JP2003302763A - Positive resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photoresist composition for far UV exposure excellent in edge roughness, etching resistance and exposure latitude. <P>SOLUTION: The positive resist composition comprises (A) a photoacid generator, (B) a resin containing a repeating unit having an alicyclic acid-decomposable group and (C) an alcohol compound having a 7-15C alicyclic hydrocarbon group and an alcoholic hydroxyl group. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention is sensitive to deep ultraviolet radiation.
Positive photoresist composition for microfabrication of semiconductor elements, etc.
For more details, see
The present invention relates to a di-type photoresist composition. [0002] In recent years, integrated circuits have been increasingly integrated.
In the manufacture of semiconductor substrates such as VLSI,
Processing of ultra-fine patterns with line widths below fum
It has come to be needed. To meet that need
Use of exposure equipment used for photolithography
Wavelengths have become shorter and are now even shorter in the far ultraviolet.
Excimer laser light (XeCl, KrF, ArF, etc.)
The use of has been considered. this
Used for lithography pattern formation in the wavelength region
There is a chemically amplified resist. As a photoresist composition for ArF light source
Alicyclic hydrocarbons for the purpose of imparting dry etching resistance
Resins in which elementary sites have been introduced have been proposed. like that
Resins include carboxylic acids such as acrylic acid and methacrylic acid.
Monomers with acid sites, hydroxyl groups and cyano groups in the molecule
Copolymerized monomer with alicyclic hydrocarbon group
The combined resin is mentioned. On the other hand, in the side chain of the acrylate monomer,
In addition to the method of introducing alicyclic hydrocarbon moieties, the polymer main chain
Dry etching utilizing alicyclic hydrocarbon moieties
A method of imparting resistance has also been studied. Japanese Patent Laid-Open Nos. 9-73173 and 1
No. 0-161313 discloses a structure containing an alicyclic group.
Protected alkali-soluble group and its alkali-soluble group
Structure that can be eliminated by acid and become alkali-soluble
A resist material using an acid-sensitive compound containing a unit is described
Has been. Used for photoresist for deep ultraviolet exposure
Resins containing acid-decomposable groups are
It is common to contain a cyclic hydrocarbon group of the group. Up
There are still many inadequacies in the technology described above, and improvements are desired.
The On the other hand, various performances of the resist are improved.
Therefore, a low molecular compound having a hydrophilic functional group is added to the composition.
It has been proposed to add. For example, JP-A-9-2
No. 74318 discloses a good pattern shape, and
Hydrophilic to reduce standing waves and halation
Alicyclic having a functional group and having 5 to 25 carbon atoms
Low molecular weight compounds and naphtho having 10 to 40 carbon atoms
It describes the addition of talenic low molecular weight compounds.
The Japanese Patent Application Laid-Open No. 2000-66396 discloses a remaining film ratio and a record.
Excellent dyst profile, resolution and adhesion, and
Resistant with excellent etching resistance and no development defects
In order to provide a strike, the resist composition
It is also possible to add a bridged hydrocarbon alcohol.
No. 2000-187327 discloses a lack of development during development.
A resist composition that eliminates the problems
For the purpose of giving hydrophilic functional groups and cyclic hydrocarbons
A low molecular compound having a basic group or a hydrophilic functional group
The addition of a naphthalene compound is described. Shi
However, even with these techniques, the resist composition and
The current situation is not yet satisfactory. [0008] Accordingly, it is an object of the present invention.
Uses far ultraviolet light, especially ArF excimer laser light
The above-mentioned micro-photofabrication performance
Positive-type photoresist composition that solves the above technical problems
In particular, edge roughness,
Deep UV with excellent etching resistance and exposure latitude
To provide a positive photoresist composition for line exposure
is there. [0009] Means for Solving the Problems The present inventors have made a positive type.
As a result of intensive studies on the constituent materials of the chemically amplified resist composition
As a result, the object of the present invention can be achieved by the following configuration.
And found the present invention. (1) (A) Photoacid generator, (B) Alicyclic acid
A resin containing a repeating unit having a degradable group, and
(C) an aliphatic cyclic hydrocarbon group having 7 to 15 carbon atoms and an alcohol
Containing an alcohol compound having a hydroxylic hydroxyl group
Di-type resist composition. Further preferred embodiments of the present invention are shown below. (2) The resin (A) is further represented by the following general formula (III)
Characterized by containing repeating units
The composition according to (1). [0012] [Chemical 1] In the general formula (III), R_ThreeIs a hydrogen atom or
Represents a methyl group. A_ThreeRepresents a single bond or a divalent linking group
The Z_ThreeRepresents a p + 1 valent alicyclic hydrocarbon group. p is 1
Represents an integer of ~ 3. (3) A repeating unit represented by the general formula (III)
The position is a repeating unit represented by the following general formula (IIIa)
The positive resist composition as described in (2) above, wherein
Stuff. [0015] [Chemical 2] In the general formula (IIIa), R₃₀Is a hydrogen atom or
Represents a methyl group. R₃₁~ R₃₃Each independently
Child, hydroxyl group or alkyl group, provided that at least one
Represents a hydroxyl group. (4) Repeat represented by the general formula (IIIa)
In units, R₃₁~ R₃₃Two of them are hydroxyl groups
The positive resist set as described in (3) above,
Adult. (5) Resin (B) is further cyclohexane lactate
, Norbornane lactone, or adamantane lactone
Containing the repeating unit having
(1) -Positive resist composition as described in (4). [0018] BEST MODE FOR CARRYING OUT THE INVENTION The components used in the present invention are as follows.
And will be described in detail. [1] (A) Photoacid generator The photoacid generator used in the present invention is an actinic ray or radiation.
It is a compound that generates an acid upon irradiation. As the photoacid generator used in the present invention,
Photoinitiator for photocationic polymerization, photoinitiation for photoradical polymerization
Agents, photodecolorants for dyes, photochromic agents, or microresists
Known light (400-200n) used for dies
m ultraviolet rays, far ultraviolet rays, particularly preferably g rays, h rays,
i-line, KrF excimer laser light), ArF excimer
-By laser light, electron beam, X-ray, molecular beam or ion beam
Appropriate selection of compounds that generate phosphoric acid and mixtures thereof
Can be used. In addition, other photoacid generators used in the present invention.
Examples of crude agents include diazonium salts and ammonium.
Salt, phosphonium salt, iodonium salt, sulfonium
Onium salts such as salts, selenonium salts and arsonium salts,
Organic halogen compounds, organometallic / organic halides, o
-Photoacid generator having a nitrobenzyl-type protecting group, imino
Photolysis, such as sulfonate
Generated compounds, disulfone compounds, diazoketosulfo
And diazodisulfone compounds.
In addition, these light-generating groups or compounds
Using a compound in which the product is introduced into the main chain or side chain of the polymer
be able to. Furthermore, V.N.R.Pillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
D.H.R.Barton etal, J. Chem. Soc., (C), 329 (1970), USA
Patent 3,779,778, European Patent 126,712
Use compounds that generate acid when exposed to light, such as
You can. Decomposition by irradiation with actinic ray or radiation
It is especially effective in combination with photoacid generators that generate acid.
The other photoacid generators will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) Oxazole derivatives represented by the general formula (PAG)
S-triazine derivative represented by 2). [0023] [Chemical 3] Where R²⁰¹Is a substituted or unsubstituted ant
Group, alkenyl group, R²⁰²Is substituted or unsubstituted
Aryl group, alkenyl group, alkyl group, -C (Y)_Three
Indicates. Y represents a chlorine atom or a bromine atom. In particular
The following compounds can be mentioned but are not limited to these:
It is not something. [0025] [Formula 4](2) represented by the following general formula (PAG3)
Represented by the general formula (PAG4)
Sulfonium salt. [0027] [Chemical formula 5] Where the formula Ar¹, Ar²Each independently
A substituted or unsubstituted aryl group is shown. R²⁰³, R²⁰⁴,
R²⁰⁵Each independently represents a substituted or unsubstituted alkyl
A group and an aryl group; Z^-Represents a counter anion, for example B
F_Four ^-, AsF₆ ^-, PF₆ ^-, SbF₆ ^-, SiF₆ ^2-, Cl
O_Four ^-, CF_ThreeSO_Three ^-Perfluoroalkane sulfone such as
Acid anion, pentafluorobenzenesulfonic acid anio
, Condensed polynuclear compounds such as naphthalene-1-sulfonic acid anion
Aromatic sulfonate anion, anthraquinone sulfonate
  Anion, sulfonic acid group-containing dye, etc.
