JP2003215805A - Radiation sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition having high transparency for radiation and excellent basic physical properties as a resist such as sensitivity, resolution, dry etching durability and pattern profile. <P>SOLUTION: The radiation sensitive resin composition contains the following resin (A) and (B) a radiation sensitive acid generator. The resin (A) is an alkali insoluble or alkali hardly soluble resin and changed into alkali-soluble by the action of an acid and the resin is, for example, a mevalonic lactone methacrylate/3-hydroxy-1-adamantyl methacrylate/1-methylcyclopentyl alkali methacrylate copolymer, a mevalonolactone methacrylate/3-hydroxyl-1-adamantyl methacrylate/[1-(2-methyl-2-norbornyl)ethoxycarbonyl]methacrylate copolymer. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a radiation-sensitive resin set.
Involved in products, more specifically, KrF excimer laser
Or far ultraviolet rays such as ArF excimer laser, electron
X-rays such as charged particle beams such as X-rays and synchrotron radiation
Chemical amplification type useful for microfabrication using various types of radiation
Radiation sensitivity that can be suitably used as a resist
It relates to a resin composition. [0002] 2. Description of the Related Art Microfabrication represented by the manufacture of integrated circuit devices.
In the field of engineering, to obtain higher integration,
In recent years, fine processing at a level of 0.20 μm or less is possible
Lithographic techniques are needed. However, conventionally
In the lithography process of
Near ultraviolet rays such as rays are used.
Is extremely sub-quarter micron
It is said to be difficult. Therefore, 0.20μm or less
In order to enable fine processing at the level of
The use of short radiation is being considered. Such a short wavelength
As the radiation, for example, the emission line spectrum of a mercury lamp,
Deep ultraviolet rays, X-rays, electron beams represented by excimer lasers
Etc., among which KrF
Excimer laser (wavelength 248 nm) or ArF
A Kisima laser (wavelength 193 nm) has attracted attention.
Radiation sensitive suitable for irradiation with such excimer laser
As a linear resin composition, a component having an acid dissociable functional group
Radiation (hereinafter referred to as "exposure") generates an acid
Conversion with generated components (hereinafter referred to as "acid generator")
Compositions utilizing the chemical amplification effect (hereinafter referred to as “chemically amplified
"Radiant composition". ) Have been proposed. Conversion
Examples of the chemically amplified radiation-sensitive composition include, for example,
No. 27660 discloses a carboxylic acid t-butyl ester.
A ter group or a phenol t-butyl carbonate group
A composition containing a polymer having an acid generator has been proposed
ing. This composition reacts to the action of acid generated by exposure.
From the t-butyl ester group or
Is the dissociation of the t-butyl carbonate group,
Acidity consisting of ruboxyl group or phenolic hydroxyl group
Group, resulting in exposure of the resist coating
Utilizing the phenomenon that the region becomes easily soluble in alkaline developer
It is. By the way, a conventional chemically amplified radiation-sensitive group is used.
Many products are based on phenolic resins
However, in the case of such resins, far ultraviolet rays are used as radiation.
When using, far ultraviolet rays due to the aromatic ring in the resin
Because it is absorbed, the exposed far ultraviolet rays
There is a disadvantage that it cannot reach the lower layer sufficiently,
Therefore, the exposure amount is large in the upper part of the resist coating, and
And the resist pattern after development is thinner at the top
As it goes to the bottom, it becomes a thick trapezoid shape, enough resolution
There was a problem that the degree could not be obtained. In addition, after development
If the resist pattern becomes trapezoidal, proceed to the next step
When performing etching or ion implantation,
Dimensional accuracy could not be achieved, which was a problem. Moreover,
If the top of the resist pattern is not rectangular, dry etching
The resist disappears faster due to etching.
In addition, there is a problem that it is difficult to control the etching conditions.
On the other hand, the shape of the resist pattern depends on the radiation of the resist film.
It can be improved by increasing the line transmittance. An example
For example, (meth) represented by polymethyl methacrylate
Acrylate resin is highly transparent to far ultraviolet rays
It is a very preferable resin from the viewpoint of radiation transmittance.
For example, in Japanese Patent Application Laid-Open No.
Chemically amplified radiation-sensitive resin set using a related resin
Products have been proposed. However, this composition
Although it is excellent in terms of fine processing performance, it also has an aromatic ring
The drawback of low dry etching resistance
Yes, even in this case, high-precision etching can be performed.
Difficult, radiation transparent and dry etching
It cannot be said to have resistance. In addition, a chemically amplified radiation-sensitive resin composition may be used.
The resist of
One of the measures to improve dry etching resistance
As a resin component in the composition,
A method for introducing an aromatic ring is known.
JP-A-234511 discloses a (meth) a having an aliphatic ring.
Chemically amplified radiation-sensitive resin using acrylate resin
Compositions have been proposed. However, with this composition
Is a conventional acid as the acid dissociable functional group of the resin component.
Groups that are relatively easily dissociated (eg, tetrahydropyra
Relatively dissociated by an acetal-based functional group such as a nyl group) or acid
Difficult groups (eg, t-butyl ester group, t-butyl
T-butyl-based functional groups such as carbonate groups)
In the case of the former resin component having an acid dissociable functional group,
The basic physical properties of the resist, especially the sensitivity and pattern shape, are good.
However, there are difficulties in the storage stability of the composition,
Conversely, the latter resin component having an acid-dissociable functional group
Good stability, but basic properties of resist, especially sensitivity
And that the pattern shape is impaired. Further
In addition, an aliphatic ring is introduced into the resin component of the composition.
Because the resin itself becomes very hydrophobic,
There was also a problem in terms of adhesiveness with respect to. So, the semiconductor element
From the viewpoint of technology development that can respond to the progress of miniaturization in
Can adapt to short-wavelength radiation represented by far ultraviolet rays
In chemically amplified radiation-sensitive compositions,
High transparency and excellent basic physical properties as resist
The development of new resin components has become an important issue. [0005] SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of radiation.
High transparency for lines, sensitivity, resolution and dryness
Base as resist such as etching resistance and pattern shape
To provide a radiation-sensitive resin composition having excellent physical properties
is there. [0006] According to the present invention, the section
The title is (A) a repeating unit represented by the following general formula (I-1)
And a repeating unit represented by the following general formula (I-2).
And a repeating unit represented by the following general formula (II)
An alkali-insoluble or alkali-insoluble resin,
A resin that becomes alkali-soluble by the action of an acid, and
(B) It is characterized by containing a radiation-sensitive acid generator.
Radiation-sensitive resin composition. Achieved by [0007] Embedded image [In the general formula (I-1) and the general formula (I-2),
R¹And R^TwoAre independently a hydrogen atom or a methyl group
And R^ThreeIs also a hydrogen atom or a straight chain having 1 to 4 carbon atoms
Or a branched alkyl group;^Four, R^FiveAnd R
⁶Represents a hydrogen atom or a hydroxyl group independently of each other
And R^Four, R^FiveAnd R⁶At least one is hidden
Roxyl group. ] [0008] Embedded image [In the general formula (II), R⁷Is a hydrogen atom or methyl
X represents a single bond or a divalent organic group having 1 to 8 carbon atoms
A group represented by R⁸Is a hydrogen atom, a straight-chain having 1 to 20 carbon atoms
Or a branched alkyl group, or one having 4 to 20 carbon atoms.
And a divalent alicyclic hydrocarbon group or a derivative thereof. ] Hereinafter, the present invention will be described in detail.(A) component The component (A) in the present invention is represented by the general formula (I-1).
The repeating unit represented by the following (hereinafter, referred to as “the repeating unit (I-
1) ". ) And the repeating unit represented by the general formula (I-2).
Repeating unit (hereinafter referred to as “repeating unit (I-2)”)
U. ) And the repeating unit represented by the general formula (II)
(Hereinafter referred to as “repeating unit (II)”).
A resin that is insoluble in alkali or hardly soluble in alkali,
Resins that become alkali-soluble by the action of
(A) ". ). The term "alkali-free"
"Soluble or slightly soluble in alkali" means that the resin (A)
Resist coating formed from a radiation-sensitive resin composition?
Used when forming a resist pattern
Under development conditions, instead of the resist film, a resin (A)
When developing a film using only
More than 50% of the thickness means the property remaining after development. In the general formula (I-1), R^ThreeCarbon number of
As the linear or branched alkyl group of 1 to 4,
For example, methyl, ethyl, n-propyl, i-propyl
Propyl group, n-butyl group, 2-methylpropyl group, 1-
Methylpropyl group, t-butyl group and the like can be mentioned.
