the unit B is coordinately bonded to the polymer chain, the structure of the unit B has a coordinated substituent, and the polymer type conjugated base and the coordinated substituent cause a ligand exchange reaction to form a complex structure, and thereby constitute a crosslinked structure.SELECTED DRAWING: None

Description

  Some embodiments of the present invention relate to polymers used in resist compositions. Further, some embodiments of the present invention relate to a resist composition containing the polymer and a method for producing a device using the resist composition.

  In recent years, manufacturing of display devices such as liquid crystal display (LCD) and organic EL display (OLED) and formation of semiconductor elements have been actively performed by making full use of photolithography technology using a photoresist. In the above-mentioned electronic parts and electronic product packages, light such as i-line having a wavelength of 365 nm, h-line (405 nm) and g-line (436 nm) having a longer wavelength is widely used as an active energy ray.

  The demand for miniaturization of lithography technology is increasing as devices are highly integrated. KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), ultrashort ultraviolet (EUV, wavelength 13.5 nm), and electron beam Light with a very short wavelength such as (EB) tends to be used for exposure. Since the lithography technique using light having a short wavelength, particularly EUV or electron beam, can be manufactured by single patterning, the necessity of a resist composition exhibiting high sensitivity to EUV or electron beam is necessary. It is expected to increase further in the future.

Along with the shortening of the wavelength of the exposure light source, the resist composition is required to improve the sensitivity to the exposure light source and the resolution of the lithography that can reproduce a pattern with fine dimensions. A chemically amplified resist is known as a resist composition that satisfies such requirements (Patent Document 1).
However, in the conventional chemically amplified resist, it is difficult to sufficiently suppress the resist pattern collapse and the reduction in line edge roughness (LER) of the line pattern as the resolution line width of the resist becomes finer. In order to suppress resist pattern collapse, there is a method of increasing mechanical strength by crosslinking using a negative chemically amplified resist. A chemically amplified negative resist using a crosslinking agent forms an ester or ether bond between the crosslinking agent and the base resin component in the presence of an acid. As a result, a negative pattern can be formed, but uncrosslinked carboxyl groups and phenolic hydroxyl groups remain in the exposed part, so that they swell during alkali development, causing defects such as bridging and rounded resists. There is a disadvantage that it becomes a pattern shape. Although there is a strong demand for prevention of resist pattern collapse and bridge formation, conventional chemically amplified resist compositions for EUV or electron beam have low absorption of EUV or electron beam, and have low sensitivity, resolution and pattern performance. It is difficult to satisfy the characteristics at the same time.

JP-A-9-90637 JP 2000-206694 A SPIEA Advances in Resist Technology and Processing XV 3333, 417 (1998)

Some aspects of the present invention provide a polymer used for a resist composition having high absorption efficiency of particle beam or electromagnetic wave, particularly electron beam or EUV, and excellent characteristics of sensitivity, resolution, and pattern performance. To do.
It is an object of some aspects of the present invention to provide a resist composition containing the polymer and a method for producing a device using the resist composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a unit A having an onium salt structure, an electromagnetic wave such as EUV, and a metal atom having higher particle beam absorption such as an electron beam and an ion beam than a carbon atom. Or it discovered that the said subject was solved by using the polymer containing the unit B which has a structure containing an antimetallic atom as a polymer of a resist composition. That is, secondary electrons are generated from the unit B by irradiating the resist composition containing the polymer with particle beams or electromagnetic waves. The secondary electron decomposes the onium salt structure of the unit A so that it becomes a nonionic compound, and in addition to the conjugate base bonded to the polymer from the unit A (hereinafter referred to as “polymer-type conjugate base”). ) And a hydrogen cation are paired. A cross-linking reaction occurs between the polymer-type conjugate base and the unit B having reactivity so that a photoresist pattern having a high cross-linking density can be constructed by a reaction between functional groups bonded to the polymer main chain. It has less swelling than the technology, has succeeded in increasing the sensitivity and suppressing pattern collapse, and has completed some aspects of the present invention.

One aspect of the present invention that solves the above problems is a polymer including unit A and unit B, wherein the unit A has an onium salt structure having an anion portion and a cation portion, and is a particle beam or electromagnetic wave. It is a unit that generates a state in which a polymer-type conjugate base and a hydrogen cation are paired by irradiation, and the onium salt structure is covalently bonded to the polymer main chain directly or via the first spacer,
The unit B has a structure containing a metal atom or a metalloid atom, and the structure of the unit B is covalently or coordinately bonded to the polymer main chain directly or via a second spacer;
When the structure of the unit B is covalently bonded to a polymer chain, the polymer-type conjugate base is added or substituted to the metal atom or metalloid atom to form an acid ester structure or an ion pair, Or
When the structure of the unit B is coordinated to a polymer chain, the structure of the unit B has a coordinating substituent, and the polymer conjugate base and the coordinating substituent are coordinated. It is a polymer characterized in that a crosslinked structure is constructed by forming a complex structure through a child exchange reaction.
Examples of the metal or metalloid atom include B, Al, Si, As, Ti, Zr, Mo, Se, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, and Ag. , Cd, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, and At.

One embodiment of the present invention is a resist composition containing the polymer.
One embodiment of the present invention includes a step of forming a resist film on a substrate using the resist composition, a step of exposing the resist film using particle beams or electromagnetic waves, and an exposed resist film. Developing a photoresist pattern to obtain a photoresist pattern.

  When used as a resist composition, the polymer according to some embodiments of the present invention has high absorption efficiency of particle beams or electromagnetic waves, and is excellent in characteristics of sensitivity, resolution, and pattern performance.

In the present invention, “particle beam or electromagnetic wave” includes an electron beam and extreme ultraviolet rays.
In the present invention, “by irradiation with particle beam or electromagnetic wave” means that at least a part of the polymer is exposed to the particle beam or electromagnetic wave. When a part of the polymer is exposed to the particle beam or the electromagnetic wave, a specific part of the polymer is excited or ionized to generate active species. A secondary reaction occurs such that the active species decomposes a part of the unit, the active species adds to the unit, or the active species desorbs the hydrogen of the unit. Occur. Here, “active species” refers to acids, radical cations, radicals, electrons, and the like.
In the present invention, the “polymer-type conjugate base” is a conjugate base covalently bonded to the polymer main chain directly or via a spacer, and examples thereof include an anion portion of sulfonic acid and an anion portion of carboxylic acid.
In the present invention, the “paired state” includes a case where a polymer-type conjugate base and a hydrogen cation are dissociated and a case where they are bonded. The dissociation occurs when the acid generated by the decomposition of the onium salt structure is a strong acid, specifically when the anion portion of the onium salt structure has, for example, a sulfonate structure. The case of bonding is when the acid generated by decomposition of the onium salt structure is a weak acid, and when the anion portion of the onium salt structure has a carboxylate structure or the like.
Hereinafter, although this invention is demonstrated concretely, this invention is not limited to this.

<1> Polymer The polymer which is some embodiments of the present invention has unit A and unit B. The unit A is a unit A that has an onium salt structure having a cation portion and an anion portion, and generates a state in which a polymer-type conjugate base and a hydrogen cation are paired by irradiation with a particle beam or electromagnetic wave. The salt structure is covalently bonded to the polymer backbone directly or via a first spacer.
The unit B has a structure containing a metal atom or a metalloid atom (hereinafter also referred to as “metal-containing structure”), and the metal-containing structure is covalently bonded or arranged directly or via a second spacer to the polymer main chain. Are linked.
When the metal-containing structure is covalently bonded to the polymer chain, the polymer-type conjugate base is added or substituted to the metal atom or metalloid atom to form an acid ester structure or ion pair, or When the metal-containing structure is coordinated to the polymer chain, the metal-containing structure has a coordinating substituent, and the polymer-type conjugate base and the coordinating substituent undergo a ligand exchange reaction. Thus, a crosslinked structure is constructed by forming a complex structure.

  The polymer containing unit A and unit B generates a state in which a polymer conjugate base and a hydrogen cation are paired by reduction of unit A by exposing at least a part of the polymer with a particle beam or electromagnetic wave. To do. The polymer-type conjugate base and the metal-containing structure of the unit B react to form a covalent bond, an ionic bond, or a coordinate bond, and a crosslinked structure can be constructed.

(Unit A)
The unit A has an onium salt structure having a cation portion and an anion portion, and at least a part of the polymer is exposed to a particle beam or electromagnetic wave, whereby the polymer-type conjugate base and the hydrogen cation are paired. It generates a state. That is, the polymer main chain and the anion portion of the onium salt structure are covalently bonded directly or via the first spacer, and the polymer-type conjugate base and hydrogen derived from the anion portion bonded to the polymer main chain by reduction of the onium salt structure. There is no particular limitation as long as it generates a paired state with a cation. Specific examples of the unit A having the onium salt structure include those represented by the following general formulas (1) and (2). However, it is not limited to these.
In the unit A represented by the general formulas (1) and (2), L ¹ and R ² correspond to the first spacer.

In the general formulas (1) and (2), R ¹ is any one selected from the group consisting of a hydrogen atom; a fluorine atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Yes, the alkyl group in R ¹ may have a substituent.

Examples of the alkyl group for R ¹ include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group;
Branched alkyl groups such as isopropyl and t-butyl groups;
And cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.
Examples of the substituent that R ¹ may have (hereinafter, also referred to as “first substituent”) include halogen atoms such as fluorine.
When fluorine is used as the first substituent, R ¹ may be, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 1,1,2,2,2- A pentafluoroethyl group etc. are mentioned.
R ¹ preferably has 1 to 6 carbon atoms, and more preferably has 1 to 2 carbon atoms. The number of carbon atoms includes the first substituent when R ¹ has the first substituent.

When R ¹ has a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond. Examples of R ¹ having an unsaturated bond include a vinyl group and an isopropenyl group.
When R ¹ has a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group. Examples of the divalent hetero atom-containing group, described below in R ^2.

R ² is not particularly limited as long as it can bind the polymer main chain and the anion portion of the onium salt structure via L ¹ , for example, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; An arylene group having 6 to 14 carbon atoms; and a heteroarylene group having 4 to 14 carbon atoms; an alkylene group, an arylene group, and a heteroarylene group in R ² are substituents. You may have.

Examples of the linear alkylene group having 1 to 12 carbon atoms of R ² include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, n -Octylene group, n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, etc. are mentioned.
Examples of the branched alkylene group having 1 to 12 carbon atoms of R ² include an isopropylene group, an isobutylene group, a tert-butylene group, an isopentylene group, a tert-pentylene group, and a 2-ethylhexylene group.
Examples of the cyclic alkylene group having 1 to 12 carbon atoms of R ² include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

When R ² has a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond.
R ² having an unsaturated bond includes linear alkenylene groups such as ethynylene group, propenylene group, butenylene group, hexenylene group, octenylene group and decanylene group;
Isopropenylene group, 1-ethylethenylene group, 2-methylpropenylene group, 2,2-dimethylbutenylene group, 3-methyl-2-butenylene group, 3-ethyl-2-butenylene group, 2-methyloctenylene Groups and branched alkenylene groups such as 2,4-dimethyl-2-butenylene groups;
And cyclic alkenylene groups such as a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group, and a cyclohexenylene group.

Examples of the arylene group having 6 to 14 carbon atoms of R ² include pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, acanthrylene, Divalent obtained by removing two hydrogen atoms from triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentaphen, pentacene, tetraphenylene, hexaphene, hexacene, rubicene, coronene, trinaphthylene, heptaphene, heptacene, pyrantrene, ovalene, etc. The aromatic hydrocarbon group of these is mentioned.
The heteroarylene group having 4 to 14 carbon atoms of R ² is obtained by removing two hydrogen atoms from furan, thiophene, imidazole, pyrazole, oxazole, pyridine, pyrimidine, quinoline, xanthene, carbazole, and acridyl. And a divalent aromatic heterocyclic group.