However, it is not limited to these. Also R²⁰³, R²⁰⁴, R²⁰⁵2 of
And Ar¹, Ar²Through each single bond or substituent
May be combined. Specific examples include the following compounds.
However, it is not limited to these. [0032] [Chemical 6] [0033] [Chemical 7][0034] [Chemical 8] [0035] [Chemical 9][0036] Embedded image[0037] Embedded image[0038] Embedded image [0039] Embedded image [0040] Embedded image [0041] Embedded image [0042] Embedded image[0043] Embedded image[0044] Embedded image[0045] Embedded image [0046] Embedded imageIn the above, Ph represents a phenyl group.
The above oni represented by the general formulas (PAG3) and (PAG4)
Ummum salts are known, for example, U.S. Pat. No. 2,807,6.
48 and 4,247,473, JP-A-53-10
It can be synthesized by the method described in No. 1,331 etc.
The (3) Represented by the following general formula (PAG5)
A disulfone derivative or an a represented by the general formula (PAG6)
Minosulfonate derivative. [0049] Embedded image Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group is shown. R²⁰⁶Is replaced
Or an unsubstituted alkyl group or aryl group. A is substitution
Or an unsubstituted alkylene group, alkenylene group,
Represents a -len group. Specific examples include the following compounds.
However, it is not limited to these. [0052] Embedded image[0053] Embedded image[0054] Embedded image [0055] Embedded image[0056] Embedded image (4) Represented by the following general formula (PAG7)
Diazodisulfone derivative. [0058] Embedded image Where R is linear, branched or cyclic alkyl.
Represents an aryl group which may be substituted. Ingredients
Examples of compounds include the following compounds, but these
It is not limited to. [0060] Embedded image[0061] Embedded image The amount of these photoacid generators added in the composition
Based on the solid content of
Used, preferably 0.3 to 20% by mass, more preferably
Preferably, it is used in the range of 0.5 to 10% by mass. Photoacid
Sensitivity when added amount of generator is less than 0.001% by mass
Tends to be low, and the addition amount is more than 30% by mass.
If the resist absorbs too much light, the profile
Deterioration and tendency to narrow process (especially baking) margin
There is a direction. In the present invention, actinic rays or radiation
A compound that decomposes by irradiation to generate sulfonic acid is preferred.
Good. [2] (B) Recurring having an alicyclic acid-decomposable group
Resin containing return unit (hereinafter referred to as “acid-decomposable resin”)
U). In the present invention, the acid-decomposable resin as component (B) is an alicyclic type.
A resin containing a repeating unit having an acid-decomposable group
Preferably, the repeating unit represented by the following general formula (I)
It is resin containing position (A1). [0064] Embedded image In the general formula (I), R₁Is a hydrogen atom or
Represents a methyl group, A represents a single bond or a linking group, AL
G is any one of the following general formulas (pI) to (pV)
Represent. [0066] Embedded image Where R₁₁Is a methyl group, an ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobuty
And Z represents a carbon atom.
The atomic groups necessary to form alicyclic hydrocarbon groups
The R₁₂~ R₁₆Each independently has 1 to 4 carbon atoms
Indicates a chain or branched alkyl group or alicyclic hydrocarbon group
The However, R₁₂~ R₁₄At least one of
R₁₅, R₁₆Any of represents an alicyclic hydrocarbon group. R₁₇
~ R_{twenty one}Are each independently a hydrogen atom, 1 to 4 carbon atoms,
A linear or branched alkyl group or alicyclic hydrocarbon group
Represents, but R₁₇~ R_{twenty one}At least one of which is alicyclic
Represents a hydrocarbon group. R₁₉, R_{twenty one}Any of the carbon
1 to 4 linear or branched alkyl groups or alicyclic rings
Represents a hydrocarbon group. R_{twenty two}~ R_{twenty five}Are each independently carbon
1 to 4 linear or branched alkyl groups or alicyclic rings
Represents a hydrocarbon group of the formula, provided that R_{twenty two}~ R_{twenty five}At least
One represents an alicyclic hydrocarbon group. R_{twenty three}And R
_{twenty four}May be bonded to each other to form a ring. In the general formula (I), the linking group of A is a
Alkylene group, substituted alkylene group, ether group, thioate
Tell group, carbonyl group, ester group, amide group, sulf group
Is it a group consisting of an amide group, a urethane group, or a urea group?
Or a combination of two or more groups selected from
Represent. As the alkylene group in A above,
The groups represented can be mentioned. -[C (R_b ) (R_c )]_r − Where R_b , R_c Is a hydrogen atom, alkyl group, substituted
Represents a kill group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As an alkyl group
Is methyl, ethyl, propyl, isopropyl
Group, and a lower alkyl group such as a butyl group is preferable and more preferable.
Or methyl, ethyl, propyl, isopropyl
Selected from the group. As a substituent of the substituted alkyl group,
Hydroxyl group, halogen atom, alkoxy group (preferably carbon
Formula 1-4 can be mentioned. As an alkoxy group
Are methoxy, ethoxy, propoxy, butoxy
Examples thereof include those having 1 to 4 carbon atoms such as a group. C
As the rogen atom, chlorine atom, bromine atom, fluorine atom
Examples thereof include a child and an iodine atom. r is 1-10
Represents an integer. In the general formulas (pI) to (pV), R₁₂
~ R_{twenty five}The alkyl group in is substituted or non-substituted
Have 1 to 4 carbon atoms, which may be any
Represents a linear or branched alkyl group. Its alkyl
Examples of the group include a methyl group, an ethyl group, and n-propyl.
Group, isopropyl group, n-butyl group, isobutyl group, s
Examples include ec-butyl group and t-butyl group. Also,
The further substituent for the alkyl group includes 1 to 4 carbon atoms.
Alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms
Child, bromine atom, iodine atom), acyl group, acyloxy
Group, cyano group, hydroxyl group, carboxy group, alkoxycal
A bonyl group, a nitro group, etc. can be mentioned. R₁₁~ R_{twenty five}Is an alicyclic hydrocarbon group
Or as an alicyclic hydrocarbon group formed by Z and a carbon atom
May be monocyclic or polycyclic. Specifically, carbon number
5 or more monocyclo, bicyclo, tricyclo, tetrasi
A group having a black structure or the like can be given. That carbon
The number is preferably 6 to 30, and particularly preferably 7 to 25 carbon atoms.
Good. These alicyclic hydrocarbon groups have a substituent.
May be. Below, among the alicyclic hydrocarbon groups, the alicyclic part
An example of the structure of the minute is shown. [0071] Embedded image[0072] Embedded image[0073] Embedded image In the present invention, preference is given to the alicyclic moiety.
New examples include an adamantyl group, noradamantyl
Group, decalin residue, tricyclodecanyl group, tetracycline
Rhododecanyl, norbornyl, cedrol, cycl
Rohexyl group, cycloheptyl group, cyclooctyl group,
Examples include cyclodecanyl group and cyclododecanyl group.
it can. More preferably, the adamantyl group and the decalin residue
Group, norbornyl group, cedrol group, cyclohexyl
Group, cycloheptyl group, cyclooctyl group, cyclodeca
Nyl group, cyclododecanyl group, tricyclodecanyl group
is there. As a substituent of these alicyclic hydrocarbon groups
Is an alkyl group, substituted alkyl group, halogen atom, hydroxyl acid
Group, alkoxy group, carboxyl group, alkoxycarbo
Nyl group is mentioned. Examples of the alkyl group include a methyl group and an alkyl group.