You. R in general formula (I-1)^ThreeAs a hydrogen source
And a methyl group are preferred. Specific examples of preferred repeating unit (I-1)
As R^ThreeIs a hydrogen atom, and R¹Is a hydrogen atom
Acrylic repeating unit; R^ThreeIs a methyl group, and R
¹An acrylic repeating unit wherein is a hydrogen atom; R^ThreeBut water
An elementary atom, R¹Is a methyl group
Return unit; R^ThreeIs a methyl group, and R¹Is a methyl group
Methacrylic repeating unit.
Among these preferred repeating units (I-1),
And R^ThreeIs a methyl group, and R¹Is a hydrogen atom
Ryl repeating unit; R^ThreeIs a methyl group, and R¹But
A methacrylic repeating unit that is a tyl group is preferred. Specific examples of the repeating unit (I-2)
Then R^FourIs a hydroxyl group, and R^TwoIs a hydrogen atom
An acrylic repeating unit which is: R^FourAnd R^FiveIs hidden
Roxyl group, R^TwoIs a hydrogen atom
Repeat unit; R^Four, R^FiveAnd R⁶Is a hydroxyl group
Yes, R^TwoAn acrylic repeating unit wherein is a hydrogen atom;
R^FourIs a hydroxyl group, is^TwoIs a methyl group
A methacrylic repeating unit which is^FourAnd R^FiveBut
A droxyl group,^TwoIs a methyl group
Tacyl repeating unit; R^Four, R^FiveAnd R⁶Is hidden
Roxyl group, R^TwoIs a methyl group
Repeating units can be mentioned. These repetitions
In the unit (I-2), particularly, R^FourIs a hydroxyl group
Yes, R^TwoAn acrylic repeating unit wherein is a hydrogen atom;
R^FourIs a hydroxyl group, is^TwoIs a methyl group
Is preferable. resin
In (A), a repeating unit (I-1) and a repeating unit
The unit (I-2) may be used alone or in combination of two or more.
Can be present. Next, in the general formula (II), the carbon number of X
Examples of the divalent organic group of 1 to 8 include a methylene group,
1,1-ethylene group, 1,2-ethylene group, propylene
Group, trimethylene group, tetramethylene group, -CH_TwoOC
(= O)-, -CH (CH_Three) OC (= O)-, -CH
(CH_Three) CH_TwoOC (= O)-, -CH_TwoCH (CH_Three)
OC (= O)-, -CH_TwoCH_TwoCH_TwoOC (= O)-
And the like. X in general formula (II)
Is a single bond, -CH (CH_Three) OC (= O)-etc. are preferred
New Further, R⁸Having 1 to 20 carbon atoms
Or a branched alkyl group, for example, a methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl
Group, 2-methylpropyl group, 1-methylpropyl group,
t-butyl group, n-pentyl group, n-hexyl group and the like.
I can do it. Further, a monovalent alicyclic carbonization having 4 to 20 carbon atoms.
As hydrogen, for example, cyclobutyl group, cyclopentene
Group, cyclohexyl group, cycloheptyl group, cyclo
Cycloalkyl groups such as octyl group and these groups
For example, methyl, ethyl, n-propyl, i-propyl
Group, n-butyl group, 2-methylpropyl group, 1-methyl
Linear group having 1 to 4 carbon atoms such as propyl group, t-butyl group, etc.
Or one or more or one or more branched alkyl groups
A group substituted above; Cyclopentenyl group, cyclohexenyl group
And the like, and these groups, for example,
Tyl group, ethyl group, n-propyl group, i-propyl group,
n-butyl group, 2-methylpropyl group, 1-methylpro
A linear or straight-chain having 1 to 4 carbon atoms such as a pill group and a t-butyl group;
Represents one or more of branched alkyl groups.
Substituted group; A norbornyl group, an isobornyl group,
Clodecanyl group, tetracyclododecanyl group, adaman
Bridged hydrocarbon groups such as tyl groups, and these groups
For example, methyl, ethyl, n-propyl, i-propyl
Group, n-butyl group, 2-methylpropyl group, 1-methyl
Linear group having 1 to 4 carbon atoms such as propyl group, t-butyl group, etc.
Or one or more or one or more branched alkyl groups
Examples include the groups substituted above. The derivation of the above monovalent alicyclic hydrocarbon group
As a body, for example, a carboxyl group; an oxo group (immediately
Hydroxy group, 1-hydroxyd)
Tyl group, 2-hydroxyethyl group, 1-hydroxypro
Pill group, 2-hydroxypropyl group, 3-hydroxyp
Ropyl group, 1-hydroxybutyl group, 2-hydroxybutyrate
Tyl group, 3-hydroxybutyl group, 4-hydroxybutyi
Hydroxyalkyl groups having 1 to 4 carbon atoms, such as
Si group, ethoxy group, n-propoxy group, i-propoxy
Group, n-butoxy group, 2-methylpropoxy group, 1-meth
A C 1 -C 4 group such as a tylpropoxy group or a t-butoxy group;
Alkoxyl group; cyano group; cyanomethyl group, 2-cya
Noethyl group, 3-cyanopropyl group, 4-cyanobutyl
A substituent such as a cyanoalkyl group having 2 to 5 carbon atoms such as
Groups having at least one or more species
You. R in the general formula (II)⁸As 1-
Methylcyclopentyl group, 1-ethylcyclopentyl
Group, 1-methylcyclohexyl group, 1-ethylcyclohexyl
Xyl group, 2-methyl-2-norbornyl group, 2-ethyl
Ru-2-norbornyl group, 2-methyl-2-adamanti
And a 2-ethyl-2-adamantyl group. Specific examples of preferred repeating units (II)
X is a single bond, R⁸Is 1-methylcyclopen
A tyl group or a 1-ethylcyclopentyl group;⁷
Is a hydrogen atom or a methyl group.
A repeating unit; X is a single bond;⁸Is 1-methylsic
A rohexyl group or a 1-ethylcyclohexyl group
R⁷Is a hydrogen atom or a methyl group.
Ryl repeating unit; X is a single bond;⁸Is 2-me
Tyl-2-norbornyl group or 2-ethyl-2-nor
A bornyl group;⁷Is a hydrogen atom or a methyl group
(Meth) acrylic repeating unit; X is a single bond
R⁸Is a 2-methyl-2-adamantyl group or 2-
An ethyl-2-adamantyl group;⁷Is a hydrogen atom
A (meth) acrylic repeating unit which is a methyl group or a methyl group; X is --CH (CH_Three) OC (= O)-
R⁸Is a 1-methylcyclopentyl group or 1-ethyl
A cyclopentyl group, R⁷Is a hydrogen atom or methyl
A (meth) acrylic repeating unit which is a phenyl group;
H (CH_Three) OC (= O)-and R⁸Is 1-methylsi
Chlorohexyl or 1-ethylcyclohexyl
R⁷Is a hydrogen atom or a methyl group.
X is -CH (CH_Three) OC (= O)
-And R⁸Is a 2-methyl-2-norbornyl group or
Is a 2-ethyl-2-norbornyl group;⁷Is hydrogen
(Meth) acrylic repeating which is an atom or a methyl group
Unit; X is -CH (CH_Three) OC (= O)-and R⁸
Is a 2-methyl-2-adamantyl group or 2-ethyl-
A 2-adamantyl group;⁷Is a hydrogen atom or methyl
(Meth) acrylic repeating units, etc.
be able to. In the resin (A), the repeating unit (I
I) may be present alone or in combination of two or more. The resin (A) comprises a repeating unit (I-1),
Other than the repeating unit (I-2) and the repeating unit (II)
Repeating unit (hereinafter referred to as "other repeating unit")
May be included. Give another repeating unit
Examples of the obtained monomer include (meth) acrylic acid 2-
Hydroxyethyl, 2-hydroxy (meth) acrylate
Propyl, 3-hydroxypropyl (meth) acrylate
, 2-cyclopropyloxycal (meth) acrylate
Bonylethyl, 2-cyclopentyl (meth) acrylate
Oxycarbonylethyl, 2-meth (acrylic acid) acrylate
Rohexyloxycarbonylethyl, (meth) acrylic
2-cyclohexenyloxycarbonylethyl acid,
(T) 2- (4-methoxycyclohexyl) acrylate
(Meth) acrylic acid esters such as xyloxyethyl
And α-hydroxymethyl acrylate, α-hydrid
Ethyl roxymethyl acrylate, α-hydroxymethyl
N-propyl acrylate, α-hydroxymethylacrylic
Α-hydroxymethyl acrylate such as n-butyl
Steals; Vinyl acetate, vinyl propionate, vinyl butyrate
Vinyl esters such as nil; (meth) acrylonitrile
, Α-chloroacrylonitrile, crotonitrile,
Maleinnitrile, Fumaronitrile, Mesaconitrile
, Citraconitrile, itaconitrile, etc.