It is preferable that a part or all of hydrogen contained in R ² is substituted with a fluorine atom.
When R ² has a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
Examples of the divalent heteroatom-containing group include —O—, —CO—, —COO—, —OCO—, —O—CO—O—, —NHCO—, —CONH—, and —NH—CO—O—. , —O—CO—NH—, —NH—, —N (R ^b ) (R ^b is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent. .), —N (Ar ^b ) — (Ar ^b is an aryl group having 4 to 14 carbon atoms which may have a substituent), —S—, —SO—, —SO ₂ — and the like. And a group selected from the group consisting of
Examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms that is R ^b include the same alkyl groups as exemplified in R ^{3 to} R ⁵ described later.
Examples of the aryl group having 1 to 12 carbon atoms, which is Ar ^b , include the same aryl groups as exemplified in R ^{3 to} R ⁵ described later.

As a substituent that R ² may have (hereinafter, also referred to as “second substituent”), in addition to the first substituent, a hydroxy group, a cyano group, a mercapto group, a carboxy group, an alkoxy group (— OR ⁶ ), acyl group (—COR ^b ), alkoxycarbonyl group (—COOR ^b ), aryl group (—Ar ^b ), aryloxy group (—OAr ^b ), amino group, alkylamino group (—NHR ^b ), Dialkylamino group (—N (R ⁶ ) ₂ ), arylamino group (—NHAr ^b ), diarylamino group (—N (Ar ^b ) ₂ ), N-alkyl-N-arylamino group (—NR ^b Ar ^b ), phosphino group, a silyl group, a halogen atom, a trialkylsilyl group _{^{(-Si- (R b) 3)}} , at least one of substituents in Ar ^b alkyl group of the trialkylsilyl group Silyl group, an alkylsulfanyl group (-SR ^b) and although arylsulfanyl can be exemplified Le group (-SAr ^b) such as but not limited to.
^R b in the second substituent, Ar ^b is ^R b, those similar to the Ar ^b include in the divalent heteroatom-containing group.
The number of carbon atoms of R ² is, if R ² has a second substituent, and that including the second substituent.

L ¹ is not particularly limited as long as the polymer main chain and the anion portion of the onium salt structure can be bonded via R ^2. For example, L ¹ is directly bonded; carbonyloxy group; carbonylamino group; linear, branched or cyclic An alkylenecarbonyloxy group; a linear, branched or cyclic alkylenecarbonylamino group; an arylenecarbonyloxy group; and an arylenecarbonylamino group; an amino group in L ¹ , an alkylene group, and The arylene group may have a substituent (hereinafter also referred to as “third substituent”).
The arylene group in L ¹ may be a heteroarylene group.
As the third substituent, an alkyl group, a hydroxy group, a mercapto group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylsulfanylcarbonyl group, an arylsulfanyl group, an alkylsulfanyl group, Aryl group, heteroaryl group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, arylsulfonyl group, (meth) acryloyloxy group, hydroxy (poly) alkyleneoxy group, amino group, cyano One selected from the group consisting of a group, a nitro group and a halogen atom.

When L ¹ is an alkylene group or a group having an alkylene group, specific examples of the alkylene group include the same alkylene groups as those exemplified below for R ² .
When L ¹ is an arylene group or a group having an arylene group, specific examples of the arylene group include those similar to the arylene group and heteroarylene group exemplified by R ² described later.
When L ¹ has a carbon atom, the number of carbon atoms including the third substituent is preferably 1 to 12.

  As a structure represented by the said General formula (1), the structure which has a sulfonate shown below is mentioned, for example.

  As a structure represented by the said General formula (2), the structure which has the carboxylate shown below is mentioned, for example.

M ⁺ is a sulfonium cation represented by the general formula (3) or an iodonium cation represented by the general formula (4).
The structure of the cation portion M ⁺ of the onium salt is a sulfonium cation or an iodonium cation, and specific examples include those represented by the following general formulas (3) and (4).

R ^{3 to} R ⁵ are each a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms that may have a substituent; an aryl group having 6 to 14 carbon atoms that may have a substituent; And a heteroaryl group having 4 to 14 carbon atoms which may have a substituent.
R ³ and R ⁴ form a ring structure together with a sulfonium cation or an iodonium cation to which R ³ and R ⁴ are bonded either directly or through a group selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group. May be.
When R ^{3 to} R ⁵ have a methylene group, at least one of the methylene groups may be substituted with the divalent hetero atom-containing group.

Examples of the linear alkyl group having 1 to 12 carbon atoms of R ^{3 to} R ⁵ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-heptyl. , N-octyl group, n-nonyl, n-decyl group, n-undecyl, n-dodecyl and the like.
Examples of the branched alkyl group having 1 to 12 carbon atoms of R ^{3 to} R ⁵ include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, tert-pentyl group, and 2-ethylhexyl group. Can be mentioned.
Examples of the cyclic alkyl group having 1 to 12 carbon atoms of R ^{3 to} R ⁵ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantane-1-yl group, an adamantane-2-yl group, and norbornane-1- And yl group and norbornan-2-yl group.

When R ^{3 to} R ⁵ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with an unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond. Good. R ^{3 to} R ⁵ having an unsaturated bond include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, 1-methylallyl group, 2-methylallyl group, 4-pentenyl group and 5-hexenyl group. ;
Isopropenyl group, isobutenyl group, 3-butenyl group, 2-butenyl group, isopentenyl group, 2-ethyl 2-hexenyl group, neopentenyl group, isohexenyl group, isotridecenyl group, isooctadecenyl group and isotriaconte Branched alkenyl groups such as nyl groups;
And cyclic alkenyl groups such as a cyclopentenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

Examples of the aryl group having 6 to 14 carbon atoms of R ^{3 to} R ⁵ include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a naphthyl group, an anthryl group, a phenanthrenyl group, a pentarenyl group, an indenyl group, and an indacenyl group. Acenaphthyl group, fluorenyl group, heptalenyl group, naphthacenyl group, pyrenyl group, chrycenyl group, tetracenyl group and the like.
Examples of the heteroaryl group having 4 to 14 carbon atoms of R ^{3 to} R ⁵ include a furanyl group, a thienyl group, a pyranyl group, a sulfanylpyranyl group, a pyrrolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, a pyrazoyl group, and a pyridyl group. , Pyrimidyl group, isobenzofuranyl group, benzofuranyl group, isochromenyl group, chromenyl group, pyrazyl group, purinyl group, quinolinyl group, isoquinolinyl group, chromenyl group, thianthenyl group, dibenzothiophenyl group, phenothiazinyl group, phenoxazinyl group, phenoxazinyl group Group, phenazinyl group, indolyl group, isoindolyl group, benzimidazolyl group, xanthenyl group, aquadinyl group, carbazoyl group and the like.

R ^{3 to} R ⁵ may have a substituent (hereinafter also referred to as “fourth substituent”), and examples of the fourth substituent include the same as the third substituent.
R ³ to R number of carbon atoms of the ^5, if R 3 to R ⁵ has a fourth substituent, and that including the fourth substituent.

  Examples of the sulfonium cation and the iodonium cation as the cation portion of the onium salt structure include those having a structure shown below.

(Unit B)
The unit B has a structure containing a metal atom or a metalloid atom, and the structure is covalently or coordinately bonded to the polymer main chain directly or via a second spacer. When covalently bonded to the chain, the polymer-type conjugate base is added or substituted to the metal atom or metalloid atom to form an acid ester structure or an ion pair, or the structure is added to the polymer chain. When coordinated, the structure has a coordinating substituent, and the polymer-type conjugated base and the coordinating substituent form a complex structure through a ligand exchange reaction to form a crosslinked structure. There is no particular limitation as long as the body is constructed.
In addition, as a ratio in the polymer of the said unit A and the unit B, it is preferable that it is 5: 95-95: 5.

The metal atom or metalloid atom is preferably one having higher absorption of particle beam or electromagnetic wave than carbon atom, and one having higher absorption to EUV, electron beam or ion beam than carbon atom. preferable. Specific examples of such metal atoms or metalloid atoms include B, Al, Si, As, Ti, Zr, Mo, Se, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Ga. , Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, and At Preferred is at least one selected atom. The metal atom or metalloid atom is preferably one having high absorption with respect to EUV, electron beam or ion beam, but it is exemplified above if it reacts with the polymer type conjugate base to construct a crosslinked structure. Other metals may be used. Preferably, it is any atom selected from the group consisting of Sn, Sb, Ge, Bi, and Te.
Since the polymer contains the unit B, it contains atoms having a large specific gravity compared to carbon and oxygen, and contains atoms that have a large absorption of electromagnetic waves such as particle beams such as electron beams or EUV. The generation efficiency of secondary electrons when irradiated with EUV can be improved. Thereby, the sensitivity of the resist can be increased.

The structure of the unit B is at least one of the structures represented by the following general formulas (5) to (7).
In the unit B represented by the general formula (5), L ¹ and R ² correspond to the second spacer.
In the unit B represented by the general formulas (6) and (7), L ¹ , R ² and C ¹ correspond to the second spacer.

In the above general formulas (5) to (6), R ¹ , R ² and L ¹ are each independently selected from the same options as R ¹ , R ² and L ^{1 in the} general formula (1).
R ⁶ is selected from the same options as R ⁵ described above, and when two or more R ⁶ are present, R ⁶ may form a ring directly or through any one of an oxygen atom, a nitrogen atom, a sulfur atom and a methylene group. May be.
X is the above metal atom or metalloid atom.

h is valence-1 of X and 0 to 3.
i is 1 to 6, j is 0 to 5, and is determined by the valence of X and the coordination state of C ¹ and C ² .
k is to be determined by the state of coordination and the X 0-5 valence and C ^1.
In the general formulas (6) and (7), → represents a coordination bond.

As the structure represented by the general formula (5), alkyl tin, aryl tin, alkyl antimony, aryl antimony, alkyl germane, aryl germane, alkyl bismuthine, aryl bismuthine, alkyl tellurite having high absorption with respect to particle beam or electromagnetic wave And any structure selected from the group consisting of aryl tellurites is preferably a unit bonded to the * part of the following general formula (15) at any position of the structure.
In the general formula (5), two or more of R ² and the plurality of R ⁶ are bonded to each other directly by a single bond or via a group selected from the group consisting of methylene groups. A ring structure may be formed together with X.

In the general formula ^(15), R 1, ^{R 2} and ^{L 1} is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in formula (1).

  As the unit B, units represented by the following general formulas (16) to (22) are preferable because they can be synthesized particularly easily.

In the general formulas (16) to (22), R ¹ , R ² , R ⁶ and L ¹ are selected from the same options as in the general formula (5).

  Specifically as unit B, 4-vinylphenyl-triphenyltin, 4-vinylphenyl-tributyltin, 4-isopropenylphenyl-triphenyltin, 4-isopropenylphenyl-trimethyltin, trimethyltin acrylate, acrylic acid Tributyltin, triphenyltin acrylate, trimethyltin methacrylate, tributyltin methacrylate, triphenyltin methacrylate, 4-vinylphenyl-diphenylantimony, 4-isopropenylphenyl-diphenylantimony, 4-vinylphenyl-triphenylgermane, 4 -Vinylphenyl-tributylgermane, 4-isopropenylphenyl-triphenylgermane and 4-isopropenylphenyl-trimethylgermane, 4-vinylphenyl-triphenyle Silane, (1-fluorovinyl) methyl diphenyl silane, 4-vinylphenyl boronic acid 1,3-propanediol, and is composed of units from monomers such as 4-vinylphenyl boronic acid catechol.