Low such as til, propyl, isopropyl, butyl
A secondary alkyl group is preferred, more preferably a methyl group,
Selected from the group consisting of til, propyl and isopropyl
Represents a selected substituent. As a substituent of a substituted alkyl group
Is a hydroxyl group, a halogen atom or an alkoxy group
Can do. Examples of the alkoxy group include a methoxy group and eth
1 to 4 carbon atoms such as xoxy group, propoxy group, butoxy group
Can be mentioned. In addition, the pattern at the time of observation with a scanning electron microscope
From the point of small size variation (SEM resistance), general formula
In (I), A is a single bond, and ALG is
Particularly preferred are repeating units which are groups. [0077] Embedded image R₂₆And R₂₇Each independently has 1 to 1 carbon atoms.
4 linear or branched alkyl groups are represented. Hereinafter, the repeating unit represented by the general formula (I) is used.
Specific examples of monomers corresponding to the positions are shown. [0080] Embedded image[0081] Embedded image [0082] Embedded image[0083] Embedded image [0084] Embedded image[0085] Embedded image The acid-decomposable resin (B) of the present invention is
In addition to the return unit (A1), -COOR (R is fat
A hydrocarbon group having a cyclic group, but bonded to a —COO group
Has an alicyclic group when the carbon atom is a tertiary carbon atom
Which represents a non-acid-decomposable hydrocarbon group)
The position (A2) may be contained. Next, a repeating unit having -COOR
(A2) will be described. R is carbonized having an alicyclic group
A hydrogen group, provided that 3 carbon atoms are bonded to the —COO group.
When it is a secondary carbon atom, it has a non-acid-decomposable alicyclic group
Represents a hydrocarbon group. Here, the alicyclic group is monocyclic,
Or polycyclic. Specifically, products with 5 or more carbon atoms
Cyclo, bicyclo, tricyclo, tetracyclo structures, etc.
The group which has can be mentioned. Its carbon number is 5-30
Preferably 6 to 25 carbon atoms, particularly 6 to 15 carbon atoms
Is preferred. For specific examples of the alicyclic group, the general formula (I)
R in the definition of ALG₁₁~ R_{twenty five}As alicyclic carbonization
Aliphatic hydrocarbons formed by hydrogen groups or Z and carbon atoms
You can list the same ones listed for the group
The However, the alicyclic group in R is a substituent other than an alkyl group.
It does not have. The carbon atom constituting the alicyclic ring is -C
It may be bonded to the oxygen atom in OO- through a linking group.
However, it is preferable that they are directly bonded. As a linking group
Is defined in the same manner as A in formula (I) above.
Xylene group, ether group, carbonyl group, ester group or
Can include combinations of these. R smell
The carbon atom bonded to the —COO group is a tertiary carbon atom.
R is a non-acid-decomposable hydrocarbon group having an alicyclic group.
For example, the tertiary carbon atom forms an alicyclic ring.
A carbon atom that consists of three tertiary carbon atoms.
All bonds to other atoms constituting the alicyclic ring
(For example, when an adamantyl group is formed)
Can be. As the repeating unit (A2), for example,
Examples of the repeating unit represented by the following general formula (II)
be able to. [0089] Embedded image R₁And A are the same as those in formula (I).
It is righteousness. A is preferably a single bond. R is an alicyclic group
Which is bonded to the —COO group.
When the carbon atom is a tertiary carbon atom, non-acid-decomposable fat
A hydrocarbon group having a cyclic group is represented. Specific examples of the repeating unit (A2) are shown below.
However, it is not limited to these. [0092] Embedded image The acid-decomposable resin as the component (B)
It is present that it contains a repeating unit represented by the general formula (III).
This is preferable in terms of improving image quality. [0094] Embedded image In the general formula (III), R_ThreeIs a hydrogen atom or
Represents a methyl group. A_ThreeRepresents a single bond or a divalent linking group
The Z_ThreeRepresents a p + 1 valent alicyclic hydrocarbon group. p is 1
Represents an integer of ~ 3. That is, -Z_Three-(OH) p is alicyclic
This represents a group in which p hydrocarbon groups are substituted on a hydrocarbon group. A_ThreeAs the divalent linking group, the general formula
The same as A in (I) can be mentioned.
The same applies to the preferred group. Z_ThreeAlicyclic hydrocarbons
As the group, R in the general formula (I)₁₁~ R_{twenty five}As fat
Cyclic hydrocarbon groups, and preferred groups
But the same is true. p hydroxyl groups are Z_ThreeAlicyclic hydrocarbons
The basic group itself and the substituent part of the alicyclic hydrocarbon
Any of them may be substituted. It should be noted that the line pattern is formed by underexposure.
The general formula (II
As a repeating unit represented by (I), the following general formula (IIIa)
The repeating unit represented is preferred. [0098] Embedded image In the general formula (IIIa), R₃₀Is a hydrogen atom or
Represents a methyl group. R₃₁~ R₃₃Each independently
Child, hydroxyl group or alkyl group, provided that at least one
Represents a hydroxyl group. In addition, a hole pattern by underexposure
The general formula (I
In the repeating unit represented by IIa), R₃₁~ R₃₃No
More preferably, the two are hydroxyl groups. The following repeating formula (III)
Specific examples of units are listed below, but are not limited to these.
Yes. [0102] Embedded image [0103] Embedded image[0104] Embedded image Also, acid decomposition added to the composition of the present invention.
In terms of suppressing hole deformation during etching,
Containing a repeating unit having an alicyclic lactone structure
Is preferred. A repeating unit having an alicyclic lactone structure;
For example, cyclohexane lactone, norborna
Repeating with lactone or adamantane lactone
And unit. For example, having cyclohexanelactone
As the repeating unit, the following general formulas (V-1) and (V
A repeating unit having a group represented by -2), norborna
As a repeating unit having lactone, the following general formula
Repeat having groups represented by (V-3) and (V-4)
A repeating unit having an adamantane lactone and
The repeating unit having a group represented by the following general formula (VI):
A return unit can be mentioned. [0107] Embedded image In the general formulas (V-1) to (V-4),
R_1b~ R_5bEach independently has a hydrogen atom or a substituent.
Alkyl group, cycloalkyl group or alkeni
Represents a ru group. R_1b~ R_5bTwo of them combine to form a ring
You may make it. In the general formulas (V-1) to (V-4),
R_1b~ R_5bThe alkyl group in is linear or branched
And may have a substituent.
Yes. The linear or branched alkyl group has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups are preferred,
More preferably, it is linear or branched having 1 to 10 carbon atoms.
Alkyl group, more preferably methyl group, ethyl
Group, propyl group, isopropyl group, n-butyl group, iso
Butyl group, sec-butyl group, t-butyl group, pentyl
Group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group. R_1b~ R_5bAs a cycloalkyl group in
Are cyclopropyl, cyclopentyl, cyclohexane
Charcoal such as xyl group, cycloheptyl group, cyclooctyl group
Those having a prime number of 3 to 8 are preferred. R_1b~ R_5bA
Lucenyl groups include vinyl, propenyl, buteni
Preferred are those having 2 to 6 carbon atoms such as a ru group or a hexenyl group.
Yes. R_1b~ R_5bA ring formed by combining two of
As cyclopropane ring, cyclobutane ring, cyclo
Such as pentane ring, cyclohexane ring, cyclooctane ring, etc.
