감방사선성 수지 조성물, 레지스트 패턴 형성 방법, 중합체 및 화합물의 제조 방법

<Radiation-sensitive resin composition >

The radiation-sensitive resin composition polymer, acid generator and a and and comprising at organic solvent. The radiation-sensitive resin composition as a component suitable, diffusion of acid control body, characteristic reinforcement, a powdered other than polymer-containing polymer (hereinafter, '[ E] polymer' also referred to as), fluorine atom containing polymer (hereinafter, '[ F] polymer' also referred to as) containing and may be, the present effect of the invention, without damage to it, in a range in which the output, other optional components may containing. The radiation-sensitive resin composition 2 1 each of which are associated one or each said at least one is as described above may be containing. Hereinafter, .also disclosed to each component.

<[A] 중합체 >

[A] polymer formula (1) that is connected to a represented by (hereinafter, 'to (I)' also referred to as) including a structural units (hereinafter, 'structural units (I)' also referred to as) is polymers having. The radiation-sensitive resin composition (I) polymer is by having structural units, while exhibiting wide focal depth, small LWR, each pixel having excellent rectangular mother pipe having a cross sectional shape in addition so as to form a resist pattern can be. The radiation-sensitive resin composition by having said configuration, said exerting a pounding effect reason although not clear so that, for example, can be symbol filtering unit hereinafter. I.e., polymer formula (1) that is connected to a represented by (-CO-CO-OR^P) has a. Is an ester groups (-CO-OR) than bit lines 110a, 110b is having high polarity. Furthermore, R^P is reinforcement, a powdered characteristic when due, due to said specific structure, not high as compared with an ester due R^P ellipsoid MWmax is high, the α-generating dissociated in addition the CO-CO-OH compared to carboxylic groups generated from ester groups is draws. As a result, polymer a developer solubility of a can be appropriately adjusted, in addition with wide generated from acid generator and a a length can be to expect. As a result, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape can be improved is think.

[A] (I) structural units said polymer addition, formula refers to (2) a constituent unit which is represented by (II), formula (3-1) to (3-4) a constituent unit which is represented by at least selected from the group consisting of 1 types (III) structural units, lactone structure, structure sultone structure and with cyclic carbonate for at least selected from the group consisting of structural units including structure of species 1 (IV) and/or a hydroxy group having (V) structural units including may, these in addition to the is which may have structural units. polymer one or said leg structure 1 unit cell 2 is which may have at least one. Hereinafter, .also disclosed unit leg structure.

[Structural units (I)]

Formula has an (I) structural units (1) is represented by including group that is structural units.

Said type (1) during, R^P hydrogen atom, alkyl having is organic group is 1. * Combined exhibits losses.

Said R^P as which appears as the organic group is 1, which is not particularly limited in, for example, and may be non-reinforcement, a powdered characteristic contributions, reinforcement, a powdered characteristic contributions. may be. 'Reinforcement, a powdered characteristic to' email widow, a web page or, -OH the hydrogen atom of the substituted a group, acid group that dissociated by the action of circulation promoted.. R^P non-reinforcement, a powdered characteristic when due, structural units polymer is the (I) having reinforcement, a powdered characteristic is a dissociated when solubility of more appropriately adjusted. can be used. Furthermore, R^P is reinforcement, a powdered characteristic when due, characteristic reinforcement, a powdered polymer is polymer-containing, MWmax characteristic is dissociated (I) structural units, in this case, more solubility of polymer can be appropriately adjusted. Or escrowed some aspects, polymer a developer solubility of a sparingly than can be appropriately adjusted. Furthermore, with wide generated from acid generator and a a length can be to expect. As a result, the radiation-sensitive resin composition performance LWR, soluble, focus and rectangular mother pipe having a cross sectional shape deep can be ensuring excellent.

Said non-reinforcement, a powdered characteristic not into, for example (1) 1 of hydrocarbons of 1 to 20 carbon atoms having hydrogen atoms hydrogen giga polar some or all of an elongated substituted (hereinafter, 'to (1)' also referred to as), (2) hydrocarbons of 1 to 20 carbon atoms of carbon-carbon hydrogen 1 between-O-, -CO-, -COO and-SO₂ O-selected from the group consisting of to including at least 1 species (hereinafter, 'to (2)' also referred to as), or (3) 1 1 to 20 carbon atoms of carbon-carbon hydrogen hydrocarbons of between-O-, -CO-, -COO and-SO₂ 8880002 892888 selected from the group consisting of at least 1 with a Lewis acidity and, in addition hydrogen atom some or all of an elongated substituted polar (hereinafter, 'to (3)' also referred to as) as to the aromatic hydrocarbon.

1 of said carbon atoms as hydrocarbon group of 1 to 20, for example 1 to 20 carbon atoms of hydrocarbon group chain of 1, 1 of 3 to 20 carbon atoms of alicyclic hydrocarbon group, aromatic is 1 of 6 to 20 carbon atoms as to the aromatic hydrocarbon hydrocarbon group.

Said chain of 1 to 20 carbon atoms of hydrocarbon group as 1, for example

Methyl, ethyl, writing profile, butyl to, neopentyl such as alkyl;

neel ethenyl, propenyl to, vice-reel Neel , pen reel Neel such as alkenyl group;

neel ethinyl, Prophy neel , neel butyrate, alkynyl such as pen mote Neel can be mentionned machine or the like.

1 of 3 to 20 carbon atoms of said alicyclic hydrocarbon group as,

Writing profile cycloalkyl, cycloalkyl butyl , [...] cycloalkyl, cycloalkyl group, a cycloalkyl group, an [...]only annularity such as group;

Nor [...] , adamantyl group-, tree hour claw group, tetra as many as hour clawmulti annularity group, a cycloalkyl group, an such as group;

vice-reel Neel cycloalkyl, pen reel Neel cycloalkyl, cycloalkyl such as [...]only annularity cyclo alkenyl group;

Nor [...] , tree hour claw three Neel such as as to the aromatic hydrocarbon multi annularity cyclo alkenyl group.

Of said 6 to 20 carbon atoms as aromatic hydrocarbon group of 1, for example

Phenyl, [...] , reel it will grow , mesh trityl, [...] , [...] such as aryl;

Benzyl, trityl phenate, [...] , [...] as to the aromatic hydrocarbon C1 to C16 aralkyl such as.

As said polar group, for example hydroxy, carboxyl, cyano group, amino group as to the aromatic hydrocarbon. Among them hydroxy, carboxyl, cyano group are preferably present in the salt, hydroxyl groups, is preferably cyano group.

To said (1) as, for example hydroxymethyl, cyano polar group such as alkyl substituted roh ethyl ; carboxylic [...] group, hydroxy [...] , [...] polar group such as substituted alkyl, amino phenyl , hydroxy phenyl such as as to the aromatic hydrocarbon aryl substituted polar group. Among them are preferably present in the salt alkyl substituted polar group, hydroxy [...] , preferably than [...].

To said (2) as, for example oxy [...] , oxy [...] having an elongate ether structure an annulus group, oxo [...] , oxo [...] group, oxo [...] an annulus ketone having an elongate structure, butyrolactone-yl group, nor [...] -yl group, oxy [...] -yl group such as lactone structure having an elongate, -yl group sultone propionate, nor [...] -yl group such as sultone structure as to the aromatic hydrocarbon having an elongate. Among them annular ketone having an elongate structure, having an elongate lactone group, sultone structure is preferably having, oxy [...] , butyrolactone-yl group, nor [...] -yl group, oxy [...] -yl group, nor [...] -yl group is preferably.

To said (3) as, for example hydroxy tetra draw blood column -yl group such as having an elongate ether structure annular substituted polar group, cyano polar group such as-yl group [...] having an elongate structure ketone annular substituted, [...] cyano-yl group, such as-yl group [...] cyano polar group substituted lactone structure having an elongate, cyano polar group such as-yl group [...] having an elongate structure sultone substituted as to the aromatic hydrocarbon. Among them polar group substituted lactone structure is preferably having, -yl group is preferably [...] cyano.

To said (1) to (3) in, to (I) synthesis of monomer with pushed outwardly to in terms (1), to (2) are preferably present in the salt, to (2) is preferably.

Said reinforcement, a powdered characteristic not into, but is not particularly limited in, which are for example represented by formula (p) as to the aromatic hydrocarbon that is connected to a.

During (p) type said, R^p1 is hydrogen atom, of 1 to 10 carbon atoms is 1 of chain hydrocarbon group. R^p2 and R^p3 are each independently, 1 chain of 1 to 10 carbon atoms of hydrocarbon group of carbon number of 3 to 20 or alicyclic hydrocarbon group of 1, or combine with each other and is, the tightening of the screw connection that these and the carbon atoms of the reduced water 3 to 20 exhibits and, pill structure.

Said R^p1, R^p2 and R^p3 of 1 to 10 carbon atoms represented by 1 as hydrocarbon group chain of, for example to said (1) of the illustrated as hydrocarbon group chain of 1 in 1 to 10 carbon atoms as to the aromatic hydrocarbon in.

Said R^p2 and R^p3 of 3 to 20 carbon atoms represented by 1 as alicyclic hydrocarbon group of, for example to said (1) 1 of the illustrated as alicyclic hydrocarbon group of the same machine or the like can be mentionned.

Said R^p2 and R^p3 is combined each other, the tightening of the screw connection that these and the carbon atoms of the reduced water 3 to 20 as, pill structure, for example cyclopropane structure, cyclo butane structure, cyclopentane structure, structure cyclohexane, cyclo heptane structure, bicyclo octane structure, cyclo nonan structure, cyclo decane structure, nor [...] structure, structure cycloalkane such as having adamantane structure; cyclobutene structure, cyclopentene structure, cyclohexene structure, structure hepten cycloalkyl, cycloalkyl octene structure, cyclo hexadecene structure, norbornene structure nor the as to the aromatic hydrocarbon of cycloalkene structure.

Said reinforcement, a powdered characteristic not into, having losses coupled to class 3 alkyl carbon atoms, carbon atoms of a cyclotrisiloxane having a losses coupled to class 3 alkyl substituted alkyl, 1-alkyl substituted group, a cycloalkyl group, an-1-, allyl position of carbon atoms of a cyclotrisiloxane having a losses coupled to class 2 as to the aromatic hydrocarbon alkenyl group.

Said R^P as, preferably organic group is 1.

As structural units (I), which are for example formula (1-1) or (1-2) a constituent unit which is represented by (hereinafter, each 'structural units (I-1) (I-2) structural units' , '' also referred to as) as to the aromatic hydrocarbon.

Said type (1-1) and (1-2) during, R^P the type (1) is and copper.

Said type (1-1) during, R¹ is hydrogen atom, or a substituted or unsubstituted carbon can copyright 2000 5 to 1. R² the methylene groups, 1015 per square meter 10 to 2 carbon atoms, [...] of 3 to 20 carbon atoms, arylene groups of 6 to 20 carbon atoms, or said 1015 per square meter and [...] carbon-carbon between-CO-, -COO and-SO₂ O-selected from the group consisting of. double including at least 1 species.

Said type (1-2) during, R³ is hydrogen atom, or a substituted or unsubstituted carbon can copyright 2000 5 to 1. Sum epitaxial silicon the L, -COO or-CONR^N-is. R^N is hydrogen atom or carbon atoms of hydrocarbon group of 1 to 10 is 1. R⁴ 1 to 5 alkyl the carbon atoms, carbon atoms of carbon number 1 to 5 alkoxy group is it will know of 2 to 5. R⁵ the epitaxial silicon sum, methylene groups, 1015 per square meter 10 to 2 carbon atoms, [...] of 3 to 20 carbon atoms, arylene groups of 6 to 20 carbon atoms, or said 1015 per square meter and [...] carbon-carbon between-CO-, -COO and-SO₂ O-selected from the group consisting of. double including at least 1 species. The a is integer number of 1 to 5. The b is integer number of 0 to 4. Stage, is the a+b 5 hereinafter. R^P, R⁴ and R⁵ a desired respectively, plurality of R^P, R⁴ and R⁵ each. which may be the same or different.

Said R¹ and R³ represented by 1 to 5 carbon atoms as alkyl, for example methyl, ethyl, n-writing, writing-i, to-butyl n, i to-butyl, sec-butyl to, to-butyl t, as to the aromatic hydrocarbon [...] -n.

Said R¹ and R³ is replaced with a signal expressed by alkyl as substituents which may be, for example fluorine atom, chlorine atom, bromine atoms, iodine atoms of a halogen, such atoms, hydroxy, carboxyl, cyano group, amino group as to the aromatic hydrocarbon.

Said R¹ and R³ as, , e.g., for hydrogen atoms, methyl, trifluoromethyl as to the aromatic hydrocarbon.

Of said L-CONR^N-in R^N of 1 to 10 carbon atoms represented by 1 of as hydrocarbon group, for example alkyl 1 to 10 carbon atoms, alkyl of 3 to 20 carbon atoms, to 6 carbon atoms as to the aromatic hydrocarbon 20 aryl.

As said L, sum epitaxial silicon, -COO-preferably, preferably than ROM for storing programs epitaxial silicon.

Said R⁴ 1 to 5 carbon atoms is represented by as alkyl, for example said R¹ 1 to 5 carbon atoms is represented by the illustrated as alkyl same: such as.

Said R⁴ 1 to 5 carbon atoms is represented by as alkoxy group, for example so2ch2ch2ox, [...] , width time -n, width time -i, to n-butoxy, i to-butoxy, sec-butoxy to, to-butoxy t, as to the aromatic hydrocarbon [...] -n.

Said R⁴ is represented by as it will know of 2 to 5 carbon atoms, for example acetyl to, neel propionate, butyrate reel , this cow departmentmote reel , ballet reel , ballet reel isocyanate, an acyl group such as-pivalate, saturation; acryloyl group-, Prophy at this year diary, methacryloyl diary, crotonobetaine diary, such as diary roh crow toe isocyanate as to the aromatic hydrocarbon unsaturated an acyl group with.