Nitrile compound; (meth) acrylamide, N, N-di
Methyl (meth) acrylamide, crotonamide, male
Inamide, fumaramide, mesaconamide, citraco
Unsaturated amide compounds such as amide and itaconamide; N
-Vinyl-ε-caprolactam, N-vinyl pyrrolide
Nitrogen, vinylpyridine, vinylimidazole, etc.
Polyvinyl compound; crotonic acid, maleic acid, maleic anhydride
Acid, fumaric acid, itaconic acid, itaconic anhydride, citrus
Unsaturated acids such as conic acid, citraconic anhydride, mesaconic acid, etc.
Bonic acid (anhydride) s; (meth) acrylic acid 2-carboxy
Siethyl, 2-carboxypropyl (meth) acrylate
, 3-carboxypropyl (meth) acrylate, (meth
T) unsaturated carboxy such as 4-carboxybutyl acrylate
Monofunctional monomer such as carboxyl group-containing esters of acid
Body and Methylene glycol di (meth) acrylate
G, ethylene glycol di (meth) acrylate, pro
Pyrene glycol di (meth) acrylate, 1,6-he
Xandiol di (meth) acrylate, 2,5-dimethyl
Chill-2,5-hexanediol di (meth) acrelay
G, 1,8-octanediol di (meth) acrelay
G, 1,9-nonanediol di (meth) acrylate,
1,4-bis (2-hydroxypropyl) benzenedi
(Meth) acrylate, 1,3-bis (2-hydroxy
Propyl) benzenedi (meth) acrylate, 1,2-
Adamantanediol di (meth) acrylate, 1,3
-Adamantanediol di (meth) acrylate, 1,
4-adamantanediol di (meth) acrylate,
Licyclodecanyl dimethylol di (meth) acrylate
And the like. In the resin (A), the repeating unit (I-
The content of 1) is usually 5 to 5 with respect to all repeating units.
70 mol%, preferably 5 to 60 mol%, more preferably
Or 10 to 50 mol%. In this case, the repeating unit
If the content of (I-1) is less than 5 mol%, the dissolution in a solvent
Properties, adhesion to resist substrate, developability, etc.
Tends to decrease, while if it exceeds 70 mol%, the
There is a tendency that the resolution as a dist is reduced. Also,
The content of the repeating unit (I-2) is based on all repeating units.
And usually 5 to 40 mol%, preferably 10 to 40 mol%
%, More preferably 10 to 30 mol%. this
In this case, the content of the repeating unit (I-2) is less than 5 mol%.
In this case, the dry etching resistance of the resist decreases.
On the other hand, if it exceeds 40 mol%, the resist
During the formation of the turn, the pattern collapses or peels off, or
Swelling tends to occur easily. The content of the repeating unit (II) is
Usually, 10 to 70 mol%, preferably,
15 to 60 mol%, more preferably 20 to 60 mol%.
Mol%. In this case, the content of the repeating unit (II)
Is less than 10 mol%, the resolution as a resist is reduced.
On the other hand, when it exceeds 70 mol%, the resist
Tends to decrease the contrast. further,
The content of other repeating units is
And usually not more than 20 mol%, preferably not more than 10 mol%
It is. The resin (A) is, for example,
The mixture of corresponding monomers is treated with hydroperoxides,
Alkyl peroxides, diacyl peroxides,
Use a radical polymerization initiator such as
Polymerization in a suitable solvent in the presence of a chain transfer agent.
Can be manufactured more. Solvent used for the polymerization
For example, n-pentane, n-hexane, n-
Heptane, n-octane, n-nonane, n-decane, etc.
Alkanes: cyclohexane, cycloheptane, cyclo
Cycloalkanes such as octane, decalin and norbornane
Benzene, toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene; chlorobutanes, bromo
Hexanes, dichloroethanes, hexamethylene dibro
Halogenated hydrocarbons such as amide and chlorobenzene; acetic acid
Ethyl, n-butyl acetate, i-butyl acetate, propion
Saturated carboxylic esters such as methyl methacrylate; 2-butano
, 4-methyl-2-pentanone, 2-heptanone, etc.
Ketones; tetrahydrofuran, dimethoxyethanes,
Eiles such as diethoxyethanes may be mentioned.
Wear. These solvents may be used alone or in combination of two or more.
Can be used. Also, the reaction in the polymerization
The temperature is usually 40-120 ° C, preferably 50-90 ° C.
° C, and the reaction time is usually 1 to 48 hours, preferably
Is 1 to 24 hours. The resin (A) in the present invention comprises a halogen,
The less impurities such as metal, the better.
Sensitivity, resolution, process stability, and putter
Shape and the like can be further improved. Resin (A)
Purification methods include, for example, chemical refining such as water washing and liquid-liquid extraction.
Manufacturing methods, their chemical purification methods, ultrafiltration, centrifugation, etc.
Combination with the physical purification method of
You. Gel permeation chroma of resin (A)
Weight flatness in terms of polystyrene by GPC
The average molecular weight (hereinafter, referred to as “Mw”) is usually 3,0.
00 to 300,000, preferably 4,000 to 20
000, more preferably 5,000 to 100,0
00. In this case, the Mw of the resin (A) is 3,000
If it is less than 30, the heat resistance of the resist tends to decrease.
On the other hand, if it exceeds 300,000,
Developability tends to decrease. Also, the Mw of the resin (A)
And gel permeation chromatography (GPC)
Number average molecular weight (hereinafter “Mn”)
That. ) (Mw / Mn) is usually 1 to 5,
It is preferably 1-3. In the present invention, the resin (A)
Can be used alone or as a mixture of two or more.
Wear. [0030](B) component The component (B) in the present invention comprises visible light, ultraviolet light,
Generates acid by exposure to radiation such as external rays, electron beams, X-rays
Radiation-sensitive acid generator (hereinafter referred to as "acid generator (B)")
That. ). The acid generator (B) is generated by exposure
The acid generated in the resin (A) is decomposed by the action of the generated acid.
The dissociated groups are dissociated, and as a result, the exposed portions of the resist film are exposed.
Positive resist pattern because it is easily soluble in Lucari developer
It has an action of forming a pattern. Such acid generation
As the raw material (B), for example, onium salt compounds, halo
Gen-containing compounds, diazoketone compounds, sulfone compounds
And sulfonic acid compounds. these
Examples of the acid generator (B) include the following.
Can be. Onium salt compound: Onium salt compound
For example, iodonium salts, sulfonium salts (tetra
Contains lahydrothiophenium salts. ), Phosphonium
Salts, diazonium salts, pyridinium salts and the like.