In order to construct a crosslinked structure by the reaction of the polymer-type conjugate base and unit B, the ability of R ⁶ to desorb from X should be the same as or higher than R ² covalently bonded to the polymer main chain via L ^1. Is desirable. De Hanareno of R ⁶ from X as a method of increasing than R ^2, or that R ² R ⁶ has many electron-donating group than R ² has many electron attractive group than R ⁶ It is preferable.
Examples of the electron donating group possessed by R ⁶ include an alkyl group, an alkenyl group, and an alkoxy group (—OR ^3a ) and an alkylthio group (—SR ^3a ) bonded to the ortho or para position of the aryl group; For example, when R ² is a phenylene group, R ⁶ is preferably a 4-alkylphenyl group, a 4-alkoxyphenyl group, a 4-alkylsulfanylphenyl group, a 4-dialkylaminophenyl group, or the like.
R ² has an electron-withdrawing group as an acyl group, an acyloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a nitro group, a nitroso group, a trifluoromethyl group, and an aryl group. And any one selected from the group consisting of an alkoxy group substituted at the meta position, an aryloxy group, an alkylsulfanyl group, and an arylsulfanyl group. For example, when R ⁶ is a phenyl group, R ² is preferably a ² -acylphenylene group, a 3-cyanophenylene group, a 2,3,5,6, -tetrafluorophenylene group or the like, but the present invention is not limited thereto.

C ¹ in the structure represented by the general formula (6) is a monodentate ligand or a polydentate ligand covalently bonded to R ² and is a monovalent organic group having at least one coordination atom.
C ² is an independent monodentate ligand or an independent polydentate ligand as the coordinating substituent, and is a molecule having at least one coordination atom. Specific examples of C ² include the following.
Examples of the C ² independent monodentate ligand include molecules such as cyanide, cyanate, thiocyanate, and hydrocarbon compounds containing π electrons. Examples of the C ² independent polydentate ligand include molecules having two or more coordination atoms, and those represented by the following general formula (23), but the present invention is not limited thereto.
R ^19- (Y) _k (23)
The compound represented by the general formula (23) has a structure as it is, or when there are s active protons such as a hydroxy group and s electron withdrawing group α-position protons such as a carbonyl group, they are eliminated. The resulting s-valent anion structure can be a multidentate ligand. s is an integer of 0-4.

Examples of hydrocarbon compounds containing π electrons include chain olefins such as ethylene and propylene, and cyclic olefins such as cyclopentene, cyclohexene and norbornene;
Chain dienes such as butadiene and isoprene;
Cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene and norbornadiene;
And aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene and indene.

In the general formula (23), R ¹⁹ is a k-valent organic group which may have a substituent, and at least one methylene group may be substituted with the divalent heteroatom-containing group. , Y is —OH, —COOH, —NCO, —PR ^a ₂ , —P (OR ^a ) ₂ , —P (O) R ^a ₂ , —SO ₃ H, —COOR ^a or —NHR ^a . R ^a represents a hydrogen atom or a monovalent alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a heteroaryl having 4 to 14 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom. It is a group. k is an integer of 1 to 4. When k is 2 or more, the plurality of Y may be the same or different. R ^a is selected from the same options as R ³ above.
The substituent that R ¹⁹ may have is the same option as the substituent (third substituent) of L ^{1 in} the general formula (1).

Examples of the k-valent hydrocarbon group include alkanes such as methane, ethane, propane, and butane;
Alkenes such as ethene, propene, butene and pentene;
A chain hydrocarbon having 1 to 30 carbon atoms such as alkyne such as ethyne, propyne, butyne and pentyne;
An alicyclic hydrocarbon having 3 to 30 carbon atoms such as cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane and adamantane, cycloalkene such as cyclopropene, cyclobutene, cyclopentene, cyclohexene and norbornene;
Hydrocarbons such as aromatic hydrocarbons having 6 to 30 carbon atoms such as arenes such as benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, dimethylnaphthalene and anthracene; groups in which k hydrogen atoms have been removed from etc. Is mentioned.

Examples of the above (23) include hydroxy esters such as glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, salicylic acid ester, acetylacetone, methylacetylacetone, ethylacetylacetone, 2,4- Β-diketones such as pentanedione and 3-methyl-2,4-pentanedione, acetoacetate, α-alkyl-substituted acetoacetate, β-ketopentanoate, benzoyl acetate, 1,3-acetone dicarboxylate Β-ketoesters such as, malonic acid diester, α-substituted malonic acid diester, α-cycloalkyl substituted malonic acid ester, α-aryl substituted malonic acid ester, etc. β-dicarboxylic acid esters, ethylene glycol, propylene glycol Dialkylene glycols such as coal, butylene glycol, hexamethylene glycol diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol;
Cycloalkylene glycols such as cyclohexanediol, cyclohexanedimethanol, norbornanediol, norbornanedimethanol, adamantanediol;
Alkanetriols such as 1,4-benzenedimethanol, 2,6-naphthalenediethanolcatechol, resorcinol, hydroquinone, glycerin, 1,2,4-butanetriol;
Cycloalkanetriols such as 1,2,4-cyclohexanetriol, 1,2,4-cyclohexanetrimethanol;
Alkanetetraols such as 1,2,4-benzenetrimethanol, 2,3,6-naphthalenetrimethanol, pyrogallol, 2,3,6-naphthalenetriol, erythritol, pentaerythritol;
Polyols such as 1,2,4,5-cyclohexanetetraol 1,2,4,5-benzenetetramethanol, 1,2,4,5-benzenetetraol, oxalic acid, malonic acid, succinic acid, glutaric acid Chain saturated dicarboxylic acids such as adipic acid;
Maleic acid, fumaric acid, 4-cyclohexanedicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,2,3-propanetricarboxylic acid Acid, 1,2,3-propenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, trimellitic acid, 2,3,7-naphthalenetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1 , 2,3,4-butadienetetracarboxylic acid, 1,2,5,6-cyclohexanetetracarboxylic acid, 2,3,5,6-norbornanetetracarboxylic acid, pyromellitic acid, 2,3,6,7- Carboxylic acids such as naphthalenetetracarboxylic acid, ethylene diisocyanate, trimethylene diisocyanate , Tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, 1,4-benzene diisocyanate, 4,4′-diphenylmethane diisocyanate, trimethylene triisocyanate, 1,2,4- Isocyanates such as cyclohexane triisocyanate, 1,2,4-benzenetriisocyanate, tetramethylenetetraisocyanate, 1,2,4,5-cyclohexanetetraisocyanate, 1,2,4,5-benzenetetraisocyanate, ethylenediamine, N- Methylethylenediamine, N, N'-dimethylethylenediamine, trimethylenediamine, N, N'-dimethyltrimethylenediamine, tetramethylene 1,4-cyclohexanediamine, 1,4-di (aminomethyl) cyclohexane, 1,4-diaminobenzene, 4,4′-diaminodiphenylmethane, triaminopropane, N, N ′, N ″ -trimethyltriaminopropanediamine N, N′-dimethyltetramethylenediamine, 1,2,4-triaminocyclohexane, 1,2,4-triaminobenzene, tetraaminobutane, 1,2,4,5-tetraaminocyclohexane, 2,3 , 5,6-tetraaminonorbornane, 1,2,4,5-tetraaminobenzene and other amines.

Specific examples of C ^{1 in the} structure represented by the general formula (6) include organic groups obtained by removing one hydrogen atom from R ^{26 in the} general formula (23).

  Examples of the monomer constituting the structure represented by the general formulas (6) to (7) include the following.

(Unit C)
The polymer in one embodiment of the present invention has an acid dissociable group in addition to the above units A and B, and the acid dissociable group is deprotected in the presence of an acid decomposed by the onium salt structure. Thus, a unit C whose reactivity with the unit B is increased may be further contained.
The content of the unit C in the polymer is preferably 0 to 4 molar equivalents relative to the total amount of the unit A and unit B.

  Specific examples of the unit C include those represented by the following general formulas (8) to (11).

R ^{1, R 2} and ^{L 1} in the general formula (8) to (11) in is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in the general formula (1).
R ⁷ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent.
R ⁸ and R ⁹ are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent.
Two or more of R ⁷ , R ⁸ and R ⁹ may form a ring structure either directly by a single bond or via any selected from the group consisting of methylene groups.
R ¹⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent.
R ¹¹ and R ¹² are each independently selected from the group consisting of a hydrogen atom; and a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms that may have a substituent. .
Two or more of R ¹⁰ , R ¹¹ and R ¹² may form a ring structure either directly by a single bond or via any selected from the group consisting of methylene groups.
Each R ¹³ is independently selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, amino, cyano, nitro and halogen atoms. If any of them have carbon as a substituent, these have a substituent.
When R ^{7 to} R ¹³ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond;
When R ^{7 to} R ¹³ have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
l ¹ is an integer of ¹ to 2, m ¹ is an integer of 0 to 4 when l ¹ is 1, and an integer of 0 to 6 when l ¹ is 2,
n ¹ is 1-5 when ^{l 1} is 1, and 1-7 integer when ^{l 1} is 2,
m ¹ + n ¹ is 1 to 5 when l ¹ is 1, and ¹ to 7 when l ¹ is 2.

As R < ⁸ > -R < ¹⁰ >, the same thing as the alkyl group of said R < ³ > is mentioned. For example, methyl, ethyl, n-propyl, n-butyl, isopropyl, t-butyl, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantane-1-yl group, adamantane-2-yl group, norbornane-1- And alkyl groups such as yl group and norbornane-2-yl group.
Examples of the alkyl group represented by R ^{11 to} R ¹² include the same alkyl groups as those described above for R ³ .

A part of hydrogen atoms of R ¹³ is preferably substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group or the like.

  Specifically, the following structures can be exemplified. However, the present invention is not limited to this.

(Unit D)
The polymer in one embodiment of the present invention preferably contains a unit D that can act as a sensitizer and increase sensitivity to particle beams and electromagnetic waves, in addition to the units A to C described above.
The content of the unit D in the polymer is preferably 0 to 1 molar equivalent relative to the total amount of the unit A and unit B.

Unit D is a compound in which the compounds represented by the following general formulas (12) to (14) are bonded to R ² at the position of * in the above general formula (15).

In the general formulas (12) to (14), R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently selected from the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group. And
At least one of R ¹⁴ and R ¹⁵ is the electron donating group, and at least one of R ¹⁶ is the electron donating group.
R ¹⁷ is any one selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent. The alkyl group of R ¹⁷ is selected from the same options as the alkyl group of R ³ .
Each of R ¹⁸ is independently selected from the group consisting of a hydrogen atom; and an optionally substituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; One R ¹⁸ may be bonded to each other to form a ring structure. The alkyl group of R ¹⁸ is selected from the same options as the alkyl group of R ³ .
When R ^{14 to} R ¹⁸ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond.
When R ^{14 to} R ¹⁸ have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group.
E is any selected from the group consisting of a direct bond, an oxygen atom, a sulfur atom and a methylene group.
m ³ is an integer of 0 or 1, n ⁵ and n ⁶ are each an integer of 0 to 2, n ⁵ + n ⁶ is 2, and when n ⁵ is 1, n ³ is 0 to 4 When n ⁵ is 2, n ³ is an integer from 0 to ⁶ , when n ⁶ is 1, n ⁴ is an integer from 0 to 4, and when n ⁶ is 2, n ⁴ is from 0 to 6 an integer, ^{n 7} is an integer of 0 to 7, ^{n 8} is 1 or 2, ^{n 7} when ^{n 8} is 1 is an integer of 0 to 5, when ^{n 8} is 2 ^{n 7} Is an integer from 0 to 7.