Said R² and R⁵ 2 to 10 carbon atoms is represented by as 1015 per square meter, to ethylene for example, to propylene, polybutylene to, [...] , [...] , [...] , curing accelerator, inorganic filler, modifier as to the aromatic hydrocarbon midifiers targeting.

Said R² and R⁵ is represented by as [...] of 3 to 20 carbon atoms, cyclo propylene for example, cyclo [...] , [...] cycloalkyl, cycloalkyl [...] , [...] cycloalkyl, cycloalkyl [...] , nor [...] , as to the aromatic hydrocarbon [...] adamantyl group in the ortho position.

Said R² and R⁵ is represented by as 5 arylene groups of 6 to 20 carbon atoms, for example polyphenylene to, [...] , [...] , to [...] , [...] , as to the aromatic hydrocarbon [...].

Said R² and R⁵[...] and 1015 per square meter which appears as the carbon-carbon between-CO-, -COO or-SO₂ O-a not into including, for example (cyclo) alkyl [...] (cyclo) 1015 per square meter, (cyclo) (cyclo) alkyl [...] 1015 per square meter, (cyclo) (cyclo) alkyl [...] as to the aromatic hydrocarbon 1015 per square meter.

R² and R⁵ as, methylene groups, 2 to 5 carbon atoms preferably [...] alkyl, preferably than is methylene.

As said a, 1 or 2 are preferably present in the salt, . is more preferred to set a 1.

As said b, is preferably 0 or 1, 0. is more preferred to set a.

As structural units (I), which are for example formula (1-1-1) to (1-2-16) a constituent unit which is represented by (hereinafter, 'structural units (I-2-16) to (I-1-1)' is, sometimes referred to as) as to the aromatic hydrocarbon.

Said type (1-1-1) to (1-1-29) during, R¹ the type (1-1) is and copper.

Said type (1-2-1) to (1-2-16) during, R³ the type (1-2) is agree and a.

As, resulting in a lower limit of ratio of the structural units (I), constituting a overall structure the unit are preferably present in the salt 10 mole %, preferably is 20 mole %, more preferably, the is 30 mole %. As an upper limit of 1,000,000 and an ratio of the structural units (I) are preferably present in the salt 90 mole %, preferably is 70 mole %, more preferably, the is 50 molar %. (I) said ratio of the structural units by is regulated to, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound..

Monomer for providing (I) structural units (hereinafter, 'compound (i)' is, sometimes referred to as) as, formula (i-1-1) to (i-2-16) in terms of compound (hereinafter, '(i-2-16) to (i-1-1) compound' is, sometimes referred to as) as to the aromatic hydrocarbon.

During (i-1-29) to (i-1-1) type said, R¹ the type (1-1) is and copper.

During (i-2-16) to (i-2-1) type said, R³ the type (1-2) is agree and a.

Compound (i) as manufacturing method of, for example,

Compound formula is (i) (i-1) compounds represented by (hereinafter, '(i-1) compound' is, sometimes referred to as) when, compounds represented by formula (i-a) (hereinafter, '(i-a) compound' is, sometimes referred to as) and compounds represented by formula (i-b-1) (hereinafter, '(i-b-1) compound' is, sometimes referred to as) having a step for reacting method is,

Compound formula is (i) (i-2) compounds represented by (hereinafter, '(i-2) compound' is, sometimes referred to as) when, formula (i-a ') compounds represented by (hereinafter, ' compound (i-a ')' is, sometimes referred to as) and compounds represented by formula (i-b-2) (hereinafter, '(i-b-2) compound' is, sometimes referred to as) having a step for reacting may while the method.

According to said manufacturing method, compound (i) conveniently yield good in addition can be produced.

Said type (i-a), during (i-1) and (i-b-1), R^P hydrogen atom, alkyl having is organic group is 1. X represent halogen is. R¹ is hydrogen atom, or a substituted or unsubstituted carbon can copyright 2000 5 to 1. R² the methylene groups, 1015 per square meter 10 to 2 carbon atoms, [...] of 3 to 20 carbon atoms, arylene groups of 6 to 20 carbon atoms, or said 1015 per square meter and [...] carbon-carbon between-CO-, -COO and-SO₂ O-selected from the group consisting of. double including at least 1 species.

Said type (i-a '), during (i-2) and (i-b-2), R^P hydrogen atom, alkyl having is organic group is 1. X represent halogen is. R³ is hydrogen atom, or a substituted or unsubstituted carbon can copyright 2000 5 to 1. Sum epitaxial silicon the L, -COO or-CONR^N-is. R^N is hydrogen atom or carbon atoms of hydrocarbon group of 1 to 10 is 1. R⁴ 1 to 5 alkyl the carbon atoms, carbon atoms of carbon number 1 to 5 alkoxy group is it will know of 2 to 5. R⁵ the epitaxial silicon sum, methylene groups, 1015 per square meter 10 to 2 carbon atoms, [...] of 3 to 20 carbon atoms, arylene groups of 6 to 20 carbon atoms, or said 1015 per square meter and [...] carbon-carbon between-CO-, -COO and-SO₂ O-selected from the group consisting of. double including at least 1 species. The a is integer number of 1 to 5. The b is integer number of 0 to 4. Stage, is the a+b 5 hereinafter. R^P, R⁴ and R⁵ a desired respectively, plurality of R^P, R⁴ and R⁵ each. which may be the same or different.

Said X is halogen atoms, and, in its turn, for example fluorine atom, chlorine atom, bromine atoms, iodine atoms as to the aromatic hydrocarbon. Among them compound (i-a) and (i-a '), the reactivity of the target substance in terms the motor chamber receives a motor for preferred, chlorine atom, bromine atoms are preferably present in the salt, preferably is bromine atoms.

Compound (i-a) propanamines/water mixture solvent for (i-b-1) and compounds such as by solvent during, is (i-1) compound are obtained. Furthermore, compound (i-a')for (i-b-2) and compounds, as well as said by reacting a, is (i-2) compound are obtained.

Said compound (i-a')and compound (i-a) the indolepyruvic halo 3-COCOOH-such as and halogen compounds having groups, said type (1) in R^P compound an alcohol group, dimethylamino pyridine such as base and 1-ethyl-3-[ 3-(dimethylamino) profile] carboxylic [...] (EDCI) bsed dehydrating such as in the presence of material is obtained by reacting.

[Structural units (II)]

Structural units (II) detects a formula (2) is a constituent unit which is represented by. (II) structural units of-CR⁷ R⁸ R⁹ represented by a reinforcement, a powdered characteristic that is connected to a. double. The radiation-sensitive resin composition (II) polymer is by having structural units, which is improved in the sensitivity, as a result LWR performance, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound..

Said type (2) during, R⁶ is hydrogen atom, fluorine atom, methyl or trifluoromethyl is. The Y sum epitaxial silicon, carbonyl jade city hour claw alkane D diary 4 to 20 carbon atoms, carbonyl the jade time which will be a jade city hour claw alkane D 4 to 20 carbon atoms, 6 to 20 carbon atoms of 7 to 20 diary [...] carbonyl [...] is of carbon number. R⁷ carbon atoms of 10 to 1 1 of chain hydrocarbon group of carbon number of 3 to 20 is alicyclic hydrocarbon group of 1. R⁸ and R⁹ independently from each other, 1 chain of 1 to 10 carbon atoms of hydrocarbon group of carbon number of 3 to 20 or alicyclic hydrocarbon group of 1, or their is combine with each other and, the tightening of the screw connection that these open and the carbon atoms of 20 to 3 carbon atoms exhibits and alicyclic structure.

Said Y is represented by carbonyl jade city hour claw alkane D diary as 4 to 20 carbon atoms, for example

Carbonyl jade city hour claw pro petal D diary, carbonyl jade city hour claw Bhutan D diary, carbonyl jade city hour claw pentane D diary, such as diary carbonyl [...]only annularity carbonyl jade city hour claw alkane D diary;

Carbonyl [...] diary, carbonyl the jade hour Ada bay the D it burns diary, carbonyl jade hour tree hour claw space D diary, such as diary carbonyl jade hour tetra hour claw space D as to the aromatic hydrocarbon multi annularity carbonyl jade city hour claw alkane D diary.

Said Y is represented by carbonyl the jade time which will be a jade city hour claw alkane D as 4 to 20 carbon atoms, for example

Carbonyl the jade time which will be a jade city hour claw pro petal D , carbonyl the jade time which will be a jade city hour claw Bhutan D , carbonyl the jade time which will be a jade city hour claw pentane D , such as carbonyl [...]the jade time which will be a jade city hour claw alkane D carbonyl only annularity ;

Carbonyl [...] , carbonyl the jade hour Ada bay the jade time which will be a D it burns , carbonyl the jade time which will be a jade hour tree hour claw space D , such as carbonyl the jade time where also the jade hour tetra hour claw will be space D as to the aromatic hydrocarbon the jade time which will be a jade city hour claw alkane D carbonyl multi annularity.

Said Y is represented by as [...] of 6 to 20 carbon atoms, for example

Benzene di diary, diary di toluene, xylene di diary, diary di [...] , naphthalene di diary, as to the aromatic hydrocarbon anthracene di diary.

Said Y is represented by as carbonyl [...] 7 to 20 carbon atoms, for example

Carbonyl jade hour benzene D diary, carbonyl [...] diary, carbonyl jade hour xylene D diary, carbonyl [...] , carbonyl jade hour naphthalene D diary, as to the aromatic hydrocarbon carbonyl jade hour anthracene D diary.

As said Y, sum epitaxial silicon, carbonyl the jade time which will be a jade city hour claw alkane D 4 to 20 carbon atoms, preferably 6 to 20 carbon atoms of [...] , sum epitaxial silicon, carbonyl multi annularitythe jade time which will be a jade city hour claw alkane D , preferably than d diary benzene, sum epitaxial silicon, more preferably, the benzene d diary.

Said R⁶ as, (II) structural units copolymerizable of monomers provides in terms of, hydrogen atom, preferably methyl group, preferably is methyl.

Said R⁷, R⁸ and R⁹ of 1 to 10 carbon atoms is represented by 1 as hydrocarbon group chain of, for example

Methyl, ethyl, n-writing, such as writing-i alkyl;

neel ethenyl, propenyl to, vice-reel Neel such as alkenyl group;

neel ethinyl, Prophy neel , alkynyl such as neel butyrate can be mentionned machine or the like.

Said R⁷, R⁸ and R⁹ of 3 to 20 carbon atoms is represented by 1 as alicyclic hydrocarbon group of, for example

[...] cycloalkyl, cycloalkyl group, a cycloalkyl group, an [...]only annularity such as group;

pen reel Neel cycloalkyl, cycloalkyl such as [...]only annularity cyclo alkenyl group;

Nor [...] , adamantyl group-, tree hour clawmulti annularity group, a cycloalkyl group, an such as group;

Nor [...] , tree hour claw three Neel such as as to the aromatic hydrocarbon multi annularity cyclo alkenyl group.

Combine with each other and is their said, the tightening of the screw connection that these open and the carbon atoms and represented as alicyclic structure of 3 to 20 carbon atoms, for example

Cyclopropane structure, cyclo butane structure, cyclopentane structure, structure cyclohexane, cyclo heptane structure, such as structure cycloalkane only annularity bicyclo octane structure;

Nor [...] structure, having adamantane structure, tree hour claw space structure, tetra as many as hour claw space structure such as as to the aromatic hydrocarbon multi annularity cycloalkane structure.

As structural units (II), formula (2-1) to (2-7) a constituent unit which is represented by (hereinafter, 'structural units (II-7) to (II-1)' is, sometimes referred to as) Na:K is preferably.

Said type (2-1) to (2-7) during, R⁶ to R⁹ the type (2) and a is agree. I and j independently from each other is integer number of 1 to 4.

As (II-7) to (II-1) structural units, which are for example which is as to the aromatic hydrocarbon structural units.

In formula said, R⁶ the type (2) and a is agree.

As (II) structural units, (II-1) structural units, structural units (II-2), (II-5) structural units, structural units are preferably present in the salt (II-6), 1-alkyl-1-cyclobutane, and R4 represents cyclopentyl (meth) acrylate derived from a constituent unit which, 2-alkyl-2-adamantyl (meth) acrylate derived from a constituent unit which, (jade hour carbonyl jade city -alkyl t) 3-one-1-adamantyl (meth) acrylate, p-(t-(cyclo) alkyloxycarbonyl) styrene preferably is a constituent unit which is derived from.

As ratio of the structural units (II), constituting a overall structure the unit 10 mole % to 80 mole % are preferably present in the salt, 20 mole % to 75 mole % is preferably, 30 mole % to 70 mole % and more preferably, 35 mole % to 60 mole % is preferably in particular. By containing said said ratio ranges from, the radiation-sensitive resin composition the implant is also more sensitivity, performance LWR as a result, resolution, focus and rectangular mother pipe having a cross sectional shape. than deep. Containing said lower limit if less than said ratio, the radiation-sensitive resin composition pattern forming to a DC voltage. when. Said ratio exceeds a containing said upper limit, resist pattern adhesion to a substrate includes a..

[Structural units (III)]

Structural units (III) formula has an (3-1) to (3-4) at least selected from the group consisting of structural units in terms of species 1 (hereinafter, ' (III-4) to (III-1) structural units' also referred to as) is. The radiation-sensitive resin composition (III) polymer is by having structural units, obtained adhesion to a substrate of a resist pattern of poor etching the objective compound.. Furthermore, KrF exposure, when EUV exposure or electron beam exposure, the radiation-sensitive resin composition can be the magnets.

Said type (3-1) to (3-4) during, R^C independently from each other, hydrogen atom or C1-C6 copyright 2000 5 to 1.