it can. Specific examples of preferred onium salt compounds include
Diphenyliodonium trifluoromethanesulfone
G, diphenyliodonium nonafluoro-n-butane
Sulfonate, diphenyliodonium perfluoro-
n-octanesulfonate, bis (4-t-butylphenol)
Nyl) iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium nonaflu
Oro-n-butanesulfonate, bis (4-t-butyl
Phenyl) iodonium perfluoro-n-octance
Rufonate, triphenylsulfonium trifluorome
Tansulfonate, triphenylsulfonium nonaflu
Oro-n-butanesulfonate, triphenylsulfoni
Umperfluoro-n-octanesulfonate, trif
Enylsulfonium 10-camphorsulfonate,
Cyclohexyl 2-oxocyclohexyl methyls
Ruphonium trifluoromethanesulfonate, dicyclo
Hexyl-2-oxocyclohexylsulfonium tri
Fluoromethanesulfonate, 2-oxocyclohexyl
Dimethylsulfonium trifluoromethanesulfone
G, 1-naphthyldimethylsulfonium trifluoromethyl
Tansulfonate, 1-naphthyldiethylsulfonium
Trifluoromethanesulfonate, 4-cyano-1-na
Futyldimethylsulfonium trifluoromethanesulfo
, 4-nitro-1-naphthyldimethylsulfonium
Muttrifluoromethanesulfonate, 4-methyl-1-
Naphthyldimethylsulfonium trifluoromethanesulfur
Phonate, 4-cyano-1-naphthyldiethylsulfoni
Trifluoromethanesulfonate, 4-nitro-1
-Naphthyldiethylsulfonium trifluoromethanes
Rufonate, 4-methyl-1-naphthyldiethylsulfo
Trifluoromethanesulfonate, 4-hydroxy
C-1-naphthyldimethylsulfonium trifluorome
Tansulfonate, 1- [1- (4-hydroxynaphthyl)]
Tetrahydrothiophenium trifluoromethanesulfo
Nate, 1- [1- (4-hydroxynaphthyl)] tet
Lahydrothiophenium nonafluoro-n-butanesul
Phonate, 1- [1- (4-hydroxynaphthyl)] te
Trahydrothiophenium perfluoro-n-octane
Sulfonate, 1- [1- (4-methoxynaphthyl)]
Tetrahydrothiophenium trifluoromethanesulfo
Nate, 1- [1- (4-methoxynaphthyl)] tetra
Hydrothiophenium nonafluoro-n-butanesulfo
Nate, 1- [1- (4-methoxynaphthyl)] tetra
Hydrothiophenium perfluoro-n-octanesul
Phonate, 1- [1- (4-ethoxynaphthyl)] tet
Lahydrothiophenium trifluoromethanesulfone
G, 1- [1- (4-ethoxynaphthyl)] tetrahydr
Rothiophenium nonafluoro-n-butanesulfone
G, 1- [1- (4-ethoxynaphthyl)] tetrahydr
Rothiophenium perfluoro-n-octanesulfone
1- [1- (4-n-butoxynaphthyl)] tet
Lahydrothiophenium trifluoromethanesulfone
G, 1- [1- (4-n-butoxynaphthyl)] tetra
Hydrothiophenium nonafluoro-n-butanesulfo
Nate, 1- [1- (4-n-butoxynaphthyl)] te
Trahydrothiophenium perfluoro-n-octane
Sulfonate, 1- [1- (4-methoxymethoxynaphthy)
Le)] tetrahydrothiophenium trifluoromethane
Sulfonate, 1- [1- (4-methoxymethoxynaph
Tyl)] tetrahydrothiophenium nonafluoro-n
-Butanesulfonate, 1- [1- (4-methoxymethoate)
Xinaphthyl)] tetrahydrothiophenium perflu
Oro-n-octanesulfonate, 1- [1- (4-E
Toximethoxynaphthyl)] tetrahydrothiophenyl
Trifluoromethanesulfonate, 1- [1- (4-
Ethoxymethoxynaphthyl)] tetrahydrothiopheny
Umnonafluoro-n-butanesulfonate, 1- [1
-(4-ethoxymethoxynaphthyl)] tetrahydrothio
Ophenium perfluoro-n-octanesulfone
G, 1- [1- {4- (1-methoxyethoxy) naphthy
Ru] tetrahydrothiophenium trifluoromethane
Sulfonate, 1- [1- {4- (1-methoxyethoxy)
C) Naphthyl｝] tetrahydrothiophenium nonaflu
Oro-n-butanesulfonate, 1- [1- {4- (1
-Methoxyethoxy) naphthyl}] tetrahydrothiophene
Perfluoro-n-octanesulfonate, 1
-[1- {4- (2-methoxyethoxy) naphthyl}]
Tetrahydrothiophenium trifluoromethanesulfo
Nate, 1- [1- {4- (2-methoxyethoxy) na]
Phthyl}] tetrahydrothiophenium nonafluoro-
n-butanesulfonate, 1- [1- {4- (2-meth
Xiethoxy) naphthyl}] tetrahydrothiophenyl
Mperfluoro-n-octanesulfonate, 1- [1- (4-methoxycarbonyloxy)
Sinaphthyl)] tetrahydrothiophenium trifluoro
Methanesulfonate, 1- [1- (4-methoxycal
Bonyloxynaphthyl)] tetrahydrothiophenium
Nonafluoro-n-butanesulfonate, 1- [1-
(4-methoxycarbonyloxynaphthyl)] tetrahi
Drothiophenium perfluoro-n-octanesulfo
Nate, 1- [1- (4-ethoxycarbonyloxyna)
Phthyl)] tetrahydrothiophenium trifluorome
Tansulfonate, 1- [1- (4-ethoxycarboni)
Ruoxynaphthyl)] tetrahydrothiophenium nona
Fluoro-n-butanesulfonate, 1- [1- (4-
Ethoxycarbonyloxynaphthyl)] tetrahydrothi
Ophenium perfluoro-n-octanesulfone
G, 1- [1- (4-n-propoxycarbonyloxy)
Naphthyl)] tetrahydrothiophenium trifluoro
Methanesulfonate, 1- [1- (4-n-propoxy)
Carbonyloxynaphthyl)] tetrahydrothiopheny
Umnonafluoro-n-butanesulfonate, 1- [1
-(4-n-propoxycarbonyloxynaphthyl)]
Tetrahydrothiophenium perfluoro-n-octa
Sulfonate, 1- [1- (4-i-propoxyl)
Bonyloxynaphthyl)] tetrahydrothiophenium
Trifluoromethanesulfonate, 1- [1- (4-i
-Propoxycarbonyloxynaphthyl)] tetrahydride
Rothiophenium nonafluoro-n-butanesulfone
G, 1- [1- (4-i-propoxycarbonyloxy)
Naphthyl)] tetrahydrothiophenium perfluoro
-N-octanesulfonate, 1- [1- (4-n-butoxycarbonyl)
Oxynaphthyl)] tetrahydrothiophenium trif
Fluoromethanesulfonate, 1- [1- (4-n-buto)
Xycarbonyloxynaphthyl)] tetrahydrothiophene
Enium nonafluoro-n-butanesulfonate, 1-
[1- (4-n-butoxycarbonyloxynaphthy)
L)] tetrahydrothiophenium perfluoro-n-
Octanesulfonate, 1- [1- (4-t-butoxy)
Carbonyloxynaphthyl)] tetrahydrothiopheny
Trifluoromethanesulfonate, 1- [1- (4
-T-butoxycarbonyloxynaphthyl)] tetrahi
Drothiophenium nonafluoro-n-butanesulfone
1- [1- (4-t-butoxycarbonyloxy)
Naphthyl)] tetrahydrothiophenium perfluoro
-N-octanesulfonate, 1- [1- {4- (2-
Tetrahydrofuranyloxy) naphthyl}] tetrahydride
Rothiophenium trifluoromethanesulfonate, 1
-[1- {4- (2-tetrahydrofuranyloxy) na]
Phthyl}] tetrahydrothiophenium nonafluoro-
n-butanesulfonate, 1- [1- {4- (2-tetra
Lahydrofuranyloxy) naphthyl}] tetrahydrothi
Ophenium perfluoro-n-octanesulfone
G, 1- [1- {4- (2-tetrahydropyranyloxy)
C) Naphthyl}] tetrahydrothiophenium trifur
Oromethane sulfonate, 1- [1- {4- (2-tetra
Lahydropyranyloxy) naphthyl}] tetrahydrothi
Offenium nonafluoro-n-butanesulfonate,
1- [1- {4- (2-tetrahydropyranyloxy)
Naphthyl｝] tetrahydrothiophenium perfluoro
-N-octanesulfonate, 1- [1- (4-benzyloxynaphthy)
Le)] tetrahydrothiophenium trifluoromethane
Sulfonate, 1- [1- (4-benzyloxynaphthy)
L)] tetrahydrothiophenium nonafluoro-n-
Butanesulfonate, 1- [1- (4-benzyloxy)
Naphthyl)] tetrahydrothiophenium perfluoro
-N-octanesulfonate, 1- (1-naphthylacetate)
Tomethyl) tetrahydrothiophenium trifluorome
Tansulfonate, 1- (1-naphthyl acetomethyl)
Tetrahydrothiophenium nonafluoro-n-butane
Sulfonate, 1- (1-naphthyl acetomethyl) tet
Lahydrothiophenium perfluoro-n-octance
Rufonate, 1- (3,5-dimethyl-4-hydroxy
Phenyl) tetrahydrothiophenium trifluorome
Tansulfonate, 1- (3,5-dimethyl-4-hydride
Roxyphenyl) tetrahydrothiophenium nonaflu
Oro-n-butanesulfonate, 1- (3,5-dimethyl)
Ru-4-hydroxyphenyl) tetrahydrothiopheny
Umperfluoro-n-octanesulfonate and the like.
Can be Halogen-containing compound: Halogen-containing compound
As, for example, a haloalkyl group-containing hydrocarbon compound
Products, haloalkyl group-containing heterocyclic compounds, etc.
Can be. Specific examples of preferred halogen-containing compounds
Is phenylbis (trichloromethyl) -s-triazine
4-methoxyphenylbis (trichloromethyl)-
s-Triazine, 1-naphthylbis (trichloromethyl
(Trichloromethyl) -s- such as -s-triazine
Triazine derivatives and 1,1-bis (4'-chlorophene)
Nyl) -2,2,2-trichloroethane
Can be. Diazoketone compounds: Examples of diazoketone compounds
For example, 1,3-diketo-2-diazo compounds, diazobens
Zoquinone compounds, diazonaphthoquinone compounds, etc.
be able to. Specific examples of preferred diazoketones
Is 1,2-naphthoquinonediazide-4-sulfonylc
Loride, 1,2-naphthoquinonediazide-5-sulfoni
Luchloride, 2,3,4,4'-tetrahydroxyben
1,2-Naphthoquinonediazide-4-sul of zophenone
Fonate or 1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,1,1-tris (4-h
1,2-Naphthoquinonedia of droxyphenyl) ethane
Zid-4-sulfonic acid ester or 1,2-naphthoxy
Nondiazide-5-sulfonic acid ester
Can be. Sulfone compound: As a sulfone compound
Is, for example, β-ketosulfone, β-sulfonylsulfo
And α-diazo compounds of these compounds.
