JP2003255542A - Positive photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive composition excellent in suitability to a halftone phase shifting mask (side lobe light resistance) and improved in development defects. <P>SOLUTION: The positive photosensitive composition comprises (A) a sulfonium salt having a substituent which generates an acid upon irradiation with an actinic ray or a radiation, (B) a resin whose solubility in a specified alkali developer increases and (C) a mixed solvent comprising at least one selected from the following group A of solvents and at least one selected from the following group B of solvents or a mixed solvent comprising at least one selected from the group A of solvents and at least one selected from the following group C of solvents; group A: propylene glycol monoalkyl ether alkoxylates, group B: propylene glycol monoalkyl ethers, alkyl lactates and alkyl alkoxypropionates, group C: γ-butyrolactone, ethylene carbonate and propylene carbonate. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a semiconductor device such as an IC.
Manufacturing process, manufacture of liquid crystal, thermal head and other circuit boards
Used in other photofabrication processes.
The present invention relates to a positive photosensitive composition. [0002] BACKGROUND OF THE INVENTION A positive photoresist is a semi-conductive film.
Conductor wafer, glass, ceramics or metal
0.5 on the substrate by spin coating or roller coating
It is applied to a thickness of ~ 2 μm. Then heat, dry,
Circuit patterns etc. are exposed to UV radiation etc. through an exposure mask.
Baking, developing after exposure bake if necessary
Thus, a positive image is formed. Furthermore, this positive image is masked.
As a pattern on the substrate by etching as
Can be processed. Typical applications include IC
Semiconductor manufacturing processes such as liquid crystal, thermal head, etc.
Plate manufacturing, other photofabrication processes, etc.
is there. Conventionally, the resolution is improved and the pattern shape is good.
To obtain image reproduction, it has high contrast (γ value)
The use of resists that are advantageous and meet these objectives
Technical development of resist compositions has been carried out. Such technology
There are numerous publications that disclose. Especially positive type
As for the resin that is the main part of
Many features with respect to polymer composition, molecular weight distribution, synthesis methods, etc.
Permit applications have been filed and have achieved certain results. Ma
The photosensitive material, which is another major component, is also very expensive.
Disclosed are compounds with many structures that are effective for trusting
Has been. Positive photo using these technologies
If a resist is designed, a pattern with dimensions comparable to the wavelength of light
To develop ultra-high resolution resists that can resolve
It has become possible. However, integrated circuits are increasingly integrated.
In the manufacture of semiconductor substrates such as VLSI
Is an ultrafine pattern with a line width of 0.5 μm or less.
Turn processing is becoming necessary. On the other hand, exposure technology or mask technology, etc.
Various attempts to further improve resolution by using super-resolution technology
Attempts have been made. Light source surface and mask for super-resolution technology
Various super-resolution technologies have been studied for each of the plane, pupil plane, and image plane.
ing. On the light source side, a light source called the modified illumination method,
In other words, resolving power is improved by making the shape different from the conventional circular shape.
There is technology to try to improve. On the mask surface, phase shift
Control phase with mask, ie pass through mask
Give phase difference to light and make good use of its interference
A technique for obtaining high resolution is reported. (For example,
Tokuhisa Ito: Stepper optics (1) to (4), optical technology
Nact, Vol.27, No.12,762 (1988), Vol.28, No.1,59 (199
0), Vol. 28, No. 2, 108 (1990), Vol, 28, No. 3, 165 (1990),
JP 58-173744, JP 62-50811, JP 62-67514, JP 1-14
(Disclosed in 7458, 1-283925, 2-213451, etc.) It is also described in Japanese Patent Application Laid-Open No. 8-15851.
In addition, registration using a halftone phase shift mask
The strike exposure method uses the aerial image and contrast of the projected image.
Although it is attracting particular attention as a practical technology to improve,
The light intensity distribution of the exposure light reaching the resist has a main peak
In addition to so-called sub-peaks (sidelobe light)
And even the part of the resist that should not be exposed
In particular, the higher the degree of coherence (σ), the more
The peak is larger. Such sub-peaks occur
In a positive resist, the resist after exposure and development
Unevenness due to sub-peaks is formed on the
Yes. Thus, a projection optical system for optical lithography.
Has been devised for various miniaturization and various super solutions.
The combination of image technology is also being studied extensively.
(For example, halftone phase shift mask and annular illumination:
C.N.Ahnetal; SPIE, Vol. 2440, 222 (1995), T. Ogawa et
al; SPIE, Vol. 2726, 34 (1996). However, when the above super-resolution technique is applied,
In the case of conventional positive photoresist, the resolution is degraded.
Exposure margin and exposure latitude were insufficient.
As a result, unevenness (film loss) occurs, and the resist performance deteriorates.
Cases have been reported so far. example
For example, C.L.Lin et al.
Have reported that the density dependence of patterns deteriorates due to sound.
(SPIE, vol. 2726, 437 (1996)), N. Samarakone et al.
And I.B.Hur et al. Used a halftone phase shift mask.
When forming a large contact hole pattern,
The periphery of the hole pattern is uneven due to the influence of the robe light.
(SPIE, Vol. 2440, 61
(1995), SPIE, Vol. 2440,278 (1995)). Side robe
To reduce the effects of light, the positive resist is removed after exposure.
Although the device such as surface treatment with Lucari has been made (T.Y
asuzato etal; SPIE, Vol.2440,804 (1995))
There is a problem such as becoming miscellaneous. JP-A-11-109632 discloses a pole.
Release resin containing functional group-containing alicyclic functional group and acid-decomposable group.
It is described that it is used for a ray-sensitive material. Japanese Patent Laid-Open No. 9-73173 and Japanese Patent Laid-Open No. 9-73173
Japanese Patent Laid-Open No. 9-90637 and Japanese Patent Laid-Open No. 10-161313
The gazette states that alkalis protected with structures containing alicyclic groups are acceptable.
The soluble group and its alkali-soluble group are eliminated by acid,
Acid sensitization with structural units that make them alkali-soluble
A resist material using a compound is described. JP 1
No. 0-130340 discloses a norbornene structure as a main chain.
A terpolymer having a specific repeating structural unit
Chemically amplified resists containing benzene are disclosed. Japanese Patent No. 3042618 discloses a lactone structure.
(Meth) acrylate derivatives with other structures are made polymerizable
Photoresist containing a polymer obtained by copolymerization with a compound
A dyst composition is described. In Japanese Patent Laid-Open No. 2001-81139, the main chain
Repeat with specific oxygen-containing alicyclic structure such as lactone skeleton
Dry etching by using resin containing unit
Improvements in resistance have been proposed. JP 11-30544 A
No. 4 includes a repeating structure having an adamantane structure in the side chain.
Structure unit and maleic anhydride as repeating structural units
A resin is disclosed. JP2001-1368
No. 8 is transparency, dry etching resistance, sensitivity, resolution,
Radiation-sensitive resin composition with excellent pattern shape and storage stability
For the purpose of providing products, the main chain has a norbornene structure.
Repeating unit having structure, having maleic anhydride structure
Repeating units, including repeating units having a hydroxyl group in the side chain
The composition containing the resin which has is proposed. JP 20
In 01-209181, norbornene is also present in the main chain.
Repeating unit with structure, maleic anhydride structure
A composition containing a resin containing a repeating unit is proposed
Has been. JP 2001-200016 discloses a lower film.
Improves adhesion to quality and dry etch resistance
For the purpose of alkyl vinyl ether monomers and
A composition containing a copolymer of maleic anhydride is described.
The In Japanese Patent Laid-Open No. 11-38628, sensitivity and pattern profile are described.
For the purpose of improving profile and substrate adhesion.
Contains a copolymer of nyl ether and maleate
A composition is described. However, these conventional resist materials
Even if you use a halftone phase shift mask,
Sidelobe light when forming a contact hole pattern
Insufficient resistance to development and development defects
There was a title. [0015] Accordingly, it is an object of the present invention.
Uses far ultraviolet light, especially ArF excimer laser light
To improve the performance of micro photofabrication
The halftone phase difference
Excellent shift mask suitability (sidelobe light resistance), development
Positive photosensitive compositions improved in terms of defects, these properties
Good profile with no pattern collapse
It is an object of the present invention to provide a positive photosensitive composition which forms [0016] [Means for Solving the Problems] The above problems are solved by the following structure.
This was achieved with a positive photosensitive composition. (1) (A) Activity represented by the general formula (SI)
A compound that generates acid upon irradiation with actinic rays or radiation, and
And (B) the repeating unit represented by formula (I) and one
It has a repeating unit represented by the general formula (II) and acts as an acid.
Which increases the solubility in alkaline developer
A resin, and (C) at least selected from the following solvent group A
And at least one selected from the following solvent B group
Less than selected from mixed solvent or solvent A group
And at least one selected from the following solvent C group
And a mixed solvent containing
Type photosensitive composition. Group A: Propylene glycol monoalkyl ether al
Coxilate Group B: propylene glycol monoalkyl ether, milk
Alkyl acids and alkoxypropionates Group C: γ-butyrolactone, ethylene carbonate, and
Propylene carbonate [0018] [Chemical 3] [0019] [Formula 4] In the general formula (SI), Rs_Four~ Rs₆Each
Independently, alkyl group, cycloalkyl group, alkoxy
Group, alkoxycarbonyl group, acyl group, acyloxy group
Group, nitro group, halogen atom, hydroxyl group, or carboxy
Represents a ru group. l: 1-5 m: 0 to 5 n represents 0-5. When l + m + n = 1, Rs_FourIs an alkyl group, cycloal
Kill group, alkoxy group, alkoxycarbonyl group,
Represents an alkyl group or an acyloxy group. Xs^-: R-SO_Three ^-, R: represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In general formula (I), R_1aHas a hydrogen atom or substituent
Represents an optionally substituted hydrocarbon group, R_2aHas a substituent
Represents a hydrocarbon group that may be present. R_1aAnd R _2aAnd each other
May be combined to form a ring. In general formula (II)
Z is —O— or —N (R_3a)-. here
R _3aIs a hydrogen atom, hydroxyl group, alkyl group, haloalkyl
Group or -OSO₂-R_4aRepresents. Also R_4aIs an alkyl
Group, haloalkyl group, cycloalkyl group or camphor residue
Represent. (2) Good profile without pattern collapse
In order to make the formation of the foil more reliable, (D)
Contains nitrogen-based and / or silicon-based surfactants
The positive photosensitive composition as described in (1) above,
Can be mentioned. Further, as a more preferred embodiment, the following configuration is used.
Can be mentioned. (3) The acid-decomposable resin is represented by the general formula (pI) to
Having a group that is decomposed by the action of an acid represented by (pV)
The above (1) or characterized in that it contains a repeating unit.