Said type (3-1) to (3-3) during, c independently from each other, is integer number of 1 to 3. R^A independently from each other, copyright 2000 1 to 5 carbon atoms. D independently from each other, is integer number of 0 to 4. Stage, is the c+d 5 hereinafter. R^A is a desired, plurality of R^A each. which may be the same or different.

Said type (3-4) during, L³ and L⁴ the epitaxial silicon sum, methylene groups, 1015 per square meter 5 to 2 carbon atoms, [...] of 3 to 15 carbon atoms, arylene groups of 6 to 20 carbon atoms, or groups-O and-CO-selected from the group consisting of at least 1 species in combination with. double of 2. R^D hydrogen atom, carboxyl, 1 1 to 5 chain of carbon atoms of hydrocarbon group, alkoxy group 1 to 5 carbon atoms, hour carbonyl alkoxide 2 to 5 carbon atoms, or the end of the solvent having hydroxy groups the hydroxy adjacent carbon atoms of at least 1 fluorine atom or a fluorinated alkyl group having.. The e is integer number of 1 to 5. L⁴ and R^D a desired respectively, plurality of L⁴ and R^D each. which may be the same or different.

Said R^A and R^C 1 to 5 carbon atoms is represented by as alkyl, for example methyl, ethyl, linear or branched profile of writing, butyl to, as to the aromatic hydrocarbon [...].

Said R^C as, (II) structural units copolymerizable of monomers provides in terms of, hydrogen atom, preferably methyl group, preferably than hydrogen atoms.

Said R^B as, preferably methyl group. As d, preferably 0.

Said L³ and L⁴ 2 to 5 carbon atoms is represented by as 1015 per square meter, to ethylene for example, to propylene, polybutylene to, as to the aromatic hydrocarbon [...].

Said L³ and L⁴ is represented by as [...] of 3 to 15 carbon atoms, cyclo propylene for example, cyclo [...] , [...] cycloalkyl, cycloalkyl [...] , nor [...] , as to the aromatic hydrocarbon [...] adamantyl group in the ortho position.

Said L³ and L⁴ is represented by as 5 arylene groups of 6 to 20 carbon atoms, for example polyphenylene to, [...] , [...] , [...] , as to the aromatic hydrocarbon [...].

Said L³ and L⁴ which appears as the groups-O and-CO-selected from the group consisting of at least 1 species in combination with not into of 2, for example (cyclo) alkyl [...] , (cyclo) alkyl [...] , (cyclo) alkyl [...] , (cyclo) alkyl [...] , [...] , [...] , [...] , as to the aromatic hydrocarbon [...].

Said R^D of 1 to 5 carbon atoms is represented by 1 as hydrocarbon group chain of, for example

Methyl, ethyl, writing profile, butyl, such as an alkyl;

neel ethenyl, propenyl to, vice-reel Neel such as alkenyl group;

neel ethinyl, Prophy neel , alkynyl such as neel butyrate can be mentionned machine or the like.

Said R^D 1 to 5 carbon atoms is represented by as alkoxy group, for example so2ch2ch2ox, [...] , width time profile, butoxy to, as to the aromatic hydrocarbon [...].

Said R^D 1 to 5 carbon atoms is represented by hour carbonyl as alkoxide, for example [...] , [...] , as to the aromatic hydrocarbon width hour carbonyl profile.

Said R^D to is represented by adjacent hydroxy the solvent having hydroxy groups at least carbon atoms of fluorine atom or a fluorinated alkyl 1 having not into, for example hydroxy-di (trifluoromethyl) methyl, hydroxy-methyl-trifluoromethyl methyl, hydroxy-di ([...]) methyl as to the aromatic hydrocarbon.

As (III) structural units, structural units (III-1), are preferably present in the salt (III-4) structural units, structural units is preferably (III-1).

As ratio of the structural units (III), constituting a overall structure the unit 0 mole % to 50 mole % are preferably present in the salt, 0 mole % to 30 mole % is preferably. The radiation-sensitive resin composition (III) structural units polymer is by having, resist pattern more adhesion to a substrate the objective compound.. Furthermore, KrF exposure, EUV exposure and electron beam exposure at the objective compound. than.

[Structural units (IV)]

The lactone structure (IV) structural units, with cyclic carbonate for structure and sultone structure selected from the group consisting of structural units including at least 1 species (stage, acid except a (I) structural units) is. (IV) a constituent unit which polymer by having further, further solubility of a developer can regulate the, as a result, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound.. Furthermore, the radiation-sensitive resin composition which is made from resist pattern and adhesion to substrates the objective compound..

As (IV) structural units, which are for example which is as to the aromatic hydrocarbon structural units.

In formula said, R^L1 is hydrogen atom, fluorine atom, methyl or trifluoromethyl is.

As (IV) structural units, structural units including structure [...] nor among them, γ-butyrolactone structure including structural units, structural units including ethylene polycarbonate structure, nor [...] are preferably present in the salt structural units including structure, nor [...] -yl (meth) acrylate derived from a constituent unit which, cyano [...] -yl (meth) acrylate derived from a constituent unit which, oxy [...] -yl (meth) acrylate derived from a constituent unit which, butyrolactone-yl (meth) acrylate derived from a constituent unit which, nor [...] -yl (meth) acrylate derived from a constituent unit which is preferably.

As ratio of the structural units (IV), constituting a overall structure the unit 0 mole % to 70 mole % are preferably present in the salt, 0 mole % to 60 mole % is preferably, molar 20% to 55% is more preferably, the molar. By containing said said ratio ranges from, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound. than. In addition the radiation-sensitive resin composition of a resist pattern formed more adhesion to a substrate the objective compound..

[Structural units (V)]

The (V) structural units a constituent unit which solvent having hydroxy groups (stage, acid except a (I) structural units) is. (V) a constituent unit which polymer by having further, further solubility of a developer can regulate the, as a result, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound..

As (V) structural units, which are for example which is as to the aromatic hydrocarbon structural units.

In formula said, R^B hydrogen atom, fluorine atom, methyl or trifluoromethyl is.

(V) as ratio of the structural units, constituting a overall structure the unit 0 mole % to 70 mole % are preferably present in the salt, 0 mole % to 60 mole % is preferably, molar 20% to 55% is more preferably, the molar. By containing said said ratio ranges from, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound. than.

[A] (I) to (V) structural units said polymer addition, other structural units is even when they have a. As said other structural unit, e.g.-carbonyl group to, cyano group, carboxyl, nitro, of gas burner for amino group as to the aromatic hydrocarbon structural units. Carbonyl group-ketone among them are preferably present in the salt has a structural unit having, oxo methyladamantyl (meth) acrylate derived from a constituent unit which is preferably. These as the content ratio of structural units, are preferably present in the salt 30 molar % hereinafter, is preferably 20 mole % hereinafter. Furthermore, as said other structural unit, for example a phenolic hydroxyl of reinforcement, a powdered hydrogen atoms substituted characteristic including a structure in which a can be mentionned room to guide the structural units. Said reinforcement, a powdered characteristic not into, for example 3, such as an-butyl t it is a hand alkyl class carbon is coupled, such as diary-2-1-3 class carbon is coupled [...]it is a hand alkoxy as to the aromatic hydrocarbon CD alkyl methyl. As said structural units, among them t-alkyl [...] derived from a constituent unit which, [...] alkoxy derived from a constituent unit which are preferably present in the salt, derived from-butoxystyrene t a constituent unit which is preferably. These as the content ratio of structural units, are preferably present in the salt 80 molar % hereinafter, is preferably 60 mole % hereinafter. polymer structural units said addition, other structural is which may have units.

[A] as content of polymer, the radiation-sensitive resin composition based on the total solid component preferably 25 mass % or more. The radiation-sensitive resin composition is regulated to heightening the content of the polymer by said, LWR performance, resolution, focal depth and rectangular mother pipe having a cross sectional shape than can be ensuring excellent. content of polymer if it is less than said range, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the matrix polymer and tends to guide plate. In addition 'based on the total solid component' rotation, radiation-sensitive resin composition solvent circulation promoted. total of salts of sulfonyl. as content of polymer, the radiation-sensitive resin composition based on the total solid component and is more preferred to set a 40 mass % or more, 60 mass % or more, and more preferably in a and, in particular preferably at least 80 mass %, preferably in addition in particular at least 85 mass %.

<[A] 중합체의 합성 방법 >

[A] polymer, each structural units monomers provided, the disclosure number radical polymerization, with a suitable solvent polymerising an can be synthesized by.

Disclosure agent said radical polymerization, azo bis isobutyrate polyacrylonitrile (AIBN), 2, 2 '-azo bis (4-methoxy -2, 4-dimethyl valeronitriles), 2, 2' -azo bis (2-cyclo pro the pro which will bloom bloom the knit reel), 2, 2 '-azo bis (2, 4-dimethyl valeronitriles), dimethyl 2, 2' -azo bis isobutyrate such as azo-based radical disclosure number; benzoyl peroxide, [...] -butyl t, such as radical the light emitting property by interrupting peroxide [...] as to the aromatic hydrocarbon disclosure number. Among them AIBN, dimethyl 2, 2' are preferably present in the salt isobutyrate bis-azo, . is more preferred to set a AIBN. Such radicals disclosure alone or in species 1 agent by mixing the at least one 2, use can be made of,.

As solvent used in the polymerization said, for example

N-pentane, n-hexanediol, n-heptane, n-octane rating, n-nonane, of an alkane such as decane-n;

Cyclohexane, cyclo heptane, bicyclo octane, azadecalin, nor [...] current cycloalkane such as;

Benzene, toluene, xylene, ethylbenzene, cumene strain of an aromatic hydrocarbons;

Chlorobutane to form a polyolefin and withdrawing current, bromo hexane current, dichloroethane current, hexa [...] , trichlorobenzene of a halogen, such hydrocarbon current;

Acetic acid ethyl, acetic acid n-butyl, acetic acid i-butyl, [...] carboxylic saturation such as methyl propionic acid;

Acetone, methyl ethyl ketone, 4-methyl-2-pentanone, 2- [...] such as ketones;

Propanamines, [...] , [...] such as ethers;

Methanol, ethanol, 1-propanol, 2-propanol, 4-methyl-2-pentanols such as as to the aromatic hydrocarbon alcohols. These used in the polymerization solvent alone or in species 1 may which practices a at least one 2.

As said reaction temperature in the polymerization of ethylene, 150 °C to 40 °C conventional, preferably is 120 °C to 50 °C. As reaction time, conventional time 48 hr to 1, preferably 1 hr to 24 time.

[A] polymer gel permeation chromatography, by weight average molecular weight (GPC) polystyrene terms but is not particularly limited in the (Mw), 1,000 or more are preferably present in the salt 50,000 hereinafter, 30,000 hereinafter is preferably 2,000 or more, more preferably 20,000 hereinafter or more 3,000, 5,000 is in particular preferably 15,000 or more. Mw is regulated to said polymer by a, the radiation-sensitive resin composition coating and developing. inhibitory deficiency. polymer Mw is said lower limit if less than, sufficient heat resistance for use in a resist film having a. of a fuel cell may be obtained. polymer exceeds a upper limit said is Mw, resist film development, developability with an. includes a.

[A] polymer polystyrene terms by GPC number average molecular weight (Mn) for typically (Mw/Mn) non Mw 1 or more and 5 hereinafter, are preferably present in the salt 3 hereinafter 1 or more, more preferably, the 1 or more is 2 hereinafter.

The present specification of the polymer in the Mn and Mw hereinafter (GPC) gel permeation chromatography, a conditions be measured by use of a value.

GPC column: two G2000HXL 2, two G3000HXL 1, G4000HXL 1 two (or more, stone bovine manufacturing)

Column temperature: 40 °C

Elution solvent: propanamines (Tajawako [...]high school manufacturing)

Flow rate: 1.0 ml/min

Concentration: 1.0 mass %

Sample injection amount: 100 μ L

Detector: parallax refractometer

Standards: monodispersed polystyrene

[A] as content of portion a low molecular weight polymer, are preferably present in the salt 0.5 mass % hereinafter, is preferably 0.2 mass % hereinafter, more preferably, the is 0.1 mass % hereinafter. heightening the content of the portion of the low molecular weight polymer is regulated to by said, the radiation-sensitive resin composition. inhibitory deficiency developing. Furthermore, polymer a low molecular weight portion circulation promoted. portion of 1,000 hereinafter molecular weight acids to epoxygenated fatty acids therein.

The present specification of the polymer in low molecular weight portion (portion of molecular weight 1,000 hereinafter) (mass %)content of the hereinafter a conditions to reverse phase high performance liquid chromatography (HPLC) be measured by use of a value.

HPLC column: Intersil ODS-25 micro m, 4.6 mm φ× 250 mm (GLV [...] manufacturing)

Elution solvent: acrylonitrile/0.1 mass % phosphoric acid aqueous solution

Flow: 1.0 ml/min

Concentration: 1.0 mass %

Sample injection amount: 100 μ L

Detector: parallax refractometer

<[B] 산 발생체 >

[B] acid generator and a an exposure of generating an acid when a material that has. Acid of the tread is generated polymer refers to polymer or a non-woven fabric is covered such as reinforcement, a powdered characteristic dissociated is the process using a carboxyl, a developer these polymers vary with the solubility of, the radiation-sensitive from such resin compositions having a capable of forming a resist pattern, the radiation-sensitive resin composition in embodiment of the acid generator and a, refers to as form of molecular weight compound (hereinafter, properly 'number acid generator' also referred to as) even ear, polymer as part of acid generator incorporated in the porous dielectric carrier, even in the form of, .may be in the form of a both.

[B] acid generator agent, for example onium salt compound, N-sulfonyl [...] compounds, halogen-containing compounds, diazo ketone can be mentionned compounds and the like.