As the electron donating group for R ¹⁴ , R ¹⁵ and R ¹⁶ , an optionally substituted alkyl group having 1 to 12 carbon atoms (—R ^c ); and an aromatic ring with respect to a hydroxyl group or an acetal group And an alkoxy group (—OR ^c ) and an alkylthio group (—SR ^c ) bonded to the ortho or para position.

R ^c is selected from the same options as the alkyl group as R ³ . A silyl group-substituted alkyl group in which one of hydrogen atoms of the alkyl group of R ³ is substituted with a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, or a dimethylethylsilyl group; in the alkyl group, the compound (11) Preferable examples also include an alkyl group in which at least one of hydrogen atoms of carbon atoms not directly bonded to the aromatic ring of (13) is substituted with a cyano group or a fluoro group.

The electron-withdrawing group for R ¹⁴ , R ¹⁵ and R ¹⁶ includes —C (═O) R ^c ; —C (═O) Ar ^b ; —C (═O) OR ^c ; —SO ₂ R ^c ; SO ₂ Ar ^b ; nitro group; nitroso group; trifluoromethyl group; —OR ^c substituted at the meta position with respect to the hydroxyl group or acetal group; —OR ²⁰ (substituted at the meta position with respect to the hydroxyl group or acetal group) R ²⁰ is any one selected from the group consisting of an optionally substituted alkylsulfanyl group, arylsulfanyl group, and alkylsulfanylphenyl group); substituted at the meta position with respect to a hydroxyl group or an acetal group; SR ^c; -SAr ^b is substituted meta to the hydroxyl group or an acetal group; the ^{-C (= O) R 21 (} R 21 is a part or all of the hydrogen atoms substituted by fluorine atoms A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms which may have a substituent; and 4 to 4 carbon atoms which may have a substituent A group in which at least one of the carbon-carbon single bonds in —C (═O) OR ^c , —SO ₂ R ^c and —SR ²¹ is substituted with a carbon-carbon double bond; Or a group substituted with a carbon-carbon triple bond;
The alkyl group, aryl group and heteroaryl group of R ²¹ can be selected from the same options as R ³ .

Examples of the compounds represented by the general formulas (12) to (14) bonded to the R ² group at * in the general formula (15) include those specifically shown below.

(Unit E)
In addition to the above units A to D, the polymer in one embodiment of the present invention acts as an acid proliferating agent that generates a sulfonic acid by a decomposition reaction accompanied by a dehydration reaction when the polymer acid generated from the unit A acts. It is preferable to contain a unit E (hereinafter also referred to as “unit E”) that can increase sensitivity to particle beams and electromagnetic waves.

  Examples of the unit E include compounds represented by the following general formulas (24a) to (24d).

R ^{24 to} R ^{26 in the} above general formulas (24a) to (24d) are each selected from the same options as R ³ represented by the above general formulas (3) and (4), and similarly to R ³ and R ⁴ , ^{24 to} R ²⁶ may form a ring structure with each other through a single bond, a direct bond, or any one selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group.
R ^{7 to} R ⁹ and R ^{18 in the} general formulas (24a) to (24d) are respectively selected from the same options as R ^{7 to} R ⁹ and R ^{18 in the} general formulas (8) and (14).

  Examples of the unit E include those having the structure shown below, but the present invention is not limited to this.

  The content of the unit E in the polymer is preferably 0 to 4 molar equivalents relative to the total amount of the unit A and the unit B.

(Other units)
The polymer in one aspect of the present invention may have units that are usually used as a resist composition in addition to the units A to E, as long as the effects of the present invention are not impaired.
For example, a unit having a skeleton containing an ether group, a lactone skeleton, a sultone skeleton, a sulfolane skeleton, an ester group, a hydroxy group, an epoxy group, a glycidyl group, an oxetanyl group or the like in the * part of the general formula (15) (hereinafter, “ Unit F ”).

  Examples of those containing a lactone skeleton, a sultone skeleton, and a sulfolane skeleton in the * part of the general formula (15) are shown below. However, the present invention is not limited to this.

  The unit F having a hydroxy group in the * part of the general formula (15) can serve as a hydrogen source when the unit A forms a pair of the polymer-type conjugate base and a hydrogen cation. The generation efficiency can be improved and high sensitivity is preferable. More preferably, the reactivity with respect to the unit B is low and it can be a hydrogen source.

  Examples of the unit F having a hydroxy group at the * portion of the general formula (15) include those shown below. However, the present invention is not limited to this.

  Spin-on-glass (SoG) in a photoresist that builds a multilayer film with different etching resistance by incorporating the siloxane unit having high oxygen etching resistance in the same manner as the unit B having high oxygen etching resistance by including a siloxane unit in the polymer. ) The layer can be omitted and the pattern can be easily transferred directly to the SoC layer, so that the throughput can be improved. Therefore, it is also preferable to contain a siloxane unit in addition to the units A to F.

  As the siloxane unit, silsesquioxane (POSS) is preferable.

  Examples of the above-mentioned silose siloxane include acrylol POSS, acrylol isobutyl POSS, methacryl isobutyl POSS, methacrylate cyclohexyl POSS, methacrylate isobutyl POSS, methacrylate ethyl POSS, methacrylate ethyl POSS, methacrylate isooctyl POSS, methacryl isooctyl POSS, methacryl phenyl. Examples thereof include compounds such as POSS.

Further, by introducing silyl ethers such as tris (trimethylsilyloxy) silyl group as shown in the following general formula (25) into the unit B, the oxygen is generated from the unit A while maintaining high etching resistance of oxygen plasma. It is preferable because it can be crosslinked by a hydrolysis reaction using an acid as a catalyst.

(Method for synthesizing compounds constituting each unit)
Several examples of the compound constituting the unit A are exemplified in the examples described later. Further, for example, it can also be obtained by semi-processing JP 2009-263487 A.
Several examples of the synthesis of the compound constituting the unit B are given in the examples described later. Other methods include the following.
For example, when the unit B is represented by the general formula (6), the compound constituting the unit B includes a compound having a structure represented by the following general formula (26). The compound represented by the following general formula (26) is synthesized, for example, by the following method. First, a halide of the metal atom or metalloid atom X and a diamine covalently bonded to a polymerizable group having R ¹ via (L ¹ and R ² ) which are part of the second spacer in a solution. Mix to obtain a complex. Subsequently, silver sulfate is added and the precipitated silver chloride is filtered off, and then oxalic acid and an aqueous sodium hydroxide solution are added and stirred overnight. A compound represented by the following formula (26) can be obtained by collecting the obtained precipitate.

The unit C can be synthesized by an ordinary method for synthesizing a monomer having an acid dissociable group. For example, Japanese Patent Publication No. WO2009 / 110388 may be quasi-treated.
Several examples of the synthesis of unit D will be given in the examples described later. Other methods include, for example, WO2016 / 130773.
The unit E can be synthesized by an ordinary method for synthesizing a monomer having a structure that acts as an acid proliferating agent. For example, Journal of Photopolymer science and Technology 17 (2004) 427-432 may be semi-processed.
The unit F can be synthesized by an ordinary method for synthesizing a monomer containing a lactone, a sultone skeleton or the like. For example, Japanese Patent Application Laid-Open No. 2011-184390 may be semi-processed.

<2> Resist composition The resist composition of one aspect of the present invention is characterized by containing the above-mentioned polymer. In addition to the above polymer, it may optionally contain components such as a sensitizing compound, an organometallic compound, and an organometallic complex. Hereinafter, each component will be described.

(Sensitizing compound)
The resist composition of one embodiment of the present invention may contain only the above polymer, but in addition to the above polymer, other components such as the above general formulas (12) to (14) contained in the unit D may be used. ) May be further contained as a single unit, not as a polymer unit. By containing these in the resist composition, it can act as a sensitizer and can increase the sensitivity to particle beams or electromagnetic waves.

  The content of the sensitizing compound in the resist composition is preferably 0 to 1 molar equivalent relative to the total amount of the unit A and the unit B.

(Organometallic compounds and organometallic complexes)
It is preferable that the resist composition of one embodiment of the present invention further contains either an organometallic compound or an organometallic complex.
The metals are Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Hf, Ta, W, The unit A and the unit B are sensitized to be at least one selected from the group consisting of Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn, and Ra. It is preferable because it is possible.

Examples of the organometallic compound include tetraaryl tin, tetraalkyl tin, and bis (alkylphosphine) platinum.
Examples of the organometallic complex include hafnium (IV) acrylate, zirconium (IV) acrylate, bismuth (III) acrylate, bismuth (III) acetate, and tin (II) oxalate.
The amount of the organometallic compound and organometallic complex in the resist composition is preferably 0 to 0.5 molar equivalents relative to unit A.

(Other ingredients)
In any embodiment, the resist composition of one embodiment of the present invention may contain other components as long as the effects of the present invention are not impaired. As components that can be blended, known additives, such as fluorine-containing water-repellent polymers, acid diffusion control agents, surfactants, fillers, pigments, antistatic agents, flame retardants, light stabilizers, antioxidants, You may add at least 1 chosen from an ion supplement agent, organic carboxylic acid, a dissolution inhibitor, a solvent, etc.

  Examples of the fluorine-containing water-repellent polymer include those usually used in an immersion exposure process, and it is preferable that the fluorine atom content is higher than that of the polymer. Accordingly, when the resist film is formed using the resist composition, the fluorine-containing water-repellent polymer can be unevenly distributed on the resist film surface due to the water-repellent property of the fluorine-containing water-repellent polymer. .

  The surfactant is preferably used for improving the coating property. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Agents, fluorosurfactants, organosiloxane polymers, and the like.

  The content of the surfactant is preferably 0.0001 to 2 parts by mass and more preferably 0.0005 to 1% by mass with respect to 100 parts by mass of the resist composition component.

  The acid diffusion control agent controls the diffusion phenomenon of the acid generated from the photoacid generator in the resist film, and has an effect of controlling an undesirable chemical reaction in the non-exposed region. Therefore, the storage stability of the resulting resist composition is further improved, the resolution as a resist is further improved, and changes in the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing can be suppressed. Thus, a resist composition having excellent process stability can be obtained.

  Examples of the acid diffusion controller include a compound having one nitrogen atom in the same molecule, a compound having two, a compound having three nitrogen atoms, an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. It is done. Further, as the acid diffusion controlling agent, a photodegradable base that is sensitized by exposure to generate a weak acid can also be used. Examples of the photodegradable base include onium salt compounds and iodonium salt compounds that lose acid diffusion controllability by being decomposed by exposure.

  Specific examples of the acid diffusion control agent include Japanese Patent No. 3577743, Japanese Patent Application Laid-Open No. 2001-215589, Japanese Patent Application Laid-Open No. 2001-166476, Japanese Patent Application Laid-Open No. 2008-102383, Japanese Patent Application Laid-Open No. 2010-243773, and Japanese Patent Application Laid-Open No. 2011-37835. Examples thereof include compounds described in Kai 2012-173505.

  The content of the acid diffusion controller is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resist composition component. More preferably, it is 3 parts by mass.

  Examples of the organic carboxylic acid include aliphatic carboxylic acid, alicyclic carboxylic acid, unsaturated aliphatic carboxylic acid, oxycarboxylic acid, alkoxycarboxylic acid, ketocarboxylic acid, benzoic acid derivative, phthalic acid, terephthalic acid, isophthalic acid, 2 -Naphthoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, etc. can be mentioned. When performing electron beam exposure in a vacuum, there is a risk of volatilizing from the resist film surface and contaminating the drawing chamber. Therefore, preferred organic carboxylic acids include aromatic organic carboxylic acids, among which, for example, benzoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxy-3-naphthoic acid are preferred.