A 3-8 membered ring is mentioned. The general formula (V-1) to
R in (V-4)_1b~ R_5bConstitutes a cyclic skeleton
It may be linked to any carbon atom present. Also, the above alkyl groups and cycloalkyl
Group, a preferred substituent that the alkenyl group may have
Is an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a
Nitrogen atom, chlorine atom, bromine atom, iodine atom), carbon number
2 to 5 acyl groups, 2 to 5 acyloxy groups, and cyan
Group, hydroxyl group, carboxy group, alkoxy group having 2 to 5 carbon atoms
A cicarbonyl group, a nitro group, etc. can be mentioned. Represented by the general formulas (V-1) to (V-4).
As the repeating unit having a group, the following general formula (AI)
The repeating unit represented by these can be mentioned. [0113] Embedded image In the general formula (AI), R_b0Is a hydrogen atom,
A rogen atom, or a substituted or unsubstituted C1-C4
Represents an alkyl group. R_b0May have an alkyl group
As preferred substituents, the general formula (V-1) to
R in (V-4)_1bAs the alkyl group has
Examples of preferred substituents that may be mentioned are those exemplified above.
It is done. R_b0As the halogen atom, fluorine atom, salt
There may be mentioned an atomic atom, a bromine atom and an iodine atom. R
_b0Is preferably a hydrogen atom. A 'is a single bond, ether
Group, ester group, carbonyl group, alkylene group, or
The divalent group which combined these is represented. B₂Is the general formula
A group represented by any one of (V-1) to (V-4)
Represents. As A ′, the combined divalent group
For example, the following formula is exemplified. [0115] Embedded image In the above formula, R_ab, R_bbThe hydrogen field
Child, alkyl group, substituted alkyl group, halogen atom, hydroxy acid
Represents an alkoxy group, both of which are the same or different
Also good. Alkyl groups include methyl, ethyl, and
Lower alkyl such as propyl, isopropyl and butyl
Group, more preferably methyl group, ethyl group,
Selected from a propyl group and an isopropyl group. Substituted alk
As the substituent of the ru group, hydroxyl group, halogen atom, carbon number
There may be mentioned 1-4 alkoxy groups. Alkoki
Si groups include methoxy, ethoxy and propoxy
A group having 1 to 4 carbon atoms such as a butoxy group
Can do. Halogen atoms include chlorine and bromine
Examples thereof include a child atom, a fluorine atom, and an iodine atom. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2. In the following, the repetition represented by the general formula (AI)
Specific examples of the unit are given below, but the content of the present invention is not limited to these.
It is not specified. [0118] Embedded image[0119] Embedded image[0120] Embedded image[0121] Embedded image[0122] Embedded image[0123] Embedded image[0124] Embedded imageRepeated unit having adamantane lactone
The position is a repeating unit represented by the following general formula (VI).
Can be listed. [0126] Embedded image In the general formula (VI), A₆Is a single bond,
Alkylene group, cycloalkylene group, ether group, thio
From the group consisting of ether group, carbonyl group, ester group
Table of selected single or combination of two or more groups
The R_6aIs a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Group or a halogen atom. In the general formula (VI), A₆The Archile
Examples of the group include groups represented by the following formulas.
The -[C (Rnf) (Rng)] r- In the above formula, Rnf and Rng are a hydrogen atom, an alkyl group,
Substituted alkyl group, halogen atom, hydroxyl group, alkoxy group
And both may be the same or different. Alkyl
Groups include methyl, ethyl, propyl, and isop
A lower alkyl group such as a propyl group or a butyl group is preferred.
Preferably, methyl group, ethyl group, propyl group, isop
Selected from ropyl groups. As a substituent of a substituted alkyl group
Include hydroxyl groups, halogen atoms, and alkoxy groups.
You can. Alkoxy groups include methoxy and eth
1 to 4 carbon atoms such as xoxy group, propoxy group, butoxy group
Things can be mentioned. Halogen atoms include salts
List elemental atoms, bromine atoms, fluorine atoms, iodine atoms, etc.
You can. r is an integer of 1-10. In the general formula (VI), A₆Cycloa
Examples of the alkylene group include those having 3 to 10 carbon atoms.
Cyclopentylene group, cyclohexylene group,
Examples include a looctylene group. Z₆The bridged alicyclic ring containing
You may do it. Examples of substituents include halogen atoms.
Child, alkoxy group (preferably having 1 to 4 carbon atoms), alkoxy
Sicarbonyl group (preferably having 1 to 5 carbon atoms), acyl group
(For example, formyl group, benzoyl group), acyloxy group
(For example, propylcarbonyloxy group, benzoylo
Xyl group), alkyl group (preferably having 1 to 4 carbon atoms), carbon
Ruboxyl group, hydroxyl group, alkylsulfonylsulfamo
Yl group (-CONHSO₂CH_ThreeEtc.). still,
The alkyl group as a substituent further includes a hydroxyl group and a halogen atom.
Substituent, substituted with alkoxy group (preferably having 1 to 4 carbon atoms)
May be. In the general formula (VI), A₆Combined with
The oxygen atom of the ester group is Z₆Arihashi alicyclic including
Bonded at any position of the carbon atoms constituting the ring structure
Good. In the following, the repetition represented by the general formula (VI)
Specific examples of units are given below,
There is no. [0133] Embedded image [0134] Embedded imageThe acid-decomposable resin as component (B) of the present invention is
Have a lactone structure represented by the following general formula (IV)
Repeating units can be included. [0136] Embedded image In the general formula (IV), R_1aIs a hydrogen atom or
Represents a methyl group. W₁Is a single bond, an alkylene group,
Tell group, thioether group, carbonyl group, ester group
A group of two or more groups selected from the group consisting of
Represents a match. R_a1, R_b1, R_c1, R_d1, R_e1Each
Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The m and n each independently represents an integer of 0 to 3, m + n
Is 2 or more and 6 or less. R_a1~ R_e1An alkyl group having 1 to 4 carbon atoms of
Are methyl, ethyl, propyl, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl
Group, t-butyl group and the like. In the general formula (IV), W₁The Archile
Examples of the group include groups represented by the following formulas.
The -[C (Rf) (Rg)] r₁− In the above formula, Rf and Rg are a hydrogen atom, an alkyl group, or a substituent.
Indicates an alkyl group, halogen atom, hydroxyl group, or alkoxy group
Both may be the same or different. Alkyl group and
Are methyl, ethyl, propyl, isopropyl
And lower alkyl groups such as butyl and butyl are preferred.
Preferably, methyl, ethyl, propyl, isopropyl
Group. As a substituent of a substituted alkyl group
Is a hydroxyl group, a halogen atom or an alkoxy group
Can do. Examples of the alkoxy group include a methoxy group and an ethoxy group.
1 to 4 carbon atoms, such as silyl group, propoxy group, butoxy group
Can be mentioned. Halogen atoms include chlorine
List atoms, bromine atoms, fluorine atoms, iodine atoms, etc.
Can do. r₁Is an integer from 1 to 10. As a further substituent in the above alkyl group
Carboxyl group, acyloxy group, cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Lucoxy group, substituted alkoxy group, acetylamide group, amine
Examples include a alkoxycarbonyl group and an acyl group. here
Alkyl groups include methyl, ethyl, and propyl
Group, isopropyl group, butyl group, cyclopropyl group,
Lower alkyl groups such as chlorobutyl and cyclopentyl groups
Can be mentioned. As a substituent of a substituted alkyl group
Is a hydroxyl group, a halogen atom or an alkoxy group
Can do. As the substituent of the substituted alkoxy group,
Examples thereof include a xyl group. As an alkoxy group
Are methoxy, ethoxy, propoxy, butoxy
Examples thereof include those having 1 to 4 carbon atoms such as a group. Reed
Examples of the ruoxy group include an acetoxy group. C
As the rogen atom, chlorine atom, bromine atom, fluorine atom
Examples thereof include a child and an iodine atom. Hereinafter, the repetition represented by the general formula (IV)
Specific examples of the monomer corresponding to the unit are shown below.