Is a positive photosensitive composition as described in (2). [0024] [Chemical formula 5] 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. (4) The resin (B) is further a lactone residue or
Containing a repeating unit having an alicyclic lactone residue
The positive photosensitive property as described in (1) to (3) above,
Composition. (5) In the above structure, a mixed solvent
(C) is at least one selected from solvent A group,
Or at least one selected from agent B group and solvent C group
Mixed solvent containing at least one selected from
Any one of (1) to (4) above,
Composition. [0028] DESCRIPTION OF THE PREFERRED EMBODIMENTS [1] (A) Actinic rays or radiation
Compounds that generate acid upon irradiation The composition of the present invention is represented by the general formula (SI).
(A) Generation of acid upon irradiation with actinic rays or radiation
Contains compound (photoacid generator). In the general formula (SI), Rs_Four~ R
s₆As the alkyl group, a substituent which may have a substituent
Til, ethyl, propyl, n-butyl, isobut
Tyl group, sec-butyl group, t-butyl group, pentyl
Group, hexyl group, heptyl group, octyl group, t-amyl
Group, decanyl group, dodecanyl group, hexadecanyl group
Examples thereof include those having 1 to 25 carbon atoms. Cycloal
As the kill group, a cyclopropyl which may have a substituent.
Group, cyclopentyl group, cyclohexyl group, cyclohexane
Cutyl group, cyclododecanyl group, cyclohexadecanyl
Examples thereof include those having 3 to 25 carbon atoms such as groups. A
As the alkoxy group, methoxy which may have a substituent
Group, ethoxy group, propoxy group, isopropoxy group, n
-Butoxy group, isobutoxy group, sec-butoxy group
Or t-butoxy group, pentyloxy group, t-amylo
A xyl group, an n-hexyloxy group, an n-octyloxy group,
1 to 25 carbon atoms such as n-dodecanoxy group
Can be mentioned. The alkoxycarbonyl group includes a substituent.
Methoxycarbonyl group, ethoxycal
Bonyl group, propoxycarbonyl group, isopropoxyca
Rubonyl group, n-butoxycarbonyl group, isobutoxy
A carbonyl group, a sec-butoxycarbonyl group, or
t-Butoxycarbonyl group, pentyloxycarbonyl
Group, t-amyloxycarbonyl group, n-hexyloxyca
Rubonyl group, n-octyloxycarbonyl group, n-do
2 to 25 carbon atoms such as decanoxycarbonyl group
Can be mentioned. As an acyl group, it has a substituent.
May be formyl group, acetyl group, butyryl group,
Ryl group, hexanoyl group, octanoyl group, t-butyl
Carbon such as carbonyl group, t-amylcarbonyl group, etc.
The thing of several 1-25 is mentioned. As an acyloxy group
May have a substituent, an acetoxy group,
Xyl group, butyryloxy group, t-butyryloxy group, t
-Amylyloxy group, n-hexane carbonyloxy group,
n-octanecarbonyloxy group, n-dodecanecarboni
Roxy group, n-hexadecane carbonyloxy group, etc.
Examples thereof include those having 2 to 25 carbon atoms. Halogen field
As a child, fluorine atom, chlorine atom, bromine atom or
Mention may be made of iodine atoms. Preferred as a substituent for these groups
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. Ma
When l + m + n = 1, Rs_FourHas a substituent
May be an alkyl group or an optionally substituted cycloa
Alkyl group, optionally substituted alkoxy group,
Optionally substituted alkoxycarbonyl group, substituted
An acyl group which may have a group, or a substituent.
Represents a good acyloxy group. In this case, Rs_FourIs
2 or more carbon atoms are preferred, more preferably 4 carbon atoms
That's it. Among the above, Rs_Four ~ Rs₆A substituent of
Examples of the alkyl group that may be contained include a methyl group and an alkyl group.
Til, propyl, isopropyl, butyl, t-
Butyl group, n-pentyl group, t-amyl group, n-hexyl
Group, n-octyl group and decanyl group are preferred.
As the alkyl group, a cycloalkyl group which may have a substituent.
Xyl, cyclooctyl and cyclododecanyl groups are preferred.
Preferably, the alkoxy group may have a substituent.
Methoxy group, ethoxy group, isopropoxy group, n-
Butoxy group, sec-butoxy group, t-butoxy group,
N-tyloxy group, t-amyloxy group, n-hexyloxy group
Group, n-octyloxy group and n-dodecanoxy group are preferred.
Preferably, the alkoxycarbonyl group has a substituent.
Methoxycarbonyl group, ethoxycarbonyl
Group, isopropoxycarbonyl group, n-butoxycar
Bonyl group, sec-butoxycarbonyl group, t-butoxy
Sicarbonyl group, pentyloxycarbonyl group, t-a
Myloxycarbonyl group, n-hexyloxycarbonyl
Group, n-octyloxycarbonyl group, n-dodecano
A xycarbonyl group is preferred, and the acyl group is substituted
May have a group, formyl group, acetyl group, butyryl
Group, valeryl group, hexanoyl group, octanoyl group, t
-Butylcarbonyl group, t-amylcarbonyl group are preferred
In addition, the acyloxy group may have a substituent,
An acetoxy group, an ethylyloxy group, a butyryloxy group,
t-butyryloxy group, t-amylyloxy group, n-he
Xantylcarbonyloxy group, n-octanecarbonyloxy
Groups are preferred. Of the above substituents, more preferred R
s_Four~ Rs₆Specific examples of methyl group, ethyl group,
Propyl, isopropyl, n-butyl, t-butyl
Group, n-pentyl group, t-amyl group, n-hexyl group,
n-octyl group, cyclohexyl group, methoxy group, eth
Xoxy group, isopropoxy group, n-butoxy group, t-but
Xy group, pentyloxy group, t-amyloxy group, hex
Ruoxy group, n-octyloxy group, methoxycarboni
Group, ethoxycarbonyl group, n-butoxycarbonyl
Group, t-butoxycarbonyl group, t-amyloxycarbo
Nyl group, hexyloxycarbonyl group, n-octylo
Xoxycarbonyl group, formyl group, acetyl group, butyryl
Group, hexanoyl group, octanoyl group, t-butyl cal
Bonyl, t-amylcarbonyl, acetoxy,
Tyryloxy group, butyryloxy group, t-butyryloxy
Si group, t-amylyloxy group, n-hexane carbonillo
Xyl group, n-octane carbonyloxy group, hydroxyl group, chlorine
An atom, a bromine atom, and a nitro group are mentioned. These groups may have a substituent and are preferably
Preferred substituents include methoxy group, ethoxy group, t-
Butoxy group, chlorine atom, bromine atom, cyano group, hydroxyl group,
Methoxycarbonyl group, ethoxycarbonyl group, t-butyl
Toxylcarbonyl group, t-amyloxycarbonyl group
I can get lost. L, m, and n are each preferably 1 to 3
That's right. It is represented by the general formula (SI) used in the present invention.
The sulfonium compound is a counter anion, Xs^-When
And the specific structure R-SO as described above_Three ^-Sul with
Phonic acid is used. Preferred examples of the aliphatic hydrocarbon group for R include
Preferably it is a straight or branched alkane having 1 to 20 carbon atoms.
A kill group or a cyclic alkyl having a substituent
Also good. In addition, the aromatic group as R is preferably
Is an aromatic group having 6 to 14 carbon atoms and has a substituent.
May be. The alkyl group for R has a substituent.
Methyl group, ethyl group, propyl group, n-but
Til, n-pentyl, n-hexyl, n-octyl
Group, 2-ethylhexyl group, decyl group, dodecyl group, etc.
And the cyclic alkyl group has a substituent.
Cyclopentyl group, cyclohexyl group, cyclo
Octyl group, cyclododecyl group, adamantyl group, nor
Bornyl, camphor, tricyclodecanyl, menthyl
Groups and the like. As an aromatic group, a substituent
Which may have a phenyl group, naphthyl group, etc.
You can. Preferred substituents are those having 1 to 15 carbon atoms.
Alkyl group, alkoxy group, alkoxycarbonyl
Groups, halogen atoms, etc., specifically, methyl
Group, t-butyl group, methoxy group, ethoxy group, t-butoxy
Si group, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxy
Sicarbonyl group, ethoxycarbonyl group, t-butoxy
A carbonyl group, a t-amyloxycarbonyl group, etc.
It is. As R, specifically, methyl group, tri
Fluoromethyl group, ethyl group, pentafluoroethyl
Group, 2,2,2-trifluoroethyl group, n-propyl
Group, n-butyl group, nonafluorobutyl group, n-penty
Group, n-hexyl group, n-octyl group, heptadecuff
Urooctyl group, 2-ethylhexyl group, decyl group,
Dodecyl group, cyclopentyl group, cyclohexyl group, 樟
Brain group, phenyl group, naphthyl group, pentafluoropheny
Group, p-toluyl group, p-fluorophenyl group, p-
Chlorophenyl group, p-hydroxyphenyl group, p-meth
Xylphenyl, dodecylphenyl, mesityl,
Riisopropylphenyl group, 4-hydroxy-1-naphth
List til, 6-hydroxy-2-naphthyl, etc.
You can. As a more preferred specific example of R, methyl
Group, trifluoromethyl group, ethyl group, pentafluoro
Ethyl group, 2,2,2-trifluoroethyl group, n-butyl
Til group, nonafluorobutyl group, n-hexyl group, n-
Octyl group, heptadecafluorooctyl group, 2-ethyl
Ruhexyl group, camphor group, phenyl group, naphthyl group, pen
Tafluorophenyl group, p-toluyl group, p-fluoro
Phenyl group, p-chlorophenyl group, p-methoxyphene
Nyl, dodecylphenyl, mesityl, triisopropyl
Propylphenyl group, 4-hydroxy-1-naphthyl group,
A 6-hydroxy-2-naphthyl group may be mentioned. The total number of carbon atoms of the acid generated is 1-30.
Is preferred. More preferably, it is 1-28, and even more preferable
The number is preferably 1 to 25. Its total carbon number is less than 1
In case of t-top shape, there is a hindrance to pattern formation.
If it exceeds 30, development residue will be generated.
It is not preferable, for example. The general formula (S
Specific examples of the compound represented by I) are shown below.
However, it is not limited to this. These compounds are
It is used alone or in combination of two or more. [0039] [Chemical 6] [0040] [Chemical 7][0041] [Chemical 8][0042] [Chemical 9][0043] Embedded image[0044] Embedded imageAddition of a photoacid generator represented by the general formula (SI)
The added amount is usually 0.00 based on the solid content in the composition.