Onium salt compound, araliphatic sulfonium salts for example, tetra [...] , [...] , phosphonium, diazonium salt, as to the aromatic hydrocarbon [...] pyrido.

Araliphatic sulfonium salts as, for example tree [...] , tree [...] -n-butane sulfonate, tree [...] -n-octane rating sulfonate, tree 2-bicyclo [2.2.1] [...] methylhept-2-one -1, 1, 2, 2-tetra [...] , tree [...] methylhept-2-one -1, 1-2-bicyclo [2.2.1] [...] -1, 4 content, tree [...] , 4-cyclo [...] , 4-cyclo [...] -n-butane sulfonate, 4-cyclo [...] -n-octane rating sulfonate, 2-bicyclo [2.2.1] [...] cycloalkyl 4-methylhept-2-one -1, 1, 2, 2-tetra [...] , in 4-, Х [...][...][...] type [...][...] , 4-methane [...] , 4-methane [...] -n-butane sulfonate, methane sulfonate-octane rating 4- [...] -n, 4-bicyclo [2.2.1] [...] phenyl methanesulfonylethyl 2-methylhept-2-one -1, 1, 2, 2-tetra [...] , 4-methane [...] , tree [...] 1, 1, 2, 2-tetrafluoro-6-(1-adamantane carbonyloxy)-1-sulfonate as to the aromatic hydrocarbon-hexanediol.

Tetra [...] as, for example 1-(-1-naphthalene-butoxy 4-n one) tetra [...] , 1-(-1-naphthalene-butoxy 4-n one) tetra [...] -n-butane sulfonate, 1-(-1-naphthalene-butoxy 4-n one) tetra [...] -n-octane rating sulfonate, 1-(-1-naphthalene-butoxy 4-n one) tetra [...] 2-bicyclo [2.2.1]-1, 1, 2, 2-tetra [...] methylhept-2-one, 1-(-1-naphthalene-butoxy 4-n one) tetra [...] , 1-(chlorotrifluoro [...] 6-n-butoxy-2-one) tetra [...] , 1-(-2-naphthalene-butoxy 6-n one) tetra [...] -n-butane sulfonate, 1-(-2-naphthalene-butoxy 6-n one) tetra [...] -n-octane rating sulfonate, 1-(-2-naphthalene-butoxy 6-n one) tetra [...] 2-bicyclo [2.2.1]-1, 1, 2, 2-tetra [...] methylhept-2-one, 1-(-2-naphthalene-butoxy 6-n one) tetra [...][...] sulfonate, 1-(3, 5-dimethyl-4-hydroxyphenyl) tetra [...] light, 1-(3, 5-dimethyl-4-hydroxyphenyl) tetra [...] -n-butane sulfonate, 1-(3, 5-dimethyl-4-hydroxyphenyl) tetra [...] -n-octane rating sulfonate, 1-(3, 5-dimethyl-4-hydroxyphenyl) tetra [...] 2-bicyclo [2.2.1]-1, 1, 2, 2-tetra [...] methylhept-2-one, 1-(3, 5-dimethyl-4-hydroxyphenyl) as to the aromatic hydrocarbon [...] tetra.

As [...] , for example [...] , [...] -n-butane sulfonate, [...] -n-octane rating sulfonate, 2-bicyclo [2.2.1] [...] methylhept-2-one -1, 1, 2, 2-tetra [...] , [...] , bis (4-t-butyl phenyl) [...] , bis (4-t-butyl phenyl) [...] -n-butane sulfonate, bis (4-t-butyl phenyl) [...] -n-octane rating sulfonate, bis (4-t-butyl phenyl) bicyclo [2.2.1] [...] 2-methylhept-2-one -1, 1, 2, 2-tetra [...] , bis (4-t-butyl) [...]) as to the aromatic hydrocarbon [...].

N-sulfonyl [...] compound, for example N-(triple base Oro methane alcoholic beverage gun Neel jade city) bicyclo [2.2.1]-2, 3-n-5-methylhept polyimide testing, N-(nonafluoro-n-butane, chlorosulfonyloxy) bicyclo [2.2.1]-2, 3-n-5-methylhept polyimide testing, N-(perfluoro-n-octane rating, chlorosulfonyloxy) bicyclo [2.2.1]-2, 3-n-5-methylhept polyimide testing, N-(2-bicyclo [2.2.1] methylhept-2-one -1, 1, 2, 2-tetra [...]) bicyclo [2.2.1]-2, 3-n-5-methylhept polyimide testing, N-(2-(3-tetra cyclo [4.4.0.1^2,5. 1^7,10] use of Saccharomyces cerevisiae neel car)-1, 1--1, 4 content base Oro ethane alcoholic beverage gun Neel jade city) bicyclo [2.2.1]-2, 3-n-5-methylhept polyimide testing, N-(sulfonyl camphorsulfonate) bicyclo [2.2.1]-2, 3-n-5-methylhept as to the aromatic hydrocarbon polyimide testing.

[B] acid generator agent, formula (4) preferred are those compounds which appears as the. dispersed in the aqueous media in a agent acid generator, polymer or polymer is by interaction with structure a polarity, patterns to be exposed by the same resist film in the portion in an acid diffusion length is appropriately prevent the inner diameter of is considered that, as a result, the radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape the objective compound. than.

Said type (4) during, R¹⁰ the reduced water 6 or more alicyclic structure including 1 of or reduced water 6 or more aliphatic heterocyclic structure. group of including 1. R¹¹anger alkane D diary is fluorine substitution in 1 to 10 carbon atoms. X⁺ the 1 of is cationic onium photo-degradable.

R¹⁰ in 'reduced water' email widow, a web page or, , pill structure heterocyclic and aliphatic alicyclic structure constituting an atomic water numeral key, multi annularitymulti annularity and alicyclic structure when the aliphatic heterocyclic structure, is multi annularity circulation promoted. water of atoms.

Said R¹⁰ in terms of reduced water 6 or more alicyclic structure into of not including 1, for example

[...] cycloalkyl, strolling, cycloalkyl, cycloalkyl group used, such as CH3CH2, cycloalkyl group, a cycloalkyl group, an only annularity ;

jade reel Neel cycloalkyl, cycloalkyl such as three Neelonly annularity cyclo alkenyl group;

Nor [...] , adamantyl group-, tree hour claw group, tetra as many as hour clawmulti annularity group, a cycloalkyl group, an such as group;

Nor [...] , tree hour claw three Neel such as as to the aromatic hydrocarbon multi annularity cyclo alkenyl group.

Said R¹⁰ in terms of reduced water 6 or more aliphatic heterocyclic structure into of not including 1, for example

Nor [...] to-yl group such as lactone structure including;

Nor [...] including structure sultone such as to-yl group;

Oxa [...] , oxa [...] to heterocyclic containing oxygen atoms such as;

Aza [...] group, aza [...] , bicyclo octane diazabicyclo-yl group such as to heterocyclic nitrogen atom-contained;

Thia [...] , thia [...] such as the sulfur atom-containing heterocyclic machine or the like can be mentionned.

R¹⁰ not represented by number reduction of, the above-mentioned with wide in terms the motor chamber receives a motor for suitable the epitaxial layer is lower, and is preferably at least 8, preferably is 9 to 15, more preferably, the is 10 to 13.

R¹⁰ as, among them reduced water 9 or more alicyclic structure of is including 1, reduced water 9 or more aliphatic heterocyclic structure including 1 of preferably a, adamantyl group-, hydroxy [...] , nor [...] -yl group, 5-oxo-4-oxatricyclo [4.3.1.1^3,8] undecane-yl group is preferably, more preferably, the [...] adamantyl group in the ortho position.

Said R¹¹ is represented by 1 to 10 carbon atoms as d diary alkane for fluorinatind, for example methane di diary, ethane di diary, 1 to 10 carbons such as diary di propane can d diary of a hydrogen atoms of the one or more 1-up Image and an nuclear reactor a fluorine can be mentionned machine or the like.

Among them SO₃^- onto carbon atoms adjacent to fluorine atom is bonded to one preferably fluorinated alkane d diary , SO₃^- onto carbon atoms adjacent to 2 of fluorine atom is bonded to one fluorinated alkane d diary and more preferably, 1, 1-diary base Oro methane D -1, 4 content, diary base Oro ethane D -1, 4 content 1, 1-, 1, 1, 3, 3, 3-pentafluoro -1, 2-propane di diary, 1, 1, 2, 2-tetra [...] diary, 1, 1, 2, 2-tetra [...] diary, more preferably, the 1, 1, 2, 2-tetra [...].

Said X⁺ 1 which appears as the onium photo-degradable of water is decomposed by illuminated exposure the cations is a cationic. Exposed part in, cationic onium photo-degradable is produced, by means of the decomposition of a proton and, sulfonate anion from sulfonic acid which has a weight corresponding to weight. Said X⁺ 1 of which appears as the as cationic onium photo-degradable, S for example, I, O, N, P, Cl, Br, F, As, Se, Sn, Sb, Te, including element such as Bi: cationic onium degradable radiation. S as bovine won as cationic including a (sulfur), cationic sulfonium for example, tetra [...] and as to the aromatic hydrocarbon cationic, as a third element to as cationic including a I (iodine), as to the aromatic hydrocarbon [...] cationic. Among them formula (X-1) which appears as the sulfonium cationic, agent composed of is represented by formula (X-2) [...] cationic, signal expressed by formula (X-3) [...] preferably cationic.

During said type (X-1), R^a1, R^a2 and R^a3 are each independently, a substituted or unsubstituted carbon atoms 1 to 12 linear or branched alkyl, a substituted or unsubstituted aromatic hydrocarbon group 6 to 12 carbon atoms, as, -OSO₂-R^P or-SO₂-R^Q or, not less than 2 in or combine with each other and exhibits and a ring structure. R^P and R^Q independently from each other, a substituted or unsubstituted carbon atoms 1 to 12 linear or branched alkyl, a substituted or unsubstituted alicyclic hydrocarbon group of 5 to 25 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group is 6 to 12 carbon atoms. K1, k2 k3 and are each independently, is integer number of 0 to 5. R^a1 to R^a3 and R^P and R^Q a desired respectively, plurality of R^a1 to R^a3 and R^P and R^Q each. which may be the same or different.

During said type (X-2), R^b1 substituted or substituted carbon can 1 to 8 linear or branched alkyl, or a substituted or unsubstituted carbon atoms is 6 to 8 aromatic hydrocarbon group. K4 is integer number of the 0 to 7. R^b1 a desired, plurality of R^b1 is may be identical to or different from, in addition plurality of R^b1 is combined each other a ring structure can exhibit. R^b2 the a substituted or unsubstituted carbon atoms 1 to 7 linear or branched alkyl, or a substituted or unsubstituted aromatic hydrocarbon group is 7 or 6 carbon atoms. K5 is integer number of the 0 to 6. R^b2 is a desired, plurality of R^b2 the same or is different from the, plurality of in addition R^b2 is combined each other a ring structure can exhibit. T is integer number of the 0 to 3.

During said type (X-3), R^c1 and R^c2 independently from each other, a substituted or unsubstituted carbon atoms 1 to 12 linear or branched alkyl, a substituted or unsubstituted aromatic hydrocarbon group 6 to 12 carbon atoms, as, -OSO₂-R^R or-SO₂-R^S or, not less than 2 in or combine with each other and exhibits and a ring structure. R^R and R^S independently from each other, a substituted or unsubstituted carbon atoms 1 to 12 linear or branched alkyl, a substituted or unsubstituted alicyclic hydrocarbon group of 5 to 25 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group is 6 to 12 carbon atoms. K6 k7 and are each independently, is integer number of 0 to 5. R^c1, R^c2, R^R and R^S a desired respectively, plurality of R^c1, R^c2, R^R and R^S each. which may be the same or different.

Said R^a1 to R^a3, R^b1, R^b2, R^c1 and R^c2 having an unsubstituted is represented by as atoms in a linear alkyl, for example methyl, ethyl, n-writing, can be n-butyl machine or the like.

Said R^a1 to R^a3, R^b1, R^b2, R^c1 and R^c2 branched unsubstituted which appears as the as alkyl, for example writing-i, i to-butyl, sec-butyl to, can be mentionned t-butyl machine or the like.

Said R^a1 to R^a3, R^c1 and R^c2 is a nonsubstituted aromatic hydrocarbon group as, for example phenyl, [...] , reel it will grow , mesh trityl, [...] such as aryl; benzyl, trityl phenate as to the aromatic hydrocarbon C1 to C16 aralkyl such as.

Said R^b1 and R^b2 is a nonsubstituted aromatic hydrocarbon group as, for example phenyl, [...] , benzyl machine or the like can be mentionned.

Said alkyl group and aromatic hydrocarbons having hydrogen giga is replaced with a hydrogen atoms as substituent which may be, for example fluorine atom, chlorine atom, bromine atoms, iodine atoms of a halogen, such atoms, hydroxy, carboxyl, cyano group, nitro, alkoxy groups, hour carbonyl alkoxy, alkoxycarbonyl jade time , an acyl group, as to the aromatic hydrocarbon the jade time which it will know.

Preferably halogen atoms from among them, fluorine atom is preferably.

Said R^a1 to R^a3, R^b1, R^b2, R^c1 and R^c2 as, unsubstituted a linear or branched alkyl, fluorine alkyl group, unsubstituted aromatic hydrocarbon group is 1 of, -OSO₂-R ",-SO2-R" are preferably present in the salt, fluorine alkyl group, unsubstituted aromatic hydrocarbons of 1 of preferably than hydrogen giga , fluorine alkyl group is more preferably, the. R " the, 1 of unsubstituted alicyclic hydrocarbon group of of or unsubstituted hydrocarbon group is aromatic is 1.

In said type (X-1) as k3 and k1, k2, preferably integer of 0 to 2, and is more preferred to set a 0 or 1, more preferably, the is 0.