It is not specified. [0142] Embedded image [0143] Embedded image[0144] Embedded imageIn the specific example of the general formula (IV), dew
From the point that the optical margin becomes better (IV-1
7) to (IV-36) are preferable. The acid-decomposable resin as component (B)
In addition to repeating units, dry etching resistance and standard development
Liquid suitability, substrate adhesion, resist profile,
Resolving power, heat resistance, and feeling, which are general required properties of dies
Contains various repeating units for the purpose of adjusting the degree, etc.
You can. Such repeating units include the following:
Mention may be made of repeating structural units corresponding to monomers.
However, it is not limited to these. This
Performance required for acid-decomposable resin, especially (1) coating solvent
(2) Film-forming property (glass transition point),
(3) Alkali developability, (4) Film slip (hydrophobic, Al
(5) Adhesion of unexposed part to substrate
And (6) dry etching resistance, etc. can be finely adjusted
Become. As such a monomer, for example, acrylic acid ester
Tells, methacrylates, acrylamides,
Methacrylamide, allyl compound, vinyl ether
Addition polymerization selected from the group, vinyl esters, etc.
Examples thereof include compounds having one sum bond. Specifically, the following monomers may be mentioned.
it can. Acrylic esters (preferably carbon number of alkyl group)
1 to 10 alkyl acrylate): methacrylic acid
, Ethyl acrylate, propyl acrylate, acrylic
Amyl acid, cyclohexyl acrylate, ethyl acrylate
Ruhexyl, octyl acrylate, acrylic acid-t-o
Cutyl, chloroethyl acrylate, 2-hydroxyethyl
Tyl acrylate, 2,2-dimethylhydroxypropy
Acrylate, 5-hydroxypentyl acrylate
, Trimethylolpropane monoacrylate, penta
Erythritol monoacrylate, benzyl acrylate
, Methoxybenzyl acrylate, furfuryl acrylic
Rate, tetrahydrofurfuryl acrylate and the like. Methacrylic acid esters (preferably al
Alkyl metaacrylate having 1 to 10 carbon atoms in the kill group
G): methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate
, Amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate
, Chlorobenzyl methacrylate, octyl methacrylate
Rate, 2-hydroxyethyl methacrylate, 4-hydroxy
Droxybutyl methacrylate, 5-hydroxy pliers
Methacrylate, 2,2-dimethyl-3-hydroxy
Propyl methacrylate, trimethylolpropane mono
Methacrylate, pentaerythritol monomethacrylate
, Furfuryl methacrylate, tetrahydrofurf
Ril methacrylate, etc. Acrylamides: Acrylamide, N-
Alkylacrylamide (the alkyl group has 1 carbon atom)
-10, such as methyl, ethyl, propyl
Group, butyl group, t-butyl group, heptyl group, octyl
Group, cyclohexyl group, hydroxyethyl group, etc.
The ), N, N-dialkylacrylamide (alkyl)
Examples of the group include those having 1 to 10 carbon atoms such as methyl group,
Til, butyl, isobutyl, ethylhexyl,
Cyclohexyl group, etc.), N-hydroxyethyl-
N-methylacrylamide, N-2-acetamidoethyl
Lu-N-acetylacrylamide and the like. Methacrylamide: Methacrylamide,
N-alkyl methacrylamide (the alkyl group is charcoal
Those having a prime number of 1 to 10, for example, methyl group, ethyl group, t-
Butyl, ethylhexyl, hydroxyethyl,
Chlorohexyl group, etc.), N, N-dialkylmetac
Rilamide (alkyl groups include ethyl, propyl
Group, butyl group, etc.), N-hydroxyethyl-N-
Methyl methacrylamide and the like. Allyl compounds: allyl esters (for example,
Allyl acetate, allyl caproate, allyl caprylate,
Allyl urinate, allyl palmitate, stearic acid
Lyl, allyl benzoate, allyl acetoacetate, allyl lactate
Etc.), allyloxyethanol and the like. Vinyl ethers: alkyl vinyl ether
(E.g. hexyl vinyl ether, octyl vinyl ether)
Ether, decyl vinyl ether, ethyl hexyl vinyl
Ether, methoxyethyl vinyl ether, ethoxy ether
Til vinyl ether, chloroethyl vinyl ether, 1
-Methyl-2,2-dimethylpropyl vinyl ether,
2-ethylbutyl vinyl ether, hydroxyethyl vinyl
Nyl ether, diethylene glycol vinyl ether,
Dimethylaminoethyl vinyl ether, diethylamino
Ethyl vinyl ether, butyl aminoethyl vinyl ether
Tellurium, benzyl vinyl ether, tetrahydrofurfuryl
Ruvinyl ether, etc. Vinyl esters: vinyl butyrate, vinyl
Nyl isobutyrate, vinyl trimethyl acetate, vinyl
Nil diethyl acetate, vinyl valate, vinyl cap
Loate, vinyl chloroacetate, vinyl dichloroa
Cetate, vinyl methoxyacetate, vinyl butoxy
Acetate, vinyl acetoacetate, vinyl lactate
Vinyl-β-phenylbutyrate, vinylcyclohexane
Xyl carboxylate and the like. Dialkyl itaconates;
Dimethyl itaconate, diethyl itaconate, itaconic acid
Dibutyl etc. Dialkyl esters of fumaric acid or
Noalkyl esters; dibutyl fumarate and the like. Other crotonic acid, itaconic acid, maleic anhydride
Inic acid, maleimide, acrylonitrile, methacryloni
Tolyl, maleonitrile, etc. In addition to the above, the above various repeating units have a phase.
Addition-polymerizable unsaturation that is copolymerizable with the corresponding monomer.
If it is a compound, it may be copolymerized. In the acid-decomposable resin, each repeating unit
The molar ratio is based on resist dry etching resistance and standard
Image liquid suitability, substrate adhesion, resist profile, and more
Is the general required performance of resist, resolution, heat resistance,
It is set as appropriate to adjust the sensitivity and the like. In the acid-decomposable resin (B) of the present invention, the general formula
The content of the repeating unit (A1) represented by (I) is
In the repeating unit, 20 to 55 mol% is preferable, and more preferable.
Preferably it is 24-50 mol%, More preferably, it is 28-45.
Mol%. Repeat having a group represented by -COOR
The content ratio of the unit (A2) is 5 to 3 in all repeating units.
0 mol% is preferred, more preferably 8-26 mol%,
More preferably, it is 10-22 mol%. General formula (II
The content of the repeating unit represented by I)
5 to 50 mol% is preferable in the position, more preferably 10
-45 mol%, more preferably 15-40 mol%
The Content of repeating unit having alicyclic lactone structure
Is preferably 5 to 60 mol% in all repeating units, more
Preferably it is 10-55 mol%, More preferably, it is 15-5
0 mol%. The side chain represented by the general formula (IV)
The content of repeating units having a ton structure is
5 to 60 mol% is preferable in the unit, more preferably 10%.
To 50 mol%, more preferably 15 to 45 mol%.
The When the composition of the present invention is for ArF exposure, ArF
From the viewpoint of transparency to light, acid-decomposable resins have aromatic groups.
Preferably not. The acid-decomposable resin used in the present invention is in accordance with a conventional method.
(For example, radical polymerization) can be synthesized. Example
For example, as a general synthesis method, monomer species are collectively
Alternatively, charge the reaction vessel in the middle of the reaction and use it as necessary.
Reaction solvents such as tetrahydrofuran, 1,4-dio
Ethers such as xanthone and diisopropyl ether
Cases such as til ethyl ketone and methyl isobutyl ketone
Tons, ester solvents such as ethyl acetate, and even later
Propylene glycol monomethyl ether acetate described above
Dissolved in a solvent that can dissolve various monomers.
Inert gas atmosphere such as nitrogen or argon
Under heating as necessary, commercially available radical initiator (azo
Polymerization using initiators, peroxides, etc.)