It is used in the range of 1 to 20% by weight, preferably 0.01
-15% by weight, more preferably 0.1-10% by weight.
Used in enclosures. Addition amount of photoacid generator is 0.001
If the amount is less than%, the sensitivity is low and pattern formation is difficult
Tend to be. Also, the added amount is more than 20% by weight
And resist light absorption becomes too high, resulting in poor profile
Or process (especially bake) margin, exposure mark
Gin tends to narrow. The compound represented by the general formula (SI) is, for example,
For example, arylglycol such as arylmagnesium bromide
Nyar reagent and substituted or unsubstituted phenyl sulfoxide
And the resulting triarylsulfonium halai
Can be synthesized by the method of salt exchange with the corresponding sulfonic acid.
The In addition, substituted or unsubstituted phenyl sulfoxide
The corresponding aromatic compound is methanesulfonic acid / diphosphorus pentoxide
Alternatively, condensation using an acid catalyst such as aluminum chloride,
Salt exchange method, diaryliodonium salt and diary
Condensation and salt exchange of sulfides using catalysts such as copper acetate
It can be synthesized by the method to do. Salt exchange once
After introducing the halide salt, use a silver reagent such as silver oxide.
How to convert to sulfonate or ion exchange resin
It can also be used for salt exchange. Also used in salt exchange
Use commercially available sulfonic acid or sulfonate.
Or hydrolysis of commercially available sulfonic acid halides, etc.
Can be obtained by: [2] Photoacid generator that may be used in combination Examples of the photoacid generator that may be used in the present invention include
Photo-initiator, photo-radio for photocationic polymerization other than specified
Photopolymerization photoinitiator, pigment photodecolorant, photochromic agent
Or well-known light (4
Ultraviolet rays of 00 to 200 nm, far ultraviolet rays, particularly preferred
Is g-line, h-line, i-line, KrF excimer laser light),
ArF excimer laser light, electron beam, X-ray, molecular beam or
Compounds that generate acid by ion beam and their mixtures
Compound etc. are mentioned. Addition of photoacid generator that may be used in combination
The amount is relative to the photoacid generator represented by the general formula (SI).
1000% by weight or less, preferably 700% by weight
Or less, more preferably 500% by weight or less.
For example, diazonium salt, ammonium salt, phosphoniu
Salt, iodonium salt, sulfonium salt, selenonium
Salts, onium salts such as arsonium salts, organic halogen compounds
, Organometallic / organic halide, o-nitrobenzyl
For photoacid generators and imide sulfonates with type protecting groups
A compound that generates sulfonic acid upon photolysis
Sulfone compounds, diazoketosulfone, diazodisulfone
And the like. Also in these lights
More acid-generating groups or compounds can be attached to the main chain of the polymer.
Alternatively, a compound introduced into the side chain can be used. 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
Light described in Patent 3,779,778, European Patent 126,712, etc.
A compound capable of generating an acid can also be used. Of the above-mentioned compounds that generate acids, they are effectively combined.
What is used is described below. As the photoacid generator used in combination, actinic rays or
Phenacyl sulfone that generates acid when irradiated
Compounds having a nium salt structure and sulfur without an aromatic ring
A compound having a phonium salt structure is preferred. Acid is generated by irradiation with actinic rays or radiation.
A compound having a phenacylsulfonium salt structure
As a compound represented by the above general formula (A2I)
Can. [0052] Embedded image In the general formula (A2I), R_1c~ R
_5cEach independently represents a hydrogen atom, an alkyl group, or alkoxy.
Represents a group or a halogen atom. R_6cAnd R_7cEach
Standingly represents a hydrogen atom, an alkyl group, or an aryl group.
Rx and Ry each independently represents an alkyl group, 2-oxoa
Alkyl group, alkoxycarbonylmethyl group, allyl group,
Or represents a vinyl group. R_1c~ R_7cAny two or more
And Rx and Ry are bonded to form a ring structure.
This ring structure may be an oxygen atom, sulfur atom,
It may contain an alkyl bond or an amide bond. X^-Is Anio
Represents In the above general formula (A2I), R_1c~ R
_5cEach independently represents a hydrogen atom, an alkyl group, or alkoxy.
Represents a group or a halogen atom. R_6cAnd R_7cEach
Standingly represents a hydrogen atom, an alkyl group, or an aryl group.
Rx and Ry each independently represents an alkyl group, 2-oxoa
Alkyl group, alkoxycarbonylmethyl group, allyl group,
Or represents a vinyl group. R_1c~ R_7cAny two or more
And Rx and Ry combine to form a ring structure.
This ring structure may be an oxygen atom, sulfur atom,
It may contain an alkyl bond or an amide bond. X^-Anio
For example, sulfonic acid, carboxylic acid or
Mention may be made of an anion of sulfonylimide. R_1c~ R_5cThe alkyl group as is linear,
It may be either branched or cyclic, for example, having 1 to 1 carbon atoms
10 alkyl groups, preferably straight chain having 1 to 5 carbon atoms
Branched alkyl groups (eg, methyl, ethyl, straight chain)
Or branched propyl group, linear or branched butyl group, linear or
Branched pentyl group), C3-C8 cyclic alkyl group (example)
For example, cyclopentyl group, cyclohexyl group)
be able to. R_1c~ R_5cAs an alkoxy group
It may be any of chain, branched and cyclic, such as carbon number
1-10 alkoxy groups, preferably 1-5 carbon atoms
Linear and branched alkoxy groups (eg methoxy, eth
Xoxy group, straight chain or branched propoxy group, straight chain or branched but
Xy group, linear or branched pentoxy group), having 3 to 8 carbon atoms
Cyclic alkoxy group (for example, cyclopentyloxy group,
Cyclohexyloxy group). Like
Or R_1c~ R_5cAny of these are linear, branched, or cyclic
An alkyl group or a linear, branched, or cyclic alkoxy group,
More preferably R_1cTo R_5cThe sum of carbon numbers
is there. As a result, the solvent solubility is improved,
Particle generation is suppressed. R_6cAnd R_7cAs for alkyl group
Is R_1c~ R_5cThe same as the alkyl group as
Can be. As the aryl group, for example, the number of carbon atoms
List 6-14 aryl groups (eg, phenyl groups)
be able to. The alkyl group as Rx and Ry is R_1c
~ R_5cThe same as the alkyl group as
it can. 2-oxoalkyl group is R_1c~ R_5cAs
Mentioning a group having> C = O at the 2-position of the alkyl group
it can. Arco in an alkoxycarbonylmethyl group
For the xoxy group, R_1c~ R_5cAn alkoxy group as
The same can be mentioned. Rx and Ry combine
As the group formed by the above, butylene group, pentylene group, etc.
Can be mentioned. The compound of formula (A2I) forms a ring;
As a result, the three-dimensional structure is fixed and the optical resolution is improved. R_1c
~ R_7cWhen any two of them combine to form a ring structure
R_1c~ R_5cAny one and R_6cAnd R
_7cAny one of these bonds to form a single bond or a linking group
In the case of forming a ring, particularly R_5cAnd R_6cOr
R_7cCombine to form a single bond or linking group to form a ring
The case is preferred. As a linking group, it has a substituent.
May be an alkylene group or an alkenyl optionally having a substituent.
Nylene group, -O-, -S-, -CO-, -CONR-
(R is a hydrogen atom, an alkyl group or an acyl group), and
The group which combines these two or more
Furthermore, an alkylene group which may have a substituent,
Alkylene group containing oxygen atom, alkyle containing sulfur atom
Preferred is an aryl group. As the substituent, an alkyl group (preferably
Or an aryl group (preferably having 6 carbon atoms).
-10, for example phenyl group), acyl group (for example carbon
Mathematical formulas 2 to 11). In addition,
Group, ethylene group, propylene group, -CH₂-O-,-
CH₂A linking group that forms a 5- to 7-membered ring such as -S- is preferred.
Preferably, ethylene group, -CH₂-O-, -CH₂-S-
Particularly preferred is a linking group that forms a 6-membered ring. 6
By forming a member ring, the carbonyl plane and C-S +
Guma coupling becomes closer to vertical, and orbital interaction causes light
Resolution is improved. R_1c~ R_7cAnd Rx and Ry
Bonded at any position via a single bond or a linking group,
It may be a compound having two or more structures of the formula (A2I)
Yes. X^-Is preferably a sulfonate anion
More preferably, the 1-position is substituted by a fluorine atom
Alkanesulfonate anion or electron withdrawing group
Substituted benzene sulfonic acid. Alkanesulfo
The alkane part of the acid anion is an alkoxy group (for example,
Carbon number 1-8), perfluoroalkoxy group (for example, charcoal)
It may be substituted with a substituent such as a prime number of 1 to 8). Ma
Electron-withdrawing groups include chlorine, bromine, and nitrite.
B group, cyano group, alkoxycarbonyl group, acyloxy
Group, acyl group and the like. X^-Further
Preferably a perfluoroalkane sulfone having 1 to 8 carbon atoms
Acid anion, particularly preferably perfluorooctane
Sulfonate anion, most preferably perfluorobutane
Sulfonic acid anion, trifluoromethanesulfonic acid ani
Is on. Decomposing acid-decomposable groups by using these
Improved speed, better sensitivity, and control of acid diffusivity
And resolution is improved. The following is a list of frames that can be used in the present invention.
Specific examples of compounds having an enacilsulfonium salt structure
However, the present invention is not limited to these examples. [0059] Embedded image [0060] Embedded image [0061] Embedded image[0062] Embedded image[0063] Embedded image[0064] Embedded image[0065] Embedded image [0066] Embedded image [0067] Embedded image[0068] Embedded image Acid is generated by irradiation with actinic rays or radiation.
Having a sulfonium salt structure without an aromatic ring
As a compound, an alkyl represented by the following general formula (A2II)
And rusulfonium salt compounds. [0070] Embedded image In the general formula (A2II), R^1b~ R^3b
Each independently represents an alkyl group. The alkyl group is 2
Even a 2-oxoalkyl group having> C = O at the position
Good. R^1b~ R^3bAre two of them bonded to each other
A structure may be formed. X^-Represents an anion. In the above general formula (A2II), R^1b~
R^3bEach independently represents an alkyl group. Alkyl group
Is a 2-oxoalkyl group having> C═O at the 2-position
May be. R^1b~ R^3bAre two of them connected to each other
Thus, a ring structure may be formed. X^-Represents anions
The R^1b~ R^3bThe alkyl group as is linear, branched or ring
Any of the shape may be sufficient, Preferably, it is C1-C1.