As in said type (X-2) k4, preferably integer of 0 to 2, and is more preferred to set a 0 or 1, more preferably, the is 1. K5 as, preferably integer of 0 to 2, and is more preferred to set a 0 or 1, more preferably, the is 0.

In said type (X-3) as k7 and k6, preferably integer of 0 to 2, and is more preferred to set a 0 or 1, more preferably, the is 0.

Said type (4) an acid generator agent is represented by, which are for example formula (4-1) to (4-11) compounds represented by (hereinafter, 'compound (4-1) to (4-11)' is, sometimes referred to as) as to the aromatic hydrocarbon.

[B] acid generator agent, preferred are those compounds onium salt among them and, preferably than [...] , araliphatic sulfonium salts having anion including adamantane structure, nor [...] araliphatic sulfonium salts having anion including structure, sulfonamide structure [...] more preferably having, compound (4-2) is preferably in particular.

[B] as content of acid generator and a, is acid generator and a when as acid generator, the radiation-sensitive resin composition in terms of ensuring and developing sensitivity, polymer 100 parts by mass of hereinafter parts by mass of 0.1 parts by mass of 30 or more are preferably present in the salt, hereinafter parts by mass of 0.5 parts by mass of is preferably 20 or more, 15 or more parts by mass of 1 hereinafter parts by mass of more preferably, 3 parts by mass of is parts by mass of in particular preferably 15 or more. acid generator by said content agent is regulated to, the radiation-sensitive resin composition sensitivity and development, developability with an. is. one or a acid generator and a 1, use can be made of, at least one 2.

<[C] 유기 용매 >

The radiation-sensitive resin compositions contain conventional and comprising at organic solvent. organic solvent having, at least polymer, acid generator and a and according to the hope contained in the such as control body diffusion of acid solubilizing or dispersing solvates has is not particularly limited in if.

[C] as organic solvent, for example alcohol solvent, -4-hydroxy-solvent, ketone-based organic solvent, amide-based solvent, an ester-based organic solvent, as to the aromatic hydrocarbon hydrocarbon solvent.

Alcohol as solvent, for example

Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanols, iso-pentanols, 2-methyl butanol, sec-pentanols, tert-pentanols, [...] 3-, n-cyclohexanol, pentanols methyl 2-, sec-cyclohexanol, 2-ethylbutanol, sec-heptanols, 3-heptanols, n-octanol, 2-ethylhexanol, sec-octanol, roh Neel alcohol -n, 2, 6-dimethyl-4-heptanols, n-tridecanols, sec- fortune thread alcohol , tree methyl Roh Neel alcohol , midifiers targeting-sec alcohol, sec- [...] , [...] alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3, 3, 5-trimethyl cyclohexanol, benzyl alcohol, diaryl three ton alcohol such as mono alcohol solvent;

Ethylene glycol, 1, 2-propylene glycol, 1, 3-butylene glycol, 2, 4-pentanediol, 2-methyl -2, 4-pentanediol, 2, 5-hexanediol, 2, 4- [...] , 2-ethyl -1, 3-hexanediol, diethylene glycol, dipropyleneglycol methyletheracetate and, TEG, tree solvent is regulated so as to have of the polyhydric alcohol, ethylene glycol, propylene;

Ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether, ethylene [...] , ethylene glycol biphenyl ether, ethylene glycol-2-ethyl butyl ether, d ethylene glycol mono methyl ether , d ethylene glycol mono ethyl ether , d ethylene glycol mono pro the ether which will bloom , d ethylene glycol mono butyl ether , [...] , propylene glycol monomethyl ether, propylene glycol mono ethyl ether, propylene glycol mono propyl ether, propylene glycol monobutyl ether, deep [...] , deep [...] , deep [...] such as of the polyhydric alcohol, as to the aromatic hydrocarbon as a partially etherified solvent is regulated so as to have.

-4-hydroxy-solvent as, for example

30 parts by weight of diethyl ether, deep with the ether which will bloom , such as d butyl etherd alkyl ether orgin solvent;

Propanamines, tetrahydropyran an annulus-4-hydroxy-solvent;

d phenyl ether , not having an aromatic ring such as brush (the preparatio) as to the aromatic hydrocarbon containing-4-hydroxy-solvent.

As ketone-series solvent, for example acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-isobutyl ketone, d ethyl ketone , methyl-iso-isobutyl ketone, 2-(methyl-n- [...]) [...] , ethyl-n-isobutyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone-iso, tree roh or rice field methyl ketone-series solvent chain such as:

Cyclopentanone, cyclohexanone, [...] cycloalkyl, cycloalkyl non octahydro, trimethylcyclohexanone an annulus ketone-series solvent:

2, 4- pentane D it comes , neel acetone alkylacetoacetoates, as to the aromatic hydrocarbon alkylacetoacetoates phenones.

Amide-based solvent as, for example N, N '-dimethyl already will be and the D rice field which will doze , N-methylpyrrolidone an annulus amide-based solvent;

N-methyl formamide, N, N-dimethylformamide, N, d ethyl gun roentgen per hour at one meter amide -N, acetamide, N-methylacetamides, N, cement clinker using ironworks slag N, such as N-methyl propionamide, as to the aromatic hydrocarbon chain amide-based solvent.

Ester-based solvent as, for example

Acetic acid methyl, acetic acid ethyl, n-propyl acetic acid, acetic acid iso-propyl, acetic acid n-butyl, acetic acid iso-butyl, acetic acid sec-butyl, acetic acid n-pentyl, acetic acid i-pentyl, acetic acid sec-pentyl, acetic acid 3- [...] , [...] acetic acid, 2-ethyl butyl acetic acid, acetic acid 2-ethylhexyl, acetic acid benzyl, aminocyclohexyl acetic acid, acetic acid [...] , acetic acid n-isononylesters tioester acetic acid, such as a solvent;

Ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, d ethylene glycol mono methyl ether acetate , d ethylene glycol mono ethyl ether acetate , d ethylene glycol mono -n-butyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol mono ethyl ether acetate, propylene glycol mono propyl ether acetate, propylene glycol monobutyl ether acetate, deep [...] , deep [...] considering permeabilities as a partially etherified of the polyhydric alcohol, such as solvent;

Dimethyl polycarbonate, carboxylate [...][...] solvent;

Diaryl the set it buys the glycol , acetic acid [...] , phenylpropion-acid ethyl, propionic acid n-butyl, amyl-iso propionic acid, oxalic acid diethyl, oxalic acid di-n-butyl, methyl acetic acid acid synthase, acetohydroxy acetic acid ethyl, lactic acid methyl, lactic acid ethyl, lactic acid n-butyl, lactic acid n-amyl, malonic it buys the D ethyl , phthalic dimethyl, phthalic diethyl as to the aromatic hydrocarbon.

Hydrocarbon solvent as, for example

N-pentane, iso-pentane, n-hexanediol, iso-hexanediol, n-heptane, iso-heptane, 2, 2, 4-tree methyl pentane , n-octane rating, iso-octane rating, cyclohexane, methyl cyclohexane for example, aliphatic hydrocarbon solvent;

Benzene, toluene, xylene, [...] , ethylbenzene, trimethyl benzene, methyl ethyl benzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, tree ethylbenzene, di-iso-propylbenzene, n- oh wheat naphthalene strain of an aromatic hydrocarbon solvent as to the aromatic hydrocarbon.

Among them ester-based solvent, ketone-series solvent are preferably present in the salt, a polyhydric alcohol as a partially etherified considering permeabilities solvent, ketone-series solvent is preferably annular, propylene glycol monomethyl ether acetate, cyclohexanone is more preferably, the. The radiation-sensitive resin composition 2 1 an organic solvent containing one or at least one is as described above may be.

<[D] 산 확산 제어체 >

The radiation-sensitive resin composition demands a process, may containing control body diffusion of acid.

[D] by an exposure control body diffusion of acid an acid from acid generator and a resist layer where by controlling the diffusion phenomenon, in non-exposure region undesirable chemical reaction suppression the cracking the, obtained radiation-sensitive resin composition and much improved storage stability, resolution as resist in addition more ratio is improved, exposure from developing treatment post exposure delay time is generated between resist pattern line width change lines are, process stabilization rolled mass, and is excellent in radiation-sensitive resin composition are obtained. concerned in control body diffusion of acid the radiation-sensitive resin composition containing in embodiment, compounds of glass (hereinafter, properly '[ D] acid diffusion control number' constitution: a method) may in the form of, polymer even form, incorporated in the porous dielectric carrier, as part of, .may be in the form of a of both.

[D] acid diffusion control agent, which are for example formula (5a) compounds represented by (hereinafter, 'nitrogen containing compounds (I)' is, sometimes referred to as), two nitrogen atoms in in same molecule compounds having 2 (hereinafter, 'nitrogen containing compounds (II)' is, sometimes referred to as), compounds having two 3 nitrogen atoms (hereinafter, 'nitrogen containing compounds (III)' is, sometimes referred to as), amide containing compound, urea compound, nitrogen-containing heterocyclic ring compounds and the like can be mentionned.

Said type (5a) during, R¹², R¹³ and R¹⁴ independently from each other, hydrogen atom, substituted which may be linear, branched or annular alkyl, an aryl group or C1 to C16 aralkyl is.

As nitrogen containing compounds (I), for example such as n- [...] of mono-alkyl amines current; di-n-butylamine, d alkyl amine type such as; triethylamine, tree n- [...] such as trialkyl amine current; such as aromatic amine such as aniline :.

As nitrogen containing compounds (II), such as ethylene diamine, N, N, N ', N' -tetramethyl ethylenediamine as to the aromatic hydrocarbon.

Nitrogen containing compounds (III) as, , for instance, polyethylene imine, polyaryl amine such as polyamine compound; dimethylamino phenethyl acrylamides as to the aromatic hydrocarbon polymer such as.

The compound containing amide, for example formamide, N-methyl formamide, N, N-dimethylformamide, acetamide, N-methylacetamides, N, N-dimethyl acetamide, propionamide, benzamide, pyrrolidone, as to the aromatic hydrocarbon N-methylpyrrolidone.

Urea compound, for example element, methyl urea, 1, 1-dimethyl urea, urea dimethyl 1, 3-, 1, 1, 3, 3-tetramethyl urea, 1, 3-diphenylurea, as to the aromatic hydrocarbon butyl mote five thunder Oh tree.

Nitrogen-containing heterocyclic compound ring, for example pyridine, 2-methylpyridine such as pyridine current; composting apparatus-propyl N, N-(undecane-1- one carbonyl jade hour ethyl) morpholin such as morpholin current; pyrazine, pyrazole as to the aromatic hydrocarbon.

In addition said comprising nitrogen compound, reinforcement, a powdered characteristic using compounds having anchoring groups may be loaded with. Such reinforcement, a powdered characteristic compound comprising nitrogen group, for example N-t-butoxycarbonyl piperidine, N-t-butoxycarbonyl imidazole, benzimidazole-butyloxycarbonyl N-t, N-t-butoxycarbonyl-2-phenylbenzimidazoles, N-(t-butoxycarbonyl) di-n- [...] , N-(t-butyloxycarbonyl) diethanolamines, N-(t-butyloxycarbonyl) DC [...] , N-(t-butoxycarbonyl) diphenylamine, N-t-butoxycarbonyl-4-hydroxy piperidine, oh wheat jade hour carbonyl -N-t as to the aromatic hydrocarbon-4-hydroxy piperidine.

Furthermore, as acid diffusion control number, the photosensitive patterns to be exposed by the same collapsible optical for generating the weak may be loaded with using base. Optical collapsible base as, for example exposure capable of decomposing under the diffusion of acid controlling capability with an onium of the plate is lost can be mentionned compounds and the like. Onium salt compound, which are for example formula (5b-1) which appears as the sulfonium salts, formula (5b-2) [...] which appears as the can be mentionned compounds and the like.

Said type (5b-1) and formula (5b-2) during, R¹⁵ to R¹⁹ independently from each other, hydrogen atom, alkyl, alkoxy groups, is hydroxy or halogen atom. E^- and Q^- independently from each other, OH^-, R^β-COO^-, R^β-SO₃^- or formula (5-3) is an anionic represented by. Stage, R^β the alkyl, an aryl group or C1 to C16 aralkyl is.

Said type (5b-3) during, R²⁰ is hydrogen atom some or all of the fluorine nuclear reactor carbon atoms which may be substituted 1 to 12 linear or branched alkyl, of carbon number 1 to 12 linear or branched alkoxy group is on. The u is integer number of 0 to 2.

As base collapsible optical said, which are for example which is can be mentionned compounds and the like.

As base collapsible optical said, among them [...] preferably, preferably than [...] triazine, tree [...] , more preferably, the sulphonate is 10- [...][...] tree.

[D] as content of control body diffusion of acid, acid diffusion control body is when as control diffusion of acid, polymer 100 parts by mass of 20 to parts by mass of 0 and is preferably a mass, 0.1 parts by mass to 15 parts by mass of preferably is, 0.3 parts by mass of more preferably to 10 parts by mass of, in particular is parts by mass of 5 to parts by mass of 0.5 preferably. acid diffusion control agent exceeds a upper limit said content, the radiation-sensitive resin composition. when is etched.

<[E] 중합체 >

[E] characteristic reinforcement, a powdered polymer-containing a polymer having a (stage, polymer by except that corresponding to). The radiation-sensitive resin composition characteristic reinforcement, a powdered polymer is when the, which does not have groups,, it is necessary that polymer. characteristic reinforcement, a powdered polymer and a constituent unit and including groups is preferably in the. Is reinforcement, a powdered characteristic groups as structural units including, for example (II) polymer structural unit and gives similar to the structural unit and gives the illustrated as as to the aromatic hydrocarbon.