Can be. Specific examples of preferred sulfone compounds
Is 4-trisphenacyl sulfone, mesityl phenacy
Sulfone, bis (phenylsulfonyl) methane, etc.
I can do it. Sulfonic acid compounds: Examples of sulfonic acid compounds
For example, alkyl sulfonic acid ester, alkyl sulfonic acid
Imide, haloalkylsulfonic acid ester, aryls
To mention sulfonic acid esters, iminosulfonates, etc.
Can be. Specific examples of preferred sulfonic acid compounds
Is benzoin tosylate, pyrogallol tris
Trifluoromethanesulfonate), nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate
G, trifluoromethanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide,
Nafluoro-n-butanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide,
-Fluoro-n-octanesulfonylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarbodiimid
, N-hydroxysuccinimide trifluoromethanes
Rufonate, N-hydroxysuccinimide nonafluoro
-N-butanesulfonate, N-hydroxysuccinimi
Doperfluoro-n-octanesulfonate, 1,8-
Naphthalenedicarboxylic acid imide trifluoromethanesulfur
Phonate and the like can be mentioned. Of these acid generators (B), in particular,
Phenyliodonium trifluoromethanesulfone
G, diphenyliodonium nonafluoro-n-butane
Sulfonate, diphenyliodonium perfluoro-
n-octanesulfonate, bis (4-t-butylphenol)
Nyl) iodonium trifluoromethanesulfonate,
Bis (4-t-butylphenyl) iodonium nonaflu
Oro-n-butanesulfonate, bis (4-t-butyl
Phenyl) iodonium perfluoro-n-octance
Rufonate, triphenylsulfonium trifluorome
Tansulfonate, triphenylsulfonium nonaflu
Oro-n-butanesulfonate, triphenylsulfoni
Umperfluoro-n-octanesulfonate, cyclo
Hexyl 2-oxocyclohexyl methylsulfoni
Trifluoromethanesulfonate, dicyclohexyl
Le-2-oxocyclohexylsulfonium trifluoro
Romethanesulfonate, 2-oxocyclohexyldim
Tylsulfonium trifluoromethanesulfonate, 4
-Hydroxy-1-naphthyldimethylsulfonium tri
Fluoromethanesulfonate, 1- [1- (4-hydroxynaphthyl)]
Tetrahydrothiophenium trifluoromethanesulfo
Nate, 1- [1- (4-hydroxynaphthyl)] tet
Lahydrothiophenium nonafluoro-n-butanesul
Phonate, 1- [1- (4-hydroxynaphthyl)] te
Trahydrothiophenium perfluoro-n-octane
Sulfonate, 1- [1- (4-n-butoxynafti)
Le)] tetrahydrothiophenium trifluoromethane
Sulfonate, 1- [1- (4-n-butoxynafti)
L)] tetrahydrothiophenium nonafluoro-n-
Butanesulfonate, 1- [1- (4-n-butoxyna)
Phthyl)] tetrahydrothiophenium perfluoro-
n-octanesulfonate, 1- (1-naphthylacetoacetate)
Methyl) tetrahydrothiophenium trifluorometa
Sulfonate, 1- (1-naphthyl acetomethyl) te
Trahydrothiophenium nonafluoro-n-butane
Rufonate, 1- (1-naphthylacetomethyl) tetra
Hydrothiophenium perfluoro-n-octanesul
Phonate, 1- (3,5-dimethyl-4-hydroxyphenyl)
Enyl) tetrahydrothiophenium trifluorometa
Sulfonate, 1- (3,5-dimethyl-4-hydro)
Xyphenyl) tetrahydrothiophenium nonafluoro
2-n-butanesulfonate, 1- (3,5-dimethyl)
-4-Hydroxyphenyl) tetrahydrothiophenium
Mperfluoro-n-octanesulfonate, Trifluoromethanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodii
Mido, nonafluoro-n-butanesulfonylbicyclo [
2.2.1] Hept-5-ene-2,3-dicarbodii
Mido, perfluoro-n-octanesulfonylbicyclo
[2.2.1] Hept-5-ene-2,3-dicarbodi
Imide, N-hydroxysuccinimide trifluorometa
Nsulfonate, N-hydroxysuccinimide nonaflu
Oro-n-butanesulfonate, N-hydroxysuccinate
Imido perfluoro-n-octanesulfonate, 1,
8-Naphthalenedicarboxylic acid imide trifluoromethane
Sulfonates and the like are preferred. In the present invention, the acid generator (B) may be used alone
Or a mixture of two or more. acid
The amount of the generator (B) used depends on the sensitivity as a resist and
From the viewpoint of ensuring the developability, 100 parts by weight of resin (A)
On the other hand, usually 0.1 to 10 parts by weight, preferably 0.5
７7 parts by weight. In this case, the amount of the acid generator (B) used
Is less than 0.1 part by weight, sensitivity and developability are reduced.
On the other hand, when it exceeds 10 parts by weight,
Transparency is reduced and a rectangular resist pattern is obtained.
Tends to be difficult. [0043]Various additives The radiation-sensitive resin composition of the present invention generates an acid upon exposure.
Of acid generated from agent (B) in resist film
Unwanted chemical reactions in unexposed areas
Acid diffusion controlling agent having the action of suppressing
preferable. By incorporating such an acid diffusion controller,
Storage stability of the radiation-sensitive resin composition obtained.
And the resolution as a resist is further improved.
And the withdrawal time from exposure to development (P
Suppress line width change of resist pattern due to fluctuation of ED)
Composition with excellent process stability.
can get. Acid diffusion control agents include
Basicity does not change due to exposure or heat treatment during the formation process
Nitrogen-containing organic compounds are preferred. Such nitrogen-containing organic treatment
As the compound, for example, the following general formula (III) [0044] Embedded image [In the general formula (III), each R⁹Are independent of each other
, Substituted or unsubstituted, linear, branched or cyclic
An alkyl group, a substituted or unsubstituted aryl group or
It represents a substituted or unsubstituted aralkyl group. ] A compound represented by the following formula (hereinafter referred to as "nitrogen-containing compound")
(B). ), Having two nitrogen atoms in the same molecule
(Hereinafter referred to as “nitrogen-containing compound (b)”),
Polyamino compounds and polymers having three or more nitrogen atoms
(Hereinafter, these are collectively referred to as "nitrogen-containing compounds (c)."
U. ) Quaternary ammonium hydroxide compounds, amides
Group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.
Can be mentioned. As the nitrogen-containing compound (A), for example, n
-Hexylamine, n-heptylamine, n-octyl
Amine, n-nonylamine, n-decylamine, cyclo
Mono (cyclo) alkylamines such as hexylamine;
Di-n-butylamine, di-n-pentylamine, di-
n-hexylamine, di-n-heptylamine, di-n
-Octylamine, di-n-nonylamine, di-n-de
Silamine, cyclohexylmethylamine, dicyclo
Di (cyclo) alkylamines such as xylamine; tri
Ethylamine, tri-n-propylamine, tri-n-
Butylamine, tri-n-pentylamine, tri-n-
Hexylamine, tri-n-heptylamine, tri-n
-Octylamine, tri-n-nonylamine, tri-n
-Decylamine, cyclohexyldimethylamine,
Clohexylmethylamine, tricyclohexylamine
Tri (cyclo) alkylamines such as aniline, N-
Methylaniline, N, N-dimethylaniline, 2-methyl
Luaniline, 3-methylaniline, 4-methylanili
, 4-nitroaniline, diphenylamine, triphe
And aromatic amines such as nylamine and naphthylamine.
Can be As the nitrogen-containing compound (b), for example,
Tylenediamine, N, N, N ', N'-tetramethylethyl
Rangeamine, tetramethylenediamine, hexamethyle
Diamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-di
Aminobenzophenone, 4,4'-diaminodiphenyl
Amine, 2,2-bis (4-aminophenyl) propa
2- (3-aminophenyl) -2- (4-aminophenyl
Enyl) propane, 2- (4-aminophenyl) -2-
(3-hydroxyphenyl) propane, 2- (4-amido)
Nophenyl) -2- (4-hydroxyphenyl) propa
1,4-bis [1- (4-aminophenyl) -1-
Methylethyl] benzene, 1,3-bis [1- (4-A
Minophenyl) -1-methylethyl] benzene, bis
(2-dimethylaminoethyl) ether, bis (2-di
Ethylaminoethyl) ether and the like.