0 linear or branched alkyl groups (eg methyl group, ethyl
Group, propyl group, butyl group, pentyl group), carbon number 3
To 10 cyclic alkyl groups (cyclopentyl group, cyclohexane
Xyl group, norbornyl group). R
^1b~ R^3bThe 2-oxoalkyl group as
It may be either a ring or a ring, preferably the above
Mentioning a group having> C = O at the 2-position of the alkyl group
it can. R^1b~ R^3bIs a halogen atom or an alkoxy group
(For example, carbon number 1-5), hydroxyl group, cyano group, nitro group
May further be substituted. R^1b~ R^3bOut of
Two may combine to form a ring structure, with oxygen atoms in the ring.
Child, sulfur atom, ester bond, amide bond, carbonyl
It may contain a group. R^1b~ R^3bTwo of the
Examples of the groups formed include alkylene groups (for example, butylene
Group and pentylene group). Photoreactive
From the viewpoint of R^1b~ R^3bAny one of the alkyls
Carbon-carbon double bond or carbon-oxygen double bond in the chain
A group having a bond may be present. X^-As anion of
Is for example a sulfonate anion, preferably in position 1
An alkanesulfonic acid substituted with a fluorine atom
Nione, benzenesulfonic acid substituted with electron withdrawing group
More preferably, it is a C1-C8 perfluororear
Lucan sulfonate anion, most preferably
Fluorobutane sulfonate anion, perfluorooctane
It is a sulfonate anion. By using these, acid
Degradable group decomposition rate is improved, sensitivity is excellent, and generated acid
Diffusivity is controlled and resolution is improved. Electron suction
Groups include chlorine, bromine, nitro, cyano
Group, alkoxycarbonyl group, acyloxy group, acyl group
Etc. Chemical formula represented by general formula (A2II)
Compound R^1b~ R^3bAt least one of the general formula (A2I
R of other compounds represented by I)^1b~ R^3bAt least one of
You may take the structure combined with one. The following is used in the present invention.
Of compounds having an alkylsulfonium salt structure that can be used
Preferred specific examples are shown, but the present invention is limited to these.
It is not a thing. [0073] Embedded image[0074] Embedded image [0075] Embedded imageAs the photoacid generator used in combination, the following
Iminosulfonate derivatives represented by the general formula (PAG6)
And diazodisulfo represented by the following general formula (PAG7)
Can be mentioned. [0077] Embedded image Where R²⁰⁶Is substituted or unsubstituted al
A kill group and an aryl group are shown. A is substituted or unsubstituted
An alkylene group, an alkenylene group, or an arylene group is shown.
Specific examples include the compounds shown below.
It is not limited to that. [0079] Embedded image [0080] Embedded image[0081] Embedded image[0082] Embedded image [0083] 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. [0085] Embedded image[0086] Embedded image [3] (B) Decomposed by the action of acid
Resin with increased solubility in potash developer The resin used in the present invention is a resin represented by the general formula (I).
Repeating unit and repeating unit represented by formula (II)
And decomposes by the action of an acid in an alkaline developer.
Resin with increased solubility (hereinafter abbreviated as “acid-decomposable resin”)
Is). [0088] Embedded image In the general formula (I), R_1aIs a hydrogen atom or
Represents a hydrocarbon group which may have a substituent, and R_2aIs
The hydrocarbon group which may have a substituent is represented. R_1a
And R _2aAnd may be bonded to each other to form a ring. R_1aThe hydrocarbon group as is preferably charcoal
Prime number 1-10, particularly preferably 1-5,
And an alkyl group (preferably a methyl group).
The R _1aIs preferably a hydrogen atom or a methyl group. R_2aThe hydrocarbon group as is preferably charcoal
Prime number 1-20, particularly preferably 1-10, for example
An alkyl group and a cycloalkyl group can be mentioned.
R_1aAnd R_2aThe hydrocarbon group as has a substituent
Also good. As for carbon number of a substituent, 1-30 are preferable. Substituent
For example, hydroxyl group, halogen atom, alkoxy
Group, acyl group, acylcarbonyl group, acyloxy group, etc.
Can be mentioned. Ring structures in these substituents
May contain heteroatoms, hydroxyl groups,
Kill group (preferably having 1 to 5 carbon atoms), alkoxy group (preferably
It may have a substituent such as 1 to 5 carbon atoms.
Yes. R_1aAnd R_2aAnd combine to form a ring
Examples of the ring include, for example, tetrahydrofuran ring, tetra
Examples thereof include 4- to 8-membered rings such as a hydropyran ring.
This ring structure may have a substituent as described above. In the following, the repetition represented by the general formula (I)
Specific examples of units are listed below, but are not limited to these.
Yes. [0094] Embedded image The acid-decomposable resin of the present invention further comprises the formula (II)
The repeating unit represented by these is contained. [0096] Embedded image In the general formula (II), Z represents -O- or
Is -N (R_3a)-. Where R _3aA hydrogen atom, water
Acid group, alkyl group, haloalkyl group or -OSO₂-R
_4aRepresents. Also R_4aIs an alkyl group, a haloalkyl group,
Represents a cycloalkyl group or a camphor residue. R above_3aAnd R_4aAs an alkyl group in
Is a straight or branched alkyl having 1 to 10 carbon atoms.
Group, more preferably a straight chain having 1 to 6 carbon atoms
Or a branched alkyl group, more preferably
Til, ethyl, propyl, isopropyl, n-
Butyl group, isobutyl group, sec-butyl group, t-butyl
Group. R above_3aAnd R_4aHaloalkyl groups in
As trifluoromethyl group, nanofluorobutyl
Group, pentadecafluorooctyl group, trichloromethyl
Groups and the like. R above_4aCycloa in
Examples of the alkyl group include a cyclopentyl group and a cyclohexyl group.
Group, cyclooctyl group and the like. R_3aAnd R_4aAs alkyl group, halo
Rukiru group, R_4aAs cycloalkyl group or camphor residue
May have a substituent. As such a substituent
Are, for example, hydroxyl, carboxyl, cyano, halo
Gen atom (for example, chlorine atom, bromine atom, fluorine source)
Child, iodine atom), an alkoxy group (preferably having a carbon number of 1
4, such as methoxy, ethoxy, propoxy,
Toxyl groups), acyl groups (preferably having 2 to 5 carbon atoms, eg
For example, formyl group, acetyl group, etc.), acyloxy group
(Preferably having 2 to 5 carbon atoms such as an acetoxy group), a
A reel group (preferably having 6 to 14 carbon atoms such as phenyl
Group) and the like. The repetition represented by the above general formula (II) is as follows.
Specific examples of repeating units are given, but are limited to these
is not. [0101] Embedded image [0102] Embedded image The acid-decomposable resin of the present invention is produced by the action of acid.
A group that decomposes and becomes alkali-soluble is represented by the above general formula.
You may have in the repeating unit of (I) or (II)
And may be contained in other repeating units. Acid production
As a group that decomposes by use, -COOA⁰ , -OB
⁰ The group shown by group can be mentioned. Furthermore, these
As a group to be included, -R⁰ -COOA⁰ Or -A_r -O
-B⁰ The group shown by these is mentioned. Where A⁰ Is -C
(R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹) (R⁰²)
(R ⁰³), -C (R⁰⁴) (R⁰⁵) -O-R⁰⁶Group or
Indicates a lactone group. B⁰ Is -A⁰ Or -CO-O-A
⁰ Indicates a group. R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵It
Each may be the same or different, hydrogen atom, alkyl
Groups, cycloalkyl groups, alkenyl groups, aralkyl groups
Or an aryl group, R⁰⁶Is an alkyl group, cyclic al
A kill group or an aryl group is shown. However, R⁰¹~ R⁰³of
At least two of them are groups other than hydrogen atoms, and R ⁰¹
~ R⁰³And R⁰⁴~ R⁰⁶Two groups of
It may be formed. R⁰Has a single bond or a substituent
Divalent or higher aliphatic or aromatic hydrocarbons
-Ar- has a monocyclic or polycyclic substituent
The aromatic group more than bivalence which may be present is shown. Here, examples of the alkyl group include a methyl group and an alkyl group.
Til, propyl, n-butyl, sec-butyl
Group having 1 to 4 carbon atoms such as t-butyl group is preferred.
Cycloalkyl groups include cyclopropyl and cyclyl groups.
Such as butyl, cyclohexyl, and adamantyl groups
Those having 3 to 30 carbon atoms are preferred,
Of vinyl, propenyl, allyl, and butenyl groups
Are preferably those having 2 to 4 carbon atoms such as aryl groups.
Are phenyl, xylyl, toluyl, cumenyl
Group having 6 to 1 carbon atoms such as naphthyl group and anthracenyl group
Four are preferred. As the cyclic alkyl group,
Examples thereof include those having 3 to 30 primes, specifically cyclo
Propyl, cyclopentyl, cyclohexyl, a
Damantyl group, norbornyl group, boronyl group, tricycle
Rodecanyl group, dicyclopentenyl group, nobornane epoxy
Xyl group, menthyl group, isomenthyl group, neomenthyl group
Group, tetracyclododecanyl group, steroid residue, etc.
I can make it. The aralkyl group has 7 to 7 carbon atoms.
There are 20 examples, which may have a substituent.
Examples include a benzyl group, a phenethyl group, and a cumyl group. In addition, examples of the substituent include a hydroxyl group and a halogen atom.
Child (fluorine, chlorine, bromine, iodine), nitro group, cyano
Group, the above alkyl group, methoxy group, ethoxy group, hydride
Roxyethoxy group, propoxy group, hydroxypropoxy
Si group, n-butoxy group, isobutoxy group, sec-but
Alkoxy groups such as xy group and t-butoxy group, methoxy group
Alkoxycals such as rubonyl and ethoxycarbonyl groups
Bonyl, benzyl, phenethyl, cumyl, etc.
Aralkyl group, Aralkyloxy group, Formyl group, Acetyl
Ru group, butyryl group, benzoyl group, cyanamyl group, barre
Acyloxy such as acyl group such as ryl group and butyryloxy group
Group, the above-mentioned alkenyl group, vinyloxy group / propenyl
Al, such as oxy group, allyloxy group, butenyloxy group
Such as kenyloxy group, the above aryl group, phenoxy group, etc.
Aryloxy groups such as aryloxy groups and benzoyloxy groups
Mention may be made of the xylcarbonyl group. In addition, the above
Examples of the kuton group include the following structures. [0106] Embedded image In the above formula, R^a, R^b, R^cAre each independently
A hydrogen atom and an alkyl group having 1 to 4 carbon atoms are represented. n is
Represents an integer from 2 to 4. ArF excimer laser as a light source for exposure
When using-, it is a group that decomposes under the action of an acid.