  The content of the organic carboxylic acid is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the resist composition component. It is.

  Examples of the organic solvent include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether. Acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone Alcohol, N-methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetoa Mido, propylene carbonate, ethylene carbonate and the like are preferable. These organic solvents are used alone or in combination.

  The resist composition component is preferably dissolved in the solvent at a solid content concentration of 1 to 40% by mass. More preferably, it is 1-30 mass%, More preferably, it is 3-20 mass%. By setting the solid content concentration in such a range, the above film thickness can be achieved.

  When the resist composition of one embodiment of the present invention contains a polymer, the polymer preferably has a weight average molecular weight of 2000 to 200000, more preferably 2000 to 50000, and further preferably 2000 to 15000. preferable. The preferable dispersion degree (molecular weight distribution) (Mw / Mn) of the polymer is 1.0 to 1.7, more preferably 1.0 to 1.2, from the viewpoint of sensitivity. The weight average molecular weight and dispersity of the polymer are defined as polystyrene converted values by GPC measurement.

  The composition of one aspect of the present invention is obtained by mixing the components of the above composition, and the mixing method is not particularly limited.

<3> Method for Preparing Resist Composition The method for preparing the resist composition according to one aspect of the present invention is not particularly limited, and is prepared by a known method such as mixing, dissolving, or kneading the polymer and other optional components. be able to.
The polymer can be synthesized by appropriately polymerizing monomers constituting the units A and B and, if necessary, monomers constituting other units by a usual method. However, the method for producing the polymer according to the present invention is not limited to this.

<4> Device Manufacturing Method One embodiment of the present invention includes a step of forming a resist film on a substrate using the resist composition, a step of exposing the resist film using particle beams or electromagnetic waves, And developing the exposed resist film to obtain a pattern.

Examples of the particle beam or electromagnetic wave used for exposure in the exposure step include an electron beam and EUV.
The amount of light irradiation varies depending on the type and blending ratio of each component in the resist composition and the film thickness of the coating film, but is preferably 1 J / cm ² or less or 1000 μC / cm ² or less.
When the resist composition is contained as a sensitizing unit (unit D) in the polymer or as a sensitizing compound, it is irradiated with a first active energy ray such as a particle beam or an electromagnetic wave and then second active with ultraviolet rays or the like. It is also preferable to perform irradiation with energy rays.

One embodiment of the present invention includes a step of forming a resist film, a step of irradiating a first active energy ray, a step of irradiating a second active energy, and a step of forming a pattern using the composition. The manufacturing method of the board | substrate which has a pattern before including an individualization chip | tip may be sufficient.
One embodiment of the present invention comprises a step of forming a coating film on a substrate using the above composition, and exposing the coating film using a first active energy ray and optionally a second active energy ray, And a device manufacturing method including a step of obtaining an insulating film.

The first active energy ray and the second active energy ray are not particularly limited as long as the onium salt structure according to some embodiments of the present invention has no significant absorption in the second active energy ray. When the energy beam is a particle beam, the second active energy beam is preferably an electromagnetic wave. When the first active energy ray is an electromagnetic wave, the wavelength of the first active energy ray is preferably shorter than the wavelength of the second active energy ray. Each active energy ray is illustrated below.
The first active energy ray is not particularly limited as long as an active species such as an acid can be generated in the resist film after irradiation with the resist film. For example, KrF excimer laser light, ArF excimer laser light, electron beam or extreme Ultraviolet rays (EUV) and the like are preferable.

  As the second active energy ray, the sensitizing compound of the general formula (XI) or the acetal or thioacetal part of the unit D having the same is deprotected by the acid generated in the resist film after the irradiation of the first active energy ray. Any light that can activate the ketone derivative thus produced may be used. For example, it means KrF excimer laser light, UV, visible light, and the like, and it is particularly preferable to use light in the 365 nm (i-line) to 436 nm (g-line) region of UV light.

The substrate is not particularly limited, and a known substrate can be used. For example, a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, copper, chromium, or aluminum; a glass substrate;
In one embodiment of the present invention, active energy rays used for exposure in a photolithography process used for obtaining an interlayer insulating film or the like for LSI fabrication include UV, KrF excimer laser light, ArF excimer laser light, electron beam or Preferably, extreme ultraviolet (EUV) is used.

  In one embodiment of the present invention, the thickness of the resist film formed from the resist composition is preferably 10 to 200 nm. The resist composition is applied onto the substrate by an appropriate application method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, and the like, and is performed at 60 to 150 ° C. for 1 to 20 minutes, preferably 80 to A thin film is formed by prebaking at 120 ° C. for 1 to 10 minutes. The thickness of this coating film is 5 to 200 nm, and preferably 10 to 100 nm.

In one aspect of the present invention, the film formed of the resist composition is applied at 60 to 150 ° C. for 1 to 20 minutes after the first active energy ray irradiation and between the second active energy ray irradiation, preferably Post-bake at 80-120 ° C. for 1-10 minutes.
By performing the post-baking, the cross-linking reaction between the acid bonded to the polymer generated after the first active energy ray irradiation and the unit B proceeds, and the cross-linking density of the polymer chain can be improved.

Hereinafter, some embodiments of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
In the present invention, the molar extinction coefficient is at 365 nm in a chloroform solvent measured with a UV-VIS spectrophotometer using chloroform as a solvent.
<Synthesis of Compound A1 Constructing Unit A>
Synthesis Example 1 Synthesis of dibenzothiophene-9-oxide

  Dissolve 7.0 g of dibenzothiophene in 21.0 g of formic acid to 35 ° C. To this, 4.1 g of 35% by mass hydrogen peroxide solution is added dropwise and stirred at 25 ° C. for 5 hours. After cooling, the reaction solution is dropped into 50 g of pure water to precipitate a solid. The precipitated solid is separated by filtration, washed twice with 20 g of pure water, and then recrystallized using acetone. This is filtered and then dried to obtain 7.6 g of dibenzothiophene-9-oxide.

Synthesis Example 2 Synthesis of 9-phenyldibenzothiophenium-methanesulfonate

  7.0 g of dibenzothiophene-9-oxide obtained in Synthesis Example 1 and 2.7 g of benzene are dissolved in 33 g of methanesulfonic acid to 25 ° C. To this, 2.6 g of diphosphorus pentoxide is added and stirred at room temperature for 15 hours. Thereafter, 105 g of pure water was added and the mixture was further stirred for 5 minutes, and then washed twice with 35 g of ethyl acetate to obtain 115 g of an aqueous 9-phenyldibenzothiophenium-methanesulfonate solution.

Synthesis Example 3 Synthesis of 9-phenyldibenzothiophenium-para-styrene sulfonate (Compound A1)

115 g of the 9-phenyldibenzothiophenium-methanesulfonate aqueous solution obtained in Synthesis Example 2 above, 5.8 g of para-styrenesulfonate, and 220 g of methylene chloride are mixed and stirred at 25 ° C. for 3 hours. After stirring, the organic layer was recovered and washed with 100 g of pure water three times. The recovered organic layer was concentrated, and the resulting solid was dried to give 9-phenyldibenzothiophenium-para-styrenesulfonate (compound A1 9.9 g). The obtained compound has a molar extinction coefficient at 365 nm of 1.0 × 10 ⁵ cm ² / mol or less.

<Synthesis of Compound A2 Constructing Unit A>
Synthesis Example 4 Synthesis of 9-phenyldibenzothiophenium-4-methacryloxy-1,1,2-trifluorobutanesulfonate (Compound A2)

  9-phenyldibenzothiophenium was obtained by performing the same operation as in Synthesis Example 3 except that sodium 4-methacryloxy-1,1,2-trifluorobutanesulfonate was used in place of sodium para-styrenesulfonate. 12 g of -4-methacryloxy-1,1,2-trifluorobutanesulfonate (compound A2) is obtained.

<Synthesis of Compound A3 Constructing Unit A>
Synthesis Example 5 Synthesis of sodium 2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate

  Mix 1,7.5 g of sodium 2,3,5,6-tetrafluoro-4-hydroxybenzenesulfonate with 6.2 g of methacrylic acid and 50 ml of tetrafluoroacetic acid. After cooling to 0 ° C., add 22 ml of trifluoroacetic anhydride for 30 minutes. Stir. Thereafter, volatile components were distilled off by a rotary evaporator, and the obtained white solid was washed with 100 ml of acetone and then dried to obtain 21 g of sodium 2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate. obtain.

Synthesis Example 6 Synthesis of 9-phenyldibenzothiophenium-2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate (Compound A3)

  9-Phenyldibenzothio was obtained by performing the same procedure as in Synthesis Example 3 except that sodium 2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate was used in place of sodium para-styrenesulfonate. 12.8 g of phenium-2,3,5,6-tetrafluoro-4-methacryloxybenzenesulfonate (compound A3) is obtained.

Synthesis Example 7 Triphenylsulfonium-methanesulfonate

  115 g of triphenylsulfonium-methanesulfonate aqueous solution is obtained by performing the same operation as in Synthesis Example 2 except that diphenylsulfoxide is used instead of dibenzothiophene-9-oxide.

<Synthesis of Compound A4 Constructing Unit A>
Synthesis Example 8 Synthesis of N-methacryl-N-methylaminoethanesulfonic acid

  Add 3.6 g of methacrylic acid and 32.5 g of diisopropylethylamine to 752 g of dichloromethane, cool to −30 ° C., add 13.7 g of diethyl cyanophosphate and stir. After 20 minutes, the temperature is raised to −20 ° C., and 47 g of a dichloromethane solution of 4.9 g of N-methylaminoethanesulfonic acid is added. Two hours later, 252 g of 1N hydrochloric acid aqueous solution was added, the organic layer was recovered, and the composition obtained by concentration was purified by column chromatography to obtain 5.8 g of N-methacryl-N-methylaminoethanesulfonic acid. .

Synthesis Example 9 Synthesis of triphenylsulfonium-N-methacryl-N-methylaminoethanesulfonate (Compound A4)

  5.8 g of N-methacryl-N-methylaminoethanesulfonic acid obtained in Synthesis Example 8 and 1.1 g of sodium hydroxide were dissolved in 30 g of pure water, and then triphenylsulfonium-methane obtained in Synthesis Example 7 was used. Add 125 g of sulfonate aqueous solution and 220 g of dichloromethane and stir for 3 hours. Thereafter, the organic layer was recovered and washed three times with 100 g of pure water, and then the recovered organic layer was concentrated, and the resulting solid was dried to give 9-phenyldibenzothiophenium-N-methacryl-N-methylamino. 11 g of ethanesulfonate (compound A4) are obtained.

<Synthesis of Compound A5 Constructing Unit A>
Synthesis Example 10 Synthesis of triphenylsulfonium-4-vinylbenzoate (Compound A5)

  Triphenylsulfonium-4-vinylbenzoate (Compound A5) was converted to 2 by performing the same procedure as in Synthesis Example 9 except that 4-vinylbenzoic acid was used instead of N-methacryl-N-methylaminoethanesulfonic acid. .8 g is obtained.

Synthesis Example 11 Synthesis of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium-methanesulfonate

  1- (4-methoxynaphthalene-1-) is obtained by performing the same operation as in Synthesis Example 2 except that tetramethylene sulfoxide is used instead of dibenzothiophene-9-oxide and 1-methoxynaphthalene is used instead of benzene. Yl) 114 g of tetrahydrothiophenium-methanesulfonate aqueous solution is obtained.