You. Examples of the nitrogen-containing compound (c) include polyethylene
Nimine, polyallylamine, 2-dimethylaminoethyl
And a polymer of ruacrylamide. Previous
As the quaternary ammonium hydroxide compound, for example,
For example, tetramethylammonium hydroxide,
Tyl ammonium hydroxide, tetra-n-propyl
Ammonium hydroxide, tetra-n-butylammonium
And sodium hydroxide. As the amide group-containing compound, for example,
For example, Nt-butoxycarbonyldi-n-octylamino
, Nt-butoxycarbonyldi-n-nonylamino
, Nt-butoxycarbonyldi-n-decylamino
, Nt-butoxycarbonyldicyclohexylamino
, Nt-butoxycarbonyl-1-adamantylua
Min, Nt-butoxycarbonyl-N-methyl-1-
Adamantylamine, N, N-di-t-butoxycarbo
Nyl-1-adamantylamine, N, N-di-t-but
Xycarbonyl-N-methyl-1-adamantylamido
, Nt-butoxycarbonyl-4,4'-diamino
Diphenylmethane, N, N'-di-t-butoxycarbo
Nylhexamethylenediamine, N, N, N'N'-tetra
Tert-butoxycarbonylhexamethylenediamine,
N, N'-di-t-butoxycarbonyl-1,7-dia
Minoheptane, N, N'-di-t-butoxycarbonyl
-1,8-diaminooctane, N, N'-di-t-but
Xycarbonyl-1,9-diaminononane, N, N'-
Di-t-butoxycarbonyl-1,10-diaminodeca
, N, N'-di-t-butoxycarbonyl-1,12
-Diaminododecane, N, N'-di-t-butoxycal
Bonyl-4,4'-diaminodiphenylmethane, Nt
-Butoxycarbonylbenzimidazole, Nt-butyl
Toxicarbonyl-2-methylbenzimidazole, N
-T-butoxycarbonyl-2-phenylbenzimida
Nt-butoxycarbonyl group-containing amination such as sol
Compounds, formamide, N-methylformamide,
N, N-dimethylformamide, acetamide, N-meth
Tilacetamide, N, N-dimethylacetamide,
Lopionamide, benzamide, pyrrolidone, N-methyl
Rupyrrolidone and the like can be mentioned. Examples of the urea compound include urine
Element, methylurea, 1,1-dimethylurea, 1,3-
Dimethylurea, 1,1,3,3-tetramethyluree
A, 1,3-diphenylurea, tri-n-butylthio
Urea and the like can be mentioned. The nitrogen-containing heterocyclic compound
As the substance, for example, imidazole, 4-methylimida
Sol, 4-methyl-2-phenylimidazole, ben
Zimidazole, 2-phenylbenzimidazole, etc.
Imidazoles; pyridine, 2-methylpyridine, 4-
Methylpyridine, 2-ethylpyridine, 4-ethylpyri
Gin, 2-phenylpyridine, 4-phenylpyridine,
2-methyl-4-phenylpyridine, nicotine, nicotine
Acid, nicotinamide, quinoline, 4-hydroxy
Pyridine such as noline, 8-oxyquinoline, and acridine
And piperazine, 1- (2-hydroxyethyl) pipera
In addition to piperazines such as gin, pyrazine, pyrazole,
Pyridazine, quinosaline, purine, pyrrolidine, piperi
Gin, 3-piperidino-1,2-propanediol,
Ruphorin, 4-methylmorpholine, 1,4-dimethylpi
Perazine, 1,4-diazabicyclo [2.2.2] octane
And the like. Of these nitrogen-containing organic compounds, amides
Group-containing compounds, nitrogen-containing heterocyclic compounds and the like are preferable, and
Among the amide group-containing compounds, Nt-butoxycarboni
And a nitrogen-containing heterocyclic compound.
Among them, imidazoles are preferred. The acid diffusion controller
Can be used alone or as a mixture of two or more.
Wear. The compounding amount of the acid diffusion controller is 100% by weight of the resin (A).
Parts by weight, usually 15 parts by weight or less, preferably 10 parts by weight
Parts by weight or less, more preferably 5 parts by weight or less. this
When the amount of the acid diffusion controller exceeds 15 parts by weight,
Sensitivity as resist and developability of exposed part tend to decrease
There is. In addition, the compounding amount of the acid diffusion controlling agent is 0.001 weight
Parts, the resist and depending on the process conditions,
Pattern shape and dimensional fidelity may be reduced.
You. In addition, the radiation-sensitive resin composition of the present invention
Indicates dry etching resistance, pattern shape,
An acid-dissociable organic group that has the effect of further improving
An alicyclic additive can be blended. like this
Examples of the alicyclic additives include, for example, 1-adamantanka
T-butyl rubonate, t- 1-adamantane carboxylic acid
Butoxycarbonylmethyl, 1,3-adamantandica
Di-t-butyl rubonate, t-butyl 1-adamantane acetate
Tyl, 1-adamantane acetate t-butoxycarbonyl
Butyl, di-t-butyl 1,3-adamantane diacetate, etc.
Adamantane derivatives; t-butyl deoxycholate,
T-butoxycarbonylmethyl deoxycholate, deo
2-ethoxyethyl xycholate, deoxycholic acid 2
-Cyclohexyloxyethyl, deoxycholic acid 3-
Oxocyclohexyl, tetrahydrodeoxycholate
Pyranyl, deoxycholic acid mevalonolactone ester
Deoxycholate esters; lithocholic acid t-butyl ester
Tyl, tert-butoxycarbonylmethyl lithocholic acid,
2-ethoxyethyl tocholate, 2-cyclotolic acid
Rohexyloxyethyl, 3-oxolithocholic acid
Rohexyl, tetrahydropyranyl lithocholic acid, litho
Lithocholic acid such as mevalonolactone cholic acid ester
Stels and 2,5-dimethyl-2,5-di (adaman
Tylcarbonyloxy) hexane and the like.
You. These alicyclic additives may be used alone or in combination of two or more.
They can be mixed and used. Amount of alicyclic additive
Is usually 50 parts by weight based on 100 parts by weight of the resin (A).
Parts by weight, preferably 30 parts by weight or less. in this case,
If the amount of the alicyclic additive exceeds 50 parts by weight,
The heat resistance of the glass tends to decrease. In addition, the radiation-sensitive resin composition of the present invention
Is a surfactant that has the effect of improving coatability, developability, etc.
Can be blended. Examples of the surfactant include:
For example, polyoxyethylene lauryl ether, polyoxy
Siethylene stearyl ether, polyoxyethylene
Rail ether, polyoxyethylene n-octylfe
Nyl ether, polyoxyethylene n-nonylphenyl
Ether, polyethylene glycol dilaurate, poly
Nonionic interface such as ethylene glycol distearate
In addition to activators, KP341 (Shin-Etsu Chemical Co., Ltd.)
Industry Co., Ltd.), Polyflow No. No. 75, the same No. 95
(Manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, E-top
F303, EF352 (Tochem Products Co., Ltd.)
), Megafax F171, F173
Nuki Chemical Industry Co., Ltd.), Florado FC430, F
C431 (manufactured by Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, Same
SC-102, SC-103, SC-104, S
C-105 and SC-106 (made by Asahi Glass Co., Ltd.)
I can do it. These surfactants can be used alone or
Can be used as a mixture of two or more. Surface activity
The mixing amount of the agent is a total of 1 for the resin (A) and the acid generator (B).
It is usually 2 parts by weight or less based on 00 parts by weight. Further
In addition, as additives other than the above, an antihalation agent,
Adhesion aids, storage stabilizers, defoamers, etc.
You. [0053]Preparation of composition solution The radiation-sensitive resin composition of the present invention is usually used for its use.
And the total solid concentration is usually 5 to 50% by weight, preferably
Or 10 to 25% by weight in a solvent.
That is, for example, filtration with a filter having a pore size of about 0.2 μm
Thereby, it is prepared as a composition solution. The composition
Examples of the solvent used for preparing the solution include, for example, 2-
Butanone, 2-pentanone, 3-methyl-2-butano
2-hexanone, 4-methyl-2-pentanone, 3
-Methyl-2-pentanone, 3,3-dimethyl-2-bu
Linear forms such as tanone, 2-heptanone, 2-octanone, etc.