-C (= O) -X₁-R₀Using a group represented by
Is preferred. Where R₀ As t-butyl group, t
-Tertiary alkyl group such as amyl group, isobornyl group, 1-
Ethoxyethyl group, 1-butoxyethyl group, 1-isobutyl
Toxiethyl group, 1-cyclohexyloxyethyl group, etc.
1-alkoxyethyl group, 1-methoxymethyl group, 1-
Alkoxymethyl group such as ethoxymethyl group, tetrahydride
Ropyranyl group, tetrahydrofuranyl group, trialkyl
Silyl group, 3-oxocyclohexyl group, the above lactone
Groups and the like. X₁Is oxygen atom, sulfur source
Represents a child, preferably an oxygen atom. In particular, from general formula (pI) to general formula (pV)
Containing a repeating unit having an acid-decomposable group represented by
It is preferable to have. Contain these repeating units.
Improves image formation and dry etching resistance.
The Embedded imageIn the formula, 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 above general formula (pI) to general formula (pV)
And the linking group of A is an alkylene group or a substituted alkylene group.
Group, ether group, thioether group, carbonyl group,
Tell group, amide group, sulfonamide group, urethane group,
Or a single group selected from the group consisting of urea groups, or 2
Represents a combination of two or more groups. Alky in A above
Examples of the len group include groups represented by the following formulas.
Yes. -[C (R_b ) (R_c )]_r -Where R_b , R_c
Is a hydrogen atom, alkyl group, substituted alkyl group, halogen
Represents an atom, hydroxyl group, or alkoxy group.
It may be. 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,
It is selected from a til group, a propyl group, and an isopropyl group.
Examples of the substituent of the substituted alkyl group include a hydroxyl group and a halogen atom.
Child, alkoxy group (preferably having 1 to 4 carbon atoms)
be able to. Alkoxy groups include methoxy and eth
1 to 4 carbon atoms such as toxi group, propoxy group, butoxy group
Individuals can be mentioned. As a halogen atom
Includes chlorine, bromine, fluorine, iodine, etc.
I can make it. r represents an integer of 1 to 10. 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. [0114] Embedded image[0115] Embedded image[0116] 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 substituents for 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,
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 the following, the general formulas (pI) to (pV)
Corresponds to a repeating unit having a group represented by
Specific examples of the monomer will be shown. [0120] Embedded image[0121] Embedded image[0122] Embedded image[0123] Embedded image[0124] Embedded image [0125] Embedded imageAlso, contact hole resolution, default
It has lactone residues to improve the rust
It is preferable that the repeating unit contains
Reducing the number of repeating units having an alicyclic lactone residue.
It is preferable to contain a position. Alicyclic lactone is cyclic
A structure in which a hydrocarbon group and a lactone ring are condensed, or many
Cyclic hydrocarbon group (combination of two or more cycloalkane rings)
A cycloalkane ring of a ringed cyclic hydrocarbon ring)
Means a structure in which one is substituted with a lactone ring. Lactone
Residues include butyrolactone (a1) and alicyclic lactone
(A2) norbornane lactone, (a3)
Chrohexanelactone and (a4) adamantanelac
Tons. A repeating unit having a lactone residue (a
As 1), the repetition represented by the following general formula (BL)
Units can be mentioned. [0128] Embedded image In the general formula (BL), R₁Is a hydrogen atom or
Represents a methyl group. W is a single bond, alkylene group, ether
Group, thioether group, carbonyl group, ester group
A single group or a group of two or more groups selected from the group consisting of
Represents a combination. Ra, Rb, Rc, Rd, Re are each independently
Standingly represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represents an integer of 0 to 3, and m + n is 2
It is 6 or less. In the general formula (BL), Ra to Re charcoal
As the alkyl group having 1 to 4 primes, methyl group, ethyl
Group, propyl group, isopropyl group, n-butyl group, iso
List butyl group, sec-butyl group, t-butyl group, etc.
be able to. The alkylene group for W is represented by the following formula:
Can be mentioned. -[C (Rf) (R
g)] r- In the above formula, Rf and Rg are a hydrogen atom, an alkyl,
Group, substituted alkyl group, halogen atom, hydroxyl group, alcohol
Represents a xoxy group, and they may be the same or different. A
As the alkyl group, a methyl group, an ethyl group, a propyl group,
Lower alkyl groups such as isopropyl and butyl are preferred
More preferably, a methyl group, an ethyl group, a propyl group,
Selected from the isopropyl group. Substitution of substituted alkyl group
Examples of the group include a hydroxyl group, a halogen atom, and an alkoxy group.
I can make it. As an alkoxy group, methoxy
Group, ethoxy group, propoxy group, butoxy group, etc.
1-4 may be mentioned. As halogen atoms
The chlorine atom, bromine atom, fluorine atom, iodine atom, etc.
Can be mentioned. r is an integer of 1-10. 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 (BL)
Specific examples of the monomer corresponding to the unit are shown below.
It is not specified. [0133] Embedded image[0134] Embedded image[0135] Embedded imageIn the acid-decomposable resin of the present invention, the nor of (a2)
Borane lactone monomers and (a3) cyclohex
As the sun lactone monomers, the above general formulas (V
-1) to (V-2) and (V-3) to (V-4)
A repeating unit having a group is preferred. Repeats having norbornane lactone (a2)
As the repeating unit, the following general formula (V-1) or (V-
Mentioning a repeating unit having a group represented by 2)
it can. [0138] Embedded image In the general formulas (V-1) to (V-2),
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. As cyclohexanelactone (a3)
Is a group represented by the following general formula (V-3) or (V-4)
The repeating unit which has can be mentioned. [0141] Embedded image In the general formulas (V-3) 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. In addition, 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. [0147] 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. [0149] 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. [0152] Embedded image [0153] Embedded image[0154] Embedded image[0155] Embedded image[0156] Embedded image[0157] Embedded image[0158] Embedded imageAs adamantane lactone (a4),
The repeating unit represented by the following general formula (AL) is preferred.
Yes. [0160] Embedded image In the general formula (AL), A is a single bond,
Alkylene group, cycloalkylene group, ether group, thioe
Selected from the group consisting of ether, carbonyl and ester groups
A single or combination of two or more groups selected
The R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, cyano
Represents a group or a halogen atom. In general formula (AL), alkylene of A
Examples of the group include a group represented by the following formula.
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 (AL), the cycloalkyl of A
Examples of the xylene group include those having 3 to 10 carbon atoms.
Cyclopentylene group, cyclohexylene group, cyclo
Examples include an octylene group. The bridged alicyclic ring containing Z has a substituent.
It may be. 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
IL 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 general formula (AL), bonded to A
The oxygen atom of the ester group is a bridged alicyclic ring containing Z
Bonded at any position of the carbon atoms constituting the ring structure
Also good. The repeating unit represented by the general formula (AL) is shown below.
Specific examples are not limited to these.
Yes. [0165] Embedded image [0166] Embedded imageIn addition, the acid-decomposable resin of the present invention particularly has
It is represented by the following general formula (III) for improving the giraffe
It is also preferable to contain a repeating unit. [0168] Embedded image In the general formula (III), 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. Also, a hole pattern by underexposure
The general formula (I
In the repeating unit represented by II), R₃₁~ R₃₃No
More preferably, the two are hydroxyl groups. Specific examples are given below, but the present invention is not limited to these.
It is not something. [0172] Embedded imageFurthermore, especially heat resistance and etching resistance are improved.
In order to make the repeating unit represented by the general formula (IV)
It is preferable to contain. [0174] Embedded image In the general formula (IV): R₁~ R_FourAre independent
A hydrogen atom, a halogen atom, a cyano group, -COOH,
Optionally substituted hydrocarbon group, -COOR_Five,
-C (= O) -X-A-R₆Or by the action of acid
R, and R₁~ R_FourAt least two of them
To form a ring. Where R_FiveHas a substituent
Represents an optionally hydrocarbon group or lactone residue. R₆
Is a hydrogen atom, -COOH, -COOR_Five, -CN, water
Acid group, alkoxy group optionally having substituent, substituent
The hydrocarbon group or lactone residue which may have
The X is an oxygen atom, a sulfur atom, -NHSO₂-Or
-NHSO₂NH- is represented. A is a single bond, alkylene
Group, cycloalkylene group, ether group, thioether
Group, carbonyl group, ester group, sulfonamide group, and
And an N-sulfonylamide group
It represents a single group or a combination of two or more groups. n is 0 or
Represents 1. As a structure of a group that decomposes by the action of an acid
Is -C (= O) -X₁-R_p It is represented by Where R_p
As a tertiary alkyl such as t-butyl group, t-amyl group, etc.
Group, isobornyl group, 1-ethoxyethyl group, 1-butyl group
Toxiethyl group, 1-isobutoxyethyl group, 1-cycl
1-alkoxyethyl groups such as a rohexyloxyethyl group,
Al, such as 1-methoxymethyl group and 1-ethoxymethyl group
Coximethyl group, 3-oxoalkyl group, tetrahydro
Pyranyl group, tetrahydrofuranyl group, trialkyl group
Ryl ester group, 3-oxocyclohexyl ester
Group, 2-methyl-2-adamantyl group, mevalonic group
Kuton residue, 2- (γ-butyrolactonyloxycarbo
Nyl) -2-propyl group and the like. X₁
Is an oxygen atom, a sulfur atom, -NH-, -NHSO₂ -Also
Is -NHSO₂ NH- is represented. R above₁~ R_FourAs a halogen atom in
Includes chlorine, bromine, fluorine, iodine, etc.
I can make it. R above₁~ R_Four, R_Five, R₆Charcoal in
The hydride group is preferably a linear, branched or cyclic alkyl group.
And rubridged hydrocarbon groups. Linear
Or as a branched alkyl group, it is C1-C10.
Are preferably linear or branched alkyl groups, more preferably
Preferably, it is a linear or branched alkyl having 1 to 6 carbon atoms.
More preferably a methyl group, an ethyl group, a pro
Pill group, isopropyl group, n-butyl group, isobutyl
Group, sec-butyl group and t-butyl group. Annular al
Examples of the kill group and the bridged hydrocarbon group include cyclopropyl
Pyr group, cyclopentyl group, cyclohexyl group, adam
Nyl group, 2-methyl-2-adamantyl group, norbol
Nyl group, boronyl group, isobornyl group, tricyclodeca
Nyl group, dicyclopentenyl group, nobornane epoxy
Group, menthyl group, isomenthyl group, neomenthyl group, te
A tracyclododecanyl group etc. can be mentioned. The above R₁~ R_FourAt least two of them are combined
Examples of the ring formed in this way include, for example, a lactone ring, cyclo
Pentene, cyclohexene, cycloheptane, cycloo
C5-C12 rings, such as a kutan, are mentioned. R above₆
The alkoxy group in is preferably methoxy
Group, ethoxy group, propoxy group, butoxy group, etc.