<Synthesis of Compound A6 Constructing Unit A>
Synthesis Example 12 Synthesis of 2,6-difluoro-4-vinylbenzoic acid

  8.3 g of 4-vinyl-2,6-difluoro-benzoic acid and 8.4 g of magnesium sulfate, 4.2 g of 2,4,6-trivinylcyclotriboroxane / pyridine complex, 0.44 g of tetrakistriphenylphosphine palladium, 7.0 g of calcium carbonate is dissolved in 150 g of pure water and 477 g of 1,2-dimethoxyethane and refluxed for 20 hours. Thereafter, 500 g of ethyl acetate was added and the collected organic layer was concentrated and purified by column chromatography to obtain 5.2 g of 2,6-difluoro-4-vinylbenzoic acid.

Synthesis Example 13 Synthesis of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium-2,6-difluoro-4-vinylbenzoate (Compound A6)

  Except for using 2,6-difluoro-4-vinylbenzoic acid in place of N-methacryl-N-methylaminoethanesulfonic acid and using 5-naphthyltetramethylenesulfonium-methanesulfonate in place of triphenylsulfonium-methanesulfonate The same operation as in Synthesis Example 9 is performed to obtain 4.4 g of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium-2,6-difluoro-4-vinylbenzoate (Compound A6).

<Synthesis of Compound A7 Constructing Unit A>
Synthesis Example 14 Synthesis of methyl 1-methacryl-4-piperidinecarboxylate

  5.9 g of methyl 1-methacryl-4-piperidinecarboxylate is obtained by performing the same operation as in Synthesis Example 8 except that methyl 4-piperidinecarboxylate is used in place of N-methylethanesulfonic acid.

Synthesis Example 15 Synthesis of triphenylsulfonium-1-methacryl-4-piperidinecarboxylate (Compound A7)

  Instead of N-methacryl-N-methylaminoethanesulfonic acid, methyl 1-methacryl-4-piperidinecarboxylate was used and heated to 70 ° C. for 1 hour to cool to 25 ° C. after hydrolysis, and then triphenylsulfonium- 2.3 g of triphenylsulfonium-1-methacryl-4-piperidinecarboxylate (Compound A7) is obtained by performing the same operation as in Synthesis Example 9 except that methanesulfonate is added.

<Synthesis of Compound A8 Constructing Unit A>
Synthesis Example 16 Synthesis of dibenzothiophen-2-yl-dibenzothiophenium-methanesulfonate

  118 g of dibenzothiophen-2-yl-dibenzothiophenium-methanesulfonate aqueous solution is obtained by performing the same operation as in Synthesis Example 2 except that dibenzothiophene is used instead of benzene.

Synthesis Example 17 Synthesis of 2,2,3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanoic acid

  7.1 g of 4-bromostyrene is dissolved in 32 g of tetrahydrofuran, and 39 ml of 1 mol / L methylmagnesium bromide in THF is added dropwise at 5 ° C. or lower. After dropping, the mixture is stirred at 5 ° C. or lower for 30 minutes to obtain a THF solution of 4-vinylphenylmagnesium bromide. To a solution of 9.5 g of 2,2,3,3,4,4-hexafluoropentanedioic anhydride in 15 g of THF, a THF solution of 4-methylthiophenylmagnesium bromide was added dropwise at 10 ° C. or lower, and then 25 Stir for 1 hour at ° C. After stirring, 50 g of a 10% by mass aqueous ammonium chloride solution is added at 20 ° C. or lower and the mixture is further stirred for 10 minutes, and the organic layer is extracted with 80 g of ethyl acetate. The solid obtained by distilling off ethyl acetate and tetrahydrofuran after washing with water was purified by column chromatography to obtain 2,2,3,3,4,4-hexafluoro-4- (4-vinylbenzoyl). ) Obtain 9.1 g of butanoic acid.

Synthesis Example 18 Synthesis of dibenzothiophen-2-yl-dibenzothiophenium-2,2,3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanate (Compound A8)

  Use 2,2,3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanoic acid instead of N-methacryl-N-methylaminoethanesulfonic acid and replace with triphenylsulfonium-methanesulfonate 9- (2-dibenzothiophenyl) dibenzothiophenium-2,2, by performing the same operation as in Synthesis Example 9 except that dibenzothiophen-2-yl-dibenzothiophenium-methanesulfonate is used. 11.6 g of 3,3,4,4-hexafluoro-4- (4-vinylbenzoyl) butanate (compound A8) is obtained.

<Synthesis of Compound A9 Constructing Unit A>
Synthesis Example 19 Synthesis of bis (4-tert-butylbenzene) iodonium-4-methacryloxy-1,1,2-trifluorobutanesulfonate (Compound A9)

  To 36 g of sulfuric acid, 9.1 g of 1-iodo-4-tert-butylbenzene is added, and then 35 g of potassium persulfate is added little by little at 10 ° C. or lower and stirred for 30 minutes. After stirring, 62.8 g of t-butylbenzene is added and further stirred at 25 ° C. for 3 hours. After stirring, 68.2 g of pure water was added at 10 ° C. or lower, 90 g of methylene chloride and 11.5 g of sodium 4-methacryloyloxy-1,1,2-trifluorobutanesulfonate were added, and the mixture was stirred at 25 ° C. for 2 hours. Stir to the extent. This is separated, washed three times with water, and methylene chloride is distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography (methylene chloride / methanol = 90/10 (volume ratio)) to give bis (4-tert-butylbenzene) iodonium-4-methacryloxy-1,1,2-trifluoro. 18.7 g of butanesulfonate (compound A9) are obtained.

<Synthesis of Compound A10 Constructing Unit A>
Synthesis Example 20 Synthesis of 4-bromo-4′-phenylsulfanylbenzophenone

  Add 3.0 g of aluminum chloride to 28 g of methylene chloride and bring to 0 ° C. To this is added 4.0 g of diphenyl sulfide, and then 3.4 g of 4-bromobenzoyl chloride is dissolved in 6.8 g of methylene chloride and added dropwise over 30 minutes. After dropping, the mixture is stirred at 25 ° C. for 1 hour, added with 60 g of pure water, further stirred for 5 minutes, and then washed twice with 20 g of toluene. This is separated, and the obtained organic layer is evaporated. The obtained residue is purified by recrystallization using 30 g of isopropyl alcohol to obtain 5.2 g of 4-bromo-4′-phenylsulfanylbenzophenone.

Synthesis Example 21 Synthesis of 4-bromo-4′-phenylsulfanylbenzophenone dimethyl acetal

  Dissolve 5.0 g of 4-bromo-4′-phenylsulfanylbenzophenone obtained in Synthesis Example 20 in 30 g of methanol, add 5.0 g of trimethyl orthoformate and 30 mg of concentrated sulfuric acid, and stir at 60 ° C. for 4 hours. To do. After stirring, 150 g of 3% by mass sodium bicarbonate water is added and the mixture is further stirred for 10 minutes to precipitate a solid. The precipitated solid is filtered off and redissolved in 30 g of methylene chloride. After washing this with water three times, methylene chloride was distilled off to obtain 5.0 g of 4-bromo-4′-phenylsulfanylbenzophenone dimethyl acetal.

Synthesis Example 22 Synthesis of {4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenyl} diphenylsulfonium-para-styrenesulfonate (Compound A10)

To the pre-dried flask, 2.0 g of tetrahydrofuran, 0.4 g of magnesium and 1,2-dibromoethane are added to activate the magnesium. After confirming the activation, the solution was heated to 50 ° C., and 4.0 g of 4-bromo-4′-phenylsulfanylbenzophenone dimethyl acetal obtained in Synthesis Example 20 was dissolved in 6.0 g of THF. Is dripped. After the dropwise addition, the mixture is stirred at 50 ° C. for 5 hours to obtain a THF solution of 4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenylmagnesium bromide. In a solution of 1.9 g of diphenyl sulfoxide, 1.8 g of trimethylsilyl chloride and 0.8 g of triethylamine in 9.5 g of methylene chloride, a THF solution of 4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenylmagnesium bromide was added. The solution is added dropwise at 10 ° C or lower, and then stirred at 25 ° C for 1 hour. After stirring, 30 g of a 10% by mass aqueous ammonium chloride solution is added at 5 ° C. or lower, and the mixture is further stirred for 10 minutes and washed twice with 5.0 g of isopropyl ether. Thereafter, 40 g of methylene chloride and 2.2 g of sodium para-styrenesulfonate are added and stirred at 25 ° C. for about 2 hours. This is separated and washed three times with water, and then methylene chloride is distilled off to obtain crude crystals. The crude crystals are purified by silica gel column chromatography (methylene chloride / methanol = 90/10 (volume ratio)) to give {4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenyl} diphenylsulfonium-para-styrenesulfonate. 5.4 g of (Compound A10) is obtained. The obtained compound has a molar extinction coefficient at 365 nm of 1.0 × 10 ⁵ cm ² / mol or less.

Synthesis Example 23 Synthesis of [4- (4-phenylsulfanylbenzoyl) phenyl] diphenylsulfonium-para-styrenesulfonate (Compound A11)

Dissolve 2.0 g of {4- [dimethoxy- (4-phenylsulfanylphenyl) methyl] phenyl} diphenylsulfonium-para-styrenesulfonate obtained in Synthesis Example 22 in 20 g of methanol. To this solution, 0.05 g of methanesulfonic acid is added and stirred at 30 ° C. for 2 hours. After stirring, 0.1 g of triethylamine is added, and then methanol is distilled off. By purifying the obtained crude crystals by silica gel column chromatography, 1.3 g of [4- (4-phenylsulfanylbenzoyl) phenyl] diphenylsulfonium-para-styrenesulfonate (compound A11) is obtained. The obtained compound has a molar extinction coefficient of 365 nm of 7.0 × 10 ⁶ cm ² / mol.

<Synthesis of Compound B1 Constructing Unit B>
(Synthesis Example 23) Synthesis of 4-vinylphenyl-triphenyltin (Compound B1)

  Add 1.2 g of magnesium and 6 g of THF to a flask from which moisture has been removed. A solution prepared by dissolving 6.0 g of 4-vinylbromobenzene in 12.0 g of THF is dropped into this over 1 hour. After stirring for 1 hour after the dropwise addition, the resulting 4-vinylphenylmagnesium bromide solution is added dropwise at 5 ° C. over 30 minutes into a flask prepared by separately adding 7.3 g of triphenyltin chloride and 36 g of THF. After dripping, after stirring for 30 minutes, 600 g of 1% ammonium chloride aqueous solution is added, and further stirred for 10 minutes. Then, THF is distilled off and extraction is performed using 60 g of toluene. This is separated, and the obtained organic layer is washed three times with 60 g of pure water. Then, the organic layer obtained by liquid separation was distilled off and then purified by column chromatography (ethyl acetate / hexane = 5/95 (volume ratio)) to give 4-vinylphenyl-triphenyltin (compound 5.6 g of B1) are obtained.

<Synthesis of Compound B2 Constructing Unit B>
Synthesis Example 24 Synthesis of 4-isopropenylphenyl-triphenyltin (Compound B2)

  7.1 g of 4-isopropenylphenyl-triphenyltin (compound B2) is obtained by performing the same operation as in Synthesis Example 23 except that 4-isopropenylbromobenzene is used instead of 4-vinylbromobenzene.

<Synthesis of Compound B3 Constructing Unit B>
(Synthesis Example 25) Synthesis of 4-vinylphenyl-tributyltin (Compound B3)

  5.1 g of 4-vinylphenyl-tributyltin (compound B3) is obtained by performing the same operation as in Synthesis Example 23 except that tributyltin chloride is used instead of triphenyltin chloride.

<Synthesis of Compound B4 Constructing Unit B>
(Synthesis Example 26) Synthesis of 4-vinylphenyl-triphenylgermane (Compound B4)

  3.1 g of 4-vinylphenyl-tributylgermane (compound B4) is obtained by performing the same operation as in Synthesis Example 23 except that triphenylgermanium chloride is used instead of triphenyltin chloride.