The Add initiator or add in portions as desired,
After completion of the reaction, put it in a solvent and collect powder or solid
The desired polymer is recovered by the method. Reaction concentration is 20 fold
% By weight or more, preferably 30% by weight or more, more preferably
It is preferably 40% by weight or more. The reaction temperature is 10 ° C to 1
50 ° C, preferably 30 ° C to 120 ° C, more preferably
Preferably it is 50-100 degreeC. The resin according to the present invention has a weight average molecular weight of G
As a polystyrene conversion value by the PC method, 3,000 to
100,000 is preferred, more preferably 4,000
0 to 50,000, more preferably 5,000 to 3
0,000. The weight average molecular weight is less than 3,000
Because deterioration of heat resistance and dry etching resistance is seen
It is not so preferable.
Degradation and film forming properties deteriorate due to extremely high viscosity
Results in less favorable results. Further, the dispersion degree of the resin according to the present invention (Mw /
Mn) is preferably in the range of 1.3 to 4.0, more
Preferably 1.4 to 3.8, more preferably 1.5 to 1.5.
3.5. In the positive resist composition of the present invention,
The compounding amount in the entire composition of all the resins according to the present invention is as follows:
40 to 99.99% by weight of total resist solid content is preferred
More preferably, it is 50 to 99.97% by weight. [3] (C) Aliphatic ring having 7 to 15 carbon atoms
Alcohol having a hydrocarbon group and an alcoholic hydroxyl group
Compound The alcohol compound used in the present invention is aliphatic and carbon.
A cyclic hydrocarbon having a number of 7 to 15, preferably 10 to 12
Group and an alcoholic hydroxyl group. Aliphatic cyclic hydrocarbon
Specific examples of groups include norbornane and adamanta.
, Tricyclodecane, tetracyclododecane, decali
Can be mentioned. In addition, a cyclic hydrocarbon group
May have a substituent and may have a substituent.
As the group, carboxyl group, ester group, ketone group,
Examples include aldehyde groups and lactone groups. Like
Or an ester group, a ketone group, or a lactone group. A
If at least one alcoholic hydroxyl group is contained,
Preferably 1 to 3, more preferably 1 to 2
It is desirable that it is contained. Specific examples include:
The compounds of (1) to (28) are mentioned. [0164] Embedded image [0165] Embedded imageIn the above specific examples, particularly preferred compounds
(1) to (3), (6) to (16), (1
8), (23) and (24). In the present invention, (C) an alcohol compound
Is added based on the solid content in the composition of the present invention.
Usually 0.1 to 20% by mass, preferably 0.3 to 15% by mass
%, More preferably 0.5 to 10% by mass. Addition amount
If the amount is too small, the curing of the present invention is not exhibited, and the quality is 20
Exceeding the amount% is preferable because significant film loss occurs.
Yes. These compounds may be added alone or
Also, some combinations can be added. [4] Other additives If necessary, the positive resist composition of the present invention may further include
Surfactant, organic basic compound, acid-decomposable dissolution inhibiting compound
In products, dyes, plasticizers, photosensitizers, and developers
The compound etc. which promote property can be contained. (D) Surfactant The positive resist composition of the present invention is a surfactant, preferably
Or contains fluorine and / or silicon surfactants
The The positive resist composition of the present invention has a fluorine-based surface active.
, Silicon surfactant, fluorine atom and silicon atom
Either one or two surfactants containing both
It is preferable to contain the above. Positive type resist of the present invention
Composition contains the acid-decomposable resin and the surfactant
This is particularly useful when the pattern line width is narrower.
And development defects are further improved. As these surfactants, for example,
62-36663, JP-A 61-226746, Special
Japanese Utility Model Publication No. 61-226745, Japanese Patent Application Laid-Open No. 62-170950
JP-A-63-334540, JP-A-7-23016
5, JP-A-8-62834, JP-A-9-54432
No. 9-5988, US Pat. No. 5,405,720
No., No. 5360692, No. 5529881, No. 5
296330, 54336098, 557614
3, No. 5294511, No. 5824451
The following commercially available surfactants can be mentioned.
Can be used as they are. Examples of commercially available surfactants that can be used include
F-top EF301, EF303, (Shin-Akita Kasei
), Florard FC430, 431 (Sumitomo 3E)
(Mu Co., Ltd.), Mega Fuck F171, F173, F17
6, F189, R08 (Dainippon Ink Co., Ltd.), Sir
Freon S-382, SC101, 102, 103, 10
4, 105, 106 (Asahi Glass Co., Ltd.), Troisol S
-366 (manufactured by Troy Chemical Co., Ltd.)
Mention may be made of a surfactant or a silicon-based surfactant.
Polysiloxane polymer KP-341 (Shin-Etsu Chemical Co., Ltd.)
Also used as a silicon-based surfactant
Can do. The compounding amount of the surfactant is in the composition of the present invention.
Usually, 0.001% by mass to 2% by mass based on the solid content of
%, Preferably 0.01% by mass to 1% by mass. this
These surfactants may be added alone, or
It can also be added in several combinations. Other than the above, usable surface activity
As the agent, specifically, polyoxyethylene lauryl
Ether, polyoxyethylene stearyl ether, poly
Lioxyethylene cetyl ether, polyoxyethylene
Polyoxyethylene alkyl ethers such as oleyl ether
Tells, polyoxyethylene octylphenolate
Such as polyoxyethylene nonylphenol ether
Polyoxyethylene alkyl allyl ethers, Polio
Xylene / Polyoxypropylene Block Copolymer
ー kind, sorbitan monolaurate, sorbitan monopal
Mitate, sorbitan monostearate, sorbitan
Nooleate, sorbitan trioleate, sorbitan
Sorbitan fatty acid esters such as tristearate,
Lioxyethylene sorbitan monolaurate, polyoxy
Siethylenesorbitan monopalmitate, polyoxye
Tylene sorbitan monostearate, polyoxyethylene
Sorbitan trioleate, polyoxyethylene sol
Polyoxyethylene sorbites such as bittan tristearate
Nonionic surfactants such as tan fatty acid esters
I can make it. Compounding amount of these other surfactants
Per 100 parts by weight of solid content in the composition of the present invention.
Usually, it is 2 parts by mass or less, preferably 1 part by mass or less. (E) Organic basic compound The positive resist composition of the present invention contains an organic basic compound.
It is preferable to contain. Preferred organic basic compounds and
Therefore, it is a compound having a stronger basicity than phenol.
Of these, nitrogen-containing basic compounds are preferable, for example,
Examples include structures represented by (A) to (E). [0175] Embedded image Here, R²⁵⁰, R²⁵¹And R²⁵²Each
Independently, hydrogen atom, alkyl group having 1 to 6 carbon atoms, carbon number
1-6 aminoalkyl groups, C1-C6 hydroxy
Alkyl group or substituted or unsubstituted of 6 to 20 carbon atoms
An aryl group, where R²⁵¹And R²⁵²Are joined together
To form a ring. [0177] Embedded image (Wherein R²⁵³, R²⁵⁴, R²⁵⁵And R
²⁵⁶Each independently represents an alkyl group having 1 to 6 carbon atoms.
) Further preferred compounds are those with different chemical environments per molecule.
A nitrogen-containing basic compound having two or more nitrogen atoms,
Particularly preferably, a substituted or unsubstituted amino group and nitrogen
Compounds containing both ring structures containing atoms or alkyl
It is a compound having an amino group. As a preferred embodiment
Is substituted or unsubstituted guanidine, substituted or unsubstituted
Substituted aminopyridine, substituted or unsubstituted amino
Alkyl pyridine, substituted or unsubstituted aminopyrrolidi
Substituted or unsubstituted indazole, substituted or
Unsubstituted pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted
Purines, substituted or unsubstituted imidazolines, substituted
Or unsubstituted pyrazoline, substituted or unsubstituted pipette
Razine, substituted or unsubstituted aminomorpholine,
Substituted or unsubstituted aminoalkylmorpholine, etc.
I can get lost. Preferred substituents are amino groups, aminoalkyls.