One to four can be mentioned. The above hydrocarbon
Group, alkoxy group may further have a substituent,
Examples of the substituent include a hydroxyl group, a carboxyl group, and a shear group.
Group, halogen atom (eg chlorine atom, bromine atom, fluorine atom)
Element, iodine, etc.), alkoxy group (preferably carbon
1 to 4, for example, methoxy group, ethoxy group, propoxy
Si group, butoxy group, etc.), acyl group (for example, formyl group,
Acetyl group etc.), acyloxy group (eg acetoxy group)
Etc.). As the alkylene group in A above,
A group represented by the formula can be given. -[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. R_FiveAnd R₆As a lactone residue as
Is, for example, the following -Y
it can. The -Y group; [0181] Embedded image In the above -Y group, R_{twenty one}~ R₃₀Each
Independently, it represents a hydrogen atom or an alkyl group. a and b are 1
Or 2 is represented. R above_{twenty one}~ R₃₀As an alkyl group in
For example, methyl group, ethyl group, propyl group, isop
A propyl group, a butyl group, etc. can be mentioned. R_{twenty one}~ R
₃₀The alkyl group as may have a substituent. This
As the substituent of, for example, a hydroxyl group, a carboxyl group,
Cyano group, halogen atom (eg chlorine atom, bromine atom)
Child, fluorine atom, iodine atom), alkoxy group (preferred
Or 1 to 4 carbon atoms such as methoxy, ethoxy,
Roxy group, butoxy group, etc.), acyl group (preferably charcoal)
Prime number 2 to 5, such as formyl group, acetyl group, etc.), a
A siloxy group (preferably having 2 to 5 carbon atoms such as aceto
Xyl group), aryl group (preferably having 6 to 14 carbon atoms, eg
For example, a phenyl group). The following repeating formula (IV)
Specific examples of units are listed below.
Absent. [0184] Embedded image[0185] Embedded image Embedded image [0186] Embedded image[0187] Embedded image [0188] Embedded image [0189] Embedded image[0190] Embedded image [0191] Embedded image [0192] Embedded image [0193] Embedded image[0194] Embedded image[0195] Embedded image[0196] [Chemical Formula 86][0197] Embedded image[0198] Embedded image[0199] Embedded image[0200] Embedded image [0201] Embedded image[0202] Embedded image[0203] Embedded image[0204] Embedded image [0205] Embedded image The acid-decomposable resin as component (B) is as described above.
In addition to repeating structural units, dry etching resistance and standard
Developer suitability, substrate adhesion, resist profile,
In addition, resolution and heat resistance, which are general necessary properties of resists
Various repeating structural units for the purpose of adjusting properties, sensitivity, etc.
Can be contained. As such a repeating structural unit,
The repeating structural unit corresponding to the monomer
However, it is not limited to these. This
The performance required for acid-decomposable resins, especially (1) coating
Solubility in solvents, (2) film-forming properties (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
-Polymerizable unsaturation selected from vinyl esters, vinyl esters, etc.
Examples include compounds having one bond. Of the acid-decomposable resin, it is represented by the general formula (I)
The content of repeating units is 2 to 5 in all repeating structural units.
0 mol% is preferred, more preferably 4-45 mol%,
More preferably, it is 6-40 mol%. Formula (II)
The content of the repeating unit represented by
15-60 mol% is preferable in the position, more preferably 20
-55 mol%, more preferably 25-50 mol%
The The total amount of repeating units having an acid-decomposable group is
20 to 70 mol% in the returning structural unit is preferable, more preferable
25 to 65 mol%, more preferably 30 to 60 mol%.
Le%. Groups represented by formulas (pI) to (pVI)
The content of repeating units possessed by all repeating structural units
10-60 mol% is preferable, More preferably, 15-5
It is 0 mol%, More preferably, it is 20-40 mol%. one
The content of the repeating unit represented by the general formula (III) is
3 to 40 mol% is preferable in the repeating structural unit, and more preferable.
Preferably 5 to 35 mol%, more preferably 8 to 40 mol%.
%. Including the repeating unit represented by formula (IV)
The content is preferably 3 to 40 mol% in all repeating structural units.
More preferably 5 to 35 mol%, still more preferably 8
-40 mol%. Lactone residue or alicyclic lactone
The content of repeating units possessed by all repeating structural units
5-50 mol% is preferable, More preferably, it is 10-40
It is mol%, More preferably, it is 12-30 mol%. still,
When the composition of the present invention is for ArF exposure, to ArF light
From the viewpoint of transparency, the resin preferably has no aromatic group.
That's right. 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
The composition of the present invention such as
In an inert gas atmosphere such as nitrogen or argon
Heat as needed, commercially available radical initiator (azo-based start
Polymerization is started using an agent, peroxide, etc.).
Add initiator or add in portions as desired to react
After completion, put into solvent and recover powder or solid
To recover the desired polymer. The concentration of the reaction is 20% by weight
Or more, preferably 30% by weight or more, more preferably
Or 40% by weight or more. The reaction temperature is 10 ° C to 150 ° C.
° C, preferably 30 ° C to 120 ° C, more preferred
It is 50-100 degreeC. The weight average molecule of the acid-decomposable resin according to the present invention
The amount is preferred as a polystyrene conversion value by the GPC method.
1,000 to 200,000, preferably 3,0
00 to 50,000, more preferably 5,000 to 3
0,000. The weight average molecular weight is less than 1,000
Because deterioration of heat resistance and dry etching resistance is seen
It is not preferable, and if it exceeds 200,000, developability
Degradation and film forming properties deteriorate due to extremely high viscosity
Results in less favorable results. In the positive photosensitive composition of the present invention, the present
The compounding amount in the whole composition of the acid-decomposable resin according to the invention is:
40 to 99.99% by weight in the total solid content is preferred
More preferably, it is 50 to 99.97% by weight. [4] (C) Mixed solvent The positive photosensitive composition of the present invention is mixed as component (C)
Contains solvent. As this mixed solvent, propylene glycol
Small number of coal monoalkyl ether carboxylates
At least one type (also called Group A solvent) and propylene group
Recall monoalkyl ether, alkyl lactate and al
At least one of alkyl coxipropionates (B
And / or γ-butyrolactone,
Tylene carbonate and propylene carbonate (Group C
Can also be mentioned as a mixed solvent containing
it can. That is, the component (C) includes a group A solvent and a group B.
Combinations of solvents, combinations of Group A solvents and Group C solvents
Combination of Group A solvent, Group B solvent and Group C solvent
Use a match. Propylene glycol monoalkyl ether
As the carboxylate, propylene glycol
Nomethyl ether acetate, propylene glycol
Nomethyl ether propionate, propylene glycol
Lumonoethyl ether acetate, propylene glycol
Preferred is lumonoethyl ether propionate
be able to. Propylene glycol monoalkyl ether
Propylene glycol monomethyl ether
And propylene glycol monoethyl ether
Can be mentioned. Examples of alkyl lactate include lactate
Preferable examples include chill and ethyl lactate. Al
Examples of alkyl oxypropionate include 3-ethoxy
Ethyl lopionate, methyl 3-methoxypropionate,
Ethyl 3-methoxypropionate, 3-ethoxypropionate
A preferred example is methyl onate. The weight ratio of the solvent of the group A to the solvent of the group B
The ratio (A: B) is preferably 90: 10-15: 85,
More preferably, it is 85: 15-20: 80, and even more preferable
Preferably, it is 80: 20-25: 75. Group A
Weight ratio (A: C) of the agent and the solvent of Group C is 99.
9: 0.1-75: 25 is preferred, more preferably 9
9: 1 to 80:20, more preferably 97: 3 to
85:15. When combining these three solvents,
The weight ratio of the solvent of group C is 0.1 to the total solvent.
25% by weight is preferred, more preferably 1 to 20%
%, More preferably 3 to 17% by weight. In the present invention
The solid content of the composition containing the above components is mixed and dissolved.
It is preferable to dissolve 3 to 25% by weight as a solid content concentration in the agent.
More preferably, it is 5 to 22% by weight, more preferably
It is preferably 7 to 20% by weight. Propylene glycol mono in the present invention
Mixed solvent containing alkyl ether carboxylate
As a preferred combination of Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate +
Ethyl lactate Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate Propylene glycol monomethyl ether acetate +
γ-butyrolactone Propylene glycol monomethyl ether acetate +
Ethylene carbonate Propylene glycol monomethyl ether acetate +
Propylene carbonate Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + γ-butyro
Lactone Propylene glycol monomethyl ether acetate +
Ethyl lactate + γ-butyrolactone Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate + γ-butyrolacto
N Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + ethylene carbonate
-Bonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + ethylene carbonate Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate + ethylene carbonate
The Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + propylene
Carbonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + propylene carbonate Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate + propylene carbonate
Nate It is. Particularly preferred solvent combinations are: Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + γ-butyro
Lactone Propylene glycol monomethyl ether acetate +
Ethyl lactate + γ-butyrolactone Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate + γ-butyrolacto
N Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + ethylene carbonate
-Bonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + ethylene carbonate Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate + ethylene carbonate
The Propylene glycol monomethyl ether acetate +
Propylene glycol monomethyl ether + propylene
Carbonate Propylene glycol monomethyl ether acetate +
Ethyl lactate + propylene carbonate Propylene glycol monomethyl ether acetate +
3-Ethoxyethyl propionate + propylene carbonate
Nate It is. Each of the above mixed solvents of the present invention is effective for the present invention.
Add other non-essential solvents as long as they do not interfere with the results.
Good. The amount of such other solvents added is generally
30 parts by weight or less with respect to 100 parts by weight of each mixed solvent of the invention
It is. Other solvents are essential for each of the above mixed solvents.
In addition to the solvents exemplified as the solvent,
, Cyclohexanone, cyclopentanone, methyl ethyl
Ketone, toluene, N, N-dimethylformamide,
Dimethyl sulfoxide, N-methylpyrrolidone, tetra
And hydrofuran. [5] (D) Fluorine-based and / or silicon
Surfactants The positive photosensitive resin composition of the present invention has no pattern collapse.