[E] as polymer, for example polymer structural unit and gives (II) to (V) and other structural units as to the aromatic hydrocarbon polymer.

[E] as content of polymer, characteristic reinforcement, a powdered polymer is, at the same time, when group, polymer 100 parts by mass of 200 to parts by mass of 20 and is preferably a mass, 50 parts by mass to 150 parts by mass of preferably is.

<[F] 중합체 >

[F] a polymer having a fluorine atom-containing resin polymer ([A] polymer by except that corresponding to). The radiation-sensitive resin composition polymer by comprising some specific properties, as, when forming a resist film, of fluorine-containing polymer film in the portion in characterized by foot meteor , resist film adjacent the surface uneven distribution of distribution is a tend, connections necessary hitherto acid generator is given during immersion exposure number control diffusion of acid to eluting with an immersion medium and the like is suppressed. Furthermore, polymer is characterized by sexual and the water repellency of at, resist coating and a desired contact angle advance of an immersion medium can be range, bubble can suppress generation of deficiency. Furthermore, retraction of resist film and the immersion medium in closely, and the hanging sill is droplets can be exposure scan high speed. Thus the radiation-sensitive resin composition polymer by comprising some specific properties, as, suitable pick immersion exposure can be material, and forming a coating film resist.

[F] as polymer, a polymer having fluorine atoms, but is not particularly limited in, the radiation-sensitive resin composition in water polymers fluorine atom content (mass %)and has high preferably. polymers by a high active component content and an fluorine atom, the above-mentioned uneven distribution of larger than in the degree of is, obtained dissolution control water-repellent and anti-adhesive film presence of..

[F] as polymer fluorine atom content, is preferably 1 mass % or more, 2 mass % to 60 mass % is preferably, 4 mass % to 40 mass % and more preferably, 7 mass % to 30 mass % is preferably in particular. polymer fluorine atom content lower limit if less than said, resist of the outer surface of a membrane. includes a hydrophobic. In addition polymer fluorine atom content (mass %)the 13C-NMR spectrum measurement by the determined a probable structure of of the polymer, can be calculated from the generated structure thereof.

[F] as polymer, structural units and structural units a (Fa) (Fb) selected from the group consisting of having at least 1 species it is preferable that the. (Fa) a constituent unit which polymer structural units and one or each (Fb) 1 is which may have at least one 2.

[Structural units (Fa)]

Formula has an (Fa) structural units (6a) is a constituent unit which is represented by. by having a constituent unit which polymer (Fa), it is possible to adjust the fluorine atom content.

Said type (6a) during, R^D hydrogen atom, methyl or trifluoromethyl is. G sum the epitaxial silicon, oxygen atoms, sulfur atoms, -CO-O-, -SO₂-O-NH-, -CO-NH or-is-O-CO-NH. R^E having fluorine atoms of at least 1 carbon atoms of 6 to 1 1 of chain hydrocarbon group of 1 or at least 4 to 20 carbon atoms having fluorine atoms of hydrocarbon group is annular aliphatic of 1.

Said R^E at least represented by having fluorine atoms of 1 to 6 carbon atoms as 1 of chain hydrocarbon group, for example trifluoromethyl, 2, 2, 2-trifluoro ethyl, purple base Oro ethyl , 2, 2, 3, 3, 3- [...] writing, writing profile 1, 1, 1, 3, 3, 3-hexafluoropropane, perfluoro n-writing, perfluoro i-writing, perfluoro n-butyl to, perfluoro i-butyl to, perfluoro t to-butyl, 2, 2, 3, 3, 4, 4, 5, 5- [...] octahydro, as to the aromatic hydrocarbon purple [...] group.

Said R^E at least represented by having fluorine atoms of 1 to 4 carbon atoms as hydrocarbon group annular aliphatic 20, for example mono [...] , [...] -1, 4 content, purple [...] , mono [...] group, [...] -1, 4 content, purple [...] , fluoro [...] , fluoro [...] , fluoro [...] , fluoro [...] , fluoro tree hour claw group, fluoro tetra hour claw as to the aromatic hydrocarbon group.

(Fa) as monomer for providing said structural units, for example trifluoromethyl (meth) acrylic esters, (meth) acrylic esters 2, 2, 2-trifluoroethyl, 2, 2, 2-triple base Oro ethyl jade hour carbonyl methyl (meth) acrylic esters, (meth) acrylic esters base Oro ethyl purple, perfluoro n-propyl (meth) acrylic esters, perfluoro i-propyl (meth) acrylic esters, perfluoro n-butyl (meth) acrylic esters, perfluoro i-butyl (meth) acrylic esters, perfluoro t-butyl (meth) acrylic esters, 2-(1, 1, 1, 3, 3, 3-hexafluoropropane profile) (meth) acrylic esters, 1-(2, 2, 3, 3, 4, 4, 5, 5-octahydro) [...][...][...] kurtosis) (meth) acrylic esters, (meth) acrylic esters [...] purple, 1-(2, 2, 3, 3, 3- [...]) (meth) acrylic esters, mono [...] (meth) acrylic esters, (meth) acrylic esters [...] -1, 4 content, purple [...] (meth) acrylic esters, (meth) acrylic esters mono [...] , [...] -1, 4 content (meth) acrylic esters, (meth) acrylic esters [...] purple, fluoro [...] (meth) acrylic esters, (meth) acrylic esters methyladamantyl fluoro, fluoro isobornyl (meth) acrylic esters, (meth) acrylic esters [...] fluoro, fluoro tricyclodecyl (meth) acrylic esters, (meth) acrylic esters tricyclodecyl tetra fluoro as to the aromatic hydrocarbon.

Among them base Oro ethyl jade hour carbonyl methyl triple 2, 2, 2-(meth) acrylic acid esters are preferably.

(Fa) as ratio of the structural units, constituting a overall structure the unit 5 mole % to 95 mole % are preferably present in the salt, 10 mole % to 90 mole % is preferably, 30 mol % to 85 mol % is more preferably, the. Such the content ratio achieved by applying it to an immersion exposure control the speed of the resist of the outer surface of a membrane contact angle a large dynamic than. and capable of expression.

[Structural units (Fb)]

Formula has an (Fb) structural units (6b) is a constituent unit which is represented by. (Fb) by having a constituent unit which polymer to the web hydrophobic, the radiation-sensitive resin formed from the compositions resist of the outer surface of a membrane dynamic contact angle can be further improved..

Said type (6b) during, R^F hydrogen atom, methyl or trifluoromethyl is. R²¹ (s+1) of 1 to 20 carbon atoms which hydrogen hydrocarbons of, R²¹ of R²² side at the end of the oxygen atoms, sulfur atoms, -NR '-, carbonyl group to, -CO-O or-CO-NH-bonded structure may be.. R ' is hydrogen atom, alkyl having organic group is 1. R²² sum the epitaxial silicon, 1 to 10 carbon atoms of carbon number 2 of chain hydrocarbon group of 4 to 20 of annular aliphatic of hydrocarbon group is 2. X² having fluorine atoms of at least 1 carbon atoms of hydrocarbon group chain of 1 to 20 is 2. A¹ the oxygen atoms, -NR "-, -or *-CO-O-SO₂-O-* is. R " is hydrogen atom, alkyl having organic group is 1. * A R²¹ exhibits and site which binds to the. R²³ is hydrogen atom or is organic group is 1. The s is integer number of 1 to 3. Stage, when s is 2 or 3, plurality of R²², X², A¹ and R²³ each. which may be the same or different.

Said R²³ when the hydrogen atom is, polymer alkali developer-solubility of a preferably in signal is arranged to correspond.

Said R²³ as organic group is 1 in terms of, for example, a powdered characteristic to, alkali-dissociative or may substituents 1 to 30 carbon atoms as to the aromatic hydrocarbon hydrocarbon group of.

Said structural units as (Fb), which are for example formula (6b-1) to (6b-3) signal expressed by as to the aromatic hydrocarbon structural units.

Said type (6b-1) to (6b-3) during, R^21' 1 to 20 of the carbon atoms 2 is linear, branched or annular, saturated or unsaturated hydrocarbon group is of. R^F, X², R²³ s and the type (6b) and a is agree. When s is 2 or 3, plurality of X² and R²³ each. which may be the same or different.

Said structural units (6b) as ratio of the, constituting a overall structure the unit 0 mole % to 90 mole % are preferably present in the salt, 5 mole % to 85 mole % is preferably, 10 mole % to 80 mole % is more preferably, the. Such the content ratio achieved by applying it to an, the radiation-sensitive resin formed from the compositions resist film surface lowering alkali development in dynamic contact angle the objective compound. degree.

[Structural units (Fc)]

[F] polymer (Fa) addition (Fb) and said structural units, structural units including reinforcement, a powdered characteristic groups (hereinafter, 'structural units (Fc)' also referred to as) is even when they have a a (stage, structural units (Fb) except that corresponding to by). (Fc) polymer is by having structural units, the shape of the pattern is obtained carried out, the amount of shift is better. Structural units as (Fc), the above-mentioned in polymers as to the aromatic hydrocarbon (II) structural units.

Said (Fc) as ratio of the structural units, constituting a overall structure the unit 5 mole % to 90 mole % are preferably present in the salt, 10 mole % to 70 mole % is preferably, 15 mole % to 60 mole % and more preferably, 15 mole % to 50 mole % is preferably in particular. Ratio of the structural units (Fc) said lower limit if less than, for development, developability resist pattern surface to deficiency might not be. Said structural units (Fc) exceeds a ratio of the upper limit, hydrophobic of the outer surface of a membrane obtained. includes a.

[Structural units other]

Furthermore, structural units said addition polymer, for example structural units including alkali-soluble groups, lactone structure, structure sultone structure and with cyclic carbonate for at least selected from the group consisting of structural units including structure of species 1, alicyclic groups structural units including another payload such as is which may have structural units. Alkali-soluble into said and, in its turn, for example carboxyl, sulfonamide amide , as to the aromatic hydrocarbon sulfo group. Lactone structure, structure sultone structure and with cyclic carbonate for at least selected from the group consisting of 1 as a constituent unit which of species, the above-mentioned in polymers as to the aromatic hydrocarbon (IV) structural units.

As the content ratio of structural units said other, constituting a overall structure the unit, conventional and 30 molar % hereinafter, is preferably 20 mole % hereinafter. Of structural units containing said other said ratio exceeds a upper limit, the radiation-sensitive resin composition pattern forming to a DC voltage. when.

The radiation-sensitive resin composition in as content of polymer, 100 parts by mass of polymer, and is preferably a mass 20 to 0, to 15 parts by mass of 0.5 parts by mass of is preferably, 10 to parts by mass of 1 more preferably, the is parts by mass of. polymer content of said exceeds a upper limit, the radiation-sensitive resin composition pattern forming to a DC voltage. when.

<Other optional components >

The radiation-sensitive resin composition to said addition, other optional components is as described above may be containing. Said other optional components as, for example and localized promoter, surfactant, alicyclic framework containing compound, increase/decrease as to the aromatic hydrocarbon number. Such other optional components 1 each one or at least one may which practices a 2.

(And localized promoter)

And localized promoter is the radiation-sensitive resin composition containing in when the child, polymer to more efficiently resist film surface segregate to the effect it is. The radiation-sensitive resin upon the composition and localized by a promoter,, the amount of the polymer thereby reducing the number of errors conventional. Therefore, LWR, developing deficiency, such as pattern collapse resistance without impairing the fundamental aspects resist, resist pattern or further reducing the release of an immersion fluid to component, capable of performing high-speed scan by speed than, liquid-immersion exposure can be, as a result watermark deficiency derived immersion such as resist for inhibiting the deficiency hydrophobic of the outer surface of a membrane the objective compound.. Such and localized as those that can be used as promoters for, 30 or more dielectric constant 200 hereinafter and, pressure boiling point at 1 100 °C: molecular weight compound or more. As such compounds, specifically, lactone compound, carbonate compound, nitrile compounds, a polyhydric alcohol as to the aromatic hydrocarbon.

As embodiments of said lactone compounds, for example γ-butyrolactone, ballet propoxybenzeneacetic acid, [...] , nor [...] as to the aromatic hydrocarbon.

As embodiments of said carbonate compound, as for example propylene polycarbonate, ethylene polycarbonate, polybutylene polycarbonate, as to the aromatic hydrocarbon polycarbonate vinylene.

As said of nitrile compounds embodiment, for example as to the aromatic hydrocarbon [...]. Said embodiment the polyhydric alcohol, as, for example glycerin as to the aromatic hydrocarbon.

As content the level of accelerator is and localized, the radiation-sensitive resin composition of the polymer in 100 parts by mass of total amount 500 to parts by mass of 10 and is preferably a mass, is preferably 30 to 300 parts by mass of.

(Surfactant)

Therefrom surfactant, streaking radiation, development, developability with an a shows an ornamenting effect by being of measuring the such as. Surfactant, the jade hour ethylene the ether which it will soak , for example, , poly [...] , comprises a polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n- roh Neel phenyl ether , polyethylene [...] , nonionic surfactant such as polyethylene [...] ; as commercial products, KP341 (accomplishing musician [...]high school manufacturing), poly flow No.75, copper No.95 (or more, of an un-cross-linked it buys manufacturing accomplishing musician), f top EF301, copper EF303, copper EF352 (or more, manufacturing [...][...]), mega face F171, copper F173 (or more, manufacturing DIC), FC430-flora, copper FC431 (or more, manufacturing PCM three [...]), AG710 guard asahi , supple magnetron S-382, copper SC-101, copper SC-102, copper SC-103, copper SC-104, copper SC-105, copper SC-106 (or more, manufacturing high school glass asahi) as to the aromatic hydrocarbon. The radiation-sensitive resin composition in as content of surfactant, polymer 100 parts by mass of 2 parts by mass of normal is hereinafter.