<Synthesis of Compound B5 constituting Unit B>
Synthesis Example 27 Synthesis of phenyl-4-styrenyl telluride (Compound B5)

  8.6 g of phenyl-4-styrenyl telluride (Compound B5) is obtained by performing the same operation as in Synthesis Example 23 except that diphenyl detelluride is used instead of triphenyltin chloride.

<Synthesis of Compound Constructing Unit D1>
Synthesis Example 28 Synthesis of 4- (2-vinyloxy) ethylthiobromobenzene

  4-Bromothiophenol 5.0 g, chloroethyl vinyl ether 5.7 g and potassium carbonate 7.3 g were dissolved in acetone 20 g and stirred at reflux temperature for 3 hours. Then, it cooled to room temperature, 60 g of pure waters were added, and it stirred for 5 minutes. To this, 90 g of toluene was added for extraction, followed by separation and washing with water. Thereafter, toluene is distilled off to obtain 6.4 g of 4- (2-vinyloxy) ethylthiobromobenzene.

Synthesis Example 29 Synthesis of 4- (2-vinyloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone

  10.2 g of 4- (2-vinyloxy) ethylthiobromobenzene is dissolved in 32 g of tetrahydrofuran, and 39 ml of 1 mol / L methylmagnesium bromide in THF is added dropwise at 5 ° C. or lower. After dropping, the mixture is stirred at 5 ° C. or lower for 30 minutes to obtain a THF solution of 4-methylthiophenylmagnesium bromide. To a solution of 8.8 g of 2,4-dimethoxybenzoyl chloride dissolved in 15 g of THF, a THF solution of 4-methylthiophenylmagnesium bromide is dropped at 10 ° C. or lower, and then stirred at 25 ° C. for 1 hour. After stirring, 50 g of a 10% by mass aqueous ammonium chloride solution is added at 20 ° C. or lower and the mixture is further stirred for 10 minutes, and the organic layer is extracted with 80 g of ethyl acetate. After washing with water, ethyl acetate and tetrahydrofuran are distilled off to obtain crude crystals. The crude crystals are recrystallized from 120 g of ethanol to obtain 8.4 g of 4- (2-vinyloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone).

Synthesis Example 30 Synthesis of 4- (2-hydroxy) ethylthio-2 ′, 4′-dimethoxybenzophenone

  4- (2-vinyloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone (5.0 g), pure water (3.3 g) and pyridinium-p-toluenesulfonic acid (0.44 g) were added to acetone (30 g) at reflux temperature. Stir for 3 hours. After cooling to room temperature, 85 g of pure water was added and the mixture was stirred for 5 minutes and extracted with ethyl acetate. After separating and washing this with water, the ethyl acetate was distilled off to obtain 4.6 g of 4- (2-hydroxy) ethylthio-2 ′, 4′-dimethoxybenzophenone.

Synthesis Example 31 Synthesis of 4- (2-methacryloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone

4- (2-Hydroxy) ethylthio-2 ′, 4′-dimethoxybenzophenone (5 g) and methacrylic anhydride (2.9 g) are dissolved in THF (15 g), and 1.9 g of triethylamine is added dropwise to the mixture so that the temperature is 20 ° C. or lower. To do. After dripping, after stirring at 25 degreeC for 3 hours, 40 g of pure waters are added, and also it stirs for 10 minutes. This is extracted with 50 g of ethyl acetate and separated and washed with pure water. Thereafter, ethyl acetate is distilled off to obtain 5.1 g of the desired 4- (2-methacryloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone. The obtained compound has a molar extinction coefficient at 365 nm of 1.1 × 10 ⁶ cm ² / mol.

Synthesis Example 32 Synthesis of 4-[(2-methacryloxy) ethylthio] -phenyl- (2 ′, 4′-dimethoxyphenyl) dimethoxymethane (Compound D1)

4- (2-Methacryloxy) ethylthio-2 ′, 4′-dimethoxybenzophenone (6.7 g), sulfuric acid (47 mg) and trimethyl orthoformate (13.5 g) are dissolved in methanol (12.5 g), and this is stirred at reflux temperature for 3 hours. . Thereafter, the mixture is cooled to room temperature, and 50 g of a 5% by mass aqueous sodium hydrogen carbonate solution is added thereto, followed by further stirring for 10 minutes, and the precipitated crystals are filtered. The crystals are recovered, redissolved in 50 g of ethyl acetate and washed with water. Then, 2.6 g of 4-[(2-methacryloxy) ethylthio] -phenyl- (2 ′, 4′-dimethoxyphenyl) dimethoxymethane (Compound D) is obtained by distilling off ethyl acetate.
The obtained compound has a molar extinction coefficient at 365 nm of 1.0 × 10 ⁵ cm ² / mol or less.

<Synthesis of Polymer 1>
(Synthesis Example 33) Synthesis of Polymer 1

3.6 g of compound A1 constituting unit A, 5.3 g of compound B1 constituting unit B, and 0.31 g of dimethyl-2,2′-azobis (2-methylpropionate) as a polymerization initiator Deoxygenated by dissolving 0.06 g of 2-mercaptoethanol in a mixed solution of 9 g of methanol, 9 g of γ-butyrolactone, and 9 g of cyclohexanone. This is added dropwise over 4 hours to a mixed solution of 3 g of methanol, 3 g of γ-butyrolactone, and 3 g of cyclohexanone, which has been heated to 70 ° C. in advance. After dropping, the mixture is stirred for 2 hours and then cooled. After cooling, it is reprecipitated by adding dropwise to 90 g of diisopropyl ether. This is filtered and vacuum-dried to obtain 5.4 g of the target polymer 1.
Although the polymer unit ratios are disclosed above, the polymers of some embodiments of the present invention are not so limited.

<Synthesis of polymers 2 to 28>
(Synthesis Example 34) Synthesis of Polymers 2 to 28 Following Synthesis Example 33, the compounds A1 to A6 constituting the unit A, the compounds B1 to B5 constituting the unit B, the monomers C1 to C5 constituting the unit C, Polymers 2-28 were synthesized using the compound D1 constituting the unit D, the monomer E1 constituting the unit E, the monomers F1 to F3 constituting the unit F, and the monomer G1 having low reactivity with respect to the acid. Monomers C1 to C2 and monomers F1 and F3 are purchased products, and monomers E1 and F2 and monomer G1 were synthesized by esterifying an alcohol form serving as a precursor of the compound according to the above publications and documents. The structure is shown below.
Details of each synthesized polymer are shown in Table 1.
Monomer C1: 4-tert-butoxystyrene monomer C2: 1-ethoxyethoxy methacrylate monomer E1: 2-hydroxypinanyl-3-parastyrene sulfonate monomer F1: α-methacryloxy-γ-butyrolactone monomer F2: 2-methacryloyloxy- 1,3-propane sultone monomer F3: 3-hydroxyadamantane-1-methacrylate monomer G1: triphenyl- (4-methacryloxyphenyl) methane additive A: (4-methylthio) phenyl- (4′-phenylthio) phenyl- Dimethoxymethane

<Preparation of resist composition>
(Sample preparation of Examples 1-6 and Comparative Example 1)
400 mg of any of the above polymers is dissolved in a mixed solvent of 4 ml of γ-butyrolactone and 4 ml of cyclohexanone to prepare resist composition samples of Examples 1 to 6 and Comparative Example 1. For the sample of Example 5, 45 mg of additive A is further added as a sensitizing compound. The composition of the sample is described in Table 2 and Table 3.

(Adjustment of the sample of Comparative Example 2)
350 mg of p-hydroxystyrene (molecular weight 8000), 1,3,4,6-tetrakis (methoxymethyl) glycoluril 30 mg as a crosslinking agent, 20 mg triphenylsulfonium-nonafluorosulfonate as an acid generator and trioctyl as an acid diffusion controller Sample 5 shown in Comparative Example 2 is prepared by dissolving 1.5 mg of amine in 8 ml of cyclohexanone.

<Preparation of developer>
Among the polymers 1 to 28, pure water, methanol, tetrahydrofuran (THF), acetonitrile (so that 15% by mass of each polymer is dissolved in the polymers 1, 2, 11, 13, 18 and 28 used in the sensitivity evaluation. AN) and methyl ethyl ketone (MEK) are blended so that the composition is in the range of 0 to 90% by volume, respectively, and a developer corresponding to each polymer is prepared. The results for polymers 1, 2, 11, 13, 18 and 28 are shown in Table 2.

<Electron beam sensitivity evaluation>
The resist composition sample 1 is spin-coated on a silicon wafer previously modified with hexamethylene disilazane. This is pre-baked on a hot plate at 110 ° C. for 1 minute to obtain a substrate on which a coating film having a thickness of 200 nm is formed. On the coating film of the substrate, an electron beam drawing apparatus is used to draw a 2 μm line and space pattern with a 30 keV electron beam. The substrate after electron beam irradiation is post-baked on a hot plate at 130 ° C. for 5 minutes, developed for 1 minute using the developer, and then rinsed with pure water to obtain a 2 μm line-and-space pattern. Sensitivity by electron beam irradiation is determined with the irradiation amount at this time being E _max [μC / cm ² ]. Moreover, it is evaluated whether the rectangular pattern is obtained by observing the shape of the obtained pattern. The case where a rectangular pattern is obtained is evaluated as ◯, the case where a tapered pattern shape is obtained is evaluated as Δ, and the case where a pattern is not obtained is evaluated as ×.
For the samples 2 to 4 in Examples 1 to 3 and Comparative Example 1, the sensitivity was evaluated in the same manner as described above, and only the sample 5 in Comparative Example 2 was 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAH). ) To develop the sensitivity.
The results are shown in Table 3. In Table 3, the sensitivity of Example 1 is set to 100, and the evaluation results of the samples (Examples 2 and 3 and Comparative Examples 1 and 2) are calculated as relative values.

  In Examples 1 to 3 of Table 3, the solubility is changed by the crosslinking reaction between the generated polymer acid and the unit B by heating after the electron beam irradiation, and a pattern can be obtained. On the other hand, in the case of the comparative example 1 which used the unit G which does not have a metal atom instead of the unit B, even if it irradiates 5 times or more of Example 1, it cannot pattern. This is because the unit B has a dissolution contrast between the exposed part and the unexposed part due to the cross-linking reaction between the polymer-type conjugated base and the unit B is important in the construction of the cross-linked structure. It can be seen that it is.

  From the comparison between Example 1 and Comparative Example 2 in Table 3, it can be seen that the results of Example 1 are superior to Comparative Example 2 in sensitivity and pattern shape. In Example 1, the efficiency of secondary electron generation by electron beam irradiation is improved by introducing the unit B having a structure containing a metal atom or an antimetal atom (a structure containing a tin atom). Thereby, the decomposition efficiency of the unit A increases. Therefore, the sensitivity is higher than that of Comparative Example 2 which utilizes the catalytic reaction of a slight acid generated by electron beam irradiation. By dispersing units A and B uniformly in the polymer by polymerization, the polymer acid is uniformly distributed in the film. It can be said that the pattern shape is improved due to the occurrence. Since the tin atom contained in the unit B is also an atom having high EUV absorption, the same effect can be expected in EUV.

From the comparison between Example 1 and Example 2, the compound has a flexible fluoroalkyl group as a spacer structure between the polymer main chain and the acid structure, such as Compound A2 introduced into the polymer 2 of Example 2. Compared with the compound A1 having a phenylene group as a spacer structure, it undergoes molecular motion by heating, so that the cross-linking reaction easily occurs and becomes rigid, and the sensitivity is higher than that of the polymer 1 of Example 1. The spacer structure corresponds to the L ¹ and R ² portions of the above general formulas (1) and (2).