Fluorine-based and / or
Or silicon surfactants (fluorine surfactants and
Recon surfactants, containing both fluorine and silicon atoms
One or two or more surfactants)
It is preferable to have. The positive photosensitive composition of the present invention is
By containing the (F) surfactant, 250
nm or less, particularly when using an exposure light source of 220 nm or less,
Good sensitivity and resolution, low adhesion and development defects
A resist pattern can be provided. these
(F) As a surfactant, for example, JP-A-62-36663,
Kaisho 61-226746, JP61-226745, JP62-170
950, JP 63-34540, JP 7-230165, JP 8
-62834, JP-A-9-54432, JP-A-9-5988, US
No. 5405720, 5360692, 5529881, 5296330
No. 5436098 No. 5576143 No. 5294511 No. 5824
The surfactant described in No. 451 can be mentioned, and the following commercially available products
These surfactants can also be used as they are. Can be used
For example, F-top EF301, E
F303 (made by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (Sumi
(Manufactured by Tomo 3M Co., Ltd.), Mega Fuck F171, F173, F17
6, F189, R08 (Dainippon Ink Co., Ltd.), Surflon S
-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass
Manufactured by Co., Ltd.), Troisol S-366 (Troy Chemical)
Fluorine-based surfactants or silicon-based interfaces
Mention may be made of activators. Also polysiloxane poly
Mar KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
It can be used as a surfactant. The amount of the surfactant used is the positive photosensitive composition.
Preferably 0.000, based on total amount of material (excluding solvent)
1 to 2 wt%, more preferably 0.001 to 1 wt%
is there. [6] (E) Acid-decomposable dissolution inhibiting compound The positive photosensitive composition of the present invention is (E) due to the action of acid.
Groups that decompose and increase solubility in alkaline developers
A dissolution inhibiting low molecular weight compound having a molecular weight of 3000 or less (hereinafter referred to as
And (also referred to as “(E) acid-decomposable dissolution inhibiting compound”).
It is preferable to have. Especially the transmittance of 220nm or less
Proceeding of SPIE, 2724,355 (19
96) Cholic acid derivatives containing acid-decomposable groups
An alicyclic or aliphatic compound containing an acid-decomposable group such as
Are preferred as (E) acid-decomposable dissolution inhibiting compounds. Acid content
The decomposable group and alicyclic structure include those of the above acid-decomposable resins.
The thing similar to what was described in the above is mentioned. (E) Acid
The decomposable dissolution inhibiting compound is added in a positive photosensitive composition.
Preferably 3 to 50% by weight, based on the solids content of the total composition
More preferably, it is 5 to 40% by weight. less than
(E) Specific examples of acid-decomposable dissolution inhibiting compounds are shown below.
It is not limited to it. [0223] Embedded image[7] (F) Nitrogen-containing basic compound The positive photosensitive composition of the present invention has a process from exposure to heating.
(F) Nitrogen-containing bases to reduce performance change over time
It is preferable to contain a functional compound. With a preferred structure
The structures represented by the following formulas (A) to (E)
Can do. [0225] Embedded image Where R²⁵⁰, R²⁵¹And R²⁵²Each
Vertically, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 1 carbon atom
-6 aminoalkyl group, hydroxyal having 1-6 carbon atoms
Kill group or substituted or unsubstituted ant having 6 to 20 carbon atoms
R group, where R²⁵⁰And R²⁵¹Are linked to each other
May be formed. [0227] Embedded image(Wherein R²⁵³, R²⁵⁴, R²⁵⁵And R
²⁵⁶Each independently represents an alkyl group having 1 to 6 carbon atoms.
) Preferred examples include substituted or unsubstituted
Guanidine, substituted or unsubstituted aminopyridine,
Substituted or unsubstituted aminoalkylpyridines, substituted
Or unsubstituted aminopyrrolidine, substituted or unsubstituted
Indazole, substituted or unsubstituted pyrazole, substituted
Or unsubstituted pyrazine, substituted or unsubstituted pyrazine
Midine, substituted or unsubstituted purine, substituted or unsubstituted
Substituted imidazoline, substituted or unsubstituted pyrazoly
Substituted or unsubstituted piperazine, substituted or unsubstituted
Substituted aminomorpholine, substituted or unsubstituted amino
Noalkyl morpholine, mono, di, tri
Alkylamine, substituted or unsubstituted aniline, substituted
Or unsubstituted piperidine, mono or diethano
And ruamine. Preferred substituents are amino
Group, aminoalkyl group, alkylamino group, amino ant
Group, arylamino group, alkyl group, alkoxy
Group, acyl group, acyloxy group, aryl group, aryl group
A xyl group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine,
1,1-dimethylguanidine, 1,1,3,3-teto
Lamethylguanidine, 2-aminopyridine, 3-amino
Pyridine, 4-aminopyridine, 2-dimethylaminopi
Lysine, 4-dimethylaminopyridine, 2-diethyla
Minopyridine, 2- (aminomethyl) pyridine, 2-a
Mino-3-methylpyridine, 2-amino-4-methylpi
Lysine, 2-amino-5-methylpyridine, 2-amino
-6-methylpyridine, 3-aminoethylpyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, pipette
Razine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidino
Piperidine, 2-iminopiperidine, 1- (2-amino
Ethyl) pyrrolidine, pyrazole, 3-amino-5-methyl
Tilpyrazole, 5-amino-3-methyl-1-p-to
Rilpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyri
Midine, 4,6-dihydroxypyrimidine, 2-pyrazo
Phosphorus, 3-pyrazoline, N-aminomorpholine, N-
(2-aminoethyl) morpholine, 1,5-diazabi
Cyclo [4.3.0] non-5-ene, 1,8-diaza
Bicyclo [5.4.0] undec-7-ene, 2,4,
5-triphenylimidazole, tri (n-butyl) a
Min, tri (n-octyl) amine, N-phenyldie
Tanolamine, N-hydroxyethylpiperidine,
2,6-diisopropylaniline, N-cyclohexyl
-N'-morpholinoethylthiourea
However, it is not limited to this. These (F) nitrogen-containing basic compounds are simple compounds.
Used alone or in combination of two or more. (F) Nitrogen-containing
The amount of basic compound used is the solid content of the photosensitive resin composition.
As a standard, usually 0.001 to 10% by weight, preferably
Is 0.01 to 5% by weight. Less than 0.001% by weight
The effect of adding the above nitrogen-containing basic compound cannot be obtained.
On the other hand, if the amount exceeds 10% by weight, the sensitivity decreases and the non-exposed area
There is a tendency for image quality to deteriorate. [8] (G) Alkali-soluble resin The composition of the present invention does not contain an acid-decomposable group,
(G) Contains a resin that is insoluble in water and soluble in an alkaline developer.
This improves the sensitivity. In the present invention
Novolak with a molecular weight of about 1000 to 20000
Resins, polyhydro with a molecular weight of about 3000 to 50000
Using xylstyrene derivatives as such resins
However, they absorb light below 250nm
Because it is large, use partly hydrogenated or all resin
It is preferably used in an amount of 30% by weight or less of the amount. Ma
In addition, it contains a carboxyl group as an alkali-soluble group
Resins can also be used. Contains a carboxyl group
In the resin, a single ring for improving dry etching resistance, or
Preferably has a polycyclic alicyclic hydrocarbon group.
Specifically, it has an alicyclic hydrocarbon structure that does not exhibit acid decomposability.
Of methacrylic acid ester and (meth) acrylic acid
Combined or alicyclic hydrocarbons having a carboxyl group at the end
Examples of basic (meth) acrylic acid ester resins
be able to. [9] Other additives In the positive photosensitive composition of the present invention, if necessary, further
Dyes, plasticizers, surfactants other than the above component (D), photosensitizing
Sensitizers, compounds that promote solubility in developers, etc.
Can be contained. Developer that can be used in the present invention
Is a phenolic OH group.
1 or more, or molecular weight having one or more carboxy groups,
It is a low molecular compound of 000 or less. Has a carboxy group
Alicyclic or aliphatic compounds are preferred for the same reason as above.
Good. The preferred addition amount of these dissolution promoting compounds is
(A) 2 to 50% by weight based on the acid-decomposable resin,
More preferably, it is 5 to 30% by weight. Over 50% by weight
With the added amount, the development residue deteriorates, and the pattern during development
A new disadvantage of deforming the
Yes. Such a pheno having a molecular weight of 1000 or less
For example, JP-A-4-122938,
2-28531, US Pat. No. 4,916,210, European patent
With reference to the methods described in No. 219294, etc., those skilled in the art
Can be easily synthesized. Carboxyl group
Specific examples of the alicyclic or aliphatic compound having
Steroids such as formic acid, deoxycholic acid, lithocholic acid
Carboxylic acid derivative having a amide structure, adamantanecarbo
Acid derivatives, adamantane dicarboxylic acid, cyclohexa
Carboxylic acid, cyclohexanedicarboxylic acid, etc.
However, it is not limited to these. In the present invention, the above (D) fluorine-based and
And / or other surfactants other than silicon surfactants
It can also be added. Specifically, polyoxyethylene
Lauryl ether, polyoxyethylene stearyl ether
Tellurium, polyoxyethylene cetyl ether, polyoxy
Polyoxyethylene alcohol such as ethylene oleyl ether
Kill ethers, polyoxyethylene octylphenol
Ether, polyoxyethylene nonylphenol A
Polyoxyethylene alkyl allyl ether such as Tell
Polyoxyethylene / polyoxypropylene block
Copolymers, sorbitan monolaurate, sorbita
Monopalmitate, sorbitan monostearate,
Rubitan monooleate, sorbitan trioleate,
Sorbitan fatty acid ester such as sorbitan tristearate
Tells, polyoxyethylene sorbitan monolaurate
Polyoxyethylene sorbitan monopalmitate,
Polyoxyethylene sorbitan monostearate, poly
Oxyethylene sorbitan trioleate, polyoxy
Polyoxye such as ethylene sorbitan tristearate
Nonionic interfaces such as tylene sorbitan fatty acid esters
An activator etc. can be mentioned. These surfactants are
It can be added alone or in some combination
Can also be added. The positive photosensitive composition dissolved in the solvent is
It is applied on a fixed substrate as follows. That is, the above
The photosensitive composition is used in the manufacture of precision integrated circuit devices.
On a substrate (eg silicon / silicon dioxide coating)
Apply by an appropriate coating method such as pinner or coater.
After coating, expose through a specified mask, bake and
Image. In this way, a good resist pattern
Can be obtained. The exposure light here is preferably
Wavelength of 250 nm or less, more preferably 220 nm or less
Of far ultraviolet rays. Specifically, KrF excimer laser
-(248nm), ArF excimer laser (193n
m), F₂Excimer laser (157 nm), X-ray, electricity
A child beam etc. are mentioned. As the developer in the development process, hydroxylation is used.
Sodium, potassium hydroxide, sodium carbonate, silicic acid
Sodium, sodium metasilicate, ammonia water, etc.