Or branched ketones; cyclopentanone, 3-methyl
Rucyclopentanone, cyclohexanone, 2-methyl
Clohexanone, 2,6-dimethylcyclohexanone,
Cyclic ketones such as isophorone; propylene glycol
Monomethyl ether acetate, propylene glycol
Monoethyl ether acetate, propylene glycol
Mono-n-propyl ether acetate, propylene glycol
Recall mono-i-propyl ether acetate, pro
Pyrene glycol mono-n-butyl ether acetate
G, propylene glycol mono-i-butyl ether
Acetate, propylene glycol mono-sec-butyl
Ether acetate, propylene glycol mono-t-
Propylene glycol molybdenum such as butyl ether acetate
Noalkyl ether acetates; 2-hydroxypro
Methyl pionate, ethyl 2-hydroxypropionate,
N-propyl 2-hydroxypropionate, 2-hydro
I-propyl xypropionate, 2-hydroxypropionate
N-butyl onate, i-butyl 2-hydroxypropionate
Tyl, sec-butyl 2-hydroxypropionate, 2
2-hydroxy such as t-butyl hydroxypropionate
Alkyl cypropionates; 3-methoxypropionic acid
Methyl, ethyl 3-methoxypropionate, 3-ethoxy
Methyl cypropionate, 3-ethoxypropionate
Alkyl 3-alkoxypropionates such as N-propyl alcohol, i-propyl alcohol
Alcohol, n-butyl alcohol, t-butyl alcohol
, Cyclohexanol, ethylene glycol monomethyl
Ether, ethylene glycol monoethyl ether,
Ethylene glycol mono-n-propyl ether, ethi
Lenglycol mono-n-butyl ether, diethylene
Glycol dimethyl ether, diethylene glycol di
Ethyl ether, diethylene glycol di-n-propyl
Diether, diethylene glycol di-n-butylate
Ter, ethylene glycol monomethyl ether acetate
G, ethylene glycol monoethyl ether acetate
G, ethylene glycol mono-n-propyl ether
Acetate, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene
Glycol mono-n-propyl ether, toluene,
Silene, 2-hydroxy-2-methylpropionic acid ethyl ester
, Ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybuty
Ruacetate, 3-methyl-3-methoxybutyl acetate
, 3-methyl-3-methoxybutyl propionate
G, 3-methyl-3-methoxybutyl butyrate, acetic acid
Ethyl, n-propyl acetate, n-butyl acetate, acetovinegar
Acid methyl, ethyl acetoacetate, methyl pyruvate, pill
Ethyl borate, N-methylpyrrolidone, N, N-dimethyl
Ruformamide, N, N-dimethylacetamide, ben
Jil ethyl ether, di-n-hexyl ether, die
Tylene glycol monomethyl ether, diethylene glycol
Coal monoethyl ether, caproic acid, caprylic acid,
1-octanol, 1-nonanol, benzyl alcohol
Benzyl acetate, ethyl benzoate, diethyl oxalate
, Diethyl maleate, γ-butyrolactone, carbonic acid
Tylene, propylene carbonate and the like can be mentioned. These solvents may be used alone or in combination of two or more.
It can be used as a mixture,
Are branched ketones, cyclic ketones, propylene glycol
Coal monoalkyl ether acetates, 2-hydro
Alkyl xypropionates, 3-alkoxypropio
Alkyl acids and the like are preferred. [0056]Method of forming resist pattern The radiation-sensitive resin composition of the present invention is particularly suitable for a chemically amplified type resin.
Useful as a strike. The chemically amplified resist smell
Of acid generated from acid generator (B) by exposure
As a result, the acid dissociable group in the resin (A) is dissociated, and
Boxyl groups, and as a result,
The solubility in the potash developer is increased, and
Dissolved and removed by potash developer, positive resist
A pattern is obtained. The radiation-sensitive resin composition of the present invention
When forming a resist pattern from the composition solution
Suitable application means such as spin coating, casting coating, roll coating, etc.
Thus, for example, silicon wafers and aluminum
By applying it on a substrate such as a covered wafer,
A distaste film is formed, and a heat treatment (hereinafter, referred to as
It is called "PB". ), And then apply the specified resist pattern.
The resist film is exposed to form a pattern. That
The radiation used when the acid generator used
Depending on the type, visible light, ultraviolet light, far ultraviolet light, electron beam,
X-rays etc. are appropriately selected and used, but ArF excimer
Laser (193nm wavelength) or KrF excimer
(Wavelength 248 nm) is preferred. In the present invention
Means heat treatment (hereinafter referred to as “PEB”) after exposure.
It is preferred to do so. By this PEB, in the resin (A)
The dissociation reaction of the acid-dissociable organic group proceeds smoothly. PEB
The heating conditions depend on the composition of the radiation-sensitive resin composition.
Usually varies from 30 to 200 ° C., preferably from 50 to 200 ° C.
170 ° C. In the present invention, the radiation-sensitive resin composition
In order to maximize the potential of
No. 12452, etc.
An organic or inorganic anti-reflective coating on a substrate
It can also be stored in the atmosphere
To prevent the influence of impurities and the like, see, for example, JP-A-5-18.
No. 8,598, the resist coating is disclosed.
A protective film can be provided on the film, or these techniques can be used.
Surgery can also be used in combination. Then, the exposed resist
The resist pattern is developed by developing
To form As a developer used for development, for example,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate
, Sodium silicate, sodium metasilicate, ammo
Near water, ethylamine, n-propylamine, diethyl
Amines, di-n-propylamine, triethylamine,
Methyl diethylamine, ethyl dimethylamine, trie
Tanolamine, tetramethylammonium hydroxy
Do, pyrrole, piperidine, choline, 1,8-diazabi
Cyclo- [5.4.0] -7-undecene, 1,5-di
Alka such as azabicyclo- [4.3.0] -5-nonene
Alkaline aqueous solution in which at least one kind of alkaline compound is dissolved
Liquids are preferred. The concentration of the alkaline aqueous solution is usually
10% by weight or less. In this case, the alkaline aqueous solution
If the concentration exceeds 10% by weight, the unexposed areas will also dissolve in the developer.
It is not preferable because it may cause Further, the development comprising the above-mentioned alkaline aqueous solution
For example, an organic solvent can be added to the liquid. Said
Examples of the organic solvent include acetone and methyl ethyl ketone.
Ton, methyl i-butyl ketone, cyclopentanone,
Clohexanone, 3-methylcyclopentanone, 2,6
-Linear, branched or branched such as dimethylcyclohexanone
Is a cyclic ketone; methyl alcohol, ethyl alcohol
, N-propyl alcohol, i-propyl alcohol
, N-butyl alcohol, t-butyl alcohol,
Clopentanol, cyclohexanol, 1,4-hexyl
Al such as sundiol and 1,4-hexane dimethylol
Coals; ethers such as tetrahydrofuran and dioxane
, Ethyl acetate, n-butyl acetate, i-amyl acetate, etc.
Esters; aromatic hydrocarbons such as toluene and xylene
Phenol, acetonylacetone, dimethylform
Muamide and the like. These organic solvents
Can be used alone or as a mixture of two or more.
Wear. The amount of organic solvent used is relative to the alkaline aqueous solution.
Therefore, it is preferably 100% by volume or less. In this case, the organic solvent
If the amount of used exceeds 100% by volume, the developability decreases.
Therefore, there is a possibility that the undeveloped portion of the exposed portion is increased. Also,
Surfactants and the like are used in the developer consisting of the alkaline aqueous solution.
An appropriate amount can be added. In addition, alkaline aqueous solution
After developing with a developing solution, generally wash with water.
dry. [0059] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described by way of examples.
Embodiments will be described more specifically. However, the present invention
Is not limited to these embodiments. This
Here, parts are by weight unless otherwise specified. Example
Each measurement and evaluation in the comparative example was performed as follows.
Was. Mw: Tosoh Corporation GPC column (G2000HXL 2
Book, one G3000HXL, one G4000HXL)
1.0 mL / min flow rate, elution solvent tetrahydride
Under the analytical conditions of rofuran and column temperature of 40 ° C,
Gel permeation chromatography with styrene as standard
It was measured by Raffy (GPC). Radiation transmittance: spin coating of the composition solution on quartz glass
On a hot plate kept at 90 ° C
0.34 μm thick register formed by performing PB for 60 seconds
The absorbance at 193 nm
Then, the radiation transmittance is calculated, and the transmittance in the deep ultraviolet region is calculated.
It was a measure of lightness. Sensitivity: As a substrate, a film having a thickness of 820 ° was formed on the surface.
ARC25 (Brewer Science)
Silicone wafer with film (ARC25)
Each composition solution is spin-coated on the substrate using
Apply and apply PB on a hot plate under the conditions shown in Table 2.
The resist film with a thickness of 0.34 μm formed by performing
Nikon Corporation ArF excimer laser exposure system (Len
(The numerical aperture is 0.55 and the exposure wavelength is 193 nm).