  From the comparison between Example 1 and Example 3, the polymer acid of the carboxylic acid produced by deprotection by the polymer acid generated from unit A by introducing unit C which is the acid dissociable group unit of Example 3 is exposed. By subsequent heating, a crosslinking reaction with unit B occurs. As a result, the crosslink density is improved and the sensitivity is superior. Since unit B has reactivity with acid, it can be deactivated competitively even if a unit that generates polymer acid with an acid catalyst such as unit C is introduced, so an acid diffusion controller is added. The pattern can be formed without doing so.

<Photosensitization evaluation>
After samples 6 to 8 were drawn using an electron beam so as to form a 2 μm line-and-space pattern after spin coating in the same manner as in the electron beam evaluation, the extracted wafer was exposed to a wavelength of 365 nm using a bandpass filter. Using a black light (FL8BL, manufactured by Hitachi Appliances, Inc.) adjusted to ± 5 nm, the entire surface of the wafer is irradiated with 500 mJ / cm ² . The substrate after UV irradiation is post-baked on a hot plate at 130 ° C. for 5 minutes, developed for 1 minute using the developer, and then rinsed with pure water to obtain a 2 μm line and space pattern. Sensitivity by electron beam irradiation is determined with the irradiation amount at this time being E _max [μC / cm ² ]. The results are shown in Table 4. In Table 4, the sensitivity of Example 1 in Table 3 was set as 100, and the evaluation result of the sample relative thereto was calculated as a relative value.

From comparison with Examples 4 to 7 in Table 4, polymer 1 that does not produce a compound having photosensitivity at 365 nm by acid-catalyzed reaction has a molar extinction coefficient at 365 nm as small as 1.0 × 10 ⁵ cm ² / mol or less. The sensitivity was not increased by light irradiation. On the other hand, when compound A10 which becomes compound A11 by acid-catalyzed reaction as unit A, or compound D1 and additive A which increases absorption at 365 nm by acid-catalyzed reaction are added to the polymer, acid is generated by absorbing 365 nm light. Or by acting as a sensitizer, it is possible to increase the sensitivity by promoting acid generation of the unit A.

  According to some embodiments of the present invention, it is possible to provide a polymer having a high absorption efficiency of particle beams such as EUV or electromagnetic waves and excellent in characteristics of sensitivity, resolution, and pattern performance, and a resist composition containing the polymer.

Claims (14)

A polymer comprising unit A and unit B,
The unit A has an onium salt structure having an anion portion and a cation portion, and generates a state in which a polymer-type conjugate base and a hydrogen cation are paired by irradiation with a particle beam or electromagnetic wave. The salt structure is covalently bonded to the polymer backbone directly or through a first spacer,
The unit B has a structure containing a metal atom or a metalloid atom, and the structure of the unit B is covalently or coordinately bonded to the polymer main chain directly or via a second spacer;
When the structure of the unit B is covalently bonded to a polymer chain, the polymer-type conjugate base is added or substituted with the metal atom or metalloid atom to form an acid ester structure or an ion pair; Or
When the structure of the unit B is coordinated to a polymer chain, the structure of the unit B has a coordinating substituent, and the polymer-type conjugate base and the coordinating substituent are coordinated. A polymer that builds a cross-linked structure by forming a complex structure through a child exchange reaction.   The metal atom or metalloid atom is B, Al, Si, As, Ti, Zr, Mo, Se, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rh, Pd, Ag. At least one atom selected from the group consisting of Cd, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, and At The polymer according to claim 1, wherein The polymer according to claim 1 or 2, wherein the unit A has at least one of the structures represented by the following general formulas (1) and (2).
(In the general formulas (1) and (2), R ¹ is any one selected from the group consisting of a hydrogen atom; a fluorine atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; And the alkyl group in R ¹ may have a substituent,
R ² is selected from the group consisting of a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms; an arylene group having 6 to 14 carbon atoms; and a heteroarylene group having 4 to 14 carbon atoms. And the alkylene group, arylene group, and heteroarylene group in R ² may have a substituent,
L ¹ is a direct bond; a carbonyloxy group; a carbonylamino group; a linear, branched or cyclic alkylenecarbonyloxy group; a linear, branched or cyclic alkylenecarbonylamino group; an arylenecarbonyloxy group; and an arylenecarbonylamino group; And the amino group, alkylene group and arylene group in L ¹ may have a substituent,
When R ¹ , R ² and L ¹ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond;
When having a methylene group in R ¹ , R ² and L ¹ , at least one of the methylene groups may be substituted with a divalent heteroatom-containing group;
M ⁺ is a sulfonium cation represented by the general formula (3) or an iodonium cation represented by the general formula (4). )
(In the general formulas (3) and (4), R ^{3 to} R ⁵ are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an aryl group having 6 to 14 carbon atoms; A heteroaryl group having 4 to 14 carbon atoms; any one selected from the group consisting of these, which may have a substituent,
When R ^{3 to} R ⁵ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond;
When R ^{3 to} R ⁵ have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group;
R ³ and R ⁴ form a ring structure together with a sulfonium cation or an iodonium cation to which R ³ and R ⁴ are bonded either directly or through a group selected from the group consisting of an oxygen atom, a sulfur atom and a methylene group. May be. ) The polymer according to claim 1, wherein the unit B has at least one of structures represented by the following general formulas (5) to (7).
(In the general formulas (5) to (7), R ¹ , R ² and L ¹ are each independently selected from the same options as R ¹ , R ² and L ^{1 in the} general formula (1),
R ⁶ is selected from the same options as R ^{5 in the} general formula (3),
X is the metal atom or metalloid atom,
C ¹ is a monodentate or multidentate ligand covalently bonded to R ² ,
C ² is an independent monodentate ligand or an independent polydentate ligand which is the coordinating substituent,
In the general formula (5), two or more of R ² and the plurality of R ⁶ are bonded to each other directly by a single bond or via a group selected from the group consisting of a methylene group. A ring structure may be formed together with X,
In the general formula (7), two or more of R ² , C ¹ and a plurality of R ⁶ are directly selected from a group consisting of a single bond or a methylene group. May form a ring structure together with X to which
h is the valence of X-1 and 0 to 3,
i is 1-6,
j is intended to be determined by the valency and coordination state of C ¹ and C ² of and X 0-5,
k is 0 to 5 and is determined by the valence of X and the coordination state of C ¹ ;
The polymer as described in any one of Claims 1-3 in which-> in the said General formula (6) and (7) shows a coordinate bond.   The polymer according to any one of claims 1 to 4, wherein X in the general formulas (5) to (7) has an atom selected from the group consisting of Sn, Sb, Ge, Bi, and Te. The polymer according to any one of claims 1 to 5, further comprising a unit C, wherein the unit C has any of the structures represented by the following general formulas (8) to (11).
(R ^{1, R 2} and ^{L 1} in the general formula (8) to (11) is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in the general formula (1),
R ⁷ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent,
R ⁸ and R ⁹ are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent,
Two or more of R ⁷ , R ⁸ and R ⁹ may form a ring structure either directly by a single bond or via any one selected from the group consisting of methylene groups,
R ¹⁰ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent,
R ¹¹ and R ¹² are each independently selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent. ,
Two or more of R ¹⁰ , R ¹¹ and R ¹² may form a ring structure either directly by a single bond or via any one selected from the group consisting of methylene groups,
R ¹³ is independently selected from the group consisting of an alkyl group; a hydroxy group; an alkoxy group; an alkylcarbonyl group; an alkylsulfanyl group; an alkylsulfinyl group; an alkylsulfonyl group; an amino group; a cyano group; a nitro group; And when the substituent has carbon, these have a substituent,
When R ^{7 to} R ¹³ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond;
When R ^{7 to} R ¹³ have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group;
l ¹ is an integer of ¹ to 2, m ¹ is an integer of 0 to 4 when l ¹ is 1, and an integer of 0 to 6 when l ¹ is 2,
n ¹ is 1-5 when ^{l 1} is 1, and 1-7 integer when ^{l 1} is 2,
m ¹ + n ¹ is 1 to 5 when l ¹ is 1, and ¹ to 7 when l ¹ is 2. ) Unit D is further contained, and the unit D has a structure in which any of the compounds represented by the following general formulas (12) to (14) is bonded to the R ² group of the following general formula (15). The polymer as described in any one of these.
(In the general formulas (12) to (14),
R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently selected from the group consisting of a hydrogen atom; an electron donating group; and an electron withdrawing group;
At least one of R ¹⁴ and R ¹⁵ is the electron donating group,
At least one of R ¹⁶ is the electron donating group,
R ¹⁷ is any one selected from the group consisting of a hydrogen atom; and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms which may have a substituent;
Each of R ¹⁸ is independently selected from the group consisting of a hydrogen atom; and an optionally substituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; Two R ¹⁸ may be bonded to each other to form a ring structure;
When R ^{14 to} R ¹⁸ have a carbon-carbon single bond, at least one of the carbon-carbon single bonds may be substituted with a carbon-carbon double bond or a carbon-carbon triple bond;
When R ^{14 to} R ¹⁸ have a methylene group, at least one of the methylene groups may be substituted with a divalent heteroatom-containing group;
E is any one selected from the group consisting of a direct bond, an oxygen atom; a sulfur atom and a methylene group;
m ³ is an integer of 0 or 1,
n ⁵ and n ⁶ are each an integer of 0 to 2, n ⁵ + n ⁶ is 2,
When n ⁵ is 1, n ³ is an integer from 0 to 4, when n ⁵ is 2, n ³ is an integer from 0 to 6, and when n ⁶ is 1, n ⁴ is an integer from 0 to 4. , When n ⁶ is 2, n ⁴ is an integer from 0 to 6,
n ⁷ is an integer of 0 to 7,
n ⁸ is 1 or 2, ^{n 7} when ^{n 8} is 1 is an integer of 0 to 5, ^{n 7} when ^{n 8} is 2 is an integer of 0-7. )
^(R 1, ^{R 2} and ^{L 1} in the general formula (15) is selected from the same options as ^R 1, ^{R 2} and ^{L 1} in the general formula (1),
* Represents a binding site with the compound represented by the general formulas (12) to (14). )   The resist composition containing the polymer as described in any one of Claims 1-7. Forming a resist film on a substrate using the resist composition according to claim 8;
Exposing the resist film using a particle beam or electromagnetic beam;
And developing the exposed resist film to obtain a pattern. Applying the composition according to claim 8 on a substrate to form a resist film;
Irradiating the resist film with a first active energy ray;
Irradiating the resist film after the first active energy ray irradiation with a second active energy ray;
And developing a resist film after the second active energy ray irradiation to obtain a pattern. The first active energy ray is a particle beam or an electromagnetic wave;
When the first active energy ray is a particle beam, the second active energy ray is an electromagnetic wave, and when the first active energy ray is an electromagnetic wave, the second active energy ray is the electromagnetic wave of the first active energy ray. The device manufacturing method according to claim 10, wherein the device has an electromagnetic wave longer than the wavelength of the device.   The device manufacturing method according to claim 10, comprising a step of heating with a heating wire or a laser between the step of irradiating the first active energy ray and the step of irradiating the second active energy ray. . Generating a first active species from the composition in the resist film by irradiation with the first active energy ray;
The onium salt of the unit A is structurally changed by the first active species,
The method for manufacturing a device according to claim 10, wherein a second active species is generated from the structurally changed onium salt by irradiation with the second active energy ray.   The device manufacturing method according to claim 13, wherein the structurally changed onium salt is a ketone derivative.