(Alicyclic framework containing compound)

Alicyclic framework containing compound dry etch resistance, pattern shape, the adhesion between the material surface and substrate cracking rolled soundproof wall improved in..

(Increase/decrease number)

Sensitizer number wherein the formation of acid to acid generator for increasing action is, the radiation-sensitive resin composition 'apparent sensitivity' . cracking to improve.

Increase/decrease agent, for example carboxylic it will doze, type , lung rice field type alkylacetoacetoates, benzophenone current, naphthalene current, phenol, via diacetyl, texturing, it cuts it will go direct reduction process for iron-oxide, [...] , anthracene current, as to the aromatic hydrocarbon lung looking old Oh position type. These sensitizer may be used alone and may which practices a at least one 2. The radiation-sensitive resin composition as content agent increase/decrease in, polymer 100 parts by mass of 2 parts by mass of normal is hereinafter.

<Manufacturing method radiation-sensitive resin composition >

The radiation-sensitive resin composition, for example polymer, acid generator and a, as needed contained in the control diffusion of acid number, polymer, polymer and optional components, and an organic solvent by combination in desired proportions can be produced. The radiation-sensitive resin composition after mixing and, for example pore diameter 0.2 micro m degree of filter and so forth it is preferable that the filtration of the slurry suspension is. The radiation-sensitive resin composition as solid content, 0.1 mass % to 50 mass % is conventional, 0.5 mass % to 30 mass % are preferably present in the salt, 1 mass % to 20 mass % is preferably.

The radiation-sensitive resin composition comprises an alkali a positive film is illuminated by light even for forming pattern, containing organic solvent negative film is illuminated by light, use can be made of, even for forming pattern. At, film is illuminated by light containing organic solvent negative respectively, the radiation-sensitive resin composition higher resolution exhibiting can be exerted.

<Method of forming resist pattern >

The method the forming resist pattern,

The using a radiation-sensitive resin composition, a process forming a resist film (hereinafter, ' resist film forming process' is, sometimes referred to as),

Said resist layer is exposed a process for etching multiple (hereinafter, ' exposure process' is, sometimes referred to as) and

Flood exposed to light, and said process developing resist film (hereinafter, ' developing process' is, sometimes referred to as)

Has.

Forming resist pattern according to the method, the above-mentioned the a radiation-sensitive resin composition use is made of an electrolyte, while wide shift mask exhibits EL, small LWR, each pixel, in addition having excellent rectangular mother pipe having a cross sectional shape so as to form a resist pattern can be. Hereinafter, each process. also disclosed.

[Resist film forming process]

In the process, the a radiation-sensitive resin composition. forming a resist film using. As a substrate forming a resist film is, e.g., silicon wafer, silicon dioxide, such as a wafer coated aluminum as to the aromatic hydrocarbon of publicly known conventional. Furthermore, for example Japanese patent notification call 59-93448 bovine patent disclosure Japanese or Official Gazette call 6-12452 flat Official Gazette or the like is-up of said organic-based or inorganic system disclosure includes an anti-reflection film forming a may. Method applied as, for example, spin coating (spin coating), applied flexible, roll applications as to the aromatic hydrocarbon. After applying the, as needed, to is volatilized for solvent in coating, pre baking (PB). it is possible. As temperature PB, and 140 °C to 60 °C conventional, preferably is 120 °C to 80 °C. As time PB, conventional 5 seconds to 600 seconds, preferably 10 seconds to 300 superplasticizer. Forming a resist film thickness of the as, are preferably present in the salt 10 nm to 1,000 nm, preferably 10 nm to 500 nm is.

Environment basic contained in order to preventing influence of impurities, for example Japanese patent disclosure flat 5-188598 call Official Gazette is disclosure or the like is installed on the semiconductor layer which is not resist film may be. Furthermore, resist from the film such as acid generator for preventing leakage of the, for example Japanese patent disclosure number 2005-352384 call Official Gazette or the like a disclosure immersion passivation layer is resist film may be is installed on. Furthermore, these techniques can be combination.

[Exposure process]

In the process, said resist film formed in the resist film forming process, through photomask (optionally, prevents the immersion such as water) an exposed irradiating exposure light. Exposure light as, intended to according to line width of a pattern, for example visible light, ultraviolet, deep ultraviolet, extreme ultraviolet (13.5 nm, EUV), X ray, a partial region of one face of line γ; electron beam, α line as to the aromatic hydrocarbon charged particle line. These, among other things, , deep ultraviolet, EUV, electron beam is preferably, ArF excimer laser beam (wavelength 193 nm), KrF excimer laser beam (wavelength 248 nm), EUV, electron beam is more preferred to set a and, ArF excimer laser beam, EUV, more preferably, the electron beam is.

Outputs the immersion exposure exposure, as immersion fluid using, for example water, fluorine-based inert liquid as to the aromatic hydrocarbon. immersion misfortune and transparent to exposure wavelength, in addition a projected on the optical Image distortion a mixture amounting to at least a person's name and the temperature coefficients of refractive index from that of the to is as small as possible preferably the liquid, in particular exposure light source when ArF excimer laser beam (wavelength 193 nm), in addition to the above-mentioned aspect, and ease of available, and ease of handling in such as it is preferably. On the water when, and reduces the surface tension of the of, slightly an additive which enhances the force surfactant is added to ratio of may. They are disposed over a wafer, and without dissolving the resist film of, optical coating of the lower surface of lens in addition can ignore the out of order then, the influence to is preferably in the. As a water using Na:K is preferably distilled.

Said post exposure, post exposure baking unit (PEB) is performed, in portion exposure resist film, patterns to be exposed by the same light originating from the acid generator and a acid polymer such as reinforcement, a powdered characteristic of a non-woven fabric is covered it is preferable that the promoting dissociation of. By PEB is, exposure, solubility in the developer and allows the optical preparaed pin. difference in. As PEB temperature, and 180 °C to 50 °C conventional, Na:K is preferably 130 °C to 80 °C. PEB time as, conventional 5 seconds to 600 seconds, preferably 10 seconds to 300 superplasticizer.

[Developing process]

In the process, the film is illuminated by light, developing a resist film exposure exposure process. The, predetermined resist pattern formed is. Said developer as, for example alkaline developing solution, an organic solvent-containing a developer as to the aromatic hydrocarbon. The developer 107 first pattern in response to the shape may be selected. Mask pattern by exposing when projected on the resist film, high strength light irradiation by developing the aqueous solutions of an alkaline region, additional exposure or more a specified threshold, dissolved, removed to only positive as to form a resist pattern of can be. While, mask pattern projected on the resist film by exposing when optical irradiation intensity area is weak, thus the user, containing organic solvent by developing the solution that uses a high-, a specified threshold, dissolved additional exposure hereinafter, negative removed to only can be as to form a resist pattern of. Won an offshore of the three or more injection nozzles are arranged these according to pattern shape may be loaded with the developing combination.

Said as alkaline developing solution, for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium silicate metadata, ammonia, triethylamine, n-propyl amine, d ethyl amine , di-n-propyl amine, triethylamine, methyl d ethyl amine , ethyl dimethylamine, triethanolamin, tetra [...] (TMAH), pyrrole, piperidine, choline, 1, 8-diazabicyclo-[ 5.4.0]-7- fortune it counted , 1, 5-diazabicyclo-[ 4.3.0]-5-nonene such as alkaline at least 1 a species as to the aromatic hydrocarbon alkaline aqueous solution.

Said an organic solvent-containing organic solvent as a developer contained in the, for example to the radiation-sensitive resin composition organic as a solvent 1 of solvent which enumerate the one or at least one as to the aromatic hydrocarbon 2. These, among other things, , -4-hydroxy-solvent, ester-based solvent, ketone-series solvent is preferably. -4-hydroxy-solvent as, preferably solvent is-4-hydroxy-containing aromatic, preferably than overspeed not.

As ester-based solvent, preferably solvent is tioester acetic acid, acetic acid n-butyl is more preferred to set a.. As ketone-series solvent, chain ketone-series solvent are preferably present in the salt, preferably than [...] 2-.

As content of developer of organic solvent, and is preferably at least 80 mass %, 90 mass % or more and is more preferred to set a, 95 mass % or more, and more preferably in a and, in particular preferably at least 99 mass %. Developer of organic solvent ranges from heightening the content of the by said, preparaed exposure, bottom electrode is installed under the second layer consists of a contrast, as a result, while having a coating layer exhibiting a wider EL, LWR and CDU into smaller one while can be a resist pattern. Furthermore, as salts of organic solvent, for example water, : such as silicone oil.

The developer, in order to by can add. Entangling surfactant, ionic or non-ionic fluorine-and/layer or a silicon-based surfactant, use can be made of,.

Developing method as, for example crude during developing solution filled, immersing time the semiconductor substrate on (the dipping law) method, substrate surface three or more injection nozzles are arranged by the surface tension [...] developing time constant is varied based on n frame periods (it ladles, the wild law) method, three or more injection nozzles are arranged substrate surface method spraying (spray method), that rotate at constant velocity rate on a substrate ([...]) developer derived developer while scanning the surface nozzle continues to deriving a method (dynamic dispense method) as to the aromatic hydrocarbon.

Said developed with the use of the water, alcohol such as after rinse using rinse solution, it is preferable that the drying. Said rinse method as, for example constant velocity that rotate at a lower part of the window pattern continues to deriving a rinse solution method (spin coating method), during crude cleaning method (the dipping law), immersing time the semiconductor substrate on, substrate surface method spraying rinse solution as to the aromatic hydrocarbon (spraying, pouring,).

In the embodiment

Hereinafter, for the present invention embodiment which specifically, based aspect, the present invention refers to these embodiment aspect limited not. Method for measurement of material properties when applied to various showed to hereinafter.

[Weight average molecular weight (Mw), number average molecular weight (Mn) and degree of dispersion (Mw/Mn)]

The Mn and Mw polymer GPC column (G2000HXL: 2 two, G3000HXL: 1 two, G4000HXL: two 1, stone bovine manufacturing) using, flow: 1.0 ml/min, elution solvent: propanamines, concentration: 1.0 mass %, sample injection amount: 100 μL, column temperature: 40 °C, detector: in conditions analysis of parallax refractometer, monodispersed of polystyrene standard a gel permeation chromatography, it was determined that by (GPC). Furthermore, degree of dispersion (Mw/Mn) a Mw and Mn was calculated from the generated the result of measurement of a standard.

[Low molecular weight portion content]

[A] polymer in low molecular weight portion (portion of less than 1,000 molecular weight) content of (mass %)to reverse phase high performance liquid chromatography (HPLC) by the, strength of the brew [...] GLV (Intersil ODS-25 micro m, 4.6 mm φ× 250 mm) HPLC column using, it was determined that conditions hereinafter.

Elution solvent: acrylonitrile/0.1 mass % phosphoric acid aqueous solution

Flow: 1.0 ml/min

Concentration: 1.0 mass %

Sample injection amount: 100 μ L

Detector: parallax refractometer

[¹³ C-NMR analysis]

The content ratio of structural units each in polymers (molar %)to obtain a¹³ C-NMR device nuclear magnetic resonance analysis (ECX400-JNM, nihonat the time of which is burnt manufacturing) which is obtained by using a, measuring as a solvent was carried out using with middle claw gun roentgen per hour at one meter.

<Synthesis of compound >

[Synthesis example 1] (compound synthesis of (M-1))

According to known as a raw material of the, a fullerene derivative is represented by formula (M-1) have been synthesised.

3-bromo indolepyruvic 9.21g (55.5mmol, 1-ethyl-3-[ 3-(dimethylamino) profile] carboxylic [...] (EDCI) 10.6g (55.5mmol), dimethylamino pyridine (DMAP) 6.78g (55.5mmol) methane dichloro as solvent and in branch multi function cap is enclosed in a 150 ml 500 ml stirring section. Thereto, 3-hydroxy-γ-butyrolactone 5.67g (55.5mmol) 50 ml of methane solution was dripped slowly at room temperature. After time 48 at room temperature, is stopped on the transmission side and react [...] , dichloro methane on aside. After concentrated, by of column chromatography for purifying, [...] bromo 3-9.89g obtained (71% yield).

Continue to, said obtained 3-bromo [...] 5.0g (19.9mmol) sodium acid and methacrylic acid 4.30g (39.8mmol) to, and water as solvent by adding a 20.0g 30.0g propanamines, in 60 °C 20 time stirring section. After cleaning the concentrated within separating , by of column chromatography for purifying, 3.47g for (M-1) compound obtained (yield 68%).

[Synthesis example 2 to 39] (compound synthesis of (M-39) to (M-2))

The appropriately selecting the precursor, by an input as well in the embodiment 1, formula (M-2) to (M-39) have been synthesised of a compound which is represented by.

<Synthesis of polymer >

Each polymer in the synthesis of said monomer other than using monomer showed to hereinafter.

< polymer synthesis (1) >

(Synthesis of polymer (A-1)) [in the embodiment 1]

Said compound (M-1) 10.08g (40 molar %)and compound (M-49) 9.92g (60 molar %)of 2-butanone which 40g, AIBN 0.81g as disclosure number radical polymerization in addition (compound total of 5 mole % relative to moles) matter by monomer solution have been prepared. Furthermore, 100 ml of 2-butanone whereinto the rice field 20g of a multi function cap opening 3 after nitrogen purge ingredient 30, with stirring, in a the same circuit, is heated to 80 °C, said manufacturing a monomer solution is dripped to funnel 3 was dripped over time. Dripping disclosure disclosure an acid processing time is a of the polymerization reaction, the polymerization of the embodiment the time 6. After polymerization, polymerization reaction solution was cooled to 30 °C hereinafter by starting water. 400g of methanol cooled during the used polymerization reactor, was a powdery white and to classify the filtering. Filtration fractionation white powder after cleaning the times 2 to 80g of methanol, filtration fractionation and, in 50 °C 17 time and drying the obtained a (A-1) polymer state powdery white (14.8g, 74% yield). Polymer (A-1) is the Mw of 7,300, is 1.53 the Mw/Mn, the content of the low molecular weight portion was 0.04 mass %.¹³ C-NMR the results of the analysis, (M-1) (M-49) and the content ratio of structural units each derived from each was 39.7 molar % and 60.3 molar %.