Exposure through a mask pattern. Then, the conditions shown in Table 2
2.38% by weight of tetramethyl
60% at 25 ° C with aqueous ammonium hydroxide solution
Develop for 2 seconds, wash with water, dry, and apply a positive resist pattern.
Formed. At this time, a line with a line width of 0.15 μm
・ And space pattern (1L1S) is one-to-one line
The exposure amount formed in the width is defined as the optimal exposure amount.
Was taken as the sensitivity. Resolution: The smallest resist pattern that can be resolved at the optimum exposure
The dimensions of the button were defined as the resolution. Dry etching resistance:
Apply by spin coating on cone wafer, dry
0.5 μm thick resist film
Use MT dry etching system (Pinnacle8000)
The etching gas is CF_Four And a gas flow rate of 75 scc
m, pressure 2.5mTorr, output 2,500W
Perform dry etching, measure the etching rate,
Etching speed of coating made of cresol novolak resin
Evaluate relative etching rate by relative value to degree
Was. The lower the etching rate, the better the dry etching resistance
It means that it has excellent properties. Pattern shape: line and stripe with line width of 0.15 μm
Bottom dimension L of square section of pace pattern (1L1S)
b and the upper side dimension La are measured by a scanning electron microscope,
0.85 ≦ La / Lb ≦ 1 and pattern shape
If the pattern is not good,
When 0.85> La / Lb, the pattern shape is
Paper shape ". Resin Synthesis Example 1 Under nitrogen atmosphere, mevalonic lactone methacrylate
22 g, 3-hydroxy-1-adamantic methacrylate
17.5 g and 1-methylcyclopent methacrylate
Dissolve chill 10.5 in 2-butanone 150g and dissolve uniformly
Azobisisovalerate as a polymerization initiator
Add 3.3 g of chill and heat to 80 ° C under nitrogen atmosphere
And polymerized for 6 hours. After the reaction is completed, bring the reaction solution to room temperature.
After cooling and adding 100 g of 2-butanone,
Put into 1,000 g of heptane and precipitate the white powder
Filter, wash and vacuum dry to yield 37.5 g of resin (yield
75% by weight). This resin has Mw of 9,100
Yes, mevalonic lactone methacrylate, methacrylate
3-hydroxy-1-adamantyl luate and methacrylic acid
The copolymerization molar ratio of 1-methylcyclopentyl luate is 45 /
It was a 30/25 copolymer. The resin (A)
-1). Resin Synthesis Example 2 Under nitrogen atmosphere, mevalonic lactone methacrylate
22.5 g, 3-hydroxy-1-adama methacrylate
10.7 g of methyl ethyl and 2-ethyl-2-methacrylate
Dissolve 16.8 g of adamantyl in 150 g of 2-butanone
To obtain a homogeneous solution, and then use azobis
3.0 g of methyl sovalate was added, and the mixture was heated to 80 ° C.
And polymerized for 6 hours. After the reaction is completed, the reaction solution is
After cooling to room temperature, 100 g of 2-butanone was added.
And put into 1,000 g of 2-heptane to precipitate white
The color powder is filtered off, washed and dried under vacuum to give resin 33.0.
g (yield 66% by weight). This resin has Mw of 8,
100, mevalonic lactone methacrylate,
3-hydroxy-1-adamantyl methacrylate and
Copolymerization of 2-ethyl-2-adamantyl methacrylate
Was 50/20/30. This resin
Is referred to as a resin (A-2). Resin Synthesis Example 3 Under nitrogen atmosphere, mevalonic lactone methacrylate
4.3 g, 3-hydroxy-1-adaman methacrylate
15.3 g of chill and 2-methyl-2-a-methacrylate
Dissolve 30.4 g of damantyl in 150 g of 2-butanone
Azobisisopropane as a polymerization initiator
Add 2.8 g of methyl valerate and bring to 80 ° C under nitrogen atmosphere
Heated and polymerized for 6 hours. After the reaction is completed, the reaction solution is
After cooling to warm, 100 g of 2-butanone was added.
And put into 1,000 g of 2-heptane to precipitate white
The color powder was filtered off, washed, and dried in vacuum to obtain resin 39.0.
g (yield 78% by weight). This resin has Mw of 8,
800, mevalonic lactone methacrylate,
3-hydroxy-1-adamantyl methacrylate and
Copolymerization of 2-methyl-2-adamantyl methacrylate
The copolymer had a copolymer ratio of 10/30/60. This resin
Is referred to as a resin (A-3). Resin Synthesis Example 4 Under nitrogen atmosphere, mevalonic lactone methacrylate
16.1 g, 3-hydroxy-1-adama methacrylate
8.2 g of methyl and [1- (2-methyl-2-norbo)
Lunyl) ethoxycarbonyl] methacrylate 25.7
g was dissolved in 150 g of 2-butanone to obtain a homogeneous solution.
That is, methyl azobisisovalerate 3.0 was used as a polymerization initiator.
g and heated to 80 ° C. in a nitrogen atmosphere,
I combined. After completion of the reaction, the reaction solution is cooled to room temperature and
-After addition of 100 g of butanone, 2-heptane 1,
2,000 g, and the precipitated white powder is filtered off and washed.
And dried under vacuum to obtain 36.0 g of a resin (yield: 72% by weight).
Got. This resin has a Mw of 9,200,
Nick lactone methacrylate, 3-hydr methacrylate
Roxy-1-adamantyl and [1- (2-methyl-
2-norbornyl) ethoxycarbonyl] methacrylate
Is a copolymer having a copolymerization molar ratio of 35/15/50.
Was. This resin is referred to as resin (A-4). Examples 1 to 4 and Comparative Example 1 Various evaluations were made for each composition solution comprising the components shown in Table 1.
Value. Table 3 shows the evaluation results. Tree in Table 1
The components other than the fats (A-1) to (A-4) are as follows.
You. Other resin a-1: t-butyl methacrylate / methyl methacrylate /
Methacrylic acid copolymer (copolymer molar ratio = 40/40/2)
0, Mw = 20,000) Acid generator (B) B-1: 1- [1- (4-n-butoxynaphthyl)] tetra
Lahydrothiophenium nonafluoro-n-butanesul
Honate B-2: 1- (3,5-dimethyl-4-hydroxyphenyl)
B) tetrahydrothiophenium nonafluoro-n-butyl
Tansulfonate B-3: triphenylsulfonium nonafluoro-n-bu
Tansulfonate Acid diffusion control agent C-1: Nt-butoxycarbonyl-2-phenylben
Zimidazole C-2: 2-phenylbenzimidazole Other additives D-1: t-butyl deoxycholate solvent E-1: Propylene glycol monomethyl ether acete
To E-2: 2-heptanone [0067] [Table 1] [0068] [Table 2][0069] [Table 3] [0070] The radiation-sensitive resin composition of the present invention has an activity
Radiation, especially an ArF excimer laser (wavelength 193n)
m) Chemically amplified resist sensitive to deep UV rays
High transparency, high sensitivity to radiation,
Cash register for resolution, dry etching resistance, pattern shape, etc.
Excellent basic physical properties, as well as good developability and substrate
Adhesion to the material is also good, and if further miniaturization progresses in the future,
Very suitable for use in the production of anticipated semiconductor devices.
Can be

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Atsuko Kataoka             Jay 11-2-24 Tsukiji, Chuo-ku, Tokyo             SRL Co., Ltd. F-term (reference) 2H025 AA01 AA02 AA03 AA09 AB16                       AC04 AC08 AD03 BE00 BE10                       BG00 CB14 CB41 FA17                 4J100 AL08P AL08Q AL08R BA03Q                       BA11P BC02R BC09Q BC53P                       CA05 FA08 FA19 JA32

Claims (1)

Claims: (A) A repeating unit represented by the following general formula (I-1), a repeating unit represented by the following general formula (I-2), and a repeating unit represented by the following general formula (II) A resin which has an alkali-insoluble or hardly alkali-soluble resin having a repeating unit represented by the formula (A) and which is alkali-soluble by the action of an acid; and (B) a radiation-sensitive acid generator. Resin composition. Embedded image [In the general formula (I-1) and the general formula (I-2),
R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁴ , R ⁵ and R
⁶ independently represent a hydrogen atom or a hydroxyl group, and at least one of R ⁴ , R ⁵ and R ⁶ is a hydroxyl group. [Chemical formula 2] [In the general formula (II), R ⁷ represents a hydrogen atom or a methyl group, X represents a single bond or a divalent organic group having 1 to ⁸ carbon atoms, and R ⁸ represents a hydrogen atom, a 1 to 20 carbon atoms. A linear or branched alkyl group, or a C 4-20 alkyl group
And a divalent alicyclic hydrocarbon group or a derivative thereof. ]