Group, alkylamino group, aminoaryl group, aryl
Amino, alkyl, alkoxy, acyl, acyl
Roxy group, aryl group, aryloxy group, nitro group,
A hydroxyl group and a cyano group; Preferred specific examples of nitrogen-containing basic compounds
Guanidine, 1,1-dimethylguanidine, 1,
1,3,3-tetramethylguanidine, 2-aminopi
Lysine, 3-aminopyridine, 4-aminopyridine, 2
-Dimethylaminopyridine, 4-dimethylaminopyridy
2-diethylaminopyridine, 2- (aminomethyl)
E) Pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methyl
Pyridine, 2-amino-6-methylpyridine, 3-amino
Noethylpyridine, 4-aminoethylpyridine, 3-a
Minopyrrolidine, piperazine, N- (2-aminoethyl)
L) Piperazine, N- (2-aminoethyl) piperidi
4-amino-2,2,6,6-tetramethylpiperi
Gin, 4-piperidinopiperidine, 2-iminopiperidi
, 1- (2-aminoethyl) pyrrolidine, pyrazol
, 3-amino-5-methylpyrazole, 5-amino-
3-methyl-1-p-tolylpyrazole, pyrazine, 2
-(Aminomethyl) -5-methylpyrazine, pyrimid
2,4-diaminopyrimidine, 4,6-dihydroxy
Cypyrimidine, 2-pyrazoline, 3-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morph
Oline, 1,5-diazabicyclo [4.3.0] nona
5-ene, 1,8-diazabicyclo [5.4.0] un
Deca-7-ene, 1,4-diazabicyclo [2.2.
2] Octane, 2,4,5-triphenylimidazole
, N-methylmorpholine, N-ethylmorpholine, N
-Hydroxyethylmorpholine, N-benzylmorpholine
, Cyclohexylmorpholinoethylthiourea (CH
Tertiary morpholine derivatives such as METU), JP-A-11-5
Hindered amines described in Japanese Patent No. 2575 (for example, the
This is the one described in the publication [0005].
It is not limited to. A particularly preferred embodiment is 1,5-diazabi.
Cyclo [4.3.0] non-5-ene, 1,8-diaza
Bicyclo [5.4.0] undec-7-ene, 1,4-
Diazabicyclo [2.2.2] octane, 4-dimethyl
Aminopyridine, hexamethylenetetramine, 4,4-
Dimethylimidazoline, pyrroles, pyrazoles,
Midazoles, pyridazines, pyrimidines, CHME
Tertiary morpholines such as TU, bis (1,2,2,6,6
-Pentamethyl-4-piperidyl) hin such as sebagate
Examples thereof include dard amines. Among them, 1,
5-diazabicyclo [4.3.0] non-5-ene,
1,8-diazabicyclo [5.4.0] undec-7
Ene, 1,4-diazabicyclo [2.2.2] octa
, 4-dimethylaminopyridine, hexamethylene tet
Lamin, CHMETU, bis (1,2,2,6,6-pe
Ntamethyl-4-piperidyl) sebagate is preferred. These nitrogen-containing basic compounds are used alone.
Or two or more types are used in combination. Nitrogen-containing basic
The amount of the compound used is the total composition of the resist composition of the present invention.
Usually, 0.001 to 10% by mass, based on the solid content of
It is 0.01-5 mass%. 0.001% by mass not yet
If not, the effect of adding the above nitrogen-containing basic compound cannot be obtained.
Yes. On the other hand, if it exceeds 10% by mass, the sensitivity decreases and the non-exposed area
The developability tends to deteriorate. The positive resist composition of the present invention comprises the above-mentioned respective
The components are dissolved in a solvent that dissolves and coated on the support. This
Solvents used here include ethylene dichloride and silane.
Clohexanone, cyclopentanone, 2-heptanone,
γ-butyrolactone, methyl ethyl ketone, ethylene glycol
Recall monomethyl ether, ethylene glycol mono
Ethyl ether, 2-methoxyethyl acetate, ethyl
Lenglycol monoethyl ether acetate, propylene
Ren glycol monomethyl ether (PGME), pro
Pyrene glycol monomethyl ether acetate (PG
MEA), ethylene carbonate, toluene, ethyl acetate
Butyl acetate, methyl lactate, ethyl lactate, methoxy
Methyl lopionate, ethyl ethoxypropionate, pills
Methyl binate, ethyl pyruvate, propirate pyruvate
N, N-dimethylformamide, dimethylsulfoxy
Sid, N-methylpyrrolidone, tetrahydrofuran, etc.
Preferably, these solvents are used alone or in combination.
The Of these, preferred solvents are
Pyrene glycol monomethyl ether acetate, 2-
Heptanone, γ-butyrolactone, ethylene glycol
Monomethyl ether, ethylene glycol monoethyl ester
Ether, ethylene glycol monoethyl ether acetate
, Propylene glycol monomethyl ether, pro
Pyrene glycol monoethyl ether, ethylene carbo
Nate, butyl acetate, methyl lactate, ethyl lactate, methoxy
Methyl cypropionate, ethyl ethoxypropionate,
List N-methylpyrrolidone and tetrahydrofuran
You can. Such a positive resist composition of the present invention.
Is applied onto the substrate to form a thin film. Film thickness of this coating
Is preferably 0.2 to 1.2 μm. Can be used
The substrate to be used is a normal BareSi substrate, SOG substrate, or
Is a substrate having an inorganic antireflection film described below, etc.
be able to. If necessary, commercially available inorganic or
Organic antireflective coatings can be used. As the antireflection film, titanium and titanium dioxide are used.
, Titanium nitride, chromium oxide, carbon, α-silicon
Inorganic film type such as, and organic film made of light absorber and polymer material
A mold can be used. The former is a vacuum deposition device for film formation.
Equipment, CVD equipment, sputtering equipment, etc.
To do. As an organic antireflection film, for example, Japanese Patent Publication No. 7-69.
Diphenylamine derivatives described in No. 611 and formaldehyde
Condensates with hydride-modified melamine resins, alkali-soluble trees
Made of fat, light absorber, US Pat. No. 5,294,680
Reaction of maleic anhydride copolymer and diamine type light absorber
Resin binder described in JP-A-6-188631
Containing a methylol melamine thermal crosslinking agent and JP,
Carboxylic acid group and epoxy group described in JP-A-6-118656
Acrylic resin type anti-reflective that has a light-absorbing group in the same molecule
Methylol melamine described in JP-A-8-87115
And a benzophenone light absorber, Japanese Patent Laid-Open No. 8-1
Low molecular weight polyvinyl alcohol resin described in 79509
The thing etc. which added the light absorber are mentioned. Also organic reflection
DUV3 manufactured by Brewer Science as a protective film
0 series, DUV-40 series, ARC25,
AC-2, AC-3, AR19, AR20 made by Play
Etc. can also be used. The above resist solution is used to manufacture precision integrated circuit elements.
Substrates such as those used in silicon (eg silicon / silicon dioxide)
(If necessary, the above-mentioned antireflection film is provided)
On the substrate), suitable for spinner, coater, etc.
After applying more, expose through a predetermined mask and perform baking.
Develop a good resist pattern
You can. Here, the exposure light is preferably 150.
It is light with a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248nm), ArF excimer
Laser (193 nm), F₂Excimer laser (157
nm), X-rays, electron beams, and the like. As the developer, sodium hydroxide, hydroxide
Potassium halide, sodium carbonate, sodium silicate, meta
Inorganic alkalis such as sodium silicate and aqueous ammonia,
Primary amines such as ethylamine and n-propylamine,
Secondary amines such as diethylamine and di-n-butylamine
, Triethylamine, methyldiethylamine, etc.
Amines, dimethylethanolamine, triethanol
Alcohol amines such as amines, tetramethylammoni
Um hydroxide, tetraethylammonium hydroxide
Quaternary ammonium salts such as Cid, pyrrole, pihelidine
Use alkaline aqueous solutions such as cyclic amines
Can do. In addition, the alkaline aqueous solution
Can be used with an appropriate amount of surfactant added.