Inorganic alkalis, ethylamine, n-propylamine, etc.
Primary amines, diethylamine, di-n-butylamino
Secondary amines such as ethylene, triethylamine, methyldiethyl
Tertiary amines such as ruamine, dimethylethanolamine
Alcohol amines such as ethanol and triethanolamine,
Tramethylammonium hydroxide, tetraethyla
Quaternary ammonium salts such as ammonium hydroxide,
Alkaline water such as cyclic amines such as rolls and pihelidine
A solution can be used. Furthermore, the alkaline
Add appropriate amounts of alcohol and surfactant to the aqueous solution.
It can also be used. [0237] EXAMPLES Hereinafter, the present invention will be described in detail based on examples.
As will be apparent, the scope of the present invention is somewhat limited by the examples.
Not limited. Synthesis of resin (1) Acetoxyethyl vinyl ether, maleic anhydride,
Rubornene carboxylic acid tBu ester at a molar ratio of 10 /
Charge the reaction vessel at 50/40 and add to tetrahydrofuran.
Dissolved to prepare a 40% solids solution. This is nitrogen
Heated at 65 ° C. under flow. When the reaction temperature is stable,
1 mol% of radical initiator V-601 made by Kojun Pharmaceutical Co., Ltd. was added
The reaction was started. After heating for 14 hours, the reaction mixture is
After diluting twice with tetrahydrofuran, the reaction mixture
Pour into 10 times volume hexane / ethyl acetate = 9/1 combined solution
And white powder was deposited. Precipitated powder is filtered out
This is dissolved in tetrahydrofuran and 10 times the volume
Reprecipitate in hexane / ethyl acetate = 9/1 mixed solvent
The resulting white powder was collected by filtration, dried, and the target resin (1)
Got. Molecular weight analysis of the obtained resin (1) by GPC
Of 9200 in terms of polystyrene (weight average
Average). Moreover, resin (1) from NMR spectrum
The composition of acetoxyethyl vinyl ether / maleic anhydride
Acid / norbornenecarboxylic acid tBu ester = 12 /
51/37 (molar ratio). Same as synthesis example (1)
Resins (2) to (12) were synthesized by the following method. (Repetition
The return unit is the order from the left of the structural formula. ) [0239] [Table 1]The structures of the resins (1) to (12) are as follows:
Show. [0241] Embedded image[0242] Embedded image[0243] Embedded image<Resist preparation> Examples 1-12 and Comparative Examples 1 and 2 (Preparation and evaluation of positive resist composition) Shown in Table 2
Resin synthesized in the above synthesis example (2 g), photoacid generator
(Amount shown in Table 2), organic basic compound (4 mg), necessary
Add surfactant (5mg) if necessary, solid content 12 layers
After dissolving in the solvent shown in Table 2 so that the amount becomes 0%, 0.
Filter with a 1 μm microfilter and Examples 1-12
The positive resist compositions of Comparative Examples 1 and 2 were prepared.
In addition, the ratio at the time of multiple use about each component in Table 2 is
It is a weight ratio. [0245] [Table 2](Description of Table 2) Resin R1 is disclosed in JP-A-2001.
According to Synthesis Example 6 (Sample No. 2) of No. 200016
The resin having the following repeating units prepared in the above manner. [0247] Embedded image The acid generator is the compound exemplified above. However
The PAGs 1 and 2 used in Comparative Examples 1 and 2 are as follows:
It is a compound of this. [0249] Embedded image The symbols for the surfactant are as follows. W1: Megafuck 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) Symbols for basic compounds are as follows:
The E1: 1,5-diazabicyclo [4.3.0] -5-no
Nen (DBN) E2: N, N-bis (2-pyroxyethyl) aniline E3: Trioctylamine E4: Triphenylimidazole E5: Antipyrine E6: 2,6-diisopropylaniline E7: Triisobutylamine E8: Triisodecylamine Symbols for the solvent are as follows. S1: Propylene glycol monomethyl ether acetate
The S2: Ethyl lactate S3: Butyl acetate S4: 2-heptanone S5: Propylene glycol monomethyl ether S6: Ethyl ethoxypropionate S7: γ-butyrolactone S8: Ethylene carbonate S9: Propylene carbonate (Evaluation test) [Development defects] First Brewer as antireflection film
Use ARC-29 from Science as a spin coater
Applied to a silicon wafer at 85 nm and dried.
After that, apply the positive resist composition obtained on it,
Bake at 130 ° C for 90 seconds and coat with a film thickness of 0.40μm
did. Next, 0.20 μm contact hole pattern
Via a test mask (Hole Duty ratio = 1: 3)
ArF excimer laser stepper (ISI A
rF exposure machine 9300) after exposure and then post-exposure heating
Performed at 130 ° C. for 90 seconds. 2.38% by weight T
MAH (tetramethylammonium hydroxide in water
Solution) for 45 seconds and then washed with pure water for 20 seconds.
Spin dried. Antireflection of the sample obtained in this way
The number of development defects remaining on the film
Measured with a KLA-2112 machine manufactured by Le Co., Ltd.
The primary data value was defined as the number of development defects. [Side lobe light resistance] As an antireflection film
Brewer Science ARC-29
85nm on a Bare Si substrate using a coater
Then, each resist film is applied to 0.40 μm.
Cloth and vacuum suction hot plate at 130 ° C for 60 seconds
Dried. Next, 0.180 μm contact hole pattern
Half-hole (Hole Duty ratio = 1: 10)
Through an I-mask (80% transmittance)
Exposed with a tepper. After exposure, at 130 ° C for 60 seconds
Followed by 2.38 wt% TMAH
After paddle development for 60 seconds, spin with pure water for 30 seconds and spin
Images were obtained by drying. At this time, the diameter of 0.18 μm
Retained contact hole (mask) to 0.14 μm
The exposure amount that appears is the optimum exposure amount Eopt, and the side exposure
Eli is the minimum amount of exposure that can be transferred onto the resist substrate
mit and their ratio Elimit / Eopt
It was used as an index of light resistance. At this time, the value of Comparative Example 1 was set to 1.
Other sidelobe light by standardization and relative evaluation with it
Showed tolerance. The larger this value is, the more resistant the sidelobe light is.
Excellent, smaller means less. [Profile] Bre as an antireflection film
spin code ARC-29 manufactured by weScience
85nm film thickness on Bare Si substrate
Then, each resist film is applied to 0.30 μm,
Dry on a vacuum adsorption hot plate at 130 ° C for 60 seconds
It was. Next, 0.130 μm line and space (La
In / space = 1/10) through ISI
It exposed with the ArF stepper made from. After exposure, 130
Heat treatment for 60 seconds at ℃, followed by 2.38 weight
After 60 seconds paddle development with% TMAH, 30 seconds with pure water
Images were obtained by washing with water and spin drying. The resulting pattern
The cross section was evaluated with a scanning electron microscope (SEM).
It was. [Pattern collapse] Bre as an antireflection film
spin code ARC-29 manufactured by weScience
85nm film thickness on Bare Si substrate
Then, each resist film is applied to 0.30 μm,
Dry on a vacuum adsorption hot plate at 130 ° C for 60 seconds
It was. Next, 0.130 μm line and space (La
Made by ISI through a mask of in / space = 1/1)
Exposed with an ArF stepper. 130 ° C after exposure,
Heat treatment for 60 seconds, followed by 2.38 wt% T
After paddle development with MAH for 60 seconds, rinse with pure water for 30 seconds
Images were obtained by spin drying. Pattern during overexposure
The maximum line width that causes the fall of the pattern
did. The results are shown in Table 3. [0257] [Table 3]From the results shown in Table 3, the composition of the present invention
Is excellent in the above properties. [0259] The present invention provides development defects and sidelobe light resistance.
Positive photosensitive composition with significantly improved performance, and further
Forms a good profile without causing turnover
To provide a positive photosensitive composition that can be formed
Can do. Therefore, the positive photosensitive composition of the present invention is
Miku using ultraviolet light, especially ArF excimer laser light
It is suitably used for low photofabrication.

─────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme code (reference) G03F 7/004 503 G03F 7/004 503A H01L 21/027 H01L 21/30 502R F-term (reference) 2H025 AA03 AA04 AB16 AC04 AC08 AD03 BE07 BE10 BG00 CB08 CB10 CB41 CC03 4J100 AE02P AE04P AE06P AE09P AE10P AK32Q AL08R AL08S AM43Q AM45Q AM47Q AR11R AR32P AR32R BA03P BA03Q BA03S BA05P BA06P BA10P BA11Q BA11S BA15P BA15R BA20R BA40S BA55Q BB01P BB18Q BC04P BC08P BC08Q BC09P BC09R BC09S BC12P BC12R BC53P BC53S CA04 CA05 CA06 JA38

Claims (1)

[Claims] (A) Actinic rays represented by the general formula (SI)
Or a compound that generates an acid upon irradiation with radiation, and
(B) Repeating unit represented by general formula (I) and general formula
(II) having a repeating unit represented by the action of an acid
Which decomposes and increases its solubility in alkaline developer
And (C) at least selected from the following solvent A group
1 type and at least 1 type selected from the following solvent B group
At least selected from a mixed solvent or solvent A group
And at least one selected from the following solvent C group:
Positive type characterized by containing a mixed solvent containing
Photosensitive composition. Group A: Propylene glycol monoalkyl ether al
Coxilate Group B: propylene glycol monoalkyl ether, milk
Alkyl acids and alkoxypropionates Group C: γ-butyrolactone, ethylene carbonate, and
Propylene carbonate [Chemical 1] [Chemical 2] In general formula (SI), Rs_Four~ Rs₆Each independently
Kill group, cycloalkyl group, alkoxy group, alkoxy
Carbonyl group, acyl group, acyloxy group, nitro group,
Represents a rogen atom, a hydroxyl group, or a carboxyl group; l: 1-5 m: 0 to 5 n represents 0-5. When l + m + n = 1, Rs_FourIs an alkyl group, cycloal
Kill group, alkoxy group, alkoxycarbonyl group,
Represents an alkyl group or an acyloxy group. Xs^-: R-SO_Three ^-, R: represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In general formula (I), R_1aHas a hydrogen atom or substituent
Represents an optionally substituted hydrocarbon group, R_2aHas a substituent
Represents a hydrocarbon group that may be present. R_1aAnd R _2aAnd each other
May be combined to form a ring. In general formula (II)
Z is —O— or —N (R_3a)-. here
R _3aIs a hydrogen atom, hydroxyl group, alkyl group, haloalkyl
Group or -OSO₂-R_4aRepresents. Also R_4aIs an alkyl
Group, haloalkyl group, cycloalkyl group or camphor residue
Represent.