[In the embodiment 2 to 9, 10 and 16 to 18 and synthetic e.g. 40 to 99 and 105 to 107] (polymer (A-2) to (A-37) and (A-43) to (A-45) and polymer synthesis of (a-41) to (a-39) and (a-33) to (a-1))

Shown in table 1 and table 2 couple whereof the type and the amount of use of the besides from being monomers, by an input as well in the embodiment 1, polymer (A-2) (a-33) to (a-1) and (A-45) to (A-43) and (A-37) to and have been synthesised each (a-41) to (a-39). (%) Yield of polymer the axial direction of the wafer handling, Mw, content of portion and a low-molecular Mw/Mn (mass %)to table 1 and table 2 value of exhibits together.

< polymer synthesis (2) >

(Synthesis of polymer (A-38)) [in the embodiment 11]

Compound (M-30) 55.0g (50 mole %)and compound (M-75) 31.0g (50 mole %), AIBN 4g as radical disclosure number, and 1g [...] -dodecene t as propylene glycol monomethyl ether 100g particles having a diameter of, in nitrogen atmosphere to, a truck is provided to maintain an 70 °C reaction temperature, visitor is checked through a copolymerized time 6. After polymerization, polymerization a reaction solution are 1,000g n of the dropping an-hexanediol, purified of solidifying a polymer. Said polymer back to continue to monomethyl ether propylene glycol after is added is 150g, 150g methanol in addition, triethylamine 34g and water 6g is applied to, , m-in boiling, hydrolysis reaction and time 8 was performed. After reaction, solvent and the distilling off of decompressing triethylamine, the resulting polymers are 150g with the particles having a diameter of, 2,000g solidifying the liquid is dropped on the oil-in-water, a powdery white generated, is filtered and, in 50 °C 17 time and drying the obtained a (A-38) polymer state powdery white (50.6g, 65% yield). Polymer (A-38) of the Mw is 6,500, the Mw/Mn was 1.62.¹³ C-NMR the results of the analysis, (M-30) and p-hydroxystyrene the content ratio of structural units each derived from 49.7 molar % and each was 50.3 molar %.

[In the embodiment 12 to 15 and synthetic e.g. 100 to 104] (polymer (A-39) to (A-42) synthesis of (a-38) to (a-34) and polymer)

Table 1 which indicates to the besides from being monomers like a tap generation block and in the embodiment 11, polymer and polymer (A-42) to (A-39) have been synthesised for (a-38) to (a-34).

<[F] 중합체의 합성 >

[Synthetic e.g. 108] (synthesis of polymer (F-1))

Said compound (M-56) 79.9g (70 mole %)and compound (M-75) 20.91g (30 mole %)of 2-butanone dissolved in rice field of 100g, 2, 2 dimethyl as disclosure number radical polymerization in addition '-azo bis isobutyrate for 4.77g monomer solution melted to have been prepared. Furthermore, 1,000 ml of 2-butanone rice field whereinto the 100g of a multi function cap opening 3 after nitrogen purge ingredient 30, with stirring, in a the same circuit, is heated to 80 °C, said manufacturing a monomer solution is dripped to funnel 3 was dripped over time. Dripping disclosure the time a disclosure of the polymerization reaction, the polymerization of the embodiment the time 6. After polymerization, polymerization reaction solution was cooled to 30 °C hereinafter by starting water. The polymerization solution after in the atmosphere which it will peelseparating 2L, 150g of dilution and uniformly-hexanediol n, 600g of methanol are input, in the mixed. Continue to of charging a distilled water of 30g, the political ingredient 30 by stirring in addition. Furthermore, is recovered and allowed to lower, a (F-1) polymer including propylene glycol monomethyl ether acetate solution is obtained (yield 60%). Polymer (F-1) of the Mw is 7,200, the Mw/Mn was 2.00.¹³ C-NMR the results of the analysis, (M-56) (M-75) and the content ratio of structural units each derived from each was 71.1% molar 28.9 and molar %.

<Manufacturing radiation-sensitive resin composition >

Radiation-sensitive resin composition a use in the production of acid generator number, organic solvent, acid diffusion control number and and localized respect to promoter showed to hereinafter.

[Number acid generator]

B-1: tree [...] 2-(adamantane-1- one carbonyl jade city)-1, 1, 3, 3, 3-pentafluoropropane-1-sulfonate (compounds represented by formula (B-1))

B-2: tree [...][...] -2-yloxy (compounds represented by formula (B-2))

B-3: tree [...] 3-(N-piperidine sulfonyl)-1, 1, 2, 2, 3, 3-hexafluoropropane-1-sulfonate (in terms of compound formula (B-3))

[[ C] organic solvent]

C-1: acetic acid propylene glycol monomethyl ether

C-2: cyclohexanone

[Control diffusion of acid number]

D-1: tree [...] (compounds represented by formula (D-1))

D-2: tree [...] 10- [...] sulfonate (compounds represented by formula (D-2))

D-3:N-(undecane-1- one carbonyl jade hour ethyl) morpholin (in terms of compound formula (D-3))

D-4:2, 6-isopropyl aniline (compounds represented by formula (D-4))

D-5: tree [...] -n (compounds represented by formula (D-5))

[[ G] and localized promoter]

G-1: γ-butyrolactone

[In the embodiment 19]

[A] polymer (A-1) 100 parts by mass of as, number acid generator (B-1) 8.5 parts by mass of as, (C-1) 2,240 (C-2) 960 parts by mass of organic as solvent, and, acid diffusion control number (D-1) 2.3 parts by mass of as, (F-1) 3 parts by mass of as polymer, and and localized promoting composition (G-1) 30 parts by mass of (J-1) radiation-sensitive resin composition by mixing the manufacturing processes and the cost of production.

[In the embodiment 20 to 63 and comparison example 1 to 41]

A shown in table 3 and table 4 each component of the couple whereof the type and the in a blended amount using the except, as well in the embodiment 1 the operated by an, radiation-sensitive resin composition (J-2) to (J-45) (CJ-41) to (CJ-1) and manufacturing processes and the cost of production.

< 레지스트 패턴의 형성(I)>

(In the embodiment 19 to 47 and 53 to 55, and comparison example 1 to 28)

[For forming resist pattern (1) (alkali development)]

12 inch of on silicon wafer surfaces, spin coater (CLEAN TRACK ACT12, Tokyo electron manufacturing) using, lower composition for formation of antireflection film (ARC66, termination brewing [...] manufacturing) after the application the, 60 seconds in 205 °C 105 nm film thickness by heating the lower layer anti-reflective film. The underlayer colored fluorescent film on anti-reflective coating using spin coater said each manufacturing said photoresist is applied on the a radiation-sensitive resin composition, in 90 °C PB is performed, the after 60 seconds, 30 seconds and cooling the 23 °C in, was forming a resist film of 90 nm film thickness. Furthermore, the resist layer, immersion exposure excimer laser ArF device using a (NSR-S610C, NIKON manufacturing), NA=1.3, dipole (sigma 0.977/0.782) in optical conditions, 40 nm periphery having a different (1L1S) adaptation exposure through mask patterns. Post exposure, PEB was performed in 90 °C 60 seconds. Furthermore, alkali developer-as TMAH 2.38 mass % of unit develops a alkali aqueous solution is used, and rinsed with water, drying the adhesive was as to form a resist pattern of positive. The resist in pattern formation, target dimension 1 to 1 in 40 nm periphery having a different surge formed mask a width of, 1 to 1 in 40 nm line width a periphery having a different optimum exposure amount is produced.

[For forming resist pattern (2) (organic solvent developing)]

Said for forming resist pattern (1) in, TMAH instead acetic acid n-butyl using unit develops a organic solvent, their application as a in addition performs cleaning not except that the, said for forming resist pattern (1) as well as the CCD camera or the character string, are formed at the, negative resist pattern.

<Evaluation >

To forming said resist pattern therewith by measuring the method according to, radiation-sensitive resin composition performance LWR, resolution, focal depth and rectangular mother pipe having a cross sectional shape was assessed. Showed to the result, table 5. Said resist pattern measurement of length the scanning type electron microscope (S-9380, tech hitachi[...] manufacturing) by cylinder to have. Furthermore, in the embodiment each evaluation sensor/actuator senses the outer situation exhibits compared to come off to 5 table thereby, the cold air flows.

[LWR performance]

Resist pattern is said scanning type electron microscope using, pattern has been observed on from the upper. Total point in any line width measuring point 50, the measurement from distribution of 3 sigma value is found the, same is (nm) LWR performance. LWR performance and the values are smaller than blades, presenting a preferred. Performance LWR, compares the examples of the comparison of evaluation standard among an electric 15% or more enhanced (LWR 85% hereinafter value of performance) is disclosed to 'A' when the, improved of less than 15% 10% or more (LWR performance value of oil film bearing sleeve has a cylindrical 85% 90% hereinafter) when the 'B' to, improved of less than 10% (LWR value of performance exceeds 90%)was assessed to when the 'C'.

[Resolution]

Said optimum exposure judge the presence or the absence in minimal a marine the measuring a dimension of a resist pattern, is (nm) resolution value is measured. Resolution the resolution the smaller the value exhibits a good shape. Resolution the, compares the examples of the comparison of evaluation standard among an electric 15% or more enhanced (minimum resist pattern sizes in 85% hereinafter) is disclosed to 'A' when the, improved 10% or more of less than 15% (minimum resist pattern sizes in oil film bearing sleeve has a cylindrical 85% 90% hereinafter) when the 'B' to, improved of less than 10% (minimum resist pattern sizes in exceeds 90%)was assessed to when the 'C'.

[-rectangular mother pipe having a cross sectional shape]

A marine in said optimum exposure judge the presence or the absence for monitoring a calculates cross-sectional shapes of the resist pattern, resist pattern line width in intermediate (lb) and membrane of the measurement is carried out with the line width in upper portion of the reactor (La), each from La/Lb was calculated. The rectangular mother pipe having a cross sectional shape, when the 'A' to 0.95 ≤ (La/Lb) ≤ 1.05, 0.9 ≤ (La/Lb) < (La/Lb)≤1.1 < 0.95 to 1.05 or when the 'B' , when < (La/Lb) (La/Lb) < 0.9 or 1.1 was assessed to the 'C'.

[Shift mask]

Marine in said optimum exposure judge the presence or the absence in a resist pattern, has changed focus in depth direction when observed by the dimensions of the, bridge or combusted for the reference and pattern size without 90% to 110% entering the determining the clearance depth direction, light with the measuring results to the focal depth. Measurements for a larger shift mask exhibits a good shape. Shift mask when compared to examples of the comparison of reference an evaluation, 15% or more enhanced (115% or more deep focus) is disclosed to 'A' when the, improved of less than 15% 10% or more (deep focus 110% or more less than 115%)when the 'B' to, improved of less than 10% when the (deep focus less than 110%)was assessed to 'C'.

< 레지스트 패턴의 형성(II)>

(In the embodiment 48 to 52 and 56 to 63, and comparison e.g. 29 to 41)

[For forming resist pattern (3) (alkali development)]

12 inch on silicon wafer surfaces of, applying a composition for formation of antireflection film lower after, 205 °C 60 seconds in 25 nm film thickness by heating the lower layer anti-reflective film. On anti-reflective coating the underlayer colored fluorescent film, photoresist is applied on the each a radiation-sensitive resin composition, was performed in 100 °C PB 60 seconds. In 23 °C and cooling the 30 seconds then, was forming a resist film of 50 nm film thickness. Furthermore, the resist layer EUV exposure device using (NXE3100, ASML manufacturing), NA=0.25, dipole optical conditions in, 35 nm periphery having a different (1L/1S) through mask patterns for for forming resist pattern of the exposure section. Post exposure, PEB was performed in 100 °C 60 seconds. Furthermore, mass 2.38% TMAH with an aqueous solution, in 23 °C 30 performs a developed per seconds, continue to, 7 seconds using pure water of ultra-pure water rinsing and drying, then, 2,000rpm, by dry spindle centrifugal separator 15 seconds, 35 nm periphery having a different (1L/1S) was as to form a resist pattern of positive-working. Surge a width of, 1 to 1 in 35 nm line width a periphery having a different optimum exposure amount is produced.

[For forming resist pattern (4) (organic solvent developing)]

Said for forming resist pattern (3) in, TMAH instead acetic acid n-butyl using unit develops a organic solvent, their application as a in addition performs cleaning not except that the, said for forming resist pattern (3) as well as the CCD camera or the character string, are formed at the, negative resist pattern.

<Evaluation >

Respect to said obtained resist pattern, in the case of (I) said for forming resist pattern unit photographs a similar method was by. Showed to the result, table 5.

Table 5 of apparent as seen in the, embodiment the first deoxygenator radiation-sensitive resin composition, alkali development and an organic solvent of both when LWR performance, resolution, was excellent in shift mask and mother pipe having a cross sectional shape.

[Industrial applicability]

Of the present invention radiation-sensitive resin composition and resist pattern formation method according to, while exhibiting wide focal depth, small LWR, each pixel having excellent rectangular mother pipe having a cross sectional shape in addition so as to form a resist pattern can be. Polymer of the present invention the radiation-sensitive resin composition polymer component can be appropriately used as. Processes for preparing the manufacturing method of the present invention compounds suitable as a starting material for polymer compound in a simple manner in addition good yield can be produced. Therefore, these then more activated by a expected to be for semiconductor device manufacture, use can be made of, to a head and.