The [0188] The present invention will be described in more detail with reference to the following examples.
As will be described, the present invention is limited to the following examples.
There is no. Synthesis Example (1) Synthesis of Resin (1) 2-adamantyl-2-propyl methacrylate, nor
Bornan lactone acrylate, dihydroxyadaman
Preparation of tan methacrylate at a ratio of 35/50/15
PGMEA (propylene glycol monomethyl ether
Teracetate) / PGME (propylene glycol model)
Nomethyl ether) = 70/30 (mass ratio)
450 g of a solution having a solid content concentration of 22% by mass was prepared. this
Oil-soluble azo polymerization initiator in solution (manufactured by Wako Pure Chemical Industries, V-6
01) was added, and this was added in a nitrogen atmosphere for 6 hours.
PGMEA (propylene rubber) heated to 100 ° C
Recall monomethyl ether acetate) / PGME
(Propylene glycol monomethyl ether) = 70 /
30 (mass ratio) was added dropwise to 40 g. After dropping, reaction
The solution was stirred for 4 hours. After completion of the reaction, the reaction solution is cooled to room temperature.
To 5 L of a mixed solvent of hexane / ethyl acetate = 9/1.
The powder obtained after crystallizing and filtering the precipitated white powder.
Recycle the body with a mixed solvent of hexane / ethyl acetate = 9/1.
The resin is the target product after filtration and drying.
(1) was recovered. The polymer composition ratio determined from NMR was 2-a.
Damantyl-2-propyl methacrylate / norborna
Lactone acrylate / dihydroxyadamantane
Tacrylate = 34/50/16. Also, GP
Standard polystyrene equivalent mass average determined by C measurement
The number of children was 10100. In the same manner as in the above synthesis example,
(12) was synthesized. Repetition of resins (1) to (12)
The structure of the repeat unit is shown below. Also, these resins
Table 1 shows the content of repeating units and the weight average molecular weight.
The The ratio of repeating units in Table 1 is shown below.
In the repeat unit structure, the order from the left repeat unit
It is. [0192] Embedded image [0193] Embedded image[0194] Embedded image [0195] [Table 1]Examples 1 to 12 and Comparative Examples 1 to 3 (Preparation and evaluation of positive resist composition) Table 2
Resin (1.8 g) synthesized in the above synthesis example,
Photoacid generator (blending amount shown in Table 2), component (C)
(0.2g) Organic basic compound (4 mg), surfactant if necessary
(10 mg) is added so that the solid content is 14% by mass.
After dissolving in the solvents shown in Table 2, 0.1 μm
Filter with a filter, and use the samples of Examples 1-14 and Comparative Examples 1 and 2.
A di-type resist composition was prepared. Each component in Table 2
The ratio when using a plurality of minutes is a mass ratio. The resin R1 used in Comparative Example 1 is disclosed in JP
Resin A described in Example 1 of 2000-187327
(1.4 g), and the resin R2 used in Comparative Example 2 is
Resin described in Example 4 of JP 2000-187327 A
D (1.4 g). [0198] [Table 2] The symbols for each component in Table 2 are as follows. [Surfactant] W1: Mega Fuck F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W2: Megafuck R08 (Dainippon Ink Co., Ltd.)
(Fluorine and silicone) W3: Polysiloxane polymer KP-341 (Shin-Etsu Chemical)
Manufactured by Kogyo Co., Ltd.) W4: Polyoxyethylene nonylphenyl ether W5: Troisol S-366 (Troy Chemical Co., Ltd.)
Made) [Basic compounds] 1: 1,5-diazabicyclo [4.3.0] -5-none
(DBN) 2: N, N-bis (2-hydroxyethyl) aniline
(2HE) 3: Trioctylamine 4: Triphenylimidazole 5: Antipyrine 6: 2,6-diisopropylaniline Represents. [Solvent] S1: Propylene glycol monomethyl ether acetate
The S2: Propylene glycol monomethyl ether S3: γ-butyrolactone S4: Cyclohexanone S5: Ethyl lactate S6: Butyl acetate [Line edge roughness] Br on the Si substrate
Ewer Science's anti-reflective coating ARC-29 film is 8
The resist solution prepared above is formed on it with a thickness of 5 nm.
Coating, 120 ° C, 90 seconds baking, 0.30μm film thickness
It was painted with. The wafer thus obtained was converted into ArF exci
Marase Stepper (ArF exposure machine 930 manufactured by ISI)
0) with a resolution mask and changing the exposure amount
Exposed. Then in a clean room at 120 ° C for 90 seconds
After heating, tetramethylammonium hydroxide
Developed for 60 seconds with a developer (2.38% by mass), distilled water
Rinse and dry to obtain a pattern. 1 in the mask
25 nm line pattern (line / space = 1 /
125 nm obtained with the minimum exposure to reproduce 1)
For the range of 5 μm edge in the longitudinal direction of the line pattern
The distance from the reference line where there should be an edge is made by Hitachi, Ltd.
Measure 50 points with S-9220 made by Sakusho.
The difference was calculated and 3σ was calculated. The smaller the value, the better
Indicates that [Etching resistance] Brewer S on Si substrate
The film of the anti-reflection film ARC-29 manufactured by cience is 85 nm thick.
And apply the resist solution prepared above on it,
Bake at 120 ° C for 90 seconds to coat 0.50μm thick
did. The resist film thus obtained was exposed using an ArF stepper.
Light, post-heat and develop at 120 ° C to form a pattern
It was. The obtained film was made into a reactive ion etch manufactured by ULVAC.
CF using a cinch device (CSE-1110)_Fourgas
The etching rate with respect to was measured. Regis of Example 1
The phase of each resist when the etching rate of the resist is 1.0
Etching rate ratio for each example
Speed / etching speed of the resist of Example 1)
It was used as an index of etching resistance. The higher this value, the more
The lower the value, the better the etching.
It shows that. [Exposure latitude] Brewer on Si substrate
 The antireflection film ARC-29 manufactured by Science Co.
m, and apply the resist solution prepared above on it.
Cloth, 120 ° C, 90 seconds baking, with a film thickness of 0.30μm
Painted. The resist film thus obtained was used as an ArF stepper.
To form patterns by post-heating and development at 120 ° C.
went. 130nm (1/1 line and space)
The exposure amount that reproduces the mask line width is the optimum exposure amount, and the exposure amount
Target line when the optimal exposure fluctuates ± 5%
Measure the line width of (mask = 130 nm)
The line width variation rate was calculated based on the following equation. Exposure latitude (%) = {([optimum exposure amount -5%]
Line width when exposed with exposure amount)-([optimum exposure amount + 5%]
Line width when exposed at an exposure amount)} / 130 (nm) × 1
00 The evaluation results are shown in Table 3 below. [0205] [Table 3]From the results shown in Table 3, the composition of the present invention has
Large roughness, etching resistance and exposure latitude
It turns out that it is very good. [0207] According to the present invention, edge roughness and resistance to edges are improved.
Positive type resist with excellent ching characteristics and exposure latitude
A composition can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA03 AA09 AB16 AC04 AC05                       AC08 AD03 BE00 BG00 CC20                       FA03 FA12 FA17                 4J100 AL03Q AL08P AL08Q AL08R                       AL08S BA03R BA03S BA11Q                       BA20Q BC08R BC08S BC09P                       BC09Q BC09S BC12P BC12R                       BC12S BC53Q CA05 CA06                       FA03 FA19 HA08 JA38

Claims (1)

1. A photoacid generator, (B) a resin containing a repeating unit having an alicyclic acid-decomposable group, and (C)
A positive resist composition containing an alcohol compound having an aliphatic cyclic hydrocarbon group having 7 to 15 carbon atoms and an alcoholic hydroxyl group.